A METHOD OR METHODS OF TREATING CERTAIN GASES, AND MANUFACTURING SULPHURIC ACID, MURIATIC ACID, ACETIC ACID, AND CERTAIN SALTS OF POTASH, SODA, AND AMMONIA
Year: 1846

page_text: TO ALL TO WHOM THESE PRESENTS SHALL COME, I, FRANK
HILLS, of Deptford, in the County of Kent, Manufacturing Chemist, send
greeting.
WHEREAS Her present most Excellent Majesty Queen Victoria, by Her
Royal Letters Patent under the Great Seal of Great Britain, bearing date at
Westminster, the Eleventh day of August, in the tenth year of Her reign, did,
for Herself, Her heirs and successors, give and grant unto me, the said Frank
Hills, my exors, admors, and assigns, Her especial licence, full power, sole
privilege and authority, that I, the said Frank Hills, my exors, admors, and
assigns, or such others as I, the said Frank Hills, my exors, admors, or
assigns, should at any time agree with, and no others, from. time to time
and at all times during the term of years therein expressed, should and law-
fully might make, use, exercise, and vend, within England, Wales, and the
Town of Berwick-upon-Tweed, my Invention of "A METHOD OR METHODS OF
TREATING CERTAIN GASES, AND MANUFACTURING SULPHURIC ACID, MURIATIC ACID,
ACETIC ACID, AND CERTAIN SALTS OF POTASH, SODA, AND AMMONIA;" in which said
Letters Patent is contained a proviso, that I, the said Frank Hills, should cause
a particular description of the nature of my said Invention, and in what manner
the same is to be performed, by an instrument in writing under my hand and
seal, to be inrolled in Her said Majesty's High Court of Chancery within six
calendar months next and immediately after the date of the said in part
recited Letters Patent, as in and by the same, reference being thereunto
had, will more fully and at large appear.

page_text: NOW KNOW YE, that in compliance with the said proviso, I, the said
Frank Hills, do hereby declare that the nature of my said Invention, and
the manner in which the same is to be performed, are fully described and
ascertained in and by the following statement thereof, reference being had to
the Drawings thereunto annexed, and to the figures and letters marked
thereon, that is to say :-
I will now describe the different processes of which my Invention consists.
The first is for purifying illuminating gas from those gases which injure its
illuminating power, and which consist principally of ammonia and its com-
pounds, cyanogen and its compounds, and sulphuretted hydrogen.
My first method is to pass the gas through sulphate and muriate of the
peroxide of iron, either in solution or in a solid state. If the salts are used in
solution, then a vessel similar to a wet lime purifier may be used; but if they
are used in a solid state, a vessel similar to a dry lime purifier should be used,
and the salts should be damp when used. The deteriorating gases above men-
tioned will combine to a certain extent with the acid and base of the salts, and
the illuminating gas will be much purer.
.
My second method is to introduce muriate of magnesia into the retorts in
which the gas is generated, either mixed with the coals or in a little iron pot
or other vessel to be put into the retorts with the coals, or a separate retort
(connected with the bed of retorts) may be employed to decompose the muriate
of magnesia. The heat of the retorts will decompose the muriate of magnesia,
driving off its acid, which will combine with the ammonia of the gas, forming
muriate of ammonia, which will condense with the gas liquor.
I claim, under this head of my Invention, the purification of illuminating
gas, by passing it through the sulphate and muriate of the peroxide of iron,
either in solution or in a solid form, and the use of muriate of magnesia, as
herein-before described.
My process for manufacturing sulphuric acid consists of the following
methods:-
My first method is to manufacture sulphuric acid from sulphuretted hydrogen,
by burning it in a furnace so contrived that atmospheric air may come in con-
tact with the burning sulphuretted hydrogen at a succession of points or places
in its passage through the furnace. A furnace of the following description
auswers very well-A series of shelves or flues of fire tiles are placed in a
furnace, one over the other, about four inches apart, and are heated by a fire
beneath the bottom shelf and up the sides of the series, so as to keep them red
hot. The back end of the bottom shelf or flue connects with the back end of
the shelf above it, and the front end of this shelf with the front end of the
:

page_text: next above it, and so on to the top of the series, so that the burning sul-
phuretted hydrogen passes upwards from bottom to top, backwards and forwards,
through the succession of shelves which form one flue. Air is admitted at one
end of each shelf to come in contact with the sulphuretted hydrogen as it
passes up, so that by the time it arrives at the top it is completely decomposed,
and converted into sulphurous acid, which is converted into sulphuric acid in
the usual way in a leaden chamber, into which the flue from the furnace enters.
My second method in the manufacture of sulphuric acid relates to its con-
centration, which I effect by boiling it in glass retorts or bolt heads, and when
concentrated drawing part of the charge of the retorts off, either in a constant
stream or occasionally, and filling them up again with weaker acid quite hot
from a leaden boiler. By this means the retorts are not obliged to be cooled
at all to draw them off, but may be kept constantly concentrating. The hot
concentrated acid should be drawn off by a platinum syphon through a cooling
pipe of platinum placed in water. If the acid is run into the retorts in a con-
tinuous stream, it should at the same time be run out in a continuous streami
by keeping the syphon set so as to keep the height of the acid uniform.
I claim, under this head of my Invention, the manufacture of sulphuric
acid from sulphuretted hydrogen, by burning it in such a furnace as described;
or in such a manner that atmospheric air may come repeatedly in contact with
it at successive points of its passage through the furnace to the condensing
chamber.
I claim, secondly, concentrating sulphuric acid in glass vessels by drawing
off part of the charge of the vessels (when sufficiently concentrated) while
hot, either in a continuous stream or occasionally, and filling them up again
with weaker acid, which had better be as hot as possible.
My next process is for condensing the vapours of muriatic acid. To effect
this I first cause the acid gas to pass through a condenser constructed as
follows:-A series of stone-ware or earthen pipes closed at the bottom are
placed vertically in a long rectangular flue, situated intermediately between. the
furnace where the acid is generated and the chimney. The top of this flue
forms a water bath, and the earthen pipes are placed in the flue beneath,
through holes which are made for that purpose in the bottom of the water
bath. These holes must be made water-tight after the pipes are put through
them with pitch or cement, so as to prevent the water running into the flue
beneath. The water in the bath being higher than the top of the earthen
pipes, keeps them full of water; the muriatic acid gas enters at one end of
this flue, and comes in contact with the cold surfaces of the pipes, which are
kept full of cold water, and the acid is immediately condensed. Cold water

page_text: must be pumped into the water bath, which will descend into the earthen
pipes and keep them cool; steam should be admitted with the muriatic acid
gas, which will assist the condensation. To the end of this apparatus I con-
nect a series of shallow covered vessels partly filled with water, over which
the muriatic acid gas passes in its way to the chimney, by which means any
romaining muriatic acid vapor is absorbed by the water.
I claim, under this head of my Invention, condensing the vapor of muriatic
acid in flat covered chambers containing water placed at the end of a pipe
condenser, constructed as described.
My next process is to manufacture acetic acid, by decomposing the acetates
with muriatic acid instead of sulphuric acid, which is ordinarily employed; and
I claim, accordingly, the substitution of muriatic acid for sulphuric acid in the
manufacture of acetic acid by the decomposition of the acetates.
My next process is for manufacturing nitrate of potash, which I effect by
decomposing nitrate of soda by muriate of potash; a double decomposition
takes place, both substances being decomposed, the nitric acid leaves the soda
and combines with the potash, and the muriatic acid leaves the potasli
and combines with the soda, forming nitrate of potash and muriate of soda.
The salts must be added in the equivalent proportions. To effect the decom-
position of these salts, I use a wrought or cast iron boiler or pan with a fire
under it, in which I dissolve the chloride of potassium or muriate of potash in
a sufficient quantity of water; I then put in the equivalent proportion of
nitrate of soda, which decomposes the muriate of potash, as described; I then
evaporate the liquid until nearly the whole of the muriate of soda, which is the
most insoluble salt, is precipitated to the bottom of the pan, from whence it is
fished out and washed. The nitrate of potash remaining in the boiler or pan
is then run off to crystallize, and is made quite pure by recrystallization, as in
the usual mode of refining it, and which is well understood.
;
I claim, under this head of my Invention, manufacturing nitrate of potash
by the mutual decomposition of nitrate of soda and muriate of potash.
My next process is for manufacturing silicates of potash and soda, usually
called glass. I take white sand or silica and fuse it in a reverberatory furnace
with sulphate of potash or soda, in about the proportion of three parts of the
latter to two of the former; as soon as the sulphate is decomposed by the silica
(which decomposition will be accelerated by the addition of a small quantity of
lime), enough potash or soda must be added in the furnace to make a soluble
silicate of the alkali employed. This silicate should then be dissolved in water,
and carbonic acid gas (which may be obtained from a lime kiln) should then
be pumped or forced through the solution, which will make a carbonate of

page_text: the alkali employed, which may be evaporated and dried, and the pure silica.
will be precipitated. To this pure silica, when dried, the usual proportion of
potash of soda should be added to form silicate of potash or soda, usually
called glass. I finish its manufacture to fit it for the market by polishing it
with the native chromate of iron, instead of emery as heretofore used.
•
The chromate of iron, which, by the grinding process it undergoes with
the glass, is reduced to a fine powder, I employ to form the chromates and
bichromates of potash and soda in the usual way.
.
I claim, under this head of my Invention, producing silicate and carbonate
of potash and soda in manner described; and also the use of native chromato
of iron for finishing the manufacture of the silicates of potash and soda,
produced in any way, when they require to be polished to fit them for the
market as glass.
My next process relates to the manufacture of the cyanide of potassium and
sodium, and consists in the employment of the charcoal of peat, which is pro-
duced by the destructive distillation of peat in retorts or close vessels, in lieu of
the animal matter usually employed; this charcoal is to be treated in the same
manner as the charcoal obtained from animal matter is usually treated to
obtain the cyanides.
I claim, under this head of my Invention, obtaining the cyanides of potassium
and sodium from the charcoal or coke of peat, peat moss, bog earth, or turf.
.
My next process is one for manufacturing or producing the salts of am-
monia from ammoniacal liquor, from whatever source obtained, and nearly
resembles one which has been employed for the distillation of alcohol.
Figures 1 and 2 represent in section two modifications of the apparatus; in
Figure 1 the heat employed to volatilize the ammonia being transmitted
through metallic media, whilst in Figure 2 it acts directly upon the ammonia-
cal liquor to be distilled. a, a, Figure 1, is a vertical column, formed preferably
of wrought or cast iron, which I call the still; and b, b, is a similar column or
a continuation of the former, and denominated the "concentrator." The still
and concentrator are divided into a series of cells or compartments by shallow
horizontal trays c, c. These trays do not extend quite across the column, thereby
leaving a space d between one end of each tray and the side of the column,
so that each compartment is open to those above and those below it, and tho
trays are so. arranged that the space at their ends occurs alternately at opposite
sides of the column, so that a zig-zag passage is formed from the bottom to
the top of the apparatus. Upon each tray in the still there is a zig-zag coil
of thin metallic pipe e, e, communicating at one end with the coil immediately
below it, and at the opposite end with the coil immediately above it, the lowest

page_text: coil leading off to a steam boiler, or hot air or hot water apparatus, and the
uppermost coil opening into the atmosphere at x. The concentrator may
consist of merely the column and trays, but it will be rendered more efficient
by placing below.cach tray a similar coil of pipe (f, f) to those in the still,
cach coil connected with the one immediately above it and the one imme-
diately below it, the upper end of the upper coil communicating with the stop
cock g, attached to the cistern h, containing the ammoniacal liquor to be
distilled, and the lower end of the lower coil opening into the upper compart-
ment of the still at y. At the commencement of the operation the ammoniacal
liquor (which if it is to form carbonate of ammonia, must, of course, be the
same in solution, is admitted through the cock g, on to the upper tray of
the still, which it overflows, and then descends to the one below it, and so on
to the next, and when all the trays are filled the cock g is closed, and a current
of steam, hot water, or hot air is caused to pass through the pipes c, e. (If
hot air is employed the pipes should be larger than when steam is employed.)
This heats the ammoniacal liquor on the trays, and when the ammoniacal
vapour begins to ascend, the ammoniacal liquor from the cistern is then turned
on into the still in a regulated stream.. The ammonia which is volatilized will
rise in combination with a portion of watery vapour, but in its passage through
the concentrator it has to pass over the surfaces of the trays which are cooler
than those in the still, and also over the surfaces of the pipes (when they are
employed) through which the ammoniacal liquor is flowing from the cistern
into the still, and a portion of the heat of the vapour is thereby abstracted
and conveyed to the ammoniacal liquor, and, consequently, the aqueous vapor
will be condensed, and the ammonia become more concentrated. From the
concentrator it passes off by the pipo k, to one or more subliming balloons to
be sublimed, and may afterwards be refined to fit it for the market. By the
time the liquor being distilled arrives at the bottom of the column it will be
exhausted of its ammonia, and then passes off by the wasto pipe m. In lieu
of the pipes in the still and the concentrator, the trays may be constructed
hollow, and connected together by short elbow pipes at their opposite ends,
and the steam, hot air, or hot water in the one case, and the ammoniacal
liquor in the other case, will traverse theso hollow trays.
Figure 2 represents an arrangement of a still in which the heat is applied
directly to or in immediate contact with the ammoniacal liquor. The only
essential differenco in the two arrangements is the suppression of the pipes on
the trays of the still, the same parts therefore are indicated by the same
letters in each Figure. A flue n, from a coke oven, or a furnace in which
coke is the fuel employed, enters the still below the bottom disc, and the heated

page_text: air, carbonic acid, gas, &c., from the burning fuel pass under and over the
series of trays, through the openings before described, to the top of the still,
and from thence through the concentrator to a chimney, and by their heat
drive off the volatile ammonia, and at the same time the carbonic acid unites
with the ammonia, forming carbonate of ammonia. If more carbonic acid
than the coke yields is required to form the carbonates of ammonia, chalk may
be mixed with the coke, or (when it is intended to form solid carbonate of
ammonia) a sufficient quantity of carbonic acid from a lime kiln, with a close
top or cover, may be pumped into the ammoniacal liquor before it is distilled
in either form of still.
Between the concentrator and the chimney several chambers, usually called
balloons, are placed, in which the carbonate of ammonia from the ammoniacal
liquor distilled is sublimed. A flat shallow vessel with a tight cover, con-
taining weak sulphuric acid, should be placed between the balloons and the
chimney to absorb or fix any ammonia that may not have been condensed
before.
:
As a modification of my second arrangement, instead of having discs or
diaphragms in the still, it may be filled with bricks or clinkers, so placed as to
leave spaces between for the heated air and ammonia to ascend and for the
ainmoniacal liquor to descend. The concentrator before described, should also
be employed in connection with this column in the same manner as described
for the column constructed with trays, and the ammoniacal liquor to be dis-
tilled should be run through the pipes of the concentrator, and be distilled in
the same manner as described for the column. with trays (Figure 2). When
the beated air or gases are brought in immediate contact with the ammoniacal
liquor to be distilled, the air or gases should be injected in at the bottom of
the apparatus, or a draft should be established by connecting a pipe from the
sulphuric acid vessel either with a draft flue or with an exhausting apparatus.
When it is merely intended to obtain a strong solution of ammonia or its
volatile compounds, and not a solid carbonate of ammonia, from the ammoniacal
liquor to be distilled, a concentrator or condenser of the following description
will be preferable to that herein-before described :-
A, Fig. 3, is a cast-iron pipe of any convenient size, placed inside another
cast-iron pipe B, B, leaving the space of a few inches between them. Round
the inner pipe A is placed a coil of pipe C, C, C. The liquor to be distilled
runs from the reservoir D through the pipe A, and from thence through the
coil of pipe C, C, C, into the top of the still, as shewn in the Drawing. The
ammoniacal vapour from the still passes between the two pipes A and B, and
over the surface of the coil C, C, C, by which means the vapour is condensed
'

page_text: into liquid and cooled, and runs out at the bottom through the pipe E, and the
ammoniacal liquor. to be distilled is at the same time heated. A pipo F.
leading to a refrigerator, may be attached to the concentrator to carry off and
condense any ammoniacal vapor which is not condensed by the action of the
concentrator.
These stills and concentrators (as; before stated) act on the principle of
a distillatory apparatus employed for the distillation of alcohol; I; therefore
do not claim them for that purpose, nor do I claim a column with discs for
distilling ammonia when steam is admitted into the open column to distil
off the ammonia passing upwards between the diaphragms or trays and
coming in mutual contact with the liquor to be distilled, this plan having been
patented before, and being also a modification of a well-known apparatus used
in distilling alcohol, oil, &c.; but what I claim is, the distillation of ammonia
and its volatile compounds from ammoniacal solutions in stills, such as
described (or any modification of them acting on the same principle, and
whether combined or not with a concentrator, either by the agency of heat
obtained from heated air or gases coming in contact with the ammoniacal
liquor in its passage through the still, or by the agency of heat derived from
steam, hot water, or heated air or gases, passing through pipes or hollow
vessels, but not coming in contact with the ammoniacal liquor.
Secondly, as regards the concentrators or condensers, I do not confine my
claim to any particular form or position of them, as it may be considerably
varied; but what I claim under this head of my Invention is, a condenser,
such as described, or any other acting on the same principle, in which the
ammoniacal vapour from any form of still comes in contact with pipes or
small hollow vessels, through which is conveyed or is passing the ammoniacal
liquor to be distilled, whereby the ammoniacal vapour is condensed and cooled,
and its heat conveyed to the ammoniacal liquor to be distilled.
I claim thirdly, obtaining carbonic acid from a lime kiln for the purpose of
combining with ammonia to make its carbonates.
My next process is for obtaining some of the salts of ammonia from peat,
peat moss, bog earth, or turf, by burning it in a furnace to which air is
admitted. An upright furnace with fire bars and ash-pit at the bottom, and
with a covered top, answers the purpose. The top of the furnace is connected
by a flue to a condenser. A fire of peat is made in the furnace, and as it
burns away more peat is added to keep the fire up. The volatile products of
the combustion are drawn through the condenser by connecting it with a
chimney; or mechanical means may be employed to draw or force them through
the condenser, which may be formed of a shallow vessel containing cold water,

page_text: over which the gases pass, or of a pipe surrounded by cold water, through
which the gases pass; the ammonia given off from the peat, which is princi-
pally carbonate, will be condensed in the condenser. By admitting steam into
the furnace along with the air which supports the combustion, a larger quantity
of ammonia will be obtained, but care must be taken not to damp the fire by
admitting too much steam. The ammonia may be obtained as a muriate by
admitting muriatic acid gas into the furnace along with the steam and air..
I claim, under this head of my Invention, obtaining animonia or carbonate
of ammonia from peat, peat moss, bog earth, or turf, burnt in a furnace, with
the admission of air or air and steam, and also obtaining muriate of ammonia
by bringing the ammonia, as described, in contact with the muriatic acid; but
I do not claim obtaining ammonia from peat by its destructive distillation.
My next process is for manufacturing sesqui-carbonate of ammonia from
the bicarbonate of ammonia found in guano, by sublimation, in the usual way,
or by any other convenient means. Before subliming it should be mixed with
a considerable quantity of charcoal or coke dust, or any other substance capable
of depriving it of its offensive smell.
I claim, under this head of my Invention, making sesqui-carbonate of
ammonia (the carbonate of ammonia of commerce) from the bicarbonate of
ammonia found in guano.
In witness whereof, I, the said Frank Hills, have hereunto set my hand
and seal, this Ninth day of February, in the year of our Lord One