CN104789285A - Rosin-based anionic coal water slurry dispersing agent and preparation method thereof - Google Patents
Rosin-based anionic coal water slurry dispersing agent and preparation method thereof Download PDFInfo
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- CN104789285A CN104789285A CN201510187559.4A CN201510187559A CN104789285A CN 104789285 A CN104789285 A CN 104789285A CN 201510187559 A CN201510187559 A CN 201510187559A CN 104789285 A CN104789285 A CN 104789285A
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- DUWJNTHAEHZXLO-UHFFFAOYSA-N CCC(C)(CCC1)C2C1(C)c1ccc(C(C)C)cc1CC2 Chemical compound CCC(C)(CCC1)C2C1(C)c1ccc(C(C)C)cc1CC2 DUWJNTHAEHZXLO-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a rosin-based anionic coal water slurry dispersing agent and a preparation method thereof. The method comprises the steps that cyanuric chloride serves as a crosslinking monomer; dehydroabietylamine and polyethylene glycol are sequentially connected in cyanuric chloride molecules via a nucleophilic substitution reaction; half ester is generated via a reaction with maleic anhydride; and finally sulphonation is performed by sodium sulfite to form the rosin-based anionic coal water slurry dispersing agent. The dispersing agent can better combine with the surface of coal, and is good in dispersity and stability and wide in applicable coal type range.
Description
Technical field
The invention belongs to coal water slurry dispersing agent technical field, particularly a kind of rosinyl anionic coal water slurry dispersing agent and preparation method thereof.
Background technology
Coal water slurry is a kind of New type coal base flow body clean fuel, by certain complete processing, the coal grain that certain particle size distributes is scattered in a kind of pulpous state coarse particles suspension system obtained in water, wherein coal accounts for 60-70%, water accounts for 29-39%, in addition also comprises the chemical additive of about 1%.Coal water slurry had both maintained the original physicochemical characteristic of coal, there is again the same mobility of oil and stability, can store, pumping, atomization and stable burning, there is the advantages such as be convenient to Cemented filling, efficiency of combustion is high, disposal of pollutants is low and cost is low.In addition, coal water slurry also can be used as gasified raw material for the production of synthesizing methanol, synthetic ammonia etc.
Apply more dispersion agent mainly naphthalenesulfonate condensation compound and sulfonated lignin condenses in the market.How to be that dispersion agent has preferably dispersing property usually, and slurry flow pattern is good, weak point is less stable, easily produces hard-caked sediment, also there is problem on the high side in addition.The major advantage of Lignins dispersion agent is abundant raw material, cheap, pulping good stability, and shortcoming is that slurrying viscosity is large, and flow pattern is coarse, and foreign matter content is large, difficult treatment.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, the object of the present invention is to provide a kind of rosinyl anionic coal water slurry dispersing agent and preparation method thereof, this dispersion agent can be formed with coal surface and better combine, and dispersed and stability is well, and has the advantages that to be suitable for coal wide ranges.
To achieve these goals, the technical solution used in the present invention is:
A kind of rosinyl anionic coal water slurry dispersing agent, its structural formula is:
Wherein, n value is 9-27.
Present invention also offers the preparation method of this rosinyl anionic coal water slurry dispersing agent, comprise the following steps:
1) 7.1g dehydroabietylamine is dissolved in 50.0g trichloromethane and makes dehydroabietylamine solution, 4.6g cyanuric chloride and 40.0g trichloromethane are added in reaction flask, 10min is stirred under ice-water bath, described dehydroabietylamine solution is dripped with dropping funnel, add in 30min, then keep system pH to be 5-6 with alkaline conditioner, ice-water bath insulation reaction is constant to pH value;
2) 10.0-29.9g polyoxyethylene glycol and 40.0g trichloromethane are added in another reaction flask, stirring and dissolving, be warming up to 35-40 DEG C, and by step 1) whole products slowly instill, 4h dropwises, then keep system pH to be 6-7 with alkaline conditioner, insulation reaction is constant to pH value;
3) 10.0-29.9g polyoxyethylene glycol and 40.0g trichloromethane are added in the 3rd reaction flask, stirring and dissolving, is warming up to 80 DEG C, condensing reflux, and by step 2) whole products slowly instill, 4h dropwises, then system pH is kept to be 7.5-8.5 with alkaline conditioner, be warming up to 100-110 DEG C to react, until reacting liquid pH value no longer reduces, be cooled to room temperature, underpressure distillation, use acetone repetitive scrubbing, dry, obtain faint yellow solid;
4) add 4.9g maleic anhydride in the reactor, be warming up to 100 DEG C and melt, by step 3) whole products add reactor, in 90-100 DEG C of insulation esterification 4h, be cooled to 60 DEG C for subsequent use;
5) in step 4) product in add 5.7-7.5g sulphonating agent, be warming up to 90-100 DEG C of insulation sulfonation 1.5-2h, cooling, obtains light yellow transparent liquid and rosinyl anionic coal water slurry dispersing agent.
Described alkaline conditioner is sodium hydroxide or potassium hydroxide.
The molecular weight of described polyoxyethylene glycol is 400-1200.
Described sulphonating agent is sodium bisulfite, S-WAT or Sodium Pyrosulfite.
Compared with prior art, beneficial effect of the present invention is embodied in:
1. a kind of rosinyl anionic coal water slurry dispersing agent prepared by the present invention, ternary aliphatic ring structure is comprised in its molecule, make can form stronger hydrophobic adsorbent effect between dispersant molecule with the same coal molecule with ring texture, thus make coal surface can more fully replace by dispersant molecule, adsorptive capacity is comparatively large, dispersed and stability is better.
2. a kind of rosinyl anionic coal water slurry dispersing agent prepared by the present invention, comprises hydrophilic Soxylat A 25-7 long-chain, sulfonic group and carboxylic acid group in its molecule.When dispersant molecule diffuses to coal surface, hydrophobic ternary aliphatic ring structure can form stronger physical adsorption with the hydrophobic region on coal surface by hydrophobic interaction, and hydrophilic Soxylat A 25-7 long-chain, sulfonic group and carboxylic acid group are then towards in water.This orientation makes coal surface by hydrophobic and change into hydrophilic, thus serves good dispersion and stabilization.
3. the rosin output of China is at the forefront in the world, and the present invention is that coal water slurry dispersing agent prepared by raw material with rosin Amine D, for the comprehensive utilization of natural product and the Molecular Structure Design of coal water slurry dispersing agent provide new thinking.
Embodiment
Embodiments of the present invention are described in detail below in conjunction with embodiment.
Embodiment 1
1) 7.1g dehydroabietylamine is dissolved in 50.0g trichloromethane and makes solution.4.6g cyanuric chloride and 40.0g trichloromethane are added in reaction flask, under ice-water bath, stirs 10min.Drip above-mentioned dehydroabietylamine solution with dropping funnel, add in 30min.Then keep system pH to be 5 with the sodium hydroxide solution that mass concentration is 10%, ice-water bath insulation reaction is constant to pH value, obtains intermediate product I.
2) 10.0g PEG-4000 and 40.0g trichloromethane are added in another reaction flask, stirring and dissolving.Be warming up to 35 DEG C, and whole intermediate product I is slowly added dropwise to reaction flask, 4h dropwises.Then keep system pH to be 6 with the sodium hydroxide solution that mass concentration is 10%, insulation reaction is constant to pH value, obtains intermediate product II.
3) add in another reaction flask by 10.0g PEG-4000 and 40.0g trichloromethane, stirring and dissolving, be warming up to 80 DEG C, condensing reflux, and whole intermediate product II is slowly added dropwise to reaction flask, 4h dropwises.Then keep system pH to be 7.5 with the sodium hydroxide solution that mass concentration is 10%, be warming up to 100 DEG C and react, until reacting liquid pH value no longer reduces.Be cooled to room temperature, underpressure distillation, use acetone repetitive scrubbing, dry, obtaining faint yellow solid is intermediate product III.
4) add 4.9g maleic anhydride in the reactor, be warming up to 100 DEG C and melt.Whole intermediate product III is added reactor, in 90 DEG C of insulation esterification 4h, is cooled to 60 DEG C, obtains intermediate product IV.
5) in whole intermediate product IV, add 6.2g sodium bisulfite, be warming up to 100 DEG C of insulation sulfonation 2h, cooling, obtains light yellow transparent liquid and rosinyl anionic coal water slurry dispersing agent.
Its structural formula is:
Wherein, n is 9.
Embodiment 2
1) 7.1g dehydroabietylamine is dissolved in 50.0g trichloromethane and makes solution.4.6g cyanuric chloride and 40.0g trichloromethane are added in reaction flask, under ice-water bath, stirs 10min.Drip above-mentioned dehydroabietylamine solution with dropping funnel, add in 30min.Then keep system pH to be 6 with the potassium hydroxide solution that mass concentration is 10%, ice-water bath insulation reaction is constant to pH value, obtains intermediate product I.
2) 15.0g polyoxyethylene glycol-600 and 40.0g trichloromethane are added in another reaction flask, stirring and dissolving.Be warming up to 40 DEG C, and whole intermediate product I is slowly added dropwise to reaction flask, 4h dropwises.Then keep system pH to be 6 with the potassium hydroxide solution that mass concentration is 10%, insulation reaction is constant to pH value, obtains intermediate product II.
3) add in another reaction flask by 15.0g polyoxyethylene glycol-600 and 40.0g trichloromethane, stirring and dissolving, be warming up to 80 DEG C, condensing reflux, and whole intermediate product II is slowly added dropwise to reaction flask, 4h dropwises.Then keep system pH to be 8.5 with the potassium hydroxide solution that mass concentration is 10%, be warming up to 100 DEG C and react, until reacting liquid pH value no longer reduces.Be cooled to room temperature, underpressure distillation, use acetone repetitive scrubbing, dry, obtaining faint yellow solid is intermediate product III.
4) add 4.9g maleic anhydride in the reactor, be warming up to 100 DEG C and melt.Whole intermediate product III is added reactor, in 100 DEG C of insulation esterification 4h, is cooled to 60 DEG C, obtains intermediate product IV.
5) in whole intermediate product IV, add 7.5g S-WAT, be warming up to 90 DEG C of insulation sulfonation 1.5h, cooling, obtains light yellow transparent liquid and rosinyl anionic coal water slurry dispersing agent.
Its structural formula is:
Wherein, n is 14.
Embodiment 3
1) 7.1g dehydroabietylamine is dissolved in 50.0g trichloromethane and makes solution.4.6g cyanuric chloride and 40.0g trichloromethane are added in reaction flask, under ice-water bath, stirs 10min.Drip above-mentioned dehydroabietylamine solution with dropping funnel, add in 30min.Then keep system pH to be 5 with the sodium hydroxide solution that mass concentration is 10%, ice-water bath insulation reaction is constant to pH value, obtains intermediate product I.
2) 29.9g polyoxyethylene glycol-1200 and 40.0g trichloromethane are added in another reaction flask, stirring and dissolving.Be warming up to 40 DEG C, and whole intermediate product I is slowly added dropwise to reaction flask, 4h dropwises.Then keep system pH to be 7 with the sodium hydroxide solution that mass concentration is 10%, insulation reaction is constant to pH value, obtains intermediate product II.
3) add in another reaction flask by 29.9g polyoxyethylene glycol-1200 and 40.0g trichloromethane, stirring and dissolving, be warming up to 80 DEG C, condensing reflux, and whole intermediate product II is slowly added dropwise to reaction flask, 4h dropwises.Then keep system pH to be 8.5 with the sodium hydroxide solution that mass concentration is 10%, be warming up to 110 DEG C and react, until reacting liquid pH value no longer reduces.Be cooled to room temperature, underpressure distillation, use acetone repetitive scrubbing, dry, obtaining faint yellow solid is intermediate product III.
4) add 4.9g maleic anhydride in the reactor, be warming up to 100 DEG C and melt.Whole intermediate product III is added reactor, in 100 DEG C of insulation esterification 4h, is cooled to 60 DEG C, obtains intermediate product IV.
5) in whole intermediate product IV, add 5.7g Sodium Pyrosulfite, be warming up to 90 DEG C of insulation sulfonation 1.5h, cooling, obtains light yellow transparent liquid and rosinyl anionic coal water slurry dispersing agent.
Its structural formula is:
Wherein, n is 27.
Embodiment 4
1) 7.1g dehydroabietylamine is dissolved in 50.0g trichloromethane and makes solution.4.6g cyanuric chloride and 40.0g trichloromethane are added in reaction flask, under ice-water bath, stirs 10min.Drip above-mentioned dehydroabietylamine solution with dropping funnel, add in 30min.Then keep system pH to be 6 with the potassium hydroxide solution that mass concentration is 10%, ice-water bath insulation reaction is constant to pH value, obtains intermediate product I.
2) 19.9g PEG-8 00 and 40.0g trichloromethane are added in another reaction flask, stirring and dissolving.Be warming up to 35 DEG C, and whole intermediate product I is slowly added dropwise to reaction flask, 4h dropwises.Then keep system pH to be 6 with the potassium hydroxide solution that mass concentration is 10%, insulation reaction is constant to pH value, obtains intermediate product II.
3) add in another reaction flask by 19.9g PEG-8 00 and 40.0g trichloromethane, stirring and dissolving, be warming up to 80 DEG C, condensing reflux, and whole intermediate product II is slowly added dropwise to reaction flask, 4h dropwises.Then keep system pH to be 8 with the potassium hydroxide solution that mass concentration is 10%, be warming up to 100 DEG C and react, until reacting liquid pH value no longer reduces.Be cooled to room temperature, underpressure distillation, use acetone repetitive scrubbing, dry, obtaining faint yellow solid is intermediate product III.
4) add 4.9g maleic anhydride in the reactor, be warming up to 100 DEG C and melt.Whole intermediate product III is added reactor, in 95 DEG C of insulation esterification 4h, is cooled to 60 DEG C, obtains intermediate product IV.
5) in whole intermediate product IV, add 7.5g S-WAT, be warming up to 95 DEG C of insulation sulfonation 1.5h, cooling, obtains light yellow transparent liquid and rosinyl anionic coal water slurry dispersing agent.
Its structural formula is:
Wherein, n is 18.
In sum, content of the present invention is not limited to cited by embodiment, and the conversion of those of ordinary skill in the art by reading specification sheets of the present invention to any equivalence that technical solution of the present invention is taked, is claim of the present invention and contains.
Effect compares: select the refined long coal in Shaanxi to be research object, by fragmentation, ore grinding, screening and grating, coal water slurry (massfraction 65%) 500g of obtained same concentrations, the size grading of coal: D (0.5)=22 μm after stirring; D (0.9)=110 μm; <75 μm=80%; <5 μm=20%; Median size=45 μm.Dispersion agent add-on is 0.4% (accounting for butt coal wt%), and the pulpability test result of dispersion agent to refined long coal that invention is implemented is as shown in table 1 below.From table 1, described in this patent, a kind of rosinyl anionic coal water slurry dispersing agent is at 24h, 48h, 72h, and the dispersion effect of 7 days and 14 days is stablized, and effect is better than commercially available naphthalenesulfonate formaldehyde condensation compound dispersion agent.
The slurry performance of each embodiment product of table 1 compares
Claims (5)
1. a rosinyl anionic coal water slurry dispersing agent, its structural formula is:
Wherein, n value is 9-27.
2. a preparation method for rosinyl anionic coal water slurry dispersing agent described in claim 1, is characterized in that, comprise the following steps:
1) 7.1g dehydroabietylamine is dissolved in 50.0g trichloromethane and makes dehydroabietylamine solution, 4.6g cyanuric chloride and 40.0g trichloromethane are added in reaction flask, 10min is stirred under ice-water bath, described dehydroabietylamine solution is dripped with dropping funnel, add in 30min, then keep system pH to be 5-6 with alkaline conditioner, ice-water bath insulation reaction is constant to pH value;
2) 10.0-29.9g polyoxyethylene glycol and 40.0g trichloromethane are added in another reaction flask, stirring and dissolving, be warming up to 35-40 DEG C, and by step 1) whole products slowly instill, 4h dropwises, then keep system pH to be 6-7 with alkaline conditioner, insulation reaction is constant to pH value;
3) 10.0-29.9g polyoxyethylene glycol and 40.0g trichloromethane are added in the 3rd reaction flask, stirring and dissolving, is warming up to 80 DEG C, condensing reflux, and by step 2) whole products slowly instill, 4h dropwises, then system pH is kept to be 7.5-8.5 with alkaline conditioner, be warming up to 100-110 DEG C to react, until reacting liquid pH value no longer reduces, be cooled to room temperature, underpressure distillation, use acetone repetitive scrubbing, dry, obtain faint yellow solid;
4) add 4.9g maleic anhydride in the reactor, be warming up to 100 DEG C and melt, by step 3) whole products add reactor, in 90-100 DEG C of insulation esterification 4h, be cooled to 60 DEG C for subsequent use;
5) in step 4) product in add 5.7-7.5g sulphonating agent, be warming up to 90-100 DEG C of insulation sulfonation 1.5-2h, cooling, obtains light yellow transparent liquid and rosinyl anionic coal water slurry dispersing agent.
3. the preparation method of rosinyl anionic coal water slurry dispersing agent according to claim 2, is characterized in that: described alkaline conditioner is sodium hydroxide or potassium hydroxide.
4. the preparation method of rosinyl anionic coal water slurry dispersing agent according to claim 2, is characterized in that: the molecular weight of described polyoxyethylene glycol is 400-1200.
5. the preparation method of rosinyl anionic coal water slurry dispersing agent according to claim 2, is characterized in that: described sulphonating agent is sodium bisulfite, S-WAT or Sodium Pyrosulfite.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114702659A (en) * | 2022-03-28 | 2022-07-05 | 江苏斯德瑞克化工有限公司 | Rosin-based defoaming agent for cleaning electronic devices and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102911313A (en) * | 2012-08-14 | 2013-02-06 | 陕西科技大学 | Preparation method of anion sulfonate type coal water slurry dispersant |
| US20130061516A1 (en) * | 2010-03-15 | 2013-03-14 | Qinzhou Aurasource Technology Inc. | Preparation method for ultra low ash coal-water slurry |
| CN104152195A (en) * | 2014-08-01 | 2014-11-19 | 陕西科技大学 | Amphoteric humate coal water slurry dispersant as well as preparation and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130061516A1 (en) * | 2010-03-15 | 2013-03-14 | Qinzhou Aurasource Technology Inc. | Preparation method for ultra low ash coal-water slurry |
| CN102911313A (en) * | 2012-08-14 | 2013-02-06 | 陕西科技大学 | Preparation method of anion sulfonate type coal water slurry dispersant |
| CN104152195A (en) * | 2014-08-01 | 2014-11-19 | 陕西科技大学 | Amphoteric humate coal water slurry dispersant as well as preparation and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114702659A (en) * | 2022-03-28 | 2022-07-05 | 江苏斯德瑞克化工有限公司 | Rosin-based defoaming agent for cleaning electronic devices and preparation method thereof |
| CN114702659B (en) * | 2022-03-28 | 2023-08-08 | 江苏斯德瑞克化工有限公司 | Rosin-based defoamer for cleaning electronic devices and preparation method thereof |
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Effective date of registration: 20220112 Address after: 713302 Xue Lu Zhen pan Zhou Cun, Qian County, Xianyang City, Xi'an City, Shaanxi Province Patentee after: XIANYANG PANZHOU MODERN AGRICULTURE CO.,LTD. Address before: 710021 Shaanxi province Xi'an Weiyang university campus of Shaanxi University of Science and Technology Patentee before: SHAANXI University OF SCIENCE & TECHNOLOGY |
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