Process for the Manufacture of Glutinous Substances or Sizes.
Year: 1897

page_text: Date of Application, 29th Mar., 1897
Complete Specification Left, 29th Dec., 1897-Accepted, 12th Mar.,
1898
PROVISIONAL SPECIFICATION.
Process for the Manufacture of Glutinous Substances or Sizes.
I, Professor Dr. ALEXANDER MITSCHERLICH, of Friburg, Baden, Germany,
do hereby declare the nature of this invention to be as follows:-
This invention relates to a new process for the manufacture of a glutinous
substance or size from matters containing horn or ceratine masses or similar
bodies, in employing lye of sulphite cellulose, and for rendering it in particular
suitable by means of resin, for sizing paper.
This invention is based on the observation that resin combined with alkalies
together with the glutinous substance improves the properties of the original
products for the sizing of paper in an unexpected manner.
The manufacture of the glutinous substance is effected advantageously first by
dissolving either directly in the Iye the matters containing the horn or ceratine
and similar bodies and by treating them then as hereinafter described, or by
dissolving them in water in iron kettles protected by lining with lead and
refractory bricks against any prejudicial action of the liquids, at a temperature
superior to 100° C., or by dissolving them in large vats at a temperature inferior
to 100° C. by means of liquids containing dilute alkalies. From these solutions
they are precipitated by means of ye advantageously in adding acids, and these
precipitates are dissolved again in an aqueous solution of soda.
In order to render, in this new process of manufacturing the glutinous sub-
stance, the lye of sulphite cellulose advantageously useful for dissolving directly
the horn substances &c. all the admixtures, rendering the lye unfit for the
dissolving process must be removed.
This is effected by precipitating the detrimental constituents by means of lime
and soda or in general by alkaline carbonates, sulputes or silicates.
For dissolving with certainty the horn substances &c.; in the lye, an addition
of protoxide of sodium or potassium or an addition of soda ter potash and of burnt
lime is necessary. Together with lyes thus prepared the horn is then heated
for some time at a temperature which need not be higher than
C.
The liquid is saturated as desired either almost entirely or partially with
horn &c. and it is then furthermore still appropriate to dissolve large quantities
of resin. This process is practically carried out as follows:-First the lye is
treated separately for this process in the following manner.
Hot lye is mixed in large vats with lime-paste or preferably with the hereinafter
indicated sludge up to a weakly alkaline reaction for precipitating the free or
semi bound sulphurous acid &c. At a specific weight of 1.04 of the original lye
there are now added 6 per cent. anhydrous soda in a pulverulent form (in this
process in place of soda of course potash may also be used), this quantity of soda
being modified correspondingly for other specific weights.
The mass is stirred up for some time and after having been allowed to stand for
sometime a whitish precipitate consisting of carbonate and sulphite of calcium,
carbonate of magnesia &c. is deposited on the bottom. There are then added to

page_text: the hot liquid 3 per cent. of burnt lime in the form of a finer lime-paste or
preferably as burnt lime which soon is slaked. Other specific weights of the
lye require of course a corresponding addition of lime. By the added lime the
soda is transformed, under separation of the lime as carbonate of lime, partly
into protoxide of sodium or into such sodium compounds which abundantly dissolve
horn at a temperature inferior to 100° C. The addition of lime and soda, pro-
ducing a strong separation, is effected in avoiding dilutions as much as possible.
The sludge produced by the settling of the mass is used, as above mentioned,
for neutralising the free acid of the lye, and as soon as there has gathered too
large a quantity of sludge in the vats, it is removed therefrom.
This purification of the lye may advantageously be carried out also in the
following manner:
The lye is mixed with the same quantity of burnt lime as formerly after the
slaking operation; it is then stirred up therewith and allowed to stand for a short
time, the produced compound is pressed off after settling, and mixed with a
quantity of soda dissolved in water nearly equal to the former quantity. After
the deposit has been stirred up therewith, and has then be allowed to stand and is
pressed off, this purified lye containing protoxide of sodium is appropriate for
the subsequent solution (when potash is used the liquids contain, of course,
protoxide of potassium).
In this process, the tanning materials of the lye combine first with the lime
and are then brought by the soda solution, in separating carbonate of lime &c.
into a solution capable of dissolving horn and the like.
For dissolving horn and the like in practice in a continuous working, the clear
liquid is caused to flow permanently into a cask-system arranged in the form of
a terrace in such a manner, that there is a fall from the uppermost cask to the
lowermost, and that the escaping liquid flows through tubes at bottom from
each upper cask into the top of the subsequent lower cask. Each cask is provided
below with an inserted perforated bottom, through which passes only the liquid
running off so that a clogging of the tubes by swelled horn etc. is avoided. By
means of a heating device arranged in each cask a higher temperature may easily
be obtained.
The purified bodies to be dissolved are suitably packed up in pieces (say horn
pieces) in these casks. The supplied ligud gradually fills the casks and flows
then permanently with a fall through the whole system. From the last cask
the solution flows into a receiver, entering at bottom for clarification and flowing
off at top after separation of the impurities. The number of the casks and the
strength of the current of the liquid as well as the height of the temperature
is regulated according to the quantity of horn which is desired in solution. The
clarified solution may further be treated as required and the glue material may
be separated by precipitation. In the paper manufacture this is effected by pre-
cipitating it in the paper pulp, like rosin-size by means of acids or of sulphate
of alumina, so that the fibres cohere together.
This glutinous substance even if employed only in small quantities is capable
of freeing, "the rosin-size from a very detrimental property. By means of a
calcareous liquid, say gypsiferous water and the like, resin is separated from the
rosin-size, and rendered ineffective, so that always a defective sizing of the paper
takes place. If the glue-material is present in the rosin-size, a chemical com-
bination probably takes place between the two substances, which prevents the
precipitation. This new product containing resin possesses the good properties
of the glue material contained therein, i.e., direct applicability and always the
same quality, good sizing in bad water; moreover, the paper manufactured there-
from is more sounding, of a better touch, smoother, stronger and less easily
decomposable by light than the paper sized with rosin-size.
The product has furthermore the good quality of the rosin-size, which in part
is wanting in the glue-material, i.e., the imperviousness to ink, the latter being

page_text: ordinarily greater than that of the rosin-size itself; and moreover, the product
is produced with an economical consumption of soda, by considerably smaller
quantities of sulphate of alumina than the rosin-size.
In the manufacture of the new product by directly dissolving the horn in the
lye, the observed fact is important, that lye of sulphite cellulose treated as above
described, when it is saturated with horn etc. to such a degree, that it hardly
dissolves any more, is, notwithstanding, still capable of dissolving large quantities
of resin.
The liquid thus obtained can then be used directly for sizing paper by precipi-
tation by means of acids or acid salts; preferably by means of sulphate of alumina.
For manufacturing this new material I proceed, as follows:-
Resin is dissolved, as indicated, in the liquid highly saturated, with horn, or
resin is dissolved separately in the lye of sulphite cellulose freed from lime by
means of soda in excess and this solution is mixed with the horn etc. solution
obtained as above described, or aqueous solutions of horn or the like prepared in
any suitable manner are mixed with rosin soap and with lye of sulphite cellulose
freed from lime.
The first solution is advantageously prepared in the following manner:-
In the horn solution prepared as above described the resin is dissolved at a
temperature which need not be higher than 100° C., in such a manner, that the
whole quantity of resin to be dissolved flows gradually in a melted condition into
the relatively small quantity of horn-solution at a temperature of about 100° C. in
permanently stirring up the liquid. The resin remaining undissolved is com-
pletely suspended by the stirring up in the liquid. The remainder of the hot
iye is then added under continuous stirring. If there were contained in the liquid
larger quantities of carbonic acid, the solution of the resin would naturally take
place under a more violent frothing than with a smaller development of carbonic
acid. The resin may of course be dissolved in this horn-solution in very different
proportions; when very large quantities of resin are to be dissolved, either
larger quantities of soda etc. must be added to the lye treated as described, or a
larger quantity of the treated lye having a small yield of horn must be employed.
It has been found advantageous in the product, that no larger quantities of resin
are added to the dissolved horn etc. than about 3:1. If larger quantities of resin
are contained therein, a separation of resin will be produced in the dilute solution
by gypsum which may be dissolved in the waste-water, or by other calcareous
substances.
The horn etc. solution, if it is present in a sufficient quantity in the concentrated
liquid has the effect that all is dissolved so as to form a transparent liquid from
which nothing is eliminated when cold
Larger quantities of resin produce a turbidity by resin soap or a greater
separation of the latter.
The product obtained is a viscid tough mass easily moveable at a higher tempera-
bure dissolving clearly in a little hot water, ordinarily becoming turbid in a large
quantity of water, and ready for being forwarded to the paper manufactories for
sizing the paper in the rag engine.
Dated this 29th day of March 1897.
ABEL & IMRAY,
Agents for the Applicant.
I,
Process for the Manufacture of Glutinous Substances or Sizes.
Professor Dr.
ALEXANDER MITSCHERLICH, of Friburg, Baden, Germany,
do hereby declare the nature of this invention and in what manner the same is to

page_text: be performed, to be particularly described and ascertained in and by the following
statement:
This invention relates to a new process for the manufacture of a glutinous
substance or size from matters containing horn or ceratine masses or similar
bodies, in employing lye of sulphite cellulose, and for rendering it in particular
suitable by means of resin, for sizing paper.
This invention is based on the observation that resin combined with alkalies
together with the glutinous substance improves the properties of the original
products for the sizing of paper in an unexpected manner.
The manufacture of the glutinous substance is effected advantageously first by
dissolving either directly in the lye the matters containing the horn or ceratine
and similar bodies and by treating them as hereinafter described, or by
dissolving them in water in iron kettles protected by lining with lead and
refractory bricks against any prejudicial action of the liquids, at a temperature
superior to 100° C., or by dissolving them in large vats at a temperature inferior
to 100° C. by means of liquids containing dilute alkalies. From these solutions
they are precipitated by means of waste lye of sulphite cellulose, either alone,
or, if the latter does not contain a very considerable excess of acid, under addition
of acid, such as sulphuric or hydrochloric acid. From this precipitate the liquid
is separated and it is then again dissolved in an aqueous carbonate of soda
solution.
In order to render, in this new process of manufacturing the glutinous sub-
stance, the lye of sulphite cellulose advantageously useful for dissolving directly
the horn substances &c. all the admixtures, rendering the lye unfit for the
dissolving process must be removed.
This is effected by precipitating the detrimental constituents by means of lime
and soda or in general by alkaline carbonates, sulphates or silicates.
For dissolving with certainty the horn substances &c., in the lye, an addition
of protoxide of sodium or potassium or an addition of soda or potash and of burnt
lime is necessary. Together with lyes thus prepared the horn is then heated
for some time at a temperature which need not be higher than 100° C.
The liquid is saturated as desired either almost entirely or partially with
horn &c. and it is then furthermore still appropriate to dissolve large quantities
of resin. This process is practically carried out as follows:-First the lye is
treated separately for this process in the following manner.
Hot lye is mixed in large vats with lime-paste or preferably with the hereinafter
indicated sludge up to a weakly alkaline reaction for precipitating the free or
semi-bound sulphurous acid &c. At a specific weight of 1.04 of the original lye
there are now added 6 per cent. anhydrous soda in a pulverulent form (in this
process in place of soda of course potash may also be used) this quantity of soda
being modified correspondingly for other specific weights.
The mass is stirred up for some time and after having been allowed to stand for
some time a whitish precipitate consisting of carbonate and sulphite of calcium,
carbonate of magnesia &c. is deposited on the bottom. There are then added to
the hot liquid 3 per cent. of burnt lime in the form of a finer lime-paste or
preferably as burnt lime which soon is slaked. Other specific weights of the
lye require of course a corresponding addition of lime. By the added lime the
soda is transformed, under separation of the lime as carbonate of lime partly
to protoxide of sodium or into such sodium compounds which abundantly dissolve
horn at a temperature inferior to 100° C. The addition of lime and soda, pro-
ducing a strong separation, is effected in avoiding dilutions as much as possible.
The sludge produced by the settling of the mass is used, as above mentioned,
for neutralising the free acid of the lye, and as soon as there has gathered too
large a quantity of sludge in the vats, it is removed therefrom.
This purification of the lye may advantageously be carried out also in the
following manner:-

page_text: The waste lye is mixed with 3 p. c. of burnt lime immediately after this has
been slaked, it is then stirred up therewith and allowed to stand for a short time,
the produced compound is pressed off after settling, and mixed with a quantity of
soda dissolved in water nearly equal to the former quantity. After the deposit
has been stirred up therewith, and has then been allowed to stand and is pressed
off, this purified Ive containing protoxide of sodium is appropriate for the subse-
quent solution (when potash is used the liquids contain, of course, protoxide of
potassium).
In this process, the tanning materials of the lye combine first with the lime
and are then brought by the soda solution, in separating carbonate of lime &c.
into a solution capable of dissolving horn and the like.
For dissolving horn and the like in practice in a continuous working, the clear
liquid is caused to flow permanently into a cask-system arranged in the form of
a terrace in such a manner, that there is a fall from the uppermost cask to the
lowermost, and that the escaping liquid flows through tubes at bottom from
each upper cask into the top of the subsequent lower cask. Each cask is provided
below with an inserted perforated bottom, through which passes only the liquid
running off so that a clogging of the tubes by swelled horn etc. is avoided. By
means of a heating device arranged in each cask a higher temperature may easily
be obtained.
The purified bodies to be dissolved are suitably packed up in pieces (say horn
pieces) in these casks. The supplied liquid gradually fills the casks and flows
then permanently with a fall through the whole system. From the last cask
the solution flows into a receiver entering at bottom for clarification and flowing
off at top after separation of the impurities. The number of the casks and the
strength of the current of the liquid as well as the height of the temperature
is regulated according to the quantity of horn which is desired in solution. The
clarified solution may further be treated as required and the glue material may
be separated by precipitation. In the paper manufacture this is effected by pre-
cipitating it in the paper pulp, like rosin-size by means of acids or of sulphate
of alumina, so that the fibres cohere together.
This glutinous substance even if employed only in small quantities is capable
of freeing the rosin-size from a very detrimental property. By means of a
calcareous liquid, say gypsiferous water and the like, resin is separated from the
rosin-size, and rendered ineffective, so that always a defective sizing of the paper
takes place. If the glue-material is present in the rosin-size, a chemical com-
bination probably takes place between the two substances, which prevents the
precipitation. This new product containing resin possesses the good properties
of the glue material contained therein, .e. direct applicability and always the
same quality, good sizing in bad water; moreover, the paper manufactured there-
from is more sounding, of a better touch, smoother, stronger and less easily
decomposable by light than the paper sized with rosin-size.
The product has furthermore the good quality of the rosin-size, which in part
is wanting in the glue-material, i.e. the imperviousness to ink, the latter being
ordinarily greater than that of the rosin-size itself; and moreover, the product
is produced with an economical consumption of soda, by considerably smaller
quantities of sulphate of alumina than the rosin-size.
In the manufacture of the new product by directly dissolving the horn in the
lye, the observed fact is important, that lye of sulphite cellulose treated as above
described, when it is saturated with horn etc. to such a degree, that it hardly
dissolves any more, is, notwithstanding, still capable of dissolving large quantities
of resin.
The liquid thus obtained can then be used directly for sizing paper by precipi-
tation by means of acids or acid salts; preferably by means of sulphate of alumina.
For manufacturing this new material I proceed, as follows:-
Resin is dissolved, as indicated, in the liquid highly saturated with horn, or
resin is dissolved separately in the lye of sulphite cellulose freed from lime by

page_text: means of soda in excess and this solution is mixed with the horn &c., solution
obtained as above described, or aqueous solutions of horn or the like prepared in
any suitable manner are mixed with rosin soap and with lye of sulphite cellulose
freed from lime.
The first solution is advantageously prepared in the following manner:-
In the horn solution prepared as above described the resin is dissolved at a
temperature which need not be higher than 100° C., in such a manner, that the
whole quantity of resin to be dissolved flows gradually in a melted condition into
the relatively small quantity of horn-solution at a temperature of about 100° C. in
permanently stirring up the liquid. The resin remaining undissolved is com-
pletely suspended by the st rring up in the liquid. The remainder of the hot
lye is then added under continuous stirring. If there were contained in the liquid
larger quantities of carbonic acid, the solution of the resin would naturally take
place under a more violent frothing than with a smaller development of carbonic
acid. The resin may of course be dissolved in this horn-solution in very different
proportions; when very large quantities of resin are to be dissolved, either
large quantities of soda etc. must be added to the lye treated as described, or a
larger quantity of the treated lye having a small yield of horn must be employed.
The horn &c. solution, if it is present in a sufficient quantity in the concentrated
liquid has the effect that all is dissolved so as to form a transparent liquid from
which nothing is eliminated when cold.
The product obtained is a viscid tough mass easily moveable at a higher tempera-
ture dissolving clearly in a little hot water, ordinarily becoming turbid in a large
quantity of water, and ready for being forwarded to the paper manufactories for
sizing the paper in the rag engine.
Having now particularly described and ascertained the nature of my said
invention and the manner in which the same is to be performed I declare that
what I claim is:-
1. The process of manufacturing glutinous substances or sizes from matters
containing horn and similar bodies by means of lye of sulphite cellulose consisting
either in dissolving the said substances in the lye containing alkali, which is
treated with lime and carbonate of soda or potash or with protoxide of sodium
or of potassium, for removing matters detrimental to the solution and for intro-
ducing the alkali, or in dissolving the same in the solution which is produced
from a precipitate obtained from the waste lye by means of lime after treatment
with carbonate of soda or potash, substantially as described.
a
2. In the process referred to in the first claim, the addition of resin to the said
alkaline solution of horn or similar substances for the purpose of producing
glutinous substance particularly suitable for sizing paper material substantially
as described.
3. The modification of the process referred to in the second claim, consisting in
preparing separate solutions respectively of the substances containing horn or the
like, and of the resin, in the sulphite lye containing alkaline carbonate, or prepared
as set forth in the first claim, and then mixing the said solutions together, or in
preparing solutions of horn and resin in aqueous caustic alkaline or alkaline car-
bonate solutions, and then adding these to the sulphite lye treated as set forth in
the first claim, substantially as described.
4. For carrying out the process set forth in the first claim in a continuous
manner, a system of heated recipients charged with the substances containing
horn and the like, preferably arranged in terrace form in such manner that the
waste lye introduced into the top vessel, is made to pass from the bottom thereof
into the top of the next lower one, substantially as described.
5. As a new manufacture the glutinous substance produced as set forth in the
first claim as sizing material for paper material, substantially as described.
6. As a new manufacture, the glutinous substance produced as set forth in 5
Claims 2 and 3 serving as size for paper material and composed of substances

page_text: containing horn and similar material, waste sulphite lye, resin and soda, which
size forms a clear solution with a little hot water, while when cold it is of a tough
viscous nature, increasing in fluidity as the temperature is raised, and which
when treated with acid, separates a product consisting of resin and a tannin
compound, substantially as described.
Dated this 20th day of Danamba 1907
ABEL & IMRAY,
Agents for the Applicant.