CN103764875A - Cavitation assisted sonochemical hydrogen production system - Google Patents
Cavitation assisted sonochemical hydrogen production system Download PDFInfo
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- CN103764875A CN103764875A CN201280038937.7A CN201280038937A CN103764875A CN 103764875 A CN103764875 A CN 103764875A CN 201280038937 A CN201280038937 A CN 201280038937A CN 103764875 A CN103764875 A CN 103764875A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/02—Process control or regulation
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
Embodiments of the invention are directed to an electrolyte composition of matter comprising an aqueous solvent, at least one inorganic salt dissolved in said solvent; and at least one organic acid or salt thereof, the acid being substantially soluble in the aqueous solvent and being present at a concentration sufficient to support cavitation-assisted electrolytic combustion. Low molecular weight organic acids and inorganic salts are demonstrated herein as being useful for generating hydrogen.
Description
Relate generally to of the present invention is efficiently prepared hydrogen, relates more specifically to original position and prepares hydrogen.
Water is comprised of two parts of hydrogen and a oxygen (with quality or volumeter).Under given energy input E1, two mole of water produce one mole of oxygen (O by the defection of any-mode solution
2) and two mol of hydrogen (H
2).When combining by any-mode, hydrogen and oxygen react to form water, thereby discharge given energy output E2.With regard to all known physics and chemistry principles, E1>E2, therefore with regard to thermodynamics, described method is not favourable when direct effect.For hydrogen can must be taken measures to reduce the dissociation energy of water or provide energy with certain alternate manner in described process as the energy economic use, for example, use catalysis to strengthen or all aforesaid ways.
Hydrogen can be produced by various chemical substances (including but not limited to water, hydrocarbon, plant, rock etc.) by variety of way (including but not limited to chemistry, electricity, heat, radiolysis etc.).In the present invention, water is used as to hydrogen source, and uses the catalyzed combination of electrolysis and cavitation to produce hydrogen.Cavitation process can pass through variety of way (acoustics, inertia flow mechanics, non-inertia flow mechanics, machinery, electromagnetism etc.) or its arbitrary combination realizes.
As the abundantest element of content on the earth and in universe, hydrogen is hopeful especially as the fuel source on the earth and in space.Hydrogen can be family and factory, mode of transportation (aircraft, train and vehicle) provide power.Therefore, hydrogen can be used to thoroughly eliminate the carbon fuel of electric power in the epoch, in the contribution aspect hommization process, land climate change is reduced only thus by it.As described in numerous summaries of hydrogen applications, there are four significant " obstacles ".As described below separately:
1. produce-produce a large amount of hydrogen as the mode of efficient, safety, environment " close friend " how.
2. store-how to store low-density inflammable gas.
3. distribute-because hydrogen is difficult to store, be therefore difficult to transportation.
4. use-in view of first two, can how to use hydrogen is a larger obstacle.
Therefore, need a kind of method and system that overcomes the problem running in prior art, and a kind of hydrogen production process and device of economy are provided.
Provide a kind of by hydrogeneous liquid as water generates hydrogen (H
2) method and apparatus.In one embodiment, described structure is to be provided with the electrolyzer that catalysis strengthens, so that the volume of prepared hydrogen and quality maximization, and energy input is minimized, make thus running cost be down to minimum.In the following way this equipment is carried out to the special formation that strengthens dissociating of water and hydrogen with catalysis that arranges: the 1) vessel assembly of electromagnetic field configuration; 2) use sonochemistry and cavitation; And 3) in described equipment, use suitable solute and the solvent of the pH, ionic condition and the partial potential that change this equipment solution.
Cavitation can produce in several ways, includes but not limited to: acoustic energy, hydromeehanics (inertia, non-inertia), machinery and electromagnetic energy etc. or its arbitrary combination.
As described in numerous summaries of hydrogen applications, there are four significant " obstacles ".As described below separately
1. produce-produce a large amount of hydrogen as the mode of efficient, safety, environment " close friend " how.This patent can be prepared hydrogen by water, and makes itself and oxygen recombine again to form water by any-mode, and does not produce any pollution, and makes water return to its original form.
2. store-how to store low-density inflammable gas.This patent is by providing scalable technique to eliminate storage requirements to generate hydrogen at needs place by water original position.Therefore eliminated dangerous, expensive and harmful storage and the demand of transportation.
3. distribute-because hydrogen is difficult to store, be therefore difficult to transportation.Again, this patent is by providing scalable technique to eliminate to storage and therefore to the demand of transporting to generate hydrogen at needs place by water original position.There is not the demand to dangerous, expensive and harmful storage, distribution and transportation.
4. use-in view of first two, can how to use hydrogen is a larger obstacle.Solving under these two problems, it is even also economical for middle class that the relative cost of use fuel cell becomes.Due to without postcombustion or minimum by the demand of postcombustion is down to, use the ability of fuel cell in the modern life, will become general.
Disclose a kind of method and apparatus for the preparation of hydrogen, it comprises and applies electric current with the aqueous solution of flowing through.In the described aqueous solution, produce cavitation, its cavitation has reduced the amount that disconnects the required energy of the chemical bond of the described aqueous solution.
Embodiment of the present invention also relate to improve electrolytical hydrogen richness and be used in methods described herein and device in produce the chemical structure classification of hydrogen.An embodiment of electrolyte composition comprises aqueous solvent, at least one is dissolved in the inorganic salt in described solvent; With at least one organic acid or its salt, wherein said acid dissolves in described aqueous solvent and to be enough to the supporting concentration of cavitation assisted electrolysis burning to exist substantially.Another embodiment of the present invention comprises electrolyte composition, and wherein based on weight/volume, described aqueous solvent accounts for described electrolytical at least 50%.Another embodiment of the present invention comprises electrolyte composition, and wherein based on weight/volume, described aqueous solvent accounts for described electrolytical about 50-approximately 95%.Another embodiment of the present invention comprises electrolyte composition, in wherein said aqueous solvent, is dissolved with rare gas.Another embodiment of the present invention comprises rare gas argon gas.Another embodiment of the present invention comprises with the saturated solvent of rare gas.
Another embodiment of the present invention comprises electrolyte composition, and wherein said inorganic salt comprise the positively charged ion that is selected from sodium, lithium and potassium.Another embodiment of the present invention can comprise inorganic salt, and it comprises the negatively charged ion that is selected from fluorion, chlorion, bromide anion and iodide ion.Another embodiment of the present invention comprises electrolyte composition, and wherein said inorganic salt comprise NaCl.Another embodiment of the present invention comprises electrolyte composition, and wherein said inorganic salt comprise NaI.
Another embodiment of the present invention comprises electrolyte composition, and wherein said organic acid is present in described ionogen in the concentration (with concentration) of about 1-approximately 10%.Another embodiment of the present invention comprises electrolyte composition, and wherein said organic acid comprises a plurality of carboxyls.
Another embodiment of the present invention comprises electrolyte composition, and wherein said organic acid dissolves in described electrolyte solution substantially.The organic acid that " substantially solvable " means at least 10 % by weight dissolves in described electrolyte solution.Another embodiment of the present invention comprises electrolyte composition, and wherein said at least one organic acid solubleness is that approximately 10 % by weight-Yue 90 % by weight is solvable.
Another embodiment of the present invention comprises electrolyte composition, and wherein said organic acid is included in main the carbochain (" C in main chain with 1-8 carbon
1-C
8").
Another embodiment of the present invention comprises electrolyte composition, and wherein said organic acid is selected from acetic acid, citric acid, formic acid, oxysuccinic acid, propanedioic acid, amygdalic acid, toxilic acid, isocitric acid, fumaric acid, lactic acid, oxyacetic acid, R-Glyceric acid, caproic acid, enanthic acid, sad, valeric acid, n-nonanoic acid, propionic acid, 3-hydroxy-propionic acid, tartrate and 2-tartronic acid.
Another embodiment of the present invention comprises electrolyte composition, and wherein said at least one organic acid is citric acid.Citric acid can be present in described ionogen with the concentration of the about 5.0M of about 0.05-.In preferred embodiments, described electrolyte composition has the citric acid concentration of about 0.1M.Another embodiment of the present invention comprises electrolyte composition, and wherein the concentration of citric acid is about 0.1M, and NaCl is about 0.5-5 % by weight, and NaI exists with trace.
Another embodiment of the present invention comprises electrolyte composition, wherein with the argon gas of the amount that is enough to promote that cavitation assisted electrolysis is burnt, makes described ionogen saturated.
Another embodiment of the present invention comprises electrolyte composition, and wherein said organic acid comprises following structural formula:
C
nH
2n＋1-COOR
Wherein R can be any in H or any alkaline-earth metal independently; And
N is 2-8.
Another embodiment of the present invention comprises electrolyte composition, and wherein said organic acid comprises following structural formula:
ROOC-C
nH
2n-COOR
Wherein R can be any in H or any alkaline-earth metal independently; And
N is 2-8.
Another embodiment of the present invention comprises electrolyte composition, and wherein said organic acid comprises following structural formula:
ROOC-(CHR
2)
n-C(R
2)
2-(CHR
2)
n-COOR
Wherein R can be any in H or any alkaline-earth metal independently;
R
2can be H, OH or COOR; And
N can be 1-3.
Another embodiment of the present invention comprises electrolyte composition, and wherein said organic acid is alpha hydroxy acid soluble in water or beta-hydroxy acid substantially.
Another embodiment of the present invention comprises the electrolyte composition of material, and it comprises aqueous solvent, and at least one is dissolved in inorganic salt and at least one organic acid or its salt in described solvent, and wherein said acid has following structural formula:
C
nH
2n＋1-COOR
Wherein R can be any in H or any alkaline-earth metal independently; And
N is 2-8.
As shown in drawings, above-mentioned and further feature of the present invention and advantage are by by below the more specifically description of the preferred embodiment of the invention being become apparent.
Fig. 1 is according to the schematic diagram of the first embodiment of hydrogen preparation system of the present invention.
Fig. 2 is according to the schematic diagram of the second embodiment of hydrogen preparation system of the present invention.
Fig. 3 is the schematic diagram of the conical funnel assembly of Fig. 2.
Fig. 4 is according to the schematic diagram of the 3rd embodiment of hydrogen preparation system of the present invention.
Fig. 5 is according to the schematic diagram of the first cavitation subsystem of the present invention.
Fig. 6 is according to the schematic diagram of the second cavitation subsystem of the present invention.
Fig. 7 is for affecting the schematic diagram of principal element prepared by hydrogen.
Fig. 8 is the angular perspective figure of computer-aided mapping of single pond acoustic-electric chemical devices of the 4th embodiment.
Fig. 9 obtains from front and towards the similar figure of horizontal transducer enclosure, wherein effuser, anode and bottom transducer enclosure are partially transparent.
Figure 10 obtains from front and by the similar figure of Fig. 9 half-twist.
Figure 11 is the decomposition view of the device of Fig. 8-10.
Figure 12 is for being used the curve of the hydrogen data of this embodiment generation.
Figure 13-16 are the curve description to time data to the collected hydrogen of a series of organic acids of testing in cavitation assisted electrolysis embodiment of the present invention.
It should be understood that following embodiment is only the many advantageously used example of innovative teachings herein.Generally speaking, the description of doing in present specification not must limit any each invention required for protection.In addition, some are described applicable to some features of the present invention, and are not suitable for further feature.Generally speaking, except as otherwise noted, otherwise odd number key element can represent with plural form, and vice versa, and loss of generality not.
In this patent, when using following these words, applicable following definitions:
Cavitation-cavitation is in fluid, and hydrodynamicpressure is down to the phenomenon that forms steam bubble (no matter mechanism) in the region lower than its vapour pressure.Cavitation can be divided into two class behaviors: inertia (or transient state) cavitation and non-inertia cavitation.Thereby inertia cavitation refers to that the cavitation bubbles in liquid subsides fast produces the process of shockwave.Non-inertia cavitation refers to that the input of the energy (such as sound field) due to certain form makes the size of the bubble in fluid or the process that shape is forced to vibration.
Acoustic energy-for the object of this patent, ultrasonic energy refers to those frequencies of 16kHz to 2mHz (comprising 2mHz)." power ultrasonic " is understood to include the 20kHz-100kHz range of frequency that cavitation wherein occurs conventionally.The ultrasonic clinical imaging that is mainly used in higher than 100kHz.Equally for the object of this patent, any frequency in acoustic energy and electromagnetic spectrum or any radiation of wavelength all can with single-frequency (wavelength) or its any combination of frequency (as discrete and, difference, harmonic wave, subharmonic, general frequency, sequence etc.) form use.
" electrolysis " used herein refers to that applicant is for the preparation of the general terms of hydrogen, yet uses this term to be not to recognize that the method is for electrolysis process.In this article, applicant confirms that hydrogen passes through ultrasonic electrochemical method but not prepared by pure electrolysis process.Yet, the acoustic-electric chemistry hydrogen preparation method that term " electrolysis " is developed for referring to below in simple mode sometimes.
The term " extractor " that can exchange use with " device " refer to that hydrogen as herein described prepares pond embodiment.
Term " burning of cavitation assisted electrolysis " is will to dissolve in any suitable hydrocarbons in ionogen and be converted into the method for hydrogen and/or carbonic acid gas in each embodiment of device disclosed herein.Can not infer accordingly that this processing step only limits to device as herein described, but under these instructions, those skilled in the art can make the method be applicable to any suitable cavitation assisted electrolysis equipment.That is, described method independence and be different from described device.
Fig. 1 is according to the cross-sectional side view of hydrogen preparation system 100 of the present invention.Hydrogen preparation system 100 comprises the vessel assembly 102 that is the electrolyzer form that can store tank solution 160.Solution 160 is comprised of solvent and solute.Described solvent is preferably water or another kind of containing aqueous solution of hydrogen.Described solute be for can take charged compound, i.e. ionogen.The side of vessel assembly 102 is preferably non-conductive.Two conducting strips 130 and 132 are retained on the base assemblies 105 of vessel assembly 120 by supporting component 106 and 108 respectively.Conducting strip 130 is connected to the negative terminal 112 of power supply 110.Therefore, conducting strip 130 is negative electrode.Similarly, conducting strip 132 is connected to the positive terminal 114 of power supply 110.Therefore, conducting strip 132 is anode.The cylindrical tube 120 of hollow is connected to and passes the top assembly 104 of vessel assembly 102.Pipe 120 bottom expands outwardly, and is positioned, and makes to manage 120 bottom lower than negative electrode 130 bottoms, but the base assemblies 105 of not touching vessel assembly 102.Similarly, the cylindrical tube 122 of hollow is connected to and passes the top assembly 104 of vessel assembly 102.Pipe 122 bottom expands outwardly, and is positioned, and makes to manage 122 bottom lower than anode 132 bottoms, but the base assemblies 105 of not touching vessel assembly 102.Finally, transverter 140 is connected to a side of vessel assembly 102.Wire 142 is connected to power supply 110 by transverter 140.
As described above, power supply 110 makes negative electrode 130 electronegative and make anode 132 positively charged.Therefore, between negative electrode 130 and anode 132, produced electric current.Described electric current makes solution 160 electrolysis, and causes forming hydrogen around and forming oxygen around at anode 132 at negative electrode 130.Pipe 120 is collected hydrogen and (by arrow 150, is represented) for further use from vessel assembly 102, for example, be used to hydrogen fuel cell that fuel is provided or for directly for engine provides power.Similarly, pipe 122 is collected oxygen (being represented by arrow 155) from vessel assembly 102.Because solution 160 electrolysis and component gas are moved out of system 100, can add extra solution via import 170.
Fig. 2 is the cross-sectional side view that is called another embodiment of the present invention of hydrogen preparation system 200.Hydrogen preparation system 200 comprises the vessel assembly 202 of the electrolyzer form that is energy storage solutions 160.The side of vessel assembly 102 is preferably non-conductive.The columniform conducting strip 230 of hollow is retained on the base assemblies 207 of vessel assembly 202 by supporting component 232.The second conductive component 234 is retained on the base assemblies 207 of vessel assembly 202 by supporting component 205.Conducting strip 230 is connected to the positive terminal 214 of power supply 210.Therefore, conducting strip 230 is anode.Similarly, conducting strip 234 is connected to the negative terminal 212 of power supply 210.Therefore, conducting strip 234 is negative electrode.The cylindrical tube 220 of hollow is connected to and passes the top assembly 206 of vessel assembly 202.The bottom of pipe 220 expands outwardly, and is positioned such that a part for negative electrode 234 is positioned at pipe 220.Finally, transverter 240 is connected to a side of vessel assembly 202.Wire 242 is connected to power supply 210 by transverter 240.
As described above, between negative electrode 234 and anode 230, mobile electric current makes solution 160 electrolysis, and causes forming hydrogen around and forming oxygen around at anode 230 at negative electrode 234.Pipe 250 is collected hydrogen and (by arrow 250, is represented) for further use from vessel assembly 202.Referring to Fig. 3, on the top of anode 230, be placed with conical sheet 310.Conical sheet 310 is collected oxygen (being represented by arrow 340) from vessel assembly 202.Refer again to Fig. 2, because solution 160 electrolysis and component gas are moved out of system 100, can add extra solution via import 280.
Fig. 4 is the cross-sectional side view that is called another embodiment of the present invention of hydrogen preparation system 400.Hydrogen preparation system 400 comprises the cylindrical vessel device 402 of the electrolyzer form that is energy storage solutions 160.Vessel assembly 402 has conductive inner wall 403 and non-conductive outer wall 470.Conducting strip 430 is retained on the base assemblies 407 of vessel assembly 402 by supporting component 405.Conductive inner wall 403 is connected to the positive terminal 414 of power supply 410.Therefore, conductive inner wall 403 is anode.Conducting strip 430 is connected to the negative terminal 412 of power supply 410.Therefore, conducting strip 430 is negative electrode.The cylindrical tube 420 of hollow is connected to and passes the top assembly 480 of vessel assembly 402.The bottom of pipe 420 expands outwardly, and is positioned such that the some parts of negative electrode 430 is positioned at pipe 420.Finally, transverter 440 is connected to the base assemblies 407 of vessel assembly 402.Wire 444 is connected to power supply 410 by transverter 440.
As mentioned before, between negative electrode 430 and anode 403, mobile electric current makes solution 160 electrolysis, and causes forming hydrogen around and forming oxygen around at anode 403 at negative electrode 430.Pipe 420 is collected hydrogen and (by arrow 450, is represented) for further use from vessel assembly 402.The top assembly 480 of the cone shape of vessel assembly 402 is collected oxygen (shown in arrow 455) from vessel assembly 402.Because solution 160 electrolysis and component gas are moved out of system 400, can add extra solution via import 490.
In to the description in the whole text of hydrogen preparation system 100,200 and 400, use cylindrical tube, the hydrogen that manage 120, pipe 250 and pipe 420 form to be captured in negative electrode around, and hydrogen is derived to this system.It will be clear to someone skilled in the art that available any member substitutes pipe 120, pipe 250 and pipe 450 to trap and to derive hydrogen.This class A of geometric unitA includes but not limited to: conduit, membrane filtration member, diffusive evaporation member, dividing potential drop member and the solution air guide of pipe and analogous shape.
In to the description in the whole text of hydrogen preparation system 100,200 and 400, use transverter 140,240 and 440 to be created in the acoustic energy wave 144,244 and 442 that causes cavitation in solution 160.It will be clear to someone skilled in the art that available any member substitutes transverter 140,240 and 440 to produce cavitation.Such member for generation of cavitation includes but not limited to: acoustic member, mechanical component, hydromeehanics member, electromagnetic component and ionizing rays member.
Fig. 1,2 and 4 has shown embodiment of the present invention, and its cavitation produces by specific acoustic impedance member, by using transverter to make acoustic energy wave pass solution 160.Yet, can use other acoustic member to produce cavitation.It will be clear to someone skilled in the art that such acoustic member includes but not limited to: transverter, speaker and loud speaker.
For causing that in hydrogen preparation system 100,200 and 400 example of the mechanical component of cavitation includes but not limited to: be included in the propeller system in vessel assembly 102,202 and 402, when water screw causes cavitation when its axle rotates.Fig. 5 has shown the viewgraph of cross-section of such propeller system.As illustrated, propeller blade 520 rotates around the axle of propeller system 510, thereby produces cavitation in solution 160.Propeller system 510 can be driven by power supply 110,210 or 410.It will be clear to someone skilled in the art that and can use other mechanical component to produce cavitation.Such mechanical component includes but not limited to: propeller system, piston, shock tubing and light-gas gun.
For example, for causing that in hydrogen preparation system 100,200 and 400 example of the hydromeehanics mode of cavitation includes but not limited to: by pressurized gas, pressurized air injects vessel assembly 102,202 and 402 to cause cavitation.Fig. 6 has shown the viewgraph of cross-section of such pressurized gas injected system.As illustrated, pressurized gas injected system 610 is attached to vessel assembly 102,202 or 402.Pressurized gas (being represented by arrow 640) arrives pressurized gas injected system 610 via pipe 630 from compressor (not shown).Pressurized gas is flowed through and is managed 620, and introduces in solution 160 as bubble, i.e. cavitation.In one embodiment, can be by allow pressurized gas to see through film transmission and prevent that solution 160 from entering porous-film in pneupress system 610 so that pressurized gas injected system 610 and solution 160 isolation simultaneously.The example of such film is Gore-Tex.It will be clear to someone skilled in the art that and can use other hydromeehanics member to produce cavitation.Such hydromeehanics member includes but not limited to: pressurized gas injector system and any can be by momentum transfer to solution 160 and not by mass transfer to the equipment in solution 160, for example, strike plate or paint shaker.
For causing that in hydrogen preparation system 100,200 and 400 example of the electromagnetic component of cavitation includes but not limited to: laser beam, is imported in solution 160 to be created in the shockwave that causes cavitation in solution 160.It will be understood by those skilled in the art that and can use other electromagnetic mode to produce cavitation.Described electromagnetic mode includes but not limited to: the electromagnetic radiation that laser beam, X ray, gamma ray, high-velocity electrons, electric arc, magnetic compression, plasma body generate and produced by electronics or the alpha proton reaction of any type.
Finally, for causing that in hydrogen preparation system 100,200 and 400 example of the ionizing rays mode of cavitation includes but not limited to: high energy proton is passed into solution 160, thereby produce cavitation around at proton.Generally speaking, ionizing rays is anyly can remove from chemical bond the radiation of electronics.What therefore, it will be understood by those skilled in the art that is that such ionizing rays mode includes but not limited to: all energy higher than the electromagnetic radiation of uv-radiation and high energy particle as photon, proton, neutron and charged and charge atom core not.
Describing in the whole text and causing that in the example of variety of way of cavitation, cavitation it is said in the interior generation of solution 160 in hydrogen preparation system 100,200 and 400.What it will be understood by those skilled in the art that is at solution 160 " interior ", to cause that cavitation means in electrolysis zone, to cause cavitation.
Fig. 7 is the schematic diagram that affects principal element prepared by hydrogen according to the present invention.Solution factor 710 is for affecting the principal element of solution 160.These solution factors comprise solvent and solute.As described above, described solvent is that water or other are containing aqueous solution of hydrogen.Described solute is compound, for example acid (as HI or HCl), alkali (NaOH) or salt (as KI or NaI), and it is maintained at the density of specific unit solvent volume so that the specific conductivity of described solution reaches maximum.Described solution has specific pH, and no matter is in hydrogen preparation system 100,200 or in 400, all remains under specific temperature and pressure, so that disconnect the required energy minimization of chemical bond of solvent.Finally, described solution has specific ion and covalency state (partial potential).
Power factor 720 is that impact is delivered to negative electrode 130,234 and 430 and the principal element of the power of anode 132,230 and 403.It will be readily apparent to one skilled in the art that power factor 720 comprises applied voltage, the electric current applying and the total power applying.In addition, although show that hydrogen preparation system 100,200 and 400 has single negative electrode and Sole anode, it will be readily apparent to one skilled in the art that the quantity that can increase voltage/current application point, and does not affect the spirit and scope of the invention.Similarly, it will be readily apparent to one skilled in the art that and can change negative electrode 130,234 and 430 and the size and dimension of anode 132,230 and 403, and do not affect the spirit and scope of the invention.Finally, it will be readily apparent to one skilled in the art that power supply 110,210 and 410 can be any power and produces equipment, for example battery, solar panels or fuel cell.
Material compositing factor 730 is the principal elements that affect the material of hydrogen preparation system 100,200 and 400.Anticathode 130,234 and 430 and anode 132,230 and 403 contained materials selected so that specific conductivity maximizes.Such material includes but not limited to: metal is as copper, platinum, and high price nonlinear crystal, includes but not limited to Lithium niobium trioxide and lithium tantalate.
For strengthening the catalysis factor 740 of also hydrogen catalyzed preparation, it is the principal element that affects solution 160 self-energy balances.By necessary electrolysis input energy Δ E
1be down to Δ E
2non-energy input catalysis factor include but not limited to: (1) technological temperature is (as Δ Ε
cavitation, Δ Ε
2, species the function of inclined to one side volumetric molar concentration), (2) container character (composition, shape), (3) SOLUTION PROPERTIES (catalyzer that solute/solvent forms [species, concentration etc.], pH, partial potential, pressure, add [loaded catalyst, gas as rare gas etc.]), the electromagnetism field structure [energising, energising] that (4) electrode property (forming [element, isotopic, chemical], shape, microcosmic surface [crystal face etc.]), macro surface [hole, edge etc.] and (5) apply).
With reference to table 1, it has described one group of equation, though its shown in the situation that there is cavitation, implement the electrolysis of solution 160 to produce the energy being produced when the required energy of hydrogen is still recombinated with oxygen higher than hydrogen.Therefore, it will be readily apparent to one skilled in the art that instruction as herein described not relates to perpetua mobilia.On the contrary, due to the caused net energy loss of the electrolysis of solution 160, shown in power supply 110,210 and 410, by energy drawing-in system 100,200 and 400 with driving electrolysis and catalytic process.
Table 1
Referring again to Fig. 7, electrolysis is inputted to energy by Δ E
1be down to Δ E
2energy input factor 750 include but not limited to: (1) Δ E
other(the necessary energy such as temperature control and measurement, machinery, stirring); And (2) Δ E
cavitation(cavitation device performance [size, shape, composition], configuration [density of quantity, unit surface/volume etc.], power input [f (V, I)], audio spectrum input, electromagnetic spectrum input).As mentioned above, cavitation device can be any equipment that can cause cavitation.
Advantageously show, in an embodiment of hydrogen preparation system 400, following factor has greatly improved hydrogen output of the present invention: (1) is used specific sound spectrum so that the cavitation in solution 160 maximizes; (2) in solution 160, use sodium iodide or iodate sylvite so that the specific conductivity of solution 160 and partial potential maximize; (3) rare gas of significant quantity is dissolved in solution 160 so that described rare gas is dissolved in solution completely, thereby with electromagnetic mode, improve the generation of cavitation, make thus the generation of hydrogen maximize-in the present embodiment, described rare gas is preferably argon gas, and treats that the significant quantity that is dissolved in the rare gas in solution 160 is completely up to (5%) 5 percent under standard temperature and pressure (STP); (4) electrode shape and configuration, for hydrogen preparation system 400, this comprises conductive inner wall 403 and conduction internal sheets 430, thereby make: (i) mechanical separation of hydrogen and oxygen product maximizes, and (ii) by using cylindrical electrode structure (it is by making the ratio multiplication of interior outside radius that electric field is maximized) so that electrolysis electric field maximizes; And the shape of (5) container, thereby for example hydrogen preparation system 400 comprises that the conductive inner wall 403 being included in non-conductive outer wall 470 is by the function of hydrogen preparation system 400 and extraneous electricity isolation.
Similarly, although be clear that to those skilled in the art solution 160 can be exposed under any temperature and/or pressure, and solution 160 can be included in sealing or unencapsulated container, yet for an embodiment of hydrogen gas system 400, advantageously show and use the hydrogen preparation of instruction described herein preferably approximately under standard temperature and pressure (STP) (STP), in sealing, in non-pressurised vessel, carrying out.
The 4th embodiment of the present invention is the device shown in Fig. 8-11.Device 500 is described to have overall arrangement and the assembly of electrolyzer, the ultrasonic transducer of additional two orthogonal placements conventionally.What should emphasize is that described device itself is not used in enforcement electrolysis, but for causing acoustic-electric chemical reaction process.Therefore, described equipment is called " sound electrolyzer " 500.
Attention is gone to Fig. 8, and it has shown sound electrolyzer 500 with angular perspective.In operational process, sound electrolyzer 500 is positioned at for keeping liquid as the internal tank of aqueous electrolyte.Yet for the clear object of setting forth, this figure has omitted described container.Described pond comprises the cylindrical anode 520 being arranged on anode-supported plate 525, be positioned at anode 520 inside cylindrical cathode 530 (preferably referring to Fig. 9-10), be arranged on anode-supported plate 525 times and the directed bottom ultrasonic transducer 540 with the axle transmission along negative electrode 530, and the horizontal transverter 550 of installing at an angle of 90 with bottom transverter 540.Each transverter has pairs of posts 541a and a 541b who is respectively used to positive wire and cathode conductor.These not shown for driving the electronics of described transverter, the power supply of electrode or shift out member for shifting out the gas of the hydrogen of any generation.
Support frame comprises four back up pads 510,512,514 and 525.Bottom support plate 510 has for holding and/or supporting various structure and function assemblies as the various through holes of connecting rod 527 and anode 520.Bottom anode-supported plate 525 has had the stepped otch 526 of supporting anodes 520 lower end effects.Top anode-supported plate 512 has similar otch, it allows two anode-supported plates 512,525 when tightening relative nut 528 that anode " is clipped in " therebetween, thus by the position between anode difference " being clipped in " top anode-supported plate and bottom anode-supported plate 512,525.Isolation supporter 513 is for being threaded support bar 527 and provide the non-conductive pipe of extra structure rigidity for described equipment on it.Effuser back up pad 514 is the 4th back up pad and is positioned at anode-supported plate top, top.It has the otch for effuser 515, and effuser 515 extends to effuser junctor (not shown) by the top of bottom transducer enclosure 544.Electrode (negative electrode 530) and between anode and the internal diameter of negative electrode in effuser 515 surrounds.In one embodiment, the diameter of described pipe can be 1 ＂, is 2 ＂ in another embodiment.The effect of effuser 515 is to be collected in the hydrogen that produces in negative electrode 530 ionogen volume around, described gas is usingd and is entrained in fluid stream or as upwards guiding of bubble, and its electromagnetic field that also can produce electrode has focusing effect.Described back up pad also can have directed indicating unit, as groove 516.Described plate can horizontal orientation as illustrated, or vertical orientation.In this case, described plate is by approximately 1/4 inch
(DuPont, Wilmington, Delaware) makes, although other material is applicable to too, as long as it can keep some structure rigidities.Described four blocks of plates keep horizontal orientation by four connecting rods 527 (it is also NYLON), and its end has screw thread to accept nut 528.Also there is power lead (positive wire (not shown) and cathode wire 532).Cathode power is defined as negative, and anode is positive.By two wires (not shown in this embodiment), to bottom transverter and horizontal transverter, apply power.
Fig. 9 and 10 has shown anode 520 and effuser 515, its for partially transparent so that can see inner cathode.Anode 520 and negative electrode 530 can be made by any suitable conducting metal being generally used in electrolysis.Cylindrical anode 520 is by being of a size of 5.4cm OD * 5.1cm ID and high making for the solid copper pipe of 6cm; Grainger, streamlined copper pipe, Fulton, MS type M NSE/ANSL, 61-G.Negative electrode 530 is two sheets, No. 14, center copper cash (2mm OD) and the approximately 2mm OD sliding thereon, the cylindrical solid copper mesh 533 of 2mm ID, high 6cm; The copper mesh of 99.9% purity; 0.010 is thick; Stock no.6095, K & S Engineering, Chicago, IL.Cathode shape is concentric column shape, and it has according to the internal diameter of external anode being compared to the ratio of the fixed diameter with respect to anode for about 1:25 recording with the external diameter of inner cathode and being positioned at anode interior.Described negative electrode arranges with one heart along the axle of anode volume.Copper cash derives from Home Depot, and is copper cash-No. 14 of 99.9% purity; 600 volts; VW-1 is specified; Distribution numbering YM-680,590.
Figure 11 has shown the supporting way of horizontal transverter 550.Laterally transverter cap 553 covers and directly contacts with horizontal transverter 550.For terminal stud 541a, b provide net 551 to permeate.Net 551 is glued to horizontal transverter back up pad 555.Lid 553 is fixed to plate 555 similarly, wraps thus and receives horizontal transverter 550 and support and be directly positioned at anode 520 sides with vertical mode.Transverter 540 bags in bottom are contained in bottom transverter shell block 546 and bottom transverter cap 544.They are all tightened to hold each other.Split ring 543 and net 545 support transverter 540.The top of bottom transverter cap 544 is fixed to the bottom of bottom anode-supported plate 525, thereby makes when being screwed into bottom transverter shell block 546, it is close to all elements.
Use DC power supply (30 volts/3 amperes) (3 passage BK Precision able to programme Model 903) to drive described sound electrolysis process.Frequency generator drives described transverter.
The ionogen of preparing data for generation of appended hydrogen is the aqueous solution of citric acid, NaCl and NaI.121.731g NaCl (Deer Park, TX, Cat. number S2675-2KG for ACS level reagent, the aqueous solution) is dissolved in 2 premium on currency of purifying by reverse osmosis.Then, 20.560g citric acid (Cat numbers 42356-0020 for ACS level, ACROS) is dissolved in same solution.Then, by 3.54mg from MP Biomedicals, Solon, Ohio, the SILVER REAGENT NaI of Cat numbering 193979 is dissolved in described electrolyte solution.Before use, thus make argon gas bubbling be enough to replace other gas dissolved by described solution.
Hydrogen is according to following electrolysis program preparation.Except as otherwise noted, otherwise mentioned all electromotive forces are direct current (DC).First, make electrolyte solution " charged " or there is electromotive force.Startup (priming) or charged for apply the method for electromotive force to described solution, described solution retains a part of electric charge between the whole reaction period and after reaction finishes.Now, be understood that described solution has dielectric functions ε, therefore performance is similar to the effect of resistance-capacitance network.For all methods, charged step is all to cause hydrogen to prepare necessary.Make solution there is electromotive force and alleviated the delay relevant with initialize electrolysis conventionally.On molecular level, this causes ionic channel to start " flowing ", and promotes electron exchange.The operation first that makes described solution have electromotive force is relatively simple.Make the ionogen in device reach the setting electric current of 1.5 peaces and the setting voltage of 20V.When electric current reaches the set(ting)value of 1.5 peaces, observing voltage is 6-8 volt.Described solution is remained under these values to approximately 5 minutes, then close applied power.This specific program carries out at least one times, twice sometimes.Now, described solution is regarded as charged (having electromotive force).
Cathode power supply line is connected to anode; Cathode conductor is connected to negative electrode.Described transverter is connected to function/frequency generator (if using cavitation).By power settings, be to float under 20V overhead voltage, ampere be set in to fixed value (its scope is 250mA to 2.0A) simultaneously.Can use any suitable function generator to drive described transverter, yet preferred producer comprise PROTEK B8012 or QUAKKO 5000 digital signal generators.Described transverter is set as to 3.3V, obtains about 10-20mv.For laterally/horizontal transverter is 38.248kHz by frequency setting, and described bottom transverter is set as to 76kHz.Laterally transverter 550 is positioned at 2.6cm place, Ju Chi center; It is 5.2cm place that bottom transverter 540 is positioned at by described transducer face measurement Ju center.Two transverters are all towards the center oriented in described pond.Therefore, the central zone in described pond is considered as to " reaction zone " of this device 500.The present invention's transverter used is Piezo Air Transducer, Part No.SMUTF40TR I 8A, Steminc (Steiner & Martins, Inc.), Miami, FL.Hydrogen is with the amount preparation (Figure 12) described in accompanying drawing.
Work as H
+thereby ionic current to negative electrode when producing hydrogen with electronic combination in reduction reaction, pure water (H
2o) there is electrolysis.Similarly, hydroxide ion (OH
-) flow to anode to discharge electronics and H
+thereby ion is Preparation of oxygen in oxidizing reaction.When interpolation NaCl can carry the ionogen of significantly more electric charge (higher electric density) with generation, described reaction skew.The standard electrolytic reaction of the NaCl aqueous solution causes water molecules to be reduced into OH at negative electrode place
-and hydrogen (H
2), wherein cl anion is still oxidized to chlorine at anode place.Net result is along with H
2the generation of gas, obtains alkalescence and progressively becomes large NaOH solution.Yet the embodiment of this system does not produce chlorine under normal running (operation) conditions.
Set up sonochemistry field, described sonochemistry field by ultrasound energy transfer to liquid H
2there is cavitation (Mason, Sonochemistry 2-4 (1999)) in O.The cavitation of water makes H
2o is especially dissociated into H
*and OH
*free radical, subsequently H
*free radical recombinates to form H
2gas (the same, 16-17 page).
Embodiment of the present invention relate to and comprise aqueous solvent, at least one is dissolved in inorganic salt in described solvent and the electrolyte composition of at least one organic acid or its salt, and wherein said at least one acid dissolves in described aqueous solvent and to be enough to the supporting concentration of cavitation assisted electrolysis burning to exist substantially.
In electrolyte composition of the present invention, in water base NaCl ionogen, add citric acid (C
6h
8o
7) to obtain 0.1M solution.When applying electrolysis and cavitation, with the raw hydrogen of relatively pure volume production and carbon dioxide.Carbon monoxide or other less desirable by product do not detected.At present, contriver believes that a possible equation of the whole chemical reactions of explanation is following equation:
C
6H
8O
7+5H
2O→9H
2+6CO
2
The gas ratio of the gained gaseous product that this reclaims by measurement and measuring.By Rowland/Blake Research Group, Dept.of Chemistry, the gasometry that U.California/Irvine carries out shows, the H of the merging gas sample being produced by citric acid-based ionogen in the device of embodiment disclosed herein
2/ CO
2than being 7.76.Described gas is in the combination of 1 hour or 2 hours four independent samples taking out in above-mentioned tentative gas manifold system of run duration (citric acid-based ionogen experience sound electrolytic process of the present invention during this period) in the 4th embodiment.The pond of described pond and the 4th embodiment is slightly different, and it has single bottom transverter and does not have effuser.All other assemblies are all substantially the same with operation standard.
Described chemical paths is similarly free radical initiation, and (at anode, CO is prepared at place to have the oxidation occurring in possible independent path
2) and reduction (at negative electrode, hydrogen is prepared at place) indication.Some possibilities that also exist are if hydrogen is to produce under hot environment, the alkane component generation pyrolysis of citric acid.Yet other mechanism is also possible, and embodiment of the present invention not rely on any be the concrete mechanism that science is correct by final certification.We claim that the method is " burning of cavitation assisted electrolysis ".
The aqueous solvent of described electrolyte composition accounts for described electrolytical at least about 50%, based on weight by volume.Because described electrolytical water molecules is dissociated into free radical under cavatition, and those free radicals are converted in hydrogen and carbonic acid gas and have katalysis at organic acid, are therefore enough to support the water concentration of cavitation assisted electrolysis burning believed as at least 50%.That is, the share of water is at least about half, more preferably at least about 60%, most preferably at least about 70% water.The preferable range of water concentration is described electrolytical about 50%-approximately 95%, based on weight by volume.
Embodiment of the present invention can comprise the rare gas being dissolved in aqueous solvent.It is believed that a certain amount of rare gas as argon gas to operation of the present invention, may be favourable.By making before use argon gas bubbling by electrolyte solution, argon gas is dissolved in described ionogen, the method is called " injection ".Injection has discharge and is present in airborne other gas as the effect of oxygen, carbonic acid gas, nitrogen etc.It is front by applying vacuum and degassed step to ionogen that injection is included in argon gas bubbling.This has by first reducing the dividing potential drop of all gas dissolvedes the effect promoting with argon replaces air.Then, argon gas bubbling makes described liquid saturated by heavier inert argon.Also available other rare gas substitutes and is known, as helium, neon, Krypton etc.The saturated of solution typically obtaining after approximately 30 minutes with many bubbles frit (frit) bubbling.With regard to argon gas, saturated it is believed that reaches approximately 5% weight by volume, although most of air that spray technology can dissolve by argon replaces effectively.
Embodiment of the present invention comprise inorganic salt, as sodium-chlor, sodium iodide, or can be by charge-conduction by the inorganic salt of the aqueous solution.Salt comprises positively charged ion (positively charged ionic species) and negatively charged ion (electronegative ionic species).Preferred positively charged ion is selected from sodium, lithium and potassium.Can be used for sodium cation embodiment of the present invention is sodium-chlor (salt) and sodium iodide.The embodiment of lithium comprises lithium chloride and lithium iodide.The embodiment of potassium comprises potassiumiodide, Repone K.As described in above salt being discussed, negatively charged ion is also essential for ionogen.Preferred negatively charged ion includes but not limited to be selected from the negatively charged ion of fluorion, chlorion, bromide anion and iodide ion.
Embodiment of the present invention also comprise at least one weight-volumetric concentration with about 1-approximately 10% and are present in the organic acid in described ionogen.According to definition, carboxylic acid contains at least one carboxyl (COOH) structure division, and poly carboxylic acid is known and comprise citric acid, tricarboxylic acid.Other exemplary poly carboxylic acid comprises fumaric acid (2), oxysuccinic acid (2), propanedioic acid (2) and tartronic acid (2).Embodiment of the present invention also comprises at least one and substantially dissolves in the organic acid in described electrolyte solution." substantially solvable " means described acid solubleness in water under normal pressure and temperature to be enough to produce hydrogen in cavitation assisted electrolysis combustion processes.Under described at least one organic acid preferred dissolution degree, being limited at least 10 % by weight dissolves in described electrolyte solution.Preferred scope is that approximately 10 % by weight-Yue 90 % by weight is solvable.Low molecular weight organic acid seems in water, to have excellent solubleness, especially has C
1-C
8those of main carbochain.
Embodiment of the present invention can comprise one or more and be selected from but the organic acid that is not limited to following group: acetic acid, citric acid, formic acid, oxysuccinic acid, propanedioic acid, amygdalic acid, toxilic acid, isocitric acid, fumaric acid, lactic acid, oxyacetic acid, R-Glyceric acid, caproic acid, enanthic acid, sad, valeric acid, n-nonanoic acid, propionic acid, 3-hydroxy-propionic acid and 2-tartronic acid.This list is only for exemplary purpose, and is not considered as limiting the present invention.Substantially other organic acid in water soluble as α-and beta-hydroxy acid also within scope of the present invention.
Embodiment of the present invention comprise citric acid, and the concentration of citric acid in described ionogen is the about 5.0M of about 0.05M-.Particularly preferred concentration is about 0.1M.Preferred citric acid-based ionogen has about 0.1M citric acid, about 0.5-5 % by weight NaCl and trace NaI.Another preferred embodiment comprises with being enough to promote the argon gas of cavitation assisted electrolysis burning to make described ionogen saturated.
In this article, electrolytical other embodiment of the present invention comprises electrolyte composition, and wherein said at least one organic acid comprises following structural formula:
C
nH
2n＋1-COOR
Wherein R can be any in H or any alkaline-earth metal independently; And n is 2-8.
In this article, electrolytical other embodiment of the present invention comprises electrolyte composition, and wherein said at least one organic acid comprises following structural formula:
ROOC-C
nH
2n-COOR
Wherein R can be any in H or any alkaline-earth metal independently; And n is 2-8.
In this article, electrolytical other embodiment of the present invention comprises the electrolyte composition of claim 1, and wherein said at least one organic acid comprises following structural formula:
ROOC-(CHR
2)
n-C(R
2)
2-(CHR
2)
n-COOR
Wherein R can be any in H or any alkaline-earth metal; R
2can be H, OH or COOR; And n can be 1-3.
In this article, electrolytical other embodiment of the present invention comprises electrolyte composition, and wherein said at least one organic acid is alpha hydroxy acid or the beta-hydroxy acid in water soluble substantially.The example of alpha hydroxy acid includes but not limited to oxyacetic acid, lactic acid, 2-hydroxy-iso-butyric acid, 2-hydroxyl-2-phenylpropionic acid, amygdalic acid, 2-hydroxyl-3,3-dimethyl-4-butyrolactone and 4-methyl-thiobutanoic acid.The non-enclosed list that can be used for the beta-hydroxy acid in the present invention comprises 3-hydroxycaproic acid, 3-Hydroxyoctanoic acid, 3-hydroxydecanoic acid, 3-hydroxy-dodecanoic acid, 3-Hydroxyoctanoic acid, Whitfield's ointment, 3-hydroxybutyrate, 3-hydroxypentanoic acid, 3-hydroxy-propionic acid and composition thereof.
Embodiment of the present invention relates to other chemical substance after tested, comprises citric acid and the material except citric acid.In following table, the test procedure of data is as follows:
Program: the gas generation research of various carboxylic acids
The object of this group test is to set up with the hydrogen of comparing four kinds of carboxylic acids and/or its sodium salt by the value that citric acid obtains to prepare potentiality.
Method:
Should organize test, only two variablees are carboxylic acid kind and the amount being added in each LSF aliquots containig.It is constant that the amount of sodium-chlor and sodium iodide keeps.In order to ensure the total concn of described salt, will be by 1152g sodium-chlor (NaCl)/5 gallon (18.9L) deionization H
2the masterbatch of the salt brine solution that O forms is for these tests.The carboxylic acid that takes out aliquots containig and add specified quantitative from this batch of material is to obtain respectively the do for oneself aliquots containig of 0.1M and 1.0M of concentration.In each this program, the ability of testing the generation hydrogen of each sour enriched material.The results are shown in Figure 10-13 of citric acid, acetic acid, propionic acid and propanedioic acid.
Prepare 5 gallons of (18.9L) batch of material salts solutions:
By 5 gallons of (18.9L) deionization H
2o measures in 5 gallons of (18.9L) Samson Stackable API HDPE Kirk containers.1152g ACS SILVER REAGENT NaCl (CAS#7647-14-5) is measured to the circular Pyrex watch glass ware being arranged on A & D Ex-300A electronic balance, similarly 3.37g ACS SILVER REAGENT NaI (CAS#7681-82-5) is measured to the circular Pyrex watch glass ware being arranged on Sauter RE 1614 electronic balances; Once weigh, two kinds of salt added in 5 gallons of (18.9L) containers.By the gentle mixing of this batch of material solution.
The operation of hydrogen extractor:
Sound electrolyzer used herein (also referred to as " extractor ") is similar to the extractor described in the 4th embodiment, and it is according to following specific setting or condition operation.Each aliquots containig of solution is added in the groove of described extractor with its test concentrations.The electricity of described extractor is input as 500mA and sets electric current (i
set) and 30V ceiling voltage, it is provided by BK Precision 1901 Switching Mode Power Supply 1-30VDC/30A power supplys.A pair of transverter described in vocal input the as shown in Figure 8 with four embodiment provides.Laterally transverter produces 38.248kHz; Bottom transverter produces 76kHz.Two transverters are all connected to 20mHz 100MS a/s Rigol DG1022 Dual Channel Function/Arbitrary Waveform Generator.By Parker 12V T1-1 HD-12-1 surge pump, product (hydrogen and carbon dioxide) was taken out to the collecting manifold that is equipped with Pall PTF045LHOP-SAMP film.Parker pump is by Power Design, Inc., and model Model 6050 multiple power sources drive.The time length of each run is once to obtain following data in 5 minutes and 1 minute during each run: by Fluke8845A 6 1/2
electric current (the i that Digit Precision Multimeter observes
observe) and the voltage (v that observes
observe); Use Alicat Scientific M-10SLPM-D 15M H
2the flow hydrogen gas speed that calibrating quality flowmeter survey makes (in standard liter/min (SLPM)).Background air leak in four contrast running series is similar, and is shown in the curve shown in Figure 10.In the U.S. Patent application the 13/170th that on June 27th, 2011 submits to, the extra acoustic-electric chemical devices that can implement these operations has been described for No. 115, at this, by reference it is all incorporated to herein.
Test following organic acid-electrolyte solution and in device described herein, be converted into the ability of hydrogen.
Solution #1-citric acid
19.2g ACS SILVER REAGENT citric acid (CAS#77-92-9) is measured to the aliquots containig that is arranged in the circular Pyrex watch glass ware on A & D Ex-300A electronic balance and is added into 1L batch of material salts solution to obtain 0.1M solution.This 0.1M solution is placed in to hydrogen extractor also according to moving at the general operation procedure described in the 4th embodiment above.After operation first, in this 0.1M solution, add extra 172.8g citric acid to obtain 1.0M solution and to be placed in hydrogen extractor for operation for the second time.After this takes turns end, abandon solution.The results are shown in Figure 10.The line of below is average deionized water operation.It approaches air leak.The average SLPM (standard liters per minute) of deionized water is 2.47+/-0.36.By any, be greater than the evidence that 2.83 result is considered as producing gas.The average SLPM of 0.1M and 1.0M citric acid is respectively 3.28 and 3.23.
Solution #2-acetic acid
For residue operation, repeat to move identical general procedure with citric acid, except following content.Use 6.0g ACS level 99.7+% Glacial acetic acid to prepare 0.1M solution.Described solution is placed in to hydrogen extractor operation.After operation first, in this 0.1M solution, add extra 54g acetic acid to obtain 1.0M solution, and be placed in hydrogen extractor for operation for the second time.The results are shown in Figure 11.The SLPM of acetic acid is 3.88/3.56.
Solution #3-propionic acid
Repeat to move identical general procedure with citric acid, except following content.Use 7.4gACS level 99+% propionic acid to obtain 0.1M solution.After operation first, in this 0.1M solution, add extra 66.6g propionic acid to obtain 1.0M solution.The results are shown in Figure 12.The SLPM of propionic acid is 4.12/3.65.
Solution #4-propanedioic acid
Repeat to move identical general procedure with citric acid, except following content.Use 10.4gACS level 99.5+% propanedioic acid to obtain 0.1M solution.In this 0.1M solution, add extra 93.6g propanedioic acid to obtain 1.0M solution.The results are shown in Figure 13.The SLPM of propanedioic acid is 5.58/5.30.
Under restricted test condition as herein described, propanedioic acid looks like best hydrogen and produces body.Although hydrochlorate, Sodium Propionate, Sodium propanecarboxylate and Sodium octoate move in extractor, however after this operation starts owing to producing at once toxic gas, therefore image data not.
Embodiment of the present invention also relate to a kind of method that is produced hydrogen by water and hydrocarbon feed, and it comprises provides rich, high temperature electronics aqueous environments, wherein make water decomposition with described raw material reaction and make described hydrocarbon be converted into hydrogen and carbonic acid gas.Described hydrocarbon feed can be one or more organic acids, to combine or to use separately, or can comprise that other Water-soluble Organic Substances with the hydrogen atom of dissociation is easily as alcohol.
Embodiment of the present invention also relate to a kind of method that is produced hydrogen by water and hydrocarbon feed, and it is included in the aqueous electrolyte liquid of hydrocarbon-containing feedstock and produces cavitation and external electrical source is provided wherein, prepares thus hydrogen and carbonic acid gas.As disclosed herein, the acoustic transducer importing in the electrolyte solution described in each embodiment by use produces cavitation.According to each embodiment, also by a pair of coaxal electrode being immersed in ionogen external electrical source is provided under different voltage and current set(ting)values.
In addition, self-evidently, instruction as herein described and embodiment concentrate on the input of energy are minimized, and make the output of hydrogen maximize simultaneously.The most important factor that affects total input energy is electrolysis voltage.Therefore, self-evidently, input voltage that need to be lower to the given hydrogen generating quantity of identical (or higher), this causes input energy that need to be still less, needs thus power input still less.Due to needs power input still less, input-output thermodynamics difference is down to minimum, and because the power input of greater share can be produced by energy source (as solar cell, storage battery group etc.), the hydrogen total amount maximization that therefore makes total efficiency and produce.
Although disclose specific embodiment of the invention scheme, yet it will be understood by those skilled in the art that and can change and not depart from the spirit and scope of the invention this specific embodiments.Similarly, it will be understood by those skilled in the art that instruction herein can bi-directional scaling size to improve or to reduce hydrogen output, and do not affect the scope and spirit of the present invention.Therefore, scope of the present invention is not limited to described specific embodiments, and its object is that claims contain any and all such application, improvement and the embodiment in the scope of the invention.
Claims (29)
1. the electrolyte composition of material, it comprises:
Aqueous solvent;
At least one is dissolved in the inorganic salt in described solvent; With
At least one organic acid or its salt, described at least one acid dissolves in described aqueous solvent and to be enough to the supporting concentration of cavitation assisted electrolysis burning to exist substantially.
2. according to the electrolyte composition of claim 1, wherein said aqueous solvent accounts for described electrolytical at least about 50%, based on weight/volume meter.
3. according to the electrolyte composition of claim 1, wherein said aqueous solvent accounts for described electrolytical about 50-approximately 95%, based on weight/volume meter.
4. according to the electrolyte composition of claim 1, wherein rare gas is dissolved in described aqueous solvent.
5. according to the electrolyte composition of claim 4, wherein said rare gas is argon gas.
6. according to the electrolyte composition of claim 4, wherein said rare gas makes described solvent saturated.
7. according to the electrolyte composition of claim 1, wherein said at least one inorganic salt comprise the positively charged ion that is selected from sodium, lithium and potassium.
8. according to the electrolyte composition of claim 1, wherein said at least one inorganic salt comprise the negatively charged ion that is selected from fluorion, chlorion, bromide anion and iodide ion.
9. according to the electrolyte composition of claim 1, wherein said at least one inorganic salt comprise NaCl.
10. according to the electrolyte composition of claim 1, wherein said at least one inorganic salt comprise NaI.
11. according to the electrolyte composition of claim 1, and wherein said at least one organic acid is present in described ionogen with the concentration of about 1%-approximately 10%.
12. according to the electrolyte composition of claim 1, and wherein said at least one organic acid comprises a plurality of carboxyls.
13. according to the electrolyte composition of claim 1, and wherein said at least one organic acid dissolves in described electrolyte solution substantially.
14. according to the electrolyte composition of claim 12, and wherein said at least one organic acid at least 10 % by weight dissolve in described electrolyte solution.
15. according to the electrolyte composition of claim 1, and wherein said at least one organic acid solubleness is that approximately 10 % by weight-Yue 90 % by weight is solvable.
16. according to the electrolyte composition of claim 1, and wherein said at least one organic acid contains C
1-C
8main carbochain.
17. according to the electrolyte composition of claim 1, and wherein said at least one organic acid is selected from acetic acid, citric acid, formic acid, oxysuccinic acid, propanedioic acid, amygdalic acid, toxilic acid, isocitric acid, fumaric acid, lactic acid, oxyacetic acid, R-Glyceric acid, caproic acid, enanthic acid, sad, valeric acid, n-nonanoic acid, propionic acid, 3-hydroxy-propionic acid and 2-tartronic acid.
18. according to the electrolyte composition of claim 1, and wherein said at least one organic acid is citric acid.
19. according to the electrolyte composition of claim 18, and wherein said citric acid is present in described ionogen with the concentration of the about 5.0M of about 0.05M-.
20. according to the electrolyte composition of claim 18, and the concentration of wherein said citric acid is about 0.1M.
21. according to the electrolyte composition of claim 18, and wherein the concentration of citric acid is about 0.1M, and described inorganic salt comprise that concentration is the NaCl of about 0.5-5 % by weight, and the second inorganic salt comprise trace NaI.
22. according to the electrolyte composition of claim 21, and wherein said ionogen is to be enough to promote the argon gas of amount of cavitation assisted electrolysis burning saturated.
23. according to the electrolyte composition of claim 1, and wherein said at least one organic acid comprises following structural formula:
C
nH
2n＋1-COOR
Wherein R can be any in H or any alkaline-earth metal independently; And
N is 2-8.
24. according to the electrolyte composition of claim 1, and wherein said at least one organic acid comprises following structural formula:
ROOC-C
nH
2n-COOR
Wherein R can be any in H or any alkaline-earth metal; And
N is 2-8.
25. according to the electrolyte composition of claim 1, and wherein said at least one organic acid comprises following structural formula:
ROOC-(CHR
2)
n-C(R
2)
2-(CHR
2)
n-COOR
Wherein R can be any in H or any alkaline-earth metal;
R
2can be H, OH or COOR; And
N can be 1-3.
26. according to the electrolyte composition of claim 1, and wherein said at least one organic acid is the alpha hydroxy acid in water soluble substantially.
27. according to the electrolyte composition of claim 1, and wherein said at least one organic acid is the beta-hydroxy acid in water soluble substantially.
28. produce the methods of hydrogen by water and hydrocarbon feed, and it comprises provides rich, high temperature electronics aqueous environment, wherein make water decomposition with the reacting and make described hydrocarbon be converted into hydrogen and carbonic acid gas of described raw material.
29. produce the methods of hydrogen by water and hydrocarbon feed, and it is included in the aqueous electrolyte liquid of hydrocarbon-containing feedstock and produces cavitation and external electrical source is provided wherein, prepares thus hydrogen and carbonic acid gas.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13/170,132 US20120055805A1 (en) | 2008-07-02 | 2011-06-27 | Cavitation assisted sonochemical hydrogen production system |
| US13/170,132 | 2011-06-27 | ||
| PCT/US2012/044457 WO2013003496A1 (en) | 2011-06-27 | 2012-06-27 | Cavitation assisted sonochemical hydrogen production system |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103764875A true CN103764875A (en) | 2014-04-30 |
Family
ID=47424530
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280038937.7A Pending CN103764875A (en) | 2011-06-27 | 2012-06-27 | Cavitation assisted sonochemical hydrogen production system |
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| Country | Link |
|---|---|
| US (1) | US20120055805A1 (en) |
| EP (1) | EP2723917A1 (en) |
| JP (1) | JP2014520958A (en) |
| CN (1) | CN103764875A (en) |
| WO (1) | WO2013003496A1 (en) |
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| US9476133B2 (en) | 2013-03-19 | 2016-10-25 | Brian Daniel Gilman | Portable hydrogen and oxygen supply system |
| US20150138923A1 (en) * | 2013-11-18 | 2015-05-21 | Frac Innovations, Inc. | Acoustic cavitation in fluids |
| FR3026315B1 (en) * | 2014-09-26 | 2018-01-26 | Centre National De La Recherche Scientifique | METHOD FOR CONTROLLING AT LEAST ONE GAS BUBBLE PRODUCED IN A LOCALIZED MANNER |
| JP6338648B2 (en) * | 2016-12-28 | 2018-06-06 | 株式会社日省エンジニアリング | Portable electrolyzer |
| WO2020243473A1 (en) * | 2019-05-29 | 2020-12-03 | Davis Technologies, LLC | High efficiency hydrogen oxygen generation system and method |
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| US6638413B1 (en) * | 1989-10-10 | 2003-10-28 | Lectro Press, Inc. | Methods and apparatus for electrolysis of water |
| US7220166B2 (en) * | 2000-08-30 | 2007-05-22 | Micron Technology, Inc. | Methods and apparatus for electromechanically and/or electrochemically-mechanically removing conductive material from a microelectronic substrate |
| JP3805621B2 (en) * | 2000-12-19 | 2006-08-02 | 株式会社富永製作所 | Electrolyzed water generator |
| US7160432B2 (en) * | 2001-03-14 | 2007-01-09 | Applied Materials, Inc. | Method and composition for polishing a substrate |
| JP2003328168A (en) * | 2002-05-08 | 2003-11-19 | Research Institute Of Innovative Technology For The Earth | Method of producing hydrogen |
| AUPS220302A0 (en) * | 2002-05-08 | 2002-06-06 | Chang, Chak Man Thomas | A plasma formed within bubbles in an aqueous medium and uses therefore |
| US20040154931A1 (en) * | 2003-02-12 | 2004-08-12 | Akihisa Hongo | Polishing liquid, polishing method and polishing apparatus |
| US7189146B2 (en) * | 2003-03-27 | 2007-03-13 | Asm Nutool, Inc. | Method for reduction of defects in wet processed layers |
| US20050173255A1 (en) * | 2004-02-05 | 2005-08-11 | George Bokisa | Electroplated quaternary alloys |
| WO2007077654A1 (en) * | 2005-12-28 | 2007-07-12 | Omsi Co., Ltd. | Process for producing carbon dioxide solution, production apparatus, and carbonated water |
| JP4728846B2 (en) * | 2006-03-14 | 2011-07-20 | 日本電信電話株式会社 | Electrolysis cell and hydrogen supply system |
| WO2007124443A2 (en) * | 2006-04-20 | 2007-11-01 | Benjamin Pless | Electrolytic cell with cavitating jet |
| AU2008247280A1 (en) * | 2007-05-04 | 2008-11-13 | Principle Energy Solutions, Inc. | Production of hydrocarbons from carbon and hydrogen sources |
| US7947184B2 (en) * | 2007-07-12 | 2011-05-24 | Kimberly-Clark Worldwide, Inc. | Treatment chamber for separating compounds from aqueous effluent |
| US20100000876A1 (en) * | 2008-07-02 | 2010-01-07 | Sandbox Energy Systems, LLC | Caviation assisted sonochemical hydrogen production system |
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| EP2723917A1 (en) | 2014-04-30 |
| JP2014520958A (en) | 2014-08-25 |
| US20120055805A1 (en) | 2012-03-08 |
| WO2013003496A1 (en) | 2013-01-03 |
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Application publication date: 20140430 |