CN104725183B - A kind of environment-friendly treatment method of hexachloro-benzene - Google Patents
A kind of environment-friendly treatment method of hexachloro-benzene Download PDFInfo
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Abstract
The invention discloses a kind of environment-friendly treatment method of hexachloro-benzene, comprises the following steps that (1) by hexachloro-benzene and active fluorinated potassium solution organic solvent, is put into single-reactor；(2) pressure testing leakage detection and nitrogen displacement are carried out to the single-reactor equipped with reaction solution；(3) single-reactor is warming up to 200~300 DEG C, boosts to 2.0~3.0MPa；10~15h is reacted under reaction temperature and reaction pressure；(4) reaction product in single-reactor is steamed, collected after condensation；(5) phenyl-hexafluoride and a chlorine phenyl-pentafluoride of rectifying separation reaction product；(6) fluorochlorobenzene (accessory substance) and organic solvent collected in single-reactor are evaporated under reduced pressure；Potassium chloride residue in single-reactor is then taken out, rejoins in single-reactor and is continuing with after then fluorochlorobenzene being dried processing.The reaction condition is gentle, and conversion ratio and yield are higher, obtains practical chemical intermediate while reducing and polluting, has a extensive future.
Description
Technical field
The present invention relates to a kind of method of comprehensive utilization of chemical byproduct, especially a kind of environmental protection treatment side of hexachloro-benzene
Method.
Background technology
Hexachloro-benzene is UNEP (United Nations Environment Program)《Convention of Stockholm on persistence organic pollutant (PoPs)》First
One of 3 class, 12 kinds of controlled chemistry materials announced are criticized, the pollution of harm and environment to human health is extremely urgent.Chlordene
Benzene has full symmetric structure, and chlorine substitution number is more, and toxicity is big, and degraded is extremely difficult.According to investigations, the country is every year in chemical industry
600 tons of hexachloro-benzenes are at least produced in production process, the hexachloro-benzene waste being mothballed has the risk of leakage and diffusion, and periphery is given birth to
Huge hidden danger be present in state Environmental security.Hexachloro-benzene is typically to be handled using simple burning method, and there may be two in burning process
Evil English, larger harm is caused to environment.Therefore actively seek high-efficiency environment friendly hexachloro-benzene processing method have it is very important
Meaning.
Dong Yuhuan et al. is prepared for a kind of new double supported bimetal catalysts：PVP-PdCl2-MnXm/MontK10-
PEG400, catalysis dechlorination is carried out to the hexachloro-benzene in aqueous phase using hydrogen migration method, reaction condition is gentle, can convert hexachloro-benzene
Rate reaches 100%, but catalyst preparation is excessively complicated, it is difficult to a large amount of productions, difficulty is separated after reaction, noble metal recovery is tired
Difficulty, the reaction time is relatively long, because solubility of the hexachloro-benzene in aqueous phase is low, so in the unit interval hexachloro-benzene treating capacity
Also it is few.
Xiao Yong et al. discusses the progress of hexachloro-benzene degraded in recent years and minimizing technology, and domestic and foreign scholars are mainly logical
Cross following methods and expand the research to hexachloro-benzene degraded, such as：Photochemical catalytic oxidation, microbial degradation, irradiation method, electrochemical process and
Catalytic hydrogenation method, degraded of these methods to hexachloro-benzene all has certain effect, but more counting methods remain in laboratory
And theoretical research stage, due to each side reason and difficulty, there is presently no the method that can be adapted to practical application.
Phenyl-hexafluoride and a chlorine phenyl-pentafluoride can synthesize a variety of doctors as the important intermediate of synthesis perfluoro aromatic compound
Medicine, agricultural chemicals, liquid crystal material and special copolymer etc., found in recent years in the research of exploitation liquid crystal material, using perfluor benzene and
The liquid-crystal compounds that one chlorine phenyl-pentafluoride derives has preferable performance, therefore has boundless development prospect.According to mesh
Preceding data shows that the study on the synthesis of phenyl-hexafluoride and a chlorine phenyl-pentafluoride is not yet carried out at home, does not retrieve relevant this aspect
Data, the research report of phenyl-hexafluoride and a chlorine phenyl-pentafluoride is also few abroad, according to the data grasped at present, phenyl-hexafluoride and one
The synthetic route of chlorine phenyl-pentafluoride mainly has following several：
Method one：Dehydrofluorination method using benzene as raw material
1956, Godsell, Stacey and Tatlow obtained hexafluoro by nine fluorine hexamethylene dehydrofluorinations in alkali lye
Benzene.But nine fluorine hexamethylenes are needed under the conditions of 150 DEG C by benzene vapour and CoF3React to prepare, conversion ratio is relatively low, limits
It is applied.
Method two：High-temperature cracking method using fluorotribromomethane as raw material
Nineteen fifty-five, Desirant report more direct and effective method：CFBr3, in 630~640 DEG C of platinotron
Pintsch process prepares phenyl-hexafluoride.
6CFBr3→C6F6+9Br2
Although this method is simple, the complexity of radical polymerization causes product also more complicated, not high, the yield of selectivity
It is low, and cost of material is high, is unfavorable for industrialized production.
Method three：Using hexachloro-benzene as raw material direct fluorination
Mcbee, Lindgren and Ligett et al., successively using BrF3、SbF5, zinc powder processing hexachloro-benzene, can be lacked
The phenyl-hexafluoride of amount, other accessory substances have the cyclohexene and cyclohexadiene compound of perfluor, fluorine chlorine.Equally it is to use hexachloro-benzene conduct
Raw material, Vorozhtsov, Platonov and Yakobson attempt to substitute chlorine atom to prepare phenyl-hexafluoride using anhydrous K F.Reaction exists
Carried out in autoclave, 450~500 DEG C of temperature, be finally separating out C6F6(yield 2l%) and incomplete fluoro fluorochlorobenzene
(C6F5C1：20%；C6F4C12：14%；C6F3C13：12%).
This method process route is short, and cost of material is low, but low there is also yield, and reactor coking is serious, limits industrialization
Application.
In summary, there is conversion ratio is relatively low, yield is low, anti-for the synthetic method of existing phenyl-hexafluoride and a chlorine phenyl-pentafluoride
Answer device coking serious, be unfavorable for the weak point of industrialized production.
The content of the invention
It is an object of the invention to provide a kind of environment-friendly treatment method of hexachloro-benzene, using chemical industry by-product hexachloro-benzene as raw material,
Using the potassium fluoride of high activity as fluorization agent, using single-reactor, phenyl-hexafluoride and the fluorine of a chlorine five are prepared under organic solvent effect
Benzene.The reaction condition is gentle, and conversion ratio and yield are higher, and practical chemical intermediate, application are obtained while reducing and polluting
Have a extensive future.
In order to solve the above-mentioned technical problem, adopt the following technical scheme that：
A kind of environment-friendly treatment method of hexachloro-benzene, it is characterised in that comprise the following steps：
(1) hexachloro-benzene and active potassium fluoride are used as raw material, by hexachloro-benzene and active fluorinated potassium solution organic solvent, shape
Into reaction solution, reaction solution is put into single-reactor；
(2) pressure testing leakage detection is carried out to the single-reactor equipped with reaction solution, after pressure testing leakage detection, be passed through into single-reactor
Nitrogen, displace the air in single-reactor；
(3) single-reactor is heated, the temperature of single-reactor starts to raise, and programming rate is controlled 2~3
DEG C/min, be warming up to 200~300 DEG C of reaction temperature, at the same by the pressure of single-reactor rise to reaction pressure 2.0~
3.0MPa；10~15h is reacted under reaction temperature and reaction pressure, after reaction terminates, stops heating and cooling；
(4) single-reactor is cooled to less than 130 DEG C, opens the air valve of single-reactor, by single-reactor
Reaction product is steamed, and condensation reaction product is simultaneously collected；
(5) reaction product of condensation is subjected to rectification process, the phenyl-hexafluoride and the fluorine of a chlorine five of reaction product is separated after rectifying
Benzene, and phenyl-hexafluoride and a chlorine phenyl-pentafluoride are collected respectively；
(6) after reaction product is run out of in step (4), it is evaporated under reduced pressure the fluorochlorobenzene (accessory substance) collected in single-reactor
And organic solvent, fluorochlorobenzene include dichloro-tetrafluoro benzene (C6F4C12), trichlorine trifluoro-benzene (C6F3C13), tetrachloro difluorobenzene
(C6F2C14), pentachloro- phenyl-monofluoride (C6FC15)；Potassium chloride residue in single-reactor is then taken out, then fluorochlorobenzene is done
Rejoin in single-reactor and be continuing with after dry processing.
After it is preferred that, the purity of hexachloro-benzene is more than 90%, and the moisture of hexachloro-benzene is less than 30ppm, before reaction, using vacuum
Drying means removes water to hexachloro-benzene.
After it is preferred that, in step (1), hexachloro-benzene and active potassium fluoride mole the ratio between be 1: (6~10).
After it is preferred that, organic solvent is tri-n-butylamine, and the mass ratio of hexachloro-benzene and tri-n-butylamine is 1: (2~10).
After it is preferred that, in step (1), processing tri-n-butylamine is dried using molecular sieve before reacting, after drying, three positive fourths
The water content of amine is less than 30ppm.
Due to using above-mentioned technical proposal, having the advantages that：
The present invention is a kind of environment-friendly treatment method of hexachloro-benzene, using chemical industry by-product hexachloro-benzene as raw material, with the fluorine of high activity
Change potassium is fluorization agent, and using single-reactor, phenyl-hexafluoride and a chlorine phenyl-pentafluoride are prepared under organic solvent effect.The reaction condition
Gently, conversion ratio and yield are higher, obtain practical chemical intermediate while reducing and polluting, have a extensive future.This hair
Bright reaction process is simple, and reaction product can be easily separated, and can largely put into production, and not only reduces production cost, and produce
Good economic benefit and environmental benefit
Phenyl-hexafluoride difficult degradation, and there is huge pollution to environment, human health is endangered, the present invention turns waste into wealth, and avoids
Phenyl-hexafluoride pollution environment, endanger human health.Meanwhile raw material proportioning of the invention, reaction temperature, reaction pressure are by preferred
Obtain, therefore reaction danger coefficient is low, feed stock conversion is high, and product purity is high, and by-products content is low.Without using catalyst, letter
Change separation process, reduce production cost.
Embodiment
The present invention is directed to hexachloro-benzene difficult degradation, and pollution and the harm of human health to environment, without using catalyst
Under conditions of, the potassium fluoride of high activity is used as fluorization agent, under conditions of tri-n-butylamine is solvent, obtains conversion ratio and yield
Higher phenyl-hexafluoride and a chlorine phenyl-pentafluoride, practical chemical intermediate is obtained while reducing and polluting.Its production process bag
Include following steps：
(1) hexachloro-benzene and active potassium fluoride are used as raw material, hexachloro-benzene and active potassium fluoride mole the ratio between be 1: (6~
10)；The purity of hexachloro-benzene is more than 90%, and the moisture of hexachloro-benzene is less than 30ppm, before reaction, using vacuum drying method pair
Hexachloro-benzene is removed water；Hexachloro-benzene and active potassium fluoride are dissolved in organic solvent, reaction solution is formed, reaction solution is put into single
In reactor；Organic solvent is tri-n-butylamine, and the mass ratio of hexachloro-benzene and tri-n-butylamine is 1: (2~10)；Before reaction, use
Molecular sieve tri-n-butylamine is dried processing, and after drying, the water content of tri-n-butylamine is less than 30ppm.
(2) pressure testing leakage detection is carried out to the single-reactor equipped with reaction solution, after pressure testing leakage detection, be passed through into single-reactor
Nitrogen, displace the air in single-reactor；
(3) single-reactor is heated, the temperature of single-reactor starts to raise, and programming rate is controlled 2~3
DEG C/min, be warming up to 200~300 DEG C of reaction temperature, at the same by the pressure of single-reactor rise to reaction pressure 2.0~
3.0MPa；10~15h is reacted under reaction temperature and reaction pressure, after reaction terminates, stops heating and cooling；
(4) single-reactor is cooled to less than 130 DEG C, opens the air valve of single-reactor, by single-reactor
Reaction product is steamed, and condensation reaction product is simultaneously collected；
(5) reaction product of condensation is subjected to rectification process, the phenyl-hexafluoride and the fluorine of a chlorine five of reaction product is separated after rectifying
Benzene, and phenyl-hexafluoride and a chlorine phenyl-pentafluoride are collected respectively；
(6) after reaction product is run out of in step (4), it is evaporated under reduced pressure the fluorochlorobenzene (accessory substance) collected in single-reactor
And organic solvent, fluorochlorobenzene include dichloro-tetrafluoro benzene (C6F4C12), trichlorine trifluoro-benzene (C6F3C13), tetrachloro difluorobenzene
(C6F2C14), pentachloro- phenyl-monofluoride (C6FC15)；Potassium chloride residue in single-reactor is then taken out, then fluorochlorobenzene is done
Rejoin in single-reactor and be continuing with after dry processing.
With reference to specific embodiment, the invention will be further described, but the present invention is not limited solely to following implementation
Example：
Embodiment 1
Hexachloro-benzene 200g, the potassium fluoride 408g of high activity are added in single-reactor, is added through dry organic molten
Agent tri-n-butylamine 2000g, to single-reactor pressure testing leakage detection and nitrogen displacement after charging.It is then turned on stirring, and slowly
280 DEG C of reaction temperature, and isothermal reaction 15h are warming up to, the pressure of single-reactor rises to 2.0~3.0Mpa of reaction pressure, with
Reaction to carry out, reaction pressure gradually rises.Reaction stops heating after terminating, and is cooled to 130 DEG C, opens the gas of single-reactor
Valve, the reaction product in single-reactor is steamed to condensation in the lump and collected, obtains phenyl-hexafluoride and a chlorine phenyl-pentafluoride；Then start to subtract
Fluorochlorobenzene (dichloro-tetrafluoro benzene, trichlorine trifluoro-benzene, tetrachloro difluorobenzene, five of incomplete fluoro in single-reactor are collected in pressure distillation
Chlorine phenyl-monofluoride) and tri-n-butylamine, then take out the potassium chloride residue in single-reactor；Meanwhile dried fluorine chlorine will be passed through
Benzene is rejoined in single-reactor and is continuing with, and reaction is completed.The yield data for measuring reaction product is shown in Table one：
| Embodiment | C6F6% | C6F5Cl% | Other fluorochlorobenzene % | Other high-boiling components % |
| 1 | 42.3 | 32.4 | 22.8 | 2.5 |
Table one
Other high-boiling components refer to other products in addition to reaction product and fluorochlorobenzene；
Embodiment 2
Hexachloro-benzene 200g, the potassium fluoride 408g of high activity are added in single-reactor, is added through dry organic molten
Agent tri-n-butylamine 2000g, to single-reactor pressure testing leakage detection and nitrogen displacement after charging.It is then turned on stirring, and slowly
200 DEG C of reaction temperature, and isothermal reaction 15h are warming up to, the pressure of single-reactor rises to 2.0~3.0Mpa of reaction pressure, with
Reaction to carry out, reaction pressure gradually rises.Reaction stops heating after terminating, and is cooled to 130 DEG C, opens the gas of single-reactor
Valve, the reaction product in single-reactor is steamed to condensation in the lump and collected, obtains phenyl-hexafluoride and a chlorine phenyl-pentafluoride；Then start to subtract
Fluorochlorobenzene (dichloro-tetrafluoro benzene, trichlorine trifluoro-benzene, tetrachloro difluorobenzene, five of incomplete fluoro in single-reactor are collected in pressure distillation
Chlorine phenyl-monofluoride) and tri-n-butylamine, then take out the potassium chloride residue in single-reactor；Meanwhile dried fluorine chlorine will be passed through
Benzene is rejoined in single-reactor and is continuing with, and reaction is completed.The yield data for measuring reaction product is shown in Table two：
| Embodiment | C6F6% | C6F5Cl% | Other fluorochlorobenzene % | Other high-boiling components % |
| 2 | 28.4 | 22.2 | 48.4 | 1.0 |
Table two
Other high-boiling components refer to other products in addition to reaction product and fluorochlorobenzene；
Embodiment 3
Hexachloro-benzene 200g, the potassium fluoride 408g of high activity are added in single-reactor, is added through dry organic molten
Agent tri-n-butylamine 2000g, to single-reactor pressure testing leakage detection and nitrogen displacement after charging.It is then turned on stirring, and slowly
230 DEG C of reaction temperature, and isothermal reaction 15h are warming up to, the pressure of single-reactor rises to 2.0~3.0Mpa of reaction pressure, with
Reaction to carry out, reaction pressure gradually rises.Reaction stops heating after terminating, and is cooled to 130 DEG C, opens the gas of single-reactor
Valve, the reaction product in single-reactor is steamed to condensation in the lump and collected, obtains phenyl-hexafluoride and a chlorine phenyl-pentafluoride；Then start to subtract
Fluorochlorobenzene (dichloro-tetrafluoro benzene, trichlorine trifluoro-benzene, tetrachloro difluorobenzene, five of incomplete fluoro in single-reactor are collected in pressure distillation
Chlorine phenyl-monofluoride) and tri-n-butylamine, then take out the potassium chloride residue in single-reactor；Meanwhile dried fluorine chlorine will be passed through
Benzene is rejoined in single-reactor and is continuing with, and reaction is completed.The yield data for measuring reaction product is shown in Table three：
| Embodiment | C6F6% | C6F5Cl% | Other fluorochlorobenzene % | Other high-boiling components % |
| 3 | 34.8 | 29.2 | 34.2 | 1.8 |
Table three
Other high-boiling components refer to other products in addition to reaction product and fluorochlorobenzene；
Embodiment 4
Hexachloro-benzene 200g, the potassium fluoride 408g of high activity are added in single-reactor, is added through dry organic molten
Agent tri-n-butylamine 2000g, to single-reactor pressure testing leakage detection and nitrogen displacement after charging.It is then turned on stirring, and slowly
260 DEG C of reaction temperature, and isothermal reaction 15h are warming up to, the pressure of single-reactor rises to 2.0~3.0Mpa of reaction pressure, with
Reaction to carry out, reaction pressure gradually rises.Reaction stops heating after terminating, and is cooled to 130 DEG C, opens the gas of single-reactor
Valve, the reaction product in single-reactor is steamed to condensation in the lump and collected, obtains phenyl-hexafluoride and a chlorine phenyl-pentafluoride；Then start to subtract
Fluorochlorobenzene (dichloro-tetrafluoro benzene, trichlorine trifluoro-benzene, tetrachloro difluorobenzene, five of incomplete fluoro in single-reactor are collected in pressure distillation
Chlorine phenyl-monofluoride) and tri-n-butylamine, then take out the potassium chloride residue in single-reactor；Meanwhile dried fluorine chlorine will be passed through
Benzene is rejoined in single-reactor and is continuing with, and reaction is completed.The yield data for measuring reaction product is shown in Table four：
| Embodiment | C6F6% | C6F5Cl% | Other fluorochlorobenzene % | Other high-boiling components % |
| 4 | 41.9 | 30.5 | 25.3 | 2.3 |
Table four
Other high-boiling components refer to other products in addition to reaction product and fluorochlorobenzene；
Embodiment 5
Hexachloro-benzene 200g, the potassium fluoride 408g of high activity are added in single-reactor, is added through dry organic molten
Agent tri-n-butylamine 2000g, to single-reactor pressure testing leakage detection and nitrogen displacement after charging.It is then turned on stirring, and slowly
300 DEG C of reaction temperature, and isothermal reaction 15h are warming up to, the pressure of single-reactor rises to 2.0~3.0Mpa of reaction pressure, with
Reaction to carry out, reaction pressure gradually rises.Reaction stops heating after terminating, and is cooled to 130 DEG C, opens the gas of single-reactor
Valve, the reaction product in single-reactor is steamed to condensation in the lump and collected, obtains phenyl-hexafluoride and a chlorine phenyl-pentafluoride；Then start to subtract
Fluorochlorobenzene (dichloro-tetrafluoro benzene, trichlorine trifluoro-benzene, tetrachloro difluorobenzene, five of incomplete fluoro in single-reactor are collected in pressure distillation
Chlorine phenyl-monofluoride) and tri-n-butylamine, then take out the potassium chloride residue in single-reactor；Meanwhile dried fluorine chlorine will be passed through
Benzene is rejoined in single-reactor and is continuing with, and reaction is completed.The yield data for measuring reaction product is shown in Table five：
| Embodiment | C6F6% | C6F5Cl% | Other fluorochlorobenzene % | Other high-boiling components % |
| 5 | 44.5 | 31.7 | 20.2 | 3.6 |
Table five
Other high-boiling components refer to other products in addition to reaction product and fluorochlorobenzene；
Comparative example 1, embodiment 2, embodiment 3, embodiment 4 and embodiment 5, it is found that when reaction temperature is higher, reaction
The yield of product is higher.
Embodiment 6
Hexachloro-benzene 200g, the potassium fluoride 227g of high activity are added in single-reactor, is added through dry organic molten
Agent tri-n-butylamine 2000g, to single-reactor pressure testing leakage detection and nitrogen displacement after charging.It is then turned on stirring, and slowly
280 DEG C of reaction temperature, and isothermal reaction 15h are warming up to, the pressure of single-reactor rises to 2.0~3.0Mpa of reaction pressure, with
Reaction to carry out, reaction pressure gradually rises.Reaction stops heating after terminating, and is cooled to 130 DEG C, opens the gas of single-reactor
Valve, the reaction product in single-reactor is steamed to condensation in the lump and collected, obtains phenyl-hexafluoride and a chlorine phenyl-pentafluoride；Then start to subtract
Fluorochlorobenzene (dichloro-tetrafluoro benzene, trichlorine trifluoro-benzene, tetrachloro difluorobenzene, five of incomplete fluoro in single-reactor are collected in pressure distillation
Chlorine phenyl-monofluoride) and tri-n-butylamine, then take out the potassium chloride residue in single-reactor；Meanwhile dried fluorine chlorine will be passed through
Benzene is rejoined in single-reactor and is continuing with, and reaction is completed.The yield data for measuring reaction product is shown in Table six：
| Embodiment | C6F6% | C6F5Cl% | Other fluorochlorobenzene % | Other high-boiling components % |
| 6 | 26.6 | 25.7 | 45.5 | 2.2 |
Table six
Other high-boiling components refer to other products in addition to reaction product and fluorochlorobenzene；
Embodiment 7
Hexachloro-benzene 200g, the potassium fluoride 302g of high activity are added in single-reactor, is added through dry organic molten
Agent tri-n-butylamine 2000g, to single-reactor pressure testing leakage detection and nitrogen displacement after charging.It is then turned on stirring, and slowly
280 DEG C of reaction temperature, and isothermal reaction 15h are warming up to, the pressure of single-reactor rises to 2.0~3.0Mpa of reaction pressure, with
Reaction to carry out, reaction pressure gradually rises.Reaction stops heating after terminating, and is cooled to 130 DEG C, opens the gas of single-reactor
Valve, the reaction product in single-reactor is steamed to condensation in the lump and collected, obtains phenyl-hexafluoride and a chlorine phenyl-pentafluoride；Then start to subtract
Fluorochlorobenzene (dichloro-tetrafluoro benzene, trichlorine trifluoro-benzene, tetrachloro difluorobenzene, five of incomplete fluoro in single-reactor are collected in pressure distillation
Chlorine phenyl-monofluoride) and tri-n-butylamine, then take out the potassium chloride residue in single-reactor；Meanwhile dried fluorine chlorine will be passed through
Benzene is rejoined in single-reactor and is continuing with, and reaction is completed.The yield data for measuring reaction product is shown in Table seven：
| Embodiment | C6F6% | C6F5Cl% | Other fluorochlorobenzene % | Other high-boiling components % |
| 7 | 26.6 | 39.8 | 26.7 | 31.3 |
Table seven
Other high-boiling components refer to other products in addition to reaction product and fluorochlorobenzene；
Comparative example 1, embodiment 6 and embodiment 7, find the mol ratio of hexachloro-benzene and active potassium fluoride in embodiment 1
Under, the yield of reaction product is higher, less side products.
Embodiment 8
Hexachloro-benzene 200g, the potassium fluoride 408g of high activity are added in single-reactor, is added through dry organic molten
Agent tri-n-butylamine 2000g, to single-reactor pressure testing leakage detection and nitrogen displacement after charging.It is then turned on stirring, and slowly
280 DEG C of reaction temperature, and isothermal reaction 10h are warming up to, the pressure of single-reactor rises to 2.0~3.0Mpa of reaction pressure, with
Reaction to carry out, reaction pressure gradually rises.Reaction stops heating after terminating, and is cooled to 130 DEG C, opens the gas of single-reactor
Valve, the reaction product in single-reactor is steamed to condensation in the lump and collected, obtains phenyl-hexafluoride and a chlorine phenyl-pentafluoride；Then start to subtract
Fluorochlorobenzene (dichloro-tetrafluoro benzene, trichlorine trifluoro-benzene, tetrachloro difluorobenzene, five of incomplete fluoro in single-reactor are collected in pressure distillation
Chlorine phenyl-monofluoride) and tri-n-butylamine, then take out the potassium chloride residue in single-reactor；Meanwhile dried fluorine chlorine will be passed through
Benzene is rejoined in single-reactor and is continuing with, and reaction is completed.The yield data for measuring reaction product is shown in Table eight：
| Embodiment | C6F6% | C6F5Cl% | Other fluorochlorobenzene % | Other high-boiling components % |
| 8 | 38.8 | 26.5 | 32.7 | 2.0 |
Table eight
Other high-boiling components refer to other products in addition to reaction product and fluorochlorobenzene；
Embodiment 9
Hexachloro-benzene 200g, the potassium fluoride 408g of high activity are added in single-reactor, is added through dry organic molten
Agent tri-n-butylamine 2000g, to single-reactor pressure testing leakage detection and nitrogen displacement after charging.It is then turned on stirring, and slowly
280 DEG C of reaction temperature, and isothermal reaction 13h are warming up to, the pressure of single-reactor rises to 2.0~3.0Mpa of reaction pressure, with
Reaction to carry out, reaction pressure gradually rises.Reaction stops heating after terminating, and is cooled to 130 DEG C, opens the gas of single-reactor
Valve, the reaction product in single-reactor is steamed to condensation in the lump and collected, obtains phenyl-hexafluoride and a chlorine phenyl-pentafluoride；Then start to subtract
Fluorochlorobenzene (dichloro-tetrafluoro benzene, trichlorine trifluoro-benzene, tetrachloro difluorobenzene, five of incomplete fluoro in single-reactor are collected in pressure distillation
Chlorine phenyl-monofluoride) and tri-n-butylamine, then take out the potassium chloride residue in single-reactor；Meanwhile dried fluorine chlorine will be passed through
Benzene is rejoined in single-reactor and is continuing with, and reaction is completed.The yield data for measuring reaction product is shown in Table nine：
| Embodiment | C6F6% | C6F5Cl% | Other fluorochlorobenzene % | Other high-boiling components % |
| 9 | 40.8 | 31.8 | 25.2 | 2.2 |
Table nine
Other high-boiling components refer to other products in addition to reaction product and fluorochlorobenzene；
Comparative example 1, embodiment 8 and embodiment 9, it is found that the reaction time is longer, the yield of reaction product is higher, by-product
Thing is fewer.
Embodiment 10
Hexachloro-benzene 200g, the potassium fluoride 408g of high activity are added in single-reactor, is added through dry organic molten
Agent tri-n-butylamine 400g, to single-reactor pressure testing leakage detection and nitrogen displacement after charging.It is then turned on stirring, and slowly rises
Temperature arrives 280 DEG C of reaction temperature, and isothermal reaction 15h, the pressure of single-reactor rise to 2.0~3.0Mpa of reaction pressure, with
Reaction is carried out, and reaction pressure gradually rises.Reaction stops heating after terminating, and is cooled to 130 DEG C, opens the gas of single-reactor
Valve, the reaction product in single-reactor is steamed to condensation in the lump and collected, obtains phenyl-hexafluoride and a chlorine phenyl-pentafluoride；Then start to subtract
Fluorochlorobenzene (dichloro-tetrafluoro benzene, trichlorine trifluoro-benzene, tetrachloro difluorobenzene, five of incomplete fluoro in single-reactor are collected in pressure distillation
Chlorine phenyl-monofluoride) and tri-n-butylamine, then take out the potassium chloride residue in single-reactor；Meanwhile dried fluorine chlorine will be passed through
Benzene is rejoined in single-reactor and is continuing with, and reaction is completed.The yield data for measuring reaction product is shown in Table ten：
| Embodiment | C6F6% | C6F5Cl% | Other fluorochlorobenzene % | Other high-boiling components % |
| 10 | 25.6 | 26.7 | 45.4 | 2.3 |
Table ten
Other high-boiling components refer to other products in addition to reaction product and fluorochlorobenzene；
Embodiment 11
Hexachloro-benzene 200g, the potassium fluoride 408g of high activity are added in single-reactor, is added through dry organic molten
Agent tri-n-butylamine 1600g, to single-reactor pressure testing leakage detection and nitrogen displacement after charging.It is then turned on stirring, and slowly
280 DEG C of reaction temperature, and isothermal reaction 15h are warming up to, the pressure of single-reactor rises to 2.0~3.0Mpa of reaction pressure, with
Reaction to carry out, reaction pressure gradually rises.Reaction stops heating after terminating, and is cooled to 130 DEG C, opens the gas of single-reactor
Valve, the reaction product in single-reactor is steamed to condensation in the lump and collected, obtains phenyl-hexafluoride and a chlorine phenyl-pentafluoride；Then start to subtract
Fluorochlorobenzene (dichloro-tetrafluoro benzene, trichlorine trifluoro-benzene, tetrachloro difluorobenzene, five of incomplete fluoro in single-reactor are collected in pressure distillation
Chlorine phenyl-monofluoride) and tri-n-butylamine, then take out the potassium chloride residue in single-reactor；Meanwhile dried fluorine chlorine will be passed through
Benzene is rejoined in single-reactor and is continuing with, and reaction is completed.The yield data for measuring reaction product is shown in Table 11：
| Embodiment | C6F6% | C6F5Cl% | Other fluorochlorobenzene % | Other high-boiling components % |
| 11 | 35.1 | 27.8 | 34.7 | 2.4 |
Table 11
Other high-boiling components refer to other products in addition to reaction product and fluorochlorobenzene；
Comparative example 1, embodiment 10 and embodiment 11, find the mass ratio of hexachloro-benzene and tri-n-butylamine in embodiment 1
When, the yield of reaction product is high, and accessory substance is few.
The specific embodiment of the present invention is these are only, but the technical characteristic of the present invention is not limited thereto.It is any with this hair
Based on bright, to solve essentially identical technical problem, essentially identical technique effect is realized, made ground simple change, etc.
With replacement or modification etc., all it is covered by among protection scope of the present invention.
Claims (2)
1. a kind of environment-friendly treatment method of hexachloro-benzene, it is characterised in that comprise the following steps：
(1) hexachloro-benzene and active potassium fluoride are used as raw material, the hexachloro-benzene and the active potassium fluoride are dissolved in organic solvent
In, reaction solution is formed, the reaction solution is put into single-reactor；Wherein, the purity of the hexachloro-benzene is described more than 90%
The moisture of hexachloro-benzene is less than 30ppm, and before reaction, the hexachloro-benzene is removed water using vacuum drying method；Described six
Chlorobenzene and the active potassium fluoride mole the ratio between be 1: (6~10)；The organic solvent is tri-n-butylamine, the hexachloro-benzene with
The mass ratio of the tri-n-butylamine is 1: (2~10)；
(2) pressure testing leakage detection is carried out to the single-reactor equipped with the reaction solution, after pressure testing leakage detection, to the single reaction
Nitrogen is passed through in device, displaces the air in the single-reactor；
(3) single-reactor is heated, the temperature of the single-reactor starts to raise, and programming rate is controlled 2
~3 DEG C/min, 200~300 DEG C of reaction temperature is warming up to, while the pressure of the single-reactor is risen into reaction pressure 2.0
~3.0MPa；10~15h is reacted under reaction temperature and reaction pressure, after reaction terminates, stops heating and cooling；
(4) single-reactor is cooled to less than 130 DEG C, opens the air valve of the single-reactor, will be described single anti-
Answer the reaction product in device to steam, condense the reaction product and collect；
(5) reaction product of condensation is subjected to rectification process, the phenyl-hexafluoride and a chlorine of the reaction product is separated after rectifying
Phenyl-pentafluoride, and the phenyl-hexafluoride and the chlorine phenyl-pentafluoride are collected respectively；
(6) after reaction product is run out of described in step (4), it is (secondary to be evaporated under reduced pressure the fluorochlorobenzene collected in the single-reactor
Product) and the organic solvent, the fluorochlorobenzene include dichloro-tetrafluoro benzene (C6F4C12), trichlorine trifluoro-benzene (C6F3C13), tetrachloro
Difluorobenzene (C6F2C14), pentachloro- phenyl-monofluoride (C6FC15)；Potassium chloride residue in the single-reactor is then taken out, then to institute
State after processing is dried in fluorochlorobenzene and rejoin in the single-reactor and be continuing with.
A kind of 2. environment-friendly treatment method of hexachloro-benzene according to claim 1, it is characterised in that：In the step (1), reaction
Preceding the tri-n-butylamine to be dried processing using molecular sieve, after drying, the water content of the tri-n-butylamine is less than 30ppm.
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