IMPROVEMENTS IN THE MANUFACTURE OF ALKALIES
Year: 1878

page_text: In the Matter of Letters Patent granted to Edward William Parnell of the
City of Liverpool in the County of Lancaster Manufacturing Chemist, for
the Invention of "IMPROVEMENTS IN THE MANUFACTURE OF ALKALIES
bearing date the 21st day of October 1878 N° 4188.
"J
TO ALL TO WHOM THESE PRESENTS SHALL COME We EDWARD
WILLIAM PARNELL and JAMES SIMPSON both of the City of Liverpool in the County
of Lancaster Manufacturing Chemists, Send Greeting
WHEREAS Her present Majesty Queen Victoria by Her Letters Patent under
the Great Seal of the United Kingdom of Great Britain and Ireland bearing date
the twenty first day of October One thousand eight hundred and seventy eight in
the forty second year of Her reign did grant unto me the said Edward William
Parnell my executors administrators and assigns the sole privilege during the term
of fourteen years thence next ensuing to make use exercise and vend within the
United Kingdom of Great Britain and Ireland the Channel Islands and Isle of
Man for "IMPROVEMENTS IN THE MANUFACTURE OF ALKALIES."
an Invention
&
And whereas in pursuance of the Conditions of the said Letters Patent I the said
Edward William Parnell did on the twenty first day of April One thousand eight
hundred and seventy nine cause a Specification of the said Invention in writing
under my hand and seal to be filed in the Great Seal Patent Office
And whereas by an Indenture dated the second day of, May One thousand
eight hundred and eighty one and duly registered made between me Edward
William Parnell of the one part and me James Simpson of the other part the said
Invention and Letters Patent and all privileges and advantages by the said Letters
Patent granted were assigned by me Edward William Parnell unto us Edward
William Parnell and James Simpson our executors administrators and assigns as
tenants in common for the residue of the said term of fourteen years and any
further time for which any extension or renewal of the said Letters Patent might
be obtained.

page_text: And whereas since the filing of the said Specification we have discovered that
the first and third parts and the first and third claims in the Specification of the
said Letters Patent are or may be of doubtful validity and we wish to avoid
objections which may be made thereto.
NOW KNOW YE that we the said Edward William Parnell and James
Simpson do hereby for the aforesaid reasons (by and with the leave of Her
Majesty's Solicitor General) alter and amend the said Specification in manner
following that is to say:
33
On page 3 of the Specification as it is printed by Her Majestys Printers to
insert the word "an between the words " Chemist" and "Improvements" and
strike out the letter "s" in the said word "Improvements" in line 5.
Also on the saine page to strike out the words "compounds of" and "with
alkalies" and add the letters "ets" to the word "sulphur" in line 7 so as to make
it read "sulphurets
"
Also on the same page to add the letters "ets" to the word "sulphur " in line 8
so as to make it read "sulphurets."
Also on the same page to strike out all the words commencing with the word
"compound" in line and terminating with the word "again" in line 10 that is
to strike out "compound and of recovering the re-agent employed therein so that
the latter may be used over and over again."
Also on the same page to add the letters "ets" to the word "sulphur " to make
it "sulphurets" and to strike out the word "compounds "in line 11
Also on the same page to strike out all the words commencing with the word
"for" in line 12 and terminating with the word "forth" in line 20.
Also on the same page to strike out all the words commencing with the word
"I" in line 21 and terminating with the word "manner
"in line 37.
Also on the same page to strike out the words "the said " in line-38.
Also on the same page to strike out all the words commencing with the word
"The "in line 39 and ending with the word "continuously" in line 40.
Also on the same page to substitute the word "add" for "employ" and to strike
out the words "for adding" in line 40.
Also on the same page to add the letter "s" to each of the words "solution'
and strike out the letter "s" in the word "combines" in line 41.
"
Also on the same page to strike out all the words commencing with the word
"settle" in line 42 and ending with the word "described" in line 51.
Also on the same page to insert after the word "to" in line 42 the words
"subside, after which the purified alkaline solution is drawn off."
Also on the same page to strike out the letter "s" in the word "improvements"
in line 53
Also on the same page to strike out the whole of the lines 54 and 55 being the
first Claiming Clause.
On page 4 to strike out the word "second" in line 1.
" after
Also on the same page to add "made according to the Le Blanc process
the words "impure alkaline solutions" in line 1 and the words "consisting of"
after the words "with a solution" in the same line. and the words "for the
purpose and after the words "caustic alkali" in the second line and to substitute
the words "in the manner " for the word as in the same line and to strike
out the words "under the second part" in the same line.
"
Also on the same page to strike out the whole of lines 3 and 4 being the third
Claiming Clause
And in order that the effect of this disclaimer and memorandum of alteration
may be better understood the following Copy of the Specification as it will appear
when such disclaimer and memorandum of alteration has been made as aforesaid
is appended
EDWARD WILLIAM PARNELL of Liverpool in the County of Lancaster Manu-

page_text: Crude solutions of alkali obtained in the manufacture of alkalies by the
Le Blanc process are invariably contaminated with sulphurets. This invention
consists of an improved method of removing the said sulphurets and the object
is to purify the said alkalies and render them to a great extent free from the
said sulphurets by a cheap and efficient method of treatment.
In carrying my invention into practice I dissolve by boiling zinc or zinc oxide
in caustic alkali solution of about 40° Twaddel I add this solution to the crude
alkaline solutions above mentioned-The sulphurets in the said solutions combine
with the zinc and the zinc sulphuret formed is allowed to subside after which
the purified alkaline solution is drawn off.
Having now described the nature of the said invention in such manner that
others will be enabled to carry my improvement into effect I claim Treating
impure alkaline solutions made according to the Leblanc process with a solution
consisting of zinc or zinc oxide in caustic alkali for the purpose and substantially
in the manner set forth.
In witness whereof we the said Edward William Parnell and James Simpson
have bereunto set our hands and seals the first day of August in the
year of our Lord One thousand eight hundred and eighty two in the
presence of
I hereby grant my Fiat giving leave to the above named Edward William
Parnell and James Simpson to file in the Office of the Commissioners of Patents
for Inventions with the Specification to which the samo relates the foregoing
Disclaimer and Memorandum of Alteration; but nevertheless upon condition that
no proceedings for infringement be taken against Messieurs Mort Liddell & C° of
Widnes in the County of Lancaster in respect of the use or continued use of the
patented process in and by means of the two iron vessels each 9 feet inches in
diameter and 5 feet 6 inches and 5 feet 7 inches in depth respectively now in use
by them for dissolving zinc and the necessary appliances now in use by them for
connecting the same with the causticizers as stated in a Declaration filed with me
on the 9th of March 1883.
Dated this thirtieth day of May One thousand eight hundred & eighty three.

page_text: LETTERS PATENT to Edward William Parnell, of Liverpool, in the County of
Lancaster, Manufacturing Chemist, for the Invention of "IMPROVEMENTS IN
THE MANUFACTURE OF ALKALIES."
Sealed the 10th April 1879, and dated the 21st October 1878.
"
PROVISIONAL SPECIFICATION left by the said Edward William Parnell at
the Office of the Commissioners of Patents on the 21st October 1878.
EDWARD WILLIAM PARNELL, of Liverpool, in the County of Lancaster, Manu-
facturing Chemist. "IMPROVEMENTS IN THE MANUFACTURE OF ALKALIES.'
Crude solutions of alkalies obtained in the manufacture of alkalies by the Leblanc
process are invariably contaminated with compounds of sulphur with alkalies.
This Invention consists of an improved method of removing the said sulphur
compounds and of recovering the re-agent employed therein, so that the latter may
be used over and over again.
The object of my Invention is to purify the said alkalies, and render them free
from the said sulphur compounds by a cheap and efficient method of treatment; for
this purpose I take advantage of the following re-actions:-
When metallic zine is brought into contact with a solution of a caustic alkali, the
metal is dissolved and hydrogen gas is evolved, and if an alkaline sulphuret be
present in the solution, the sulphur contained therein will combine with the zinc
and form an insoluble compound; moreover, if in addition to the alkaline sulphuret
there are compounds, such as sulphite and byposulphite of the alkali, such com-
pounds will become reduced by the action of the nascent hydrogen to the state of
sulphuret, which will then combine with the zinc to form an insoluble sulphuret, as
above set forth.
In carrying my Invention into practice I first bring the crude alkaline solutions
into contact with metallic zinc, and heat and agitate the mixture until only a trace
of sulphur remains in the solution, in combination with the alkali as sulphuret.
Should this point have been passed and zinc be found in solution, more crude alkali

page_text: is to be added, and the sulphuret therein will instantly re-act on the zinc and form
a sulphuret of zinc. On the completion of the re-action the solution is allowed to
settle and the zinc sulphuret to subside to the bottom of the vessel, after which the
purified supernatent alkaline solution is drawn off.
Secondly. I prepare zinc for use in the above re-actions in the following manner:
-I dissolve the said zinc or zinc oxide in caustic alkali, and I employ this solution
for adding to the crude alkaline solution above mentioned. The sulphurets in the
said solution combines with the zinc, and the zinc sulphuret formed is allowed to
settle out, as before described. In this case however the sulphites and hypo-
sulphites in the crude alkaline solutions are not acted on, only the sulphurets being
removed.
Thirdly. I collect the zinc sulphuret formed in the above re-actions dry, and
calcine it in a suitable furnace, and mix the resulting compound, or mixture of
compounds, with fresh zinc sulphurot if necessary, and recalcine it in such a
manner as to produce zinc oxide. This oxide I then treat with strong caustic alkali
and employ the solution obtained for operation on fresh crude alkaline solutions, as
above described.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent filed by
the said Edward William Parnell in the Great Seal Patent Office on the 21st
April 1879.
EDWARD WILLIAM PARNELL, of Liverpool, in the County of Lancaster, Manu-
facturing Chemist. "IMPROVEMENTS IN THE MANUFACTURE OF ALKALIES."
Crude solutions of alkali obtained in the manufacture of alkalies by the Leblanc
process are invariably contaminated with compounds of sulphur with alkalies.
This Invention consists of an improved method of removing the said sulphur
compound, and of recovering the re-agent employed therein, so that the latter may
be used over and over again, and the object is to purify the said alkalies and render
them to a great extent free from the said sulphur compounds by a cheap and
efficient method of treatment; for this purpose I take advantage of the following re-
actions When the metallic lime is brought into contact with a solution of a caustic
alkali, the metal is dissolved and hydrogen gas is evolved, and if an alkaline sulphuret
be present in the solution, the sulphur contained therein will combine with the zinc
and form an insoluble compound; moreover, if in addition to the alkaline sulphuret
there are compounds such as sulphite and hyposulphite of the alkali, such com-
pounds will become reduced by the action of the nascent hydrogen to the sate of
sulphuret, which will then combine with the zinc to form an insoluble sulphuret, as
above set forth.
--
In carrying my Invention into practice, I first bring the crude alkaline solutions
into contact with metallic zinc, and heat and agitate the mixture until only a trace
of sulphur remains in the solution, in combination with the alkali as sulphuret.
Should this point have been passed and zinc be found in solution, more crude
alkali is to be added, and the sulphuret therein will instantly re-act on the zinc
and form a sulphuret of zinc. On the completion of the re-action the solution is
allowed to settle and the zinc sulphuret to subside to the bottom of the vessel, after
which the purified supernatant alkaline solution is drawn off.
In the treatment first above-mentioned zinc in excess is added to the alkali to be
purified, and the mixture is heated and agitated until no signs of sulphurets are
discovered on testing; the mass is then allowed to settle, and the purified alkali is
run off. If on testing the purified alkali some zinc is found in solution, sufficient
impure alkali is added to precipitate the said zinc. Although the above process is
capable of not only removing the sulphurets, but also the bysulphurets and posul-
phites from the impure alkali solution, it is rather slow in operation, and I prefer to
employ the process herein-after described under the second head.
Secondly. I prepare zinc for use in the above re-actions in the following manner:
-I dissolve by boiling the said zinc or zinc oxide in caustic alkali solution of about
40° Twaddel. The zinc or zinc oxide and caustic alkali solutions are added and
withdrawn continuously. I employ this solution for adding to the crude alkaline
solution above mentioned. The sulphurets in the said solution combines with tho
zinc, and the zinc sulphuret formed is allowed to settle out as before described. In
this case however the sulphites and hyposulphites in the crude alkaline solution are
not acted on, only the sulphurets being removed.
Thirdly. I collect the zinc sulphuret formed in the above re-actions, wash, dry,
and calcine it in any suitable furnace, and mix the resulting compound of zinc
sulphate or mixture of compounds of zinc sulphate and sulphuret, with fresh zinc
sulphuret if necessary, and re-calcine it; during this recalcination the sulphuret and
sulphate re-act on each other, and zinc oxide is formed. This oxide I then treat
with strong caustic alkali, and employ the solution obtained for operation on fresh
crude alkaline solutions, as above described.
Having now described the nature of the said Invention in such manner that others
will be enabled to carry my improvements into effect, I claim,―
First. Treating and agitating a mixture of impure alkaline solution with metallic
zinc for the purposes set forth.

page_text: Second. Treating impure alkaline solutions with a solution of zinc or zinc oxide
in caustic alkali, substantially as set forth under the second part.
Third. Treating zinc sulphuret in the mauner and for the purposes set forth under
the third head.
In witness whereof, I, the said Edward William Parnell, have hereunto set
my hand and seal, this Eighteenth day of April, in the year of our Lord One
thousand eight hundred and seventy-nine.
Signed, sealed, and delivered by the
said Edward William Parnell in
the presence of
JAMES JOHNSON,
Patent Office,
4, Clayton Square,
Liverpool.
E. W. PARNELL. (L.S.)