CA1229841A - Catalyst for oxyhalogenation and condensation of alkanes - Google Patents
Catalyst for oxyhalogenation and condensation of alkanesInfo
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- CA1229841A CA1229841A CA000476865A CA476865A CA1229841A CA 1229841 A CA1229841 A CA 1229841A CA 000476865 A CA000476865 A CA 000476865A CA 476865 A CA476865 A CA 476865A CA 1229841 A CA1229841 A CA 1229841A
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- catalyst
- zsm
- alumina
- deacon
- zeolite
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- 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
-
- 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
- C07C17/15—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination
- C07C17/152—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
ABSTRACT
A dual-function chlorination-condensation catalyst composition comprises (a) a Deacon catalyst comprising cupric halide, alkaline earth metal halide and/or alkali metal halide, and/or rare earth metal halide and (b) a crystalline aluminosilicate zeolite such as ZSM-5 type zeolite.
A dual-function chlorination-condensation catalyst composition comprises (a) a Deacon catalyst comprising cupric halide, alkaline earth metal halide and/or alkali metal halide, and/or rare earth metal halide and (b) a crystalline aluminosilicate zeolite such as ZSM-5 type zeolite.
Description
F-2703-L ~2~
CATALYST FOR OXYHALOGENATION
A~D CONDENSATION DF ALKAN~S
This invention relates to a composite catalyst for converting natural gas and other alkane feedstocks into higher hydrocarbons, such as gasoline blending stocks and petrochemical materials.
The relative abundance of methane in natural gas and the high cost of petroleum raw materials has led workers in the ~ield of fossil fuel technology to seek economic processes for the conversion of lower alkanes into higher hydrocarbons in the gasoline and diesel boiling ranges. The C5~ aliphatic and aromatic hydrocarbons are particularly useful as liquid fuels for spark ignition internal combustion engines. Steam reforrning of methane-rich feedstocks to produce CO and ~12 (syngas) can be followed by conventional methanol synthesis or Fischer-Tropsch reactions to provide oxygenated feeristock suitable for hydrocarbon conYersion over catalysts comprising crystalline, medium pore zeolites, such as ZSM-5 zeolite.
A substantial ef~or-t has been made in developing a methanol-to-gasoline ("MTG") process, as described in U.S. Patents 3,894,107, 4,013,731, 4,11~,431, and ~,251,484. ûther processes involving the use of ZSM-5 type zeolites for conYerting ~ynthesis gas into gasoline-range hydrocarbons are described in U.S. Patents 4,159,995 and 4,093,029.
A dual functinn composite catalyst has been devised comprising an intimate mixture of a Deacon catalyst and a mediurn pore acird zeolite. This catalyst can be employed in an integrated process for halogenating alkanes and condensing the haloalkane intermediate to produce higher hydrocarbons. In a preferred embodiment, the dual-~unction catalyst comprises a Deacon catalyst , j.
deposited on alumina and composited with ~ZSM-5 crystals. Typical Deacon catalysts include CuC12, alkali metal chloride or alkaline earth metal chloride, and rare earth chloride impregnated on a solid carrier.
Halohydrocarbons can be made From lower aliphatic compounds by a number of halogenation processes. Emohasis is placed herein on the chlorination of methane and other components of natural gas as a preferred economic process for making higher hydrocarbons. Cl to C3 paraffins are abundant in nature, frequently occuring with carbon dioxide and trace amounts of C4~ hydrocarbons. A typical dry gas feedstock may contain 90+ vol. ~ C~ and lesser amounts of C2 and ethane.
A suitable halogenation gas may include molecular chlorine (C12) or hydrogen chloride (HCl) with oxygen. It i5 well known that halogen gases rnay be generated by heating hydrog~n halide in contact with an oxygen-containing gas, such as alr. ~hen combined with heated methane over a Deacon catalyst, a typical halogenation reaction occurs as follows:
C~l4-~HCl + 1/2 ~72 ~ C~ Cl ~ H20 Deacon catalysts are well-known materials and are commonly used in halogenation reactions, especially where HCl is oxidi~ed as part of the reaction. Although catalyst melts are known, partlculate catalysts such as obtaine~ by impregnating cupric hallde on calcined alumina are preferred, especially those L7eacon catalysts which consist essentially o~ clJpric chloride, alkali metal chloride and rare earth chloride calcined on alomin~. Preparation of suitable catalysts is described in U.S. Patents 3,184,515, 3,634,330 and 4,323,716. ~-lalogenation processes are describeci in U.S. Patents
CATALYST FOR OXYHALOGENATION
A~D CONDENSATION DF ALKAN~S
This invention relates to a composite catalyst for converting natural gas and other alkane feedstocks into higher hydrocarbons, such as gasoline blending stocks and petrochemical materials.
The relative abundance of methane in natural gas and the high cost of petroleum raw materials has led workers in the ~ield of fossil fuel technology to seek economic processes for the conversion of lower alkanes into higher hydrocarbons in the gasoline and diesel boiling ranges. The C5~ aliphatic and aromatic hydrocarbons are particularly useful as liquid fuels for spark ignition internal combustion engines. Steam reforrning of methane-rich feedstocks to produce CO and ~12 (syngas) can be followed by conventional methanol synthesis or Fischer-Tropsch reactions to provide oxygenated feeristock suitable for hydrocarbon conYersion over catalysts comprising crystalline, medium pore zeolites, such as ZSM-5 zeolite.
A substantial ef~or-t has been made in developing a methanol-to-gasoline ("MTG") process, as described in U.S. Patents 3,894,107, 4,013,731, 4,11~,431, and ~,251,484. ûther processes involving the use of ZSM-5 type zeolites for conYerting ~ynthesis gas into gasoline-range hydrocarbons are described in U.S. Patents 4,159,995 and 4,093,029.
A dual functinn composite catalyst has been devised comprising an intimate mixture of a Deacon catalyst and a mediurn pore acird zeolite. This catalyst can be employed in an integrated process for halogenating alkanes and condensing the haloalkane intermediate to produce higher hydrocarbons. In a preferred embodiment, the dual-~unction catalyst comprises a Deacon catalyst , j.
deposited on alumina and composited with ~ZSM-5 crystals. Typical Deacon catalysts include CuC12, alkali metal chloride or alkaline earth metal chloride, and rare earth chloride impregnated on a solid carrier.
Halohydrocarbons can be made From lower aliphatic compounds by a number of halogenation processes. Emohasis is placed herein on the chlorination of methane and other components of natural gas as a preferred economic process for making higher hydrocarbons. Cl to C3 paraffins are abundant in nature, frequently occuring with carbon dioxide and trace amounts of C4~ hydrocarbons. A typical dry gas feedstock may contain 90+ vol. ~ C~ and lesser amounts of C2 and ethane.
A suitable halogenation gas may include molecular chlorine (C12) or hydrogen chloride (HCl) with oxygen. It i5 well known that halogen gases rnay be generated by heating hydrog~n halide in contact with an oxygen-containing gas, such as alr. ~hen combined with heated methane over a Deacon catalyst, a typical halogenation reaction occurs as follows:
C~l4-~HCl + 1/2 ~72 ~ C~ Cl ~ H20 Deacon catalysts are well-known materials and are commonly used in halogenation reactions, especially where HCl is oxidi~ed as part of the reaction. Although catalyst melts are known, partlculate catalysts such as obtaine~ by impregnating cupric hallde on calcined alumina are preferred, especially those L7eacon catalysts which consist essentially o~ clJpric chloride, alkali metal chloride and rare earth chloride calcined on alomin~. Preparation of suitable catalysts is described in U.S. Patents 3,184,515, 3,634,330 and 4,323,716. ~-lalogenation processes are describeci in U.S. Patents
2,957,92~, 3J314~76O, 1,654,821 and 4~199J533.
In U.S. Patent 2,489,093 s~ch an oxyhalogenation first stage is combined with a catalytic second stage condensation to produce higher hydrocarbons, including C2-C4 par~f~ins and olefins and C5~ aliphatlcs and aromatics. The catalysts involved include alumina~ silica and related condensation catalysts. The second stage dehydrohalogenation reaction may be simplified as follows-(n) CH3Cl [HC3~nHCl.
It is recognized that the hydrocarbon products (HC) mayinclude light gases such as ethane, propane, propylene and butanes, as well as the condensed liquid hydrocarbon products and halogenated by-products.
A process for converting aliphatic halides using ZSM-5 type zeolites is described in U.S. Patent 3,894,107. The preferred catalysts comprise crystalline aluminosilicates having a silica to alumina ratio of at least 12 and a constraint index of 1 to 12. In the acid form these are often denominated HZSM-5 type materials.
Co-extruded with alumina, these active zeolites are available in various forms and sizes such as 1.6 mm cylindrical extrudate particles.
The zeolites that are useful as components of the composite catalysts of the invention are those having a silica to alumina mole ratio greater than 12:1, preferably greater than 30:1, and a constraint index of 1 to 12, and are exemolified by the shape-selective, medium-pore, siliceous zeolites ZSM-5, ZSM~5/ZSM-ll intermediate, ZSM-ll, ZSM-12, ZSM-22, ZSM-23, ZSM-35, Z5M-~ and ZSM-~18O
Of those zeolites, ZSM-5 is described in U.S. Patents
In U.S. Patent 2,489,093 s~ch an oxyhalogenation first stage is combined with a catalytic second stage condensation to produce higher hydrocarbons, including C2-C4 par~f~ins and olefins and C5~ aliphatlcs and aromatics. The catalysts involved include alumina~ silica and related condensation catalysts. The second stage dehydrohalogenation reaction may be simplified as follows-(n) CH3Cl [HC3~nHCl.
It is recognized that the hydrocarbon products (HC) mayinclude light gases such as ethane, propane, propylene and butanes, as well as the condensed liquid hydrocarbon products and halogenated by-products.
A process for converting aliphatic halides using ZSM-5 type zeolites is described in U.S. Patent 3,894,107. The preferred catalysts comprise crystalline aluminosilicates having a silica to alumina ratio of at least 12 and a constraint index of 1 to 12. In the acid form these are often denominated HZSM-5 type materials.
Co-extruded with alumina, these active zeolites are available in various forms and sizes such as 1.6 mm cylindrical extrudate particles.
The zeolites that are useful as components of the composite catalysts of the invention are those having a silica to alumina mole ratio greater than 12:1, preferably greater than 30:1, and a constraint index of 1 to 12, and are exemolified by the shape-selective, medium-pore, siliceous zeolites ZSM-5, ZSM~5/ZSM-ll intermediate, ZSM-ll, ZSM-12, ZSM-22, ZSM-23, ZSM-35, Z5M-~ and ZSM-~18O
Of those zeolites, ZSM-5 is described in U.S. Patents
3,702,886, Re. 29,948 and 4,061,724; ZS~-5/ZSM-ll intermediate is described in U.S. Patent 4,229,424; ZSM-ll is described in lJ. S.
Patent 3,709,979; ZSM-12 is described in U. S. Patent 3,8~2,449;
ZSM-23 is described in U. S. Patent 4,076,842; ZSM-35 is described in U. S. Patent 4,016,245; ZSM-38 is described in U. S. Patent
Patent 3,709,979; ZSM-12 is described in U. S. Patent 3,8~2,449;
ZSM-23 is described in U. S. Patent 4,076,842; ZSM-35 is described in U. S. Patent 4,016,245; ZSM-38 is described in U. S. Patent
4,046,859; and ZSM-48 is described in European Patent C0 15 132.
Such zeolites may obe used in the catalysts of the invention in the hydrogen form or they may be base exchansed or impregnated to contain a metal cation. It is desirable to calcine the zeolite after base exchange.
F~2703_L
The catalyst compositions of the invention may be prepared in various ways. For example1 the components may be separately prepared in the form of particles such as pellets or extrudates, and lntimately mixed in the required proportions. The sizes of the individual component particles may be quite small, or they may be as large as up to about 13 mm. Alternatively, the components may be mixed as powders and formed into composite pellets or extrudate, each pellet containing both components in substantially the required proportions.
It is desirable to incorporate the zeolite component of the composition in a matrix. Such a matrix is useful as a binder and imparts greater resistance to the catalyst towards severe temperature, pressure and velocity conditions. Hydrated alumina ( ~ -A1203 ~ O) is a preferred zeolite binder. Other matrix materials include both synthetic and natural substances.
Such substances include clays, silica and/or metal oxides. The latter may be either naturally occurring or in the form of gelatinous precipitates, sols or gels including mixtures o~ silica and metal oxides. Frequently, zeolite materials have been incorporated into naturally occurring clays, for example, bentonite and kaolin. In addition, the zeolite may be composited with a porous matrix material such as silica-alumina, silica-rnagnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, as well as ternary compositions such as silica-al~mina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia. The matrix can be in the form of a co-gel. A mlxture of clay in cornbination with silica or any of` the above speciFied co-gels may be used to form a matrlx.
In general, the crystalline zeolites are ordinarily ion exchanged with a desired cation to replace alkali metal present in the zeolite as found naturally or as synthetically prepared. Tne exchange treatment is such as to reduce the alkali metal content to less than about 50% by weight of the original alkali metal contained ln the zeolite as synthesized, usually 0.5 weight percent or less.
~æ~
The purpose of ion exchange is to substantially remove alkali metal cations which are known to be deleterious to catalytic activity, as well as to introduce particularly desired catalytic activity by means of the various cations used in the exchange medium. For the hydrocarbon conversion operation described hereint preferred cations are hydrogen, ammonium, rare earth and mixtures thereofg with particular preference being accorded to rare earth. Ion exchange is suitably accomplished by conventional contact of the zeolite with a suitable salt solution of the desired cation such as, for example, the sulfate, chloride or nitrate.
The ZSM-5 type zeolite used in the catalysts of the invention has the particular advantage of a hydrophobic nature and resistance to halogen acid deterioration. These characteristics are not readily ~ound in known condensation catalysts. By eliminating interstage separation of corrosive inorganic halogen materials and water from the haloalkanes, an economic process is achieved.
In general, conversion of alkyl halides to useful hydrocarbon product takes place in the temperature range of ~00 to 50ûC in the presence or absence o~ hydrogen. Pressures from below atmospheric to about 7000 kPa may be used, those of 5 to 500 kPa being preferred. Typicaliy, a weight hourly space velocity of about 0.5 to 50 WHSN based on zeolite content is employed in the catalyst bed.
The various products may oe recovered or recycled according to process needs. Unconverted methane and other light gases may be separated and recycled to the catalyst zone. Inorganic halogen-containing gases may be separated for recycle!-Legeneration or disposal, according to their composition. Halohydrocarbons may be recovered as product or recycled.
The following Examples illustrate the invention.
E A``1PLE 1 A Deacon chlorination catalyst was prepared by impregnatin~
30 parts by weight of a low surface area (14 m2/g) and medium porosity (0.25 ml~g) alumina with a solution o~ 6.1 parts by weight of CuCL2 . 2H20, 4.2 parts by weight of KCl and 6.4 parts by weight of REC13 in 60 parts by weight of water; it was then dried at 110C and calcined at 371C for 3 hours. An acid ZSM~5 was prepared by calcining the "as synthesized" ZSM 5 (SiO2/A1203 =
40) at 538C in N2 for 3 hours. The calcined zeolite was ion exchanged with NH4N03 solution to reduce Na -to less than 0.02~
by weight, -then converted into acid form by air calcination at 538C
for 3 hours. One part of chlorination catalyst and four parts of acid ZSM-5 were then composited together.
. _ A feedstock of me-thane and chlorine was reacted over the composite catalyst of Example 1 in a downflow tubular reactor. The operating conditions and results are shown Table I.
TAELE I
__ Catalyst: Chlorination and ZSM-5 Catalyst Composite Total Weight: 5 Grams Run No. 2A 2B 2C
Feedstock Methanet ml/min 23.5 23.5 23.5 Chlorine, ml/min 5.0 5.0 5.û
oerating Conditions Temperature, C 427 427 454 Pressure, kPa 100 lûO 100 Time on Stream, hours 1.5 3.0 1.0 CH4 Conversion, mol % 6.09 7.3 5.08 Product Distribution mol ~
C ~ - ' 93.91 92.70 94.92 C2 0.46 1.14 1.48 C3 4.83 3.~ 1.83 C4-~ 0.82 2.26 1.77 A Deacon chlorination catalyst was prepared by impregnating 100 parts by weight of particles of calcined alumina (Alcoa A-3) with 6.1 parts by weight of CuC12 . 2~ 0, 2.7 parts by weight of MgC12 and 6.2 parts by weight of rare earth chloride in 61 parts by weiyht of water. The impregnated particles were dried at about 100C to remove water and then calcined at about 370C for 3 hours.
This catalyst was mixed with HZSM-5 as described in Example 1, in the proportions descrlbed in Example 1.
A Deacon oxychlorination catalyst was prepared by impregnating 103 parts by weight of particles of calcined alumina !Alcoa A-3) with 10.1 parts by weight CuC12 . 2~09 7.0 parts by weight KCl, and 10.6 parts by weight rare earth chloride dissolved in 100 parts by weight of water. rne impregnated particles were dried at about llOQC to rrmove water and calcined at about 370C for three hours. The Deacon catalyst was then mixed with a standard commercially available acid ZSM-5 catalyst containing 65 wt. ~ ZSM-5 and 35% alumina in 1.6 mm extrudate form. rne composite catalyst contained four parts by weight of ZSM 5 ex-trudate and one part by weight of Deacon catalyst.
The Deacon catalyst components may be deposited on a zeolite condensation catalyst as carrier. Typically, the active halogenation components comprise about 1 to 20 weight percent of the active zeolite, with about 3 tc 12 wt% being preferred. Typically~
a fixed bed catalyst comprises about 10 to 90% active catalytic components, the remainder being inert bînder.
In the oxyhalogenation of alkanes, it is advantageous to control the relative amounts of reactant gases to minimize formation of polyhalogenated alkanes, such as methylene chloride (C ~C12), chloroform and dihalo ethanes, for e~ample. This may be achleved in a continuous process by regulating the flow of hydrocarbon gas to maintain a stoichiometric excess relative to the halogen.
Ordinarily, the mole ratio of alkane to halogen is in the range of æ~8~
F~2703-L
1:1 to 10:1. To avoid deleterious effec-ts in the system, it may be desirable to limit halogen-acid gas concentration, especially where gases such as HCl or HBr could combine wi-th water.
Direct halogenation of lower alkanes is a well~known industrial p~ocess. In the absence of light or catalyst, thermal chlorination of methane is carried out as a chain reaction by thermal dissoclation of C12. A lower activation energy is required for catalytic chlorination. Direct chlorination may be depicted by the following:
CH4 ~ C12 ~ CH3Cl + HC1.
Both direct chlorination and oxychlorination are believed to proceed by generating chlorine atoms, which react with methane to form HCl and a methyl radical. The CH3 ra~ical in turn reacts with chlorine to form chloromethane.
The addition of oxygen to halogenation gases is well known. Hydrogen halides ~HX) are converted to halogen and water by heating with an oxygen-containing gas sucn as air or pure 2 Where oxygen is maintained in a stoichiometric excess to HX, little if any hydrogen halide gas will escape the halogenation zonP. For this reason, oxyhalogenation is advantageous as compared to direct halogenation. Where 2 and C12 are present in the halogenation gas, HCl formed is reacted with alkane and 2 for further conversion .
Such zeolites may obe used in the catalysts of the invention in the hydrogen form or they may be base exchansed or impregnated to contain a metal cation. It is desirable to calcine the zeolite after base exchange.
F~2703_L
The catalyst compositions of the invention may be prepared in various ways. For example1 the components may be separately prepared in the form of particles such as pellets or extrudates, and lntimately mixed in the required proportions. The sizes of the individual component particles may be quite small, or they may be as large as up to about 13 mm. Alternatively, the components may be mixed as powders and formed into composite pellets or extrudate, each pellet containing both components in substantially the required proportions.
It is desirable to incorporate the zeolite component of the composition in a matrix. Such a matrix is useful as a binder and imparts greater resistance to the catalyst towards severe temperature, pressure and velocity conditions. Hydrated alumina ( ~ -A1203 ~ O) is a preferred zeolite binder. Other matrix materials include both synthetic and natural substances.
Such substances include clays, silica and/or metal oxides. The latter may be either naturally occurring or in the form of gelatinous precipitates, sols or gels including mixtures o~ silica and metal oxides. Frequently, zeolite materials have been incorporated into naturally occurring clays, for example, bentonite and kaolin. In addition, the zeolite may be composited with a porous matrix material such as silica-alumina, silica-rnagnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, as well as ternary compositions such as silica-al~mina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia. The matrix can be in the form of a co-gel. A mlxture of clay in cornbination with silica or any of` the above speciFied co-gels may be used to form a matrlx.
In general, the crystalline zeolites are ordinarily ion exchanged with a desired cation to replace alkali metal present in the zeolite as found naturally or as synthetically prepared. Tne exchange treatment is such as to reduce the alkali metal content to less than about 50% by weight of the original alkali metal contained ln the zeolite as synthesized, usually 0.5 weight percent or less.
~æ~
The purpose of ion exchange is to substantially remove alkali metal cations which are known to be deleterious to catalytic activity, as well as to introduce particularly desired catalytic activity by means of the various cations used in the exchange medium. For the hydrocarbon conversion operation described hereint preferred cations are hydrogen, ammonium, rare earth and mixtures thereofg with particular preference being accorded to rare earth. Ion exchange is suitably accomplished by conventional contact of the zeolite with a suitable salt solution of the desired cation such as, for example, the sulfate, chloride or nitrate.
The ZSM-5 type zeolite used in the catalysts of the invention has the particular advantage of a hydrophobic nature and resistance to halogen acid deterioration. These characteristics are not readily ~ound in known condensation catalysts. By eliminating interstage separation of corrosive inorganic halogen materials and water from the haloalkanes, an economic process is achieved.
In general, conversion of alkyl halides to useful hydrocarbon product takes place in the temperature range of ~00 to 50ûC in the presence or absence o~ hydrogen. Pressures from below atmospheric to about 7000 kPa may be used, those of 5 to 500 kPa being preferred. Typicaliy, a weight hourly space velocity of about 0.5 to 50 WHSN based on zeolite content is employed in the catalyst bed.
The various products may oe recovered or recycled according to process needs. Unconverted methane and other light gases may be separated and recycled to the catalyst zone. Inorganic halogen-containing gases may be separated for recycle!-Legeneration or disposal, according to their composition. Halohydrocarbons may be recovered as product or recycled.
The following Examples illustrate the invention.
E A``1PLE 1 A Deacon chlorination catalyst was prepared by impregnatin~
30 parts by weight of a low surface area (14 m2/g) and medium porosity (0.25 ml~g) alumina with a solution o~ 6.1 parts by weight of CuCL2 . 2H20, 4.2 parts by weight of KCl and 6.4 parts by weight of REC13 in 60 parts by weight of water; it was then dried at 110C and calcined at 371C for 3 hours. An acid ZSM~5 was prepared by calcining the "as synthesized" ZSM 5 (SiO2/A1203 =
40) at 538C in N2 for 3 hours. The calcined zeolite was ion exchanged with NH4N03 solution to reduce Na -to less than 0.02~
by weight, -then converted into acid form by air calcination at 538C
for 3 hours. One part of chlorination catalyst and four parts of acid ZSM-5 were then composited together.
. _ A feedstock of me-thane and chlorine was reacted over the composite catalyst of Example 1 in a downflow tubular reactor. The operating conditions and results are shown Table I.
TAELE I
__ Catalyst: Chlorination and ZSM-5 Catalyst Composite Total Weight: 5 Grams Run No. 2A 2B 2C
Feedstock Methanet ml/min 23.5 23.5 23.5 Chlorine, ml/min 5.0 5.0 5.û
oerating Conditions Temperature, C 427 427 454 Pressure, kPa 100 lûO 100 Time on Stream, hours 1.5 3.0 1.0 CH4 Conversion, mol % 6.09 7.3 5.08 Product Distribution mol ~
C ~ - ' 93.91 92.70 94.92 C2 0.46 1.14 1.48 C3 4.83 3.~ 1.83 C4-~ 0.82 2.26 1.77 A Deacon chlorination catalyst was prepared by impregnating 100 parts by weight of particles of calcined alumina (Alcoa A-3) with 6.1 parts by weight of CuC12 . 2~ 0, 2.7 parts by weight of MgC12 and 6.2 parts by weight of rare earth chloride in 61 parts by weiyht of water. The impregnated particles were dried at about 100C to remove water and then calcined at about 370C for 3 hours.
This catalyst was mixed with HZSM-5 as described in Example 1, in the proportions descrlbed in Example 1.
A Deacon oxychlorination catalyst was prepared by impregnating 103 parts by weight of particles of calcined alumina !Alcoa A-3) with 10.1 parts by weight CuC12 . 2~09 7.0 parts by weight KCl, and 10.6 parts by weight rare earth chloride dissolved in 100 parts by weight of water. rne impregnated particles were dried at about llOQC to rrmove water and calcined at about 370C for three hours. The Deacon catalyst was then mixed with a standard commercially available acid ZSM-5 catalyst containing 65 wt. ~ ZSM-5 and 35% alumina in 1.6 mm extrudate form. rne composite catalyst contained four parts by weight of ZSM 5 ex-trudate and one part by weight of Deacon catalyst.
The Deacon catalyst components may be deposited on a zeolite condensation catalyst as carrier. Typically, the active halogenation components comprise about 1 to 20 weight percent of the active zeolite, with about 3 tc 12 wt% being preferred. Typically~
a fixed bed catalyst comprises about 10 to 90% active catalytic components, the remainder being inert bînder.
In the oxyhalogenation of alkanes, it is advantageous to control the relative amounts of reactant gases to minimize formation of polyhalogenated alkanes, such as methylene chloride (C ~C12), chloroform and dihalo ethanes, for e~ample. This may be achleved in a continuous process by regulating the flow of hydrocarbon gas to maintain a stoichiometric excess relative to the halogen.
Ordinarily, the mole ratio of alkane to halogen is in the range of æ~8~
F~2703-L
1:1 to 10:1. To avoid deleterious effec-ts in the system, it may be desirable to limit halogen-acid gas concentration, especially where gases such as HCl or HBr could combine wi-th water.
Direct halogenation of lower alkanes is a well~known industrial p~ocess. In the absence of light or catalyst, thermal chlorination of methane is carried out as a chain reaction by thermal dissoclation of C12. A lower activation energy is required for catalytic chlorination. Direct chlorination may be depicted by the following:
CH4 ~ C12 ~ CH3Cl + HC1.
Both direct chlorination and oxychlorination are believed to proceed by generating chlorine atoms, which react with methane to form HCl and a methyl radical. The CH3 ra~ical in turn reacts with chlorine to form chloromethane.
The addition of oxygen to halogenation gases is well known. Hydrogen halides ~HX) are converted to halogen and water by heating with an oxygen-containing gas sucn as air or pure 2 Where oxygen is maintained in a stoichiometric excess to HX, little if any hydrogen halide gas will escape the halogenation zonP. For this reason, oxyhalogenation is advantageous as compared to direct halogenation. Where 2 and C12 are present in the halogenation gas, HCl formed is reacted with alkane and 2 for further conversion .
Claims (6)
1. A catalyst composition comprising (a) a Deacon catalyst comprising cupric halide, alkaline earth metal halide and/or alkali metal halide, and/or rare earth metal halide and (b) a crystalline aluminosilicate zeolite having a silica to alumina mole ratio greater than 12:1 and constraint index of 1 to 12.
2. A catalyst composition according to claim 1, wherein the Deacon catalyst component comprises from 1 to 20 weight percent of the zeolite component.
3. A catalyst composition according to claim 2, which comprises from 10 to 90 weight percent of an alumina binder.
4. A catalyst composition according to claim 1, 2 or 3, wherein the zeolite component is acid ZSM-5 having a silica:alumina mole ratio greater than 30:1.
5. A catalyst composition according to claim 1, 2 or 3, wherein the Deacon catalyst components are deposited on alumina and composited with HZSM-5.
6. A catalyst composition according to claim 1, 2 or 3, wherein the Deacon catalyst includes CuCl2, alkali metal chloride or alkaline earth chloride, and rare earth chloride, impregnated on alumina.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US594,583 | 1984-03-29 | ||
| US06/594,583 US4513092A (en) | 1984-01-04 | 1984-03-29 | Composite catalyst for halogenation and condensation of alkanes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1229841A true CA1229841A (en) | 1987-12-01 |
Family
ID=24379501
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000476865A Expired CA1229841A (en) | 1984-03-29 | 1985-03-19 | Catalyst for oxyhalogenation and condensation of alkanes |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4513092A (en) |
| EP (1) | EP0156634B1 (en) |
| JP (1) | JPS60225647A (en) |
| AU (1) | AU575923B2 (en) |
| CA (1) | CA1229841A (en) |
| DE (1) | DE3564082D1 (en) |
| NZ (1) | NZ211452A (en) |
| ZA (1) | ZA852416B (en) |
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| US4910176A (en) * | 1982-10-18 | 1990-03-20 | The Dow Chemical Company | Catalytic process for ethylene dichloride |
| IT1176856B (en) * | 1984-10-05 | 1987-08-18 | Montedipe Spa | METHOD FOR THE SYNTHESIS OF IODOBENZENE |
| IT1176981B (en) * | 1984-10-16 | 1987-08-26 | Montedipe Spa | METHOD FOR THE SYNTHESIS OF IODOBENZENE |
| US4769504A (en) * | 1987-03-04 | 1988-09-06 | The United States Of America As Represented By The United States Department Of Energy | Process for converting light alkanes to higher hydrocarbons |
| US4792642A (en) * | 1987-03-25 | 1988-12-20 | Eastman Kodak Company | Process for preparing iodinated aromatic compounds |
| US4778940A (en) * | 1987-03-25 | 1988-10-18 | Eastman Kodak Company | Process for preparing iodinated substituted aromatic compounds |
| US4795737A (en) * | 1987-03-25 | 1989-01-03 | Eastman Kodak Company | Process for the iodination of aromatic compounds over solid catalysts |
| US4778939A (en) * | 1987-03-25 | 1988-10-18 | Eastman Kodak Company | Low temperature oxyiodination of aromatic compounds |
| US4788355A (en) * | 1987-10-16 | 1988-11-29 | Eastman Kodak Company | Oxyiodination catalyst |
| US4788356A (en) * | 1987-10-16 | 1988-11-29 | Eastman Kodak Company | Novel method for oxyiodination product partial purification |
| US5329057A (en) * | 1991-04-19 | 1994-07-12 | The Dow Chemical Company | Process for the cyclodimerization of 1,3-butadienes to 4-vinylcyclohexenes |
| US7230150B2 (en) * | 2001-04-18 | 2007-06-12 | Grt, Inc. | Zone reactor |
| US7019182B2 (en) * | 2001-04-18 | 2006-03-28 | Grt, Inc. | Method of hydrocarbon preservation and environmental protection |
| US6525230B2 (en) * | 2001-04-18 | 2003-02-25 | Grt, Inc. | Zone reactor |
| US7838708B2 (en) | 2001-06-20 | 2010-11-23 | Grt, Inc. | Hydrocarbon conversion process improvements |
| US20030078456A1 (en) * | 2001-06-20 | 2003-04-24 | Aysen Yilmaz | Integrated process for synthesizing alcohols, ethers, aldehydes, and olefins from alkanes |
| US20030069452A1 (en) * | 2001-06-20 | 2003-04-10 | Sherman Jeffrey H. | Method and apparatus for synthesizing from alcohols and ethers from alkanes, alkenes, and aromatics |
| US7161050B2 (en) * | 2001-06-20 | 2007-01-09 | Grt, Inc. | Method and apparatus for synthesizing olefins, alcohols, ethers, and aldehydes |
| US20050171393A1 (en) | 2003-07-15 | 2005-08-04 | Lorkovic Ivan M. | Hydrocarbon synthesis |
| WO2005021468A1 (en) | 2003-07-15 | 2005-03-10 | Grt, Inc. | Hydrocarbon synthesis |
| US20080275284A1 (en) | 2004-04-16 | 2008-11-06 | Marathon Oil Company | Process for converting gaseous alkanes to liquid hydrocarbons |
| US7674941B2 (en) | 2004-04-16 | 2010-03-09 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons |
| US8173851B2 (en) * | 2004-04-16 | 2012-05-08 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons |
| US8642822B2 (en) | 2004-04-16 | 2014-02-04 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons using microchannel reactor |
| US20060100469A1 (en) * | 2004-04-16 | 2006-05-11 | Waycuilis John J | Process for converting gaseous alkanes to olefins and liquid hydrocarbons |
| US7244867B2 (en) | 2004-04-16 | 2007-07-17 | Marathon Oil Company | Process for converting gaseous alkanes to liquid hydrocarbons |
| US20060229475A1 (en) * | 2005-04-11 | 2006-10-12 | Weiss Michael J | Synthesis of hydroxylated hydrocarbons |
| US20060229228A1 (en) * | 2005-04-11 | 2006-10-12 | Zachary John Anthony Komon | Method of making alkoxylates |
| RU2409547C2 (en) * | 2005-05-04 | 2011-01-20 | Дау Глобал Текнолоджиз Инк. | Method for oxidative halogenation and method of producing halogenated c1 product |
| EP2457887A1 (en) | 2006-02-03 | 2012-05-30 | GRT, Inc. | Continuous process for converting natural gas to liquid hydrocarbons |
| EP1993951B1 (en) | 2006-02-03 | 2014-07-30 | GRT, Inc. | Separation of light gases from bromine |
| US20090163749A1 (en) * | 2006-03-20 | 2009-06-25 | Microvast Technologies, Ltd. | Conversion of methane into c3˜c13 hydrocarbons |
| CN100582064C (en) * | 2006-03-20 | 2010-01-20 | 微宏科技（湖州）有限公司 | Flow process for synthesizing C3 to C13 high hydrocarbons by methane through non-synthetic gas method |
| CN101765574A (en) * | 2007-05-24 | 2010-06-30 | Grt公司 | Zone reactor incorporating reversible hydrogen halide capture and release |
| US8282810B2 (en) | 2008-06-13 | 2012-10-09 | Marathon Gtf Technology, Ltd. | Bromine-based method and system for converting gaseous alkanes to liquid hydrocarbons using electrolysis for bromine recovery |
| US20090312586A1 (en) * | 2008-06-13 | 2009-12-17 | Marathon Gtf Technology, Ltd. | Hydrogenation of multi-brominated alkanes |
| AU2009270801B2 (en) | 2008-07-18 | 2014-04-24 | Reaction 35, Llc | Continuous process for converting natural gas to liquid hydrocarbons |
| US8367884B2 (en) | 2010-03-02 | 2013-02-05 | Marathon Gtf Technology, Ltd. | Processes and systems for the staged synthesis of alkyl bromides |
| US8198495B2 (en) | 2010-03-02 | 2012-06-12 | Marathon Gtf Technology, Ltd. | Processes and systems for the staged synthesis of alkyl bromides |
| US8815050B2 (en) | 2011-03-22 | 2014-08-26 | Marathon Gtf Technology, Ltd. | Processes and systems for drying liquid bromine |
| US8436220B2 (en) | 2011-06-10 | 2013-05-07 | Marathon Gtf Technology, Ltd. | Processes and systems for demethanization of brominated hydrocarbons |
| US8829256B2 (en) | 2011-06-30 | 2014-09-09 | Gtc Technology Us, Llc | Processes and systems for fractionation of brominated hydrocarbons in the conversion of natural gas to liquid hydrocarbons |
| US8802908B2 (en) | 2011-10-21 | 2014-08-12 | Marathon Gtf Technology, Ltd. | Processes and systems for separate, parallel methane and higher alkanes' bromination |
| US9193641B2 (en) | 2011-12-16 | 2015-11-24 | Gtc Technology Us, Llc | Processes and systems for conversion of alkyl bromides to higher molecular weight hydrocarbons in circulating catalyst reactor-regenerator systems |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL288318A (en) * | 1962-02-01 | |||
| NL298347A (en) * | 1962-09-27 | |||
| US3546306A (en) * | 1967-08-22 | 1970-12-08 | Donal E Mccarthy | Production of alkylene dihalides |
| FR1579562A (en) * | 1968-04-24 | 1969-08-29 | ||
| CA920775A (en) * | 1968-05-13 | 1973-02-13 | Vadekar Mohan | Oxidation of hydrogen chloride using molecular sieve catalysts |
| US3914328A (en) * | 1971-05-17 | 1975-10-21 | Stauffer Chemical Co | Catalyst regeneration |
| US3926847A (en) * | 1973-06-04 | 1975-12-16 | Vulcan Materials Co | Catalysts comprising a metal halide salt on an interstratified synthetic aluminosilicate carrier and chlorination processes, etc. |
| IT1030646B (en) * | 1974-10-04 | 1979-04-10 | Sir Soc Italiana Resine Spa | PROCEDURE FOR THE PRODUCTION OF DICHLOROETHANE |
| US4096163A (en) * | 1975-04-08 | 1978-06-20 | Mobil Oil Corporation | Conversion of synthesis gas to hydrocarbon mixtures |
| US4297328A (en) * | 1979-09-28 | 1981-10-27 | Union Carbide Corporation | Three-way catalytic process for gaseous streams |
| CA1216273A (en) * | 1982-10-18 | 1987-01-06 | Ronald W. Diesen | Catalytic process for ethylene dichloride |
-
1984
- 1984-03-29 US US06/594,583 patent/US4513092A/en not_active Expired - Fee Related
-
1985
- 1985-03-15 NZ NZ211452A patent/NZ211452A/en unknown
- 1985-03-19 CA CA000476865A patent/CA1229841A/en not_active Expired
- 1985-03-22 AU AU40283/85A patent/AU575923B2/en not_active Ceased
- 1985-03-22 DE DE8585302011T patent/DE3564082D1/en not_active Expired
- 1985-03-22 EP EP85302011A patent/EP0156634B1/en not_active Expired
- 1985-03-29 JP JP60064086A patent/JPS60225647A/en active Granted
- 1985-03-29 ZA ZA852416A patent/ZA852416B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| US4513092A (en) | 1985-04-23 |
| NZ211452A (en) | 1987-07-31 |
| AU575923B2 (en) | 1988-08-11 |
| JPS60225647A (en) | 1985-11-09 |
| JPH0535021B2 (en) | 1993-05-25 |
| ZA852416B (en) | 1986-11-26 |
| DE3564082D1 (en) | 1988-09-08 |
| AU4028385A (en) | 1985-10-03 |
| EP0156634B1 (en) | 1988-08-03 |
| EP0156634A3 (en) | 1986-05-14 |
| EP0156634A2 (en) | 1985-10-02 |
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