FR2577936A1 - Stable compositions in the form of miniparticles or powders with dry fluid flow, containing a chemically or physically unstable product to be protected, and process for the preparation of these compositions - Google Patents

Abstract

The composition is in the form of miniparticles or powders with dry fluid flow, consisting essentially of a mixture of a complex of gelatine and the product to be protected, optionally containing water, and of pulverulent compounds with dry fluidising action. The composition may additionally comprise various additives, especially reinforcers of the gel structure, lubricants and waterproofing agents. The process of preparation consists in mixing an aqueous gelatine solution with the product to be protected, hot, to obtain a homogeneous and stable dispersion in which the product to be protected is sequestered by the gelatine, in cooling the dispersion to gel it and to divide the gel into miniparticles or even into a powder by grinding predried miniparticles, and in then mixing the miniparticles or the powder with fluidising powders, the various optional additives being added either to the hot aqueous dispersion or during or after the division of the gel. Application in particular to the stabilisation of choline chloride to be incorporated into feedstuff premixes for cattle.

Description

The subject of the present invention is compositions, which are stable, non-denaturing protected presentations, of water-soluble or water-dispersible products (substances or mixtures of substances), which, isolated, have in particular - either fragile chemical conservation characteristics, - or marked hygroscopicity characteristics, which may
go to a very strong deliquescence, - either a conjunction in different degrees of the two characters
previous techniques, - either reactive potentials to be kept in reserve in
mixtures with other dry constituents, awaiting
mobilization of these potentials by aqueous dispersion.

The invention also relates to a method of
preparation of these stable compositions.

I1 is known to prepare dry compositions, by placing on powdery supports, which are water acceptors (silica, silicates) or inert substances (clays, flours, various plant by-products). However, these supports do not prevent the disintegration or the risks of contaminating diffusion of a component in the others
t components. It is also known to prepare dry compositions by placing on insoluble polymers (resin foams) or on fatty supports (fats, soaps). These latter compositions do not immediately release, at the desired time, the unstable component which they contain, by simple dispersion in lukewarm water.

 The present invention aims to remedy these drawbacks. To this end, it relates to stable compositions, containing at least one product that is chemically or physically unstable to protect, characterized in that they are in the form of minigrains or dry powder ferment nut powders, constituted essentially by a mixture of 'a gelatin complex - product to be protected, possibly containing water, and powdery compounds with a dry fluidizing effect. In general, said complex represents the major phase quantitatively. These compositions are stable on storage in ordinary surroundings without any conditioning requirement and they are non-reactive vis-à-vis the other constituents of the dry mixes in which they are incorporated, because the product to be protected is sequestered by gelatin.

These qualities, which are linked to the physical and chemical protective properties of gelatin, are optimal when preparing said compositions by the process according to the invention, which is characterized by the following successive stages a) Preparation of a homogeneous hot aqueous dispersion1 and
stable of the product to be protected in an aqueous solution
hot gelatin, S protect product being added
with hot gelatin solution as a solid
dry, or as an aqueous solution, gradually
and with stirring ensuring good homogenization,
and the dispersion obtained containing a gelatin complex
product to protect.

b) Dispersion gelation by refrigeration and division
jelly to make it into mini-grains or even,
after intermediate drying, powder obtained by
grinding of dry minigrains.

c) Mixing minigrains or powder with compounds
powders with dry leakage effect of mineral origin,
vegetable or animal, providing a composition in mini
grains or powder of dry fluid flow, said mixture
being performed during or after the division operation
jelly.

 Generally, the hot aqueous dispersion is at a temperature between 35- and 85 ° C, the hot aqueous gelatin solution is at a temperature of 40 to 85 C, and the gelling of the dispersion is carried out at a temperature of between -10- and + 200C in most cases.

The industrial applications of the process concern many fields of activity. As examples, we can cite - In the food and parapharmaceutical sector, the sta
mobilization of fruit essences, vegetable aromas, peptisates.

- In the livestock feed sector, stabilization
choline chloride for incorporation in the state
dry product in food premixes, called
hereinafter "premixes". This latest application is
jet of a particular development at the end of the presentation, in
the examples.

The development of these new compositions im
so fold successive steps, which are explained
below.

I. BASIC CONDITIONS OF THE PREPARATION a) preparation of aqueous, homogeneous, stable dispersions,
essentially based on a gelatin-substance complex
to protect, this with wide possibilities for
respective dry substance titles of these two consti
killing.

The gelatins used are, depending on the destination
tion of the final product, of compulsory food quality
or optional. They can come either
of various types of raw materials or technical uti
for the manufacture of gelatins, without requirement
particular class of jelly strength and viscosity.

"Modified" gelatins, subject to legal approval,
are also usable.

The chemical and physico-chemical parameters of gelatins
used are adjusted, in each case, to obtain
compatibility with the substance to be protected, ensure
blocking (zero syneresis), while respecting the rules
of satisfactory composition and development for the
destination of the product.

al) Treatment of the dispersion to obtain a jelly
having good structural qualities and good pro
additional properties.

The jelly should have good hardness, a touch
dry, easy and clean slicing possibility at time
normal room temperature. These qualities can result
simple cooling of the defined aqueous dispersion
in a) and produced with such a reduced water content
as possible.

However, many substances, interested classes
by protection against instability, have a strong poten
such as jelly depressants vis-à-vis gelatin.

This effect will be corrected at the level of liquid production
- either by incorporating additional gelling agents
food classes or not according to requirement, which one
commonly found in commerce (algae extracts,
polysaccharides from various sources, cellulose derivatives
etc.),
- either by treatment with gelatin hardening agents,
- either by adding soluble products with a reinforcing effect
by concentration of the dry extract,
- either by adding fillers with pending texturing effect
if we,
either by combining two or more of the patches
(gel boosters) above.

In improvement, with the particular aim of giving
some gel lubricated character, or to facilitate
redispersion during implementation in product
final, oil derivatives and similar agents are incorporated
dispersed for certain achievements.

For economic balances of formulation or
additional qualitative contributions, incorporations
very diverse in soluble substances or fillers will resolve
the problems.

Some achievements with special requirements can
wind benefit from jelly reinforcers; their elabo
ration in this case uses cryogenics.

b) Cooling of the dispersion for gelation - Divi
sion of the gel in mini-particles.

An application variant consists of preceding
the final division of a partial drying operation
or strong enough, which then gives a semi-solid product
or solid, to which is applied, after fine division,
the treatment c).

c) Dispersion of gel uni-particles in a complement
powdery.

This amalgam leads to a product with a character d2Fcou-
slightly dry fluid.

The powders used must be acceptable for
the destination of the final product and agree to ensure
dry flow and good performance characteristics
to the ambiance.

They are as appropriate
either of mineral origin (oxides, bydroxides, carbonates,
silicates, sulfates, phosphates, natural silicas
or activated, clays etc.),
either of plant origin (natural celluloses or elabo
rees, starches and derivatives, sugars, flours and bran, various
its proteins, gums etc.),
either of animal origin (dairy derivatives, proteins,
bones, fatty substances and derivatives).

Their dosage is carried out according to the guaranteed title
as a product protected from the final commercial powder.

For high demands on insensitivity to wear
in the environment, the protective potential of gelatin
can be reinforced by spraying, on minigrains
of jelly, during or at the end of division, of a film
water repellent protector made of material derivatives
oily (such as calcium stearate) or waxy,
with suitable dispersant.

The constituents used to prepare the composition
are generally implemented so that the composite
stable final tion contains, by weight, for example,
20 to 70 S of the product to be protected, 4 to 15 S of gelatin
dry (or higher dosages for applica
particular conditions), 0 to 60 S of water, 8 to 30 S of compounds
powders with dry fluidizing effect, the complement to
100 S being constituted by the various possible additives.

II. TECHNIQUES AND MATERIALS USED
a) Preparation of the dispersion
The gelatin solution is made separately. She
is obtained according to the usual protocols, namely
- direct dispersion by mixing in hot water at a
temperature from 40 to 85 C, or
- melting by heating at a temperature of 40 to 85 C
after swelling in cold water.

It can also correspond to a direct debit
solution to the required title on a fabric sling
tion of gelatin in the factory.

The product to be protected is added to the solution of
gelatin either in its dry form, with introduction
and gradual dispersion, either as a solution
or dispersion, in aqueous or other media
solvents, always with gradual introduction and
good homogenization by stirring. Solvents
can be very diverse; they are chosen according to
the nature of the product treated, if this is impossible
dissolving or dispersing it in water.

The addition of products with a strengthening effect
gel structure can precede, be simultaneous with,
or follow that of the product to be protected.

Various types of agitated tanks or mixers, continuous
or not, can be used subject to quality
chemical inertness kit of the material, of a heater
regulated fage, homogenization efficiency and
of sanitary normality.

b) Freezing by refrigeration and division of the jelly
They are carried out according to practices already used
for gelatin.

 The two phases can be successive or simultaneous.

1) Obtaining the jelly in continuous tape on the surface
refrigerated (endless belt or drum) at a tempera
ture from -10 to +20 C. Possibly cryogenic quenching,
at the temperature of the fluid used.

2) Fine division. It can be obtained by various
systems of slicers, choppers, cutters.

Simultaneous:
Either refrigerated extrusion at a temperature of -70-
at 120 C, with slicing at the outlet of the dies of a
extruder-exchanger with scraped surfaces or an extruder
with capillary line, completed by passage over cutter
either mini-beading on a cooling surface or in a
refrigerant, at a temperature of -10 to +20 C,
either spraying on cryogenic medium, at temp
specific erasure of the fluid used.

When subsequent drying takes place, the same
gelation techniques are valid, but the requirement
of division is less.

bl) Possible drying followed by grinding
Drying accommodates the devices and processes used
for gelatin alone: ventilated carpet dryers
in hot dehydrated air (static or con
tinues) - vacuum dryers - drying drums - beds
fluidized - atomization (without going through the gel phase).

The grinding will be carried out with the various types of grinders
used for dry gelatin.

c) Mixing with fluidizing powders:
It can be combined with cutting, or follow it.

The selected powders may, in case of multiplicity,
be introduced as a single mixture or in separate phases
successive.

The usual mixers for dry, continuous products
or not, are suitable for these operations.

APPLICATION EXAMPLES
They concern the application of the protection process
by choline chloride gelatin intended for food
animal feed.

This product, characterized by a strong deliquescence,
is thus incorporated into protected formulations sta
wheat, in flowing powders, guaranteed
in choline chloride, which will be used for the preparation
of premixes.

This new development does not present the insuf
dry commercial forms for chloride
of choline hitherto available and gives advantages
tages specific to the premixes containing it
These premixes benefit from blocking both
the decay of choline chloride, and the risks
contaminating diffusion afferents in their others
components.

They allow the immediate availability of the chlo
choline rure, by simple lukewarm aqueous dispersion,
and the stabilization of this phase dispersion both
watery than fatty by a colloido-protection conferred
by gelatin.

They facilitate and dry storage, by the
blocking of choline chloride in minigrains
of gel, and handling by the apparent density
high powder and very low powderiness
volatile.

They provide protection for vitamins and additives
fragile included in food formulations
animal.

They benefit, also because of the presence of
gelatin, a contribution of essential amino acids and
original and with an emulsifying and stabilizing potential
favorable for assimilation processes.

EXAMPLE 1 Preparation of a 50-fold powder in chloride
choline
a) Preparation of a homogeneous solution by incorporation
hot (at a temperature of 65 C) of a solution
concentrated aqueous choline chloride in a
concentrated aqueous gelatin solution. The titles
are adjusted separately to have parts by weight
for this liquid preparation
50 Dry choline chloride
6 Dry commercial gelatin
8 Gel structuring agents
15 Water
Structuring agents are introduced with the solution
choline chloride.

b) Gelling and cutting up to mini dimension
grains. Powdering during cutting with
2 Calcium stearate
c) Mixing the cut and powdered preparation with,
successively
17 Alumina mineral silicate
2 Calcium stearate
The total of the constituents represents 100 parts
in weight.

EXAMPLE 2 Production of a 50-fold powder in chloride
of choline.

a) Preparation of a single solution by incorporation
hot at a temperature of 65 C of an aqueous solution of
choline chloride in a concentrated aqueous solution
gelatin.

The titles are adjusted to have parts in
weight
50 Dry choline chloride
8 Commercial dry gelatin
0.5 Tanning agent (gel hardener)
-22 Water
The tanning agent, in solution in the appropriate solvent,
is added after incorporation of choline chloride.

b) Gelling and cutting until mini is obtained
grains under coating spray with
2 Water repellent composition
c) Mixing of the prepared preparation with, successively
vement
10 Magnesium carbonate
7 Calcium carbonate
0.5 Calcium stearate
The total of the constituents represents 100 parts
in weight.

EXAMPLE 3 Realization of a powder as title 70 in chloride
of choline.

a) Preparation of a single solution by incorporation
hot (at 85 C) chloride
choline in a concentrated aqueous solution of gela
tine to have in parts by weight
70 Dry choline chloride
10 Dry commercial gelatin
8 Water b) Gelling and cutting into mini-grains.

c) Mixing of the prepared preparation with, successively
vement
10 Magnesium carbonate
2 Calcium stearate
The total of the constituents represents 100 parts
in weight.

Detailed modifications of the equivalents domain
techniques can be applied to the process described
above, without going beyond the framework
of the present invention.

Claims (6)

 10) Stable composition containing at least one chemically or physically unstable product to be protected, this product being water-soluble or water-dispersible, characterized in that it is in the form of minigrains or powders of dry fluid flow, essentially consisting of a mixture of a gelatin complex product to be protected, possibly containing water, and powdery compounds with a dry fluidizing effect.  20) A stable composition according to claim 1, characterized in that it contains, in addition, at least one member of at least one of the following groups of additivesbrenforcers of the gel structure of the gelatin complex-product to be protected, lubricants , charges for economic purposes, products conferring complementary qualities, water-repellent agents.  3) A stable composition according to claim 1 or 2, characterized in that it contains, by weight, 20 to 70% of the product R protect, 4 to 15% of dry gelatin, 0 to 60% of water, 8 to 30% of powdery compounds with a dry fluidizing effect, the complement to 100% consisting of the various optional additives.  40) Composition according to Claim 3, characterized in that it contains, by weight, 50% of dry choline chloride, 6% of dry gelatin, 15% of water, 17% of aluminum silicate, as compound with fluidizing effect, 8% of gel structuring agents, and Li% of calcium stearate as water-repellent agent.  50) Composition according to claim 3, characterized in that it contains, by weight, 50% of dry choline chloride, 8% of dry gelatin, 22% of water, 10% of magnesium carbonate and 7% of carbonate of calcium as compounds with fluidizing effect, 0.5 do of tanning agent as gel hardener, 2% of a water repellent composition and 0.5 of calcium stearate also as water repellent.  6) Composition according to claim 3, characterized in that it contains, by weight, 70% of dry choline chloride, 10% of dry gelatin, 8% of water, 10% of magnesium carbonate as compound with fluidizing effect , and 2% calcium stearate as a water repellent.  70) Process for the preparation of a stable composition containing at least one chemically or physically unstable product to be protected, this product being water-soluble or water-dispersible, characterized by the following successive steps a) Preparation of a hot, homogeneous and stable aqueous dispersion of the product to be protected in a hot aqueous gelatin solution, the product to be protected being added to the hot gelatin solution in the form of a dry solid, or in the form of an aqueous solution or dispersion or in other solvents, gradually and with stirring ensuring good homogenization, and the dispersion obtained containing a gelatin-product complex to be protected. b) Gelation of the dispersion by refrigeration and division of the jelly to form it in the form of minigrains or even, after intermediate drying, of powder obtained by grinding the dry minigrains. c) Mixing minigrains or powder with pulverulent compounds with a dry fluidizing effect of mineral, vegetable or animal origin, providing a composition of minigrains or powder of dry fluid flow, said mixing being carried out during or after the operation of division of the jelly.  80) Method according to claim 7, characterized in that the gelling and the division of the jelly into minigrains are carried out successively.  9;) Method according to claim 7, characterized in that the gelation and the division of the jelly into minigrains are carried out simultaneously.  10) Process according to any one of Claims 7 to 9, characterized in that at least one member of at least one of the following groups of additives is added to the said hot aqueous dispersion: gel structure enhancers , lubricants, charges for economic purposes, products conferring complementary qualities.  110) Process according to any one of claims 7 to 10, characterized in that at least one water-repellent agent is added to the gel, during or after its division.  120) Process according to any one of claims 7 to 11, characterized in that the constituents of the composition are used so as to obtain a stable final composition containing, by weight, 20 to 70 g of the product to be protected , 4 to 15% of dry gelatin, 0 to 60% of water, 8 to 30% of pulverulent compounds with a dry fluidizing effect, the complement to 100% consisting of the various optional additives.