CN-119192051-B - Coal tar pitch-based surfactant, and preparation method and application thereof

CN119192051BCN 119192051 BCN119192051 BCN 119192051BCN-119192051-B

Abstract

The invention discloses a coal tar pitch-based surfactant, a preparation method and application thereof, which belongs to the technical field of surfactants, wherein coal tar pitch is used as a raw material, chlorosulfonic acid groups are introduced into benzene rings in a molecular structure of the coal tar pitch through a sulfonylation reaction of chlorosulfonic acid and phosphorus oxychloride after impurity removal, and then generating sulfonate through esterification reaction between chlorosulfonic acid groups and hydroxyl at the upper end of hydrophilic chains, introducing the hydrophilic chains to the molecular structure edge of the coal tar pitch, and endowing the coal tar pitch with surface activity to obtain the coal tar pitch-based surfactant containing hydrophobic aromatic rings and hydrophilic long chains. The central multi-aromatic ring structure of the coal tar pitch-based surfactant is highly similar to the surface structure of Shenhua coal, the coal tar pitch-based surfactant and the Shenhua coal have stronger pi-pi action and hydrophobic action, the adsorption fastness is high, meanwhile, the long hydrophilic chains grafted at the edges can effectively provide steric hindrance, a physical barrier is formed between adjacent coal particles, the coal particles are effectively prevented from being aggregated, so that the coal water slurry has lower viscosity and good dispersibility and stability.

Inventors

ZHANG KANG
ZHANG YIXUAN
Ren Wanliang
WANG CHEN
YANG XIAOWU

Assignees

陕西科技大学

Dates

Publication Date: 20260512
Application Date: 20240929

Claims (5)

1. The preparation method of the coal tar pitch-based surfactant is characterized by comprising the following steps of: S1, dissolving coal pitch in a first organic solvent, filtering and drying to obtain an intermediate product I, adding the intermediate product I into a second organic solvent, adding chlorosulfonic acid under the protection of N 2 , uniformly mixing, heating and stirring for reaction, slowly adding phosphorus oxychloride, continuously stirring for reaction, and cooling, filtering, washing and drying to obtain an intermediate product II; S2, dissolving the intermediate product II in a first part of a second organic solvent, uniformly mixing to obtain a solution containing the intermediate product II, dissolving a hydrophilic monomer in a second part of the second organic solvent, uniformly mixing to obtain a solution containing the hydrophilic monomer, adding the solution containing the hydrophilic monomer into the solution containing the intermediate product II, uniformly stirring, heating, continuously stirring for reaction, and cooling, filtering, washing and drying to obtain the coal tar pitch-based surfactant; In the step S1, the coal tar pitch is any one of high-temperature coal tar pitch, medium-temperature coal tar pitch and low-temperature coal tar pitch, the first organic solvent is any one of benzene, toluene and quinoline, and the mass ratio of the coal tar pitch to the first organic solvent is 1 (2-3.5); In the step S1, the second organic solvent is any one of dichloromethane, chloroform and carbon tetrachloride, and the mass ratio of the intermediate product I to the second organic solvent to the chlorosulfonic acid to the phosphorus oxychloride is 1 (2-3.5) (0.2-0.5) (0.1-0.3); in the step S2, the hydrophilic monomer is any one of polyethylene glycol 200, polyethylene glycol 400 and polyethylene glycol 600, the mass ratio of the intermediate product II to the hydrophilic monomer is 1 (4-5) (0.9-1.1), and the second organic solvent comprises a first part of second organic solvent and a second part of second organic solvent, wherein the mass ratio of the first part of second organic solvent to the second part of second organic solvent is 1 (1-1.5).
2. The method for preparing the coal tar pitch-based surfactant according to claim 1, wherein in the step S1, the conditions of the heating and stirring reaction are that stirring is carried out for 1-2 hours at 0-5 ℃, and the time of the continuous stirring reaction is 2-4 hours.
3. The method for preparing a coal tar pitch-based surfactant according to claim 1, wherein in step S2, the condition for heating and continuing to stir the reaction is 60-80 ℃ for 6-12 hours.
4. A coal tar pitch-based surfactant, characterized by being prepared by the preparation method of any one of claims 1 to 3.
5. The application of the coal tar pitch-based surfactant prepared by the preparation method according to any one of claims 1-3 in preparation of Shenhua coal water slurry, which is characterized in that the water separation rate of the Shenhua coal water slurry is 1.59-1.76 wt%.

Description

Coal tar pitch-based surfactant, and preparation method and application thereof Technical Field The invention belongs to the technical field of surfactants, and particularly relates to a coal tar pitch-based surfactant, and a preparation method and application thereof. Background Coal pitch is the residue after distillation of coal tar, and the yield of the coal pitch is about 50% -60% of the total amount of the coal tar. With the development of coking industry, a large amount of coal tar pitch is underutilized, and the comprehensive utilization efficiency of coal resources is seriously affected. Therefore, the novel method is utilized to develop the coal tar pitch with universality and high efficiency, so that the energy crisis can be effectively relieved, and the overall economic benefit and social benefit of the coal industry can be improved. Currently, coal pitch is mainly used for preparing electrodes, activated carbon, carbon fibers, needle coke, impregnant, road building materials and the like. However, since the structure and composition of coal pitch are changed by the properties of raw coal and the coking process, coal tar quality and distillation conditions, it is difficult to maintain the stability of the properties of the carbon material prepared therefrom. Based on the analysis of physicochemical properties of coal tar pitch, the structure of the asphalt mainly comprises polycyclic aromatic hydrocarbons, polycyclic aromatic hydrocarbons and derivatives thereof, and the asphalt is strong in hydrophobicity as a whole. If hydrophilic functional groups are introduced into the molecular structure, a surfactant with high added value and wide application range can be obtained. The water-coal slurry is a high-concentration coal water suspension, can be directly combusted or used as a coal gasification raw material, has the advantages of low pollution, high efficiency and pipeline transportation, and is considered to be one of important components of clean coal technology. The water-coal slurry mainly comprises coal particles, water and additives, wherein the additives play an important role in slurry performance. In the additive, the surfactant is an amphiphilic substance, can improve the surface property and interface structure of coal by adsorption, increase electrostatic repulsive force and steric hindrance energy among coal particles, prevent the aggregation of the coal particles and the adsorption of moisture, and further reduce the viscosity of the coal water slurry, so that the coal water slurry has good dispersibility and stability. The molecular structure of coal pitch is very similar to the coal surface, and stronger pi-pi action and hydrophobic action exist between the molecular structure and the coal surface, so that a necessary premise is provided for improving the coal surface structure. However, only the preparation of sulfonated coal pitch by sulfonation means has been reported at present, and such surfactants are difficult to effectively increase steric hindrance between coal particles, resulting in poor stability of slurry. Therefore, in order to widen the utilization mode of coal tar pitch and improve the performance of the coal tar pitch-based surfactant in the coal water slurry, it is necessary to develop a novel coal tar pitch-based surfactant with a steric hindrance effect, thereby improving the application performance of the coal water slurry. Disclosure of Invention In order to overcome the defects of the prior art, the invention aims to provide a coal tar pitch-based surfactant, and a preparation method and application thereof, so as to solve the technical problem of poor slurry stability caused by weak steric hindrance in pulping of the existing sulfonated coal tar pitch. In order to achieve the above purpose, the invention is realized by adopting the following technical scheme: The invention discloses a preparation method of a coal tar pitch-based surfactant, which comprises the following steps: S1, dissolving coal pitch in a first organic solvent, filtering and drying to obtain an intermediate product I, adding the intermediate product I into a second organic solvent, adding chlorosulfonic acid under the protection of N 2, uniformly mixing, heating and stirring for reaction, slowly adding phosphorus oxychloride, continuously stirring for reaction, and cooling, filtering, washing and drying to obtain an intermediate product II; s2, dissolving the intermediate product II in a first part of a second organic solvent, uniformly mixing to obtain a solution containing the intermediate product II, dissolving a hydrophilic monomer in a second part of the second organic solvent, uniformly mixing to obtain a solution containing the hydrophilic monomer, adding the solution containing the hydrophilic monomer into the solution containing the intermediate product II, uniformly stirring, heating, continuously stirring for reaction, and cooling, filtering, washing and drying to obtain the