CN111334257A - Wide-area efficient environment-friendly composite snow and ice melting material and preparation method thereof - Google Patents
Wide-area efficient environment-friendly composite snow and ice melting material and preparation method thereof Download PDFInfo
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- CN111334257A CN111334257A CN202010327143.9A CN202010327143A CN111334257A CN 111334257 A CN111334257 A CN 111334257A CN 202010327143 A CN202010327143 A CN 202010327143A CN 111334257 A CN111334257 A CN 111334257A
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Abstract
The invention discloses a wide-area efficient environment-friendly composite snow and ice melting material and a preparation method thereof, belonging to the technical application chemistry field of highway engineering maintenance materials. Comprises the following components in percentage by mass: environment-friendly additive (80-99.9): (0.1-20), the environment-friendly additive comprises the following components in percentage by mass: cycloalkyl imidazoline quaternary ammonium salt: zinc dihydrogen phosphate salt: thiourea ═ (4-12): (1-3): (4-12). During preparation, the chlorine salt is mixed and crushed according to a proportion, then the solution prepared by the environment-friendly additive with corresponding quality is uniformly sprayed on the surface of the chlorine salt, and the preparation is finished after the solution is dried. The material for melting snow and ice can be widely applied to places such as roads, airports, railways, squares and the like, has the advantages of high melting speed, high efficiency, low corrosion damage, no damage to green plants, wide temperature application range and the like, obviously reduces the wet and slippery of ice and snow pavements, improves the running safety of vehicles, ensures smooth traffic and the safety of lives and properties of people, and has higher economic popularization and application values.
Description
The technical field is as follows:
the invention belongs to the technical field of highway engineering maintenance materials and applied chemistry, and particularly relates to a wide-area efficient environment-friendly composite snow and ice melting material and a preparation method thereof.
Background art:
the snow and ice melting material is a chemical substance which can melt ice and snow which is solid water into liquid at the temperature of below 0 ℃. The action mechanism is that the water containing the snow-melting and deicing material does not condense into solid water (ice and snow) but liquid water in a certain temperature range below zero. The snow-melting and ice-melting material can reduce the freezing point of water to ensure that the water is not condensed into a solid state within a certain temperature range below zero to realize the purposes of snow melting and ice melting, is used for snow melting, ice melting and freezing prevention in places such as roads, airports, railways, squares and the like, quickly removes ice and snow attached to the surface, opens traffic as early as possible, reduces the wet and slippery road surface, improves the driving safety of vehicles, ensures the smooth traffic and the safety of lives and properties of people, and ensures the stable and harmonious traffic transportation and social life. The snow melting material is used in European and American countries in the last 50 th century at the earliest time, the snow melting material with the largest usage amount at home and abroad is a chlorine salt snow melting material and a snow melting material with the longest usage history, and the usage amount at present still accounts for more than 90% and comprises chlorine salts such as sodium chloride, calcium chloride, magnesium chloride and the like. The material for melting snow and ice is easy to obtain from nature, has large quantity and good effect of melting snow and ice, and is still applied to snow and ice melting places which are still predominant, including sea salt, rock salt and the like, aqueous solution thereof and the like. The application of the chloride as the snow-melting agent for decades causes that human beings have to bear the negative effects brought by the snow-melting agent, for example, the chloride snow-melting material has serious corrosion and damage to vehicles, roads, bridges and other infrastructure, and is easy to cause withering of vegetation along the line and salinization and pollution to water and soil. Therefore, people begin to search for non-chlorine salt snow-melting materials with the functions of melting snow and ice. The snow-melting agent is represented by calcium magnesium acetate CMA, and the application of the calcium magnesium acetate is determined by a purification technology and a snow-melting and deicing effect. The calcium acetate magnesium snow-melting agent on the market has low purity, high price, poor snow-melting and ice-melting effect, failure at the temperature lower than minus 10 ℃, water-insoluble impurities and pollution to the environment and application places. The non-chlorine salt snow-melting material is not easy to obtain, has high cost and far lower snow-melting and ice-melting effect than chlorine salt, so the application of the non-chlorine salt snow-melting material for melting snow and ice is greatly limited. The wide-area efficient environment-friendly composite snow and ice melting material is developed by taking chloride as a main material and adopting a composite technology according to the wide-area temperature application range, high efficiency, environmental protection, easy availability, universality and economic principle, and has wide application prospect, social benefit and environmental benefit.
The invention content is as follows:
the invention aims to overcome the defects of large corrosion and damage effects, environment pollution, damage to vegetation, extreme low-temperature failure and the like of the conventional snow melting material on traffic infrastructure, combines the snow melting and deicing principle, the corrosion and protection mechanism and the vegetation damage mechanism, integrates various performances and requirements, and provides a wide-area efficient environment-friendly composite snow melting and deicing material and a preparation method thereof. The wide-area efficient environment-friendly composite snow-melting and deicing material prepared by the method has wide application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
a wide-area efficient environment-friendly composite snow and ice melting material comprises the following components in percentage by mass: main materials of chloride salt: environment-friendly additive (80-99.9): (0.1-20), wherein the environment-friendly additive comprises the following components in percentage by mass: cycloalkyl imidazoline quaternary ammonium salt: zinc dihydrogen phosphate salt: thiourea (4-12): (1-3): (4-12).
The main material of the chlorine salt is one or more of sodium chloride, calcium chloride and magnesium chloride, when the main material is several, the mixing ratio is any ratio, and the chlorine salt is chlorine salt containing crystal water or chlorine salt without crystal water.
The main materials of the chlorine salt are anhydrous NaCl and MgCl2·6H2O and CaC12·2H2O is 10: (20-60): (30-70) mixing.
In the main material of the chlorine salt, anhydrous NaCl and MgCl2·6H2O and CaC12·2H2The mass ratio of O is 10: 20: 70.
the addition mass of the environment-friendly additive accounts for 0.75-2.1% of the mass of the main material of the chlorine salt.
In the environment-friendly additive, imidazoline quaternary ammonium salt: zinc dihydrogen phosphate: 12, (2-3) and (4-18) the addition mass of the environment-friendly additive accounts for 1.1-2.1% of that of the main material of the chlorine salt.
In the environment-friendly additive, imidazoline quaternary ammonium salt: zinc dihydrogen phosphate: thiourea ═ (4-12): (2-3): (8-12), wherein the addition mass of the environment-friendly additive accounts for 1.1-1.52% of the mass of the main material of the chlorine salt.
In the environment-friendly additive, imidazoline quaternary ammonium salt: zinc dihydrogen phosphate: the thiourea is 6:1:2, and the addition mass of the environment-friendly additive accounts for 1.52% of that of the main material of the chlorine salt.
The main materials of the chlorine salt are as follows: 96-98.5 parts of environment-friendly additive: 1.5-4 parts of environment-friendly additive, wherein the addition mass of the environment-friendly additive accounts for 0.75-4% of the mass of the main material of the chlorine salt.
The main materials of the chlorine salt are as follows: 98.5 parts of an environment-friendly additive: 1.5 parts of the environment-friendly additive, wherein the addition mass of the environment-friendly additive accounts for 1.52% of the mass of the main material of the chlorine salt.
The molecular formula of the naphthenic imidazoline quaternary ammonium salt is as follows:
wherein:
R′＝R″-CH2-R ═ any-type hydrocarbyl.
The zinc dihydrogen phosphate salt is added in the form of phosphoric acid and zinc oxide, and the molar ratio of the two is phosphoric acid: and (3) zinc oxide is 2:1, so as to generate zinc dihydrogen phosphate, and the generation quality of the zinc dihydrogen phosphate is ensured to be 10-50 parts.
The equation for the reaction of phosphoric acid and zinc oxide to produce zinc dihydrogen phosphate is: 2H3PO4+ZnO＝Zn(H2PO4)2+H2O
The preparation method of the naphthenic imidazoline quaternary ammonium salt in the environment-friendly additive comprises the following steps:
(1) in terms of molar ratio, organic acid: mixing organic amine and organic amine (1.2-1.4), adding a catalyst, stirring and heating to 120 ℃, freely discharging water through stepwise heating at the temperature of 120-200 ℃, sequentially performing intermolecular and intramolecular dehydration to obtain amide, and cyclizing to obtain an oil-soluble naphthenic imidazoline intermediate;
in the step (1), the organic acid is naphthenic acid, and the organic amine is diethylenetriamine.
In the step (1), the catalyst is H3BO3The mass of the additive is 0.3 to 0.5 percent of that of the naphthenic acid.
In the step (1), the specific stirring and heating process comprises the following steps:
stirring and heating to 120 ℃, carrying out reflux reaction for 5 hours, heating to 160 ℃ again, and reacting for 2 hours until no water is separated out, thereby completing amidation reaction;
the temperature is continuously increased to 170 ℃ for reaction for 3h, the temperature is 200 ℃ for reaction for 1.5h, and the temperature is 220 ℃ for reaction for 2.5h, thus completing cyclization.
(2) Cooling the intermediate of the naphthenic imidazoline, dissolving the intermediate in an organic solvent, and dripping an alkylating reagent into the intermediate of the naphthenic imidazoline according to a molar ratio: and (3) keeping the temperature reduction point of the alkylating reagent 1 (1.4-1.6), continuing to react for 1-3h after the dropwise addition is finished, and evaporating the organic solvent to prepare the viscous and transparent water-soluble cycloalkyl imidazoline quaternary ammonium salt, wherein the temperature reduction point of the intermediate is 10-20 ℃ lower than the boiling point of the organic solvent.
In the step (2), the imidazoline intermediate is dissolved in an organic solvent with equal mass.
In the step (2), the organic solvent is isopropanol, and the temperature of the naphthenic imidazoline intermediate is reduced to 50 ℃.
In the step (2), the alkylating reagent is sulfuric acid di-ethyl ester or phosphorous acid di-ethyl ester.
In the step (2), the alkylating reagent is dimethyl sulfate or dimethyl phosphite.
In the step (2), the dripping speed of the alkylating reagent is 20 drops/min.
In the step (2), the boiling point of the organic solvent is 30-50 ℃ lower than that of the product.
In the step (1), the reaction principle of amide and cyclization is as follows:
the preparation method of the wide-area efficient environment-friendly composite snow and ice melting material comprises the following steps:
(1) taking 80-99.9 parts of chlorine salt main material and 0.1-20 parts of environment-friendly additive according to the mixture ratio; crushing a main chlorine salt material to obtain chlorine salt particles, wherein the particle size of the chlorine salt particles is less than or equal to 3 mm;
(2) preparing the environment-friendly additive into an aqueous solution with the concentration of 20-60%;
(3) uniformly spraying the aqueous solution of the environment-friendly additive on the surfaces of the chloride particles, and uniformly stirring to realize infiltration to prepare a wet composite snow-melting and deicing primary product;
in the step (3), the stirring time is 10-30 min.
(4) And (3) drying the wet composite snow-melting and ice-melting primary product, and granulating or not granulating according to use requirements to prepare the wide-area efficient environment-friendly composite snow-melting and ice-melting material.
In the step (4), the drying temperature is less than or equal to 105 ℃.
In the step (4), if the granulation operation is performed, a suitable granulator is selected according to the use requirement.
In the step (4), the prepared wide-area efficient environment-friendly composite snow and ice melting material comprises the following components in parts by weight:
melting ice at-10 deg.C at 13.5-20mL (60min), dissolving at 25 deg.C at 13.9-15.0g/min, and pH at 7.02-8.18;
the addition amount accounts for 10-40% of the mass ratio of ice and snow to be melted, the freezing point reaches-3.0 ℃ to-40 ℃, and the relative snow melting and deicing capacity is as follows: 1700% at the temperature of minus 10 ℃ to minus 30 ℃; wherein the temperature is 1700% at-10 ℃, 1300% at-20 ℃ and 900% at-30 ℃;
the corrosion rate of the carbon steel is 0.0053-0.0165mm/a, and the stripping amount of the C30 concrete per unit area is 1.61-2.52g/m2The germination rate of the grass seeds is 85-94% of 1% solution and 70-79% of 2% solution, and the friction attenuation of the pavement is as follows: 1.5 percent of dry basis and 1.5 to 2.5 percent of 20 percent of wet basis;
the slow release rate η of the snow-melting and deicing material is 91-98.5% at 40 + -1 deg.C under the condition of the chloride concentration of 30 g/L.
In the invention, nitrogen atoms on an imidazoline ring in the molecular structure of the environment-friendly additive have lone pair electrons, and an empty d orbit exists on the metal surface, so that the two are firmly coordinated, the anode activation energy of the carbon steel in a corrosive medium is improved, the corrosion rate of an anode is reduced, and imidazoline quaternary ammonium salt molecules can form a thick hydrophobic film on the metal surface to prevent the corrosive medium from contacting with the metal surface. And the phosphate and the zinc salt are cooperated to form a three-dimensional steel protective film. Since the thiourea has two hybridized nitrogen atoms and one hybridized sulfur atom in the molecule, the thiourea can react with Fe2+Complexing, and finally converting into an insoluble iron sulfide protective film; the zinc dihydrogen phosphate accelerates film formation, improves the phosphating speed, shortens the phosphating time, regulates and stabilizes the pH value, and prolongs the service life of the treating agent. Zinc dihydrogen phosphate is formulated from phosphoric acid and zinc oxide, and is distinguished from sodium dihydrogen phosphate or non-hydrolyzable zinc salts (such as ZnSO)4Etc.), zinc dihydrogen phosphate has hydrolyzability and can react to form insoluble Zn on the cathode plate of steel3(PO4)2A precipitation film (zinc phosphating of steel). Zinc dihydrogen phosphate can be ionized to form insoluble FePO on steel surface4Precipitation film (iron and steel series phosphating), Zn2+Then Zn (OH)2Form a cathode-type deposited film on the surface of steel, which is not firm but has synergistic effect, and its function is similar to that of using non-hydrolytic zinc salt (such as ZnSO)4Etc.) are the same. The thiourea has two hybridization atoms N and S in the thiourea molecule, which can react with Fe2+Complexing and finally converting into insoluble iron sulfide protective film, HPO containing dissolved oxygen4 2-Or PO4 3-Isokinetic energy of Fe3+Reacting to form insoluble gamma-Fe2O3And FePO4·2H2The oxide film has defects and pores, and plays roles of filling the pores and filling the defects when being mixed with phosphate and zinc salt for use, so as to reduce active points and finally form a three-dimensional protective film.
The invention has the beneficial effects that:
the wide-area efficient environment-friendly composite snow and ice melting material prepared by the method has a wide temperature application range of 0-minus 40 ℃, and is widely suitable for airports, highways, railways and places needing snow melting, ice melting and freeze prevention; under the same condition, the usage amount of the snow and ice melting material is reduced by more than 20%, and the speed or efficiency of snow and ice melting is improved by more than 25%; the corrosion degree of the metal and the structure thereof is reduced by more than 90 percent; the corrosion degree of the cement concrete structure is reduced by more than 60 percent; has nutrition improving effect on soil and vegetation growing environment; and the raw materials are low in cost, easy to obtain and high in cost performance. The snow melting and ice melting device has the advantages of being rapid, efficient, environment-friendly, economical and the like, can reduce or even eliminate adverse effects to the maximum extent while realizing perfect snow melting and ice melting, and has high popularization and application values.
The specific implementation mode is as follows:
the present invention will be described in further detail with reference to examples.
A wide-area efficient environment-friendly composite snow and ice melting material comprises the following components in percentage by mass: main materials of chloride salt: environment-friendly additive (80-99.9): (0.1-20), wherein the environment-friendly additive comprises the following components in percentage by mass: cycloalkyl imidazoline quaternary ammonium salt: zinc dihydrogen phosphate salt: thiourea (4-12): (1-3): (4-12), the main material of the chlorine salt is one or more of sodium chloride, calcium chloride and magnesium chloride, and when the main material is several, the mixing ratio is any ratio, and the chlorine salt is chlorine salt containing crystal water or chlorine salt without crystal water.
The main material of the chloride is anhydrous NaCl and MgCl2·6H2O and CaC12·2H2O is 10: (20-60): (30-70) mixing.
Preferably, the main material of the chlorine salt is anhydrous NaCl and MgCl2·6H2O and CaC12·2H2The mass ratio of O is 10: 20: 70.
preferably, the addition mass of the environment-friendly additive accounts for 0.75-2.1% of the mass of the main material of the chlorine salt.
Preferably, in the environment-friendly additive, imidazoline quaternary ammonium salt: zinc dihydrogen phosphate: 12, (2-3) and (4-18) thiourea, wherein the addition mass of the environment-friendly additive accounts for 1.1-2.1% of the mass of the main material of the chlorine salt.
Preferably, in the environment-friendly additive, imidazoline quaternary ammonium salt: zinc dihydrogen phosphate: thiourea ═ (4-12): (2-3): (8-12), wherein the addition mass of the environment-friendly additive accounts for 1.1-1.52% of the mass of the main material of the chlorine salt.
Preferably, in the environment-friendly additive, imidazoline quaternary ammonium salt: zinc dihydrogen phosphate: thiourea is 6:1:2, and the addition mass of the environment-friendly additive accounts for 1.52 percent of the mass of the main material of the chloride salt.
Preferably, the main materials of the chlorine salt are as follows: 96-98.5 parts of environment-friendly additive: 1.5-4 parts of environment-friendly additive, wherein the addition mass of the environment-friendly additive accounts for 0.75-4% of the mass of the main material of the chlorine salt.
Preferably, the main materials of the chlorine salt are as follows: 98.5 parts of an environment-friendly additive: 1.5 parts of environment-friendly additive accounting for 1.52 percent of the mass of the main material of the chlorine salt.
The molecular formula of the naphthenic imidazoline quaternary ammonium salt is as follows:
wherein:
R′＝R″-CH2-R ═ any-type hydrocarbyl.
The zinc dihydrogen phosphate salt is added in the form of phosphoric acid and zinc oxide raw materials, and the molar ratio of the two is phosphoric acid: and (3) zinc oxide is 2:1, so as to generate zinc dihydrogen phosphate, and the generation quality of the zinc dihydrogen phosphate is ensured to be 10-50 parts.
The equation for the reaction of phosphoric acid and zinc oxide to produce zinc dihydrogen phosphate is: 2H3PO4+ZnO＝Zn(H2PO4)2+H2O
The preparation method of the naphthenic imidazoline quaternary ammonium salt in the environment-friendly additive comprises the following steps:
(1) in molar ratio, naphthenic acid: (1.2-1.4), mixing the two, and adding H3BO3Adding 0.3-0.5% of naphthenic acid, stirring and heating to 120 ℃, carrying out reflux reaction for 5 hours, heating to 160 ℃, reacting for 2 hours to realize intermolecular dehydration, and completing amidation reaction until no water is separated out;
continuously heating to 170 ℃ for reaction for 3h, reacting at 200 ℃ for 1.5h, and reacting at 220 ℃ for 2.5h to realize intramolecular dehydration and complete cyclization to prepare an oil-soluble cycloalkyl imidazoline intermediate;
(2) cooling the naphthenic imidazoline intermediate to 50 ℃, dissolving the naphthenic imidazoline intermediate in isopropanol with equal mass, dropwise adding dimethyl sulfate into the naphthenic imidazoline intermediate, wherein the dropwise adding speed is 20 drops/min, and the molar ratio of the imidazoline intermediate is as follows: and (3) keeping the temperature of the dimethyl sulfate to be 1.4-1.6, continuing to react for 1-3 hours after the dropwise addition is finished, and evaporating the organic solvent to prepare the viscous and transparent water-soluble cycloalkyl imidazoline quaternary ammonium salt.
The principle of the reaction between the amide and the cyclization is as follows:
the preparation method of the wide-area efficient environment-friendly composite snow and ice melting material comprises the following steps:
(1) taking 80-99.9 parts of chlorine salt main material and 0.1-20 parts of environment-friendly additive according to the mixture ratio; crushing a main chlorine salt material to obtain chlorine salt particles, wherein the particle size of the chlorine salt particles is less than or equal to 3 mm;
(2) preparing the environment-friendly additive into an aqueous solution with the concentration of 20-60%;
(3) uniformly spraying the aqueous solution of the environment-friendly additive on the surfaces of the chloride salt particles, and stirring for 10-30min until the mixture is uniform, so as to realize infiltration and prepare a wet composite snow-melting and ice-melting primary product;
(4) drying the wet composite snow-melting and ice-melting primary product at the temperature of less than or equal to 105 ℃, and then selecting a proper granulator for granulation or non-granulation according to the use requirements to prepare the wide-area efficient environment-friendly composite snow-melting and ice-melting material, wherein the composite snow-melting and ice-melting material comprises the following components in parts by weight:
melting ice at-10 deg.C at 13.5-20mL (60min), dissolving at 25 deg.C at 13.9-15.0g/min, and pH at 7.02-8.18;
the addition amount accounts for 10-40% of the mass ratio of ice and snow to be melted, the freezing point reaches-3.0 ℃ to-40 ℃, and the relative snow melting and deicing capacity is as follows: 1700% at the temperature of minus 10 ℃ to minus 30 ℃; wherein the temperature is 1700% at-10 ℃, 1300% at-20 ℃ and 900% at-30 ℃;
the corrosion rate of the carbon steel is 0.0053-0.0165mm/a, and the stripping amount of the C30 concrete per unit area is 1.61-2.52g/m2The germination rate of the grass seeds is 85-94% of 1% solution and 70-79% of 2% solution, and the friction attenuation of the pavement is as follows: 1.5 percent of dry basis and 1.5 to 2.5 percent of 20 percent of wet basis, and basically has negligible attenuation effect on the road surface friction;
the slow release rate η of the snow-melting and deicing material is 91-98.5% at 40 + -1 deg.C under the condition of the chloride concentration of 30 g/L.
1. The specific preparation method of the cycloalkyl imidazoline quaternary ammonium salt adopted in the following examples and comparative examples is as follows:
(1) in molar ratio, naphthenic acid: diethylenetriamine (1: 1.2), mixing the two, and adding H3BO3Adding 0.3 percent of naphthenic acid by mass, stirring and heating to 120 ℃, refluxing for 5 hours, then heating to 160 ℃, reacting for 2 hours to realize intermolecular dehydration, and completing amidation reaction until no water is separated out;
continuously heating to 170 ℃ for reaction for 3h, reacting at 200 ℃ for 1.5h, and reacting at 220 ℃ for 2.5h to realize intramolecular dehydration and complete cyclization to prepare an oil-soluble cycloalkyl imidazoline intermediate;
(2) cooling the naphthenic imidazoline intermediate to 50 ℃, dissolving the naphthenic imidazoline intermediate in isopropanol with equal mass, dropwise adding dimethyl sulfate into the naphthenic imidazoline intermediate, wherein the dropwise adding speed is 20 drops/min, and the molar ratio of the imidazoline intermediate is as follows: and (3) keeping the temperature of the dimethyl sulfate to be 1:1.5, continuing to react for 2 hours after the dropwise addition is finished, and evaporating the organic solvent to obtain the viscous and transparent water-soluble cycloalkyl imidazoline quaternary ammonium salt.
2. In the following examples, the ice melting rate test and results demonstrate that:
(1) the test method comprises the following steps:
at present, there are two general methods for measuring the ice melting rate: one is a fixed time to measure the amount of ice melted within the fixed time, and the other is to measure the time required for a certain mass of the snow-melting agent to completely melt a certain mass of ice. In view of simplicity and operability, the former, namely:
a plurality of 100mL porcelain evaporation dishes are filled with 50mL of water with the same amount, after the porcelain evaporation dishes are completely frozen into ice blocks, snow-melting and ice-melting materials with different components and adding amounts capable of realizing ice melting at corresponding temperatures are scattered on ice blocks, and the ice-melting amount is measured after 15 min, 30min, 45 min and 60min by using a pouring method. Comparing the accumulated water yield of the ice melting in different time, the ice melting rate can be compared.
(2) Experimental procedure
① adding 50mL distilled water into a porcelain evaporation dish, placing in a freezer, freezing at-10 deg.C, -15 deg.C, -20 deg.C, -25 deg.C, -30 deg.C, -35 deg.C for 12 hr to form ice.
② the refrigerator door is opened, the temperature is adjusted to-10 deg.C, -15 deg.C, -20 deg.C, -25 deg.C, -30 deg.C and-35 deg.C, the porcelain evaporation dishes are arranged in order according to a certain order.
③ the snow-melting and ice-melting material l0g was evenly spread on the ice surface of the porcelain dish within one minute, and the melted ice water was poured out after 15,30,45 and 60 minutes respectively, and the volume of the water output was measured.
④ the speed of snow and ice melting by different snow melting agents was evaluated by comparing the volumes of the amounts of water melted at the same temperature for the same time.
3. The influence of the main components and the proportion of the chlorine salt on the snow and ice melting performance is researched:
formulation one (LB-1): w (CaC 1)2·2H2O)＝70％，w(MgCl2·6H2O)＝20％，w(NaCl)＝10％；
Formulation two (LB-2): w (CaC 1)2·2H2O)＝50％，w(MgCl2·6H2O)＝40％，w(NaCl)＝10％；
Formulation III (LB-3): w (CaC 1)2·2H2O)＝30％，w(MgCl2·6H2O)＝60％，w(NaCl)＝10％；
Formulation one to three and NaCl, MgCl2·6H2O and CaCl2·2H2The ice melting rate results of different formulations of chlorine salt main materials of O at different temperatures are shown in Table 1, the freezing point data of different amounts of the chlorine salt main materials at different temperatures are shown in Table 3, and the summary table of the characteristics of the chlorine salt main materials of different formulations is shown in Table 4.
TABLE 1 Ice melting test results
4. Dissolution capacity test:
formulation one to three and NaCl, MgCl2·6H2O and CaCl2·2H2The ice melting rate results of different formulations of chlorine salt main materials of O at different temperatures are shown in Table 2, and the specific process of the dissolving capacity experiment is as follows:
weighing 40.0g of a chlorine salt main material solid snow melting agent sample at 25 ℃, putting the chlorine salt main material solid snow melting agent sample into a beaker, adding 200mL of water, starting a precision electric stirrer, adjusting the rotating speed to 100r/min for stirring, starting timing, observing the dissolving condition until the chlorine salt main material solid snow melting agent sample is completely dissolved, and recording the complete dissolving time(s). The dissolution speed is calculated according to the data processing method of the dissolution capability experiment in GB-T-23851 and 2017.
TABLE 2 dissolution Rate test results
TABLE 3 freezing Point test results
Note: the mass percentage concentration is as follows: the mass of the snow-melting agent accounts for the mass percentage of the ice.
TABLE 4 summary of characteristics
In combination with the above, LB-1 is the best formula of the main material of the chloride salt in consideration of deliquescence stability and snow and ice melting effect.
5. Environment-friendly additive formula
In the research experiment of the formula of the environment-friendly additive, the corrosion rate in saline water is increased along with the increase of the mass percentage concentration of the chloride, but the corrosion rate reaches the highest point when the concentration is 3 percent, namely 30g/L, and then is reduced along with the increase of the concentration, which is mainly caused by the reduction of the solubility of oxygen in a concentrated solution. In order to evaluate the corrosion performance of the main components in the main formula of the snow-melting agent obtained in the research, the main material of the chlorine salt is prepared into a solution with the concentration of 30g/L, the solution is compared with a basic sample in a simulation mode, and the environment-friendly additive is investigated and screened so as to achieve the effect of effectively inhibiting corrosion, namely the corrosion inhibition effect.
The study carried out the corrosion experiment at 40 + -1 ℃ according to the GB-T-23851 and 2017 standard. The temperature of 40 +/-1 ℃ is the harsh test condition relative to low temperature, and the antiseptic effect of the preservative can completely show the experimental result in the low-temperature environment.
The specific operation is as follows:
the wide-area efficient environment-friendly composite snow and ice melting material prepared in the embodiments 1 to 9 is used as a chloride salt main material as a formula I, and the environment-friendly additive is prepared by selecting imidazoline quaternary ammonium salt, zinc dihydrogen phosphate and thiourea with different addition ratios to perform an orthogonal experiment, and specifically, the wide-area efficient environment-friendly composite snow and ice melting material prepared in the embodiments 1 to 9 is prepared by mixing the raw materials in parts by mass: dissolving the snow-melting and deicing material in water according to the proportion of 30g to 1L to prepare a snow-melting and deicing material solution with the chloride concentration of 30g/L, and carrying out an environment-friendly additive component screening experiment.
The selection factor levels for the imidazoline quaternary ammonium salt, zinc dihydrogen phosphate, and thiourea for the different addition ratios of examples 1-9 are shown in table 5 below. Taking 100mg/L of level 1, A (imidazoline quaternary ammonium salt) as an example, 100mg of imidazoline quaternary ammonium salt is added into the snow melting ice material solution with the chloride concentration of 30 g/L. The orthogonal experiment corrosion inhibition rate data is shown in Table 6, taking example 1 as an example, the factor levels of imidazoline quaternary ammonium salt, zinc dihydrogen phosphate and thiourea are 100mg/L, 25mg/L and 100mg/L, namely the adding mass ratio of the imidazoline quaternary ammonium salt, the zinc dihydrogen phosphate and the thiourea is 4:1:4, and the total adding amount of 225mg accounts for 0.75% of 30g of chloride salt.
TABLE 5 environmental protection additive formulation selection factor levels
TABLE 6L9(34) Results of orthogonal experiments
In combination, the optimal mass ratio of 3 components in the raw materials of the environment-friendly additive is as follows: imidazoline quaternary ammonium salt: zinc dihydrogen phosphate: thiourea was 6:1: 2.
Among these, examples 2/4 and 6 were able to obtain the same freezing point data as in example 1, and examples 3, 5, 9 and 7 were all affected by increasing the addition ratio of the eco-friendly solvent.
Example 1
(1) Taking materials in three groups in parallel, wherein each group is 1: 7: 2, respectively taking NaCl, CaC12·2H2O and MgCl2·6H2O, putting the three into a mortar, grinding the three into powder, and uniformly stirring the powder to obtain a chlorine salt main material LB-1 of the snow melting material;
(2) preparing the following three groups of environment-friendly additives in parallel:
the weight ratio is as follows: imidazoline quaternary ammonium salt, zinc dihydrogen phosphate and thiourea, 4:1:4, preparing an environment-friendly additive a1, wherein the mass of the environment-friendly additive a1 accounts for 0.75% of that of the chlorine salt main material LB-1, dissolving the environment-friendly additive a1 in water with the mass being 3 times that of the environment-friendly additive, and stirring and dissolving at normal temperature to form a transparent environment-friendly additive solution;
(3) uniformly spraying the solution obtained in the step (2) on the surface of the step (1) by using a small spraying pot, and uniformly stirring while spraying;
and (3) putting the mixture obtained in the step (3) into a watch glass, and drying the mixture in a constant-temperature oven at 105 ℃ for more than 4 hours to obtain a wide-area efficient environment-friendly composite snow and ice melting material for later use, wherein the slow release rate η of the snow and ice melting material is 91.37% at 40 +/-1 ℃ under the condition that the concentration of chloride salt is 30 g/L.
Example 2
(1) According to the mass ratio of 1: 7: 2, respectively taking NaCl, CaC12·2H2O and MgCl2·6H2O, putting the three into a mortar, grinding the three into powder, and uniformly stirring the powder to obtain a chlorine salt main material LB-1 of the snow melting material;
(2) preparing the following three groups of environment-friendly additives in parallel:
the weight ratio is as follows: imidazoline quaternary ammonium salt, zinc dihydrogen phosphate and thiourea are 4:2:8, an environment-friendly additive b1 is prepared, the mass ratio of the environment-friendly additive b1 to the chlorine salt main material LB-1 is 1.16%, the environment-friendly additive a1 is dissolved in water with the mass 3 times that of the environment-friendly additive, and the mixture is stirred and dissolved at normal temperature to form a transparent environment-friendly additive solution;
(3) uniformly spraying the solution obtained in the step (2) on the surface of the step (1) by using a small spraying pot, and uniformly stirring while spraying;
and (3) putting the mixture obtained in the step (3) into a watch glass, and drying the mixture in a constant-temperature oven at 105 ℃ for more than 4 hours to obtain a wide-area efficient environment-friendly composite snow and ice melting material for later use, wherein the slow release rate η of the snow and ice melting material is 97.39% at 40 +/-1 ℃ under the condition that the concentration of chloride salt is 30 g/L.
Example 3
(1) According to the mass ratio of 1: 7: 2, respectively taking NaCl, CaC12·2H2O and MgCl2·6H2O, putting the three into a mortar, grinding into powder, and uniformly stirring to obtain the snow melting materialThe main material LB-1 of the chlorine salt;
(2) preparing the following three groups of environment-friendly additives in parallel:
the weight ratio is as follows: imidazoline quaternary ammonium salt, zinc dihydrogen phosphate and thiourea are 4:3:12, an environment-friendly additive c1 is prepared, the mass ratio of the environment-friendly additive c1 to the chlorine salt main material LB-1 is 1.58%, the environment-friendly additive c1 is dissolved in water with the mass 3 times that of the environment-friendly additive, and the mixture is stirred and dissolved at normal temperature to form a transparent environment-friendly additive solution;
(3) uniformly spraying the solution obtained in the step (2) on the surface of the step (1) by using a small spraying pot, and uniformly stirring while spraying;
and (3) putting the mixture obtained in the step (3) into a watch glass, and drying the mixture in a constant-temperature oven at 105 ℃ for more than 4 hours to obtain a wide-area efficient environment-friendly composite snow and ice melting material for later use, wherein the slow release rate η of the snow and ice melting material is 94.78% at 40 +/-1 ℃ under the condition that the concentration of chloride salt is 30 g/L.
Example 4
(1) According to the mass ratio of 1: 7: 2, respectively taking NaCl, CaC12·2H2O and MgCl2·6H2O, putting the three into a mortar, grinding the three into powder, and uniformly stirring the powder to obtain a chlorine salt main material LB-1 of the snow melting material;
(2) preparing the following three groups of environment-friendly additives in parallel:
the weight ratio is as follows: imidazoline quaternary ammonium salt, zinc dihydrogen phosphate and thiourea are 8:1:8, an environment-friendly additive d1 is prepared, the mass ratio of the environment-friendly additive d1 to the chlorine salt main material LB-1 is 1.42%, the environment-friendly additive d1 is dissolved in water with the mass 3 times of that of the environment-friendly additive, and the mixture is stirred and dissolved at normal temperature to form a transparent environment-friendly additive solution;
(3) uniformly spraying the solution obtained in the step (2) on the surface of the step (1) by using a small spraying pot, and uniformly stirring while spraying;
and (3) putting the mixture obtained in the step (3) into a watch glass, and drying the mixture in a constant-temperature oven at 105 ℃ for more than 4 hours to obtain a wide-area efficient environment-friendly composite snow and ice melting material for later use, wherein the slow release rate η of the snow and ice melting material is 98.29% at 40 +/-1 ℃ under the condition that the concentration of chloride salt is 30 g/L.
Example 5
(1) According to the mass ratio of 1: 7: 2Separately taking NaCl, CaC12·2H2O and MgCl2·6H2O, putting the three into a mortar, grinding the three into powder, and uniformly stirring the powder to obtain a chlorine salt main material LB-1 of the snow melting material;
(2) preparing the following three groups of environment-friendly additives in parallel:
the weight ratio is as follows: imidazoline quaternary ammonium salt, zinc dihydrogen phosphate and thiourea are 8:2:12, an environment-friendly additive e1 is prepared, the mass ratio of the environment-friendly additive e1 to the chlorine salt main material LB-1 is 1.83%, the environment-friendly additive e1 is dissolved in water with the mass 3 times of that of the environment-friendly additive, and the mixture is stirred and dissolved at normal temperature to form a transparent environment-friendly additive solution;
(3) uniformly spraying the solution obtained in the step (2) on the surface of the step (1) by using a small spraying pot, and uniformly stirring while spraying;
and (3) putting the mixture obtained in the step (3) into a watch glass, and drying the mixture in a constant-temperature oven at 105 ℃ for more than 4 hours to obtain a wide-area efficient environment-friendly composite snow and ice melting material for later use, wherein the slow release rate η of the snow and ice melting material is 98.29% at 40 +/-1 ℃ under the condition that the concentration of chloride salt is 30 g/L.
Example 6
(1) According to the mass ratio of 1: 7: 2, respectively taking NaCl, CaC12·2H2O and MgCl2·6H2O, putting the three into a mortar, grinding the three into powder, and uniformly stirring the powder to obtain a chlorine salt main material LB-1 of the snow melting material;
(2) preparing the following three groups of environment-friendly additives in parallel:
the weight ratio is as follows: imidazoline quaternary ammonium salt, zinc dihydrogen phosphate and thiourea are 8:3:4, an environment-friendly additive f1 is prepared, the mass ratio of the environment-friendly additive f1 to the chlorine salt main material LB-1 is 1.25%, the environment-friendly additive f1 is dissolved in water with the mass 3 times that of the environment-friendly additive, and the mixture is stirred and dissolved at normal temperature to form a transparent environment-friendly additive solution;
(3) uniformly spraying the solution obtained in the step (2) on the surface of the step (1) by using a small spraying pot, and uniformly stirring while spraying;
and (3) putting the mixture obtained in the step (3) into a watch glass, and drying the mixture in a constant-temperature oven at 105 ℃ for more than 4 hours to obtain a wide-area efficient environment-friendly composite snow and ice melting material for later use, wherein the slow release rate η of the snow and ice melting material is 97.71% at 40 +/-1 ℃ under the condition that the concentration of chloride salt is 30 g/L.
Example 7
(1) According to the mass ratio of 1: 7: 2, respectively taking NaCl, CaC12·2H2O and MgCl2·6H2O, putting the three into a mortar, grinding the three into powder, and uniformly stirring the powder to obtain a chlorine salt main material LB-1 of the snow melting material;
(2) preparing the following three groups of environment-friendly additives in parallel:
the weight ratio is as follows: imidazoline quaternary ammonium salt, zinc dihydrogen phosphate and thiourea are 12:1:12, an environment-friendly additive g1 is prepared, the mass ratio of the environment-friendly additive g1 to the chlorine salt main material LB-1 is 2.1%, the environment-friendly additive g1 is dissolved in water with the mass 3 times of that of the environment-friendly additive, and the mixture is stirred and dissolved at normal temperature to form a transparent environment-friendly additive solution;
(3) uniformly spraying the solution obtained in the step (2) on the surface of the step (1) by using a small spraying pot, and uniformly stirring while spraying;
and (3) putting the mixture obtained in the step (3) into a watch glass, and drying the mixture in a constant-temperature oven at 105 ℃ for more than 4 hours to obtain a wide-area efficient environment-friendly composite snow and ice melting material for later use, wherein the slow release rate η of the snow and ice melting material is 97.32% at 40 +/-1 ℃ under the condition that the concentration of chloride salt is 30 g/L.
Example 8
(1) Taking materials in three groups in parallel, wherein each group is 1: 7: 2, respectively taking NaCl, CaC12·2H2O and MgCl2·6H2O, putting the three into a mortar, grinding the three into powder, and uniformly stirring the powder to obtain a chlorine salt main material LB-1 of the snow melting material;
(2) preparing the following three groups of environment-friendly additives in parallel:
8-1: the weight ratio is as follows: imidazoline quaternary ammonium salt, zinc dihydrogen phosphate and thiourea are 6:1:2, an environment-friendly additive h1 is prepared, the mass ratio of the environment-friendly additive h1 to the chlorine salt main material LB-1 is 1.52%, the environment-friendly additive h1 is dissolved in water with the mass 3 times that of the environment-friendly additive, and the mixture is stirred and dissolved at normal temperature to form a transparent environment-friendly additive solution;
8-2: the weight ratio is as follows: imidazoline quaternary ammonium salt, zinc dihydrogen phosphate and thiourea are 6:1:2, an environment-friendly additive h2 is prepared, the mass ratio of the environment-friendly additive h2 to the chlorine salt main material LB-1 is 4%, the environment-friendly additive h2 is dissolved in water with the mass 3 times that of the environment-friendly additive, and the mixture is stirred and dissolved at normal temperature to form a transparent environment-friendly additive solution;
(3) uniformly spraying the solution obtained in the step (2) on the surface of the step (1) by using a small spraying pot, and uniformly stirring while spraying;
putting the mixture obtained in the step (3) into a watch glass, and drying the mixture in a constant-temperature oven at 105 ℃ for more than 4 hours to obtain a wide-area efficient environment-friendly composite snow and ice melting material for later use, wherein the slow release rate η of the snow and ice melting material obtained under the condition of 8-1 ℃ is 98.43% under the condition of 30g/L of chloride salt, the carbon steel corrosion is carried out by adopting the GB/T18175 and 2000 standard, the corrosion inhibition rate is 99.1% relative to sodium chloride, and the slow release rate η of the snow and ice melting material obtained under the condition of 8-2 at 40 +/-1 ℃ is 97.87%.
Comparative example 8-1
The comparative example is the same as the example 8-1, except that the environment-friendly additive is replaced by imidazoline quaternary ammonium salt with the corresponding mass, namely the addition amount of the imidazoline quaternary ammonium salt is 1.52 percent of that of the chloride salt main material LB-1, the rest operations are the same, and tests show that the slow release rate η of the obtained snow-melting and deicing material at the temperature of 40 +/-1 ℃ is 57.24 percent under the condition that the concentration of the chloride salt is 30 g/L.
Comparative examples 8 to 2
The comparative example is the same as the example 8-1, except that the environment-friendly additive is replaced by zinc dihydrogen phosphate with the corresponding mass, namely the adding amount of the zinc dihydrogen phosphate is 1.52 percent of that of the main material LB-1 of the chlorine salt, the rest operations are the same, and tests show that the slow release rate η of the obtained snow-melting and deicing material at 40 +/-1 ℃ is 52.56 percent under the condition that the concentration of the chlorine salt is 30 g/L.
Comparative examples 8 to 3
The comparative example is the same as the example 8-1, except that the environment-friendly additive is replaced by thiourea with the corresponding mass, namely the adding amount of the thiourea is 1.52 percent of that of the main material LB-1 of the chloride salt, the rest operations are the same, and tests show that the slow release rate η of the obtained snow-melting and deicing material is 45.20 percent at the temperature of 40 +/-1 ℃ under the condition that the concentration of the chloride salt is 30 g/L.
Example 9
(1) According to the mass ratio of 1: 7: 2, respectively taking NaCl, CaC12·2H2O and MgCl2·6H2O, putting the three into a mortar, grinding the three into powder, and uniformly stirring the powder to obtain a chlorine salt main material LB-1 of the snow melting material;
(2) preparing the following three groups of environment-friendly additives in parallel:
the weight ratio is as follows: imidazoline quaternary ammonium salt, zinc dihydrogen phosphate and thiourea are 12:3:8, an environment-friendly additive j1 is prepared, the mass ratio of the environment-friendly additive j1 is 1.92% of that of the main material LB-1 of the chloride salt, the environment-friendly additive j1 is dissolved in water with the mass 3 times that of the environment-friendly additive, and the mixture is stirred and dissolved at normal temperature to form transparent environment-friendly additive solution;
(3) uniformly spraying the solution obtained in the step (2) on the surface of the step (1) by using a small spraying pot, and uniformly stirring while spraying;
and (3) putting the mixture obtained in the step (3) into a watch glass, and drying the mixture in a constant-temperature oven at 105 ℃ for more than 4 hours to obtain a wide-area efficient environment-friendly composite snow and ice melting material for later use, wherein the slow release rate η of the snow and ice melting material is 98.05% at 40 +/-1 ℃ under the condition that the concentration of chloride salt is 30 g/L.
Example 10
(1) According to the mass ratio of 1: 5: 4, respectively taking NaCl and CaC12·2H2O and MgCl2·6H2O, putting the three into a mortar, grinding the three into powder, and uniformly stirring the powder to obtain a chlorine salt main material LB-2 of the snow melting material;
(2) the weight ratio is as follows: imidazoline quaternary ammonium salt, zinc dihydrogen phosphate and thiourea, 6:1:2, preparing an environment-friendly additive j1, wherein the mass of the environment-friendly additive j1 accounts for 1.52% of that of the chlorine salt main material LB-1, dissolving the environment-friendly additive j1 in water with the mass being 3 times that of the environment-friendly additive, and stirring and dissolving the mixture at normal temperature to form a transparent environment-friendly additive solution;
(3) uniformly spraying the solution obtained in the step (2) on the surface of the step (1) by using a small spraying pot, and uniformly stirring while spraying;
and (3) putting the mixture obtained in the step (3) into a watch glass, and drying the mixture in a constant-temperature drying oven at 105 ℃ for more than 4 hours to obtain a wide-area efficient environment-friendly composite snow and ice melting material for later use, wherein the slow release rate η of the snow and ice melting material at 40 +/-1 ℃ is 98.12% under the condition that the concentration of chloride is 30g/L, and the carbon steel corrosion is carried out by adopting the GB/T18175-adulterate 2000 standard, and the corrosion inhibition rate is 93.2% relative to sodium chloride.
Example 11
(1) According to the mass ratio of 1: 3: 6, respectively taking NaCl, CaC12·2H2O and MgCl2·6H2O, putting the three into a mortar, grinding the three into powder, and uniformly stirring the powder to obtain a chlorine salt main material LB-3 of the snow melting material;
(2) the weight ratio is as follows: imidazoline quaternary ammonium salt, zinc dihydrogen phosphate and thiourea, 1: 1:1, preparing an environment-friendly additive k1, wherein the mass ratio of the environment-friendly additive k1 to the chlorine salt main material LB-1 is 1.52%, dissolving the environment-friendly additive k1 in water with the mass 3 times that of the environment-friendly additive, and stirring and dissolving at normal temperature to obtain a transparent environment-friendly additive solution;
(3) uniformly spraying the solution obtained in the step (2) on the surface of the step (1) by using a small spraying pot, and uniformly stirring while spraying;
and (3) putting the mixture obtained in the step (3) into a watch glass, and drying the mixture in a constant-temperature drying oven at 105 ℃ for more than 4 hours to obtain a wide-area efficient environment-friendly composite snow and ice melting material for later use, wherein the slow release rate η of the snow and ice melting material at 40 +/-1 ℃ is 91.05% under the condition that the concentration of chloride is 30g/L, and the carbon steel corrosion is carried out by adopting the GB/T18175-adulterate 2000 standard, and the corrosion inhibition rate is up to 91.3% relative to sodium chloride.
The related performance test items and test results of the wide-area efficient environment-friendly composite snow and ice melting material prepared in the above examples 1 to 11 are shown in the following tables 7-1 and 7-2, wherein the ice melting speed and the dissolving speed are both in accordance with the operation process in the corresponding performance test of the chlorine salt main material, and the difference is that the chlorine salt main material is adjusted to be the prepared wide-area efficient environment-friendly composite snow and ice melting material. TABLE 7-1 snow-melting material Performance test items and Experimental results
TABLE 7-2 tables
Claims (10)
1. The wide-area efficient environment-friendly composite snow and ice melting material is characterized by comprising the following components in percentage by mass: main materials of chloride salt: environment-friendly additive (80-99.9): (0.1-20), wherein:
the main materials of the chlorine salt are anhydrous NaCl and MgCl2·6H2O and CaC12·2H2O, NaCl: MgCl2·6H2O：CaC12·2H2O10: (20-60): (30-70) mixing;
the environment-friendly additive comprises the following components in percentage by mass: cycloalkyl imidazoline quaternary ammonium salt: zinc dihydrogen phosphate salt: thiourea (4-12): (1-3): (4-12).
2. The wide-area efficient environment-friendly composite snow-melting and ice-melting material as claimed in claim 1, wherein the main material of the chlorine salt comprises, by mass, anhydrous NaCl: MgCl2·6H2O：CaC12·2H2O10: 20: 70, the adding mass of the environment-friendly additive accounts for 0.75-2.1% of the mass of the main material of the chloride salt, the zinc dihydrogen phosphate salt is added in the form of phosphoric acid and zinc oxide, and the molar ratio of the two is phosphoric acid: and (3) zinc oxide is 2:1, so as to generate zinc dihydrogen phosphate, and the generation quality of the zinc dihydrogen phosphate is ensured to be 10-50 parts.
3. The wide-area efficient environment-friendly composite snow and ice melting material as claimed in claim 1, wherein in the environment-friendly additive, imidazoline quaternary ammonium salt: zinc dihydrogen phosphate: 12, (2-3) and (4-18) the addition mass of the environment-friendly additive accounts for 1.1-2.1% of that of the main material of the chlorine salt.
4. The wide-area efficient environment-friendly composite snow and ice melting material as claimed in claim 5, wherein in the environment-friendly additive, imidazoline quaternary ammonium salt: zinc dihydrogen phosphate: thiourea ═ (4-12): (2-3): (8-12), wherein the addition mass of the environment-friendly additive accounts for 1.1-1.52% of the mass of the main material of the chlorine salt.
5. The wide-area efficient environment-friendly composite snow and ice melting material as claimed in claim 1, wherein the main material of the chlorine salt is: the environment-friendly additive is 98.5: 1.5; in the environment-friendly additive, imidazoline quaternary ammonium salt: zinc dihydrogen phosphate: thiourea was 6:1: 2.
6. The preparation method of the wide-area efficient environment-friendly composite snow and ice melting material as claimed in claim 1, characterized by comprising the following steps:
(1) according to the mixture ratio, 80-99.9 parts of chlorine salt main material and 0.1-20 parts of environment-friendly additive are taken, wherein the environment-friendly additive comprises the following components in percentage by mass: cycloalkyl imidazoline quaternary ammonium salt: zinc dihydrogen phosphate salt: thiourea (4-12): (1-3): (4-12); crushing a main chlorine salt material to obtain chlorine salt particles, wherein the particle size of the chlorine salt particles is less than or equal to 3 mm;
(2) preparing the environment-friendly additive into an aqueous solution with the concentration of 20-60%;
(3) uniformly spraying the aqueous solution of the environment-friendly additive on the surfaces of the chloride particles, and uniformly stirring to realize infiltration to prepare a wet composite snow-melting and deicing primary product;
(4) and (3) drying the wet composite snow-melting and ice-melting primary product, and then granulating or not granulating according to use requirements to prepare the wide-area efficient environment-friendly composite snow-melting and ice-melting material.
7. The method for preparing the cycloalkylimidazoline quaternary ammonium salt in the environment-friendly additive according to claim 6, comprising the following steps:
(1) in terms of molar ratio, organic acid: mixing organic amine and organic amine (1.2-1.4), adding a catalyst, stirring and heating to 120 ℃, freely discharging water through stepwise heating at the temperature of 120-200 ℃, sequentially performing intermolecular and intramolecular dehydration to obtain amide, and cyclizing to obtain an oil-soluble naphthenic imidazoline intermediate;
(2) cooling the intermediate of the naphthenic imidazoline, dissolving the intermediate in an organic solvent, and dripping an alkylating reagent into the intermediate of the naphthenic imidazoline according to a molar ratio: and (3) keeping the temperature reduction point of the alkylating reagent 1 (1.4-1.6), continuing to react for 1-3h after the dropwise addition is finished, and evaporating the organic solvent to prepare the viscous and transparent water-soluble cycloalkyl imidazoline quaternary ammonium salt, wherein the temperature reduction point of the intermediate is 10-20 ℃ lower than the boiling point of the organic solvent.
8. The method for preparing cycloalkylimidazoline quaternary ammonium salt as claimed in claim 6, wherein the step (1) comprises:
the organic acid is naphthenic acid, and the organic amine is diethylenetriamine;
the catalyst is H3BO3Adding naphthenic acid in 0.3-0.5 wt%;
the concrete stirring and heating processes are as follows: stirring and heating to 120 ℃, carrying out reflux reaction for 5 hours, heating to 160 ℃ again, and reacting for 2 hours until no water is separated out, thereby completing amidation reaction; the temperature is continuously increased to 170 ℃ for reaction for 3h, the temperature is 200 ℃ for reaction for 1.5h, and the temperature is 220 ℃ for reaction for 2.5h, thus completing cyclization.
9. The method for preparing cycloalkylimidazoline quaternary ammonium salt as claimed in claim 6, wherein in the step (2), the imidazoline intermediate is dissolved in an organic solvent of equal mass, the organic solvent is isopropanol, the cycloalkylimidazoline intermediate is cooled to 50 ℃, the alkylating agent is dimethyl sulfate or dimethyl phosphite, the dropping rate of the alkylating agent is 20 drops/min, and the boiling point of the organic solvent is 30-50 ℃ lower than that of the resultant.
10. The method for preparing the wide-area efficient environmentally friendly composite snow and ice melting material as claimed in claim 6, wherein in the step (4), the prepared wide-area efficient environmentally friendly composite snow and ice melting material is prepared by:
melting ice at-10 deg.C at 13.5-20mL (60min), dissolving at 25 deg.C at 13.9-15.0g/min, and pH at 7.02-8.18;
the addition amount accounts for 10-40% of the mass ratio of ice and snow to be melted, the freezing point reaches-3.0 ℃ to-40 ℃, and the relative snow and ice melting capacity is as follows: 1700% at the temperature of minus 10 ℃ to minus 30 ℃; wherein the temperature is 1700% at-10 ℃, 1300% at-20 ℃ and 900% at-30 ℃;
the corrosion rate of the carbon steel is 0.0053-0.0165mm/a, and the stripping amount of the C30 concrete per unit area is 1.61-2.52g/m2The germination rate of the grass seeds is 85-94% of 1% solution and 70-79% of 2% solution, and the friction attenuation of the pavement is as follows: 1.5 percent of dry basis and 1.5 to 2.5 percent of 20 percent of wet basis;
the slow release rate η of the snow-melting and deicing material is 91-98.5% at 40 + -1 deg.C under the condition of the chloride concentration of 30 g/L.
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|---|---|---|---|---|
| CN114507032A (en) * | 2021-12-08 | 2022-05-17 | 四川省交通勘察设计研究院有限公司 | Anti-freezing agent and preparation method and application thereof |
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| CN111334257B (en) | 2022-08-16 |
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