CN106008145A - Preparation method of 2,3,3,3-tetrafluoropropylene - Google Patents
Preparation method of 2,3,3,3-tetrafluoropropylene Download PDFInfo
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- CN106008145A CN106008145A CN201610351922.6A CN201610351922A CN106008145A CN 106008145 A CN106008145 A CN 106008145A CN 201610351922 A CN201610351922 A CN 201610351922A CN 106008145 A CN106008145 A CN 106008145A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- 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
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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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Abstract
The invention discloses a preparation method of 2,3,3,3-tetrafluoropropylene. The preparation method comprises the following steps: mixing methine halide, tetrafluoroethylene and diluent gas according to the volume ratio of (1-5):1:(0.85-24), and continuously reacting to obtain the 2,3,3,3-tetrafluoropropylene, wherein the reaction temperature is 400-800 DEG C, the reaction pressure is 0.1-0.4 MPa, and the material retention time is 0.5-10 seconds. The method has the advantages of simple technique, high product selectivity, low cost, and can easily implement industrialization.
Description
Technical field
The present invention relates to the preparation method of Fluorine containing olefine, particularly to the preparation method of a kind of 2,3,3,3-tetrafluoropropenes.
Background technology
2,3,3,3-tetrafluoropropenes, molecular formula is CF3CF=CH2, boiling point-28.3 DEG C, No. CAS: 754-12-1, its ODP
Being 0, GWP is 4, has good lifetime climate performance, atmospheric lifetime only 11 days；There is excellent physical and chemical performance,
Its molecular weight and HFC-134a are close, have a saturated vapor pressure higher when relatively low boiling point and room temperature, and with
HFC-134a has close density and critical point, is therefore considered as " the direct substitute " of HFC-134a, becomes
Has one of potential forth generation low-carbon (LC) cold-producing medium.
According to document and patent, current 2,3,3,3-tetrafluoropropene synthetic routes are divided by initiation material mainly to be had: tetrafluoroethene method,
Trifluoropropyne method, trifluoro propene method, C3-Fluoroalcohol. method, hexafluoropropene method (HFP), tetrachloropropylene method, HCFC-242 method,
Difluorochloromethane method, CF3COCH2COCF3Method, HFO-1234ze isomerization process etc..Wherein hexafluoropropene method is to grind
Study carefully one of most route.As US20070179324A, CN102267869A, CN102026947A etc. disclose by
Hexafluoropropene is initiation material, and through hydrogenation, dehydrofluorination, the four-step reaction such as repeated hydrogenation, dehydrofluorination obtains
CF3CF=CH2.While it is true, the method that these patents provide yet suffers from, processing step is many and complicated, equipment investment big,
The shortcomings such as energy consumption is big, " three wastes " more.
CN104169246A discloses the manufacture method of a kind of 2,3,3,3-tetrafluoropropenes, and it is a kind of by containing a chlorine difluoro first
Alkane and the feedstock composition of chloromethanes, manufacture 2,3,3,3-tetrafluoropropenes by the synthetic reaction along with thermal decomposition.
CN102675038A also discloses the preparation method of a kind of 2,3,3,3-tetrafluoropropenes, with F-22
It is raw material with chloromethanes, uses at N2In the presence of gas, under 600～1000 DEG C of hot conditionss, heat scission reaction prepares 2,
3,3,3-tetrafluoropropenes.
In preparation method disclosed in above two patents, although F-22 and chloromethanes can prepare 2 with single step reaction,
3,3,3-tetrafluoropropenes, substantially reduce technological process, but two kinds of reaction raw materials F-22s and chloromethanes are relatively
Heat scission reaction the most easily occurs under high-temperature, and the product component causing reaction to generate is complicated, 2,3,3,3-tetrafluoropropenes
Poor selectivity.
CN102442880A discloses the preparation method of a kind of 2,3,3,3-tetrafluoropropenes, with formula CHXYZ's
Compound and tetrafluoroethene are reaction raw materials, and under catalyst action, reaction prepares 2,3,3,3-tetrafluoropropenes, reaction
Temperature is 400～700 DEG C, and reaction pressure is 0.3～0.5Mpa, and residence time of material is 2～150s.This invention raw material
Being easy to get, productivity is higher, and weak point is to need to occur catalytic pyrolysis to react at relatively high temperatures, catalyst easily carbon distribution,
Cause catalyst life short, and easily block pipeline, without industrial prospect.
Summary of the invention
For the deficiencies in the prior art, technique is simple, product selectivity is high, low cost to the invention provides one, Yi Gong
The preparation method of the 2,3,3,3-tetrafluoropropene of industry.
In order to solve above-mentioned technical problem, the present invention is achieved by the following technical solutions: a kind of 2,3,3,3-tetrafluoros third
The preparation method of alkene, after a halide, tetrafluoroethene, diluent gas by volume 1～5: 1: 0.85～24 mixing
Be carried out continuously reaction prepare 2,3,3,3-tetrafluoropropenes, described reaction temperature is 400～800 DEG C, reaction pressure be 0.1～
0.4Mpa, residence time of material is 0.5～10s.
A described halide is preferably the one in chloromethanes, bromomethane, iodomethane, and a described halide is more
It is preferably bromomethane or iodomethane.
Described diluent gas is preferably steam or nitrogen.
A described halide, tetrafluoroethene, the volume ratio of diluent gas are preferably 1～3: 1: 1～4.
Described reaction temperature is preferably 500～700 DEG C.
Described residence time of material is preferably 2～6s.
Described reaction pressure is preferably 0.1～0.25Mpa.
Preferably, can react again after a halide, tetrafluoroethene, diluent gas preheating, described preheating temperature
Lower 100～300 DEG C than reaction temperature.
The 2 of the present invention, the preparation method of 3,3,3-tetrafluoropropenes, using a halide and tetrafluoroethene is raw material, by heat
Cracking reaction prepares 2,3,3,3-tetrafluoropropene.Although being also heat scission reaction, but only need a halide generation higher temperature
Thermal cracking de-hydrogen halide, side reaction is less.Therefore, the method have flow process short, 2,3,3,3-tetrafluoropropenes select
Property industrialized advantage higher, easy.
The present invention, under nitrogen or water vapour atmosphere, uses a halide and tetrafluoroethene to react preparation 2,3,3,3-tetrafluoro third
Alkene.Methylene Cabbeen is generated by a halide cracking dehydrohalogenationMethylene CabbeenAgain with tetrafluoro second
Alkene reaction generates ptfe ring propane, and ptfe ring propane is generated target product 2,3,3,3-by the most rearranged isomery of thermally labile
Tetrafluoropropene.Reaction equation is as follows:
Product is except 2, outside 3,3,3-tetrafluoropropenes, also include a small amount of other by-product such as vinylidene, methane, three
Fluorothene, hexafluoropropene, Perfluorocyclobutane etc., can obtain highly purified product after rectification.
Compared with prior art, the method have the advantages that
1, technique is simple, low cost.Present invention process flow process is short, only i.e. can get 2,3,3,3-tetra-by single step reaction
Fluoropropene, and product is easily separated, reduces production cost and energy consumption；
2, operating flexibility is big, easy industrialization.Present invention process is simple, and reaction condition is gentleer, and product is easily separated, behaviour
Make elastic big, it is not necessary to catalyst, without carbon distribution, easy industrialization large-scale production；
3, by-product is few, and selectivity is good.Using a halide and tetrafluoroethene is raw material, by heat scission reaction system
Standby 2,3,3,3-tetrafluoropropenes, only need the thermal cracking de-hydrogen halide of a halide generation higher temperature therein, secondary
Product is few, and selectivity is greatly improved, and 2,3,3,3-tetrafluoropropene selectivitys, more than 80.2%, reach as high as 91.3%.
Detailed description of the invention
By the following examples the present invention is carried out more specific description, but the present invention is not limited to described embodiment.
Embodiment 1: each pipeline of reaction unit is passed through nitrogen purging, until oxygen content is less than 15ppm, the most by volume flow
Than being passed through monochloro methane, tetrafluoroethene and water vapour continuously for 5:1:24, again through 500 DEG C of preheaters after the mixing of blended tank
After preheating, entering rustless steel tubular reactor, set reaction temperature 800 DEG C, pressure 0.3Mpa, material is permanent at reactor
Warm area effective time of staying 6s, outlet gaseous mixture through alkali cleaning, alcohol is washed, calcium chloride wash, sample after drying gas chromatogram divides
Analysis, the results are shown in Table 1.
Embodiment 2: each pipeline of reaction unit is passed through nitrogen purging, until oxygen content is less than 15ppm, the most by volume flow
Than being passed through monochloro methane, tetrafluoroethene and water vapour continuously for 3:1:4, again through 500 DEG C of preheaters after the mixing of blended tank
After preheating, entering rustless steel tubular reactor, set reaction temperature 700 DEG C, pressure 0.4Mpa, material is permanent at reactor
Warm area effective time of staying 3s, outlet gaseous mixture through alkali cleaning, alcohol is washed, calcium chloride wash, sample after drying gas chromatogram divides
Analysis, the results are shown in Table 1.
Embodiment 3: each pipeline of reaction unit is passed through nitrogen purging, until oxygen content is less than 15ppm, the most by volume flow
Than being passed through a bromomethane, tetrafluoroethene and water vapour continuously for 1:1:0.85, again through 400 DEG C of preheatings after the mixing of blended tank
After device preheating, entering rustless steel tubular reactor, set reaction temperature 600 DEG C, pressure 0.1Mpa, material is at reactor
Flat-temperature zone effective time of staying 1s, outlet gaseous mixture through alkali cleaning, alcohol is washed, calcium chloride is washed, sample gas chromatogram after drying
Analyze, the results are shown in Table 1.
Embodiment 4: each pipeline of reaction unit is passed through nitrogen purging, until oxygen content is less than 15ppm, the most by volume flow
It is passed through a bromomethane, tetrafluoroethene and water vapour than for 1:1:4, preheats through 400 DEG C of preheaters again after the mixing of blended tank
After, entering rustless steel tubular reactor, set reaction temperature 700 DEG C, pressure 0.1Mpa, material is in reactor flat-temperature zone
Effectively time of staying 6s, outlet gaseous mixture through alkali cleaning, alcohol is washed, calcium chloride is washed, sample gas chromatographic analysis after drying,
The results are shown in Table 1.
Embodiment 5: each pipeline of reaction unit is passed through nitrogen purging, until oxygen content is less than 15ppm, the most by volume flow
Than being passed through a bromomethane, tetrafluoroethene and water vapour continuously for 3:1:4, again through 400 DEG C of preheaters after the mixing of blended tank
After preheating, entering rustless steel tubular reactor, set reaction temperature 700 DEG C, material effectively stops in reactor flat-temperature zone
Time 6s, set pressure 0.15Mpa, outlet gaseous mixture through alkali cleaning, alcohol is washed, calcium chloride is washed, sample gas phase after drying
Chromatography, the results are shown in Table 1.
Embodiment 6: each pipeline of reaction unit is passed through nitrogen purging, until oxygen content is less than 15ppm, the most by volume flow
Than being passed through a bromomethane, tetrafluoroethene and water vapour continuously for 3:1:24, again through 400 DEG C of preheaters after the mixing of blended tank
After preheating, entering rustless steel tubular reactor, set reaction temperature 500 DEG C, pressure 0.2Mpa, material is permanent at reactor
Warm area effective time of staying 3s, outlet gaseous mixture through alkali cleaning, alcohol is washed, calcium chloride wash, sample after drying gas chromatogram divides
Analysis, the results are shown in Table 1.
Embodiment 7: each pipeline of reaction unit is passed through nitrogen purging, until oxygen content is less than 15ppm, the most by volume flow
Than being passed through a bromomethane, tetrafluoroethene and water vapour continuously for 3:1:4, again through 400 DEG C of preheaters after the mixing of blended tank
After preheating, entering rustless steel tubular reactor, set reaction temperature 600 DEG C, pressure 0.25Mpa, material is at reactor
Flat-temperature zone effective time of staying 10s, outlet gaseous mixture through alkali cleaning, alcohol is washed, calcium chloride wash, sample after drying gas phase color
Analysis of spectrum, the results are shown in Table 1.
Embodiment 8: each pipeline of reaction unit is passed through nitrogen purging, until oxygen content is less than 15ppm, the most by volume flow
Than the iodomethane, tetrafluoroethene and the water vapour that are passed through continuously for 3:1:4 through gasification, again through 200 after the mixing of blended tank
After the preheating of DEG C preheater, entering rustless steel tubular reactor, set reaction temperature 400 DEG C, pressure 0.1Mpa, material exists
Reactor flat-temperature zone effective time of staying 2s, outlet gaseous mixture is through washing, sampling gas chromatographic analysis after drying, and result is shown in
Table 1.
Embodiment 9: each pipeline of reaction unit is passed through nitrogen purging, until oxygen content is less than 15ppm, the most by volume flow
Than the iodomethane, tetrafluoroethene and the water vapour that are passed through continuously for 1:1:4 through gasification, again through 200 after the mixing of blended tank
After the preheating of DEG C preheater, entering rustless steel tubular reactor, set reaction temperature 600 DEG C, pressure 0.1Mpa, material exists
Reactor flat-temperature zone effective time of staying 6s, outlet gaseous mixture is through washing, sampling gas chromatographic analysis after drying, and result is shown in
Table 1.
Embodiment 10: each pipeline of reaction unit is passed through nitrogen purging, until oxygen content is less than 15ppm, the most by volume flow
Than being passed through a bromomethane, tetrafluoroethene and nitrogen continuously for 1:1:4, after warm blending tank mixing, enter rustless steel
Tubular reactor, sets reaction temperature 700 DEG C, and pressure 0.1Mpa, material is in reactor flat-temperature zone effective time of staying
6s, outlet gaseous mixture through alkali cleaning, alcohol is washed, calcium chloride is washed, sample gas chromatographic analysis after drying, the results are shown in Table 1.
Table 1 embodiment 1～10 analysis result
| Embodiment | TFE conversion ratio (%) | HFO-1234yf selectivity (%) |
| 1 | 89.6 | 80.2 |
| 2 | 79.4 | 82.3 |
| 3 | 85.4 | 84.6 |
| 4 | 91.8 | 85.9 |
| 5 | 93.5 | 86.6 |
| 6 | 87.2 | 89.4 |
| 7 | 92.7 | 88.3 |
| 8 | 79.9 | 91.3 |
| 9 | 88.2 | 83.6 |
| 10 | 90.5 | 83.3 |
Claims (9)
1. one kind 2, the preparation method of 3,3,3-tetrafluoropropenes, it is characterised in that by a halide, tetrafluoroethene, dilution
It is carried out continuously reaction after gas 1～5: 1: 0.85～24 mixing by volume and prepares 2,3,3,3-tetrafluoropropenes, described reaction
Temperature is 400～800 DEG C, and reaction pressure is 0.1～0.4Mpa, and residence time of material is 0.5～10s.
The preparation method of 2,3,3,3-tetrafluoropropenes the most according to claim 1, it is characterised in that a described halo
Methane is the one in chloromethanes, bromomethane, iodomethane.
The preparation method of 2,3,3,3-tetrafluoropropenes the most according to claim 2, it is characterised in that a described halo
Methane is bromomethane or iodomethane.
The preparation method of 2,3,3,3-tetrafluoropropenes the most according to claim 1, it is characterised in that described carrier gas
Body is steam or nitrogen.
The preparation method of 2,3,3,3-tetrafluoropropenes the most according to claim 1, it is characterised in that a described halo
Methane, tetrafluoroethene, the volume ratio of diluent gas are 1～3: 1: 1～4.
The preparation method of 2,3,3,3-tetrafluoropropenes the most according to claim 1, it is characterised in that described reaction temperature
Degree is 500～700 DEG C.
The preparation method of 2,3,3,3-tetrafluoropropenes the most according to claim 1, it is characterised in that described material stops
Staying the time is 2～6s.
The preparation method of 2,3,3,3-tetrafluoropropenes the most according to claim 1, it is characterised in that described reaction pressure
Power is 0.1～0.25Mpa.
The preparation method of 2,3,3,3-tetrafluoropropenes the most according to claim 1, it is characterised in that by a halide,
Reacting after the preheating of tetrafluoroethene, diluent gas, described preheating temperature is lower 100～300 DEG C than reaction temperature again.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102442880A (en) * | 2011-10-22 | 2012-05-09 | 山东东岳高分子材料有限公司 | Preparation method of 2, 3, 3, 3-tetrafluoropropene |
| JP2014101326A (en) * | 2012-11-21 | 2014-06-05 | Asahi Glass Co Ltd | Method for producing 2,3,3,3-tetrafluoro-propene |
| JP2014129273A (en) * | 2012-12-28 | 2014-07-10 | Asahi Glass Co Ltd | Method for producing 2,3,3,3-tetrafluoropropene |
| JP2016027004A (en) * | 2012-11-22 | 2016-02-18 | 旭硝子株式会社 | Production method of 2,3,3,3-tetrafluoropropene |
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- 2016-05-25 CN CN201610351922.6A patent/CN106008145A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102442880A (en) * | 2011-10-22 | 2012-05-09 | 山东东岳高分子材料有限公司 | Preparation method of 2, 3, 3, 3-tetrafluoropropene |
| JP2014101326A (en) * | 2012-11-21 | 2014-06-05 | Asahi Glass Co Ltd | Method for producing 2,3,3,3-tetrafluoro-propene |
| JP2016027004A (en) * | 2012-11-22 | 2016-02-18 | 旭硝子株式会社 | Production method of 2,3,3,3-tetrafluoropropene |
| JP2014129273A (en) * | 2012-12-28 | 2014-07-10 | Asahi Glass Co Ltd | Method for producing 2,3,3,3-tetrafluoropropene |
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