Process for the Utilization of Liquors Containing Sulphate of Alumina or Ferric Sulphate.
Year: 1893

page_text: Date of Application, 18th Jan., 1893
Complete Specification Left, 11th Aug., 1893-Accepted, 30th Sept., 1893
PROVISIONAL SPECIFICATION.
A Process for the Utilization of Liquors Containing Sulphate of
Alumina or Ferric Sulphate.
We, LEBERECHT TRALLS, of Dux, Bohemia, in the Empire of Austria,
Superintendent of Mines, and EDWARD BURMEISTER, of 16, Brandswiete,
Hamburg, in the Empire of Germany, Merchant, do hereby declare the nature of
this invention to be as follows:-
Coal pits, especially those from which coal for fuel is raised, are subject to a
source of loss arising from the very large quantity, often amounting to 30%, of
refuse or waste coal, or so-called slack coal. The commercial success of such
mines, and therewith the working of the seam of coal mined, may thereby be
rendered very doubtful, if the fact be taken into consideration that the cost of
handling the whole of the slack must be borne by the marketable coal. The slack
moreover requires a certain amount of storage room, which again represents a
certain cost, if it cannot be removed, and this again involves a certain amount of
expenditure, which on account of the worthlessness of the material has no set-off.
For the above reasons efforts have been made to utilize the slack, and make it
available for manufacturing purposes, which have been chiefly successful when
directed to the production of ammonia, from the nitrogenous and ash constituents,
by adding gypsum to the slack, roasting or burning it, and treating the product so
obtained by lixiviation. From the liquor so produced alum was then obtained.
The exhausted mother liquor, of no value, obtained as a bye-product constituted
then another source of difficulty from its containing sulphate of alumina and ferric
sulphate with other salts, so that it could not without further treatment be allowed
to run away, in consequence of its injurious action upon animal and plant life, not
only in rivers but also in arable and meadow land. Furthermore except in presence
of an immediate demand for alum the treatment of the ash-lixivium for the
production of alum is of no economic advantage.
The object in view was, then, to render mother liquor (which had either been
employed in the production of alum or which, in consequence of the commercial
outlook, it was not desired to employ for the purpose) innocuous, and if possible, to
utilize it. Since the sulphate of alumina and ferric sulphate constituted by far the
largest portion of the injurious salts, it was to their removal that the efforts to
utilize the mother liquor by rendering it innocuous or even useful were directed.
In order to be sure of obtaining a marketable product it appeared to be necessary
to seek for such a method of utilizing the mother liquors as to produce a commodity
which should be as nearly certain as possible to meet a widely felt want.
By our invention slack, or liquor containing sulphate of alumina and ferric
sulphate is utilized for the production of manure, in view of the fact that alumina
and oxide of iron are of themselves in no way hurtful to land and that the sulphuric
acid combined with these bases is calculated to prevent the escape of the free or
volatile ammonia the nitrogen of which is so valuable in agriculture and also to
destroy the chlorides which if present in large quantity are injurious to the latter.
Our process for utilizing liquors containing sulphate of alumina or ferric
sulphate, especially the lixivium of shale ashes, or the waste mother liquor in the
manufacture of alum, consists in their conversion into sulphate manure by saturating
substances containing ammonia, ammonium carbonate, or sal ammoniac, or calcarcons
or chlorinated materials with such liquors; or by saturating the liquors referred to
with substances containing carbonate of ammonia such as watery products of
listillation of nitrogenous organic materials such as coal, bones, or the like, or with

page_text: calcareous (or chlorinated) substances, such as quicklime, lime ashes, lime or soda
mud, phosphates from any source preferred, or the like if desired, in association
with substances containing carbonate of ammonia such as those hereinbefore
referred to for the conversion of the ferric sulphate or sulphate of alumina.
When saturating the said liquors with substances containing carbonate of
ammonia we carry out our process by mixing the liquors containing the sulphate of
alumina or ferric sulphate in an evaporated state with the materials containing
ammonium carbonate therein referred to. Or in order to enrich the resulting
product in nitrogen, we reconvert the hydrate of aluminium or iron contained in
the resulting product into their corresponding sulphates and then again reduce the
latter by the use of the ammoniacal substances referred to, which process may be
repeated as often as desired.
Dated this 18th day of January 1893
G. F. REDFERN & Co.,
4, South Street, Finsbury, London, Agents for the Applicants.
COMPLETE SPECIFICATION.
A Process for the Utilization of Liquors Containing Sulphate of
Alumina or Ferric Sulphate.
We, LEBERECHT TRALLS, of Dux, Bohemia, in the Empire of Austria,
Superintendent of Mines, and EDWARD BURMEISTER, of 73/77 Reichenstrasse,
Hamburg, in the Empire of Germany, Merchant, 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:-
Coal pits, especially those from which coal for fuel is raised, are subject to a
source of loss arising from the very large quantity, often amounting to 30%, of
refuse or waste coal, or so-called slack coal. The commercial success of such
mines, and therewith the working of the seam of coal mined, may thereby be
rendered very doubtful, if the fact be taken into consideration that the cost of
handling the whole of the slack must be borne by the marketable coal. The slack
morcover requires a certain amount of storage room, which again represents a
certain cost, if it cannot be removed, and this again involves a certain amount of
expenditure, which on account of the worthlessness the material has no set-off.
For the above reasons efforts have been made to utilize the slack, and make it
available for manufacturing purposes, which have been chiefly successful when
directed to the production of ammonia, from the nitrogenous and ash constituents,.
by adding gypsum to the slack, roasting or burning it, and treating the product so
obtained by lixiviation. From the liquor so produced alum was then obtained.
The exhausted mother liquor, of no value, obtained as a bye product constituted
then another source of difficulty from its containing sulphate of alumina and ferric
sulphate with other salts, so that it could not without further treatment be allowed
to run away, in consequence of its injurious action upon uimal and plant life, not
only in rivers but also in arable and meadow land. Furthermore except in
presence of an immediate demand for alum the treatment of the ash-lixivium for
the production of alum is of no economic advantage.
The object in view was, then, to render liquor (which had either been employed
in the production of alum or which, in consequence of the commercial outlook, it
was not desired to employ for the purpose) innocuous, and if possible, to utilize it.
Since the sulphate of alumina and ferric sulphate constituted by far the largest
portion of the injurious salts, it was to their removal that the efforts to utilize the
mother liquor by rendering it innocuous or even useful were directed. In order to
be sure of obtaining a marketable product it appeared to be necessary to seek for
such a method of utilizing the mother liquors as to produce a commodity which
should be as nearly certain as possible to meet a widely felt want.

page_text: By our invention the slack, or the mother liquor containing sulphate of alumina
and ferric sulphate is utilized for the production of manure, in view of the fact
that alumina and oxide of iron are of themselves in no way hurtful to land and
that the sulphuric acid combined with these bases is calculated to prevent the
escape of the free or volatile ammonia the nitrogen of which is so valuable in
agriculture and also to destroy the chlorides which if present in large quantity are
injurious to the latter.
According to our invention the utilization of mother liquors containing sulphate
of alumina and ferric sulphate, especially such as result from the manufacture of
alum, and from the refuse of shale works, is effected by employing them for the
manufacture of manure.
As is well known, it is of great importance in agriculture to maintain the
nitrogenous constituents of the soil at a certain standard by means of suitable
manures. To this end there may be employed such materials as contain ammonia
or those which contain nitrogen not only in the form of ammonia, ammonium
carbonate, or sal ammoniac, but those which tend to be easily converted into one
of the latter forms. Such materials, containing nitrogen, ammonia, ammonium
carbonate, or sal ammoniac, are found amongst the bye-products of manufacturing
processes, especially in the utilization and conversion of pit coal, shale, peat,
bones, viz. the watery products obtained by the distillation of such materials,
which watery products contain ammonia, ammonium carbonate sal ammoniac, or
bodies allied to ammonia, and are hereinafter spoken of generally under the name
of gas liquor.
By the addition of such materials it is possible to effect the utilization of liquors
containing sulphate of alumina or ferric sulphate by treating the latter with the
former for a length of time sufficient to transform the sulphate of alumina or ferric
sulphate, and this may in general be recognised by the fact that gas (carbonic acid)
is no longer given off, and that the acid reaction of the liquor has given place to a
neutral one in the final product. The resulting mass, or if desired the fluid
separated by filtration or otherwise from the solid constituents may then be
evaporated, and the resulting product is a substance which may contain as much
as 10% of ammonia.
If
The oxides or hydroxides of aluminium and iron are set free in this process.
it be intended to produce a material specially rich in nitrogen or aminonia, it is
possible, especially if sulphuric acid can be had at a very low price, to add to the
mass containing the oxides of alumina and iron the quantity of sulphuric acid
required to re-form the ferric sulphate or sulphate of alumina, and then, as above
described, again to add the substances containing nitrogen or carbonate of ammonia
before referred to until the sulphate of alumina or ferric sulphate reproduced is
reconverted. This operation may be repeated as often as desired.
The liquors
containing sulphate of alumina and ferric sulphate may also be utilized by treatment
with substances which develop ammonia or contain ammonium carbonate by first
evaporating the liquors alone, and then adding the ammonia-generating material
to the residue left after evaporation, which process may be easily carried out at
the place where the former has accumulated, In the product resulting from
this process the ammonia is always present in the form of sulphate of ammonia.
Since in many cases the presence not only of ammoniacal but also of calcareous
manure stuffs is necessary, and since it frequently happens that the latter (especially
spodium or quicklime or materials containing caustic lime, such as lime ashes,
Thomas slag) on account of their basic character give rise to the formation of free
ammonia and the consequent loss of the latter, liquors containing sulphate of
alumina or ferric sulphate may be so treated as to meet this requirement by acting
upon them with calcareous materials until the complete conversion of the ferric
sulphate or sulphate of alumina is effected, and this conversion may be effected by
the addition of such calcareous materials (also phosphates from any source desired)
as well as by the materials previously referred to containing ammonia or ammonium

page_text: carbonate. In the latter case (i.e. when both calcareous and ammoniacal ingredients
are added) the product would contain not only a large proportion of lime (with
phosphoric acid) but also nitrogen (as ammonia) in a condition of intimate mixture,
but in both cases the lime is reduced to a form in which it is no longer capable of
driving off the ammonia and causing it to be lost.
If there be employed as the calcareous material in the method just described for
converting the ferric sulphate or sulphate of alumina the waste product formed in
the soda manufacture which gives rise to so much trouble, and which contains lime
and is known as lime or soda mud, by saturating this mud preferably at a high
temperature, with the liquor under consideration, that is to say, until the chlorine
of the mud has been driven off as hydrochloric acid, it is possible to effect simul-
taneously the profitable utilization of this waste product also as a sulphate manure.
By this method not only the chlorinated soda mud, but also other chlorinated sub-
stances, such as the chlorinated waste product in the manufacture of potassium
salts, may be treated with the liquors containing ferric sulphate or sulphate of
alumina, and so the chlorine which gives rise to the formation of the injurious
chlorides may be driven off. As with the calcareous or chlorinated materials
already referred to so in this case the liquor may be saturated partly with the
substances already mentioned as containing ammonium carbonate and partly with
those containing lime.
The employment of liquors containing the ferric sulphate or sulphate of alumina,
in themselves so injurious to the life of animals and plants, and especially of such
liquors as are produced in the manufacture of alum, and in the lixiviation of coal
or shale ashes, for the production of sulphate manures by using materials containing
ammonium carbonate, such as gas liquor, or calcareous or chlorinated materials or
waste products, not only makes them innocuous but offers a method of utilizing
them in which at one time waste products containing ammonium carbonate, and
the troublesome ones which are calcareous or chlorinated are alike turned to
advantage. There is thus offered a prospect of working slack at a considerable
percentage of profit for collieries by the production of substances for which there
will always be a market in agriculture, especially when it is borne in mind that, as
has been stated, this turning to advantage can be effected merely by the use of
products or substances such as are yielded by the processes carried on in working
shale mines, tar distilleries and similar industries, with, if desired, the use of other
materials which are thereby also utilized.
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. A process for utilizing liquors containing sulphate of alumina or ferric
sulphate, especially the lixiviation of shale ashes, or the waste liquor in the manu-
facture of alum, by their conversion into sulphate manure by saturating substances
containing ammonia, ammonium carbonate, or sal ammoniac, or calcareous or
chlorinated materials with such liquors; or by saturating the liquors referred to:
(a) with substances containing carbonate of ammonia such as watery products
of distillation of nitrogenous organic materials such as coal, bones or the
like, or
(b) with calcareous (or chlorinated) substances, such as quicklime, lime ashes,
lime or soda mud, phosphates from any source preferred, or the like, if
desired, in association with the materials referred to under (a) for the
conversion of the ferric sulphate or sulphate of alumina.
2. A method of carrying out the process described in Claim 1 (a) consisting in
mixing the liquors containing the sulphate of alumina or ferric sulphate in an
evaporated state with the materials containing ammonium carbonate therein
referred to.
3. A further method of carrying out the process described in Claim 1 (a) so as to

page_text: enrich the resulting product in nitrogen by reconverting the hydroxide of
aluminium or iron contained in the resulting product into their corresponding
sulphates and then again reducing the latter by the use of the ammoniacal
substances referred to, which process may be repeated as often as desired.
Dated the 11th day of August 1893.
G. F. REDFERN & Co.,
4, South Street, Finsbury, London, Agents for the Applicants.