CN112979877A - Cellulose-based dispersing agent, preparation method and application thereof, and coal water slurry - Google Patents
Cellulose-based dispersing agent, preparation method and application thereof, and coal water slurry Download PDFInfo
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- CN112979877A CN112979877A CN202110198290.5A CN202110198290A CN112979877A CN 112979877 A CN112979877 A CN 112979877A CN 202110198290 A CN202110198290 A CN 202110198290A CN 112979877 A CN112979877 A CN 112979877A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
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Abstract
The invention belongs to the technical field of auxiliaries, and particularly relates to a cellulose-based dispersing agent, and a preparation method and application thereof. The preparation method of the cellulose-based dispersing agent provided by the invention comprises the following steps: mixing carboxymethyl cellulose and 2-bromine isobutyryl bromide in an organic solvent for acylation reaction to obtain an initiator; and mixing the initiator and sodium styrene sulfonate in the presence of a catalyst to perform atom transfer radical copolymerization reaction to obtain the cellulose-based dispersing agent. According to the invention, firstly, carboxymethyl cellulose and 2-bromoisobutyryl bromide are acylated in an organic solvent to synthesize an initiator, then sodium styrene sulfonate is used as a monomer, the initiator is used for initiating an atom transfer radical copolymerization reaction, and a polystyrene sulfonic acid group is grafted on the carboxymethyl cellulose to obtain the cellulose-based dispersing agent with a cellulose framework and a sodium polystyrene sulfonate side chain.
Description
Technical Field
The invention belongs to the technical field of auxiliaries, and particularly relates to a cellulose-based dispersing agent, a preparation method and application thereof, and coal water slurry.
Background
The coal water slurry is a coal-based clean fluidized fuel and generally comprises 60-75 wt.% of coal powder, 24-39 wt.% of water and 1 wt.% of dispersant. Currently, the dispersant classes for coal water slurries include synthetic polymers, natural compounds and natural compound derivatives. Among them, the preparation method of synthetic polymer dispersants (such as naphthalenesulfonic acid-formaldehyde condensate, polycarboxylic acid, or sulfonated acetone-formaldehyde) generally requires a large amount of expensive stone materials, for example, synthesis of naphthalenesulfonic acid-formaldehyde condensate generally requires naphthalene, sulfuric acid, and formaldehyde as main raw materials; natural compound dispersants (e.g., lignin or carboxymethyl cellulose) and natural compound dispersant derivatives have the advantages of abundant sources and low cost, but natural dispersants have poor dispersing properties.
Disclosure of Invention
In view of the above, the present invention provides a cellulose-based dispersant and a preparation method thereof, and the cellulose-based dispersant obtained by the preparation method provided by the present invention has excellent price dispersibility and good static stability.
In order to achieve the purpose of the invention, the invention provides the following technical scheme:
the invention provides a preparation method of a cellulose-based dispersing agent, which comprises the following steps:
mixing carboxymethyl cellulose and 2-bromine isobutyryl bromide in an organic solvent for acylation reaction to obtain an initiator;
and mixing the initiator and sodium styrene sulfonate in the presence of a catalyst to perform atom transfer radical copolymerization reaction to obtain the cellulose-based dispersing agent.
Preferably, the molar ratio of the carboxymethyl cellulose to the 2-bromoisobutyryl bromide is (0.8-1): (1.2-1.5).
Preferably, the carboxymethyl cellulose and the 2-bromoisobutyryl bromide are mixed in an organic solvent by dropwise adding the 2-bromoisobutyryl bromide into an organic solution of the carboxymethyl cellulose, wherein the organic solution of the carboxymethyl cellulose comprises the carboxymethyl cellulose and the organic solvent; the dropping temperature is-5 ℃, and the dropping speed is 5-8 mL/min.
Preferably, the temperature of the acylation reaction is 18-40 ℃, and the time is 5-10 h.
Preferably, the molar ratio of the initiator to the sodium styrene sulfonate is (0.5-0.8): (2-2.4).
Preferably, the atom transfer radical copolymerization reaction conditions include: the pH value is 8-11; the temperature is 50-70 ℃, and the time is 7-10 h.
Preferably, the catalyst is a copper catalyst, a cobalt catalyst or a nickel catalyst.
The invention also provides the cellulose-based dispersing agent prepared by the preparation method of the technical scheme, and the cellulose-based dispersing agent has a cellulose skeleton and a sodium polystyrene sulfonate side chain.
The invention also provides the cellulose-based dispersing agent prepared by the preparation method of the technical scheme or the application of the cellulose-based dispersing agent in the water-coal-slurry.
The invention also provides coal water slurry which comprises coal powder, water and a dispersant, wherein the dispersant is a cellulose-based dispersant prepared by the preparation method of the technical scheme or the cellulose-based dispersant of the technical scheme.
The invention provides a preparation method of a cellulose-based dispersing agent, which comprises the following steps: mixing carboxymethyl cellulose and 2-bromine isobutyryl bromide in an organic solvent for acylation reaction to obtain an initiator; and mixing the initiator and sodium styrene sulfonate in the presence of a catalyst to perform atom transfer radical copolymerization reaction to obtain the cellulose-based dispersing agent. According to the invention, firstly, carboxymethyl cellulose and 2-bromoisobutyryl bromide are acylated in an organic solvent to synthesize an initiator, then sodium styrene sulfonate is used as a monomer, the initiator is used for initiating an atom transfer radical copolymerization reaction, and a polystyrene sulfonic acid group is grafted on the carboxymethyl cellulose to obtain the cellulose-based dispersing agent with a cellulose framework and a sodium polystyrene sulfonate side chain. According to the invention, the prepared cellulose-based dispersing agent takes a cellulose structure as a main chain, and an anionic group sulfonic acid group capable of enhancing the electrostatic repulsion of coal particles is introduced into a side chain of the main chain of the cellulose structure, so that the cellulose-based dispersing agent can be better adsorbed to the surfaces of the coal particles, the electronegativity of the surfaces of the coal particles is increased, and the electrostatic repulsion is increased; the ester side chain is dispersed in a water-coal-slurry system and forms hydrogen bond combination with water molecules, so that the hydrophilic characteristic of the dispersing agent is enhanced, and the stability of slurry is facilitated; the steric hindrance acting force can be increased by the aromatic ring structure of the monomer in the side chain of the main chain of the cellulose structure, so that coal particles are not easy to gather and are dispersed in a water system to form stable coal water slurry.
The test results of the embodiment show that the cellulose-based dispersing agent obtained by the preparation method provided by the invention has excellent viscosity, good static stability and good coal water slurry dispersing effect, and can obviously reduce the using amount of the dispersing agent in the coal water slurry and save the cost.
Detailed Description
The invention provides a preparation method of a cellulose-based dispersing agent, which comprises the following steps:
mixing carboxymethyl cellulose and 2-bromine isobutyryl bromide in an organic solvent for acylation reaction to obtain an initiator;
and mixing the initiator and sodium styrene sulfonate in the presence of a catalyst to perform atom transfer radical copolymerization reaction to obtain the cellulose-based dispersing agent.
In the present invention, unless otherwise specified, commercially available products well known to those skilled in the art are used for each component in the preparation method.
In the invention, carboxymethyl cellulose and 2-bromine isobutyryl bromide are mixed in an organic solvent for acylation reaction to obtain an initiator.
In the invention, the molar ratio of the carboxymethyl cellulose to the 2-bromoisobutyryl bromide is preferably (0.8-1): (1.2-1.5), more preferably (0.85-0.95): (1.25-1.45). In the present invention, the organic solvent is preferably methyl chloride, more preferably CH2Cl2Or CHCl3. The amount of the organic solvent used in the present invention is not particularly limited so as to form a uniform organic phase with carboxymethyl celluloseThe solution is the standard.
In the present invention, the mixing of the carboxymethyl cellulose and the 2-bromoisobutyryl bromide in the organic solvent is preferably performed by dissolving the carboxymethyl cellulose in the organic solvent to obtain an organic solution of the carboxymethyl cellulose, and then adding dropwise the 2-bromoisobutyryl bromide to the organic solution of the carboxymethyl cellulose. In the invention, the mass percentage concentration of the carboxymethyl cellulose in the organic solution of the carboxymethyl cellulose is preferably 1-10%. In the invention, the dripping temperature is preferably-5 ℃, and more preferably-4 ℃. In the invention, the dripping speed is preferably 5-8 mL/min, and more preferably 5.5-7.5 mL/min.
In the invention, the temperature of the acylation reaction is preferably 18-40 ℃, and more preferably 20-30 ℃; the time is preferably 5 to 10 hours, and more preferably 6 to 9 hours.
In the present invention, the reaction system for carrying out the acylation reaction preferably further comprises an acylation reaction catalyst. In the present invention, the acylation reaction catalyst is preferably triethylamine. In the invention, the molar ratio of the 2-bromoisobutyryl bromide to the acylation reaction catalyst is preferably (1.2-1.5): (0.05-0.1), more preferably (1.25-1.45): (0.06-0.09).
After the acylation reaction, the solid-liquid mixture is preferably subjected to solid-liquid separation, and the obtained solid substance is dried to obtain the initiator. The solid-liquid separation is not particularly limited in the present invention, and may be performed by a solid-liquid separation known to those skilled in the art, specifically, by filtration. In the invention, the drying temperature is preferably 45-65 ℃, and more preferably 50-60 ℃; the time is preferably 30 to 60min, and more preferably 35 to 40 min.
After the initiator is obtained, the initiator and sodium styrene sulfonate are mixed to carry out atom transfer radical copolymerization reaction in the presence of a catalyst, so as to obtain the cellulose-based dispersing agent.
In the present invention, the catalyst is preferably a copper catalyst, a cobalt catalyst or a nickel catalyst. In the present invention, the copper catalyst is preferably CuCl, Cu (NO)3)2Or CuCO3. In the present inventionIn the invention, when the catalyst is a copper catalyst, the mass ratio of the catalyst to the mixed solution is preferably 1: (15-20), more preferably 1: (16-19). In the present invention, the cobalt catalyst is preferably cobalt acetate (C)4H6O4·Co·4H2O) or sulfonated titanium cobalt cyanide ((C)32H16N8Co(SO3)2). In the present invention, when the catalyst is a cobalt catalyst, the mass ratio of the catalyst to the mixed liquid is preferably 1: (10-15), more preferably 1: (11-14). In the present invention, the nickel catalyst is preferably raney nickel. In the present invention, when the catalyst is a nickel catalyst, the mass ratio of the catalyst to the mixed solution is preferably 1: (5-8), more preferably 1: (5.5-7.5). In the present invention, the molar ratio of the sodium styrene sulfonate to the catalyst is preferably 100: (5-20), more preferably 100: (7-18).
In the invention, the molar ratio of the initiator to the sodium styrene sulfonate is preferably (0.5-0.8): (2-2.4), more preferably (0.55-0.75): (2.1-2.3).
The mixing of the initiator and the sodium styrene sulfonate is not particularly limited in the present invention, and may be a mixing well known to those skilled in the art.
Before the atom transfer radical copolymerization reaction, the mixed solution of the initiator and the sodium styrene sulfonate is preferably subjected to nitrogen bubbling treatment. In the present invention, the time for the nitrogen bubbling treatment is preferably 10 to 50min, and more preferably 15 to 45 min. In the invention, the flow rate of the nitrogen in the nitrogen bubbling treatment is preferably 15-30 mL/min, and more preferably 20-25 mL/min. The invention uses nitrogen bubbling to strengthen mass transfer and plays a role in stirring; nitrogen is an inert gas and does not react with the solution.
In the invention, the pH value of the reaction liquid in the atom transfer radical copolymerization reaction is preferably 8-11, and more preferably 8.5-10.5. In the present invention, the pH adjustor which adjusts the pH in the atom transfer radical copolymerization reaction preferably includes NaOH or KOH.
In the invention, the temperature in the atom transfer radical copolymerization reaction is preferably 50-70 ℃, and more preferably 55-65 ℃; the time is preferably 7 to 10 hours, and more preferably 7.5 to 9.5 hours.
In the present invention, it is preferable that a redox indicator is further included in the reaction system of the atom transfer radical copolymerization reaction. In the present invention, the redox indicator is preferably 2,2' -bipyridine. In the present invention, the redox indicator is used to detect the catalyst metal ion in the reaction system of the atom transfer radical copolymerization reaction. The amount of the redox indicator used is not particularly limited, and is based on the detection of the catalyst metal ions.
In the present invention, the solvent in the reaction system of the atom transfer radical copolymerization reaction is preferably water, and more preferably deionized water. The amount of water used in the present invention is not particularly limited, and may be any amount known to those skilled in the art. In the invention, the water adjusts the viscosity of a reaction system of the atom transfer radical copolymerization reaction so as to ensure the atom transfer radical copolymerization reaction to be carried out.
After the atom transfer radical copolymerization reaction, the invention preferably carries out dialysis and drying on the obtained copolymerization product in sequence to obtain the cellulose-based dispersing agent.
In the invention, the dialysis molecular weight cut-off is preferably 1000, and the dialysis time is preferably 2-3 h, and more preferably 2.2-2.8 h. The invention removes the catalyst and unreacted sodium styrene sulfonate through dialysis.
In the present invention, the drying is preferably freeze-drying. The freeze-drying method of the present invention is not particularly limited, and freeze-drying known to those skilled in the art may be employed.
In an embodiment of the present invention, the cellulose-based dispersant is prepared by the following formula:
the invention also provides the cellulose-based dispersing agent prepared by the preparation method of the technical scheme, and the cellulose-based dispersing agent has a cellulose skeleton and a sodium polystyrene sulfonate side chain. In the present invention, the sodium polystyrene sulfonate side chains are grafted onto the cellulose backbone. In the invention, the grafting rate of the sodium polystyrene sulfonate side chain on the cellulose skeleton is preferably 50-60%.
In the invention, the critical micelle concentration of the cellulose-based dispersing agent is 1.5-4.3 g/L; the surface tension is 26.08-39.15 mN/m.
The invention also provides the cellulose-based dispersing agent prepared by the preparation method of the technical scheme or the application of the cellulose-based dispersing agent in the water-coal-slurry.
The application of the dispersant in the coal water slurry is not particularly limited, and the dispersant is applied to the coal water slurry, which is well known to those skilled in the art.
The invention also provides coal water slurry which comprises coal powder, water and a dispersant, wherein the dispersant is a cellulose-based dispersant prepared by the preparation method of the technical scheme or the cellulose-based dispersant of the technical scheme.
In the invention, the content of the cellulose-based dispersing agent in the coal water slurry is preferably 0.8-1.4 wt.%, and more preferably 0.9-1.3 wt.%.
In the invention, the content of the coal powder in the coal water slurry is preferably 60-70 wt.%, and more preferably 63-67 wt.%.
In the invention, the coal water slurry contains the balance of water.
The preparation method of the coal water slurry is not particularly limited, and the coal water slurry preparation method known by the technical personnel in the field can be adopted. In the present invention, the preparation method of the coal water slurry preferably comprises the following steps:
mixing a dispersant with water to obtain a dispersant aqueous solution;
and under the condition of stirring, adding coal powder into the dispersant aqueous solution, and stirring again to obtain the coal water slurry.
In the present invention, the water is preferably distilled water. In the present invention, the stirring and re-stirring rates are independently preferably 800 to 1400rpm, and more preferably 900 to 1300 rpm. In the invention, the time for re-stirring is preferably 3-15 min, and more preferably 5-10 min.
In order to further illustrate the present invention, the following examples are provided to describe the cellulose-based dispersant, the preparation method and the application thereof, and the coal water slurry in detail, but they should not be construed as limiting the scope of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The reagents used in the examples are all commercially available.
Example 1
By mass, 0.8 part of carboxymethyl cellulose, 0.07 part of triethylamine and 0.5 part of CH2Cl2Mixing to obtain an organic solution of carboxymethyl cellulose; dropwise adding 1.5 parts of 2-bromoisobutyryl bromide into an organic solution of carboxymethyl cellulose at the speed of 6mL/min at the temperature of 0 ℃, preserving the temperature for 7 hours at room temperature after dropwise adding to perform acylation reaction, filtering the obtained solid-liquid mixture, washing the obtained solid substance with water, and drying at the temperature of 50 ℃ for 40 minutes to obtain an initiator;
mixing all the initiators obtained in the previous step, 2.2 parts of sodium vinyl sulfonate, 0.6 part of 2,2' -bipyridine and 1.2 parts of deionized water, adjusting the pH value of the system to be 9-10 by adopting NaOH, carrying out nitrogen bubbling on the obtained mixed system for 20min, wherein the nitrogen flow is 20mL/min, then adding 0.5 part of catalyst CuCl into the mixed system, carrying out atom transfer radical copolymerization at 50 ℃ for 8h, exposing the mixed system to air for reaction termination, carrying out distilled water dialysis (the molecular weight cutoff is 1000) on the obtained copolymerization product for 72h, and then carrying out freeze drying to obtain the solid powdery cellulose-based dispersing agent.
The cellulose-based dispersant obtained in the embodiment is tested by a surface tension meter according to the measurement of the surface tension of GB/T22237-2008 surfactant, and the test shows that the critical micelle concentration of the cellulose-based dispersant obtained in the embodiment is 1.5g/L, and the surface tension of the cellulose-based dispersant is 28.42 mN/m.
Application example 1
0.5g of the cellulose-based dispersant obtained in example 1 and 34.5mL of distilled water were mixed to obtain a dispersant aqueous solution;
and under the stirring condition of 1200rpm, 65g of coal powder is added into the obtained dispersant aqueous solution, and after the addition is finished, the mixture is stirred for 5min at 1200rpm to obtain the coal water slurry.
The viscosity of the coal water slurry is 700mPa & s through testing; the volume average particle diameter was 32.46 μm; the Zeta potential is-40.5 mV; the suspension rate after standing for 15 days under the conditions of normal temperature and normal pressure is 89.95 percent, and no layering exists.
Application example 2
0.5g of the cellulose-based dispersant obtained in example 1 and 34.5mL of distilled water were mixed to obtain a dispersant aqueous solution;
and under the stirring condition of 800rpm, adding 65g of coal powder into the obtained dispersant aqueous solution, and stirring for 15min at 800rpm after the addition is finished to obtain the coal water slurry.
The viscosity of the coal water slurry is 685mPa & s through testing; the volume average particle diameter is 35.46 mu m; the Zeta potential is-40.2 mV; the suspension rate after standing for 15 days under the conditions of normal temperature and normal pressure is 86.73 percent, and no layering exists.
Application example 3
0.5g of the cellulose-based dispersant obtained in example 1 and 34.5mL of distilled water were mixed to obtain a dispersant aqueous solution;
and under the stirring condition of 1200rpm, 65g of coal powder is added into the obtained dispersant aqueous solution, and after the addition is finished, the mixture is stirred for 3min at 1400rpm to obtain the coal water slurry.
The viscosity of the coal water slurry is 715mPa & s through testing; the volume average particle diameter was 33.46 μm; the Zeta potential is-42.2 mV; the suspension rate after standing for 15 days under the conditions of normal temperature and normal pressure is 89.73%, and no layering exists.
Example 2
The preparation method of the initiator comprises the following steps: by mass, 0.8 part of carboxymethyl cellulose, 0.07 part of triethylamine and 0.5 part of CH2Cl2Mixing to obtain an organic solution of carboxymethyl cellulose; at-5 deg.C, 1.5 parts of 2-bromoisobutyryl bromide was added dropwise to the carboxylic acid at a rate of 6mL/minAfter dropwise adding the methyl cellulose into an organic solution, preserving the temperature for 5 hours at room temperature for acylation reaction, filtering the obtained solid-liquid mixture, washing the obtained solid substance with water, and drying at 55 ℃ for 40 minutes to obtain an initiator;
the rest of the technical means are the same as the embodiment 1, and the cellulose-based dispersing agent in solid powder form is obtained.
As with the test method of example 1, the cellulose-based dispersant obtained in this example was found to have a critical micelle concentration of 1.8g/L and a surface tension of 30.08 mN/m.
Application example 4
0.5g of the cellulose-based dispersant obtained in example 2 and 34.5mL of distilled water were mixed to obtain a dispersant aqueous solution;
and under the stirring condition of 1200rpm, 65g of coal powder is added into the obtained dispersant aqueous solution, and after the addition is finished, the mixture is stirred for 5min at 1200rpm to obtain the coal water slurry.
The viscosity of the coal water slurry is 732 mPas through testing; the volume average particle diameter is 30.66 mu m; the Zeta potential is-38.5 mV; the suspension rate after standing for 15 days under the conditions of normal temperature and normal pressure is 85.38%, and no layering exists.
Example 3
The preparation method of the initiator comprises the following steps: by mass, 1 part of carboxymethyl cellulose, 0.1 part of triethylamine and 0.5 part of CH2Cl2Mixing to obtain an organic solution of carboxymethyl cellulose; dropwise adding 1.5 parts of 2-bromoisobutyryl bromide into an organic solution of carboxymethyl cellulose at the speed of 6mL/min at the temperature of 5 ℃, preserving the temperature for 10 hours at room temperature after dropwise adding to perform acylation reaction, filtering the obtained solid-liquid mixture, washing the obtained solid substance with water, and drying at the temperature of 60 ℃ for 40 minutes to obtain an initiator;
the rest of the technical means are the same as the embodiment 1, and the cellulose-based dispersing agent in solid powder form is obtained.
As with the test method of example 1, the cellulose-based dispersant obtained in this example was found to have a critical micelle concentration of 4.3g/L and a surface tension of 39.15 mN/m.
Application example 5
0.5g of the cellulose-based dispersant obtained in example 3 and 34.5mL of distilled water were mixed to obtain a dispersant aqueous solution;
and under the stirring condition of 800rpm, adding 65g of coal powder into the obtained dispersant aqueous solution, and stirring for 15min at 800rpm after the addition is finished to obtain the coal water slurry.
The viscosity of the coal water slurry is 550mPa & s through testing; the volume average particle diameter was 62.39 μm; the Zeta potential is-35.2 mV; the suspension rate after standing for 15 days under the conditions of normal temperature and normal pressure is 76.73%, and a small amount of layering exists.
Example 4
The initiator was prepared in the same manner as in example 1 to give an initiator;
mixing all the obtained initiators, 2 parts of sodium styrene sulfonate, 0.6 part of 2,2' -bipyridine and 0.72 part of deionized water, adjusting the pH value of the system to be 8-9 by adopting NaOH, carrying out nitrogen bubbling on the obtained mixed system for 40min, wherein the nitrogen flow is 20mL/min, then adding 0.5 part of catalyst CuCl into the mixed system, carrying out atom transfer radical copolymerization reaction at 70 ℃ for 7h, terminating the reaction after exposure to air, carrying out distilled water dialysis (the molecular weight cut-off is 1000) on the obtained copolymerization product for 48h, and then carrying out freeze drying to obtain the solid powdery cellulose-based dispersing agent.
As with the test method of example 1, the cellulose-based dispersant obtained in this example was found to have a critical micelle concentration of 1.7g/L and a surface tension of 26.08 mN/m.
Application example 6
0.5g of the cellulose-based dispersant obtained in example 4 and 34.5mL of distilled water were mixed to obtain a dispersant aqueous solution;
and under the stirring condition of 1200rpm, 65g of coal powder is added into the obtained dispersant aqueous solution, and after the addition is finished, the mixture is stirred for 3min at 1400rpm to obtain the coal water slurry.
The viscosity of the coal water slurry is 720mPa & s through testing; the volume average particle diameter was 32.16 μm; the Zeta potential is-43.5 mV; the suspension rate after standing for 15 days under the conditions of normal temperature and normal pressure is 85.53%, and no layering exists.
Example 5
The initiator was prepared in the same manner as in example 1 to give an initiator;
mixing the obtained initiator, 2.4 parts of sodium styrene sulfonate, 0.6 part of 2,2' -bipyridine and 0.72 part of deionized water, adjusting the pH value of the system to 10-11 by adopting NaOH, carrying out nitrogen bubbling on the obtained mixed system for 15min, wherein the nitrogen flow is 40mL/min, then adding 0.5 part of catalyst CuCl into the mixed system, carrying out atom transfer radical copolymerization reaction at 55 ℃ for 10h, exposing the mixed system to the air for reaction termination, carrying out distilled water dialysis (the molecular weight cut-off is 1000) on the obtained copolymerization product for 84h, and then carrying out freeze drying to obtain the solid powdery cellulose-based dispersing agent.
As with the test method of example 1, the cellulose-based dispersant obtained in this example was found to have a critical micelle concentration of 1.9g/L and a surface tension of 27.42 mN/m.
Application example 7
0.5g of the cellulose-based dispersant obtained in example 5 and 34.5mL of distilled water were mixed to obtain a dispersant aqueous solution;
and under the stirring condition of 1200rpm, 65g of coal powder is added into the obtained dispersant aqueous solution, and after the addition is finished, the mixture is stirred for 3min at 1400rpm to obtain the coal water slurry.
The viscosity of the coal water slurry is 675mPa & s through testing; the volume average particle diameter was 44.79. mu.m; the Zeta potential is-32.8 mV; the suspension rate after standing for 15 days under the conditions of normal temperature and normal pressure is 82.58%, and no layering exists.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a cellulose-based dispersant is characterized by comprising the following steps:
mixing carboxymethyl cellulose and 2-bromine isobutyryl bromide in an organic solvent for acylation reaction to obtain an initiator;
and mixing the initiator and sodium styrene sulfonate in the presence of a catalyst to perform atom transfer radical copolymerization reaction to obtain the cellulose-based dispersing agent.
2. The preparation method according to claim 1, wherein the molar ratio of the carboxymethyl cellulose to the 2-bromoisobutyryl bromide is (0.8-1): (1.2-1.5).
3. The method according to claim 1, wherein the carboxymethyl cellulose and the 2-bromoisobutyryl bromide are mixed in an organic solvent by adding the 2-bromoisobutyryl bromide dropwise to an organic solution of the carboxymethyl cellulose, the organic solution of the carboxymethyl cellulose comprising the carboxymethyl cellulose and the organic solvent; the dropping temperature is-5 ℃, and the dropping speed is 5-8 mL/min.
4. The method according to any one of claims 1 to 3, wherein the acylation reaction is carried out at a temperature of 18 to 40 ℃ for 5 to 10 hours.
5. The preparation method according to claim 1, wherein the molar ratio of the initiator to the sodium styrene sulfonate is (0.5-0.8): (2-2.4).
6. The production method according to claim 1 or 5, wherein the conditions of the atom transfer radical copolymerization reaction include: the pH value is 8-11; the temperature is 50-70 ℃, and the time is 7-10 h.
7. The method of claim 1, wherein the catalyst is a copper catalyst, a cobalt catalyst, or a nickel catalyst.
8. The cellulose-based dispersant prepared by the preparation method of any one of claims 1 to 7, wherein the cellulose-based dispersant has a cellulose skeleton and a sodium polystyrene sulfonate side chain.
9. The cellulose-based dispersing agent prepared by the preparation method of any one of claims 1 to 7 or the application of the cellulose-based dispersing agent of claim 8 in coal water slurry.
10. A coal water slurry comprising coal fines, water and a dispersant, wherein the dispersant is the cellulose-based dispersant of claim 8.
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