CA1065012A

CA1065012A - Substance and device for the absorption of catalyst poisoning gases out of the oxyhydrogen gas mixture

Info

Publication number: CA1065012A
Application number: CA177,417A
Authority: CA
Inventors: Norbert Lahme; Gunter Sassmannshausen
Original assignee: Accumulatorenwerk Hoppecke Carl Zoellner and Sohn KG
Current assignee: Accumulatorenwerk Hoppecke Carl Zoellner and Sohn KG
Priority date: 1972-08-02
Filing date: 1973-07-26
Publication date: 1979-10-23
Also published as: JPS548195B2; SE403009B; JPS4945887A; JPS53140293A; BE796947A; BR7303361D0; DD102863A5; IT987381B; SE7603614L; FR2195075A1; AT341025B; DE2237950C3; FR2195075B1; SE411277B; DE2237950B2; GB1437811A; DE2237950A1; CH607348A5; GB1450526A

Abstract

ABSTRACT
A substance, a method of producing it, and a device for using the substance in the absorption of catalyst poisoning gases out of the oxyhydro-gen gas mixture produced by lead-acid storage batteries, the substance effecting the oxidation of the unstable catalyst poisoning gases SbH3 and AsH3 to produce hydrolysis-resistant intermetallic compounds. As absorbing substances are usable heavy-metal manganites, heavy-metal oxides and catalytic agents. As a device, the absorbing substance is combined with an oxygen and hydrogen recombination unit.

Description

~0~0 i~
The present invention relates to absorbing substances for the removal of catalyst poisoning gases, viz. the compounds of hydrogen with the elements of Group V of the Periodic Table of Elements, particularly with arsenic (As) and antimony (Sb), from the oxyhydrogen mixtures which are generated during the operation of lead-acid storage batteries. The invention further relates to methods of producing such absorbing substances, and to the application of such substances in combination with a special catalyst 1ln;t taking the place of a closure plug on a lead-acid storage battery~ the purpose of this catalyst unit being to catalytically recombine the hydrogen and oxygen gases generated during the operation of the lead-acid storage battery to obtain water which is re-turned to the battery electrolyte.
It is known that considerable problems still exist in connection with the catalytic recombination of hydrogen and oxygen produced by lead-acid storage batteries~ as a result of the poisoning of the active catalyst material through the gaseous compounds of antimony-hydrogen and arsenic_hydrogen~
the so-called catalyst poisoning gases. These catalyst poison-ing gases are produced through the reaction of hydrogen with certain alloy components of the lead used in the manufacture ~.-.,.

.. .

, .

- 2 -:' , ~

, . : . .. . , , . . . . ~ .. ~ :
.: . :... . ~

1~6501Z
of lead-acid storage batteries. Primarily for reasons of improved quality, the lead alloys used for a wide variety of lead-acid storage cells fre-quently contain arsenic and antimony components. These alloy components combine with hydrogen to form the volatile, rather unstable, gaseous compounds of antimony hydride (SbH3) and arsenic hydride (AsH3), both being very effective as catalyst poisoning gases.
It has been variously attempted in the past to remove these so-called catalyst poisoning gases from the oxyhydrogen gas mixtures which are generated by electrical lead-acid storage batteries. For instance, one approach (Un;ted States Patent No. 3,102,059) suggests that the oxyhydrogen gases, before reaching the catalyst, are made to flow over a granular bed of alumina or of a mixture of alumina and lead-dioxide on an alumina carrier. It is further known (United States Patent No. 3,o38,954) to arrange a bed of lead-oxide on a carrier of aluminum-oxide powder in--~ side a battery plug in the flow path of the gases ahead of the catalytic material which recombines the hydrogen and oxygen generated by the battery.
A particular shortcoming of these prior art substances is their very short ; span of effectiveness which can be measured in days.
e present invention provides for a con'position for the elimination ofcatalyst poisoning gases, such as antimony hydride, arsenic hydride or other hydrides of Group V elements, from the oxyhydrogen gas mixture produced by lead-acid storage batteries which comprises at least one heavy metal oxygen compound, chosen from the oxides and man~anites, together with an inert carrier of an element chosen from the group comp~is-; ing iron, cobalt, nickel, tin, gallium, indium, thallium, molybdenum, tung-sten, and manganese.
Furthermore, the invention provides for a method of producing such a composition ccmprising the steps of:
preparing a solution of a salt of at least one element which, in its oxidic state, reacts with antimony-hydride or arsenic-hydride to produce antimonide or arsenide, respectively, or their oxides;

introducing into said solution, at an elevated temperature, a

- 3 -,: . . - . . . . . . . . . -, ~06S~Z
carrier materlal;
subse~uent to a period of interaction, introducing the mixture into a sodium carbonate solution, or its e~uivalent, for the precipitation of the carbonate; and washing, drying and calcinating the product.

,,-,~ .

: :
, .' ' ~ - 3a - :

.. ..
. -~06SOlZ
The invention also proYides for an improved device for the catalytic recombination of the oxyhydrogen gases generated during battery operation to water, the improvement being aimed at a substantially increased ~- duration of effectiveness of the catalyst.
me present invention suggests the use of heavy-metal manganites of one or several metals as absorbing substances preference being given to copper manganite. In place of this preferred group of compounds, it is also - 10 possible to use heavy-metal oxides for the removal of catalyst poisoning ~ases from the oxyhydrogen gas mixture generated by lead-acid storage batteries. For example, one may use the oxides of the elements iron, cobalt, nickel, tin, gallium, indium, and thallium, either separately or in combination, for a reaction with the antimony-hydride -and arsenic-hydride to obtain hydrolysis-resistant arsenides and antimonides in the form of inter-metallic - compounds These heavy-metal oxides may also be employed in combination with the aforementioned heavy-metal manganites to obtain a suitable absorbing subsbance.
The present invention further proposes that the ~. , .
absorbing substance includes oxidic compounds of elements, either of one or several types, or as an additive to the heavy-metal oxides, these oxidic compounds being reduced in the reaction with the antimony-hydride and arsenic-hydride, under oxidation of the latter. Especially suitable for this .
~'' , ~' '.
'.', ' .', ., . :

~-, - 4 _ ~"
~ '', .

. : . ,,. , , .,, , :... . ~ .. ... . .. . .

106SOlZ

purpose are: molybedenum trioxide (MoO3)~ tungsten trioxide (W03), and manganese dioxide (MnO2). Lastly, the invention suggests that the absorbing substance include oxides which are catalytically active as oxygen transfer agents, the oxides being used sèparately or incombinalt~on, or in addition to the heavy-metal oxides. Suitable examples of such oxygen transfer oxides are, in particular, ferric oxide (Fe203), vanadium pentoxide (V205), and chromium trioxide (Cr203).
These oxygen transfer agents cause an oxidation of the antimony-hydride and arsenic-hydride, when they come in contact with these gases.
,~, From the above, it can be seen that the various approaches to the basic solution proposed by the invention relate to different reaction mechanisms which are operative in the reaction between the oxidic absorbing substances, and the antimony_hydride and arsenic-hydrideO Thus~ the first group of oxidic compounds produces antimonides and arsenides, while the two other groups produce oxidic compounds of antimony and :
arsenic. In the first case, the oxidation of the catalyst `~ 20 poisoning gases is obtained through the action of an oxidation `~ agent~ uhereas the second case involves the catalytic transfer of oxygen. However, it should be understood that the foregoing explanation of the reaction mechanisms is based upon hypothe- ;
.
tical assumptions which were reached as a result of the research underlying the present inventionO The nventors, therefore, do not pretend that their hypotheses regarding the afore-mentioned reaction mechanisms are necessarily complete and correctO However, it has been found that each one of the .

,: , : : . : . ~ . .

~06S0~2 substances listed herein materially contributed to an improved de-poisoning of the oxyhydrogen gas mixture which is given off in lead-acid storage batteries during operation. Particularly good results have been obtained with heavy-metal manganites, especially with copper manganite.
The present invention also suggests ways of improving the effectiveness of the aforementioned absorbing substances still further, by arranging the substance on a carrier material, preferably an alumina gel. The carrier itself is preferably in granular form, the grain size for use in conjunction with conventional automobile batteries ranging between 0.1 mm and 1 mm, and preferably between 0.2 mm and 0.5 mm.
The present invention further suggests a method of producing the absorbing substances mentioned earlier, the method being characterized in that a solution of a salt of the element, or elements, is produced which, in its oxidic form, reacts with antimony-hydride and arsenic-hydride to create antimonide or arsenide, or their oxides, respectively, and that - the carrier material is introduced into this solution at an - 20 elevated temperature, that following a period of interaction, the mixture is introduced into a sodium carbonate solution or the liks in order to precipitate the carbonate, and that the substance is then washed, dried, and calcinated. Preferred operating conditions for the method of the invention are listed in the various specific examples given further below.
Lastly~ the invention suggests a novel device for the catalytic recombination of the hydrogen and oxygen gases produced during the operation of a lead-acid storage battery, ' .,:
.. . .
.' , ? ~ -6 : .

.:

10650~Z

to obtain water and to return the latter to the electrolyte of the batteryO mis device is characterized by a generally cylindrical housing which includes a stub connection on its outside and a porous body mounted against one housing face, adjacent to which is arranged a catalyst body, the latter being surrounded by a uniform layer of a granular absorbing substance contained inside a sleeve surrounding the catalyst body. me catalyst body is preferably in the shape of a rod and retained by its ends inside flanges in opposite end faces of the housing, whereby the flanges also serve to position the ~; gas_permeable sleeve concentrically in relation to the catalyst rod, the annular space between the sleeve and rod containing the absorbing substance.
me gas-permeable sleeve is preferably of a ceramic materialO However~ it may also be in the form of a cylindrical screen~ for example~ a sleeve of wire mesh.
` It was found to be advantageous to arrange one mounting flange in the housing as outwardly oriented extension, and to use a putty seal as a closure for the flange opening, the putty seal also serving to position and secure the catalyst rod, the absorbing substance, and the gas-permeable sleeve.
Further special features and advantages of the invention will become apparent from the description following below, when taken together with the accompanying drawing which illustrates, by way of example, a preferred embodiment of the invention in the form of a catalytic recombination device, 106S0~'~
:

represented in the figure as follows:
The figure of the drawing illustrates in an elevational view~ partially shown in longitudinal cross-section~ a device embodying the inventionO
; Commercially available lead-acid batteries of the type 12 volts - 45 amp hours with 5 positive and 6 negative plates in each cell were used to test the novel absorbing substance of the invention. The grid of each cell plate was made of a lead alloy which contained approximately 5.5 percent antimony and O.lS percent arsenic~ Each ceIl was closed hermetically by mounting in its opening a recombination device - of the type illustrated in the drawingO The purpose of such a device is to recombine the hydrogen and oxygen gases generated -during the operation of the battery to waterO The recombination ... ~ .
device includes a catalyst consisting of a catalyst carrier material, prèfe~ably palladium, the catalyst being pro~ided in the form of a rod 1, or in some other suitable geometric form. The length of the catalyst rod 1 is several times larger than its diameterO This catalyst body is accommodated inside a housing 4 of plastic material which has a substantially semi-cylindrical cross section~ the bottom 3 of housing 4 being inclin~d toward a downwardly extending hollow stub connection 5 through which the gas mixture enters into the housing and the recombined water returne to the electrolyte of the battery.
One end face of housing 4 has a lateral opening 6, a porous body 7 surrounded by a plastic plug 11 closing the opening 6 ,' . ' .; ,.

/

, . , .. , . -: ., .~ ~ . . - . : .

~06SUlZ
against the outside. m e plastic plug 11 includes an inwardly oriented hollow flange 8 extending into the housing 4 in the direction of an opposite end face. This opposite end face of the housing includes an outwardly extending flange 9 in alignment with flange extension 8 of the plastic plug 11. m e catalyst rod 1 of the device extends between these two flanges 8 and 9, the opening of flange 9 being closed after assembly by a putty seal.
m e porous body 7 consists of a ceramic mass which is made hydrophobic by a known treatmentO m e inside of housing 4 thus forms a convenient reaction space inside which the exother-mic reaction of recombining the hydrogen and oxygen gases to water under the infl~ence of the earlier-mentioned catalyst takes place.
In order to prevent the premature poisoning of the catalyst material, a ceramic tube 10 is arranged between the flange extension 8 and flange 9 of the housing in concentric arrangement with the catalyst rod 1 so as to provide an annular space around the latter. Within this annular space between tube 10 and the catalyst rod 1 is contained a granular bed of absorbing material 13, which thus surrounds the catalyst rod 1 in a uniform thicknessO mis bed of absorbing material 13 is preferably approximately S mm thicko m e aforementioned batteries were subjected to a test in which they were overloaded with a current of 3 amps until the catalyst failed as a result of poisoningO Whenever a battery was exhausted, the test - devices would be transferred to new batteriesO m e following absorbing substances have been tested:

: : .
:

,: _ g _ '' , . . , ~ .
.
.
. . .: . . .

106SO~Z

Substance Effectiveness Silicagel 3 days Alumina gel 9 days ~ Various Microfiltersmax. 7 days ; From the above listing, it can be seen that the effectiveness span of these materials is extraordinarily short.
However, it was found that if a commercially available type of alumina gel is used as a carrier material for a heavy-metal oxide, a considerable improvement was ~` 10achievable. The effectiveness in this case was extended to - 483 days. This absorbing material was produced in the following manner:
Example No. 1: A solution o 2.62 moles of CuS04 -5 H20 per liter was produced and into each liter of solution were introduced 0.66 kg of dried alumina gel, grain size 0.2 to 0.5 mm, at 80C temperature. Following some reaction time, the mixture was introduced into a 5-percent sodium carbonate ~, solution at 50C temperature, whereupon the copper carbonate was precipitated. Following washing, drying and calcination 20at 350C to 400C, the substance was ready for use.
- A markedly greater improvement of the effectiveness span was achieved through the use of heavy-metal manganites.
Heavy-metal manganites containing for example, between 50 and 95 percent MnO2 and, for example, between 5 and 40 percent CuO, with a corresponding admixture of Co3O4, Ni203, and Ag20, as well as mixtures of the aforementioned oxides, when prcpared on an alumina gel carrier or some other suitable carrying material, are capable of increasing the longevity of the catalyst to in .

: . .

~106501Z
excess of 550 days. An absorbing substance of this type was produced as follows:
Example No. 2: A solution of 1.50 moles per liteT
of MnS04 - 4 1l20, 1.10 moles per liter of CuS04 - 7 H20, and 0.15 moles per liter of NiSO4 - 7 H20 was prepared. Into one liter of this solution, heated at 80C temperature, were introduced 0.66 kg of dried alumina gel, grain size 0.2 to 0.5 mm.
Following a reaction time of 90 minutes (under occasional stirring), the mixture was introduced into 3 liters of a 5 to 10-percent solution of Na2CO3 at 50C temperature, so that the corresponding combination carbonates were formed. Following a further reaction time of 30 minutes ~under occasional stirring), the product was washed, dried and calcinated for 30 to 60 minutes at a temperature between 350 and 400C, after which the substance was ready for use.
During the aforementioned calcination treatment, under simultaneous exposure to air, the manganese and copper combination carbonates would create copper manganites. The effectiveness span of this substance was found to be 5~8 days.
This remarkable improvement in the span of effective-ness has been confirmed in connection with other substances which are available in oxidic form, the primary characteristics ; developed through these research experiments and tests on ; absorbing substances capable of removing the hydrogen compounds of arsenic and antimony, elements of Group V of the Periodic Table of Elements, being the capability of forming arsenide -and antimonide, respectively, with the component substances of the absorbing substance, and the capability of oxidation or ,~

. A :
. --11- . :

10~50~
of oxygen transfer of the component substances in the absorbing substance. As oxidation substances in this context should be understood those compounds which are reduced in reaction with AsH3 and SbH3. Oxygen transfer agents, on the other hand, are compounds whose catalytic effect produces the reaction of AsH3 and SbH3 with 2 Consequently, a suitable absorbing substance may be composed of oxides of elements which create hydrolysis-resistant arsenides and antimonides, or respectively, oxidic compounds of arsenic and antimony. As examples for such elements may be mentioned tin, nickel, cobalt, iron, copper, silver, gallium, indium, and thallium, but it should be noted that the hydrolysis-resistant arsenides and antimonides of - these elements no longer possess the characteristics of a salt, but are presumably intermetallic compounds.
Apart from these oxides which are suitable for use as absorbing substances, other elements in oxidic form may be used which qualify as oxidation agents and oxygen transfer ; agents~ such as for example V205~ Cr23' Fe23' Mo3~ and wo3.
The aforementioned absorbing substances may be used separately or as a combination of several arsenide and antimonide forming substances, prepared either as a powder or in granular form, or as a preparation on a carrier material such as alumina gel, for example. Furthermore, these absorbing substances, in addition to containing the aforementioned arsenide and antimonide forming compounds, may be admixed to one or several oxidation ' '~ ' :

~ 12-~ - .
'., ~ ' ~

106~0~

agents or oxygen transfer agents in powder form or granular form, or used as a preparation on a suitable carrier such as alumina gel, for example. Lastly, these absorbing substances may be composed of one or several oxidation agents or oxidation transfer agents in powder form or granular form, or be in the form of a preparation on a suitable carrier material, such as alumina gel, for example.
It should be understood, of course, that the foregoing disclosure describes only preferred embodiments of the invention and that it is intended to cover all changes and modifications of these examples of the invention ~hich fall within the scope of the appended claims.

'~''`
' ' ~G j -13--. ., :

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A composition for the elimination of catalyst poisoning gases, such as antimony hydride, arsenic hydride or other hydrides of Group V
elements, from the oxyhydrogen gas mixture produced by lead-acid storage batteries which comprises at least one heavy metal oxygen compound, chosen from the oxides and manganites, together with an inert carrier of an element chosen from the group comprising iron, cobalt, nickel, tin, gallium, indium, thallium, molybdenum, tungsten, and manganese.

2. A composition according to claim 1 wherein the heavy metal oxygen compound is a heavy metal manganite.

3. A composition according to claim 1 wherein the heavy metal oxygen compound is a heavy metal oxide.

4. A composition according to claim 1 or 2 wherein the heavy metal manganite is copper manganite.

5. A composition according to claim 1 or 3 wherein the heavy metal oxygen compound is from copper oxide.

6. A composition according to claim 1 wherein the heavy metal oxygen compound is a mixture of copper manganite and at least one oxide chosen from copper oxide and ferric oxide.

7. A composition according to claim 1 wherein the heavy metal oxygen compound is copper oxide admixed with ferric oxide.

8. A composition according to claim 1 wherein the heavy metal oxygen compound is at least one member of the group of oxides comprising Fe2O3, V2O5 and Cr2O3.

9. A method of producing an absorbing substance for the elimination of catalyst poisoning gases, such as antimony-hydride or arsenic-hydride or other hydrogen combinations with Group V elements, from the oxyhydrogen gas mixture produced by lead-acid storage batteries during their operation, the method comprising the steps of:
preparing a solution of a salt of at least one element which, in its oxidic state, reacts with antimony-hydride or arsenic-hydride to produce antimonide or arsenide, respectively, or their oxides;
introducing into said solution, at an elevated temperature, a carrier material;
subsequent to a period of interaction, introducing the mixture into a sodium carbonate solution, or its equivalent, for the precipitation of the carbonate; and washing, drying, and calcinating the product.

10. A method as defined in Claim 9, wherein:
the step of preparing a salt solution involves the use of manganese sulfate and copper sulfate;
the step of introducing a carrier material involves heating of the sulfate solution and introducing a granulated alugel as the carrier material;
the step of reacting with a sodium carbonate solution involves a 5 to 10-percent sodium carbonate solution; and the calcination treatment is performed at a temperature between 350 and 400°C.

11. A composition according to claim 1 wherein the heavy metal oxygen compound is supported on a particulate alumina carrier.

12. A composition according to claim 11 wherein the alumina carrier has a particle size of from about 0.1 mm to about 1 mm.

13. A composition according to claim 12 wherein the alumina carrier has a particle size of from about 0.2 mm to about 0.5 mm.