EP0273688B1 - Procédé pour la fabrication d'une poudre détergente séchée par pulvérisation - Google Patents

Procédé pour la fabrication d'une poudre détergente séchée par pulvérisation Download PDF

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Publication number
EP0273688B1
EP0273688B1 EP87311311A EP87311311A EP0273688B1 EP 0273688 B1 EP0273688 B1 EP 0273688B1 EP 87311311 A EP87311311 A EP 87311311A EP 87311311 A EP87311311 A EP 87311311A EP 0273688 B1 EP0273688 B1 EP 0273688B1
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EP
European Patent Office
Prior art keywords
slurry
detergent
active compound
wholly
acid form
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP87311311A
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German (de)
English (en)
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EP0273688A1 (fr
Inventor
Elfed Huw Evans
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Publication of EP0273688A1 publication Critical patent/EP0273688A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/02—Preparation in the form of powder by spray drying

Definitions

  • the present invention relates to a process for the production of detergent powders containing anionic detergent-active compounds, by slurry-making and spray-drying.
  • Spray-dried detergent powders are generally produced by preparing an aqueous slurry of detergent-active compounds, builder and other salts, sodium silicate, fluorescers and other non-heat-sensitive ingredients, and then spray-drying the slurry to form a free-flowing powder. Ingredients unsuitable for spray-drying, such as bleaches, perfumes and enzymes, may be postdosed subsequently to the spray-dried base powder.
  • Anionic detergent-active compounds such as alkylbensene sulphonates are incorporated in spray-dried detergent powders via the slurry.
  • Alkylbenzene sulphonates are manufactured by sulphonation of the corresponding alkylbensene to give a sulphonic acid which can then be neutralised with a suitable base, for example, sodium or potassium hydroxide, sodium carbonate, ammonia or triethanolamine, to give the salt of the desired cation.
  • a suitable base for example, sodium or potassium hydroxide, sodium carbonate, ammonia or triethanolamine, to give the salt of the desired cation.
  • the sodium salt which is the most commonly used salt in detergent powders, is generally prepared by neutralisation with aqueous sodium hydroxide solution to yield a paste containing 50% or more water, and that material can be incorporated directly in the slurry.
  • EP-A-242138 published 21.10.87, forms part of the state of the art by reason of Article 54(3) EPC. This document discloses a procedure in which alkylbenzene sulphonic acid is added to slurry containing sodium carbonate.
  • a significant characteristic of the invention is the incorporation of an anionic detergent-active compound wholly or predominantly in its acid form at a relatively late stage in the slurry-making process, when a large reservoir of alkaline material is already present in the slurry.
  • the invention is applicable to the incorporation of any anionic detergent-active compound having a stable acid form. It is of especial interest in relation to sulphonic acids, especially alkylaryl sulphonic acids, more especially C8-C15 alkylbenzene sulphonic acids, both linear and branched. It may be advantageous for the sulphonic acid to be partially neutralised, for example, up to 10% by weight neutralised, before introduction into the slurry-making vessel: a neutralisation level of about 5% appears to be especially beneficial. This can be helpful in stabilising the sulphonic acid and preventing it from darkening in colour during storage. When the sodium salt of the sulphonic acid is desired, such preneutralisation is conveniently carried out with aqueous sodium hydroxide solution. For convenience, acid or partially neutralised acid added to the slurry will be referred to hereinafter simply as "sulphonic acid".
  • alkaline material As is required fully to neutralise the sulphonic acid.
  • This will generally be constituted in part by a base such as sodium hydroxide which is especially intended for the purpose, in part by alkaline sodium salts present as builders, and possibly in part by alkaline sodium silicate.
  • the detergent composition prepared in accordance with the invention is to include alkaline sodium silicate
  • the silicate is preferably incorporated in the slurry before the sulphonic acid, and thus contributes to the alkaline material, mentioned previously, that must be present in at least a twofold amount relative to the sulphonic acid at the time when the latter component is added.
  • alkaline builder salts present in the slurry when the sulphonic acid is added are sodium tripolyphosphate, sodium carbonate and mixtures of these. These materials are commonly used in detergent powders as builders which sequester or precipitate calcium and magnesium salts in the wash liquor. They generally comprise at least 25% by weight of the detergent powder so that if they are incorporated in the slurry before addition of the sulphonic acid they can serve as a large alkaline buffer to prevent or minimise any adverse interaction between sodium silicate and sulphonic acid. Efficient stirring in the slurry-making vessel also helps to eliminate such adverse interaction.
  • any alkali added to the slurry specifically for neutralisation of the sulphonic acid makes an additional contribution to the reservoir of alkaline material in the slurry.
  • the amount of sodium hydroxide required to neutralise the sulphonic acid completely generally ranges from 10 to 20g per 100g sulphonic acid. This relatively large variation occurs because the amount of sulphuric acid present as a by-product in the sulphonic acid can vary quite widely: it is likely to be higher in sulphonic acids prepared by oleum sulphonation than in sulphonic acids prepared by sulphur trioxide sulphonation.
  • Sodium hydroxide solution of specific gravity 1.5 is conveniently used as the neutralising alkali.
  • a neutralising alkali When a neutralising alkali is used, it need not be introduced into the slurry before the sulphonic acid, provided that sufficient alkaline material from other sources is present when the sulphonic acid is added. It may be preferable to add the alkali and sulphonic acid simultaneously.
  • the process of the invention gives several worthwhile advantages.
  • Sodium silicate is a desirable ingredient in detergent compositions because it improves powder structure, prevents corrosion of washing machine parts in use, and provides building capacity (towards magnesium ions).
  • the process of the invention is, however, also beneficial for the production of silicate-free powders and gives other advantages applicable both to silicate-containing and to silicate-free powders.
  • a less aerated slurry is also obtained by the process of the invention, especially when other, high-foaming anionic, surfactants such as alkyl sulphates or alkyl ether sulphates are absent.
  • a less aerated slurry gives a spray-dried powder of higher particle density, and allows high bulk density powders to be prepared without the need for a separate deaeration step.
  • a less aerated slurry is also less bulky so that larger batches of slurry can be processed in a given slurry-making vessel: for powders containing high levels of alkylbenzene sulphonate (20% or more) an increase in batch size of up to 20% has been achieved, leading to a corresponding increase in the output of the slurry making plant. Pumping of a less aerated slurry is also easier because its viscosity is lower and cavitation problems are less likely to occur.
  • sodium tripolyphosphate is a major building and structuring component of the powder: in a preferred embodiment of the invention, all sodium tripolyphosphate is added before the addition of the sulphonic acid.
  • the temperature of the slurry at the time at which the sodium tripolyphosphate is added is then lower than in the prior art process in which the sulphonic acid neutralisation step has already occurred and raised the slurry temperature.
  • the sodium tripolyphosphate can dissolve and hydrate more quickly at a lower temperature: this ensures that less degradation of the tripolyphosphate occurs during spray-drying, and also favours the growth of very small sodium tripolyphosphate hexahydrate crystals in the slurry, thus giving spray-dried powders of improved structure and absorptivity.
  • a period of at least 2 minutes may be allowed to lapse between addition of the sodium tripolyphosphate and addition of the sulphonic acid to the slurry, in order to maximise hydration of the sodium tripolyphosphate before any temperature increase due to the neutralisation reaction occurs.
  • the finished slurry is pumped, first via low-pressure pipes and then via high-pressure pipes, to a distribution manifold for the atomising nozzles of a spray-drying tower.
  • the sulphonic acid in the slurry-making vessel itself, it may be injected either into the low-pressure pump or pipes, or into the high-pressure pump or pipes. It has been found especially beneficial to inject the sulphonic acid into the high-pressure pump or pipes, very shortly before the slurry arrives at the spray-nozzle distribution manifold.
  • Alkylbenzene sulphonic acids are fairly viscous liquids at ambient temperatures but can be pumped without too much difficulty using positive displacement pumps. It has been found that sulphonic acid can be used at ambient temperature if it is to be added to the slurry-making vessel. When the alternative procedure of injection into a slurry transfer pump or pipe is to be used, however, the sulphonic acid is preferably heated to a temperature of about 50 to 60°C to lower its viscosity to a value at which accurate metering with a pump of the piston type is possible.
  • An alternative method of reducing the viscosity of the sulphonic acid is to premix it with a viscosity-lowering ingredient, especially a nonionic surfactant, but this method is suitable only for preparing powders in which the viscosity-lowering ingredient is required.
  • the process of the invention may be used with advantage to prepare any spray-dried detergent powder containing an anionic detergent-active compound having a stable acid form.
  • an anionic detergent-active compound having a stable acid form This will normally be a sulphonate-type anionic detergent, especially an alkylaryl sulphonate and more especially a C8-C15 linear alkylbenzene sulphonate.
  • Other anionic detergent-active compounds may also be present, for example, primary and secondary alkyl sulphates, olefin sulphonates, alkane sulphonates, alkyl ether sulphates, and fatty acid ester sulphonates.
  • Nonionic surfactants may also be used in detergent powders prepared according to the invention. These include the primary and secondary alcohol ethoxylates, especially the C12-C15 primary and secondary alcohols ethoxylated with an average of from 3 to 20 moles of ethylene oxide per mole of alcohol.
  • soaps of fatty acids are preferably sodium soap derived from naturally occurring fatty acids, for example, the fatty acids from coconut oil, beef tallow, sunflower or hardened rape seed oil.
  • the total amount of detergent-active material (surfactant), excluding soap, in detergent powders prepared according to the invention is generally within the range of from 5 to 40% by weight.
  • the preferred range is from 5 to 20% by weight, with a weight ratio of anionic surfactant to nonionic surfactant not exceeding 10:1, and preferably not exceeding 6:1.
  • the present invention is especially applicable to the manufacture of medium- and high-sudsing powders containing higher levels of anionic surfactant and/or higher ratios of anionic surfactant to nonionic surfactant.
  • Detergent powders prepared in accordance with the invention will also comprise one or more detergency builders, suitably in an amount of from 10 to 60% by weight.
  • Detergency builders are very well known to those skilled in the art and include sodium tripolyphosphate, orthophosphate and pyrophosphate; crystalline and amorphous sodium aluminosilicate; sodium carbonate; and monomeric and polymeric polycarboxylates, for example, sodium citrate, nitrilotriacetate and polyacrylate, and acrylic copolymers.
  • at least some of the builders incorporated in the powder must be alkaline salts.
  • inorganic salts without a detergency building function for example, sodium sulphate, may also be included in detergent powders prepared according to the invention.
  • Detergent powders prepared according to the invention will also generally contain various additives to enhance the efficiency of the product, notably bleach systems, antiredeposition agents, fluorescers, lather suppressors, enzymes and perfumes. These may be added to the slurry or postdosed into the spray-dried powder in accordance with their known suitability for undergoing spray-drying processes.
  • a slurry was prepared in a batch slurry-making apparatus from the following ingredients, added in the order listed:
  • the contents of the slurry-making vessel were stirred continuously during the preparation of the slurry.
  • the temperature of the slurry rose from about 80°C to about 85°. It was noticeable that much less air than usual was entrained in the slurry during its preparation.
  • the slurry was transferred via low and high-pressure transfer pipes to a spray-drying tower, 162 parts of a nonionic surfactant being injected into the high-pressure slurry transfer pipe just before it entered the spray jet distribution manifold.
  • the solubility of the powder was assessed by stirring 4g into 400 ml of water at a temperature of 40°C for 2 minutes and then filtering the undissolved material.
  • the weight of undissolved material under these test conditions should be less than 0.16g for a detergent powder, equivalent to 4% undissolved powder: the weight of undissolved material is greatly affected by the amount of insoluble siliceous material present.
  • Example 1 Under the above testing conditions, the level of undissolved material in the detergent powder of Example 1 was very satisfactory at 1.1%.
  • the sulphonic acid used in Example 1 had been prepared by sulphonating an alkylbenzene with sulphur trioxide and air on a falling film reactor. It was of very good quality and contained only 0.9% by weight of free sulphuric acid.
  • This Example describes the preparation of a high-sudsing detergent powder containing 20% by weight of alkylbenzene sulphonate.
  • the alkylbenzene sulphonic acid used had been prepared by reacting the corresponding alkylbenzene directly with 20% oleum and then allowing the resulting mixture of sulphonic and sulphuric acids to separate into two layers; its sulphuric acid content was 6.9% by weight.
  • a slurry was prepared in a batch slurry-making vessel by adding the following ingredients with mixing, in the order stated:
  • the slurry temperature before addition of the sodium tripolyphosphate was 56°C and this rose to 72°C after a 2-minute period to allow the sodium tripolyphosphate to hydrate: this temperature rise indicated that 93% hydration has been achieved.
  • the temperature rose by a further 22°C to a final value of 94°C; at no time during the slurry-making process was heat from an external source applied to the vessel.
  • the degree of aeration of the slurry after all the slurry ingredients had been added was significantly less than normal.
  • the slurry was easy to pump.
  • the slurry was transferred to a spray-drying tower and spray-dried to give a free-flowing powder having a bulk density of 413 g/litre.
  • Example 1 The standard dissolution test described in Example 1 established that the dissolving properties of the detergent powder were very good. The amount of undissolved material remaining after 2 minutes' stirring was only 0.1%. This result confirmed that no adverse reaction between the sulphonic acid and the sodium silicate had occurred in the slurry.
  • Example 2 During addition of the sulphonic acid the temperature in the slurry-making vessel rose by 42°C. The extent of hydration of the sodium tripolyphosphate was 83%. The slurry was considerably more aerated than that of Example 2, so that a smaller batch size (about 80% of that of Example 2) had to be used. The slurry was spray-dried to form a powder having a bulk density of 390 g/litre.
  • This Example illustrates an alternative procedure according to the invention, in which alkylbenzene sulphonic acid was injected continuously into the slurry immediately before the slurry reached the distribution manifold for the spray nozzles of the spray-drying tower.
  • the slurry was pumped through low and high-pressure pipes to the distribution manifold.
  • the alkylbenzene sulphonic acid used in Example 1 (689 parts) was injected continuously at a pressure of 50 bar into the slurry just before it entered the manifold: the slurry pressure at this point was 45 bar.
  • a simple static in-line mixer installed after the injection point ensured that the sulphonic acid mixed well with the slurry. Further and more intense local mixing also took place in the high shear swirl type of spray jets in the spray-drying tower.
  • the spray dried detergent powder had very good physical properties and a bulk density of 490 g/litre.
  • the level of undissolved material remaining after 2 minutes' stirring in water at 40°C was 0.1%. This very low result confirmed that no unusual adverse reaction had occurred between the injected sulphonic acid and the silicate in the slurry leading to the formation of high levels of insoluble siliceous material.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (12)

  1. Procédé de fabrication d'une composition détergente particulaire, qui consiste :
    (i) à préparer une bouillie aqueuse comprenant un (ou plusieurs) composé détergent actif anionique non savonneux et un (ou plusieurs) sel minéral alcalin, et
    (ii) à sécher par pulvérisation la bouillie pour former une poudre ;
    procédé dans lequel au stade (i) on incorpore un composé détergent actif anionique sous forme entièrement ou de façon prédominante acide dans la bouillie après incorporation de la matière alcaline en une proportion telle qu'un total d'au moins deux équivalents de matière alcaline par équivalent dudit détergent actif acide soit présent, à la condition que le carbonate de sodium ne soit pas utilisé comme seul sel minéral alcalin.
  2. Procédé selon la revendication 1, dans lequel le composé détergent actif anionique incorporé dans la bouillie sous forme totale ou prédominante d'un acide est l'acide alkylbenzènesulfonique en C8-15.
  3. Procédé selon la revendication 1 ou 2, dans lequel la matière alcaline incorporée dans la bouillie avant l'incorporation du détergent anionique actif sous une forme entièrement ou principalement acide contient de l'hydroxyde de sodium.
  4. Procédé selon l'une quelconque des revendications 1 à 3, dans lequel la matière alcaline incorporée dans la bouillie avant l'incorporation du détergent actif anionique sous une forme entièrement ou principalement acide comprend un (ou plusieurs) sel adjuvant alcalin.
  5. Procédé selon la revendication 4, dans lequel les sels adjuvants alcalins comprennent du tripolyphosphate de sodium, du carbonate de sodium ou un mélange de ceux-ci.
  6. Procédé selon la revendication 5, dans lequel le détergent actif sous forme entièrement ou principalement acide est incorporé dans la bouillie après l'introduction d'un tripolyphosphate de sodium.
  7. Procédé selon l'une quelconque des revendications précédentes, dans lequel la matière alcaline incorporée dans la bouillie avant l'incorporation du détergent actif anionique sous une forme entièrement ou principalement acide contient du silicate de sodium alcalin.
  8. Procédé sel on l'une quelconque des revendications précédentes, dans lequel on incorpore le détergent anionique actif sous une forme entièrement ou principalement acide dans la bouillie en une quantité qui correspond à 20% en poids ou plus de la matière détergente active neutralisée dans la poudre séchée par pulvérisation.
  9. Procédé selon l'une quelconque des revendications précédentes, dans lequel le détergent actif anionique est incorporé dans la bouillie sous une forme neutralisée de 0 à 10% en poids.
  10. Procédé selon l'une quelconque des revendications précédentes, dans lequel on prépare la bouillie dans un récipient de production de bouillie et, ensuite, on le pompe par des conduites jusqu'à une tour de séchage par pulvérisation, caractérisé en ce que le composé détergent actif anionique sous une forme entièrement ou principalement acide est injecté dans une conduite ou une pompe entre le récipient de production de bouillie et la tour de séchage par pulvérisation.
  11. Procédé selon la revendication 10, dans lequel on mélange au préalable le détergent actif anionique sous une forme entièrement ou principalement acide avec un détergent actif non ionique liquide avant l'incorporation dans la bouillie.
  12. Procédé selon la revendication 10, dans lequel on chauffe le détergent actif anionique sous une forme entièrement ou principalement acide à une température de 50 à 60°C avant de l'incorporer dans la bouillie.
EP87311311A 1986-12-23 1987-12-22 Procédé pour la fabrication d'une poudre détergente séchée par pulvérisation Expired - Lifetime EP0273688B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB868630726A GB8630726D0 (en) 1986-12-23 1986-12-23 Manufacture of spray-dried detergent powder
GB8630726 1986-12-23

Publications (2)

Publication Number Publication Date
EP0273688A1 EP0273688A1 (fr) 1988-07-06
EP0273688B1 true EP0273688B1 (fr) 1991-09-04

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EP87311311A Expired - Lifetime EP0273688B1 (fr) 1986-12-23 1987-12-22 Procédé pour la fabrication d'une poudre détergente séchée par pulvérisation

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EP (1) EP0273688B1 (fr)
DE (1) DE3772739D1 (fr)
ES (1) ES2025672T3 (fr)
GB (1) GB8630726D0 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7811980B1 (en) 2009-06-09 2010-10-12 The Procter & Gamble Company Spray-drying process
US7842657B2 (en) 2008-06-25 2010-11-30 The Procter & Gamble Company Spray-drying process

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69707480T2 (de) * 1996-08-26 2002-08-14 THE PROCTER & GAMBLE COMPANY, CINCINNATI Sprühtrocknungsverfahren zur herstellung von waschmittelzusammensetzungen unter vormischung eines modifizierten polyamins
DE19936613B4 (de) * 1999-08-04 2010-09-02 Henkel Ag & Co. Kgaa Verfahren zur Herstellung eines Waschmittels mit löslichem Buildersystem
CN103002878B (zh) 2010-04-09 2015-07-01 帕西拉制药有限公司 用于配制大直径合成膜囊泡的方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0242138A2 (fr) * 1986-04-14 1987-10-21 Unilever Plc Procédé de fabrication de détergents en poudre

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1355187A (en) * 1970-07-10 1974-06-05 Unilever Ltd Production of detergent compositions
GB1371101A (en) * 1971-02-03 1974-10-23 Unilever Ltd Production of detergent compositions
PH10800A (en) * 1972-10-31 1977-09-07 Procter & Gamble Detergent composition
GB8502032D0 (en) * 1985-01-28 1985-02-27 Unilever Plc Detergent powder

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0242138A2 (fr) * 1986-04-14 1987-10-21 Unilever Plc Procédé de fabrication de détergents en poudre

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7842657B2 (en) 2008-06-25 2010-11-30 The Procter & Gamble Company Spray-drying process
US7811980B1 (en) 2009-06-09 2010-10-12 The Procter & Gamble Company Spray-drying process

Also Published As

Publication number Publication date
ES2025672T3 (es) 1992-04-01
GB8630726D0 (en) 1987-02-04
EP0273688A1 (fr) 1988-07-06
DE3772739D1 (de) 1991-10-10

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