CN1918268A - Fuel blends for hydrogen generators - Google Patents

Abstract

The present invention relates to improved aqueous fuels for hydrogen generators and a method for using them in the production of hydrogen. The present invention also relates to a system of using the subject aqueous fuels to generate hydrogen gas for use in a fuel cell or other device. The subject fuels contain a mixture of boron hydrides, at least one of which is a metal salt, including metal borohydrides, higher boranes and metal higher boron hydrides. The subject aqueous fuels contain a mixture of boron hydrides having a positive ionic charge (<+>IC) to boron ratio of between 0.2 and 0.4 or between 0.6 and 0.99. Preferred fuels contain a mixture of boron hydrides having an (<+>IC) to boron ratio between 0.2 and 0.3 or between 0.7 and 0.8. Mixtures containing a metal borohydride also contain a metal hydroxide to stability it against premature hydrolysis in the aqueous fuel media.

Description

The fuel mixture that is used for hydrogen generator

Invention field

The present invention relates to be used for the hydroborate salt mixture that hydrogen takes place.

Background of invention

Many hydroboratess are also referred to as hydroborate here, and particularly their metal-salt is used for the hydrogen generation, and this it is well known that five in a decade or so.Also known hydrogen is by generally being realized by the hydrolytic process of acid or metal catalytic, as Schlesinger etc. " Sodium Borohydride:Its Hydrolysis and Its use as a Reducing Agent in the Generation of Hydrogen(sodium borohydride: its hydrolysis and in hydrogen takes place as the purposes of reductive agent) ", J.Am.Chem.Soc., Vol 75, pp215-219,1953 and G.W.Parshall " Hydrogen Generation by Hydrolysis Or Alcoholysis of a Polyhydropolyborate-Group VIII Metal Mixture(taking place) by polyhydropolyborates (the Polyhydropolyborate)-hydrolysis of VIII family metal mixture or the hydrogen of alcoholysis " United States Patent (USP) 3,166,514 in reported like that.Along with the research and development of controlled hydrogen gas generating system as required, these early stage work are improved.United States Patent (USP) 6,534,033 has described by the contact hydroborate aqueous solution and has controlled the method that hydrogen takes place, and this solution of pumping is by containing the chamber of metal catalyst, thus make hydroborate according to reaction formula 1 to be converted into hydrogen and borate near quantitative productive rate.

(1)

The selection of the concrete borohydride salt that uses in the method for many factor decision reaction formula 1.Primary in these factors is solubleness in water.The solubleness of hydroborate in water is generally about 7% to about 35% weight in the time of 25 ℃.Lithium borohydride has 7% solubleness, and the solubleness of POTASSIUM BOROHYDRIDE is about 19%, and sodium borohydride is with about 35% dissolving.Other reason that comprises safety and accessibility for this reason and particularly selects sodium borohydride as the salt that is used for the fuel solution of hydrogen generator.Sodium borohydride also is preferred for implementing the present invention, and it has under the envrionment temperature the high hydrogen storage density of analyzing by weight of about 7.4% weight in the saturated solution.

In the strong solution of for example above-described sodium borohydride, originally exist enough water be used for sodium borohydride complete hydrolysis and be used for borate product is remained on solution.But, shown in reaction formula 1, along with the carrying out of hydrolysis, consume water, the quantity that has and can be used for borate product is remained on the water in the solution then reduces.If the quantity of water drops to wherein that borate is precipitated out in the system from the solution hydrogen-catalyst reactor, or when being deposited in any connection hold-up vessel to reactor ducted, hydrogen generator will stop up the degree that it is closed, dismantles and cleans of having to gradually.

Borate product may from solution sedimentary result be, the concentration limit that is used for the sodium borohydride of the fuel solution that hydrogen takes place is about 15% to 20% weight, and let it be to the greatest extent, and solubleness is higher relatively.On behalf of the hydrogen of about 4.25% weight, this solution take place.This is considered to the actual limit that hydrogen takes place, for example referring to the United States Patent (USP) 3 of Von Dohren " Raney Catalyst forGenerating Hydrogen by Decomposition of Boranes (being used for decompose taking place the Raney catalyzer of hydrogen) " by borine, 615,215.This limitation causes the reduction of corresponding hydrogen storage capacity, and this is not optimal under the situation that capacity comes into one's own.Normal conditions are exactly so, and special hope has the intensive fuel of hydrogen, make the hydrogen store content maximization of per unit volume fuel.The invention provides this fuel.

Summary of the invention

The invention provides and be used for the fuel mixture that contains the hydroborates mixture that hydrogen takes place, described hydroborates comprises at least a borohydride salt that has the positive ion that is selected from alkali metal cation, alkaline earth metal cation, aluminium cations and ammonium cation, make mixture have predetermined solvation positive ion electric charge ( ⁺IC) with the mol ratio of boron atom, boratory thus solubleness is maximized.This fuel mixture helps to can be used for the fuel with high hydrogen storage of analyzing by weight that hydrogen takes place and reduces concern to the premature setting problem of the borate product in hydrogen formation apparatus.Be equivalent to contain 30% to 38% weight sodium borohydride solution (the hydrogen storage density of Fen Xiing is 6.4% to 8% weight by weight) fuel mixture effectively hydrolysis generate hydrogen and do not have the shortcoming of known fuel.Also provide and utilized fuel mixture described herein to carry out improving one's methods and system of hydrogen generation.

Detailed Description Of The Invention

The present invention relates to be used for the aqueous fuel that contains some hydroborates mixture that hydrogen takes place.Hydroborates refers to the negatively charged ion of borine (comprising the polyhedron borine) and hydroborate or polyhedron borine herein.More specifically, the present invention relates to comprise solvation positive ion electric charge ( ⁺ICs) mol ratio with the boron atom is the aqueous fuel of the hydroborates mixture of preset value.Have been found that this ratio can't cause the solubleness maximization of fuel element, but the solubleness maximization of the borate product of the hydrolysis reaction that causes causing that hydrogen takes place.The maximization of this solubleness mean with fuel in the concentration dependent borate product of hydroborate reach best solubleness, the hydrolysis (for example hydroborate in the reaction formula (1)) owing to hydroborates causes the consumption of water to produce minimumization of the sedimentary possibility of borate product in the hydrogen generating process thereby make.

With an alkali metal salt is example, according to following mode of the present invention determine the positive ion electric charge ( ⁺IC) with the ratio of boron.Alkali metal borate is write as j M usually ₂Ok B ₂O ₃X H ₂The form of O, wherein M is selected from lithium, sodium and potassium.For different borates, the value of j, k and X is different.For example for mineral borax (Borax), j=1, k=2, therefore X=10 can be written as Na ₂O2B ₂O ₃10H ₂O or Na ₂B ₄O ₇10H ₂O.Those of ordinary skill in the art can recognize that almost any ratio of j and k all can form solid-state borate crystal, but the such solubleness of crystal in water will be different.Have two solubleness maximum values that depend on temperature, the ratio that they appear at j and k respectively is 0.2 to 0.4 and 0.6 to 0.99.

For many years people have known that boratory solubleness is the function of the ratio of j and k.For example can be with reference to Nies and Holbert, Journal of Chemical and EngineeringData, Vol.12, No.3, pp 303-313,1967, Adams, " Boron, Metallo-Boron Compounds and Boranes(boron, metal diboride compound and borine) ", John Wiley ﹠amp; Sons, the 81st page, 1964 and Garret, " Borates, Handbook of Deposits, Processing, Properties and use (borate deposition, processing, character and purposes handbook) ", Academic Press, 1998, the 454 pages.The salt (wherein M is potassium or lithium) that provides of molecular formula has similar solubleness maximum value in the above, referring to Adams ibid, and 81 and 83 pages and Reburn and Gale, Journal of Physical Chemistry, Vol.59, No.19,1955.Though for many years can in disclosed document, obtain these data and other countless data, not recognize the value of these data in being identified for the fuel mixture of hydrogen generator up to now as yet.

According to the present invention, select to be used for the fuel mixture of hydrogen generator, make them comprise the hydroborates mixture, wherein the positive ion electric charge ( ⁺ICs) be 0.2 to 0.4 with the mol ratio of boron atom, preferred 0.2 to 0.3, perhaps 0.6 to 0.99, preferred 0.7 to 0.8.Fuel mixture of the present invention comprises hydroborates salt and at least a other hydroborates to meet the requirements of ratio, and the positive ion of wherein said hydroborates salt (M) is selected from the positive ion of basic metal (for example sodium, lithium, potassium), alkaline-earth metal, aluminium or ammonium.Suitable hydroborates includes but not limited to borohydride salt (MBH ₄), three borohydride salt (MB ₃H ₈), decahydro ten borate (M ₂B ₁₀H ₁₀), 13 hydrogen, ten borate (MB ₁₀H ₁₃), dodecahydrododecaborates (M ₂B ₁₂H ₁₂) and ten octahydros, 20 borate (M ₂B ₂₀H ₁₈) and the relevant neutral borane compound compatible with hydroborates salt, for example Decaboron tetradecahydride (14) (B ₁₀H ₁₄), wherein M is basic metal, alkaline-earth metal or aluminium cations.

Use within the scope of the invention such high-grade hydroborates mixture with obtain the positive ion electric charge ( ⁺ICs) with the mol ratio of the requirement of boron atom.Mixture although it is so can comprise as those borines that provide above, but also be necessary to have at least a hydroborates salt with obtain requiring ( ⁺ICs) with the ratio of boron.The preferred positive ion hydroborates of the present invention mixture includes but not limited to: metal borohydride, preferred sodium borohydride, and Decaboron tetradecahydride (14); Metal three hydroborates and metal dodecahydrododecaborates; Metal borohydride and metal three hydroborates; And metal borohydride and metal dodecahydrododecaborates.As for hydroborates mixture in the fuel of being discussed ⁺IC/B ratio is that the both is favourable between 0.2 to 0.4 or be not critical between 0.6 to 0.99.Select the component hydroborates and obtain ⁺IC/B ratio can consider determine from economic aspect, for example the relative availability of each hydroborates and cost and each hydroborates chemical reactivity and to health effects.Being in one of them or another scope as for concrete mixture can be determined by the consideration of others, the operating temperature range that requires of the relative solubility of various hydroboratess, mixture etc. for example is within these scopes that all one skilled in the relevant art grasped.

Except the alkali metal cation of reference hydroborate narration, the positive ion component of above-mentioned senior hydroborate can also be alkaline earth metal cation or aluminium cations.Preferred positive ion is selected from sodium, lithium, potassium, beryllium, magnesium, calcium or aluminium.When the fuel mixture of being discussed comprises more than a kind of borohydride salt, and do not require that positive ion component wherein is identical.As mentioned above, the positive ion component that is used for the metal borohydride of the fuel mixture discussed is preferably sodium.Those of ordinary skill in the art will appreciate that wherein borohydride salt is present among the aqueous fuel mixture that is used for hydrogen generator, and hydrolysis will take place easily for it, unless in the presence of highly basic anti-hydrolysis and stabilization.Suitable for this purpose alkali is the oxyhydroxide of the respective metal that provides above, and they are highly basic, for example are sodium hydroxide when this component is sodium borohydride.Comprise in the preferred fuel mixture of borohydride salt in the present invention, when as to be discussed below, calculate the positive ion electric charge ( ⁺During IC) with the mol ratio of boron, the positive cationic components of stablizer must enter into equation.Equally, for preparing stable Decaboron tetradecahydride (14) aqueous solution, must there be the alkali stablizer; The metallic cation component of stablizer to fuel mixture contribution positive ion electric charge ( ⁺IC).Many rich hydroborates (M for example ₂B ₁₂H ₁₂, M ₂B ₁₀H ₁₀And M ₂B ₂₀H ₁₈) be stable in neutral aqueous solution.

According to the present invention, carry out in the following manner the positive ion electric charge ( ⁺IC) with the calculating of the mol ratio of boron.As example, as only positive ion hydroborate be the stable fuel aqueous solution that adds 3% weight sodium hydroxide, be example for the sodium borohydride that comprises 35% weight with 100 gram fuel solutions, j that determines by following mode and the ratio of k are 1.08.In this example, all boron are from sodium borohydride, therefore can be as follows from fuel solution the concentration of hydroborate directly calculate the mole number of boron.

$20g{\mathrm{NaBH}}_4\left(\frac{1\mathrm{mol}{\mathrm{NaBH}}_4}{37.83g{\mathrm{NaBH}}_4}\right)\left(\frac{1\mathrm{mol\; B}}{1\mathrm{mol}{\mathrm{NaBH}}_4}\right)=0.529\mathrm{mol\; B}$

Adopt same account form as can be known, sodium borohydride also provides 0.925 mole Na, because wherein sodium and boron exist by 1: 1 mol ratio.But also exist the other sodium that provides by the sodium hydroxide stabilized agent ( ⁺IC), as follows its can be determined by the mode similar to the contribution of definite boron.

$3\mathrm{g\; NaOH}\left(\frac{1\mathrm{mol\; NaOH}}{40.00\mathrm{g\; NaOH}}\right)\left(\frac{1\mathrm{mol\; Na}}{1\mathrm{mol\; NaOH}}\right)=0.075\mathrm{mol\; Na}$

In case known with the positive ion electric charge ( ⁺IC) mole number of suitable sodium, can be by as follows by calculating described ratio divided by the total mole number of boron with the total mole number of sodium:

$\left(\frac{0.529\mathrm{mol\; Na}+0.075\mathrm{mol\; Na}}{0.529\mathrm{mol\; B}}\right)=1.14\mathrm{Na}:B$

Therefore, comprise 35% weight sodium borohydride and 3% weight sodium hydroxide solution ( ⁺IC) ratio with boron is 1.08, and this is outside above-mentioned maxima solubility scope ratio.Can not be precipitated out the obstruction that causes equipment if do not add other water when reaction continues to carry out to guarantee borate product and can remain in the solution, this can effectively limit the such purposes of dense fuel solution in hydrogen generator.

As described above, can regulate the ratio of j and k in the existence of the middle-and-high-ranking hydroborates of fuel solution, make it to be reduced to the preferred ratio of the present invention, this is that senior hydroborates is rich boron owing to compare with the metal component in the fuel mixture.The boratory solubleness of product in this fuel, can comprise the hydroborate of greater amt in the fuel solution, thereby comprise the hydrogen of greater amt because borate product solidified risk reduces significantly greater than the sodium borohydride aqueous solution of routine.The further advantage of fuel mixture of the present invention is that the senior hydroborates of many rich boron is stable in the aqueous solution, do not need as add alkaline stabiliser in metal borohydride (for example sodium borohydride) situation.The other advantage of the mixed fuel solution of being discussed is, some senior hydroborates hydrolysis in the aqueous solution, generate some acid products, these acid products can play the effect of part neutral for any metal hydroxides stablizer that exists, compare with the mixture of the metal metaphosphate borate/metal hydroxides that uses the fuel generation that only comprises metal borohydride and metal hydroxides, the discharging current material alkalescence of generation is lower.

The additional advantage of the aqueous fuel mixture of novelty of the present invention is, even in hydrolysis reactor some curing may take place during cooling, product is also soluble in water.On the contrary, the dissolving of the borate mixture that (for example hydroborate of sodium and oxyhydroxide) forms when fuel only comprises metal borohydride and oxyhydroxide is slowly, can form the sclerderm that is difficult to remove in catalyst chamber.The borate mixture that uses fuel mixture of the present invention to form can be removed easily by means of the simple means of water rinsing vessel chamber and relevant device, stops using the repair time with the normal of minimizing hydrogen gas generation system thereby prolong catalyst life.The cleaning of the requirement of easy cleaning and hydrogen gas generation system and the remarkable economic advantages that the lengthening in the attended operation timed interval is fuel mixture of the present invention.

Compare with the product that forms from the fuel mixture that only comprises metal borohydride (for example sodium borohydride) from the product that fuel mixture of the present invention forms, dissolubility difference can be interpreted as the negative heat of the common solvation that is associated with borate.For example, sodium metaborate demonstrates very strong solvent cooling effect when entering solution, thereby has slowed down solubilizing reaction.On the contrary, the positive ion electric charge ( ⁺IC) the boric acid sodium salt of mol ratio within maxima solubility scope of the present invention with boron shows positive hot solvation, therefore in fact can promote solubilizing reaction, therefore promote the generation of hydrogen, USP No.2 referring to O ' Brien etc. " Amorphous Sodium BorateComposition (amorphous boric acid composition of sodium) ", 998,310.

The term of Shi Yonging " aqueous fuel " comprises that all components all are dissolved in liquid, aqueous and/or some components dissolved wherein and some components are slurry of dissolved solids not herein.Water-alcohol mixture also helps preparing aqueous fuel of the present invention, and this is that they can reduce the zero pour of fuel, thereby expands its operating temperature range.Generally speaking, senior hydroborates is not only solvable but also stable often in water-alcohol solution, especially exists stablizer with under the situation that improves pH.The alcohol that the preparation water-alcohol solution uses is lower alcohol, particularly methyl alcohol and ethanol.What estimate is that the aqueous fuel for the saving of handling and storing with the slurry form preparation should combine the solution that meets the component of maxima solubility ratio described herein with formation with competent water in use herein.

The invention provides and be used for the improved method and system that hydrogen takes place.Described method comprise with discussed have specific positive ion electric charge ( ⁺IC) with the improved hydroborates aqueous fuel mixture of the molar ratio of boron be used to promote the catalyzer of hydroborates hydrolysis to contact to generate hydrogen.System provided by the invention comprises hydroborates aqueous fuel mixture and the contacted device of catalyzer.This device is included in when not needing hydrogen the device with catalyzer physical sepn from fuel.But when needing hydrogen, the fuel aqueous solution can be contacted with catalyzer, thereby hydrolysis reaction take place and generate hydrogen.That the separation of catalyzer can adopt that those skilled in the art can understand easily is any machinery, chemistry, the method for electricity and/or magnetic.In one embodiment, use different chamber separating catalysts from the fuel aqueous solution.Aqueous fuel can be stored in the fuel reservoir, from then on it is pumped in the catalyst chamber to contact with catalyzer, thus the hydrolysis reaction generation hydrogen by the metal borohydride shown in the reaction formula (1).For selecting in the embodiment, can in the storage tank that contains the hydride solution of discussing to some extent, insert and remove catalyzer.

In further embodiment, the catalyzer that is used for hydrolysis is acid, and fuel and catalyzer all are can pump into the interior liquid form with generation hydrogen of reaction chamber.In this embodiment, fuel and catalyst solution must be stored in the container separately, and pump into respectively in the reactor to cause and to keep hydrolysis reaction.Preferred acid catalyst is a strong inorganic acid, particularly hydrochloric acid, sulfuric acid and phosphoric acid.

Can the improved fuel solution of the present invention be pumped in the system partial or continuous mode.Further, catalyst chamber can comprise at least one conduit, can fuel solution directly be imported described indoor and derive from described chamber in the different steps of catalyzed reaction by it.Described conduit can also play the effect of the output channel of the hydrogen that discharges the hydrolysis reaction generation.

It must be noted that, when the metal that uses insoluble petal or be bonded to, be trapped in and/or be coated to matrix during as the catalyzer in the reaction shown in the reaction formula (1), be not that chamber separately must be arranged.The suitable matrix that is used for metal catalyst includes but not limited to plastics, polymkeric substance, fabric, metal, metal oxide, pottery or carbonaceous material.In preferred embodiments, system of the present invention comprises tightness system, wherein catalyzer be captured on porous matrix or the nonporous matrix by physics or chemical means and/or within, described matrix comprises as United States Patent (USP) 6,534,033 described metallic mesh and fiber, this patent is attached to herein by reference.In these any embodiments, hydrogen gas generation system can only comprise a chamber, wherein realize the separation of catalyzer from aqueous fuel by from solution, removing catalyzer insoluble or load, thus contacting between blocking-up catalyzer and the hydroborates there.Therefore, when requiring to generate hydrogen, can catalyzer be inserted into again in the aqueous fuel with the above-mentioned reaction of catalysis (1) simply.

Because the improved aqueous fuel of the present invention is stable when not having catalyzer, then take place with the hydrogen that contacting of catalyzer just can carefully be controlled according to reaction (1) by the hydroborates of regulating the there.According to the actual setting and the structure thereof of hydrogen gas generation system, can realize described control to the mobile of catalyzer or by from fuel solution, removing catalyzer by regulating aqueous fuel.In the system of application load or deposited catalyst, can be by the generation that contacts with the hydroborates fuel solution or the catalyzer of separation and combination is controlled hydrogen from the hydroborates fuel solution.For example, catalyst metal can be invested the demand that can respond hydrogen and move on fuel solution and piston that from fuel solution, shifts out or the similar object.Perhaps, supported catalyst can be contained in the independent chamber, controls fuel solution by valve and suitable adjuster device and flows into described chamber.For homogeneous catalyst acid solution for example, by regulate the hydroborates fuel solution flow or catalyst solution flow or both flowing all can be controlled hydrogen and take place.The preferred mixing section that uses wherein will described two kinds of solution injects or pumps into described indoorly, makes their mix generation hydrolysis reaction.

In another embodiment, (hydronium(ion) (hydronium) salt for example, wherein positive ion is H can to use the acid-salt of polyhedral boranes ⁺And ammonium salt, wherein positive ion is NH ₄ ⁺) as being used for composite fuel component and the promotor that hydrogen takes place.Suitable promoter component comprises H ₂B ₁₂H ₁₂, H ₂B ₁₀H ₁₀, (NH ₄) ₂B ₁₂H ₁₂(NH ₄) ₂B ₁₀H ₁₀In such system, do not need other catalyst system, also can be as required in conjunction with a kind of catalyst system with optimization hydrogen generation rate.In this embodiment, acid polyhedral boranes salt (promotor) with comprise the fuel mixture separate storage of one or more hydroboratess, each material is as required in conjunction with preparation hydrogen.At least a in preferred accelerators or the fuel mixture is that the aqueous solution is to promote mixing.Yet every kind of component or both (fuel mixture and promotor) can save as dry powder to eliminate the needs to stablizer.In this case, hydrogen requires independent water supply, will do component and liquid ingredient with any method well known to those skilled in the art and join in the mixing section in the ratio of determining.Select kind, concentration and the mixing rate of hydroborates according to the present invention described above, make the borate that obtains have 0.2 to 0.4 or 0.6 to 0.99 suitable ⁺IC/B ratio.Only, the hydration hydrogen salt is used as neutral hydroborates handles in order to calculate purpose, for example for the contribution of determining boron with H ₂B ₁₂H ₁₂Be used as B ₁₂H ₁₄Handle.When requiring hydrogen to take place, the promotor metering infeeded in the reactor with hydroborates fuel mixture and water that all are essential mix.Thereby acid polyhedral boranes salt plays the effect of promotor promotes that hydrogen reacts, and hydrolysis generates hydrogen, and the contributes boron atom is contributed positive charge to fuel mixture under the situation of ammonium salt.

Have been found that the hydrogen and the liquid borate product that form in the hydrolysis reaction flow out jointly.Therefore, in preferred embodiments, use gas-liquid separator separating hydrogen gas from effluent solution.In addition, for the hydrogen that needs at once is provided, preferably in native system, be used in combination little surge tank.In such embodiments, small-sized surge tank includes the hydrogen supply of satisfied needs at once always.In case remove hydrogen from surge tank, the pressure of generation falls and can generate more hydrogen to keep the level constant of there hydrogen by initiating system.

Can be directed into fuel cell or hydrogen consumer device by the hydrogen that native system takes place and directly use.In alternatives, can be as mentioned above with hydrogen storage in gas reservoir or surge tank for using in the future.

Be subjected to the influence of 2 considerations according to the fuel mixture of the present invention's preparation.At first be exactly positive ion electric charge discussed herein ( ⁺IC) with the molar ratio of atomic boron.Second to select be exactly relative solubility in order to each salt that forms mixture.Those of ordinary skill in the art can recognize, the given maximum ratio parameter discussed herein and the relative solubility (these data are easy to obtain) of each salt just can prepare and have the fuel solution that maximum ratio and all components dissolve in moisture media.Adopt the following examples to illustrate this method of calculation, its purpose is to illustrate, the scope that is not intended to limit the present invention.

Embodiment 1

General method from fuel mixture generation hydrogen

In fuel mixture, use sodium borohydride, Decaboron tetradecahydride, sodium hydroxide and water as sample system, test is taken place hydrogen do general description.Prepare fuel mixture under the condition in the open.The sodium hydroxide of a mixing water and a stabilization adds Decaboron tetradecahydride therein during beginning, adds the sodium borohydride of appropriate amount subsequently, meets the requirements of ratio.

For catalysis discharge fuel mixture, use the Parr reactor that places on the hot plate.Reactor combines with two thermopairs in the run duration non-stop run, and one of them is used for measuring the temperature of fuel solution, and another is used for measuring near the head space temperature of reactor head.When second thermopair records 95 ℃ threshold temperature, second cooling loop that cycles through reactor that thermopair control starts.But practical situation are that even used hot plate, temperature of reaction is also seldom above 90 ℃.Pressure transmitter continuously measured internal pressure.At first fill six blocks of nickel catalyzators that apply ruthenium in reactor, every heavy 0.095 to 0.105g.Inject the fuel mixtures (weight of accurate known each run) of about 10 grams and with described mouthful sealing by admission port.Open hot plate then.When pressure no longer increases with measurable speed, hot plate is closed, allow reactor cooling to room temperature.When the average gas temperature of reactor head is mated the medial temperature of reaction soln, interrupt data gathering and also measure last pressure.Can come together to calculate the mole output of hydrogen with last pressure and temperature and reactor volume.Described mole output is compared with the output of estimating from the quantity and the concentration of fuel, determine percentage yield.

Thermolysis to be carrying out with the same mode of catalysis discharging, but in the Parr reactor catalyst filling not, only the heat of hot plate is the reason that causes the mixture hydrolysis.

Embodiment 2

7.0% weight hydrogen, ⁺IC/B ratio=0.8

Mix following substances according to the method among the embodiment 1 and can discharge 7.0% weight H to obtain 100g ₂And the ratio of sodium and boron is 0.8 fuel mixture: sodium borohydride 27.16g; Sodium hydroxide 3g; Decaboron tetradecahydride (14) 3.34g and water 66.5g.According to reaction formula (1), every mole of sodium borohydride produces four mol of hydrogen.

(1)

According to reaction formula (2), every mole of Decaboron tetradecahydride (14) produces 22 mol of hydrogen.

(2)

Generate H by calculating ₂Total mole number and determine the hydrogen storage capacity of this mixture divided by the initial weight of mixture.

From NaBH ₄In:

$27.16g{\mathrm{NaBH}}_4\left(\frac{1\mathrm{mol}{\mathrm{NaBH}}_4}{37.83g{\mathrm{NaBH}}_4}\right)\left(\frac{4\mathrm{mol}{H}_2}{1\mathrm{mol}{\mathrm{NaBH}}_4}\right)\left(\frac{2.0158g{H}_2}{1\mathrm{mol}{H}_2}\right)=5.79g{H}_2$

From B ₁₀H ₁₄In:

$3.34g{B}_{10}{H}_{14}\left(\frac{1\mathrm{mol}{B}_{10}{H}_{14}}{122.21g{B}_{10}{H}_{14}}\right)\left(\frac{22\mathrm{mol}{H}_2}{1\mathrm{mol}{B}_{10}{H}_{14}}\right)\left(\frac{2.0158g{H}_2}{1\mathrm{mol}{H}_2}\right)=1.21g{H}_2$

Total hydrogen output is the 5.79+1.21=7 gram, or 7% weight.

By following calculating ⁺IC: B ratio:

From NaBH ₄In:

$27.16g{\mathrm{NaBH}}_4\left(\frac{1\mathrm{mol}{\mathrm{NaBH}}_4}{37.83g{\mathrm{NaBH}}_4}\right)\left(\frac{1\mathrm{molB}}{1\mathrm{mol}{\mathrm{NaBH}}_4}\right)=0.718\mathrm{molB}$

From B ₁₀H ₁₄In:

$3.34g{B}_{10}{H}_{14}\left(\frac{1\mathrm{mol}{B}_{10}{H}_{14}}{122.21g{B}_{10}{H}_{14}}\right)\left(\frac{10\mathrm{molB}}{1\mathrm{mol}{B}_{10}{H}_{14}}\right)=0.273\mathrm{molB}$

From NaBH ₄In:

$27.16g{\mathrm{NaBH}}_4\left(\frac{1\mathrm{mol}{\mathrm{NaBH}}_4}{37.83g{\mathrm{NaBH}}_4}\right)\left(\frac{1\mathrm{mol}{\mathrm{Na}}^{+}}{1\mathrm{mol}{\mathrm{NaBH}}_4}\right)\left(\frac{1\mathrm{mo}{l}^{+}\mathrm{IC}}{1\mathrm{mol}{\mathrm{Na}}^{+}}\right)=0.718\mathrm{mo}{l}^{+}\mathrm{IC}$

From NaOH:

$3.00\mathrm{gNaOH}\left(\frac{1\mathrm{molNaOH}}{40.00\mathrm{gNaOH}}\right)\left(\frac{1\mathrm{mol}{\mathrm{Na}}^{+}}{1\mathrm{molNaOH}}\right)\left(\frac{1\mathrm{mo}{l}^{+}\mathrm{IC}}{1\mathrm{mol}{\mathrm{Na}}^2}\right)=0.075{\mathrm{mol}}^{+}\mathrm{IC}$

$\left(\frac{0.718+0.075{\mathrm{mol}}^{+}\mathrm{IC}}{0.718+0.273\mathrm{molB}}\right)={0.800}^{+}\mathrm{IC}:B$

So Na of this mixture: the B mol ratio is 0.8.

Embodiment 3

6.8% weight hydrogen, ⁺IC/B ratio=0.25

Mix following substances according to the method among the embodiment 1 and can discharge 6.8% weight H to obtain 100g ₂And the ratio of sodium and boron is 0.25 fuel mixture: three sodium borohydride 13.74g; Ten dihydros, ten hypoboric acid sodium 13.74g and water 76.09g.According to reaction formula (3), every mole ten dihydro ten hypoboric acid sodium produce 25 mol of hydrogen.

(3)

According to reaction formula (4), every mole three sodium borohydride produces nine mol of hydrogen.

(4)

Generate H by calculating ₂Total mole number and determine the hydrogen storage capacity of this mixture divided by the initial weight of mixture.

From Na ₂B ₁₂H ₁₂In:

$10.17g{\mathrm{Na}}_2{B}_{12}{H}_{12}\left(\frac{1\mathrm{mol}{\mathrm{Na}}_2{B}_{12}{H}_{12}}{187.79{\mathrm{Na}}_2{B}_{12}{H}_{12}}\right)\left(\frac{25\mathrm{mol}{H}_2}{1\mathrm{mol}{\mathrm{Na}}_2{B}_{12}{H}_{12}}\right)\left(\frac{2.0158g1H_2}{1\mathrm{mol}{H}_2}\right)=2.87g{H}_2$

From NaB ₃H ₈In:

$13.74g{\mathrm{NaB}}_3{H}_8\left(\frac{1\mathrm{mol}{\mathrm{NaB}}_3{H}_8}{63.48g{\mathrm{NaB}}_3{H}_8}\right)\left(\frac{9\mathrm{mol}{H}_2}{1\mathrm{mol}{\mathrm{NaB}}_3{H}_8}\right)\left(\frac{2.0158g{H}_2}{1\mathrm{mol}{H}_2}\right)=3.93g{H}_2$

Total hydrogen output is the 2.87+3.93=6.8 gram, or 6.8% weight.Also can be by following calculating ⁺IC: B ratio:

From Na ₂B ₁₂H ₁₂In:

$10.17g{\mathrm{Na}}_2{B}_{12}{H}_{12}\left(\frac{1\mathrm{mol}{\mathrm{Na}}_2{B}_{12}{H}_{12}}{187.79{\mathrm{Na}}_2{B}_{12}{H}_{12}}\right)\left(\frac{12\mathrm{mol}B}{1\mathrm{mol}{\mathrm{Na}}_2{B}_{12}{H}_{12}}\right)=0.650\mathrm{molB}$

From NaB ₃H ₈In:

$13.74g{\mathrm{NaB}}_3{H}_8\left(\frac{1\mathrm{mol}{\mathrm{NaB}}_3{H}_8}{63.48g{\mathrm{NaB}}_3{H}_8}\right)\left(\frac{3\mathrm{molB}}{1\mathrm{mol}{\mathrm{NaB}}_3{H}_8}\right)=0.649\mathrm{molB}$

From Na ₂B ₁₂H ₁₂In:

$10.17g{\mathrm{Na}}_2{B}_{12}{H}_{12}\left(\frac{1\mathrm{mol}{\mathrm{Na}}_2{B}_{12}{H}_{12}}{187.79{\mathrm{Na}}_2{B}_{12}{H}_{12}}\right)\left(\frac{{2\mathrm{molNa}}^2}{1\mathrm{mol}{\mathrm{Na}}_2{B}_{12}{H}_{12}}\right)\left(\frac{1{\mathrm{mol}}^{+}\mathrm{IC}}{1\mathrm{mol}{\mathrm{Na}}^{+}}\right)=0.108{\mathrm{mol}}^{+}\mathrm{IC}$

From NaB ₃H ₈In:

$13.74g{\mathrm{NaB}}_3{H}_8\left(\frac{1\mathrm{mol}{\mathrm{NaB}}_3{H}_8}{63.48g{\mathrm{NaB}}_3{H}_8}\right)\left(\frac{1\mathrm{mol}{\mathrm{Na}}^{+}}{1\mathrm{mol}{\mathrm{NaB}}_3{H}_8}\right)\left(\frac{{1\mathrm{mol}}^{+}\mathrm{IC}}{1\mathrm{mol}{\mathrm{Na}}^{+}}\right)=0.216{\mathrm{mol}}^{+}\mathrm{IC}$

$\left(\frac{0.108+0.216{\mathrm{mol}}^{+}\mathrm{IC}}{0.650+0.649\mathrm{molB}}\right)={0.25}^{+}\mathrm{IC}:B$

So Na of this mixture: the B mol ratio is 0.25.

Embodiment 4

5% weight hydrogen, ⁺IC/B ratio=0.25

Mix following substances according to the method among the embodiment 1 and can discharge 5.0% weight H to obtain 100g ₂And the ratio of metallic cation and boron is 0.25 fuel mixture: three POTASSIUM BOROHYDRIDE 12.95g; Ten dihydros, ten hypoboric acid magnesium 6.76g and water 80.03g.

According to reaction formula (5), every mole ten dihydro ten hypoboric acid magnesium generate 25 mol of hydrogen.

(5)

According to reaction formula (6), every mole three POTASSIUM BOROHYDRIDE generates nine mol of hydrogen.

(6)

Generate H by calculating ₂Total mole number and determine the hydrogen storage capacity of this mixture divided by the initial weight of mixture.

From MgB ₁₂H ₁₂In:

$6.76g{\mathrm{MgB}}_{12}{H}_{12}\left(\frac{1\mathrm{mol}{\mathrm{MgB}}_{12}{H}_{12}}{166.12g{\mathrm{MgB}}_{12}{H}_{12}}\right)\left(\frac{25\mathrm{mol}{H}_2}{1\mathrm{mol}{\mathrm{MgB}}_{12}{H}_{12}}\right)\left(\frac{2.0158g{H}_2}{1\mathrm{mol}{H}_2}\right)=2.05g{H}_2$

From KB ₃H ₈In:

$12.95g{\mathrm{KB}}_3{H}_8\left(\frac{1\mathrm{mol}{\mathrm{KB}}_3{H}_8}{79.59g{\mathrm{KB}}_3{H}_8}\right)\left(\frac{9{\mathrm{molH}}_2}{1\mathrm{mol}{\mathrm{KB}}_3{H}_8}\right)\left(\frac{2.0158g{H}_2}{1\mathrm{mol}{H}_2}\right)=2.95g{H}_2$

Total hydrogen output is the 2.05+2.95=5.0 gram, or 5% weight.Also can be by following calculating ⁺IC: B ratio:

From MgB ₁₂H ₁₂In:

$6.76g{\mathrm{MgB}}_{12}{H}_{12}\left(\frac{1\mathrm{mol}{\mathrm{MgB}}_{12}{H}_{12}}{166.12g{\mathrm{MgB}}_{12}{H}_{12}}\right)\left(\frac{12\mathrm{molB}}{1\mathrm{mol}{\mathrm{MgB}}_{12}{H}_{12}}\right)=0.488\mathrm{molB}$

From KB ₃H ₈In:

$12.95g{\mathrm{KB}}_3{H}_8\left(\frac{1\mathrm{mol}{\mathrm{KB}}_3{H}_8}{79.59g{\mathrm{KB}}_3{H}_8}\right)\left(\frac{3\mathrm{molB}}{1\mathrm{mol}{\mathrm{KB}}_3{H}_8}\right)=0.488\mathrm{molB}$

From MgB ₁₂H ₁₂In:

$6.76g{\mathrm{MgB}}_{12}{H}_{12}\left(\frac{1\mathrm{mol}{\mathrm{MgB}}_{12}{H}_{12}}{166.12g{\mathrm{MgB}}_{12}{H}_{12}}\right)\left(\frac{1\mathrm{mol}{\mathrm{Mg}}^{2+}}{1\mathrm{mol}{\mathrm{MgB}}_{12}{H}_{12}}\right)\left(\frac{2{\mathrm{mol}}^{+}\mathrm{IC}}{1\mathrm{mol}{\mathrm{Mg}}^{2+}}\right)=0.081{\mathrm{mol}}^{+}\mathrm{IC}$

From KB ₃H ₈In:

$12.95g{\mathrm{KB}}_3{H}_8\left(\frac{1\mathrm{mol}{\mathrm{KB}}_3{H}_8}{79.59g{\mathrm{KB}}_3{H}_8}\right)\left(\frac{1\mathrm{mol}{K}^{+}}{1\mathrm{mol}{\mathrm{KB}}_3{H}_8}\right)\left(\frac{1{\mathrm{mol}}^{+}\mathrm{IC}}{1\mathrm{mol}{K}^{+}}\right)=0.163{\mathrm{mol}}^{+}\mathrm{IC}$

$\left(\frac{0.081+0.163{\mathrm{mol}}^{+}\mathrm{IC}}{0.488+0.488\mathrm{molB}}\right)=0{.25}^{+}\mathrm{IC}:B$

So this mixture ⁺IC: the B mol ratio is 0.25.

Embodiment 5-8

By similar calculating, be prepared as follows fuel mixture according to the method for embodiment 1:

Embodiment #	Fuel mixture is formed	+IC	B	+IC/B	H% weight
						5	3.92gNaBH 4 0.78gNaOH 0.63gB 10H 14 14.69H 2O	0.124	0.156	0.79	5.3％
6	6.13gNaBH 4 0.8gNaOH 0.8gB 10H 14 17.33H 2O	0.182	0.227	0.8	6.4％
						7	7.26gNaBH 4 0.78gNaOH 0.87gB 10H 14 16.54H 2O	0.214	0.263	0.81	7.5％
8	3.22gNaBH 4 0.47gNaOH 0.40g B 10H 14 6.18H 2O	0.095	0.118	0.81	8.1％

Embodiment 9

5.6% weight hydrogen, ⁺IC/B ratio=0.7

For the purposes of proof hydroborates as promotor, sodium borohydride (20mg), decahydro ten boric acid, two ammoniums (5mg) and water (75mg) are mixed, the hydrogen of accompanied by intense takes place immediately.This mixture with ⁺The ratio of IC and boron is 0.7 and can to discharge the fuel mixture of 5.6% weight hydrogen suitable.According to reaction formula (1), every mole of sodium borohydride produces four mol of hydrogen.

(1)

According to reaction formula (7), every mole of decahydro ten boric acid two ammoniums produce 21 mol of hydrogen.

(7)

Generate H by calculating ₂Total mole number and determine the hydrogen storage capacity of this mixture divided by the initial weight of mixture.

From NaBH ₄In:

$20\mathrm{mg}{\mathrm{NaBH}}_4\left(\frac{1\mathrm{mmol}{\mathrm{NaBH}}_4}{37.83\mathrm{mg}{\mathrm{NaBH}}_4}\right)\left(\frac{4\mathrm{mmol}{H}_2}{1\mathrm{mmol}{\mathrm{NaBH}}_4}\right)\left(\frac{2.0158\mathrm{mg}{H}_2}{1\mathrm{mmol}{H}_2}\right)=4.26\mathrm{mg}{H}_2$

$5\mathrm{mg}{\left({\mathrm{NH}}_4\right)}_2{B}_{10}{H}_{10}\left(\frac{1\mathrm{mmol}{\left({\mathrm{NH}}_4\right)}_2{B}_{10}{H}_{10}}{154.26\mathrm{mg}{\left({\mathrm{NH}}_4\right)}_2{B}_{10}{H}_{10}}\right)\left(\frac{21\mathrm{mmol}{H}_2}{1\mathrm{mmol}{\left({\mathrm{NH}}_4\right)}_2{B}_{10}{H}_{10}}\right)\left(\frac{2.0158\mathrm{mg}{H}_2}{1\mathrm{mmol}{H}_2}\right)=1.40\mathrm{mgl}$

Total hydrogen output is the 4.26+1.40=5.66 milligram, or 5.6% weight.Also can be by following calculating ⁺IC: B ratio:

From (NH ₄) in:

$5\mathrm{mg}{\left({\mathrm{NH}}_4\right)}_2{B}_{10}{H}_{10}\left(\frac{1\mathrm{mmol}{\left({\mathrm{NH}}_4\right)}_2{B}_{10}{H}_{10}}{154.26\mathrm{mg}{\left({\mathrm{NH}}_4\right)}_2{B}_{10}{H}_{10}}\right)\left(\frac{10\mathrm{mmolB}}{1\mathrm{mmol}{\left({\mathrm{NH}}_4\right)}_2{B}_{10}{H}_{10}}\right)=0.324\mathrm{mmolB}$

From NaBH ₄In:

$20\mathrm{mg}{\mathrm{NaBH}}_4\left(\frac{1\mathrm{mmol}{\mathrm{NaBH}}_4}{37.83\mathrm{mg}{\mathrm{NaBH}}_4}\right)\left(\frac{1\mathrm{mmolB}}{1\mathrm{mmol}{\mathrm{NaBH}}_4}\right)=0.529\mathrm{mmolB}$

From (NH ₄) ₂Among the B:

$5\mathrm{mg}{\left({\mathrm{NH}}_4\right)}_2{B}_{10}{H}_{10}\left(\frac{1\mathrm{mmol}{\left({\mathrm{NH}}_4\right)}_2{B}_{10}{H}_{10}}{154.26\mathrm{mg}{\left({\mathrm{NH}}_4\right)}_2{B}_{10}{H}_{10}}\right)\left(\frac{2\mathrm{mmol}{{\mathrm{NH}}_4}^{+}}{1\mathrm{mmol}{\left({\mathrm{NH}}_4\right)}_2{B}_{10}{H}_{10}}\right)\left(\frac{1\mathrm{mmo}{l}^{+}\mathrm{IC}}{1\mathrm{mmol}{{\mathrm{NH}}_4}^{+}}\right)=0.0648{\mathrm{mmol}}^{+}\mathrm{IC}$

From NaBH ₄In:

$20\mathrm{mg}{\mathrm{NaBH}}_4\left(\frac{1\mathrm{mmol}{\mathrm{NaBH}}_4}{37.83\mathrm{mg}{\mathrm{NaBH}}_4}\right)\left(\frac{1\mathrm{mmol}{\mathrm{Na}}^{+}}{1\mathrm{mmol}{\mathrm{NaBH}}_4}\right)\left(\frac{1{\mathrm{mmol}}^{+}\mathrm{IC}}{1\mathrm{mmol}{\mathrm{Na}}^{+}}\right)=0.529{\mathrm{mmol}}^{+}\mathrm{IC}$

$\left(\frac{0.529+0.0648{\mathrm{mmol}}^{+}\mathrm{IC}}{0.529+0.324\mathrm{mmolB}}\right)={0.70}^{+}\mathrm{IC}:B$

Therefore this and Na: the B mol ratio is that 0.70 fuel mixture is suitable.

Embodiment 10

7.4% weight hydrogen, ⁺IC/B ratio=0.38

According to the method for embodiment 9, make sodium borohydride (17g), B ₁₂H ₁₂ ^-2Hydration hydrogen salt (11g), sodium hydroxide (3g) and water (70g) mix so that hydrogen to take place.This mixture with ⁺The ratio of IC and boron is 0.38 and can to discharge the fuel mixture of 7.4% weight hydrogen suitable.According to reaction formula (1), every mole of sodium borohydride produces four mol of hydrogen.

(1)

According to reaction formula (8), every mole of H ₂B ₁₂H ₁₂Produce 25 mol of hydrogen.

(8)

Generate H by calculating ₂Total mole number and determine the hydrogen storage capacity of this mixture divided by the initial weight of mixture.

From NaBH ₄In:

$17g{\mathrm{NaBH}}_4\left(\frac{1\mathrm{mol}{\mathrm{NaBH}}_4}{37.83g{\mathrm{NaBH}}_4}\right)\left(\frac{4\mathrm{mol}{H}_2}{1\mathrm{mol}{\mathrm{NaBH}}_4}\right)\left(\frac{2.0158g{H}_2}{1\mathrm{mol}{H}_2}\right)=3.62g{H}_2$

From H ₂B ₁₂H ₁₂In:

$11g{H}_2{B}_{12}{H}_{12}\left(\frac{1\mathrm{mol}{H}_2{B}_{12}{H}_{12}}{143.84g{H}_2{B}_{12}{H}_{12}}\right)\left(\frac{25\mathrm{mol}{H}_2}{1\mathrm{mol}{H}_2{B}_{12}{H}_{12}}\right)\left(\frac{2.0158g{H}_2}{1\mathrm{mol}{H}_2}\right)=3.85g{H}_2$

Total hydrogen output is the 3.62+3.85=7.47 gram, or 7.4% weight.Also can be by following calculating ⁺IC: B ratio:

From H ₂B ₁₂H ₁₂In:

$11g{H}_2{B}_{12}{H}_{12}\left(\frac{1\mathrm{mol}{H}_2{B}_{12}{H}_{12}}{143.84g{H}_2{B}_{12}{H}_{12}}\right)\left(\frac{12\mathrm{molB}}{1\mathrm{mol}{H}_2{B}_{12}{H}_{12}}\right)=0.918\mathrm{molB}$

From NaBH ₄In:

$17g{\mathrm{NaBH}}_4\left(\frac{1\mathrm{mol}{\mathrm{NaBH}}_4}{37.83g{\mathrm{NaBH}}_4}\right)\left(\frac{1\mathrm{molB}}{1\mathrm{mol}{\mathrm{NaBH}}_4}\right)=0.449\mathrm{molB}$

From NaOH:

$3\mathrm{gNaOH}\left(\frac{1\mathrm{molNaOH}}{40.00\mathrm{gNaOH}}\right)\left(\frac{1\mathrm{mol}{\mathrm{Na}}^{+}}{1\mathrm{molNaOH}}\right)\left(\frac{1{\mathrm{mol}}^{+}\mathrm{IC}}{1\mathrm{mol}{\mathrm{Na}}^{+}}\right)=0.075{\mathrm{mol}}^{+}\mathrm{IC}$

From NaBH ₄In:

$17g{\mathrm{NaBH}}_4\left(\frac{1\mathrm{mol}{\mathrm{NaBH}}_4}{37.83g{\mathrm{NaBH}}_4}\right)\left(\frac{1\mathrm{mol}{\mathrm{Na}}^{+}}{1\mathrm{mol}{\mathrm{NaBH}}_4}\right)\left(\frac{1{\mathrm{mol}}^{+}\mathrm{IC}}{1\mathrm{mol}{\mathrm{Na}}^{+}}\right)=0.449{\mathrm{mol}}^{+}\mathrm{IC}$

$\left(\frac{0.449+0.075{\mathrm{mol}}^{+}\mathrm{IC}}{0.449+0.918\mathrm{molB}}\right)=0{.38}^{+}\mathrm{IC}:B$

Therefore this and Na: the B mol ratio is that 0.38 fuel mixture is suitable.

Claims (39)

1. aqueous fuel that is used for hydrogen generator, described aqueous fuel contains the aqueous solution or the water-alcohol solution or the slurry of the hydroborates mixture that comprises at least a hydroborates salt, described at least a hydroborates salt has the positive ion that is selected from basic metal, alkaline-earth metal and aluminium cations, the positive ion electric charge of described hydroborates mixture ( ⁺IC) ratio with boron is 0.2 to 0.4 or 0.6 to 0.99.

2. the aqueous fuel of claim 1, the positive ion electric charge of wherein said hydroborates mixture ( ⁺IC) ratio with boron is 0.2 to 0.3 or 0.7 to 0.8.

3. the aqueous fuel of claim 1, wherein said hydroborates is selected from borohydride salt (MBH ₄), three borohydride salt (MB ₃H ₈), decahydro ten borate (M ₂B ₁₀H ₁₀), 13 hydrogen, ten borate (MB ₁₀H ₁₃), dodecahydrododecaborates (M ₂B ₁₂H ₁₂), ten octahydros, 20 borate (M ₂B ₂₀H ₁₈) and Decaboron tetradecahydride (14) (B ₁₀H ₁₄), wherein M is selected from basic metal, alkaline-earth metal and aluminium cations.

4. the aqueous fuel of claim 1, wherein said mixture comprises the borohydride salt with the positive ion that is selected from sodium, lithium and potassium cationic.

5. the aqueous fuel of claim 4, wherein said mixture contains the stablizer that is used for described borohydride salt in water-bearing media in addition, and described stablizer comprises the oxyhydroxide that is selected from sodium hydroxide, lithium hydroxide and potassium hydroxide.

6. the aqueous fuel of claim 5, wherein said borohydride salt is a sodium borohydride, described stablizer is a sodium hydroxide.

7. the aqueous fuel of claim 3, wherein said hydroborates mixture comprises borohydride salt and Decaboron tetradecahydride, described fuel also contains the stablizer that is used for described borohydride salt in water-bearing media, and described stablizer comprises the oxyhydroxide that is selected from sodium hydroxide, lithium hydroxide and potassium hydroxide.

8. the aqueous fuel of claim 7, wherein said hydroborates mixture comprises sodium borohydride and Decaboron tetradecahydride, and described stablizer is a sodium hydroxide.

9. the aqueous fuel of claim 3, wherein said hydroborates mixture comprises three borohydride salts and dodecahydrododecaborates.

10. the aqueous fuel of claim 9, wherein said three borohydride salts are three POTASSIUM BOROHYDRIDE, described dodecahydrododecaborates is ten dihydros, ten hypoboric acid magnesium.

11. the aqueous fuel of claim 3, wherein said hydroborates mixture comprises borohydride salt and dodecahydrododecaborates, described fuel also contains the stablizer that is used for described borohydride salt in water-bearing media, and described stablizer comprises the oxyhydroxide that is selected from sodium hydroxide, lithium hydroxide and potassium hydroxide.

12. the aqueous fuel of claim 11, wherein said hydroborates salt is sodium borohydride, and described dodecahydrododecaborates is ten dihydros, ten hypoboric acid sodium, and described stablizer is a sodium hydroxide.

13. the aqueous fuel of claim 3, wherein said hydroborates mixture is borohydride salt and three borohydride salts, described fuel also contains the stablizer that is used for described borohydride salt in water-bearing media, and described stablizer comprises the oxyhydroxide that is selected from sodium hydroxide, lithium hydroxide and potassium hydroxide.

14. the aqueous fuel of claim 13, wherein said borohydride salt is a sodium borohydride, and described three borohydride salts are three sodium borohydrides, and described stablizer is a sodium hydroxide.

15. the method for a speciogenesis hydrogen, described method comprises aqueous fuel is contacted with hydrogen generation catalyzer, described aqueous fuel contains the aqueous solution or the water-alcohol solution or the slurry of the hydroborates mixture that comprises at least a hydroborates salt, described at least a hydroborates salt has the positive ion that is selected from basic metal, alkaline-earth metal and aluminium cations, the positive ion electric charge of described hydroborates mixture ( ⁺IC) ratio with boron is 0.2 to 0.4 or 0.6 to 0.99, and described hydrogen generation catalyzer is selected from acid and transition metal.

16. the method for the generation hydrogen of claim 15, the positive ion electric charge of wherein said hydroborates mixture ( ⁺IC) ratio with boron is 0.2 to 0.3 or 0.7 to 0.8.

17. the method for the generation hydrogen of claim 15, wherein said hydroborates is selected from borohydride salt (MBH ₄), three borohydride salt (MB ₃H ₈), decahydro ten borate (M ₂B ₁₀H ₁₀), 13 hydrogen, ten borate (MB ₁₀H ₁₃), dodecahydrododecaborates (M ₂B ₁₂H ₁₂), ten octahydros, 20 borate (M ₂B ₂₀H ₁₈) and Decaboron tetradecahydride (14) (B ₁₀H ₁₄), wherein M is selected from basic metal, alkaline-earth metal and aluminium cations.

18. the method for the generation hydrogen of claim 15, wherein said mixture contains borohydride salt, and wherein M is selected from sodium, lithium and potassium.

19. the method for the generation hydrogen of claim 18, wherein said mixture also contains the stablizer that is used for described borohydride salt in water-bearing media, and described stablizer comprises sodium hydroxide, lithium hydroxide and potassium hydroxide.

20. the method for the generation hydrogen of claim 15, wherein said catalyzer are the acid that is selected from hydrochloric acid, sulfuric acid and phosphoric acid.

21. the method for the generation hydrogen of claim 1, wherein said catalyzer comprise one or more transition metal that are selected from nickel, cobalt and ferrous metal family.

22. the method for the generation hydrogen of claim 21, wherein said catalyzer are ruthenium, cobalt or its mixture.

23. a hydrogen gas generation system, described system comprises

(a) aqueous fuel, described aqueous fuel contains the aqueous solution or the water-alcohol solution or the slurry of the hydroborates mixture that comprises at least a hydroborates salt, described at least a hydroborates salt has the positive ion that is selected from basic metal, alkaline-earth metal and aluminium cations, the positive ion electric charge of described hydroborates mixture ( ⁺IC) ratio with boron is 0.2 to 0.4 or 0.6 to 0.99;

(b) be selected from the acid and the hydrogen generation catalyzer of transition metal; With

(c) described aqueous fuel is contacted with described catalyzer so that the device of hydrogen to take place.

24. the method for the generation hydrogen of claim 23, the positive ion electric charge of wherein said hydroborates mixture ( ⁺IC) ratio with boron is 0.2 to 0.3 or 0.7 to 0.8.

25. the hydrogen gas generation system of claim 23, wherein said hydroborates is selected from borohydride salt (MBH ₄), three borohydride salt (MB ₃H ₈), decahydro ten borate (M ₂B ₁₀H ₁₀), 13 hydrogen, ten borate (MB ₁₀H ₁₃), dodecahydrododecaborates (M ₂B ₁₂H ₁₂), ten octahydros, 20 borate (M ₂B ₂₀H ₁₈) and Decaboron tetradecahydride (14) (B ₁₀H ₁₄), wherein M is selected from basic metal, alkaline-earth metal and aluminium cations.

26. the hydrogen gas generation system of claim 23, wherein said mixture comprises the borohydride salt with the positive ion that is selected from sodium, lithium and potassium cationic.

27. the hydrogen gas generation system of claim 23, wherein said hydrogen generation catalyzer is the acid that is selected from hydrochloric acid, sulfuric acid and phosphoric acid, and described acid and aqueous fuel are stored in the container separately.

28. the hydrogen gas generation system of claim 23, wherein said hydrogen generation catalyzer comprises combination, catches and/or apply the matrix of transition metal molecule, described contact device comprises the tightness system that is used for described catalyzer, makes catalyzer to realize contacting and disengaging with aqueous fuel.

29. the hydrogen gas generation system of claim 23, described system comprises gas-liquid separator in addition with separating hydrogen gas from effluent.

30. the hydrogen gas generation system of claim 23, at least a portion water in the wherein said aqueous fuel derives from the reaction product of hydrogen consumer, but described device is connected with described system with operating method.

31. the hydrogen gas generation system of claim 30, wherein said hydrogen consumer is selected from fuel cell, oil engine, internal combustion turbine and combination thereof.

32. a hydrogen gas generation system, described system comprises

(a) fuel mixture, described fuel mixture comprise at least a hydroborates salt with the positive ion that is selected from basic metal, alkaline-earth metal and aluminium cations;

(b) promotor is selected from the hydronium(ion) of polyhedral boranes and the acid polyhedral boranes salt of ammonium salt described promotor comprising, the positive ion electric charge of the mixture of wherein said hydroborates and promotor ( ⁺IC) ratio with boron is 0.2 to 0.4 or 0.6 to 0.99; With

(c) fuel mixture and water are contacted with promotor so that the device of hydrogen to take place.

33. the method for the generation hydrogen of claim 32, the positive ion electric charge of the mixture of wherein said hydroborates and promotor ( ⁺IC) ratio with boron is 0.2 to 0.3 or 0.7 to 0.8.

34. the hydrogen gas generation system of claim 35, wherein said hydroborates is selected from borohydride salt (MBH ₄), three borohydride salt (MB ₃H ₈), decahydro ten borate (M ₂B ₁₀H ₁₀), 13 hydrogen, ten borate (MB ₁₀H ₁₃), dodecahydrododecaborates (M ₂B ₁₂H ₁₂), ten octahydros, 20 borate (M ₂B ₂₀H ₁₈) and Decaboron tetradecahydride (14) (B ₁₀H ₁₄), wherein M is selected from basic metal, alkaline-earth metal and aluminium cations.

35. the hydrogen gas generation system of claim 32, wherein said promotor are H ₂B ₁₂H ₁₂

36. the hydrogen gas generation system of claim 32, wherein said promotor are (NH ₄) ₂B ₁₀H ₁₀

37. the hydrogen gas generation system of claim 32, wherein said mixture comprises borohydride salt, and wherein positive ion is selected from sodium, lithium and potassium.

38. the hydrogen gas generation system of claim 32, wherein at least a portion water derives from the reaction product of hydrogen consumer, but described device is connected with described system with operating method.

39. the hydrogen gas generation system of claim 38, wherein said hydrogen consumer is selected from fuel cell, oil engine, internal combustion turbine and combination thereof.