Cleaning agent for water-cooling system of engine and preparation method of cleaning agent

Abstract

The invention discloses an engine water cooling system cleaning agent and a preparation method thereof, and relates to the technical field of cleaning agents. The cleaning agent for the water cooling system of the engine prepared by the invention is prepared by mixing modified activated carbon, modified polythiophene, sodium citrate, N, N-bis (hydroxyethyl) dodecyl amide, a Lan-826 pickling corrosion inhibitor, dodecyl betaine, triethanolamine, polyaspartic acid tetracarboxylic acid ethyl ester and ethylene glycol monobutyl ether, and then adding the modified activated carbon, the modified polythiophene, the sodium citrate, the N, N-bis (hydroxyethyl) dodecyl amide, the Lan-826 pickling corrosion inhibitor, the dodecyl betaine, the triethanolamine and the ethylene glycol monobutyl ether. The modified activated carbon is obtained by treating loaded activated carbon obtained by reacting activated carbon, bismuth nitrate pentahydrate and ferric nitrate with a silane coupling agent and then reacting with 6-acrylamido-beta-cyclodextrin under the irradiation of a mercury lamp; the modified polythiophene is obtained by reacting dibromo terpyridyl with (4-(dimethylamino) thiophene-2-yl) boric acid, then reacting with 2, 7-bis (bromomethyl) pyrene, and then reacting with thiophene. The engine water cooling system cleaning agent prepared by the invention has good thermal degradation efficiency, cleaning efficiency and antibacterial performance.

Description

Technical Field

[0001] The invention relates to the technical field of cleaning agents, in particular to a cleaning agent for an engine water cooling system and a preparation method thereof. Background Art

[0002] Engine water cooling system cleaning agent is a chemical agent specially designed to remove deposits, scale and corrosion products in the engine cooling system. During long-term use, the engine water cooling system may accumulate various impurities, such as metal debris, scale, grease, additive residues in old coolant, and deposits caused by corrosion. These impurities will not only reduce the efficiency of the cooling system, but also may cause damage to engine components, such as blocking waterways, affecting heat dissipation, and even causing engine overheating.

[0003] In order to effectively remove these impurities, engine water cooling system cleaning agents usually contain a variety of active ingredients. Among them, common ingredients include organic acids, inorganic acids, surfactants, corrosion inhibitors and dispersants. Organic and inorganic acids can dissolve and peel off deposits and scale; surfactants help disperse and suspend impurities for subsequent flushing; corrosion inhibitors can protect the metal parts of the cooling system from corrosion by the acidic components in the cleaning agent; dispersants can ensure that impurities will not be redeposited during the cleaning process.

[0004] It is necessary to prepare an efficient, safe and environmentally friendly cleaning agent for engine water cooling system, which should be able to quickly and thoroughly remove various impurities in the cooling system without causing any damage to the system. Summary of the invention

[0005] The purpose of the present invention is to provide an engine water cooling system cleaning agent and a preparation method thereof, so as to solve the problems existing in the prior art.

[0006] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0007] The invention discloses an engine water cooling system cleaning agent, comprising the following components: modified activated carbon, modified polythiophene, sodium citrate, N,N-bishydroxyethyl dodecylamide, Lan-826 pickling corrosion inhibitor, dodecyl betaine, triethanolamine, polyaspartic acid tetracarboxylic acid ethyl ester, ethylene glycol monobutyl ether, and 30wt% hydrogen peroxide.

[0008] Preferably, the modified activated carbon is obtained by reacting activated carbon, bismuth nitrate pentahydrate and ferric nitrate through alkaline hydrothermal reaction, which is treated with vinyltrimethoxysilane and then reacted with 6-acrylamide-β-cyclodextrin under irradiation of a mercury lamp.

[0009] Preferably, the modified polythiophene is obtained by reacting 5,5'-dibromo-2,2':6',2"-terpyridine with thienyl bipyridine obtained by reacting (4-(dimethylamino)thiophen-2-yl)boric acid with 2,7-bis(bromomethyl)pyrene, and then polymerizing with thiophene.

[0010] A method for preparing an engine water cooling system cleaning agent comprises the following preparation steps:

[0011] (1) bismuth nitrate pentahydrate, ferric nitrate, 10 wt% nitric acid and activated carbon were ultrasonically mixed for 5 min, the pH was adjusted to 10 with a 6 mol / L potassium hydroxide solution, filtered and washed with pure water 4 times to obtain a precipitate, the precipitate, 2 mol / L potassium hydroxide solution and potassium nitrate were mixed, stirred for 30 min, transferred to a Teflon-lined stainless steel reactor, heated at 160° C. for 6 h, cooled to room temperature, washed with pure water, and vacuum dried at 50° C. to obtain loaded activated carbon;

[0012] (2) Vinyltrimethoxysilane, anhydrous ethanol and pure water were mixed at a mass ratio of 1:1:5 for 10 minutes, and activated carbon loaded with twice the mass of vinyltrimethoxysilane was added, the temperature was raised to 110° C., refluxed for 4 hours, filtered and washed with anhydrous ethanol for 4 times, and vacuum dried to obtain pretreated activated carbon;

[0013] (3) Pretreated activated carbon, 6-acrylamide-β-cyclodextrin, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, and 2.5 wt% methanol solution were mixed in a mass ratio of 1:(0.2-0.3):(0.002-0.003):400, and ultrasonicated for 50-60 min under nitrogen protection, and then irradiated under a 500 W high-pressure mercury lamp for 4-5 h, filtered and washed with pure water for 3-4 times, and vacuum dried at 50-60 ° C for 12 h to obtain modified activated carbon;

[0014] (4) Under nitrogen protection, 5,5"-dibromo-2,2':6',2"-terpyridine, (4-(dimethylamino)thiophene-2-yl)boric acid, tetrakis(triphenylphosphine)palladium, ethylene glycol dimethyl ether, and 2 mol / L potassium carbonate solution were mixed, heated to 110-120°C for reaction for 24 hours, and after the reaction, cooled to room temperature, filtered and recrystallized from toluene to obtain thienyl bipyridine; thienyl bipyridine, 2,7-bis(bromomethyl)pyrene, acetonitrile, and potassium iodide were mixed in a mass ratio of 1:(0.8-1.0):(20-30):0.3, reacted at 40-50°C for 10-15 hours, and after the reaction, the modified thiophene was obtained by vacuum distillation;

[0015] (5) Weighing thiophene and anhydrous ferric chloride in a mass ratio of 1:(14-16); mixing thiophene, modified thiophene and chloroform in a mass ratio of 1:(0.1-0.2):(10-12) to obtain a thiophene mixed solution; mixing anhydrous ferric chloride and chloroform in a mass ratio of 1:(20-30), adding the thiophene mixed solution at 0-5°C and reacting for 6 hours, then heating to room temperature and continuing to react for 24 hours. After the reaction is completed, filtering and washing with pure water for 3-4 times to obtain modified polythiophene;

[0016] (6) The following components: modified activated carbon, modified polythiophene, sodium citrate, N,N-bis(hydroxyethyl) dodecylamide, Lan-826 pickling corrosion inhibitor, dodecyl betaine, triethanolamine, polyaspartic acid tetracarboxylic acid ethyl ester, ethylene glycol monobutyl ether, and 30 wt % hydrogen peroxide are mixed to obtain an engine water cooling system cleaning agent.

[0017] Preferably, in step (1), the molar ratio of bismuth nitrate pentahydrate, ferric nitrate and potassium nitrate is 1:1:20; the molar ratio of bismuth nitrate pentahydrate, ferric nitrate and potassium nitrate is 1:1:20; the mass ratio of bismuth nitrate pentahydrate, activated carbon and 10wt% nitric acid is 1:0.3:50, and the volume ratio of 10wt% nitric acid and 2mol / L potassium hydroxide solution is 1:8.

[0018] Preferably, the molar ratio of 5,5"-dibromo-2,2':6',2"-terpyridine, (4-(dimethylamino)thiophene-2-yl)boric acid and tetrakis(triphenylphosphine)palladium in step (4) is 1:2.5:0.05, and the tetrakis(triphenylphosphine)palladium and ethylene glycol are preferably used in the following amounts: by mass: 5-6 parts of modified activated carbon, 20-30 parts of modified polythiophene, 10-15 parts of sodium citrate, 5-8 parts of N,N-bis(hydroxyethyl)dodecylamide, 2-3 parts of Lan-826 pickling corrosion inhibitor, 2-3 parts of dodecyl betaine, 5-6 parts of triethanolamine, 10-15 parts of polyaspartic acid tetracarboxylic acid ethyl ester, 50-60 parts of ethylene glycol monobutyl ether, and 1-2 parts of 30wt% hydrogen peroxide.

[0019] Preferably, the activated carbon is of GB-1 type.

[0020] Preferably, the cleaning temperature of the engine water cooling system cleaning agent is 65-75°C.

[0021] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0022] When preparing the cleaning agent for the engine water cooling system, the invention comprises the following steps: firstly, the loaded activated carbon obtained by alkaline hydrothermal reaction of activated carbon, bismuth nitrate pentahydrate and ferric nitrate is treated with vinyl trimethoxysilane, and then reacted with 6-acrylamide-β-cyclodextrin under the irradiation of a mercury lamp to obtain modified activated carbon; secondly, the thienyl bipyridine obtained by the reaction of 5,5"-dibromo-2,2':6',2"-terpyridine and (4-(dimethylamino)thiophene-2-yl)boric acid is reacted with 2,7-bis(bromomethyl)pyrene, and then polymerized with thiophene to obtain modified polythiophene; finally, the modified activated carbon, the modified polythiophene, sodium citrate, N,N-bishydroxyethyl dodecylamide, Lan-826 pickling corrosion inhibitor, dodecyl betaine, triethanolamine, polyaspartic acid tetracarboxylic acid ethyl ester and ethylene glycol monobutyl ether are mixed to obtain the cleaning agent.

[0023] Firstly, activated carbon, bismuth nitrate pentahydrate and ferric nitrate are reacted through a one-step alkaline hydrothermal reaction to obtain activated carbon loaded with bismuth ferrite of bismuth bismuth ore phase. The activated carbon itself has good adsorption capacity and can adsorb impurities. After being treated with vinyltrimethoxysilane, the surface of the activated carbon has vinyl groups, which can be polymerized by free radicals through irradiation of a high-pressure mercury lamp and 6-acrylamide-β-cyclodextrin containing double bonds under the action of a photocatalyst. The cavity inside the β-cyclodextrin can adsorb a variety of substances. At the same time, the bismuth ferrite of bismuth ore phase on the surface of the activated carbon, as a precursor, will form bismuth oxycarbonate under the irradiation of a high-pressure mercury lamp, and form a heterojunction with the remaining bismuth ferrite of bismuth ore phase, which promotes the separation of electrons and holes. It has a strong thermal catalytic degradation efficiency under the synergistic effect of hydrogen peroxide, and can degrade phenolic organic matter during the cleaning process, such as the residue of phenolic organic matter in the coolant, thereby achieving the purpose of environmentally friendly cleaning.

[0024] Secondly, thienyl bipyridine obtained by the reaction of 5,5"-dibromo-2,2':6',2"-terpyridine and (4-(dimethylamino)thiophene-2-yl)boric acid is reacted with 2,7-bis(bromomethyl)pyrene to generate a quaternary ammonium salt structure with antibacterial properties, which is then polymerized with thiophene to obtain modified polythiophene. The thiophene and bipyridine structures have good complexing ability for metal ions and can complex scale metal ions in the water cooling system. The pyrene structure can adsorb pollutants containing benzene ring structures through ππ stacking. DETAILED DESCRIPTION

[0025] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of 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.

[0026] The activated carbon used in the following examples and comparative examples is GB-1 type; the molar ratio of bismuth nitrate pentahydrate, ferric nitrate and potassium nitrate used is 1:1:20; the mass ratio of bismuth nitrate pentahydrate, activated carbon and 10wt% nitric acid used is 1:0.3:50, and the volume ratio of 10wt% nitric acid and 2mol / L potassium hydroxide solution used is 1:8; the molar ratio of 5,5"-dibromo-2,2':6',2"-terpyridine, (4-(dimethylamino)thiophene-2-yl)boric acid and tetrakis(triphenylphosphine)palladium used is 1:2.5:0.05, and the mass ratio of tetrakis(triphenylphosphine)palladium, ethylene glycol dimethyl ether and 2mol / L potassium carbonate used is 1:50:30.

[0027] Embodiment 1:

[0028] A method for preparing an engine water cooling system cleaning agent, the method comprising the following preparation steps:

[0029] (1) bismuth nitrate pentahydrate, ferric nitrate, 10 wt% nitric acid and activated carbon were ultrasonically mixed for 5 min, the pH was adjusted to 10 with a 6 mol / L potassium hydroxide solution, filtered and washed with pure water 4 times to obtain a precipitate, the precipitate, 2 mol / L potassium hydroxide solution and potassium nitrate were mixed, stirred for 30 min, transferred to a Teflon-lined stainless steel reactor, heated at 160° C. for 6 h, cooled to room temperature, washed with pure water, and vacuum dried at 50° C. to obtain loaded activated carbon;

[0030] (2) Vinyltrimethoxysilane, anhydrous ethanol and pure water were mixed at a mass ratio of 1:1:5 for 10 minutes, and activated carbon loaded with twice the mass of vinyltrimethoxysilane was added, the temperature was raised to 110° C., refluxed for 4 hours, filtered and washed with anhydrous ethanol for 4 times, and vacuum dried to obtain pretreated activated carbon;

[0031] (3) pretreated activated carbon, 6-acrylamide-β-cyclodextrin, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, and 2.5wt% methanol solution were mixed in a mass ratio of 1:0.2:0.002:400, and ultrasonicated for 60 min under nitrogen protection, and then irradiated under a 500W high-pressure mercury lamp for 5 h, filtered and washed with pure water for 4 times, and vacuum dried at 60°C for 12 h to obtain modified activated carbon;

[0032] (4) Under nitrogen protection, 5,5"-dibromo-2,2':6',2"-terpyridine, (4-(dimethylamino)thiophene-2-yl)boric acid, tetrakis(triphenylphosphine)palladium, ethylene glycol dimethyl ether, and 2 mol / L potassium carbonate solution were mixed, heated to 120°C for reaction for 24 hours, and after the reaction, cooled to room temperature, filtered and recrystallized from toluene to obtain thienyl bipyridine; thienyl bipyridine, 2,7-bis(bromomethyl)pyrene, acetonitrile, and potassium iodide were mixed in a mass ratio of 1:0.8:20:0.3, reacted at 50°C for 15 hours, and after the reaction, the modified thiophene was obtained by vacuum distillation;

[0033] (5) Weigh thiophene and anhydrous ferric chloride in a mass ratio of 1:14; mix thiophene, modified thiophene and chloroform in a mass ratio of 1:0.1:10 to obtain a thiophene mixed solution; mix anhydrous ferric chloride and chloroform in a mass ratio of 1:20, add the thiophene mixed solution at 5°C and react for 6 hours, then heat to room temperature and continue to react for 24 hours. After the reaction is completed, filter and wash with pure water 4 times to obtain modified polythiophene;

[0034] (6) The following components, measured by mass, are mixed: 5 parts of modified activated carbon, 20 parts of modified polythiophene, 10 parts of sodium citrate, 5 parts of N,N-bis(hydroxyethyl)dodecylamide, 2 parts of Lan-826 pickling corrosion inhibitor, 2 parts of dodecyl betaine, 5 parts of triethanolamine, 10 parts of polyaspartic acid tetracarboxylic acid ethyl ester, 50 parts of ethylene glycol monobutyl ether, and 1 part of 30 wt% hydrogen peroxide to obtain an engine water cooling system cleaning agent.

[0035] Embodiment 2:

[0036] A method for preparing an engine water cooling system cleaning agent, the method comprising the following preparation steps:

[0037] (1) bismuth nitrate pentahydrate, ferric nitrate, 10 wt% nitric acid and activated carbon were ultrasonically mixed for 5 min, the pH was adjusted to 10 with a 6 mol / L potassium hydroxide solution, filtered and washed with pure water 4 times to obtain a precipitate, the precipitate, 2 mol / L potassium hydroxide solution and potassium nitrate were mixed, stirred for 30 min, transferred to a Teflon-lined stainless steel reactor, heated at 160° C. for 6 h, cooled to room temperature, washed with pure water, and vacuum dried at 50° C. to obtain loaded activated carbon;

[0038] (2) Vinyltrimethoxysilane, anhydrous ethanol and pure water were mixed at a mass ratio of 1:1:5 for 10 minutes, and activated carbon loaded with twice the mass of vinyltrimethoxysilane was added, the temperature was raised to 110° C., refluxed for 4 hours, filtered and washed with anhydrous ethanol for 4 times, and vacuum dried to obtain pretreated activated carbon;

[0039] (3) pretreated activated carbon, 6-acrylamide-β-cyclodextrin, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, and 2.5 wt% methanol solution were mixed in a mass ratio of 1:0.25:0.0025:400, and ultrasonicated for 55 min under nitrogen protection, and then irradiated under a 500 W high-pressure mercury lamp for 4.5 h, filtered and washed with pure water for 3 times, and vacuum dried at 55 ° C for 12 h to obtain modified activated carbon;

[0040] (4) Under nitrogen protection, 5,5"-dibromo-2,2':6',2"-terpyridine, (4-(dimethylamino)thiophene-2-yl)boric acid, tetrakis(triphenylphosphine)palladium, ethylene glycol dimethyl ether, and 2 mol / L potassium carbonate solution were mixed, heated to 115°C for reaction for 24 hours, and after the reaction, cooled to room temperature, filtered and recrystallized from toluene to obtain thienyl bipyridine; thienyl bipyridine, 2,7-bis(bromomethyl)pyrene, acetonitrile, and potassium iodide were mixed in a mass ratio of 1:0.9:25:0.3, reacted at 45°C for 12 hours, and after the reaction, the modified thiophene was obtained by vacuum distillation;

[0041] (5) Weigh thiophene and anhydrous ferric chloride in a mass ratio of 1:15; mix thiophene, modified thiophene and chloroform in a mass ratio of 1:0.15:11 to obtain a thiophene mixed solution; mix anhydrous ferric chloride and chloroform in a mass ratio of 1:25, add the thiophene mixed solution at 4°C and react for 6 hours, then heat to room temperature and continue to react for 24 hours. After the reaction is completed, filter and wash with pure water three times to obtain modified polythiophene;

[0042] (6) The following components, measured by mass, are mixed: 5.5 parts of modified activated carbon, 25 parts of modified polythiophene, 13 parts of sodium citrate, 7 parts of N,N-bis(hydroxyethyl)dodecylamide, 2.5 parts of Lan-826 pickling corrosion inhibitor, 2.5 parts of dodecyl betaine, 5.5 parts of triethanolamine, 12 parts of polyaspartic acid tetracarboxylic acid ethyl ester, 55 parts of ethylene glycol monobutyl ether, and 1.2 parts of 30 wt % hydrogen peroxide to obtain an engine water cooling system cleaning agent.

[0043] Embodiment 3:

[0044] A method for preparing an engine water cooling system cleaning agent, the method comprising the following preparation steps:

[0045] (1) bismuth nitrate pentahydrate, ferric nitrate, 10 wt% nitric acid and activated carbon were ultrasonically mixed for 5 min, the pH was adjusted to 10 with a 6 mol / L potassium hydroxide solution, filtered and washed with pure water 4 times to obtain a precipitate, the precipitate, 2 mol / L potassium hydroxide solution and potassium nitrate were mixed, stirred for 30 min, transferred to a Teflon-lined stainless steel reactor, heated at 160° C. for 6 h, cooled to room temperature, washed with pure water, and vacuum dried at 50° C. to obtain loaded activated carbon;

[0046] (2) Vinyltrimethoxysilane, anhydrous ethanol and pure water were mixed at a mass ratio of 1:1:5 for 10 minutes, and activated carbon loaded with twice the mass of vinyltrimethoxysilane was added, the temperature was raised to 110° C., refluxed for 4 hours, filtered and washed with anhydrous ethanol for 4 times, and vacuum dried to obtain pretreated activated carbon;

[0047] (3) Pretreated activated carbon, 6-acrylamide-β-cyclodextrin, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, and 2.5 wt% methanol solution were mixed in a mass ratio of 1:0.3:0.003:400, and ultrasonicated for 50 min under nitrogen protection, and then irradiated for 4 h under a 500 W high-pressure mercury lamp, filtered and washed with pure water for 3 times, and vacuum dried at 50 ° C for 12 h to obtain modified activated carbon;

[0048] (4) Under nitrogen protection, 5,5"-dibromo-2,2':6',2"-terpyridine, (4-(dimethylamino)thiophene-2-yl)boric acid, tetrakis(triphenylphosphine)palladium, ethylene glycol dimethyl ether, and 2 mol / L potassium carbonate solution were mixed, heated to 110°C for reaction for 24 hours, and after the reaction, cooled to room temperature, filtered and recrystallized from toluene to obtain thienyl bipyridine; thienyl bipyridine, 2,7-bis(bromomethyl)pyrene, acetonitrile, and potassium iodide were mixed in a mass ratio of 1:1.0:30:0.3, reacted at 40°C for 10 hours, and after the reaction, the modified thiophene was obtained by vacuum distillation;

[0049] (5) Weigh thiophene and anhydrous ferric chloride in a mass ratio of 1:16; mix thiophene, modified thiophene and chloroform in a mass ratio of 1:0.2:12 to obtain a thiophene mixed solution; mix anhydrous ferric chloride and chloroform in a mass ratio of 1:30, add the thiophene mixed solution at 0°C and react for 6 hours, then heat to room temperature and continue to react for 24 hours. After the reaction is completed, filter and wash with pure water three times to obtain modified polythiophene;

[0050] (6) The following components, measured by mass, are mixed: 6 parts of modified activated carbon, 30 parts of modified polythiophene, 15 parts of sodium citrate, 8 parts of N,N-bis(hydroxyethyl)dodecylamide, 3 parts of Lan-826 pickling corrosion inhibitor, 3 parts of dodecyl betaine, 6 parts of triethanolamine, 15 parts of polyaspartic acid tetracarboxylic acid ethyl ester, 60 parts of ethylene glycol monobutyl ether, and 2 parts of 30 wt% hydrogen peroxide to obtain an engine water cooling system cleaning agent.

[0051] Comparative Example 1:

[0052] The difference between the preparation method of the engine water cooling system cleaning agent of Comparative Example 1 and Example 2 is that step (6) is modified as follows: the following components, in parts by mass, are mixed: 25 parts of modified polythiophene, 13 parts of sodium citrate, 7 parts of N,N-bis(hydroxyethyl)dodecylamide, 2.5 parts of Lan-826 pickling corrosion inhibitor, 2.5 parts of dodecyl betaine, 5.5 parts of triethanolamine, 12 parts of polyaspartic acid tetracarboxylic acid ethyl ester, and 55 parts of ethylene glycol monobutyl ether to obtain an engine water cooling system cleaning agent.

[0053] Comparative Example 2:

[0054] The preparation method of the engine water cooling system cleaning agent of Comparative Example 2 differs from that of Example 2 in that step (6) is modified as follows: the following components, in parts by mass, are mixed: 5.5 parts of modified activated carbon, 13 parts of sodium citrate, 7 parts of N,N-bishydroxyethyl dodecylamide, 2.5 parts of Lan-826 pickling corrosion inhibitor, 2.5 parts of dodecyl betaine, 5.5 parts of triethanolamine, 12 parts of polyaspartic acid tetracarboxylic acid ethyl ester, 55 parts of ethylene glycol monobutyl ether, and 1.2 parts of 30wt% hydrogen peroxide to obtain an engine water cooling system cleaning agent.

[0055] Test Example 1:

[0056] Thermal degradation performance test:

[0057] Test method: The thermal catalytic degradation of phenol wastewater was carried out in a water bath at a temperature of 65°C. 50 mg of the cleaning agent prepared in the embodiment and the comparative example was added to 5 mL of a 10 mg / L p-chlorophenol solution, and ultrasonicated for 1.0 min to make it dispersed evenly. After 60 min, the degradation rate of p-chlorophenol was analyzed using a high performance liquid chromatograph. The results are shown in Table 1.

[0058] Table 1 Degradation performance test results

[0059]

[0060]

[0061] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 2 in Table 1, it can be found that the engine water cooling system cleaning agent prepared by the present invention has good thermal degradation performance.

[0062] By comparison, the degradation rate of p-chlorophenol in Examples 1 to 3 is greater than that of p-chlorophenol in Comparative Example 1, indicating that the activated carbon loaded with bismuth ferrite of soft bismuth mineral phase is obtained by a one-step alkaline hydrothermal reaction of activated carbon, bismuth nitrate pentahydrate and ferric nitrate, the activated carbon itself has good adsorption and can adsorb impurities, and after being treated with vinyltrimethoxysilane, the surface of the activated carbon has vinyl groups, which can be irradiated by a high-pressure mercury lamp and polymerized by free radicals with 6-acrylamide-β-cyclodextrin containing double bonds under the action of a photocatalyst, and the cavity inside the β-cyclodextrin can adsorb a variety of substances; at the same time, the bismuth ferrite of soft bismuth mineral phase on the surface of the activated carbon, as a precursor, will form bismuth carbonate under the irradiation of a high-pressure mercury lamp, and form a heterojunction with the remaining bismuth ferrite of soft bismuth mineral phase, which promotes the separation of electrons and holes, and has a strong thermal catalytic degradation efficiency under the synergistic effect of hydrogen peroxide, and can degrade phenolic organic matter during the cleaning process, such as the residue of phenolic organic matter in the coolant, thereby achieving the purpose of environmentally friendly cleaning.

[0063] Test Example 2:

[0064] Decontamination test:

[0065] Test method: The detergency test was conducted in accordance with standard GBT31027-2014, and the cleaning efficiency was calculated. The results are shown in Table 2.

[0066] Table 2 Decontamination ability test results

[0067] Cleaning efficiency (%) Cleaning efficiency (%) Example 1 96.42 Comparative Example 1 89.31 Example 2 96.57 Comparative Example 2 63.25 Example 3 97.01

[0068] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 2 in Table 2, it can be found that the engine water cooling system cleaning agent prepared by the present invention has good cleaning efficiency.

[0069] By comparison, the cleaning efficiency of Examples 1 to 3 and is greater than that of Comparative Examples 1 to 2, indicating that the activated carbon, bismuth nitrate pentahydrate, and ferric nitrate are reacted by a one-step alkaline hydrothermal reaction to obtain activated carbon loaded with bismuth ferrite phase. The activated carbon itself has good adsorption properties and can adsorb impurities. After being treated with vinyl trimethoxysilane, the surface of the activated carbon has vinyl groups, which can be irradiated by a high-pressure mercury lamp under the action of a photocatalyst and polymerized by free radicals with 6-acrylamide-β-cyclodextrin containing double bonds. The cavity inside the β-cyclodextrin can Adsorb a variety of substances; secondly, the thienyl bipyridine obtained by the reaction of 5,5"-dibromo-2,2':6',2"-terpyridine and (4-(dimethylamino)thiophene-2-yl)boric acid is reacted with 2,7-bis(bromomethyl)pyrene to generate a quaternary ammonium salt structure with antibacterial properties, which is then polymerized with thiophene to obtain modified polythiophene. The thiophene and bipyridine structures have good complexing ability for metal ions and can complex scale metal ions in the water cooling system. The pyrene structure can adsorb pollutants containing benzene ring structures through ππ stacking.

[0070] Embodiment 3:

[0071] Antibacterial performance test:

[0072] Test method: The antibacterial rate of the high-efficiency and environmentally friendly flocculants prepared in the examples and comparative examples was tested according to standard WS / T 650-2019. The results are shown in Table 3.

[0073] Table 3 Antibacterial performance test results

[0074] Antibacterial rate (%) Antibacterial rate (%) Example 1 98.75 Comparative Example 1 96.53 Example 2 98.74 Comparative Example 2 26.74 Example 3 99.01

[0075] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 2 in Table 3, it can be found that the cleaning agent prepared by the present invention has good antibacterial properties.

[0076] By comparison, the antibacterial rates of Examples 1 to 3 are greater than that of Comparative Example 2, indicating that 5,5"-dibromo-2,2':6',2"-terpyridine, thienyl bipyridine obtained by the reaction of (4-(dimethylamino)thiophene-2-yl)boric acid, and 2,7-bis(bromomethyl)pyrene react to generate a quaternary ammonium salt structure with antibacterial properties.

[0077] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations within the meaning and scope of the equivalent elements of the claims be included in the invention. Any marking in a claim should not be considered as limiting the claim to which it relates.

Claims

1. An engine water cooling system cleaning agent, characterized in that: The engine water cooling system cleaning agent comprises the following components: modified activated carbon, modified polythiophene, sodium citrate, N,N-bishydroxyethyl dodecylamide, Lan-826 pickling corrosion inhibitor, dodecyl betaine, triethanolamine, polyaspartic acid tetracarboxylic acid ethyl ester, ethylene glycol monobutyl ether, and 30wt% hydrogen peroxide; The modified activated carbon is obtained by reacting activated carbon, bismuth nitrate pentahydrate and ferric nitrate through alkaline hydrothermal reaction, and then treated with vinyl trimethoxysilane and 6-acrylamide-β-cyclodextrin under the irradiation of a mercury lamp. The modified polythiophene is obtained by reacting 5,5'-dibromo-2,2':6',2"-terpyridine with (4-(dimethylamino)thiophene-2-yl)boric acid to obtain thienyl bipyridine, reacting with 2,7-bis(bromomethyl)pyrene, and then polymerizing with thiophene.

2. A method for preparing an engine water cooling system cleaning agent, characterized in that: The method comprises the following preparation steps: (1) bismuth nitrate pentahydrate, ferric nitrate, 10 wt% nitric acid and activated carbon were ultrasonically mixed for 5 min, the pH was adjusted to 10 with a 6 mol / L potassium hydroxide solution, filtered and washed with pure water 4 times to obtain a precipitate, the precipitate, 2 mol / L potassium hydroxide solution and potassium nitrate were mixed, stirred for 30 min, transferred to a Teflon-lined stainless steel reactor, heated at 160° C. for 6 h, cooled to room temperature, washed with pure water, and vacuum dried at 50° C. to obtain loaded activated carbon; (2) Vinyltrimethoxysilane, anhydrous ethanol and pure water were mixed at a mass ratio of 1:1:5 for 10 minutes, and activated carbon loaded with twice the mass of vinyltrimethoxysilane was added, the temperature was raised to 110° C., refluxed for 4 hours, filtered and washed with anhydrous ethanol for 4 times, and vacuum dried to obtain pretreated activated carbon; (3) Pretreated activated carbon, 6-acrylamide-β-cyclodextrin, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, and 2.5 wt% methanol solution were mixed in a mass ratio of 1:(0.2-0.3):(0.002-0.003):400, and ultrasonicated for 50-60 min under nitrogen protection, and then irradiated under a 500 W high-pressure mercury lamp for 4-5 h, filtered and washed with pure water for 3-4 times, and vacuum dried at 50-60 ° C for 12 h to obtain modified activated carbon; (4) Under nitrogen protection, 5,5"-dibromo-2,2':6',2"-terpyridine, (4-(dimethylamino)thiophene-2-yl)boric acid, tetrakis(triphenylphosphine)palladium, ethylene glycol dimethyl ether, and 2 mol / L potassium carbonate solution were mixed, heated to 110-120°C for reaction for 24 hours, and after the reaction, cooled to room temperature, filtered and recrystallized from toluene to obtain thienyl bipyridine; thienyl bipyridine, 2,7-bis(bromomethyl)pyrene, acetonitrile, and potassium iodide were mixed in a mass ratio of 1:(0.8-1.0):(20-30):0.3, reacted at 40-50°C for 10-15 hours, and after the reaction, the modified thiophene was obtained by vacuum distillation; (5) Weighing thiophene and anhydrous ferric chloride in a mass ratio of 1:(14-16); mixing thiophene, modified thiophene and chloroform in a mass ratio of 1:(0.1-0.2):(10-12) to obtain a thiophene mixed solution; mixing anhydrous ferric chloride and chloroform in a mass ratio of 1:(20-30), adding the thiophene mixed solution at 0-5°C and reacting for 6 hours, then heating to room temperature and continuing to react for 24 hours. After the reaction is completed, filtering and washing with pure water for 3-4 times to obtain modified polythiophene; (6) The following components: modified activated carbon, modified polythiophene, sodium citrate, N,N-bis(hydroxyethyl) dodecylamide, Lan-826 pickling corrosion inhibitor, dodecyl betaine, triethanolamine, polyaspartic acid tetracarboxylic acid ethyl ester, ethylene glycol monobutyl ether, and 30 wt % hydrogen peroxide are mixed to obtain an engine water cooling system cleaning agent.

3. The method for preparing an engine water cooling system cleaning agent according to claim 2, characterized in that: The molar ratio of the bismuth nitrate pentahydrate, ferric nitrate and potassium nitrate in step (1) is 1:1:20; the molar ratio of the bismuth nitrate pentahydrate, ferric nitrate and potassium nitrate is 1:1:20; the mass ratio of the bismuth nitrate pentahydrate, activated carbon and 10wt% nitric acid is 1:0.3:50, and the volume ratio of the 10wt% nitric acid and 2mol / L potassium hydroxide solution is 1:

8.

4. The method for preparing an engine water cooling system cleaning agent according to claim 2, characterized in that: The molar ratio of 5,5"-dibromo-2,2':6',2"-terpyridine, (4-(dimethylamino)thiophene-2-yl)boric acid, and triphenylphosphine (phosphine) palladium in step (4) is 1:2.5:0.05, and the mass ratio of tetrakis (triphenylphosphine) palladium, ethylene glycol dimethyl ether, and 2 mol / L potassium carbonate is 1:50:

30.

5. The method for preparing an engine water cooling system cleaning agent according to claim 2, characterized in that: The amounts of the components in step (5) are as follows: by mass: 5-6 parts of modified activated carbon, 20-30 parts of modified polythiophene, 10-15 parts of sodium citrate, 5-8 parts of N,N-bishydroxyethyl dodecylamide, 2-3 parts of Lan-826 pickling corrosion inhibitor, 2-3 parts of dodecyl betaine, 5-6 parts of triethanolamine, 10-15 parts of polyaspartic acid tetracarboxylic acid ethyl ester, 50-60 parts of ethylene glycol monobutyl ether, and 1-2 parts of 30wt% hydrogen peroxide.

6. The method for preparing an engine water cooling system cleaning agent according to claim 3, characterized in that: The activated carbon is of GB-1 type.

7. The cleaning temperature of the engine water cooling system cleaning agent according to claim 1 is 65-75°C.

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