CN1075332A - In the sulfonic acid and make the method for granulated detergent - Google Patents

Abstract

The method of manufacturing granular detergent is to express the anion in the acid form The surfactant is neutralized with a finely powdered neutralizer in a high shear mixer, The dosage is in excess of the stoichiometric amount, and the average particle size of the powder is less than 5 microns rice. Also includes free-flowing detergent combinations made by this method thing.

Description

This invention relates to a process for the dry neutralization of sulfonic acids and detergent compositions made thereby.

Granular detergents have hitherto been mainly produced by spray drying. In spray drying, the individual detergent ingredients such as surfactants and builders are slurried with up to 35-50% water. Heating and spray drying the slurry is energy intensive and expensive equipment is used. If there is an effective method that does not need to be made into a water slurry and then dried, it will be less expensive.

"Dry" neutralization (ie substantially free of water) is well known and used by detergent manufacturers to produce high bulk granular detergents, especially to neutralize the acid form of anionic surfactants.

However, it is desired to achieve agglomerates with cleaning performance comparable to conventional spray-dried granules.

It has been found that the rate and completeness of the neutralization reaction can affect the performance and dissolution rate of the detergent granules and are therefore important requirements in the industrial application of this process.

It has now surprisingly been found that the neutralization reaction is optimized if the neutralizing agent used is finely divided particles within a defined narrow range and that high bulk densities are obtained from such "dry" neutralization. Both performance and dissolution rate of the detergent granules are benefited. The bulk density of the detergent granules obtained by the process of the invention is greater than 650 g/l.

US 4515707 published on May 7, 1985 describes a dry neutralization process in which detergent sulfuric acid or sulfonic acid is neutralized with sodium carbonate powder in a high shear mixer in the presence of powdered sodium tripolyphosphate. The resulting powdery product can be used to make solid detergent bars.

Japanese Patent 60 072999 discloses a batch process in which detergent sulfonic acid, sodium carbonate, water and other selected ingredients are mixed together in a high shear mixer, then cooled to 40°C or below, and made of zeolite powder powder and granulate it.

EPA 0420317, published April 3, 1991, discloses a continuous process for mixing together detergent sulfonic acid, granular inorganic material, water and other optional ingredients in a high speed mixer/thickener. The material is then processed in a moderate speed granulator/thickener. The addition of fine powder in the second step or between the first and second steps is said to be beneficial to this aggregation process.

EPA 0430603 published on June 5, 1991 discloses a method for preparing high-active substance detergent aggregates, which uses a fine-grained filler with a high oil absorption value as a processing aid in the aggregation process.

The present invention relates to a kind of method for manufacturing granular detergent, is to neutralize an anionic surfactant in an acid form in a high-shear mixer, neutralize using a stoichiometrically excessive fine granular neutralizer, the average particle size of which is The diameter is less than 5 microns.

The present invention also includes free-flowing detergent compositions made by this method.

A dry powder stream is sent to a high shear mixer where it is mixed with a liquid or pasty anionic surfactant acid and optionally with other liquid binders. The powder stream includes a particulate neutralizing agent, typically a basic inorganic salt, and neutralization is initiated and continued in the high shear mixer. The invention is characterized in that the granular neutralizing agent in the powder stream is in the form of a finely ground powder.

The powder stream contains a particulate neutralizing agent. Preferred neutralizing agents comprise any salt of carbon or bicarbonate or mixtures thereof. The neutralizing agent should be used in stoichiometric excess relative to the anionic surfactant acid. Preferably there should be at least 5 times as much neutralizing agent as is required for stoichiometric neutralization.

The powder stream may also contain any other suitable detergent powders. Preferred powders are those active in the washing process, including zeolites, sodium tripolyphosphate, silica, silicates, polymers including copolymers of maleic and acrylic acid, carboxymethyl cellulose, optical brighteners agents, ethylenediaminetetraacetic acid, and inorganic salts such as sulfates. Other suitable ingredients operable as solids, including additional surfactants, are described below.

It has been found that the use of finely powdered neutralizers improves the cleaning performance, dissolution profile, and cake strength of the final detergent composition. The average particle size of the neutralizing agent should be less than 5 microns. The definition of the average particle diameter is described below.

It is believed that the high specific surface area of the neutralizer particles can increase the efficiency of the neutralization reaction. It is preferable that the particle size distribution is narrow and the average particle size is small. Preferably 90% by volume of the particles have an equivalent particle size of less than 10 microns.

The terms particle size and average particle size used herein are defined as follows:

The particle size of any given particle is the diameter of a sphere of the same volume as the particle.

The average (or median) particle size is the particle size such that 50% by volume of the particles are smaller than the selected particle size.

All particle size data for the neutralizer particles used herein were determined using a Malvern 2600 series optical laser.

Any type of pulverizer suitable for grinding the neutralizing agent particles to the desired particle size can be used. The disc-disc jet mill supplied by Trade Micronizer (Kent, UK) and the air sorting mill supplied by Hosokawa Micron have been found to be particularly suitable.

Suitable anionic surfactant acids include the reaction products of organic sulfuric acids having an alkyl group of about 9 to about 20 carbon atoms in the molecular structure and a sulfonic acid. Examples of such synthetic surfactants are alkylbenzene sulfonic acids, the alkyl group of which is straight or branched, having from about 9 to about 15 carbon atoms.

A particularly suitable anionic surfactant acid is a linear alkylbenzene sulfonic acid having an alkyl group of about 11 to about 13 carbon atoms.

Other useful surfactant acids include alpha-sulfonated fatty acid methyl esters, olefin sulfonates and beta-alkoxyalkane sulfonates.

Mixtures of the above may also be used.

Other types of liquid binders can also be sprayed into the high shear mixer, including aminopolyphosphate, diethylenetriaminepentaacetic acid and additional anionic surfactants (in neutralized salt form), nonionic, Cationic, amphoteric and zwitterionic surfactants.

Particularly suitable aminopolyphosphonates include diethylenetriaminepentamethylenephosphonic acid and ethylenediaminetetramethylenephosphonic acid.

Particularly suitable additional anionic surfactants are the water-soluble salts of higher fatty acids. These include "soaps," which are useful anionic surfactants in the compositions of the present invention, including alkali metal soaps, such as sodium, potassium, ammonium, and alkylammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, preferably about 12 to 18 carbon atoms. Soap can be made by direct saponification of oil or fat, or by neutralizing free fatty acids. Particularly suitable are the sodium or potassium salts of mixtures of coconut and tallow fatty acids, ie sodium or potassium tallow and coconut soaps.

Useful anionic surfactants also include water-soluble salts of organic sulfuric acid reaction products, preferably alkali metal, ammonium and alkylammonium salts, containing from about 10 to about 20 carbon atoms in the molecular structure and a sulfonate or Sulfate group. (The term "alkyl" includes the alkyl portion of an acyl group.) Such synthetic surfactants as the sodium and potassium alkyl sulfates, especially the sulfated products of higher alcohols (C ₈ -C ₁₈ ), Such alcohols are obtained, for example, by reducing glycerides of tallow or coconut oil.

Other anionic surfactants are the sodium or potassium salts of alkylphenoloxyethylene ether sulfates containing from about 1 to about 10 ethylene oxide units per molecule and from about 8 to about 12 in the alkyl group carbon atom. Also available are the sodium or potassium salts of alkyloxyethylene ether sulfates containing from about 1 to about 10 ethylene oxide units per molecule and whose alkyl groups contain from about 10 to about 20 carbon atoms.

Water-soluble nonionic surfactants may also be used as secondary surfactants in the compositions of the present invention. A particularly preferred paste contains a blend of nonionic and anionic surfactants in a ratio of from about 0.01:1 to about 1:1, preferably about 0.05:1. The amount of nonionic surfactant can reach the same amount as the main surfactant at most. Such nonionic materials include polycondensation products of organic hydrophobic compounds and alkylene oxides (having a hydrophilic character), the former being either aliphatic or aromatic. The polyoxyalkylene chain length polycondensed on the hydrophobic base can be easily adjusted to obtain a water-soluble product with a desired balance of hydrophilicity and lipophilicity.

Suitable nonionic surfactants include oxyethylene polycondensates of alkylphenols, for example polycondensates of alkylphenols having an alkyl group of about 6 to 16 carbon atoms, the alkyl groups of which may be linear or branched, About 4-25 moles of ethylene oxide per mole of alkylphenol.

A preferred nonionic substance is a water-soluble polycondensation product of an aliphatic alcohol with 8-22 carbon atoms, which may be linear or branched, with 4-25 moles of ethylene oxide per mole of alcohol. Particular preference is given to polycondensation products obtained from C ₁ -C ₁₅ alcohols, and polycondensation products of propylene glycol with ethylene oxide.

Semi-polar nonionic surfactants include water-soluble amine oxides containing one alkyl moiety of about C ₁₀ -C ₁₈ and two moieties selected from about C ₁ -C ₃ alkyl and hydroxyalkyl; water soluble Phosphine oxides containing an alkyl moiety of about C ₁₀ -C ₁₈ and two alkyl and hydroxyalkyl moieties selected from about C ₁ -C ₃ ; and water-soluble sulfones containing a moiety of about C ₁₀ -C ₁₈ an alkyl moiety and one selected from about C ₁ -C ₃ alkyl and hydroxyalkyl moieties.

Amphoteric surfactants including derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines, wherein the aliphatic moiety may be linear or branched, wherein one of each aliphatic component is about _C8 to _C18 , at least one aliphatic component contains an anionic water-soluble group.

Zwitterionic surfactants include aliphatic quaternary ammonium, phosphonium and sulfonium compounds wherein one of each aliphatic component is about _C8 - _C18 .

Available cationic surfactants include water-soluble quaternary ammonium compounds of the form R ₄ R ₅ R ₆ R ₇ N ^{+ X-} , wherein R ₄ is C ₁₀ -C ₂₀ alkyl, preferably C ₁₂ -C ₁₈ , R ₅ , R ₆ , R ₇ are each C ₁ -C ₇ alkyl; X ^- is an anion such as chloride ion. Examples of such trimethylammonium compounds include C ₁₂ -C ₁₄ alkyltrimethylammonium chloride, and cocoalkyltrimethyl-ammonium methylsulfate.

It should be noted that some of the components may be handled in solid form, in which case they should be considered part of the powder stream rather than the liquid binder.

Ratio of anionic surfactant/binder to powder stream

The ratio of liquid ingredients (anionic surfactant acid and binder) to powder ingredients is limited by the cohesiveness of the resulting powder. Preferably 1:1 to 1:4, most preferably 1:2 to 1:3.

A preferred high shear mixer is the Loedige R CB series, manufactured by Loedige Maschinenbau GmbH (Paderhorn, Germany). Its machine speed range is 500-2000 rpm, preferably about 10 seconds. The resulting granulate required further processing to yield an aggregate product, as described below. Another suitable high shear mixer is considered to be the Zig-Zig Blender (Zig-Zag Blender, manufactured by P K Niro, Denmark). Also suitable is the Eirich R batch mixer (manufactured by Gustau Eirich, Hardheim, Germany). In such a batch mixer, aggregates can be obtained directly with a mixing time of about 1 minute without further processing.

Powder material may be fed into the high shear mixer by suitable powder handling and conveying systems.

Anionic surfactant acids and other liquid materials are generally pumped into the high shear mixer through conventional nozzles, including spray nozzles.

The granules produced as described above are suitable for further processing into detergent aggregates. Said further processing comprises the continuous neutralization of the anionic surfactant acid with the particulate neutralizer. This can be further mixed in a medium speed granulator. Suitable mixers include the Loedige R KM mixer described.

The residence time therein is from 1 to 20 minutes, preferably about 5 minutes, with cooling if necessary.

Additional liquid or powder material can optionally be added to the medium speed granulator, or added between blends. Any suitable detergent ingredient may be used, including any of the foregoing.

The resulting granules can then be dried by one or more cooling or drying steps. Suitable equipment includes fluid bed dryers and air lifters available in the industry.

Fine particles (less than about 150 microns) present can be removed from the final powder stream and can be recycled to the process via the high shear mixer. Any commercially available air separation equipment may be used, if desired with appropriate filters. Suitable techniques are well known to those skilled in the art. If fines separation and recycling is effectively practiced, no or very little finely divided neutralizing agent will be detectable in the finished composition. However, if fines separation and recycling are not implemented or are not sufficiently effective, some finely divided, particulate neutralizer will be present in the finished composition.

The resulting aggregates should have a bulk density greater than 650 g/l and should be brittle particles of low porosity.

Finished detergent composition

The agglomerates can be mixed with other powder ingredients to give a free-flowing granular detergent composition. Alternatively, the aggregate can be used as the finished composition. Detergent compositions made by the process of the present invention should comprise 50-100% by weight of such aggregates, preferably 80-100%.

Other detergent ingredients can be sprayed onto the detergent granules, e.g. non-ionic surfactants, perfumes, or added to the aggregate as dry powders, e.g. bleaches and bleach activators, enzymes, polymers, including polyethylene glycol.

Example

Neutralize with C ₁₁ -C ₁₃ linear alkylbenzene sulfonic acid and sodium carbonate to prepare detergent aggregates. The sodium carbonate (ICI's light soda ash) is prepared in 5 kinds of particle sizes, that is, 5 kinds from A to E.

A). Sodium carbonate ground in a disc jet mill (from Trade Micronizing);

B). Sodium carbonate ground in an air sorting attritor (manufactured by Hosokawa Micron);

C). Sodium carbonate ground in a nail mill (from Alpine);

D).Sodium carbonate ground in a hammer mill (from Alpine);

E). Commercially available sodium carbonate (light soda ash) supplied by ICI.

Particle size of sodium carbonate (micron)* A B C D E

Median <50% 3.4 5.7 18.3 59.6 73.2

<90% 4.2 15.3 69.1 152.8 209

Specific surface area (m/ ^cm3 ) 1.68 1.31 0.98 0.25 0.25

＊The particle size of sodium carbonate is measured using MALVERN 2600 series laser particle analyzer. The median value means that 50% by volume of the particles are smaller than the given particle size. Accordingly, <90% by volume is less than the given particle size.

The following ingredients were blended in an Eirich batch mixer. Optionally add the powdered ingredients to the mixer. Add the liquid ingredients last. The aggregate was formed with a mixing time of 1 minute.

liquid material

Linear alkylbenzene sulfonic acid 23%

Phosphonic acid 2%

powder

Carbonate 21%

Zeolite 4-6%

Pentasodium tripolyphosphate 40%

Sodium silicate 6%

Other (polymers, etc.) Balance

The aggregates discharged from the Eirich mixer were prepared for physical property testing, and then made into finished products for performance testing, as listed below:

A B C D E

Rinse off stain removal (PSU) ¹ 0 -0.8 -0.6 -0.7 -1.0

Aggregate block strength2 ⁰ 2.5 6.4 10.5 9.4

Solubility Level ³ 3 1 2 2 0

Density (g/L) 850 822 602 600 664

Aggregate average particle size (micron) ⁴ 370 336 333 337 347

1. The bleachable stain removal rate is determined as follows: 85% by weight of the aggregate is mixed with 15% by weight of sodium perborate mixed with a bleach activator to obtain the final product. Use Japanese NATIONAL semi-automatic double-slot Lab J28 washing machine. Pour 70 grams of the above finished product into 30 liters of water, the water hardness is 2.0 mmol Ca ²⁺ /liter, the water temperature is 30°C, which contains 1-2 kg of clothes optimized for pollution and a set of bleachable stains (coffee, tea, black grapes) etc). The final aggregate product was compared for rinse-off stain removal with an identical formulation using a conventional spray-dried detergent. The listed scores are the scores given by the evaluation team (PUS), ranging from -4 to +4. A score of 0 means that the stain removal effect is the same as that of the control, and a negative value means that it is worse than the control.

2. Aggregate block strength is determined as follows: 100 grams of aggregate is placed in a test pan and a 10 kg load is applied for 2 minutes. The resulting block is then broken with a crossing needle. The force required to break the block is recorded as 0-11 lbs. It is stipulated that between 0-3 is qualified, 0 means that the block is easy to break, and 3 means the upper limit of the strength of the qualified block.

3. Solubility level is determined as follows: pour 90 grams of the finished product made in the same way as in item "2" into an acrylic fabric bag (the size of the bag is 20 x 40 cm), sew up the mouth of the bag, and put it in " In the washing machine used in item 2", add 30 liters of water to the machine, and the temperature is 30 ℃, and there are 1.5 kg of clean clothes. After 10 minutes of gentle agitation, the bag was opened and the amount of undissolved detergent left on the fabric was examined and rated on a scale of 0 to 4, with 0 being worst and 4 being excellent. Based on the evaluation of commercially available granular detergents, a rating of 3 and above was specified as pass.

4. The average particle size of the aggregates is measured with a standard Tyler sieve. The corresponding component weights were converted to a lognormal distribution, from which the average particle size was reported.

From the above it can be seen that the finished compositions of aggregates made from Sample A (finest ground sodium carbonate) according to the invention provide significant benefits in cleaning performance and physical properties which are comparable to those of samples B to E (carbonic acid Sodium particle size outside the scope of the present invention) aggregates compared to the results of the finished composition. The above results also show that the cleaning performance of the finished detergent composition according to the present invention (Sample A) is comparable to that of the same composition prepared by conventional spray drying.

Claims (10)

1, a kind of method of making granulated detergent, comprise that the anion surfactant (a) with sour form neutralizes with the excessive particulate state neutralizing agent (b) of stoichiometry in high shear mixer, it is characterized in that described particulate state neutralizing agent has its particle diameter of particle of 50% (volume) less than 5 microns.

2, the method for claim 1 is characterized in that, the 90%(volume of described particulate state neutralizing agent) its particle diameter is less than 10 microns.

3, the method for claim 1 is characterized in that, described anion surfactant (a) is an alkyl benzene sulphonate (ABS).

4, the method for claim 1 is characterized in that, described neutralizing agent (b) is a kind of sodium salt or the calcium salt of carbonic acid.

5, make the method for washing composition aggregate by claim 1, further comprise:

(I) reunites this detergent particles in the tablets press/enrichment machine of middling speed, and has or do not have another powder material stream;

(II) carries out drying and/or cooling.

6, by the loose density of the method manufacturing of claim 5 washing composition aggregate greater than 650 grams per liters.

7, by the washing composition aggregate of the method manufacturing of claim 5, it is characterized in that, be less than the 40%(weight of this aggregate by the sour form anion surfactant (a) and the content of particulate state neutralizing agent (b) neutral salt form anion surfactant).

8, by the washing aggregate of the method manufacturing of claim 5, it is characterized in that, be less than the 28%(weight of this aggregate by the sour form anion surfactant (a) and the content of particulate state neutralizing agent (b) neutral salt form anion surfactant).

9, a kind of free flowing granule shape cleaning composition wherein contains 50-100%(weight) the washing composition aggregate of claim 1.

10, a kind of free flowing granule shape detergent composition wherein contains 80-100%(weight) the washing composition aggregate of claim 6.