IMPROVEMENTS BIL
Year: 1883

page_text: LETTERS PATENT to Thomas Wade Appleyard the younger and Walter Knapp
Appleyard both of Leeds in the county of York and James Longshaw of
Manchester in the county of Lancaster for an Invention of "IMPROVEMENTS
TX BILD
PROVISIONAL SPECIFICATION left by the said Thomas Wade Appleyard,
the younger, and Walter Knapp Appleyard and James Longshaw at the Oilice
of the Commissioners of Patents on the 6th June 1883.
..
THOMAS WADE APPLEYARD the Younger and WALTER KNAPP APPLEYARD both
of Leeds in the county of York and JAMES LONGSHAW of Manchester in the
county of Lancaster IMPROVEMENTS IN THE MANUFACTURE OF SOLUBLE BLACK
The object of our invention is to improve the production of the above mentioned
Soluble Black from substances or liquors containing Gallic Acid, whereby we obtain
a product which can be used as an ingredient in the manufacture of various articles
now made, wherein a cheap soluble or partially soluble Black could be used and
wholly or partially displace some of the more expensive agents now employed. As
an example we mention ordinary blacking.
The source of gallic acid we prefer is spent tan liquor after the whole or nearly
all the tannic acid has been extracted by the ordinary tauning process.
This we treat with various percentages of caustic Lime, Soda, or Potash, or
carbonates of Potash or Soda according to the quality of the liquor under treatment
and by preference use Caustic Soda.
The liquor thus treated we evaporate quickly by any suitable means until the
density or specific gravity ranges between 40 degrees to 70 degrees Twaddle
or even higher. We then add to this liquor certain percentages of soluble iron
salts by preference using sulphate of the protoxide of Iron commonly called Green
vitriol, and thus after exposure to the air obtain one thick dense Black product.
Soluble Black.
By using salts of the per oxide of iron we obtain the desired blackness of liquor
at once,

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent filed by the
said Thomas Wade Appleyard, the younger, and Walter Knapp Appleyard and
James Longshaw in the Great Seal Patent Office on the 6th December 1883.
THOMAS WADE APPLEYARD, the younger and WALTER KNAPP APPLEYARD both
of Leeds in the county of York and JAMES LONGSHAW of Manchester in the county
of Lancaster "IMPROVEMENTS IN THE MANUFACTURE OF SOLUBLE BLACK
"
The object of our invention is to improve the production of the above mentioned
soluble black from substances or liquors containing gallic acid, whereby we obtain a
product which can be used as an ingredient in the manufacture of various articles
now made, wherein a cheap soluble or partially soluble black could be used, and
wholly or partially displace some of the more expensive agents now employed.
As an example we mention ordinary blacking.
The source of gallic acid we prefer is spent tan materials and liquor, especially
the latter, but the solid matters are also useful.
It has long been known that an inferior kind of ink can be made by boiling
down spent tan liquors, that is liquors out of which nearly all the tannin is already
extracted, and treating with iron or ferruginous matters, but in practice all these
attempts have been commercial failures owing to the material having
a strong acid
reaction and largely precipitating in the process of boiling down. Now we have
discovered that if to the spent tan liquor we add sufficient caustic alkali, or even
caustic lime to take up or neutralize all the gallic acid and other acids present in
the solution, we get excellent results and little or no precipitate during the boiling.
We prefer for this purpose caustic soda.
Our manner of operating is as follows.
We add to the tan materials sufficient caustic soda to combine chemically with
all the acid matter present whether in the liquid or in the solid spent material, and
until by any ordinary test uncombined caustic is found to be present; we now add
sufficient fresh liquor to supply acid for the free caustic present and filter or strain
the liquor so as to remove the solid refuse, then evaporate the liquid quickly by
any suitable means to a density or specific gravity of from forty degrees to seventy
degrees Twaddle, the exact density depending upon the purpose to which it is
afterwards to be applied. We now add to this liquor green vitriol (ferrous sulphate)
or other soluble salt of iron, the more basic it is the better, sufficient in amount for
its acid to combine with nearly all the soda present, and expose it to the air to get
the necessary amount of oxidation.
The result is a thick dense black product, the soluble black required. It is in
fact a mixture of gallate of iron and salts of soda. If a ferric salt has been used,
the desired blackness is obtained at once without oxidation or exposure to air.
It would be possible to reverse the process, boil down first and then add the iron
Balt and the caustic, and the result would be a somewhat similar but inferior
material, but it would be a very troublesome operation, owing to the precipitate
that forms in boiling and the difficulty in again dissolving that precipitate or of
preventing it caking or burning while the liquor is being boiled down. One main
point to be considered if the best results be desired is to add no more iron than
the vegetable acids present in the liquor when free are capable of combining with
and to add only such quantity of caustic to the liquor as shall be just sufficient to
chemically combine with all the acid of the original iron salt, leaving the iron free
to combine with the vegetable acids. (1) The iron, (2) the mineral acid of its
salta, (3) the soda and other alkaline base present, (4) the vegetable acids present
are consequently all chemically equivalent proportions to each other,

page_text: As an example we will describe the process of making the soluble black from the
refuse of one of our tanning operations merely premising that it is impossible to
give quantities that will be right for all spent tan materials, as these differ very
widely both as they are formed originally of different materials and as the processes
they have undergone differ materially. To every 80,000 gallons of spent tan liquor
of say two and a half degrees Twaddle, and to every two tons of solid material
such as that made from myrabolams, divi divi, or valonia, we add one hundred-
weight of caustic soda of sixty five to seventy per cent purity. If the spent liquid
only be used, we boil it down with constant stirring till the liquid increases in
density from about two and a half degrees Twaddle or less to 56 degrees Twaddle.
We now separate the solid material by filtration or decantation. If originally
solid spent material and caustic only be used, about sufficient water or spent liquor
must be added to well cover the solid material before boiling, but if solid and
liquid matters be taken together in the proportions produced at the tannery no
water need be added. To every twenty pounds of the liquor at fifty six degrees
Twaddle produced, we now add one pound of ferric sulphate dissolved in the
smallest practicable quantity of hot water and mix well and boil at the same time
till the excess of water added with the iron salt has evaporated. During this time
by any suitable means such as blowing air through it, the liquor is thoroughly
exposed to the air.
Having now described our invention and the best mode known to us of carrying
it into effect, we wish it to be understood that what we believe to be new and
desire to protect under the letters patent is :-
1st. The black material manufactured from waste tan materials, substantially as
and for the purposes described
2nd. The process of manufacturing a finely divided or soluble black, which
consists in treating waste tan liquor or other substance or liquor, rich in gallic acid
or gallates, with alkali, separating the insoluble residue, concentrating and adding
a soluble salt of iron, substantially as described.
In witness whereof we the said Thomas Wade Appleyard the younger, Walter
Knapp Appleyard and Janes Longshaw have hereunto set our hands and seals
this fifth day of December in the year of our Lord one thousand eight hundred
and eighty three.
THOMAS WADE APPLEYARD JR (L.S.)
WALTER KNAPP APPLEYARD (L.S.)
JAMES LONGSHAW
(L.S.)