A New or Improved Process for the Purification of Mineral Oils and for Producing Alcohol.
Year: 1889

page_text: Date of Application, 29th Aug., 1889
´omplete Specification Left, 23rd May, 1890-Accepted, 28th June, 1890
PROVISIONAL SPECIFICATION.
A New or Improved Process for the Purification of Mineral Oils
and for Producing Alcohol.
A communication from abroad by PAUL MARIX, of Paris, in the Republic of
France, Proprietor, and NAUM NOTKIN, of Moscow, in the Empire of Russia,
Chemist.
I, WILLIAM PHILLIPS THOMPSON F.C.S., M.I.M.E., of the Agency for Foreign
Patent Solicitors, 6, Lord Street, Liverpool & 6, Bank Street, Manchester, both
in the County of Lancaster & 323 High Holborn, in the County of Middlesex, Civil
Engineer, do hereby declare the nature of this invention to be as follows :-
:-
Naphtha and mineral oils contain, besides the hydrocarbons, a certain quantity of
organic substances which are eliminated by the treatment of these oils by acid
(especially by sulphuric acid).
The combination and mixture of these acids with the organic substances form a
dark and dense mass known as pitch.
This pitch is always acid, in consequence of the employment of an excess of
sulphuric acid for obtaining a complete purification of the inineral oil.
The objects of the present invention are the processes for, on the one hand,
changing into alcohol the vegetable matters acted on by the sulphuric acid, and, on
the other hand, for the direct employment of the excess of sulphuric acid used in the
purification, for changing into alcohol such products as are capable of forming
glucose and of fermenting. Further, this utilisation of the acid has the effect of
yielding a better purification of the mineral oils, as will be seen in the following
description.
(a) To mineral oils or naphtha, before undergoing the usual purification, is added
a quantity, varying from 1% to 5% (or more in special cases) of vegetable matters,
such as wood, straw, paper, bran, leaves, moss, etcetera, etcetera, in fact any suitable
substance capable of forming glucose by the addition of acids.
This addition of vegetable substances has the effect:-
1st. Of increasing the quantity of vegetable matter found in the pitch, so as to
absorb the excess of acid.
2nd. Of rendering more perfect the purification of the oils which become clearer
and more limpid and lose their acrid creosote smell.
This addition of vegetable matters having been accomplished, the process of
purifying the oils proceeds as usual in the case of naphtha, its sub-products, and
mineral oils, however produced, (crude petroleum, shale oil, ozokerit, paraffin,
etcetera, etcetera) by allowing the deposit of the pitchy matters to go on for about
12 hours.
This pitchy deposit contains then a quantity of fermentable matters corresponding
to the quantity of acid employed for the purifying, and these fermentable matters can
be utilised for the production of alcohol, as will be shown later.
(6) Instead of adding the vegetable substances for the purpose of absorbing the
excess of sulphuric acid and producing fermentable matters, before the purification,
the same result as regards the production of alcohol can be obtained by the addition
of vegetable sul stances to the acid pitch usually obtained by the ordinary processes
for the manufacture and purification of naphtha, its sub-products or of mineral oils;
by the addition to these same pitchy products, of vegetable substances, under the
following conditions.
The pitch is heated to 85° or 90° Centigrade, with the addition, according to their
density, of from 40 % to 75°. of vegetable substances, as enumerated above. The
mixture is stirred frequently and kept at this temperature for 24 hours.
с
(c) The pitch obtained from the first or second method of treatment or even the

page_text: acid pitch resulting from the usual mode of treatment for purifying mineral oils
transformed into alcohol in the following manner :-
About five times its weight of hot water is added to it and kept at boiling point
for 6 hours.
When the mass has cooled, the acids contained are neutralise by means of chalk,
lime, or other alkaline substances, and it is allowed to stand until the salts formed
(gypsum, etcetera) are deposited on the bottom.
The portion remaining liquid is then decanted and evaporated until the whole
is of a consistency of 5 or 6 degrees by Beaume's aréometer at a temperature of
19° Centigrade.
When the mixture has cooled to 30° Centigrade, 15 litres of yeast from beer per
1000 litres of the mixture are added.
The fermentation and distillation are then proceeded with according to the ordinary
known methods for manufacturing alcohol. Instead of absorbing the sulphuric acid
in the acid pitch, by means of vegetable substances, it can also be absorbed by
lighting gas for forming alcohol, as it is known that lighting gas can be transformed
into alcohol by means of sulphuric acid. But up to now, this mode of manufacturing
alcohol has not been utilised industrially because of the large quantity of sulphuric
acid required, and consequently, of the high cost of production.
The following is the way in which it is rendered possible to obtain alcohol
Industrially by means of lighting gas, by substituting the acid pitch arising from the
purification of mineral oils for the sulphuric acid of commerce.
The pitch from mineral oils and the subproducts of naphtha, obtained during the
ordinary processes of purification and rectification with the addition of vegetable
substances, can be utilised in the production of alcohol in the manufacture of benzole,
where a considerable quantity of lighting gas is obtained as a waste product, and
that by treating the pitch with ethylene (CH).
The ordinary pitch without the addition of vegetable substances is saturated with
ethylene at 70 Centigrade by passing lighting gas through it under strong pressure.
The ethylene contained in the lighting gas combines with the sulphuric acid, and
forms sulphates of ethylene (CHS O) which, by decomposition and distillation,
yield alcoliol.
The liquid remaining in the distilling apparatus is evaporated in its turn for
manufacturing asphalt. If the pitch, on the other hand, contains vegetable matters
after the alcohol is distilled, it is treated by the method described above, so that it can
be again utilised for the distillation of alcohol.
The details of operation, the proportions of chemicals used, and the temperatures,
etcetera, recommended, are not to be considered absolute, as slight variations therein
may be made without departing from the essential points of the invention.
Dated this 28th day of August 1889.
WM. P. THOMPSON & Co.,
Agents for the Applicant.
COMPLETE SPECIFICATION.
A New or Improved Process for the Purification of Mineral Oils
and for Producing Alcohol.
A communication from abroad by PAUL MARIX, of Paris, in the Republic of
France, Proprietor, and NAUM NOTKIN, of Moscow, in the Empire of Russia,
Chemist.
I, WILLIAM PHILLIPS THOMPSON, F.C.S., M.I.M.E., of the Agency for Foreign
Patent Solicitors, 6, Lord Street, Liverpool, and 6, Bank Street, Manchester, both in
the County of Lancaster, and 323, High Holborn, in the County of Middlesex, Civil
Engineer, do hereby declare the nature of this invention and in what manner the
same is to be performed, to be particularly described and ascertained in and by the
following statement :-
Naphtha and mineral oils contain, besides the hydrocarbons, a certain quantity of

page_text: organic substances which are eliminated by the treatment of these oils by acid
(especially by sulphuric acid).
The combination and mixture of these acids with the organic substances form a
dark and dense mass known as pitch.
This pitch is always acid, in consequence of the employment of an excess of
sulphuric acid for obtaining a complete purification of the mineral oil.
The objects of the present invention are the processes for, on the one hand,
changing into alcohol the vegetable matters acted on by the sulphuric acid, and, on
the other hand, for the direct employment of the excess of sulphuric acid used in the
purification, for changing into alcohol such products as are capable of forming
glucose and of fermenting. Further, this utilisation of the acid has the effect of
yielding a better purification of the mineral oils, as will be seen in the following
description.
(a) To mineral oils or naphtha, before undergoing the usual purification, is added a
quantity, varying from 1 per cent. to 5 per cent. (or more in special cases) of vegetable
matters, such as wood, straw, paper, bran, leaves, moss, etcetera, etcetera, in fact any
suitable substance capable of forming glucose by the addition of acids.
This addition of vegetable substances has the effect:-
1st. Of increasing the quantity of vegetable matter found in the pitch, so as to
absorb the excess of acid.
2nd. Of rendering more perfect the purification of the oils which become clearer
and more limpid and lose their acrid creosote smell.
This addition of vegetable matters having been accomplished, the process of
purifying the oils proceeds as usual in the case of naphtha, its sub-products, and
mineral oils, however produced, (crude petroleum, shale oil, ozokerit, paraffin,
etcetera, etcetera) by allowing the deposit of the pitchy matters to go on for about
12 hours.
This pitchy deposit contains then a quantity of fermentable matters corresponding
to the quantity of acid employed for the purifying, and these fermentable matters can
be utilised for the production of alcohol, as will be shown later.
(b) Instead of adding the vegetable substances for the purpose of absorbing the
excess of sulphuric acid and producing fermentable matters, before the purification,
the same result as regards the production of alcohol can be obtained by the addition
of vegetable substances to the acid pitch usually obtained by the ordinary processes
for the manufacture and purification of naphtha, its sub-products or of mineral oils;
by the addition to these same pitchy products, of vegetable substances, under the
following conditions. The pitch is heated to 85 degrees or 90 degrees Centigrade,
with the addition, according to their density, of from 40 per cent. to 75 per cent. of
vegetable substances, as enumerated above. The mixture is stirred frequently and
kept at this temperature for 24 hours.
(c) The pitch obtained from the first or second method of treatment or even the
acid pitch resulting from the usual mode of treatment for purifying mineral oils is
transformed into alcohol in the following manner:
About five times its weight of hot water is added to it and kept at boiling point for
6 hours. When the mass has cooled, the acids contained are neutralised by means of
chalk, lime, or other alkaline substances, and it is allowed to stand until the salts
formed (gypsum, etcetera) are deposited on the bottom. The portion remaining liquid
is then decanted and evaporated until the whole is of a consistency of 5 or 6 degrees
by Beaumé's aréometer at a temperature of 19 degrees Centigrade. When the
mixture has cooled to 30 degrees Centigrade, 15 litres of yeast from beer per
1000 litres of the mixture are added. The fermentation and distillation are then
proceeded with according to the ordinary known methods for manufacturing alcohol.
Instead of absorbing the sulphuric acid in the acid pitch, by means of vegetable
substances, it can also be absorbed by lighting gas for forming alcohol, as it is known
that lighting gas can be transformed into alcohol by means of sulphuric acid. But
up to now, this mode of manufacturing alcohol has not been utilised industrially

page_text: because of the large quantity of sulphuric acid required, and consequently, of the high
cost of production.
The following is the way in which it is rendered possible to obtain alcohol
industrially by means of lighting gas, by substituting the acid pitch arising from the
purification of mineral oils for the sulphuric acid of commerce.
The pitch from mineral oils and the subproducts of naphtha, obtained during the
ordinary processes of purification and rectification with the addition of vegetable
substances, can be utilised in the production of alcohol in the manufacture of benzole,
where a considerable quantity of lighting gas is obtained as a waste product, and that
by treating the pitch with ethylene (CH).
The ordinary pitch without the addition of vegetable substances is saturated with
ethylene at 37 degrees Centigrade by passing lighting gas through it under strong
pressure. The ethylene contained in the lighting gas combines with the sulphuric
acid, and forms sulphates of ethylene (C2H SO) which, by decomposition and
distillation, yield alcohol.
The liquid remaining in the distilling apparatus is evaporated in its turn for
manufacturing asphalt. If the pitch, on the other hand, contains vegetable matters
after the alcohol is distilled, it is treated by the method described above, so that it can
be again utilised for the distillation of alcohol.
The details of operation, the proportions of chemicals used, and the temperatures,
etcetera, recommended, are not to be considered absolute, as slight variations therein
may be made without departing from the essential points of the invention.
Having now particularly described and ascertained the nature of the said inven-
tion, and in what manner the same is to be performed, as communicated to me
by my foreign correspondents, I declare that what I claim is :-
1. The process for facilitating the clarification and purification of mineral oils and
for making the residual pitch capable of being converted on a commercial scale into
alcohol, the said process consisting in adding to the mineral oils before their purifica-
tion from 1 per cent. to 5 per cent. of vegetable matter capable of producing glucose
under the action of the acids employed for the purification of the oils aforesaid,
substantially as described in paragraph (a).
2nd. The converting into alcohol of the acid pitchy matters obtained as described
in the preceding claim or otherwise by the process described in paragraph (e), said
process consisting in adding to such pitch five times its weight of hot water, in
keeping the mixture at boiling point for about 6 hours, in then allowing the mass to
cool, neutralizing the acids therein, allowing it to settle, decanting the liquid portion
thereof, evaporating said portion to a density of from 5 degrees to 6 degrees Beaumé,
at a temperature of 19 degrees Centigrade, adding to the resultant mixture, when it
has cooled to 30 degrees Centigrade, 15 litres of beer yeast per 1000 litres of the
mixture, and finally fermenting and distilling it as in the usual processes for
manufacturing alcohol, substantially as described.
3. The process for preparing the acid pitch, obtained in the ordinary purification
of mineral oils, the said process consisting in heating the pitch to about 85 degrees
Centigrade, adding thereto from 40 per cent. to 75 per cent. of vegetable matter
capable of being transformed into glucose by the action of acids, and agitating the
mass at this temperature of 85 degrees Centigrade for about 24 hours, whereby the
acid pitch is enriched prior to its conversion into alcohol, substantially as described
in paragraph (b).
4. The production of alcohol by the passage of lighting gas, resulting from the
manufacture of benzole or from other source, through acid pitch, the residue from the
purification of mineral oils, in such a manner as to form sulphates of ethylene, which
by decomposition and distillation yield alcohol, substantially as described.
Dated this 22nd day of May 1890.
WM. P. THOMPSON & Co.,
Agents for the Applicant.