Process for the Treatment of Vegetable Fibres by Means of Acid, Neutral, and Alkaline Residues of Naphtha Manufacture, or Specially Prepared Substances Analogous to such Residues.
Year: 1889

page_text: Date of Application, 15th May, 1889
Complete Specification Left. 11th Feb., 1890-Accepted, 29th Mar., 1890
PROVISIONAL SPECIFICATION,
Process for the Treatment of Vegetable Fibres by Means of Acid,
Neutral, and Alkaline Residues of Naphtha Manufacture, or
Specially Prepared Substances Analogous to such Residues.
We, VLADIMIR SCHEVELIN, of Balakhna, Russia, Technological Engineer, and
PETER MINDOVSKY, of Moscow, Russia, hereditary honorary Citizen, do hereby
declare the nature of this invention to be as follows:-
In mineral oil factories which produce illuminating, lubricating and other mineral
oils, there is obtained, when treating the mineral oils or the products obtained by
distillation therefrom with sulphuric acid, and after the removal of the mineral oil, a
dark coloured tar like product of variable consistency which in practice obtains various
names, such as acid deposit, acid sludge, acid tar, resin sludge &c. All these special
names are included under the generic term "acid residues." The mineral oil, first
purified by sulphuric acid, is, after separation of the so-called acid residues, treated
with alkalis (mostly caustic soda) whereby there aro separated from the mineral oil
together with the alkali, products of various colours and consistency, to which in
practice various names have been given, such as kerosene glue, kerosene soap,
bleaching glue, bleaching water, bleaching oil, soda-tar &c. All these special names
are included under the generic term "soda residues."
Up to the present time, the acid and soda residues only constitute a comparatively
useless drug in the mineral oil manufacturing industry because the acid residues could
only be used in small quantities for the regeneration of the free sulphuric acid con-
tained therein, while the soda residues only serve for the regeneration of the small
quantity of soda contained therein.
The large quantities of soda and acid residues which are at present obtained in the
factories in working mineral oils and their products can, according to our experiments,
be employed for working fibrous plants such as flax, hemp and the like and for
the preparation from these of not only coloured but also white spun threads, for
which purpose we employ either the acid and soda residues as they are produced
at the works that make illuminating, lubricating, and other mineral oils, or we prepare
such residues ourselves, either in the same way as they are prepared in the factories,
or according to the following method.
The mineral oil distillates or the mineral oil itself is mixed carefully with sulphuric
acid at a temperature of from 15° to 35° C. during from to 2 hours, the sulphuric
acid being employed in the proportion of from 5 to 12 per cent. by weight. The
mixture is then allowed to stand for not less than two hours. The mineral oil that
floats on the top is then separated from the acid residues below, is neutralised with
alkalies (caustic soda or carbonate of soda) under stirring, and heated to from 70°
to 80° (. It is then allowed to stand again, when the soda residue will separate.
The mineral oil separated from the soda residue and heated to from 35° to 90° C. is
again treated with from 15 to 20 per cent. of sulphuric acid with an addition of from
one to three per cent. of chromic acid (or the corresponding quantity of potassium
bichromate with sulphuric acid). There is then again produced an acid residue, while
the oil separated from the same is again neutralised by alkali and beated, thus again
obtaining soda residue. If this alternate treatment with acid and then with alkali is
repeated several times, the greater part of the mineral oil product can be converted
into the acid and soda residues, which was not possible with the treatment generally
used at the factories.
The acid residues of the factories, as also those produced as above described always
contain free sulphuric acid, which is removed by repeated washing with hot water, or
by treating with steam and then neutralising by an alkali, such as caustic soda or

page_text: carbonate of soda (or even lime) until a weak alkaline re-action is obtained. By this
means a neutralised acid residue is obtained.
In employing the neutralised acid residues for the treatment of fibrous plants, the
following process is used: About one part of the residues and nine parts of water are
well stirred together at a temperature of from 25° to 35° C. and the mixture
is allowed to stand. The layer of oil floating on the solution is removed and the
solution is introduced directly into boilers in which are contained the prepared
solution for treating the plants. If it is desired to obtain a fine colour for the fibres,
there is added a 10 per cent, solution of the soda residues which are obtained in the
treatment of kerosene and other illuminating oils, to the extent of about one half the
weight of the former.
The soda residues resulting from the treatment of kerosene and other mineral
illuminating oils are employed directly in an aqueous solution with a preparation not
exceeding 10 per cent. of the residues. When the residues contain unconverted
mineral oil, they are first washed carefully by stirring in warm or hot water.
The opalescent washing water thus produced is employed directly, while the oil
floating upon the same is removed and after evaporating therefrom the water
contained, is first treated with sulphuric acid of from 64 to 66 per cent. and then with
alkalis.
Acid and soda residues are thus again produced which are treated as above
described.
The process for the separation of the fibres from the woody matter by means of
the soda residues and neutralised acid residues consists in the following: The fibrous
plants are boiled at from 90° to 95° C. in the aqueous solution of the residues (the
proportion of which does not exceed 10 per cent.). The re-action of the solution is
first alkaline and afterwards, in order to obtain a lighter colour for the fibres, is
rendered acid by saturation of the solution with sulphur dioxide.
On boiling the fibrous plants, the solution of the residues, having an alkaline
re-action, destroys the connection of the fibres with the woody matter, in consequence
of which the fibre separates from the woody matter.
A similar but weaker decomposing action is also effected by a solution of the
residues having a weak acid re-action, but in this case a lighter coloration of the fibres
is obtained.
The duration of the boiling depends upon the quality of the plants treated, and
varies from half an hour to three hours. Thus, for instance, fresh flax is operated
upon more quickly than flax which is a year old.
The operation of separating the fibre from the woody matter is effected as
follows
:-
The fibrous plants are boiled for a time not exceeding three hours, at a temperature
of from 70° to 95° C., and without pressure, in boilers or tanks filled with a 10 per
cent. solution of the residues, having alkaline reaction. They are then removed and
passed through the usual pressing rollers in order to remove the solution contained
in them together with the different substances and dirt dissolved in the same; the
pressed plants are then passed through rollers, water being poured upon the rollers
and plants so as to wash the latter. The last pair of rollers presses the plants dry,
and these are then introduced into the drying chamber. After drying, they are
broken and scutched, either by means of machinery or by hand, whereupon the finished
fibre is again passed through rollers.
If a light coloured fibre is to be obtained, the operation is modified in the following
manner After the solution of residues with alkaline re-action has been pressed out
of the fibre by rollers, together. with the dirt which has been carried with the plants
from the vats, the plants are not at once washed but are again boiled for a time not
exceeding one hour at a temperature of from 70° to 90° C. in a 10 per cent. solution
of the residues, which must be previously saturated to an acid reaction by means of
sulphur dioxide. The plants are removed from the solution and then pressed between
rollers and at the same time washed by means of water poured over them. They are
then again pressed and dried and treated in the usual manner.

page_text: For obtaining white flax or hemp the following process is employed: The plants
are boiled for from to 3 hours at a temperature of from 70° to 95° C. in a 10 per
cent. solution having alkaline re-action. They are then removed from the boilers or
tanks, passed through rollers, washed with water and then introduced into the solution
of a mixture of chloride of lime with an excess of soda, where they are left from two
to three hours (part. chloride of lime to 1 part soda and 60 parts water). On
removal from the chloride of lime solution the plants are again pressed and washed
with water several times and are then dried between rollers and further treated as
above described.
If a coloured fibre is to be obtained the fibrous plants, after boiling in the solutions
of the residues and subsequent pressing and washing, are again boiled for from to
hour in a mixture of the solutions of any organic colouring matter and the residues,
whereupon they are again pressed, washed with water and passed through a vat heated
to from 25° to 35° C. containing a solution of aluminium salts. On removal from the
vat, they are well washed, dried, and then further treated in the usual manner.
Dated this 15th lov of Nov 1880
ABEL & IMRAY,
Agents for the Applicants.
COMPLETE SPECIFICATION.
Process for the Treatment of Vegetable Fibres by Means of Acid,
Neutral, and Alkaline Residues of Naphtha Manufacture, or
Specially Prepared Substances Analogous to such Residues.
We, VLADIMIR SCHEVELIN of Balakhna, Russia, Technological Engineer, and
PETER MINDOVSKY, of Moscow, Russia, hereditary honorary Citizen, do hereby
declare the nature of this invention and in what manner the same is to be per-
formed to be particularly described and ascertained in and by the following
statement:-
In mineral oil factories which produce illuminating, lubricating and other mineral
oils, there is obtained, when treating the mineral oils or the products obtained by
distillation therefrom with sulphuric acid, and after the removal of the mineral oil, a
dark-coloured tar-like product of variable consistency which, in practice, obtains
various names, such as acid deposit, acid sludge, acid tar, resin sludge &c. All theso
special names are included under the generic term "acid residues." The mineral oil,
first purified by sulphuric acid, is, after separation of the so called acid residues,
treated with alkalis (mostly caustic soda) whereby there are separated from the
mineral oil together with the alkali, products of various colours and consistency, to
which in practice various names have been given, such as kerosene glue, kerosene
soap, bleaching glue, bleaching water, bleaching oil, soda tar &c. All these special
names are included under the generic term "soda residues."
Up to the present time, the acid and soda residues only constitute a comparatively
useless drug in the mineral oil manufacturing industry, because the acid residues
could only be used in small quantities for the regeneration of the free sulphuric acid
contained therein, while the soda residues only serve for the regeneration of the small
quantity of soda contained therein.
The large quantities of soda and acid residues which are at present obtained in the
factories in working mineral oils and their products can, according to our experiments,
he employed for working fibrous plants such as flax, hemp and the like and for the
preparation from these of not only coloured but also white spun threads, for which
purpose we employ either the acid and soda residues as they are produced at the
works that make illuminating, lubricating, and other mineral oils, or we prepare such
residues ourselves, either in the same way as they are prepared in the factories, or
according to the following method.
The mineral oil distillates or the mineral oil itself is mixed carefully with sulphuric
acid at a temperature of from 15° to 35° C. during from to 2 hours, the sulphuric
acid being employed in the proportion of from 5 to 12 per cent. by weight. The

page_text: mixture is then allowed to stand for not less than 2 hours. The mineral oil that
floats on the top is then separated from the acid residues below, is neutralized with
alkalies (caustic soda or carbonate of soda) under stirring and heated to from 70°
to 80° C. It is then allowed to stand again, when the soda residue will separate.
The mineral oil separated from the soda residue and heated to from 35° to 90° C.
is again treated with from 15 to 20 per cent. of sulphuric acid with an addition of
from one to three per cent. of chromic acid (or the corresponding quantity of
potassium bichromate with sulphuric acid). There is then again produced an acid
residue, while the oil separated from the same is again neutralized by alkali and
heated, thus again obtaining soda residue.
If this alternate treatment with acid and then with alkali is repeated soveral
times, the greater part of the mineral oil product can be converted into the acid
and soda residues, which was not possible with the treatment generally used at
the factories.
The acid residues at the factories, as also those produced as above described
always contain free sulphuric acid, which is removed by repeated washing with
hot water, or by treating with steam and then neutralising by an alkali, such
as caustic soda or carbonate of soda (or even lime) until a weak alkaline reaction
is obtained. By this means a neutralised acid residue obtained.
In employing the neutralised acid residues for the treatment of fibrous plants,
the following process is used. About one part of the residues and nine parts of
water are well stirred together at a temperature of from 25° to 35° C. and the
mixture is allowed to stand.
The layer of oil floating on the solution is removed and the solution is intro-
duced directly into boilers in which are contained the prepared solution for treating
the plants. If it is desired to obtain a fine colour for the fibres, there is added
a 10 per cent. solution of the soda residues which are obtained in the treatment of
kerosene and other illuminating oils, to the extent of about one half the weight
of the former.
The soda residues resulting from the treatment of kerosene and other mineral
illuminating oils are employed directly in an aqueous solution with a preparation
not exceeding 10 per cent. of the residues. When the residues contain unconverted
mineral oil, they are first washed carefully by stirring in warm or hot water.
The opalescent washing water thus produced is employed directly, while the oil
floating upon the same is removed and after evaporating therefrom the water
contained, is first treated with sulphuric acid of from 64 to 66 per cent. and then
with alkalis.
Acid and soda residues are thus again produced, which are treated as above
described.
The process for the separation of the fibres from the woody matter by means
of the soda residues and neutralised acid residues consists in the following.
The fibrous plants are boiled at from 90° to 95° C. in the aqueous solution of the
residues, the proportion of which does not exceed 10 per cent. The reaction of the
solution is first alkaline, and afterwards in order to obtain a lighter colour for
the fibres, is rendered acid by saturation of the solution with sulphur dioxide.
On boiling the fibrous plants, the solution of the residues, having an alkaline
reaction, destroys the connection of the fibres with the woody matter, in consequence
of which the fibre separates from the woody matter.
A similar but weaker decomposing action is also effected by a solution of the
residues having a weak acid re-action, but in this case a lighter coloration of the fibres
is obtained.
The duration of the boiling depends upon the quality of the plants treated and varies
from half an hour to three hours. Thus, for instance, fresh flax is operated upon more
quickly than flax which is a year old.
The operation of separating the fibre from the woody matter is effected as
follows:-
-
The fibrous plants are boiled for a time not exceeding three hours at a temperature

page_text: of from 70° to 95° C. and without pressure in boilers or tanks filled with a 10 per cent.
solution of the residues having alkaline reaction. They are then removed and passed
through the usual pressing rollers in order to remove the solution contained in them
together with the different substances and dirt dissolved in the same; the pressed
plants are then pressed through rollers, water being poured upon the rollers and
plants so as to wash the latter. The last pair of rollers presses the plants dry and
these are then introduced into the drying chamber. After drying, they are broken
and scutched, either by means of machinery or by hand, whereupon the finished fibre
is again passed through rollers.
If a light coloured fibre is to be obtained, the operation is modified in the following
manner.
After the solutions of residues with alkaline re-action has been pressed out of the
fibre by rollers, together with the dirt which has been carried with the plants from
the vats, the plants are not at once washed but are again boiled for a time not exceed-
ing. one hour at a temperature of from 70° to 90° C. in a 10 per cent. solution of
the residues, which must be previously saturated to an acid reaction by means of
sulphur dioxide. The plants are removed from the solution and then pressed between
rollers and at the same time washed by means of water poured over them. They
are then again pressed and dried and treated in the usual manner.
For obtaining white flax or hemp the following process is employed: The plants
are boiled for from to 3 hours at a temperature of from 70° to 95° C. in a
10 per cent. solution having alkaline reaction. They are then removed from the
boilers or tanks, passed through rollers, washed with water and then introduced into
the solution of a mixture of chloride of lime with an excess of soda, where they are
left from two to three hours (2 part chloride of lime to 1 part soda and 60 parts
water).
On removal from the chloride of lime solution the plants are again pressed and
washed with water several times and are then dried between rollers and further
treated as above described.
If a coloured fibre is to be obtained the fibrous plants after boiling in the solutions
of the residues and subsequent pressing and washing, are again boiled for from
lohour in a mixture of the solutions of any organic colouring matter and the
residues, whereupon they are again pressed, washed with water, and passed through
a vat heated to from 25° to 35° C. containing a solution of aluminium salts.
removal from the vat they are well washed, dried and then further treated in the
usual manner.
Ön
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed we declare that what we
claim is
The treatment of vegetable fibres by means of acid, neutral or alkaline residues
of naphtha manufacture or of specially prepared substances analogous to such residues,
in combination with a mechanical treatment of the fibres, substantially as and for the
purposes herein set forth.
111111 John 1800
ABEL & IMRAY,
Agents for the Applicants.