WO2017004551A1

WO2017004551A1 - Hydrogen production method and system

Info

Publication number: WO2017004551A1
Application number: PCT/US2016/040747
Authority: WO
Inventors: Morten A. Lund
Original assignee: Exen Holdings, Llc
Priority date: 2015-07-02
Filing date: 2016-07-01
Publication date: 2017-01-05

Abstract

A system for hydrogen production may include at least one infusion tube; a gaseous reactant inlet in fluid communication with the infusion tube; a recirculation loop in fluid communication with an outlet of the infusion tube and an inlet of the infusion tube; a gas processing unit configured to receive hydrocarbon liquid from a hydrocarbon liquid inlet, to receive a mixture of hydrocarbon liquid and gaseous reactant from the infusion tube, and to provide at least some of a recovered liquid fraction to the recirculation loop; and an outlet on the gas processing unit configured to connect to a storage vessel to collect produced hydrogen gas.

Description

HYDROGEN PRODUCTION METHOD AND SYSTEM

BACKGROUND

] Hydrogen gas is a versatile compound/reactant that finds use in a variety of applications in the petrochemical, semiconductor, chemical and electronics industries, among others. Additionally, hydrogen may be used to improve the efficiency of combustion processes occurring in automotive engines. Further, hydrogen fuel-cell technology, is envisioned as an environmentally conscionable way to potentially provide electricity for powering businesses, homes, and automobiles in the future.

] While hydrogen can be prepared by a variety of different methods, some of the most utilized processes involve the removal of hydrogen from hydrocarbons and the gasification of carbonaceous materials including coal and petroleum processing byproducts. However, these processes are typically used in large industrial operations that use energy intensive conditions and produce byproducts which may require further processing or be difficult and/or expensive to dispose of. For example, the steam reforming of hydrocarbons typically involves reacting steam with a hydrocarbon feedstock (often natural gas) at high temperatures (700 - 1 100 °C) and pressures (-20 atm), with gasification processes using similarly elevated temperatures and pressures to achieve their products. In some instances the presence of a metal- based catalyst is used to modify and increase the efficiency of steam reforming processes. ] The electrolysis of water has also been investigated as a way to cleanly produce hydrogen on a variety of scales spanning personal use for home or transportation to industrial scale for the production of high purity hydrogen. Nevertheless, water electrolysis systems often require the use of specialized cells containing high-cost metal electrodes along with the need to apply a substantial overpotential to the system to effectively produce hydrogen.

SUMMARY

] This summary is provided to introduce a selection of concepts that are further described below in the detailed description. This summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to be used as an aid in limiting the scope of the claimed subject matter.

[0005] In this disclosure the term "hydrogen production system" is intended to encompass any system that may be capable of producing hydrogen from gaseous and hydrocarbon liquid reactants introduced therein.

[0006] In this disclosure the use of the term "hydrocarbon liquid" is intended to encompass any liquid that is substantially comprised of molecules having hydrogen and carbon as their primary constituents. For example, a hydrocarbon liquid may be crude oil, diesel, bio-diesel, gasoline, jet fuel, fuel oil and vegetable oil, etc. Further, the molecules having hydrogen and carbon as their primary constituents may adopt a variety of (and not necessarily the same) chemical bonding motifs.

[0007] In this disclosure the use of the term "gaseous reactant" is intended to encompass a substance that is in a gaseous state at atmospheric conditions and includes hydrogen gas, a hydrogen containing gas, or mixtures thereof. For example, a hydrogen containing gas may include methane, ethane, butane, propane, natural gas. In particular embodiments, hydrogen gas having a purity of at least 95 %, or at least 97 %, or at least 99.5 % may be utilized as the gaseous reactant, although less pure streams may also be utilized. For example, in one or more embodiments, at least a portion of the produced gases may as be used as a gaseous reactant.

[0008] In this disclosure the terms "upstream" and "downstream" may be used and are intended to denote the placement of certain components of the system in relation to the flow of the mixture of the hydrocarbon liquid and gaseous reactant through the hydrogen production system to the gas processing unit. For example a gaseous reactant and/or a virgin hydrocarbon liquid may be input at an upstream position within a hydrogen production system, while produced gases (including hydrogen) may be extracted at a downstream position within the hydrogen production system.

[0009] In this disclosure the term "recirculation" may be used and is intended to refer to the propagation of previously input components through specific portions of the hydrogen production system more than once. For example, and as discussed in more detail later in this disclosure, the hydrogen production system may contain a recirculation loop that serves to feed outgassed hydrocarbon liquid through the system more than once in order to generate more produced gases from the hydrocarbon liquid feedstock.

[0010] In one aspect, embodiments disclosed herein relate to a system for hydrogen production, including: at least one infusion tube; a gaseous reactant inlet in fluid communication with the infusion tube; a recirculation loop in fluid communication with an outlet of the infusion tube and an inlet of the infusion tube; a gas processing unit configured to receive hydrocarbon liquid from a hydrocarbon liquid inlet, to receive a mixture of hydrocarbon liquid and gaseous reactant from the infusion tube, and to provide at least some of a recovered liquid fraction to the recirculation loop; and an outlet on the gas processing unit configured to connect to a storage vessel to collect produced hydrogen gas.

[0011] In another aspect, embodiments disclosed herein relate to a system, including: a hydrogen consuming unit; at least one infusion tube; a gaseous reactant inlet in fluid communication with the infusion tube; a hydrocarbon liquid inlet in fluid communication with the infusion tube; a recirculation loop in fluid communication with an outlet of the infusion tube and an inlet of the infusion tube; a gas processing unit configured to receive a mixture of hydrocarbon liquid and gaseous reactant from the infusion tube and to provide at least some of a recovered liquid fraction to the recirculation loop; an outlet on the gas processing unit, the outlet in fluid communication with the hydrogen consuming unit.

[0012] In yet another aspect, embodiments disclosed herein relate to a method for producing hydrogen, including: inputting gaseous reactant into a hydrocarbon liquid at a first pressure; infusing the gaseous reactant and the hydrocarbon liquid under a second pressure to create a homogenous mixture of gaseous reactant and hydrocarbon liquid; outgassing a gaseous mixture comprising produced hydrogen gas from the homogenous mixture of gaseous reactant and hydrocarbon liquid at a third pressure; and collecting the outgassed gaseous mixture.

[0013] Other aspects and advantages of the claimed subject matter will be apparent from the following description and the appended claims.

BRIEF DESCRIPTION OF DRAWINGS [0014] FIG. 1 depicts a diagram of a hydrogen production system according to embodiments of this disclosure.

[0015] FIG. 2 depicts a diagram of another configuration of a hydrogen production system according to embodiments of this disclosure.

[0016] FIG. 3 depicts a diagram of another configuration of a hydrogen production system according to embodiments of this disclosure.

[0017] FIG. 4 depicts a diagram of another configuration of a hydrogen production system according to embodiments of this disclosure.

[0018] FIG. 5 depicts a uni-flow infusion tube according to an embodiment of this disclosure.

[0019] FIG. 6 depicts a bi-flow infusion tube according to an embodiment of this disclosure.

[0020] FIG. 7 depicts a gas concentrator according to an embodiment of this disclosure.

[0021] FIG. 8 depicts a diagram of another configuration of a hydrogen production system according to embodiments of this disclosure.

[0022] FIG. 9 depicts a configuration for a gas processing unit according to an embodiment of this disclosure.

[0023] FIG. 10 depicts another configuration for a gas processing unit according to an embodiment of this disclosure.

[0024] FIG. 1 1 depicts another configuration for a gas processing unit according to an embodiment of this disclosure

[0025] FIG. 12 depicts a system for consuming at least some of the hydrogen produced by a hydrogen production system according to this disclosure.

[0026] FIG. 13 is a graph showing the cumulative gas outgassed over time for the experiments discussed in the examples.

[0027] FIG. 14 is a graph showing the hydrogen concentration over time for the experiments discussed in the examples. [0028] FIG. 15 shows a flow chart that is generally applicable to embodiments of the present disclosure.

[0029] FIG. 16 shows a plot of the diesel composition before and after processing.

[0030] FIG. 17 shows a plot of the diesel' s isoparaffin mole fraction before and after processing.

[0031] FIG. 18 shows a plot of the diesel's paraffin mole fraction before and after processing.

[0032] FIG. 19 shows a plot of the diesel's napthene mole fraction before and after processing.

[0033] FIG. 20 shows a plot of the diesel's aromatic mole fraction before and after processing.

DETAILED DESCRIPTION

[0034] In one aspect, embodiments disclosed herein relate to hydrogen production methods and systems. The hydrogen production methods and systems disclosed herein may provide a highly efficient and economically feasible path toward hydrogen production for a variety of applications. More specifically, embodiments disclosed herein relate to methods and systems for producing hydrogen from a hydrocarbon liquid via the input of a gaseous reactant into the hydrocarbon liquid. In some embodiments, these systems and methods may operate at substantially room temperature and/or at greatly reduced pressures compared to conventional steam reforming or gasification processes.

[0035] In one or more embodiments, a hydrogen production system according to this disclosure may be a standalone system capable of producing hydrogen for commercial or household/personal uses. For example, a standalone hydrogen production system may be used to produce hydrogen for a generator or hydrogen fuel cells powering businesses, homes, and/or vehicles. In other embodiments, a hydrogen production system according to this disclosure may be a smaller system that may be integrated and mounted onto a vehicle. In this way, hydrogen may be produced and used on- demand for either a fuel cell vehicle or a vehicle that utilizes hydrogen in its hydrocarbon liquid fuel mix to increase combustion efficiency.

[0036] Hydrogen Production System

[0037] FIG. 1 depicts a diagram of a hydrogen production system 100 according to an embodiment of the present disclosure. The system includes a hydrocarbon liquid inlet 102 and a gaseous reactant inlet 104. The hydrocarbon liquid inlet 102 provides hydrocarbon liquid to a lift pump 106, after which the hydrocarbon liquid proceeds to gas processing unit 108. The gaseous reactant inlet 104 provides gaseous reactant to a recirculation loop 1 10 (the loop includes everything encompassed by the dashed box) that is in fluid communication with at least one infusion tube 112. The at least one infusion tube 1 12 has an inlet 113 and an outlet 115 at the entrance and egress, respectively, of infusion tube 1 12. The recirculation loop 1 10 may also have a circulation pump 1 14 to allow for recirculation of the components at a desired pressure and rate within the recirculation loop 1 10. A filter element 134 that filters contaminants from the flow in the recirculation loop 110 may also be included to further enhance the blending processes as discussed further below. As an example, filter systems could involve a wire mesh or monolithic honeycomb structure, providing advantages as the size and number of cell passages creates fine bubbles of liquid hydrocarbon and gas reactant. A gas concentrator 1 16 may be immediately downstream from the outlet 115 of the at least one infusion tube 1 12. The gas concentrator 1 16 may be in fluid communication to both the recirculation loop 1 10 and the gas processing unit 108. The gas processing unit 108 may have an outlet 105 in fluid communication with the recirculation loop 110 and an outlet 107 in fluid communication with a produced gas outlet 1 18. In some embodiments, a pressurizing pump 120 may be in line between the outlet 105 from the gas processing unit 108 to the recirculation loop 110.

[0038] In some embodiments, the system 100 may include a gas sensor 128 in line between the gas processing unit 108 and the produced gas outlet 1 18 in order to monitor at least one characteristic of the gas exiting the gas processing unit (e.g., pressure, flow rate, composition, etc.). Further, in some embodiments the produced gas outlet 1 18 may be in fluid communication with and provide the produced gas to a pressurized storage vessel to collect the produced gas including hydrogen and achieve the highest utility for specific needs. The following paragraphs will discuss each particular part of the system in further detail.

[0039] Further, it is envisioned that optical sensors or float sensors may be included at any point, or within any component, of the system so that the relative concentration of gaseous reactant infused/impregnated into the hydrocarbon liquid and/or the amount of hydrocarbons liquid (infused/impregnated with gas or not) may be ascertained. The optical sensors may operate by sensing the density of the liquid hydrocarbon, which changes with the amount of infused/impregnated gaseous reactant, and this may facilitate the movement of feedstock into and through the system. For example, an optical density sensor may alert the system that more gaseous reactant needs to be input in order to maintain an appropriate gaseous reactant amount. The float sensors may generally operate by sensing the liquid-gaseous ratio or concentration within a particular component of the system, with at least one threshold value set for the system that triggers an input of gas or liquid hydrocarbon into the system until the threshold value is met. The application of these sensors in specific components will be discussed in further detail in later paragraphs.

[0040] In one or more embodiments, the hydrocarbon liquid inlet 102 may be connected to a tank or other source of hydrocarbon liquid 126. The hydrocarbon liquid capable of being processed by systems according to this disclosure may include crude oil. diesel (including bio-diesel), gasoline, jet fuel, and mixtures thereof. While the hydrogen production system 100 may be typically operated without any temperature control and at ambient temperatures ranging from about 5°C to about 40°C, in embodiments utilizing crude oil as the hydrocarbon liquid (or component thereof) it may be necessary to operate the hydrogen production system 100 (or at least particular parts of the system) at an elevated temperature to achieve adequate flow characteristics of the crude oil throughout the system 100 and to reduce the risk of precipitates forming within the system 100.

[0041] In its natural, unrefined state, crude oil ranges in density and consistency, from very thin, light weight and volatile fluidity to an extremely thick, semi-solid heavy weight oil depending upon that particular field that it is extracted from. The general properties of the crude oil/petroleum will give an indication if there is a requirement for adding a heating process or not. In particular, "viscosity" relates to the oil's resistance to flow. In some embodiments, "heavier" crude oils have a higher viscosity and may require heating to facilitate the creation of a fluid capable of moving rapidly through the system. For example, the crude oil may necessitate controlling the temperature within the hydrogen production system 100 at about 40°C - 100°C (or higher) via any means commonly known in the art. Thus in some embodiments, it may be preferable to use the very light, light and medium crude oils that have lower viscosities and may not require heating. Further, in some embodiments, the crude oil may be filtered prior to inputting it into the hydrogen production system 100 to remove certain components (e.g., sulfur, containing contaminants and marine sediments including organic materials, sand, clay, and minerals) that may damage or foul the system 100 by corrosion or creating precipitates within the system 100).

[0042] After entering the hydrogen production system 100 the hydrocarbon liquid feed may be pressurized to an appropriate pressure by lift pump 106, although in other embodiments the hydrocarbon liquid feed may be appropriately pressurized prior to entry. In some embodiments, the pressure of hydrocarbon liquid, either after entering or before entering hydrogen production system 100, may be at least about 10 psi, or at least about 20 psi, or at least 30 psi. Further, in some embodiments, the pressure of hydrocarbon liquid, either after entering or before entering hydrogen production system 100, may be at most about 60 psi, or at most 75 psi, or at most 100 psi. After appropriate pressurization (if necessary), in some embodiments the hydrocarbon liquid feed may be fed to a gas processing unit 108.

[0043] In one or more embodiments, the gaseous reactant inlet 104 may receive the gaseous reactant from a gaseous reactant source 122 (e.g., a tank, electrolysis unit, etc.). In one or more embodiments, some of the gaseous hydrogen that is produced by the hydrogen production system 100 may be used as a source of gaseous reactant. In some embodiments, the gaseous reactant infeed is performed in pulses of gaseous reactant with the pulses controlled by either a set time interval or by a sensor on the system 100 that monitors the gaseous reactant content in the system to keep the gaseous reactant amount substantially constant relative to the hydrocarbon liquid amount. In some embodiments, a float and or an optical sensor may be used to measure, via density correlations, the amount of gaseous reactant contained within the hydrocarbon liquid.

[0044] For example, the gaseous reactant may be provided in a controlled manner

(e.g., amount, timing of pulses, etc.) from the gaseous reactant source 122 to the gaseous reactant inlet 104 by a programmable gaseous reactant flow control unit 124, which may be configured to input a quantity of gaseous reactant at constant time intervals ranging generally from every 0.1 to 60 minutes. In more particular embodiments, the system may be configured to input a quantity of gaseous reactant at constant time intervals ranging from every 0.1 to 1 minute, every 1 to 5 minutes, every 5 to 10 minutes, every 10 to 20 minutes, every 20 to 40 minutes, or every 40 to 60 minutes for as long as the system is in operation. In some embodiments, the gaseous reactant may be input continuously with the amount varying dependent upon the amount of liquid hydrocarbon within the system and on the desired amount of hydrogen gas produced. In some embodiments, the input of gaseous reactant may be directly correlated with the quantity of produced gas desired. For example, a smaller amount of gaseous reactant may be input if a smaller amount of produced gas is desired and vice-versa. In general, for a given amount of hydrocarbon liquid in the system, when the amount of input gaseous reactant is doubled the amount of produced hydrogen is doubled.

[0045] FIG. 2 depicts an alternate embodiment, similar to FIG. 1 , where the hydrocarbon liquid inlet 102 may provide the hydrocarbon liquid feed directly to the recirculating loop 110, via bypass line 1 17, which then feeds to at least one infusion tube 1 12. FIG. 3 depicts yet another alternate embodiment, where the hydrocarbon liquid inlet 102 may provide the hydrocarbon liquid feed directly to at least one infusion tube 112 via bypass line 119. In the embodiments shown in FIGS. 2 and 3, the pressure of the hydrocarbon liquid infeed via bypass line 1 17 or 1 19 would need to be higher than the pressure within the recirculation loop 1 10/infusion tube 1 12 in order for the hydrocarbon liquid to be infed into the recirculating loop 1 10/infusion tube 1 12. Additionally, FIG. 4 depicts an alternate embodiment, wherein the gaseous reactant feed from inlet 104 may enter the hydrogen production system 100 and be fed directly to at least one infusion tube 1 12, via bypass line 121 , rather than be fed to the recirculating loop 1 10 that feeds directly to at least one infusion tube 1 12, as is shown in FIG. 1. In these alternate embodiments, like elements are numbered according to their numbering in FIG. 1 for convenience. Further, it is the express intent of this disclosure that any of the embodiments presented herein may be combined as may be desired to form a similar hydrogen production system.

[0046] In one or more embodiments, the infusion tube 1 12 may serve to substantially blend and infuse/impregnate the hydrocarbon liquid feed with the gaseous reactant feed. The hydrocarbon liquid and gaseous reactant mixture entering the infusion tubes 1 12 is relatively non-homogenous, with relatively large bubbles of gas non- uniformly distributed within the liquid. The non-uniformity of the bubble distribution may be even more pronounced when the gaseous reactant is introduced in pulses or bursts after a corresponding predetermined volume of liquid has been introduced to the system. The mixture's traversal through infusion tubes 1 12 at a predetermined velocity (e.g., in the range of 1 to 10 gallons per minute) serves to break up and evenly distributes the gaseous component within the mixture into relatively small and relatively uniformly sized bubbles. Further, the process of breaking up and distributing the gaseous component homogenously within the hydrocarbon liquid is accomplished within infusion tube 1 12 by maintaining relatively high pressure along with various mechanisms including, for example, one or more of friction, agitation, and turbulence. Friction, agitation, and turbulence within infusion tube 1 12 may be caused by impact with structures within (e.g., sidewalls, end walls), and connecting, the infusion tube 1 12 to the system as the fluid mixture flows through the infusion tube 1 12. Additionally, changes (contractions and expansions) in the volume through which the mixture flows may serve to increase the friction and turbulence experienced by the mixture as it flows through the infusion tube 1 12. The pressurized mixture is retained within the infusion tube 1 12 long enough for these mechanisms to render the mixture of hydrocarbon liquid and gaseous reactant essentially homogenous. In some embodiments, the infusion tube 112 shown in FIG. 1 may actually be one or more infusion tubes connected in series to achieve the homogenous blending.

[0047] The infusion tubes can be of varying configurations and sizes, e.g., flow- through (uni-flow), or "reverse-flow"' (bi-flow), straight, coiled, curved serpentine or such other shapes as necessary to provide the requisite infusion. The tubes may be sized, of certain geometry, disposed, and distributed to fit in the particular system as necessary. For example FIGS. 5 and 6 show embodiments of infusion tubes according to this disclosure. Referring to FIG. 5, a uni-flow infusion tube 1 1 16 (shown as straight in FIG. 5, although it could be curved or serpentine, etc.) includes a body 1200, defining an interior volume 1218. In some embodiments, the body 1200 may be a tube of predetermined length and diameter, enclosed with end walls 1202 and 1214. . Further, body 1200 may include passages 1204 and 1206 through end walls 1202 and 1214, respectively, providing fluid communication with the interior volume 1218. In some embodiments, connectors 1208 and 1210, associated with passages 1204 and 1206, respectively, may be included to facilitate connection of the infusion tube 1116 to the rest of the system. End walls 1202 and 1214 may be suitably secured in place within the wall of body 1200 by using a slip fit and o-ring 1216 seal along with a mechanical retaining ring 1212. The components of the infusion tube 11 16 may be formed from any suitable material, although in some embodiments aluminum may be particularly useful. Further, the amount of hydrogen produced by the system may be influenced by the choice of materials used to fabricate components therein. For example, while plastics that are compatible with the liquid hydrocarbon and gaseous reactants may be used in components of the systems, metal components may provide a catalytic effect that may facilitate the production of increased amounts of hydrogen from the system. In use, the hydrocarbon liquid and gaseous reactant mixture may enter one end of infusion tube 1 1 16 through first passage 1204 in end wall 1202, flowing through volume 1218 and out through passage 1206 in end wall 1214. In the infusion tube 1 1 16 of FIG. 5, the volume 1218 of the infusion tube is defined by the inside length, from first 1202 and second 1214 end walls, and inside diameter of the tube wall 1200. In one or more embodiments, the diameter of infusion tube 1 1 16 may range from about 0.75 inch to 2.5 inches. The length-to-diameter ratio of infusion tubes according to this disclosure may range from about 10: 1 to about 100: 1. The general configuration of an infusion tube, allows for the infusion tube 1 1 16 interior volume 1218 to provide for a volumetric expansion region for the hydrocarbon liquid and gaseous reactant mixture as it enters the interior volume 1218 from the smaller volume passage 1204. This expansion facilitates the breaking up of the larger gas bubbles into smaller gas bubbles by inducing turbulence and friction in the flow thereby homogenizing and infusing/impregnating the hydrocarbon liquid with the gaseous reactant.

[0049] Referring now to FIG. 6, a single reverse-flow infusion tube 1 1 14 is shown.

Reverse-flow infusion tube 11 14 includes a body 1302 defining an internal volume 1300. In some embodiments, the body 1302 may be a tube of predetermined length and diameter, enclosed with end walls 1304 and 1316. End wall 1316 may have an interior surface 1318 disposed facing the exit of inlet tube 1312. While depicted in FIG. 6 as flat, in some embodiments interior surface 1318 may be roughened or of any particular geometry to create or increase the turbulence of the hydrocarbon liquid and gaseous reactant mixture within the internal volume 1300 of the infusion tube 1 1 14. End walls 1304 and 1316 are secured in place within their respective ends of the body 1302 by employing o-rings 1320 and retaining rings 1314, although any other configuration and assembly technique may be used to retain the end walls 1304 and 1316 in place.

[0050] In use, the hydrocarbon liquid and gaseous reactant mixture enters infusion tube 1 1 14 through inlet passage 1306 formed in end wall 1304 and through inlet 1312, exiting the inlet 1312 generally adjacent to end wall 1316. The mixture exiting from inlet 1312 tends to impact interior surface 1318 of end wall 1316 while passing through internal volume 1300 before exiting through passage 1308 formed in end cap 1304. Thus, the reverse flow infusion tube 1 1 14 shown in FIG. 6 uses the velocity of the hydrocarbon liquid and gaseous reactant mixture along with surface friction (from impacting the interior surface 1318) to break apart the larger and non-homogenous gas bubbles, along with the volume expansion discussed above for FIG. 5, as the mixture flows through the internal volume 1300 to provide for smaller gaseous reactant bubbles and a more homogenous mixture. Therefore, the infusion tubes need not be disposed in any particular orientation, e.g., it is not necessary that the flow of the mixture enter the internal volume 1300 downwardly so that the bubbles may rise upwardly against this down-flow; however, in some embodiments this orientation may promote a more homogenous infusion.

[0051] In one or more embodiments, multiple infusion tubes may be used within a single hydrogen production system. In these instances, each infusion tube may be connected serially so that the exiting mixture from one infusion tube outlet connects to the inlet of another infusion tube. The use of multiple infusion tubes may facilitate the homogenous infusion/impregnation of the hydrocarbon liquid with the gaseous reactant. For example, the pressurized liquid-gaseous mixture entering a first infusion tube may be relatively non-homogenous, with relatively large bubbles of gaseous reactant non-uniformly distributed within the mixture. With each successive volume contraction and expansion, from passing through an infusion tube inlet into its internal volume and out again, in addition to the surface interactions inherent in this flow, further breaking up and distribution of the gas bubbles may occur. In some embodiments, by the time the hydrocarbon liquid and gaseous reactant mixture exits a final infusion tube in a series (or potentially a single infusion tube) the gas bubbles may be micro-sized, virtually imperceptible to the naked eye, and substantially uniformly distributed through the mixture.

[0052] Referring once again to the system 100 in FIG. 1, the mixture of infused/impregnated hydrocarbon liquid and gaseous reactant that is created in the infusion tubes may exit the infusion tube 1 12 at outlet 115 and proceed to a gas concentrator 116. In one or more embodiments, upon flowing to gas concentrator 1 16 from the infusion tube 112, the infused/impregnated and homogenous mixture of hydrocarbon liquid and gaseous reactant may experience a separation of at least some of the gas from the liquid fraction as the bubbles combine in the less turbulent upper portion of the gas concentrator 1 15. This separated gas may include a quantity of produced hydrogen gas. The gas that separates in the gas concentrator 116 may gather in an upper portion of the gas concentrator 1 16 where it may then exit via outlet 130 to proceed to the gas processing unit 108. Alternatively, in some embodiments, a quantity of the mixture of hydrocarbon liquid and gaseous reactant infused/impregnated in the infusion tube 112 may exit the gas concentrator 1 16 via outlet 130 and proceed to the gas processing unit.

[0053] The liquid fraction (containing the hydrocarbon liquid and residual amounts of infused/impregnated gases) that remains in gas concentrator 1 16 may exit via outlet 132 and proceed through the recirculation loop 110 to be infused/impregnated with gaseous reactant at least once more. In some embodiments, the liquid fraction exiting via outlet 132 may proceed through the recirculation loop 110 in a substantially continuous manner to be repeatedly infused/impregnated with gaseous reactant so that hydrogen gas may be produced continuously. Indeed, in embodiments where primarily gas is exiting via outlet 130, only a small portion of the hydrocarbon liquid may exit gas concentrator 116 along with the separated gas via outlet 130. Accordingly, the majority of the hydrocarbon liquid may be recirculated back to the hydrogen production system 100 (specifically recirculation loop 1 10) via outlet 132. In general, the recirculation loop 110 may be equipped with a circulation pump 1 14 that may enable a steady flow-rate and the necessary pressure to the fluids circulating therein. In some embodiments, at least 90% of the volume of impregnated/infused hydrocarbon liquid is recirculated back to the system via outlet 132, or at least 95% may be recirculated back to the system, or at least 98% may be recirculated back to the system for further production of hydrogen gas therefrom.

[0054] To meet the description of the gas concentrator 116 presented above, known gas separators may be used. Generally, they may be grouped into: gas/liquid separators, centrifugal separators, filter separators, cyclone separators, vacuum pump separators, slug catchers or a combination of these designs can be utilized to achieve the highest performance for specific needs (e.g., system size, production volume, etc.). Commonly, industrial separator designs are engineered-to-order, with virtually unlimited configuration options, suitable for any piping, instrumentation, or orientation arrangement, and to suit a myriad of applications. Thus, a gas concentrator 116 appropriate for the present hydrogen production system 100 may also be referred to as an oil/gas separator, gas/liquid separator, degasser, deliquilizer, scrubber, or trap.

[0055] FIG. 7 depicts an example of a gas concentrator 600 according to one or more embodiments of this disclosure. The gas concentrator 600 generally includes a body 602, with top and bottom end caps 606 and 608, surrounding an interior volume 604. While, FIG. 7 depicts the body 602 as generally cylindrical, it is contemplated that any shape may be used, with a shape having increased volume at the upper portion (e.g., the portion the gas would occupy) compared to a lower portion being a potentially beneficial shape. The interior volume 604 provides a space for gas (including produced gas as well as infed gaseous reactant) to separate out from the infused/impregnated liquid hydrocarbon. End caps 606 and 608 may be sealed against the cylindrical body 602 by first and second o-rings, 610 and 612, respectively. The infused/impregnated hydrocarbon liquid inlet 614 and recovered hydrocarbon liquid (after the separation of at least some of the infused/impregnated gas) outlet 605 are provided in bottom end cap 608 and produced gas outlet 607, is provided in top end cap 606.

[0056] In the interior volume 604 of the gas concentrator 600 is a cylindrical float

616. Float 616 may include at least one magnet 618 (four are shown in the inset 622) attached to the upper end cap 624 of the cylindrical float 616. Lower end cap 626, without any magnets, is provided on the opposite end of the cylindrical float 616. Alternatively, in other embodiments, at least one magnet 618 may be attached to the lower end cap 626 of the cylindrical float 616, with the upper end cap 624 free of magnets. Regardless, the cylindrical float 616 is designed to trigger at least one magnetically activated sensor 620 outside the body 602 as the cylindrical float 616 moves up and down in response to a changing gas-liquid density. Thus, the cylindrical float 616 is used as a device to dynamically control the extent of increase and/or drop of gas to liquid ratio in the hydrogen production system. At least one magnetic sensor 620 is connected to an electronic control unit that may input either hydrocarbon liquid or gaseous reactant into the system in response to the position of the cylindrical float 616.

[0057] The inset 622 shows a top down view of the upper end cap 624 of the cylindrical float 616 showing the orientation of the magnets 618 and the magnetic sensors 620. In operation, as the infused fluid flows into infused/impregnated hydrocarbon liquid inlet 614 the volume expands and some produced gas/infused gas may separate and migrate to the upper region of interior volume 604. The cylindrical float 616 will move up or down depending upon liquid to gas ratio and once the ratio of gas is too low and the cylindrical float 616 moves away from the magnetic sensors 620, allowing more gaseous reactant to be input into the system to maintain the proper liquid to gas ratio. The cylindrical float 616 size may be customized depending upon the size of the gas concentrator and the amount of fluid flow through inlet 614. In some embodiments, a circular magnetic sensor ring may be placed around the circumference of the body 602 instead of the two discrete sensors shown in FIG. 7. Alternatively, or in combination with one of the magnetic sensors described above, the one or more magnets 618 may be provided so long as the one or more magnets produce the required magnetic field to trigger the sensor or sensors.

[0058] The advantage of this design is that there is no need to measure the infused/impregnated liquid mixture's flow rate or density in order to ascertain the required liquid to gas ratio. The infused/impregnated liquid mixture enters through the inlet 614 and flows into the interior volume 604 with excess flowing to outlet 605 also positioned at the bottom of the body 602. The concentration of gas increases toward the top of the tube, where it exits for further processing. The gas concentrator may be located within the re-circulation loop.

[0059] In an alternative embodiment, shown in FIG. 8, the hydrogen production system may be configured so that the gas that is separated in gas concentrator 1 16 may exit via outlet 130 and proceed through gas sensor 128 to produced gas outlet 118. In this embodiment, the gas processing unit 108 is bypassed by the produced gas and may be completely omitted from the hydrogen production system 100 if the liquid hydrocarbon infeed is directed into the system as is shown in FIGS. 2 and 3 and previously discussed. In these embodiments, the liquid hydrocarbon fraction may be similarly recycled back into the system via outlet 132. A system utilizing the embodiment shown in FIG. 8 may require additional post-processing of the produced gas due to the omission of the gas processing unit which efficiently separates the produced gas from a recovered liquid fraction as will be discussed in detail later.

[0060] In embodiments utilizing systems similar to those shown in FIGS. 1-4, the stream (regardless of its composition) exiting outlet 130, may be sent to a gas processing unit 108 for outgassing. In the gas processing unit 108 produced gas is outgassed from the mixture of gaseous reactant and hydrocarbon liquid contained in the stream exiting outlet 130 by the reduced/lower pressure within the gas processing unit 108. Thus, two products are produced within the gas processing unit: (1) an outgassed gas containing produced gas along with input gaseous reactant and (2) a recovered liquid fraction of the hydrocarbon liquid (which may still retain small residual amounts of gaseous reactant or produced gas therein). In one or more embodiments, the produced gas may include at least one of hydrogen, nitrogen, oxygen, methane, propane, etc. [0061] In one or more embodiments, the recovered liquid fraction of the hydrocarbon liquid may be blended with an amount of virgin hydrocarbon liquid added to the gas processing unit 108 via the hydrocarbon liquid inlet 102 for further use in the hydrogen production system 100. Further, in one or more embodiments, the recovered liquid fraction (in some instances blended with virgin hydrocarbon liquid) may be fed from the gas processing unit 108 to the recirculation loop 110 for further use in the hydrogen production system 100. In some embodiments, the gas processing unit 108 may be equipped to maintain fluid level control in the unit and to generally regulate the hydrocarbon liquid infeed into the system (e.g., the hydrocarbon liquid feed may be stopped when the infusion tubes 1 12 are already full and the gas processing unit is at a maximum determined capacity). If the infusion tubes 1 12 are not full then an amount of hydrocarbon liquid from the gas processing unit 108 may be sent to the recirculation loop 1 10 so that it may keep the capacity constant.

[0062] FIG. 9 depicts an embodiment of a gas processing unit 700 according to this disclosure. Gas processing unit 700 includes a body 200 defining an interior volume 204; a detector assembly 174 disposed within the interior volume 204; a gaseous reactant and hydrocarbon liquid mixture inlet 214; a hydrocarbon liquid inlet 702; a gas outlet 107; and a recovered liquid outlet 105. Gaseous reactant and hydrocarbon liquid mixture inlet 214, hydrocarbon liquid inlet 702, gas outlet 107, and recovered liquid outlet 105 provide fluid communication between interior volume 204 and the lines connecting to the gas concentrator 116, hydrocarbon liquid source 126, produced gas outlet 1 18, and recirculation loop 1 10 shown in FIGS. 1-4, respectively.

[0063] In general, the gaseous reactant and hydrocarbon liquid mixture are introduced by inlet 214 into interior volume 204 wherein a predetermined relatively low pressure is established. In one or more embodiments, the pressure within the interior volume 204 may be substantially atmospheric pressure. The hydrocarbon liquid and gaseous reactant mixture resides in the interior volume 204 for at least a period of time sufficient to permit the outgassing of a gaseous component, including produced hydrogen, through gas outlet 107. Factors that may be considered in determining the desired residence time may include the anticipated volume and temperature of the gaseous reactant and hydrocarbon liquid mixture to be outgassed and the diameter and pressure of recovered liquid outlet 105. For example, such residence times may be on the order of from 2-20 seconds, or from 30 seconds to 1 minute, or from 1 minute to 5 minutes, although residence times outside of that range are contemplated and determined depending on the type of hydrogen production system (e.g. standalone, vehicular mounted, etc.).

[0064] The outgassing decreases the amount of gaseous reactant blended with the hydrocarbon liquid and thus once outgassed, the recovered liquid hydrocarbon fraction may be reintroduced to the recirculation loop 1 10 by recovered liquid outlet 105, where it may be re-infused/impregnated with gaseous reactant to undergo the process, as discussed above, again. In some embodiments, during or after the outgassing, an amount of virgin hydrocarbon liquid may be input into the interior volume 204 through hydrocarbon liquid inlet 702 so as to maintain a relatively constant volume of hydrocarbon liquid within the system 100. As will be described, gas processing unit 700 may, if desired, also include provisions for preventing hydrocarbon liquid from exiting through gas outlet 107.

[0065] Body 200 may be made of any material that is compatible with the hydrocarbon liquid and the gaseous reactant contemplated herein, and the body 200 may be of any dimensions/configuration that provides a suitable interior volume 204, inlets 214 and 702, and outlets 105 and 107 for the application intended (e.g., a standalone unit or a unit mounted on a vehicle). For example, body 200 may be made from various metals or plastics, so long as the metals or plastics do not chemically react or physically degrade in the presence of the hydrocarbon liquid and gaseous reactant capable of entering the gas processing unit 700.

[0066] In the embodiment of Fig. 9, body 200 includes a hollow cylindrical tube 202 of predetermined diameter and length, cooperating with top and bottom end caps 206 and 208. In some embodiments, the length of cylindrical tube 202 may be at least twice its diameter. End caps 206 and 208 may be sealed against body 202 by first and second o-rings, 210 and 212, respectively. Gaseous reactant and hydrocarbon liquid mixture inlet 214 and gas outlet 107, are provided in top end cap 206 and hydrocarbon liquid inlet 702 and recovered liquid outlet 105 are provided in bottom end cap. [0067] Top end cap 206 includes a generally cylindrical body 236 having a predetermined diameter (suitably equal to or greater than the outer diameter of tube 202), a stepped down diameter portion 238 closely conforming to the interior diameter of tube 202, a smaller diameter cylindrical extension 240 (preferably coaxial), a bottom edge 242 and respective passageways 244, 246 and 248. Additional passageways through end cap 206 may be provided to accommodate additional inlets if desired. Stepped down diameter portion 238 is preferably centrally disposed (e.g., coaxial) on body 236 extending upwardly a predetermined distance from the bottom edge 242, adapted to be closely received within the interior of tube 202, and in cooperation with o-ring 210 sealingly fixed therein. Cylindrical extension 240 is likewise preferably centrally disposed, and suitably of a predetermined diameter, and disposed on the bottom surface 242, extending downwardly a predetermined distance into the interior of tube 202 and having a bottom surface 252. In some embodiments, the ratio of height to diameter of extension 240 may be approximately 4 to 1. As will be explained, extension 240 supports hydrocarbon liquid level detector assembly 174, and includes a central cylindrical recess 250 extending upwardly from bottom surface 252 for that purpose. Passageway 244 provides fluid communication between gas outlet 107 and interior volume 204; in the embodiment of FIG. 8, passageway 244 terminates in an opening 254 on the bottom surface 252 of extension 240. Passageway 246 provides fluid communication between inlet 214 and interior volume 204, preferably terminating in an opening 216 in bottom surface 242. Passageway 248 provides a line through which electrical connections may be made to hydrocarbon liquid level detector assembly 174.

[0068] A gaseous reactant and hydrocarbon liquid mixture is introduced into gas processing unit 700 through gaseous reactant and hydrocarbon liquid mixture inlet 214. While Fig. 9 depicts only one mixture inlet 214, it is contemplated that top end cap 206 can include multiple gaseous reactant and hydrocarbon liquid mixture inlets 214 communicating with interior volume 204 through one or more (individual or interconnected) passageways 246. For example, a large standalone gas producing system may have a single gas processing unit 700 to outgas the gaseous reactant and hydrocarbon liquid mixtures provided by multiple infusion tube/gas concentrator components. [0069] Bottom end cap 208 suitably comprises a generally cylindrical body 260 having a predetermined diameter closely conforming to the interior diameter of tube 202. Recovered liquid outlet 105, suitably extends through bottom end cap 208 to provide fluid communication with interior volume 204 such that the recovered liquid hydrocarbon liquid fraction and/or virgin hydrocarbon liquid exit gas processing unit 700 and are directed to recirculation loop 110.

[0070] The internal volume 204 of gas processing unit 700 may generally range from about 1 liter to about 25 liters for vehicular mounting applications. For diesel engines having displacements in the range used in most road vehicles, the volume 204 of gas processing unit 700 ranges from about 1 liter to about 10 liters; in many passenger vehicles the volume of gas processing unit 104 is suitably about 1 liter. Volumes larger than 10 liters, and in some cases larger than 25 liters, may be used in connection with various applications, such as, marine engines, locomotives, and stationary diesel engines and standalone units. Volumes less than 1 liter, may be also used in connection with various applications, such as, small engine gen-sets.

[0071] Hydrocarbon liquid level detector assembly 174 may be configured to be responsive to either the level of liquid and/or the ratio of hydrocarbon liquid to gas in gas processing unit 700 in order to maintain proper volumes of hydrocarbon liquid and airspace within gas processing unit 700. In the embodiment of FIG. 9, hydrocarbon liquid level detector assembly 174 includes a float and magnet assembly 222 (communicating with wire 154), a guide shaft 224, and an anti-slosh tube 232. In general, float and magnet assembly 222 is disposed on guide shaft 224 within the interior of anti-slosh tube 232 and actuated or deactivated to generate a control signal 154 depending upon the level of liquid and/or the ratio of hydrocarbon liquid to gas in interior volume 204, maintaining the level of liquid and/or the ratio of hydrocarbon liquid to gas in interior volume 204 within a predetermined range. Anti-slosh tube 232 may be employed to minimize the effects of transient changes in the level of the hydrocarbon liquid interacting with float and magnet assembly 222 due to "sloshing" caused by motion or momentary tilting of gas processing unit 700, such as might result from movement of a vehicle employing system 100 and to prevent hydrocarbon liquid from entering passageway 244 leading to gas outlet 107. [0072] Guide shaft 224 and anti-slosh tube 232 are concentrically disposed, with guide shaft 224 within the interior of tube 232, attached to top end cap 206 (suitably detachably), and extending substantially vertically into interior volume 204. Guide shaft 224 is suitably received in recess 242 of extension 240, and includes an interior channel 256 communicating with passageway 248 of end cap 206 to facilitate electrical connection of wire 154 to float and magnet assembly 222. Anti-slosh tube 232 is received on cylindrical extension 240, e.g., has a predetermined inner diameter generally corresponding to the diameter of extension 240 and the top end of tube 232 closely fits about extension 240. If desired, a securing device, such as, adhesive or a pin extending through a tube 232 into extension 240, can be utilized. As will be discussed, anti-slosh tube 232 extends downwardly a predetermined distance (from e.g., 0.5 to 1.5 inch) beyond guide shaft 224, and, particularly, float and magnet assembly 222.

[0073] In general, floating magnetic element 226 moves axially along guide shaft 224 in accordance with the level of liquid or gas in gas processing unit 700. When the fluid or gas level in interior volume 204 (or more particularly, within anti-slosh tube 232) falls below a predetermined level, floating magnetic element 226 is moved out of proximity of switch 230 such that a control signal is generated within wire 154 to initiate activation of lift pump 106 (FIG. 1) associated with hydrocarbon liquid source 126 to add a predetermined amount of liquid to gas processing unit 700 (and actuation of gaseous reactant flow control unit 124 to add more gaseous reactant to the system). Thus, the position of magnetic switch 230 on guide shaft 224 effectively stabilizes the maximum (as well as the minimum) surface level of the liquid or gas within volume 204. That position may be chosen, taking into account a predetermined amount of gaseous reactant and hydrocarbon liquid mixture to provide sufficient distance from gas outlet 107 to avoid the possibility of liquid entering into the gaseous outlet stream through passageway 244; and to establish sufficient low pressure air space above the surface of the liquid in gas processing unit 700 to accommodate outgassing of the produced gaseous component.

[0074] While, for example, in vehicular applications, movement of system 100 may cause the liquid to slosh within gas processing unit 700, anti-slosh inner tube 232 keeps transient splashing from causing significant motion for floating magnetic element 226 or from entering the flow of outgassed gaseous component. Tube 232 is of relatively small interior diameter (suitably in the range of 1 to 1.5 inch) and of predetermined length (suitably in the range of 80 to 150 mm), with a distal opening 258. As noted above, anti-slosh tube 232 extends downwardly a predetermined distance (e.g., 1/2 inch) beyond guide shaft 224, and, particularly, float and magnet assembly 222, such that opening 258 is disposed below the anticipated surface level of the liquid mixture retained in volume 204. The effect of sloshing is minimized by: (a) the fact that tube 232 extends beyond the surface of the liquid in interior volume 204; (b) the relatively small diameter of tube 232 and (c) the relatively close fit between floating element 226 and the interior of tube 232. The relatively small diameter of tube 232 and disposition of opening 258 below the liquid surface minimizes the effect of angular movement at the surface of the liquid mixture (e.g„ tilt, sloshing or splashing) on the position of floating element 226. Since opening 254 of passageway 244 (connected to gas outlet 107) is disposed within the confines of tube 232, the relatively close fitting relationship between floating element 226 and the interior of tube 232 tends to prevent sloshing liquid from advancing beyond floating magnetic element 226 and entering passageway 244. The flow of outgassed gaseous component is further isolated from the liquid, by use of gas vent passage 234. In the gas processing unit embodiment of FIG. 9, the primary outgassing of the liquid takes place exterior to anti-slosh inner tube 232. Gas vent passage 234, through which gaseous component released from the liquid mixture in interior volume 204 enters the interior of tube 232 (and passageway 244), is disposed a predetermined distance from float and magnet assembly 222, and thus the anticipated liquid surface so that sloshing liquid will not reach gas vent passage 234. Gas vent passage 234 is of relatively small diameter so that it can allow the passage of gaseous component, but does not allow liquid to flow readily there through. In addition, since the primary outgassing takes place outside anti-slosh inner tube 232, the pressure of outgassed component is greater outside anti-slosh inner tube than inside anti-slosh inner tube 232. Thus, the flow of outgassed component is from the exterior of anti-slosh inner tube 232 to the interior. The outgassed component rises within gas processing unit 700 to vent 234, passageway 244 and gas outlet 107. [0076] In some embodiments, hydrocarbon liquid level detector assembly 174 can he positioned on the bottom of gas processing unit 800, as depicted in the gas processing unit embodiment shown in FIG. 10. The embodiment of gas processing unit 800 in Fig. 10 is substantially identical to the embodiment shown in Fig. 9 (with similar numbering indicated similar features) flipped 180 degrees except that the magnetic switching is reversed, mixture inlet 214 and liquid outlet 105 are disposed in bottom end cap 208, anti-slosh tube 232 extends upwardly such that distal opening 258 is disposed a predetermined distance above the anticipated surface level of the liquid mixture in interior volume 204 and gas vent passage 234 in tube 232 is replaced by a somewhat larger diameter passageway 300 (disposed below the anticipated surface level) to allow liquid to traverse into and out of anti-slosh inner tube 232, thus, permitting the liquid to act upon floating magnetic element 226. Gas outlet 107 suitably extends through end cap 206 into interior volume 204. Additionally, FIG. 1 1 depicts an embodiment of a gas processor 1 100 that further provides for a level detector assembly 174 included within the gas processor 1 100 depiction shown in FIG. 10. The apparatus illustrated in FIG. 1 1 combines elements already described with respect to FIGS. 9 and 10 and similar numbering indicates similar features. Gas processor 1 100 may be particularly useful because it may allow for the simultaneous detection of the level of the liquid and the gas within the system. When measurements are taken over time and coupled with appropriate controls, gas processor 1 100 further allows for the level control as a response to displacement expansion within the infusion volume. A maximum and minimum liquid to gas ratio can thus be controlled. Further, in some embodiments a mechanical level detector in a gas processing unit may be used according to known technology.

[0077] Thus, the general method for hydrogen production may be said to include infeeding gaseous reactant into a hydrocarbon liquid at a first pressure; infusing the gaseous reactant and the hydrocarbon liquid under a second pressure to create a homogenous mixture of gaseous reactant ini used/impregnated into the hydrocarbon liquid; outgassing a gaseous mixture comprising produced hydrogen gas from the homogenous mixture of gaseous reactant and hydrocarbon liquid at a third pressure; and collecting the outgassed gaseous mixture. [0078] In one or more embodiments, the outgassed gaseous mixture, including the produced hydrogen, may be fed into a gas purification system after leaving the hydrogen production system 100 via outlet 1 18. The gas purification system may serve to substantially remove any remaining liquids or particulate matter that may be contained within the gaseous stream exiting outlet 1 18. In some embodiments, the purification system may be capable of separating the hydrogen from any other gases that may be exiting the system via outlet 1 18 so that substantially pure hydrogen may be collected. In one or more embodiments, the gaseous stream exiting the hydrogen production system 100 via outlet 1 18 may be pressurized into a vessel for later use and/or for transportation to another location where the produced gas may be used. In some embodiments, the produced gases may be pressurized into a vessel for efficient storage and transportation.

[0079] While not being bound by theory it is believed that two processes may be occurring during the operation of the system described above. First during the infusion/impregnation process (e.g., the homogenous blending of the hydrocarbon liquid feedstock and the gaseous reactant) longer chain hydrocarbons may be formed via catenation reactions. During the outgassing, hydro-cracking of the hydrocarbon chain may occur, which may produce appreciable quantities of hydrogen gas. The produced and outgassed hydrogen gas may be mixed with other liberated gases (some of which may be produced by similar hydro-cracking reactions) such as nitrogen, oxygen, methane, propane, helium etc. during the outgassing. In some embodiments, a single input of gaseous reactant into a hydrocarbon liquid feedstock may facilitate the system generating produced gas for up to about 120 minutes or up to about 180 minutes, or up to about 300 minutes, at which point another input of gaseous reactant into the hydrocarbon liquid feedstock may be necessary to maintain the hydrogen production within the system. Thus, the repeated input of gaseous reactant into the hydrocarbon liquid feedstock may facilitate the continuous production of hydrogen gas from the system.

[0080] Application of Hydrogen Production System

[0081] In some embodiments, the hydrogen production system 100 described above may be included in a larger system 900, wherein at least some of the hydrogen produced is consumed by a hydrogen consuming unit 902. In these embodiments, substantially all of the hydrogen produced by the hydrogen production system 100 may be sent to the hydrogen consuming unit 902 or some of the hydrogen may be sent to unit 902 with the remaining portion being pressurized in a vessel and stored for later use. A generalized system 900 is shown in FIG. 12. Gas produced by hydrogen production system 100 may exit at produced gas outlet 1 18, which is in fluid communication with a hydrogen consuming unit 902. In some embodiments, the produced gas exiting system 100 may be cleaned or otherwise processed (e.g., scrubbed of particular components and/or separated into component gases as discussed above) prior to entering hydrogen consuming unit 902. In some embodiments, the hydrogen consuming unit may be one of a fuel cell, a hydrogen filling station, a chemical synthesis unit, or an enhanced fuel blending device connected to a combustion engine, among others. For example, an enhanced fuel blending device may blend a small amount of the produced gas (including hydrogen) and a hydrocarbon liquid fuel to form an enhanced fuel. In one or more embodiments, the enhanced fuel blending device may substantially resemble system 100 and use infusion tubes 112 to blend the enhanced fuel including produced hydrogen gas and a liquid hydrocarbon fuel, although other blending modes may also be used to formulate an enhanced fuel. Further, FIG. 12 depicts an optional embodiment (see dashed lines), wherein the enhanced fuel so formed may then be fed to a combustion engine 904 where it can be combusted as an enhanced fuel. In one or more embodiments, the combustion engine may be that of a transportation vehicle or that of a stationary generator (gen-set). The blending of the hydrogen containing gas with hydrocarbon liquid fuels to form an enhanced fuel may facilitate the combustion of the hydrocarbon liquid fuel that occurs during the combustion of fuels in an engine. This may result in increased fuel economy, fewer pollutants emitted, and fewer combustion byproducts forming within the engine (e.g., a potentially longer engine life). Further, in some embodiments, the engine 904 may not completely utilize the enhanced fuel formed in the enhanced fuel blending device 902, in which case the enhanced fuel may be returned to the hydrogen production system 100 (specifically the gas processing unit 108) via return line 906 for use in producing more hydrogen. [0083] In other embodiments, the hydrogen consuming unit 902 may directly consume the produced hydrogen as in a fuel cell, where hydrogen and oxygen may be used as reactants to generate electricity, or in chemical synthesis applications where hydrogen may be used as a useful reactant (e.g. to form ammonia via the Haber-Bosch process, or in hydrogenation reactions, etc.).

[0084] EXAMPLES

[0085] Example 1

[0086] A system according to the present disclosure was tested for its ability to produce hydrogen from a diesel feedstock. Prior to each testing run, the system was purged with air for about two to three hours to substantially remove all of the hydrocarbon liquid and/or gaseous reactant contained therein. The temperature within the system varied with the ambient temperature and was between about 23°C - 28°C for the test runs. The infusion tube volume was 21.2 liters for the system used and a substantially comparable amount of diesel was input into the system. The hydrogen infeed pressure was set to 140 psi for all of the runs. The system pressure (i.e., pressure in the infusion tubes and recirculation loop) was varied for each run with 30 psi, 60 psi, and 100 psi being used. Each test was performed for 60 minutes with hydrogen being input into the recirculation loop of the system at 5 minute intervals in the amount of between 13-27.5 seem. The cumulative amount of gas outgassed was also measured at 5 minute intervals and the hydrogen percentage of the outgassed gas was analyzed using a gas analyzer available from Divesoft s.r.o., Roudnice nad Labem, Czech Republic.

[0087] The in-house gas analyzer was calibrated to detect hydrogen gas according to the instructions provided within the owner's manual provided by Divesoft. The calibration was confirmed via sampling of the measured gas and subsequent independent lab testing of the samples by a gas analysis according to ASTM D1946. The independent testing results showed that sample specimens had a concentration of hydrogen within about 2 weight percent of the measurements of the in-house gas analyzer.

[0088] FIG. 13 shows the cumulative outgassing amount over time for the three experimental runs. It can be seen that over the course of the experiment that lower system pressure directly correlated with an increase in the cumulative amount of gas outgassed. From the data it can be seen that each of the runs followed a general linear increase the cumulative amount of gas outgassed from the system over time.

[0089] FIG. 14 shows how the hydrogen concentration in the cumulative outgassed gas changed over the course of the three experimental runs. It can be seen that over the course of the experiment that lower system pressure directly correlated with an increase in the concentration of hydrogen in the cumulative amount of gas outgassed. From the data it can be seen that for the runs performed at the lowest system pressure (i.e., 30 psi and 60 psi) the increase in hydrogen concentration seemingly followed an exponential trend, while the increase in hydrogen concentration for the higher pressure run (100 psi.) followed a linear trend. Regardless, each run demonstrates that the system is capable of producing a greater amount of hydrogen from the diesel than that which is input into the system. Indeed, while the amount of gas being outgassed is shown to obey a linear relationship in FIG. 13, FIG. 14 demonstrates that at lower system pressures a greater amount of that gas being outgassed is hydrogen by the exponential trend seen in the hydrogen concentration plot over time.

[0090] Comparative Example

[0091] The same system used for the above testing was utilized in the comparative example. The system pressure during this test was set to 50 psi and no hydrogen gas was input into the system during the 60 minute test. The results of the hydrogen concentration and cumulative outgassing during the test are shown in Table 1 below.

Table 1 - Com arative Exam le Out assin Results

25 1.5 266

30 1.5 322

35 1.4 370

40 1.4 422

45 1.3 457

50 1.3 510

55 1.2 562

60 1.2 623

[0092] From the results shown in Table 1 it is clear that the input of hydrogen gas into the hydrogen production system, and its subsequent infusion into the diesel therein, is required for the production of hydrogen gas.

[0093] Example 2

[0094] In this example unadulterated or virgin diesel along with a sample of diesel that had been utilized within the system to produce hydrogen (processed diesel) were compositionally analyzed by various American Standardization for Testing and Materials (ASTM) methods. The "processed diesel" had been utilized within the system for 60 minutes prior to its collection and analysis. The results of these analyses are shown in Table 2 below. In the table, FIA references "fluorescent indicator absorption", while IBP and FBP reference the "initial" and the "final" boiling points, respectively.

Table 2 - Com ositional Anal sis Results

FIA-Olefins 0.86% 1.46%

FIA-Aromatics 17.44% 19.95%

ASTM D2887 Homogenous

Sample

IBP 279 °F 276 °F

FBP 837 °F 815 °F

FIA-Saturates

IBP 277 °F 303 °F

FBP 843 °F 800 °F

FIA-Olefins

IBP 181 °F 169 °F

FBP 791 °F 782 °F

FIA-Aromatics

IBP 250 °F 270 °F

FBP 788 °F 797 °F

[0095] The results of this analysis show that the processed diesel contains increased amounts of olefins and aromatics relative to the unadulterated diesel and, while not being bound by theory, any reactions that may convert saturated hydrocarbons to olefins and aromatics would have the potential to liberate hydrogen.

[0096] Example 3

[0097] In this example the same system as used in Example 1 was charged with approximately 20 liters of unadulterated synthetic diesel, which was then infused with about 20 standard liters of hydrogen, the gaseous reactant, during each test run (e.g., the same 20 liters of diesel was re-used for each run). During the gaseous reactant introduction time, the circulation pump is running, and a valve on the line connecting the gas concentrator to the gas processor is closed. Due to the valve being closed the liquid mixture exits the infusion tubes, bypasses the gas processor, moves through the circulation loop and re-enters the infusion tubes. The pressurization pump is used during the hydrogen introduction time and also to achieve a pressure of about 100 psi in the infusion tubes and the system. Once the desired amount of gaseous reactant has been introduced and infused, the valve is opened, allowing the mixture of hydrogen infused diesel to flow from the gas concentrator to the gas processor, which releases the gas. The step of releasing gas may be omitted by keeping the valve closed, which may effectively encourage changes in the chemical composition of the mixture, i.e. molecules and carbon range shift in diesel feedstock and transportation fuels. In this process, there is no requirement for heating or cooling the hydrogen, diesel feedstock, or the mixture. No exothermic reaction occurred when the hydrogen is processed with the diesel within the system.

[0098] The process described above can be generalized to the flow chart shown in

FIG. 15. Further, the flow chart shown in FIG. 15 may also be generally applicable to other embodiments of this present disclosure. In Phase #1 (1502), the diesel and the hydrogen form a low pressure infusion. In Phase #2 (1504), the infusion is recirculated and hydrogen outgassing occurs. In phase #3 (1506), the hydrogen outgassed is collected/dispensed.

[0099] A sample of the outgassed product was taken after each of four separate inputs and infusions of hydrogen during the 4 hours of using the diesel within the system. Table 3 shows the results of the samples taken from the four runs performed with the single diesel input. The units for all of the values in Table 3 are standard liters.

Net ¾ 30.73 30.61 30.06 34.04 125.44

Production

[00100] Further, the virgin diesel and the processed mixture was analyzed by Southern Petroleum Laboratories, Inc. (Houston, Texas) by the Hydrocarbon Forensic Analysis/Piano (PONA) analysis to identify changes in molecular composition and shifts in the hydrocarbon stream. The results of these analyses are shown in Table 4 below.

[00 Further, the unadulterate and processed synthetic diesel was independently analyzed by GTI laboratory for API Gravity and Specific Gravity. The pre-test, unadulterated synthetic diesel sample measure 33.7° API and 0.857 Specific Gravity. The post-test sample of the processed synthetic diesel measured 34.3° API and 0.853 Specific Gravity.

[00102] Example 4

[00103] In this example the same system as used in Example 1 was charged with approximately 20 liters of unadulterated diesel, which was then infused with about 25 standard liters of hydrogen, the gaseous reactant, during each test run (e.g., the same 20 liters of diesel was re-used for each run). During the gaseous reactant introduction time, the circulation pump is running, and a valve on the line connecting the gas concentrator to the gas processor is closed. Due to the valve being closed the liquid mixture exits the infusion tubes, bypasses the gas processor, moves through the circulation loop and re-enters the infusion tubes. The pressurization pump is used during the hydrogen introduction time and also to achieve a pressure of about 100 psi in the infusion tubes and the system. Once the desired amount of gaseous reactant has been introduced and infused, the valve is opened, allowing the mixture of hydrogen infused diesel to flow from the gas concentrator to the gas processor, which releases the gas. The step of releasing gas may be omitted by keeping the valve closed, which may effectively encourage changes in the chemical composition of the mixture, i.e. molecules and carbon range shift in diesel feedstock and transportation fuels. In this process, there is no requirement for heating or cooling the hydrogen, diesel feedstock, or the mixture. No exothermic reaction occurred when the hydrogen is processed with the diesel within the system. ] In each of four runs, the gaseous reactant is introduced over approximately five minutes and then the produced gas is monitored over the course of 20 to 25 minutes. During the gas production stage (outgassing), the spray of the return mixture from the gas concentrator into the gas processor creates approximately a 1 cm thick foam layer on the liquid contained in the gas processor. After approximately 7 minutes a periodic fluctuation in the produced gas flow rate occurs, and this is accompanied by rhythmic and highly turbulent oscillating flow. In the following 10 to 15 minutes, the liquid in the infusion tubes is undergoing changes from being uniformly dispersed to gaseous which is caused by the pressure drop from the starting pressure of 100 psi to ambient pressure within the infusion tubes as the valve is opened allowing the mixture of hydrogen infused diesel to flow from the gas concentrator to the gas processor. As shown in Table 3 below, the excess production of gas is repeatable - with approximately two times more gas produced than the infeed.

Table 5

(Standard Liters)

Cumulative 47.035 47.475 47.812 45.48 Produced Gas

(Standard Liters) ] Further, the virgin diesel and the processed mixture was analyzed by Southern Petroleum Laboratories, Inc. (Houston, Texas) by the Hydrocarbon Forensic Analysis/Piano (PONA) analysis to identify changes in molecular composition and shifts in the hydrocarbon stream. The results of these analyses are shown in Table 6 below and FIGS. 16-20. Including the runs indicated above, the processed diesel in Table 6 below had been re-used for 200 hours within the system.

Table 6

[00106] The results, presented in FIGS. 16-20 show shifts of carbon containing components and the isomerized fraction of alkanes (saturated hydrocarbons). There is evidence that in this process, during the exposure of virgin diesel and hydrogen at ambient temperature, a molecular weight distribution of napthenes is observed. Conventionally, the standard conditions for this type of shift to occur is when high temperatures (approximately 650 to 1000 degrees F and higher) are employed in the hydrocracking process (required for distillation and during refinery operations). As can be seen in FIGS. 16-19, the carbon range of virgin diesel is C4-C28, and the carbon range of the mixture is formed in a range of C3-C27, C4-C27, and C5-C27 and C5-C28. Further, in this example, the surface tension of the virgin diesel was 29.7 dynes/cm, while the surface tension of the processed mixture collected after the run was 26.5 dynes/cm.

[00107] Thus in this method diesel may be upgraded by causing significant changes in the isomers of the alkanes and a shifting of the napthenes. Specifically, isomerization reactions occur where chain molecules get converted into ring bearing molecules with an excess of hydrogen being produced. In the processed sample the octane rating is increased due to the molecular changes, making the processed fuel have better combustion properties.

[00108] Importantly, in the systems and methods disclosed the isomerization reaction occurs spontaneously and without applying high pressures and/or high temperatures to treat and convert the hydrocarbon feedstock. The hydrocarbon feedstock can be processed steadily and continuously, lasting for at least about 300 hours within the system. Another important advantage of methods disclosed herein is that no CO or C0₂ are produced by this method, there is no waste to be processed, and no exotic materials are used. Thus, the presently disclosed methods may be used industrially for production of hydrogen for Fisher-Tropsch processes, for processing hydrocarbon gases, and for an overall simplification of hydrocarbon distillation by reducing the need for heat and power consumption during oil refining.

[00109] Although only a few example embodiments have been described in detail above, those skilled in the art will readily appreciate that many modifications are possible in the example embodiments without materially departing from this invention. Accordingly, all such modifications are intended to be included within the scope of this disclosure as defined in the following claims.

Claims

CLAIMS What is claimed:

1. A system for hydrogen production, comprising:

at least one infusion tube;

a gaseous reactant inlet in fluid communication with the infusion tube;

a recirculation loop in fluid communication with an outlet of the infusion tube and an inlet of the infusion tube;

a gas processing unit configured to receive hydrocarbon liquid from a hydrocarbon liquid inlet, to receive a mixture of hydrocarbon liquid and gaseous reactant from the infusion tube, and to provide at least some of a recovered liquid fraction to the recirculation loop; and

an outlet on the gas processing unit configured to connect to a storage vessel to collect produced hydrogen gas.

2. The system for hydrogen production of claim 1, further comprising:

a programmable gaseous reactant flow control unit configured to provide gaseous reactant at a first pressure to gaseous reactant inlet from a gaseous reactant source.

3. The system for hydrogen production of claim 1 , further comprising:

a programmable gaseous reactant flow control unit configured to provide gaseous reactant at a first flow rate to gaseous reactant inlet from a gaseous reactant source.

4. A system, comprising:

a hydrogen consuming unit;

at least one infusion tube;

a gaseous reactant inlet in fluid communication with the infusion tube;

a hydrocarbon liquid inlet in fluid communication with the infusion tube;

a recirculation loop in fluid communication with an outlet of the infusion tube and an inlet of the infusion tube; a gas processing unit configured to receive a mixture of hydrocarbon liquid and gaseous reactant from the infusion tube and to provide at least some of a recovered liquid fraction to the recirculation loop;

an outlet on the gas processing unit, the outlet in fluid communication with the hydrogen consuming unit.

5. The system of claim 4, wherein the hydrogen consuming unit is selected from a fuel cell, a hydrogen filling station, an enhanced fuel blending device, or a chemical synthesis unit.

6. The system of claim 4, wherein the hydrogen consuming unit directly consumes the hydrogen.

7. The system of claim 5, wherein the hydrogen consuming unit is an enhanced fuel blending device in fluid communication with a combustion engine.

8. A method for producing hydrogen, comprising:

inputting gaseous reactant into a hydrocarbon liquid at a first pressure;

blending the gaseous reactant and the hydrocarbon liquid under a second pressure to create a homogenous mixture of gaseous reactant and hydrocarbon liquid; outgassing a gaseous mixture comprising produced hydrogen gas from the homogenous mixture of gaseous reactant and hydrocarbon liquid at a third pressure; and

collecting the outgassed gaseous mixture.

9. The method of claim 8, wherein the hydrocarbon liquid is selected from crude oil, diesel, bio-diesel, gasoline, jet fuel, and mixtures thereof.

10. The method of claim 8, wherein the gaseous reactant is selected from hydrogen, methane, ethane, butane, propane, natural gas, and mixtures thereof.

11. The method of claim 8, wherein the first pressure is higher than the second pressure and the third pressure.

12. The method of claim 1 1 , wherein the second pressure is higher than the third pressure.

13. The method of claim 12, wherein the third pressure is substantially atmospheric pressure.

14. The method of claim 8, wherein the first pressure is from about 100 to 200 psi.

15. The method of claim 8, wherein the second pressure is from about 20 to 100 psi.

16. The method of claim 8, wherein the inputting is a pulsed input at a constant time interval from every 0.1 to 60 minutes.

17. The method of claim 8, wherein the blending occurs during the flow of the gaseous reactant and hydrocarbon liquid through an infusion tube, the infusion tube allowing for the expansion and contraction of the flow.

18. The method of claim 8, further comprising:

providing a programmable gaseous reactant flow control unit configured to provide gaseous reactant at a first flow rate to gaseous reactant inlet from a gaseous reactant source;

selecting at least some of homogenous mixture of gaseous reactant and hydrocarbon liquid; and

further blending the provided gaseous reactant with the at least some of the homogenous mixture.

19. A system including a float assembly for controlling a control unit, comprising:

the float assembly including:

an inlet in fluid communication with a source of infused fluid, the infused fluid being a mixture of infused/impregnated hydrocarbon liquid and gaseous reactant;

a float, the float including:

a cap; and

at least one magnet; and

at least one magnetic sensor provided in proximity to the magnet; and

a gaseous reactant flow control unit in fluid communication with the inlet; wherein the at least one magnet is disposed on or within the cap such that the magnetic sensor and magnet are in communication; and

the sensor is in communication with the control unit to provides a signal to adjust a flow of the gaseous reactant provided to the inlet.

20. A treated hydrocarbon fuel prepared according to method of claim 8, wherein the treated hydrocarbon fuel is comprised of at least a portion of the gaseous reactant and the hydrocarbon liquid.

21. The treated hydrocarbon fuel of claim 20, wherein the treated hydrocarbon fuel has a carbon range of C5-C27.

22. The treated hydrocarbon fuel of claim 20, wherein the treated hydrocarbon fuel has a carbon range of C4-C27.

23. The treated hydrocarbon fuel of claim 20, wherein the treated hydrocarbon fuel has a carbon range of C5-C28.

24. The treated hydrocarbon fuel of claim 20, wherein the hydrocarbon liquid has an initial mass fraction ratio (%) of paraffins and the treated hydrocarbon fuel has a mass fraction (%) ratio of paraffins which is lower than the initial mass fraction (%) ratio.

25. The treated hydrocarbon fuel of claim 20, wherein the hydrocarbon liquid has an initial mass fraction ratio (%) of iso-paraffins and the treated hydrocarbon fuel has a mass fraction (%) ratio of iso-paraffins which is greater than the initial mass fraction (%) ratio.

26. The treated hydrocarbon fuel of claim 20, wherein the hydrocarbon liquid has an initial mass fraction ratio (%) of napthenes and the treated hydrocarbon fuel has a mass fraction (%) ratio of napthenes which is lower than the initial mass fraction (%) ratio.

27. The treated hydrocarbon fuel of claim 20, wherein the hydrocarbon liquid has an initial mass fraction ratio (%) of aromatics and the treated hydrocarbon fuel has a mass fraction (%) ratio of aromatics which is lower than the initial mass fraction (%) ratio.

28. The method of claim 8, wherein the homogenous mixture is a recirculated stream.

29. The method of claim 8, wherein the homogenous mixture is isolated from the outgassing, wherein the homogenous mixture contains hydrocarbon liquid with excess amount of gas.

30. The method of claim 8, wherein the method does not include a temperature increase.

31. The method of claim 8, wherein at least a portion of the gaseous reactant is provided from a stream of the outgassed gaseous mixture.