IMPROVEMENTS IN MANUFACTURE OF BERZORE, NATTRA, NATTRAMINE, ANTENE, AND CARDOLIC ACID
Year: 1861

page_text: LETTERS PATENT to John Barrow, of the Dalton Chemical. Works,
West Gorton, near Manchester, for the Invention of "IMPROVEMENTS IN
MANUFACTURE OF BERZORE, NATTRA, NATTRAMINE, ANTENE, AND CARDOLIC
ACID."
Sealed the 6th May 1862, and dated the 7th November 1861.
PROVISIONAL SPECIFICATION left by the said John Barrow at the
Office of the Commissioners of Patents, with his Petition, on the 7th
November 1861.
I, JOHN BARROW, of the Dalton Chemical Works, West Gorton, near
Manchester, do hereby declare the nature of the Invention for "IMPROVE-
MENTS IN THE MANUFACTURE OF BENZOLE, NAPTHA, NAPTHALINE, ANILINE, AND
CARBOLIC ACID," to be as follows:-
Heretofore, in the manufacture of benzole, naptha, napthaline, aniline, and
carbolic acid, the coal tar of gasworks has been employed, which has of late
become of such value and so insufficient in quantity as to greatly increase the
cost of the manufacture of benzole, naptha, napthaline, aniline, and carbolic
acid. I have discovered that by treating coal directly with a view to the
manufacture of these products, and by avoiding as much as may be the pro-
duction of gas, I am enabled more advantageously to manufacture the above-
mentioned hydrocarbons. For these purposes I employ retorts, ovens, or
other suitable apparatus heated by any convenient means, or (and by preference)

page_text: stills, the lower parts only of which are acted upon by heat, so that the lower
strata of coal shall first be heated, and the vapours evolved be protected from
excessive heat, so as to prevent as much as possible their decomposition into
permanent gases or other bodies. Into these stills I put a charge of coal,
using, by preference, that kind of coal known in the neighbourhood of Wigan
as cannel slack; and I then heat the stills, gradually increasing it up to bright
red, collecting and condensing the vapours evolved by any of the well-known
means. By thus directly treating coal with a view to obtain benzole and the
other substances above mentioned, I am enabled to obtain a larger product of
the crude oils from a given weight of coal than when distilling to obtain
gas as a primary product. These crude oils or products I partially rectify by
distillation in ordinary stills,
The partially rectified oils I put into a boiler, connected with which is a
condensing apparatus, and I blow into the oils jets of steam, which distil over
only a certain portion of these oils, leaving in the boiler the heavier and less
volatile bodies. The lighter distilled portion is a mixture of several hydro-
carbons and constitutes crude mineral naptha containing benzole.
Having thus separated the crude naptha from the other oils with which it
was mixed, I proceed to rectify it by means of acids and alkalies or alkaline
earths, and after their application I again distil by steam, collecting apart that
portion which distils over, at, or below the temperature of 212° Fahrenheit,
which portion contains the crude benzole. The remaining portion, or all of it
that distils over by the agency of a jet of steam blown into it, is fit for sale as
mineral naptha. In some cases I separate not only the benzole but an oil
suitable for lamps. The crude benzole I further rectify by acids, oxidizing
agents, and alkalies or alkaline earths, and I again distil it. It may be further,
purified, if required, by freezing and pressure.
To obtain aniline and carbolic acid, I treat the crude oils of the first dis-
tillation with mineral or vegetable acids, which unite with the aniline and
separate it from the other oils, and the remaining oils I treat with alkaline S
solutions or solutions of alkaline earths, which unite with the carbolic acid, and
separate it from the remaining oils. From the acid solution of aniline and the
alkaline solution of carbolic acid, I then separate these two bodies, and after-
wards purify them. The remaining oils after the separation of aniline and
carbolic acid are neutral oils, which I distil by means of a jet of steam to 3
obtain the naptha and benzole which they will contain.
The napthaline I obtain as a crystalline deposit when the oils are cooled
down, which I separate by pressure and purify by sublimation or otherwise,

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent, filed
by the said John Barrow in the Great Seal Patent Office on the 7th
May 1862.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, JOHN
BARROW, of the Dalton Chemical Works, West Gorton, near Manchester,
send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her Letters
Patent, bearing date the Seventh day of November, in the year of our Lord
One thousand eight hundred and sixty-one, in the twenty-fifth year of Her
reign, did, for Herself, Her heirs and successors, give and grant unto me, the
said John Barrow, Her special licence that I, the said John Barrow, my
executors, administrators, and assigns, or such others as I, the said John
Barrow, my executors, administrators, and assigns, should at any time agree
with, and no others, from time to time and at all times thereafter during the
term therein expressed, should and lawfully might make, use, exercise, and
vend, within the United Kingdom of Great Britain and Ireland, the Channel
Islands, and Isle of Man, an Invention for "IMPROVEMENTS IN THE MANUFACTURE
OF BENZOLE, NAPTHA, NAPTHALINE, ANILINE, AND CARBOLIC ACID," upon the con-
dition (amongst others) that I, the said John Barrow, my executors or adminis
trators, by an instrument in writing under my, or their, or one of their hands
and seals, should particularly describe and ascertain the nature of the said In-
vention, and in what manner the same was to be performed, and cause the
same to be filed in the Great Seal Patent Office within six calendar months
next and immediately after the date of the said Letters Patent.
NOW KNOW YE, that I, the said John Barrow, do hereby declare the
nature of the said Invention, and in what manner the same is to be performed,
to be particularly described and ascertained in and by the following state-
ment thereof, that is to say:-
Heretofore in the manufacture of benzole, naptha, napthaline, aniline, and
carbolic acid, the coal tar of gasworks has been employed, which has of late.
become of such value and so insufficient in quantity as to greatly increase the
cost of the manufacture of benzole, naptha, napthaline, aniline, and carbolic
acid;
I have discovered that by treating coal directly with a view to the manu-
facture of these products, and by avoiding as much as may be the production
gas, I am enabled more advantageously to manufacture the above-mentioned
substances. For these purposes I employ, by preference, retorts like ordinary
iron gas retorts, set horizontally, but in such a manner that while the bottom and
sides are capable of being heated to bright redness, the upper portion of the retort
of

page_text: above the charge is carefully protected by brickwork from the fire and heat;
the retorts are made capable of holding from 8 to 12 cwt., and I connect a
series of pipes to each retort for the purpose of condensing the vapours
evolved; these pipes may or may not be surrounded with water. The condensing
pipes from several stills I cause to terminate in one large pipe, which I call
the main pipe, and from which I draw off the condensed oils. Having charged
the stills with coal, using by preference that kind of coal known in the neigh-
bourhood of Wigan as cannel slack, (although any coal suitable for the manu-
facture of gas will answer the purpose,) I allow it to remain in the stills as
long as any oils are distilled over, and then rake out the cokes, and again
charge the stills with slack. I do not find that the production of oils is mate-
rially increased or improved by allowing the stills to cool between each
operation, although this may be done, and I therefore maintain the heat con-
tinuously at a bright red, so as to save time. It is advantageous to introduce
steam into the retort during the process, or at least at the end of the distilla-
tion of each charge to sweep out of the retort the vapours-which it contains.
This method of distilling differs from that ordinarily practiced in distilling coal,
in that whilst the bottom and sides of the retort are capable of being highly
heated, the top is carefully protected from the heat; this is an important
feature of my arrangement, as were the vapours when produced allowed to
remain in contact with a highly heated surface, they would be rapidly decom-
posed into permanent gas; this is what the gas maker desires, and it is what
I, on the contrary, especially desire to avoid.
The crude oils thus obtained I partially purify by one distillation in iron
stills, heated by fire beneath, until nothing is left in them but a small portion
of pitch. In some cases the crude oil, and also the oil after the first distilla-
tion, deposits on cooling crystals of napthaline; when this is the case I separate
these crystals of napthaline and press them dry; I afterwards purify the
napthaline by sublimation or otherwise, as is well understood.
When I desire to separate aniline and carbolic acid as is most frequently
the case, I treat the crude oils of the first distillation with acid (using by pre-
ference hydrochloric acid), which unites with the aniline and separates it from
the other oils, and the remaining oils I treat with alkaline solutions or solutions
of alkaline earths (using by preference caustic soda), which unite with the
carbolic acid and separate it from the remaining oils. From the acid solution
of aniline and the alkaline solution of carbolic acid, both of which readily
separate from the oil, I then obtain the aniline and carbolic acid, and after-
wards purify them by any of the methods at present used by chemists. The
remaining oils, after the separation of the aniline and carbolic acid, if this

page_text: separation is to be effected, or otherwise the partially rectified oils, I put into a
boiler, connected with which is a condensing apparatus, which is to -be-kept
very cold by a good supply of water, and I heat the oils by means of pipes
supplied with steam, coiled round the inside of the stills, or by any other method.
of applying this temperature, and I collect separately. the oils which distil over
by the application of this temperature, which will be at or below 212° Fahren-
heit; these oils will contain benzole and several other bodies...When these
have ceased to come over, I cause jets of steam to blow into the oils, which
distils over a second quantity of oils, leaving in the boiler the heavier and less
volatile oils. The second quantity of oils distilled over is a mixture of several
hydrocarbons, and constitutes crude mineral naptha.
Having thus separated the crude. naptha, I proceed to rectify it by similar
means to those which are employed for rectifying naptha obtained from gas
tar, and which are well known, viz., by means of acids and alkalies or alkaline
earths, (using by preference sulphuric acid and caustic soda,) and to effect-
this rectification, I agitate the crude naptha with strong sulphuric acid, and
after allowing the sulphuric acid to settle, I decant the naptha and agitate it
with a solution of caustic soda, and after their application I again distill by
steam (in coils of pipes or steam jacket), collecting apart that portion which
distils over at or below the temperature of 212° Fahrenheit, which portion I
add to the benzole already obtained. The remaining portion, or all of it that
distils over by the agency of a jet of steam blown into it is fit for sale as
mineral naptha.
The crude benzole I further rectify by distillation, by acids, oxidizing agents,
and alkalies or alkaline earths, in the manner usually practised by chemists ;
it may be still further purified, if required, by freezing and pressure.
In some cases, after separating the benzole, I distil the remaining oils by
steam and fire, until the whole is brought over, and I treat these oils with con-
centrated nitric acid, using the most concentrated acid I can obtain, or a mix-
ture of less concentrated nitric acid and sulphuric acid, or a mixture of a nitrate,
as, for instance, nitrate of soda and a double equivalent of sulphuric acid, until
the oils separate naturally into a heavy nitrogenous compound and a lighter
fluid oil, which floats on the top. If the first quantity of nitric acid added does
not produce this separation, I add more, until the separation takes place. The-
lighter oil I decant and again treat with nitric acid, and afterwards wash with
caustic soda to free it from acid compounds, and I thus obtain an oil having
the property of burning in lamps without smoke, and which I
purpose using
as a substitute for animal or vegetable burning oils, and for other purposes.
Having thus described the nature of my Invention, and the manner of per-

page_text: forming the same, I would have it understood that I do not confine myself to
the exact details described; but what I claim is, the manufacture of benzole,
naptha, napthaline, aniline, and carbolic acid, in the manner herein-before set.
forth.
In witness whereof, I, the said John Barrow, have hereunto set my
hand and seal, this Sixth day of May, in the year of our Lord One
thousand eight hundred and sixty-two.
JOHN BARROW. (L.S.)