CN1331067A - 245fa的制备 - Google Patents

245fa的制备 Download PDF

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CN1331067A
CN1331067A CN01104779.8A CN01104779A CN1331067A CN 1331067 A CN1331067 A CN 1331067A CN 01104779 A CN01104779 A CN 01104779A CN 1331067 A CN1331067 A CN 1331067A
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fluoro
propylene
chloro
formula
catalyzer
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CN1205157C (zh
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陈冰
M·Y·埃尔斯海克
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Arkema Inc
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Arkema Inc
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00Preparation of halogenated hydrocarbons
    • C07C17/093Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/21Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms with simultaneous increase of the number of halogen atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00Preparation of halogenated hydrocarbons
    • C07C17/38Separation; Purification; Stabilisation; Use of additives
    • C07C17/383Separation; Purification; Stabilisation; Use of additives by distillation

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)

Abstract

在金属盐催化剂的存在下使1233zd氢氟化成245fa的方法中,所作的改进包括使用式CF3-aClaCH=CHbCl2-b的烯类杂质含量低于100ppm的1233zd作为原料,式中a为1、2或3,b为0、1或2。

Description

245fa的制备
本发明涉及改进由1,1,1-三氟-3-氯-2-丙烯(“1233zd”)制备1,1,1,3,3-五氟丙烷(“245fa”)的方法,其中在金属盐催化剂的存在下使1233zd与氟化氢(“HF”)接触,尤其是通过使用式CF3-aClaCH=CHbCl2-b(式中a为1、2或3,b为0、1或2)的烯类杂质含量低于100ppm的1233zd作为原料,提高所述催化剂的寿命。1,1,1,3,3-五氟丙烷已知可用作发泡剂和制冷剂。
原料1233zd通常是通过含氯烯烃(如1,1,3,3-四氯丙烯(1230za),参见美国专利5,877,359)或含氯烷烃(如1,1,1,3,3-五氯丙烷(240fa),参见美国专利5,710,352)氟化制得的,这些方法通常都会由于氟化不充分而导致存在上述烯类杂质。为了使这些不纯的1233zd原料氢氟化的企图,会导致用于这些氢氟化反应的金属盐催化剂去活化(缩短其寿命)。
在金属盐催化剂的存在下使1233zd氢氟化成245fa的方法中,所作的改进包括使用式CF3-aClaCH=CHbCl2-b的烯类杂质含量低于100ppm的1233zd作为原料,式中a为1、2或3,b为0、1或2。
现已发现,使用上述烯类杂质含量低的1233zd原料会大大提高金属盐氢氟化催化剂的寿命,参见下文。
当1233zd原料中这些杂质的含量较高时,用常规的方法对1233zd进行预处理,如蒸馏,以使其中杂质的含量降低至100ppm以下,最好在10ppm以下。当杂质含量达到100ppm及更高时,上述催化剂的活性开始降低。我们发现常规的蒸馏对于使烯类杂质(如1,1-二氟-1,3-二氯-2-丙烯和1-氟-1,1,3-三氟-2-丙烯)的含量达到用气相色谱不能测出,即达到10ppm以下是有效的。
该方法可用于任何常规的承载的或未承载的金属盐催化剂,所述金属包括铬、镍、钴、铁、铜、锌、铝、锂、钾、钠、镁、锰、锑、钛、锡、钽、铌、钼、铑及其混合物。较好的催化剂是铬(III)基的,如承载在氟化铝载体上的铬/镍催化剂,参见欧洲专利486333。所述盐通常是卤化物,如氯化物或氟化物。这些金属卤化物催化剂可通过金属氧化物与HCl或HF反应而制得。关于常用的催化剂、载体、活化方法以及共用空气或氯共进料可参见美国专利5,811,603,该文献中关于催化剂和共进料的内容在此引作参考。
氢氟化反应的温度通常为25-600℃,较好为50-400℃。压力通常为15-600psig,较好为50-400psig。HF与1233zd的摩尔比通常为2-200,较好为3-50。
在下面的非限制性实施例中对本发明作更详细的说明,该实施例中使用欧洲专利486333中的Cr-Ni/AlF3催化剂,使1233zd氢氟化成245fa:
实施例
使用两种不同的原料,(a)1233zd,其中上述式CF3-aClaCH=CHbCl2-b的杂质含量达到不能测出,以及(b)1233zd,其中杂质1,1-二氟-1,3-二氯-2-丙烯的含量为1600ppm。将上述1233zd和HF反应物预混合,并在约380℃的温度和约155psig的压力下从催化剂上通过,其中所用的HF/1233zd摩尔比约为4∶1,并用空气共进料。当不纯的1233zd反应时,催化剂的寿命为140小时,而对于纯的1233zd原料,所用催化剂在400小时以上仍然具有活性。

Claims (3)

1.在金属盐的催化剂的存在下,使1,1,1-三氟-3-氯-2-丙烯氢氟化成1,1,1,3,3-五氟丙烷的方法,其特征在于所述方法中使用式CF3-aClaCH=CHbCl2-b的烯类杂质含量低于100ppm的1,1,1-三氟-3-氯-2-丙烯作为原料,式中a为1、2或3,b为0、1或2。
2.如权利要求1所述的方法,其特征在于所述催化剂是铬基的。
3.如权利要求1所述的方法,其特征在于对所述1,1,1-三氟-3-氯-2-丙烯原料进行预处理,以减少所述烯类杂质的含量。
CN01104779.8A 2000-05-08 2001-02-21 245fa的制备 Expired - Lifetime CN1205157C (zh)

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US56716900A 2000-05-08 2000-05-08
US09/567,169 2000-05-08

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CN1331067A true CN1331067A (zh) 2002-01-16
CN1205157C CN1205157C (zh) 2005-06-08

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EP (1) EP1153906B1 (zh)
JP (1) JP4750304B2 (zh)
CN (1) CN1205157C (zh)
AT (1) ATE240919T1 (zh)
DE (1) DE60100284T2 (zh)
ES (1) ES2198385T3 (zh)
MX (1) MXPA01002921A (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104080759A (zh) * 2011-10-14 2014-10-01 塞尔马·贝克特什维克 生产2,3,3,3-四氟丙烯的方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2748473B1 (fr) * 1996-05-13 1998-07-24 Atochem Elf Sa Synthese du 1-chloro-3,3,3 trifluoropropene et sa fluoration en 1,1,1,3,3 pentafluoropropane
JPH11180908A (ja) * 1997-12-19 1999-07-06 Daikin Ind Ltd 1,1,1,3,3−ペンタフルオロプロパンの製造方法及びその製造中間体の製造方法
JPH11180907A (ja) * 1997-12-19 1999-07-06 Daikin Ind Ltd 1,1,1,3,3−ペンタフルオロプロパンの製造方法
US5877359A (en) * 1998-01-27 1999-03-02 Elf Atochem North America, Inc. Uncatalyzed liquid phase fluorination of 1230ZA
DE69909860T2 (de) * 1998-02-26 2004-05-27 Central Glass Co., Ltd., Ube Verfahren zur Herstellung von fluorierten Propanen
US5981814A (en) * 1998-03-23 1999-11-09 Laroche Industries Inc. Vapor phase process for preparing fluorinated aliphatic compounds
JP3518321B2 (ja) * 1998-03-23 2004-04-12 ダイキン工業株式会社 1,1,1,3,3−ペンタフルオロプロパンの製造方法
JP3804289B2 (ja) * 1998-09-22 2006-08-02 ダイキン工業株式会社 1,1,1,3,3−ペンタフルオロプロパン及び/又は1−クロロ−3,3,3−トリフルオロプロペンの製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104080759A (zh) * 2011-10-14 2014-10-01 塞尔马·贝克特什维克 生产2,3,3,3-四氟丙烯的方法
US9359273B2 (en) 2011-10-14 2016-06-07 Honeywell International Inc. Process for producing 2,3,3,3-tetrafluoropropene

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DE60100284D1 (de) 2003-06-26
MXPA01002921A (es) 2002-04-24
EP1153906B1 (en) 2003-05-21
ATE240919T1 (de) 2003-06-15
EP1153906A1 (en) 2001-11-14
JP2001316305A (ja) 2001-11-13
ES2198385T3 (es) 2004-02-01
CN1205157C (zh) 2005-06-08
JP4750304B2 (ja) 2011-08-17
DE60100284T2 (de) 2004-05-13

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Granted publication date: 20050608