A coal water slurry additive prepared by using industrial by-products and a preparation method thereof

Abstract

The application discloses a water coal slurry additive prepared by using industrial by-products, which comprises the following raw material components in parts by weight: amino benzene sulfonic acid 10-20 parts, meta-amino phenol 10-20 parts, sulfite 5-15 parts, a basic adjusting agent in an appropriate amount and water 50-70 parts. The water coal slurry additive is prepared by directly using industrial by-products, realizes resource recycling, and has high slurry concentration, low viscosity, good fluidity and stability.

Description

Technical Field

[0001] This invention relates to a coal-water slurry additive, and more particularly to a coal-water slurry additive prepared using industrial by-products and its preparation method. Background Technology

[0002] Fine chemicals are a vital pillar industry of the national economy and an important component of the national economic system. The production process of fine chemicals is characterized by long processes, complex raw materials, numerous side reactions, and multiple separation steps. Therefore, fine chemical industries generate a significant amount of industrial wastewater, which contains substantial amounts of finished products and byproducts. Traditional wastewater treatment processes, such as incineration or biochemical treatment, are difficult and expensive, significantly increasing operating costs for enterprises and wasting resources. Therefore, optimizing wastewater treatment solutions and fully utilizing industrial byproducts to achieve resource recycling has become a development trend in the industry.

[0003] Coal-water slurry additives are essential auxiliary agents in the preparation of coal-water slurry. Because coal is hydrophobic and the coal particles in the slurry are very fine with a large specific surface area, they easily aggregate spontaneously, thus the concentration of the coal-water slurry will not be too high. The hydrophobic groups in the coal-water slurry additives can adsorb onto the hydrophobic groups in the coal due to hydrophobic interactions. The hydrophilic groups, such as amino, phenolic hydroxyl, and sulfonate groups, face towards the water, thereby increasing the fluidity and stability of the coal-water slurry system. Therefore, coal-water slurry additives play a crucial role in the dispersibility, stability, and fluidity of the coal slurry. Coal-water slurry is characterized by low pollution, ease of pumping, atomization, and combustion, making it a clean coal-based fuel that replaces oil. Through high-temperature and high-pressure reaction, the coal, water, and additives' C, H, and O are ultimately converted into industrial raw materials CO2 and H2. It is an important component of clean coal technology and also an effective means of resource recovery and utilization, possessing high environmental value.

[0004] Because the wastewater generated by fine chemical industries is diverse, and the industrial byproducts within it are often unusable due to low purity, resulting in resource waste, extracting byproducts from fine chemical industrial wastewater and applying them in the preparation of coal-water slurry additives has become an important research direction for the development of novel coal-water slurry additives. Summary of the Invention

[0005] To overcome the shortcomings of existing technologies, this invention provides a coal-water slurry additive prepared from industrial by-products and its preparation method. The coal-water slurry additive is prepared directly from industrial by-products, realizing resource recycling. Moreover, the prepared coal-water slurry additive has high slurry concentration, low viscosity, good fluidity and stability.

[0006] The technical solution adopted by this invention to solve its technical problem is:

[0007] A coal-water slurry additive prepared using industrial by-products, the coal-water slurry additive comprising the following raw material components in parts by weight: 10-20 parts of aminobenzenesulfonic acid, 10-20 parts of m-aminophenol, 5-15 parts of sulfite, an appropriate amount of alkaline regulator, and 50-70 parts of water.

[0008] The above-mentioned coal-water slurry additive prepared using industrial by-products, wherein the aminobenzenesulfonic acid is one or more of aminobenzenesulfonic acid, aminopolysulfonic acid, or alkylated aminobenzenesulfonic acid.

[0009] The above-mentioned coal-water slurry additive prepared using industrial by-products, wherein the aminobenzenesulfonic acid is a mixture of m-aminobenzenesulfonic acid and p-aminobenzenesulfonic acid, with a molar ratio of 1:(0.1-0.2).

[0010] The above-mentioned coal-water slurry additive prepared using industrial by-products, wherein the aminopolysulfonic acid is a mixture of aniline-2,5-disulfonic acid and aniline-2,3,5-trisulfonic acid, with a molar ratio of 1:(0.15-0.25).

[0011] The above-mentioned coal-water slurry additive prepared using industrial by-products, wherein the alkylated aminobenzenesulfonic acid is a mixture of 3-sulfonic acid-N,N-diethylaniline and 3-sulfonic acid-N-monoethylaniline, with a molar ratio of 1:(0.05-0.1).

[0012] The above-mentioned coal-water slurry additive prepared using industrial by-products, wherein the m-aminophenol is a mixture of m-aminophenol, p-aminophenol and m-phenylenediamine, and the molar ratio of the three is 1:(0.05-0.1):(0.05-0.1).

[0013] The above-mentioned coal-water slurry additive prepared using industrial by-products includes a sulfite that is one or a mixture of two of sodium sulfite and potassium sulfite, by-products of the alkaline fusion of m-aminobenzenesulfonic acid to produce m-aminophenol; and an alkaline regulator that is one or a mixture of several of sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.

[0014] A method for preparing a coal-water slurry additive using industrial by-products, the method comprising: adding formulated amounts of aminobenzenesulfonic acid, m-aminophenol, sulfite and water to a reactor, heating to 50-60℃, adjusting the pH of the system to 10-12 with an alkaline regulator, and stirring for 2-5 hours to obtain the coal-water slurry additive.

[0015] The above-mentioned method for preparing coal-water slurry additives using industrial by-products includes the following: the aminobenzenesulfonic acid compounds include a mixture of m-aminobenzenesulfonic acid and p-aminobenzenesulfonic acid obtained by evaporating, concentrating, and cooling crystallizing the mother liquor of m-aminobenzenesulfonic acid produced during the sulfonation and hydrogenation process of nitrobenzenesulfonation to produce m-aminobenzenesulfonic acid; a mixture of aniline-2,5-disulfonic acid and aniline-2,3,5-trisulfonic acid obtained by evaporating, concentrating, and cooling crystallizing the mother liquor of aniline-2,5-disulfonic acid produced during the sulfonation process of m-aminobenzenesulfonic acid to produce aniline-2,5-disulfonic acid monosodium salt; or a mixture of 3-sulfonic acid-N,N-diethylaniline and 3-sulfonic acid-N-monoethylaniline obtained by evaporating, concentrating, and cooling crystallizing the mother liquor of 3-sulfonic acid-N,N-diethylaniline produced during the alkylation and alkali fusion process of m-aminobenzenesulfonic acid to produce 3-hydroxy-N,N-diethylaniline.

[0016] The above-mentioned method for preparing coal-water slurry additives using industrial by-products, wherein the m-aminophenol is a mixture of m-aminophenol, p-aminophenol and m-phenylenediamine obtained by evaporating, concentrating and cooling crystallizing the m-aminophenol mother liquor produced by the alkaline fusion process of sodium m-aminobenzenesulfonate to produce m-aminophenol.

[0017] The above-mentioned method for preparing coal-water slurry additives using industrial by-products, wherein the coal-water slurry additives have a solid content of 43.90% and are a dark brown liquid.

[0018] The beneficial effects of this invention are:

[0019] This invention provides a coal-water slurry additive prepared using industrial by-products. The main raw materials of this additive are industrial by-products obtained after processing mother liquor during fine chemical production, including a mixture of m-aminobenzenesulfonic acid and p-aminobenzenesulfonic acid, a mixture of aniline-2,5-disulfonic acid and aniline-2,3,5-trisulfonic acid, a mixture of 3-sulfonic-N,N-diethylaniline and 3-sulfonic-N-monoethylaniline, and a mixture of m-aminophenol, p-aminophenol, and m-phenylenediamine. These mixtures are industrial by-products and do not require separate separation and purification; they can be used in the preparation of the coal-water slurry additive of this invention, achieving resource recycling and utilization. This additive has the advantages of low cost, simple production process, and mild production conditions.

[0020] The coal-water slurry additive of this invention contains both aminobenzenesulfonic acid and aminophenol compounds, which have hydrophobic groups such as benzene rings and ethyl groups, allowing them to bind tightly with hydrophobic substances in coal. Each aminobenzenesulfonic acid or aminophenol raw material contains at least two hydrophilic groups, which effectively increase the binding of coal and water, thereby increasing the dispersibility of coal in water. The phenolic hydroxyl groups in aminophenols can form stable hydrogen bonds with water, thus increasing the stability of the coal-water slurry system. Sulfites have reducing properties, thus effectively increasing their binding with different coal types. The addition of an alkaline regulator reduces the oiliness of coal, thereby effectively improving the fluidity of the coal-water slurry system. The coal-water slurry additive prepared by this invention has strong adaptability to different coal types and, when used in coal-water slurry preparation, produces slurry with high concentration, low viscosity, good fluidity, and good stability. Detailed Implementation

[0021] The coal-water slurry additive of this invention contains both aminobenzenesulfonic acid and aminophenol components. Aminosulfonic acid and aminophenol can be adsorbed onto the coal surface through hydrophobic interactions between the benzene ring and the aromatic ring on the coal surface. The hydrophilic amino groups, sulfonic acid groups, and phenolic hydroxyl groups face the water, effectively improving the hydrophilicity of the coal surface. However, a single component tends to form a regularly arranged hydrophilic layer on the coal surface, which may not be dense enough. When two or more components work together, the regularity of a single component can be broken. Due to differences in molecular size, intermolecular interactions, and molecular conformations, gaps in the hydrophilic layer can be filled, increasing the density of the hydrophilic layer and resulting in better hydrophilicity of the coal surface.

[0022] The present invention will be further described below with reference to the embodiments.

[0023] Example 1

[0024] A coal-water slurry additive prepared using industrial by-products is composed of the following raw materials in parts by weight: 20 parts of aminobenzenesulfonic acid (m-aminobenzenesulfonic acid: p-aminobenzenesulfonic acid (n:n) = 1:0.1), 15 parts of m-aminophenol (m-aminophenol: p-aminophenol: m-phenylenediamine (n:n:n) = 1:0.05:0.05), 10 parts of sodium sulfite, appropriate amount of sodium hydroxide, and 55 parts of water.

[0025] A coal-water slurry additive prepared using industrial by-products includes the following steps: adding aminobenzenesulfonic acid, m-aminophenol, sodium sulfite and water to a reactor, heating to 50-60℃, adjusting the pH of the system to 10-12 with sodium hydroxide, and stirring for 3 hours to obtain the coal-water slurry additive.

[0026] The solid content of the above-mentioned coal-water slurry additive is 43.90%, and it is a dark brown liquid.

[0027] Example 2

[0028] A coal-water slurry additive prepared using industrial by-products is composed of the following raw materials in parts by weight: 15 parts of aminobenzenesulfonic acid (m-aminobenzenesulfonic acid: p-aminobenzenesulfonic acid (n:n) = 1:0.2), 15 parts of m-aminophenol (m-aminophenol: p-aminophenol: m-phenylenediamine (n:n:n) = 1:0.05:0.05), 10 parts of sodium sulfite, appropriate amount of sodium hydroxide, and 60 parts of water.

[0029] A coal-water slurry additive prepared using industrial by-products includes the following steps: adding aminobenzenesulfonic acid, m-aminophenol, sodium sulfite and water to a reactor, heating to 50-60℃, adjusting the pH of the system to 10-12 with potassium hydroxide, and stirring for 3 hours to obtain the coal-water slurry additive.

[0030] The solid content of the above-mentioned coal-water slurry additive is 40.35%, and it is a dark brown liquid.

[0031] Example 3

[0032] A coal-water slurry additive prepared using industrial by-products is composed of the following raw materials in parts by weight: 20 parts of aminopolysulfonic acid (aniline-2,5-disulfonic acid: aniline-2,3,5-trisulfonic acid (n:n) = 1:0.15), 15 parts of m-aminophenol (m-aminophenol: p-aminophenol: m-phenylenediamine (n:n:n) = 1:0.1:0.1), 5 parts of sodium sulfite, appropriate amount of sodium hydroxide, and 60 parts of water.

[0033] A coal-water slurry additive prepared using industrial by-products includes the following steps: adding aminopolysulfonic acid, m-aminophenol, sodium sulfite and water to a reactor, heating to 50-60℃, adjusting the pH of the system to 10-12 with potassium hydroxide, and stirring for 3 hours to obtain the coal-water slurry additive.

[0034] The solid content of the above-mentioned coal-water slurry additive is 40.55%, and it is a dark brown liquid.

[0035] Example 4

[0036] A coal-water slurry additive prepared using industrial by-products is composed of the following raw materials in parts by weight: 10 parts of aminopolysulfonic acid (aniline-2,5-disulfonic acid: aniline-2,3,5-trisulfonic acid (n:n) = 1:0.25), 10 parts of m-aminophenol (m-aminophenol: p-aminophenol: m-phenylenediamine (n:n:n) = 1:0.1:0.1), 15 parts of sodium sulfite, an appropriate amount of sodium hydroxide, and 65 parts of water.

[0037] A coal-water slurry additive prepared using industrial by-products includes the following steps: adding aminopolysulfonic acid, m-aminophenol, sodium sulfite and water to a reactor, heating to 50-60℃, adjusting the pH of the system to 10-12 with potassium carbonate, and stirring for 3 hours to obtain the coal-water slurry additive.

[0038] The solid content of the above-mentioned coal-water slurry additive is 35.40%, and it is a dark brown liquid.

[0039] Example 5

[0040] A coal-water slurry additive prepared using industrial by-products is composed of the following raw materials in parts by weight: 20 parts of aminopolysulfonic acid (aniline-2,5-disulfonic acid: aniline-2,3,5-trisulfonic acid (n:n) = 1:0.20), 15 parts of m-aminophenol (m-aminophenol: p-aminophenol: m-phenylenediamine (n:n:n) = 1:0.05:0.1), 10 parts of potassium sulfite, appropriate amount of sodium hydroxide, and 55 parts of water.

[0041] A coal-water slurry additive prepared using industrial by-products includes the following steps: adding aminopolysulfonic acid, m-aminophenol, potassium sulfite and water to a reactor, heating to 50-60℃, adjusting the pH of the system to 10-12 with potassium carbonate, and stirring for 3 hours to obtain the coal-water slurry additive.

[0042] The solid content of the above-mentioned coal-water slurry additive is 45.20%, and it is a dark brown liquid.

[0043] Example 6

[0044] A coal-water slurry additive prepared using industrial by-products is composed of the following raw materials in parts by weight: 20 parts of alkylated aminobenzenesulfonic acid (3-sulfonyl-N,N-diethylaniline: 3-sulfonyl-N-monoethylaniline (n:n) = 1:0.05), 20 parts of m-aminophenol (m-aminophenol: p-aminophenol: m-phenylenediamine (n:n:n) = 1:0.05:0.05), 5 parts of potassium sulfite, appropriate amount of sodium hydroxide, and 55 parts of water.

[0045] A coal-water slurry additive prepared using industrial by-products includes the following steps: adding alkylated aminobenzenesulfonic acid, m-aminophenol, potassium sulfite and water to a reactor, heating to 50-60℃, adjusting the pH of the system to 10-12 with potassium carbonate, and stirring for 3 hours to obtain the coal-water slurry additive.

[0046] The solid content of the above-mentioned coal-water slurry additive is 45.38%, and it is a dark brown liquid.

[0047] Comparative Example 1

[0048] This example provides a commercially available additive, which is a mixture of sodium lignosulfonate, naphthalenesulfonic acid, and water in a mass ratio of 1:1:3.

[0049] The water-coal slurry additives of Examples 1-6 and Comparative Example 1 were used to conduct slurry formation experiments. The additive dosage was 0.2%, the water used was laboratory pure water, and the coal used was a low-rank coal sample from the same batch of Shenhua coal.

[0050] Characterization of coal-water slurry properties generally includes factors such as concentration (solid content), viscosity, flow state, water absorption rate, and whether hard sedimentation occurs after 48 hours of settling. To more quickly determine the quality of coal-water slurry additives by assessing the properties of the prepared slurry, current characterization methods for coal-water slurries of the same concentration mainly include the slurry's concentration, viscosity, flow state, and the presence of hard sedimentation after 48 hours. The flowability test was conducted visually. The prepared coal-water slurry was slowly poured into another beaker at 25°C, and the flow pattern was visually assessed. Based on the flow characteristics, it was classified into four grades: A - continuous flow, B - intermittent continuous flow, C - intermittent discontinuous flow, and D - no flow. Viscosity testing was performed according to GB / T18855-2014. Generally, the higher the concentration of the coal-water slurry, the better the effect of the additive; the lower the viscosity of the coal-water slurry, the better the effect of the additive; the better the flow state of the coal-water slurry, the better the effect of the additive; and the absence of hard sedimentation after 48 hours indicates a better additive effect.

[0051] The performance of the coal-water slurry after slurry formation was tested, and the test results are shown in Table 1.

[0052] Table 1 Performance test results of coal-water slurry additives

[0053] serial number Added amount / % Types of additives concentration / % Viscosity (mPa·s) Flow state Is there any hard sediment? 1 0.5 Example 1 63.59 874 A no 2 0.5 Example 2 63.75 872 A no 3 0.5 Example 3 63.82 824 A no 4 0.5 Example 4 63.64 844 A no 5 0.5 Example 5 63.73 858 A no 6 0.5 Example 6 63.78 825 A no 7 0.5 Comparative Example 1 62.69 1098 A no

[0054] As shown in Table 1, the coal-water slurry additives prepared in Examples 1-6 of this invention, when applied to the preparation of low-rank coal for Shenhua, produce coal-water slurry with good performance, significantly better than that of commercially available coal-water slurry additive Comparative Example 1. They can meet the needs of industrial production, have advantages such as good dispersibility and wide adaptability, and have high slurry concentration, making them a better coal-water slurry additive.

[0055] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claimed invention. The scope of protection claimed by the appended claims and their equivalents is defined.

Claims

1. A coal-water slurry additive, characterized in that: The coal-water slurry additive is composed of the following raw materials in parts by weight: 10-20 parts of aminobenzenesulfonic acid; 10-20 parts of a mixture of m-aminophenol, p-aminophenol and m-phenylenediamine; 5-15 parts of sulfite; an appropriate amount of alkaline regulator and 50-70 parts of water; The method for preparing the coal-water slurry is as follows: the formulated amounts of aminobenzenesulfonic acid, a mixture of m-aminophenol, p-aminophenol and m-phenylenediamine, sulfite and water are added to a reactor, the temperature is raised to 50-60℃, the pH of the system is adjusted to 10-12 with an alkaline regulator, and the mixture is stirred for 2-5 hours to obtain the coal-water slurry additive. The aminobenzenesulfonic acids include one or more of the following: a mixture of m-aminobenzenesulfonic acid and p-aminobenzenesulfonic acid obtained by evaporating, concentrating, and cooling crystallizing the mother liquor of m-aminobenzenesulfonic acid produced during the sulfonation and hydrogenation process of nitrobenzenesulfonation to produce m-aminobenzenesulfonic acid; a mixture of aniline-2,5-disulfonic acid and aniline-2,3,5-trisulfonic acid obtained by evaporating, concentrating, and cooling crystallizing the mother liquor of aniline-2,5-disulfonic acid produced during the sulfonation process of m-aminobenzenesulfonic acid to produce aniline-2,5-disulfonic acid monosodium salt; or a mixture of 3-sulfonic acid-N,N-diethylaniline and 3-sulfonic acid-N-monoethylaniline obtained by evaporating, concentrating, and cooling crystallizing the mother liquor of 3-sulfonic acid-N,N-diethylaniline produced during the alkylation and alkali fusion process of m-aminobenzenesulfonic acid to produce 3-hydroxy-N,N-diethylaniline. The mixture of m-aminophenol, p-aminophenol, and m-phenylenediamine is obtained by evaporating, concentrating, cooling, and crystallizing the m-aminophenol mother liquor produced during the alkaline fusion process of sodium m-aminobenzenesulfonate to produce m-aminophenol. The molar ratio of m-aminobenzenesulfonic acid to p-aminobenzenesulfonic acid is 1:(0.1-0.2). The molar ratio of aniline-2,5-disulfonic acid and aniline-2,3,5-trisulfonic acid is 1:(0.15-0.25). The molar ratio of 3-sulfonyl-N,N-diethylaniline and 3-sulfonyl-N-monoethylaniline is 1:(0.05-0.1). The molar ratio of m-aminophenol, p-aminophenol and m-phenylenediamine is 1:(0.05-0.1):(0.05-0.1).

2. The coal-water slurry additive according to claim 1, characterized in that: The sulfite is one or a mixture of two of the byproducts sodium sulfite and potassium sulfite produced during the alkaline fusion of m-aminobenzenesulfonic acid to produce m-aminophenol; the alkalinity regulator is one or a mixture of several of sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.