DE1950791A1 - Process for making agglomerated detergent compositions - Google Patents

Description

Process for the production of agglomerated detergent feed

aam wetting

The invention relates to a method for producing a Detergent composition using known detergent components, e.g. a detergent composition for Dishwashers that hardly need to be aged or ground after production. The inventive method is characterized in that finely divided detergent components components are introduced into an agglomeration zone, in this zone a freely falling soleplate made of these detergent components is formed, the finely divided components in this veil are brought into contact with a liquid material so that they agglomerate, at the Ifusse of this falling Veil a moving sohioht. formed from agglomerating components and the agglomerated material from this Agglomeration zone is withdrawn.

Commercially available dishwashing detergents for

can be produced according to a process, * as did ü0Xt (■

U.S. Patent 2,895,916. The ·· Suiamtntetau || g || i '.'. * _? ; ... \

00 ^ 816/1701

BADORKa (NAL

<Y- / ⁵ Y. Yi-

contain a water-soluble condensed alkali metal phosphate, a water-soluble alkali metal silicate and chlorinated trisodium aiophate. The process consists of the following stages adding an essentially anhydrous condensed alkali metal phosphate, a certain alkali metal silicate and water in an amount which is at least sufficient to add the condensed phosphate wet so that agglomeration begins, but does not ^excite; » ¹ ^ ^{to destroy the individual particles typical for the} mixture of condensed phosphate and silicate, moving the mixture, taking care that the temperature does not rise above about 54 ⁰ C, adding chlorinated trisodium phosphate to this mixture, moving the resulting mixture, Aging of this mixture in order to largely complete the hydration, whereby the mixture is agitated from time to time, and comminution of the agglomerates formed to the desired size. The total amount of added water, excluding the water introduced with the chlorinated trisodium phosphate, is about 12 to about 25 wt * - #, based on the finished detergent composition »

This known process thus requires a first stage in which sodium tripolyphosphate, sodium silicate and water mixed together under specific conditions to initiate agglomeration and a second stage, in which the chlorinated trisodium phosphate is added separately to this partially agglomerated mixture. The resulting Mixture is agitated and then aged to keep hydration to be completed with occasional agitation. Aging takes about 4 hours. The term "aging" used here is intended to denote the time required to complete the hydration of the constituents

We * used the hydra during this aging period tization of the iripolyphosphate essentially boiled to the end Then · the agglomerates formed are au; ie ge wishes t GrSase shredded before they are packaged.

o o d dι $ / 1? Ot

i m J m

/ for a nooh older process eur production of a similar ·; Ι_ chen Detergens-ZueaEDJBeneeteung »that in the same part eu

VergleiohaaWsoksn is mentioned, an even longer age is given , ruDgsperio.de

The SA patent 3 247 11B describes a process for the production of oesophiric disinfectants which are used by the USA patent 2 895 916 tthnlioh oindj in this process is 41 »aging "• 1" on e ^ wa an hour of speech "indicates this procedure At the same time, the level in which the air is ventilated is hot is passed over 4m agglomerating * · aranulate, while the-. i eat is carried in a rotating drum.

S * has now been found that Betergtns compositions for

well, a process

Vftrdiei can "which no aging stage before the Vfrpeoken""change only requires cooling to room temperature and Jj a very" the "agglomerates formed before the" packaging ι foht "reduced vtrAtxi, but also lind \ Ai #" rf | tiain | i | * iaU | · dergeittllten! »etergeni-EutammeneetBun-I) ' it $ ϊψ * 1 rUlMend, Hioht clumping and not crumbling»' V $ M * ^ ^d ohloretabil And know near Btiarf a high _: ;.; tiglceiti content.

Aieeer fcrfinitial l ^ t «in a novel process for the production

von Detergeiüf * fcuiammtnitt «: ungen _# with white · ■ must- * t, in a · Velffahr * negang finely divided constituent parts of your quantity, components containing active chlorine, and then add liquid materials, whereby in particular the aging and grinding stages required up to now are omitted can and preducts can be obtained »the honogenic, free-flowing, ohloa ^ stable, largely dust-free and not clumping a * and never soaped»

These goals "are" achieved with the following procedure

If the product is to be manufactured continuously, for example, who * den the components of the Petergene team, as, B, die

009816/1701 BAD

Components of a dishwashing detergent for automatic dishwashers, in finely divided form, for example powdery or \ \ finely crystalline, introduced into a layer of material that is agglomerated in a suitable agglomeration zone. | The agglomeration zone preferably consists of a delimited, cylindrical, elongated zone which is rotated about its longitudinal axis and which is equipped with suitable devices; is equipped with which a freely falling soleplate is equipped; Detergent ingredients can be formed which is maintained between an upper portion of the confined zone and a portion of the material on the floor of the zone. Zuzusetzen- D _as the detergent composition and _{the like} de explained in more detail below liquid material is sprayed in the form of individual droplets by appropriate spray nozzles. The droplets are brought into contact with the finely divided constituents in the falling veil, which preferably have a constant density, where they wet these particles and form agglomerates, preferably without; be sprayed on any part of the apparatus used to <i. The wetted particles fall onto the material layer formed at the bottom of Agglomerierungszone 'where they are subjected to shear forces that the few large agglomerates that form random, au particles of the desired ^ize break. Under the rotational • undfDaumelwirkung of the layer are agglomerated particles from the detergent Gene composition formed by the desired size * The particle size of the agglomerates can be controlled such that the rotational speed of the drum, the rotational time and / or the applied amount of liquid can be varied.

The invention is illustrated with reference to the drawing, which shows a preferred device for carrying out the method according to the invention shows, explained in more detail, According to Figure 1, this device can consist of a frame 10, which in its inclination adjustable support 12, drive devices that can move up and down 14 for the selective adjustment of the support

009816/1701

12 at any angle to the horizontal, one cylindrical Drum 16, devices 18 and 20 for the rotatable mounting of the drum on the support 12 and at speed adjustable drive devices 22, 24 and 26 for rotating the drum.

The drum 16 consists of: a cylindrical outer shell or wall 28, an annular end plate 32 with an inlet opening 34 for the introduction of the finely divided components 36, an annular end plate 38 having an outlet port 40 through which the agglomerated detergent composition 44 exits and enters the shaft 42, a spiral conveyor rib 52 to the finely divided components and / or partially agglomerated particles 36 through the Drum to move towards the inlet opening 34, and a spiral conveyor rib 46 to move the fine particles 36 and / or agglomerated particles 44 in the direction of the outlet opening 40, one with a plurality of spaced apart spray nozzles 58 provided feed pipe 56 (Figure 2), and a cylindrical j Bundles of spokes 60 arranged parallel to one another and at a distance from one another, which develop the falling veil, supported between the conveyor ribs 46 and 52 and between the end plates 32 and 38 lie. With the exception of the inlet pipe 56, all components of the drum 16 rotate together as a unit.

Another device which is suitable for carrying out the method according to the invention is described in US patent application 652,922. The constituents that can be used for the production of a detergent composition for household automatic dishwashers are known to those in the know and are described in numerous patents, e.g. USA patents 2 895 916, 2 756 214, 2 689 225, 3 ¹ O ') 207 and 3 247 118.

009816/1701 ^ßAD original

The "preferred ingredients for the detergent composition, especially for dishwashing detergents, (A) condensed alkali metal phosphate, (B) a compound containing active chlorine, (0) sodium or potassium silicates, (D) surfactants, and (B) water.

The condensed alkali metal phosphates preferably have an Na ₂ O / P ₂ O ₅ or K ₂ O / P ₂ O ₅ ratio of about 1: 1 to 2: 1. Particularly preferred are the pyrophosphates and polyphosphates, especially those which hydrate rapidly. The most preferred condensed alkali phosphate is sodium tripolyphosphate. The composition can contain about 20 to 80 parts by weight, preferably about 30 to 60 parts by weight, of condensed alkali metal phosphate per 100 parts by weight. The condensed alkali metal phosphate can be used in anhydrous form, hydrated form or partially hydrated form, but preferably in anhydrous form.

Another component of the detergent composition made in accordance with the present invention is an active chlorine containing compound. The compound containing active chlorine gives the detergent composition germicidal, bleaching, water · = film-forming and protein-removing effects. The compounds containing active chlorine which can be used according to the invention include chlorinated trisodium phosphate, trichlorocyanuric acid, the sodium salt of dichlorocyanuric acid, the potassium salt of dichlorocyanuric acid, sodium hypochlorite and i ^ -dichloro-SjS-dimethylhydantoin. λ -.-. f 100 parts of detergent composition, 0.5 to 35 parts of active chlorine-containing compound can be used. If chlorinated trisodium phosphate is used, an amount of 35 parts of the chlorine compound is preferred, since the chlorine available in chlorinated trisodium phosphate is about 3.0%. Much higher amounts of chlorine are available in the chlorinated cyanuric acids and when these are used , therefore 0.5 to 10 parts of chlorine compound are preferred. In general, the amount of chlorine compound used depends

009816/1701

mm ξ Λ **

of the intended use of the detergent combination

\\\ composition from * »

; Al · sodium or potassium partial are preferred solohe that

tin Ia ₂ 0 / Si0 ₂ - or K ₂ 0 / Si0 ₂ -Y obtained from about 1 * 3.75 to. jL 2 * 1 have · Particularly preferred are sodium silicates with 1 »j« inera Na ₂ 0 / Si0 ₂ - ^ ratio of about 1 * 3.22 to 1 * 2.5 · Pre

Approximately 3 to 30 parts by weight of silicate are preferably used 'Anhydrous basis per 100 parts by weight of detergent used.

A particularly preferred ratio is about 4 to 15. The silicate can be used in its anhydrous form or in its hydrated form or as an aqueous solution or as a combination of these forms.
_r ι

Aqueous solutions of silicates are known as "liquid silicates"! They are mostly sodium silicates with an Na ₂ O / SiO ₂ ratio of about 1 * 1.60 to 1 * 3.75.

Here, "surface-active agent is preferably a non-ionic 'Bchee, which has little tendency to foam of a schauabildenden Sohmutzes by itself or in the presence, Bs is preferably verträglioh with the chlorine-containing compound or not. Oberflächenaktive.Mittel that are particularly compatible with chlorine-containing compounds _s are US Patents 2,856,434, 3,281,475 and 3,310,496, French Patent 1,395,977 and the Dutch Patent 65 / O5OJ55 described · The niohtioniaohen surfactants are well known and, for example, in U.S. Patents 3,390,092, 3,356,612

and 3 359 207 described

Generally about 0.5 to 3 parts by weight will be surfactant Medium, preferably non-ionic surfactant Medium, for 100 parts by weight detergent composition used. Lesser amounts of an anionic surfactant can be used with the nonionic Funds are used.

The substances used in the manufacture of the detergent composition

009816/1701

The amount of water is critical and needs to be about 5 to about 50 Make up parts by weight per 100 parts detergent B composition, depending on the amount of finely divided anhydrous used Ingredients, at least enough water should be present to fully hydrate the condensed Alkali phosphate and preferably all hydratable Enable components. The water can be used as such or in the form of a solute-containing component solution can be added *

Other ingredients may optionally be used for "specific purposes." can be added. These include aluminum sulfate, sodium sulfate, calcined soda, sodium aluminum phosphate, anhydrous Trinatriurophosphate, sodium aluminate, boric acid and Borax,

The components of the detergent composition are summarized in the following ^w else:

^! According to one method, all finely divided components are mixed into a homogeneous mixture, v; exm they are not already present as a mixture. These finely divided constituents are a) condensed alkali metal phosphate, b) compound containing active chlorine and optionally other finely divided constituents, such as • eg calcined soda,

Then the "liquid materials" are sprayed into a freely falling layer made of these finely divided components. The "liquid materials ^1" are (1) the surfactant and (2) either a solution of the silicate or water. Optionally, water, a solution of some of the other finely divided ingredients, or a solution of other optional ingredients than "liquid Materials "can be used. The various liquid materials can be sprayed in any order; preferably, the surfactant is applied in an anhydrous state to the finely divided ingredients that do not contain any

009816/1701

contain free water. No part of free water the hydration water of the finely divided Beatand parts

According to another embodiment of the invention, the surface-active agent is sprayed onto a falling soleplate made of finely divided constituents. An aqueous solution of the silicate is then sprayed onto a falling veil on the finely divided constituents and the surface-active agent. Is when the amount of water required nioht added with the silicate, the rest can be added by spraying in ähnlioher W _e i _se * as with the above-* - fläohenaktiven agent and the aqueous solution is done of the silicates *

If the use is erwünsoht a silicate in solid lorm ^v, it can be added with the above ingredients together finely divided "In this case, is sprayed onto the curtain of dry Bestandteileil and surfactant instead of the aqueous solution of the silicate of water.

When a cyanurate as an active chlorine-containing compound is used, it is preferably mixed into the agglomerated particles formed in trooker form.

The size of the agglomerates in the inventive Process can be formed is between about 0.25 and 1.65 mm, preferably between about 0.4 and about 1.4 mm medium durometer. Typically, the particles of the agglomerates used in making the agglomerates have trookene constituents a particle diameter of about 0.075 mm.

The drawing shows a preferred device for conducting the process according to the invention. These Device has been explained in more detail above.

The following examples serve to explain the invented

009816/1701 ■

- χ ι rj ilj »· ti <·

- 10 -

according to the method · The quantities of Beatand parts are given in kg, unless otherwise stated.

Example 1 _m

A typical agglomeration is carried out in batches in one Agglomerating device similar to that explained in the drawing carried out using the following recipe:

1) ^ one-piece components

Sodium tripolyphosphate, 30.0

Calcined soda 7.0

Chlorinated trisodium phosphate 31.0

Sodium aluminate 0.5

2) Liquid, nonionic surfactant Amine polyglycol condensate type agent 0.6

Sodium salt of disulfonated dodecyldiphenyl oxide 0.5

3) Water 11.5 4Ϊ Liquid Sodium Silicate 19.0.

First, the cellular ingredients are combined and dry blended, usually for about 2 minutes, to form a homogeneous mixture. Thereafter, a mixture of the liquid surface-active agents is applied to a freely falling layer of the mixed finely divided constituents from the spray nozzles 58 under a pressure of about 2.1 to 4 »2 kg / cm at a temperature of about 60 to 100 ^° C in about 1 Sprayed up to minutes. Then, the water is sprayed at about 1.4 to 2.1 kg / cm in a similar ^w else such as the liquid surfactant. Finally, the liquid sodium silicate at a temperature of 30 to 10O ⁰ C unte'r a ^ is ruck 2.8 to 5.6 kg / cm for about 10 minutes sprayed.

The rotation is continued for about 20 to 30 minutes to cool the agglomerates formed.

009816/1701

The agglomerated composition can be used immediately after Silicate addition can be removed from the apparatus ^ to desired if necessary in a rotating cooler for the duration of to be cooled down for at least »10 to 15 minutes.

Example 2

The detergent for automatic dishwashers produced according to Example 1 was tested together with two commercially available detergents for household automatic dishwasher as follows: "Bulk weight and fragility were determined in a common procedure. A 100 g sample is examined for sohtittgewioht. This robe is then subjected to a sieve analysis on a Ro-Tap machine. The sieve fractions are weighed, combined again and placed in a 2 liter beaker together with 4 hard rubber balls of 3.8 µm in diameter. The beaker is placed on a Rollma _Sc hi _ne 30 minutes at 60 rpm rolled. this sample has a second determination of the bulk density is made. the difference awieohen the original and the last value is recorded as fragility. the observed in some samples negative values on water losses in the absence • of minor breakage the agglomerated particles are zurüokgeführt. the Genchirrspül efficacy is determined daduroh that soiled with a milk / margarine Standardgemisoh plates are washed. a mobile woad-GtesohirrspülmaBchine of General Electric is with Leitungewasser from 51 to 6O ⁰ O and 5 ppm used hardness. The plates are examined for streaks, leaks and streaks and are examined by three people n subjectively rated. For the sake of Einfaohheit the numerical ^w were erte in ratings of "excellent" bia converted "bad."

The calculated fourths for available chlorine were compared to the actual values. The stability of the available chlorine was determined by aging at 4Q ⁰ O in closed beakers and at Kaurat temperature in open beakers.

009816/1701

The composition prepared according to Example 1 was obtained >. |

the designation sample 2, and the two commercially available additions -, Λ Bame wetting was given the designations sample A and Sample B: The test results of the three samples bind in

Table I summarized »· ¹ ^.

In addition, several other agglomerated Uttergehs associations were formed Prepared according to the procedure of Example 1 and tested according to the methods described above, if nothing else is indicated,.

The formulations and test results are summarized in Table I under samples 2 to 9 »

009816/1701

! table I, /

Agglomerated dishwashing detergents for household machines

Sample ur. A B 1 2 3® 4 5 6 7 8 9 10

Sodium tripolyphosphate 32 30.0 50.6 50.6 46.5 29.6 51.0 32 37 51

Chlorinated trisodium phosphate - - 30.2 31.0 24.3 24.3 00 30.9 - 30 24

Uatrium hypochlarite ($ 12) - -. - - - - ·. - - 9-. «,

o Potassium dichlorocyanurate - *, '- -, -, i _f 5_ i _f 5 _ -,

«Calcined soda - - 9.3 7.0 - 7.3 - - - - ^ j _e :

^ vasserfreias Iri- ₍ f |

_ »Natriumphospnat *». «, - .—, - · - 25.0 - - 22 - - i

oHatriumaluniiBat - "0.3 0.5 0.5 0 _# 5 0.5 0.3 0.5 0.5 0 _f 5 0.5 S

Uichtionisch.es above-

Area activity means "Ί

yypy

ether type · ». ^. Q _t 5 0.6 - - - 0 _t 6 - · - * · * -

Hichtionic surfactant.

from the amine polyglycol ·. .

condensate type. - «· * · - 0.7 0.7 1.5 - 1.0 1.5 0 _# 9 0.7 -a

Sodium salt of the sulfonated * 'üi

Dodecyldiphenyloxl * · - m, ■ 0.4 0.5 0.3 0 * 3 0.5 0.4 Q, 5 0.5 0.9 0.3 O

Sample Mr. . AB 1 2 3 4 5 6 7 8 9 10

Water - 7.2 9.4 2.8 "2.8 12 * 5 9.6 9.0 20 11 2.8

Sodium silicate

(liquid) - - 17.4 19.0 20.8 20.8 12.0 19.1 54.0 1.5 10 ^ 0 20.8

Sodium metasilicate - - - - - - - - 10.0 »-

Water - - 2.9 2.0 - - - 2.2 3.0 - _; -j

¹ S quality of agglo- * J

£, meration --GZZ ZGZAGGZ ΐ "·· ί

co ■ + 1

- * Maximum shift ♦; '

σ> temperature ( ⁰ C) - - 41 48 - «ρ- 48 68 - 47. i \]

^ Ι » oil, theoretically - - 1.11 1.14 0.9 0.9 0.86 1.14 0.9. 1.1 1.1 0.90 k "" 1

^ $> Cl, after Agglo— ^ ₁ · t I

meration 0.77 0.48 ^c 1.01 1.12 0.82 0.83 0.64 1.12 0.46. 0 1.1 0.83 Ί

$> Gl loss

Agglomeration, - 9 2 9 8 26 32 34 100 0 8

fo Gl loss 3Q ^{- location}

open at 22 ° C 94 10 4 34 17 16 2 9 22 -. - 16

io Cl loss 30 surplus _o

closed at 4O ⁰ C 45 17 56 20 26 26 29 47 70 - - 26 * - *

G-esclairrspülv / effective- C

ability AA SG Z - Z, - - SL - -. O

Bulk / cm ³ ) 0.745 0.745 0.745 0.69 - - 0.745 - - - ■ 0.745 -

Fragility -0.3 -0.4 -0.4 -0.7 - - +0.1 - - - «0.5 -

ψ

rf * tt * * t t

«F rt «» »« * * T <f

- 15 -

«Ereeeiellt in the example 1j,

ο) and ο) l analysis immediately after opening locked. /; iener packs}

- d) l A-Excellent, SGMSvery goodJ O-Goodj Z * Satisfactory 3L-8poor {

^: e) t added surfactants after adding the. Silicate / Vaeier GeraischeB,

The commercially available sample A is based on a formulation similar in terms of components and amounts to sample 2 "ν DIi Brgebniese" that sample Z only has 34% of its available chlorine after 30 days in air at room temperature

compared with £ 94 loss in sample A 'In the case of open containers, sample 2O ^ of the available Ohlora and sample A lost 45t,

₄ v The other commercial sample B is similar in components

λ And amounts of sample 5 · The result · * show that the

||: Sample 5 during 30 were only 2 ^ of theirs at room temperature

, ',, Available Ohlorlr and Ale sample S 103 * lost ·

The results obtained for samples 3 and 4 show ^, because the reliance on the addition of the liquid materials

- * · 'tu ^ iikt critical IeIu "V'. _: ? |. ^Λ -

r ■ * ■■; ■. ■ '■■ - · ■ .-. - λ

009816/1701

Claims (1)

- M - PATENT CLAIMS t "'■■ Μ: 1. Process for the production of agglomerates from Detergena * ·; Components »marked» that one '\ (1) finely divided Betergene components in an agglomerationa * · | zone introduces, (2) in this zone a free fall veil from these Components "forms, '..". ".' (3) the components in this falling veil with a j brings liquid material into contact to make this fine; Partial material to agglomerate »L (4) at the pusee of this falling veil an overturned one. 'Layer of agglomerating detergent components "bit .--. , Det, and * _)' _ ■ ^; - ■ £ ι ' (5) agglomerated material from this agglomeration zone subtracts, · i ■ 2. The method according to claim 1, characterized in that; as - ^ etergent components a) condensed AlkaliphQS- _; 'ί phate, b) compounds containing active chlorine, c) sodium or potassium silicate, d) surface-active agents and e) water. ' ι. 3 · The method according to claim 1, characterized in that the process is carried out continuously. ' 4. The method according to claim 1, characterized in that mail used as detergent components »a) about 20 to 80 parts by weight of a condensed alkali metal phosphate with a Na ₂ 0 / P ₂ 0 ₅ - or KgO / P ^ ratio of about 1: 1 to 2j1, b) about 0.5 to 35 parts by weight of chlorinated sodium phosphate, trichlorocyanuric acid, sodium salt of dichlorocyanuric acid, potassium salt of dichlorocyanuric acid, sodium hypochlorite / or 1,3-dichloro-5,5-dimethylhydantoin, c) about 3 to 30 Parts by weight of sodium or potassium silicate with a NagO / SlOg- ·. or K ₂ 0 / Si0 ₂ ratio of about 1: 3 »75 to 2: 1, d) about 009816/1701 O _t 3 1} 1b 3 parts by weight tine »niohtioniaohen surface active a and β) about 5 to 50 parts by weight per part by weight 5. Procedure naoh Anapruol * 4, thereby gtkennielohnet that all Setergene components Temfendeif * a) about 30 to 60 % triumtripolyphoeift) .Ät | b) about 10 to 35 ^ ohloriertei! Drinatritimphoepliat, o) about 4 to 19 SewiöHllti UiSW'l'Blil Natriumeilikati with a lfegQ / SiOg, -VerjbältniB τοη about 1t3 »75 *> ie 2i1» d) about 0.5 to 3 öe- * Iorteile a niohtioniaohen surface-activating means »^ the aelbat or in blessing aohamn-forming Sohmutzes nioht or is only slightly aloof and is compatible with chlorinated trisodium phosphate, and e) Waaaer in sufficient quantity, to at least the complete hydration of the sodium tripoly-. to enable phosphates »" ..,. 6 «Method according to Anapruoh 4i daduroh characterized that all detergent components are used a) about 30 to 60 parts by weight of sodium tripolyphoid acid, b) about 0.5 to 10 parts by weight of potassium or sodium chloride, c) about 3 bia 30 Gewiohtateile a · ^ atriumailikata with a Na ₂ 0 / Si0 ₂ of about -Verhältnia tt5 # 75 bi.e 211) d is about -0.5 to 3 Gewichtateile a niohtioniaonln ¹¹ ^ «irilädftehaic-" tive agent aelbat little or no foaming tinea aohaumbildenden Schmutzea and iat compatible with sodium or Kaliumdichloriaooyanurat, and e) water in sufficient close ^M to zumindeat vollatändige the hydration of the Natriumtripolyphoaphata to allow, or in the presence of... 7 * procedure NaOH Anapruoh 2 _t daduroh geliennzeiohnet that one said Detergena components optionally Nooh _calcinated; added soda. 009816/1701 "■ ** ■ 8. The method naoh claim 2, daduroh characterized daae the detergent components mentioned can also optionally be served with calcined soda and borax. fftir * Stauffer Ohemical Company Lawyer 009816/1701 INSPECTED