Protection method for preventing marine fouling organisms from being attached to seawater cooling system and medicament used in protection method

Abstract

The invention relates to a protection method for preventing marine fouling organisms from being attached to a seawater cooling system and an agent used by the protection method. The invention discloses a protection method for preventing marine fouling organisms from being attached to a seawater cooling system. The protection method is characterized by comprising the following steps: 1) preparing novel multi-tube micro-channel emulsification equipment; 2) preparing a raw material reagent for preventing the marine fouling organisms from being attached to the seawater cooling system; (3) preparing a medicament for preventing marine fouling organisms from being attached to the seawater cooling system: starting a heater and an ultrasonic probe in the novel multi-tube micro-channel emulsification equipment; and (4) injecting the medicament for preventing the marine fouling organisms from being attached to the seawater cooling system into a pipeline of the seawater cooling system, so that the concentration content of the medicament in the seawater is 1-5mg / L. According to the method and the medicament used by the method, adhesion and breeding of marine fouling organisms on the seawater cooling system can be effectively prevented, so that the problem of blockage of the seawater cooling system is avoided, and safe operation of the seawater cooling system is ensured.

Description

Technical Field

[0001] The invention relates to a protective method for preventing marine fouling organisms from attaching to a seawater cooling system and a used agent. Background Art

[0002] In order to cope with the increasingly severe challenge of water shortage, large industrial water users such as thermal power plants in coastal areas have actively adopted the strategy of replacing fresh water with seawater, taking it as a key policy to solve the serious water shortage problem in coastal cities, and vigorously promoting the application of comprehensive seawater utilization technologies such as direct or recycled seawater utilization. Comprehensive seawater utilization technology has achieved remarkable results in alleviating water shortages. However, this technology also faces the problem of marine fouling organisms attaching and growing in seawater cooling systems. This problem mainly stems from the presence of marine fouling organisms, mainly bivalve mollusks, in seawater. They survive by feeding on plankton, algae and absorbing organic matter in the water. They float in the seawater and once they encounter suitable environmental conditions, they will attach and reproduce on hard surfaces.

[0003] The operating environment of the seawater cooling system is particularly suitable for the attachment and reproduction of marine fouling organisms. In addition, the intensification of environmental pollution, the increase in water turbidity and eutrophication have further promoted the growth of fouling organisms. If there is a lack of scientific treatment measures, it may cause serious damage to the system. The main impacts include: first, when a large number of marine fouling organisms attach and reproduce, it may cause pipe blockage, thereby reducing water flux; secondly, for systems that rely on seawater for heat exchange, the reduction in water flux will affect the heat exchange efficiency, resulting in a decrease in the temperature difference between the inlet and outlet water ends. In extreme cases, severe blockages may even cause unplanned downtime accidents; in addition, the mucus secreted by the attachment points of fouling organisms has a strong corrosive effect on metals and can accelerate the corrosion process, which poses a serious threat to the safe operation of the system.

[0004] In order to solve the problems caused by the attachment and breeding of marine fouling organisms in the system, mechanical methods, physical methods, antifouling coating methods, chemical methods and biological methods are mainly used. Among them, chemical methods and coating methods are preventive measures, while mechanical methods and physical methods are used to remove attached fouling. As the main means of eliminating the attachment of marine fouling organisms, the chemical method is carried out by introducing chlorine gas, electrolyzing seawater to produce chlorine, or directly adding chemical agents. These water-soluble chemicals can effectively prevent the attachment and breeding of marine fouling organisms in the seawater pipeline system. However, these agents are evenly distributed in seawater, and only the parts in contact with the surface of the seawater cooling system can play an anti-attachment role. Therefore, when the residual chlorine content in the water exceeds 0.5mg / L or even higher, it can achieve a certain effect when used in large doses, but it not only causes a great waste of agents, but may also cause secondary environmental pollution. The national seawater discharge standard "Seawater Cooling Water Discharge Requirements GB / T39361-2020" sets a limit of no more than 0.1mg / L on the residual chlorine content in discharged seawater. This has put forward new requirements for those units that use chlorine-containing oxidizing chemicals to prevent the attachment of marine fouling organisms. They must face the dual challenge of ensuring the killing effect while meeting the emission standards. In particular, when the residual chlorine emission standards are met, the effect of preventing the attachment of marine fouling organisms may be affected, which is a new risk that needs to be paid attention to.

[0005] In order to deal with the problems caused by the attachment and reproduction of marine fouling organisms in the system, the main measures currently taken include mechanical methods, physical methods, antifouling coating methods, chemical methods and biological methods. Among these methods, chemical methods and coating methods mainly play a preventive role, while mechanical methods and physical methods are used to remove already attached fouling organisms. Chemical methods are the main means, which are implemented by injecting chlorine, electrolyzing seawater to produce chlorine, or directly applying chemical agents. These chemical agents are usually easily soluble in water and can effectively inhibit the attachment and growth of marine fouling organisms in seawater pipeline systems. However, since these agents are evenly distributed in seawater, only the part in contact with the surface of the system can play its anti-attachment role. For example, when the residual chlorine content in the water exceeds 0.5mg / L or even higher, a certain effect can be achieved, but this method not only leads to a large amount of waste of agents, but may also cause secondary environmental pollution. According to the technical requirements of the seawater discharge standard "Seawater Cooling Water Discharge Requirements GB / T39361-2020", the residual chlorine content in the discharged seawater shall not exceed 0.1mg / L. This standard poses new challenges to entities that use chlorine-containing oxidizing chemicals to prevent the attachment of marine fouling organisms. While they need to ensure that the chemicals they use are effective in preventing the attachment and growth of marine fouling organisms to ensure the safe operation of the system, they also need to assume social responsibility to ensure that the emission standards are met. This dual requirement constitutes a new risk that requires special attention. Summary of the invention

[0006] The object of the present invention is to provide a protective method for preventing marine fouling organisms from attaching to a seawater cooling system and a drug used therein. The method and the drug used therein can effectively prevent the attachment and growth of marine fouling organisms on the seawater cooling system, thereby avoiding the problem of clogging the seawater cooling system and ensuring the safe operation of the seawater cooling system.

[0007] To achieve the above object, the technical solution adopted by the present invention is: a protective method for preventing marine fouling organisms from attaching to a seawater cooling system, characterized in that it comprises the following steps:

[0008] 1) Prepare a new multi-tube microchannel emulsification equipment;

[0009] 2) Prepare raw materials and reagents to prevent marine fouling organisms from attaching to the seawater cooling system;

[0010] 3) Preparation of agents for preventing marine fouling organisms from attaching to seawater cooling systems: Turning on the heater and ultrasonic probe in the novel multi-tube microchannel emulsification device;

[0011] The emulsifying aid and water in the raw material reagent are stirred evenly to obtain a continuous phase solution, which is input into the main pipeline 12 through the first branch pipe 2 and the first pump 1 of the novel multi-tube microchannel emulsification equipment, with a flow rate of 5-20 liters per hour and a temperature of 40-50° C. (the temperature is adjusted by a heater);

[0012] The (C 14 -C 30 ) Long fatty chain alkylamine, penetrant and stabilizer are prepared into a dispersed phase solution of component A in a mass ratio of 7:2:1, stirred evenly, and input into the main pipeline 12 through the second branch pipe 7, the second pump 8 and the first small hole 6 on the second branch pipe 7 of the novel multi-tube microchannel emulsification device; the flow rate is 0.5-2 liters per hour;

[0013] (C6-C 12 ) The dispersed phase solution of component B composed of short fatty chain alkylamine, the remaining penetrant and the remaining stabilizer is stirred evenly and input into the main pipeline 12 through the third branch pipe 10, the third pump 9 (high-pressure metering pump) and the second small hole 11 on the third branch pipe 10; the flow rate is 0.5-2 liters per hour;

[0014] Each ultrasonic probe has a frequency of 40KHz and a power of 30W. Ultrasonic waves are radiated to the main pipeline 12. The pressure in the main pipeline 12 is 1-2Mpa. The raw material reagent (mixture) flows in the main pipeline 12 for 5-30 minutes. The continuous phase solution and the dispersed phase solution of component A form a micron-level emulsion. The continuous phase solution and the dispersed phase solution of component B form a nano-level emulsion, which is discharged through the outlet 13 of the main pipeline 12 to obtain a drug used to prevent marine fouling organisms from attaching to the seawater cooling system. According to the measurement of the nanoparticle detector, the drug contains two main emulsion particles, one is 80-160 nanometers and the other is 5-50 micrometers. The drug used has the characteristics of uniformity, stability and excellent performance.

[0015] 4) Inject the agent used to prevent marine fouling organisms from attaching to the seawater cooling system into the pipes of the seawater cooling system, so that the concentration of the agent in the seawater is 1-5 mg / L (that is, the agent is applied to the seawater cooling system), 1-7 times a week, and each dosing time is 1-12 hours (dosing means adding the agent).

[0016] A raw material reagent for preventing marine fouling organisms from attaching to a seawater cooling system for realizing the above method, characterized in that it is mainly composed of alkylamine, penetrant, emulsifying aid, stabilizer and water (these materials are prepared into an emulsion with micron and nano structures by a novel multi-tube microchannel emulsifying device); the mass percentage of each material is: alkylamine 5-25%, penetrant 1-5%, emulsifying aid 0.1-2%, stabilizer 1-5%, water 63%-92.9%;

[0017] The alkylamine is mainly composed of (C 14 -C 30 ) long fatty chain alkylamines and (C6-C 12 ) short fatty chain alkylamine, among which (C 14 -C 30 ) The mass ratio of long fatty chain alkylamines is 20-60%, (C6-C 14 )The mass ratio of short fatty chain alkylamine is 40-80%.

[0018] The (C 14 -C 30 ) The long fatty chain alkylamines include any one of N-oleyl-1,3-propylene diamine, N-tetradecyl-1,3-propylene diamine, N1-hexadecyl-1,3-propylene diamine, N-octadecyl-1,3-propylene diamine, N-docosylpropane-1,3-diamine, etc., or a mixture of two or more thereof in any proportion.

[0019] The (C6-C 12) The short fatty chain alkylamine includes any one of N-coconut oil-1,3-propylene diamine, N-dodecyl-1,3-propylene diamine, N-(3-aminopropyl)-N-dodecyl-1,3-propylene diamine, etc., or a mixture of two or more in any ratio.

[0020] The penetrant is composed of any one of saturated or unsaturated carbon chain fatty amine polyoxyethylene ether or the like, or a mixture of two or more of them in any proportion.

[0021] The penetrant includes any one of octadecylamine polyoxyethylene ether, oleylamine polyoxyethylene ether, dodecylamine polyoxyethylene ether, tetradecyl polyoxyethylene ether, hexadecyl polyoxyethylene ether, coconut oil amine polyoxyethylene ether, etc., or a mixture of two or more in any proportion.

[0022] The emulsifying aid includes any one of dodecylbenzene sulfonic acid, sodium dodecylbenzene sulfonate, ammonium dodecylbenzene sulfonate, etc., or a mixture of two or more of them in any proportion.

[0023] The stabilizer includes any one of diethylene glycol, dipropylene glycol, 2-amino-2-methyl-1-propanol, 2-(methylamino)ethanol, etc., or a mixture of two or more of them in any proportion.

[0024] Long-term studies have shown that alkylamines can be easily adsorbed on metal surfaces to form thin films. They not only have excellent functions of sterilization and algae removal and inhibition of microbial growth, but can also effectively remove biological slime, have a certain corrosion inhibition effect, and can be biodegraded. By utilizing these characteristics of alkylamines, we can effectively prevent the deposition of organic nutrients such as biological slime on the surface of the seawater cooling system, thereby depriving bacteria and algae of the environment for growth and preventing marine fouling organisms from attaching and growing on the seawater cooling system. From an economic point of view, we can prepare alkylamines into emulsions that are slightly soluble in seawater. Due to the uneven distribution of emulsion agents in seawater and the effect of the surface tension of the emulsion, the concentration of agents on the surface of objects in contact with seawater is higher, thereby reducing the concentration of agents used and reducing the amount of alkylamines used. At the same time, the study also found that when the emulsion has both nano and micro structures, it will show more excellent functions in preventing the attachment of marine fouling organisms. However, if only conventional emulsification methods are used, that is, simply mixing various materials and then subjecting them to high-speed shearing, it will be difficult to form emulsions of different particle sizes, and it will also be impossible to achieve the coordinated synergistic function of two emulsions of different particle sizes in preventing the attachment of marine fouling organisms.

[0025] The beneficial effects of the present invention are: 1. When the alkylamine emulsion has both nano and micro structures, it can more effectively prevent the attachment of marine fouling organisms, thereby successfully solving the problem of the growth and attachment of marine fouling organisms in the seawater cooling system. The method and its agent can effectively prevent the attachment and growth of marine fouling organisms on the seawater cooling system, thereby avoiding the problem of clogging the seawater cooling system and ensuring the safe operation of the seawater cooling system. The seawater discharge of the present invention fully complies with the relevant emission limits in the "GB 8978-1996 Comprehensive Sewage Discharge Standard", especially for the problem that the residual chlorine in the drainage water exceeds the standard due to the addition of chlorine-containing agents to prevent the attachment of marine fouling organisms in the seawater cooling system, and cannot meet the "GB / T 39361-2020 Seawater Cooling Water Discharge Standard". The present invention provides a solution to ensure the safe and economical operation of the seawater cooling system, while achieving the dual goals of economy and environmental protection.

[0026] 2. The present invention prepares an emulsion with a micro-nano structure through a new multi-tube microchannel emulsification device (or a new multi-component emulsion forming device) that can simultaneously form two emulsion structures of different sizes, which not only reduces costs but also greatly promotes the efficiency of industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 It is a schematic structural diagram of the novel multi-tube microchannel emulsification equipment of the present invention.

[0028] In the figure: 1-first pump, 2-first branch pipe, 3-heater, 4-ultrasonic probe, 5-fin, 6-first small hole, 7-second branch pipe, 8-second pump, 9-third pump, 10-third branch pipe, 11-second small hole, 12-main pipe, 13-export. DETAILED DESCRIPTION

[0029] The preferred embodiments of the present invention are described in detail below with reference to the accompanying drawings.

[0030] Embodiment 1:

[0031] A protective method for preventing marine fouling organisms from attaching to a seawater cooling system comprises the following steps:

[0032] 1) preparing a novel multi-tube microchannel emulsification device (as described below);

[0033] 2) preparing raw materials and reagents for preventing marine fouling organisms from attaching to seawater cooling systems (as described below);

[0034] 3) Preparation of agents for preventing marine fouling organisms from attaching to seawater cooling systems: Turning on the heater and ultrasonic probe in the novel multi-tube microchannel emulsification device;

[0035] The emulsifying aid and water in the raw material reagent are stirred evenly to obtain a continuous phase solution, which is input into the main pipeline 12 through the first branch pipe 2 and the first pump 1 of the novel multi-tube microchannel emulsification equipment, with a flow rate of 5-20 liters per hour and a temperature of 40-50° C. (the temperature is adjusted by a heater);

[0036] The (C 14 -C 30 ) Long fatty chain alkylamine, penetrant and stabilizer are prepared into a dispersed phase solution of component A in a mass ratio of 7:2:1, stirred evenly, and input into the main pipeline 12 through the second branch pipe 7, the second pump 8 and the first small hole 6 on the second branch pipe 7 of the novel multi-tube microchannel emulsification device; the flow rate is 0.5-2 liters per hour;

[0037] (C6-C 12 ) The dispersed phase solution of component B composed of short fatty chain alkylamine, the remaining penetrant and the remaining stabilizer is stirred evenly and input into the main pipeline 12 through the third branch pipe 10, the third pump 9 (high-pressure metering pump) and the second small hole 11 on the third branch pipe 10; the flow rate is 0.5-2 liters per hour;

[0038] Each ultrasonic probe has a frequency of 40KHz and a power of 30W. Ultrasonic waves are radiated to the main pipeline 12. The pressure in the main pipeline 12 is 1-2Mpa. The raw material reagent (mixture) flows in the main pipeline 12 for 5-30 minutes. The continuous phase solution and the dispersed phase solution of component A form a micron-level emulsion. The continuous phase solution and the dispersed phase solution of component B form a nano-level emulsion, which is discharged through the outlet 13 of the main pipeline 12 to obtain a drug used to prevent marine fouling organisms from attaching to the seawater cooling system. According to the measurement of the nanoparticle detector, the drug contains two main emulsion particles, one is 80-160 nanometers and the other is 5-50 micrometers. The drug used has the characteristics of uniformity, stability and excellent performance.

[0039] 4) Inject the agent used to prevent marine fouling organisms from attaching to the seawater cooling system into the pipes of the seawater cooling system so that the concentration of the agent in the seawater is 1.8-2.2 mg / L (about 2.0 mg / L, the agent is applied to the seawater cooling system), 3-5 times a week, each time adding the agent for 4-6 hours (add the agent when the concentration is lower than 1.8 mg / L, keep the agent injected into the pipes of the seawater cooling system, so that the concentration of the agent in the seawater is 1.8-2.2 mg / L).

[0040] like Figure 1As shown, the novel multi-tube microchannel emulsification equipment (capable of simultaneously forming two emulsion structures of different sizes) comprises a first pump 1, a first branch pipe 2, a heater 3, an ultrasonic probe 4, a fin 5, a second branch pipe 7, a second pump 8, a third pump 9, and a third branch pipe 10; one end of the main pipe 12 is an inlet end and is closed, and the inlet end of the main pipe 12 is provided with insertion holes for the first branch pipe, the second branch pipe, and the third branch pipe (used for inserting the first branch pipe, the second branch pipe, and the third branch pipe into the main pipe 12, respectively); the other end of the main pipe 12 is provided with an outlet 13, and annular fins 5 are provided along the pipe wall of the main pipe 12 at intervals of 20 mm from the inlet end to the outlet 13; ultrasonic probes 4 are distributed in an array at intervals of 150 mm from the inlet end to the outlet 13 outside the main pipe 12, and the frequency of each ultrasonic probe 4 is 40KHZ and the power is 30 watts;

[0041] One end of the first branch pipe 2 is the outlet end, and one end of the first branch pipe 2 is inserted into the main channel from the inlet end of the main pipeline 12. The other end of the first branch pipe 2 is provided with a first pump 1 (the other end of the first branch pipe 2 is located outside the main pipeline 12, and a high-pressure metering pump can be used to input the continuous phase solution of water and emulsifying aid into the main pipeline 12); the outer wall of the other end of the first branch pipe 2 is installed (sheathed) with a heater 3 (an electric heater can be used);

[0042] One end of the second branch pipe 7 is a closed end. One end of the second branch pipe 7 is inserted into the main channel from the inlet end of the main pipeline 12. The second branch pipe 7 located in the main pipeline 12 has first small holes 6 with a diameter of 10 microns distributed every 10 mm from the inlet end to the outlet direction. The second branch pipe 7 located in a section of the main pipeline 12 is spirally arranged in the main pipeline 12; the other end of the second branch pipe 7 is located outside the main pipeline 12. The other end of the second branch pipe 7 is provided with a second pump 8 {the second pump can be a high-pressure metering pump, which can be used to (C 14 -C 30 ) The dispersed phase solution of component A composed of long fatty chain alkylamine, penetrant and stabilizer is introduced into the main pipeline 12 through the first small hole 6 thereon};

[0043] One end of the third branch pipe 10 is a closed end. One end of the third branch pipe 10 is inserted into the main channel from the inlet end of the main pipe 12. The third branch pipe 10 located in the main pipe 12 has second small holes 11 with a diameter of 3 microns distributed every 10 mm from the inlet end to the outlet direction. The third branch pipe 10 located in the main pipe 12 is arranged in a spiral shape in the main pipe 12; the other end of the third branch pipe 10 is located outside the main pipe 12. The other end of the third branch pipe 10 is provided with a third pump 9 {the third pump can be a high-pressure metering pump, (C6-C 12 ) The dispersed phase solution of component B composed of short fatty chain alkylamine, the remaining penetrant and the remaining stabilizer is input into the main pipeline 12 through the 3-micron second small hole 11 thereon.

[0044] In this embodiment: the main pipe 12 of the novel multi-tube microchannel emulsification equipment is 5 meters long, 30 mm in diameter, 2 mm in wall thickness, and is made of 316 stainless steel; the first branch pipe 2 is 1 meter long, 10 mm in diameter, 1 mm in wall thickness, and is made of 316 stainless steel; the second branch pipe 7 is 6 meters long, 4 mm in diameter, 1 mm thick, and is made of 316 stainless steel; the third branch pipe 10 is also 6 meters long, 2 mm in diameter, 0.5 mm in wall thickness, and is made of 316 stainless steel.

[0045] A raw material reagent for preventing marine fouling organisms from attaching to a seawater cooling system for realizing the above method, mainly composed of alkylamine, penetrant, emulsifying agent, stabilizer and water (these materials are prepared into an emulsion with micron and nano structures by a novel multi-tube microchannel emulsifying device); the mass percentage of each material is: alkylamine 15%, penetrant 3%, emulsifying agent 1%, stabilizer 3%, water 78%;

[0046] The alkylamine is mainly composed of (C 14 -C 30 ) long fatty chain alkylamines and (C6-C 12 ) short fatty chain alkylamine, among which (C 14 -C 30 ) The mass ratio of long fatty chain alkylamine is 30%, (C6-C 12 )The mass ratio of short fatty chain alkylamine is 70%.

[0047] The (C 14 -C 30 ) The long fatty chain alkylamine is N-oleyl-1,3-propylene diamine. 12 ) The short fatty chain alkylamine is N-cocoyl-1,3-propylene diamine.

[0048] The penetrant is octadecylamine polyoxyethylene ether.

[0049] The emulsifying aid is dodecylbenzenesulfonic acid.

[0050] The stabilizer is diethylene glycol.

[0051] Embodiment 2:

[0052] A protective method for preventing marine fouling organisms from attaching to a seawater cooling system is substantially the same as Example 1, except that:

[0053] The (C 14 -C 30 ) The long fatty chain alkylamine is N-tetradecyl-1,3-propylene diamine. 12 ) The short fatty chain alkylamine is N-dodecyl-1,3-propylene diamine.

[0054] The penetrant is oleylamine polyoxyethylene ether.

[0055] The emulsifying aid is sodium dodecylbenzene sulfonate.

[0056] The stabilizer is dipropylene glycol.

[0057] Embodiment 3:

[0058] A protective method for preventing marine fouling organisms from attaching to a seawater cooling system is substantially the same as Example 1, except that:

[0059] The (C 14 -C 30 ) The long fatty chain alkylamine is N1-hexadecyl-1,3-propylenediamine. 12 ) The short fatty chain alkylamine is N-(3-aminopropyl)-N-dodecyl-1,3-propanediamine.

[0060] The penetrant is dodecylamine polyoxyethylene ether.

[0061] The emulsifying aid is ammonium dodecylbenzene sulfonate.

[0062] The stabilizer is 2-amino-2-methyl-1-propanol.

[0063] Embodiment 4:

[0064] A protective method for preventing marine fouling organisms from attaching to a seawater cooling system is substantially the same as Example 1, except that:

[0065] The (C 14 -C 30 ) The long fatty chain alkylamine is N-octadecyl-1,3-propylenediamine. 12 ) The short fatty chain alkylamine is N-cocoyl-1,3-propylene diamine.

[0066] The penetrant is tetradecyl polyoxyethylene ether.

[0067] The emulsifying aid is dodecylbenzenesulfonic acid.

[0068] The stabilizer is 2-(methylamino)ethanol.

[0069] Application effect test of a protective method for preventing marine fouling organisms from attaching to a seawater cooling system in Example 1-4: 1. Test water quality

[0070] The test water quality is seawater, which is taken from the forebay of a thermal power plant that uses seawater as the circulating cooling water system (i.e., seawater cooling system).

[0071] 2. Test equipment

[0072] The test device includes a power supply, a flow meter, a water pump, water inlet and outlet pipes and a test box. The test box is made of PP plastic and is divided into three parts: a seawater inlet tank, an intermediate marine organism placement tank and a drainage tank by PP plastic plates. The three parts are interconnected by drill holes.

[0073] 3. Test supplies

[0074] 1) Beakers, measuring cylinders, volumetric flasks, pipettes, balances and metering pumps, etc.

[0075] 4. Experimental marine organisms

[0076] The marine organisms used in the experiment are mussels and clams. The mussels and clams are collected from the sea and acclimatized in seawater for at least seven days before being tested.

[0077] 5. Judgment criteria

[0078] 5.1 Criteria for judging the death of marine organisms

[0079] (1) Mussel death standard: The shell cannot be closed after being opened; the mortality rate of mussels in the blank test chamber and the mortality rate of mussels in the drug-added test chamber are counted.

[0080] (2) Clam death standard: the shell cannot be closed after being opened; the mortality rate of clams in the blank monitoring box and the mortality rate of clams in the drug-added test box are counted.

[0081] 5.2 Criteria for judging the growth of marine organisms

[0082] After a test cycle of 15 days, observe or touch the inner wall of the drainage tank in the blank test box and the drug-added test box to see if there is any growth of marine organisms.

[0083] 6. Test methods

[0084] 6.1 After the test device is connected, turn on the power to make the water pump run normally, and ensure the stability of seawater flow by adjusting the valves on the pipeline and calibrating the flow meter;

[0085] 6.2 Place a certain amount of mussels and clams into the test chamber of the test box;

[0086] 6.3 Calculate the dosage of the test agent according to the flow rate of the test seawater, then start the metering pump to make the concentration of the agent in the seawater 2mg / L, and add the agent for 8 hours;

[0087] 6.4 Add medicine once every other day according to method 6.3;

[0088] 6.5 Perform a blank test at the same time;

[0089] 6.5 The test will be terminated after fifteen days, and the death, attachment and reproduction of marine organisms will be observed.

[0090] 7. Test results

[0091] Table 1 Marine biological test data

[0092]

[0093] 8. Experimental conclusion

[0094] The above experimental results show that the agent of the present invention is suitable for preventing the attachment and breeding of marine organisms in industrial cooling water circulation systems using seawater as a supplementary water source, and the seawater discharge fully complies with the relevant emission limits in the "GB 8978-1996 Integrated Sewage Discharge Standard". In particular, in seawater cooling systems, the addition of chlorine-containing agents to prevent the attachment of marine fouling organisms causes the residual chlorine in the drainage water to exceed the standard, which cannot meet the "GB / T 39361-2020 Seawater Cooling Water Discharge Standard". The present invention provides a solution to ensure the safe and economical operation of the system, while achieving the dual goals of economy and environmental protection.

[0095] Embodiment 5:

[0096] A protective method for preventing marine fouling organisms from attaching to a seawater cooling system is basically the same as the one in Examples 1-4, except that the mass percentages of the materials are: 5% alkylamine, 1% penetrant, 0.1% emulsifier, 1% stabilizer, and 92.9% water.

[0097] Embodiment 6:

[0098] A protective method for preventing marine fouling organisms from attaching to a seawater cooling system is basically the same as the one in Example 1, except that the mass percentages of the materials are: 25% alkylamine, 5% penetrant, 2% emulsifier, 5% stabilizer, and 63% water.

[0099] Embodiment 7:

[0100] A protective method for preventing marine fouling organisms from attaching to a seawater cooling system is basically the same as Example 1, except that: Step 4) injecting an agent used to prevent marine fouling organisms from attaching to a seawater cooling system into a pipe of the seawater cooling system so that the concentration of the agent in the seawater is 1-2 mg / L, 1-3 times a week, and each addition lasts 10-12 hours.

[0101] Embodiment 8:

[0102] A protective method for preventing marine fouling organisms from attaching to a seawater cooling system is basically the same as Example 1, except that: Step 4) injecting an agent used to prevent marine fouling organisms from attaching to a seawater cooling system into a pipe of the seawater cooling system so that the concentration of the agent in the seawater is 4.5-5 mg / L, 6-7 times a week, and each addition lasts 1-4 hours.

[0103] The application effect test of Example 5-Example 8 is the same as the above method, and the results are as follows:

[0104] Table 2 Marine biological test data

[0105]

[0106] The above experimental results show that the agent of the present invention is suitable for preventing the attachment and breeding of marine organisms in industrial cooling water circulation systems using seawater as a supplementary water source, and the seawater discharge fully complies with the relevant emission limits in the "GB 8978-1996 Integrated Sewage Discharge Standard". In particular, in seawater cooling systems, the addition of chlorine-containing agents to prevent the attachment of marine fouling organisms causes the residual chlorine in the drainage water to exceed the standard, which cannot meet the "GB / T 39361-2020 Seawater Cooling Water Discharge Standard". The present invention provides a solution to ensure the safe and economical operation of the system, while achieving the dual goals of economy and environmental protection.

[0107] The upper and lower limits, interval values ​​of the raw materials of the present invention, as well as the upper and lower limits, interval values ​​of the process parameters (such as temperature, time, etc.) can all realize the present invention, and the embodiments are not listed one by one here.

[0108] The preferred embodiments of the present invention are described in detail above, but the contents are only preferred embodiments of the present invention and cannot be considered to limit the scope of implementation of the present invention. All equivalent changes and improvements made according to the scope of application of the present invention should still be within the scope of the patent coverage of the present invention.

Claims

1. A method for preventing marine fouling organisms from attaching to a seawater cooling system, characterized in that The steps include: 1) Prepare a new multi-tube microchannel emulsification equipment; The novel multi-tube microchannel emulsification device comprises a first pump (1), a first branch pipe (2), a heater (3), an ultrasonic probe (4), a fin (5), a second branch pipe (7), a second pump (8), a third pump (9), and a third branch pipe (10); one end of the main pipe (12) is an inlet end and is closed, and the inlet end of the main pipe (12) is provided with insertion holes for the first branch pipe, the second branch pipe, and the third branch pipe; the other end of the main pipe (12) is provided with an outlet (13), and annular fins (5) are provided in the main pipe (12) along the pipe wall every (20) mm from the inlet end to the outlet (13); ultrasonic probes (4) are arranged in an array every 150 mm from the inlet end to the outlet (13) outside the main pipe (12), and the frequency of each ultrasonic probe (4) is 40KHZ and the power is 30 watts; One end of the first branch pipe (2) is an outlet end, one end of the first branch pipe (2) is inserted into the main channel from the inlet end of the main pipeline (12), and the other end of the first branch pipe (2) is provided with a first pump (1); a heater (3) is installed on the outer wall of the other end of the first branch pipe (2); One end of the second branch pipe (7) is a closed end. One end of the second branch pipe (7) is inserted into the main channel from the inlet end of the main pipe (12). The second branch pipe (7) located in the main pipe (12) has first small holes (6) with a diameter of 10 micrometers distributed every 10 millimeters in the direction from the inlet end to the outlet. The second branch pipe (7) located in a section of the main pipe (12) is arranged in a spiral shape in the main pipe (12); the other end of the second branch pipe (7) is located outside the main pipe (12). A second pump (8) is provided at the other end of the second branch pipe (7); One end of the third branch pipe (10) is a closed end. One end of the third branch pipe (10) is inserted into the main channel from the inlet end of the main pipe (12). The third branch pipe (10) located in the main pipe (12) has second small holes (11) with a diameter of 3 micrometers distributed every 10 mm in the direction from the inlet end to the outlet. The third branch pipe (10) located in the main pipe (12) is arranged in a spiral shape in the main pipe (12); the other end of the third branch pipe (10) is located outside the main pipe (12). The other end of the third branch pipe (10) is provided with a third pump (9); 2) Prepare raw materials and reagents to prevent marine fouling organisms from attaching to the seawater cooling system; The raw material reagents for preventing marine fouling organisms from attaching to the seawater cooling system are mainly composed of alkylamine, penetrant, emulsifier, stabilizer and water; the mass percentage of each material is: alkylamine 5-25%, penetrant 1-5%, emulsifier 0.1-2%, stabilizer 1-5%, water 63%-92.9%; The alkylamine is mainly composed of (C 14 -C 30 ) long fatty chain alkylamines and (C6-C 12 ) short fatty chain alkylamine, among which (C 14 -C 30 ) The mass ratio of long fatty chain alkylamines is 20-60%, (C6-C 14 ) The mass ratio of short fatty chain alkylamine is 40-80%; 3) Preparation of agents for preventing marine fouling organisms from attaching to seawater cooling systems: Turning on the heater and ultrasonic probe in the novel multi-tube microchannel emulsification device; The emulsifying aid and water in the raw material reagent are stirred evenly to obtain a continuous phase solution, which is input into the main pipeline (12) through the first branch pipe (2) and the first pump (1) of the novel multi-tube microchannel emulsification equipment at a flow rate of 5-20 liters per hour and a temperature of 40-50°C; The (C 14 -C 30 ) a long fatty chain alkylamine, a penetrant and a stabilizer are prepared into a dispersed phase solution of a mixed liquid component A in a mass ratio of 7:2:1, stirred evenly, and introduced into a main pipeline (12) through a second branch pipe (7), a second pump (8) and a first small hole (6) on the second branch pipe (7) of the novel multi-tube microchannel emulsification device; the flow rate is 0.5-2 liters per hour; (C6-C 12 ) a dispersed phase solution of component B composed of a short fatty chain alkylamine, the remaining penetrant and the remaining stabilizer is stirred uniformly and introduced into the main pipeline (12) through the third branch pipe (10), the third pump (9) and the second small hole (11) on the third branch pipe (10); the flow rate is 0.5-2 liters per hour; Each ultrasonic probe has a frequency of 40KHz and a power of 30W. Ultrasonic waves are radiated to the main pipeline (12) with ultrasonic waves. The pressure in the main pipeline (12) is 1-2Mpa. The raw materials and reagents flow in the main pipeline (12) for 5-30 minutes. The continuous phase solution and the dispersed phase solution of the component A form a micron-level emulsion. The continuous phase solution and the dispersed phase solution of the component B form a nano-level emulsion, which is discharged through the outlet (13) of the main pipeline (12), thereby obtaining a drug used to prevent marine fouling organisms from attaching to the seawater cooling system. 4) Inject the agent used to prevent marine fouling organisms from attaching to the seawater cooling system into the pipes of the seawater cooling system so that the concentration of the agent in the seawater is 1-5 mg / L, 1-7 times a week, and each addition time is 1-12 hours.

2. A method for preventing marine fouling organisms from attaching to a seawater cooling system according to claim 1, characterized in that: The (C 14 -C 30 ) The long fatty chain alkylamines include any one of N-oleyl-1,3-propylene diamine, N-tetradecyl-1,3-propylene diamine, N1-hexadecyl-1,3-propylene diamine, N-octadecyl-1,3-propylene diamine, N-docosylpropane-1,3-diamine, etc., or a mixture of two or more thereof in any proportion.

3. A method for preventing marine fouling organisms from attaching to a seawater cooling system according to claim 1, characterized in that: The (C6-C 12 ) The short fatty chain alkylamine includes any one of N-coconut oil-1,3-propylene diamine, N-dodecyl-1,3-propylene diamine, N-(3-aminopropyl)-N-dodecyl-1,3-propylene diamine, etc., or a mixture of two or more in any ratio.

4. A method for preventing marine fouling organisms from attaching to a seawater cooling system according to claim 1, characterized in that: The penetrant is composed of any one of saturated or unsaturated carbon chain fatty amine polyoxyethylene ether or the like, or a mixture of two or more of them in any proportion.

5. A method for preventing marine fouling organisms from attaching to a seawater cooling system according to claim 1 or 4, characterized in that: The penetrant includes any one of octadecylamine polyoxyethylene ether, oleylamine polyoxyethylene ether, dodecylamine polyoxyethylene ether, tetradecyl polyoxyethylene ether, hexadecyl polyoxyethylene ether, coconut oil amine polyoxyethylene ether, etc., or a mixture of two or more in any proportion.

6. A method for preventing marine fouling organisms from attaching to a seawater cooling system according to claim 1, characterized in that: The emulsifying aid includes any one of dodecylbenzene sulfonic acid, sodium dodecylbenzene sulfonate, ammonium dodecylbenzene sulfonate, etc., or a mixture of two or more of them in any proportion.

7. A method for preventing marine fouling organisms from attaching to a seawater cooling system according to claim 1, characterized in that: The stabilizer includes any one of diethylene glycol, dipropylene glycol, 2-amino-2-methyl-1-propanol, 2-(methylamino)ethanol, etc., or a mixture of two or more of them in any proportion.

8. A method for preventing marine fouling organisms from attaching to a seawater cooling system according to claim 1, characterized in that: The main pipe (12) is 5 meters long, 30 mm in diameter, 2 mm thick, and made of 316 stainless steel; the first branch pipe (2) is 1 meter long, 10 mm in diameter, 1 mm thick, and made of 316 stainless steel; the second branch pipe (7) is 6 meters long, 4 mm in diameter, 1 mm thick, and made of 316 stainless steel; the third branch pipe (10) is also 6 meters long, 2 mm in diameter, 0.5 mm thick, and made of 316 stainless steel.

9. A medicament for preventing marine fouling organisms from attaching to a seawater cooling system in accordance with the above method, characterized in that: The raw materials and reagents for preventing marine fouling organisms from attaching to the seawater cooling system are processed by a new multi-tube microchannel emulsification device; The raw material reagents for preventing marine fouling organisms from attaching to the seawater cooling system are mainly composed of alkylamine, penetrant, emulsifier, stabilizer and water; the mass percentage of each material is: alkylamine 5-25%, penetrant 1-5%, emulsifier 0.1-2%, stabilizer 1-5%, water 63%-92.9%; The alkylamine is mainly composed of (C 14 -C 30 ) long fatty chain alkylamines and (C6-C 12 ) short fatty chain alkylamine, among which (C 14 -C 30 ) The mass ratio of long fatty chain alkylamines is 20-60%, (C6-C 14 ) The mass ratio of short fatty chain alkylamine is 40-80%; Turn on the heater and ultrasonic probe in the new multi-tube microchannel emulsification equipment; The emulsifying aid and water in the raw material reagent are stirred evenly to obtain a continuous phase solution, which is input into the main pipeline (12) through the first branch pipe (2) and the first pump (1) of the novel multi-tube microchannel emulsification equipment at a flow rate of 5-20 liters per hour and a temperature of 40-50°C; The (C 14 -C 30 ) a long fatty chain alkylamine, a penetrant and a stabilizer are prepared into a dispersed phase solution of a mixed liquid component A in a mass ratio of 7:2:1, stirred evenly, and introduced into a main pipeline (12) through a second branch pipe (7), a second pump (8) and a first small hole (6) on the second branch pipe (7) of the novel multi-tube microchannel emulsification device; the flow rate is 0.5-2 liters per hour; (C6-C 12 ) a dispersed phase solution of component B composed of a short fatty chain alkylamine, the remaining penetrant and the remaining stabilizer is stirred uniformly and introduced into the main pipeline (12) through the third branch pipe (10), the third pump (9) and the second small hole (11) on the third branch pipe (10); the flow rate is 0.5-2 liters per hour; Each ultrasonic probe has a frequency of 40KHz and a power of 30W. Ultrasonic waves are radiated to the main pipeline (12) with ultrasonic waves. The pressure in the main pipeline (12) is 1-2Mpa. The raw material reagent flows in the main pipeline (12) for 5-30 minutes. The continuous phase solution and the dispersed phase solution of the component A form a micron-level emulsion. The continuous phase solution and the dispersed phase solution of the component B form a nano-level emulsion, which is discharged through the outlet (13) of the main pipeline (12), thereby obtaining a medicine used to prevent marine fouling organisms from attaching to the seawater cooling system.

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