CA1098343A - Method for manufacture of magnesium composite and method for manufacture of hydrogen by said composite - Google Patents
Method for manufacture of magnesium composite and method for manufacture of hydrogen by said compositeInfo
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- CA1098343A CA1098343A CA222,198A CA222198A CA1098343A CA 1098343 A CA1098343 A CA 1098343A CA 222198 A CA222198 A CA 222198A CA 1098343 A CA1098343 A CA 1098343A
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Abstract
ABSTRACT OF THE DISCLOSURE
A method for the manufacture of a magnesium composite comprising placing magnesium and a metal powder selected from the group consisting of chromium, iron, manganese, nickel, zinc and oxides thereof in a container; applying mechanical force to the magnesium and metal powder mixture whereby 0.01% to 30% by weight of the metal powder is embedded in the magnesium; and removing any excess of the metal powder not embedded in the magnesium.
A method for the manufacture of a magnesium composite comprising placing magnesium and a metal powder selected from the group consisting of chromium, iron, manganese, nickel, zinc and oxides thereof in a container; applying mechanical force to the magnesium and metal powder mixture whereby 0.01% to 30% by weight of the metal powder is embedded in the magnesium; and removing any excess of the metal powder not embedded in the magnesium.
Description
1~8343 This invention relates to a method for the manufacture of a magnesium composite capable of generating hydrogen upon introduction into water and to a method for the manufacture of hydrogen by use of the composite manufactured by said method.
In recent years, hydrogen has come to attract in-creasing attention as a prospective fuel. Hydrogen possesses excellent properties as a fuel in that the combustion thereof does not entail generation of air-polluting substances such as, for example, sulfur oxides or nitrogen oxides. If a method is established which permits easy and convenient generation of hydrogen, then the hydrogen obtained by this method can be used as an energy source in various fields, ranging from small-scale household uses to heavy-duty industrial uses involving the operation of automobiles, marine vessels, etc. For the manu-facture of hydrogen, various methods have been developed and put to commercial uses. A method which produces hydrogen by the electrolysis of water, methods which produce hydrogen in the form of a by-product in the modification of petroleum and coal gases and in the electrolysis of common salt and other similar methods are examples. However, these methods invariably require large-scale manufacturing apparatuses.
It is universally known that when magnesium is allowed to react with water, the reaction proceeds as indicated by the following equation to generate hydrogen.
Mg + 2H2O -~ Mg(OH)2 + H2 In the above reaction, if magnesium prepared in the form of a mixture with iron, nickel, copper, etc. or in the form of an alloy with any of the metals described above is allowed to react with water, then the forward reaction proceeds at an accelerated rate. This is known to the art in view of, e.g., British Patent . , q~
10"8343 No. 579,246 and U.S.P. No, 2,623,812.
An object of the invention is to provide a method for producing magnesium composites useful for liberating hydrogen from water.
According to one embodiment of the invention there is provided a method for the manufacture of a magnesium composite capable of generating hydrogen upon contact with water contain-ing at least 1% by weight of a salt selected from the group consisting of NaCQ, KCQ, Na2SO4, K2SO4 and mixtures thereof;
the method comprising placing magnesium and a metal powder selected from the group consisting of chromium, iron, manganese, nickel, zinc and oxides thereof in a container; applying mechanical force to the magnesium and metal powder mixture whereby 0.01~ to 30~ by weight of the metal powder is embedded in the magnesium; and removing any excess of the metal powder not embedded in the magnesium.
Firstly, a method for manufacturing a magnesium compo-site having deposited on its surface at least one member selected from the group consisting of iron, nickel, zinc, chromium and manganese and prepared in the form of a metal powder or an oxidized metal powder is described.
The form in which magnesium is used is not specifically fixed. It can be used in the form of powder, granules, plates, foils, etc. To meet requirements arising from practical con-siderations, it may be used in the form of helically shaped plates or foils or of cylindrically shaped rods, for example.
From the practical point of view, use of magnesium in the form of plates having a thickness of not more than 1 mm results in the formation of a magnesium composite which generates hydrogen at an increased rate.
` ~V~8343 When magnesium is used in the form of powder or granules, it is only natural that the particle diameter thereof should be greater than that of the pure metal powder or oxidized metal powder which is bein~ deposited thereon.
The metal powder or oxidized metal powder to be de-posited on the magnesium desirably has a particle size not coarser than 200 mesh as measured by the Tyler's standard sieves.
It is further desirable to include finer particles of the order of 10 microns, for example.
Adhesion of such metal powders or oxidized metal powders to the surface of the magnesium is accomplished by pressurized friction. This adhesion by means of pressurized friction con-stitutes one of the salient features of the present invention.
The term "pressurized friction" refers to an action whereby the magnesium and the powder desired to be deposited thereon are moved relative to each other while the two substances are held pressed against each other. For example, the metal powder or oxidized metal powder can be attached to the surface of the magnesium, used in the form of granules, foils or plates, by placing them both in a suitable container such as, for example, a mortar and stirring the contents 30 to 100 turns with a pestle.
In this case, the amount of the metal powder or oxidized metal powder to be attached to the surface of the magnesium is required to fall in the range of from 0.01 to 30% by weiyht based on the weight of magnesium. The required adhesion can be accomplished by placing in the mortar the metal powder or oxidized metal pow-der in an amount roughly 5 to 100 times in excess as is desired to be attached to the magnesium and rotating the pestle in the mortar as described above. When the magnesium used in this case is in the form of foils or plates, the metal powder or oxidized ~(3198343 metal powder which has escaped adhesion to magnesium can be recovered with extreme ease. When the magnesium is in the form of granules, the removal of the metal powder or oxidized metal powder can eas~ly be effected by any known technique for powder separation, such as, for example, simple sifting or centrifu-gation. The powder which has escaped adhesion and then is recovered can be used in its unmodified form for the subsequent cycle of magnesium adhesion.
The composite of magnesium and metal or metal oxide can further be manufactured by placing the magnesium plate or foil in the metal powder or metal oxide powder and moving the plate or foil while applying pressure thereto.
The pressurized friction between the magnesium and the powder can also be effected by placing the magnesium in the form of foils or plates in a mass of the metal powder or oxidized metal powder and beating the mass mildly, such as with a hammer, for example, to afford the desired composite of magnesium and metal powder or oxidized metal powder.
The aforementioned composite can otherwise be manu-factured by a technique similar to the process employed for sur-face polishing.
Magnesium is a metal which abounds in malleability and exhibits a lower degree of hardness at normal room temperature than iron, zinc, chromium and manganese. Thus, any of the treat-ments described above permits the metal powder or oxidized metal powder to be attached to the magnesium, giving rise to the desired magnesium composite. The amount of the metal powder or oxidized metal powder to be deposited on the surface of the magnesium can be adjusted e.g. by suitably fixing the number of revolu~ions of the pestle and the amount of powder placed in the lOg8343 container or regulating the conditions of pressurized friction.
A microscopic observation of the magnesium composite reveals that granules or particles of either the metal powder or the oxidized metal powder are inserted into the recesses formed on the surface of the magnesium matrix in conformity to the shape of the granules or particles. The magnesium powder requires careful handling so as to preclude the possibility of ignition.
When magnesium of a particle size coarser than lO0 mesh is subjected to pressurized friction, however, no particular care is required in its handling, except it is best treated in a dry state.
The amount of the metal powder or oxidized metal powder to be incorporated in the composite is selected with respect to the purpose for which the produced hydrogen is used, with due consideration being paid to the fact that this amount is correlated to some extent with the rate at which hydrogen gen-eration proceeds. It has been confirmed that the magnesium com-posite is still effective when the amount of the metal powder or oxidized metal powder incorporated therein is in the range of 0.01 - 2~ by weight based on the weight of magnesium. The com-posite fails to produce the desired effect when the amount of the metal powder or oxidized metal powder is lower than 0.01~
by weight and no increase of effect is gained when the amount exceeds 30~ by weight. The fact that the magnesium composite is effective even when the amount of the metal powder or oxidized metal powder falls in the range of 0.01% - Q.1%, for example, by weight based on the weight of magnesium as descrihed above has been neither disclosed nor suggested anywhere in the literature published to date.
When the magnesium aomposite is introduced into water ~.
10~8343 containing therein at least one member selected from the group consisting of NaC~, KC~, Na2SO4 and K2SO4, hydrogen is generated.
As is demonstrated in the preferred embodiments and comparative examples given herein below, the rate at which the generation of hydrogen proceeds in this system is extremely high, as compared with, a system in which a mixture of magnesium and a metal manu-factured by the conventional method is introduced in water. If impurities are present in the magnesium and in the iron, nickel, zinc, chromium or manganese to be used in the manufacture of the composite, they have no adverse effect upon the amount of hydro-gen generated. River water, town water, sea water or any other ordinary water can be used for the generation of hydrogen through contact with the magnesium composite. In the case of sea water, otherwise required addition of metal salts can be dispensed with, for it contains NaCQ and other salts.
In the case of ordinary fresh water, the amount of NaCQ, KCQ, Na2SO4 or K2SO4 to be incorporated is required to be not less than 1% by weight.
A possible explanation for the enhanced generation of hydrogen by the magnesium composite is as follows: The metal powder or oxidized metal powder is uniformly attached in fine particles to the entire surface of the magnesium metal. This means that the area of contact between the powder particles and the magnesium metal is extremely large. When this composite is brought into contact with water to generate hydrogen, the pro-portion of the surface of the magnesium covered by Mg(OH)2 is small, so that no measurable decline of the activity of magnesium is observed. This means that the generation of hydrogen con-tinues.
The hydrogen which is generated by the method of this invention has been assayed by gas chromatography to have a purity "~ 10~ 3 exceeding 99.999%. Further, Mg(OH)2 produced in the reaction can easily be converted into magnesium, which can be put to cyclic use in the formation of magnesium composite.
As is clear from the foregoing description, the method of this invention enables any ordinary water to generate hydro-gen of high purity in large volumes at a high rate, indicating that the present invention enjoys high practical value. When the magnesium composite is manufactured in advance, hydrogen can be obtained at virtually any place where ordinary water is available. Thus, the present invention can be used in virtually all fields requiring supply of hydrogen. Moreover, the magnesium composite can be formed quite easily in any desired shape to suit the purpose and use.
This invention will now be described with reference to working examples and comparative examples which use iron, nickel and chromium as typical metals for the formation of the magnesium composite. The inventor has confirmed that use of manganese and zinc brings about similarly desirable effects.
Example 1:
In a mortar, 8 g of magnesium 50 mesh and 4 g of iron 200 mesh were stirred 80 times with a pestle to produce a mixture consisting of magnesium particles having iron powder attached thereto and free iron powder. When this mixture was sieved to separate therefrom the free iron powder which had escaped being attached to the magnesium particles, there was obtained 8.012 g of magnesium particles having 0.15% by weight of iron powder attached to the surface thereof. The magnesium particles were combined with 10 g of NaC~ and introduced into 1500 cc of city water. Consequently, a total of 3600 cc (N.T.P.) of hydrogen was generated within 20 minutes. The hydrogen thus yenerated was found to have purity of 99.999%.
Comparative Example l:
Exactly the same amounts of magnesium particles and iron powder as used in Example l were placed in a container and homogeneously blended by gently swirling the contents. The resulting mixture was allowed to react with water under entirely the same conditions as in Example l. In this case, a total of 40 cc (N.T.P.) of hydrogen was generated within 20 mir.utes.
It is seen from Example 1 and Comparative Example 1 that, when the admixture was effected in the absence of mechani-cal pressure, the quantity of hydrogen generated was only one-ninetieth of the quantity obtained when the admixture was made in the presence of mechanical pressure. In Comparative Example 1, 4 g of iron powder i.e., 50% by weight based on the amount of magnesium was used for the generation ~f hydrogen. The com-parison shows that the magnesium composite according to this invention had a pronounced effect.
Example 2:
A ribbon of magnesium measuring 0.3 cm in width, 0.02 cm in thickness and 12.96 cm in length and weighing 0.14439 g was placed in a mortar containing 5 g of iron and stirred 50 times with a pestle. The ribbon of magnesium was then weighed. The weighing showed that 0.000119 g of iron powder had been attached to the ribbon surface. Calculation shows that the amount of iron powder thus attached was about 0.08% by weight.
When this composite ribbon of magnesium was thrown in 400 cc of water containing lO g of NaCQ, there ensued vigorous generation of hydrogen which lasted for 50 minutes. The rate of hydrogen generation was 4.35 cc/min (N~T.P.~. The purity of the hydrogen was found to be 99.999%.
~og8343 Comparative Example 2:
Under exactly the same conditions as in Example 2, a mixture of 0.14439 g of magnesium particles 50 mesh with 0.00011 g of iron powder (200 mesh) was processed and then tested. In this case, the quantity of hydrogen generated in 30 minutes was 0.7 cc (N.T.P.).
It is seen from Example 2 and Comparative Example 2 that the composite ribbon of magnesium according to this inven-tion was more effective.
Similar results were obtained when the procedure was repeated by using Na2SO4 or K2SO4 in place of NaCQ.
Example 3:
A ribbon of magnesium measuring 3.1 mm in width, 0.2 mm in thickness and 474 mm in length, weighing 0.5321 g and having a purity of 99.9% was placed on an iron plate having scattered thereon 50 g of iron powder having a particle size not larger than 300 mesh. By rolling a cylinder of steel plate 3.5 cm in diameter and 30 cm in length so as to press the ribbon lightly, the iron powder adhered to the ribbon of magnesium. The amount of iron powder thus attached was 0.0051 g. When the ribbon of magnesium having the iron powder attached thereto was immersed in 1000 cc of sea water, generation of hydrogen followed. The relation between the cumulative volume of hydrogen generated and the length of time of the ribbon's immersion in the sea water is shown below:
Time (minute) 5 10 15 20 25 30 Cumulative volume 70 135 185 232 272 304 (cc) of hydrogen This rate of hydrogen generation is unusually large as compared with that obtainable with the known method.
~0~8343 Example 4:
A ribbon of magnesium measuring 3 mm in width, 0.2 mm in thickness and 475 mm in length, weighing 0.5339 g and having a purity of 99~ was placed in ferric oxide powder. The ribbon of magnesium was moved around in the powder by virtue of strong pressure applied thereto with a cylinder of steel plate 3.5 cm in diameter and 30 cm in length. Consequently, 0.0002 g of the ferric oxide powder adhered to the ribbon of magnesium. When the ribbon of magnesium having the ferric oxide powder attached thereto was immersed in 1000 cc of sea water, hydrogen was gen-erated as follows:
Length of time (min) 10 20 30 40 50 60 70 80 Cumulative volume 85 165 228 298 357 404 438 465 This rate of hydrogen generation is unusually large as compared with that obtainable with the known method.
Example 5:
A ribbon of magnesium measuring 0.3 cm in width, 0.02 cm in thickness and 13.1 cm in length and weighing 0.14705 g and 10 g of nickel powder having a maximum particle size of 200 mesh were placed in a mortar and were stirred by revolving a pestle about 60 times inside themortar to effect pressurized friction thereof. Consequently, 0.00092 g of nickel powder was deposited onto the ribbon of magnesium. When the magnesium composite thus obtained was introduced into 400 cc of sea water, hydrogen was generated vigourously. This generation of hydrogen lasted for 45 minutes. The rate of hydrogen generation was 4.37 cc~minute (N.T.P.).
Example 6:
A ribbon of magnesium measuring 0.3 cm in width, 0.0~ cm ~. , lOg8343 in thickness and 12.56 cm in length and weighing 0~13285 g and 10 g of chromium powder having a maximum particle size of 200 mesh were placed on an iron plate. A cylindrical iron bar measuring 3.5 cm in diameter and 30 cm in length was rolled on its side over the iron plate to move the ribbon of magnesium relative to the metal powder and consequently effect pressurized fricton. Thus there was obtained a magnesium composite having 0.00121 g of chromium powder deposited thereon. When this composite was placed in 400 cc of tap water having 10 g of NaCQ
dissolved in advance therein, hydrogen was generated vigorously.
This hydrogen generation lasted for 70 minutes. The average rate of hydrogen generation was 3.85 cc/minute (N.T.P.).
In recent years, hydrogen has come to attract in-creasing attention as a prospective fuel. Hydrogen possesses excellent properties as a fuel in that the combustion thereof does not entail generation of air-polluting substances such as, for example, sulfur oxides or nitrogen oxides. If a method is established which permits easy and convenient generation of hydrogen, then the hydrogen obtained by this method can be used as an energy source in various fields, ranging from small-scale household uses to heavy-duty industrial uses involving the operation of automobiles, marine vessels, etc. For the manu-facture of hydrogen, various methods have been developed and put to commercial uses. A method which produces hydrogen by the electrolysis of water, methods which produce hydrogen in the form of a by-product in the modification of petroleum and coal gases and in the electrolysis of common salt and other similar methods are examples. However, these methods invariably require large-scale manufacturing apparatuses.
It is universally known that when magnesium is allowed to react with water, the reaction proceeds as indicated by the following equation to generate hydrogen.
Mg + 2H2O -~ Mg(OH)2 + H2 In the above reaction, if magnesium prepared in the form of a mixture with iron, nickel, copper, etc. or in the form of an alloy with any of the metals described above is allowed to react with water, then the forward reaction proceeds at an accelerated rate. This is known to the art in view of, e.g., British Patent . , q~
10"8343 No. 579,246 and U.S.P. No, 2,623,812.
An object of the invention is to provide a method for producing magnesium composites useful for liberating hydrogen from water.
According to one embodiment of the invention there is provided a method for the manufacture of a magnesium composite capable of generating hydrogen upon contact with water contain-ing at least 1% by weight of a salt selected from the group consisting of NaCQ, KCQ, Na2SO4, K2SO4 and mixtures thereof;
the method comprising placing magnesium and a metal powder selected from the group consisting of chromium, iron, manganese, nickel, zinc and oxides thereof in a container; applying mechanical force to the magnesium and metal powder mixture whereby 0.01~ to 30~ by weight of the metal powder is embedded in the magnesium; and removing any excess of the metal powder not embedded in the magnesium.
Firstly, a method for manufacturing a magnesium compo-site having deposited on its surface at least one member selected from the group consisting of iron, nickel, zinc, chromium and manganese and prepared in the form of a metal powder or an oxidized metal powder is described.
The form in which magnesium is used is not specifically fixed. It can be used in the form of powder, granules, plates, foils, etc. To meet requirements arising from practical con-siderations, it may be used in the form of helically shaped plates or foils or of cylindrically shaped rods, for example.
From the practical point of view, use of magnesium in the form of plates having a thickness of not more than 1 mm results in the formation of a magnesium composite which generates hydrogen at an increased rate.
` ~V~8343 When magnesium is used in the form of powder or granules, it is only natural that the particle diameter thereof should be greater than that of the pure metal powder or oxidized metal powder which is bein~ deposited thereon.
The metal powder or oxidized metal powder to be de-posited on the magnesium desirably has a particle size not coarser than 200 mesh as measured by the Tyler's standard sieves.
It is further desirable to include finer particles of the order of 10 microns, for example.
Adhesion of such metal powders or oxidized metal powders to the surface of the magnesium is accomplished by pressurized friction. This adhesion by means of pressurized friction con-stitutes one of the salient features of the present invention.
The term "pressurized friction" refers to an action whereby the magnesium and the powder desired to be deposited thereon are moved relative to each other while the two substances are held pressed against each other. For example, the metal powder or oxidized metal powder can be attached to the surface of the magnesium, used in the form of granules, foils or plates, by placing them both in a suitable container such as, for example, a mortar and stirring the contents 30 to 100 turns with a pestle.
In this case, the amount of the metal powder or oxidized metal powder to be attached to the surface of the magnesium is required to fall in the range of from 0.01 to 30% by weiyht based on the weight of magnesium. The required adhesion can be accomplished by placing in the mortar the metal powder or oxidized metal pow-der in an amount roughly 5 to 100 times in excess as is desired to be attached to the magnesium and rotating the pestle in the mortar as described above. When the magnesium used in this case is in the form of foils or plates, the metal powder or oxidized ~(3198343 metal powder which has escaped adhesion to magnesium can be recovered with extreme ease. When the magnesium is in the form of granules, the removal of the metal powder or oxidized metal powder can eas~ly be effected by any known technique for powder separation, such as, for example, simple sifting or centrifu-gation. The powder which has escaped adhesion and then is recovered can be used in its unmodified form for the subsequent cycle of magnesium adhesion.
The composite of magnesium and metal or metal oxide can further be manufactured by placing the magnesium plate or foil in the metal powder or metal oxide powder and moving the plate or foil while applying pressure thereto.
The pressurized friction between the magnesium and the powder can also be effected by placing the magnesium in the form of foils or plates in a mass of the metal powder or oxidized metal powder and beating the mass mildly, such as with a hammer, for example, to afford the desired composite of magnesium and metal powder or oxidized metal powder.
The aforementioned composite can otherwise be manu-factured by a technique similar to the process employed for sur-face polishing.
Magnesium is a metal which abounds in malleability and exhibits a lower degree of hardness at normal room temperature than iron, zinc, chromium and manganese. Thus, any of the treat-ments described above permits the metal powder or oxidized metal powder to be attached to the magnesium, giving rise to the desired magnesium composite. The amount of the metal powder or oxidized metal powder to be deposited on the surface of the magnesium can be adjusted e.g. by suitably fixing the number of revolu~ions of the pestle and the amount of powder placed in the lOg8343 container or regulating the conditions of pressurized friction.
A microscopic observation of the magnesium composite reveals that granules or particles of either the metal powder or the oxidized metal powder are inserted into the recesses formed on the surface of the magnesium matrix in conformity to the shape of the granules or particles. The magnesium powder requires careful handling so as to preclude the possibility of ignition.
When magnesium of a particle size coarser than lO0 mesh is subjected to pressurized friction, however, no particular care is required in its handling, except it is best treated in a dry state.
The amount of the metal powder or oxidized metal powder to be incorporated in the composite is selected with respect to the purpose for which the produced hydrogen is used, with due consideration being paid to the fact that this amount is correlated to some extent with the rate at which hydrogen gen-eration proceeds. It has been confirmed that the magnesium com-posite is still effective when the amount of the metal powder or oxidized metal powder incorporated therein is in the range of 0.01 - 2~ by weight based on the weight of magnesium. The com-posite fails to produce the desired effect when the amount of the metal powder or oxidized metal powder is lower than 0.01~
by weight and no increase of effect is gained when the amount exceeds 30~ by weight. The fact that the magnesium composite is effective even when the amount of the metal powder or oxidized metal powder falls in the range of 0.01% - Q.1%, for example, by weight based on the weight of magnesium as descrihed above has been neither disclosed nor suggested anywhere in the literature published to date.
When the magnesium aomposite is introduced into water ~.
10~8343 containing therein at least one member selected from the group consisting of NaC~, KC~, Na2SO4 and K2SO4, hydrogen is generated.
As is demonstrated in the preferred embodiments and comparative examples given herein below, the rate at which the generation of hydrogen proceeds in this system is extremely high, as compared with, a system in which a mixture of magnesium and a metal manu-factured by the conventional method is introduced in water. If impurities are present in the magnesium and in the iron, nickel, zinc, chromium or manganese to be used in the manufacture of the composite, they have no adverse effect upon the amount of hydro-gen generated. River water, town water, sea water or any other ordinary water can be used for the generation of hydrogen through contact with the magnesium composite. In the case of sea water, otherwise required addition of metal salts can be dispensed with, for it contains NaCQ and other salts.
In the case of ordinary fresh water, the amount of NaCQ, KCQ, Na2SO4 or K2SO4 to be incorporated is required to be not less than 1% by weight.
A possible explanation for the enhanced generation of hydrogen by the magnesium composite is as follows: The metal powder or oxidized metal powder is uniformly attached in fine particles to the entire surface of the magnesium metal. This means that the area of contact between the powder particles and the magnesium metal is extremely large. When this composite is brought into contact with water to generate hydrogen, the pro-portion of the surface of the magnesium covered by Mg(OH)2 is small, so that no measurable decline of the activity of magnesium is observed. This means that the generation of hydrogen con-tinues.
The hydrogen which is generated by the method of this invention has been assayed by gas chromatography to have a purity "~ 10~ 3 exceeding 99.999%. Further, Mg(OH)2 produced in the reaction can easily be converted into magnesium, which can be put to cyclic use in the formation of magnesium composite.
As is clear from the foregoing description, the method of this invention enables any ordinary water to generate hydro-gen of high purity in large volumes at a high rate, indicating that the present invention enjoys high practical value. When the magnesium composite is manufactured in advance, hydrogen can be obtained at virtually any place where ordinary water is available. Thus, the present invention can be used in virtually all fields requiring supply of hydrogen. Moreover, the magnesium composite can be formed quite easily in any desired shape to suit the purpose and use.
This invention will now be described with reference to working examples and comparative examples which use iron, nickel and chromium as typical metals for the formation of the magnesium composite. The inventor has confirmed that use of manganese and zinc brings about similarly desirable effects.
Example 1:
In a mortar, 8 g of magnesium 50 mesh and 4 g of iron 200 mesh were stirred 80 times with a pestle to produce a mixture consisting of magnesium particles having iron powder attached thereto and free iron powder. When this mixture was sieved to separate therefrom the free iron powder which had escaped being attached to the magnesium particles, there was obtained 8.012 g of magnesium particles having 0.15% by weight of iron powder attached to the surface thereof. The magnesium particles were combined with 10 g of NaC~ and introduced into 1500 cc of city water. Consequently, a total of 3600 cc (N.T.P.) of hydrogen was generated within 20 minutes. The hydrogen thus yenerated was found to have purity of 99.999%.
Comparative Example l:
Exactly the same amounts of magnesium particles and iron powder as used in Example l were placed in a container and homogeneously blended by gently swirling the contents. The resulting mixture was allowed to react with water under entirely the same conditions as in Example l. In this case, a total of 40 cc (N.T.P.) of hydrogen was generated within 20 mir.utes.
It is seen from Example 1 and Comparative Example 1 that, when the admixture was effected in the absence of mechani-cal pressure, the quantity of hydrogen generated was only one-ninetieth of the quantity obtained when the admixture was made in the presence of mechanical pressure. In Comparative Example 1, 4 g of iron powder i.e., 50% by weight based on the amount of magnesium was used for the generation ~f hydrogen. The com-parison shows that the magnesium composite according to this invention had a pronounced effect.
Example 2:
A ribbon of magnesium measuring 0.3 cm in width, 0.02 cm in thickness and 12.96 cm in length and weighing 0.14439 g was placed in a mortar containing 5 g of iron and stirred 50 times with a pestle. The ribbon of magnesium was then weighed. The weighing showed that 0.000119 g of iron powder had been attached to the ribbon surface. Calculation shows that the amount of iron powder thus attached was about 0.08% by weight.
When this composite ribbon of magnesium was thrown in 400 cc of water containing lO g of NaCQ, there ensued vigorous generation of hydrogen which lasted for 50 minutes. The rate of hydrogen generation was 4.35 cc/min (N~T.P.~. The purity of the hydrogen was found to be 99.999%.
~og8343 Comparative Example 2:
Under exactly the same conditions as in Example 2, a mixture of 0.14439 g of magnesium particles 50 mesh with 0.00011 g of iron powder (200 mesh) was processed and then tested. In this case, the quantity of hydrogen generated in 30 minutes was 0.7 cc (N.T.P.).
It is seen from Example 2 and Comparative Example 2 that the composite ribbon of magnesium according to this inven-tion was more effective.
Similar results were obtained when the procedure was repeated by using Na2SO4 or K2SO4 in place of NaCQ.
Example 3:
A ribbon of magnesium measuring 3.1 mm in width, 0.2 mm in thickness and 474 mm in length, weighing 0.5321 g and having a purity of 99.9% was placed on an iron plate having scattered thereon 50 g of iron powder having a particle size not larger than 300 mesh. By rolling a cylinder of steel plate 3.5 cm in diameter and 30 cm in length so as to press the ribbon lightly, the iron powder adhered to the ribbon of magnesium. The amount of iron powder thus attached was 0.0051 g. When the ribbon of magnesium having the iron powder attached thereto was immersed in 1000 cc of sea water, generation of hydrogen followed. The relation between the cumulative volume of hydrogen generated and the length of time of the ribbon's immersion in the sea water is shown below:
Time (minute) 5 10 15 20 25 30 Cumulative volume 70 135 185 232 272 304 (cc) of hydrogen This rate of hydrogen generation is unusually large as compared with that obtainable with the known method.
~0~8343 Example 4:
A ribbon of magnesium measuring 3 mm in width, 0.2 mm in thickness and 475 mm in length, weighing 0.5339 g and having a purity of 99~ was placed in ferric oxide powder. The ribbon of magnesium was moved around in the powder by virtue of strong pressure applied thereto with a cylinder of steel plate 3.5 cm in diameter and 30 cm in length. Consequently, 0.0002 g of the ferric oxide powder adhered to the ribbon of magnesium. When the ribbon of magnesium having the ferric oxide powder attached thereto was immersed in 1000 cc of sea water, hydrogen was gen-erated as follows:
Length of time (min) 10 20 30 40 50 60 70 80 Cumulative volume 85 165 228 298 357 404 438 465 This rate of hydrogen generation is unusually large as compared with that obtainable with the known method.
Example 5:
A ribbon of magnesium measuring 0.3 cm in width, 0.02 cm in thickness and 13.1 cm in length and weighing 0.14705 g and 10 g of nickel powder having a maximum particle size of 200 mesh were placed in a mortar and were stirred by revolving a pestle about 60 times inside themortar to effect pressurized friction thereof. Consequently, 0.00092 g of nickel powder was deposited onto the ribbon of magnesium. When the magnesium composite thus obtained was introduced into 400 cc of sea water, hydrogen was generated vigourously. This generation of hydrogen lasted for 45 minutes. The rate of hydrogen generation was 4.37 cc~minute (N.T.P.).
Example 6:
A ribbon of magnesium measuring 0.3 cm in width, 0.0~ cm ~. , lOg8343 in thickness and 12.56 cm in length and weighing 0~13285 g and 10 g of chromium powder having a maximum particle size of 200 mesh were placed on an iron plate. A cylindrical iron bar measuring 3.5 cm in diameter and 30 cm in length was rolled on its side over the iron plate to move the ribbon of magnesium relative to the metal powder and consequently effect pressurized fricton. Thus there was obtained a magnesium composite having 0.00121 g of chromium powder deposited thereon. When this composite was placed in 400 cc of tap water having 10 g of NaCQ
dissolved in advance therein, hydrogen was generated vigorously.
This hydrogen generation lasted for 70 minutes. The average rate of hydrogen generation was 3.85 cc/minute (N.T.P.).
Claims (12)
1. A method for the manufacture of a magnesium compo-site capable of generating hydrogen upon contact with water containing at least 1% by weight of a salt selected from the group consisting of:
NaC?, KC?, Na2SO4, K2SO4 and mixtures thereof;
said method comprising:
placing magnesium and a metal powder selected from the group consisting of chromium, iron, manganese, nickel, zinc and oxides thereof in a container;
applying mechanical force to said magnesium and metal powder mixture whereby 0.01% to 30% by weight of said metal powder is embedded in said magnesium; and removing any excess of said metal powder not embedded in said magnesium.
NaC?, KC?, Na2SO4, K2SO4 and mixtures thereof;
said method comprising:
placing magnesium and a metal powder selected from the group consisting of chromium, iron, manganese, nickel, zinc and oxides thereof in a container;
applying mechanical force to said magnesium and metal powder mixture whereby 0.01% to 30% by weight of said metal powder is embedded in said magnesium; and removing any excess of said metal powder not embedded in said magnesium.
2. The method of claim 1, wherein said magnesium is in a form selected from the group consisting of:
powders, granules, plates, foils and rods.
powders, granules, plates, foils and rods.
3. The method of claim 1 or 2, wherein said metal pow-der has a particle size not larger than 200 mesh.
4. The method of claim 1 or 2, wherein said metal pow-der includes particles of the order of 10 microns.
5. The method of claim 2, wherein said magnesium pow-der or granule has a particle size larger than said metal powder.
6. The method of claim 1 or 2, wherein said metal powder is embedded in said magnesium by stirring said metal powder and magnesium together under pressure.
7. The method of claim 2, wherein said metal powder is embedded in said magnesium by moving said magnesium plate, foil or rod in said metal powder under pressure.
8. The method of claim 1 or 2, wherein said metal powder is embedded in said magnesium by mildly beating a mixture of said metal powder and said magnesium.
9. The method of claim 1 or 2, wherein said metal powder is embedded in said magnesium by a surface polishing process.
10. The method of claim 1 or 2, wherein 0.01% to 2% by weight of said metal powder is embedded in said magnesium.
11. The method of claim 1 or 2, wherein 0.01% to 0.1 by weight of said metal powder is embedded in said magnesium.
12. A magnesium composite when produced by the method of claim 1, 2 or 5.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA222,198A CA1098343A (en) | 1975-03-17 | 1975-03-17 | Method for manufacture of magnesium composite and method for manufacture of hydrogen by said composite |
| CA330,267A CA1074532A (en) | 1975-03-17 | 1979-06-21 | Method for manufacture of magnesium composite and method for manufacture of hydrogen by said composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA222,198A CA1098343A (en) | 1975-03-17 | 1975-03-17 | Method for manufacture of magnesium composite and method for manufacture of hydrogen by said composite |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1098343A true CA1098343A (en) | 1981-03-31 |
Family
ID=4102539
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA222,198A Expired CA1098343A (en) | 1975-03-17 | 1975-03-17 | Method for manufacture of magnesium composite and method for manufacture of hydrogen by said composite |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1098343A (en) |
-
1975
- 1975-03-17 CA CA222,198A patent/CA1098343A/en not_active Expired
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