CN107652160A - A kind of method for preparing the trans trifluoro propene of 1 chlorine 3,3,3 - Google Patents
A kind of method for preparing the trans trifluoro propene of 1 chlorine 3,3,3 Download PDFInfo
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- CN107652160A CN107652160A CN201711006541.5A CN201711006541A CN107652160A CN 107652160 A CN107652160 A CN 107652160A CN 201711006541 A CN201711006541 A CN 201711006541A CN 107652160 A CN107652160 A CN 107652160A
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- butylamine
- metal halide
- chloro
- alkali
- alkali compounds
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/09—Geometrical isomers
Abstract
The invention discloses the method that one kind prepares the trans trifluoro propene of 1 chlorine 3,3,3, and this method is using alkali compounds and metal halide as composite catalyst, hydrogen fluoride and 1,1,1,3, the trifluoro propene of 3 pentachloropropane liquid-phase fluorination synthesis of trans, 1 chlorine 3,3,3, wherein metal halide are TiCl4、SnCl4、TiF4Or SnF4, alkali compounds is alkali halide, organic amine, ethers or sulfone class, and the mol ratio of alkali compounds and metal halide is 1:0.3~3.The method for preparing the trans trifluoro propene of 1 chlorine 3,3,3 of the present invention has the advantages of reaction selectivity is high, reaction condition is gentle.
Description
Technical field
The present invention relates to a kind of method for preparing anti-form-1-chloro-3,3,3 ,-trifluoropropene, more particularly to hydrogen fluoride and 1,
1,1,3,3- pentachloropropanes are the method that raw material liquid-phase fluorination prepares anti-form-1-chloro- 3,3,3- trifluoro propenes.
Background technology
The latent value of the ozone depletion of anti-form-1-chloro-3,3,3 ,-trifluoropropene (HCFO-1233zd (E)) is 0.00024, greenhouse
The latent value of effect is 7.0, and environmental-protecting performance is excellent, and toxicity is low, non-ignitable under normality, safe to use, is foamed using HCFO-1233zd (E)
The RPUF combination property of system synthesis is good, and heat-insulating property is excellent, disclosure satisfy that adiabatic heat-insulation industry
Demand, it is considered to be 1,1- bis- chloro- 1- fluoroethanes (HCFC-141b) and 1, the reason of 1,1,3,3- pentafluoropropane (HFC-245fa)
Think substitute.
Industrially typically with hydrogen fluoride and 1,1,1,3,3- pentachloropropane (HCC-240fa) is raw material, through gas phase fluorination or
Person's liquid-phase fluorination synthesis HCFO-1233zd (E).Chinese patent CN1166479A discloses one kind with Cr-Ni/AlF3For catalysis
Agent, gas phase fluorination HCC-240fa synthesizes HCFO-1233zd (E), 250 DEG C of reaction temperature, time of contact in tubular reactor
2s, HF/HCC-240fa mol ratio are 14:1, HCC-240fa conversion ratio is 100%, and selectivity is 72%, and Main By product is
Excessive fluoride (8.2% HFO-1234ze and 8.5% HFC-245fa) and cis HCFO-1233zd, this method HCFO-
1233zd (E) selectivity is not high, and reaction temperature is high, and energy consumption is big.Chinese patent CN103189339A is reported without using catalysis
Agent, liquid-phase fluorination HCC-240fa synthesizes HCFO-1233zd in tank reactor, 110 DEG C, anti-under 1.72~2.42MPa (G)
9.5h is answered, the yield that HCC-240fa conversion ratios are 96.8%, HCFO-1233zd (E) is 36.2%, HCFO-1233zd's (Z)
Yield is 1.48%, and Main By product is primary fluorinated product CFCl2CH2CHCl2(HCFC-241fa, yield 38.7%), should
Method HCFO-1233zd (E) poor selectivity.
The content of the invention
It is insufficient present in background technology it is an object of the invention to overcome, there is provided a kind of reaction selectivity is high, condition temperature
The method for preparing anti-form-1-chloro- 3,3,3- trifluoro propenes of sum.
In order to realize the purpose of the present invention, the present invention has formulated one kind and answered by alkali compounds with what metal halide formed
Catalyst is closed, the catalyst is acid adjustable amphoteric catalyst, and wherein metal halide, which provides acidity, makes HCC-240fa
Fluorination reaction, alkali compounds provide alkalescence and promote dehydrochlorination generation alkene HCFO-1233zd.
The technical scheme that specifically uses of the present invention for：Using hydrogen fluoride and 1,1,1,3,3- pentachloropropanes as raw material liquid-phase fluorination
1- chloro-3,3,3 ,-trifluoropropenes are synthesized, wherein metal halide is TiCl4、SnCl4、TiF4Or SnF4, alkali compounds is alkali
Metal halide, organic amine, ethers or sulfone class.
Heretofore described metal halide is preferably TiCl4Or SnCl4。
According to the alkalescence of alkali compounds, compound urge can be adjusted by adjusting the mol ratio of alkali compounds and metal halide
The acidity of agent, different catalytic effects is obtained, the mol ratio of suitable alkali compounds and metal halide is 1:0.3~3,
Further preferred mol ratio is 1:0.5~2.
Heretofore described alkali halide is KF, KCl, CsF or CsCl, and described organic amine is n-propylamine, different
Propylamine, n-butylamine, tert-butylamine, n-amylamine, di-n-propylamine, di-n-butylamine, triethylamine, tripropyl amine (TPA), tri-n-butylamine, diisopropylethylamine
Or pyridine, described ethers are ether, propyl ether, tetrahydrofuran or dioxane, described sulfone class is dimethyl sulfoxide or sulfolane.
In the present invention preferable alkali compounds be KF, butylamine, diisopropylethylamine, di-n-butylamine, tri-n-butylamine, ether or
Dimethyl sulfoxide, or their mixture.
The method for preparing HCFO-1233zd (E) of the present invention can be carried out intermittently or serially.In a batch process, HF and
HCC-240fa is disposably added to reactor, rises to corresponding reaction temperature, preferable reaction condition is HCC-240fa and HF
Molar ratio be 1:5~1:30, HCC-240fa inventory and the mol ratio of metal halide are 0.1：1~5：1, instead
It is 80 DEG C~130 DEG C to answer temperature, and the reaction time is 0.5h~10h, and reaction pressure is 1.25~2.0MPA.In a continuous process,
HF and HCC-240fa continuously enters reactor, and preferable reaction condition is：HCC-240fa and HF mol ratio is 1:3~1:
10, HCC-240fa inventory and the mol ratio of metal halide are 0.1：1~1：1, reaction temperature is 100 DEG C~120 DEG C,
Reaction pressure is 1.0~2.0MPA.
Compared with prior art, the advantage of the invention is that：
(1) reaction selectivity is high, the composite catalyst being made up of alkali compounds and metal halide that the present invention formulates
It is acid adjustable amphoteric catalyst, has good selectivity to HCFO-1233zd (E), under suitable conditions HCFO-
1233zd (E) selectivity is selective up to more than 90% under conditions of more excellent up to more than 85%.
(2) present invention prepares HCFO-1233zd (E) using liquid phase method, and reaction temperature is at 80 DEG C~130 DEG C, less than gas phase
250 DEG C of method, condition milder.
Embodiment
It is following the present invention to be described in further detail in conjunction with the embodiments explanation, but do not limit the scope of the invention.
Embodiment 1
Interval liquid phase fluorination reaction is carried out in the 300mL stainless steel autoclaves with stirring.Put into successively into reactor
57g TiCl4, 8.7g KF, add 60g HF and carry out fluorination treatment, processing procedure excludes the HCl of generation, control by gas phase mouth
Pressing pressure is within 0.25MPa.60 DEG C are warming up to, constant temperature 1h, processing procedure terminates.
32g HCC-240fa are added into reactor, reaction temperature is 115 DEG C, and gas phase mouth row pressure in course of reaction is stable
Reactor pressure is 1.5MPa, is cooled after reacting 2h.Washing bottle of the gas material of discharge through being placed in -5 DEG C of cold baths removes
After acid, phase point is stood, collects lower floor's about 15.8g organic phases.Gas chromatographic analysis organic phase, the results showed that HCFO-1233zd (E)
Selectivity be 86.1%, HCFO-1233zd (Z) selectivity be the tetrafluoropropane (HCFC- of 7.2%, 3- chloro- 1,1,1,3-
Selectivity 244fa) is 5.2%.
Embodiment 2~7
The method that embodiment 2~7 prepares HCFO-1233zd (E) is same as Example 1, except that changing organic base
Property compound, reaction result are as shown in table 1.
Table 1
Embodiment 8
The method that embodiment 8 prepares HCFO-1233zd (E) is same as Example 1, except that using SnCl4Instead of
TiCl4.It is collected into about 16.2g organic phases.Gas chromatographic analysis organic phase shows that HCFO-1233zd (E) selectivity is
85.8%, HCFO-1233zd (Z) selectivity are 7.5%, 3- chloro- 1, the selection of 1,1,3- tetrafluoropropane (HCFC-244fa)
Property is 6.4%.
Embodiment 9
Put into 57.1g TiCl successively into reactor in equipment same as Example 14, 22.2g ether, add
60g HF carry out fluorination treatment, and processing procedure excludes the HCl of generation by gas phase mouth, and control pressure is within 0.25MPa.Heating
To 60 DEG C, constant temperature 1h, processing procedure terminates.
43g HCC-240fa are added into reactor, reaction temperature is 115 DEG C, and gas phase mouth row pressure in course of reaction is stable
Reactor pressure is 1.5MPa, is cooled after reacting 2h.Washing bottle of the gas material of discharge through being placed in -5 DEG C of cold baths removes
After acid, phase point is stood, collects lower floor's about 22.5g organic phases.Gas chromatographic analysis organic phase, the results showed that HCFO-1233zd (E)
Selectivity be 88.1%, HCFO-1233zd (Z) selectivity be 6.8%, HCFC-244fa selectivity be 4.9%.
Embodiment 10~12
The method that embodiment 10~12 prepares HCFO-1233zd (E) is same as Example 9, except that changing organic
Alkali compounds, reaction result are as shown in table 2.
Table 2
Embodiment 13
Continuous Liquid Phase fluorination is carried out in 2L stainless steel autoclaves, and the top of autoclave is equipped with destilling tower and reflux condensation mode
Device, bottom are heated using oil cauldron, and tower top material is collected in -20 DEG C of cold baths after washing alkalescence deacidification.Into reactor
500g TiCl are put into successively4, 280g tri-n-butylamines, 800g HF, the HCl of generation is excluded by gas phase mouth, control system pressure is not
More than 0.25MPa, 60 DEG C are warming up to, constant temperature 2h.Then continuously HCC-240fa and HF are squeezed into reactor by measuring pump
In, HCC-240fa feed rate is 200g/h, and HF feed rate is that 95g/h, HCC-240fa and HF mol ratio are 1：
5.1, reaction temperature is 112~116 DEG C, and reaction pressure is 1.4~1.6MPA.Analyze the composition of top gaseous phase material, reaction knot
Fruit is shown in Table 3.As shown in Table 3, continuously in operation 800h, HCFO-1233zd (E) selectivity is urged more than 88% in course of reaction
Agent keeps good stability.
Table 3
Claims (5)
1. a kind of method for preparing anti-form-1-chloro-3,3,3 ,-trifluoropropene, with hydrogen fluoride and 1,1,1,3,3- pentachloropropane is original
Feed liquid phase fluorination prepares anti-form-1-chloro-3,3,3 ,-trifluoropropene, it is characterised in that using alkali compounds and metal halide is multiple
Catalyst is closed, wherein metal halide is TiCl4、SnCl4、TiF4Or SnF4, alkali compounds is alkali halide, organic
The mol ratio of amine, ethers or sulfone class, alkali compounds and metal halide is 1:0.3~3.
A kind of 2. method for preparing anti-form-1-chloro-3,3,3 ,-trifluoropropene according to claim 1, it is characterised in that institute
The metal halide stated is TiCl4Or SnCl4。
A kind of 3. method for preparing anti-form-1-chloro-3,3,3 ,-trifluoropropene according to claim 1, it is characterised in that institute
The alkali compounds and the mol ratio of metal halide stated are 1:0.5~2.
A kind of 4. method for preparing anti-form-1-chloro-3,3,3 ,-trifluoropropene according to claim 1, it is characterised in that institute
The alkali halide stated is KF, KCl, CsF or CsCl, described organic amine be n-propylamine, isopropylamine, n-butylamine, tert-butylamine,
N-amylamine, di-n-propylamine, di-n-butylamine, triethylamine, tripropyl amine (TPA), tri-n-butylamine, diisopropylethylamine or pyridine, described ethers are
Ether, propyl ether, tetrahydrofuran or dioxane, described sulfone class are dimethyl sulfoxide or sulfolane.
A kind of 5. method for preparing anti-form-1-chloro-3,3,3 ,-trifluoropropene according to claim 1, it is characterised in that institute
The alkali halide stated is KF, and described organic amine is tert-butylamine, diisopropylethylamine, di-n-butylamine, tri-n-butylamine, described
Ethers is ether, and described sulfone class is dimethyl sulfoxide.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110283043A (en) * | 2019-07-26 | 2019-09-27 | 西安近代化学研究所 | A method of preparing the chloro- 1,1,1,4,4,4- hexafluoro -2- butylene of 2- |
| CN110283042A (en) * | 2019-07-26 | 2019-09-27 | 西安近代化学研究所 | A method of the synthesis chloro- 1,1,1,4,4,4- hexafluoro -2- butylene of 2- |
| CN112645793A (en) * | 2020-12-18 | 2021-04-13 | 西安近代化学研究所 | Process system and method for producing trans-1-chloro-3, 3, 3-trifluoropropene |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103189338A (en) * | 2010-09-03 | 2013-07-03 | 霍尼韦尔国际公司 | Integrated process to coproduce trans-1-chloro-3,3,3-trifluoropropene, trans-1,3,3,3-tetrafluoropropene, and 1,1,1,3,3-pentafluoropropane |
-
2017
- 2017-10-25 CN CN201711006541.5A patent/CN107652160A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103189338A (en) * | 2010-09-03 | 2013-07-03 | 霍尼韦尔国际公司 | Integrated process to coproduce trans-1-chloro-3,3,3-trifluoropropene, trans-1,3,3,3-tetrafluoropropene, and 1,1,1,3,3-pentafluoropropane |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110283043A (en) * | 2019-07-26 | 2019-09-27 | 西安近代化学研究所 | A method of preparing the chloro- 1,1,1,4,4,4- hexafluoro -2- butylene of 2- |
| CN110283042A (en) * | 2019-07-26 | 2019-09-27 | 西安近代化学研究所 | A method of the synthesis chloro- 1,1,1,4,4,4- hexafluoro -2- butylene of 2- |
| CN110283043B (en) * | 2019-07-26 | 2021-10-01 | 西安近代化学研究所 | Method for preparing 2-chloro-1, 1,1,4,4, 4-hexafluoro-2-butene |
| CN110283042B (en) * | 2019-07-26 | 2022-05-24 | 西安近代化学研究所 | Method for synthesizing 2-chloro-1, 1,1,4,4, 4-hexafluoro-2-butene |
| CN112645793A (en) * | 2020-12-18 | 2021-04-13 | 西安近代化学研究所 | Process system and method for producing trans-1-chloro-3, 3, 3-trifluoropropene |
| CN112645793B (en) * | 2020-12-18 | 2023-02-14 | 西安近代化学研究所 | Process system and method for producing trans-1-chloro-3, 3-trifluoropropene |
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Application publication date: 20180202 |