IMPROVEMENTS IN PURIFYING CERTAIN GABES AND LIQUIDS FROM SULPHURETTED HYDROGEN
Year: 1860

page_text: LETTERS PATENT to Richard Laming, formerly of Clifton Villas, Maida
Hill West, and now of Priory Road, Kilburn, and Charles Smith,
formerly of Gloucester Street, Regent's Park, and now of Church Street,
Brompton, for the Invention of "IMPROVEMENTS IN PURIFYING CERTAIN
GABES AND LIQUIDS FROM SULPHURETTED HYDROGEN."
Sealed the 21st December 1860, and dated the 30th June 1860.
PROVISIONAL SPECIFICATION left by the said Richard Laming and
Charles Smith at the Office of the Commissioners of Patents, with their
Petition, on the 30th June 1860.
We, RICHARD LAMING, of Clifton Villas, Maida Hill West, Middlesex, and
Charles Smith, of 8, Gloucester Street, Regent's Park, Middlesex, do hereby
declare the nature of the said Invention for "IMPROVEMENTS IN PURIFYING
CERTAIN GASES AND LIQUIDS FROM SULPHURETTED HYDROGEN," to be as follows:-
Oxides of iron and manganese are either anhydrous or hydrated, that is to
say, they either have not any or only a small portion of water in chemical
combiuntion. These hydrated oxides when precipitated from solution, carry
down along with them more water than suffices for their hydration, and that
excess they retain even after their removal from the liquids from which they
have been thrown down, until they have by exposure to the air or other means
assumed the state of dry hydrates,

page_text: Now it is well known to chemists that the hydrated oxides which have been
precipitated from solution are more susceptible of chemical action when first
obtained than after they have become old and dry; and also, that the dried
hydrated oxides are, in general, more energetic than corresponding oxides in
the anhydrous state, facts which have suggested a prevalent belief that the
presence of water in the oxides is the efficient cause of their chemical action.
This Invention is derived from another belief suggested to us by observing
that some hydrated oxides (those, for example, which are found native,) are
hardly more susceptible of chemical action than other corresponding oxides,
which are anhydrous, our belief being that the cause of great chemical
energy in the oxides is simply a perfect isolation of their molecules or minute
particles from one another,and whichisolation the presence of combined water
is only a means of establishing.
In practice, native ores or compounds of iron, or manganese with oxygen
whether hydrated or anhydrous, and also artificial compounds of iron and
oxygenwhichhavesustained a redheat withouthaving somekindof fixedmatter
between their molecules or minute particles to keep them apart, have here-
tofore been useful, or nearly so, for the purification of coal gas, by reason of
theirlimited capacity for firstabsorbingsulphurettedhydrogen,and afterwards
for undergoing what is known as atmospheric revivification, that is to say, for
becoming sulphides while exposed to thegas,and for returningtooxides when
subsequently exposed to the air. Such substances taken both from the native
class and the artificial class have been ground into powder and submitted to
trials, but the results obtained have been so unsatisfactory that their use for
gas purifying is now either altogether abandoned, or made tolerable by an
admixture of other chemical reagents,so that the oxides generally used forthe
purpose are attained artificially by precipitation; although when so madethey
are more costly.
Now we have practically discovered that the comparativelyinert and cheap
substances of either of the two classes, whether they be hydrated or an-
hydrous, may be made equal to the expensive precipitated oxides, both in their
power of absorbing sulphuretted hydrogen, and afterwards in undergoing
atmospheric revivification by applying them in a stateof extreme disintegra-
tion, such as we can confer upon them by mechanical means, as careful
grinding with elutriation or sifting, and which we know to pervade the whole
of a mass whenever a small portion of it diffused in a little water lets fall no
particles, which when caused to slide down an inclined plane covered with a
film of water, exhibit to careful observation an appearance of intestine com-
motion, or rolling over upon successive sides or faces, as displayed by ever-

page_text: varying angles of reflected light, but such only as pass down the plane'
almost as little apparent difficulty as the fluid itself.
The Invention consists in purifying coal and other gases and liquids con-
taining sulphuretted hydrogen, by means of the comparativelyinert substances.
above indicated, after their molecules or minute particles have been isolated
from one another, and made energetic by extreme mechanical disintegration,
and also in prolongingthepurifying agency of revivifiable oxides of manganese,
by causing the sulphuretted hydrogen which they are to withdraw from gas to
be accompanied into the purifying vessels by about its chemical equivalent of
oxveen either as oxygen ons or as atmospheric air.
SPECIFICATION in pursuance of the conditions of the Letters Patent, filed
bythe said Richard Laming and Charles Smith in the Great Seal Patent
Office on the 29th December 1860.
TO ALL TO WHOM THESE PRESENTS SHALL COME, we, RICHARD
LAMING, formerly of Clifton Villas, Maida Hill West, and now of Priory
Road, Kilburn, and CHARLES SMITH, formerly of Gloucester Street, Regent's
Park, and now of Church Street, Brompton, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her Letters
Patent, bearing date the Thirtieth day of June, in the year of our Lord One
thousand eight hundred and sixty, in the twenty-fourth yearof Herreign,did, for
Herself, Her heirs and successors, give and grant unto us, the said Richard
Laming and Charles Smith, Her special licence that we, the said Richard
Laming and Charles Smith, our executors, administrators, and assigns, or
such others as we,the said Richard Laming and Charles Smith, our executors,
administrators, and assigns, should at any time agree with, and no others,
from time to time and at all times thereafter during the term therein expressed,
should and lawfully might make, use, exercise, and vend, within the
United Kingdom of Great Britain and Ireland, the Channel Islands, and
Isle of Man, an Invention for "IMPROVEMENTS IN PURIFYING CERTAIN GASES AND
LIQUIDS FROM SULPHURETTED HYDROGEN," upon the condition (amongst others)
that we, the said Richard Laming and Charles Smith, our executors or
administrators, by an instrument in writing under our, or one of our, or their,
or one of their hands and seals, should particularly describe and ascertain the
nature of the said Invention, and in what mauuer the same was to be per-
formed, and cause the same to be filed in the Great Seal Patent Office
within six calendar months. next and immediately after the date of the said
Letters Patent.

page_text: NOW KNOW YE, that I, the said Richard Laming, on behalf of myself
and the said Charles Smith, do hereby declare the nature of our said
Invention, and in what manner the same is to be performed, to be par-
ticularly described and ascertained in and by the following statement :-
Our Invention consists in depriving of sulphuretted hydrogen the gases
obtained by distilling coal and similar matters, and also solutions of hydro-
sulphate of ammonia, by the repeated use of oxides of manganese and iron, so
prepared by mechanical means or heat as to have their molecules or minute
particles in a state of extreme division similar to that which has heretofore
been conferred upon oxides on manganese and iron-repeatedly used for the
said purification only by or after precipitating them from their solutions.
The Invention also consists in applying to the same purposes hydrated and
precipitated oxide of iron, to the purifying energy of which increased per-
manence has been given by mechanically distributing the pure unmixed oxide
while in its fresh undried state over the surfaces of dry sawdust or other
absorbent and porous matter.
We will point out a natural principle implicated in our Invention, in order
more clearly to make known in what the Invention cousists, and the means
for carrying it into effect.
Certain oxides of manganese and iron are what is called hydrated, that is to
say, they have a small proportion of water chemically combined with them in
a dry state, and sometimes when those hydrated oxides are formed by pre-
cipitation from their solutions they carry down along with them some other
water in addition, the excess of water over and above what is necessary for
their hydration making them wet or damp, and clinging to them mechanically,
as it is called, more tenaciously than if the oxides had been only wetted with
water after they had become dry hydrates by exposure to the air. Now it is
well known that hydrated oxides, generally speaking, are more susceptible of
chemical action than such as are anhydrous, and that fact has suggested a
prevalent belief that hydration of the oxides is the necessary condition of their
chemical activity; but this Invention is derived from another belief, namely,
that the cause of great chemical energy in oxides is a condition of perfect
separation between their molecules or minute particles, however produced,and
which condition hydration is only one among other means of establishing, for
whenmechanical water is carried down with a precipitated oxide it confers upon
it a greater volume than the water of hydration alone would give it, and at the
same time makes it more chemically energetic. Our belief was founded too
open another fuct which we had observed, namely, that when care has been
taken to keep the molecules or minute particles of an anhydrous oxide from

page_text: coalescing, from the moment of its formation its chemical activity is sometimes
greater than that of hydrated oxides, whose molecules or particles have had
nothing solid between them to prevent their coalescing into a compact
mass.
Oxides of manganese and iron may be made by several chemical processes,
with their molecules or minute particles widely separated, but we have ascer-
tained that the state of separation, which may be given by cheaper mechanical
means to the molecules or minute particles of such of the said oxides as are
found ready made either in nature or as residues of processes in the arts, also
confers upon them great effectiveness.
Firstly, with reference to oxides of manganese.-Native black oxide of
manganese in its commercial condition of coarse powder has in times past been
applied to the purifying of the above-named gases, an attempt being made to
recover from it after use some oxide that would be repeatedly serviceable for
the purifying. The first cost of the oxide being considerable, and the roasting
process inefficientaswell as expensive, the process was unsatisfactoryandsoon
abandoned.
We use among others the native black oxides of manganese, and recover
from them after use and by inexpensive means a revivifiable oxide that may
be satisfactorily used for purifying the gases a great number of times is
succession. All the native oxides of manganese that we have tried answer
our purpose, but we prefer such as are most free from earthy impurities, and
most easily reduced to powder. We find, too, that instead of the native oxides
we can with effect substitute for them the red or brown oxides of manganese
that commonly result from raising artificial or native compounds of the metal
to a high temperature. Having selected the oxide we intend to use, our first
care is to reduce it, as far as is convenient, to an impalpable powder by
grinding it either dry or wet, as, for example, is practised upon various
materials by colour makers and potters, and that done, we prefer to follow
the operation of grinding by an elutriation or water washing, whereby to float
away the finer particles from among the grosser, and cause them to be
deposited separately in another vessel. This process of elutriation is well
known in the arts,and needs here but few words of description. We practice
it by stirring the ground oxide into water contained in a tank that may be
three or four yards square, and as many feet deep, until we have reason
to believe that the whole of it is thoroughly mixed with the water.
next allow the contents of the tank to remain at rest until the gritty
particules of the oxide have subsided to the bottom, for which a few
seconds will generally suffice; and then we run off the supernatant water
We

page_text: by a large opening into a second tank placed at a lower level, into which
the water carries with it the impalpably fine particles of the oxide which
it has temporarily suspended, and there very soon deposits them. Should
too long a rest have been allowed, much of the impalpable powder will
have gone down in the first tank with the grosser particles, in which
case a repetition of the operation should be had recourse to for transferring
it into the lower tank. After some minutes rest in the second tank wo
run off the water from it without disturbing the sediment, we collect the fine
deposit, drain it on a sand or other filter,and thon either dry it at atmospheric
temperatures or by air heated to about 80 or 90 degrees of Fahrenheit, or we
mix it while. wet with as much dry sawdust or other porous matter as will
make it into a damp, granular, and pervious mass. There is an oxide of
manganese, which is made artificially by heating the carbonate of the metal
until it parts with its carbonic acid; the process for making it was described
in the original Specification of a Patent granted to Richard Laming, and-
bearing date the Fourth day of November, One thousand eight hundred and.
forty-seven, which also directed it to be used for purifying gas. The oxide so
made is either black or brown, and we now find that after exposing freely to
the air the sulphide of manganese which results from passing through it the
gases foul with sulphuretted hydrogen; that it contains a revivifiable oxide
susceptible of being used witheffect in place of the other oxides of manganese
above-mentioned, and for which we purpose occasionally to substitute it.
We use for our Invention of purifying the gases one or other of theabove-
named oxides which we prefer to make pervious by admixture with sawdust
or other porous matter; we then put the mass in thick layers, and in a damp
condition, into dry purifiers, and continue it there, subject to the action of the
passing impure gases, until the oxide has become a sulphide of manganese,
when we expose it to the action of the atmosphere, either in or out of the
vessels, as is practised in the case of gas purification by oxide of iron. That
exposure changes the sulphide into an oxide fit for, and which we apply to,
initiating a repetitionof the alternate purifying and revivifying operations an
indefinite number of times; or, instead of so frequently alternating the gas
purification and the oxide revivification as two distinct operations, we propose
sometimes to mix with the gases about to be purified a volume of oxygen gas
about as great as that of the sulphuretted hydrogen contained in it, or in place
of oxygen, about five times the volume of atmospheric air, by which means
the purifying action of a charge of oxide may be greatly prolonged, and the
revivifying process proportionately postponed.
We use for our Invention of purifying from sulphuretted hydrogen gas

page_text: liquors, gas washings, and other solutions of hydrosulphate of ammonia, one
or other of the above named oxides, by bringing it in sufficient quantity into
temporary contact with all the liquor to be purified,and which we effect either
by well stirring the oxide in its wet or dry state into the liquor, or by using it
mixed with porous material as a filter to pass the liquor through. In both
cases we convert the sulphide of manganese which results from the purification
into a revivifiable oxide for repeated use by freely exposing it totheal mosphere
at ordinary temperatures in any known manner that may at the time be most
convenient.
Secondly, with reference to oxides of iron. We take hæmatite native oxides
of iron generally, and other compounds containing that metalandoxygen, which
result as residues from different operations in the arts conducted at a red or
other high temperature, preferring in all cases such as are purer, softer, and
more friable than the rest, and having reduced them to the condition of fine
powder so far as is convenient by grinding, we next separate the impalpable
from the grosser parts by elutriation, as already described with respect to
oxides of manganese; and then having collected and drained the impalpable
portion, we proceed at once to mix it while wet with as much dry sawdust or
other convenient absorbant matter as will give to the resulting mixture the
form of a damp, granular, and porous mass. We here explain, that by thus
promptlymixingthe finely-divided oxide with theporousmatter, we perpetuate
the good effected by the elutriation, as we thus keep separated the molecules
or minute particles of the oxide, and which we find, in the cases both of iron
and manganese, to have a tendency to recombine into a hard and compara-
tively inefficacious mass whenever they are long left close together, even when
they have been produced by precipitation from solution. We sometimes
separate the precipitate of hydrated oxide of iron when it has been thrown
down unmixed from its solutions, and prolong its purifying energy by thus
absorbing it while yet wet into dry sawdust or other convenient absorbent
matter. With the porous material made as above said we purify the gases
and liquors above mentioned, using it and revivifying it in the manner already
practiced with the artificially precipitated oxides of iron, and also with native
oxides of iron prepared by mechanical means without elutriation. When the
purifying vessels are sufficiently large, the elutriated oxides may be dried in
the air at ordinary temperatures, or a few degrees higher, and used upon the
gases without being first mixed with porous materials, but we do not recom-
mend that manner of using them. And we propose sometimes to mix with
the elutriated oxides of iron, when to be used for purifying the gases, whether
alone or made into a more porous mass, about five or ten per cent. of slaked

page_text: lime or chalk in order to impede their gradual conversion into the less useful
subsulphate of the metal during the process of revivification.
Weclaim with respect to oxides of manganese purifying from sulphuretted
hydrogen, first, the gases obtained by distilling coal and similar matters; and,
secondly,gas liquors and similar solutions, by the agency of native or artificial
oxides of manganese reduced to powder by mechanical means, or of oxides
made by heating the artificial carbonate, conjoined with the repeated use of
the oxide which is produced in an effective condition by exposing to the air at
atmospheric temperatures, or thereabout, the metallic sulphide which results
from each purifying operation.
We claim also the said purifications of the same gases by the said mecha-
nically prepared oxides when it is done simultaneously with the use of
oxygen gas, or of atmospheric air, mixed with the gases preparatory to their
purification.
We claim, with respect to oxides of iron purifying from sulphuretted
hydrogen, the gases obtained by distilling coal and similar matters by means,
firstly,of elutriated oxides of iron in contradistinction tothose which are either
reduced to the impalpable state by precipitation from solution, or left by
the unaided process of grinding in the condition of gross powder, parts of
which latter are necessarily too coarse to be very effective; and, secondly, of
oxides of iron generally when incorporated mechanically while in a state of
extreme division, and in a wet conditiou, in the absence of earthy matter with
dry absorbent materials, whereby their minute parts are prevented injuriously
contracting upon one another by age, or by becoming dry. The claim
extending in all cases to the said oxides after their atmospheric revivifications,
although their chemical character or composition may have become thereby
changed.
In witness whereof, I, the said Richard Laming, on behalf of myself
and the said Charles Smith, have hereunto set my hand and seal, this
Twenty-ninth day of December, in the year of our Lord One thousand
eight hundred and sixty.
RICHARD LAMING. (L.S.)