CN1239506A

CN1239506A - Process for making detergent compsn. by non-tower process

Info

Publication number: CN1239506A
Application number: CN97180278.5A
Authority: CN
Inventors: A·G·德尔格雷科; W·E·贝梅施; M·坎达萨麦
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1996-10-04
Filing date: 1997-06-05
Publication date: 1999-12-22
Anticipated expiration: 2017-06-05
Also published as: ES2178778T3; CA2268060C; CN1156560C; CN1156563C; AU3478397A; AU3303097A; EP0929649B1; CA2268055A1; CA2268062C; JP3299985B2; CA2267424A1; AR010507A1; CN1133738C; DE69726439D1; AU3478597A; JP2000503715A; BR9711865A; DE69723986T2; JP3299981B2; EP0929650A1

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 a surfactant, and coating the surfactant with fine powder in a mixer, wherein first agglomerates are formed; (b) spraying finely atomized liquid onto the first agglomerates in a mixer, wherein second agglomerates are formed; and (c) granulating the third agglomerates in one or more fluidizing apparatus. The process can also comprise further step (b'), i.e., thoroughly mixing the second agglomerates in a mixer, between step (b) and step (c).

Description

Make the method for cleaning composition with non-tower process

Invention field

The present invention relates generally to produce the non-tower method of granular detergent compositions.More specifically, The present invention be directed to a kind of successive method, this method comprises adding tensio-active agent and coat last material in a series of mixing tank produces detergent agglomerate.This method is produced the free-pouring cleaning composition of a kind of energy, and its density can be adjusted in the needed wide range of human consumer, and said composition can be sold on market.

Background of invention

Quite interested in detergent for washing clothes " densification ", that the use volume is little in detergent industry recently.In order to promote the production of these so-called low consumption washing composition, to produce high bulk density for example density be that washing composition more than the 600g/l has carried out many explorations.Because low consumption washing composition is saved resource, and can with to the human consumer more easily small packages sell, so at present it is in great demand.Yet the compactness extent that modern Betengent product need reach does not in fact also solve.In fact, many human consumers', particularly developing country human consumer still likes bigger consumption in their laundry processes separately.

The method of preparing washing agent particle or powder generally has two big classes.First kind method is included in the aqueous washing composition slurry of spraying drying in the spray-drying tower, produces very loose detergent particles (tower process of for example production low density cleaning composition).In second class methods, with various detergent ingredients dry blending, adopt binding agent then, tensio-active agent for example non-ionic type or anionic earlier, make their agglomeration, produce highdensity detergent composition (for example producing the agglomeration method of high density detergent).In above two kinds of methods, the important factor of the detergent particle granule density that control is produced is described coating of particles, porosity and size-grade distribution, the density of various raw materials, the shape of various raw materials and chemical constitution separately thereof.

For the method that improves detergent particles or powder density is provided, many trials in this area, have been carried out.Especially notice and adopt (Post tower) behind the tower to handle compaction spray-dried granules.For example, a kind of process of attempting using an interruption is arranged, in this process, make the detergent powder densification of the spray-dired or granulation that contains tripoly phosphate sodium STPP and sodium sulfate, and make its nodularization in a Marumerizer .In this equipment, comprise that one is level, coarse rotating disk basically, it is positioned at one is the bottom of slick cylinder on vertical, the wall basically.Yet this method is the method for an interruption basically, thereby is not suitable for producing on a large scale detergent powder.Recently, for forming the continuation method that improves " behind the tower " drying or spray-dried detergent pellet density.Other trials have been carried out.These methods need be pulverized or grind the particulate primary equipment usually and improve by the second set of pulverized particles density by nodulizing.Though these methods are handled " behind the tower " drying or spray-dired particle or made its densification, have reached the requirement that improves density, do not have encapsulation steps subsequently, the ability that makes their improve tensio-active agent effective content is restricted.In addition, from the viewpoint of economics (investment cost height) and complicated operation degree, it is disadvantageous adopting " behind the tower " processing or densification.And all above-mentioned methods are mainly at densification, or in other words, are at handling spray-dired particle.In the production of granulated detergent, the relative populations and the kind of the material of process spray drying treatment are restricted at present.For example in the cleaning composition of producing, obtain high-load tensio-active agent and be difficult to, this is the principal element that promotes to produce with more efficient methods washing composition.Therefore, need a kind of method that can not be subjected to the production cleaning composition of restriction that conventional spray drying technology adds.

Also there are many open source informations that carry out the method for cleaning composition agglomeration process for this purpose this area.For example mixed zeolite and/or lamellated silicate in mixing tank carry out the agglomerant trial of scrubbed component, can free-pouring agglomerate so that make.Though these trials show, their method can be applied to produce detergent agglomerate, but they do not propose and can effectively pasty state, liquid be agglomerated into mechanism crisp, the free-pouring detergent agglomerate of energy with the exsiccant detergent raw material.

Therefore, this area also needs a kind of method (non-tower method) of continuous production high density detergent composition agglomerate, and its high-density is directly produced by the washing composition original composition, can preferably reach this density by regulating working condition.Yet needing a kind of (1) can adapt to the final densities of final product composition having and (2) and can adapt to several dissimilar detergent ingredients (particularly Ye Tai detergent ingredients) in the adition process, more effective, more flexible and more economical method is so that produce washing composition on a large scale.

As follows at the reference that makes spray-dired particle densification: people's such as A Peier United States Patent (USP) 5,133,924 (Lever); People's such as rich holder loti United States Patent (USP) 5,160,657 (Lever); People's such as Johnson English Patent 1,517,713 (Unilever); European patent application 451,894 with Ke Disi.

As follows at the reference that adopts agglomeration method production washing composition: than people's such as treasure patent, publication number is WO93/23,523 (Henkel), people's such as Lu thatch United States Patent (USP) 4,992,079 (FMC Corp.); People's such as Bo Laxike United States Patent (USP) 4,427,417 (Korex); People's such as Bill's Si grade United States Patent (USP) 5,108,646 (Procter ﹠amp; Gamble); People's such as Ka Peixi United States Patent (USP) 5,366,652 (Procter; Gamble); People's such as Hollingworth european patent application 351,937 (Unilever); People's such as Si Watelin United States Patent (USP) 5,205,958; People's such as Da Erwodika patent, publication number are WO96/04,359 (Unilever).

For example, open application is WO93/23, and the method that 523 (Henkel) are narrated is comprising adopting the pre-agglomeration of slow-speed mixer and adopting the further agglomerant step of super mixer, to obtain highdensity cleaning composition, wherein diameter is lower than 25% (weight) greater than the particle of 2mm.United States Patent (USP) 4,427,417 (Korex) have narrated the successive agglomeration method, and this method has reduced the agglomerate of caking and oversized dimensions.

There is not a kind of prior art that all these advantages of the present invention and benefit can be provided.

Summary of the invention

The invention provides a kind of method of producing high-density granulated cleaning composition, satisfied the above-mentioned needs of this area.The present invention also provides a kind of method by agglomeration technique (for example non-tower method) production granular detergent compositions that can adapt to the final product composition having final densities, has satisfied the above-mentioned needs of this area.This method does not adopt conventional spray-drying tower, and this tower is restricted in the high Composition Aspects of production surfactant content at present.In addition, method of the present invention various cleaning composition that available present method is produced are all more effective, both economical and adaptability is stronger.And because present method does not adopt the common spray-drying tower that can give out particle and volatile organic compounds in atmosphere, it more can stand the check of environmental protection aspect.

Term used herein " agglomerate " means the employing binding agent, and for example tensio-active agent and/or inorganic solution/organic solvent and polymers soln make the particle that the raw material agglomeration is made.Term used herein " granulation " means and makes agglomerate fluidisation fully that producing can free-pouring, spherolitic agglomerate.Term used herein " mean residence time " means to give a definition:

Mean residence time (h)=quality (kg)/flow (kg/h)

Except as otherwise noted, all percentage used herein are all represented with weight percentage.Except as otherwise noted, all ratios all are weight ratios." comprising " used herein means and can add other step and other composition that does not influence the result.This term contained term " by ... form " and " basically by ... composition ".

According to an aspect of the present invention, provide a kind of method for preparing granular detergent compositions, the density of said composition is at least about 600g/l.

This method may further comprise the steps:

(a) in mixing tank, disperse a kind of tensio-active agent, and be that the fine powder of 0.1-500 μ coats this tensio-active agent with diameter, wherein the operational condition of mixing tank comprises: (i) mean residence time about 2 is to about 50s, (ii) terminal velocity about 4 is to about 25m/s, (iii) energy state about 0.15 is made first agglomerate therein to 7kj/kg;

(b) in mixing tank with the spray liquid of mistization to first agglomerate, wherein the operational condition of mixing tank comprises: (i) mean residence time about 0.2 is to about 5s, (ii) terminal velocity about 10 is to about 30m/s, (iii) energy state about 0.15 is made second polymkeric substance therein to about 5kj/kg; With

(c) in one or more fluidizing apparatus, make second agglomerate carry out granulation, wherein the operational condition of every fluidizing apparatus comprises: (i) mean residence time about 1 is to about 10min, (ii) quiet bed height about 100 is to about 300mm, (iii) The droplet sizes is not more than about 50 μ, (iv) spray height about 175 is to about 250mm, (v) fluidizing velocity about 0.2 to about 1.4m/s and (vi) bed temperature about 12 is to about 100 ℃.

The present invention also provides a kind of method for preparing granular detergent compositions, and the density of said composition is at least about 600g/l, and this method may further comprise the steps:

(a) in mixing tank, disperse a kind of tensio-active agent, and coat this tensio-active agent with the fine powder of diameter 0.1-500 μ, wherein the operational condition of mixing tank comprises: (i) mean residence time about 2 is to about 50s, (ii) terminal velocity about 4 is to about 25m/s, (iii) energy state about 0.15 is made first agglomerate therein to about 7kj/kg;

(b) in mixing tank with the spray liquid of mistization to first agglomerate, wherein the operational condition of mixing tank comprises: (i) mean residence time about 0.2 is to about 5s, (ii) terminal velocity about 10 is to about 30m/s, (iii) energy state about 0.15 is made second polymkeric substance therein to about 5kj/kg;

(b ') be thorough mixing second agglomerate in mixing tank, and wherein the operational condition of mixing tank comprises: (i) mean residence time about 0.5 to about 15min and (ii) energy state about 0.15 make terpolymer therein to about 7kj/kg; With

(c) in one or more fluidizing apparatus, make the 3rd agglomerate carry out granulation, wherein the operational condition of each fluidizing apparatus comprises: (i) mean residence time about 1 is to about 10min, (ii) quiet bed height about 100 is to about 300mm, (iii) The droplet sizes is not more than about 50 μ, (iv) spray height about 175 is to about 250mm, (v) fluidizing velocity about 0.2 to about 1.4m/s and (vi) bed temperature about 12 is to about 100 ℃.

The present invention also provides the highdensity granular detergent compositions of being produced by the embodiment of any method as herein described, and wherein density is at least about 600g/l.

Therefore, the purpose of this invention is to provide a kind of method of continuous production cleaning composition, by energy input, the residence time and the terminal velocity condition in the control mixing tank, the density of regulating finished product neatly.Another object of the present invention provides a kind of scale operation of being convenient to, more effective, more flexible and more economical method.To those skilled in the art, by below reading to the detailed description of preferred embodiment and claims, these and other objects of the present invention, feature and attendant advantages are clearly.

The accompanying drawing summary

Fig. 1 is the process flow sheet according to one embodiment of the invention, comprising adopt earlier first mixing tank, then adopt second mixing tank, adopt the agglomeration process of fluidizing apparatus then, production density is at least the granular detergent compositions of 600g/l.

Fig. 2 is the process flow sheet according to one embodiment of the invention, comprising adopt earlier first mixing tank, then adopt second mixing tank, then adopt the 3rd mixing tank, adopt the agglomeration process of fluidizing apparatus at last, production density is at least the granular detergent compositions of 600g/l.

Fig. 3 is a process flow sheet that can carry out various agglomeration process, and these agglomeration process are selected from first mixing tank, second mixing tank, the 3rd mixing tank, fluidizing apparatus and their combination, to produce the granulous cleaning composition.

The detailed description of preferred embodiment

The present invention be directed to the method for the free-pouring granulated detergent agglomerate of production energy, agglomeration The density of thing is at least about 600g/l. The method is by surfactant water-based and/or nonaqueous Produce granular detergent agglomerate, surfactant is used the fine powder of diameter 0.1-500 μ subsequently Coat, in order to obtain low-density particle.

Method

Referring now to Fig. 1,, this figure is explanation embodiment of the present invention, below namely comprising The flow chart of method of first step, second step (i) and third step; With referring to Fig. 2, Fig. 2 is explanation embodiment of the present invention, namely comprises following first step, second step Suddenly (i) and (ii) and the flow chart of the method for third step. Now referring again to Fig. 3, Fig. 3 It is the flow chart of the various embodiments that the present invention includes of an explanation. First step (step (a))

In the first step of this method, with surfactant 11, namely one or more are Powdered , water-based pasty state and/or liquid and/or nonaqueous surfactant and diameter 0.1-500 μ, preferred about 1 to about 100 μ fine powder 12 adds in first blender 13, so that Make agglomerate. (at length having narrated hereinafter the definition of surfactant and fine powder) Except fine powder, can choose wantonly in the fluidizing apparatus described in the third step 27 hereinafter Produce, diameter 0.1 to the interior circular flow of about 300 μ powder 30 adds in the blender. Described The amount of powder 30 interior circular flows can be finished product 29 0 to about 60% (weight).

In another embodiment of the invention, can be before above-mentioned step, begin with Surfactant 11 add a blender or premixer (for example conventional screw extruder or Other similar blender) in, then the detergent materials that mixes is added described herein first Carry out agglomeration in the blender of step.

In general, the mean residence time of preferred first blender is about 2 to about 50s, first The tip speed of blender is that about 4m/s is to about 25m/s, the energy of the first blender per unit mass Amount (energy state) is extremely about 7kj/kg of about 0.15kj/kg, and more preferably first blender is average The time of staying is about 5 to about 30s, the tip speed of first blender for about 6m/s to pact 18m/s, the energy of the first blender per unit mass (energy state) for about 0.3kj/kg extremely About 4kj/kg, more preferably the mean residence time of first blender is about 5 to about 20s, first is mixed The tip speed of closing device is that about 8m/s is to about 18m/s, the energy of the first blender per unit mass (energy state) is that about 0.3kj/kg is to about 4kj/kg.

The example of first step blender can be arbitrary kind known to those skilled in the art The blender of type is as long as this blender can keep the above-mentioned condition of first step. L  dige company The L  dige CB blender that (Germany) makes can be an example. Obtain by first step Made product 16 (first agglomerate that has fine powder on the surface of agglomerate). Second step (step (b)/step (b '))

As a preferred embodiment, two kinds of selections are arranged, namely only have second step (i), Or at second step (i) then second step (ii) afterwards. Second step (i) (step (b)): with made product 16, i.e. first agglomerate Add in second blender 17, then in second blender 17 with liquid 18 spray of mist Be spread across on first agglomerate. The optional meticulous powder that will form in first step is added to second In the step, if meticulous powder is added in the second step (i), spray the liquid of mist To being effective on the surface that meticulous powder is bonded to agglomerate. Can in blender 17, add Enter about 0-10%, the more preferably from about various Powdered washing in first step, used of 2-5% Agent composition and/or other detergent ingredients.

In general, the mean residence time of preferred second blender is about 0.2 to about 5s, The tip speed of two blenders is that about 10m/s is to about 30m/s, the second blender per unit mass Energy (energy state) is extremely about 5kj/kg of about 0.15kj/kg, and more preferably second blender is flat All the time of staying is about 0.2 to about 5s, and the tip speed of second blender is about 10m/s pact extremely 30m/s, the energy of the second blender per unit mass (energy state) for about 0.15kj/kg extremely About 5kj/kg, most preferably the mean residence time of second blender is about 0.2 to about 5s, second is mixed The tip speed of closing device is that about 15m/s is to about 26m/s, the energy of the second blender per unit mass Amount (energy state) is that about 0.2kj/kg is to about 3kj/kg.

The example of second blender 17 can be any type well known by persons skilled in the art Blender is as long as this blender can keep the above-mentioned condition of second step (i). Schugi company (lotus Orchid) the Felexomic Model that makes can be an example. By second step, obtain institute The product 20 of system. Make then made product 20 (second agglomerate) through second step (ii) Or third step.

Second step (ii) (step (b ')): the product 20 that second step (i) is made (second agglomerate) adds in the 3rd blender 21, namely fully mixes at the 3rd blender 21 The product that second blender is made, and it is sheared fully, so that agglomerate becomes circle and long Greatly. Can choose wantonly will about 0-10%, more preferably from about 2-5% is at first step and/or second step (i) the various pulverous detergent ingredients that uses in and/or other detergent ingredients add second In the step (ii). The shredding mechanism that can preferably use the 3rd blender to install is pulverized undesirable surpassing The agglomerate of size. Therefore the method comprises the 3rd blender 21 that shredding mechanism is housed, to subtracting The agglomerate amount of oversize is effective in few finished product. This method be of the present invention one excellent The embodiment of choosing.

In general, the mean residence time of preferred the 3rd blender is about 0.5 to about 15min, The energy of the 3rd blender per unit mass (energy state) is about 0.15 to about 7kj/Kg, more The mean residence time of preferred the 3rd blender is about 3 to about 6min, the 3rd blender per unit The energy of quality (energy state) is about 0.15 to about 4kj/kg.

The example of the 3rd blender 21 can be any type well known by persons skilled in the art Blender is as long as this blender can keep the above-mentioned condition of second step (ii). L  dige company The L  dige KM blender that (Germany) makes can be an example. By second step (ii) Obtain made product 24. I.e. circular particle. Third step (step (c))

In the third step of this method, the product that second step is made, i.e. made product 20 or made product 24, add fluidizing apparatus 27 for example in the fluid bed, to strengthen granulation Effect, producing can free-pouring high density granular. Third step can be in one or more fluidised forms Change equipment (for example with dissimilar fluidizing apparatus, for example fluidized bed dryer and fluid bed Cooler combines) in carry out. In third step, make the made product of second step Fully fluidization is so that the particle that third step is made is circular. Can choose wantonly about 0 To about 10%, the various powder detergent materials that in first step, use of 2-5% more preferably from about Material and/or other detergent ingredients add in the third step. Also can choose wantonly with about 0 to about 20%, 2 to about 10% various liquid detergents that in first step, second step, use more preferably from about Material and/or other detergent ingredients add in this step, to strengthen granulation and to be coated on On the surface of grain.

In general, in order to reach density at least about 600g/l, preferably be higher than 650g/l, the operating condition of fluidizing apparatus can be:

Mean residence time: about 1 to about 10min

Quiet bed height: about 100 to about 300mm

The droplet sizes: be not more than about 50 μ

Spray height: about 175 to about 250mm

Fluidization rate: about 0.2 to about 1.4m/s

Bed temperature: about 12 to about 100 ℃ more preferably:

Mean residence time: about 2 to about 6min

Quiet bed height: about 100 to about 250mm

The droplet sizes: less than about 50 μ

Spray height: about 175 to about 200mm

Fluidization rate: about 0.3 to about 1.0m/s

Bed temperature: about 12 to about 80 ℃

If use two kinds of dissimilar fluidizing apparatuss, the overall average residence time of third step can be about 2 to about 20min, and more preferably from about 2 to 12min.

In order to improve the mobile of cleaning composition and/or undue nodulizing wherein to be reduced to minimum, can add coating in the one or more following place of present method: (1) can directly add coating after fluidized bed cooler or fluidized bed dryer, (2) can between fluidized bed dryer and fluidized bed cooler, add coating, and/or (3) can directly add coating in the 3rd mixing tank 21 and the fluidized bed dryer.Coating is preferably from aluminosilicate, silicate, carbonate and composition thereof.Coating can not only strengthen the free-flowing property of made cleaning composition, and this flowability is that the human consumer is needed, because it dips washing composition in use easily with spoon, and can also be by avoiding or reducing excessive nodulizing and control agglomerate.Because those skilled in the art is fully aware of, excessively agglomeration can cause the finished product washing composition to have very undesirable flowability and outward appearance.

The Schugi mixing tank that is fit to inject at least two kinds of liquid components in the CB mixing tank that adopts at least two kinds of liquid components of (1) suitable injection, (2), the suitable fluidized-bed that injects at least two kinds of liquid components in KM mixing tank, (4) that (3) are fit at least a liquid component of injection realize that under the situation of method of the present invention, this method can add 7 kinds of dissimilar liquid components during the course.Therefore, for liquid state, quite valuable, the detergent raw material than more difficult transportation of solid material and/or storage joins in the granulation process sometimes, the method for being recommended is useful to those skilled in the art.

Need from industry, the present invention who is recommended also is practical, because those skilled in the art can be provided with a series of equipment (for example shown in Figure 3) in factory, and, enable those skilled in the art to select diverse ways to satisfy desired end properties (for example granularity, density and formulating of recipe) by adopting the reverser that some can connection/disconnection between each equipment.These variations not only comprise method of the present invention, promptly as shown in Figure 3, (i) the first mixing tank 13-(line 16)-second mixing tank 17-(line 26)-fluidizing apparatus 27-(line 28)-finished product 29, the (ii) first mixing tank 13-(line 16)-second mixing tank 17-(line 20) the-the 3rd mixing tank 21-(line 24)-fluidizing apparatus 27-(line 28)-finished product 29, but also comprise the (iii) first mixing tank 17-(line 16 ') the-the 3rd mixing tank 21-(line 24)-fluidizing apparatus 27-(line 28)-finished product 29, the (iv) first mixing tank 13-(line 16 ') the-the 3rd mixing tank 21-(line 23)-second mixing tank 17-(line 26)-fluidizing apparatus 27-(line 28)-finished product 29 and (the v) first mixing tank 13-(line 16 ")-fluidizing apparatus 27-(line 28)-finished product 29.

Detergent raw material

In the made product of the present invention, the total amount of tensio-active agent is calculated with percentage, is generally about 5% to about 60%, and more preferably from about 12% to about 40%, more preferably from about 15 to about 35%, they are included in the liquid and washing composition added ingredients of following detergent materials, mistization again.The tensio-active agent that comprises in above-mentioned materials can for example add from one of first step of the present invention, second step and/or third step from arbitrary part of method of the present invention.Detergent surfactant (water-based/nonaqueous)

The consumption of the tensio-active agent of present method by the finished product total of method gained of the present invention, can be about 5% to about 60%, and more preferably from about 12% to about 40%, and more more preferably from about 15 to about 35%.

The tensio-active agent of present method that is used as the above-mentioned detergent raw material of first step is the raw material of Powdered, pasty state or liquid form.

The kind of tensio-active agent itself is preferably from anionic, non-ionic type, amphoteric ion type, amphoteric, cationic and compatible mixture.United States Patent (USP) 3 the Norris of on May 23rd, 1972 promulgation, the people's such as Lao Kelin of promulgation on December 30th, 664,961 and 1975 United States Patent (USP) 3,929, narrate the used detergent surfactant of the present invention in 678, be incorporated herein these two parts of patents as a reference.Used cats product also is included in the United States Patent (USP) 4 of the Cockerell of promulgation on September 16th, 1980,222,905 and at the luxuriant and rich with fragrance United States Patent (USP) 4,239 of the China ink of on December 16th, 1980 promulgation, described in 659 those are also introduced these two parts of patents as a reference at this.In tensio-active agent, anionic and non-ionic type are preferred, and anionic is most preferred.

The non-limiting example of the preferred anionic surfactants tensio-active agent of Shi Yonging comprises conventional C in the present invention ₁₁-C ₁₈Alkylbenzene sulfonate (" LAS "); Have main chain, side chain and random C ₁₀-C ₂₀Alkyl sulfuric ester salt (" AS "), general formula is CH ₃(CH ₂) _x(CHOSO ₃ ^-M ⁺) CH ₃And CH ₃(CH ₂) _y(CHOSO ₃ ^-M ⁺) CH ₂CH ₃C ₁₀-C ₁₈(2,3) alkyl sulfuric ester salt in addition, x and (y+1) be at least about 7 integer in the formula, preferably at least about 9, M is a water-soluble cationic, particularly sodium; Undersaturated sulfuric acid, for example oleyl alcohol sulfuric acid; And C ₁₀-C ₁₈Alkyl alkoxy sulfuric acid (" AE _xS "; EO 1-7 oxyethyl group sulfuric acid particularly).

The anion surfactant that uses also comprises the water-soluble salt of 2-acyloxy-alkane-1-sulfonic acid, wherein contains about 2-9 carbon atom in acyl group, contains about 9 to about 23 carbon atoms in the alkane chain; The water-soluble salt of alkenes sulfonate wherein contains about 12-24 carbon atom; β-alkoxyl group alkyl sulfonate, wherein alkyl contains about 1-3 carbon atom, contains about 8-20 carbon atom in the alkane chain.

Other exemplary surfactants of using with pasty state in the present invention, the optional C that comprises ₁₀-C ₁₈Alkyl alkoxy carboxylate salt (particularly ethoxy carboxylate), C ₁₀-C ₁₈Glyceryl ether, C ₁₀-C ₁₈The poly-glycosides and the C of alkylpolyglycosides and corresponding sulphating ₁₂-C ₁₈α-sulfonated fatty acid ester.If desired, in total composition, also can comprise conventional non-ionic type and tensio-active agent amphoteric, for example comprise the C of the alkylethoxylate at so-called narrow peak ₁₂-C ₁₈Alkylethoxylate (" AE ") and C ₆-C ₁₂Alkyl phenolic alkoxy thing (particularly ethoxylate and blended oxyethyl group/propoxy-), C ₁₀-C ₁₈Amine oxide etc.Also can use C ₁₀-C ₁₈Many hydroxy fatty acids of N-alkyl acid amides.Typical example comprises C ₁₂-C ₁₈The N-methyl glucose amide.See WO9,206,154.Other sucrose deutero-tensio-active agent comprises many hydroxy fatty acids of N-alkoxyl group acid amides, for example C ₁₀-C ₁₈N-(3-methoxy-propyl) glucamide.Also can use the N-propyl group to N-hexyl C ₁₂-C ₁₈Glucamide reduces foam.Also can use C ₁₀-C ₂₀Conventional soap.Many if desired foams can use branched C ₁₀-C ₁₆Soap.The mixture of anionic and nonionic surface active agent is a particularly suitable.In the textbook of standard, listed other tensio-active agent commonly used.

Also can adopt cationic surfactant as detergent surfactant of the present invention, suitable quaternary ammonium surfactant is selected from a C ₆-C ₁₆, preferred C ₆-C ₁₀N-alkyl or alkylene quaternary ammonium surfactant, wherein Sheng Xia N position is replaced by methyl, hydroxyethyl or hydroxypropyl.Also can adopt amphoterics as detergent surfactant of the present invention, comprising the aliphatic derivatives of heterocyclic secondary and tertiary amine; Zwitterionics is comprising the derivative of aliphatic quaternary ammonium, Phosphonium, sulfonium compound; The water-soluble salt of α-sulfonated fatty acid ester; Sulfated alkyl ether; The water-soluble salt of alkene sulfonate; β-alkoxyl group alkyl sulfonate; General formula is R (R ¹) ₂N ⁺R ²COO ^-Trimethyl-glycine, R is C in the formula ₆-C ₁₈Alkyl, preferred C ₁₀-C ₁₆Alkyl or C ₁₀-C ₁₆Amidoalkyl, each R ¹Be generally C ₁-C ₃Alkyl, preferable methyl, and R ²Be C ₁-C ₅Alkyl, preferred C ₁-C ₃Alkylidene group, more preferably C ₁-C ₂, alkylidene group.The example of suitable trimethyl-glycine comprises coconut amido propyl-dimethyl trimethyl-glycine; The hexadecyldimethyl benzyl ammonium trimethyl-glycine; C _12-14Amido propyl betaine; C _8-14Amido hexyl diethyl betaines; 4 (C _14-16Acyl group methylamino-diethyl ammonium)-1-carboxylic butane; C _16-18The amido dimethyl betaine; C _12-16Amido pentane diethyl betaines; And C _12-16Acyl group methylamino-dimethyl betaine.Preferred trimethyl-glycine is C _12-18Dimethyl-ammonium hexanoate and C _10-18Amido propane (or ethane) dimethyl (or diethyl) trimethyl-glycine; With general formula be R (R ¹) ₂N ⁺R ²SO ₃ ^-The sulfonation trimethyl-glycine, R is C in the formula ₆-C ₁₈Alkyl, preferred C ₁₀-C ₁₆Alkyl, more preferably C ₁₂-C ₁₃Alkyl, each R ¹Be generally C ₁-C ₃Alkyl, preferable methyl, R ²Be C ₁-C ₆Alkyl, preferred C ₁-C ₃Alkylidene group or preferred hydroxy alkylidene.The example of suitable sulfonation trimethyl-glycine comprises C ₁₂-C ₁₄Dimethylammonium-2-hydroxypropyl sulfonate, C ₁₂-C ₁₄Amino third ammonium-2-hydroxypropyl sulfonation trimethyl-glycine, C ₁₂-C ₁₄Dihydroxy ethyl ammonium propane sulfonate, and C ₁₆-C ₁₈Dimethylammonium hexane sulfonate, and C preferably ₁₂-C ₁₄Amido third ammonium-2-hydroxypropyl sulfonation trimethyl-glycine.Fine powder

The fine powder amount that present method is used in first step can be about 94%-30% of first step raw material total amount, preferred 86%-54%.The powder internal recycle stream that the fine powder raw material of present method preferably produces from ground SODA ASH LIGHT 99.2, pulverous tripoly phosphate sodium STPP (STPP), hydration tri-polyphosphate, ground sodium sulfate, aluminosilicate, crystalline layered silicate, nitrilotriacetic acid(NTA) salt (NTA), phosphoric acid salt, sedimentary silicate, polymkeric substance, carbonate, Citrate trianion, pulverous tensio-active agent (for example pulverous alkyl sulfonic acid) and method of the present invention, wherein the mean diameter of powder is 0.1-500 μ, preferred 1-300 μ, more preferably 5-100 μ.Adopting under the situation of hydration STPP as fine powder of the present invention, it is preferred that hydration levels is not less than 50% STPP.Preferably calcium ion-exchanged capacity and the high aluminosilicate ion exchange material of exchange velocity are used as washing synergistic agent of the present invention.Though do not expect to be subjected to theoretical constraint, be sure of that this high calcium ion exchange rate and capacity are the functions of producing the correlation factors of aluminosilicate ion exchange material method.Thus, the used aluminosilicate ion exchange material of the present invention is preferably pressed people's such as section Kiel United States Patent (USP) 4,605,509 (Procter ﹠amp; Gamble) produce, be incorporated herein its disclosure as a reference.

Preferred aluminosilicate ion exchange material is " sodium " type, because the exchange velocity of the aluminosilicate of potassium type and Hydrogen and capacity are not as the height of sodium type.In addition, preferred aluminosilicate ion exchange material is over-drying form, is beneficial to produce frangible detergent agglomerate described herein.The aluminosilicate ion exchange material that the present invention uses preferably has the particle diameter as washing synergistic agent best results.Term used herein " particle diameter " is meant uses conventional method of analysis, and for example measurement microscope and scanning electronic microscope (SEM) are measured the median size of specifying aluminosilicate ion exchange material.The preferred particle diameter of aluminosilicate is extremely about 10 μ of about 0.1 μ, and more preferably from about 0.5 μ is to about 9 μ.Most preferably particle diameter is that about 1 μ is to about 8 μ.

The general formula of preferred aluminosilicate ion exchange material is Na _z[(AlO ₂) _z(SiO ₂) _y] _xH ₂O, z and y are integers in the formula, are at least 6, and z is about 1 to about 5 to the molecule ratio of y, and x is about 10 to about 264.More preferably the general formula of aluminosilicate is Na ₁₂[(AlO ₂) ₁₂(SiO ₂) ₁₂] xH ₂O, x is about 20 to about 30, preferred about 27 in the formula.These preferred aluminosilicates can have been bought on market, for example trade mark zeolite A, zeolite B and X zeolite.Adopt another kind of scheme, natural or with the aluminosilicate ion exchange material of the present invention that is applicable to of synthetic method preparation, can be incorporated herein its disclosure as a reference by people's such as Crewe Mel United States Patent (USP) 3,985,669 described preparations.

The feature of the aluminosilicate that the present invention is used also is their loading capacity, presses butt and calculates, and is at least about 200meg CaCO ₃Hardness/g is preferably about 300-352megCaCO ₃Hardness/g.In addition, the feature of this aluminosilicate ion exchange material is that also they are at least about 2grains (grain) Ca to the exchange velocity of calcium ion ⁺⁺/ gallon/min/-g/ gallon.2grains Ca more preferably from about ⁺⁺/ gallon/min/-g/ gallon is to about 6grains Ca ⁺⁺/ gallon/min/-g/ gallon.The liquid of mistization

The amount of liquid of present method mistization can be finished product total amount that method of the present invention obtains about 1% to about 10% (active group), preferred 2% to about 6% (active group).The mist liquid that present method is used can be selected from liquid silicate; Anionic or cationic tensio-active agent, these tensio-active agents are liquid, water-based or nonaqueous polymers solns; Water and composition thereof.Other optional example of the mist liquid that the present invention uses can be carboxymethylcellulose sodium solution, polyoxyethylene glycol (PEG) and dimethylene triamine pentamethyl-phosphonic acids (DETMP).

Can be used as the preferred embodiment of the anionic surfactant solution of mist liquid in the present invention, be the active HLAS of about 88-97%, the active NaLAS of about 30-50%, about 28% active A E3S solution, the active liquid silicate of about 40-50% etc.

Also can adopt cationic surfactant as mist liquid of the present invention, suitable quaternary ammonium surfactant is selected from single C ₆-C ₁₆, preferred C ₆-C ₁₀N-alkyl or alkenyl quaternary ammonium surfactant, wherein Sheng Xia N position is replaced by methyl, hydroxyethyl or hydroxypropyl.

Can be in the present invention as preferred embodiment water-based or nonaqueous polymers soln of the mist liquid polyamine that is modification, comprising the polyamine main chain that is equivalent to following formula: The general formula of its modified polyamine is V _(n+1)W _mY _nZ, or be equivalent to the polyamine main chain of following formula: The general formula of its modified polyamine is V _(n-k+1)W _mY _nY ' _kZ, k is less than or equal to n in the formula, and before modification, the molecular weight of described polyamine main chain is greater than about 200 dalton (dalton), wherein:

(i) the V unit is the terminal units with following formula:

(ii) the W unit is the skeleton unit with following formula:

(iii) the Y unit is the cladon with following formula:

With

(iv) the z unit is the end-blocking unit with following formula:

Wherein connect basic R unit on the main chain and be selected from C ₂-C ₁₂Alkylidene group, C ₄-C ₁₂Alkylene group, C ₃-C ₁₂Hydroxy alkylidene, C ₄-C ₁₂Alkyl sub-dihydroxy, C ₈-C ₁₂The dialkyl group arylidene ,-(R ¹O) _xR ¹-,-(R ¹O) _xR ⁵(OR ¹) _x-,-(CH ₂) CH (OR ²) CH ₂O) _z(R ¹O) _yR ¹(OCH ₂CH (OR ²) (CH ₂) _w-,-CO (R ⁴) _rC (O)-,-(CH ₂) CH (OR ²) CH ₂-and composition thereof, R wherein ¹Be C ₂-C ₆Alkylidene group and composition thereof; R ²Be hydrogen ,-(R ¹O) _xB, and composition thereof; R ³Be C ₁-C ₁₈Alkyl, C ₇-C ₁₂Aralkyl, C ₇-C ₁₂Alkyl substituting aromatic base, C ₆-C ₁₂Aryl and composition thereof; R ⁴Be C ₁-C ₁₂Alkylidene group, C ₄-C ₁₂Alkylene group, C ₈-C ₁₂Aryl alkylene, C ₆-C ₁₀Arylidene and composition thereof; R ⁵Be C ₁-C ₁₂Alkylidene group, C ₃-C ₁₂Hydroxy alkylidene, C ₄-C ₁₂Alkyl sub-dihydroxy, C ₈-C ₁₂The dialkyl group arylidene ,-C (O)-,-C (O) NHR ⁶NHC (O)-,-R ¹(OR ¹)-,-C (O) (R ⁴) _rC (O)-,-CH ₂CH (OH) CH ₂-,-CH ₂CH (OH) CH ₂O (R ¹O) _yR ¹OCH ₂CH (OH) CH ₂-and composition thereof; R ⁶Be C ₂-C ₁₂Alkylidene group or C ₆-C ₁₂Arylidene; The E unit is selected from hydrogen, C ₁-C ₂₂Alkyl, C ₃-C ₂₂Alkenyl, C ₇-C ₂₂Aralkyl, C ₂-C ₂₂Hydroxyalkyl ,-(CH ₂) _pCO ₂M ,-(CH ₂) _qSO ₃M ,-CH (CH ₂CO ₂M) CO ₂M ,-(CH ₂) _pPO ₃M ,-(R ¹O) _xB ,-C (O) R ³And composition thereof; Oxide compound; B is hydrogen, C ₁-C ₆Alkyl ,-(CH ₂) _qSO ₃M ,-(CH ₂) _pCO ₂M ,-(CH ₂) _q(CHSO ₃M) CH ₂SO ₃M ,-(CH ₂) _q-(CHSO ₂M) CH ₂SO ₃M ,-(CH ₂) _pPO ₃M ,-PO ₃M and composition thereof; M is hydrogen or the water-soluble cationic that satisfies the q.s of charge balance; X is a water soluble anion; The m value is 4 to about 400; The n value is 0 to about 200; The p value is 1-6; The q value is 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 most preferred polymine is that to have molecular weight be 1800 polymine, again by oxyethylation with its modification, (PEI 1800, E7) to reach the degree of residual about 7 oxyethane of each nitrogen.For above-mentioned polymers soln, preferably with aniorfic surfactant NaLAS coordinate solution in advance for example.

Can be used as the water-based of mist liquid among the present invention or other preferred examples of nonaqueous polymers soln, is polymeric multi-carboxylate dispersion agent, and dispersion agent can preferably adopt the monomer of acid type by suitable polymerization of unsaturated monomers or copolymerization.Can polymerization prepare suitable multi-carboxylate polymer's unsaturated acids monomer, comprise vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, methylene-succinic acid, equisetic acid, methylfumaric acid, citraconic acid and methylene radical propanedioic acid.In the multi-carboxylate polymer that the present invention uses, do not contain carboxylate radical, for example monomer segmental existence such as vinyl methyl ether, vinylbenzene, ethene also suit, but press the weight calculating of polymkeric substance, and these segments must not surpass about 40%.

Molecular weight is the homopolymerization multi-carboxylate more than 4,000, and is for example described below, is preferred.Shi Yi homopolymerization multi-carboxylate can be prepared by vinylformic acid especially.These used acrylic acid based polymers of the present invention are water-soluble salts of polymeric acrylic acid.Press acid type and calculate, preferably the molecular-weight average of this base polymer is 4,000-10, and more than 000, preferably 4,000-7, more than 000 and most preferably 4,000-5 is more than 000.The water-soluble salt of this class acrylate copolymer comprises for example ammonium salt of basic metal, ammonium and replacement.

Also can use copolymerization multi-carboxylate, for example vinylformic acid/maleic copolymer.This class material comprises the water-soluble salt of vinylformic acid and maleic acid.Calculate with acid type, preferably the molecular-weight average of this analog copolymer is about 2,000-100,000, more preferably from about 5,000-75,000, most preferably from about 7,000-65,000.Acrylate was generally about 30: 1 to about 1: 1 maleate segmental ratio in this analog copolymer, more preferably from about 10: 1 to 2: 1.The water-soluble salt of this class vinylformic acid/maleic acid can comprise for example ammonium salt of basic metal, ammonium and replacement.Preferably make for example LAS coordination in advance of above-mentioned polymers soln and anion surfactant.The washing composition auxiliary ingredients

The detergent raw material of present method can comprise other washing composition batching, and/or can in some follow-up steps of present method any other batching be added in the cleaning composition.These auxiliary ingredients comprise decontamination synergistic agent, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, suds booster or defoamer, anti-tarnishing agent and sanitas, soil-suspending agent, soil releasing agent, sterilant, pH regulator agent, no synergistic agent alkali source, sequestrant, smectic clays, enzyme, enzyme stabilizers and spices.See the people's such as little Baskerville of promulgation on February 3rd, 1976 United States Patent (USP) 3,936,537, be hereby incorporated by.

Other synergistic agent generally can be selected from various water miscible basic metal, ammonium or replace phosphoric acid salt, poly-phosphate, phosphonate, polyphosphonate, carbonate, borate, polyhydroxy sulfonate, polyacetic acid salt, carboxylate salt and the multi-carboxylate of ammonium.Above-mentioned an alkali metal salt, particularly sodium salt are preferred.That preferred use is phosphoric acid salt, carbonate, C in the present invention ₁₀-C ₁₈Lipid acid, multi-carboxylate and composition thereof.Two succinates of tripoly phosphate sodium STPP, tetrasodium pyrophosphate, Citrate trianion, tartrate monosuccinic acid salt and tartrate and composition thereof (seeing below) more preferably.

Compare with unbodied water glass, laminar crystal sodium silicate obviously increases the loading capacity of calcium, magnesium.In addition, lamina sodium silicate is better than commutativity to calcium ion to magnesium ion, to guaranteeing that it is necessary removing all " hardness " from washing water basically.Yet these lamellated crystalline sodium disilicates are generally expensive than unbodied silicate and other synergistic agent.Therefore in order to prepare a kind of economically viable detergent for washing clothes, must determine to use the ratio of laminar crystal sodium silicate carefully.In the people's such as section Kiel that this paper is incorporated herein by reference previously United States Patent (USP) 4,605,509, these laminar crystal sodium silicates have been discussed.

The specific examples of inorganic phosphate synergistic agent is that tri-polyphosphate, pyrophosphate salt, the polymerization degree of sodium and potassium is polymetaphosphate and the orthophosphoric acid salt of about 6-21.The example of polyphosphonate synergistic agent is the sodium salt of ethylidene diphosphonic acid and sylvite, ethane 1-hydroxyl-1, the sodium salt of 1-di 2 ethylhexyl phosphonic acid and sylvite and ethane-1,1, the sodium salt of 2-tri methylene phosphonic acid and sylvite.In United States Patent (USP) 3,159,581; 3,213,030; 3,422,021; 3,422,137; Disclose other phosphorous synergist compound in 3,400,176 and 3,400,148, be incorporated herein all these patents as a reference.

The example of the inorganic synergistic agent of phosphorated is not ten hydration tetraborates, SiO ₂To the weight ratio of alkalimetal oxide is about 0.5 to about 4.0 silicate, preferred about 1.0 to about 2.4.The water miscible not phosphorated organic synergistic agent of Shi Yonging in the present invention comprises various basic metal, ammonium and replaces polyacetic acid salt, carboxylate salt, multi-carboxylate and the polyhydroxy sulfonate of ammonium.The example of polyacetic acid salt and multi-carboxylate's synergistic agent is the ammonium salt of sodium, potassium, lithium, ammonium and the replacement of ethylenediamine tetraacetic acid (EDTA), nitrilotriacetic acid(NTA), oxo disuccinic acid, mellitic acid, benzene polycarboxylic acid and citric acid.

In the United States Patent (USP) 3,308,067 of the Deere of on March 7th, 1967 promulgation, narrated polymeric multi-carboxylate synergistic agent.Be incorporated herein its disclosure as a reference.This class material comprises aliphatic carboxylic acid, for example the homopolymer of toxilic acid, methylene-succinic acid, methylfumaric acid, fumaric acid, equisetic acid, citraconic acid and methylene radical propanedioic acid and the water-soluble salt of multipolymer.Some is used as water-soluble anionic polymer hereinafter described in these materials, but just with the non-soap anionic surfactant thorough mixing time.

Other suitable multi-carboxylate that the present invention uses is the United States Patent (USP) 4 the people such as Crutchfield of promulgation on March 13rd, 1979,144, in 226 and at the people's such as Crutchfield of on March 27th, 1979 promulgation United States Patent (USP) 4,246, polyacetal carboxylation described in 495 is incorporated herein these two parts of patents as a reference.These polyacetal carboxylations can be by adding preparation together with hydrated glyoxylate and polymerization starter under polymerizing condition, with chemical process resulting polyacetal carboxylic acid ester is connected on the stable end group then, make the polyacetal carboxylation that rapid depolymerization not take place in basic solution, the polyacetal carboxylic acid ester changes into corresponding salt simultaneously, and adds in the cleaning composition.The carboxylate salt enhancer composition that particularly preferred multi-carboxylate's synergistic agent is an ether, United States Patent (USP) 4 comprising the people such as Bush that issue on May 5th, 1987,663, the mixture of the two succinates of tartrate monosuccinic acid salt described in 071 and tartrate is incorporated herein its disclosure as a reference.

Having narrated SYNTHETIC OPTICAL WHITNER and activator in the United States Patent (USP) 4,412,934 of the Qiu Dengren of November 1 nineteen eighty-three promulgation and in the Hartmann's of promulgation on November 20th, 1984 the United States Patent (USP) 4,483,781, be incorporated herein these two parts of patents as a reference.In people's such as Bush United States Patent (USP) 4,663,071, walk to 18 hurdles, 68 row from 17 hurdles the 54th and also narrated some sequestrants, be hereby incorporated by.The foam modifying agent also is an optional ingredients, at the people's such as Ba Tuolita of on January 20th, 1976 promulgation United States Patent (USP) 3,933, the Gao Er top grade people's who issues with on January 23rd, 1979 in 672 United States Patent (USP) 4, existing narration is incorporated herein these two parts of patents as a reference in 136,045.

Be fit to the smectic clays used in the present invention, walk to existing narration in 7 hurdles, 24 row, be hereby incorporated by on 6 hurdles 3 of the people's such as Plutarch of promulgation on August 9th, 1988 United States Patent (USP) 4,762,645.Other washing synergistic agent that is fit to use in the present invention walks to existing enumerating in 16 hurdles, 16 row and the United States Patent (USP) 4,663,071 the people such as Bush of promulgation on May 5th, 1987 on patent 13 hurdles 54 of Baskerville, is incorporated herein these two parts of patents as a reference.

Optional processing step

Present method can be chosen the step of spraying auxiliary binder in the one or more mixing tanks that are included in first, second and/or the 3rd mixing tank of the present invention wantonly.The purpose that adds tackiness agent is to provide " bonding " or " adhesion " agent to strengthen nodulizing to detergent ingredients.Tackiness agent is preferably from water, aniorfic surfactant, nonionic surface active agent, liquid silicate, polyoxyethylene glycol, polyvinylpyrrolidone, polyacrylic ester, citric acid and composition thereof.The jointing material that other is suitable comprises these that this paper lists, at people's such as Bill's Si grade United States Patent (USP) 5,108,646 (Procter ﹠amp; Gamble company) existing narration is incorporated herein its disclosure as a reference in.

Other optional step that present method is considered comprises that the employing screening plant sifts out the detergent agglomerate of oversize, and screening plant can adopt and include but not limited to sieve for reaching the various forms of routines that the granularity requirements of finished product washing composition is selected.Other optional step comprises utilizes aforesaid equipment to make agglomerate adjust detergent agglomerate through additional desiccation.

Another optional step of present method is the made detergent agglomerate of the whole bag of tricks finishing that sprays and/or mix other conventional detergent ingredients by comprising.For example finishing step comprises on by the agglomerate of finishing sprays spices, whitening agent and enzyme, makes detergent composition more completely, and these technology and composition are well-known in this area.

Another optional step of present method is the manufacturing processed that tensio-active agent is stuck with paste body, for example before process of the present invention, adopts forcing machine to add and sticks with paste the body hardened material, makes aqueous aniorfic surfactant stick with paste body and hardens.Co-applications PCT/US96/15960 (on October 4th, 1996 submitted to) discloses the detailed content that tensio-active agent is stuck with paste the system making method.

For the present invention is more readily understood, can stipulate that these embodiment are illustrative with reference to the following examples, scope of the present invention is not limited.

EXAMPLE Example 1:

Be an embodiment who makes the high-density agglomerate below, comprising adopt earlier L  digeCB mixing tank (CB-30), then adopt Schugi FX-160 mixing tank, then adopt L  dige KM mixing tank (KM-600), adopt the further granulation of fluidized bed plant at last.

(step 1) utilizes the cylindricality utensil (Pintools) of CB-30 mixing tank that the aqueous coconut Fatty Alcohol(C12-C14 and C12-C18) of 250-270kg/h sulfuric acid tensio-active agent is stuck with paste body (C ₁₇-C ₁₈, active ingredient 71.5%) disperse with the internal recycle of the Powdered STPP of 220kg/h (mean particle size 40-75 μ), 160-200kg/h ground SODA ASH LIGHT 99.2 (mean particle size 15 μ), 80-120kg/h ground sodium sulfate (mean particle size 15 μ) and 200kg/h powder stream.Tensio-active agent is stuck with paste body and is added down at about 40-52 ℃, and powder at room temperature adds.The operational condition of CB-30 mixing tank is as follows:

Mean residence time: 10-18s

Terminal velocity: 7.5-14m/s

Energy state: 0.5-4kj/kg

Mixer speed: 550-900rpm

Jacket temperature: 30 ℃

(step 2 (i)) will add from the agglomerate of CB-30 mixing tank in the Schugi FX-160 mixing tank.Under about 50-60 ℃ in the Schugi mixing tank with 30kg/h HLAS (C ₁₁-C ₁₈The acid presoma of alkylbenzene sulfonate, active ingredient 94-97%) is dispersed into the liquid of mistization.In the Schugi mixing tank, add 20-80kg/h SODA ASH LIGHT 99.2 (the about 10-20 μ of mean particle size).The operational condition of Schugi mixing tank is as follows:

Mean residence time: 0.2-5s

Terminal velocity: 16-26m/s

Energy state: 0.15-2kj/kg

Mixer speed: 2000-3200rpm

(step 2 (ii)) will add the further agglomeration of KM-600 mixing tank from the agglomerate of Schugi mixing tank, make agglomerate become circle and grow up.Also in the KM mixing tank, add the 30kg/h zeolite.The chopping mechanism of available KM mixing tank reduces the agglomerate amount of oversize.The operational condition of KM mixing tank is as follows:

Mean residence time: 3-6min

Energy state: 0.15-2kj/kg

Mixer speed: 100-150rpm

Jacket temperature: 30-40 ℃

(step 3) will add fluidized bed drying equipment from the agglomerate of KM mixing tank, make the agglomerate drying, become circle and grow up.Also can be with 20-80kg/h liquid silicate (43% solid, 2.0R) adding fluidized bed drying equipment under 35 ℃.The operational condition of fluidized bed drying equipment is as follows:

Mean residence time: 2-4min

Quiet bed height: 200mm

The droplet sizes: less than 50 μ

Spray height: 175-250mm (more than grid distributor)

Fluidizing velocity: 0.4-0.8m/s

Bed temperature: 40-70 ℃

The particulate density that makes from step 3 is about 700g/l, can choose wantonly to make it through optional cooling, screening and/or attrition process.Embodiment 2:

(step 1) adopts the cylindricality utensil of CB-30 mixing tank with about 50 ℃ 15kg/h-30kg/h HLAS (C ₁₁-C ₁₈The acid presoma of alkylbenzene sulfonate, active ingredient 95%) and the aqueous coconut Fatty Alcohol(C12-C14 and C12-C18) of 250-270kg/h sulfuric acid tensio-active agent paste body (C ₁₂-C ₁₈, active ingredient 71.5%), disperse with the internal recycle of the Powdered STPP of 220kg/h (mean particle size 40-75 μ), 160-200kg/h ground SODA ASH LIGHT 99.2 (mean particle size 15 μ), 80-120kg/h ground sodium sulfate (mean particle size 15 μ) and 200kg/h powder stream.Tensio-active agent is stuck with paste body and is added down at about 40-52 ℃, and powder at room temperature adds.The operational condition of CB-30 mixing tank is as follows:

Mean residence time: 10-18s

Terminal velocity: 7.5-14m/s

Energy state: 0.5-4kj/kg

Mixer speed: 550-900rpm

Jacket temperature: 30 ℃

(step 2 (i)) will add from the agglomerate of CB-30 mixing tank in the Schugi FX-160 mixing tank.Under about 30-40 ℃ in the Schugi mixing tank with 35kg/h neutral AE ₃S liquid (effective constituent 28%) is dispersed into the liquid of mistization.In the Schugi mixing tank, add the 20-S0kg/h SODA ASH LIGHT 99.2.The operational condition of Schugi mixing tank is as follows:

Mean residence time: 0.2-5s

Terminal velocity: 16-26m/s

Energy state: 0.15-2kj/kg

Mixer speed: 2000-3200rpm

(step 2 (ii)) will add further agglomeration in the KM-600 mixing tank from the agglomerate of Schugi mixing tank, make agglomerate become circle and grow up.Also in the KM mixing tank, add 60kg/h ground SODA ASH LIGHT 99.2 (mean particle size 15 μ), can adopt the chopping mechanism of KM mixing tank to reduce the agglomerate amount of oversize.The operational condition of KM mixing tank is as follows:

Mean residence time: 3-6min

Energy state: 0.15-2kj/kg

Mixer speed: 100-150rpm

Jacket temperature: 30-40 ℃

(step 3) will add from the agglomerate of KM mixing tank be made the agglomerate drying, becomes circle and grow up in the fluidized bed drying equipment.Also can be with 20-80kg/h liquid silicate (43% solid, 2.0R) adding fluidized bed drying equipment under 35 ℃.The operational condition of fluidized bed drying equipment is as follows:

Mean residence time: 2-4min

Quiet bed height: 200mm

The droplet sizes: less than 50 μ

Spray height: 175-250mm (more than grid distributor)

Fluidizing velocity: 0.4-0.8m/s

Bed temperature: 40-70 ℃

To add the fluidized-bed cooling apparatus from the agglomerate that fluidized bed drying equipment makes.The operational condition of fluidized-bed cooling apparatus is as follows:

Mean residence time: 2-4min

Quiet bed height: 200mm

Fluidizing velocity: 0.4-0.8m/s

Bed temperature: 12-60 ℃

The particulate density that makes from step 3 is about 700g/l, can choose wantonly to make it through optional screening and/or attrition process.Embodiment 3:

Be an embodiment who makes the high-density agglomerate below, comprising adopt earlier L  digeCB mixing tank (CB-30), then adopt Schugi FX-160 mixing tank, adopt the further agglomeration of fluidized bed plant then.

(step 1) adopts the cylindricality utensil of CB-30 mixing tank that the coconut Fatty Alcohol(C12-C14 and C12-C18) sulfuric acid tensio-active agent of 250-270kg/h water-based is stuck with paste body (C ₁₂-C ₁₈, active ingredient 71.5%), disperse with the internal recycle of the pulverous STPP of 220kg/h (mean particle size 40-75 μ), 160-200kg/h ground SODA ASH LIGHT 99.2 (mean particle size 15 μ), 80-120kg/h ground sodium sulfate (mean particle size 15 μ) and 200kg/h powder stream.Tensio-active agent is stuck with paste body and is added down at about 40-52 ℃, and powder at room temperature adds.The operational condition of CB-30 mixing tank is as follows:

Mean residence time: 10-18s

Terminal velocity: 7.5-14m/s

Energy state: 0.5-4kj/kg

Mixer speed: 550-900rpm

Jacket temperature: 30 ℃

(step 2 (i)) will add from the agglomerate of CB-30 mixing tank in the Schugi FX-160 mixing tank.In the Schugi mixing tank under about 50-60 ℃ with 30kg/h HLAS (C ₁₁-C ₁₈Alkylbenzene sulfonate acid presoma acid, active ingredient 94-97%) is dispersed into the liquid of mistization.In the Schugi mixing tank, add the 20-80kg/h SODA ASH LIGHT 99.2.The operational condition of Schugi mixing tank is as follows:

Mean residence time: 0.2-5s

Terminal velocity: 16-26m/s

Energy state: 0.15-2kj/kg

Mixer speed: 2000-3200rpm

(step 3) will add from the agglomerate of Schugi mixing tank be made the agglomerate drying, becomes circle and grow up in the fluidized bed drying equipment.Also can be with 20-80kg/h liquid silicate (43% solid, 2.0R) adding fluidized bed drying equipment under 35 ℃.The operational condition of fluidized bed drying equipment is as follows:

Mean residence time: 2-4min

Quiet bed height: 200mm

The droplet sizes: less than 50 μ

Spray height: 175-250mm (more than grid distributor)

Fluidizing velocity: 0.4-0.8m/s

Bed temperature: 40-70 ℃

The particulate density that makes from step 3 is about 600g/l, can choose wantonly to make it through optional cooling, screening and/or attrition process.

Now at length narrated the present invention,, obviously can make various changes and do not exceed scope of the present invention, should not think that the present invention is only limited in the content described in the specification sheets for those skilled in the art.

Claims

1. non-tower method for preparing granular detergent compositions, the density of said composition is at least about 600g/l, comprising following steps:

(a) in mixing tank, disperse and with the fine powder clad surface promoting agent of diameter 0.1-500 μ, wherein the operational condition of mixing tank comprises: (i) mean residence time about 2 is to about 50s, (ii) terminal velocity about 4 is to about 25m/s, (iii) energy state about 0.15 is made first agglomerate therein to 7kj/kg;

(c) in one or more fluidizing apparatus, make the second agglomerate granulation, wherein the operational condition of each fluidizing apparatus comprises: (i) mean residence time about 1 is to about 10min, (ii) quiet bed height about 100 is to about 300mm, (iii) The droplet sizes is not more than about 50 μ, (iv) spray height about 175 is to about 250mm, (v) fluidizing velocity about 0.2 to about 1.4m/s and (vi) bed temperature about 12 is to about 100 ℃.

2. non-tower method for preparing granular detergent compositions, the density of said composition is at least about 600g/l, comprising following steps:

(b) in mixing tank on spray liquid to the first agglomerate with mistization, wherein the operational condition of mixing tank comprises: (i) mean residence time about 0.2 is to about 5s, (ii) terminal velocity about 10 is to about 30m/s, (iii) energy state about 0.15 is made second polymkeric substance therein to about 5kj/kg;

(c) in one or more fluidizing apparatus, make the 3rd agglomerate granulation, wherein the operational condition of each fluidizing apparatus comprises: (i) mean residence time about 1 is to about 10min, (ii) quiet bed height about 100 is to about 300mm, (iii) The droplet sizes is not more than about 50 μ, (iv) spray height about 175 is to about 250mm, (v) fluidizing velocity about 0.2 to about 1.4m/s and (vi) bed temperature about 12 is to about 100 ℃.

3. according to the method for claim 1 or 2, wherein said tensio-active agent is selected from anionic, non-ionic type, cationic, amphoteric ion type and tensio-active agent amphoteric and composition thereof.

4. according to the method for claim 1 or 2, wherein said tensio-active agent is selected from alkylbenzene sulfonate, alkyl alkoxy sulfuric acid, alkylethoxylate, alkyl sulfuric ester salt, coconut fatty alcohol sulfuric acid and composition thereof.

5. according to the method for claim 1 or 2, wherein meticulous powder forms in step (a), wherein this meticulous powder is added in the step (b).

6. according to the method for claim 1 or 2, wherein water-based or nonaqueous polymers soln disperse in step (a) with described tensio-active agent.

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

8. according to the method for claim 1 or 2, wherein the liquid of mistization is selected from the polymers soln of liquid silicon hydrochlorate, aniorfic surfactant, cationic surfactant, water-based, nonaqueous polymers soln, water and composition thereof.

9. according to the method for claim 1 or 2, wherein also will add in the step (a) from the powder internal recycle stream of fluidizing apparatus.

10. granular detergent compositions according to the preparation of the method for claim 1 or 2.