• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    abstract method for gas generation control; and electrically initiated and controlled liquid composition is the development of an electrically initiated and controlled liquid composition comprising an oxidant, fuel soluble additive (s) and other optional additives to enhance chemical or ballistic properties, or a combination thereof. The liquid composition further comprises stabilizers for enhancing thermal stability, sequestrants for minimizing detrimental effects of transition metal contaminants and maximizing efficiency of combustion enhancers. Heavy metal buffers and sequestrants or complex agents may be used in combination to achieve the highest degree of thermal stability. Additional ionic co-oxidants may be added to the liquid composition to stabilize the liquid oxidant and further lower the freezing point. The liquid phase of matter allows flow through pipes or tubes of tanks, reservoirs or other containers through metering valves, followed by ignition or combustion modulation when electrically or static stimulated by electrodes. 1/1
    公开号:BR112015009169A2
    申请号:R112015009169
    申请日:2013-10-24
    公开日:2019-12-10
    发明作者:D Mcpherson Michael；Manship Tim
    申请人:Digital Solid State Propulsion Inc；
    IPC主号:
    专利说明:

    METHOD FOR GAS GENERATION CONTROL; AND
    NET COMPOSITION STARTED AND ELECTRICALLY CONTROLLED
    RELATED ORDERS [001] This request claims the priority of the request
    provisional From U.S with serial number 61/718132, deposited in October 24 in 2012 and the non- request provisional From U.S with serial number 14 / 040.442, deposited in 09/27/2013. At revelations of the demands provisional and non-provisional are embedded in the present
    document as fully established.
    BACKGROUND OF THE REVELATION
    FIELD OF REVELATION TECHNIQUE [002] The present modality is related, in general, to propellants and, in particular, to a variety of improvements to the previously disclosed electronically controlled solid propellants, in which said propellants are in liquid state.
    DESCRIPTION OF THE RELATED TECHNIQUE [003] The compositions that generate gas are, in this document, defined as any material that stores chemical energy in a fixed volume. Explosives, propellants, pyrotechnics and other compositions that generate gas are examples of materials that can vary significantly in their performance. The reaction in these compositions usually results from shock or heat. Explosives and propellants can also be considered simply as a gas storage medium as a solid. Pyrotechnics typically release much of their energy as heat. Materials that generate energy gas often consist of fuels and oxidants that are intimately mixed. Incorporate fuels and
    2/25 oxidants in a molecule, or through chemical or physical mixtures of separate fuels and oxidizing ingredients, is generally sufficient to mix the composition. The material can also contain other constituents, such as binders, plasticizers, stabilizers, pigments, etc.
    [004] Propellant compositions that generate gas have numerous applications, such as rocket propulsion systems, fire suppression systems, oil field services, gas field services, mining, torpedoes, airbag security systems and others uses where rapidly expanded gas is used depending on its performance. Often, in these applications, it is desirable to control the ignition, burning rate and extinction of a propellant by applying an electric current.
    [005] One of the main disadvantages of solid propellants has always been the lack of control of the choke and the ability to start the engine again, once it has been started. Conventional solid propellants also continue to be hazardous for production, transportation and use, as they are subject to being accidentally ignited from flames or sparks. Once ignited, conventional solid propellants only allow for minimal control and are not easily extinguished or triggered again. These characteristics limit the function and increase the cost of the propellant systems. Typically, such conventional propellants are classified in the Department of Transport's (DOT) hazardous goods transport resolution, as Class 1.1 to 1.3 Explosives. In many of these cases, an electrically controlled propellant
    3/25 can allow propellant duration and burn rate to be precisely controlled, while still allowing for cost savings, mission flexibility, all with lower hazard ratings, simplifying delivery or transportation.
    [006] In some commercial, space and military applications, a low-emission or smokeless propellant is required. Such formulations typically do not contain metal fuels or chlorine-based oxidants, such as ammonium perchlorate. Conventional formulations use oxidants called nitroamines instead of ammonium perchlorate. In other applications, high burn rate composites are required, in which nitroamines (RDX, HMX) are used in combination with nitroglycerin or nitrocellulose. Explosive These types of propellants are normally considered to be Class 1.1, which requires additional safety precautions during production, transport and storage. In addition, high specific impulse propellants (I sp ) are usually formed with aluminum-containing ammonium perchlorate composites. These types of composites generate smoke from the combustion of aluminum and hydrochloric acid generated when the composition interacts with moisture. Finally, all current propellants are sensitive to spark, which means that accidents that occur from stray static charges can, at any time, cause the propellants to ignite during production.
    [007] In the past, poly (tetra fluoroethylene) (PTFE) and other substances have been used as electrically controlled propellants, but these prior art propellants suffer from two significant disadvantages. First,
    4/25 they often do not extinguish as quickly as desired after an electrical current has stopped. Second, these propellants do not supply any energy of their own, since all the energy for the gas generation of the propellant comes from the source of electrical energy. Additionally, compositions produced from fluoro carbides and active metal fuels require the use of flammable solvent in the production, which can result in spontaneous ignition and disastrous results. Once the mixture is reached, the flammable solvent needs to be removed and recovered, adding costs to the production process.
    [008] Compared to conventional liquid propellants, conventional solid propellants whose combustion is with electrical energy traditionally require high voltage pulse discharges (in the kilogram volts range), resulting in ablation of the propellant's surface to produce ionizing gas species which are then accelerated by an electromagnetic field. Propellants like these suffer two serious disadvantages. First, conventional solid propellants will not be extinguished immediately after the electric current ceases, thereby reducing the control accuracy. Second, solid non-energetic propellants do not provide any propulsion of their own, since the main portion of the propulsion is generated by the acceleration of the gas generation ions formed from the electrical energy source. In some cases, it would be beneficial to generate the propulsion directly from the gas generated by the chemical combustion of the propellant. To date, there is no gas, solid or liquid phase propellant that can provide a dual-purpose propulsion system,
    5/25 providing chemical propulsion for faster movement and damage prevention combined with the potential for high specific, low propulsion applications.
    [009] One of the existing electrically controlled propellants comprises a binder, an oxidizer and a cross-linking agent. It has been found that boric acid (the crosslinking agent as a physical property enhancing additive) interacts physically and chemically with the high molecular binder used to produce the propellant, thereby enhancing the ability of the composition to resist combustion without melting. The propellant may also include 5-amino tetrazole (5-ATZ) as a stability-enhancing additive. The propellant binder can include polyvinyl alcohol (PVA) and / or the polyvinyl alcohol / polyvinyl amine nitrate (PVA / PVAN) copolymer. However, sustainable combustion at pressures below 1.38 MPa (200 psi) without the application of continuous electrical input is not normally achieved with the use of the propellant. In addition, burning rates at pressures above 1.38 MPa (200 psi) (at which propellants would sustain combustion) are lower than conventional solid composite propellants.
    [010] Another existing, electrically controlled propellant comprises an ionomer oxidizing polymer-based binder, an oxidant mixture that includes at least one oxidant salt and at least one eutectic material and a mobile phase comprising at least one ionic liquid . The PVAN polymer in the propellant can be medium (> 100,000) to high molecular weight (<1,000,000). The propellant can also include controlled crosslinking of the polymer through the use of
    6/25 epoxy resins, the use of a moisture barrier coating and the addition of combustible additives, such as chromium III and polyethylene glycol polymer. However, under certain circumstances, the propellant may melt or soften during combustion, thus decreasing its effectiveness. More particularly, fusion can impair the propellant's ability to be used in situations where the propellant needs to be ignited and extinguished multiple times. In addition, the liquid phase of the propellants in this application has sufficient volatility to slowly evaporate from the surface of the propellant, making its application unsuitable for use in the vacuum of space.
    [011] Another existing composition has the capacity to produce both solid propellant grains, as well as monopropellants in gel and liquid, all being electronically flammable and with sustainable combustion capacity controlled at ambient pressure. Applications for the compositions include, among other applications, use in small micropropellers, solid propellant grains with a large firing core, charges of explosives designed for military application and monopropellants in liquid and gel that can be pumped or explosive for military or commercial mining or oil and gas recovery. In alternative embodiments, the above compositions may also incorporate a nitrate polymer, burn rate modifiers and / or metal fuel (s). The formulation of high power electronic propulsion (HiPEP) makes it possible to ignite and sustain combustion under ambient and vacuum conditions without continuous electrical energy, while providing faster burning rates.
    7/25 [012] There are several other pyrotechnic compositions that include metastable intermolecular composites (MICs), which provide liquid oxidizers instead of traditional solvents, thereby eliminating the need for solvent extraction. The liquid oxidizer serves as a medium in which the 3D nanostructure formed by the crosslinked polymer (PVA) is suspended and cultivated. As a consequence, the 3D structure traps the liquid oxidizer, preventing it from evaporating, thus eliminating the need for solvent extraction and preserving the 3D nanostructure shape. In addition, the liquid oxidant matrix produced provides a mechanism through which ignition and combustion can be controlled. The combustion rate of the material can be adjusted / accelerated by adjusting the amount of electrical power supply and can even be extinguished by completely removing the electrical power supply. The repeated on / off operation to ignite / extinguish is possible through repeated application and removal of the electric current.
    [013] While the propellants revealed above provide many advantages, such as the ability to electrically control both the operation of inflating and extinguishing propellants, as well as multiple controlled cycles of initiation and extinction, these electrically controlled propellants (ECPs) may still be improved. Specifically, the previously revealed ECPs can be improved through selective formulation changes, the result of which is that propellants take on liquid form.
    [014] Based on the arguments mentioned above, there is a clear need for a liquid composition that can be started and controlled electrically. Such
    The necessary composition would have the ability to electrically control both the igniting and extinguishing propellant operations, as well as providing multiple controlled cycles of initiation and extinction. The liquid composition would comprise additives that act as viscosity modifiers for selective adjustment of viscosity and flow characteristics (rheology). The additives would provide enhanced chemical, ballistic, rheological and conductive properties, as well as better storage stability or use at high temperatures. In addition, the additives would sequester contaminants in transition metals that could destabilize the liquid composition, resulting in unwanted gas release or premature decomposition and increase hazard characteristics such as sensitivity to impact or friction. In addition, the additives would provide a route to introduce non-polar compounds to the liquid composition, usually polar, which gives desirable burning speeds, improved ignition capacity, flame spread, gas output and other benefits that would otherwise would not be possible due to immiscible behavior. Electrical ignition, combustion adjustment through power controls, modulation of gas generation quantities through liquid flow control techniques, all of these capabilities exist to develop the science of propulsion performance, either alone or in combination, that accomplish this without combustion catalysts or pyrotechnic ignitors used separately to assist in ignition or combustion in a permanent state of liquid propellants. Finally, the liquid composition would allow the addition of nano-engineered fuel additives (particulate modifiers)
    9/25 to achieve very high burning speeds and other aspects of energy monitoring for use in gas generators or propellants. The present modality overcomes the gaps of the prior art in reaching such essential objectives.
    SUMMARY OF THE INVENTION [015] In order to minimize the limitations found in the prior art and to minimize other limitations that will become evident upon reading the specification, the preferred embodiment of the present invention provides electrically controlled and initiated liquid compositions, be they the same propellants, explosives, gas generators or pyrotechnics.
    [016] The present invention discloses a liquid propellant composition, which produces gas and is conductive of electricity that can be ignited and controlled by the application of electrical energy of ideal voltage or current. That is, passing electric current at ideal voltages (typically 200 to 600V, 10 to 100 mA) through the propellant causes ignition / combustion to occur, thereby avoiding the need for pyrotechnic ignition of the propellant or the use combustion aids, such as catalysts to generate hot gases or combustion
    sustainable needed. THE present invention reveals an variety of improvements what intensify at properties chemical and ballistics or an combination of me smas, of an class of Forms of liquid electrically controlled . THE
    liquid composition provides electrical control of both the ignition and extinction of the propellant, as well as providing multiple controlled cycles of initiation and extinction.
    [017] The present invention describes a class of
    10/25 liquid compositions (whether propellants, explosives, gas generators or pyrotechnics) that enhance the previously disclosed electrically controlled or initiated solid compositions (ECPs). The propellants disclosed in this document can be used to stimulate the production of subsurface oil or gas and as a substitute for conventional explosives for mining purposes, while maintaining the usefulness of the applications previously revealed in electrically controlled propellants for chemical propulsion.
    [018] Other improvements provided by compositions in the liquid phase of matter include controllable flow through pipes or tubes of tanks, reservoirs or other containers through metering valves, followed by ignition or combustion modulation when stimulated by electrified contacts (electrodes). The electrodes can be energized when the liquid composition is static or in contact, or moving through flow while it is still in contact with measurement holes that also function as electrode surfaces. Additionally, electrically conductive propellant flow currents can be initiated when directed to impact opposing load resources of models in chambers, rocket engines or combustion devices that generate gas, whether they are contained for direct gas output or not. . Propellant chains that flow from a single composition, when they allow to receive opposite electrical charges through separate channels, can also be directed to collide with the other, allowing the ignition and combustion of combustion droplets, similar to the operation of rocket engines that use hypergolic pairs.
    11/25
    These characteristics allow energy monitoring of the hot gas outlet for propulsive effects, pressurization or other benefits of products based on gas phase outlet, especially when combined with other aspects of these electronically controlled liquid compositions, specifically flow control with use. of valves or devices for measuring or controlling power through electrodes in contact with the propellant, either statically or dynamically.
    [019] According to one aspect of the present invention, the electrically initiated and controlled liquid composition typically comprises an oxidizer, soluble fuel additive (s) and other optional additives to enhance chemical or ballistic properties, or a combination of them. In this context, chemical optimization is intended to allow optimal combustion through electrodes by modifying the ingredients and additives to maximize the utility of the invention. According to an embodiment of the present invention, the oxidant is hydroxylammonium nitrate or hydroxylamine nitrate (HAN). Preferred fuel additives include soluble CHO compounds, such as cyclo dextrins, other complex saccharides such as xylitol, as an example, and hydroxyl substituted cellulosics such as, but not limited to, hydroxy ethyl and hydroxy propyl cellulose. Optional additives can include stabilizers to enhance thermal stability, scavengers to remove contaminants from transition metals, and combustion enhancers. Buffers and scavengers of heavy metals or complex agents can be used in combination to achieve the highest degree of
    12/25 thermal stability. Additional co-oxidants can be added to the liquid composition to stabilize the liquid oxidant and further lower the freezing point. Preferred co-oxidants include ammonium nitrate, organosubstituted amine nitrates such as methyl ammonium nitrate and various soluble homologues in the HAN liquid oxidant matrix. Additionally, additives can be included in the formulations, according to the known technology.
    [020] A first objective of the present invention is to provide a variety of additives that enhance the properties of electronically controlled propellants, such as liquid compositions.
    [021] A second objective of the present invention is to provide a liquid composition that has the ability to flow through pipes or tubes from tanks, reservoirs or other containers, through metering valves, followed by ignition or combustion modulation when stimulated by electrodes, during the flow movement or when static.
    [022] A third objective of the present invention is to provide a selective adjustment of the viscosity of flow characteristics that affect the currents when sprayed through injectors into the combustion chambers, or in atomization of liquid propellant-filled droplets, of the liquid composition.
    [023] Another objective of the present invention is to provide high initial temperatures of the exothermic reaction of the propellant which produces formulations of reduced hazards to inadvertent ignition from heat.
    [024] An additional objective of the present invention is
    13/25 provide the ability to sequester or retain contaminants in transition metals, which inadvertently shorten the storage life of electrical formulations.
    [025] An additional objective of the present invention is to provide a route for introducing non-polar compounds into the generally polar liquid compositions through inclusion complexes in complex saccharides such as cyclo dextrins.
    [026] A final objective of the present invention is to provide high burning speeds without the addition of metallic destabilizer or metalloid additives.
    [027] These and other advantages and features of the present invention are specifically described in order to make the present invention understandable to those skilled in the art.
    BRIEF DESCRIPTION OF THE FIGURES [028] The elements in the Figures were not necessarily represented in scale in order to enhance their clarity and improve the understanding of the various elements and modalities of the invention. Additionally, the elements that are known to be common and well understood by those in the sector are not portrayed in order to provide a clear view of the various modalities of the invention, therefore, the drawings are generalized in form, aiming at clarity and conciseness.
    [029] Figure 1 shows an example of a liquid composition that has been found to be effective for oil and gas, as well as for fracturing, when demonstrated in small-scale capillarities that simulate subsurface passages of 70 microns or less, and provides a line composition
    14/25 basis for related applications in chemical propulsion, pyrotechnics, commercial explosives, when intentionally formulated for specific applications in these areas;
    [030] Figures 2A shows the molecular structure of a type of cyclo dextrin (cyclic saccharides) according to the present invention;
    [031] The Figures 2B shows the structure molecular in one of the types of dextrin cycle (saccharides cyclical) in wake up with the present invention; [032] The Figures 2C shows the structure molecular in one of the types of dextrin cycle (saccharides cyclical) in wake up with the present invention;
    [033] Figure 2D shows a table of properties of the three main types of cycle dextrins (cyclic saccharides); and [034] Figure 3 is a differential scanning calorimetry (DSC) plane showing Heat Flow in W / g on the Y axis and Temperature in ° C on the X axis.
    DETAILED DESCRIPTION OF THE FIGURES [035] In the following discussion, which refers to the numerous modalities and applications of the present invention, reference is made to the accompanying drawings that form a part of it, and which are shown by way of illustration of specific modalities in which the invention can be practiced. It should be understood that other modalities can be used and modifications can be made without departing from the scope of the present invention.
    [036] Several inventive features are described below that can each be used independently of one another.
    15/25 other, or in combination with different resources. However, any individual feature of the invention cannot refer to any of the problems discussed above or only refer to one of the problems discussed above. In addition, one or more of the issues discussed above may not be fully addressed by any of the resources described above.
    [037] The present invention is an electrically controlled and initiated liquid composition comprising an oxidizer and at least one fuel additive. The electronically controlled liquid composition (be it propellants, explosives, gas generators or pyrotechnics) can be ignited and controlled by applying electrical voltage. The liquid composition further comprises a variety of additives that enhance chemical or ballistic properties or a combination of both.
    [038] Figure 1 shows an example of a liquid composition that has been found to be effective for oil and gas, as well as for fracturing, when demonstrated in small-scale capillarities that simulate subsurface passages of 70 microns or smaller. The liquid composition provides a baseline composition for related applications in chemical propulsion, pyrotechnics, commercial explosives, when intentionally formulated for specific applications in these areas. In preferred embodiments, the oxidant used is hydroxylammonium nitrate (NH3OHNO3) or hydroxylamine nitrate (HAN). The electrically initiated and controlled liquid composition typically comprises hydroxylammonium nitrate (NH3OHNO3) of 65 to 79 weight percent, soluble fuel additive in 15 to 30 percent, in
    16/25 weight, and various additives to enhance chemical and ballistic properties.
    [039] Stabilizers can be added to the liquid composition to enhance thermal stability and scavengers can be included to remove contaminants from transition metals such as iron, copper and nickel. Buffers and scavengers of heavy metals or complex agents can be added in combination to achieve the highest degree of thermal stability in the liquid composition. Proper selection of these additives will increase the peak exothermic temperature by 100 degrees F or more. Preferred buffers are ammonium dihydrogen phosphates or organic amines such as ΝΗ 4 Η 2 ΡΟ 4 , or monohydrogen diorganic phosphates or diamons, such as (ΝΗ 4 ) 2 ΗΡΟ 4 although other suitable buffers can also be used. Preferred sequestering agents are 2,2'-Bipyridyl and its substituted ring derivatives. Additionally, additives can be included in the liquid composition, according to known technology.
    [040] The liquid composition comprises a stabilizer and scavenger added from 0.1 to 1.0 weight percent. In the preferred embodiment, the stabilizer and scavenger is 2,2'-Bipyridyl (CioHgN 2 ). As a stabilizer, 2,2'-Bipyridyl acts as a base that can neutralize any acid generated due to HAN decomposition. As a sequestrant, 2,2'-Bipyridyl is an effective chelating agent that forms complexes with many transition metals. The liquid composition further comprises a buffer added in 0.1 to 1.0 weight percent. In the preferred embodiment, the buffer is ammonium dihydrogen phosphate or monoammonium phosphate
    17/25 (NH4H2PO4), which acts as a buffer composed of any nitric acid generated due to HAN decomposition. Ammonium dihydrogen phosphate and 2,2'-bipyridyl stabilize the HAN liquid oxidant. The liquid composition also comprises water as an aid to the process. Water acts as a processing aid and desensitizes the liquid composition from 1 to 3 percent by weight.
    [041] The liquid composition comprises soluble additive (s) for fuel (s) of 15 to 30 percent by weight. The fuel additive is selected from the group consisting of cyclic saccharides that include a-cyclo dextrin, β-cyclo dextrin and γ-cyclo dextrin; complex sugars / polysaccharides that include xylose, sorbitol, amylose, amylopectin and plant-based starches; and polyhydroxyl compounds that include hydroxyethylcellulose, hydroxypropylcellulose and methyl hydroxyethylcellulose soluble in the liquid HAN oxidizing matrix.
    [042] Polyhydroxyl compounds, such as cellulose compounds with ethyl hydroxyl, hydroxypropyl-, methyl hydroxy ethyl- and related substitutions and cellulosic esters, such as methyl hydroxy ethyl cellulose (MHEC) can be added to the liquid composition. The polyhydroxyl compounds act as viscosity modifiers for selective adjustment of viscosity and flow characteristics (that is, rheology) of the composition. The modification of viscosity allows beneficial and superior application of the liquid composition in specific places, such as subsurface such as electrically initiated fracture fluids or in devices that have flow capabilities through electrodes. In the preferential modality, there is a benefit in adjusting the
    18/25
    viscosity and characteristics of flow, rheology gives formulation, nature hydraulic and capacity to keep or suspend additions particulates without separation or
    classification, when selected.
    [043] Cyclic saccharides (cycle dextrins) can be added to the liquid composition. The molecular structures of numerous, such as cyclo dextrins, are shown in Figures 2A to 2C. These materials are formulated in a wide percentage range that allows the ability to customize the performance of liquid compositions, based on their solubility, from 0 to more than 25 percent, by weight, in liquid oxidizer, an important aspect of utility in electric liquid compositions. These compounds are highly soluble in the liquid HAN oxidizing matrix and provide high shelf life and stability. In addition, the cycle dextrins can sequester unwanted contaminants, such as transition metal ions that could destabilize the liquid composition, resulting in an unwanted gas release or premature decomposition and increase hazard characteristics such as sensitivity to impact or friction. The addition of these cyclic saccharides (cycle dextrins) beneficially increases the initial temperature of the propellant's exothermic reaction. Cyclic saccharides can be a-cyclo dextrin, β-cyclo dextrin or γ-cyclo dextrin, with or without substituents, which add to the mechanical or ballistic performance. Figure 2D shows a table of properties of the three main types of cycle dextrins.
    [044] With reference to Figures 2A to 2C, the cycle dextrins consist of units of glycopyranose-a-D
    19/25 cross-linked (α-1,4) and contains some central lipophilic activity and a hydrophilic outer surface. The dextrin cycle a, β and γ consists of six, seven and eight units of glycopyranose, respectively. Due to the conformation of the glycopyranose units chain, the cyclo dextrins are formed as a truncated cone with secondary hydroxyl groups extending from a wider edge and the primary hydroxyl groups from the narrower edge. The central cavity is lined with skeletal carbons and ethereal oxygen from the glucose residues, which gives it a lipophilic character. All three cycle dextrins have similar structures (ie, connection lengths and orientations) separate from the structural needs to provide a different number of glucose residues. The cavities have different diameters, depending on the number of glucose units. The depth of the side flap is the same (at about 0.8 nm) for all three cycle dextrins. Cycle dextrin rings are unsympathetic with the widest flap showing groups 2 and 3-OH and the narrowest flap showing groups 6-OH on its flexible arm. These polar groups are on the outer side of the molecular cavity, while the inner surface is non-polar. Therefore, the opposite polarity cycle dextrin molecules have the ability to form inclusion complexes with non-polar molecules due to the unique nature conferred by their structure.
    [045] As shown in Figures 2A to 2C, the 3D structures of cyclic saccharides (cycle dextrins) provide the ability to sequester or retain transition metal contaminants, and provide the mentioned benefits of improved ballistic, rheological and conduction properties
    20/25 with the use of its cavity structure to form inclusion compounds, as well as greater storage stability or use at high temperatures. The 3D structure of cyclic saccharides (cycle dextrins) also provides a route to introduce non-polar compounds to the generally polar liquid composition. Such non-polar compounds can comprise additive benefits that provide desirable burning speeds, improved ignition capacity, flame propagation, gas output and other benefits that would otherwise not be possible due to immiscible behavior. Preferably, cyclic saccharides (cyclo dextrins) are added, at approximately 30 weight percent, to the liquid composition.
    [046] Complex sugars or polysaccharides, such as, but not limited to, xylose, sorbitol, amylose, amylopectin, and which include the aforementioned cycle dextrins, and plant-based starches, can be added to the liquid composition. When added between 5 percent to approximately 25 percent by weight, these compounds provide burning speeds from 152.4 to 1524 centimeters per minute (1 to 10 ips - inches per second) at 0.01 MPa (1000 psi ) while remaining highly soluble in mixtures of liquid ionic oxidant and HAN. Currently, such burning speeds are unattainable without the addition of metalloid additives or metallic destabilizers.
    [047] The liquid composition comprises a processing aid surfactant of 0.1 to 0.5 weight percent. In the preferred embodiment, the surfactant is n-octanol.
    [048] The net composition also comprises a
    21/25 sequestering combustion intensifier and stabilizer added by 1-3 weight percent. The combustion enhancer may be a polynitrogen compound selected from the group consisting of, but not limited to, 5 amino tetrazole (5-ATZ) and 1,2,4-triazole. Polynitrogen compounds such as, but not limited to, 1,2,4-triazole and 5-amino tetrazole or substituted triazoles, and tetrazools can be added to the liquid composition to increase stability and initial temperatures. Preferably, the polynitrogen compounds are added in 0.01 to 5 weight percent, but can be added in greater or lesser amounts. It was observed that the addition of 1,2,4 triazole changes the initial temperature from 172 ° C to 213 ° C. A plan for the initial temperature change due to the addition of 1,2,4-triazole is shown in Figure 3. 5-amino tetrazole is amphoteric in nature and acts as a buffer to absorb both acid and base to maintain the proper acidity of the oxidant , and its stability to readily form insoluble complexes with heavy metals effectively eliminates their destabilizing effects.
    [049] Figure 3 shows a differential scanning calorimetry (DSC) showing Heat Flow in W / g on the geometric Y axis and Temperature in ° C on the geometric X axis. The differential scanning calorimetry (DSC) plane represents the heat rate vs. temperature produced at a peak exothermic temperature, whose initial and peak temperatures were recorded as indications of thermal stability of formulations containing different combustion intensifiers. The scheme shows, preferably, the location of increasing low peak to
    22/25 higher temperatures (initial exothermic temperatures) of substituted nitrogen heterocyclic compounds (polynitrogen compounds) such as triazoles and tetrazoles in the liquid composition. The progression, from low temperature to high preferred temperatures, is liquid oxidizer S-HAN (stabilized hydroxylammonium nitrate) at 163.88 ° C, liquid oxidizer S-HAN enhanced at 183.81 ° C, liquid oxidizer with 5-amino stabilizer tetrazole at 210.06 ° C, and liquid oxidizer with 1,2,4-triazole stabilizer at 215.07 ° C. Higher initial temperatures indicate improved stability of liquid oxidant solutions.
    [050] The liquid composition comprises a co-oxidant added from 2 to 7 weight percent. The co-oxidant is selected from the group consisting of, but not limited to, ammonium nitrate, methyl ammonium nitrate, ethyl hydroxide formate and other soluble ingredients favorable to oxygen balance. These compounds were found to lower the HAN crystallization temperature. Additional liquid ionic co-oxidants can be added to the liquid composition to stabilize the liquid composition and further depress the freezing point. The liquid ionic co-oxidant may comprise, but is not limited to, 0.01 to 20 weight percent ethyl hydroxide formate, the addition of which lowers the freezing point of the liquid composition to less than -70 ° C. Additional soluble salts can be added to the liquid composition to lower freezing points and add additional benefits, such as improvements in ignition response, gas output and rapid combustion propagation in passages
    23/25 less than 100 microns in any dimension, such as monomethylammonium nitrate, which has been shown to be soluble up to 50 percent by weight or greater in electrically ignited liquid compositions.
    [051] Nano-engineered fuel additives (particulate modifiers) can be added to the liquid composition to achieve very high burning speeds. Such compounds comprise Al, B, Si, or Ti. With these combustible additives, the liquid composition burns more than 152.4 to 1524 cm / m (1 ips to 10 ips) faster than 3.45 MPa at 10.34 MPa (500 to 1500 psi). Generally, additives have an approximate diameter of 100 nanometers or less. Refractory nano-designed materials, such as SiO2, TiO 2 , zeolites and similar high melting point compounds can also be included to provide heterogeneous catalytic behavior to enhance combustion or customize combustion products in the liquid composition. Levels of these nano-engineered fuel additives are effective at low concentrations of less than 5 percent, preferably.
    [052] In the preferred embodiment of the present invention, the electrically initiated and controlled liquid composition typically comprises 65 to 7 9 percent by weight hydroxylammonium nitrate (HAN), soluble additive (s) for fuel (s) ) by 15 to 30 weight percent, and optional additives such as 2.2'Bipyridyl (stabilizer and scavenger) by 0.1 to 1.0 weight percent, ammonium dihydrogen phosphate (buffer) at 0, 1 to 1.0 percent, by weight, water (desensitizer, production artifact) in 1 to 3 percent, by weight, n-octanol
    24/25 (surfactant) in 0.1 to 0.5 weight percent, 5-amino tetrazole (combustion intensifier) in 1 to 3 weight percent, 1,2,4-triazole (or substituted triazoles and tetrazools, such as combustion enhancers and stabilizers) by 1 to 3 weight percent, and a co-oxidant (such as ammonium nitrate or other soluble ingredients favorable to oxygen balance) by 2 to 7 weight percent . In addition, additives can be included in the composition, according to known technology.
    [053] The liquid composition has several applications, such as stimulating the production of oil or subsurface gas wells, a substitute for conventional explosives for mining purposes, in chemical propulsion and pyrotechnics. The liquid composition improves the solid compositions initiated or controlled electrically previously revealed through the selective formulation modifications, resulting in the liquid form of the propellants. The liquid phase of the matter allows the flow through pipes or tubes of tanks, reservoirs or other containers, and through measurement valves, followed by ignition or combustion modulation when stimulated by electrified contacts (electrodes). The electrodes can be energized when the liquid composition is static or in contact, or moving through flow while it is still in contact with measurement holes that also function as electrode surfaces. The electrodes can be, without limitation, foams, rods, wires, fibers, conductively coated particles, mesh structures or woven structures. In one embodiment while the electrode is in contact with the gas generation composition, an electrical voltage is applied to said composition through
    25/25 of the electrode.
    [054] The above description of the preferred embodiment of the present invention has been presented for purposes of illustration and description. It is not intended to deepen or limit the invention to the precise form disclosed. Many modifications and variations are possible in light of the above teachings. It is intended, therefore, that the scope of the present invention is not limited by this detailed description, but by the claims and equivalents to the claims attached to this document.
    权利要求:
    Claims (16)
    [1]
    1. METHOD FOR GAS GENERATION CONTROL, the method characterized by understanding the steps of:
    The. provide an electrically controlled gas generation composition comprising:
    1. 65 to 79 weight percent oxidant;
    ii. fuel additive of 15 to 30 percent by weight; and iii. a stabilizer and scavenger from 0.1 to 1.0 weight percent;
    B. providing an electrode in contact with said gas generation composition; and
    ç. applying an electrical voltage to said gas generation composition through said electrode.
    [2]
    2. METHOD, according to claim 1, characterized by the oxidant being hydroxylammonium nitrate (HAN).
    [3]
    3. METHOD, according to claim 1, characterized in that the fuel additive is selected from the group consisting of cyclic saccharides, complex sugars / polysaccharides and polyhydroxyl compounds soluble in a liquid HAN oxidizing matrix.
    [4]
    METHOD, according to claim 1, characterized in that the stabilizer and scavenger are 2,2'bipyridine.
    [5]
    5. METHOD according to claim 1, characterized in that the gas generation composition also comprises a buffer of 0.1 to 1.0 weight percent.
    [6]
    6. METHOD, according to claim 5, characterized in that the buffer is ammonium dihydrogen phosphate.
    2/5
    METHOD, according to claim 1, characterized in that said gas generation composition further comprises a desensitizer of 1 to 3 weight percent.
    [7]
    8. METHOD, according to claim 7, characterized in that said desensitizer is water.
    [8]
    9. METHOD, according to claim 1, characterized in that said gas generation composition also comprises a surfactant of 0.1 to 0.5 weight percent.
    [9]
    10. METHOD, according to claim 9, characterized by the surfactant being n-octanol.
    [10]
    11. METHOD according to claim 1, characterized in that said gas generation composition also comprises a combustion intensifier of 1 to 3 weight percent.
    [11]
    12. METHOD according to claim 11, characterized in that the combustion intensifier is a polynitrogen compound selected from the group consisting of 5-aminotetrazole and 1,2,4-triazole.
    [12]
    13. METHOD, according to claim 1, characterized in that said gas generation composition further comprises a co-oxidant of 2 to 7 weight percent.
    [13]
    14. METHOD, according to claim 13, characterized by the co-oxidant being selected from the group consisting of ammonium nitrate methylammonium nitrate and ethylammonium hydroxide formate.
    [14]
    15.
    COMPOSITION
    NET STARTED AND
    SUBSIDIARY
    ELECTRICALLY, characterized by understanding:
    3/5
    The. Oxidizer from 65 to 79 percent by weight;
    B. Stabilizer and sequesterer by 0.1 to 1.0 percent by weight;
    ç. Buffer from 0.1 to 1.0 weight percent;
    d. Desensitizer from 1 to 3 weight percent;
    and. Fuel additive of 15 to 30 percent by weight;
    f. Surfactant from 0.1 to 0.5 weight percent;
    g. Combustion intensifier by 1 to 3 percent by weight; and
    H. Co-oxidant 2 to 7 weight percent.
    [15]
    16. NET COMPOSITION, according to claim 15, characterized in that the oxidant is hydroxylammonium nitrate (HAN).
    [16]
    17. NET COMPOSITION, according to claim 15, characterized in that the fuel additive is selected from the group consisting of cyclic saccharides, which include α-cycle dextrin, β-cycle dextrin and γcycle dextrin; complex sugars / polysaccharides that include xylose, sorbitol, amylose, amylopectin and plant-based starches; and polyhydroxyl compounds that include hydroxyethylcellulose, hydroxypropylcellulose and methylhydroxyethylcellulose.
    18. NET COMPOSITION, in wake up with The claim 15, characterized fur stabilizer and kidnapper be 2,2'-bipyridine. 19. NET COMPOSITION, in wake up with The claim 15, characterized by plug be dihydrogen ammonium. 20. NET COMPOSITION, in wake up with The
    4/5
    claim 15, characterized by the desensitizer being
    Water .
    21. NET COMPOSITION, according to claim 15, characterized by the fact that the surfactant
    is n-octanol.
    22. NET COMPOSITION, according to claim 15, characterized by the
    combustion is a polynitrogen compound selected from the group consisting of 5-aminotetrazole and 1,2,4 triazole.
    23. NET COMPOSITION, according to claim 15, characterized by the co-oxidant being
    selected from the group consisting of ammonium nitrate, methylammonium nitrate and hydroxyethylammonium formate.
    24. NET COMPOSITION INITIATED AND CONTROLLED ELECTRICALLY, characterized by understanding: The. hydroxylammonium nitrate 65 to 79 per
    percent by weight;
    B. 2,2'-bipyridine from 0.1 to 1.0 percent, in
    Weight;
    ç. ammonium dihydrogen phosphate from 0.1 to 1.0 percent in Weight; d. 1 to 3 percent water by weight; and. Fuel additive by 15 to 30 percent,
    by weight;
    f. n-octanol from 0.1 to 0.5 weight percent; g. 5-aminotetrazole from 1 to 3 weight percent; H. 1,2,4-triazole from 1 to 3 weight percent; and i. Co-oxidant of 2 to 7 weight percent.
    5/5
    25. NET COMPOSITION, according to claim 24, characterized in that the fuel additive is selected from the group consisting of cyclic saccharides that include α-cyclo dextrin, β-cyclo dextrin and γ-cyclo dextrin; complex sugars / polysaccharides that include xylose, sorbitol, amylose, amylopectin and plant-based starches; and polyhydroxyl compounds that include hydroxyethylcellulose, hydroxypropylcellulose and methyl hydroxyethylcellulose.
    26. COMPOSITION LIQUID, in a deal with The claim 24, characterized fur co-oxidant to be selected a from the group that consists of nitrate in ammonium, nitrate methylammonium and formate in hydroxyethylammonium. 27. COMPOSITION LIQUID, in a deal with The
    claim 24, characterized by also comprising nano-designed particulate modifiers, selected from the group consisting of aluminum, boron, silicon and tin.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112015009169A2|2019-12-10|method for gas generation control; and electrically initiated and controlled net composition
    CA2762065C|2016-08-23|Family of modifiable high performance electrically controlled propellants and explosives
    Zhang et al.2013|Ionic liquid propellants: future fuels for space propulsion
    Ahmad et al.2014|Laser ignition of energetic materials
    Zhang et al.2011|Ionic liquids as hypergolic fuels
    Kim et al.2016|Micro-and nanoscale energetic materials as effective heat energy sources for enhanced gas generators
    US9447672B2|2016-09-20|Method and apparatus for ballistic tailoring of propellant structures and operation thereof for downhole stimulation
    US8317953B2|2012-11-27|Family of metastable intermolecular composites utilizing energetic liquid oxidizers with nanoparticle fuels in sol-gel polymer network
    Kumar2018|An overview on properties, thermal decomposition, and combustion behavior of ADN and ADN based solid propellants
    Liu2015|Liquid explosives
    Jin et al.2014|Combustion Effects of Nitrofulleropyrrolidine on RDX‐CMDB Propellants
    Ahmad et al.2009|Laser‐Induced Deflagration of Unconfined HMX–The Effect of Energetic Binders
    Shoaib et al.2018|Effect of alcohol carbon chain on enthalpy of combustion and ignition delay time for gelled hypergolic propellant system
    Serushkin et al.2013|Combustion mechanism of triaminoguanidine nitrate
    CN107108389B|2019-12-24|O-chlorobenzylidene malononitrile | type self-igniting pyrotechnic composition with low ignition temperature
    Kumar2018|Defence Technology
    Sasidharan et al.2018|Combustion Studies of 4‐Nitramino‐1, 2, 4‐Triazole | and Its Salts: High Impulse Nitrogenous Fuels for Propellant Composite Materials
    Kumar2020|An overview over dinitramide anion and compounds based on it
    DÎRLOMAN et al.2020|Eco-Oxidizers for Composite Propellants: Ammonium Nitrate and Ammonium Dinitramide
    Liu2015|Liquid Explosive Mixtures
    RU2531293C1|2014-10-20|Pyrotechnic composition
    Liu2015|Formulation Design of Liquid Explosives
    Boyer et al.2002|Combustion characteristics of non-toxic non-hypergolic bi-propellants
    Fischer2012|Nitrogen-rich high energy density materials: synthesis, characterization and testing
    Liu2015|Explosion Features of Liquid Explosive Materials
    同族专利:
    公开号 | 公开日
    AR093776A1|2015-06-24|
    US9182207B2|2015-11-10|
    US20140109788A1|2014-04-24|
    CN105008311A|2015-10-28|
    AU2013375231B2|2017-04-20|
    EP2911998A4|2016-08-10|
    US9534880B2|2017-01-03|
    CA2888922C|2019-09-10|
    US20150266791A1|2015-09-24|
    EP2911998A1|2015-09-02|
    AU2013375231A1|2015-04-30|
    RU2015116947A|2016-12-20|
    US9328034B2|2016-05-03|
    US20160245633A1|2016-08-25|
    CA2888922A1|2014-07-31|
    WO2014116311A1|2014-07-31|
    RU2018101255A|2019-02-22|
    RU2643551C2|2018-02-02|
    ZA201503546B|2016-08-31|
    RU2018101255A3|2021-02-12|
    EP2911998B1|2021-06-02|
    MX362926B|2019-02-26|
    ZA201507800B|2017-08-30|
    MX2015005108A|2015-11-16|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3214305A|1952-06-04|1965-10-26|Standard Oil Co|Solid propellant|
    US3698969A|1965-09-10|1972-10-17|Thiokol Chemical Corp|Solid stabilized hydrazinium diperchlorate propellant|
    GB1153680A|1966-12-06|1969-05-29|Canadian Ind|Explosive Compositions|
    US5223057A|1969-03-28|1993-06-29|The United States Of America As Represented By The Secretary Of The Navy|Monopropellant aqueous hydroxyl ammonium nitrate/fuel|
    GB2293820B|1988-12-20|1996-07-03|Aerojet General Co|Liquid oxidizer compositions and their use in energetic formulations|
    US6254705B1|1999-02-26|2001-07-03|Svenska Rymdaktiebolaget|Liquid propellant|
    US6509473B1|2000-10-16|2003-01-21|The United States Of America As Represented By The Secretary Of The Air Force|Energetic triazolium salts|
    RU2209334C1|2001-11-22|2003-07-27|Военный инженерно-космический университет им. А.Ф. Можайского|Liquid-propellend thruster|
    JP4102183B2|2002-12-27|2008-06-18|株式会社東芝|battery|
    US8857342B2|2005-01-10|2014-10-14|Ncc Nano, Llc|NANO-enhanced kinetic energy particles|
    US8317952B2|2006-04-13|2012-11-27|Digital Solid State Propulsion, Llc|High performance electrically controlled solution solid propellant|
    JP5110256B2|2006-12-12|2012-12-26|独立行政法人宇宙航空研究開発機構|Gas generant composition|
    AU2008204725A1|2007-01-10|2008-07-17|Newcastle Innovation Limited|Methods for gassing explosives especially at low temperatures|
    WO2010039290A1|2008-05-16|2010-04-08|Digital Solid State Propulsion, Llc|Family of modifiable high performance electrically controlled propellants and explosives|US9382168B2|2012-08-27|2016-07-05|Digital Solid State Propulsion Llc|Solid electrically controlled propellants|
    US8950329B2|2012-12-24|2015-02-10|Raytheon Company|Electrically operated propellants|
    US9457761B2|2014-05-28|2016-10-04|Raytheon Company|Electrically controlled variable force deployment airbag and inflation|
    US10508538B2|2014-12-01|2019-12-17|Evolution Engineering Inc.|Fluid pressure pulse generator for a downhole telemetry tool|
    US20170057883A1|2015-08-28|2017-03-02|The United States Government As Represented By The Secretary Of The Army|Combustible Triazine Combinations|
    CN106699489B|2015-11-12|2019-01-11|比亚迪股份有限公司|A kind of gas generant composition in accordance for air bag and preparation method thereof and a kind of gas generator for automobile safety gas bag|
    CN106365935A|2016-08-26|2017-02-01|湖北航天化学技术研究所|High-strength electric-control solid propellant|
    US11124464B2|2016-09-09|2021-09-21|Terves, Llc|High density hybrid rocket motor|
    CN106495972A|2016-10-21|2017-03-15|重庆大学|A kind of electric ignition solid propellant of fuel-rich containing aluminum and preparation method thereof|
    CN106565390A|2016-10-21|2017-04-19|重庆大学|Electronically-controlled combustion solid propellant and preparation method thereof|
    CN106478323A|2016-10-21|2017-03-08|重庆大学|Automatically controlled solid propellant of a kind of high-performance and preparation method thereof|
    CN106542942A|2016-10-21|2017-03-29|重庆大学|A kind of boracic fuel-rich electric ignition solid propellant and preparation method thereof|
    US11142977B2|2016-10-27|2021-10-12|Halliburton Energy Services, Inc.|Electrically controlled propellant in subterranean operations and equipment|
    CA3046917C|2017-01-23|2021-03-30|Halliburton Energy Services, Inc.|Enhancing complex fracture networks in subterranean formations|
    WO2018136095A1|2017-01-23|2018-07-26|Halliburton Energy Services, Inc.|Fracturing treatments in subterranean formations using electrically controlled propellants|
    US10738582B2|2017-01-23|2020-08-11|Halliburton Energy Services, Inc.|Fracturing treatments in subterranean formation using inorganic cements and electrically controlled propellants|
    CN109851457B|2019-03-22|2021-10-01|湖北航天化学技术研究所|Electrically-controlled solid propellant containing metal fuel and preparation method thereof|
    WO2020197607A1|2019-03-27|2020-10-01|Halliburton Energy Services, Inc.|Enhancing treatment fluid placement in a subterranean formation|
    US11053786B1|2020-01-08|2021-07-06|Halliburton Energy Services, Inc.|Methods for enhancing and maintaining effective permeability of induced fractures|
    法律状态:
    2019-12-17| B15I| Others concerning applications: loss of priority|Free format text: PERDA DA PRIORIDADE US61/718,132 DE 24/10/2012 POR NAO CUMPRIMENTO DE EXIGENCIA REFERENTE A COMPROVACAO DE DIREITO DE PRIORIDADE. |
    2020-03-24| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-09-15| B11B| Dismissal acc. art. 36, par 1 of ipl - no reply within 90 days to fullfil the necessary requirements|
    2021-10-13| B350| Update of information on the portal [chapter 15.35 patent gazette]|
    优先权:
    申请号 | 申请日 | 专利标题
    US201261718132P| true| 2012-10-24|2012-10-24|
    US14/040,442|US9182207B2|2012-10-24|2013-09-27|Liquid electrically initiated and controlled gas generator composition|
    PCT/US2013/066705|WO2014116311A1|2012-10-24|2013-10-24|Liquid electrically initiated and controlled gas generator composition|
    [返回顶部]