CN113969197B

CN113969197B - Multi-copolymer dispersant based on humic acid, preparation method thereof and application thereof in coal water slurry

Info

Publication number: CN113969197B
Application number: CN202010711920.XA
Authority: CN
Inventors: 朱伯淞; 乔敏; 吴井志; 陈健; 单广程; 高南箫; 冉千平; 洪锦祥
Original assignee: Sobute New Materials Co Ltd; Bote New Materials Taizhou Jiangyan Co Ltd; Nanjing Bote New Materials Co Ltd
Current assignee: Sobute New Materials Co Ltd; Bote New Materials Taizhou Jiangyan Co Ltd; Nanjing Bote New Materials Co Ltd
Priority date: 2020-07-22
Filing date: 2020-07-22
Publication date: 2023-04-14
Anticipated expiration: 2040-07-22
Also published as: CN113969197A

Abstract

The invention discloses a humic acid-based multipolymer dispersant, a preparation method thereof and application thereof in coal water slurry. The humic acid-based multi-component copolymer dispersant is prepared by polycondensation of humic acid and salts thereof, benzenesulfonic acid and derivative monomer A thereof and aromatic polyether B. The coal water slurry dispersion/powder is prepared by using humate, naphthalenesulfonic acid, polyether and the like as raw materials, and has high hydrophilicity, high dispersion and high stability. The polymer synthesis reaction adopts a polycondensation mechanism, and the reaction efficiency is high. The humic acid-based multipolymer dispersant can obviously improve the dispersibility of the water-coal-slurry and keep better fluidity. The product is a liquid or powder product prepared by using chemical raw materials through processes of multi-component condensation, physical drying and the like, and the cost of reaction raw materials is low. The reaction has low requirement on equipment, simple and convenient operation, short production period, no waste generation and controllable scale. The product of the invention is compounded with the traditional inorganic dispersant for use, and can achieve the purposes of not only being stronger than the performance of the inorganic dispersant, but also reducing the cost and being beneficial to large-scale popularization and use.

Description

Multi-copolymer dispersant based on humic acid, preparation method thereof and application thereof in coal water slurry

Technical Field

The invention relates to the technical field of dispersion liquid and dispersant of coal water slurry and production, in particular to a humic acid-based multipolymer dispersant, a preparation method thereof and application thereof in coal water slurry.

Background

The water-coal-slurry is a fluid fuel formed by adding water and coal and adding additive through mechanical grinding, and contains 60-70% of coal, 30-40% of water and about 1% of dispersing agent. The coal water slurry can be used for preparing gas from coal, the produced hydrogen and carbon monoxide can be used as synthesis gas for preparing a plurality of basic chemical raw materials such as ethylene glycol, ammonia and the like, the coal water slurry can also replace crude oil, and the combustion of the coal water slurry has obvious advantages in economic benefit or social benefit compared with the combustion of the crude oil. Therefore, the wide application of the coal water slurry has great strategic significance on energy supply and social sustainable development in China.

Coal is made into coal water slurry by using a dispersing agent (surfactant), and the coal water slurry can be atomized, stored and stably ignited and combusted. Generally, the quality requirements for coal water slurries are low viscosity, high concentration, and good flow and stability. The coal water slurry dispersing agent is the key influencing the quality of the coal water slurry and also influencing the production cost of the coal water slurry. Common water-coal-slurry dispersants are largely classified into anionic, nonionic, and zwitterionic dispersants, with the anionic being widely used due to cost and performance advantages. The anionic dispersant comprises a naphthalene dispersant, a lignin dispersant and a humic acid dispersant, wherein humic acid is a natural surface active substance with wide source and low price, has similarity with a coal structure, contains a plurality of active functional groups such as carboxyl, phenolic hydroxyl, carbonyl and the like in a molecular structure, has good adsorption performance with the surface of coal particles, and has a good structure modification foundation, but the previous research result shows that the humic acid salt as the coal water slurry dispersant has the problems of good dispersibility, poor hydrophilicity and poor stability.

Patent CN201410376029.X an amphoteric humate coal water slurry dispersing agent and a preparation and application thereof, humic acid, formaldehyde and a sulfonating agent are adopted for reaction, and the problem exists that the structure of sulfonated humic acid has a plurality of benzene rings, and gel products with body structures are easy to appear in the polycondensation reaction with formaldehyde, so that the dispersing performance is reduced.

The patent CN201410709800.0 adopts a method for preparing a water-coal-slurry dispersing agent by copolymerizing sodium sulfite, acetone, formaldehyde, methyl benzenesulfonic acid, acrylic acid, acrylamide and the like serving as raw materials, and the technical defect is that the preparation method is complex, the obtained sulfonated acetone-formaldehyde condensate needs to be subjected to reduced pressure distillation and dehydration and then is copolymerized with the acrylic acid and the like, and the method is high in operation difficulty in production, so that the cost of a final product is increased, and the cost performance is low.

The patent CN201711009339.8 adopts a method for preparing a water-coal-slurry dispersing agent by using a polycarboxylic acid series dispersing agent and derivatives thereof, and has the advantages that the comb-shaped structure of the polycarboxylic acid dispersing agent is large in steric hindrance, the dispersing effect is good, and the defects that the price of polyether for preparing raw materials is high and the using amount of polyether is large.

Therefore, aiming at the defects of the prior art, how to develop a macromolecular dispersant with excellent performance, lower cost and easily controlled reaction process to improve the fluidity of the coal water slurry and improve the stability of the coal water slurry by a compounding technology.

Disclosure of Invention

The invention provides a humic acid-based multipolymer dispersant, a preparation method thereof and application thereof in coal water slurry. The multipolymer dispersant synthesized based on humic acid can be used for the dispersion of coal water slurry, and is coal water slurry dispersion liquid/powder which is prepared by taking humate, naphthalenesulfonic acid, polyether and the like as raw materials and has high hydrophilicity, high dispersion and high stability. The polymer synthesis reaction adopts a polycondensation mechanism, and has high reaction efficiency.

The humic acid-based multi-copolymer dispersant can obviously improve the dispersibility of the water-coal-slurry and keep better fluidity. The product is a liquid or powder product prepared by chemical raw materials through processes of multicomponent condensation, physical drying and the like, and the cost of reaction raw materials is low. The reaction has low requirement on equipment, simple operation, short production period, no waste material and controllable scale. The product of the invention is compounded with the traditional inorganic dispersant for use, and can achieve the purposes of not only being stronger than the performance of the inorganic dispersant, but also reducing the cost and being beneficial to large-scale popularization and use.

The humic acid-based multi-component copolymer dispersant is prepared by polycondensation of humic acid and salts thereof, benzenesulfonic acid and derivative monomer A thereof and aromatic polyether B.

The humic acid and its salt are selected from fulvic acid, potassium fulvate, sodium fulvate, ammonium fulvate, black humic acid, potassium black humic acid, sodium black humic acid or ammonium black humic acid;

the benzenesulfonic acid and derivative monomer A is selected from one or a mixture of more of beta-naphthalenesulfonic acid, benzenesulfonic acid, sulfanilic acid or p-hydroxybenzene sulfonic acid;

the aromatic polyether B has the following structural general formula:

in the structural general formula of the aromatic polyether monomer B, the weight average molecular weight of the aromatic polyether monomer B is between 1000 and 3000, m and n are the average addition mass numbers of ethylene oxide and propylene oxide respectively, m = 0-73, n = 0-53 (m and n are integers).

The weight average molecular weight of the humic acid-based multipolymer dispersant is 15000-35000.

The humic acid-based multipolymer dispersant can be a liquid product and can also be dried to obtain a powdered product.

In order to facilitate transportation, the humic acid-based multi-copolymer dispersant can improve the stability disadvantage of a humic acid modified product by screening out a stabilizer through compounding.

The stabilizer product is selected from gellan gum, welan gum, rhamsan gum, diutan gum, xanthan gum, guar gum and the like;

the dosage of the stabilizer product is 0.01-0.5% of that of the dispersant.

As an improvement, the humic acid is sulfonated by a sulfonating agent and then participates in the polycondensation reaction, and the sulfonating agent is one or a mixture of sodium sulfite, sodium sulfite and concentrated sulfuric acid.

The specific steps of the humic acid sulfonation are as follows:

step one, sequentially adding humate and distilled water into water according to a mass ratio, stirring and dissolving to form a uniform solution;

and step two, adding a sulfonating agent into the humate solution, heating to 75-100 ℃, stirring for reacting for 2-4 hours, cooling to room temperature, adding liquid alkali, and adjusting the pH value to 7-10 to obtain sulfonated humate.

The preparation method of the humic acid-based multipolymer is characterized by preparing the multipolymer by humic acid, sulfonating agent, monomer A, aromatic polyether monomer B, 37 percent formaldehyde solution and water according to the mixing ratio of 100 (15-36) to (4-14) to (28-101) to (25-50) to (165-490), wherein the length of the multipolymer is 2-6 h.

The preparation method of the humic acid-based multipolymer specifically comprises the following steps:

mixing humate or sulfonated humate with the monomer A and the monomer B, heating the mixed solution to 85-95 ℃, slowly dripping the formaldehyde aqueous solution into the solution while stirring, and finishing dripping within 40-80 minutes; preserving the heat for 2-6h, cooling to room temperature to obtain a dark red liquid, namely the humic acid-based multi-component copolymer dispersant, and spray drying at the high temperature of 280-350 ℃ to obtain a powder dispersant with the water content of 1-9%.

The stabilizer product is added into the liquid or powder dispersant, so that the water precipitation rate of the prepared water-coal-slurry can be effectively improved.

The application of the humic acid-based multipolymer dispersant is used for preparing the compound coal water slurry.

The coal water slurry comprises the following components in parts by weight:

55 to 70 portions of coal powder,

30-45 parts of water, namely,

0.1 to 0.5 portion of multi-copolymer dispersant based on humic acid.

Compared with the prior art, the invention has the advantages that:

1. according to the sulfonated humic acid multipolymer, the sulfonated humic acid multipolymer is introduced into the comonomer with the sulfonic acid group and the aromatic polyether for polycondensation reaction, and the mixture is easily generated in a linear copolymerization mode, so that the risk of body type polymerization is reduced, and the sulfonated humic acid multipolymer is not easy to gel;

2. according to the invention, aromatic polyether is introduced to participate in polycondensation, so that the steric hindrance effect of the polymer can be improved, the dispersing performance is improved, meanwhile, the molecular weight of the side chain is maintained on the premise of not influencing the polycondensation reaction, the hydrophobicity of the polymer is greater than the hydrophilicity, and the water solubility of the polymer is maintained;

3. the application mixing amount of the synthesized water-coal-slurry dispersing agent is usually between 0.1 and 0.5 percent, compared with the mixing amount of an inorganic dispersing agent, the application mixing amount is extremely low, the relative dispersibility is obviously improved, products are all organic matters, the possibility of introducing non-evaporable inorganic impurities does not exist, and compared with naphthalene series, aliphatic series and polycarboxylic acid series, the raw material cost is obviously reduced;

4. the monomer conversion rate in the multi-polymerization process is high and can reach about 90 percent;

5. the coal water slurry is compounded with the stabilizer, so that the long-acting stability of the coal water slurry is obviously improved;

6. the production process of the invention has no three wastes and no pollution to the environment.

Detailed Description

The present invention will be further described with reference to the following examples.

Raw materials for comparative examples of the following examples

Table 1: composition table of synthetic raw materials of examples and comparative examples

Example 1 (EO 2000+ Diyoujiao)

1) Firstly, sodium Humate (HA) and sodium sulfite (S) are mixed according to a mass ratio of HA: s =100: 20, adding a few drops of concentrated sulfuric acid, stirring at 100 ℃ for 3h under reflux, pouring off acid liquor, adjusting the pH value to 9 by potassium hydroxide, and drying to obtain sulfonated humate;

2) Sulfonating sodium humate according to the mass ratio: (β -naphthalenesulfonic acid + sulfanilic acid): aromatic polyether: formaldehyde solution: water =100: (3+2) 80. And cooling to room temperature to obtain the modified humic acid multi-component copolymerization coal water slurry dispersing agent with the weight average molecular weight of about =26000, and compounding with 0.1% diutan.

Example 2 (EO, 1500)

1) Firstly, potassium fulvate (HA) and concentrated sulfuric acid are mixed according to the ratio of HA: mixing S =100: 15, refluxing and stirring at 100 ℃ for 3h, pouring out acid liquor, adjusting the pH value to 8 by sodium hydroxide, and drying to obtain sulfonated humic acid;

2) Sulfonating sodium humate according to the mass ratio: benzene sulfonic acid: polyether: formaldehyde solution: water =100: 6. And cooling to room temperature to obtain the modified humic acid multi-copolymerization coal water slurry dispersing agent with the weight-average molecular weight of about 30000, and compounding with 0.2% of guar gum.

Example 3 (PO, 3000)

1) First, potassium fulvate (HA), sodium sulfite (S) were mixed according to HA: mixing S =100: 36, dripping a few drops of concentrated sulfuric acid, stirring at 100 ℃ for 4h under reflux, pouring off acid liquor, adjusting the pH value to 8 by potassium hydroxide, and drying to obtain sulfonated humic acid;

2) Sulfonating sodium humate according to the mass ratio: (sulfanilic acid + benzenesulfonic acid): polyether: formaldehyde solution: water =100 (4+3): 101. And cooling to room temperature to obtain the modified humic acid multi-copolymerization coal water slurry dispersing agent with the weight-average molecular weight =32000, and compounding with 0.5% of gellan gum.

Example 4 (EO + PO +, xanthan gum)

1) First, potassium black Humate (HA), sodium sulfite (S) were mixed according to HA: mixing S =100: 15, dripping a few drops of concentrated sulfuric acid, stirring at 75 ℃ under reflux for 2h, pouring off acid liquor, adjusting the pH value to 7 by sodium hydroxide, and drying to obtain sulfonated humic acid;

2) Sulfonating sodium humate according to the mass ratio: p-hydroxybenzene sulfonic acid: polyether: formaldehyde solution: water =100: 4. And cooling to room temperature to obtain the modified humic acid multi-element copolymerization coal water slurry dispersing agent with the weight average molecular weight of about =25000, and compounding with 0.01% of xanthan gum.

Example 5

1) First, fulvic acid (HA), (sodium sulfite + sodium bisulfite) was mixed according to HA: mixing sulfonating agents in a mass ratio of 100: 33, refluxing and stirring for 3 hours at 75 ℃, adjusting the pH value to 10 by using sodium hydroxide, and drying to obtain sulfonated humate;

2) And (2) sulfonating sodium humate according to the mass ratio: beta-naphthalenesulfonic acid: aromatic polyether: formaldehyde solution: water =100: 5. And cooling to room temperature to obtain the modified humic acid multi-element copolymerization coal water slurry dispersing agent with the weight average molecular weight of about =20000, and compounding with 0.01% of xanthan gum.

Example 6

1) According to the mass ratio of potassium fulvate: p-aminobenzene sulfonic acid: aromatic polyether: formaldehyde solution: water =100: 5. And cooling to room temperature to obtain the modified humic acid multi-component copolymerization coal water slurry dispersing agent with the weight average molecular weight of about =15000, and compounding with 0.01% diutan.

Example 7

1) According to the mass ratio of black humic acid: (beta-naphthalenesulfonic acid + p-hydroxybenzenesulfonic acid): aromatic polyether: formaldehyde solution: water =100: (4+3) 100. And cooling to room temperature to obtain the modified humic acid multi-element copolymerization water-coal-slurry dispersing agent with the weight-average molecular weight of about =35000, and compounding with 0.1% diutan.

Comparative example 1

1) First, sodium Humate (HA), sodium sulfite (S) were mixed as follows: s =100, dripping a few drops of concentrated sulfuric acid, refluxing and stirring for 3h at 100 ℃, pouring off acid liquor, adjusting the pH value to 8 by potassium hydroxide, and drying to obtain sulfonated humate;

2) Sulfonating sodium humate according to the mass ratio: naphthalene sulfonic acid: formaldehyde solution: water =100, 50. And cooling to room temperature to obtain the modified humic acid multi-component copolymerization coal water slurry dispersing agent with the weight average molecular weight of 8000, and compounding with 0.1% of rhamnella rubber.

Comparative example 2

1) First, sodium Humate (HA), sodium sulfite (S) were mixed as HA: mixing S =100:22, dripping a few drops of concentrated sulfuric acid, stirring at 100 ℃ for 3h under reflux, pouring off acid liquor, adjusting the pH value to 9 by potassium hydroxide, and drying to obtain sulfonated humate;

2) Sulfonating sodium humate according to the mass ratio: polyether: formaldehyde solution: water =100, 35, formaldehyde was added dropwise over 1h, the solution pH was around 8, and the reaction was stirred at 93 ℃ for 3h. And cooling to room temperature to obtain the modified humic acid multi-copolymerization coal water slurry dispersing agent with the weight-average molecular weight of 11000, and compounding with 0.05% of thermocline gum.

Comparative example 3

1) First, sodium Humate (HA), sodium sulfite (S) were mixed as HA: mixing S =100:22, dripping a few drops of concentrated sulfuric acid, refluxing and stirring for 3h at 100 ℃, pouring off acid liquor, adjusting the pH value to 8 by sodium hydroxide, and drying to obtain sulfonated humate;

2) And (2) sulfonating sodium humate according to the mass ratio: benzene sulfonic acid: aromatic polyether (Mw = 4000): formaldehyde solution: water =100: 6. And cooling to room temperature to obtain the modified humic acid multi-copolymerization coal water slurry dispersing agent.

Comparative example 4

1) First, sodium Humate (HA), sodium sulfite (S) were mixed as follows: mixing S =100: 18, dripping a few drops of concentrated sulfuric acid, refluxing and stirring for 3 hours at 100 ℃, pouring out acid liquor, adjusting the pH to 9 by potassium hydroxide, and drying to obtain sulfonated humate;

2) Sulfonating sodium humate according to the mass ratio: beta-naphthalenesulfonic acid: aromatic polyether: formaldehyde solution: water =100: 5. And cooling to room temperature to obtain the modified humic acid multi-copolymerization coal water slurry dispersing agent with the weight average molecular weight =26000, and compounding with 1% diutan.

Comparative example 5

1) First, sodium Humate (HA) and sodium bisulfite (S) were mixed in the following ratio of HA: mixing S =100: 30, dripping a few drops of concentrated sulfuric acid, refluxing and stirring for 3 hours at 100 ℃, pouring out acid liquor, adjusting the pH to 8 by potassium hydroxide, and drying to obtain sulfonated humate;

2) Sulfonating sodium humate according to the mass ratio: beta-naphthalenesulfonic acid: aromatic polyether: formaldehyde solution: water =100: 5. And cooling to room temperature to obtain the modified humic acid multi-component copolymerization coal water slurry dispersing agent with the weight average molecular weight = 27000. The elm coal is used for preparing the coal water slurry, and the industrial analysis data of the elm coal are as follows:

TABLE 1 Ullin coal Industrial analysis

The elm coal was ground to coal fines having a particle size distribution as shown in the table below by a vibratory mill and tested for slurrification, flowability and stability.

Table 2: particle size distribution of elm coal

	D10	D50	D90	D(4,3)
					Particle size/. Mu.m	2.54	24.54	258.8	79.8

TABLE 3 Dispersion Effect of coal-water slurries

And (3) the fluidity judgment standard is as follows: a: linear fluid, relatively dilute in appearance B: a thick fluid, which can flow slowly

C: require external force to flap to flow D: can not flow

And (4) stability judgment standard: a: bottom no hard precipitate B: a small amount of soft precipitate at the bottom and stirring can be recovered

C: bottom massive precipitation, difficult to stir to recover D: the bottom was hard settling and could not be recovered.

Claims

1. A multi-component copolymer dispersant based on humic acid is characterized in that the dispersant is prepared by condensation polymerization of humic acid and salt thereof, benzenesulfonic acid and derivative monomer A thereof and aromatic polyether B;

the aromatic polyether B has the following structural general formula:

in the structural general formula of the aromatic polyether monomer B, the weight average molecular weight of the aromatic polyether monomer B is between 1000 and 3000, m and n are the average addition mass number of ethylene oxide and propylene oxide respectively, m = 0-73, n = 0-53, m and n are integers;

the weight average molecular weight is 15000-35000;

the preparation method of the humic acid-based multipolymer dispersant comprises the steps of carrying out multipolymer copolymerization on humic acid, a sulfonating agent, a monomer A, an aromatic polyether monomer B, 37 percent formaldehyde solution and water according to the feeding mass ratio of 100 (15-36): (4-14): 28-101): 25-50): 165-490, wherein the multipolymer copolymerization has the duration of 2-6 h; heating to 85-95 ℃; the humic acid is sulfonated by a sulfonating agent and then participates in a polycondensation reaction, and the sulfonating agent is one or a mixture of sodium sulfite and concentrated sulfuric acid.

2. The humic acid-based multipolymer dispersant of claim 1, wherein the humic acid-based multipolymer dispersant is a liquid product or is dried to obtain a dusted product.

3. The humic acid-based multipolymer dispersant according to claim 1, wherein the humic acid-based multipolymer dispersant is formulated with a stabilizer;

the stabilizer is selected from gellan gum, welan gum, rhamsan gum, diutan gum, xanthan gum and/or guar gum;

the dosage of the stabilizer is 0.01-0.5% of that of the dispersant.

4. The humic acid based multipolymer dispersant of claim 1, wherein the specific steps of the sulfonation of the humic acid are as follows:

5. The process for the preparation of humic acid based multipolymer dispersants of any of claims 1-4, characterized by the following specific steps:

mixing humate or sulfonated humate with the monomer A and the monomer B, heating the mixed solution, slowly dripping the formaldehyde aqueous solution into the solution under stirring, and finishing dripping within 40-80 minutes; preserving the heat for 2-6h, cooling to room temperature to obtain a dark red liquid, namely a liquid product of the humic acid-based multipolymer dispersant, and performing spray drying at the high temperature of 280-350 ℃ to obtain a powder product with the water content of 1-9%.

6. A method according to claim 5, characterized in that a stabilizer product is added to the liquid or powder dispersion.

7. Use of the humic acid based multipolymer dispersant according to any of claims 1 to 4 for the preparation of a reconstituted coal water slurry.

8. The application of the coal water slurry as claimed in claim 7, wherein the coal water slurry comprises the following components in parts by weight:

55 to 70 portions of coal powder,

30-45 parts of water, namely,

0.1 to 0.5 portion of multi-copolymer dispersant based on humic acid.