IMPROVEMENTS IN MANUFACTURING IRON, AND IN MANUFACTURING AND PURIFYING COKE
Year: 1851

page_text: TO ALL TO WHOM THESE PRESENTS SHALL COME, I, FREDERICK
CRACE CALVERT, of Manchester, in the County of Lancaster, Professor of
Chemistry and Analytical Chemist, send greeting.
WHEREAS Her present most Excellent Majesty Queen Victoria, by Her
Royal Letters Patent under the Great Seal of the United Kingdom of Great
Britain and Ireland, bearing date at Westminster, the Thirtieth day of October,
One thousand eight hundred and fifty-one, in the fifteenth year of Her reign,
did, for Herself, Her heirs and successors, give and grant unto me, the said
Frederick Crace Calvert, my exors, adiñiors, and assigns, Her especial licence,
full power, sole privilege and authority, that I, the said Frederick Crace Cal-
vert, my exors, adñiors, and at assigns, or such others as I, the said Frederick
Crace Calvert, my exors, adññors, or assigns, should at any time agree with,
and no others, from time to time and all times during the term of years
therein expressed, should and lawfully might make, use, exercise, and vend,
within England, Wales, and the Town of Berwick-upon-Tweed, my Inven-
tion of "IMPROVEMENTS IN MANUFACTURING IRON, AND IN MANUFACTURING AND
PURIFYING COKE;" in which said Letters Patent is contained a proviso, that I,
the said Frederick Crace Calvert, shall cause a particular description of the
nature of my said Invention, and in what manner the same is to be performed,
by an instrument in writing under my hand and seal, to be enrolled in Her
Majesty's High Court of Chancery within six calendar months next and

page_text: immediately after the date of the said in part recited Letters Patent, as in
and by the same, reference being thereunto had, will more fully and at large
appear.
NOW KNOW YE, that in. compliance with the said proviso, I, the said
Frederick Crace Calvert, do hereby declare that the nature of my Invention,
and the manner in which the same is to be performed, are particularly
described and ascertained in and by this present Specification or instrument
in writing, reference being had to the Drawing hereunto annexed by way of
illustration only (that is to say):-
My said Invention consists, firstly, in applying chlorine or hydrochloric acid,
chlorides, or hypochlorites to the materials from which iron is smelted or
made, for the purpose of obtaining the iron free or more free than hitherto
from sulphur, and also from any phosphorus, or any compounds of either of
these substances which may be found in the ore from which the iron is made.
And, secondly, of the application of chlorine or other chemical agents to
coal during the process of manufacturing coke, or to coke after it has been
manufactured, for the purpose of obtaining coke or partially coked coal free
or more free than hitherto from sulphur or phosphorus (if any contained in
the coal), and the compounds of those substances, or fixing such substances
and their compounds in such a manner as to prevent the injurious effects; or for
purpose of purifying the coke or partially coked coal after the same has been
manufactured from those substances and their compounds, or fixing the same
in such a manner as to prevent the injurious effects of those substances or
their compounds, when the coke or partially coked coal is employed as fuel,
or as an agent for reduction.
the
For the purpose of manufacturing iron according to the first part of my
Invention, I either bring chlorine into contact with the materials from which
the iron is made when heated in a blast furnace, or I bring chlorine or hydro-
chloric acid into contact with the ore when it is roasted previous to its' being
introduced into the blast furnace, and the chlorine may be used or applied
either in a gaseous state, or by means of some compound containing chlorine;
and the material which I prefer to employ for this purpose is the chloride of
sodium, but any chloride or hypochlorite which can be obtained sufficiently
cheap may be used. The furnaces used in manufacturing or smelting iron
from the ore, and also the mode of charging and working such furnaces, are
well known, and need not therefore be described. When I use chlorine in a
state of gas in the manufacturing of iron in the blast furnace, I introduce
it into the furnace about ten feet from the top of the charge at a place where
the ore has been acted upon by the heat, but before the reduction of the

page_text: iron which it contains into a reguline state. For this purpose I perforate
the sides of the furnace at the proper position with several holes, through
which I introduce a continuous stream of the gas, by means of pipes leading
from the retort or chamber where the gas is generated, during the whole
time of the working of the furnace. The action of chlorine will, I believe,
be as follows: The chlorine on coming in contact with the materials in the
furnace will combine with much, if not all, the sulphur or phosphorus (if any),
and form the chloride of sulphur or phosphorus (as the case may be), which
will then pass off in a gaseous state; and the materials being thus freed from
sulphur and phosphorus, or nearly so, the iron, when ultimately smelted and
reduced from the ore, will be freed from the whole or the greater part of those
substances. When I use chloride of sodium, or any other chloride, or any
hypochlorite, in the manufacturing of iron in the blast furnace, I introduce the
chloride or hypochlorite into the top of the furnace together with the ore, fuel,
lime, and other materials (if any), and as it gradually descends into the furnace
together with the other materials and becomes subjected to the action of the
fire, the chlorine of the chloride of sodium or other chloride or hypochlorite will
combine with the sulphur or phosphorus (if any) contained in the ore, or the
greater portion of it, and then the chloride of sulphur or phosphorus will be
driven off in a gaseous state, leaving the materials behind greatly, if not entirely,
purified from sulphur and phosphorus, and the result will be that the iron
obtained will be free from these substances, or nearly so.
'
The use of the chlorides or hypochlorites will also, I believe, be found bene-
ficial for the purposes of my Invention in this respect, that the sodium or other
material with which the chlorine is combined will unite with a portion of the
sulphur or phosphorus, and thus cause it to pass into the slag without being
united with the iron. As a general rule, from one to six parts of the chloride
of sodium to every two hundred parts of all the other materials with which
the blast furnace is usually charged will be found to be sufficient; but the pro-
portion of the chloride or hypochlorite may be regulated with greater accuracy
by analysing a portion of the materials used, and thus ascertaining the amount
of sulphur to be removed by the chloride or hypochlorite, every sixteen parts of
sulphur requiring about fifty-eight parts of the chloride of sodium for their
removal, and every thirty-two parts of phosphorus about fifty-eight parts of the
same chloride for their removal. Any other chloride or any hypochlorite which
can be obtained sufficiently cheap may be used in the same manner as chloride
of sodium, in every case employing such a quantity of the substituted chloride
or hypochlorite as shall contain a quantity of chlorine equivalent to that con-
tained in the chloride of sodium.

page_text: Instead of applying chlorine or hydrochloric acid to the ore in the blast
furnace, as already described, chlorine, either as a gas, or combined so as to
form a chloride or hypochloric acid gas, may be applied to the ore at the time
it is roasted previous to its being introduced into the blast furnace, where the
roasting takes place in a furnace or in the open air; but if the application be
made to ore roasted in the open air, the most convenient mode of performing
the Invention is to apply chlorine to the iron ore, by mixing the requisite
proportion of chloride of sodium, or other chloride or hypochlorite, with the ore
previous to the roasting, the proportion of the chloride or hypochlorite depend-
ing in each case upon the quantity of sulphur or phosphorus (if any), or of the
compounds of either of those substances, which may be contained in the iron
ore and in the fuel, by means of which it may be roasted.
If chlorine or
hydrochloric acid be used in a gaseous state, it may be introduced into the
roasting kiln in the same or a similar manner as herein-before described with
respect to the introduction of chlorine into the blast furnace. I prefer to
introduce the gas into that part of the kiln where the fuel is in a state of
incipient combustion, taking care in every case that the quantity of gas
introduced is not so great as to stop or materially retard the combustion.
Secondly, the materials which I employ for the purpose of obtaining coke or
coal partially coked free or more free than hitherto from sulphur or phos-
phorous, or any compound of those substances, or for fixing such substances or
compounds in manner aforesaid, according to the second part of my Invention,
as chlorine, hydrochloric acid, chlorides, hypochlorites, alkalies, and alkaline
carbonates. When I use chlorine for this purpose, during the process of coking
I cause chlorine gas or hydrochloric acid gas to pass through the coke or coals,
commencing a few hours before the coke is drawn out of the oven or furnace,
either after or before the extinction of the fire, and keeping up the introduction
of the gas until the volatile products of sulphur cease to be evolved, or nearly so.
It is not, however, essential that the gas should be passed through the coke or
coal partially coked during its manufacture; for when found more convenient,
the sulphur or phosphorus and their compounds may be removed by passing
the chlorine or hydrochloric acid gas through or into the coke or coal partially
coked after it has been manufactured, and then re-heating it to a red heat in
a suitable furnace. To pass the chlorine or hydrochloric acid gas through
coke at the temperature of the atmosphere or at a red heat, any kind of
furnace may be used; but I prefer to employ for the percolation or passage of
the gas used a furnace constructed with channels, in the manner shewn in the
annexed Drawing, but which I do not intend to claim as forming any part of
my Invention.

page_text: The channels, marked A, B, C, D, E, and F, in the accompanying Drawing,
are covered with fire brick tiles, having a hole of about an inch diameter in
the centre of each; these tiles are so placed that the holes are about one foot
apart, therefore the gas is uniformly distributed through the mass of the coke.
By this arrangement the channels or main passages for the chlorine or other
gas are of easy access, and can be readily cleaned out. When I employ
chlorides or hypochlorites, such as those of sodium, potassium, ammonium,
calcium, iron, manganese, (but I prefer chloride of sodium, as it is cheap and
readily obtained,) they may be applied in several ways. One of these modes
consists in mixing the chloride or hypochlorite either dry, or dissolved in water
with the coal, either previous to its introduction, or during its introduction, or
after it is introduced into the coke oven; and when the contents of the oven
are heated, the chloride or hypochlorite will act upon the sulphur or phos-
phorus, and the sulphur or phosphorus, or the greater part of those substances,
will be driven off; and in some cases a portion of them may be combined with
the body or material with which the chlorine was previously combined, and
become fixed in such a manner as to prevent their injurious effects.
These chlorides or hypochlorites may be applied in the manner I have
described, either when the coke or partially coked coal is made in closed ovens,
kilns in the open air, or in any other manner. I find that the admixture of
from one to five per cent. of chloride of sodium with the coal intended to be
made into coke is generally sufficient; of course the quantity of chloride or
hypochlorite employed varies with the proportion of sulphur or phosphorus
and their compounds existing in the coal intended to be transformed into coke
or coal partially coked; and if the quantity of sulphur or phosphorus contained
in the coal be known or ascertained, the quantity of chloride or hypochlorite
required will be known from what I have herein-before stated in describing.
the first part of my Invention. I can also employ these chlorides, hypochlorites,
either dry or dissolved in water, by mixing them with the coke, or coal par-
tially coked, after it has been completely manufactured and cool. But for this
class of compounds to act on the sulphur, phosphorus, and their compounds,
contained in the coke or coal partially coked, manufactured by the known
processes and cooled, it is necessary to re-heat this coke or coal partially
coked to a red heat, either in a suitable or special furnace or oven. When I
employ an alkali or alkaline carbonate, such as common soda or potash,) for
purifying coke or coal partially coked from sulphur or phosphorus, or their
compounds, I employ such a proportion of the material as will combine with
or neutralise the sulphur or phosphorus contained in the coke or partially
coked coal, and for this purpose, for every sixteen parts of sulphur thirty-one

page_text: parts of soda or forty-seven parts of potash will be required, or alkaline
carbonates containing equivalent quantities of those bases. The proportions
just stated apply to the several materials in the anhydrous state, and therefore
allowance must be made for the water with which they will be combined when
hydrated. I can also use chlorine, hydrochloric acid, chlorides, hypochlorites,
alkalies, and alkaline carbonates to purify coke or partially coked coal, by
dissolving them in the water intended to cool or extinguish the coke or coals
partially coked, either before removing them from the furnace or oven, or after
they have been removed from the same.
Having now described the nature of my Invention, and the manner in
which the same is to be performed, I hereby declare that I claim as of my
Invention,
Firstly, the application of chlorine, hydrochloric acid, chlorides, and hypo-
chlorites to the manufacturing of iron, in manner herein-before described, for
the purpose of obtaining such iron free or more free than hitherto from
sulphuric phosphorus, and the compounds of those substances.
Secondly, the application of chlorine, hydrochoric, and chlorides, hypo-
chlorites, alkalies, and alkaline carbonates, in the manufacturing and purifying
of coke and partially coked coal, in manner and for the purposes herein-before
described.
In witness whereof, I, the said Frederick Crave Calvert, have hereunto
set my hand and seal, this Thirtieth day of April, in the year of
our Lord One thousand eight hundred and fifty-two.
Enrolled the Thirtieth day of April, in the year of our Lord One
thousand eight hundred and fifty-two.