CN104177219B - A kind of method for preparing 1,3,3,3 tetrafluoropropenes - Google Patents
A kind of method for preparing 1,3,3,3 tetrafluoropropenes Download PDFInfo
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- CN104177219B CN104177219B CN201410377685.1A CN201410377685A CN104177219B CN 104177219 B CN104177219 B CN 104177219B CN 201410377685 A CN201410377685 A CN 201410377685A CN 104177219 B CN104177219 B CN 104177219B
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Abstract
The invention discloses the method that one kind prepares 1,3,3,3 tetrafluoropropenes, including following preparation process：350g~550g alkaline aqueous solutions are first added in reactor, and solvent is added to reactor, form the dicyandiamide solution of reaction；Then after heating terminates, 100g~320g 1,1,1,3,3 pentafluoropropane is added to reactor, controls the alkali and 1 in alkaline aqueous solution, the mol ratio of 1,1,3,3 pentafluoropropane is in (0.75~7) to 10 DEG C~150 DEG C of reaction temperature for warming while stirring：In the range of 1；Then start to react, the reaction time is 5min~60min, ultimately generates the tetrafluoropropene of reaction product 1,3,3,3.The present invention is improved on the basis of existing, the shortcomings that overcoming in 1,3,3,3 tetrafluoropropene methods of existing preparation.It is reaction raw materials from 1,1,1,3,3 pentafluoropropane, 1,1,1,3,3 pentafluoropropane is added in the alkaline aqueous solution containing solvent and reacted, 1,3,3,3 tetrafluoropropenes is finally made.Not only production efficiency significantly improves, and preparation process is more economically environmentally friendly.
Description
Technical field
The present invention relates to a kind of method for preparing tetrafluoroethene, more particularly, to utilizing 1,1,1,3,3- pentafluoropropane
(HFC-245fa) method for preparing 1,3,3,3- tetrafluoropropenes (HFC-1234ze).
Background technology
1,3,3,3- tetrafluoropropene, there is the latent value (GWP) of relatively low greenhouse effects and the latent value (ODP) of zero ozone depletion, quilt
Be considered the most potential forth generation ODS substitutes for substituting HFA 134a (HFC-134a), be widely used as refrigerant,
Foaming agent, aerosol propellant, solvent etc..Have high fever steady in addition, 1,3,3,3- tetrafluoropropene (HFC-1234ze) is synthesis
The base stock of qualitative high-elasticity thermoplastic material, has chemical inertness to aromatic hydrocarbons and aliphatic, easily vulcanization, can make plating membrane material
Material, the resistance to heat-insulating material of high temperature resistant, is widely used in the fields such as fire-fighting, space flight, aviation.
The known tetrafluoropropene compound for preparing has a variety of methods.For example, patent US6548719B1 is disclosed, turn in phase
Under shifting catalyst effect, chemical formula uses at least one alkali metal hydrogen for the compound of CF3C (R1aR2b) C (R3cR4d) classification
Oxide dehydrohalogenation prepares the method for a variety of fluoroolefins compounds, and wherein R substituent is as defined in the patent, condition
It is at least one hydrogen wherein be present and a halogen on adjacent carbon atom be present.It is a kind of effectively and suitable for system disclosing
While the method for standby a variety of tetrafluoropropene class compounds, the patent and the side for not specifically disclosing the tetrafluoropropene of preparation 1,3,3,3-
Method.The method that 1,3,3,3- tetrafluoropropenes of a variety of preparations are disclosed in patent CN200580020412.0, this method are included in phase
Transfer catalyst effect under, make chemical formula be CF3CH2CHFX classes compound in aqueous alkali dehydrohalogenation.The method needs
To use expensive phase transfer catalyst, the defects of reaction time is long, yield is low be present.
Patent US5986151, US6124510, EP974571, CN200480027096.5, CN200780023672.2 etc.
The method that one kind prepares 1,3,3,3- tetrafluoropropenes is disclosed in patent, this method is included in the presence of metallic catalyst, gas
Mutually make CF3CH2CF2H (HFC-245fa) dehydrofluorination, including make CF3CH2CF2H (HFC-245fa) at relatively high temperature
Time enough is contacted with catalyst, CF3CH2CF2H (HFC-245fa) is changed into 1,3,3,3- tetrafluoropropenes.Such method
It is required to use catalyst, and has that reaction temperature is higher, and the easy coking and deactivation of catalyst, the continuous production cycle is shorter, conversion
The defects of rate is not high.
In the patents such as patent US5986151, US6124510, US6548719B1, EP974571, CN200480027096.5
Disclose the method for preparing 1,3,3,3- tetrafluoropropenes.These methods are with CF3CH2CF2H (HFC- in caustic solution
1,3,3,3- tetrafluoropropenes 245fa) are produced for raw material dehydrofluorination, the defects of reaction time is long or reaction yield is low be present.
The content of the invention
It is an object of the invention to provide the method that one kind prepares 1,3,3,3- tetrafluoropropenes, this method is on the basis of existing
It is improved, the shortcomings that overcoming in 1,3,3,3- tetrafluoropropene methods of existing preparation.It is anti-from 1,1,1,3,3- pentafluoropropanes
Raw material is answered, 1,1,1,3,3- pentafluoropropane is added in the alkaline aqueous solution containing solvent and reacted, is finally made 1,3,3,
3- tetrafluoropropenes.Not only production efficiency significantly improves, and preparation process is more economically environmentally friendly.
In order to solve the above-mentioned technical problem, adopt the following technical scheme that：
The method that one kind prepares 1,3,3,3- tetrafluoropropenes, it is characterised in that including following preparation process：First in reactor
Interior addition 350g~550g alkaline aqueous solutions, and solvent is added to reactor, form the dicyandiamide solution of reaction；Then while stirring
10 DEG C~150 DEG C of reaction temperature is warming up to, after heating terminates, 100g~320g 1,1,1,3,3- five fluorine third is added to reactor
Alkane, the alkali and 1 in alkaline aqueous solution is controlled, the mol ratio of 1,1,3,3- pentafluoropropane is in (0.75~7)：In the range of 1；Then open
Begin to react, the reaction time is 5min~60min, ultimately generates the tetrafluoropropene of reaction product 1,3,3,3-.
After it is preferred that, alkaline aqueous solution includes sodium hydrate aqueous solution, potassium hydroxide aqueous solution, aqueous sodium carbonate, carbonic acid
Aqueous solutions of potassium and its mixture.The selection object variation of alkaline aqueous solution, convenient material drawing.
After it is preferred that, the alkali weight concentration of alkaline aqueous solution is 5%~50%.In the range of the alkali concn, alkaline aqueous solution
Solubility property it is optimal, have promote reaction function.
After it is preferred that, solvent includes the organic matter containing alkyl and aryl nitrile, the organic matter containing alkyl and aryl ether, contained
The organic matter and its mixture of sulfoxide.The scope of selecting material of solvent is wide, therefore convenient material drawing.
After it is preferred that, solvent include acetonitrile, adiponitrile, 2- methyltetrahydrofurans, tetrahydrofuran, dimethyl sulfoxide (DMSO), sulfolane,
Diethylene glycol dimethyl ether and its mixture.The scope of selecting material of solvent is wide, therefore convenient material drawing.
After it is preferred that, reaction temperature is preferably 30 DEG C~100 DEG C.In the range of reaction temperature, reaction speed, conversion ratio are most
Good, reaction is more steady.
After it is preferred that, the reaction time is preferably 10min~30min.In the reaction time range, reaction speed, conversion ratio are most
Good, reaction cost is relatively low, can avoid causing cost to increase because the reaction time is long.
After it is preferred that, the alkali in alkaline aqueous solution and 1, the mol ratio of 1,1,3,3- pentafluoropropane is preferably (1~5)：1.Should
In molar ratio range, the solute effect of 1,1,1,3,3- pentafluoropropane is optimal.
Due to using above-mentioned technical proposal, having the advantages that：
The method that the present invention prepares 1,3,3,3- tetrafluoropropenes for one kind, this method are improved on the basis of existing, gram
The shortcomings that taking in existing preparation 1,3,3,3- tetrafluoropropene methods.It is reaction raw materials from 1,1,1,3,3- pentafluoropropane, by 1,
1,1,3,3- pentafluoropropane, which is added in the alkaline aqueous solution containing solvent, to be reacted, and 1,3,3,3- tetrafluoropropenes are finally made.
Not only production efficiency significantly improves, and preparation process is more economically environmentally friendly.
Solvent has solubilization-aid effect, and 1,1,1,3,3- pentafluoropropane is not easily dissolved in alkaline aqueous solution, adds solvent
Afterwards, solvent can help 1,1,1,3,3- pentafluoropropane to be dissolved in alkaline aqueous solution, can effectively facilitate reaction, reaction speed,
Production efficiency etc. is obviously improved.In reaction, aqueous phase or inorganic phase exist due to alkali lye, and organic phase is solvent and a small amount of
1,1,1,3,3- pentafluoropropane, upper organic phase can return reaction system and participate in reacting again, therefore reduce solvent load, show
Writing reduces production cost.The present invention has that equipment requirement is simple, production is easily controlled, side reaction is few simultaneously, and solvent can circulate
Apply mechanically, production cost is relatively low, the advantages of high income.The yield of the 1,3,3,3- tetrafluoropropenes of production is reacted up to more than 95%.
Embodiment
The method that the present invention prepares 1,3,3,3- tetrafluoropropenes for one kind, it is former for reaction from 1,1,1,3,3- pentafluoropropane
Material prepares 1,3,3,3- tetrafluoropropenes by a series of technological process.The 1,3,3,3- tetrafluoropropenes prepared include
Its cis-isomer and transisomer, its chemical equation reacted are：
During preparation, prepare an autoclave first, the autoclave is made up of mechanical agitator and reflux condenser.
Previously prepared alkaline aqueous solution is answered before starting to feed intake：Solid base is included into sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate
Or their mixture is put into a certain amount of water, alkaline aqueous solution is prepared in stirring, and by the way that control alkali is diluted with water
Weight concentration in the range of 5%~50% because in the range of the alkali concn, the solubility property of alkaline aqueous solution is optimal, tool
There is the function of promoting to react.
After alkaline aqueous solution is prepared, the alkaline aqueous solution is put into reactor, input amount control 350g~
In the range of 550g.Then solvent, solvent huge number are added to reactor, solvent is organic matter and must contain alkyl and aryl
Nitrile, alkyl and aryl ether or sulfoxide these groups, therefore mainly it is taken from nitrile organic matter, ethers organic matter, sulfoxide type organic
Or their mixture.Concretely, solvent is selected from acetonitrile, propionitrile, butyronitrile, methyl cellosolve acetate glutaronitrile, adiponitrile, benzonitrile, carbonic acid
1,2- ethyls, carbonic acid 1,2- Asias propyl ester, methyl ethyl ketone, methyl isoamyl ketone, DIBK, methyl phenyl ethers anisole, 2- methyl four
Hydrogen furans, tetrahydrofuran, dioxane, diethylene glycol dimethyl ether, TRIGLYME, tetraethyleneglycol dimethyl ether, ring
Fourth sulfone, dimethylformamide, dimethyl sulfoxide (DMSO), perfluor-N-methymorpholine or its mixture.Excellent preferred solvent bag is obtained through experiment
Include acetonitrile, adiponitrile, 2- methyltetrahydrofurans, tetrahydrofuran, dimethyl sulfoxide (DMSO), sulfolane, diethylene glycol dimethyl ether or it is mixed
Compound.
The dicyandiamide solution for being adapted to reaction is formed after solvent is added in reactor, then the material side in reactor is stirred
Side is heated up, and is finally warming up to 10 DEG C~150 DEG C of reaction temperature, and preferable reaction temperature is obtained as 30 DEG C~100 DEG C through experiment.
After being warming up to reaction temperature, 100g~320g 1,1,1,3,3- pentafluoropropane is added into reactor.The reaction ultimately formed
In system, the alkali in alkaline aqueous solution and 1, the mol ratio of 1,1,3,3- pentafluoropropane is in (0.75~7)：In the range of 1, through experiment
It is (1~5) to obtain its preferred molar ratio:1；The weight of solvent is 0.1~1 times of 1,1,1,3,3- pentafluoropropane weight.
After the completion of above-mentioned all raw material additions, to close reactor and start to react, the reaction time is controlled in 5min~60min,
It is 10min~30min to obtain preferred reaction time through experiment.Reaction product is finally given, and is directly adopted using straight cold finger
Sample is to on-line gas chromatography analyzer, analytical reactions product component.
With reference to specific embodiment, the invention will be further described：
Embodiment 1：
Add 50% potassium hydroxide solution 380g into the autoclave being made up of mechanical agitator, reflux condenser, two
Methyl sulfoxide 200g, stirring are warming up to 100 DEG C, and 1,1,1,3,3- pentafluoropropane 300g is added by dipping tube.Straight after 10min
On-line gas chromatography analysis is directly sampled at shape condenser pipe, have about 99.49% 1,3,3,3- tetrafluoropropenes, 0.22%
1,1,1,3,3- pentafluoropropanes.
1,3,3, the 3- tetrafluoropropene very high purities that the embodiment obtains, impurity content is few, compared with existing preparation method
Its reaction speed, conversion ratio are obviously improved.
Embodiment 2
Add 50% sodium hydroxide solution 400g into the autoclave being made up of mechanical agitator, reflux condenser, four
Hydrogen furans 50g, stirring are warming up to 45 DEG C, and 1,1,1,3,3- pentafluoropropane 150g is added by dipping tube.It is cold in straight after 20min
On-line gas chromatography analysis is directly sampled at solidifying pipe, have about 95.18% 1,3,3,3- tetrafluoropropenes, the 1 of 1.78%, 1,
1,3,3- pentafluoropropanes.
1,3,3, the 3- tetrafluoropropene purity that the embodiment obtains are higher, and impurity content is less, with existing preparation method phase
There is faint lifting than its reaction speed, conversion ratio.
Embodiment 3
25% sodium carbonate liquor 400g, acetonitrile are added into the autoclave being made up of mechanical agitator, reflux condenser
100g, stirring are warming up to 60 DEG C, and 1,1,1,3,3- pentafluoropropane 168g is added by dipping tube.In straight cold finger after 15min
Place directly sample on-line gas chromatography analyze, have about 96.21% 1,3,3,3- tetrafluoropropenes, the 1 of 1.69%, 1,1,3,
3- pentafluoropropanes.
1,3,3,3- tetrafluoropropene purity that the embodiment obtains are high, and impurity content is few, compared with existing preparation method its
Reaction speed, conversion ratio have lifting.
Embodiment 4
40% solution of potassium carbonate 400g, ring fourth are added into the autoclave being made up of mechanical agitator, reflux condenser
Sulfone 100g, stirring are warming up to 60 DEG C, and 1,1,1,3,3- pentafluoropropane 150g is added by dipping tube.Condensed after 30min in straight
Directly sampled at pipe on-line gas chromatography analysis, have about 98.32% 1,3,3,3- tetrafluoropropenes, the 1 of 1.43%, 1,1,
3,3- pentafluoropropanes.
1,3,3,3- tetrafluoropropene purity that the embodiment obtains are high, and impurity content is few, compared with existing preparation method its
Reaction speed, conversion ratio are obviously improved.
Embodiment 5
Add 20% potassium hydroxide solution 500g into the autoclave being made up of mechanical agitator, reflux condenser, two
Methyl sulfoxide 50g, stirring are warming up to 100 DEG C, and 1,1,1,3,3- pentafluoropropane 150g is added by dipping tube.Straight after 30min
On-line gas chromatography analysis is directly sampled at shape condenser pipe, have about 97.82% 1,3,3,3- tetrafluoropropenes, 2.00%
1,1,1,3,3- pentafluoropropanes.
1,3,3,3- tetrafluoropropene purity that the embodiment obtains are high, and impurity content is few, compared with existing preparation method its
Reaction speed, conversion ratio are obviously improved.
The specific embodiment of the present invention is these are only, but the technical characteristic of the present invention is not limited thereto.It is any with this hair
Based on bright, to solve essentially identical technical problem, essentially identical technique effect is realized, made ground simple change, etc.
With replacement or modification etc., all it is covered by among protection scope of the present invention.
Claims (6)
1. the method that one kind prepares 1,3,3,3- tetrafluoropropenes, it is characterised in that including following preparation process：First in reactor
350g~550g alkaline aqueous solutions are added, and solvent is added to the reactor, form the dicyandiamide solution of reaction；Then side is stirred
While being warming up to 10 DEG C~150 DEG C of reaction temperature, after heating terminates, the 1,1,1,3,3- of 100g~320g is added to the reactor
Pentafluoropropane, controls the alkali and described 1 in the alkaline aqueous solution, the mol ratio of 1,1,3,3- pentafluoropropane be preferably (1~
5)：1；Then start to react, the reaction time is 10min~30min, ultimately generates the tetrafluoropropene of reaction product 1,3,3,3-.
2. the method that one kind prepares 1,3,3,3- tetrafluoropropenes according to claim 1, it is characterised in that：The alkalescence is water-soluble
Liquid includes sodium hydrate aqueous solution, potassium hydroxide aqueous solution, aqueous sodium carbonate, wet chemical and its mixture.
3. the method that one kind prepares 1,3,3,3- tetrafluoropropenes according to claim 1, it is characterised in that：The alkalescence is water-soluble
The alkali weight concentration of liquid is 5%~50%.
4. the method that one kind prepares 1,3,3,3- tetrafluoropropenes according to claim 1, it is characterised in that：The solvent includes
Organic matter containing alkyl and aryl nitrile, the organic matter containing alkyl and aryl ether, organic matter and its mixture containing sulfoxide.
5. the method that one kind prepares 1,3,3,3- tetrafluoropropenes according to claim 4, it is characterised in that：The solvent includes
Acetonitrile, adiponitrile, 2- methyltetrahydrofurans, tetrahydrofuran, dimethyl sulfoxide (DMSO), sulfolane, diethylene glycol dimethyl ether and its mixing
Thing.
6. the method that one kind prepares 1,3,3,3- tetrafluoropropenes according to claim 1, it is characterised in that：The reaction temperature
Preferably 30 DEG C~100 DEG C.
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| CN104945221B (en) * | 2015-06-11 | 2017-07-18 | 浙江衢州巨新氟化工有限公司 | A kind of method of the tetrafluoropropene of coproduction 2,3,3,3 and 1,3,3,3 tetrafluoropropenes |
| KR20180041689A (en) * | 2015-09-11 | 2018-04-24 | 더 케무어스 컴퍼니 에프씨, 엘엘씨 | Dehydrohalogenation of Hydrochlorofluorocarbons |
| CN112054262A (en) * | 2020-08-28 | 2020-12-08 | 甘肃电气装备集团生物科技工程有限公司 | Leaching solvent suitable for electrolyte in retired lithium battery and method for separating and recycling electrolyte from retired lithium battery by using leaching solvent |
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| US5986151A (en) * | 1997-02-05 | 1999-11-16 | Alliedsignal Inc. | Fluorinated propenes from pentafluoropropane |
| EP0974571A2 (en) * | 1998-07-21 | 2000-01-26 | Elf Atochem North America, Inc. | Preparation of 1,1,1,3-tetrafluoropropene( 1234ze ) |
| CN1589248A (en) * | 2001-09-25 | 2005-03-02 | 霍尼韦尔国际公司 | Process for producing fluoroolefins |
| US7230146B2 (en) * | 2003-10-27 | 2007-06-12 | Honeywell International Inc. | Process for producing fluoropropenes |
| CN102112421A (en) * | 2007-05-22 | 2011-06-29 | 霍尼韦尔国际公司 | Method for producing trans-1, 3, 3, 3-tetrafluoropropene |
| CN103483142A (en) * | 2013-08-29 | 2014-01-01 | 巨化集团技术中心 | Method for realizing liquid-phase continuous preparation of 2,3,3,3-tetrafluoropropene |
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2014
- 2014-08-01 CN CN201410377685.1A patent/CN104177219B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5986151A (en) * | 1997-02-05 | 1999-11-16 | Alliedsignal Inc. | Fluorinated propenes from pentafluoropropane |
| EP0974571A2 (en) * | 1998-07-21 | 2000-01-26 | Elf Atochem North America, Inc. | Preparation of 1,1,1,3-tetrafluoropropene( 1234ze ) |
| CN1589248A (en) * | 2001-09-25 | 2005-03-02 | 霍尼韦尔国际公司 | Process for producing fluoroolefins |
| US7230146B2 (en) * | 2003-10-27 | 2007-06-12 | Honeywell International Inc. | Process for producing fluoropropenes |
| CN102112421A (en) * | 2007-05-22 | 2011-06-29 | 霍尼韦尔国际公司 | Method for producing trans-1, 3, 3, 3-tetrafluoropropene |
| CN103483142A (en) * | 2013-08-29 | 2014-01-01 | 巨化集团技术中心 | Method for realizing liquid-phase continuous preparation of 2,3,3,3-tetrafluoropropene |
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