CA1177464A - Process and catalyst for converting synthesis gas to liquid hydrocarbon mixture - Google Patents
Process and catalyst for converting synthesis gas to liquid hydrocarbon mixtureInfo
- Publication number
- CA1177464A CA1177464A CA000412380A CA412380A CA1177464A CA 1177464 A CA1177464 A CA 1177464A CA 000412380 A CA000412380 A CA 000412380A CA 412380 A CA412380 A CA 412380A CA 1177464 A CA1177464 A CA 1177464A
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- Prior art keywords
- catalyst
- weight
- cobalt
- thoria
- mixture
- Prior art date
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
ABSTRACT OF THE DISCLOSURE
Synthesis gas containing CO and H2 is converted to a high-octane hydrocarbon liquid in the gasoline boiling point range by bringing the gas into contact with a heterogeneous catalyst including, in physical mixture, a zeolite molecular sieve, cobalt at 6-20% by weight, and thoria at 0.5-3.9%
by weight. The contacting occurs at a temperature of 250-300°C, and a pressure of 10-30 atmospheres. The conditions can be selected to form a major portion of the hydrocarbon product in the gasoline boiling range with a research octane of more than 80 and less than 10% by weight aromatics.
Synthesis gas containing CO and H2 is converted to a high-octane hydrocarbon liquid in the gasoline boiling point range by bringing the gas into contact with a heterogeneous catalyst including, in physical mixture, a zeolite molecular sieve, cobalt at 6-20% by weight, and thoria at 0.5-3.9%
by weight. The contacting occurs at a temperature of 250-300°C, and a pressure of 10-30 atmospheres. The conditions can be selected to form a major portion of the hydrocarbon product in the gasoline boiling range with a research octane of more than 80 and less than 10% by weight aromatics.
Description
~ 1 77~L64 PROCESS AND CATALYST FOR CONVERTING
SYNTHESIS GAS TO LIQUID HYDROCARBO~ MIXTURE
. . _ The present invention relates to a method for converting synthesis gas containing carbon monoxide and hydrogen to hydrocarbon mixtures suitable for fuel use or as feedstock in petrochemical industries. The invention also relates to catalysts in which mixtures of metals having reductive catalytic activity are dispersed within a crystalline aluminosilicate molecular sieve. In particular the process involves production of high octane, liquid hydrocarbon products that are in the gasoline boiling range. The present catalyst and method selectively produce branched aliphatic hydrocarbons rather than aromatics to obtain a high octane product.
In response to the shortage of petroleu~ products in the past several years, there has been substantial interest in the conversion of coal to both liquid and gaseous hydrocarbon products. Much work has been done in the area of coal gasification by reaction with water and oxygen to produce carbon monoxide, hydrogen and carbon dioxide as well as of other gàses. It is well known that these gasification products can be converted to valued hydrocarbons for use as motor fuels, petrochemical feedstocks and fuel gases.
; ' , ' :~
', .~ ,:
, ! ! 77~4 A detailed trea~ment of one well known conversion process is given in Storch, The Fischer-Tropsch and Related Synthesis.
This work describes the use of the various reductive catalytic metals such as cobalt, nickel and iron in mixture with promoters such as thoria, magnesia and manganese and diluent carriers such as kieselguhr, pumice or infusorial earth to convert synthesis gas to a wide range of hydrocarbons. In particular, considerable work was reported involving cobalt catalysts promoted with thoria on amorphous kieselguhr carrier. However, the hydrocarbon product resulting from the use of this catalyst is generally of low octane rating with straight chain aliphatic hydrocarbons constituting the liquids within the gasoline boiling point range. The Fischer-Tropsch process often was regarded as one that could best be used for the production of aliphatic chemicals and special products such as waxes and high grade lubricants rather than fuels.
In recent years there has been considerable interest in the use of zeolite or aluminosilicate molecular sieve supports for Fischer-Tropsch's catalysts. U.S. Patent number 4,086,262 suggests the use of a number of zeolites including 2SM-5 having a uniform pore diameter of about 5-6 angstroms as a support for various Fischer-Tropschs catalysts. Catalytic metals including iron, cobalt, nickel, ruthenium, thorium, rhodium, and osmium are suggested. This patent reports the use of a thoria catalyst on acid substituted zS~-5 zeolite to produce a hydrocarbon product from the conversion of a synthesis gas containing carbon monoxide and hydrogen.
This catalyst was used at temperatures above 400 C to 77~6~
result in a liquid product rich in aromatics, but which generally represents a low percentage of the total product.
Accordingly, it is an object of the present invention to provide a method of producing a high octane liquid hydro-carbon from the converslon of a synthesis gas.
It is a further object to provide a method of obtaining a high conversion of carbon monoxide and hydrogen in a synthesis gas to a liquid having a major portion thereof as C5 and higher hydrocarbons and with a high research octane number.
It is also an object to provide a catalyst for the reaction of carbon monoxide and hydrogen gases to form liquid hydrocarbons of high research octane rating but with a low aromatic content.
In accordance with the present invention, a ~ethod of producing a hydrocarbon product having a major proportion by weight of C5 and higher hydrocarbons in the gasoline boiling point range includes the steps of forming a catalyst with a mixture of cobalt, thoria and a crystalline alumino-silicate (2eolite) having a pore size of 5-6 angstroms with cobalt included at 6-20% and thoria at`0.5-3~ by weight followed by contacing the catalyst with a gas mixture including hydrogen and carbon monoxide at a temperature of about 250-300 C at 10-30 atmospheric pressure.
In more specific aspects of the invention the catalyst is contacted with the hydrogen and carbon monoxide gas at a temperature of about 280 C and a pressure of about 20 atmospheres. The zeolite is in the acid substituted form with a silica to alumina ratio of about 25-50 and is included in the catalyst at about 75-93~ by weight.
~ ~ 77~64 In preparing the catalyst for the method of the present invention, a solution of soluble cobalt and thorium salts such as nitrates can be prepared in sufficient concentration of each metal to permit inclusion at the desired level in the completed catalyst. The metals can be precipitated as carbonates or other insoluble salts, then after drying, blended with the selected support material. Heating and reduction steps will provide cobalt metal and thorium dioxide (thoria) within the finished catalysts. The cobalt preferably is included in the catalyst at a weight of about 4-10 times that of the thoria. Suitable catalysts for use include about 6-20~
by weight cobalt and 0.5-3~ by weight thoria, with a preferred range of about 6-14% by weight cobalt and 0.7-2~ by weight thoria.
The support material for the catalyst is a crystalline aluminosilicate molecular sieve also known as a zeolite.
Such zeolites are described in the published li~erature and can be prepared by well defined processes, for instance as is presented in U.S. Patent Number 3,702,886. The zeolite employed in the present catalyst preferably includes pores of uniform diameter of about 5-6 angstroms. It is intended that the catalyst with this support used in accordance with the invention will be selective to the production of aliphatic hydrocarbons in the range of about C5 to C12 with substantial branched chains to enhance the octane rating of the liquid product.
The catalytic metals can be incorporated with the ~eolite support material in several ways. As suggested the cobalt and thorium can be precipitated from solution as ~ ~ 7 7 ~ 6 4 carbonates, dried and calcined to their oxides. The precipitate is crushed, classified to size and blended in a physical mixture with the zeolite in granular form. It is preferred that granules of about 80 ~icrometers (200 mesh) or less be used for both the metal oxide and zeolite. Alternatively, a solution of the cobalt and thorium soluble salts can be used to permeate into the zeolite which is subsequently dried and heated to a su~ficient temperature to convert the catalytic metals to the oxide. In either of these instances aqueous or acetone solutions are suitable for preparing the catalyst. Prior to use the cobalt oxide dispersed throughout the zeolite is reduced, with for instance hydrogen gas at a temperature of about 350 C and a pressure of typically 20 atmospheres to form cobalt metal.
The catalyst as thus described is used in the process of this invention by contacting it with a flow of synthesis gas containing hydrogen and carbon monoxide. It nas been found that the temperature of contact is of importance in obtaining a high percentage of the product liquid within the gasoline boiling range and in obtaining a high proportion of that liquid as branched chain olefins so as to provide a high octane number and thereby increase the value of the product as a fuel for internal combustion engines. For this purpose contact temperatures of about 250-300 C are required with a preferred temperature of about 280 C. Reaction temperatures much above this range not only decrease the total amount of liquid in the product includinq that within the gasoline boiling range but also increase the aromatic I li77464 content of thé remaining liquid. Although aromatics can be useful in increasing the octane rating of the fuel, they may carry with them undesirable health effects. It is therefore suggested that the problem of exhaust gas cleanup, may be ameliorated through the selection of branched chain olefins (and possibly pariffins) for imparting high octane characteristics to a liquid hydrocarbon fuel.
In the selection of other process conditions the sythesis gas pressure should be sufficien~ly high to provide good concentrations of the reactants hydrogen and carbon monoxide in contact with the catalyst but not so high as to raise instrumentation and mechanical problems. Typically pressures of about 1-70 atmospheres are contemplated for use with a preferred range of about 10-30 atmospheres. Space velocities of about 500-50,000 gas volumes per hour in respect to the catalyst are typical in processes of this type and can be selected to provide the desired conversion and production.
The heterogeneous catalyst can be contained in a fixed or a fluidized bed whilè contacting the synthesis gas flow.
At the reaction temperatures and pressures, the product stream is a mixture of liquids and gases which can be recovered by well known techniques. The gasoline fraction can be separated from the remaining products in a suitable distilation process.
The following examples are presented as an illustration and comparsion of the present process and catalyst with previous catalysts and methods.
A mixture of cobalt and thorium compounds with substan-tially more cobalt than thorium is pre~ipitated from,a nitrate l ~ 77~4 solution by the addition of sodium carbonate followed by heating to a boiling temperature. The precipitate is washed and then dried at about 110 C. The material is crushed to pass through 200 mesh (80 micro~eters) and mixed with about 4 weight parts of the zeolite ZSM-5 in granules of about the same size. The resulting ~ixture was pelleti~ed to about 1/2 cm diameter pellets. Following calcining and reduction wi~h ~2 gas at 350 C, the catalyst prepared in this manner contained about 10-11% by weight cobalt and about 1-2% by weight thoria~
About 60 grams of this catalyst was contacted with a continuous flow of synthesis gas containing about a 1:1 CO/H2 ratio at a gas volume hourly space velocity of about 1000, a pressure of about 20 atmospheres and a te~perature of 280 C in a stirred Berty reactor. The resulting product included over 60% by weight C5 and heavier hydrocarbon liquid. About 89% of this liquid was within the gasoline boiling range below about 200 C
while 11~ was in the diesel fuel range boiling between about 200-340 C. The liquid was found to have a research octane number of 86 but with only about 3% by weight aromatics.
Additional data respecting the Exa~ple along with a second run under si~ilar conditions is given below in Table 1. Table I
also includes for co~parison data fro~ U.S. Patent No.
4,086,262 (Table I) respecting a thoria and ZSM-5 catalyst in about equal parts used to convert a sythesis gas to hydro-carbons.
.
I ~77~64 CATALYST _ZSM-S(Co,ThO ) ZSM-5 + ThO2
SYNTHESIS GAS TO LIQUID HYDROCARBO~ MIXTURE
. . _ The present invention relates to a method for converting synthesis gas containing carbon monoxide and hydrogen to hydrocarbon mixtures suitable for fuel use or as feedstock in petrochemical industries. The invention also relates to catalysts in which mixtures of metals having reductive catalytic activity are dispersed within a crystalline aluminosilicate molecular sieve. In particular the process involves production of high octane, liquid hydrocarbon products that are in the gasoline boiling range. The present catalyst and method selectively produce branched aliphatic hydrocarbons rather than aromatics to obtain a high octane product.
In response to the shortage of petroleu~ products in the past several years, there has been substantial interest in the conversion of coal to both liquid and gaseous hydrocarbon products. Much work has been done in the area of coal gasification by reaction with water and oxygen to produce carbon monoxide, hydrogen and carbon dioxide as well as of other gàses. It is well known that these gasification products can be converted to valued hydrocarbons for use as motor fuels, petrochemical feedstocks and fuel gases.
; ' , ' :~
', .~ ,:
, ! ! 77~4 A detailed trea~ment of one well known conversion process is given in Storch, The Fischer-Tropsch and Related Synthesis.
This work describes the use of the various reductive catalytic metals such as cobalt, nickel and iron in mixture with promoters such as thoria, magnesia and manganese and diluent carriers such as kieselguhr, pumice or infusorial earth to convert synthesis gas to a wide range of hydrocarbons. In particular, considerable work was reported involving cobalt catalysts promoted with thoria on amorphous kieselguhr carrier. However, the hydrocarbon product resulting from the use of this catalyst is generally of low octane rating with straight chain aliphatic hydrocarbons constituting the liquids within the gasoline boiling point range. The Fischer-Tropsch process often was regarded as one that could best be used for the production of aliphatic chemicals and special products such as waxes and high grade lubricants rather than fuels.
In recent years there has been considerable interest in the use of zeolite or aluminosilicate molecular sieve supports for Fischer-Tropsch's catalysts. U.S. Patent number 4,086,262 suggests the use of a number of zeolites including 2SM-5 having a uniform pore diameter of about 5-6 angstroms as a support for various Fischer-Tropschs catalysts. Catalytic metals including iron, cobalt, nickel, ruthenium, thorium, rhodium, and osmium are suggested. This patent reports the use of a thoria catalyst on acid substituted zS~-5 zeolite to produce a hydrocarbon product from the conversion of a synthesis gas containing carbon monoxide and hydrogen.
This catalyst was used at temperatures above 400 C to 77~6~
result in a liquid product rich in aromatics, but which generally represents a low percentage of the total product.
Accordingly, it is an object of the present invention to provide a method of producing a high octane liquid hydro-carbon from the converslon of a synthesis gas.
It is a further object to provide a method of obtaining a high conversion of carbon monoxide and hydrogen in a synthesis gas to a liquid having a major portion thereof as C5 and higher hydrocarbons and with a high research octane number.
It is also an object to provide a catalyst for the reaction of carbon monoxide and hydrogen gases to form liquid hydrocarbons of high research octane rating but with a low aromatic content.
In accordance with the present invention, a ~ethod of producing a hydrocarbon product having a major proportion by weight of C5 and higher hydrocarbons in the gasoline boiling point range includes the steps of forming a catalyst with a mixture of cobalt, thoria and a crystalline alumino-silicate (2eolite) having a pore size of 5-6 angstroms with cobalt included at 6-20% and thoria at`0.5-3~ by weight followed by contacing the catalyst with a gas mixture including hydrogen and carbon monoxide at a temperature of about 250-300 C at 10-30 atmospheric pressure.
In more specific aspects of the invention the catalyst is contacted with the hydrogen and carbon monoxide gas at a temperature of about 280 C and a pressure of about 20 atmospheres. The zeolite is in the acid substituted form with a silica to alumina ratio of about 25-50 and is included in the catalyst at about 75-93~ by weight.
~ ~ 77~64 In preparing the catalyst for the method of the present invention, a solution of soluble cobalt and thorium salts such as nitrates can be prepared in sufficient concentration of each metal to permit inclusion at the desired level in the completed catalyst. The metals can be precipitated as carbonates or other insoluble salts, then after drying, blended with the selected support material. Heating and reduction steps will provide cobalt metal and thorium dioxide (thoria) within the finished catalysts. The cobalt preferably is included in the catalyst at a weight of about 4-10 times that of the thoria. Suitable catalysts for use include about 6-20~
by weight cobalt and 0.5-3~ by weight thoria, with a preferred range of about 6-14% by weight cobalt and 0.7-2~ by weight thoria.
The support material for the catalyst is a crystalline aluminosilicate molecular sieve also known as a zeolite.
Such zeolites are described in the published li~erature and can be prepared by well defined processes, for instance as is presented in U.S. Patent Number 3,702,886. The zeolite employed in the present catalyst preferably includes pores of uniform diameter of about 5-6 angstroms. It is intended that the catalyst with this support used in accordance with the invention will be selective to the production of aliphatic hydrocarbons in the range of about C5 to C12 with substantial branched chains to enhance the octane rating of the liquid product.
The catalytic metals can be incorporated with the ~eolite support material in several ways. As suggested the cobalt and thorium can be precipitated from solution as ~ ~ 7 7 ~ 6 4 carbonates, dried and calcined to their oxides. The precipitate is crushed, classified to size and blended in a physical mixture with the zeolite in granular form. It is preferred that granules of about 80 ~icrometers (200 mesh) or less be used for both the metal oxide and zeolite. Alternatively, a solution of the cobalt and thorium soluble salts can be used to permeate into the zeolite which is subsequently dried and heated to a su~ficient temperature to convert the catalytic metals to the oxide. In either of these instances aqueous or acetone solutions are suitable for preparing the catalyst. Prior to use the cobalt oxide dispersed throughout the zeolite is reduced, with for instance hydrogen gas at a temperature of about 350 C and a pressure of typically 20 atmospheres to form cobalt metal.
The catalyst as thus described is used in the process of this invention by contacting it with a flow of synthesis gas containing hydrogen and carbon monoxide. It nas been found that the temperature of contact is of importance in obtaining a high percentage of the product liquid within the gasoline boiling range and in obtaining a high proportion of that liquid as branched chain olefins so as to provide a high octane number and thereby increase the value of the product as a fuel for internal combustion engines. For this purpose contact temperatures of about 250-300 C are required with a preferred temperature of about 280 C. Reaction temperatures much above this range not only decrease the total amount of liquid in the product includinq that within the gasoline boiling range but also increase the aromatic I li77464 content of thé remaining liquid. Although aromatics can be useful in increasing the octane rating of the fuel, they may carry with them undesirable health effects. It is therefore suggested that the problem of exhaust gas cleanup, may be ameliorated through the selection of branched chain olefins (and possibly pariffins) for imparting high octane characteristics to a liquid hydrocarbon fuel.
In the selection of other process conditions the sythesis gas pressure should be sufficien~ly high to provide good concentrations of the reactants hydrogen and carbon monoxide in contact with the catalyst but not so high as to raise instrumentation and mechanical problems. Typically pressures of about 1-70 atmospheres are contemplated for use with a preferred range of about 10-30 atmospheres. Space velocities of about 500-50,000 gas volumes per hour in respect to the catalyst are typical in processes of this type and can be selected to provide the desired conversion and production.
The heterogeneous catalyst can be contained in a fixed or a fluidized bed whilè contacting the synthesis gas flow.
At the reaction temperatures and pressures, the product stream is a mixture of liquids and gases which can be recovered by well known techniques. The gasoline fraction can be separated from the remaining products in a suitable distilation process.
The following examples are presented as an illustration and comparsion of the present process and catalyst with previous catalysts and methods.
A mixture of cobalt and thorium compounds with substan-tially more cobalt than thorium is pre~ipitated from,a nitrate l ~ 77~4 solution by the addition of sodium carbonate followed by heating to a boiling temperature. The precipitate is washed and then dried at about 110 C. The material is crushed to pass through 200 mesh (80 micro~eters) and mixed with about 4 weight parts of the zeolite ZSM-5 in granules of about the same size. The resulting ~ixture was pelleti~ed to about 1/2 cm diameter pellets. Following calcining and reduction wi~h ~2 gas at 350 C, the catalyst prepared in this manner contained about 10-11% by weight cobalt and about 1-2% by weight thoria~
About 60 grams of this catalyst was contacted with a continuous flow of synthesis gas containing about a 1:1 CO/H2 ratio at a gas volume hourly space velocity of about 1000, a pressure of about 20 atmospheres and a te~perature of 280 C in a stirred Berty reactor. The resulting product included over 60% by weight C5 and heavier hydrocarbon liquid. About 89% of this liquid was within the gasoline boiling range below about 200 C
while 11~ was in the diesel fuel range boiling between about 200-340 C. The liquid was found to have a research octane number of 86 but with only about 3% by weight aromatics.
Additional data respecting the Exa~ple along with a second run under si~ilar conditions is given below in Table 1. Table I
also includes for co~parison data fro~ U.S. Patent No.
4,086,262 (Table I) respecting a thoria and ZSM-5 catalyst in about equal parts used to convert a sythesis gas to hydro-carbons.
.
I ~77~64 CATALYST _ZSM-S(Co,ThO ) ZSM-5 + ThO2
2 __ H2/co in feed 1.0 1.0 1.0 Pressure (PSIG)300 300 1200 Temperature C280.0 279.0 426.7 CO Conversion ~78.3 82.2 22.4 H2 Conversion %92.4 94.4 15.2 Methane 28.2 19.8 17.3 10 C2 - C4 Hydrocarbons 10.8 10.6 73.8 C5+ (Liquid) -61.0 69O6 8.9 Aromatics in C5+3.0 41.6 Research Octane No. 86.0 It is clear from an examination of Table I that the catalyst and method of the present invention unexpectedly provides a high level of liquid hydrocarbons having a high octane rating without the presence of substantial aromatics.
It is also seen that this is advantageously accomplished at less severe temperature and pressure than that employed with the ZSM-5 + Th02 catalyst.
Use of Amorphous Support for Cobalt-Th02 Catalyst A mixture of cobalt and thoria precipitated from an aqueous solution as in Example 1 was mixed and pelletized with amorphous or poorly crystalline gamma alumina as a support.
On carrying out the reaction at 280 C within a stirred contin-uous flow Berty reactor it was found that the product included proportionally less hydrocarbon liquid than that obtained with the catalyst of the above Example. In the gasoline boiling ~ E77464 g range only 68~6 of the liquid boiled below about 200 C while 30% boiled in the diesel range of about 200-340 C. In addition the product included about 10~ solid wax material not present with the catalyst illustrated in the Example of the invention.
In a nuclear magnetic residence Ir.easurement the amount of branch chaining in the liquid product was found to be substantially less than in the product of the above Example leading to the implication of a lower octàne number. Additional comparitive data or use of this catalyst with that of the present invention 10 are given below in Table II.
10.8%Co, 1.2% ThO2io.8% Co, 1.296 ThO2 ., Conversion 96 -H2 93.3 91.7 CO 74.2 69.0 Hydrocarbon Product Distribution (wt%):
Methane 23.4 22.5 C2 ~ C4 13.8 14.6 C5~ (liquid) 61.0 52.6 20 Wax 1.8 10.3 Hydrocarbon Liquid Distribution (wt96):
Gasoline 89 68 Diesel 11 30 Residual ( 340 C) --- 2 Aromatics 4 2 Olefins 76 43 Saturates 20 _ 55 The liquid hydrocarbon product from use of the catalyst ~ ~77~64 of cobalt and thoria on zeolite support is seen to include a high percentage of olefins which on subsequent analyses were found to include to a large degree internal (or B) olefins.
Furthermore, the product of this catalyst in accordance with the method of this invention included substantial amounts of branched olefins and paraffins, thus yielding a high research octane number (about 86). In contrast, the product of the catalyst on the alumina support contained a high percentage of straight chain hydrocarbons.
Use of Co - ZSM-5 Catalyst A catalyst containing cobalt on ZSM-5 zeolite but without thoria was prepared as in the proceeding examples. The catalyst was contacted in a stirred Berty reactor with a synthesis gas having a hydrogen to carbon monoxide ratio of about 1 at about 20 atmospheres and a gas volume hourly space velocity of about 1000. Table III below compares the Co - ZSM-5 Catalyst with the catalyst of the present method at a temperature of 260 and 280C.
(8.3~ Co, 1.5~ Th CATALYST (6.8%, ZSM-5) ZSM-5) Temp C 260 280 260 280 CO Conversion %28.3 30.0 53.5 78.3 H2 Conversion %52.7 59.6 88.1 92.4 Liquid CHN % 58.1 34.4 66.4 61.0 Liquid Hydrocarbon Characteristics Aromatics % 5.0 4.5 1.5 3.0 Olefins ~ 23.5 21.5 83.0 68.0 Paraffins % 71.5 74.0 15.5 29.0 Research Octane No. 37.7 59.9 62.1 86.0 ~`
! i 7 7 ~ 6 ~
The table clearly shows that the catalyst used in accord-ance wi~h the present invention provides an unexpectedly large quantity of liquid hydrocarbons within the gasoline boiling range and with a high percentage of olefins and a high research octane rating.
It is therefore seen that the present invention provides a novel method and catalyst for the selective production of liquid hydrocarbons within the gasoline boiling range having a high octane number without the production of less desirable aromatics.
It will also be~clear that although the presen~ invention has been described in terms of specific embodiments and process conditions that one skilled in the art can make various modifications in accordance with the invention as defined in the accompanying claims.
It is also seen that this is advantageously accomplished at less severe temperature and pressure than that employed with the ZSM-5 + Th02 catalyst.
Use of Amorphous Support for Cobalt-Th02 Catalyst A mixture of cobalt and thoria precipitated from an aqueous solution as in Example 1 was mixed and pelletized with amorphous or poorly crystalline gamma alumina as a support.
On carrying out the reaction at 280 C within a stirred contin-uous flow Berty reactor it was found that the product included proportionally less hydrocarbon liquid than that obtained with the catalyst of the above Example. In the gasoline boiling ~ E77464 g range only 68~6 of the liquid boiled below about 200 C while 30% boiled in the diesel range of about 200-340 C. In addition the product included about 10~ solid wax material not present with the catalyst illustrated in the Example of the invention.
In a nuclear magnetic residence Ir.easurement the amount of branch chaining in the liquid product was found to be substantially less than in the product of the above Example leading to the implication of a lower octàne number. Additional comparitive data or use of this catalyst with that of the present invention 10 are given below in Table II.
10.8%Co, 1.2% ThO2io.8% Co, 1.296 ThO2 ., Conversion 96 -H2 93.3 91.7 CO 74.2 69.0 Hydrocarbon Product Distribution (wt%):
Methane 23.4 22.5 C2 ~ C4 13.8 14.6 C5~ (liquid) 61.0 52.6 20 Wax 1.8 10.3 Hydrocarbon Liquid Distribution (wt96):
Gasoline 89 68 Diesel 11 30 Residual ( 340 C) --- 2 Aromatics 4 2 Olefins 76 43 Saturates 20 _ 55 The liquid hydrocarbon product from use of the catalyst ~ ~77~64 of cobalt and thoria on zeolite support is seen to include a high percentage of olefins which on subsequent analyses were found to include to a large degree internal (or B) olefins.
Furthermore, the product of this catalyst in accordance with the method of this invention included substantial amounts of branched olefins and paraffins, thus yielding a high research octane number (about 86). In contrast, the product of the catalyst on the alumina support contained a high percentage of straight chain hydrocarbons.
Use of Co - ZSM-5 Catalyst A catalyst containing cobalt on ZSM-5 zeolite but without thoria was prepared as in the proceeding examples. The catalyst was contacted in a stirred Berty reactor with a synthesis gas having a hydrogen to carbon monoxide ratio of about 1 at about 20 atmospheres and a gas volume hourly space velocity of about 1000. Table III below compares the Co - ZSM-5 Catalyst with the catalyst of the present method at a temperature of 260 and 280C.
(8.3~ Co, 1.5~ Th CATALYST (6.8%, ZSM-5) ZSM-5) Temp C 260 280 260 280 CO Conversion %28.3 30.0 53.5 78.3 H2 Conversion %52.7 59.6 88.1 92.4 Liquid CHN % 58.1 34.4 66.4 61.0 Liquid Hydrocarbon Characteristics Aromatics % 5.0 4.5 1.5 3.0 Olefins ~ 23.5 21.5 83.0 68.0 Paraffins % 71.5 74.0 15.5 29.0 Research Octane No. 37.7 59.9 62.1 86.0 ~`
! i 7 7 ~ 6 ~
The table clearly shows that the catalyst used in accord-ance wi~h the present invention provides an unexpectedly large quantity of liquid hydrocarbons within the gasoline boiling range and with a high percentage of olefins and a high research octane rating.
It is therefore seen that the present invention provides a novel method and catalyst for the selective production of liquid hydrocarbons within the gasoline boiling range having a high octane number without the production of less desirable aromatics.
It will also be~clear that although the presen~ invention has been described in terms of specific embodiments and process conditions that one skilled in the art can make various modifications in accordance with the invention as defined in the accompanying claims.
Claims (8)
1. A method of converting a major fraction of carbon monoxide within a gas mixture including hydrogen and carbon monoxide to produce an aliphatic hydrocarbon product with less than 10% by weight aromatics, said product having a major proportion by weight of C5 and higher hydrocarbons in the gasoline boiling point range, said method comprising forming a catalyst including a mixture of cobalt, thoria and a crystalline zeolite having a pore size of 5 to 6 angstroms wherein cobalt is included at 6-20%, thoria is included at 0.5-3% weight, and crystalline zeolite is included at 75-93% by weight; and contacting said catalyst with the gas mixture including hydrogen and carbon monoxide at a temperature essentially of 280°C at 10-30 atmospheres pressure whereby said hydrocarbon product is formed.
2. The method of claim 1 wherein the crystalline zeolite is in the acid substituted form with a silica to alumina ratio of about 25-50.
3. The method of claim 1 wherein the catalyst is contacted with the gas mixture at a gas volume space velocity of about 1000 per hour at about 20 atmospheres pressure.
4. The method of claim 1 wherein the catalyst mixture is in the form of pellets of about 0.3-0.7 cm diameter made of compacted granules of less than about 80 micrometers, the granules including granules of crystalline zeolite in mixture with granules of precipitated cobalt and thoria.
5. The method of claim 1 wherein the catalyst mixture includes about 6-14% cobalt and about 0.7-2% thoria by weight.
6. The method of claim 1 wherein the hydrocarbon product is a liquid having a boiling point range of about 200°C and lower at atmospheric pressure, a research octane rating of more than 80 while containing less than 10% by weight aromatics.
7. A catalyst for the conversion of a major fraction of hydrogen and carbon monoxide gases at a temperature essentially of 280°C to a liquid aliphatic hydrocarbon product with less than 10% by weight aromatics, said product having a major proportion of C-5 and higher hydrocarbons in the gasoline boiling range comprising a crystalline zeolite molecular sieve having a uniform pore size of about 5-6 angstroms diameter;
about 6-20 weight percent cobalt and about 0.5-3 weight percent thoria dispersed through about 75-93 weight percent zeolite molecular sieve in physical mixture therewith.
about 6-20 weight percent cobalt and about 0.5-3 weight percent thoria dispersed through about 75-93 weight percent zeolite molecular sieve in physical mixture therewith.
8. The catalyst of claim 7 wherein the catalyst is in the form of pellets of about 0.3-0.7 cm diameter including compacted granules of about 80 micrometers diameter of precipitated cobalt and thoria in mixture with crystalline zeolite.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US31024681A | 1981-10-09 | 1981-10-09 | |
| US310,246 | 1981-10-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1177464A true CA1177464A (en) | 1984-11-06 |
Family
ID=23201621
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000412380A Expired CA1177464A (en) | 1981-10-09 | 1982-09-28 | Process and catalyst for converting synthesis gas to liquid hydrocarbon mixture |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS5871987A (en) |
| AU (1) | AU575016B2 (en) |
| CA (1) | CA1177464A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2561640A1 (en) * | 1984-03-22 | 1985-09-27 | Shell Int Research | PROCESS FOR PRODUCING HYDROCARBONS FROM SYNTHESIS GAS |
| US4579830A (en) * | 1984-06-27 | 1986-04-01 | Union Carbide Corporation | Enhanced catalyst for converting synthesis gas to liquid motor fuels |
| EP1825194B1 (en) | 2004-12-08 | 2021-02-17 | LPP Combustion, LLC | Method and apparatus for conditioning liquid hydrocarbon fuels |
| US8529646B2 (en) * | 2006-05-01 | 2013-09-10 | Lpp Combustion Llc | Integrated system and method for production and vaporization of liquid hydrocarbon fuels for combustion |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3702886A (en) * | 1969-10-10 | 1972-11-14 | Mobil Oil Corp | Crystalline zeolite zsm-5 and method of preparing the same |
| CA1062285A (en) * | 1974-04-24 | 1979-09-11 | Mobil Oil Corporation | Conversion of synthesis gas to hydrocarbon mixtures |
| US4086262A (en) * | 1976-09-20 | 1978-04-25 | Mobil Oil Corporation | Conversion of synthesis gas to hydrocarbon mixtures |
| US4207248A (en) * | 1978-12-18 | 1980-06-10 | Mobil Oil Corporation | Conversion of synthesis gas with cobalt-containing fluid catalyst |
| NZ201262A (en) * | 1981-07-17 | 1984-12-14 | British Petroleum Co | Catalytic conversion of synthesis gas to hydrocarbons |
-
1982
- 1982-09-28 CA CA000412380A patent/CA1177464A/en not_active Expired
- 1982-09-30 AU AU88929/82A patent/AU575016B2/en not_active Ceased
- 1982-10-08 JP JP57177465A patent/JPS5871987A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| AU575016B2 (en) | 1988-07-21 |
| JPS5871987A (en) | 1983-04-28 |
| AU8892982A (en) | 1983-04-14 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEC | Expiry (correction) | ||
| MKEX | Expiry |