CN1077486A - High active detergent pastes - Google Patents

Abstract

A detergent slurry composition, it contains 50%-94% (weight) of anionic surfactant; 1%-30% (weight) of alkyl ethoxy sulfate and 5%-35% (weight) of water. The viscosity of the slurry at 70° C. was measured to be greater than 10 Pa·s at a shear rate of 25 s ⁻¹ . The rheological properties of the slurry make it well suited for further processing into high active detergent bars which can be used in free-flowing granular detergent compositions.

Description

The present invention relates to pumpable high active surfactant slurries suitable for further processing into detergent granules and to a process for the preparation of such slurries.

So far, granular detergents have been mainly prepared by spray drying. In the spray drying process, detergent components such as surfactants and builders are mixed with up to 35-50% water to form a slurry. The resulting slurry is heated and spray dried, which is expensive. However, a good agglomeration process is less expensive.

There are many non-spray-drying methods available in the prior art for the production of detergent granules. Most require direct neutralization of anionic surfactant acids prior to or during the granulation step.

However, these methods have certain limitations. The close coupling of the neutralization and granulation steps greatly limits the range of processing conditions used. Moreover, if the selected anionic surfactant is unstable in the acid form (such as alkyl sulfate), the sulfonation must be closely combined with the neutralization and granulation steps. As a result, the logistics and/or design of the equipment used in these processes will be greatly limited, and the complexity and difficulty of the overall process control system will be greatly increased.

It is an object of the present invention to provide a high active anionic surfactant slurry having rheological properties suitable for pumping, storage, transport between manufacturing sites and further processing by agglomeration into high active detergent granules. An important feature of the present invention is that the granulation/agglomeration step is completely separated from the sulfonation step.

It has now been found that the addition of small amounts of alkyl ethoxy sulfate greatly improves the rheological properties of the surfactant paste.

GB 2021141 published 28 November 1979 describes surfactant slurry compositions within a narrow concentration range in the fluid laminar ('G') phase.

GB 2116200 published on September 21, 1983 describes slurry compositions composed of up to about 40% (by weight) of anionic surfactants containing ethylated surfactants as dissolution aids, and the products produced by these compositions blocks.

EP 403148 published December 19, 1990 describes high active surfactant compositions containing less than 14% water. The use of process aids to reduce the viscosity of highly reactive slurries in the neutralization circuit is also mentioned. Polyethylene glycol and ethoxylated nonionic surfactants are also disclosed as suitable process aids.

High active surfactant compositions described in EP 399581, published November 28, 1990, contain ethoxylated anionic surfactants and ethoxylated nonionic surfactants.

The present invention relates to a detergent slurry composition comprising 50%-94% by weight of anionic surfactant; 1%-30% by weight of alkyl ethoxy sulfate and 5%-35% (weight) of water. The viscosity of the slurry at a temperature of 70° C. was measured to be greater than 10 Pa.S at a shear rate of 25 ^s . The invention also includes a preparation method of the slurry.

The alkyl ethoxy sulfates herein have been found to be useful as rheology modifiers to impart pure shear diluent (having one pour point) properties to the anionic surfactant paste. Thus, very thick slurries of the present invention can also be pumped without necessarily thickening during processing.

Surfactant Paste

Surfactant slurries in the form of concentrated solutions are typically described by non-Newtonian, shear-weakened rheological models with multiple pour points. These slurries typically have lower viscosities as the shear rate increases (see Figure 1).

Unexpectedly, it has now been found that under certain conditions (surfactant type, concentration, inorganic content, unsulfonated content, temperature, etc.), these slurries exhibit a rheological profile, i.e., at a certain shear rate, Viscosity increases with shear rate. This phenomenon is known as shear thickening.

The shear thickening present in these slurries often makes transport, storage and handling a very difficult task. These shear-thickened slurries that can be generated during pumping and conveying can cause significant pressure drops and can plug pipes. For the delivery of these slurries (a forceful operation) to be suitable for industrial applications, it is necessary to ensure that no shear thickening occurs and that the rheology of the slurries becomes that of a typical shear-weakened fluid (with one or no flow point).

This then allows for a complete separation of the neutralization and granulation steps to produce the finished detergent granule. The slurry can be stored between these two steps. Alternatively, transport between two manufacturing locations is also possible. This means that the preparation process is greatly simplified and becomes more flexible.

Physical Properties of Slurry

The slurry has a high viscosity, greater than 10 Pa.S at 70°C measured at a shear rate of 25 s ^-1 , but it has rheological properties to make it easy to pump and further agglomerated. The viscosity of the slurry at 70°C is preferably greater than 20 Pa.S.

The preparation method of this slurry is also described below.

The slurry is composed of two main ingredients, anionic surfactant ("active" component) and alkyl ethoxy sulfate ("rheology modifier"). A more detailed description of these components follows.

anionic surfactant

The aqueous surfactant paste contains an organic surfactant selected from anionic surfactants and mixtures thereof. Surfactants useful in the present invention are described in US 3,664,961, Norris, issued May 23, 1972, and US 3,919,678, Laughlin et al., issued December 30, 1975.

The slurry contains a high concentration of anionic surfactant, which accounts for 50%-94% of the slurry weight, preferably 60%-85%.

The anionic surfactants useful in the compositions of the present invention are water-soluble salts of higher fatty acids, ie "soaps". These include alkali metal soaps such as the sodium, potassium, ammonium and alkylammonium salts of higher fatty acids containing 8 to 24 carbon atoms, preferably about 12 to 18 carbon atoms. These soaps are obtained by direct saponification of fats and oils or by neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of fatty acid mixtures obtained from coconut oil and tallow, ie sodium or potassium tallow and coconut soap.

Useful anionic surfactants also include those having an alkyl group of about 10-20 carbon atoms and a sulfonic acid or sulfate ester group (the term "alkyl" includes the alkyl portion of an acyl group) in the molecular structure. Water-soluble salts of the organosulfur reaction products, preferably the alkali metal, ammonium and alkylammonium salts thereof. Examples of such synthetic surfactants are sodium and potassium alkyl sulfates, especially sulfuric acid from higher alcohols (C ₈ -C ₁₈ carbon atoms) such as those obtained by reduction of glycerides of tallow or coconut oil Alkyl sulphates obtained by sulfation; and sodium and potassium alkylbenzene sulphonates, wherein the alkyl group contains about 9-15 carbon atoms and is in a linear or branched structure, as described in US 2220099 and US 2477383 the types mentioned above. Particularly useful are the linear linear alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is about 11-13, abbreviated _C11 - _C13 LAS.

Other suitable anionic surfactants in the present invention include the water-soluble salts of α-sulfonated fatty acid methyl esters containing about 6-20 carbon atoms in the fatty acid group and about 1-20 carbon atoms in the ester group. 10 carbon atoms; water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids having about 2 to 9 carbon atoms in the acyl group and about 9 to 23 carbon atoms in the alkane moiety atoms; water-soluble salts of olefin sulfonates of about 12 to 24 carbon atoms; beta-alkoxyalkane sulfonates with about 1 to 3 carbon atoms in the alkyl The base part contains about 8-20 carbon atoms.

Preferred anionic surfactant pastes are linear or branched alkylbenzene sulfonates (having an alkyl group of 10-16 carbon atoms) and alkyl sulfates (having an alkyl group of 10-18 carbon atoms) mixture. These slurries are usually produced by reacting a liquid organic with sulfur trioxide to form sulfonic or sulfuric acid, and then neutralizing the acid to form a salt of the acid. The salt is the surfactant paste described throughout. The sodium salt is preferred because it facilitates final implementation relative to other neutralizing agents and the cost of NaOH is low, but it is not necessary because other agents such as KOH can also be used.

Particularly preferred surfactants for use in the present invention include: linear C ₁₁ -C ₁₃ alkylbenzene sulfonates of sodium; alpha olefin sulfonates, triethanolammonium C ₁₁ -C ₁₃ alkylbenzene sulfonates; Sulfates (tallow, coconut, palm, synthetic sources such as C ₁₄ -C ₁₅ , etc.) methyl ester sulfonates and water soluble sodium and potassium salts of coconut and tallow fatty acids.

Most preferred are sodium linear C ₁₁ -C ₁₃ alkylbenzene sulfonates, tallow alkyl sulfonates and mixtures thereof.

Alkyl Ethoxy Sulfate

The rheology modifier in this slurry is selected from the alkali metal, alkaline earth metal, ammonium or substituted ammonium salts of alkyl ethylene oxide ether sulfates (commonly known as alkyl ethoxy sulfates) containing about 1-7 units of ethylene oxide in which the alkyl group contains about 10-18 carbon atoms. The content of alkyl ethoxy sulfate is 1%-30% of the weight of the slurry, preferably 1%-15%.

Preferred are the sodium or potassium salts of alkyl ethoxy sulfates containing about 2-4 units of ethylene oxide.

Most preferred are the sulfated products of synthetic, branched _C13 - _C15 , _C14 - _C15 or _C12 - _C15 ethoxylated alcohols containing an average of about 3 units of ethylene oxide per molecule.

The ratio of anionic surfactant to alkyl ethoxy sulfate will vary with the rheological properties of the anionic surfactant chosen. This ratio can vary from 2:1 (as in the case where the anionic surfactant is tallow alkyl sulfate) to 50:1 (as in the case where the anionic surfactant is a mixture of 75% LAS and 25% tallow alkyl sulfate). case). A preferred ratio of 9:1 applies where the anionic surfactant is a C ₁₄ -C ₁₅ alkyl sulfate.

The water content of the slurry

The water content of the slurry is from 5% to 35% by weight. A low water content is preferred in order to be able to produce highly active detergent granules during the granulation/agglomeration step.

optional ingredients

Other ingredients conventionally used in detergent compositions may be present in the pastes of the present invention. These components include additional surfactants, hydrotropes, foam boosters or suppressors, antistaining and preservatives, stain suspending agents, soil release agents, bactericides, pH regulators, enzyme stabilizers, fragrances , polymers (including polyacrylates) and copolymers (including copolymers of maleic acid and acrylic acid).

Additional surfactants are selected from anionic, zwitterionic, amphoteric, cationic and nonionic surfactants.

Suitable anionic surfactants include alkyl polyglucosides, alkyl glyceryl ethoxy sulfonates and alkyl glucamides.

Suitable nonionic surfactants include polyvinyl oxide condensates of alkylphenols, and water-soluble condensation products of fatty alcohols with 8-22 carbon atoms, which can be linear or branched, per mole Alcohols contain 4-25 moles of ethylene oxide.

Semi-polar nonionic surfactants including amine oxides, phosphine oxides, and sulfoxides are also suitable for this slurry.

Amphoteric surfactants include those derived from secondary and tertiary amines, zwitterionic surfactants include those derived from fatty quaternary ammoniums, and phosphorus and sulfonium compounds are also useful.

craft

The surfactant slurry is preferably produced in a continuous neutralization system, such as the continuous neutralization loop commercially available from USA Chemical Company in Seattle, WA. In a continuous neutralization loop, a concentrated solution of organic sulfur/sulfonic acid and metal hydroxide (approximately greater than 45% by weight hydroxide) is added to the loop where the neutralization takes place. For the present invention, it is preferred to use an alkali metal hydroxide solution with a hydroxide concentration of 50% to 75%, since higher concentrations result in less water in the final slurry.

The loop also adds additional steam, or mixes with the metal hydroxide to achieve the desired water level in the final slurry.

Organosulfur/sulfonic acids for the preparation of surfactant slurries are best prepared by the sulfonation process with _SO3 in a sedimentation film reactor, see "Synthetic Detergents" 7th edition, ASDavidson and B. Milwidsky , John Wiley and Sons, Inc., 1987, pp. 151-168.

The alkali metal hydroxide is preferably present in a slight excess of the stoichiometric amount required to neutralize the organic sulfur/sulfonic acid. However, the residual (free) alkalinity should not exceed about 1.5% _M2O (where M is a metal), otherwise the slurry would be difficult to circulate due to its high viscosity. If the residual alkalinity drops below about 0.1%, the surfactant paste will not be long-term stable due to hydrolysis. Thus, the residual alkalinity (as determined by acid titration) of the slurry in the neutralization system is preferably from about 0.1% to 1.5%, preferably from 0.2% to 1.0%, most preferably from about 0.3% to 1.0%.

The organic sulfur/sulfonic acid and the alkali metal hydroxide are placed in a continuous neutralization loop, preferably in a high shear mixer within the neutralization loop, so that they mix together as quickly as possible.

Alkyl ethoxy sulfate may be added at any suitable step in the process, including to the slurry after a neutralization cycle, or even in a storage tank, provided sufficient mechanical energy is provided to oxidize the alkyl ethoxylate. The base sulfate is finally mixed with the salt of the anionic surfactant.

A preferred embodiment of the invention is to feed the alkyl ethoxy sulfate directly into the neutralization circuit. In this way, the rheological properties of the present invention are manifested in the slurry within the neutralization circuit. And there is no need for an additional mixing step afterwards.

Another approach is to simultaneously sulfonate the ethoxylated alcohol with the sulfonation of the anionic surfactant. The two components can then be neutralized together in a neutralization circuit to obtain a slurry of the desired composition.

Further processing of slurry

The slurries of the present invention can be processed into high active detergent bars using any conventional granulation/agglomeration steps. The slurry is usually agglomerated by mixing it with dry detergent powder.

By adding other components that can increase the viscosity of the slurry and/or increase the melting point and/or reduce the viscosity to the liquid stream containing the anionic surfactant and/or other surfactants, the extremes in the preferred embodiments of the present invention can be achieved. Attractive option to further increase the concentration of surfactant in the final granule. In a preferred embodiment of the method of the invention, these ingredients can be added to the pipeline when the slurry is pumped into the agglomerator. Examples of such ingredients are various powders including zeolites, carbonates, silicas, silicates, citrates, phosphates, perborates, etc., and process aids such as starch.

powder flow

While the preferred embodiment of the method of the present invention includes the introduction of the anionic surfactant through the slurry as described above, it is still possible that a certain amount passes through the powder stream, for example in the form of a porous powder. In these embodiments, the viscosity and humidity of the powder stream must be kept low in order to prevent the anionic surfactant "loading" from increasing and resulting lumps containing too high a concentration of surfactant. The stream from the preferred agglomeration process can also be used to introduce other surfactants and/or polymers. This can be done by premixing the surfactant into one of the liquid streams, or alternatively, by introducing various liquid streams into the agglomerator. These two process implementations can lead to differences in the properties of the finished granules (partitioning, gelling, dissolution rate, etc.), especially when mixed surfactants are produced prior to granule formation. For each preferred process, these differences can then find a suitable application.

It has also been found that, using the methods described herein, high levels of certain compounds (e.g., non-ionic, citric acid) can be introduced into the final formula by any other known processing route, without certain key properties of the matrix. (caking, compression, etc.) No adverse effects.

reunion steps

As used herein, the term "agglomeration" means mixing and/or granulating the above mixture in a fine dispersing mixer at a blade tip speed of about 5 m/s - 50 m/s (unless otherwise specified) . The total residence time of the mixing and granulation process is preferably 0.1-10 minutes, more preferably 0.1-5 minutes, most preferably 0.2-4 minutes. More preferred mixing and granulation tip speeds are about 10-45 m/sec, and about 15-40 m/sec.

Any equipment, apparatus or assembly suitable for handling surfactants may be used to carry out the method of the present invention. Suitable equipment includes, for example, sedimentation membrane sulfonation reactors, digesters, esterification reactors, and the like. For mixing/agglomeration, many mixers/agglomerators are available. In a preferred embodiment, the process of the invention is carried out continuously. Particularly preferred is a mixer of the Fukae ^R FS-G series manufactured by Fukae Powtech Kogyo Co., Japan; the device is substantially in the shape of a bowl-shaped container, fed through the top, and has an agitator at the bottom, essentially Having a vertical shaft with a cutter on its side wall, the agitator and cutter operate independently of each other and their speeds are independently variable. The vessel may be fitted with a cooling jacket or, if desired, a cryogenic unit.

Other similar mixers have also been found suitable for use in the process of the present invention, including the Diosna ^R V series from Dierks and Sohne, Germany, and the Pharma Matrix ^R from TK Fielder Ltd., England. Other mixers believed to be suitable for use in the process of the present invention are the Fuji ^R VG-C series from Fuji Sangyo Co., Japan and the Roto ^R from Zanchetta and Cosrl Italy.

Other preferred suitable equipment may include Eirich ^R RV series manufactured by Gustau Eirich Hardheim, Germany, Lodige ^R FM series manufactured by Lodige Mashinenbau GmbH, Paderborn Germany (for batch mixing), Baud KM series (for continuous mixing/agglomeration ; the Drais ^R T160 series manufactured by Drais Werke GmbH, Mannheim Germany; and the Winkworth ^R RT25 series manufactured by Winkworth Machinery Ltd., Bershire, England.

Two examples of suitable mixers are the Littleford Mixer with Internal Chopping Blade, Model #FM-130-D-12, and the Cuisinart Food Processor with 7.75" (19.7cm) Blade, Model #DCX- Plus. Any other mixer capable of finely dispersing mixing and granulating with a residence time between 0.1 and 10 minutes can be used. Preferred are "turbine-type" propeller mixers with several blades on a rotating shaft. The present invention can be carried out in a batch or continuous process.

operating temperature

It is also preferred that the operating temperature be as low as possible, since this results in a higher concentration of surfactant in the finished granulate. The temperature of the agglomeration process is preferably below 100°C, more preferably 10-90°C, most preferably 20-80°C. The low operating temperatures suitable for the process of the present invention can be achieved by many methods known in the art, such as nitrogen cooling, cold water jacketing of equipment, solid _CO2 , and the like, the best method being nitrogen cooling.

final block composition

The present invention produces high density blocks for use in detergent compositions. Preferred final block components for incorporation into granular detergents have a high surfactant concentration. By increasing the concentration of surfactant, the granules/agglomerates prepared by the present invention are more suitable for various formulations. These high-surfactant granule agglomerates require only minor finishing to form the final block, thereby eliminating the need for the use in other processing steps (spray drying, dedusting, etc.) of the entire detergent preparation process. A large amount of processing aids (inorganic powder, etc.).

The blocks produced according to the invention are large, low dust and free flowing, preferably having a bulk density of about 0.4-1.2 g/cm ³ , and preferably about 0.6-0.8 g/cm ³ . The average particle size by weight of the particles of the present invention is about 200-1000 microns. The particles so produced preferably have a particle size of 200-2000 microns. A more preferred granulation temperature is about 10-60°C, most preferably about 20-50°C.

dry

The desired moisture content in the free-flowing blocks of the present invention can be adjusted to a level suitable for the desired use by drying in common powder drying equipment, such as fluid bed dryers. If a hot air fluidized bed dryer is used, care must be taken to avoid decomposition of heat-sensitive components of the granules. It is also advantageous to employ a cooling step prior to bulk storage. This step can also be carried out in a conventional fluidized bed operated with cold air. The drying/cooling of the block can also be carried out in any other equipment suitable for powder drying (such as rotary dryer, etc.).

For detergent applications, the final moisture content of the block needs to be kept low to facilitate storage and transport of the block. The exact humidity will depend on the composition of the block, but typically the concentration of free water (ie water not bound to any block seeds) is 1-8%, preferably 2-4%.

Granular detergent composition containing the block

The present invention also includes free-flowing granular detergent compositions comprising the agglomerates described above and a process for their preparation;

The detergent composition may contain additional detergency builders and powders which are added to the block to obtain a free-flowing granular detergent composition. The additional detergency aid and powder can be mixed into an aqueous slurry and spray dried to produce a powder, and/or simply added to a block as a dry powder.

In a preferred embodiment of the invention, at least a portion of the builder is added to a surfactant-free slurry whose physical properties make it suitable for spray drying by conventional methods. Free-flowing granular detergent compositions are then prepared by mixing these spray-dried granules with the agglomerates of the present invention and any other detergency aids and powders.

Decontamination Aids & Powders

Any suitable detergency aid or builder mixture or powder can be used in the methods and compositions of the present invention.

The detergent compositions of the present invention may contain a crystalline aluminosilicate ion exchange material of the formula,

wherein Z and Y are at least about 6, the molar ratio of Z to Y is about 1.0-0.4, and Z is about 10-264. Amorphous hydrated aluminosilicate materials suitable for use in the present invention have the empirical formula

wherein M is sodium, potassium, ammonium or substituted ammonium _, Z is about 0.5-2, and Y is 1, the material has a magnesium ion exchange capacity of at least about 50 meq CaCO per gram of anhydrous aluminosilicate hardness. Hydrated sodium zeolite A having a particle size of about 1-10 microns is preferred.

The aluminosilicate ion exchange aid materials of the present invention are in hydrated form and contain from about 10% to 28% by weight of water if crystalline, and may contain greater amounts of water if amorphous. More preferred crystalline aluminosilicate ion exchange materials contain from about 18% to about 22% water in their crystalline matrix. The crystalline aluminosilicate ion exchange material is also characterized by a particle size of about 0.1-10 microns. Amorphous materials are typically small, such as less than 0.01 microns. Preferred ion exchange materials have a particle size of about 0.2-4 microns. As used herein, the term "particle size" means the average particle diameter of a given weight of ion exchange material microscopically determined by conventional analytical methods, such as scanning electron microscopy. Another characteristic that the crystalline aluminosilicate ion exchange materials herein typically have is their calcium ion exchange capacity, which is at least about 200 mg equivalent _CaCO3 water hardness/g aluminosilicate (on an anhydrous basis), typically in the range of about It is 300-352mg eq/g. Still another feature of the aluminosilicate ion exchange materials herein is a calcium ion exchange rate of at least about 2 grains Ca2 ⁺ /gallon/minute/gram/gallon aluminosilicate (anhydrous basis), which ranges typically Approximately 2-6 grains/gallon/minute/gram/gallon based on calcium ion hardness. Optimum aluminosilicates for use as builders have calcium ion exchange rates of at least about 4 grains/gallon/minute/gram/gallon.

单位）进行测试时，无定形材料未显示可见的衍射图。Amorphous aluminosilicate ion exchange materials typically have a Mg ⁺² exchange capacity of at least about 50 mg equivalent CaCO ₃ /g (12 mg Mg ⁺² /g) and a Mg ⁺² exchange rate of at least about 1 grain/gallon/ min/gram/gallon. When using Cu radiation (1.54

Amorphous materials show no visible diffraction pattern when tested.

Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available. Aluminosilicates suitable for use in the present invention may be crystalline or amorphous in structure and may be naturally occurring aluminosilicates or synthetically derived. Aluminosilicate ion exchange materials are produced as described in US 3,985,669 (Krummel et al., issued October 12, 1976, incorporated herein by reference). Preferred synthetic crystalline aluminosilicate ion exchange materials for use in the present invention are commercially available as Zeolite A, Zeolite B and Zeolite X. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:

Where x is about 20-30, especially about 27, the particle size is usually less than about 5 microns.

The granular detergents of the present invention may contain neutral or alkaline salts having a pH of 7 or greater in solution and being organic or inorganic in nature. The co-salt contributes to the desired density and bulk of the detergent granules of the present invention. Although some of the salts are inert, many of them also function as detergency builders in the wash liquor.

Examples of neutral water soluble salts include the alkali metal, ammonium or substituted ammonium chlorides, fluorides and sulfates. Of the above salts, alkali metal, especially sodium, salts are preferred. Sodium sulphate is commonly used in detergent granules and is a particularly preferred salt. Citric acid and generally any other organic or inorganic acid can be added to the granular detergents of the present invention provided they are chemically compatible with the other ingredients of the block composition.

Other useful water-soluble salts include compounds well known for use as detergent builders. Builders are generally selected from the various water-soluble alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates and polyhydroxysulfonates salt. Preference is given to the abovementioned alkali metals, especially the sodium salts.

Specific examples of inorganic phosphate builders are sodium and potassium tripolyphosphates, pyrophosphates, polymeric metaphosphates with a degree of polymerization of about 6-21, and orthophosphates. Examples of polyphosphate builders are the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane 1-hydroxy-1,1-diphosphonic acid, and ethane, 1,1,2-triphosphonic acid sodium and potassium salts. Other phosphorus builder compounds are described in US 3159581, 3213030, 3422021, 3422137, 3400176 and 3400148 (herein incorporated by reference).

Examples of inorganic additives other than phosphorus are sodium and potassium carbonates, bicarbonates, sesquicarbonates, tetraborate decahydrate, and silicates in which the molar ratio of _SiO2 to alkali metal oxide is about 0.5-4.0, preferably about 1.0-2.4. Compositions made by the process of the present invention do not require excess carbonate for processing and preferably do not contain more than 2% finely powdered calcium carbonate (as described in US 4,196,093, issued April 1, 1980 to Clarke et al.) , and preferably without the calcium carbonate.

The above-mentioned powders commonly used in detergents, such as zeolite, carbonate, silicon dioxide, silicate, citrate, phosphate, perborate, etc., as well as process aids such as starch, can be used in the preferred method of the present invention. Examples.

Brief description of the drawings

Figure 1 shows a graph of shear stress and viscosity versus shear rate. The test slurry was a 77% by weight solution of sodium _C₁₁ - _C₁₃ linear alkylbenzene sulfonate, measured at 70°C.

Figure 2 shows a plot of shear stress and viscosity versus shear rate. The slurry tested was a 76% by weight solution of _C₁₄ - _C₁₅ alkyl sodium sulfate, measured at 70°C.

Figure 3 shows a plot of shear stress versus shear velocity for five different slurry compositions. C ₁₄ -C ₁₅ alkyl sodium sulfate solution: C ₁₃ -C ₁₅ alkyl ethoxy sodium sulfate (average 3 ethoxy groups) by weight percentage is (a) 70:0, (b) 68:2, (c) 66.5:3.5, (d) 63:7, (e) 56:14.

The temperature of the aqueous slurry was 70°C for each test.

Figure 4 shows a plot of shear stress and viscosity versus shear rate. The slurry tested was a 78% by weight mixture of sodium _C₁₁ - _C₁₃ linear alkylbenzene sulfonate and sodium tallow alkyl sulfate. These two surfactants are present in equal amounts. The test temperature of the aqueous slurry was 70°C.

Figure 5 shows a plot of shear stress and viscosity versus shear rate. The slurry tested was a 74.8% by weight mixture of sodium _C₁₁ - _C₁₃ linear alkyl sulfonate and sodium tallow alkyl sulfate. Both surfactants are present in equal amounts. The slurry also contained 3.2% by weight of sodium _C13 - _C15 alkyl ethoxysulfate (average of 3 ethoxy groups). The test temperature of the aqueous slurry was 70°C.

Example

1. In each of the following embodiments, by fatty alcohol sulfation, then in the continuous neutralization loop, neutralize with 48-50% aqueous sodium hydroxide solution to make anionic surfactant slurry, the production speed is 1-2 tons/hour.

A 76% active slurry of sodium C ₁₄ -C ₁₅ alkyl sulfate has a rheology diagram as shown in FIG. 2 . There is an obvious shear thickening zone when the shear rate is about 20-40S ^-1 .

The following examples ae illustrate the improvement of the rheogram by the addition of sodium _C13 - _C15 alkyl ethoxysulfate (having an average of 3 ethoxy groups). In example be, alkyl ethoxysulfate is injected into the neutralization loop.

a b c d e

Alkyl Sulfate 70 68 66.5 63 56

Alkyl Ethoxy Sulfate 0 2 3.5 7 14

Water (and impurities) ^* 30 30 30 30 30

The shear thickening properties of compositions a-c can be seen from Figure 3, in contrast, examples d and e do not show shear thickening properties, but they exhibit the properties of shear weakening fluids (with a pour point).

2. In the following example, a mixture of C ₁₁ -C ₁₃ linear alkylbenzene sulfonate and tallow alkyl sulfate (equal weight of each component) was prepared by neutralizing with 48-50% aqueous sodium hydroxide solution , the production speed is 1-2 tons/hour.

F(Figure 4) G(Figure 5)

C ₁₁ -C ₁₃ LAS 39 37.1

TAS 39 37.4

Alkyl ethoxy sulfate 0 3.2

Water (and impurities) ^* 22 22

In Example F (see Figure 4) the composition exhibited instability in the neutralization circuit, with large fluctuations in pressure due to the rheological properties of the composition. This made it impossible for us to produce this slurry composition stably through a continuous neutralization circuit.

In Example G (see Figure 5) the composition contained 3.2% by weight of C13- _C15 alkyl ethoxy sulfate (average 3 ethoxy groups), which gave the resulting slurry composition Shear weakens the properties of a liquid.

Note: In Examples 1 and 2, the total percentage of water also includes a small amount of impurities, mainly unsulfonated substances, such as alcohols, fatty acids.

Claims (14)

1, a kind of washing composition paste composition, it contains:

(a) anion surfactant of 50%-94% (weight), this tensio-active agent is selected from following salt:

C ₁₂-C ₂₀Alkyl-sulphate, side chain or linear C ₁₀-C16 alkylbenzene sulfonate, C ₁₄-C ₁₆Alkene or alkane sulfonate, senior (C ₁₂-C ₁₈) salt of lipid acid, C ₁₂-C ₂₀Alkyl methyl sulfonated ester and composition thereof;

(b) 1%-30% (weight) chemical formula is R (OC ₂H ₄) _nOSO ₃The alkyl ethoxy sulfate of M

Wherein R is a kind of aliphatic hydrocarbon group, and side chain or linearity contain 10-18 carbon atom, and ethoxylation group mean number n is 1-7, and M is the ammonium of a kind of basic metal, alkaline-earth metal ammonium or replacement,

(c) water of 5%-35% (weight);

This slurry is 25S in velocity of shear ^-1The time viscosity under 70 ℃ of temperature recording greater than 10Pa.S.

2, by a kind of detergent paste of claim 1, the content that it is characterized by anion surfactant (a) is the 60%-85% of said composition weight.

3, by a kind of detergent paste of claim 1 or 2, it is characterized by alkyl ethoxy sulfate (b) content is the 1%-15% of said composition weight.

4, by each a kind of detergent paste of claim 1-3, it is characterized by in velocity of shear is 25S ^-1The time record this slurry viscosity under 70 ℃ of temperature greater than 20Pa.S.

5, by each a kind of detergent paste of claim 1-4, the mean value n that it is characterized by the ethoxylation group in alkyl ethoxy sulfate (b) is 2-4.

6, by each a kind of detergent paste of claim 1-5, the ratio that it is characterized by anion surfactant (a) and alkyl ethoxy sulfate (b) is 9: 1-50: 1.

7, by each a kind of detergent paste of claim 1-3, it is characterized by anion surfactant (a) and comprise tallow alkyl sulfate, C ₁₁-C ₁₃Linear alkyl benzene sulfonate, or its mixture; And alkyl ethoxy sulfate (b) comprises the side chain C that on average has 3 ethoxylation groups ₁₂-C ₁₅Alkyl ethoxy sulfate.

8, a kind of high-activity detergent piece material, it contains 30%-80%(weight) as each the slurry of claim 1-7.

9, a kind of high-activity detergent piece material by claim 8 contains a kind of washing composition dry powder, and this powder is selected from zeolite, carbonate, silicon-dioxide, silicate, Citrate trianion, phosphoric acid salt, perborate, starch and composition thereof.

10, by a kind of preparation method of the paste compound of claim 1-7, comprise and use a kind of basic metal, the oxyhydroxide that is preferably sodium in and this anion surfactant (a) that neutralizes continuously in the loop.

11,, it is characterized by adding alkyl ethoxy sulfate (b) after neutralize anionic surfactant (a) by a kind of method of claim 10.

12, by a kind of method of claim 10, it is characterized by in neutralize anionic surfactant (a) process, in during alkyl ethoxy sulfate (b) is added to salt form and the loop.

13,, make anion surfactant (a) and alkyl ethoxy sulfate (b) cosulfonate before it is characterized by neutralization by a kind of method of claim 10.

14, a kind of preparation method of unrestricted flow granulated detergent; comprise with significant quantity as each the described a kind of detergent paste of claim 1-7 and the washing composition dry powder blend of significant quantity; generate a kind of uniform mixture fast by this mixture; make this mixture be granulated into dispersive detergent bar material, and this this detergent composition of detergent bar material and remaining is mixed mutually.

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