Washing Powders.
Year: 1887

page_text: Date of Application, 17th Nov., 1887
Complete Left, 6th June, 1888
Complete Accepted, 6th July, 1888
and to Washing Powders.
I, CHARLES WILLIAMS, of 1, Leadenhall Street, in the city of London and county of
Middlesex, Civil and Chemical Engineer, do hereby declare the nature of this
invention to be as follows:-
:-
To a nearly boiling solution of caustic Soda having from 1.10 to 1.15 specific gravity,
I add calcium phosphate which has been previously reduced to a fine powder and calcined
in a reverberating furnace. In the case of mineral phosphates I add, during the last
stage of the calcining process, ground sodium sulphate and sodium bi-sulphate in
quantities depending on the quantity of lime and iron which are contained in the
mineral phosphate.
Instead of the mineral or other tertiary calcium phosphate thus treated, acid calcium
phosphate in a dry or moist state may be added to the soda solution.
The calcium phosphate must be mixed with the soda solution in such quantity, that
there are from 3 to 4 equivalents (in exceptional cases even more) of caustic soda
for every equivalent of phosphoric acid. In using acid calcium phosphate, the two
first equivalents of soda of the hot alkali-solution may be replaced by sodium
carbonate or by the soda of caustic lyes from other sources.
While gradually adding the phosphate to the lye, the latter is agitated by means of
a steam-injector or by a mechanical appliance, the mixture is heated to the boiling
point as rapidly as possible (preferably by means of steam) and kept at this heat until
all particles of mineral matter have been dissolved. If mineral phosphates are used
which contain a low per centage of phosphoric acid, it is necessary to add water.
Having dissolved the mineral matter in about 30 to 40 minutes, I add sufficient
oleic acid to neutralize the excess of free soda and as soon as a test with silver nitrate
discloses the absence of free caustic soda, I filter the mass through filter presses,
preferably by means of high pressure steam, the washing of the residue being effected
with supersaturated steam.
Or in lieu of this process, I may filter in the ordinary manner by means of a
compression pump or compressed air, and wash the residue with water. The water
which has been used for washing may then be employed for the following
ananations

page_text: My purifying compounds may also be obtained by the following process. To a
boiling solution of phosphoric acid of 20° B. I add sodium-carbonate (preferably
Solvay-soda) in such quantity that there are from two to three equivalents of soda (or
in some cases 4 equivalents of soda) for every equivalent of phosphoric acid. In other
cases I first add only from 1 to 2 equivalents of soda in the shape of sodium-carbonate,
and afterwards caustic soda in saturated solution in such quantity as to have
1, 2, or 3 equivalents of sodium hydrate, or lastly I may add a saturated solution of
caustic soda, in such quantity as to have at least 4 equivalents of sodium hydrate to
one equivalent of phosphoric acid in this process a portion of the soda may be
replaced by potash.
The phosphoric acid solutions are again boiled and stirred during the gradual
introduction of alkalis. For boiling I use pans of iron or of copper.
After boiling
from 10 to 30 minutes, I add oleic acid until all free alkali has been neutralised, after
which I resort again to filtration in the manner stated above.
The solution thus obtained by means of calcium phosphate or by means of phosphoric
acid may be employed for many purposes either direct or in a diluted state. It may
also be concentrated and caused to deposit crystals in the usual manner.
As a rule,
however, I boil it down to about 35 to 38 degrees B. (1.320 to 1.350 specific gravity)
in pans provided with steam or hot air jackets and as soon as a drop of the liquid
will rapidly, harden on a glass plate, I. place the liquid in pans around which cold
water is flowing, and stir constantly, either by hand or by a mechanical stirrer. As
soon as the mass assumes the shape of a powder, but is still warm, I add finely divided
sodium aluminate while carefully stirring. The quantity of the latter which should
be previously heated, may be from 1 to 50 per cent. of the weight of the phospho-
oleic-alkali product, according to the purpose for which the finished product is to be
used.
After having mixed for about 10 to 15 minutes, I place the mass in a circular
steam-heated pan containing a roller which rolls slowly over the mass in a circular
path, (as in an edge-runner) so that there results a finely divided non-granular product,
while at the same time all adhering moisture is evaporated.
During the grinding process I add to the mass from 3 to 5 per cent., of its weight
of sodium silicate solution of 100 degrees B., saturated with peroxide of hydrogen.
After careful mixing, grinding and drying, I spread the finished product (which I
call Phospho-Oleo-Purifier) over a stone-floor, and finally pack it for transport.
The product thus obtained, which may vary as regards the proportions of its
components, according to the purpose it is intended to serve, may be dissolved in
water, and the solutions used for cleansing wool, either in the fleece, or as crude
wool or woollen fabrics or shoddy, before or during the manufacture as well as for
cleansing silk fibre or vegetable fibre or fabrics, either before or during the manufacture.
By conveniently choosing the proportion of its constituents or adding other chemicals
the product may also be rendered applicable as a washing powder for ordinary household
purposes.
The product intended for cleaning the crude woollen fleece contains, with a smaller
per centage of sodium aluminate, the individual constituents in such quantities that
after the product has been used, the said constituents may be wholly or partly
recovered, and the valuable substances contained in the yolk of the wool may also
be obtained.
In some cases I mix the above products, either in the half finished or in the finished
condition, with finely powdered sodium carbonate or pearl-ash, or I add to the products
crystallized or anhydrous double or triple sodium phosphate or both, or lastly mix the
products with a finely divided caustic lime eventually with the addition of calcium
carbonate.
Dated this 14th day of November 1907
FAIRFAX & WETTER,
433, Strand, London,
Agents for the Applicant,

page_text: COMPLETE SPECIFICATION:
Improvements relating to Purifying Compounds for Textile Materials
and to Washing Powders.
I CHARLES WILLIAMS, of 1 Leadenhall Street, in the City of London, Civil &
Chemical Engineer 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 :-
I heat a solution of caustic soda, having a specific gravity of from 1.10 to 1.15,
in a suitable vessel, and when the boiling point is reached, I gradually add calcium
or other mineral phosphate, which has previously been finely pulverised and roasted
or calcined in a reverberatory, or other suitable furnace, with sulphate or bi-sulphate
of soda and carbon, in a manner well understood, and in proportions suitable to the
component parts of the material used.
In lieu of the calcium, or other mineral phosphate, treated as described, an acid
calcium, or other acid phosphate, either in a dry or wet state, may be added to
the soda solution. The quantity of calcium or other mineral phosphate (as above
treated) or acid calcium or other acid phosphate, to be added to the soda or alkali
solution, is to be so proportioned, that for each equivalent of phosphoric acid in the
phosphate, there shall be from 3 to 4 (and in exceptional cases even more)
equivalents of real soda present in the solution. When using an acid calcium, or
other acid phosphate, two of the equivalents of soda in the heated alkali solution
may be obtained from sodium carbonate. During the gradual addition of the
phosphate, ground and furnaced as stated, to the solution, I mix the mass intimately
by mechanical means, or preferably by means of a steam injector and bring the
mass as quickly as possible to the boiling point (preferably by means of steam) and
continue boiling until all particles are dissolved and thoroughly assimilated and
mixed in the mass. When using mineral phosphates of lime of low percentage in
phosphoric acid, an additional quantity of water is necessary. When the mineral
or inorganic matters are dissolved, as above described, which will occupy a period
of from 30 to 40 minutes, I add sufficient oleic acid, or other oil or fat, such as is
usually employed in soap making, or a portion of either of these may be substituted by
rosin, to combine with and neutralise the excess of free soda, and when a rough test by
means of a neutral solution of silver nitrate, proves that no free alkali is present, I
filter the mass through filter-presses, preferably by means of high pressure steam, and/
wash the residue with saturated steam.
In place of the above order of procedure, I may if preferred, filter the caustic
soda solution after the addition thereto of the phosphates and boiling for 30 or 40
minutes, and then add oleic acid, or oil or fat, and boil until the silver nitrate test
proves the absence of free alkali, and then filter again if necessary. If the use of
high pressure and saturated steam is not available, I may filter in the usual way.
through filter presses by the ordinary compression pump, or compressed air from an

page_text: accumulator, or employ any other suitable means of filtration and wash the residue with
water and utilise the wash water for succeeding operations in a manner well understood.
As an alternative method I may proceed as follows; to a heated solution of phosphoric
acid of about 1152 specific gravity, when at boiling point, I add sodium carbonate
previously dissolved in water and in such proportions that there should be present from
two to three equivalents of real soda for each equivalent of phosphoric acid in the solution
In some instances I may add an amount of sodium carbonate equal to four equivalents
of real soda, or even more in special cases, in other instances I add such quantities of
sodium carbonate as are only equal to from 1 to 2 equivalents of real soda, and then add
caustic soda in saturated solution, or other suitably prepared alkaline lye sufficient for 1,
2 or 3 additional equivalents of real soda, or I may add instead of the above a saturated
solution of caustic soda, or other suitably prepared alkaline lye containing a quantity
of real soda equal to 4 equivalents for one equivalent of phosphoric acid present. In
special cases I even exceed this limit, or I substitute one or more equivalents of potash
for soda, or I may reverse the procedure and add the phosphoric acid solution to the
alkali solution. The solutions so obtained are kept boiling in iron or copper pans during
the gradual addition of the alkalis, or vice versa, preferably by means of steam and are
agitated preferably by a steam injector. After an interval of boiling varying from
10 to 30 minutes, I add sufficient oleic acid, or oil or fat, to neutralise all free alkali
present, and when the neutral silver nitrate test shows that this is effected, I filter the
liquor as in the foregoing case.
As a further alternative mode of proceeding, I may incorporate, in the same manner
as above explained, phosphate of soda or potash with soda or potash and oleic acid, so
as to obtain the same product as obtained by the foregoing processes.
The liquors obtained by any of the said processes may be used for certain purposes
as they are, or in a diluted form, or I concentrate them by boiling down in iron or
copper pans, or in some instances crystallise them out, in the usual and well known
manner, but I prefer to boil them down in steam-jacketted, or hot air pans, to about
say 1-320 to 1.350 specific gravity. When the liquor has reached such consistency
that a small quantity dropped on a glass plate rapidly solidifies when cooling, I
immediately run the mixture which is a chemically constituted Phospho-oleo-Alkali,
into shallow pans, cooled by a cold water circulation around them, these pans are
provided with stirring apparatus in order to agitate the mass and so cool it more
rapidly. As soon as the mass takes the pulverulent form and while yet warm, I add,
and intimately mix therewith, aluminate of soda (by preference that obtained from
cryolite). This aluminate should be in a finely divided state, and partially heated at
the time of mixing, and the proportion may range from one per cent. of aluminate of
soda in the final product to equal parts of the aluminate and the said Phospho-oleo-
Alkali. Even more aluminate may be used in special cases, the proportions being
determined by the varying requirements to which the final products are destined.
After mixing the aluminate with the mass for from 10 to 15 minutes, I run the mixture
by gravitation or otherwise on to a steam heated circular pan, provided with rollers
having a combined sliding and revolving motion and travelling around and over the
pan after the manner of ordinary edge runners. By this means I obtain a finely divided
and evenly grained powder free from water of crystallization, or adherent moisture.
During the grinding process and when partially cooled down, I add to the mass from
3 to 5 per cent. of its weight of 100° solution of silicate of soda, saturated with hydrogen
peroxide and then spread the product, which 1 call "Phospho-oleo-Detergent," on a
stone floor to get completely cold. It may be packed for conveyance in any suitable
way, either in the shape of a dry powder, or be converted into blocks by adhesive
mixture and compression, or other suitable means.
I wish it to be understood that I do not necessarily confine myself to the particular
proportions of the various materials employed in carrying out my invention as herein-
before stated, as such proportions may from time to time be varied to meet the different
requirements of the finished product. And again, potassa or potash alkalis, may be
used in part or whole substitution for the soda in the sodium carbonate, caustic soda, or

page_text: soda solution described. In like manner instead of calcium, or other mineral lime
phosphate, or its derivates, I may use bone-marl, alumina, or other suitable phosphate,
or their acid preparations, or substitute manufactured di-phosphates or precipitated
phosphates, in the manner or for the purposes above described. I use either the
finished product, or the product as obtained at the first stage, dissolved in water for
cleaning fleeces, raw wool, woollen goods or shoddy, silk and vegetable fibres, or
fabrics, either previous to or during the process of manufacture; or I arrange the
proportions of the constituent parts of the product, so that it may be suitable with or
without the addition of other ingredients for ordinary use as a washing powder. For
fleece cleaning, the special object is to so proportion the constituent parts of the
product, as to afford a much larger proportion of available alkali than obtainable
otherwise in preparations of an analogous nature, as well as to provide against the
possibility of excess of uncombined alkali in the solutions by means of soluble alumina,
and further more to allow the solutions to be used with the greatest advantage in the
recovery of potash and wool fat from the yolk, the medium used, to be itself recoverable,
wholly or in part.
For some purposes, other than those of wool or fibre cleaning, I mix the product
either in the wholly or partly finished state with carbonate of soda or pearlash, or
may add to either of the products sodium-di or tri-phosphate, either in the crystallized
or anhydrous state, or I may add both at the same time.
Having now particularly described and ascertained the nature of this invention
and in what manner the same is to be performed, I declare that what I claim is :-
1. The preparation of the "Phospho-oleo-Alkali" product, either from phosphates
of lime or alumina, acid phosphates of lime, or alumina, or phosphoric acid, or
phosphate of soda, or potash, in the manner and for the purposes substantially as herein
set forth.
2. The mixing with the "Phospho-oleo-Alkali " product aforesaid, of aluminates of
soda in varying quantities and proportions, in the manner and for the purposes
substantially as herein set forth.
3. The combination of proxide of hydrogen, with silicate of soda in solution and
its incorporation with the aforesaid detergent products in the manner substantially as
herein set forth.