CN114561196A - Antifreeze fluid using coal-to-ethylene glycol byproduct as raw material - Google Patents

Abstract

The invention relates to an antifreezing solution using coal-to-ethylene glycol byproduct as a raw material. The antifreeze solution comprises a coal glycol byproduct with the mass percentage of 38-60%, triethanolamine, sodium benzoate, benzotriazole, sebacic acid, sodium phytate, phenol red and distilled water. The invention utilizes the components of glycol, butanediol and other dihydric alcohols mainly contained in the coal-to-ethylene glycol byproduct to realize the freezing point depression of the solution, thereby realizing the anti-freezing function. The antifreeze solution is prepared by utilizing the byproducts of the coal-to-ethylene glycol based on the sustainable development requirements of byproduct recycling and high-value utilization, and has the advantages of low freezing point, high boiling point and good economy.

Description

Antifreeze fluid using coal-to-ethylene glycol byproduct as raw material

Technical Field

The invention belongs to the field of high-value utilization of low-value products, and particularly relates to an antifreezing solution prepared from a coal-to-ethylene glycol byproduct

Background

The by-product 1, 2-butanediol in the ethylene glycol synthesis process has a boiling point very close to that of ethylene glycol, and forms an azeotrope with ethylene glycol to be difficult to separate, and 30-40 ten thousand tons of the by-products are generated each year and generally sold at a low value or used as a fuel.

The by-product mainly contains glycol, butanediol and a small amount of other components, the physical properties of the by-product accord with the preparation requirements of the antifreeze, the chemical properties of the by-product are stable, the raw material price is low, and the by-product has the economic advantage of being used as the antifreeze; as the freezing point of the contained 1, 2-butanediol is lower than that of the ethylene glycol, the separation of the ethylene glycol and the butanediol is not needed, the energy consumption can be saved, and the antifreeze can be converted into antifreeze products with higher added values, and has the advantage of low production cost. The research on preparing the antifreeze solution from the coal-to-glycol waste liquid is carried out, and the research on preparing the antifreeze solution from the coal-to-glycol waste liquid (Hou' an research on preparing the automobile antifreeze solution from the coal-to-glycol process waste liquid [ D ]. Beijing university of chemical industry, 2017) and the like, and the used raw materials have the following problems that firstly, the antifreeze solution contains more light components such as methanol, ethanol and water, secondly, the content of 1, 2-butanediol is relatively low, thirdly, the raw materials are treated by alkaline hydrolysis reaction, and the pretreatment requirement on the raw materials is high.

Disclosure of Invention

The invention aims to provide an antifreezing solution taking a coal-to-ethylene glycol byproduct as a raw material, aiming at the defects in the prior art. The antifreeze solution realizes the freezing point reduction of the solution by using glycol, butanediol and other dihydric alcohol components mainly contained in the coal-to-ethylene glycol byproduct, thereby realizing the antifreeze function. The antifreeze solution is prepared by utilizing the byproducts of the coal-to-ethylene glycol based on the sustainable development requirements of byproduct recycling and high-value utilization, and has the advantages of low freezing point, high boiling point and good economy.

In order to achieve the above purpose, the invention adopts the following technical scheme

An antifreezing solution taking coal-to-ethylene glycol byproducts as raw materials comprises the following components in percentage by mass:

wherein, the components of the coal-to-ethylene glycol byproduct comprise: the mass fraction is as follows: 65 to 80 percent of ethylene glycol, 15 to 25 percent of 1 to 2 butanediol, 1.5 to 3.5 percent of other butanediol (2, 3-butanediol, 1, 3-butanediol and the like), and 0.2 to 1.2 percent of esters (gamma-butyrolactone, propylene carbonate and the like).

The antifreezing solution also comprises one or two of sodium phytate and phenol red, wherein the weight percentage of the sodium phytate is 0.1-0.3%, and the phenol red is 0.01-0.03%.

The preparation method of the antifreeze solution using the coal-to-ethylene glycol byproduct as the raw material comprises the following steps:

according to the proportion, the related components and distilled water are added into the coal-to-ethylene glycol byproduct, and the mixture is stirred for 10-20 min at 40-60 ℃ to obtain the antifreezing solution.

The invention has the substantive characteristics that:

compared with the antifreezing solution which takes ethylene glycol or propylene glycol as a main component in the traditional antifreezing solution, the antifreezing solution provided by the invention is prepared by adding a small amount of anti-corrosion additive and part of distilled water, wherein the main antifreezing solution comprises two dihydric alcohols of ethylene glycol and butanediol with very low freezing points. The antifreezing property is mainly that substances with lower freezing points, such as glycol and water, are mixed in different proportions, so that the freezing point of water is reduced to different degrees to achieve the antifreezing property and the aim, the freezing point of 1, 2-butanediol is lower than that of glycol, the antifreezing effect is improved because the antifreezing agent contains more 1, 2-butanediol.

The sodium phytate is a pure natural green additive, has strong chelation with metal ions and strong oxidation resistance, is used as an anti-corrosion additive, and has strong safety performance. The phenol red is a dye, and a small amount of the phenol red is added to change the color of the antifreeze solution, so that the antifreeze solution has more obvious color and is convenient to distinguish from other solutions.

The invention has the beneficial effects that:

the invention prepares a series of antifreeze by using the by-product of the coal-to-ethylene glycol, the main components of the by-product of the coal-to-ethylene glycol are ethylene glycol and butanediol, and the by-product is used as the main component of the antifreeze, rather than the pure ethylene glycol in the traditional antifreeze. The coal-to-ethylene glycol by-product, a small amount of additive and distilled water are simply heated and stirred to prepare the novel efficient, safe and antifreezing solution. Meanwhile, through tests, the freezing point of the antifreeze prepared by the formula is as low as-55 ℃, and is as low as 3 ℃ compared with the freezing point of the ethylene glycol antifreeze with the same alcohol content of-52 ℃; the boiling point can reach 114.9 ℃ at most, which is far higher than the national standard requirement. At present, most of the commercially available antifreeze solutions do not add inorganic salt corrosion inhibitors any more, but favor more organic and organic acid additives with higher safety, and the organic acid corrosion inhibition additives also become the development trend of antifreeze solution additives in the future due to the green and safe characteristics of the additives. The invention also selects a plurality of organic corrosion inhibitors and organic acid corrosion inhibitors, does not add additives of inorganic salts with higher toxicity such as phosphate, nitrate and the like, and adds natural green additives such as sodium phytate and the like, thereby having stronger safety performance and lower freezing point.

The by-product of the coal-based glycol is sold at 3000-.

Detailed Description

The main component of the invention is coal-made glycol by-product, the rectification process of coal-made glycol generally comprises two processes, one process comprises that crude glycol sequentially passes through a methanol removing tower, an ester removing tower, a light component removing tower (removing butanediol) and a product tower to obtain glycol products, and the other process comprises that crude glycol sequentially passes through the methanol removing tower, a dehydration tower/the light component removing tower (removing butanediol, methyl glycolate and dimethyl oxalate) and the product tower to obtain glycol products. The invention uses a coal-to-ethylene glycol byproduct obtained by a manufacturer adopting the first process and provided with a rectifying tower with a degreasing function, wherein the coal-to-ethylene glycol byproduct comprises the following components: 75% of ethylene glycol, 23% of 1-2 butanediol, 1.5% of other butanediol (2, 3-butanediol, 1, 3-butanediol and the like), 0.4% of esters (gamma-butyrolactone, propylene carbonate and the like), and the content of methyl glycolate and dimethyl oxalate is less than 0.1%. In the preparation process, the ester substances of the non-dihydric alcohol have no influence on the performance of the product and no influence such as pollution and the like because the dilution content is less than 0.1 percent.

The present invention will be described in further detail with reference to specific examples below:

example 1: the efficient and economical antifreezing solution is prepared by the following steps:

adding the coal-to-glycol by-product into a beaker, adding triethanolamine, benzotriazole, sodium benzoate, sebacic acid, sodium phytate, phenol red and distilled water into the beaker, and stirring for 15min at 55 ℃ to obtain the efficient economical antifreezing solution.

The antifreezing solution comprises the following components in percentage by mass: 60% of coal glycol byproduct, 0.5% of triethanolamine, 0.3% of benzotriazole, 0.2% of sebacic acid, 0.2% of sodium phytate, 0.5% of sodium benzoate, 0.03% of phenol red and 38.27% of distilled water.

Performance testing

Freezing point test: referring to the national petrochemical industry standard SH/T0090 engine coolant freezing point determination method, the test method comprises the following steps: measuring 75-100mL of sample antifreeze solution, adding the sample antifreeze solution into a cooling pipe with a stirring device moving up and down, cooling the sample by adopting a refrigerant or other methods, wherein the cooling speed is within 1 ℃/min, and the stirring speed is adjusted to be 60-80 times per minute. Carefully observing, recording the temperature of the sample per minute, drawing a temperature curve graph, drawing the intersection point of a crystallization curve and a cooling curve of the reagent, wherein the ordinate of the intersection point is the freezing point of the sample. When the supercooling phenomenon occurs in the test, the highest temperature to which the reagent is raised after supercooling is the freezing point.

Test samples: example 1, control 1

Control 1 is the current basic glycol-type antifreeze: contains 60% of glycol, 0.4% of triethanolamine serving as a corrosion inhibitor, 0.25% of sodium benzoate, 0.15% of sodium metasilicate and the balance of distilled water.

The high-efficiency economical antifreeze obtained in the embodiment 1.

The freezing point of example 1 was-55 ℃ and that of control 1 was-52 ℃. Therefore, compared with pure glycol type antifreeze, when the alcohol content is the same, the antifreeze prepared by the formula has a lower freezing point which reaches-55 ℃, and meanwhile, the main component of the formula is derived from a byproduct of coal glycol, so that the antifreeze is directly prepared and has low production cost.

Example 2

An efficient and economical antifreezing solution comprises the following components in parts by mass: 38% of coal glycol byproduct, 0.5% of triethanolamine, 0.3% of benzotriazole, 0.2% of sebacic acid, 0.2% of sodium phytate, 0.5% of sodium benzoate, 0.03% of phenol red and 60.27% of distilled water. The freezing point is-22.2 ℃, and is 0.2 ℃ lower than the freezing point of the pure glycol type antifreeze solution with the glycol content of 38 percent at-22 ℃.

Example 3

An efficient and economical antifreezing solution comprises the following components in parts by mass: 44% of coal glycol byproduct, 0.5% of triethanolamine, 0.3% of benzotriazole, 0.2% of sebacic acid, 0.2% of sodium phytate, 0.5% of sodium benzoate, 0.03% of phenol red and 54.27% of distilled water. The freezing point is-28.4 ℃, and is 0.4 ℃ lower than that of the pure glycol type antifreeze solution with the content of 44 percent of glycol at-28 ℃.

Example 4

An efficient and economical antifreezing solution comprises the following components in parts by mass: 50% of coal glycol byproduct, 0.5% of triethanolamine, 0.3% of benzotriazole, 0.2% of sebacic acid, 0.2% of sodium phytate, 0.5% of sodium benzoate, 0.03% of phenol red and 48.27% of distilled water. The freezing point is-37.1 ℃, and is 1.1 ℃ lower than that of the pure glycol type antifreeze solution with the glycol content of 50 percent at-36 ℃.

Example 5

An efficient and economical antifreezing solution comprises the following components in parts by mass: 56% of coal glycol byproduct, 0.5% of triethanolamine, 0.3% of benzotriazole, 0.2% of sebacic acid, 0.2% of sodium phytate, 0.5% of sodium benzoate, 0.03% of phenol red and 42.27% of distilled water. The freezing point is-46.1 ℃, and is 2.1 ℃ lower than that of pure glycol type antifreeze solution with 56 percent of glycol at-44 ℃.

The embodiment shows that the antifreeze solution with more excellent freezing point performance and lower production energy consumption can be obtained, and an effective path is provided for resource utilization of the coal-to-ethylene glycol byproduct.

The above description is only for the specific embodiments of the present invention, and the present invention is not limited to the above embodiments, and any modifications, substitutions, improvements, etc. made by those skilled in the art without departing from the scope of the present invention should be within the protection scope of the present invention.

The invention is not the best known technology.

Claims (4)

1. An antifreezing solution taking coal-to-ethylene glycol byproducts as raw materials is characterized by comprising the following components in percentage by mass:

。

2. the antifreeze solution using coal-derived ethylene glycol byproducts as raw materials according to claim 1, wherein the components of said coal-derived ethylene glycol byproducts comprise: the mass fraction is as follows: 65 to 80 percent of ethylene glycol, 15 to 25 percent of 1 to 2 butanediol, 1.5 to 3.5 percent of other butanediol (2, 3-butanediol, 1, 3-butanediol and the like), and 0.2 to 1.2 percent of esters (gamma-butyrolactone, propylene carbonate and the like).

3. The antifreeze fluid using coal-based ethylene glycol byproducts as raw materials according to claim 1, wherein the antifreeze fluid further comprises one or two of sodium phytate and phenol red in a mass percentage of 0.1-0.3%.

4. The method for preparing the antifreeze solution using the byproduct of the ethylene glycol prepared from coal as the raw material according to claim 1, wherein the method comprises the following steps:

according to the proportion, the related components and distilled water are added into the coal-to-ethylene glycol byproduct, and the mixture is stirred for 10-20 min at 40-60 ℃ to obtain the antifreezing solution.