Classifications

• • 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
  • C05G5/00—Fertilisers characterised by their form
  • C05G5/30—Layered or coated, e.g. dust-preventing coatings
• • 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
  • C05G5/00—Fertilisers characterised by their form
  • C05G5/30—Layered or coated, e.g. dust-preventing coatings
  • C05G5/37—Layered or coated, e.g. dust-preventing coatings layered or coated with a polymer

Definitions

• Salts are used, inter alia, as fertilizer and drying agent or as additive for foods, cleaning agents and the production of glass and porcelain.
• inorganic salts Before it reaches its final use, inorganic salts often undergo a long-term storage and/or intercontinental transport. Therefore, granulate should not cake together, absorb moisture and/or form dust. In order to obtain robust granulates, small amounts of chemicals are added to the salts.
• a known example is prussiate of potash for sodium chloride (see e.g. US 3.174.825) .
• Coatings on the basis of oil and paraffins have been examined very intensively and several compositions are claimed (see e.g. WO 03/006399 and references therein) .
• the power is that these coatings mostly give an excellent performance in very low doses.
• Commonly used amounts are between 0.05 and 0.15 percent by weight, based on the weight of the treated fertilizer.
• Cake formation of ammonium nitrate-containing fertilizers can be reduced by using polyalkylene glycols as coating (GB 1.026.023).
• Most polyalkylene glycols are soluble in water, low-toxic and biodegradable.
• the optimum dose is between 0.3 and 1.0 percent by weight, based on the weight of the treated fertilizer. This is considerably higher than common with oil- paraffin-containing products.
• water-soluble biodegradable polymers can be used, inter alia, as coating for the so-called “slow-release” fertilizers, i.e. that the plant nutrients are released slowly to the soil through slow decomposition of the coating (DE 198 20 297-A1) .
• the effect is only realized when relatively large amounts of coating (1-10% based on the weight of the treated fertilizer) are applied.
• Cake formation of the final product can be limited by adding inert powder, such as talc.
• Another process for obtaining "slow release” fertilizers has been reported in JP 8-277191.
• initially water-soluble coatings are made insoluble by heating at 200 0 C. Because of that, cross-linking of the polymers takes place (cross-linking) . Due to the required heating (and the subsequent cooling) , this process is not profitable for bulk processes.
• the caking tendency of sodium chloride can be reduced strongly by treating it with metal complexes of hydroxyl poly carboxylic acids, preferably an iron complex of meso-tartaric acid (WO 00/59828) .
• metal complexes of hydroxyl poly carboxylic acids preferably an iron complex of meso-tartaric acid (WO 00/59828) .
• These compounds prove not to satisfy as treating agent for granulate with a strong tendency of lump formation and/or moisture absorption, such as most kinds of fertilizer, for example NPK 1 s, urea and ammonium nitrates.
• Another approach has been reported in WO 01/38263 and
• WO 02/090295 a part of the paraffin and oil has been replaced by natural oils, such as rapeseed oil.
• natural oils such as rapeseed oil.
• the products are inherently biodegradable, but still contain mineral oil or derivatives thereof.
• natural oils are sensitive to polymerization and oxidation, causing it to be only limitly imperishable.
• GB-A-I 217 106 describes a process for reducing of caking of urea by using a polyvinyl alcohol having a high molecular weight as an additive in order to prevent caking. More particularly, according to this process, an aqueous solution of the additive is mixed with an aqueous solution of urea.
• an amount of additive of 0.005 to 5 % by weight, based on the weight of the urea is admixed.
• concentration of the aqueous urea solution is initially 80%, according to the example given; after admixing the solution of the additive, concentration to 95% takes place at increased temperature, after which one lets the urea crystallize through cooling.
• concentration to 95% takes place at increased temperature, after which one lets the urea crystallize through cooling.
• concentration to 95% takes place at increased temperature, after which one lets the urea crystallize through cooling.
• WO 02/20471 mentions a process wherein a combination of a polyvinyl compound and inorganic salts are mixed with urea melt. The crushing strength as well as the impact resistance of the obtained granulate prove to be improved in comparison with untreated urea.
• US 4,063,919 describes a fertilizer composition containing a polyvinyl alcohol and a plasticizer for the polyvinyl alcohol, wherein this plasticizer is preferably chosen from glycerol, sorbitol, glycol, polyglycols having A- 20 C-atoms, and mixtures thereof.
• this plasticizer is preferably chosen from glycerol, sorbitol, glycol, polyglycols having A- 20 C-atoms, and mixtures thereof.
• mannitol and sucrose are mentioned as plasticizers in this publication.
• sorbitol, mannitol and sucrose are sugars, they are referred to as polyglycols in this publication.
• sugars will colour at increased temperatures (> 100 0 C), the so-called caramelizing.
• the presence of small polar substances can result in higher hygroscopicity of urea, as a result of which recrystallization can take place and consequently the dust formation will increase drastically.
• the object of the invention is to provide a free-flowing, mineral oil-free granulate of a plant auxiliary agent, as well as a process for manufacturing the same.
• Another object of the invention is the use of residual flows of natural origin, preferably vegetable waste flows, such as corn and wheat residues, as additive for plant auxiliary agents, such as fertilizer.
• the products can be added in the melting phase of the granulation process or on the produced granules after the granulation.
• Another object of the invention is the use of a particular polyoxy ethylene-containing organic component having an HLB value between 2 and 11 as additive for plant auxiliary agents, such as fertilizer.
• the invention relates to free-flowing, mineral oil-free, granulate particles of a plant auxiliary agent, consisting of the reaction product of a nitrogen-, phosphor- and/or potassium-containing plant auxiliary agent and a nitrogen compound (s) -containing waste flow of natural material.
• the plant auxiliary agent is preferably a urea- or ammonium nitrate-containing fertilizer; whereas the waste flow preferably originates from the starch preparation from products such as corn, wheat, soy, barley and potatoes.
• the protein and/or amino acid content of the waste stream to be used can be supplemented with a protein-rich or amino acid-rich source, such as soy protein, or chicken egg protein.
• the invention also relates to the preparation of said granulate particles by treating the granules with a nitrogen- rich additive of natural origin at increased temperature.
• the additive (s) is (are) mixed in a polar solvent, if desired. If desired, this solvent, if present, can be removed after adding the additive solution according to a way known per se. It is noted that the treatment according to the invention can be applied for crystals, granules and prills; for simplification, the invention is explained by means of granules .
• the new additive is a natural waste flow of vegetable origin from the group of corn, potatoes, wheat, barley, soy, which preferably has a protein and amino acid content of more than 10% (w/w) , in particular granular corn derivatives.
• the (co) polymer is preferably synthesized of 2 to 2,000,000 units.
• the tendency of lump formation can be further reduced by adding (preferably) linear alkyl alcohols (ClO- C30), preferably C16-C22 alcohols to the granulate of a plant auxiliary agent.
• linear alkyl alcohols ClO- C30
• C16-C22 alcohols preferably C16-C22 alcohols
• a biodegradable ethoxylated organic component can be added, which has a HLB value between 2 and 11.
• the moisture absorption by granulate particles can be further reduced by adding a linear alkane having an alkyl chain length between C16 and C40, which has a solidification range between 50 and 10 0 C.
• Coatings on the basis of natural waste flows are known per se and are used for example in the paper industry (see US 2002/0121222) .
• corn products can serve as coating for tableware and cutlery (CN 1458189) .
• Vegetable waste flows are in some cases used as a fertilizer. In that way, maize gluten promote the growth of grass, but inhibit the formation of weed (US 5030268).
• Patent GB 8150829 claims an effect of a protein-rich polymer as a treating agent for fertilizer.
• the fertilizer is first provided with an inorganic layer.
• Patent GB 2110518 mentions the use of a water-soluble protein of natural origin and a metal salt as part of a hydrophilic, water-insoluble bioactive coating for the protection of plants and seeds.
• polyvinyl amine can be used as part of laminating films (EP 0 644 247) .
• Compositions with polyvinyl amine-graft polymers are claimed as treating agent for textile (WO 02/095122) .
• Polyvinyl amine can even be added as polyelectrolyte to fertilizer in order to condition soil (GB 734 504).
• Polyallyl amine can be used as coating on e.g. textile in order to absorb harmful gases (WO 93/17760) .
• Polyaspartic acid can serve as a surface coating for medicines and food (US 5.175.285). Besides, polyaspartic acid, in combination with fertilizer, can enhance the productivity of the plant (US 5,861,356)
• polyalkenyl amines and polyaspartic acid are the good biodegradability, relatively low toxicity and good irascibility with water. Use of these products as additive for salts will therefore result in a much lower burden for the environment relative to the current situation: badly water- soluble, toxic fatty amines in oil and/or paraffins.
• Coating products on the basis of (modified) polyalkylene alcohols are known per se.
• GB 1 383 444 describes the use of mixtures of polyalkylene alcohols and a surface active substance as coating for fertilizer for reducing lump and dust formation during storage and handling.
• a biodegradable ethoxylated organic component is added, which has a HLB value between 2 and 11.
• polyoxy ethylenes on fertilizer has been reported (DE 2330847) per se. However, these compounds are mixed with mineral oil, of which the use can however be overcome by the present invention. Polyoxy ethylenes are also used as a part of compositions for coatings, which can establish controlled release of particular agrochemicals in fertilizers (see e.g. JP 2003081705).
• the moisture absorption of inorganic salts can be further reduced by coating the granules with a mixture consisting of residue flows of natural origin and linear alkanes. Adding linear alkanes to salt granulate is known per se (WO03/006399) , but then it relates to a fully apolar medium, consisting of paraffin and oil. However, no combinations with natural residue products are claimed.
• the molten plant auxiliary agent results in a significant decrease of the compressibility and the tendency of caking of the granulate being formed thereafter. Moreover, the granulate is not sensitive to recrystallization by moisture absorption during storage and handling.
• the natural waste materials can be added to the molten plant auxiliary agent either separately or together with the polyalkenyl compound, whether or not as an aqueous mixture or solution. According to a preferred embodiment, the total added amount of the natural waste material is at most 10% b.w., based on the total amount of plant auxiliary agent. It is noted that the treatment according to the invention can be applied to all kinds of grains, such as crystals, granules or prills.
• the new additive is a waste flow of natural origin, particularly of vegetable origin, such as maize, potatoes, wheat, barley, soy, which preferably has a protein and/or amino acid content of more than 10% (w/w) , in particular granular maize derivatives.
• the (co) polymer is preferably synthesized of 2 to 2,000,000 units.
• use is made of polyvinyl alcohol and/or polyvinyl amine and/or polyaspartic acid.
• the invention therefore relates to a urea composition as defined in the accompanying claims which has a reduced compressibility, tendency of cake formation and dust formation through recrystallization, compared with a common urea composition.
• the granulate (1.0 kilogram per sample) is kept in sealed plastic jars in an oven at 35 0 C for 16 hours.
• the treatment takes place as follows: the granulate is brought into a rotating coating drum, which has a temperature of about 5O 0 C. Thereafter, 0-5000 ppm of a coating is dripped onto the granulate, followed by rotating the drum for yet another 5 minutes.
• the thus treated granulate is dumped into a broad plastic tank, where the granulate can "evaporate" for 5 minutes. Subsequently, the treated granulate is transferred into a plastic jar. After sealing the jar, the grains are allowed to cool to room temperature over a period of 24 hours.
• T approx. 133 0 C
• urea pellets were formed by dropping the molten urea drops separately from a height of 1 cm onto a glass plate. After solidification, the pellets were scraped off the glass plate and the fine dust was removed by means of a sieve. The pellets were collected and kept in an air tight flask until the compressibility and tendency of cake formation were measured.
• a transparent round tube with an internal diameter of 3 cm was filled with 40 g urea pellets.
• a plunger was arranged, which caused a pressure of about 600 kPa to be exerted on the sample.
• the height of the urea column was measured.
• the relative difference in height which is a measure for the compressibility, was calculated from these two values ( ⁇ height (%) ) .
• the degree of cake formation can be determined by measuring the breaking strength (expressed in kilograms) of the compressed urea sample.
• a representative test for simulating caking of granulate was performed as follows. Polyethylene tube foil was closed on one side by means of sealing (70 mm wide, 300 mm long) . At the bottom of the formed pouch, a plastic chip (48 mm diameter) was brought. The pouch was filled with 125 gram granulate. Subsequently, another plastic chip was put on the granulate. The pouch was evacuated and closed by a seal. The obtained pouch was suspended from a metal pin. This procedure was repeated twice for the same sample. All sealed pouches with granulate were subsequently placed in an autoclave. The samples were kept for a week at 2 bar gauge pressure at a temperature of 35 or 50 0 C. Subsequently the pouches were carefully cut open. The hardness of the baked sample was measured in a breaking apparatus. The force required to break the sample was read electronically. The obtained values (expressed in kilograms) were the average of at least three samples
• Two plastic beakers of 200 ml were filled with 160 gram (blank or treated) fertilizer.
• the weights of the beakers as well as the fertilizer are measured with an analytical balance.
• the total weight is calculated (m to t) •
• the beakers are placed in a climate chamber with the following conditions: 80% relative air humidity and a temperature of 2O 0 C. After 72 hours, the samples are removed from this climate chamber and subsequently the weight is determined (m na ) and the appearance is examined. Thereafter, the moisture absorption can be calculated as follows :
• a Petri dish with a diameter of approximately 8.5 cm was filled with 15.0 gram urea pellets. This was subsequently placed in a climate chamber with a relative air humidity of 80% and a temperature of 20 0 C. After 24 hours, the increase in weight as a result of moisture absorption by the granulate was measured, after which the Petri dish was closed with the corresponding cover. The dish was put aside in the dark at room temperature. After two weeks, the content of the dish was examined by looking at the granulate under a loupe.
• the abbreviation ghk stands for no recrystallization, whereas hk stands for recrystallization after moisture absorption and drying.
• the relative amount of dust particles of the granulates was determined as follows. 40 grams (accurately weighed) of fertilizer was brought into a three- neck round-bottom flask of 500 ml. The flask was provided with a glass column and a gas capillary, connected with a compressed air cylinder. The end of the gas capillary was placed in the granulate. Air (2 bar gauge pressure) was blown through the granulate for 75 seconds, by which a fluidised bed system was created. The weight of the remaining granulate was determined accurately on an analytical balance. The loss in weight is a measure for the amount of free dust particles and the dust particles created by friction. The determinations were at least performed twice.
• the used grain maize residue consists of the steep liquid resulting from the extraction of starch from grain maize, possibly after concentration of the slurry for restricting the added amount of liquid.
• Example 2 The natural residue products mentioned in Example 1, were tested as suspension in water. Since the presence of water in case of hygroscopic granulate often causes accellerated cake formation, it has been checked whether the use of other solvents resulted in improvement of the anti-baking properties. In order to investigate this, 20% w/w very fine ( ⁇ 60 micron) soy protein powder was mixed with several polar solvents. The obtained slurries were applied to calcium ammonium nitrate, CAN (27% N) via the coating process.
• 2% (w/w) polyvinyl amine (molecular mass 10,000 g/mol, hydrolysis degree > 90%) was added to the natural waste material.
• the obtained mixtures were coated onto calcium ammonium nitrate, CAN (27% N) , by means of spraying.
• a paraffin product A has been taken in the test. It had the following properties: solidification point 45°C, viscosity 7 mPa . s (8O 0 C).
• the composition is as follows: tallow fat amine content 7.0% w/w, mineral oil 20% w/w and 73% w/w low-melting paraffin wax.
• Another process for reducing the caking of granulate is adding a fatty alcohol (C10-C30) to the vegetable waste material.
• C10-C30 a fatty alcohol
• 5% (w/w) has been mixed with grain maize residue at a temperature of approx. 60 0 C.
• the obtained mixtures were coated onto calcium ammonium nitrate granules (27% N) .
• paraffin-containing product A has been taken in the test.
• the formulations in Table 9 consist of 95% grain maize residue and 5% moisture resistant active compound. These formulations (temperature approx. 6O 0 C) were applied to calcium ammonium nitrate (CAN, 27% N) .
• a formulation B has been made, having the following composition: 85% (w/w) aqueous grain maize residue, 10% (w/w) polyoxyethylene (2) stearyl ether and 5% (w/w) tallow fat alcohol. This mixture has been applied as coating in different doses.
• a moisture resistant coating C has been taken, in accordance with WO 03/006399 (7.5% (w/w) tallow fat amine (C16-C18), 7.5% (w/w) 2-ethyl hexyl phosphate acid ester, 85% (w/w) paraffin wax (> 50% linear alkane) , melting point 45°C) .
• Table 10 The results are mentioned in Table 10.
• the protection against moisture absorption of moisture-sensitive inorganic salts can therefore also be established by applying mixtures on the basis of natural residue products and linear alkanes.
• the following examples relate to the use of vegetable waste flows as granulation additive, to the urea melt.
• the above example proves that waste flows of natural origin have a positive influence on decreasing the compressibility and the cake formation.
• the grain maize residue gives a performance which is at least equivalent to urea treated with urea-formaldehyde in all measured properties .

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