CN102839026B - Method for producing coal water slurry additive by utilizing heterocyclic ring aromatic hydrocarbon-enriched component - Google Patents
Method for producing coal water slurry additive by utilizing heterocyclic ring aromatic hydrocarbon-enriched component Download PDFInfo
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- CN102839026B CN102839026B CN201210343450.1A CN201210343450A CN102839026B CN 102839026 B CN102839026 B CN 102839026B CN 201210343450 A CN201210343450 A CN 201210343450A CN 102839026 B CN102839026 B CN 102839026B
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Abstract
The invention relates to a method for producing a coal water slurry additive by utilizing a heterocyclic ring aromatic hydrocarbon-enriched component. The method comprises the following steps of: after mixing the heterocyclic ring aromatic hydrocarbon-enriched component and diluted materials according to a weight ratio being 3:1-7:1, carrying out sulfonation reaction through liquid sulfur trioxide (or more than or equal to 95 percent of concentrated sulfuric acid), and producing a intermediate goods benzenesulfonic acid through hydrolysis and formaldehyde condensation; and neutralizing the benzenesulfonic acid through sodium hydroxide or organic amine, dehydrating, and generating benzene sulfonate of a heterocyclic ring so as to be used as the coal water slurry additive. The coal water slurry produced by the invention has the characteristics of good storage stability and low production cost compared with that of a naphthyl product. In addition, the liquid sulfur trioxide is used as sulfonating agent to produce the heterocyclic ring benzene sulfonate coal water slurry additive, the emission of waste acid water can be reduced by more than 80 percent, and the environment protection is favored. In addition, the invention provides a novel utilization field of existing coal water slurry additive production raw materials.
Description
Technical field
The present invention relates to slurries additive agent production technical field, specifically refer to a kind of by high method of producing slurries additive agent containing heteroaromatic hydrocarbon component.
Background technology
Coal water slurry is the current comparatively a kind of clean coal technology of reality of China.Commercially available slurries additive agent is made raw material by NAPTHALENE FLAKES. (INDUSTRIAL GRADE）, adopts concentrated acid sulfonation.Its shortcoming is that the high coal water slurry production cost that causes of cost of material is high; A large amount of waste acid waters must be discharged with concentrated acid sulfonation, environmental friendliness green production can not be realized.
Summary of the invention
The invention provides a kind ofly by high method of producing slurries additive agent containing heteroaromatic hydrocarbon component, have the advantages that stability in storage is better, production cost is low compared with naphthyl product by the coal water slurry of this Additive Production.
For this reason, the technical scheme adopting is: a kind of by high method of producing slurries additive agent containing heteroaromatic hydrocarbon component, after described height is mixed with the ratio of weight ratio 3:1-7:1 containing heteroaromatic hydrocarbon component and dilution material, carry out sulfonation reaction with sulfan (or >=95% vitriol oil), after hydrolysis, formaldehyde condensation, produce middle product Phenylsulfonic acid; Again this Phenylsulfonic acid is neutralized and slough moisture with sodium hydroxide or organic amine, generate the benzene sulfonate of heterocycle, as slurries additive agent.
Described sulfonation reaction temperature is: 50-139 DEG C; Homogenizing pump discharge pressure is 0.1-1.5Mpa.
Described dilution material is from the heavy compound of aromatic device by-product, and its quality standard is: flash-point >=25 DEG C, density (20/4) >=0.85, moisture vestige, the machine < 0.03% that mixes.This diluted material >=60% is participated in sulfonation reaction, and can regulate the viscosity of slurries additive agent.
Described height is greater than 70% containing heteroaromatic hydrocarbon content in heteroaromatic hydrocarbon component.
Described height contains heteroaromatic hydrocarbon component from the cracking masout of refinery catalytic cracking unit's by-product or the tar of ethylene producing device by-product.
The application in slurries additive agent is produced of the cracking masout of described refinery catalytic cracking unit's by-product or the tar of ethylene producing device by-product.
With the coal water slurry that the present invention produces have stability in storage better, feature that production cost is low compared with naphthyl product.And make sulphonating agent with sulfan, and produce heterocycle benzene sulfonate slurries additive agent, waste acid water discharge can reduce more than 80%, is conducive to protection of the environment.The slurries additive agent product quality indicator that the present invention produces is: purity actual measurement, pH value 7-9, moisture actual measurement, the machine < 0.03% that mixes.
The present invention is raw materials used is not only the cracking masout of refinery catalytic cracking unit's by-product, can also be the tar of ethylene producing device by-product, and is not less than 70% containing heterocyclic arene; Diluted material, from the heavy compound of aromatic device by-product, provides a kind of field that utilizes of brand-new existing slurries additive agent raw materials for production.
Brief description of the drawings
Fig. 1 is process flow diagram of the present invention.
Embodiment
Embodiment 1, at 3M
3in enamel reaction still, add the diluted material containing 1.5 tons of the heteroaromatic hydrocarbon cracking masouts that is 70% and 0.5 ton of refinery catalytic cracking unit's by-product, mix and blend is warming up to 50 DEG C, the sulfan that starts input and aforementioned mixture equimolar ratio carries out sulfonation reaction, and homogenizing pump discharge pressure is 0.1-1.5Mpa.Reacting rear material enters another 3M
3in enamel reaction still, keep 135 DEG C ± 2 to continue aging reaction 2 hours.Keep 120 ± 5 DEG C to pass into water vapor hydrolysis, while reaching 15% ~ 30% to acidity, stop.Pump into the formaldehyde that accounts for weight of material 4.0%, control temperature 110 DEG C ± 5 and continue to force condensation reaction 2 hours.Be warming up to 130 DEG C ± 5, equimolar ratio pumps into sodium hydroxide and neutralizes, and generates heterocycle benzene sulfonic acid sodium salt slurries additive agent; Under whipped state, slough moisture and small part diluted material that reaction generates simultaneously.By heterocycle benzene sulfonic acid sodium salt at whipped state borehole cooling to 92 DEG C of <, slowly add water to do high speed shearing homogenizing.Continuing to be cooled to 25 DEG C ± 5, to pump into storage tank for subsequent use.This heterocycle benzene sulfonic acid sodium salt additive is joined in the fine coal powder of Jingyuan by ratio of components, and the coal water slurry product cost of producing is minimum low 5 yuan/ton compared with naphthyl product.
Embodiment 2, at 3M
3in enamel reaction still, add the diluted material containing 1.75 tons of the heteroaromatic hydrocarbon pyrolysis fuel oils that is 85% and 0.25 ton of ethylene producing device by-product, mix and blend is warming up to 60 DEG C, the sulfan of input and aforementioned mixture equimolar ratio carries out sulfonation reaction, and homogenizing pump discharge pressure is 0.1-1.5Mpa.Reacting rear material enters another 3M
3in enamel reaction still, keep 137 DEG C ± 2 to continue aging reaction 2 hours.Keep 120 ± 5 DEG C to pass into water vapor hydrolysis, while reaching 15% ~ 30% to acidity, stop.Be warming up to 145 DEG C ± 5,1:1.05 pumps into organic amine in molar ratio, generates heterocycle Phenylsulfonic acid amine slurries additive agent; Under whipped state, slough moisture and small part diluted material that reaction generates simultaneously.By heterocycle Phenylsulfonic acid amine at whipped state borehole cooling to 92 DEG C of <, slowly add water to do high speed shearing homogenizing.Continuing to be cooled to 25 DEG C ± 5, to pump into storage tank for subsequent use.This heterocycle Phenylsulfonic acid amine additive is joined in the fine coal powder of Jingyuan by ratio of components, and the coal water slurry product cost of producing is minimum low 5 yuan/ton compared with naphthyl product.
By above-described embodiment product: water: the proportional range of coal dust is that 1-10:5-35:65-80 mix, and produces coal water slurry; Finally for subsequent use to storage tank by pump delivery.Concrete: at 10M
3in carbon steel mixing tank, add water and the present invention of ratio of components, open and stir.Slowly add and grind thin coal dust and stir; Force homogenizing 1-4 hours with homogenizing pump again, pump into storage tank for subsequent use.Wherein: coal water slurry homogenization temperature is 1.0-50 DEG C; Homogenization pressures is 0.1-2.5Mpa.
Claims (5)
1. produce the method for slurries additive agent containing heteroaromatic hydrocarbon component with height for one kind, it is characterized in that: after described height is mixed with the ratio of weight ratio 3:1-7:1 containing heteroaromatic hydrocarbon component and dilution material with sulfan or >=95% vitriol oil carries out sulfonation reaction, product Phenylsulfonic acid in the middle of producing after hydrolysis, formaldehyde condensation; Again this Phenylsulfonic acid is neutralized and slough moisture with sodium hydroxide or organic amine, generate the benzene sulfonate of heterocycle, as slurries additive agent; Described height contains heteroaromatic hydrocarbon component from the cracking masout of refinery catalytic cracking unit's by-product or the tar of ethylene producing device by-product.
2. according to claim 1 a kind of by high method of producing slurries additive agent containing heteroaromatic hydrocarbon component, it is characterized in that: described sulfonation reaction temperature is: 50-139 DEG C, top hole pressure is 0.1-1.5Mpa.
3. according to claim 1 a kind of by high method of producing slurries additive agent containing heteroaromatic hydrocarbon component, it is characterized in that: described dilution material is from the heavy compound of aromatic device by-product, and its quality standard is: flash-point >=25 DEG C,
Relative density 20/4 DEG C >=0.85, moisture vestige, the machine < 0.03% that mixes, this diluted material >=60% is participated in sulfonation reaction, and can regulate the viscosity of slurries additive agent.
4. according to claim 1 a kind of by high method of producing slurries additive agent containing heteroaromatic hydrocarbon component, it is characterized in that: described height is greater than 70% containing heteroaromatic hydrocarbon content in heteroaromatic hydrocarbon component.
5. according to claim 1 a kind of by high method of producing slurries additive agent containing heteroaromatic hydrocarbon component, the application in slurries additive agent is produced of the cracking masout of described refinery catalytic cracking unit's by-product or the tar of ethylene producing device by-product.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210343450.1A CN102839026B (en) | 2012-09-17 | 2012-09-17 | Method for producing coal water slurry additive by utilizing heterocyclic ring aromatic hydrocarbon-enriched component |
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| CN201210343450.1A CN102839026B (en) | 2012-09-17 | 2012-09-17 | Method for producing coal water slurry additive by utilizing heterocyclic ring aromatic hydrocarbon-enriched component |
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| CN102839026B true CN102839026B (en) | 2014-07-09 |
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| CN105647605A (en) * | 2016-02-04 | 2016-06-08 | 常州市奥普泰科光电有限公司 | Preparation method of water-coal slurry dispersing agent |
| CN106190377A (en) * | 2016-08-24 | 2016-12-07 | 内蒙古伊泰煤制油有限责任公司 | A kind of recoverying and utilizing method of Fischer-Tropsch synthesis oil waste water |
| CN106905195B (en) * | 2017-03-10 | 2019-04-05 | 合肥工业大学 | A kind of method that styrene tar recycling and reusing prepares sulfonate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1053443A (en) * | 1989-12-21 | 1991-07-31 | 埃尼里塞尔什联合股票公司 | The technology of preparation sulfonated dispersants from petroleum asphalt fractions |
| CN1084099A (en) * | 1993-07-12 | 1994-03-23 | 安徽新源石油化工技术开发有限公司 | With catalytic cracking recycle oil solvent extract heavy aromatic hydrocarbons is the short-side chain condensed-nuclei aromatics mixed sulfonate type surfactant of raw material |
| CN101333469A (en) * | 2008-01-22 | 2008-12-31 | 南京信息工程大学 | Synthesizing and using method of coal water slurry additive agent |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1206704B (en) * | 1984-05-29 | 1989-04-27 | Anic Spa | FLUIDIFYING AND STABILIZING ADDITIVE AND ITS PREPARATION METHOD. |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1053443A (en) * | 1989-12-21 | 1991-07-31 | 埃尼里塞尔什联合股票公司 | The technology of preparation sulfonated dispersants from petroleum asphalt fractions |
| CN1084099A (en) * | 1993-07-12 | 1994-03-23 | 安徽新源石油化工技术开发有限公司 | With catalytic cracking recycle oil solvent extract heavy aromatic hydrocarbons is the short-side chain condensed-nuclei aromatics mixed sulfonate type surfactant of raw material |
| CN101333469A (en) * | 2008-01-22 | 2008-12-31 | 南京信息工程大学 | Synthesizing and using method of coal water slurry additive agent |
| 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 |
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