Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
WO 93/02168 r 1 1 3 4 1 3 lusg2/0s6sg
PROCESS FOR PRODUCING A DETER6ENT COMPOSITION CONTAINING AL~YL
SULFATE PARTICLES AND BASE ~RANULES
fIELD OF THE INYENTION
The present invention relates to a process for preparing
granular detergent compositions by separately prepar~ng spray
dried base granules and alkyl sulfa~e parttcles~ and then admixing
them.
BACK6RW ND OF THE INVENTION
The traditional ~ethod hr productng detergent granules is
spray dry~ng. Typically detergent ingredients such as
surfactant builder sillcate and carbonate are ~ixed in a tank to
for~ a slurry which ts about 35% to 50% water. This slurry is
then ato~tzed 1n a spray dry1ng tower to reduce ~oisture. It is
poss1ble to compact spray dried particles to ~ake dense detergent
gr _ les. See U.S. Patent 4 7lS 97g Hoore et al. issued
Oe:~ber 29 1987. However spray drying ~ethods generally
~ 0volve a 1tmited a~ount (less than 40X) of organic co~ponents; such as surfactant for environ~ental and safety reasons.
;~ An ~lternative ~ethod for ~ak1ng detergent particles is by
eont~nuous neutrallzation in for exa~ple ~ a continuous
neutral1zation loop follo~ed by particle for~ation. Copending
U.S. Patent Application Ser1al No. 647 338 Mueller et al filep
January 28 l9gl wh~ch is a cont~nuation-in-part of Serial No.
364~721 filed June 9 1989 describes the formation of high
actlve (>50% act~ve) detergent granules using a cont~nuous
neutral1zation system followed by part~cle fonmat~on.
Polyethylene glycol and/or certaln ethoxylated nonionic
sur~actants are added dur1ng neutral1zatiQn of alkyl sulfur1c
and/or al bl benzene sulfonic ac~ds w1th concentrated sodium
hydroxide (~ about 62X). The process and parttcles made by the
process are 1ncluded. Th~s case published as EP 90 306 139.8 on
December 12 l990.
Copending U.S. P~tent Application Serial No. 552 663
~; Ofosu-~ ante et al f~led July 16 l990 (allowed~ describes a
~ process for produc1ng ~high active detergent partt~les wh~ch
,,; .
. .
SUBSTITUTE SHEET
2~13~13
~' 93/0216~ PCI`/US92/056S9
includes reacting ~n a cont~nuous neutrallzation system the acid
form of an anionic surfactant w~th alkal~ metal hydroxide and
add~ng to the neutral~za~ion system during h rmation of the
neutralized product an ~-aminodicarboxyllc acid selected from the
group cons~st1ng of gluta~ic ac1d, aspart1c acid, amino~alon1e
actd, a~tnoad~p~c actd, and 2-a~no-2^~ethylpentanedto1c acid, or
their alkali mætal salts. H~gh actlve detergent part~cles are
tncluded.
Copending U.S. Patent Applicatlon Ser~al No. 288,759, Strauss
lo et al, f11ed Dece~ber 22, 1988 (allowed), describes a process for
~; ~ prepartng concentrated surfactant granules fro~ a h19h act~ve
surfactant paste us~ng M ne d1spersion cold granulat~on. Th1s
publ~shed as EP 89 306 335~4 on January 3, 1990.
U.S. Patent ~,534,8~9, Idtng et al, issued August 13, 1985,
dtscloses a process for ~ak1ng t~proved synthetic surfactant
akes from a roll dru~ drled paste containing sodlum alkyl
sulfate, sodium alkylbenzene sulfonate, and water-soluble
~norganic salts. The hot flakes are cooled in a low Eoisture
envtronment having a low dew po~nt.
o None of the above d~sclose the tnstant process for producing
a granular detergent compos1t10n by adm~xing high active alkyl
- sulfate part~cles wtth spray dried base granules containing little.
to no alkyl sulfate, nor to they disclose a co~posit~on compris1ng
partlcles with high levels of alkyl sulfate, and C10 16 l~near
~5 alkylbenzane sulfonate and/or C12_1g soap, along with granules
containing detergency bu~lder and soluble s~licate, which are
essentially free of alkyl sulfate.
SUMMARY OF T~E INVENTION
The preseht invent~on relates to a process for the protuct10n
of a granular detergent compos~t~on, compr~stng:
(a) spray drying a slurry comprising, by weight of the spray
dr~ed granules: less than about 2~ of alkyl sulfate;
from O to about 40Z of an~onic surfactant other than
~nDg3/02168 P~:r/us92/o56s9
- 3 - ~ 1 ~ 3 ~ 1 3
atkyl sulfate; from about 10 to 80X of detergency
butlder; and fro~ about 1 to 15% of soluble slltcate;
(b) produc1ng alkyl sulfate parttcles by steps co~pris~ng ;~
cont~nuous htgh acttve neutral~zatton, satd particles
, ~ co~prtsing, by weight of the alkyl sulfate part~cles:
fro~ about 60 to 99X Of Cl2~l8 alkrl sulfat~ ethoxylated
wlth fro~ O to about 4 ~oles of ethylene ox~de per mole
o~ alkyl sulfate; and -
(c) ~ad~1xtng sa1d spray drled granules wlth sa~d alkyl
~ sulfate parttcles, respectlvely, ~n a ratto between
about lO:9O and 99~
OESCR~PTION OF THE INVENTION
As an effort ~ntt1allr to reduce plu~e e~ission fro~ the
spray dry1ng tower and ~prove physical properttes of h~gh
~surfactant spray drted partlcles, alkyl sulf~te WtS remoYed from
tbe~spray dry1ng process and included tn a separately made ~a.lkyl
sul`fate~part~cle~. It has been found that re~oval of the alkyl
sulfate fro~ tho spray drytng tower reduces the total a~ount of
st1c b or~an~c ~atertal 1n spray drted ~base granules~, thus
i~proving lu~ping and cak~ng properttes. It has ~lso been found
thàt~add1ng the alkyl sulfate outside the spray drying tower ~ia a
separate process reduces the total organic load in the tower, thu~
réduclnQ vis~ble plu~e and reductng env~ronmental ~pact.
It has further been found that production rates for nit-P (no
phosphate) granu~es can be ~ncreased (up t~ about 30X; based on
equiva~nt tower drying loads and crutcher mo~s~ures) if the alkyl
sulfate i5 added as a separate part1cle.
It ~s bel1eved that remova~ of the other pr~dominant~
frequently-used anion1c su~factant, 11near alkylbenzene sulfonate
~LAS~, fram the spray dry1ng tower alone ~oes not result in
ptume reduc~ion as does alkyl sulfate.
Product~on af alk~yl sulfate part~cles by continuous
neutral~zat10n is described in Copendlng U.S. Patent Applicatton
Ser~al Nu~bers 647~338 and 5~2,663 c1ted above.
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93/02168 ~ ! l t 3 ~ 1 3 P~r/us92/os6s9
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rn th~s process, spray dr~et granules are made by
convent~onal spray dry~ng means. They are comprtsed of less than
about 2Z alkyl sulfate, detergency builder, and soluble sll~cate.
Other detergent ~ngredlents conventtonally added tnto spray dr1ed
granules may also be added here. Alkyl sulfate particlRs are made
~n a separate process using a continuous hlgh act~ve
neutral~zatlon system (see below). The spray drted granules are
then ad~xed ~lth the alkyl sulfate part1cles. Other convent~onal
detergent 1ngred~ents ~ay also be ad~1xed.
10A consu~er acceptable product wh1ch can be made w1th less
`~ ~ plume e~lsslon, h~gher product10n rates, and ~proved phys~cal
properties is achtevable using th~s ~nvention. Also, surfactant
leYels in a detergent compos~t10n can be easily increaset by
~; add~ng more alkyl sulfate part~cles to the co~postt~on. High
, dens~ty granular tetergent composittons ara more eas~ly made
because of the flexib~llty of mixing the alkyl sulfate parttcles.
Detergency bu~lder, soluble sil~cate, anion1c surfactant, and
other des~red lngred~ents can be atded via the spray drled
granules, and htgher levels of the alkyl sulfate, wh~ch are
o d1 ff~cult to put into the spray dried granules, can be added v~a
the alkyl sulfate part1cles.
The term part~cles is used interchangeably with granules
herein. -
I. ~lkYl Sulfate Part~cles
~5Alkyl sulfate part1cles are produced by steps comprls~ng
cont~nuous high act1ve neutralization. These part~cle~ are
comprised of, by weight of the alkyl sulfate particles, from about
60 to 9SX., preferably about 70 to 90Z. of C12 18, preferably
Cl4_l6, alkyl sulfate ethoxylated w~th from O to about 4 moles of
ethylene oxide per mole of alkyl sulfate. The alkyl sulfate ispreferably not ethoxylated (O motes of ethylene oxide)~ It ~s
preferred that the alkyl sulfate particles contain from about 4 to
25X, preferably about 8 to 14%, by weight of the alkyl sulfate
part~cles, of Clo l6, preferably Cll l4, linear alkylbenzene
-3~
~nD93/02168 P~r/usg2los6ss
~113~13
sulfonate, especlally where nonethoxylated alkyl sulfate is used.
M1xtures of alkyl sulfate and alkyl ethoxy sulfate may be used.
~here alkyl ethoxy sulfate 1s uset, fro~ about 0.5 to 2 moles of
ethylene oxide per ~ole of alkyl sylfate is preferred. Alkyl
sulfate flakes are preferr~d.
Useful alkyl sulf~te surfactants are the water soluble salts,
part1cularly th~ alkal1 metal, aJ~onium and alkanola D nium (e.g.,
monoethanola~ontu~ or trtethanolam~oniu~) salts of C12 16 ltnear
or branched alkyl sulfates.
The alkyl sulfate partlcle making process co~prises the
followlng steps.
A~ Add~tton of Ac~d and Caust1c
The f1rst step of th1s process is reacting 1n a continuous
neutral1zat10n syste~ C12 18 alkyl (ethoxylated) ~sulfuric ae1d,-~
and preferably Cl0-l6 alkyl benzene sulfonic acid or ~1xtures
thereof, w1th a sod1u~ hydroxide solution, which is greater than
or equal to about 62X by w~1ght of the hydroxide, preferably
w~thout knead1ng, to produce a neutral1zed product. The
neutral1zed product pref~rably has less than or equal to about l2S
~o ~Y weight of water.
~;~ rt is preferred that the materials of the detergent
co~position not be kneaded in the co~t~nuous neutral1zatioR
system. The cont1nuous neutral1zation system preferably does not
lnclude an a1r~ight-type kneader.
2~ It is preferred that the continuous neutralizat10n system be
substant~ally free of atdttion~l crude ma~ar~als of the detergent
composition. In other words, crude materials other than
surfactant, caustic and~or polyethylene glycol are preferably not
fed into the system~ For example, less than about 5X, preferably
less than about 1%, of add1tlonal crude mater1als should be
present in the cont1nuous neutralizatton system. It ts most
preferred that essent1ally no detergency builders or add1t10nal
.organ1c mater1a~1s are fed into the continuous neutralizat10n
system.
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~113413 :
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The C12 18 alkyl (ethoxylated) sulfurtc acid and C10-l6 alkyl
benzene sulfonic ac~d can be 0ade by any sulfation/sulfonat~on
process, but preferably are sulfonated with S03 in air in a
falling fflm reactor. See Svnthetic Deteraents, 7th ed., A.S.
Oavidson ~ B. Milwidsky, John ~1ley ~ Sons, Inc., 1987, pp.
151-168.
C12 18 alkyl sulfuric acit, and mixtures of it and C10~16
linear alkyl benzene sulfontc actd, are preferred for use heretn.
M1xtures of the two are ~ost preferred because of i~proved
d~sperslbtlity of detergent particles formed fro~ a paste ~ade
wtth the ~ixture. The two actds can be added as separate strea~s
to the conttnuous neutral~zatton--system or mt%ed before additton.
Alternatively, pastes ~ade from each separate actd can be mixed
after neutraltzation.
In thts process, it is preferred that the final ratio of
C12 18 sodiu~ alkyl sulfate to C10-l6 sodium linear alkyl benzene
sulfonate be between 75:25 and 96:4, preferably between 80:2C and
95:~.
C14_16 alkyl sulfuric actd is preferred for use in step (a)
of thts process over C12_1g alkyl sulfurtc acidr C14 15 atkyl
sulfuric acid is most preferred.
C11 14 linear alkyl benzene sulfonic acid is preferred oven
Clo~l6 alkyl ben~ene sulhnic acid. C12 13 linear alkyl benzene
sulfonlc acid ~s most preferred h r use herein.
The sodtum hydroxide used ~n step (a) to neutralize the alkyl
sulfuric acid and/or alkyl benzene sulfonic acid is greater than
or equal to about 62%, preferably greater than or equal to about
68X~ most preferably abaut 73%, by weight of the hydroxide. This
highly concentrated caustic solutton melts at a htgh temperature
so the caust~c feed system mùst be carefully matntained at the
required temperature to prevent ~cold spots~. A ncold spot~ ls
any point tn the hed syste~, pumps, metertnS syste~s, ptpes or
valves where the system has reached a temperature below the
melttng potnt of the caustic (155-f or 68.3-C for 73% caustic, for
3s
WOg3J02168 P~/US92~05CS9
~tt3913
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example). Such a ~cold spot~ can cause crystal`l~zatton of the
caust~c and blockage of the feed system. Typtcally "cold spots~
are avoided by hot water ~ackets, electrlcal trac1ng, and
etectrically heated enclosures.
The sod1u~ hydroxide is preferably present in sltght excess
of the stoich1Ometric a~ount necessary to neutral~ze the acit. If
excess alkal1nlty ~exeess causttc) in the neutral~zatton syste~
exce~ds about l.SX M20 (where M ls ~et-l), the paste ls dt~ftcutt
to circulate through the cont1nuous neutral1~atton system because
0 of lts h~gh v~scostty. If excess alkalin~ty drops below about
O.lX, the alkyl paste ~a~ not be stable long term because of
-` hydrolysis. It ts therefore preferred that excess alkalinity,
whtch can be ~e2sured by tttratton with acid, of the molten paste
~n the neutr~l1zatlon syste~ bc between about 0.1% and 1.5%, ~ore
1~ preferably bet~een about O.ZX and l.OX, most preferably between
about 0.3X and 0.7X.
The acid and causttc are put tnto the cont~nuous neutraliz-
atlon system separately, pref~rably via a htgh shear m~xer so that
they ~ix together as rapidly as posslble. The h~gh shear mixer ls
~o preferably spec1ff cally destgnet for complete mtxlng of viscous
liqutds.
6enerally, in a cont~nuous neutralization loop, the
ingredients enter the syst~m through a pump ~typically
centrifugal) wh1ch circulates the material through a heat
exchanger ~n the loop and back through the pump, where new
mRterials are introduced. The material in the system continually
recirculates, w1th as much product exiting as is enter1ng.
Product ~xits through a control valve which is usually after the
pump. The recirculat1On rat1a of a cont~nuous neutralizat1On loop
is between about 1:1 and S0:}. ~he temperature o~ the
neutralization reaction can be controlted somewhat by ad~usttng
the a~ount of cooling by the heat exchanger. The ~throughput~ can
be controlled by modifying the amount of acid and caustic
1ntroduced~
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7113~13
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The continuous neutralizatton loop should be modiff ed as
follows to practice this process:
(1) Insulate the loop;
(2) Change the centr~fugal pump to a pos1t~Ye d1splacement
pu~p, wh1ch is better able to handle very v1scous r
~ater~al;
(3) Install a caust~c feed syste~ wh~ch can handle
~; concentrated caustic (greater than about 50% sol~ds);
lo ~4) Introduce ~ater~als through a h~gh shear mtxer installed
; ~ in-line;
~-~ ' (S) Install a ~etering syste~ for the polyethylene glycol
and/or ethoxylated non~on~c surfactant, preferab~y after
the high shear mixer; ant
(6) Pos1t~on the inco~ing streams of ac1d and caustic at the
h~gh shear mixer so that the highest degree of mixing
posstble takes place.
(7) The temperature of the loop should be sufff ciently high
to ach~eve a low v1scos~ty of the paste to ensure
;:
adequate reclrculat1On and m~xing. The te~perature
should not be so high however that it causes hydrolysis
of the alkyl sulfuric acid or the alkyl sulfate.
Typical paste temperatures in the loop are between about~
180-F (82.2-C) and 230-F (llO-C), preferably about 200-F
(93.3-C3 to 210~F (98.9-C~.
. Addition of PolvethYlene Glvcol and/or Ethoxvlated Nonion~c
Surhctant
An optional second step of this process is adding to the
continuous neutralization system tur~ng formation of the
neutral~zed product polyethylene glycol of a molecular we19ht
between about 2,000 and 50,000 and/or ethoxylated non~onic
surfactant of the h nmula R(OC2H4)nOH, wherein R is a C12 18 alkyl
group or a Cg l6 alkyl phenol group and n is from about 9 to about
~- 80, witb~a ~eltSng point greater than or equal to about 120-F
3~ -
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WOg3/02168 2 1 1 3 4 1 3 pcr/us92~o5c59
(48 9 C) The wetght rat~o of the addlt~ve of step (b) to the
mixture of step (a) 1s fro~ about 1 5 to about 1 20
The polyethylene glycol and/or the ethoxylated nonlontc
surfactant can be added separately or as a m1xture to the
contlnuous neutral~zatlon syste~ at any polnt. In a
nèutral~zat~on loop these add1tlve(s) prefer~bly enter the loop
aftQr the h~gh shear ~xer ~nd before the rectrculatlon pu~p The
atdlt1ves ~ust be ~elted before addtt10n to the neutraltzatton
syste~ so that they can be ~etered ~n
These two add1tl~es are chosen because they enhance detergent
p~rfor~ance and are sol1d at below about 120-f (~8 9 C~ so that a
detergent part1cle whtch ts finm at amb1ent temperature can be
made from the neutralized paste ~hey are also chosen because
each add1t~ve acts as ~ process aid by reducing the viscos~ty of
the-h~gh acttve paste in the neutral~zer loop Thts viscostty
reductlon is part1cularly l~portant dur1ng the start up of the
neutralizer loop where the s~rfactant concentrat~on is ~ncreased
through the ~ddle phase~ reg1On. So~e alkyl sulfate ch~tn
lengths have very high ~tddle phase~ vtscosttles - typ1ctlly
o between concentrations of 40X and 60% r
Polyeth~lene glycol of a molecular weight between abou~ 2 000
and 50 000 is pre~erred over the ethoxylated nonionic surfactants,
Polyethylene glyco~ of a ~oleeular weight between about 3 000 and
20 000 pre h rably 7 000 and 12 000 ts ~ore preferred and ~4st
preferred is pol~ethylene glycol wtth a moletular we~ght of 8 00Q
PEG 8 000~) In thts invent~on the preferred wetght ratto of
polyethylene glycol to the actd/causttc mi`xture of step ~a) ts
from about 1 8 to about 1 12~ For polyethylene glycol with a
molecular weigh~ of 8 000 the preferred weight ratio is one part
3~ PEG 8 000 to ten parts actd~causttc mtxture
Polyethylene glycol is for~ed by the polymerlzatton of
ethylene glycol w~th ethglene oxtde ~n an a~ount suff~c~ent to
provtde a co~pound with a ~olecular weight between about 2 000 and
50 000 It can be obtatned from Unton Carbtde (~anbury CT)
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The preferred ethoxylated nonionic surfactant material is of
the hrmula R(OC2H4)nOH, wherein R is a C12_1g alkyl group and n
i`s from about 12 to about 30. Most preferret ~s tallow alcohol
ethoxylated with 18 moles of ethylene ox~de per mole of alcohol
; (~TAE 18~). The prefcrred ~elt~ng point for the ethoxylated
non~on~c surfactant ~s gr~ater than about 140-F (60^C).
Examples of other ethoxylated non~onics here~n are the
condensat~on products of one mole of decyl phenol w~th 9 moles of
: ethylene ox~de, one mole of dodecyl phenol with 16 moles of
lo etbylene ox~de, one mole of tetradecyl phenol with 20 moles of
: etbylene ox~de, or one mole of hexadecyl phcnol w~th 30 moles of
ethylene ox~de.
Cont~nuous neutral~zat~on can be conducted by a process
co~pr~s~ng the steps of:
(a) reacting ~n a h~gh act1ve cont~nuous neutralization loop
the ac~d form of sa~d alkyl sulfate w~th sodium
hydrox~de sotutton, wh~ch ~s abut 30 to 75% by weight of
: the hydrox~de and is present in sto1ch~ometric amount to
; slight sto~ch1O~etrlc excess, th produce a neutral1zed
~o product;
(b) adding to said cont1nuous high act~ve neutral~zat~on
loop, during formation of sa~d neutral~ted product, an
~-aminodicarboxyl~c acid selectet from the group
cons~sting of glutamic acid, aspartic acid, aminomalonic
acid, a~inoad~p~c acid, and
2-aminio-2-methyl-pentaned~otc acid, or the~r alkali
metal salts, such that partlcles formet from the product
of step (b) are compr~sed of from about 0.2 to 15 weight
% of the ~-a~inodicarbo%yl~c acid salt.
30 An alkali metal salt of glutamic acid or aspart~c acid is
preferably added to the neutral~zat~on loop. Preferably, from
about l to 10 we~ght % mono- and/or d~sod~um gluta~ate ~s added to
; the neutral~zat~on loop.
~ ~ 3
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WOg3/021C8 PCr/US92!05659
~'1 13~13
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The alkal~ metal hydroxide solution is preferably about 62 to
73X by weight of the hydroxide. Sodiu~ hydroxlde is preferred.
The neutralized product preferably has less than or equal to
about 12% by weight of water.
C. formatton of Part1cles
The th~rd step of th1s alkyl sulfate particle-making process
is for~ing detergent part~cles. Detergent particles can be formed
tn var~ous ways fro~ the neutral1zed product ex~t~ng the
cont~nuous neutral~zation system. k tesirable detergent particle
s1ze dlstribut~on has a range of about 100 to 1200 microns,
preferably about lS0 to 600 ~icrons, with an average of 300
, ~
~lcrons.
The ~olten p~ste fro~ a cont1nuous neutral1zatton loop can be
ato~ized into droplets ~n a prilling (cooling) tower. To avoid
IS~ pr~lt~ng at all, the molten paste can be s~multaneously cooled and
extruded " nd cut or ground ~nto desirable particle sizes.
A thtrd cho~ce is to allow the ~4lten paste to cool on a `~chill roll, or any heat exchange un1t unt~l it reaches a doughy
cons~stency~ at whlch point other detergent lngredients can be
0 kneaded in. The resulting dough can then be- granulated by
mechanical ~eans.
A fourth and preferred choice is to cool the molten paste
into flak~s on a chlll roll, then grind the flakes to the des~red
part~cle s~ze. If add~ttonal drying is requ~red, the cooled
~5 --flakes can be dried in a rotary drum with hot air or ~n a flu~d
bed prior to grinding.
` II. rav Dried 6ranules
The spray dried granules for use in this process can be made~
by any conventional spray drying process. They are made by a
spray drying process compris~ng spray dry~ng a slurry compris~ng,
by weight of the spray dr~ed granules: less than about 2X of alkyl
sulfate; from 0 to about 40X of anionic surfactant other than
. ..
~ ~ alkyl sul~ate; fro~ about 10 to 80% of detergency bu~lder; and
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V~l93/OQ1C8 Py~rruss2/os6ss
'113413
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from about 1 to 15%, prehrably 2 to 5%, of soluble sil~cate (as a
structurantJ.
From about S to 30X of anionic surfactant is preferred. The
anionic surfactant is preferably a satt of C10-l6 linear
alkylbenzene sulfonate. From about 10 to 20X of sodium Cll l4 r
linear alkylbenzene sutfonate is mast prehrred.
Nil-P granules are preferred. The spray dried granules are
preferabl~ co~prised of fro~ about 30 to 60 weight % of detergency
builder selected from the group consisting of carbonate, c~trate,
alu~inosillcate, and mixtures thereof. Host preferably, from
about 5 to 60 welght X of sod~um carbonate and/or water-soluble
inorganic salt, preferably sodiu~ sulfate, is included.
In one embodiment, the spray dried granules are comprised of
fro~ about S to 50 weight % of sodlu~ aluminosilicate.
Applicable spray drying processes are described in U.S.
~` Patents 4,715,979, Moore et al, issued December 29, 1981,
;; 4,963,226, Chamberlain, issued October 16, 1990, and 4,344,871, -~
Allaway et al, issued August 17, 1982, which are incorporated
here~n by reference.
o III. Admix r
The spray dr~ed granules and the alkyl sulfate particles are
ad~ixed~ respectively, at a ratio between about 10:90 and 99~
more preferably between about ~0:50 and 99:1, more preferably
between about 70:30 and 9Q:10, most preferably about 85:15.
Admixing can be by conventtonal means. Preferably, from about 2
to 40%, by weight of the ff nished composition, of detergency
builder is admixed with the (finished) granules.
The alkyl sulfate particles and said spray dried granules are
preferably ad~ixed with from about 3 to 1~X, by weight of the
f~nished composit~on, of citric acid and effective amounts of
perfume and enzy~es.
IV. Comoos~tion Claims
Two inventions are believed to be contained herein: the
process for making the co~position, and the composition itself.
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~113913
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The latter comprises alkyl sulfate particles which include from
about 4 to 20% of C10 16 linear alkylbenzene sulfonate and/or
C12-18 (coconut) soap for enhanced solub~l~ty in cold water. the
alkyl sulfate is included in the high acttve part~cles rather than
in the base granules for the.same reasons as are stated ab~ve.
Included is a granul~r detergent com4osit~on compristng bj
welght of the f1n~shed co~pos~tton:
(a) fro~ about 1 to 90X of alkyl sulfate partlcles
compr~stng by weight of the alkyl sulfate particles:
from ~bout 60 to 99% of C12 18 alkyl sulfate ethoxylated
w~th fro~ 0 to about 4 moles of ethylene oxlde per ~ole
of alkyl sulfate; fro~ about 4 to 20~ of C10_16 l~near
alkylbenzene sulfonate and/or C12-l8 soap; and :
. (b)...from about 10 to 99X of base granules comprised of by
:~ 15 weight of the granules less than about 2% alkyl sulfate
. and fro~ 0 to about 40X of anionic surfactant other than
alkyl sulfate; from about 10 to 80~ of detergency
~: builder; and fro~ about 1 to 15X of soluble silicate~; A preferred granul~r detergent co~pasttlon herein co~prises ~o by we~ght of the f~ntshed composlt~on: ~
(a) from about 1 to 90X of alkyl sulfate part kles
consistlng essent1ally of by wetght of the alkyl
sulfate part~cles from about 60 to 9~% of C~2 18 alkyl
sulfate; from about 4 to ~OX of Clo i6 l~netr
alkylbenzene sul hnate and/or C12 18 soap; from about 5
to 2~Z of polyethylen.e glycol of molecular we19ht
betwaen about 2 000 and S0 000; from about 0.2 to 15X of
an ~-aminod~carboxyl~c acid sele~tet ~rom the group
eonsi.sting of gluta~ic acid aspartic acid aminomalonic
ac~d aminoadipic acid and 2-amino-2-methyl-pentane-
d~oic ac1d or the~r alkali metal salts; and from about
1 to 15% of water and/or unreacteds; and
(b) from about 10 to 99~ of base granules comprtsed of less
than about 2% phosphorus.
~ 93/02168 P~:r/USg2/05659
~113413
- 14 -
The spray dried granules are preferably comprised of from 0
to about 40%, preferably about 2 to 40% of anionic surfactant
other than alkyl sulfate; from about 10 to 80% of detergency
builder; and fro~ about 1 to 15% of soluble s~licate.
3 The spray dried granules are pre h rably co~prised of from
about 1~ to 20X of C10 16 l~near alkylbenzene sulfonate and from
about 2 to 5X of soluble sodiu~ silicate. The spray dr~ed
g n nules are also preferably comprised of from about 30 to 60
weight % of a detergency builder selected from the group
consisting of carbonate, citrate, aluminosil~cate, and mixtures
tbereof. They are ~ore preferably co~prlsed of fro~ about S to 60
weight % of sodiu~ carbonate and~or sadlu~ sulfate.
The spray dried granules are preferably further comprised of
fro~ about 1 to lOX of a ho~opoly~er or copolymer of acryl~c acid
or its salts having an a~erage molecular weight be~ween about
1,000 and 10,000. ~he granular detergent composition herein
preferably has a phosphorus content of less than about 2.0,
preferably 0.
The foltowing are separately preferred for the alkyl sulfate
,0 ~particles of (a): 11near alkylbenzene sul h nate range is fro~
about 6 to 12% of Cll l4 LAS; alkyl sutfate range is from about 65
to 90% of C14 16 alkyl sulfate; polyethylene glycol range is fro~
about 5 to i5% at a ~olecular weight between about 4,000 and
12,000; a-aminod~carboxylic ac~d s~lt range is from about 1 to 3%
5 and is most preferably mono- and/or disodium glutamate; and the
water and/or unreacted materials range ~s from about 2 to 8X.
Preferably, the ratio of LAS to alkyl sulfate is between
about 60:40 and 80:20, most preferably ~0:30.
The composition preferably further comprises ~adm~xed on top
f both types of granules~: (c) from about 2 to 40X, preferably S
to 15%, by we~ght of the finished composition, of detergency
bu~lder, or (c) fro~ about 3 to 10%, by weight of the finished
co~position, of citric ac~d and effective amounts of perfume and
en2ymes. Enzy~es. preferably protease~ lipase and/or cellulase,
3~ ~
:~ ~
~WD93/02168 P~r/us92~o56s9
~113413
,5
comprise less than about 3X by weight of the composit~on, as do
perfumes.
The rat~o of ta) to (b), respect~vely, is preferably between
about 50:50 and 1:99, ~ost preferably between about 30:70 and
10:90. :~.
V. QDt~onal In~redients
Exa~ples of detergent surfactants which can be è~ployed
here1n are descr1bed ~n U.S. Patent 3,57g,454, Collter, issued May
la, 1971, ~ncorporated herein by reference, fro~ Column 11, line
..
45 through Column 13, l~ne 64. An extensive tiscussion of
surfactants ls cont~1n~d 1n U.S. Patent 3,936,537, incorporated
herein by reference part1cularly Column 11, line 39 through Colu~n
13, line 52. Anion~c synthetic surfactants are particularly
preferred.
Cat1Onic surfactants can also be included in such finished
detergent co~pQsit1Ons. A more co~plete disclosure of these and
~`~ other cationic surfactants useful herein can be found in U.S.
Patent 4,228,044, Ca bre, ~ssued October 14, 1980, incorporated
herèin by reference. - -
Other opt1Onal ingredients which may be included in the
detergent compositions herein include detergency builders,
chelating agents, bleaching agents, antitarnish and anticorrosion
agents, perfumè and color add1t~ves, and other opt~onal
ingredients enumerated ~n the Basker~itle patent, U.S. Patent
~S 3,936,537, from Column 19, l~ne 53 through Column 21, line 21,
incorporated herein by reference. Ch~lat~ng agents are also
described in U.S. Patent 4,663,071, Bush et al., from Column 17,
line S4 through Column 18, line 6~, incorporated herein by
reference. Suts mod1f~ers are also opt~onal ingred1ents and are
describe~ in U.S. Patents 3,933,672, issued January 20, 1976 to
Bartoletta et al., and 4,136,045, issued January 23, 1979 to Gault
et al., both incorporated herein by reference. ~etergency
. builders are enumerated in tbe Baskerville patent from Column 13,
-~ ~ line 54 through ~olumn 16, l~ne 16, and in U.S. Patent 4,663,07I,
`'"~ 93/02168 P~/US92/05659
~113~13
- 16 -
Bush et al., issued May 5, 1987, both ~ncorporated herein by
reference. Such builders ~nclude, hr example, phosphates, -
aluminosil~cates, silicates, carbonates. C10-C18 alkyl
monocarboxylates, polycarboxylates, `and polyphosphonates, and -
m1xtures thereof.
Alt parts, percentages and rattos used here~n are by weight
unless otherwfse speciff ed.
EXAMPLE I
An alkyl sulfate part~cle is made according to the following
for~ula:
~ ~ei~ht
- Sodiu~ (C14 15) alkyl sulfate 72.8Sod~um linear (C12 3J alkyl benzene sulfonate 10.6
~ater 2.0
-~ I; Sod~u~ sulfate 1.6Polyethylene glycol tM~ 8000) 8.3
Mono/d1sod~um glutamate 2.1
H~seellaneous 2.6
Detergent compositions are made by first spray drying aqueous
0 slurries according to the following for~ula: '
Weiaht X
Product A Product B
~Control) tT~st)
Sodium linear (C12.3~ alkyl- 14.88 15.39
'5 benzene sul hnate
Sodium (C14_1S) alkyl sulfate 6.38 0.00
Sodlum carbonate 10.96 I2.02
Sot~um polyacrylate (MW-4SOO) 3.51 3.8S
Sodium aluminos~licate 29.48 32.34
Sodium sil~cate (1.6 S~02:Na20) 2.41 2.64
fluorescent whitening agent 0.30 0.32
Sodium sulfate 21.S8 22.79
Polyethylene glycol (M~-8000) 1.62 0.99
Oeaerant* 0.11 0.12
- 3,
~ ~ ~ .. ........ ....
WO 93/02168 P~/US~ 659
~113413
Moisture 8.77 9.54
*Dow Corning DC-544
Spray dry~ng was performed in a ten foot diameter counter
current spray drying tower with a single nozzle at 740 lb/hr,
~nlet a1r temperature of approxtmately 390-F and exhaust
te~perature of approxl~ately 200-F.
F~n~l d~t~r~ent co~postt~ons are then madQ by ad~xing
aeeord1ng to the following formula: -
Spray drted granules 91.24 83.16
t1tr~c ac~d 5 5 5-5
0.30 0.34
Protease/A~yl~se 0.9 0.9
A~oniu~ sulfate 2 2
Alkyl sulfate parttcles . 0 8.01
~ s Suds sùppressor 0.06 0.06
;~ ** Alcalas~R~p1dase (Novo)
Product A represents a control detergent compositton,
produced as descr~b~d ~bove. Product B ts st~ilarly produced
except for the ~nclus10n of ad~ixed alkyl sulfate part~cles. It
20 1s che~tcally equ1valent to the control.
~, .
Results
- ~hen the two laundry products described above are evaluated
by consu~ers dùrtng a t~o week per10d in their homc washing
machines tstngle product blind tes~, they are rated equal.
?5 Cat~clusiQn
The alkyl sulfate part~tle/spray dried granula admix al~ows
product~on of laundry detergents which are chemically equivalent
to current detergent compositions wi~h no changs in consumer
percept10n. The admix provides the processing advantage of
1ncreased capacity and reduced organic em~ssions from the spray
drying tower.
EXAMPLE II
Alkyl sulfate part~cles as described in Example I can be used
:
in tbe fo~lowing detergent formulation.
'`; ~' ` '
, ,
. ~ .
~`") 93/02168 PCI~/USg2/0565g
Z113~13
- 18 -
~eiaht %
~ Product C Product D
:: (Control) (Test)
Sod~um linear (C12.3) a?kyl- ` 9.70 8.29
benzene sulfonate
Sod1um (C1~ 1S) alk~l sulfate 9.70 0.00
Sodtu~ c~rbonate 10 10
Sod1u~:poly~cr~rlate (M'~l 4500) 3.2 3.2 ~;
Sod~u~:alu~nosillcate 26.9 26.9
0 ~ Sod~us~s1llcate~ -6 5lo2:Na2o) 2.2 2.2
Fluore~sc nt:wh~:ten~ng agent 0.27 0.27
Sod~`u~ sulfate : 19.69 18.82
Polyethylene glycol (M~8000) 1.48 0.37
r~ o l 0 1 :~
Ad~xed-::
C~tr~c~c~d 5.5 5.5
~e 0.30 Q.34
Proteas-/~lase 0.9 0.9
o~ Ammon~u~ sulfate 2 2
Al-kyl sulfate part1cle 0 13.32
Suds suppressor 0.06 0.06
~: *Dow Corning DC-~44
: ** Alcalase/Rapidase (NoYo)
These for~ulae are again chemically e~u~valent to each other.
Product C, the control, ~s the same as Product A? the control in
Example I, except the rat1O of the surhctants a1ky1
sulfate:linear alkylbenzene sul hnate is changed from 30:70 to
50:50. Product C is no longer manufacturable by spray drying due
0 to env~ronmental constra1nts on the res~tual organics introduced
to the spray drytng tower by the addltlonal alkyl sulf~te.
Ho~ever,~Product:0 can:be produced w~th less environmental i~pact
than~:-`evèn~Product A. Product: D would be expected to perfor~
WO g3/02168 Pcr/uss2/0s6ss
~113~13
,9 :
better in contexts where a!kyl sulfate is the preferred
surfactant.
EXAMPLE III
Alkyl sulfate parttcles as descr1bed 1n Example I can be used
' in the followtng detergent for~ul~t~ons:
~e1aht %
Product E Product f
(Control) (~est)
Sodlu~ l~near (C12.3) alkyl- l9.09 17.90
b~nzene sulfon~te
Sodlu~ ~Cl4 l~) alkyl sulfate 8.18 0
Sod~u~carbonate ~ lO lO
Sod1u~ polyacrylate (M~ 4500) 3.2 3.2
Sodtu~ ~lu~1nos~1ic~te 26.9 26.9
Sodtu~stl1cate (1.6 St0?.:N~20) 2.2 2.2
Fluorescent whttenlng agent 0.27 0.27
Sod~u~ sulfate 11.82 11.06
Pol~ethylene glycol ~M~-8000) 1.48 0.55
D~aerant* 0.1 O.l
0 ~Mo1sture 8. ~ 7.78
Ad~lx~d
-
C~trlc ac~d 5.5 5~5
Perfu~e 0.30 - 0-34
Protease/Amyl?se 0.9 C.9
7~ Ammon1um sul~ate 2 2
kyl sulfate particles 0 11.24
Suds suppressor 0.06 0.06
*~ow Corning DC-544
*~ Alcalase!Rapidase ~Novo)
These formulae are che~cally equivalent to each other.
Product E, the control, is the same as Product A, the control in
Ex w le- I, except the total surfactant (11near alkylbenzene
; suifonate plus alkyl sulfate) in the fonmula is increased ~ro~
19.40% to 27.27X~ Product~E can no longer be manufactured by
35~
~ 93/02168 PCI~/USg2/05659
~ 113413
- 20 -
spray drying for reasons of safety and environmental impact and
because the physical properties of the spray drled granules would
be expected to be poor (~.e. lu~ping and cak1ng). However,
Product F îs ~anufacturable by the co~binatton of spray drying and
admix~ng of alkyl sulfate part~cles. This product would be
expected to perfon~ better than Product A on surfactant sensitiYe
soils.
EXAMPLE IV
~he hllowing detergent compositions are mate on a ten-foot
10 di _ ter counter current spray drying tower:
Control 1~
Sodium C12 3 alkylbenzene sulfonate 11.45 11.27
Sodiu~ C14.s alkyl sulfate 11.45 o
Sodium~alu~inosilicate (hydrated, 28.90 28.90
20% water)
Sod1u~ carbonate 17.00 17.00
Sodiu~ silicate (1.6 Sio2:Na2or) 5 35 5 35
Sodiu~ polyacrylate (M~-4500) 3.5 3.5
Polyethylene glycol (MW-8000) 1.2 0
Fluorescent whitening agent 0.22 ~ 0.22
Tallow fatty ac~d 1.28 1.28
~atert sodiu~ sulfate rest rest
Cake 6rade Resul~s:
Force (lbs/in2) to break cake 5.2 2.3
~5 under 20 lb load
Water by analysis 11.4 11.1
The impro~ed physical property (lower cake grade) o~ the test
product de~onstrates the advantage of minimizing the surfactant
content of spray dr~ed granules. This is true even though the
crispening aid, polyethylene glycol (MW~8000), is remoYed along
with the ~ost crisp surfactant, alkyl sulfate.
EXAMPLE V
Preparation of high active detergent material suitable for
granulation to a free flowing particulate is as follows.
,~
~r.o g3/02168 PCr/US92/OSCSg
,t.~.'113~13
- 21 -
9uiDment - .
A falling f~lm S03 reactor ~s used to prepare the aclt form
of Cl4 15 alkyl sulfate. The ac~d is fed to a h~gh acttve
neutralizat~on system supplled by Chem~thon Corporation of
Seattle, Wash1ngton. Th~s custo~ized neutralization system
consists of a recycle loop contain1ng a heat exchanger for
cooltng, a rectrculation pump sultable for hlghly viscous fluids,
and a h1gh shear mlxer w1th whtch the reactants are introduced.
In order to attaln the very low ~otsture levels necessary for
a free-flowtng, h~gh act1ve part~cles, the neutral~zatlon l~op is
mod1fted to handle 70X sodtu~ hydroxide ~elt rather than the
38-50X non~ally used with the neutral~zat1On loop. The
~odlftcat1On conststs of hot water ~ackets and electr~cal heating
of the caust~c feed syste~ to ~a~ntatn the 70X caust~c above the
caust~c melttng potnt of about 155-F (68.3-C).
Another necessary modlficat~on is the addttlon of a ~etering
system whtch in~ects the polyethylene glycol into the
~ neutral~2atlon loop at the dlscharge s~de of the hlgh shear ~xer.
- - The presence of the polyethylene glycol facilttates pumping of the
~o paste ~n the rec1rculat1On loop and reduces stick~ness of the
flnished mater~al. Polyethylene glycol having a molecular weight
of about 8000 ~s added ?s a ~elt (about 160-F or 71.1-C) at a rate
o~ about 1 part polyethylene glycol 8000 t~ lO parts Cl4 l~ sodium
alkyl sulfate active.
peration
At start up, the neutrali-zation loop is filted with water and
the system is maintained at 180-Z30-F (82..2-llO-C) by using hot
water in the heat exchanger and tn the double wall pipe comprising
the recycle loop. The recycle pump and h~Qh shear mixer are
started.
The 70% sodium hydroxide and Cl4 15 al~yl su~furic acid are
~ introduced into the btgh shear mixer and allowed to react. The
;~ sod~u~ hydrox~de and C14 15 alkyl sulfuric acid are metered to
allow a slight excess of sodium hydroxide. Material displaced
~ ~ .
.
~'' g3/02168 PCI~/US92/O!KS9
'~113413
- 22 -
from the recirculation loop is discharged through a back pressure
control valve.
As operation continues, the water is displaced from the loop
and the concentration of the sodium C14 15 alkyl sulfate is
lncreased to over 70% act~ve. Operatlon ~s continued until the
des1red a~ount of h~gh act1ve, lo~ ~o~sture ~aterial is produced.
The reactant feed ~s then shut off and the react~on loop is washed
w~th bot water.
Results
0 The ~olten paste produced is cooled and manually ground to a
fre~-flow1ng part~culate product having the follow~ng compos1t10n.
Sod~u~ C14 15 alkyl s~lfate- 74.S~
Polyethylene glycol 8000 8.5
~ter g.1
.
~5 Sodiu~ hydroxide 0.6
Unreactants/~iscellaneous 6.9
EXAMPLE VI
An alkyl sulfate particle is ~ade accord1ng to the following
for~ula:
o Nominal Wt%
~: Sodium (C14 15) alkyl sulfate 75.0
~ater 11.0
Sod~um sulfate 2.5
Polyethylene glycol ~ 8000) 7.5
~; Miscetlaneous 4.0
Detergent compositions are made by first spray drying aqueous
slurr~es according to the hllowing formula;
We~aht 70
Product A Produ~t B
(Control) (Test)
Sodiu~ linear (C12.3) alkyl- 11.90 13.25
benzene sulfonate
;~ Sod~um~(C14 1s) alkyl sulfate 11.02 0.00
~ Sod~um carbonate 18.21 18.87
~ ~ 33
~0 93/02168 Pcr/us92/o56s9
~113~ 13
- 23 -
Sodium polyacrylate (M~-~500) 3.34 4.12
Sodium alumtnosil~cate 23.39 31.40
Sodium silicate (1.6 5~02:Na2o) 1.82 1.90
Fluorescent whitentng agent 0.31 0.28
Sod~um sul~ate . 15.08 20.94
Polyethylene glycol (M~8000) 0.94 0.32
Sodtun tallow sope 1.03 1.36
Motsture 7.96 7.56
Spray dry~ng is perfor~ed ~n a ten foot diameter counter
current spray drying tower wtth a slngle nozzle at 740 lb/hr,
tnlet a~r te~pertture of approxtmately 390-F and exhaust
- temperature of approx1mately 2~0-f.
ftnal dete~gent co~postttons are then made by admixing
according to the follow~ng for~ula: -
Spray drled granules 100.00 84.37
Al bl sul~ate parttcle 0 15.63
Product A represents a control detergent composttton,~
produced as descrtbed above. Protuct B 1s stmilarly produced
except for the tncluston of ad~1xed alkyl sulfate particle. It ts
che~lcally eq~ivalent t~ the control.
Conclus10n
The alkyl sulfate particle/spray dried granule admlx allo~s
product10n of laundry detergents which are chemically equivalent
to current detergent co~posltions. The admix pr~vides the
2~ processing advantages of increased capacity and reduced organ1c
e~iss~ons from the spray drying tower.
