KR930007990B1 - Fluorine substitution in 1,1,1 trichloro ethane - Google Patents
Fluorine substitution in 1,1,1 trichloro ethane Download PDFInfo
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- KR930007990B1 KR930007990B1 KR1019900019103A KR900019103A KR930007990B1 KR 930007990 B1 KR930007990 B1 KR 930007990B1 KR 1019900019103 A KR1019900019103 A KR 1019900019103A KR 900019103 A KR900019103 A KR 900019103A KR 930007990 B1 KR930007990 B1 KR 930007990B1
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- C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
Abstract
Description
본 발명은 1,1,1-트리클로로에탄과 HF를 활성탄에 담지된 SbF3촉매의 존재하에서 기상에서 반응시켜 CH3CCl2F 및 CH3CClF2를 제조하는 방법에 관한 것이다.The present invention relates to a method for producing CH 3 CCl 2 F and CH 3 CClF 2 by reacting 1,1,1-trichloroethane and HF in the gas phase in the presence of an SbF 3 catalyst supported on activated carbon.
CH3CCl2F 및 CH3CClF2는 기존 CFC(Chloro flurocarbon)에 비해 오존층 파괴능이 현저히 낮을뿐 아니라 CH3CCl2F는 폴리우레탄 발포제, 전자회로판 세척재로, CH3CCl2F는 냉매 또는 에어로졸 분사제로서 우수한 물리적 성질을 지니고 있어 그 수요가 점차 증가하는 추세에 있다.Not only does CH 3 CCl 2 F and CH 3 CClF 2 have significantly lower ozone depletion capacity than conventional CFCs (Chloro flurocarbon), CH 3 CCl 2 F is a polyurethane foam and electronic circuit board cleaning agent, and CH 3 CCl 2 F is a refrigerant or As aerosol propellants have excellent physical properties, the demand is gradually increasing.
현재 CH3CCl2F 및 CH3CClF2의 제조방법은 다수 알려져 있다. 예를들면 일본특허 공보특공 소50-5681호에는 CH3CCl3를 무촉매상태에서 과량의 HF와 반응시키는 방법이 기재되어 있는데 이 방법은 수율 및 선택성이 낮고 고압이 필요하여 장치비가 많이 드는 결점이 있고, 다른 방법들은 대개 할로겐 교환촉매 존재하에서 액상 또는 기상 반응시키는 것으로 일본특허공보특공소 53-24924호에는 오염화몰리브덴을 촉매로 사용하는 방법이 기재되어 있고, 일본특허공보특공소 47-39086호 비닐리덴클로라이트와 HF를 반응시키는 방법이 일본특허공보특공소 59-46211호에는 안티모니펜타 할라이드 촉매와 용매를 사용하는 방법이 기재되어 있으나 이들 방법은 CH3CCl2F 및 CH3CClF2로의 선택성이 나쁘거나 용매를 사용하므로 분리공정이 추가로 필요한 결점이 있으며, 또한 액상 반응에서는 주로 안티모니할라이드 계통의 촉매가 사용되는데 반응이 진행됨에 따라 산화수가 5인 Sb(V)가 산화수인 3인 Sb(Ⅲ)로 환원되면서 촉매의 활성이 급격히 떨어지는 경향이 있다. 촉매의 재생은 염소(Cl2)를 가함으로써 해결할 수 있으나 이때 반응계중에 존재하는 불포화화합물(CH2=CCl2, CH2=CClF등)과 염소가 다음반응식과 같이 반응하여 부산물이 생기는 문제점이 있고,At present, a number of methods for preparing CH 3 CCl 2 F and CH 3 CClF 2 are known. For example, Japanese Patent Publication No. 50-5681 describes a method of reacting CH 3 CCl 3 with excess HF in the absence of a catalyst, which is a disadvantage in that the yield and selectivity are low and high pressure is required, resulting in high equipment costs. Other methods are usually liquid or gas phase reactions in the presence of a halogen exchange catalyst. Japanese Patent Laid-Open No. 53-24924 describes a method of using molybdenum pentachloride as a catalyst, and Japanese Patent Laid-Open No. 47-39086 Japanese Patent Publication No. 59-46211 discloses a method of reacting vinylidene chlorite with HF, using a method of using an antimonypenta halide catalyst and a solvent, but these methods include CH 3 CCl 2 F and CH 3 CClF 2. Due to the poor selectivity of the furnace or the use of solvents, there is a drawback that requires an additional separation process. Also, in the liquid phase reaction, an antimony halide catalyst is mainly used. As reduced to the Sb (V) is in the Sb (Ⅲ) 3 oxidation in accordance with the oxidation number 5 is used the reaction proceeds, there is a tendency that the catalyst activity rapidly drops. Regeneration of the catalyst can be solved by adding chlorine (Cl 2 ), but there is a problem that by-products are generated by the reaction of unsaturated compounds (CH 2 = CCl 2 , CH 2 = CClF, etc.) and chlorine in the reaction system as shown in the following reaction formula. ,
CH2=CCl2+Cl2→CH2Cl-CCl3 CH 2 = CCl 2 + Cl 2 → CH 2 Cl-CCl 3
CH2=CClF+Cl2→CH2C1-CCl2FCH 2 = CClF + Cl 2 → CH 2 C1-CCl 2 F
기상반응의 촉매로서는 Cr 또는 Al계의 촉매가 알려져 있으나 반응온도가 높아 (300-400℃ CH3CF3의 생성이 증가하는 문제점이 있다.Cr or Al-based catalysts are known as gas phase reaction catalysts, but the reaction temperature is high (300-400 ° C. CH 3 CF 3 production increases.
본 발명은 활성탄에 담지된 SbF3를 촉매로 하여 1,1,1-트리클로로에탄과 불화수소를 반응시켜 반응 전환율과 선택성이 높게 1,1-디콜로-1플루오로에탄 및 1-클로로-1,1-디플루오로에탄올을 제조하는 방법으로 종래의 액상 불소화 반응의 단점 즉, 고압반응으로 인한 과도한 장치비가 소요되고, 반응 공정이 복잡하며, 액상촉매를 사용함으로써 필연적으로 야기되는 장치의 심각한 부식 문제 및 타르의 형성, 내구성이 작은 고가의 촉매를 사용하는데 따른 제품의 원가 상승 문제를 해결하고 또한 Cr 또는 Al계 촉매를 사용하는 종래의 기상 불소화 반응의 문제점인 과불화물인 CH3CF3의 생성을 최소화할 수 있는 개선된 방법이다.In the present invention, 1,1,1-trichloroethane and hydrogen fluoride are reacted by using SbF 3 supported on activated carbon as a catalyst, so that the conversion and selectivity of 1,1-dicolo-1fluoroethane and 1-chloro- are high. The method for producing 1,1-difluoroethanol is a disadvantage of the conventional liquid fluorination reaction, that is, excessive equipment cost due to the high pressure reaction, the reaction process is complicated, and serious problems of the device inevitably caused by using a liquid catalyst It solves the problem of corrosion, the formation of tar, the cost increase of the product due to the use of expensive catalysts with low durability, and the CH 3 CF 3 which is a perfluoride which is a problem of the conventional gas phase fluorination reaction using Cr or Al-based catalyst. It is an improved way to minimize production.
이때, CH3CCl3와 HF의 반응은 염소원자와 불소 원자의 교환반응 [반응식 (1)(2)]과 탈염화수소 및 불화수소첨가반응[반응식(3)-(6)]이 동시에 일어난다.At this time, the reaction of CH 3 CCl 3 and HF simultaneously occurs the exchange reaction of chlorine and fluorine atoms (Scheme (1) (2)) and the addition of dehydrochlorination and hydrogen fluoride (Scheme (3)-(6)).
〈CL-F교환반응〉<CL-F exchange reaction>
CH3CCl3+HF→CH3CCl2F+HCl…………………………(1)CH 3 CCl 3 + HF → CH 3 CCl 2 F + HCl... … … … … … … … … … (One)
CH3CCl2F+HF→CH3CClF2+HCl……………………… (2)CH 3 CCl 2 F + HF → CH 3 CClF 2 + HCl... … … … … … … … … (2)
〈탈염화수소 및 불화수소첨가반응〉<Dehydrochlorination and hydrogen fluoride addition reaction>
CH3CCl2+CH2=CCl2+HCl……………………………… (3)CH 3 CCl 2 + CH 2 = CCl 2 + HCl. … … … … … … … … … … … (3)
CH2=CCl2+HF→CH3CCl2F……………………………… (4)CH 2 = CCl 2 + HF → CH 3 CCl 2 F... … … … … … … … … … … … (4)
CH2CCl2F→CH2=CClF+HCl…………………………… (5)CH 2 CCl 2 F → CH 2 = CClF + HCl... … … … … … … … … … … (5)
CH2=CClF+HF→CH2CClF2…………………………… (6)CH 2 = CClF + HF → CH 2 CClF 2 . … … … … … … … … … … (6)
본 발명에서 사용하는 촉매는 SbF3를 일정량의 메탄올 또는 아세톤에 용해시켜 활성탄과 혼합한 후 건조하여 제조하는데 이렇게 제조한 촉매는 적당한 용기에 옮겨서 100-200℃에서 30-300분간 질소기류하에서 완전히 건조하고 100-200℃에서 30-300분간 HF로 예비처리한다. 이때 사용되는 활성탄의 형태는 펠릿, 분말 또는 과립이며, 활성탄에 대한 SbF2의 양은 5-80%, 바람직하기로는 20-50%이다.The catalyst used in the present invention is prepared by dissolving SbF 3 in a predetermined amount of methanol or acetone, mixing with activated carbon, and drying the catalyst. The catalyst thus prepared is completely dried under nitrogen stream at 100-200 ° C. for 30-300 minutes. And pre-treated with HF at 100-200 ° C. for 30-300 minutes. The form of activated carbon used at this time is pellets, powders or granules, and the amount of SbF 2 for activated carbon is 5-80%, preferably 20-50%.
1,1,1-트리클로로에탄과 불화수소간의 기상반응은 50-200℃, 바람직하기로는 100-150℃에서 수행하는데 100℃이하의 온도에서는 반응속도가 낮아 공업적 생산을 위하여는 대형 반응기를 필요로 하며, 150℃이상의 온도에서는 촉매가 휘발할 우려가 있을뿐 아니라 CH3CF3의 생성이 증가한다.The gas phase reaction between 1,1,1-trichloroethane and hydrogen fluoride is carried out at 50-200 ° C, preferably 100-150 ° C. At temperatures below 100 ° C, the reaction rate is low and large reactors are used for industrial production. At temperatures above 150 ° C., there is a risk of volatilization of the catalyst and an increase in the production of CH 3 CF 3 .
촉매외의 접촉시간은 1-60초 바람직하기로는 5-30초이나, 1,1,1-트리클로로에탄과 불화수소의 몰비는 1,1,1-트리클로로에탄 1몰에 대하여 불화수소1-10몰, 바람직하기로는 2-5몰이다. 압력은 중요하지 않으나 염화수소 분리조작등 후처리를 위하여 대기압-10기압 바람직하기로는 0.5-3기압이다.The contact time other than the catalyst is 1-60 seconds, preferably 5-30 seconds, but the molar ratio of 1,1,1-trichloroethane and hydrogen fluoride is hydrogen fluoride 1-to 1 mole of 1,1,1-trichloroethane. 10 moles, preferably 2-5 moles. The pressure is not important, but atmospheric pressure -10 atm, preferably 0.5 -3 atm, for post-treatment such as hydrogen chloride separation.
반응기의 재질은 Inconel-600이다.The material of the reactor is Inconel-600.
본 발명의 실시예를 들면 다음과 같다.Examples of the present invention are as follows.
실시예에서 특별한 기재가 없으면 %는 몰%이고, 압력은 기압단위이며, 반응생성물의 분석은 OV-101 칼럼을 사용하는 기체크로마토그래피 및 질량크로마토그래피에 의하였다.Unless otherwise specified in the examples,% is mole%, pressure is in barometric pressure, and reaction products were analyzed by gas chromatography and mass chromatography using an OV-101 column.
[실시예 1(촉매제조)]Example 1 (catalyst production)
200g의 메탄올에 완전히 용해된 SbF320g을 활성탄 40g과 잘 혼합시켜 SbF3를 활성탄에 충분히 담지시킨 후 메탄올을 증발시켜 건조시켰다.20 g of SbF 3 completely dissolved in 200 g of methanol was mixed well with 40 g of activated carbon to sufficiently support SbF 3 in activated carbon, and methanol was evaporated to dryness.
건조된 촉매의 무게는 58g이었으며, 활성탄에 대해 45%의 SbF3가 담지되었다. 이렇게 제조된 촉매 29g을 반응기에 (2.54㎝직경, 30㎝길이 인코넬튜브)에 충전시키고 50ml/분의 속도로 질소기체를 공급하면서 반응기의 온도를 150℃까지 가열한 후 그 온도에서 2시간 유지시켜 촉매를 완전히 건조시켰다. 촉매가 완전 건조된 후에는 HF와 N2(:몰비)를 통과시키면서 점차 HF의 양을 증가시켰으며, 마지막에는 순수한 HF만을 반응기에 공급하였고 온도를 180℃로 올려 약 1시간 유지시켰다.The dried catalyst weighed 58 g and was loaded with 45% SbF 3 for activated carbon. 29 g of the catalyst thus prepared was charged in a reactor (2.54 cm diameter, 30 cm length inconel tube), the nitrogen gas was supplied at a rate of 50 ml / min, and the temperature of the reactor was heated to 150 ° C. and maintained at that temperature for 2 hours. The catalyst was completely dried. After the catalyst was completely dried, the amount of HF was gradually increased while passing through HF and N 2 (: molar ratio). Finally, only pure HF was supplied to the reactor, and the temperature was raised to 180 ° C. and maintained for about 1 hour.
[실시예 2-5]Example 2-5
[1,1,1-트리클로로에탄의 불소화][Fluorination of 1,1,1-trichloroethane]
실시예 1에서 제조한 예비처리된 촉매 존재하에 표 1의 조건하에서 1,1,1-트리클로로에탄과 HF을 반응시킨 결과를 표 1에 나타내었다. 1,1,1-트리클로로에탄과 불화수소는 150℃로 가열된 증발기에서 기화시킨 다음 반응기로 도입하였고, 반응기에서 빠져나온 유출물은 MgO현탁수용액 및 물로 세척하여 HF 및 HCL을 제거하고 CaCl2건조시킨 후 -60℃에서 냉각 포집하였다.Table 1 shows the results of reacting 1,1,1-trichloroethane with HF under the conditions of Table 1 in the presence of a pretreated catalyst prepared in Example 1. 1,1,1-trichloroethane and hydrogen fluoride were vaporized in an evaporator heated to 150 ° C. and introduced into the reactor, and the effluent from the reactor was washed with MgO suspension and water to remove HF and HCL, and CaCl 2 After drying it was collected by cooling at -60 ℃.
[표 1]TABLE 1
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