NZ202535A - Granulation of particles of a magnesium salt of an organic peroxycarboxylic acid - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £02535 • - • -- ....-' . I •• • 202535 Priority Date(s): Complete Specification Filed: //?.'.{/.J?-' Class: &9.V. - A??J. .CP.?.Q .

Publication Date: .....! .1 $f.... P.O. Journal, No: .A?, ?.^F. m mmmu Patents Form No.5 NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION "GRANULATION" -*,WE INTEROX CHEMICALS LIMITED, a British company, of Hanover House, 14, Hanover Squars, London, W1R OBE England, hereby declare the invention, for which ~I~/we pray that a patent may be granted to me-/us, and the method by which it is to be performed, to be particularly described in and by the following statement (followed by page I A.) - „.l ■- ' '•'',./ • 202535 - Ifr- GC124 Granulation The present invention relates to a process for the granulation of peroxygen compounds and the granules obtained thereby, and in particular to such a process and granules in 5 which the peroxygen compounds is a magnesium salt of an organic peroxyacid carboxylate. v In European Patent Specification 27693 in the name,of Interox Chemicals Limited there are described and claimed certain magnesium salts which are useful inter alia as 10 bleaching agents and are:- In solid form, the magnesium salt of:' Class (l)-an aromatic carbocyclic compound substituted around the aromatic nucleus by a carboxylate group and a peroxycarboxylic acid group^both groups being 15 derivable from the corresponding aromatic carbocyclic anhydride by reaction with hydrogen peroxide, said aromatic carboxylic compound optionally being further substituted by at least one of the groups selected from alkyl, carboxylate, sulphonate, nitro, chloro and 20 bromo groups or Class (2)-a cycloaliphatic compound substituted around the cycloaliphatic nucleus by a carboxylate group and a peroxycarboxylic acid group^both groups being derivable from the corresponding cycloaliphatic 25 carbocyclic anhydride by reaction with hydrogen peroxide, said cycloaliphatic carboxylic compound optionally being further substituted by at least one 4 14 MAR 1986 7 202535 - 2 - GC124 of the groups selected from alkyl, carboxylate, sulphonate, nitro, chloro and bromo groups or Class (3)- an olefinically unsaturated aliphatic compound substituted by a carboxylate group and a 5 peroxycarboxylic acid group, the carbonyl group of the carboxylate substituent being conjugated with the carbonyl group of, the peroxycarboxylic acid via the olefinic unsaturation within the aliphatic compound,both substituents being derivable from the 10 corresponding anhydride by reaction with hydrogen peroxide..

The specification also describes the manufacture of such salts by reaction between an anhydride, aqueous hydrogen peroxide and a magnesium base in an inert organic 15 reaction medium such as ethyl acetate. In many instances, the solid product obtained directly in such a process has a lower average particle size than would be preferred for incorporation in detergent powder compositions.

In European Patent Specification A-66992 also in the name of Interox Chemicals Limited there is described an alternative method for manufacturing magnesium salts of classes (1) and (3) defined hereinabove in which the solid salt is precipitated from a substantially aqueous medium. In many instances the product is obtained with a 25 higher average particle size than from the inert organic reaction medium. Whilst this is advantageous from the viewpoint of its incorporation and non-segregation in detergent compositions, the measured rate of solubility of the salt was found to decline as the average size increased.

Investigations were made into ways of granulating or agglomerating small particles of the magnesium salts to produce granules within which term is included agglomerates. In view of the superior solubility of the magnesium salts in comparison with conventional solid peroxygen bleaches, e.g. sodium perborate tetrahydrate and sodium percarbonate at temperatures at or near ambient, it might be expected that agglomeration could readily be carried out using water r- 205535 GC124 alone, but agglomeration of the magnesium salts does not occur when using a fluidised bed granulator and when using a pan ball granulator the resultant product has an impaired solubility.

It will be recognised that many inorganic and organic compounds have been suggested in the past as granulating aids or coating agents-.for solid peroxygen compounds. There have b2«..n included amongst the classes of inorganic compounds, a solution of the peroxygen compound itself or its non-peroxygenated analogue and amongst the classes of organic compounds glycol polymers. . When compounds within. such classes, such as magnesium phthalate and polyethyleneglycol were tried as granulating aids in granulation of the magnesium salts herein using a fluidised bed the resultant product in general was little different from when water alone was used, i.e. little or no ^. granulation occurred. This was demonstrated by no more than a small amount of product of acceptable particle size being obtained, and even that product being unacceptably friable. A similarly poor result was obtained when dextrin or isinglass or a gum such as gum acacia were used. fcN T In addition, when a commonly used coating agent for inorganic persalts was used, namely sodium silicate solution, substantial decomposition of the magnesium persalts occurred. Other agents such as sodium or magnesium sulphate, described as coating agents for perphthalic acids in USP 3494787 amongst others have virtually no or little positive effect on the friability of the product. This demonstrates that it is not possible to transfer granulating technology directly from one group of peroxygen compounds to the magnesium salts described herein with any reasonable predictability. Consequently all the many published patent specifications are of background guidance to what has been tried 17 wrw®6' - -i n 202535 - 4 - GC124 for other percompounds and cannot act as a clean pointer to what should be used for the instant magnesium persalts. „ According to the present invention there is provided a process for granulating particles of one or more of the 5 magnesium salts of organic peroxyacid carboxylates described hereinbefore, comprising the steps of agitating the particles, thereby bringing them into contact with each* other from time to time whilst simultaneously spraying onto the agitated particles an aqueous solution of an hydroxylated 10 organic polymer as herein defined to provide at least 0.1% by weight-of polymer based on the dry product, and drying the product, an< maintaining the temperature of the particles throughout the process at not more than 65°C.

Herein, the invention will be described with u particular reference to the magnesium salt of monoperoxyphthalic acid which is ^an hydrated salt having empirical formula:- r a n.c ve -"C03H i it C02 - - & -J Mg2+.6H20 The other magnesium salts of classes (1), (2) and (3) can 25 likewise be emDloyed in the invention, mutatis mutandis.

Herein, there is meant by the term "hydroxylated organic polymer" a synthetic polymer obtained from an hydroxyl-substituted monomer or monomer in which the hydroxyl group is masked and is subsequently unmasked after 3Q polymerisation. One very acceptable class of such polymers comprises polyvinylalcohols (PVA) . The PVA polymer desirably has an average degree of polymerisation of at least 500, preferably at least 1,000 and in many preferred embodiments at least 1,500. Generally the PVA polymer has an average degree of 35 polymerisation of not more than 4,000 and often less than 3,000. In particularly preferred embodiments the average degree of polymerisation of the PVA polymer is from l,50$Kf -:'1- V r> 20253S \ > t - 5 - GC124 2,500. It will be recognised that a blend of two or more PVA polymers can be employed, for example one containing,a minor proportion of a lower molecular weight polymer such as 5 to 15% w/w of a polymer having a degree of polymerisation 5 of 500 to 1,000 and the balance of the polymer blend having a degree of polymerisation of 1,500 to 2,500, possibly containing also if desired a small proportion of PVA having an even higher degree of polymerisation. As an alternative to using a preformed blend, two or more polymer solutions can be added separately either simultaneously or sequentially, with preferably the lower molecular weight . polymer being added first. The PVA polymer used is typically one that has been hydrolysed to above 80%, and those hydrolysed to 87-90% have been employed most successfully. ' It has been found that the carboxylated derivatives of the PVA polymers can be used successfully also.

The polymer is usually employed in aqueous solution at a concentration so selected that the solution can be sprayed 2Q using the selected apparatus. Naturally, the maximum concentration usable is dependent upon the molecular^ weight of the polymer and the temperature of the solution. Typically, the concentration of polymer is selected in the range of 1 to 12% by weight. For a polymer having a degree 25 of polymerisation in the region of 2,000, a very effective concentration of polymer is thus in the region of 4 to 5% by weight. Conveniently, the solution can be employed at ambient temperature, but if desired the solution can be sprayed in at a temperature of up to 65°C.

The amount of agglomerating agent employed is normally selected within the range of 0.1 to 5% of polymer,often at least 0.2% and in many cases at least 0.5%,percentages of polymer used herein being by weight, based on the dried products. In practice, it is preferable to employ up to 35 about 2.5% of polymer, the amount often being selected in the range of 0.8 to 2.0% of polymer. It will be understood that as a general rule, the more agglomerating agent that.L;is • ■. - ■' T O *4MAR!986' n ) 202535 - 6 - GC124 added, the larger is the average particle size of the resultant dried product, but that to some extent, there is a tendency for existing agglomerates to grow rather than for new agglomerates to be formed. Naturally, the amount of 5 agglomerating agent is selected taking into account the average size of the feed particle and the desired size of the product. We have found that it is suitable to select the amount within the range of 0.3% to 2.0% and particularly 0.8% to 1.5% by weight of the dried product, where it 10 desired to produce an agglomerate of which a substantial proportion has a particle size in the range of 0.15 tol.Omm employing a feed containing at least 75% by weight of particles of less than 0.2mm diameter, the feed preferably containing at least 80% by weight of particles of less than 15 0.15mm diameter.

After the agglomerate has been dried, it is often . preferable to sieve it so as to isolate a fraction having a specified range of particle sizes, for example the aforementioned range or a narrower one of 0.2mm to 0.85mm. 20 Undersize particles (fines) can be recycled to the agglomerator. Oversize particles can be crushed or jnilled, preferably only to the extent of obtaining a substantial proportion of agglomerates within that specified range of particle sizes, any fines resulting, again being recycled. 25 Substantially all the feed material for the agglomeration process of the present invention has a particle size of below 0.5mm and in practice a large proportion of the particles is usually below 0.2mm, in many instances from 75 to 90% by weight or even higher. It is 30 most convenient to employ a feed having a weight measured geometric mean particle diameter of 75 to 100 microns. The particles can be obtained from the processes described in the aforementioned EP a-27693 and ep a-66992. Where otherwise they would be larger than preferred, they can be crushed or 35 milled. As desired, the feed can be either dry or wet, the actual operating conditions being adjusted to take into account the free water content of the particles. - •- .,,.;_/ 202535 - 7 - GC124 convenient to employ for example, damp solid obtained from the filter or centrifuge in the route described in EP A-66992, possibly after gentle crushing or alternatively or additionally to employ dried and where needed milled particles of the magnesium salt. It will be understood that a proportion of the feed particles can be particles of similar size of materials compatible with the aforementioned magnesium salts of classes (1), (2) and (3). Such materials could desirably be selected from the compounds described in said European Patent Specification 27693 as being a particularly important class of desensitising diluents and comprising the alkali metal or alkaline earth metal salts of halogen-free acids having a first dissociation constant of at least 1x10""-^ for example sodium or magnesium sulphate or 15 the various sodium phosphates. It will also be understood that the particles of magnesium salt, by virtue of their method of manufacture can often contain some additional substance, such as the magnesium salt of the corresponding non-peroxygenated acid, which in the case of magnesium monoperoxyphthalate is magnesium phthalate, and/or possibly various crystal modifiers. • In one important aspect of the present invention a particular feature is the use of an inert gas for agitating the particles and especially using the gas to fluidise a bed 25 of the particles. By so doing, it is possible to obtain ' agglomerates of magnesium salt particles that have an apparent free flowing bulk density somewhat lower than when employing, for example rotating pan or drum granulators.

This can be of especial benefit where the agglomerates are intended for incorporation in powder detergent compositions in that such a bulk density can more closely match that of spray-dried products which generally form a substantial proportion of such compositions and thereby minimise bleach/detergent segregation within the composition during 25 handling. Consequently, according to one aspect of the invention there is provided an agglomerate of one or more magnesium salts described hereinbefore, and especially 2&25Z magnesium monoperoxyphthalate having a particle size in the range of 0.2 to 1.0mm, a weight averaged particle size in * the range of 0.4 to 0.65mm and an apparent free flowing bulk density within the range of 0.3 to 0.6kg/l, particularly when obtained by the agglomeration of feed particles of the magnesium salt of which at least 75% by weight are below 0.2mm and preferably at least 80% by weight are below 0.2mm. Such agglomerates can be produced in particular by the use of a fluidised bed granulator in conjunction with the hydroxyl substituted organic polymer especially PVA and < carboxylated PVA described herein.

The inert gas employed to agitate the particles is most conveniently air, but it can be nitrogen or any other gas that does not react with the magnesium salt or the agglomerating agent under the conditions of contact. In practice, of course, the influent inert gas is unsaturated v.. with respect to water vapour, an effect which occurs naturally when the gas is heated and/or dried before being used to agitate the particles.

In a fluidised bed process, the bed of magnesium salt particles is fluidised throughout by an updraft of the inert gas, typically air, and the gas flow is adjusted in accordance with the particles' sizes and weights as in conventional practice to maintain the particles in suspension in the fluidising chamber, and where possible not to carry out therefrom more than a very minor proportion of the particles, which can be subsequently separated off often using e.g. blowback filters, such control and operation of a fluidised bed being well known and needing no further clarification herein.

In batch operation, granulation in the fluidised bed comprises the stages of charging a fluidising chamber with a bed of feed particles of magnesium salt, and bringing the bed of particles to a desired temperature, spraying agglomerating agent in aqueous solution into or preferably onto the bed, drying the bed and generally cooling the bed before discharging the granulates. It will be recognised I—t n 20253 5 - 9 - GC124 that the various stages can be effected in the same or different chambers and that alternatively, the process can be carried out continuously using a segmented chamber or plurality of chambers in which, for example, the feed 5 particles and/or agglomerates, as the case may be, pass from one segment or chamber to the next by, for example, overflow over a weir. v.

Preferably, the inert gas is employed at an inlet temperature of from 40 to 80°C especially at least 50°C, and 10 most preferably from 60 to 65°C during the stages prior to cooling. During the cooling stage, the gas temperature at the inlet can be lowered progressively or immediately to within the range of below 30°C, typically from 5 to 25°C and most conveniently ambient.

The bed of particles is preferably brought to a temperature in the range of 35 tov 50°C, often from 40 to 45°C prior to being sprayed. During the spraying stage,..the bed is maintained at a temperature of at least 25°C and usually not above 50°C by heat supplied by the fluidising 20 gas and optionally by heating elements disposed within or around the fluidising chamber having contact surfaces-preferably not above 65°C. As is well known in the art the rate of introduction of the aqueous solution of agglomerating agent into the fluidised bed is controlled in 25 conjunction with the flow of the fluidising gas and other bed parameters so as to maintain the bed in a fluidised condition and thus avoid the condition known as "wetting out". Such control is within the competence of the skilled man,and takes into account external conditions such as the 30 temperature and humidity of the ambient air. In practice we find it convenient on many occasions to introduce the agglomerating agent solution gradually over a limited period of at least 20 minutes and often within the range of 20 to 30 minutes, and to maintain a temperature in the region of 35 about 30°C, typically 28 to 33°C. Alternatively, the solution can be introduced in small increments rather than continuously. The solution is introduced in the form of a i - 10 - GC124 spray and as is known, some variation in the particle size of the granulate can be obtained by variation in the size of the spray droplets. We have found it particularly convenient to spray from a jet having orifices of diameter selected within the range 1.2mm to 2.4mm and an atomising air pressure selected in the range of 1 to 4 bar, especially at about 1.8mm at an atomising air pressure of 1.8 bar, or other equivalent orifices/atomising pressures combinations, depending inter alia upon the scale of operation.

The agglomerates are very preferably dried in the fluidised bed so as to avoid the formation of cakes which-, might otherwise occur if they were discharged wet from the bed. The drying is preferably carried out until the effluent gas has attained a steady temperature, the precise value of which "will depend, naturally, upon the influent gas temperature and the apparatus itself. When influent gas at v. 60-65°C is employed, an effluent gas temperature from the filters usually blow-back filter of up to about 55-60°C is typical. The drying time is generally within the range of 5 to 20 minutes when carried out in the bed. The subsequent cooling with cool gas often lasts a further 5 to 10 minutes, and thus in total the granulation process normally takes from 40 to 80 minutes, often 45 to 60 minutes from the start of introduction of the agglomerating agent.

By the use of the fluidising bed granulation process, and where desired appropriate sieving afterwards especially to remove residual fines, a granular product can be obtained that meets the criteria for particle size and bulk density described hereinbefore. Advantageously, the product of such a process is free flowing and its resistance to attrition can be judged from the fact that it has survived the abrasive conditions prevalent in a fluidised bed, but further improvement can be obtained by including a grinder within the bed, if desired. Furthermore, the product tends to cause in general, less dye damage when washing than does a product of comparable particle size but higher density obtained using a pan ball granulator. Finally, it has been / 2 0Z538 GC124 found that by carrying out the fluidised bed granulation quickly in the manner, described herein the resultant product loses no more than a small proportion of its available oxygen (avox), in many cases being less than 5% loss leaving often a product containing at least 6% avox which is similar to that in the feed particles.

The product of the present invention can be readily incorporated in bleaching and detergent compositions.

Having described the invention in general terms, specific embodiments thereof will now be described by way of example and without limitation. Modifications thereof in accordance with the foregoing disclosure or with the background skill and knowledge of the artisan can be made without departing from the spirit of the invention.

In the Examples, the feed particles were obtained by milling through a cross beater mill fitted with a 2mm screen, a dried sample of magnesium monoperoxy phthalate produced substantially in accordance with a scaled-up version of Example 17 of EP A-66992. On analysis, about 90% of the feed particles by weight had a diameter of below 212 microns after milling.

In each batch, a small pilot scale fluidised bed chamber was charged with approximately 15kg of the feed particles at ambient temperature and then the bed was fluidised with an updraft of hot air, having an inlet temperature maintained within the range of 60-65°C. The bed temperature was monitored, and when it had reached 40°C, introduction commenced of an aqueous solution of polyvinyl alcohol having an average molecular weight of about 2400 to 2500 (ambient temperature of about 20°C, 4% concentration by weight) through a jet having nominal apertures of 1.8mm under a pressure of 1.8 bar. 2000mls of solution were sprayed in during the next 20 to 30 minutes. The bed temperature fell slightly during the spraying by virtue mainly of evaporation but was maintained at near 30°C throughout. Fluidisation with the warm air continued for about 15 minutes or so after introduction of f .N _ 202535 GC124 polyvinylalcohol solution ceased, by which time the bed temperature had risen, to 55 to 57°C and the air at the », outlet had attained a steady temperature of about 40°C, indicating that the bed was substantially dry. The bed was 5 then fluidised for a few minutes with ambient air and when the granules h \C cooled to 35 to 40°C, the product was discharged and then roughly sieved. Typically, the yield of product in the nominal range of + 212 microns to -710 microns was about 7.5kg, that of -212 microns was about 10 4.5kg and that of + 710 microns was about 3kg. The oversize material was milled in the aforementioned mill to yield a-further 40% of product in the range +212 to -710 microns and the undersize material was recycled.

The product in the preferred range had a free-flowing 15 apparent bulk density, measured substantially in accordance with the method and apparatus described in British Patent Specification 1600106, and when it was substantially free. from retained undersize particles which was in the range of 0.35 to 0.41 kg/1. The solubility of the product was 20 measured by stirring 0.25g solid at 50 rpm in 25ml water at 20°C in a centrifuge tube for 15 seconds, centrifuging the tube for 30 seconds, and finally decanting off the supernatant liquid and measuring its available oxygen (avox) content. By comparing the dissolved avox with the known 25 avox of the solid product, the solubility of active oxygen can then be calculated. Typically, the invention product in the preferred particle size range had a solubility in the range 70 to 90% by weight, whereas when the same test was carried out on pan ball granulated material, the solubility 30 was only just over 50% by weight, which is considerably worse . That same pan ball granulated product also tended to have a higher apparent bulk density, generally from 0.6 to 0.7 kg/1 J . Substantially the same results were obtained when the Example was repeated using the same fluid bed apparatus and conditions except that the magnesium monoperoxyphthalate feed particles had a weight geometric mean of about 90 I 13 ~ 202*5 35 microns and various other sources of polyvinyl alcohol having average degrees of polymerisation varying from 17D0 to 2400, degrees of hydrolysis about 88% were used, as before in aqueous solution, providing a 1% w/w loading of 5 polymer on the dry product. Such products not only had acceptable rates of solubility but also an acceptable resistance to attrition.

In a modification, the Example was repeated using a futher sample of the latter batch of magnesium salt feed 10 particles, and as binding agent an aqueous solution of a carboxylated derivative of PVA. At a loading of 2% on the dry product, there was a tendency for oversize product to form, but it had excellent resistance to attrition and good solubility. This indicates that the carboxylated derivative 15 of PVA is substantially as effective a binder for the present purpose as PVA itself.

By way of comparison, the Example was also repeated, using the same apparatus and conditions and latter feed particles, but using other binding agents in aqueous 20 solution. Gum acacia, isinglass, magnesium phthalate, sodium sulphate, methyl cellulose, and dextrin all could granulate only a small fraction of the feed particles, and even those granules were easily attrited. . 14 - 202535

Claims (19)

WHAT WE CLAIM IS:

1. A process for granulating particles of one or more of the magnesium salts of an organic peroxyacid carboxylate described hereinbefore, comprising the steps of agitating the particles, thereby bringing them into contact with each other from time to time whilst simultaneously spraying onto the agitated particles an aqueous solution of an hydroxylated organic polymer as herein defined to provide at least 0.1% by weight of polymer based on the dry product, and drying the product, and maintaining the temperature of the particles throughout the process at not more than 65°C.

2. A process according to claim 1 in which the polymer is a polyvinylalcohol or a carboxylated derivative thereof.

3. A process according to claim 2 in which the polyvinylalcohol has an average degree of polymerisation of from .1000 to 3000.

4. A process according to claim 3 in which the polyvinylalcohol has an average degree of polymerisation of from 1500 to 2500.

5. A process according to any one of the preceding claims in which the polymer is employed at a concentration in the aqueous solution selected in the range of from 1 to 12% by weight.

6. A process according to any one of the preceding claims in which the amount of polymer employed is selected in the range of from 0.5 to 2.5% by weight based upon the dried anular product. - 15 - 202535

7. A process according to any one of the preceding claims in which the amount of polymer employed is selected in the range of from 0.8 to 2.0% by weight based upon the dried granular product.

8. A process according to any one of the preceding claims in which at least 75% of feed particles are less than 0.2mm diameter.

9. A process according to any one of the preceding claims in which the particles are agitated and fluidised by an inert fluidising gas, the bed being maintained at a temperature of at least 25°C during the introduction of the aqueous solution of polymer.

10. A process according to claim 9 in which the bed is maintained at a temperature of 28-33°C during the introduction of the aqueous solution of polymer.

11. A process according to claim 10 in which the fluidising gas has an inlet temperature of from 50 to 60°C.

12. A process according to any one of claims 9, 10 or 11 in which the agglomerates formed are subsequently dried in a fluidised bed until the effluent fluidising gas has attained a substantially constant temperature.

13. A process according to claim 12 in which the dried agglomerates are subsequently cooled to below 40°C by fluidisation with cool fluidising gas before discharge from the bed.

4. A process according to any one of the preceding claims n which the fraction of the product having a particle size of - 16 - 202 535 from 0.15 to l.Oiran is subsequently isolated.

15. A process according to any one of the preceding claims in which the feed particles have a geometric mean diameter of 75 to 100 microns.

16. A process according to any one of the preceding claims in which the magnesium salt is magnesium monoperoxyphthalate.

17. A process for the granulation of particles of magnesium salts substantially as described herein with respect to any run of the Example.

18. A granular magnesium salt of a compound'in .classes' (1) , (2) and (3) described herein whenever obtained by a process according to any preceding claim.

19. A granular magnesium salt of a canpound in classes. (1), (2) and 3 described herein having a particle size of from 0.15 to 1.0mm and a free-flowing bulk density of from 0.3 to 0.6 kg/1. X CHEMICALS LIMITED torneys N & CAREY