Process for the Production of Substances of Great Catalytic Activity.
Year: 1899

page_text: Date of Application, 11th July, 1899
Complete Specification Left, 26th Mar., 1900- Accepted, 16th June, 1900
PROVISIONAL SPECIFICATION.
Process for the Production of Substances of Great Catalytic Activity.
We, OSCAR EFRÉM, Proprietor of the Auer-Branch Establishment, of II.
Taborstrasse 10, Vienna, Austria, and JOSEF KLAUDY, Professor at the Imperial
and Royal Technological Trades Museum, of IX Vahringerstrasse 59, Vienna,
Austria do hereby declare the nature of this invention to be as follows:
-
In the case of all those substances' having catalytic power which have been
hitherto proposed for use and especially those which consist of a platinum wire
provided with an igniting pellet for effecting ignition of the mixtures of air and
gas in Bunsen burners the catalytic substance proper consists of platinum in a
fine state of subdivision embedded in a porous refractory base or foundation.
Except the substance produced according to Duke's process described in the
German Patent No. 91284, none of the products above referred to are capable
of effecting a rapid and certain ignition during a long period.
The reason of this lies in the fact that the state of fine subdivision of the
platinum which has hitherto been obtained in these products is by no means
sufficient to increase its catalytic action to such an extent as enables it to effect
certain and permanent ignition at ordinary temperature, that is to say to produce
the active increase of the reaction-velocity of a mixture of air and gas which
causes the igniting mass to become incandescent.
Now the present invention relates to a process for the manufacture of sub..
stances of great catalytic power which act certainly and permanently even in
the cold.
In the process described in the German Patent No. 91284 above referred to,
the reduction of the platinum salt employed is effected in the pores of the solid
bodies which serve to support it, by means of a current of hydro-carbons with
the exclusion of air, in the present process the main feature consists in the
physical preparation of the surface, and the reduction is effected by means of
other agents which may also be added to the substance to be reduced. In
carrying out this process, first the refractory base or material, meerschaum,
clay or the like, that supports the catalytic substance proper is subjected to a
preparatory treatment with strong acids, such as aqua-regia or sulphuric acid,
and a washing out carefully of the salts so formed, whereby any hygrocophic
salts that may be present and that would fuse in the heat of the Bunsen Hame and
the presence of which would considerably and injuriously affect the catalytic
action, are removed, or their formation is prevented. For the purpose of im-
parting the highest possible degree of porosity to the catalysing mass, there
are mixed with the basic substance, which is already a porous body of itself.
preferably compounds or substances such as ammonium or mercury salts, which
are volatile at a red heat, and there is also added to the mass the platinum or
platinum salt which acts as a catalyser. The mixture must be as intimate as
possible. For this purpose the ingredients of the mixture so far as they are

page_text: coluble, are mixed together in solution and are intimately mixed with the
insoluble constituents. There is now added to the mass thus produced which
consists substantially of the refractory basic substance, the cataliser, and, if
desired, also of a substance of the kind above mentioned which volatises at a
red-heat an organic substance that acts as a reducing agent, for example sugar;
and also if desired, finely subdivided carbon.
Furthermore there is added to the mass and this constitutes an essential
feature of the process of this invention a volatile acid, for example, hydrofluosilicic
acid or hydrofluoric acid which by its hardening and cementing action upon
silicates in the subsequent drying or heating of the mass, ensures its firm con-
sistence without destroying its porosity and also aids the reducing process by
driving out the acid that is contained in the platinum salt employed.
But the chief action of the added acid is that it etches or corrodes the small
particles of the mass and increases its active surface in such a manner as to
produce a considerable increase of its catalytic power. :
The doughy mass produced as above described is finally moulded, dried, and
heated to redness in the usual manner. It is advisable in so doing first to dry
the mass gently, and then to heat it to redness upon a sheet of platinum until
a sample shows that the substance has become active. We lay special stress
upon the fact that according to the present invention masses of catalytic power
weaker but sufficient for many purposes, may be obtained simply by adding
large quantities of solid bodies of the kind specified such as ammonium or mer-
cury salts, organic substances and the like which are volatile when heated to
the platinum salt which is distributed in the pulverised refractory basic sub-
stance. But the products so obtained have considerably less hardness, and per-
manence of action than the products obtained by addition of organic substances
such as sugar and the like, together with a volatile acid such as silicic-hydro-
flouric acid which etches the particles of the refractory basic material and
which acts at the same time with a hardening and binding effect. The reduction
with organic substances alone produces masses having a catalytic action, but
such masses have only a slow action that lasts for a short time whereas masses
of greater strength as also of the greatest possible permanency and rapidity of
the catalytic action, can only be produced by mixing refractory bodies, with a
platinum salt, and with an organic substance such as sugar, and with a volatile
acid, preferably silicic-hydro-fluoric acid which etches the refractory body, and
by diving and heating to redness, a mixture of this kind. The bodies so pro-
duced which have a catalytic action in the cold, may be employed not only for
igniting mixtures of combustible gas or vapour with air, but also in general
for effecting all those chemical processes in which it is desired to produce an
increased reaction velocity of the mutually interacting constituents of a mixture
of several substances especially of several gases, by means of a catalytic or con-
tact substance such as is the case, for example in the production of sulphuric
acid, anhydride, chlorine, formaldehyde, etc. With respect to the catalytic
power (which is considerably increased as compared to the activity of former
catalisers which become active only when heated) of the masses which are pro-
duced according to the present invention, and which act in the cold, these latter
of course are very much better than the first mentioned catalisers (platinised
asbestos and the like) in power, rapidity and permanence of action.
Dated this 11th day of July 1800.
ABEL & IMRAY,
Agents for the Applicants.

page_text: Process for the Production of Substances of Great Catalytic Activity.
We, OSCAR EFRÉM, Proprietor of the Auer-Branch Establishment, of II.
Taborstrasse 10, Vienna, Austria, and JOSEF KLAUDY, Professor at the Imperial
and Royal Technological Trades Museum, of IX. Vahringerstrasse 59, Vienna,
Austria, do hereby declare the nature of this invention and in what manner the
same is to be performed, to be particularly described and ascertained in and by
the following statement;-
10
In the case of all those substances having catalytic power which have been
hitherto proposed for use and especially those which consist of a platinum wire
provided with an igniting pellet for effecting ignition of the mixtures of air and
gas in Bunsen burners the catalytic substance proper consists of platinum in a
fine state of subdivision embedded in a porous refractory base or foundation.
+
Except the substance produced according to Duke's process described in the
German Patent No. 91284, none of the products above referred to are capable
of effecting a rapid and certain ignition during a long period.
The reason of this lies in the fact that the state of fine subdivision of the
platinum which has hitherto been obtained in these products is by no means
sufficient to increase its catalytic action to such an extent as enables it to effect
certain and permanent ignition at ordinary temperature, that is to say to produce
the active increase of the reaction velocity of a mixture of air and gas which
causes the igniting mass to become incandescent.
Now the present invention relates to a process for the manufacture of sub-
stances of great catalytic power which act certainly and permanently even in
the cold.
In the process described in the German Patent No. 91284 above referred to,
the reduction of the platinum salt employed effected in the pores of the solid
bodies which serve to support it, by means of a current of hydro-carbons with
the exclusion of air, in the present process the main feature consists in the
physical preparation of the surface, and the reduction is effected by means of
other agents which may also be added to the substance to be reduced. In
carrying out this process, first the refractory base or material, meerschaum,
clay or the like, that supports the catalytic substance proper is subjected to a
preparatory treatment with strong acids, such as aqua-regia or sulphuric acid,
and a washing out carefully of the salts so formed, whereby any hygroscopic
salts that may be present and that would fuse in the heat of the Bunsen flame and
the presence of which would considerably and injuriously affect the catalytic
action, are removed, or their formation is prevented. For the purpose of im-
parting the highest possible degree of porosity to the catalysing mass, there
are mixed with the basic substance, which is already a porous body of itself,
preferably compounds, or substances such as ammonium or mercury salts, which
are volatile at a red heat, and there is also added to the mass the platinum or
platinum salt which acts as a catalyser. The mixture must be as intimate as
possible. For this purpose the ingredients of the mixture so far as they are
soluble, are mixed together in solution and are intimately mixed with the
insoluble constituents. There is now added to the mass thus produced which
consists substantially of the refractory basic substance, the catalyser, and, if
desired, also of a substance of the kind above mentioned which volatises at a
red-heat an organic substance that acts as a reducing agent, for example sugar;
and also if desired, finely subdivided carbon.
Furthermore there is added to the mass and this constitutes an essential
feature of the process of this invention a volatile acid, for example, hydrofluosilicic

page_text: acid or nydronuoric acid which by its hardening and cementing action upo
silicates in the subsequent drying or heating of the mass, ensures its firm con
sistence without destroying its porisity and also aids the reducing process by
driving out the acid that is contained in the platinum salt employed.
But the chief action of the added acid is that it etches or corrodes the smal
particles of the mass and increases its active surface in such a manner as t
produce a considerable increase of its catalytic power.
Suitable proportions of the above named ingredients, when volatile substances
are not used, are as follows:-
2
1
parts by weight of meerschaum
29
chloride of platinum”
part
"
0-25 part »
0.5 "
وو
وو
39
33
» sugar
> hydrofluosilicic acid
These figures are given merely as an example for the composition may vary
within considerable limits.
The doughy mass produced as above described is finally moulded, dried, and
heated to redness in the usual manner. It is advisable in so doing first to dry
the mass gently, and then to heat it to redness upon a sheet of platinum unti
a sample shews that the substance has become active. We lay special stress
upon the fact that according to the present invention masses of catalytic power
weaker but sufficient for many purposes may be obtained simply by adding
large quantities of solid bodies of the kind specified such as ammonium or mer
cury salts, organic substances and the like which are volatile when heated to
the platinum salt which is distributed in the pulverised refractory basic sub-
stance. But the products so obtained have considerably less hardness, and per-
manence of action than the products obtained by addition of organic substances
such as sugar and the like, together with a volatile acid such as silicic-hydro-
Houric acid which etches the particles of the refractory basic material and
which acts at the same time with a hardening and binding effect. The reduction
with organic substances alone produces masses having a catalytic action, but
such masses have only a slow action that lasts for a short time whereas masses
of greater strength as also of the greatest possible permanency and rapidity of
the catalytic action, can only be produced by mixing refractory bodies, with a
platinum salt, and with an organic substance such as sugar, and with a volatile
acid, preferably silicic-hydro-fluoric acid which etches the refractory body, and
by drying and heating to redness, a mixture of this kind. The bodies so pro-
duced which have a catalytic action in the cold, may be employed not only for
igniting mixtures of combustible gas or vapour with air, but also in general
for effecting all those chemical processes in which it is desired to produce an
increased reaction velocity of the mutually interacting constituents of a mixture
of several substances especially of several gases, by means of a catalytic or con-
tact substance such as is the case, for example in the production of sulphuric
acid, anhydride, chlorine, formaldehyde, etc. With respect to the catalytic
power (which is considerably increased as compared to the activity of former
catalisers which become active only when heated) of the masses which are pro-
duced according to the present invention, and which act in the cold, these latter
of course are very much better than the first mentioned catalisers (platinised
asbestos and the like) in power, rapidity and permanence of action.
Having now particularly described and ascertained the nature of our said
invention and in what manner the same is to be performed, we declare that what
we claim is;-
1. The herein described process for the production of substances of great
catalytic power suitable for automatic ignition of combustible gases or vapours
mixed with air, or generally for producing increased reaction velocity in mixtures
of several bodies, as in the production of sulphuric acid, anhydride, chlorine,

page_text: formaldehyde etc. the said process consisting in treating a refractory body such
as meerschaum, clay or the like, with powerful acids such as aqua-regia, sulphuric
acid etc. for the purpose of removing or preventing formation of fusible or
hygroscopic salts, washing the same, mixing it with a platinum salt, and with an
organic substance such as sugar which serves for reducing and increasing the
porosity and with a volatile acid such as hydro-fluosilicic acid, or hydro fluoric
acid which etches the particles, accelerates the reduction and acts to harden and
bind the mass, the mixture thus produced being finally moulded, dried, and freed
by heating from all volatile constituents.
2. The modified process for producing substances of great catalytic power, but
of only a small degree of firmness, which process consists in producing great
porosity by addition of large quantities of volatile solid substances, such as
ammonium or mercury salts, or organic substances instead of the volatile acid.
3. The modified process which consists in adding for further increasing porosity
volatile solid substances of the kind referred to in Claim 2, to the mixture of
the refractory substance prepared as set forth, with a platinum salt, an organic
substance or carbon which acts as a reducing agent and increases the porosity,
and a volatile acid for etching the particles of the mass.
Dated this 26th day of March 1900.
ABEL & IMRAY,
Agents for the Applicants.