CN1063676A - 高级氯甲烷的脱氯方法 - Google Patents

高级氯甲烷的脱氯方法 Download PDF

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CN1063676A
CN1063676A CN91102768A CN91102768A CN1063676A CN 1063676 A CN1063676 A CN 1063676A CN 91102768 A CN91102768 A CN 91102768A CN 91102768 A CN91102768 A CN 91102768A CN 1063676 A CN1063676 A CN 1063676A
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chloromethane
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metal
hydrogen
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CN1031991C (zh
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伊夫斯·科雷亚
约瑟夫·诺沃西恩
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Arkema France SA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/42—Platinum

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  • Chemical Kinetics & Catalysis (AREA)
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  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Saccharide Compounds (AREA)

Abstract

本发明涉及一种在以铜族金属或铂族贵金属为 主要成分的催化剂存在下用氢和氧使高级氯甲烷脱 氯的方法。

Description

本发明是一种高级氯甲烷，即氯仿（CHCl3）和四氯化碳（CCl4）的脱氯方法。
工业规模合成氯甲烷类的方法基于甲烷或氯甲烷（CH3Cl）的氯化，由于此反应容易进行，所以完全没有选择性。例如，不可能只生产二氯甲烷（CH2Cl2）而不生成氯仿和四氯化碳。
所有的氯甲烷类都是合成中间体，例如，如果只使用氯仿，那么不知道四氯化碳该怎么办。因此，为了制造含氯量少的氯甲烷或甲烷本身，安排一些氯甲烷脱氯的方法是有用的。
美国专利3，579，596描述了一种在铂催化剂存在下，气相的四氯化碳或氯仿与氢的反应。按照这种先有技术，四氯化碳被退减为氯仿或甲烷。用这种方法进行反应，发现催化剂会被污染，反应温度也不稳定。
在《催化杂志》（Journal  of  Catalysis）1971年22期245-254页，ALVIN  H.WEISS、BALJIT  SINGH  GAMBHIR和RICHARD  B.LEON的《四氯化碳的加氢脱氯》一文中描述了一种相似的反应。
现已发现，可以在催化剂作用下，借助于氢和氧进行高级氯甲烷的脱氯反应，并且这个反应的温度是稳定的，催化剂也不受污染。
因此，本发明是一种借助于氢和以铜族金属或Ⅷ族贵金属为主要成分的催化剂使高级氯甲烷脱氯的方法，其特征在于该反应在氧存在下进行。
本发明的方法可以使四氯化碳脱氯制造氯仿和甲烷，或者使氯仿脱氯制造二氯甲烷和甲烷。进行高级氯甲烷类的混合物的脱氯也不超出本发明的范围。对混合物进行该反应，就可成功地使最大部分的四氯化碳脱氯。比较有利的是对气相的高级氯甲烷实施本发明的方法。
可以使用氧或含氧的气体，只要在本发明的反应条件下该含氧气体中的非氧组分是惰性的即可。比较有利的是使用空气。
催化剂可由沉积在载体上的金属组成。该金属选自铜族金属即铜、银和金，也选自Ⅷ族贵金属即钌、铑、钯、锇、铱和铂;也可包括这些金属的混合物。
所述载体比较有利的是由比表面为20至300米2/克的氧化铝和氧化钛构成。金属含量一般为0.05～5%，最好为0.1～1%（以催化剂的总重量计，即以金属和载体的总重量计）。可用如下方法实施本发明的方法，即将氯甲烷、氢和氧（或空气）的气流通过一个固定床或流化床的催化剂。然后用换热器进行简单的冷却以分离（ⅰ）未反应的氢和氧（或空气）以及反应过程中形成的甲烷和氢氯酸（HCl）和（ⅱ）含氯烃类。
例如，如果对四氯化碳实施本发明的方法，所述含氯烃类就可以是未反应的四氯化碳、氯仿、二氯甲烷、四氯乙烯（C2Cl4）、六氯乙烷（C2Cl6）和一氯甲烷（CH3Cl）。然后可将这些含氯烃类部分或全部分离，再将四氯化碳以与氢和氧的混合物形式循环到本发明方法中使用。
该反应可在负压或等于或超过大气压的压力（最高可达10巴）下进行。反应温度比较有利的是30～350℃，最好为100～250℃。
H2/高级氯甲烷的摩尔比大于1，最好为1～10。可以空气形式使用的氧比较有利的是氢的0.01～5%（摩尔）。由催化剂的体积与氢反应物、高级氯甲烷和氧或含氧气体的总流量（在正常条件下，即大气压和0℃下）之比所定义的停留时间为0.1～10秒，最好为0.5～5秒。
实例
一个反应器由一个具有双夹套的玻璃垂直管组成，内管内径26毫米，高850毫米。从上面开始在该内管中放置600毫米5mm×5mm的玻璃环，然后放110毫米催化剂，最后是60毫米的前述的玻璃环。
从上面向反应器中通入反应物。在催化剂内放置3个温度探测器，从催化剂最高面向下20毫米处为T1，在T1下面30毫米，即从催化剂最高面向下50毫米处为T2，在T2下面50毫米，即从催化剂最高面向下100毫米处为T3。在反应器出口装有一个-30℃的冷凝器，用来截留含氯烃类，然后用水洗涤所通过的气体以除去HCl，最后残余气体流过一个流量计。
在上述反应器中装入在比表面为125米2/克的氧化铝上沉积了0.5%铂的催化剂，通入CCl4、氢和空气的混合物。
反应条件和结果列于表1。
作为对比例，按如下方法进行：
-停止加入空气，就会发现，四氯化碳的转化率、床层产率下降，而全氯乙烯（PER）和六氯乙烷（Hexa）含量增加。反应条件和结果列于表1底部。
-使用新催化剂，在同样条件下但不用空气进行试验。反应条件和结果列于表2。
通过这些试验，可以看到，加入氧能够避免污染催化剂并能更好地控制温度;氧几乎完全转变为水。
在表1和表2中，停留时间是用催化剂的体积与标准条件TPN（即常温常压）下反应物、氮气、四氯化碳、氧气和氢气的总流量之比来表示的。
在这两个表中，浴温为双层夹套中循环流体的温度，H2/CCl4比是摩尔比，空气用加入的氢气的体积百分数表示。
Figure 911027688_IMG2

Claims (9)

1、借助于氢和以铜族金属或Ⅷ族贵金属为主要成分的催化剂，使高级氯甲烷脱氯的方法，其特征在于，该反应在氧存在下进行。
2、按照权利要求1的方法，其特征在于，所述高级氯甲烷是四氯化碳。
3、按照权利要求1或2的方法，其特征在于，所述催化剂由在比表面为20至300米2/克的氧化铝和氧化钛载体上沉积的所述金属组成。
4、按照权利要求3的方法，其特征在于，所述金属的含量为金属和载体总重量的0.5～5%，最好为0.1～1%。
5、按照权利要求1至4中任何一项的方法，其特征在于，所述温度为30～350℃，最好为100～250℃。
6、按照权利要求1至5中任何一项的方法，其特征在于，停留时间为0.1至10秒。
7、按照权利要求1至6中任何一项的方法，其特征在于，氢与高级氯甲烷的摩尔比大于1，最好为1至10。
8、按照权利要求1至7中任何一项的方法，其特征在于，氧与氢的摩尔比为0.01～5%。
9、按照权利要求1至8中任何一项的方法，其特征在于所述金属为铂。
CN91102768A 1990-05-03 1991-05-03 高级氯甲烷的脱氯方法 Expired - Fee Related CN1031991C (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9005567 1990-05-03
FR9005567A FR2661671B1 (fr) 1990-05-03 1990-05-03 Procede de dechloration des chloromethanes superieures.

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CN1063676A true CN1063676A (zh) 1992-08-19
CN1031991C CN1031991C (zh) 1996-06-12

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EP (1) EP0455547B1 (zh)
JP (1) JPH07112989B2 (zh)
KR (1) KR950006519B1 (zh)
CN (1) CN1031991C (zh)
AT (1) ATE113022T1 (zh)
CA (1) CA2041744C (zh)
DE (1) DE69104644T2 (zh)
DK (1) DK0455547T3 (zh)
ES (1) ES2061198T3 (zh)
FI (1) FI94128C (zh)
FR (1) FR2661671B1 (zh)
NO (1) NO172742C (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100423833C (zh) * 2003-10-08 2008-10-08 株式会社德山 多氯代烷烃还原用催化剂、其制备方法以及低级氯代烷烃的制备方法

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ES2018748A6 (es) * 1989-12-22 1991-05-01 Ercros Sa Procedimiento para la fabricacion de cloroformo.
US5621151A (en) * 1990-10-09 1997-04-15 E. I. Du Pont De Nemours And Company Halocarbon hydrogenolysis
US5334782A (en) * 1991-04-23 1994-08-02 Ag Technology Co., Ltd. Method for producing a hydrogen-containing chloromethane
BE1005797A3 (fr) * 1992-05-14 1994-02-01 Solvay Procede de dechloration des chloromethanes superieurs.
US5453557A (en) * 1992-10-01 1995-09-26 The Dow Chemical Company Processes for converting chlorinated byproducts and waste products to useful materials
EP0662940B1 (en) * 1992-10-01 1997-10-22 The Dow Chemical Company Process for converting 1,1,2-trichloroethane to vinyl chloride and/or ethylene
US5426252A (en) * 1993-10-15 1995-06-20 Akzo Nobel Nv Catalytic hydrodechlorination of a chloromethane
US5811628A (en) * 1994-07-26 1998-09-22 Leuna-Katalysatoren Gmbh Method for the complete hydrodechlorination of chlorinated hydrocarbons
DE4426391C1 (de) * 1994-07-26 1995-12-14 Leuna Katalysatoren Gmbh Verfahren zur vollständigen Hydrodechlorierung von Chlorkohlenwasserstoffen
EP1753532A1 (en) * 2004-05-14 2007-02-21 Dow Gloval Technologies Inc. High selectivity catalyst for the conversion of carbon tetrachloride to chloroform

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US1930350A (en) * 1931-12-04 1933-10-10 Dow Chemical Co Method of making tetrachlorethylene and hexachlorethane
US2152890A (en) * 1936-07-07 1939-04-04 Herman B Kipper Process for the production of chlorinated unsaturated petroleum hydrocarbons
US3579596A (en) * 1968-03-29 1971-05-18 Dow Chemical Co Hydrogenolysis of carbon tetrachloride and chloroform
US4157380A (en) * 1976-11-26 1979-06-05 Prahl Walter H Recovery of hydrogen chloride and chlorine from chlorine-containing organic wastes
US4983783A (en) * 1989-07-25 1991-01-08 Illinois Institute Of Technology Reduction in carbon oxides in oxidative pyrolysis of halogenated methanes

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100423833C (zh) * 2003-10-08 2008-10-08 株式会社德山 多氯代烷烃还原用催化剂、其制备方法以及低级氯代烷烃的制备方法

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ES2061198T3 (es) 1994-12-01
EP0455547B1 (fr) 1994-10-19
FR2661671B1 (fr) 1992-07-17
JPH04225928A (ja) 1992-08-14
FI94128B (fi) 1995-04-13
FI912134A0 (fi) 1991-05-02
DE69104644D1 (de) 1994-11-24
DE69104644T2 (de) 1995-05-18
NO911722D0 (no) 1991-05-02
NO172742C (no) 1993-09-01
CA2041744A1 (fr) 1991-11-04
CN1031991C (zh) 1996-06-12
CA2041744C (fr) 2001-11-20
NO911722L (no) 1991-11-04
EP0455547A1 (fr) 1991-11-06
US5097081A (en) 1992-03-17
FI94128C (fi) 1995-07-25
KR910019940A (ko) 1991-12-19
KR950006519B1 (ko) 1995-06-16
FI912134A (fi) 1991-11-04
NO172742B (no) 1993-05-24
FR2661671A1 (fr) 1991-11-08
DK0455547T3 (da) 1995-01-09
JPH07112989B2 (ja) 1995-12-06
ATE113022T1 (de) 1994-11-15

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