Improvements in the Manufacture and Treatment of Detergent and Bleaching Compounds, and in Apparatus employed therein.
Year: 1896

page_text: Date of Application, 22nd Aug., 1896
Complete Specification Left, 22nd May, 1897-Accepted, 21st Aug, 1897
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture and Treatment of Detergent and
Bleaching Compounds, and in Apparatus employed therein.
We JOIN HARGREAVES of Widnes in the County of Lancaster Chemist and
RICHARD ARMSTRONG of Preston in the County of Lancaster Soap Manufacturer do
hereby declare the nature of this invention to be as follows:-
Our invention relates to improvements in the manufacture and treatment of
detergent and bleaching compounds for domestic, laundry, and general purposes, and
in apparatus employed therein.
In the manufacture of detergent compounds, we suitably treat and employ as a
source of alkali, impure solutions of soda, obtained from black ash lixiviating tanks
of Leblanc process, hereinafter referred to as vat liquor; or we use suitable solutions
of carbonate of soda, obtained by clectrolytic decomposition of chloride of sodium.
When employing vat liquor, we separate insoluble impurities therefrom and wholly
or partially carbonate caustic soda, and decompose sulphide of sodium contained
therein, in any well known manner; or, and preferably, by adding suitable bicarbonate
of soda to said vat liquor, and maintaining the mixture at suitable temperature to
produce desired reactions; or, we cool said vat liquor, obtain crystals of impure
carbonate of soda; after separation from mother liquor, we heat said crystals, and
treat impure solution of carbonate of soda so obtained, as herein before described; or
we neutralize caustic soda therein, by suitable oils or acid fats.
To obtain solutions of carbonate of soda suitable for use in the manufacture of
detergent compounds, by electrolytic decomposition of chloride of sodium, such as
the Hargreaves and Bird electrolytic process in which unsubmerged diaphragms are
employed, steam and carbonic acid gas injected into decomposing cells, and soda
obtained as solution of carbonate of soda; we control working of clectrolytic process
in manner to produce said solutions of soda of desired density containing as small an
amount of undecomposed chloride of sodium as may be practicable. After removal
of insoluble impurities, if any. from solutions of carbonate of soda, herein before
described, we obtain detergent compound by evaporating said solutions until
sufficient "salts" are formed, or we add suitable carbonate or sulphate of soda, in
quantity sufficient, so that when intimately mixed with said solutions shall when
cooled, form a dry detergent compound, containing desired relative proportions of
soda and water of crystallization.
The said detergent compound is rendered saponaceous by incorporating therewith
at suitable stage in the manufacture, suitable oils, fats, their fatty acids, resin or
residual discoloured soap, "Niger" obtained in the manfacture of ordinary soap. The
detergent compounds are pulverized to form detergent powder.
Caustic soda contained in "Niger" may be neutralized with acid fats or corbonated
by admixture of sesgui or bicarbonate of soda, to render said "Niger" suitable for
general use in the manufacture of saponaceous detergent powders.

page_text: Slight bleaching properties are imparted to detergent compounds by suitable
admixture therewith of hypochlorite of soda, which we preferably combine with
commercial essential oil of camphor.
When it is desired to incorporate perfume, ammonia compounds, or hypochlorite
of soda, with detergent powder, we add such materials during, or subsequent to
pulverising detergent compounds, to form detergent powder.
To minimise loss of volatile materials from, or absorption of atmospheric moisture
by detergent compounds or powders, we, varnish or coat paper or other materials
employed to envelope or enclose the said compounds, or powders with solution of
silicate of soda or the like.
Apparatus we employ in manufacture of detergent compounds consists of a trough
like vessel or vessels provided with agitator for mixing, and perforated pipes suitably
arranged for blowing air through and cooling the mass, with arrangements for tilting
the vessel to discharge the finished products.
Dated this 20th day of August 1896.
JOHN HARGREAVES.
RICHARD ARMSTRONG.
Improvements in the Manufacture and Treatment of Detergent and
Bleaching Compounds, and in Apparatus employed therein.
We, JOHN HARGREAVES, of Widnes, in the County of Lancaster, Chemist, and
RICHARD ARMSTRONG, of Preston, in the County of Lancaster, Soap Manufacturer, 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 :-
Our invention relates to the manufacture and treatment of detergent compounds
for domestic, laundry and general purposes, and to apparatus applicable for use
therein; one of the primary objects of our invention being to utilise solutions of
carbonates of soda yielded in the course of their manufacture and obtainable at low
cost, in place of employing carbonate of soda in a solid state. Amongst such
solutions may be mentioned impure solutions of carbonate of soda obtained in the
manufacture of soda by the Leblane process, the comparately pure solutions of
carbonates of soda obtained in the Hargreaves & Bird process for the electrolytic
decomposition of sodium chloride, and the motber liquors obtained in the
manufacture of bicarbonate, sesqui carbonate, and crystals of carbonate of soda.
According to one mode of carrying out our invention, wo einploy as a source of
alkali and suitably treat impure solutions of soda, obtained from the lixivinting tanks
used in the Leblanc process and hereinafter referred to as 'vat liquor.' From the
vat liquor, we separate the insoluble impurities, wholly or partially carbonate the
caustic soda, and decompose the sulphide of sodium contained therein. This may be
accomplished by passing the products of combustion from a lime kiln, or carbonic
acid gas obtained from any other convenient source, through or amongst the vat
liquor. Or, we cool the vat liquor and obtain crystals of impure carbonate of soda;
the mother liquor containing the greater part of the caustic soda originally present
in the vat liquor. The said crystals, on being heated, yield impure solutions of
carbonate of soda, the caustic soda therein contained being carbonated by the
addition of bicarbonate of soda, preferably in large excess; a suitable temperature
being meanwhile maintained in order to produce the desired reactions. Or, we
neutralise caustic soda, and form soap in the impure solution of carbonate of soda

page_text: above referred to, by admixture therewith of suitable oils or acid fats. If the vat
liquor be carbonated before crystallising, the mother liquor yielded is suitable for user
in the manner hereinafter described in connection with the employment of mother
liguor from monohydrated crystals of carbonate of soda ("salts").
Where relatively pure solutions of carbonates of soda are available for the purpose of
our invention, as for instance in the electrolytic decomposition of sodium chloride
(such as by the Hargreaves & Bird electrolytic process, in which unsubmerged
diaphragms are employed, steam and carbonic acid gas are injected into the
electrolytic cell, and soda is obtained as a solution of carbonates of soda), we control
the working of the cells in such a manner as to produce solutions of soda of as high
a density, and containing as small an amount of the undecomposed chloride of sodium,
as may be economically practicable. To facilitate decomposition, the solution of
chloride of sodium is preferably heated before entering the electrolytic cell. Good
results are obtained by so regulating the quantity of steam injected into the
cells that a solution of carbonate of soda of about forty degrees Twdle. is obtained. We
limit the amount of undecomposed chloride of sodium present in the solution of
carbonates of soda, by, from time to time and in the usual manner, farnishing the
cells with fresh diaphragms. When employing diaphragms of medium
quality, we prefer not to renew the diaphragms in the electrolytic cells until the
solutions contains about one per cent. or even more of chloride of sodium. When
the process is worked under normal conditions, a solution containing a mixture of
mono-carbonate and sesqui-carbonate of soda is obtained. When desired, we
increase the relative proportion of the sesqui-carbonate, or form bi-carbonate by
injecting a greater excess of carbonic acid gas into the cells; the solution of
carbonates of soda derived from the cathode compartments being cooled whilst in
contact with said excess of carbonic acid gas.
Solutions of mono-sesqui-, or bi-carbonate of soda obtained in or from the
manufacture of carbonates of soda and sufficiently pure for the purpose of our
invention may be directly employed in the manufacture of detergent compounds; or
the solutions may be concentrated, or they may be evaporated, and monohydrated
crystals of carbonate of soda (salta) obtained. Or, as herein before described,
concentrated solutions of carbonate of soda inay be cooled and crystals of carbonate of
soda obtained; the mother liquor therefrom being employed as a solution of
carbonates of soda as hereinafter described.
In the production of detergent compounds, we incorporate, with the solution of
carbonates of soda obtained as above described, carbonate of soda, preferably
monohydrated carbonate, or soda ash, such as is known under the name of "light"
or "light-roasted aah" obtained by the ammonia-soda process; or sulphate of soda,
free from iron may be added; but in any case in sufficient quantity to form with the
said solutions, when cooled, a dry compound composed of carbonate or carbonates of
soda and water of combination in the desired relative proportions. Sesqui- or
bi-carbonate of soda requires a relatively smaller proportion of water than is
necessary for mono-carbonate of soda.
In practice, we find that a readily soluble detorgent compound is obtained by
incorporating monohydrated carbonate of soda with a concentrated solution of
carbonate of soda, preferably at a temperature of about 80° Fahr. The detergent
compound is rendered saponaceous by incorporating therewith, whilst in a state of
solution or magma of carbonate of soda, suitable oils, fats, their fatty acids, resin or
discoloured soap" niger" (obtained in the manufacture of ordinary soap), or ordinary
soap may be added. "When it is desired to incorporate glycerine with saponaceous
detergent compounds, we employ soap that has not been "curded" or "parted "and
which therefore contains glycerine. When acid fats are incorporated with solution
or magma of mono-carbonate of soda, sesqui- and bi-carbonate of soda are formed,
which are less injurious to the hands or to woollen goods. When employing "niger"
soap, containing free caustic soda, in the manufacture of saponaceous detergent
compounds, we neutralise the said caustic soda with acid fats, or by means of sesqui-
or bi-carbonate of soda.

page_text: 30 parts.
Water
Soap (estimated as fatty acids)
35 parts.
15 parts.
Slight bleaching properties inay be imparted to detergent compounds by the
addition of a sinall percentage, according to the degree of bleaching effect desired,
of hypochlorite of soda in combination with commercial essential oil of camphor.
When hypochlorite of soda, perfume, or ammonia compounds, are incorporated with
saponaceous detergent compounds they are added during or subsequent to the
pulverising of the detergent compounds in the production of detergent powders.
Apparatus adapted for use in the inanufacture of detergent compounds according
to our improved method is illustrated diagrammatically in the accompanying
drawings. Figs. 1 and 2 represent respectively a side elevation and an end view of
a construction comprising a mixer (similar in form to the well-known horizontal
dough-mixtures) provided with means for admitting air to the mass or compound and
a cooling vessel. Fig. 3 is an elevation and Fig. 4 a transverse section of another
construction wherein a 'plauetary' type of mixer is employed. Fig. 5 is a vertical
section and Fig. 6 a corresponding plan of a vessel wherein the materials are jointly
agitated, mixed and cooled by injecting air therein.
Referring to the example shown in Figs. 1 and 2, the apparatus may comprise a
trough-like vessel A, fitted with an agitator B for mixing the compound; the mass
being partially cooled by blowing air through the perforated shaft b of the stirrer. The
vessel may bo tilted (as shown in dotted lines in Fig. 2) for the purpose of discharging
the finished products. In practice, however, we find it expedient to employ two
vessels, a mixing vessel and a cooling vessel. Referring to the example shown in
Figs. 3 and 4, the mixing vessel A', wherein are incorporated the materials under
treatment, is arranged vertically, the agitators or beaters having a planetary motion
within such vessel. Upon a vertical spindle C is keyed a toothed-wheel c, which
meshes with toot bed-wheels d d carried in bosses at the extremities of the rotating
arms DD; the wheels caud d d being provided with agitators or beaters c¹ and d³, di
respectively. The arms D¹ D¹ are furnished with ecmpers. Motion is imparted to
the vertical spindle C by means of bevel gearing E. An opening F is provided at or
near the bottom of the mixing vessel for enabling the finished materials to be with-
drawn. The opening may be closed by means of a door f provided with a fastening,
such as . According to the arrangement illustrated in Figs. 5 and 6, air is
employed for jointly agitating, mixing and partially cooling the materials under
treatment in the vessel Ax; the air for the purpose being forced into tho pipe Cx and
emerging through the perforations bx in the branch pipes Bx. f is a door for closing
the discharge opening F; f being the fastening. The warm or partially cooled
detergent compound magma upon being discharged from the mixing vessel passes
along a shoot G into the cooling vessel, which consists of a long covered trough or
trough-like vessel H provided with an Archimedian or like feed-screw I, the latter
serving to agitate and propel the saponaceous detergent compounds. Air is caused to
enter the trough-like vessel nt K; same traversing the vessel in n direction opposite
to that pursued by the saponaceous detergent compounds. The cooled pulverulent
saponaceous detergent compounds are pulverised in an suitable manner to form
saponaceous detergent powders.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed, we claim :-
1. In the manufacture of saponaceous detergent compounds, the employment,
substantially as herein described, of solutions of a carbonate of soda directly yielded

page_text: in the Leblanc, electrolytic or other process for the manufacture or treatment of
carbonato of soda.
2. In the manufacture of saponaceous detergent compounds, incorporating
monohydrated carbonate of soda, soda ash or sulphate of soda, and soap, or soap
forming materials, with solution of a carbonate of soda yielded in or directly resulting
from the process of manufacturing carbonates of soda.
3. In the manufacture of sapouaccous detergent compounds, evaporating a solution
of carbonate of soda, obtaining crystals of monohydrated carbonate of soda, mixing
the latter with the mother liquor yielded in the process of crystallisation, adding
saponaceous material and then cooling the compound.
4. In the manufacture of saponaceous detergent compounds, the employment of
acid fats, in conjunction with a solution of carbonate of soda directly yielded in the
manufacture or treatment of carbonate of soda, substantially as and for the purpose
herein described.
5. In the manufacture of saponaceous detergent compounds, the employment of
'niger' soap, substantially as and for the purpose herein described.
6. In the manufacture of a detergent and bleaching compound, incorporating
hypochlorite of soda combined with commercial essential oil of camphor with
detergent compounds, substantially as and for the purpose set forth.
7. In the manufacture of saponaceous detergent compounds, the improved means
for mixing and cooling the inaterials, constructed or operating substantially as herein
described.
8. In the manufacture of saponaceous detergent compounds, the improved method
of cooling and agitating the compound by forcing atmospheric air through the saine.
9. The herein described means applicable for use in the manufacture of sapouaceons
detergent compounds and operating substantially as set forth.
10. In the manufacture of detergent compounds, the employment of a mixing
device in conjunction with a cooling vessel, such as H, provided with an agitating and
propelling device, such as I, and with means for supplying air to the said vessel,
substantially as and for the purposes set forth.
Dated this 21st day of May 1897.
For the Applicants,
G. G. M. HARDINGHAM,
191, Fleet Street, London, EC., Chartered Patent Agent.