CN101016223B - Preparing method of pentafluorodichloropropane - Google Patents
Preparing method of pentafluorodichloropropane Download PDFInfo
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- CN101016223B CN101016223B CN200710020166XA CN200710020166A CN101016223B CN 101016223 B CN101016223 B CN 101016223B CN 200710020166X A CN200710020166X A CN 200710020166XA CN 200710020166 A CN200710020166 A CN 200710020166A CN 101016223 B CN101016223 B CN 101016223B
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Abstract
The invention discloses a making method of pentafluoride dichloropropane, which comprises the following steps: making composite catalyst; synthesizing pentafluoride dichloropropane; rectifying and purifying pentafluoride dichloropropane; flashing pentafluoride dichloropropane after telomerizing fluolefin and halocarbon paraffin.
Description
Technical field
The present invention relates to a kind of method for preparing pentafluorodichloropropane.
Background technology
Pentafluorodichloropropane have do not fire, high chemistry and thermostability, boiling point is 51～53 ℃ and is in the same area with Freon 113, and has the identical equilibrated cleansing power that reaches.Freon 113 has excellent cleaning function as the CFC clean-out system, is widely used in degreasing, removes soldering paste, fields such as dedusting, dry-cleaning.But because the ozone depletion value (0DP) of Freon 113 is 0.8, Greenhouse effect value (HGWP) is 1.4.According to the spirit of Montreal Protocol condition, to the reduction of Freon 113 and all process quickenings of forbidding, so the substitute of research and development Freon 113 becomes the urgent task of fluorine chemical industry.And the ozone depletion value of pentafluorodichloropropane be about 0.025 and the Greenhouse effect value be about 0.1, and its physical properties and cleansing power almost be equal to Freon 113, so pentafluorodichloropropane is the optimal selection that substitutes Freon 113.In addition, pentafluorodichloropropane also is good whipping agent and refrigerant.
Originally preparation pentafluorodichloropropane method is that telomerization under High Temperature High Pressure is made with fluorochloroparaffins and fluoroolefin, because reaction is adopted the primary lewis acid catalyst and is carried out under High Temperature High Pressure, make the reaction product more complicated, especially isomerization reaction takes place in fluorochloroparaffins under this condition, generated many and pentafluorodichloropropane azeotropic impurity, thereby cause a lot of rectifiying plate number of needs when the rectification and purification pentafluorodichloropropane, the rectifying complexity.The yield of fluorochloroparaffins is low in this technology, the rectification and purification process energy consumption height of 3～4 towers, and yield poorly.As document US 2,462,402, US2,449,360, US3,795,710 grades are the type technology.
The shortcoming of document technology is that output is little, and the energy consumption height is unwell to suitability for industrialized production.
Summary of the invention
Task of the present invention be to provide a kind of reaction conditions gentleness, processing step simple and be easy to control, the saving energy, product yield is high and use the preparation method who satisfies the pentafluorodichloropropane that the industrialization volume production requires.
Task of the present invention is finished like this, a kind of preparation method of pentafluorodichloropropane, comprise the synthesis step of preparation process, the five fluorodioxy propane of composite catalyst, to the rectification and purification step of pentafluorodichloropropane synthetics, described pentafluorodichloropropane synthetic is meant the directly flash distillation after telomerization in the presence of the composite catalyst by fluoroolefin and halocarbon alkane.
In one embodiment of the present of invention, the mol ratio of described fluoroolefin and halocarbon alkane is, fluoroolefin: halocarbon alkane=0.9～5.5: 1, preferred mol ratio is 0.9～2.5: 1, the consumption of described composite catalyst is 0.5～7% of a halocarbon alkane molar weight, and preferred consumption is 0.5～3% of a halocarbon alkane molar weight.
In another embodiment of the present invention, the preparation of described composite catalyst is earlier metal halide admixture to be dissolved in the water under 40～60 ℃ temperature, feeds ammonia gas react 4～8h, flash distillation moisture content, and vacuum drying obtains the finished product composite catalyst then.
In another embodiment of the present invention, the mol ratio of described metal halide admixture and ammonia is 1: 0.2～3.5.
In yet another embodiment of the present invention, described metal halide admixture is IA family metal villiaumite or IA family metal villaumite, IIA family metal villiaumite or IIA family metal villaumite, IVB family metal villiaumite or IVB family metal villaumite, group vib metal villiaumite or group vib metal villaumite, IIIA family metal villiaumite or IIIA family metal villaumite, IVA family metal villiaumite or IVA family metal villaumite, two or more mixture in VA family metal villiaumite or the VA family metal villaumite.
In another embodiment of the present invention, the temperature of reaction of described telomerization is 6～20h for-30～70 ℃, reaction times, and preferred temperature of reaction is 6～12h for-30～30 ℃, preferred reaction times.
More of the present invention and among embodiment, the molecular formula of described fluoroolefin is R
1CF=CBD, wherein: R
1For-Cl ,-F or-H, B is-Cl ,-F or-H, D is-Cl ,-F or-H, wherein: preferred R
1Being-F, B is-Cl ,-F, D is-Cl ,-F; And the molecular formula of described halocarbon alkane is RCXYZ, wherein: R is-H ,-Cl ,-F or-CH
3, X is-H ,-Cl ,-F or-CH
3, Y is-H ,-Cl ,-F or-CH
3, Z is-H ,-Cl ,-F or-CH
3, preferred R be-H ,-Cl ,-F, preferred X be-H ,-Cl ,-F, preferably Y be-H ,-Cl ,-F, preferably Z be-H ,-Cl ,-F; Described telomerization general formula is: RCXYZ+R
1CF=CBD=C (RBD) C (FR
1) C (XYZ).
In of the present invention and then embodiment, described direct flash distillation is meant and flashes off the telomerization thing that under 60～110 ℃ preferred temperature is 60～90 ℃.
Of the present invention again more and among embodiment, the temperature of described rectification and purification is 50～90 ℃, is preferably 50～70 ℃.
In again of the present invention and then embodiment, described rectification and purification is for adopting stuffing rectification column, and described filler is glass ring or ceramic ring, is preferably glass ring.
Bottleneck factor restriction on preparation method of the present invention does not have to produce in whole process can be carried out under suitable temperature, pressure, the convenient easily control of technological operation, and the saving energy can be suitable for the industrialization volume production.
Embodiment
Example given below is used for illustrating the invention that is provided.The testing tool of the product of embodiment adopts Agilent 6890N/5937 (GC/MS) gas chromatography instrument.
Embodiment 1
The preparation of composite catalyst: 5L has and adds deionized water 2000 grams in the stainless steel still of chuck and steam heating coil and reflux exchanger, Sodium Fluoride 50 grams, zinc chloride 100 grams, barium fluoride 50 grams, chromium chloride 100 grams, high-speed stirring half an hour, stirring velocity is 100 rev/mins, from the feeding of falling bottom tube ammonia 14 grams, the stainless steel still is warmed up to 40 ℃ with steam, stirred 5 hours, and opened condenser clamp jacket water terminal valve, the stainless steel still is warming up to 120 ℃ with steam heating, open the stainless steel still and be connected valve with condenser, flash distillation moisture content when the condenser outlet at bottom does not have water droplet to go out, stops logical steam heating, be cooled to the room temperature discharging, be placed into the vacuum drying oven oven dry then, the vacuum drying oven temperature remains 140 ℃, and vacuum tightness remains-0,09MPa, be incubated 8 hours, be placed in the moisture eliminator cooling then and obtain composite catalyst, stand-by;
Synthesizing of pentafluorodichloropropane: the 10L stainless steel autoclave has chuck and cooling water coil and condenser, adding is by composite catalyst 300 grams of the rapid gained of previous step, in the stainless steel autoclave chuck, feed-35 ℃ of chilled brines, be pressed into trifluorochloromethane 3135 grams then, stir half an hour, slowly feed difluoro one vinylchlorid then, speed is 350 Grams Per Hours, when difluoro one vinylchlorid feeding total amount is 3546 grams, stop charging, continue to stir 5 hours, stop to feed chilled brine, open the cooling water intakeoutfall valve of condenser and the terminal valve of condenser material, in stainless steel autoclave chuck coil pipe, feed steam, the flash distillation telomer, the still temperature control of stainless steel autoclave is at 80 ℃, at the thick product of condensator outlet collection pentafluorodichloropropane, obtain pentafluorodichloropropane synthetics 4710 grams;
The rectification and purification of pentafluorodichloropropane synthetics: 5L four-hole glass flask has the glass column of Φ 40 * 2000, loads 1900 millimeters high glass ring filler in the glass column, the cock that condenser is housed on the glass column and regulates reflux ratio.Glass flask adopts the oil bath heating, glass column adopts the heat tape insulation, 4710 gram pentafluorodichloropropane syntheticss are joined in the 5L glass flask, open the cooling water intakeoutfall valve of condenser, the still temperature of control 5L glass flask is about 100 ℃, glass column middle part temperature is about 80 ℃, the glass column head temperature is about 58 ℃, whole rectifying process begins to adopt total reflux half an hour, sampling analysis heats up in a steamer before collecting then, when pentafluorodichloropropane purity reaches 98.5% when above, collect the finished product pentafluorodichloropropane, obtain pentafluorodichloropropane finished product 4200 grams at last.The transformation efficiency of whole process trifluorochloromethane is 95.1%, and yield is 68.99%.
Embodiment 2
The preparation of composite catalyst: 5L has and adds deionized water 2000 grams in the stainless steel still of chuck and steam heating coil and reflux exchanger, Potassium monofluoride 50 grams, magnesium chloride 100 grams, aluminum chloride 50 grams, chromium chloride 100 grams, high-speed stirring half an hour, stirring velocity is 100 rev/mins, and from the feeding of falling bottom tube ammonia 21 grams, the stainless steel still is warmed up to 40 ℃ with steam, stirred 5 hours, open condenser clamp jacket water terminal valve, the stainless steel still is warming up to 120 ℃ with steam heating, opens the stainless steel still and is connected valve with condenser, flash distillation moisture content, when the condenser outlet at bottom does not have water droplet to go out, stop logical steam heating, be cooled to the room temperature discharging, be placed into the vacuum drying oven oven dry then, the vacuum drying oven temperature remains 140 ℃, and vacuum tightness remains-0.09MPa, is incubated 8 hours, be placed in the moisture eliminator cooling then and obtain composite catalyst, stand-by;
Synthesizing of pentafluorodichloropropane: the 10L stainless steel autoclave has chuck and cooling water coil and condenser, adding is by composite catalyst 300 grams of the rapid gained of previous step, in the stainless steel autoclave chuck, feed-35 ℃ of chilled brines, be pressed into trifluorochloromethane 3135 grams then, stir half an hour, slowly feed difluoro one vinylchlorid then, speed is 350 Grams Per Hours, when difluoro one vinylchlorid feeding total amount is 3546 grams, stop charging, continue to stir 5 hours, stop to feed chilled brine, open the cooling water intakeoutfall valve of condenser and the terminal valve of condenser material, in the chuck coil pipe, feed steam, the flash distillation telomer, the still temperature control of stainless steel autoclave is at 80 ℃, at the thick product of condensator outlet collection pentafluorodichloropropane, obtain pentafluorodichloropropane synthetics 5120 grams;
The rectification and purification of pentafluorodichloropropane synthetics: 5L four-hole glass flask has the glass column of Φ 40 * 2000, load 1900 millimeters high glass ring filler in the glass column, the cock that condenser is housed on the glass column and regulates reflux ratio, glass flask adopts the oil bath heating, glass column adopts the heat tape insulation, 5120 gram pentafluorodichloropropane syntheticss are added in the 5L glass flask, open the cooling water intakeoutfall valve of condenser, the still temperature of control 5L glass flask is about 100 ℃, glass column middle part temperature is about 80 ℃, the glass column head temperature is about 58 ℃, whole rectifying process begins to adopt total reflux half an hour, and sampling analysis heats up in a steamer before collecting then, when pentafluorodichloropropane purity reaches 98.5% when above, collect the finished product pentafluorodichloropropane, obtain pentafluorodichloropropane finished product 4815 grams at last.The transformation efficiency of whole process trifluorochloromethane is 97%, and yield is 79.09%.
Embodiment 3
The preparation of composite catalyst: 5L has and adds deionized water 2000 grams in the stainless steel still of chuck and steam heating coil and reflux exchanger, tin tetrachloride 50 grams, zinc chloride 100 grams, bariumchloride 50 grams, chromium chloride 100 grams, high-speed stirring half an hour, stirring velocity is 100 rev/mins, and from the feeding of falling bottom tube ammonia 12 grams, the stainless steel still is warmed up to 40 ℃ with steam, stirred 5 hours, open condenser clamp jacket water terminal valve, the stainless steel still is warming up to 120 ℃ with steam heating, opens the stainless steel still and is connected valve with condenser, flash distillation moisture content, when the condenser outlet at bottom does not have water droplet to go out, stop logical steam heating, be cooled to the room temperature discharging, be placed into the vacuum drying oven oven dry then, the vacuum drying oven temperature remains 140 ℃, and vacuum tightness remains-0.09MPa, is incubated 8 hours, be placed in the dry device cooling then and obtain composite catalyst, stand-by;
Synthesizing of pentafluorodichloropropane: the 10L stainless steel autoclave has chuck and cooling water coil and condenser, adding is by composite catalyst 300 grams of the rapid gained of previous step, in the stainless steel autoclave chuck, feed-35 ℃ of chilled brines, be pressed into trifluorochloromethane 3135 grams then, stir half an hour, slowly feed difluoro one vinylchlorid then, speed is 350 Grams Per Hours, when difluoro one vinylchlorid feeding total amount is 3546 grams, stop charging, continue to stir 5 hours, stop to feed chilled brine, open the cooling water intakeoutfall valve of condenser and the terminal valve of condenser material, in the chuck coil pipe, feed steam, the flash distillation telomer, the still temperature control of stainless steel autoclave is at 80 ℃, at the thick product of condensator outlet collection pentafluorodichloropropane, obtain pentafluorodichloropropane synthetics 4510 grams;
The rectification and purification of pentafluorodichloropropane synthetics: 5L four-hole glass flask has the glass column of Φ 40 * 2000, load 1900 millimeters high glass ring filler in the glass column, the cock that condenser is housed on the glass column and regulates reflux ratio, glass flask adopts the oil bath heating, glass column adopts the heat tape insulation, 4510 gram pentafluorodichloropropane syntheticss are joined in the 5L glass flask, open the cooling water intakeoutfall valve of condenser, the still temperature of control 5L glass flask is about 100 ℃, glass column middle part temperature is about 80 ℃, the glass column head temperature is about 58 ℃, whole rectifying process begins to adopt total reflux half an hour, and sampling analysis heats up in a steamer before collecting then, when pentafluorodichloropropane purity reaches 98.5% when above, collect the finished product pentafluorodichloropropane, obtain pentafluorodichloropropane finished product 4150 grams at last.The transformation efficiency of whole process trifluorochloromethane is 94.5%, and yield is 68.16%.
Embodiment 4
The preparation of composite catalyst: 5L has and adds deionized water 2000 grams in the stainless steel still of chuck and steam heating coil and reflux exchanger, Sodium Fluoride 50 grams, zinc chloride 100 grams, barium fluoride 50 grams, chromium chloride 100 gram, high-speed stirring half an hour, stirring velocity is 100 rev/mins, from the feeding of falling bottom tube ammonia 14 grams, the stainless steel still is warmed up to 40 ℃ with steam, stirs 5 hours, opens condenser clamp jacket water terminal valve, the stainless steel still is warming up to 120 ℃ with steam heating, open the stainless steel still and be connected valve with condenser, flash distillation moisture content is not when the condenser outlet at bottom has water droplet to go out, stop logical steam heating, be cooled to the room temperature discharging, then, be placed into the vacuum drying oven oven dry, the vacuum drying oven temperature remains 140 ℃, vacuum tightness remains-0.09MPa, is incubated 8 hours, then, be placed in the moisture eliminator cooling and obtain composite catalyst, stand-by;
Synthesizing of pentafluorodichloropropane: the 10L stainless steel autoclave has chuck and cooling water coil and condenser, adding is by composite catalyst 300 grams of the rapid gained of previous step, in the stainless steel autoclave chuck, feed-15 ℃ of chilled brines, be pressed into difluorochloromethane 2235 grams then, stir half an hour, slowly feed trifluorochloroethylene then, speed is 400 Grams Per Hours, when trifluorochloroethylene feeding total amount is 3728 grams, stop charging, continue to stir 5 hours, stop to feed chilled brine, open the cooling water intakeoutfall valve of condenser and the terminal valve of condenser material, in the chuck coil pipe, feed steam, the flash distillation telomer, the still temperature control of stainless steel autoclave is at 80 ℃, at the thick product of condensator outlet collection pentafluorodichloropropane, obtain pentafluorodichloropropane synthetics 4320 grams;
The rectification and purification of pentafluorodichloropropane synthetics: 5L four-hole glass flask has the glass column of Φ 40 * 2000, load 1900 millimeters high glass ring filler in the glass column, the cock that condenser is housed on the glass column and regulates reflux ratio, glass flask adopts the oil bath heating, glass column adopts the heat tape insulation, 4320 gram pentafluorodichloropropane syntheticss are added in the 5L glass flask, open the cooling water intakeoutfall valve of condenser, the still temperature of control 5L glass flask is about 100 ℃, glass column middle part temperature is about 80 ℃, the glass column head temperature is about 58 ℃, whole rectifying process begins to adopt total reflux half an hour, and sampling analysis heats up in a steamer before collecting then, when pentafluorodichloropropane purity reaches 98.5% when above, collect the finished product pentafluorodichloropropane, obtain pentafluorodichloropropane finished product 4005 grams at last.The transformation efficiency of whole process difluorochloromethane is 92.6%, and yield is 65.78%.
Embodiment 5
The preparation of composite catalyst: 5L has and adds deionized water 2000 grams in the stainless steel still of chuck and steam heating coil and reflux exchanger, Potassium monofluoride 50 grams, magnesium chloride 100 grams, aluminum chloride 50 grams, chromium chloride 100 grams, high-speed stirring half an hour, stirring velocity is 100 rev/mins, and from the feeding of falling bottom tube ammonia 21 grams, the stainless steel still is warmed up to 40 ℃ with steam, stirred 5 hours, open condenser clamp jacket water terminal valve, the stainless steel still is warming up to 120 ℃ with steam heating, opens the stainless steel still and is connected valve with condenser, flash distillation moisture content, when the condenser outlet at bottom does not have water droplet to go out, stop logical steam heating, be cooled to the room temperature discharging, be placed into the vacuum drying oven oven dry then, the vacuum drying oven temperature remains 140 ℃, and vacuum tightness remains-0.09MPa, is incubated 8 hours, be placed in the moisture eliminator cooling then and obtain composite catalyst, stand-by;
Synthesizing of pentafluorodichloropropane: the 10L stainless steel autoclave has chuck and cooling water coil and condenser, adding is by composite catalyst 300 grams of the rapid gained of previous step, in the stainless steel autoclave chuck, feed-15 ℃ of chilled brines, be pressed into difluorochloromethane 2235 grams then, stir half an hour, slowly feed trifluorochloroethylene then, speed is 400 Grams Per Hours, when trifluorochloroethylene feeding total amount is 3728 grams, stop charging, continue to stir 5 hours, stop to feed chilled brine, open the cooling water intakeoutfall valve of condenser and the terminal valve of condenser material, in the chuck coil pipe, feed steam, the flash distillation telomer, the still temperature control of stainless steel autoclave is at 80 ℃, at the thick product of condensator outlet collection pentafluorodichloropropane, obtain pentafluorodichloropropane synthetics 5247 grams;
The rectification and purification of pentafluorodichloropropane synthetics: 5L four-hole glass flask has the glass column of Φ 40 * 2000, load 1900 millimeters high glass ring filler in the glass column, the cock that condenser is housed on the glass column and regulates reflux ratio, glass flask adopts the oil bath heating, glass column adopts the heat tape insulation, 5247 gram pentafluorodichloropropane syntheticss are added in the 5L glass flask, open the cooling water intakeoutfall valve of condenser, the still temperature of control 5L glass flask is about 100 ℃, glass column middle part temperature is about 80 ℃, the glass column head temperature is about 58 ℃, whole rectifying process begins to adopt total reflux half an hour, and sampling analysis heats up in a steamer before collecting then, when pentafluorodichloropropane purity reaches 98.5% when above, collect the finished product pentafluorodichloropropane, obtain pentafluorodichloropropane finished product 5019 grams at last.The transformation efficiency of whole process difluorochloromethane is 97%, and yield is 82.44%.
Embodiment 6
The preparation of composite catalyst: 5L has and adds deionized water 2000 grams in the stainless steel still of chuck and steam heating coil and reflux exchanger, Sodium Fluoride 50 grams, zinc chloride 100 grams, barium fluoride 50 grams, chromium chloride 100 grams, high-speed stirring half an hour, stirring velocity is 100 rev/mins, and from the feeding of falling bottom tube ammonia 14 grams, stainless steel still steam is warmed up to 40 ℃, stirred 5 hours, open condenser clamp jacket water terminal valve, the stainless steel still is warming up to 120 ℃ with steam heating, opens the stainless steel still and is connected valve with condenser, flash distillation moisture content, when the condenser outlet at bottom does not have water droplet to go out, stop logical steam heating, be cooled to the room temperature discharging, be placed into the vacuum drying oven oven dry then, the vacuum drying oven temperature remains 140 ℃, and vacuum tightness remains-0.09MPa, is incubated 8 hours, be placed in the moisture eliminator cooling then and obtain composite catalyst, stand-by;
Synthesizing of pentafluorodichloropropane: the 10L stainless steel autoclave has chuck and cooling water coil and condenser, adding is by composite catalyst 300 grams of the rapid gained of previous step, in the stainless steel autoclave chuck, feed-15 ℃ of chilled brines, be pressed into dichloromonofluoromethane 3090 grams then, stir half an hour, slowly feed tetrafluoroethylene then, speed is 400 Grams Per Hours, when tetrafluoroethylene feeding total amount is 3200 grams, stop charging, continue to stir 5 hours, stop to feed chilled brine, open the cooling water intakeoutfall valve of condenser and the terminal valve of condenser material, in the chuck coil pipe, feed steam, the flash distillation telomer, the still temperature control of stainless steel autoclave is at 80 ℃, at the thick product of condensator outlet collection pentafluorodichloropropane, obtain pentafluorodichloropropane synthetics 5113 grams at last;
The rectification and purification of pentafluorodichloropropane synthetics: 5L four-hole glass flask has the glass column of Φ 40 * 2000, load 1900 millimeters high glass ring filler in the glass column, the cock that condenser is housed on the glass column and regulates reflux ratio, glass flask adopts the oil bath heating, glass column adopts the heat tape insulation, 5113 gram pentafluorodichloropropane syntheticss are added in the 5L glass flask, open the cooling water intakeoutfall valve of condenser, the still temperature of control 5L glass flask is about 100 ℃, glass column middle part temperature is about 80 ℃, the glass column head temperature is about 58 ℃, whole rectifying process begins to adopt total reflux half an hour, and sampling analysis heats up in a steamer before collecting then, when pentafluorodichloropropane purity reaches 98.5% when above, collect the finished product pentafluorodichloropropane, obtain pentafluorodichloropropane finished product 4901 grams at last.The transformation efficiency of whole process dichloromonofluoromethane is 95%, and yield is 80.50%.
Embodiment 7
The preparation of composite catalyst: 5L has and adds deionized water 2000 grams in the stainless steel still of chuck and steam heating coil and reflux exchanger, Potassium monofluoride 50 grams, magnesium chloride 100 grams, aluminum chloride 50 grams, chromium chloride 100 grams, high-speed stirring half an hour, stirring velocity is 100 rev/mins, and from the feeding of falling bottom tube ammonia 21 grams, the stainless steel still is warmed up to 40 ℃ with steam, stirred 5 hours, open condenser clamp jacket water terminal valve, the stainless steel still is warming up to 120 ℃ with steam heating, opens the stainless steel still and is connected valve with condenser, flash distillation moisture content, when the condenser outlet at bottom does not have water droplet to go out, stop logical steam heating, be cooled to the room temperature discharging, be placed into the vacuum drying oven oven dry then, the vacuum drying oven temperature remains 140 ℃, and vacuum tightness remains-0.09MPa, is incubated 8 hours, be placed in the moisture eliminator cooling then and obtain composite catalyst, stand-by;
Synthesizing of pentafluorodichloropropane: the 10L stainless steel autoclave has chuck and cooling water coil and condenser, adding is by composite catalyst 300 grams of the rapid gained of previous step, in the stainless steel autoclave chuck, feed-15 ℃ of chilled brines, be pressed into dichloromonofluoromethane 3090 grams then, stir half an hour, slowly feed tetrafluoroethylene then, speed is 400 Grams Per Hours, when tetrafluoroethylene feeding total amount is 3200 grams, stop charging, continue to stir 5 hours, stop to feed chilled brine, open the cooling water intakeoutfall valve of condenser and the terminal valve of condenser material, in the chuck coil pipe, feed steam, the flash distillation telomer, the still temperature control of stainless steel autoclave is at 80 ℃, at the thick product of condensator outlet collection pentafluorodichloropropane, obtain pentafluorodichloropropane synthetics 5073 grams;
The rectification and purification of pentafluorodichloropropane synthetics: 5L four-hole glass flask has the glass column of Φ 40 * 2000, load 1900 millimeters high glass ring filler in the glass column, the cock that condenser is housed on the glass column and regulates reflux ratio, glass flask adopts the oil bath heating, glass column adopts the heat tape insulation, 5073 gram pentafluorodichloropropane syntheticss are added in the 5L glass flask, open the cooling water intakeoutfall valve of condenser, the still temperature of control 5L glass flask is about 100 ℃, glass column middle part temperature is about 80 ℃, the glass column head temperature is about 58 ℃, whole rectifying process begins to adopt total reflux half an hour, and sampling analysis heats up in a steamer before collecting then, when pentafluorodichloropropane purity reaches 98.5% when above, collect the finished product pentafluorodichloropropane, obtain pentafluorodichloropropane finished product 4867 grams at last.The transformation efficiency of whole process dichloromonofluoromethane is 95%, and yield is 79.94%.
Embodiment 8
The preparation of composite catalyst: 5L has and adds deionized water 2000 grams in the stainless steel still of chuck and steam heating coil and reflux exchanger, Sodium Fluoride 50 grams, titanium chloride 100 grams, magnesium fluoride 50 grams, chromium chloride 100 grams, high-speed stirring half an hour, stirring velocity is 100 rev/mins, and from the feeding of falling bottom tube ammonia 14 grams, stainless steel is warmed up to 40 ℃ with steam, stirred 5 hours, open condenser clamp jacket water terminal valve, the stainless steel still is warming up to 120 ℃ with steam heating, opens the stainless steel still and is connected valve with condenser, flash distillation moisture content, when the condenser outlet at bottom does not have water droplet to go out, stop logical steam heating, be cooled to the room temperature discharging, be placed into the vacuum drying oven oven dry then, the vacuum drying oven temperature remains 140 ℃, and vacuum tightness remains-0.09MPa, is incubated 8 hours, be placed in the moisture eliminator cooling then and obtain composite catalyst, stand-by;
Synthesizing of pentafluorodichloropropane: the 10L stainless steel autoclave has chuck and cooling water coil and condenser, adding is by composite catalyst 300 grams of the rapid gained of previous step, in the stainless steel autoclave chuck, feed-15 ℃ of chilled brines, be pressed into difluorochloromethane 2235 grams then, stir half an hour, slowly feed trifluorochloroethylene then, speed is 400 Grams Per Hours, when trifluorochloroethylene feeding total amount is 3728 grams, stop charging, continue to stir 5 hours, stop to feed chilled brine, open the cooling water intakeoutfall valve of condenser and the terminal valve of condenser material, in the chuck coil pipe, feed steam, the flash distillation telomer, the still temperature control of stainless steel autoclave is at 80 ℃, at the thick product of condensator outlet collection pentafluorodichloropropane, obtain pentafluorodichloropropane synthetics 5319 grams;
The rectification and purification of pentafluorodichloropropane synthetics: 5L four-hole glass flask has the glass column of Φ 40 * 2000, load 1900 millimeters high glass ring filler in the glass column, the cock that condenser is housed on the glass column and regulates reflux ratio, glass flask adopts the oil bath heating, glass column adopts the heat tape insulation, 5319 gram pentafluorodichloropropane syntheticss are added in the 5L glass flask, open the cooling water intakeoutfall valve of condenser, the still temperature of control 5L glass flask is about 100 ℃, glass column middle part temperature is about 80 ℃, the glass column head temperature is about 58 ℃, whole rectifying process begins to adopt total reflux half an hour, and sampling analysis heats up in a steamer before collecting then, when pentafluorodichloropropane purity reaches 98.5% when above, collect the finished product pentafluorodichloropropane, obtain pentafluorodichloropropane finished product 5236 grams at last.The transformation efficiency of whole process difluorochloromethane is 97%, and yield is 86.0%.
Claims (9)
1. the preparation method of a pentafluorodichloropropane, comprise the synthesis step of preparation process, the pentafluorodichloropropane of composite catalyst, to the rectification and purification step of pentafluorodichloropropane synthetics, what it is characterized in that described pentafluorodichloropropane syntheticly is meant the directly flash distillation after telomerization in the presence of the composite catalyst by fluoroolefin and halocarbon alkane, the preparation of described composite catalyst is earlier metal halide admixture to be dissolved in the water under 40～60 ℃ temperature, feed ammonia gas react 4～8h, flash distillation moisture content, vacuum drying obtains the finished product composite catalyst then.
2. the preparation method of pentafluorodichloropropane according to claim 1, the mol ratio that it is characterized in that described fluoroolefin and halocarbon alkane is, fluoroolefin: halocarbon alkane=0.9～5.5: 1, the consumption of described composite catalyst is 0.5～7% of a halocarbon alkane molar weight.
3. the preparation method of pentafluorodichloropropane according to claim 1, the mol ratio that it is characterized in that described metal halide admixture and ammonia is 1: 0.2～3.5.
4. the preparation method of pentafluorodichloropropane according to claim 3, it is characterized in that described metal halide admixture is IA family metal villiaumite or IA family metal villaumite, IIA family metal villiaumite or IIA family metal villaumite, IVB family metal villiaumite or IVB family metal villaumite, group vib metal villiaumite or group vib metal villaumite, IIIA family metal villiaumite or IIIA family metal villaumite, IVA family metal villiaumite or IVA family metal villaumite, two or more mixture in VA family metal villiaumite or the VA family metal villaumite.
5. the preparation method of pentafluorodichloropropane according to claim 1, the temperature of reaction that it is characterized in that described telomerization is 6～20h for-30～70 ℃, reaction times.
6. the preparation method of pentafluorodichloropropane according to claim 1, the molecular formula that it is characterized in that described fluoroolefin is R1CF=CBD, wherein: R1 is-Cl ,-F or-H, B is-Cl ,-F or-H, D is-Cl ,-F or-H; And the molecular formula of described halocarbon alkane is RCXYZ, wherein: R is-H ,-Cl or-F, X is-H ,-Cl or-F, Y is-H ,-Cl or-F, Z is-H ,-Cl or-F; Described telomerization general formula is: RCXYZ+R
1CF=CBD → C (RBD) C (F R
1) C (XYZ).
7. the preparation method of pentafluorodichloropropane according to claim 1 is characterized in that described direct flash distillation is meant to flash off the telomerization thing under 60～110 ℃.
8. the preparation method of pentafluorodichloropropane according to claim 1, the temperature that it is characterized in that described rectification and purification is 50～90 ℃.
9. according to the preparation method of claim 1 or 8 described pentafluorodichloropropanes, it is characterized in that described rectification and purification for adopting stuffing rectification column, described filler is glass ring or ceramic ring.
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|---|---|---|---|---|
| US2449360A (en) * | 1943-08-11 | 1948-09-14 | Du Pont | Preparation of highly halogenated fluoroalkanes |
| US2456027A (en) * | 1944-04-01 | 1948-12-14 | Minnesota Mining & Mfg | Method of making fluorocarbons |
| US3795710A (en) * | 1962-10-09 | 1974-03-05 | Pechiney Saint Gobain | Process for preparing fluoro-halogenated propane derivatives and use thereof |
| US5177274A (en) * | 1990-01-08 | 1993-01-05 | Daikin Industries Ltd. | Process for preparing pentafluorodichloropropanes |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2449360A (en) * | 1943-08-11 | 1948-09-14 | Du Pont | Preparation of highly halogenated fluoroalkanes |
| US2456027A (en) * | 1944-04-01 | 1948-12-14 | Minnesota Mining & Mfg | Method of making fluorocarbons |
| US3795710A (en) * | 1962-10-09 | 1974-03-05 | Pechiney Saint Gobain | Process for preparing fluoro-halogenated propane derivatives and use thereof |
| US5177274A (en) * | 1990-01-08 | 1993-01-05 | Daikin Industries Ltd. | Process for preparing pentafluorodichloropropanes |
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| Title |
|---|
| US 5177274 A,说明书第2－4栏. |
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