CN102958880B - 通过244bb的选择性脱氯化氢合成1234yf - Google Patents
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Abstract
公开制造2,3,3,3-四氟丙烯的方法,包括:(a)使1,1,1,2-四氟-2-氯丙烷与包含氧化铬(III)和至少1%的碱金属的催化剂接触,以产生包括2,3,3,3-四氟丙烯的产物混合物;和(b)从以上步骤(a)中产生的产物混合物中回收所述2,3,3,3-四氟丙烯。
Description
相关申请的交叉引用
本申请要求2010年7月6日提交的美国临时申请61/361,713的优先权。
发明背景.。
发明领域
本公开内容一般性涉及合成氟化烯烃的方法。
相关技术的说明
氟烃工业已经花费过去几十年研究以寻找由于蒙特利尔协议而被逐步淘汰的臭氧消耗氯氟烃(CFC)和氢氯氟烃(HCFC)的替代致冷剂。许多申请的解决方案为用作致冷剂、溶剂、灭火剂、发泡剂和推进剂的氢氟烃(HFC)的工业化。本时代最广泛使用的这些新的化合物,例如HFC致冷剂、HFC-134a和HFC-125,具有零臭氧消耗潜势,并因此不受由于蒙特利尔协议而逐步淘汰的现行规章的影响。
除臭氧消耗关切之外,全球变暖是许多这些申请中的另一个环境关切。因此,对于满足低臭氧消耗标准和具有低全球变暖潜势两者的组合物存在需求。某些氢氟烯烃据信满足这两个目的。因此,对于提供同样具有低全球变暖潜势的不含氯的卤代烃和氟烯烃的制造方法存在需求。
此外,在研发用于移动空调市场的全球变暖潜势降低的新致冷剂方面存在相当大的兴趣。
都具有零臭氧消耗和低全球变暖潜势的HFC-1234yf (CF3CF=CH2)和HFC-1234ze (CF3CH=CHF),作为潜在的致冷剂已经得到确认。美国专利公开号2006/0106263 A1公开通过CF3CF2CH3或CF3CHFCH2F的催化汽相脱氟化氢制造HFC-1234yf,以及通过CF3CH2CHF2的催化汽相脱氟化氢制造HFC-1234ze (E-和Z-异构体的混合物)。美国专利公开号2007/0197842公开利用活性碳、C上的Pd、C上的Pt或Ni网催化剂,通过CF3CFClCH3的催化汽相脱卤化氢制造HFC-1234yf。美国专利公开号2009/0030247公开利用CsCl和MgF2的催化剂,通过CF3CFClCH3的催化汽相脱氯化氢制造HFC-1234yf。
对于制造HFC-1234yf的更加选择性和有效的制造方法存在持续需求。
发明内容
在一个方面,公开制造2,3,3,3-四氟丙烯的方法,包括:使1,1,1,2-四氟-2-氯丙烷与包含(comprised of)氧化铬(III)和至少1%的碱金属的催化剂接触,以产生包含2,3,3,3-四氟丙烯的产物混合物;和从产生的产物混合物中回收所述2,3,3,3-四氟丙烯。
上述一般说明和下面的详细说明都仅仅是示例性和说明性的,并非本发明的限制,本发明如所附权利要求中定义的。
详细说明
在一个方面,公开制造2,3,3,3-四氟丙烯的方法,包括:使1,1,1,2-四氟-2-氯丙烷与包含(comprised of)氧化铬(III)和至少1%的碱金属的催化剂接触,以产生包含2,3,3,3-四氟丙烯的产物混合物;和从产生的产物混合物中回收所述2,3,3,3-四氟丙烯。
许多方面和实施方案已经如上所述,其仅为示例而非限制。阅读本说明书之后,本领域技术人员理解在不脱离本发明范围的基础上,可以有其它方面和实施方案。
任何一个或多个实施方案的其它特征和优点将由以下详细说明和权利要求而变得显而易见。
阐明如下所述实施方案的细节之前,定义或澄清某些术语。
氢氟烃或氢氯氟烃催化脱卤化氢制造氢氟烯烃通常使用脱卤化氢催化剂,在汽相中进行。汽相脱卤化氢催化剂在本领域中是公知的。这些催化剂包括但不限于氧化铝,氟化铝,氟化氧化铝,氟化铝上的金属化合物,氟化氧化铝上的金属化合物;氧化铬,氟化氧化铬,和立方体三氟化铬;镁、锌以及镁和锌和/或铝的混合物的氧化物、氟化物和氟氧化物;氧化镧和氟化氧化镧;碳,酸洗碳,活性碳,三维基质含碳材料;和碳上担载的金属化合物。金属化合物为选自钠,钾,铷,铯,钇,镧,铈,镨,钕,钐,铬,铁,钴,铑,镍,铜,锌及其混合物的至少一种金属的氧化物、氟化物和氟氧化物。汽相脱氯化氢的催化剂包括活性碳,碳上的钯,碳上的铂,镍网,和CsCl和氟化镁的组合。
在通过CF3CFClCH3的脱卤化氢制备HFC-1234yf中,可以获得HFC-1234yf或HCFC-1233xf,取决于发生脱氯化氢还是脱氟化氢。
使用包括氧化铬(III),和碱金属的催化剂,通过竞争脱氟化氢,可以以高选择性和极少HCFC-1233xf形成,将CF3CClFCH3 (HFC-244bb)脱氯化氢成为HFC-1234yf。制造HFC-1234yf的选择性可以用副产物相对于HFC-1234yf的量的百分之几来表示。例如,由HFC-244bb脱氯化氢形成的包括60%HFC-1234yf和20%HCFC-133xf的产物混合物将具有33 pph的HCFC-1233xf。在一个实施方案中,碱金属以至少1 wt%的量存在。在另一个实施方案中,碱金属以至少1.5
wt%的量存在于催化剂中。在一个实施方案中,碱金属选自钠、钾、铷和铯。在一些实施方案中,催化剂进一步包括硼。
在一个实施方案中,催化剂包括氧化铬(III),0.1%至3%的硼和至少1000 ppm的钾。在另一个实施方案中,催化剂包括氧化铬(III),0.5%至2%的硼和至少1000 ppm的钾。在另一个实施方案中,催化剂包括氧化铬(III),0.5%至2%的硼和至少2000 ppm的钾。在另一个实施方案中,催化剂包括氧化铬(III)和至少1000
ppm的钾。在另一个实施方案中,催化剂包括氧化铬(III)和至少1500 ppm的钾。
在一个实施方案中,可以通过在500-800℃下熔合3份至16份硼酸和1份重铬酸钾的混合物,在空气中冷却该混合物,将固体破碎来制造粉末,水解,过滤,干燥,研磨和过筛来制备催化剂。本领域中可以找到制备古纳特绿(Guignet's
green)的许多实例,包括US 3,413,363,在此将其公开内容引入作为参考。
在另一个实施方案中,可以通过将古纳特绿铬与另外的钾掺杂来制备催化剂。在另一个实施方案中,可以通过将氧化铬与钾掺杂来制备催化剂。
催化剂的物理形状并非关键,可以例如包球粒、粉末或粒料。
反应压力可以为低于大气压、常压或超过大气压。通常,接近大气压是优选的。但是,脱氟化氢可以有利地在减压(即压力低于一个大气压)下进行。
在一个实施方案中,催化脱氟化氢在惰性气体例如氮气、氦气或氩气存在下进行。添加惰性气体可用于提高脱氟化氢程度。值得注意的是其中惰性气体对经历脱氟化氢的氢氟烃的摩尔比为约5:1至约0.5:1的方法。在一个实施方案中,氮气为惰性气体。
如在此使用的,术语“包含(comprises,comprising)”、“包括(includes,including)”、“具有(has,having)”或其任何其它变化用来覆盖非排他性包含。例如,包括一系列元素的工艺、方法、制品或装置并非必须只限于那些元素,而是可以包括并未明确列出的或者这种工艺、方法、制品或装置固有的其它元素。此外,除非相反地明确说明,“或”表示与或,和不表示异或。例如,以下任何一个满足条件A或B:A为真(或存在)和B为假(或不存在),A为假(或不存在)和B为真(或存在),以及A和B都为真(或存在)。
此外,使用“一个”或“一种”来描述在此描述的元素和组分。这仅是为了方便起见以及给出本发明范围的一般含义。这种说明应解读为包括一个(种)或至少一个(种),并且单数还包括复数,除非显然其以另外方式表示。
对应于元素周期表内各列的族号使用如CRC Handbook of Chemistry and Physics,第81版(2000-2001)中所示的“新符号(New Notation)”协定。
除非另外定义,在此使用的所有科技术语具有与由本发明所属领域的本领域普通技术人员通常理解的相同含义。虽然与在此所述的那些相似或等效的方法和材料都可以用于本发明实施方案的实践或测试,但是以下描述合适的方法和材料。将在此提及的所有出版物、专利申请、专利和其它参考文献全部引入作为参考,除非引用特定的段落。在冲突的情况下,本说明书,包括定义,将是对照物。另外,材料、方法和实施例仅是说明性的,并不意图进行限制。
实施例
在此描述的构思将在以下实施例中做进一步描述,该实施例并不限制权利要求中描述的本发明的范围。
实施例1
实施例1说明掺杂有钾的氧化铬催化剂的制备。
在1000 ml Teflon®烧杯中,将200
ml去离子水中的KHCO3 (4.35 gm)溶液与氧化铬(古纳特绿,购自Elementis
Chromium)混合。伴随偶尔搅拌,将料浆在室温下放置1小时。蒸干之后,将所得固体破碎至均匀粉末并放入陶瓷盘中。将其经 4小时加热至400℃,然后在静态空气中保持在400℃下。在冷却到室温之后称量固体,得到88.56
gm。将粉末加压至30,000 psi,破碎所得固体并过筛至12/20目。由ICP分析粉末,发现包含以下微量组分:B,1.92%;Ca,3040 ppmw;Fe,960 ppmw;K,2.01%;Mg,605 ppmw;Na,4920 ppmw;Si,41 ppmw;Sr,25 ppmw。
实施例2
实施例2说明244bb利用实施例1中制备的掺杂氧化铬催化剂的脱氯化氢。
将铬镍铁合金管(1/2英寸OD)填充4 cc (5.03 gm)的实施例1的催化剂。以0.82 ml/小时将HFC-244bb进料通过设置在40℃的蒸发器,使用3.0 sccm的N2吹扫,产生约33秒的总接触时间,同时经18小时使温度上升直至525℃。检测无245cb。
表
1
实施例3利用高钾氧化铬催化剂的脱氯化氢。
将铬镍铁合金管(1/2英寸OD)充满4 cc (3.87 gm)的钾含量高的古纳特绿的商业试样。以0.82
ml/小时将HFC-244bb进料通过设置在40℃的蒸发器,使用3.0 sccm的N2吹扫,产生约33秒的总接触时间,同时经18小时使温度上升直至525℃。检测无245cb。结果在下表中以摩尔百分比的形式标明。
表
2
由ICP分析该催化剂的试样,发现包含以下微量组分:B,1.6 wt%,K,1.7 wt%,Ca,50 ppm,Fe,72 ppm,Na,49 ppm,Si,75 pm,Zr,17 ppm。
实施例4
实施例4说明244bb在古纳特绿的无掺杂商业试样上的脱卤化氢。
将铬镍铁合金管(1/2英寸OD)充满4 cc (3.32 gm)的以上实施例1中使用的无掺杂氧化铬。以0.82 ml/小时将HFC-244bb进料通过设置在40℃的蒸发器,使用3.0 sccm的N2吹扫,产生约33秒的总接触时间,同时经24小时使温度上升直至525℃。
表
3
由ICP分析该催化剂的试样,发现包含以下微量组分:B,1.6 wt%,K,150 ppm,Ca,2800 ppm,Fe,820 ppm,Na,4550 ppm,Si,135 pm,Zr,<1 ppm。
实施例5
实施例5说明在活性碳催化剂存在下,2-氯-1,1,1,2-四氟丙烷的脱氯化氢。
将铬镍铁合金管(1/2英寸OD)充满4 cc (1.99 gm)的购自Calgon的酸洗PCB Polynesian椰子壳基碳(6-10目)。将HFC-244bb以1.04 ml/小时进料通过设置在40℃的蒸发器,使用2.4 sccm (4.0×10-8
m3)的N2吹扫,产生约32秒的总接触时间,同时将反应器温度控制在400℃。
表4中的数据表明利用活性碳催化剂,通过15小时运行时间的HCl脱除,产生HFO-1234yf的该方法的特性。
表
4
注意以上概述或实施例中描述的所有活性并非都需要,可能不需要一部分特殊活性,除描述的那些之外,可以表现一种或多种其它活性。更进一步,其中所列活性的顺序并非必然是其中表现它们的顺序。
在上述说明书中,已经根据特殊实施方案描述构思。但是,本领域普通技术人员理解可以进行各种改进和变化而不脱离如以下权利要求中阐明的本发明的范围。因此,说明书和附图被认为是说明性的而非限制性的含义,以及意图将所有这种改进包括在本发明范围内。
以上根据特殊实施方案描述了各好处、其它优点和问题的解决方案。但是,可能导致任何好处、优点或解决方案出现或变得更加显著的的好处、优点、问题解决方案和任何一种或多种特征并不被认为是任何或所有权利要求的关键、所需或必要的特征。
应理解为了清楚,在独立的实施方案的背景下描述的某些特征也可以在单一实施方案中以组合的形式提供。相反地,为了简便起见,单一实施方案的背景下描述的各个特征也可以单独地或以任何再组合的形式提供。此外,范围中说明的各值包括该范围内的每一个值。
Claims (9)
1.制造2,3,3,3-四氟丙烯的方法,包括:(a)使1,1,1,2-四氟-2-氯丙烷与包含氧化铬(III)和至少1%碱金属的催化剂接触,以产生包含2,3,3,3-四氟丙烯的产物混合物;和(b)从(a)中产生的所述产物混合物中回收所述2,3,3,3-四氟丙烯。
2.权利要求1的方法,其中所述接触步骤发生在加热的容器中,其中温度设定值为至少400℃。
3.权利要求1的方法,其中所述接触步骤发生在加热的容器中,其中温度设定值为至少470℃。
4.权利要求1的方法,其中所述产物混合物包含低于15%的2-氯-3,3,3-三氟丙烯。
5.权利要求1的方法,其中所述产物混合物包含低于10%的2-氯-3,3,3-三氟丙烯。
6.权利要求1的方法,其中所述产物混合物包含低于5%的2-氯-3,3,3-三氟丙烯。
7.权利要求1的方法,其中所述催化剂包含至少1 wt%的钾。
8.权利要求1的方法,其中所述催化剂包含至少1.5 wt%的钾。
9.权利要求1的方法,其中所述催化剂包含至少1 wt%的铯。
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US9180433B2 (en) | 2013-03-14 | 2015-11-10 | Honeywell International, Inc. | Catalysts for 2-chloro-1,1,1,2-tetrafluoropropane dehydrochlorination |
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