DE1467381A1 - Process for the production of non-dusting and non-caking, easily storable fertilizers - Google Patents

Description

Badische Anilin- & Soda-Fabrik AG

P 14 67 581.5 February 15, 1963

Ludwigshafen / Rheinj

OZ 22 315 June 3, 1968 BR / Da

Process for the production of non-dusting and non-caking, easily storable fertilizers

When storing mineral fertilizers, in particular those that contain hygroscopic components, the individual fertilizer grains or salt crystals stick together. This makes the handling very difficult and can lead to a complete Hardening of the initially loosely positioned control room »

To eliminate this disadvantage it has long been known that the fertilizer grains can be covered with a protective layer of a finely divided or powdery substance that is suitable for a mutual contact of the hygroscopic salt surface prevent and possibly absorb a certain amount of moisture can. For example, kieselguhr, clay or finely divided lime are used as "powdering agents" for this purpose. The powdered ones However, fertilizers only have a limited shelf life; in addition, they show an annoying dust when handling, by a Part of the applied amount of powder is rubbed off again. Also through the use of substances with adhesive properties

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or 'network properties to promote adhesion of the powder to the Dtingergranalien, dusting can not be completely eliminated "Another laughing part of powdering is that the nutrient content of the fertilizer by the inert portion, which is up to 6 $ powder decreases _o

There has been no lack of attempts to replace the "powdering" of fertilizers with a suitable other measure.

For example, attempts have been made to achieve an "anti-caking" effect by adding surface-active substances to the fertilizer grains. Z ₀ B ₀ condensation products of formaldehyde with aryl sulfonic acids or their salts, condensation products of higher alcohols with ethylene oxide, fatty amines and derivatives etc "(vglo French patent specification 1" 100 686, English patents 743 600 and 800 794, Belgian patent specification 606 734) ο Such compounds should give a water-repellent layer on the granules and prove to be effective even in small amounts. However, you cannot prevent the air humidity from affecting the fertilizer while it is being stored. That is why it is necessary to powder the fertilizer treated in this way. "

It is also known that in order to prevent the caking of fertilizers, the surfaces of the granules with for example paraffin oil, tar oil, vegetable oils, petroleum jelly or Wax or coated with mixtures of such compounds

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(cf. e.g. French patents 734 728 and 1 016 367, Austrian patent 168 833, Swiss patent 202 254, English patent 583 388, US patents 2,118,438 and 2,399,987, German patent 1,062 713 and German patent specification 1,137,049 ) "but such oils exhibit a low tendency to adhere to the salt-like Dtingerkörnern so that their effectiveness is lost through attrition partially again" even they can from the porous salt surface partially or completely absorbed, so that the protection is "layer destroyed _e Finally, even with Use of these substances in many cases an additional powdering with finely divided substances is recommended «

If you want to do without powder at all, a relatively large amount of a film-forming compound must be added to the fertilizer, from Z ₉ B _{9 more than $ 1.} One uses ζ _β Β _β urea-formaldehyde condensates or other resins or plastics, such as, for example, polyoxyalkylenes (cf., inter alia, US Patents 2,502 and 2,734,002, Belgian Patent 600,133). The application of larger quantities is both technically and economically unfavorable, continues to reduce the nutrient content of the treated fertilizer, is in view of; dangerous to nitrate fertilizers and can also have an unfavorable effect on the solubility and rapid effect of the fertilizer salts »

A protective layer on fertilizer granules with the help of synthetic polymerization products of diolefins is mentioned in English patent 359 163. However, let's see

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The customary, commercially available polymers of this type are only used to a limited extent for the purpose described, since they It takes a very long time to harden on fertilizer granulate in a stream of hot air and the same when it has not hardened, above like other hydrocarbons, e.g. paraffin. This means that there is no sufficiently effective "antiback" Effect. The same applies to the herbal drying agents proposed in US Pat. No. 1,648,861 evil.

It has now been found that there are non-dusting and non-caking Fertilizers by coating fertilizers with drying oily substances and drying the coatings in particular advantageously obtained when the fertilizer is 0.01 to 0.6 percent by weight, based on the amount of fertilizer, drying applies oily polyene polymers that are isomerized and / or made reactive by passing air or oxygen through them and the coatings dry in the usual way.

Surprisingly, with the reactive polyene polymers used according to the invention in amounts of 0.05 to 0.1 $>, based on the weight of the fertilizer, an almost completely enveloping, thin protective layer curable in a short time is obtained on the granulate Prevents air humidity from reaching the hygroscopic fertilizer salt and makes crystal growth between the surfaces of the individual grains impossible. This achieves the intended purpose of preventing the grains from being too aaanaaenbaoken. In some

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_O cases is already accessible by 0 _r 01 to _O9 I 5 ^ favorable "anticaking ¹ '-Wirkung Specifically, the optimum amount depends on the composition of the reactive polyene polymer used and on the hygroscopicity of the fertilizer to be treated from ₀

A particular advantage of the process is that you can do without the use of powder materials and completely dust-free product receives “Of course it is also possible, in addition To apply powder materials,

The excellent film-forming ability of the reactive polyene polymers used in the process according to the invention is attributable to the fact that the polyene polymers which have been made reactive are initially distributed in the liquid phase over the grain surface and then rapidly harden _{or the like}

Suitable drying, reactive oily or plastic polyene polymers are obtained, for example, by polymerizing dienes or greens, such as isoprene, piperylene, cyclopentadiene, cyclohexadiene _S 3 or, preferably, butadiene, 3 = methylheptatriene "1j, 4i> £? N-decatriene" j = 1, 5j9 or copolymerization of one or more polyenes with up to 50 G-ewi chtsprozent mischpolymerisier- 'Barer compounds such as ethylene, propylene, butylene. isobutylene, vinyl acetylene and preferably styrene and acrylonitrile, and by treatment of the polymers or copolymers of _o , which makes the polyene polymers so reactive that they are in

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dry for a short time.

Ala such treatment is particularly an isomerization of the oily polyene polymers at a higher temperature in question, preferably in the presence of small amounts of transition metals of VI. to VIII. Group of the Periodic Table of the Elements and / or of compounds in which these metals are present in the zero-valent state, as described in the German patent (B 69 075 IVd / 39c) for polybutadiene. This treatment probably causes a shift in the double bonds in the polyene polymers. As a result, the polyene polymers are made more accessible to crosslinking reactions and the reaction with oxygen. As a result, such isomerized polyene polymers can harden particularly quickly. The curing times are about 5 to 15 times shorter than with non-isomerized polyene polymers.

The polyene polymers used according to the invention can can also be made reactive by passing air or oxygen through, optionally with heating and / or addition of transition metal or heavy metal compounds. Finally, the polyene polymers can also be used during or after the addition are isomerized to fertilizers "on the grain". Also in this Pail are catalysts based on transition and Heavy metals or their compounds in question, such as iron carbonyls, elemental copper, manganese salts, lead compounds, such as tetraethyl lead, cobalt and nickel salts, such as cobalt naphtha

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Uickelacetylacetonat ete

The oily or plastic reactive polyene polymers used according to the invention can also contain 50 percent by weight of other polymers that cannot be further polymerized, such as polystyrene or polyacrylonitrile ; such as styrene, or acrylic «= nitrile, are added _o

The average molecular weights of the polyene polymers used in this invention are in general 500-40 OQOo However, it _s can be also products with smaller -mittleren 'molecular weights used provided that the resulting higher vapor pressure "d ₀ h ₀ the higher combustibility or explosiveness of the (Jasatmosphäre Above- "the- good does not interfere _o On the other hand, polyene polymers with medium molecular weight

then th of more than 40,000 used "But you have to / with higher viscosities expected in processing _o

The drying time, which is shortened by the use of particularly reactive oily polyene polymers, can be reduced even further by adding catalysts to the polymers before, during or after the addition to the fertilizer ^ r = fχγά, ϋ s azo compounds or heavy metal compounds -

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possibly in combination with radical formers - in question. Transition metal compounds are also suitable

As a fertilizer, which is obtained by applying the reactive polyene polymers Inorganic salts, for example, should be made stable, non-dusting and non-caking or salt mixtures, the alkali metals, alkaline earth metals or ammonium as a cation, phosphates, nitrates, chlorides, or sulfates Containing carbonates as anions, or urea, derivatives of urea or urea salts in embossing «, such fertilizers can also contain parts of eye metals or transition metals, such as copper, manganese, zinc or their salts. Finally, they can be wholly or partly animal or vegetable more likely to be origin «,

To the fertilizers, which generally granulated or lumpy admitting the reactive oily or plastic polyene polymers are _v let the normally present in fertilizer production plants devices, such as stirrers, a fluidized bed apparatus, vibrating feeders, vibrating screens j auger, Hauer son corners Fallschäehte and spray towers, in particular, however, use rotating drums, with or without internals, "The reactive polyene polymers can be added in a particularly simple manner as a liquid jet". They distribute themselves on the surface of the item to be treated ", but they can also be used in the form of fine droplets or as an aerosol in order to achieve an optimum of even distribution"

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The working temperature is at room temperature or elevated temperature up to 30O ⁰ C _8, preferably 50 to 160 ⁰ C ₉ It is recommended to generate the increased temperatures in the apparatus with a stream of hot air, because at the same time the amount of oxygen required for hardening is supplied becomes =

In all cases, fertilizers are obtained which have excellent storage stability are, even under unfavorable weather conditions, that show no tendency to cake and that are perfect can be handled dust-free ^

Other advantages of the new method are as follows

The use of organic solvents can be avoided * The residence time of the fertilizer granules in the apparatus, in to which the reactive polyene polymers are added can be kept very small,

The amount of reactive polyene polymers used is in economically favorable limits and has practically no influence on the speed of dissolution of the fertilizer grains by the soil water * The protective layer formed on the fertilizer grains is unlike that produced by known processes abrasion resistant *

The parts and percentages given in the following examples are, unless otherwise stated, units of weight.,

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General test of the tendency to caking %

Pressed cubes are produced from the fertilizer granulate or salt to be tested for storage stability or tendency to caking; The granulate or salt is exposed to a force of 175 kg in a metallic cube form with a side surface of 50 cm for two hours at constant room temperature and humidity _o The weight which is necessary to destroy the pressed part "is indicated by the apparatus". It is a measure of the tendency of the fertilizer salt investigated to stick together.

Yon a granular fertilizer (composition ^ Έ / Pp ° 5 / Kp ^{0 r:} 13/13/21) ^{of the} Korndur --hm it se rs 2 to 4 mm who to, as described, produced and this machine 10 Preßwürfel _a smashed The The shattering value for a cube with a ^{side area of 50 cm 2} is on average 210 kg _{or the like}

Example 2

The granular fertilizer used in Example 1 is "powdered" with 0.5 $ kieselguhr "The destruction of value for a Preßwürfel of 50 cm side surface is on average 116 kg ₀

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Example 3

The fertilizer granules used in Example 1 is with a treated aqueous solution of a surface-active alkyl sulfonate, so that 0.1 $ of this substance on the surface of the Granules adhere, and then dried. As described, 10 pressed cubes are produced and their average fragmentation value determined "Br is 142 kg"

Example 4

The granular fertilizer used in Example 1 is then treated first as in Example 3 according to Example 2 so that 0.1 # surfactant alkyl sulfonate and 0.5 $ diatomaceous adhere to its surface "The Preßwürfel give a, medium destruction value of 71 kg _E

The fertilizer granulate used in Example 1 is $ 0.2 liquid paraffin treated «The pressed cubes have an average crush value of 112 kg«

Example _m 6

The granular fertilizer used in Example 1 is in a rotating drum with 0.2 # isomerized polybutadiene having an average molecular weight of 4: 000, cryoscopically determined treated The thin polybutadiene Pilm, which has formed on the surface of the grains, is at 110 ⁰ C with hot =

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air dried in 10 minutes The pressed cubes have an average crushing value of 3 kg _e

Example 7

According to Example 6 is the same polybutadiene, which has not been pretreated by isomerization, given in an amount of 0.2 $ .. After 10 minutes, hot air treatment at 110 ⁰ C, the protective layer on the fertilizer granules is oily and is not hardened or _o dried The pressed cubes show an average crush value of 123 kg «

B_example __8

The granular fertilizer used in Example 1 (about average molecular weight 8000) treated in a vibrating trough at 120 ⁰ C with 0.15 $> reactive homemade by isomerization polyene polymer 'consisting of 80 $ butadiene and 20 $ styrene and the oily protective layer cured at 120 ⁰ C by blowing hot air Härtungszeits 7 minutes "the Preßwürfel show a disintegration value of <1 kg d" h ", the dice decompose by itself in the removal from the mold *

Example Q /

The isomerized polybutadiene oil used in Example 6 is added to a Mefcge'Yon '0 ^ 2 fi & xg-elv & n multi-nutrient fertilizer of the composition U / P ₂ Oc / KgO - ■■ 15/15/15 of the grain size 2 bit 4-mm and in the rotary drum with hot air at 11O ⁰ C in 8 minutes hardened the mean value of the disintegration Preßwürfel is 13 kg of _o

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The procedure “as stated in Example 8, but using a multi-nutrient fertilizer granulated to a grain size of 2 to 4 mm and having the composition Έ / P ₃ O ₅ / K ₂ O ---- 12/12/20” is used 5 kg *

"Beis piel 11

From a prilled calcium ammonium nitrate 64 f <> Ammonnitrat- and 36 fa Galeiumcarbonat content, particle size 2 mm to 3, 10 Preßwürfel be prepared "The destruction of value for a cube of 50 em ² side surface is on average 580 kg _e

Example 13

As in Example 12, 0.1 $ reactive, isomerized Polybutadiene oil applied to lime ammonium nitrate »The shattering value a pressed cube is on average 7 kg.

Example 14

The lime ammonium nitrate used in Example 11 is made according to Example 6 with polybutadiene oil. isomerized, in amounts of 0.2; 0.3i 0.4 * 0.5 and 0.6 treated "In all cases the crushing value of the pressed cubes is <1 kg _s d _u h _o , the cubes disintegrate by themselves when they are removed from the mold"

Crystalline potassium chloride is found in an untreated condition

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checked his inclination to cheek. The pressed cubes show shattering. values between 150 and 220 kg. According to Example 6, the potassium chloride is treated with 0.05% isomerized polybutadiene oil. The pressed cubes produced with the treated product show an average crush value of 21 kg.

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Claims (2)

- 15 - O.Z. 22 515 Claims ■ 1 J process for the production of non-dusting and non-caking fertilizers by coating fertilizers with drying oily substances and drying the coatings, characterized in that the fertilizers 0.01 to 0.6 percent by weight, based on the amount of fertilizer, drying oily Applies polyene polymers that have been isomerized and / or made reactive by passing air or oxygen through them, and the coatings are dried in the usual way. 2. The method according to claim 1, characterized in that one applies to the fertilizers 0.01 to 0.6 percent by weight, based on the fertilizer amountj drying oily polyene polymers which in the presence of transition metals of VI. to VIII. Group of the Periodic Table of the Elements and / or of compounds in which these metals are present in the zero-valent state, have been isomerized, and the coatings are dried in the usual way. Badische Anilin- & Soda-Fabrik AG * U6 Ϊ interfesen IAH. 7 g ι From ₈ .2 No. 1 sentence 3 of the amendment «. * 4.9.1 * 67} twofold 80980 9/0947