KR100957770B1 - Recycling treatment system of hydroflourocarbons and method thereof - Google Patents

Abstract

PURPOSE: A recycling treatment system of hydro flouro carbon, and a recycling treatment method thereof are provided to reduce the energy consumption by processing the hydro flouro carbon at low temperature. CONSTITUTION: A recycling treatment system of hydro flouro carbon(HFC) comprises the following: a cooling condensing device(100) forming a liquid hydro flouro carbon by cool-condensing the HFC; an alkalization reaction device(200) synthesizing a carbon fluoride salt composition by reacting the liquid hydro flouro carbon with a solvent and a basic compound; and a separation recovery device(300) separating an unreacted HFC, A by-product and the solvent from the carbon fluoride salt composition, and collecting the carbon fluoride salt composition.

Description

Recycling treatment system of hydrofluorocarbon and its recycling method {RECYCLING TREATMENT SYSTEM OF HYDROFLOUROCARBONS AND METHOD THEREOF}

The present invention relates to a system for synthesizing and recycling hydrogen fluorocarbons that promote global warming to fluorocarbon salts, and in particular, cooling and condensing hydrogen fluorocarbons at low temperatures without synthesizing them at low temperatures and thus synthesizing them with fluorocarbon salts. The present invention relates to a hydrogen fluorocarbon recycling treatment system and a method for recycling the fluorocarbon salt which can greatly reduce the fluorocarbon salt and use the synthesized fluorocarbon salt 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 the Clean Mechanism for Development (CDM) and the Joint Implementation Scheme (JI), the Emission Trading Scheme (ET), have been ratified and implemented.

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), as well as very high as 6300, the efficiency of removal of hydrogen fluoride with carbon (DRE: Destruction & removal Efficency) has been required to remove 90% or more.

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 contaminant gas is passed through a packing layer to adsorb and remove contaminant gas to fine pores of the adsorbent. Hydrogen fluorocarbon adsorption method using the fluoride carbon adsorption amount is too small, the adsorption function is not suitable when the micropores of the adsorbent is blocked, 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 is stable up to 1150 ° C., there is a problem in that removal efficiency cannot be expected even if it is incinerated above 800 ° C.

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, there is a problem that carbon dioxide is generated when liquefied natural gas is combusted, and the global warming material is discharged again, and as a result, there is a need for a separate neutralization facility as well as device corrosion. Hydrogen fluoride, a secondary pollutant, is generated to corrode the device, resulting in a separate neutralization facility as well as device corrosion. There is a problem that is needed.

Accordingly, an object of the present invention is to cool condensate at low temperature without combusting hydrogen fluorocarbon at 1200 ℃ or more and synthesized into a fluorocarbon salt, thereby greatly reducing energy consumption, and synthesized fluorocarbon salt as a raw material of chemical industry. The present invention provides a recycling treatment system for hydrofluorocarbons and a recycling treatment method thereof.

In order to achieve the above object, the present invention provides a cooling condensation apparatus for cooling and condensing hydrogen fluorocarbon to form liquefied hydrogen fluorocarbon, and reacting the liquefied hydrogen fluoride carbon condensed in the cooling condensation with a solvent and a basic compound. Alkalization reaction apparatus formed to synthesize into the fluorocarbon salt composition, and the fluorocarbon salt composition synthesized in the alkalizing reaction apparatus is classified by the boiling point difference to separate the residual solvent, basic compounds, by-products and to recover the fluorocarbon salt Provided is a recycling system for hydrofluorocarbons comprising a recovery device.

In the present invention, the step of cooling and condensing the hydrogen fluorocarbon to -93 ~ -47 ℃ in a cooling condensation apparatus to form liquefied hydrogen fluorocarbon, dimethylformamide and dimethylformamide in the alkalizing reaction apparatus Derivatives or solvents that are dimethyl sulfoxide and dimethyl sulfoxide derivatives, KOH, t-BUO-K ⁺ , CH ₃ OK ⁺ , C ₂ H ₅ OK ⁺ , C ₃ H ₇ OK, C ₄ H ₉ OK ⁺ , NaOH, mixed with at least one basic compound selected from the group consisting of t-BUO-Na, CH ₃ O-Na, C ₂ H ₅ O-Na, C ₃ H ₇ O-Na ⁺ , and C ₄ H ₉ O-Na Reacting at −70 to −40 ° C. for 30 minutes to 2 hours to synthesize the fluorocarbon salt composition, and classifying the fluorocarbon salt composition by boiling point difference in a fractionation recovery apparatus to separate residual solvents, basic compounds, and by-products. And, the hydrofluorocarbon ash comprising the step of recovering the fluorocarbon salts This processing method is provided for.

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 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.

The present invention relates to recovering fluorocarbon salts by synthesizing into a fluorocarbon salt composition by cooling and condensing hydrogen fluorocarbon at a low temperature, reacting with a basic compound, and classifying and purifying the fluorocarbon salt composition without heating the hydrogen fluorocarbon to 1200 ° C. I do it with a thought.

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%). Further, 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 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 the reaction rate with the basic compound, while the hydrogen fluorocarbon in the liquid state reacts rapidly with the basic compound, liquefied hydrogen fluorocarbon formed by cooling and condensing the hydrogen fluorocarbon is used. To synthesize a fluorocarbon salt.

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.

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. Should 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 reaction apparatus 200.

In addition, the hydrogen fluorocarbon recycling treatment system of the present invention includes an alkalizing reaction device that is formed to react the liquefied hydrogen fluoride carbon condensed in the cooling condensation device with a solvent, a basic compound to synthesize a fluorocarbon salt composition.

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.

↓

↓ t-BUO-K

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 meet the above conditions include dimethylformamide (DMF) and dimethylformamide derivatives, or dimethyl sulfoxide (DMSO) and dimethyl sulfoxide derivatives. The reaction of the hydrogen fluorocarbon and the basic compound may proceed by using a solvent alone or by using two or more kinds thereof in combination.

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 device 200 is a solvent storage tank 240 for supplying a solvent to the alkalizing reactor 220, the alkalizing reactor 220 to synthesize a fluorocarbon salt composition by reacting a mixture of a solvent, a basic compound to liquefied hydrogen fluorocarbons And a basic compound storage tank 230 for supplying a basic compound to the alkalizing reactor 200.

The solvent supplied from the solvent storage tank 240 and the basic compound supplied from the basic compound storage tank 230 are mixed with the liquefied hydrogen fluorocarbon inside the alkalizing reactor 220 and stirred with a stirrer 250 to give a solution. When reacted for 30 minutes to 2 hours at -70 to -40 ℃ while forming a, the basic compound in the solution to remove the hydrogen ions of the hydrogen fluorocarbon to form a hydrogen fluorocarbon anion, the hydrogen fluorocarbon anion It is combined with the cation of the basic compound to synthesize a fluorocarbon salt to form a 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 in the alkali reactor 220, the liquefied hydrogen fluorocarbon in the solution is vaporized to react with the basic compound. 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.

The fluorocarbon salt composition contains unreacted hydrogen fluorofluorocarbons, by-products (mainly alcohols), and solvents, in addition to the fluorocarbon salts in which hydrogen fluorocarbon anions are combined with a cation of a basic compound. 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 evaporated 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 unreacted hydrogen fluorocarbon stored in the unreacted hydrogen fluorocarbon storage container is returned to the cooling condensation device 100 and cooled and condensed again, and the solvent stored in the solvent storage container is purified and returned to the alkalizing reaction device 200 to be liquefied hydrogen fluoride. The alcohol, which is the main component of the by-product stored in the by-product storage container, can also be purified and used for other purposes.

In addition, the fluorocarbon salt and the unreacted basic compound remaining in the evaporator 310 are transferred to the carbon fluoride 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 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 condenser of a cooling condenser to form liquefied hydrogen fluorocarbon, and the liquefied hydrogen fluorocarbon is pressurized by a transfer pump to an alkalizing reaction device. Transfer. In addition, hydrogen fluorocarbon, which is partially vaporized inside the cooling condensation apparatus and forms a gas state, is also transferred to an alkalizing reactor of the alkalizing reaction apparatus by a blower.

In addition, the method for recycling the hydrofluorocarbon of the present invention is a dimethylformamide and a dimethylformamide derivative, or a dimethyl sulfoxide and a dimethyl sulfoxide derivative in the alkalizing reaction apparatus of the liquefied hydrogen fluorocarbon, 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 ⁺ , C ₄ H ₉ O-Na mixed with at least one basic compound selected from the group and reacted for 30 minutes to 2 hours at -70 ~ -40 ℃ to the fluorocarbon salt composition Synthesis is included.

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. The dimethylformamide and dimethylformamide derivatives, or the dimethyl sulfoxide and dimethyl sulfoxide derivatives may be used alone or in combination of two or more thereof to support maintaining the reaction of the fluorocarbon and the basic compound.

Therefore, liquefied hydrogen fluorocarbons, dimethylformamide and dimethylformamide derivatives, or dimethyl sulfoxide and dimethyl sulfoxide derivatives, KOH, t-BUO-K ⁺ , CH ₃ OK ⁺ , C in the alkalizing reactor of the alkaline reaction apparatus 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 ⁺ , Unreacted hydrogen fluorocarbon in addition to the fluorocarbon salts by mixing with a basic compound selected from the group consisting of C ₄ H ₉ O-Na and reacting for 30 minutes to 2 hours at -70 to -40 ° C while stirring with a stirrer. And a fluorocarbon salt composition containing by-products (mainly alcohols) and solvents, and transferring the fluorocarbon salt composition to a fractionation recovery apparatus.

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 alkaline reaction field 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 forming a Sieve Plate Columm structure, and unreacted hydrogen fluorocarbon vapor, by-product vapor, and solvent vapor are sequentially condensed and discharged from the fractionation tower.

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 the chemical industry.

For example, a fluorocarbon salt is reacted with phosgene (Phosgen, COCl ₂ ) to produce an acid, an amide, an ester, an hydride or the like 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.

1 is an overall configuration diagram of a hydrofluorocarbon treatment system according to 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 180: liquefied hydrogen fluorocarbon storage tank

181: transfer pump 200: alkalizing reaction device

220: alkalizing reactor 230: basic compound storage tank

240: solvent storage tank 250: stirrer

300: classification recovery device 310: evaporator

320: classification tower 360: fluorocarbon salt recovery container

Claims (12)

A cooling condensation apparatus for cooling and condensing hydrofluorocarbons (HFCs) to form liquefied hydrogen fluorocarbons; An alkalizing reaction device configured to react the liquefied hydrogen fluorocarbon condensed with cooling in the cooling condensation device with a solvent and a basic compound to synthesize a fluorocarbon salt composition; 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. The apparatus of claim 1, wherein the cooling condensation device comprises: a heat exchanger for cooling and condensing hydrofluorocarbon; A transfer pump transferring the hydrogen fluorocarbon condensed and cooled in the heat exchanger to an alkalizing reactor; And And a blower configured to transfer gaseous hydrogen fluorocarbon to an alkalizing reactor. 3. The system of claim 2, wherein the heat exchanger is configured to cool and condense the hydrofluorocarbon to -93 to -47 [deg.] C. to form liquefied hydrogen fluorocarbon. The method of claim 2, wherein the heat exchanger is connected to a cooler capable of cooling by liquid nitrogen, latent heat of vaporization of liquefied natural gas, sensible heat, or cooling to -140 ° C, and configured to cool and condense hydrogen fluorocarbon. Hydrocarbon Recycling Treatment System. The method of claim 1, wherein the alkalizing apparatus comprises an alkalizing reactor for mixing the liquefied hydrogen fluorocarbon transferred from the cooling condensation unit with a solvent and a basic compound to synthesize a fluorocarbon salt composition; A solvent storage tank for supplying a solvent to the alkalizing reactor; And And a basic compound storage tank configured to supply a basic compound to the alkalizing reactor. The method of claim 5, wherein the solvent mixed with liquefied hydrogen fluorocarbon in the alkalizing reactor is dimethylformamide (DMF: DiMethyl Formamide), dimethyl sulfoxide (DMSO: DiMethyl SulfOxide) is characterized in that used alone or mixed Hydrocarbon Recycling Treatment System. The method of claim 5, wherein the basic compound mixed with liquefied hydrofluorocarbons in the alkalizing reactor 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 At least one selected from the group consisting of -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) Hydrogen fluorocarbon recycling treatment system, characterized in that selected. According to claim 1, wherein the alkalizing reactor of the alkalizing apparatus is configured to mix the liquefied hydrogen fluorocarbon, the solvent, the basic compound and react for 30 minutes to 2 hours at -70 to -40 ℃ to synthesize a fluorocarbon salt composition Hydrogen fluorocarbon recycling treatment system, characterized in that the. 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 9, 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. Cooling and condensing the hydrofluorocarbon at -93 to -47 [deg.] C. in the cooling condensation apparatus to form liquefied hydrogen fluorocarbon; Solvent in which dimethylformamide and dimethylsulfoxide are used alone or in a mixture of the liquefied hydrogen fluorocarbon in an alkali reaction unit, 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 ⁺ , C ₄ H ₉ O-Na Mixing with at least one basic compound selected from the group consisting of and reacting at -70 to -40 ° C for 30 minutes to 2 hours to synthesize a fluorocarbon salt composition; And The fluorocarbon salt composition is classified by the boiling point difference in the fractionation recovery apparatus to separate unreacted hydrofluorocarbon, by-products, and solvent. A method of recycling a hydrofluorocarbon comprising recovering a fluorocarbon salt and an unreacted basic compound. 12. The method of claim 11, further comprising 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.

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