CN1025325C - 制备1,1,1,2-四氟乙烷的方法 - Google Patents
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- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
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Abstract
在载于AlF3的Cr2O3催化剂存在下,使三氯乙烯于气相与1,1,1-三氟氯乙烷和氢氟酸反应,制得1,1,1,2-四氟氯乙烷,其中三氯乙烯/1,1,1-三氟氯乙烷摩尔比为5/95-50/50。
本方法提供的1,1,1,2-四氟乙烷产率高于90%,且催化剂的寿命意外地长。本发明方法通过使未反应的三氯乙烯和1,1,1-三氟氯乙烷进行循可以进行连续操作,这弥补了反应物总转化率低的缺陷。
Description
本发明涉及通过三氯乙烯(CHCl=CCl2)与氢氟酸在催化剂存在下于气相中进行反应制备1,1,1,2-四氟乙烷的方法。
已知通过1,1,1-三氟氯乙烷(下文称为133a)与氢氟酸进行如下气相催化反应:
可以得到1,1,1,2-四氟乙烷(下文称为134a)。
根据US4,129,603,所述反应可于300-400℃在氧化铬或至少部分碱性氟化铬催化剂的存在下进行,133a的转化率为20%134a的产率为91%。
根据所述的方法,由于133a脱氟化氢的缘故还形成CF2=CHCl,其沸点仅比134a高9℃,这使得不易将其分离,也不经济。
因此,比利时专利号863,913中介绍了一种减少或除去反应产物中上述杂质的方法,它包括用同样类型的催化剂于低温进行烯烃后氟化处理。
根据加拿大专利号1,124,265所述的另一方法,通过令133a氟化产物与KMnO4水溶液接触将这种烯烃的含量减至5-10ppm。
日本专利申请80-27138和联邦德国专利申请2,932,934介绍了其它通过用基于氧化铬的催化剂氟化133a来制备134a的方法。根据上述申请,转化率分别为21%和31%,134a产率分别为91%和98%。
欧洲专利号300,724介绍了一种在基于囟化锑的催化剂存在于液相对133a进行氟化来制备134a的方法。所述方法的缺点是选择性不高,尤其是产生相当量的五氟乙烷。在所述方法中,提到了通过在气相对三氯
乙烯进行氟化来制备134a所遇到的困难。
事实上,本申请者已经通过试验查明,于气相中采用诸如铬的氟氧化物之类的催化剂对三氯乙烯进行直接氟化,仅能得到产率为3%的134a,尽管133a的产率较高,三氯乙烯的转化率为92%。
此外,催化剂的活性迅速衰减,因此为了用这种方法制备具有可接受产率的134a,需要经常对催化剂进行再活化,这显然不利于工业规模的应用。
另一种方法是分别地在液相对三氯乙烯进行氟化来制备133a,然后在气相对133a进行氟化来制备134a。
然而,这种方法会带来显著的经济负担,因为这将需要两套具有不同技术要求的设备。
本申请者业已发现可以提供一种于气相制备134a且具有工业上可接受的转化率的方法,此方法还具有较高的选择性,具体做法是在由载于三氟化铝的Cr2O3组成的催化剂存在下,使三氯乙烯/133a摩尔比为5/95-50/50的混合物与氢氟酸反应。
在此方法中(提供该方法是本发明的目的),出人预料地发现,所用催化剂在很长时间范围内(数百小时)可以充分保持其活性,因此可以工业规模连续操作。
实施上述方法的优选模式是,首先向含有催化剂的反应器添加上述比例的三氯乙烯和133a混合物,以及氢氟酸,在反应器出口将生成的134a与其它反应产物(其中主要含有133a)相分离,然后向所述反应产物中补加三氯乙烯和氢氟酸以保持反应物的上述比例,并且将此反应产物循环回反应器。
三氯乙烯、133a和氢氟酸之间的反应一般在300-400℃,最好330-380℃,以及大气压或直至15个大气压的较高压力下进行。
优选的进料条件是三氯乙烯/133a摩尔比约为15/85。一般HF/(三
氯乙烯+133a)摩尔比不低于3,此比例不存在上限。然而,较好的是HF/(三氯乙烯+133a)摩尔比为3/1-10/1,最好4/1-6/1。
反应物与催化剂的接触时间只要高于一秒钟的最低限度就没有什么重要影响。一般讲接触时间为1-50秒,最好5-20秒。
本方法即可间歇操作,即仅在催化剂上操作一次便收集产物,也可连续操作,即如前所述在补加反应物使其保持预定比例后,将未反应的三氯乙烯和133a循环回反应器。
本发明方法中使用的催化剂包括载于γ形和/或β形AlF3的三氧化二铬。
具有较大表面积(如25-30m2/g的量级)的载体通常是优选的。
Cr2O3的用量一般为1-15%(重量)(以该载体催化剂中的Cr计算)。Cr2O3的百分数是γ形AlF3表面积的函数。
载体可以是粒度为20-200μ的粉末,然而,如果需要,也可以是颗粒形式。
AlF3除了γ和/或β形式外,还可含有δ形式,其含量可达30%(重量)。
α形AlF3也可使用,但其含量应加以限制,因为这种构形的活性小。
本发明的催化剂可用若干方法制备,其中一种优选的方法是:按照现有技术,在湿润或干燥条件下,用可溶的三价铬盐(如CrCl3·6H2O)的溶液浸泡上述晶型的AlF3载体。
对该催化剂进行干燥,以便除去其中的水份,然后添加到反应器中,任选在蒸汽和/或结晶水(它可作为氧化剂)存在下用空气或氮气对其进行活化处理。
活化处理一般是于200-600℃,最好于350-500℃温度进行,以便将铬转化为氧化物的形式。
上述AlF3的同素异形结构是已知的,可由X射线衍射谱鉴别,如J.C.P.D.S 1981和法国专利号1,387,927所述。
上述γ-C、δ-C和β-C相在法国专利号1,383,927中已有介绍。α相在Anal.Chem,29,984(1957)中已有介绍。
经长时间使用后,可通过高温(350-500℃)空气处理将催化剂再活化。
下列实例是为更好地说明本发明,并不对本发明构成限制。
例1
向一个直径为8cm长为100cm的装有烧结的铬镍铁合金多孔折流板的电加热铬镍铁合金管式反应器中,添加1680克按下述方法制备的催化剂。载体为AlF3,主要是γ形式,比表面为26m2/g,用CrCl3·6H2O水溶液浸泡该载体,比例为每千克AlF3492克CrCl3·6H2O。该溶液含492克CrCl3·6H2O和152毫升水,体积为450毫升,分为大约三等份依次加到AlF3上,每次添加后,将催化剂在大气压下于120℃干燥4小时。第三次干燥后,将该催化剂过筛并加到反应器中。
在加热到400℃的反应器中用氮气流(约100升/小时)将该催化剂流化10小时,然后将反应器置于操作温度。
例2 对比试验
向加热至380℃的上述反应器添加1.536摩尔/小时的三氯乙烯和9.137摩尔/小时的无水HF,HF/C2HCl3摩尔比为6。接触时间为9.6秒,它是根据非流化催化剂的比例和反应物在反应温度和压力(反应压力稍高于大气压)下的体积流量计算出来的。将离开反应器的气体取出1小时;吸收水中的HCl和HF,以及用氢氧化钠水溶液洗涤反应产物后,回收到182克产物,其摩尔组成如下:
CF3CH2Cl 87.9%
CF3CH2F 2.0%
C2HCl34.9%
余量主要是CF3CHF2和CF3CH3。C2HCl3的转化率为95.1%,CF3CH2Cl选择性为92.4%,而CF3CH2F选择性为2.1%。这些结果是在约50小时的操作期间得到的,未做任何其它变动,其后催化剂开始失活。
例3
于350℃和稍高于大气压的压力下,向上述反应器添加0.072摩尔/小时C2HCl30.62摩尔/小时CF3CH2Cl和3.814摩尔/小时无水HF,接触时间为19.5秒,HF/有机产物的摩尔比为5.5,C2HCl3在全部有机产物中的含量为10.4%。
按例2方法操作,回收80克产物,其摩尔组成如下:
CF3CH2Cl 82.1%
CF3CH2F 16.5%
余量主要是少量的CF2=CHCl、CHCl=CCl2、CF3CHF2和CF3CH3。三氯乙烯的转化几乎是定量的,总转化率为17.7%,CF3CH2F选择性为93.2%。
例4
在例3所述的条件下向上述反应器添加0.194摩尔/小时C2HCl3,1.010摩尔/小时CF3CH2Cl和7.403摩尔/小时无水HF,因而接触时间为10.2秒,HF/有机产物摩尔比为6.2,C2HCl3在全部有机产物中的含量为16.1%。
按类似于上述实例的方法进行操作,得到140克产物,其摩尔组成如下:
CF3CH2Cl 85.0%
CF3CH2F 13.6%
副产物与例3相同。三氯乙烯的转化几乎是定量的,总转化率为
14.5%,CF3CH2F选择性为93.8%。
例5
在例3所述的条件下向上述反应器添加0.250摩尔C2HCl3,0.714摩尔/小时CF3CH2Cl和7.468摩尔/小时无水HF,因而接触时间为10.4秒,HF/有机产物摩尔比为7.8,C2HCl3在全部有机产物中的含量为25.9%。
按类似于上述实例的方法进行操作,得到112克产物,其摩尔组成如下:
CF3CH2Cl 86.9%
CF3CH2F 11.8%
副产物与例3相同。三氯乙烯的转化几乎是定量的,总转化率为12.9%,CF3CH2F选择性为91.5%。
在这些条件下以及在上述实例的条件下,经过大约200小时的操作催化剂活性并没有明显下降。
例6
通过添加一个分离柱将上述实例中的反应器改装成能够连续操作的装置,轻产物(包括134a)在该分离柱处被取出,而CF3CH2Cl和较高沸点的产物与补加的新鲜三氯乙烯和HF一起被泵送回反应器,以便补充消耗掉的反应物。
为了保持三氯乙烯/CF3CH2Cl和HF/有机产物比例恒定,补加的新鲜物质量随时间变化会稍有波动。参考性的反应条件为:反应温度=350℃;接触时间=10秒;HF/有机产物摩尔比=6;在反应器入口处三氯乙烯/CF3CH2Cl摩尔比=15/85。
在将上述装置调整到操作条件及添加预制的三氯乙烯/CF3CH2Cl混合物后,于6小时内添加1.08摩尔新鲜三氯乙烯和4.50摩尔新鲜无水HF,而从蒸馏柱的顶部排出约1摩尔CF3CH2F和少量与前述实例相同的副产物。
Claims (6)
1、制备1,1,1,2-四氟乙烷的方法,它包括在载于三氟化铝上的三氧化二铬催化剂的存在下,其中铬的含量以该载体催化剂中的Cr计算为1-15%(重量),使三氯乙烯在气相中与1,1,1-三氟氯乙烷和氢氟酸在300-400℃进行反应,其中三氯乙烯/1,1,1-三氟氯乙烷的摩尔比为5/95-50/50,反应物与催化剂的接触时间不低于1秒。
2、按权利要求1的方法,其中反应是在330-380℃进行的。
3、按权利要求1或2的方法,其中接触时间为1-50秒。
4、按权利要求1或2的方法,其中接触时间为5-20秒。
5、按权利要求1或2的方法,其中三氟化铝的表面积为25-30m2/g。
6、按权利要求1或2的方法,它是按连续的方式操作的。
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IT8921159A IT1230779B (it) | 1989-07-12 | 1989-07-12 | Procedimento per preparare 1,1,1,2 tetrafluoroetano. |
IT21159A/89 | 1989-07-12 |
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CN1048699A CN1048699A (zh) | 1991-01-23 |
CN1025325C true CN1025325C (zh) | 1994-07-06 |
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EP (1) | EP0408005B1 (zh) |
JP (1) | JP2999229B2 (zh) |
KR (1) | KR0145411B1 (zh) |
CN (1) | CN1025325C (zh) |
AU (1) | AU627907B2 (zh) |
BR (1) | BR9003345A (zh) |
CA (1) | CA2020853C (zh) |
DE (1) | DE69006951T2 (zh) |
ES (1) | ES2062212T3 (zh) |
IT (1) | IT1230779B (zh) |
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-
1989
- 1989-07-12 IT IT8921159A patent/IT1230779B/it active
-
1990
- 1990-07-10 CA CA002020853A patent/CA2020853C/en not_active Expired - Fee Related
- 1990-07-11 DE DE69006951T patent/DE69006951T2/de not_active Expired - Lifetime
- 1990-07-11 UA UA4830540A patent/UA18253A/uk unknown
- 1990-07-11 RU SU904830540A patent/RU1838288C/ru active
- 1990-07-11 EP EP90113264A patent/EP0408005B1/en not_active Expired - Lifetime
- 1990-07-11 ES ES90113264T patent/ES2062212T3/es not_active Expired - Lifetime
- 1990-07-12 KR KR1019900010578A patent/KR0145411B1/ko not_active IP Right Cessation
- 1990-07-12 CN CN90104695A patent/CN1025325C/zh not_active Expired - Fee Related
- 1990-07-12 AU AU58931/90A patent/AU627907B2/en not_active Ceased
- 1990-07-12 JP JP2185166A patent/JP2999229B2/ja not_active Expired - Lifetime
- 1990-07-12 BR BR909003345A patent/BR9003345A/pt not_active IP Right Cessation
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1994
- 1994-11-10 US US08/337,128 patent/US5463151A/en not_active Expired - Lifetime
-
1995
- 1995-07-25 US US08/507,644 patent/US5608125A/en not_active Expired - Lifetime
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1996
- 1996-11-19 US US08/752,685 patent/US5880316A/en not_active Expired - Fee Related
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- 1998-12-11 US US09/209,942 patent/US6037508A/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
DE69006951D1 (de) | 1994-04-07 |
JPH0348632A (ja) | 1991-03-01 |
CN1048699A (zh) | 1991-01-23 |
KR910002751A (ko) | 1991-02-26 |
EP0408005A1 (en) | 1991-01-16 |
US5880316A (en) | 1999-03-09 |
KR0145411B1 (ko) | 1998-07-15 |
CA2020853C (en) | 1999-09-28 |
BR9003345A (pt) | 1991-08-27 |
AU5893190A (en) | 1991-01-17 |
IT1230779B (it) | 1991-10-29 |
US5608125A (en) | 1997-03-04 |
US6037508A (en) | 2000-03-14 |
AU627907B2 (en) | 1992-09-03 |
ES2062212T3 (es) | 1994-12-16 |
EP0408005B1 (en) | 1994-03-02 |
UA18253A (uk) | 1997-12-25 |
DE69006951T2 (de) | 1994-06-09 |
RU1838288C (ru) | 1993-08-30 |
IT8921159A0 (it) | 1989-07-12 |
JP2999229B2 (ja) | 2000-01-17 |
US5463151A (en) | 1995-10-31 |
CA2020853A1 (en) | 1991-01-13 |
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