DESCRIPTION OF THE INVENTION
The invention thus relates to an organic-inorganic complex, consisting of
or consisting essentially of urea and mineral particles, for use for increasing at
10 least one zootechnical performance figure of a farm animal, characterized in that
said mineral particles comprise at least one fibrous clay and at least one
nonfibrous clay, and in that the urea is adsorbed on the clays.
According to one embodiment, the mineral particles consist of at least one
fibrous clay and at least one nonfibrous clay.
15 According to a particular embodiment, preferably the mineral particles
comprise a combination of at least one fibrous clay, and of at least one nonfibrous
clay including necessarily montmorillonite.
The adsorption of urea at the surface or in the interlayer space of the
clays may be observed by any method known by a person skilled in the art,
20 notably by scanning electron microscopy, more precisely by SEM-EDX.
In one embodiment, the organic-inorganic complex consists of or consists
essentially of urea and mineral particles comprising at least one attapulgite and a
nonfibrous clay, the urea being adsorbed on the surface of the mineral particles,
and said surface may be that of their lamellae or those of their pores.
25 The mineral particles may consist of at least one attapulgite and at least
one nonfibrous clay.
Advantageously, the complex increases the zootechnical performance of
an animal compared to a simple mixture of urea and mineral powders that are
sources of at least one fibrous clay and at least one nonfibrous clay, a mixture in
30 which urea is not adsorbed on the surface of the clays.
Zootechnical performance of the animal in the sense of the invention may
consist of a daily weight gain and/or an increase in milk production.
The complex of the invention notably makes it possible to improve an
animal's milk production performance. The amount of milk produced may be
35 increased at constant quality. In particular, the butterfat content, the protein
content, the somatic cells count and the urea level may be kept constant without
adversely affecting the health of the animal's liver.
The farm animal is for example a ruminant.
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The inventors have in fact found, surprisingly, that a mixture of a
nonfibrous clay and a fibrous clay combined with urea, in the form of a complex
administered to a ruminant, makes it possible to improve fermentation in the
rumen considerably.
5 The complex also makes it possible to combat mycotoxins, in particular
aflatoxins and fumonisins. Finally, it can increase the daily weight gain of farm
animals.
Finally, the complex of the invention and the supplement of the invention
offer many advantages relative to the various existing urea substitutes. The
10 complex of the invention makes it possible to achieve zootechnical performance
equivalent to that of the prior art using lower doses of urea and of aluminosilicates
(clays and/or zeolites).
The mineral powders are preferably natural rocks that have been
extracted from the ground, and have optionally undergone transformations such
15 as grinding, sieving, tribomechanical activation or calcination, each of these rocks
essentially consisting of a material of interest; such as fibrous clay or nonfibrous
clay, the fibrous clay preferably being attapulgite and the nonfibrous clay
preferably being a montmorillonite. For example, bentonite is a rock containing
predominantly montmorillonite.
20 According to another preferred embodiment of the present invention, the
mineral particles comprise, besides the two clays, at least one zeolite. In this
embodiment, the nonfibrous clay may be montmorillonite.
The zeolite, when present, may represent between 0 and 60 wt% of the
mineral particles.
25 In the rest of the description, the word "zeolite" may denote the mineral
or the rock containing this mineral, unless stated otherwise. For example,
heulandite is a rock comprising predominantly zeolite.
It has been documented that zeolites reduce the amount of ammonium
produced in excess in the rumen of ruminants whose ration is supplemented with
30 urea (GB 1 356 313). Zeolites have already been combined with particular clays for
which complementarity in the presence of ammonium has been demonstrated.
Zeolites are in fact more selective at low concentrations of available cations, and
thus bind them more effectively than the clays, whereas the total ammonium
absorption capacity of the clays exceeds that of the zeolites and prolongs
35 absorption at higher concentrations. These mechanisms have been demonstrated
for varieties of clays such as smectites, kaolinite and attapulgite (US 5 079 201).
The benefits of using a mixture of zeolite, fibrous clay and nonfibrous clay
for adsorbing urea are all the more surprising in that, in the prior art, only the
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5
combination of zeolite and nonfibrous clay has been described, and in that the
benefits of this combination flow from the absorption of the ammonium produced
in excess in the rumen, by the mineral particles. The results of the invention are
also all the more surprising in that the combinations of urea and zeolite on the one
5 hand and the combinations of urea and bentonite on the other hand have only
been used for improving ruminal fermentation.
The mineral particles contained in the complex of the invention preferably
comprise more than 40 wt%, preferably more than 50 wt%, or even more than
80 wt% of the mixture of clays, or of the mixture of clays and zeolite when the
10 latter is present, knowing that the mineral particles may comprise water as well as
other minerals that are present naturally in the rocks used for making the
complex.
In a particular embodiment, the fibrous clay or the mixture of fibrous
clays may represent from 10 to 70 wt% of the sum of the weights of all the clays
15 and of the weight of zeolite, when the latter is present; the nonfibrous clay or the
mixture of nonfibrous clays may represent from 10 to 60 wt% of the sum of the
weights of all the clays and of the weight of zeolite, when the latter is present, the
total of the two percentages being greater than 40%.
In one embodiment, the mineral powders are made up of a combination
20 of at least one fibrous clay, at least one nonfibrous clay and at least one zeolite so
that the total weight of the mineral particles is equal to the weight of zeolite(s),
fibrous clay(s) and nonfibrous clay(s).
In one embodiment in which the complex does not comprise zeolite, the
sum of the weights of the fibrous and nonfibrous clays is at least equal to a value
25 selected from the group consisting of 40, 50, 60, 70, 80, 90 and 95 wt% of the
total weight of the fibrous and nonfibrous clays. In this embodiment, the fibrous
clay is preferably attapulgite and the nonfibrous clay is preferably montmorillonite.
In one embodiment in which the complex comprises zeolite, the sum of
the weights of each of the two clays and of the weight of the zeolite is at least
30 equal to a value selected from the group consisting of 50, 60, 70, 80, 90 and
95 wt% of the total weight of the mineral particles. In this embodiment, the
fibrous clay is preferably attapulgite and the nonfibrous clay is preferably
montmorillonite.
In a preferred embodiment, zeolite (or the transformed rock used as the
35 source of zeolite as stated above) represents between 30 and 60 wt%, preferably
between 35 and 55 wt%, more preferably between 45 and 55 wt%, and more
preferably between 48 and 52 wt%, relative to the total weight of the mineral
particles of zeolite, attapulgite and nonfibrous clay. In another preferred
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embodiment, zeolite (or the transformed rock used as the source of zeolite as
stated above) represents between 0 and 60 wt%, preferably between 0 and
50 wt%, more preferably between 0 and 40 wt%, and more preferably between 0
and 35 wt%, relative to the total weight of mineral particles of fibrous clay,
5 nonfibrous clay and zeolite.
Attapulgite (or the transformed rock used as the source of attapulgite)
represents for example between 10 and 50 wt%, preferably between 15 and
45 wt%, more preferably between 20 and 30 wt%, more preferably between 23
and 28 wt%, relative to the total weight of the mineral particles of fibrous clay,
10 nonfibrous clay and zeolite.
The fibrous clay preferably represents between 10 and 65 wt% of the
weight of the mineral particles.
The fibrous clay, which is preferably an attapulgite, or the mineral
containing it, represents for example between 0 and 70 wt%, preferably between
15 10 and 65 wt%, more preferably between 20 and 60 wt%, more preferably
between 30 and 60 wt%, relative to the total weight of the mineral particles of
fibrous clay, nonfibrous clay and zeolite.
The fibrous clay is preferably of natural origin. The clays whose lamellae
are discontinuous and form ribbons are regarded as fibrous clays in the sense of
20 the invention. The main types are sepiolite and attapulgite (also called
palygorskite).
Its water content, measured by any method known by a person skilled in
the art, may be between 10 and 25%. One of these methods consists of
measuring the water content by the weight loss in a stove at 105°C to constant
25 weight.
It may have a granulometry such that the oversize on a sieve of 75
microns by the dry method is less than 20%, preferably less than 15%. Its
apparent density may be of the order of 0.3 to 0.6 g/cm3
.
The fibrous clay preferably has a specific surface area between 80 and
140 m2
30 /g.
The nonfibrous clay preferably represents from 10 to 60 wt% of the
weight of the mineral particles.
The nonfibrous clay, which is preferably montmorillonite, or the mineral
containing it, may represent between 10 and 60 wt%, preferably between 20 and
35 50 wt%, more preferably between 25 and 45 wt%, the percentages being
expressed relative to the total weight of the mineral particles of fibrous clay,
nonfibrous clay and zeolite.
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The nonfibrous clay, which is preferably montmorillonite, or the mineral
containing it, may represent between 10 and 35 wt%, preferably between 15 and
30 wt%, more preferably between 22 and 28 wt%, the percentages being
expressed relative to the total weight of attapulgite, nonfibrous clay and zeolite.
5 The nonfibrous clay may be selected from montmorillonite, saponite,
vermiculite and kaolinite. A bentonite may be a source of montmorillonite. In one
embodiment, the montmorillonite is a bentonite preferably having a water content
below 15%, swelling greater than 10 ml/g, a granulometry such that less than
20% of the bentonite particles are larger than 90 microns, and a pH of the order
10 of 9.5.
The nonfibrous clay preferably has a cation exchange capacity (CEC)
ranging from 2 to 150 cmol/kg, for example from 30 to 120 cmol/kg, and
preferably from 40 to 100 cmol/kg. The cation exchange capacity is defined as the
capacity of the clay for exchanging the cations present in the interlayer spaces
15 with other cations or other organic or inorganic molecules.
The nonfibrous clay may advantageously have, besides one of the CEC
values stated above, a specific surface area from 10 to 700 m2
/g, from 400 to 600
m
2
/g, or preferably from 450 to 550 m2
/g.
The nonfibrous clay, for example such as montmorillonite, may
advantageously have a specific surface area from 450 to 550 m2
20 /g, and a CEC
from 40 to 100 cmol/kg.
A natural lamellar zeolite, for example of sedimentary origin, is preferred.
The zeolite may be derived from a rock, for example such as heulandite,
preferably comprising at least 70 wt%, at least 75 wt% or even at least 80 wt% of
25 clinoptilolite.
The rock used as the zeolite source may contain, besides clinoptilolite, a
clay, feldspar, mica, cristobalite and illite.
The zeolite may be a zeolite having a crystalline structure of the type
ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38 or ZSM 48 for example. The
30 diameter of its crystalline structure may be of the order of 0.3-0.5 nm.
The size of the zeolite particles may range from 1 micron to 250 microns;
the proportion of particles having a size from 5 microns to 65 microns is preferably
between 50 and 75 wt%, and the proportion of particles having a size from 5
microns to 125 microns may range from 75 to 95 wt% or from 85 to 95 wt%. The
35 granulometric distribution of the particles of zeolite may be measured by any
method known by a person skilled in the art.
The zeolite may be derived from the chabazites, heulandites, stilbites or
natrolites.
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The zeolite preferably has a specific surface area between 350 and 400
m
2
/g.
The zeolite is moreover advantageously characterized by values of zeta
potential between -18 and 35 mV depending on the pH. The zeta potential allows
5 estimation of the surface charge, which determines the degree of adsorption of
organic molecules. When a zeta potential is measured as a function of pH, there is
a pH value for which the zeta potential is cancelled. The potential decreases but
does not change sign when the concentration of the adsorbed ion increases.
Its water content, measured by any method known by a person skilled in
10 the art, may be below 8%. One of these methods consists of measuring the
weight loss in a stove at 105°C to constant weight.
Its apparent density may be of the order of 0.6-0.9 g/cm3
. It preferably
has a capacity for NH4
+
substitution of the order of 20000 mg NH4
+
/kg to
27000 mg NH4
+
/kg. Finally its cation exchange capacity is preferably above 60
15 meq/100 g. The specific characteristics of the zeolite described above may
correspond either to the zeolite in the organic-inorganic complex comprising urea,
or to the state of the zeolite that is used as the starting compound for preparing
the organic-inorganic complex.
In one embodiment, i) the weight ratio of urea to the mixture consisting
20 of attapulgite, montmorillonite and zeolite in the organic-inorganic complex of the
invention or ii) the weight ratio of urea to the mineral powders, is between 40/60
and 80/20, preferably between 50/50 and 70/30, more preferably of the order of
60/40. The stated percentage of the mineral powders may be the percentage of
the powders that are used for making the organic-inorganic complex, or the
25 percentage of the powders that are included in the complex, if the latter can be
measured.
The concentration of element N in the mixture of urea and the minerals of
the mixture is advantageously between 20% and 45% or between 30% and 40%.
The concentration of element N in the mixture of urea and the minerals of the
30 mixture is advantageously between 10% and 40% or between 15% and 35%.
The organic-inorganic complex included in the composition of the
invention may be prepared by a method known by a person skilled in the art,
using water.
For example, a method using water may comprise four steps: a step of
35 dissolving the urea, a step of suspending at least two clays in the urea solution, a
filtration step followed by a drying step. According to one embodiment, the urea is
dissolved in water at 65% of urea/35% of water minimum, at a temperature of
55°C-60°C with stirring so as to obtain a urea solution containing at least 35 wt%
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9
of water. After complete dissolution of the urea, the clays and the zeolite are
added and the mixture is stirred for 30 min to 1 hour at a temperature of 40°C50°C, before a filtration step and a drying step. Drying may be carried out under
air at 40°C.
5 The powders may be mixed with one another in one or more steps so as
to obtain the mixture of powders, which is then put in a reactor, with stirring. The
powders may also be fed into the reactor sequentially, optionally preparing
premixes of some of these powders.
According to one embodiment, the method for making an organic10 inorganic complex of the invention consists of mixing urea and mineral powders
comprising a source of fibrous clay, a source of nonfibrous clay and a source of
zeolite, the source of zeolite representing from 30 to 60 wt% of the weight of the
mineral powders, the source of fibrous clay representing from 10 to 50 wt% of the
weight of the mineral powders, the nonfibrous clay representing from 10 to
15 35 wt% of the weight of the mineral powders, and the weight ratio of urea to the
mineral powders being between 40/60 and 80/20.
The complex of the invention may be formed into granules or powder.
The granules may be obtained by wet granulation using any binder known by a
person skilled in the art.
20 The invention further relates to a dietary supplement for ruminants or a
product for feeding ruminants containing the organic-inorganic complex.
In the dietary supplement, the fibrous clay or the fibrous clays are
preferably present at a minimum content of 13 wt%, whereas the nonfibrous clay
or the nonfibrous clays are preferably present at a minimum content of 10 wt%.
25 The supplement may comprise, besides the mixture or the organicinorganic complex described above, other ingredients selected from the group
consisting of vitamins, minerals, byproducts of distillation of cereals with or
without solubles (DDG and DDGS), concentrated solubles of cereals (condensed
distiller's solubles, CDS), prebiotic fibers, probiotics, amino acids, proteins, omega
30 3 fatty acids, lignans, digestive enzymes, essential oil of Thymus vulgaris, chestnut
extracts, leonardite, peat, chestnut tannins, flax seeds, polyphenols, saponins,
advantageously the steroid and/or triterpene saponins, microalgae such as
chlorella or Spirulina (important natural nitrogen source in the form of essential
amino acids), macroalgae or extracts of algae.
35 The Spirulina preferably contains 65 wt% of proteins, 15 wt% of
carbohydrates, 7 wt% of lipids (linoleic acid = 8 g/kg; gamma-linolenic acid (GLA)
= 10 g/kg), 7% of minerals (calcium = 10000 mg/kg; chromium = 3 mg/kg;
copper = 12 mg/kg; iron = 1800 mg/kg; magnesium = 4000 mg/kg; manganese
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= 50 mg/kg; phosphorus = 8000 mg/kg; potassium = 14000 mg/kg; sodium =
9000 mg/kg; zinc = 30 mg/kg), 2 wt% of fibers, amino acids (alanine = 47 g/kg;
arginine = 43 g/kg; aspartic acid = 61 g/kg; cystine = 6 g/kg; glutamic acid =
91 g/kg; glycine = 32 g/kg; histidine = 10 g/kg; isoleucine = 35 g/kg; leucine =
5 54 g/kg; lysine = 29 g/kg; methionine = 14 g/kg; phenylalanine = 28 g/kg;
proline = 27 g/kg; serine = 32 g/kg; threonine = 32 g/kg; tryptophan = 9 g/kg;
tyrosine = 30 g/kg; valine = 40 g/kg), 5 wt% of vitamins and 2 wt% of water.
The dietary supplement may comprise, besides the complex described
above, at least one mineral compound selected from the group consisting of
10 Ca(H₂PO₄)₂, CaHPO₄, terrestrial limestone, marine limestone, MgO, Na2SO4,
NaHSO4, Na2CO3, NaHCO3 and CaSO4.
The dietary supplement may also comprise sugars, fats, waxes or flours.
The dietary supplement may thus be obtained by a method of granulation
or compaction of the complex, optionally adding an aqueous solution that may
15 contain molasses, CDS, lignosulfonates or any other binder known by a person
skilled in the art.
The dietary supplement according to the invention may be in various
forms, notably in powder, granules or blocks. The granules may be obtained by
spraying an aqueous solution containing the ingredients and the complex, or
20 alternatively by spraying an aqueous solution containing the ingredients on the
complex.
The invention also relates to a composition for feeding ruminants
comprising a mixture consisting of or consisting essentially of urea and mineral
powders comprising at least one zeolite, at least one attapulgite and at least one
25 nonfibrous clay. This mixture may be in the form of a complex in which urea is
adsorbed on the surface of the particles of clays and zeolite.
The invention also relates to a method for feeding ruminants, which
consists of supplementing the animal's daily ration with the organic-inorganic
complex described above.
30 The mixture may consist of urea, at least one zeolite, at least one
attapulgite and at least one nonfibrous clay.
The invention also relates to a method of feeding a ruminant that consists
of giving the animal the organic-inorganic complex or the dietary supplement
described above.
35 The dietary supplement or the complex may be given to the animal
independently of the ration or may be incorporated in the ration in the form of
granules or powder.
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The method of feeding a ruminant may consist of giving a daily ration
supplying the animal with 5 to 50 g/day of zeolite, 5 to 30 g/day of attapulgite,
from 1 to 20 g/day of montmorillonite and from 50 to 180 g/day of urea. It has in
fact been discovered in the context of the invention that the particular combination
5 described above makes it possible to achieve an equivalent quality of fermentation
at lower doses of urea, or improve the quality of fermentation at equivalent doses
of urea. The quality of fermentation is evaluated by any method known by a
person skilled in the art, such as investigating the milk quality or investigating the
weight gain.
10 In a particular embodiment, the complex or the supplement described
above is added to the ruminant's daily ration advantageously at a rate from 50 to
250 g of composition/mixture per kilogram of ration.
This ration may for example be made up of fodder of all types and in all
forms (green, dehydrated, ensiled, agglomerated), fodder grasses, fodder cereals
15 (barley, maize, oat, wheat, sorghum, soybean, rye), legumes (pea, horse bean,
lupine, soybean, alfalfa, sainfoin, clovers), roots, tubers and byproducts thereof
(beets, beet pulp, potato, potato pulp), cabbage, colza, sunflower, vegetable
waste (tops, stalks, husks of cereals, wheat bran, rye bran, shelled maize cobs,
bagasse) and potato starches, food industry byproducts (starch factory, potato
20 starch works, ethanol plant, brewery, flour milling), as well as oilseed cakes
(soybean cake), syrups and ammonium salts.
According to one embodiment, the daily ration comprises hay, maize
silage, grass silage, cereals, oilseed cakes, and a soluble nitrogen source.
The ruminant may be selected from bovines, sheep and goats. The
25 bovines include in particular the cow, in particular the dairy cow, suckling cow,
heifer, calf, grazing animal, bull calf, antelope, ox, fatstock, bull, buffalo, yak,
gayal and banteng. Sheep include in particular mouflon, sheep, ewe, two-year-old
ewe not yet having borne young, and lamb. Finally, goats include in particular
female goat, male goat, kid and ibex.
30 According to one embodiment, it is a milk-producing animal such as a
cow, a ewe or a goat.
The invention is illustrated by the following examples. The
physicochemical parameters that are mentioned in the present application may be
measured by any method that is known by a person skilled in the art and is
35 suitable for the technical problem solved by the invention.
EXAMPLES 1 to 8: Preparation of complexes of the invention and of
comparative complexes
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a) Firstly, organic-inorganic complexes according to the invention as well as
complexes of the prior art were prepared. Their compositions are given in
detail in Tables 1, 2 and 3.
5
Table 1 – Composition of complexes of the invention
Percentages by weight
Components Example 1 Example 2 Example 3
Urea 66% 50% 60%
Zeolite 17% 12.5% 18%
Attapulgite 8.5% 6.25% 14%
Montmorillonite 8.5% 6.25% 8%
Total 100%
Parameters
Weight ratio: urea/mineral powders 2/1 1/1 1.5/1
Weight ratio:
Zeolite/Attapulgite/Montmorillonite
50/25/25 50/25/25 45/35/20
Concentration of element N 36% 26% 27%
Table 2 - Composition of complexes of the invention
10
Percentages by weight
Components Example 4 Example 5 Example 6 Example 7
Urea 60% 61% 67% 63%
Zeolite 20% 17% 13% 0%
Attapulgite 10% 14% 13% 21%
Montmorillonite 10% 8% 7% 16%
Total 100%
Parameters
Weight ratio: urea/mineral
powders
1.5/1 1.6/1 2/1 1.7/1
Weight ratio Zeolite/
Attapulgite/Montmorillonite
50/25/25 45/35/20 40/40/20 0/67/33
Concentration of N 27% 28% 31% 29%
Table 3 – Composition of comparative complexes
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Percentages by weight
Components
Comparative
example UZ
21
Comparative
example UA
21
Comparative
example UM
21
Urea 66% 66% 66%
Zeolite 33%
Attapulgite 33%
Montmorillonite 33%
Total 100%
Parameters
Weight ratio: urea/mineral powders 2/1 2/1 2/1
Concentration of N 30.5 31.4 30.1
The urea was dissolved in water at a temperature of 55°C-60°C with
stirring so as to obtain a urea solution containing at least 35 wt% of water. After
complete dissolution of the urea, the zeolite (of grade Zeofirst®, company
5 ACTIFEED) and the clays (attapulgite of grade Clarsol® ATC-NA, company
CLARIANT, and montmorillonite of grade AGRI® Bond 400, company IMERYS)
were added and the mixture obtained was stirred for 30 min to 1 hour at a
temperature of 40°C-50°C. A filtration step and a drying step under air at 40°C for
24 hours were then carried out.
10
An organic-inorganic complex was obtained in which the urea is located in
the zeolite pores and in the clay lamellae.
It is shown in a photograph of Example 1 taken by scanning electron
15 microscopy (see Fig. 1).
b) Secondly, a supplement according to the invention was prepared in the
form of granules with the following composition presented in Table 4.
20
Table 4 – Composition of Example 8 of the invention

Example 8 wt%
Complex from Example 3 68-75%
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DDG or DDGS 5-20%
CDS 5-20%
Mixture of prebiotic fibers, probiotics, amino acids,
proteins, omega 3, lignans and digestive enzymes
Balance to
100%
This product was prepared by wet granulation of the mixture of the various
ingredients.
5 EXAMPLE 9: Tests of degradation in saliva
The kinetics of the concentration of NH4
+
in saliva was studied at 39°C and pH 6.5
for 24 hours, of examples 1, 2 and 4 to 6 of complexes of the invention.
10 Their kinetics was compared with that of soybean, prilled urea, and of the product
Optigen®16 (supplier Alltech; urea coated with a fat film for protection in the
rumen).
1.1 Test setup
15 The setup consists of 250-ml bottles containing 200 ml of buffered artificial saliva
at pH 6.5. This saliva consists of:
• Buffering substances: carbonate of Na+
and of NH4
+
• Macro-elements: Na, P, K and Mg
• Trace elements: Ca, Mn, Co and Fe
20
1.2 Treatments
Each product is put in a porous paper sachet that allows dissolution of the
elements with a granulometry below 500µm. Four repetitions of each variant are
put in the same bottle of artificial saliva. The degradation of the product is
25 monitored over a period of 24h (30 min, 1h, 2h, 4h, 6h and 24h) in a stove with
elliptical stirring (set at 39°C and 40 rpm). Each variant comprises 24 sachets
containing 2g of product.
After measuring the kinetics at each kinetics measurement point, the sachets are
recovered and dried in a lyophilizer for 24h before being analyzed to determine the
30 residual concentration of nitrogen in the product.
1.3 Processing the results
The results are analyzed with the SAS software according to the GLM model.
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1.4 Results
A first series of results is presented in Figs. 2 and 3.
In Fig. 2, the points of the curve from Example 1 merge with the points of the
5 curve from Example 2.
The following elements may be observed in the two figures:
Total release after 2h for urea
Gradual release up to 60% for Examples 1 and 2
Release below 50% Optigen®16.
10
A second series of results is presented in Fig. 3.
The following elements may be concluded:
Significant effect of the attapulgite dose (p=0.0232): 40% > 25% > 35%
Significant effect of the urea dose (p<0.001): 2 >1.6 >1.5
15 Taking the results into account, the optimal dose of attapulgite in the invention
(favorable concentration of N + protection of this N on release) is 35%.
Incorporation of urea is ideally 60% to offer a product rich in N allowing optimal
controlled release.
20
EXAMPLE 10: Study of fermentation in an artificial rumen
The effect of the release of NH4
+
on fermentation in the rumen was quantified by
measuring the rate of production of gases over a period of 24 hours with examples
25 1 and 2 of the invention.
They were compared with that of the examples of comparative complexes UA 21,
UZ 21 and UM 21, that of soybean, that of prilled urea, and that of the product
Optigen®16 (supplier Alltech; urea coated with a fat film for protection in the
rumen).
30 The protocol of the study of fermentation in an artificial rumen that was followed
was as follows.
1.1 Test setup
The setup consists of fifty 100mL bottles containing 60mL of an inoculum based on
35 rumen juice and buffered artificial saliva (1:3). This saliva consists of:
• Buffering substances: carbonate of Na+
and of NH4
+
• Macro-elements: Na, P, K and Mg
• Trace elements: Ca, Mn, Co and Fe
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• Colored indicator
• Reducing solution allowing verification of anaerobiosis of the medium to
simulate the environment of the rumen
This inoculum is incubated in conditions of anaerobiosis at 39°C with a limiting
5 substrate for N (6g of straw), to simulate physiological conditions. To compensate
the supply of soluble nitrogen and allow the bacteria to use this substrate
correctly, a source of quickly available energy must be supplied: maize starch, at a
rate of a ratio 1/2 (urea/starch), i.e. 0.2 g/bottle.
10 1.2 Treatments
Each study consists of two controls, a negative control without nitrogen
supplementation and a positive control with urea so as to be able to compare the
different test products. A minimum of four repetitions is necessary for statistical
analysis of the results.
15 To determine the rate of fermentation of each variant, the production of gases is
monitored in real time using the RF recording system from Ankom.
1.3 Processing the results
The results are analyzed with the SAS software according to the GLM model.
20
1.4 Results
The results are presented in Figs. 4 and 5. In Fig. 5, the curves from Examples 1
and 2 and the curve of the product Optigen®16 are reproduced for better
visualization of the differences.
25 The curves shown comprise, over a period of 24 hours representative of the
animal's biological rhythm, one or two fermentation peaks.
A first peak corresponds to the N utilization of the ration and of the unprotected
product, which is therefore immediately available: this first peak is observed in all
the variants. It occurs for example at about 6 hours for Examples 1 and 2, and at
30 about 4 hours for UM 21 and UZ 21.
A second peak, when present, corresponds to the utilization of the N of the
protected nitrogen, which is released gradually. It may be visualized at about 10
hours for Example 1, at about 13 hours for Example 2, and at about 17 hours for
35 the comparative example UA 21.
The complexes of the invention advantageously comprise two peaks, which makes
it possible to prolong the utilization of nitrogen and make it more gradual.
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A single peak occurs with the urea since it is not protected: the peak corresponds
to immediate release of the N.
For the products comprising protected urea, such as the product Optigen®16 and
the comparative complex UM 21, the peak observed corresponds to immediate
5 release of the N. A second peak corresponding to delayed release of the urea
ought to be observed, but this is not the case, very probably because it occurs
after 24 hours. The urea is too protected and its release is too delayed.
The complexes of the invention therefore have better performance than the
products for which a single peak is observed, because all the urea that they
10 contain is released immediately, or because the urea is too protected to be
released within a reasonable time.
Examples 1 and 2 of the invention and comparative examples UA 21 and UZ 21
are among the products generating two fermentation peaks within 24 hours.
15 The first peak of fermentation of the examples of the invention occurs later than
that of the comparative examples, so that release of the N available in the first few
hours is greater, quantitatively, it takes place over a longer period and it is more
gradual (see the slopes of the curves).
Moreover, the second peaks of the examples of the invention occur between about
20 10 and 13 hours. They are observed much later with the comparative examples
(for example after 17 hours or 18 hours).
Now, it is far more beneficial for the animal if fermentation takes place in as
regular a manner as possible and over a period of at most 14 hours, so that its
chronobiological rhythm is respected.
25
Thus, the complexes of urea and mineral powders of the invention make it
possible to maintain high, smooth fermentation kinetics over a period of the order
of 12 to 14 hours. This kinetic profile had never been obtained before. It makes it
possible to improve the animal's zootechnical performance.
30
The rate of fermentation is stabilized over a period of about 8 hours. It gradually
increases until complete consumption of the N available, then it is maintained
because the protected N takes over. In the prior art, the peaks observed are very
narrow and spaced apart, which does not allow high kinetics to be maintained for
35 a period of 6 to 8 hours.
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EXAMPLE 11: Test of absorption of mycotoxins by the complex from
Example 2
The absorption of the mycotoxins AFB1, FB1 and FB2 was studied in two
5 conditions of pH (pH = 3 and pH = 7).
4.1 Protocol
The test product is mixed at a dose of 1 kg/T with a buffered solution (pH 3 and
10 pH 7) contaminated individually with the mycotoxins described in Table 5.
Table 5 – Condition of the test of absorption of mycotoxins
Mycotoxins Concentration (ppb)
Aflatoxin B1 (AFB1) 5000
Fumonisin B1 (FB1) 50
Fumonisin B2 (FB2) 50
15
The solutions are mixed at 200 rpm for 90 minutes at 37°C. They are then
analyzed by LC-MS/MS to determine the remaining concentration of each
mycotoxin, which makes it possible to find the amount of toxin fixed by the
product.
20
4.2 Results
The results are summarized in Table 6 below.
25 Table 6 - Absorption of the mycotoxins by the complex of the invention
Percentage fixation
Mycotoxin pH 3 pH 7
AFB1 89% 70%
FB1 42% 5%
FB2 39% 6%
4.3 Conclusions
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The complex in Example 2 of the invention reduces the impact of the aflatoxin B1
and of the fumonisins (B1 and B2) in the test conditions in vitro.
5 EXAMPLE 12: In vivo study in a dairy cow farm, of the effects of the
complex from Example 1
The objective of the study was to test the product in vivo on a batch of cows for 1
month to evaluate the effect on milk production, fat content (BC), protein content
10 (PC) and the urea level in the milk.
1) Materials and method:
1.1 Animals, characteristics of the batches:
15 • 2 batches of dairy cows (Holstein breed): 9 animals per homogeneous
batches (n=20), one animal was removed in the course of the study.
• in stalls, without grazing and identical milking conditions (by robot)
The parameters at the start of the test are given in Table 7 below.
20 Table 7 – Parameters at the start of the study
Parameters at the start of
the test
Test Control
Number of animals 9 9
Average lactation rank (year) 2.1 2.0
Average lactation days (d) 202 186
Average milk production (kg) 38.6 39.1
Butterfat content (g/kg) 42.5 44.0
Protein content (g/kg) 32.5 32.9
Cells (*1000) 35 53
Urea (mg/kg) 199 220
1.2 Feeding:
25 Control: product of the prior art
• Basic ration:
Hay, maize silage, grass silage, triticale (cereal resulting from crossing wheat and
rye), mixture of soybean cake (70%) and colza (30%) (product AlimDuo®).
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• Individual supplementation by robot:
Nitrogen-containing correctant (AdeliaTanePro® combining soluble nitrogen and
soybean cake semi-protected by a tanning process marketed by the company
5 TRISKALIA) and Aliment VL ("Feed DC"), the whole at a rate of 500 g/dairy cow.
Test (iso energy and iso nitrogen):
• Basic ration
Identical to that of the Control:
10 • Individual supplementation by robot:
Identical to that of the Control described above, from which 535g of the nitrogencontaining correctant of the prior art is removed (i.e. half), 200g of product from
Example 1 in 100 mL of water is added by dosing, and 440g of triticale is added to
the trough in order to make up the energy deficit following withdrawal of the
15 correctant.
2) Results
2.1) Milk production:
20
The results obtained are presented in Fig. 6.
2.2) Milk quality:
25 The results are presented in Figs. 7 to 10.
Conclusions:
The complex of the invention offers many advantages relative to the nitrogen30 containing correctant of the prior art (identified as control in the figures).
In this test, conducted in France at a dairy cow farm, the results obtained with the
supplement of the invention, supplying a delayed-release urea, are very
advantageous. At lower doses:
- The iso-N and iso-energy replacement of the nitrogen-containing correctant
35 of the prior art AdeliaTanePro® (535 g) with a mixture made up of the
protected urea from Example 1 (200 g) and triticale (400 g), makes it
possible to maintain the animal's performance.
- Milk production is identical in the 2 batches (p>0.05).
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- Milk quality stays the same in the 2 batches: there is no of loss of content
(p>0.05) for the fat content (BC) and the protein content (PC).
- The product from Example 1 does not have a negative impact on the urea
level in the milk (p>0.05): the results are similar to those obtained with the
5 product of the prior art.
- There is no effect of the supplementation (p>0.05) on the somatic cells
count.
10 EXAMPLE 13: In vivo study at a dairy cow farm, of the effects of the
complex from Example 3
The objective of this study was to test the dietary supplement from Example 3 in
vivo on a batch of dairy cows for 60 days to evaluate its effect on milk production,
15 milk quality (BC, PC and Cells) and the urea level in the milk.
1) Materials and method:
20 • 3 batches of dairy cows (DCs):
- 7 animals per homogeneous batches (n=21).
- In stalls, without grazing and identical milking conditions (by robot).
• Feed:
25 - Basic ration: 10 kg/DC/d of a mixture of barley (20%), soybean
cake 48 (5%), maize (50%) and wheat bran (25%); alfalfa hay ad
libitum.
• Treatments:
- Control: basic ration described above.
30 - Test 1 (iso-supplies) = basic ration from which soybean has been
removed (500 g) and to which 145 g of the supplement from
Example 3 and 500 g of maize have been added.
- Test 2 (non-iso-supplies) = basic ration from which soybean has
been removed and to which 145 g of the supplement from Example
35 3 has been added.
Results:
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2.1) Milk production over a period of 60 days
The results for milk production are presented in Fig. 11.
A significant improvement in milk production performance is observed starting
5 from the 13th day. The results obtained for a mixed breed (Baltata romaneasca)
therefore show a large gain in milk production of up to 4 L of milk/day at the end
of a period of monitoring of two months.
2.2) Milk quality
10
The results are presented in Figs. 12 and 13.
Supply of the complex from Example 3 without iso supply (Test 2) tends to
increase the BC in the milk. No difference is observed for the PC. The large
increase in milk production did not lead to dilution of these levels. The cows have
15 therefore produced more milk but also more fat and protein matter to maintain the
level of BC and PC.
COMPARATIVE EXAMPLE 14: Mixture of urea and mineral powders
according to the prior art
20
The objective of this study was to compare the supplement from Example 7 and a
mixture of urea with the same mineral powders in the same proportions, but on
which the urea is not absorbed, in order to evaluate their effect on milk production
at a dairy cow farm.
25
1) Materials and method
• 2 batches of 7 cows of Prim’Holstein breed
• Test duration: 2 months
30 • Substitution for the batch Example 7
- Feed removed: 750g of soybean cake
- Feed added: 250g Example 7
• Substitution for the batch Powder Base + Urea
- Feed removed: 750g of soybean cake
35 - Feed added: 150g urea + 100g mineral base (same proportion as
Example 7)
2) Results for milk production
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The results are presented in Fig. 14.
A significant effect (p<0.05) of Example 7 is observed relative to the simple
5 mixture of the powder base + urea on the animals' milk production. After 60 days,
an increase in daily production equal to 1.2L of milk is obtained with example 7
relative to the Powder Base + Urea.

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CLAIMS
1. An organic-inorganic complex consisting of or consisting essentially
of urea and mineral particles, for use for increasing at least one zootechnical
5 performance of a farm animal, characterized in that said mineral particles comprise
at least one fibrous clay and at least one nonfibrous clay, and characterized in that
urea is adsorbed on the clays.
2. The organic-inorganic complex as claimed in the preceding claim,
characterized in that the weight ratio of urea to the mineral particles is between
10 30/70 and 80/20.
3. The organic-inorganic complex as claimed in claim 1, characterized
in that the fibrous clay represents between 10 and 65 wt% of the weight of the
mineral particles.
4. The organic-inorganic complex as claimed in one of the preceding
15 claims, characterized in that the fibrous clay is an attapulgite.
5. The organic-inorganic complex as claimed in the preceding claim,
characterized in that the attapulgite has granulometry such that an oversize
retained on a 75 micron sieve is less than 20% when measured by a dry sieving
method.
20 6. The organic-inorganic complex as claimed in one of the preceding
claims, characterized in that the nonfibrous clay represents from 5 to 60 wt% of
the weight of the mineral particles.
7. The organic-inorganic complex as claimed in one of the preceding
claims, characterized in that the nonfibrous clay has a cation exchange capacity
(CEC) from 2 to 150 cmol/kg, and a specific surface area from 10 m2
25 /g to 700
m
2
/g.
8. The organic-inorganic complex as claimed in one of the preceding
claims, characterized in that the nonfibrous clay is a bentonite.
9. The organic-inorganic complex as claimed in one of the preceding
30 claims, characterized in that the mineral particles comprise at least one zeolite.
10. The organic-inorganic complex as claimed in the preceding claim,
characterized in that the zeolite represents between 0 and 60 wt% of the weight
of the mineral particles.
11. The organic-inorganic complex as claimed in the preceding claim,
35 characterized in that the proportion, in the zeolite, of particles having a size from 5
microns to 125 microns ranges from 75 to 95 wt% or from 85 to 95 wt%.
12. The organic-inorganic complex as claimed in one of the preceding
claims, characterized in that the farm animal is a ruminant.
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13. The organic-inorganic complex as claimed in one of the preceding
claims, characterized in that the zootechnical performance of the animal consists
of a daily weight gain and/or an increase in milk production.
14. A dietary supplement for ruminants comprising an organic-inorganic
5 complex as claimed in one of the preceding claims and at least one other
ingredient selected from the group consisting of vitamins, minerals, byproducts of
distillation of cereals with or without solubles (DDG and DDGS), solubles of
concentrated cereals (CDS), prebiotic fibers, probiotics, amino acids, proteins,
omega 3 fatty acids, lignans, digestive enzymes, essential oil of Thymus vulgaris,
10 chestnut extracts, leonardite, peat, chestnut tannins, flax seeds, polyphenols,
saponins, advantageously steroid and/or triterpene saponins, microalgae such as
chlorella or Spirulina (important natural nitrogen source in the form of essential
amino acids), macroalgae or extracts of algae.
15. A method of feeding a ruminant that consists of giving the animal
15 the organic-inorganic complex as claimed in one of claims 1 to 13, or the dietary
supplement as claimed in claim 14.
16. The method of feeding a ruminant as claimed in the preceding
claim, characterized in that the animal is additionally given a daily ration
comprising hay, maize silage, grass silage, cereals, oilseed cakes, and a soluble
20 nitrogen source.