IMPROVEMENTS IN THE TREATMENT OF SACCHARINE JUICES AND SYRUPS
Year: 1872

page_text: LETTERS PATENT to Jean Vincent Prosper Lagrange, of the Firm of
Royer, Lagrange, and Curely, of Paris, Boulevard de Strasbourg,
No. 23, for the Invention of "IMPROVEMENTS IN THE TREATMENT OF
SACCHARINE JUICES AND SYRUPS."
Sealed the 1st November 1872, and dated the 11th May 1872.
PROVISIONAL SPECIFICATION left by the said Jean Vincent Prosper
Lagrange at the Office of the Commissioners of Patents, with his
Petition, on the 11th May 1872.
I, JEAN VINCENT PROSPER LAGRANGE, of the Firm of Royer, Lagrange,
3 and Curely, of Paris, Boulevard de Strasbourg, No. 23, do hereby de-
clare the nature of the said Invention for "IMPROVEMENTS IN THE TREATMENT
OF SACCHARINE JUICES AND SYRUPS," to be as follows :—
In saccharine juices and syrups, independently of other salts, there is
found lime combined with organic and mineral acids. These salts of
lime which carbonation has not been able to decompose exert not only an
injurious action upon the crystallization and the finish of the sugar, but

page_text: render the syrups viscid, make the baking operation difficult to perform,
and, above all, communicate a yellowish tinge to white or loaf sugar.
Of all the agents capable of eliminating these salts of lime which resist
the action of carbonic acid, I have found that the one which presents the
greatest advantage and gives the best result in sugar making and refining
is the tribasic phosphate of ammonia (or phosphate of ammonia with
three equivalents of ammonia, that is to say, one equivalent of phosphoric
acid to three equivalents of ammonia) chemically pure and free from any
other soluble salt. The purity of the tribasic phosphate of ammonia is
indispensable to its application. A badly prepared phosphate of ammonia
may, according to the mode of its preparation, enclose considerable
proportions of sulphate of ammonia, which like all other sulphates exerts
a very injurious action upon sugar. Not only does it cause a loss of
sugar like other salts but it also acidifies the syrups when they are in a
state of ebullition, and "turns" the sugar. It exercises also at a certain
"dose" an action of the greatest consequence upon the sugary products, it
hinders the setting of the caked masses and the draining of the loaves,
it is therefore indispensable to employ in the purification of sugary juices
and syrups only tribasic phosphate of ammonia free from sulphate of
ammonia and chemically pure. A no less weighty reason has deter-
mined me to choose phosphate of ammonia with three equivalents of
ammonia. If phosphate of ammonia with one or two equivalents of
ammonia be employed, two equivalents or one equivalent of organic
acids are set at liberty, and the sugary juices or syrups become acid,
whilst the phosphate of ammonia with three equivalents of ammonia
completely neutralizes the organic acids, and endows the syrups with
alkalinity. Sulphate of ammonia ought to be considered as one of the
most dangerous of salts. In spite of the employment of a chemically
pure phosphate containing three equivalents of ammonia, it will be
always formed by double decomposition of the sulphate of ammonia,
when the crude sugars and the syrups contain sulphate of lime in the
proportions of from 0·10 to 0-50 per cent.
The tribasic phosphate of ammonia forms an insoluble phosphate of
lime and sulphate of ammonia which remains in the syrup. In order to
avoid the formation of the latter salt, and to completely eliminate sul-
phate of lime, I employ hydrate of baryta. The baryta lays hold of the
sulphuric acid of the sulphates in order to form a flaky precipitate of

page_text: insoluble sulphate of baryta, and puts the bases, lime, potash, and soda,
at liberty, according as the sulphuric acid is in the state of sulphate of
lime, potash, or soda. The addition of the tribasic phosphate of ammonia
then comes to lay hold of the lime.
The following is my method of working :—
1st. In Sugar Making. After carbonation I treat the juices and
syrups with a quantity of hydrate of baryta proportionate to the sulphates
contained in these products; then I add the necessary quantity of
tribasic phosphate of ammonia (or phosphate containing three equivalents
of ammonia) in order to eliminate all the lime, and I proceed to the
boiling. A double precipitate of sulphate of baryta and insoluble phos-
phate of lime is formed, and this double precipitate possesses a very
peculiar flaky character, on that account very purifying, and capable of
absorbing organic matters. I then send the mass to the decantees, or
through Taylor or other filters. Phosphate of lime, on account of its
properties of absorbing organic matters, and above all in consequence of
its peculiar affinity for albuminous gelatinous and pectic matters, takes
with it when precipitating a considerable proportion of these organic
matters.
2ndly. The Refining. -I commence the purification of the syrups at
the bakery; I agitate the mixture; all the sulphuric acid of the sulphate
is precipitated in a flaky form. Then I add a solution of phosphate with
three equivalents of ammonia (tribasic phosphate of ammonia) propor-
tionate to the lime contained in the syrup. I obtain an insoluble
phosphate of lime, which is found mixed with sulphate of baryta. The
syrup arriving at the clarifying boilers is carried to the boiling point, the
precipitate (the flakes of which become more and more large under the
influence of the heat) becomes separated and rises to the surface of
the boiler, clarifying the contents thereof admirably. There is therefore
produced at the same time a veritable chemical purification, and an
excellent mechanical clarification. I then send the syrup upon the
Taylor filters, and the operations follow their usual course as in the
ordinary processes.

page_text: facture and refining of the sugar, and especially in cleansing the filters.
The ammonia introduced into the sugary juices and into the syrups
prevents them from spoiling, no matter in what temperatures they may
be, and assures not only their preservation but permits also their being
sent on journeys, or conducted by pipes, or any other means.
The baryta may be added indifferently before or after the phosphate of
ammonia. In the first case sulphate of ammonia is not formed, the
sulphuric acid is removed directly, and the lime which the phosphate
afterwards removes is set at liberty. In the second case phosphate of
lime and sulphate of ammonia are formed, the latter of which the baryta 1
decomposes while setting the ammonia at liberty. Thus in both cases
the same end is attained, viz., the complete elimination of the lime
and the sulphate of lime while avoiding the formation of the sulphate of
ammonia.
The employment of baryta for the elimination of the alkaline sulphates 1
contained in sugars, syrups, and juices has never been made in
refining any more than in sugar making; I therefore am the first to
apply this substance to the elimination of sulphates; I can also replace
the hydrated baryta or not by a double salt, the double fluoride of
baryum and ammonium.
By the aid of this body I can completely eliminate the sulphate of
potash; I therefore eliminate surely two sulphates, the sulphate of lime,
and the sulphate of potash.
It will have been gathered from the preceeding that the points of my
Invention arc,—
1st. The application of baryta to the elimination of sulphates in sugar
making and refining, either separately or simultaneously, in the hydrated
state with phosphate of ammonia containing three equivalents of am-
monia (tribasic phosphate of ammonia).
2nd. The process as above explained for the treatment of saccharine

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent,
filed by the said Jean Vincent Prosper Lagrange in the Great Scal
Patent Office on the 9th November 1872.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, JEAN
VINCENT PROSPER LAGRANGE, of the Firm of Royer, Lagrange, and
Curely, of Paris, Boulevard de Strasbourg, No. 23, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her
Letters Patent, bearing date the Eleventh day of May, in the year of our
Lord One thousand eight hundred and seventy-two, in the thirty-fifth
year of Her reign, did, for Herself, Her heirs and successors, give and
grant unto me, the said Jean Vincent Prosper Lagrange, Her special
licence that I, the said Jean Vincent Prosper Lagrange, my executors,
administrators, and assigns, or such others as I, the said Jean Vincent
Prosper Lagrange, my 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 THE TREATMENT OF SACCHARINE JUICES AND SYRUPS,"
upon the condition (amongst others) that I, the said Jean Vincent
Prosper Lagrange, my executors or administrators, by an instrument in
writing under my, or their, or one of their hands and seals, should
particularly describe and ascertain the nature of the said Invention,
and in what manner the same was to be performed, 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.
NOW KNOW YE, that I, the said Jean Vincent Prosper Lagrange, do
hereby declare the nature of my said Invention, and in what manner
the same is to be performed, to be particularly described and ascer-
tained in and by the following statement thereof, that is to say :-
In saccharine juices and syrups, independently of other salts, there is
found lime combined with organic and mineral acids. These salts of
lime which carbonation has not been able to decompose exert not only
an injurious action upon the crystallization and the finish of the sugar,
but render the syrups viscid, make the baking operation difficult to per-

page_text: form, and, above all, communicate a yellowish tinge to white or loaf
sugar. Of all the agents capable of eliminating these salts of lime
which resist the action of carbonic acid I have found that the one which
presents the greatest advantages and gives the best result in sugar
making and refining is the tribasic phosphate of ammonia (or phos-
phate of ammonia with three equivalents of ammonia, that is to say, one
equivalent of phosphoric acid to three equivalents of ammonia) chemi-
cally pure and free from any other soluble salt. The purity of the
tribasic phosphate of ammonia is indispensable to its application. A
badly prepared phosphate of ammonia may, according to the modo of
its preparation, enclose considerable proportions of sulphate of ammonia,
which like all other sulphates exerts a very injurious action upon sugar.
Not only does it cause a loss of sugar like other salts, but it also acidifics
the syrups when they are in a state of ebullition, and "turns” the sugar.
It exercises also at a certain "dose" an action of the greatest conse-
quence upon the sugary products, it hinders the setting of the caked
masses, and the draining of the loaves "titlers." It is therefore
indispensable to employ in the purification of sugary juices and syrups
only tribasic phosphate of ammonia free from sulphate of ammonia, and
chemically pure. A no less weighty reason has determined me to choose
phosphate of ammonia with three equivalents of ammonia. If phosphate
of ammonia with one or two equivalents of ammonia be employed, two
equivalents, or one equivalent of organic acids are set at liberty, and the
sugary juices or syrups become acid, whilst the phosphate of ammonia
with three equivalents of ammonia completely neutralizes the organic
acids, and endows the syrups with alkalinity. Sulphate of ammonia
ought to be considered as one of the most dangerous of salts. In spite
of the employment of a chemically pure phosphate containing three
equivalents of ammonia it will be always formed by double decomposition
of the sulphate of ammonia, when the crude sugars and the syrups con-
tain sulphate of lime in the proportions of from 0·10 to 0.50 per cent.
The tribasic phosphate of ammonia forms an insoluble phosphate of
lime and sulphate of ammonia, which remains in the syrup. In order
to avoid the formation of the latter salt, and to completely eliminate
sulphate of lime, I employ hydrate of baryta. The baryta lays hold of
the sulphuric acid of the sulphates in order to form a flaky precipitate
of insoluble sulphate of baryta, and puts the bases, lime, potash, and

page_text: soda at liberty, according as the sulphuric acid is in the state of sulphate
of lime, potash, or soda. The addition of the tribasic phosphate of
ammonia then comes to lay hold of the lime.
The following is my method of working:―
1st. In Sugar Making.-I treat the juices and syrups with a quantity
of hydrate of baryta proportionate to the sulphates contained in theso
products; then I add the necessary quantity of tribasic phosphate of
ammonia (or phosphate containing three equivalents of ammonia) in
order to eliminate all the lime, and I proceed to the boiling. A double
precipitate of sulphate of baryta and insoluble phosphate of lime is
formed, and this double precipitate possesses a very peculiar flaky
character, on that account very purifying, and capable of absorbing
organic matters. I then send the mass to the decanters, or through
Taylor or other filters. Phosphate of lime, on account of its properties
of absorbing organic matters, and above all in consequence of its peculiar
affinity for albuminous, gelatinous, and pectic matters, takes with it
when precipitating a considerable proportion of these organic matters.
2ndly. The Refining.-I commence the purification of the syrups at
the bakery. I dispense with blood and fine animal black, and I use
in their place hydrate of baryta in the proportion of the sulphates con-
tained in the syrups. I agitate the mixture; all the sulphuric acid of
the sulphates is precipitated in a flaky form; then I add a solution of
phosphate with three equivalents of ammonia (tribasic phosphate of
ammonia) proportionate to the lime contained in the syrup. I obtain
an insoluble phosphate of lime, which is found mixed with sulphate of
baryta. The syrup arriving at the clarifying boilers is carried to the
boiling point, the precipitate (the flakes of which become more and more
large under the influence of the heat) becomes separated, and rises to
the surface of the boiler, clarifying the contents thereof admirably.
There is therefore produced at the same time a veritable chemical
purification, and an excellent mechanical clarification. I then send the
syrup upon the Taylor filters, and the operations follow their course as
in the ordinary processes.
3rdly. Sugar Making and Refining.-I employ variable doses of
ammoniacal water, as described in the Specification of my Patent dated
23rd day of November 1871, No. 3180, at all temperatures in the various

page_text: phases of the manufacture and refining of the sugar, and especially in
cleansing the filters. The ammonia introduced into the sugary juices
and into the syrups prevents them from spoiling, no matter in what
temperatures they may be, and assures not only their preservation, but
permits also their being sent on journeys, or conducted by pipes or E
any other means.
The baryta may be added indifferently before or after the phosphato
of ammonia. In the first case sulphate of ammonia is not formed, the
sulphuric acid is removed directly, and the lime which the phosphate
afterwards removes is set at liberty. In the second case phosphate of 1
lime and sulphate of ammonia are formed, the latter of which the baryta
decomposes while setting the ammonia at liberty. Thus in both cases
the same end is attained, viz., the complete elimination of the lime and
the sulphate of lime, while avoiding the formation of the sulphate of
ammonia.
J
The employment of baryta for the climination of the alkaline sul-
phates contained in sugars, syrups, and juices has never been made in
refining any more than in sugar making; I therefore am the first to
apply this substance to the elimination of sulphates; I can also replace
the hydrated baryta or not by a double salt, the double fluoride of 5
baryum and ammonium.
By the aid of this body I can completely climinate the sulphate of
potash, I therefore climinate surely two sulphates, the sulphate of lime,
and the sulphate of potash.
And having now described the nature of my said Invention, and in
what manner the same is to be performed, I declare that I claim as my
Improvements in the Treatment of Saccharine Juices and syrups,”-
66
1stly. The employment of pure tribasic phosphate of ammonia (that is
to say, phosphate of ammonia containing three equivalents of ammonia
to one of phosphoric acid), cither alone or simultaneously with baryta, a
for the purposes and in the manner herein-before described.
2ndly. The employment of caustic or hydrated baryta, either alone or
followed by the employment of tribasic phosphate of ammonia, for the
purpose of eliminating the sulphuric acid held in the condition of sul-
phates in saccharine juices and syrups, as herein-before described.

page_text: And, 3rdly. The treatment substantially as herein-before described for
operating upon saccharine juices and syrups.
In witness whereof, I, the said Jean Vincent Prosper Lagrange,
have hereunto set my hand and seal, this Fourth day of No-
vember One thousand cight hundred and seventy-two.
J. V. P. LAGRANGE. (L.S.)
Witness,
Charles ArmenGAUD, JEUNE,
Civil Engineer,
Boulevard de Strasbourg, No. 23,
Paris.