IMPROVEMENTS IN THE MANUFACTURE OF CERTAIN ACIDS; ALSO IMPROVEMENTS IN DECOMPOSING CERTAIN ACIDS, AND APPLYING THE PRODUCTS RESULTING THEBEFROM TO THE PRODUCTION OF CERTAIN CHEMICAL COMPOUNDS
Year: 1846

page_text: TO ALL TO WHOM THESE PRESENTS SHALL COME, I, JAMES
THOMAS JULLION, of Stratford, in the County of Essex, Analytical Chemist,
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 Twenty-second day of October, in the tenth year of Her
reign, did, for Herself, Her heirs and successors, give and grant unto me, the
said James Thomas Jullion, Her especial license, that I, the said James
Thomas Jullion, my executors, administrators, and assigns, or such others as I,
the said James Thomas Jullion, my 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, the Town of Berwick-
upon-Tweed, and in the Islands of Jersey, Guernsey, Alderney, Sark, and
Man, and also in all Her Colonies and Plantations abroad, my Invention of
"IMPROVEMENTS IN THE MANUFACTURE OF CERTAIN ACIDS; ALSO IMPROVEMENTS IN
DECOMPOSING CERTAIN ACIDS, AND APPLYING THE PRODUCTS RESULTING THEBEFROM
TO THE PRODUCTION OF CERTAIN CHEMICAL COMPOUNDS;" in which said Letters
Patent is contained a proviso obliging me, the said James Thomas Jullion,
by an instrument in writing under my hand and seal, particularly to describe
and ascertain the nature of my said Invention, and in what manner the
same is to be performed, and to cause the same to be enrolled in Her

page_text: 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.
NOW KNOW YE, that in compliance with the said proviso, I, the said
James Thomas Jullion, do bereby declare that the nature of my said
Invention to consist (first, as regards my improvements in the manufacture of
certain acids) in the collecting of those gases and vapours, being oxides of
nitrogen, which are usually allowed to escape in the manufacture of oxalic
acid and other substances, and treating them with oxygen and otherwise, as
herein-after described, and so producing nitrous and nitric acids from what is
usually wasted; also the production of sulphuric acid by the decomposition
of water by means of chlorine and sulphurous acid, as herein-after described.
And secondly (as regards my improvements in decomposing certain acids, and
applying the products resulting therefrom to the production of certain chemical
compounds), my Invention consists in decomposing hydrochloric acid and
formic acid, as herein-after described, and in applying the oxalates produced
from the said decomposition of formic acid to the production of oxalic acid and
binoxalate of potash. And in further compliance with the said proviso, I, the
said James Thomas Jullion, do hereby describe the manner in which my said
Invention is to be performed, by the following statement thereof, reference
being had to the Drawing annexed and to the letters of reference marked
thereon; and I will proceed at once to give a short description of the apparatus
shewn by the Drawing, in order that the description of my various processes
may be more readily understood.
DESCRIPTION OF THE DRAWING.
A, the decomposing vessel set in a water bath. B, the water bath, to be
heated with steam. C, large stoppered opening for introducing the materials and
their withdrawal by means of a syphon. D, small stoppered opening for intro-
ducing a thermometer to ascertain the temperature of the liquor. E, pipe for
supply of atmospheric air or oxygen, to be connected with a gas holder or blast
pump. I, cover to vessel, ground air-tight. G, exit pipe connected with
main. H, tho main. J, vessel or tube containing platinum, or other contact
substance. K, the furnaco by which the vessel J is heated. L, dip arm or
refrigerating pipe. M, M, M, part of a series of two-necked receivers for
condensation. N, terminal dip pipe. O, exit pipe for waste gasses.
I will now proceed to describe the mode of operating with this apparatus in
order to carry into effect the first part of my Invention, which relates to
A. the decomposing vessel set in a water bath. B, the water bath, to be
heated with steam. C, large stoppered opening for introducing the materials and
their withdrawal by means of a syphon. D, small stoppered opening for intro-
ducing a thermometer to ascertain the temperature of the liquor. E, pipe for
supply of atmospheric air or oxygen, to be connected with a gas holder or blast
pump. F, cover to vessel, ground air-tight. G, exit pipe connected with
main. H, the main. J, vessel or tube containing platinum, or other contact
substance. K, the furnaco by which the vessel J is heated. L, dip arm or
refrigerating pipe. M, M, M, part of a series of two-necked receivers for
condensation. N, terminal dip pipe. O, exit pipe for waste gasses.
I will now proceed to describe the mode of operating with this apparatus in
order to carry into effect the first part of my Invention, which relates to

page_text: Improvements in the Manufacture of certain Acids. In the first place, instead
of using the ordinary jars or open vessels for the manufacture for instance of
oxalic acid, I place the mother liquid, together with the organic substance to
be acted upon, in closed or covered vessels formed of earthenware (which I pro-
pose to call decomposing vessels) capable of containing about one hundred
gallons each, having the necessary pipes and openings, as shewn in the accom-
panying Drawing, which represents the apparatus I employ for the pur-
pose. A is a decomposing vessel, of which there may be several if required.
These vessels are set in a water bath B, which is heated by steam or in any
other convenient manner. The materials to be operated upon are supplied to
the decomposing vessel through the aperture C, which is stoppered, and when
the materials are decomposed the residuum or products are withdrawn from the
vessel through the same aperture by means of a syphon. A small stoppered
opening D is made in the air-tight cover F for the purpose of applying a
thermometer to ascertain the temperature of the contents of the vessel, and E
is a pipe for supplying the vessel with atmospheric air or oxygen. The gases
evolved from the decomposition of the materials in the vessel A pass off' through
the pipe G to the main F. The pipe E for the supply of atmospheric air or
oxygen gas is connected with a gas holder, so that a proper supply of air or
gas may always be maintained in the vessel A, or it may be drawn in by an
exhausting apparatus, arranged suitably for the purpose. The main H is con-
nected with a vessel or tube J. filled with platinum in the stato of sponge, or
the mineral known as asbestos, coated or covered with platinum, which tube is
kept at an elevated temperature by means of the furnace K. I prefer heating
the vessel J to from six hundred to nine hundred degrees of Fahrenheit's
thermometer, but do not confine myself to that heat. The apparatus being
properly connected and arranged, and a portion of nitric acid having
been added, in the usual way for making oxalic acid, to the contents of
the decomposing vessel A; heat is applied to it. As soon as decomposi-
tion of the materials commences, and the gases or oxides of nitrogen
begin to be liberated, I blow or force through the pipe E into the
decomposing vessel, and directly upon the surface of its contents, a regular
stream of oxygen gas or atmospheric air, either at common temperatures or in
a heated state; by which means the oxides of nitrogen are converted into higher
states of oxidation, one portion remaining in the liquor, and another portion,
by condensing with aqueous vapour on the cooler parts of the vessel, being
returned to the said liquor and there performing the same part as a new
addition of nitric acid, and thus diminishing the quantity of nitric acid required
to complete the operation; and the remainder of the gases which have escaped

page_text: condensation pass off in conjunction with the excess of oxygen or atmospheric
air through the exit pipe G into the main H, by which they are conducted
into the tube J, containing the platinum or platinized asbestos, where a com-
bination takes place with the formation of nitrous and nitric acids. Tho
acids so produced, together with the excess of oxygen or atmospheric air, must
be must be passed through a pipe L. into a condensing apparatus, which
should be formed of a series of vessels M, M, of a description similar to those
used in the ordinary process of manufacturing or distilling nitric acid, in
which water or dilute nitric acid should be placed. The delivering or exit
pipe N from the last of these receivers should be made to dip about an inch or
an inch and a half into water or dilute nitric acid in another vessel M, so as
to place the condensing acids under slight pressure, and the uncondensed
vapours may pass off through the exit pipe O. Care should be taken in this
process that such a quantity of atmospheric air or oxygen gas be supplied to
the decomposing vessel that a portion of oxygen shall still be mingled with the
gases that pass off through the water after the conversion of the whole of
the oxides of nitrogen into nitrous and nitric acids. In all cases where the
oxides of nitrogen are comparatively dry, as in the early part of the process
for manufacturing oxalic acid, when the heat employed for the decomposition
of the materials is insuflicient to raise any great amount of water in the state
of vapour, I recommend that a jet of steam should be passed, along with
the mixed gases, through the tube containing the platinum or platinized
asbestos, the presence of aqueous vapour greatly assisting the formation of
nitric acid.
Ju the foregoing process for the conversion of the oxides of nitrogen into
nitrous and nitric acid, I do not confine myself to the use of platinum only.
but any of the substances known to chemists ns catalytic or contact sub-
stances may be employed, of which mention has only been made of platinum
Instead of the platinum and tube J, a closed vessel
used, which decomposes hyponitrous and nitrous acids,
as a type of the class.
containing water may be
giving rise to nitric acid.
This principle I have applied in the following ways
(that is to say):-The oxides of nitrogen as evolved from the liquor in the
decomposing vessel as before mentioned coming in contact with oxygen as
already described, are converted into hyponitrous or nitrous acid, which upon
being mingled with steam are decomposed into nitric acid and binoxide of
nitrogen, or the introduction of steam may be obviated by using heated air or
oxygen in the decomposing vessel, by which means moisture will be furnished
from the liquor; the amount of evaporation thus caused will also prevent an
inconvenient increase in the quantity of mother liquor. The compounds thus

page_text: ormed are then passed into a refrigerating vessel or apparatus, which may be
either an earthenware worm surrounded by water, or a series of receivers,.
such as are ordinarily used for the condensation of nitric acid, and if the
atmospheric air or oxygen so supplied has been in slight excess the whole of
the gases, or nearly all, will be condensed as a nitric acid. It may be as well
here to observe, that by forcing in atmospheric air or oxygen gas at any other
part of the apparatus than as described, the same effect as far as regards the
conversion of the gaseous oxides of nitrogen into hyponitrous, nitrous, and
nitric acids may be obtained.
Having described the nature of this part of my Invention, and the appli-
cation of the same to the manufacture of oxalic acid, it must be evident that
in any other operation where nitric acid may be applied to impart oxygen a
similar or slightly modified arrangement to suit the peculiar circumstances
may be adopted. And I would have it understood, that I do not confine myself
to the oxygenation of the gas or gases arising from the manufacture of oxalic
acid only, but what I do claim is the conversion of any of the compounds of
nitrogen into hyponitrous, nitrous, and nitric acids in closed vessels, and by
the addition of oxygen gas or atmospheric air as herein-before described.
The first of these
Secondly, for the purpose of manufacturing sulphuric acid, I decompose
water by means of chlorine in conjunction with sulphurous acid, when
sulphuric and hydrochloric acids are obtained. The apparatus used in this
process may be an ordinary Woolfe's apparatus, consisting of a vessel which,
when used for my process, I call a conversion vessel, and which may be made
of earthenware, having three openings, into each of which a pipe may be fitted,
either by grinding or otherwise, so as to be air-tight, and capable of bearing
an atmospheric pressure equal to about one foot of water.
pipes serves for the admission of sulphurous acid, and may be connected with
a furnace or other convenient apparatus for the generation of sulphurous
acid under pressure; the second pipe serves for the transmission of chlorine
gas from the chlorine apparatus, and the third should be connected with a
The pipes for
series of receivers for the condensation of hydrochloric acid.
the supply of the sulphurous acid and chlorine gases dip below the surface of
the water, the admission of the gases into the conversion vessel being regulated
by stopcocks. There is likewise another opening for the admission of water
and withdrawal of its contents, and which has a plug or stopper ground to fit
air-tight. This conversion vessel is so arranged that heat may be applied to
it either by a sand bath, or by the passage of hot air round its side and under
The whole having been
its bottom, or by any other convenient method.
properly arranged and supplied with water, sulphurous acid and chlorine may

page_text: be admitted by opening the stopcocks, when they will be condensed by the
water, which will be decomposed, its oxygen combining with the sulphurou
acid forming sulphuric acid, and its hydrogen combining with the chlorine
forming hydrochloric acid. The hydrochloric acid may be expelled from th
sulphuric acid by applying heat to the conversion vessel, which will cause the
hydrochloric acid to pass over in the gaseous state into a series of condensing
vessels, having water at the bottom, where it will be absorbed and form liquid
hydrochloric acid. The sulphuric acid may then be withdrawn from the con-
version vessel by means of a syphon, and placed in vessels for use.
Or a
saturated solution of sulphurous acid may be formed by passing sulphurous
acid into the water contained in the conversion vessel, and when no more is
absorbed chlorine may be passed into it: water will be decomposed as before
with the formation of sulphuric and hydrochloric acids. The latter may be
driven off and condensed as before described. Or a solution of chlorine may
be formed by passing chlorine into the water contained in the conversion
vessel, and when saturated, sulphurous acid may be passed into it. The
contents of the conversion vessel may be heated, if that be preferred, during
the process, so as to accelerate the operation; and should the temperature of
the liquid be raised to the point of ebullition the distillation of the hydro-
chloric acid will take place simultaneously with the formation of sulphuric
neid; or the chlorine and sulphurous acid gases may be mixed together in
equal volumes in the decomposing vessel of the apparatus herein-before
described, and passed through that apparatus: a jet of steam being substi-
tuted for the jet of air before described, and no platinum being required in the
tube, when the same reaction will take place with the formation of sulphuric
and hydrochloric acids. The tube here referred to I call the conversion tube,
which may be connected with an earthenware worm or other convenient
apparatus surrounded with water, which water may be maintained at a
temperature of 212° of Fahrenheit's thermometer. This arrangement will
have the effect of condensing the sulphuric acid which will remain in the first
receiver, while the hydrochloric acid will pass on into a series of receivers, in
which water has been placed, where it will be condensed.
I do not confine myself to any particular form or arrangement of apparatus
in this process, as it will admit of considerable variation, but what I claim is
the manufacturing of sulphuric acid by decomposing water by means of a
sulphurous acid and chlorine.
The second part of my Invention, which relates to "Improvements in De-
composing certain Acids," consists, firstly, in decomposing hydrochloric acid by
oxygen gas by means of certain substances, as follows (that is to say), hydro-

page_text: chloric acid, as obtained from chloride of sodium by means of sulphuric acid,
is to be rendered as dry as may be by passing it over chloride of calcium
which has been fused, and is contained in a vessel which I term the desiccating
vessel; or it may be passed through sulphuric acid or up a pipe filled with flint
or other convenient matter, and which matter is kept continually moistened by
a stream of sulphuric acid trickling downwards. The hydrochloric acid gas by
either of these methods is rendered sufficiently free from water for the purpose
of decomposition by oxygen, which I will now proceed to describe. One
volume of hydrochloric acid gas is to be mingled with half its volume of
oxygen gas; the mixed gases are then to be passed through a tube or furnace
containing platinum in the state of sponge, or the mineral known as asbestos
coated or covered with platinum, as shown in the Drawing annexed, which
tube or furnace must be kept at an elevated temperature, preference being to
a range of from 300° to 600° Fahrenheit's thermometer; decomposition of the
hydrochloric acid takes place with the formation of water and liberation of
chlorine in the gaseous state, which, having been cooled by any convenient
method, may then be passed through a small quantity of water to purify the
gas from any hydrochloric acid that may have escaped decomposition, where it
would be condensed, and the chlorine may be employed for any of the purposes
to which chlorine is applicable. In this process for the decomposing bydro-
chloric acid I do not confine myself to the use of platinum only, but any of
the substances known to chemists as catalytic or contact substances may be
employed, of which, as I have before stated, platinum has been mentioned as
a type of the class.
Having thus described the nature of this part of my Invention, and the
manner in which the same may be performed, I would have it understood that
I claim as my Invention the decomposition of hydrochloric acid by means of
oxygen gas, in conjunction with platinum or any other catalytic substance, at
an elevated temperature. Secondly, formic acid is to be saturated by a solution
of caustic or hydrate of potash, and to the solution so obtained an excess of
solution of caustic potash is to be added, which excess I prefer to amount to
one half of the quantity that was required to saturate the formic acid. The
whole is then to be evaporated and heated to a temperature not exceeding
560° of Fahrenheit's thermometer; swelling of the mass ensues with the
liberation of gas, and when that has subsided the operation may be judged to
be complete. The formic acid by this process will be found to have been
converted into oxalic acid, which will be in combination with a portion of
the potash or oxalate of postash. Or formic acid may be saturated by carbonate
of potash or sulphurate of potassium, or formiate of potash may be formed by

page_text: decomposing any earthy or metallic formiate by a salt of potash. The solution
of formiate of potash so obtained may then be evaporated to dryness and
mixed with caustic potash in the proportion of eighty-five parts of dried
formiate of potash to thirty parts of fused caustic potash. The fused caustic
potash is then to be dissolved in water, and the whole is to be treated as
before described. In these cases where potash is mentioned soda may be
substituted for the potash, when oxalate of soda will be obtained. When
formiate of soda is employed the proportions may be sixty-nine parts of dried
formiate of soda to twenty parts of caustic soda, which is also called fused or
hydrate of soda. Any of the alkaline earths may be used in this process in
lieu of the alkalies, if preferred.
Having thus described the nature of this part of my Invention, I would
have it understood that I claim as my Invention the decomposing of formic
acid, when in combination with any alkali or alkaline earths, as aforesaid, by
heating or fusing those combined substances together with an additional
quantity or excess of any alkali or alkaline earth, as herein-before described.
The third part of my Invention, which relates to "Applying the Products
resulting therefrom to the Production of certain Chemical Compounds," consists
in decomposing the oxalates produced as just described by a solution of sul-
phuret of barium, bydrate of baryta, or of any of the soluble salts of baryta,
and which is to be performed by adding to the solution of such oxalate a
solution of sulphuret of barium until no further precipitate be obtained, when
oxylate of baryta subsides in the form of a white powder. The solution
having been drawn from off the precipitate, the latter is to be washed with
clear water to free it from any soluble matter, when it will be ready for
decomposing by sulphuric acid. For this purpose forty-nine parts of sulphuric
acid, sp. gr. 1.845, is to be diluted with twice its weight of water, and poured
upon one hundred and twenty-two parts of oxalate of baryta, when sulphate.
of baryta will be formed, and a solution of oxalic acid obtained, which latter
may be evaporated to procure the oxalic acid in the crystalline state. Or the
oxalate of baryta may be decomposed by a solution of bisulphate of potash,
when sulphate of baryta will be formed as before, and a solution of binoxalate
of potash will be obtained. The solution of bisulphate of potash may be
formed by dissolving in water eighty-eight parts of sulphate of potash, and
adding thereto forty-nine parts of sulphuric acid, specific gravity 1.845, which
quantity will be sufficient to decompose two hundred and forty-four parts of
oxalate of baryta. The solution of binoxalate of potash may be evaporated
so as to obtain crystals of the binoxalate of potash upon couling. And as
regards this part of my said Invention I claim the production of oxalic acid

page_text: and binoxalate of potash from the oxalates produced, as herein-before described,
from the decomposition of formic acid.
And such my said Invention being, to the best of my 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 or Town of Berwick-upon-Tweed, nor in
either 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,
I do hereby declare this to be my Specification of the same, and that I do
verily believe this my 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 I hereby claim to main-
tain exclusive right and privilege to my said Invention.
In witness whereof, 1, the said James Thomas Jullion, have hereunto set
my hand and seal, this Twenty second day of April, in the year of our
Lord One thousand eight hundred and forty-seven.
JAMES THOMAS JULLION. (L.S.)
AND BE IT REMEMBERED, that on the same Twenty-second day of
April, in the year above mentioned, the aforesaid James Thomas Jullion
20 came before our Lady the Queen in Her Chancery, and acknowledged the
Specification aforesaid, and all and every thing therein contained, in form
above written. And also the Specification aforesaid was stamped according
to the tenor of the Statute in that case made and provided.
daw of Annil in the rose above writton