CN110194823B - Graft copolymer coal water slurry dispersant and preparation method thereof - Google Patents
Graft copolymer coal water slurry dispersant and preparation method thereof Download PDFInfo
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- CN110194823B CN110194823B CN201910438416.4A CN201910438416A CN110194823B CN 110194823 B CN110194823 B CN 110194823B CN 201910438416 A CN201910438416 A CN 201910438416A CN 110194823 B CN110194823 B CN 110194823B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/18—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenols substituted by carboxylic or sulfonic acid groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
- C08G8/32—Chemically modified polycondensates by organic acids or derivatives thereof, e.g. fatty oils
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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
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
- C10L1/2462—Organic compounds containing sulfur, selenium and/or tellurium macromolecular compounds
- C10L1/2475—Organic compounds containing sulfur, selenium and/or tellurium macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon to carbon bonds
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- C—CHEMISTRY; METALLURGY
- 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
- C10L1/326—Coal-water suspensions
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Abstract
The invention discloses a graft copolymer coal water slurry dispersant and a preparation method thereof, and the preparation method specifically comprises the following steps: 1) mixing the melted phenol with concentrated sulfuric acid solution, and carrying out sulfonation reaction at the temperature of 90-110 ℃ to obtain solution B; 2) adding a formaldehyde solution into the solution B, carrying out polymerization reaction at the temperature of 80-120 ℃, adding distilled water for dissolving after the reaction is finished, and uniformly mixing to obtain a solution C; 3) adjusting the pH value of the solution C to 10-12, then adding a benzoyl chloride solution, and carrying out an acylation reaction at the temperature of 80-100 ℃ to obtain a crude product; 4) and standing and precipitating the crude product for multiple times, and distilling the precipitate under reduced pressure to obtain viscous liquid, namely the coal water slurry dispersing agent. The graft copolymer coal water slurry dispersing agent is a comb-shaped amphiphilic molecule, has high sulfonation degree and high hydrophilicity, has main structural units of benzene ring hydrophobic groups and sulfonic hydrophilic groups, and has obvious pulping effect on low-order coal, and good viscosity reducing effect and dispersing effect.
Description
Technical Field
The invention relates to the technical field of dispersants, and particularly relates to a graft copolymer coal water slurry dispersant and a preparation method thereof.
Background
The coal water slurry technology is a clean coal utilization mode, and is gaining more and more attention at present. The coal water slurry is generally prepared by processing 60-70% of coal powder, 30-40% of water and about 1% of chemical additives (dispersing agent, stabilizing agent and the like) by a physical method. As a coarse dispersion system, the coal water slurry has to realize high concentration and high stability by virtue of the dispersion stability of the additive, and particularly, the function of the additive is particularly critical when preparing high-concentration coal water slurry. The existing dispersant types of the coal water slurry mainly comprise lignin dispersants, aliphatic dispersants, naphthalene dispersants and polycarboxylic acid dispersants. The low-rank coal is a coal which is difficult to be pulped, the traditional coal water slurry dispersing agent is lack of pertinence, the pulping effect is general, and the development and utilization of the low-rank coal are severely restricted.
Disclosure of Invention
The invention aims to provide a graft copolymer coal water slurry dispersing agent and a preparation method thereof, and aims to solve the technical problems of difficult slurrying and poor slurrying effect of low-rank coal.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a preparation method of a graft copolymer coal water slurry dispersing agent comprises the following steps:
step 1) taking a certain amount of phenol, heating and stirring for 10-15 min at 40-60 ℃, and obtaining a solution A after the phenol is melted; then adding concentrated sulfuric acid solution into the solution A, continuously stirring for 1-3 h at the temperature of 90-110 ℃, and carrying out sulfonation reaction to obtain solution B;
step 2) adding a formaldehyde solution into the solution B, stirring for 2-4 h at 80-120 ℃, carrying out polymerization reaction, adding distilled water for dissolving after the reaction is finished, and uniformly mixing to obtain a solution C;
step 3) adjusting the pH value of the solution C to 10-12 by using an alkaline regulator, then adding a benzoyl chloride solution, stirring for 1.5-3.5 h at the temperature of 80-100 ℃, and carrying out acylation reaction to obtain a crude product;
and 4) standing and precipitating the crude product for multiple times, and distilling the precipitate under reduced pressure to obtain viscous liquid, namely the graft copolymer coal water slurry dispersing agent.
Preferably, in step 1), the molar ratio of phenol to concentrated sulfuric acid solution is 1: 1 to 1.4.
Preferably, in the step 2), the molar ratio of the formaldehyde solution to the phenol is 0.7: 1, wherein the mass fraction of the formaldehyde solution is 37%.
Preferably, in the step 3), the molar ratio of the benzoyl chloride solution to the phenol is 1.5: 1, the mass fraction of the benzoyl chloride solution is more than 95 percent.
Preferably, in step 3), the alkaline regulator is sodium hydroxide and/or potassium hydroxide.
Further, step 4) also includes: and drying the viscous liquid to facilitate storage and transportation of the dispersing agent.
The invention also provides a graft copolymer coal water slurry dispersing agent prepared by the preparation method, and the structural formula of the coal water slurry dispersing agent is shown in the specification
Wherein M is one of Na and K.
The organic matter of the coal consists of two parts, wherein one part is a cyclic macromolecular compound and mainly has an aromatic structure; the other part is a chain low-molecular compound. The cyclic macromolecular compound is the main component of the coal organic matter and generally accounts for more than 90 percent; the research shows that when the carbon content in the coal is 70-83%, the average ring number of the structural unit is about 2. The graft polymer coal water slurry dispersant of the invention has 2 benzene rings in each structural unit, and the matching degree of the hydrophobic functional group of the dispersant and the cyclic macromolecular substance in the low-order coal molecule is higher, thus achieving the degree of tight combination.
Compared with the prior art, the invention has the following beneficial effects:
1. the graft copolymer prepared by the invention is a comb-shaped amphipathic molecule, the main structural units of the graft copolymer are benzene ring hydrophobic groups and sulfonic hydrophilic groups, the graft copolymer has high sulfonation degree and high hydrophilicity, and the graft copolymer is used as a water-coal-slurry dispersing agent, has an obvious pulping effect on low-rank coal, and has a good viscosity reducing effect and a good dispersing effect. Compared with the two common dispersants (lignin dispersant and naphthalene dispersant), the graft copolymer coal water slurry dispersant has better fluidity and dispersibility.
2. The preparation method is simple, the intermediate product does not need post-treatment, can be directly used as the raw material for the next reaction, and is suitable for industrial mass production.
Drawings
FIG. 1 is an infrared spectrum of a graft copolymer coal-water slurry dispersant prepared in example 1 of the present invention;
FIG. 2 is a graph showing the contact angle test of the dispersant of the graft copolymer prepared in example 1 of the present invention with pure water;
FIG. 3 is a rheological profile for a slurry of the graft copolymer water-coal-slurry dispersant prepared in example 1 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
In the following examples, unless otherwise specified, the starting materials were commercially available, and the experimental procedures were carried out in a conventional manner.
The chemical reaction process for preparing the graft polymer coal water slurry dispersant in the following examples is as follows:
example 1
A preparation method of a graft copolymer coal water slurry dispersing agent comprises the following steps:
step 1) taking 0.1mol of phenol, heating and stirring for 15min at 40 ℃, and obtaining a solution A after the phenol is melted; then adding 0.12mol of concentrated sulfuric acid solution into the solution A, continuously stirring for 1h at the temperature of 90 ℃, and carrying out sulfonation reaction to obtain solution B;
step 2) adding 0.07mol of formaldehyde solution (mass fraction is 37%) into the solution B, stirring for 2h at 80 ℃, carrying out polymerization reaction, adding a proper amount of distilled water for dissolving, and uniformly mixing to obtain a solution C;
step 3) adjusting the pH value of the solution C to 10 by using 1mol/L sodium hydroxide solution, then adding 0.15mol of benzoyl chloride solution (the mass fraction is more than 95%), stirring for 1.5h at the temperature of 80 ℃, and carrying out acylation reaction to obtain a crude product;
and 4) standing and precipitating the crude product for multiple times, and distilling the precipitate under reduced pressure to obtain a reddish brown viscous liquid, namely the coal water slurry dispersing agent.
The dispersant for coal water slurry prepared in the embodiment is placed in an infrared spectrometer for detection, as shown in figure 1, 3440cm-1Is a stretching vibration peak of 2930cm which belongs to phenolic hydroxyl on a benzene ring-1Is methylene (-CH)2-) asymmetric stretching vibration peak, 1614cm-1And 1460cm-1Is a C ═ C stretching vibration peak which is peculiar to a benzene ring framework. 1200cm-1Belonging to sulfonic acid groups (-SO)3 2-) 1736cm in peak of stretching vibration-1Stretching vibration absorption peak of metal C ═ O (benzoic acid), 1240cm-1Is the stretching vibration peak of the aromatic ether. It shows that sulfonic acid group and benzene ring functional group are introduced into the molecular structure. According to the judgment of the analysis result, the synthetic polymer is a target product.
The pure water and the dispersant solution were respectively dropped on the surface of the Shenfu low-rank coal by a micro syringe, then the contact angle was measured by a contact angle measuring instrument and photographed, and the change of the contact angle after one minute was observed, as a result, as shown in FIG. 2, it was seen that the pure water was spread on the coal surface after dropping on the coal interface, the spreading was slow after one minute, the contact angle was changed from 74.32 to 64.66, and the contact angle was changed from 70.23 to 53.15 after one minute, and the spreading was fast with the increase of time after the synthesized dispersant solution was dropped on the coal surface. The dispersant improves the wettability of the coal surface, so that the water and the coal surface are in a compatible state, and the water can be rapidly combined with the coal.
Example 2
A preparation method of a graft copolymer coal water slurry dispersing agent comprises the following steps:
step 1) taking 0.5mol of phenol, heating and stirring for 15min at 50 ℃, and obtaining a solution A after the phenol is melted; then adding 0.5mol of concentrated sulfuric acid solution into the solution A, continuously stirring for 2 hours at the temperature of 100 ℃, and carrying out sulfonation reaction to obtain solution B;
step 2) adding 0.35mol of formaldehyde solution (mass fraction is 37%) into the solution B, stirring for 2h at 100 ℃, carrying out polymerization reaction, adding a proper amount of distilled water for dissolving, and uniformly mixing to obtain a solution C;
step 3) adjusting the pH value of the solution C to 11 by using 1mol/L sodium hydroxide solution, then adding 0.75mol of benzoyl chloride solution (the mass fraction is more than 95%), stirring for 2 hours at 85 ℃, and carrying out acylation reaction to obtain a crude product;
and 4) standing and precipitating the crude product for multiple times, and distilling the precipitate under reduced pressure to obtain a reddish brown viscous liquid, namely the coal water slurry dispersing agent.
The infrared spectrogram of the coal water slurry dispersing agent prepared in the embodiment is similar to that of the embodiment 1.
Example 3
A preparation method of a graft copolymer coal water slurry dispersing agent comprises the following steps:
step 1) taking 1mol of phenol, heating and stirring for 10min at the temperature of 60 ℃, and obtaining a solution A after the phenol is melted; then adding 1.4mol of concentrated sulfuric acid solution into the solution A, continuously stirring for 3 hours at the temperature of 110 ℃, and carrying out sulfonation reaction to obtain solution B;
step 2) adding 0.7mol of formaldehyde solution (mass fraction is 37%) into the solution B, stirring for 4h at 120 ℃, carrying out polymerization reaction, adding a proper amount of distilled water for dissolving, and uniformly mixing to obtain a solution C;
step 3) adjusting the pH value of the solution C to 12 by using 1mol/L potassium hydroxide solution, then adding 1.5mol of benzoyl chloride solution (the mass fraction is more than 95%), stirring for 3.5h at the temperature of 100 ℃, and carrying out acylation reaction to obtain a crude product;
and 4) standing and precipitating the crude product for multiple times, and distilling the precipitate under reduced pressure to obtain a reddish brown viscous liquid, namely the coal water slurry dispersing agent.
The infrared spectrogram of the coal water slurry dispersing agent prepared in the embodiment is similar to that of the embodiment 1.
The prepared viscous liquid dispersant can be dried to obtain a solid dispersant for convenient storage and transportation.
Selecting three types of comb-shaped dispersants, lignin dispersants and naphthalene dispersants, selecting Shenfu low-rank coal for pulping, and testing the fixed viscosity concentration, the fluidity and the stability of the slurry when the addition amount of the dispersants is 0.5%.
FIG. 3 is the shear rate versus apparent viscosity of the comb-shaped dispersant prepared in example 1 for different concentrations of Shenfu low-rank coal water slurry. As can be seen from the figure, under different pulping concentrations, the apparent viscosity of the same dispersant is reduced more slowly along with the increase of the pulping concentration, and finally, the apparent viscosity of the dispersant is gradually balanced. The performance of shear thinning is shown, the prepared slurry belongs to Bingham plastic fluid, and the industrial production requirement is met.
TABLE 1 comparison of pulping effectiveness of additives
Note: a, the precipitated water accounts for less than or equal to 2 percent of the volume of the coal slurry; b-2% < the precipitated water amount is less than or equal to 5% of the volume of the coal slurry; c-5% < the precipitated water amount is less than or equal to 10% of the volume of the coal slurry; depending on the particular circumstances of stability, it may also be subdivided into "+" - "levels.
As can be seen from Table 1, by comparing the pulping experiments of the comb-shaped dispersant, the lignin dispersant and the naphthalene dispersant, the fixed viscosity concentration of the coal water slurry system added with the comb-shaped dispersant is slightly higher than that of the slurry of other dispersants under the same addition amount, and the fluidity of the coal water slurry system is better than that of the slurry of other dispersants, and the stability of the coal water slurry system is not greatly different. The comb-shaped dispersing agent contains a unit structure with 2 benzene rings, the matching degree of the comb-shaped dispersing agent and low-rank coal is higher, the more the coal surface dispersing agent is adsorbed, the stronger the effect of dispersing and viscosity reducing is, and the better the fluidity is.
Claims (4)
1. A preparation method of a graft copolymer coal water slurry dispersant is characterized by comprising the following steps:
step 1) taking a certain amount of phenol, heating and stirring for 10-15 min at 40-60 ℃, and obtaining a solution A after the phenol is melted; then adding concentrated sulfuric acid solution into the solution A, continuously stirring for 1-3 h at the temperature of 90-110 ℃, and carrying out sulfonation reaction to obtain solution B; wherein the molar ratio of phenol to concentrated sulfuric acid solution is 1: 1 to 1.4;
step 2) adding a formaldehyde solution into the solution B, stirring for 2-4 h at 80-120 ℃, carrying out polymerization reaction, adding distilled water for dissolving after the reaction is finished, and uniformly mixing to obtain a solution C; wherein the molar ratio of the formaldehyde solution to the phenol is 0.7: 1, wherein the mass fraction of the formaldehyde solution is 37%;
step 3) adjusting the pH value of the solution C to 10-12 by using an alkaline regulator, then adding a benzoyl chloride solution, stirring for 1.5-3.5 h at the temperature of 80-100 ℃, and carrying out acylation reaction to obtain a crude product; wherein the mole ratio of the benzoyl chloride solution to the phenol is 1.5: 1, the mass fraction of the benzoyl chloride solution is more than 95 percent;
and 4) standing and precipitating the crude product for multiple times, and distilling the precipitate under reduced pressure to obtain viscous liquid, namely the graft copolymer coal water slurry dispersing agent.
2. The method for preparing the graft copolymer coal-water slurry dispersant according to claim 1, wherein in the step 3), the alkaline regulator is sodium hydroxide or potassium hydroxide.
3. The method for preparing the graft copolymer coal-water slurry dispersant according to claim 1, wherein the step 4) further comprises: the viscous liquid was dried.
4. The graft copolymer coal-water slurry dispersant prepared by the preparation method of any one of claims 1 to 3, wherein the formula is
Wherein M is one of Na and K.
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Citations (6)
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| US4457762A (en) * | 1983-01-07 | 1984-07-03 | Diamond Shamrock Chemicals Company | Stabilized water slurries of carbonaceous materials |
| CN1404912A (en) * | 2002-11-08 | 2003-03-26 | 华南理工大学 | Modified lignin sulfosalt dispersant of water coal slurry |
| CN101735870A (en) * | 2009-12-16 | 2010-06-16 | 北京海淀华煤水煤浆技术开发中心 | Coal water slurry additive and preparation method and application thereof |
| CN102863599A (en) * | 2012-09-21 | 2013-01-09 | 陕西科技大学 | Preparation method of epoxy sulfonated phenolic resin coal water slurry dispersants |
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| CN107189073A (en) * | 2017-06-16 | 2017-09-22 | 陕西科技大学 | A kind of graft copolymer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2733126B2 (en) * | 1990-07-31 | 1998-03-30 | 花王株式会社 | Dispersion stabilizer for water slurry of coal powder |
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| US4457762A (en) * | 1983-01-07 | 1984-07-03 | Diamond Shamrock Chemicals Company | Stabilized water slurries of carbonaceous materials |
| CN1404912A (en) * | 2002-11-08 | 2003-03-26 | 华南理工大学 | Modified lignin sulfosalt dispersant of water coal slurry |
| CN101735870A (en) * | 2009-12-16 | 2010-06-16 | 北京海淀华煤水煤浆技术开发中心 | Coal water slurry additive and preparation method and application thereof |
| CN102863599A (en) * | 2012-09-21 | 2013-01-09 | 陕西科技大学 | Preparation method of epoxy sulfonated phenolic resin coal water slurry dispersants |
| CN103509617A (en) * | 2013-01-17 | 2014-01-15 | 湖南东盈煤化工技术开发有限公司 | Special composite coal water slurry additive for coal gasification |
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