IM- PROVEMENTS IN TREATING MADDER AND PLANTS OF THE SAME FAMILY AND PRE- LETTERS
Year: 1859

page_text: LETTERS PATENT to James Higgin, of the City of Manchester, in the
County of Lancaster, Manufacturing Chemist, for the Invention of "IM-
PROVEMENTS IN TREATING MADDER AND PLANTS OF THE SAME FAMILY AND PRE-
LETTERS PAT
to James Higgin, of the City of Manchester, in the
County of Lancaster, Manufacturing Chemist, for the Invention of "IM-
PROVEMENTS IN TREATING MADDER AND PLANTS OF THE SAME FAMILY AND PRE-
PARATIONS THEREFROM.
Sealed the 19th October 1859, and dated the 25th April 1859.
PROVISIONAL SPECIFICATION left by the said James Higgin at the
Office of the Commissioners of Patents, with his Petition, on the 25th
April 1859.
I, JAMES HIGGIN, of the City of Manchester, in the County of Lancaster,"
Manufacturing Chemist, do hereby declare the nature of the said Invention for
"IMPROVEMENTS IN TREATING MADDER AND PLANTS OF THE SAME FAMILY AND PRE-
PARATIONS THEREFROM," to be as follows:-
In treating madder or plants of the same family, or preparations therefrom,
for the purpose of making a concentrated coloring matter, and also for the
purpose of eliminating or destroying the vegetable and mineral substances
which detract from the purity of the shades dyed, it is usual to employ acids,
generally sulphuric or muriatic, which are for the most part used in two ways,
either the ground madder in the natural state, or after undergoing a pre-
liminary washing, steeping, or fermenting process, is mixed with the acid along
with a small quantity of water, and steam passed through the mass for a suffi-
cient time. Or the madder, or prepared or steeped madder, or a preparation
therefrom, is mixed with the acid and a larger quantity of water, and the
mixture boiled by steam or in any other suitable manner for a sufficient time.
In either case the acid mixture is then drained and washed by percollation or

page_text: repeated affusion of water until the acid is removed. The preparations of
madder, called garancine and garanceux, are thus made, and are used either
in the wet state or pressed, dried, and ground. It is usual with garancine
makers to add before using or drying a portion of alkali or chalk, so as to
ensure the neutralizing of the acid. Some garancine makers prefer to add a
soluble alkali to the last washing water, and thus neutralize and wash away
the last traces of acid.
My improvement consists in causing the madler, or prepared madder, or
any preparation of such, to remain in contact with the acid for a much longer
period than usual, and also by the means I employ to become more completely
acted on than is generally done by the ordinary means. My improvement can
either be applied to the product obtained by boiling or steaming madder, or a
preparation of it, with an acid in the ordinary way, or can he applied to
madder direct. In the former case I take the acid mixture after boiling and
drain away or press out the superfluous acid water, or where madder is steamed
in the dry way with acid, I mix with a little water and drain as before. In
either case I leave the mixture distinctly sour to the taste; if this is then put
aside for a sufficient time, especially if assisted by a gentle heat, a gradual
change takes place in the substance, the time required to produce which varies
with the sort of madder employed. But a more expeditious and better way is
to dry the moist acid substance, either at the ordinary atmospheric tempera-
ture or by artificial heat. When I find the moist substance is sufficiently
acted upon by prolonged contact with the acid, or when by the other method
the moist acid substance is dried, I put it on a filter, and with water wash
away the acid till the water passes away neutral. In some cases this washing
may be unnecessary, and a sufficient quantity of a neutralizing substance
added. It is then ready for use, or may be still further improved by being
treated in the manner patented by me on the Twenty-eighth day of November
1856, N° 2815. When I act upon madder direct, I moisten it with a mixture
of acid and water, and after letting the mass stand till the madder is thoroughly
wetted I put it aside for a sufficient time, either keeping it warm or not, or I
dry it as before stated. In some cases I prefer to wet the madder with water
first, and allow it to remain wetted for a period before adding the acid, and
then proceed as before. After prolonged contact with acid, or after drying the
acid mixture, I wash on a filter as before, or add a sufficient quantity of
neutralizing substance, and the substance is ready for use, or may be further
purified as before stated.
Another portion of my improvements consist in the use of certain corrosive
salts of metallic oxides, wholly or in part in place of acids, in the manufacture

page_text: of preparations of madder, the method of using which I will fully describe in
my Final Specification.
Another portion of my Invention relates to the manufacture of an extract
of madder. For this purpose I exhaust madder with water or other suit-
able fluid, and after adding an alkali or basic oxide to the liquor, I oxidize
by a stream of air or by other means. By this means I obtain a precipitate,
which is decomposed by acid, and a concentrated coloring matter obtained
therefrom. The exhausted madder and the liquor separated from the preci-
pitate are treated with acid, either mixed or separate, and a weaker coloring
matter obtained; or I nix madder with an alkali or alkaline salt, or basic
oxide and water, and oxidise by a stream of air or in other suitable manner,
and then filter, and to the filtered liquor add metallic oxide, or a salt of such,
and obtain a precipitate which is treated as before stated, and the spent
madder and liquor economized as before.
It may be observed that when in this foregoing I speak of madder, I include
under that name all plants of the family rubiacea, by whatever name they are
known in commerce.
SPECIFICATION in pursuance of the conditions of the Letters Patent, filed
by the said James Higgin in the Great Seal Patent Office on the 25th
October 1859.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, JAMES
HIGGIN, of the City of Manchester, in the County of Lancaster, Manufacturing
Chemist, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her Letters
Patent, bearing date the Twenty-fifth day of April, in the year of our Lord
One thousand eight hundred and fifty-nine, in the twenty-second year of Her
reign, did, for Herself, Her heirs and successors, give and grant unto me,
the said James Higgin, Her special licence that I, the said James
Higgin, my executors, administrators, and assigns, or such others as I, the
said James Higgin, 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 TREATING MADDER AND PLANTS OF THE SAME FAMILY AND
PREPARATIONS THEREPROM," upon the condition (amongst others) that I, the

page_text: said James Higgin, by an instrument in writing under my hand and seal,
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 calender months next
and immediately after the date of the said Letters Patent.
NOW KNOW YE, that I, the said James Higgin, do hereby declare the
nature of my said Invention, and the manner in which the same is to be per-
formed, to be particularly described and ascertained in and by the following
statement (that is to say):-
In treating madder, or plants of the same family, or preparations therefrom,
for the purpose of making a concentrated coloring matter, and at the same
time of eliminating or destroying the vegetable aud mineral substances which
are injurious to the dye stuff, it is usual to employ acids, generally sulphuric
or muriatic, which are used in two ways, either the ground madder in the
natural state, or after undergoing a preliminary washing, steeping, or fer-
menting process, is mixed with the acid, along with a small quantity of water,
and steam passed through the mass for a sufficient time; or the madder or
prepared or steeped madder, or a preparation therefrom is mixed with the
acid and a larger proportion of water, and the mixture boiled in any suitable
manner for a sufficient time; in either case the acid mixture is then drained
and washed until the acid is removed. The preparations of madder called
garancine and garanceux are thus made:-Most garancine makers add to the
mass, when washed, a portion of chalk or alkali, so as to ensure the neutralizing
of the acid, but some prefer to add a soluble alkali to the last washing water,
and thus wash away the last traces of acid.
press out the super-
My improvements consist in causing the madder or a preparation of it to
remain in contact with the acid for a much longer period than usual, and by
the peculiar means I employ to be more completely acted on than is done by
the ordinary processes. This improvement can either be applied to the product
obtained by boiling or steaming madder with an acid in the usual way of
making garancine, or can be applied to madder direct. In the former case I
take the acid mixture, after boiling, and drain away or
fluous acid liquor, or where the madder is steamed in the dry way with acid,
I mix with a little water, and drain or press as before; in either case, instead
of washing with water at once, I leave the mixture distinctly sour to the
taste, and allow it to remain thus acid for a prolonged period. The time will
vary with the sort of madder under treatment; in general from five to ten
days will be sufficient to improve the garancine enough, and experience only
can be the guide; it is then broken up and washed free from acid, and, if

page_text: necessary, dried and ground. Or, instead of putting the acid moist mass
aside for a long period, I dry it at once by artificial heat; when dry, break
up, and wash away the acid in the usual way. The improved garancine may
then be dried and ground, or may be subjected to the treatment patented by
me on the Twenty-eighth day of November, One thousand eight hundred and
fifty-six, No. 2815. When I act upon madder direct, I moisten it with water,
and, after letting it stand thus moist for three or four hours, I add muriatic or
sulphuric acid diluted a little with water, and mix well in. I then heap it up,
and leave it for several days, say, from three to ten days, according to the
sort of madder under treatment. The quantity of acid added is such as is
usually employed in making garancine, and will also vary according to the
sort of madder, from fifteen to twenty-five per cent. of the weight of the
madder being sufficient; or, instead of leaving the acid mixture for a long
period, I press it, leaving in sufficient acid to give a distinctly sour taste to
the pressed stuff, and dry by artificial heat. In either case I break up and
wash in the usual way with water till freed from acid. Or, I mix madder
with sufficient water to make it tolerably fluid, and after allowing it to stand
a few hours I add muriatic or sulphuric acid, as usual for garancine, but
instead of boiling, let the mixture stand cold for several days, stirring up
occasionally; then run off, and wash free from acid. Or, after steeping in
water, and adding acid, I run off, drain, and press, leaving the mass sufficiently
acid to be distinctly sour to the taste; this pressed stuff is then put aside for
several days, or dried as before stated; in either case being ultimately broken
up, and washed with water till free from acid; these preparations being usually
ground and dried, as usual for garancine.
Another portion of my improvements consists in the use of corrosive metallic
salts partly in place of acid. In this process I give the madder a preliminary
steeping or fermenting, as above described, and instead of adding acid, I add
a portion of a metallic salt, such as chloride of zinc, chloride of calcium, or
sulphate of zinc; most of the metallic chlorides will answer the purpose, but I
prefer to use chloride of zinc, as being very corrosive. The mixture, after
standing a few hours, is pressed, allowing sufficient chloride or other metallic
salt to remain in, to give a distinct taste to the stuff. It is then dried by
artificial heat, as usual, for garancine; when dry, broken up and covered with
water, to which about ten per cent. of the weight of the original madder in
sulphuric or muriatic acid is added. The mixture is allowed to stand till the
acid has thoroughly permeated the stuff, or for from twelve to twenty-four hours;
but by heating the mixture, the time may be reduced to three or four hours.
It is not necessary to boil it. It is then filtered and washed free from acid,

page_text: and may then be pressed, dried, and ground. The quantity of metallic salt
employed may be from five to ten per cent. of the weight of the madder in the
dry salt. If the madder contains chalk, or a basic salt of alkaline earth, it is
better to neutralize this first with a little acid before adding the metallic salt,
or a mixture of a metallic salt and a mineral acid, such as sulphuric or
muriatic acid may be added to the steeped or fermented madder, which is then
treated as above described where the metallic salt only is used.
Another portion of my Invention consists in the manufacture of an extract
of madder. For this purpose I make use only of those madders which abound
in the yellow coloring matter soluble in water, which has been variously
designated rubian and xanthine; the fresher also the madder the better; and
madder roots fresh pulled, and not dried but chopped fine, are the best of all.
Dutch madder abounding in this principle is well adapted for this manufacture.
It is also well known to chemists that madder of the above description contains
in addition a fermenting principle, which when water is added to such madder
speedily causes the rubian to change into coloring matters insoluble in water,
and it is essential to my process that this change should not take place; there
are several ways of doing this, either by adding an acid to the water, or any
salt capable of coagulating the fermenting principle, and also by putting the
madder into boiling water and boiling a few minutes, but since boiling water
also extracts other matters than the rubian, and which would deteriorate the
extract somewhat, I prefer to arrest the conversion of the rubian by a metallic
salt or an acid, and I have found acetate of lead to be sufficiently effective ;
different madders will require different quantities of the arresting substances,
but I have found that from three to six per cent. of the weight of the madder
in acetate of lead is generally sufficient. Whatever be the substance used I
mix it with the water, which should be cold, and then add the madder, stirring
well, and after the lapse of an hour or so I filter the mixture and wash with
cold water till no more yellow liquor comes away. The yellow liquor then, if
sufficiently freed from other matters, will give no colored precipitate with acetate
of lead. It should be observed that if the madder contains chalk or a basic
salt of an alkaline earth, a sufficient quantity of acetic acid should be added to
the water to neutralize this substance, and so prevent loss of the metallic salt.
Of course when an acid is used to arrest the change of rubian, the acetic acid
is unnecessary. The crude solution of rubian is then mixed with an alkali or
an alkiline salt, and a current of air blown in for several hours, the liquor
being kept warm. Ammonia answers very well for this purpose, though other
alkalies will do. After continuing the action for several hours a salt of an
alkaline earth, such as muriate of lime is added, when a red precipitate falls, or

page_text: to the rubian liquor is added a mixture of ammonia and muriate of lime, and
air blown in as before; and when no more red precipitate falls the process may
be stopped, or lime may be added at once to the rubian liquor and oxidation
produced as before. In any case the red precipitate is filtered out and mixed
with a small quantity of water, and sufficient muriatic or sulphuric acid added
to make it very sour. It is then boiled for about an hour, more or less, cooled,
filtered, and the resulting extract washed till neutral. It is then a very con-
centrated extract of madder, and may be used in the wet state for dyeing or
printing, or may be dried and ground.
Another way of obtaining the oxidized rubian is by adding madder of the
above class to water containing a soluble alkali, and oxidizing by a current
of air as before, then filtering and washing out the red liquor, to which
is added a salt of lime or other alkaline earth as long as any precipitate
falls; this precipitate is then boiled with acid, &c., as before stated, but as the
alkali extracts also other substances than rubian, the resulting extract is not
so pure as by the other processes.
Having thus fully described my improved processes for treating madder, be
it known that I do not confine myself to the exact details here given, but I
claim as my Invention,-
First, the subjecting madder, or a preparation of it, to a prolonged contact
with acid at the ordinary temperature of the air previous to washing.
Second, the drying a mixture of madder, or a preparation of it, and acid,
subsequently washing out the acid.
Third, the use of corrosive metallic salts, in the manner herein described.
And, fourth, the manufacture of an extract of madder from the rubian
contained therein in the manner herein described.
In witness whereof, I, the said James Higgin, have hereunto set my
hand and seal, this Twenty-fourth day of October, in the year of
our Lord One thousand eight hundred and fifty-nine.
JAMES HIGGIN. (L.S.)
Witness to the signature of the said
James Higgin,
GEO. SEP. HUGHES, 17, Cross Street,
Manchester.