CN110372471A - The catalysis conversion method of hexachlorobutadiene - Google Patents
The catalysis conversion method of hexachlorobutadiene Download PDFInfo
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- CN110372471A CN110372471A CN201910682832.9A CN201910682832A CN110372471A CN 110372471 A CN110372471 A CN 110372471A CN 201910682832 A CN201910682832 A CN 201910682832A CN 110372471 A CN110372471 A CN 110372471A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/087—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated halogenated hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/21—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms with simultaneous increase of the number of halogen atoms
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Abstract
The invention discloses a kind of catalysis conversion methods of pollutant hexachlorobutadiene, using hexachlorobutadiene and anhydrous hydrogen fluoride as raw material, in the presence of liquid-phase fluorination catalyst and catalyst aid, synthesis obtains 2- chloro- 1,1,1,4,4,4- hexafluoro -2- butylene and 1,2- bis- chloro- 1,1, the mixture of 4,4,4- five fluoro- 2- butylene.The present invention provides a kind of catalysis conversion methods of pollutant, are mainly used for the green conversion of hexachlorobutadiene.
Description
Technical field
The present invention relates to a kind of method for transformation of pollutant more particularly to the catalyzed conversions of hexachlorobutadiene.
Background technique
The environmental problems such as water pollution have become one of challenge of human survival, the pair that when industrial production tetrachloro-ethylene generates
Product hexachlorobutadiene is one of ten kinds of water pollutants, can be done great damage to water body, soil etc..As the mankind are to water
The attention of the environmental problems such as matter, there is an urgent need to find the conversion scheme of this pollutant.
Hexachlorobutadiene boiling point is 210-220 DEG C, has perchloro- diene structure, and chemical property is highly stable, it is difficult to carry out
Chemical reaction, the conversion process of existing hexachlorobutadiene often use the fluoride of chemical quantity to react with hexachlorobutadiene, are fluorinated
Object be it is disposable, can not circular regeneration, industrial applicability is poor.
Currently, about 3000 tons of hexachlorobutadiene annual output, due to lacking suitable catalysis conversion method, environmental pollution is extremely
Seriously, it is badly in need of the feasible conversion scheme of industry, document report is urged using anhydrous hydrogen fluoride and hexachlorobutadiene as raw material through liquid phase
Change fluorination reaction, can convert pollutant hexachlorobutadiene to fluorine chemical intermediate 2- chloro- 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- fourths
Alkene, scheme have step short, and commercial viability is high, are ideal hexachlorobutadiene green conversion schemes.
The key of hexachlorobutadiene and anhydrous hydrogen fluoride reaction is the design of liquid-phase fluorination catalyst system, due to traditional liquid
The disadvantages of phase fluorination catalysts Antimony pentachloride exists, and valence state reduces inactivation, thermal stability is poor, and the reactivity of hexachlorobutadiene
Low, stability is high, and therefore, Yao Shixian hexachlorobutadiene is reacted with the catalysis of the circulation of anhydrous hydrogen fluoride, and it is steady that urgent need develops a kind of heat
Qualitative height, acid strong and stable liquid phase fluorination reaction catalyst system, patent CN 103193586B, CN 104072333B report
A kind of liquid phase fluorination reaction of hexachlorobutadiene and anhydrous hydrogen fluoride in road, although reaction conversion ratio selectivity is higher, due to
Traditional metal antimony catalyst is used, it is difficult to realize catalytic cycle, it is disposable, less economical, environment that catalyst, which uses,
It pollutes also big；Patent CN 106008147A reports the gas phase fluorination of a kind of hexachlorobutadiene and anhydrous hydrogen fluoride, although
The problems such as reaction conversion ratio is high, but that there are selectivity of product is poor, and catalyst life is short.
Summary of the invention
Can be recycled the technical problem to be solved by the present invention is in view of the deficiencies of the prior art, providing a kind of catalyst,
The high hexachlorobutadiene catalyzed conversion scheme of selectivity of product.
The method for transformation of hexachlorobutadiene of the present invention uses hexachlorobutadiene and anhydrous hydrogen fluoride for raw material,
In the presence of liquid-phase fluorination catalyst, catalyst aid and solvent, synthesis obtains 2- chloro- 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene and
1,2- bis- chloro- 1, Isosorbide-5-Nitrae, the mixture of 4,4- five fluoro- 2- butylene, reaction equation is as follows:
Wherein, liquid-phase fluorination catalyst is oxide, chloride or the fluoride of titanium, alum, niobium or tantalum, and catalyst aid is alkane
Base amine, alkylphosphines or alkyl sulfonic acid, solvent are sulfuric acid, halogenated hydrocarbons or ionic liquid；Reaction condition are as follows: hexachlorobutadiene with it is anhydrous
Hydrogen fluoride molar ratio is 6~20:1, and the molar ratio of liquid-phase fluorination catalyst and hexachlorobutadiene is 0.25~2:1, catalyst aid
It is 1~10:1 with the molar ratio of hexachlorobutadiene, the molar ratio of solvent and hexachlorobutadiene is 1~50:1, reaction temperature 50
~200 DEG C, the reaction time is 2~8h.
The liquid-phase fluorination catalyst is titanium dioxide, vanadium pentoxide, niobium pentaoxide, tantalum pentoxide, tetrachloro
Change titanium, phosphoric alum, columbium pentachloride, tantalic chloride or titanium tetrafluoride, five fluorination alum, niobium (Nb) pentafluoride, tantalum pentafluoride.
The catalyst aid is tripropylamine, tri-butylamine, tripropyl phosphine, tributylphosphine, potassium fluoride, sodium fluoride, sulphur
Or mixtures thereof potassium hydrogen phthalate, potassium sulfate, chlorosulfonic acid potassium, fluosulfonic acid potassium, trifluoromethanesulfonic acid potassium, benzene sulfonic acid potassium.
The solvent is 1,2- dichloroethanes, anhydrous slufuric acid, sulfonic acid, chlorosulfonic acid, fluosulfonic acid, trifluoromethanesulfonic acid or benzene sulphur
Or mixtures thereof acid.
The bis- fluoro- 2- fourth of chloro- 1,1,4,4,4- five of the chloro- 1,1,1,4,4,4- hexafluoro -2- butylene of the product 2- and 1,2-
Alkene includes two kinds of configurations of cis and trans.
The reaction condition is hexachlorobutadiene and anhydrous hydrogen fluoride molar ratio is 10~15:1, liquid-phase fluorination catalyst
Be 0.5~1.5:1 with the molar ratio of hexachlorobutadiene, the molar ratio of catalyst aid and hexachlorobutadiene is 2~8:1, solvent with
The molar ratio of hexachlorobutadiene is 5~25:1, and reaction temperature is 80~180 DEG C, and the reaction time is 3~6h.
The present invention has the advantages that
(1) hexachlorobutadiene thermal stability is high, reactivity is low, using Traditional liquid phase fluorination catalyst Antimony pentachloride, urges
Agent can not be recycled, and catalyst thermal stability is poor, and metallic antimony is easy to be reduced to trivalent by pentavalent, lead to catalyst inactivation,
Although being passed through chlorine is able to maintain quinquevalence antimony, the selectivity of product, by-product dichloro hexafluorobutene poison can be reduced using chlorine
Property it is higher, and under optimum condition of the present invention, hexachlorobutadiene be can reach close to 100% conversion, and batch process uses catalyst energy
It is enough recycled 15-20 times, therefore, the present invention has higher prospects for commercial application；(2) Traditional liquid phase fluorination catalyst pentachloro-
It is extremely strong to change metaantimmonic acid, often results in reaction kettle corrosion leakage, brings great security risk, the liquid-phase fluorination catalysis that the present invention designs
Agent system, acidity are lower than Antimony pentachloride, significantly reduce to the corrosion of stainless steel cauldron, therefore, reaction it is highly-safe.
Specific embodiment
Below by specific embodiment, invention is further described in detail, but not does in any form to the present invention
Limitation.
Embodiment 1:
45 grams of vanadium pentoxides of addition into 300mL stainless steel band stirring autoclave, 50 grams of anhydrous hydrogen fluorides, 20 grams
Potassium fluoride and 10 grams of anhydrous slufuric acids are warming up to 100 DEG C of reactions, vacuumize removing superfluous water after above-mentioned reaction solution is stirred at room temperature
Point.
Into kettle be added 52 grams of hexachlorobutadienes, 40 grams of anhydrous hydrogen fluorides, after be warming up to 150 DEG C of reactions 3-4 hours, control
Pressure is 1.5-1.7MPa, and discharge material is collected with cold-trap.
Product is after rectifying separates, nuclear-magnetism detection, and data are as follows:
1H NMR(500MHz,CDCl3) δ 6.64 (q, 1H, J=6.5Hz)；
13C NMR(500MHz,CDCl3) δ 132.0 (qq, J=39.3Hz, J=5.4Hz), 121.9 (q, J=37.5Hz),
120.6 (q, J=270Hz), 119.1 (q, J=272.5Hz)；
19F NMR(470MHz,CDCl3)δ-71.3(m,CF3),-61.3(m,CF3).
Above-mentioned data prove that it is exactly the chloro- 1,1,1,4,4,4- hexafluoro -2- butylene of 2- that product, which is made,.
1H NMR(500MHz,CDCl3) δ 6.60 (q, 1H, J=5Hz)；
13C NMR(500MHz,CDCl3) δ 136.8 (tq, J=129Hz, J=21.5Hz), 122.0 (t, J=1161Hz),
121.9 (t, J=1080Hz), 119.8 (qt, J=200Hz, J=20.5Hz)；
19F NMR(470MHz,CDCl3)δ-60.7(m,CF3),-57.8(m,CF3).
Above-mentioned data prove that it is exactly the fluoro- 2- butylene of the chloro- 1,1,4,4,4- five of 1,2- that product, which is made,.
Embodiment 2~8
Embodiment 2~8 prepares the chloro- 1,1,1,4,4,4- hexafluoro -2- fourth of 2- according to preparation method identical in embodiment 1
Alkene, except that the catalyst in embodiment 1 is vanadium pentoxide, and telomerization ratio is respectively titanium dioxide in embodiment 2~8
Titanium, niobium pentaoxide, tantalum pentoxide, titanium tetrachloride, phosphoric alum, columbium pentachloride, tantalic chloride.The reaction of embodiment 2~8
The results are shown in Table 1.
1 catalyst screening of table
Embodiment 9~13:
Embodiment 9~13 prepares the chloro- 1,1,1,4,4,4- hexafluoro -2- fourth of 2- according to preparation method identical in embodiment 1
Alkene except that the catalyst aid in embodiment 1 is potassium fluoride, and is respectively tripropylamine, tributyl in embodiment 9~13
Phosphine, potassium acid sulfate, chlorosulfonic acid potassium, benzene sulfonic acid potassium.The reaction result of embodiment 9~13 is as shown in table 2.
The screening of 2 catalyst aid of table
| Embodiment | Catalyst aid | Yield (%) |
| 9 | Tripropylamine | 52.8 |
| 10 | Tributylphosphine | 44.2 |
| 11 | Potassium acid sulfate | 62.6 |
| 12 | Chlorosulfonic acid potassium | 66.6 |
| 13 | Benzene sulfonic acid potassium | 57.6 |
Embodiment 14~17:
Embodiment 14~17 prepares the chloro- 1,1,1,4,4,4- hexafluoro -2- fourth of 2- according to preparation method identical in embodiment 1
Alkene, except that in embodiment 1 using solvent be anhydrous slufuric acid, and in embodiment 14~17 be respectively 1,2- dichloroethanes,
Chlorosulfonic acid, trifluoromethanesulfonic acid or benzene sulfonic acid.The reaction result of embodiment 14~17 is as shown in table 3.
The influence of 3 solvent of table
| Embodiment | Solvent | Yield (%) |
| 14 | 1,2- dichloroethanes | 50.9 |
| 15 | Chlorosulfonic acid | 71.7 |
| 16 | Trifluoromethanesulfonic acid | 75.0 |
| 17 | Benzene sulfonic acid | 52.3 |
Embodiment 18~21:
Embodiment 18~21 prepares the chloro- 1,1,1,4,4,4- hexafluoro -2- fourth of 2- according to preparation method identical in embodiment 1
Alkene, except that hexachlorobutadiene and anhydrous hydrogen fluoride molar ratio are 12:1 in embodiment 1, and divide in embodiment 18~21
It Wei not 6:1,10:1,15:1,20:1.The reaction result of embodiment 18~21 is as shown in table 4.
The influence of 4 reaction ratio of table
| Embodiment | Molar ratio | Yield (%) |
| 18 | 6:1 | 47.5 |
| 19 | 10:1 | 63.7 |
| 20 | 15:1 | 68.8 |
| 21 | 20:1 | 40.3 |
Embodiment 22~25:
Embodiment 22~25 prepares the chloro- 1,1,1,4,4,4- hexafluoro -2- fourth of 2- according to preparation method identical in embodiment 1
Alkene, except that the molar ratio of liquid-phase fluorination catalyst and hexachlorobutadiene is 1:1 in embodiment 1, and embodiment 22~25
In be respectively 0.25:1,0.5:1,1.5:1,2:1.The reaction result of embodiment 22~25 is as shown in table 5.
The influence of 5 catalyst ratio of table
| Embodiment | Catalyst amount | Yield (%) |
| 22 | 0.25:1 | 34.0 |
| 23 | 0.5:1 | 54.1 |
| 24 | 1.5:1 | 63.0 |
| 25 | 2:1 | 45.1 |
Embodiment 26~29:
Embodiment 26~29 prepares the chloro- 1,1,1,4,4,4- hexafluoro -2- fourth of 2- according to preparation method identical in embodiment 1
Alkene, except that the molar ratio of catalyst aid and hexachlorobutadiene is 3:1 in embodiment 1, and in embodiment 26~29 respectively
For 1:1,2.5:1,5:1,10:1.The reaction result of embodiment 26~29 is as shown in table 6.
The influence of 6 catalyst aid ratio of table
| Embodiment | Catalyst amount | Yield (%) |
| 26 | 1:1 | 28.7 |
| 27 | 2.5:1 | 44.4 |
| 28 | 5:1 | 56.8 |
| 29 | 10:1 | 41.4 |
Embodiment 30~34:
Embodiment 30~34 prepares the chloro- 1,1,1,4,4,4- hexafluoro -2- fourth of 2- according to preparation method identical in embodiment 1
Alkene, except that the molar ratio of catalyst aid and hexachlorobutadiene is 10:1 in embodiment 1, and in embodiment 30~34 respectively
For 1:1,5:1,15:1,25:1 and 50:1.The reaction result of embodiment 30~34 is as shown in table 7.
The influence of 7 solvent ratios of table
| Embodiment | Solvent ratios | Yield (%) |
| 30 | 1:1 | 15.6 |
| 31 | 5:1 | 31.1 |
| 32 | 15:1 | 53.5 |
| 33 | 25:1 | 57.0 |
| 34 | 50:1 | 28.4 |
Claims (6)
1. a kind of method for transformation of hexachlorobutadiene, it is characterised in that using hexachlorobutadiene and anhydrous hydrogen fluoride as raw material, in liquid
In the presence of phase fluorination catalysts, catalyst aid and solvent, synthesis obtains 2- chloro- 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene and 1,2-
Two chloro- 1, Isosorbide-5-Nitrae, the mixture of 4,4- five fluoro- 2- butylene, wherein liquid-phase fluorination catalyst be titanium, alum, niobium or tantalum oxide,
Chloride or fluoride, catalyst aid are alkylamine, alkylphosphines or alkyl sulfonic acid, and solvent is sulfuric acid, halogenated hydrocarbons or ionic liquid；
Reaction condition are as follows: hexachlorobutadiene and anhydrous hydrogen fluoride molar ratio are 6~20:1, liquid-phase fluorination catalyst and hexachlorobutadiene
Molar ratio is 0.25~2:1, and the molar ratio of catalyst aid and hexachlorobutadiene is 1~10:1, and solvent and hexachlorobutadiene rub
You are than being 1~50:1, and reaction temperature is 50~200 DEG C, and the reaction time is 2~8h.
2. the method for transformation of hexachlorobutadiene according to claim 1, it is characterised in that the liquid-phase fluorination catalyst is
It is titanium dioxide, vanadium pentoxide, niobium pentaoxide, tantalum pentoxide, titanium tetrachloride, phosphoric alum, columbium pentachloride, phosphoric
Tantalum, titanium tetrafluoride, five fluorination alum, niobium (Nb) pentafluoride or tantalum pentafluoride.
3. the method for transformation of hexachlorobutadiene according to claim 1, it is characterised in that catalyst aid is tripropylamine, three
Butylamine, tripropyl phosphine, tributylphosphine, potassium fluoride, sodium fluoride, potassium acid sulfate, potassium sulfate, chlorosulfonic acid potassium, fluosulfonic acid potassium, trifluoro
Or mixtures thereof methanesulfonic acid potassium or benzene sulfonic acid potassium.
4. the method for transformation of hexachlorobutadiene according to claim 1, it is characterised in that solvent is anhydrous slufuric acid, 1,2- bis-
Or mixtures thereof chloroethanes, chlorosulfonic acid, fluosulfonic acid, trifluoromethanesulfonic acid or benzene sulfonic acid.
5. the method for transformation of hexachlorobutadiene according to claim 1, it is characterised in that product 2- chloro- 1,1, Isosorbide-5-Nitrae, 4,4-
Hexafluoro -2- butylene and the bis- fluoro- 2- butylene of chloro- 1,1,4,4,4- five of 1,2- include two kinds of configurations of cis and trans.
6. the method for transformation of hexachlorobutadiene according to claim 1, it is characterised in that reaction condition is hexachlorobutadiene
It is 10~15:1 with anhydrous hydrogen fluoride molar ratio, the molar ratio of liquid-phase fluorination catalyst and hexachlorobutadiene is 0.5~1.5:1,
The molar ratio of catalyst aid and hexachlorobutadiene is 2~8:1, and the molar ratio of solvent and hexachlorobutadiene is 5~25:1, reaction temperature
Degree is 80~180 DEG C, and the reaction time is 3~6h.
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