CN1239995A - Process for making detergent composition by non-tower process - Google Patents

Abstract

A non-tower process for continuously preparing granular detergent composition having a density of at least about 600 g/l is provided. The process comprises the steps of (a) dispersing an aqueous or non-aqueous surfactant, and coating the surfactant with fine powders having a diameter from 0.1 to 500 microns, in the mixer to obtain irregular shape granules and excessive fine powders, and (b) granulating the agglomerates in one or more fluidizing apparatus. The process can also comprise further step (a'), i.e., spraying finely atomized liquid onto the first agglomerates in a mixer, between step (a) and step (b).

Description

Process for preparing detergent compositions by non-tower process

field of invention

The present invention generally relates to non-tower processes for producing granular detergent compositions. More particularly, the present invention relates to a continuous production process in which detergent agglomerates are produced by feeding surfactants and coating materials to a series of mixers. The process of the present invention produces free-flowing detergent compositions whose densities can be adjusted within a wide range of consumer needs and which are marketable.

Background of the invention

Concentrated products with lower dosage volumes have attracted much attention in the laundry detergent industry in recent years. In order to facilitate the production of these so-called low-dosage detergents, attempts have been made to produce detergents with higher bulk densities, eg 600 g/l or higher. Demand for such low-dosage detergents is increasing because they save resources and can be sold in smaller packages that are more convenient for consumers. In practice, however, there is uncertainty about exactly how "concentrated" modern detergent products should be. In fact, many consumers, especially in developing countries, still prefer to use high dosages of detergent per wash operation.

In general, the methods of making detergent granules or powders include two main types. The first method involves spray drying an aqueous detergent slurry in a spray drying tower to produce porous detergent granules (eg, a tower step for low density detergent compositions). In the second method, the various detergent components are dry blended, after which they are agglomerated using binders such as nonionic or anionic surfactants to produce high density detergent compositions (e.g. with agglomeration in high density detergent compositions). In both of the above methods, important factors controlling the density of the detergent particles formed are the shape, porosity and size distribution of the particles, the density of the various materials, the shape of the various materials and their respective chemical compositions.

There have been attempts in the art to provide means of increasing the density of detergent granules or powders. In particular, the spray-dried granules are densified by a post-tower process. For example, one approach involves performing batch production in which a spray-dried or granulated detergent powder comprising sodium tripolyphosphate and sodium sulfate is densified and pelletized in ^a Marumerizer(R). The equipment pack will be a substantially horizontal, rough and rotatable table within and as its base a substantially vertical smooth-inner cylindrical shell. However, since this process is mainly a batch operation, it is not suitable for large-scale production of detergent powders. Finally, attempts have been made to provide a continuous process for increasing the density of the "post-tower" or spray-dried detergent granules. Typically, such methods require a first means for comminuting or grinding the particles, and a second means for increasing the density of the comminuted particles by agglomeration. Although these methods achieve the desired increase in density by treating or densifying the "bottom product" or spray-dried particles, they are limited in their ability to increase the degree of surface activity without a subsequent coating step. Furthermore, treatment or densification by "post-processing" methods is not economically viable (high cost) and the production process is complex. Furthermore, all of the above methods mainly involve densification or spray drying of the particles. Currently, a large number and type of substances are limited in the detergent production process to the spray drying process. For example, it would be difficult to achieve high levels of surfactants in the resulting detergent compositions and to conveniently manufacture detergents in a more efficient manner. Therefore, it remains desirable to find a method of producing detergent compositions which is not limited by conventional spray drying techniques.

For this reason, various methods necessary to agglomerate detergent compositions have also been proposed in the art. For example, the detergent builder is agglomerated by mixing the zeolite and/or layered silicate in a mixer to form free flowing agglomerates. Such attempts suggest that the above methods can be used to produce detergent agglomerates; however, they do not provide a mechanism by which pasty, liquid and dry matter detergent raw materials can be efficiently agglomerated into Friable, free-flowing detergent agglomerates.

Therefore, there is still a need in the art to find an agglomeration method (non-tower method) for the continuous production of high-density detergent compositions directly from detergent raw materials, preferably the density can be achieved by adjusting the processing conditions. Likewise, it remains desirable to find a more efficient, adaptable and economical method for the large-scale production of detergents that would allow (1) greater flexibility in the final density of the finished detergent composition, and (2) ) allows more flexibility in the addition of various detergent components, especially liquid detergent components.

The following references relate to the densification of spray-dried granules: Appel et al., US 5,133,924 (Lever); Bortolotti et al., US 5,160,657 (Lever); Johnson et al., GB 1,517,713 (Unilever); and Curtis, EP 451,894.

The following references relate to the production of detergents by agglomeration: Beujean et al., WO 93/23,523 (Henkel); Lutz et al., US 4,992,079 (FMC Corporation); Porasik et al., US 4,427,417 (Korex); Beerse et al., US 5,108,646 (Procter &Gamble); Capeci et al., US 5,366,652 (Procter &Gamble); Hollingsworth et al., EP 351,937 (Unilever); Swatling et al., US 5,205,958; Dhalewadikar et al., International Application Publication WO96/04359 (Unilever).

For example, WO93/23,523 (Henkel) discloses a method comprising pre-agglomeration by a low-speed mixer and further agglomeration by a high-speed mixer to obtain a high-density detergent composition, which is less than 25wt % of the particles had a particle size greater than 2 mm. A continuous process for agglomeration is described in US 4,427,417 (Korex) which reduces caking and over-agglomeration phenomena.

None of the prior art has the advantages and beneficial effects of the present invention.

Summary of the invention

The present invention provides a process for producing high density granular detergent compositions which fulfills the above needs in the art. The present invention also provides a process for producing granular detergent compositions by agglomeration (eg, non-column) processes with some flexibility in the final density of the final composition, thereby meeting the above needs in the art. The process does not employ conventional spray drying towers which are limited in the preparation of high surfactant content compositions. Furthermore, the process of the present invention appears to be more efficient, more economical and more flexible in view of the variety of detergent compositions that can be produced in said process. Furthermore, the method of the present invention is also environmentally beneficial because it does not employ spray drying towers that would normally release particulate matter and volatile organic compounds into the atmosphere.

Herein, the term "agglomerate" refers to particles formed by agglomerating raw materials with binders such as surfactants and/or inorganic/organic solvents and polymer solutions. As used herein, the term "granulation" refers to the complete fluidization of agglomerates for the purpose of producing free-flowing round granular agglomerates. The term "average residence time" is defined herein as follows:

Average residence time (hours) = material (kg) / flow rate (kg/hour)

All percentages herein are by weight unless otherwise stated. All ratios are by weight unless otherwise indicated. The term "comprising" herein means that other steps and other components that do not affect the results of the invention may also be added. Included within this term are the terms "consisting of" and "consisting essentially of".

According to one aspect of the present invention there is provided a process for preparing a granular detergent composition having a density of at least about 600 g/l.

The method comprises the steps of:

(a) dispersing the surfactant in a mixer, and coating the surfactant with a fine powder of 0.1-500 μm in diameter, wherein the conditions of the mixer include: (1) an average residence time of about 0.5-15 minutes , and (2) energy conditions of about 0.15-7kj/kg, wherein agglomerates are formed; and

(b) granulation of the agglomerates in one or more fluidization equipment, where the conditions of each fluidization equipment include (1) average residence time of about 1-10 minutes, (2) unfluidized bed depth is about 100 to about 300 mm, (3) the droplet spray particle size is no more than about 50 μm, (4) the spray height is about 1 75 to about 250 mm, (5) the fluidization velocity is about 0.2 to 1.4 m/s, and ( 6) The temperature of the fluidized bed is about 12-100°C.

The present invention also provides a process for preparing a granular detergent composition having a density of at least about 600 g/l.

The method comprises the steps of:

(a) dispersing the surfactant in a mixer, and coating the surfactant with a fine powder of 0.1-500 μm in diameter, wherein the conditions of the mixer include: (1) an average residence time of about 0.5-15 minutes, (2) The energy condition is about 0.15-7kj/kg, wherein the first agglomerate is formed;

(a') Spraying a finely atomized liquid on the first agglomerate in a mixer, wherein the conditions of the mixer include: (1) an average residence time of about 0.2-5 seconds, (2) a peripheral velocity of about 10-30 m/s, and (3) energy conditions of about 0.15-5 kj/kg, wherein a second agglomerate is formed; and

(b) granulating the second agglomerate in one or more fluidized equipment, wherein the conditions of each fluidized equipment include (1) average residence time of about 1-10 minutes, (2) non-fluidized The bed depth is about 100-300mm, (3) the droplet spray size does not exceed about 50μm, (4) the spray height is about 175-250mm, (5) the fluidization velocity is about 0.2-1.4m/s, and (6 ) The temperature of the fluidized bed is about 12-100°C.

The present invention also provides high density granular detergent compositions having a density of at least about 600 g/l prepared by any of the process embodiments of the present invention.

It is therefore an object of the present invention to provide a process for the continuous production of detergent compositions in which the density of the end product can be more adaptable by controlling the energy input, residence time conditions and peripheral velocity conditions of the mixer . Another object of the present invention is to provide a more efficient, flexible and economical process to facilitate large-scale production. These objects, features and advantages of the present invention will become apparent to those skilled in the art from a reading of the following detailed description of the preferred embodiments of the present invention together with the claims. Detailed description of the invention

The present invention relates to a process for producing free-flowing granular detergent agglomerates having a density of at least about 600 g/l. The process produces granular detergent agglomerates from aqueous or anhydrous surfactants on which fine powders with a diameter of 0.1-500 μm are coated to obtain low-density granules.

Method first step (i) [step (a)]

In the first step (i) of the method of the present invention, one or more aqueous or anhydrous surfactants in powder form, paste form and/or liquid form are mixed with a diameter of 0.1-500 μm, preferably about 1-about 100 μm The fine powder is added to the first mixer to prepare agglomerates. (The definition of surfactant and fine powder will be described in detail below.) In addition to fine powder, it is also possible to produce a diameter of about An internally recirculated powder stream of 0.1 to about 300 microns is fed into the mixer. This internally circulated powder stream can comprise from 0 to about 60% by weight of the final product.

A shredder connectable to the first mixer is preferably used for shredding undesirably large agglomerates. Therefore, the method comprising a second shredder with a second mixer with a shredder is suitable to reduce the content of excessive agglomerates in the final product, so this method is one of the preferred embodiments of the present invention.

In another embodiment of the present invention, before the above, the surfactant used in the first step (i) can be added to a mixer or premixer (such as a conventional screw extruder or other similar mixing machinery) , thereafter, the mixed detergent material is added to the first mixer for agglomeration as described in the present invention.

Generally speaking, preferably, the average residence time of the first mixer should be about 0.5 to about 15 minutes, and the energy per unit mass (energy condition) in the first mixer is about 0.15 to about 7 kj/kg, more preferably the first The mixer average residence time is about 3 to about 6 minutes, and the energy per unit mass (energy condition) in the first mixer is about 0.15 to about 4 kj/kg.

An example of the first mixer may be any type of mixer known in the art as long as the mixer can maintain the above-mentioned conditions for the first step. A specific example is the Lödige KM mixer produced by the Lödige company (Germany). As a result of the first step (i) agglomerates (first agglomerates) are produced. The first agglomerate is then either (1) subjected to a second step, or (2) subjected to a first step (ii) followed by a second step. Step one (ii) [step (a')]

The product obtained from the first step (i), ie the first agglomerate, is fed into the second mixer. After the first agglomerate is added to the second mixer, the agglomerates are sprayed with a finely atomized liquid in the second mixer. Optionally, excess fines formed in the first step (i) are added to the first step (ii). If an excess of fines is added to step (ii), a spray of finely atomized liquid is used to bind the excess of fines to the surface of the agglomerate. About 0-10%, preferably about 2-5%, of the powdered detergent components used in the first step (i) and/or other detergent components may be added to the second mixer.

In general, preferably, the average residence time of the second mixer should be about 0.2 to about 5 seconds, the peripheral speed of the second mixer should be about 10 to about 30 m/s, and the energy per unit mass in the second mixer ( energy condition) is about 0.15-about 5kj/kg, more preferably, the average residence time of the second mixer should be about 0.2-about 5 seconds, the peripheral speed of the second mixer should be about 10-30m/s, the second The energy per unit mass (energy condition) in the mixer is about 0.15 to about 5 kj/kg, most preferably, the average residence time of the second mixer should be about 0.2 to about 5 seconds, and the peripheral speed of the second mixer should be About 15 to about 26 m/s, the energy per unit mass (energy condition) in the second mixer is about 0.2 to about 3 kj/kg.

Examples of the second mixer may be any type of mixer known in the art as long as the mixer can maintain the above-mentioned conditions for the first step (ii). A specific example is the Flexomic type mixer produced by the company Schugi (Netherlands). As a result of the first step (ii), a second agglomerate can be obtained. Second step [step (b)]

In the second step of the process of the present invention, the first agglomerate obtained from the first step (i) or the second agglomerate obtained from the first step (ii) is fed into a fluidization device such as a fluidized bed, Enhanced granulation is used to produce free-flowing high-density granules. The second step can be carried out in one or more fluidization equipment (for example, a combination of various fluidization equipment, such as a fluidized bed dryer and a fluidized bed condenser). Optionally, about 0-10%, preferably about 2-5%, of the powdered detergent material used in the first step and/or other detergent ingredients can be added to the second step. Optionally, about 0 to about 20%, more preferably about 2 to 10%, of the liquid detergent material used in the first step (i), the first step (ii) and/or other detergent components Added to this step to enhance granulation and coating on the particle surface.

Generally speaking, in order to achieve a density of at least about 600 g/l, preferably higher than 650 g/l, the conditions of the fluidization equipment are as follows: average residence time: about 1-10 minutes

Non-fluidized bed depth: about 100-300mm

Droplet spray particle size: not higher than about 50 microns

Spray height: about 175-250mm

Fluidization velocity: about 0.2-1.4m/s

Bed temperature: about 12-100°C,

More preferably:

Average dwell time: about 2-6 minutes

Non-fluidized bed depth: about 100-250mm

Droplet spray particle size: less than about 50 microns

Spray height: about 175-200mm

Fluidization velocity: about 0.3-1.0m/s

Bed temperature: about 12-80°C.

If two types of fluidization equipment are used, the total average residence time in the second step can be about 2-20 minutes, more preferably about 2-12 minutes.

A coating agent for improving flow and/or for reducing the particle size of the agglomerates in the detergent composition may be added at one or more of the following points in the process: (1) in the fluid bed cooler Add coating agent directly after fluid bed dryer; (2) add coating agent between fluid bed dryer and fluid bed cooler; and/or (3) add coating agent directly in fluid bed dryer coating agent. The coating agent is preferably selected from the group consisting of aluminosilicates, silicates, carbonates and mixtures thereof. The coating agent not only enhances the free-flowing properties of the resulting detergent composition, but also controls agglomeration, preventing or reducing over-agglomeration, where free-flowing compositions are desired by users as this characteristic facilitates washing Use the scoop when using the medicine. It is well known to those of ordinary skill in the art that overagglomeration can result in very unfavorable flow and poor appearance of the finished detergent article. Detergent Raw Materials

Surfactants in products made according to the present invention are contained in the following detergent materials, finely atomized liquids and builder ingredients, generally at a level of about 5-60%, preferably about 12-40%, more preferably about 15% -35%. The surfactant contained therein may come from any part of the process of the invention, for example from any of the first step (i), first step (ii) and/or second step. Detergent Surfactants (Aqueous and/or Anhydrous)

Based on the total amount of the final product obtained by the method of the present invention, the surfactant used in the method may be used in an amount of about 5-60%, preferably about 12-40%, more preferably about 15-35%.

The surfactant of the method of the present invention is used as the detergent raw material in the first step above, and this surfactant can be in the form of powder, paste or liquid raw material.

The surfactant itself is preferably selected from anionic, nonionic, zwitterionic, amphoteric, and cationic surfactants, and compatible mixtures thereof. Useful detersive surfactants are disclosed in US 3,664,961 (Norris, issued May 23, 1972), US 3,929,678 (Laughlin et al, issued December 30, 1975), both of which are incorporated herein by reference. Cationic surfactants that can be used also include those disclosed in the following documents: US 4,222,905 (Cockrell, 1980.9.16 authorization) and US 4,239,659 (Murphy, 1980.12.16 authorization), these two documents are also incorporated herein as a reference. Described surfactant, preferably adopt anionic surfactant and nonionic surfactant, anionic surfactant is most preferred.

Non-limiting examples of anionic surfactants preferred for use herein include: conventional C ₁₁ -C ₁₈ alkylbenzene sulfonates ("LAS"), primary, branched and random C ₁₀ -C ₂₀ alkyl Sulfate ("AS"), a C ₁₀ -C ₁₈ secondary (2,3) alkyl sulfate of the formula: CH ₃ (CH ₂ ) _x (CHOSO ₃ ⁻ M ⁺ )CH ₃ and CH ₃ (CH ₂ ) _y ( _CHOSO3 ^- M ⁺ ) _CH2CH3 , wherein x and (y+1) are integers of at least about 7, preferably at least about 9, and M is _a water-solubilizing cation, especially sodium, unsaturated sulfate such as oil base sulfates, C ₁₀ -C ₁₈ alkyl alkoxy sulfates ("AE _x S", especially EO1-7 ethoxy sulfates.

Useful anionic surfactants also include water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing about 2-9 carbon atoms in the acyl group and about 9-23 carbon atoms in the alkane moiety; Water-soluble salts of olefin sulfonic acids of about 12-24 carbon atoms; beta-alkoxyalkane sulfonates containing about 1-3 carbon atoms in the alkyl moiety and about 8-20 carbon atoms in the alkane moiety.

Optionally, other examples of surfactants useful in the present invention include: C ₁₀ -C ₁₈ alkyl alkoxy carboxylates (especially ethoxy carboxylates of EO1-5), C ₁₀ -C ₁₈ glycerol Ethers, C ₁₀ -C ₁₈ alkyl polyglycosides and corresponding sulfated polyglycosides and C ₁₂ -C ₁₈ α-sulfonated fatty acid esters. If desired, conventional nonionic and amphoteric surfactants such as: C ₁₂ -C ₁₈ alkyl ethoxylates (“AE”), including so-called narrow peak alkyl Ethoxylates and C ₆ -C ₁₂ alkylphenol alkoxylates (especially ethoxylates and mixtures of ethoxylates and propoxylates); C ₁₀ -C ₁₈ amine oxides, etc. C ₁₀ -C ₁₈ N-alkyl polyhydroxy fatty acid amides may also be used. Typical examples thereof include C ₁₂ -C ₁₈ N-methyl glucamides. See WO 9,206,154. Other sugar-derived surfactants include N-alkoxy polyhydroxy fatty acid amides such as C ₁₀ -C ₁₈ N-(3-methoxypropyl) glucamide. The N-propyl to N-hexyl C ₁₂ -C ₁₈ glucamides can be used in low sudsing detergents. C ₁₀ -C ₂₀ conventional soaps may also be used. If high suds is desired, branched _C10 - _C16 soaps can be used. Mixtures of anionic and nonionic surfactants are preferably used. Other conventionally used surfactants are listed in standard textbooks.

Cationic surfactants can also be used as detergent surfactants in the present invention, suitable quaternary ammonium surfactants are selected from the group consisting of: mono C ₆ -C ₁₆ , preferably C ₆ -C ₁₀ N-alkyl or alkenyl ammonium surfactants Active agent, wherein the remaining N position can be substituted by methyl, hydroxyethyl or hydroxypropyl. Amphoteric surfactants are also useful as detergent surfactants in the present invention, including aliphatic derivatives of heterocyclic secondary and tertiary amines; zwitterionic surfactants, which may include aliphatic quaternary ammonium, quaternary phosphonium, and quaternary sulfonium Derivatives of compounds; water-soluble salts of alpha-sulfonated fatty acid esters; alkyl ether sulfates; water-soluble salts of alkenesulfonic acids; beta-alkoxyalkanesulfonates; formula R(R ¹ ) ₂ N ⁺ R ² COO ^- betaine, wherein R is C ₆ -C ₁₈ hydrocarbon group, preferably C ₁₀ -C ₁₆ alkyl or C ₁₀ -C ₁₆ amidoalkyl, and each R ¹ is usually C ₁ -C ₃ alkane A group, preferably a methyl group, R ² is a C ₁ -C ₅ hydrocarbon group, preferably a C ₁ -C ₃ alkylene group, more preferably a C ₁ -C ₂ alkylene group. Examples of suitable betaines include: cocamidopropyl dimethyl betaine; hexadecyl dimethyl betaine; C ₁₂ -C ₁₄ amidopropyl betaine; C ₈ -C ₁₄ amidohexyl Diethyl betaine; 4[C ₁₄ -C ₁₆ acylmethylamidodiethylammonium]-1-carboxylic acid butane; C ₁₆ -C ₁₈ amidodimethyl betaine C ₁₂ -C ₁₆ acyl acyl Aminopentanediethylbetaine; C ₁₂ -C ₁₆ acylmethylamidodimethylbetaine. Preferred betaines are C ₁₂ -C ₁₈ dimethylammonium hexanoate and C ₁₀ -C ₁₈ acylamidopropane (or ethane) dimethyl (or diethyl) betaine; and the formula R(R ¹ ) ₂ N ⁺ R ² SO ₃ ^- sultaines, wherein R is a C ₆ -C ₁₈ hydrocarbon group, preferably a C ₁₀ -C ₁₆ alkyl group, more preferably a C ₁₂ -C ₁₃ alkyl group, and each R ¹ is usually is C ₁ -C ₃ alkyl, preferably methyl, and R ² is C ₁ -C ₆ hydrocarbon, preferably C ₁ -C ₃ alkylene, or preferably hydroxyalkylene. Examples of suitable sultaines include C ₁₂ -C ₁₄ dimethylammonium-2-hydroxypropyl sulfonate, C ₁₂ -C ₁₄ amidopropylammonium-2-hydroxypropyl sultaine, C ₁₂ -C ₁₄ dihydroxyethylammonium propanesulfonate and C ₁₆ -C ₁₈ dimethylammonium hexanesulfonate, preferably C ₁₂ -C ₁₄ amidopropylammonium-2-hydroxypropyl sulfobeet alkali. powder

Based on the total amount of raw materials used in the first step, the amount of fine powder used in the method of the present invention in the first step may be about 94-30%, preferably 86-54%. The fine powder starting material for the process of the invention is preferably selected from ground soda ash, powdered sodium tripolyphosphate (STPP), hydrated tripolyphosphate, ground sodium sulfate, aluminosilicates, crystalline layered silicates, Nitrilotriacetate (NTA), phosphates, precipitated silicates, polymers, carbonates, citrates, powdered surfactants (such as powdered alkanesulfonic acids) and internal A circulating powder flow, wherein the average diameter of the powder is 0.1-500 μm, preferably 1-300 μm, more preferably 5-100 μm. When hydrated STPP is used as the fine powder of the present invention, it is preferable that the degree of hydration of STPP should not be less than 50%. The aluminosilicate ion exchange materials used as builders in the present invention preferably have both a high calcium ion exchange capacity and a high exchange rate. While not being bound by any theory, it is believed that this high calcium ion exchange rate and capacity is a function of a number of interacting factors derived from factors in the process by which the aluminosilicate ion exchange material is produced . Thus, the aluminosilicate ion exchange materials used in the present invention are preferably produced in accordance with US 4,605,509 (Corkill et al., Procter & Gamble), which is incorporated herein by reference.

The "sodium" form of aluminosilicate ion exchange materials is preferred since neither the potassium nor hydrogen forms of aluminosilicates exhibit the high exchange capacity and speed afforded by the sodium form. Furthermore, the aluminosilicate ion exchange material is preferably in overdried form to facilitate the production of crisp detergent agglomerates according to the present invention. The aluminosilicate ion exchange materials used herein preferably have a particle size diameter that optimizes their effectiveness as a builder. Herein, the term "particle size diameter" refers to the average particle size diameter of the aluminosilicate ion exchange material, as determined using conventional analytical techniques, such as microscopy and scanning electron microscopy (SEM). The particle size of the aluminosilicate is preferably about 0.1-10 μm, more preferably about 0.5-9 μm, most preferably about 1-8 μm.

Preferred aluminosilicate ion exchange materials have the formula

Na _z [(AlO ₂ ) _z ·(SiO ₂ ) _y ]xH ₂ O

Wherein, z and y are integers of at least 6, the molar ratio of z to y is about 1-5, and x is about 10-264. More preferably the aluminosilicate has the formula

Na ₁₂ [(AlO ₂ ) ₁₂ ·(SiO ₂ ) ₁₂ ]xH ₂ O

Wherein, x is about 20-30, preferably about 27. These preferred aluminosilicates are commercially available, for example as Zeolite A, Zeolite B and Zeolite X. Alternatively, natural or synthetic aluminosilicate ion exchange materials suitable for use in the present invention can be prepared as described in US 3,985,669 (Krummel et al.), which is incorporated herein by reference.

The aluminosilicates useful in the present invention are further characterized in that they have an ion exchange capacity of at least about 200 meq calcium carbonate hardness/g, on a dry basis, preferably in the range of about 300-352 meq calcium carbonate hardness/g g. In addition, another feature of the aluminosilicate ion exchange materials of the present invention is that they have a calcium ion exchange rate of at least about 2 grains Ca ⁺⁺ /gallon/min/-gram/ug, more preferably about 2-6 grains Gram Ca ⁺⁺ /rulun/min/-gram/rulun. fine atomized liquid

The amount of finely atomized liquid in the method of the invention is about 1-10% (based on activity), preferably about 2-6% (based on activity), based on the total amount of the final product obtained by the method of the invention. The finely atomized liquid of the method of the present invention may be selected from liquid silicates, anionic or cationic surfactants, which may be in liquid form, aqueous or non-aqueous polymer solutions, water and mixtures thereof. Other optional examples of finely atomized liquids for use in the present invention may be sodium carboxymethylcellulose solution, polyethylene glycol (PEG) and dimethylenetriaminepentamethylphosphonic acid (DETMP).

Preferred examples of anionic surfactant solutions that can be used as finely atomized liquids in the present invention are about 88-97% active HLAS, about 30-50% active NaLAS, about 28% active AE3S solution, about 40-50% active Liquid silicates, etc.

Cationic surfactants and suitable quaternary ammonium surfactants which can be used as finely atomized liquids according to the invention are selected from mono C ₆ -C ₁₆ , preferably C ₆ -C ₁₀ N-alkyl or alkenyl ammonium surfactants, Wherein, the remaining N positions are substituted by methyl, carboxyethyl or hydroxypropyl.

A preferred example of an aqueous or non-aqueous polymer solution that can be used as a finely atomized liquid in the present invention is a modified polyamine comprising a polyamine backbone corresponding to the formula: A modified polyamine having the formula V _(n+1) W _m Y _n Z or a polyamine backbone corresponding to the formula A modified polyamine having the formula V _(n-k+1) W _m Y _n Y' _k Z, wherein k is less than or equal to n, and the molecular weight of the polyamine backbone before modification is greater than about 200 Daltons, in

或

或

i) The V unit is an end unit having the following formula:

or

or

或 ii) The W unit is a skeletal unit with the following formula: or

or

或

；和iii) The Y unit is a branched unit having the formula: or

or

;and

或

iv) The Z unit is a terminal unit having the following formula:

or

Wherein, the backbone chain R unit is selected from the following groups: C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxyalkylene Alkyl, C ₈ -C ₁₂ dialkylarylene, -(R ¹ O) _x R ¹ -, -(R ¹ O) _x R ⁵ (OR ¹ ) _x -,

-(CH ₂ CH(OR ² )CH ₂ O) _z (R ¹ O) _y R ¹ (OCH ₂ CH(OR ² )-CH ₂ ) _w -, -C(O)(R ⁴ ) _r C(O )-, -CH ₂ CH(OR ² )CH ₂ -, and mixtures thereof; wherein, R ¹ is C ₂ -C ₆ alkylene and mixtures thereof; R ² is hydrogen, -(R ¹ O) _x B, and mixtures thereof; R ³ is C ₁ -C ₁₈ alkyl, C ₇ -C ₁₂ arylalkyl, C ₇ -C ₁₂ alkyl substituted aryl, C ₆ -C ₁₂ aryl, and mixtures thereof; R ⁴ is C ₁ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₈ -C ₁₂ aralkylene, C ₆ -C ₁₀ arylene, and mixtures thereof; R ⁵ is C ₁ - C ₁₂ alkylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxyalkylene, C ₈ -C ₁₂ dialkylarylene, -C(O)-, -C(O )NHR ⁶ NHC(O)-, -R ¹ (OR ¹ )-, -C(O)(R ⁴ ) _r C(O)-, -CH ₂ CH(OH)CH ₂ -, -CH ₂ CH( OH)CH ₂ O(R ¹ O) _y R ¹ OCH ₂ CH(OH)CH ₂ -, and mixtures thereof; R ⁶ is C ₂ -C ₁₂ alkylene or C ₆ -C ₁₂ arylene; E unit Groups selected from the group consisting of hydrogen, C ₁ -C ₂₂ alkyl, C ₃ -C ₂₂ alkenyl, C ₇ -C ₂₂ arylalkyl, C ₂ -C ₂₂ hydroxyalkyl, -(CH ₂ ) _p CO ₂ M, -(CH ₂ ) _q SO ₃ M, -CH(CH ₂ CO ₂ M)CO ₂ M, -(CH ₂ ) _p PO ₃ M, -(R ¹ O) _x B, -C( O) R ³ , and mixtures thereof; oxides; B is hydrogen, C ₁ -C ₆ alkyl, -(CH ₂ ) _q SO ₃ M, -(CH ₂ ) _p CO ₂ M, -(CH ₂ ) _q (CHSO ₃ M)CH ₂ SO ₃ M, -(CH ₂ ) _q -(CHSO ₂ M)CH ₂ SO ₃ M, -(CH ₂ ) _p PO ₃ M, -PO ₃ M, and mixtures thereof; M is hydrogen or a water-soluble cation in an amount sufficient to satisfy charge balance; X is a water-soluble anion; m has a value of 4 to about 400; n has a value of 0 to about 200; p has a value of 1-6 and q has a value of 0-6; The r value is 0 or 1; the w value is 0 or 1; the x value is 1-100; the y value is 0-100; the z value is 0 or 1. An example of the most preferred polyethyleneimine is polyethyleneimine having a molecular weight of 1800 and further modified by ethoxylation to about 7 ethylene oxide residues per nitrogen ( PEI, 1800, E7). Preferably the above polymer solution is premixed with an anionic surfactant such as NaLAS.

Other preferred examples of aqueous or non-aqueous polymer solutions that can be used as the finely atomized liquids of the present invention are polycarboxylate dispersants which can be obtained by polymerizing suitable unsaturated monomers, preferably in the acid form, or prepared by copolymerization. Unsaturated monomeric acids that can be polymerized to form suitable polycarboxylates include: acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence in the polycarboxylates of monomeric segments containing non-carboxylic acid groups such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight of the polymer.

Homopolycarboxylates having a molecular weight greater than 4,000 are preferably employed. Particularly suitable homopolycarboxylates are obtainable from acrylic acid. Such acrylic acid-based polymers useful in the present invention are water-soluble salts of polymerized acrylic acid. The average molecular weight of such acid form polymers is preferably greater than 4,000 to 10,000, preferably greater than 4,000 to 7,000, most preferably greater than 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers include, for example, alkali metal, ammonium and substituted ammonium salts.

Copolymeric polycarboxylates such as acrylic/maleic based copolymers may also be used. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such acid form copolymers is preferably from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000. The ratio of acrylic acid segments to maleic acid segments in the copolymer is generally from about 30:1 to 1:1, more preferably from about 10:1 to 2:1. Examples of water-soluble salts of such acrylic acid/maleic acid copolymers include alkali metal, ammonium and substituted ammonium salts thereof. The above polymer solution is preferably pre-complexed with an anionic surfactant such as LAS. Builder ingredients

Other detergent ingredients may be included in the detergent raw material of the method of the present invention and/or various other ingredients may be incorporated into the detergent composition in subsequent steps of the method of the present invention. These adjunct ingredients include other builders, bleaching agents, bleach activators, suds suppressors or boosters, anti-tarnishing agents, preservatives, soil suspending agents, soil release Alkaline sources, chelating agents, smectites, enzymes, enzyme stabilizers and fragrances. See, US Pat. No. 3,936,537 (issued Feb. 3, 1976 to Baskerville, Jr. et al.), incorporated herein by reference.

Other builders are generally selected from the various water-soluble alkali metal, ammonium or substituted ammonium salt. Preference is given to the alkali metal salts, especially the sodium salts, of the abovementioned acids. Preferably used are phosphates, carbonates, C ₁₀ -C ₁₈ fatty acids, polycarboxylates and mixtures thereof. More preferred are sodium tripolyphosphate, tetrasodium pyrophosphate, citrates, tartrates, mono- and disuccinates, and mixtures thereof (see below).

Compared with amorphous sodium silicate, crystalline layered sodium silicate shows significantly enhanced calcium and magnesium ion exchange capacity. In addition, layered sodium silicates prefer magnesium ions over calcium ions, a feature that is necessary to ensure that substantially all "hardness species" are removed from the wash water. However, these crystalline layered sodium silicates are generally more expensive than amorphous silicates and other builders. Thus, in order to provide an economically viable laundry detergent, the proportion of crystalline layered sodium silicate used must be carefully selected. Such crystalline layered sodium silicates are described in US 4,605,509 (Corkill et al.), which is incorporated herein by reference.

Specific examples of inorganic phosphate builders are the sodium and potassium tripolyphosphoric acid, pyrophosphoric acid, polymeric metaphosphoric acid having a degree of polymerization of about 6-21, and orthophosphoric acid. Examples of polyphosphonate 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- Sodium and potassium salts of triphosphonic acid. Other phosphorus builder compounds are disclosed in US 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148; all of which are incorporated herein by reference.

Examples of phosphorus-free inorganic detergency builders are tetraborate decahydrate and silicates having a weight ratio of _SiO2 to alkali metal oxide of about 0.5-4.0, preferably about 1.0-2.4. The water-soluble phosphorus-free organic additives used in the present invention include various alkali metal salts, ammonium salts and substituted ammonium salts of polyacetic acid, carboxylic acid, polycarboxylic acid and polyhydroxysulfonic acid. Examples of polyacetic acid and polycarboxylate builders are sodium, potassium, lithium, ammonium and substituted ammonium salt.

Polymeric polycarboxylate builders are described in US 3,308,067, issued March 7, 1967 to Diehl, which is incorporated herein by reference. Such materials include the water-soluble salts of homopolymers and copolymers of aliphatic carboxylic acids such as maleic, itaconic, mesaconic, fumaric, aconitic, citraconic and methylenemalonic acids . Some of these materials can be used as the water-soluble anionic polymers described below, but only if they form an affinity mixture with the non-soap anionic surfactants.

Other polycarboxylates suitable for use in the present invention are polyacetal carboxylates as described in US 4,144,226 (authorized to Crutchfield et al. on March 13, 1979) and US 4,246,495 (authorized to Crutchfield et al. All documents are incorporated herein by reference. These polyacetal carboxylates can be prepared by bringing together, under polymerization conditions, esters of glyoxylic acid and a polymerization initiator. The formed polyacetal carboxylate is then attached to a chemically stable end group to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, converted into the corresponding salt, and added to the detergent composition middle. A particularly preferred polycarboxylate builder is an ether carboxylic acid builder composition comprising a combination of tartrate monosuccinate and tartrate disuccinate as described in US 4,663,071 (granted to Bush et al. on May 5, 1987) , which is incorporated herein by reference.

Bleaching agents and activators are described in US 4,412,934 (Chung et al. issued Nov. 1, 1983) and US 4,483,781 (Hartman issued Nov. 20, 1984), both of which are incorporated herein by reference. Chelating agents are also disclosed in US 4,663,071 (Bush et al.) at column 17, line 54 to column 18, line 68, which is incorporated herein by reference. Foam modifiers are also optional ingredients and are disclosed in US 3,933,672 (Bartoletta et al., issued January 20, 1976) and US 4,136,045 (Gault et al., issued January 23, 1979), both of which are incorporated herein by reference.

Smectite clays suitable for use in the present invention are described in US 4,762,645 (issued August 9, 1988 to Tucker et al.), column 6, line 3 to column 7, line 24, which is incorporated herein by reference. Other detergency builders suitable for use in the present invention are listed in the Baskerville patent literature (column 13, line 54 to column 16, line 16), and are described in US 4,663,071 (authorized May 5, 1987 to Bush et al.), Both are incorporated herein by reference. optional processing steps

The method of the present invention may also optionally include spraying other binders in one or more of the first mixer, second mixer and/or third mixer used in the present invention. Binders are added to enhance agglomeration performance by providing a "binder" or "sticker" for the detergent ingredients. The binder is preferably selected from water, anionic surfactants, nonionic surfactants, liquid silicates, polyethylene glycol, polyvinylpyrrolidone, polyacrylates, citric acid and mixtures thereof. Other suitable binder materials include those described in US 5,108,646 (Beerse et al., Procter & Gamble Co.), which is incorporated herein by reference.

Other optional steps of the process of the present invention include screening the oversized detergent agglomerates in screening equipment which may take various forms including screens commonly used in the desired particle size of the final detergent product, But it doesn't stop there. Other optional steps include the step of further drying the agglomerates by means of the aforementioned apparatus to condition the detergent agglomerates.

Another optional step of the process of the present invention involves conditioning the detergent agglomerates formed by various methods including spraying and/or premixing other conventional detergent ingredients. For example, the finishing step includes spraying perfumes, brighteners and enzymes onto the finished agglomerates to provide a more complete detergent composition. Such techniques and ingredients used are also well known to those skilled in the art.

Another optional step in the process of the present invention involves the formation of the surfactant paste, eg, hardening the aqueous anionic surfactant paste by adding a paste hardening material with an extruder prior to the process of the present invention. A detailed description of the method of surfactant paste construction is found in co-appln. no. PCT/US96/15960 (filed Oct. 4, 1996).

In order to make the present invention easier to understand, the present invention is described with reference to the following examples, but these examples are only for illustrating the present invention and do not limit the scope of the present invention in any way.

Embodiment Embodiment 1:

The following is an example of the preparation of agglomerates with high density using a Lödige KM mixer (KM-600) followed by a Schugi FX-160 mixer followed by a fluidized bed apparatus.

[Step 1] Acid chopper and/or precursor of 120-260 kg/hr HLAS (C ₁₁ -C ₁₈ alkylbenzene sulfonate; 95 % activity) at 45-60°C with 220kg/hr of powdered STPP (average particle size 40-75μm), 160-200kg/hr of ground soda ash (average particle size of 15μm), 80-120kg/hr of Ground sodium sulphate (average particle size 15 μm) was dispersed together with a 200 kg/hr internally circulating powder flow. Toothed paddles can be used as mixing parts in KM mixers. Shredders for KM mixers can be used to reduce the level of oversized agglomerates. The operating conditions of the KM mixer are as follows:

Average dwell time: 3-6 minutes

Energy condition: 0.15-2kj/kg

Mixing speed: 100-150rpm

Heating mantle temperature: 30-50°C

[Step 2] Add the agglomerates from the KM-600 mixer to the Schugi FX-160 mixer. 10-20 kg/hr HLAS (acid precursor of C ₁₁ -C ₁₈ alkylbenzene sulfonate; 94-97% active) was dispersed as a finely atomized liquid in a Schugi mixer at about 50-60°C. 20-80 kg/hr of soda ash (average particle size about 10-20 μm) was added to the Schugi mixer. The operating conditions of the Schugi mixer are as follows:

Average dwell time: 0.2-5 seconds

Peripheral speed: 16-26m/s

Energy condition: 0.15-2kj/kg

Mixing speed: 2000-3200rpm

[Step 3] The agglomerates in the Schugi mixer were fed into the fluidized bed drying equipment for drying, rounding and agglomerate growth. 20-80 kg/hr of liquid silicate (43% solids, 2.0R) was also added in a fluidized bed drying apparatus at 35°C. The operating conditions of the fluidized bed drying equipment are as follows:

Average dwell time: 4-8 minutes

Non-fluidized bed depth: 200mm

Spray droplet size: less than 50μm

Spray height: 175-250mm (above distribution plate)

Fluidization velocity: 0.4-0.8m/s

Bed temperature: 40-70°C

The product obtained from step 3 has a density of about 700 g/l, optionally subjected to cooling, classifying and/or grinding steps. Example 2:

The following is an example of the preparation of agglomerates with high density using a Lödige KM mixer (KM-600) followed by a Schugi FX-160 mixer followed by a fluidized bed apparatus.

[Step 1] 15-30 kg/hr HLAS (C ₁₁ -C ₁₈ Acid Precursor of Alkylbenzene Sulfonate ; 95% active) with 220kg/hr of powdered STPP (average particle size 40-75μm), 160-200kg/hr of ground soda ash (average particle size of 15μm), 80-120kg/hr of ground sulfuric acid Sodium (average particle size 15 μm) is dispersed together with a 200 kg/hr internal circulating powder flow. Toothed paddles can be used as mixing parts in KM mixers. Shredders for KM mixers can be used to reduce the level of oversized agglomerates. The operating conditions of the KM mixer are as follows:

Average dwell time: 3-6 minutes

Energy condition: 0.15-2kj/kg

Mixing speed: 100-150rpm

Heating mantle temperature: 30-50°C

[Step 2] Add the agglomerates from the KM-600 mixer to the Schugi FX-160 mixer. 10-25 kg/hr neutral _AE3S liquid (25-28% active) was dispersed into a fine atomized liquid in a Schugi mixer at about 30-40°C. 20-80 kg/hr of soda ash was added to the Schugi mixer. The operating conditions of the Schugi mixer are as follows:

Average dwell time: 0.2-5 seconds

Peripheral speed: 16-26m/s

Energy condition: 0.15-2kj/kg

Mixing speed: 2000-3200rpm

[Step 3] The agglomerates in the Schugi mixer were fed into the fluidized bed drying equipment for drying, rounding and agglomerate growth. 20-80 kg/hr of liquid silicate (43% solids, 2.0R) was also added in a fluidized bed drying apparatus at 35°C. The conditions of fluidized bed drying equipment are as follows:

Average dwell time: 2-4 minutes

Non-fluidized bed depth: 200mm

Droplet spray particle size: less than 50μm

Spray height: 175-250mm (above distribution plate)

Fluidization velocity: 0.4-0.8m/s

Bed temperature: 40-70°C

The product obtained from step 3 has a density of about 700 g/l, optionally subjected to cooling, classifying and/or grinding steps. Example 3:

The following is an example of the preparation of agglomerates with a high density using a Ldige KM mixer (KM-600) followed by further agglomeration using fluidized bed equipment.

[Step 1] 250-270kg/hr, aqueous coconut oil fatty alcohol sulfate surfactant paste (C ₁₁ -C ₁₈ , 71.5% active), 40-80kg/hr HLAS (C ₁₁ -C ₁₈ alkylbenzene sulfonic acid acid precursor of the salt; 94-97% active) and 220 kg/hr of powdered STPP (average particle size 40-75 μm), 160-200 kg/hr of ground soda ash (average particle size 15 μm), 80-120 kg /hr of ground sodium sulfate (average particle size 15 μm) was fed into the KM-600 mixer together with a 200 kg/hr internal circulation powder flow. Add surfactant paste at 40-52°C and powder at room temperature. Shredders for KM mixers can be used to reduce the level of oversized agglomerates. The conditions of the KM mixer are as follows:

Average dwell time: 3-6 minutes

Energy condition: 0.15-2kj/kg

Mixing speed: 100-150rpm

Heating mantle temperature: 30-50°C

[Step 2] The agglomerates in the KM mixer are fed into the fluidized bed drying equipment for drying, rounding and agglomerate growth. 20-80 kg/hr of liquid silicate (43% solids, 2.0R) was also added in a fluidized bed drying apparatus at 35°C. The conditions of fluidized bed drying equipment are as follows:

Average dwell time: 2-4 minutes

Non-fluidized bed depth: 200mm

Droplet spray particle size: less than 50μm

Spray height: 175-250mm (above distribution plate)

Fluidization velocity: 0.4-0.8m/s

Bed temperature: 40-70°C

The product obtained from step 3 has a density of about 700 g/l, optionally subjected to cooling, classifying and/or grinding steps.

The present invention has been described in detail above, and those skilled in the art can clearly see that various modifications can be made without departing from the scope of the present invention, and the present invention is not limited by the content described above.

Claims (10)

1, a kind ofly prepare the non-tower process that density is at least about the granular detergent composition of 600g/l, this method comprises the steps:

(a) scatter table surface-active agent in mixing tank, be coated with this tensio-active agent with the fine powder that with diameter is 0.1-500 μ m, the condition of wherein said mixing tank comprises: (1) mean residence time is about 0.5-15 minute and (2) energy condition is about 0.15-7kj/kg, wherein forms agglomerate; With

(b) in one or more fluidizing devices, agglomerate is carried out granulation, wherein the condition of each fluidizing device comprises that (1) mean residence time is about 1-10 minute, (2) the fluidizing bed degree of depth is not the about 300mm of about 100-, (3) the drop spray particle diameter is no more than about 50 μ m, (4) spray height is the about 250mm of about 175-, (5) fluidizing velocity is about 0.2-1.4m/s, and (6) fluidized-bed temperature is about 12-100 ℃.

2, a kind ofly prepare the non-tower process that density is at least about the granular detergent composition of 600g/l,

This method comprises the steps:

(a) scatter table surface-active agent in mixing tank, and be that the fine powder of 0.1-500 μ m is coated with this tensio-active agent with diameter, the condition of wherein said mixing tank comprises: (1) mean residence time is about 0.5-15 minute, and (2) energy condition is about 0.15-7kj/kg, wherein forms first agglomerate;

(a ') is in mixing tank, the fine atomized liquid of spraying on first agglomerate, the condition of wherein said mixing tank comprises: (1) mean residence time is about 0.2-5 second, and (2) tip velocity is about 10-30m/s, (3) energy condition is about 0.15-5kj/kg, wherein forms second agglomerate; With

(b) in one or more fluidizing devices, second agglomerate is carried out granulation, wherein the condition of each fluidizing device comprises that (1) mean residence time is about 1-10 minute, (2) the fluidizing bed degree of depth is not about 100-300mm, (3) the drop spray particle diameter is no more than about 50 μ m, (4) spray height is about 175-250mm, (5) fluidizing velocity is about 0.2-1.4m/s, and (6) fluidized-bed temperature is about 12-100 ℃.

3, according to the method for claim 1 or 2, wherein, described tensio-active agent is selected from anion surfactant, nonionogenic tenside, cats product, zwitterionics, amphoterics and its mixture.

4, according to the method for claim 1 or 2, wherein, described tensio-active agent is selected from alkylbenzene sulfonate, alkyl alkoxy sulfate, alkylethoxylate, alkyl-sulphate, coco fatty alcohol sulfate and its mixture.

5, according to the method for claim 1 or 2, wherein, in step (a) with described surfactant-dispersed moisture or non-aqueous polymer solution.

6, according to the method for claim 1 or 2, wherein, described fine powder is selected from SODA ASH LIGHT 99.2, powdery tripoly phosphate sodium STPP, hydration tri-polyphosphate, sodium sulfate, silico-aluminate, crystalline layered silicate, phosphoric acid salt, precipitated silicate, polymkeric substance, carbonate, Citrate trianion, nitrilotriacetic acid(NTA) salt, powdery surface promoting agent and composition thereof.

7, according to the method for claim 1 or 2, wherein also in the future the internal recycle flow of powder of self-fluidized type equipment join in the step (a).

8, according to the method for claim 2, wherein fine atomized liquid is selected from liquid silicon hydrochlorate, anion surfactant, cats product, aqueous polymers solution, non-aqueous polymer solution, water and composition thereof.

9, according to the method for claim 2, wherein in step (a), form excessive fine powder, and wherein this excessive fine powder is added in the step (a ').

10, a kind of granular detergent composition for preparing by the method for claim 1 or 2.