Note: Descriptions are shown in the official language in which they were submitted.
C6184 '
__ ~ ~~.4~8f 9
g~~'rR~°'~1T COMPOSITION AND FROCESS FOR ITS PRODUCTION
TAchn~cal Field of the Invention
This invention relates generally to a process for the
production of detergent powder by spray-d=ying.
3ackeroLnd
Traditional mixed active builder containing slurries utilize
water as the carrier system for both the active te.g.
surfactant) and solids (e. g. builders such as zeolite,
carbonate, and the like). This usually results in high
slurry moisture content (i.e. 40-50~).
Liquid active blends on the other hand allow for water and
active together to act as a carrier for the solids. The
active has changed =is function in the slurry. The active
instead of being a "solid additive" which must be suspended
in the liquid water carrier has itself become part of the
liquid carrier system. This change allows for a reduction in
the amount of water needed in the slurry as a carrier,
because the active substitutes for part of the water.
In the spray-drying process there are frequently opposing
factors; for example, more water present in a slurry,
requires more evaporation, with a resultant increase in
costs. If less water is used to save costs, the slurry
becomes correspondingly more viscous until a point is reached
at which it cannot be pumped and metered. An additional
factor, due to market considerations is that the finished
product requires higher quantities of surfactant. Spray-
drying, for example, increased quantities and certain types
of nonionic surfactant lead to pluming from the spray tower.
High temperatures contribute to this pluming. Generally
a
AMENDED SHEET
C6181
~.. ~ ~~14~8~9
- 2 -
other things being equal, spray-drying of a slurry having a
lower water content leads to less heat input in the tower
than higher water content. It is thus desirable to be able
S to spray-dry low water content slurries while minimizing
the problem of high slurry viscosity. A further advantage
is that high density powders may be thus obtained.
U.S Patent 4,738,793 employs low moisture slurr=~es for
spray-drying but this is accomplished using nonionic
surfactants in the substantial absence of anionic
surfactant (less than 2% anionic is taught)..
The current art describes the use of high shear mechanical
devices to achieve high powder density (>600 g/L) with
zeolite layering to control particle size distribution of
the final product U.S. 4,869,843. Also described in use of
nonionic surfactant sprayed onto base powder with addition
of secondary materials to achieve high powder density (>450
g/L). U.S. 5,030,379 to Knight et al. Specific
preparative methods for low water content compositions are
disclosed in U.S. 5,075,041.
EP-A-0270240 describes a spray dried zero-phosphate
detergent powder and discloses a zeolite built powder of
very high bulk density formed by spray drying a slurry
-having a defined water content, low or zero levels of
electrolyte and.polymeric polycarboxate present. Nonionic
detergent is optionally present in the slurry in a range of
1 to lOwt~. EP-A-0228011 describes a process for preparing
a phosphate-reduced detergent composition containing inter
alia an anionic surfactant and optionally a nonionic
detergent. The nonionic is primarily introduced into the
detergent powder by spraying on to particles already formed
by a spray drying process. The resulting powder is admixed
with another spray dried detergent powder which can contain
_ _ _ ____~.~- . mr~nED SHEET
C6181 '
._ ~1438~~
- 2a -
up to 5wto nonionic in such small amounts that pluming and
anyviscosity problems are said not to be present. Moreover
the slurry from which the second potentially ~onionic-
containing powder is spray dried may contain a polymeric
carboxylic acid.
The method employed by the art for lowering slurry moisture
and avoiding pluming from high temperatures or high
nonionic concentrations have not beer. completely
satisfactory.
~efinitior. of the Inventior_
A method of slurry preparation and a slurry composition
which exhibits exceptionally low viscosity even at low
water content, thus enabling it to be spray-dried to a high
surfactant concentration without unacceptable pluming has
now been discovered. In addition, it has been found that a
spray-dried powder of exceptionally high density can be
obtained.
AMENDED SHEET
w
C61~34
,~,_ - ' . - z1 438 69
J
Simple mixtures of water and nonionic surfactant, typically
result in a very viscous gel. Gel formation may be avoided
in producing a liquid active mixture by using a preferred
order of addition: water plus caustic, then nonionic plus the
acidic form of the anionic surfactant. Water plus caustic
changes the characteristic viscosity curve so that when the
nonionic is added an emulsion is formed in place of a gel.
emulsion viscosity, of ccurse, ~s much less than gel
viscosity. The acid prec~.:rsor of the anionic may then be
added and is preferably eutralized in situ. This makes the
liquid active mixture Tore :~~scous, but still avoids the gel
state. Once this is done, solids addition of the builder,
_.e. zeolite and/or carbonate as well as other builders such
as NTA and the like may be carried out.
in U.S. Patent No. 4, 923, 630' Blackburn and U.S. Patent No.
a, 826, 632 Blackburn, there are disclosed liquid surfactant
compositions that can be sprayed onto spray-dried powders to
increase the bulk density thereof. while these ~densified~
spray dried powders have not been produced by mechanical
densification, the disadvantages of using a spray dried
powder as a starting point remain.
A blend of surfactants may be used such as that disclosed in
Hsu et al. U.S. Patent No. 5,219,495. In the blend, in
addition to a neutralized or partially neutralized anionic
surfactant, nonionic surfactants are included.
low moisture content detergent slurry is manufactured
utilizing liquid active surfactant blends containing anionic
and nonionic surfactants. This low moisture slurry is then
spray-dried using standard spray-drying techniques yielding,
if desired, a concentrated or high density base powder.
Accordingly, the invention provides a process for preparing
;~~'
21 438 fig
C6184
_ 4 _
by spray-drying, washing powders containing anionic active,
nonionic active and builder, i.e., carbonate and zeolite,
for example, crystalline and/or amorphous aluminosilicate
including the zeolites disclosed in EP 384,070A and EP
448,297A. The builders are used in a proportion of at least
about 5 to 50% of anionic to 1 to 50% of nonionic to 5 to 70
% of a builder.
The slurry is prepared by forming an aqueous mixture of a
nonionic and anionic surfactant to which a builder is and
other detergent components may be added to produce the
slurry for spray-drying. The aqueous anionic-nonionic
mixture comprises water, a nonionic surfactant and an
anionic surfactant wherein the anionic is incorporated as
the acid form of an anionic surfactant and the mixture
further contains a neutralising agent whereby the acid is
neutralised in situ to form the anionic surfactant.
In a preferred embodiment, the present invention provides a
process for preparing, by spxay drying, washing powders
comprising 5 to 50% alkylbenzene sulphonate as anionic
surfactant, 1 to 50% nonionic surfactant and 5 to 70% of a
builder selected from the group consisting of zeolite,
sodium carbonate, sodium citrate and mixtures thereof,
wherein the process comprises the steps of:
A, preparing under agitation a mixture of water and at
least sufficient alkali metal hydroxide to result in
neutralisation of the acidic foam of the anionic
surfactant;
21 X38 69
06184
_ 5 _
B. adding under agitation to the mixture, sufficient
nonionic active to prepare said powder, thus resulting
in a nonionic surfactant mixture:
C. adding under agitation to the nonionic surfactant
mixture a sufficient amount of the acidic form of the
anionic active to result in said powder, thus forming
an
anionic-nonionic surfactant mixture;
D, adding under sufficient agitation to the anionic-
nonionic surfactant mixture sufficient builder, and
optionally other detergent adjuvants to result in said
final powder, to form a final slurry mixture having a
maximum water Content of 35%;
E. adjusting, if necessazy, the temperature of the final
slurzy mixture to 57.2 to 90.5/0 t135/F to 195/F) and
spray-drying the final slurry mixture
i
...
21 438 69
cs~a4
_s_
characterised in that a viscosity adjuster is added, in an
amount up to 50% of the mixture, at any time during the
slurry process to result in a viscosity of the final slurry
mixture of 1000 x 10-' to 20,000 x 10-' Pa.s (1000 to 20,000
cps) measured at a shear rate of 17 to 18 sec 1 and a
temperature of 65.5 to 90.S/C (150/ to 195/F).
Suitably, the viscosity adjuster is added in step A or
between steps D and E.
CA 02143869 1999-12-O1
Preferably the water content will be from 10$ to 35% by
weight of the slurry, in which case it will be possible to
spray-dry the powder to a bulk density above 500 g/liter,
desirably from 500 to 900 g/liter. Generally, it will be
preferred to reduce the water content to the minimum
practical level, although the percentage at which this
minimum occurs will vary with the content of the other
components of the formulation as explained in mope detail
below.
Viscosity is extremely important since for ease of operation any
composition, e.g. a slurry, must be capable of being sprayed at pressures
commonly used such as 68947.5 Pa.s (10 psi) to 6894757 Pa.s (1000 psi)
through nozzle sizes of about 0.1 mm to 11 mm or more at temperatures
of about room temperature of about 18.3°C (65°F) up to about
93.3°C
(200°F). Such low temperatures avoid excess evaporation. Typically, the
viscosity of such composition is about 1000x10-3 Pa.s (1000 centipoise) to
20,000x10-3 Pa.s (20,000 centipoise) at a temperature of 65.5°C
(150°F) to
85°C (185°F) or even somewhat higher at a shear rate of 17 to 18
seen.
Compositions having a ratio of anionic surfactant to nonionic
surfactant of 1:3 to 3:1 may be employed but 1:2 to 2:1 are
of especial interest.
Preferably, the composition of a slurry should be formulated so that the
viscosity of the final slurry is about 7000x10-3 Pa.s (7,000 centipoise) to
20,000x10-3 Pa.s (20,000 centipoise), preferably less than 20,000x10-3 Pa.s
(20,000 centipoise), more preferably less than 10,000x10-3 Pa.s (10,000
centipoise), measured at a shear rate of 17 to 18 secs-1 at a temperature of
65.5°C (150°) to 85°C (185°F). The slurry must be
sufficiently fluid to allow
thorough mixing of all of the components in the mixer. After mixing is
finished, the slurry must remain sufficiently fluid to-------------------------
-----
C6184
w ~~~8~9
pump it out of a mixing vessel to a spray tower. As better
and more efficient mixers become available processing of more
viscous systems becomes easier. Conversely, as pumps are
improved, higher viscosity slurried can be pumped. The
S viscosity must be such that the desired physical mixing and
pumping can be done economically and chemical reactions if
any, such as neutralization take place readily. The final
pcint prior to spray-drying is the actual atomization of the
slurry in the tower spray nozzles. There are many different
designs of spray nozzles well known to those skilled in the
art with which to achieve appropriate atomization.
Lia_uid mixing can be defined as a Reynolds number (NR~) where
N~~ is defined as foil ows
ND2P ~
where N~~ is Reynolds Number, N is impeller speed, D is
impeller diameter, p is specific gravity and a is viscosity
at a shear .ate of Nn sec-l.
~0
.n order to provide appropriate impeller mixing, the final
slurry '_:~ the mixer should have a flow with a Reynolds Number
or about 1 to 10,000 which is conveniently produced by an
appropriate impeller design.
vr_S~pSTTY ADJUSTERS
The viscosity of the slurry thus depends upon many functional
parameters. The viscosity to be achieved rt~ust be appropriate
for the slurry to be mixed, pumped and atomized in a spray
tower. The viscositll thus may vary within fairly wide
ranges.
AMENDED cNFFT
CA 02143869 1999-12-O1
C618~ . . ,.
The viscosity of the slurry can be adjusted by the addition of an organic or
inorganic additive in a sufficient amount to result in a viscosity in the
final slurry of about 1000x106 Pa.s (1000) to 20,000x106 Pa.s (20,000 cps) at
a
centipoise) at a shear rate of 17 to 18 sec-1 and a temperature of
65.5°C
(150°) to 85°C (185°F). Examples of viscosity adjusters
are nonionic
surfactants, hydrotropes (e.g., sodium xylene sulfonate), polyethylene
glycol, polypropylene glycol and
inorganic salts fe.g., t.la,SO,). This viscosity adjuster may
be introduced into the water at the beginning or optionally
during the process or may even be added after the anionic
precursor but it is preferably added prior to most of the
zeolite or other builder solids to insure proper fluidity.
Tre viscosity adjuster may also be put into any of the
additives as a mixture and added in this way.
The amount of viscosity adjuster employed is sufficient to
insure slurry fluidity and varied from about 0.5% of the
slurry weight to about 30% of the slurry weight. It also
must be realised that when an anionic sulfated or sulfonated
precursor is prepared, a certain amount of free or acidic
sulfate will be formed. Due to these impurities in the
precursor, some sulfate salt will be present. In normal
commercial products, this is usually insufficient to fully
fluidize the slurry. Of course, if excess sulfuric or other
acid were added intentionally to the precursor, or if the
sulfonation or sulfation reaction forming the precursor were
terminated prematurely sufficient sulfate or~other anion
could be introduced with the precursor and the salt formed in
situ to fluidize the slurry without adding excess viscosity
adjuster.
Temperature during the processing should be carefully
controlled. Temperatures of 93.3°C (200°F) or more have
destabilized
the slurry and degraded the components.
3~
AMENDED SHEET
CA 02143869 1999-12-O1 ;
C6184 , . ,- _ ..
- 10 -
It is essential to the successful application of the process
of the invention that the slurry should contain a nonionic
surfactant. Preferably the nonionic surfactant will be an
ethoxylated or ethoxylated propoxylated primary or secondary
linear or branched chain alcohol having a carbon chain length
in the hydrophobic portion of from 5 to 25, and containing
from about 5 to about 35 moles of ethylene/oxide and/or
propylene oxide per mole of alcohol. Examples of such
materials are ethoxylates she Dobanol and Neodol (Registered
Trade Mark) alcohols, sold by Shell Chemicals and the
Tergitol (Registered Trade Mark) ethoxylated alcohols sold by
Union Carbide Corporation. However, other types of nonionic
surfactants can also be used, alkyl phenol ethoxylates for
example, inc?~iding in particular the reaction products of
alkylene osices, usually ethylene oxide, with alkyl (C6-C~~)
phenols, generally 5-25 EO, i.e. 5-25 units of ethylene oxide
per molecule; and products made by condensation of ethylene
oxide with the reaction products of propylene oxide and
ethylene diamine. Other so-galled nonionic surfact-actives
that may be used include alkyl polyglycosides, long chain
tertiary amine oxides, long chain tertiary phosphine oxides
and dialkyl sulphoxides.
The amount of nonionic in the final powder will be about 1 to 50%,
preferably 5 to 50%, more preferably 10 to 30%.
ANIONIC
Anionic surfactants which may be formed from precursors
(e. g., sulfonic acids) are also essential.
Typical anionic surfactants include sodium alkylbenzene
sulphonates, sodium alkyl sulphates, sodium alkane
.~
AM~NDED SHEET
C6184 ' _ _
~~- ~ ~~ 21 438 fig
_" -
sulphonates and sodium alkyl ether sulphates. More
particularly, C9-C:, primary and secondary alkyl or alcohol
sulfates Cg-CZ, secondary alkane sulfonates, CB-C2, olefin
sulfonates, Cto-C,2 soaps and the like may be employed,
preferably, sodium or potassium alkylbenzene sulfonates or
alkyl sulfates are employed. Particularly suitable
alkylbenzene sulfonates are sodium C;1-Cls alkylbenzene
sulfonates. Suitable alkyl sulfates are C11-Cls alkyl
sulfates, although other alkyl sulfates and sulfonates
outside this carbon chain length range, may also be used.
The acid form of the precursor is neutralized in the mixture
with sodium, potassium or ammonium hydroxide.
The amount of anionic in the final powder will be about 5 to
50~, preferably about .0 to 40~.
BLENDS
In addition to the use of individual actives as discussed
above, prepared liquid active blends of nonionic and anionic
surfactants may be used. These blends and methods for their
preparation and use are disclosed in U.S. Patents 4,637,891;
x,826,632; 4,923,636; 5,045,238; 5,075,041 as well as EP
88,612A and 0,265,203; French patent 2,645,876 and GB Patent
1,169594. These blends may be employed with the instant
invention, particularly those disclosed in U.S. patents
4,826,632, 4,923,636 and 5,219,495.
The method of preparation of the blend is important. Simple
admixture of normally 50% aqueous neutralized alkylbenzene
sulphonate paste and liquid nonionic surfactant in the
desired proportions will give not a mobile isotropic liquid
but a highly viscous gel which is difficult to handle.
1
C6184
12 - 214~~~~
Liquid nonionic surfactant may be gradually added to an
alkyibenzene sulphonate paste (neutral salt) which will
typically have an active matter content of about S0~ by
weight. The resulting viscous material, containing more than
loo water, is then heated to a sufficiently high temperature
_for a sufficient period of time for the water content to fall
below 10% by evaporatio.~.. ~ clear mobile liquid is obtained
and this remains clear and mobile when allowed to cool to
ambient temperature.
i0
ccording to a second ~et'_~.od, alkylbenzene sulphonic acid may
be mixed ~,aith nonionic surfactant, and the mixture treated
with concentrated aaueous scdiu~-n hydroxide or potassium
hydroxide to effect partial or complete neutralization.
if :fixtures fluid at 20° to 80°C and containing about 6 to 7o
by
weight of water maybe produced by this method.
~ccordira to a variar_t of the second method, the alkylbenzene
sulphonic _acid starting material may be in partially
20 neutralized form.
~n a third method, a range of compositions containing anionic
surfactant, nonionic surfactant end water in relatively high
amounts up to about 35$ may be prepared containing sodium or
?5 potassium hydroxide i~ excess of that necessary to neutralize
~.'.he anionic sulfonic acid if a precursor is used. These
compositions are sufficiently mobile at temperatures no
higher than about 90°C. The blends employed are liquid
surfactant compositions mobile at a temperature within the
3p range of about 15° to °0°C or if the anionic to
nonionic
ratio is appropriate and the type of nonionic is appropriate
even down to about S°C. This composition contains
preferably;
r
AMEIaDED SHEEP
C6184 '
,3 _ ~~.438~9
;a) a sodium or potassium salt of an alkylbenzene sulfonate
or alkyl sulfate in an amount not exceeding 80% by weight and
preferably S to 80% or aven 20% to 60o by weight,
(b) an ethoxylated nonionic surfactant in an amount not
exceeding 80$ by weig:~t, preferably S to 80o and most
preferably 20% to 60% by weight,
(c) sodium or potassium hydroxide in an amount of about 2~
to 15~ by weight, depend=ng on the ratio of anionic to
nonionic. nor very high anionic to nonionic ratios of 2:1 up
to 4:1 a greater excess of caustic is preferred whereas for
lower ratios of 0.125:1 smaller excess amounts such as 2~ are
sufficient, and
(d) water in an amount of 0~-35~ by weight preferably 5~ to
20% by weight most pre=erably about 10% up to about 20% by
weight.
Higher water contents, that is, contents greater than about
10~, when included in a composition of anionic and nonionic
surfactants typically result in gel formation even with low
ratios of anionic to nonionic such as 0.125:1. The addition
of concentrated aqueous hydroxide solution (50 w/w~) prevents
gel formation and reduces the viscosity of the composition
even though water =s added to 'the composition by the
introduction of the aqueous hydroxide solution. The ability
to increase the water content of such compositions greatly
expands the operation caindow. The reduction of the viscosity
facilitates the ease of operation by improving pumpability
and the like.
viscosity of the blend is extremely important since for ease
of operation any composition must be capable of being
processed. Typically, the viscosity of such compositions is
AMENDED SHEET
C6~184 CA 02143869 1999-12-O1
- 14 -
about 50x10-3 Pa.s (50 centipoise) to 5000x10-3 Pa.s (5000 cenHpoise) at a
temperature of 60°C or even somewhat higher.
Compositions having a ration of anionic surfactant to
S nonionic surfactant of 0.125:1 to 4:1 may be employed but 1:1
to 3:1 are of especial interest.
In addition, an improvement with regard to the processability
properties may be obtained in the blend if 0.5-80% by weight
of a C,-C,2 fatty acid is incorporated in the liquid
surfactant composition.
In this case, the blend provides a liquid surfactant
composition which is mobile at a temperature within the range
IS of 20 to 80°C and which comprises a sodium or potassium salt
of an alkylbenzene~sulfphonate or alkyl sulphate in an amount
preferably not exceeding 70% by weight; an ethoxylated
nonionic surfactant in an amount preferably not exceeding 80%
by weight; and water in an amount preferably not exceeding
20% by weight, more preferably not exceeding 10% by weight;
characterized in that it further comprises 0.5 to 80% by
weight of a fatty acid having 8 to 22 carbon atoms.
According to yet another aspect of the invention, there is
provided a process for the manufacture of the above liquid
surfactant composition, by mixing said nonionic surfactant
with a concentrated aqueous alkali metal hydroxide solution
having about 80% to 98% of the stoichiometric amount of said
alkali metal .ydroxide necessary to neutralize an acid
precursor of said sulphate or sulphonate, to form a nonionic
alkali dispersion; mixing said acid precursor with said
dispersion form a blend; adjusting the pH to about 7; and
then mixing the blend with the fatty acid to form the mobile
composition.
AMENDED SHEET
C6184 '
.- ~~.~69
The compositions include in addition 0.5-70~, preferably 2-
150, more preferably 2-7o by weight of a fatty acid having 8
t o 22 carbon atoms. It is preferred if the fatty acid
possesses I2 to 20 carbon. atoms, and more in particular 16 to
S 18 carbon atoms. A suitable fatty acid is coconut fatty
acid.
i0 Selected builder materials are added to the slurry. The
builders are preferab3y zeolite and/or sodium carbonate.
Other substantially solution materials which have a
detergency builder action may be used by including them in
the slurry. Of course, these builders may be added by post
1S dosing to the composition produced by the spray-drying step.
Examples of substantially soluble detergency builders are
sodium tiproly-, pyro- and orothophosphates, sodium citrate
and various organic detergency builders such as sodium
nitrilotriacetate, ODS; TMS/TDS homopolymers of acrylic acid
20 and copolymers of acrylic and malefic acids. Substantially
insoluble builders are, for example, sodium aluminosilicates
including zeolites, crystalline, amorphous, as well as
calcite, and the like. Generally detergency builders will be
present in amounts of from S to 70o by weight of the final
25 product, amounts of from 25 to 40o by weight being more
general.
pmuFR DETERGENT ADJLJVANTS
The slurries can also contain a number of optional components
such as lather controllers, anti-redeposition agents such as
sodium carboxymethlycellulose, fabric softening agents such
as quaternary ammonium salts either alone or in combination
3S With clays, anti-ashing aids, starches, slurry stabiliziers
~MEND~Q SHFFr
C6184
--w ~ ~r~~ss9
- 16 -
suc:~ as homopolymers of ac=~,rlic acid and copolymers of
ac ~ylic acid and malefic acid; ethylene and malefic anhydride,
and cf vinyl methyl ether and malefic anhydride, usually in
salt form; antioxidants and fluorescers.
~z a final process stage the spray-dried powder produced can
be dosed with ingredients that are incompatible with the
spray-ding process conditions fir. the amounts required to
. produce a finished powder. Components may be incompatible
for many reasons, including heat sensitivity, pH
se:lSiti-~it=; , cegradatic:: -_n aqueous systems and the like.
The usual heat-sensitive ~witterionic surfactants such as
derivatives of alphiphatic quanternary ammonium phosphonium
acid, sulphonium compounds in which one of the aliphatic
constituents contains an anionic water solubilizing group may
be added. Additional components whit'.~. may be added in this
manner are sodium perborate mono- and tetrahydrates, sodium
percarbonates and acid bleacz precursors such as
tetracetylethylene diamine, tetracetylglycouril and sodium
nor_yl ox~.-benzene sulphcnate, perfumes, enzymes and composite
adjuncts. The process is especially suitable for use where
it is i__~.tended to add composite adjuncts to the spray-dried
powder _:~ a dry-dosing step, since such adjuncts normally
nave very high bulk density and tend to separate from lighter
~5 powders. ?xamples of composite adjuncts are antifoam
_ranules, for vnstance, granules based on a starch core
having a coating of a mixture of liquid and waxy
hydrocarbons; composite colored speckles prepared in any way,
e.g., containing spray-dried base powder granulated with a
colored binder solution; and adjuncts containing calcium
carDOnate seed crystals such as high surface area calcite
(80-90 m=g-') .
'='he following e:campl2s wil~_ more fully illustrate that
embodiments of this invention. All parts, percentages and
PH~T~~~P~.' I C~~C
AMENDED SHEET
C6184 ' CA 02143869 1999-12-O1 _- ' ' ,
_. a , _
- i?
proportions referred to herein and in the appended claims are
by weight of the total composition unless otherwise stated.
The mixer includes a Lightnin~R~ A-320 impeller to promote mixing. 114.3
kg (252 lbs.) of water is charged into the mixer and heated to 37.7-
48.8°C
(100-120°F). The agitator is set at 40 RPM. 54.88 kg (121 lbs.) of 50%
caustic
solution (enough for the neutralisation reactions of precursor
alkylbenzene sulfonic acid and citric acid) is added next while maintaining
the agitator at about 0.66 rad s-1 (40 RPM). A temperature rise to 54.4-
60°C
(130-140°F) is observed.
At this point 90.7kg (200 lbs.) of nonionic surfactant (in this case, Neodol
25-7, a 7E0 nonionic) are pumped into the mixer with the agitation still set
at about 0.66 rad sn (40 RPM). The temperature is observed to decrease
approximately 5.5°C (10°F) to 48.8-54.4°C (120-
130°F). Close to the end of
or after the nonionic charge the agitator may be increased to about 0.83 rad
sn (50 RPM). 88.9 kg (196 lbs.) of alkylbenzene sulfonic acid is then added.
As the acid neutralizes the temperature increases and the mixture turns
from a transparent emulsion to a brown liquid to a white paste. As the
mixture reaches the white paste stage, the slurry mixture becomes
significantly thicker. It may be necessary to increase the agitation to about
1
rad s-1 (60 RPM) during the acid addition in order to promote good mixing
and quicker neutralisation, a short period of about three minutes after the
end of the acid addition is beneficial in order to help ensure full
neutralisation. The temperature increase from the neutralisation reaction
is about 16.6 - 22.2°C (30-40°F) resulting in a slurry
temperature of 71.1 -
73.8°C (160-165°F).
After neutralisation 43.09 kg (95 lbs.) of citric acid (for example,
Citrosol'R' 503, a SO$ solution) is charged into the mixer. A
second neutralisation reaction takes place and the
C618~ CA 02143869 1999-12-O1 '
.. _ _ _ "_
18 -
.,
temperature rises 5.5-11.1°C (10-20°F) to 79.4-85°C (175-
185°F). Increasing
the agitation to about 1.16 rad S-1 (70 RPM) and a two minute hold time is
beneficial after the citric acid addition in order to facilitate mixing and
completion of the reaction. 26.3 kg (58 lbs.) of sodium sulfate, a viscosity
adjuster, is added at this point. A few minutes may be necessary for
complete mixing of the sodium sulfate. No effective temperature change
is observed. 0.0725kg (0.16 lbs.) of Silicone defoamer is added in order to
help remove entrapped air bubbles from the slurry. Removal of entrapped
air results in a denser slurry which in turn will result in a denser spray-
dried powder. Prior to the zeolite solids addition, the agitator should be
increased to about 1.33 rad s-1 (80 RPM).
At this point 199.5 kg (440 lbs.) of 4A zeolite is charged into the mixer. The
addition of room temperature solids decreases the temperature of the
slurry to 68.3 - 73.8°C (155-165°F). As the solids are mixed,
the slurry
viscosity increases and it may be necessary to increase agitation to about 1.5
rad s-1 (90 RPM) during zeolite addition or at the end of zeolite addition
prior to sodium carbonate addition. 79.83 kg (176 lbs) of sodium carbonate
are now charged into the mixer. An increase of 2.77 - 5.55°C (5-
10°F) to a
slurry temperature of 71.1-76.6°C (160-170°F) is observed as the
sodium
carbonate hydrates. The slurry appears thinner (i.e. lower viscosity) at this
point. 2.31 kg (5.1 lbs) of a fluorescent whitener is added next. No
temperature increase is observed. Once the whitener is added, the
agitation is increased to about 1.66 rad s-1 (100 RPM) and the slurry is
heated to a final temperature of 82.2-85°C (180-185°F). A final
hold time of
minutes may be employed to ensure complete mixing of all ingredients.
A calculation of Reynolds Number NRe on the final slurry is as follows:
C6184 ' CA 02143869 1999-12-O1
~~ -'
_ ,g _
~ 2~
N = impeller speed
D = impeller diameter
p = density (speci~ic gravity)
a = viscosity (at Nn shear rate)
N = 100 RPM = 1.667 ~ voiuc'_or.s (rev>
32C
D = 23 inches - 58.42 cm
p = 1400 g/L = 1.4 kg/L
Nn= (1.667 rev> (3.1416 '_ ) - 5.2
sec =ev sec
a = 36,725 cP at 5.2
sec
1i = 3 . 1416
1. 667 sec~58 .42 can]~ 100cm,~1.4~~ ~lOL3m3~3 .1416 rev
(36,725 cP] ~ 1 x 10'3m~ sect
1 C JP
NRQ = 6 8
Careful temperature control is important since batches which
have been heated above 93.3°C (200°F) have been observed to
separate
and char the nonionic. The slurry described herein may be
made, pumped and circulated through piping without physical
separation issues provided appropriate temperatures are
maintained.
AMENDED SHEET
C6184 -"
. -.
20 -
rnvnTr-~r yIcCOcI~'" PROF'IL~ DA'T'A FROM A MODEL SLURRY AS IN
Fxn.~rpr,F I I~, AS FOLLOWS
She Rate viscosity C( cP ~) c~ 3('~.
-
** 5.2 36,7
7.615 27,270 (T=~59og,~~j~G>
11.86
19,170
* 17.92 13,800*
27.49
9,858
i0 42.17 6,997
64.71 5,045
99.26 3,637
152.6 I 2,611
,;
* value is typically used fo_r reporting purposes.
** interpolated value.
ENDED SHEET
C6184 ,. -
,.~.
- 21 -
X~~SPLE T
c
J
h powder is prepared _rcm the slurry of this invention
containing the following ingredients:
F T -iED POWDER PR~'PPRED FR01~. 30 o SLURRY MOISTURE CONTENT
(zn order of Addition)
TOWER: o IN FINISHED
PRODUCT:
_;, water ~ 12.60
Sodium Hydroxide, S0o soin ---*'
Alcohol Ethoxylate, %EO 12.00*
Sodium Alkyibenzene Sulfonate 12.00*
(neutralized 'rom the suifonic acid)
15 Sodium Citrate 4.00
(neutralized from citric acid)
Silicone Defoamer 0.01
Zeolite, anhydrous 22.00
Alcohol Ethoxylate, 11E0 1.00
20 Sodium Carbonate 14.00
Fluorescent whitening Agent 0.30
Miscellaneous Solids 0.02
Reserved 22.07
(for post-dose ingredients,
2S colorants, perfumes, extra builders,
and the like)
4
AMENDED SHEEN
C6184
.-.
2i 4 38 69
_ .22 _
these are tine components for tine liquid active blend 1:1
Linear alkylbenzene sulfonate (LAS>:7E0 (Nonionic) to yield
24o active in the finished product.
consumed in neutral=nation reactions.
AM~NDED SHEET
CA 02143869 1999-12-O1
C6184 _ _ . , . . . . .
- 23 -
~XA~rpLE. II r II
SOW MOISTUR.E CONTENT MODEL SLURRY
pROC~~STr1- =N ORDER OF ADDITION
(725.7kg (16001bs)), fi~ished product bath size)
TEMPERATURE AFTER
RAW ~ ADDITION COMPLETE Kg(LBS)
water I 22.2C (72F) 129.7 (285.94)
50~ sodium hydroxide 41.1C (106'F) 55.6 (122.70)
nonionic, 7EO 38.3'C (101'F) 9g,7 (217.60)
alkylbenzene sulfonic 63.3'C (146'F) 92.3 (203.50)
acid
sodium sulfate 61.1C (142'F) 63.9 (141.02)
citric acid, 50$ 68.3C (155Fl 43.2 (95.26)
silicone defoamer 65C (149F) 0.0725 (0.16)
4A zeolite 60C (140F) 199.5 (440.00)
(may have to add heat
during zeolite addition
in order to maintain about
67.7C (140F)
?0 sodium carbonate 67.7C (154F) 79.8 (176.00)
fluorescer whitener 67.2C
(153F)~ ~ 2.29 (5.05)
Heat finished slurry batch
to 85-93.3C (185-200F)
This slurry formulation will yield an approximate Slurry
Moisture Content (S.MC) of 30$. Water losses due to
evaporation may result in a lower SMC measurement. Extra
water can be added to compensate.
AMENDED SHEET
C6184
~.... .
21 4 3s s 9
- 24 -
~~~7 ivIOISTUzt~' !"ONTG'N'T' MODEL SLURRY
F~'I~~AL PORMLJLATION
RAW $ FINAL PRODUCT
j water
1 6
ron,~o.~.ic , i e0 12 . S
linear a'_icylbenzene
sulfonate sodium salt !LAS) 12.5
sodium su'_~ate 8.814
sodiv,:.m citrate 4.0
silicone defoamer 0.01
4A zeolite 22.0
soci~.:rn carbonate 11.0
f~uorescer whitener 0.3
S miscellaneous solids 0.2018
POST-DOSED
4A zeolite 4.0
Derf~.:me 0.4
sodium carbonate 10.0
?0 _ sDec~:les 1.0
enzymes 0,.6742
TOTAL
1 00 . 00
- AAAFNDED SHEEt
C6184
21 ~r38 69
iv
Slurries were prepared as =n S,xample _T but the ingredients
were varied.
S
A. LAS/NI 1:~
Slurry Moiscura 'cntent 300
Zeolite
Sodium Sul~ate 8%
.0
In order o~ Addition
ENDED SHEET
CA 02143869 1999-12-O1
C6184 ~ - . . ~ _ ~ . . _
__ . -' '
-:
_ pp M ~ ~ ~ N
. Cs O W O p ~ N p
.x ~ ~' .~ ~
a ~ ~ M p .~.~ g O
M Q; ~ ~ N M ~ M
N ' l!~ ~D o
o. o o ~ ~ c~~'~ ~ ~ .fir
ro ~ ~ ~ ~ ~ ~ ~ M ~
U
O O O O O O O O O O O
o O o o O O O O O O O
p O O O O O O O O O O O
E. e-i .-~ r-1 ~--~ ~i .-I r-I ~,~1.-~ ~--ir-1
w O O o O O O O O O O O
ao o O o o O o O o O O O
.-~
U1 O O O N O O O O O O O
'.
U O O O O O O O O O O O
dP O O O O O O O O O O O
U1
.O O O N o O O O O 1f1 O
S-r o O O O O O O O O O O
v o 0 0 0 0 0 0 ~ 0 0 0
L . . . . . . . . . . ,
0 0 0 0 0 0 o c~ o 0 0
3 ,n 'n
_ N
O O O O ~ O O O O O O O
O O O O O O O C~ O O O d,
.rl . C~
dP O O O ~D O O O O O lf) O
1J o u1 O o~ ~n O O ~ O a~ O .d
U
,
o O O O o O O O O O 1f1 O
r; 0 0 o O O O O O O O tf1
O O o O o o r-I O o O CO o
,~ o ~ ~ O o o O O ~~~1c~
ro
dP N O N N C' CO O N .-1 O ~D d,
c r W --1 .-i N r-) '-1
.rl
(L , x f"1
y.,
N ~ W
N E a
~0 ro
X
.~ b w ~ .~ O
w
...~~ D Sr 1~
c U O Q U a ro 41 dy
E ~ a
c~ ~ ~ ~.U-~ U cn U U ~
o a E O ~.~E o
W o ~ c ~~ a v a s~ a
a w w "' ~' ~ v ,~ o 'v
3 . ..~ o .., a~ o ~ o x
a v~ z a a cn v~ N ~n w x
a a
ui O .. o
N
AMENDED SHEFt
C6184 . _ - v 21~~ 8 f 9 -
COMPOSITION o
g,p,W F=VAL POWDER ~ BASE POWDER
WATER .2.5000 15.0872
NONIONIC ~ =?.3000 14.9675
LAS =_.000 14.9675
SODIUM CITRATE ~ .0000 4.7896
SODIUM SULFATE _.:OCO 9.5792
SILICONE ~ .,.0100 0.0120
ZEOLITE ~* ~ 2.0000 26.3427
i0 SODIUM CARBONATE ~ __.~J000 13.1714
FLUORESCER 0.3000 0.3592
MISC. SOLIDS ~ G.5045 0.7238
HOLE' ~ _0.4855
TOTAL 100.0000 ~ 100.0000
to be post dosed
A;vAEt~D~D SHEET
C6184 - - ~ --
-: v :-
- 28 -
3. LAS/NI 1:1 25o total
Slurry Mois~ure 300
Zeolite 4A
Sodium Sulfate 40
In order of Addition
. A~AFNDED SHEEN
CA 02143869 1999-12-O1
., .~ ~.
C6184~ _ _ '
. r : '~ : :- _ ; ~ ..
x a OIv.~ ~..,
3 ~ ~ O ~ ~ M ~ ~ ~ N
~ ~ d" ~~ ~ ~ ~ O ~ O
~ O O
~ '~ ri ~ O M l!7 N W O
O LW 1~
U
0 o O o O o o 0 0 o o
a o 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0 0 0
N
w o 0 0 0 0 0 0 0 0 0 0
dP 0 0 0 0 0 0 0 0 0 0 0
,-, ~
0
V7 O O O O N O O O O O O
~
U o o o o O o O O o O o
~
da o o 0 o O o o O O O o
m
O O O O N O O O O !f1 O
~
1.1 O O O O O O O O O O O
U O O O O O O O O O O O
dp
y,~ O O O O O O O O O O O
1f1 N
0 0 0 0 0 0 0 0 0 0 0
> 0 0 0 0 0 0 0 0 0 0 0
dA O O O O ~O O O O O 111 O
aJ o u~ o o rn w o ao o a~ o
U
a
0 0 0 0 0 0 0 0 0 0 ~n
0 0 0 0 0 0 0 0 0 0 ~n
w 0 0 0 0 0 0 ~ 0 0 o a~
n o w o m o 0 0 o cn a
dP N O N cr N C~ O N r-1 O O
~ e1 ri ~-I N r-I, N
rl
[i,
O
N N d
O ~ 'O w O
w .a 'O Ul .L~
.d ~ U .~, A a s~ s~
i,J ~, G a U ~t't0 (1J
U O U: a O U U
U U U
-.-~ ~ U G ~ U w
F v w .-i O ~..~
E G C~ . ~ U .~-t~ ~
ci~ ..~ .-~..~ o o
o a o c 'v o ~ .-, o 'o
o a .,~ .~, .,~ ~, o ~,
U 3 ~1 o ~' cn a c U cn N cn
Z a --
a
u, o
AMENOEO SHEET
C6184
- - . - 2 ~ ~-"~_8-6 ~ _ _ ,
- 30 -
COMPOSITT_ON o
Rpw ( FINAL POWDER BASE POWDER
wATER L2.6000 15.8462
NONIONIC 12.5000 15.7204
LAS 12.5000 15.7204
SODIUM CITRATE i 4.0000 5.0305
SODIUM SULFATE ~ ~-_.0000 5.0305
SILICONE 0.0100 0.0126
ZEOLIT~,' 4A 22.0000 27.6679
SODIUM CARBONATE ~. L1.0000 13.8340
F:~UORESC~R 0 . 3 00 0 0 . 3773
MISC. SOLIDS 0.6045 0.7602
::OLE* 20.4855
TOTAL ,100.0000 ~ 100.0000
- to be pos' dosed
AMENDED SHEET
C6184 : . 21~~~69
- 31 -
C. LAS/NI 1:1 35o total
Slurr<~ Moisture 250
Zeolite 4A
Sodium Sul~ate 4%
S
In order of Addition
~pIENDEO ~E~
CA 02143869 1999-12-O1 I
C6184 - . . -
32 _ _ .. . -
n
~
.x 3 ~ ~ M O ~ N
~ ~ ~ ~ ~ p .- ~-.cV
~ .
O~ ~ d~ Os ~ ~ ~ O ~ if
c~ ~ ~p 0
ro n ~ p ~ ~ p O
Oi0 ~ ~ O ~ ~ ~
.
U ~
O O O O O O O O O O O
1.~ O O O o O o o O o O O
O O O O o O O O o O O o
w O O o O O O O O O O O
dP ~ O O O O O O O O O O O
U1 O O O N O O O O O O O
C
U o o o 0 o o o o o o O
da U7 o o O o o O O O o O O
.,.,
O O O N O O O O O lf1 O
1.1 O O O O O O O O O O O
O O O O O O O O O O O
do y~
ro O O O O O O O O O O O
lf1 tf1 N
0 0 0 0 0 0 0 0 0 0 0
> 0 0 0 0 0 0 0 0 0 0 0
a~ ~ 0 0 0 ~ 0 0 0 0 0 ~n o
U O u1 O aw n o o CO o a~ O
a .-r ~ .-a ~--i ~ ,-a
O O O O O O O O O O
O O O O O O O O O O ~T
O O O O O O e-i O O O N
.--i ~D O tflw fl O O O O O c'1 ('''1
dp ~ N O t~ t~ C' C' O N '-IO O
-.-1 ~ .-i '-1 N e-i e-~
'd ~ L
a~ ro ro
x ~ o
o ~ ro w o
-.~ ~ w N .t7
v U -~ .-~ o a
~., a U a a' ro
C x U O ~ ~ v U U
-.~ a c u~ ~n
w
C ~ C c'~ --~ U E O L E
O oG ~ O i ~ C -~ ~ U -.~ O f.~
C. W ~.~ -.~ cl1 Sa -.~ -.~ .-r -~ O W
~~ O
-.a a 'p ~ O 'a ~ .a
~
o a o o := c -~ o -.~ a~ o .~ o
U 3 ~ 2 U v a U ~ ~1 N c~ t~. x
u~ o w
AMENDED SHED
6184 _ 2-I43869 : '
.....
- 33 -
rOMPOSITT_ON $
RAW F INAL P04v'DER BASE POWDER
WATER
12.5000 14.0506
NONIONIC '_7.5000 19.5148
LAS 17.J000 19.5148
SODIUM CITRATE -'_.0000 4.4605
SODIUM SULFATE _.0000 4.4605
SILICONE 0.0100 0.0112
ZEOLITE 4A ~2.G000 24.5329
SODIUM CARBONATE ~ 11.0000 12.2664
FLUORESCER 0.3000 0.3345
MISC. SOLIDS 0.7656 0.8537
HOLE* ~ 10.3244
TOTAL 1100.0000 100.0000
* to be post dosed
,~aE~DE4 sHEET
.-.- w 21~-~~r9
_ 3a_ _
D. ~AS/NI 1:1 35o total
Slurry Moisture 25 0
Zeolite 4A
Sodium Sulfate 8$
In order of Addition
AIvIE~,',~Fn ~~, .
CA 02143869 1999-12-O1
C6184 . , . _ .
- 35 - _ . _ - _
~
O
O N
N ... .-. ~~ O ~ ~
~ ~ ~ ~ ~ O O
~ er Q\ N W p O ~
M O M O ''1O ~G O
C te ~
. N ~..'iN N ~ ''a ~ r "r
,,
U 'r ~ '. '. v ~ ..r ..r
~
rl o O o 0 0 ( O O O O O
o
LJ O O O O O O O O O O O
O O o O o O O O O O o O
w O o o O o o O O O O O
dP O O O O o O O O O O O
r1
~f! O O O N O O O O O O O
U O O O O O O O O O O O
dP O O O O O O O O O O O
fn
O O O N O O O O O lI7 O
S-1 O O O O O O O O O O O
N O O O O O O O O O O O
dp .
y~
ftS O O O O O O O O O O O
tl1 N
a7 0 0 0 0 0 0 0 0 0 0 0
> 0 0 0 0 0 0 0 0 0 0 0
aP 0 0 0 ~ 0 0 0 0 0 ~n o
~
U o m o a~ ui o o ao o a~ O
Q,' r-1 ri r~ ~ e--i v-i
O o O o o O O O O O
O O O O O O O O O O
O O O O O O r-1O O O N
.-1 O O lIW I1 O O O O O c~1 C~
~ O O I' t~ C~ N O N r-1 O O
dP
_ v- W -1 rl N .--i
r1
~r
'~ ~ LJ
-r1 O t0
X
O
O ~
.O W N
p U -~ ~ fa ~ lr Sr
~ a U
G x U O ~ ~ ~ U
. ~
C ~~ C t~ ~~ a ~ O E 4J
O CY.."~' O ~ C -~ a U ri ~ S-a x
CL W -.~ .-i v1 S..iw w ~ -~.~O W
~ O
" Ts .-~o ~ ~ a
~
o a o o ~ c -.~ o -.~v o ~ o
a 3 cn Z a -- a cn cn N cn o. x
a
u, o w
4ra~~a~c s~rE~
C6184 ~ . _ - -,21 ~.~8-6 9 .
..
- 36 -
OM ION
RAW ~ FINAL POWDER BASE POWDER
WATER 10.0000 10.9799
NONIONIC 17.5000 19.2148
LAS ~ 17.5000 19.2148
SODIUM CITRATE ~ 4.0000 4.3920
SODIUM SULFATE 4.0000 8.7839
SILICONE 0.0100 0.0110
ZEOLITE 4A I 22.0000 24.1558
SODIUM CARBONATE 11.0000 12.0779
)
FLUORESCER 0.3000 0.3294
MISC. SOLIDS 0.7656 0.8406
HOLE* 8.9244
TOTAL 100.0000 100.0000
* to be host dosed
AMENDED SHEET
6184 _ ,. ~2143~~69
- 37 -
E. LAS/NI 1:1 40$
Slurry Moisture 20~
Zeolite 4A
Sodium Sulfate 4~
S
In order of Addition
~~N'~~'p SH ~
06184 CA 02143869 1999-12-O1 ,
- , -. " . ., ,
.-.38 -. . '._ - - . _ _ ~ ~ _
p p 00
' .x ~ n ~ ~ N ~ O ~ d~ o~
3 ~ n p
p -. ~ ~ N ~,, -~ N .
ri ~ O ~ p C~
~0 ,-~-~ ~ N ~ '-~p ~D O p
~ v ~ ~ v O ~ v ~
.,~
U
.-1O O O O O O O O O O O
a o 0 o O o 0 o O o O o
O O O O O O O O O O O O
E, .-.a~ ,~ ~--~ ~--~.-~ ~--r
W O O O O O O O O O O O
dP ~-1O O O O O O O O O O O
Cn O O O N O O O O O O O
U O O O O O O O O O O O
dP U! O O O O O O O O O O O
O O O N O O O O O ~f1 O
f-IO O O O O O O O O O O
O O O O O O O O O O O O
dp a
r0 O O O O O O O O O O O
3 ~n u~ N
a7 0 0 0 0 0 0 0 0 0 0 0
O O O O D O O O O O O
dP a O O O t0 O O O O O ~ O
U O lI1 O Q1 l11 O O CO O 01 O
a
O O O O O O O O O O Q1
O O O O O O O O O O c~1
O O O O O O r-1O O O C~
..-i~O O O O O O O O O f'~1N
dP ~ N O O O V~ C~ O N ,-.1O tf1
-rirl N N N .-1
CL
v N 4l
b ~ a
-ri O (0 t6
X a O C
O 'D ~ W O
~.1 ri '~
v ..~ ~ o a
a ~, a a a a b v
c x v o a cn a~ a v
U .~ W U C O N
C E C t~ -~ U E O a E v
O CL: ~~ O ~ C .~ ~ U -.-1~ ~ x
a w .,~ ..~~ ~n o ~ -~, ..~.-~ .,~ o w
E E-' 'L3 G a ..ra 'p ~ O 'p ~ ,.a
o a o o a c .~ o .~ v o ~ o
a 3 ~n z a -- a a cn cn N cn w x
u, o m
AMENDED SHEET
C 618 4 . . . _ _ ~ 1 ~~' ~-~'~
. . . .
_ 39 _
COMPOSITION o
RAW FINAL ?OWDER BASE POWDER
WATER .2.6000 13.2973
S NONIONIC 20.0000 21.1068
LAS 20.0000 21.1068
SODIUM CITRATE 4.0000 4.2214
SODIUM SULFATE 4.0000 4.2214
SILICONE 0.0100 0.0106
ZEOLITE 4A 22.0000 23.2175
SODIUM CARBONATE 11.0000 11.6088
FLUORESCER 0.3000 0.3166
MISC. SOL_TDS 0.8461 0.8929
HOLE* x.2439
TOTAL 100.0000 100.0000
* to be post dosed
AMEi~DED SHEET
C6184
,.,..~
- 40 -
F. LAS/NI 1:1 25$ total
Slurry Moisture Content 30$
Zeolite 4A
Sodium Xylene Sulfonate 1$
S
In order of Addition
AII~fENDE p ~EE7,
CA 02143869 1999-12-O1
C6184 ~ . . , .,~ " ,. ., ~ '
:_4;--:' : ~ ~.'._- ;_v.
e~' $' r'' O
Os N~ (V ~ ~ ~D O Ov
3 ~
O M 0 00 M 00 O ~. N ~ N
0
N .~ ~ ~ ~ ~. ~ C~ ''~ l~ ~ N
O Os O CO vD ~ ~ ~ O
'~ 00 N ~ tfj O ~ O ~ ~ O
N 00 O~ p ~" ~ N
~
.r .r
O O O O O O O O O O O O
b
1J O O O O O O O O O O O O
O O O O O O O O O O O O O
w O O O O o O O O O O O O
dP O O O O O O O O O O O O
.-1
U1 O O O N O O O O O O O O
U O O O O O O O O O O O O
dP O O O O o O o 0 o 0 o O
U1
,'f'",O O O N O O O O O O lf1O
f.1 O O O O O O O O O O O O
O O O O O O O O O O O O
do
y~
O O O O O O O O O O O O
lf1 lf1 ~D N
0 0 0 0 0 0 0 0 0 0 0 0
> 0 0 0 0 0 0 0 0 0 0 0 0
dP o 0 0 .a o 0 0 0 0 0 ~n o
a
U O u1 O a n c~ o m o O Ov o
a
O O O O O O O O O O O N
~
O O O O O O O O O O O C
O O O O O O ~ O O O O I',
rW D O O O O O O O O O t~1O
d C N O N N V~ ~ O N ~ C~ O rl
r1 v-1 n e-1 N e-~ N
W
U N
iJ
~ p
b
- ~
a ?, ~ U ?, O ~ U
U
G x U O a >C ~ U W U U
a
U -.-~ U r0 ~ N -~ al
W ri
C E - C .,., U ~ ~ O ~ C ~ ~ N
r.
O aG ~ O ~ -- -.i ~ O U -~ O ~ O f-~*
C W
L1 W .r ..~ v1 ~r -.-~ ..-~~ -.i -.-aO
~ O w ~
'
E-~ 'd G ~ ~ ~.~ ~ O -i .-i O G ' ~ ~ O
" ~
o a o o a c -.~ o ~ -.~ v o o ,
a w
a 3 ~n z v ~ U ~ v1 ~1 N Z a ~
u, o w o
N
AMc~DEO S~iEET
CA 02143869 1999-12-O1 ~ , y~::
C6184
- ° . ~" ... ~, ~,
. ~ . , -, . ; :'. .:
- 42 -
R.AW Temp . Ob s a nra t ions
Pre-Addition
water (97.8F) 36.5C --
Caustic (97.6F) 36.4C cloudy
Neodol 25-7 (112.1F) 44.5C more cloudy
(LAS) Acid (109.7F) 43.2C Like mayonnaise, fluffy
Sodium Citrate (148.8F) 64.9C slightly thinner, still
..
fluffy, like mayonnaise
Sodium xylene (156F) 68.9C creamier
Sulfonate
Silicone (145F) 62.8C no change
Zeolite 4A (145F) 62.8C thick, very slightly
moving around the A-320
impeller
Nonionic (125F) 51.7C Heat up, smooth, slightly
C:Z_ 15-7 EO mixing
Sodium Carbonate (140F) 60C thick but mixes in,
slightly moving
( Fluorescer (154.7F) 68.2C lost moisture, not mixing
as well as when sodium
carbonate was added,
looks thick
26.7% measured moisture
AMENDED SHEET
C6184 ~14.3~~9
- 43 -
COMPOSITION
F.AW ~ FINAL POWDER ~ BASE POWDER
WATER 12.6000 15.9644
S ANIONIC ACID 12.0000 15.2042
LAS 12.0000 15.2042
SODIUM CITRATE 4.0000 5.0681
SODIUM XYLENE 1.0000 1.2670
SULFATE
SILICONE 0.0100 0.0127
ZEOLITE 4A 22.0000 27.8743
NONIONIC 1.0000 1.2670
SODA ASH 14.0000 17.7382
FLUORESCER 0.3000 0.3801
1S MISC. SOLIDS O.O1S8 0.3801
HOLE* 21.0742
TOTAL 100.0000 100.0000
to be post dosed
AMENDED SHEET
C6184
~~=4~~~69
- 44 -
G. LAS/NI 1:1 25~ total
(premanufactured and neutralized blend)
Slurry Moisture Content 30$
Zeolite 4A
Sodium Sulfate 4~
In order of Addition
CA 02143869 1999-12-O1
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AMENDED SHEET
C6184
- 46 -
COMPOSITION o
FINAL POWDER BASE POWDER
WATER 12.6000 15.9268
BLEND 25.0000 31.6008
SODIUM CITRATE 4.0000 5.0561
SODIUM SULFATE 4.0000 5.0561
SILICONE 0.0100 0.0126
ZEOLITE 22.0000 27.8087
TINOPAL FLUORESCER 0.3000 0.3792
MISC. SOLIDS 0.2018 0.2551
HOLE* ~ 20.8882 ____
TOTAL ~ 100.0000 100.0000
* to be post dosed
AMENDED SHEET
6184 ~1~3869
- 47 -
The compositions of Example I, II, III and IV A through F all
use separate mixing of the anionic and nonionic actives.
Example IVG is a prepared neutralized blend. In Example I,
II, III and IV A through F, the surfactant mixtures were
prepared as taught herein. Premanufactured or prepared
blends either neutralized or not could be employed in place
of the individual addition.
The blends may be prepared as follows:
LAS: Sodium Salt of C11-C,5 Alkylbenzene sulfonic acid
(Stephan trademark Bio-Soft S-100)
NI: Nonionic surfactant (C:2-C=5 alcohol ethoxylates),
Shell trademark Neodol 25-7
N13E0: Nonionic surfactant (C:2-C1, alcohol ethoxylates),
Shell trademark Neodol 25-3
L: liquid phase
G: gel formation
AMENDED SHEEN
6184 214-3869
- 48 -
FXANtpr,ES V-VII
The neutralized mobile liquid surfactant mixture listed in
Example V is prepared by mixing the nonionic surfactant with
the indicated amount of concentrated aqueous sodium hydroxide
solution (50 w/w~) and subsequently mixing with alkylbenzene
sulfonic acid, Stepan Bio-Soft S-100. Examples V-VII
indicate that a higher NaOH content maintains the liquid
state for a higher level of water present in the composition.
The percentages reported in the following Table are based on
the final total content of materials.
Example V VI VII
(~ by weight)
LAS 43.0 35.3 27.5
NI 43.6 35.8 27.8
water 10.4 24.6 33.0
NaOH ( 10 0 0
Excess 3.0 4.3 11.7
Phase * ~ L L L
* at room temperature
EXAMPLES VIII-X
The following liquid surfactant mixtures are prepared by
mixing the nonionic surfactant with concentrated aqueous
sodium hydroxide solution (SO w/w~) in an amount
stoichiometric to the alkylbenzene sulfonic acid plus the
excess quantity of NaOH solution. This mixture is then mixed
with the alkylbenzene sulfonic acid. The viscosity is
AMEt~SDE~ ~E;
c6184 2143869 ~ ,
- 49 -
measured by a Contraves Rheomat model 108E at room
temperature. Examples VIII-X demonstrate the effect of the
excess of sodium hydroxide in reducing the viscosity of the
surfactant compositions.
Example VIII IX X
($ by weight)
LAS 57.1 54.5 52.1
i0 NI 28.6 27.1 25.9
Water 12.1 13.8 15.4
NaOH (100$)
Exceed 2.4 4.6 6.6
Shear Rate, 1/sec 9.85 9.85 9.85
viscosity, cP 4120 532 537
The following mobile liquid surfactant mixtures are prepared
by mixing the nonionic surfactant with concentrated aqueous
sodium hydroxide solution (50~ w/v) in an amount which is
slightly less than stoichiometric to the alkylbenzene
sulphonic acid, adding the Clo-C1, alkyl benzene sulphonic
acid and then a small amount of a 50$ (w/v) sodium hydroxide
solution to bring the pH to a value of about 8. Due to the
exothermic neutralization reaction, the temperature is raised
to about 80°C.
Finally, the indicated amount of the fatty acid are added to
the mixture.
AMENDED SHEEN
c6184 2~.~~$6~
- 50 -
Example XI XII XIII XIV
(% by
weight)
Nonionic.3E0 21.14 20.50 19.86 19.23 18.60
Nonionic.7E0 21.15 20.51 19.87 19.24 18.61
NaOH (50%) 11.18 10.84 10.50 10.17 9.84
ABS (acid) 45.93 44.55 43.16 41.80 40.52
NaOH (50%) 0.60 0.58 0.56 0.54 0.53
C16-C18 Fatty Acid 0.0 3.02 6.05 9.02 ~ 12.00
The pH of the mixtures of Examples XII-XV was between 5.5 and
7 at a temperature of about 80°C.
It is understood that the examples and embodiments described
herein are for illustrative purposes only and that various
modifications or changes in the light thereof will be
suggested to persons skilled in the art and are to be
included within the spirit and purview of this application
and the scope of the appended claims.
,~,1A~NDED St'~E~
