Year: 1887

page_text: Date of Application, 23rd Dec., 1887
Complete Specification Left, 15th Sept., 1888
Complete Specification Accepted, 9th Nov., 1888
hereby declare the nature of this invention to be as follows
This invention has for its object, a novel improved and economical method of pro-
ducing the carbonates of potassium, sodium, and ammonium.
To effect this object phenate or cresylate of calcium, or the bodies obtained by the
union of lime or slaked lime with crude phenols (including thereby the higher
homologues of the phenol series) when coal tar oils or blast furnace or coke oven oils
are agitated with milk of lime, is used.
This compound or solution of crude phenols in milk of lime, is now treated with a
solution of sulphate of sodium or potassium or ammonium the said solutions may be
heated to facilitate the action or re-action of one body on the other. As a result of the
action, we have sulphate of lime precipitated as a fine crystalline powder, whilst
phenate or cresylate of sodium, or potassium, or ammonium a combination of sodium,
potassium and ammonium with the higher homologues of the phenol series, is left in
the watery solution.
The combination of phenols with sodium or potassium or ammonium is now treated
with carbonic acid gas in closed vessels, and when the solution is saturated with
carbonic acid gas, the contents of the vessels on standing, separate into two layers,
the lower layer containing a solution of carbonate of sodium, potassium ammonium,
whilst the upper layer consists of crude phenols. These crude phenols after being
separated from the solution of carbonates are again used in the process to form the
lime compounds of the phenols. Or the solution of phenols in sodium, etcetera as
above obtained may be so treated with carbonic acid gas as to form bicarbonates as
well as carbonates.
These solutions of carbonates or of sodium potassium, ammonium, which still contain
2 or 3 per cent. of phenols are evaporated to dryness in closed vessels, the distillate
containing phenols is received in a vessel containing slaked lime, whereby the lime
compound of the phenols is obtained, which may again be used. Or in the process,

page_text: an excess of the respective sulphates of the metals may be taken, so that as a result we
have produced solutions containing phenols in combination or solution with the
respective metals, sodium, potassium, ammonium, these solutions on being treated with
carbonic acid gas, yield the bicarbonates of sodium, potassium, ammonium, which are
precipitated. The excess of sulphates being left in solution, the phenols being less
soluble in these solutions of sulphates than in the solutions of carbonate of sodium,
potassium or ammonium separate more readily, and less phenols are left in the
solutions. The solutions of sulphates are again used in the process. A suitable
temperature is employed to maintain the sulphates in solution, whilst the bicarbonates
are being precipitated.
P T
1009
WM. P. THOMPSON & Co.,
Of 6, Lord Street, Liverpool,
Agents for the Applicant.

page_text: Improvements in the Manufacture of Alkaline Carbonates.
I, WILLIAM WRAY STAVELEY, of Baghill, Pontefract, in the County of York,
Manufacturing Chemist 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: :—
This invention has for its object a novel, improved and economical method of pro-
ducing the carbonates of sodium and potassium.
To effect this object, the phenoloid compounds of calcium (formed by the union of
phenol, cresol, or their higher homologues with calcium hydrate, slaked lime) after-
wards called calcium phenolates, are treated with a solution of sulphate of sodium or
potassium. As a result of the action, we have sulphate of calcium precipitated as a
fine crystalline powder, whilst the phenoloid compounds of sodium or potassium
(afterwards called sodium or potassium phenolates) are left in solution.
The phenolates of sodium or potassium, after filtration, are now submitted in closed
vessels to the action of a current of lime kiln or flue gases, until, by means of the
carbonic acid contained in the gases, the solutions are decomposed, with the formation
of sodium or potassium carbonates, with some bicarbonates, the phenoloid bodies being
liberated.
On discontinuing the current of gas through the vessels, and allowing the contents
of the vessels to remain undisturbed for one or two hours, the contents of the vessel
separate into two layers, the upper layer consisting mainly of the phenoloid bodies,
whilst the lower layer consists of a solution of carbonate, and some bicarbonate of
sodium or potassium.
In order to carry out the process on a manufacturing scale, I proceed as follows:
The quantities of each material and the bulk of the solutions being stated as for the
production of one ton of pure sodium or potassium carbonate or their equivalent in
poorer qualities.
1st. Process for sodium carbonate :-
11 cwts. of freshly burnt lime, Ca O, are slaked and made into milk of lime, the
bulk of which shall measure from 400 to 450 gallons. This milk of lime
on cooling, is gradually added 430 gallons, about 2 tons' weight, of distilled
phenoloid bodies, (phenol, cresol, or their higher homologues as obtained from coal
tar oils, coke oven or blast furnace oils), or a corresponding quantity of crude
phenoloid bodies. The phenoloids best suited for this purpose are those which distil
between 190 degrees Centigrade and 250 degrees Centigrade. We thus have a
solution of 830 to 880 gallons calcium phenolates. This solution may be made in any
open iron vessel provided with agitating apparatus, it being essential that the mixture
be agitated whilst being made.

page_text: This solution of calcium phenolates is now gradually added to a lot solution of 850
to 900 gallons, containing 293 cwts. of 95 per cent. salt cake, sulphate of soda, which
is contained in a vessel provided with apparatus for thoroughly agitating the contents.
The solution of calcium phenolates is run in during a period of about two hours, the
contents of the vessel being briskly agitated meanwhile. After the whole of the
solution of calcium phenolates has been run in, the agitation is continued for another
hour or two, the temperature of the contents of the vessel being maintained from the
beginning to the finish of the operation at about 35 degrees Centigrade.
At the end of the operation we shall have in the decomposing vessel, supposing 95
per cent. of the sulphate of soda has been decomposed, 1680 to 1780 gallons bulk,
containing soda, in the shape of phenolates, equal to 20 cwts. pure sodium carbonate.
430 gallons phenoloids 25 cwts. anhydrous calcium sulphate Ca SO,, or 32.4 cwts.
Ca SO, (H, O), and 1.4 cwts. about, of unchanged sodium sulphate.
The contents of decomposer are allowed to settle. On settling, the insoluble calcium
sulphate falls to the bottom of the decomposer, whilst the sodium phenolates
remain in solution. In well conducted operations, about 75 per cent. of the solution
of sodium phenolates may be decanted. The remaining mixture of sodium phenolates
and calcium sulphate is now run or pumped into suitable filtering apparatus; the
filtering beds, connected with vacuum pumps, as used for filtering the lime mud from
causticizing pans, being well suited for the purpose, or filter presses may be used.
The calcium sulphate left on the filters is now washed with 600 to 700 gallons hot
water, the washings containing some sodium phenolates being used to dissolve the
sulphate of sodium required in the first part of the process.
The sulphate of calcium, after removal from the filters, may be dried and after-
wards disposed of for manure or making stucco, or rough plaster of Paris.
The sodium phenolates solution is now treated in suitable vessels with fuel or lime
kiln gases, until, by means of the carbonic acid in the said gases, the solution is
carbonated, and a little bicarbonate formed, the stream of gases being discontinued, and
the contents of the vessel allowed to remain undisturbed for several hours, when the
liberated phenoloids separate and float, as an oily fluid, on the surface of the lower
layer of the solution, which consists mainly of carbonate of sodium. The phenoloid
bodies, which now contain about 10 to 15 per cent. of water or solution of carbonate,
are separated by suitable means, and may be again used in the decomposition or
conversion of another batch of sodium sulphate.
The carbonate of sodium solution, which still retains about 1 per cent. or 2 per
cent. of its bulk of phenoloids, may now be evaporated and calcined in the ordinary
evaporating pans and calcining furnaces, as used in the alkali works, the resulting
calcined mass being commercial soda ash. In this case, the phenoloids held in solution
by the sodium carbonate are, of course, lost. In order to avoid this, a quantity of
sodium hydrate sufficient to combine with the phenoloids, and to convert the bicarbonate
into carbonate of sodium, is added to the carbonate in the evaporating pan. The
phenoloid bodies are thus retained in the mother liquors on evaporation, which is con-
tinued until the sodium carbonate separates out and is fished, as in the ordinary process
of obtaining fished salts from the solutions obtained by the Leblanc process of making
.soda ash..
The mother liquors containing sodium carbonate, sodium sulphate, and sodium
phenolates, may be added to next operation in the decomposing vessel, thus permitting
the use of an excess of lime or calcium phenolates in the decomposing. of sodium
sulphate, and thus increasing the probability of a complete decomposition. The free
lime present would be converted into carbonate and sulphate of calcium and any free
phenoloids into sodium phenolates. The presence of uncombined lime or calcium
hydrate impedes the settling and filtration of the contents of decomposer. Or the
carbonate of sodium solution, instead of being evaporated and calcined may be con-
verted into bicarbonate as follows:-
To the solution of carbonate of sodium, is added as much sulphate of sodium.as it
will dissolve at a temperature of 34 or 35 degrees Centigrade. The solution of sodium
carbonate and sulphate thus obtained is now treated with lime kiln gases, the solution

page_text: being maintained at 34 to 35 degrees Centigrade, till bicarbonate of sodium is
formed, which falls to the bottom of the high cylindrical vessel in which the
bicarbonating is carried on. When the bicarbonate ceases to fall, the operation is
discontinued, the bicarbonate crystals removed, drained, washed with a little water
and calcined in a closed furnace in order to recover the carbonic acid gas evolved
during the calcining, or if the carbonic acid gas so obtained does not cover the
expense of calcining in closed furnaces, the bicarbonate may be calcined in ordinary
calcining furnaces.
From the solution, mother liquor of sodium bicarbonate and sulphate, from which
the bicarbonate has been precipitated, on cooling, a small quantity of phenoloids
separates out and floats on the surface, these may be removed by skimming or
decantation. After the removal of the phenoloids, the mother liquor may be con-
centrated in closed vessels, the distillate containing some phenoloids being used for
slaking the lime required in the process. If the quantity of phenoloids recovered
by concentrating in closed vessels, be not sufficient to cover the extra expense
incurred thereby, the solution may be concentrated in open vessels.
The con-
centrated solution of sodium carbonato and sulphate thus obtained is added to next
batch of sodium carbonate that is about to be converted into bicarbonate.
Or the mother liquor of bicarbonate and sulphate of soda, without concentration
and without removal of phenoloids, may be added to the next batch of sodium
phenolates that is about to be carbonated, thus utilizing the carbonic acid of the
bicarbonate present in the mother liquor, and which would be partly lost in
concentrating. Supposing the decomposition of sodium sulphate into sodium
phenolates, in the first part of process, is not complete, it will be necessary to
crystallize out the excess of sodium sulphate periodically, from these mother
liquors from bicarbonate. The sodium sulphate being used again in the first part
of process.
Where the process is used for the production of potassium carbonate, the process is
as follows:
29.5 cwts. of 90 per cent. potassium sulphate are dissolved in 1400 gallons water at
a temperature of 80 to 90 degrees Centigrade.
There is then run into this solution, gradually and with constant agitation, a
solution of calcium phenolates, made by mixing 350 gallons cold milk of lime, con-
taining about 9 cwts. quicklime, Ca Ŏ, with 350 gallons refined phenoloids, or a
corresponding quantity of crude phenoloids. The solution of calcium phenolates is
to be run in gradually during two or three hours, and after the whole of the calcium
phenolates has been run in, the agitation is continued for another hour or two, or till
the conversion of potassium sulphate into potassium phenolate ceases.
As a result we should have in the decomposer a bulk of about 2100 gallons,
consisting of, when 95 per cent. of the potassium sulphate has been converted
into phenolates, potash, in the shape of phenolates, equal to 20 cwts. potassium
carbonate
1.3 cwts. unchanged potassium sulphate,
19.75 cwts. calcium sulphate, anhydrous, or
24.8 cwts. Ca SO (H, O)..
along with other impurities, K Cl etcetera, originally present in the potassium
sulphate, and
350 gallons phenoloids in the shape of potassium phenolates.
These contents of decomposer after cooling and settling are filtered and washed as
in the production of sodium carbonate. The potassium phenolates solution is car-
bonated, with fuel or lime kiln gases, till a little bicarbonate has been formed. The
contents of the carbonating vessels are now left undisturbed for several hours, when
the liberated phenoloids collect, and float on the surface of the lower solution, which
consists mainly of potassium bicarbonate.
The phenoloids are removed by decantation and again used for the conversion of
potassium sulphate into potassium phenolates.
The potassium carbonate solution, which still contains a small percentage of

page_text: phenoloids, is now evaporated, the first part of the evaporation being carried
out in closed vessels, the distillate containing phenoloids being utilized for
dissolving potassium sulphate, or for mixing with the milk of lime required in
the process.
After this partial evaporation, the potassium carbonate solution is evaporated in
open vessels, and calcined in the usual well known way.
The calcined potassium carbonate is then in the form of commercial potassium
carbonate, and may be sold as such. Or the potassium carbonate solution may be
causticized by means of quick lime, and the resulting solution of potassium hydrato
after concentration may then be used for the manufacture of soft soap, or other
rough potash soaps.
In the above processes it is not necessary that the calcium phenolates solution
shall be first formed and then added as such, to the solution of sodium or
potassium sulphate, though I prefer this. The milk of lime may be added to
the solution of sodium or potassium sulphate, and the phenoloids gradually run in,
with agitation.
Instead of phenoloids, oils containing phenoloid bodies may be used, in this case
it is necessary to use a volume of oil which shall contain the quantity of phenoloids
aforementioned. The contents of the decomposing vessel would also require to be
treated in a different way, the unacted upon oil which would form the upper layer in
the decomposer, being first removed by decantation, by means of taps placed in the
sides of the decomposer at various levels. The remaining mixture of phenolates,
calcium sulphate, and some oil in admixture, would be filtered or treated as previously
described.
The process is applicable to the utilisation of sodium sulphate contained in waste
liquors, as the waste liquors from copper works, or alizarine and other works.
There are no special difficulties as regards plant in carrying out this process.
The plant, however, used for the Schaffner and Helbig process for the recovery
of sulphur from the tank waste of Leblanc alkali makers, will be useful for this
purpose.
Having now particularly described and ascertained the nature of the said invention,
and in what manner the same is to be performed, I declare that it has been well
known before the date of my invention that phenoloid bodies would combine with lime
or with the alkalies, and could afterwards be separated from the solution by means of
strong mineral acids, and I make no claim for this principle broadly, but that what I
claim is
1. The manufacture of a sodium or potassium carbonate, by the action of sodium or
potassium sulphate, upon a solution of calcium salt (or salts) of phenol, or one or more
phenoloid bodies such as described, and the decomposition of the resultant solution by
carbonic acid.
2. The utilisation of sulphate of soda solution, hitherto almost a waste product, for
the purpose of obtaining alkaline carbonates, substantially as described.
Dated this 14th lay of Santambar 1888
WM. P. THOMPSON & Co.,
Of 6, Lord Street, Liverpool,
Patent Agents for the Applicant..