CN103157511A - Carbon-based solid sulfonic acid preparation method using waste polystyrene foam - Google Patents
Carbon-based solid sulfonic acid preparation method using waste polystyrene foam Download PDFInfo
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- CN103157511A CN103157511A CN 201110425565 CN201110425565A CN103157511A CN 103157511 A CN103157511 A CN 103157511A CN 201110425565 CN201110425565 CN 201110425565 CN 201110425565 A CN201110425565 A CN 201110425565A CN 103157511 A CN103157511 A CN 103157511A
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- polystyrene foam
- waste polystyrene
- charcoal base
- base solid
- solid sulfoacid
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Abstract
The invention relates to a carbon-based solid sulfonic acid preparation method using waste polystyrene foam. Carbon-based solid sulfonic acid prepared in the method can be used as catalytic agents prepared from biodiesel and catalytic agents for esterification reactions. The method includes the steps of dissolving the waste polystyrene foam in organic solvent, adding a little concentrated sulfuric acid in the solvent, then heating and stirring the solvent, firstly carrying out a sulfonation reaction, secondly recycling the organic solvent, and then continuously heating and partially carbonizing the organic solvent, and then filtering and washing with water and alcohol the organic solvent to obtain the carbon-based solid sulfonic acid. The preparation method has the advantages of being simple in operation, and the obtained carbon-based solid sulfonic acid is high in acid density and convenient to complement in an industrial mode, and the like. A novel method and a novel way are provided for recycle of the waste polystyrene foam.
Description
Technical field
The present invention relates to a kind of method that is prepared charcoal base solid sulfoacid by waste polystyrene foam, belong to the technical field for preparing solid acid.
Background technology
Charcoal base solid sulfoacid be a kind of take charcoal as matrix, contain sulfonic acid group, partially carbonized, the not only novel acid material of water-fast but also organic solvent-resistant, can be according to its performance applications in the acid catalyzed reaction of many chemical needs.2004, the people such as Hara (Angrew.Chem., Int.Ed., 2004,43 (22): 2955-2958) utilize sulfuric acid at 200 ℃-300 ℃, naphthalene to be carried out partly sulfonated and carbonization, synthesized the charcoal base solid sulfoacid that contains sulfonic acid group, proposed the concept of charcoal base solid sulfoacid.(the Nature such as Toda in 2005,2005 (438): 178) introduced and utilize dextrose plus saccharose first to carry out at low temperatures incomplete carbonization, then introduce sulfonic acid group by sulfuric acid sulfonation, obtained the charcoal base solid sulfoacid based on biological material, its catalytic activity is equal to sulfuric acid, Toda etc. also are applied to the synthetic of biodiesel, thereby have caused the research interest of chemist to charcoal base solid sulfoacid catalyst.Afterwards, many based on above-mentioned preparation thinking, select the preparation method of different material in succession to report, its raw materials has respectively glucose, sucrose, starch, citric acid, millet, wood powder, straw, coconut husk and furfural etc.But sulfuric acid or oleum that these methods are used are all greatly excessive, use the system of sulfuric acid to react at 200-250 ℃ for a long time, vacuum distillation is subsequently removed excessive sulfuric acid or is diluted to remove sulfuric acid with a large amount of water, all is unfavorable for a large amount of preparations of charcoal base solid sulfoacid.
On the other hand, waste polystyrene foam is the higher macromolecular material of a kind of phosphorus content, contain phenyl ring in its structure, can carry out sulfonating reaction under the concentrated sulfuric acid exists prepares flocculant and at high temperature carries out the research that carbonization prepares active carbon and have been reported (C.Grossi, et.al, Fuel, 2010,89:257-259; Wang Xichao, Jiang Rishan, chemical research and application, 2010,22 (6): 770-773; Liu Bo, Du Chunlin, Liaodong College journal, 2005,2:41-43,24; Li Haichao, Zhang Xiaoxiang, Hu Xu, chemistry of forest product and industry, 2009,29 (4): 117-120).But with a small amount of concentrated sulfuric acid, waste polystyrene foam is carried out sulfonation, then carry out at suitable temperature partially carbonized, prepare a kind of water insoluble, be insoluble to acid-base solution, the research that is insoluble to the carbon-based solid acid material of most of organic solvents yet there are no report.
Summary of the invention
For the deficiencies in the prior art, technical problem to be solved by this invention is that a kind of method that is prepared charcoal base solid sulfoacid by waste polystyrene foam is provided.Method provided by the invention is: get a certain amount of waste polystyrene foam and be dissolved in organic solvent, add under thermal agitation and carry out sulfonating reaction with the concentrated sulfuric acid.Then reclaim organic solvent, further temperature reaction is carried out partially carbonizedly, last, obtains charcoal base solid sulfoacid through filtration, washing and drying.This preparation method has avoided using a large amount of sulfuric acid, have simple to operate, the charcoal base solid sulfoacid that obtains acid density is high and be convenient to the characteristics such as industrializing implementation.
the technical scheme that the present invention solves described preparation charcoal base solid sulfoacid technical problem is, design a kind of method that is prepared charcoal base solid sulfoacid by waste polystyrene foam, this preparation method is applicable to charcoal base solid sulfoacid of the present invention, concrete technology is: waste polystyrene foam is dissolved in the mixture of one or more organic solvents, take waste polystyrene foam as primary standard substance, the concentrated sulfuric acid that adds 0.5～6 times of quality of waste polystyrene foam molal quantity, add thermal agitation, keep 50～160 ℃ of temperature, separate the water that generates, react after 0.3～6 hour, reclaim organic solvent, then continue 200～320 ℃ of heating part carbonizations 1～8 hour, filter the washing alcohol wash, can obtain charcoal base solid sulfoacid.
Compare with the charcoal base solid sulfoacid preparation method of prior art, the present invention is to provide a kind of novel preparation method.The raw material that uses is waste polystyrene foam, and the concentrated sulfuric acid amount of use is less, utilizes organic solvent first to dissolve waste polystyrene foam, reduces its volume, promotes sulfonating reaction.Preparation technology is simple simultaneously, and the charcoal base solid sulfoacid acid density that obtains is high, suitable large-scale industrial production.
The specific embodiment
Further narrate the present invention below in conjunction with embodiment.Specific embodiment does not limit claim of the present invention.
charcoal base solid sulfoacid preparation method technical scheme of the present invention is, adopt waste polystyrene foam and the concentrated sulfuric acid to prepare charcoal base solid sulfoacid, this preparation method is applicable to charcoal base solid sulfoacid of the present invention, concrete technology is: waste polystyrene foam is dissolved in cyclohexane or carbon tetrachloride and their mixture, take waste polystyrene foam as primary standard substance, the concentrated sulfuric acid that adds 1～3 times of quality of waste polystyrene foam molal quantity, add thermal agitation, keep 80～140 ℃ of temperature, separate the water that generates, react after 1～3 hour, reclaim organic solvent, then continue 200～260 ℃ of heating part carbonizations 1～8 hour, filter the washing alcohol wash, can obtain charcoal base solid sulfoacid.
The charcoal base solid sulfoacid acid density that obtains of the present invention is high, and high acid value can reach the 5.0mmol/g left and right.In the scope of applicant's retrieval, there are no using the method to prepare the bibliographical information of charcoal base solid sulfoacid.Be easy to obtain on market and the waste polystyrene foam of less expensive is synthesis material because charcoal base solid sulfoacid of the present invention adopts again, have the advantage that cost is low, be easy to industrialization and practical application.Development and utilization for waste polystyrene foam simultaneously provides a kind of new approach.
The present invention does not address part and is applicable to prior art.
Embodiment 1:
The 5.0g waste polystyrene foam is dissolved in the 30mL cyclohexane, then under agitation drips 6g 98% sulfuric acid.Reaction temperature is controlled at 80～140 ℃, reacts after 3 hours the Distillation recovery cyclohexane.Be warming up to afterwards 220 ℃, heating part carbonization 2 hours, solids adds poach to boiling, suction filtration, hot wash to filtrate are neutral, then use a small amount of ethanol washing leaching cake at least three times, drying and dehydrating can obtain charcoal base solid sulfoacid 8.2g, sour density 4.48mmol/g.
Embodiment 2:
The 5.0g waste polystyrene foam is dissolved in the 30mL carbon tetrachloride, then under agitation drips 10g 98% sulfuric acid.Reaction temperature is controlled at 80～140 ℃, reacts after 3 hours the Distillation recovery carbon tetrachloride.Be warming up to afterwards 220 ℃, heating part carbonization 3 hours, solids adds poach to boiling, suction filtration, hot wash to filtrate are neutral, then use a small amount of ethanol washing leaching cake at least three times, drying and dehydrating can obtain charcoal base solid sulfoacid 7.6g, sour density 4.62mmol/g.
Embodiment 3
The 5.0g waste polystyrene foam is dissolved in the 30mL cyclohexane, then under agitation drips 14g98% sulfuric acid.Reaction temperature is controlled at 80～140 ℃, reacts after 3 hours the Distillation recovery cyclohexane.Be warming up to afterwards 220 ℃, heating part carbonization 1 hour, solids adds poach to boiling, suction filtration, hot wash to filtrate are neutral, then use a small amount of ethanol washing leaching cake at least three times, drying and dehydrating can obtain charcoal base solid sulfoacid 8.2g, sour density 4.98mmol/g.
Embodiment 4
The 5.0g waste polystyrene foam is dissolved in the 30mL cyclohexane, then under agitation drips 14g98% sulfuric acid.Reaction temperature is controlled at 80～140 ℃, reacts after 3 hours the Distillation recovery cyclohexane.Be warming up to afterwards 260 ℃, heating part carbonization 2 hours, solids adds poach to boiling, suction filtration, hot wash to filtrate are neutral, then use a small amount of ethanol washing leaching cake at least three times, drying and dehydrating can obtain charcoal base solid sulfoacid 7.0g, sour density 2.49mmol/g.
Embodiment 5
The 5g waste polystyrene foam, the 30mL cyclohexane, the 9.5g concentrated sulfuric acid, 120～140 ℃ add hot reflux and steam cyclohexane after 1 hour.Be warming up to 200 ℃, reacted 5 hours, the solid that obtains is got 5 parts, every part of 2.0g.Part carburizing reagent 3 hours under 200,220,240,260,290 ℃ of outer bath conditions of glycerine respectively, then solids adds poach to boiling, suction filtration, hot wash to filtrate is neutral, with a small amount of ethanol washing leaching cake at least three times, drying and dehydrating obtains corresponding charcoal base solid sulfoacid, and sour density is respectively: 4.98,4.33,2.38,1.62 and 0.87mmol/g.
Claims (5)
1. method that is prepared charcoal base solid sulfoacid by waste polystyrene foam, it is characterized in that method provided by the invention is: waste polystyrene foam is dissolved in the mixture of one or more organic solvents, take waste polystyrene foam as primary standard substance, the concentrated sulfuric acid that adds 0.5～6 times of quality of waste polystyrene foam molal quantity, add thermal agitation, keep 50～160 ℃ of temperature, separate the water that generates, react after 0.3～6 hour, reclaim organic solvent, then continue 200～320 ℃ of heating part carbonizations 1～8 hour, filter the washing alcohol wash, can obtain charcoal base solid sulfoacid.
2. a kind of method that is prepared charcoal base solid sulfoacid by waste polystyrene foam according to claim 1, it is characterized in that mixture at described one or more organic solvents is that carbon atoms is the organic compound of 1～18 all kinds of hydrocarbon, halogenated hydrocarbons, alcohol, phenol, ether, aldehyde, ketone, carboxylic acid and derivative thereof, nitrogenous and sulfur-bearing, preferentially selects cyclohexane and carbon tetrachloride.
3. a kind of method that is prepared charcoal base solid sulfoacid by waste polystyrene foam according to claim 1, the molal quantity that it is characterized in that the described use concentrated sulfuric acid is 0.5～6 times of waste polystyrene foam molal quantity, preferentially selects 1～3 times.
4. a kind of method that is prepared charcoal base solid sulfoacid by waste polystyrene foam according to claim 1, it is characterized in that described reaction temperature is 50～160 ℃, more suitable temperature is 80～140 ℃, and partially carbonized more suitable temperature is 220～260 ℃.
5. a kind of method that is prepared charcoal base solid sulfoacid by waste polystyrene foam according to claim 1, is characterized in that the described reaction time is 0.3～6 hour, and the more suitable time is 1～3 hour, and the partially carbonized more suitable time is 2～3 hours.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108383108A (en) * | 2018-04-11 | 2018-08-10 | 郑州大学 | A method of graphene film is prepared on a large scale using polystyrene foam |
| CN111496178A (en) * | 2020-05-28 | 2020-08-07 | 苏州兴业材料科技股份有限公司 | Sulfonic acid curing agent for furan resin prepared from waste polystyrene and method thereof |
| CN113430022A (en) * | 2021-05-18 | 2021-09-24 | 南京大学 | Method for preparing sodium polystyrene sulfonate by sulfonating waste polystyrene and application of sodium polystyrene sulfonate in coal water slurry |
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2011
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108383108A (en) * | 2018-04-11 | 2018-08-10 | 郑州大学 | A method of graphene film is prepared on a large scale using polystyrene foam |
| CN108383108B (en) * | 2018-04-11 | 2021-06-25 | 郑州大学 | Method for preparing graphene sheet in large scale by using polystyrene foam |
| CN111496178A (en) * | 2020-05-28 | 2020-08-07 | 苏州兴业材料科技股份有限公司 | Sulfonic acid curing agent for furan resin prepared from waste polystyrene and method thereof |
| CN113430022A (en) * | 2021-05-18 | 2021-09-24 | 南京大学 | Method for preparing sodium polystyrene sulfonate by sulfonating waste polystyrene and application of sodium polystyrene sulfonate in coal water slurry |
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Application publication date: 20130619 |