CN101628849A - Preparation method of Z-1,2,3,3,3-pentafluoropropylene - Google Patents
Preparation method of Z-1,2,3,3,3-pentafluoropropylene Download PDFInfo
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- CN101628849A CN101628849A CN200910162611A CN200910162611A CN101628849A CN 101628849 A CN101628849 A CN 101628849A CN 200910162611 A CN200910162611 A CN 200910162611A CN 200910162611 A CN200910162611 A CN 200910162611A CN 101628849 A CN101628849 A CN 101628849A
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Abstract
The invention discloses a preparation method of Z-1,2,3,3,3-pentafluoropropylene (Z-HFO-1225ye), which comprises the following steps: a. adding hydrogen and hexafluoropropylene into a first reactor and reacting under the existence of a hydrogenation catalyst; b. leading a product prepared in the step a to flow into a first distillation tower for separation and returning a tower component to the first reactor; c. adding N2 and a tower reactor component 1,1,2,3,3-hexafluoropropane (HFC-263ea) prepared in the step b into a second reactor and reacting the 1,1,2,3,3-hexafluoropropane under the existence of dehydrofluorination catalyst; d. leading a product prepared in the step c to flow into a third reactor and reacting with E-HFO-1225ye under the existence of an isomerization catalyst; e. leading a product prepared in the step d to flow into a second distillation tower for separation and returning a tower component to the second reactor; f. adding a tower reactor component prepared in the step e into a third distillation tower and separating the tower component with a system to obtain the Z-HFO-1225ye after treatment; and g. adding a tower reactor component prepared in the step f into a phase separator for separation, returning an organic phase with rich HFC-236es to the second reactor and separating an organic phase with rich HF from the system. The invention is mainly used for the preparation of the Z-HFO-1225ye.
Description
Technical field
The present invention relates to a kind of Z-1,2,3,3, the preparation method of 3-five fluorine propylene (Z-HFO-1225ye), relating in particular to a kind of is raw material with hydrogen and R 1216 (HFP), elder generation's hydrogenation in the presence of hydrogenation catalyst, and dehydrofluorination and isomerization obtain Z-1 under the effect of dehydrofluorination isomerization catalyst again, 2,3,3, the preparation method of 3-five fluorine propylene.
Background technology
Z-1,2,3,3,3-five fluorine propylene (Z-HFO-1225ye) and E-1,2,3,3,3-five fluorine propylene (E-HFO-1225ye) are 1,2,3,3, the geometrical isomer of 3-five fluorine propylene.Both compare, and Z-HFO-1225ye has more excellent refrigeration performance.1,2,3,3, when 3-five fluorine propylene (HFO-1225ye) use as refrigeration agent, require Z-HFO-1225ye and E-HFO-1225ye ratio greater than 90%.
" Preparation of E-1,2,3,3,3-pentafluoropropene, Z-1,2,3,3,3-pentafluoropropene and E-iodopentafluoropropene " Journal of FluorineChemistry, 1989, it is the method for feedstock production Z-HFO-1225ye with R 1216 (HFP) that 44:167-174 has reported a kind of, is reacted down at-78 ℃ by R 1216 and tributyl phosphorus earlier to generate E-1-(1-fluorine tributyl phosphorus) five fluorine propylene, then in the presence of triglyme, E-1-(1-fluorine tributyl phosphorus) five fluorine propylene and water reaction generate E-HFO-1225ye, and in the presence of antimony pentafluoride, catalysis E-HFO-1225ye isomerization reaction takes place obtains Z-HFO-1225ye at last, with the starting raw material R 1216 is benchmark, and the total recovery of Z-HFO-1225ye is 84.5%.There is the low defective of total recovery in this preparation method.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiency that exists in the background technology, and a kind of gas-phase reaction is provided, the Z-1 that total recovery is higher, 2,3,3, the preparation method of 3-five fluorine propylene.
The present invention is raw material with the R 1216, and the principal reaction of generation is as follows:
CF
3CF＝CF
2+H
2→CF
3CHFCHF
2 (1)
HFP HFC-236ea
CF
3CHFCHF
2→CF
3CF＝CHF+HF (2)
The mixture of Z-HFO-1225ye and E-HFO-1225ye
E-HFO-1225ye→Z-HFO-1225ye (3)
The present invention adopts three reactors, and first reactor mainly carries out H
2The reaction of hydrogenation HFP, under proper reaction conditions, the transformation efficiency of HFP can reach 100%, mainly react (1), product is HFC-236ea; Second reactor mainly carries out the reaction of HFC-236ea dehydrofluorination, and react (2), reaction product is Z-HFO-1225ye and E-HFO-1225ye; The 3rd reactor mainly carries out the isomerized reaction of E-HFO-1225ye, and react (3), reaction product is Z-HFO-1225ye.
The invention provides a kind of Z-1,2,3,3, the preparation method of 3-five fluorine propylene may further comprise the steps:
A. hydrogen and R 1216 enter first reactor, react in the presence of hydrogenation catalyst, and reaction conditions is: the mol ratio 1～5 of reaction pressure 0.1MPa～1.0MPa, hydrogen and R 1216, R 1216 air speed 120h
-1～1800h
-1, 0 ℃～200 ℃ of temperature of reaction, comprise in the product stream that reaction generates 1,1,1,2,3,3-HFC-236fa and unreacted hydrogen and R 1216, wherein hydrogenation catalyst is a palladium carbon catalyst, the palladium charge capacity is 05%～5%;
B. the product of step a flows to first distillation tower and separates, and tower still component is 1,1,1,2,3, and 3-HFC-236fa, cat head component are hydrogen and R 1216, and the cat head component is back to first reactor;
C. the tower still component 1,1,1 that obtains of nitrogen and step b, 2,3, the 3-HFC-236fa enters second reactor, 1,1,1,2,3, the 3-HFC-236fa is carried out dehydrofluorination in the presence of Dehydrofluorination catalyst, reaction conditions is: reaction pressure 0.1MPa～1.0MPa, 1,1,1,2,3,3-HFC-236fa air speed 30h
-1～300h
-1, 250 ℃～380 ℃ of temperature of reaction, comprise the Z-1 of generation in the product stream, 2,3,3,3-five fluorine propylene, E-1,2,3,3,3-five fluorine propylene, unreacted 1,1,1,2,3,3-HFC-236fa and nitrogen, wherein the quality percentage composition of Dehydrofluorination catalyst is Cr
3+: 50%～80%; Al
3+: 5%～30%; Zn
2+: 1%～10%; Ni
3+: 1%～10%;
D. the product stream of step c flows to the 3rd reactor, in the presence of isomerization catalyst, and E-1,2,3,3,3-five fluorine propylene carry out isomerization reaction, and reaction conditions is: reaction pressure 0.1MPa～1.0MPa, E-1,2,3,3,3-five fluorine propylene air speed 72h
-1～720h
-1, 25 ℃～100 ℃ of temperature of reaction, comprise Z-1 in the product stream, 2,3,3,3-five fluorine propylene, unreacted E-1,2,3,3,3-five fluorine propylene, 1,1,1,2,3,3-HFC-236fa and nitrogen, wherein the quality percentage composition of isomerization catalyst is an aluminum trifluoride: 85%～95%; Tin tetrafluoride: 5%～15%;
E. the product of steps d flows to into second column and separates, and tower still component is Z-1, and 2,3,3,3-five fluorine propylene, E-1,2,3,3,3-five fluorine propylene, hydrogen fluoride and 1,1,1,2,3,3-HFC-236fa, cat head component are nitrogen, and the cat head component is back to second reactor;
F. the tower still component of step e enters the 3rd distillation tower and separates, and tower still component is hydrogen fluoride and 1,1, and 1,2,3,3-HFC-236fa, cat head component are Z-1,2,3,3,3-five fluorine propylene, E-1,2,3,3,3-five fluorine propylene, cat head component detachment system through aftertreatment technologys such as deacidification, dehydration, rectifying, obtains target product Z-1,2,3,3,3-five fluorine propylene;
G. the tower still component of step f enters phase separator and is separated, and the organic phase that is rich in HFC-236ea is back to second reactor, is rich in the inorganic system that is separated of HF.
The reaction conditions of the present invention's first reactor is preferably: the mol ratio 1.5～2 of reaction pressure 0.3MPa～0.6MPa, hydrogen and R 1216, the air speed 360h of R 1216
-1～720h
-1, 50 ℃～100 ℃ of temperature of reaction.
The reaction conditions of the present invention's second reactor is preferably: reaction pressure 0.3MPa～0.6MPa, 1,1,1,2,3, the air speed 100h of 3-HFC-236fa
-1～200h
-1, 300 ℃～350 ℃ of temperature of reaction.
The reaction conditions of the present invention's the 3rd reactor is preferably: reaction pressure 0.3MPa～0.6MPa, E-1,2,3,3,3-five fluorine propylene air speed 100h
-1～200h
-1, 50 ℃～80 ℃ of temperature of reaction.
Among the present invention, the reaction product of first reactor enters first distillation tower separates, and tower still component is 1,1,1,2,3, and 3-HFC-236fa, cat head component are hydrogen and a small amount of R 1216.The present invention can suitably select according to the level of equipment, general facilities, the working pressure of reactive system and factors such as composition to be separated to the operational condition of distillation tower without limits.Working pressure is 0.1MPa～1.0MPa, preferred 0.3MPa～0.6MPa.Generally speaking, for easy and simple to handle, the working pressure of distillation tower is consistent with reactive system.Tower top temperature and tower still temperature are by working pressure and material component decision thereof.
Among the present invention, the reaction product of the 3rd reactor enters second column separates, and tower still component is 1,2,3,3,3-five fluorine propylene, hydrogen fluoride and 1,1,1,2,3, and 3-HFC-236fa, cat head component are nitrogen.The present invention can suitably select according to the level of equipment, general facilities, the working pressure of reactive system and factors such as composition to be separated to the operational condition of distillation tower without limits.Working pressure is 0.1MPa～1.0MPa, preferred 0.3MPa～0.6MPa.Generally speaking, for easy and simple to handle, the working pressure of distillation tower is consistent with reactive system.Tower top temperature and tower still temperature are by working pressure and material component decision thereof.
Among the present invention, the tower still component of second column enters the 3rd distillation tower separates, and tower still component is HF and HFC-236ea, and the cat head component is Z-1, and 2,3,3,3-five fluorine propylene and E-1,2,3,3,3-five fluorine propylene.The present invention can suitably select according to the level of equipment, general facilities, the working pressure of reactive system and factors such as composition to be separated to the operational condition of distillation tower without limits.Working pressure is 0.1MPa～1.0MPa, preferred 0.3MPa～0.6MPa.Generally speaking, for easy and simple to handle, the working pressure of distillation tower is consistent with reactive system.Tower top temperature and tower still temperature are by working pressure and material component decision thereof.
The hydrogenation catalyst that the present invention uses is a palladium carbon catalyst, and the palladium charge capacity is 0.5%～5%.Except palladium carbon catalyst, hydrogenation catalyst can also be nickel catalyst, copper catalyst, cobalt catalyst, platinum group catalyst, ruthenium catalyst, rhodium catalyst, iridium catalyst, osmium catalyst etc.The hydrogenation catalyst difference that adopts, reaction conditions difference then comprises the mol ratio of temperature of reaction, reaction pressure, duration of contact and material.
The quality percentage composition of the Dehydrofluorination catalyst that the present invention uses is Cr
3+: 50%～80%; Al
3+: 5%～30%; Zn
2+: 1%～10%; Ni
3+: 1%～10%, its preparation method is seen Chinese patent CN100372607C disclosed method.Except above-mentioned catalyzer, Dehydrofluorination catalyst can also be chromic oxide, fluorizated chromic oxide, aluminum fluoride, fluorizated aluminum oxide, be carried on chromic oxide on gac, aluminum fluoride, the magnesium fluoride, contain the chromic oxide of multiple metal (as Zn, Co, Ni, Ge, In etc.) etc.The Dehydrofluorination catalyst difference that adopts, reaction conditions difference then comprises the mol ratio of temperature of reaction, reaction pressure, duration of contact and material.
The quality percentage composition of the isomerization catalyst that the present invention uses is aluminum trifluoride: 85%～95%; Tin tetrafluoride: 5%～15%, its preparation method may further comprise the steps: (1) mixes aluminium hydroxide, tindioxide by mass ratio, and compression moulding obtains catalyst precursor; (2) catalyst precursor that step (1) is obtained carries out roasting after 6～15 hours at 300 ℃～450 ℃, and 250 ℃～350 ℃ with hydrogen fluoride activation 6～15 hours, makes isomerization catalyst.Except above-mentioned catalyzer, isomerization catalyst can also be that a kind of in tin tetrachloride, titanium tetrachloride, tantalum pentachloride, antimony pentachloride, tin tetrafluoride, titanium tetrafluoride, tantalum pentafluoride or the antimony pentafluoride or several are carried on gac, fluorine alumina, aluminum fluoride or other fluorine (or oxygen) and change the thing supported catalyst.The isomerization catalyst difference of the employing of this catalyzer, reaction conditions difference then comprises the mol ratio of temperature of reaction, reaction pressure, duration of contact and material.
The type of reactor that the present invention is used for hydrogenation reaction, dehydrofluorination and isomerization reaction is not crucial, can use tubular reactor, fluidized-bed reactor etc.In addition, adiabatic reactor or isothermal reactor are also available.
Advantage of the present invention: total recovery height of the present invention, the Z-HFO-1225y once through yield can reach 99.5%, and the Z-HFO-1225ye total recovery of prior art is 84.5%.
Description of drawings
Fig. 1 table Z-1,2,3,3, preparation technology's schema of 3-five fluorine propylene.
Label meaning in Fig. 1 is as follows.Pipeline: 1,2,3,5,6,8,9,10,12,14,15,17,18,20,21 and 23; First reactor: 4; First distillation tower: 7; Second reactor: 11; The 3rd reactor: 13; Second column: 16; The 3rd distillation tower: 19; Phase separator: 22.
Embodiment
The present invention is described in more detail with reference to Fig. 1.But do not limit the present invention.Through the fresh HFP of pipeline 1 feeding, with the fresh H that feeds through pipeline 2
2, entering in first reactor 4 that is filled with hydrogenation catalyst by pipeline 3 together and react, the reaction product pipeline 5 of flowing through enters first distillation tower 7 and separates; First distillation tower, 7 cat head components are H
2With small amount of H FP, be back to first reactor 4 by pipeline 6 and pipeline 3; The first distillation Tata still component is HFC-236ea, through pipeline 8 and the fresh N that feeds through pipeline 9
2Enter second reactor 11 that is filled with Dehydrofluorination catalyst by pipeline 10 together, feed N
2Make HFC-236ea under nitrogen protection, carry out dehydrofluorination, play the effect that prolongs the Dehydrofluorination catalyst life-span.Reactant flow enters the 3rd reactor 13 through pipeline 12, and it is nitrogen that reactant flow enters second knockout tower, 16, the second knockout towers, 16 cat head components by pipeline 14, is back to second reactor 11 through pipeline 15 and pipeline 10; Second knockout tower, 16 tower still components are Z-HFO-1225ye, E-HFO-1225ye, HF and HFC-236ea, and entering the 3rd knockout tower 19, the three knockout towers 19 tower still components through pipeline 17 is HF and HFC-236ea, enters phase separator 22 through pipeline 20 and is separated; The upper strata of phase separator 22 is the inorganic phase that is rich in HF, through pipeline 21 detachment systems, through treatment steps such as dehydrations, obtains the byproduct anhydrous HF; The lower floor of phase separator 22 is the organic phase that is rich in HFC-236ea, is back to second reactor 11 by pipeline 23 and pipeline 10; The 3rd knockout tower 19 cat head components are Z-HFO-1225ye, E-HFO-1225ye, through pipeline 18 detachment systems, through post-processing steps such as deacidification, dehydration, rectifying, obtain target product Z-HFO-1225ye.
Analytical instrument: the glad chromatogram GC-930 in sea, Shanghai, hydrogen flame detector, Tianjin, island GC-MS2010, chromatographic column is capillary column Al
2O
3/ S " 50m * 0.320mm * 0.25 μ m " (manufacturing of chromatographic technique research and development centre of Lanzhou Inst. of Chemical Physics, Chinese Academy of Sciences).
Gas chromatography analysis method: reaction product is got gaseous sample and is carried out gas chromatographic analysis after washing, alkali cleaning and drying.High purity nitrogen and hydrogen are as carrier gas.Testing conditions is 200 ℃ of temperature of vaporization chamber, 220 ℃ of auxiliary furnace 2 temperature, 220 ℃ of detector temperatures, 150 ℃ of post stove initial temperatures.
The GC-MS analytical procedure: reaction product is got gaseous sample and is carried out the GC-MS analysis after washing, alkali cleaning and drying.170 ℃ of column temperatures, 200 ℃ of detector temperatures, 220 ℃ of temperature of vaporization chamber.
The preparation of Dehydrofluorination catalyst: its preparation method of Dehydrofluorination catalyst is seen Chinese patent CN100372607C disclosed method.
The preparation of isomerization catalyst: aluminum nitrate is dissolved in the water, add precipitation agent ammoniacal liquor at 60 ℃, between control pH value of solution 5.5～6.5 scopes, it is fully precipitated under agitation condition, with the slurry by filtration that forms, to neutral, 150 ℃ of dryings 12 hours, obtain Al (OH) with deionized water wash then
3
With gained Al (OH)
3Compare uniform mixing with tindioxide by required quality, compression molding, make catalyst precursor, catalyst precursor 400 ℃ of roastings 10 hours in retort furnace, the tubular reactor of packing into then is warming up to 300 ℃, feeding hydrogen fluoride gas fluoridized 2 hours, temperature rise rate with 1 ℃/min is warming up to 350 ℃ then, continues to fluoridize 10 hours, makes isomerization catalyst.
At internal diameter is to add 50 milliliters of commercially available 2%Pd/C catalyzer in the carbon steel pipe of 38mm.First temperature of reactor is 50 ℃, feeds H
2And HFP, control H
2With the mol ratio of HFP be 2, the HFP air speed is 360h
-1, reaction pressure 0.1MPa behind the reaction 20h, with organic composition in the gas chromatographic analysis reaction product, the results are shown in Table 1.
At internal diameter is to add 50 milliliters of commercially available 5%Pd/C catalyzer in the Glass tubing of 38mm.First reactor is in 0 ℃ of ice bath, feeds H
2And HFP, control H
2With the mol ratio of HFP be 2, the HFP air speed is 480h
-1, reaction pressure 0.1MPa behind the reaction 20h, with organic composition in the gas chromatographic analysis reaction product, the results are shown in Table 1.
Operation substantially the same manner as Example 1, different is that temperature of reaction is 100 ℃, the results are shown in Table 1.
Operation substantially the same manner as Example 1, different is that temperature of reaction is 200 ℃, catalyzer is commercially available 0.5%Pd/C, the results are shown in Table 1.
Operation substantially the same manner as Example 1, different is that the HFP air speed is 1800h
-1, the results are shown in Table 1.
Operation substantially the same manner as Example 1, different is that the HFP air speed is 720h
-1, the results are shown in Table 1.
Operation substantially the same manner as Example 1, different HFP air speeds be 120h
-1, the results are shown in Table 1.
Operation substantially the same manner as Example 1, that different is H
2With the mol ratio of HFP be 1, the results are shown in Table 1.
Operation substantially the same manner as Example 1, that different is H
2With the mol ratio of HFP be 1.5, the results are shown in Table 1.
Operation substantially the same manner as Example 1, that different is H
2With the mol ratio of HFP be 5, the results are shown in Table 1.
Operation substantially the same manner as Example 1, different is that reaction pressure is 0.3MPa, the results are shown in Table 1.
Operation substantially the same manner as Example 1, different is that reaction pressure is 0.6MPa, the results are shown in Table 1.
Operation substantially the same manner as Example 1, different is that reaction pressure is 1.0MPa, the results are shown in Table 1.
Table 1
At internal diameter is to add 50 milliliters of Dehydrofluorination catalysts in the carbon steel pipe of 38mm, and its quality percentage composition is Cr
3+: 70%; Al
3+: 28%; Zn
2+: 1%; Ni
3+: 1%.Second temperature of reactor is 350 ℃, feeds N
2And HFC-236ea, N
2Air speed 200h
-1, HFC-236ea air speed 100h
-1, reaction pressure 0.1MPa, behind the reaction 20h, reaction product with organic composition in the GC-MS analytical reaction product, the results are shown in Table 2 after HF is removed in washing, alkali cleaning.
Operation substantially the same manner as Example 14, different is that temperature of reaction is 250 ℃, the quality percentage composition of Dehydrofluorination catalyst is Cr
3+: 50%; Al
3+: 30%; Zn
2+: 10%; Ni
3+: 10%.The results are shown in Table 2.
Operation substantially the same manner as Example 14, different is that temperature of reaction is 330 ℃, the quality percentage composition of Dehydrofluorination catalyst is Cr
3+: 60%; Al
3+: 20%; Zn
2+: 10%; Ni
3+: 10%.The results are shown in Table 2.
Operation substantially the same manner as Example 14, different is that temperature of reaction is 380 ℃, the quality percentage composition of Dehydrofluorination catalyst is Cr
3+: 80%; Al
3+: 10%; Zn
2+: 5%; Ni
3+: 5%.The results are shown in Table 2.
Operation substantially the same manner as Example 14, different is that the HFC-236ea air speed is 300h
-1, the results are shown in Table 2.
Operation substantially the same manner as Example 14, different is that the HFC-236ea air speed is 30h
-1, the results are shown in Table 2.
Operation substantially the same manner as Example 14, different is that the HFC-236ea air speed is 200h
-1, the results are shown in Table 2.
Operation substantially the same manner as Example 14, different is that reaction pressure is 0.3MPa, the results are shown in Table 2.
Operation substantially the same manner as Example 14, different is that reaction pressure is 0.6MPa, the results are shown in Table 2.
Operation substantially the same manner as Example 14, different is that reaction pressure is 1.0MPa, the results are shown in Table 2.
Table 2
Embodiment 24
At internal diameter is to add 50 milliliters of isomerization catalysts in the carbon steel pipe of 38mm, and its quality percentage composition is an aluminum trifluoride: 95%; Tin tetrafluoride: 5%.The 3rd temperature of reactor is 50 ℃, feeds E-HFO-1225ye, and the E-HFO-1225ye air speed is 200h
-1, reaction pressure 0.1MPa behind the reaction 20h, with organic composition in the GC-MS analytical reaction product, the results are shown in Table 3.
Embodiment 25
Operation substantially the same manner as Example 24, different is that temperature of reaction is 25 ℃, the results are shown in Table 3.
Embodiment 26
Operation substantially the same manner as Example 24, different is that temperature of reaction is 75 ℃, the quality percentage composition of isomerization catalyst is an aluminum trifluoride: 90%; Tin tetrafluoride: 10%.The results are shown in Table 3.
Embodiment 27
Operation substantially the same manner as Example 24, different is that temperature of reaction is 100 ℃, the quality percentage composition of isomerization catalyst is an aluminum trifluoride: 95%; Tin tetrafluoride: 5%.The results are shown in Table 3.
Embodiment 28
Operation substantially the same manner as Example 24, different is that the E-HFO-1225ye air speed is 720h
-1, the results are shown in Table 3.
Embodiment 29
Operation substantially the same manner as Example 24, different is that the E-HFO-1225ye air speed is 72h
-1, the results are shown in Table 3.
Embodiment 30
Operation substantially the same manner as Example 24, different is that the E-HFO-1225ye air speed is 100h
-1, the results are shown in Table 3.
Embodiment 31
Operation substantially the same manner as Example 24, different is that reaction pressure is 0.3MPa, the results are shown in Table 2.
Embodiment 32
Operation substantially the same manner as Example 24, different is that reaction pressure is 0.6MPa, the results are shown in Table 2.
Embodiment 33
Operation substantially the same manner as Example 24, different is that reaction pressure is 1.0MPa, the results are shown in Table 2.
Table 3
Claims (2)
1, a kind of Z-1,2,3,3, the preparation method of 3-five fluorine propylene may further comprise the steps:
A. hydrogen and R 1216 enter first reactor, react in the presence of hydrogenation catalyst, and reaction conditions is: the mol ratio 1～5 of reaction pressure 0.1MPa～1.0MPa, hydrogen and R 1216, R 1216 air speed 120h
-1～1800h
-1, 0 ℃～200 ℃ of temperature of reaction, comprise in the product stream that reaction generates 1,1,1,2,3,3-HFC-236fa and unreacted hydrogen and R 1216, wherein hydrogenation catalyst is a palladium carbon catalyst, the palladium charge capacity is 05%～5%;
B. the product of step a flows to first distillation tower and separates, and tower still component is 1,1,1,2,3, and 3-HFC-236fa, cat head component are hydrogen and R 1216, and the cat head component is back to first reactor;
C. the tower still component 1,1,1 that obtains of nitrogen and step b, 2,3, the 3-HFC-236fa enters second reactor, 1,1,1,2,3, the 3-HFC-236fa is carried out dehydrofluorination in the presence of Dehydrofluorination catalyst, reaction conditions is: reaction pressure 0.1MPa～1.0MPa, 1,1,1,2,3,3-HFC-236fa air speed 30h
-1～300h
-1, 250 ℃～380 ℃ of temperature of reaction, comprise the Z-1 of generation in the product stream, 2,3,3,3-five fluorine propylene, E-1,2,3,3,3-five fluorine propylene, unreacted 1,1,1,2,3,3-HFC-236fa and nitrogen, wherein the quality percentage composition of Dehydrofluorination catalyst is Cr
3+: 50%～80%; Al
3+: 5%～30%; Zn
2+: 1%～10%; Ni
3+: 1%～10%;
D. the product stream of step c flows to the 3rd reactor, in the presence of isomerization catalyst, and E-1,2,3,3,3-five fluorine propylene carry out isomerization reaction, and reaction conditions is: reaction pressure 0.1MPa～1.0MPa, E-1,2,3,3,3-five fluorine propylene air speed 72h
-1～720h
-1, 25 ℃～100 ℃ of temperature of reaction, comprise Z-1 in the product stream, 2,3,3,3-five fluorine propylene, unreacted E-1,2,3,3,3-five fluorine propylene, 1,1,1,2,3,3-HFC-236fa and nitrogen, wherein the quality percentage composition of isomerization catalyst is an aluminum trifluoride: 85%～95%; Tin tetrafluoride: 5%～15%;
E. the product of steps d flows to into second column and separates, and tower still component is Z-1, and 2,3,3,3-five fluorine propylene, E-1,2,3,3,3-five fluorine propylene, hydrogen fluoride and 1,1,1,2,3,3-HFC-236fa, cat head component are nitrogen, and the cat head component is back to second reactor;
F. the tower still component of step e enters the 3rd distillation tower and separates, and tower still component is hydrogen fluoride and 1,1, and 1,2,3,3-HFC-236fa, cat head component are Z-1,2,3,3,3-five fluorine propylene, E-1,2,3,3,3-five fluorine propylene, cat head component detachment system through aftertreatment technologys such as deacidification, dehydration, rectifying, obtains target product Z-1,2,3,3,3-five fluorine propylene;
G. the tower still component of step f enters phase separator and is separated, and the organic phase that is rich in HFC-236ea is back to second reactor, is rich in the inorganic system that is separated of HF.
2, according to the described Z-1 of claim 1,2,3,3, the preparation method of 3-five fluorine propylene is characterized in that the reaction conditions of first reactor described in the step a is: the mol ratio 1.5～2 of reaction pressure 0.3MPa～0.6MPa, hydrogen and R 1216, the air speed 360h of R 1216
-1～720h
-1, 50 ℃～100 ℃ of temperature of reaction; The reaction conditions of second reactor described in the step c is: reaction pressure 0.3MPa～0.6MPa, 1,1,1,2,3, the air speed 100h of 3-HFC-236fa
-1～200h
-1, 300 ℃～350 ℃ of temperature of reaction; The reaction conditions of the 3rd reactor described in the steps d is: reaction pressure 0.3MPa～0.6MPa, E-1,2,3,3,3-five fluorine propylene air speed 100h
-1～200h
-1, 50 ℃～80 ℃ of temperature of reaction.
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Cited By (5)
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| CN111484391A (en) * | 2020-03-19 | 2020-08-04 | 山东东岳化工有限公司 | Method for preparing 1,2,3,3, 3-pentafluoropropene from hexafluoropropene |
| CN112794787A (en) * | 2021-04-08 | 2021-05-14 | 北京宇极科技发展有限公司 | Method for continuously preparing 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propylene in gas phase |
| CN113527042A (en) * | 2020-04-22 | 2021-10-22 | 浙江省化工研究院有限公司 | cis-HFO-1234ze production process and production system |
| CN113527048A (en) * | 2020-04-22 | 2021-10-22 | 浙江省化工研究院有限公司 | Process for isomerizing transHFO-1234 ze and catalyst support therefor |
| CN113527041A (en) * | 2020-04-22 | 2021-10-22 | 中化近代环保化工(西安)有限公司 | Process for preparing cis-HFO-1234 ze from mixture containing HCFC-244fa |
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| US9290424B2 (en) | 2013-03-14 | 2016-03-22 | Honeywell International Inc. | Processes for the hydrogenation of halogenated alkenes and the manufacture of fluorinated olefins |
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| CN111484391A (en) * | 2020-03-19 | 2020-08-04 | 山东东岳化工有限公司 | Method for preparing 1,2,3,3, 3-pentafluoropropene from hexafluoropropene |
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| CN113527042A (en) * | 2020-04-22 | 2021-10-22 | 浙江省化工研究院有限公司 | cis-HFO-1234ze production process and production system |
| CN113527048A (en) * | 2020-04-22 | 2021-10-22 | 浙江省化工研究院有限公司 | Process for isomerizing transHFO-1234 ze and catalyst support therefor |
| CN113527041A (en) * | 2020-04-22 | 2021-10-22 | 中化近代环保化工(西安)有限公司 | Process for preparing cis-HFO-1234 ze from mixture containing HCFC-244fa |
| CN113527042B (en) * | 2020-04-22 | 2023-10-03 | 浙江省化工研究院有限公司 | Production process and production system of cis HFO-1234ze |
| CN113527048B (en) * | 2020-04-22 | 2024-02-06 | 浙江省化工研究院有限公司 | Method for isomerising transHFO-1234 ze and catalyst carrier therefor |
| CN112794787A (en) * | 2021-04-08 | 2021-05-14 | 北京宇极科技发展有限公司 | Method for continuously preparing 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propylene in gas phase |
| CN112794787B (en) * | 2021-04-08 | 2021-07-09 | 泉州宇极新材料科技有限公司 | Method for continuously preparing 3,3, 3-trifluoro-2- (trifluoromethyl) -1-propylene in gas phase |
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