Hydrogen peroxide steam generator

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Method and apparatus for producing steam and method for manufacturing said apparatus

Description

This disclosure relates generally to apparatus, systems, and methods for creating vapor from a liquid, such as, for example, liquid solutions of hydrogen peroxide, and, in one embodiment, for example, apparatus, systems, and methods for creating vapor from liquid hydrogen peroxide solutions of moderate concentration.

The production rate of an oil well depends on several factors, including, for example, the viscosity of the oil and the flow rate of oil through the casing, tubing and/or oil formation. The production of an oil well often declines over time due to blockages that form in the perforated casing tube, tubing, and/or oil formation. In some cases, for example, paraffin wax from crude oil can lodge in and around openings in the perforated tube of the casing until one or more of the openings become blocked. Obstructions in the perforated casing tube, tubing and/or oil formation limit the flow of oil and thus produce slowly from the well. In other cases, solids in the oil can plug and impair the oil's ability to flow during the production phase of an oil well. In addition, a formation may include heavy oils that naturally have a high viscosity and therefore move more slowly through the casing, tubing, and/or oil formation.

To clear blockages in the casing tube, tubing and/or oil formation, and/or to decrease the viscosity and/or increase the flow rate of heavy oils, steam can be pumped into the tubing. and/or oil formation. The heat from the steam can reduce the viscosity and/or increase the flow rate of heavy oil to increase flow through the reservoir and to the surface in a process known as enhanced oil recovery. Steam used in enhanced oil recovery can also be used for other oilfield operations, such as cleaning pipes, tanks, and other oilfield equipment.

Steam used in enhanced oil recovery and other oil field operations is traditionally generated using expensive boiler systems and steam piping systems that are built at the oil well site or adjacent to an oil field. These boiler systems are expensive to build, maintain, and operate. Furthermore, such systems are expensive to transport and set up/disguise at the well site. The steam/water vapors generated by these boiler systems are produced through the combustion of fossil fuels that produce pollutants such as SOx, NOx, and green plant contributors. Other boiler systems generate steam/water vapor through the reaction of high concentration liquid hydrogen peroxide with a catalyst in a shell or vessel. The catalyst is often very expensive and is poisoned by elements in the liquid used to generate steam, thus making the catalyst unable to produce steam. High concentration liquid peroxide is also expensive as it is often dangerous to transport and use if not handled with extreme care.

The apparatus, systems, and methods described herein, in one embodiment, but not by way of limitation, use liquid hydrogen peroxide of moderate concentration to produce steam for injection into an oil well as part of enhanced oil recovery or for other oilfield operations, such as cleaning oilfield equipment, heating hydrogen peroxide or other liquids, heat living spaces in an area of ​​oil fields or other uses. As described in more detail below, the catalyst of the apparatus, systems, and methods is relatively inexpensive to manufacture and is resistant to flooding and poisoning when used with a moderate concentration hydrogen peroxide solution. The use of moderate concentration liquid hydrogen peroxide reduces the total cost of the system and reduces the risks associated with the transport and reaction of liquid hydrogen peroxide.

In a first aspect, a method of producing steam for use in oil field applications, such as stimulating a geological formation to increase oil production, is provided. The method may include providing a catalyst that includes a plurality of ceramic bodies impregnated with an alkali-promoted manganese oxide and contacting the catalyst with a liquid hydrogen peroxide having a concentration between about 30 and about 70 weight percent to produce vapor. The method may also include injecting the steam into a geological formation to increase oil production from the geological formation.

In some embodiments, the liquid hydrogen peroxide has a concentration of from about 50 to about 65 weight percent.

In other embodiments, the liquid hydrogen peroxide has a concentration of about 60 weight percent.

In yet other embodiments, the liquid hydrogen peroxide has a concentration below the self-heating concentration of liquid hydrogen peroxide.

In other embodiments, the ceramic bodies are spheres.

In yet another embodiment, the ceramic bodies have a diameter between 1.5875 mm and 6.35 mm.

In some embodiments, each of the ceramic bodies has one of three different diameters.

In other embodiments, the three different diameters are 6.35mm, 3.175mm, and 1.5875mm.

In another embodiment, the ceramic bodies are tightly packed in a container.

In yet another embodiment, a reaction of liquid hydrogen peroxide and catalyst occurs at a temperature below the self-heating concentration of liquid hydrogen peroxide.

In other embodiments, the alkali-promoted manganese oxide catalyst is formed by the dehydration and calcination of alkali permanganates such as potassium, sodium, and/or calcium permanganates.

In yet another embodiment, the alkali-promoted manganese oxide includes the calcined product of sodium permanganate.

In still other embodiments, the alkali-promoted manganese oxide catalyst is formed by the dehydration and calcination of sodium manganate.

In some embodiments, the alkali-promoted manganese oxide catalyst is formed by dehydration and calcination of alkali manganates.

In yet other embodiments, the alkali-promoted manganese oxide is formed by dehydration and calcination of fugitive manganese compounds to form manganese oxides and the addition of one or more alkali promoters during impregnation.

In yet other embodiments, the alkali-promoted manganese oxide includes alkali-promoted manganese dioxide.

In other embodiments, the alkali-promoted manganese oxide includes the calcined product of potassium permanganate.

In other embodiments, the steam has a pressure of up to 10.35 MPa.

In a second aspect, an apparatus for producing steam for use in oilfield applications, such as, but not limited to, stimulating a geological formation to increase oil production is disclosed. In some embodiments, the apparatus includes a catalyst that includes a plurality of ceramic bodies impregnated with an alkali-promoted manganese oxide. The apparatus may also include a source of liquid hydrogen peroxide, wherein the source of liquid hydrogen peroxide includes liquid hydrogen peroxide having a concentration between about 30 and about 70 weight percent. The apparatus may also include a first conduit that couples the source of liquid hydrogen peroxide to the catalyst, and a second conduit that couples the catalyst to a geological formation.

In some embodiments, the ceramic bodies are spheres.

In other embodiments, the ceramic bodies have a diameter between 1.5875 mm and 6.35 mm.

In other embodiments, the liquid hydrogen peroxide has a lower concentration than is necessary to reach a self-heating temperature during a reaction with the catalyst.

In other embodiments, the catalyst and source of liquid hydrogen peroxide are located remote from the geological formation.

In a third aspect, a method of making an apparatus for producing steam for use in oil field applications, such as, but not limited to, stimulating a geological formation to increase oil production, is disclosed. In some embodiments, the method includes providing a catalyst, wherein providing a catalyst includes: providing a plurality of ceramic bodies; impregnating or soaking the plurality of ceramic bodies in a catalytic solution; drying the plurality of ceramic bodies; and firing the plurality of ceramic bodies. The method may also include providing a liquid hydrogen peroxide source and coupling the liquid hydrogen peroxide source to the catalyst. The method may also include coupling the catalyst to a steam dispenser or geological formation.

In another embodiment, drying the plurality of ceramic bodies includes placing the plurality of ceramic bodies in an oven at about 150 degrees Celsius.

In other embodiments, soaking the plurality of ceramic bodies in a catalyst solution includes soaking the plurality of ceramic bodies for less than about 1 hour.

In other embodiments, firing the plurality of ceramic bodies includes placing the ceramic bodies in a kiln at between about 200 and about 500 degrees Celsius.

In other embodiments, the liquid hydrogen peroxide source includes liquid hydrogen peroxide having a concentration between about 30 and about 70 weight percent.

In another embodiment, the liquid hydrogen peroxide source includes liquid hydrogen peroxide having a concentration between about 50 and about 65 weight percent.

In a fourth aspect, a method of producing steam for use in stimulating a geological formation to increase oil production is provided. The method includes providing a plurality of bodies comprising an active metal oxide and contacting the plurality of bodies with a liquid hydrogen peroxide having a concentration between about 30 and about 70 weight percent to produce vapor. The method may also include injecting the steam into a geological formation.

In some embodiments, the active metal oxide includes manganese dioxide.

In other embodiments, the active metal oxide includes alkali-promoted manganese oxide.

In other embodiments, the plurality of bodies consists essentially of an alkali-promoted manganese oxide.

In another embodiment, the liquid hydrogen peroxide has a concentration of from about 50 to about 65 weight percent.

In yet another embodiment, the liquid hydrogen peroxide has a concentration of about 60 weight percent.

In yet another embodiment, the liquid hydrogen peroxide has a concentration below the self-heating concentration of liquid hydrogen peroxide.

In some embodiments, the plurality of bodies have a diameter between 1.5875 mm and 6.35 mm.

In other embodiments, the plurality of bodies have three different diameters.

In other embodiments, the three different diameters are 6.35mm, 3.175mm, and 1.5875mm.

In another embodiment, the plurality of bodies are tightly packed in a container.

In some embodiments, a reaction of liquid hydrogen peroxide and catalyst occurs at a temperature below the self-heating concentration of liquid hydrogen peroxide.

In a fifth aspect, an apparatus for producing steam for use in stimulating a geological formation to increase oil production is provided. In some embodiments, the apparatus includes a catalyst having a plurality of bodies consisting essentially of an active metal oxide. In some embodiments, the apparatus includes a source of liquid hydrogen peroxide including liquid hydrogen peroxide having a concentration between about 30 and about 70 weight percent. The apparatus may also include a first conduit that couples the liquid source of hydrogen peroxide to the catalyst; and a second conduit that couples the catalyst to a geological formation.

In some embodiments, the active metal oxide is an alkali-promoted manganese oxide.

In another embodiment, the plurality of bodies are spheres.

In a sixth aspect, a method of producing steam for use in stimulating a geological formation is provided including providing a catalyst including a plurality of ceramic bodies impregnated with manganese oxide; contacting the catalyst with a liquid hydrogen peroxide having a concentration between about 30 and about 70 weight percent to produce steam; and injecting the steam into a geological formation.

In some embodiments, the liquid hydrogen peroxide has a concentration between about 50 and about 65 weight percent.

In other embodiments, the liquid hydrogen peroxide has a concentration of about 60 weight percent.

In other embodiments, the liquid hydrogen peroxide has a concentration below the self-heating concentration of liquid hydrogen peroxide.

In other embodiments, the ceramic bodies include spheres.

In another embodiment, the spherical ceramic bodies have a diameter between about 1.5875 mm and about 6.35 mm.

In yet another embodiment, the spherical ceramic bodies have at least three different diameters.

In yet another embodiment, the at least three different diameters include diameters of about 6.35mm, 3.175mm, and 1.5875mm.

In some embodiments, the ceramic bodies are tightly packed in a container.

In other embodiments, the manganese oxide includes an alkali-promoted manganese oxide including the calcined product of sodium permanganate.

In other embodiments, the manganese oxide includes alkali-promoted manganese dioxide.

In other embodiments, the manganese oxide includes an alkali-promoted manganese oxide including the calcined product of potassium permanganate.

In another embodiment, the steam has a pressure of up to about 10.35 MPa.

In a seventh aspect, an apparatus for producing steam for use in stimulating a geological formation is provided, the apparatus including a catalyst including a plurality of ceramic bodies impregnated with an alkali-promoted manganese oxide; a liquid hydrogen peroxide source, wherein the liquid hydrogen peroxide source includes liquid hydrogen peroxide having a concentration between about 30 and about 70 weight percent; a first coupling configured to provide a first fluid communication path between the source of liquid hydrogen peroxide and the catalyst; and a second coupling configured to provide a second fluid communication path between the catalyst and a geological formation.

In some embodiments, the ceramic bodies include spheres.

In other embodiments, a portion of the spherical ceramic bodies has a diameter between about 1.5875 mm and about 6.35 mm.

In other embodiments, the liquid hydrogen peroxide has a concentration below the self-heating concentration of liquid hydrogen peroxide.

In other embodiments, the catalyst and source of liquid hydrogen peroxide are located remote from the geological formation.

In an eighth aspect, a method of making an apparatus for producing steam for use in stimulating a geological formation is provided, the method including providing a catalyst, wherein providing a catalyst includes providing a plurality of ceramic bodies, impregnating the plurality of ceramic bodies in a catalytic solution, drying the plurality of ceramic bodies, and calcining the plurality of ceramic bodies; providing a liquid source of hydrogen peroxide; providing a first fluid communication path between the source of liquid hydrogen peroxide and the catalyst; and providing a second fluid communication path between the catalyst and a geological formation.

In some embodiments, drying the plurality of ceramic bodies includes placing the plurality of ceramic bodies in an oven above about 150 degrees Celsius.

In other embodiments, impregnating the plurality of ceramic bodies in a catalyst solution includes soaking the plurality of ceramic bodies for less than about one hour.

In other embodiments, calcining the plurality of ceramic bodies includes heating the ceramic bodies in a kiln to between about 200 and about 500 degrees Celsius.

In other embodiments, the liquid hydrogen peroxide source includes liquid hydrogen peroxide having a concentration between about 30 and about 70 weight percent.

In another embodiment, the liquid hydrogen peroxide source includes liquid hydrogen peroxide having a concentration between about 50 and about 65 weight percent.

In a ninth aspect, a method of producing steam for use in stimulating a geological formation is provided, the method including providing a plurality of bodies including an active metal oxide, and wherein at least a portion of the plurality of bodies provided in a spherical configuration; contacting the plurality of bodies with a liquid hydrogen peroxide having a concentration between about 30 and about 70 weight percent to produce vapor; and injecting the steam into a geological formation.

In some embodiments, the active metal oxide includes manganese dioxide.

In other embodiments, the active metal oxide includes alkali-promoted manganese oxide.

In other embodiments, the active metal oxide includes one or more elements selected from the group consisting of: Mn, Ag, Ru, Pb, V, Cr, Co, Cu, and Pt.

In another embodiment, the plurality of bodies consists essentially of an alkali-promoted manganese oxide.

In yet another embodiment, the liquid hydrogen peroxide has a concentration of from about 50 to about 65 weight percent.

In some embodiments, the liquid hydrogen peroxide has a concentration of about 60 weight percent.

In other embodiments, a portion of the plurality of bodies that are provided in a spherical configuration has a diameter between 1.5875mm and 6.35mm.

In some embodiments, a portion of the plurality of bodies that are provided in a spherical configuration has at least three different diameters.

In another embodiment, the at least three different diameters include diameters of approximately 6.35mm, 3.175mm, and 1.5875mm.

In yet another embodiment, the plurality of bodies are tightly packed in a container.

In yet another embodiment, a reaction of liquid hydrogen peroxide and catalyst occurs at a temperature below the self-heating concentration of liquid hydrogen peroxide.

In a tenth aspect, there is provided an apparatus for producing steam for use in stimulating a geological formation, the apparatus including a catalyst including a plurality of bodies including an active metal oxide, and wherein at least a portion of the plurality of bodies are provided in a spherical configuration; a liquid hydrogen peroxide source, wherein the liquid hydrogen peroxide source includes liquid hydrogen peroxide having a concentration between about 30 and about 70 weight percent; a first coupling configured to provide a first fluid communication path between the source of liquid hydrogen peroxide and the catalyst; and a second coupling configured to provide a second fluid communication path between the catalyst and a geological formation.

In some embodiments, the active metal oxide includes an alkali-promoted manganese oxide.

Other aspects, features and advantages will become apparent from the following detailed description, taken in conjunction with the accompanying drawings, which are a part of this description and which illustrate, by way of example, principles of the disclosed inventions.

DESCRIPTION OF THE FIGURES

The attached drawings facilitate the understanding of the various embodiments.

FIG. 1 is a block diagram illustrating one embodiment of an apparatus for producing steam for use in oilfield applications, such as, but not limited to, stimulating a geological formation to increase oil production, clearing clogged pipelines or tanks, heating hydrogen peroxide or other fluids, or heat living spaces at a well site or elsewhere, in accordance with this description.

FIG. 2 is a block diagram illustrating one embodiment of a method of manufacturing an apparatus for producing steam for use in oil field applications, such as stimulating a geological formation to increase oil production, clearing pipelines or tanks. clogged, or other fluids, or heating quarters of life at a well site, in accordance with this description.

FIG. 3 is a block diagram illustrating one embodiment of a method of making a catalyst for use in steam creation in accordance with this disclosure.

FIG. 4 is a block diagram illustrating one embodiment of a method of producing steam for use in oilfield applications, such as, but not limited to, stimulating a geological formation to increase oil production, cleaning clogged lines or tanks, heating hydrogen peroxide or other fluids, or heating at a well site, in accordance with this description.

FIG. 5 is a block diagram illustrating one embodiment of a method of producing steam for use in oilfield applications, such as, but not limited to, stimulating a geological formation to increase oil production, cleaning clogged pipes or tanks, heating hydrogen peroxide or other fluids, or heating at a well site, in accordance with this description.

FIG. 6 is a graph showing the injection rate and flow rate of hydrogen peroxide for one embodiment of an apparatus for producing steam using 60% H2O2, in accordance with this disclosure.

FIG, 7 is a table showing the data illustrated in the graph of FIG, 6.

FIG. 8 is a graph showing the injection rate and flow rate of hydrogen peroxide for one embodiment of an apparatus for producing steam using 60% H2O2, in accordance with this disclosure.

Figs. 9A and 9B are tables showing the data illustrated in the graph of FIG. 8.

DETAILED DESCRIPTION

Referring to Fig. 1, there is shown an embodiment of an apparatus 100 for producing steam for use in oil field applications, such as, for example, stimulating a geological formation 112 to increase oil production. Apparatus 100 includes a liquid hydrogen peroxide source 102, a catalyst 104, a first conduit 106 connecting liquid hydrogen peroxide source 102 to catalyst 104, a pump 108 for moving liquid hydrogen peroxide from the liquid hydrogen peroxide source of liquid hydrogen 102 to catalyst 104 and a second conduit 110 connecting catalyst 104 to a geological formation 112 and/or to a pipeline, tank, or other oil field application 113. As described in more detail below, apparatus 100 can be used with moderate concentration hydrogen peroxide which is less hazardous to store, transport and handle, and is less expensive to purchase. In addition, apparatus 100 includes a catalyst 104 that may include a porous ceramic substrate that is less expensive to manufacture and avoids many of the problems associated with previous catalysts, such as flooding and premature catalyst poisoning, as will be described in more detail below. . Steam produced by apparatus 100 may be used in various oilfield applications, such as, but not limited to, enhanced oil recovery, equipment cleaning, heating hydrogen peroxide or other liquids, heating homes at a field site petroleum or other uses.

It was previously believed that the use of moderate concentration liquid hydrogen peroxide was not suitable for producing steam and could cause catalyst flooding and/or lead to a high rate of catalyst quench or deactivation. It was also thought that stabilizers in moderate concentration hydrogen peroxide would adhere to the catalyst in a short period of time to poison or deactivate the catalyst. However, it has been unexpectedly found that the catalyst of the present disclosure does not flood when contacted with moderate concentration hydrogen peroxide for long periods of time and it has been found that the rate of deactivation or poisoning rate of the present catalyst when in contact with a moderate concentration of hydrogen peroxide for long periods of time it is greatly reduced, as will be described in more detail below.

Referring again to Fig. 1, liquid hydrogen peroxide source 102 includes liquid hydrogen peroxide of moderate concentration and may be any suitable source, such as, for example, a mobile container of liquid hydrogen peroxide. In some embodiments, liquid hydrogen peroxide source 102 contains liquid hydrogen peroxide having a concentration between about 30 and about 70 weight percent. In some embodiments, liquid hydrogen peroxide source 102 contains liquid hydrogen peroxide having a concentration between about 50 and about 65 weight percent. In other embodiments, liquid hydrogen peroxide source 102 contains liquid hydrogen peroxide having a concentration of about 60 weight percent. In some embodiments, liquid hydrogen peroxide source 102 contains liquid hydrogen peroxide having a concentration below the self-heating concentration of liquid hydrogen peroxide (approximately 64.7 weight percent). In some embodiments, the liquid hydrogen peroxide is mixed with water, one or more stabilizers that may be added by the manufacturer of the hydrogen peroxide, and/or a mixture of other elements to create the weight percentages described above. In some embodiments, the stabilizer includes one or more phosphoric acids, phosphonic acids, inorganic stannates such as sodium stannate, other similar substances, or additives.

As illustrated in the embodiment of Fig. 1, liquid hydrogen peroxide source 102 is coupled to catalyst 104 via first conduit 106 to supply liquid hydrogen peroxide to catalyst 104 at a predetermined rate. In some embodiments, the rate at which liquid hydrogen peroxide is supplied to catalyst 104 through first conduit 106 is variable and is controlled by pump 108. In some embodiments, the first conduit 106 also includes one or more valves (not shown), flow meters (not shown), or other mechanisms to measure and/or control the flow rate of liquid hydrogen peroxide from the liquid hydrogen peroxide source. 102 to catalyst 104. First conduit 106 may be any suitable pathway or coupling mechanism for transporting liquid hydrogen peroxide from liquid hydrogen peroxide source 102 to catalyst 104, such as, for example, a pipe, hose, or chamber. In some embodiments, liquid hydrogen peroxide source 102, pump 108, and catalyst 104 are located remote from geological formation 112, as shown in FIG. 1, to reduce the possibility of liquid hydrogen peroxide solution entering geological formation 112. Therefore, in some embodiments, catalyst 104 is not located within geological formation 112 but is located adjacent at a distance specified geological formation 112. As such, in some embodiments, the liquid hydrogen peroxide solution is not pumped into geological formation 112, but is instead reacted to form vapor at catalyst 104, which is located remotely from geological formation 112.

In some embodiments, catalyst 104 includes a plurality of ceramic bodies. In some embodiments, the ceramic bodies include spheres of various diameters. In some embodiments, the ceramic bodies are packed within a container such that the space between larger spheres is at least partially filled with smaller spheres. In some embodiments, smaller spheres fit between larger spheres such that most of the volume containing catalyst 104 is filled by the ceramic bodies. In some embodiments, the spheres have a diameter between 1.5875 mm and 6.35 mm. In some embodiments, the maximum compression of the sphere is obtained by a defined trimodal distribution of spheres. In some embodiments, the trimodal distribution is approximately 45 percent, 35 percent, and 20 percent by volume for 6.35 mm diameter, 3.175 mm diameter, and 1.5875 mm diameter activated alumina spheres, respectively. In some embodiments, sphere packing is obtained by a defined bimodal distribution of spheres. In some embodiments, the bimodal distribution is approximately 45 volume percent 6.35 mm diameter spheres and 55 volume percent 3.175 mm diameter spheres. Thus, in some embodiments, the spheres have three different diameters (trimodal distribution), in other embodiments the spheres have two different diameters (bimodal distribution), while in other embodiments the spheres have four or more different diameters. In other embodiments, catalyst 104 includes spheres having a diameter. In other embodiments, catalyst 104 includes spheres having more than 3 different diameters. In other embodiments, the ceramic bodies include other shapes, such as, for example, a square shape, a rectangular shape, or a triangular shape.

In other embodiments, the ceramic bodies may have any other suitable shape and may be chips, extrudates, pieces, granules, or a combination thereof closely bonded. In some embodiments, the ceramic bodies are tightly packed in a container (not shown).

The ceramic catalyst bodies 104 may be made of any suitable ceramic material. For example, in some embodiments, the ceramic bodies are made of one or more of alumina, silica, silica-alumina, or other alumino-silicate, zirconia, activated carbon, or other refractory ceramic oxide. In other embodiments, the ceramic bodies also include zeolite molecular sieves or other shape-selective ceramics. In some embodiments, the ceramic bodies are made from a combination of ceramic materials. In some embodiments, the ceramic bodies are porous and therefore have internal and external surface areas. In other embodiments, the ceramic bodies are non-porous. In alternate embodiments, the catalyst does not include a plurality of bodies, but instead includes a single body, such as a porous monolith or honeycomb body, that at least partially fills a catalyst vessel. In some embodiments, the ceramic bodies are activated because they have a high surface area, beyond the expected outer surface area. In some embodiments, the internal surface area contributes greatly to the abstraction of the catalyst in formation, and the usefulness (activity) of the dispersed catalyst in use.

In some embodiments, the ceramic catalyst bodies 104 are impregnated with an alkali-promoted manganese oxide, alkali-promoted manganese dioxide, or other catalytic agent. As described below, in some embodiments, the ceramic bodies are impregnated by soaking the ceramic edges in the catalytic agent for a period of time. In embodiments where the ceramic bodies are porous or otherwise include an inner surface and an outer surface, the inner and outer surface areas of the ceramic bodies become impregnated as the ceramic bodies are soaked in the catalytic agent. In some embodiments, the catalytic agent includes at least one cation having a defined valence state, the cationic species being Mn, Ag, Ru, Pb, V, Cr or Co or other transition metals or noble metals such as Cu or Pt. . In some embodiments, the catalytic agent includes an alkaline promoted cationic species, such as, but not limited to, those described above. An embodiment of a catalyst manufacturing process 104 is described in more detail below in conjunction with Fig. 3. In some embodiments, the catalytic agent includes one or more of sodium permanganate and sodium manganate. In other embodiments, the catalytic agent includes sodium hydroxide and potassium hydroxide which are then calcined to form an alkali-promoted manganese oxide (or dioxide). Typical manganese compounds with fugitive anions are manganese nitrate, manganese acetate, and the like.

In another embodiment, catalyst 104 includes a plurality of bodies formed of an active ceramic oxide in a consolidated state without an underlying ceramic body. For example, in some embodiments, a cationic species such as Mn, Ag, Ru, Pb, V, Cr, or Co, or another transition metal or noble metal such as Cu or Pt is used as the active ceramic oxide by itself in a consolidate to form a plurality of bodies. In some embodiments, the bodies are spheres of various diameters. In some embodiments, the bodies are packed within a container such that the space between larger spheres is at least partially filled with smaller spheres. In some embodiments, smaller spheres fit between larger spheres such that more of the volume of catalyst 104 is filled by the bodies. In some embodiments, the spheres have a diameter between 1.5875 mm and 6.35 mm. In some embodiments, the maximum compression of the sphere is obtained by a defined trimodal distribution of spheres. In some embodiments, the trimodal distribution is 45 percent, 35 percent, and 20 percent by volume for 6.35 mm diameter, 3.175 mm diameter, and 1.5875 mm diameter spheres, respectively. In some embodiments, sphere packing is obtained by a defined bimodal distribution of spheres. In some embodiments, the bimodal distribution is 45 volume percent 6.35 mm diameter spheres and 55 volume percent 3.175 mm diameter spheres. Therefore, in some embodiments, the spheres have three different diameters (trimodal distribution) while in other embodiments the spheres have two different diameters (bimodal distribution). In other embodiments, catalyst 104 includes spheres having a diameter. In other embodiments, catalyst 104 includes spheres having more than 3 different diameters. In other embodiments, the ceramic bodies have other shapes, such as, for example, a square shape, a rectangular shape, or a triangular shape. In other embodiments, the bodies may be in any other suitable form and may be chunks, extrudates, pieces, pellets, or a combination thereof. In some embodiments, the bodies are tightly packed in a container (not shown). In alternate embodiments, the catalyst does not include a plurality of bodies, but instead includes a single body that includes an active ceramic oxide itself, in a consolidated manner.

In other embodiments, catalyst 104 may include a metal oxide body, such as an active metal oxide body. In such embodiments, the metal oxide body may be formed or shaped in any desirable shape, such as one or more of the shapes described herein in connection with the shape of ceramic bodies.

In some embodiments, the steam produced by the interaction of catalyst 104 and hydrogen peroxide has a pressure of up to about 10.35 MPa. In other embodiments, the steam produced by the interaction of catalyst 104 and hydrogen peroxide has a pressure of up to about 20.69 MPa. Higher pressures are projected to be achievable as equipment to transport and otherwise utilize steam is improved.

Referring again to Fig. 1. In some embodiments, a second conduit 110 couples the catalyst 104 to a geological formation 112 or a steam applicator to clear blockages from oil and gas pipelines, tanks, or other equipment 113. The second Conduit 110 may be any suitable mechanism for transporting vapor produced by the interaction of liquid hydrogen peroxide and catalyst 104, such as, for example, a tube, hose, or chamber. For example, geological formation 112 may include a tubing and second conduit 110 may couple catalyst 104 to the tubing. In some embodiments, second conduit 110 transports steam from catalyst 104 to another location, such as, for example, a steam applicator for cleaning oilfield equipment 113, a heat exchanger for heating hydrogen peroxide or other liquids, a heat exchanger for heating housing in an oil field, or any other suitable location. As discussed above, the steam produced by apparatus 100 can be used in various oilfield applications and is not limited to the specific applications described herein. In some embodiments, for example, the vapor travels through the second conduit 110 to an applicator to remove obstructions from pipelines, tanks, or other oilfield equipment. In some embodiments, second conduit 110 is of sufficient length to allow hydrogen peroxide source 102 and catalyst 104 to be positioned remotely from geological formation 112 to reduce the likelihood of unreacted hydrogen peroxide passing into the formation. geological 112.

FIG. 2 is a block diagram illustrating a method 200 of manufacturing an apparatus 100 for producing steam for use in an oil field application. In some embodiments, method 200 begins and catalyst 104 is provided, as shown in block 202. As described above, in some embodiments, catalyst 104 includes a plurality of ceramic bodies that are impregnated with a catalytic agent, such as a promoted alkaline agent, manganese oxide, or an active metal oxide. As described above, in some embodiments the ceramic bodies may be impregnated with other elements or a combination of elements. In other embodiments, the catalyst includes one or more bodies that are comprised of an active ceramic oxide itself, as described above. In some embodiments, the ceramic bodies (or bodies formed from an active ceramic oxide itself) are placed or packaged in a container that allows the entry of liquid hydrogen peroxide and allows the release of vapor produced by the decomposition of the hydrogen peroxide. liquid Contacts catalyst 104. A source of liquid hydrogen peroxide 102 is also provided, as shown in block 204, and is coupled to catalyst 104, for example, via a first conduit 106, as shown in block 206. In some embodiments, the catalyst 104 is then attached to a geological formation 112 and/or an applicator to clean a pipeline, tank, or other oilfield application via a second conduit 110, as shown in blocks 208 and 209. As described above, the catalyst can also be coupled to other oilfield applications, such as heat exchangers for heating hydrogen peroxide or other liquids or heat exchangers for heating homes in an oilfield area. As described above, catalyst 104 may be contained within a container that is coupled to first and second conduits 106 and 110 and may be located remote from geological formation 112.

The F1G. 3 is a block diagram illustrating one embodiment of a method 300 of manufacturing a catalyst 104 for producing steam. Catalyst 104 produced using the illustrated method may be similar to the catalyst described in US-A-6,991,772, entitled H2O2 Decomposition Catalyst for the Present Inventor, which is hereby incorporated by reference in its entirety for all purposes. Method 300 begins and a catalytic agent is provided, as shown at block 302, and a ceramic substrate is provided, as shown at block 304. As described above, the catalytic agent may include any suitable catalytic substance, such as alkali-promoted manganese oxide, alkali-promoted manganese dioxide, or a combination of catalyst substances. As described above, the ceramic substrate can include a plurality of porous ceramic bodies. In some embodiments, a high surface area porous ceramic substrate in the form of a single monolith or honeycomb is selected to form the ceramic substrate. In other embodiments, a high surface area porous ceramic substrate is selected in the form of a plurality of closely bonded chunks, extrudates, pieces, granules, spheres, or a combination thereof, to form the ceramic substrate.

As shown at block 306, the ceramic substrate is impregnated with the catalytic agent. In some embodiments, a soluble salt of a desired catalyst cation is mixed in a solvent therefor, the cationic species being Mn, Ag, Ru, Pb, V, Cr, or Co, or other transition metals or noble metals, such as Cu or pt. In some embodiments, a catalytic agent is poured in solution onto the ceramic substrate in an amount sufficient to imbibe the ceramic substrate and impregnate it through the pores thereof with the catalytic agent. The ceramic substrate is soaked in the catalytic agent for a period of time to impregnate the ceramic substrate. In some embodiments, the ceramic substrate is soaked in the catalytic agent for less than about 1 hour. In some embodiments, the substrate is soaked in the catalytic agent for about 15 minutes. In some embodiments, a catalyst cation loading is calculated based on a defined percentage of the final cationic species. As an example, a filler may include 1% w/w manganese (+4) on a zeolite molecular sieve (ZMS) substrate. The calculated amount of catalytic agent is then added to the catalyst solution as described above.

In some embodiments, a catalytic (or ionic) promoter may be added to the catalyst solution. In some embodiments, the catalytic (or ionic) promoters are chosen from groups I and II of the Periodic Table of the Elements, such as sodium (Na+), potassium (K+), ammonium ion (NH4+), lithium ( Li +), Calcium (Ca ++), strontium (Sr ++) and barium (Ba ++).

As shown at block 308, the impregnated ceramic substrate is then dried to remove solvent from the catalyst solution. In some embodiments, the ceramic substrate is dried in an oven that is approximately 150 degrees Celsius. In some embodiments, the ceramic substrate dries for between about 60 and about 120 minutes. In other embodiments, the impregnated material is dried until constant weight is released or no visible moisture is released.

As shown at block 310, the dried impregnated substrate is then calcined to form an activated bulk catalyst. In some embodiments, the substrate is calcined by placing the impregnated substrate in an oven between about 200 and about 500 degrees Centigrade for between about 0.5 and about 24 hours. In some embodiments, the manganese-based material is calcined until it forms a uniform brown to black color depending on catalyst loading. In some embodiments, the initial color of the catalyst is a shade of purple.

As shown at block 312, catalyst 104 is then terminated. In some embodiments, catalyst 104 is placed in a container that includes an inlet to receive liquid hydrogen peroxide and an outlet to release vapor, as described above. In some embodiments, catalyst 104 is packaged in the container to reduce or eliminate movement of catalyst components during reaction with liquid hydrogen peroxide.

In another embodiment, a method of providing a steam producing apparatus is started and a catalytic agent is provided. As described above, the catalytic agent may include any suitable catalytic substance, such as alkali-promoted manganese oxide, alkali-promoted manganese dioxide, or a combination of catalytic substances. The catalytic agent may be in a consolidated state which may be formed into a plurality of bodies which may have any suitable shape, such as generally spherical shapes. The ceramic bodies can then be dried in a kiln and calcined to form an activated bulk catalyst. In some embodiments, the bodies are then placed in a container that includes an inlet to receive liquid hydrogen peroxide and an outlet to release vapor, as described above. In some embodiments, the bodies are packed in the container to reduce or eliminate movement of the bodies during reaction with liquid hydrogen peroxide.

FIG. 4 is a block diagram illustrating a method 400 for producing steam for use in stimulating a geological formation 112 to increase oil production, for use in cleaning or cleaning a pipeline, tank or other oil field equipment or for use in another oilfield application, for example, but not limited to, heating hydrogen peroxide or heating dwellings at an oilfield site. In some embodiments, the method 400 includes providing a catalyst 104 that includes a plurality of ceramic bodies impregnated with an alkali-promoted manganese oxide or a plurality of bodies that are made essentially of an active ceramic oxide, as shown in block 402. In some, the catalyst 104 is contacted with a moderate concentration liquid hydrogen peroxide to produce steam, as shown in block 404. In some embodiments, the liquid hydrogen peroxide has a concentration between about 30 and about 70 percent. Steam is produced when hydrogen peroxide contacts the catalyst and breaks down to produce steam and oxygen. It was previously believed that the use of moderate concentration liquid hydrogen peroxide to produce steam with a catalyst that included a porous ceramic substrate could cause catalyst flooding and/or cause a high rate of catalyst deactivation or poisoning. For example, it was thought that absorbent ceramics, such as those described herein, used to react with hydrogen peroxide of moderate concentration below the self-heating concentration of hydrogen peroxide would flood the catalyst. It was also thought that stabilizers in moderate concentration hydrogen peroxide would adhere to the catalyst in a short period of time to poison or deactivate the catalyst. However, it has been found that the catalyst 104 of the present disclosure, although porous and absorbent, does not flood when contacted with moderate concentration hydrogen peroxide for long periods of time because the decomposition mechanism is in the same timing order as Adsorption/Desorption. Furthermore, it has been found that the rate of deactivation or poisoning rate of catalyst 104 when contacted with moderate concentration hydrogen peroxide for long periods of time is greatly reduced due to the fact that non-metal catalysts do not form insoluble phosphates in the active compound Catalyst. In some embodiments, catalyst 104 produces vapor for much longer periods of time than solid precious metal catalysts or liquid catalysts, which typically have a life of a few minutes for most rocket applications and consume hydrogen peroxide. significantly higher per unit of time. Test data showing steam production over long periods of time is described in more detail below in connection with Figs. 5-8B. Although the test data below shows steam production for specified time periods (54 hours in Figures 5 and 6 and 91 hours in Figures 7-8B), it is anticipated that production may last for longer periods. without catalyst deactivation or flooding.

Referring back to Fig. 4, the steam is then directed to a geological formation 112 to, in one embodiment, increase oil production from the geological formation 112 or be directed to another oilfield application, such as a application to remove blockages from a pipe or tank, as shown in block 406. For example, steam may be directed to the production pipe of a geological formation 112. As explained above, steam can be directed to other locations in other embodiments. For example, in some embodiments the steam is directed to a steam applicator for cleaning oilfield equipment, a heat exchanger for heating hydrogen peroxide or other liquids, or a heat exchanger for heating homes at an oilfield location. .

FIG. 5 is a block diagram illustrating a method 500 for producing steam for use in stimulating a geological formation 112 to increase oil production, for use in cleaning or flushing a pipeline, tank, or other oil field equipment or for use in another oilfield application, for example, but not limited to, heating hydrogen peroxide or heating dwellings on an oilfield site. In some embodiments, the method 500 includes providing a catalyst 104 that includes a plurality of bodies that include an active metal oxide, as shown in block 502. In some embodiments, the bodies are formed by molding an active metal oxide in a constituted state. in a plurality of spherical shapes, or in one or more shapes previously described in connection with ceramic bodies. In some embodiments, the active metal oxide includes manganese dioxide or an alkali-promoted manganese oxide.

In some embodiments, catalyst 104 is contacted with a moderate concentration liquid hydrogen peroxide to produce vapor, as shown in block 504. In some embodiments, liquid hydrogen peroxide has a concentration between about 30 and about 70 percent, between about 50 and about 65 weight percent, or about 60 weight percent. In some embodiments, the liquid hydrogen peroxide has a concentration below the self-heating concentration of liquid hydrogen peroxide. Steam is produced when hydrogen peroxide contacts the catalyst and breaks down to produce steam and oxygen. The steam is then directed to a geological formation 112 to increase oil production from the geological formation 112 or is directed to another oilfield application, such as an application to remove blockages from a pipeline or tank, as shown in block 506. For example, steam can be directed to the piping production piping in communication with or connected to a geological formation 112. As explained above, steam can be directed to other locations in other embodiments. For example, in some embodiments the steam is directed to a steam applicator for cleaning oilfield equipment, a heat exchanger for heating hydrogen peroxide or other liquids, or a heat exchanger for heating homes at an oilfield location. .

FIG. 6 is a graph showing injection temperature and hydrogen peroxide flow rate for a test of one embodiment of an apparatus for producing steam using 60 weight percent hydrogen peroxide. FIG. 7 is a table showing the data illustrated in the graph of FIG. 6. In tests, the catalyst included spherical ceramic bodies impregnated with promoted alkali manganese dioxide. As shown in Figs. 6 and 7, the steam produced by the apparatus had a temperature of approximately 400 degrees Fahrenheit with flow rates ranging from 0 gallons per minute (GPM) to approximately 2.5 GPM. The catalyst remained active during the 54 hour test period and did not flood or poison. The catalyst is expected to have remained active without flooding or poisoning for a period of time longer than the test period. As such, the significant plateau in catalyst activity and system performance is of great merit when applied to a variety of oilfield conditions.

FIG. 8 is a graph showing injection temperature and hydrogen peroxide flow rate for a second test of an embodiment of an apparatus for producing steam using 60 weight percent hydrogen peroxide. Figs. 9A and 9B are tables showing the data illustrated in the graph of FIG. 8. As shown in Figs. 8, 9A and 9B, the steam produced by the apparatus has a temperature of about 400 degrees Fahrenheit with flow rates ranging from 0 GPM to about 1 GPM. The catalyst remained active during the 91 hour test period and did not flood or poison. The catalyst is expected to have remained active without flooding or poisoning for a period of time longer than the test period. As such, the significant plateau in catalyst activity and system performance is of great merit when applied to a variety of oilfield conditions.

In the foregoing description of certain embodiments, specific terminology has been resorted to for the sake of clarity. However, the description is not intended to be limited to the specific terms so selected, and each specific term is to be understood to include other technical equivalents that function in a similar manner to achieve a similar technical purpose.

In this specification, the word comprise and include or including is to be understood in its open sense, that is, in the sense of at least including, and is therefore not limited to its closed sense, which is the sense of consisting only of . A corresponding meaning is attributed to the corresponding words understand, understood and comprises where they appear.

Furthermore, the foregoing describes only some embodiments of the invention, and alterations, modifications, additions and/or changes may be made thereto without departing from the scope and spirit of the described embodiments, the embodiments being illustrative and non-restrictive.

Further, the inventions have been described in connection with what are presently considered to be the most practical and preferred embodiments, it is to be understood that the invention is not to be limited to the embodiments described, but rather is intended to cover various modifications and equivalent arrangements including within the spirit and scope of the invention or inventions. Furthermore, the various embodiments described above may be implemented in conjunction with other embodiments, eg, aspects of one embodiment may be combined with aspects of another embodiment to realize other embodiments. Furthermore, each independent feature or component of any given assembly may constitute an additional embodiment.

Havana January 2019

Grethel Gil Vidal

Official Agent. Lex SA