IMPROVEMENTS IN PURIFYING SEWAGE AND FOUL WATER, AND IN TREATING WATER FOR BOILER PURPOSES
Year: 1876

page_text: LETTERS PATENT to Joe Frost, of Huddersfield, in the County of York,
Manufacturing Chemist, for the Invention of "IMPROVEMENTS IN PURIFYING
SEWAGE AND FOUL WATER, AND IN TREATING WATER FOR BOILER PURPOSES."
PROVISIONAL SPECIFICATION left by the said Joe Frost at the Office of the
Commissioners of Patents on the 26th August 1870.
JOE FROST, of Huddersfield, in the County of York, Manufacturing Chemist.
"IMPROVEMENTS IN PURIFYING SEWAGE AND FOUL WATER, AND IN TREATING
WATER FOR BOILER PURPOSES."
In carrying out my Invention I propose to employ the following ingredients,
viz.-The sulphides and hydrates of barium, hydrates of iron, and the precipitated
hydrates, sulphydrates and sulphides of the same metal, the sulphides of soda, slaked
lime, carbonate of lime, and sulphuric acid. These may be employed either separately
or in a variety of combinations, according to the character of the sewage or water
under treatment.
For example. Into a tank or receptacle containing dye or sewage water I intro-
duce sulphide of barium (with or without lime or hydrate of iron). The contents of
the tank are then agitated, and allowed to settle until the precipitation ceases. If
it is desired to free the water perfectly from barium compounds, colouring matter,
sulphuretted hydrogen sulphides remaining in solution, I draw the water off into a
second tank, and treat it with hydrate of iron or sulphate of lime, or a small quantity
of sulphuric acid, and then add hydrate of iron The water is then agitated in this
tank, and either allowed to settle or to run on to filter beds composed partly of iron
compounds and sulphate of lime.
Ex. 2. Mix with the water to be clarified a quantity of sulphide, sulphydrate, or
hydrate of iron previouly precipitated with lime or any other alkaline body, agitate
the whole thoroughly, and allow the precipitate to settle.
Ex. 3. Mix with the water a quantity of crude sulphide of soda, and add thereto
hydrate of iron.
Ex. 4. Take a quantity of the residue obtained by fusing together salt cake or
any sulphide of soda with an excess of small coal and dissolving out the hydrate

page_text: and sulphide of soda; the residue thus obtained consists of sulphide of iron and
finely divided carbon. Add this to the water along with lime, agitate, and allow to
settle as in previous cases.
The advantages obtained by using the substances heroin named are,—
Firstly. The hydrates and sulphydrates of iron are in a suitable condition for
uniting with the colouring matteis to form precipitates.
Secondly. The quantity of lime and other alkali required is small, there being no
acids to neutralize as when salts of iron are used; therefore there is less residuum
to be delt with.
Thirdly. The quantity of soluable salts in the water after treatment is considerably
less.
Fourthly. The residuum may be collected and used again for the same purpose,
and thus reduce the cost of the purifying operations.
-
SPECIFICATION in pursuance of the conditions of the Letters Patent filed by
the said Joe Frost in the Great Seal Patent Office on the 26th February
1877.
JOE FROST, of Huddersfield, in the County of York, Manufacturing Chemist.
"IMPROVEMENTS IN PURIFYING SEWAGE AND FOUL WATER, AND IN TREATING WATER
FOR BOILER PURPOSES"
In carrying out my Invention I propose to employ the following ingredients,
viz: The sulphides and hydrates of barium, hydrates of iron, and the precipitated
hydrates, sulphydrates and sulphides of the same metal, the sulphides of soda, slaked
lime, carbonate of lime, and sulphuric acid; these may be employed either separately
or in a variety of combinations, according to the character of the sewage or water
under treatment.
For example Into a tank or receptacle containing dye or sewage water I intro-
duce sulphide of barium or the hydrate of barium, which I obtain by boiling the
crude sulphide with hydrate of iron, the resulting mixture being the hydrate of
barium and sulphide of iron, this mixture I either use as it is, or I treat the same
with more water, and use only the soluble portion, which consists of the hydrate of
barium, with varying proportions of the several sulphides of barium, according to
the proportion of hydrate of iron which has been used. If the water to be treated be
not highly coloured, and contains a little sulphuric acid, as dye waters usually do,
then the addition of the barium mixture will be sufficient to clarify the water by
forming the insoluble sulphate of barium, or I add finely ground sulphate of barium,
which carries down the colouring matters If the water does not contain sufficient
sulphuric acid a quantity of the same must be added. In addition to the sulphuric
acid being precipitated the barium forms a number of other insoluble compounds
with colouring matters found in dye waters Waters clarified in this manner may
be used over again for various purposes, as for boilers, if free from the soluble
sulphides. If the waters to be treated are very dirty, through dyes and sewage, I
mix the barium sulphide with a quantity of lime, with or without the application of
heat, and add this to the water, or I first treat the waters with the lime and then
with the barium mixture I allow these to settle in the tank, and then treat the
same water in either a second tank or in the same after settling with sulphate of
lime, the hydrate of iron, or the partly oxidized sulphide or sulphydrate, or a small
quantity of sulphuric acid. By this treatment when in a second tank the iron
compounds used may be again recovered and used over again for the same purpose,
being free from the greater portion of organic and other matters, the water is also
freed from the soluble sulphides. The water is then agitated in this tank, and
either allowed to settle or to run on to filter beds composed partly of iron com-
pounds and sulphate of lime The hydrate of iron above mentioned I obtain by
the well known method of treating the soluble salts of iron with an alkaline hydrate,

page_text: as the hydrate of soda, potash, ammonia, or lime. For example, I take a peroxide
or hydrated peroxide of iron, and convert this into persulphate or any other salt,
then treat the same with sufficient lime to convert the same into hydrate In place
of lime I use hydrate of soda or the crude mixture of hydrate and carbonate, and
recover the sulphate of soda.
Example 2 Mix with the water to be clarified a quantity of sulphide, sulphy-
drate, or hydrate of iron previously precipitated with lime or any other alkaline
body; agitate the whole thoroughly, and allow the the precipitate to settle. The
sulphide of iron or the sulphydrate I obtain by treating a salt of iron, preferably a
persalt, with sulphide of soda as prepared by method herein-after described. The
resulting sulphate of soda from the iron compound may be then used again. If
nitrate of iron be used the resulting nitrate of soda may be mixed with residuum to
make it more valuable as manure. The mixture I sometimes expose to the air until
it becomes partly oxidized, the object being to obtain a quantity of iron in the
per" condition, as this has the greatest power of clarifying and deodorizing sewage
by giving up its oxygen to organic substances; I use lime at the same time if required
in a second tank, and if any iron is remaining in the water it is precipitated by the
water being made alkaline
Example 3. Mix with the water a quantity of crude sulphide of soda, and add
thereto perhydrate of iron. Only sufficient sulphide of soda need be used to make
the water slightly alkaline.
To
Example 4. Take a quantity of the residue obtained by fusing together salt cake
or any sulphate of soda with an excess of small coal (preferably in a vessel lined
with carbon), and dissolving out the hydrate and sulphide of soda; the residue thus
obtained consists of sulphide of iron and finely divided carbon. Add this to the
water along with lime, agitate, and allow to settle as in previous cases.
render this mixture more effective I take a quantity and boil the same with water,
or mix it with hot water. By this treatment the compounds take up a large
quantity of water, becoming gelatinous. This affinity, of this for colouring matters
is now very much increased, particularly in presence of a small quantity of lime.
If the sulphate of soda or salt cake used be free from iròn I introduce the same in
any condition, metallic, hydrate, or oxide. With this mixture I at times heat the
sulphide of baun with or without the iron compounds, and in any proportion. If
with an excess of the oxide or hydrate of iron the soluble or caustic soda which is
formed will be available for the formation of the hydrate of iron, and the resulting
sulphide of soda may be used again for producing fresh quantities of the sulphide or
sulphydrate of iron.
The residues may be used over again for a variety of purposes. Where the
residues containing the iron, can be collected separately I first drain well, and then
expose the same to the air, so that it may become oxidized into sulphates and
oxides and used again or made into sulphate by the action of sulphuric acid, or the
same may be sold for the production of sulphate of iron. Where the hydrate of
barium and sulphide are used principally the residues are collected, often containing
sufficient carbonaceous matter to effect the reduction, if not a little carbonaceous
matter may be added, so that it may be used over again for the same purposes as
before described. At times I use in second or other tank a small quantity of
sulphuric acid, with or without barium mixture to render the water neutral or
acid, as a great number of colouring matters are dissolved by an excess of lime and
other alkalies, and precipitated by the acid.
When the water is to be treated for boiler purposes or scouring I proceed as
follows: For waters containing sulphate of lime and magnesia I add to a given
quantity of water its equivalent of hydrate of barium; the sulphates of lime and
magnesia become changed into bydrates, and the sulphuric acid as sulphate of
barium. If the water in this condition be exposed to the air for some time
the lime and magnesia are precipitated as carbonates. If the time cannot be
allowed then I add carbonate of soda, soda ash, or crystal, and the lime and
magnesia then fall as carbonates, together with the barium, if an excess
•

page_text: has been used; or barium sulphide is added to the water containing the sulphates,
which then forms the sulphate of barium and sulphide of calcium. Per chloride of
iron is then added, which converts any soluble sulphide of calcium into sulphide of
iron and chloride of calcium. Time is then allowed for the iron to settle and to
oxidize if any be dissolved, this must be done in order to prevent sulphur compounds
passing into the boiler.
The advantages obtained by using the substances herein named are,-
Firstly. The hydrates and sulphydrates of ion are in a suitable condition for
uniting with the colouring matters to form precipitates.
Secondly. The quantity of lime and other alkali required is small, there being no
acids to neutralize as when salts of iron are used, therefore there is less residuum to
bo dealt with.
Thirdly. The quantity of soluble salts in the water after treatment is considerably
less.
Fourthly. The residuum may be collected and used again for the same purpose,
and thus reduce the cost of the purifying operations.
Fifthly. The small per centage of barium compounds used cannot possibly
interfere with the quality of the water, and providing a small quantity should
escape the effluent the rivers which are constantly fed by springs containing soluble
sulphates would at once turn it into the harmless sulphate, which would rapidly
precipitate.
Sixthly. That the compounds I use, and the manner in which I use the same,
both the acid and the base are precipitated, and have at the same time an affinity
for colouring matters.
Having thus described the nature of my Invention, and the manner in which the
same is to be performed, I would have it understood that I lay no claim to the
whole of the chemicals herein mentioned, as some of them are not new for the
purpose, but what I do claim as my Invention is,—
Firstly. The use of the sulphides, sulphates, sulphydrates, and hydrates of barium,
as herein described.
Secondly. The use in combination with the above substances of the hydrates,
sulphydrates, and sulphides of iron, the sulphides of soda, slaked lime, and sulphuric
acid
In witness whereof, I, the said Joe Frost, have hereunto set my hand and seal,
this Twenty-fourth day of February, in the year of our Lord One thousand
eight hundred and seventy-seven.
Witness,
A. B. CROSSLEY,
Clerk to W. Tasker,
Patent Agent,
Halifax.
JOE FROST. (L.S.)