[0001] This invention relates to detergents, and more particularly, to free flowing, high
active anionic detergents.
[0002] High active detergents, for the purposes of the present invention, may be defined
as detergents comprising more than 12% active matter.
[0003] Free flowing, for the purposes of the present invention, may be defined as sufficiently
mobile as to be capable of being poured or dispensed reproducably as a measured quantity.
[0004] It is desirable that detergent powders exemplify certain characteristics, namely,
the detergent powder should be non-dusty, free flowing, easily handled, easily dissolved
and stable under normal storage conditions.
[0005] A large proportion of the worldwide detergent market uses high foaming powder surfactants,
most of which are based on anionic active matter ingredients.
[0006] It has hitherto been common practice to produce detergents in powder form by making
up a slurry of the various ingredients in water and subsequently spray drying the
slurry to yield a powder of typical bulk density 0.2 to 0.5 gms/ml. This method of
manufacture is expensive because heat is required to evaporate the water which was
initially added and yet is not required in the final product.
[0007] A further method of manufacture of detergents in powder form is by so called 'dry
neutralisation'. Dry neutralisation and associated agglomeration is normally regarded
as a three part process:
1. Dry adsorption of an alkyl aryl sulphonic acid onto the surface of an alkaline
base.
2. Addition of water to affect the reaction of the alkali and sulphonic acid to form
an alkaline sulphonate which binds the constituents to produce a neutralised detergent
agglomerate; and
3. Coating the outside of the agglomerate with a layer of dessicant material such
as sodium tripolyphosphate, sodium carbonate or silicate.
[0008] It has previously been assumed that: there is a reasonably well described limitation
on the amount of alkyl aryl sulphonic acid which can be adsorpted onto the surface
of various alkaline bases without first causing over agglomeration or poor flow properties.
For example it has been claimed that the adsorptive characteristics of tripolyphosphate
or other adsorptive materials are a function of their surface area. Therefore, sodium
tripolyphosphate (STPP) in powder form must have greater adsorptivity than in granular
form. Definitive tables of the adsorptivity of STPP and other alkalies have been published
in the past giving the adsorptivity of various powders with regard to the uptake of
alkyl aryl sulphonic acid, for example do decyl benzene sulphonic acid (DDBSA.) This,
theoretically, limits the amount of active matter which can be formulated into a detergent
powder produced by dry neutralisation.
[0009] The table (A) below shows commonly accepted limitations of the adsorptivity of various
bases.
TABLE A
g DDBSA/100g alkali salt |
|
STPP Powder |
32.5 |
STPP low density granular |
2.0 |
STPP regular density granular |
2.1 |
soda ash (powder) |
2.2 |
soda ash (granular) |
0.2 |
Sodium metasilicate anhydrous |
0.1 |
Sodium metasilicate 5H₂O |
0.1 |
[0010] It has previously been assumed that the addition of approximately 1-2 % of water
was necessary to cause in situ neutralisation of sulphonic acids with alkaline bases.
The product was not thought to be stable until this reaction had been completed. It
has previously been assumed that a dessicant should be used to coat the outside of
the agglomerate to adsorb free water, usually by hydration of the dessicant, to obtain
a free flowing product.
[0011] According to a first aspect of the present invention, there is provided a method
of producing a free flowing, high active, anionic detergent comprising the step of
adsorbing an anionic surfactant acid onto a powdered or granular material to form
an agglomerate without the addition of water in the agglomeration stage.
[0012] It has been discovered that the powdered or granular detergent composition derived
from this method suprisingly has a substantially uniform particle size and may comprise
high levels of surfactant acid successfully exceeding the maximum surfactant acid
content of the prior art.
[0013] According to a second aspect of the present invention there is provided a free flowing,
high active, anionic powdered or granular detergent composition comprising an anionic
surfactant acid adsorped onto a powdered or granular material, said detergent composition
having a particle size distribution substantially within the range from 248 microns
to 1752 microns.
[0014] According to a third aspect of the present invention there is provided a free flowing,
high active, anionic, powdered or granular detergent composition comprising a surfactant
acid adsorped onto a powdered or granular material the surfactant acid being present
in the range from 12 to 40% by weight of the total composition and the powdered or
granular material being present within the range from 20 to 50% by weight of the total
composition.
[0015] In a preferred embodiment of the invention, the anionic surfactant acid is adsorbed
onto heated, dry, powdered, or granular material. In a preferred embodiment of the
invention the anionic surfactant acid is adsorbed onto heated dry powdered or granular
form preferably in a fluidised bed.
[0016] In a further preferred embodiment, the agglomerate so formed is then coated by the
application of a silicate and/or alkali, preferably in a fluidised bed. The temperature
of the inital part of the fluidised bed is preferably above 50°C and more preferably
in the range from 85 to 95°C.
[0017] Any suitable anionic surfactant acid may be used. Suitable examples of such are as
follows: alkyl aryl sulphonic acids, fatty acid sulphonic acids, olefin sulphonic
acids, fatty alcohol ether sulphuric acid, fatty methyl ester sulphonic acid, alkane
sulphonic acids. More particularly alkyl aryl sulphonic acids containing an alkyl
group with 9-20 carbon atoms and a sulphonic acid or sulphuric acid ester group (included
in the term alkyl is the alkyl portion of the aryl groups), or fatty acid sulphuric
acids obtained by sulphating alcohols with 8-18 carbon atom chains. Especially valuable
are linear straight chain alkyl benzene sulphonic acids in which the average number
of carbon atoms in the alkyl group is from 11 to 13. The amount of anionic surfactant
acid added is preferably in the range 12% to 40%, more preferably from 12% to 35%
and even more preferably from 12% to 30% of the final product weight for weight.
[0018] We have discovered that we can adsorb up to at least 50gm DDBDA/100gm STPP powder
when operating under the conditions of the invention thus significantly exceeding
the amounts known to have been adsorbed in previously published work, whilst still
retaining the free flowing nature of the end product.
[0019] The powdered or granular material may comprise any suitable alkali, or alkalies,
alone, or in combination with other additional ingredients. Examples of suitable alkalies
are as follows: Sodium phosphates, for example sodium tripolyphosphate, sodium carbonate,
sodium bicarbonate, sodium silicate or other similar alkalies including potassium
or magnesium salts. The amount of alkali is preferably in the range 10% to 95% and
more preferably 60% to 95% final product weight for weight.
[0020] Additional ingredients may include the following: bleaching agents for example Sodium
Perborate, corrosion inhibitors or alkaline additives, for example, Sodium Silicates,
inert fillers, for example Sodium Sulphate, surfactants, optical brighteners, preventors
of soil redeposition, (for example, sodium carboxy-methyl cellulose,) dedusting agents
and solubilisers, such as sodium xylene sulphonate, enzymes, chelating agents, perfumes,
softening agents, defoamers, bleach activators, soap, and non ionic active material.
[0021] Any suitable apparatus may be used, but this may have to be adapted to run under
the appropriate conditions so as to maintain dry conditions during the agglomeration
stage. Examples of such apparatus are as follows:
1. Static or moving machines with dividers or blades or paddles to mix the powders.
These include twin shell blenders or V blenders, baffled drums and ribbon or paddle
blenders.
2. Air suspension machines which suspend the particles in air whilst liquid is sprayed
onto said particles. The particle size increases until the particles are too heavy
to be suspended at which time they fall from the air stream.
3. Apparatus in which air is used to fluidise the particles making them act in a similar
manner to a liquid, for example, a fluidised bed.
[0022] Sample powdered or granular detergents derived from this method exhibit the following
characteristics:
Particle Size
no more than 3% by weight of the particles are larger than 1700 microns
no more than 1% by weight of the particles are less than 250 microns
average particle size 1100 to 1300 microns
Bulk density: untapped 600-720 gm/ml
tapped: 730-830 gm/ml
moisture content: less than 4% W/W
angle of repose average: 37 to 38°C
with minimum 36° maximum 41°
sliding angle: minimum 25° maximum 28°
flowrate: 30-41 cc/sec through standard orifice.
compressibility: 7-15%
Composition of anionic detergent granulate:
[0023] The detergent composition comprises 5 to 40% preferably 10 to 35% and more preferably
12 to 30% by weight of the final composition of an anionic surfactant acid for example
Sodium alkyl aryl sulphate. The detergent composition comprises 20 to 50% preferably
25 to 45% and more preferably 30 to 40% by weight of the final composition of the
powdered or granular material such as the alkaline material sodium tripolyphoshphate.
The detergent composition may also comprise any of the optical ingredients listed
on page 5 including for example any of the following: soda ash, sodium sulphate, sodium
carboxy methyl cellulose, optical bleaches, sequestering agents, sodium silicates
etc.
[0024] For the purpose of the present invention:-
the angle of repose is defined as the angle from the horizontal to the line of slope
of a heap of powder, the heap having been formed by directing powder through a funnel
into the centre of a circular horizontal surface. The funnel is slowly raised to allow
the heap to form immediately beneath it.
[0025] The flow rate of the powder is defined as the rate in cubic centimetres per second
that will flow through a 1.25cm diameter orifice with a smooth PVC funnel expanding
at 10° to the vertical above the orifice.
[0026] The angle of slide is defined as the minimum angle between the horizontal and an
inclined surface when a powder slides by gravity en masse down that surface, the surface
being a smooth, wooden unpolished medium. The powder is scattered as a layer no more
than 20mm deep on the surface. The surface is raised slowly until the sliding condition
is achieved
[0027] The compressibility of the powder is defined as the percentage of initial volume
lost when a sample is subjected to a compressive load, the compressive load being
provided by a 10Kg weight which is applied to a cylinder of powder of 69mm diameter
for a period of 3 minutes.
[0028] The invention will now be described further by the following Examples:
EXAMPLE 1
[0029] The following mixture was prepared by dry blending and then fed at a rate of typically
1.83 kg per minute onto a horizontal fluidised bed. No water was added. The inital
part of the fluidised bed was heated to above 80°C and retained at this temperature
during the experiment.
Material |
% W/W |
Sodium Tripolyphosphate |
44.8 |
Sodium Carbonate |
23.4 |
Sodium Carboxy-Methyl Cellulose |
2.40 |
Sodium Sulphate |
29.00 |
Optical Brightener (TINOPAL* CBS-X) |
0.40 |
*TINOPAL is a Trade Mark of Ciba-Geigy. |
[0030] Two liquids, as defined below, were sprayed sequentially along the fluidising bed
onto the fluidised powder.
LIQUID 1. Do Decyl Benzene Sulphonic Acid (DDBSA) at a spray rate of 390g/min.
LIQUID 2. A solution comprising
|
|
% W/W |
a) |
Sodium Silicate (2:1 SiO₂:Na₂O) |
40.00 |
b) |
Pigment blue 15:1 (46% Dispersion |
0.18 |
c) |
Tetra sodium salt of ethylene diamine tetra acetic acid |
3.66 |
d) |
Water |
56.16 |
[0031] The solution was applied at a spray rate of 390g/min. The combined addition of alkyl
aryl sulphonic acid and silicate solution equated to a 30.0% w/w combined percentage
liquid additions.
[0032] After processing, chemical analysis indicated the powders had the following chemical
content.
|
% W/W |
Active Detergent (calculated as Sodium Alkyl Aryl Sulphonate - Molecular Weight 322) |
15.6 |
Sodium Tripolyphosphate (calculated as P₂O₅) |
32.4 |
Moisture |
1.53 |
[0033] The product was a dust free, free flowing granular agglomerate.
EXAMPLE 2
[0034] The following powder mixtures were prepared and used as in EXAMPLE 1.
|
% W/W |
Sodium Tripolyphosphate |
57.60 |
Sodium Carbonate |
23.00 |
Sodium Carboxy-Methyl Cellulose |
2.40 |
Sodium Sulphate |
16.60 |
Optical Brightener (TINOPAL* CBS-X) |
0.40 |
*TINOPAL is a Trade Mark of Ciba-Geigy. |
[0035] The composition of the two liquids sprayed along the fluidised bed was as in EXAMPLE
1.
LIQUID 1 was applied at a spray rate of 600g/min.
LIQUID 2 was applied at a spray rate of 390g/min
[0036] The combined addition of alkyl aryl sulphonic and silicate solultion equated to a
combined percentage liquid addition of 35.0% W/W.
[0037] After processing, chemical analysis indicated the powder had the following chemical
content.
|
% W.W. |
Active Detergent (calculated as Sodium Alkyl Aryl Sulphonate - Molecular Weight 332) |
23.9 |
Sodium Tripolyphosphate (calculated as P₂O5) |
41.7 |
Moisture |
1.73 |
[0038] The powder produced was a dust free, free flowing granular agglomerate.
[0039] The method enabled a liquid addition of 35.0% W/W to the fluid bed which is comfortably
in excess of the limit of 20% imposed by known methods.
[0040] Active matter content was as high as 23.9%, which is almost twice the maximum amount
of 12% of active matter achieved by known methods, utilising a fluid bed apparatus.
[0041] The amount of alkyl aryl sulphonic acid adsorped onto the tripolyphosphate and other
alkalies present was well in excess of the previously know adsorptive figures quoted
in literature as shown in TABLE A.
[0042] In EXAMPLE 1 the theoretical maximum for successful adsorption of alkyl aryl sulphonic
acid is calculated to be 15.075g of sulphonic acid per 100 g of initial powder mixture.
The practical result of use of the claimed method is calculated to be 21.311g of sulphonic
acid per 100g of initial powder mixture which is well in excess of the results from
previously known methods.
[0043] Similarly in EXAMPLE 2 the figures for theoretical maximum and practical results
are 19.226g and 32.311g of alkyl aryl sulphonic acid per 100g of initial powder mixture.
[0044] Prior art methods of dry neutralisation in whatever apparatus have always assumed
the presence of added water and have always restricted the ratio of the amount of
alkyl aryl sulphonates to the amount of alkali to a limit which the invention successfully
exceeds. The present invention provides a cost efficient method of producing a high
active, non-dusty, free flowing, stable anionic detergent powder which may be easily
handled and easily stored.
1. A method of producing a free flowing, high active, anionic detergent comprising
the step of adsorbing an anionic surfactant acid onto a powdered or granular material
to form an agglomerate without the addition of water in the agglomeration stage.
2. A method of producing a free flowing, high active detergent as claimed in claim
1, wherein said material is heated and is substantially dry prior to adsorption of
the anionic surfactant acid.
3 A method of producing a free flowing, high active detergent as claimed in claim
1 or claim 2, wherein at least a part of the anionic surfactant acid is adsorbed onto
the powdered or granular material in a fluidised bed.
4 A method of producing a free flowing, high active detergent as claimed in any preceding
claim, wherein the anionic surfactant acid comprises any of the following alone or
in combination: alkyl aryl sulphonic acids, fatty acid sulphonic acids, olefin sulphonic
acids, fatty alcohol ether sulphuric acid, fatty methyl ester sulphonic acid, alkane
sulphonic acids.
5. A method of producing a free flowing, high active detergent, wherein the anionic
surfactant acid comprises any of the following either alone or in combination: alkyl
aryl sulphonic acids containing an alkyl group with 9-20 carbon atoms and a sulphonic
acid or sulphuric acid ester group, fatty acid sulphuric acids obtained by sulphating
alcohols with 8-18 carbon atom chains and linear straight chain alkyl benzene sulphonic
acids in which the average number of carbon atoms in the alkyl group is from 11 to
13.
6. A method of producing a free flowing, high active detergent as claimed in any preceding
claim, wherein the amount of anionic surfactant acid is in the range from 12% to 40%
by weight based on the weight of the final product.
7. A method of producing a free flowing, high active detergent as claimed in any preceding
claim, wherein the amount of anionic surfactant acid is in the range from 12% to 35%
by weight based on the weight of the final product.
8. A method of producing a free flowing, high active detergent as claimed in any preceding
claim, wherein the amount of anionic surfactant acid is in the range from 12% to 30%
by weight based on the weight of the final product.
9. A method of producing a free flowing, high active detergent as claimed in any preceding
claim, wherein said powdered or granular material comprises alkaline material.
10. A method of producing a free flowing, high active detergent as claimed in any
preceding claim, wherein said powdered or granular material comprises solely or in
combination with other ingredients, a phosphate, carbonate, bicarbonate, sulphate
or silicate salt of an alkali metal or an alkaline earth metal.
11. A method of producing a free flowing, high active detergent as claimed in any
preceding claim, wherein the amount of powdered or granular material is in the range
from 60 to 95% by weight based on the weight of the final product.
12. A method of producing a free flowing, high active detergent as claimed in any
preceding claim, wherein said method further comprises the coating of said agglomerate
with a silicate.
13. A method of producing a free flowing, high active detergent as claimed in any
preceding claim, wherein said method further comprises the coating of said agglomerate
with an alkali, or an alkaline salt.
14. A free flowing, high active anionic detergent prepared by the method as claimed
in any preceding claim.
15. A free flowing, high active, anionic, powdered or granular detergent composition
comprising an anionic surfactant acid adsorped onto a powdered or granular material
wherein at least 96% by weight of said detergent composition has a particle size distribution
substantially within the range from 250 microns to 1700 microns.
16. A free flowing, high active, anionic powdered or granular detergent composition
as claimed in claim 15, wherein the anionic surfactant acid is present in the range
from 12 to 40% by weight of the total composition and the powdered or granular material
is present within the range from 20 to 50% by weight at the total composition.
17. A free flowing, high active, anionic, powdered or granular detergent composition
comprising an anionic surfactant acid adsorped onto a powdered or granular material
anionic surfactant acid being present in the range from 12 to 40% by weight of the
total composition and the powdered or granular material being present within the range
from 20 to 50% by weight of the total composition.
18. A free flowing, high active, anionic powdered or granular detergent composition
as claimed in claim 17, wherein at least 96% by weight of said detergent composition
has a particle size distribution substantially within the range from 250 microns to
1700 microns.
19. A free flowing, high active, anionic, powdered or granular detergent composition
as claimed in any of claims 15 to 18, wherein said detergent composition has an average
particle size substantially in the range from 1100 to 1300 microns.
20. A free flowing, high active, anionic, powdered or granular detergent composition
as claimed in any of claims 15 to 19, wherein said detergent composition has an untapped
bulk density in the range from 600 to 720 gm/ml.
21. A free flowing, high active, anionic powdered or granular detergent composition
as claimed in any of claims 15 to 20, wherein said detergent composition has a tapped
bulk density in the range from 730 to 830 gm/ml.
22. A free flowing, high active, anionic, powdered or granular detergent composition
as claimed in any of claims 15 to 21, wherein said detergent composition has a mositure
content less than 4% by weight of the total composition.
23. A free flowing, high active, anionic powdered or granular detergent composition
as claimed in any of claims 15 to 22, wherein said detergent composition has an angle
of repose within the range from 36° to 41°.
24. A free flowing, high active, anionic, powdered or granular detergent composition
as claimed in any of claims 15 to 23, wherein said detergent composition has a sliding
angle in the range from 25° to 28°.
25. A free flowing, high active, anionic powdered or granular detergent composition
as claimed in any of claims 15 to 24, wherein said detergent composition has a flowrate
in the range from 30 to 41 cc/sec.
26. A free flowing, high active, anionic, powdered or granular detergent composition
as claimed in any of claims 15 to 25, wherein said detergent composition has a compressibility
in the range from 7 to 15%.
27. A free flowing, high active, anionic powdered or granular detergent composition
as claimed in any of claims 15 to 26 wherein the anionic surfactant acid is present
in the range from 12 to 30% by weight of the total composition.
28. A free flowing, high active, anionic, powdered or granular detergent composition
as claimed in any of claims 15 to 27, wherein said powdered or granular material is
present in the range from 30 to 40% by weight of the total composition.
29. A free flowing, high active, anionic powdered or granular detergent composition
as claimed in any of claims 15 to 28, wherein said powdered or granular material comprises
alkaline material.
30. A free flowing, high active, anionic, powdered or granular detergent composition
as claimed in any of claims 15 to 29, wherein said powdered or granular material comprises
any of the following either alone or in combination: a phosphate, carbonate, bicarbonate,
sulphate, or silicate salt of an alkali metal or an alkaline earth metal.
31. A free flowing, high active, anionic, powdered or granular detergent as claimed
in any of claims 15 to 30, wherein said anionic surfactant acid comprises any of the
following alone or in combination: alkyl aryl sulphonic acids, fatty acid sulphonic
acids, olefin sulphonic acids, fatty alcohol ether sulphuric acid, fatty methyl ester
sulphonic acid, alkane sulphonic acids.
32. A free flowing, high active, anionic powdered or granular detergent composition
as claimed in any of claims 15 to 31, wherein said anionic surfactant acid comprises
any of the following ether alone or in combination: alkyl aryl sulphonic acids containing
an alkyl group with 9-20 carbon atoms and a sulphonic acid or sulphuric acid ester
group, fatty acid sulphuric acids obtained by sulphating alcohols with 8-18 carbon
atom chains, and linear straight chain alkyl benzene sulphonic acids in which the
average number of carbon atoms in the alkyl group is from 11 to 13.