CA1333127C - Anti-clumping products, compositions and treatments for salts, simple and complex fertilizers - Google Patents
Anti-clumping products, compositions and treatments for salts, simple and complex fertilizersInfo
- Publication number
- CA1333127C CA1333127C CA000595995A CA595995A CA1333127C CA 1333127 C CA1333127 C CA 1333127C CA 000595995 A CA000595995 A CA 000595995A CA 595995 A CA595995 A CA 595995A CA 1333127 C CA1333127 C CA 1333127C
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- Prior art keywords
- clumping
- weight
- composition
- group
- product
- Prior art date
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
- B01J2/30—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic using agents to prevent the granules sticking together; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/20—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for preventing the fertilisers being reduced to powder; Anti-dusting additives
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/30—Anti-agglomerating additives; Anti-solidifying additives
Abstract
An anti-clumping product for salts and for simple and complex fertilizers is essentially constituted by a combination of one or several amine salts of alkylary-1-sulfonic acids and of one or several amine salts of acid phosphate esters, in the presence possibly of an excess of amine.
Description
13331~7 ANTI-CLUMPING PRODUCTS, ~OIIrOSITIONS AND TREATMENTS
FOR SALTS, SIMPLE AND COMPLEX FERTILIZERS
The invention relates to anti-clumping products, compositions and treatments for preventing the setting solid of salts and of simple and complex fertilizers.
Among the salts and simple fertilizers concerned by the invention, may be mentioned nitrogenous salts such as ammonium, potassium and calcium nitrates as well as mono-ammonium and diammonium sulphates and fertilizers containing urea.
Complex fertilizers are binary or ternary mixtures of elements of the group constituted by nitrogen, phosphorus or potassium; these fertilizers are identified by formulae of the type Nx Py Kz in which x, y, z repre-sent numbers which denote respectively the percentages of nitrogen, phosphoric anhydride and K20 constituting the complex fertilizer.
All fertilizers undergo generally a setting solid or clumping during storage.
The tendency to clumping is greater or less according to:
- the method of granulation, the grain occurring in the form of granules, grains, beads, spherules, small cylin-ders or prills; the fertilizer can also be compacted, - the origin of the constituent raw materials of the fertilizer, - the nature of the additives introduced into the mass 3o before granulation.
Among the numerous factors which influence clump-ing may be mentioned:
- the intrinsic humidity of the fertilizer as well as the outside humidity, - the temperature, - the storage time, 13~3127 - the storage pressure, - the structural polymorphisme particularly the phase transitions of ammonium nitrate, - the physical form and chemical composition of the grain.
The setting solid can sometimes reach proportions such that the fertilizer takes the form of a hard, compact mass or of large blocks extremely difficult to break up;
the fertilizer is then no longer utilizable as such. In the case of a storage in a silo, the setting solid may be such that the crust formed must be broken by heavy mecha-nical means. The storage, handling and spreading of the fertilizer are rendered more difficult, the setting solid then resulting in a considerable and unacceptable addi-tional economic expense.
To combat the setting solid, it has been proposed to resort to organic substances such as anionic and catio-nic surface-active agents, formulated into oily or waxy derivatives and associated possibly with other substances such as certain polymers or non-ionic surface-active agents.
Among the cationic surface-active agents proposed, may be mentioned aminated oils.
Among the anionic surface-active agents already proposed, may be mentioned - amine alkylaryl-sulfonates whose application is des-cribed in French Patent No. 2,460,706 belonging to the Assignee, - amino salts of acid phosphate esters whose application 3o in association with a mineral oil, a microcrystalline wax and a macrocrystalline wax, is described in Euro-pean Patent No. 113 687, as well as - potassium salts of acid phosphate esters whose use is described in U.S.S.R. Patent No. SU 1,131,859.
These products according to the prior art general-ly give satisfaction but, in face of the always increasing 1~3127 demands of users, Applicants have pursued their research in order to develop still more effective products.
And they have had the merit of finding that, surprisingly and unexpectedly, the simultaneous employment of two types of anti-clumping agents constituted respec-tively by amino salts of alkylaryl-sulfonic acids and amino salts of acid phosphate esters potentiated the anti-clumping properties of each of the two types of agents, which enables recourse to be had, in the case of their simultaneous utilization according to the invention, to an amount of active material less than that which is neces-sary to obtain the same anti-clumping effect when one or the other of the two types of agents is used alone, said simultaneous utilization permitting in addition, still for the same anti-clumping effect, the reduction, or even the elimination of coating charges generally necessary.
By means of the invention, it becomes possible to solve the problem of the setting solid of fertilizers very sensitive to the clumping phenomenon, such as ammonium nitrates containing sulphates in the mass or complex fertilizers.
It follows that the anti-clumping product accord-ing to the invention for salts and for simple and complex fertilizers is essentially constituted by a combination of one or several amino salts of alkylaryl-sulfonic acids and of one or several amino salts of acid phosphate esters, in the presence, as the case may require, of an excess of amine, said combination being producible by neutralization or ~over-neutralization" of a mixture of the one or more alkylaryl-sulfonic acids and of the one or more acid phosphate esters by means of one or several amines.
By the term ~alkylaryl-sulfonic acids", is meant mixtures of mono-, di- or trisulfonic acids of which the aromatic portion, preferably benzenic or naphthalenic, more particularly naphthalenic, is mono- or polyalkyl-substituted, the degree of substitution being an average 1 3 ~ 7 degree corresponding to the alkyl/aryl molar ratios used for the synthesis, it being understood that, for each of the contemplated degrees of substitution, namely generally from 1 to 4, it is possible to have complex mixtures of isomers of sulfonic acids; preferably, the total number of carbon atoms of the alkyl portion does not exceed 16 in the mixtures concerned.
By way of example, it is indicated that, in the case of 1.3-isopropyl-naphthalene-sulfonic acid, the average molar ratio isopropyl/naphthalene is equal to 1.3.
By the term "esters of acid phosphates" which may be prepared by the direct reaction of a compound with a hydroxyl group such as an alcohol, alkylphenol or alkyl-naphthol with, for example, phosphoric anhydride, the preferred ones are those which correspond to the following general formulae:
OH OH
O = P / O - (RlO)nl - R2 and O = P - OH
\ o - (RlO)n2 ~ R3 \ o - (RlO)n3 - R4 (I) (II) in which - Rl represents an alkylene group having from 2 to 4 carbon atoms, - R2, R3 and R4 represent an alkyl group having from 8 to 20 carbon atoms or an alkylaryl group of which the alkylated portion has from 8 to 12 carbon atoms, and 3o - n1, n2 and n3 represent a number from 0 to 15 and preferably from 0 to 5.
In general, the reaction recalled above for the preparation of these esters leads to mixtures of mono- and diesters.
For economic reasons, a mixture of compounds with - a hydroxyl group is often chosen, for example a mixture of 133~1~7 fatty alcohols.
For the preparation of the anti-clumping product according to the invention, a mixture of alkylaryl-sulfo-nic acids and of acid phosphates esters is formed, which mixture is then neutralized and even "over-neutralized" by one or several amines.
As amine, recourse is preferably had to alkyl-amines, cycloalkylamines or aromatic amines and possibly alkanolamines; said amines can be primary, secondary or tertiary.
The amine may be oxyalkylenated.
Advantageously, recourse is had to fatty alkyl-amines and preferably to alkylamines --or to mixtures of such amines-- whose number of carbon atoms varies from 12 to 20; technical stearylamine or hydrogenated suet amine give good results.
When there is over-neutralization, the latter does not exceed 25% molar excess of amine and is preferably limited to 10%.
The invention also relates to anti-clumping compo-sitions comprising, besides the abovesaid anti-clumping products according to the invention, at least one other anti-clumping product selected advantageously from the group of fatty acids and their salts as well as at least one formulation agent selected advantageously from the group comprising mineral oils and their mixtures with macrocrystalline waxes.
Among the fatty acids, recourse is advantageously had to those having 12 to 20 carbon atoms and preferably to stearic acid.
Among the salts of fatty acids, recourse is advantageously had to calcium or magnesium salts and preferably aluminum salts; still more particularly, recourse is had to an aluminum salt in which the molar ratio "aluminum/stearic acidH is in the vicinity of 2.
Generally oils with a paraffinic or naphthenic character are used, for example - the naphthenic oil marketed by the NYNAS Company under the trademark NYTEX and corresponding to the following specifications:
- density : 0.894 - kinematic viscosity at 40C : 23 cSt - hydrocarbon c Ipo~ition . aromatic : 10%
. naphthenic : 46%
. paraffinic : 44%, ou - the paraffinic oil marketed by BP ~rance under the trademark ENERPAR and corresponding to the following specifications:
- density : 0.925 ~ kinematic viscosity at 40C : 620 cSt - hydrocarbon composition . aromatic : 12%
. naphthenic : 22%
. paraffinic : 66%.
When the formulation is formed by means of a macrocrystalline wax, recourse is advantageously had to a paraffin wax having the following characteristics:
- melting point : 58-60C
- kinematic viscosity at 100C : 9 cSt ~ penetration at 25C : 16 - blocking temperature : 40.
The abovesaid anti-clumping compositions according to the invention are frequently of type I or II defined below in Table A and which differ from one another by the 3o proportion of the constituents.
TABLE A
Constituent Composition Composition in % weight of type I of type II
5 Anti-clumping product (according to the invention) 5 - 35 60 - 100 Fatty acid or one of its salts 0 - 10 0 - 10 Mineral oil 20 - 90 0 - 30 Macrocrystalline wax 0 - 50 0 - 15 In types I and II, the anti-clumping product according to the invention comprises:
- from 15 to 85% of alkylarylsulfonic acids, - from ~5 to 15% of acid phosphates esters and preferably - from 30 to 70% of alkylarylsulfonic acids, - from 70 to 30% of acid phosphates esters.
The anti-clumping treatment according to the in-vention is characterized by the fact that there is incor-porated with a salt, or with a simple or complex ferti-lizer, preferably at the exit from the drum or fluidized bed, the product to be treated having at that moment acquired almost all of its final r?ch~nical properties, an effective amount of the anti-clumping product according to the invention, preferably employed in the form of anti-clumping composition according to the invention.
The abovesaid effective amount of product according to the invention is advantageously from 0.005 to 0.05% by weight with respect to the salt, or to the simple 3o or complex fertilizer.
More particularly, there is incorporated with a salt, or with a simple or complex fertilizer, - either an anti-clumping composition of type I, by spraying, in an amount of 0.03 to 0.4% and, prefera-bly, from 0.05 to 0.2% by weight with respect to the treated product; thls spraying can be followed or 133~1~7 prece~e~ by coating by means of a charge of the group comprising chalk, infusorial earth, talc, clays or the like, - or a so-called doped charge obtained by treatment by means of an anti-clumping composition of type II of a charge of the group comprising chalk, infusorial earth, talc, clays, the proportion of composition II
with respect to the charge being from 1 to 10%, preferably from 1 to 6% by weight, the doped charge being employed by coating in the proportion of 0.1 to 1%, preferably from 0.2 to 0.6% by weight with respect to the treated product, it being understood that, in both cases, the proportion of anti-clumping product according to the invention intro-duced into the salts, or into the simple or complex fertilizers is comprised between 0.005 and 0.05% by weight with respect to the mass of salts, or of simple or complex fertilizers treated.
It is well known that it is not desirable to pre-pare the doped charge using substances cont~; ni ng too muchoil.
The coating of a salt, or of a simple or complex fertilizer by means of a doped charge is generally follow-ed by the spraying of an oil, vaseline or waxy products.
Heavy fuel is also much used. These substances serve to stick on the charge and to avoid dust.
At the exit from the cooling drum or at the end of the fluidized bed, the temperature of the treated product is generally below 40C and often below 32C, which 3o corresponds for ammonium nitrate, to the transition tempe-rature from phases IV to III which is well known to manu-facturers. The humidity is generally, at this stage, less than 1%.
In certain particular cases, the anti-clumping treatment may be done on a fertilizer partly cooled between 80 and 40C~ The cooling is then continued after 1333l27 incorporation of the anti-clumping agent.
In the case of the employment of an anti-clumping composition of type I, the latter may be sprayed at a te p~rature of about 80C by a suitable system permitting its ~ ~~eneous distribution on the fertilizer; the coat-ing amount whose possible application follows or pre~ee~s that of the anti-clumping composition of type I, may reach 2% by weight with respect to the treated product but mostly does not exceed 0.5%.
Advantageously, the anti-clumping compositions according to the invention enable to avoid the use of mineral coatings whose influence on the rescattering of dust is well known.
To illustrate the anti-clumping properties of the products according to the invention, a certain number of comparative trials were carried out.
For these trials, a concrete mixer was used in which an anti-clumping treatment according to the inven-tion was applied to 20 kg of fertilizer.
The fertilizer was then packaged in polyethylene bags and then stacked in a clumping module of the type illustrated by the single figure.
This clumping module comprises a metal framework constituted by uprights 1, a loading platform 2, cross braces 3 and a fixed platform 4.
Polyethylene bags 5, filled with product to be tested, were stacked as shown on the platform 2.
A platform 6 bearing a lifting cushion 7 was placed on the pile of bags. By inflating the cushion with 3o compressed air between the moveable platform 6 and the fixed platform 4, pressure was transmitted to the pile of bags.
This applied pressure was variable and could simulate a pile of bags 12 m high.
The fertillzer was kept under pressure for a period of greater or shorter duration, generrally from 10 to 45 days, sometimes several months. At the end of the test, the bags were opened, the clumps were weighed and the hardness of the clumps was measured by means of a dynamometer.
The clumping is expressed as the percentage of clumps (between 0 and 100). Generally, the hardness of the clumps is comprised between 0 and 100 N but can reach 200N
for untreated controls.
A clumping index is defined as being the product of the percentage of clumps multiplied by the hardness of the clumps.
Each measurement resulted from the average of several bags (generally 4 bags).
An anti-clumping treatment was applied to an NPK
granulated complex fertilizer of formula 15.12.24 by using - an anti-clumping composition A according to the inven-tion, - an anti-clumping composition B comprising one of the two agents entering into the constitution of the anti-clump-ing product of composition A, - a composition C comprising the other of the two agents entering into the constitution of the anti-clumping product of composition A, - an anti-clumping composition according to the prior art.
The anti-clumping composition A was constituted - in a proportion of 15% by weight of the product of neutralization of a mixture with 66% by weight of 1.3-isopropyl naphthalenesulfonic acid and 37% by weight of an acid laurylphosphate with 3 moles of ethylene oxide with stearylamine, - in a proportion of 60% by weight of a mineral oil, - in a proportion of 25% by weight of a macrocrystalline wax.
The anti-clumping ,~ ition B was constituted - in a proportion of 15% by weight of the product of 13331~?7 neutralization of 1.3-isopropyl naphthalenesulfonic acid with stearylamine, - in a proportion of 60% by weight of a mineral oil, - in a proportion of 25% by weight of a macrocrystalline wax.
The anti-clumping composition C was constituted - in a proportion of 15% by weight of the product of neutralization of an acid laurylphosphate with 3 moles of ethylene oxide (50/50 molar mixture of mono- and diesters) with stearylamine, - in a proportion of 60% by weight of a mineral oil, - in a proportion of 25% by weight of a macrocrystalline wax.
The anti-clumping compositions A, B and C are applied by spraying at 80C in the proportion of 0.15% by weight with respect to the fertilizer, this application being preceded by the application of an inert clay in the proportion of 0.3% by weight with respect to the ferti-lizer.
The anti-clumping composition according to the prior art was constituted by a doped clay with 3% by weight of stearylamine. It was applied in the proportion of 0.6% by weight with respect to the fertilizer, this application being followed by spraying of 0.2% by weight with respect to the fertilizer, of a vaseline.
The treated fertilizer was packaged in polyethy-lene bags and was sub;ected to a clumping test in the clumping module described above. The duration of the stacking was 20 days under a pressure of 1.5 kg/cm2.
3o At the end of this test, the bags were opened carefully. The clumps were weighed and the hardness of the clumps was measured by means of a dy~a ?ter.
The results of these measurements are collected in Table B.
TABLE B
% Hardness Clumping Treatment clumping of clumps Index 5 Clay doped with 3% amine 0.6 % 88 62 5500 Mineral oil 0.2 %
(prior art) Clay 0.3 % 35 46.5 1630 10 Composition A 0.15%
(according to the invention) Clay 0.3 % 71 59 4200 Composition B 0.15%
Clay 0.3 % 50 47 2400 Composition C 0.15~
Untreated control 100 160 16000 The results collected in Table B show that it is possible to reduce the dose of coating agent by one half with respect to an anti-clumping agent constituted by a commercial doped charge and that the combination of anti-clumping agents according to the invention shows potentia-tion of the anti-clumping properties of the two consti-tuent active materials of the combination.
An anti-clumping treatment is applied to an ammo-nium nitrate titrating 33.5% of nitrogen and containing 3~
of ammonium sulphate in the mass. The fertilizer was treated at 30C.
3 Four tests were carried out in which the anti-clumping treatment consisted respectively of spraying at 80C of 0.1% by weight with respect to the fertilizer of anti-clumping compositions D, E and F described below, and an anti-clumping composition according to the prior art constituted by a commercial aminated oil containing 18% of stearylamine and sprayed under the same conditions.
~3~3127 Composition D was constituted:
- in the proportion of 19% by weight of the product of neutralization with stearylamine of a mixture contain-ing 66% by weight of a 1.3-isopropylnaphthalenesulfo-nic acid and 37% by weight of an acid laurylphosphate (mixture of 50/50 of mono- and diesters), - in the proportion of 6% by weight of stearic acid, - in the proportion of 50% by weight of a mineral oil, - in the proportion of 25% by weight of a macrocrystal-line wax.
Composition E was constituted:
- in the proportion of 19% by weight of the product of neutralization of a 1.3-isopropyl naphthalenesulfonic acid with stearylamine, ~ in the proportion of 6% by weight of stearic acid, - in the proportion of 50% by weight of a mineral oil and - in the proportion of 25% by weight of a macrocrystal-line wax.
Composition F was constituted:
- in the proportion of 19% by weight of the product of neutralization of an acid laurylphosphate (mixture 50/50 of mono- and diesters) with stearylamine, - in the proportion of 6% by weight of stearic acid, ~ in the proportion of 50% by weight of a mineral oil and - in the proportion of 25% by weight of a macrocrystal-line wax.
The compositions D, E and F were applied in the 3o proportion of 0.1% by weight with respect to the ferti-lizer.
The treated fertilizer was subjected to the test described in Example 1 and the same measurements were carried out.
The results of these measurements are collected in Table C.
l33~l~7 TABLE C
% Hardness Clumping Treatment clumping of clumpsIndex Composition D 6 20 120 (according to the invention) Composition E 50 55 2750 Composition F 27 45 1200 Commercial aminated oil25 39 1000 (according to prior art) Untreated control 100 200 20000 The results collected in Table C show that the combination according to the invention shows a potentia-tion of the anti-clumping properties with respect to the properties of each of the constituent agents of the combination taken separately and formulated in the same manner.
An anti-clumping treatment was applied to an NPK
complex fertilizer of formula 16.10.5 known to be diffi-cult to anti-clump and which has a temperature of 35C.
Recourse was had to a composition G according to the invention constituted ~ in the proportion of 10% by weight of the product of neutralization with stearylamine of a mixture contain-ing 75% by weight of 1.3-isopropylnaphthalene sulfonic acid and 25% by weight of an acid alkylphosphate (50/50 molar mixture of mono- and diesters) of which 3o the alkyl portion was constituted by a chain compris-ing essentially a mixture of Cl6 et en Cl8, - in the proportion of 90% by weight of a mineral oil.
There was first applied, in a proportion of 0.3%
by weight with respect to the fertilizer, a clay and then sprayed at 80C the composition G in the proportion of 0.2% by weight wlth respect to the fertilizer.
133~127 Two comparative experiments were carried out by means of two compositions according to the prior art, denoted by "Control Nl" and "Control N2".
Control Nl was an alkylaryl sulfonate marketed by Compagnie Française de Produits Industriels under the trademark "GALORYL ATH 24n~ It was employed within the scope of a treatment which consisted of coating by means of 0.7~ by weight with respect to the fertilizer of a clay, followed by spraying at 80C of 0.2% by weight with respect to the fertilizer of a mixture containing 15% by weight of Control Nl in heavy fuel N2.
Control N2 was constituted by vaseline. It was employed within the scope of a treatment which consisted of a coating in a proportion of 0.5% by weight with res-pect to the fertilizer of a clay doped with 3% by weightof a composition based on stearylamine, followed by spraying at 80C of 0.2% by weight with respect to the fertilizer, of said control.
The treated fertilizer was subjected to the test described in Example 1 and the same measurements were carried out.
The results of these measurements are collected in Table D.
TABLE D
% Hardness Clumping Treatment clumping of clumps Index ( O . 7 % clay Control n-1 ( 0.03% GALORYL ATH 24 74 96 7100 ( o. 17Z heavy fuel 3o Control n- 2 ( o:25 %% vaSPeline Y 95 85 8070 COmPosition G ( -3 % clay 50 2150 ( 0.2 % composition G
Untreated control 100 20 20000 133~l27 The results collected in Table D show that, on a fertilizer extremely difficult to anti-clump, the inven-tion enables the amounts of mineral oil coating to be reduced, hence the ratio of rescattering of dust signi-ficantly reduced whilst improving the anti-clumping performance.
Anti-clumping composition G does not include mac~GcLys~alline wax.
An anti-clumping treatment is applied to an NPK
granulated complex fertilizer of formula 15.12.24 by using:
- anti-clumping compositions H and I according to the invention, - the anti-clumping composition B of Example 1, - an anti-clumping composition J comprising the other of the two agents entering into the constitution of the anti-clumping product of compositions H and I, - an anti-clumping composition according to the prior art.
The anti-clumping composition H was constituted - in the proportion of 15% by weight of the product of neutralization with stearylamine of a mixture contain-ing 65% by weight of 1.3-isopropylnaphthalene sulfonic acid and 35% by weight of an acid alkylphosphate defined in composition J, - in the proportion of 60% by weight of a mineral oil and - in the proportion of 25% by weight of a macrocrystal-line wax.
The anti-clumping composition I is constituted in the same manner as composition H, with the slight diffe-rence that the 60~ by weight of mineral oil are replaced by a mixture of 57% of mineral oil and 3% of aluminum stearate.
The anti-clumping composition J is constituted 13~127 - in the proportion of 15% by weight of the product of neutralization with stearylamine of an acid alkyl-phosphate (50/50 molar mixture of mono- and diesters) of which the alkyl portion is constituted by a chain comprising essentially a mixture of C8 and of C10, - in the proportion of 60% by weight of a mineral oil and - in the proportion of 25% by weight of a macloc~ystal-line wax.
The anti-clumping compositions B, H, I et J are applied by spraying at 80C in the proportion of 0.15% by weight with respect to the fertilizer, this application being preceded by the application of an inert clay in the proportion of 0.3% by weight with respect to the ferti-lizer.
The composition according to the prior art is constituted by a doped clay with 3% by weight of stearyl-amine.
It is applied in the proportion of 0.6% by weight with respect to the fertilizer, this application being followed by the spraying of vaseline in the proportion of 0.2% by weight with respect to the fertilizer.
The treated fertilizer is packaged in polyethylene bags and is subjecteed to a clumping test in the clumping module described above. The duration of the stacking is 40 days under a pressure of 1.5 kg/cm2.
At the end of this test, the polyethylene bags are opened carefully. The clumps are weighed and the hardness of the clumps is measured by means of a dynanometer.
3o The results of these measurements are collected in Table E.
13331~77 % Hardness Clumping Treatment clumping of clumps Index 5 Doped clay with 3%
amine 0.6 % 89 79 7030 Mineral oil 0.2 %
(prior art) Clay 0.3 %
10 Composition B 0.15%
Clay 0.3 %
Composition H 0.15%
(according to the invention) Clay 0.3 %
Composition I 0.15%
(according to the invention~
Clay 0.3 %
Composition J 0.15%
This example illustrates the pontentiation of the anti-clumping properties of the two active materials constituting the composition associated with aluminum stearate.
An anti-clumping treatment is applied to ammonium nitrate titrating 33.3% and containing 4% of ammonium sulphate in the mass. The fertilizer is treated at 30C.
Four trials were carried out in which the anti-clumping treatment consisted respectively of a spraying at80C of 0.1% by weight with respect to the fertilizer of the anti-clumping compositions K, L and M described below, and of an anti-clumping composition according to the prior art constituted by a commercial aminated oil containing 18% of stearylamine and sprayed under the same conditions.
The composition K according to the invention is constituted:
- in the proportion of 22% by weight of the product of neutralization with stearylamine of a mixture contain-ing 55% by weight of a tributyl-naphthalenesulfonic acid and 45% by weight of an acid stearylphosphate (50/50 mixture of mono- and diesters), - in the proportion of 10% by weight of stearic acid, - in the proportion of 45% by weight of a paraffin oil, - in the proportion of 23% by weight of a macrocrystal-line wax.
The composition L comprises one of the two agents entering into the constitution of anti-clumping product of the compositon K.
It is constituted:
~ in the proportion of 22% by weight of the product of neutralization of a tributyl-naphthalenesulfonic acid with stearylamine, - in the proportion of 10% by weight of stearic acid, - in the proportion of 45% by weight of a paraffin oil, - in the proportion of 23% by weight of a macrocrystal-line wax.
The composition M comprises the other of the two agents entering into the constitution of the anti-clumping product of composition K. It is constituted:
Z5 - in the proportion of 22% by weight of the product of neutralization of an acid stearylphosphate (50/50 mix-ture of mono- and diesters) with stearylamine, - in the proportion of 10% by weight of stearic acid, - in the proportion of 45% by weight of a paraffin oil, 3o - in the proportion of 23% by weight of a macrocrystal-line wax.
The treated fertilizer was sub;ected to the test described in Example 1 and the same measurements were carried out. The duration of stacking was, in this case, 45 days under a pressure of 1 kg/cm2.
The results of these measurements are collected in 133~1 ~7 Table F.
TABLE F
% Hardness Clumping Treatment clumping of clumps Index Composition K 45 30 1350 (according to the invention) Composition L 95 80 7600 Composition M 95 72 6840 Commercial aminated oil67 32 2140 (according to prior art) Untreated control 100 200 20000 The results collected in Table F show that the combination according to the invention causes the appea-rance of a potentiation of the anti-clumping properties with respect to the properties of each of the constituent agents of the combination taken separately and formulated in the same manner.
An anti-clumping treatment is applied to an NPK
complex fertilizer of formula 15.11.22 known to be diff-icult to anti-clump and which is at a temperature of 35C
using, by spraying with a proportion of 0.1~ by weight with respect to the treated fertilizer, an anti-clumping composition N according to the invetnion and an anti-clumping composition according to the prior art consti-tuted by a doped clay in the proportion of 3~ by weight of stearylamine.
The composition N is constituted:
- in the proportion of 15% by weight of the product of neutralization with stearylamine of a mixture contain-ing 50% of 1.3-isopropyl-naphthalenesulfonic acid and 50% of an acid laurylphosphate (50/50 molar mixture of mono- and diesters), - in the proportion of 60% by weight of a mineral oil 21 133~127 and - in the proportion of 25% by weight of a macrocrystal-line wax.
TABLE G
% Hardness Clumping Treatment clumping of clumps Index Composition N 37 35 1300 (according to the invention) 10( 0.6% doped clay 44 47 2070 Control ( 0.2% vaseline Untreated control 100 16016000 This example illustrates the fact that acomposition according to the invention permits the elimination of the mineral coating.
Advantageously, this remarkable anti-clumping performance is accompanied by suppression of the rescattering of the dust.
An anti-clumping treatment is applied to a urea-based fertilizer granulated with a charge in the mass by using an anti-clumping composition 0 according to the invention and an anti-clumping composition according to the prior art.
The anti-clumping composition 0 is constituted:
- in the proportion of 19% by weight of the product of neutralization with stearylamine of a mixture contain-ing 75% of the 1.3-isopropyl-naphthalenesulfonic acid and 25% of an acid laurylphosphate (50/50 molar 3 mixture of mono- and diesters), - in the proportion of 5% by weight of stearic acid, - in the proportion of 53% by weight of a mineral oil and - in the proportion of 23% by weight of a macrocrystal-line wax.
The anti-clumping composition according to the 133~127 prior art is constituted by a commercial aqueous solution of an alkylsulfate associated with soluble polymer of the ethylene vinyl acetate type.
The anti-clumping compositions are sprayed on the fertilizer in the proportion of 0.1% by weight with res-pect to the fertilizer.
The test is that described in Example 1. The dura-tion of stacking was 20 days under a pressure of 1 kg/cm2.
TABLE H
% Hardness Clumping Treatment clumping of clumps Index Solution according to the prior art 100 47 4700 15 Composition 0 (according to the invention, 30 22 660 Untreated control 100 60 6000 This example illustrates the anti-clumping pro-perties of the composition according to the invention.
The composition K described in Example 5, and the formulae called "coating mixture A, B and C" described in EP Patent 113 687, were tested comparatively.
The tests were carried out on a 33.5% ammonium nitrate containing 4% of ammonium sulphate.
The treatment consisted of spraying at 80C of 0.1% by weight with respect to the fertilizer of different anti-clumping compositions.
The treated fertilizer was subjected to the test 3 described in Example 1 and the same measurements were carried out. The duration of stacking was, in this case, 45 days under a pressure of 1 kg/cm2.
The results are collected in Table I.
-133~127 TABLE I
~ Hardness Clumping Treatment clumping of clumps Index 5. Composition K
(according to the invention) 45 50 1350 Coating mixture A 100 100 10000 Coating mixture B 100 100 10000 Coating mixture C 100 100 10000 This example illustrates the decisive superiority of the anti-clumping compositions according to the inven-tion with respect to the prior art on a fertilizer having a very strong tendency to setting solid.
FOR SALTS, SIMPLE AND COMPLEX FERTILIZERS
The invention relates to anti-clumping products, compositions and treatments for preventing the setting solid of salts and of simple and complex fertilizers.
Among the salts and simple fertilizers concerned by the invention, may be mentioned nitrogenous salts such as ammonium, potassium and calcium nitrates as well as mono-ammonium and diammonium sulphates and fertilizers containing urea.
Complex fertilizers are binary or ternary mixtures of elements of the group constituted by nitrogen, phosphorus or potassium; these fertilizers are identified by formulae of the type Nx Py Kz in which x, y, z repre-sent numbers which denote respectively the percentages of nitrogen, phosphoric anhydride and K20 constituting the complex fertilizer.
All fertilizers undergo generally a setting solid or clumping during storage.
The tendency to clumping is greater or less according to:
- the method of granulation, the grain occurring in the form of granules, grains, beads, spherules, small cylin-ders or prills; the fertilizer can also be compacted, - the origin of the constituent raw materials of the fertilizer, - the nature of the additives introduced into the mass 3o before granulation.
Among the numerous factors which influence clump-ing may be mentioned:
- the intrinsic humidity of the fertilizer as well as the outside humidity, - the temperature, - the storage time, 13~3127 - the storage pressure, - the structural polymorphisme particularly the phase transitions of ammonium nitrate, - the physical form and chemical composition of the grain.
The setting solid can sometimes reach proportions such that the fertilizer takes the form of a hard, compact mass or of large blocks extremely difficult to break up;
the fertilizer is then no longer utilizable as such. In the case of a storage in a silo, the setting solid may be such that the crust formed must be broken by heavy mecha-nical means. The storage, handling and spreading of the fertilizer are rendered more difficult, the setting solid then resulting in a considerable and unacceptable addi-tional economic expense.
To combat the setting solid, it has been proposed to resort to organic substances such as anionic and catio-nic surface-active agents, formulated into oily or waxy derivatives and associated possibly with other substances such as certain polymers or non-ionic surface-active agents.
Among the cationic surface-active agents proposed, may be mentioned aminated oils.
Among the anionic surface-active agents already proposed, may be mentioned - amine alkylaryl-sulfonates whose application is des-cribed in French Patent No. 2,460,706 belonging to the Assignee, - amino salts of acid phosphate esters whose application 3o in association with a mineral oil, a microcrystalline wax and a macrocrystalline wax, is described in Euro-pean Patent No. 113 687, as well as - potassium salts of acid phosphate esters whose use is described in U.S.S.R. Patent No. SU 1,131,859.
These products according to the prior art general-ly give satisfaction but, in face of the always increasing 1~3127 demands of users, Applicants have pursued their research in order to develop still more effective products.
And they have had the merit of finding that, surprisingly and unexpectedly, the simultaneous employment of two types of anti-clumping agents constituted respec-tively by amino salts of alkylaryl-sulfonic acids and amino salts of acid phosphate esters potentiated the anti-clumping properties of each of the two types of agents, which enables recourse to be had, in the case of their simultaneous utilization according to the invention, to an amount of active material less than that which is neces-sary to obtain the same anti-clumping effect when one or the other of the two types of agents is used alone, said simultaneous utilization permitting in addition, still for the same anti-clumping effect, the reduction, or even the elimination of coating charges generally necessary.
By means of the invention, it becomes possible to solve the problem of the setting solid of fertilizers very sensitive to the clumping phenomenon, such as ammonium nitrates containing sulphates in the mass or complex fertilizers.
It follows that the anti-clumping product accord-ing to the invention for salts and for simple and complex fertilizers is essentially constituted by a combination of one or several amino salts of alkylaryl-sulfonic acids and of one or several amino salts of acid phosphate esters, in the presence, as the case may require, of an excess of amine, said combination being producible by neutralization or ~over-neutralization" of a mixture of the one or more alkylaryl-sulfonic acids and of the one or more acid phosphate esters by means of one or several amines.
By the term ~alkylaryl-sulfonic acids", is meant mixtures of mono-, di- or trisulfonic acids of which the aromatic portion, preferably benzenic or naphthalenic, more particularly naphthalenic, is mono- or polyalkyl-substituted, the degree of substitution being an average 1 3 ~ 7 degree corresponding to the alkyl/aryl molar ratios used for the synthesis, it being understood that, for each of the contemplated degrees of substitution, namely generally from 1 to 4, it is possible to have complex mixtures of isomers of sulfonic acids; preferably, the total number of carbon atoms of the alkyl portion does not exceed 16 in the mixtures concerned.
By way of example, it is indicated that, in the case of 1.3-isopropyl-naphthalene-sulfonic acid, the average molar ratio isopropyl/naphthalene is equal to 1.3.
By the term "esters of acid phosphates" which may be prepared by the direct reaction of a compound with a hydroxyl group such as an alcohol, alkylphenol or alkyl-naphthol with, for example, phosphoric anhydride, the preferred ones are those which correspond to the following general formulae:
OH OH
O = P / O - (RlO)nl - R2 and O = P - OH
\ o - (RlO)n2 ~ R3 \ o - (RlO)n3 - R4 (I) (II) in which - Rl represents an alkylene group having from 2 to 4 carbon atoms, - R2, R3 and R4 represent an alkyl group having from 8 to 20 carbon atoms or an alkylaryl group of which the alkylated portion has from 8 to 12 carbon atoms, and 3o - n1, n2 and n3 represent a number from 0 to 15 and preferably from 0 to 5.
In general, the reaction recalled above for the preparation of these esters leads to mixtures of mono- and diesters.
For economic reasons, a mixture of compounds with - a hydroxyl group is often chosen, for example a mixture of 133~1~7 fatty alcohols.
For the preparation of the anti-clumping product according to the invention, a mixture of alkylaryl-sulfo-nic acids and of acid phosphates esters is formed, which mixture is then neutralized and even "over-neutralized" by one or several amines.
As amine, recourse is preferably had to alkyl-amines, cycloalkylamines or aromatic amines and possibly alkanolamines; said amines can be primary, secondary or tertiary.
The amine may be oxyalkylenated.
Advantageously, recourse is had to fatty alkyl-amines and preferably to alkylamines --or to mixtures of such amines-- whose number of carbon atoms varies from 12 to 20; technical stearylamine or hydrogenated suet amine give good results.
When there is over-neutralization, the latter does not exceed 25% molar excess of amine and is preferably limited to 10%.
The invention also relates to anti-clumping compo-sitions comprising, besides the abovesaid anti-clumping products according to the invention, at least one other anti-clumping product selected advantageously from the group of fatty acids and their salts as well as at least one formulation agent selected advantageously from the group comprising mineral oils and their mixtures with macrocrystalline waxes.
Among the fatty acids, recourse is advantageously had to those having 12 to 20 carbon atoms and preferably to stearic acid.
Among the salts of fatty acids, recourse is advantageously had to calcium or magnesium salts and preferably aluminum salts; still more particularly, recourse is had to an aluminum salt in which the molar ratio "aluminum/stearic acidH is in the vicinity of 2.
Generally oils with a paraffinic or naphthenic character are used, for example - the naphthenic oil marketed by the NYNAS Company under the trademark NYTEX and corresponding to the following specifications:
- density : 0.894 - kinematic viscosity at 40C : 23 cSt - hydrocarbon c Ipo~ition . aromatic : 10%
. naphthenic : 46%
. paraffinic : 44%, ou - the paraffinic oil marketed by BP ~rance under the trademark ENERPAR and corresponding to the following specifications:
- density : 0.925 ~ kinematic viscosity at 40C : 620 cSt - hydrocarbon composition . aromatic : 12%
. naphthenic : 22%
. paraffinic : 66%.
When the formulation is formed by means of a macrocrystalline wax, recourse is advantageously had to a paraffin wax having the following characteristics:
- melting point : 58-60C
- kinematic viscosity at 100C : 9 cSt ~ penetration at 25C : 16 - blocking temperature : 40.
The abovesaid anti-clumping compositions according to the invention are frequently of type I or II defined below in Table A and which differ from one another by the 3o proportion of the constituents.
TABLE A
Constituent Composition Composition in % weight of type I of type II
5 Anti-clumping product (according to the invention) 5 - 35 60 - 100 Fatty acid or one of its salts 0 - 10 0 - 10 Mineral oil 20 - 90 0 - 30 Macrocrystalline wax 0 - 50 0 - 15 In types I and II, the anti-clumping product according to the invention comprises:
- from 15 to 85% of alkylarylsulfonic acids, - from ~5 to 15% of acid phosphates esters and preferably - from 30 to 70% of alkylarylsulfonic acids, - from 70 to 30% of acid phosphates esters.
The anti-clumping treatment according to the in-vention is characterized by the fact that there is incor-porated with a salt, or with a simple or complex ferti-lizer, preferably at the exit from the drum or fluidized bed, the product to be treated having at that moment acquired almost all of its final r?ch~nical properties, an effective amount of the anti-clumping product according to the invention, preferably employed in the form of anti-clumping composition according to the invention.
The abovesaid effective amount of product according to the invention is advantageously from 0.005 to 0.05% by weight with respect to the salt, or to the simple 3o or complex fertilizer.
More particularly, there is incorporated with a salt, or with a simple or complex fertilizer, - either an anti-clumping composition of type I, by spraying, in an amount of 0.03 to 0.4% and, prefera-bly, from 0.05 to 0.2% by weight with respect to the treated product; thls spraying can be followed or 133~1~7 prece~e~ by coating by means of a charge of the group comprising chalk, infusorial earth, talc, clays or the like, - or a so-called doped charge obtained by treatment by means of an anti-clumping composition of type II of a charge of the group comprising chalk, infusorial earth, talc, clays, the proportion of composition II
with respect to the charge being from 1 to 10%, preferably from 1 to 6% by weight, the doped charge being employed by coating in the proportion of 0.1 to 1%, preferably from 0.2 to 0.6% by weight with respect to the treated product, it being understood that, in both cases, the proportion of anti-clumping product according to the invention intro-duced into the salts, or into the simple or complex fertilizers is comprised between 0.005 and 0.05% by weight with respect to the mass of salts, or of simple or complex fertilizers treated.
It is well known that it is not desirable to pre-pare the doped charge using substances cont~; ni ng too muchoil.
The coating of a salt, or of a simple or complex fertilizer by means of a doped charge is generally follow-ed by the spraying of an oil, vaseline or waxy products.
Heavy fuel is also much used. These substances serve to stick on the charge and to avoid dust.
At the exit from the cooling drum or at the end of the fluidized bed, the temperature of the treated product is generally below 40C and often below 32C, which 3o corresponds for ammonium nitrate, to the transition tempe-rature from phases IV to III which is well known to manu-facturers. The humidity is generally, at this stage, less than 1%.
In certain particular cases, the anti-clumping treatment may be done on a fertilizer partly cooled between 80 and 40C~ The cooling is then continued after 1333l27 incorporation of the anti-clumping agent.
In the case of the employment of an anti-clumping composition of type I, the latter may be sprayed at a te p~rature of about 80C by a suitable system permitting its ~ ~~eneous distribution on the fertilizer; the coat-ing amount whose possible application follows or pre~ee~s that of the anti-clumping composition of type I, may reach 2% by weight with respect to the treated product but mostly does not exceed 0.5%.
Advantageously, the anti-clumping compositions according to the invention enable to avoid the use of mineral coatings whose influence on the rescattering of dust is well known.
To illustrate the anti-clumping properties of the products according to the invention, a certain number of comparative trials were carried out.
For these trials, a concrete mixer was used in which an anti-clumping treatment according to the inven-tion was applied to 20 kg of fertilizer.
The fertilizer was then packaged in polyethylene bags and then stacked in a clumping module of the type illustrated by the single figure.
This clumping module comprises a metal framework constituted by uprights 1, a loading platform 2, cross braces 3 and a fixed platform 4.
Polyethylene bags 5, filled with product to be tested, were stacked as shown on the platform 2.
A platform 6 bearing a lifting cushion 7 was placed on the pile of bags. By inflating the cushion with 3o compressed air between the moveable platform 6 and the fixed platform 4, pressure was transmitted to the pile of bags.
This applied pressure was variable and could simulate a pile of bags 12 m high.
The fertillzer was kept under pressure for a period of greater or shorter duration, generrally from 10 to 45 days, sometimes several months. At the end of the test, the bags were opened, the clumps were weighed and the hardness of the clumps was measured by means of a dynamometer.
The clumping is expressed as the percentage of clumps (between 0 and 100). Generally, the hardness of the clumps is comprised between 0 and 100 N but can reach 200N
for untreated controls.
A clumping index is defined as being the product of the percentage of clumps multiplied by the hardness of the clumps.
Each measurement resulted from the average of several bags (generally 4 bags).
An anti-clumping treatment was applied to an NPK
granulated complex fertilizer of formula 15.12.24 by using - an anti-clumping composition A according to the inven-tion, - an anti-clumping composition B comprising one of the two agents entering into the constitution of the anti-clump-ing product of composition A, - a composition C comprising the other of the two agents entering into the constitution of the anti-clumping product of composition A, - an anti-clumping composition according to the prior art.
The anti-clumping composition A was constituted - in a proportion of 15% by weight of the product of neutralization of a mixture with 66% by weight of 1.3-isopropyl naphthalenesulfonic acid and 37% by weight of an acid laurylphosphate with 3 moles of ethylene oxide with stearylamine, - in a proportion of 60% by weight of a mineral oil, - in a proportion of 25% by weight of a macrocrystalline wax.
The anti-clumping ,~ ition B was constituted - in a proportion of 15% by weight of the product of 13331~?7 neutralization of 1.3-isopropyl naphthalenesulfonic acid with stearylamine, - in a proportion of 60% by weight of a mineral oil, - in a proportion of 25% by weight of a macrocrystalline wax.
The anti-clumping composition C was constituted - in a proportion of 15% by weight of the product of neutralization of an acid laurylphosphate with 3 moles of ethylene oxide (50/50 molar mixture of mono- and diesters) with stearylamine, - in a proportion of 60% by weight of a mineral oil, - in a proportion of 25% by weight of a macrocrystalline wax.
The anti-clumping compositions A, B and C are applied by spraying at 80C in the proportion of 0.15% by weight with respect to the fertilizer, this application being preceded by the application of an inert clay in the proportion of 0.3% by weight with respect to the ferti-lizer.
The anti-clumping composition according to the prior art was constituted by a doped clay with 3% by weight of stearylamine. It was applied in the proportion of 0.6% by weight with respect to the fertilizer, this application being followed by spraying of 0.2% by weight with respect to the fertilizer, of a vaseline.
The treated fertilizer was packaged in polyethy-lene bags and was sub;ected to a clumping test in the clumping module described above. The duration of the stacking was 20 days under a pressure of 1.5 kg/cm2.
3o At the end of this test, the bags were opened carefully. The clumps were weighed and the hardness of the clumps was measured by means of a dy~a ?ter.
The results of these measurements are collected in Table B.
TABLE B
% Hardness Clumping Treatment clumping of clumps Index 5 Clay doped with 3% amine 0.6 % 88 62 5500 Mineral oil 0.2 %
(prior art) Clay 0.3 % 35 46.5 1630 10 Composition A 0.15%
(according to the invention) Clay 0.3 % 71 59 4200 Composition B 0.15%
Clay 0.3 % 50 47 2400 Composition C 0.15~
Untreated control 100 160 16000 The results collected in Table B show that it is possible to reduce the dose of coating agent by one half with respect to an anti-clumping agent constituted by a commercial doped charge and that the combination of anti-clumping agents according to the invention shows potentia-tion of the anti-clumping properties of the two consti-tuent active materials of the combination.
An anti-clumping treatment is applied to an ammo-nium nitrate titrating 33.5% of nitrogen and containing 3~
of ammonium sulphate in the mass. The fertilizer was treated at 30C.
3 Four tests were carried out in which the anti-clumping treatment consisted respectively of spraying at 80C of 0.1% by weight with respect to the fertilizer of anti-clumping compositions D, E and F described below, and an anti-clumping composition according to the prior art constituted by a commercial aminated oil containing 18% of stearylamine and sprayed under the same conditions.
~3~3127 Composition D was constituted:
- in the proportion of 19% by weight of the product of neutralization with stearylamine of a mixture contain-ing 66% by weight of a 1.3-isopropylnaphthalenesulfo-nic acid and 37% by weight of an acid laurylphosphate (mixture of 50/50 of mono- and diesters), - in the proportion of 6% by weight of stearic acid, - in the proportion of 50% by weight of a mineral oil, - in the proportion of 25% by weight of a macrocrystal-line wax.
Composition E was constituted:
- in the proportion of 19% by weight of the product of neutralization of a 1.3-isopropyl naphthalenesulfonic acid with stearylamine, ~ in the proportion of 6% by weight of stearic acid, - in the proportion of 50% by weight of a mineral oil and - in the proportion of 25% by weight of a macrocrystal-line wax.
Composition F was constituted:
- in the proportion of 19% by weight of the product of neutralization of an acid laurylphosphate (mixture 50/50 of mono- and diesters) with stearylamine, - in the proportion of 6% by weight of stearic acid, ~ in the proportion of 50% by weight of a mineral oil and - in the proportion of 25% by weight of a macrocrystal-line wax.
The compositions D, E and F were applied in the 3o proportion of 0.1% by weight with respect to the ferti-lizer.
The treated fertilizer was subjected to the test described in Example 1 and the same measurements were carried out.
The results of these measurements are collected in Table C.
l33~l~7 TABLE C
% Hardness Clumping Treatment clumping of clumpsIndex Composition D 6 20 120 (according to the invention) Composition E 50 55 2750 Composition F 27 45 1200 Commercial aminated oil25 39 1000 (according to prior art) Untreated control 100 200 20000 The results collected in Table C show that the combination according to the invention shows a potentia-tion of the anti-clumping properties with respect to the properties of each of the constituent agents of the combination taken separately and formulated in the same manner.
An anti-clumping treatment was applied to an NPK
complex fertilizer of formula 16.10.5 known to be diffi-cult to anti-clump and which has a temperature of 35C.
Recourse was had to a composition G according to the invention constituted ~ in the proportion of 10% by weight of the product of neutralization with stearylamine of a mixture contain-ing 75% by weight of 1.3-isopropylnaphthalene sulfonic acid and 25% by weight of an acid alkylphosphate (50/50 molar mixture of mono- and diesters) of which 3o the alkyl portion was constituted by a chain compris-ing essentially a mixture of Cl6 et en Cl8, - in the proportion of 90% by weight of a mineral oil.
There was first applied, in a proportion of 0.3%
by weight with respect to the fertilizer, a clay and then sprayed at 80C the composition G in the proportion of 0.2% by weight wlth respect to the fertilizer.
133~127 Two comparative experiments were carried out by means of two compositions according to the prior art, denoted by "Control Nl" and "Control N2".
Control Nl was an alkylaryl sulfonate marketed by Compagnie Française de Produits Industriels under the trademark "GALORYL ATH 24n~ It was employed within the scope of a treatment which consisted of coating by means of 0.7~ by weight with respect to the fertilizer of a clay, followed by spraying at 80C of 0.2% by weight with respect to the fertilizer of a mixture containing 15% by weight of Control Nl in heavy fuel N2.
Control N2 was constituted by vaseline. It was employed within the scope of a treatment which consisted of a coating in a proportion of 0.5% by weight with res-pect to the fertilizer of a clay doped with 3% by weightof a composition based on stearylamine, followed by spraying at 80C of 0.2% by weight with respect to the fertilizer, of said control.
The treated fertilizer was subjected to the test described in Example 1 and the same measurements were carried out.
The results of these measurements are collected in Table D.
TABLE D
% Hardness Clumping Treatment clumping of clumps Index ( O . 7 % clay Control n-1 ( 0.03% GALORYL ATH 24 74 96 7100 ( o. 17Z heavy fuel 3o Control n- 2 ( o:25 %% vaSPeline Y 95 85 8070 COmPosition G ( -3 % clay 50 2150 ( 0.2 % composition G
Untreated control 100 20 20000 133~l27 The results collected in Table D show that, on a fertilizer extremely difficult to anti-clump, the inven-tion enables the amounts of mineral oil coating to be reduced, hence the ratio of rescattering of dust signi-ficantly reduced whilst improving the anti-clumping performance.
Anti-clumping composition G does not include mac~GcLys~alline wax.
An anti-clumping treatment is applied to an NPK
granulated complex fertilizer of formula 15.12.24 by using:
- anti-clumping compositions H and I according to the invention, - the anti-clumping composition B of Example 1, - an anti-clumping composition J comprising the other of the two agents entering into the constitution of the anti-clumping product of compositions H and I, - an anti-clumping composition according to the prior art.
The anti-clumping composition H was constituted - in the proportion of 15% by weight of the product of neutralization with stearylamine of a mixture contain-ing 65% by weight of 1.3-isopropylnaphthalene sulfonic acid and 35% by weight of an acid alkylphosphate defined in composition J, - in the proportion of 60% by weight of a mineral oil and - in the proportion of 25% by weight of a macrocrystal-line wax.
The anti-clumping composition I is constituted in the same manner as composition H, with the slight diffe-rence that the 60~ by weight of mineral oil are replaced by a mixture of 57% of mineral oil and 3% of aluminum stearate.
The anti-clumping composition J is constituted 13~127 - in the proportion of 15% by weight of the product of neutralization with stearylamine of an acid alkyl-phosphate (50/50 molar mixture of mono- and diesters) of which the alkyl portion is constituted by a chain comprising essentially a mixture of C8 and of C10, - in the proportion of 60% by weight of a mineral oil and - in the proportion of 25% by weight of a macloc~ystal-line wax.
The anti-clumping compositions B, H, I et J are applied by spraying at 80C in the proportion of 0.15% by weight with respect to the fertilizer, this application being preceded by the application of an inert clay in the proportion of 0.3% by weight with respect to the ferti-lizer.
The composition according to the prior art is constituted by a doped clay with 3% by weight of stearyl-amine.
It is applied in the proportion of 0.6% by weight with respect to the fertilizer, this application being followed by the spraying of vaseline in the proportion of 0.2% by weight with respect to the fertilizer.
The treated fertilizer is packaged in polyethylene bags and is subjecteed to a clumping test in the clumping module described above. The duration of the stacking is 40 days under a pressure of 1.5 kg/cm2.
At the end of this test, the polyethylene bags are opened carefully. The clumps are weighed and the hardness of the clumps is measured by means of a dynanometer.
3o The results of these measurements are collected in Table E.
13331~77 % Hardness Clumping Treatment clumping of clumps Index 5 Doped clay with 3%
amine 0.6 % 89 79 7030 Mineral oil 0.2 %
(prior art) Clay 0.3 %
10 Composition B 0.15%
Clay 0.3 %
Composition H 0.15%
(according to the invention) Clay 0.3 %
Composition I 0.15%
(according to the invention~
Clay 0.3 %
Composition J 0.15%
This example illustrates the pontentiation of the anti-clumping properties of the two active materials constituting the composition associated with aluminum stearate.
An anti-clumping treatment is applied to ammonium nitrate titrating 33.3% and containing 4% of ammonium sulphate in the mass. The fertilizer is treated at 30C.
Four trials were carried out in which the anti-clumping treatment consisted respectively of a spraying at80C of 0.1% by weight with respect to the fertilizer of the anti-clumping compositions K, L and M described below, and of an anti-clumping composition according to the prior art constituted by a commercial aminated oil containing 18% of stearylamine and sprayed under the same conditions.
The composition K according to the invention is constituted:
- in the proportion of 22% by weight of the product of neutralization with stearylamine of a mixture contain-ing 55% by weight of a tributyl-naphthalenesulfonic acid and 45% by weight of an acid stearylphosphate (50/50 mixture of mono- and diesters), - in the proportion of 10% by weight of stearic acid, - in the proportion of 45% by weight of a paraffin oil, - in the proportion of 23% by weight of a macrocrystal-line wax.
The composition L comprises one of the two agents entering into the constitution of anti-clumping product of the compositon K.
It is constituted:
~ in the proportion of 22% by weight of the product of neutralization of a tributyl-naphthalenesulfonic acid with stearylamine, - in the proportion of 10% by weight of stearic acid, - in the proportion of 45% by weight of a paraffin oil, - in the proportion of 23% by weight of a macrocrystal-line wax.
The composition M comprises the other of the two agents entering into the constitution of the anti-clumping product of composition K. It is constituted:
Z5 - in the proportion of 22% by weight of the product of neutralization of an acid stearylphosphate (50/50 mix-ture of mono- and diesters) with stearylamine, - in the proportion of 10% by weight of stearic acid, - in the proportion of 45% by weight of a paraffin oil, 3o - in the proportion of 23% by weight of a macrocrystal-line wax.
The treated fertilizer was sub;ected to the test described in Example 1 and the same measurements were carried out. The duration of stacking was, in this case, 45 days under a pressure of 1 kg/cm2.
The results of these measurements are collected in 133~1 ~7 Table F.
TABLE F
% Hardness Clumping Treatment clumping of clumps Index Composition K 45 30 1350 (according to the invention) Composition L 95 80 7600 Composition M 95 72 6840 Commercial aminated oil67 32 2140 (according to prior art) Untreated control 100 200 20000 The results collected in Table F show that the combination according to the invention causes the appea-rance of a potentiation of the anti-clumping properties with respect to the properties of each of the constituent agents of the combination taken separately and formulated in the same manner.
An anti-clumping treatment is applied to an NPK
complex fertilizer of formula 15.11.22 known to be diff-icult to anti-clump and which is at a temperature of 35C
using, by spraying with a proportion of 0.1~ by weight with respect to the treated fertilizer, an anti-clumping composition N according to the invetnion and an anti-clumping composition according to the prior art consti-tuted by a doped clay in the proportion of 3~ by weight of stearylamine.
The composition N is constituted:
- in the proportion of 15% by weight of the product of neutralization with stearylamine of a mixture contain-ing 50% of 1.3-isopropyl-naphthalenesulfonic acid and 50% of an acid laurylphosphate (50/50 molar mixture of mono- and diesters), - in the proportion of 60% by weight of a mineral oil 21 133~127 and - in the proportion of 25% by weight of a macrocrystal-line wax.
TABLE G
% Hardness Clumping Treatment clumping of clumps Index Composition N 37 35 1300 (according to the invention) 10( 0.6% doped clay 44 47 2070 Control ( 0.2% vaseline Untreated control 100 16016000 This example illustrates the fact that acomposition according to the invention permits the elimination of the mineral coating.
Advantageously, this remarkable anti-clumping performance is accompanied by suppression of the rescattering of the dust.
An anti-clumping treatment is applied to a urea-based fertilizer granulated with a charge in the mass by using an anti-clumping composition 0 according to the invention and an anti-clumping composition according to the prior art.
The anti-clumping composition 0 is constituted:
- in the proportion of 19% by weight of the product of neutralization with stearylamine of a mixture contain-ing 75% of the 1.3-isopropyl-naphthalenesulfonic acid and 25% of an acid laurylphosphate (50/50 molar 3 mixture of mono- and diesters), - in the proportion of 5% by weight of stearic acid, - in the proportion of 53% by weight of a mineral oil and - in the proportion of 23% by weight of a macrocrystal-line wax.
The anti-clumping composition according to the 133~127 prior art is constituted by a commercial aqueous solution of an alkylsulfate associated with soluble polymer of the ethylene vinyl acetate type.
The anti-clumping compositions are sprayed on the fertilizer in the proportion of 0.1% by weight with res-pect to the fertilizer.
The test is that described in Example 1. The dura-tion of stacking was 20 days under a pressure of 1 kg/cm2.
TABLE H
% Hardness Clumping Treatment clumping of clumps Index Solution according to the prior art 100 47 4700 15 Composition 0 (according to the invention, 30 22 660 Untreated control 100 60 6000 This example illustrates the anti-clumping pro-perties of the composition according to the invention.
The composition K described in Example 5, and the formulae called "coating mixture A, B and C" described in EP Patent 113 687, were tested comparatively.
The tests were carried out on a 33.5% ammonium nitrate containing 4% of ammonium sulphate.
The treatment consisted of spraying at 80C of 0.1% by weight with respect to the fertilizer of different anti-clumping compositions.
The treated fertilizer was subjected to the test 3 described in Example 1 and the same measurements were carried out. The duration of stacking was, in this case, 45 days under a pressure of 1 kg/cm2.
The results are collected in Table I.
-133~127 TABLE I
~ Hardness Clumping Treatment clumping of clumps Index 5. Composition K
(according to the invention) 45 50 1350 Coating mixture A 100 100 10000 Coating mixture B 100 100 10000 Coating mixture C 100 100 10000 This example illustrates the decisive superiority of the anti-clumping compositions according to the inven-tion with respect to the prior art on a fertilizer having a very strong tendency to setting solid.
Claims (19)
1. Anti-clumping product for mixing with compounds essentially used as simple or complex fertilizers for preventing clumping consisting of a combination of 15 to 85% of at least one amine salt of an alkylaryl-sulfonic acid and of 85 to 15% of at least one amine salt of an acid phosphate ester, wherein the alkylaryl-sulfonic acid is selected from the group consisting of mono-, di- or trisulfonic acids in which the alkylaryl portion is selected from the group consisting of mono- and polyalky-substituted benzene and naphthalene and wherein the acid phosphates esters correspond to a formula selected from the group consisting of IMP and (I) (II) in which -R1 represent an alkylene group having from 2 to 4 carbon atoms, -R2, R3 and R4 represent an alkyl group having from 8 to 20 carbon atoms or an alkylaryl group of which the alkylated portion has from 8 to 12 carbon atoms, and -n1, n2 and n3 represent a number from 0 to 15.
2. Anti-clumping product according to claim 1, wherein said at least one amine salt of an alkylaryl-sulfonic acid is present in an amount of 30 to 70% and said at least one amine salt of an acid phosphate ester is present in an amount of 70 to 30%.
3. Anti-clumping product according to claim 1 , wherein n1, n2 and n3 represent a number from 0 to 5.
4. Anti-clumping composition for use essentially with a simple or complex fertilizer, comprising 5-35 weight-% of at least one anti-clumping product according to claim 1, further comprising an excess amine.
5. Anti-clumping product according to claim 1, wherein the alkylaryl-sulfonic acid is 1,3-isopropyl-naphthalene-sulfonic acid.
6. Anti-clumping product according to claim 1, wherein the amine salt is derived from an amine selected from the group consisting of alkylamines, cycloalkylamines, aromatic amines, alkanolamines and their oxyalkylenated homologs.
7. Anti-clumping product according to claim 6, wherein the amine is an alkylamine in which the number of carbon atoms is from 12 to 20.
8. Anti-clumping product according to claim 6, wherein the amine is a technical stearylamine.
9. Anti-clumping composition according to claim 4, comprising an excess of amine which is less than 25% molar.
10. Anti-clumping composition for use essentially with a simple or complex fertilizer, comprising 5-35 weight-%
of at least one anti-clumping product according to claim 1 and at least one formulation agent selected from the group consisting of mineral oils and the mixtures of the latter with macrocrystalline waxes.
of at least one anti-clumping product according to claim 1 and at least one formulation agent selected from the group consisting of mineral oils and the mixtures of the latter with macrocrystalline waxes.
11. Anti-clumping composition for use essentially with a simple or complex fertilizer, comprising 5-35 weight-%
of at least one anti-clumping product according to claim 1, at least one other anti-clumping product selected from the group consisting of fatty acids and their salts and at least one formulation agent selected from the group consisting of mineral oils and the mixtures of the latter with macrocrystalline waxes.
of at least one anti-clumping product according to claim 1, at least one other anti-clumping product selected from the group consisting of fatty acids and their salts and at least one formulation agent selected from the group consisting of mineral oils and the mixtures of the latter with macrocrystalline waxes.
12. Anti-clumping composition for use essentially with a simple or complex fertilizer, comprising 5-35 weight-%
of at least one anti-clumping product according to claim 1, at least one other anti-clumping product selected from the group consisting of fatty acids having 12 to 20 carbon atoms and their salts and at least one formulation agent selected from the group consisting of mineral oils and the mixtures of the latter with macrocrystalline waxes,
of at least one anti-clumping product according to claim 1, at least one other anti-clumping product selected from the group consisting of fatty acids having 12 to 20 carbon atoms and their salts and at least one formulation agent selected from the group consisting of mineral oils and the mixtures of the latter with macrocrystalline waxes,
13. Anti-clumping composition for use essentially with a simple or complex fertilizer, comprising 5-35 weight-%
of at least one anti-clumping product according to claim 1, another anti-clumping product consisting of stearic acid or its salts and at least one formulation agent selected from the group consisting of mineral oils and the mixtures of the latter with macrocrystalline waxes.
of at least one anti-clumping product according to claim 1, another anti-clumping product consisting of stearic acid or its salts and at least one formulation agent selected from the group consisting of mineral oils and the mixtures of the latter with macrocrystalline waxes.
14. Anti-clumping composition for use essentially with a simple or complex fertilizer, comprising 5-35 weight-%
of at least one anti-clumping product according to claim 1, at least one other anti-clumping product selected from the group consisting of the salts of calcium, magnesium and aluminum, of stearic acid in which the molar ratio aluminum/stearic acid is close to 2, and at least one formulation agent selected from the group consisting of mineral oils and the mixtures of the latter with macrocrystalline waxes.
of at least one anti-clumping product according to claim 1, at least one other anti-clumping product selected from the group consisting of the salts of calcium, magnesium and aluminum, of stearic acid in which the molar ratio aluminum/stearic acid is close to 2, and at least one formulation agent selected from the group consisting of mineral oils and the mixtures of the latter with macrocrystalline waxes.
15. Anti-clumping composition, comprising:
-from 5 to 35% by weight of the anti-clumping product according to claim 1, -from 0 to 10% of a fatty acid or of one of its salts, -from 20 to 90% by weight of a mineral oil and -from 0 to 50% by weight of macrocrystalline wax.
-from 5 to 35% by weight of the anti-clumping product according to claim 1, -from 0 to 10% of a fatty acid or of one of its salts, -from 20 to 90% by weight of a mineral oil and -from 0 to 50% by weight of macrocrystalline wax.
16. A method for treating products essentially used as simple or complex fertilizers in order to prevent the clumping of said products, comprising the steps of:
a) preparing a product for use essentially as a fertilizer including discharging the product from a preparation zone after the product has substantially acquired its final mechanical properties, and b) substantially at the moment of discharge, incorporating into the product a composition comprising at least one amine salt of an alkylaryl-sulfonic acid and at least one amine salt of an acid phosphate ester, and wherein the incorporating step is effected by spraying on the product an amount of the composition of 0.03 to 0.4% by weight with respect to the product and wherein the composition comprises:
a) from 5 to 35% by weight of a combination of 15 to 85% of at least one amine salt of an alkylaryl-sulfonic acid and of 85 to 15% of at least one amine salt of an acid phosphate ester, wherein the alkylaryl-sulfonic acid is selected from the group consisting of mono-, di- or trisulfonic acids in which the alkylaryl portion is selected from the group consisting of mono- or polyalkyl-substituted benzene and naphthalene and wherein the acid phosphates esters correspond to a formula selected from the group consisting of and (I) (II) in which -R1 represents an alkylene group having from 2 to 4 carbon atoms, -R2, R3 and R4 represent an alkyl group having from 8 to 20 carbon atoms or an alkylaryl group of which the alkylated portion has from 8 to 12 carbon atoms, and -n1, n2 and n3 represent a number from 0 to 15;
b) from 0 to 10% of a fatty acid or of one of its salts;
c) from 20 to 90% by weight of a mineral oil; and d) from 0 to 50% by weight of macrocrystalline wax.
a) preparing a product for use essentially as a fertilizer including discharging the product from a preparation zone after the product has substantially acquired its final mechanical properties, and b) substantially at the moment of discharge, incorporating into the product a composition comprising at least one amine salt of an alkylaryl-sulfonic acid and at least one amine salt of an acid phosphate ester, and wherein the incorporating step is effected by spraying on the product an amount of the composition of 0.03 to 0.4% by weight with respect to the product and wherein the composition comprises:
a) from 5 to 35% by weight of a combination of 15 to 85% of at least one amine salt of an alkylaryl-sulfonic acid and of 85 to 15% of at least one amine salt of an acid phosphate ester, wherein the alkylaryl-sulfonic acid is selected from the group consisting of mono-, di- or trisulfonic acids in which the alkylaryl portion is selected from the group consisting of mono- or polyalkyl-substituted benzene and naphthalene and wherein the acid phosphates esters correspond to a formula selected from the group consisting of and (I) (II) in which -R1 represents an alkylene group having from 2 to 4 carbon atoms, -R2, R3 and R4 represent an alkyl group having from 8 to 20 carbon atoms or an alkylaryl group of which the alkylated portion has from 8 to 12 carbon atoms, and -n1, n2 and n3 represent a number from 0 to 15;
b) from 0 to 10% of a fatty acid or of one of its salts;
c) from 20 to 90% by weight of a mineral oil; and d) from 0 to 50% by weight of macrocrystalline wax.
17. A method according to claim 16, wherein the amount of said composition incorporated is from 0.005 to 0.05% by weight with respect the product.
18. A composition comprising a material essentially used as a fertilizer and an anti-clumping product according to claim 1 in an amount from about 0.005% to about 0.05% by weight with respect to the amount of said material.
19. A composition according to claim 18, further including a charge selected from the group consisting of chalk, infusorial earth, talc and clays.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8804614 | 1988-04-07 | ||
| FR8804614A FR2629815B1 (en) | 1988-04-07 | 1988-04-07 | ANTIMOTANT PRODUCTS, COMPOSITIONS AND TREATMENTS FOR SALTS, SIMPLE AND COMPLEX FERTILIZERS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1333127C true CA1333127C (en) | 1994-11-22 |
Family
ID=9365074
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000595995A Expired - Lifetime CA1333127C (en) | 1988-04-07 | 1989-04-07 | Anti-clumping products, compositions and treatments for salts, simple and complex fertilizers |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0341102B1 (en) |
| AT (1) | ATE77813T1 (en) |
| CA (1) | CA1333127C (en) |
| DE (1) | DE68901948T2 (en) |
| ES (1) | ES2032662T3 (en) |
| FI (1) | FI95238C (en) |
| FR (1) | FR2629815B1 (en) |
| GR (1) | GR3005222T3 (en) |
| NO (1) | NO179202C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2687933B1 (en) * | 1992-02-28 | 1994-05-20 | Cfpi | ANTIMOTTANT PRODUCTS, COMPOSITIONS CONTAINING SUCH PRODUCTS AND TREATMENTS USING SUCH PRODUCTS. |
| FR2701408B1 (en) * | 1993-02-16 | 1995-04-21 | Prod Ind Cfpi Franc | Composition and anti-clumping process for fertilizers. |
| FR2722427B1 (en) * | 1994-07-13 | 1997-01-24 | Francais Prod Ind Cfpi | PROCESS FOR THE TREATMENT OF FERTILIZERS TO COMBAT MOISTURE RECOVERY |
| FR2724851B1 (en) | 1994-09-26 | 1997-01-17 | Francais Prod Ind Cfpi | SIMULTANEOUSLY ANTIMOTTANT AND WATERPROOFING COMPOSITION FOR SALTS, SINGLE AND COMPLEX FERTILIZERS AND METHOD FOR IMPLEMENTING SAME |
| ES2121694B1 (en) * | 1996-10-08 | 1999-09-16 | Kao Corp Sa | ANTI-HAIR COMPOSITIONS FOR SOLID GRANULAR FERTILIZERS, THEIR USE AND METHOD OF APPLICATION THEREOF. |
| US6475259B1 (en) * | 1999-10-29 | 2002-11-05 | Mississippi Chemical Corporation | Coating agent and coated particulate fertilizers |
| WO2003006399A1 (en) | 2001-07-10 | 2003-01-23 | Holland Novochem B.V. | Fertilizer granules containing ammonium nitrate |
| ES2319367B1 (en) * | 2007-07-03 | 2010-01-12 | Kao Corporation, S.A. | ANTIAPELMAZANTES COMPOSITIONS FOR FERTILIZERS. |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB742636A (en) * | 1952-12-08 | 1955-12-30 | Nitroglycerin Ab | A method of treating ammonium nitrate for reducing or preventing its tendency to cake |
| FR2460706A1 (en) * | 1979-07-13 | 1981-01-30 | Produits Ind Cie Fse | ANTIMOTTANT PRODUCTS AND TREATMENTS BASED ON AMINE SALTS |
| NL8300043A (en) * | 1983-01-06 | 1984-08-01 | Azote Sa Cie Neerlandaise | AMMONIUM NITRATE CONTAINING FERTILIZER GRANULES AND COATING MIXTURE THEREFOR. |
| SU1131859A1 (en) * | 1983-07-08 | 1984-12-30 | Предприятие П/Я Р-6603 | Method for preventing caking of ammonia sulpetre |
| FR2575084A1 (en) * | 1984-12-24 | 1986-06-27 | Produits Ind Cie Fse | METHOD AND COMPOSITION FOR ANTIMOTTING SALTS OR NON-POWDERY FERTILIZERS |
-
1988
- 1988-04-07 FR FR8804614A patent/FR2629815B1/en not_active Expired - Lifetime
-
1989
- 1989-04-04 DE DE8989400923T patent/DE68901948T2/en not_active Expired - Lifetime
- 1989-04-04 AT AT89400923T patent/ATE77813T1/en not_active IP Right Cessation
- 1989-04-04 EP EP89400923A patent/EP0341102B1/en not_active Expired - Lifetime
- 1989-04-04 ES ES198989400923T patent/ES2032662T3/en not_active Expired - Lifetime
- 1989-04-06 FI FI891647A patent/FI95238C/en not_active IP Right Cessation
- 1989-04-06 NO NO891423A patent/NO179202C/en not_active IP Right Cessation
- 1989-04-07 CA CA000595995A patent/CA1333127C/en not_active Expired - Lifetime
-
1992
- 1992-07-16 GR GR920401553T patent/GR3005222T3/el unknown
Also Published As
| Publication number | Publication date |
|---|---|
| FI891647A0 (en) | 1989-04-06 |
| NO179202B (en) | 1996-05-20 |
| DE68901948D1 (en) | 1992-08-06 |
| NO891423L (en) | 1989-10-09 |
| FI95238B (en) | 1995-09-29 |
| FI95238C (en) | 1996-01-10 |
| FR2629815B1 (en) | 1991-10-18 |
| EP0341102B1 (en) | 1992-07-01 |
| FI891647A (en) | 1989-10-08 |
| FR2629815A1 (en) | 1989-10-13 |
| ES2032662T3 (en) | 1993-02-16 |
| ATE77813T1 (en) | 1992-07-15 |
| EP0341102A1 (en) | 1989-11-08 |
| NO179202C (en) | 1996-08-28 |
| NO891423D0 (en) | 1989-04-06 |
| GR3005222T3 (en) | 1993-05-24 |
| DE68901948T2 (en) | 1993-02-04 |
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