Efficient biochar filler for treating internal cooling water as well as preparation and treatment methods of efficient biochar filler

Abstract

The invention discloses efficient biochar filler for treating internal cooling water and a preparation and treatment method, and belongs to the technical field of internal cooling water treatment.The efficient biochar filler is prepared from municipal sludge and straw through a microwave co-heating method; loading humic acid on the biochar to prepare efficient biochar; finally, the efficient biochar is prepared into filler, and the efficient biochar filler for treating the internal cooling water is obtained. The method is used for treating Cu < 2 + > and HCO3 <-> in cold water in the generator. The preparation process of the efficient biochar is simple and easy to operate, the filler can be directly placed in bypass treatment equipment, and the operation is simple and convenient. And the adopted efficient biochar filler is low in cost, the treatment effect is remarkable, and the treatment cost of the internal cooling water can be greatly reduced. By inhibiting copper corrosion, the downtime of the generator caused by corrosion is reduced, the power generation efficiency is improved, the service life of equipment is prolonged, and the method is simple and convenient to operate, easy to popularize and remarkable in economic and environmental benefits and has important application and popularization prospects.

Description

Technical Field

[0001] The invention belongs to the technical field of internal cooling water treatment, and in particular relates to a high-efficiency biochar filler for treating internal cooling water and a preparation and treatment method thereof. Background Art

[0002] The corrosion of the stator bar hollow conductor by the internal cooling water of the generator seriously affects the efficiency and service life of the generator. The main reason is that CO2 in the air dissolves in the internal cooling water, causing the pH of the internal cooling water to drop, causing corrosion to the copper material of the hollow conductor. 2+ The copper oxides accumulated in the solution will deposit and cause blockage, affecting the flow of cooling water in the generator and reducing the heat exchange efficiency. When the blockage is serious, it will cause the motor to burn out.

[0003] At present, the bypass anion and cation exchange resin method is generally used to treat the cooling water inside the generator. The anion and cation exchange resin has a short life, the regeneration operation is cumbersome, and the cost of using and maintaining the anion and cation exchange resin is high. Chinese invention patent CN115925045A discloses a static cooling water conductivity automatic regulation control system and method. The internal cooling water is treated using four ion exchangers: a front static cooling ion exchanger, a sodium ion exchanger, a hydrogen ion exchanger, and a rear static cooling ion exchanger. The cost of the treatment device is high, there are multiple ion exchange resins in the system, and the regeneration operation is complicated. Moreover, the patent only provides the conductivity and pH of the water sample under operation, and does not provide information on CO2 and Cu in the water sample. 2+ The function is unknown. Chinese utility model patent CN221275543U discloses a generator internal cooling water alkali adding device. The device retains the original generator factory standard internal cooling water treatment equipment, and adds an automatic alkali adding device to assist in the treatment of internal cooling water. The invention actually uses alkali solution to increase the pH in the liquid phase and slow down the corrosion of CO2 on the hollow conductor of the stator wire rod. The amount of alkali required is difficult to control, and the patent does not show the effect of treating internal cooling water.

[0004] Therefore, there is an urgent need for a low-cost, effective generator internal cooling water treatment technology to inhibit copper corrosion in the generator internal cooling water, improve the efficiency and service life of the generator, and overcome the defects of the existing treatment methods such as high cost and cumbersome operation. Summary of the invention

[0005] In order to overcome the shortcomings of the prior art, the present invention aims to provide a high-efficiency biochar filler for treating internal cooling water and a preparation and treatment method thereof, so as to solve the problem of Cu 2+ and HCO3 - The presence of this leads to corrosion of the cooling water copper inside the generator, resulting in technical problems such as low efficiency and service life of the generator.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions: The present invention discloses a method for preparing a high-efficiency biochar filler for treating internal cooling water, comprising the following steps: First, municipal sludge and straw are co-heated by microwave to obtain biochar; then, the biochar is loaded with humic acid to obtain high-efficiency biochar; finally, the high-efficiency biochar is prepared into filler to obtain high-efficiency biochar filler for treating internal cooling water; Highly efficient biochar filler for treating internal cooling water for treating Cu in generator internal cooling water 2+ and HCO3 - .

[0007] Preferably, the mass ratio of municipal sludge to straw is (1-4):(6-9); and the length of the straw is 1-5 cm.

[0008] Preferably, the microwave co-thermal method comprises: placing the mixed municipal sludge and straw in a microwave oven, and introducing high-purity nitrogen to perform microwave co-thermal decomposition.

[0009] More preferably, the introduction rate of high-purity nitrogen is 15-25 mL / min; and the introduction time of high-purity nitrogen is 10-20 min.

[0010] More preferably, the power of microwave co-pyrolysis is 50-400 W; and the time of microwave co-pyrolysis is 25-35 min.

[0011] Preferably, the method of loading humic acid on biochar comprises: adding biochar to a humic acid solution, stirring and mixing, filtering, washing, and freeze-drying to obtain high-efficiency biochar for treating internal cooling water.

[0012] Further preferably, the humic acid solution is prepared by dissolving humic acid in a NaOH solution and then adjusting the pH to 6.9-7.1 with a hydrochloric acid solution; the concentration of the humic acid solution is 50-200 mg / L; The mass ratio of biochar to humic acid solution is 1000:(50~200).

[0013] Further preferably, the stirring condition is: stirring at a constant temperature of 20-30° C. and a rotation speed of 150-180 rpm for 5-10 days; the washing condition is: washing with high-purity water for 3-6 times.

[0014] The invention also discloses a high-efficiency biochar filler for treating internal cooling water, which is prepared by the above-mentioned preparation method.

[0015] The present invention also discloses a method for treating inner cooling water by bypass using a high-efficiency biochar filler, comprising: placing the high-efficiency biochar filler for treating inner cooling water prepared by the above preparation method in an inner cooling water bypass treatment device, the inner cooling water of the generator enters the bypass treatment device, and the Cu in the inner cooling water is treated by the high-efficiency biochar filler. 2+ and HCO3 - .

[0016] Compared with the prior art, the present invention has the following beneficial effects: The invention discloses a method for preparing an efficient biochar filler for treating internal cooling water. First, municipal sludge and straw are subjected to a microwave co-heating method to prepare biochar. Municipal sludge and straw are common wastes. They are converted into biochar by the microwave co-heating method, which realizes the resource utilization of wastes and reduces environmental pollution. Municipal sludge and straw are widely available and low in cost, which reduces the preparation cost of biochar. The microwave co-heating method has low energy consumption, and nitrogen is introduced during the preparation process to exclude oxygen, thereby avoiding the generation of harmful gases and meeting green environmental protection requirements. Microwave heating has a fast speed and high thermal efficiency, and the preparation of biochar can be completed in a short time. Then, biochar is loaded with humic acid to prepare efficient biochar. Humic acid has rich functional groups and strong adsorption capacity. After being loaded on the surface of biochar, the adsorption performance of biochar on Cu²⁺ and HCO3⁻ is significantly improved. The combination of humic acid and biochar enhances the stability of the filler, making it less likely to fail in long-term use. The loading of humic acid improves the surface properties of biochar, increases its specific surface area and pore structure, and further improves the adsorption efficiency. Finally, the high-efficiency biochar is prepared into a filler to obtain a high-efficiency biochar filler for treating internal cooling water; the high-efficiency biochar is prepared into a filler form, which is convenient for direct application in bypass treatment equipment and easy to operate. The filler has a high specific surface area and abundant adsorption sites, and can efficiently remove Cu²⁺ and HCO3⁻ from the internal cooling water. The stability and high efficiency of the filler give it a long service life, reducing the replacement frequency and maintenance cost. The high-efficiency biochar filler can effectively adsorb Cu²⁺ and HCO3⁻ in the internal cooling water, inhibit copper corrosion of the internal cooling water of the generator, and extend the service life of the equipment. By reducing copper corrosion, the failure rate and downtime of the generator are reduced, and the power generation efficiency is improved. The low cost and high efficiency of the filler reduce the use of chemical agents and equipment maintenance costs for internal cooling water treatment. Compared with traditional chemical treatment methods, this method does not require the addition of chemical agents, reduces secondary pollution to the environment, and has significant environmental benefits. The filler for treating inner cooling water of the present invention has low cost, wide sources, and a green and environmentally friendly preparation process. 2+ and HCO3 - It has good processing effect and important application value.

[0017] Furthermore, the mass ratio of municipal sludge to straw is (1-4):(6-9); the length of the straw is 1-5 cm; a reasonable mass ratio and straw length can ensure that the mixture is evenly heated during the pyrolysis process, improve the pyrolysis efficiency, and avoid the problem of uneven pyrolysis caused by straw that is too long or too short.

[0018] Furthermore, the microwave co-thermal method includes: placing the mixed municipal sludge and straw in a microwave oven and introducing high-purity nitrogen for microwave co-thermal decomposition; microwave heating is fast and has high energy utilization, which can significantly shorten the pyrolysis time. The nitrogen environment helps to generate more pyrolysis product biochar and reduce the generation of harmful gases.

[0019] Furthermore, the introduction rate of high-purity nitrogen is 15-25 mL / min; the introduction time of high-purity nitrogen is 10-20 min; the appropriate nitrogen introduction rate and time can effectively maintain an oxygen-free environment and ensure the stability of the pyrolysis process and the quality of the product.

[0020] Furthermore, the power of microwave co-pyrolysis is 50-400 W; the time of microwave co-pyrolysis is 25-35 min; reasonable power and time settings can ensure that the pyrolysis reaction is fully carried out to generate high-quality biochar while avoiding energy waste.

[0021] Furthermore, the method of loading humic acid on biochar includes: adding biochar to a humic acid solution, stirring and mixing, filtering, washing, and freeze-drying to obtain high-efficiency biochar for treating internal cooling water; the biochar loaded with humic acid has a stronger adsorption capacity, can more effectively treat pollutants in internal cooling water, and improve water treatment efficiency.

[0022] Furthermore, the humic acid solution is prepared by dissolving humic acid in a NaOH solution and then adjusting the pH to 6.9-7.1 with a hydrochloric acid solution; the concentration of the humic acid solution is 50-200 mg / L; the appropriate pH and concentration can ensure the stability of humic acid in the solution, so that it can be evenly loaded on the biochar, improving the adsorption performance of the biochar. The mass ratio of biochar to humic acid solution is 1000: (50~200); the reasonable mass ratio can ensure that the humic acid is evenly loaded on the biochar and optimize the adsorption performance of the biochar.

[0023] Furthermore, the stirring conditions are: stirring at a constant temperature of 20-30°C and a speed of 150-180 rpm for 5-10 days; the washing conditions are: washing with high-purity water 3-6 times; appropriate stirring and washing conditions can ensure that humic acid is evenly loaded on the biochar, remove impurities, and improve the adsorption performance and stability of the biochar.

[0024] The present invention also discloses a highly efficient biochar filler for treating inner cooling water, which is prepared by the above-mentioned preparation method. The biochar prepared by co-pyrolysis of municipal sludge and straw realizes the recycling of waste resources and has both environmental and economic benefits. The humic acid loading further enhances the adsorption performance of the biochar, enabling it to efficiently remove specific pollutants such as Cu in the inner cooling water. 2+ and HCO3 - The biochar filler has a high specific surface area, rich pore structure and surface active sites, can effectively adsorb pollutants in water, and is highly efficient, stable and renewable, making it suitable for industrial water treatment.

[0025] The present invention also discloses a method for treating inner cooling water by bypass using high-efficiency biochar filler. The method applies high-efficiency biochar filler to inner cooling water bypass treatment equipment, and treats Cu in the inner cooling water of the generator by bypass treatment. 2+ and HCO3 - Bypass treatment can treat circulating water without stopping the system to ensure stable operation of the system. High-efficiency biochar fillers can effectively remove Cu through surface adsorption and ion exchange. 2+ , to prevent its accumulation in the system and avoid corrosion and damage to the generator equipment. - It is a common alkaline ion in water. Its high concentration may cause the pH value of water to increase, which in turn causes equipment scaling problems. Biochar fillers can adsorb HCO3 through the action of surface functional groups. - , adjust the water pH and reduce the risk of scaling. This method uses waste resources, municipal sludge and straw, to prepare biochar, which reduces the treatment cost, avoids the use of chemical agents, and reduces the risk of secondary pollution. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 It is a schematic diagram of a device for treating internal cooling water by bypassing a high-efficiency biochar filler disclosed in the present invention; Figure 2 This is a diagram showing the effect of biochar filler prepared at different microwave powers disclosed in Example 1 of the present invention on CO2 treatment in internal cooling water; Figure 3 The biochar filler prepared at different humic acid addition amounts disclosed in Example 2 of the present invention has an effect on Cu in cold water. 2+ The processing effect diagram; Figure 4 The present invention discloses a flow chart of a method for treating internal cooling water by bypassing with a high-efficiency biochar filler. DETAILED DESCRIPTION

[0027] The technical solution of the present invention will be described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0028] In the present invention, unless otherwise specified, all the embodiments and preferred implementation methods mentioned herein can be combined with each other to form a new technical solution.

[0029] In the present invention, unless otherwise specified, all technical features and preferred features mentioned herein can be combined with each other to form a new technical solution.

[0030] In the present invention, unless otherwise specified, percentage (%) or part refers to the weight percentage or weight part relative to the composition.

[0031] In the present invention, unless otherwise specified, the components or preferred components involved can be combined with each other to form a new technical solution.

[0032] In the present invention, unless otherwise specified, the numerical range "ab" represents an abbreviation of any real number combination between a and b, where a and b are real numbers. For example, the numerical range "6-22" means that all real numbers between "6-22" have been listed in this document, and "6-22" is just an abbreviation of these numerical combinations.

[0033] The “range” disclosed in the present invention is in the form of a lower limit and an upper limit, which can be one or more lower limits, and one or more upper limits, respectively.

[0034] In the present invention, the term "and / or" used herein refers to any combination and all possible combinations of one or more of the associated listed items, and includes these combinations.

[0035] In the present invention, unless otherwise specified, each reaction or operation step can be carried out sequentially or in accordance with the sequence. Preferably, the reaction method herein is carried out sequentially.

[0036] Unless otherwise specified, the professional and scientific terms used herein have the same meanings as those familiar to those skilled in the art. In addition, any method or material similar or equivalent to the described content may also be applied to the present invention.

[0037] The present invention provides a method for treating internal cooling water by bypassing with high-efficiency biochar filler, comprising the following steps: Step 1: preparing biochar from municipal sludge and pretreated straw by microwave co-heating; Step 2: Loading the obtained biochar with humic acid to prepare high-efficiency biochar; Step 3: Prepare the obtained high-efficiency biochar into filler and place it in the bypass treatment equipment to treat the cooling water in the generator.

[0038] The pretreatment includes: crushing the straw into small segments with a length of 1-5 cm, and the crushing length is preferably 1-2 cm.

[0039] The municipal sludge and the crushed straw are mixed in a mass ratio of municipal sludge: straw of 1:9 to 4:6, and preferably in a mass ratio of municipal sludge: straw of 2:8 to 3:7.

[0040] The mixed municipal sludge and straw are placed in a microwave oven, and high-purity nitrogen is passed at a rate of 15-25 mL / min for 10-20 min to exclude possible oxygen. Subsequently, microwave co-pyrolysis is performed at a microwave power of 50-400 W, preferably 100-200 W, and the treatment time of microwave co-pyrolysis is 25-35 min.

[0041] The present invention provides a method for preparing high-efficiency biochar by loading humic acid with biochar, comprising the following steps: Step 1: Dissolve humic acid in 0.1 mol / L NaOH solution, and then adjust the pH to 7.0 ± 0.1 with 1 mol / L hydrochloric acid solution to prepare a humic acid solution. The concentration of the humic acid solution is 50-200 mg / L, preferably 50-150 mg / L.

[0042] Step 2: Add 1 g / L of biochar to the humic acid solution, and stir at a constant temperature of 20-30°C and a speed of 150-180 rpm for 5-10 days, preferably 7-8 days.

[0043] Step 3: Filter the mixture obtained after stirring, take a solid sample, and wash it with high-purity water for 3-6 times. After freeze-drying the washed solid sample, high-efficiency biochar is obtained.

[0044] When using high-efficiency biochar filler to bypass the internal cooling water, high-efficiency biochar is used as filler and added into the internal cooling water bypass treatment equipment. The internal cooling water enters the bypass treatment facility and is treated with high-efficiency biochar filler to remove Cu 2+ and HCO3 - , inhibiting copper corrosion in the cooling water of the generator.

[0045] The present invention provides a method for treating inner cooling water by bypass using high-efficiency biochar filler. First, municipal sludge and straw are prepared into biochar by microwave co-heating method. Then, the biochar is loaded with humic acid to prepare high-efficiency biochar. Finally, the high-efficiency biochar is prepared into filler and placed in bypass treatment equipment. The inner cooling water enters the bypass treatment facility and is treated with high-efficiency biochar filler to remove Cu 2+ and HCO3 - , inhibiting copper corrosion in the cooling water of the generator. The filler for treating the cooling water of the invention has low cost, wide sources, and a green and environmentally friendly preparation process. 2+ and HCO3 - It has good processing effect and important application value.

[0046] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments. The components of the embodiments of the present invention described and shown in the drawings here can usually be arranged and designed in various different configurations. Therefore, the following detailed description of the embodiments of the present invention provided in the drawings is not intended to limit the scope of the claimed invention, but merely represents selected embodiments of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0047] Example 1 A method for treating internal cooling water by bypassing with high-efficiency biochar filler comprises the following steps: The straw was crushed into small pieces with a length of 2 cm. Then, the municipal sludge and the crushed straw were mixed, and the mass ratio of the mixture was municipal sludge: straw = 2: 8. The mixed municipal sludge and straw were placed in a microwave oven and high-purity nitrogen was passed at a rate of 20 mL / min for 15 min to exclude possible oxygen. Then it was divided into 5 parts and microwave co-pyrolysis was carried out at microwave powers of 100 W, 150 W, 200 W, 300 W and 350 W respectively. The treatment time of microwave co-pyrolysis was 30 min; 5 biomasses prepared with different microwave powers were obtained.

[0048] Humic acid was dissolved in 0.1 mol / L NaOH solution, and then adjusted to pH 7.0 ± 0.1 with 1 mol / L hydrochloric acid solution to prepare a humic acid solution with a concentration of 100 mg / L. 1 g / L biomass prepared with 5 different microwave powers was added to the humic acid solution and stirred at 160 rpm for 7 days at a constant temperature of 25°C. The mixture obtained after stirring was filtered, and the solid sample was taken and washed with high-purity water 5 times. After freeze-drying the washed solid sample, 5 kinds of high-efficiency biochar were obtained.

[0049] Five kinds of high-efficiency biochar were added as fillers into the internal cooling water bypass treatment facility (see Appendix Figure 1 The internal cooling water enters the bypass treatment facility and is treated with high-efficiency biochar filler to remove the Cu 2+ and HCO3 - , inhibiting copper corrosion in the cooling water of the generator.

[0050] Take the treated water samples and test the CO2 treatment effect.

[0051] Figure 1 The schematic diagram of the device for treating inner cooling water by bypassing with high-efficiency biochar filler disclosed in the present invention; as can be seen from the figure, the high-efficiency biochar filler is added into the inner cooling water bypass treatment equipment, and the Cu 2+ and HCO3 - , which can inhibit the copper corrosion of the cooling water in the generator.

[0052] Figure 2 The figure is a diagram showing the treatment effect of biochar fillers prepared at different microwave powers disclosed in Example 1 of the present invention on CO2 in inner cooling water; it can be seen from the figure that the treatment amounts of CO2 in inner cooling water by biochar fillers prepared at microwave powers of 100W, 150W, 200W, 300W and 350W are 30.63 mg / g, 41.84 mg / g, 37.45 mg / g, 32.98 mg / g and 34.95 mg / g respectively. Among them, the biochar filler prepared at 150W microwave power has the best treatment effect on CO2 in inner cooling water.

[0053] Example 2 A method for treating internal cooling water by bypassing with high-efficiency biochar filler comprises the following steps: The straw was crushed into small pieces with a length of 2 cm. Then, the municipal sludge and the crushed straw were mixed, and the mass ratio of the mixture was municipal sludge: straw = 2: 8. The mixed municipal sludge and straw were placed in a microwave oven, and high-purity nitrogen was passed at a rate of 20 mL / min for 15 minutes to exclude possible oxygen. Then, microwave co-pyrolysis was performed at a microwave power of 150W. The treatment time of microwave co-pyrolysis was 30 minutes; biomass was obtained.

[0054] Three portions of humic acid of different masses were dissolved in 0.1 mol / L NaOH solution, and then the pH was adjusted to 7.0 ± 0.1 with 1 mol / L hydrochloric acid solution to prepare three humic acid solutions of different concentrations. The concentrations of the humic acid solutions were 0 mg / L, 100 mg / L, and 200 mg / L, respectively. Three portions of 1 g / L biomass were added to humic acid solutions of different concentrations, and stirred at 160 rpm for 7 days at a constant temperature of 25°C. The mixture obtained after stirring was filtered, and the solid sample was taken and washed 5 times with high-purity water. After freeze-drying the washed solid sample, three kinds of high-efficiency biochar were obtained.

[0055] Three kinds of high-efficiency biochar were added as fillers into the internal cooling water bypass treatment facility (see Appendix Figure 1 The internal cooling water enters the bypass treatment facility and is treated with high-efficiency biochar filler to remove the Cu 2+ and HCO3 - , inhibiting copper corrosion in the cooling water of the generator.

[0056] The treated water samples were respectively subjected to Cu 2+ Treatment effect test.

[0057] Figure 3 The biochar filler prepared at different humic acid addition amounts disclosed in Example 2 of the present invention has an effect on Cu in cold water. 2+ The treatment effect diagram; It can be seen from the figure that the biochar filler prepared at the concentration of humic acid solution of 0 mg / L, 100 mg / L and 200 mg / L has an effect on Cu 2+ The removal amounts of biochar filler prepared at a concentration of 100 mg / L humic acid solution were 14.9 mg / g, 23 mg / g and 17.3 mg / g, respectively. 2+ The processing effect is best.

[0058] Figure 4This is a flow chart of the method for treating inner cooling water by bypass using high-efficiency biochar filler disclosed in the present invention; as can be seen from the figure, municipal sludge and straw are first prepared into biochar by microwave co-heating method, then biochar is loaded with humic acid to make high-efficiency biochar, and finally the high-efficiency biochar is prepared into filler and placed in the bypass treatment equipment. The inner cooling water enters the bypass treatment facility, and the Cu 2+ and HCO3 - , inhibiting copper corrosion in the cooling water of the generator.

[0059] Example 3 A method for treating internal cooling water by bypassing with high-efficiency biochar filler comprises the following steps: The straw was crushed into small pieces with a length of 1 cm. Then, the municipal sludge and the crushed straw were mixed, and the mass ratio of the mixture was municipal sludge: straw = 1: 9. The mixed municipal sludge and straw were placed in a microwave oven, and high-purity nitrogen was passed at a rate of 15 mL / min for 10 minutes to exclude possible oxygen. Then, microwave co-pyrolysis was performed at a microwave power of 50W. The treatment time of microwave co-pyrolysis was 25 minutes; biomass was obtained.

[0060] Humic acid was dissolved in 0.1 mol / L NaOH solution, and then the pH was adjusted to 7.0 ± 0.1 with 1 mol / L hydrochloric acid solution to prepare a humic acid solution with a concentration of 50 mg / L. 1 g / L of biomass was added to the humic acid solution and stirred at 150 rpm for 5 days at a constant temperature of 20°C. The mixture obtained after stirring was filtered, and the solid sample was taken and washed 3 times with high-purity water. After freeze-drying the washed solid sample, efficient biochar was obtained.

[0061] Use high-efficiency biochar as filler and add it into the internal cooling water bypass treatment facility (attached Figure 1 The internal cooling water enters the bypass treatment facility and is treated with high-efficiency biochar filler to remove the Cu 2+ and HCO3 - , inhibiting copper corrosion in the cooling water of the generator.

[0062] Example 4 A method for treating internal cooling water by bypassing with high-efficiency biochar filler comprises the following steps: The straw was crushed into small pieces with a length of 5 cm. Then, the municipal sludge and the crushed straw were mixed, and the mass ratio of the mixture was municipal sludge: straw = 4: 6. The mixed municipal sludge and straw were placed in a microwave oven, and high-purity nitrogen was passed at a rate of 25 mL / min for 20 min to exclude possible oxygen. Then, microwave co-pyrolysis was performed at a microwave power of 400 W. The treatment time of microwave co-pyrolysis was 35 min; biomass was obtained.

[0063] Humic acid was dissolved in 0.1 mol / L NaOH solution, and then the pH was adjusted to 7.0 ± 0.1 with 1 mol / L hydrochloric acid solution to prepare a humic acid solution with a concentration of 200 mg / L. 1 g / L of biomass was added to the humic acid solution and stirred at 180 rpm for 10 days at a constant temperature of 30°C. The mixture obtained after stirring was filtered, and the solid sample was taken and washed 6 times with high-purity water. After freeze-drying the washed solid sample, efficient biochar was obtained.

[0064] Use high-efficiency biochar as filler and add it into the internal cooling water bypass treatment facility (attached Figure 1 The internal cooling water enters the bypass treatment facility and is treated with high-efficiency biochar filler to remove the Cu 2+ and HCO3 - , inhibiting copper corrosion in the cooling water of the generator.

[0065] Example 5 A method for treating internal cooling water by bypassing with high-efficiency biochar filler comprises the following steps: The straw was crushed into small pieces with a length of 3 cm. Then, the municipal sludge and the crushed straw were mixed, and the mass ratio of the mixture was municipal sludge: straw = 3: 7. The mixed municipal sludge and straw were placed in a microwave oven, and high-purity nitrogen was passed at a rate of 18 mL / min for 12 min to exclude possible oxygen. Then, microwave co-pyrolysis was performed at a microwave power of 180 W. The treatment time of microwave co-pyrolysis was 22 min; biomass was obtained.

[0066] Humic acid was dissolved in 0.1 mol / L NaOH solution, and then the pH was adjusted to 7.0 ± 0.1 with 1 mol / L hydrochloric acid solution to prepare a humic acid solution with a concentration of 120 mg / L. 1 g / L of biomass was added to the humic acid solution and stirred at 170 rpm for 8 days at a constant temperature of 22°C. The mixture obtained after stirring was filtered, and the solid sample was taken and washed 4 times with high-purity water. After freeze-drying the washed solid sample, efficient biochar was obtained.

[0067] Use high-efficiency biochar as filler and add it into the internal cooling water bypass treatment facility (attached Figure 1 The internal cooling water enters the bypass treatment facility and is treated with high-efficiency biochar filler to remove the Cu 2+ and HCO3 - , inhibiting copper corrosion in the cooling water of the generator.

[0068] Example 6 A method for treating internal cooling water by bypassing with high-efficiency biochar filler comprises the following steps: The straw was crushed into small pieces with a length of 4 cm. Then, the municipal sludge and the crushed straw were mixed, and the mass ratio of the mixture was municipal sludge: straw = 2:7. The mixed municipal sludge and straw were placed in a microwave oven and high-purity nitrogen was passed at a rate of 22 mL / min for 18 minutes to exclude possible oxygen. Then, microwave co-pyrolysis was performed at a microwave power of 250W. The treatment time of microwave co-pyrolysis was 28 minutes; biomass was obtained.

[0069] Humic acid was dissolved in 0.1 mol / L NaOH solution, and then the pH was adjusted to 7.0 ± 0.1 with 1 mol / L hydrochloric acid solution to prepare a humic acid solution with a concentration of 150 mg / L. 1 g / L of biomass was added to the humic acid solution and stirred at 190 rpm for 9 days at a constant temperature of 28°C. The mixture obtained after stirring was filtered, and the solid sample was taken and washed with high-purity water 5 times. After freeze-drying the washed solid sample, efficient biochar was obtained.

[0070] Use high-efficiency biochar as filler and add it into the internal cooling water bypass treatment facility (attached Figure 1 The internal cooling water enters the bypass treatment facility and is treated with high-efficiency biochar filler to remove the Cu 2+ and HCO3 - , inhibiting copper corrosion in the cooling water of the generator.

[0071] The present invention provides a method for treating internal cooling water by bypassing with high-efficiency biochar filler, and the municipal sludge and straw used are common wastes with wide sources and low cost. Municipal sludge is a byproduct in the sewage treatment process, and straw is agricultural waste. Both usually need to be treated or disposed of. Using them to prepare biochar not only reduces the cost, but also realizes the resource utilization of waste. The preparation of biochar by microwave co-heating method has a simple process and low energy consumption, which further reduces the production cost. Municipal sludge and straw, as wastes, may cause environmental pollution if not treated. The present invention realizes the resource utilization of waste and reduces environmental pollution by converting them into biochar. In the process of preparing biochar by microwave co-heating method, high-purity nitrogen is introduced to exclude oxygen, avoid the generation of harmful gases, and the preparation process is green and environmentally friendly. By loading humic acid on biochar, the prepared high-efficiency biochar has a large specific surface area and rich functional groups, which can effectively adsorb Cu²⁺ and HCO3⁻ in the internal cooling water and inhibit copper corrosion of the internal cooling water of the generator. Experiments show that the method has a good treatment effect on Cu²⁺ and HCO3⁻ in the internal cooling water, which can effectively extend the service life of the generator and reduce maintenance costs. The preparation process of high-efficiency biochar is simple and easy to operate, and the filler can be directly placed in the bypass treatment equipment, which is easy to operate. The method is not only suitable for the treatment of internal cooling water of the generator, but can also be extended to other industrial cooling water systems, and has broad application prospects. Cu²⁺ and HCO3⁻ in the internal cooling water are the main causes of copper corrosion. The present invention effectively inhibits copper corrosion through high-efficiency biochar filler treatment, extends the service life of the generator, reduces the frequency of equipment maintenance and replacement, and reduces operating costs. By optimizing the mixing ratio of municipal sludge and straw, microwave power and treatment time, the efficient preparation of biochar is ensured and the adsorption performance is improved. By controlling the concentration, stirring time and pH value of the humic acid solution, the effective load of humic acid on biochar is ensured, and the adsorption capacity of biochar is further improved. Compared with the traditional chemical treatment method, the high-efficiency biochar filler used in the present invention is low in cost and has a significant treatment effect, which can greatly reduce the cost of internal cooling water treatment. By inhibiting copper corrosion, the downtime of the generator caused by corrosion problems is reduced, the power generation efficiency is improved, and significant economic benefits are brought. Traditional internal cooling water treatment usually requires the addition of chemical agents, which may cause secondary pollution to the environment. The present invention uses biochar filler treatment, which does not require the addition of chemical agents and reduces the negative impact on the environment. By converting municipal sludge and straw into biochar, the greenhouse gas emissions generated by the decomposition of these wastes in the natural environment are reduced, which has a significant carbon emission reduction effect.

[0072] In summary, the present invention provides a low-cost, green and environmentally friendly internal cooling water treatment method by using municipal sludge and straw to prepare high-efficiency biochar filler. This method can not only effectively treat Cu²⁺ and HCO3⁻ in internal cooling water, inhibit copper corrosion, and extend the service life of equipment, but also has the advantages of simple operation, easy promotion, significant economic and environmental benefits, etc., and has important application value and promotion prospects.

[0073] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a highly efficient biochar filler for treating internal cooling water, characterized in that: The following steps are involved: First, municipal sludge and straw are co-heated by microwave to obtain biochar; then, the biochar is loaded with humic acid to obtain high-efficiency biochar; finally, the high-efficiency biochar is prepared into filler to obtain high-efficiency biochar filler for treating internal cooling water; The high-efficiency biochar filler for treating internal cooling water is used to treat Cu in the internal cooling water of the generator. 2+ and HCO3 - .

2. The method for preparing a high-efficiency biochar filler for treating internal cooling water according to claim 1, characterized in that: The mass ratio of the municipal sludge to the straw is (1-4):(6-9); the length of the straw is 1-5 cm.

3. The method for preparing a high-efficiency biochar filler for treating internal cooling water according to claim 1, characterized in that: The microwave co-thermal method comprises: placing the mixed municipal sludge and straw in a microwave oven, and introducing high-purity nitrogen to perform microwave co-thermal decomposition.

4. The method for preparing a high-efficiency biochar filler for treating internal cooling water according to claim 3, characterized in that: The introduction rate of the high-purity nitrogen gas is 15-25 mL / min; the introduction time of the high-purity nitrogen gas is 10-20 min.

5. The method for preparing a high-efficiency biochar filler for treating internal cooling water according to claim 3, characterized in that: The power of the microwave co-pyrolysis is 50-400 W; the time of the microwave co-pyrolysis is 25-35 min.

6. The method for preparing a high-efficiency biochar filler for treating internal cooling water according to claim 1, characterized in that: The method for loading humic acid on biochar comprises: adding biochar into a humic acid solution, stirring and mixing, filtering, washing, and freeze-drying to obtain high-efficiency biochar for treating internal cooling water.

7. The method for preparing a high-efficiency biochar filler for treating internal cooling water according to claim 6, characterized in that: The humic acid solution is prepared by dissolving humic acid in a NaOH solution and then adjusting the pH to 6.9-7.1 with a hydrochloric acid solution; the concentration of the humic acid solution is 50-200 mg / L; The mass ratio of the biochar to the humic acid solution is 1000:(50-200).

8. The method for preparing a high-efficiency biochar filler for treating internal cooling water according to claim 6, characterized in that: The stirring condition is: stirring at a constant temperature of 20-30° C. and a rotation speed of 150-180 rpm for 5-10 days; the washing condition is: washing with high-purity water for 3-6 times.

9. A highly efficient biochar filler for treating internal cooling water, characterized in that: The method is prepared by any one of claims 1 to 8.

10. A method for treating internal cooling water by bypassing with high-efficiency biochar filler, characterized in that: include: The high-efficiency biochar filler for treating internal cooling water prepared by the preparation method according to any one of claims 1 to 8 is placed in an internal cooling water bypass treatment device, and the internal cooling water of the generator enters the bypass treatment device, and the Cu in the internal cooling water is treated by the high-efficiency biochar filler. 2+ and HCO3 - .

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