CA1117053A - Process for gasifying coal wherein a catalyst is incorporated by ion exchange after partial oxidation of the coal - Google Patents
Process for gasifying coal wherein a catalyst is incorporated by ion exchange after partial oxidation of the coalInfo
- Publication number
- CA1117053A CA1117053A CA000300949A CA300949A CA1117053A CA 1117053 A CA1117053 A CA 1117053A CA 000300949 A CA000300949 A CA 000300949A CA 300949 A CA300949 A CA 300949A CA 1117053 A CA1117053 A CA 1117053A
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- CA
- Canada
- Prior art keywords
- coal
- ion exchange
- further characterized
- accomplished
- cation
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0903—Feed preparation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/093—Coal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0983—Additives
- C10J2300/0986—Catalysts
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
An improved method of distributing catalysts in coal comprising oxidizing the coal and ion-exchanging the active sites thus formed with a cation which exhibits catalytic activity when used in a subsequent coal conversion process.
The ion exchange may be accomplished simultaneously with or subsequent to the oxidation step. After the ion exchange the coal can then be subjected to conversion via a gasification process. Ion exchange with the alkali and alkaline earth metal cations is particularly effective when the coal is subsequently converted via a gasification reaction. Incorporation of the cations into the coal via the method of this invention results in increased conversion rate and, generally, higher conversions to more desirable products.
The method is particularly effective in the conversion of subbituminous and higher ranking coals and is most effective in processes wherein bituminous coal is converted.
An improved method of distributing catalysts in coal comprising oxidizing the coal and ion-exchanging the active sites thus formed with a cation which exhibits catalytic activity when used in a subsequent coal conversion process.
The ion exchange may be accomplished simultaneously with or subsequent to the oxidation step. After the ion exchange the coal can then be subjected to conversion via a gasification process. Ion exchange with the alkali and alkaline earth metal cations is particularly effective when the coal is subsequently converted via a gasification reaction. Incorporation of the cations into the coal via the method of this invention results in increased conversion rate and, generally, higher conversions to more desirable products.
The method is particularly effective in the conversion of subbituminous and higher ranking coals and is most effective in processes wherein bituminous coal is converted.
Description
1 BACKGROUND _F ~IE I. ~NTION
2 This invention relates co an improved process or
3 converting coal or carbonaceous materials derived from coal.
4 More particularly, this invention relates to a process for conver~ing coal or carbonaceous materials derived from coal 6 wherein cations exhibiting catalytic activity for the 7 particular conversion process involved are effectively dis-8 tributed through the coal or carbonaceous material derived 9 from coal prior to subjecting the same to the particular 0 conversion process involved.
11 As is we'~]. known, coal has long been used as a fuel 12 in many areas. For several reasons such as handling problems, 13 waste disposal problems, pollution problems and the like, coal 14 has not been a particularly desirable fuel from the ultimate consumers point of view. As a result, oil and gas have 16 en;oyed a dominant position, fron the standpoint of fuel 17 sources, throughout the world.
18 As is also w~ll known, proven petroleum and gas 19 reserves are shrinking throughout the world and the need for alternate sources of energy is becoming more and more 21 apparent. One such alternate source is, of course, coal 22 since coal is an abundant fossil fuel, particularly in the 23 United States. Before coal will be widely accepted as a 24 fuel, however, it is believed necessary to convert the same to a form which will not suffer from the several disadvan~
26 tages alluded to previously.
27 To this end, several processes ~lerein coal is 28 either liqueied and/or gasified have been proposed heretofore.
~ Many of the.se processes have employed a variety of catalytic materials that have been more or less successful in promoting ~il7Q53 1 the desired conversion. In order ~or such materials to be 2 completely effective, however, it is important that the cata-3 lytie material be uniformly distributed throughout the 4 coal structure. Due to the soli.d nature of coal, however, the neeessary distribution has been difficult and as a result 6 many potential eatalytieally aetive materials eannot be 7 effeetively employed with eonventional techniques.
8 Recently, it has been taught in Catalytie Review -9 Seience Engineering 14(1), 131-152 (1976) that this problem ean be avoided with lower ranking coals by first ion-11 exchanging a lower ranking coal with an alkali or an alkaline 12 earth metal cation and, particularly, sodium or calciurn. As 13 indieated in the artiele, this teehnique was not partieularly 14 effeetive in higher ranking eoals and the effect was not signifieant in bituminous coal chars. The problem still 16 exists, then, with the higher ranking coals and, indeed, 17 the method proposed in the aforementioned article is not, 18 apparently, the ultimate solution even with respect to lower 19 ranking coals. The need, then, continues for a method of distributing eatalytieally aetive materials in a higher 21 ranking coal whieh is destined for ultimate conversion, 22 particularly via-liqu~faetion arld/o~ gasifieation techniques.
23 Moreover, the need exists for still further improvement with 24 respect to eatalyst distribution even within the lower rank-ing coals and particularly those which do not have suffieient 26 aeid sites to permit effective ion exchange.
27 SUMMA~Y OF THE INVENTION
28 It has now, surprisingly, been diseovered that the 29 foregoing and other disadvantages of the prior art eatalyst distribution rnethods ean be overeome with the rnethod of the 7~53 present invention and a method for effectively distributing catalytic materials in higher ranking coals and an improved method of distributing catalytic materials in lower ranking coals provided thereby. It is, therefore, an object of this invention to provide a method for distributing catalytic mater-ials throughout coal and carhonaceous materials derived from coal. It is another object of this invention to provide such a process which is particularly effective in the distribution of catalytic materials throughout higher ranking coals and such a process which can be used to improve distribution throughout lower ranking coals. It is still a further object of this in-vention to provide such a process which can be used in combin-ation with gasification and other coal conversion processes.
These and other objects and advantages will become apparent from the description set forth hereinafter.
In accordance with this invention, the foregoing and other objects and advantages are accomplished by subjecting the coal to partial oxidation and then subjecting the oxidized coal to ion exchange with a suitable metal cation. As indicated more fully hereinafter, it is important that the oxidation be care-fully controlled so as to prevent unnecessary loss of the coal durin~ this pretreatment step. As is also more fully indicated hereinafter, the particular cation used during the ion exchange step will depend upon the particular catalytic activity desired in the subsequent conversion. After the partial oxidation and ion exchange has been completed, the thus treated coal will be more easily converted in a gasification or similar conversion process.
,~
~1~70S3 , DETA I LE~ DE S CR I PT I ON OF TIIE I NV13NT I ON
. _ _ . . ~ . .. . . _ _ _ 2 ~s indicated supra, the present invention relates to 3 a method of distributing catalytically active materials 4 throughout a coal or a carbonaceous material derived from coal, The distribution is accomplished by treating the coal 6 or the carbonaceous material derived from coal so as to 7 impart sites therein which can then be reacted with the 8 catalytic material. After this treatment, or simultane- ¦
ously therewith, these sites are then converted to the desired catalytic site. The thus treated coal or carbon-aceous material derived from coal will then be subjected 12 to a conversion operation such as gasification__liquofaotion or the like.
14 In general, the distribution method of the present S invention can be used with any coal including anthracite, bituminous, subbituminous, lignite, peat, brown coal, and the like. As previously indicated, however, the lowest ~-ranking coals will generally have sufficient exchangeable sites to permit effective distribution of the catalytic material without prior treatment, The method of the present invention is, then, most effective with the higher ranking coals, which do not have sufficient sites to permit distri-2 bution without pretreatment and the method of this invention is particularly effective with the bituminous and subbitumi-nous coals.
26 In general, the coal will be ground to a finely divided state, The particular particle size, or particle 28 size range, actually employed will depend a great deal uponthe optimum size to be used in the subsequent conversion process, although the actual particle size range employed
11 As is we'~]. known, coal has long been used as a fuel 12 in many areas. For several reasons such as handling problems, 13 waste disposal problems, pollution problems and the like, coal 14 has not been a particularly desirable fuel from the ultimate consumers point of view. As a result, oil and gas have 16 en;oyed a dominant position, fron the standpoint of fuel 17 sources, throughout the world.
18 As is also w~ll known, proven petroleum and gas 19 reserves are shrinking throughout the world and the need for alternate sources of energy is becoming more and more 21 apparent. One such alternate source is, of course, coal 22 since coal is an abundant fossil fuel, particularly in the 23 United States. Before coal will be widely accepted as a 24 fuel, however, it is believed necessary to convert the same to a form which will not suffer from the several disadvan~
26 tages alluded to previously.
27 To this end, several processes ~lerein coal is 28 either liqueied and/or gasified have been proposed heretofore.
~ Many of the.se processes have employed a variety of catalytic materials that have been more or less successful in promoting ~il7Q53 1 the desired conversion. In order ~or such materials to be 2 completely effective, however, it is important that the cata-3 lytie material be uniformly distributed throughout the 4 coal structure. Due to the soli.d nature of coal, however, the neeessary distribution has been difficult and as a result 6 many potential eatalytieally aetive materials eannot be 7 effeetively employed with eonventional techniques.
8 Recently, it has been taught in Catalytie Review -9 Seience Engineering 14(1), 131-152 (1976) that this problem ean be avoided with lower ranking coals by first ion-11 exchanging a lower ranking coal with an alkali or an alkaline 12 earth metal cation and, particularly, sodium or calciurn. As 13 indieated in the artiele, this teehnique was not partieularly 14 effeetive in higher ranking eoals and the effect was not signifieant in bituminous coal chars. The problem still 16 exists, then, with the higher ranking coals and, indeed, 17 the method proposed in the aforementioned article is not, 18 apparently, the ultimate solution even with respect to lower 19 ranking coals. The need, then, continues for a method of distributing eatalytieally aetive materials in a higher 21 ranking coal whieh is destined for ultimate conversion, 22 particularly via-liqu~faetion arld/o~ gasifieation techniques.
23 Moreover, the need exists for still further improvement with 24 respect to eatalyst distribution even within the lower rank-ing coals and particularly those which do not have suffieient 26 aeid sites to permit effective ion exchange.
27 SUMMA~Y OF THE INVENTION
28 It has now, surprisingly, been diseovered that the 29 foregoing and other disadvantages of the prior art eatalyst distribution rnethods ean be overeome with the rnethod of the 7~53 present invention and a method for effectively distributing catalytic materials in higher ranking coals and an improved method of distributing catalytic materials in lower ranking coals provided thereby. It is, therefore, an object of this invention to provide a method for distributing catalytic mater-ials throughout coal and carhonaceous materials derived from coal. It is another object of this invention to provide such a process which is particularly effective in the distribution of catalytic materials throughout higher ranking coals and such a process which can be used to improve distribution throughout lower ranking coals. It is still a further object of this in-vention to provide such a process which can be used in combin-ation with gasification and other coal conversion processes.
These and other objects and advantages will become apparent from the description set forth hereinafter.
In accordance with this invention, the foregoing and other objects and advantages are accomplished by subjecting the coal to partial oxidation and then subjecting the oxidized coal to ion exchange with a suitable metal cation. As indicated more fully hereinafter, it is important that the oxidation be care-fully controlled so as to prevent unnecessary loss of the coal durin~ this pretreatment step. As is also more fully indicated hereinafter, the particular cation used during the ion exchange step will depend upon the particular catalytic activity desired in the subsequent conversion. After the partial oxidation and ion exchange has been completed, the thus treated coal will be more easily converted in a gasification or similar conversion process.
,~
~1~70S3 , DETA I LE~ DE S CR I PT I ON OF TIIE I NV13NT I ON
. _ _ . . ~ . .. . . _ _ _ 2 ~s indicated supra, the present invention relates to 3 a method of distributing catalytically active materials 4 throughout a coal or a carbonaceous material derived from coal, The distribution is accomplished by treating the coal 6 or the carbonaceous material derived from coal so as to 7 impart sites therein which can then be reacted with the 8 catalytic material. After this treatment, or simultane- ¦
ously therewith, these sites are then converted to the desired catalytic site. The thus treated coal or carbon-aceous material derived from coal will then be subjected 12 to a conversion operation such as gasification__liquofaotion or the like.
14 In general, the distribution method of the present S invention can be used with any coal including anthracite, bituminous, subbituminous, lignite, peat, brown coal, and the like. As previously indicated, however, the lowest ~-ranking coals will generally have sufficient exchangeable sites to permit effective distribution of the catalytic material without prior treatment, The method of the present invention is, then, most effective with the higher ranking coals, which do not have sufficient sites to permit distri-2 bution without pretreatment and the method of this invention is particularly effective with the bituminous and subbitumi-nous coals.
26 In general, the coal will be ground to a finely divided state, The particular particle size, or particle 28 size range, actually employed will depend a great deal uponthe optimum size to be used in the subsequent conversion process, although the actual particle size range employed
- 5 -!
1~170S3 1 will have some effect on the rate of pretreatment and the 2 rate of catalyst distribution. In this regard, it should 3 be noted that the coal would, generally, when treated in 4 accordance with this invention, be ground to a particle size of less than about l/4-inch and preferably to a particle size
1~170S3 1 will have some effect on the rate of pretreatment and the 2 rate of catalyst distribution. In this regard, it should 3 be noted that the coal would, generally, when treated in 4 accordance with this invention, be ground to a particle size of less than about l/4-inch and preferably to a particle size
6 of less than about 8 mesh NBS sieve size. With respect to
7 particle size, it should be noted that the smaller sizes
8 will enhance both the pretreatment reaction rate snd at the same time will enhance catalyst distribution. For these reasons, then, the actual particle size employed will be 11 as small as is practically consistent with the requirements 12 for further processirlg and utilizing the coal.
13 In general, the active sites imparted on the coal 1 as a result of the pretreatment could be essentially any g type of chemical site which would permit s1lbsequent or 16 simultaneous reaction with a desired catalytic compound.
Acidic sites are, however, most convenient to impart into 18 the coal and, therefore, will generally be the site o~
choice.
2 It will be appreciated that these sites could be 2 provided via any suitable technique and in accordance with the theories set forth hereinafter. When acidic sites are used, however, these can be provided via essentially any known oxidizing technique. For example, the acidic sites can be provided by oxidizing the finely divided coal 26 either with oxygen or an oxygen-containing gas such as air 27 or a flu gas, or the same may be provided through the use 28 of an oxidizing agent such as an acid, a peroxide, various 29 salts such as a perman~anate, a hypochlorite,'or the like.
~hen an acid is used essentially any acid, such as nitric ~1~7~53 1 acid and sulfur:Lc ac:~d, known ~o be useful as an oxidizing 2 agent càn be used. When a peroxide is used essentially 3 any peroxide including hydrogen peroxide, the various 4 organic peroxides, the various metal peroxides and the like would be effective, When a salt such as a permanganate or 6 hypochlorite is used essentially any such salt would be 7 effective but it will be most convenient to use a salt 8 containing a cation identical to that to be used in the
13 In general, the active sites imparted on the coal 1 as a result of the pretreatment could be essentially any g type of chemical site which would permit s1lbsequent or 16 simultaneous reaction with a desired catalytic compound.
Acidic sites are, however, most convenient to impart into 18 the coal and, therefore, will generally be the site o~
choice.
2 It will be appreciated that these sites could be 2 provided via any suitable technique and in accordance with the theories set forth hereinafter. When acidic sites are used, however, these can be provided via essentially any known oxidizing technique. For example, the acidic sites can be provided by oxidizing the finely divided coal 26 either with oxygen or an oxygen-containing gas such as air 27 or a flu gas, or the same may be provided through the use 28 of an oxidizing agent such as an acid, a peroxide, various 29 salts such as a perman~anate, a hypochlorite,'or the like.
~hen an acid is used essentially any acid, such as nitric ~1~7~53 1 acid and sulfur:Lc ac:~d, known ~o be useful as an oxidizing 2 agent càn be used. When a peroxide is used essentially 3 any peroxide including hydrogen peroxide, the various 4 organic peroxides, the various metal peroxides and the like would be effective, When a salt such as a permanganate or 6 hypochlorite is used essentially any such salt would be 7 effective but it will be most convenient to use a salt 8 containing a cation identical to that to be used in the
9 subsequent catalyst distribution.
In general, any cation could be distributed 11 throughout the coal or a carbonaceous material derived 12 from coal after the pretreatment of this invention and, 3 surprisingly, any cation will impart some degree of cata-4 lytic activity in subsequent conversion processes. Cations 15 that can be used in accordance with this invention, then, L
16 include those cations which are known to act as catalysts 17 in the various coal conversion processes. Surprisingly, 18 however, and in accordance with the present invention, 19 cations known to exhibit slight or limited catalytic properties, by virtue of being physically intermixed with 21 the coal structure, have been found to exhlbit greatly 22 improved catalytic properties when chemically combined.
23 Cations which will exhibit catalytic activity when 24 incorporated into the coal in accordance with the present invention include the alkali metals and the alkaline earth 26 metals of Groups I-A and II-A of the Periodic Chart of the 27 Elements (as reprinted in the Chemical Engineers Handbook, 28 th Edition, Percy ~ Shulton, published by McGraw-Hill Book 29 Company, New York, 1973). Effe,ctive cations also include the metals o~ Groups I-B and II-B and the metals of Groups 1~17Q53 IV-~, IV-B, VI-B, VII-B and Group VIII. Of these, the alkali and alkaline earth metals are particularly effective when the coal is ultimately converted via a gasification reaction.
While the inventors do not wish to be bouhd by any particular theory, it is believed that when oxidization is used to impart the desired active sites, the reactions and subsequent ion exchange proceeds throughout the significant internal pore surface area of the coal, which is commonly of a magnitude of several hundred square meters per gram of coal. It is also believed that peroxides are first formed and the peroxides thus formed decompose to yield acids. The acidic hydrogens can then be ion-exchanged in accordance with the present invention.
With respect to the foregoing, and while the inven-tors still do not wish to be bound by any particular theory, it is believed that coal contains a plurality of aromatic rings which are highly substituted; e.g., fused to other aromatics or hydroaromatics or attached to alkyl, ether, hydroxyl or the like, groups. Additionally, it is believed that coal exhibits secondary structural characteristics such as hydrogen bonding, interatomic ring bonds and the like, which generate the three-dimensional structure of coal. As a result, oxidation of coal can result in a broad range of free-radical or acid sites. The formation of one such site, which would be possible from a condensed structure containing three aromatic rings, can be illustrated by the following equations:
;
--- i 1~7053 1 ~ + 2 -2 ~.
3 ~ - b 4 As will be readily apparent, the free-radical sites illus-5 trated in the second formula would readily react with 6 essentially any cation. As will also be readily apparent, f 7 especially in light of the complex coal structure and signif-8 icant pore surface area, an unlimited number of such sites 9 are possible. Moreover, and with respect to the lower-
In general, any cation could be distributed 11 throughout the coal or a carbonaceous material derived 12 from coal after the pretreatment of this invention and, 3 surprisingly, any cation will impart some degree of cata-4 lytic activity in subsequent conversion processes. Cations 15 that can be used in accordance with this invention, then, L
16 include those cations which are known to act as catalysts 17 in the various coal conversion processes. Surprisingly, 18 however, and in accordance with the present invention, 19 cations known to exhibit slight or limited catalytic properties, by virtue of being physically intermixed with 21 the coal structure, have been found to exhlbit greatly 22 improved catalytic properties when chemically combined.
23 Cations which will exhibit catalytic activity when 24 incorporated into the coal in accordance with the present invention include the alkali metals and the alkaline earth 26 metals of Groups I-A and II-A of the Periodic Chart of the 27 Elements (as reprinted in the Chemical Engineers Handbook, 28 th Edition, Percy ~ Shulton, published by McGraw-Hill Book 29 Company, New York, 1973). Effe,ctive cations also include the metals o~ Groups I-B and II-B and the metals of Groups 1~17Q53 IV-~, IV-B, VI-B, VII-B and Group VIII. Of these, the alkali and alkaline earth metals are particularly effective when the coal is ultimately converted via a gasification reaction.
While the inventors do not wish to be bouhd by any particular theory, it is believed that when oxidization is used to impart the desired active sites, the reactions and subsequent ion exchange proceeds throughout the significant internal pore surface area of the coal, which is commonly of a magnitude of several hundred square meters per gram of coal. It is also believed that peroxides are first formed and the peroxides thus formed decompose to yield acids. The acidic hydrogens can then be ion-exchanged in accordance with the present invention.
With respect to the foregoing, and while the inven-tors still do not wish to be bound by any particular theory, it is believed that coal contains a plurality of aromatic rings which are highly substituted; e.g., fused to other aromatics or hydroaromatics or attached to alkyl, ether, hydroxyl or the like, groups. Additionally, it is believed that coal exhibits secondary structural characteristics such as hydrogen bonding, interatomic ring bonds and the like, which generate the three-dimensional structure of coal. As a result, oxidation of coal can result in a broad range of free-radical or acid sites. The formation of one such site, which would be possible from a condensed structure containing three aromatic rings, can be illustrated by the following equations:
;
--- i 1~7053 1 ~ + 2 -2 ~.
3 ~ - b 4 As will be readily apparent, the free-radical sites illus-5 trated in the second formula would readily react with 6 essentially any cation. As will also be readily apparent, f 7 especially in light of the complex coal structure and signif-8 icant pore surface area, an unlimited number of such sites 9 are possible. Moreover, and with respect to the lower-
10 ranking coals which contain significant oxygen concentrations,
11 active sites different from those already contained in such
12 coals can be imparted through controlled oxidation. The .
13 method of the present invention is, therefore, effective in
14 the treatment of such coals and especially such which do not
15 contain su~ficient exchangeable active sites,
16 In general, any amount of oxidation will provide
17 an increased number of reactive sites, especially in the
18 higher ranking coals and, therefore, will be beneficial
19 in the method of the present invention and will, generally,
20 increase the catalytic activity of any cation or cations
21 subsequently exchanged on to these sites. Best results
22 will, however, be obtained only after a suf~icient number
23 of active sites have been imparted into the coal to permit
24 the inclusion of from about l to about is Wt% of calcium or
25 equivalent amounts of another desired cation or cations.
26 In this regard, it should be noted that when monovalent
27 cations or cations heavier than calcium are used the equi-
28 valent amount ion exchanged will represent a greater
29 percentage by weight of the coal while with lighter or
30 trivalent cations the weight percentage could be less. The ~1~7t~53 1 key, then, is really the number of catalytic sites per unit 2 weight of coal and sufficient catalytic activity will be 3 imparted when the coal contains between about 5 x 10 4 and 4 8 x 10-3 gram atomic equivalents of catalytic-active cation per gram of coal.
6 With respect to the amount of catalytic-active 7 material being incorporated into the coal, it should be 8 noted that in those cases where the objective is to convert 9 the coal to either a-liquid-or- gaseous fuel, the prior oxi-0 dation, to the extent that it converts a portion of the coal 11 to water and carbon oxides, will reduce the overall effi-12 ciency of the conversion process by reducing the quantity of 13 coal available for subsequent conversion. The treatment 14 does, on the other hand, improve the ef~iciency of the overall process by increasing catalytic activity and thereby reducing 16 the holding time and/or temperature required in the subsequent 17 conversion operation, The overall efficiency of the 18 improved process or processes of this invention is, then, 9 a balance resu~ting from these considerations. In this regard, however, it should be noted that the advantages 21 resulting from ei'fective distribution of the catalyst far 22 outweigh the disadvantage resulting ~rom premature conver-23 sion of the coal to C02 and H20 so a s to affect catalyst 24 distribution. Notwithstanding this, however, careshould be exercised so as to avoid unnecessary oxidation of the 26 coal during the pretreatment step, 27 In general, any method known in the prior art 28 to be effective in controlling the rate and extent of 29 oxidation in a hydrocarbon can be used to affect the desired oxidation of the coal in the method of this in-~1~7Q53 1 vention. 5uch methods include, but are not necessarily 2 limited to, control of oxidizing reagent concentration and 3 the temperature o~ oxidation. Control oI oxidizin~ reagent 4 concentration can, of course, be controlled by mixing the reagent with a sui.table diluent during contacting. This 6 method would, of course, be most effective when a liquid 7 or solid oxidizing agent is employed but could be used even 8 when a gaseous-reducing agent is employed, In any case, 9 and even when oxidizing-agent concentration is controlled during contacting it will, generally, be necessary to control 11 temperature primarily to insure that oxidation does occur 12 within a reasonable period of time. Effective oxidizing-13 agent concentrations and effective oxidizing temperatures 14 are, of course, well within the ordinary skill o~ the art and need not be set forth in detail herein.
,16 ~otwithstanding that effective concentrations and 17 temperatures are within the ordinary skill of the art, it 18 should be noted that when a gas, such as air, is employed 19 as the oxidizing agent, essentially any temperature and pressure can be used during the oxidation and the exteIlt 21 of oxidation can be controlled by controlling the amount 22 of air actually contacting the coal and the temperature 23 at which contacting i9 accomplished. In th~s regard it 24 should be noted that sufficient oxidation of dry coal will occur autogeneously at room temperature but at least five 26 to seven days exposure are generally required. As a 27 result, elevated temperatures are most effective but 28 temperatures approaching combustion temperature should 29 be avoided. Temperatures within the range from about 18C
,to about 425C are, then, considered effective. Tempera-~7Q53 1 tures within ~he range from about 175C.~o about 300C. are, 2 however, preferred since temperatures helow about 175C. do 3 not provide suf~icient re~ction rates while temperatures 4 above 300C. result in reaction rates approaching those S of combustion. Due to the well-known time-temperature 6 effect, reaction times can vary from a few minu~es at the 7 higher temperatures to se~eral hours at the lower temper-8 atures.
9 In general, any of the ion exchange techniques known to be effective ~or exchanging any cation ~or a 11 hydrogen ion or a different cation can be used to effect 12 the desired catalyst distribution in the method of the 13 present inven~ion. These techniques include direct 14 contacting with a metal hydroxide in aqueous solution where the metal correspond~s to the desired catalytic cation 16 and the various techniques wherein a me~al salt ls used to 17 efect the desired ion exchange. Again, when metal salts 18 are used the metal portion of the salt will correspond to 19 the cation sought to be imparted into the coal. In general, aqueous solutions of a hydroxide or a salt of a weak acid 21 will be employed to effect the ion exchange. As is well 22 known, the ion exchange will occur at a basic pH; i.e., 23 a pH ~reater than 7. The coal may, o~ course, be pre-24 treated; i.e., prior to the ion exchange, with an organic or inorganic acid such as formic acid or the like, to 26 remove undeslrable, naturally occurring, complexed elements.
27 When this is done, care should be exercised to insure that 28 the acid employed will not impart an undesirable anion into 29 the coal. Also, it will, gener~lly, be necessary to wash out or neutralize the acidity of the aqueous medium prior ~117~53 to ion exchanqe. Such neutralization can, of course, be accomplishecl in accordance with known techniques and need not be discussed in detail herein. Notwithstanding this, however, it should be noted that ammonia can be effectively used to control the pH and that ammonia is particularly effective when an acid pretreat is used and when alkali and alkaline salts, particularly the halide salts, are used to effect the desired ion exchange. The anion can then later be removed by water washing or the like.
In the method heretofore desc~ibed, the pretreatment or oxidation is accomplished prior to the ion exchange. It is, however, within the scope of this invention to effect both oxidation and ion exchange simultaneously. When this is done, oxygen will either be bubbled through the ion exchange solution during contacting with the coal, or another suitable oxidizing agent will be incorporated into the ion exchange solution. As in the previously described embodiment, the simultaneous oxidation-ion exchange will be accomplished in accordance with techniques known in the prior art.
As indicated previously, the particular cation or cations incorporated into the coal will depend upon the subsequent conversion process employed. For example, and as indicated previously, where the subsequent conversion is to be via gasification, alkali and alkaline earth metals will preferably be employed.
~i ~il70~3 1 In general, any o~ the gasification processes 2 known in the prior art can be improved with respect to 3 ei.ther yield, conversion rate of both when the catalyst 4 distribution method of this invention is employed prior to effecting the gasification reaction. In general, these 6 gasification processes comprise a step wherein coal is 7 .reacted with a gaseous species or a mixture of gaseous 8 species at an elevated temperature, and, generally, an 9 elevated pressure to produce other, more desirable gases. The gaseous species generally employed as react-11 ants include oxygen, steam, carbon oxides such as carbon 12 dioxide, and hydrogen. Generally, temperature, pressure, 13 and flow rate in these processes as well as the mole ratio 1i 14 or relative ratio of reacting gases to coal will depend on the specific process employed and the actual products desired 16 therefrom. In this regard, it should be noted that the 17 composition of the gaseous products from these processes 18 cal also be altered by the particular catalyst employed.
19 For example, and as is known in the prior art, the products resulting from the gasification of coal with steam can be 21 enriched in methane through the use of an alkali metal that 22 promotes the conversion of carbon monoxide and hydro~en 23 to methane.
24 As previously indicated, the method of this invention ~or distributing catalysts uniformly throughout 26 finely divided coal o~fers several advantages even when the 27 thus treated coal is to be consumed in a combustion process.
28 First, when an oxidation catalyst such as the noble metals 29 of Group VIII is used, the combustion will proceed more rapidly to completion and, indeed, complete combustion would 11~7~S3 be effected at a lower temperature. Second, when the cation imparted via the method of this invention reacts with sulfur dioxide and/or sulfur trioxide at the conditions of combustion a significant portion of the sulfur contained in the coal will be removed, in the form of metal sulfates, sulfites and sulfides, generally remaining in the ash. The net results, then, would be to reduce nitrogen oxide and particulate emission to the atmosphere as a result of lower temperature or more complete combusti~on and to reduce sulfur oxide and sulfur trioxide emissions to the atmosphere as a result of the reaction with a cation.
A still further advantage of the present invention is realized in gasification processes wherein the coal is rapidly heated in a gaseous medium or in a vacuum and wherein the coal particles have been previously treated such that a cation is uniformly distributed therethrough. In this regard, it should be noted that untreated coals of bituminous ran]c generally soften and swell to a plastic consistency when heated in this manner and often adhere to each other or to the walls of the reactor system. This sticking or adhering tendency is, however, significantly reduced or eliminated when the coal has been pretreated so as to contain a uniformly distributed cation by the method of this invention. This advantage is particularly pronounced when the cation incorporated into the coal is selected from the alkali and alkaline earth metals.
. .
DESCRIPTION OF THE PREFERRED EMBODIMENT
In a preferred embodiment of the present invention, a higher ranking coal; i.e., a coal containing less oxygen in an active form than would be required to impart from about - 15 ~
-11~7053 2 to about 10 Wt~ calcium ion, will be oxidized with air such that the resulting oxidized coal will contain between about 10 and 20 Wt~ oxygen and suffic~ent active sites to impart between about 1 x 10 3 and 5 X 10 3 gram atoms equivalents of a metallic cation per gram of coal, the thus oxidized coal will be ion exchanged with an alkali or alkaline earth metal cation and then subjected to gasification. In the preferred embodiment, the air oxidation of the coal will be accomplished in a fluid bed at a temperature within the range from about 175 to about 300C and with an air flow rate ~ 16 1~17~53 1 within the range from about 20 to about 10,000 V/V/Hr.
2 The ion exchange will be accomplished either with the 3 hydroxide of the desired alkali or alkaline earth metal 4 or a suitable salt thereof. Alternately, the ion exchange could be accomplished by first contacting the oxidized coal 6 with sodium hydroxide or other suitable sodium salt and 7 thereafter completely exchanging the sodium ion imparted into 8 the coal with the desired alkali or alkaline earth metal ion.
9 The second ion exchange will also be accomplished either with the hydroxide of the desired alkali or alkaline earth metal 11 or a suitable salt thereof. Generally, both ion exchanges 12 will be accomplished at a temperature within the range from 3 about 18C to about 110C and at a pH within the range from 4 about 7 to about 14. In those cases where sodium or potassium is the desired cation to be distributed throughout the coal 16 the hydro~ide could be used and the second exchange will, 7 of course, not be necessary. Sodium or potassium will be most 18 preferred when maximum methane production from gasification by 19 steam is desired. Calcium, on the other hand, will be most preferred when production of carbon monoxide and hydrogen by 21 steam gasification is desired.
22 Gasification of the thus treated coal will be 23 accomplished by contacting the coal with steam at a temper-24 ature within the range from about 400C to about 1000 C at a steam flow-rate within the range from about 0.2 to about 26 5Q W/W/Hr. In general, essentially any pressure could be 27 used during this contacting, but pressures within the range 28 from about 0 to about 1000 psig are mos+ preferred.
29 Having thus broadly described the present invention ~ and set forth a preferred embodiment thereof, it is believed !
~il7~53 i I that the same will become ~ven more ~pparent by re~erence to 2 the following examples. These examples are, however, 3 intended solely for the purpose of illustration and should 4 not be construed so as to limit the invention, 5 EXhMPLE 1 6 In this example, two 15-gram samples of a bituminous 7 rank coal from Illinois were oxidized with air and then ion-8 exchanged with sodium hydroxide so as to distribute sodium 9 cation uniformly through the coal, Prior to oxidation, the 10 coal was ground to a particle size range ranging from about 11 0.15 mm to about 0.59 mm. Both oxidations were accomplished 12 at a temperature of about 200-230C and the holding time 3 was varied to produce a product having different oxygen 14 contents. The coal was maintained in a fluidized state 15 during oxidation. Before oxidation, the coal contained 16 14 Wt% oxygen. After oxidation, the first sample contained 17 about 17.5 Wt% oxygen and the second sample contained about 18 18.0 Wt% oxygen. Following oxidation, the oxidized coal lg samples were placed in an aqueous solution of sodium hydroxide 20 and allowed to remain in this solution for several days. The 21 ion exchange was accomplished at room temperature (Ca 18C).
22 The samples were then washed with pure water for several days 23 so as to ensure complete removal of any sodium cations not 24 actually exchanged with the coal. The i.on exchanged coal 2S samples were then analyzed to determine cation content. The 26 results obtained are summarized in the following table which 27 also includes the results obtained with an unoxidized coal 28 identical to that used in this sample, ~117~`53 Increased Oxygen Sodium Cation 2 Content, Wt~o Wt%
0 1.9 3.5 5.8 4 4.0 6.3 As will be readily apparent from the foregoing, the maximum 6 amount of sodium cation which can be incorporated into the 7 coal at the ion exchange conditions employed, increased with 8 increasing oxygen content.
In this example, the procedure of Example l.was 11 repeated except that ion exchange was accomplished with 12 potassium hydroxide rather than sodium hydroxide. Also, 3 five samples of coal identical to that used in Example 1 14 were oxidized to different oxygen levels instead of just two. The final oxygen content and the amount of potassium 16 ion incorporated into the coal are summarized in the table 17 set forth below. For purposes of comparison, the amount of 18 potassium incorporated via the same ion exchange techniques 19 into an unoxidized coal is also included in the table.
20Increased OxygenPotassium Cation Content, Wt% Wt%
O 4.0 22 1.3 5.5 3.5 6.2 23 3.8 7.2 4.8 8.9 24 7.4 11.2 From the foregoing, it will again be apparent that the 26 maximum amount of potassium incorporated into the coal 27 at the ion exchange conditions employed increased signifi-28 cantly with increased oxygen content.
~117~53 2 In this example, the procedure of Example l was 3 repeated except that ion exchange was accomplished with 4 calcium hydroxide rather than sodium hydroxide. Also, S eight samples o~ coal identical to that used in Example l 6 were oxidized to different oxygen levels instead of just 7 two, The final oxygen content and the amount of calcium 8 ion incorporated into the coal are summariæed in the table 9 set forth below. For purposes of comparison, the amount of calcium incorporated via the same ion exchange techniques 11 into an unoxidized coal is also included in the table.
12Increased Oxygen Calcium Cation Content ~t% Wt%
13 0 l.O
14 l 83 l 5 16 3 8 3 l As again will be apparent from the foregoing the maximum amount of calcium incorporated into the coal generally in-creased as the oxygen content increased. The variations indicated as oxygen content increased are, of course, within 22 experimental error.
EXA~PLE 4 24 In this example, a series of coking-gasi~ication tests were completed with ion exchange coals prepared in accordance with techniques described in Examples 1-3. For 2 purposes of comparison, identical runs were also made with 28 coal samples identical to those used in Examples 1-3, which 2~ contain sodium carbonate or potassium càrbonate in physical admixture therewith rather than by ion exchange. In all 1~17~53 1 runs, the coking-gasification was accomplished with steam 2 at a flow rate of about 50 W/W/Hr at a te~.perature of 760C
3 and at atmospheric pressure. The results obtained at 4 different cation concentrations are summarized in a table set forth below. For convenience, the results are compared 6 on the basis of the reaction rate at 50% conversion and the 7 rate is expressed as percent initial carbon converted per hour.
8 For reference purposes, the method by which the ion was 9 ineorporated into the coal is also set forth in the table Atoms Cation/
Atoms Carbon ~ethod ofGasifieation 11 CationIn Coke Incorporation Rate 12 Na 0.017 ion exchange120 Na 0.021 ion exchange250 13 Na 0.054 ion exchange375 Na 0.095 ion exchange420 14 K 0.048 ion exehange430 K 0.071 ion exchange605 Ca 0.015 ion exchange150 Ca 0.047 ion exchange595 16 Na ,019 Physical ~d-34 mixture 17 Na ,028 Physical Ad-94 mixture 18 K ,018 Physieal Ad-ll9 mixture 19 K ,028 Physieal Ad-214 mixture Ca ,018 Physical Ad-17 mixture 21 None -- None lO
22 The data clearly indieate that the gasification rate is 23 significantly increased with increased concentration of 24 both alkali and alkaline earth metal cations. The data also show that calcium, which is known to be relatively 26 non-catalytie when incorporated by physical admixture, 27 becomes quite aetive, catalytieally, when the same is incor-~a porated via ion exchange. This discovery is, of course, 29 quite surprising. The data also show that when the eations are incorporated via ion exchange, even with the alkali
6 With respect to the amount of catalytic-active 7 material being incorporated into the coal, it should be 8 noted that in those cases where the objective is to convert 9 the coal to either a-liquid-or- gaseous fuel, the prior oxi-0 dation, to the extent that it converts a portion of the coal 11 to water and carbon oxides, will reduce the overall effi-12 ciency of the conversion process by reducing the quantity of 13 coal available for subsequent conversion. The treatment 14 does, on the other hand, improve the ef~iciency of the overall process by increasing catalytic activity and thereby reducing 16 the holding time and/or temperature required in the subsequent 17 conversion operation, The overall efficiency of the 18 improved process or processes of this invention is, then, 9 a balance resu~ting from these considerations. In this regard, however, it should be noted that the advantages 21 resulting from ei'fective distribution of the catalyst far 22 outweigh the disadvantage resulting ~rom premature conver-23 sion of the coal to C02 and H20 so a s to affect catalyst 24 distribution. Notwithstanding this, however, careshould be exercised so as to avoid unnecessary oxidation of the 26 coal during the pretreatment step, 27 In general, any method known in the prior art 28 to be effective in controlling the rate and extent of 29 oxidation in a hydrocarbon can be used to affect the desired oxidation of the coal in the method of this in-~1~7Q53 1 vention. 5uch methods include, but are not necessarily 2 limited to, control of oxidizing reagent concentration and 3 the temperature o~ oxidation. Control oI oxidizin~ reagent 4 concentration can, of course, be controlled by mixing the reagent with a sui.table diluent during contacting. This 6 method would, of course, be most effective when a liquid 7 or solid oxidizing agent is employed but could be used even 8 when a gaseous-reducing agent is employed, In any case, 9 and even when oxidizing-agent concentration is controlled during contacting it will, generally, be necessary to control 11 temperature primarily to insure that oxidation does occur 12 within a reasonable period of time. Effective oxidizing-13 agent concentrations and effective oxidizing temperatures 14 are, of course, well within the ordinary skill o~ the art and need not be set forth in detail herein.
,16 ~otwithstanding that effective concentrations and 17 temperatures are within the ordinary skill of the art, it 18 should be noted that when a gas, such as air, is employed 19 as the oxidizing agent, essentially any temperature and pressure can be used during the oxidation and the exteIlt 21 of oxidation can be controlled by controlling the amount 22 of air actually contacting the coal and the temperature 23 at which contacting i9 accomplished. In th~s regard it 24 should be noted that sufficient oxidation of dry coal will occur autogeneously at room temperature but at least five 26 to seven days exposure are generally required. As a 27 result, elevated temperatures are most effective but 28 temperatures approaching combustion temperature should 29 be avoided. Temperatures within the range from about 18C
,to about 425C are, then, considered effective. Tempera-~7Q53 1 tures within ~he range from about 175C.~o about 300C. are, 2 however, preferred since temperatures helow about 175C. do 3 not provide suf~icient re~ction rates while temperatures 4 above 300C. result in reaction rates approaching those S of combustion. Due to the well-known time-temperature 6 effect, reaction times can vary from a few minu~es at the 7 higher temperatures to se~eral hours at the lower temper-8 atures.
9 In general, any of the ion exchange techniques known to be effective ~or exchanging any cation ~or a 11 hydrogen ion or a different cation can be used to effect 12 the desired catalyst distribution in the method of the 13 present inven~ion. These techniques include direct 14 contacting with a metal hydroxide in aqueous solution where the metal correspond~s to the desired catalytic cation 16 and the various techniques wherein a me~al salt ls used to 17 efect the desired ion exchange. Again, when metal salts 18 are used the metal portion of the salt will correspond to 19 the cation sought to be imparted into the coal. In general, aqueous solutions of a hydroxide or a salt of a weak acid 21 will be employed to effect the ion exchange. As is well 22 known, the ion exchange will occur at a basic pH; i.e., 23 a pH ~reater than 7. The coal may, o~ course, be pre-24 treated; i.e., prior to the ion exchange, with an organic or inorganic acid such as formic acid or the like, to 26 remove undeslrable, naturally occurring, complexed elements.
27 When this is done, care should be exercised to insure that 28 the acid employed will not impart an undesirable anion into 29 the coal. Also, it will, gener~lly, be necessary to wash out or neutralize the acidity of the aqueous medium prior ~117~53 to ion exchanqe. Such neutralization can, of course, be accomplishecl in accordance with known techniques and need not be discussed in detail herein. Notwithstanding this, however, it should be noted that ammonia can be effectively used to control the pH and that ammonia is particularly effective when an acid pretreat is used and when alkali and alkaline salts, particularly the halide salts, are used to effect the desired ion exchange. The anion can then later be removed by water washing or the like.
In the method heretofore desc~ibed, the pretreatment or oxidation is accomplished prior to the ion exchange. It is, however, within the scope of this invention to effect both oxidation and ion exchange simultaneously. When this is done, oxygen will either be bubbled through the ion exchange solution during contacting with the coal, or another suitable oxidizing agent will be incorporated into the ion exchange solution. As in the previously described embodiment, the simultaneous oxidation-ion exchange will be accomplished in accordance with techniques known in the prior art.
As indicated previously, the particular cation or cations incorporated into the coal will depend upon the subsequent conversion process employed. For example, and as indicated previously, where the subsequent conversion is to be via gasification, alkali and alkaline earth metals will preferably be employed.
~i ~il70~3 1 In general, any o~ the gasification processes 2 known in the prior art can be improved with respect to 3 ei.ther yield, conversion rate of both when the catalyst 4 distribution method of this invention is employed prior to effecting the gasification reaction. In general, these 6 gasification processes comprise a step wherein coal is 7 .reacted with a gaseous species or a mixture of gaseous 8 species at an elevated temperature, and, generally, an 9 elevated pressure to produce other, more desirable gases. The gaseous species generally employed as react-11 ants include oxygen, steam, carbon oxides such as carbon 12 dioxide, and hydrogen. Generally, temperature, pressure, 13 and flow rate in these processes as well as the mole ratio 1i 14 or relative ratio of reacting gases to coal will depend on the specific process employed and the actual products desired 16 therefrom. In this regard, it should be noted that the 17 composition of the gaseous products from these processes 18 cal also be altered by the particular catalyst employed.
19 For example, and as is known in the prior art, the products resulting from the gasification of coal with steam can be 21 enriched in methane through the use of an alkali metal that 22 promotes the conversion of carbon monoxide and hydro~en 23 to methane.
24 As previously indicated, the method of this invention ~or distributing catalysts uniformly throughout 26 finely divided coal o~fers several advantages even when the 27 thus treated coal is to be consumed in a combustion process.
28 First, when an oxidation catalyst such as the noble metals 29 of Group VIII is used, the combustion will proceed more rapidly to completion and, indeed, complete combustion would 11~7~S3 be effected at a lower temperature. Second, when the cation imparted via the method of this invention reacts with sulfur dioxide and/or sulfur trioxide at the conditions of combustion a significant portion of the sulfur contained in the coal will be removed, in the form of metal sulfates, sulfites and sulfides, generally remaining in the ash. The net results, then, would be to reduce nitrogen oxide and particulate emission to the atmosphere as a result of lower temperature or more complete combusti~on and to reduce sulfur oxide and sulfur trioxide emissions to the atmosphere as a result of the reaction with a cation.
A still further advantage of the present invention is realized in gasification processes wherein the coal is rapidly heated in a gaseous medium or in a vacuum and wherein the coal particles have been previously treated such that a cation is uniformly distributed therethrough. In this regard, it should be noted that untreated coals of bituminous ran]c generally soften and swell to a plastic consistency when heated in this manner and often adhere to each other or to the walls of the reactor system. This sticking or adhering tendency is, however, significantly reduced or eliminated when the coal has been pretreated so as to contain a uniformly distributed cation by the method of this invention. This advantage is particularly pronounced when the cation incorporated into the coal is selected from the alkali and alkaline earth metals.
. .
DESCRIPTION OF THE PREFERRED EMBODIMENT
In a preferred embodiment of the present invention, a higher ranking coal; i.e., a coal containing less oxygen in an active form than would be required to impart from about - 15 ~
-11~7053 2 to about 10 Wt~ calcium ion, will be oxidized with air such that the resulting oxidized coal will contain between about 10 and 20 Wt~ oxygen and suffic~ent active sites to impart between about 1 x 10 3 and 5 X 10 3 gram atoms equivalents of a metallic cation per gram of coal, the thus oxidized coal will be ion exchanged with an alkali or alkaline earth metal cation and then subjected to gasification. In the preferred embodiment, the air oxidation of the coal will be accomplished in a fluid bed at a temperature within the range from about 175 to about 300C and with an air flow rate ~ 16 1~17~53 1 within the range from about 20 to about 10,000 V/V/Hr.
2 The ion exchange will be accomplished either with the 3 hydroxide of the desired alkali or alkaline earth metal 4 or a suitable salt thereof. Alternately, the ion exchange could be accomplished by first contacting the oxidized coal 6 with sodium hydroxide or other suitable sodium salt and 7 thereafter completely exchanging the sodium ion imparted into 8 the coal with the desired alkali or alkaline earth metal ion.
9 The second ion exchange will also be accomplished either with the hydroxide of the desired alkali or alkaline earth metal 11 or a suitable salt thereof. Generally, both ion exchanges 12 will be accomplished at a temperature within the range from 3 about 18C to about 110C and at a pH within the range from 4 about 7 to about 14. In those cases where sodium or potassium is the desired cation to be distributed throughout the coal 16 the hydro~ide could be used and the second exchange will, 7 of course, not be necessary. Sodium or potassium will be most 18 preferred when maximum methane production from gasification by 19 steam is desired. Calcium, on the other hand, will be most preferred when production of carbon monoxide and hydrogen by 21 steam gasification is desired.
22 Gasification of the thus treated coal will be 23 accomplished by contacting the coal with steam at a temper-24 ature within the range from about 400C to about 1000 C at a steam flow-rate within the range from about 0.2 to about 26 5Q W/W/Hr. In general, essentially any pressure could be 27 used during this contacting, but pressures within the range 28 from about 0 to about 1000 psig are mos+ preferred.
29 Having thus broadly described the present invention ~ and set forth a preferred embodiment thereof, it is believed !
~il7~53 i I that the same will become ~ven more ~pparent by re~erence to 2 the following examples. These examples are, however, 3 intended solely for the purpose of illustration and should 4 not be construed so as to limit the invention, 5 EXhMPLE 1 6 In this example, two 15-gram samples of a bituminous 7 rank coal from Illinois were oxidized with air and then ion-8 exchanged with sodium hydroxide so as to distribute sodium 9 cation uniformly through the coal, Prior to oxidation, the 10 coal was ground to a particle size range ranging from about 11 0.15 mm to about 0.59 mm. Both oxidations were accomplished 12 at a temperature of about 200-230C and the holding time 3 was varied to produce a product having different oxygen 14 contents. The coal was maintained in a fluidized state 15 during oxidation. Before oxidation, the coal contained 16 14 Wt% oxygen. After oxidation, the first sample contained 17 about 17.5 Wt% oxygen and the second sample contained about 18 18.0 Wt% oxygen. Following oxidation, the oxidized coal lg samples were placed in an aqueous solution of sodium hydroxide 20 and allowed to remain in this solution for several days. The 21 ion exchange was accomplished at room temperature (Ca 18C).
22 The samples were then washed with pure water for several days 23 so as to ensure complete removal of any sodium cations not 24 actually exchanged with the coal. The i.on exchanged coal 2S samples were then analyzed to determine cation content. The 26 results obtained are summarized in the following table which 27 also includes the results obtained with an unoxidized coal 28 identical to that used in this sample, ~117~`53 Increased Oxygen Sodium Cation 2 Content, Wt~o Wt%
0 1.9 3.5 5.8 4 4.0 6.3 As will be readily apparent from the foregoing, the maximum 6 amount of sodium cation which can be incorporated into the 7 coal at the ion exchange conditions employed, increased with 8 increasing oxygen content.
In this example, the procedure of Example l.was 11 repeated except that ion exchange was accomplished with 12 potassium hydroxide rather than sodium hydroxide. Also, 3 five samples of coal identical to that used in Example 1 14 were oxidized to different oxygen levels instead of just two. The final oxygen content and the amount of potassium 16 ion incorporated into the coal are summarized in the table 17 set forth below. For purposes of comparison, the amount of 18 potassium incorporated via the same ion exchange techniques 19 into an unoxidized coal is also included in the table.
20Increased OxygenPotassium Cation Content, Wt% Wt%
O 4.0 22 1.3 5.5 3.5 6.2 23 3.8 7.2 4.8 8.9 24 7.4 11.2 From the foregoing, it will again be apparent that the 26 maximum amount of potassium incorporated into the coal 27 at the ion exchange conditions employed increased signifi-28 cantly with increased oxygen content.
~117~53 2 In this example, the procedure of Example l was 3 repeated except that ion exchange was accomplished with 4 calcium hydroxide rather than sodium hydroxide. Also, S eight samples o~ coal identical to that used in Example l 6 were oxidized to different oxygen levels instead of just 7 two, The final oxygen content and the amount of calcium 8 ion incorporated into the coal are summariæed in the table 9 set forth below. For purposes of comparison, the amount of calcium incorporated via the same ion exchange techniques 11 into an unoxidized coal is also included in the table.
12Increased Oxygen Calcium Cation Content ~t% Wt%
13 0 l.O
14 l 83 l 5 16 3 8 3 l As again will be apparent from the foregoing the maximum amount of calcium incorporated into the coal generally in-creased as the oxygen content increased. The variations indicated as oxygen content increased are, of course, within 22 experimental error.
EXA~PLE 4 24 In this example, a series of coking-gasi~ication tests were completed with ion exchange coals prepared in accordance with techniques described in Examples 1-3. For 2 purposes of comparison, identical runs were also made with 28 coal samples identical to those used in Examples 1-3, which 2~ contain sodium carbonate or potassium càrbonate in physical admixture therewith rather than by ion exchange. In all 1~17~53 1 runs, the coking-gasification was accomplished with steam 2 at a flow rate of about 50 W/W/Hr at a te~.perature of 760C
3 and at atmospheric pressure. The results obtained at 4 different cation concentrations are summarized in a table set forth below. For convenience, the results are compared 6 on the basis of the reaction rate at 50% conversion and the 7 rate is expressed as percent initial carbon converted per hour.
8 For reference purposes, the method by which the ion was 9 ineorporated into the coal is also set forth in the table Atoms Cation/
Atoms Carbon ~ethod ofGasifieation 11 CationIn Coke Incorporation Rate 12 Na 0.017 ion exchange120 Na 0.021 ion exchange250 13 Na 0.054 ion exchange375 Na 0.095 ion exchange420 14 K 0.048 ion exehange430 K 0.071 ion exchange605 Ca 0.015 ion exchange150 Ca 0.047 ion exchange595 16 Na ,019 Physical ~d-34 mixture 17 Na ,028 Physical Ad-94 mixture 18 K ,018 Physieal Ad-ll9 mixture 19 K ,028 Physieal Ad-214 mixture Ca ,018 Physical Ad-17 mixture 21 None -- None lO
22 The data clearly indieate that the gasification rate is 23 significantly increased with increased concentration of 24 both alkali and alkaline earth metal cations. The data also show that calcium, which is known to be relatively 26 non-catalytie when incorporated by physical admixture, 27 becomes quite aetive, catalytieally, when the same is incor-~a porated via ion exchange. This discovery is, of course, 29 quite surprising. The data also show that when the eations are incorporated via ion exchange, even with the alkali
31 metal eations that do impart eatalytie aetivity when phy-~1 ,,, 1 sically admixed, the catalytic activity is improved.
2 While the present invention has been described and 3 illustrated by reference to particular embodiments thereof, 4 it will be appreciated by those o~ ordinary skill in the art that the same lends itself to variations not necessarily illustrated herein. For this reason, then, reference should be made solely to the appended claims ~or purposes of determining the true scope of the present invention.
_ ~S --
2 While the present invention has been described and 3 illustrated by reference to particular embodiments thereof, 4 it will be appreciated by those o~ ordinary skill in the art that the same lends itself to variations not necessarily illustrated herein. For this reason, then, reference should be made solely to the appended claims ~or purposes of determining the true scope of the present invention.
_ ~S --
Claims (16)
IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method for catalytically gasifying coal which does not have sufficient sites to permit catalyst incorporation via ion exchange without pretreatment characterized by the steps of:
(a) oxidizing finely divided coal;
(b) ion exchanging the oxidized coal with a metallic cation; and (c) subjecting the exchanged coal to a conversion process under conversion reaction conditions.
(a) oxidizing finely divided coal;
(b) ion exchanging the oxidized coal with a metallic cation; and (c) subjecting the exchanged coal to a conversion process under conversion reaction conditions.
2. A method according to claim 1 further characterized in that the metal cation is selected from the group consisting of the alkali metal ions and the alkaline earth metal ions.
3. A method according to claim 1 or claim 2 further characterized in that the ion exchange is accomplished with a metal hydroxide.
4. A method according to claim 1 or claim 2 further characterized in that the ion exchange is accomplished with a metal salt.
5. A method according to claim 1 or claim 2 further characterized in that the ion exchange is effected at a pH within the range from about 7 to about 14.
6. A method according to claim 1 or claim 2 further characterized in that the ion exchanged coal contains from about 5 x 10-4 to about 8 x 10-3 gram atomic equivalents of incorporated cation per gram of coal.
7. A method according to claim 1 or claim 2 further characterized in that the ion exchange is accomplished silumtaneously with the oxidation step.
8. A method according to claim 1 or claim 2 further characterized in that the ion exchange is accomplished subsequent to the oxidation step.
9. A method according to claim 1 or claim 2 further characterized in that the coal is oxidized such that the oxygen content thereof is increased by an amount within the range from about 1 to about 10 wt. %.
10. A method according to claim 1 further characterized in that the conversion reaction is a gasification reaction which is accomplished by heating the ion exchange coal to a temperature within the range from about 400 to about 1000°C.
11. A method according to claim 10 further characterized in that the gasification is accomplished in the presence of steam at a flow rate within the range from about .2 to 50 W/W/Hr.
12. A method according to claim 10 or claim 11 further characterized in that the gasification is accomplished in the presence of hydrogen at a flow rate within the range from about .2 to about 50 W/W/Hr.
13. A method according to claim 1 or claim 2 further characterized in that the cation is a transition metal cation.
14. A method according to claim 1 further characterized in that said conversion reaction is a coal liquefaction reaction which is accomplished by heating the ion exchange coal to a temperature within the range from about 350°C to about 800°C.
15. A method according to claim 14 further characterized in that the liquefaction is accomplished in the presence of a slurrying hydrocarbon liquid within the range from about 1 to about 4 W/W/.
16. A method according to claim 14 or claim 15 further characterized in that the liquefaction is accomplished in the presence of hydrogen or carbon monoxide and hydrogen at a pressure within the range from about 100 to about 4000 psig.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US81203277A | 1977-07-01 | 1977-07-01 | |
| US812,032 | 1977-07-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1117053A true CA1117053A (en) | 1982-01-26 |
Family
ID=25208280
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000300949A Expired CA1117053A (en) | 1977-07-01 | 1978-04-12 | Process for gasifying coal wherein a catalyst is incorporated by ion exchange after partial oxidation of the coal |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS5413507A (en) |
| AU (1) | AU516041B2 (en) |
| BR (1) | BR7802372A (en) |
| CA (1) | CA1117053A (en) |
| DE (1) | DE2816891A1 (en) |
| FR (1) | FR2395779A1 (en) |
| GB (1) | GB1599932A (en) |
| ZA (1) | ZA782036B (en) |
Families Citing this family (64)
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| GB2010315B (en) * | 1977-12-19 | 1982-05-26 | Exxon Research Engineering Co | Gasification process |
| US4468231A (en) * | 1982-05-03 | 1984-08-28 | Exxon Research And Engineering Co. | Cation ion exchange of coal |
| EP0152506A1 (en) * | 1984-02-22 | 1985-08-28 | DECHEMA Deutsche Gesellschaft für chemisches Apparatewesen e.V. | Process for the oxidative conversion of coal |
| FR2579219A1 (en) * | 1985-03-22 | 1986-09-26 | Raffinage Cie Francaise | Process for catalytic steam-gasification of heavy carbonaceous and hydrocarbon feedstocks |
| JPS6395292A (en) * | 1986-10-09 | 1988-04-26 | Univ Tohoku | Catalytic gasification of coal using chloride |
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Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2693452A (en) * | 1949-08-20 | 1954-11-02 | Directie Staatsmijnen Nl | Preparation of cation exchange material from coal |
| US3893943A (en) * | 1971-01-20 | 1975-07-08 | Caw Ind Inc | Novel catalyst and process for preparing the same |
| ZA763382B (en) * | 1975-06-18 | 1977-05-25 | Battelle Memorial Institute | Converting fuels |
| GB2010315B (en) * | 1977-12-19 | 1982-05-26 | Exxon Research Engineering Co | Gasification process |
-
1978
- 1978-04-06 GB GB13521/78A patent/GB1599932A/en not_active Expired
- 1978-04-10 AU AU34913/78A patent/AU516041B2/en not_active Expired
- 1978-04-10 ZA ZA00782036A patent/ZA782036B/en unknown
- 1978-04-12 CA CA000300949A patent/CA1117053A/en not_active Expired
- 1978-04-13 JP JP4273378A patent/JPS5413507A/en active Pending
- 1978-04-17 BR BR7802372A patent/BR7802372A/en unknown
- 1978-04-18 DE DE19782816891 patent/DE2816891A1/en active Granted
- 1978-04-20 FR FR7811724A patent/FR2395779A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| FR2395779A1 (en) | 1979-01-26 |
| JPS5413507A (en) | 1979-02-01 |
| FR2395779B1 (en) | 1984-03-16 |
| ZA782036B (en) | 1979-03-28 |
| AU3491378A (en) | 1979-10-18 |
| AU516041B2 (en) | 1981-05-14 |
| DE2816891C2 (en) | 1988-04-14 |
| DE2816891A1 (en) | 1979-01-11 |
| GB1599932A (en) | 1981-10-07 |
| BR7802372A (en) | 1979-04-17 |
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