CN101633594B - Environmental-friendly Friedel-Crafts reaction postprocessing method - Google Patents
Environmental-friendly Friedel-Crafts reaction postprocessing method Download PDFInfo
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- CN101633594B CN101633594B CN2009101847300A CN200910184730A CN101633594B CN 101633594 B CN101633594 B CN 101633594B CN 2009101847300 A CN2009101847300 A CN 2009101847300A CN 200910184730 A CN200910184730 A CN 200910184730A CN 101633594 B CN101633594 B CN 101633594B
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- reaction
- friedel
- environmental protection
- lewis acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/32—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by introduction of halogenated alkyl groups into ring compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/389—Separation; Purification; Stabilisation; Use of additives by adsorption on solids
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention discloses an environmental-friendly Friedel-Crafts reaction postprocessing method which comprises the following main steps: after the alkylation or acylation reaction of an aromatic ring is promoted by lewis acid, adsorbing reaction liquid by non-metallic mine adsorbent for appropriate time and then separating the adsorbent and the reaction liquid; adsorbing the catalyst lewis acid by the adsorbent; recovering solvent by the reaction liquid and then refining to obtain a product. The method effectively removes the lewis acid in Friedel-Crafts reaction by the non-metallic mine adsorbent, is simple, practical and environmental-friendly, has low cost and is easy to be applied in industrialized production.
Description
Technical field
The present invention relates to a kind of Friedel-Crafts reaction postprocessing method of environmental protection, relate to the lewis acidic absorption of Friedel-Crafts reaction end rear catalyst particularly and remove method.
Background technology
Fu Ke (Friedel-Crafts) reaction generates the reaction of korenyl or acyl group benzene under the Lewis acid effect for phenyl ring and halohydrocarbon or carboxylic acid halides; Friedel-Crafts reaction is one of important method of synthetic various substituted benzenes, on fine chemicals synthetic with in the industrial chemicals preparation, all obtains widespread use.Lewis acid commonly used in the Friedel-Crafts reaction is AlCl
3, TiCl
4, FeCl
3, ZnCl
2Deng.Lewis acidic use makes troubles to aftertreatment, and classic methods is to add the negatively charged ion that acid makes Lewis acid generation metal halide, for example AlCl
3Generate AlCl
4 -Be dissolved in water, and reaction product is stayed in the organic solvent, thereby reached isolating purpose.Such treatment process will certainly produce a large amount of acid waste water, brings severe contamination to environment.
Summary of the invention
The Friedel-Crafts reaction postprocessing method that the purpose of this invention is to provide a kind of environmental protection.The main sorbent material of using the nonmetalliferous ore class is removed Friedel-Crafts reaction and is finished the back lewis acid catalyst.
The present invention is achieved through following technical scheme:
A kind of Friedel-Crafts reaction postprocessing method of environmental protection comprises the following step: with Lewis acid such as AlCl
3, TiCl
4, FeCl
3, ZnCl
2After the Friedel-Crafts reaction end Deng alkylation that promotes aromatic ring or acylations; The sorbent material that in reaction solution, adds one or more nonmetalliferous ore classes; After absorption reaction for some time; The sorbent material of lewis acid catalyst has been adsorbed in removal, can directly make with extra care behind the material recovery solvent after the processing and obtain product.
The sorbent material of the nonmetalliferous ore class that the present invention adopts is one or more the mixture in following: zeyssatite, potter's clay, atlapulgite, high mountain range carclazyte, wilkinite, Attapulgite, zeolite, silica, fluorite, ls, muddy limestone; Be good with zeyssatite, atlapulgite, high mountain range carclazyte, wilkinite, Attapulgite, zeolite wherein, such sorbent material is the particulate state of indefinite form, Powdered, spherical, column or sheet.
The Lewis acid that the present invention adopts and the weight ratio of sorbent material are 1: 0.5～30, and preferable weight ratio is 1: 0.5～15.
Preferable absorption reaction temperature of the present invention is 0～60 ℃, and the preferable absorption reaction time is 10～50 minutes.
Absorption reaction of the present invention finishes the back sorbent material and separates with reaction solution, and adsorbents adsorb catalyzer Lewis acid can be used as the material of construction etc. of paving the way after the drying.After reaction solution after the adsorption treatment reclaimed solvent, product can directly be made with extra care and obtain.Reagent that the present invention is used and sorbent material are all commercially available to be got.
Positive progressive effect of the present invention is: the present invention has screened the sorbent material of nonmetalliferous ore class; After making that Friedel-Crafts reaction finishes; Remove the Lewis acid in the dereaction with sorbent material cheap and easy to get, method is simple, practical, cost is low, environmental protection, be prone to be applied to suitability for industrialized production.The present invention is through removing the catalyzer Lewis acid after Friedel-Crafts reaction finishes with absorption method; Not only overcome in the existing Friedel-Crafts reaction last handling process and to have produced the pollution problem of great amount of wastewater environment, and comparatively convenient, and cost is low; Even can refuse reclamation, reach the purpose of protection environment.
Embodiment
Through embodiment the present invention is further specified below, its purpose only is better to understand content of the present invention, and therefore, the example of being lifted does not limit protection scope of the present invention.
Embodiment 1:
In the 1000ml exsiccant four-hole boiling flask of spherical condensating tube and a TM and an addition funnel of having installed mechanical stirring, band moisture eliminator; Drop into benzene 850ml; Under agitation throw FERRIC CHLORIDE ANHYDROUS 36g, be cooled to 5 ℃, under this temperature, drip tert-butyl chloride 100ml; Dropping temperature is no more than 10 ℃, drip to finish back insulation reaction 3 hours under this temperature.After reaction is accomplished, in reaction flask, add zeyssatite 54g and stirred 10 minutes, filter, filter cake is done his in addition and is used with collecting after the benzene flushing 2 times.Merging filtrate and washing lotion get the tert.-butylbenzene bullion behind the recovery benzene.167-169 ℃/760mmHg cut is collected in bullion rectifying, gets colourless liquid tert.-butylbenzene 94.5g, content 99.6% (vapor-phase chromatography GC).
Embodiment 2:
In the 500ml exsiccant four-hole boiling flask of spherical condensating tube and a TM and an addition funnel of having installed mechanical stirring, band moisture eliminator; Drop into benzene 300ml, under agitation throw titanium tetrachloride 26ml, be cooled to 10 ℃; Under this temperature, drip tertiary amyl alcohol 40ml; Dropping temperature is no more than 10 ℃, and dropping is warming up to 60 ℃ after finishing, and insulation reaction is 1.5 hours under this temperature.After the reaction completion, reduce to room temperature, in reaction flask, add Attapulgite 75g and stirred 10 minutes, filter, collect after filter cake washes 2 times with benzene and make his usefulness in addition.Merging filtrate and washing lotion get the tert.-amylbenzene bullion behind the recovery benzene.70-75 ℃/12mmHg cut is collected in bullion rectifying, gets colourless liquid tert.-amylbenzene 38g, content 98.5% (GC).
Embodiment 3:
In the 2000ml exsiccant four-hole boiling flask of spherical condensating tube and a TM and an addition funnel of having installed mechanical stirring, band moisture eliminator; Drop into benzene 1550ml; Under agitation throw aluminum trichloride (anhydrous) 30g, be warming up to 60 ℃, under this temperature, drip 1; 2-ethylene dichloride 124g drips in one hour and finishes.Drip to finish the back 65 ℃ of insulation reaction 2 hours.Reaction solution is lowered the temperature, when question response liquid is cooled to 30 ℃, adds atlapulgite 60g and stirred 10 minutes, filter, collect after filter cake washes 2 times with benzene and make his usefulness in addition.Merging filtrate and washing lotion get 1,2-diphenylethane bullion behind the recovery benzene.132-135 ℃/10mmHg cut is collected in bullion rectifying, gets white solid 1,2-diphenylethane 186.5g, m.p.51-53 ℃, content 99.6% (GC) after the cooling.
Embodiment 4:
To being furnished with reflux exchanger, stir, add the benzene of 400ml in the four-hole boiling flask of TM and tap funnel, stir the aluminum trichloride (anhydrous) that drops into 84.1g down.At 20 ℃ of aceticanhydrides that begin to drip 30.6g, there is hydrogen chloride gas to emit thereupon.Continue to drip, in 1 hour, drip and finish.Afterwards, slowly be warming up to backflow,, treat that hydrogen chloride gas stops to get rid of the back and finishes reaction along with the hydrogen chloride gas of discharging that reacts reduces gradually.Reaction solution is reduced to 30 ℃, add wilkinite and zeyssatite mixture 170g, stirred 15 minutes, filter, collect after filter cake washes 2 times with benzene and make his usefulness in addition.Merging filtrate and washing lotion get the methyl phenyl ketone bullion behind the recovery benzene.88-89 ℃/16mmHg cut is collected in bullion rectifying, gets colourless liquid methyl phenyl ketone 25g, content 98.4% (GC).
Embodiment 5:
To being furnished with reflux exchanger, stir, add the benzene of 350ml in the 500ml four-hole boiling flask of TM and tap funnel, stir the aluminum trichloride (anhydrous) that drops into 90g down.Room temperature Dropwise 5 6g Benzoyl chloride 99min., 30 minutes dropping time.After dripping end, temperature rising reflux 2 hours is not emitted to there being hydrogen chloride gas.Reaction finishes.Reaction solution is reduced to 50 ℃, add high mountain range carclazyte 180g, stirred 30 minutes, filter, collect after filter cake washes 2 times with benzene and make his usefulness in addition.Merging filtrate and washing lotion get the UVNUL MS-40 bullion behind the recovery benzene.165-170 ℃/13mmHg cut is collected in the bullion distillation, gets white crystal UVNUL MS-40 40g, and m.p.48-50 ℃, content 99.0% (GC).
Embodiment 6:
In the 1000ml exsiccant four-hole boiling flask of spherical condensating tube and a TM and an addition funnel of having installed mechanical stirring, band moisture eliminator; Drop into benzene 500ml; Under agitation throw Zinc Chloride Anhydrous 40g; Be warming up to 75 ℃ afterwards, under this temperature, drip the mixture of 100ml benzene and 48g 4-chlorobenzyl chloride, drip and finished afterwards under this temperature insulation reaction 8 hours.After the reaction completion, reduce to room temperature and in reaction flask, add zeolite 80g stirring 10 minutes, filter, collect after filter cake washes 2 times with benzene and make his usefulness in addition.Merging filtrate and washing lotion must be to chlorodiphenyl methane bullions behind the recovery benzene.Bullion distillation, collects 148～150 ℃ /～the 20mmHg cut, must colourless liquid to chlorodiphenyl methane 42.5g, content 98.5% (GC).
Embodiment 7:
In a 5000ml exsiccant four-hole boiling flask that has installed mechanical stirring, dribbling type condensing surface and TM and addition funnel, drop into benzene 2700g, under agitation throw aluminum trichloride (anhydrous) 60g; Be warming up to 60 ℃; Under this temperature, drip 1,2-ethylene dichloride 248g drips in 1 hour and finishes.Drip to finish the back 65 ℃ of insulation reaction 2 hours.Be cooled to 30 ℃ again, obtain reaction solution.With reaction solution with volume pump with the speed of 10 milliliters of PMs from the bottom through a 500ml fluidized-bed reactor that 90g zeyssatite is housed in advance and is full of benzene; Feed nitrogen at reactor bottom simultaneously; Reactor drum insulation is at 40 ℃, after the reaction solution charging is accomplished, continues into benzene 2 hours.Collect and get 1,2-diphenylethane bullion after all reactor stream fluids concentrate recovery benzene.132-135 ℃/10mmHg cut is collected in bullion rectifying, gets white solid 1,2-diphenylethane 370g, content 99.7% after the cooling.
Embodiment 8:
In a 5000ml exsiccant four-hole boiling flask that has installed mechanical stirring, dribbling type condensing surface and TM and addition funnel, drop into benzene 2700g, under agitation throw aluminum trichloride (anhydrous) 60g; Be warming up to 60 ℃; Under this temperature, drip 1,2-ethylene dichloride 248g drips in 1 hour and finishes.Drip to finish the back 65 ℃ of insulation reaction 2 hours.Be cooled to 30 ℃ again, obtain reaction solution.With reaction solution with volume pump with the speed of 10 milliliters of PMs from the bottom through 500ml fixed-bed reactor that 450g zeyssatite are housed in advance and are full of benzene, reactor drum is incubated at 40 ℃, after the reaction solution charging is accomplished, continues into benzene 2 hours.Collect and get 1,2-diphenylethane bullion after all reactor stream fluids concentrate recovery benzene.132-135 ℃/10mmHg cut is collected in bullion rectifying, gets white solid 1,2-diphenylethane 374g, content 99.6% after the cooling.Fixed-bed reactor can be handled 5 continuously and pull on and state reaction solution in present method.
Embodiment 9:
In the 1000ml exsiccant four-hole boiling flask of spherical condensating tube and a TM and an addition funnel of having installed mechanical stirring, band moisture eliminator; Drop into benzene 748g; Under agitation throw FERRIC CHLORIDE ANHYDROUS 36g, be cooled to 5 ℃, under this temperature, drip tert-butyl chloride 84g; Dropping temperature is no more than 10 ℃, drip to finish back insulation reaction 3 hours under this temperature.Obtain reaction solution.With reaction solution with volume pump with the speed of 10 milliliters of PMs from the bottom through 500ml fixed-bed reactor that the 380g atlapulgite are housed in advance and are full of benzene, reactor drum is incubated at 40 ℃, after the reaction solution charging is accomplished, continues into benzene 2 hours.Collect and get the tert.-butylbenzene bullion after all reactor stream fluids concentrate recovery benzene.167-169 ℃/760mmHg cut is collected in bullion rectifying, gets colourless liquid tert.-butylbenzene 94g, content 99.6% (GC).Fixed-bed reactor can be handled 7 continuously and pull on and state reaction solution in present method.
Embodiment 10:
Adopt the identical reaction conditions of embodiment 1, after reaction is accomplished, in reaction flask, add zeyssatite 54g and stirred 10 minutes, filter, filter cake is done his in addition and is used with collecting after the benzene flushing 2 times.Merging filtrate and washing lotion stir and to add water 50g washing 10 minutes down, behind the standing demix, tell organic layer, and under agitation hydro-oxidation sodium solution in water layer does not gradually have the ferric hydroxide precipitate appearance in the solution.
Embodiment 11:
Present embodiment is the Comparative Examples of embodiment 1, adopts the identical reaction conditions of embodiment 1, after reaction is accomplished; In reaction flask, add water 50g gradually and stirred 10 minutes; Catalyzer is hydrolyzed, and behind the standing demix, tells organic layer; Under agitation hydro-oxidation sodium solution in water layer gradually engenders a large amount of ferric hydroxide precipitate in the solution.
Claims (8)
1. the Friedel-Crafts reaction postprocessing method of an environmental protection; It is characterized in that; Comprise the following step: promote the alkylation or acylation reaction end of aromatic ring with Lewis acid after, after reaction solution adopts nonmetalliferous ore class adsorbents adsorb reaction appropriate time, separate sorbent and reaction solution; The catalyzer Lewis acid is adsorbed agent absorption, and reaction solution carries out the refining product that obtains after the solvent recuperation;
Described nonmetalliferous ore class sorbent material is a kind of, the perhaps two or more mixture in zeyssatite, Attapulgite, atlapulgite, wilkinite, high mountain range carclazyte, the zeolite.
2. the Friedel-Crafts reaction postprocessing method of a kind of environmental protection as claimed in claim 1 is characterized in that, the particulate state that described nonmetalliferous ore class sorbent material is an indefinite form, Powdered, spherical, column or sheet.
3. the Friedel-Crafts reaction postprocessing method of a kind of environmental protection as claimed in claim 1 is characterized in that, the weight ratio of described Lewis acid and sorbent material is 1: 0.5～30.
4. the Friedel-Crafts reaction postprocessing method of a kind of environmental protection as claimed in claim 3 is characterized in that, the weight ratio of described Lewis acid and sorbent material is 1: 0.5～15.
5. the Friedel-Crafts reaction postprocessing method of a kind of environmental protection as claimed in claim 1 is characterized in that, described absorption reaction is carried out under whipped state.
6. the Friedel-Crafts reaction postprocessing method of a kind of environmental protection as claimed in claim 1 is characterized in that, the form of sorbent material being dressed up fixed-bed reactor or fluidized-bed reactor is adopted in described absorption reaction, and reaction solution feeds the reactor drum mode to carry out.
7. the Friedel-Crafts reaction postprocessing method of a kind of environmental protection as claimed in claim 1 is characterized in that, described absorption reaction temperature is 0～60 ℃.
8. the Friedel-Crafts reaction postprocessing method of a kind of environmental protection as claimed in claim 1 is characterized in that, the described absorption reaction time is 10～50 minutes.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101847300A CN101633594B (en) | 2009-08-20 | 2009-08-20 | Environmental-friendly Friedel-Crafts reaction postprocessing method |
| PCT/CN2009/074668 WO2011020255A1 (en) | 2009-08-20 | 2009-10-28 | Environment-friendly post-treatment method for friedel-crafts reaction |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009101847300A CN101633594B (en) | 2009-08-20 | 2009-08-20 | Environmental-friendly Friedel-Crafts reaction postprocessing method |
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| CN101633594A CN101633594A (en) | 2010-01-27 |
| CN101633594B true CN101633594B (en) | 2012-12-05 |
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| WO (1) | WO2011020255A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101633594B (en) * | 2009-08-20 | 2012-12-05 | 镇江市海通化工有限公司 | Environmental-friendly Friedel-Crafts reaction postprocessing method |
| CN103319298B (en) * | 2013-06-26 | 2015-09-02 | 四川东材科技集团股份有限公司 | Louis acid catalysis prepares the method for phenyl ethylbenzene ethane capacitor insulation oil |
| CN104276925B (en) * | 2013-07-10 | 2016-02-24 | 江苏英力科技发展有限公司 | One prepares 2, and 2 ', 4,4 ', 6, the method for 6 '-hexamethyl bibenzyl |
| CN107759812B (en) * | 2017-10-10 | 2020-12-15 | 深圳大学 | Crosslinked polymer based on waste polystyrene, and preparation method and application thereof |
| CN107803156A (en) * | 2017-11-09 | 2018-03-16 | 大丰鑫源达化工有限公司 | A kind of new speed up gas and liquid or the device of liquid liquid mixing |
| CN109456138A (en) * | 2018-10-25 | 2019-03-12 | 泰州百力化学股份有限公司 | A kind of method and its continuous device of ionic liquid-catalyzed synthesis 1,2- diphenylethane |
| CN114133058B (en) * | 2021-10-29 | 2024-02-20 | 山东京博农化科技股份有限公司 | Friedel-crafts reaction aluminum-containing wastewater recycling method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5126487A (en) * | 1991-03-26 | 1992-06-30 | The Procter & Gamble Company | Process for the preparation of 2-alkyl-4-acyl-6-tert-butylphenol compounds |
| US5300721A (en) * | 1990-08-27 | 1994-04-05 | Nippon Steel Chemical Co., Ltd. | Method for separating 2,6-diethylnaphthalene |
| CN101058587A (en) * | 2006-04-20 | 2007-10-24 | 天津科技大学 | Bi(4-(4-fluorobenzoyl)phenyl)phenyl phosphine oxide monomer and synthetic method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101633594B (en) * | 2009-08-20 | 2012-12-05 | 镇江市海通化工有限公司 | Environmental-friendly Friedel-Crafts reaction postprocessing method |
-
2009
- 2009-08-20 CN CN2009101847300A patent/CN101633594B/en not_active Expired - Fee Related
- 2009-10-28 WO PCT/CN2009/074668 patent/WO2011020255A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5300721A (en) * | 1990-08-27 | 1994-04-05 | Nippon Steel Chemical Co., Ltd. | Method for separating 2,6-diethylnaphthalene |
| US5126487A (en) * | 1991-03-26 | 1992-06-30 | The Procter & Gamble Company | Process for the preparation of 2-alkyl-4-acyl-6-tert-butylphenol compounds |
| CN101058587A (en) * | 2006-04-20 | 2007-10-24 | 天津科技大学 | Bi(4-(4-fluorobenzoyl)phenyl)phenyl phosphine oxide monomer and synthetic method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张祯等.微波辅助的Friede1-Crafts反应.《化学进展》.2008,第20卷(第2/3期),312-317. * |
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| CN101633594A (en) | 2010-01-27 |
| WO2011020255A1 (en) | 2011-02-24 |
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