Sulphide Waste of Le Blanc Soda Manufactures.
Year: 1888

page_text: Sulphide Waste of Le Blanc Soda Manufactures.
We, JOHN SAMUEL RIGBY of 35 Bagot Street, Liverpool in the County of
Lancaster, and ANDREW MACDONALD of Neptune Street, Liverpool in the County
of Lancaster, Manufacturing Chemist and Oil Merchant, respectively, do hereby
declare the nature of this invention to be as follows:-
Many attempts have been made to extract the sulphur from alkali waste, mainly
sulphide of calcium, and some of these bid fair to be successful, but little or no efforts
have been made to utilize the lime thereof.
Now our invention is designed for this purpose, and consists in making hydraulic
mortar or cement therefrom. In carrying out our invention, we mix the fresh waste
with water and then pass carbonic acid through, on the old plan invented and
patented by Gossage in England, in 1852, or the modification thereof, lately patented
by Chance of Birmingham, the result is, sulphuretted hydrogen, which passes off and
is burned to make sulphuric acid, or utilised in any known way, and crude
carbonate of lime. This latter is so largely contaminated with sulphur and its
compounds as to be useless for cement making by the ordinary process. We,
however, mix it with clay, ground shale, or other equivalent material till there is
about 10 of alumina and iron and 22 of silica to 60 of lime (Ca O). The mixture
is now placed in a furnace or kiln and roasted at about 200 degrees Centigrade till
the free sulphur has been driven off. This can either escape into the atmosphere, or if
that be objected to, the fumes can be passed through milk of lime or caustic soda
solution and a sulphite formed. After this the mixture is further raised to a dull
red heat and the sulphide of iron decomposed, the sulphur passing off as sulphurous
acid, and any sulphate of soda present decomposed by the silica and carbon. The
material can now be made into bricks with a little water, dried and calcined in a
Dietzch cement kiln, or the entire process after mixing the waste with the aluminous
material can be continuously carried on in a furnace revolving on a horizontal axis.

page_text: In this latter case, the mixture is put into the revolving furnace, dried and heated
to 200 degrees Centigrade to drive off the free sulphur, then to a higher temperature
to roast the sulphides and form oxides thereof, and lastly, to a heat sufficient to drive
off the carbonic acid and form cement.
If desired, the waste can be dried, heated and roasted prior to adding the 5
aluminous materials, but there are little or no advantages in this plan, while by
roasting the two together, the mixture becomes more intimate; and is more open to
the action of the surrounding heated gases.
Dnted this 4th day of Inly 1888
WM. P. THOMPSON & Co.,
Of 6, Lord Street, Liverpool,
Patent Agents for the Applicants.

page_text: Sulphide Waste of Le Blanc Soda Manufactures.
We, JOHN SAMUEL RIGBY of 35 Bagot Street Liverpool in the County of
Lancaster and ANDREW MACDONALD of Neptune Street Liverpool in the County of
Lancaster, Manufacturing Chemist and Oil Merchant respectively 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:
Many attempts have been made to extract the sulphur from alkali waste, which
consists mainly of sulphide of calcium, and some of these bid fair to be successful, but
little or no efforts have been made to utilise the lime thereof.
Now our invention is designed for this purpose, and consists in making bydraulic
mortar or cement therefrom.
In carrying out our invention, we mix the fresh waste with water in a vat having
an agitating device, or otherwise, and then pass carbonic acid through on the old
plan invented and patented by Gossage in England in 1852, or the modification
thereof, lately patented by Chance No. 24958 dated 20th February 1888 of Birmingham,
the result is, sulphuretted hydrogen, (which passes off and is burned to make
sulphuric acid or utilised in any known way) and crude carbonate of lime. This
latter is so largely contaminated with sulphur and its compounds, and other soluble
salts, as to be useless for cement making by the ordinary process. We, however, mix
it with clay or other equivalent material in about the proportion of 34 parts waste to
1 of clay, both dry, the resulting mixture having about 10 alumina and iron,
22 silica and 60 lime. The mixture is now placed in a furnace or kiln and roasted
at a little above 440 degrees Centigrade till the free sulphur has been driven off.
This can either escape into the atmosphere, or if that be objected to, the fumes can be
passed through milk of lime or caustic soda solution and a sulphite formed. After
this the mixture may be raised to a dull red heat, and the sulphide of iron decom-
posed, the sulphur passing off as sulphurous acid. The material can now be made
into bricks with a little water, dried and calcined in a cement kilu, or the entire process
after mixing the waste with the aluminous material can be carried on in a Dietzsch
kiln or a furnace revolving on a horizontal axis.
If desired, the waste can be dried, heated and roasted, prior to adding the aluminous
materials, but there are little or no advantages in this plan, while by roasting the two
together, the mixture becomes more intimate, and is more open to the action of the
surrounding heated gases.
To extract any sulphate of lime contained in the residue, where old waste is used
(if the original waste has been exposed long to the air before being operated upon),
an excess of vat liquor (solution of alkaline carbonate) is added, sufficient to dissolve
out or decompose this sulphate. The material is again well washed in water, finely
divided clay or equivalent silica-aluminous matter in the requisite well known
proportions to form cement is now added, (this is about 3 of waste to one of clay

page_text: both in the dry state). The exact quantity required depends on the quality of the
clay. The latter is mixed in, and the mass is put into a cement kiln, preferably one
of those which revolves on a horizontal axis, and the heat is gradually raised to tho
degree requisite to drive off the carbonic acid in the usual way, the mass is then
ground and purged, that is, exposed to the air for a time in the usual manner.
Having now particularly described and ascertained the nature of our said inven-
tion, and in what manner the same is to be performed, we declare that what we
claim is :-
1. The manufacture of cement from Le Blanc alkali waste, by first expelling the
greater part of the sulphur by carbonic acid, then extracting the remaining
sulphur and sulphur salts in the manner substantially as described, mixing with clay
or its equivalent, and then calcining, grinding, and purging.
2. The manufacture of cement from Le Blanc alkali waste, substantially as herein
described.

page_text: Date of Application, 5th July, 1888
Complete Specification Left, 31st Jan., 1889
Complete Specification Accepted, 23rd Mar., 1889
Sulphide Waste of Le Blanc Soda Manufactures.
We, JOHN SAMUEL RIGBY of 35 Bagot Street, Liverpool in the County of
Lancaster, and ANDREW MACDONALD of Neptune Street, Liverpool in the County
of Lancaster, Manufacturing Chemist and Oil Merchant, respectively, do hereby
declare the nature of this invention to be as follows:-
Many attempts have been made to extract the sulphur from alkali waste, mainly
sulphide of calcium, and some of these bid fair to be successful, but little or no efforts
have been made to utilize the lime thereof.
Now our invention is designed for this purpose, and consists in making hydraulic
mortar or cement therefrom. In carrying out our invention, we mix the fresh waste
with water and then pass carbonic acid through, on the old plan invented and
patented by Gossage in England, in 1852, or the modification thereof, lately patented
by Chance of Birmingham, the result is, sulphuretted hydrogen, which passes off and
is burned to make sulphuric acid, or utilised in any known way, and crude
carbonate of lime. This latter is so largely contaminated with sulphur and its
compounds as to be useless for cement making by the ordinary process. We,
however, mix it with clay, ground shale, or other equivalent material_till there is
about 10 of alumina and iron and 22 of silica to 60 of lime (Ca O). The mixture
is now placed in a furnace or kiln and roasted at about 200 degrees Centigrade till
the free sulphur has been driven off. This can either escape into the amosphere, or if
that be objected to, the fumes can be passed through milk of lime or caustic soda
solution and a sulphite formed. After this the mixture is further raised to a dull
red heat and the sulphide of iron decomposed, the sulphur passing off as sulphurous
acid. and any sulphate of soda present decomposed by the silica and carbon. The
material can now be made into bricks with a little water, dried and calcined in a
Dietzch cement kiln, or the entire process after mixing the waste with the aluminous
material can be continuously carried on in a furnace revolving on a horizontal axis.

page_text: In this latter case, the mixture is put into the revolving furnare, dried and heated
to 200 degrees Centigrade to drive off the free sulphur, then to a higher temperature
to roast the sulphides and form oxides thereof, and lastly, to a heat sufficient to drive
off the carbonic acid and form cement.
If desired, the waste can be dried, heated and roasted prior to adding the
aluminous materials, but there are little or no advantges in this plan, while by
roasting the two together, the mixture becomes more intimate; and is more open to
the netion of the surrounding hented gases.
WM. P. THOMPSON & Co.,
Of 6, Lord Street, Liverpool,
Patent Agents for the Applicants.

page_text: Sulphide Waste of Le Blanc Soda Manufactures.
We. JOHN SAMUEL RIGBY of 35 Bagot Street Liverpool in the County of
Lancaster and ANDREW MACDONALD of Neptune Street Liverpool in the County of
Lancaster, Manufacturing Chemist and Oil Merchant respectively 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 :-
Many attempts have been made to extract the sulphur from alkali waste, which
consists mainly of sulphide of calcium, and some of these bid fair to be successful, but
little or no efforts have been made to utilise the lime thereof.
Now our invention is designed for this purpose, and consists in making hydraulic
mortar or cement therefrom.
In carrying out our invention, we mix the frosh waste with water in a vat having
an agitating dovice, or otherwise, and then pass carbonic acid through on the old
plan invented and patented by Gossage in England in 1852, or the modification
thereof, lately patented by Chance No. 249588 dated 20th February 1888 of Birmingham,
the result is, sulphuretted hydrogen, (which passes off and is burned to make
sulphuric acid or utilised in any known way) and crude carbonate of lime. This
Intter is so largely contaminated with sulphur and its compounds, and other soluble
salts, as to be useless for cement making by the ordinary process. We, however, mix
it with clay or other equivalent material in about the proportion of 3 parts waste to
1 of clay, both dry, the resulting mixture having about 10 alumina and iron,
22 silica and 60 lime. The mixture is now placed in a furnace or kiln and roasted
at a little above 440 degrees Centigrade till the free sulphur has been driven off.
This can either escape into the atmosphere, or if that be objected to, the fumes can be
passed through milk of lime or caustic soda solution and a sulphite formed. After
this the mixture may be raised to a dull red heat, and the sulphide of iron decom-
posed, the sulphur passing off as sulphurous acid. The material can now be made
into bricks with a little water, dried and calcined in a cement kiln, or the entire process
after mixing the waste with the aluminous material can be carried on in a Dietzsch
kiln or a furnace revolving on a horizontal axis.
If desired, the waste can be dried, heated and roasted, prior to adding the aluminous
materials, but there are little or no advantages in this plan, while by roasting the two
together, the mixture becomes more intimate, and is more open to the action of the
surrounding heated gases.
-
A variation in the process is as follows:-
We add lime in excess of the equivalent of the free sulphur remaining in the
mass, to the waste, after the surphuretted hydrogen has been driven off, and steam
it with agitation, till the sulphur has combined with the lime, this usually takes
half an hour or more. This is again carbonated. The soluble salts are now washed
out with water.

page_text: To extract any sulphate of lime contained in the residue, where old waste is used
(if the original waste has been exposed long to the air before being operated upon),
an excess of vat liquor (solution of alkaline carbonate) is added, sufficient to dissolve
out or decompose this sulphate. The material is again wall washed in water, finely
divided clay or equivalent silica-aluminous matter in the requisito well known
proportions to form cement is now mulded, (this is about 34 of waste to one of clay
both in the dry state). The exact quantity required depends on the quality of the
clay. The latter is mixed in, and the mass is put into a coment kiln, proforably one
of those which revolves on a horizontal axis, and the heat is gradually raised to the
degree requisite to drive off the carbonic acid in the usual way, the mass is thon
ground and purgod, that is, exposed to the air for a time in the usual manner.
Having now particularly described and ascertained the nature of our said invon-
tion, and in what manner the same is to be performed, wo declare that what wo
alaim is :-
1. The manufacture of cement from Le Blanc alkali waste, by first expelling tho
greater part of the sulphur by carbonic acid, then extracting the remaining
sulphur and sulphur salts in the mannor substantially as described, inixing with clay
or its equivalent, and then caleining, grinding, and purging.
2. The utilisation of the line mul resulting from the Gossago or (hance sulphur
recovery process, or other similar process, for recovery of sulphur from Le Blanc soda
waste by converting the residual free sulphur into a soluble sulphide, washing out,
oxidising or decomposing, and washing out the remaining sulphur salts and using the
residue in place of ordinary limo or chalk for comment umnufacture.
8. The manufacture of cement from Le Blanc alkali waste, substantially as heroin
described.
Unted thin 30th day of January 1880.