IM- PROVEMENTS IN THE MANUFACTURE OF AGENTS FOR THE PURIFICATION OF SEWAGE AND FOR OTHER PURPOSES
Year: 1877

page_text: [FOURNIER'S PATENT.]
En the Matter of a Patent granted to GEORGE FOURNIER, of No. 42, Boulevart
de Strasbourg, in the City of Paris, Chemist, for the Invention of "IM-
PROVEMENTS IN THE MANUFACTURE OF AGENTS FOR THE PURIFICATION OF
SEWAGE AND FOR OTHER PURPOSES," bearing date the 14th day of August,
A.D. 1877, No. 3096.
DISCLAIMER AND MEMORANDUM OF ALTERATION proposed to be
entered by The Native Guano Company, Limited, pursuant to the Statutes in
that case made and provided.
(Limited),
WHEREAS since the filing of the Specification of the Letters Patent granted
to George Fournier, the same have been assigned, and are now vested in the Native
Guano Company, A and the said assignees have been advised that the claim made in
the said Specification taken in connexion with the description of the Invention is
too wide, and may be construed as claiming more than was intended to be claimed,
and therefore that so much thereof as relates to the refrigeration of the mixturés
therein referred to should be amended, so as to limit the claim in that respect to
the use of a process of artificial refrigeration by the use of a refrigerant at tempera-
tures below 32° Fahrenheit, we, the said Native Guano Company, therefore wish
to amend the said Specification by striking out the words "either natural or
artificial, say a temperature," on line 38, page 3 of the Specification, as printed by
the Queen's Printers, and substituting the words artificially applied, the tempera-
ture thereof being, and by striking out the brackets enclosing the sentence beginning
with the said word "say," and ending with the word "Fahrenheit," and by inserting
Driss 31

page_text: "
Anal Specification when thus altered will read as follows.
" TO ALL TO WHOM THESE PRESENTS SHALL COME, I, GEORGE
FOURNIER, of No. 42, Boulevart de Strasbourg, in the City of Paris, Chemist,
" send greeting.
"
66
6. " WHEREAS Her most Excellent Majesty Queen Victoria, by Her Letters
"Patent bearing date the Fourteenth day of August, in the year of our Lord One
"thousand eight hundred and seventy-seven, in the Forty-first year of Her reign, did
" for herself, her heirs and successors, give and grant unto me, the said George
"Fournier, Her special license that I, the said George Fournier, my executors,
" administrators, and assigns, or such others as I, the said George Fournier, 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 MANUFACTURE OF AGENTS
"FOR THE PURIFICATION OF SEWAGE AND FOR OTHER PURPOSES," upon the condition
(amongst others) that I, the said George Fournier, 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 iminediately
"after the date of the said Letters Patent :-
«
"
"NOW KNOW YE, that I, the said George Fournier, do hereby declare the
"nature of the said Invention, and in what manner the same is to be performed,
"to be particularly described and ascertained in and by the following statement
thereof, that is to say:-
"
"1
My Invention relates to the manufacture of the chlorides of aluminium and
"iron, which substances or agents are used in the treatment of sewage and other
foul waters, and for other purposes.
"
"
"6
My said Invention consists of the improvements herein-after described in the
"manufacture of the said chlorides of aluminium and iron, by which improvements
I so prepare these agents that the cost thereof shall be wholly or in great
part defrayed by the bye products which I obtain in the course of their manu-
❝ facture.
"
"
6
I take pyritic schists or shales, and either roast them or expose them to the
"weather until a considerable portion of the sulphur present has been oxidised
"to sulphuric acid, which forms sulphates with the iron and alumina contained
" in the said schists or shales. (In case the schist or shale is not sufficiently pyritic,
"I make it so by adding pyrites:) After roasting or exposing the said schists or
shales, I lixiviate them with water, and place the resulting lixivium in suitable
vessels in contact or admixture with iron, either cast iron, sheet iron, scrap iron,
" iron borings, or iron of any kind in a sufficiently divided state, my object in
doing this being to reduce all iron present in the said lixivium to the state of a
proto salt. This result is obtained in about 48 hours, or it can be hastened by
heating the said lixivium in contact with the iron. The density of the liquor
"which previous to this treatment would be about 28° to 30° Beaumé is thus
increased to about 33° to 35°. I then draw off the liquor from the aforesaid
vessels, which I then recharge with more lixivium to be treated in the same way.
I concentrate the liquor by heat (after its treatment with the iron) to about
"38° Beaumé, and leave it to crystallize, and on cooling it deposits crystals of
sulphate of iron (copperas) equal to about 10 to 12 per cent. of the weight of the
"concentrated liquor. I thus eliminate part of the sulphuric acid and iron in the
"
«
"
"

page_text: <6
<
"form of the sulphate of iron aforesaid, which is a valuable bye product. Thus
"far my process is similar to some of the processes by which alum has been
prepared from aluminous shists or schales. I mix the mother liquids remaining
"after the crystallization of the sulphate of iron with an equivalent quantity of
"chloride of sodium (common salt), so as to cause an exchange to take place
"between the acids and the bases, and I submit the mixture to the action of cold
artificially applied, the temperature thereof being below 32° Fahrenheit. Under
"the influence of the low temperature, sulphate of soda is deposited in crystals
by reason of its being almost insoluble in water, cooled below 32° Fahrenheit,
" and a solution of chloride of aluminium and chloride of iron remains, which does
"not solidify at that temperature; I then take out the crystals of sulphate of
"soda. I thus obtain the said chlorides of aluminium and iron for use in pre-
cipitating sewage, or for other purposes in addition to the sulphate of iron and
sulphate of soda, the sale of which bye products will defray or reduce the cost of
"the solution of chloride of aluminium and chloride of iron.
The mother liquor
containing the said chlorides of aluminium and iron may be either run direct
" into the sewage to be treated, or it may be evaporated until it will form a nearly
"solid mass on cooling.
"
"
«
"If desirable the crystals of sulphate of iron aforesaid may be dissolved in water,
"and the solution may be treated with an equivalent quantity of chloride of
"sodium, and refrigerated so as to obtain sulphate of soda and chloride of iron.
"C
"
"
"
"
"The operations of adding chloride of sodium to solutions containing sulphates,
" and refrigerating, as herein-before described, may be applied with advantage in
processes in which sulphates of iron or sulphates of alumina are used, either
together or separately, for the treatment of sewage, the said operations trans-
forming the sulphate of iron into sulphate of soda, and chloride of iron and
"the sulphate of alumina into sulphate of soda and chloride of aluminium ;
thus, for instance, I add chloride of sodium to a solution of commercial
sulphate of alumina, and I refrigerate the mixture as herein-before described.
"In some cases instead of treating the lixivium from the shale with iron, as
"herein-before described, I omit that stage of my process, and concentrate the said
" lixivium without treating it with iron, and allow the sulphate of iron contained
"in the said lixivium to crystallize out on cooling, and then treat the mother liquid
"with chloride of sodium and refrigerate, as herein-before described. This gives
"a smaller yield of sulphate of iron and a less neutral residue of the chlorides of
"aluminium and iron than the process herein first described.
"In some cases, instead of crystallizing out the sulphate of iron after digesting
or boiling the aforesaid lixivium with metallic iron, I mix the said lixivium (after
digesting or boiling, as aforesaid) with chloride of sodium, and then refrigerate,
"and thus obtain a larger quantity of sulphate of soda than by either of the
foregoing processes, and a larger quantity of chloride of iron in the residue.
"When it is desirable to save time, and where the purity of the products is not
"of much importance, I take the lixivium resulting from the lixiviation of the
shale, as aforesaid, and (without treating it with iron and concentrating, as
"herein-before described) add chloride of sodium to the said lixivium, and
refrigerate the mixture, as herein-before described. I thus obtain sulphate of
"soda in crystals, and the mother liquor containing the chlorides of aluminium
"and iron.
"
"
«
Having thus described the nature of my Invention, and the manner in which
"it is to be performed, I wish it to be understood that I do not limit myself to
"the precise details described, as they may be varied without departing from the
"nature of my Invention, and that I do not claim per se either the lixiviation
"of the shale or the treatment of the resulting lixivium with iron, or the concen-
"tration by heat of the resulting liquor, nor do I claim, per se, the addition of
"chloride of sodium to the said liquor, but I claim as my said Invention the im-
provements herein-before described in the manufacture of chloride of aluminium,
66

page_text: "chloride of iron, and sulphate of soda, that is to say, adding chloride of sodium to
"the mother liquors or solutions, herein-before referred to, and then artificially
refrigerating the mixture, essentially as herein-before described."
"
.
In witness whereof, we, the said Company, have hereunto caused our common
seal to be affixed, this Fifth day of June, in the year of our Lord One 5
thousand eight hundred and seventy-eight.
I hereby grant my Fiat, giving leave to the above-named Company (The
Native Guano Company, Limited), as assignees of the Letters Patent granted to
George Fournier, to file in the Great Seal Patent Office, with the Specification
to which the same relates, the above written Disclaimer and Memorandum of
Alteration.
HARDINGE GIFFARD,
Solicitor-General.

page_text: "
LETTERS PATENT to George Fournier, of No. 42, Boulevart de Strasbourg,
in the City of Paris, Chemist, for the Invention of IMPROVEMENTS IN THE
MANUFACTURE OF AGENTS FOR THE PURIFICATION OF SEWAGE AND FOR
OTHER PURPOSES."
Sealed the 20th October 1877, and dated the 14th August 1877.
PROVISIONAL SPECIFICATION left by the said George Fournier at the
Office of the Commissioners of Patents on the 14th August 1877.
.
GEORGE FOURNIER, of No. 42, Boulevart de Strasbourg, in the City of Paris,
Chemist. "IMPROVEMENTS IN THE MANUFACTURE OF AGENTS FOR THE PURIFI-
CATION OF SEWAGE AND FOR OTHER PURPOSES."
My Invention relates to the manufacture of the chlorides of aluminum and iron,
which substances or agents are used in the treatment of sewage and other foul waters,
and for other purposes.
My said Invention consists of the improvements herein-after described in the
manufacture of the said chlorides of aluminum and iron, by which improvements I
so prepare these agents that the cost thereof shall be wholly or in great part
defrayed by the bye products which I obtain in the course of their manufacture.
In making the chlorides of aluminum and iron according to my Invention I pro-
ceed as follows:-I lixiviate roasted or unroasted aluminous schists with water and
boil the resulting lixiviation in suitable vessels for about 48 hours in contact or
admixture with iron, either cast iron, sheet iron, scrap iron, iron borings, or iron in
any other form, my object in doing this being to reduce all iron present to the state
of a proto salt. The density of the liquor, which previous to this boiling was
about 28° to 30° Beaumé, is increased by the boiling to about 33° to 35°. I then
draw off the boiled liquor from the aforesaid vessels, which I then recharge with
more liquor to be boiled. I concentrate the boiled liquor by heat while hot to
about 38° Beaumé and leave it to settle, and on cooling it deposits crystals of
sulphate of iron (copperas) equal to about 10 to 12 per cent. of the weight of the
concentrated liquor. I thus eliminate part of the sulphuric acid and iron in the
Illains 11

page_text: form of the sulphate of iron aforesaid, which is a valuable bye product. Thus far
my process is similar to some of the processes by which alum has been prepared
from aluminous schists. I mix the mother liquors remaining after the crystallization
of the sulphate of iron with a sufficient quantity of chloride of sodium (common
salt), and submit the mixture to the action of cold, either natural or artificial (say a
temperature below 32° Fahrenheit). Under the influence of the low temperature
an exchange takes place between the acids and the bases, sulphate of soda is formed
and precipitated in crystals by reason of its insolubility in water cooled below
32° Fahrenheit, and a solution of chloride of iron and chloride of aluminum remains.
I thus obtain the said chlorides of iron and aluminum for use in precipitating
sewage or for other purposes in addition to the sulphate of iron and sulphate of
soda, the sale of which bye products will defray or reduce the cost of the solution of
chloride of iron and chloride of aluminum.
If desirable the crystals of sulphate of iron aforesaid may be dissolved in water
and the solution may be treated with a further quantity of common salt, and refri-
gerated so as to obtain sulphate of soda and chloride of iron.
The operations of adding common salt and refrigerating, as herein-before described,
may be applied with advantage in processes in which sulphates of iron or sulphates
of alumina are used, either together or separately, for the purification of sewage, the
said operations transforming the sulphate of iron into sulphate of soda and chloride
of iron, and the sulphate of alumina into sulphate of soda and chloride of aluminum.
Thus, for instance, I add cominon salt to a solution of commercial sulphate of
alumina (which is generally prepared by the action of sulphuric acid on china clay),
and I refrigerate the mixture, as herein-before described. The same result may be
obtained by heat, and I reserve to myself the right of proceeding in this way.
My Invention consists further of a cheap mode, herein-after described, of obtaining
calcic solutions to be used in the treatment of sewage. I select a phosphate of lime
containing a considerable proportion of carbonate of lime. Phosphates of this kind
are but little in request for agricultural and manufacturing purposes in consequence
of their poverty in phosphoric acid, and may consequently be obtained at a low
price. They are to be obtained in abundance near Lille, in France, near Mons, in
Belgium, and in Yorkshire and Dorsetshire in England. I burn the said phosphates
in an ordinary lime-kiln so as to expel the carbonic acid from the carbonate of lime.
The resulting product, which consists of carbonate of lime and quicklime, is then
slaked or lixiviated with water or with sewage (purified or unpurified), so as to
form a milk of lime, which may be run into the sewage to be purified, the phosphate
of lime, which is of greater density, being precipitated. When all the lime has been
remoyed by the aforesaid lixiviation the phosphate of lime will be found to be
nearly free from its inert matter, and its per-centage of phosphoric acid being
considerably increased the said phosphate will be readily saleable.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent filed by
the said George Fournier in the Great Seal Patent Office on the 14th
February 1878.
GEORGE FOURNIER, of No. 42, Boulevart de Strasbourg, in the City of Paris,
Chemist. "IMPROVEMENTS IN THE MANUFACTURE OF AGENTS FOR THE PURIFI-
CATION OF SEWAGE AND FOR OTHER PURPOSES."
My Invention relates to the manufacture of the chlorides of aluminium and iron,
which substances or agents are used in the treatment of sewage and other foul
waters, and for other purposes.
My said Invention consists of the improvements herein-after described in the
manufacture of the said chlorides of aluminium and iron, by which improvements I
so prepare these agents that the cost thereof shall be wholly or in great part
defrayed by the bye products which I obtain in the course of their manufacture.
I take pyritic schists or shales, and either roast them or expose them to the
weather until a considerablé portion of the sulphur present has been oxidised to
sulphuric acid which forms sulphates with the iron and alumina contained in
the said schists or shales. (In case the schist or shale is not sufficiently pyritic I
make it so by adding pyrites.) After roasting or exposing the said schists or shales
I lixiviate them with water and place the resulting lixivium in suitable vessels in
contact or admixture with iron, either cast iron, sheet iron, scrap iron, iron
borings, or iron of any kind in a sufficiently divided state, my object in doing
this being to reduce all iron present in the said lixivium to the state of a proto
salt. This result is obtained in about 48 hours, or it can be hastened by
heating the said lixivium in contact with the iron. The density of the liquor,
which previous to this treatment would be about 28° to 30° Beaumé, is thus
increased to about 33° to 35°. I then draw off the liquor from the aforesaid
vessels, which I then recharge with more lixivium, to be treated in the same
way. I concentrate the liquor by heat (after its treatment with the iron) to
about 38° Beaumé and leave it to crystallize, and on cooling it deposits crystals
of sulphate of iron (copperas) equal to about 10 to 12 per cent. of the weight
of the concentrated liquor. I thus eliminate part of the sulphuric acid and iron
in the form of the sulphate of iron aforesaid, which is a valuable bye product.
Thus far my process is similar to some of the processes by which alum bas
been prepared from aluminous schists or shales. I mix the mother liquids
remaining after the crystallization of the sulphate of iron with an equivalent
quantity of chloride of sodium (common salt), so as to cause an exchange to
take place between the acids and the bases, and I submit the mixture to the
action of cold, either natural or artificial (say a temperature below 32° Fahrenheit).
Under the influence of the low temperature sulphate of soda is deposited in crystals
by reason of its being almost insoluble in water cooled below 32° Fahrenheit, and a
solution of chloride of aluminium and chloride of iron remains which does not
solidify at that temperature. I then take out the crystals of sulphate of soda;
I thus obtain the said chlorides of aluminium and iron for use in precipitating
sewage or for other purposes in addition to the sulphate of iron and sulphate
of soda, the sale of which bye products will defray or reduce the cost of the
solution of chloride of aluminium and chloride of iron. The mother liquor
containing the said chlorides of aluminium and iron may be either run direct
into the sewage to be treated, or it may be evaporated until it will form a
nearly solid mass on cooling.
If desirable the crystals of sulphate of iron aforesaid may be dissolved in water,
and the solution may be treated with an equivalent quantity of chloride of sodium
and refrigerated so as to obtain sulphate of soda and chloride of iron.
The operations of adding chloride of sodium to solutions containing sulphates and
refrigerating, as herein-before described, may be applied with advantage in processes

page_text: in which sulphates of iron or sulphates of alumina are used, either together or
separately, for the treatment of sewage, the said operations transforming the
sulphate or iron into sulphate of soda and chloride of iron, and the sulphate of
alumina into sulphate of soda and chloride of aluminium. Thus, for instance, I add
chloride of sodium to a solution of commercial sulphate of alumina and I refrigerate
the mixture as herein-before described.
In some cases instead of treating the lixivium from the shale with iron, as herein-
before described, I omit that stage of my process and concentrate the said lixivium
without treating it with iron, and allow the sulphate of iron contained in the said
lixivium to crystallize out on cooling and then treat the mother liquor with chloride
of sodium and refrigerate as herein-before described. This gives a smaller yield of
sulphate of iron and a less neutral residue of the chlorides of aluminium and iron
than the process herein first described.
In some cases instead of crystallizing out the sulphate of iron after digesting or
boiling the aforesaid lixivium with metallic iron, I mix the said lixivium (after
digesting or boiling as aforesaid) with chloride of sodium and then refrigerate, and
thus obtain a larger quantity of sulphate of soda than by either of the foregoing
processes, and a larger quantity of chloride of iron in the residue.
When it is desirable to save time, and where the purity of the products is not of
much importance, I take the lixivium resulting from the lixiviation of the shale, as
aforesaid and (without treating it with iron and concentrating, as herein-before
described) add chloride of sodium to the said lixivium and refrigerate the mixture,
as herein-before described. I thus obtain sulphate of soda in crystals and the
mother liquor containing the chlorides of aluminium and iron.
Having thus described the nature of my Invention, and the manner in which it
is to be performed, I wish it to be understood that I do not limit myself to the
precise details described, as they may be varied without departing from the nature
of my Invention, and that I do not claim per se either the lixiviation of the shale.
or the treatment of the resulting lixivium with iron, or the concentration by heat of
the resulting liquor; nor do I claim per se the addition of chloride of sodium to the
said liquor; but I claim as my said Invention the improvements herein-before
described in the manufacture of chloride of aluminium, chloride of iron, and sulphate
of soda, that is to say, adding chloride of sodium to the mother liquors or solutions
lerein-before referred to, and then refrigerating the mixture, essentially as herein-
before described.
In witness whereof, I, the said George Fournier, have hereunto set my
hand and seal, this Eleventh day of February, in the year of our Lord
One thousand eight hundred and seventy-eight.
GEORGE FOURNIER. (L.S.)