Patent Publication Number: US-6214176-B1

Title: Method of and apparatus for manufacturing methanol

Description:
CROSS REFERENCE TO RELATED APPLICATIONS 
     This application is a continuation-in-part of prior application Ser. No. 09/368,404 filed Aug. 4, 1999, currently pending which is a continuation-in-part of prior application Ser. No. 09/224,394 filed Dec. 31, 1998, now U.S. Pat. No. 6,129,818 which is a continuation-in-part of prior application Ser. No. 09/058,494, filed Apr. 10, 1998, now U.S. Pat. No. 5,954,925. 
    
    
     TECHNICAL FIELD 
     This invention relates generally to the manufacture of methanol, and more particularly to a method of and apparatus for manufacturing methanol from methane, and to a method of and apparatus for manufacturing methanol, ethanol, and propanol from natural gas. 
     BACKGROUND AND SUMMARY OF THE INVENTION 
     Methanol, the simplest of the alcohols, is a highly desirable substance which is useful as a fuel, as a solvent, and as a feedstock in the manufacturer of more complex hydrocarbons. In accordance with the method of methanol manufacture that is currently practiced in the petroleum industry, methane is first converted to synthesis gas, a mixture of carbon monoxide and hydrogen. The synthesis gas is then converted over an alumina-based catalyst to methanol. The formation of synthesis gas from methane is an expensive process. 
     Although often identified as methane, the feedstock for the foregoing synthesis gas process is typically natural gas. As is well known, natural gas often contains significant percentages of sulphur. Since sulphur poisons the catalyst required for its operation, the synthesis gas process for making methanol is further limited by the scarcity of low sulphur natural gas. 
     As will be apparent, methane and methanol are closely related chemically. Methane comprises a major component of natural gas and is therefore readily available. Despite the advantages inherent in producing methanol directly from methane, no commercially viable system for doing so has heretofore been developed. 
     The present invention comprises a method of and apparatus for manufacturing methanol from methane or natural gas which overcomes the foregoing and other deficiencies which have long since characterized the prior art. The method involves a gas permeable partition upon which a light-activated catalyst capable of producing hydroxyl radicals from water is deposited, it being understood that as used herein the term “light-activated catalyst” means any catalyst that is activated by electromagnetic radiation regardless of wave length. 
     Water is present on the catalyst side of the partition and methane or natural gas at positive pressure is present on the opposite side of the partition. The catalyst is exposed to radiation while relative movement is effected between the water and the partition. The radiation-exposed catalyst reacts with the water molecules to form hydroxyl radicals. The gas is forced through the semipermeable partition forming small bubbles in the water. The hydroxyl radicals in the water then undergo a free-radical reaction with the methane in the water to form methanol, and if natural gas is used in the process, ethanol and propanol. 
     In accordance with the broader aspects of the invention there is generated a stream of sub-micron sized gas bubbles. Due to their extremely small size, the gas bubbles present an extremely large surface area which increases reaction efficiency. Smaller pores in the gas permeable partition facilitate the formation of smaller bubbles. Additionally, higher relative velocity across the partition surface aids in shearing the bubbles off the surface while they are still small. 
     In accordance with first, second, and third embodiments of the invention, a gas permeable tube has an exterior coating comprising a titanium-based catalyst. The gas permeable tube is positioned within a glass tube and water is caused to continuously flow through the annular space between the two tubes. Methane or natural gas is directed into the interior of the gas permeable tube and is maintained at a pressure high enough to cause gas to pass into the water and prevent the flow of water into the interior of the gas permeable tube. As the water passes over the gas permeable tube, gas bubbles are continually sheared off of its surface. The gas bubbles thus generated are sub-micron in size and therefore present an extremely large surface area. 
     Electromagnetic radiation generated, for example, by ultraviolet lamps is directed through the glass tube and engages the titanium-based catalyst to generate hydroxyl radicals in the flowing water. The hydroxyl radicals undergo a free-radical reaction with the methane forming methanol, among other free-radical reaction products. Subsequently, the methanol and other products are separated from the reaction mixture by distillation. 
     In accordance with fourth, fifth, sixth, seventh, and eighth embodiments of the invention, there is provided a hollow disk which supports a gas permeable partition having an exterior coating comprising a titanium-based catalyst. The disk is positioned within a water filled container. Methane or natural gas is directed into the interior of the disk and is maintained at a pressure high enough to cause gas to pass outwardly through the partition and into the water and to prevent the flow of water into the interior of the disk. The disk and the partition are moved at high speed relative to the water. As the gas permeable partition moves relative to the water, gas bubbles are continually sheared off of its surface. The gas bubbles thus generated are sub-micron in size and then therefore present an extremely large surface area. 
     Electromagnetic radiation generated, for example, by ultraviolet lamps within the container engages the titanium-based catalyst to generate hydroxyl radicals in the water. The hydroxyl radicals undergo a free-radical reaction with the methane forming methanol, and, if natural gas is used in the process, ethanol and propanol. Subsequently, the methanol and other reaction products are separated from the reaction mixture by distillation. 
     In the practice of the fifth, sixth, seventh, and eighth embodiments of the invention, utilization of the energy comprising the electromagnetic radiation is maximized by providing a mirror within the hollow disk to reflect electromagnetic radiation passing through the porous partition back to the catalytic material. The mirror may comprise either a mirrored surface of the hollow disk or a separate mirror plate. Fluorescent material is utilized to convert broad-band electromagnetic radiation to radiation having a band width which is specific to the selected catalyst. The fluorescent material may be combined with the porous partition, or with the catalytic layer, or may comprise a distinct layer. 
     In accordance with a ninth embodiment of the invention, a plurality of parallel porous partitions each having a photocatalytic layer on its exterior surface are mounted in an array. The array further comprises sources of electromagnetic radiation positioned between each of the tubular porous partition/photocatalytic layer assemblies. Methane or natural gas from a first manifold is directed into the interior of each of the parallel porous partitions. Water from a second manifold is directed across the surface of the photocatalytic layers in the manner of the first three embodiments of the invention. In addition to activating the photocatalytic layers, energy from the electromagnetic radiation sources generally provides sufficient heat to distill the resulting methanol and higher alcohols from the water. 
     In accordance with a tenth embodiment of the invention, an oxidizer such as oxygen, peroxide, etc. is mixed with methane or natural gas. The mixture is then directed through a porous partition having a photocatalytic layer on its exterior surface. Water is continuously directed across the exterior surface of the porous partition in the manner of the first nine embodiments of the invention. In this manner the reaction is rendered self-sustaining. 
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS 
     A more complete understanding of the invention may be had by reference to the following Detailed Description when taken in conjunction with the accompanying Drawings wherein: 
     FIG. 1 is a diagrammatic illustration of a method and apparatus for manufacturing methanol comprising a first embodiment of the present invention. 
     FIG. 2 is a diagrammatic illustration of a second embodiment of the apparatus of the present invention with a rotating sintered stainless steel tube. 
     FIG. 3 is a diagrammatic illustration of a third embodiment of the apparatus of the present invention with a rotating sintered stainless steel tube with turbines. 
     FIG. 4 is a diagrammatic illustration of a fourth embodiment of the apparatus of the present invention. 
     FIG. 5 is an enlargement of a portion of FIG.  4 . 
     FIG. 6 is an illustration similar to FIG. 5 showing an alternative construction useful in the practice of the invention. 
     FIG. 7 is an exploded view of a modification of the hollow disk of FIG. 4 comprising a fifth embodiment of the invention. 
     FIG. 8 is an assembly view of the fifth embodiment of the invention. 
     FIG. 9 is an exploded view of a modification of the hollow disk of FIG. 4 comprising a sixth embodiment of the invention. 
     FIG. 10 is an assembly view of the sixth embodiment of the invention. 
     FIG. 11 is an exploded view of a modification of the hollow disk of FIG. 4 comprising a seventh embodiment of the invention. 
     FIG. 12 is an assembly view of the seventh embodiment of the invention. 
     FIG. 13 is an exploded view of a modification of the hollow disk of FIG. 4 comprising an eighth embodiment of the invention. 
     FIG. 14 is an assembly view of the eighth embodiment of the invention. 
     FIG. 15 is a diagrammatic illustration of a ninth embodiment of the invention. 
     FIG. 16 is a flow chart illustrating a tenth embodiment of the invention. 
    
    
     DETAILED DESCRIPTION 
     Referring now to the Drawings, and particularly to FIG. 1 thereof, there is shown an apparatus for manufacturing methanol  10  comprising a first embodiment of the invention. The apparatus  10  includes a gas permeable tube  12  positioned within a glass tube  14 . The tube  12  can comprise sintered stainless steel, or sintered glass, sintered ceramic materials, or a photocatalytic material. As illustrated in FIG. 1, both the gas permeable tube  12  and the glass tube  14  comprise right circular cylinders with the tube  12  extending concentrically relative to the tube  14 . Other geometrical configurations of and positional relationships between the gas permeable tube  12  and the glass tube  14  may be utilized in accordance with the requirements of particular applications of the invention. 
     If not formed from a photocatalytic materiel, the gas permeable tube  12  has a light-activated catalyst layer  16  formed on the exterior surface thereof. The catalyst layer  16  is preferably a titanium-based catalyst; however, it will be understood that any light-activated catalyst which forms hydroxyl radicals from water may be utilized in the practice of the invention, if desired. A plurality of electromagnetic radiation sources  18 , such as ultraviolet lamps, are positioned around the exterior of the glass tube  14 , it being understood that while only one source  18  is illustrated in FIG. 1, in actual practice a plurality of energy sources  18  are employed and are disposed around the entire periphery of the tube  14 . As illustrated by the waves  20  in FIG. 1, the sources  18  generate energy in the form of, for example, ultraviolet light which is directed through the glass tube  14  and onto the catalytic layer  16  formed on the exterior surface of the gas permeable tube  12 . 
     In the operation of the apparatus for manufacturing methanol  10 , a quantity of water is received in a reservoir  22 . Water from the reservoir  22  is directed into the annular space between the gas permeable tube  12  and the glass tube  14  through piping  24 . During the operation of the apparatus  10  water flows through the annulus between the gas permeable tube  12  and the glass tube  14  on a continuous basis. 
     A quantity of methane or natural gas is stored in a reservoir  26 . In the operation of the apparatus  10 , gas is directed from the reservoir  26  into the interior of the gas permeable tube  12  through piping  28 . The gas within the gas permeable tube  12  is maintained at a pressure high enough to cause the gas to pass through the walls of the tube  12  into the water and to prevent the flow of water into the interior of the tube  12 . 
     In the operation of the apparatus for manufacturing methanol  10 , the water flowing through the annular space between the gas permeable tube  12  and the glass tube  14  causes gas bubbles to be continuously stripped off the exterior surface of the tube  12 . In this manner the size of the gas bubbles is maintained in the sub-micron range. The sub-micron size of the gas bubbles provides an enormous methane surface area which in turn results in unprecedented reaction efficiency. 
     As the sub-micron size gas bubbles are produced by the flow of water over the exterior surface of the gas permeable tube  12 , energy from the sources  18  continuously engages the catalytic surface  16  formed on the exterior of the tube  12 . This generates hydroxyl radicals in the flowing water. It is theorized that the hydroxyl radicals homolyticaly cleave one or more of the carbon-hydrogen bonds in the methane thereby forming either molecules of hydrogen or molecules of water, depending upon the initiating radical, and methyl radicals. The methyl radicals combine either with the hydroxyl radicals to form methanol or with the hydrogen radicals to form methane. 
     Those skilled in the art will appreciate the fact that other chemical reactions are possible in the operation of the apparatus for manufacturing methanol  10 . For example there exists the possibility of a methyl-methyl radical reaction, and also the possibility of a hydrogen-hydrogen radical reaction. Both of these possibilities are extremely remote due to the relatively low concentrations of methyl radicals and hydrogen radicals at any given time. 
     It will be further understood that natural gas typically comprises up to 10% ethane and up to 2% propane in addition to methane. Therefore, if natural gas is used in the practice of the invention, the reaction products include ethanol, normal propanol, and isopropanol in addition to methanol. 
     The water flowing from the annulus between the gas permeable tube  12  and the glass tube  14  having the reaction products contained therein is directed to a distillation apparatus  30  through piping  32 . The distillation apparatus  30  separates the outflow from the space between the tube  12  and the tube  14  into at least four streams, including a stream of unreacted methane  34  which is returned to the reservoir  26 , a stream of water  36  which is returned to the reservoir  22 , a stream of other reaction products  38  which are recovered, and a stream of methanol  40 . The stream of other reaction products  38  may be further separated into its component parts, if desired. 
     The present invention further comprises a method of making methanol. In accordance with the method there is provided a continuously flowing stream of water. Sub-micron size bubbles of methane are continuously injected into the flowing water. Hydroxyl radicals are continuously generated from the water. It is theorized that the hydroxyl radicals cleave the hydrogen-carbon bonds of the methane to form methyl radicals. The methyl radicals combine with the hydroxyl radicals to form methanol. 
     In accordance with more specific aspects of the method, a gas permeable tube having a catalytic layer on the exterior surface thereof is positioned within a glass tube. Water is directed through the annulus between the gas permeable tube and the glass tube, and methane or natural gas is directed into the interior of the gas permeable tube. The water flowing between the gas permeable tube and the glass tube continuously strips sub-micron size bubbles from the exterior surface of the gas permeable tube. 
     Electromagnetic radiation from, for example, ultraviolet lamps is directed through the glass tube and engages the catalytic surface on the exterior of the gas permeable tube, thereby forming hydroxyl radicals from the flowing water. It is theorized that the hydroxyl radicals homolyticaly cleave one or more of the carbon-hydrogen bonds in the methane to form either molecules of hydrogen or molecules of water, and methyl radicals. The methyl radicals combine either with the hydroxyl radicals to form methanol or with the hydrogen radicals to form methane. Ethanol and propanol are also produced if natural gas is used in the process. 
     The use of an internal gas permeable partition cylinder is shown in FIG.  1 . One skilled in the art would also recognize that a vast number of shapes and orientations could be used to accomplish the same purpose. For example, the glass tube  14  does not need to be shaped as a tube in order to be functional as a housing. In fact, such a housing need only be partially transparent to electromagnetic radiation for the apparatus to function. Additionally, the orientation of the gas inside an inner tube with water between the inner tube and a housing is not required. One skilled in the art could envision a housing bisected by a gas permeable partition creating a water chamber and a gas chamber. The only requirements of such an embodiment is that the water chamber has a water source and a product outlet, which leads to an isolation apparatus, preferably a distillation apparatus; the gas chamber has a gas source; the gas permeable partition has a catalytic layer that is exposed to electromagnetic energy on the water side of the partition; and the gas permeable partition allows the penetration of gas bubbles that are sheared off by the relative movement of water in the water chamber relative to the gas permeable membrane. 
     Referring now to FIG. 2, there is shown an apparatus for manufacturing methanol comprising a second embodiment of the invention. The apparatus  50  comprises numerous component parts which are substantially identical in construction and function to the apparatus for manufacturing methanol  10  shown in FIG.  1  and described hereinabove in conjunction therewith. Such identical component parts are designated in FIG. 2 with the same reference numerals utilized in the description of the apparatus  10 , but are differentiated therefrom by means of a prime (′) designation. 
     In the apparatus for manufacturing methanol  50 , the gas permeable tube  12 ′ is supported for rotation relative to the glass tube  14 ′ by sealed bearings  52 . Those skilled in the art will appreciate the fact that bearing/seal assemblies comprising separate components may be utilized in the practice of the invention, if desired. 
     A motor  54  is mounted at one end of the glass tube  14 ′ and is operatively connected to the gas permeable tube  12 ′ to effect rotation thereof relative to the glass tube  14 ′. The glass tube  14 ′ includes an end portion  56  which is isolated from the remainder thereof by a seal  58 . The portion of the tube  12 ′ extending into the end portion  56  of the glass tube  14 ′ is provided with a plurality of uniform or nonuniform apertures  60 . 
     In the operation of the apparatus for manufacturing methanol  50 , methane or natural gas is directed from the reservoir  26 ′ through the piping  28 ′, through the end portion  56  of the glass tube  14 ′ and through the apertures  60  into the interior of the gas permeable tube  12 ′. Water flows from the reservoir  22 ′ through the piping  24 ′ and into the portion of the glass tube  14 ′ that is isolated from the end portion  56  by the seal  58 . Water flows out of the glass tube  14 ′ through piping  32 ′ to the distillation apparatus  30 ′. 
     The operation of the apparatus for manufacturing methanol  50  of FIG. 2 differs from the operation of the apparatus for manufacturing methanol  10  of FIG. 1 in that in the operation of the apparatus  50 , the relative movement between the bubbles forming on the surface of the gas permeable tube  12 ′ and the water contained within the glass tube  14 ′ is controlled by the motor  54  rather than the flow rate of the water as it passes through the glass tube  14 ′. This is advantageous in that it allows the gas permeable tube  12 ′ to be rotated at a relatively high velocity relative to the water contained within the glass tube  14 ′, thereby assuring that sub-micron size bubbles will be sheared from the surface of the gas permeable tube  12 ′. Meanwhile, the velocity of the water passing through the interior of the glass tube  12 ′ can be relatively slow, thereby assuring a maximum number of sub-micron size bubbles entering the water per unit volume thereof. 
     An apparatus for manufacturing methanol comprising a third embodiment of the invention is illustrated in FIG.  3 . The apparatus for manufacturing methanol  60  comprises numerous component parts which are substantially identical in construction and function to component parts of the apparatus for manufacturing methanol  10  illustrated in FIG.  1  and described hereinabove in conjunction therewith. Such identical component parts are designated in FIG. 3 with the same reference numerals utilized in the description of the apparatus  10 , but are differentiated therefrom by means of a double prime ( 41  ) designation. 
     The apparatus for manufacturing methanol  60  comprises a gas permeable tube  12 ″ which is supported for rotation relative to the glass tube  14 ″ by sealed bearings  62 . Those skilled in the art will appreciate the fact that the apparatus  60  may be provided with bearing/seal assemblies comprising separate components, if desired. 
     The gas permeable tube  12 ″ is provided with one or more turbines  64 . The pitch of the turbines  64  is adjusted to cause the tube  12 ″ to rotate at a predetermined speed in response to a predetermined flow rate of water through the glass tube  14 ″. 
     Similarly to the apparatus for manufacturing methanol of FIG. 2, the use of the apparatus for manufacturing methanol  60  is advantageous in that the gas permeable tube  12 ″ can be caused to rotate relatively rapidly in response to a relatively low flow rate of water through the glass tube  14 ″. This assures that sub-micron size bubbles will be stripped from the outer surface of the gas permeable tube  12 ″ and that a maximum number of bubbles will be received in the water flowing through the glass tube  14 ″ per unit volume thereof. The use of the apparatus for manufacturing methanol  60  is particularly advantageous in applications of the invention wherein water flows through the system under the action of gravity, in that the use of the turbines  64  eliminates the need for a separate power source to effect rotation of the gas permeable tube  12 ″ relative to the glass tube  14 ″. 
     Referring now to FIGS. 4 and 5, there is shown a method of and apparatus for manufacturing methanol and other alcohols  70  comprising a fourth embodiment of the invention. In accordance with a fourth embodiment of the invention, there is provided a distillation unit  72  comprising a tank having a quantity of water  74  contained therein. One or more electromagnetic radiation sources  76  are also positioned in the tank  72 . The distillation unit  72  includes a heat source, which may comprise the radiation sources  76 , sufficient to effect distillation of methanol and other alcohols from water. 
     A hollow disk  78  is mounted in the lower portion of the tank  78 . As is best shown in FIG. 5, the disk  78  includes a gas permeable partition  80  supported on a tube  82  for rotation within the tank  72  under the operation of a motor  84 . The partition  80  may comprise sintered stainless steel, sintered glass, or sintered ceramic materials, or may be formed entirely from a catalytic material, depending upon the requirements of particular applications of the invention. Natural gas received from a supply  86  is directed through piping  88  and a suitable commutator  90  into the tube  82  and through the tube  82  into the interior of the hollow disk  78 . The tube  82  has a hollow interior  90  and the disk  78  has a hollow interior  92  connected in fluid communication therewith. The gas permeable partition  80  is coated with a light-activated catalytic layer  94 . 
     The disk  78  is supplied with natural gas at a pressure just high enough to overcome to head pressure of the water  74 . The disk  78  is rotated by the motor  84  at an appropriate speed in contact with the water  74  such that a shearing phenomenon occurs at the surface of the photocatalytic layer  94  thus producing bubbles of natural gas of extremely small size. The extreme small size of the bubbles thus produced results in a surface area to volume ratio of small bubbles which significantly improves the efficiency of the reaction. 
     As the sub-micron size gas bubbles are produced by movement of the exterior surface of the gas permeable partition  80  in the water  74 , electromagnetic energy from the sources  76  continuously engages the catalytic surface  94  formed on the exterior of the partition  80 , it being understood that depending on the characteristics of the catalytic layer  94 , energy comprising various portions of the electromagnetic spectrum may be used in the practice of the invention. 
     Activation of the catalytic layer  94  generates hydroxyl radicals in the water. It is theorized that the hydroxyl radicals homolyticaly cleave one or more of the carbon-hydrogen bonds in the methane, ethane, propane, etc., thereby forming either molecules of hydrogen or molecules of water, depending upon the initiating radical, and methyl, ethyl, and propyl radicals which combine either with the hydroxyl radicals to form methanol, ethanol, and propanol, or with the hydrogen radicals to form methane, ethane, and propane. 
     The methanol produced by the operation of the distillation unit  72  is recovered at outlet  96 . A pressure swing absorber  97  receives natural gas and hydrogen from the distillation unit  72 . Unreacted natural gas is recovered from the pressure swing absorber  97  at outlet  98  and is returned to the distillation unit  72  through piping  88 . Byproduct hydrogen produced in the distillation unit  72  is recovered at outlet  100  and is directed to a fuel cell  102 . 
     Within the fuel cell  102 , hydrogen recovered from the distillation unit  72  is combined with oxygen from the atmosphere to produce electricity which is recovered at terminal  104  and water which is recovered at outlet  106  and returned to the distillation unit  72  through piping  108 . As will be appreciated by those skilled in the art, a conventional engine/generator may be used in lieu of the fuel cell  102 ; however, the use of a fuel cell is preferred due to its greater efficiency. 
     The use of the hydrogen recovered from the distillation unit  72  to produce electricity comprises an important advantage in the use of the present invention in that the electricity thus produced may be utilized to provide artificial lighting in those instances in which the apparatus  70  is situated at a remote location and/or to provide heating for the distillation unit  72 . As is shown in FIG. 4, electricity from the fuel cell  102  may also be used to operate the radiation sources and  76  the motor  84 . 
     In addition to producing methanol, the apparatus  70  converts other alkanes present in the natural gas to their respective alcohols, namely: ethanol, normal propanol, and isopropanol. The higher alcohols thus produced are recovered from the distillation  72  at outlet  110  and are directed to a reverse osmosis unit  112 , and from the reverse osmosis unit  112  to a secondary distillation unit  114  to produce purer forms of the higher alcohols. Like the distillation unit  72 , the distillation unit  114  is provided with a heat source adequate to effect the desired distillation. Unrecovered materials from the secondary distillation unit  114  are returned to the reverse osmosis unit  112  through piping  116 . The reverse osmosis unit  112  also produces water which is returned to the distillation unit  72  through the piping  108 . 
     Typically, the water which is returned to the distillation unit  72  from the fuel cell  102  and the reverse osmosis unit  112  is sufficient to maintain a predetermined quantity of water therein. The distillation unit  72  is initially filled from a water supply  118  which is also available to supplement the water received from the fuel cell  102  and the reverse osmosis unit  112  if necessary to maintain an adequate supply of water in the distillation unit  72 . 
     In lieu of the motor  84 , the disk  78  may be oscillated using a torsion motor or reciprocated using a motor and crank assembly. Other apparatus for effecting relative movement between the partition  80  and the water  74  will suggest themselves to those skilled in the art. 
     As will be appreciated by those skilled in the art, it is known to produce gas permeable partitions entirely from photocatalytic material, including titanium-based catalytic materials. FIG. 6 illustrates a hollow disk  78  having a gas permeable partition  120  formed entirely from one or more catalytic materials. Such construction eliminates the need of forming a catalytic layer on the surface of a gas permeable partition. 
     Those skilled in the art will appreciate the fact that the method and apparatus of the present invention can be utilized to convert gases other than methane and natural gas into valuable products. For example, the method and apparatus of the present invention can be utilized to convert carbon dioxide to methanol and methane. The adaptation of other chemical processes to the method and apparatus of the present invention will readily suggest themselves to those skilled in the art. 
     Referring to FIGS. 7 and 8, there is shown a hollow disk assembly  130  comprising a fifth embodiment of the invention. The hollow disk assembly  130  includes a hollow disk  132  which is supported on a hollow tube  134  for rotation, oscillation, or reciprocation relative to a quantity of water (not shown in FIGS.  7  and  8 ). The hollow disk assembly  130  further includes a porous partition  136  supported on the hollow disk  132  and a layer or plate of catalyst material  138  supported on the porous partition  136 . 
     The hollow disk assembly  130  comprising the fifth embodiment of the invention differs from the hollow disk assembly of FIG. 4 in two significant aspects. First, the hollow disk  132  is provided with a mirrored surface  140  formed on the interior surface of the hollow disk  132  opposite the porous partition  136 . Thus, the mirrored surface  140  functions to reflect electromagnetic radiation passing through the catalytic material  138  and the porous partition  136  back to the catalytic material  138 , thereby substantially increasing the efficiency of the interaction between the electromagnetic radiation and the catalytic material  138 . 
     Additionally, the porous plate  136  includes a quantity of a fluorescent material. The fluorescent material which is included in the porous partition  136  is selected to respond to broad-band electromagnetic radiation to produce an output comprising narrow band electromagnetic radiation which is specifically matched to the band width of the radiation which activates the catalytic material  138 . In this manner, the efficiency of the catalytic reaction is substantially increased because the portion of the electromagnetic radiation which would otherwise be unused is transformed by the fluorescent material into radiation within the band width comprising the input requirements of the catalytic material. 
     Referring to FIGS. 9 and 10, there is shown a hollow disk assembly  150  comprising a sixth embodiment of the invention. The hollow disk assembly  150  includes a hollow disk  152  which is supported on a hollow tube  154  for rotation, oscillation, or reciprocation relative to a quantity of water (not shown in FIGS.  9  and  10 ). The hollow disk assembly  150  further includes a porous partition  156  supported on the hollow disk  152  and a layer or plate of catalyst material  158  supported on the porous partition  156 . 
     The hollow disk assembly  150  comprising the sixth embodiment of the invention differs from the hollow disk assembly of FIG. 4 in two significant aspects. First, the hollow disk  152  is provided with a mirrored surface  160  formed on the interior surface of the hollow disk  152  opposite the porous partition  156 . Thus, the mirrored surface  160  functions to reflect electromagnetic radiation passing through the catalytic layer  158  and the porous partition  156  back to the catalytic layer  156 , thereby substantially increasing the efficiency of the interaction between the electromagnetic radiation and the catalytic layer. 
     Additionally, the catalyst material  158  includes a quantity of a flourescent material. The flourescent material which is included in the catalyst material  158  is selected to respond to broad-band electromagnetic radiation to produce an output comprising narrow band electromagnetic radiation which is specifically matched to the band width of the radiation which activates the catalytic material  158 . In this manner, the efficiency of the catalytic reaction is substantially increased because the portion of the electromagnetic radiation which would otherwise be unused is transformed by the flourescent material into radiation within the band width comprising the input requirements of the catalytic layer. 
     Referring to FIGS. 11 and 12, there is shown a hollow disk assembly  170  comprising a seventh embodiment of the invention. The hollow disk assembly  170  includes a hollow disk  172  which is supported on a hollow tube  174  for rotation, oscillation, or reciprocation relative to a quantity of water (not shown in FIGS.  11  and  12 ). The hollow disk assembly  170  further includes a porous partition  176  supported on the hollow disk  172  and a layer or plate of catalyst material  178  supported on the porous partition  176 . 
     The hollow disk assembly  170  comprising the seventh embodiment of the invention differs from the hollow disk assembly of FIG. 4 in two significant aspects. First, the hollow disk  172  is provided with a mirrored surface  180  formed on the interior surface of the hollow disk  172  opposite the porous partition  176 . Thus, the mirrored surface  180  functions to reflect electromagnetic radiation passing through the catalytic layer  178  and the porous partition  176  back to the catalytic layer  176 , thereby substantially increasing the efficiency of the interaction between the electromagnetic radiation and the catalytic layer. 
     Second, in addition to the porous plate  176  and the layer or plate of catalyst material  178 , the seventh embodiment includes a plate  182  comprising a flourescent material. The flourescent material which is included in the plate  182  is selected to respond to broad-band electromagnetic radiation to produce an output comprising narrow band electromagnetic radiation which is specifically matched to the band width of the radiation which activates the catalytic material  178 . In this manner, the efficiency of the catalytic reaction is substantially increased because the portion of the electromagnetic radiation which would otherwise be unused is transformed by the flourescent material into radiation within the band width comprising the input requirements of the catalytic layer. 
     In FIGS. 13 and 14 there is shown a hollow disk assembly  190  comprising an eighth embodiment of the invention. The hollow disk assembly  190  includes a hollow disk  192  which is supported on a hollow tube  194  for rotation, oscillation, or reciprocation relative to a quantity of water (not shown in FIGS.  13  and  14 ). A porous partition  196  is supported on the hollow disk  192  and in turn supports a plate or layer of catalytic material  198 . 
     The hollow disk assembly  190  differs from the hollow disk assemblies  130 ,  150 , and  170  in that rather than employing a mirrored surface formed directly on the hollow disk  192 , there is provided a separate reflective disk  199 . The reflective disk  199  may be fabricated from glass or transparent plastic, in which case the interior surface thereof is provided with a reflective layer in the manner of a conventional mirror. Alternatively, the reflective disk  199  may comprise stainless steel or other metal having a highly polished exterior surface. 
     Those skilled in the art will appreciate the fact that a mirrored surface formed on an appropriate interior surface may be used in any of the embodiments of the invention illustrated in FIGS. 1 through 12, inclusive, and described hereinabove in conjunction therewith. Likewise, a separate mirrored member or members having a variety of geometric configurations can be used in conjunction with any of the embodiments of the invention illustrated in FIGS. 1 through 12, inclusive, and described hereinabove in conjunction therewith. Likewise, any of the flourescent material constructions illustrated in FIGS. 7 through 12, inclusive, and described hereinabove in conjunction therewith can be utilized in conjunction with any of the embodiments of the invention illustrated in FIGS. 1 through 6, inclusive,  13  and  14  and described hereinabove in conjunction therewith. 
     Referring to FIG. 15, there is shown a method of and apparatus for manufacturing methanol from methane or natural gas  200  comprising a ninth embodiment of the invention. In accordance with a ninth embodiment, a plurality of porous partitions  202  are mounted in a predetermined array which may be either linear, circular, three-dimensional, etc. The porous partition  102  may be tubular in shape, however, any desired geometrical configuration may be utilized in the construction of the porous partitions  102  depending upon the requirements of particular applications of the invention. Each of the porous partitions  202  has a photocatalytic layer formed on its exterior surface. 
     A partition  204  which is transparent to electromagnetic radiation is positioned on each side of each porous partition  202 . Within each transparent partition  204  there is provided a source of electromagnetic radiation  206  which may comprise, for example, a source of ultraviolet light, it being understood that other sources of electromagnetic radiation providing the same or different types of radiation may be utilized in the practice of the invention depending upon the requirements of particular applications thereof. 
     Methane or natural gas received from a source  208  is directed into the interior of each porous partition  202  from a first manifold  210 . Simultaneously, water received from a source  212  is directed through a second manifold  214  into the spaces between the porous partitions  202  and the electromagnetic radiation transparent partitions  204 . Within each porous partition  202  the pressure of the methane or natural gas is maintained just high enough to cause methane or natural gas to flow outwardly through the porous partition while preventing the flow of water inwardly through the porous partition. 
     In the operation of the apparatus  200 , relative movement is continuously effected between the water and the exterior surfaces of the porous partitions  202  using, for example, the techniques shown in FIGS. 1,  2 , and  3  and described hereinabove in conjunction therewith. Electromagnetic radiation from the sources  206  activates the catalytic layers on the exterior surfaces of the porous partitions  202  to form hydroxyl radicals from the water. The hydroxyl radicals combine with the methane to form methanol, and if natural gas is used in the operation of the apparatus  200 , to form methanol and higher alcohols. The energy from the electromagnetic radiation sources  206  is sufficient to distill the methanol, and, if present, the higher alcohols from the water for recovery at an outlet  216 . The remaining water is recovered at an outlet  218  and is returned to the manifold  214  for reuse. 
     A method of manufacturing methanol and higher alcohols from natural gas is shown in the flow chart comprising FIG. 16 which depicts a tenth embodiment of the invention. In accordance with the tenth embodiment, natural gas or methane is mixed with an oxidizer such as oxygen, peroxide, etc. in accordance with a predetermined ratio. The mixture comprising natural gas or methane and an oxidizer is then directed through a porous partition having a photocatalytic exterior surface. The photocatalytic exterior surface is surrounded by a quantity of water, and relative movement is continuously maintained between the photocatalytic surface and the water. Electromagnetic energy is directed onto the photocatalytic layer which forms hydroxyl radicals from the water. The hydroxyl radicals combine with methyl radicals from the methane to form methanol. If natural gas is used, the hydroxyl radicals combine with methyl, ethyl, and propyl radicals to form methanol and higher alcohols. The alcohol(s) thus produced are recovered along with byproduct hydrogen. The presence of the oxidizer in the mixture causes the reaction to be self-sustaining. 
     Although preferred embodiments of the invention have been illustrated in the accompanying Drawing and described in the foregoing Detailed Description, it will be understood that the invention is not limited to the embodiments disclosed but is capable of numerous rearrangements, modifications, and substitutions of parts and elements without departing from the spirit of the invention.