CN103626625B - A kind of preparation method of 1,1,1,3,3-pentafluoropropane - Google Patents
A kind of preparation method of 1,1,1,3,3-pentafluoropropane Download PDFInfo
- Publication number
- CN103626625B CN103626625B CN201310386304.1A CN201310386304A CN103626625B CN 103626625 B CN103626625 B CN 103626625B CN 201310386304 A CN201310386304 A CN 201310386304A CN 103626625 B CN103626625 B CN 103626625B
- Authority
- CN
- China
- Prior art keywords
- reaction
- hydrofluoric acid
- anhydrous hydrofluoric
- reactor
- chloro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a kind of method of liquid phase continuous production 1,1,1,3,3-pentafluoropropane, comprise the following steps: (1) adds fluorination catalyst and anhydrous hydrofluoric acid in reactor, the mol ratio of fluorination catalyst and anhydrous hydrofluoric acid is 1:2 ~ 6; (2) by anhydrous hydrofluoric acid and 1,1-bis-chloro-3,3,3-trifluoro propane continuously adds in reactor reacts in molar ratio at 2 ~ 10: 1, and temperature of reaction is 50 DEG C ~ 120 DEG C, and reaction pressure is 0.3 ~ 1.0MPa, fluorination catalyst and per hourly add 1 of reactor, the mol ratio of chloro-3,3, the 3-trifluoro propane of 1-bis-is 2 ~ 20:1; (3) collecting reaction product through washing, namely obtain 1,1,1,3,3-pentafluoropropane after alkali cleaning.The present invention has the advantage that technique is simple, reaction conditions is gentle, transformation efficiency is high, selectivity is good.
Description
Technical field
The present invention relates to the synthetic method of hydrogen fluorochlorohydrocarbon, particularly a kind of synthetic method of 1,1,1,3,3-pentafluoropropane.
Background technology
Hydrochlorofluorocar,ons is widely used in industry in numerous applications, comprises as refrigeration agent, whipping agent, aerosol propellants, gaseous dielectric medium etc.But due to the series of environmental problems that the use of this type of material causes, comprise relatively high ozone depletion value (ODP) and global warming potential (GWP), suffered limit production and the use of majority state.
1,1,1,3,3-pentafluoropropane ozone depletion value is 0, and global warming potential is low, and be a kind of carbon-fluorine-hydrogen compound that development in recent years is got up, it has broad application prospects in fields such as whipping agent, solvent, aerosol and refrigeration equipment working medium.Owing to possessing good thermophysical property, 1,1,1,3,3-pentafluoropropane also has a lot of application in heat conduction and refrigeration equipment working medium.Meanwhile, 1,1,1,3,3-pentafluoropropane or one prepare the important source material of 1,1,1,3-tetrafluoeopropene.
1,1,1, the preparation method of 3,3-pentafluoropropane mainly with 1,1,1,3,3-pentachloropropane, 1, the halogenated alkanes such as the fluoro-3-chloropropane of 1,1,3-tetra-and anhydrous hydrofluoric acid are raw material, there are liquid phase method and vapor phase process two kinds, vapor phase process generally adopts the oxide compound of Cr, Al etc. as catalyzer, and reaction preference, transformation efficiency are all better, but there is a series of shortcomings such as temperature of reaction is high, energy consumption is large.
Liquid phase method generally adopts the muriate of Sb, Sn or Ti to make catalyzer, and temperature of reaction is lower, energy consumption is low, but is generally batch operation, and industrialization difficulty is large.
As China Patent Publication No. CN101560138A relate to 1,1,1,3,3-pentafluoropropane preparation method, adopt trifluorodichloropropane as reaction raw materials, but its trifluorodichloropropane is obtained by vinyl fluoride and Refrigerant 12 telomerization 1, chloro-1,3, the 3-trifluoro propane of 1-bis-.It obtains product through rectifying, purity 99.6%, yield 87.38% by after chloro-for 1,1-bis-1,3,3-trifluoro propane liquid-phase fluorination.This reaction is batch production, and exist raw material be difficult to preparation and raw materials cost costliness etc. problem.
Summary of the invention
The present invention is directed to the deficiencies in the prior art part, the method for liquid phase continuous production 1,1,1,3, the 3-pentafluoropropane that a kind of technique is simple, reaction conditions is gentle, transformation efficiency is high, selectivity is good is provided.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is: a kind of method of liquid phase continuous production 1,1,1,3,3-pentafluoropropane, comprises the following steps:
(1) in reactor, add fluorination catalyst and anhydrous hydrofluoric acid, the mol ratio of described fluorination catalyst and anhydrous hydrofluoric acid is 1:2 ~ 6;
(2) by anhydrous hydrofluoric acid and 1,1-bis-chloro-3,3,3-trifluoro propane continuously adds in reactor reacts in molar ratio at 2 ~ 10: 1, and described temperature of reaction is 50 DEG C ~ 120 DEG C, and reaction pressure is 0.3 ~ 1.0MPa, described fluorination catalyst and per hourly add 1 of reactor, the mol ratio of chloro-3,3, the 3-trifluoro propane of 1-bis-is 2 ~ 20:1;
(3) collecting reaction product through washing, namely obtain 1,1,1,3,3-pentafluoropropane after alkali cleaning.
Further:
One in the antimony pentachloride of fluorination catalyst preferably through fluoridizing described in step (1), tin tetrachloride, titanium tetrachloride, zinc chloride, columbium pentachloride.
Fluorination catalyst described in step (1) and the mol ratio of anhydrous hydrofluoric acid are preferably 1:3 ~ 5;
Temperature of reaction described in step (2) is preferably 60 ~ 80 DEG C.
Reaction pressure described in step (2) is preferably 0.4 ~ 0.6MPa.
The mol ratio of the anhydrous hydrofluoric acid described in step (2) and chloro-3,3, the 3-trifluoro propane of 1,1-bis-is preferably 4 ~ 6: 1.
Step (2) described fluorination catalyst and the mol ratio adding 1,1-bis-chloro-3,3,3-trifluoro propane of reactor per hour are preferably 7.2 ~ 16: 1.
In the present invention, anhydrous hydrofluoric acid is that reaction raw materials can be used as again dissolution with solvents fluorination catalyst, and fluorination catalyst is better contacted with reaction raw materials, increases reaction conversion ratio and reaction efficiency.The mol ratio of fluorination catalyst and anhydrous hydrofluoric acid is too little, and the consumption of solvent is too large, and waste reaction compartment, affects reaction efficiency; The mol ratio of fluorination catalyst and anhydrous hydrofluoric acid is too large, solvent load is too little, and fluorination catalyst can not fully dissolve in a solvent, causes reaction efficiency to reduce, therefore in the present invention, the mol ratio of fluorination catalyst and anhydrous hydrofluoric acid is 1:2 ~ 6, is preferably 1:3 ~ 5.
The mol ratio of chloro-3,3, the 3-trifluoro propane of 1,1-bis-and anhydrous hydrofluoric acid has impact to transformation efficiency, and the mol ratio of chloro-3,3, the 3-trifluoro propane of 1,1-bis-and anhydrous hydrofluoric acid is too large, causes the waste of anhydrous hydrofluoric acid; Too little, affect chloro-3,3, the 3-trifluoro conversion of propane of 1,1-bis-, therefore in the present invention, the mol ratio of 1,1-bis-chloro-3,3,3-trifluoro propane and anhydrous hydrofluoric acid is 1: 2 ~ 10, is preferably 1: 4 ~ 6.
Temperature of reaction has impact to reaction preference and reaction efficiency, and temperature of reaction is too high, and by product increases, and strengthens the corrodibility to reactor simultaneously; Temperature of reaction is too low, and speed of response is excessively slow, affects reaction efficiency, and therefore, the temperature of reaction in the present invention is 50 ~ 120 DEG C, is preferably 60 ~ 80 DEG C.
Reaction pressure has impact to reaction efficiency, and reaction pressure is too large, can strengthen the requirement to equipment, cause the waste of equipment and materials; Reaction pressure is too little, then can not ensure that anhydrous hydrofluoric acid liquefies, and affects reaction efficiency, and therefore, the reaction pressure 0.3 ~ 1.0MPa in the present invention, is preferably 0.4 ~ 0.6MPa.
Fluorination catalyst in the present invention can select the one in the muriate of Sb, Ti, Sn, Ta, Nb, Zn, Hf or their Chlorine fluoride compound, the one in the antimony pentachloride preferably through fluoridizing, tin tetrachloride, titanium tetrachloride, zinc chloride, columbium pentachloride.
Fluorination catalyst and the mol ratio adding 1,1-bis-chloro-3,3,3-trifluoro propane of reactor per hour have impact to transformation efficiency, and mol ratio is too large, and waste reaction compartment affects reaction efficiency; Mol ratio is too little, and material concentration is excessive, causes reaction thoroughly not affect transformation efficiency, and therefore in the present invention, fluorination catalyst is 2 ~ 20:1 with the mol ratio hour adding 1,1-bis-chloro-3,3,3-trifluoro propane of reactor, is preferably 7.2 ~ 16: 1.
Compared with prior art, the present invention has the following advantages:
1, technique is simple, reaction conditions is gentle, efficiency is high, achieves liquid phase continuous prodution;
2, transformation efficiency is high, and selectivity is good, and transformation efficiency, more than 94%, reaches as high as 98.9%, and selectivity, more than 95%, reaches as high as 99.1%.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
As shown in the figure: chloro-3,3, the 3-trifluoro propane storage tanks 2 of anhydrous hydrofluoric acid storage tank 1,1,1-bis-, reactor 5, condenser 6, water wash column 7, soda-wash tower 8, product-collecting groove 9, charge pump 3,4, pipeline 10 ~ 17.
Embodiment
As shown in Figure 1: in reactor 5, first add catalyzer and the anhydrous hydrofluoric acid of certain mole, to reactor 5, anhydrous hydrofluoric acid is passed into through pipeline 10, charge pump 3 and pipeline 13 again, simultaneously from 1,1-bis-chloro-3 from anhydrous hydrofluoric acid storage tank 1,3,3-trifluoro propane storage tank 2 passes into 1,1-bis-chloro-3 by pipeline 11, charge pump 4 and pipeline 12,3 in reactor 5,3-trifluoro propane, controls temperature of reaction kettle and starts reaction.The valve on pipeline 14 opened by question response still 5 after reaching setting reaction pressure, reaction gas-phase product and on a small quantity unreacted 1,1-bis-chloro-3,3,3-trifluoro propane and anhydrous hydrofluoric acid are after pipeline 14 passes through condenser 6 condensation, 1,1-bis-chloro-3,3,3-trifluoro propane and anhydrous hydrofluoric acid are back to reactor and continue reaction, uncooled gas-phase product, after pipeline 15 washes removing byproduct hydrogen chloride by water wash column 7, removes a small amount of hydrogenchloride through pipeline 16 by soda-wash tower 8 alkali cleaning, product 1 further, 1,1,3,3-pentafluoropropane enters product-collecting groove 9 through pipeline 17.
By the following examples more specific description is carried out to the present invention, but the present invention is not limited to described embodiment.
Embodiment 1
4.32 moles of antimony pentachlorides through fluoridizing and 12.96 moles of anhydrous hydrofluoric acids are added in 2L liquid phase reaction still, after being warming up to 80 DEG C, by chloro-for 3,3-bis-1,1,1-trifluoro propane (0.72 mol/hr) and anhydrous hydrofluoric acid (3.6 mols/hr) mol ratio with 1: 5 are passed in reactor continuously reacts, and maintaining reactor pressure is 0.6MPa, collects gas-phase reaction product and namely obtains 1 through cooling, washing, alkali cleaning, 1,1,3,3-pentafluoropropane product.After sustained reaction 72h, the product collected is analyzed, reaction conversion ratio 97.8%, selectivity 98.7%.
Embodiment 2
6 moles of tin tetrachloride through fluoridizing and 12 moles of anhydrous hydrofluoric acids are added in 2L liquid phase reaction still, after being warming up to 120 DEG C, by chloro-for 3,3-bis-1,1,1-trifluoro propane (0.6 mol/hr) and anhydrous hydrofluoric acid (1.2 mols/hr) mol ratio with 1: 2 are passed in reactor continuously reacts, and maintains reactor pressure 1.0MPa, collects gas-phase reaction product and through namely obtaining 1 through cooling, washing, alkali cleaning, 1,1,3,3-pentafluoropropane product.After sustained reaction 72h, the product collected is analyzed, reaction conversion ratio 94.2%, selectivity 95.1%.
Embodiment 3
0.6 mole of titanium tetrachloride through fluoridizing and 3.6 moles of anhydrous hydrofluoric acids are added in 1L liquid phase reaction still, after being warming up to 100 DEG C, by chloro-for 3,3-bis-1,1,1-trifluoro propane (0.3 mol/hr) and anhydrous hydrofluoric acid (3 mols/hr) mol ratio with 1: 10 are passed in reactor continuously reacts, and maintains reactor pressure 0.8MPa, collects gas-phase reaction product and through namely obtaining 1 through cooling, washing, alkali cleaning, 1,1,3,3-pentafluoropropane product.After sustained reaction 72h, the product collected is analyzed, reaction conversion ratio 94.2%, selectivity 96.0%.
Embodiment 4
6 moles of zinc chloride through fluoridizing and 12 moles of anhydrous hydrofluoric acids are added in 1L liquid phase reaction still, after being warming up to 50 DEG C, by chloro-for 3,3-bis-1,1,1-trifluoro propane (0.3 mol/hr) and anhydrous hydrofluoric acid (2.4 mols/hr) mol ratio with 1: 8 are passed in reactor continuously reacts, and maintains reactor pressure 0.3MPa, collects gas-phase reaction product and through namely obtaining 1 through cooling, washing, alkali cleaning, 1,1,3,3-pentafluoropropane product.After sustained reaction 72h, the product collected is analyzed, reaction conversion ratio 95.0%, selectivity 95.5%.
Embodiment 5
4 moles of columbium pentachlorides through fluoridizing and 16 moles of anhydrous hydrofluoric acids are added in 1L liquid phase reaction still, after being warming up to 70 DEG C, by chloro-for 3,3-bis-1,1,1-trifluoro propane (0.25 mol/hr) and anhydrous hydrofluoric acid (1.0 mols/hr) mol ratio with 1: 4 are passed in reactor continuously reacts, and maintains reactor pressure 0.4MPa, collects gas-phase reaction product and through namely obtaining 1 through cooling, washing, alkali cleaning, 1,1,3,3-pentafluoropropane product.After sustained reaction 72h, the product collected is analyzed, reaction conversion ratio 97.5%, selectivity 98.5%.
Embodiment 6
The antimony pentachloride of 4.8mol through fluoridizing and 24mol anhydrous hydrofluoric acid is added in 2L liquid phase reaction still, after being warming up to 60 DEG C, by chloro-for 3,3-bis-1,1,1-trifluoro propane (0.5 mol/hr) and anhydrous hydrofluoric acid (3.0 mols/hr) mol ratio with 1: 6 are passed in reactor continuously reacts, and maintains reactor pressure 0.5MPa, collects gas-phase reaction product and through namely obtaining 1 through cooling, washing, alkali cleaning, 1,1,3,3-pentafluoropropane product.After sustained reaction 72h, the product collected is analyzed, reaction conversion ratio 98.9%, selectivity 99.1%.
Claims (1)
1. the preparation method of a pentafluoropropane, is characterized in that comprising the following steps:
(1) in reactor, add fluorination catalyst and anhydrous hydrofluoric acid continuously, the mol ratio of described fluorination catalyst and anhydrous hydrofluoric acid is 1:3 ~ 5, the columbium pentachloride that described fluorination catalyst is selected from the antimony pentachloride through fluoridizing or fluoridizes;
(2) by anhydrous hydrofluoric acid and 1,1-bis-chloro-3,3,3-trifluoro propane continuously adds in reactor reacts in molar ratio at 4 ~ 6: 1, and described temperature of reaction is 60 DEG C ~ 80 DEG C, and reaction pressure is 0.4 ~ 0.6MPa, described fluorination catalyst and per hourly add 1 of reactor, the mol ratio of chloro-3,3, the 3-trifluoro propane of 1-bis-is 2 ~ 16:1;
(3) collecting reaction product through washing, namely obtain 1,1,1,3,3-pentafluoropropane after alkali cleaning.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310386304.1A CN103626625B (en) | 2013-08-29 | 2013-08-29 | A kind of preparation method of 1,1,1,3,3-pentafluoropropane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310386304.1A CN103626625B (en) | 2013-08-29 | 2013-08-29 | A kind of preparation method of 1,1,1,3,3-pentafluoropropane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103626625A CN103626625A (en) | 2014-03-12 |
| CN103626625B true CN103626625B (en) | 2015-09-23 |
Family
ID=50208120
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310386304.1A Active CN103626625B (en) | 2013-08-29 | 2013-08-29 | A kind of preparation method of 1,1,1,3,3-pentafluoropropane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103626625B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023141794A1 (en) * | 2022-01-26 | 2023-08-03 | Honeywell International Inc. | Preparation of an improved composition from 1-chloro-3, 3, 3-trifluoropropene (hfo-1233zd) high boiling residue by-product |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1152904A (en) * | 1994-07-11 | 1997-06-25 | 联合讯号公司 | Process for preparing 1,1,1,3,3,-pentafluoropropane |
| US6362383B1 (en) * | 1998-02-26 | 2002-03-26 | Solvay (Societe Anonyme) | Hydro-fluorination of chlorinated hydrocarbons |
| US6521802B1 (en) * | 1999-11-29 | 2003-02-18 | Daikin Industries, Ltd. | Process for preparing fluorine-containing halogenated hydrocarbon compound |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6846963B2 (en) * | 1999-11-15 | 2005-01-25 | Daikin Industries, Ltd. | Process for producing 1,1,1,3,3-pentafluoropropane |
-
2013
- 2013-08-29 CN CN201310386304.1A patent/CN103626625B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1152904A (en) * | 1994-07-11 | 1997-06-25 | 联合讯号公司 | Process for preparing 1,1,1,3,3,-pentafluoropropane |
| US6362383B1 (en) * | 1998-02-26 | 2002-03-26 | Solvay (Societe Anonyme) | Hydro-fluorination of chlorinated hydrocarbons |
| US6521802B1 (en) * | 1999-11-29 | 2003-02-18 | Daikin Industries, Ltd. | Process for preparing fluorine-containing halogenated hydrocarbon compound |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103626625A (en) | 2014-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1902152B (en) | Process for producing fluoropropenes | |
| CN101265155B (en) | Process for the production of HFO trans-1234ze from HFC-245fa | |
| CN104072333B (en) | A kind of 2-chloro-1,1, Isosorbide-5-Nitrae, the preparation method of 4,4-hexafluoro-2-butylene | |
| CN101466656A (en) | Method for producing 1,3,3,3-tetrafluoropropene | |
| CN104105681A (en) | Process for producing fluorine-containing olefin | |
| CN103508840B (en) | Preparation method of 2, 3, 3, 3-tetrafluoropropene | |
| JP6778812B2 (en) | Method for simultaneous production of multiple types of halogenated olefins and alkane fluorides | |
| CN104936935A (en) | Synthesis of 3, 3, 3-trifluoropropyne | |
| CN103270009A (en) | Use of copper-ickel catalyst for dehalogenation of chlorofluorocompounds | |
| CN111875473B (en) | Preparation method of HFC-365mfc and HFC-245fa | |
| JP2019531358A (en) | Simultaneous production method of low carbon foaming agent | |
| CN104529695A (en) | Method for preparing 1,1,1,4,4,4-hexafluoro-2-butene | |
| CN103626625B (en) | A kind of preparation method of 1,1,1,3,3-pentafluoropropane | |
| CN108383679A (en) | A kind of co-production of anti-form-1-chloro- 3,3,3- trifluoro propenes and 2,3,3,3- tetrafluoropropenes | |
| WO2017028442A1 (en) | Method for preparing 2,3,3,3-tetrafluoropropene using methyl magnesium chloride | |
| US11014861B1 (en) | Method for co-producing 2,3,3,3-tetrafluoropropene and trans-1,3,3,3-tetrafluoropropene | |
| CN103772136B (en) | The production technique of hexafluoroethane | |
| CN102267866B (en) | Preparation method for trifluoroethylene and tetrafluoroethane | |
| CN103449962B (en) | Synthesis method of 2-chloro-1,1,1,2-tetrafluoropropane | |
| CN105753638A (en) | 2,3,3,3-tetrafluoropropene synthetic method | |
| CN103449958A (en) | Synthesis method of 2-chloro-3,3,3-trifluoropropene | |
| CN106316777B (en) | A kind of preparation method of 2,3,3,3- tetrafluoropropene | |
| CN101703947B (en) | Complexation-system ionic liquid catalyst-HF solution, preparation method and application thereof | |
| CN107337576A (en) | Constant temperature catalyzing synthesizes the fluoride trifluoro toluene of 2 bromine 5 | |
| CN100577646C (en) | Method for preparing trifluoro methylpyridine compounds |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170913 Address after: Technology center of Juhua Group Kecheng District 324004 Zhejiang city of Quzhou Province Co-patentee after: Zhejiang Quzhou Lianzhou Refrigerant Co., Ltd. Patentee after: Technology Center of Juhua Group Address before: Technology center of Juhua Group Kecheng District 324004 Zhejiang city of Quzhou Province Patentee before: Technology Center of Juhua Group |