Patent Application
20110194988
The disclosed embodiments relate to the remediation of hydrazine, 1,1-dimethylhydrazine, and/or monomethyl-hydrazine from a hydrazine-contaminated gas. The disclosed embodiments further relate to active chemicals (i.e. dicarbonyl compounds) and absorbent materials for the removal of hydrazine, 1,1-dimethylhydrazine, and/or monomethyl-hydrazine from a hydrazine-contaminated gas. The disclosed embodiments also relate to absorbent materials that can act as support matrices for active chemicals, whether the active chemicals are in solutions, dry powders or granules, or coatings on the absorbent materials. As utilized herein, the term “hydrazine” can refer to all hydrazines listed above (i.e., hydrazine, 1,1-dimethylhydrazine, monomethyl-hydrazine, and/or other hydrazine derivatives in which one nitrogen is an NH2 group).
Numerous industries utilize hydrazine on a daily basis. Highly toxic hydrazine fuels, for example, are respectively utilized by the United States Air Force and NASA as an emergency power source on the F-16 and as rocket propellant. The civilian industry also requires hydrazine in the manufacture of agricultural chemicals and pharmaceuticals, in photography, and also, for example, as an oxygen scavenger to prevent corrosion in boners. Additionally, large volumes of such chemicals are shipped across the highways and rail systems annually, increasing the probability of an accidental spill.
An inadvertent release of hydrazine to the environment can be extremely hazardous due to the mutagenic nature of such chemicals, which can induce tumor growth in human beings years following even a low-level exposure. Hydrazine compounds are classified as suspected human carcinogens and the permissible levels of exposure have been reduced to 10 parts per billion (ppb) over an eight-hour workday. A hydrazine spill remediation process, to be developed, should not only remediate the hydrazine, but also should not generate other hazardous materials. An in-situ processing method involving direct application of the treatment reagent or process to the spill is preferred.
An accident involving a transport trader, for example, may spill four to five thousand gallons of the hydrazine, whereas a catastrophic failure of a fuel storage vessel at a launch facility may release twenty thousand gallons or more of the propellant. For example, a rail car derailment resulting in a release of hydrazine occurred in Southern California on Jul. 28, 1991.
Hydrazine and hydrazine derivatives are readily combustible reducing agents that react violently with oxidizing agents and thus present a serious safety hazard. Hydrazine and hydrazine derivatives are well known components of liquid rocket fuels in conjunction with an oxidizing agent such as dinitrogen tetroxide. Thus, at facilities where liquid-fueled rockets are prepared for flight, there is a particular need to provide reliable and sensitive methods and systems for decontaminating objects such as fighter jets and maintenance equipment thereof, and exposed environments which can become contaminated with hydrazine. Ideally, such hydrazine remediation methods and systems should also have a limited, if negligible, effect on the environment.
Examples of hydrazine neutralization techniques are known. One example of such a technique is disclosed in U.S. Pat. No. 4,804,527, entitled “Method and Composition for Safely Decomposing Hydrazine,” which issued to Tatarchuk, et al. on Feb. 14, 1989. As described in U.S. Pat. No. 4,804,527, hydrazine can be safely rendered harmless by contacting it with a composition comprising cupric oxide on a porous support. Neutralization can be achieved by drawing the hydrazine into the pellet pores where a reduction reaction of cupric oxide takes place. The critical consideration is to avoid flashing or spontaneous thermal decomposition of the hydrazine. Heat of reaction is quenched by the heat capacity of the pellet and water dilution.
The conversion of hydrazine group compounds to stable organic compounds as a result of a reaction with a dicarbonyl-compound like ketoglutaric acid is described in the U.S. Patent Application Publication No, 2004/0024251 by Helvenston, et al. entitled “Methods and Systems for Hydrazine Remediation”. In U.S. Patent Application Publication No, 2004/0024251, which is incorporated herein by reference, the conversion assists in the remediation of the hydrazine group compound from the object. The stable organic compound produced as a result of the reaction between the dicarbonyl-compound and hydrazine group compound can then be treated with a metal catalyst and hydrogen to produce glutamine or a derivative thereof. The compound then becomes yet another non-hazardous material. Such an approach is also described in U.S. Pat. No. 7,074,959, which issued to Helvenston, et al. on Jul. 11, 2006 and which is also incorporated herein by reference in its entirety.
The present invention is a novel application of the reaction between hydrazine and a dicarbonyl compound for remediating spilled hydrazine using a spill pad treated with a dicarbonyl compound.
The following summary of the invention is provided to facilitate an understanding of some of the innovative features unique to the present invention and is not intended to be a full description. A full appreciation of the various aspects of the invention can be gained by taking the entire specification, claims, drawings, and abstract as a whole.
It is, therefore, one aspect of the disclosed embodiments to provide for an apparatus for remediating hydrazine, 1,1-dimethylhydrazine, monomethyl-hydrazine and/or other hydrazine derivatives.
It is, therefore, another aspect of the present invention to provide for an apparatus for remediating spills of hydrazine, 1,1-dimethylhydrazine, monomethyl-hydrazine, and/or other hydrazine derivatives.
The aforementioned aspects of the invention and other objectives and advantages can now be achieved as described herein. An apparatus for remediating hydrazine and a method of manufacturing the apparatus for remediating hydrazine are disclosed. Note that as utilized herein the term “hydrazine” can refer simply to hydrazine and/or, 1,1-dimethylhydrazine, and/or monomethyl-hydrazine, and/or other hydrazine derivatives. Pads or wipes can be utilized to remediate hydrazine spills. In its operational form, the dicarbonyl compound may be present on or in the absorbent material in a solution (e.g., wet or dry form).
The disclosed embodiments include a pad treated with a dicarbonyl compound. The pad can be utilized to remediate hydrazine spills or hydrazine-contaminated surfaces. The apparatus to remediate hydrazine includes a pad comprising an absorbent medium pre-treated with a dicarbonyl compound, wherein a solution, surface, device, or component contaminated with hydrazine reacts with the dicarbonyl compound of the pad to convert the hydrazine into a stable organic compound, thereby decontaminating the spill. The pad itself may include a porous surface cover surrounding an inert absorbent medium component of the pad that in turn supports a dicarbonyl compound that reacts with the hydrazine from the surface. The absorbent medium can be a pad, fibrous material, granular material, or an aqueous absorbent medium. The absorbent medium generally comprises a porous outer fabric surface covering that allows solutions or vapors to pass into the pad's interior.
The disclosed embodiments further include an apparatus for remediating hydrazine comprising a pad. The pad comprises an absorbent medium pre-treated with a dicarbonyl compound, wherein said hydrazine reacts with said dicarbonyl compound of said pad to effect decontamination by converting said hydrazine into a stable organic compound. The pad further comprises a porous surface cover surrounding an inert said absorbent medium to absorb liquids contaminated with said hydrazine into a dicarbonyl-supported interior component of said pad. The absorbent medium comprises at least one absorbent material selected from the following groups of materials: a pad, a fibrous material, a granular material, and an aqueous absorbent medium. The dicarbonyl compound comprises at least one of the following: ketoglutaric acid, a beta-dicarbonyl compound, a gamma-dicarbonyl compound, a remote dicarbonyl compound, a compound selected from a carbonyl-like functional group, acetoacetonitrile, a dry powder, and a spray. The remote dicarbonyl compound comprises at least one of the following compounds: acetoacetone, propanedial, ethyl acetoacetate, levulinic acid, ethyl levulinate, and 1,3-diphenylpropane-1,3-dione. The pad can be pre-treated with said dicarbonyl compound. The pre-treatment comprises pre-treating the pad with at least one of the following: a dicarbonyl solution, a deposited dicarbonyl solid, or a suspended dicarbonyl solid.
The disclosed embodiments also include an apparatus for remediating hydrazine from ammonia borane to efficiently regenerate spent said ammonia borane as a hydrogen storage material, said apparatus comprising a pad. The pad comprises an absorbent medium pre-treated with a dicarbonyl compound, wherein said hydrazine reacts with said dicarbonyl compound in said pad to effect decontamination by converting said hydrazine into a stable organic compound. The pad further comprises a porous surface cover surrounding an inert said absorbent medium to absorb liquids contaminated with said hydrazine into a dicarbonyl-supported interior component of said pad. The absorbent medium comprises at least one absorbent material selected form the following groups of materials: a pad, a fibrous material, a granular material, and an aqueous absorbent medium. The dicarbonyl compound comprises at least one of the following: ketoglutaric acid, a beta-dicarbonyl compound, a gamma-dicarbonyl compound, a remote dicarbonyl compound, a compound selected from a carbonyl-like functional group, a dry powder, a granular absorbent or support material coated with a dry dicarbonyl compound, suspended dry dicarbonyl compounds, a liquid solution containing dicarbonyl compound supported by an absorbent material, a neat liquid dicarbonyl compound, and a spray of said neat liquid. The remote dicarbonyl compound comprises at least one of the following compounds: acetoacetone, propanedial, ethyl acetoacetate, levulinic acid, ethyl levulinate, and 1,3-diphenylpropane-1,3-dione. The dicarbonyl compound selected from a carbonyl-like functional group comprises at least one of the following: acetoacetonitrile, a dry material, or an aerosol.
A method for manufacturing a pad to remediate hydrazine is disclosed. The method comprises providing a pad comprising an absorbent medium wherein said absorbent medium comprises an outer surface and an absorbent inner surface for absorbing hydrazine or a hydrazine-containing solution into said pad, and pre-treating said pad with a dicarbonyl compound, wherein said hydrazine reacts with said dicarbonyl compound in said pad to effect decontamination by converting said hydrazine into a stable organic compound. The pad further comprises a porous surface cover surrounding an inert said absorbent medium to absorb liquids contaminated with said hydrazine into a dicarbonyl-supported interior component of said pad. Said absorbent medium comprises at least one absorbent material selected form the following groups of materials: a pad, a fibrous material, a granular material, and an aqueous absorbent medium. Said dicarbonyl compound comprises at least one of the following: ketoglutaric acid, a beta-dicarbonyl compound, a gamma-dicarbonyl compound, a remote dicarbonyl compound, a compound selected from a carbonyl-like functional group, acetoacetonitrile, a dry powder, a granular absorbent or support material coated with a dry dicarbonyl compound, suspended dry dicarbonyl compounds, a liquid solution supported by an absorbent material, and a neat liquid. Said remote dicarbonyl compound comprises at least one of the following compounds: acetoacetone, propanedial, ethyl acetoacetate, levulinic acid, ethyl levulinate, and 1,3-diphenylpropane-1,3-dione.
The accompanying figures, in which like reference numerals refer to identical or functionally-similar elements throughout the separate views and which are incorporated in and form a part of the specification, further illustrate the present invention and, together with the detailed description of the invention, serve to explain the principles of the present invention.
The particular values and configurations discussed in these non-limiting examples can be varied and are cited merely to illustrate at least one embodiment of the present invention and are not intended to limit the scope of the invention.
The disclosed embodiments stem from the examination of several classes of compounds that quantitatively react with hydrazine to form stable organic products. The reaction of 2-ketoglutaric acid with hydrazine reacts to provide a greater than 99% yield of 6-oxo-1,4,5,6-tetrahydro-pyridazine-3-carboxylic acid (PCA) based on hydrazine as the limiting reagent. It has been found that this compound allows for the facile remediation of hydrazine under a variety of conditions. The focus of the disclosed embodiments concerns the use of 2-ketoglutaric acid or other dicarbonyl compounds for the remediation of hydrazine.
Several classes of organic compounds have been examined by the present inventors. Such compounds react rapidly and quantitatively with hydrazine to form stable organic products. The solid-state reaction (on a milligram scale) of a hydrazine complex with 2-ketoglutaric acid (2KG) has been demonstrated. Such a reaction can produce 6-oxo-1,4,5,6-tetrahydro-pyridazine-3-carbonic acid in near quantitative yield (98%) based on hydrazine as the limiting reagent. The present inventors have found that this compound allows for the facile remediation of hydrazine under a variety of conditions. The present inventors have also ascertained that 2KG has an excellent potential to reduce the hazards associated with the handling and storage of hydrazine fuels. The present inventors have executed extensive work on the reaction between Hz and 2KG. Such a reaction has been found to be very effective at converting technical grade hydrazine to less than ppm levels (none detected by Draeger Tube measurement and other methods). The remediation of hydrazine occurs in less than one hour without the evolution of excessive heat.
An examination of the use of various keto-acids (e.g., such as 2-ketoglutaric acid and other dicarbonyl compounds) for the production of a hydrazine filter has been performed. Such an examination relates to the development of the hydrazine filter, which is disclosed in greater detail herein and is based on determining the optimal solid support (e.g., carbon, etc.) and keto-acid to maximize filter efficiency, along with the development of methods for the extraction of the hydrazine adduct.
The inventors have found that inexpensive solid supports offer a cost saving option for more efficient use of the keto-acid. An air filtration system passes gas over a solid reactant, for example; it is reasonable to expect that reagent near the surface reacts readily, while interior portions react slowly. The inventors have demonstrated that this is an effective approach for the remediation of hydrazine (e.g., hydrazine, 1,1-dimethylhydrazine, and/or monomethyl-hydrazine). However, such a configuration can lead to poor utilization of the reagent. Thus, attempts at coating a variety of glass, ceramic, and carbon supports of different particle size were undertaken. Aqueous and methanolic solutions of the keto-acid were deposited onto substrates by vacuum evaporation of solvents while continuously rotating the container. In most cases, this process resulted in clumped aggregates rather than coated particles even from relatively dilute solutions of keto-acid. However, sand appears to coat uniformly based on appearance and microscopic observations. Smaller particles of silica and glass helices clumped or gave poor uniformity of deposition. Larger grains or gravel provide too little surface area relative to the large mass they bring. Consequently, sand coated with different loadings of reagent was pursued further and the remediation results are described later herein. Spraying or otherwise applying a slurry of the active chemical can also be used for coating support materials.
Attempts to coat ceramic saddles by spraying the pieces with concentrated solutions of keto-acid and allowing for air drying afforded poor uniformity of coating. Solvent appeared to leach towards the most exposed sites where most of the evaporation of solvent occurred. Ceramic saddles afford high surface area relative to their mass and have higher airflow capacity. The saddles are well suited to air filtration and are being explored with a solution based counter-flow apparatus of similar design to the full scale air filtration apparatus NASA, for example, currently uses at launch sites.
A variety of pyridazine ring systems have been used extensively for a variety of medical applications. These include pharmaceuticals for heart disease, HIV, Alzheimer's disease, antidepressants, and even cognitive enhancement drugs. The MSDS (HMIS rating) hazard classification and the DOT classifications for the hydrazine reagents and the compounds described above appear in Table 1 below:
Hydrazine group compounds hydrazine (Hz), monomethyl-hydrazine (MMH), and 1,1-dimethylhydrazine (UDMH) are widely used as fuels (in rocket propulsion systems and fighter jets), corrosion inhibitors (e.g. electric power generating industries), catalysts, emulsifiers, or dyes. It also is a common precursor in the synthesis of a number of polymers, plasticizers, and pesticides. Recently, a variety of medicinal drugs have incorporated the hydrazine molecule. The inventors are currently examining compounds that will react with hydrazine rapidly and quantitatively.
Two classes of compounds that were examined are keto-acids and keto-esters.
The amount of heat that is produced from this reaction is dependent on the concentration of 2KG.
An extraction method was not necessary because the 3-pyridazinecarboxylic acid, 1,4,5,6-tetrahydro-1-methyl-6-oxo- was a solid, which precipitated from the reaction. The cyclic compounds can be treated with hydrogen gas over a palladium catalyst in water to produce D,L-glutamine as illustrated in the scheme 60 depicted in
The container 101 includes a removable lid 104 thereon to which a water dripping mechanism 105 may be attached. The water dripping mechanism 105 can be utilized, for example, to spray or drip water onto the absorbent material 106 arranged within the container 101. Note that in one embodiment, the absorbent material 106 may be provided as a wipe or wipes. In another embodiment, such absorbent material 106 may be implemented as one or more absorbing spill pads, filters, wipes, or other such appropriate media. A fan or vacuum pump 107 can be attached near the side of the outlet port 103 and can be used to draw contaminated gas into the container 101. The disclosed spill pad can be used to remediate hydrazine-contaminated parts or components (e.g., container 101, removable lid 104, fan or vacuum pump 107, etc.) of the disclosed filtration device or any spilled hydrazine within the device. For example, the disclosed spill pad can be used at the inlet port 102 and outlet port 103 to remediate hydrazine that may inadvertently exit from these ports 102, 103. The disclosed spill pad can typically be used independently of a filtration system described in
If in the form of a spill pad or filter, for example, the absorbent material 106 may be formed from appropriate materials within containment net. A typical pad can be shaped like a sleeping pillow of the variety that has polyester batting inside. Examples of such materials include excelsior (wood wool), aspen wood fiber, etc. Other potential materials include plastic derived absorbent wools and melamine paper. The thickness of the padding media may play a part in the decontamination efficiency, allowing for longer contact as gas flows through the pad. For example, an eight-inch-thick spill pad with its increased surface area may be more efficient than a one-inch pad. Depending on design objects, such as Hz concentration reduction targets, back pressure, absorbent materials can be optimized. As used herein, absorbent materials refers to an inert support matrix as opposed to a reagent that in some sense absorbs Hz into its chemical structure to neutralize it.
The absorbent material 106 may be saturated with a solution (e.g., aqueous) of a dicarbonyl compound such as, for example, ketoglutaric acid. Also, the absorbent material 106 may be coated with supporting granules of or suspending a dry powder of dry dicarbonyl compound such as, for example, ketoglutaric acid. In some embodiments, the dicarbonyl compound preferably may constitute a dry powder after treatment of the absorbent material. A power supply 108 may also be incorporated within and/or integrated with or separate from the container 101. As indicated in the configuration depicted in
In accordance with one embodiment, the absorbent material 106 can include a porous outer fabric surface covering that allows passage of a hydrazine containing phase (neat hydrazine, a solution with hydrazine or gas containing hydrazine) from a chemical release on a substrate or present in solution into the absorbing spill pad. The surface covering material may be desirably a chemically resistant cloth or cloth-like material which will shape and maintain the integrity of the pad while containing the inner components and absorbed liquid during use.
An absorbent component can be disposed inside the outer fabric bag with an absorbent interior or core. The absorbent interior or core of the spill pad is generally disposed or embedded within the absorbent component and can include dicarbonyl compounds (e.g., aqueous solution or dry chemical) such as, for example, ketoglutaric acid for reacting with hydrazine in the gas phase, in aqueous solution or in a liquid spill.
In use, the spilled hydrazine may or may not be diluted with water before the spill pad or wipe is applied to clean up the spill. The water in the aqueous solution, for example, assists in the chemical reaction by allowing the hydrazine to migrate to the absorbent interior or core where the aqueous hydrazine is converted into a stable organic compound by reacting with the dicarbonyl compound in the pad. Water also assists in moderating the heat formed during the reaction. The amount of water to be added is not strictly defined and can be varied by those skilled in the art.
It can be appreciated that system 100 is also capable of remediating hydrazine without the absorbent material 106 as described above. For example, a “dry” implementation of system 100 can be configured, in accordance with an alternative embodiment, in which a spray is employed in place of the absorbent material 106, wherein such a spray may contain an aqueous or dry powder composed of, for example, ketoglutaric acid.
The disclosed system and methodology offer a number of advantages and is particularly useful to those industries where hydrazine is utilized and potentially leads to contamination. The electrical generating industry, for example, is one area where hydrazine contamination presents a significant possibility. As such, the approach disclosed herein would be particularly useful in this environment.
In the aerospace industry, for example, a particular turbine engine may provide emergency hydraulic and electric power. When the hydrazine and water mixture is released and passes across an iridium catalyst, for example, it spontaneously ignites, creating hot expanding gases, which drive the turbine. The power created is transmitted through a gearbox to drive an electrical generator and hydraulic pump. The hydrazine is contained in a sealed, nitrogen charged accumulator. When the system is armed, the hydrazine is released whenever the engine-driven generators go off-line, or if all engine-driven hydraulic pumps fail. Such hydrazine, when released, will pose a hazard to human health. Hydrazine may also be released when the system is serviced. The disclosed hydrazine spill pad can be used to remediate any released hydrazine or contaminated surface.
Electrical fuel cell applications are another example where hydrazine contamination may come into effect. For example, some fuel cell technology may eliminate the need for platinum, a precious metal that has been an essential material in the electrode catalyst in conventional fuel cells for automobiles. However, such technology also fixes hydrazine hydrate inside the fuel tank to ensure its safe use as a fuel, resulting in no tailpipe CO2 emissions. Thus, if hydrazine fuel cell technology, in particular, is widely adopted in the future, the potential for hydrazine leakage is possible.
Renowned as a rocket propellant, hydrazine can be used to efficiently regenerate spent ammonia borane as a hydrogen storage material and advance development of hydrogen fuel cells for powering vehicles, for example, as implemented in the embodiments disclosed in
Ammonia borane can contain about twenty percent hydrogen by weight and can release over two equivalents of molecular hydrogen per molecule. When ammonia borane releases hydrogen, it becomes polyborazylene. For ammonia borane to controllably deliver hydrogen and be used commercially, it can be regenerated from polyborazylene using hydrazine and ammonia. Hydrazine in liquid ammonia can almost quantitatively regenerate ammonia borane at a centralized and industrial scale, or aboard individual vehicles or devices. The disclosed spill pad can be used to remediate hydrazine-contaminated parts or components on-board vehicles or within devices that regenerate ammonia borane using hydrazine. An application of this system would be removal of hydrazine from ammonia borane by recirculation of gas through a bed of ammonia borane in the gas purifying system of
It will be appreciated that variations of the above-disclosed and other features and functions, or alternatives thereof, may be desirably combined into many other different systems or applications. Also, that various presently unforeseen or unanticipated alternatives, modifications, variations or improvements therein may be subsequently made by those skilled in the art which are also intended to be encompassed by the following claims.
This patent application is a continuation-in-part of U.S. patent application Ser. No, 12/504,917, entitled “Air Filtration and Absorption Method and System for the Remediation of Hydrazine,” which was filed on Jul. 17, 2009, the disclosure of which is incorporated herein by reference in its entirety. This patent is also a continuation-in-part of U.S. patent application Ser. No. 12/838,632, entitled “Hydrazine Decontamination Wipes,” which was filed on Jul. 19, 2010, the disclosure of which is incorporated herein by reference in its entirety. This patent is also a continuation-in-part of U.S. patent application Ser. No. 13/082,126, entitled “Hydrazine Filtration Method and System,” which was filed on Apr. 7, 2011, the disclosure of which is incorporated herein by reference in its entirety.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 12504917 | Jul 2009 | US |
| Child | 13092433 | US | |
| Parent | 12838632 | Jul 2010 | US |
| Child | 12504917 | US | |
| Parent | 13082126 | Apr 2011 | US |
| Child | 12838632 | US |
