CA2064655C

CA2064655C - Process for preparing detergent compositions

Info

Publication number: CA2064655C
Application number: CA002064655A
Authority: CA
Inventors: Huig Euser; Philip Stephen Jackson; Amanda Jane Jeffreys; David William Roberts
Original assignee: Unilever PLC
Current assignee: Unilever PLC
Priority date: 1991-04-04
Filing date: 1992-04-01
Publication date: 1996-12-10
Anticipated expiration: 2012-04-01
Also published as: CA2064655A1; ZA922465B; EP0507402B1; IN173189B; KR950013226B1; JPH05112797A; EP0507402A1; KR920019919A; BR9201203A; DE69228330T2; JPH0778234B2; GB9107092D0; AU1405392A; AU652812B2; ES2127202T3; DE69228330D1

Abstract

A process for preparing a liquid surfactant composition comprising an anionic surfactant and a nonionic surfactant and having a relatively low water content, whereby essen-tially equimolar amounts of a neutralizing agent and a liquid acid precursor of the anionic surfactant are blended simultaneously in the presence of the nonionic surfactant.
The process is especially suitable for preparing mixtures of nonionic and primary alkyl sulphate.

Description

r 206465S
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C 7257 (R) PRO~ESS FOR pREPARINç DET~RrENT COMPOSITIONS
5 TECHNICAL FIELD ~ =
The present invention relates to a process for preparing liquid detergent compositions comprising an anionic surfac-tant and a nonionic surfactant. More in particular, it relates to a process f or the continuous preparation of a 10 liquid detergent composition comprising an anionic and a nonionic surfactant, and having a high surfactant content.
BAC~GROUNP AND PRIOR ART __ EP-A-265 203 (Unilever) discloses liquid surfactant com-15 positions which are mobile at 20 to 80 C and contain a sodium or potassium salt of an alkylbenzene sulphonate or alkyl sulphate in an amount not exceeding 80% by weight; an ethoxylated nonionic surfactant in an amount not exceeding 80% by weight; and water in an amount not exceeding 10% by 20 weight. Such liquid surfactant composition may be used as a concentrated liquid detergent, for example as a dishwashing liquid. Alternatively, the liquid surfactant composition may be sprayed onto a solid particulate absorbent material, for instance a porous spray-dried base powder having a low bulk 25 density and containing no or little actives, to form a detergent base powder having an increased bulk density.
EP-A-265 203 describes two methods for preparing such con-centrated liquid surfactant compositions. According to the 30 first method, liquid nonionic surfactant is gradually added to a neutralized alkylbenzene paste (neutralized salt) which will typically have an active matter content of about 50% by weight. The resulting viscous mixture containing more than 10% water, is then heated to evaporate a sufficient amount 35 of water such that the final water content will fall below 10%. ~

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2 C 7257 (R) According to the second method, alkylbenzene sulphonic acid is mixed with nonionic surf actant, and the mixture is subse-quently treated with a suf f icient amount of concentrated aqueous sodium hydroxide or potassium hydroxide to effect 5 partial or complete neutralization.
By means of the above processes good results may be obtained in the preparation of liquid detergent compositions.
However, the first method involves the evaporization of lO water and is theref ore time consuming and energy consuming .
A drawback of the second method is that prolonged interac-tion between a nonionic surf actant and an acid substance such as an acid anionic surfactant precursor may cause chemical degradation of the nonionic whereby dioxane may be 15 f ormed .
It is therefore an object of the present invention to provide an improved process for preparing a liquid surfac-tant composition comprising an anionic surfactant and a 20 nonionic sur~actant and having a relatively low water con-tent .
We have now f ound that an improved process f or the preparation of the afore mentioned kind of liquid suefactant 25 composition may be obtained according to the present inven-tion. In this process, essentially equimolar amounts of a liquid acid anionic surfactant precursor and a neutralizing agent are blended simultaneously in the presence of nonionic surf actant .
DEFINITION OF THE INVENTIPN
The present invention provides a process f or preparing a liquid surfactant composition comprising an anionic surfac-tant and a nonionic surfactant and having a relatively low 35 water content, whereby essentially equimolar amounts of a neutralizing agent and a liquid acid precursor of the anionic surfactant are blended simultaneously in the 2~6~65~

3 C 7257 (R) presence of the nonionic surfactant. Preferably, the process is carried out continuously, }nore preferably in a loop reactor .
5 DErrATT T~n DESCRTPTI~N QF TTTT~ INVENTION --The principle of the process of the invention is to neutralize the acid corresponding to the anionic surfactant with a neutralizing agent of a strength such as to lead to the desired low level of water in the finaI product by 10 adding these two materials to a fluid which comprises the nonionic and which acts as a solvent or diluent for the neutralized anionic surfactant.
The liquid acid corresponding to the ani~nic surfactant or 15 acid anionic surfactant precursor is usually a stable or-ganic compound which is commercially available. An example is Dobanic 113, C12-C~5 alkylbenzene sulphonic acid, which can be obtained from Shell.
20 However, the acid anionic surfactant precursors of primary alkyl sulphates are believed to be less stable and are therefore advantageously prepare~l directly before the neutralization reaction by sulphating the corresponding alcoho ls .
The neutralizing agent can be in principle any suitable alkaline substance, preferably in a concentrated aqueous solution. Concentrated aqueous solutions of an alkali metal hydroxide, such as a 50% by weight solution of sodium 30 hydroxide in water are the preferred neutralizing agents.
Alternatively, concentrated alkaline silicate solutions could be used.
The process of the invention ~or preparing the surfactant 35 mixtures may }~e carried out batch-wise, for instance by adding equimolar amounts of the anion Lc precursor a~nd the neutralizing agent to a reaction vessel containing the _ _ , . . . . . ... . .. . . .. . .

206~6~5 .

4 C 7257 (R) required amount of nonionic surfactant under continuous stirring and at a controlled temperature.
Preferably, however, the process is carried out continuous-5 ly, by f eeding the anionic surf actant precursor, the nonionic surfactant and the neutralizing agent continuously and in the required amounts into a reactor and colleeting the formed liquid surfactant compositlon after neutralization has taken place.
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Aeeording to an especially preferred embodiment of the invention, the process is carried out continuously in a loop reactor. Such loop reactors are known in the art and have, as far as we are aware, only been used for carrying out the neutralization of acid anionic surfactant precursors with aqueous sodium hydroxide.
The liquid surfactant compositions prepared according to the present invention usually correspond to the liquid surfae-tant compositions described in the European patent ap-plication 265,203, but also liquid compositions having a higher water content may be prepared. The water content of the surfactant mixtures prepared according to the present invention is less than 25% by weight, preferably less than 15% by weight. A water content of less than 10% by weight is especially preferred.
The prepared liquid surfactant compositions comprise 1 to 80%, preferably 15 to 80% by weight of one or more anionic surfactants, 10 to 99%, preferabiy 10 to 8596 by weight of one or more nonionic surfactants and as little water as possible, in order to keep the composition mobile in the temperature range of 20-95 C. Most preferred ranges for the surfactants are 30 to 70% by weight for the anionic and 30 to 70% by weight for the nonionic.

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C 7257 (R) The anionic surfactant component in the composition may be a sodium or potassium salt of a liquid acid surfactant precur-sor. It may be an alkyl sulphate, an alkylbenzene sul- -~
phonate, an alkyl ether sulphate or an fatty acid ether 5 sulphate. Particularly suitable are sodium alkyl sulphates wherein the alkyl group possesses 10 to 20, preferably 12 to 18 carbon atoms, and sodium alkyl benzene sulphonates wherein the alkyl group possesses 10 to 18 carbon atoms.
Mixtures of these anionic surfactants may also be used.
The nonionic surfactant may be any suitable nonionic surfac-tant that is liquid or readily liguefiable at temperatures up to about 80C. Suitable types of nonionic surfactants for this purpose are the ethoxylated fatty alcohols, for example a C12-C15 aliphatic alcohol ethoxylated with 2 to 10 moles of ethylene oxide per mole of alcohol. Examples of preferred nonionics are the C13-C1~ fatty alcohols condensated with 3 or 7 ethoxy groups, such as those commercially available from ICI as Synperonics A3 or A7 (Trade Marks).
The weight ratio between the anionic surfactant and the nonionic surfactant in the obtained surfactant mixture is preferably in the range of 0.125:1 to 4:1. However, com-positions having a high an anionic to nonionic ratio of more 25 than about 1. 5 :1 were found to be in general more viscous and are therefore less preferred. The especially preferred compositions prepared according to the present process have an anionic to nonionic ratio of from 0 . 2 :1 to 2 :1.
30 The liquid surfactant compositions prepared according to the process of the present invention may additionally contain free fatty acid. Thus they may additionally comprise 0.5 to 20%, preferably 2 to 15%, more preferably 2 to 796 by weight of a fatty acid having 8 to 22 carbon atoms. It is preferred 35 if the fatty acid possesses 12 to 20 carbon atoms, and more in particular 16 to 18 carbon atoms.

206~655 6 C 7257 (R) The liquid surfactant compositions prepared according to the process of the present invention may be favourably applied in a process for making high bulk density granular detergent compositions having a high active detergent level, as disclosed by EP-A- 367 339.
The invention is further illustrated by the following non-limiting Examples, in whïch parts and percentages are by weight, unless otherwise indicated.
lO The following abbreviations are used:
ABS : C12-C15 aIkylbenzene sulphonic acid, Dobanic 113 ex Shell PAS : Primary alkyl sulphate, obtained by sulphating a C12-C13 or C12-C1s alcohol (Lial 123 or 125 respectively, ex Enichem) LES : Lauryl ether sulphate NI ~ : Nonionic surfactant (ethoxylated Cl3-C15 fatty alcohol) EXAMPr ~ 1- 3 - -The following mobile liquid Alkylbenzene sulphonate/Nonionic surfactant mixtures were prepared in a conventional 25 neutralization loop reactor. The reactor is essentially in the form of a closed loop and comprises an in-line mixer.
Down stream is a heat exchanging facility and before the mixer there are three inlets which are used for the liquid acid anionic precursor, the nonionic and the aqueous sodium 3 0 hydroxide . Further up stream an outlet is provided through which the neutralized surfactant composition may be bled off, the majority of the product being recirculated into the loop .
35 For start up the loop was filled with nonionic surfactant, a blend of Synperonic A3 and Synperonic A7 in a ratio of 4:
3 Subsequently, the nonionic surfactant mixture, aqueous _ ~ ... , . , . . . . . _ _ .... .. ..

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7 C 7257 (R) 48% by weight sodium hydroxide solution and liquid anionic acid precursor (Dobanic 113) were dosed in continuously, whereby the amount of sodium hydroxide was chosen to be just sufficient to neutralize the acid. In order to obtain dif-5 ferent anionic to nonionic ratios, the nonionic feed ratewas set at three different levels. The feed rates of the starting materials and the calculated compositions of the obtained surfactant blend are-given below. The coolant temperature was 50C.

Examp 1 e 1 ~ - 2 3 Anionic acid Feed Rate (kg/hr) 10 10 10 NaOH (489~;) Feed Rate (kg/hr) 2.59 2.59 2.59 NI Feed Rate (kg/hr) 21 11. 5 5 . 25 15 ~ Anionic detergent 30.7 ~ 44.0 54.7 96 Nonionic detergent 63 . 6 48 . 3 35 . 7 ~ H2O 5 . 7 7 . 7 10 Ratio Anionic/Nonionic 0. 5 1 2 The surfactant compositions of Examples 1 and 2 were easily handleable in the loop and were mobile liquids at room temperature. The composition of Example 3 was more viscous and was therefore more difficult to handle.

EXA~Pr~FS 4-6 ._ - ~
The Examples 1-3 were repeated, except that a primary alkyl sulphate (PAS) was used as anionic surfactant and Synperonic A7 as the only nonionic surfactant. The PAS acid precursor was preparea by sulphating Lial 123, a C12-C13 alkanol with S03 in a falling film reactor (FFR). The PAS acid was fed into the loop reactor directly after it was prepared. The f eed rates of the starting materials and the calculated com-position of the obtained surfactant blend are given below.
The coolant temperature was 50C and the pH of the final composition was between 11 an~ 14.

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8 C 7257 (R) Example = = 4 ~ 5 6 Lial 123 to FFR Feed Rate (kg/hr) 10 10 10 S03 (4% in air) to FFR
Feed Rate (kg~hr) 4 . 9 4 . 9 4 . 9 5 NaOH (48%) Feed Rate (kg/hr) 4.2 4.2 4.2 NI Feed Rate (~g/hr) 29 14.5 7.25 96 Anionic detergent 31.5 45.4 58.3 96 Nonionic detergent 61.3 44.2 28.4 % HzO 6.5 9.4 12.1 10 Ratio Anionic/Nonionic 0 . 5 1 2 The surfactant compos~ tions of Examples 4 and 5 were easily handleable in the loop and were mobile liquids at room temperature. The composition of Example 6 was more viscous 15 and was therefore more difficult to handle.
EXAMPLES 7--8 ~ ~
The Examples 4-6 were repeated, under slightly different conditions and using Lial~125 (a C1z~C1s alcohol) as starting 20 alcohol. The feed rates of the starting materials and the composition of the obtained surfactant blend are given below .
Examplç ~ 7 ~ - 8 25 ~ial 125 to FFR Feed Rate (kg/hr) 10 - 10 S03 (4% in air) to FFR
Feed Rate (k~/hr) 4.42 4.42 NaOH (48%) Feed Rate (kg/hr) 4.17 4.17 NI Feed Rate (kg/hr) 25 . 2 12 . 6 30% Anionic detergent (analyzed) 28 . 4 41.1 % Nonionic detergent (calculated) 58.4 41.2 % H2O 7.1 10.0 Ratio Anionic/Nonionic 0 . 5 206~65~
g C 7257 (R) .
EX~MPL~ 9 _ ~ --The Examples 4-6 were repeated, except that lauryl ether --sulphate (LES) was used as anionic surfactant. The LES acid 5 precursor was prepared by sulphating Synperonic A3 nonionic in a falling film reactor (FFR). Synperonic A7 was used as the only nonionic. The feed rate of the starting materials and the composition of the obtained surfactant blend (as analyzed) are given below. The coolant temperature was 50C
10 and the pH of the final composition was between 11 and 14.
Exam~?le - 9 Synperonic A3 to FFR Feed Rate (kg/hr) lO
S03 (4% in air) to FFR Feed Rate (kg/hr) 4 . 54 15 NaOH (48%) Feed Rate (kg/hr) 4.1 NI Feed Rate (kg/hr) 29 % Anionic detergent 30.4 % Nonionic detergent 62 . 5 % H2O 7.1 20 Ratio Anionic/Nonionic 0.5 The obtained surfactant composition was easily handleable in the loop and was f luid at room temperature.

Claims

1. A process for preparing a liquid surfactant composition comprising an anionic surfactant and a nonionic surfactant the weight ratio of which ranges from 0.2:1 to

2:1, and having a water content of less than 25% by weight, whereby essentially equimolar amounts of a neutralizing agent and a liquid acid precursor of the anionic surfactant are blended simultaneously in the presence of a nonionic surfactant.
2. A process according to Claim 1, wherein the process is carried out continuously.

3. A process according to Claim 1, wherein the process is carried out continuously in a loop reactor.

4. A process according to Claim 1, wherein the anionic surfactant is an alkylbenzene sulphonate.

5. A process according to Claim 1, wherein the anionic surfactant is a primary alkyl sulphate.

6. A process according to Claim 1, wherein the nonionic surfactant is an ethoxylated fatty alcohol.

7. A process according to Claim 6, wherein the nonionic surfactant is a C12-C15 fatty alcohol, ethoxylated with 3 to 7 ethoxy groups.

8. A process according to Claim 1, wherein the neutralizing agent is concentrated aqueous alkali metal hydroxide.