Membrane-normal-temperature hydrogen regeneration redox resin deoxidizing device

Abstract

The utility model discloses a membrane-normal-temperature hydrogen regeneration redox resin deoxygenization device. The device comprises a pre-deoxygenization device, a hydrogenation device, a normal-temperature hydrogen regeneration redox resin chemical deoxygenization device and a deoxygenization water tank which are sequentially connected and arranged in a process, the hydrogenation device comprises a cylinder, hydrogenation hollow fiber membrane tubes and end covers, the end covers are arranged at the two ends of the cylinder, and the hydrogenation hollow fiber membrane tubes are arranged in the cylinder; a water chamber is arranged in the hydrogenation hollow fiber membrane tube, and a gas chamber is arranged between the hydrogenation hollow fiber membrane tube and the cylinder body; one end of the water chamber is connected with the pre-deaerator water outlet pipe, and the other end is connected with the hydrogenated water output pipe; the gas chamber is connected with a hydrogen source. The device does not consume steam, is low in electricity consumption, saves energy and water, and only consumes 0.01 kgce / t of deoxygenization energy for each ton of water.

Description

Technical Field

[0001] The utility model belongs to the field of water treatment technology and equipment, and particularly relates to a membrane-normal temperature hydrogenation regeneration redox resin deoxidation device which combines physical and chemical deoxidation principles. Background Art

[0002] Dissolved oxygen in water will cause electrochemical reactions on the surfaces of metals such as steel and copper, causing corrosion. Taking steel as an example, the specific process is that cementite is used as the anode, ferrite absorbs oxygen as the cathode, and countless primary cells are formed through the transmission of chemical currents of anions and cations in water, causing the surface of steel to be corroded. Because this electrochemical corrosion is non-uniform corrosion, many small pits will eventually form on the steel, causing perforation of boiler equipment. Therefore, for industrial boilers, medium and high pressure boilers in power plants, and ultra-high pressure boilers, there are strict regulations on the residual oxygen content in boiler feed water. According to the national standard GB1576-2018 "Boiler Water Quality Standard": The oxygen content of hot water boiler feed water is ≤100ppb, the oxygen content of low-pressure steam boiler feed water is ≤50ppb, the oxygen content of medium-pressure steam boiler feed water is ≤15ppb, the oxygen content of high-pressure boiler feed water is ≤7ppb, and the oxygen content of ultra-high pressure boiler feed water is ≤5ppb. For the cooling of microwave tubes in the electronics industry, the dissolved oxygen in ultra-pure water is ≤50ppb. Utility Model Content

[0003] The utility model aims to provide a membrane-normal temperature hydrogenation regeneration redox resin deoxygenation device. The utility model is a deoxygenation device which can continuously produce deoxygenated water, the amount of hydrogen in the water can be effectively controlled, and the production and operation safety is improved.

[0004] In order to achieve the above purpose, the utility model adopts the following technical solutions:

[0005] A membrane-normal temperature hydrogen regeneration redox resin deoxygenation device, the device comprising a pre-deoxygenator, a hydrogenator, a normal temperature hydrogen regeneration redox resin chemical deoxygenator and a deoxygenation water tank which are sequentially connected and arranged in a process;

[0006] The hydrogenator comprises a cylinder, a hydrogenation hollow fiber membrane tube and an end cap, the end caps are arranged at both ends of the cylinder, and the hydrogenation hollow fiber membrane tube is arranged in the cylinder; the interior of the hydrogenation hollow fiber membrane tube is a water chamber, and the space between the hydrogenation hollow fiber membrane tube and the cylinder is an air chamber; one end of the water chamber is connected to the water outlet pipe of the pre-deaerator, and the other end is connected to the hydrogenation water output pipe; the air chamber is connected to the hydrogen source;

[0007] The hydrogenated water output pipe is connected to the water inlet flange of the normal temperature hydrogen regeneration redox resin chemical deoxygenator, the water outlet flange of the normal temperature hydrogen regeneration redox resin chemical deoxygenator is connected to the water inlet of the deoxygenated water tank through the deoxygenator water outlet pipe, and a deoxygenator water intake valve and a deoxygenator oxygen meter are arranged on the deoxygenator water outlet pipe;

[0008] The room temperature hydrogen regeneration redox resin chemical deaerator comprises a cylinder, an upper head and a lower head are respectively arranged at both ends of the cylinder, an upper water distribution pan is arranged at the connection between the upper head and the cylinder on the upper part of the cylinder, and a lower water distribution pan is arranged at the connection between the lower head and the cylinder on the lower part of the cylinder, and room temperature hydrogen regeneration redox resin is filled between the upper water distribution pan and the lower water distribution pan; a plurality of filter caps are respectively arranged on the upper water distribution pan and the lower water distribution pan; the upper water distribution pan is connected to the upper water pipe, and the lower water distribution pan is connected to the lower water pipe; the upper water pipe is connected to the water inlet flange through the water inlet tee, and the upper water pipe is connected to the water outlet flange through the water outlet tee; the lower water pipe is connected to the water inlet flange through the water inlet tee, and the lower water pipe is connected to the water outlet flange through the water outlet tee.

[0009] Further, the pre-deaerator comprises a pre-deaerator body, a water ring vacuum pump steam-water separator, a water ring vacuum pump, and a chiller;

[0010] The pre-deaerator body is connected to a water source via a water inlet pipe;

[0011] The pre-deaerator body is connected to the water ring vacuum pump through an exhaust pipe, the water ring vacuum pump is connected to the water ring vacuum pump steam-water separator through a pipeline, the water ring vacuum pump is connected to the chiller through a chiller output pipe and a chiller return pipe respectively, the chiller is connected to the water ring vacuum pump steam-water separator through a steam-water separator return pipe; a water ring vacuum pump exhaust valve is arranged on the water ring vacuum pump steam-water separator;

[0012] The air extraction pipe is provided with a water ring vacuum pump solenoid valve and a vacuum pressure gauge;

[0013] The pre-deaerator body is connected to the hydrogenator through the pre-deaerator water outlet pipe.

[0014] Furthermore, a pre-deoxygenation hollow fiber membrane tube is arranged in the pre-deoxygenation hollow fiber membrane tube, the inside of the pre-deoxygenation hollow fiber membrane tube is an air chamber connected to the air extraction pipe; the outside of the pre-deoxygenation hollow fiber membrane tube is a water chamber connected to the water inlet pipe.

[0015] Furthermore, a water inlet valve, a pipeline pump and a water pressure gauge are sequentially arranged on the water inlet pipe, a raw water sampling valve and a raw water oxygen meter are arranged on the water inlet pipe between the water inlet valve and the pipeline pump; a pre-deaerator water outlet sampling valve and a pre-deoxygenated water oxygen meter are arranged on the pre-deaerator water outlet pipe.

[0016] Furthermore, the hydrogen source includes a hydrogen cylinder, which is connected to the gas chamber of the hydrogenator through a hydrogenation pipe; the hydrogenation pipe is provided with a hydrogen solenoid valve, a hydrogen flowmeter, a hydrogen regulating valve, a low-pressure hydrogen pressure gauge, a high-pressure hydrogen pressure gauge, and a hydrogen main valve.

[0017] Furthermore, an upper water inlet valve is arranged on the water inlet tee connecting the water inlet flange and the upper water pipe, and a lower water inlet valve is arranged on the water inlet tee connecting the water inlet flange and the lower water pipe; an upper water outlet valve is arranged on the water outlet tee connecting the water outlet flange and the upper water pipe, and a lower water outlet valve is arranged on the water outlet tee connecting the water outlet flange and the lower water pipe.

[0018] Furthermore, the deoxygenated water tank comprises a water tank body, a water tank top cover, and an isolating air bag; the water tank top cover is arranged on the top of the water tank body, and the isolating air bag is arranged on the inner side of the water tank top cover.

[0019] Furthermore, a liquid level gauge is arranged on the water tank body, the water tank body is connected to a water-using device via a water tank outlet pipe, and a water tank outlet valve and a water supply pump are arranged on the water tank outlet pipe.

[0020] The utility model further provides a membrane-normal temperature hydrogen regeneration redox resin deoxygenation method, the deoxygenation method comprising:

[0021] 1) Pre-deoxygenation:

[0022] The raw water enters the water chamber of the pre-deaerator through the water inlet pipe, and the water ring vacuum pump is turned on to evacuate the air chamber. The dissolved oxygen in the water flowing along the wall of the pre-deaerator hollow fiber membrane tube in the water chamber quickly diffuses into the hollow fiber membrane tube through the microporous water film on the wall of the pre-deaerator hollow fiber membrane tube, and is then vacuumed away by the water ring vacuum pump; the steam-water mixture discharged by the water ring vacuum pump enters the steam-water separator of the water ring vacuum pump, and the steam is discharged from the exhaust valve after separation, and part of the dissolved oxygen in the water is also discharged;

[0023] 2) Hydrogenation:

[0024] Hydrogen enters the hydrogenator gas chamber from the hydrogen source, pre-deoxygenated water enters the water chamber of the hydrogenator, water flows in the hydrogenation hollow fiber membrane tube, hydrogen is outside the hydrogenation hollow fiber membrane tube wall, water is hydrogenated in the process of flowing from the water chamber at one end of the hydrogenator to the water chamber at the other end, and the water with hydrogen enters the normal temperature hydrogen regeneration redox resin chemical deoxygenator through the hydrogenation water output pipe;

[0025] 3) Chemical deoxidation:

[0026] The operation of the room temperature hydrogen regeneration redox resin chemical deaerator is co-current or counter-current. The hydrogenated water is further deoxygenated by the room temperature hydrogen regeneration redox resin filled in the deaerator. The deoxygenated water enters the deoxygenation water tank through the outlet flange. The residual oxygen content in the water after deoxygenation by the room temperature hydrogen regeneration redox resin chemical deaerator is ≤5ppb.

[0027] 4) Deoxygenated water storage:

[0028] The deoxygenated water is stored in a deoxygenated water tank for use.

[0029] The utility model provides a membrane-normal temperature hydrogen regeneration redox resin deoxygenation device, comprising a pre-deoxygenator (physical deoxygenation technology equipment), a hydrogenator, a normal temperature hydrogen regeneration redox resin chemical deoxygenator (chemical deoxygenation technology equipment) and a deoxygenation water tank, which are arranged in sequence in the process.

[0030] 1) Pre-deaerator:

[0031] In the above membrane-normal temperature hydrogen regeneration redox resin deoxygenation device, the pre-deoxygenator is started, raw water (deionized water or softened water) is passed into the water chamber of the pre-deoxygenator, and the air in the air chamber is pumped out using a water ring vacuum pump. The hollow fiber membrane tube wall in the pre-deoxygenator is covered with micropores with a diameter of 20 to 50 nanometers. Due to the hydrophobicity of the hollow fiber membrane tube material, the water outside the tube cannot enter the tube through the tube wall holes, but the gas dissolved in the water outside the tube can enter the tube through the micropores. When the water outside the tube flows through the outside of the fiber membrane tube in a turbulent state, when the tube is evacuated, the dissolved oxygen in the water enters the tube through the micropores and is discharged into the atmosphere with the evacuated gas, completing the pre-deoxygenation process.

[0032] 2) Redox resin deaerator with hydrogen reduction regeneration

[0033] Deoxygenation principle: dissolved oxygen in water and dissolved hydrogen in water undergo redox reaction on the reduced redox resin. The reaction formula is as follows:

[0034] O2+2H2=2H2O;

[0035] The redox resin deaerator is a deaerator equipped with a 1000mm layer of reduced redox resin. Water flows through the resin bed with a residence time of 30 to 60 seconds and a deoxygenation temperature of room temperature (5 to 40°C). The deoxygenation reaction of the reduced redox resin is as follows:

[0036] Assume R is a polymer skeleton, palladium is adsorbed on the skeleton in the state of metal atoms, and one palladium atom can adsorb about 700 hydrogen molecules to form a hydrogen-palladium coordination compound, which reacts with dissolved oxygen in water to generate water. The reaction equation is as follows:

[0037] 2R-[PdH2] n +n2O2=2nH2O;

[0038] The coordination compound formed by the dissolved hydrogen in water and the palladium atoms on the palladium resin is a reducing functional group. The higher the hydrogen concentration, the more reducing functional groups on the resin, the greater the deoxygenation capacity, and the better the deoxygenation effect. According to the reaction equation, as long as the molar amount of dissolved hydrogen in water is slightly greater than the molar amount of dissolved oxygen in water, the reaction will occur and the purpose of deoxygenation will be achieved.

[0039] In the hydrogen regeneration redox resin deoxygenation device and deoxygenation method provided by the utility model, the hydrogen regeneration resin utilizes membrane hydrogenation to make the hydrogenation amount controllable, and the hydrogen content in the water after deoxygenation is also controllable, thereby ensuring production safety while deoxygenating.

[0040] The steps of the utility model deoxygenation method are as follows:

[0041] The raw water first enters the pre-deaerator for pre-deoxygenation, then is hydrogenated, and then enters the redox resin deaerator for further deoxygenation. The qualified deoxygenated water after deoxygenation enters the deoxygenation water tank for storage. The specific steps are as follows:

[0042] 1. Pre-deoxygenation:

[0043] Turn on the water ring vacuum pump to remove the air in the air chamber of the pre-deaerator. The raw water oxygen meter can measure the oxygen content (mg / L) in the raw water. Turn on the pipeline pump to increase the raw water pressure to 0.3-0.6MP. The raw water enters the water chamber of the pre-deaerator through the water inlet pipe and flows out from the pre-deaerator outlet pipe at the other end. The pre-deaerator outlet pipe is equipped with a pre-deaerator outlet water sampling valve and a pre-deaerator outlet water oxygen meter. According to the value of the pre-deaerator outlet water oxygen meter, adjust the vacuum degree so that the oxygen content in the water is less than 2ppm. The pre-deaerator outlet pipe is connected to the water inlet pipe of the hydrogenator. If the ambient temperature is too high, the chiller needs to be turned on before the deaerator is operated to take cold water below 15 degrees for the water ring vacuum pump. The oxygen in the air chamber of the pre-deaerator is sucked in by the water ring vacuum pump and enters the water ring vacuum pump steam-water separator, where steam and water are separated. Oxygen is discharged from the exhaust valve along with the air, and the separated water returns to the chiller tank for use in the chiller.

[0044] 2. Membrane hydrogenation:

[0045] The pre-deoxygenated water enters the hydrogenator for hydrogenation treatment. The hydrogenator consists of a stainless steel shell, a hydrogenation hollow fiber membrane tube and a stainless steel end cap. The pre-deoxygenated water is hydrogenated, and the hydrogen content is controlled at 0.5-1 mg / L, and then enters the redox resin deoxygenator for further deoxygenation.

[0046] 3. Resin deaerator deoxygenation:

[0047] The resin deaerator can be operated in both downstream and reverse flow. The deaerator is filled with hydrogen-reduced redox resin. The hydrogenated water enters the resin deaerator through the hydrogenated water output pipe, and a hydrogenated water flowmeter is provided on the pipe. The upper water inlet valve of the resin deaerator is opened, and the hydrogenated water enters the deaerator through the upper water pipe. The lower water outlet valve is opened, and the deoxygenated water enters the deoxygenated water tank through the lower water pipe. Alternatively, the lower water inlet valve of the resin deaerator is opened, and the hydrogenated water enters the deaerator through the lower water pipe. The upper water outlet valve is opened, and the deoxygenated water enters the deoxygenated water tank through the upper water pipe. A deoxygenated water sampling valve and a deoxygenated water oxygen meter are provided on the pipeline where the deoxygenated water enters the deoxygenated water tank, and the deoxygenated water oxygen meter reads the residual oxygen content of the deoxygenated water. The residual oxygen content in the water can be controlled by adjusting the hydrogen regulating valve so that the deoxygenated water meets the qualified requirements.

[0048] 4. Deaeration water tank:

[0049] The water deoxygenated by the hydrogen-regenerated redox resin deaerator is stored in the deoxygenated water tank for use by the water-using device (which can be a boiler). A water tank outlet valve is set on the outlet pipe of the deoxygenated water tank. The downstream of the water tank outlet valve is connected to a feed water pump to supply water to the boiler. When the liquid level in the deoxygenated water tank rises, the air in the air-isolating airbag is discharged through the suction and exhaust pipes; when the liquid level in the deoxygenated water tank decreases, the air-isolating airbag sucks air into the airbag through the suction and exhaust pipes. The airbag and the water tank form a sealed system so that the water in the water tank is never in contact with the air, so as to ensure the quality of the deoxygenated water.

[0050] 5. The utility model may further include an electric control cabinet to control various solenoid valves, water ring vacuum pumps, chillers, oxygen meters, liquid level meters, and hydrogen regulating valves to achieve automatic control.

[0051] The utility model relates to a redox resin deoxidation device and a deoxidation method for membrane-hydrogen reduction regeneration at room temperature, and the equipment includes a membrane physical pre-deoxidizer and a chemical deoxidizer for redox resin regeneration by membrane hydrogenation reduction at room temperature. The utility model is improved on the basis of the company's previous invention patents ZL9522264.3 "Redox resin deoxidizer" and ZL201310078532.2 "Redox resin membrane deoxidation device and deoxidation method" and ZL00135755.7 spherical hydrazine coordinated sulfonated phenolic type redox resin preparation method.

[0052] Features of the utility model: 1. A membrane pre-deoxygenator is added to the equipment; 2. Quantitative hydrogenation is performed by membrane method; 3. The residual oxygen content in the deoxygenated water can be less than 5pp; 4. The hydrogen content in the deoxygenated water is less than 0.1ppm; 5. The amount of redox resin used for hydrogen reduction is significantly reduced; 5. No electrolyte is added to the deoxygenated water. The membrane hydrogenation technology adopted in the utility model increases the contact area between hydrogen and water, making hydrogen more soluble in water. After the water passes through the membrane pre-deoxygenation device, about 80% of the dissolved oxygen can be removed, and the remaining dissolved oxygen is then removed by the redox resin regenerated by hydrogen reduction. This saves the amount of deoxygenation resin used and reduces the cost of deoxygenation. In addition, the equipment can also remove 50% of the CO2 dissolved in the water while deoxygenating.

[0053] The deoxygenation device and deoxygenation method provided by the utility model have the following advantages:

[0054] The utility model has the characteristics of a membrane separation deaerator and a hydrogen regeneration redox resin deaerator, fully combines the advantages of physical deoxygenation and chemical deoxygenation, overcomes the disadvantage of low hydrogen dissolution efficiency of the hydrogenation method in Chinese patent ZL95222624.3, and the membrane hydrogenation component used greatly increases the hydrogen-water contact area, accelerates the hydrogen dissolution rate, and eliminates the hydrogenation water spray pump. Since the utility model adopts a pre-deaerator, the amount of redox resin palladium resin used for hydrogen regeneration is significantly reduced, thereby greatly reducing the deoxygenation cost. The oxygen content in the deoxygenated water produced by the utility model is ≤5ppb, and no electrolyte is added to the deoxygenated water. The utility model technology is also fully in line with green environmental protection, energy saving and carbon reduction. Because it is room temperature deoxygenation, compared with the currently commonly used thermal deoxygenation, it does not consume steam, consumes less electricity, saves energy and water, and the energy consumption for deoxygenation per ton of water is only 0.01kgce / t. BRIEF DESCRIPTION OF THE DRAWINGS

[0055] Figure 1 This is a schematic diagram of the structure of the membrane-normal temperature hydrogen regeneration redox resin deoxygenation device of the utility model;

[0056] Figure 2 It is a schematic diagram of deoxygenation of the pre-deoxygenated hollow fiber membrane tube;

[0057] Figure 3 A front view of a normal temperature hydrogen regeneration redox resin chemical deaerator of the utility model;

[0058] Figure 4 It is a side view of the room temperature hydrogen regeneration redox resin chemical deaerator of the utility model.

[0059] Figure numerals: 1, pre-deaerator; 1-1, water inlet valve; 1-2, sampling valve; 1-3, raw water oxygen meter; 1-4, pipeline pump; 1-5, water inlet pipe; 1-6, exhaust pipe; 1-7, water ring vacuum pump solenoid valve; 1-8, vacuum pressure gauge; 1-9, water ring vacuum pump steam-water separator; 1-10, water ring vacuum pump exhaust valve; 1-11, water ring vacuum pump; 1-12, chiller; 1-13, cold water output pipe; 1-14, chiller return pipe; 1-15, steam-water separator return pipe; 1-16, pre-deaerator outlet pipe; 1-17, pre-deaerator outlet water oxygen meter; 1-18, water pressure gauge;

[0060] 2. Hydrogenator; 2-1. Hydrogenation pipe; 2-2. Hydrogenation water flow meter; 2-3. Hydrogenation water output pipe; 2-4. Hydrogen solenoid valve; 2-5. Hydrogen flow meter; 2-6. Hydrogen regulating valve; 2-7. Low-pressure hydrogen meter; 2-8. High-pressure hydrogen meter; 2-9. Hydrogen main valve; 2-10. Hydrogen cylinder;

[0061] 3. Resin deaerator; 3-1. Cylinder; 3-2. Water inlet flange; 3-3. Water outlet flange; 3-4. Upper head; 3-5. Lower head; 3-6. Upper water pipe; 3-7. Lower water pipe; 3-8. Upper water distribution tray; 3-9. Lower water distribution tray; 3-10. Filter cap; 3-11. Water inlet tee; 3-12. Water outlet tee; 3-13. Upper water inlet valve; 3-14. Upper water outlet valve; 3-15. Lower water inlet valve; 3-16. Lower water outlet valve; 3-17. Resin installation flange assembly; 3-18. Resin removal flange assembly; 3-19. Deaerator outlet pipe; 3-20. Deoxygenated water sampling valve; 3-21. Deoxygenated water oxygen meter; 3-22. Deaerator exhaust pipe;

[0062] 4. Deoxygenated water tank; 4-1. Water tank body; 4-2. Water tank top cover; 4-3. Air isolation airbag; 4-4. Liquid level gauge; 4-5. Water tank outlet valve; 4-6. Water supply pump; 4-7. Air intake and exhaust pipes. DETAILED DESCRIPTION

[0063] The technical solution of the utility model is described in detail below with reference to the accompanying drawings and embodiments.

[0064] Examples 1-5

[0065] like Figure 1 A membrane-normal temperature hydrogen regeneration redox resin deoxygenation device is shown, the deoxygenation device comprises a pre-deoxygenator 1, a hydrogenator 2, a normal temperature hydrogen regeneration redox resin chemical deoxygenator 3 and a deoxygenation water tank 4 which are sequentially connected and arranged in the process;

[0066] 1) Pre-deaerator 1:

[0067] The pre-deaerator 1 comprises a pre-deaerator body, a water ring vacuum pump steam-water separator 1-9, a water ring vacuum pump 1-11, and a chiller 1-12; the pre-deaerator body is connected to a water source via a water inlet pipe 1-5; the pre-deaerator body is connected to the water ring vacuum pump 1-11 via an exhaust pipe 1-6, the water ring vacuum pump 1-11 is connected to the water ring vacuum pump steam-water separator 1-9 via a pipeline, and the water ring vacuum pump 1-11 is connected to the water ring vacuum pump steam-water separator 1-9 via a pipeline, and the water ring vacuum pump 1-11 is connected to the water ring vacuum pump steam-water separator 1-9 via a chiller output pipe 1-6 respectively. -13 and the chiller return pipe 1-14 are connected to the chiller 1-12, and the chiller 1-12 is connected to the water ring vacuum pump steam-water separator 1-9 through the steam-water separator return pipe 1-15; an exhaust valve 1-10 is arranged on the water ring vacuum pump steam-water separator 1-9; a water ring vacuum pump solenoid valve 1-7 and a vacuum pressure gauge 1-8 are arranged on the exhaust pipe 1-6; the pre-deaerator body is connected to the hydrogenator 2 through the pre-deaerator outlet pipe 1-16.

[0068] The pre-deoxygenator body is provided with a pre-deoxygenation hollow fiber membrane tube, the inside of the pre-deoxygenation hollow fiber membrane tube is an air chamber, which is connected to the exhaust pipe 1-6; the outside of the pre-deoxygenation hollow fiber membrane tube is a water chamber, which is connected to the water inlet pipe.

[0069] The water inlet pipe is provided with a water inlet valve 1-1, a pipeline pump 1-4 and a water pressure gauge 1-18 in sequence; a raw water sampling valve 1-2 and a raw water oxygen meter 1-3 are provided on the water inlet pipe between the water inlet valve 1-1 and the pipeline pump 1-4; a pre-deaerator water outlet sampling valve and a pre-deoxygenated water oxygen meter 1-17 are provided on the pre-deaerator water outlet pipe 1-16.

[0070] The pre-deaerator body is an oblong hard polyethylene shell with end caps at both ends of the shell. The shell is equipped with pre-deoxygenated hollow fiber membrane tubes in a bundle-like structure. The material of the pre-deoxygenated hollow fiber membrane tubes is polypropylene. The pre-deoxygenator body consists of an air chamber, a water chamber, a pre-deoxygenated hollow fiber membrane tube and a membrane shell. When the water ring vacuum pump 1-11 is turned on to evacuate the air chamber, the dissolved oxygen in the water flowing along the outside of the hollow fiber membrane tube wall in the water chamber will diffuse rapidly into the hollow fiber membrane tube through the microporous water film on the hollow fiber membrane tube wall, and then be vacuumed away by the water ring vacuum pump to achieve the purpose of deoxygenation. Figure 2As shown, a is the water flow layer outside the hollow fiber membrane tube wall, b is the hollow fiber membrane tube wall, c is the hollow fiber membrane tube, and d is the route of dissolved oxygen in water passing through the microporous water film of the hollow fiber membrane into the membrane tube. One end of the water chamber of the pre-deaerator body is connected to the water inlet pipe, and the other end is connected to the pre-deaerator outlet pipe 1-16, and the air chamber is connected to the exhaust pipe 1-6. The inner diameter of the hollow fiber membrane tube is 220μm-300μm, and the membrane shell is bonded to the hollow fiber membrane tube as a whole, and then connected to the water inlet pipe, the pre-deaerator outlet pipe 1-16, and the exhaust pipe 1-6. The water in the water inlet pipe flows into the water distribution pipe, sprays out from the hole in the water distribution pipe wall, and flows to the hollow fiber membrane tube. Under a pressure of 0.4Mpa, the water flow direction is perpendicular to the hollow fiber membrane tube. In order to avoid excessively high temperature of circulating water in the water ring vacuum pump, a chiller 1-12 is arranged in series in the circulating water circuit of the water ring vacuum pump. The chiller is provided with a cold water tank. The cold water cooled by the chiller 1-12 flows into the cold water tank. The water in the cold water tank is pumped into the water ring vacuum pump 1-11 through the chiller output pipe 1-13 by the magnetic pump. The water that circulates and heats up many times in the water ring vacuum pump 1-11 is cooled by the chiller 1-12 and then returns to the chiller water tank through the chiller return pipe 1-14. The steam-water mixture discharged by the water ring vacuum pump 1-11 will enter the steam-water separator 1-9. After separation, the steam will be discharged by the exhaust valve 1-10, and part of the dissolved oxygen in the water will also be discharged. The water separated by the steam-water separator 1-9 will return to the water ring vacuum pump 1-11 through the steam-water separator return pipe 1-15 for continued circulation. The water lost during the operation of the water ring vacuum pump 1-11 is replenished by the chiller magnetic pump sucking water from the chiller water tank.

[0071] 2) Hydrogenator:

[0072] The hydrogenator 2 includes a cylinder, a hydrogenation hollow fiber membrane tube and end covers, end covers are arranged at both ends of the cylinder, and a hydrogenation hollow fiber membrane tube is arranged in the cylinder; the interior of the hydrogenation hollow fiber membrane tube is a water chamber, and the space between the hydrogenation hollow fiber membrane tube and the cylinder is an air chamber; one end of the water chamber is connected to the pre-deaerator water outlet pipe 1-16, and the other end is connected to the hydrogenation water output pipe 2-3; the air chamber is connected to the hydrogen source; the hydrogen source includes a hydrogen bottle 2-10, and the hydrogen bottle 2-10 is connected to the air chamber of the hydrogenator 2 through the hydrogenation pipe 2-1; the hydrogenation pipe 2-1 is provided with a hydrogen solenoid valve 2-4, a hydrogen flowmeter 2-5, a hydrogen regulating valve 2-6, a low-pressure hydrogen pressure gauge 2-7, a high-pressure hydrogen pressure gauge 2-8, and a hydrogen main valve 2-9.

[0073] The chemical deoxidation component is a deoxidizing resin device for hydrogenation reduction. The hydrogenator 2 is generally composed of a stainless steel shell, a hydrogenation hollow fiber membrane tube and a stainless steel end cap. The stainless steel shell is an oblong cylindrical shell with a diameter of 200mm and a length of 1000m. End caps are provided at both ends. Dn10 hydrogen pipes are provided on the end caps, and hydrogenation hollow fiber membrane tubes are provided in the cylinder. The hydrogenation hollow fiber membrane tube is composed of a hollow fiber membrane tube bundle, a porous stainless steel disc, and a stainless steel water distribution and water collection pipe. A hydrogenation tube 2-1 is arranged inside the stainless steel discs at both ends of the cylinder. The end cap of the hydrogenator is provided with a water inlet pipe (the setting method can be welding), which is connected to the outlet pipe of the pre-deoxidizer. The other end cap of the hydrogenator is welded with a hydrogenated water output pipe 2-3 after hydrogenation, and a hydrogenated water flowmeter 2-2 is arranged on the hydrogenated water output pipe 2-3. After the pre-deoxidized water is filled with hydrogen, it enters the oxidized original resin deoxidizer 3 for hydrogen reduction regeneration. The hydrogenation process is as follows: hydrogen enters the hydrogenator gas chamber from the hydrogenation pipe 2-1, pre-deoxygenated water enters the water chamber of the hydrogenator, water flows in the hollow fiber membrane tube, and hydrogen is outside the hollow fiber membrane tube wall. Water flows from the water chamber at one end of the hydrogenator to the water chamber at the other end for hydrogenation, and the water with hydrogen flows into the resin deaerator. The water that has completed hydrogenation flows into the deaerator from the hydrogenation water output pipe 2-3, enters from the water inlet flange 3-2 of the deaerator, and flows out from the water outlet flange 3-3.

[0074] 3) Resin deaerator:

[0075] like Figure 3-4 As shown, the room temperature hydrogen regeneration redox resin chemical deoxygenator 3 includes a cylinder 3-1, an upper water distribution tray 3-8 is arranged on the upper part of the cylinder 3-1, and a lower water distribution tray 3-9 is arranged on the lower part of the cylinder, and room temperature hydrogen regeneration redox resin is filled between the upper water distribution tray 3-8 and the lower water distribution tray 3-9; the upper water distribution tray 3-8 is connected to the upper water pipe 3-6, and the lower water distribution tray 3-9 is connected to the lower water pipe 3-7; the upper water pipe 3-6 is connected to the water inlet flange 3-2 through the water inlet tee 3-11, and the upper water pipe 3-6 is connected to the water outlet flange 3-3 through the water outlet tee 3-12; the lower water pipe 3-7 is connected to the water inlet flange 3-2 through the water inlet tee 3-11, and the lower water pipe 3-7 is connected to the water outlet flange 3-3 through the water outlet tee 3-12.

[0076] The chemical deaerator is provided with an inlet flange 3-2, which is connected to the hydrogenated water output pipe 2-3 upstream and to the inlet tee 3-11 downstream. The other two connections of the inlet tee 3-11 are respectively connected to the upper inlet valve 3-13 and the lower inlet valve 3-14; one connection of the outlet tee 3-12 is connected to the outlet flange 3-3, and the other two connections are respectively connected to the upper outlet valve 3-15 and the lower outlet valve 3-16.

[0077] The hydrogen regenerated redox resin deaerator is filled with hydrogen regenerated redox resin. Among them: the cylinder 3-1 is a cylindrical cylinder made of 304 stainless steel; an upper water distribution tray 3-8 and a lower water distribution tray 3-9 are respectively arranged on the cylinder 3-1. The lower side wall of the cylinder 3-1 is provided with a resin loading flange assembly 3-17, and the upper side wall is provided with a resin unloading flange assembly 3-18. The cylinder 3-1 is a stainless steel container. The chemical deaerator generally includes a cylinder 3-1, an upper head 3-4, a lower head 3-5, a lower water distribution tray 3-7, an upper water distribution tray 3-8, a water inlet flange 3-2, a water outlet flange 3-3, etc. It can also include the following components: a deaerator cylinder flange, a deaerator head flange, a deaerator foot, a deaerator exhaust pipe 3-22 and a stainless steel filter cap 3-10. The two ends of the cylinder 3-1 are respectively an upper head 3-4 and a lower head 3-5. The upper head 3-4 is provided with a deaerator exhaust pipe 3-22, and the upper water distribution tray 3-8 and the lower water distribution tray 3-9 are respectively provided with a plurality of stainless steel filter caps 3-10.

[0078] 4) Deaeration water tank:

[0079] The water tank body 4-1 of the deoxygenated water tank 4 is a cylindrical body with a diameter of 2300x4500 rolled from a steel plate, with a bottom and a cover. An air-isolating airbag 4-3 is arranged in the water tank body 4-1, arranged below the water tank top cover 4-2 and bonded and fixed to the water tank top cover 4-2. A Dn25 air intake and exhaust pipe 4-7 is arranged on the water tank top cover. A flap-type liquid level gauge 4-4 is arranged outside the water tank wall, and a deoxygenated water sampling valve 3-20 and a deoxygenated water oxygen meter 3-21 are arranged on the deaerator water outlet pipe 3-19. The water inlet of the deoxygenated water tank 4 is 20 cm away from the bottom of the water tank. The water outlet pipe and the water inlet pipe of the deoxygenated water tank 4 are installed at the same height. A water tank outlet valve 4-5 is provided on the outlet pipe of the deoxygenated water tank, and a feed water pump 4-6 of a boiler is connected to the downstream of the water tank outlet valve 4-5. When the liquid level in the deoxygenated water tank rises, the air in the air-isolating airbag 4-3 is discharged through the air intake and exhaust pipe 4-7. When the liquid level in the water tank decreases, the air-isolating airbag 4-3 sucks air into the airbag through the air intake and exhaust pipe 4-7. The airbag and the water tank form a sealed system, so that the water in the water tank is never in contact with the air, so as to ensure the quality of the deoxygenated water.

[0080] In the room temperature hydrogen regeneration resin membrane deoxidation device of the utility model, the size of the pre-deoxidizer is 495x800mm, the rigid polyvinyl chloride shell, and the total area of ​​the hollow fiber membrane tube is 129m 2 The water pressure entering the pre-deaerator must be maintained at 0.4MP. If the pressure is not reached, the automatic control system will start pipeline pumps 1-4.

[0081] The vacuum system in the pre-deaerator includes a water ring vacuum pump 1-11, an exhaust pipe 1-6, a vacuum pressure gauge 1-8, a water ring vacuum pump solenoid valve 1-7, a steam-water separator 1-9 and a water ring vacuum pump exhaust valve 1-10. The cold water output pipe 1-13 of the chiller 1-12 is connected to the circulating cooling water inlet pipe, the chiller return pipe 1-14 is connected to the circulating cooling water outlet pipe, the water ring vacuum pump exhaust valve 1-10 is arranged on the top of the steam-water separator 1-9, and the water ring vacuum pump 1-11 is connected to the top of the steam-water separator 1-9 through a pipe. When the water ring vacuum pump is running, the condensed water of the steam-water separator flows back to the chiller 1-12 through the steam-water separator return pipe 1-15.

[0082] The hydrogenator includes a stainless steel membrane shell, a hydrogenation membrane component, a porous plastic disc, a central water distribution pipe, a central water collection pipe, a water chamber, an air chamber, a hydrogenation pipe 2-1, a hydrogenation water flow meter 2-2, and a hydrogenation water output pipe 2-3. The hydrogen cylinder 2-10 enters the hydrogen flow meter 2-5 through the hydrogen main valve 2-9, the low-pressure hydrogen valve, and the hydrogen regulating valve 2-6, and enters the hydrogenator 2 through the hydrogen solenoid valve 2-4. A high-pressure hydrogen meter 2-8 and a low-pressure hydrogen meter 2-7 are set on the hydrogen pipeline.

[0083] Connect the power supply during operation, start the pre-deaerator, open the water inlet valve 1-1 of the pre-deaerator first, and wait for the raw water to enter the water chamber of the pre-deaerator 1. Open the vacuum pump exhaust valve 1-10, and the gas extracted by the water ring vacuum pump enters the steam-water separator 1-9 for dehydration. The gas is discharged from the vacuum pump exhaust valve 1-10, and the water returns to the water ring vacuum pump from the steam-water separation return pipe 1-15. The exhaust pipe 1-16 inhales air from the air chamber of the pre-deaerator, the water ring vacuum pump 1-11 and the circulating cold water inlet pipe from the chiller outlet. Adjust the opening of the vacuum pump exhaust valve 1-10 so that the water flow rate is 40t per hour. Tap water, softened water, and desalted water enter through the water inlet pipe 1-5. The vacuum degree in the hollow fiber membrane tube in the pre-deaerator is maintained at 50mmHg, that is, the membrane pressure is maintained at -710mmHg. The water flow rate outside the hollow fiber membrane tube is controlled at 2800~3000m per hour. 3, the time for water to flow through the pre-deaerator is 0.8 to 1.0 seconds, the water temperature is room temperature, and the deoxygenation temperature is 5 to 40°C. The pre-deoxygenated water enters the hydrogenator 2 through the pre-deaerator outlet pipe 1-16, the hydrogenated water output pipe 2-3 is connected to the water inlet flange 3-2 on the resin deaerator 3, and the gas chamber of the hydrogenator 2 is connected to the hydrogen bottle 2-10 or pipeline hydrogen of the hydrogen source through the hydrogenation pipe 2-1. A hydrogen solenoid valve 2-4, a hydrogen flowmeter 2-5, a hydrogen regulating valve 2-6, a low-pressure hydrogen meter 2-7, a high-pressure hydrogen meter 2-8 and a hydrogen main valve 2-9 are set between the hydrogenation pipe 2-1 and the hydrogen source. Open the hydrogen main valve 2-9, then open the hydrogen regulating valve 2-6 and the hydrogen fine-tuning valve, and the hydrogen solenoid valve 2-4 to allow hydrogen to enter the hydrogenator gas chamber to hydrogenate the pre-deoxygenated water. The hydrogen flowmeter 2-5 displays the amount of hydrogenation. The residual oxygen content of the pre-deoxygenated water from the pre-deoxygenator 1 is 1-2 mg of dissolved oxygen per liter of water, and the hydrogenation rate of the 40t deoxygenator per hour is about 3.0L / hr. The outlet water of the hydrogenator is connected to the water inlet flange of the resin deoxygenator, and the upper water inlet valve 3-13 and the lower water outlet valve 3-16 are opened, and the resin deoxygenator operates in a downstream mode. Adjust the hydrogen regulating valve 2-6, and the opening degree makes the dissolved oxygen in the output water of the resin deoxygenator 3 reach below 5-10ppb. The deoxygenation results are shown in Table 1 below.

[0084] Table 1

[0085]

[0086] The hydrogen regeneration redox resin membrane deaerator is a floating bed redox resin deaerator. Taking the deaerator with a capacity of 40t / h as an example, the deaerator body has an overall size of 900×2300mm and contains 300kg of palladium redox resin. Open the water inlet valve 1-1, connect the water source, adjust the opening of the water inlet valve 1-1, open the upper water inlet valve 3-13 and the lower water outlet valve 3-16 downstream, or open the lower water inlet valve 3-14 and the upper water outlet valve 3-15 upstream, so that the hydrogenation water flow meter 2-2 indicates 40t / h, adjust the valve opening of the hydrogen bottle, control the hydrogen flow rate at 0-100ml / min, and make the residual oxygen content in the deoxygenated water downstream of the resin deoxygenated water output valve ≤5ppb, and then enter the deoxygenated water tank 4. The air isolation airbag 4-3 in the deoxygenated water tank is connected to the atmosphere through the air intake and exhaust pipe 4-3 on the deoxygenated water tank cover. As the deoxygenated water level rises and falls, the air in the airbag under the water tank cover is discharged or sucked in, so that the water tank is kept in balance with the atmosphere. A flap level gauge 4-4 is installed on the side of the water tank to indicate the deoxygenated water tank level, which is linked to the pipeline pump 1-4 and the boiler feed water pump 4-6 through the electric control cabinet. The residual oxygen content in the water after deoxygenation by the deaerator is measured by the deoxygenated water oxygen meter 3-21, and it is ≤5ppb. The operation results are listed in Table 2.

[0087] Table 2 Hydrogen regeneration resin membrane deaerator operation data table

[0088]

[0089]

[0090] Any content not described in detail in the present invention can be based on the conventional technical knowledge in the field.

[0091] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the utility model and are not intended to limit it. Although the utility model is described in detail with reference to the embodiments, a person skilled in the art should understand that any modification or equivalent replacement of the technical solution of the utility model does not deviate from the spirit and scope of the technical solution of the utility model, and should be included in the scope of the claims of the utility model.

Claims

1. A membrane-normal temperature hydrogen regeneration redox resin deoxygenation device, characterized in that: The device comprises a pre-deaerator, a hydrogenator, a normal temperature hydrogen regeneration redox resin chemical deaerator and a deaeration water tank which are sequentially connected and arranged in the process; The hydrogenator comprises a cylinder, a hydrogenation hollow fiber membrane tube and an end cap, the end caps are arranged at both ends of the cylinder, and the hydrogenation hollow fiber membrane tube is arranged in the cylinder; the interior of the hydrogenation hollow fiber membrane tube is a water chamber, and the space between the hydrogenation hollow fiber membrane tube and the cylinder is an air chamber; one end of the water chamber is connected to the water outlet pipe of the pre-deaerator, and the other end is connected to the hydrogenation water output pipe; the air chamber is connected to the hydrogen source; The hydrogenated water output pipe is connected to the water inlet flange of the normal temperature hydrogen regeneration redox resin chemical deoxygenator, the water outlet flange of the normal temperature hydrogen regeneration redox resin chemical deoxygenator is connected to the water inlet of the deoxygenated water tank through the deoxygenator water outlet pipe, and a deoxygenator water intake valve and a deoxygenator oxygen meter are arranged on the deoxygenator water outlet pipe; The room temperature hydrogen regeneration redox resin chemical deaerator comprises a cylinder, an upper head and a lower head are respectively arranged at both ends of the cylinder, an upper water distribution pan is arranged at the connection between the upper head and the cylinder on the upper part of the cylinder, and a lower water distribution pan is arranged at the connection between the lower head and the cylinder on the lower part of the cylinder, and room temperature hydrogen regeneration redox resin is filled between the upper water distribution pan and the lower water distribution pan; a plurality of filter caps are respectively arranged on the upper water distribution pan and the lower water distribution pan; the upper water distribution pan is connected to the upper water pipe, and the lower water distribution pan is connected to the lower water pipe; the upper water pipe is connected to the water inlet flange through the water inlet tee, and the upper water pipe is connected to the water outlet flange through the water outlet tee; the lower water pipe is connected to the water inlet flange through the water inlet tee, and the lower water pipe is connected to the water outlet flange through the water outlet tee.

2. The membrane-normal temperature hydrogen regeneration redox resin deoxygenation device according to claim 1 is characterized in that: The pre-deaerator comprises a pre-deaerator body, a water ring vacuum pump steam-water separator, a water ring vacuum pump, and a chiller; The pre-deaerator body is connected to a water source via a water inlet pipe; The pre-deaerator body is connected to the water ring vacuum pump through an exhaust pipe, the water ring vacuum pump is connected to the water ring vacuum pump steam-water separator through a pipeline, the water ring vacuum pump is connected to the chiller through a chiller output pipe and a chiller return pipe respectively, the chiller is connected to the water ring vacuum pump steam-water separator through a steam-water separator return pipe; a water ring vacuum pump exhaust valve is arranged on the water ring vacuum pump steam-water separator; The air extraction pipe is provided with a water ring vacuum pump solenoid valve and a vacuum pressure gauge; The pre-deaerator body is connected to the hydrogenator through the pre-deaerator water outlet pipe.

3. The membrane-normal temperature hydrogen regeneration redox resin deoxygenation device according to claim 2 is characterized in that: The pre-deoxygenator body is provided with a pre-deoxygenation hollow fiber membrane tube, the inside of the pre-deoxygenation hollow fiber membrane tube is an air chamber connected to the air extraction pipe; the outside of the pre-deoxygenation hollow fiber membrane tube is a water chamber connected to the water inlet pipe.

4. The membrane-normal temperature hydrogen regeneration redox resin deoxygenation device according to claim 2, characterized in that: A water inlet valve, a pipeline pump and a water pressure gauge are arranged on the water inlet pipe in sequence; a raw water sampling valve and a raw water oxygen meter are arranged on the water inlet pipe between the water inlet valve and the pipeline pump; a pre-deaerator water outlet sampling valve and a pre-deoxygenated water oxygen meter are arranged on the pre-deaerator water outlet pipe.

5. The membrane-normal temperature hydrogen regeneration redox resin deoxygenation device according to claim 1, characterized in that: The hydrogen source comprises a hydrogen cylinder, which is connected to the gas chamber of the hydrogenator through a hydrogenation pipe; a hydrogen solenoid valve, a hydrogen flow meter, a hydrogen regulating valve, a low-pressure hydrogen pressure gauge, a high-pressure hydrogen pressure gauge, and a hydrogen main valve are arranged on the hydrogenation pipe.

6. The membrane-normal temperature hydrogen regeneration redox resin deoxygenation device according to claim 1, characterized in that: An upper water inlet valve is arranged on the water inlet tee connecting the water inlet flange and the upper water pipe, and a lower water inlet valve is arranged on the water inlet tee connecting the water inlet flange and the lower water pipe; an upper water outlet valve is arranged on the water outlet tee connecting the water outlet flange and the upper water pipe, and a lower water outlet valve is arranged on the water outlet tee connecting the water outlet flange and the lower water pipe.

7. The membrane-normal temperature hydrogen regeneration redox resin deoxygenation device according to claim 1, characterized in that: The deoxygenated water tank comprises a water tank body, a water tank top cover, and an isolating air bag; the water tank top cover is arranged on the top of the water tank body, and the isolating air bag is arranged on the inner side of the water tank top cover.

8. The membrane-normal temperature hydrogen regeneration redox resin deoxygenation device according to claim 7, characterized in that: A liquid level gauge is arranged on the water tank body, and the water tank body is connected to a water-using device through a water tank outlet pipe, and a water tank outlet valve and a water supply pump are arranged on the water tank outlet pipe.

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