AN IMPROVED PROCESS OF MANUFACTURING BENZINE AND ITS HOMOLOGUES BY THE DISTILLATION OF COAL, WOOD, TURF, OIL AND OTHER SIMILAR SUBSTANCES
Year: 1884

page_text: PROVISIONAL SPECIFICATION.
I NARCISSE ALFRED HÉLOUIS of Boulevard Saint Denis 1 at Paris Chemist
Engineer do hereby declare the nature of my invention for AN IMPROVED PROCESS
OF MANUFACTURING BENZINE AND ITS HOMOLOGUES BY THE DISTILLATION OF
COAL, WOOD, TURF, OIL AND OTHER SIMILAR SUBSTANCES to be as follows:-
When organic bodies are submitted to the itamediate action of a high temperature
they tend to resolvo into their constituent elemonts.
Hydrocarburets for example are reduced into carbon more or less condensed and
into free hydrogen, this latter being mixed with the four fundamental carburets :—

page_text: This chain of inverse and successive reactions produced by the dissociating action
of heat considerably limits the production of carburets of the aromatic (polyace-
tilenic) series of which benzine is both the type and the base.
Benzine (pure crystallizable benzol) does not pre-exist in coal; it is the result of
the pyrogenated reactions; its actual generator is acetylene, a gaseous hydrocarburet
having for its formula C* H².
My process is based on the rational and permanent production of acetylene, a
production which I favor throughout the entire distillation of coal.
This result is obtained by the intervention of three influences acting simul-
taneously-1. A fixed temperature nover exceeding dull red in my retorts. 2. The
permanent action of a current of gas and steam previously superheated and led into
the retorts during the whole time of the distillation. 3. The influence of a mean
pressure of a fifth of an atmosphere maintained in the retorts by means of a pressure
regulator arranged at the series of barrols.
If instead of submitting the coal suddenly to the dissociating action of a high
temperature (as is the practice in gas works) its decomposition is effected by the
application of a progressive heat, that is to say, a heat regularly increasing, there
are obtained intermediary syntheses and condensations passing successively through
the series of the aromatic carburets, benzine (or benzo!) styrolene (or styrol)
naphthaline, anthracene &c.
These hydrocarburets which are formed by successive condensations and combi-
nations in proportion to the increase of the temperature have all a common
generator-acetylene. It is for this reason that they constitute the series of
polyacetilenic carburets..
Acetylene is the first carburet of hydrogen which is formed in the decomposition
of organic substances subinitted to a dull red heat. At this heat it can already be
condensed into bonzine, but it does not give rise to the formation of the other
carburets except at a greater heat.
We may therefore already infer that a larger proportion of tars rich in benzine
corresponds to a relatively low heat, while to a very high heat from the beginning
of the distillation corresponds the maximum production of gas to the detriment of
the tarry products which are decomposed.
Acetylene is produced:-(1) When fatty, resinous, bituminous and other like
bodies are decomposed at a dull red (2) By the incomplete combustion of lighting
gas. (3) By the action of suporheated steam on lighting gas.
I have said that at a dull red the acetylene produced can be condensed into
benzino
3 (CH³) = C¹ H
(3 atoms of acetylene producing one atom of benzine).
This characteristic reaction takes up all the chemical energy of acetylene,-
energy which I utilize in a general manner in my system of distillation.
The law of chemical energies is that which resides in the stability of bodies.
Bodies are the more difficult to decomposo by heat the greater the disengagement
of heat which they require for their formation.
Example: Formene, marsh gas (which represents in lighting gas the proportion
of 70 per cent) answers for its molecular weight to a disengagement of 22,000
calories. The formation of water represents a disengagement of 69000 calories.
Formene as well as steam will reinain inort in reactions effected at dull red.
They become active only at bright red, that is to say, when there is given to
their elements the quantity of live force which corresponds to the work of their
formation.
Therefore their atoms delivered by dissociation from their powerful reciprocal
attractions will act as if they were free.
The formation of acetylene, the reverse of that of formene answers to an absorp-
tion of about 40,000 calories. Acetylene may therefore be considered as charged
with calorific forces and on account of its chemical energies it acts the part of a
real radical compound.

page_text: ⋅
Submitted to a bright red heat it combines with hydrogen and realizes the
synthesis of ethylene, dimethyle and formene.
Submitted to the action of a dull red heat it condenses, that is to say, combines
with itself to form benzine C¹* Hº.
Then combining with cach carburet which it engenders it produces successively
benzine, styrolene, naphthaline, anthracene &c, this work being effected by the solo
action of its chemical affinities.
The following table expresses the mechanism of these various formations :—
(1) 3 (C' H³) = C¹³ Hº)
Acetylene. Benzine.
(2) CH* + CHỔ
Acetylene. Benzine.
(3) C'H + C¹º H³
Acetyleno. Styroleue.
=
C16 HB
Styrolenė.
=
Ca H10
IIydruret of
Naphthalino.
(4) .C0 g10
= C20 HB
+ H³
Hydruret of
Naphthalinė.
Naphthaline. Hydrogen.
(5) CH + C²° H³ = 0% 0
Acetylene. Naphthalino.
Anthracene.
and so on. This indefinite train of progressive combinations is developed by the
prolonged action of heat on acetylene.
To summarize :-The 3 influences which constitute and characterize my process
have for result:-(1) To produce the permanent formation of acetylene (generator
of benzine). (2). To preserve the benzine from more complex combinations having
for result the production of condensed carburets which constitute heavy oils of less
commercial value.
To effect this object I arrango apparatus for distilling coal as follows:- -Cast iron
vertical retorts are placed in a furnace or oven the temperature of which is constant
and never exceeds dull red. The coal is charged by upper openings and the coke
is discharged by lower openings-The products of distillation escape in the state
of gas and vapor under pressure by tubes which communicate with barrels and from
these they flow to the different condensers and then to the ordinary gas holders.
A steam jet extractor in the neighbourhood of the retorts continuously withdraws
the gas from the gus holders and returns it (after a previous superheating at bright
red) to the retorts. The gas mixed with steam gives rise in traversing the
superheating apparatus to the following reactions :—
1. Complete combustion of the lighting gas under the influence of the oxygen of
the water with production of acetylene.
2. Dishydrogenation of the formene, dimethyle and ethylone.
C'H CH² + 2 H³
Acetylene. Hydrogen.
Dimethyle.
C* H*
=
C* H*
+ H

page_text: Here a fresh influence comes into action. Under the ordinary conditions the
nascent vapors of benzine combine (at dull red) with the acetylene to form
styrolene
CHC H = C10 H³
Acetylene. Benzine. Styrolene.
and after this reaction would form successively the indefinite train of polyacetilenic
carburets more and more condensed.
Now the benzine is completely preserved from these reactions by the atmosphere
of nascent hydrogen with which it is diluted. Hydrogen, the chemical affinities of
which are so little pronounced in the normal conditions, becomes extremely 1
active in the nascent state and under pressure. It is thus that it decomposes by
hydrogenation all the carburets rich in carbon such as styrolene, naphthaline,
anthracene &c.
(1) Action of hydrogen on styrolene (at dull red)..
CH+H'
=
CH + CH*
Styrolene. Hydrogen. Benzine. Ethylene.
(Inverse reaction which limits the production of Styrolene).
(2) Action of hydrogen on naphthaline (at bright red).
C208 + H* : = CH2 CH*
Naphthaline. Hydrogen. Acetyleno. Benzine.
(3) Action of hydrogen on Anthracene (at bright red).
CH2 H² = 2 (C¹² H³)
Anthracene. Hydrogen. Benzinc.
"
+ C* H*
Acetylene.
1
2
The importance of the action of hydrogen which forms with acetylene very
nearly the whole of the atmosphere of my retorts will thus be seen. Owing to its 2
influence the light carburets, that is to say, those saturated with hydrogen escape
the complex reactions, while the heavy carburets (that is to say those more and
more charged with carbon) which tend to form or which are brought into my
retorts with the injected gases are almost immediately decomposed by hydrogenation ·
into light carburets (benzine) and into gas (acetylene).
In short the hydrogen in excess and under pressure in the nascent state preserves
from condensations the carburets of the benzenic series represented by the general
formula C H on which it acts only feebly and slowly at dull red.
The diluted light hydrocarbons as they become formed by the gaseous current
under pressure thus escape the action of the heat.
8
3

page_text: I NARCISSE ALFRED HÉLOUIS of Boulevard Saint Denis 1 at Paris, Chemist
Engineer do hereby declare the nature of my invention for "AN IMPROVED
PROCESS OF MANUFACTURING BENZINE AND ITS HOMOLOGUES BY THE DISTILLATION
OF COAL, WOOD, TURF, OIL AND OTHER SIMILAR SUBSTANCES" and in what manner
the same is to be performed, to be particularly described and ascertained in and by
the following statement :--
When organic bodies are submitted to the immediate action of a high temperature
they tend to resolve into their constituent elements.
Hydro-carburets, for example, are reduced into carbon more or less condensed
O and into free hydrogen, this latter being mixed with the 4 fundamental

page_text: Benzine does not pre-exist in coal; it is the result of the pyrogenated reactions;
its actual generator is acetylene, a gaseous hydro-carburet having for its formula
.C* H*..
My process is based on the rational and permanent production of acetylene,
a production which I favour throughout the entire distillation of coal.
=
This result is obtained by the intervention of 3 influences acting simultaneously :-
1. A fixed temperature never exceeding dull red in my retorts. 2. The permanent
action of a current of gas and steam previously super-heated and led into the
retorts during the whole time of the distillation. 3. The influence of a mean
pressure of a fifth of an atmosphere above atmospheric pressure maintained in the
retorts by means of a pressure regulator arranged at the series of barrels.
If instead of submitting the coal suddenly to the dissociating action of a bigh
temperature (as is the practice in gas works) its decomposition is effected by the
application of a progressive heat, that is to say, a heat regularly increasing, there
are obtained intermediary syntheses and condensations passing successively through
the series of the aromatic carburets, benzine (or benzol), styrolene (or styrol),
naphthaline, anthracene, &º.
These hydro-carburets which are formed by successive condensations and com-
binations in proportion to the increase of the temperature have all a common
generator-acetylene. It is for this reason that they constitute the series of
polyacetilenic carburets.
Acetylene is the first carburet of hydrogen which is formed in the decomposition
of organic substances submitted to a dull red heat. At this heat in can already
be condensed into benzine, but it does not give rise to the formation of the other
carburets except at a greater heat.
We may therefore already infer that a larger proportion of tars rich in benzine
corresponds to a relatively low heat, while to a very high heat from the beginning
of the distillation corresponds the maximum production of gas to the detriment of
the tarry products which are decomposed.
Acetylene is produced: -(1) When fatty, resinous, bituminous and other like
bodies are decomposed at a dull red. (2) By the incomplete.combustion of lighting
gas. (3) By the action of superheated steam on lighting gas.
I have said that at a dull red the acetylene produced can be condensed into
benzine
3 (C** H³) = C¹³ He
(3 atoms of acetylene producing one atom of benzine).
This characteristic reaction shows all the chemical energy of acetylene,―energy
which I utilize in a general manner in my system of distillation.
The law of chemical energies is that which resides in the stability of bodies.
Bodies are the more difficult to decompose by heat the greater the disengagement of
heat which they require for their formation.
Example: Formene, marsh gas (which represents in lighting gas the pro-
portion of 70 per cent) answers for its molecular weight to a disengagement of
22,000 calories. The formation of water represents a disengagement of
69,000 calories.
Formene, as well as steam, will remain inert in reactions effected at dull red.
They become active only at bright red that is to say, when there is given to their
elements the quantity of live force which corresponds to the work of their
formation.
Therefore their atoms delivered by dissociation from their powerful reciprocal
attractions will act as if they were free.
The formation of acetylene, the reverse of that of formene, answers to an
absorption of about 40,000 calories. Acetylene may therefore be considered as
charged with calorific forces and on account of its chemical energies it acts the part
of a real radical compound.
:Submitted to a bright red heat it combines with hydrogen and realizes the
synthesis of ethylene, dimethyle and formene,

page_text: Submitted to the action of a dull red heat it condenses, that is to say, combines
with itself to form benzine C¹ H*.
Then combining with each carburet which it engenders it produces successively
benzine, styrolene, naphthaline, anthracene, &, this work being effected by the
sole action of its chemical affinities.
The following table expresses the mechanism of these various formations :-
(1). 3 (C' H³)
Acetylene. Benzine.
= C¹² H°
.(2). C* H*
+
C H =
C1 H
Acetylene. Benzine.
(3) CH +
Acetylene.
Styrolene.
C16 H8 =
C20 HID
Styrolene.
Hydruret of
Naphthaline.
(4) C20 H10
=
C20 H8
+ H2
Naphthaline.
Naphthaline.
Hydrogen.
and so on,
Hydruret of
(5) C'H + C²º HB = Cº Ho
Acetylono. Naphthaline. Anthracene.
This indefinite train of progressive combinations is developed by the
prolonged action of heat on acetylene.
.'
To summarize: The 3 influences which constitute and characterize my process
have for result(1) To produce the permanent formation of acetylene (generator
of benzine). (2) To preserve the benzine from more complex combinations having
for result the production of condensed carburets which constitute heavy oils of less
commercial value.
To effect this object I arrange apparatus for distilling coal as represented in the
annexed drawing. 3, 3 are vertical cast iron retorts placed in a furnace or oven 1,
the temperature of which is constant and never exceeds dull red. At the bottom of
each retort is a coil for super-heating steam. 4, 4 are sheet iron holders with false
bottoms. They are filled with the coal or substance to be distilled, and are lowered
into the retorts by means of chains and pulleys on a carriage that runs on an over-
head way. 8 is a carriage to support the holders. 9 is a crusher from which the
holders are filled, these being at the time lowered into the pit 10. At 5 are shown
a disengaging tube and barrel: 11 is a steam generator and 12 an engine. The
retorts are charged by upper openings and the coke is discharged by lower openings.
The products of distillation escape in the state of gas and vapor under pressure by
tubes which communicate with barrels 5 and from these they flow to the different
condensers and then to the ordinary gas-holders. A steam jet extractor in the
neighborhood of the retorts continuously withdraws the gas from the gas holders
and returns it (after a previous superheating at bright red) to the retorts. The gas
mixed with steam gives rise in traversing the super-heating apparatus to the
following reactions :-
=
1. Incomplete combustion of the lighting gas under the influence of the oxygen
of the water with production of acetylene.
2. Dishydrogenation of the formene, dimethyle and ethylene.
CH=CH' + 2 H
Dimethyle. Acetylene. Hydrogen.

page_text: denses into benzene in passing through the body.or Carbon
3 (CH)=C H
Here a fresh influence comes into action. Under the ordinary conditions the
nascent, vapors of benzine combine (at dull red) with the acetylene to form
styrolene.
CHC2 H° = C¹ H⁹
Acetylene. Benzine. Styrolene.
and after this reaction would form successively the indefinite train of polyacetilenic
carburets inore and more condensed.
Now the benzine is completely preserved from these reactions by the atmosphere
of nascent hydrogen with which it is diluted. Hydrogen, the chemical affinities of
which are so little pronounced in the normal conditions, becomes extremely active
in the nascent state and under pressure. It is thus that it decomposes by
hydrogenation all the carburets rich in carbon such as styrolene, naphthaline, 1
anthracene, &c.
(1) Action of hydrogen on styrolene (at dull red)
•
CH³ + H* =
C¹³¹³ ³ + C'È¹
Styroleno. Hydrogen. Benzine. Ethylene.
(Inverse reaction which limits the production of styrolene).
(2) Action of hydrogen on naphthaline (at bright red)
C20 H& + H = 0 H° + 20' H
Naphthaline. Hydrogen. Acetylene.
(3) Action of hydrogen on anthracene (at bright red)
C28102 H² =
Anthracene. Hydrogen.
Benzino.
2 (CH) + C'H'
Benzine. Acetylene.
The importance of the action of hydrogen which forms with acetylene and a little
oxide of carbon very nearly the whole of the atmosphere of my retorts will thus be
seen. Owing to its influence the light carburets, that is to say, those saturated with
hydrogen escape the complex reactions, while the heavy carburets (that is to say,
those more and more charged with carbon) which tend to form or which are brought
into my retorts with the injected gases are almost immediately decomposed by
hydrogenation into light carburets (benzine) and into gas (acetylene).
In short the hydrogen in excess and under pressure in the nascent state preserves
from condensations the carburets of the benzenic series represented by the general
formula C H on which it acts only feebly and slowly at dull red.
The diluted light hydrocarbons as they become formed by the gaseous current
under pressure thus escape the action of the heat.
A further advantage obtained by my process is due to the influence of the hydro-
gen on the production of ammonia. I have found that the super-beated steam and 4
gas admitted continuously to the retorts during the process of distillation cause a
production of ammonia about 6 per cent more than is obtained by distillation in the
ordinary way. As with benzine, the hydrogen seems to exercise. a manifest influence
on the nitrogen products of the coal not only in favoring the 'formation of ammonia
but also in protecting it from decomposition in contact with the retorts.
Having now particularly described. and ascertained the nature of my said
Invention, and in what manner the same is to be performed, I declare that what
I claim is
1. The process heroin before described of manufacturing benzine and its homo-
logues by the distillation of coal, wood, turf, oil and other similar substances.
2. The permanent production as hereinbefore described of benzine by the dis-
tillation of coal or other similar substance at a dull red heat under the constant
influence or action of super-heated steam and gas admitted simultaneously into the
retorts.
:

page_text: 3. The maintenance or fixing of the benzine as heroinbefore described by the aid
of nascent hydrogen under pressure which transforms or tends to transform by
hydrogenation the heavy products such as naphthaline, styrolene and anthracene
into light products such as benzine and its homologues.
4. The carrying out of my said process by means of apparatus such as that
herein before described the said apparatus comprising cast iron retorts which during
the process are kept at a dull red heat.
D
T
J. C. MEWBURN,
169, Fleet Street, London,
Agent.