CN104692998A - Preparation method of 1,1-difluoro-2-chloroethane - Google Patents
Preparation method of 1,1-difluoro-2-chloroethane Download PDFInfo
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- CN104692998A CN104692998A CN201510072012.XA CN201510072012A CN104692998A CN 104692998 A CN104692998 A CN 104692998A CN 201510072012 A CN201510072012 A CN 201510072012A CN 104692998 A CN104692998 A CN 104692998A
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Abstract
The invention discloses a preparation method of 1,1-difluoro-2-chloroethane. The method comprises the following steps: contacting 1,1,2-trichloroethane or a mixture of cis-1,2-dichloroethylene or trans-1,2-dichloroethylene and 1,1,2-trichloroethane at 150-350 DEG C under 0.1-1.1MPa (absolute pressure) for 15-150s; adding a chromium-magnesium fluoride catalyst under a condition that the mole ratio of HF to a chlorine-containing raw material is (2-40) to 1, carrying out gas phase catalysis fluoridation by virtue of a fixed-bed reactor, collecting a product, and condensing, liquid-phase layering, neutralizing, drying and rectifying so as to obtain high-purity 1,1-difluoro-2-chloroethane. The preparation process disclosed by the invention is simple, low in cost and good in yield; and the preparation method is good in industrial application prospect, and is especially suitable for industrial production on a large scale.
Description
Technical field
The present invention relates to the preparation method of the fluoro-2-monochloroethane of 1,1-bis-, belong to organic synthesis field.
Background technology
The fluoro-2-monochloroethane of 1.1-bis-(freon 142) is preparation 2, the intermediate product of 2-difluoroethanol, current various countries are considering to use freon 142 to substitute freon 113,141b, 140a etc., clean for solid surface, the aerosol of dry, degreasing and whipping agent field, R142 has good market outlook.This product preparation method patent has been reported abroad, but data is few, domesticly reports without similar patent.The method of producing the fluoro-2-monochloroethane of 1.1-bis-is gas phase catalytic fluorination, and its synthetic route can be divided into following two kinds according to the difference of starting raw material, and reaction formula is as follows:
Article 1, synthetic route:
Article 2 synthetic route:
Catalyzer is influence factor most crucial in synthesis 1.1-bis-fluoro-2-monochloroethane process, and between different synthetic method, topmost difference is the difference of selected catalyst type.
If freon 142 preparation method in known patent (EP 1008575, C07C 17/20,14.06.2000) is trichloroethane and hydrogen fluoride gas-phase reaction under catalysts conditions, then from reactant, be separated freon 142.The Cr of fluoridation that what catalyzer was selected be through
2o
3.Except Cr
2o
3outward, catalyzer can contain or not contain one or more metal pentafluoride salt carriers: as chromium, iron, niobium, nickel, antimony, tin, tantalum, titanium etc.Reaction conditions is as follows: temperature 100 DEG C ~ 380 DEG C, pressure 0.1MPa (0psig) ~ 2.86MPa (400psig), HF and 140 to 2 ~ 20,1 ~ 100 second duration of contact.
Byproduct hydrogen chloride (HCl) is by distilling or absorption extraction in water or alkali lye.Unreacted HF, by distilling or absorption extraction in water or alkali lye, adopts and is separated or semi-permeable membranes separation.Other organic by-products can pass through fractionation by distillation.Unsaturated organic by-products can be reacted by product and chlorine or bromine and be processed before fractionation by distillation.
In embodiment, catalyst chromium oxide compound (Cr
2o
3) (20 с м
3, 27g) and activation temperature 380 DEG C, at HF (6.6g/h) and air (100cm
3/ point) purge 18 hours under gas mixture condition.Trichloroethane and hydrogen fluoride gas phase gas mixture is passed at reactor, temperature 220 DEG C, mol ratio=7.8:1 (10.1g/h HF and 0.1 с м of hydrogen fluoride and trichloroethane when freon 142 synthesizes
3/ point trichloroethane), pressure 1.13MPa (150psig), 34 seconds duration of contact, the selectivity generating freon 142 is 70.2%.
And for example known patent (EP 1008574, C07C 17/10,07.12.1999), with 1,2-Ethylene Dichloride is raw material fluorinatedly prepare freon 142, is Ethylene Dichloride and HF gas-phase reaction under catalysts conditions, and then from reactant, is separated freon 142.This invention catalyzer, synthesis and freon 142 separation condition are similar to EP 1008575.Ethylene Dichloride and HF are carried out in an embodiment at chromated oxide (Cr
2o
3) react in catalyzer, pass into Ethylene Dichloride and HF gas phase gas mixture to reactor, temperature 220 DEG C, mol ratio=6.5:1 (10.1g/h HF and 0.1 с м of hydrogen fluoride and Ethylene Dichloride
3/ point Ethylene Dichloride), pressure 1.13MPa (150psig), 34 seconds duration of contact, Ethylene Dichloride transformation efficiency 88.3%, the selectivity generating freon 142 is 84.2%.
Although the transformation efficiency of freon 142 prepared by trichloroethane (Ethylene Dichloride) and selectivity is higher, unfortunately catalyzer is Powdered, instead of particle, is not well suited for industrialization catalyticreactor.It is larger that catalyst preparing system with carrier in embodiment and reality prepare result difference.
What freon 142 prepared that patent (WO 2013/053800, B01J 23/06,18.04.2013) illustrates is HF and trichloroethane and/or Ethylene Dichloride carry out gas-phase reaction under catalysts conditions, and method for preparing catalyst is the FeCl using chromium aluminium base
3and MgCl
2co-precipitated catalyst, or the Cr (NO of activated carbon substrates
3)
3with Ni (NO
3)
2co-precipitated catalyst, or aluminum oxide and ZnCl
2co-precipitated catalyst.Freon 142 preparation flow temperature 200 ~ 350 DEG C, atmospheric pressure or under pressure is to 2.5MPa (25 bar), mol ratio=2 ~ the 30:1 of hydrogen fluoride and trichloroethane and/or Ethylene Dichloride, 10 ~ 200 seconds duration of contact, the outward appearances such as the sheet that catalyzer can use aforesaid method to prepare or particle.
Synthesize front ready catalyzer 120 ~ 140 DEG C of nitrogen treatment 1 ~ 50 hour, 10 ~ 40 seconds duration of contact.And then process under 150 ~ 400 DEG C of conditions by HF or HF and nitrogen or air Mixture, finally with HF, activation is carried out 20 ~ 30 hours to catalyzer at 375 DEG C.
In embodiment, freon 142 synthesizes and carries out in above-mentioned catalyzer, and the catalyzer of use is Cr
2o
3/ Al
2o
3/ FeCl
3/ MgCl
2, synthesis temperature 220 ~ 240 DEG C, pressure 0.5MPa (5 bar), HF and trichloroethane mol ratio=6.5:1,90 seconds duration of contact, the transformation efficiency 90 ~ 98% of trichloroethane, generate the selectivity 22 ~ 34% of freon 142, and the selectivity generating Ethylene Dichloride is 45 ~ 54%.
Use Al
2o
3/ ZnCl
2the temperature of catalyzer synthesis freon 142 is 220 ~ 240 DEG C, pressure 0.5MPa (5 bar), HF and trichloroethane mol ratio=7.3 ~ 8.7:1,127 ~ 142 seconds duration of contact, the transformation efficiency 92 ~ 97% of trichloroethane, generate the selectivity 26 ~ 35% of freon 142, and the selectivity generating Ethylene Dichloride is 48 ~ 61%.
At use carried by active carbon Cr (NO
3)
3with Ni (NO
3)
2during catalyzer, freon 142 synthesis temperature 230 ~ 240 DEG C, pressure 0.5MPa (5 bar), HF and trichloroethane mol ratio=7.9 ~ 8.9:1,94 ~ 135 seconds duration of contact, the transformation efficiency 94 ~ 99% of trichloroethane, generate the selectivity 65% of freon 142, and the selectivity generating Ethylene Dichloride is 28%.The temperature that HF and Ethylene Dichloride synthesize freon 142 under this catalysts conditions is 240 DEG C, pressure 0.5MPa, HF and trichloroethane mol ratio=1:5.6 ~ 7.2,130 ~ 139 seconds duration of contact, the transformation efficiency 60.6 ~ 63.8% of Ethylene Dichloride.
Use Cr
2o
3/ Al
2o
3/ FeCl
3/ MgCl
2and Al
2o
3/ ZnCl
2the not foot point of catalyzer is and use carried by active carbon Cr (NO
3)
3with Ni (NO
3)
2it is lower that the selectivity generating freon 142 compared by catalyzer, Cr
2o
3/ Al
2o
3/ FeCl
3/ MgCl
2catalyzer contains Cr
2o
3about 40%, which increase the cost of catalyzer, too increase the manufacturing cost of freon 142 equally.
In addition, carried by active carbon Cr (NO
3)
3with Ni (NO
3)
2cannot supporting reactions under the condition that catalyzer reduces in activity.It is known that catalyst surface reduces activity due to generation carbon black or lipid aggregate thing in continuous process, these materials are all feed material degradation products or synthetics.The regeneration of decaying catalyst is exactly allow catalyzer process in high temperature air or oxygen, ensures that the carbon black of catalyst surface or lipid aggregate thing can burn to the greatest extent.Therefore, it is impossible for carrying out manipulation of regeneration to the charcoal supported catalysts of WO 2013/053800 Patent design, and this incites somebody to action reduction of service life greatly, and this is also a real not foot point.
Embodiment
The preparation method of the fluoro-2-monochloroethane of the present invention 1,1-bis-, comprises the steps:
1) first the chromium magnesium fluoride catalysts containing 10 ~ 15% chromium fluorides (trivalent) and 85 ~ 90% magnesium fluorides is added reactor to react, and stirred by agitator, chromium magnesium fluoride catalysts is particulate state, and active ingredient is Cr
3+, wherein active ingredient accounts for 10% ~ 15% in chromium magnesium fluoride catalysts, and preferably, the carrier of chromium magnesium fluoride catalysts is MgF
2, by blower pump with the speed of 6 ~ 10 marks l/h by nitrogen purging reactor 2 ~ 5 hours, then by vaporizer, temperature is controlled to carry out predrying at 100 ~ 200 DEG C, and supply hydrogen fluoride by vaporizer, hydrofluoric feed speed is 100 ~ 200g/h, activation continues 4 ~ 8 hours, then the chromium magnesium fluoride catalysts after predrying is carried out activation treatment with hydrogen fluoride at 200 ~ 350 DEG C of temperature, at the end of process to be activated, the temperature of vaporizer is set in 150 ~ 350 DEG C, vaporizer and reactor are all provided with electric heater, be convenient to control the temperature in vaporizer and reactor, the temperature in each stage meets the needs of reaction process to make vaporizer and reactor in preparation process, reactor is provided with tensimeter and variable valve, tensimeter and variable valve are for keeping the pressure of reaction system necessity, guarantee that reaction is carried out smoothly,
2) above-mentioned chromium magnesium fluoride catalysts after hydrogen fluoride activation treatment is added the fixed-bed reactor with catalyst layer, then by 1, 1, 2-trichloroethane (its physical properties is as shown in table 1) or suitable 1, 2-Ethylene Dichloride, anti-1, 2-Ethylene Dichloride and 1, 1, the mixture of 2-trichloroethane, it is 150 ~ 350 DEG C in temperature of reaction, reaction pressure (absolute pressure) is 0.1 ~ 1.1MPa, duration of contact is 15 ~ 150 seconds, under the condition of HF and chloride material molar ratio=2 ~ 40:1, pass into fixed-bed reactor and carry out gas phase catalytic fluorination reaction, and in fixed-bed reactor, pass into hydrogen fluoride and trichloroethane or Ethylene Dichloride when synthesizing by vaporizer, regulate the reaction pressure in fixed-bed reactor simultaneously, preferably, temperature of reaction is 220 ~ 280 DEG C, reaction pressure is 0.6 ~ 0.9MPa, duration of contact is 20 ~ 50 seconds, HF and chloride material molar ratio=4 ~ 10:1,
3) then will pass into condenser through the reacted sintetics of above-mentioned gas phase catalytic fluorination and carry out condensation, preferably, condenser is recoverable condenser, the condensing rate through the reacted sintetics of gas phase catalytic fluorination can be improved, save preparation time, condenser is provided with refrigerant chuck, reduce the temperature in condenser, condensed synthetics carries out layering again, after making separation, upper strata is hydrogen fluoride, lower floor is for containing freon 142, along Ethylene Dichloride, the gaseous state synthetic product of anti-Ethylene Dichloride and trichloroethane, gaseous state synthetic product is released through condensator outlet, and continue to pass into hydrogen fluoride and trichloroethane or Ethylene Dichloride,
4) after hydrogen to be fluorinated and trichloroethane have supplied, liquid phase synthesis product through top and bottom process liquid phase separation is released bottom collector, the hydrogen fluoride be separated is used for lower batch of use, the liquid phase synthesis product of bottom is organic mixture, and with basic solution, organic mixture is neutralized, then use zeolite NaA dry, obtain 1 finally by after rectifying, the fluoro-2-monochloroethane of 1-bis-, the suitable Ethylene Dichloride after rectifying separation and anti-Ethylene Dichloride are used for the synthesis of lower batch of freon 142.
Neutralization, dry object are separated freon 142 and contain along 1,2-Ethylene Dichloride, anti-1,2-Ethylene Dichloride and 1,1, the mixture of 2-trichloroethane, the raw material that this mixture can synthesize as freon 142, rectificating method can isolate object product freon 142, and the synthesis of lower batch of freon 142 is may be used for along Ethylene Dichloride and anti-Ethylene Dichloride, in synthesis, reuse hydrogen fluoride simultaneously and hydrogen fluoride can be made to reach high conversion.
The physical properties of table 1 vinyl trichloride
Embodiment is as follows:
Embodiment 1
Testing laboratory's synthesizer of freon 142 is made up of vaporizer, nickel reactant device, condenser, collector, vaporizer supply liquid phase HF and trichloroethane or Ethylene Dichloride, reactor volume V=1L is with fixed catalytic oxidant layer, condenser is recoverable condenser, and collector is for collecting synthetic product and HF.Vaporizer and reactor are provided with electric heater, and refrigerant chuck installed by condenser, and condensator outlet releases gaseous state synthetic product (HCl, gently boil fluorochlorohydrocarbon), are provided with tensimeter and variable valve for keeping the pressure of reaction system necessity.
Reactor adds the chromium Mg catalyst that 860g is prepared by Russia patent RU 2005539, drying was carried out to catalyzer in 4 hours dewater with the nitrogen purging reactor of 6 ~ 10 marks l/h, evaporator temperature is set in 100 DEG C, and reactor temperature rises to 200 DEG C from 100 DEG C gradually.
In reactor, under normal pressure, temperature rises to 350 DEG C from 200 DEG C gradually and carries out catalyst activation, and supply hydrogen fluoride speed 100 ~ 200g/h, activation continues 5 hours.At the end of activation flow process, evaporator temperature is set in 250 DEG C, reactor temperature is 240 ~ 250 DEG C, system pressure 0.9MPa, reverse condenser temperature-30 DEG C.
Hydrogen fluoride feed speed 290 ~ 300g/h during synthesis, trichloroethane feed speed 350 ~ 360g/h, reactor pressure 0.75 ~ 0.9MPa.After reaction, sintetics passes into reverse condenser, in this layering: upper strata HF, and lower floor is mainly containing freon 142, suitable Ethylene Dichloride, anti-Ethylene Dichloride, trichloroethane.Condenser exhaust gas contains hydrogenchloride and the product that gently boils.
HF and trichloroethane have supplied rear liquid phase synthesis product and have released bottom collector.Bottom liquid-phase product is organic mixture (freon 142, Ethylene Dichloride etc.), with the KOH aqueous solution (5% quality) neutralization, dry with zeolite NaA, then carries out gas chromatographic analysis.Upper phase product is the reusable synthesis freon 142 of hydrogen fluoride.HF: freon 142 mol ratios=5.5:1,42 ~ 47 seconds duration of contact, trichloroethane transformation efficiency 98%, generates freon 142 selectivity 49%.
Embodiment 2
Testing laboratory's synthesizer of freon 142 is made up of vaporizer, nickel reactant device, condenser, collector, vaporizer supply liquid phase HF and trichloroethane or Ethylene Dichloride, reactor volume V=1L is with fixed catalytic oxidant layer, condenser is recoverable condenser, and collector is for collecting synthetic product and HF.Vaporizer and reactor are provided with electric heater, and refrigerant chuck installed by condenser, and condensator outlet releases gaseous state synthetic product (HCl, gently boil fluorochlorohydrocarbon), are provided with tensimeter and variable valve for keeping the pressure of reaction system necessity.
Reactor adds the chromium Mg catalyst that 860g is prepared by Russia patent RU 2005539, drying was carried out to catalyzer in 4 hours dewater with the nitrogen purging reactor of 6 ~ 10 marks l/h, evaporator temperature is set in 100 DEG C, and reactor temperature rises to 200 DEG C from 100 DEG C gradually.
In reactor, under normal pressure, temperature rises to 350 DEG C from 200 DEG C gradually and carries out catalyst activation, and supply hydrogen fluoride speed 100 ~ 200g/h, activation continues 5 hours.At the end of activation flow process, evaporator temperature is set in 150 DEG C, reactor temperature is 240 ~ 250 DEG C, system pressure 0.87MPa, reverse condenser temperature-30 DEG C.
Hydrogen fluoride feed speed 610g/h during synthesis, Ethylene Dichloride feed speed 420g/h, reactor pressure 0.75 ~ 0.9MPa.After reaction, sintetics passes into reverse condenser, in this layering: upper strata HF, and lower floor is mainly containing freon 142, suitable Ethylene Dichloride, anti-Ethylene Dichloride, trichloroethane.Condenser exhaust gas contains hydrogenchloride and the product that gently boils.
Use HF and Ethylene Dichloride synthesis freon 142, Ethylene Dichloride is a kind ofly separated the mixture after freon 142 from embodiment 1 synthetic product, consists of the suitable Ethylene Dichloride of 80%, the anti-Ethylene Dichloride of 3%, the trichloroethane of the freon 141,9% of 6%.HF and trichloroethane have supplied rear liquid phase synthesis product and have released bottom collector.Bottom liquid-phase product is organic mixture (freon 142, Ethylene Dichloride etc.), with the KOH aqueous solution (5% quality) neutralization, dry with zeolite NaA, then carries out gas chromatographic analysis.HF and Ethylene Dichloride mol ratio=7.1:1,21 seconds duration of contact, anti-Ethylene Dichloride transformation efficiency 41.5%, generates the selectivity 85% of freon 142.
In embodiment 1 and embodiment 2, optionally relation is as shown in table 2 for each reaction parameter and freon 142
The each reaction parameter of table 2 and freon 142 optionally relation
These are only specific embodiments of the invention, but technical characteristic of the present invention is not limited thereto.Any based on the present invention, for realizing substantially identical technique effect, done ground simple change, equivalent replacement or modification etc., be all covered by among protection scope of the present invention.
Summary of the invention
The present invention is directed to the deficiencies in the prior art part, there is provided 1, the preparation method of the fluoro-2-monochloroethane of 1-bis-, particularly a kind of chromium magnesium fluoride catalysts is applied to preparation 1, the fluoro-2-monochloroethane of 1-bis-, the method technique is simple, cost is low, yield is high, has good prospects for commercial application, is particularly suitable for large-scale industrial production.
In order to solve the problems of the technologies described above, the present invention adopts following technical scheme:
The preparation method of the fluoro-2-monochloroethane of 1,1-bis-, is characterized in that comprising the steps:
1) first the chromium magnesium fluoride catalysts containing 10 ~ 15% chromium fluorides (trivalent) and 85 ~ 90% magnesium fluorides is added in reactor and react, and stir with agitator, by blower pump with the speed of 6 ~ 10 marks l/h by nitrogen purging reactor 2 ~ 5 hours, then by vaporizer, temperature is controlled to carry out predrying at 100 ~ 200 DEG C, and supply hydrogen fluoride by vaporizer, hydrofluoric feed speed is 100 ~ 200g/h, activation continues 4 ~ 8 hours, then the chromium magnesium fluoride catalysts after predrying is carried out activation treatment with hydrogen fluoride at 200 ~ 350 DEG C of temperature, at the end of process to be activated, the temperature of vaporizer is set in 150 ~ 350 DEG C,
2) above-mentioned chromium magnesium fluoride catalysts after hydrogen fluoride activation treatment is added the fixed-bed reactor with catalyst layer, then by 1, 1, 2-trichloroethane or suitable 1, 2-Ethylene Dichloride, anti-1, 2-Ethylene Dichloride and 1, 1, the mixture of 2-trichloroethane, it is 150 ~ 350 DEG C in temperature of reaction, reaction pressure (absolute pressure) is 0.1 ~ 1.1MPa, duration of contact is 15 ~ 150 seconds, under the condition of HF and chloride material molar ratio=2 ~ 40:1, pass into fixed-bed reactor and carry out gas phase catalytic fluorination reaction, and listen evaporator in fixed-bed reactor, pass into hydrogen fluoride and trichloroethane or Ethylene Dichloride when synthesizing, regulate the reaction pressure in fixed-bed reactor simultaneously,
3) then will pass into condenser through the reacted sintetics of above-mentioned gas phase catalytic fluorination and carry out condensation, condensed synthetics carries out layering again, after making separation, upper strata is hydrogen fluoride, lower floor is the gaseous state synthetic product containing freon 142, suitable Ethylene Dichloride, anti-Ethylene Dichloride and trichloroethane, gaseous state synthetic product is released through condensator outlet, and continues to pass into hydrogen fluoride and trichloroethane or Ethylene Dichloride;
4) after hydrogen to be fluorinated and trichloroethane have supplied, liquid phase synthesis product through top and bottom process liquid phase separation is released bottom collector, the hydrogen fluoride be separated is used for lower batch of use, the liquid phase synthesis product of bottom is organic mixture, and with basic solution, organic mixture is neutralized, then use zeolite NaA dry, obtain 1 finally by after rectifying, the fluoro-2-monochloroethane of 1-bis-, the suitable Ethylene Dichloride after rectifying separation and anti-Ethylene Dichloride are used for the synthesis of lower batch of freon 142.
Neutralization, dry object are separated freon 142 and contain along 1,2-Ethylene Dichloride, anti-1,2-Ethylene Dichloride and 1,1, the mixture of 2-trichloroethane, the raw material that this mixture can synthesize as freon 142, rectificating method can isolate object product freon 142, and the synthesis of lower batch of freon 142 is may be used for along Ethylene Dichloride and anti-Ethylene Dichloride, in synthesis, reuse hydrogen fluoride simultaneously and hydrogen fluoride can be made to reach high conversion.
Further, step 1) in chromium magnesium fluoride catalysts be particulate state, active ingredient is Cr
3+, wherein active ingredient accounts for 10% ~ 15% in chromium magnesium fluoride catalysts.
Preferably, the carrier of chromium magnesium fluoride catalysts is MgF
2.
Preferably, step 2) in temperature of reaction be 220 ~ 280 DEG C, reaction pressure is 0.6 ~ 0.9MPa, and duration of contact is 20 ~ 50 seconds, HF and chloride material molar ratio=4 ~ 10:1.
Preferably, step 3) in condenser be recoverable condenser, the condensing rate through the reacted sintetics of gas phase catalytic fluorination can be improved, save preparation time.
Further, condenser is provided with refrigerant chuck, reduces the temperature in condenser.
Further, vaporizer and reactor are all provided with electric heater, are convenient to control the temperature in vaporizer and reactor, the temperature in each stage meets the needs of reaction process to make vaporizer and reactor in preparation process.
Further, reactor is provided with tensimeter and variable valve, tensimeter and variable valve, for keeping the pressure of reaction system necessity, guarantee that reaction is carried out smoothly.
The present invention, owing to have employed technique scheme, has following beneficial effect:
The invention solves hydrogen fluoride condensation and the synthetic product condensation containing freon 142, suitable Ethylene Dichloride, anti-Ethylene Dichloride, and be separated the hydrogenchloride of gas phase and the low halohydrocarbon that boils under 0 ~-50 DEG C (preferably-20 ~-30 DEG C), pressure 0.1 ~ 1.1MPa (preferably 0.6 ~ 0.9MPa) condition.Liquid phase is divided two-layer: upper strata is remaining HF, can be used for lower batch of freon 142 and synthesizes, and lower floor is freon 142, suitable Ethylene Dichloride and anti-Ethylene Dichloride mixture.Rectificating method separable go out object product freon 142, and can be used for lower batch of freon 142 along Ethylene Dichloride and anti-Ethylene Dichloride and synthesize.Chromium magnesium fluoride catalysts, according to the preparation of Russia patent RU 2005539 environment-protective process, is made loose porous, active ingredient magnesium fluoride and is carried the equally distributed structure of chromium fluoride.The high reactivity of catalyzer when this structure can ensure halogenated hydrocarbon system gas product phase fluorination, although active ingredient chromium fluoride content is very low, it compares with magnesium fluoride is rare and expensive compound.Catalyzer is used in particulate state by extruding in reactor, and catalyzer is dry under 100 ~ 200 DEG C of conditions before the synthesis, with hydrogen fluoride activation (process) at 200 ~ 350 DEG C.In addition, will regenerate when catalyst activity reduces, the activity of this rear catalyst can be recovered.
Claims (8)
- The preparation method of the fluoro-2-monochloroethane of 1.1,1-bis-, is characterized in that comprising the steps:1) first the chromium magnesium fluoride catalysts containing 10 ~ 15% chromium fluorides (trivalent) and 85 ~ 90% magnesium fluorides is added in reactor and react, and stirred by agitator, by blower pump with the speed of 6 ~ 10 marks l/h by reactor described in nitrogen purging 2 ~ 5 hours, then by vaporizer, temperature is controlled to carry out predrying at 100 ~ 200 DEG C, and supply hydrogen fluoride by described vaporizer, described hydrofluoric feed speed is 100 ~ 200g/h, activation continues 4 ~ 8 hours, then the described chromium magnesium fluoride catalysts after predrying is carried out activation treatment with described hydrogen fluoride at 200 ~ 350 DEG C of temperature, at the end of process to be activated, the temperature of described vaporizer is set in 150 ~ 350 DEG C,2) above-mentioned described chromium magnesium fluoride catalysts after hydrogen fluoride activation treatment is added the fixed-bed reactor with catalyst layer, then by 1, 1, 2-trichloroethane or suitable 1, 2-Ethylene Dichloride, anti-1, 2-Ethylene Dichloride and 1, 1, the mixture of 2-trichloroethane, it is 150 ~ 350 DEG C in temperature of reaction, reaction pressure (absolute pressure) is 0.1 ~ 1.1MPa, duration of contact is 15 ~ 150 seconds, under the condition of HF and chloride material molar ratio=2 ~ 40:1, pass into described fixed-bed reactor and carry out gas phase catalytic fluorination reaction, and in described fixed-bed reactor, pass into described hydrogen fluoride and trichloroethane or Ethylene Dichloride when synthesizing by described vaporizer, regulate the reaction pressure in described fixed-bed reactor simultaneously,3) then will pass into condenser through the reacted sintetics of above-mentioned gas phase catalytic fluorination and carry out condensation, condensed synthetics carries out layering again, after making separation, upper strata is hydrogen fluoride, lower floor is the gaseous state synthetic product containing freon 142, suitable Ethylene Dichloride, anti-Ethylene Dichloride and trichloroethane, described gaseous state synthetic product is released through described condensator outlet, and continues to pass into described hydrogen fluoride and described trichloroethane or described Ethylene Dichloride;4) after described hydrogen fluoride and described trichloroethane have supplied, liquid phase synthesis product through top and bottom process liquid phase separation is released bottom collector, the hydrogen fluoride be separated is used for lower batch of use, the described liquid phase synthesis product of bottom is organic mixture, and with basic solution, described organic mixture is neutralized, use zeolite NaA dry again, finally by rectifying obtained 1, the fluoro-2-monochloroethane of 1-bis-, the described synthesis being used for lower batch of freon 142 along Ethylene Dichloride and described anti-Ethylene Dichloride after rectifying separation.
- 2. the preparation method of 1,1-bis-fluoro-2-monochloroethane according to claim 1, is characterized in that: step 1) in described chromium magnesium fluoride catalysts be particulate state, active ingredient is Cr 3+, wherein said active ingredient accounts for 10% ~ 15% in described chromium magnesium fluoride catalysts.
- 3. the preparation method of 1,1-bis-fluoro-2-monochloroethane according to claim 2, is characterized in that: the carrier of described chromium magnesium fluoride catalysts is MgF 2.
- 4. according to claim 11, the preparation method of the fluoro-2-monochloroethane of 1-bis-, it is characterized in that: step 2) in described temperature of reaction be 220 ~ 280 DEG C, described reaction pressure is 0.6 ~ 0.9MPa, described duration of contact is 20 ~ 50 seconds, described HF and described chloride material molar ratio=4 ~ 10:1.
- 5. the preparation method of 1,1-bis-fluoro-2-monochloroethane according to claim 1, is characterized in that: step 3) in described condenser be recoverable condenser.
- 6. the preparation method of 1,1-bis-fluoro-2-monochloroethane according to claim 5, is characterized in that: described condenser is provided with refrigerant chuck.
- 7. the preparation method of 1,1-bis-fluoro-2-monochloroethane according to claim 1, is characterized in that: described vaporizer and described reactor are all provided with electric heater.
- 8. the preparation method of 1,1-bis-fluoro-2-monochloroethane according to claim 7, is characterized in that: described reactor is provided with tensimeter and variable valve.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3056584A1 (en) * | 2016-09-27 | 2018-03-30 | Arkema France | PROCESS FOR THE PRODUCTION OF 1-CHLORO-2,2-DIFLUOROETHANE |
| FR3056586A1 (en) * | 2016-09-27 | 2018-03-30 | 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 |
| CN114853563B (en) * | 2022-06-27 | 2024-06-28 | 山东华安新材料有限公司 | Preparation method of 2-chloro-1, 1-difluoroethane |
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| FR3056584A1 (en) * | 2016-09-27 | 2018-03-30 | Arkema France | PROCESS FOR THE PRODUCTION OF 1-CHLORO-2,2-DIFLUOROETHANE |
| FR3056586A1 (en) * | 2016-09-27 | 2018-03-30 | Arkema France | COMPOSITION COMPRISING 1-CHLORO-2,2-DIFLUOROETHANE |
| WO2018060576A1 (en) * | 2016-09-27 | 2018-04-05 | Arkema France | Method for producing 1-chloro-2,2-difluoroethane |
| US10640439B2 (en) | 2016-09-27 | 2020-05-05 | Arkema France | Method for producing 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 |
| CN114853563B (en) * | 2022-06-27 | 2024-06-28 | 山东华安新材料有限公司 | Preparation method of 2-chloro-1, 1-difluoroethane |
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