WO2009009853A1 - Système de génération d'hydrogène - Google Patents

Système de génération d'hydrogène Download PDF

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Publication number
WO2009009853A1
WO2009009853A1 PCT/CA2007/001230 CA2007001230W WO2009009853A1 WO 2009009853 A1 WO2009009853 A1 WO 2009009853A1 CA 2007001230 W CA2007001230 W CA 2007001230W WO 2009009853 A1 WO2009009853 A1 WO 2009009853A1
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Prior art keywords
water
content
alcohol
grams
hydrogen
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PCT/CA2007/001230
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English (en)
Inventor
Boyd Davis
Chih-Ting Flora Lo
Kunal Karan
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Boyd Davis
Chih-Ting Flora Lo
Kunal Karan
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Priority to PCT/CA2007/001230 priority Critical patent/WO2009009853A1/fr
Publication of WO2009009853A1 publication Critical patent/WO2009009853A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/065—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents from a hydride
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/066—Integration with other chemical processes with fuel cells
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C01B2203/1058—Nickel catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1076—Copper or zinc-based catalysts
    • 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

Definitions

  • the field of the invention relates to hydrogen storage, generation and power systems.
  • the field of the invention relates to water/alcohol/chemical hydride systems.
  • Solid chemical hydrides such as sodium borohydride, NaBH 4
  • Hydrogen can be released by reacting the hydride with other reactants.
  • hydrogen can be generated by alcoholysis, such as methanolysis, as shown in equation A.
  • the storage capacity is calculated by dividing the weight of four moles of hydrogen by the total weight of one mole of sodium borohydride and two moles of water according to equation D:
  • Additional water can be stored on-board to maintain the hydrated sodium borate in solution and prevent precipitation. In that case, the total amount of water needed must both react with NaBH 4 and dissolve the by-product NaBO 2 .4H 2 O. Other problems arise, however, when NaBO 2 .4H 2 O is maintained in solution. Its low solubility in low temperature aqueous solutions is one example. The storage requirements of the additional water on-board will also reduce the overall system storage density.
  • the sheer volume of the hydrated sodium borate is another concern because four moles of water attach to each mole of sodium borate when hydration takes place.
  • Storage volume requirements for hydrated sodium borate also add to the total system and its density, reducing the overall volumetric storage density of hydrogen in the system.
  • Problems with hydrated borate formation are well known. See, e.g., Shang, Y. & Chen, R. Hydrogen Storage via the Hydrolysis of NaBH4 Basic Solution: Optimization of NaBH 4 Concentration. Energy & Fuels, 2006, 20, 2142-2148). An improved system is desired.
  • a system comprising a hydrogen generation reactor, a reactor inlet, a reactor outlet for controlling output, water, at least one chemical hydride of formula M(BH4) X , wherein M is an element selected from a group consisting of groups 1 and 2 of the periodic table, B is an element selected from a group consisting of group 13 of the periodic table, H is hydrogen, and x is a positive integer; at least one alcohol of formula R-OH, wherein R is an alkyl group, and wherein a water: total dissolved hydride ratio is suitable for theoretical hydrolysis of total dissolved hydride, and an alcohol: total dissolved hydride ratio is suitable for pseudo-first order alcoholysis of total dissolved hydride.
  • the system further comprises a stabilizer for stabilizing the at least one hydride with a member selected from the group consisting of the water and the alcohol.
  • the system further comprises at least one catalyst.
  • the system further comprises a catalytic content including a base metal.
  • the system further comprises a catalytic content including at least one element selected from the group consisting of copper, iron, nickel, and cobalt.
  • the system further comprises a precious metal catalytic content that is negligible.
  • the system further comprises a catalyst structure including at least one member selected from the group consisting of metal mesh, metal foam, beads, and coated substrates.
  • the system further comprises a total dissolved hydride conversion in the range from about 100% to about 10%. In another aspect, the system further comprises a total dissolved hydride conversion in the range from about 100% to about 1%.
  • the system further comprises alcohol: total dissolved hydride ratio from about 5:1 to about 100:1. In another aspect, the system further comprises alcohol: total dissolved hydride ratio from about 7:1 to about 50:1.
  • the system further comprises alcohol: total dissolved hydride ratio of about 10:1. In another aspect, the system further comprises water: total dissolved hydride ratio from about 3.0:1 to about 0.05:1. In another aspect, the system further comprises water: total dissolved hydride ratio from about 2.5:1 to about 0.5:1. In another aspect, the system further comprises water: total dissolved hydride ratio from about 2.1 to about 1.5:1. In another aspect, the system further comprises water: total dissolved hydride ratio from about 2.0:1. In another aspect, the water is at least one member selected from the group consisting of off board supplied water and fuel cell recovered water. In another aspect, the water is fuel cell recovered water. In another aspect, the water is supplied together with the alcohol.
  • the alcohol is at least one member selected from the group consisting of off board supplied alcohol, depleted reactor solution, and depleted reactor solution recovered alcohol. In another aspect, the alcohol is at least one member selected from the group consisting of the depleted reactor solution and the depleted reactor solution recovered alcohol. In another aspect, at least one hydride is at least one member selected from the group consisting of off board supplied hydride, the depleted reactor solution, and the depleted reactor solution recovered hydride. In another aspect, at least one hydride is at least one member selected from the group consisting of depleted reactor solution and depleted reactor solution recovered hydride. In another aspect, the system further comprises a storage chamber for supplying the reactor.
  • the storage chamber includes at least one dissolved hydride and alcohol. In another aspect, the storage chamber includes at least one solid hydride. In another aspect, the storage chamber supplies the reactor with at least one dissolved hydride. In another aspect, the system further comprises at least one supplemental storage chamber for supplying the reactor with at least one member selected from the group consisting of the water and the alcohol. In another aspect, the system is continuous. In another aspect, the system further comprises at least two passes. In another aspect, the reactor is a catalytic reactor.
  • a single pass total dissolved hydride conversion is from about 100% to about 10%. In another aspect, single pass total dissolved hydride conversion is from about 100% to about 1%. In another aspect, the system further comprises a process control including variable conversion rates. In another aspect, the system total storage density is independent from the single pass total dissolved hydride conversion. In another aspect, at least one chemical hydride includes sodium borohydride. In another aspect, at least one alcohol includes methanol.
  • the system produces hydrogen for about 100 hours.
  • depleted solution is recycled to the reactor.
  • hydrogen production is 3.4 grams.
  • power production is 1 Watt.
  • alcohol is methanol, methanol content is 20 ml, sodium borohydride content is 15.9 grams, water content is 15.2 grams, sodium hydroxide content is 5 percent by weight, catalyst is Ru- Al 2 O 3 pellets, and temperature is about 20 degrees Celsius.
  • water is supplied on board and the total system density excluding equipment weight is 7.1 percent by weight.
  • water is supplied from a fuel cell and the total system density excluding equipment weight is 10.5 percent by weight.
  • hydrogen production is 10.1 grams.
  • power production is 3 Watts.
  • alcohol is methanol
  • methanol content is 30 ml
  • sodium borohydride content is 47.7 grams
  • water content is 45.5 grams
  • sodium hydroxide content is 5 percent by weight
  • the catalyst is Ru-Al 2 O 3 pellets
  • temperature is about 20 degrees Celsius.
  • water is supplied on board and the total system density excluding equipment weight is 8.5 percent by weight.
  • water is supplied on board and the total system density including system equipment weight of 100 grams is 4.7 percent by weight.
  • water is supplied from a fuel cell and the total system density including system equipment weight of 100 grams is 6.0 percent by weight.
  • alcohol is methanol
  • methanol content is 20 ml
  • sodium borohydride content is 47.7 grams
  • water content is 45.5 grams
  • sodium hydroxide content is 5 percent by weight
  • the catalyst is Ru-Al 2 O 3 pellets
  • temperature is about 20 degrees Celsius.
  • water is supplied from a fuel cell and the total system density excluding equipment weight is 14.9 percent by weight.
  • the system produces hydrogen for about 50 hours.
  • depleted solution is recycled to the reactor.
  • hydrogen production rate is 10 ml/minute.
  • alcohol is methanol
  • methanol content is 200 ml
  • sodium borohydride content is 13.1 grams
  • water content is 13.0 grams
  • sodium hydroxide content is 7.9 grams
  • catalyst is Ru-Al 2 O 3
  • temperature is about 20 degrees Celsius .
  • hydrogen is produced for about 42 hours.
  • depleted solution is recycled to the reactor.
  • hydrogen production rate is 11 ml/minute.
  • alcohol is methanol
  • methanol content is 50 ml
  • sodium borohydride content is 15.0 grams
  • water content is 14.1 grams
  • sodium hydroxide content is 7.9 grams
  • catalyst is Ru- Al 2 O 3
  • temperature is about 20 degrees Celsius.
  • hydrogen is produced for about 8 hours. In another aspect, hydrogen production rate is 20 ml/min. In another aspect, alcohol is methanol, methanol content is 200 ml, sodium borohydride content is 33.0 grams, water content is 30.3 grams, sodium hydroxide content is 23.6 grams, catalyst is Ru-SiO 3 , and temperature is about 20 degrees Celsius. In another aspect, hydrogen is produced for about 150 minutes. In another aspect, hydrogen production rate is 10 ml/min. In another aspect, alcohol is methanol, methanol content is 50 ml, sodium borohydride content is 6.4 grams, water content is 6.1 grams, sodium hydroxide content is 2.0 grams, catalyst is Ru-SiO 3 , and temperature is about 20 degrees Celsius.
  • hydrogen is produced for about 14.5 minutes. In another aspect, hydrogen production rate is 23 ml/min. In another aspect, alcohol is methanol, methanol content is 30 ml, sodium borohydride content is 0.8 grams, water content is 0.8 grams, sodium hydroxide content is 1.1 grams, catalyst is Ru-Al 2 O 3 , and temperature is about 0 degrees Celsius. In another aspect, hydrogen is produced for about 18 hours. In another aspect, hydrogen production rate is 5 ml/min.
  • alcohol is methanol
  • methanol content is 100 ml
  • sodium borohydride content is 6.1 grams
  • water content is 0.006 ml/min
  • sodium hydroxide content is 4.0 grams
  • catalyst is Ru-SiO 3
  • temperature is about 20 degrees Celsius.
  • hydrogen is produced for an additional about 50 hours.
  • hydrogen production in the additional about 50 hours is varied from earlier production.
  • hydrogen production in the additional 50 hours is 1.5 ml/min.
  • hydrogen is produced for about 400 minutes. In another aspect, hydrogen production rate is 0.0008 ml/min.
  • alcohol is methanol, methanol content is 18 ml, sodium borohydride content is 0.038 grams, water content is 0.036 grams, and temperature is about 0 degrees Celsius.
  • hydrogen is produced for about 12 hours. In another aspect, hydrogen production is 0.003 ml/min.
  • alcohol is methanol, methanol content is 18 ml, sodium borohydride content is 0.4 grams, water content is 0.038 grams, and temperature is about minus 20 degrees Celsius.
  • hydrated borate formation is inhibited.
  • at least one controller controls a supply for at least one member selected from the group consisting of the off board supplied hydride, the off board supplied alcohol, the off board supplied water, the depleted reactor solution, the depleted reactor solution recovered hydride, the depleted reactor solution recovered alcohol, and the fuel cell recovered water.
  • the system further comprises a fuel cell for receiving hydrogen fuel.
  • the system further comprises a PEM fuel cell stack for receiving hydrogen fuel.
  • electric output from the fuel cell stack is sent to an electric motor.
  • fuel cell generated water is supplied to at least one member of the group consisting of an anode, a reactant heater, an alcohol vapour stripper, a water storage chamber, an exhaust outlet.
  • the system further comprises a cold start-up unit for generating hydrogen by catalytic alcoholysis of the at least one hydride.
  • a cold start-up unit releases heat to the system and shuts down when a set point temperature is reached.
  • the system supplies hydrogen to fuel cell applications in confined environments.
  • the system supplies hydrogen to fuel cell applications for portable devices.
  • the system supplies hydrogen to fuel cell applications for automotive devices.
  • the system start-up ambient operating temperature is from about minus 50 to about 60 degrees Celsius.
  • Figure 1 illustrates one embodiment of the invention as a constant volume batch reactor system for hydrogen generation from chemical hydride, water, and alcohol.
  • Figure 2a illustrates a front view of an alternate design for the reactor in Figure 1.
  • Figure 2b illustrates a side view of the reactor in Figure 2b.
  • Figure 3 illustrates another embodiment of the invention as a fuel cell system incorporating hydrogen production.
  • the present invention provides a system of hydrogen storage and production using chemical hydride in the presence of water.
  • a system using hydrogen production together with a fuel cell is also provided.
  • Hydrogen is produced in the presence of water, but typical associated production of density-decreasing by-products such as hydrated sodium borate is reduced. Equipment function is maintained and the process can be flexibly arranged. Hydrogen can be removed, and other products such as anhydrous sodium borate can be removed from the system as desired.
  • the system comprises contacting a chemical hydride with alcohol and water to form hydrogen and by-products. This promotes conversion of water to form hydrogen, or anhydrous borate and alcohol, according to reaction temperature, and reduces water available for conversion to hydrated borate.
  • Hydrated borate formation can be inhibited by contacting chemical hydride with alcohol and water, wherein an alcohol: total dissolved hydride ratio is suitable for pseudo-first order alcoholysis and a water: total dissolved hydride ratio is suitable for theoretical hydrolysis.
  • the hydride can be contacted with alcohol and water in combination, or in sequence.
  • Available hydrides are represented by the formula M(BH 4 ) X , where M is an element selected from a group consisting of groups 1 and 2 of the periodic table, B is an element selected from a group consisting of group 13 of the periodic table, H is hydrogen, and x is a positive integer.
  • Example hydrides include: NaBH 4 , LiBH 4 , Mg (BH 4 ) 2 , KBH 4 and combinations.
  • R-OH available alcohols are represented by the formula R-OH, wherein R is an alkyl group. Examples include CH 3 OH, C 2 H 5 OH, C 3 H 7 OH, C 4 H 9 OH, and combinations. Where alcoholysis occurs, water reacts with the alcoholysis by-product, M((BO-R) 4 ) X , according to equation F.
  • Equation G For example, in equation A above where the alcohol is methanol, CH 3 OH, and the alcoholysis by-product is sodium tetramethoxyborate , NaB(OCH 3 ) 4 , water reacts with the by-product according to Equation G.
  • the alcohol: total dissolved hydride ratio suitable for pseudo- first order alcoholysis is a ratio from about 5:1 to about 100:1; preferably from about 7:1 to about 50:1; and more preferably from about 10:1.
  • the water: total dissolved hydride ratio suitable for theoretical hydrolysis is a ratio from about 3.0:1 to about 0.05:1; preferably from about 2.5:1 to about 0.5:1; more preferably from about 2.1 to about 1.5:1; and more preferably from about 2.0:1.
  • depleted solution or “depleted reactor solution” means materials that were subjected to reaction at least once. These materials may contain unreacted materials, including dissolved hydride, and inert materials.
  • the depleted solution can be returned to the reactor, without treatment, for further reaction if desired.
  • the reactor contents can be subjected to further reaction.
  • a portion of the depleted solution can be separated from the depleted solution that is sent back to the reactor.
  • the water can be provided at a water: total dissolved hydride ratio suitable for theoretical hydrolysis by ratio controller or other mechanisms known in the field.
  • Solid chemical hydride can be stored in saturated solution located in storage chambers, or in the reactor with the reactants where such storage does not compromise reactor function. (It is understood that the saturation point of the saturated solution is reached when dissolved hydride solute crystallizes from solution at the same rate at which it dissolves.)
  • Sodium borohydride can be loaded to the solubility limit, then additional quantities can be stored as solids to provide feed storage and increase storage capacity. These additional solids are available for use in continuous operation, if desired, since they dissolve and replenish the sodium borohydride consumed from solution. Additional sodium borohydride can be supplied to the system after the initial load is consumed, or earlier as desired.
  • a hydride stabilizer can be added if desired.
  • Alcohol levels available to the reactor can be maintained at an alcohol: total dissolved hydride ratio suitable for pseudo-first order alcoholysis by, for example, returning depleted solution containing alcohol to the reactor. Where portions of the depleted solution are separated therefrom, alcohol can be recovered from the portion by filtration or otherwise and redirected to the reactor if desired. Where return of depleted solution is not desired, alcohol levels can be maintained by reloading to the system otherwise.
  • Example 1 is an illustrative example of alcoholysis-like kinetic behaviour and controlled hydration for pseudo-first order hydrogen generation reaction systems containing water.
  • a constant volume batch reactor was used to monitor hydrogen generation from sodium borohydride and water between -20 and +50 °C in excess solvent (here, anhydrous methanol, 99.5+% purity, water content less than 50 ppm, Fisher Scientific CanadaTM) .
  • Figure 1 illustrates the modified 100 ml three-neck flask reactor (1).
  • a first neck with digital temperature reader (2) monitored the temperature via a thermocouple (3) housed in a 1/4" closed end glass tubing inserted into the flask through an 0-ring.
  • a second neck delivered sodium borohydride to the reactor via a modified stopcock (4).
  • a third neck with valve 1 (5), a valved two-way glass fitting connected to 1/4" PVC tubing directed product hydrogen gas into a inverted 250 ml graduated cylinder (6) for volumetric analysis.
  • This third neck was also used for purging argon gas , Ar ( 7 ) .
  • the inverted graduated cylinder ensured that the vapour phase volume change in the product stream was attributed to pure hydrogen. Water placed in the cylinder effectively absorbed any methanol vapour entering therein.
  • the stopcock was weighed before and after the tests to calculate sodium borohydride in the system.
  • Anhydrous methanol was measured in an amount approximately 100 times the amount required for theoretical methanolysis of sodium borohydride.
  • a quantity of distilled water twice the number of moles of sodium borohydride was measured, then injected into the anhydrous methanol.
  • This solution was poured into the reactor through the open third neck.
  • the neck was sealed and 1/4" PVC tubing was connected to a glass outlet extending therefrom. The other end of the tubing was disconnected from inside the inverted graduated cylinder to set up the purging period.
  • the reactor was insulated in an insulated recirculating tube (9) and immersed in a temperature controlled heating/cooling fluid (10) in an open top styrofoam container.
  • the container was placed on a mechanical stirrer (11) and a chiller/heater (12) connected to the insulated recirculating tube set the recirculating heating/cooling fluid temperature.
  • the 250 ml graduated cylinder was filled with water (13) and placed in a room temperature water bath (14).
  • a magnetic stirrer (15) was activated at medium level.
  • a 20 minute low flow rate argon gas purge minimized moisture content in the system.
  • argon flow was stopped and valve 1 on the third neck was turned to permit product gas exit via the PVC tubing.
  • the open end of the PVC tubing was inserted in the inverted graduated cylinder and the initial level of distilled water therein was recorded.
  • the reaction commenced when sodium borohydride was released into the reactor from the modified stopcock hole.
  • the gas phase volume change in the inverted graduated cylinder was recorded as a function of time.
  • the reaction was determined to have reached completion when the volume displaced in the graduated cylinder matched the theoretical amount of hydrogen generated according to the ideal gas law. In trials where a small amount of powder remained in the stopcock, the reaction was determined to reach completion when the graduate cylinder volume remained constant for more than 30 minutes.
  • reactor contents were transferred to a vacuum flask, dried under argon, and analytically analyzed using techniques including x-ray diffractometry.
  • Gas captured in the graduated cylinder was confirmed as pure hydrogen by connecting the cylinder to a second reactor filled with methanol and heating to 50 °C for one hour. Since methanol has lower vapour pressures at temperatures below 50 °C and no gas phase volume change occurred in the inverted graduated cylinder, all methanol evaporated from the reactor during testing was absorbed by water in the inverted graduated cylinder.
  • k' is the pseudo-first order rate constant proportional to the concentration of methanol present at startup, of the disappearance of sodium borohydride, with units in reciprocal seconds.
  • Rate constants for reactions at corresponding temperatures .
  • Natural logarithms of the rate constants were plotted as a function of reciprocal temperature using the linearized Arrhenius equation in equation I.
  • Ea is the activation energy
  • R is the rate constant
  • T is the temperature of the reaction
  • A is the pre-exponential factor
  • Activation energies and pre-exponential factors for the hydrogen generation reactions were obtained from the slopes and the y- intercepts. Confidence limits corrected for the natural logarithm were used as final values for the error analysis. The mean of the natural logarithm of rate constants was calculated for respective temperatures, then the standard deviation and the confidence limit were obtained based on a 95% confidence interval .
  • Examples 2 to 7 were conducted at room temperature using catalysts and recycle. Examples 2 to 6 were conducted using water in the feed. Example 7 was conducted using separate water feed. Examples 2 to 7 were conducted using sodium borohydride in the feed with sodium borohydride solids in the chamber. Example 7 was conducted using sodium borohydride in the feed without solids in the chamber. Examples 8 and 9 were conducted at low temperature using no catalysts and no recycle.
  • the minimum stable hydrogen generation rate reached 23 ml/min (100% theoretical conversion) in 2 minutes, decreased to 15 ml/min (65% conversion) in 8 minutes, then increased to 23 ml/min (100% conversion) at 14.5 minutes, when catalyst destruction due to volume expansion of ion exchange resin beads in methanol (100%) was recorded.
  • the examples 2 to 9 summarized in Table 1 are merely a selection of illustrative designs that can be used to contact the reactants for hydrogen generation, and the range of available designs facilitates many applications.
  • the solid chemical hydride can be provided for contact via controller such as the pellet dispenser inlet (100) at Fig. 2.
  • controller such as the pellet dispenser inlet (100) at Fig. 2.
  • the thermocouple neck (102) and purge gas/hydrogen outlet neck (104) are also shown in example orientation).
  • Other examples include a pre- mixed cartridge chamber of saturated solution, and other variations.
  • Hydrogen generation rates less than 100 ml/min can be provided for extended periods where the continuous operation conditions are met.
  • Fuel cell applications can be designed to address specific needs in confined environments including, for example, submersible, mining/underground, and other enclosed or substantially enclosed environments. Low temperature and portable applications are possible. Where higher hydrogen generation rates are required for applications such as hydrogen refueling stations, or for large power usage in the kilowatt range or otherwise, applications can meet these needs as well.
  • Hydrogen storage density will depend in part on the weight of auxiliary equipment required by the system. Where water is supplied from outside the system, densities exceed those of comparable systems supplied from on-board water storage chambers. System density decreases when additional storage chambers are required for reactants, products, or both. On the product side, it is understood that additional product storage chambers can be downsized or eliminated, depending on the system, where additional filtration devices or other equipment control on-board alcohol content. Although these increase the overall weight, improved retention can be achieved. The large quantity of alcohol available for pseudo-first order rate reactions will assist here.
  • the system density also decreases when on-board customized equipment is required.
  • Single pass systems with high conversion catalysts can require such customization.
  • designs consistent with the present subject matter decrease dependence on single pass conversion and can rely on standard equipment instead, according to the particular application.
  • flexible design considerations associated with the subject matter herein permit use of standard-sized pumps and other equipment. This reduces comoonent weight and improves total system density.
  • Example systems with densities follow.
  • Example 10 1 Watt system. 100 hours operation
  • Example 11 1 Watt system, 100 hours operation
  • Total amount of methanol is 30 ml, NaOH is 5 wt% of methanol solution, sodium borohydride required is 47.7 g, and water required is 45.5 g. Water in this system is stored onboard.
  • the hydrogen produced is 10.1 g (121.3 L at standard condition).
  • Example 13 3 Watt system, 100 hours operation
  • Example 14 3 Watt system, 100 hours operation
  • Total amount of methanol is set to be 30 ml, NaOH is 5 wt% of methanol solution, sodium borohydride required is 47.7 g, and water required is 45.5 g. Water in this system is stored onboard.
  • the hydrogen produced is 10.1 g (121.3 L at standard condition) .
  • the system includes a plastic solvent/borohydride storage system, a stainless steel catalytic reactor with 10 g Ru-based catalysts, a filtration unit, and a plastic storage chamber for filter cake.
  • the weight of the system is assumed to be 100 g.
  • Example 15 3 Watt system, 100 hours operation
  • Total amount of methanol is set to be 30 ml, NaOH is 5 wt% of methanol solution, sodium borohydride required is 47.7 g, and water required is 45.5 g. Water in this system is recycled from the fuel cell. The fuel cell can make 91.0 g of water and a 50% water recycle rate is assumed.
  • the hydrogen produced is 10.1 g (121.3 L at Standard condition).
  • the system includes a plastic solvent/borohydride storage system, a stainless steel catalytic reactor with 10 g Ru-based catalysts, a filtration unit, and a plastic storage chamber for filter cake. The weight of the system is assumed to be 100 g.
  • Examples 10 to 15 summarized in Table 2 are illustrative and not intended to limit the scope of the invention.
  • the example cases illustrate densities in excess of the 4.8% value noted in equation B for theoretical methanolysis of sodium borohydride.
  • the example cases also illustrate that hydrogen storage density will depend in part on the weight of the components and auxiliary equipment required by the system. Where water is supplied from external sources such as the fuel cell recycle (as in cases 11, 13, and 15), densities exceed those of comparable systems supplied from on-board water storage chambers (here, example cases 10, 12, and 14, respectively).
  • the example cases also compare favourably to aqueous systems. For example, see the following two single pass aqueous system examples with 100% conversion rates and no recycle of depleted fuel components.
  • a typical PEM fuel cell operating at overall stack efficiency of approximately 80% can be combined with the hydrogen generation process to provide an overall system efficiency of approximately 75%.
  • a sample fuel cell system incorporating the hydrogen production system is illustrated at Fig. 3. The schematic describes one sample system design for the fuel cell in a battery-powered, electrically motored vehicle.
  • the normal hydrogen generator (21) has a fixed amount of methanol (22) that can be replenished. Hydrogen is generated on demand using a controller that dispenses solid sodium borohydride (23) into the hydrogen generator. Water (24) is injected in amounts suitable for theoretical hydrolysis of sodium borohydride.
  • the anhydrous sodium borate by-product is readily dissolved in methanol.
  • the vapour product stream (25) comprised of hydrogen gas, water vapour, and methanol vapour is contacted with a recycle water stream (26) to hydrate hydrogen and absorb methanol in the vapour phase.
  • Humidified hydrogen (27) is sent to the anode of the fuel cell stack (28) as the fuel feed.
  • Air (29) is pumped into the cathode of the fuel cell stack at an oxygen: hydrogen ratio suitable for increased hydrogen utilization, for example, 2:1.
  • the example PEM fuel cell stack consists of single cells connected in series with stainless steel bipolar plates interposed therebetween. Cooling plates in alternate cells remove excess heat.
  • Each cell is made of a Nafion® membrane in a membrane electrode assembly (MEA) with platinum based catalyst.
  • MEA membrane electrode assembly
  • the electrodes are made of graphite paper and the MEA is manufactured by hard compressing the components.
  • a typical working temperature is 80 °C with overall stack efficiency of 65%.
  • the electricity output from the fuel cell is sent to the electric motor (30) for constant speed driving or battery (31) recharge.
  • Water (32) is supplied to the anode assuming a back osmosis drag of up to 10% from the cathode.
  • Hot water produced in the fuel cell stack (33) can be used to heat up reactants and to strip off methanol vapour, and then be recycled back into the water storage chamber.
  • Surplus water (34) can be stored to cool the fuel cell if required, or can be disposed via an exhaust pipe. Where water produced in the fuel cell is not readily reusable, water can be sourced otherwise.
  • a cold start-up unit (35) is provided with methanol and 10 wt% cobalt chloride.
  • the cold start-up unit generates hydrogen at cold temperatures by methanolysis of sodium borohydride with the aid of the catalyst.
  • the cold start-up unit releases heat that warms the fuel cell and the normal hydrogen generating unit.
  • the start-up unit is shut down and hydrogen production continues via the normal hydrogen generator.
  • Methanol supply for the cold start-up unit can be replenished from storage. Additional catalyst supply is typically not required because the product stream is gaseous and cobalt chloride has minimal vapour pressure at normal environmental conditions .
  • the relevant industrial applicability is the area of hydrogen storage and generation, and hydrogen use in fuel cells.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Fuel Cell (AREA)

Abstract

L'invention porte sur un système de génération d'hydrogène comportant un réacteur de génération d'hydrogène ; une entrée de réacteur ; une sortie de réacteur ; de l'eau ; au moins un nitrure métallique de formule M(BH4)X, où M est un élément choisi parmi les éléments des groupes 1 et 2 de la Classification Périodique, B est un élément choisi parmi les éléments du groupe 13 de la Classification Périodique, H représente hydrogène, et x est un entier positif ; et au moins un alcool de formule R-OH, où R est un groupe alkyle. Le rapport eau/hydrure dissous total est d'environ 3,0:1 à environ 0,05:1 et le rapport alcool/hydrure dissous total est d'environ 5:1 à environ 100:1. Le système de génération d'hydrogène sert de source d'hydrogène pour des piles à combustible.
PCT/CA2007/001230 2007-07-17 2007-07-17 Système de génération d'hydrogène WO2009009853A1 (fr)

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EP2468680A3 (fr) * 2010-12-21 2012-08-22 Hynergreen Technologies, S.A. Procédé de production d'azote par hydrolyse catalysée d'un hybride complexe et installation avec réacteur semi-continu permettant d'effectuer le procédé
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Cited By (7)

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EP2468680A3 (fr) * 2010-12-21 2012-08-22 Hynergreen Technologies, S.A. Procédé de production d'azote par hydrolyse catalysée d'un hybride complexe et installation avec réacteur semi-continu permettant d'effectuer le procédé
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WO2014013246A2 (fr) * 2012-07-16 2014-01-23 Prometheus Wireless Limited Appareil à piles à combustible, composition et générateur d'hydrogène s'y rapportant
WO2014013246A3 (fr) * 2012-07-16 2014-04-03 Prometheus Wireless Limited Appareil à piles à combustible, composition et générateur d'hydrogène s'y rapportant
GB2507466A (en) * 2012-07-16 2014-05-07 Prometheus Wireless Ltd Fuel Cell Apparatus, Composition and Hydrogen Generator
GB2507466B (en) * 2012-07-16 2015-04-08 Prometheus Wireless Ltd Fuel cell apparatus

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