IMPROVEMENTS IN THE MANUFACTURE OF CERTAIN ACIDS AND SALTS, AND A NEW APPARATUS APPLICABLE TO THE SAID IMPROVEMENTS
Year: 1848

page_text: TO ALL TO WHOM THESE PRESENTS SHALL COME, we, CHARLES
CRANE, of Stratford, in the County of Essex, Manufacturing Chymist, and
JAMES THOMAS JULLION, of the same place, Analytical Chymist, send greeting.
WHEREAS Her present most Gracious Majesty Queen Victoria, by Her
Letters Patent under the Great Seal of Great Britain, bearing date at
Westminster, the Eighteenth day of January, in the eleventh year of Her
reign, did, for Herself, Her heirs and successors, give and grant unto us, the
said Charles Crane and James Thomas Jullion, Her especial license, that
we, the said Charles Crane and James Thomas Jullion, our executors, adminis-
trators, and assigns, or such others as we, the said Charles Crane and James
Thomas Jullion, our executors, administrators, 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 lawfully might make, use, exercise;
and vend, within England, Wales, and the Town of Berwick-upon-Tweed,.
in Her said Majesty's Islands of Jersey, Guernsey, Alderney, Sark, and Man,
and also in all Her said Majesty's Colonies and Plantations abroad, our
Invention of "IMPROVEMENTS IN THE MANUFACTURE OF CERTAIN ACIDS AND SALTS,
AND A NEW APPARATUS APPLICABLE TO THE SAID IMPROVEMENTS;" in which said.
Letters Patent is contained a proviso obliging us, the said Charles Crane and
James Thomas Jullion, by an instrument in writing under our or one of
our hands and seals, particularly to describe and ascertain the nature of our

page_text: said Invention, and in what manner the same is to be performed, and to cause
the same to be enrolled in Her said Majesty's High Court of Chancery within
four 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.
NOW KNOW YE, that in compliance with the said proviso, we, the said
Charles Crane and James Thomas Jullion, do hereby declare the nature of our
said Invention to. consist,-
First (as regards our improvements in the manufacture of certain acids, by
which we mean nitric and oxalic acids) in a continuous mode or method of
adding the materials to be decomposed by degrees as required to the mother
liquor, thus enabling us to employ a high temperature to the liquors or mate-
rials in the said manufacture, likewise the conversion of the oxides of nitrogen
into nitric acid by the decomposition of water by means of chlorine.
Secondly (as regards our improvements in the manufacture of salts) our
Invention consists in the oxidizing metallic substances, and in the manufacture
of nitrates at the same time by bringing oxides of nitrogen and oxygen gas, or
atmospheric air, in contact with the substances herein-after described. Also
the manufacture of tartrates of the alkaline earths by decomposing the tar-
trates of potash by means of the sulphurets of the metallic base of those
earths, as likewise the use or employment of catalyptic or contact substances
for manufacturing ammoniacal and cyanogen compounds; and,
Thirdly (as regards our new apparatus), our Invention consists of vessels
formed of slate or wood for the purpose of manufacturing acids, as also vessels
for condensing vapours or gases, as herein-after described.
And in further compliance with the said proviso we do hereby describe the
manner in which our said Invention is to be performed, by the following
statement thereof, reference being had to the Drawing annexed, and the
letters of reference marked thereon; that is to say:-
As regards the first part of our Invention, in our processes for manu-
facturing oxalic and nitric acid, mother liquor is to be placed in the closed or
covered slate vessel A, which we term a generator, in the top of which is
an opening B for the insertion of the mother liquor and the withdrawal of
the product upon the completion of the process, and which may be closed nir-
tight by the lid C. There is another opening D in the top of the generator, in
which a thermometer is fixed to shew the temperature of the contents of
the generator during the operation. E, E, are two funnel pipes with
elongated stems passing through the top of the generator and reaching
nearly to its bottom, to convey proportionably and by degrees the materials to

page_text: be decomposed or acted on from the feeding vessels F, F, which are furnished
with stopcocks so as to enable the operator to regulate the supply according to
the length of time over which it may be wished to extend the operation. G
is a pipe through which steam or hot water circulates for the purpose of
heating the liquor in the generator A. H is an opening in the top, to which
the eduction pipe I is adapted to convey away the gases generated during the
operation to the receiver K, which pipe dips below the surface of the fluid in
the said receiver, which said receiver is filled up to the overflow pipe L at the
commencement, while any excess escapes through L into the reservoir M, and
so maintains the same amount of pressure throughout the process. N is a
pipe attached to a chlorine generator, to admit a current of chlorine gas,
which pipe also dips below the surface of the fluid. 0, 0, 0, are connecting
arms for conveying the gases or vapours to the series of condensers P, P, P.
Q, Q, Q, are overflow pipes for conveying away the condensed fluid from the
condensers through the main R, which is a pipe with the necessary openings
to allow the overflow pipes Q, Q, Q, to descend to the bottom of the main ;
and S is a waste pipe or cock situated two inches from the bottom of the
main R, which discharges its contents into the collecting pan T. U is a pipe
passing from the last condenser into the exterior atmosphere, to carry off the
waste gases. The whole of the above-described apparatus having been pro-
perly arranged and a quantity of mother liquor placed in the generator A, and
nitric acid and syrup in the usual proproportion to such quantity of mother
liquor placed separately in the feeding vessels F, F, heat is to be applied, and
the temperature of the liquor raised as quickly as possible to one hundred and
eighty or two hundred degrees of Fahrenheit's thermometer. Streams of nitric
acid and syrup are then to be caused to flow by turning the stopcocks through
the funnel pipes E, E, into the liquor in such quantity that the delivery of the
whole shall occupy about eighteen hours, at the expiration of which time the
process will be completed. The gas or gases arising from the decompositiou
of the materials so supplied will pass off through the eduction pipe I into the
receiver K, where a stream of chlorine is to be introduced from the chlorine
generator through the pipe N sufficient to convert the whole of the oxides
of nitrogen into nitric acid. A portion of the water in the receiver K
will be decomposed, its hydrogen combining with the oxide of nitrogen to
form nitric acid, while its hydrogen will combine with the chlorine to form
hydrochloric acid; these mixed vapours passing onward into the condensing
vessels P, P, P, will there be condensed. The whole of the nitric acid and
syrup having been run in, and the liberation of the gases or oxides of nitrogen
having ceased, the liquor is to be drawn off from the generator A by means of

page_text: a syphon inserted in the aperture B, and placed in a convenient vessel to
crystallize. Although we have described in the above process the application
of a temperature of from one hundred and eighty to two hundred degrees as
being that which we prefer, still if it be thought desirable the liquor may be
heated even to the point of ebullition without detriment to the success of the
process.
Having thus described the nature of this part of our. Invention, and the
manner in which the same may be performed, we would have it understood
that we do not confine ourselves to the particular mode or arrangement, or to
the range of temperature above described, but we claim as our Invention any
continuous mode of adding to the mother liquor, in due proportions and by
degrees, the materials to be decomposed; also the application of a high tempe-
rature, as herein-before described; and likewise the. manufacturing of nitric
acid from the oxides of nitrogen, by decomposing water by means of chlorine,
as herein-before described.
And now as regards the second part of our Invention, which relates
to the manufacture of salts, it consists, first, in manufacturing nitrates by
means of the oxides of nitrogen and oxygen gas, or atmospheric air, in con-
junction with basic substances, as follows, namely, the oxides of nitrogen,
however procured, are to be mixed with atmospheric air or oxygen gas, and
made to pass through a chamber or other apparatus containing a metal or
metallic oxide, or any alkali or alkaline earth, the presence of which basic
substances induce a simultaneous combination of the oxide with oxygen, and
the base thus employed to form a nitrate; for example, line in the state of
quicklime, hydrate, or carbonate, is to be placed in a chamber on trays, or in
an apparatus similar to the "dry lime purifier" used in gas works (or a series
of the same), and a current of the mixed gases passed slowly through them;
and when the gas that is given off from the last vessel is found to contain
nitrous acid, the contents, which will be nitrate of lime, should be withdrawn
and the vessel replenished. We would here remark that care should be taken
to ensure the presence of a sufficient quantity of atmospheric air or oxygen in
the vessels, so as to cause the entire conversion of the oxides of nitrogen to
the highest degree of oxygenation, and their consequent combination with the
basic substance as nitrate. The following mode of ascertaining this we have
found sufficient for the purpose, namely, the absence of any of the oxides
of nitrogen, together with the presence of free oxygen in the gas that issues
from the last vessel, shews that sufficient oxygen has been furnished; on the
contrary, should red fumes make their appearance upon allowing a portion of
the gases to escape into the atmosphere, and which gases were previously

page_text: colorless, it is a proof that there has been a deficiency of oxygen, and
consequently more atmospheric air or oxygen gas must be passed into the
apparatus. When a metal
employed in the place of lime, as above-men-
tioned, we prefer to reduce it previously to small particles by granulation, or
otherwise, so as to expose a larger surface to the action of the mixed gases.
Having thus described the nature of this part of our Invention, and the
manner in which the same may be performed, we would have it understood
that we do not confine ourselves to any particular apparatus or mode of pro-
ceeding in the above process. But we claim as our Invention generally the
oxidizing metallic substances, and the manufacture of nitrates, by contact of
the oxides of nitrogen with any metal or metallic oxide, or any alkali or
alkaline earth, in conjunction with oxygen gas or atmospheric air, as herein-
before described.
Secondly, we manufacture the tartrates of the alkaline earths by decom-
posing the tartrates of potash by means of the sulphurets of the metallic bases
of those earths. Of these we prefer either the sulphuret of calcium or the
sulphuret of barium. For this purpose a solution of tartrate of potash is to be
taken, and a solution either of sulphuret of calcium or sulphuret of barium
added, until no further precipitation takes place; or either may be added in
the solid state to the solution of the other, and boiled with occasional agitation
when tartrate of lime or baryta will separate, and sulphuret of potassium
remain in solution. The solution should be examined by adding a solution of
sulphuret of calcium to ascertain whether the whole of the tartrate of potash
is decomposed, taking care to have the sulphuret in slight excess, so as to
prevent loss of tartaric acid. Or lime or baryta may be added to the solution
of tartrate of potash, and boiled, if preferred, and sulphuretted hydrogen passed
into it, until no further precipitation takes place. When all the tartrate of
potash is decomposed, the precipitate must be allowed to subside, and the clear
solution of sulphuret of potassium withdrawn from off the precipitate, which
must then be washed to free it from adhering sulphuret of potassium, when it
may be decomposed in the usual way for preparing tartaric acid, if that sub-
stance is required. When lime is used in conjunction with sulphuretted
hydrogen for the decomposition, it may be used in the following proportions,
videlecit, four parts of tartrate of potash to one part unslacked lime; or that
quantity will be sufficient to decompose the solution of neutral tartrate arising
from the decomposition by chalk of six parts of acid tartrate of potash.
We do not confine ourselves to the particular modes of operation above
described, or to the use of the particular sulphurets or bases above mentioned,
but we claim as our Invention the decomposing the tartrates of potash by

page_text: means of any sulphuret, or by sulphurettéd hydrogen, in conjunction with any
basic substance capable of forming an insoluble tartrate.
Thirdly, we manufacture ammonia in the state of carbonate, hydrocyanate,
or free ammonia, by passing any of the oxygen compounds of nitrogen, together
with any compound of hydrogen and carbon, or any mixture of hydrogen with a
compound of carbon; or even free hydrogen, through a tube or pipe containing
any catalytic or contact substance, as follows:-The oxides of nitrogen, how-
ever procured, are to be mixed in such proportion with any compound of
carbon and hydrogen, or such mixture of hydrogen and carbonic oxide or acid
as results from the contact of the vapour-of water with ignited carbonaceous
matter, that the hydrogen compound, or mixture containing hydrogen, may be
in slight excess, so as to ensure the conversion of the whole of the nitrogen
contained in the oxide so employed into either ammonia or bydrocyanic acid,
which may be known by the absence of the characteristic red fumes upon
allowing some of the gaseous matter to come in contact with atmospheric air.
The catalytic or contact substance we prefer to employ is platinum, which
may be eitlier in the state of sponge, or asbestos, coated or covered with the
platinum, may be substituted, which is to be placed in a tube, which we prefer
to heat to about six hundred degrees of Fahrenheit's thermometer. To this
tube is to be attached a pipe, of any convenient length, which is to pass
through a vessel of water kept at the point of ebullition or thereabout, so as to
reduce the temperature of the products, and at the same time prevent the
deposition of carbonate of ammonia, which passes onwards into a vessel of the
description well known, and employed for the purpose of condensing carbonate
of ammonia. This condenser, for our-purpose, must be furnished with a safety
pipe to allow of the escape of uncondensed matter, which should be made to
dip into a solution of any substance capable of combining with hydrocyanic acid
or ammonia, where they would be condensed. That which we prefer is a
solution of a salt of iron, which condenses both hydrocyanic acid and ammonia;
or a solution of hydrate of potash may be used, if it be required to condense
only the hydrocyanic acid. In the former case prussian blue may be obtained,
and in the latter ferrocyanide of potassium, by any of the usual and well-
known methods. We are aware that it has been proposed to manufacturé
ammoniacal and cyanogen compounds from the oxides of nitrogen, and com-
pounds of carbon and bydrogen, by passing them through a tube heated to
redness; but it was emphatically expressed as one of the necessary conditions
for the success of the process that the carbon should be in such excess as to
give a large precipitate in the form of lampblack. On the contrary, we do not
intend to produce, neither do we produce, precipitated carbon in our process;

page_text: in fact, the characteristic feature, and that which distinguishes our Invention
from that above mentioned, is that any liberation of carbon in the solid state
must be particularly avoided, and only so much carbon should be supplied as
would, by entering into combination either with the oxygen or the nitrogen in
the oxide, give rise to the formation of carbonic or hydrocyanic acid, otherwise
the action of the catalytic or contact substance would be either destroyed or
very much deteriorated, so that the process must be stopped.
Having thus described the nature of this part of our Invention, and the
manner in which the same may be performed, we would have it understood.
that we do not confine ourselves to the use of platinum, or the particular.
mode or arrangement above described; but we claim as our Invention the
manufacturing of ammoniacal and cyanogen compounds from the oxygen com-
pounds of nitrogen by means of hydrogen gas, or any compound or mixture of
hydrogen with carbon, in conjunction with any catalytic or contact substance,
as herein-before described.
:
And now, lastly, as regards the third part of our Invention, which relates to
our new apparatus. It consists of the vessel marked A, formed of slate or.
wood, for the purpose of manufacturing of acids, as also the vessels for con-
densing vapours or gases, and is as follows; that is to say, P is the body of
the vessel we call a condenser, of which V is the mouth, of such size that the
convex diaphragm W, W, which is perforated, and in two pieces, may be
introduced, and rest on the ledge X round the interior of the body of the
condenser. Y is the exit pipe to receive the long end of the connecting
arm 0; and Z is the cover, with an opening to receive the other end of the
said connecting arm. a, a, are the tubes, with bevelled lower ends resting
on the diaphragm W, W. 6 is one of the tubes. The materials of which
these tubes are formed, when used for the condensation of acid vapours, we
prefer to be of glass; but the choice of material must entirely depend on the
purpose to which it is to be applied. The diameter of the tubes a, a, is about
one eighth of an inch, and the length twelve inches. These are packed as
closely together as possible, so that the exterior portions form passages for the
vapours, and thereby increase the condensing surface; or, instead of tubes,
rods may be employed, or a series of perforated plates or diaphragms, either
overlying one another or supported at a distance the one from the other.
Having thus described the nature of this part of our Invention, and the
manner in which the same may be performed, we would have it understood
that we do not confine ourselves to the size of the tubes above described, as
they may be made of any size, nor to the exact form or material, so long as
the peculiar principle of our Invention be retained. But we claim as our
Invention as regards our said apparatus:-

page_text: First, the use or application of a number of tubes enclosed in a body or
case, by which a large number of passages may be obtained and applied for
the purposes of condensation, as herein-before described; and,
Secondly, the mode of feeding or supplying gradually and proportionally
from the reservoirs F, F, the material to be decomposed.
And now having stated the nature of our said Invention, and the manner in
which the same is to be performed, and such our Invention being, to the best
of our knowledge and belief, entirely new, and never before used within that
part of Her said Majesty's United Kingdom of Great Britain and Ireland
called England, Her said Dominion of Wales, and Town of Berwick-upon-
Tweed, nor in any of Her said Majesty's Islands of Jersey, Guernsey,
Alderney, Sark, and Man, nor in any of Her said Majesty's Colonies or
Plantations abroad, we do hereby declare this to be our Specification of the
same, and that we do verily believe this our said Specification doth comply in
all respects fully, and without reserve or disguise, with the proviso in the said
herein-before in part recited Letters Patent contained, wherefore we hereby
claim to maintain exclusive right and privilege to our said Invention.
In witness whereof, we, the said Charles Crane and James Thomas
Jullion, have hereunto set our hands and seals, this Seventeenth day
of May, One thousand eight hundred and forty-eight.
CHARLES (L.S.) CRANE.
JAMES THOMAS (L.S.) JULLION.
AND BE IT REMEMBERED, that on the Seventeenth day of May, in the
eleventh year of the reign of Her Majesty Queen Victoria, the said Charles
Crane and James Thomas Jullion came before our said Lady the Queen in
Her Chancery, and acknowledged the Instrument aforesaid, and all and every
thing therein contained and specified, in form above written. And also the
Instrument aforesaid was stamped according to the tenor of the Statute made
in the fifty-fifth year of the reign of His late Majesty King George the
Third.