CN104692998B - The preparation method of bis- fluoro- 2- chloroethanes of 1,1- - Google Patents
The preparation method of bis- fluoro- 2- chloroethanes of 1,1- Download PDFInfo
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- CN104692998B CN104692998B CN201510072012.XA CN201510072012A CN104692998B CN 104692998 B CN104692998 B CN 104692998B CN 201510072012 A CN201510072012 A CN 201510072012A CN 104692998 B CN104692998 B CN 104692998B
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Abstract
The invention discloses the preparation methods of 1,1 difluoro, 2 chloroethanes, include the following steps：By 1,1,2 trichloroethanes or along 1,2 dichloroethylene, anti-1,2 dichloroethylene and 1, the mixture of 1,2 trichloroethanes are 150~350 DEG C in temperature, pressure (absolute pressure) 0.1~1.1MPa, 15~150 seconds times of contact, HF and material molar ratio containing chlorine=2~40:Under the conditions of 1, chromium magnesium fluoride catalysts are added in, are reacted through fixed bed reactors gas phase catalytic fluorination, condensed product, stratified liquid, neutralization, drying and rectifying is collected and 1,1 difluoro of high-purity, 2 chloroethanes is made.Preparation process of the present invention is simple, at low cost, high income, has good prospects for commercial application, is particularly suitable for large-scale industrial production.
Description
Technical field
The present invention relates to the preparation methods of 1,1-, bis- fluoro- 2- chloroethanes, belong to organic synthesis field.
Background technology
1.1- two fluoro- 2- chloroethanes (dichlorodifluoromethan 142) are the intermediate products for preparing 2,2- difluoroethanols, current various countries are
Consider to substitute dichlorodifluoromethan 113,141b, 140a etc. using dichlorodifluoromethan 142, for surface of solids cleaning, dry, degreasing aerosol
With foaming agent field, R142 has good market prospects.The product preparation method patent it is external it has been reported that but data not
It is more, it is domestic to be reported without similar patent.The method of production bis- fluoro- 2- chloroethanes of 1.1- is gas phase catalytic fluorination, synthetic route
Difference according to starting material can be divided into following two, and reaction equation is as follows：
First synthetic route：
Article 2 synthetic route：
Catalyst is to synthesize most crucial influence factor during bis- fluoro- 2- chloroethanes of 1.1-, between different synthetic methods
The most important difference difference lies in selected catalyst type.
As 142 preparation method of dichlorodifluoromethan is trichlorine in known patent (EP 1008575, C07C 17/20,14.06.2000)
Ethane and hydrogen fluoride gas phase reaction under catalysts conditions, then detach dichlorodifluoromethan 142 from reactant.Catalyst select be
By the Cr of fluorination treatment2O3.In addition to Cr2O3Outside, catalyst can be with or without one or more of metal pentafluoride salt carriers:Such as
Chromium, iron, niobium, nickel, antimony, tin, tantalum, titanium etc..Reaction condition is as follows：100 DEG C~380 DEG C of temperature, pressure 0.1MPa (0psig)~
2.86MPa (400psig), HF and 140 to 2~20,1~100 second time of contact.
Byproduct hydrogen chloride (HCl) can pass through distillation or the absorption and separation in water or lye.Unreacted HF passes through distillation
Or the absorption and separation in water or lye, using phase separation or semi-transparent UF membrane.Other organic by-products can be separated by distillation.
Unsaturated organic by-products can be reacted before distillation detaches by product with chlorine or bromine to be handled.
In embodiment, catalyst chromium oxide (Cr2O3)(20см3, 27g) and 380 DEG C of activation temperature, in HF (6.6g/
And air (100cm h)3/ point) purge 18 hours under the conditions of gaseous mixture.When dichlorodifluoromethan 142 synthesizes trichloroethanes is passed through in reactor
With hydrogen fluoride gas phase gaseous mixture, 220 DEG C of temperature, molar ratio=7.8 of hydrogen fluoride and trichloroethanes:1 (10.1g/h HF and 0.1 с
м3/ divide trichloroethanes), pressure 1.13MPa (150psig), 34 seconds times of contact, the selectivity of generation dichlorodifluoromethan 142 is
70.2%.
For another example known patent (EP 1008574, C07C 17/10,07.12.1999), using 1,2-dichloroethene as Fluoride for Raw Material
Change prepares dichlorodifluoromethan 142, is dichloroethylene and HF gas phase reactions under catalysts conditions, then detaches fluorine chlorine from reactant again
Alkane 142.The invention catalyst, synthesis and 142 separation condition of dichlorodifluoromethan are similar to EP 1008575.Two have been carried out in embodiment
Vinyl chloride is with HF in chromated oxide (Cr2O3) react in catalyst, dichloroethylene and HF gas phase gaseous mixtures are passed through to reactor, temperature
Molar ratio=6.5 of 220 DEG C of degree, hydrogen fluoride and dichloroethylene:1 (10.1g/h HF and 0.1 с м3/ divide dichloroethylene), pressure
1.13MPa (150psig), 34 seconds times of contact, dichloroethylene conversion ratio 88.3%, the selectivity of generation dichlorodifluoromethan 142 are
84.2%.
Although trichloroethanes (dichloroethylene) prepare dichlorodifluoromethan 142 conversion ratio and selectivity it is higher, unfortunately urge
Agent is powdered rather than particle, and industrialization catalytic reactor is not well suited for.Catalyst system with carrier in embodiment
Standby system and practical preparation result difference are larger.
Dichlorodifluoromethan 142 prepares patent (WO 2013/053800, B01J 23/06,18.04.2013), and that illustrate is HF and three
Chloroethanes and/or dichloroethylene carry out gas phase reaction under catalysts conditions, and method for preparing catalyst uses chromium aluminium base
FeCl3And MgCl2Cr (the NO of co-precipitated catalyst or activated carbon substrates3)3With Ni (NO3)2Co-precipitated catalyst or oxygen
Change aluminium and ZnCl2Co-precipitated catalyst.200~350 DEG C of 142 preparation flow temperature of dichlorodifluoromethan, atmospheric pressure or under pressure to 2.5MPa (25
Bar), molar ratio=2~30 of hydrogen fluoride and trichloroethanes and/or dichloroethylene:1,10~200 seconds times of contact, catalyst can
The appearances such as the sheet prepared using the above method or particle.
Ready catalyst 120~140 DEG C of nitrogen treatments 1~50 hour, 10~40 seconds times of contact before synthesis.So
Handled under the conditions of 150~400 DEG C with HF or HF and nitrogen or air Mixture again afterwards, finally 375 DEG C with HF to urging
Agent carries out activation 20~30 hours.
Dichlorodifluoromethan 142 is synthesized in embodiment carries out in above-mentioned catalyst, and the catalyst used is Cr2O3/Al2O3/
FeCl3/MgCl2, 220~240 DEG C of synthesis temperature, pressure 0.5MPa (5 bars), HF and trichloroethanes molar ratio=6.5:1, contact
90 seconds time, the conversion ratio 90~98% of trichloroethanes generates the selectivity 22~34% of dichlorodifluoromethan 142, and generates two chloroethenes
The selectivity of alkene is 45~54%.
Use Al2O3/ZnCl2The temperature of catalyst synthesis dichlorodifluoromethan 142 is 220~240 DEG C, pressure 0.5MPa (5 bars),
HF and trichloroethanes molar ratio=7.3~8.7:1,127~142 seconds times of contact, the conversion ratio 92~97% of trichloroethanes is raw
Into the selectivity 26~35% of dichlorodifluoromethan 142, and the selectivity for generating dichloroethylene is 48~61%.
Using carried by active carbon Cr (NO3)3With Ni (NO3)2During catalyst, 230~240 DEG C of 142 synthesis temperature of dichlorodifluoromethan,
Pressure 0.5MPa (5 bars), HF and trichloroethanes molar ratio=7.9~8.9:1,94~135 seconds times of contact, trichloroethanes turns
Rate 94~99%, generates the selectivity 65% of dichlorodifluoromethan 142, and the selectivity for generating dichloroethylene is 28%.HF and dichloro
The temperature that ethylene synthesizes dichlorodifluoromethan 142 under this catalysts conditions is 240 DEG C, pressure 0.5MPa, HF and trichloroethanes mole
Than=1:5.6~7.2,130~139 seconds times of contact, the conversion ratio 60.6~63.8% of dichloroethylene.
Use Cr2O3/Al2O3/FeCl3/MgCl2And Al2O3/ZnCl2The not foot point of catalyst is with using carried by active carbon Cr
(NO3)3With Ni (NO3)2Catalyst is lower compared to the selectivity of generation dichlorodifluoromethan 142, Cr2O3/Al2O3/FeCl3/MgCl2Catalysis
Agent contains Cr2O3About 40%, the cost of catalyst is increased in this way, equally also increases the manufacture cost of dichlorodifluoromethan 142.
In addition, carried by active carbon Cr (NO3)3With Ni (NO3)2Catalyst can not supporting reactions under conditions of activity reduces.
Know, catalyst surface reduces activity due to generation carbon black or lipid aggregate object in continuous process, these substances are all
It is feed material degradation products or synthetic.The regeneration of decaying catalyst is exactly to allow catalyst in high temperature air or oxygen
Reason ensures that the carbon black of catalyst surface or lipid aggregate object can burn to the greatest extent.Therefore, to the work of 2013/053800 Patent designs of WO
Property charcoal carried catalyst to carry out regeneration treatment be impossible, this will greatly shorten service life, this is also a real deficiency
Point.
Invention content
The present invention in view of the deficiencies of the prior art, provides 1, the 1- preparation methods of bis- fluoro- 2- chloroethanes, particularly will
A kind of chromium magnesium fluoride catalysts are applied to prepare 1,1-, bis- fluoro- 2- chloroethanes, and this method is simple for process, at low cost, high income,
With good prospects for commercial application, it is particularly suitable for large-scale industrial production.
In order to solve the above-mentioned technical problem, the present invention adopts the following technical scheme that：
The preparation method of 1,1- bis- fluoro- 2- chloroethanes, it is characterised in that include the following steps：
1) the chromium magnesium fluoride catalysts containing 10~15% charomic fluorides (trivalent) and 85~90% magnesium fluorides are added first
Enter in reactor and reacted, and be stirred with blender, blown nitrogen with the speed of 6~10 marks l/h with blower pump
It sweeps reactor 2~5 hours, then temperature is controlled by evaporator and carries out predrying at 100~200 DEG C, and supplied by evaporator
To hydrogen fluoride, the feed speed of hydrogen fluoride is 100~200g/h, and activation continues 4~8 hours, then by the chromium magnesium after predrying
Fluoride catalysts carry out activation process at a temperature of 200~350 DEG C with hydrogen fluoride, by evaporator at the end of processing to be activated
Temperature is set in 150~350 DEG C；
2) the chromium magnesium fluoride catalysts after above-mentioned perfluorinated hydrogen activation process are added in into the fixed bed with catalyst layer
Reactor, then by 1,1,2- trichloroethanes or along 1,2-dichloroethene, anti-1,2-dichloroethene and 1,1,2- trichloroethanes
Mixture is 150~350 DEG C in reaction temperature, and reaction pressure (absolute pressure) is 0.1~1.1MPa, time of contact for 15~
150 seconds, HF and material molar ratio containing chlorine=2~40:Under conditions of 1, it is anti-to be passed through fixed bed reactors progress gas phase catalytic fluorination
Should, and pervaporation device is listened to be passed through hydrogen fluoride and trichloroethanes or dichloroethylene into fixed bed reactors in synthesis, it adjusts simultaneously
Save the reaction pressure in fixed bed reactors；
3) sintetics after the reaction of above-mentioned gas phase catalytic fluorination then is passed through condenser to condense, after condensation
Synthetic be layered again, upper strata is made after separation to be hydrogen fluoride, lower floor to contain dichlorodifluoromethan 142, along dichloroethylene, anti-dichloro
The gaseous state synthetic product of ethylene and trichloroethanes, the outlet of gaseous state synthetic product condensed device release, and continue to be passed through hydrogen fluoride and
Trichloroethanes or dichloroethylene；
4) after the completion of hydrogen and trichloroethanes to be fluorinated supply, the liquid phase synthesis product of layered method liquid phase separation is from collector
Bottom releases, and the hydrogen fluoride of separation uses for lower batch, and the liquid phase synthesis product of bottom is organic mixture, and molten with alkalinity
Liquid neutralizes organic mixture, then is dried with zeolite NaA, finally by bis- fluoro- 2- chloroethanes of obtained 1,1- after rectifying, essence
Suitable dichloroethylene and anti-dichloroethylene of the fraction from after are used for the synthesis of lower batch dichlorodifluoromethan 142.
Neutralize, dry purpose is separation dichlorodifluoromethan 142 and containing along 1,2- dichloroethylene, anti-1,2- dichloroethylene and 1,
The mixture of 1,2- trichloroethanes, the raw material which can synthesize as dichlorodifluoromethan 142, rectificating method can isolate mesh
Product dichlorodifluoromethan 142, and can be used for the synthesis of lower batch dichlorodifluoromethan 142 along dichloroethylene and anti-dichloroethylene, at the same
Hydrogen fluoride is reused in synthesis hydrogen fluoride to be made to reach high conversion.
Further, the chromium magnesium fluoride catalysts in step 1) be graininess, active component Cr3+, wherein active component
10%~15% is accounted in chromium magnesium fluoride catalysts.
Preferably, the carrier of chromium magnesium fluoride catalysts is MgF2。
Preferably, the reaction temperature in step 2) be 220~280 DEG C, reaction pressure be 0.6~0.9MPa, time of contact
It is 20~50 seconds, HF and material molar ratio containing chlorine=4~10:1.
Preferably, the condenser in step 3) is recoverable condenser, can be improved after gas phase catalytic fluorination reacts
The condensing rate of sintetics saves preparation time.
Further, refrigerant chuck on condenser is installed, reduces the temperature in condenser.
Further, electric heater is mounted on evaporator and reactor, convenient for the temperature in control evaporator and reactor
Degree so that evaporator and the reactor temperature in each stage in preparation process meet the needs of reaction process.
Further, pressure gauge and regulating valve are installed, pressure gauge and regulating valve are used to keep reaction system must on reactor
The pressure wanted, it is ensured that reaction is smoothed out.
The present invention is by adopting the above-described technical solution, have the advantages that：
The present invention solve hydrogen fluoride condensation and containing dichlorodifluoromethan 142, it is cold along dichloroethylene, the synthetic product of anti-dichloroethylene
It is solidifying, and detach gas under the conditions of 0~-50 DEG C of (preferably -20~-30 DEG C), 0.1~1.1MPa of pressure (preferably 0.6~0.9MPa)
The hydrogen chloride of phase and low boiling halogenated hydrocarbons.Two layers of liquid phase point：Upper strata is remaining HF, is synthesized available for lower batch dichlorodifluoromethan 142, under
Layer is dichlorodifluoromethan 142, along dichloroethylene and anti-dichloroethylene mixture.Rectificating method may separate out purpose product dichlorodifluoromethan 142,
And it is synthesized along dichloroethylene and anti-dichloroethylene available for lower batch dichlorodifluoromethan 142.Chromium magnesium fluoride catalysts are according to Russia's patent
Prepared by 2005539 environment-protective process of RU, loose porous, active component magnesium fluoride is made and carries the equally distributed structure of charomic fluoride.It is this
Structure can ensure the high activity of catalyst during halogenated hydrocarbon system product gas phase fluorination, although active component fluorination chromium content is very
It is low, but it and magnesium fluoride are relatively rare and expensive compounds.Catalyst is used by squeezing to be in granular form in reactor,
Catalyst is dry under the conditions of 100~200 DEG C before the synthesis, is activated (processing) with hydrogen fluoride at 200~350 DEG C.In addition, it urges
Agent activity will be regenerated when reducing, and the activity of this rear catalyst can be restored.
Specific embodiment
The preparation method of 1,1- of the present invention, bis- fluoro- 2- chloroethanes, includes the following steps：
1) the chromium magnesium fluoride catalysts containing 10~15% charomic fluorides (trivalent) and 85~90% magnesium fluorides are added first
Enter reactor to be reacted, and pass through blender and be stirred, chromium magnesium fluoride catalysts be graininess, active component Cr3+,
Wherein active component accounts for 10%~15% in chromium magnesium fluoride catalysts, it is preferred that chromium magnesium is fluorinated
The carrier of object catalyst is MgF2, with blower pump with the speed of 6~10 marks l/h by nitrogen purge 2~5 hours,
Then temperature is controlled by evaporator and carries out predrying at 100~200 DEG C, and hydrogen fluoride is supplied by evaporator, hydrogen fluoride
Feed speed is 100~200g/h, and activation continues 4~8 hours, then by the chromium magnesium fluoride catalysts after predrying 200
Activation process is carried out with hydrogen fluoride at a temperature of~350 DEG C, the temperature of evaporator is set in 150 at the end of processing to be activated~
350 DEG C, electric heater is mounted on evaporator and reactor, convenient for the temperature in control evaporator and reactor so that steam
Hair device and the reactor temperature in each stage in preparation process meets the needs of reaction process, be equipped on reactor pressure gauge and
Regulating valve, pressure gauge and regulating valve are used to keep the necessary pressure of reaction system, it is ensured that reaction is smoothed out；
2) the chromium magnesium fluoride catalysts after above-mentioned perfluorinated hydrogen activation process are added in into the fixed bed with catalyst layer
Reactor, then by 1,1,2- trichloroethanes (its physical property is as shown in table 1) or along 1,2-dichloroethene, bis- chloroethenes of anti-1,2-
Alkene and 1, the mixture of 1,2- trichloroethanes are 150~350 DEG C in reaction temperature, reaction pressure (absolute pressure) for 0.1~
1.1MPa, time of contact are 15~150 seconds, HF and material molar ratio containing chlorine=2~40:Under conditions of 1, it is passed through fixed bed reaction
Device carries out gas phase catalytic fluorination reaction, and is passed through hydrogen fluoride and three chloroethenes into fixed bed reactors by evaporator in synthesis
Alkane or dichloroethylene, while adjust the reaction pressure in fixed bed reactors, it is preferred that reaction temperature is 220~280 DEG C, instead
Pressure is answered as 0.6~0.9MPa, time of contact is 20~50 seconds, HF and material molar ratio containing chlorine=4~10:1；
3) sintetics after the reaction of above-mentioned gas phase catalytic fluorination then is passed through condenser to condense, preferably
, condenser is recoverable condenser, can improve the condensing rate of the sintetics after gas phase catalytic fluorination reacts, and is saved
Preparation time is equipped with refrigerant chuck on condenser, reduces the temperature in condenser, and condensed synthetic is layered again,
Upper strata is hydrogen fluoride after making separation, and lower floor is containing dichlorodifluoromethan 142, along the gas of dichloroethylene, anti-dichloroethylene and trichloroethanes
State synthetic product, the condensed device outlet of gaseous state synthetic product release, and continue to be passed through hydrogen fluoride and trichloroethanes or dichloroethylene；
4) after the completion of hydrogen and trichloroethanes to be fluorinated supply, the liquid phase synthesis product of layered method liquid phase separation is from collector
Bottom releases, and the hydrogen fluoride of separation uses for lower batch, and the liquid phase synthesis product of bottom is organic mixture, and molten with alkalinity
Liquid neutralizes organic mixture, then is dried with zeolite NaA, finally by bis- fluoro- 2- chloroethanes of obtained 1,1- after rectifying, essence
Suitable dichloroethylene and anti-dichloroethylene of the fraction from after are used for the synthesis of lower batch dichlorodifluoromethan 142.
Neutralize, dry purpose is separation dichlorodifluoromethan 142 and containing along 1,2- dichloroethylene, anti-1,2- dichloroethylene and 1,
The mixture of 1,2- trichloroethanes, the raw material which can synthesize as dichlorodifluoromethan 142, rectificating method can isolate mesh
Product dichlorodifluoromethan 142, and can be used for the synthesis of lower batch dichlorodifluoromethan 142 along dichloroethylene and anti-dichloroethylene, at the same
Hydrogen fluoride is reused in synthesis hydrogen fluoride to be made to reach high conversion.
The physical property of 1 1,1,2- trichloroethanes of table
Specific embodiment is as follows：
Embodiment 1
Laboratory's synthesizer of dichlorodifluoromethan 142 is made of evaporator, nickel reactant device, condenser, collector, and evaporator supplies
To liquid phase HF and trichloroethanes or dichloroethylene, reactor volume V=1L band fixed catalytic oxidant layer, condenser is recoverable condensation
Device, collector are used to collect synthetic product and HF.Evaporator and reactor are equipped with electric heater, condenser installation refrigerant folder
Set, condensator outlet release gaseous state synthetic product (HCl, gently boiling fluorochlorohydrocarbon), are equipped with pressure gauge and regulating valve for keeping anti-
Answer the necessary pressure of system.
Reactor adds in 860g and presses chromium Mg catalyst prepared by Russia patent RU 2005539, with the nitrogen of 6~10 marks l/h
Catalyst is dried in 4 hours water removal in gas purge, and evaporator temperature is set in 100 DEG C, and reactor temperature is gradual
200 DEG C are risen to from 100 DEG C.
Temperature gradually rises to 350 DEG C of progress activation of catalyst from 200 DEG C under normal pressure in reactor, supplies hydrogen fluoride speed
100~200g/h, activation continue 5 hours.Evaporator temperature is set in 250 DEG C at the end of activation flow, reactor temperature
It is 240~250 DEG C, system pressure 0.9MPa, reversed -30 DEG C of condenser temperature.
290~300g/h of hydrogen fluoride feed speed during synthesis, trichloroethanes 350~360g/h of feed speed, in reactor
0.75~0.9MPa of pressure.Sintetics is passed through reversed condenser after reaction, is layered herein：Upper strata HF, the main fluorine-containing chlorine of lower floor
Alkane 142, suitable dichloroethylene, anti-dichloroethylene, trichloroethanes.Condenser exhaust gas contains hydrogen chloride and light boiling product.
Liquid phase synthesis product is released from collector bottom after the completion of HF and trichloroethanes supply.Bottom liquid-phase product is organic
Mixture (dichlorodifluoromethan 142, dichloroethylene etc.) is neutralized with KOH aqueous solutions (5% mass), is dried with zeolite NaA, then carried out
Gas chromatographic analysis.Upper phase product is the reusable synthesis dichlorodifluoromethan 142 of hydrogen fluoride.HF：142 molar ratio of dichlorodifluoromethan
=5.5:1,42~47 seconds times of contact, trichloroethanes conversion ratio 98%, 142 selectivity 49% of generation dichlorodifluoromethan.
Embodiment 2
Laboratory's synthesizer of dichlorodifluoromethan 142 is made of evaporator, nickel reactant device, condenser, collector, and evaporator supplies
To liquid phase HF and trichloroethanes or dichloroethylene, reactor volume V=1L band fixed catalytic oxidant layer, condenser is recoverable condensation
Device, collector are used to collect synthetic product and HF.Evaporator and reactor are equipped with electric heater, condenser installation refrigerant folder
Set, condensator outlet release gaseous state synthetic product (HCl, gently boiling fluorochlorohydrocarbon), are equipped with pressure gauge and regulating valve for keeping anti-
Answer the necessary pressure of system.
Reactor adds in 860g and presses chromium Mg catalyst prepared by Russia patent RU 2005539, with the nitrogen of 6~10 marks l/h
Catalyst is dried in 4 hours water removal in gas purge, and evaporator temperature is set in 100 DEG C, and reactor temperature is gradual
200 DEG C are risen to from 100 DEG C.
Temperature gradually rises to 350 DEG C of progress activation of catalyst from 200 DEG C under normal pressure in reactor, supplies hydrogen fluoride speed
100~200g/h, activation continue 5 hours.Evaporator temperature is set in 150 DEG C at the end of activation flow, reactor temperature
It is 240~250 DEG C, system pressure 0.87MPa, reversed -30 DEG C of condenser temperature.
Hydrogen fluoride feed speed 610g/h during synthesis, dichloroethylene feed speed 420g/h, reactor pressure 0.75~
0.9MPa.Sintetics is passed through reversed condenser after reaction, is layered herein：Upper strata HF, lower floor is mainly containing dichlorodifluoromethan 142, along two
Vinyl chloride, anti-dichloroethylene, trichloroethanes.Condenser exhaust gas contains hydrogen chloride and light boiling product.
Using HF and dichloroethylene synthesis dichlorodifluoromethan 142, dichloroethylene is a kind of from 1 synthetic product of embodiment separation fluorine chlorine
Mixture after alkane 142, forms the suitable dichloroethylene for 80%, 3% anti-dichloroethylene, 6% dichlorodifluoromethan 141, and the three of 9%
Chloroethanes.Liquid phase synthesis product is released from collector bottom after the completion of HF and trichloroethanes supply.Bottom liquid-phase product is organic
Mixture (dichlorodifluoromethan 142, dichloroethylene etc.) is neutralized with KOH aqueous solutions (5% mass), is dried with zeolite NaA, then carried out
Gas chromatographic analysis.HF and dichloroethylene molar ratio=7.1:1,21 seconds times of contact, anti-dichloroethylene conversion ratio 41.5% is raw
Into the selectivity 85% of dichlorodifluoromethan 142.
The relationship of each response parameter and 142 selectivity of dichlorodifluoromethan is as shown in table 2 in embodiment 1 and embodiment 2
The relationship of 2 each response parameter of table and 142 selectivity of dichlorodifluoromethan
It these are only specific embodiments of the present invention, but the technical characteristic of the present invention is not limited thereto.It is any with this hair
Based on bright, to realize essentially identical technique effect, made ground simple change, equivalent replacement or modification etc., all cover
Among protection scope of the present invention.
Claims (5)
- The preparation method of 1.1,1- bis- fluoro- 2- chloroethanes, it is characterised in that include the following steps：1) it will be added in reactor containing the chromium magnesium fluoride catalysts of 10~15% charomic fluorides and 85~90% magnesium fluorides first It is reacted, the carrier of the chromium magnesium fluoride catalysts is MgF2, and pass through blender and be stirred, the chromium magnesium fluoride Catalyst is graininess, active component Cr3+, wherein the weight that the active component is shared in the chromium magnesium fluoride catalysts It is 10%~15% to measure percentage, and it is small with the speed of 6~10 marks l/h nitrogen to be purged the reactor 2~5 with blower pump When, then temperature is controlled by evaporator and predrying is carried out at 100~200 DEG C, and hydrogen fluoride, institute are supplied by the evaporator The feed speed for stating hydrogen fluoride is 100~200g/h, and activation continues 4~8 hours, is then fluorinated the chromium magnesium after predrying Object catalyst carries out activation process at a temperature of 200~350 DEG C with the hydrogen fluoride, by the evaporation at the end of processing to be activated The temperature of device is set in 150~350 DEG C；2) the chromium magnesium fluoride catalysts after above-mentioned perfluorinated hydrogen activation process are added in into the fixed bed with catalyst layer Reactor, then by 1,1,2- trichloroethanes or along 1,2-dichloroethene, anti-1,2-dichloroethene and 1,1,2- trichloroethanes Mixture, reaction temperature be 150~350 DEG C, reaction pressure be 0.1~1.1MPa, time of contact be 15~150 seconds, HF with Material molar ratio containing chlorine=2~40:Under conditions of 1, it is passed through the fixed bed reactors and carries out gas phase catalytic fluorination reaction, and Be passed through during synthesis into the fixed bed reactors by the evaporator hydrogen fluoride and the 1,1,2- trichloroethanes or The suitable 1,2-dichloroethene, the anti-1,2-dichloroethene, while adjust the reaction pressure in the fixed bed reactors；3) sintetics after the reaction of above-mentioned gas phase catalytic fluorination then is passed through condenser to condense, the condenser For recoverable condenser, condensed synthetic is layered again, and upper strata is hydrogen fluoride after making separation, and 1,1- bis- is is contained in lower floor Fluoro- 2- chloroethanes, suitable 1,2-dichloroethene, anti-1,2-dichloroethene and 1, the gaseous state synthetic product of 1,2- trichloroethanes are described Gaseous state synthetic product is released through the condensator outlet, and continues to be passed through the hydrogen fluoride and 1,1, the 2- trichloroethanes or institute It states along 1,2- dichloroethylene, the anti-1,2- dichloroethylene；4) hydrogen fluoride and the 1,1,2- trichloroethanes or the suitable 1,2- dichloroethylene, the anti-1,2- dichloroethylene are treated After the completion of supply, the liquid phase synthesis product of layered method liquid phase separation is released from collector bottom, and the hydrogen fluoride of separation is used for down Batch uses, and the liquid phase synthesis product of bottom is organic mixture, and the organic mixture is carried out with alkaline solution It neutralizes, then is dried with zeolite NaA, 1,1-, bis- fluoro- 2- chloroethanes is made finally by rectifying, it is described along 1,2- after rectifying separation Dichloroethylene and the anti-1,2- dichloroethylene are used for the synthesis of lower bis- fluoro- 2- chloroethanes of batch 1,1-.
- 2. the preparation method of 1,1-, bis- fluoro- 2- chloroethanes according to claim 1, it is characterised in that：Institute in step 2) It is 220~280 DEG C to state reaction temperature, and the reaction pressure is 0.6~0.9MPa, and the time of contact is 20~50 seconds, described HF and the material molar ratio containing chlorine=4~10:1.
- 3. the preparation method of 1,1-, bis- fluoro- 2- chloroethanes according to claim 1, it is characterised in that：On the condenser Refrigerant chuck is installed.
- 4. the preparation method of 1,1-, bis- fluoro- 2- chloroethanes according to claim 1, it is characterised in that：The evaporator and Electric heater is mounted on the reactor.
- 5. the preparation method of 1,1-, bis- fluoro- 2- chloroethanes according to claim 4, it is characterised in that：On the reactor Pressure gauge and regulating valve are installed.
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| FR3056586B1 (en) * | 2016-09-27 | 2020-05-08 | Arkema France | COMPOSITION COMPRISING 1-CHLORO-2,2-DIFLUOROETHANE |
| CN114853563A (en) * | 2022-06-27 | 2022-08-05 | 山东华安新材料有限公司 | Preparation method of 2-chloro-1,1-difluoroethane |
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