CN103012054A - Device and method for preparing ultra-high purity difluoromono-chloroethane - Google Patents
Device and method for preparing ultra-high purity difluoromono-chloroethane Download PDFInfo
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- CN103012054A CN103012054A CN2012105506966A CN201210550696A CN103012054A CN 103012054 A CN103012054 A CN 103012054A CN 2012105506966 A CN2012105506966 A CN 2012105506966A CN 201210550696 A CN201210550696 A CN 201210550696A CN 103012054 A CN103012054 A CN 103012054A
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Abstract
The invention provides a device and a method for preparing ultra-high purity difluoromono-chloroethane. The device comprises a heat exchangeable photochlorination reactor, an HCL-removing tower, a chlorine-removing tower, a dry buffer tank, a single-stage oil-free compressor, a degassing tower, a rectifying tower, a molecular sieve drier and a product tank. The method comprises the following steps: mixing raw materials and feeding the mixture into a photochlorination reactor for reaction, feeding the reactant into a two-stage water absorption HCL tower and a two-stage alkali liquor absorption chlorine gas tower to remove HCL and chlorine; feeding the obtained product into a dry buffer tank; compressing the gas from the dry buffer tank with a single-stage oil-free compressor and feeding the compressed gas into a degassing tower and a rectifying tower for degassing and rectifying to obtain difluoromono-chloroethane with moisture; and then removing the moisture with a molecular sieve drier to obtain a pure difluoromono-chloroethane product. According to the device and the method, the production flow of the difluoromono-chloroethane is shortened, the reaction conversion rate is high, the by-products are few, the rectifying efficiency is high, the raw materials and the energy consumption are reduced, the purity of the product is high and the production of the whole set of device is safe and economic.
Description
Technical field
The invention belongs to the fluorine chemical field, be specifically related to a kind of preparation facilities and method of ultra-high purity difluoromono-chloroethane.
Technical background
Along with domestic and international manufacturer requires to improve constantly, the difluoromono-chloroethane of original top grade product can not be met the need of market, particularly extremely tight to the requirement of some Small Indicators, high-purity grade difluoromono-chloroethane ability satisfying the market requirement, following table is the contrast of difluoromono-chloroethane quality index:
The preparation method of present domestic difluoromono-chloroethane is mainly light chlorination process and prepares difluoromono-chloroethane, be subjected to the restriction of the factors such as production unit, prepared difluoromono-chloroethane can only reach top grade product index request, and production cost is high, pollution is heavy, can't satisfy the now requirement of most manufacturers.A kind of preparation method of difluoromono-chloroethane is disclosed such as Chinese patent 201010108206.8, the method is by material gasification preheating, optical chlorinating reaction, compression, multistage light separation, liquid phase washing, liquid phase neutralization, rectifying and the dry difluoromono-chloroethane that obtains purity 〉=99.9% of taking off, exist raw material reaction not exclusively, HCl and chlorine absorption not thoroughly, the shortcoming such as product purity is not high; Chinese patent 200410015778.6 discloses a kind of preparation method of difluoromono-chloroethane, the method is by the difluoromono-chloroethane that raw material mixes, actinic reactor reaction, the reaction of second order reaction still, separating treatment obtain purity 〉=99.9%, exist operating procedure complexity, wastage of material, energy consumption large, pollute weigh, product purity is not high and the high in cost of production shortcoming.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of raw material consumption low, transformation efficiency is high, reaction preference is strong, and by-products content is few, and technical process is simple, safety coefficient is high, pollutes littlely, and product purity reaches the device and method of high-purity grade preparation ultra-high purity difluoromono-chloroethane.
For achieving the above object, specific embodiments of the present invention is:
A kind of ultra-high purity difluoromono-chloroethane preparation facilities, but by heat exchange optical chlorinating reaction device, take off the HCl tower, the dechlorinator, the dry type surge tank, the single-stage oil free compressor, degassing tower, rectifying tower, mole sieve drier and pan tank are connected to form successively, but described heat exchange optical chlorinating reaction device is connected in series successively from the bottom to top by the more piece conversion zone and forms, descend most the lower end of joint conversion zone to be provided with opening for feed, the upper end of going up the joint conversion zone most is provided with discharge port, described conversion zone comprises reactor and interchanger, described reactor is arranged at the interchanger lower end and is interconnected, and the middle and lower part is provided with light-source system in the reactor;
The described HCl of taking off tower is that twin-stage water absorbs the HCl tower, and it is internal reflux stainless steel casting packing tower that described twin-stage water absorbs the HCl tower, and the operating pressure of tower is 1.5～2.0MPa, and working temperature in the tower: 40～65 ℃, tower top temperature is-25～-5 ℃; Described dechlorinator is twin-stage alkali liquor absorption chlorine tower, and described twin-stage alkali liquor absorption chlorine tower is the Carbon steel stuffing material tower, and the operating pressure of tower is 1.0～1.5 MPa, working temperature in the tower: 40～80 ℃;
Described single-stage oil free compressor is that single-stage is without oily fluorine press;
Described degassing tower, rectifying tower are the wire packing tower.
Described interchanger is tube and shell heat exchanger, and the tube side of interchanger is communicated with reactor, upper and lower rising pipe and the water inlet pipe that is connected with respectively with valve of the shell side of interchanger.
The middle and upper part is equipped with the temperature inductor that connection respectively saves the conversion zone interchanger in the reactor of described more piece conversion zone.
Described light-source system is ultraviolet lamp tube.
Described reactor is carbon tube reactor or steel lining PO pipe reactor, and described interchanger is graphite tube heat exchanger or steel lining PO tube heat-exchanger.
Further, adopt a kind of ultra-high purity difluoromono-chloroethane preparation facilities to prepare the method for ultra-high purity difluoromono-chloroethane, may further comprise the steps:
(1) with after C2H4F2 C2H4F2 and chlorine preheating, the gasification in molar ratio 1.15:1 mix;
(2) mixed gas with step (1) gained passes into the optical chlorinating reaction device, make mixed gas pass through successively every joint conversion zone of optical chlorinating reaction device, regulate the flooding quantity of every joint conversion zone interchanger, the temperature that makes every joint conversion zone is 40～80 ℃, the reaction pressure of mixed gas in conversion zone is 0.05～0.1MPa, and to make mixed gas reaction time in the optical chlorinating reaction device be 60～90S;
(3) will pass into by the gas of optical chlorinating reaction device gained twin-stage water and absorb the HCl tower, changing the HCl in the gas into concentration by the twin-stage falling film absorption is 25～30% hydrochloric acid; To remove again gas behind the HCl and pass into twin-stage alkali and absorb the chlorine tower, and open alkali lye and add interchanger and cool off, the chlorine in the gas that removes behind the HCl will be transformed into clorox;
The gas that (4) will take off after HCl, the dechlorination passes in the dry type surge tank, from the dry type surge tank gas is compressed into pressure as the gas of 0.5～0.8 MPa take the intake pressure of 0.05MPa by the single-stage oil free compressor again;
(5) will carry out two stage rectification through the gas of single-stage oil free compressor compression, carry out one-level by degassing tower first degassed, slough the low-boiling-point substances such as unreacted C2H4F2 C2H4F2, and unreacted C2H4F2 C2H4F2 reclaimed through recovery tower and rewinding storage tank, remove the difluoromono-chloroethane that the difluoro ethylene dichloride obtains containing aqueous vapor by rectifying tower again;
The difluoromono-chloroethane that (6) will contain aqueous vapor removes moisture through mole sieve drier and obtains pure difluoromono-chloroethane and pass into and make the difluoromono-chloroethane finished product in the pan tank.
The tower internal pressure was 1.5～2.0MPa when described twin-stage water absorbed HCl tower absorption HCl, and service temperature is in the tower: 40～65 ℃; It is 1.0～1.5 MPa that described twin-stage alkali liquor absorption chlorine tower absorbs chlorine tower internal pressure, and the service temperature of tower is: 40～80 ℃, and the temperature of circulation alkali liquor≤40 ℃.
Described degassing tower adopts total reflux, and working pressure is 0.65～0.75MPa, and service temperature is 40～60 ℃; Described rectifying tower reflux ratio 1.5～2.5, pressure 0.3～0.4MPa, 40～60 ℃ of temperature.
The content of the difluoromono-chloroethane that described method makes 〉=99.99%, moisture content≤10PPm, evaporation of residual≤10PPm, acidity≤0.5PPm, non-condensable gas≤0.8%.
After adopting such scheme, the beneficial effect that the present invention reaches is:
(1) but this device main reactor is heat exchange optical chlorinating reaction device, this reactor adopts multi-stage light according to section and heat exchanging segment, can effectively control reacting balance carries out, suppress the generation of by product, guaranteed again the safe operation of equipment, prolonged its work-ing life, made single cover response capacity can reach 1Kt/a, and traditional optical chlorinating reaction device is the void tower structure, reaction heat moves to walk, and temperature of reaction is high, and by product is many, equipment failure is many, single cover response capacity only has 500t/a, more has some reactors to adopt spray C2H4F2 C2H4F2 method, and this method has been upset reaction ratio, low conversion rate, large-scale production do not possess operability;
(2) but the mol ratio of the raw material C2H4F2 C2H4F2 that heat exchange optical chlorinating reaction device adopts and chlorine is 1.15:1, guaranteed that chlorine reacts away as far as possible, transformation efficiency is high, can suppress simultaneously the superchlorination reaction and carry out, and reduces by product and generates; But return the reactive system reaction after the simultaneously separable recovery of excessive C2H4F2 C2H4F2 of heat exchange optical chlorinating reaction device, a small amount of chlorine is low because of price, amount is few, can adopt first scale to wash rear compression method, directly removes in caustic washing system again;
(3) HCl in the gas is answered in the absorption of this device employing twin-stage water absorption HCl tower, by the twin-stage falling film absorption, absorbs fully, and the concentration of hydrochloric acid of absorption generation is fully controlled, has prevented that the secondary of HCl from volatilizing; Twin-stage alkali absorbs the chlorine tower and adopts circulation alkali liquor to add interchanger cooling alkali lye, guaranteed that alkali liquid temperature has guaranteed that all the time below 40 ℃ absorbing the clorox that generates follows stability, has saved starting material in the absorption chlorine process, prevent environmental pollution, reduced cost; (4) the single-stage oil free compressor adopts high compression ratio, good seal performance, pressurized gas is not subjected to lubricant pollution, technique is simple simultaneously, easy to operate, and traditional technology adopts two-stage compression (1.6MPa), also needs the refueling water separator to separate stage compression and takes lubricating oil in the material to, has increased the complicacy of producing;
(5) distillation system adopts degassing tower and rectifying tower, two tower packings all adopt the Stainless Steel Cloth filler, packed height is more than 20 meters, guaranteed degassed, rectifying fully, reduced the loss of product in degassed, the rectifying, effectively avoid the corrosion of product to the loose heap of conventional filler stainless steel Pall ring, reduced maintenance and production cost;
(6) present method adopts first scale to wash, single-stage compression again, rear degassed rectifying, refrigerant adopts recirculated water, the short energy consumption of flow process is extremely low, and traditional technology adopts two-stage compression (1.6MPa), through take off the HCl tower, the dechlorinator reclaims HCl, chlorine, makes reaction gas reach neutrality through the liquid phase water alkali wash again, take off HCl tower, dechlorinator's working pressure at 1.0MPa～1.8MPa, cat head needs-35 ℃ of chilled brines to make refrigerant, complicated operation, and cost is high;
(7) present method adopts the degassed rectification method of single-stage, adopt the method for low tower top temperature, high reflux ratio, the single-stage degassing tower adopts the cat head total reflux to slough the low-boiling-point substances such as unreacted C2H4F2 C2H4F2, again through rectifying tower and from overhead collection purity 〉=99.99% difluoromono-chloroethane, and bottom product (main component is the dichloro C2H4F2 C2H4F2) can be from the extraction of rectifying tower reactor, threshold concentration is controlled at ﹤ 3%, can keep the rectifying tower component substantially constant, the bottom product of extraction is by separating, reclaiming, reduce pollution, reduced consumption; And traditional technology adopts secondary degassed, one-level rectifying, and efficient is low, and product purity does not reach high-purity level;
(8) content of difluoromono-chloroethane 〉=99.99% in the prepared difluoromono-chloroethane of present method, moisture content≤10PPm, evaporation of residual≤10PPm, acidity≤0.5PPm, non-condensable gas≤0.8% has reached high-purity grade standard.
To sum up, present device is simple to operate, and technical process is short, and energy consumption is low, and environmental pollution is little, and prepared difluoromono-chloroethane purity is high, cost is low.
Description of drawings
Fig. 1 is optical chlorinating reaction device structural representation of the present invention;
Fig. 2 is that twin-stage water of the present invention absorbs HCl tower structure schematic diagram;
Fig. 3 is that twin-stage alkali of the present invention absorbs chlorine tower structure schematic diagram;
Fig. 4 is degassing tower structural representation of the present invention;
Fig. 5 is rectifying tower structure schematic diagram of the present invention;
Fig. 6 is preparation facilities schematic diagram of the present invention.
Among the figure, optical chlorinating reaction device 1, opening for feed 101, conversion zone 102, reactor 103, interchanger 104, ultraviolet lamp tube 105, temperature sensor 106, water inlet pipe 107, valve 108, rising pipe 109, discharge port 110, twin-stage water absorbs HCl tower 2, hydrochloric acid tank 201, one-level water washing tank 202, secondary water washing tank 203, spray column 204, total inlet mouth 205, one-level water washing tank pneumatic outlet 206, secondary water washing tank inlet mouth 207, secondary water washing tank pneumatic outlet 208, spray column inlet mouth 209, spray column liquid exit 210, secondary water washing tank liquid-inlet 211, secondary water washing tank liquid exit 212, one-level water washing tank liquid-inlet 213, one-level water washing tank liquid exit 214, hydrochloric acid tank import 215, take off the pneumatic outlet 216 behind the HCl, twin-stage alkali liquor absorption chlorine tower 3, one-level alkali liquor absorption chlorine tower 301, secondary alkali liquor absorption chlorine tower 302, one-level alkali lye circulation heat exchanger 303, secondary alkali lye circulation heat exchanger 304, one-level alkali liquor absorption chlorine tower inlet mouth 305, one-level alkali liquor absorption chlorine tower air outlet 306, secondary alkali liquor absorption chlorine tower inlet mouth 307, secondary alkali liquor absorption chlorine tower air outlet 308, two dry type surge tanks 4, single-stage is without oily fluorine press 5, degassing tower 6, degassing tower steam-heated cal(l)andria reboiler 601, degassed body of the tower 602, degassing tower condenser 603, inlet mouth 604, work in-process air outlet 605, C2H4F2 C2H4F2 air outlet 606, pressure-detecting device 607, temperature-detecting device 608, wire packing 609, rectifying tower 7, rectifying tower steam-heated cal(l)andria reboiler 701, rectifying tower body of the tower 702, rectifying tower condenser 703, rectifying tower inlet mouth 704, rectifying tower wire packing 705, temperature-detecting device 706, pressure-detecting device 707 contains the difluoromono-chloroethane outlet 708 of aqueous vapor, mole sieve drier 8, pan tank 9.
Embodiment
The present invention will be further described below in conjunction with embodiment.
Shown in Figure 6, ultra-high purity difluoromono-chloroethane preparation facilities schematic diagram of the present invention, but comprise heat exchange optical chlorinating reaction device 1, twin-stage water absorbs HCl tower 2, twin-stage water absorbs chlorine tower 3, dry type surge tank 4, single-stage oil free compressor 5, degassing tower 6, rectifying tower 7, but heat exchange optical chlorinating reaction device 1 absorbs HCl tower 2 through gas reservoir and twin-stage water and is communicated with, and the air outlet that twin-stage water absorbs HCl tower 2 is communicated with the inlet mouth that twin-stage water absorbs chlorine tower 3, between twin-stage water absorption chlorine tower 3 and single-stage oil free compressor 5, be provided with dry type surge tank 4, single-stage oil free compressor 5 compressed storage tanks are communicated with the inlet mouth of degassing tower 6, and the air outlet of degassing tower 6 is communicated with the inlet mouth of rectifying tower 7, are provided with successively mole sieve drier 8 and pan tank 9 behind the rectifying tower 7.
Shown in Figure 1, optical chlorinating reaction device of the present invention comprises opening for feed 101, discharge port 110 and more piece conversion zone 102, every joint conversion zone 102 comprises reactor 103, interchanger 104, ultraviolet lamp tube 105, temperature sensor 106, water inlet pipe 107, valve 108 and rising pipe 109, reactor 103 is arranged at interchanger 104 belows, reactor 103 interior middle and lower parts are provided with ultraviolet lamp tube 105, reactor 103 interior middle and upper parts are provided with temperature sensor 106, interchanger 104 is tube and shell heat exchanger, reactor 103 is communicated with interchanger 104 tube sides, interchanger 104 shell sides are provided with, the rising pipe 109 of arranging down and water inlet pipe 107, water inlet pipe 107 be equipped with the valve 108 that connects temperature sensor 106 on rising pipe is connected, the bottom of next joint conversion zone connects opening for feed 101, and the top of going up a joint conversion zone most connects discharge port 110.
Shown in Figure 2, twin-stage water of the present invention absorbs the HCl tower and comprises from the bottom to top hydrochloric acid tank 201, one-level water washing tank 202, secondary water washing tank 203, spray column 204, spray column 204 tops are provided with spray column pneumatic outlet 216, spray column 204 two bottom sides are respectively equipped with spray column inlet mouth 209 and spray column liquid exit 210, secondary water washing tank 203 tops are provided with secondary water washing tank liquid-inlet 211 and secondary water washing tank inlet mouth 207, the middle and lower part is provided with the bottom and is provided with secondary water washing tank liquid exit 212, one-level water washing tank 202 tops are provided with total inlet mouth 205 and one-level water washing tank liquid-inlet 213, the bottom is provided with one-level water washing tank liquid exit 214 and one-level water washing tank pneumatic outlet 206, hydrochloric acid tank 201 tops are provided with hydrochloric acid import 215, one-level water washing tank pneumatic outlet 206 is communicated with secondary water washing tank inlet mouth 207, secondary water washing tank pneumatic outlet 208 is communicated with spray column inlet mouth 209, spray column liquid exit 210 is communicated with secondary water washing tank liquid-inlet 211, secondary water washing tank liquid exit 212 is communicated with one-level water washing tank liquid-inlet 213, and one-level water washing tank liquid exit 214 is communicated with hydrochloric acid import 215.
Shown in Figure 3, twin-stage alkali liquor absorption chlorine tower of the present invention comprises one-level alkali liquor absorption chlorine tower 301 and secondary alkali liquor absorption chlorine tower 302; One-level alkali liquor absorption chlorine tower 301 is respectively equipped with an inlet mouth 305, an air outlet 306 and No. two inlet mouths 307,308, numbers air outlets 306, No. two air outlets with secondary alkali liquor absorption chlorine tower 302 and is communicated with No. two inlet mouths 307; One-level alkali liquor absorption chlorine tower 301 is communicated with the top of one-level alkali liquor absorption chlorine tower 301 with secondary alkali liquor absorption chlorine tower 302 through one-level alkali lye circulation heat exchanger 303 and secondary alkali lye circulation heat exchanger 304 respectively with the bottom of secondary alkali liquor absorption chlorine tower 302.
Shown in Figure 4, degassing tower of the present invention is disposed with degassing tower steam-heated cal(l)andria reboiler 601, degassed body of the tower 602, degassing tower condenser 603 from bottom to top, degassing tower body of the tower middle and upper part is provided with inlet mouth 604, degassing tower body of the tower top is provided with pressure-detecting device 607 and temperature-detecting device 608, degassing tower body of the tower inside is provided with wire packing 609, degassing tower steam-heated cal(l)andria reboiler 601 is provided with work in-process air outlet 605, and degassing tower condenser 603 is provided with C2H4F2 C2H4F2 air outlet 606.
Shown in Figure 5, rectifying tower of the present invention comprises rectifying tower steam-heated cal(l)andria reboiler 701, rectifying tower body of the tower 702, rectifying tower condenser 703, and rectifying tower steam-heated cal(l)andria reboiler 701 is connected from bottom to top with rectifying tower body of the tower 702, and pipeline is passed through at rectifying tower body of the tower top
WithRectifying tower condenser 703 is communicated with, rectifying tower body of the tower bottom is provided with rectifying tower inlet mouth 704, equipment wire packing 705 in the rectifying tower body of the tower, the rectifying tower body is provided with temperature-detecting device 706, pressure-detecting device 707, rectifying tower condenser 703 bottoms are provided with the difluoromono-chloroethane outlet 708 that contains aqueous vapor.
Embodiment one
The method that the present invention prepares the ultra-high purity difluoromono-chloroethane may further comprise the steps:
(1) reaction: behind raw material C2H4F2 C2H4F2 and the liquid chlorine vaporizing, 1.15:1 mixes in molar ratio, enter optical chlorinating reaction device 1 and carry out optical chlorinating reaction, 40 ℃ of temperature of reaction, reaction pressure 0.05MPa, reaction time 60S, the C2H4F2 C2H4F2 charging capacity of single cover optical chlorinating reaction device is 100～150Kg/h;
(2) washing: absorb HCl tower 2 absorbing hydrogen chlorides through the reacted gas of optical chlorinating reaction device through twin-stage water, and to make the operating pressure in the tower be 1.5MPa, temperature is 40 ℃ in the tower, and the HCl of absorption is dissolved in the hydrochloric acid that water is transformed into concentration 25～30%;
(3) alkali cleaning: the gas that removes behind the HCl is removed chlorine through twin-stage alkali liquor absorption chlorine tower 3, operating pressure in the tower is 1.0MPa, working temperature is 40 ℃ in the tower, and ON cycle alkali lye interchanger makes the temperature of alkali lye≤40 ℃, and chlorine is transformed into clorox behind alkali liquor absorption;
The gas that process is taken off behind HCl, the dechlorination gas is the gas mixture (acidity≤0.5PPm), this mixed gas is passed into dry type surge tank 4 of neutral difluoromono-chloroethane and C2H4F2 C2H4F2;
(4) compression: take off that the neutral mixed gas of gained enters single-stage without oily fluorine press 5 pressure-raisings by dry type surge tank 4 behind HCl, the dechlorination gas, intake pressure is 0.05 MPa, top hole pressure 0.5MPa;
(5) enter degassing tower 6 from becoming the mixed solution that contains difluoromono-chloroethane and C2H4F2 C2H4F2 etc. after the gas of single-stage after without 5 compressions of oily fluorine press through refrigerant is the condenser condenses liquefaction of recirculated water from degassing tower 6 middle and upper parts with the pump supercharging, tower reactor pressure 0.65MPa, 40 ℃ of temperature, the cat head refrigerant is recirculated water, the cat head C2H4F2 C2H4F2 again enters the optical chlorinating reaction device with gas form and reacts as starting material, and the liquid that contains difluoromono-chloroethane in the tower reactor enters rectifying tower 7 with variable valve control flow by rectifying tower 7 middle and lower parts, the reflux in tower ratio is 1.5, tower reactor pressure is 0.3MPa, 40 ℃ of temperature, obtain containing the difluoromono-chloroethane gas of aqueous vapor from cat head, and main component is that dichloro C2H4F2 C2H4F2 bottom product interruption is from the extraction of rectifying tower reactor, threshold concentration is controlled at ﹤ 3%, keep the rectifying tower component substantially constant, the bottom product of extraction is by separating, reclaim;
(6) after the difluoromono-chloroethane that contains aqueous vapor from the extraction of rectifying tower cat head is the condenser condenses liquefaction of recirculated water through refrigerant, to water content≤10 PPm, pass into the difluoromono-chloroethane finished product that pan tank 9 obtains purity 〉=99.99% entering mole sieve drier 8 adsorption dries under the pressure 0.2MPa;
Embodiment two
The method that the present invention prepares the ultra-high purity difluoromono-chloroethane may further comprise the steps:
(1) reaction: behind raw material C2H4F2 C2H4F2 and the liquid chlorine vaporizing, 1.15:1 mixes in molar ratio, enters optical chlorinating reaction device 1 and carries out optical chlorinating reaction, 80 ℃ of temperature of reaction, reaction pressure 0.1MPa, reaction time 90S, the C2H4F2 C2H4F2 charging capacity of single cover optical chlorinating reaction device is 100～150Kg/h;
(2) washing: absorb HCl tower 2 absorbing hydrogen chlorides through the reacted gas of optical chlorinating reaction device through twin-stage water, and to make the operating pressure in the tower be 2.0MPa, temperature is 80 ℃ in the tower, and the HCl of absorption is dissolved in the hydrochloric acid that water is transformed into concentration 25～30%;
(3) alkali cleaning: the gas that removes behind the HCl is removed chlorine through twin-stage alkali liquor absorption chlorine tower 3, operating pressure in the tower is 1.5MPa, working temperature is 80 ℃ in the tower, and ON cycle alkali lye interchanger makes the temperature of alkali lye≤40 ℃, and chlorine is transformed into clorox behind alkali liquor absorption;
The gas that process is taken off behind HCl, the dechlorination gas is the gas mixture (acidity≤0.5PPm), this mixed gas is passed into dry type surge tank 4 of neutral difluoromono-chloroethane and C2H4F2 C2H4F2;
(4) compression: take off that the neutral mixed gas of gained enters single-stage without oily fluorine press 5 pressure-raisings by dry type surge tank 4 behind HCl, the dechlorination gas, intake pressure is 0.05 MPa, top hole pressure 0.8 MPa,
(5) enter degassing tower 6 from becoming the mixed solution that contains difluoromono-chloroethane and C2H4F2 C2H4F2 etc. after the gas of single-stage after without 5 compressions of oily fluorine press through refrigerant is the condenser condenses liquefaction of recirculated water from degassing tower 6 middle and upper parts with the pump supercharging, tower reactor pressure 0.75MPa, temperature 60 C, the cat head refrigerant is recirculated water, the cat head C2H4F2 C2H4F2 again enters the optical chlorinating reaction device with gas form and reacts as starting material, and the liquid that contains difluoromono-chloroethane in the tower reactor enters rectifying tower 7 with variable valve control flow by rectifying tower 7 middle and lower parts, the reflux in tower ratio is 2.5, tower reactor pressure is 0.4MPa, temperature 60 C, obtain containing the difluoromono-chloroethane gas of aqueous vapor from cat head, and main component is that dichloro C2H4F2 C2H4F2 bottom product interruption is from the extraction of rectifying tower reactor, threshold concentration is controlled at ﹤ 3%, keep the rectifying tower component substantially constant, the bottom product of extraction is by separating, reclaim;
(6) after the difluoromono-chloroethane that contains aqueous vapor from the extraction of rectifying tower cat head is the condenser condenses liquefaction of recirculated water through refrigerant, to water content≤10 PPm, pass into the difluoromono-chloroethane finished product that pan tank 9 obtains purity 〉=99.99% entering mole sieve drier 8 adsorption dries under the pressure 0.3MPa;
Embodiment three
The method that the present invention prepares the ultra-high purity difluoromono-chloroethane may further comprise the steps:
(1) reaction: behind raw material C2H4F2 C2H4F2 and the liquid chlorine vaporizing, 1.15:1 mixes in molar ratio, enter optical chlorinating reaction device 1 and carry out optical chlorinating reaction, 60 ℃ of temperature of reaction, reaction pressure 0.07MPa, reaction time 70S, the C2H4F2 C2H4F2 charging capacity of single cover optical chlorinating reaction device is 100～150Kg/h;
(2) washing: absorb HCl tower 2 absorbing hydrogen chlorides through the reacted gas of optical chlorinating reaction device through twin-stage water, and to make the operating pressure in the tower be 1.7MPa, temperature is 60 ℃ in the tower, and the HCl of absorption is dissolved in the hydrochloric acid that water is transformed into concentration 25～30%;
(3) alkali cleaning: the gas that removes behind the HCl is removed chlorine through twin-stage alkali liquor absorption chlorine tower 3, operating pressure in the tower is 1.2MPa, working temperature is 60 ℃ in the tower, and ON cycle alkali lye interchanger makes the temperature of alkali lye≤40 ℃, and chlorine is transformed into clorox behind alkali liquor absorption;
The gas that process is taken off behind HCl, the dechlorination gas is the gas mixture (acidity≤0.5PPm), this mixed gas is passed into dry type surge tank 4 of neutral difluoromono-chloroethane and C2H4F2 C2H4F2;
(4) compression: take off that the neutral mixed gas of gained enters single-stage without oily fluorine press 5 pressure-raisings by dry type surge tank 4 behind HCl, the dechlorination gas, intake pressure is 0.05 MPa, top hole pressure 0.7MPa,
(5) enter degassing tower 6 from becoming the mixed solution that contains difluoromono-chloroethane and C2H4F2 C2H4F2 etc. after the gas of single-stage after without 5 compressions of oily fluorine press through refrigerant is the condenser condenses liquefaction of recirculated water from degassing tower 6 middle and upper parts with the pump supercharging, tower reactor pressure 0.7MPa, temperature 50 C, the cat head refrigerant is recirculated water, the cat head C2H4F2 C2H4F2 again enters the optical chlorinating reaction device with gas form and reacts as starting material, and the liquid that contains difluoromono-chloroethane in the tower reactor enters rectifying tower 7 with variable valve control flow by rectifying tower 7 middle and lower parts, the reflux in tower ratio is 2, tower reactor pressure is 0.35MPa, temperature 50 C, obtain containing the difluoromono-chloroethane gas of aqueous vapor from cat head, and main component is that dichloro C2H4F2 C2H4F2 bottom product interruption is from the extraction of rectifying tower reactor, threshold concentration is controlled at ﹤ 3%, keep the rectifying tower component substantially constant, the bottom product of extraction is by separating, reclaim;
(6) after the difluoromono-chloroethane that contains aqueous vapor from the extraction of rectifying tower cat head is the condenser condenses liquefaction of recirculated water through refrigerant, to water content≤10 PPm, pass into the difluoromono-chloroethane finished product that pan tank 9 obtains purity 〉=99.99% entering mole sieve drier 8 adsorption dries under the pressure 0.25MPa;
The performance of the difluoromono-chloroethane of present method gained is as follows: difluoromono-chloroethane 〉=99.99%, moisture content≤10PPm, evaporation of residual≤10PPm, acidity≤0.5PPm, non-condensable gas≤0.8%.
Above embodiment all is preferred embodiments of the present invention, for a person skilled in the art, makes the protection domain that simple replacement all belongs to claim of the present invention on the basis of above-described embodiment.
Claims (9)
1. ultra-high purity difluoromono-chloroethane preparation facilities, but by heat exchange optical chlorinating reaction device, take off HCl tower, dechlorinator, dry type surge tank, single-stage oil free compressor, degassing tower, rectifying tower, mole sieve drier and pan tank and be connected to form successively, it is characterized in that:
But described heat exchange optical chlorinating reaction device is connected in series successively from the bottom to top by the more piece conversion zone and forms, descend most the lower end of joint conversion zone to be provided with opening for feed, the upper end of going up the joint conversion zone most is provided with discharge port, described conversion zone comprises reactor and interchanger, described reactor is arranged at the interchanger lower end and is interconnected, and the middle and lower part is provided with light-source system in the reactor;
The described HCl of taking off tower is that twin-stage water absorbs the HCl tower, and it is internal reflux stainless steel casting packing tower that described twin-stage water absorbs the HCl tower, and the operating pressure of tower is 1.5～2.0MPa, and working temperature in the tower: 40～65 ℃, tower top temperature is-25～-5 ℃;
Described dechlorinator is twin-stage alkali liquor absorption chlorine tower, and described twin-stage alkali liquor absorption chlorine tower is the Carbon steel stuffing material tower, and the operating pressure of tower is 1.0～1.5 MPa, working temperature in the tower: 40～80 ℃;
Described single-stage oil free compressor is that single-stage is without oily fluorine press;
Described degassing tower, rectifying tower are the wire packing tower.
2. a kind of ultra-high purity difluoromono-chloroethane preparation facilities according to claim 1, it is characterized in that: described interchanger is tube and shell heat exchanger, the tube side of interchanger is communicated with reactor, upper and lower rising pipe and the water inlet pipe that is connected with respectively with valve of the shell side of interchanger.
3. a kind of ultra-high purity difluoromono-chloroethane preparation facilities according to claim 1 is characterized in that: the middle and upper part is equipped with the temperature inductor that connection respectively saves the conversion zone interchanger in the reactor of described more piece conversion zone.
4. a kind of ultra-high purity difluoromono-chloroethane preparation facilities according to claim 1, it is characterized in that: described light-source system is ultraviolet lamp tube.
5. a kind of ultra-high purity difluoromono-chloroethane preparation facilities according to claim 1, it is characterized in that: described reactor is carbon tube reactor or steel lining PO pipe reactor, described interchanger is graphite tube heat exchanger or steel lining PO tube heat-exchanger.
6. method of utilizing the described ultra-high purity difluoromono-chloroethane of claim 1 preparation facilities to prepare the ultra-high purity difluoromono-chloroethane is characterized in that: may further comprise the steps:
(1) with C2H4F2 C2H4F2 and chlorine preheating, in molar ratio 1.15:1 mixing after the gasification;
(2) mixed gas with step (1) gained passes into the optical chlorinating reaction device, make mixed gas pass through successively every joint conversion zone of optical chlorinating reaction device, regulate the flooding quantity of every joint conversion zone interchanger, the temperature of controlling every joint conversion zone is 40～80 ℃, the reaction pressure of mixed gas in conversion zone is 0.05～0.1MPa, and to make mixed gas reaction time in the optical chlorinating reaction device be 60～90S;
(3) will pass into by the gas of optical chlorinating reaction device gained twin-stage water and absorb the HCl tower, be 25～30% hydrochloric acid for concentration with the washing of the HCl in the gas by the twin-stage falling film absorption; The gas that will remove again behind the HCl passes into twin-stage alkali liquor absorption chlorine tower, and opens the alkali lye circulation heat exchanger and cool off, and the chlorine alkali cleaning in the gas that removes behind the HCl is transformed into clorox;
The gas that (4) will take off after HCl, the dechlorination passes in the dry type surge tank, from the dry type surge tank gas is compressed into pressure as the gas of 0.5～0.8 MPa take the intake pressure of 0.05MPa by the single-stage oil free compressor again;
(5) will carry out two stage rectification through the gas of single-stage oil free compressor compression, carry out one-level by degassing tower first degassed, slough unreacted C2H4F2 C2H4F2, remove the difluoromono-chloroethane that the difluoro ethylene dichloride obtains containing aqueous vapor by rectifying tower again, unreacted C2H4F2 C2H4F2 reclaims through recovery tower and rewinding storage tank;
The difluoromono-chloroethane that (6) will contain aqueous vapor removes moisture through mole sieve drier and obtains pure difluoromono-chloroethane and pass into and make the difluoromono-chloroethane finished product in the pan tank.
7. the preparation method of a kind of ultra-high purity difluoromono-chloroethane according to claim 6 is characterized in that: the tower internal pressure was 1.5～2.0MPa when described twin-stage water absorbed the HCl tower and absorbs HCl, and service temperature is in the tower: 40～65 ℃; It is 1.0～1.5 MPa that described twin-stage alkali liquor absorption chlorine tower absorbs chlorine tower internal pressure, and service temperature is in the tower: 40～80 ℃, and the temperature of circulation alkali liquor≤40 ℃.
8. the preparation method of a kind of ultra-high purity difluoromono-chloroethane according to claim 6 is characterized in that: described degassing tower adopts total reflux, and working pressure is 0.65～0.75MPa, and service temperature is 40～60 ℃; Described rectifying tower reflux ratio 1.5～2.5, pressure 0.3～0.4MPa, 40～60 ℃ of temperature.
9. the preparation method of a kind of ultra-high purity difluoromono-chloroethane according to claim 6, it is characterized in that: the content of the difluoromono-chloroethane that described method makes 〉=99.99%, moisture content≤10PPm, evaporation of residual≤10PPm, acidity≤0.5PPm, non-condensable gas≤0.8%.
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| CN107382661A (en) * | 2017-06-09 | 2017-11-24 | 浙江三美化工股份有限公司 | A kind of recovery method of difluoromono-chloroethane |
| CN109364847A (en) * | 2018-11-28 | 2019-02-22 | 内蒙古三爱富万豪氟化工有限公司 | Optical chlorinating reaction device and the method for preparing difluoromono-chloroethane |
| CN110652946A (en) * | 2019-09-24 | 2020-01-07 | 安徽神剑新材料股份有限公司 | Top temperature control system and method in polyester resin production process |
| CN111099961A (en) * | 2018-10-26 | 2020-05-05 | 中昊晨光化工研究院有限公司 | Rectification method and system for production of difluoroethane and difluoromono-chloroethane |
| CN117619111A (en) * | 2023-12-28 | 2024-03-01 | 珠海百川石化工程设计有限公司 | Acid tail gas treatment device |
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Cited By (7)
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| CN107382661A (en) * | 2017-06-09 | 2017-11-24 | 浙江三美化工股份有限公司 | A kind of recovery method of difluoromono-chloroethane |
| CN107382661B (en) * | 2017-06-09 | 2020-07-10 | 浙江三美化工股份有限公司 | Recovery method of difluoro-chloroethane |
| CN111099961A (en) * | 2018-10-26 | 2020-05-05 | 中昊晨光化工研究院有限公司 | Rectification method and system for production of difluoroethane and difluoromono-chloroethane |
| CN109364847A (en) * | 2018-11-28 | 2019-02-22 | 内蒙古三爱富万豪氟化工有限公司 | Optical chlorinating reaction device and the method for preparing difluoromono-chloroethane |
| CN110652946A (en) * | 2019-09-24 | 2020-01-07 | 安徽神剑新材料股份有限公司 | Top temperature control system and method in polyester resin production process |
| CN110652946B (en) * | 2019-09-24 | 2021-11-09 | 安徽神剑新材料股份有限公司 | Top temperature control system and method in polyester resin production process |
| CN117619111A (en) * | 2023-12-28 | 2024-03-01 | 珠海百川石化工程设计有限公司 | Acid tail gas treatment device |
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