阅读说明：本技术 一种水煤浆添加剂的制备方法 (Preparation method of coal water slurry additive ) 是由 朱建余 于 2018-09-28 设计创作，主要内容包括：本发明公开了一种水煤浆添加剂的制备方法,其特征在于,以重量份数计,包括如下步骤：将羧基改性离子型三唑类纳米微球5-10份、磺丁基β-环糊精钠5-10份、改性三油酸山梨酯10-15份、月桂醇聚醚硫酸酯1-3份、水30-40份混合均匀后,加入氢氧化钠调节PH至7-8,后过200-300目筛,得到水煤浆添加剂。本发明制备方法制得的水煤浆添加剂生产成本低、性能稳定,用于水煤浆制备时,成浆浓度高、粘度低、流动性和稳定性好,用量省、适应性广。(The invention discloses a preparation method of a coal water slurry additive, which is characterized by comprising the following steps in parts by weight: 5-10 parts of carboxyl modified ionic triazole nano-microspheres, 5-10 parts of sulfobutyl beta-cyclodextrin sodium, 10-15 parts of modified sorbitan trioleate, 1-3 parts of laureth sulfate and 30-40 parts of water are uniformly mixed, then sodium hydroxide is added to adjust the pH value to 7-8, and the mixture is sieved by a 200-mesh and 300-mesh sieve to obtain the coal water slurry additive. The coal water slurry additive prepared by the preparation method has low production cost and stable performance, and when the additive is used for preparing coal water slurry, the slurry concentration is high, the viscosity is low, the fluidity and the stability are good, the dosage is saved, and the adaptability is wide.)

1. The preparation method of the coal water slurry additive is characterized by comprising the following steps of: 5-10 parts of carboxyl modified ionic triazole nano-microspheres, 5-10 parts of sulfobutyl beta-cyclodextrin sodium, 10-15 parts of modified sorbitan trioleate, 1-3 parts of laureth sulfate and 30-40 parts of water are uniformly mixed, then sodium hydroxide is added to adjust the pH value to 7-8, and the mixture is sieved by a 200-mesh and 300-mesh sieve to obtain the coal water slurry additive.

2. The preparation method of the coal water slurry additive according to claim 1, wherein the preparation method of the carboxyl modified ionic triazole nano microsphere comprises the following steps:

step S1 preparation of triazole nano-microspheres: adding 1-vinyl-1, 2, 4-triazole, poly (ethylene glycol) phenyl ether acrylic acid, itaconic acid and azo initiator into an organic solvent, heating and refluxing at 80-90 ℃ in nitrogen or inert gas atmosphere, and performing precipitation polymerization reaction, washing and drying to obtain imidazole nano microspheres;

step S2 ionization of triazole nano microspheres: adding the triazole nano-microspheres prepared in the step S1 and chloroformic acid into an alcohol solvent, stirring and reacting for 15-20 hours at 50-70 ℃, and washing and drying reaction products to obtain ionized triazole nano-microspheres;

step S3 ion exchange: and (4) adding the ionized triazole nanometer microspheres prepared in the step S2 and humic acid into water, stirring for 18-24 hours at 50-60 ℃, and performing rotary evaporation to remove water to obtain the carboxyl modified ionic triazole nanometer microspheres.

3. The preparation method of the coal water slurry additive according to claim 1, wherein the preparation method of the modified sorbitan trioleate comprises the following steps: dissolving N- (4-sulfobutyl) -4- (4- (4- (diamyl amino) phenyl) butadienyl) pyridine inner salt and sorbitan trioleate in a high-boiling-point solvent under the atmosphere of nitrogen to form a solution, adding the solution into a three-neck flask provided with a reflux condenser tube and an electric stirrer, carrying out reflux stirring reaction at the temperature of 130-140 ℃ for 12-15 hours, and then carrying out rotary evaporation to remove the solvent to obtain the modified sorbitan trioleate.

4. The method for preparing the coal water slurry additive according to claim 2, wherein the mass ratio of the 1-vinyl-1, 2, 4-triazole, the poly (ethylene glycol) phenyl ether acrylic acid, the itaconic acid, the azo initiator and the organic solvent in the step S1 is 1 (2-3) to 1 (0.04-0.06) to (40-60).

5. The method for preparing the coal water slurry additive according to claim 2, wherein the azo initiator is at least one selected from the group consisting of azobisisobutyronitrile and azobisisoheptonitrile; the organic solvent is selected from one or more of chloroform, acetonitrile, diethyl ether and ethyl acetate.

6. The preparation method of the coal water slurry additive according to claim 2, wherein the mass ratio of the triazole nano-microspheres to the chloroformic acid to the alcohol solvent in the step S2 is 1:3 (30-50); the alcohol solvent is selected from one or more of ethanol, isopropanol and ethylene glycol.

7. The preparation method of the coal water slurry additive according to claim 2, wherein the mass ratio of the ionized triazole nano-microspheres, the humic acid and the water in the step S3 is 1:0.3 (10-20).

8. The preparation method of the coal water slurry additive according to claim 3, wherein the mass ratio of the N- (4-sulfobutyl) -4- (4- (4- (dipentylamino) phenyl) butadienyl) pyridine inner salt to the sorbitan trioleate to the high-boiling-point solvent is 1:1.56 (15-20).

9. The preparation method of the coal water slurry additive according to claim 3, wherein the high boiling point solvent is one or more of dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone.

Technical Field

The invention relates to the technical field of coal water slurry additives, in particular to a coal water slurry additive and a preparation method thereof.

Background

The coal water slurry is a novel low-pollution oil-substituting fuel and can also be used as a novel raw material for producing synthesis gas. On the basis of keeping the original physical and chemical properties of coal, the coal has the mobility and stability as same as those of petroleum, is known as a liquid coal product, and is widely applied to combustion and gasification of industrial boilers, power station boilers, industrial furnaces and gasification furnaces due to the advantages of economy, safety, environmental protection, high efficiency, universality and the like.

The preparation process of the coal water slurry needs to add a small amount of additives, and the additives are low in dosage and are key for preparing the high-concentration coal water slurry. It is a chemical agent capable of promoting dispersed phase (coal particles in water coal slurry) to be uniformly dispersed in dispersion medium (water in water coal slurry), and is a chemical auxiliary agent which is largely used in the processes of combustion, gasification and transportation of water coal slurry. The coal water slurry additive with good performance can enable the coal water slurry to have higher slurry concentration, rheological property of shear thinning, good stability and excellent atomization combustion performance.

Disclosure of Invention

In order to overcome the defects in the prior art, the invention provides the coal water slurry additive which has low production cost and stable performance, is high in slurry concentration, low in viscosity, good in fluidity and stability, low in dosage and wide in adaptability, can be suitable for complex pulping working conditions and can obviously improve the atomization combustion performance when being used for preparing the coal water slurry, and the preparation method thereof.

In order to achieve the aim, the invention adopts the technical scheme that the coal water slurry additive is prepared from the following raw materials in parts by weight: 5-10 parts of carboxyl modified ionic triazole nano-microspheres, 5-10 parts of sulfobutyl beta-cyclodextrin sodium, 10-15 parts of modified sorbitan trioleate, 1-3 parts of laureth sulfate and 30-40 parts of water.

Preferably, the preparation method of the carboxyl modified ionic triazole nano-microsphere comprises the following steps:

step S1 preparation of triazole nano-microspheres: adding 1-vinyl-1, 2, 4-triazole, poly (ethylene glycol) phenyl ether acrylic acid, itaconic acid and azo initiator into an organic solvent, heating and refluxing at 80-90 ℃ in nitrogen or inert gas atmosphere, and performing precipitation polymerization reaction, washing and drying to obtain imidazole nano microspheres;

step S2 ionization of triazole nano microspheres: adding the triazole nano-microspheres prepared in the step S1 and chloroformic acid into an alcohol solvent, stirring and reacting for 15-20 hours at 50-70 ℃, and washing and drying reaction products to obtain ionized triazole nano-microspheres;

step S3 ion exchange: and (4) adding the ionized triazole nanometer microspheres prepared in the step S2 and humic acid into water, stirring for 18-24 hours at 50-60 ℃, and performing rotary evaporation to remove water to obtain the carboxyl modified ionic triazole nanometer microspheres.

Further, the washing and drying in steps S1 and S2 is carried out by washing with ethanol for 3-5 times by centrifugation, and then drying in a vacuum drying oven at 80-90 ℃ for 12-15 hours.

Furthermore, in the step S1, the mass ratio of the 1-vinyl-1, 2, 4-triazole, the poly (ethylene glycol) phenyl ether acrylic acid, the itaconic acid, the azo initiator and the organic solvent is 1 (2-3) to 1 (0.04-0.06) to (40-60).

Preferably, the azo initiator is selected from at least one of azobisisobutyronitrile and azobisisoheptonitrile; the organic solvent is selected from one or more of chloroform, acetonitrile, diethyl ether and ethyl acetate; the inert gas is at least one of helium, neon and argon.

Preferably, the reaction time of the precipitation polymerization reaction is 3 to 5 hours.

Furthermore, the mass ratio of the triazole nanometer microspheres, the chloroformic acid and the alcohol solvent in the step S2 is 1:3 (30-50).

Preferably, the alcohol solvent is selected from one or more of ethanol, isopropanol and ethylene glycol.

Furthermore, the mass ratio of the ionized triazole nanometer microspheres to the humic acid to the water in the step S3 is 1:0.3 (10-20).

Preferably, the preparation method of the modified sorbitan trioleate comprises the following steps: dissolving N- (4-sulfobutyl) -4- (4- (4- (diamyl amino) phenyl) butadienyl) pyridine inner salt and sorbitan trioleate in a high-boiling-point solvent under the atmosphere of nitrogen to form a solution, adding the solution into a three-neck flask provided with a reflux condenser tube and an electric stirrer, carrying out reflux stirring reaction at the temperature of 130-140 ℃ for 12-15 hours, and then carrying out rotary evaporation to remove the solvent to obtain the modified sorbitan trioleate.

Furthermore, the mass ratio of the N- (4-sulfobutyl) -4- (4- (4- (diamyl amino) phenyl) butadienyl) pyridine inner salt to the sorbitan trioleate to the high-boiling-point solvent is 1:1.56 (15-20).

Preferably, the high boiling point solvent is selected from one or more of dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone.

Preferably, the preparation method of the coal water slurry additive comprises the following steps: after all the raw materials are mixed uniformly, sodium hydroxide is added to adjust the PH value to 7-8, and then the mixture is sieved by a 200-mesh and 300-mesh sieve to obtain the coal water slurry additive.

The coal water slurry adopts the coal water slurry additive as an additive.

Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:

1) the coal water slurry additive provided by the invention has the advantages of easily available raw materials, low price, simple and easily operated preparation method, no toxicity, no harm, little environmental pollution, safe use and environmental protection.

2) The coal water slurry additive provided by the invention overcomes the technical problems of poor adaptability to coal and process, unsatisfactory slurry forming effect, poor stability, easy generation of hard precipitate, high price and the like existing in more or less coal water slurry additives in the prior art, and has the advantages of low production cost, stable performance, high slurry forming concentration, low viscosity, good fluidity and stability, low consumption, wide adaptability, suitability for complex slurry making working conditions and capability of obviously improving the atomizing combustion performance when being used for preparing coal water slurry.

3) The water-coal-slurry additive provided by the invention is added with the triazole nano-microsphere organic nano-material, so that the atomization combustion performance is improved, and the combustion efficiency is further improved; in addition, the nano-microsphere is modified by surface carboxyl, so that the action mode of the dispersing agent and the coal surface is changed from single hydrogen bond adsorption into double actions of hydrogen bond adsorption and electrostatic adsorption, and electrostatic repulsion and steric hindrance actions are generated among cation units, thereby greatly enhancing the dispersing effect of the dispersing agent. The hydrogen bond effect, the electrostatic effect and the steric hindrance are simultaneously strengthened, so that the dispersing effect, the adjustable stabilizing effect and the wide applicability to the coal type pulping and the water quality pulping are more excellent; a humic acid structure is introduced through ion exchange, so that the dispersibility, the stability and the fluidity are further improved; in addition, sulfobutyl beta-cyclodextrin sodium, modified sorbitan trioleate and lauryl polyether sulfate are introduced, the components have synergistic effect, so that the comprehensive performance of the coal water slurry additive is excellent, and the coal water slurry added with the coal water slurry additive has the characteristics of high concentration, low viscosity, good stability, low requirement on coal type and water quality of slurry preparation and the like.

Detailed Description

In order to make the technical solutions of the present invention better understood and make the above features, objects, and advantages of the present invention more comprehensible, the present invention is further described with reference to the following examples. The examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.

Sulfobutyl beta-cyclodextrin sodium used in the following examples of the invention was obtained from Zhiyuan Biotech, Inc. of Bingzhou, Shandong, and other materials were obtained from Xin import and export commerce, Inc. of Shanghai spring.