Anti-freezing cooling liquid as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of anti-freezing solutions, particularly relates to an anti-freezing cooling liquid and a preparation method and application thereof, and provides an all-organic heat transfer system anti-freezing cooling liquid which contains efficient all-organic adsorption acid and an anti-corrosion inhibition additive, has better anti-corrosion and anti-rust capabilities on various metals, and has a good anti-freezing effect. And the anti-corrosion agent has excellent anti-rust function for soldering tin, cast aluminum, cast iron, steel, brass, red copper and the like, especially the anti-corrosion performance of a wet cylinder sleeve of a heavy-duty vehicle. The lubricating oil has excellent cavitation erosion resistance and pitting corrosion resistance, and has an excellent protection effect on an engine cooling system. The anti-freezing cooling liquid product is free of precipitates, stable in performance, safe, non-toxic, green and environment-friendly.

Description

Technical Field

[0001] The present invention belongs to the technical field of antifreeze, and particularly relates to an antifreeze coolant, a preparation method thereof and an application thereof. Background Art

[0002] With the development of the automotive industry, people pay more and more attention to vehicle maintenance. Like lubricating oil, engine antifreeze coolant is an essential vehicle product to protect the long-term and efficient operation of the engine. At present, most domestic inorganic coolants and semi-organic coolants mixed with inorganic and organic components are still used. Such coolants contain phosphates, silicates, nitrites, and amine salts, which are harmful to the environment and human health. In addition, although the presence of silicate can effectively inhibit the corrosion of cast aluminum, it will cause the coolant to precipitate colloidal silicon dioxide, making the coolant turbid and generating precipitation. Therefore, inorganic engine coolants are difficult to meet the development and environmental protection requirements of the increasingly demanding automotive industry and industrial and civil heat exchange equipment.

[0003] The development of all-organic engine coolants is relatively late compared with inorganic coolants, but all-organic coolants can enable the engine to operate for 150,000 km and have a service life of more than 5 years. Compared with conventional inorganic salt corrosion inhibitors, the organic acids in all-organic coolants exhibit corrosion inhibition through active adsorption. Therefore, all-organic coolants will gradually and completely replace inorganic and inorganic-organic mixed coolants due to their advantages of low ion concentration, slow consumption, and long service life. All-organic coolants have been used abroad. Currently, many foreign companies such as BASF in Germany, CCI in Japan, and Texaco in the United States have launched their all-organic coolant products on the market. In contrast, the research and production of all-organic coolants in China are still in the initial stage.

[0004] After retrieval: Chinese patent documents CN1336410A, CN101768428A, CN102559152A, and CN102367379A each disclose the formulated all-organic coolants they developed, and corrosion experiments show that their coolants can have a certain inhibitory effect on the corrosion of various metals, but their long-term effectiveness still needs to be improved. Chinese patent documents CN1890344A, CN101134891A, and CN101215460A each disclose ethylene glycol-water-based coolants, but they all use phosphorus-containing compounds, which are not conducive to human health and environmental protection requirements.

[0005] In view of this, the inventor expects to design an antifreeze coolant that adopts an excellent organic acid adsorption rust prevention technology different from the components of existing technology products, which can not only prevent corrosion damage caused by scale formation on the heat transfer surface, but also better protect various metals from corrosion and rust, and can be used as a long-lasting and highly efficient antifreeze coolant product. Summary of the Invention

[0006] The object of the present invention is to overcome the above problems existing in the traditional technology, and to provide an antifreeze coolant and its preparation method and application.

[0007] To achieve the above technical object and reach the above technical effect, the present invention is realized through the following technical solutions:

[0008] An antifreeze coolant contains the following components by percentage:

[0009] Ice melting agent 20 - 70%

[0010] Corrosion inhibitor composition 0.1 - 10.0%

[0011] Defoaming agent 0.001 - 0.010%

[0012] Antibacterial agent 0.01 - 0.07%

[0013] Colorant 0.001 - 0.006%

[0014] The balance is pure water.

[0015] Further, the ice melting agent is at least one of methanol, ethanol, propanol, ethylene glycol, diethylene glycol, propylene glycol, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, and glycerol.

[0016] Further, the corrosion inhibitor composition is obtained by compounding a rust inhibitor, a copper corrosion inhibitor, a scale inhibitor, a bactericide, an antioxidant, and a pH regulator; the percentage content of each component in the corrosion inhibitor composition is as follows:

[0017] Copper corrosion inhibitor 0.1 - 16.0%

[0018] Scale inhibitor 0.05 - 1.5%

[0019] Bactericide 0.15 - 0.3%

[0020] Antioxidant 0.2 - 10.0%

[0021] pH regulator 2.0 - 50.0%

[0022] The balance is the rust inhibitor.

[0023] Further, the rust inhibitor contains an organic carboxylic acid, and the organic carboxylic acid is at least one of a monobasic acid, a dibasic acid, and a tribasic acid;

[0024] The monobasic acid is a C2-C22 alkyl acid, specifically at least one of acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, isocaprylic acid, enanthic acid, pelargonic acid, benzoic acid, capric acid, undecylenic acid, stearic acid, arachidic acid, and behenic acid;

[0025] The dibasic acid is a C2-C22 dialkyl acid, specifically at least one of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, diisocaprylic acid, terephthalic acid, p-tert-butylbenzoic acid, sebacic acid, bisundecylenic acid, distearic acid, dilaric acid, and dibehenic acid;

[0026] The tribasic acid is at least one of citric acid, triazine tricarboxylic acid, malonic acid, trimesic acid, C21 and C22 polycarboxylic acids.

[0027] Further, the copper corrosion inhibitor is one or a combination of two of benzotriazole or its derivatives, methylbenzotriazole or its derivatives, benzimidazole, and benzotetrazole.

[0028] Further, the scale and corrosion inhibitor is at least one of polyacrylic acid, polyacrylate, acrylic acid-acrylate copolymer, and acrylic acid-maleic anhydride copolymer;

[0029] The bactericide is at least one of sodium benzoate, isothiazolinone and its derivatives, and hydrolyzed maleic anhydride;

[0030] The antioxidant is at least one of BHT, bisphenol A, DLTP, and ascorbic acid;

[0031] The pH regulator is at least one of alkali metal hydroxides, ammonium salts, hydrolyzed maleic anhydride, citric acid, and amine-based basic organic substances.

[0032] Further, the defoamer is one or a combination of two of defoamer No. 3, polyoxypropylene ethylene glycerol ether, polyoxyethylene polyoxypropylene butyl ether, and silicone-based surfactants;

[0033] The antibacterial agent is at least one of sodium benzoate, isothiazolinone and its derivatives.

[0034] Further, the colorant is various colored organic dyes.

[0035] The present invention also provides a method for preparing an antifreeze coolant, the steps are as follows: Add the measured ice melting agent and pure water into a blending kettle, and stir and dissolve at 5-60°C; Under stirring, add the measured corrosion inhibitor composition and antibacterial agent, and stir for another 10-120 min. After blending evenly, measure and control the pH value and freezing point. When the detection is qualified, then add the defoamer and colorant. That is, the finished product of the antifreeze coolant is obtained.

[0036] The present invention also provides an application of an antifreeze coolant in a heat transfer system.

[0037] The beneficial effects of the present invention are as follows:

[0038] The present invention provides a fully organic heat transfer system antifreeze coolant, which contains highly efficient fully organic adsorbed acids and anti-corrosion inhibition additives, and has better anti-corrosion and rust prevention capabilities for various metals. For example, it has excellent rust prevention functions for soldering tin, cast aluminum, cast iron, steel, brass, copper, etc., especially the anti-corrosion performance of wet cylinder liners of heavy-duty vehicles. It has excellent anti-cavitation and anti-pitting capabilities and provides excellent protection for the engine cooling system. This antifreeze coolant product has no precipitates, stable performance, is safe, non-toxic, and environmentally friendly.

[0039] Of course, not necessarily all of the above advantages need to be achieved simultaneously when implementing any product of the present invention. Detailed implementation manners

[0040] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Apparently, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present invention.

[0041] Preparation of the corrosion inhibitor composition of the heat transfer system antifreeze coolant.

[0042] The following additive components are blended to obtain the required corrosion inhibitor composition of the fully organic heat transfer system antifreeze coolant.

[0043] The composition of the corrosion inhibitor composition of the heat transfer system antifreeze coolant is as follows:

[0044] Antirust and corrosion inhibitor: 10.0 - 80.0%

[0045] Copper corrosion inhibitor: 0.1 - 16.0%

[0046] Stable scale inhibitor: 0.05 - 1.5%

[0047] pH value regulator: 2.0 - 50.0%

[0048] Bactericide: 0.15 - 0.3%

[0049] Antioxidant: 0.2 - 10.0%

[0050] The antirust and corrosion inhibitor in the composition is a mixture of various organic carboxylic acids such as monobasic acid, dibasic acid, and tribasic acid. Specifically as follows:

[0051] The monobasic acid is a C2-C22 alkyl acid, such as one or a combination of acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, isocaprylic acid, enanthic acid, pelargonic acid, benzoic acid, capric acid, undecylenic acid, stearic acid, arachidic acid, behenic acid, etc.

[0052] The dibasic acid is a C2-C22 dialkyl acid, such as one or a combination of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, diisooctanoic acid, terephthalic acid, p-tert-butylbenzoic acid, sebacic acid, diundecenoic acid, distearic acid, diarachidic acid, dibehenic acid, etc.

[0053] The tribasic acid is one or a combination of citric acid, triazine tricarboxylic acid, malonic acid, trimellitic acid, C21 and C22 polycarboxylic acids, etc.

[0054] The copper corrosion inhibitor in the composition is one or a combination of benzotriazole or its derivatives, methylbenzotriazole or its derivatives, benzimidazole, benzotetrazole.

[0055] The bactericide in the composition is one or more of sodium benzoate, isothiazolinone and its derivatives.

[0056] The pH regulator in the composition is one or more of alkali metal hydroxides, ammonium salts, hydrolyzed maleic anhydride, citric acid, amine-based basic organic substances.

[0057] The stabilizer in the composition is one or a combination of polyacrylic acid, polyacrylate, acrylic acid-acrylate copolymer, acrylic acid-maleic anhydride copolymer.

[0058] The antioxidant in the composition is one or more of BHT, bisphenol A, DLTP, ascorbic acid.

[0059] Specific implementation of the corrosion inhibitor composition formulation for the heat transfer system antifreeze coolant

[0060] Select the compounding of multiple different substances to formulate the corrosion inhibitor composition. The following examples are selected for illustration, and the proportion of different substance combinations is shown in Table 1 below:

[0061] Table 1

[0062]

[0063]

[0064] Heat transfer system antifreeze coolant preparation case

[0065] Apply the above-prepared corrosion inhibitor composition to the preparation of the heat transfer system antifreeze coolant. The specific composition of the all-organic heat transfer system antifreeze coolant is as follows:

[0066] 20 - 70% ice melting agent

[0067] 30 - 80% pure water

[0068] 0.1 - 10.0% corrosion inhibitor composition

[0069] 0.001 - 0.010% defoamer

[0070] 0.001 - 0.006% colorant

[0071] The ice melting agent can be selected from alcohol - based substances such as methanol, ethanol, propanol, ethylene glycol, diethylene glycol, propylene glycol, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, glycerol, and mixed alcohols, and ethylene glycol is preferred.

[0072] The pure water is deionized water, softened water, distilled water, reverse osmosis water, etc., and deionized water or reverse osmosis water is preferred.

[0073] The corrosion inhibitor is the corrosion inhibitor composition prepared from Examples A1 - A6.

[0074] The defoamer is one or two of the following: ether esters: Defoamer No. 3, ethers: polyoxypropylene ethylene glycerol ether, polyoxyethylene polyoxypropylene butyl ether, and silicone - based surfactants, and Defoamer No. 3 is preferred.

[0075] The colorant is various organic dyes.

[0076] The preparation of the all - organic antifreeze coolant is carried out according to the following steps:

[0077] Add the metered ice melting agent and pure water into a blending kettle. At 5 - 120°C, preferably 10 - 80°C, after stirring and dissolving, while stirring, add the metered corrosion inhibitor composition and antibacterial agent, and then stir for 10 - 120 min, preferably 20 - 90 min. After blending evenly, detect the pH value and freezing point index in - process control. When the detected indexes are qualified, then add the defoamer and colorant to obtain the finished antifreeze coolant.

[0078] Specific examples of the all - organic antifreeze coolant:

[0079] There are large temperature changes in different seasons and regions, and the demand for antifreeze will also be different. For antifreeze with representative service ambient temperatures, the following examples with different ratios are given, as shown in Table 2:

[0080] Table 2

[0081]

[0082]

[0083]

[0084]

[0085] Implementation Effect of Anti-freezing Coolant for Heat Transfer System

[0086] During the use of the cooling antifreeze, it will come into contact with various metals and metal alloys. Place the coupons of typical metals and metal alloys in the cooling antifreeze for a glassware corrosion test, and test according to SH / T0085 - Method for Determining the Corrosion of Engine Coolants. Each group of metal coupons was tested in different cooling antifreezes at 88 ± 2 °C for 336 ± 2 h, and the mass change of each metal coupon was obtained. The specific results are shown in Table 3 as follows:

[0087] Table 3

[0088]

[0089]

[0090] As shown in Table 3, the corrosion inhibitor composition effectively provides anti-corrosion protection for various metals. There are slight differences in different cooling antifreezes with different temperatures and different proportion ratios, but good protection has been achieved, meeting the corrosion performance requirements of the anti-freezing coolant for the heat transfer cooling system.

[0091] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor limit the invention to the specific embodiments. Obviously, many modifications and variations can be made according to the content of this specification. These embodiments are selected and specifically described in this specification in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can well understand and utilize the present invention. The present invention is only limited by the claims and their full scope and equivalents.

Claims

1. An antifreeze coolant, characterized in that, Comprises the following components by percentage: Deicing agent 20 - 70% Corrosion inhibitor composition 0.1 - 10.0% Defoaming agent 0.001 - 0.010% Antibacterial agent 0.01 - 0.07% Colorant 0.001 - 0.006% The balance is pure water.

2. The anti-freeze coolant according to claim 1, characterized in that, The deicing agent is at least one of methanol, ethanol, propanol, ethylene glycol, diethylene glycol, propylene glycol, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and glycerol.

3. The antifreeze coolant according to claim 1, characterized in that, The corrosion inhibitor composition is obtained by compounding a rust inhibitor, a copper corrosion inhibitor, a scale inhibitor, a bactericide, an antioxidant, and a pH regulator; the percentage content of each component in the corrosion inhibitor composition is as follows: Copper corrosion inhibitor 0.1 - 16.0% Scale inhibitor 0.05 - 1.5% Bactericide 0.15 - 0.3% Antioxidant 0.2 - 10.0% pH regulator 2.0 - 50.0% The balance is the rust inhibitor.

4. The anti-freezing coolant according to claim 3, characterized in that, The rust inhibitor contains an organic carboxylic acid, and the organic carboxylic acid is at least one of a monocarboxylic acid, a dicarboxylic acid, and a tricarboxylic acid; The monocarboxylic acid is a C2 - C22 alkyl acid, specifically at least one of acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, isooctanoic acid, heptanoic acid, nonanoic acid, benzoic acid, capric acid, undecenoic acid, stearic acid, arachidic acid, and behenic acid; The dicarboxylic acid is a C2 - C22 dialkyl acid, specifically at least one of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, diisooctanoic acid, terephthalic acid, p-tert-butylbenzoic acid, sebacic acid, bis-undecenoic acid, bis-stearic acid, bis-arachidic acid, and bis-behenic acid; The tricarboxylic acid is at least one of citric acid, triazine tricarboxylic acid, malonic acid, trimellitic acid, C21 and C22 polycarboxylic acids.

5. The anti-freezing coolant according to claim 3, characterized in that, The copper corrosion inhibitor is one or a combination of two of benzotriazole or its derivatives, methylbenzotriazole or its derivatives, benzimidazole, and benzotetrazole.

6. The anti-freeze coolant according to claim 3, characterized in that, The scale inhibitor is at least one of polyacrylic acid, polyacrylate, acrylic acid - acrylate copolymer, and acrylic acid - maleic anhydride copolymer; The bactericide is at least one of sodium benzoate, isothiazolinone and its derivatives, and hydrolyzed maleic anhydride; The antioxidant is at least one of BHT, bisphenol A, DLTP, and ascorbic acid; The pH regulator is at least one of alkali metal hydroxides, ammonium salts, hydrolyzed maleic anhydride, citric acid, and amine-based basic organic substances.

7. The anti-freezing coolant according to claim 1, characterized in that, The defoaming agent is one or a combination of two of defoaming agent No. 3, polyoxypropylene ethylene glycerol ether, polyoxyethylene polyoxypropylene butyl ether, and silicone-based surfactants; The antibacterial agent is at least one of sodium benzoate, isothiazolinone and its derivatives.

8. The antifreeze coolant according to claim 1, characterized in that, The colorant is various colored organic dyes.

9. The preparation method of the antifreeze coolant according to any one of claims 1 to 8, characterized in that The steps are as follows: Add the metered deicing agent and pure water to a blending kettle, and stir and dissolve at 5 - 60°C; while stirring, add the metered corrosion inhibitor composition and antibacterial agent, and stir for another 10 - 120 min. After mixing evenly, perform in - process control to detect the pH value and freezing point. When the detection is qualified, then add the defoaming agent and colorant. Thus, the finished product of the antifreeze coolant is obtained.

10. Use of the anti-freezing coolant according to any one of claims 1 to 8 in a heat transfer system.

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