DE2136978B2 - METHOD TO PREVENT CACKAGING OF HARDENED OIL COATED PARTICLES - Google Patents

Description

not only inconvenient, but sometimes left for certain, where heat is supplied from outside

Uses completely unsuitable. In particular, becomes, the unstable crystal structure becomes stable

if the core material as a food additive transfers crystal structure, and furthermore the small ones

is to serve, it is necessary that these particles become crystals, which are present in a relatively loose arrangement,

be uniformly mixed into the food material. 5 are properly and compactly attached, so

A food additive in which the particles are stabilized in a very strong way; The on this

present caked state, fulfills its way stabilized crystal structure does not suffer

Purpose not and rather leads to deterioration changes more at temperatures below the

the quality of the food, as it corresponds to the food softening point,

product is not incorporated homogeneously. io With regard to the prevention of

To prevent this caking, baking hardened oil coated particles

an excessive deterioration in the commercial value has hitherto remained the crystal structure of the hardened oil

of the product, an additive was disregarded, and investigations

On the order of 0.3 to 5 percent by weight, with a view to preventing caking

drew completely the crystal structure of the hardened oil onto the hardened oil-coated part

a finely divided inorganic substance, and rather these sub-

such as silicic acid, magnesium aluminum silicate, magnesia exclusively for classes and quantities

sium carbonate or tertiary calcium phosphate or the inhibitors to be used for the

Alkaline earth salts are limited by higher fatty acids, such as calcium baking. As an explanation of the cause

stearate or magnesium stearate. Despite w> of caking was only assumed

the addition of these inhibitors to the composition that some of the hardened oil at a temperature

bake, however, has often been found to melt near the softening point, so that

Product in shipment from the manufacturing plant until interparticle melting occurs and

caked to the consumer. this results in a caked state.

The object of the invention is therefore the ^T creation as However, it has now surprisingly found a method for preventing the cooperation that the caking of the jaw of Hardened Oil coated with hardened oil particles, coated particles not only by the temperature at which the disadvantages , which is also influenced when the particles are left to stand using auxiliary substances, are switched off, but that the temporal temperature treatment. The caking process of the coated particles also has a major influence on this caking phenomenon of caking with hardened material.

Oil-coated particles by adding a caking-preventing substance in amounts and caking is explained on the basis of the drawing from 0.3 to 5 percent by weight, this being explained for the coating, using hardened cattle as an example oil with a melting point of 45 sebum is used. In the drawing is
having up to 85 ⁰ C, and the caking 1 comparable Fig. Ergebhindernde a graphical representation of substances, in particular silica, ma- Nissen the differential thermal analysis of gegnesiumaluminiumsilikat, magnesium carbonate, ter- härtetem beef tallow and

calcium phosphate, calcium stearate, and magne- 40 F i g. Figure 2 is a graph of the results

sium stearate are used, is characterized by an infrared absorption analysis of hardened Riri-

draws that the tallow coated with hardened oil.

Particles before the addition of the caking If a thermal differential analysis with preventive substance for at least 20 hours hardened beef tallow (melting point 59 to 6I ⁰ C) after the same at a temperature between about 25 "C and 45 heat melting of the same and then below the softening point of the used Oil cooling and solidification carried out will be left to stand. Three classes of curves are obtained which are shown in FIG.

The invention is based on the knowledge that shows which of which are used for cooling treatment the described caking are dependent on the hardened process used. The crystal oil coated particles based on change in the crystal forms of the hardened oil belonging to these three classes structure of the hardening material used as coating material result from different thermal curves, owed oil is due. are referred to as forms A, B, and C. the

The changes in the crystal structure of a hardened crystal form A is the crystal form obtained when The heat-melted hardened oil is rapidly cooled, depending on its thermal properties mix treatment. That is, the solidified mass 55 and is solidified in cold water and the, though the hardened oil consists of a majority of them stable at low temperatures, gradually becoming crystals, d. H. a congregation of small borrowed transforms into the crystal form B when the Tem crystals, and as a result there are changes in temperature rising and eventually in the crystal form C the crystal structure is transferred as a result of the thermal handling. The crystal form B is the mode of crystallization of these little crystals instead. The either «o form that is obtained when the hydrogenated oil is under cooled and solidified by cooling and solidification or precipitation in relatively mild conditions a hardened oil solvent which becomes, d. i.e., if left at room temperature is in the molten state as a result of heating. Under these conditions, the crystal will precipitate Solidified hardened oil is obtained in a form B without the step of the crystal structure before, in which a plurality of small 65 form A is traversed. The crystal form B is Crystals in unstable form together in relatively unstable and changes like crystal form A are united in a loose arrangement. Therefore, when these crystals gradually change to the crystal form C. The Krirvvduring standing for longer periods of time - stable form C is the crystal form that is obtained

5 6

when the crystal forms A and B either 15 days the same during the period where the Umwandoder be at 25 ⁰ C or 3 days, or allowed to stand in long development of the crystals of Form A and Form B in 30 ⁰ C is longer. This crystal form C the stable form C takes place, unite or where is extremely stable and shows no further changes a change of the loose arrangement of the small more at temperatures below the softening 5 crystals in a proper arrangement place point. Furthermore takes place at the same time with this environment.

Conversion a change in the attachment of the small To carry out the stabilization of the crystal crystals from a loose arrangement to an order structure of the hardened oil according to the invention, proper arrangement instead. This not only stabilizes the crystal form, ie the transition from form A to form B, but also increases the io to crystal form C and the change in the loose stability of the overall structure. According to the arrangement of the small crystals in an order graphic representation in FIG. 1 is the maximum corresponding arrangement, the hardened oil peak temperature of the crystal form A 68 ⁰ C, the coated particles at a temperature above the crystal form ^{B 64 ° C and that of the crystal 25 0} C and preferably above 30 ⁰ C form C 70 ' C so that the crystal form C left the highest 15. At temperatures below 25 ⁰ C ent-value has, while the crystal form B the nied- neither has the conversion speed extremely langrigstsn value. That is, in the case of coarse or no conversion takes place. Beitetem beef tallow, the transformation first game instance is a change in the full on the crystal form A to crystal form B with stable shape of the crystal in 15 days at 25 ⁰ C, a lower maximum peak temperature and 20 3 days at 30 ° C, 24 hours at 40 ⁰ C and 20 hours to the crystal form C, which is most stable, the one at 45 ⁰ C instead. It will thus take the time period. This type of conversion is a phenomenon during which the particles to complete, which generally have to be left standing in the case of higher fatty acids and their stability, are shown to be shorter, higher alcohols. In FIG. 2 when the temperature gets higher. With the hardened, curve I shows the infrared analysis values of the crystalline oil-coated particles, which in this way stabilized form C, and curve II shows those that were siert, are passed through a sieve and crystalline form A. The form of curve I is Compli-. lose the slight caking, which is more adorned than that of curve II, and which took place during the transformation. The difference is clear. Particles, which in this way are independent of one another

In general, those from one solvent are different, then will precipitate with 0.3 to 5 weight hardened oils of crystal form C, percent, preferably 0.5 to 3 percent by weight, however, in this case the crystal form C is still based on the particles, an inhibitor against unstable. Furthermore, the crystal structure is not yet caked, which makes the invention properly constructed, but is proper product of improved flowability in a loose arrangement. When this hardened oil 35 is obtained, which is at temperatures lower than that left to stand above a certain temperature, the softening point of the hardened oil does not collapse, If the crystals change to crystal form C, baked and consequently a high level of trade Has stability and whose crystal structure has a value. All of the above can be used shows proper arrangement. Caking inhibitors used

The curve III of FIG. 2 shows the results of a * o as long as it is the function of the core material

Infrared analysis of hardened beef suet, which by not affecting or inhibiting, and usually

Evaporation of chloroform from a chloroform, silica, magnesium aluminum silicate, ma

solution was ^{crystallized out at 20 0} C, with magnesium carbonate, tertiary calcium phosphate, CaI-

clearly the difference in appearance compared to the cium stearate or magnesium stearate favorably

Curves I and II shows. When using this hardened oil- 45.

crystals are above a certain temperature- The procedure for carrying out the stabilization is left Finding a change to stable treatment is easy. For example, you need Instead of crystals, which correspond to those of curve I - the coated particles immediately after their appearance, position only in a room with one temperature

The speed at which the crystal 50 changes higher than 25 ⁰ C, but lower than the softening structure from form A or B to form C, allow the hardened oil to stand until the temperature at which the crystals transform Crystal structure to form C finished, influenced, which is Ge. This is achieved with particles that become thin at a rate higher as the temperature of a vessel, for example a pan, becomes higher in the way. At low temperatures, where the transformations are spread, only one development does not advance on the particles, generally the minimum stress is exerted. The reason for the speed becomes very slow when the temperature falls below 15 ° C, the avoidance of exerting a greater temperature, there is a concomitant burden on the particles that the occurrence of baking with a hardened oil of crystals as much as possible occurs caking of the Form A or Form B coated particles is not fio avoided during the conversion step. Because instead, even if the particles are impossible for a long time, caking is allowed to stand during the period. To prevent conversion is a must at this stage

The caking of the hardened oil pressure caused by the contact coated particles, which takes place when the area between the particles is increased so that the crystal structure transforms from shape A or B to shape C 65 possibility of caking at this stage, can be avoided , can be explained as an appearance, reducing to a minimum,
The operation to incorporate the inhibiting the crystals of the other particles on the surface of the substance against caking is also possible

simple. A procedure whereby the prescribed amount of the caking inhibitor mixed with the coated particles using a common mixer is sufficient. The minor caking that occurred during the stabilization treatment goes completely lost during this mixing, while at the same time the caking inhibitor is uniformly mixed with the coated particles. This creates coated particles obtained with flowability in which no caking takes place.

The following examples serve to further illustrate the invention without limiting it. the Percentages in the examples are based on weight.

example 1

4 kg of hardened beef tallow was melted in the heat and kept at a temperature of 70 ° C. 1 kg of powdered sorbic acid was added to the molten hardened beef tallow, and the mixture was mixed with thorough stirring using a homomixer to obtain a homogeneous dispersion. This dispersion was sprayed in air at 20 ^° C., and upon cooling and solidification, sorbic acid particles coated with hardened oil, which were suitable as food preservatives, were obtained. The following test was carried out on the obtained coated particles.
Each class of the anti-caking inhibitors shown in Tables II to IV were added separately to the coated particles, and the coated particles were allowed to stand under the various conditions shown in Tables 1-1 to IV. On that were

ίο the coated particles in a cylindrical tube of 40 mm diameter and 60 mm height are packed and the particles are subjected to pressure by a A weight of 500 g was placed on the packed particles. The particles were left in this state for 7 days at the test temperatures given in Tables 1-1 to 1-V ditched. Then the coated particles contained in the pipe became therefrom removed, taking care that this does not affect the caked state of the particles was disturbed, whereupon the removed particles sieved with a sieve of 1.65 mm clear mesh became. The amount of coated particles remaining on the screen relative to the total amount was then calculated and given as a percentage.

This value, which is called the degree of caking (%) is given in Tables 1-1 through I-V. The larger this value, the larger the caking of the particles. Tn Tables I-T to T-V the crystal forms of the hardened beef tallow are also given before and after the experiment.

Table M.

Conditions of standing
of the particles Type and amount of
added inhibitor Attempt
temperature Caking.
extent Krista
Before the U-shape
After this against caking ( ⁰ C) (7o) attempt attempt Investigate immediately __ 10 15 to 20 A. A. after manufacture as well - 30th 90 to 95 A. C. as well tertiary calcium phosphate 10 below 1 A. A. phat, 3 »/ ₀ as well as well 30th 80 to 90 A. C. as well Silica, 3 per cent 30th 70 to 80 A. C. as well Magnesium aluminum 30th 70 to 80 A. C. silicate, 3%

Table I-II

Conditions of standing
of the particles Type and amount of
added inhibitor Attempt
temperature Aggregation
extent Krista
Before the llform
After this against caking CQ (7o) attempt attempt After 3 days of standing _ 10 10 to 20 B. B. at 25 ⁰ C after the Manufacturing as well - 30th 90 to 95 B. C. as well tertiary calcium phosphate 30th 80 to 90 B. C. phat, 3 ° / ₀ as well Silica, 3% 30th 70 to 80 B. C. as well Magnesium aluminum 30th 70 to 80 B. C. silicate, 3%

309 526/491

Table I-III

10

Conditions of standing
of the particles as well Type and amount of
added inhibitor Attempt
temperature Caking
extent Kris ta
Before the U-shape
After this »JV ^ Λ VIlVlIvI R as well against caking CC) (%) attempt attempt After standing 10 15 to 20 C. C. for 15 days as well 25 ° C after the Her as well position as well - 30th 15 to 20 C. C. tertiary calcium 10 below 1 C. C. phosphate, 2% as well 30th as well C. C. Silica, 1% / ₀ 30th as well C. C. Magnesium aluminum 30th as well C. C. silicate, 1% / ₀

Table I-JV

Conditions of standing
of the particles Type and amount of
added inhibitor Attempt
temperature Caking
extent Krista
Before the llform
After this against caking CO (° / o) attempt attempt When standing for 3 days tertiary calcium 30th 5 to 10 C. C. decrease at 30 ^° C phosphate, 0.5% / ₀ the production as well Silica, 0.5 ° / ₀ 30th 1 to 5 C. C. as well Magnesium aluminum 30th 1 to 5 C. C. silicate, 0.5% as well tertiary calcium 30th below 1 C. C. phosphate, 2% / ₀

Table I-V

Conditions of standing
of the particles Type and amount of
added inhibitor Attempt
temperature Caking
extent Krista
Before the llform
After this against caking CC) (7o) attempt attempt After 20 hours 10 15 to 20 C. C. Leave to stand at 45 ^° C as well - 35 15 to 20 C. C. as well tertiary calcium 35 below 1 C. C. phosphate, 2% / ₀ as well Silica, 2 ° / ₀ 35 as well C. C. as well Magnesium aluminum 35 as well C. C. silicate, 2 ⁰ I ₀

Example 2

Hydrogenated castor oil 3 kg (melting point 80 to 85 ⁰ C) were heat-melted. After adding 4 g of soy lecithin as a surface-active agent, 1 kg of finely divided fumaric acid was added, whereupon the equipment was agitated thoroughly and the dispersion was obtained. This dispersion was kept at 90 ^° C. and sprayed into air at 30 ^° C., whereupon it cooled and solidified. Fumaric acid particles coated with hardened castor oil were prepared.

The coated particles obtained were separated with the various ones shown in Table II Caking inhibitors decomposed and caking attempt in the same way as carried out in Example 1 under the various conditions given in Table II. The results are included in Table II.

The fumaric acid particles coated with hardened castor oil were added to a basic food material and thereby the elution of fumaric acid prevented at room temperature, but caused the acid to elute during the heating step, whereby

this was used for the purpose of lowering the pH of the food product. There how Table II shows the degree of caking

the coated particles of the present invention is low, they are particularly suitable for this purpose.

Table II

Conditions of standing
of the particles Type and amount of
added inhibitor
against caking Experimental
temperature
( ⁰ C) Together
degree of baking
(V.) Try immediately _ 10 55 to 10 after manufacture as well - 35 80 to 85 as well Magnesium aluminum 35 70 to 80 silicate, 2% / ₀ as well tertiary calcium 35 as well phosphate, 2% / ₀ as well Silica, 2% 35 as well After standing for 2 days 10 5 to 10 tempered at 45 ⁰ C after the production as well - 35 5 to 10 as well Magnesium aluminum 35 below 1 silicate, 2% / ₀ as well tertiary calcium 35 as well phosphate, 2% / ₀ as well Silica, 2 ° / ₀ 35 as well

Example 3
A glutamic acid powder with a fineness

Speaking about 0.370 mm sieve was placed in a coating pan, and with shaking a 30 _^0/0 solution of hardened beef tallow was sprayed (melting point 59 to 61 ⁰ C) in chloroform. Shaking of the powder particles was continued for a while, and after uniform wetting of the surface of the glutamic acid particles was achieved, the chloroform was evaporated off with hot air. The above operation

was repeated until the content of hardened beef tallow in the particles became 40%. This were Obtained coated glutamic acid, which can be used as a seasoning agent and as a pH lowering agent for Food products could be used.

The obtained coated glutamic acid particles became under the conditions shown in Table III left to stand, whereupon the various caking inhibitors added and the caking attempt was carried out. The results are shown in Table III keep.

Table III

Conditions of standing
of the particles Type and amount of
added inhibitor Attempt
temperature Together
degree of baking against caking ( ⁰ C) (%) Investigate immediately . - 10 10 to 15 after manufacture Calcium stearate, 3% / ₀ as well - Magnesium stearate, 3% / ₀ 35 60 to 70 as well Calcium stearate, 3% Magnesium carbonate, 35 40 to 50 as well Magnesium stearate, 3% 3 ° / o 35 as well as well Magnesium carbonate, 35 as well 3% After standing for 3 days 10 10 to 15 leave at 37 ° C as well 35 10 to 15 as well 35 below 1 as well 35 as well as well 35 as well

From the values in the tables above, it can be seen that the caking of the hardened oil-coated particles are pronounced at the point where changes in the crystal structure occur so that if the crystal structure of the hardened oil has not been stabilized, the inhibitor against the Caking, with which the coated particles are mixed, is practically ineffective and none Shows effectiveness. On the other hand, it can be seen that, if according to the invention, the caking inhibitor in coated with hardened oil

Particles after the crystalline structure of the hardened oil has been stabilized by allowing the coated one to stand Particles at temperatures higher than 25 ° C but lower than the softening point of the

hydrogenated oil, the effectiveness of the anti-caking inhibitor fully shows and stable hardened oil coated particles are obtained, the fluidity own and not at normal temperatures

ίο caking, to be preserved.

1 sheet of drawings

Claims (6)

Claim: A method of preventing caking of hardened oil coated particles by adding an anti-caking substance in amounts of 0.3 to 5% by weight, the oil used for coating having a melting point of 45 to 85 ° C and as an anti-caking Substances in particular silica, magnesium aluminum silicate, magnesium carbonate, tertiary calcium phosphate, calcium stearate and magnesium stearate are used, characterized in that the particles coated with hardened oil for at least 20 hours at a temperature between above 25 ° C and below the addition of the caking-preventing substance Softening point of the oil used can be left to stand. 3o The invention relates to a method for preventing caking of hardened oil coated particles by adding a caking preventing substance in amounts of 0.3 to 5 percent by weight, the oil used for coating having a melting point of 45 to 85 ° C and as that Caking-preventing substances in particular silica, magnesium aluminum silicate, magnesium carbonate, tertiary calcium phosphate, calcium stearate and magnesium stearate are used. Hardened oils have heretofore been used for such purposes as preventing moisture absorption, maintaining the effectiveness or preventing a reaction of drugs and chemicals in drugs for humans and animals, for agricultural chemicals, food additives and the like, using them as a surface coating for such drugs and chemicals served as core materials. In particular, when the core material consists of a food additive, application of a hardened oil coating has often been carried out with excellent results; H. Preventing the additive from eluting at room temperature, but preventing it from eluting during the step of heating the food product, thereby preventing decomposition of the core material in the food material and any deleterious effect of the core material on the food material. βο Hardened oils for use for the purpose indicated above are those with a melting point in the range of 45 to 85 ° C. In the case of a hardened oil whose melting point is below the above range, there is the possibility 6g of softening at high temperatures, such as. B. occur in summer. Particularly favorable hardened oils are, for example, hardened beef tallow (melting point 59 to 61 ° C), hardened whale oil (55 to 600C), hardened rapeseed oil (melting point 59 to 620C), hardened soybean oil (melting point 60 to 69 ° C), hardened cottonseed oil (melting point 55 to 610C) and hydrogenated castor oil (melting point 82 to 85 ° C). Numerous methods are known for coating particles such as human and animal medicaments, agricultural chemicals, and food additives with xo hardened oils, including but not limited to: 1. The spray method in which the hardened oil is melted in the heat, the particles are dispersed therein and then this dispersion into a gas Rait a temperature below that of the melting point of the hardened oil, such as air, nitrogen or carbon dioxide _ao is sprayed, so that the particles are coated, and cooled simultaneously coated particles and solidified. 2. The pan coating method in which the coating of the particles is carried out by ^a 5 an operation is repeated in which the particles are placed in a coating pan, the hardened oil dissolved in a solvent is sprayed onto the particles while shaking the pan and then the solvent is evaporated from the coated particles by blowing off, for example with hot air, and removed will. 3. The coating method by suspension in air, with the particles in a stream of air float and remove the particles by spraying a solution of a hardened oil against the Material to be coated. 4. The vacuum evaporation process, in which the hardened oil is heated in a vacuum and applied to the Particle is evaporated, so that a separation of the hardened oil from the oil vapor is effected on the surface of the particles. 5. The electrostatic coating process, whereby the particles of the core material and the Particles of the hardened oil solution opposing electrical charges are applied, so that these particles are united. 6. The melt dispersion process, in which the hardened oil is melted in a liquid by heat which does not dissolve it, the particles are dispersed in the melt, the dispersed Core material formed into small particles and then cooled and solidified will. The particle size of these coated particles, which consist of a core material with the coating of a hardened oil varies depending on the intended use. Usually own they have a particle diameter in the range of 50 to 2000 microns. It is best if the coated particles are independent of one another and have fluidity. If the overdone When particles cake together and are in a lumpy state, this is in use