CN1918068A

CN1918068A - Method and apparatus for hydrogen storage and delivery

Info

Publication number: CN1918068A
Application number: CN 200480040988
Authority: CN
Inventors: B·D·拉特纳; E·D·内米
Original assignee: Asemblon Inc
Current assignee: Asemblon Inc
Priority date: 2003-11-26
Filing date: 2004-11-24
Publication date: 2007-02-21
Also published as: ZA200605195B

Abstract

To methods, devices, and assemblies for hydrogen generation. The system (50) includes a vehicle (54) having a device (52) for generating hydrogen for use in generating energy, a service station (58), and a vehicle (60). A hydrogen generating compound (62), such as an organic mercaptan, is transferred from a service station (59) to a storage tank (64) of a device (52) located inside a vehicle (54). The compound (62) is reacted with the metal substrate (66) to produce hydrogen gas and spent compound and/or R-X compound (e.g., organothiolate) bound to the metal substrate (66), if desired. The hydrogen gas may be delivered to a hydrogen-consuming device (56) for generating energy for use in operating the vehicle (54). The R-X compound-producing used compound (68) (e.g., dimer R-X-X-R) bound to the metal substrate (66) can be separated from the metal substrate (66) by applying energy from an energy source. The spent compound (68) may be stored in a storage tank (70) and transported by a transport vehicle (60) to a service station (58) for regeneration.

Description

The method and apparatus of storing hydrogen and conveying

CROSS-REFERENCE TO RELATED APPLICATIONS

The application requires the benefit of priority of the United States serial 60/525422 submitted on November 26th, 2003 according to 35U.S.C § 119 (e), this paper introduces its full content as a reference.

Background of invention

Invention field

The present invention relates generally to storing hydrogen, generation and energy-producing application, relate more specifically to produce the method for hydrogen and exhausted compound regeneration is suitable for the method for the form that hydrogen produces and the device and the subassembly that produce hydrogen by can be again producing compound with hydrogen.

Background information

" hydrogen economy " is that wherein most of energy produces the economy by using hydrogen to act as a fuel and take place.Attractive especially and cater to the need based on the economy of hydrogen fuel, because it is indicating abundant and energy clean environment.For example, fuel cell technology continues development, and provides with efficient manner and hydrogen and oxygen (for example air) are changed into energy such as electric energy and only discharge the possibility of water.But, change into based on the system of more hydrogen fuels and need and carry Infrastructure to change and be transformed into system from worldwide petroleum chemistry production based on hydrogen fuel.

Storing hydrogen and production source just constantly are found, and technology is also improving, and the cost of producing hydrogen fuel constantly descends.But, effective utilization of these technical progresses and be subjected to up till now to transformation that available storing hydrogen and production source seriously limit based on the system of more hydrogen fuels.Present technology famine for example stores and carries the effective and practical means of hydrogen to the position that needs hydrogen to consume.

Available stores and carries the method for hydrogen fuel to comprise that for example compressed hydrogen, liquefying hydrogen, physics metal hydride store, chemical hydride stores, nanotube stores and some other at present.Compression and liquefaction store and mainly to be subjected to required method of energy-intensive and therefore expensive compressed hydrogen and the restriction that stores the required heavy groove of compression/liquefying hydrogen, and when on moving vehicle or automobile, may there be serious explosion hazard in this.Hydride stores future, but present method is extremely expensive, and for too heavy the practical application on vehicle.For example, estimate that the little metal hydride container that holds less than 2 gram hydrogen weighs 230 grams.Therefore, the hydride holder of 200 kilograms or 440 pounds when storing the Equivalent of gasoline of 8 liters or 2 U.S. gallon weighs needs, this makes this class storing hydrogen impracticable, for example for automobile use (referring to people such as for example Bossel, in April, 2003 report: " The Future of the Hydrogen Economy:Bright or Bleak? ").

Unfortunately, also find apparatus and method cheap but effective and lightweight and practicality on hydrogen-powered vehicle.Therefore, have the needs to the method and apparatus that is used for the storage of lightweight and available hydrogen, they are applicable to that producing hydrogen on hydrogen-powered vehicle when needed comes generate energy.

Summary of the invention

The present invention partly goes up based on this discovery, and promptly specific compound is applicable to that chemistry stores hydrogen, and can be used to produce quantity when needed and be enough to be used in energy-producing hydrogen.The present invention has also described exhausted compound regeneration has been suitable for the rich hydrogen form that hydrogen produces, and is used further to the hydrogen generation according to the method for describing.

Therefore, the present invention relates to use the energy-producing method of hydrogen of generation, is by enabling to produce hydrogen and having the fluid cpds of formula R-XH and the metal base reaction produces hydrogen; With utilize the hydrogen generate energy.The chemical group that is expressed as R comprises the part that for example is selected from alkyl, assorted alkyl, alkenyl, substituted alkenyl base, alkynyl, aryl, heteroaryl, alkoxyl group, cycloalkyl, heterocyclic radical, alkaryl, aralkyl, arylalkenyl, sweet-smelling alkynyl, arylidene, oxygen arylidene and their combination.In addition, X can comprise sulphur, oxygen, selenium or hydrogen.Be suitable for can comprising for example gold and silver, platinum, copper and mercury with the metal base of fluid cpds reaction generation hydrogen, and the processed metal of removing the oxide on surface coating.Metal base can comprise the mixture of pure metal base material and metal, as metal alloy and the polymkeric substance that scribbles metal.This method also comprises utilizes the hydrogen generate energy.The utilization of hydrogen for example can comprise consume hydrogen in combustion engine, fuel cell or any other hydrogen consumer.

The invention still further relates to and store and produce the method that is used for energy-producing hydrogen.In one embodiment, produce hydrogen and have formula R by enabling ₁The fluid cpds of-XH and metal base react the R that produces hydrogen and be attached to metal base ₁-X and utilize hydrogen to realize to store and produce the method for hydrogen.Radicals R ₁Comprise the part that for example is selected from alkyl, assorted alkyl, alkenyl, substituted alkenyl base, alkynyl, aryl, heteroaryl, alkoxyl group, cycloalkyl, heterocyclic radical, alkaryl, aralkyl, arylalkenyl, sweet-smelling alkynyl, arylidene, oxygen arylidene and their combination.In addition, X can comprise sulphur, oxygen or selenium.Be suitable for can comprising for example gold and silver, platinum, copper and mercury with the metal base of fluid cpds reaction generation hydrogen, and the processed metal of removing the oxide on surface coating.Metal base can comprise the mixture of pure metal base material and metal, as metal alloy.Collecting hydrogen for example can comprise at device and consume hydrogen in as combustion engine or fuel cell.

Method also can comprise from metal base separates R ₁-X produces the exhausted compound.The exhausted compound can comprise for example dipolymer, as has formula R ₁-X-X-R ₁Compound.Separate R from metal base ₁The whole bag of tricks of-X compound all is suitable for method of the present invention, comprises by applying the energy to bonded R ₁On-X the compound.Separate R ₁-X compound can comprise and for example adds the R that is thermally bonded on the metal base ₁-X compound and/or make the R that is attached on the metal base ₁-X compound contact ultraviolet (UV) light, and make the compound pickup current.

The present invention is and the last hydrogen that is used to produce the exhausted compound (for example dipolymer) of hydrogen based on regeneration of part produces the ability of capacity.Therefore, in one embodiment, the method that stores and produce hydrogen comprises that also used compound and H-H reaction generation have formula R ₁The compound of-XH is suitable for exhausted compound regeneration the form (for example can produce the compound of hydrogen from the regeneration of exhausted compound) that hydrogen produces whereby.The whole bag of tricks that is produced compound by exhausted compound regenerated hydrogen all is useful in the method for the invention, comprises that for example used compound and hydrogen are by the catalytic hydrogenation process reaction.Generation is used for the step of energy-producing hydrogen and the step of regeneration exhausted compound can take place in same position or near the position.Perhaps, hydrogen generation step can be carried out in different positions with exhausted compound regeneration step.For example, hydrogen produces step and can occur in the automobile, and that exhausted compound regeneration step can occur in automobile is outer or separate with automobile, comprises for example after removing the exhausted compound from automobile.Produce when occurring in fixed cell such as buildings (for example dwelling house, shop, shelter etc.) at hydrogen, regeneration also can occur in Architectural Services Department, as in building and near the position of hydrogen generation position in the building, maybe can occur in and builds different positions.

The method according to this invention also can produce hydrogen, wherein generation dehydrogenation when making the reaction of compound and metal base by the dehydrogenation that hydrogen produce the hydrocarbon part of compound.Therefore, in another embodiment of the present invention, produce hydrogen and have formula R by enabling ₁The fluid cpds of-XH and metal base reaction produce hydrogen and the exhausted compound is finished storage and produced the method that is used for energy-producing hydrogen.The exhausted compound can comprise: for example have formula R ₂-XH, wherein R ₂With respect to R ₁By dehydrogenation; R ₃=X, wherein R ₃With respect to R ₁By dehydrogenation; Or the compound of their combination.According to this embodiment of the present invention, R ₁, R ₂And R ₃In each all be the part that independently is selected from alkyl, assorted alkyl, alkenyl, substituted alkenyl base, alkynyl, aryl, heteroaryl, alkoxyl group, cycloalkyl, heterocyclic radical, alkaryl, aralkyl, arylalkenyl, sweet-smelling alkynyl, arylidene, oxygen arylidene and their combination.In addition, X is selected from sulphur, oxygen, selenium and hydrogen.With top similar, the metal base that is suitable for the inventive method comprises for example gold and silver, platinum, copper and mercury, and the processed metal of removing the oxide on surface coating, and can comprise the mixture of pure metal base material for example and metal, as metal alloy.

The method according to this invention, the fluid cpds that can produce hydrogen is suitable for re-using, and becomes to be suitable for the form that hydrogen produces because the exhausted compound can be reproduced.Thereby present method comprises that also used compound and H-H reaction generation have formula R ₁The compound of-XH, being regenerated by the exhausted compound whereby to produce the compound of hydrogen.Produce hydrogen and the step of the exhausted compound of regenerating can occur in for example close position (for example in same device) or in different positions.

The invention still further relates to and produce the device that is used for energy-producing hydrogen.In one embodiment, device comprises and is suitable for holding the storage tank that can produce hydrogen and have the fluid cpds of formula R-XH that wherein R is the part that is selected from alkyl, assorted alkyl, alkenyl, substituted alkenyl base, alkynyl, aryl, heteroaryl, alkoxyl group, cycloalkyl, heterocyclic radical, alkaryl, aralkyl, arylalkenyl, sweet-smelling alkynyl, arylidene, oxygen arylidene and their combination; X is selected from sulphur, oxygen and selenium.Device also comprises and is suitable for producing the R-X compound that is attached on the metal base and the metal base of hydrogen with fluid cpds reaction.

Device can comprise in addition and can separate the energy that the R-X compound produces the exhausted compound from metal base.The exhausted compound can comprise for example dipolymer, as has the compound of formula R-X-X-R.The energy can comprise for example thermal source or UV light source.

In another embodiment of the present invention, produce the device be used for energy-producing hydrogen and comprise being suitable for holding and to produce hydrogen and have formula R ₁The storage tank of the fluid cpds of-XH; With the metal base that is suitable for producing hydrogen and exhausted compound with the fluid cpds reaction.The exhausted compound can comprise for example having formula R ₂The compound of-XH, wherein R ₂With respect to R ₁By dehydrogenation; R ₃=X, wherein R ₃With respect to R ₁By dehydrogenation; Or their combination.R ₁, R ₂And R ₃In each all comprise the part that independently is selected from alkyl, assorted alkyl, alkenyl, substituted alkenyl base, alkynyl, aryl, heteroaryl, alkoxyl group, cycloalkyl, heterocyclic radical, alkaryl, aralkyl, arylalkenyl, sweet-smelling alkynyl, arylidene, oxygen arylidene and their combination.In addition, X is selected from sulphur, oxygen, selenium and hydrogen.

The metal base that is applicable to apparatus of the present invention comprises for example gold and silver, platinum, copper, mercury and the processed metal of removing the oxide on surface coating.Metal base can comprise pure metal base material and metal mixture or alloy.Metal base also can comprise various metallic forms, comprises the nanoporous metal, as nano-hole golden.In one embodiment, compound can comprise for example organic mercaptan compound.

Device of the present invention also can comprise the storage tank that is used to store the exhausted compound.In one embodiment, the storage tank that is used for storing the exhausted compound is suitable for removing the exhausted compound from device.Device can comprise regeneration room in addition, and this regeneration room is suitable for used compound and produces the compound with formula R-XH with the H-H reaction of accepting from the device external source, produces compound by exhausted compound regenerated hydrogen whereby.Device of the present invention can utilize the hydrogen generate energy.Utilize the hydrogen generate energy for example can comprise in the hydrogen consumer as consuming hydrogen in hydrogen burning engine or the fuel cell.Thereby the present invention relates to the automobile of the device with hydrogen consumer and generation hydrogen of the present invention in addition.

The invention still further relates to the method that produces compound by exhausted compound regenerated hydrogen.This method comprises that the device that is used for energy-producing hydrogen from generation accepts exhausted compound and used compound and H-H reaction and produce the compound with formula R-XH, produces compound by exhausted compound regenerated hydrogen whereby.

The invention still further relates to the subassembly that produces and utilize hydrogen.In one embodiment, subassembly of the present invention comprises the first module that is used to produce hydrogen and is used to utilize the energy-producing Unit second of hydrogen, and wherein Unit second is suitable for accepting the hydrogen from first module.First module comprises and is suitable for holding the storage tank that can produce hydrogen and have the fluid cpds of formula R-XH that wherein R is the part that is selected from alkyl, assorted alkyl, alkenyl, substituted alkenyl base, alkynyl, aryl, heteroaryl, alkoxyl group, cycloalkyl, heterocyclic radical, alkaryl, aralkyl, arylalkenyl, sweet-smelling alkynyl, arylidene, oxygen arylidene and their combination; Be selected from sulphur, oxygen and selenium with X.First module comprises that also being suitable for reacting generation with fluid cpds is attached to the R-X compound of metal base and the metal base of hydrogen.Unit second can comprise for example hydrogen consumer, as hydrogen burning engine or fuel cell.In one embodiment, subassembly of the present invention can be comprised in the automobile.

Subassembly of the present invention can comprise in addition and can separate the energy that R-X produces exhausted compound (dipolymer that for example has formula R-X-X-R) from metal base.The energy can comprise for example thermal source or UV light source.

In another embodiment of the present invention, subassembly comprises the first module that is used to produce hydrogen and is used to utilize the energy-producing Unit second of hydrogen, and wherein Unit second is suitable for accepting the hydrogen from first module.First module comprises being suitable for holding and can produce hydrogen and have formula R ₁The storage tank of the fluid cpds of-XH; With the metal base that is suitable for producing hydrogen and exhausted compound with the fluid cpds reaction.The exhausted compound can comprise for example having formula R ₂The compound of-XH, wherein R ₂With respect to R ₁By dehydrogenation; R ₃=X, wherein R ₃With respect to R ₁By dehydrogenation; Or their combination.R ₁, R ₂And R ₃In each all comprise the part that independently is selected from alkyl, assorted alkyl, alkenyl, substituted alkenyl base, alkynyl, aryl, heteroaryl, alkoxyl group, cycloalkyl, heterocyclic radical, alkaryl, aralkyl, arylalkenyl, sweet-smelling alkynyl, arylidene, oxygen arylidene and their combination.In addition, X is selected from sulphur, oxygen, selenium and hydrogen.Unit second can comprise for example hydrogen consumer, as hydrogen burning engine or fuel cell.

The metal base that is applicable to subassembly of the present invention comprises for example gold and silver, platinum, copper, mercury and the processed metal of removing the oxide on surface coating.Metal base can comprise pure metal base material and metal alloy.The reactive metal base material also can comprise various metallic forms, comprises the nanoporous metal, as nano-hole golden.In one embodiment, hydrogen generation compound can comprise for example organic mercaptan compound.

Subassembly also can comprise the storage tank that is used to store the exhausted compound.In one embodiment, the storage tank that is used for storing the exhausted compound is suitable for shifting out the exhausted compound from device.Subassembly can comprise regeneration room in addition, and this regeneration room is suitable for used compound and produces the compound with formula R-XH with the H-H reaction of accepting from the device external source, produces compound by exhausted compound regenerated hydrogen whereby.

The accompanying drawing summary

Fig. 1 has shown that hydrogen according to embodiments of the present invention produces and produced by exhausted compound regenerated hydrogen the schema of compound.

Fig. 2 illustrates hydrogen generation and the regeneration system rapidly that use is installed according to embodiments of the present invention.

Fig. 3 illustrates system and device according to embodiments of the present invention.

Fig. 4 illustrates the example of the fit for service compound according to the present invention.

Fig. 5 further illustrates the fit for service exemplary compounds according to the present invention.

Detailed Description Of The Invention

The present invention comes from some hydrogen and produces the discovery that compound is used for chemistry storage hydrogen and produces hydrogen when needed for generate energy.According to the present invention, hydrogen produces compound can produce hydrogen with the metal base reaction.Compound can be liquid form, and the usual manner (for example service station, fuel hauling truck, pipeline etc.) that can for example use according to automobile fuel and distribute uses and distributes.According to the present invention, the exhausted compound can be reprocessed by the hydrogenation of exhausted compound and be regenerated to produce and can be produced hydrogen and be suitable for being further used for the compound that hydrogen produces.Therefore, the present invention has also described by the regeneration of exhausted compound and has been suitable for the rich hydrogen form (for example hydrogen generation compound) of hydrogen generation and re-uses the regenerated compound according to described method in hydrogen produces.

With reference to figure 1, shown the flow process Figure 10 that produces and produce compound according to the hydrogen of one embodiment of this invention by exhausted compound regenerated hydrogen.The hydrogen that is used for the energy generation produces with step 12 and provides hydrogen generation compound to begin.Hydrogen of the present invention produces compound and has formula R-XH, and wherein R is an organic moiety, and X comprises sulphur, oxygen, selenium or hydrogen.Compound produces hydrogen with the metal base reaction in step 14.Except producing hydrogen, the reaction of compound and metal base also produces the exhausted compound and/or is attached to R-X compound on the metal base.Hydrogen can be collected 16, for example is used in step 18 generate energy.Hydrogen produce compound in step 14 with the metal base reaction after, can in step 20, separate any compound that is attached to metal base from metal base.The separation of R-X compound in step 20 that is attached on the metal base can be by finishing from the energy 22 intakes.In step 20, produce isolating exhausted compound (dipolymer that for example has formula R-X-X-R) from separating of metal base with bonded R-X compound by the input of energy 22.For example, the exhausted compound can be collected and regenerate (for example hydrogenation) become to be suitable for the form that hydrogen produces.Exhausted compound regeneration is suitable for the form of hydrogen generation to be finished by the compound that the generation of used compound and H-H reaction in step 24 has formula R-XH, produces compound by exhausted compound regenerated hydrogen whereby.Be used for to obtain by any hydrogen generation means, comprise for example conventional production method by the hydrogen 26 of exhausted compound regenerated hydrogen generation compound.

Therefore, the present invention relates to by utilizing the hydrogen that produces according to described method to come generate energy.In one embodiment, the fluid cpds by enabling to produce hydrogen produces hydrogen and exhausted compound as compound with formula R-XH and metal base reaction and/or the R-X compound that is attached on the base material is realized energy-producing method.The hydrogen that produces by aforesaid method can be further used in generate energy, for example comprises and using in hydrogen consumer such as combustion engine or fuel cell.

The present invention partly goes up based on this discovery, promptly compound commonly used can react the hydrogen that produces quite big quantity with metal base effectively in self-assembled monolayer (SAM) field, and the compound (for example exhausted compound) that produces as byproduct of reaction can be further with H-H reaction and be hydrogenated, used whereby compound regeneration is suitable for the form that hydrogen produces.Surprisingly, compound commonly used also can produce quantity effectively in forming SAM is enough to be used in energy-producing hydrogen, comprises for example in fuel cell or hydrogen burning engine (embodiment 1-2).

Compound such as organic mercaptan compound are known in the SAM field because of the ability that the reaction of their spontaneous and special metal base materials forms the organic mercaptan salt compound that is attached to the metallic surface.SAM is described to the organized set that closely combines molecule usually.By the self-assembled monolayer that for example forms by the chemisorption of organic molecule on metallic surface (for example gold) is the synthetic organic monolayer of feature distinctness.Referring to Ulman, An Introduction to Ultrathin OrganicFilms:From Langmuir-Blodgett to Self-Assembly, Academic Press, SanDiego, 1991; People such as Dubois, Annu.Rev.Phys.Chem.43:437 (1992).When the organic mercaptan compound is contacted with metal base, since the chemisorption of sulphur on the metal base textured surfaces, the spontaneous formation of these individual layers.Molecule organizes themselves into the lattice that matches on the surface of metal base.Referring to Porter, J.Am.Chem.Soc., 109:3559 (1987); People such as Camillone III, Chem.Phys., 98:3503 (1993); People such as Fenter, Science, 266:1216 (1994); 20; People such as Chidsey, Langmuir, 6:682 (1990); People such as Sun, Thin Solid Films, 242:106 (1994).Except forming the individual layer on the metallic surface, above-mentioned reference reaction produces a large amount of hydrogen as by product.

Term used herein " hydrogen generation compound " is meant the compound that has formula R-XH and can produce hydrogen when reacting with metal base.Can discharge hydrogen when in one embodiment, X is illustrated in and contacts with the reactive metal base material and be attached to reactive part on the metal base.Sulphur is for when having the reactive part of well-known reactive character when contacting with reactive metal base material (referring to above).Except mercaptan compound (for example comprising the compound of sulphur as the reactivity part), it also is useful having oxygen and selenium compound, because oxygen, selenium and the sulphur same gang in periodictable, and have similar reactive character.Thereby, hydrogen produce exist in the compound and be applicable to that reactive part of the present invention comprises for example sulphur, oxygen and selenium.Therefore, in one embodiment, it is " organic mercaptan " that hydrogen produces compound, or has the compound (referring to for example embodiment 1) of sulphur as any organic moiety (" R ") of reactivity part and this paper definition.

In another embodiment of the present invention, when making hydrogen produce compound and metal base reaction, can produce the dehydrogenation generation hydrogen of compound hydrocarbon part by hydrogen.Therefore, hydrogen generation compound can comprise that also hydrocarbon (for example wherein X is a hydrogen) (vide infra; Embodiment 2).

Hydrogen produces compound and also comprises organic moiety (" R ").Hydrogen produce exist in the compound and be applicable to that organic moiety of the present invention generally comprises hydrocarbon, and can comprise and can in handling process such as (for example transport, shift, reaction), keep the required phase of compound and substantially can interfering compound and any organic moiety of the reaction of reactive metal base material.The suitable R group includes but not limited to alkyl, assorted alkyl, low alkyl group, alkenyl, substituted alkenyl base, alkynyl, aryl, heteroaryl, alkoxyl group, cycloalkyl, heterocyclic radical, alkaryl, aralkyl, arylalkenyl, sweet-smelling alkynyl, arylidene, oxygen arylidene and their combination.The R group can be replacement or unsubstituted, and can comprise one or more heteroatomss.

Term used herein " alkyl " is meant to have the 1 monovalence straight or branched alkyl to about 12 carbon atoms, comprises methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-hexyl etc.For example, by in conjunction with alkyl and hydrogen atom, can obtain alkane.

Term used herein " assorted alkyl " is meant and comprises at least one heteroatomic alkyl.Term used herein " heteroatoms " is meant N, O, S etc.

" substituted alkyl " used herein be meant and also have one or more substituent alkyl, wherein substituting group be selected from hydroxyl, alkoxyl group, sulfydryl, cycloalkyl, substituted cycloalkyl, heterocyclic radical, substituted heterocyclic radical, aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, substituted aryloxy, halogen, cyano group, nitro, amino, amido ,-C (O) H, acyl group, oxygen acyl group, carboxyl, sulfonyl, sulfoamido, alkylsulfonyl etc.

" low alkyl group " used herein is meant to have 1 alkyl to about 6 carbon atoms.

" alkenyl " used herein is meant the straight or branched alkyl that has one or more carbon-to-carbon double bonds and have about 2 to 12 carbon atoms, and " substituted alkenyl base " is meant and also has one or more top listed substituent alkenyls.

" alkynyl " used herein is meant the straight or branched alkyl that has at least one carbon-to-carbon triple bond and have about 2 to 12 carbon atoms, and " substituted alkynyl " is meant and also has one or more top listed substituent alkynyls.

" aryl " used herein is meant the aromatic base with 6 to 14 carbon atoms, and " substituted aryl " is meant and also has one or more top listed substituent aryl.

" heteroaryl " used herein is meant and comprises one or more heteroatomss (for example N, O, S etc.) as a ring structure part and have the aromatic nucleus of 3 to 14 carbon atoms, " substituted heteroaryl " be meant also have one or more above listed substituent heteroaryls.

" alkoxyl group " used herein is meant part-O-alkyl, wherein alkyl as hereinbefore defined, " substituted alkoxy " be meant also have one or more above listed substituent alkoxyl groups.

" cycloalkyl " used herein is meant the cycloalkyl that contains that comprises about 3 to 8 carbon atoms, and " substituted cycloalkyl " is meant and also has one or more top listed substituent cycloalkyl.

" heterocyclic radical " used herein, when not relating to the aromatic nucleus use, be meant to comprise one or more heteroatomss (for example N, O, S etc.) as a ring structure part and have ring (promptly the containing ring) base of 3 to 14 carbon atoms, " substituted heterocyclic radical " is meant and also has one or more top listed substituent heterocyclic radicals.

" alkylaryl " used herein is meant the aryl that alkyl replaces, and " substituted alkyl aryl " is meant and also has one or more top listed substituent alkylaryls.

" aralkyl " used herein is meant the alkyl that aryl replaces, and " substituted aralkyl " is meant and also has one or more top listed substituent aralkyl.

" arylalkenyl " used herein is meant the alkenyl that aryl replaces, and " replacement arylalkenyl " is meant and also has one or more top listed substituent arylalkenyls.

" sweet-smelling alkynyl " used herein is meant the alkynyl that aryl replaces, and " replacement sweet-smelling alkynyl " is meant and also has one or more top listed substituent sweet-smelling alkynyls.

" arylidene " used herein is meant the divalent aryl with 6 to 14 carbon atoms, and " replacement arylidene " is meant and also has one or more top listed substituent arylidene.

" oxygen arylidene " used herein is meant part " O-arylidene ", and wherein arylidene is as the definition of top institute, and " replacement oxygen arylidene " is meant and also has one or more top listed substituent oxygen arylidene.

Provide to be applicable to that hydrogen of the present invention produces the various examples of compound, and do not planned to be limited to the hydrocarbon of any specific size.For example, hydrogen produces compound and can comprise having big alkyl as the molecule of 6 or above carbon (C for example ₆-C ₁₂, C ₁₂-C ₂₀Or greater than 20 carbon atoms), have the molecule (for example being less than 6 carbon atoms) of less hydrocarbon.Example comprises thiomethyl alcohol (CH ₃SH) and have a formula CH ₃(CH ₂) _nThe organic mercaptan of SH, wherein n=is less than 6 (for example 2,3,4 or 5).Example also comprises the organic mercaptan with a plurality of thiol groups.Have in each molecules of compound of a plurality of thiol groups and generally be less than 4 thiol groups (for example 2 or 3).Molecule with height-XH base (for example mercaptan) ratio passes through-X-X-key formation polymkeric substance, and its low viscosity can reduce the validity that is used for compound of the present invention.Example with compound of a plurality of-XH base comprises HS-(CH ₂) _n-SH, wherein n=is less than 6 (for example 2-3), and heteroatomic compound such as dithiothreitol (DTT).Other example that is applicable to compound of the present invention comprises HO-CH ₂-CH ₂-SH, thio phenyl (thiobenzene) and thiophenol.More many cases that is applicable to compound of the present invention is listed in the Figure 4 and 5.

In one embodiment, hydrogen generation compound of the present invention at room temperature exists with liquid form.This liquid state under the room temperature is useful, for example when needs utilize current automobile fuel apportioning method (for example air pump).Thereby it is liquid phase at room temperature generally that useful in the present invention hydrogen produces compound, and has about 20 ℃-Yue 200 ℃ boiling spread.

The organosulfur alkoxide that just makes the reaction of organic mercaptan and auri material produce hydrogen below and be attached on the auri material illustrates the step that makes hydrogen generation compound and the reaction of reactive metal base material, and is as follows:

Example:

Be used for reactive metal base material of the present invention and comprise that comprising metal also can produce any base material that the compound reaction provides the exhausted compound or is attached to the compound on the base material with hydrogen, produce compound with unreacted hydrogen and compare, exhausted compound or be attached to compound on the base material by dehydrogenation.Suitable reactive metal base material can comprise for example gold and silver, platinum, copper and mercury.Metal base also can comprise for example processed metal of removing the oxide on surface coating, strengthens the response capacity of metal base when contacting with hydrogen generation compound as herein described thus.Useful metal base is not restricted to specific size and size range.For given application, the selection of suitable metal substrate sizes is conspicuous to those skilled in the art.The reactive metal base material that uses among the present invention without limits, and can comprise for example film, sheet, paper tinsel, line, wafer, pipe, fiber, rod, ball and their arbitrary combination or complex form aspect form.The reactive metal base material also can be and is designed to increase or maximizes the long-pending form of metallic substrate surface.Have the reactive metal base material that increases surface-area and can comprise for example various forms of nanoporous metal (for example nano-hole golden), described in U.S. Patent number 6805972, this paper introduces its (also referring to U.S. Patent number 4977038) as a reference.

In one embodiment of the present invention, wherein make hydrogen produce the compound reaction and produce hydrogen and be attached to compound on the base material, the present invention comprises that also the compound (for example organic mercaptan salt compound) of separation and combination produces uncombined exhausted compound from the metal base.Term used herein " exhausted compound " is meant that reacting generation hydrogen with metal base also with the hydrogen generation compound that metal base reacts preceding compares by the non-binding compound of dehydrogenation.Therefore the exhausted compound can comprise with the metal base reaction and further from the metal base isolated compound.In some embodiments, when no separating step, produce exhausted compound (seeing below).The exhausted compound can comprise the dipolymer that for example has formula R-X-X-R, produces by the R-X from the metal base separation and combination.In one embodiment, the exhausted compound comprises the polymkeric substance that forms by from metal base isolating multiple (for example at least two kinds) R-X combination of compounds.

Just separate organic mercaptan salt compound formation disulphide molecule and illustrate the method that also produces the exhausted compound from metal base separation R-X compound whereby from the auri material, as follows:

Example:

But, it should be understood that the compound that produces by separating step can comprise except that the compound from metal base isolating multiple " X-R " combination of compounds (for example polymkeric substance).In some cases, for example, produce compound in initial hydrogen and comprise a plurality of reactive parts (HS (CH for example ₂) _nSH) time, can form the exhausted compound by two reactive parts in the connection simplification compound, as shown below:

The whole bag of tricks that separates the R-X compound from metal base all is applicable to method of the present invention, comprises for example by applying the energy.In an example, separate the R-X compound from metal base by applying heat.For example can under greater than 80 ℃ heat, separate the R-X compound from metal base.The heat that applies can comprise for example apply about 50-100 ℃, as 60-80 ℃ and more particularly about 70 ℃ thermal source.Other method can comprise and applies ultraviolet (UV) light, or apply electric current.Be generally about 50kJ/mol according to the surface interaction between bonded compound of the present invention and the metal base series from about 10kJ/mol-.Thiolate-metallographic mutual effect for example has the interaction energy of about 35kJ/mol.Therefore, must apply above the energy of 35kJ compound to the surface with release/separation and combination.Separation and combination will depend in part on compound and the combination of the metal that just using to the required concrete amount of energy of the compound on the metal base, and can easily be determined by the technician.For more discussion of separating metal base material bonded R-X compound, as the release of the organic mercaptan salt compound of temperature-driven, referring to people such as for example Walczak, Langmuir1991,7,2687-2693 from metal base; People such as Bondzie, Surface Science 431 (1999) 174-185; People such as Rowe, Langmuir 1991,7,2307-2312; People such as Ross, Langmuir 1993,9,632-636; People such as Huang, 1993, J.Am.Chem.Soc.115,3342-3343; This paper all introduces them as a reference.

The present invention also comprises from exhausted compound regenerated hydrogen generation compound.Produce compound from exhausted compound regenerated hydrogen and comprise that for example used compound and H-H reaction produce the compound with formula R-XH, produce compound by exhausted compound regenerated hydrogen whereby.Can chemical reduction exhausted compound such as the whole bag of tricks of dipolymer be well known in the art.For example, when dipolymer was disulphide, available hydrogen reduction disulphide formed mercaptan, the rich hydrogen mercaptan of regenerating whereby.For example, can make disulphide and H-H reaction form mercaptan by catalytic hydrogenation (for example with the reaction of rhodium carbonylic catalyst).For example, the whole bag of tricks of catalytic hydrogenation organic mercaptan is conspicuous (referring to for example U.S. Patent number 4767884 to those skilled in the art; People such as Bondzie, Surface Science 431 (1999) 174-185).The hydrogen of exhausted compound of being used to regenerate can produce (for example reformation of the ionization of water, hydrocarbon, high-pressure storage etc.) by any method as known in the art.For example, when on hydrogen-powered vehicle, implementing apparatus and method of the present invention, used compound regeneration is suitable for form that hydrogen produces can carry out producing the position that separate with hydrogen, and as at the vehicle D score, this moment, the restriction such as the high temperature and high pressure (for example reforming) of existing method were just not too important.

Illustrate below by exhausted compound regenerated hydrogen and produce compound.For example, available hydrogen reductive dimerization thing disulphide becomes the mercaptan rich hydrogen mercaptan of regenerating.For example, can disulphide be changed into mercaptan by catalytic hydrogenation, as illustration in following illustrated two reactions:

The method according to this invention also can partly be carried out dehydrogenation by the hydrocarbon that makes hydrogen produce compound and be produced hydrogen, and dehydrogenation wherein takes place when making the reaction of compound and metal base.Therefore, in another embodiment of the present invention, store and produce the method that is used for energy-producing hydrogen and comprise and enable to produce hydrogen and have formula R ₁The fluid cpds of-XH and metal base reaction produce hydrogen and exhausted compound.The exhausted compound can comprise for example having formula R ₂The compound of-XH, wherein R ₂With respect to R ₁By dehydrogenation; R ₃=X, wherein R ₃With respect to R ₁By dehydrogenation; Or their combination.The suitable R base as hereinbefore defined.

According to the present invention, be catalytic dehydrogenation although the dehydrogenation that produces the hydrocarbon part of compound by hydrogen produces the result of hydrogen, principle is identical with catalytic hydrogenation.Difference is that the hydrogen source by this method of hydrocarbon dehydrogenation generation hydrogen may be for wrapping hydrogenous any organic molecule.In normal catalytic hydrogenation, break to the catalyst surface homolysis key (H-H 436kJ/mol) and catalyzer and the new key of hydrogen evolution between the hydrogen molecule.Because these new key deficient in stabilities, so the part hydrogen atom leaves the surface as hydrogen.According to present hydrogen production method, the hydrocarbon part (R for example defined above) that hydrogen produces compound is a hydrogen source.This hydrocarbon partly feeds catalyzer, and catalyst surface is from hydrocarbon extracting section hydrogen and form key with it as before.Check the part bond energy (CH for example of hydrocarbon part ₃-H440kJ/mol; CH ₃CH ₂-H 421kJ/mol; CH ₃CH ₂CH ₂-H 423kJ/mol; CH ₂=CH ₂CH ₂-H 375kJ/mol; (CH ₃) ₃C-H 359kJ/mol; CH ₂=CH-H 465kJ/mol; RS-H 367kJ/mol) and relatively their bond energy and the bond energy (H-H 436kJ/mol) of hydrogen show that in these molecules any one can both lose hydrogen atom to catalyzer.But, for losing those easier (for example propylene and the 2-methylpropanes) that can produce behind the hydrogen than stable molecule.In an example, can select the cyclohexyl part, because it can lose 3 moles the highly stable aromatic structure of hydrogen evolution.It partly is that known method is (referring to for example U.S. Patent number 5189233 that the conversion aryl becomes cyclohexyl; With people such as Makal, CatalyticHydrogenation of Benzene to Cyclohexane in Gas Phase, Pol. (1989) PL 146758).In addition, because first step of method is started by homolysis, therefore in theory, can produce any atom of stablizing group and all be suitable for above-mentioned reaction.It also is effective (Fig. 5) that hydrocarbon molecule produces for hydrogen.

The exemplary compounds that is adapted to pass through hydrocarbon part dehydrogenation storage and generation hydrogen comprises for example butyl sulfhydryl, pentan-thiol, hexylmercaptan, cyclohexylmercaptan and 1,4-hexamethylene two mercaptan.Other example that is adapted to pass through the compound of hydrocarbon part dehydrogenation generation hydrogen comprises the following compound shown in the Figure 4 and 5.

According to the present invention, use compound 1, the hydrocarbon that 4-hexamethylene two mercaptan and Jin Lai illustrate by hydride hydrogen generation compound partly produces hydrogen.As shown below, when 1, during 4-hexamethylene two mercaptan contact gold surface, hydrogen is released immediately, and 1,4-hexamethylene two mercaptan are converted to exhausted compound dithio para benzoquinone and/or 1, and the 4-phenylene dimercaptan adds hydrogen.

Embodiment:

For example, by any exhausted compound dithio para benzoquinone and/or 1 of separating that is used for the whole bag of tricks of separation of hydrogen and liquid as known in the art, 4-phenylene dimercaptan and hydrogen, as utilize difference big on their boiling points or pass through membrane separating method.

Can be by the exhausted compound that dehydrogenation reaction produces by hydrogenation again, used whereby compound regeneration is suitable for the form that re-uses in hydrogen produces.According to following Example, dithio para benzoquinone and 1, the 4-phenylene dimercaptan can be become 1 by chemical reduction, 4-hexamethylene two mercaptan.In this process, molecule is by hydrogenation or " filling again " hydrogen again, and can be used for once more producing and be used for for example energy-producing hydrogen.But chemical reduction exhausted compound such as dithio para benzoquinone and 1, the whole bag of tricks of the hydrocarbon part of 4-phenylene dimercaptan molecule is well known in the art, and comprises for example catalytic hydrogenation.For more discussion of hydrocarbon hydrogenation such as catalytic hydrogenation, referring to people such as for example Botaiux, " NewestHydrogenation Catalysts ", Hydrocarb.Process, in March, 1985,51-59 page or leaf; With U.S. Patent number 6794552; This paper all introduces them as a reference.

Generation is used for the step of energy-producing hydrogen and can be taken place in same position or near the position by the step that exhausted compound regenerated hydrogen produces compound.Perhaps, hydrogen generation step can take place in different positions with exhausted compound regeneration step.For example, hydrogen produces step and can occur in the automobile or on the automobile, and exhausted compound regeneration step can occur under the automobile or separate with automobile, comprises for example after shifting out the exhausted compound from automobile.In an example, the regeneration of exhausted compound can occur in the service station, is similar to the service station (for example service station, truck service station etc.) of just using at present.Produce when occurring in fixed cell as building (for example dwelling house, shop, shelter etc.) at hydrogen, regeneration also can occur in Architectural Services Department, as in building and near the position of hydrogen generation position in the building, maybe can occur in and builds different positions.

The invention still further relates to and produce the device that is used for energy-producing hydrogen.The inventive system comprises the storage tank that is suitable for holding the hydrogen generation compound with formula R-XH, wherein R is that organic moiety and X are the reactive part that is selected from sulphur, oxygen and selenium.Device comprises that also being suitable for producing compound with hydrogen reacts the metal base that produces hydrogen and exhausted compound and/or be attached to the R-X compound on the metal base.

Produce in the embodiment of the compound that is attached to metal base at hydrogen generation compound and metal base reaction, device can comprise the energy that can produce uncombined exhausted compound (dipolymer that for example has formula R-X-X-R) from the compound of metal base separation and combination in addition.The energy can comprise for example thermal source or UV light source.For example, when device was present on the automobile, thermal source can comprise the heat that is obtained by hydrogen consumer such as hydrogen burning engine.In another embodiment, metal base can be suitable for unloading from device.In this embodiment, comprise that the complex body of metal base and bonded compound can unload from device, and be exposed to energy, so that from the compound of metal base separation and combination from the energy.

Device also can comprise the storage tank that is used to store the exhausted compound.In one embodiment, the storage tank that is used for storing the exhausted compound is suitable for removing the exhausted compound from device.Device can comprise regeneration room in addition, and this regeneration room is suitable for used compound and produces the compound with formula R-XH with the H-H reaction of accepting from the device external source, and used whereby compound regeneration is suitable for the form that hydrogen produces.Device of the present invention can utilize the hydrogen generate energy.Utilize the hydrogen generate energy for example can comprise and in hydrogen burning engine or fuel cell, consume hydrogen.

The hydrogen that Fig. 2 illustrates according to one embodiment of this invention produces and regeneration system rapidly 30 and device 32.System shown comprises that service station 34, generation are used for the device 32 of energy-producing hydrogen and shift out station 36.Device 32 comprises the storage tank 38 that is suitable for holding the hydrogen generation compound with formula R-XH, and wherein R is that organic moiety and X are selected from sulphur, oxygen and selenium.Device 32 also comprises and is suitable for producing the exhausted compound with compound reaction and/or is attached to R-X compound on the metal base 40 and the reactive metal base material 40 of hydrogen.In this illustrative embodiment, device comprises the reaction chamber 42 that comprises the metal base 40 and the energy 44, and the energy 44 is used for separation and combination and produces uncombined exhausted compound (dipolymer that for example has formula R-X-X-R) to the R-X compound on the metal base 40.Device 32 also comprises the storage tank 46 that stores the exhausted compound, and it is suitable for removing the exhausted compound from device.Storage tank 46 and storage tank can separate, or form a sequential cells that separates with for example baffle plate 47.In one embodiment, baffle plate 47 can be movably baffle plate, and wherein the position of removable baffle plate defines the volume of storage tank 38 and 46.The position of baffle plate is subjected to for example to add or removes with corresponding and is subjected to divide in storage tank 38 and 46 other hydrogen to produce the influence of compound and exhausted compound relative populations.For example, when baffle plate 47 was removable baffle plate, storage tank 38 hydrogen of packing into produced compound and can cause moving of baffle plate 47, thereby causes the expansion of storage tank 38 volumes and relative the dwindling of storage tank 46 volumes.System also can comprise the hydrogen consumer 48 that is suitable for accepting from device 32 of the present invention hydrogen.

The operation of system of the present invention and device is discussed with reference to figure 2.With hydrogen produce compound (for example liquid organic mercaptan) from the service station 34 transfer to device 32 (referring to Fig. 2, step 1).Compound (R-XH among Fig. 2) is generally liquid form, and can be stored in the storage tank 38 and (see Fig. 2, step 2).When needed, compound can produce the hydrogen (H among Fig. 2 with 40 reactions of reactive metal base material ₂) and exhausted compound and/or the R-X compound that is attached to metal base 40 (see Fig. 2, step 3).The hydrogen that reactions steps produces can be sent to hydrogen consumer 48, (sees Fig. 2, step 4) as fuel cell or hydrogen burning engine.Produce the exhausted compound by apply the R-X compound that energy can be from metal base 40 separation and combination to metal base 40 from the energy 44, as the dipolymer with formula R-X-X-R (is seen Fig. 2, step 5).Behind separating step, for example in the storage tank 46 that stores the exhausted compound, collect the exhausted compound behind condensation and the formation liquid and (see Fig. 2, step 6).Then shift out station 36 from storage tank 46, remove the exhausted compound (see Fig. 2, step 7) and subsequently regeneration be suitable for the form (for example hydrogen generation compound) of hydrogen generation.

Therefore, the invention still further relates to the subassembly that produces and utilize hydrogen.In one embodiment, subassembly comprises and is used to produce the first module of hydrogen and be used to utilize the energy-producing Unit second of hydrogen that wherein Unit second is suitable for accepting hydrogen from first module.First module comprises the storage tank that is suitable for holding the hydrogen generation compound with formula R-XH, and wherein R is that organic moiety (seeing above) and X are selected from sulphur, oxygen and selenium; Produce the metal base that the compound reaction produces hydrogen and exhausted compound and/or is attached to the R-X compound of metal base with being suitable for hydrogen.Unit second can comprise the hydrogen consumer, as hydrogen burning engine or fuel cell.Subassembly of the present invention for example can be included in vehicle or the automobile.Subassembly of the present invention can comprise in addition and can separate the energy that R-X produces exhausted compound (dipolymer that for example has formula R-X-X-R) from metal base.The energy can comprise for example thermal source or UV light source.

Subassembly also can comprise the storage tank that is used to store the exhausted compound.In one embodiment, the storage tank that is used for storing the exhausted compound is suitable for removing the exhausted compound from device.Subassembly can comprise regeneration room in addition, and this regeneration room is suitable for used compound and produces the compound with formula R-XH with the H-H reaction of accepting from the device external source, and the exhausted compound of regenerating whereby becomes to be suitable for the form that hydrogen produces.

Fig. 3 further illustrates system 50 and device 52 according to embodiments of the present invention.Device 52 of the present invention for example can be positioned at provides vehicle powered 54 inside with hydrogen consumer 56.Therefore, illustrated system 50 comprises having vehicle 54, service station 58 and the transportation means 60 that produces the device 52 that is used for energy-producing hydrogen.With hydrogen produce compound 62 (for example liquid organic mercaptan) from the service station 58 storage tanks 64 of transferring to the device 52 that is positioned at vehicle 54 inside.When needs, compound 62 can produce hydrogen and exhausted compound with metal base 66 reactions and/or be attached to the R-X compound (for example organosulfur alkoxide) of metal base 66.Hydrogen can be transported to hydrogen consumer 56 and be used to produce the used energy of vehicle 54 operations.Can produce exhausted compound (for example dipolymer R-X-X-R) by the R-X compound from metal base 66 separation and combination to metal base 66 by apply energy from the energy.Exhausted compound 68 can be stored in the storage tank 70, and finally removes from vehicle 54 and be positioned at for example service station 58.Exhausted compound 68 can be reproduced and become to be suitable for the form that hydrogen produces.Regeneration can occur in 58 places, service station or in other position.Produce compound and/or the arrival of exhausted compound and leave the service station by transportation means 60 transportation of hydrogen.Be applicable to that transportation means of the present invention can comprise any instrument from a position to another position transport liquid, for example comprise conventional vehicles transportation means (for example truck, tank wagon, ship etc.) and by pipeline or other method.

Embodiment 1

The reacted hydrogen of organic mercaptan and metal base produces

The following examples explanation is reacted the collection of the hydrogen that produces with quantitative by making organic mercaptan compound and metal base.Carry out the aitiogenic container of hydrogen and carry out illustrative reaction by providing, container comprises chamber, import and outlet.React by placing response material in the chamber of container, make the material reaction, and measure the hydrogen that produces by reaction.Material is sent in the container via import, takes out the hydrogen that produces by reaction from container via outlet.Comprise that vapor-phase chromatography (" GC-RGA ") (Reduction Gas Analyzer Trace Analytical, In., Model TA 3000) by being connected to the reducing gas analyser is analyzed and quantitative hydrogen by vapor-phase chromatography.

At first carry out positive control experiment and can detect hydrogen in container by the material reaction is produced so that confirm test set.For over against photograph, in the chamber of container, place a small amount of sodium (10-20mg), wherein the volume of chamber is about 25ml.Sealed vessel and the chamber is vacuumized then with vacuum pump.In flask, introduce water (20 μ l) again, and with the chamber in the sodium reaction that exists.Reaction between sodium and the water produces a large amount of hydrogen, is full of flask.Reaction back is presented at the hydrogen of the about 10000ppm of existence in the chamber of flask with the inclusion of GC-RGA analyzing container chamber.

Use organic mercaptan and metal base to be similar to above-mentioned experiment over against photograph.Hexylmercaptan (99%) is available from Aldrich chemical company.The bronze end, sphere, APS 5.5-9.0 micron, 99.96% (metal matrix), S.A.0.05-0.2m ²/ g is available from Alfa Aesar.Bronze end (300mg) is placed in the chamber of container (the about 5ml of volume).By vacuum pump the chamber is vacuumized behind the sealed vessel, (1ml) is incorporated in the chamber of container with hexylmercaptan.After the reaction, with the inclusion of GC-RGA analyzing container.Hydrogen in the detection receptacle, after the reaction, the about 3000ppm of quantity.

Repeated experiments as mentioned above, is placed bronze end (300mg), and will will be injected into indoor at 2% hexylmercaptan in the ethanol (1ml) after vacuum pump vacuumizes in the chamber of container.After the reaction, measure hydrogen content, approximately 2000ppm by GC-RGA.In addition, analyze air in the room so that determine the hydrogen content and the residence time.Air in the room, be shown in Table 1 over against hydrogen content experimental result according to, pure hexylmercaptan and 2% hexylmercaptan in ethanol.

Table 1

Sample	Hydrogen, ppm
Sample	Hydrogen, ppm	Air in the room	500
Over against photograph	10000	Air in the room	500
Over against photograph	10000	Pure hexylmercaptan	3000
2% hexylmercaptan in ethanol	2000	Pure hexylmercaptan	3000

Further repeat above-mentioned experiment as mentioned above, but use the vapor-phase chromatography (" GC-MC ") (Agilent GC/MS model 6890N/5973) that is connected to mass spectroscopy to carry out hydrogen analysis and quantitative.GC-MS analyzes the experimental result that has confirmed that GC-RGA analyzes, and shows by making the reaction of organic mercaptan compound and metal base produce hydrogen.Although instrument can not demonstrate the hydrogen peak value, determined the negative peak of air below the residence time in the room.This negative peak may be owing to lacking background gas (for example He) and may being to have the residence time other gas lower than air.This is interpreted as hydrogen because it provided with over against according to similar result.

Embodiment 2

The reacted hydrogen of hydrocarbon and metal base produces

The following examples explanation makes the generation and the collection of hydrocarbon and the reacted hydrogen of golden metal catalyst, and golden metal catalyst makes hydrocarbon dehydrogenation and release hydrogen.

In the present embodiment, clog the inlet of GC/MS and be heated to 175 ℃ with the bronze end.Constant speed and the heating gold after, by inlet inject 1 μ l hexalin (99%, Aldrich).Directly monitor effluent by GC/MS (seeing above).Reaction and display by GC/MS monitoring hexalin and gold goes out the negative peak that the residence time is similar to air in the room.The result shows and lacks helium in the detector or have other gas that this is interpreted as reacting the hydrogen of generation.In addition, the detected main hydrocarbon compound in reaction back is phenol (being the hexalin of dehydrogenation).Do not detect hexalin after the reaction.

In contrast, when having gold filling step, similarly do not test.In control experiment, do not detect negative peak or phenol.Detected unique compound is a hexalin, shows when lacking golden metal base not react.

Although the present invention has been described, it should be understood that change and change all to comprise within the spirit and scope of the present invention with reference to embodiment described herein.Therefore, the present invention is limited by following claim only.

Claims

1. A method of producing energy comprising:

reacting a liquid compound capable of generating hydrogen and having the formula R-XH with a metal substrate to generate hydrogen, and utilizing the hydrogen to generate energy;

wherein R is selected from the group consisting of alkyl, heteroalkyl, alkenyl, substituted alkenyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkyl, heterocyclyl, alkaryl, aralkyl , aralkenyl, aralkynyl, arylene, oxyarylene and combinations thereof; X is selected from sulfur, oxygen, selenium and hydrogen.

2. The method of claim 1, wherein the metal substrate comprises a metal selected from the group consisting of gold, silver, platinum, copper, and mercury.

3. The method of claim 1, wherein said metal substrate comprises metal that has been treated to remove surface oxide coatings.

4. The method of claim 1, wherein R is _C2 - _C8 alkyl, heteroalkyl, alkenyl or heteroalkenyl.

5. The method of claim 1, wherein utilizing the hydrogen comprises consuming the hydrogen in a combustion engine.

6. The method of claim 1, wherein utilizing the hydrogen comprises consuming the hydrogen in a fuel cell.

7. A method of storing and generating hydrogen for energy production, comprising:

reacting a liquid compound capable of generating hydrogen and having the formula R ₁ -XH with a metal substrate to produce hydrogen gas and R ₁ -X bound to the metal substrate; and

collect hydrogen;

_wherein the group R is selected from the group consisting of alkyl, heteroalkyl, alkenyl, substituted alkenyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkyl, heterocyclyl, alkaryl, moieties of aralkyl, aralkenyl, aralkynyl, arylene, oxyarylene, and combinations thereof; X is selected from sulfur, oxygen, and selenium.

8. The method of claim 7, wherein the metal substrate comprises a metal selected from the group consisting of gold, silver, platinum, copper, and mercury.

9. The method of claim 7, wherein said metal substrate comprises metal that has been treated to remove surface oxide coatings.

10. The method of claim 7, wherein the liquid compound is a _C2 - _C8 organic thiol.

11. The method of claim 7, further comprising isolating R1 _- X bound to the metal substrate to generate spent compounds.

12. The method of claim 11, wherein the used compound is a dimer having the formula _R1 - _XXR1 .

13. The method of claim 11, wherein said separating comprises heating R1 _- X bonded to the metal substrate.

14. The method of claim 11, wherein said isolating comprises exposing R1 _- X bound to the metal substrate to ultraviolet (UV) light.

15. The method of claim 11, further comprising reacting the used compound with hydrogen to produce a compound of formula _R1 -XH, whereby the hydrogen-generating compound is regenerated from the used compound.

16. The method of claim 15, wherein reacting the used compound with hydrogen comprises catalytic hydrogenation.

17. The method of claim 15, wherein generating hydrogen and regenerating spent compounds occur at different locations.

18. The method of claim 7, further comprising:

Reacting the liquid compound with the metal substrate produces hydrogen gas and used compounds comprising: (a) _R2 -XH, where _R2 is dehydrogenated relative to _R1 ; (b) _R3 =X, where R ₃ is dehydrogenated relative to R ₁ ; or (c) a combination of (a) and (b); wherein each of R ₁ , R ₂ and R ₃ is independently selected from the group consisting of alkyl, heteroalkyl, chain alkenyl, substituted alkenyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkyl, heterocyclyl, alkaryl, aralkyl, aralkenyl, aralkynyl, arylene, and Moieties in oxyarylene;

19. The method of claim 7, wherein collecting includes consuming the hydrogen in a combustion engine or a fuel cell.

20. A method of storing and generating hydrogen for energy production, comprising:

Reacting a liquid compound capable of generating hydrogen and having the formula R ₁ -XH with a metal substrate to produce hydrogen gas and a used compound comprising:

(a) R ₂ -XH, wherein R ₂ is dehydrogenated relative to R ₁ ;

(b) R ₃ =X, wherein R ₃ is dehydrogenated relative to R ₁ ; or

(c) a combination of (a) and (b); and

collect hydrogen;

wherein each of R ₁ , R ₂ and R ₃ is independently selected from the group consisting of alkyl, heteroalkyl, alkenyl, substituted alkenyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkane Moieties in radicals, heterocyclyls, alkaryls, aralkyls, aralkenyls, aralkynyls, arylenes, oxyarylenes, and combinations thereof;

and X are selected from sulfur, oxygen, selenium and hydrogen.

21. The method of claim 20, wherein the metal substrate comprises gold, silver, platinum, copper or mercury.

22. The method of claim 20, wherein said metal substrate comprises metal that has been treated to remove surface oxide coatings.

23. The method of claim 20, further comprising reacting the used compound with hydrogen to produce a compound of formula _R1 -XH, whereby the hydrogen-generating compound is regenerated from the used compound.

24. The method of claim 23, wherein reacting the used compound with hydrogen comprises catalytic hydrogenation.

25. The method of claim 23, wherein generating hydrogen and regenerating spent compounds occur at different locations.

26. The method of claim 20, further comprising reacting the R1 _- XH compound with the metal substrate to produce hydrogen gas and R1 _- X bound to the metal substrate.

27. The method of claim 26, further comprising reacting the _R2 -XH compound with the metal substrate to produce hydrogen gas and R2 _- X bound to the metal substrate.

28. The method of claim 27, further comprising isolating R ₁ -X- or R ₂ -X- bound to the metal substrate to produce R ₁ -X- or R ₂ comprising separating from the metal substrate The used compound of -X-.

29. The method of claim 28, wherein the used compound comprising _R1 -X- or _R2 -X- is selected from _R1 - _XXR1 , _R2 - _XXR2 or _R1- _XXR2 .

30. The method of claim 20, wherein said collecting includes consuming hydrogen in a combustion engine or a fuel cell.

31. An apparatus for generating hydrogen for energy generation, comprising:

Tanks suitable for containing liquid compounds capable of generating hydrogen and having the formula R-XH, wherein R is selected from the group consisting of alkyl, heteroalkyl, alkenyl, substituted alkenyl, alkynyl, aryl, heteroaryl, Moieties of alkoxy, cycloalkyl, heterocyclyl, alkaryl, aralkyl, aralkenyl, aralkynyl, arylene, oxyarylene, and combinations thereof;

and X are selected from sulfur, oxygen and selenium; and

Metal substrates suitable for reacting with liquid compounds to produce R-X compounds and hydrogen gas bound to the metal substrate.

32. The apparatus of claim 31, wherein said liquid compound comprises a _C2 - _C8 organothiol compound.

33. The device of claim 31, wherein said metal substrate comprises silver, platinum, copper, or mercury.

34. The device of claim 31, wherein said metal substrate comprises gold.

35. The device of claim 34, wherein the gold comprises nanoporous gold.

36. The device of claim 31, wherein said metal substrate comprises metal that has been treated to remove surface oxide coatings.

37. The apparatus of claim 31, further comprising an energy source capable of separating R-X from the metal substrate to produce spent compounds.

38. The device of claim 37, wherein the used compound is a dimer having the formula R-X-X-R.

39. The apparatus of claim 37, wherein the energy source comprises a heat source.

40. The device of claim 37, wherein the energy source comprises a UV light source.

41. The apparatus of claim 37, further comprising a storage tank for storing the spent compound.

42. The device of claim 41, wherein the storage tank storing the used compound is adapted to remove the used compound from the device.

43. The apparatus of claim 37, further comprising a regeneration chamber adapted to react the spent compound with hydrogen received from a source external to the apparatus to produce a compound of formula R-XH, whereby regeneration from the spent compound produces Hydrogen compounds.

44. The apparatus of claim 31, wherein hydrogen gas is used to generate energy.

45. A vehicle comprising a hydrogen consuming device and the device of claim 31.

46. The vehicle of claim 45, wherein the hydrogen consuming device comprises a hydrogen combustion engine.

47. The vehicle of claim 45, wherein the hydrogen consuming device comprises a fuel cell.

48. An apparatus for generating hydrogen for energy production, comprising:

a storage tank adapted to contain a liquid compound capable of generating hydrogen and having the formula R ₁ -XH; and

Metal substrates suitable for reaction with liquid compounds to produce hydrogen gas and spent compounds including:

(a) R ₂ -XH, wherein R ₂ is dehydrogenated relative to R ₁ ;

(b) R ₃ =X, wherein R ₃ is dehydrogenated relative to R ₁ ; or

(c) a combination of (a) and (b);

wherein each of R ₁ , R ₂ and R ₃ is independently selected from the group consisting of alkyl, heteroalkyl, alkenyl, substituted alkenyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkane Moieties in radicals, heterocyclyls, alkaryls, aralkyls, aralkenyls, aralkynyls, arylenes, oxyarylenes, and combinations thereof; and

X is selected from sulfur, oxygen, selenium and hydrogen.

49. The device of claim 48, wherein said metal substrate comprises silver, platinum, copper, or mercury.

50. The device of claim 48, wherein said metal substrate comprises gold.

51. The device of claim 50, wherein the gold comprises nanoporous gold.

52. The device of claim 48, wherein said metal substrate comprises metal that has been treated to remove surface oxide coatings.

53. The apparatus of claim 48, further comprising a storage tank for storing the spent compound.

54. The device of claim 53, wherein the storage tank storing the used compound is adapted to remove the used compound from the device.

55. The apparatus of claim 48, further comprising a regeneration chamber adapted to react the spent compound with hydrogen received from a source external to the apparatus to produce a compound of formula R ₁ -XH, whereby energy is regenerated from the spent compound Compounds that produce hydrogen.

56. The apparatus of claim 48, wherein hydrogen gas is used to generate energy.

57. A vehicle comprising a hydrogen consuming device and the device of claim 48.

58. The vehicle of claim 57, wherein said hydrogen consuming device comprises a hydrogen combustion engine.

59. The vehicle of claim 57, wherein said hydrogen consuming device comprises a fuel cell.

60. A method of regenerating a hydrogen-generating compound from a spent compound, comprising:

receiving spent compounds from the apparatus of claim 42; and

The used compound is reacted with hydrogen to produce a compound of formula R-XH, whereby the hydrogen generating compound is regenerated from the used compound.

61. A method of regenerating a hydrogen-generating compound from a spent compound, comprising:

receiving spent compounds from the apparatus of claim 54; and

The used compound is reacted with hydrogen to produce a compound of formula _R1 -XH, whereby the hydrogen-generating compound is regenerated from the used compound.

62. An assembly for generating and utilizing hydrogen comprising:

A first unit for generating hydrogen, the first unit comprising:

(a) a storage tank suitable for containing a liquid compound capable of generating hydrogen and having the formula R-XH; wherein R is selected from the group consisting of alkyl, heteroalkyl, alkenyl, substituted alkenyl, alkynyl, aryl, hetero Moieties of aryl, alkoxy, cycloalkyl, heterocyclyl, alkaryl, aralkyl, aralkenyl, aralkynyl, arylene, oxyarylene, and combinations thereof; and X is selected from from sulfur, oxygen and selenium; and

(b) a metal substrate suitable for reacting with a liquid compound to produce an R-X compound and hydrogen bound to the metal substrate; and

A second unit for generating energy from hydrogen, wherein the second unit is adapted to receive hydrogen from the first unit.

63. The assembly of claim 62, wherein said reactive metal substrate comprises silver, platinum, copper, mercury, or a metal treated to remove surface oxide coatings.

64. The assembly of claim 62, wherein said metal substrate comprises gold.

65. The assembly of claim 64, wherein the gold comprises nanoporous gold.

66. The assembly of claim 62, further comprising an energy source capable of separating R-X from the metal substrate to produce spent compounds.

67. The assembly of claim 66, wherein said spent compound comprises a dimer having the formula R-X-X-R.

68. The assembly of claim 66, wherein said energy source comprises a heat source.

69. The assembly of claim 66, wherein the energy source comprises a UV light source.

70. The assembly of claim 66, further comprising a storage tank for storing the used compound, the storage tank being adapted to remove the used compound from the device.

71. The assembly of claim 66, further comprising a regeneration chamber adapted to react the spent compound with hydrogen received from a source external to the device to produce a compound of formula R-XH, whereby energy is regenerated from the spent compound Compounds that generate hydrogen.

72. The combination of claim 62, wherein the second unit comprises a combustion engine.

73. The assembly of claim 62, wherein the second unit comprises a fuel cell.

74. The assembly of claim 62, wherein said assembly is contained in an automobile.

75. An assembly for generating and utilizing hydrogen comprising:

A first unit for producing hydrogen, the first unit comprising:

(1) a storage tank suitable for containing a liquid compound capable of generating hydrogen and having the formula R ₁ -XH, and

(2) Metal substrates suitable for reaction with liquid compounds to produce hydrogen gas and used compounds, including:

(a) R ₂ -XH, wherein R ₂ is dehydrogenated relative to R ₁ ; (b) R ₃ =X, wherein R ₃ is dehydrogenated relative to R ₁ ; or (c) (a) and (b) combination;

X is selected from sulfur, oxygen, selenium and hydrogen.

76. The assembly of claim 75, wherein said reactive metal substrate comprises silver, platinum, copper, mercury, or a metal treated to remove surface oxide coatings.

77. The assembly of claim 75, wherein said metal substrate comprises gold.

78. The assembly of claim 77, wherein the gold comprises nanoporous gold.

79. The assembly of claim 75, further comprising a storage tank for storing the used compound, the storage tank being adapted to remove the used compound from the device.

80. The assembly of claim 79, further comprising a regeneration chamber adapted to react the spent compound with hydrogen received from a source external to the device to produce a compound of formula R-XH, whereby energy is regenerated from the spent compound Compounds that generate hydrogen.

81. The combination of claim 75, wherein the second unit comprises a combustion engine.

82. The assembly of claim 75, wherein the second unit comprises a fuel cell.

83. The assembly of claim 75, wherein said assembly is contained in an automobile.