WO2009031719A1 - Method for preparing chlorinated compound from saturated hydrocarbon - Google Patents

Method for preparing chlorinated compound from saturated hydrocarbon Download PDF

Info

Publication number
WO2009031719A1
WO2009031719A1 PCT/KR2007/004235 KR2007004235W WO2009031719A1 WO 2009031719 A1 WO2009031719 A1 WO 2009031719A1 KR 2007004235 W KR2007004235 W KR 2007004235W WO 2009031719 A1 WO2009031719 A1 WO 2009031719A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
reaction
saturated hydrocarbon
chlorination
methane
Prior art date
Application number
PCT/KR2007/004235
Other languages
French (fr)
Inventor
Yong-Ho Lee
Dong-Hyun Jo
Jong-Wook Bae
Sung-Won Kim
Soon-Yeel Lee
Kyung-Seop Noh
Sang-Seung Oh
Je-Sik Jung
Ye-Hoon Kim
Ho-Jeong Chae
Gi-Moon Nam
In-Seop Kim
Kum-Hyoung Lee
Original Assignee
Lg Chem, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lg Chem, Ltd. filed Critical Lg Chem, Ltd.
Priority to PCT/KR2007/004235 priority Critical patent/WO2009031719A1/en
Priority to CN200780052860A priority patent/CN101663258A/en
Publication of WO2009031719A1 publication Critical patent/WO2009031719A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/08—Halides
    • B01J27/122—Halides of copper

Definitions

  • the present invention relates to a method for preparing chlorinated compounds from saturated hydrocarbon. More particularly, the present invention relates to the method for preparing chlorinated compounds, in which an oxidation step for a catalyst to be used for a chlorination of saturated hydrocarbon performed under oxygen and hydrogen chloride and a chlorination step for converting saturated hydrocarbon into chlorinated compounds by using the above catalyst.
  • the present invention has the advantages that the conversion rate of the saturated hydrocarbon may be enhanced; there is no need to consider explosion hazards; unreacted hydrogen chloride and corrosion of reactor may be reduced; there is no need to provide a separate device for separating CO x in exhaust gases since CO or CO 2 is not produced by a combustion reaction; by-product may not be produced; and a durability of the catalyst may be remarkably enhanced.
  • methyl chloride (CH 3 Cl) is prepared by reacting methane, oxygen and hydrogen chloride in a single step on a supported catalyst having metallic salt of copper and iron as a basal component.
  • a supported catalyst having metallic salt of copper and iron as a basal component.
  • the research about an effect and pressure caused by adding the second metal to copper salt which is a basal catalyst component, and the like have been also reported as a method for improving the stability of catalyst and the selectivity of catalyst for methyl chloride (CH 3 Cl) of a catalyst (J. Am. Chem. Soc, 107(1985), 7097; Appl. Catal, 46(1989), 251; Chem. Eng. ScL, 49(1994), 4627).
  • a method of supplying dividedly air may be used to maintain oxygen at a low concentration or a method of supplying the great quantity of saturated hydrocarbon gas may be used.
  • the method of supplying dividedly air causes a lowering of the productivity, and the excessive saturated hydrocarbon may cause a low conversion rate.
  • the process becomes complicated and the operation cost may be increased.
  • Water produced as a result of the reaction and hydrogen chloride as reactant are in contact with each other, and so the reactor is corroded. As a result, a service life time of the reactor is reduced.
  • a chlorination of saturated hydrocarbon is performed at a high temperature of 300 to 400 °C .
  • I f a catalyst is exposed to a condition of a high temperature for a long period, copper ion may be lost by sublimation of cupric chloride. Therefore, the durability of the catalyst may be lowered.
  • the conventional method for preparing chlorinated compounds through the single-step oxychlorination reaction in which gaseous mixture of saturated hydrocarbon, oxygen and hydrogen chloride is supplied simultaneously, has the problems of oxygen utilization, explosion hazards, a corrosion of reactor, a generation of CO or CO 2 and a deterioration of the catalyst durability, and so the above method is not commercially available. Accordingly, the development of method for preparing chlorinated compounds from saturated hydrocarbon, which does not have the problem as described above and is commercially available, has been required.
  • the present invention intends to solve problems of the prior art as described above, it is an object of the present invention to provide a method for preparing chlorinated compounds from saturated hydrocarbon, which can improve a conversion rate of saturated hydrocarbon, does not have to consider an explosion hazard, can reduce un-reacted hydrogen chloride to prevent a corrosion of a reactor, does not require a separate device for separating CO x from exhaust gas since CO or CO 2 caused by a combustion reaction is not produced, does not produce by-product and can enhance remarkably a durability of catalyst.
  • a method for preparing chlorinated compounds from saturated hydrocarbon comprises the steps of oxidizing a catalyst under oxygen and hydrogen chloride; and chlorinating saturated hydrocarbon under the oxidized catalyst.
  • the chlorinated compounds are prepared from methane.
  • an oxidation reaction of a catalyst and a chlorination reaction of methane are conducted separately as shown in the reaction formula (2) in which copper chloride is used as a catalyst:
  • the catalyst oxidation step performed under oxygen and hydrogen chloride for a chlorination of methane and the chlorination step for converting, for example, methane into chloromethane by using the oxidized catalyst are performed separately so that one or more chloromethane in which 1 to 4 of hydrogen of methane is substituted with chloride, that is, methyl chloride (CH 3 Cl), methylene chloride (CH 2 Cl 2 ), chloroform (CHCl 3 ) and carbon tetrachloride (CCl 4 ) are obtained.
  • the advantages which may be expected by performing separately the oxidation step and the chlorination step are as follows: a) Since the chlorination step for saturated hydrocarbon is carried out after the oxidation of a catalyst is sufficiently performed, the conversion rate of saturated hydrocarbon may be enhanced. As a result, the generation of by-product may be relatively reduced. b) Since oxygen and saturated hydrocarbon are separated from each other and are reacted with a catalyst in different steps, respectively, there is no need to consider explosion hazards. c) Since there is no need to consider explosion hazards, it is possible to supply oxygen and hydrogen chloride in the oxidation reaction in view of the stoichiometric proportion.
  • the chlorination reaction may be performed at a relatively lower temperature, and so it is possible to prevent a loss of copper ion in the catalyst caused by a high temperature. As a result, the durability of the catalyst is enhanced.
  • the above two steps are proceeded alternately in a single reactor.
  • the above two steps are proceeded independently in separate reactors and a catalyst is circulated continuously through a catalyst transferring pipe provided between these separate reactors.
  • the oxidation reaction of a catalyst and the chlorination reaction of saturated hydrocarbon may be carried out in a fixed bed reactor or a fluidized bed reactor.
  • a catalyst transferring pipe is provided between these separate reactors to circulate continuously the catalyst, it is preferable to employ the fluid bed reactor.
  • saturated hydrocarbon is used as a starting material, and preferably, an aliphatic saturated hydrocarbon having carbon numbers of 1 through 6 such as methane, ethane and propane etc. may be used. More preferably, methane or ethane may be used, and most preferably, methane may be used. If two or more kinds of saturated hydrocarbons are used, it will be apparent that a mixture thereof may be used.
  • the oxidation reaction of a catalyst is preferably performed at a temperature of 200 to 300 ° C, and more preferably at a temperature of 230 to 290 ° C . If the reaction temperature is less than 200 ° C , the oxidation reaction of the catalyst can not be performed smoothly. And, if the reaction temperature is more than 300 "C, copper ion in the catalyst may be lost so that an activity of the catalyst is deteriorated and the durability is lowered.
  • the chlorination reaction of saturated hydrocarbon needs a reaction temperature higher than that in the oxidation reaction of a catalyst.
  • a temperature which is higher than a temperature required for the oxidation reaction of catalyst should be maintained and such single-step oxychlorination reaction has a problem that a loss of the catalyst is caused by the exothermic oxidation reaction.
  • the oxidation reaction of catalyst and the chlorination reaction of saturated hydrocarbon are independently conducted, so the oxidation reaction may be performed at a relative low temperature. Also, since caloric value in the chlorination reaction conducted at a relative high temperature is not large, as compared with the conventional arts, a loss of the catalyst caused by a high temperature is extremely small.
  • a pressure condition is not particularly limited.
  • a suitable pressure condition can be selected from the range within atmospheric pressure of 1 to 20 according to a reaction equipment and the like.
  • the oxidation reaction of a catalyst may be preferably conducted at a space velocity (Weight Hour Space Velocity, WHSV) of reaction products in the range of 10 to 10,000 L/kg(cat)/hr, and more preferably in the range of 100 to 1,000 L/kg(cat)/hr.
  • space velocity Weight Hour Space Velocity
  • the above space velocity is less than 10 L/kg(cat)/hr, a production of undesired by-product may be increased, and the above space velocity is more than 10,000 L/kg(cat)/hr, unreacted material may be excessively increased to reduce the process efficiency.
  • the chlorination reaction of saturated hydrocarbon is preferably performed at a temperature of 200 ° C to 600 ° C, and more preferably 300 to 400 0 C .
  • reaction temperature is less than 200 ° C , the chlorination reaction of saturated hydrocarbon may not be conducted smoothly, and if the reaction temperature is more than 400 ° C , the durability of a catalyst is deteriorated by a loss of copper ion caused by sublimation of copper chloride.
  • saturated hydrocarbon a reactant
  • saturated hydrocarbon may be diluted with nitrogen gas and then supplied.
  • the dilution ratio may be properly determined on the basis of the operation condition.
  • a solid catalyst containing copper chloride compounds as a catalytic active component is oxidized in the oxidation reaction.
  • a solid catalyst containing copper chloride (I: CuCl) as a catalytic active component is oxidized.
  • a lso in the present invention, a catalyst obtained by adding additionally chloro salt of K, Mg and Ca in Groups IA or 2 A in Periodic Table to the copper chloride-based catalyst may be used.
  • a catalyst obtained by adding additionally chloro salt of transition metal such as Zn, La and the like to the copper chloride-based catalyst can be used to increase a reaction active site.
  • the solid catalyst used in the method for preparing chlorinated compounds of the present invention is preferably a solid catalyst in which a catalytic active component such as copper chloride compounds is supported in the carrier.
  • a catalytic active component such as copper chloride compounds
  • the carrier having a single component may be used, and the carrier obtained by supporting the component such as zeolite, titania and the like in alumina, silica and the like and then calcinating the above component may be used.
  • the catalytic active component consists of multi-components, these active components may be simultaneously or sequentially supported in the carrier prepared in advance.
  • a solid catalyst including cupric chloride (II, CuCl 2 ) as a catalytic active component is prepared first, the chlorination reaction of saturated hydrocarbon is then performed by using the solid catalyst, and the oxidation reaction of the catalyst (CuCl 2 ) utilized in the chlorination reaction is conducted. Finally, the chlorination- oxidation process is repeated. .
  • FIG 1 is a schematic view illustrating a method for preparing chlorinated compounds from methane through single-step oxychlorination reaction according to the prior art.
  • FIG 2 is a schematic view illustrating a method for preparing chlorinated compounds from methane by using oxidation and chlorination occurred alternately in a single reactor according to one embodiment of the present invention.
  • FIG 3 is a schematic view illustrating a method for preparing chlorinated compounds from methane by using oxidation and chlorination, occurred simultaneously in separate reactors capable of circulating a catalyst, according to the other embodiment of the present invention.
  • Example 1 2Og of a catalyst in which cupric chloride (II; CuCl 2 ) was supported in an alumina carrier (containing an amount of 10 % Cu by weight with respect to alumina) was supplied into the vertical tubular shaped INCOLLOY reactor (length: 60 cm; inner diameter: 1 inch), and an oxidation-chlorination reaction was then carried out on a fixed bed as follows: First, after elevating a temperature of the reactor up to 400 ° C, an chlorination reaction of methane was performed by supplying gaseous mixture of methane and nitrogen at a space velocity of 600 L/kg(cat)/hr. for 20 minutes at 400 ° C .
  • the gaseous mixture used in the chlorination reaction was obtained by diluting methane with nitrogen and had a molar ratio of 1 : 4 (methane : nitrogen). Then, a temperature in the reactor was lowered to 250 ° C for an oxidation reaction of the catalyst, and chlorinated reactants and products remained in the reactor were removed by flowing nitrogen at a space velocity of 600 L/kg(cat)/hr. And, an oxidation reaction of the catalyst was then carried out under the catalyst used in the chlorination reaction by supplying gaseous mixture of hydrogen chloride (HCl), oxgen (O 2 ) and nitrogen (N 2 ) at a space velocity of 600 L/kg(cat)/hr. for 20 minutes at 250 ° C .
  • HCl hydrogen chloride
  • O 2 oxgen
  • N 2 nitrogen
  • the gaseous mixture of HCl, O 2 and N 2 used in the oxidation reaction was obtained by diluting hydrogen chloride and oxygen with nitrogen and had a molar ratio of l : 0.5 : 3.5 (HCl : O 2 : N 2 ).
  • a temperature in the reactor was elevated up to 400 ° C for a chlorination reaction of methane and nitrogen was supplied at a space velocity of 600 L/kg(cat)/hr. to remove remainder of oxygen and hydrogen chloride in the reactor.
  • the chlorination of methane was carried out by supplying gaseous mixture of methane and nitrogen at space velocity of 600 L/kg(cat)/hr for 20 minutes at 400 ° C .
  • the gaseous mixture of methane and nitrogen used in the chlorination reaction was obtained by diluting methane with nitrogen and had a molar ratio of 1 : 4 (methane : nitrogen).
  • the above alternate oxidation-chlorination reaction was repeated up to 10 times.
  • Example 2 80g of a catalyst (which is the same as that utilized in Example 1) in which cupric chloride (II; CuCl 2 ) was supported in an alumina carrier (containing an amount of 10 % Cu by weight with respect to alumina), was supplied into the vertical tubular shaped INCOLLOY reactor (length: Im; inner diameter: 1 inch), and an oxidation- chlorination reaction was then carried out on a fluidized bed. At this time, the oxidation-chlorination reaction was performed by the manner and condition which were the same as those of Example 1 except that a space velocity of the material supplied into the reactor was 200 L/kg(cat)/hr.
  • a space velocity of the material supplied into the reactor was 200 L/kg(cat)/hr.
  • Example 3 80g of a catalyst (which is the same as that utilized in Example 1) in which cupric chloride (II; CuCl 2 ) was supported in an alumina carrier (containing an amount of 10 % Cu by weight with respect to alumina) was supplied into the vertical tubular shaped INCOLLOY reactor (length: Im; inner diameter: 1 inch), and an oxidation- chlorination reaction was then carried out on a fluidized bed as follows: First, after elevating a temperature of the reactor up to 350 ° C , the chlorination reaction of ethane was performed by supplying gaseous mixture of ethane and nitrogen at a space velocity of 500 L/kg(cat)/hr. for 20 minutes at 350 ° C .
  • the gaseous mixture used in the chlorination reaction was obtained by diluting ethane with nitrogen and had a molar ratio of 1 : 11 (ethane : nitrogen). Then, a temperature in the reactor was lowered to 250 ° C for an oxidation reaction of the catalyst, and chlorinated reactants and products remained in the reactor were removed by flowing nitrogen at a space velocity of 200 L/kg(cat)/hr. And, an oxidation reaction of the catalyst was then carried out under the catalyst used in the chlorination reaction by supplying gaseous mixture of hydrogen chloride (HCl), oxygen (O 2 ) and nitrogen (N 2 ) at a space velocity of 200 L/kg(cat)/hr. for 20 minutes at 250 ° C .
  • HCl hydrogen chloride
  • O 2 oxygen
  • N 2 nitrogen
  • the gaseous mixture of HCl, O 2 and N 2 used in the oxidation reaction was obtained by diluting hydrogen chloride and oxygen with nitrogen and had a molar ratio of l : 0.5 : 3.5 (HCl : O 2 : N 2 ).
  • a temperature in the reactor was elevated up to 350 " C for a chlorination reaction of ethane and nitrogen was supplied at a space velocity of 200 L/kg(cat)/hr. to remove remainder of oxygen and hydrogen chloride in the reactor.
  • the chlorination of ethane was carried out by supplying gaseous mixture of ethane and nitrogen at a space velocity of 500 L/kg(cat)/hr for 20 minutes at 350 ° C .
  • the gaseous mixture of ethane and nitrogen used in the chlorination reaction was obtained by diluting ethane with nitrogen and had a molar ratio of 1 : 11 (ethane : nitrogen).
  • the above alternate oxidation-chlorination reaction was repeated up to 10 times.
  • a catalyst which is the same as that utilized in Example 1 in which cupric chloride (II; CuCl 2 ) was supported in an alumina carrier (containing an amount of 10 % Cu by weight with respect to alumina), which is the same as that utilized in Example 1, was supplied into the vertical tubular shaped INCOLLOY reactor (length: Im; inner diameter: 1 inch), and a single-step oxychlorination reaction of methane was then carried out on a fluidized bed as follow.
  • the oxychlorination reaction of methane was carried out under the above catalyst by supplying gaseous mixture at a space velocity of 200 L/kg(cat)/hr. for 220 minutes at a temperature of 400 ° C .
  • the gaseous mixture was obtained by diluting methane (CH 4 ), hydrogen chloride (HCl) and oxygen (O 2 ) with nitrogen (N 2 ), which were reactants, and had a molar ratio of 1 : 1 :0.5: 2.5 (CH 4 : HCl : O 2 : N 2 ).
  • the gaseous mixture was obtained by diluting ethane (C 2 H 6 ), hydrogen chloride (HCl) and oxygen (O 2 ) with nitrogen (N 2 ), which were reactants, and had a molar ratio of 1 : 1 :0.5: 9.5 (C 2 H 6 : HCl : O 2 : N 2 ).
  • 5Og of a catalyst was prepared by supporting cupric chloride (II; CuCl 2 ) in an alumina carrier to contain an amount of about 6 % Cu by weight with respect to alumina.
  • Amount of Al and Cu in the catalyst was measured by performing the ICP (Inductively coupled plasma spectrometry) for a part of the catalyst before the catalyst was used for reaction.
  • the amount of Cu in the catalyst was 6.1% by weight with respect to the alumina (Al 2 O 3 ).
  • Example 1 A chlorination reaction of methane according to the same manner as Example 1 was performed by using 2Og of the catalyst prepared from the above, and the alternate oxidation-chlorination reaction performed in Example 1 was repeated up to 16 times (total chlorination reaction time was 340 minutes).
  • the catalyst used in the chlorination reaction conducted for total 340 minutes was analyzed through the ICP (Inductively coupled plasma spectrometry) to measure amount of Al and Cu in the catalyst.
  • the amount of Cu in the catalyst was 5.9% by weight with respect to alumina (Al 2 O 3 ).
  • amount of Cu was hardly reduced. From the above result, it could be known that even if chlorination reaction was performed for 340 minutes, Cu in the catalyst was hardly lost. Comparative example 3
  • a single-step oxychlorination reaction of methane was performed on a fixed bed by using 2Og of the catalyst which was the same as that utilized in Example 4 as follows:
  • the oxychlorination reaction of methane was carried out under the above catalyst by supplying gaseous mixture at a space velocity of 600 L/kg(cat)/hr for 340 minutes at 400 ° C .
  • the gaseous mixture was obtained by diluting methane (CH 4 ), hydrogen chloride (HCl) and oxygen (O 2 ) with nitrogen (N 2 ), which were reactants, and had a molar ratio of 1 : 1 :0.5: 2.5 (CH 4 : HCl : O 2 : N 2 ).
  • the catalyst used in the oxychlorination reaction conducted for total 340 minutes was analyzed through the ICP (Inductively coupled plasma spectrometry) to measure amount of Al and Cu in the catalyst.
  • the amount of Cu in the catalyst was only 1% by weight with respect to alumina (Al 2 O 3 ).
  • the present invention has the advantages that it possible to solve problems such as explosion hazards, a corrosion of reactor, and the like caused by the conventional oxychlorination reaction as well as to enhance the conversion rate of saturated hydrocarbon, a separate device for separating CO x from exhaust gases is not required since CO or CO 2 caused by a combustion reaction of saturated hydrocarbon is not generated, and by-product is not produced and the durability of catalyst is remarkably enhanced.

Abstract

The present invention relates to a method for preparing chlorinated compounds from saturated hydrocarbon. More particularly, the present invention relates to the method for preparing chlorinated compounds by conducting alternately an oxidation reaction of a catalyst under oxygen and hydrogen chloride, and a chlorination reaction for converting the saturated hydrocarbon into the chlorinated compounds by using the catalyst. The present invention has the advantages that the conversion rate of the saturated hydrocarbon may be enhanced; there is no need to consider erexplosion hazards; unreacted hydrogen chloride and corrosion of reactor may be reduced; a separate device for separating COx in exhaust gases may not be required since CO or CO2 is not produced in a combustion reaction; by-product may not be generated; and the durability of a catalyst may be remarkably enhanced.

Description

[DESCRIPTION]
[Invention Title]
METHOD FOR PREPARING CHLORINATED COMPOUND FROM SATURATED HYDROCARBON
[Technical Field]
The present invention relates to a method for preparing chlorinated compounds from saturated hydrocarbon. More particularly, the present invention relates to the method for preparing chlorinated compounds, in which an oxidation step for a catalyst to be used for a chlorination of saturated hydrocarbon performed under oxygen and hydrogen chloride and a chlorination step for converting saturated hydrocarbon into chlorinated compounds by using the above catalyst. The present invention has the advantages that the conversion rate of the saturated hydrocarbon may be enhanced; there is no need to consider explosion hazards; unreacted hydrogen chloride and corrosion of reactor may be reduced; there is no need to provide a separate device for separating COx in exhaust gases since CO or CO2 is not produced by a combustion reaction; by-product may not be produced; and a durability of the catalyst may be remarkably enhanced.
[Background Art]
Due to a continuous rising of oil price, the importance of research for utilizing the natural gas which is inexpensive and abundant in reserve has been increased. Many researches about a pyrolytic reaction using oxygen of methane contained in natural gas and a coupling reaction using a catalyst have been mainly reported. In particular, as a method capable of using chlorine compounds in order to utilize methane, a method of pyrolyzing methane and chlorine at a high temperature is disclosed in, for example, US Patent Nos. 4199533, 4804797, 4714796, 4983783 and the like. On the other hand, a method for preparing methyl chloride (CH3Cl) from oxychlorination of methane is disclosed in WO 84/03277, US Patent No. 4769504 and 5087786. In the above prior arts, methyl chloride (CH3Cl) is prepared by reacting methane, oxygen and hydrogen chloride in a single step on a supported catalyst having metallic salt of copper and iron as a basal component. Reg arding the above method, the research about an effect and pressure caused by adding the second metal to copper salt which is a basal catalyst component, and the like have been also reported as a method for improving the stability of catalyst and the selectivity of catalyst for methyl chloride (CH3Cl) of a catalyst (J. Am. Chem. Soc, 107(1985), 7097; Appl. Catal, 46(1989), 251; Chem. Eng. ScL, 49(1994), 4627).
The conventional method for preparing chlorinated compounds from methane through the single-step oxychlorination reaction as described above is illustrated schematically in FIG. 1. In the above method, gaseous mixture of methane, hydrogen chloride and oxygen is supplied into a reactor in which a solid catalyst (cupric chloride (CuCl2) catalyst supported in alumina (Al2O3)) for reaction is received, and the reaction represented as the below reaction formula (1) is performed. [Reaction formula 1] catalyst CH4 + HCl + -K) 2 ► CH3Cl + H2O
However, it is difficult to commercialize the single-step oxychlorination reaction due to various problems as follows: 1) in a case where air is utilized as a source of oxygen, since a great quantity of nitrogen is discharged along with a product and another by-product after the reaction is completed, there is the disadvantage that the scale of the back-end process becomes enlarge in order to treat the nitrogen, the product and by-product. 2) There is explosion hazards since saturated hydrocarbon and oxygen exist together at a high temperature. Th erefore, the mixing ratio of oxygen and saturated hydrocarbon has to out of the range of explosion hazards in order to perform safely the above reaction. For this, a method of supplying dividedly air may be used to maintain oxygen at a low concentration or a method of supplying the great quantity of saturated hydrocarbon gas may be used. However, the method of supplying dividedly air causes a lowering of the productivity, and the excessive saturated hydrocarbon may cause a low conversion rate. And, since a separation step and a re-supplying step should be performed after the reaction, the process becomes complicated and the operation cost may be increased. 3) Water produced as a result of the reaction and hydrogen chloride as reactant are in contact with each other, and so the reactor is corroded. As a result, a service life time of the reactor is reduced.
4) Since gaseous mixture of saturated hydrocarbon, oxygen and hydrogen chloride is supplied, CO or CO2 is produced by a combustion reaction between oxygen and methane. Such combustion reaction consumes oxygen in the supplied gas so that an oxychlorination reaction of the saturated hydrocarbon as the major reaction may be inhibited and the produced CO and CO2 cause a lowering of the selectivity for chlorinated compound.
5) A chlorination of saturated hydrocarbon is performed at a high temperature of 300 to 400 °C . I f a catalyst is exposed to a condition of a high temperature for a long period, copper ion may be lost by sublimation of cupric chloride. Therefore, the durability of the catalyst may be lowered.
As described above, the conventional method for preparing chlorinated compounds through the single-step oxychlorination reaction, in which gaseous mixture of saturated hydrocarbon, oxygen and hydrogen chloride is supplied simultaneously, has the problems of oxygen utilization, explosion hazards, a corrosion of reactor, a generation of CO or CO2 and a deterioration of the catalyst durability, and so the above method is not commercially available. Accordingly, the development of method for preparing chlorinated compounds from saturated hydrocarbon, which does not have the problem as described above and is commercially available, has been required.
[Disclosure] [Technical Problem] The present invention intends to solve problems of the prior art as described above, it is an object of the present invention to provide a method for preparing chlorinated compounds from saturated hydrocarbon, which can improve a conversion rate of saturated hydrocarbon, does not have to consider an explosion hazard, can reduce un-reacted hydrogen chloride to prevent a corrosion of a reactor, does not require a separate device for separating COx from exhaust gas since CO or CO2 caused by a combustion reaction is not produced, does not produce by-product and can enhance remarkably a durability of catalyst.
[Technical Solution] A method for preparing chlorinated compounds from saturated hydrocarbon, according to the present invention, comprises the steps of oxidizing a catalyst under oxygen and hydrogen chloride; and chlorinating saturated hydrocarbon under the oxidized catalyst. In one embodiment of the method for preparing chlorinated compounds of the present invention, the chlorinated compounds are prepared from methane. In this case, for example, an oxidation reaction of a catalyst and a chlorination reaction of methane are conducted separately as shown in the reaction formula (2) in which copper chloride is used as a catalyst:
[Reaction formula 2]
Oxidation: 2CuCl(catalyst) + 2HCl + £O2 ► 2CuCl2(catalyst) + H2O
Chlorination: CH4 + 2CuCl2(catalyst) ^ CH3Cl + HCl +2CuCl(catalyst)
In other words, unlike the conventional single-step oxychlorination reaction in which gaseous mixture of methane, oxygen and hydrogen chloride is simultaneously supplied and reacted under catalyst, in the embodiment of the present invention using methane as saturated hydrocarbon, the catalyst oxidation step performed under oxygen and hydrogen chloride for a chlorination of methane and the chlorination step for converting, for example, methane into chloromethane by using the oxidized catalyst are performed separately so that one or more chloromethane in which 1 to 4 of hydrogen of methane is substituted with chloride, that is, methyl chloride (CH3Cl), methylene chloride (CH2Cl2), chloroform (CHCl3) and carbon tetrachloride (CCl4) are obtained.
The advantages which may be expected by performing separately the oxidation step and the chlorination step are as follows: a) Since the chlorination step for saturated hydrocarbon is carried out after the oxidation of a catalyst is sufficiently performed, the conversion rate of saturated hydrocarbon may be enhanced. As a result, the generation of by-product may be relatively reduced. b) Since oxygen and saturated hydrocarbon are separated from each other and are reacted with a catalyst in different steps, respectively, there is no need to consider explosion hazards. c) Since there is no need to consider explosion hazards, it is possible to supply oxygen and hydrogen chloride in the oxidation reaction in view of the stoichiometric proportion. Consequentl y, it possible to reduce un-reacted hydrogen chloride, and so a corrosion of the reactor caused by a reaction between hydrogen chloride and water can be prevented. d) Since oxygen does not exist when saturated hydrocarbon is chlorinated, CO or CO2 is not generated in the combustion reaction. Therefore, the selectivity to chlorinated compounds may be increased and a separate device for separating COx in exhaust gas may not be required. e) Since the oxidation reaction of a catalyst, which is a severe exothermic reaction, and the chlorination reaction of saturated hydrocarbon are performed independently, as compared with the single-step oxychlorination reaction, the chlorination reaction may be performed at a relatively lower temperature, and so it is possible to prevent a loss of copper ion in the catalyst caused by a high temperature. As a result, the durability of the catalyst is enhanced.
According to the one embodiment of the present invention as illustrated schematically in FIG 2, the above two steps are proceeded alternately in a single reactor. On the other hand, according to another embodiment of the present invention as illustrated schematically in FIG 3, the above two steps are proceeded independently in separate reactors and a catalyst is circulated continuously through a catalyst transferring pipe provided between these separate reactors.
In the method for preparing chlorinated compounds of the present invention, the oxidation reaction of a catalyst and the chlorination reaction of saturated hydrocarbon may be carried out in a fixed bed reactor or a fluidized bed reactor. In particular, as shown in FIG 3, in a case where two steps (reactions) are independently performed in separate reactors and a catalyst transferring pipe is provided between these separate reactors to circulate continuously the catalyst, it is preferable to employ the fluid bed reactor.
In the method for preparing chlorinated compounds of the present invention, saturated hydrocarbon is used as a starting material, and preferably, an aliphatic saturated hydrocarbon having carbon numbers of 1 through 6 such as methane, ethane and propane etc. may be used. More preferably, methane or ethane may be used, and most preferably, methane may be used. If two or more kinds of saturated hydrocarbons are used, it will be apparent that a mixture thereof may be used.
When methane is utilized as the starting material, one or more of methyl chloride (CH3Cl), methylene chloride (CH2Cl2), chloroform (CHCl3) and carbon tetrachloride (CCl4) may be finally obtained. In the meantime, if ethane is used as the starting material, saturated or unsaturated chlorinated C2 compounds in which one or more of hydrogen atom of ethane is substituted with chloride may be obtained. For example, ethyl chloride (C2H5Cl), ethylene dichloride (C2H4Cl2, EDC), vinyl chloride (C2H3Cl, VCM) or mixture thereof may be obtained as a major product. And, ethylene, trichloroethane, tetrachloroethane, vinylidene chloride, dichloroethylene, trichloroethylene or mixture thereof may be obtained as a by-product. In particular, when natural gas is processed according to the present invention, EDC or VCM may be prepared from ethane in relative inexpensive natural gas. As compared with a conventional naphtha cracking process, accordingly, it is possible to reduce significantly the production cost.
In the method for preparing chlorinated compounds of the present invention, the oxidation reaction of a catalyst is preferably performed at a temperature of 200 to 300 °C, and more preferably at a temperature of 230 to 290 °C . If the reaction temperature is less than 200 °C , the oxidation reaction of the catalyst can not be performed smoothly. And, if the reaction temperature is more than 300 "C, copper ion in the catalyst may be lost so that an activity of the catalyst is deteriorated and the durability is lowered.
The chlorination reaction of saturated hydrocarbon needs a reaction temperature higher than that in the oxidation reaction of a catalyst. In the conventional single-step oxychlorination reaction, a temperature which is higher than a temperature required for the oxidation reaction of catalyst should be maintained and such single-step oxychlorination reaction has a problem that a loss of the catalyst is caused by the exothermic oxidation reaction. In the present invention, however, the oxidation reaction of catalyst and the chlorination reaction of saturated hydrocarbon are independently conducted, so the oxidation reaction may be performed at a relative low temperature. Also, since caloric value in the chlorination reaction conducted at a relative high temperature is not large, as compared with the conventional arts, a loss of the catalyst caused by a high temperature is extremely small. In the oxidation reaction of a catalyst, in addition, a pressure condition is not particularly limited. For example, a suitable pressure condition can be selected from the range within atmospheric pressure of 1 to 20 according to a reaction equipment and the like. Further, the oxidation reaction of a catalyst may be preferably conducted at a space velocity (Weight Hour Space Velocity, WHSV) of reaction products in the range of 10 to 10,000 L/kg(cat)/hr, and more preferably in the range of 100 to 1,000 L/kg(cat)/hr. If the above space velocity is less than 10 L/kg(cat)/hr, a production of undesired by-product may be increased, and the above space velocity is more than 10,000 L/kg(cat)/hr, unreacted material may be excessively increased to reduce the process efficiency.
In the mixture of oxygen and hydrogen chloride gas which are reactants, used in the oxidation reaction of a catalyst, even if a stoichiometric molar ratio of oxygen and hydrogen chloride based on a reaction formula is 1 : 4, somewhat large quantity of oxygen can be used to inhibit hydrogen chloride from being maintained in an unreacted state. And, oxygen and hydrogen chloride gas which are reactant can be diluted with nitrogen gas and then supplied, and the dilution ratio may be properly determined according to the operation condition. Air can be used as a source of oxygen. In the method for preparing chlorinated compounds of the present invention, the chlorination reaction of saturated hydrocarbon is preferably performed at a temperature of 200 °C to 600 °C, and more preferably 300 to 4000C . If the reaction temperature is less than 200 °C , the chlorination reaction of saturated hydrocarbon may not be conducted smoothly, and if the reaction temperature is more than 400 °C , the durability of a catalyst is deteriorated by a loss of copper ion caused by sublimation of copper chloride.
In addition, in the chlorination reaction of saturated hydrocarbon, it is possible to supply saturated hydrocarbon (a reactant) which is not diluted. On the contrary, saturated hydrocarbon may be diluted with nitrogen gas and then supplied. When saturated hydrocarbon is diluted with nitrogen gas, the dilution ratio may be properly determined on the basis of the operation condition.
In the method for preparing chlorinated compounds of the present invention, a solid catalyst containing copper chloride compounds as a catalytic active component is oxidized in the oxidation reaction. Preferably, a solid catalyst containing copper chloride (I: CuCl) as a catalytic active component is oxidized. A lso, in the present invention, a catalyst obtained by adding additionally chloro salt of K, Mg and Ca in Groups IA or 2 A in Periodic Table to the copper chloride-based catalyst may be used. In addition, a catalyst obtained by adding additionally chloro salt of transition metal such as Zn, La and the like to the copper chloride-based catalyst can be used to increase a reaction active site.
The solid catalyst used in the method for preparing chlorinated compounds of the present invention is preferably a solid catalyst in which a catalytic active component such as copper chloride compounds is supported in the carrier. At this time, it is preferable that one or more selected from the group consisting of zeolite, alumina, titania and silica is utilized as the carrier. The carrier having a single component may be used, and the carrier obtained by supporting the component such as zeolite, titania and the like in alumina, silica and the like and then calcinating the above component may be used. And, if the catalytic active component consists of multi-components, these active components may be simultaneously or sequentially supported in the carrier prepared in advance.
In one embodiment of the method for preparing chlorinated compounds of the present invention, a solid catalyst including cupric chloride (II, CuCl2) as a catalytic active component is prepared first, the chlorination reaction of saturated hydrocarbon is then performed by using the solid catalyst, and the oxidation reaction of the catalyst (CuCl2) utilized in the chlorination reaction is conducted. Finally, the chlorination- oxidation process is repeated. .
[Description of Drawings]
FIG 1 is a schematic view illustrating a method for preparing chlorinated compounds from methane through single-step oxychlorination reaction according to the prior art.
FIG 2 is a schematic view illustrating a method for preparing chlorinated compounds from methane by using oxidation and chlorination occurred alternately in a single reactor according to one embodiment of the present invention.
FIG 3 is a schematic view illustrating a method for preparing chlorinated compounds from methane by using oxidation and chlorination, occurred simultaneously in separate reactors capable of circulating a catalyst, according to the other embodiment of the present invention.
[Mode for Invention]
Hereinafter, the preferred examples of the present invention will be explained in more detail. The following examples are provided to explain only the illustrative examples of the present invention, and so it will be apparent that the spirit and scope of the present invention is not limited to the below examples.
Example 1 2Og of a catalyst in which cupric chloride (II; CuCl2) was supported in an alumina carrier (containing an amount of 10 % Cu by weight with respect to alumina) was supplied into the vertical tubular shaped INCOLLOY reactor (length: 60 cm; inner diameter: 1 inch), and an oxidation-chlorination reaction was then carried out on a fixed bed as follows: First, after elevating a temperature of the reactor up to 400 °C, an chlorination reaction of methane was performed by supplying gaseous mixture of methane and nitrogen at a space velocity of 600 L/kg(cat)/hr. for 20 minutes at 400 °C . Here, the gaseous mixture used in the chlorination reaction was obtained by diluting methane with nitrogen and had a molar ratio of 1 : 4 (methane : nitrogen). Then, a temperature in the reactor was lowered to 250 °C for an oxidation reaction of the catalyst, and chlorinated reactants and products remained in the reactor were removed by flowing nitrogen at a space velocity of 600 L/kg(cat)/hr. And, an oxidation reaction of the catalyst was then carried out under the catalyst used in the chlorination reaction by supplying gaseous mixture of hydrogen chloride (HCl), oxgen (O2) and nitrogen (N2) at a space velocity of 600 L/kg(cat)/hr. for 20 minutes at 250 °C . Here, the gaseous mixture of HCl, O2 and N2 used in the oxidation reaction was obtained by diluting hydrogen chloride and oxygen with nitrogen and had a molar ratio of l : 0.5 : 3.5 (HCl : O2 : N2 ).
Subsequently, a temperature in the reactor was elevated up to 400 °C for a chlorination reaction of methane and nitrogen was supplied at a space velocity of 600 L/kg(cat)/hr. to remove remainder of oxygen and hydrogen chloride in the reactor. Then, the chlorination of methane was carried out by supplying gaseous mixture of methane and nitrogen at space velocity of 600 L/kg(cat)/hr for 20 minutes at 400 °C . Here, the gaseous mixture of methane and nitrogen used in the chlorination reaction was obtained by diluting methane with nitrogen and had a molar ratio of 1 : 4 (methane : nitrogen). Thereafter, the above alternate oxidation-chlorination reaction was repeated up to 10 times.
As a result of analyzing reaction products produced in the chlorination reaction of methane, the selectivity of methylchloride (CH3CI) was 55%, the selectivity of methylene chloride (CH2Cl2) was 38% and the selectivity of COχ was 0%. The conversion rate of methane was 40%.
Example 2 80g of a catalyst (which is the same as that utilized in Example 1) in which cupric chloride (II; CuCl2) was supported in an alumina carrier (containing an amount of 10 % Cu by weight with respect to alumina), was supplied into the vertical tubular shaped INCOLLOY reactor (length: Im; inner diameter: 1 inch), and an oxidation- chlorination reaction was then carried out on a fluidized bed. At this time, the oxidation-chlorination reaction was performed by the manner and condition which were the same as those of Example 1 except that a space velocity of the material supplied into the reactor was 200 L/kg(cat)/hr.
As a result of analyzing reaction products produced in the chlorination reaction of methane, the selectivity of methylchloride (CH3Cl) was 58%, the selectivity of methylene chloride (CH2Cl2) was 36% and the selectivity of C0χ was 0%. The conversion rate of methane was 32%.
Example 3 80g of a catalyst (which is the same as that utilized in Example 1) in which cupric chloride (II; CuCl2) was supported in an alumina carrier (containing an amount of 10 % Cu by weight with respect to alumina) was supplied into the vertical tubular shaped INCOLLOY reactor (length: Im; inner diameter: 1 inch), and an oxidation- chlorination reaction was then carried out on a fluidized bed as follows: First, after elevating a temperature of the reactor up to 350 °C , the chlorination reaction of ethane was performed by supplying gaseous mixture of ethane and nitrogen at a space velocity of 500 L/kg(cat)/hr. for 20 minutes at 350 °C . Here, the gaseous mixture used in the chlorination reaction was obtained by diluting ethane with nitrogen and had a molar ratio of 1 : 11 (ethane : nitrogen). Then, a temperature in the reactor was lowered to 250 °C for an oxidation reaction of the catalyst, and chlorinated reactants and products remained in the reactor were removed by flowing nitrogen at a space velocity of 200 L/kg(cat)/hr. And, an oxidation reaction of the catalyst was then carried out under the catalyst used in the chlorination reaction by supplying gaseous mixture of hydrogen chloride (HCl), oxygen (O2) and nitrogen (N2) at a space velocity of 200 L/kg(cat)/hr. for 20 minutes at 250 °C . Here, the gaseous mixture of HCl, O2 and N2 used in the oxidation reaction was obtained by diluting hydrogen chloride and oxygen with nitrogen and had a molar ratio of l : 0.5 : 3.5 (HCl : O2 : N2 ).
Subsequently, a temperature in the reactor was elevated up to 350 "C for a chlorination reaction of ethane and nitrogen was supplied at a space velocity of 200 L/kg(cat)/hr. to remove remainder of oxygen and hydrogen chloride in the reactor. Then, the chlorination of ethane was carried out by supplying gaseous mixture of ethane and nitrogen at a space velocity of 500 L/kg(cat)/hr for 20 minutes at 350 °C . Here, the gaseous mixture of ethane and nitrogen used in the chlorination reaction was obtained by diluting ethane with nitrogen and had a molar ratio of 1 : 11 (ethane : nitrogen). Thereafter, the above alternate oxidation-chlorination reaction was repeated up to 10 times.
As a result of analyzing reaction products produced in the chlorination reaction of ethane, the selectivity of ethylchloride (C2H5Cl) was 44%, the selectivity of ethylene dichloride (C2H4Cl2, EDC) was 32%, the selectivity of vinyl chloride (C2H3Cl, VCM) was 2%, the selectivity of ethylene was 0% and the selectivity of COχ was 0%. Th e conversion rate of ethane was 62%.
Comparative example 1
80g of a catalyst (which is the same as that utilized in Example 1) in which cupric chloride (II; CuCl2) was supported in an alumina carrier (containing an amount of 10 % Cu by weight with respect to alumina), which is the same as that utilized in Example 1, was supplied into the vertical tubular shaped INCOLLOY reactor (length: Im; inner diameter: 1 inch), and a single-step oxychlorination reaction of methane was then carried out on a fluidized bed as follow.
The oxychlorination reaction of methane was carried out under the above catalyst by supplying gaseous mixture at a space velocity of 200 L/kg(cat)/hr. for 220 minutes at a temperature of 400 °C . Here, the gaseous mixture was obtained by diluting methane (CH4), hydrogen chloride (HCl) and oxygen (O2) with nitrogen (N2), which were reactants, and had a molar ratio of 1 : 1 :0.5: 2.5 (CH4: HCl : O2 : N2).
As a result of analyzing reaction products produced in the oxychlorination reaction, the selectivity of methylchloride (CH3CI) was 75%, the selectivity of methylene chloride (CH2Cl2) was 18% and the selectivity of COχ was 6%. The conversion rate of methane was only 7%.
Comparative example 2
8Og of a catalyst (which is the same as that utilized in Example 1) in which cupric chloride (II; CuCl2) was supported in an alumina carrier (containing an amount of 10 % Cu by weight with respect to alumina), which is the same as that utilized in Example 1, was supplied into the vertical tubular shaped INCOLLOY reactor (length: Im; inner diameter: 1 inch), and a single-step oxychlorination reaction of ethane was then carried out on a fluidized bed as follows. The oxychlorination reaction of ethane was carried out under the above catalyst by supplying gaseous mixture at a space velocity of 500 L/kg(cat)/hr. for 220 minutes at a temperature of 350 °C . Here, the gaseous mixture was obtained by diluting ethane (C2H6), hydrogen chloride (HCl) and oxygen (O2) with nitrogen (N2), which were reactants, and had a molar ratio of 1 : 1 :0.5: 9.5 (C2H6: HCl : O2 : N2). As a result of analyzing reaction products produced in the oxychlorination reaction, the selectivity of ethylchloride (C2H5Cl) was 36%, the selectivity of ethylene dichloride (C2H4Cl2, EDC) was 42%, the selectivity of vinyl chloride (C2H3Cl, VCM) was 0%, the selectivity of ethylene was 4% and COχ was 5%. Th e conversion rate of ethane was only 34%. Example 4
5Og of a catalyst was prepared by supporting cupric chloride (II; CuCl2) in an alumina carrier to contain an amount of about 6 % Cu by weight with respect to alumina. Amount of Al and Cu in the catalyst was measured by performing the ICP (Inductively coupled plasma spectrometry) for a part of the catalyst before the catalyst was used for reaction. As a result, the amount of Cu in the catalyst was 6.1% by weight with respect to the alumina (Al2O3).
A chlorination reaction of methane according to the same manner as Example 1 was performed by using 2Og of the catalyst prepared from the above, and the alternate oxidation-chlorination reaction performed in Example 1 was repeated up to 16 times (total chlorination reaction time was 340 minutes).
As a result of analyzing reaction products produced in the chlorination reaction of methane, the selectivity of methylchloride (CH3Cl) was 62%, the selectivity of methylene chloride (CH2Cl2) was 34% and the selectivity of COχ was 0%. The conversion rate of methane was 38%.
The catalyst used in the chlorination reaction conducted for total 340 minutes was analyzed through the ICP (Inductively coupled plasma spectrometry) to measure amount of Al and Cu in the catalyst. As a result, the amount of Cu in the catalyst was 5.9% by weight with respect to alumina (Al2O3). As compared with amount of Cu of 6.1% by weight before the catalyst was utilized in the reaction, amount of Cu was hardly reduced. From the above result, it could be known that even if chlorination reaction was performed for 340 minutes, Cu in the catalyst was hardly lost. Comparative example 3
A single-step oxychlorination reaction of methane was performed on a fixed bed by using 2Og of the catalyst which was the same as that utilized in Example 4 as follows: The oxychlorination reaction of methane was carried out under the above catalyst by supplying gaseous mixture at a space velocity of 600 L/kg(cat)/hr for 340 minutes at 400 °C . Here, the gaseous mixture was obtained by diluting methane (CH4), hydrogen chloride (HCl) and oxygen (O2) with nitrogen (N2), which were reactants, and had a molar ratio of 1 : 1 :0.5: 2.5 (CH4: HCl : O2 : N2). As a result of analyzing reaction products produced in the oxychlorination reaction, the selectivity of methyl chloride (CH3Cl) was 74%, the selectivity of methylene chloride (CH2Cl2) was 18% and the selectivity of COχ was 7%. The conversion rate of methane was only 6%.
The catalyst used in the oxychlorination reaction conducted for total 340 minutes was analyzed through the ICP (Inductively coupled plasma spectrometry) to measure amount of Al and Cu in the catalyst. As a result, the amount of Cu in the catalyst was only 1% by weight with respect to alumina (Al2O3).
[Industrial Applicability] As illustrated the above, in the process of preparing chlorinated compounds from saturated hydrocarbon such as methane, the present invention has the advantages that it possible to solve problems such as explosion hazards, a corrosion of reactor, and the like caused by the conventional oxychlorination reaction as well as to enhance the conversion rate of saturated hydrocarbon, a separate device for separating COx from exhaust gases is not required since CO or CO2 caused by a combustion reaction of saturated hydrocarbon is not generated, and by-product is not produced and the durability of catalyst is remarkably enhanced.

Claims

[CLAIMS] [Claim 1 ]
A method for preparing chlorinated compounds from saturated hydrocarbon, comprising the steps of; i) oxidizing a catalyst under oxygen and hydrogen chloride; and ii) chlorinating the saturated hydrocarbon under the oxidized catalyst.
[Claim 2]
The method according to claim 1, wherein the oxidation step and the chlorination step are alternately performed in a single reactor.
[Claim 3]
The method according to claim 1, wherein the oxidation step and the chlorination step are independently performed in separate reactors.
[Claim 4]
The method according to claim 2, wherein the oxidation step and the chlorination step are alternately performed in a fixed or fluidized bed reactor.
[Claim 5]
The method according to claim 3, wherein the oxidation step and the chlorination step are independently performed in a fluidized bed reactor.
[Claim 6] The method according to claim 1, wherein the saturated hydrocarbon is methane, ethane or mixture thereof.
[Claim 7]
The method according to claim 1, wherein the saturated hydrocarbon is methane.
[Claim 8]
The method according to claim 1, wherein oxidation reaction of the catalyst is carried out at a temperature of 200 to 300 °C, and the chlorination reaction of the saturated hydrocarbon is conducted at a temperature of 200 to 600 °C .
[Claim 9]
The method according to claim 1, wherein the oxidation reaction of the catalyst is carried out at a temperature of 230 to 290 °C, and the chlorination reaction of the saturated hydrocarbon is conducted at a temperature of 300 to 400 °C .
[Claim 10] The method according to claim 1, wherein the oxidized catalyst in the oxidation reaction contains copper chloride compounds as a catalytic active component. [Claim 11 ]
The method according to claim 1, wherein the catalyst is obtained by supporting catalytic active component in a carrier. [Claim 12]
The method according to claim 11 , wherein the carrier is one or more selected from the group consisting of zeolite, alrumina, titania and silica.
PCT/KR2007/004235 2007-09-03 2007-09-03 Method for preparing chlorinated compound from saturated hydrocarbon WO2009031719A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/KR2007/004235 WO2009031719A1 (en) 2007-09-03 2007-09-03 Method for preparing chlorinated compound from saturated hydrocarbon
CN200780052860A CN101663258A (en) 2007-09-03 2007-09-03 Method for preparing chlorinated compound from saturated hydrocarbon

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/KR2007/004235 WO2009031719A1 (en) 2007-09-03 2007-09-03 Method for preparing chlorinated compound from saturated hydrocarbon

Publications (1)

Publication Number Publication Date
WO2009031719A1 true WO2009031719A1 (en) 2009-03-12

Family

ID=40429019

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2007/004235 WO2009031719A1 (en) 2007-09-03 2007-09-03 Method for preparing chlorinated compound from saturated hydrocarbon

Country Status (2)

Country Link
CN (1) CN101663258A (en)
WO (1) WO2009031719A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010062427A2 (en) * 2008-10-27 2010-06-03 Dow Global Technologies Inc. Oxidative mono-halogenation of methane
WO2016138165A1 (en) * 2015-02-25 2016-09-01 Sgc Energia S.A. (Formerly-Gi-Gasification International S.A.) Systems, methods, and apparatuses for fischer-tropsch reactor cascade

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3730211A4 (en) * 2018-02-23 2021-01-06 Lg Chem, Ltd. Catalyst for oxychlorination process of hydrocarbon, method for producing same, and method for manufacturing oxychlorinated compound of hydrocarbon by using same

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4654449A (en) * 1982-12-09 1987-03-31 Mobil Oil Corporation Formation of halogenated hydrocarbons from hydrocarbons
US5243098A (en) * 1992-11-04 1993-09-07 Energia Andina Ltd. Conversion of methane to methanol

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4654449A (en) * 1982-12-09 1987-03-31 Mobil Oil Corporation Formation of halogenated hydrocarbons from hydrocarbons
US5243098A (en) * 1992-11-04 1993-09-07 Energia Andina Ltd. Conversion of methane to methanol

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010062427A2 (en) * 2008-10-27 2010-06-03 Dow Global Technologies Inc. Oxidative mono-halogenation of methane
WO2010062427A3 (en) * 2008-10-27 2010-07-22 Dow Global Technologies Inc. Oxidative mono-halogenation of methane
US8674149B2 (en) 2008-10-27 2014-03-18 Dow Global Technologies Llc Oxidative mono-halogenation of methane
WO2016138165A1 (en) * 2015-02-25 2016-09-01 Sgc Energia S.A. (Formerly-Gi-Gasification International S.A.) Systems, methods, and apparatuses for fischer-tropsch reactor cascade

Also Published As

Publication number Publication date
CN101663258A (en) 2010-03-03

Similar Documents

Publication Publication Date Title
RU2409547C2 (en) Method for oxidative halogenation and method of producing halogenated c1 product
KR100876032B1 (en) Oxidative Hydrohalogenation of C1 Hydrocarbons to Halogenated C1 Hydrocarbons and Their Associated Processes
US5243098A (en) Conversion of methane to methanol
EP1235772B1 (en) A process for the conversion of ethylene to vinyl chloride, and novel catalyst compositions useful for such process
US20050148805A1 (en) Process for the conversion of ethylene to vinyl chloride, and novel catalyst compositions useful for such process
AU2002256217A1 (en) Oxidative halogenation of C1 hydrocarbons to halogenated C1 hydrocarbons and integrated processes related thereto
KR20040002987A (en) Oxidative Halogenation and Optional Dehydrogenation of C3+ Hydrocarbons
JP2004534770A (en) Method for producing vinyl chloride from ethane and ethylene using air supply and alternative HCl treatment method
US20170152207A1 (en) Compositions and methods for hydrocarbon functionalization
WO2009031719A1 (en) Method for preparing chlorinated compound from saturated hydrocarbon
KR20020056935A (en) Process for vinyl chloride manufacture from ethane and ethylene with partial HCl recovery from reactor effluent
KR101017302B1 (en) Method for preparing chlorinated compound from saturated hydrocarbon
KR100843605B1 (en) The method for preparing vinyl chloride monomer using ethane in natural gas
US11780792B2 (en) Photochlorination of partially-chlorinated chloromethanes to carbon tetrachloride
KR101236099B1 (en) Novel method for the production of vinyl chloride monomer
US20110311401A1 (en) Swing reactor and process for oxychlorination
MX2008015082A (en) Method for producing pentafluoroethane.
US3453340A (en) Manufacture of chlorinated hydrocarbons
US8030530B2 (en) Swing reactor and process for oxychlorination
US9169168B2 (en) Process for producing ethylene by chlorination of ethane and dehydrochlorination of ethyl chloride
KR100843599B1 (en) The method for preparing vinyl chloride monomer using methane in natural gas
WO2020041667A1 (en) One pot dehydrochlorination/chlorination of a chloroalkane to produce a mixture of chlorinated alkenes and chlorinated alkanes
JP2011219390A (en) Catalytic reactor and catalytic oxychlorination reaction method
CA2698276A1 (en) Swing reactor and process for oxychlorination
PL185758B1 (en) Ethylene oxychlorinating method

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200780052860.8

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07808033

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 07808033

Country of ref document: EP

Kind code of ref document: A1