IMPROVEMENTS IN THE PREPARATION OR TREATMENT OF EXTRACTS OF MADDER FOR DYEING AND PRINTING PURPOSES, AND IN APPARATUS USED IN SUCH TREATMENT
Year: 1867

page_text: LETTERS PATENT to Alexander Melville Clark, of 53, Chancery Lane, in
the County of Middlesex, for the Invention of "IMPROVEMENTS IN THE
PREPARATION OR TREATMENT OF EXTRACTS OF MADDER FOR DYEING AND
PRINTING PURPOSES, AND IN APPARATUS USED IN SUCH TREATMENT."-A
communication from abroad by Gustave Adolphe Schaaff and Guillaumo
Ernest Lauth, Merchants, both of 29, Boulevart St. Martin, Paris.
PROVISIONAL SPECIFICATION left by the said Alexander Melville Clark
at the Office of the Commissioners of Patents, with his Petition, on the
11th October 1867.
1, ALEXANDER MELVILLE CLARK, of 53, Chancery Lane, in the County of
Middlesex, do hereby declare the nature of the said Invention for "INPROVE.
MENTS IN THE PREPARATION OR TREATMENT OF EXTRACTS OF MADDER FOR DYEING
AND PRINTING PURPOSES, AND IN APPARATUS USED IN SUCH TREATMENT," to be as
follows:-
This Invention relates to the preparation of extracts of madder in a
sufficiently pure state to be applied for dyeing purposes, and especially for
For printing with madder colors on fabrics it
printing threads and fabrics.
is preferable to employ two kinds of extracts of madder; one extract for violet

page_text: or lilac tints should consist of alizarine in a nearly pure state and free from
any orange or yellow coloring matters in order that a clear bluish tint shall
be produced; the other or complete extract of madder for red, rose, puce, or
black tints should on the contrary contain these matters in order that the tint
may be deeper and more nearly approach to a flame color. The extracts
should further be exempt from all fatty or resinous matters and from any
brown coloring matters.
Lastly, in order to extract the available coloring matters as completely as
possible from the madder I make use of the following processes :-
First. Treatment of Madders containing but little Earthy Carbonates, such
as those of Alsace, Holland, and other Varieties.-I first wash the madder
two or three times in water charged with sulphuric acid. With this solution
a precipitate of purpurine is first obtained, and then a green alizarine, the
acidulated mother waters of the alizarine green being utilized in the manner
herein-after described.
Preparation of Alizarine Extract of Madder for Violet and Lilac Tints.-I
treat alizarine green, well washed and dried, either with ethylated or methylated
alcohols, acetic acid, or a liquid hydrocarburet, benzine, essence of petroleum,
of turpentine, schist oil; or other agent. When treating with alcohols or hydro-
carburets at or below the boiling point I employ an apparatus producing a
continuous circulation by means of which a brownish yellow extract is obtained,
which is then ground very fine either after having been dried if it is desired to
obtain a dry alizarine extract, or after incorporation with a certain quantity of
water to form a paste. In order to extract green alizarine by means of hydro-
carburets heated above the boiling point I make use of an apparatus consisting
of an ordinary alembic in which the hydrocarburet is distilled, whence the
vapours pass into a cylinder with a false bottom containing the green alizarine,
where they are condensed and the coloring matters thereby extracted. The
false bottom is perforated and provided with a cloth filtering surface on which
the green alizarine is spread in a coarse powder. The cylinder is completely
surrounded with water, which is beated by the condensation of the hydro-
carburet, and may be cooled if necessary by a jet of cold water.
The cover
of the cylinder is hermetically closed, and bas a long vertical tube adapted to
it in which the vapours in excess of the hydrocarburet become condensed, and
it also affords an escape for any steam that may accompany the vapors into
the atmosphere. By the condensation of the vapours on the green alizarine
the yellow alizarine will be quickly extracted therefrom, the liquid hydro-
carburet charged with the same running through the false bottom and away
by a tube in the bottom of the cylinder into a metallic reservoir containing an

page_text: aqueous solution of caustic soda. By agitating this the alizarine will be entirely
given up to the bydrocarburet, which floats on the caustic soda, and is then
decanted and returned to the alembic. The hydrocarburet is again distilled
and recondensed in the green alizarine until the latter is completely extracted.
The yellow alizarine is precipitated from the soda solution by means of an
acid and collected in a filter, after which it is washed and allowed to drain and
kept in a pasty condition or dried. The alizarine extract thus prepared is free
from resinous or pectic matters, and also from purpurine and yellow or orange
coloring matters.
Preparation of the Complete Extract of Madder for Reds and Puces.-The
madder extracted by the sulphurous water is introduced into vats and treated
either hot or cold one or more times by a weak alkaline solution, or preferably
with caustic soda. The alkali dissolves the resinous pectinous matters, after
which the magma is decanted and placed in a filter and allowed to drain.
The residue is then washed with a very weak alkaline solution, or with pure
water. The alkaline solutions combined are next precipitated either in a hot
or cold state by means of an acid, and I employ for this purpose the mother
waters of the green alizarine. The yellowish or dull brown precipitate
obtained is collected on a filter and washed, after which it is kept either in a
paste or dried according to the nature of its ulterior treatment. I designate
this product pectinous extract of madder. The residue of the madder which
has furnished the above extract is removed from the filter and placed in a vat
where it is treated in a boiling state with the necessary quantity of the mother
waters of green alizarine in order that the reaction shall be purely acid. After
boiling for an hour it is run through a madder filter and washed in the ordinary
way. The residue after being drained and even squeezed is treated a second
time with a weak alkaline solution in the same manner as before described; in.
this manner a second pectinous extract is obtained' to be added to the preceding.
If the operations are carefully conducted the coloring matter will now be
completely extracted, and the madder may be thrown away, or if not it may
be treated a third time with an alkaline solution in order to obtain a further
pectinous extract therefrom. These extracts thus obtained may be used.
instead of very strong garancine for dyeing purposes, but not for printing, as
they only furnish dull tarnished colors on account of the pectiuous fatty and
resinous matters they contain. Hence they require to be purified in different
ways, as I will now proceed to describe.
1st. Treatment of the Pectinous Extract in the Form of Dry Powder by
means of Alcohols or Hydrocarburets at Boiling Points below 212 Degrees.―
I proceed in the same manner as if extracting green alizarine, and obtain a

page_text: yellowish brown extract free from pectinous substances but still containing
resinous and fatty matters. In order to remove these latter I impregnato
them in a dry state either hot or at a moderate heat with a liquid hydrocarburet
in closed vessels, and allow it to remain for twenty-four hours, after which the
magma is subjected to great pressure. The bydrocarburet liquid but slightly
dissolves the coloring matters, but the greater part of the fatty and resinous
matters are carried off with it. The extract after being subjected to pressure
and purified is dried in a stove. In order to reduce it to a paste it should be
ground with alcoholized water or dissolved in an aqueous caustic soda solution,
precipitated by an acid filtered, filtered, washed, and then allowed to drain. The
paste thus obtained is suitable for use in printing, furnishing very bright and
pure red, rose, and puce tints.
2nd. Treatment of the Pectinous Extract in Dry Powder by means of
Liquid Hydrocarburets at Boiling Points above 212 Degrees.-I proceed in
the same manner as for green alizarine, only instead of treating the beated
solution of hydrocarburet charged with coloring matter with a weak solution
of caustic soda I employ a highly concentrated solution of the latter, so as to
become almost completely solidified by its combination with the coloring
principles. The liquid hydrocarburet, schist oil, or other agent may then be
easily decanted. If a weak soda solution be used the fatty or resinous matters
would form with the caustic soda a kind of soap which would combine with
the schist oil and render their separation almost impossible. The semi-solid
alkaline magma is caused to retain a little schist oil, and is dissolved in warın
water, the coloring matters precipitated by an acid which still retains gummy
and resinous matters being precipitated by an acid. The matters are then
filtered, washed, and allowed to drain, after which the product is deposited in
bags of some very close fabric and subjected to great pressure. The water is
the first to run off, next to which the schist oil impregnating the coloring
matter is expressed, containing in solution the major part of the fatty and
resinous matters. The product is dried after pressing, or it may be pounded
with alcoholized water in order to reduce it to a pasty condition. In both
cases it will be sufficiently pure for use.
3rdly. Treatment of the Pectic Extract either in a Paste or Dried and
Pulverized by means of a Boiling Saline Solution.-For this purpose I select
a salt a boiling solution of which will dissolve the coloring matters of the
madder; salts of alumina will serve the purpose. I prefer to use the hydro-
chlorate or sulphate of alumina. Neutral salts should not be used except
with the addition of a per-centage of free acid. Sulphate of alumina of
commerce generally contains sufficient free sulphuric acid, but if alum be used

page_text: sulphuric acid should be added. The solutions should mark from 4 to 5 degrees
Beaumé in which the pectic extract is introduced and boiled from a
quarter to half an hour. The container is carefully closed and the solution
allowed to settle, after which it is decanted in a clear limpid condition, and of
a fine orange red color. The thick part is run through a filter, where it
quickly clears on being drained off, while the residue is returned to the vat
and treated several times as before. The liquors in cooling deposit the coloring
matters in red or orange flakes with a brownish tint towards the end. The
cold limpid alumina solution is decanted and is again treated in a boiling state,
and so on. The flakes of coloring matter are placed in a filter, drained, and
washed first with water containing sulphuric or hydrochloric acid, and then
with pure water. The extract is then again drained off and kept in a paste, or
it may be dried and pulverized. The residue of the pectic extract resulting
from the repeated treatment with the boiling alumina solution is lastly ex-
pressed and thrown on one side. It may be boiled with the acid mother
waters of green alizarine, or with an acid to which it cedes the alumina, and
forming after washing, drying, and pounding a kind of weak madder.
4thly. Purification of the Pectic Extract by the Aid of Concentrated Sulphuric
Acid. By mixing the dry well pulverized pectic extract with once or twice its
weight of concentrated sulphuric acid (about a pint per lb. of extract) the
mixture will become heated and the greater part of the extraneous matters
will be carbonized; the whole turns black and exhales an odour of sulphurous
gas, and if ground in water, filtered, washed, and dried a material similar to sul-
phuric charcoal is obtained but much richer in coloring matter and affording very
bright pure tints for dyeing purposes. This product may be submitted to exactly
the same extracting processes as green alizarine, and furnishes a complete extract
of madder of good quality for red rose and puce tints for printing purposes.
5thly. Purification of the Pectic Extract by the Aid of Aluminate of Soda.-
In treating the pectic extract paste with a solution of aluminate of soda, or
which is the same by first treating while hot with the salt of alumina in solution
and then gradually super-saturating it with salt of soda so as to render the
liquor alkaline, the coloring matters combine with the alumina, forming lacs
which remain insoluble in the solution of carbonate of soda while a considerable
portion of the pectinous fatty and resinous matters become dissolved. The
insoluble product, when filtered, washed and expressed, is diluted in boiling
acidulated water in order to decompose the aluminous lac and set the coloring
matters at liberty. These latter after being collected in a filter, washed, and
expressed will constitute a much purer product than the raw pectic extract

page_text: Blthough less so than the extracts obtained by the processes nerem-before
described.
Treatment of Madders rich in Earthy Carbonates, such as Madder
d'Avignon. I mix with sulphurous water a proportion of acid, by preference
hydrochloric acid corresponding to the quantity of eartby carbonates contained
in the roots in order that the sulphurous acid shall remain free, and its action
not be annihilated by its combination with the earthy or alkaline bases. I
then proceed to steep it in the same way as for non-calcareous madders, but it
will be of advantage, the first steeping liquor having been obtained by filtration,
to wash the madder in the filter a second or third time with water containing
a very weak sulphurous solution but at a high degree of heat. If the washing
be thus carried out liquors may be obtained already sufficiently rich in colorable
matters; I then proceed to precipitate the purpurine and green alizarine in
the ordinary manner. The residue of the madder treated by the sulphurous
water is then treated with alkaline and acid solutions for obtaining the pectic
extract as before described, which latter is afterwards purified also in the
manner herein before described. When it is wished to utilize the sugar con-
tained in the madder root for obtaining alcohol, while at same time steeping it
in the sulphurous water, I proceed in the following manner :-The steeping
is effected as above except that the liquors are obtained as highly concentrated
as possible. It is desirable to add to the sulphurous water from one five-
hundredth to a thousandth more sulphuric or hydrochloric acid than is required
to saturate the bases. The madder is expressed before washing with the
heated sulphurous water which only produces liquors containing an insufficient
quantity of sugar to be subjected to fermentation although rich enough in
coloring matter, purpurine and alizarine. I may also so arrange the washing
and extraction of the madder as to obtain a continuous supply of highly con-
centrated steeping liquors rich in sugar; this liquor is then heated to from
120 to 140 degrees or more so as to precipitate a certain quantity of a reddish
brown purpurine often containing alizarine. This is allowed to settle, the
clear liquor being drawn off and afterwards passed through an apparatus
similar to that before described for the preparation of sulphurous water, or
other arrangements may be adopted for bringing the liquor intimately in
contact with a current of air of sufficient amount for obtaining either the
separation of the sulphurous acid or its oxidation as sulphuric acid. The
heated liquors are cooled by passing through the oxidizing apparatus and
return to a temperature more suited to fermentation; these liquors may then
De fermented in order to convert the sugar into alcohol and distilled for

page_text: obtaining alcohol; and after this has been extracted about 2 or 3 per cent. of
sulphuric or hydrochloric acid is to be added to the liquors, which are then
boiled for some hours in order to precipitate the green alizarine. During the
passage of the liquors through the oxidizing apparatus, a certain quantity of
brown matter will form and be deposited, which is collected and treated
separately with acidulated water, washed, dried, and the coloring matter
extracted by means of alcohol, hydrocarburets and alumina solutions. It is
however practically more simple and advantageous to allow the matters
deposited and rendered insoluble to remain during the fermentation in the
liquor, and collect the whole with the green alizarine, the latter pure or mixed
with brown matters serving for the preparation of the alizarine extract for
violet shades. The residue of the madder is treated as before for obtaining
the pectic extract which in its turn serves as material for the preparation of
the purified extract for red and
puce colors.
Simplified Treatment of Madder.-The treatment of madder with sulphurous
water for the separation of purpurine and green alizarine may be considered
as the most advantageous, as the preparation of the sulphurous water occasions
but a very small expense and it serves for the complete utilization of the whole
of the acid mother waters of the green alizarine; if however it be desired
to prepare a purified extract of madder for reds and puces by the complete
extraction of the coloring matters from the madder without separating the
purpurine and green alizarine, I proceed as follows:-I treat the madder with
hot acidulated water or preferably with hydrochloric acid in the case of
calcareous madder. This treatment is continued for from 24 to 36 hours,
after which it is filtered, washed and expressed; by arranging the treatment
so as to effect a continuous washing producing only strong liquors highly
charged with sugar the said liquors may be fermented in order to obtain
alcohol by distillation. The residue after being expressed is treated with an
alkaline solution to furnish a liquor for precipitating the pectic extract by
super-saturation with an acid. The new residue after being washed and
expressed if necessary is treated with an acidulated boiling solution; the
insoluble product when washed is again treated with alkaline solution to obtain
a new supply of the pectic extract. This treatment is repeated as long as a
sufficient quantity of the extract can be obtained, after which the exhausted
residue is thrown on one side. The pectic extract is lastly purified according to
one of the modes herein-before specified. When the madder extracts how-
seever obtained do not furnish sufficiently bright or permanent tints, they
should be treated with boiling schist oil, which is then filtered and the coloring
natter separated, agitating it in an alkaline solution. This treatment by

page_text: means of schist oil possesses the double advantage, not only of separating the
utilizable coloring matter from the impurities it contains, but also of so
modifying it as to improve the brilliancy and permanency of the shades obtained.
This improvement is more especially applicable to the preparation of the
alizarine violet extracts. The foregoing are the improvements in the manufac-
ture of extracts of madder forming the subject of the present Invention by
means of which I may 1st. obtain special extracts for violet and reil tints;
2ndly, effect the extraction of the whole of the coloring matter in the madder
by the previous preparation of the pectic extract and the subsequent purifica-
tion of the same in the manner indicated; and 3rdly., obtain an advantageous
modification in the principles of the coloring matters by the aid of boiling
hydrocarburets.
For extracting and washing madder, garancine, and madder flowers, sulphuric
charcoal, and generally all products derived from madder either by means of
cold, warm, or boiling water, or cold, warm, or boiling acid alkaline or saline
solutions, I use lixiviating apparatus similar to those used for the lixiviation
of raw soda in the manufacture of chemical products by which method I am
enabled to extract and wash the madder, garancine, or madder flowers much
more perfectly than hitherto, obtaining at all times sufficiently concentrated
liquors by the extraction and without sensible loss of coloring matter during
the washing. Thus for example madder flowers and garancine may be washed
until entirely neutral without difficulty, as the coloring matter dissolved by
the pure water in those parts where the washing is almost terminated is
precipitated afresh on the madder flowers or fresh garancine while still acid,
the washing of which is then proceeded with. These latter thus enrich the
whole of the coloring matters dissolved by the pure water which is precipitated
by the acid. In cases where flowers of madder or garancine are treated
instead of madder for the preparation of extracts of madder I. treat them in
the same way as for madder, impregnating them with sulphurous water, sub-
mitting them to pressure and then washing with boiling water. Thus the
madder flowers and garancino are treated by alkaline liquors, the pectic
extract being precipitated by super-saturation by an acid, the residues are boiled
with the acid, and after washing are treated a second time by alkaline liquors,
and so on until all the available coloring principles are extracted.
The pectic
extract thus obtained is treated in a similar manner as for that extracted from
the madder by the sulphurous water; I may also but with less advantage treat
flowers of madder or garancine directly with an acidulated solution of sulphate
or hydrochlorate of alumina as before indicated with reference to the pectic
extract. The orange yellow extract obtained is then purified by treatment in

page_text: a heated state with sulphuric or hydrochloric acid diluted in water, and also
after being washed and dried by means of schist oil in the manner before
described. I have before mentioned that the sulphuretted liquors highly
charged with sugar, after being heated for the separation of the purpurine and
then oxydized for driving out or destroying the sulphurous acid, is then caused
to ferment, distilled, and lastly boiled with two or three per cent. of sulphuric
acid. It will however be of advantage before fermenting the liquors to place
them in large vats and there allow them to settle in order to draw off only the
clear limpid portion. The deposit formed of cellular matters containing color
is placed in a filter, drained, washed one or more times with warm water, and
then again drained. The extraction of the deposit may then be directly
effected by the acidulated solution of sulphate of alumina. It results from
this modification that the green alizarine obtained by boiling the fermented
liquors with the addition of from two to three per cent. of sulphuric acid will
be purer, as it no longer contains any refuse of the fermentation deposited in
the liquors. I may also after the alcobolic distillation again allow the boiling
liquors to settle and decant the clear liquid from such fresh deposit, which is
also collected, separately drained, washed, again drained and treated in turn
with the acidulated solution of sulphate of alumina. By operating in this
nanner the green alizarine obtained from the limpid liquors will be both
stronger and purer than that prepared direct with non-fermented sulphurous
steeping liquors. Instead of precipitating the green alizarine from the different
liquors either fermented or otherwise from which the purpurine has been
precipitated, I may add to it milk of lime, which after being boiled precipitates
alizarate of lime in, the form of calcareous lac; or I may decompose by the
aid of bydrochloric acid, and treat the impure alizarine with alcobols, sulphuret
of carbon, or hydrocarburets; the sulphate of lime is no impediment, but
rather proves an advantage in rendering the raw alizarine porous.
SPECIFICATION in pursuance of the conditions of the Letters Patent,
filed by the said Alexander Melville Clark in the Great Seal Patent
Office on the 9th April 1868.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, ALEXANDER
MELVILLE CLARK, of 53, Chancery Lane, in the County of Middlesex, send
greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her Letters
Patent, bearing date the Eleventh day of October, in the year of our
Lord One thousand eight hundred and sixty-seven, in the thirty-first year of

page_text: Her reign, did, for Ierself, Iler heirs and successors, give and grant unto
me, the said Alexander Melville Clark, Her special licence that I, the said
Alexander Melville Clark, my executors, administrators, and assigns, or such
others as I, the said Alexander Melville Clark, 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 PREPARATION OR TREATMENT CF EXTRACTS
OF MADDER FOR DYEING AND PRINTING PURPOSES, AND IN APPARATUS USED IN SUCH
TREATMENT," a communication to me from abroad by Gustave Adolphe Schaaff
and Guillaume Ernest Lauth, Merchants, both of 29, Boulevart St. Martin,
Paris, upon the condition (amongst others) that I, the said Alexander Melville
Clark, 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.
F
NOW KNOW YE, that I, the said Alexander Melville Clark, 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 (that is to say) :-
This Invention relates to the preparation of extracts of madder in a
sufficiently pure state to be applied for dyeing purposes, and especially for
printing threads and fabrics. For printing with madder color on fabrics it is
preferable to employ two kinds of extracts of madder, one extract for violet or
lilac tints should consist of alizarine in a nearly pure state and free from any
orange or yellow coloring matters in order that a clear bluish tint should be
produced; the other or complete extract of madder for red, rose, puce, or black
tints should on the contrary contain these matters in order that the tint may
be deeper and more nearly approach to a flame color; the extracts should
further be exempt from all fatty or resinous matters and from any brown
coloring matters.
Lastly in order to extract the available coloring matters as completely as
possible from the madder I make use of the following processes :-
1st. Treatment of Madders containing but Little Earthy Carbonates, such as
those of Alsace, IIolland, and other Varieties.-I first wash the madder after
it has been crushed or pounded two or three times in water charged with

page_text: sulphurous acid. With this solution a precipitate of purpurine is first obtained,
and then of green alizarine, the acidulated mother water of the alizarine green.
being utilized in the manner herein-after described.
Preparation of Alizarine Extract of Madder for Violet and Lilac Tints.-I
treat alizarine green, well washed and dried, either with ethylated or methylated.
alcohols, acetic acid, or aliquid hydro hydrocarburet, benzine, essence of petroleum,.
of turpentine, schist oil, or other agent. When treating with alcohols or hydro-
carburets at or below the boiling point I employ an apparatus producing a con-
tinuous circulation, by means of which a brownish yellow extract is obtained,
which is then ground very fine, either after being dried if it is desired to obtain
a dry alizarine extract, or after incorporation with a certain quantity of water to
form a paste. In order to extract green alizarine by means of hydrocarburets
heated above the boiling point I make use of an apparatus consisting of an.
ordinary alembic in which the bydrocarburet is distilled, whence the vapours.
pass into a cylinder with a false bottom containing the green álizarine, where,
they are condensed and the coloring matters thereby extracted. The false.
bottom is perforated and provided with a cloth filtering surface on which the
green alizarive is spread in a coarse powder. The cylinder is completely sur-
rounded with water, which is heated by the condensation of the hydrocarburet,
and may be cooled if necessary by a jet of cold water. The cover of the cylinder
is hermetically closed, and has a long vertical tube adapted to it, in which the
vapours in excess of the hydrocarburet become condensed, and also affords an
escape for any steam that may accompany the vapors into the atmosphere.
By the condensation of the vapors on the green alizarine the yellow alizarine.
will be quickly extracted therefrom the liquid hydrocarburet charged with the
same running through the false bottom, and away by a tube in the bottom of
the cylinder into a metallic reservoir containing an aqueous solution of caustic.
soda. By agitating this the alizarine will be entirely given up to the hydro-
carburet which floats in the caustic soda, and is then decanted and returned to
the alembic. The hydrocarburet is again distilled or recondensed on the
green alizarine until the latter is completely extracted. The yellow alizarine,
is precipitated from the soda solution by means of an acid, and collected in a
filter, after which it is washed and (allowed to drain and kept in a pasty con-
dition or dried. The alizarine extract thus prepared is free from resinous or
pectic matters, as also from purpurine and yellow or orange coloring matters.
Preparation of the Complete Extract of Madder for Reds and Puces:-The
madder extracted by the sulphurous water is introduced into vats and treated-
either hot or cold one or more times by a weak alkaline solution, or preferably
with caustic soda, the alkali dissolves the resinous pectinous coloring matters,,

page_text: after which the magma is decanted and placed in a filter and allowed to drain,
the residue is then washed with a very weak alkaline solution or with pure
water. The alkaline solutions combined are next precipitated either in a hot
or cold state by means of an acid, and I employ for this purpose the mother
waters of the green alizarine. The yellowish or dull brown precipitate obtained
is collected in a filter and washed, after which it is kept either in a paste or
dried according to the nature of the ulterior treatment. I designate this pro-
duct pectinous extract of madder. The residue of the madder which has
furnished the above extract is removed from the filters and placed in a vat, when
it is treated in a boiling state with the necessary quantity of the other waters
of green alizarine in order that the reaction shall be purely acid.
boiling for an hour it is run through a garancine filter and washed in the
ordinary way. The residue after being drained and even squeezed is treated
a second time with a weak alkaline solution in the same manner as before
described, in this manner a second pectinous extract is obtained to be
added to the preceding.
After
If the operations are carefully conducted the coloring matter will be com-
pletely extracted and the madder may be thrown away, or if not may be treated
a third time with an alkaline solution in order to obtain a further pectinous
extract therefrom. These pectinous extracts thus obtained may be used
instead of very strong garancine for dyeing purposes, but not for printing, as
they only furnish dull tarnished colors on account of the pectinous, fatty, and
resinous matters they contain, hence they require to be purified in different
ways, as I will now proceed to describe.
1
1st. Treatment of the Pectinous Extract in the Form of Dry Powder by
means of Alcohols or Hydrocarburets at Boiling Points below 212 Degrees.―
I proceed in the same manner as if extracting green alizarine, and obtain a
yellowish brown extract free from pectinous substances, but still containing
resinous and fatty matters. In order to remove these latter I impregnate them
in a dry state either cold or at a moderate beat with a liquid hydrocarburet in
closed vessels, and allow it to remain for twenty-four hours, after which the
magma is subjected to great pressure. The hydrocarburet liquid but slightly
dissolves the coloring matter, but the greater part of the fatty and resinous matters
are carried off with it. The extract after being subjected to pressure and puri-
fied is dried in a stove. In order to reduce it to a paste it should be ground with
alcoholized water or dissolved in an aqueous caustic soda solution, precipitated
by an acid, filtered, washed, and then allowed to drain, the paste thus obtained is
suitable for use in printing, furnishing very bright and pure red, rose, and puce
tints

page_text: 2nd. Treatment of the Pectinous Extract in Dry Powder by means of
Liquid Hydrocarburets at Boiling Points above 212 Degrees.-I proceed in
the same manner as for green alizarine, only instead of treating the heated'
solution of hydrocarburet charged with coloring matter with a weak solution of
caustic soda, I employ a highly concentrated solution of the latter so as to
become almost completely. solidified by its combination with the coloring
principles. The liquid hydrocarburet schist oil or other agent may then be
easily decanted. If a weak soda solution be used the fatty and resinous>
matters would form with the caustic soda a kind of soap, which would combine
with the schist oil and render their separation almost impossible. The semi-
solid alkaline magma is caused to retain a little schist oil, and is dissolved in
warm water, and the coloring matters precipitated by an acid which still:
retain gummy and resinous matters. The matters are then filtered, washed
and allowed to drain, after which the product is deposited in bags of some
very close fabric and subjected to great pressure; the water is the first to run
off, next to which the schist oil impregnating the coloring matter is expressed.
containing in solution the major part of the fatty and resinous matters; the
product is dried after pressing or it may be pounded with alcoholized water in.
order to reduce it to a pasty condition. In both cases it will be sufficiently:
pure for use.
.
3rdly. Treatment of the Pectic Extract either in a Paste, or Dried and
Pulverized by means of a Boiling Saline Solution.-For this purpose I select
a salt, a boiling solution of which will dissolve the coloring matters of the inadder.:
Salts of alumina will serve the purpose, and I prefer to use the hydrochlorate or
sulphate of alumina. Neutral salts should not be used except with the addition:
of a per-centage of free acid. Sulphate of alumina of commerce generally:
contains sufficient free sulphuric acid, but if alum.be used sulphuric acid,
.should-be added. The solutions should mark from 4 to 5 degrees Beaumé,
in which the pectic extract is introduced and boiled from a quarter to half an
hour. The container is carefully closed and the solution allowed to settle,
after which it is decanted in a clear limped condition and of a fine orange red
color. The thick part is run through a filter, where it quickly clears on
being drained off, while the residue is returned to the vat and treated several
times as before. The liquids in cooling deposit the coloring matters in red or
orange flakes with a brownish tint towards the end. The cold limpid
alumina solution is decanted and again treated in a boiling state, and so on.
The flakes of coloring matter are placed in a filter, drained and washed, first
with water containing sulphuric or hydrochloric acid, and then with pure
water.
The extract is then again drained off and kept in a paste, or it may bo

page_text: dried and pulverized. The residue of the pectic extract resulting from the
repeated treatment with the boiling alumina solution is lastly expressed and
thrown on one side, or it may be boiled with the acid mother water of green
alizarine or with an ácid to which it cedes the alumina, and forming after
washing, drying, and pounding a kind of weak madder.
4thly. Purification of the Pectic Extract by the Aid of Concentrated
Sulphuric Acid. By mixing the dry and well pulverized pectic extract with
once or twice its weight of concentrated sulphuric acid (about a pint per pound of
extract) the mixture will become beated, and the greater part of the extraneous
matters will be carbonized. The whole turns black and exhales an odour of
sulphurous gas, and if ground in water, filtered, washed, and dried, a material
similar to sulphuric charcoal is obtained, but much richer in coloring matter,
and affording very bright pure tints for dyeing purposes. This product may be
submitted to exactly the same extracting process as green alizarine, and
furnishes a complete extract of madder of good quality for red, rose, and puce
tints for printing purposes.
5thly. Purification of the Pectic Extract by the Aid of Aluminate of Soda.-
In treating the pectic extract paste with a solution of aluminate of soda, or
which is the same by first treating while hot with a salt of alumina in solution,
and then gradually supersaturating it with salt of soda so as to render the
liquor alkaline, the coloring matters combine with the alumina forming lacs
which remain insoluble in the solution of carbonate of soda, while a consider-
able proportion of the pectinous; fatty, and resinous matters become dissolved.
The insoluble product when filtered, washed and expressed, is diluted in boiling
acidulated water in order to decompose the aluminous lac, and set the coloring
matters at liberty. These latter after being collected in a filter, washed, and
expressed will constitute a much purer product than the raw pectic extract,
although less so than the extracts obtained by the process herein-before
described.
"Treatment of Madders Rich in Earthy Carbonates such as Madder
d'Avignon." I mix with sulphurous water a proportion of acid, by preference
hydrochloric acid, corresponding to the quantity of earthy carbonates contained
in the roots, in order that the sulphurous acid shall remain free, and its action
not be annihilated by its combination with the earthy or alkaline bases; I then
proceed to steep it the same as for non-calcareous madder, but it will be of
advantage, the first steeping liquor having been obtained by filtration, to wash
the madder in the filter a second and third time with water containing a very
weak sulphurous solution but at a high degree of heat. If the washing be thus
carried out liquors may be obtained already sufficiently rich in colorable

page_text: matters. I then proceed to precipitate the purpurine and green alizarine
in the ordinary manner. The residue of the madder treated by the sulphurous
water is then treated with alkaline and acid solutions for obtaining the pectic
extract as before described, which latter is afterwards purified also in the
manner herein-before described. When it is wished to utilize the sugar
contained in the madder root for obtaining alcohol while at same time
steeping it in the sulphurous water, I proceed in the following manner:-
The steeping is effected as above, except that the liquors are obtained as
highly concentrated as possible. It is advisable to add to the sulphurous water
from one five-hundredth to one-thousandth more sulphuric or bydrochloric acid
than is required to saturate the bases. The madder is expressed before
washing with the heated sulphurous water, which only produces liquor contain-
ing an insufficient quantity of sugar to be subjected to fermentation, although
rich enough in coloring matter, purpurine, and alizarine. I may also so
arrange the washing and extraction of the madder as to obtain a continuous
supply of highly concentrated steeping liquors rich in sugar. This liquor is
then heated to from 120 to 140 degrees, or more, so as to precipitate a certain
quantity of a reddish brown purpurine often containing alizarine. This is
allowed to settle, the clear liquid being drawn off and afterwards passed
through an apparatus similar to that before described for the preparation of
sulphurous water; or other arrangements may be adopted for bringing the
liquor intimately in contact with a current of air of sufficient amount for
obtaining either the separation of the sulphurous acid or its oxidation as
sulphuric acid. The heated liquors are cooled by passing through the
oxidizing apparatus and reduced to a temperature more suited to fermentation.
These liquors may then be fermented in order to convert the sugar into alcohol
and distilled for obtaining alcohol; after this has been extracted about two or
three per cent. of sulphuric or hydrochloric acid is to be added to the liquors,
which are then boiled for some hours in order to precipitate the,
green alizarine.
During the passage of the liquors through the oxidizing apparatus a certain
quantity of brown matter will form and be deposited, which is collected and
then treated separately with acidulated water, washed, dried, and the coloring
matter extracted by means of alcohol, bydrocarburets, and alumina solutions.
It is however practically more simple and advantageous to allow the matters
deposited and rendered insoluble to remain during the oxidation or during the
fermentation in the liquor and collect the whole with the green alizarine, the
latter whether pure or mixed with brown matters serving for the preparation
of the alizarine extracts for violet shades. The residue of the madder is
treated as before for obtaining the peetic extract, which in its turn serves

page_text: as a material for the preparation of the purified extract for red and puce
colors.
Simplified Treatment of Madder.-The treatment of madder with sulphu-
rous water for the separation of purpurine'and green alizarine may be considered
as the most advantageous, as the preparation of the sulphurous water occasions
but a very small expense, and it serves for the complete utilization of the whole
of the acid mother waters of the green alizarine; if however it be desired
to prepare a purified extract of madder for reds and puces by the complete
extraction of the coloring matters from the madder without separating the
purpurine and green alizarine, I proceed as follows:-I treat the madder with
hot acidulated water, or preferably with hydrochloric acid in the case of cal-
careous madder. This treatment is continued from 24 to 36 hours, after which
it is filtered, washed, and expressed. By arranging the treatment so as to
effect continuous washing producing only strong liquors lightly charged with
sugar, the said liquors may be fermented in order to obtain alcohol by dis-
tillation. The residue after being expressed is treated with an alkaline solution
to furnish a liquor, or precipitating the pectic extract by super-saturation with
an acid, the raw residue after being washed and expressed if necessary is treated
with an acidulated boiling solution. The insoluble product when washed is
again treated with an alkaline solution to obtain a new supply of the pectic
extract. This treatment is repeated as long as a sufficient quantity of the
extract can be obtained, after which the exhausted residue is thrown on one
side. The pectic extract is lastly purified according to one or other of the
modes herein-before described.
When the madder extracts obtained do not furnish sufficiently bright or
permanent tints they should be treated with boiling schist oil, which is then
filtered, and the coloring matter separated agitating it in an alkaline solution.
This treatment by means of schist oil possesses a double advantage not only
of separating the utilizable coloring matter from the impurities it contains,
but also of so modifying it as to improve the brilliancy and permanence of the
shades obtained. This improvement is more specially applicable to the pre-
paration of the alizarine violet extracts. The foregoing are the improvements
in the manufacture of extracts of madder forming the subject of the present
Invention, by means of which I may, 1st, obtain special extracts for
violet and red tints; 2ndly, effect the extraction of the whole of the coloring
matter in the madder by the previous preparation of the pectic extract, and the
subsequent purification of the same in the manner indicated; and 3rdly, obtain
an advantageous modification in the principles of the coloring matters by the
aid of boiling bydrocarburets.

page_text: For extracting and washing madder, garancine, and madder flowers, sulphuric
charcoal, and generally of all products derived from madder either by means of
cold, warm, or boiling water, or cold, warm, or boiling acid, alkaline, or saline
solutions, I use lixiviating apparatus similar to those used for the lixiviation of
raw soda in the manufacture of chemical products, by which method I am
enabled to extract and wash the madder, garancine, or mailder flowers much
more perfectly than hitherto, obtaining at all times sufficiently concentrated
liquors by extraction, and without sensible loss of coloring matter during the
washing, thus for example madder flowers and garancine inay be washed until
entirely neutral without difficulty as the coloring matter dissolved by the
pure water in those parts where the washing is almost terminated is
precipitated afresh on the madder flowers or fresh garancine while still acid,
the washing of which is then proceeded with. These latter thus enrich the
whole of the colouring matters dissolved by the pure water which is precipitated
by the acid. In cases where flowers of madder or garancine are treated
instead of madder for the preparation of extracts of madder I treat them in
the same way as for madder impregnated with sulphurous water, submitting
them to pressure, and then washing with boiling water. Thus the madder
flowers and garancine are treated by alkaline liquors, the pectic extract being
precipitated by super-saturation by an acid, and after washing are treated a secon
time by alkaline liquors, and so on until all the available coloring principles are
extracted. The pectic extract thus obtained is treated in a similar manner as
that extracted from the madder by the sulphurous water. I may also but
with less advantage treat flowers of madder or garancine directly with an acidu-
lated solution of sulphate or hydrochlorate of alumina as before indicated
with reference to the pectic extract. The orange or yellow extract obtained'
is then purified by treatment in a heated state with sulphuric or hydrochloric
acid diluted in water, and after being washed and dried by means of schist oi!
in the manner before described.
I have before mentioned that the sulphuretted liquors highly charged with
sugar, after being heated for the separation of the purpurine, and then oxidized
for driving out or destroying the sulphuric acid is then caused to ferment,
distilled, and lastly boiled with two or three per cent. of sulphuric acid. It
will however be of advantage before fermenting the liquor to place them in
large vats, and there allow them to settle in order to draw off only the clear
limpid portion, the deposit formed of cellular matters containing color is placed
in a filter, drained, washed one or more times with warm water, and then again
drained. The extraction of the deposit may then be directly effected by the
acidulated solution of sulphate of alumina. It results from this modification

page_text: that the green alizarine obtained by boiling the fermented liquors with the
addition of from two to three per cent. of sulphuric acid will be purer, as it no
longer contains any refuse of the fermentation deposited in the liquors. I
may also after the alcoholic distillation again allow the boiling liquors to settle,
and decant the clear liquid from such fresh deposit, which is also collected
separately, drained, washed again, and treated in turn with the acidulated
solution of sulphate of alumina. By operating in this manner the green
alizarine obtained from the limpid liquors will be both stronger and purer than
that prepared direct from non-fermented sulphurous steeping liquors; instead
of precipitating the green alizarine from the different liquors either fermented
or otherwise from which the purpurine has been precipitated, I may add to it
milk of lime, which after being boiled precipitates alizarate of lime under form of
calcareous lac, or I may decompose by the aid of bydrochloric acid and treat
the impure alizarine with alcohols, sulphuret of carbon, or hydrocarburets; the
sulphate of lime is no impediment, but rather proves an advantage in rendering
the raw alizarine porous.
The Invention thus comprises, first, the treatment of madders containing
but little earthy carbonate, such as those of Alsace or Holland, in which the
preparation of the alizaric extract of madder for violet and lilac tints is obtained
by means of green alizarine, ethylated or methylated alcohols, acetic acid, or a
liquid hydrocarburet, such as benzine, essence of petroleum, or turpentine, or
schist oil by means of a suitable apparatus. The Invention further comprises
the preparation of the complete extract of madder for red and puce tints by
utilizing the residues of the treatment with sulpburous water which are sub-
jected to treatment by means of alkalis and acids. The pectinous extracts
obtained by this preparation will not serve for printing purposes on account
of the fatty and resinous matters they contain, for this purpose they require to
be purified, which may be effected as follows:-1st, I may either treat the
pectinous extract when dried and ground by. means of alcohols or hydro-
carburets whose boiling points are below 212 degrees. The paste obtained in
this manner may be employed for printing purposes, and furnishes very bright
and pure red, rose, and puce tints. 2ndly, I treat the pectinous extract when
dried and ground with liquid hydrocarburets whose boiling points are above
212 degrees. 3rdly, I may treat the pectic extract either in paste or dried
and pulverized by means of a boiling saline solution. 4thly, I may purify the
pectic extract by means of concentrated sulphuric acid, or a complete extract
of madder for red, rose, or puce colors used for printing purposes may be
obtained. 5tbly, I may purify the pectic extract by means of aluminate of soda.
The second part of the Invention comprises the treatment of madders rich

page_text: in earthy carbonates, such as madder d'Avignon, by adding to the sulphurous
water a portion of the acid, and then proceeding in a similar manner as when
treating non-calcareous madder. I would here observe that when it is desired
to utilize the sugar contained in the madder for obtaining alcohol, while at
same time retaining the steeping in the sulphurous water, I so operate as to
obtain the steeping liquors as strong and concentrated as possible.
The third part of the Invention relates to the simplified treatment of madder
by means of acidulated water; it is then left for from 24 to 36 hours, filtered,
and expressed. The washing may be arranged so as to have none but
strong liquors highly charged with sugar, which liquors may be fermented
in order to obtain alcohol by distillation. When the extracts of madder
obtained in any suitable manner do not furnish sufficiently bright and especially
permanent tints, they should be treated with boiling schist oil, which is then
filtered, and the coloring matter removed and dissolved by agitating it in an
alkaline water solution. Besides these improvements, I may obtain, 1st,
special extracts for red or violet tints; 2ndly, I may effect the complete
extraction of madder in an economical manner by preparing the purpurine and
alizarine in the first place from the pectic extract, and subsequently purify said
extract in the manner before indicated; 3rdly, I may modify with advantage
the coloring principles of the extracts by the aid of boiling hydrocarburets.
I would further add, 1st, that in extracting and washing madder, garancine,
madder flowers, sulphuric charcoal, and generally of all products derived from
madders according to the processes herein-before indicated, apparatus should
be employed similar to that employed for the lixiviation of raw soda in the
manufacture of chemical products. For example, madder flowers and garancine
may be readily washed until completely neutral. 2ndly, in cases where it is
desired to use madder flowers or garancine in lieu of madder as raw materia
for the preparation of extracts of madder, I operate on them in the manner
described for madder, impregnating them with sulphurous water. The yellow
extract is treated in the manner indicated. 3rdly, it is of great advantage
before subjecting the sulphurous liquors charged with sugar to fermentation to
put the fermented liquors together into large vats, and allow them to settle.
By this modification the green alizarine produced by ebullition of the
fermented liquors with the addition of from 2 to 3 per cent. of sulphuric acid
will be obtained in a much purer condition. 4thly, instead of precipitating
the green alizarine from the different liquors, whether fermented or otherwise,
from which the purpurine has been precipitated I may add milk of lime
thereto, and on raising it to boiling point precipitate alizarate of lime in the
form of calcareous lac.

page_text: Inving described, the nature of this Invention, and the manner of
performing the same; I declare that what I claim as the Invention to be
protected by the herein-before in part recited Letters Patent is,
⚫ First. I claim in treating madders containing but little earthy carbonates,
such as those of Alsace or Holland, the preparation of an alizaric extract
of madder for violet and lilac tints by means of green alizarine with ethylated
or methylated alcohols, or acetic acid, or a liquid hydrocarburet, benzine,
essence of petroleum, or turpentine, sebist, or other agent, all as herein-before
described.
Secondly. I claim in treating madders containing but little earthy car-
bonates, such as those of Alsace or Holland, the preparation of a complete
extract of madder for red and puce colors by utilizing the residues of the
treatment with sulphurous water which I subject to the action of acids and
alkalies, all in the manner before described.
Thirdly. I claim eliminating the fatty and resinous matters from pectinous
extracts in order to render them suitable for printing purposes by means of
alcohol or hydrocarburets at boiling points either above or below 212 degrees,
or by means of a boiling saline solution or concentrated sulphuric acid or
aluminate of soda, all as herein-before described.
Fourthly. I claim in the treatment of madders rich in earthy carbonates,
such as madder d'Avignon, the addition of a proportion of acid to the sulphurous
water, so as to permit of its treatment in a similar way to the non-calcareous
madder in order to obtain products for dyeing and printing purposes, substantially
in the manner described.
Fifthly. I claim the simplified treatment of madder by means of hot
acidulated water for from 24 to 36 hours, and by filtering, washing, and ex-
pressing it in the manner before described. By arranging the washing so as
to obtain none but strong liquors well charged with sugar they may be fermented
in order to obtain alcohol by distillation.
Sixthly. I claim the treatment of those extracts of madder which do not
furnish sufficiently bright or permanent tints by means of boiling schist oil,
the oil being afterwards filtered and the dissolved coloring matter extracted
by agitating it in water containing an alkali. By this improved treatment,
1st, violet or red coloring extracts are obtained; 2ndly, the complete extraction
of the madder is obtained in an economical manner by first preparing the
purpurine and alizarine from the pectic extract, and then purifying said extract
by the processes herein-before described; 3rdly, by the employment of the
boiling hydrocarburets an important improvement in the coloring principles of
the extracts is obtainable.
<

page_text: Seventbly. I claim the employment of apparatus similar to those used for
the lixiviation of soda in the extraction and washing of madder, garancine,
madder flowers, sulpuric charcoal of madder, and generally of all products
derived from madder.
Eighthly. I claim the treatment of flowers of madder or garancine for ex-
tracting useful products therefrom operating in a similar manner as when
treating madder impregnated with sulphurous water.
Ninthly. I claim obtaining green alizarine in a highly pure condition by
mixing the sulphurous liquors of the madder charged with sugar before fer-
mentation and allowing them to settle, afterwards treating the said fermented
liquors with 2 or three per cent. of sulphuric acid.
Tenthly. I claim obtaining alizarine in the form of alizarate of lime or
calcareous lac in the fermented or other liquors by the addition of milk of lime
after the precipitation of the purpurine.
In witness whereof, I, the said Alexander Melville Clark, have hereunto
set my hand and seal, this Ninth day April, in the year of our Lord
One thousand eight hundred and sixty-eight.
A. M. CLARK. (L.B.)