KR100998883B1 - Recycling treatment system of hydroflourocarbons - Google Patents

Recycling treatment system of hydroflourocarbons Download PDF

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KR100998883B1
KR100998883B1 KR1020100008348A KR20100008348A KR100998883B1 KR 100998883 B1 KR100998883 B1 KR 100998883B1 KR 1020100008348 A KR1020100008348 A KR 1020100008348A KR 20100008348 A KR20100008348 A KR 20100008348A KR 100998883 B1 KR100998883 B1 KR 100998883B1
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fluorocarbon
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reactor
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김부열
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운해이엔씨(주)
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
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Abstract

PURPOSE: A recycling system of hydroflourocarbons is provided to reduce the amount of energy consumption by condensing hydrofluorocarbon at a low temperature and to improve the yield of carbon fluoride salts. CONSTITUTION: A recycling system of hydroflourocarbons comprises: a cooling condensing device(100) for generating liquid hydroflourocarbons through cooling condensation of hydroflourocarbons; an alkalization device(200) for forming a fluorocarbon salt composition by mixing liquid hydroflourocarbons with a solvent and an basic compound; and a sorting recovering device(300) for collecting hydroflourocarbons.

Description

Hydrogen Fluorocarbon Recycling System {RECYCLING TREATMENT SYSTEM OF HYDROFLOUROCARBONS}

The present invention relates to a system for synthesizing and recycling hydrogen fluorocarbons that promote global warming into fluorocarbon salts. Specifically, the hydrogen fluorocarbons are not condensed at high temperatures but are cooled and condensed at low temperatures and have a constant composition ratio with solvents and basic compounds. The present invention relates to a hydrogen fluorocarbon recycling treatment system and a method for recycling the fluorocarbon salts, which are greatly reduced in energy consumption, and thus synthesized fluorocarbon salts can be used as a raw material of the chemical industry.

Global warming is a big challenge for humans living in the 21st century, so much attention is being paid to the impact of greenhouse gases on the global environment.

Recognizing that greenhouse gases are the biggest cause of climate change, countries around the world signed the Climate Change Convention (UNFCC) in Rio, Brazil in March 1994, and were obliged to establish, report and implement greenhouse gas emission reduction measures. . Specific emission reduction targets were discussed again in Kyoto, Japan in December 1997, and 38 industrialized countries decided to reduce greenhouse gas emissions by 5.2% on average from 2008 to 2012 from 2008 to 2012. Economic instruments such as clean development system (CDM), joint implementation system (JI) and emission trading system (ET) are introduced and ratified.

Korea will be designated as the target of greenhouse gas reduction from 2013, and accordingly, 10 industries including power generation, refinery, petrochemical, cement, paper, automobile, semiconductor, city gas, and display will be selected as carbon emission reduction industries. The nation's carbon emission reduction is expected to be 5.2% lower than in 1995, and it is required to establish national and corporate countermeasures.

In particular, the global warming index of carbon dioxide, the global warming standard (GWP) is 1, whereas the hydrofluoric carbon group currently used as a substitute for Freon is HFC-23 (CHF 3 ) 11700, HFC-43 (C 5 H 2 F 10 ) 1300, HFC-125 (C 2 HF 5 ) 2800, HFC-143a (C 2 H 3 F 3 ) 3800, HFC-227a (C 3 HF 7 ) 2900, HFC-236 (C 3 H 2 F 7 ) It is very high as 6300, and accordingly, it is required to remove the used hydrofluorocarbon by removing more than 90% of Destruction & Removal Efficency (DRE).

Conventional methods or means for treating used hydrofluorocarbons include filling particulates in the upper part of the main body, supplying contaminant gas from the lower part of the main body to the upper part, and spraying the cleaning liquid on the surfaces of the fillings to allow the contaminated gas to pass between the fillings. Although a washing tower is disclosed in which the washing liquid contacts and dissolves while passing through, the hydrofluorocarbon treatment method using the washing column as described above has a problem in that the treatment efficiency of the hydrofluorocarbon is very low and the washing liquid generated from the waste water must be treated. .

In addition, an adsorption tower is disclosed in which an adsorbent such as carbon is filled into a chamber partitioned by a porous plate having a predetermined size, and a contaminated gas is passed through a packing layer to adsorb and remove contaminated gas to fine pores of the adsorbent. Hydrogen fluorocarbon adsorption method using the fluorocarbon adsorption method is too small, the adsorption function is lost when the micropores of the adsorbent is clogged is not suitable for the removal of fluorofluorocarbons, there is a problem that waste is generated continuously.

In addition, a ceramic media layer is formed of ceramic bricks, and a retention chamber is formed adjacent to each other. The temperature is increased by combustion heat of liquefied natural gas to preheat contaminant gas in the ceramic media layer, and the ceramic media layer is heated to 800 ° C. or higher in the retention chamber. Although combustion incineration of the polluted gas is disclosed by far-infrared rays and internally regenerated heat generated from, when citing the MERK INDEX data of the United States for the combustion incineration of the polluted gas as described above, hydrogen fluorocarbon is Since it supports a stable property up to 1150 ℃ there is a problem that can not be expected to remove efficiency even if incinerated above 800 ℃.

In addition to this, a method of decomposing and oxidizing hydrogen fluorocarbon by maintaining the temperature up to 1200 ° C by the combustion heat of supplying liquefied natural gas to the combustion chamber, or Korean Patent Publication No. 2009-5295 (Invention: PFC and HFC) The same method of treating fluorine compounds) discloses a method of decomposing and oxidizing liquefied natural gas using plasma. However, when the temperature at which the hydrofluorocarbon is decomposed is lowered below 1150 ° C., the fluorocarbon is not treated. In addition, the CO2 is generated when the liquefied natural gas is combusted, and the global warming material is discharged again, and hydrogen fluoride, a secondary pollutant having a strong corrosion effect, is generated to corrode the device. Of course, there is a problem that requires a separate neutralization facility.

In order to solve the problems described above, the present invention and the applicant in the same Korean Patent Application No. 2009-74125 is not condensed hydrogen fluorocarbon at a high temperature of more than 1200 ℃ but instead of cooling condensation at low temperature and synthesized into a fluorocarbon salt energy Disclosed are a hydrogen fluorocarbon recycling system and a recycling method of using the synthesized carbon fluoride salt as a raw material of the chemical industry. However, such a recycling system for hydrofluorocarbons and a method for recycling the hydrofluorocarbons may be used in the process of synthesizing liquefied hydrogen fluorocarbons with a solvent or a basic compound to synthesize a fluorocarbon salt composition. Since a means for adjusting the composition ratio is insufficient, at least one of the liquefied hydrogen fluorocarbon, a solvent, and a basic compound may occur. Thus, the synthesis of the fluorocarbon salt composition is very unstable, resulting in a decrease in yield.

Therefore, an object of the present invention is not to burn hydrogen fluorocarbon at a high temperature of 1200 ° C. or more, but to cool and condense at a low temperature and to mix and react a solvent and a basic compound at a constant composition ratio to synthesize fluorocarbon salts, thereby greatly reducing energy consumption. In addition, the present invention provides a recycling treatment system and a recycling treatment method of hydrogen fluorocarbon that can use the synthesized fluorocarbon salt as a raw material of the chemical industry.

In order to achieve the above object, the present invention provides a cooling condensation apparatus for cooling and condensing hydrofluorocarbons to form liquefied hydrogen fluorocarbon; An alkalizing reaction device formed to synthesize the liquefied hydrogen fluoride carbon condensed in the cooling condensation device in a predetermined composition ratio with a solvent and a basic compound to synthesize a fluorocarbon salt composition; And a fractionation and recovery device for classifying the fluorocarbon salt composition synthesized in the alkalizing apparatus by the boiling point difference to separate unreacted hydrogen fluorocarbons, by-products, and solvents, and to recover the fluorocarbon salts. This is provided.

In addition, the present invention comprises the steps of cooling and condensing the hydrogen fluorocarbon to -93 ~ -47 ℃ in a cooling condensation apparatus to form liquefied hydrogen fluorocarbon; The liquefied hydrogen fluorocarbon is a solvent which is dimethylformamide and / or dimethyl sulfoxide in an alkalizing reaction apparatus, KOH, t-BUO-K + , CH 3 OK + , C 2 H 5 OK + , C 3 H 7 OK, C At least one from the group consisting of 4 H 9 OK + , NaOH, t-BUO-Na, CH 3 O-Na, C 2 H 5 O-Na, C 3 H 7 O-Na + , C 4 H 9 O-Na Mixing with a basic compound selected above in a constant composition ratio and reacting at -70 to -40 ° C for 30 minutes to 2 hours to synthesize a fluorocarbon salt composition; And classifying the fluorocarbon salt composition by the boiling point difference in the fractionation recovery apparatus to separate unreacted hydrofluorocarbon, by-products, and solvent. Provided is a method for recycling a hydrofluorocarbon comprising recovering a fluorocarbon salt and an unreacted basic compound.

Hydrogen fluorocarbon recycling treatment system according to the present invention because the hydrofluoric carbon having a very high global warming index is treated by cooling and condensing at a low temperature without raising the temperature to 1200 ℃, the energy consumption can be significantly reduced, thereby greatly improving the economic efficiency It has

In addition, the hydrogen fluorocarbon recycling treatment system of the present invention is mixed with the liquefied hydrogen fluorocarbon in a predetermined composition ratio to synthesize a fluorocarbon salt composition, so that the synthesis of the fluorocarbon salt composition is very stable and the yield is greatly improved. This has the effect of easily controlling the synthesis of the fluorocarbon salt composition.

In addition, the hydrogen fluorocarbon recycling treatment system of the present invention does not require carbon dioxide due to liquefied natural gas combustion, and hydrogen fluoride, which is a secondary pollutant, does not require a separate facility for treating hydrogen fluoride. .

In addition, the hydrogen fluorocarbon recycling treatment system of the present invention can use the fluorocarbon salts generated during the treatment process as a raw material of the chemical industry can be expected to the effect of saving resources by utilizing waste resources.

1 is an overall configuration diagram of a hydrofluorocarbon treatment system according to the present invention

The present invention is an improved invention of Korean Patent Application No. 2009-74125, in which the applicants do not increase the hydrogen fluorocarbon to 1200 ° C., but condensate at low temperature and react with the solvent and the basic compound at a constant composition ratio to form a fluorocarbon salt composition. It is a technical idea to collect | recover and to collect | recover the fluorocarbon salt by classifying and refine | purifying the said fluorocarbon salt composition.

Hereinafter, with reference to the accompanying drawings and preferred embodiments of the hydrofluorocarbon recycling treatment system of the present invention will be described in detail. In describing the present invention, when it is determined that the detailed description of the related well-known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted.

Figure 1 shows the overall configuration of the hydrofluorocarbon treatment system according to the present invention.

Referring to Figure 1, the hydrofluorocarbon recycling processing system of the present invention includes a cooling condensation apparatus for cooling and condensing the hydrofluorocarbon to form liquefied hydrogen fluorocarbon.

In the present invention, HFC-23 (CHF 3 ), HFC-32 (CH 2 F 2 ), HFC-41 (CH 3 F), HFC-43 (C 5 H 2 F 10 ), HFC-125 ( C 2 HF 5 ), HFC-134 (C 2 H 2 F 4 ), HFC-134a (CH 2 FCF 3 ), HFC-152a (C 2 H 4 F 2 ), HFC-143 (C 2 H 3 F 3 ), HFC-143a (C 2 H 3 F 3 ), HFC-227 (C 3 HF 7 ), HFC-236 (C 3 H 2 F 7 ), HFC-245 (C 3 H 3 F 5 ), etc. The hydrofluorocarbon mixture or recycled mixture of two or more is recycled. Such hydrofluorocarbons are characterized by having a very low boiling point of -93 to -47 deg. C, depending on the type, and flammability (for example, HFC-32 has a LEL / UFL of 14 to 33.4%). In addition, since the hydrogen fluorocarbon has a very high vapor density and a very high vapor pressure, the hydrogen fluorocarbon is partially vaporized even inside the cooling condensation apparatus 100 in the cryogenic state to form gaseous hydrogen fluorocarbon.

However, since the hydrogen fluorocarbon in the gaseous state is extremely slow in reaction with the basic compound, while the hydrogen fluorocarbon in the liquid state reacts rapidly with the basic compound, the liquefied hydrogen fluorocarbon formed by cooling and condensing the hydrogen fluorocarbon is used. Synthesize fluorocarbon salts.

The cooling condensation apparatus 100 for cooling and condensing hydrogen fluorocarbon to form liquefied hydrogen fluorocarbon includes a heat exchanger 150 for cooling and condensing hydrogen fluorocarbon by a heat exchange action, and hydrogen condensed and cooled in the heat exchanger 150. Transfer pump 181 for transferring the fluorocarbon to the alkalizing reactor 220, and blower 170 for transferring the hydrogen fluorocarbon, which is part of the inside of the cooling condensation apparatus 100 to form a gas state to the alkalizing reactor 220 ) Is configured.

And, if necessary, the hydrogen fluorocarbon gas which connects the blower 170 and the heat exchanger 150 to be transported to the heat exchanger 150 to be cooled and condensed without transferring the hydrogen fluorocarbon in the gas state to the alkalinization reactor 220. The conveying piping is comprised. An opening and closing valve 171a is formed at one point of the hydrogen fluorocarbon gas conveying pipe, and a separate opening and closing valve 171b is also formed in the pipe connecting the blower 170 and the alkalizing reactor 220 to open and close the valve. And to induce or block the flow of hydrogen fluorocarbon in the gaseous state by the opening / closing operation of 171a and 171b.

That is, when the on / off valve 171a of the hydrogen fluorocarbon gas conveyance pipe is closed and the on / off valve 171b of the pipe connecting the blower 170 and the alkalizing reactor 220 is opened, the gas pressurized by the blower 170. While the hydrogen fluorocarbon in the state is transferred to the alkalizing reactor 220, the opening / closing valve 171a of the hydrogen fluorocarbon gas conveying pipe is opened and the opening / closing valve of the pipe connecting the blower 170 and the alkalizing reactor 220 ( When 171b is closed, the hydrogen fluorocarbon in the gas state pressurized by the blower 170 is returned to the heat exchanger 150 to be cooled and condensed.

The heat exchanger 150, which is a core component of the cooling condensation apparatus 100, uses liquid nitrogen having a boiling point of -196 ° C or liquefied natural gas having a boiling point of -162 ° C. It is cooled by the latent heat of vaporization and sensible heat to cool and condense the hydrogen fluorocarbon to -93 to -47 ℃. To this end, the heat exchanger 150 is connected to a refrigerant storage container 161 for storing liquid nitrogen and liquefied natural gas, or configured to be connected by a refrigerant pipeline and a refrigerant transfer pipe 162 outside the system. When the temperature for cooling and condensing the hydrofluorocarbon in the heat exchanger 150 is less than -93 ° C, the energy consumption used for cooling and condensing the hydrofluorocarbon is excessive, and the temperature for cooling and condensing the hydrofluorocarbon is -47. If it exceeds C, the hydrofluorocarbon is not cooled or condensed.

Alternatively, the cooler may be connected to the heat exchanger 150 to be configured to cool and condense the hydrofluorocarbon by the heat exchange action of the heat exchanger 150 by the cold air provided in the cooler. However, since the boiling point of the hydrofluorocarbons is a low temperature of -93 to -47 ° C, a cooler capable of providing cryogenic cold air of -140 ° C to effectively cool and condense the hydrofluorocarbons is connected to the heat exchanger 150. It must be formed.

As described above, the liquefied hydrogen fluorocarbon which is cooled by the latent heat of vaporization, sensible heat of liquid nitrogen, liquefied natural gas, or cooled in the heat exchanger 150 by cold air provided in the cooler is pressurized by the transfer pump 181 to alkalinize. It is transferred to the reactor 200 and synthesized into a fluorocarbon salt composition.

Then, to stabilize the synthesis of the fluorocarbon salt composition, the hydrogen fluorocarbon feed rate control valve 190 is provided at any point of the hydrogen fluorocarbon transport pipe connecting the cooling condensation device 100 and the alkalizing reaction device 200. It is formed, it is possible to arbitrarily appropriately control the supply rate of the liquefied hydrogen fluorocarbon and gaseous hydrogen fluorocarbon to be transferred to the alkalizing reactor 220 by operating the hydrogen fluorocarbon feed rate control valve 190.

That is, the hydrofluoric carbon, which is a liquid state and a gaseous state, transferred at a predetermined feed rate by operating the hydrofluorocarbon feed rate control valve 190 is mixed and reacted with a solvent and a basic compound at a constant composition ratio in the alkalizing reactor 220 to fluoride. It is synthesized stably with the carbon salt composition, and does not react and no substance remains in the synthesis process.

In addition, the hydrogen fluorocarbon recycling treatment system of the present invention is an alkalizing reaction device is formed so as to synthesize the liquefied hydrogen fluoride carbon condensed in the cooling condensation apparatus with a solvent, a basic compound in a constant composition ratio to synthesize a fluorocarbon salt composition Is mixed.

In terms of chemical characteristics, the reaction of liquefied hydrogen fluorocarbon with a solvent and a basic compound to be synthesized into a fluorocarbon salt composition is described in terms of chemistry. It is tempered. Therefore, when fluorine is present in the carbon compound, the fluorine-bonded carbon is deprived of electrons, so that hydrogen bonded to the carbon has a property of easily falling into a cation. In particular, the more fluorine-containing carbon is bonded, the more likely hydrogen is bound to cation.

In conclusion, the hydrogen atoms bonded to the fluorocarbons are easily separated by the fluorine atoms and basic compounds having the property of attracting electrons, and the hydrogen fluorocarbons exist in the anion form. Carbon fluoride is reacted with a basic compound to synthesize a fluorocarbon salt.

By the way, since the reaction rate with the basic compound is extremely slow in the gaseous hydrogen fluorocarbon, liquefied hydrogen fluorocarbon which can react quickly with the basic compound is used to synthesize the fluorocarbon salt.

The basic compound produced by the fluorocarbon salt by reacting with liquefied hydrogen fluorocarbon has excellent reactivity with hydrogen fluorocarbon and has a KOH (with potassium or sodium atom) which easily binds to a carbon atom of hydrogen fluorocarbon in an anion state. Potassium Hydroxide), t-BUO-K + (Potassium Tertiary Butoxide), CH 3 OK + (Potassium Methoxide), C 2 H 5 OK + (Potassium Ethoxide), C 3 H 7 OK + (Potassium Propoxide), C 4 H 9 OK + (Potassium Butoxide), NaOH (Sodium Hydroxide), t-BUO-Na (Sodium Tertiary Butoxide), CH 3 O-Na (Sodium Methoxide), C 2 H 5 O-Na (Sodium Ethoxide), C 3 H At least one basic compound selected from the group consisting of 7 O-Na + (Sodium Propoxide) and C 4 H 9 O-Na (Sodium Butoxide) is used.

As an example, the reaction between CHF 3 (HydroTriFluoro Methane), which is a type of liquefied hydrogen fluorocarbon, and t-BUO-K +, which is a basic compound, is described below. First, three fluorine groups bonded to a carbon atom of CHF 3 are illustrated. Atomic molecules attract electrons, and hydrogen atoms can be easily separated into cations. At this time, anhydrous hydrogen fluorocarbon reacts easily with t-BUO-K + , resulting in alkalized fluorocarbon CF 3 -K + . Will occur.

Figure 112010006338263-pat00001

↓

Figure 112010006338263-pat00002

↓ t-BUO-K

Figure 112010006338263-pat00003

For example, the reaction between CHF 3 , a liquefied hydrogen fluorocarbon, and K-OH, a basic compound, will first attract three fluorine atoms bonded to a carbon atom of CHF 3 to attract electrons. In this case, anhydrous hydrogen fluorocarbon reacts with K-OH to generate an alkalized fluorocarbon salt CF 3 -K + .

The reaction of liquefied hydrofluorocarbons and basic compounds proceeds in solution, wherein the solvent used can dissolve both hydrofluorocarbons and basic compounds at the same time, whereas the solvents themselves do not react with the basic compounds and hydrofluorocarbons. You must have a condition. Examples of the solvent that satisfy the above conditions include dimethylformamide (DMF) and the dimethylformamide-based solvent, or dimethyl sulfoxide (DMSO) and the dimethyl sulfoxide-based solvent, and the like. The reaction of the hydrogen fluorocarbon and the basic compound may be performed by using alone or a solvent thereof, dimethyl sulfoxide and a solvent thereof, or a mixture of two or more thereof.

Based on the above-described chemical reaction, an alkalizing reaction apparatus 200 is formed in which the liquefied hydrogen fluorocarbon transferred from the cooling condensation apparatus 100 is mixed with a solvent and a basic compound to synthesize a fluorocarbon salt composition.

The alkalizing reaction apparatus 200 is a solvent storage for supplying a solvent to the alkalizing reactor 220, the alkalizing reactor 220 to synthesize the fluorocarbon salt composition by mixing and reacting a solvent, a basic compound to a liquefied hydrogen fluorocarbon in a certain composition ratio A tank 240 and a basic compound storage tank 230 for supplying a basic compound to the alkalizing reactor 200 are included.

The solvent supply rate control valve 241 is formed at any point of a pipe connecting the solvent storage tank 240 and the alkalizing reactor 220 in the alkalizing reaction device as described above. By operating, it is possible to arbitrarily appropriately control the supply speed of the solvent to be transferred to the alkalizing reactor 220, and also to supply the basic compound supplying speed to any point of the pipe connecting the basic compound storage tank 230 and the alkalizing reactor 220. A control valve 231 is formed, and by operating the basic compound feed rate control valve 231, it is possible to arbitrarily and appropriately adjust the feed rate of the basic compound to be transferred to the alkalizing reactor 220.

Hydrofluorocarbons, solvents and basic compounds in the alkalizing reactor 220 by a flow control device comprising a hydrofluorocarbon feed rate control valve 190, a basic compound feed rate control valve 231, and a solvent feed rate control valve 241. It is precisely supplied at this preset composition ratio and reacted.

That is, the liquid and gaseous hydrogen fluorocarbon, which is supplied at a constant supply rate in the cooling condensation apparatus 100, and the constant supply in the solvent and basic compound storage tanks 230 supplied at a constant supply rate in the solvent storage tank 240. A solution having a constant composition ratio formed by mixing basic compounds supplied at a rate is stably reacted to form a fluorocarbon salt composition in high yield.

Specifically, the solvent supplied at a constant feed rate from the solvent storage tank 240 to the liquefied hydrogen fluorocarbon inside the alkalizing reactor 220 and the basic compound supplied at a constant feed rate from the basic compound storage tank 230 are mixed. When the mixture is stirred with the stirrer 250 to form a solution having a constant composition ratio, and reacted at -70 to -40 ° C for 30 minutes to 2 hours, the basic compound in the solution removes hydrogen ions of the hydrogen fluorocarbon to hydrogen fluoride. A carbon anion is formed, and the hydrofluorocarbon anion is combined with a cation of a basic compound to stably synthesize a fluorocarbon salt, thereby forming a high yield of fluorocarbon salt composition.

If the temperature at which the solution of the liquefied hydrogen fluorocarbon, the solvent, and the basic compound is reacted in the alkalinization reactor 220 to form the fluorocarbon salt composition is less than -70 ° C, the reactivity between the liquefied hydrogen fluorocarbon and the basic compound is reduced. When the temperature at which the liquefied hydrogen fluorocarbon, the solvent, and the solution of the basic compound are reacted exceeds −40 ° C., the liquefied hydrogen fluorocarbon in the solution is vaporized to react with the basic compound. An extremely delayed phenomenon occurs. In addition, when the time for reacting the solution of the liquefied hydrogen fluorocarbon, the solvent, and the basic compound in the alkali reactor 220 to form a fluorocarbon salt composition is less than 30 minutes, the liquefied hydrogen fluorocarbon and the basic compound do not sufficiently react. When the time for reacting the solution of liquefied hydrogen fluorocarbon, the solvent, and the basic compound in the inside of the alkaliization reactor 220 exceeds 2 hours, the liquefied hydrogen fluorocarbon and the basic compound no longer react, as well as the reaction time. The excessive operation cost of the alkalizing reactor 220 is increased.

Such a fluorocarbon salt composition contains a certain amount of unreacted hydrogen fluorocarbon, a by-product (mainly alcohol), and a solvent, in addition to the fluorocarbon salt in which a hydrogen fluorocarbon anion is bonded to a cation of a basic compound and synthesized in high yield. Therefore, in addition to separating the fluorocarbon salts from the fluorocarbon salt composition of the composition as described above, it is preferable to classify and recycle unreacted hydrogen fluorocarbons, by-products, and solvents, respectively. 300).

In addition, the hydrogen fluorocarbon recycling treatment system of the present invention classifies the fluorocarbon salt composition synthesized in the alkali reaction apparatus by boiling point separation to separate unreacted fluorofluorocarbons, by-products, solvents and recover fluorocarbon salts. A recovery device is included.

In addition to separating the fluorocarbon salts from the fluorocarbon salt composition, the fractionation and recovery apparatus 300 is configured to classify unreacted hydrogen fluorocarbon, by-products, and solvents, respectively.

To this end, the fractionation and recovery apparatus 300 heats the fluorocarbon salt composition transferred from the alkalizing reaction apparatus 200 to evaporate unreacted hydrogen fluorocarbon, by-products, and solvent, and evaporates in the evaporator 310. A fractionation tower 320 having a sieve plate columm type structure for classifying the unreacted hydrogen fluorocarbons, by-products, and solvents by boiling point differences, and a fluoride for recovering fluorocarbon salts remaining in the evaporator 310. A carbon salt recovery vessel 360 is included.

When the fluorocarbon salt composition transferred from the alkali reaction apparatus 200 is injected into the evaporator 310 and heated with stirring in the evaporator 310, the unreacted hydrogen fluorocarbon, a by-product, and the solvent contained in the fluorocarbon salt composition Is sequentially vaporized according to the boiling point flows into the fractionation tower 320, so that only the fluorocarbon salt and the unreacted basic compound remain in the evaporator 310.

Specifically, when the fluorocarbon salt composition is heated in the evaporator 310, first, unreacted hydrogen fluorocarbon, which has a low boiling point of −93 to −47 ° C., is first vaporized, and a by-product that has a middle boiling point of 70 to 100 ° C. is next. After evaporating, the solvent of dimethylformamide-based or dimethyl sulfoxide-based having a high boiling point of 189 ° C. or more is finally vaporized and introduced into the fractionation tower 320 having a network cylindrical structure, and unreacted hydrogen fluoride in the fractionation tower 320. Carbon vapors, by-product vapors, and solvent vapors are subsequently condensed and discharged.

To this end, the classification tower 320 stores an unreacted hydrogen fluorocarbon condenser for condensing unreacted hydrogen fluorocarbon vapor and an unreacted hydrogen fluorocarbon storage for storing unreacted hydrogen fluorocarbon condensed and discharged from the unreacted hydrogen fluorocarbon condenser. A vessel, a by-product condenser for condensing the by-product steam, and a by-product storage container for storing the by-product condensed from the by-product condenser, a solvent condenser for condensing solvent vapor, and a solvent storage container for storing the solvent condensed and discharged from the solvent condenser. It is configured to be connected to the pipe.

The fluorocarbon salt and the unreacted basic compound remaining in the evaporator 310 are transferred to the fluorocarbon salt recovery vessel 360 and recovered.

The recovered fluorocarbon salt and the unreacted basic compound are separated by a difference in solubility in an organic solvent to form a purified fluorocarbon salt, and the fluorocarbon salt may be used as a raw material of the chemical industry.

For example, a fluorocarbon salt can be reacted with phosgene (Phosgen, COCl 2 ) to produce acids, amides, esters, anhydrides, and the like containing fluorocarbon components.

As a specific embodiment thereof,

① CF 3 K + Phosgen (COCl 2 )-> CF 3 COCl (Trifluotro acetylchloride)

② CF 3 COCl + Ethanol-> CF 3 COOC 2 H5 (Trifluoro acetate)

③ CF 3 COCl + Ethylene Diamine-> CF 3 CON (C 2 H 5 ) 2 (Trifluoro aceteamide)

④ CF 3 COCL + H 2 O-> CF 3 COOH (Trifluoro aceticacid)

Etc., and thus, the effect of resource saving due to the utilization of waste resources can be expected.

The above-described recycling system for hydrofluorocarbons treats hydrofluorocarbons by cooling and condensing them at low temperatures without raising the temperature to 1200 ° C, thereby greatly reducing energy consumption and greatly improving economic efficiency.

In addition, the hydrogen fluorocarbon recycling treatment system of the present invention is mixed with the liquefied hydrogen fluorocarbon in a predetermined composition ratio to synthesize a fluorocarbon salt composition, so that the synthesis of the fluorocarbon salt composition is very stable and the yield is greatly improved. At the same time, the hydrogen fluorocarbon feed rate regulating valve for controlling the supply rate of liquefied hydrogen fluorocarbon and gaseous hydrogen fluorocarbon, the solvent supply rate regulating valve for regulating the feed rate of the solvent and the supply rate of the basic compound By the operation of the basic compound feed rate control valve, which is possible, the synthesis of the fluorocarbon salt composition can be easily controlled.

In addition, the hydrogen fluorocarbon recycling treatment system does not generate carbon dioxide due to liquefied natural gas combustion, and hydrogen fluoride, which is a secondary pollutant, does not require a separate facility for treating hydrogen fluoride.

EMBODIMENT OF THE INVENTION Hereinafter, the recycling method of the hydrofluorocarbon of this invention is demonstrated in detail with reference to a preferable Example.

The recycling method of the hydrofluorocarbon of the present invention includes the step of cooling and condensing the hydrofluorocarbon at -93 to -47 ° C in a cooling condensation apparatus to form liquefied hydrogen fluorocarbon.

HFC-23, HFC-32, HFC-41, HFC-43, HFC-125, HFC-134, HFC-134a, HFC-152a, HFC-143, HFC-143a, HFC-227, HFC- 236, HFC-245, or the like, can be recycled alone or in combination with two or more hydrofluorocarbon mixtures. Such hydrofluorocarbons are characterized by having a low boiling point of -93 to -47 deg. In addition, since the hydrogen fluorocarbon has a very high vapor density and a very high vapor pressure, a part of the hydrogen fluorocarbon is vaporized even inside the cryogenic condensation apparatus to form gaseous hydrogen fluorocarbon.

By the way, since the reaction rate with the basic compound is extremely slow in the gaseous hydrogen fluorocarbon, fluorocarbon salts are synthesized using liquefied hydrogen fluorocarbon which can react quickly with the basic compound.

To this end, gaseous hydrogen fluoride carbon is cooled and condensed at -93 to -47 ° C. in a heat exchanger of a cooling condenser to form liquefied hydrogen fluorocarbon, and the liquefied hydrogen fluorocarbon is pressurized by a transfer pump to give an alkalizing reaction device. Transfer to. The hydrogen fluorocarbon, which is partially vaporized inside the cooling condensation apparatus and forms a gas state, is also transferred to the alkalizing reactor of the alkalizing reaction apparatus by a blower, and if necessary, the gaseous hydrogen fluorofluorocarbon is returned to the heat exchanger to be cooled and condensed again. do. In the transfer of the liquefied hydrogen fluorocarbon and gaseous hydrogen fluorocarbon to the alkali reaction apparatus, the supply rate of liquefied hydrogen fluorocarbon and gaseous hydrogen fluorocarbon is appropriately controlled by operating a hydrogen fluorocarbon supply rate control valve. .

In addition, the method for recycling the hydrofluorocarbon of the present invention is a dimethylformamide and / or dimethyl sulfoxide solvent, KOH, t-BUO-K + , CH 3 OK + , C 2 H 5 OK + , C 3 H 7 OK, C 4 H 9 OK + , NaOH, t-BUO-Na, CH 3 O-Na, C 2 H 5 O-Na, C 3 H 7 O-Na + , Mixing with at least one basic compound selected from the group consisting of C 4 H 9 O-Na at a constant composition ratio and reacting at -70 to -40 ° C for 30 minutes to 2 hours to synthesize the fluorocarbon salt composition. .

The hydrogen atoms bonded to the fluorocarbons are easily separated by the fluorine atoms and basic compounds having the property of attracting electrons, and the fluorocarbons exist in the anion form, and the fluorocarbons exist in the anion form as described above. Is reacted with a basic compound to synthesize a fluorocarbon salt.

The reaction of the liquefied hydrogen fluorocarbon and the basic compound proceeds in a solution state, and the solvent used here can simultaneously dissolve the fluorocarbon and the basic compound, while satisfying the condition that it does not react with the basic compound and the fluorofluorocarbon. Dimethylformamide (DMF) and the dimethylformamide-based solvent, or dimethyl sulfoxide (DMSO) and the dimethylsulfoxide-based solvents alone or in combination of two or more of the hydrogen fluorocarbon and the basic compound It can help to keep the reaction.

Therefore, liquefied hydrogen fluorocarbon, dimethylformamide (DMF) and the dimethylformamide-based solvent, or dimethyl sulfoxide (DMSO) and the dimethylsulfoxide-based solvent, KOH, t-BUO in the alkalizing reactor of the alkaline reaction apparatus. -K + , CH 3 OK + , C 2 H 5 OK + , C 3 H 7 OK, C 4 H 9 OK + , NaOH, t-BUO-Na, CH 3 O-Na, C 2 H 5 O-Na , C 3 H 7 O-Na + , C 4 H 9 O-Na at least one or more selected from the group consisting of basic compounds mixed in a constant composition ratio and stirred with a stirrer for 30 minutes to 2 hours at -70 ~ -40 ℃ Reacting during the synthesis of fluorocarbon salts to form a fluorocarbon salt composition containing unreacted hydrogen fluorocarbons, by-products (mainly alcohols), and solvents, in addition to the fluorocarbon salts, and transferring the fluorocarbon salt composition to a sorting recovery device. do.

In addition, the method for recycling the hydrofluorocarbon of the present invention is to classify the fluorocarbon salt composition by the boiling point difference in the fractionation recovery apparatus to separate unreacted hydrofluorocarbons, by-products, and solvents. Recovering the fluorocarbon salt and the unreacted basic compound.

When the fluorocarbon salt composition transferred from the alkali reaction apparatus is injected into the evaporator and heated with stirring in the evaporator, the unreacted hydrogen fluorocarbon, by-products, and the solvent contained in the fluorocarbon salt composition are sequentially vaporized in the boiling point order. It flows into the fractionation tower, so that only the fluorocarbon salt and the unreacted basic compound remain in the evaporator.

That is, when the fluorocarbon salt composition transferred from the alkalizing reaction apparatus is heated in the evaporator of the fractionation and recovery apparatus, the low boiling unreacted hydrogen fluorocarbon is first vaporized, the middle boiling by-product is vaporized next, and the high boiling solvent is Finally, the gas is introduced into a fractionation tower having a sieve plate columm structure, and the fractionation tower condenses and discharges unreacted hydrogen fluorocarbon vapor, by-product vapor, and solvent vapor in this order.

The unreacted hydrogen fluorocarbon vapor discharged from the fractionation tower is condensed in an unreacted hydrogen fluorocarbon condenser and stored in an unreacted hydrogen fluorocarbon storage container, and the by-product vapor discharged after the unreacted hydrogen fluorocarbon vapor is condensed in a by-product condenser. And the by-product storage container, the solvent vapor discharged after the by-product steam is condensed in a solvent condenser and stored in the solvent storage container.

As described above, the unreacted hydrogen fluorocarbon stored in the unreacted hydrogen fluorocarbon storage container is returned to the cooling condensation apparatus for cooling and condensing again, and the solvent stored in the solvent storage container is purified and returned to the alkalizing reaction apparatus to alkalinize the liquefied hydrogen fluorocarbon. It is reused in the reaction and alcohol, the main component of the by-product stored in the by-product storage container, is also purified and used for other purposes.

Then, the fluorocarbon salt and the unreacted basic compound remaining in the evaporator are transferred to the fluorocarbon salt recovery vessel and recovered.

In addition, the method for recycling the hydrogen fluorocarbon of the present invention comprises the step of separating the recovered fluorocarbon salt and the unreacted basic compound by the difference in solubility in an organic solvent to form a purified fluorocarbon salt.

The recovered fluorocarbon salt and unreacted basic compound are separated by a difference in solubility in an organic solvent to form a purified fluorocarbon salt.

That is, the mixture of recovered carbon fluoride salt and unreacted basic compound is dissolved in only the fluorocarbon salt or mixed and stirred in an organic solvent having high solubility in fluorocarbon salt, and the precipitated unreacted basic compound is separated by filtration and purified. The salt can be recovered. On the other hand, the mixture of the recovered fluorocarbon salt and the unreacted basic compound may be dissolved only in the basic compound or mixed and stirred in an organic solvent having a high solubility in the basic compound, and the precipitated purified fluorocarbon salt may be filtered out.

The recovered purified fluorocarbon salt is used as a raw material of various chemical industries.

For example, a fluorocarbon salt is reacted with phosgene (Phosgen, COCl 2 ) to produce various compounds such as acids, amides, esters, and anhydrides containing a fluorocarbon component.

On the other hand, the present invention is not limited to the described embodiments, it is possible to use and change the application site, it is common in the art that various modifications and variations can be made without departing from the spirit and scope of the present invention. It is self-evident to those who have knowledge. Therefore, such modifications or variations will have to belong to the claims of the present invention.

* Explanation of symbols for the main parts of the drawings
100: cooling condensing device 150: heat exchanger
161: refrigerant storage container 162: refrigerant transfer pipe
170: blower 171: on-off valve (a, b)
180: liquefied hydrogen fluorocarbon storage tank 181: transfer pump
190: hydrofluorocarbon feed rate control valve 200: alkalizing reaction device
220: alkalizing reactor 230: basic compound storage tank
231: basic compound feed rate control valve 240: solvent storage tank
241: solvent supply rate control valve 250: agitator
300: classification recovery device 310: evaporator
320: classification tower 360: fluorocarbon salt recovery container

Claims (15)

A heat exchanger for cooling and condensing hydrofluorocarbons to cool and condense HFCs (Hydrofluorocarbons) to form liquefied hydrogen fluorocarbons, a transfer pump for cooling the condensed hydrogen fluorocarbons to an alkalizing reactor, And a blower for transferring the hydrogen fluorocarbon in gaseous state to the alkalinization reactor, and the hydrogen fluorocarbon supply rate for controlling the supply rate of cooling, condensed liquefied liquefied hydrogen fluorocarbon and gaseous hydrogen fluorocarbon in the alkalinization reactor. A cooling condensation device having a control valve, a hydrogen fluorocarbon gas conveying pipe connecting the blower and the heat exchanger, and an opening / closing valve to the hydrogen fluorocarbon gas conveying pipe;
In the cooling condensing apparatus, the liquefied hydrogen fluorocarbon condensed in the cooling condensing apparatus is mixed with a solvent and a basic compound in a constant composition ratio, and reacted at -70 to -40 ° C for 30 minutes to 2 hours to synthesize the fluorocarbon salt composition. Supplying a basic compound to the alkalinization reactor, a solvent storage tank for supplying a solvent to the alkalinization reactor to synthesize the fluorocarbon salt composition by mixing and reacting the solvent and the basic compound in a constant composition ratio to the transferred liquefied hydrogen fluorocarbon; Alkalineation consisting of a basic compound storage tank, the solvent supply rate control valve is configured in the piping connecting the solvent storage tank and the alkalizing reactor, and the basic compound supply rate control valve is configured in the piping connecting the basic compound storage tank and the alkalizing reactor Reaction apparatus; And
And a fractionation and recovery device for classifying the fluorocarbon salt composition synthesized in the alkali reaction apparatus by boiling point difference to separate unreacted hydrogen fluorocarbons, by-products, and solvents, and to recover the fluorocarbon salts. delete The system of claim 1, wherein the heat exchanger of the cooling condensation device is configured to cool and condense the hydrofluorocarbon to -93 to -47 ° C. to form liquefied hydrogen fluorocarbon. The heat exchanger of the cooling condensation apparatus is configured to cool and condense hydrogen fluorocarbons by being connected to a liquid nitrogen, latent heat of vaporization of liquefied natural gas, sensible heat, or a cooler capable of cooling to -140 ° C. Hydrogen fluorocarbon recycling treatment system, characterized in that. delete delete delete The method of claim 1, wherein the solvent mixed with the liquefied hydrogen fluorocarbons in the alkalizing reactor of the alkalizing apparatus is dimethyl formamide (DMF: DiMethyl Formamide), or dimethyl sulfoxide, characterized in that the hydrogen is used alone or mixed Recycling system for carbon fluoride. According to claim 1, wherein the basic compound to be mixed with liquefied hydrogen fluorocarbons in the alkalizing reactor of the alkalizing reaction apparatus is KOH (Potassium Hydroxide), t-BUO-K + (Potassium Tertiary Butoxide), CH 3 OK + (Potassium Methoxide) , C 2 H 5 OK + (Potassium Ethoxide), C 3 H 7 OK + (Potassium Propoxide), C 4 H 9 OK + (Potassium Butoxide), NaOH (Sodium Hydroxide), t-BUO-Na (Sodium Tertiary Butoxide) , CH 3 O-Na (Sodium Methoxide), C 2 H 5 O-Na (Sodium Ethoxide), C 3 H 7 O-Na + (Sodium Propoxide), C 4 H 9 O-Na (Sodium Butoxide) At least one selected from hydrofluorocarbon recycling treatment system. delete delete The apparatus of claim 1, wherein the fractionation and recovery device comprises: an evaporator for heating the fluorocarbon salt composition transferred from the alkali reaction device to evaporate unreacted hydrogen fluorocarbon, by-products, and solvent;
A classification tower made of a sieve plate columm structure to classify unreacted hydrogen fluorocarbons, by-products, and solvents evaporated in the evaporator by boiling point differences; And
And a fluorocarbon salt recovery container for recovering fluorocarbon salts remaining in the evaporator. The method of claim 12, wherein the fractionation tower comprises a condenser condensing unreacted hydrofluorocarbon vapor and an unreacted hydrogen fluorocarbon storage container storing condensed unreacted hydrogen fluorocarbon, a condenser condensing byproduct vapor and a condensed byproduct. A recycling system for hydrofluorocarbons, characterized in that it is configured to be connected to a by-product storage container for storing, a condenser for condensing solvent vapor and a solvent storage container for storing the condensed solvent. delete delete
KR1020100008348A 2010-01-29 2010-01-29 Recycling treatment system of hydroflourocarbons KR100998883B1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014208808A1 (en) * 2013-06-25 2014-12-31 (주) 파인텍 System for separating and recycling perfluoro compounds

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* Cited by examiner, † Cited by third party
Title
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014208808A1 (en) * 2013-06-25 2014-12-31 (주) 파인텍 System for separating and recycling perfluoro compounds
US9592473B2 (en) 2013-06-25 2017-03-14 Finetech. Co., Ltd. Separation and recycling system of perfluorinated compounds

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