CN105481638B - A kind of synthetic method of 1,3,3,3- tetrafluoropropene - Google Patents
A kind of synthetic method of 1,3,3,3- tetrafluoropropene Download PDFInfo
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- CN105481638B CN105481638B CN201510801535.3A CN201510801535A CN105481638B CN 105481638 B CN105481638 B CN 105481638B CN 201510801535 A CN201510801535 A CN 201510801535A CN 105481638 B CN105481638 B CN 105481638B
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- CDOOAUSHHFGWSA-OWOJBTEDSA-N (e)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 title claims abstract description 22
- 238000010189 synthetic method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 77
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- CEBDXRXVGUQZJK-UHFFFAOYSA-N 2-methyl-1-benzofuran-7-carboxylic acid Chemical compound C1=CC(C(O)=O)=C2OC(C)=CC2=C1 CEBDXRXVGUQZJK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 28
- 239000011630 iodine Substances 0.000 claims abstract description 26
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 11
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims abstract description 10
- KYSCILZWHIIRIW-UHFFFAOYSA-N 1-fluoro-1-iodopropane Chemical compound CCC(F)I KYSCILZWHIIRIW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000006835 compression Effects 0.000 claims abstract description 4
- 238000007906 compression Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 39
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 36
- 229910052787 antimony Inorganic materials 0.000 claims description 20
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 20
- 235000009518 sodium iodide Nutrition 0.000 claims description 13
- CDOOAUSHHFGWSA-UHFFFAOYSA-N 1,3,3,3-tetrafluoropropene Chemical class FC=CC(F)(F)F CDOOAUSHHFGWSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- -1 trifluoropropyl Alkene Chemical class 0.000 claims description 5
- FDMFUZHCIRHGRG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=C FDMFUZHCIRHGRG-UHFFFAOYSA-N 0.000 abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000006073 displacement reaction Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZDCWZRQSHBQRGN-UHFFFAOYSA-N 1,1,1,2,3-pentafluoropropane Chemical compound FCC(F)C(F)(F)F ZDCWZRQSHBQRGN-UHFFFAOYSA-N 0.000 description 2
- VJGCZWVJDRIHNC-UHFFFAOYSA-N 1-fluoroprop-1-ene Chemical compound CC=CF VJGCZWVJDRIHNC-UHFFFAOYSA-N 0.000 description 2
- ZGOMEYREADWKLC-UHFFFAOYSA-N 3-chloro-1,1,1,3-tetrafluoropropane Chemical compound FC(Cl)CC(F)(F)F ZGOMEYREADWKLC-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 206010020852 Hypertonia Diseases 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 235000021050 feed intake Nutrition 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- LDTMPQQAWUMPKS-OWOJBTEDSA-N (e)-1-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)\C=C\Cl LDTMPQQAWUMPKS-OWOJBTEDSA-N 0.000 description 1
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005796 dehydrofluorination reaction Methods 0.000 description 1
- 238000007337 electrophilic addition reaction Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- VPAYJEUHKVESSD-UHFFFAOYSA-N trifluoroiodomethane Chemical compound FC(F)(F)I VPAYJEUHKVESSD-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
- C07C17/04—Preparation of halogenated hydrocarbons by addition of halogens to unsaturated halogenated hydrocarbons
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses one kind 1,3,3, the synthetic method of 3- tetrafluoropropene, the following steps are included: the mixture of iodine, iodine pentafluoride and catalyst is added in (1) in the reactor, reaction temperature is controlled, trifluoro propene is passed through, when system pressure is stablized, stop reaction, obtains 1,3,3, the mass ratio of the tetra- iodo- propane of fluoro- 2- of 3-, iodine and iodine pentafluoride is 1:0.4~0.5, and the mass ratio of iodine and catalyst is 1:0.01~0.05, reaction temperature is -15~35 DEG C, and reaction pressure is 0.1~0.6MPa；(2) the fluoro- iodo- propane of 2- of material 1,3,3,3- tetra- in kettle is steamed, is passed through normal pressure in the reactor for fill lye and is reacted, gas-phase product obtains 1,3,3,3- tetrafluoropropene of product through drying, compression, and the reaction temperature is 35~80 DEG C.The advantages that present invention has equipment simple, and operational safety is high, and product purity is high.
Description
Technical field
The present invention relates to a kind of synthetic methods of 1,3,3,3- tetrafluoropropene.
Background technique
1,3,3,3- tetrafluoropropene (HFO-1234ze), 2,3,3,3- tetrafluoropropene (HFO- in fluorine refrigeration industry
1234yf), trifluoroiodomethane (FIC-l311) and l, 2,3,3,3- pentafluoropropene (HFC-1225ye) and for 0 ozone-depleting
Latent value (ODP), low temperature chamber effect dive (GWP=6), it is considered to be the 3rd generation refrigerant, as the extensive high GWP of alternate application
1,1,1,2- tetrafluoroethane (HFC-134a), l, the 2nd generations refrigerant replacement such as 1,1,2,2- pentafluoroethane (HFC-125).
HFO-l234ze is nontoxic, non-ignitable, and chemical property is more stable, is a kind of important HF hydrocarbon (HFOs) III.In foaming agent, system
Cryogen, aerosol propellants, cleaning agent etc. are widely used, and HFO-1234ze is important chemical materials intermediate.
The synthetic method of 1,3,3,3- tetrafluoropropene (HFO-1234ze) mainly has:
1) using HFC-245fa as raw material, through gas phase or liquid phase dehydrofluorination, HFO-1234ze is obtained.2) with 1- chloro- 3,3,
3- trifluoro propene (HCFC-1233zd) is raw material, and exchange chloride for fluoride directly occurs with HF and generates HFO-l234ze or first will
HCFC-1233zd is reacted to obtain HCFC-244fa and HFC-245fa in gas phase with HF, then HCFC-244fa take off HCl and
HFC-245fa takes off HF process and obtains HFO-1234ze.3) it with 1,1, l, 3,3- pentachloropropane (HCC-240fa) for raw material, uses
The chromium-based catalysts of Al, Zn, Mg, Nj obtain HFO-l234ze through two steps fluorination hydrofluorination.4) with 1,1,1,2,3- pentafluoropropane
It (HFC-245eb) be the method for raw material coproduction HFO-l234ze and HFO-1234yf point is vapor phase method and liquid phase method.In this method
The selectivity of HFO-l234ze is smaller, but has certain value to coproduction HFO-1234vf.5) halide and vinyl halides are first
Electrophilic addition reaction occurs under metallic catalyst Cu or AlCl catalyst action and generates halogenopropane, halogenopropane is in catalyst
Effect is lower and AHF gas phase reaction forms general formula as CF3The compound (X Cl, Br and I) of CH CFX, the compound in Fe base or
High temperature sloughs HX under Cr base catalyst action, prepares HFO-l234ze.6) with 3,3,3- trifluoro propene (HFO-1243) for raw material
Synthesize HFO-l234ze.
Sudip M etc. uses HFO-1243 and X first1、X2(X1、X2It is independent to be selected from H, F, CI, Br, I, but X1、X2When different
Addition reaction is carried out for H), generates CF3CHX1CH2X2, exchange chloride for fluoride is then carried out under gas phase, then de- HX obtains HFO-
l234ze.Such as: HFO-1243 and Cl2Under 200~400nm of ultraviolet light irradiation.Catalyst quality score is 1%~3%
Au02, reaction temperature is 0~10 DEG C of generation CF3CHClCH2Cl passes through Cr with HF after separation2O catalyst, reaction temperature are
250~400 DEG C, time of contact 550s, generate CF3CHClCH2F, CF3CHClCH2F is in Cr2O3Catalyst, reaction temperature are
425~550 DEG C, time of contact be 25~30s under the conditions of, de- HCl obtains HFO-1234ze, after separation yield be 40~
60%.
Summary of the invention
Present invention aims at deficiency of the prior art is directed to, it is simple, in high yield to provide a kind of process equipment
The synthetic method of 1,3,3,3- tetrafluoropropenes of synthesis, this method simple process, at low cost, high income have industry well
Application prospect.
It is special in order to solve the above-mentioned technical problems, the present invention provides a kind of synthetic method of 1,3,3,3- tetrafluoropropenes
Sign be the following steps are included:
(1) mixture of iodine, iodine pentafluoride and catalyst is added in the reactor, controls reaction temperature, is passed through three
Fluoropropene, when system pressure stablize when, stop reaction, obtain 1,3,3, the 3- tetra- fluoro- iodo- propane of 2-, in mixture iodine with
The mass ratio of iodine pentafluoride is 1:0.4~0.5, and the mass ratio of iodine and catalyst is 1:0.01~0.05, reaction temperature is-
15~35 DEG C, reaction pressure is 0.1~0.6MPa；
(2) the fluoro- iodo- propane of 2- of material 1,3,3,3- tetra- in kettle is steamed, is passed through in the reactor for fill lye and carries out instead
It answers, gas-phase product obtains 1,3,3,3- tetrafluoropropene of product through drying, compression, and alkali liquid temperature is 35~80 DEG C.
Further, in step (1), catalyst is the mixture of antimony and potassium iodide or antimony and sodium iodide, antimony and potassium iodide
Or the mass ratio of antimony and sodium iodide is 1:0.1~1.
After it is preferred that, mass ratio 1:0.4~0.8 of antimony and potassium iodide or antimony and sodium iodide, by control antimony and potassium iodide or
The mass ratio of antimony and sodium iodide reduces the waste of resource, has saved cost so that the reaction of material is more complete.
After it is preferred that, in step (1), the mass ratio of iodine and iodine pentafluoride is 1:0.44~0.48.
After it is preferred that, in step (1), the mass ratio of iodine and catalyst is 1:0.02~0.03, by controlling simple substance
The mass ratio of iodine and catalyst, so that the quality of material after reaction is more preferable, the reaction time is shorter, accelerates reaction rate.
After it is preferred that, in step (1), reaction temperature is 5~25 DEG C.
After it is preferred that, in step (1), reaction pressure is 0.2~0.4MPa, and production can be improved in the control of reaction pressure
Efficiency shortens the reaction time, reduces cost of investment.
Further, in step (2), concentration of lye is 10~30%.
After it is preferred that, the concentration of lye that concentration of lye is 15~20%, 15~20% can not only make reaction efficiency high,
And the product yield after reacting is also high.
After it is preferred that, in step (2), alkali liquid temperature is 45~60 DEG C.
Iodine and iodine pentafluoride feed intake would generally Choice Theory molar ratio, it is micro in iodine but in actual production
Moisture can make part iodine pentafluoride (IF5) decomposition failure, reduce its effective component.Therefore iodine pentafluoride (IF is properly increased5) dosage
The yield of product can be improved.The mass ratio that feeds intake of iodine and iodine pentafluoride is that 1:0.4~0.5 is advisable, preferably 1:0.44~
0.48。
In reaction process, catalyst and iodine pentafluoride (IF5) the higher complicated catalyst system of reaction generation catalytic effect, make
Reaction is easier to carry out, and catalyst usage amount is less, generally the 1~5% of iodine dosage, preferably 2~3%.It is added at one time,
It can repeatedly use.Compared to other techniques, in the presence of effective catalyst, reaction temperature is lower, it is subzero can be anti-
It answers.Being typically chosen -15~35 DEG C is advisable, and preferably 5~25 DEG C.Temperature is excessively high to be easy to happen depth side reaction, generates chain alkyl
Iodine.Temperature is too low, and material viscosity is excessive, reduces reaction rate, while be easy to causeing stirring problem.
In reaction process, the control of pressure is more important.Hypertonia, highly exothermic in reaction are difficult to remove, and cause
Kettle temperature should not control.Reaction pressure is too low, reduces reaction rate, extends the reaction time, reduces production efficiency.Pressure selection 0.1
~0.6MPa is advisable, preferably 0.2~0.4MPa.
1 steamed from reaction kettle, 3,3, the 3- tetra- fluoro- iodo- propane of 2-, is passed through in the reactor for fill lye and is reacted,
The concentration of lye is high, and temperature is low, and lye viscosity is big, and reaction is not easy to carry out；The concentration of lye is low, and temperature is high, reacts too fast, lye
Consumption is fast.Therefore concentration of lye is selected as 10~30%, preferably 15~20%；Temperature is selected as 35~80 DEG C, preferably 45~60
℃。
Compared with prior art, the invention has the following advantages that
1, easy to operate, equipment investment is few, high production efficiency, and catalyst does not need to be separated recyclable, is suitble to extensive
Industrialized production；
2, reaction yield is high, and selectivity is good, and yield reaches as high as 98%, selectively reaches as high as 99%.
Specific embodiment
The present invention is a kind of synthetic method of 1,3,3,3- tetrafluoropropenes, comprising the following steps:
(1) mixture of iodine, iodine pentafluoride and catalyst is added in the reactor, controls reaction temperature, is passed through three
Fluoropropene, when system pressure stablize when, stop reaction, obtain 1,3,3, the 3- tetra- fluoro- iodo- propane of 2-, in mixture iodine with
The mass ratio of iodine pentafluoride is 1:0.4~0.5, preferably after, the mass ratio of iodine and iodine pentafluoride is 1:0.44~0.48, single
The mass ratio of matter iodine and catalyst is 1:0.01~0.05, preferably after, the mass ratio of iodine and catalyst be 1:0.02~
0.03, by controlling the mass ratio of iodine and catalyst, so that the quality of material after reaction is more preferable, the reaction time is shorter, adds
Fast response rate, reaction temperature be -15~35 DEG C, preferably after, reaction temperature be 5~25 DEG C, reaction pressure be 0.1~
0.6MPa, preferably after, reaction pressure is 0.2~0.4MPa, and the control of reaction pressure can be improved production efficiency, shortens reaction
Time, cost of investment is reduced, catalyst is the mixture of antimony and potassium iodide or antimony and sodium iodide, antimony and potassium iodide or antimony and iodate
The mass ratio of sodium is 1:0.1~1, preferably after, mass ratio 1:0.4~0.8 of antimony and potassium iodide or antimony and sodium iodide passes through control
The mass ratio of antimony and potassium iodide or antimony and sodium iodide reduces the waste of resource so that the reaction of material is more complete, saves
Cost；
(2) the fluoro- iodo- propane of 2- of material 1,3,3,3- tetra- in kettle is steamed, is passed through in the reactor for fill lye and carries out instead
Answer, gas-phase product obtains 1,3,3,3- tetrafluoropropene of product through drying, compression, and alkali liquid temperature is 35~80 DEG C, preferably after, lye
Temperature be 45~60 DEG C, concentration of lye be 10~30%, preferably after, concentration of lye be 15~20%, 15~20% lye it is dense
Degree can not only make reaction efficiency high, but also the product yield after reaction is also high.
Iodine and iodine pentafluoride feed intake would generally Choice Theory molar ratio, it is micro in iodine but in actual production
Moisture can make part iodine pentafluoride (IF5) decomposition failure, reduce its effective component.Therefore iodine pentafluoride (IF is properly increased5) dosage
The yield of product can be improved.The mass ratio that feeds intake of iodine and iodine pentafluoride is that 1:0.4~0.5 is advisable, preferably 1:0.44~
0.48。
In reaction process, catalyst and iodine pentafluoride (IF5) the higher complicated catalyst system of reaction generation catalytic effect, make
Reaction is easier to carry out, and catalyst usage amount is less, generally the 1~5% of iodine dosage, preferably 2~3%.It is added at one time,
It can repeatedly use.Compared to other techniques, in the presence of effective catalyst, reaction temperature is lower, it is subzero can be anti-
It answers.Being typically chosen -15~35 DEG C is advisable, and preferably 5~25 DEG C.Temperature is excessively high to be easy to happen depth side reaction, generates chain alkyl
Iodine.Temperature is too low, and material viscosity is excessive, reduces reaction rate, while be easy to causeing stirring problem.
In reaction process, the control of pressure is more important.Hypertonia, highly exothermic in reaction are difficult to remove, and cause
Kettle temperature should not control.Reaction pressure is too low, reduces reaction rate, extends the reaction time, reduces production efficiency.Pressure selection 0.1
~0.6MPa is advisable, preferably 0.2~0.4MPa.
1 steamed from reaction kettle, 3,3, the 3- tetra- fluoro- iodo- propane of 2-, is passed through in the reactor for fill lye and is reacted,
The concentration of lye is high, and temperature is low, and lye viscosity is big, and reaction is not easy to carry out；The concentration of lye is low, and temperature is high, reacts too fast, lye
Consumption is fast.Therefore concentration of lye is selected as 10~30%, preferably 15~20%；Temperature is selected as 35~80 DEG C, preferably 45~60
℃。
More specific description is carried out to the present invention by the following examples, but the present invention is not limited to the embodiment described.
Embodiment 1:
In 10L horizontal reacting kettle, 8kg iodine, 200g Sb are put into, sodium iodide 50g is stirred after nitrogen displacement is qualified
Lower (the IF that 4.0kg iodine pentafluoride is added5), 15 DEG C of reaction temperature, accomplished continuously or intermittently it is passed through trifluoro propene, reaction pressure
0.3MPa.When pressure is stablized, stop into trifluoro propene.Reaction kettle heating is steamed into 1,3,3, the 3- tetra- fluoro- iodo- propane of 2-, is passed through
Over-richness 15%, temperature 45 C lye, dry, cool solidifying, collection obtain 1,3,3,3- tetrafluoropropene products, and purity 99.5% is received
Rate 98.2%.
Embodiment 2:
In 10L horizontal reacting kettle, 8kg iodine, 200g Sb are put into, sodium iodide 50g is stirred after nitrogen displacement is qualified
Lower (the IF that 3.2kg iodine pentafluoride is added5), 5 DEG C of reaction temperature, accomplished continuously or intermittently it is passed through trifluoro propene, reaction pressure 0.3MPa.
When pressure is stablized, stop into trifluoro propene.Reaction kettle heating is steamed into 1,3,3, the 3- tetra- fluoro- iodo- propane of 2-, through over-richness
20%, temperature 45 C lye, dry, cool solidifying, collection obtains 1,3,3,3- tetrafluoropropene products, purity 99.4%, yield
97.3%.
Embodiment 3:
In 10L horizontal reacting kettle, 8kg iodine, 267g Sb are put into, potassium iodide 133g is stirred after nitrogen displacement is qualified
Mix the lower (IF that 3.2kg iodine pentafluoride is added5), 35 DEG C of reaction temperature, accomplished continuously or intermittently it is passed through trifluoro propene, reaction pressure
0.2MPa.When pressure is stablized, stop into trifluoro propene.Reaction kettle heating is steamed into 1,3,3, the 3- tetra- fluoro- iodo- propane of 2-, is passed through
Over-richness 10%, temperature 45 C lye, dry, cool solidifying, collection obtain 1,3,3,3- tetrafluoropropene products, and purity 99.1% is received
Rate 97.3%.
Embodiment 4:
In 10L horizontal reacting kettle, 8kg iodine, 40g Sb are put into, sodium iodide 40g is stirred after nitrogen displacement is qualified
Lower (the IF that 3.5kg iodine pentafluoride is added5), -15 DEG C of reaction temperature, accomplished continuously or intermittently it is passed through trifluoro propene, reaction pressure
0.4MPa.When pressure is stablized, stop into trifluoro propene.Reaction kettle heating is steamed into 1,3,3, the 3- tetra- fluoro- iodo- propane of 2-, is passed through
Over-richness 30%, 80 DEG C of lye of temperature, dry, cool solidifying, collection obtain 1,3,3,3- tetrafluoropropene products, and purity 98.8% is received
Rate 96.9%.
Embodiment 5:
In 10L horizontal reacting kettle, 8kg iodine, 107g Sb are put into, potassium iodide 43g is stirred after nitrogen displacement is qualified
Lower (the IF that 3.5kg iodine pentafluoride is added5), 0 DEG C of reaction temperature, accomplished continuously or intermittently it is passed through trifluoro propene, reaction pressure 0.6MPa.
When pressure is stablized, stop into trifluoro propene.Reaction kettle heating is steamed into 1,3,3, the 3- tetra- fluoro- iodo- propane of 2-, through over-richness
20%, temperature 60 C lye, dry, cool solidifying, collection obtains 1,3,3,3- tetrafluoropropene products, purity 99.5%, yield
97.8%.
Embodiment 6:
In 10L horizontal reacting kettle, 8kg iodine, 83g Sb are put into, sodium iodide 67g is stirred after nitrogen displacement is qualified
Lower (the IF that 3.8kg iodine pentafluoride is added5), 10 DEG C of reaction temperature, accomplished continuously or intermittently it is passed through trifluoro propene, reaction pressure
0.2MPa.When pressure is stablized, stop into trifluoro propene.Reaction kettle heating is steamed into 1,3,3, the 3- tetra- fluoro- iodo- propane of 2-, is passed through
Over-richness 25%, 35 DEG C of lye of temperature, dry, cool solidifying, collection obtain 1,3,3,3- tetrafluoropropene products, and purity 99.5% is received
Rate 97.4%.
The above is only specific embodiments of the present invention, but technical characteristic of the invention is not limited thereto.It is any with this hair
Based on bright, to realize essentially identical technical effect, made ground simple change, equivalent replacement or modification etc. are all covered
Among protection scope of the present invention.
Claims (8)
1. the synthetic method of 1,3,3,3- tetrafluoropropene of one kind, which comprises the following steps:
(1) mixture of iodine, iodine pentafluoride and catalyst is added in the reactor, controls reaction temperature, is passed through trifluoropropyl
Alkene, when system pressure stablize when, stop reaction, obtain 1,3,3, the 3- tetra- fluoro- iodo- propane of 2-, in the mixture iodine with
The mass ratio of iodine pentafluoride is 1:0.4~0.5, and the mass ratio of iodine and catalyst is 1:0.01~0.05, reaction temperature is-
15~35 DEG C, reaction pressure is 0.1~0.6MPa, and the catalyst is the mixture of antimony and potassium iodide or antimony and sodium iodide, institute
State mass ratio 1:0.4~0.8 of antimony and the potassium iodide or the antimony and the sodium iodide；
(2) the fluoro- iodo- propane of 2- of material 1,3,3,3- tetra- in kettle is steamed, is passed through in the reactor for fill lye and is reacted, gas
Phase product obtains 1,3,3,3- tetrafluoropropene of product through drying, compression, and the alkali liquid temperature is 35~80 DEG C.
2. a kind of synthetic method of 1,3,3,3- tetrafluoropropenes according to claim 1, it is characterised in that: in the step
(1) in, the mass ratio of the iodine and the iodine pentafluoride is 1:0.44~0.48.
3. a kind of synthetic method of 1,3,3,3- tetrafluoropropenes according to claim 1, it is characterised in that: in the step
(1) in, the mass ratio of the iodine and the catalyst is 1:0.02~0.03.
4. a kind of synthetic method of 1,3,3,3- tetrafluoropropenes according to claim 1, it is characterised in that: in the step
(1) in, the reaction temperature is 5~25 DEG C.
5. a kind of synthetic method of 1,3,3,3- tetrafluoropropenes according to claim 1, it is characterised in that: in the step
(1) in, the reaction pressure is 0.2~0.4MPa.
6. a kind of synthetic method of 1,3,3,3- tetrafluoropropenes according to claim 1, it is characterised in that: in the step
(2) in, the concentration of lye is 10~30%.
7. a kind of synthetic method of 1,3,3,3- tetrafluoropropenes according to claim 6, it is characterised in that: the concentration of lye
It is 15~20%.
8. a kind of synthetic method of 1,3,3,3- tetrafluoropropenes according to claim 1, it is characterised in that: in the step
(2) in, the alkali liquid temperature is 45~60 DEG C.
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| CN101351427A (en) * | 2005-11-03 | 2009-01-21 | 霍尼韦尔国际公司 | Method for producing fluorinated organic compounds |
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| US5283380A (en) * | 1992-06-15 | 1994-02-01 | Dow Corning Corporation | Process for preparing an active telogen |
| CN1976885A (en) * | 2004-04-29 | 2007-06-06 | 霍尼韦尔国际公司 | Processes for synthesis of 1,3,3,3-tetrafluoropropene and 2,3,3,3-tetrafluoropropene |
| CN101351427A (en) * | 2005-11-03 | 2009-01-21 | 霍尼韦尔国际公司 | Method for producing fluorinated organic compounds |
| CN102241561A (en) * | 2011-05-12 | 2011-11-16 | 山东中氟化工科技有限公司 | One-step preparation method of perfluoroalkyl iodide |
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