CA1066029A

CA1066029A - Process for the preparation of non-dusty, easily wetted and readily soluble granulates

Info

Publication number: CA1066029A
Application number: CA194,048A
Authority: CA
Inventors: Alberto Rabassa; Roland Haberli; Hans Mollet
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1973-03-16
Filing date: 1974-03-05
Publication date: 1979-11-13
Also published as: ES424295A1; OA04622A; AR201499A1; IL44352A; ATA216674A; CS193030B2; IT1015852B; AU6644374A; JPS5342035B2; BR7402030D0; JPS5025481A; DK136515C; IL44352A0; AT346811B; AU502974B2; DD110770A5; FR2221178A1; DE2412369A1; DK136515B; NL7402981A

Abstract

Abstract of the Disclosure A process for the preparation of granules which comprises exposing the substance to be granulated to a liquid system consisting of a first liquid component which does not dissolve the substance and a small amount of a second liquid component which wets or dissolves the substance, and which second liquid is partially miscible with the first liquid component, and mixing the multiphase system so produced to form granules of the substance and subsequently separating the granules from the liquid system. According to this process there are obtained very stable granulates of the correspond-ing substance which possess the unexpected property of "instant" response on application.

Description

10f~60'~9 The invention relates to processes for the preparation of non-dusty, easily wetted and readily soluble granulates, of any desired size~ from a multiphase system, as well as to the non-dusty, easily wet~ed and readily soluble granulates, as an industrial product, prepared by application of these processes.
Certain commercial forms of solid substances are up to the present being marketed in the form of normally dried and finely ground powders, or as spray-dried microgranulates. Both types, however, have the disadvantage that, to a greater or lesser extent, they release dust; moreover, in consequence of poor wetting, their rate of dissolving is in many cases too low for the modern requirements of industry, a factor which in part renders necessary long operational times for the preparation of solutions, or the use of expensive ~ stirring equipment. Attempts have therefore been made ,! to improve wetting by the addition of wetting agents, particularly in dyestuff preparations.
The changeover from the conventional drying method to spray drying enables in certain cases, with identical ;~ composition of the product, wetting to be improved: in other cases, however, it is worsened. The microgranulates produced in industrial spray driers mostly have moreover a very wide range of particle sizes, with a considerable ` proportion of fines. This high proportion of fines is unfavourable not merely on account of the resulting :

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tendency for the ~orma~ion of dust to occur, but also on account of the resulting impairment of the wettabîlity of these powders due to the formation of lumps wh~n the powders are introduced into a liquid. Furthermore, it has been shown that spray-dried granulates are in many cases not sufficiently stahle mechanically, and disintegrate during storage and, in particular, during transport, with a further creation of dust occurring. These disadvantages have been known for some time in foodstuff technology;
methods have therefore been developed to eliminate the proportion of fines, one method being, e.g. the subsequent agglorneration of the powders in special apparatus.
Efforts have naturally been made for a long time in the case of dyestuffs too, with a varying measure of lS success, to separate the fine fractions and to return them to the drying process. It has however hitherto not proved possible, without very high expenditure in equipment or high losses, to obtain by spray drying a relatively coarse granulate giving a narrow particle-size distribution curve.
In recent times, therefore, efforts have been directed towards conversion of products, e.g. by compacting or e~trusion, into actual granulates having a particle size of 1 mm or more. With suitable composition, the resulting granules can have such a high degree of strength that they do not form dust, even after prolonged intensive shaking.

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But they have the disadvantage ~hat their dissolving rate is loW7 a~taining, however, in the most favourable case the values given by the corresponding powders.
A more recent commercial method for the preparation of non-dusty, readily soluble powders is vacuum freeze drying. This however produces pro-ducts having poor free-flowing properties and, for reasons of cost, is suit-able only for expensive products.
It is also known that barium sulphate suspended in fine dispersion in hydrous benzene can be agglomerated by shaking to form larger particles.
Surprisingly, it has now been found that it is possible by wet granulation to obtain mechanically very stable granulates of any desired size which are non-dusty but nevertheless easily wettable, and which possess the unexpected property of "instantl' response on application.
Accordingly the invention provides a process for the preparation of granules which comprises exposing the substance to be granulated to a liquid system consisting of a first liquid component which does not dissolve the sub-stance and a small amount of a second liquid component which wets or dissolves the substance, and which second liquid is partially miscible with the first liquid component, and mixing the multiphase system so produced to form granules of the substance and subsequently separating the granules from the liquid sys-tem.
The mixing is preferably carried out turbulently. Conveniently the process may be operated at room temperature.
In one embodiment, the second liquid is added gradually to the sus-pension of the solid in the first liquid.
It is possible to use the process according to the invention for the granulation of the most varied types of substances; they can be homogeneous substances or mixtures of substances. These accordingly belong to the most diverse classes of substances: they are, for example, dyestuffs, optical brighteners or textile auxiliaries, pharmaceutical products, pest-control agents, foodstuffs, such as coffee, milk or flour; antimicrobial agents and bacteriostatics; detergents, paper auxiliaries (e.g. sizing agents), photo-B _4_ .

.. ' ~ ' ~ - ' 10~0~9 graphic chemicals, leather chemicals, plastics and additives for plastics.
It is clear that the substances specially concerned are those which are readi-ly wettable to soluble in one of the two liquids. These substances can be pure, or they can also contain extenders, e.g. salts or further components.
By dyestuffs are meant in the present case those of all possible classes, both coloristically and chemically, which are suitable for an aqueous and organic application. The following examples are given: basic dyestuffs, acid dyestuffs, sulphur dyestuffs, vat dyestuffs, mordant dyestuffs, chrome dyestuffs, disperse dyestuffs, pigments and, in particular, direct dyestuffs, whereby these dyestuffs can contain fibre-reactive groups in the molecule.

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10~0'~'l3 Also inclu~ed are obviously ~odstuff-colouring agents and, for example, leather dyestuffs.
The dyestuffs concerned from tle chemical point of view are, for example, nitroso, nitro, monoazo, disazo, trisazo, po~yazo, stilbene, carotenoid, diphenylmethane, triarylmethane, xanthene, acridene, quinoline, methine, thiazole, indamine, indophenol, azine, oxazine, thiazine, lactone, aminoketone, hydroxyketone, anthraq~linone, indigoid and phthalocyanine dyestuffs, as well as 1:1- or 1:2-metal-complex dyestuffs.
Applicable optical brighteners, used for white tinting, are those of any desired classes of brighteners; for example, they are stilbene compounds such as cyanuric derivatives of 4,4'-diaminostilbene-2,2'-disulphonic acid or distyryl-biphenyls, coumarins, benzocoumarins, pyrazines, pyrazolines, oxazines, mono- or dibenzoxazolyl or mono- or dibenzimidazolyl compounds, as well as naphthalic acid imides, naphthotriazole and v-triazole derivatives.
By textile auxiliaries are meant chemicals required in the processing of the various textile fibres into finished fabrics: thus, e.g. raw wool detergents, - lubricants, sizing agents, milling agents, impregnating agents, preserving agents, finishing agents, desizing agents, kier-boiling agents, bleaching agents, dyeing agents such as dispersing agents and leve~ling agents, , ~ ;

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printing ~uxili~ ies, carbonising a~ents, mercerising agents, preparations ~or the acquiremel~t of resistance to creasing and to shrinkage, and antistatic prep~rations.
Pest-contro] agents are in general known: they serve, S for example, to effect the destruction of plant pests (e.g. fungicides, insecticides, acaricides, nematicides, molluscicides and rodenticides) and the prevention of plant diseases.
By antimicrobics are meant antimicrobial substances which are intended to, or serve to, retard or prevent disadvantageous changes caused by microorganisms in foodstuffs.
Bacteriostatics are substances which inhibit or prevent the growth of bacteria.
Detergents are substances which are synthesised, e.g.
from (a) a wash-active synthetic substance, a washing raw material, (b) a washing auxiliary (detergent additive), (c) special additives, such as sodium perborate, magnesium silicate, optical brighteners, wetting agents, etc. and (d) extenders. Both the detergent as such and the individual constituents thereof can be granulated according to the invention.
And, finally, plastics can be granulated; by these are meant macromolecular organic compounds obtained by the conversion of natural products or by synthesis, whereby plastic compounds are also included.

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All ~hese subs~allces c.ln be use~ according to the invention in tl~e pure form or in the commercial form or in the form of dried or moist pr~ss cakes for the preparation of granula~es. Advantageously, they S are in the form of powders ground as fine as possible;
they can, however, also be in the form of suspensions, such as are obtained, e.g.after synthesis. The process is likewise applicable, or example, to flocculated sediments, such as those occurring in waste-water purification.
The substance to be granulated is present advantageously in amounts of 1 to 150%, relative to the first liquid.
Liquids not dissolving the substances to be granulated, i.e. those used as the first liquid, are either water or organic liquids, or mixtures of organic liquids.
A suitable second liquid, which preferentially wets to dissolves the substance to be granulated, is an organic liquid im~iscible with water, or a mixture of such organic liquids, in the case where the first liquid is water, and water and/or another liquid immiscible with the first liquid, such as an organic liquid or a mixture of such organic liquids, in the case where the firs~ liquid is an organic liquid or a mixture of organic liquids. Hence, ~ there are principally three possibilities; namely:
a) 1st liquid : water, 2nd liquid : organic liquid or mixture of organic liquids;

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. j . , b) 1st liq~id : organic liquid or mixLure of organic liquids, 2nd liquid : water;
c) 1st liquid : organic liquid or or mixture of organic liquids, 2nd liquid : as defined, an organic liquid different from the 1st liquid~ or mixture vf such organic liquids.
The best results are obtained with variant b).
The requirements to be satisfied by the organic liquids used to effect granulation are dependent on the nature of the particular substance to be granulated. These organic liquids are, for example, alcohols such as

2-ethyl-1-hexanol, 1,3-dichloro-2-prvpanol, ethanol and butanol; aliphatic hydrocarbons, both open-chain and ring-shaped, such as n-hexane and ligroin or cyclohexane;
aromatic hydrocarbons such as benzene and toluene;
halogenated aliphatic hydrocarbons such as carbvn tetra-chloride, methylene chloride, chloroform and perchloro-ethylene, or rnixed halogenated hydrocarbons, such as those known ~mder the trade name of "Frigen", e.g. trichloro-trifluoroethane (Frigen 113 CR), as well as esters, such as acetic acid ethyl ester. Also applicable, as defined, are mixtures of organic liquids, advantageously in the mixture ratio of 1:1, such as, e.g. a mixture of dimethyl-sulphoxide and 1,3-dichlvro-2-propanol.

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The second li~luid is adval1tageous1.~ ~mployed in amounts of l to 60%, l~articularly 2.5 to 10~/o~ relative to the first liquid; or in amou11ts of lO to 90%, particularly l5 to 50%, rel~tive to the arQount of substance. These mixture-ra~io amounts should be largely adhered to since in the case of excessive deviations, especially upwards, undesirable continuous masses of substance could otherwise form.
Optionally, auxiliaries may be added to th.e second liquid, such as, in particular, bonding agents; and/or wetting agents, diluting agents, effervescent agents, solubilising agents, dispersing agents, acids or alkalis.
It is especially the bonding agents which serve, above all, to increase the mechanical strength of the granules. Such lS bonding agents to be mentioned are: polyvinyl alcohol, cellulose derivatives, such as carboxymethylcellulose and hydroxypropylcellulose, polyvinylpyrrolidone and also dextrine.
The process according to the invention is such that the substance to be granulated is suspended, with stirring, in a liquid or mixture of liquids not dissolving the said substance, and an addition then made, in the defined - quantity ratio, of a second liquid or mixture of liquids :
which in either case is immiscible with the first liquid, ~ and which preferentially wets to dissolves the said 25 substance~ to thus form a multiphase system, and the resulting mixture then brought into a state of intense turbulence.
This is created, for example, by vigorous stirring movements, by use of a vibromixer, or by treatment in ~ :
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~0 ~ ~0'~9 a shaking n~tlchine or Turbula.
Under these conditions, with creation o~ a suitable state of turbulance in the suspension, the second liquid or mixture of li~uids must be added in such a manner that firstly the surface of all primary particles is coated therewith. Only thus is there obtained, by a precisely dosed amount of the second liquid, a complete agglomeration. There are then formed in the multiphase system substance-agglomerates having a fairly homogeneous particle distribution. Their size is governed by the quantity ratio of the second liquid to the substance.
These agglomerates are subsequently separated from the liquid multiphase system by a manner known per se;
e.g. by filtration under suction or by normal filtration, and dried by known methods.
A preferred embodiment comprises, for example, the suspension or dispersion of four parts of dyestuff, optical brightener, textile auxiliary, bacteriostatic agent, washing raw material and detergent, paper auxiliaries or leather chenicals in 8 parts of an organic liquid, e.g.
a mixed halogenated hydrocarbon such as trichlorotrifluoro-ethane; and the addition continuously, with ~horough turbulent "'! mixing by means of a stirring or mixing apparatus, of `, 1 part of water; and the subseyuent intensive mixing together of this mixture until agglomerates form in the three-phase system.

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~0~6(~29 In a modification of the process, the substance to be granulated is added to a multiphase system consisting of a liquid or mixture of liquids not dissolving the said substance and a second liquid or mixture of liquids which wets to dissolves the substance on its own, and which is immiscible with the first liquid, the addition being made continuously, with stirring and subsequent turbulent mLxing, in such a manner that ag~omerates of the said substance are formed, which are afterwards separated from the multiphase ~; -system and dried. ;
The details initially given with regard to the ~ ;~
substance to be granulated and to the liquids apply where appropriate for this modification too.
There are obtained by these processes, the surprising , factor of which is that on application to water-soluble substances or to organosoluble substances these do not ;
dissolve in the aqueous or organic phase, but precipitate from the two-phase or multiphase system, granulates --which can have the most diverse forms, such as, for example, spherical, lenticular, elongated or rod-shaped. ~; -The diameter of these forms is preferably 50 to 500 microns, with the granules being of a very uniform size. These granulates are surprisingly of such a nature that, compared with the corresponding powder forms, they have a much higher rate of dissolving or more rapid dispersibility, ~,, '~' .

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particularly in cold water and hot ~ater, and, furthermore, that they do not create dust and are moreover very readily wettable; they are also very free flowing, and have a high bulk weight. It is possible in this manner to obtain from soluble substances granulates having "instant" properties, i.e. their decomposition in the solvent medium is instantaneous. Also to be emphasised is the high mechanical stability of the said granulates.
The yield of these granulates can amount to up to 100%. With the correct choice of liquids, granulation is in most cases complete, with the result that there is a clear separation of the liquid phase.from the solid phase.
The following examples are intehded to illustrate the invention without in any way limiting ~he scope thereof. The granulates obtained can in general be easily dispersed or dissolved in their application medium without the use of special stirring devices.

,, ~60~9 Example 1 An amount of 4 parts by weight of the dyestuff of the formula SO Na OCH3 COONa ~3 N = N ~ I~TICO~IN ~ N = N _~ OH

is added to 20 parts by volume of 2-ethyl-1-hexanol, and a suspension obtained by vigorous shaking in a Turbula*. Two parts by volume of water are then added to the suspension, and shaking of the mixture is continued, After a shaking time of 15 minutes, spherical dyestuff-agglomerates of 0.5 to 1 mm diameter are obtained: these are separated from the two-phase system by filt-ration, and dried to obtain a light-brown dyestuff granulate which is very 10 free flowing, non-dusty, easily wetted and readily soluble in cold water.
IfJ instead of 20 parts by volume of 2-ethyl-1-hexanol, identical parts of trichlorotrifluoroethane, carbon tetrachloride, n-hexane, ethyl acetate, methylene chloride, benzene, chloroform or cyclohexane are used, with otherwise the same procedure, then dyestuff granulates having similar .
properties are obtained.

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1066C)29 Exarnpl e 2 ~n amount of 4 parts by weight of tle dyestuff of the formula C~3 ~

~ ~ c~N ~ ~ YDC1 ~

is addPd to 60 parts by volume of 2-ethyl-1-hexanol, and a suspension obtained by vigorous shaking in a shaking machine. One part by volume of water is then added to the suspension, and shaking of the mixture continued for 1 hour. This procedure leads to the formation of sma]l dyestuff globules of uniform size: these are separated from the two-phase system and subsequently dried. An ochre-yellow dyestuff granulate is obtained which is very free flowing, non-dusty, easil.y wetted and readily soluble in cold water.

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E~am~~ 3 -An amount o~ 4 parts by weight of tLIe dyestuff of ~he formula . ' S03Na ; ~ N - N- ~ C~13 CO-C=C~12 ~,Cl ',, - Br Cl S03Na is added to 20 parts by volume of carbon te~rachloride, and a suspension obtained by vigorous shaking in a Turbula (shaking machine) for 20 minutes. 1.5 Parts by volume of water are added to this suspension, and the mixture is subsequently shaken for 40 minutes. Lenticular ,~ , . . .
dyestuff-agglomerates of 0.5 to 1 mm diameter are ~ ;:
i 10 obtained: these are separated from the two-phase system .~ by filtration, and dried to obtain a yellow dyestu~f

3 granulate which is very free flowing, non-dusty, easily wetted and readily soluble in cold water. .
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(pure material) . .

` is added to 20 parts by volume of n-hexane, and a ,, suspension obtained by shaking of the whole for 12 minutes in a shaking machine. One part by volume of water is added to the suspension, and the mixture then ;
shaken for 40 minutes. Spherical to elongated dyestuff-agglomerates of 0.5 to 3 mm diameter are obtained: these are separated from the two-phase system by decanting, ``
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`1 10 and dried to obtain a reddish-violet dyestuff granulate ~ `
which is very free flowing, non-dusty, easily wetted `
` and readily soluble in cold water.

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- , , , ~ ~ ~6 02~9 l~ampl.e 5 An amoun~ of 4 parts by weigh~ o~ an optical brightener of ~he formula .
,' L~ CJ~N~ 'h~C~ 3o~5~--CH3 :' , , ' .
is added to ?0 parts by volume of n-hexane, and a suspension obtained by vigorous shaking of the whole or 5 minutes. To this is added 0.5 part by volume of : water, and the mixture then shaken for 20 minutes.
:; Spherical agglomerates of 0.5 to 3 mm diameter are .~ obtained: these are separated from the two-phase system, ~ 10 and dried to give an optical brightener granulate which is very free flowing, non-dusty, easily wetted and ~33 readily soluble in cold water.
'.'J If the optical brightener employed is one of the ~:j formula ., .
~ 15 ~ - CH = CH ~ CH = CH-->

.", S03Na NaO3S
. .~ . - . this bein~ suspended in perchloroethylene and granulated with water, the procedure otherwise remaining the same, . then equally good granulates are obtained.

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If the optical brightener employed is one of the formula ;

-N~l N~03S / I/N ~ ~
NH- ~ Cll = C~ _NH ~ N~ :
03Na this being suspended in cyclohexane and granulated with water, the procedure otherwise remaining the same, then equally good granulates are obtained.
, If the optical brightener employed is one of the j formula ~7 CH = CH- ~/ ~ 3 this being suspended in water and granulated with toluene, the procedure otherwise remaining the same, - -then equally good granulates are obtained.

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1~fà60'~9 Exan~Lle 6 An amount of 4 parts by weight of the dyestuff of .1 the ormula -' j U3C - N ~ N - ~ ZnO1 i (dried press cake) is added to 20 parts by volume oE n-hexane, and a suspension obtained by vigorous shaking of the whole ;-- for 20 minutes. To this is added 0.5 part by volume of water, and the mixture then sha~en for one hour.
Spherical dyestuff agglomerates of about 1 to 3 mm diameter are obtained: these are separated from the .~. 10 two-phase system, and dried to obtain an ochre-yellow ~:
dyestuff granulate which is very free flowing, -non-dusty, easily wetted and readily soluble in cold water .q :':

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106~;~Z9 Fxample 7 An amount oE 4 parts by weight of the dyestuff of the formula S03~1 ~1 ~ Cl co c~J
C-Br S03H
C~12 (dri.ed press cake) is added to 20 parts by volume of n-hexane, and a suspension obtained by vigorous shaking for 10 minutes.
i An addition of 0.7 part by volume of water is made to the suspension~ and the mixture shaken for a further 15 minutes. Spherical dyestuff agglomerates of about 0,5 , , to 1 mm diameter are obtained: these are separated rom the two-phase system, and dried to ob~ain a yellow dyestuff granulate which is very free flowing, non dusty, easily ~-~
wetted and readily soluble in cold~water.

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-N N CH
H0 N 2:1-cobalt complex 2 2 5 ~ .
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is added to 20 par~s by volume of n-hexane, and a suspension obtained by vigorous shaking for 12 minutes. :~
~n addition of 1.5 parts by volume of water is made to ~.
the suspension, and the mixture shaken for a further ~-10 minutes. Spherical dyestuff agglomerates of uniform ~ siæe having a diameter of about 0.5 to 2 mm are obtained:
t 10 these are separated from the two-phase system, and -~
dried to obtain a dark brown dyestuff granulate which is very free flowing, non-dusty, easily wetted and readily soluble in cold water.
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10 6 60 ~9 Example 9 An amoun~ of 4 parts by weight of the dyestu~f of ; the formula (113C)3N - C~2 - CO ~ - N = N ~
Cl H3C H

is added to 20 parts by volume of n-hexane, and a suspension obtained by vigorous shaking for 10 minutes.
One part by volume of water is added to the suspension, and ~he mixture shaken for a further 20 minutes. ~:
Spherical dyestuff agglomerates of uniform size having a diameter of about 0.5 to 2 mm are obtained: these are separated from the two-phase system, and dried to obtain a light-bro~l dyestuff granulate which is very free flowing, non-dusty, easily wetted and readily soluble in cold water.

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An amoun~ of 4 parts by wei.ght of a dried dyestuff press cake containing the dyestuff of the formula Cl NH ~

02N - ~ -N - N ~ C2H5 1 NH-C~12-C~2~0H

is added to 20 parts by volume o water, and the whole vigorously shaken for 10 minutes to obtain a suspension.
An addition is made to this of 2 parts by volume o~
ethyl acetate, and the mixture shaken for a further 20 minutes; spherical dyestuff agglomerates having a diameter of about 1 to 2 mm are obtained: these are separated from the two-phase system, and dried to obtain a dark bro~n dyestuff granulate which is very :~
free flowing, non-dusty, easily wetted and readily soluble in cold water.

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~ 0 6 60 Z9 F,xample 1 1 -An a~nount of 4 parts by weight o~ the dyestuff of the ~ormula S03Na ~ Cl CO Cl ~ ' ' C-Br S03Na ;
- is added, with vigorous shaking, to a two-phase system consisting of 20 parts by volume of carbon tetrachloride -and 2 parts by volume of water, ?nd the mixture shaken in a shaking machine tTurbula) for about 40 minutes. ~ :
Spherical dyestuff agglomerates are obtained: these are separated from the two-phase system, and dried to obtain a yellow dyestuff granulate which is very free flowing, non-dus~y, easily wetted and readily soluble in cold ~ water~
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'. ' . t ' ' :' '- ' ' ": ' ' ~ ' " ' ' ' ~ ', ~ ' ' ' ~0 6 6 0 Z9 Examplc_12 An amount of 4 parts by weight of the dyestuff of the formula S03Na pC~3 ~ OONa = N-~ ~ ~IC0~1 ~ N ~ 0~1 \=/ ~ -., '' ' ~' is added ~o 8 parts by volume of n-hexane, and the whole ;
shaken vigorously for 10 minutes to obtai.n a suspension.
An addition is made to this of 2 parts by volume of - water, and shaking continued for a further 20 minutes.
. Spherical dyestuff agglomerates are formed having a diameter of 1 to 2 mm: these are separated from the two~phase system, and dried to give a light-brown dyestuff granulate which is very free flowing, non-dusty, easily wetted and readily soluble in cold water. The bulk weight of these granulates is 0.7, and is appreciably higher than that of spray-dried dyestuff.
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Example 1 3 An amount nf 4 parts by weight of ~he dyestuf of the formula HO QH
-N = N ~ ~ N -- N-- ~ N~COCH3 NaO3S N~ICO~I 503Na .~ , is added to 20 parts by volume of cornmercial benzene, and the whole vigorously shaken to obtain a suspension. ~;~
An addition is made to this o~ 1 part by volume of water, and this mixture sl-laken in a shaking machine (Turbula). ~fter a sha~ing time of 30 minutes, spherical , dyestuff agglomerates of about O.S to 1 mm diameter are formed: these are separated from the two-phase .
system, and dried to give a red dyestuff granulate ;
which is very free flowing, non-dusty, easily wetted :1 .
1 and readily soluble in cold water.

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Example 14 An amount of 4 parts by weight of the dyestuff of the formula f SO Na OCH
COONa (~3N = N~--NHCONH {~ N = N ~OII

is added to 20 parts by volume of trichlorotrifluoroethane (Frigen* 113 CR), and the whole vigorously shaken to obtain a suspension, to which is then -added 1 part by volume of water. After a shaking time of 30 minutes, spheri-cal dyestuff-agglomerates of ca. 0.5 to 1.5 mm in diameter are formed: these are separated from the two-phase system, and dried to give a light-brown dye-,'? stuff granulate which is very free flowing, non-dusty, easily wetted and 3 10 readily soluble in cold water.

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~ample 15 An amount of 4 ~rts by weigllt of ~l~e dyestuff of -~
the ormula S~O Na /OCl-13 &~3 - N = N ~ --N~ICONH~ N - N -3~a S03Na ~;

is added to 20 parts by volume of n-hexane, and the whole vigorousLy shaken to obtain a suspension. One part by volume of water is added to this, and the mixture shaken in a shaking machine (Turbula). After 0 30 minutes' shaking time, rod-shaped dyestuff agglomerates of ca. O.S mm diameter are formed: these are separated from the two-phase system, and dried to give a yellow dyestuff granulate which is very free flowing, non-dusty, easily wetted and readily soluble in cold water.

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Exan~_e 16 An amoun~ of 4 parts by weight of a textile auxiliary (dinaphthylMethane-disulphollate) is added to 20 parts by volume of 2-ethyl-1-hexanol, and the whole shaken vigorously in a shaking machine (Turbula) to obtain a suspension; to this are added 2 parts by volume of water, and shaking of the mixture is continued. After a shaking time of 15 minutes, spherical agglomerates of 0.5 to 1 mm diameter are formed: these are separated from the two-phase system by filtration, and dried to give a granulate which is very free flowing, non-dusty, easily wetted and readily soluble in cold wa~el.

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10f~60~Z9 Example 17 ; To 40 parts by weight o~ Frigen 113 are added 5 parts by weigh~ of a fungicide of the formula - COC1~13 -and the whole is vigorously shaken for 5 minutes to obtain a suspension. An addition is made to this o~
2 parts by volume of water, and the mixture then shaken for 10 minutes. Spherical agglomerates of the fungicide are obtained, which are subsequently separated and dried.

Exarnple 18

4 Parts by weight of the pharmaceutical agent 3-(4-methyl-1-piperazinyl-iminomethyl)-rifamycin SV
are added to 20 parts by volume of Frigen 113, and the whole is vigorously shaken for 2 minutes to obtain a suspension; an addition is made to this of 2 parts by ;
volume of aqueous lN hydrochloric acid solution, and the mixture shaken for 10 minutes. Spherical agglomerates of the pharmaceutical agent are obtained, which are ~hen 'i separated and dried.

'-' 106~0Z~

5 Parts by weight of the pharmaceutical agent 1-(2-allyloxy-phenoxy)-3-isopropylamino-2-propanol are added to 25 parts by weight of Frigen 113, and the whole is shaken vigorously for 2 minutes; a suspension S is thus obtained and to this are added 4 parts by weight of water; the whole is shaken for 3 minutes to obtain spherical agglomerates, whi~h are subsequently separated and dried.

Example 20 50 g of a finely powdered, heavy-duty detergent containing 16 g of the sodium salt of dodecylbenzene-sulphonate, 4 g of fatty alcohol sulphate, 3 g of coconut fatty acid monoethanolamide, 40 g of tripoly-phosphate, 4 g of sodium disilicate, 2 g of magnesium silicate, 1 g of carboxymethylcellulose, 0.5 g of Sequestrene ST, 5 g of water and 24.5 g of sodium sulphate are dispersed in butanol in the course of 5 minutes by means of a powerful stirrer. An addition is then made slowly, with stirring, of about 40 mL of water: this results in the formation of spherical agglomerates of the 20 ~ detergent, which are filtered off. The dried product is non-dusty, easily wetted, and readily soluble in water.
, :' ' ' 1()6~0Z9 Fx~mr)l~ ?l 20 g of a pulverulent, nonionic detergent containing4 g of nonylphenol added to 3 to 6 moles of ethyleTIe oY~ide, 4 g of nonylphenol added to 9 to 10 moles of ethylene oxide, 4 g of Alfol C16 18 added to 25 moles of ethylene oxide, 3 g of sodium soap, 50 g of sodium tripolyphosphate, 5 g of sodium disilicate, 2 g of magnesium silicate, 1 g of carboxymethylcellulose, lO
to 12 g of sodium sulphate, 5 g of sodium carbonate and 10 to 12 g of water is suspended in 50 g of ligroin (80 to 110C). An amount of 8 ml of water is then stirred in by means of vigorous stirring; the result is the formation of small spherical agglomerates of the detergent, which, after drying, are non-dusty, easily wetted in water and soluble.
. ~ . .

Example 22 18.5 g of finely ground coffee is suspended in ligroin (80 to 110C). There is then continuously added, with vigorous stirring, 7.5 g of a mixture of 9 parts of ethanol and 1 part o water. The resulting coffee granulate is filtered off and dried. A granulate is thus obtained ~ ;
` 20 which is instantly soluble in cold water (Instant Coffee).
Equally good results are obtained with extracted coffee powder.

Example 23 .. . . . .
100 g of spray dried milk powder (skim milk base powder) ,~ .

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: . . . . .
.. : ~ , . . . .
... . . . . . . .

lOf~:iOZ9 is suspen~led ill 300 g of ligroin (80 to 110C). An addition is then made dropwise, with vigorous stirring (500 r.p.m.), of 28 ml of water. Easily filterable granulates are ~hus obtained, which, a~er drying, readily dissolve in cold water.

Example 24 20 g of flour is suspended in 60 g of ligroin (80 to 110C); to this suspension there is then added dropwise, with vigorous s~irring, 6 to 7 ml of 1,3-dichloro-2-propanol; this results in the formation of small to medium-sized agglomerates which, after drying, give a non-dusty flour granulate.
., Example 25 100 g of a cation-active melamine-formaldehyde-resin (paper-sizing agent) is suspended in 500 g of Frigen 113, and to the suspension is slowly added dropwise, with vigorous stirring, 20 ml of 1,3-dichloro-2-propanol.
There are thus formed spherical granulates, which are dried on a glass frit with compressed air.
Identical granulates of similar quality are also obtained ~ by the additlon dropwise, with stirring (ca. 700 r.p.m.) of 18.5 ml of 1,3-dichloro-2-propanol to 100 g of cation-active melamine-formaldehyde-resin suspended in 500 g of . . .
ligroin (80 to 110C). There are thus formed small spherical agglomera~es, which are dried on a glass frit by compressed air.
, , t~ ~':~ ' , : ' ' ~ ~ ' ~' :, ' ~ ' ' . .
' ' ' ' ', ' ' :
,'. ' ,^ ': ' , , ' : ' ~C~66~Z9 Exam~26 S g of the an~imicrobial agen~ of the formula Cl~ ~ --0 ~ ~ ~ ~ Cl ~`

011 Cl is suspended in 50 g of water; there is then made~
~: with stirring, a dropw.ise addition continuously of . 5 about 6 ml of li.groin (80 to 110C). There are thus : formed small spherical agglomerates, which can be easily dried to obtain the corresponding non-dusty granulates of the antimicrobial agent.
Granulates of similar quality are obtain.ed by the slow addition dropwise, with stirring, of about 1~ ml of n-butanol to 10 g of the above antimicrobial agent suspended in 100 ml of water. The resulting aggl.omerates are spherical to angular in shape.
.3 Example 27 35 g of moist dyestuff press-cake containing the . -~ 15 dyestuff of the formula ~.

,. 3 ' ~02NHCH2CH20H ~;
:` is stirred into 60 g of n-butanol for about 10 minutes.

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106~0'~9 Ihere is sul)seq-lently added, witl~ stirring (ca. lO00 r.p.m.), lO0 g o~ Frigen ll3; an addition i~ then slowly made dropwise, to eEfect agglorneration, of 6.7 g of wa~er.
Agglomerates are thus formed, which are separated, and aterwards dried in a drying cupboard at 50C to obtain the corresponding dyestuff granulates, which dissolve very rapidly in water.
~ .
Example 28 8.5 to 9 ml of water is added dropwise, in the course of about 15 to 20 minutes, to 30 g of the dyestuff of ; lO the formula C1-13 :::' S02J.
~ ~ - N = N-., .
~ S0311 . ~
suspended in 90 g of Frigen 113. There occurs the formation of agglomerates, which are then separated from the muItiphase system, and dried at 50C in a drying cupboard to give dyestuff granulates readily soluble in water.
.

~ Example 29 .' ~
: 6 g of water is added dropwise in the course of about 15 minutes, with stirring, to 20 g of the dyestuff of the formula i - 36 :. :
.. .

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o so ~
Cl N -- N - CH - C - C~13 N
~12~--N~
l Cl .
. in 60 g of Frigen 113. This results in the formation of agglomerates, which are subsequently dried on a g].ass frit with compressed air to obtain dyestuff granulates which are very readily soluble in water.

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50 g OL tlle powdered dry d-~estufr of a self-condeils~tion produc~ of p^nitrotoluene-2-sulphonic acid in 100 g of n-butanol (suspcnsion liquid) are put into ~ reaction vessel Ater stirring ~or app. 5 minutes (app. 500 rpm~ at room temperature, 33 ml of water are added dropwise to the homogeneous suspension at th~
same stirring speed using a drip funnel. Stirring is then continued for app. 30 minutes, after which time the agglomcratiGn is terminated. The precipitated dyestuf granulate is separated using an aspirator and a BUchner suction filter and dried at 50 in vacuo.
Yield: 50 g of the above dyestuff in granulate fonn. It is characterised by a fairly l-om~geneous granulometry in the range of app, 200 to 600 microns-~nd contains no fine dust. Wh~n added to water, the granules are wetted momentarily and dissolve very rapidly.

., . .... ,~ .
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Example 31 loo g of an aqueous filter cake (33% solids and 67% water) , ............. . .
Oc the same dye ~s used in Example 30 is converted into a thin, homogeneous ~spension by adding 250 g of n-butanol with ~lomorex, and granulation is also effected during the slow addition of ,~( .
3 app. 1 ml of water with good stirring at room temperature.
~ Stirring is continued for app. 30 minutes to bring the agglo~.er-i ation ~:o completion and to harden the particles. The granulate .. . .

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precipitates~ It is collect~d using an aspirator and a BUchner suction filter and dried at 600 in vacuo. Yield: 33 g Qf the dyestuff in granula~e form~ -Ex~mple 32 200 g of Freon-113 TR (1,1,2-trichloro-1,2,2-trifluoroethane) ~ -and 20 g of the fluorescent brightener of the formula Cl ~ CH = CH ~ CH = Cll ~ Cl ,. - .j~
i, are put into a reaction vessel. After stirring for app. 5 minutes i (app. 700 rpm) at room temperature, app. 28 ml OL 1,3-dichloro-2-propanol are added dropwise at thie same stirring speed using drip funnel. The granulation is terminated about 30 minutes later. The fluorescent bri2htener granulate is isolated using ~n aspirator and a BUchner suction filte-r and dried in vacuo ~` at 50.
~ . .
~ Yield: app. 20 g of the above fluorescent brightener in 'J granulate form.
.. . . . .

~- Example 33 10 g of a powdery condensation product of formaldehyde and urea are put into a reaction vessel in 60 g of ethyl methyl ketone. After stirrin~ for app. 5 minutes (app. 700 rpm) at room tenlperature, 40 ml of water are slowly added dropwise to i~, : .
~ the viscous suspe~sion at thie same rate o~ stirring usinj~ a drip ,,~ 39 ,.. .. . .

- . ~ . . . . . . ..

10~60Z9 funnel. Granulcs are o~tained which are filtered off aftez brief stirring in vacuo and dried at 50 in a vacuum drier.
~ield: 10 g of the condcnsation product in granu]ate form.

Example 34 , With stirring (app. ~00 rpm), 115 g of an aqueous suspension of 5.7 g of the condensation product of Example 33 are run into 300 g of n-butanol at room temperature in the course of app.
10 minutes. Granules are formed during this operation. When the filtrate is clear, the granulation is terminated. The granules are filtered off in vacuo and dried at 50 in a vacuum drier.
Yield: 5~7 g of the condensation product in granulate for~.
A yield of 6.5 g of condensation product in grallulate form -is obtained by using 200 g of sec. butanol instead o~ the 300 g of n-butanol and 130 g instead of 115 g of the above aqueous suspension and otherwise carrying out the described procedure in analogous manner.

-Ex~mple 35 ~, , With stirring, 220 g of an aqueous fil~er sludge (18%
solids content) from a purification plant are added at room temperature ~o 500 ml of n-butanol. Granules form which, after brief stirring, are filtered off iD vacuo and dried at 50 in vacuo. Yield: 39.5 g or dry sludge granulate.

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' 10 660 29 Ex~mL~e 36 With stirring (app. 500 rpm), app. 300 g of n-butanol are ; rapidly run in.o 150 g of aqueous activated sludge. Granules form w~ich are filtered off in vacuo after stirring for 30 minutes and dric~ at 500 in a vacuum drier. Yield: 6 g of granulate.

Example 37 A suspension of 50 g of aqueous filter cake (44% solids content and 66% water), which contains as solid the dye of ~ormula L ~ C - N = N ~ N-CI~2CH20H]

and 80 g of ethanol is prepared at room temperature wi~h stirring.
This suspension is added slowly to lS0 g of Freon-113 TR at room temperature ~ith stirring (app. 500 rpm), whereupon dye~
stuff granules for~ after a time. The dyestuff granules are isolated using an aspirator and a BUc~ner suction filter and dried in vacuo. Yield: app. 20 g of dyestuff granulate.
3, An equally good granulate is obtained by using instead of Freon-113 TR and ethanol equal amounts oE acetone~Freon-113 TR
or diacetone alcohol/Freon-113 TR or a mixture of methyl acetate, ~ ethyl acetate, methanol and n-butanol or a mixture o~ methyl 4 ~ acetate and methanol, and otherwise carryi~g out the same procedure.

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0660;29 Exampl~ 38 33 g o aqueous filtcr cake ~3q% solids ~cntent, consisti.,~
of tlle dyestuff o~ Example 1 and salt, and 67~!o ~ater) are ~ery slowly made into a paste ~7ith 17 g of n-propanol. Granules gradually form in the liquid t~c-phase system and these deposi~.
They are filtered off and dried at 40 in vacuo to yield 10 g of dyestuff granulate.

, Example 3g With cooling, 18 g of isobutanol are added to 100 g of a ground suspension (particle size ~ 5 ~) consisting of 78 g of water and 22 g of the dyestuff of formula ~C ~ ~

After stirring for app. 15 minutes, the suspended particles have been completely converted into granules, The granùles are isolated and dried at 60. They are used for manufacturing organic printing inks for transfer printing on polyester.

, Example 40 ~ ith stirring, 0.8 g of dextrin (2% referred to solids) is dissolved in 220 g of an aqueous filter cake (18% solids content) from a purification plant, The sludge is added witll stirring at room temperature to 500 ml of n-butanol. After brief stir~in~

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,. t 10660Z9 granules arc obtained ~ ich arc filter~d o~ in vacuo and ~acuu.. dricd a~ 50~. Tl~cre ar2 obtaine~ about 40 ~ o a very hard and dry slud~e granulate.

Example 41 20 g of 1,3,4,6-tetraacety~glycoluril of forI~tla ' CH C0 OCCH
N ~N
0~ 0 ; :
are suspended in 320 g o~ Freorl-113 TR. To the suspension are slowly added w~th furtner stirring 12 ml of 1,3-dichloro-2-propanol. Small to medium large granules are ~ormed which are dried at 500. The dr~ed granules are hard and dust-free.

. 1 , . . .
Example 42 29 g of K2C03 are dissolved in lO0 g of an aqueous synthesi~
suspension of the dyestuff of formula r ~ C N N ~ ~C2H5 .'' . ~ ~ C2H4 _ C~3 _ (25% dyestuf~ content). ~ith stirring, 5 g of acetone a~e added thereto. After app. 10 minutes granules form from the liquid two-phase system. The compietely precipitated dyestuff granules are isolated using an aspirator and a BU hner suction filter ancl dried at 50 in vacuo. Yield: 25 g of the abo~e dyestuf;f in granulate forln.

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Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for the preparation of granules which comprises exposing the substance to be granulated to a liquid system consisting of a first liquid component which does not dissolve the substance and a small amount of a second liquid component which wets or dissolves the substance, and which second liquid is partially miscible with the first liquid component, and mixing the multiphase system so produced to form granules of the substance and subsequently separating the gra-nules from the liquid system.

2. A process as defined in claim 1 wherein the mixing is carried out turbulently.

3. A process as defined in claim 1 or 2 wherein the substance to be granulated is present in amount of 1 to 150%
relative to the first liquid component.

4. A process as defined in claim l wherein the substance to be granulated is present in an amount from 1 to 150%, relative to the first liquid component and the second liquid component is used in an amount from 1 to 60%, relative to the first liquid component.

5. A process as defined in claim 4 wherein the substance to be granulated is present in an amount from l to 150%, relative to the first liquid component and the second liquid component is used in an amount from 2.5 to 10% relative to the first liquid component.

6. A process as defined in claim 1 wherein the substance to be granulated is present in an amount from 1 to 150% relative to the first liquid component and the second liquid is used in an amount from 10 to 90% relative to the amount of substance to be granulated.

7. A process as defined in claim 6 wherein the substance to be granulated is present in an amount from 1 to 150% relative to the first liquid component and the second liquid is used in an amount from 15 to 50% relative to the amount of substance to be granulated.

8. A process as defined in claim 1 wherein the first liquid component is chosen from water, an organic liquid of mixture of organic liquids.

9. A process as defined in claim 1 wherein one liquid component is water and the other liquid component is an organic liquid or mixture of organic liquids.

10. A process as defined in claim 9 wherein the first liquid component is an organic liquid or mixture of organic liquids and the second liquid component is water.

11. A process as defined in claim 8 wherein the organic liquid or mixture of organic liquids is chosen from the group consisting of alcohols, halogenated aliphatic hydrocarbons and esters.

12. A process as defined in claim 11 wherein the organic liquid or mixture of liquids is chosen from the group consisting of 2-ethyl-1-hexanol, trichlorotrifluoroethane and ethyl-acetate.

13. A process as defined in claim 9 wherein the organic liquid or mixture of organic liquids is chosen from the group consisting of alcohols, halgenated aliphatic hydrocarbons and esters.

14. A process as defined in claim 13 wherein the organic liquid or mixture of liquids is chosen from the group consisting of 2-ethyl-1-hexanol, trichlorotrifluoroethane and ethyl-acetate

15. A process as defined in claim 10 wherein the organic liquid or mixture of liquids is chosen from the group consisting of alcohols, halogenated aliphatic hydrocarbons and esters.

16. A process as defined in claim 15 wherein the organic liquid or mixture of liquids is chosen from the group consisting of 2-ethyl-1-hexanol, trichlorotrifluoroethane and ethyl-acetate.

17. A process as defined in claim 10 wherein the second liquid component is water and the first liquid component is butanol or 2-ethyl-1-hexanol.

18. A process as defined in claim 8 wherein the first liquid component is 1,1,2-trichloro-1,2,2-trifluoroethane and the second liquid component 1,3-dichloro-2-plopanol.

19. A process as defined in claim 1, wherein the substance to be granulated is chosen from the group consisting of dyestuffs, optical brightners, textile auxiliaries, pharmaceutical products, pest-control agents, foodstuffs, antimicrobial agents, bacteriosta-tics, detergents, paper auxiliaries, photographic chemicals, leather chemicals, plastics and additives for plastics.

20. A process as defined in claim 4 or 6 wherein the sub-stance to be granulated is chosen from the group consisting of dye-stuffs, optical brightners, textile auxiliaries, pharmaceutical products, pest-control agents, foodstuffs, antimicrobial agents, bacteriostatics, detergents, paper auxiliaries, photographic chemi-cals, leather chemicals, plastics and additives for plastics.

21. A process as defined in claim 1, wherein the substance to be granulated is in the form of a pure substance or of commercial purity or a press cake.

22. A process as defined in claim 1 wherein the second liquid component includes auxiliaries chosen from the group consisting of bonding agents, wet-ting agents, diluting agents, effervescent agents, solubilising agents, acids, bases and dispersing agents.

23. A process as defined in claim 10 wherein the first liquid component is a ketone selected from ethyl methyl ketone, acetone and diacetone alcohol, and the second liquid component is water.

24. A process as defined in claim 1, 2 or 4, carried out at room tempera-ture.

25. A process as defined in claim 1, 4 or 9, wherein the second liquid is added gradually to the suspension of the solid in the first liquid.