AU463596B2

AU463596B2 - Hydrogen gas manufacturing process

Info

Publication number: AU463596B2
Application number: AU41103/72A
Authority: AU
Inventors: Suzuki Masahiro
Original assignee: Individual
Current assignee: Individual
Priority date: 1971-04-16
Filing date: 1972-04-13
Publication date: 1975-07-31
Also published as: GB1378820A; FR2133825B1; AU4110372A; IT966890B; CA978332A; FR2133825A1; DE2218470A1; JPS4849694A

Description

41.103/7 This invention relates to the development of a low

cost manufacturing process of hydrogen gas used in chemical

reactions or as a fuel.

According to the present invention there is provided

a process for the preparation of hydrogen gas by the

reaction of magnesium with water including the steps of

vigorously stirring magnesium and catalyst in particle or

powder form and adding water to the resultant mixture in

the presence of potassium chloride or sodium chloride to

accelerate the reaction of magnesium with water.

The vigorous stirring of magnesium and catalyst allows

catalyst to become embedded in the magnesium and the

resultant mixture permits vigorous generation of hydrogen.

The catalyst may include a metal or a non-metal which

is silicon, aluminium, iron, zinc, tin, nickel, boron, red

phosphorus, chromium, copper, manganese, carbon, calcium,

titanium, zirconium, or one or more compounds of the above-

mentioned metals and non-metals. Many of such materials are

available nearly anywhere on earth, especially through sea or waste water, or through waste powder/solutions discarded from

metal works or smelting plants, or through industrially

polluted mud accumulated in rivers or on the bottom of the

sea.

This process yields readily large quantities of

highly pure hydrogen gas which, having a very high combustion

46.3,5 96

41,103 72 as a fuel for temperature of about 20000C, can be used ships or in homes. power generation in factories, or on and moreover the The manufacturing process is simple, and used materials serving as catalysts are regenerated cost is low. repeatedly and so the manufacturing by this Furthermore, the hydrogen gas provided components either invention does not produce polluting and a great during its manufacture or during combustion, earth can be used as number of materials available on the obtained, so that a catalysts whenever magnesium can be produced anywhere pollution-free source of energy can be

4 6 3.5 96

41,10o3/

at any time.

Since the waste solutions of metals or of chlorides which

are the source of public nuisance are employed as excellent raw

materials in this hydrogen gas manufacturing process, it contri-

butes also to the solution of the pollution problem.

So far, it is well known that hydrogen gas is produced

by the addition of water to magnesium, the amount, however, of hydrogen gas produced is extremely small in this case. It is also very small even with the use of hot water, and cannot be obtained sufficiently for practical applications.

Considering the above-mentioned fact, much research was carried out over many years in the development of this invention by which the manufacture of large quantities of highly pure

hydrogen gas, in a short time, has been made successful. Accord- ing to this invention, a metal or a non-metal such as silicon,

aluminium, iron, zinc, tin, nickel, boron, phosphorus, copper,

manganese, icarbon, calcium, titanium, zirconium, or one or more compounds of the above-mentioned metals and non-metals are added

to magnesium, and water is added to the resultant mixture in the presence of potassium chloride or sodium chloride the catalytic

action of the above-mentioned elements or compounds is used to

accelerate the formation of magnesium hydroxide from the reaction

of magnesium with water. Namely, the above-mentioned elements or compounds act as catalysts in the following reaction: Mg 2H Mg(OH) 2 H 2 producing quite readily large quantities of hydrog

gas.

When elements or compounds of good quality are

463,5 96

411 0.3/7M employed, hydrogen gas is formed and evolves vigorously

as if the mixture is boiling. It is believed that this About 930 Bm-4 energy can be used for power generation. gram of magnesium although of hydrogen gas are obtained per to the nature of the some difference exists according obtained with catalysts catalysts, and highest yields are lowest ones with silicon such as chlorides or metals while and carbon. hydrogen is pro- If iron is used as the catalyst, In this case, how- duced when iron hydroxide is formed. 4 catalysts, it- !0 ever, as well as in the case of other or potassium chloride bettcr to adr' either sodium chloride effectively the to the catalyst in opdap-to increase~kmore according to the ex- formation of hydrogen gas. Namely, the reaction occurs perimental. results of this invention, above-mentioned compounds vigorously when two kinds of the epecially7 sodium are employed, one being a chloride, or. ametal ebtlrd and chloride, or potassium chloride, The evolution of hy- the other iron, chromium or copper. By comparing the amount drogen gas is then very active. formed by 2g of hydrogen gas-obtained with the mixture and 3g of iron, with magnesium, 259 of sodium chloride, by 2g of magnesium that obtained with the mixture formed and 3g of iron, it was found that, with the same reaction not reach one third of conditions, the latter amount did a chloride increases en- the former, thus indicating that formed. ormously the amount of hydrogen with As for the compounding ratio of magnesium elements, when more other elements or compounds of these elements or compounds are than two of the above-mentioned FU 463.5-96

41,103/72

used, the amount of magnesium in the mixture is 10 50%, that of

the sodium or potassium chloride 5 70% and that of the catalyst

40%. In this case, if the amount of water added is 8 times

the amount of the above mixture, hydrogen gas is formed at a satisfactory rate.

If magnesium in lump form is used, it is introduced into

water first, before adding the catalyst or the chloride.

In this case, the temperature of the solution is increasE

by the heat of the hydrogen gas formation reaction, it is, howeve

still possible to promote the formation of hydrogen gas further I

heating the solution to a safe temperature i.e. a temperature at

which hydrogen is not so vigorously generated as to cause ad-

mixture of oxygen and the generated hydrogen.

If the hydrogen gas provided by this invention is analyzE

by gas chromatography, it is observed that even the gas obtained

from the use of ordinary water or sea water contains more than

of hydrogen. Other components are oxygen and nitrogen

coming from the amount of air dissolved in the water employed,

but it is found that the amount of impurity gas present does not

reach even 0.1 ppm. Therefore, hydrogen gas having a purity

superior to 99.9999% can be readily obtained by removing the

oxygen and nitrogen of the air component in the gas.

As for the residual reaction products remaining after th4

evolution of hydrogen, in the case of water and sea water, they

are separated, regenerated chemically and used repeatedly again.

Magnesium hydroxide is transformed into magnesium

463.5 96

41.103/72 chloride, then magnesium is regenerated by electrolysis chlorides are used or by the Pidgeion process. Iron and manufac- again. The processes involved in the continuous and in ture of hydrogen, in the steam power generation, reaction the regeneration of magnesium from the residual at a plant or at a products can be carried out either

specially constructed regeneration plant. Thus it is possible in small plants or common by a source homes to replace the conventional power source line from of energy that does not require any transmission

the exterior, by the use of a small generator. of this Hereinafter, examples of some embodiments

invention will be described.

Example 1:

of magnesium, 10g of sodium chloride, 7g of At zinc and 7g of magnesium chloride were prepared.

first, magnesium and zinc were well mixed by stirring,

then water of 8 times the amount of the above-mentioned When magnesium chlor- compounds, namely 270 2 was added. gas ide and sodium chloride were introduced, hydrogen in 7 evolved vigorously and amounted to about 2,100 m

minutes. This hydrogen gas did not contain even 0.1 ppm

of impurity gas, and had a heat capacity of about 3,000 flame when Kilocalories. It burned with a blue-white suitable as fuel supplied to a burner, and so was found small plant use. for small generators destined to home or

46 3,5 9 6

41,103/72 Example -3:

8g of magnesium, 8g of iron, and 10g of cupric ch-

loride were prepared. About 9 times the amount of these

substances of sea water was taken and cupric chloride was

added to the sea water. When the well-stirred mixture

of magnesium and iron powder was added to the solution,

hydrogen gas evolved vigorously and amounted to about

2,100-am in 12 minutes.

The purity, the heat capacity and the use of

this hydrogen gas were almost identical to those of the

gas obtained in Example 1.

Example 4:

1,000g of magnesium, 800g of iron, 500g of ferrous

chloride, 2,800g of sodium chloride and 25 liters of water

were used. Iron powder and magnesium were well mixed in

water by stirring, then sodium chloride was added while

stirring was continued. Ferrous chloride was introduced

thereafter, producing large quantities of gas which evolved

very vigorously, and even at a constant rate of 208

per second during the normal period of the reaction.

According to this experiment, the hydrogen gas

obtained did not contain even 0.1 ppm of impurity gas,

and has a heat capacity of about 3,000 Kilocalories and

was therefore found suitable as fuel for power generation

at small plants or homes.

46 3,5 96

41,103/72

agnsiull,8gof zinc and log of ferrous l~gof

chloride were prepared. About 8 times the amount of these

substances of seawater was taken, and to this, ferrous the well-stirred mixture chloride was first added. Then into the solution. of magnesium and zinc was intr~oduced in 20 minutes. -,e About 1,500H* of gasi'ere obtained sodium chloride were Exan~l.:(M~agnesium chloride, and used) and of magnesium, 200g of sodium chloride introduced into a re- of magnesium chloride powder were When water was added action flask and stirred vigorously. vigorously, giving to this mixture, hydrogen gas evolved mixture. about 300 a*g of gas per gram of added to a On the other hand, when water was and lOg of magnesium stirred mixture of 20g of magnesium over a long period. chloride, the gas evolved smoothly be used with mag- In this embodiment, brine could and the hydrogen gas nesium.!f chloride and sodium chloride, of Example 1. obtained was identical to that

4 63.5 9 6

41,103 /72 Example 19: (Ferrous chloride, ferric chloride and sodium

chloride were used)

250g of sodium chloride, 20g of magnesium and

of ferrous chloride were mixed together; to this mixture,

water was added and the gas evolved was collected. The

evolution of gas progressed well and gave a large quant-

ity of gas in 3 hours. More than 300-t of gas were ob-

tained per gram of the reacting mixture. During the

reaction, water had to be added gradually because the effect ,reaction flask.was in danger of breaking under the

of the heat of the reaction. When ferric chloride was used instead of ferrous

the gas evolved more vigorously than in the chloride,

case of ferrous chloride. In this case ferrous chloride

and ferric chloride from the waste solutions discarded chlor- by smelting plants and from the slagand the sodium

ide from sea water were used.

I

Example (Red phosphorus and sea water)

The gas evolved after 10g of magnesium and 20g of water. The red phosphorus had been added to 250 4A of sea

evolution of gas was vigorous and abundant.

10 463.596

41,103/ 72

The examples B to 4 mentioned above show that

hydrogen gas of good quality can be obtained even in the

absence of magnesium chloride, if red phosphorus or nickel

chloride are used. It has been also shown that the con-

tent of sodium chloride in the compounded mixture is

appropriate and when the particles and the size of the

solid metal components (such as iron, zinc) are well chos-

en so that no light particles can be ejected out due to

the vigorous evolution of the gas, the hydrogen gas ob-

tained burns'with a remarkably transparent flame. In summary, this invention has the advantage that

it does not present the danger of producing a polluting

gas either during the manufacturing or during the com-

bustion processes and so is free from pollution problems.

Moreover, since the combustion produces water vapor at a

temperature of 2,0000C, there is no danger of drying out

the room where combustion is carried out. Extremely large

quantities of hydrogen gas can be obtained from a very

small amount of reactants. On the other hand, as the gas

manufacturing apparatus is very simple, it can be used

very easily, producing hydrogen which can be used whenever

necessary, and so is very useful. Moreover, since the

reactants can be regenerated and used repeatedly, hydrogen

gas can be produced at low cost, and so, can be used not

11 463,596

4 1,1 03 In small.plants or only as a fuel for power generation in industry homes but is also very useful for the chemical quantities and steam power generation which require large economic and tech- of hydrogen gas, and consequently, the

nical effects of this invention are very large.

12 463.596

Claims

41.103/72 THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS:

1. A process for the preparation of hydrogen gas by the

reaction of magnesium with water including the steps of or vigorously stirring magnesium and catalyst in particle in the powder form and adding water to the resultant mixture to presence of potassium chloride or sodium chloride

accelerate the reaction of magnesium with water.

2. A process according to Claim 1, wherein the catalyst

includes a metal or a non-metal which is silicon, aluminum,

iron, zinc, tin, nickel, boron, red phosphorus, chromium, or copper, manganese, carbon, calcium, titanium, zirconium,

one or mbre compounds of the above-mentioned metals or

non-metals.

3. A process according to Claim 1 substantially as

hereinbefore described with reference to the foregoing

examples.

4. Hydrogen gas whenever produced by a process as

claimed in-any one of the preceeding claims.

DATED THIS 22nd Day of MAY 1975

MASAHIRO SUZUKI

By its Patent Attorneys:

CLEMENT HACK CO. Fellows Institute of Patent Attorneys of Australia.

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