CN106905195B - A kind of method that styrene tar recycling and reusing prepares sulfonate - Google Patents
A kind of method that styrene tar recycling and reusing prepares sulfonate Download PDFInfo
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- CN106905195B CN106905195B CN201710140150.6A CN201710140150A CN106905195B CN 106905195 B CN106905195 B CN 106905195B CN 201710140150 A CN201710140150 A CN 201710140150A CN 106905195 B CN106905195 B CN 106905195B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
- C08F8/36—Sulfonation; Sulfation
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Structural Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of methods that styrene tar recycling and reusing prepares sulfonate, are that sulfonating agent is added into styrene tar, and styrene tar is converted to styrene tar sulfonate by sulfonating reaction.The present invention controls the sulfonation degree of styrene tar, improves its sulfonate yield by sulfonating reactions conditions such as molar ratio, reaction time, the reaction temperatures of control sulfonating agent and styrene tar.Styrene tar sulfonate contains sulfonic acid group, has hydrophily, can be used as the surfactants such as cement water reducing agent.
Description
Technical field
The present invention relates to a kind of recycling and reusing method of styrene tar, specifically a kind of styrene tar recycling
The method that recycling prepares sulfonate.Styrene tar sulfonate is prepared by sulfonating reaction, realizes in chemical production process and gives up
Waste resource utilizes.
Background technique
When industrially producing styrene using ethylbenzene as raw material, by reaction temperature, reaction pressure and water vapour/ethylbenzene ratio etc.
The influence of many factors also has a large amount of side reactions while main reaction occurs and generates.Selective dehydrogenation reaction occurs for ethylbenzene
Other than generating styrene, additionally it is possible to a variety of side reactions occur, generate hydrogen, benzene, toluene, tar, methane, ethylene, titanium dioxide
The by-products such as carbon and carbon monoxide.The reaction that process is related to is as follows:
Main reaction:
With some side reactions occur, as cracking reaction and hydrocracking are reacted.Such as:
When water vapor concentration is very high, conversion reaction occurs for vapor and ethylbenzene:
In ethylbenzene dehydrogenation technique, other than above-mentioned main reaction and side reaction occurs, other pairs can also occur for material ethylbenzene
Reaction generates α-methylstyrene, polystyrene and tar etc..Styrene is heated to will form free radical, when being heated to 120 DEG C from
It is obviously increased by base generating rate, resultant styrene is likely occurred polymerization, generates polystyrene and diphenyl ethylene derivatives etc..
If temperature is higher, during producing styrene, heat polymerization process can also be along with a degree of chain transfer reaction.
It is as follows to react skeleton symbol:
The thermal polymerization product of styrene is very complicated, and the polymer that may be generated has the polymerization of the benzene of polystyrene or more alkyl
Object, structure are as follows:
Since above-mentioned a variety of reactions can occur during production of styrene, after phenyl ethylene rectification purification, unavoidably
Ground generates high boiling point by-products produced and polymer tar residue etc., and tar residue amount can reach 1% or more of styrene yield.Benzene second
The main ingredient of various by-products and residue (rear abbreviation styrene tar) generated in alkene production be styrene polymer and
Styrene derivative, oligomer of complicated composition etc..
Domestic and international styrene tar is at present mainly by burning disposal, or directly uses as low value-added raw material.And make
For Organic Chemicals utilization, correlative study and the application for being converted into chemical products with high added-value are seldom.By to styrene coke
Oil carries out chemical conversion, produces the Organic Chemicals with high added value, realizes resource utilization, to reduce environmental pollution,
It has great application prospect.
Summary of the invention
The present invention can only can not largely be converted to high added value production for current styrene tar as fuel combustion
A kind of the problem of product, it is desirable to provide method that styrene tar recycling and reusing prepares sulfonate.By sulfonating reaction by benzene second
Alkene tar conversion contains sulfonic acid group at styrene tar sulfonate, styrene tar sulfonate, has hydrophily, can be used as
The surfactants such as cement water reducing agent.
For the present invention by the Nomenclature Composition and Structure of Complexes of analysis styrene tar, confirmation styrene tar is mainly that aromatic hydrocarbon is derivative
Object.The present invention, to the activation of aromatic ring, carries out sulfonating reaction, styrene tar is turned using heteroaryl structure in tar and alkyl
Turn to styrene tar sulfonate.There is oleophylic and hydrophilic group part from structural analysis styrene tar sulfonate, can express
Surfactant properties can be applied to cement water reducing agent etc.., it can be achieved that benzene compared with current industrial incineration method processing
The resource utilization of ethylene bottom oil creates certain economic benefit.
The method that styrene tar recycling and reusing of the present invention prepares sulfonate, is that sulfonation is added into styrene tar
Styrene tar is converted to styrene tar sulfonate by sulfonating reaction by agent.
The sulfonating agent is the concentrated sulfuric acid, oleum, chlorosulfonic acid or sulfur trioxide, the preferably concentrated sulfuric acid.It is of the present invention
The concentrated sulfuric acid refers to the sulfuric acid solution of mass concentration 98%, similarly hereinafter.
The molar ratio of the sulfonating agent and styrene tar is 1~2:1, preferably 1.2:1.
The temperature of sulfonating reaction is controlled at 120-160 DEG C, and preferably 140 DEG C, the sulfonating reaction time is 60min.The present invention
Influence of the different sulfonation temperatures to sulfonated phenylethylene tar within the scope of 25~160 DEG C is tested, preferably sulfonation temperature is 140 DEG C.
The method that styrene tar recycling and reusing of the present invention prepares sulfonate, specifically comprises the following steps:
200g styrene tar is added into the four-hole boiling flask equipped with mechanical agitator, thermometer, is added with stirring dense sulphur
Sour 222g, sulfonating reaction 60 minutes at 140 DEG C, after the reaction was completed into reaction solution be added 30%NaOH solution adjust pH value to
Reaction solution is transferred in separatory funnel by 9-11 while hot, and lower layer's water phase is put into beaker, is stood, is cooled to solid precipitation completely,
It filters, is dry to get styrene tar sodium sulfonate.
The present invention passes through the sulfonating reactions such as molar ratio, reaction time, the reaction temperature of control sulfonating agent and styrene tar
Condition controls the sulfonation degree of styrene tar, improves its sulfonate yield.
The present invention tests the sulfonating reaction under different reaction conditions.Wherein sulfonating agent type, reaction temperature, material rub
That generates different influences than equal to sulfonating reaction.
The present invention is finally selected using the concentrated sulfuric acid as sulfonating agent under the conditions of 140 DEG C, prepares styrene tar sulfonate.It is excellent
First select the concentrated sulfuric acid as sulfonating agent, be since it is considered that the concentrated sulfuric acid is cheap, it is from a wealth of sources, be easy to get.Reaction temperature
Control meets the requirement of styrene tar sulfonating reaction under the conditions of 140 DEG C, this temperature, and is easy to control.The present invention finally selects
Using the concentrated sulfuric acid and styrene tar molar ratio is condition one of of the 1.2:1 as sulfonating reaction.Test finds that molar ratio of material is
When 1:1, sulfonation rate is slower, and sulfonate yield is lower.Concentrated sulfuric acid consumption is excessive when molar ratio is 2:1, and reason may be to occur
Two sulfonation, more sulfonation phenomenons.Mole smaller, sulfonate low yield may be the progress with sulfonating reaction, in reaction system
There is water generation, concentrated sulfuric acid concentration reduces, and then reaction rate is caused to decline, and yield reduces.
The present invention prepares styrene tar sulphur by sulfonating reaction using the tar residue generated during production of styrene
Hydrochlorate realizes utilization of waste as resource in chemical production process.
The beneficial effects of the present invention are embodied in:
1, styrene tar waste is converted to high value added product by the present invention, realizes the recycling of styrene tar
It utilizes.
2, sulfonating agent needed for styrene tar sulfonation is preferably the concentrated sulfuric acid, for mature industrialization product, price compared with
It is low.Being translated into styrene tar sulfonate may be implemented huge economic benefit while realizing maximally utilizing for resource,
Meet the requirement of sustainable development.
Specific embodiment
The present invention is described further by following instance:
Embodiment 1: the concentrated sulfuric acid prepares tar sulfonate as sulfonating agent
200g styrene tar is added into the four-hole boiling flask equipped with mechanical agitator, thermometer, is added with stirring dense sulphur
30%NaOH solution is added into reaction solution after the reaction was completed and adjusts pH to 9- for sour 222g, sulfonating reaction 60 minutes at 140 DEG C
11.Reaction solution is transferred in separatory funnel while hot, lower layer's water phase is put into beaker, is stood, is cooled to solid precipitation completely, takes out
Filter, dry, weighing, obtain styrene tar sodium sulfonate solid 290g, yield 75%.
Embodiment 2: oleum prepares tar sulfonate as sulfonating agent
200g styrene tar is added into the four-hole boiling flask equipped with mechanical agitator, thermometer, is added with stirring smoke
Sulfuric acid 222g, sulfonating reaction 60 minutes at 140 DEG C, after the reaction was completed into reaction solution be added 30%NaOH solution adjust pH to
Reaction solution is transferred in separatory funnel by 9-11 while hot, and lower layer's water phase is put into beaker, is stood, is cooled to solid precipitation completely,
It filters, is dry, weighing, obtaining styrene tar sodium sulfonate solid 300g, yield 79%.
Embodiment 3: chlorosulfonic acid prepares tar sulfonate as sulfonating agent
Chlorosulfonic acid 222g is added into the four-hole boiling flask equipped with mechanical agitator, thermometer, stirs lower dropwise addition 200g benzene second
30%NaOH solution is added into reaction solution after the reaction was completed and adjusts pH to 9- for alkene tar, sulfonating reaction 60 minutes at 140 DEG C
11, reaction solution is transferred in separatory funnel while hot, lower layer's water phase is put into beaker, is stood, is cooled to solid precipitation completely, takes out
Filter, dry, weighing, obtain styrene tar sodium sulfonate solid 310g, yield 82%.
Claims (1)
1. a kind of method that styrene tar recycling and reusing prepares sulfonate, it is characterised in that: added into styrene tar
Enter sulfonating agent, styrene tar is converted to by styrene tar sulfonate by sulfonating reaction；Specifically comprise the following steps:
200g styrene tar is added into the four-hole boiling flask equipped with mechanical agitator, thermometer, is added with stirring sulfonating agent,
Sulfonating reaction 60 minutes at 140 DEG C are added 30% NaOH solution into reaction solution after the reaction was completed and adjust pH value to 9-11, while hot
Reaction solution is transferred in separatory funnel, lower layer's water phase is put into beaker, is stood, is cooled to solid precipitation completely, filters, is dry
It is dry to get styrene tar sodium sulfonate；
The sulfonating agent is the concentrated sulfuric acid；The molar ratio of the sulfonating agent and styrene tar is 1.2:1.
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| CN201710140150.6A CN106905195B (en) | 2017-03-10 | 2017-03-10 | A kind of method that styrene tar recycling and reusing prepares sulfonate |
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| CN201710140150.6A CN106905195B (en) | 2017-03-10 | 2017-03-10 | A kind of method that styrene tar recycling and reusing prepares sulfonate |
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| CN106905195B true CN106905195B (en) | 2019-04-05 |
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| CN110511783B (en) * | 2019-09-30 | 2023-09-29 | 中国石油化工股份有限公司 | Device and method for comprehensively utilizing styrene heavy distillate oil |
Citations (7)
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|---|---|---|---|---|
| US3904484A (en) * | 1972-09-07 | 1975-09-09 | Badger Co | Ethylbenzene-styrene separation |
| US3959395A (en) * | 1974-12-26 | 1976-05-25 | Monsanto Company | Recovery of polymerization inhibitor |
| CN1030908A (en) * | 1988-06-23 | 1989-02-08 | 魏清 | With deposed polystyrene, styrene tar preparation of styrene |
| CN1239133A (en) * | 1999-07-05 | 1999-12-22 | 王斌 | Sulfonated asphalt used for high-temp and -pressure drilling liquid and its preparing process |
| CN1450033A (en) * | 2002-04-10 | 2003-10-22 | 中国石油化工股份有限公司 | Adiabatic flash method for styrene tar oil |
| CN1775915A (en) * | 2005-12-01 | 2006-05-24 | 安徽工业大学 | Coal pitch fuel oil emulsifying agent and its preparing method |
| CN102839026A (en) * | 2012-09-17 | 2012-12-26 | 宋晓轩 | Method for producing coal water slurry additive by utilizing heterocyclic ring aromatic hydrocarbon-enriched component |
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2017
- 2017-03-10 CN CN201710140150.6A patent/CN106905195B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US3904484A (en) * | 1972-09-07 | 1975-09-09 | Badger Co | Ethylbenzene-styrene separation |
| US3959395A (en) * | 1974-12-26 | 1976-05-25 | Monsanto Company | Recovery of polymerization inhibitor |
| CN1030908A (en) * | 1988-06-23 | 1989-02-08 | 魏清 | With deposed polystyrene, styrene tar preparation of styrene |
| CN1239133A (en) * | 1999-07-05 | 1999-12-22 | 王斌 | Sulfonated asphalt used for high-temp and -pressure drilling liquid and its preparing process |
| CN1450033A (en) * | 2002-04-10 | 2003-10-22 | 中国石油化工股份有限公司 | Adiabatic flash method for styrene tar oil |
| CN1775915A (en) * | 2005-12-01 | 2006-05-24 | 安徽工业大学 | Coal pitch fuel oil emulsifying agent and its preparing method |
| CN102839026A (en) * | 2012-09-17 | 2012-12-26 | 宋晓轩 | Method for producing coal water slurry additive by utilizing heterocyclic ring aromatic hydrocarbon-enriched component |
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| 苯乙烯焦油的综合利用工艺开发;文卫东;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20161215;B017-1 |
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