阅读说明：本技术 一种防腐型防冻液的制备方法 (Preparation method of anticorrosive antifreezing solution ) 是由 陈文广 于 2019-09-27 设计创作，主要内容包括：本发明属于防冻制品技术领域,具体涉及一种防腐型防冻液的制备方法。本发明首先将蓖麻与茶籽粕干燥粉碎混合,将改性活化剂、自制防腐粉末以及其它助剂混合搅拌均匀即得防腐型防冻液,将蓖麻和茶籽粕经过酸碱液反应和高温高压处理,利用有机物中具有的羧基羟基团络合吸附与静电吸引铝离子,增加防腐性能,茶多酚具有良好的抗氧化性能,提高防冻液的防腐性能；以鳞片石墨作为原料制备石墨烯成分,增加有机纤维的强度,提高防冻液的耐久性,同时石墨烯成分的比表面大,有利于提高各成分的反应活性,提高防冻液的防冻能力,铝单质在防冻液中优先与外界环境反应生成氧化铝单质增加隔热性能,提高防冻液的防冻性能,具有广阔的应用前景。(The invention belongs to the technical field of anti-freezing products, and particularly relates to a preparation method of an anti-corrosion anti-freezing solution. According to the method, firstly, castor oil and tea seed meal are dried, crushed and mixed, a modification activating agent, self-made anticorrosive powder and other auxiliaries are mixed and stirred uniformly to obtain the anticorrosive antifreezing solution, the castor oil and the tea seed meal are subjected to acid-alkali solution reaction and high-temperature and high-pressure treatment, aluminum ions are absorbed by utilizing carboxyl and hydroxyl groups in organic matters in a complexing way and static electricity, the anticorrosive performance is improved, tea polyphenol has good antioxidant performance, and the anticorrosive performance of the antifreezing solution is improved; the graphene component is prepared by taking the crystalline flake graphite as a raw material, so that the strength of organic fibers is increased, the durability of the antifreeze is improved, meanwhile, the specific surface area of the graphene component is large, the improvement of the reaction activity of each component is facilitated, the antifreezing capability of the antifreeze is improved, the aluminum simple substance preferentially reacts with the external environment in the antifreeze to generate the aluminum simple substance, the heat insulation performance is improved, the antifreezing performance of the antifreeze is improved, and the wide application prospect is achieved.)

1. The preparation method of the anticorrosive antifreezing solution is characterized by comprising the following specific preparation steps:

adding the modified activating agent, the self-made anticorrosive powder, polyethylene glycol and glycerol into a stirrer, uniformly mixing to obtain a prefabricated mixed solution, adding the prefabricated mixed solution, sodium dodecyl benzene sulfonate and carboxymethyl cellulose into a reaction kettle, stirring for 30-40 min at the temperature of 45-50 ℃ and at the rotating speed of 1100-1200 r/min, and discharging to obtain the anticorrosive antifreezing solution;

the specific preparation steps of the modified activating agent are as follows:

(1) putting the scaly graphite and a sulfuric acid solution with the mass fraction of 20-24% into a beaker, stirring for 50-60 min at the rotating speed of 600-700 r/min by using a stirrer to prepare a solid-liquid mixture, adding potassium permanganate powder into the beaker, and stirring for 30-40 min at the rotating speed of 500-600 r/min by using a stirring device to prepare an oxidation reaction solution;

(2) adding sodium hypochlorite into a beaker, placing the beaker into an ultrasonic oscillator, oscillating for 2-3 hours under the condition that the frequency is 32-36 kHz, filtering after oscillation to obtain a filter cake, sequentially cleaning the filter cake for 3-5 times by using hydrogen peroxide and distilled water with the mass fraction of 12-16%, drying the filter cake, and then putting the filter cake into a planet ball mill to be ground and sieved by a 100-mesh sieve to obtain a modified activating agent;

the self-made anticorrosive powder is prepared by the following specific steps:

(1) putting castor-oil plants and tea seed meal into an oven, drying for 3-4 h at the temperature of 80-90 ℃, putting into a crusher after drying, crushing and mixing to obtain a dried material, putting the dried material and a sodium hydroxide solution with the mass fraction of 10-15% into a beaker, putting the beaker into a water bath kettle with the temperature of 80-90 ℃, and heating at constant temperature for 2-3 h to obtain reaction slurry;

(2) putting the reaction slurry and aluminum chloride crystal powder into a reaction kettle, hermetically filling nitrogen into the reaction kettle to increase the air pressure in the reaction kettle to 1.0-1.2 MPa, then increasing the temperature in the reaction kettle to 150-170 ℃, reacting at constant temperature and constant pressure for 60-80 min to obtain a reaction mixed solution, dropwise adding an acetic acid solution with the mass fraction of 13-15% and the mass fraction of 30-35% of the reaction mixed solution into the reaction kettle after reaction, and mixing and stirring at the rotating speed of 500-600 r/min by using a stirrer for 40-50 min to obtain an acidic reaction solution;

(3) putting the acidic reaction liquid and the simple substance iron powder into a three-neck flask, stirring for 30-40 min at a rotating speed of 500-600 r/min by using a stirring device, installing a condenser pipe in the three-neck flask after stirring, placing the three-neck flask in a resistance heating sleeve, raising the temperature in the heating sleeve to 80-100 ℃, heating at a constant temperature for condensation and reflux until the quality of a product in the beaker is constant, and cleaning the product for 3-5 times by using distilled water to prepare the self-made anticorrosive powder.

2. The method for preparing corrosion-resistant anti-freezing solution according to claim 1, which is characterized in that: preferably, the modified activating agent is 3-5 parts by weight, the self-made anticorrosive powder is 1-2 parts by weight, the polyethylene glycol is 15-17 parts by weight, and the glycerol is 8-10 parts by weight.

3. The method for preparing corrosion-resistant anti-freezing solution according to claim 1, which is characterized in that: preferably, the prefabricated mixed liquid comprises 30-32 parts by weight of sodium dodecyl benzene sulfonate and 0.4-0.6 part by weight of carboxymethyl cellulose.

4. The method for preparing corrosion-resistant anti-freezing solution according to claim 1, which is characterized in that: the specific preparation method of the modified activating agent comprises the following steps that (1) the mass ratio of the flaky graphite to a sulfuric acid solution with the mass fraction of 20-24% is 1: 10.

5. the method for preparing corrosion-resistant anti-freezing solution according to claim 1, which is characterized in that: the specific preparation method of the modified activating agent comprises the step (1) that the mass of the potassium permanganate powder added into the beaker is 5-7% of the mass of the solid-liquid mixture.

6. The method for preparing corrosion-resistant anti-freezing solution according to claim 1, which is characterized in that: the mass of the sodium hypochlorite added into the beaker in the specific preparation step (2) of the modified activating agent is 8-10% of the mass of the oxidation reaction liquid.

7. The method for preparing corrosion-resistant anti-freezing solution according to claim 1, which is characterized in that: the mass ratio of the castor-oil plants to the tea seed meal in the specific preparation step (1) of the self-made anticorrosive powder is 5:1, and the mass ratio of the dry material to a sodium hydroxide solution with the mass fraction of 10-15% is 1: 10.

8. the method for preparing corrosion-resistant anti-freezing solution according to claim 1, which is characterized in that: the mass ratio of the reaction slurry to the aluminum chloride crystal powder in the specific preparation step (2) of the self-made anticorrosive powder is 15: 1.

9. The method for preparing corrosion-resistant anti-freezing solution according to claim 1, which is characterized in that: the mass of the acetic acid solution dropwise added into the reaction kettle with the mass fraction of 13-15% is 30-35% of the mass of the reaction mixed liquid in the specific preparation step (2) of the self-made anticorrosive powder.

10. The method for preparing corrosion-resistant anti-freezing solution according to claim 1, which is characterized in that: the mass ratio of the acidic reaction liquid to the simple substance iron powder in the specific preparation step (3) of the self-made anticorrosive powder is 15: 1.

Technical Field

The invention belongs to the technical field of anti-freezing products, and particularly relates to a preparation method of an anti-corrosion anti-freezing solution.

Background

The antifreeze is also called as antifreeze coolant, and means a coolant with an antifreeze function, and can prevent the coolant from freezing to burst a radiator and freeze an engine cylinder body when the vehicle is stopped in a cold season, but the antifreeze is not only used in winter, but is required to be replaced every year when the vehicle is normally maintained, and the replacement frequency of the antifreeze of a special vehicle is high.

The antifreezing solution is a cooling solution containing special additives, is mainly used for a liquid cooling type engine cooling system, and has the excellent performances of freezing prevention in winter, boiling prevention in summer, scale prevention all the year round, corrosion prevention and the like. Compared with tap water, the water-based antifreezing solution using glycol in an amount of over 95% at home and abroad has the most obvious characteristic of preventing freezing, but cannot prevent freezing of water. And secondly, the glycol has high boiling point, small volatility, moderate viscosity, small temperature change and good thermal stability. Therefore, the ethylene glycol type antifreeze is an ideal coolant. Many driver friends are generally accustomed to using antifreeze in winter and tap water in summer to make it economically cost-effective to do so, but not. The anti-freezing liquid has the most basic functions of anti-freezing liquid, such as boiling prevention, scale prevention, corrosion prevention and the like. The antifreezing solution can effectively prevent the water tank from boiling in summer, and can prevent the water cooling system from scaling and inhibit corrosion of various metals when used all the year round.

Although the antifreeze solution used in the current market can meet general requirements, the antifreeze solution commonly used at present cannot meet the requirements on antifreeze performance, thermal stability and corrosion resistance stability along with the change of human living environment conditions and the continuous expansion of the requirements of some special vehicles, so that the development of the automobile antifreeze solution with more excellent performance is required. The antifreezing fluid for the automobile engine mainly comprises water, antifreezing fluid and other various additives, has the effects of cooling, antifreezing, corrosion prevention, scale prevention and the like, is a protective heat-radiating medium which is indispensable for the work of the automobile engine, has a vital influence on the service life of the engine, and directly influences the service life of the automobile.

According to the components of the base liquid, the conventional antifreezing solution for the automobile engine can be divided into two types of antifreezing solutions, namely ethylene glycol type antifreezing solution and propylene glycol type antifreezing solution. Two types of cooling liquid. The existing cooling liquid has good cooling effect, extremely low cost and easy degradation, but the water system cooling media can generate phenomena of scale deposit, cavitation, galvanic corrosion and the like when working for a long time, and can also form a high-pressure steam layer and an overheating peak, and simultaneously, the problem of 'boiling' is generated because the heat balance capability is poor and the engine is overheated compared with the solution under the heavy load condition.

The antifreeze solution for engines in China has low quality, and the middle-high end market is basically occupied by foreign imported products. Meanwhile, the research of the novel antifreeze solution in China is late, and related technical invention patents are few.

On the other hand, oil-based antifreeze solutions for engines are gradually emerging abroad, but the synthetic routes are quite complicated, the production cost is high, and the product price is high.

At present, the anti-freezing solution comprises: the frost resistance is general, the frost resistance effect is general, the corrosion resistance is general, and the like.

Therefore, a new preparation method of the antifreeze solution for cooling the engine needs to be developed, so that the produced antifreeze solution has excellent performance, is simple in preparation method and economical in production cost, and has positive significance in the technical field of antifreeze products.

Disclosure of Invention

The technical problems to be solved by the invention are as follows: aiming at the defects of poor freezing resistance and poor corrosion resistance of the conventional antifreeze, the preparation method of the anticorrosive antifreeze is provided.

In order to solve the technical problems, the invention adopts the technical scheme that:

the preparation method of the anticorrosive antifreezing solution is characterized by comprising the following specific preparation steps:

adding the modified activating agent, the self-made anticorrosive powder, polyethylene glycol and glycerol into a stirrer, uniformly mixing to obtain a prefabricated mixed solution, adding the prefabricated mixed solution, sodium dodecyl benzene sulfonate and carboxymethyl cellulose into a reaction kettle, stirring for 30-40 min at the temperature of 45-50 ℃ and at the rotating speed of 1100-1200 r/min, and discharging to obtain the anticorrosive antifreezing solution;

the specific preparation steps of the modified activating agent are as follows:

(1) putting the scaly graphite and a sulfuric acid solution with the mass fraction of 20-24% into a beaker, stirring for 50-60 min at the rotating speed of 600-700 r/min by using a stirrer to prepare a solid-liquid mixture, adding potassium permanganate powder into the beaker, and stirring for 30-40 min at the rotating speed of 500-600 r/min by using a stirring device to prepare an oxidation reaction solution;

(2) adding sodium hypochlorite into a beaker, placing the beaker into an ultrasonic oscillator, oscillating for 2-3 hours under the condition that the frequency is 32-36 kHz, filtering after oscillation to obtain a filter cake, sequentially cleaning the filter cake for 3-5 times by using hydrogen peroxide and distilled water with the mass fraction of 12-16%, drying the filter cake, and then putting the filter cake into a planet ball mill to be ground and sieved by a 100-mesh sieve to obtain a modified activating agent;

the self-made anticorrosive powder is prepared by the following specific steps:

(1) putting castor-oil plants and tea seed meal into an oven, drying for 3-4 h at the temperature of 80-90 ℃, putting into a crusher after drying, crushing and mixing to obtain a dried material, putting the dried material and a sodium hydroxide solution with the mass fraction of 10-15% into a beaker, putting the beaker into a water bath kettle with the temperature of 80-90 ℃, and heating at constant temperature for 2-3 h to obtain reaction slurry;

(2) putting the reaction slurry and aluminum chloride crystal powder into a reaction kettle, hermetically filling nitrogen into the reaction kettle to increase the air pressure in the reaction kettle to 1.0-1.2 MPa, then increasing the temperature in the reaction kettle to 150-170 ℃, reacting at constant temperature and constant pressure for 60-80 min to obtain a reaction mixed solution, dropwise adding an acetic acid solution with the mass fraction of 13-15% and the mass fraction of 30-35% of the reaction mixed solution into the reaction kettle after reaction, and mixing and stirring at the rotating speed of 500-600 r/min by using a stirrer for 40-50 min to obtain an acidic reaction solution;

(3) putting the acidic reaction liquid and the simple substance iron powder into a three-neck flask, stirring for 30-40 min at a rotating speed of 500-600 r/min by using a stirring device, installing a condenser pipe in the three-neck flask after stirring, placing the three-neck flask in a resistance heating sleeve, raising the temperature in the heating sleeve to 80-100 ℃, heating at a constant temperature for condensation and reflux until the quality of a product in the beaker is constant, and cleaning the product for 3-5 times by using distilled water to prepare the self-made anticorrosive powder.

Preferably, the modified activating agent is 3-5 parts by weight, the self-made anticorrosive powder is 1-2 parts by weight, the polyethylene glycol is 15-17 parts by weight, and the glycerol is 8-10 parts by weight.

Preferably, the prefabricated mixed liquid comprises 30-32 parts by weight of sodium dodecyl benzene sulfonate and 0.4-0.6 part by weight of carboxymethyl cellulose.

The specific preparation method of the modified activating agent comprises the following steps that (1) the mass ratio of the flaky graphite to a sulfuric acid solution with the mass fraction of 20-24% is 1: 10.

the specific preparation method of the modified activating agent comprises the step (1) that the mass of the potassium permanganate powder added into the beaker is 5-7% of the mass of the solid-liquid mixture.

The mass of the sodium hypochlorite added into the beaker in the specific preparation step (2) of the modified activating agent is 8-10% of the mass of the oxidation reaction liquid.

The mass ratio of the castor-oil plants to the tea seed meal in the specific preparation step (1) of the self-made anticorrosive powder is 5:1, and the mass ratio of the dry material to a sodium hydroxide solution with the mass fraction of 10-15% is 1: 10.

the mass ratio of the reaction slurry to the aluminum chloride crystal powder in the specific preparation step (2) of the self-made anticorrosive powder is 15: 1.

The mass of the acetic acid solution dropwise added into the reaction kettle with the mass fraction of 13-15% is 30-35% of the mass of the reaction mixed liquid in the specific preparation step (2) of the self-made anticorrosive powder.

The mass ratio of the acidic reaction liquid to the simple substance iron powder in the specific preparation step (3) of the self-made anticorrosive powder is 15: 1.

The beneficial technical effects of the invention are as follows:

(1) the invention firstly dries, crushes and mixes castor and tea seed meal, puts into alkali liquor for high temperature reaction to prepare reaction slurry, then mixes the reaction slurry with aluminum chloride for high temperature and high pressure reaction, then adds acetic acid to prepare acid reaction liquid, then adds iron powder into the acid reaction liquid, heats at high temperature, condenses and refluxes to prepare self-made anticorrosion powder, then reacts flaky graphite with sulfuric acid, adds potassium permanganate after reaction and stirs to prepare oxidation reaction liquid, then adds sodium hypochlorite and filters by ultrasonic oscillation to prepare modified activating agent, finally mixes and stirs the modified activating agent, the self-made anticorrosion powder and other auxiliary agents evenly to obtain the anticorrosion antifreeze solution, the invention makes castor and tea seed meal undergo acid-alkali liquor reaction and high temperature and high pressure treatment, extracts organic components such as organic fiber, cellulose, tea polyphenol and the like from the castor and tea seed meal, utilizes carboxyl hydroxyl group in the organic matter to complex and adsorb and electrostatically attract aluminum ions, aluminum ions are bonded in fiber components, organic components are dispersed in antifreeze liquid components, iron powder is used for replacement to generate an aluminum simple substance, nanoscale particles of the aluminum simple substance are generated in the antifreeze liquid, the aluminum simple substance has an oxidizing effect on microorganisms, electrolyte balance in the microorganisms is damaged, corrosion resistance is improved, the nanoscale particles of the aluminum simple substance have good oxidation resistance, and the organic components are dispersed in the antifreeze liquid, so that the oxidation resistance of the antifreeze liquid can be effectively improved, and the corrosion resistance of the antifreeze liquid can be further improved;

(2) the graphene component is prepared by taking crystalline flake graphite as a raw material, the graphene is dispersed in organic components extracted from castor-oil plants and tea seed meal, the strength of organic fibers is increased, the durability of the antifreeze is improved, meanwhile, the specific surface of the graphene component is large, adsorption of other substances in the antifreeze is beneficial to improving the reaction activity of each component, the molecular motion capability of each component under low temperature is enhanced, the antifreeze capability of the antifreeze is improved, meanwhile, an aluminum simple substance preferentially reacts with the external environment in the antifreeze to generate an aluminum simple substance to increase the heat insulation performance, the antifreeze performance of the antifreeze is further improved, and the antifreeze has wide application prospect.

Detailed Description

Putting castor-oil plants and tea seed meal into an oven according to a mass ratio of 5:1, drying for 3-4 h at the temperature of 80-90 ℃, putting into a crusher after drying, crushing and mixing to obtain a dried material, and mixing the dried material with a 10-15% sodium hydroxide solution according to a mass ratio of 1: 10, putting the mixture into a beaker, putting the beaker into a water bath kettle at the temperature of 80-90 ℃, and heating the beaker at constant temperature for 2-3 hours to prepare reaction slurry; putting the reaction slurry and aluminum chloride crystal powder into a reaction kettle according to a mass ratio of 15:1, sealing the reaction kettle, filling nitrogen into the reaction kettle to increase the air pressure in the reaction kettle to 1.0-1.2 MPa, then increasing the temperature in the reaction kettle to 150-170 ℃, carrying out constant-temperature and constant-pressure reaction for 60-80 min to obtain a reaction mixed solution, dropwise adding an acetic acid solution with a mass fraction of 13-15% and a mass fraction of 30-35% of the reaction mixed solution into the reaction kettle after the reaction, and mixing and stirring the mixture by using a stirrer at a rotating speed of 500-600 r/min for 40-50 min to obtain an acidic reaction solution; putting the acidic reaction liquid and simple substance iron powder into a three-neck flask according to the mass ratio of 15:1, stirring for 30-40 min at the rotating speed of 500-600 r/min by using a stirring device, installing a condenser pipe in the three-neck flask after stirring, placing the three-neck flask into a resistance heating sleeve, raising the temperature in the heating sleeve to 80-100 ℃, heating at constant temperature for condensation and reflux until the quality of a product in the beaker is constant, and cleaning the product for 3-5 times by using distilled water to prepare self-made anticorrosive powder for later use; the method comprises the following steps of mixing flaky graphite and a sulfuric acid solution with the mass fraction of 20-24% in a mass ratio of 1: 10, putting the mixture into a beaker, stirring the mixture for 50 to 60 minutes by using a stirrer at the rotating speed of 600 to 700r/min to prepare a solid-liquid mixture, adding potassium permanganate powder with the mass of 5 to 7 percent of the solid-liquid mixture into the beaker, and stirring the mixture for 30 to 40 minutes by using a stirring device at the rotating speed of 500 to 600r/min to prepare an oxidation reaction solution; adding sodium hypochlorite accounting for 8-10% of the mass of the oxidation reaction liquid into the beaker, placing the beaker into an ultrasonic oscillator, oscillating for 2-3 hours under the condition that the frequency is 32-36 kHz, filtering to obtain a filter cake after oscillation, sequentially cleaning the filter cake for 3-5 times by using hydrogen peroxide and distilled water accounting for 12-16% of the mass fraction, drying the filter cake, and then putting the filter cake into a planetary ball mill to be ground and sieved by a 100-mesh sieve to obtain a modified activating agent; 3-5 parts of modified activating agent, 1-2 parts of standby anticorrosive powder, 15-17 parts of polyethylene glycol and 8-10 parts of glycerol are put into a stirrer to be uniformly mixed to prepare a prefabricated mixed solution, 30-32 parts of prefabricated mixed solution, 1-2 parts of sodium dodecyl benzene sulfonate and 0.4-0.6 part of carboxymethyl cellulose are put into a reaction kettle, and the mixture is stirred for 30-40 min under the conditions of the temperature of 45-50 ℃ and the rotating speed of 1100-1200 r/min to obtain the anticorrosive antifreezing solution.