CN103965011B - A kind of preparation method of 3,3,3-trifluoro propene - Google Patents
A kind of preparation method of 3,3,3-trifluoro propene Download PDFInfo
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- CN103965011B CN103965011B CN201410188425.XA CN201410188425A CN103965011B CN 103965011 B CN103965011 B CN 103965011B CN 201410188425 A CN201410188425 A CN 201410188425A CN 103965011 B CN103965011 B CN 103965011B
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Abstract
The invention discloses a kind of preparation method of 3,3,3-trifluoro propene, with 1,1,1,3-tetra-chloropropane and hydrogen fluoride are raw material, take ionic liquid as catalyzer, one step liquid phase reaction synthesis 3,3,3-trifluoro propene, temperature of reaction is 50 DEG C ~ 160 DEG C, ionic liquid and 1,1,1,3-tetra-chloropropane mol ratio is 1:2 ~ 1:10, hydrogen fluoride and 1, the mol ratio of 1,1,3-tetra-chloropropane is 3.1:1 ~ 50:1; Wherein ionic liquid general formula is X
+a
-, X
+for C
1-C
8the imidazoles that alkyl replaces, pyridine and quaternaries cation, A
-for the metalate anions containing aluminium, iron, antimony, tantalum, niobium, titanium, tin etc.The present invention adopts ionic liquid as catalyzer, 1,1,1,3-tetra-chloropropane with fluoridize obtained 3,3, the 3-trifluoro propene of hydroformylation step liquid phase reaction, without the need to carrying out dehydrochlorination reaction with sodium hydroxide solution, reactions steps is less, technological process environmental protection.Ionic liquid is as catalyzer in addition, and activity is higher and can repeatedly use.
Description
Technical field
The present invention relates to a kind of preparation method of 3,3,3-trifluoro propene, to particularly relate to 1,1,1,3-tetra-chloropropane with hydrogen fluoride for raw material, ionic liquid is catalyzer, and a step liquid phase reaction synthesizes the preparation method of 3,3,3-trifluoro propene.
Background technology
3,3,3-trifluoro propene is the basic raw material of synthesis trifluoropropyl siloxane and the contour performance macromolecular material of fluorosilicon oil, is also excellent medicine intermediate and freonll-11 substitute.CN103044191A discloses a kind of preparation method of 3,3,3-trifluoro propene, and the method is first under catalyzer difluoro tindichloride and the effect of stopper cyclobutanone, and 1,1,1,3-tetra-chloropropane and hydrogen fluoride prepare the fluoro-3-chloropropane of 1,1,1-tri-; Again fluoro-for 1,1,1-tri-3-chloropropane is removed under sodium hydroxide and Dodecyl trimethyl ammonium chloride katalysis hydrogenchloride obtained 3,3,3-trifluoro propene, preparation method is two-step reaction, processing step is more, and adopts sodium hydroxide solution to remove HCl, and quantity of three wastes is large.
Summary of the invention
The object of the invention is to overcome the deficiency existed in background technology, provide that a kind of processing step is few, the preparation method of 3,3,3-trifluoro propenes of process environmental protection.
In order to realize object of the present invention, the present invention adopts ionic liquid as catalyzer, and 1,1,1,3-tetra-chloropropane and hydrogen fluoride are raw material, one step liquid phase reaction prepares 3,3,3-trifluoro propene, temperature of reaction is 50 DEG C ~ 160 DEG C, ionic liquid consumption and 1,1,1,3-tetra-chloropropane mol ratio is 1:2 ~ 10, hydrogen fluoride and 1, the mol ratio of 1,1,3-tetra-chloropropane is 3.1 ~ 50:1; Wherein ionic liquid general formula is X
+a
-, X
+for C
1-C
8the imidazoles that alkyl replaces, pyridine and quaternaries cation, A
-for the metalate anions containing aluminium, iron, antimony, tantalum, niobium, titanium or tin etc.
Ionic liquid of the present invention, positively charged ion X
+can be 1-ethyl-3-methylimidazole, 1-butyl-3-Methylimidazole, N-ethylpyridine, N-butyl-pyridinium, tetraethyl ammonium or TBuA, negatively charged ion A
-can be AlCl
4 -, FeCl
4 -, TiCl
5 -, SnCl
5 -, SbCl
6 -, TaCl
6 -, NbCl
6 -, Fe
2cl
7 -, Al
2cl
7 -, Sb
2cl
11 -, SbF
6 -, TaF
6 -or NbF
6 -, or their mixture.
Ionic liquid of the present invention is preferably tetraethyl ammonium heptachlor two aluminate ([NEt
4] Al
2cl
7), TBuA heptachlor two aluminate ([NBu
4] Al
2cl
7), 1-ethyl-3-methylimidazole heptachlor two aluminate ([EMIM] Al
2cl
7), 1-butyl-3-Methylimidazole heptachlor two aluminate ([BMIM] Al
2cl
7), N-ethylpyridine heptachlor two aluminate ([EPy] Al
2cl
7) or N-butyl-pyridinium heptachlor two aluminate ([BPy] Al
2cl
7).
Described ionic liquid adopts following preparation method to obtain: after by organic salt (chloro imidazoles, pyridine or quaternary ammonium salt), in glove box, recrystallization dewaters, be heated to 60 DEG C, constant temperature vacuumizes removing residual solvent; By metal halide (AlCl
3, FeCl
3, SbCl
5, TaCl
5, NbCl
5, TiCl
4, SnCl
4deng) add in reactor, namely obtain ionic liquid at 80 ~ 120 DEG C of reaction 72h.Wherein, the mol ratio of metal halide and organic salt is 2:1.
Because the present invention carries out in hydrogen fluoride atmosphere, in order to improve activity and the stability of ionic-liquid catalyst, preferably carry out activating pretreatment with hydrogen fluoride.
Temperature of reaction preferably to 60 of the present invention DEG C ~ 120 DEG C, ionic liquid and 1,1,1,3-tetra-chloropropane mol ratio preferably to 1:3 ~ 5, mol ratio preferably to the 10 ~ 30:1 of hydrogen fluoride and 1,1,1,3-tetra-chloropropane.
In the present invention, the reaction times is 0.5h ~ 10h, is preferably 1h ~ 5h.Reaction can periodical operation, also can operate continuously, reaction itself to reaction formation without obvious requirement.
Advantage of the present invention: the present invention adopts ionic liquid as catalyzer, 1,1,1,3-tetra-chloropropane with fluoridize obtained 3,3, the 3-trifluoro propene of hydroformylation step liquid phase reaction, without the need to carrying out dehydrochlorination reaction by NaOH solution, reactions steps is less, technological process environmental protection.Ionic liquid is as catalyzer in addition, and activity is higher and can repeatedly use.
Embodiment
Followingly explanation is described in further detail to the present invention in conjunction with the embodiments, but does not limit the scope of the invention.
Embodiment 1
The preparation of ionic liquid adopts aforesaid method, specific to ionic liquid [NEt
4] Al
2cl
7step is: to be equipped with magnetic agitation, temperature sleeves, condensing works 250mL stainless steel cauldron in, add the pretreated [NEt of 0.03mol
4] Cl and 0.06molAlCl
3, stir 72h at 80 DEG C of temperature lower magnetic forces, obtained ionic liquid [NEt
4] Al
2cl
7.
To [the NEt of above-mentioned preparation
4] Al
2cl
7in add the HF of 0.9mol, steady pressure is within 0.2Mpa, and be progressively warmed up to 150 DEG C with 20 DEG C/2h, row pressure is to normal pressure.In reactor, add the HF of 1.8mol successively, 1,1,1,3-tetra-chloropropane of 0.09mol, reacts 4h at 100 DEG C of temperature.Reaction product adopts gas chromatographic analysis, and result shows that 1,1,1,3-tetrachloro conversion of propane be 98.6%, 3,3,3-trifluoro propene selectivity is 98.4%.
Embodiment 2 ~ 4
The operating process of embodiment 2 ~ 4 is similar to embodiment 1, and difference is ionic liquid, and the preparation of ionic liquid adopts the similar approach in embodiment 1, and reaction result is as shown in table 1.
Table 1
| Embodiment | Ionic liquid | 1,1,1,3-tetrachloro conversion of propane (%) | 3,3,3-trifluoro propene selectivity (%) |
| 2 | [NBu 4]Al 2Cl 7 | 98.1 | 96.3 |
| 3 | [EMIM]Al 2Cl 7 | 96.8 | 96.6 |
| 4 | [EPy]Fe 2Cl 7 | 98.2 | 95.3 |
Embodiment 5 ~ 9
The operating process of embodiment 5 ~ 9 is similar to embodiment 1, and difference is temperature of reaction is 60 DEG C, and use ionic-liquid catalyst, the preparation of ionic liquid adopts the similar approach in embodiment 1, and reaction result is as shown in table 2.
Table 2
Embodiment 10 ~ 14
The operating process of embodiment 10 ~ 14 is similar to embodiment 1, and difference is temperature of reaction, and reaction result is as shown in table 3.
Table 3
| Embodiment | Temperature of reaction, DEG C | 1,1,1,3-tetrachloro conversion of propane (%) | 3,3,3-trifluoro propene selectivity (%) |
| 10 | 50 | 88.1 | 80.6 |
| 11 | 60 | 94.2 | 91.8 |
| 12 | 80 | 98.5 | 99.2 |
| 13 | 120 | 98.9 | 98.8 |
| 14 | 160 | 99.1 | 90.3 |
Embodiment 15 ~ 18
The operating process of embodiment 15 ~ 18 is similar to embodiment 1, and difference is the mol ratio of catalyst levels and hydrogen fluoride and 1,1,1,3-tetra-chloropropane, and reaction result is as shown in table 4.
Table 4
Embodiment 19
The operating process of embodiment 19 is similar to embodiment 1, and reaction after product drains, and ionic liquid carries out 8 circulating reactions, and catalytic activity is substantially constant, and reaction result is as shown in table 5.
Table 5
| Cycle index | 1,1,1,3-tetrachloro conversion of propane (%) | 3,3,3-trifluoro propene selectivity (%) |
| 1 | 98.6 | 98.4 |
| 2 | 98.8 | 97.6 |
| 3 | 99.0 | 96.3 |
| 4 | 97.8 | 98.3 |
| 5 | 98.3 | 98.2 |
| 6 | 97.8 | 98.6 |
| 7 | 98.2 | 97.3 |
| 8 | 98.3 | 98.9 |
Embodiment 20
The operating process of embodiment 20 is similar to embodiment 1, and difference is the ionic liquid used is [EMIM] Al
2cl
7, reaction after product drains, and ionic liquid carries out 8 circulating reactions, and catalytic activity is substantially constant, and reaction result is as shown in table 6.
Table 6
| Cycle index | 1,1,1,3-tetrachloro conversion of propane (%) | 3,3,3-trifluoro propene selectivity (%) |
| 1 | 98.6 | 97.4 |
| 2 | 98.3 | 97.5 |
| 3 | 98.5 | 96.7 |
| 4 | 98.1 | 98.0 |
| 5 | 98.0 | 97.8 |
| 6 | 98.0 | 98.2 |
| 7 | 98.1 | 98.1 |
| 8 | 97.9 | 98.2 |
Claims (7)
1. the preparation method of a trifluoro propene, with 1,1,1,3-tetra-chloropropane and hydrogen fluoride are raw material, it is characterized in that taking ionic liquid as catalyzer, one step liquid phase reaction synthesis 3,3,3-trifluoro propene, temperature of reaction is 50 DEG C ~ 160 DEG C, ionic liquid and 1,1,1,3-tetra-chloropropane mol ratio is 1:2 ~ 10, hydrogen fluoride and 1, the mol ratio of 1,1,3-tetra-chloropropane is 3.1 ~ 50:1; Wherein the general formula of ionic liquid is X
+a
-, X
+for C
1-C
8the imidazoles that alkyl replaces or pyridylium, A
-for the metalate anions containing aluminium, iron, antimony, tantalum, niobium, titanium or tin.
2. the preparation method of a trifluoro propene, with 1,1,1,3-tetra-chloropropane and hydrogen fluoride are raw material, it is characterized in that taking ionic liquid as catalyzer, one step liquid phase reaction synthesis 3,3,3-trifluoro propene, temperature of reaction is 50 DEG C ~ 160 DEG C, ionic liquid and 1,1,1,3-tetra-chloropropane mol ratio is 1:2 ~ 10, hydrogen fluoride and 1, the mol ratio of 1,1,3-tetra-chloropropane is 3.1 ~ 50:1; Wherein the general formula of ionic liquid is X
+a
-, X
+for C
1-C
8the quaternaries cation that alkyl replaces, A
-for the metalate anions containing aluminium, iron, antimony, tantalum, niobium, titanium or tin.
3. the preparation method of 3,3,3-trifluoro propenes according to claim 1, is characterized in that described ionic liquid, positively charged ion X
+for 1-ethyl-3-methylimidazole, 1-butyl-3-Methylimidazole, N-ethylpyridine or N-butyl-pyridinium, negatively charged ion A
-for AlCl
4 -, FeCl
4 -, TiCl
5 -, SnCl
5 -, SbCl
6 -, TaCl
6 -, NbCl
6 -, Fe
2cl
7 -, Al
2cl
7 -, Sb
2cl
11 -, SbF
6 -, TaF
6 -, NbF
6 -or their mixture.
4. according to claim 33,3, the preparation method of 3-trifluoro propene, is characterized in that described ionic liquid is 1-ethyl-3-methylimidazole heptachlor two aluminate, 1-butyl-3-Methylimidazole heptachlor two aluminate, N-ethylpyridine heptachlor two aluminate or N-butyl-pyridinium heptachlor two aluminate.
5. the preparation method of 3,3,3-trifluoro propenes according to claim 2, is characterized in that described ionic liquid, positively charged ion X
+for tetraethyl ammonium or TBuA, negatively charged ion A
-for AlCl
4 -, FeCl
4 -, TiCl
5 -, SnCl
5 -, SbCl
6 -, TaCl
6 -, NbCl
6 -, Fe
2cl
7 -, Al
2cl
7 -, Sb
2cl
11 -, SbF
6 -, TaF
6 -, NbF
6 -or their mixture.
6. the preparation method of 3,3,3-trifluoro propenes according to claim 5, is characterized in that described ionic liquid is tetraethyl ammonium heptachlor two aluminate or TBuA heptachlor two aluminate.
7. the preparation method of 3,3,3-trifluoro propenes according to the arbitrary claim of claim 1 ~ 6, is characterized in that temperature of reaction is 60 DEG C ~ 120 DEG C, ionic liquid and 1,1,1,3-tetra-chloropropane mol ratio are 1:3 ~ 5, the mol ratio of hydrogen fluoride and 1,1,1,3-tetra-chloropropane is 10 ~ 30:1.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101214447A (en) * | 2008-01-16 | 2008-07-09 | 西安近代化学研究所 | Naluminum fluoride base fluorating catalyst and preparation thereof |
| CN101306978A (en) * | 2008-05-23 | 2008-11-19 | 巨化集团公司 | Method for synthesizing 3,3,3-trifluoro propene |
| CN101679151A (en) * | 2007-05-31 | 2010-03-24 | 阿克马法国公司 | Process for preparing (hydro)(chloro)olefins |
| CN103201242A (en) * | 2010-11-15 | 2013-07-10 | 阿克马法国公司 | Process for the manufacture of 2 - chloro - 3, 3, 3 - trifluoropropene (hcfo 1233xf) by liquid phase fluorination of pentachloropropane |
-
2014
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101679151A (en) * | 2007-05-31 | 2010-03-24 | 阿克马法国公司 | Process for preparing (hydro)(chloro)olefins |
| CN101214447A (en) * | 2008-01-16 | 2008-07-09 | 西安近代化学研究所 | Naluminum fluoride base fluorating catalyst and preparation thereof |
| CN101306978A (en) * | 2008-05-23 | 2008-11-19 | 巨化集团公司 | Method for synthesizing 3,3,3-trifluoro propene |
| CN103201242A (en) * | 2010-11-15 | 2013-07-10 | 阿克马法国公司 | Process for the manufacture of 2 - chloro - 3, 3, 3 - trifluoropropene (hcfo 1233xf) by liquid phase fluorination of pentachloropropane |
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