Classifications

• • C—CHEMISTRY; METALLURGY
  • C05—FERTILISERS; MANUFACTURE THEREOF
  • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
  • C05D9/00—Other inorganic fertilisers
• • C—CHEMISTRY; METALLURGY
  • C05—FERTILISERS; MANUFACTURE THEREOF
  • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
  • C05D9/00—Other inorganic fertilisers
  • C05D9/02—Other inorganic fertilisers containing trace elements
• • C—CHEMISTRY; METALLURGY
  • C05—FERTILISERS; MANUFACTURE THEREOF
  • C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
  • C05F11/00—Other organic fertilisers
• • C—CHEMISTRY; METALLURGY
  • C05—FERTILISERS; MANUFACTURE THEREOF
  • C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
  • C05F11/00—Other organic fertilisers
  • C05F11/10—Fertilisers containing plant vitamins or hormones
• • 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
  • C05G5/10—Solid or semi-solid fertilisers, e.g. powders
  • C05G5/12—Granules or flakes

Definitions

• the present disclosure relates to fertilizer products and their process of preparation. Particularly, the present disclosure relates to sulfur based fertilizer products.
• Fertilizers are the auxiliary chemicals supplied to plants in order to externally provide nutrients essential for their growth. Fertilizers may be of inorganic or organic nature and are typically in forms such as solid - granulated or powdered, liquid, semisolid and aerosol. They contain a wide range of ingredients such as manure, bat guano, compost, peat moss, wood ash, nitrogen, phosphorus and potassium, calcium, sulfur, iron, zinc and magnesium.
• Sulfur is an extremely vital element required for the growth of plants and can be provided to plants via fertilizers either in its elemental form or in inorganic forms such as sulfate (S0 4 2" ). Plants can also use sulfur dioxide (S0 2 ) from the atmosphere. Elemental sulfur can, however, be only absorbed by plants once it is oxidized to sulfate by soil bacteria, namely Thiobacillus, in the presence of moisture/water. Furthermore, elemental sulfur is insoluble in water and in powder form, creates dust which irritates the eyes and is hazardous to health. There is also a possibility that unused sulfur can flow away with water during raining or irrigation and can thus, contaminate the water bodies.
• fertilizer products are prepared by mixing elemental sulfur with a carrier medium such as mineral clay, which is used as a soil additive.
• a carrier medium such as mineral clay
• mineral clay can add heavy metals like iron, nickel and the like to the soil. It also contains high sodium levels which lead to an increase in the salinity of the soil.
• mineral clay has low moisture absorptivity and low disintegration capacity due to which availability of the sulfur to the soil and ultimately its conversion to the required sulfate form is less.
• the present disclosure provides a process for the preparation of a fertilizer product comprising preparing a first mixture by admixing ingredients such as elemental sulfur, at least one swelling agent, at least one binding agent, at least one plant growth regulator, optionally, at least one inorganic solid material with water at a temperature ranging from 15 to 40 °C; pugging followed by kneading said first mixture to obtain dough; processing said dough to obtain shaped articles and drying said shaped articles to obtain the fertilizer product.
• ingredients such as elemental sulfur, at least one swelling agent, at least one binding agent, at least one plant growth regulator, optionally, at least one inorganic solid material with water at a temperature ranging from 15 to 40 °C
• said step of processing is at least one selected from the group consisting of pelletizing, pastilling, extruding and granulating and said shaped article is at least one selected from the group consisting of pellets, pastilles, extrudates, beads, flakes and granules.
• the fertilizer product is characterized by moisture content ranging from 0.1 to l.0 . %w/w.
• a process for the preparation of a fertilizer product initially includes preparing a first mixture by admixing the ingredients in a pre-determined quantity of water at a temperature ranging from 15 to 40 °C.
• the ingredients used for the preparation of the mixture include micronized elemental sulfur in an amount ranging from 70 to 98 % of the total weight of the mixture, at least one swelling agent in an amount ranging from 0.1 to 10 % of the total weight of the mixture, at least one binding agent in an amount ranging from 0.5 to 30 % of the total weight of the mixture, at least one plant growth regulator in an amount ranging from 0.005 to 5 % of the total weight of the mixture and optionally at least one inorganic solid material in an amount ranging from 0 to 30% of the total weight of the mixture.
• Water is used as per requirement and is typically added externally in an amount ranging from 5 to 40 % of the total weight of the mixture.
• the step of preparation of the first mixture is carried out by incorporating at least one inorganic solid material in an amount ranging from 1 to 30 %w/w and at least one binding agent in an amount ranging from 0.5 to 30 %w/w in liquid; molten sulfur being present in an amount ranging from 70 to 98 %w/w of the total weight of the mixture.
• This step is carried out at a temperature ranging from 119 to 140 °C and is accompanied by stirring to yield the first mixture wherein the inorganic solid material is finely dispersed in molten sulfur.
• the resulting first mixture is then pugged and kneaded to obtain dough which is further processed to obtain shaped articles.
• the meaning of the term 'pugging' includes working the mixture into a soft, plastic condition without air pockets; thereby making it suitable for further processing,.
• the shaped articles upon drying at a temperature ranging from 25 to 50 °C yield the fertilizer product of the present disclosure.
• the step of processing is at least one selected from the group consisting of pelletizing, pastilling, extruding and granulating and the shaped article is at least one selected from the group consisting of pellets, pastilles, extrudates, beads, flakes and granules.
• the process of the present disclosure is designed as presented herein above to achieve some specific objectives.
• the processing steps of pelletizing, pastilling, extruding and granulating are purposefully included to prepare a fertilizer product such that its constituent units (shaped articles) have definitive macromolecular dimensions.
• This is a special feature of the product of the present disclosure which is associated with plentiful advantages such as obviation of the problems accompanying sulfur dust, increase in the water holding capacity and slow release of the ingredients such as potassium, nitrogen, water and plant growth regulators into the soil; thereby making the product very well suited for agriculture and horticulture related applications.
• some of the essential ingredients used in the product are heat sensitive and can be decomposed on exposure to elevated temperatures (above 100 °C) during the process of preparation.
• the present disclosure provides a fertilizer product prepared from the afore-stated process.
• the product is in the form of shaped articles selected from the group consisting of pellets, pastilles, extrudates, beads, flakes and granules, having size ranging from 1.5 to 6 mm.
• the fertilizer product has moisture content ranging from 0.1 to 1.0 %w/w .
• the product includes the ingredients provided herein below.
• Micronized elemental sulfur is present in an amount ranging from 70 to 98 % of the total weight of the first mixture, preferably from 87 to 98 %w/w.
• Sulfur being an extremely important nutrient for plants, demonstrates a wide array of activities. Sulfur enhances availability of the necessary plant nutrients in the soil, which improves the quality and yield of the agricultural crops.
• sulfur is a vital element necessary for the synthesis of entities such as sulfur-containing amino acids and proteins, coenzyme A, biotin, thiamine, glutathione, chlorophyll, lipids and volatile oils.
• sulfur in its elemental form acts as a pesticide and fungicide against certain soil pests and micro-organisms.
• the sulfur included in the present product is of particle size ranging from 10 ⁇ to 250 ⁇ . In one embodiment, the elemental sulfur is of more than 99% purity, obtained from Claus process post hydrodesulphurization in oil refinery.
• the product contains at least one swelling agent in an amount ranging from 0.1 to 10 % of the total weight of the first mixture, preferably from 1 to 10 %w/w and is at least one selected from the group consisting of polyacrylic acid, polyacrylamide polymer, cellulose grafted polyacrylamide polymer, potassium salt of cellulose grafted polyacrylamide and starch grafted polyacrylamide.
• the function of the swelling agent is to absorb water present in the surrounding soil area such as irrigated water or precipitated atmospheric moisture once the fertilizer product is introduced in the soil. Upon absorption of water, the product expands leading to breaking of pellets, extrudates and the like to release fine sulfur particles along with other ingredients such as the plant growth regulators across a very wide perimeter.
• the elemental sulfur present in the fertilizer product disperses into fine particles having a diameter less than 30 ⁇ . As a virtue of the size reduction of the sulfur particles, they get easily oxidized into the sulfate form.
• fertilizer products which have high sulfur content and low swelling agent content have good applicability in lands with high salinity and water content. This is because less quantity of swelling agent leads to less water holding capacity which is acceptable for high water content lands. Similarly, fertilizer products with low sulfur and high swelling agent content have a high water holding capacity and are thus useful for the regions facing water scarcity.
• Binding agent(s) are included in the present product to facilitate effective binding between micronized elemental sulfur and the other ingredients in order to form an aesthetic and uniform fertilizer product.
• the product of the present disclosure contains at least one binding agent in an amount ranging from 0.5 to 30 % of the total weight of the first mixture, preferably from 1 to 13 %w/w and is selected from the group consisting of carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropylmethyl cellulose, hydroxyethylpropyl cellulose, corn starch, potato starch, starch acetates, ionic starches, polyvinyl alcohol, polyvinyl acetate, polyethylene glycol and polylactic acid.
• the product of the present disclosure also contains at least one plant growth regulator in an amount ranging from 0.005 to 5 % of the total weight of the first mixture, preferably from 0.005 to 1 %w/w and is selected from the group consisting of auxins, gibberellins, cytokinins and abscisic acid (ABA). More specifically, the plant growth regulator is at least one selected from the group consisting of indole-3 -acetic acid (IAA), gibberellic acid (GA) and 6-benzyl adenine (BA).
• IAA indole-3 -acetic acid
• GA gibberellic acid
• BA 6-benzyl adenine
• At least one inorganic solid material is present in the product of the present disclosure in an amount ranging from 0 to 30% of the total weight of the first mixture, preferably from 0 to 10 %w/w.
• the inorganic solid material is selected from the group consisting of zeolites, clays, aluminosilicates and molecular sieve; more specifically, from the group consisting of zeolite A, zeolite X, ZSM-5, clinoptilolite, phillipsite, aluminum phosphate (A1P0 4 ) zeolites, silicon aluminum phosphate (SAP0 4 ) zeolites, montmorillonite, kaolinite, hectorite, attapulgite, mordenite, molecular sieve MS-3A, molecular sieve 4A and spent Fluid catalytic cracking (FCC) catalyst.
• the inorganic solid material of the present disclosure is nanoporous.
• the inorganic materials are molecular sieves used for air drying and solvent drying in petrochemical or refining complex and can be used in powdered or granular form. Inclusion of the nanoporous inorganic solids is advantageous as these substances have a tendency to trap the heavy metal ions present in soil, so that the heavy metals do not get accumulated in the plants. Furthermore, their high water adsorption capacities in the dehydrated state and their high ion-exchange capacities make many natural zeolites effective carriers of herbicides, fungicides, and pesticides.
• the zeolites are also efficient in modifying the soil texture - removing the alkalinity of the soil due to their ion exchange capability. Zeolites upon mixing with soil help in retaining its moisture and maintaining sufficient aeration which enhances the crop yield.
• the inorganic solid material of the present disclosure also contains plant nutrients absorbed into their framework. Upon their introduction into the soil, the inorganic solid material releases the nutrients as a result of which the crops are enormous benefited.
• the plant nutrient present in the inorganic solids is at least one selected from the group consisting of K, Mg, Ca, Fe, Mn, Mo, P0 , NH 3 , Zn, Cu, B, and Co.
• Water is included in the product to facilitate formation of dough. Typically, it is present in an amount ranging from 5 to 40 % of the total weight of the first mixture, preferably from 10 to 33 %w/w.
• the fertilizer product of the present disclosure consists of elemental sulfur, at least one swelling agent, at least one binding agent, at least one plant growth regulator and water.
• the fertilizer product of the present disclosure consists of elemental sulfur, at least one swelling agent, at least one binding agent, at least one plant growth regulator, at least one inorganic solid material and water.
• the effectiveness of the fertilizer product of the present disclosure lies in its preparation in the form of shapes such as pellets, pastilles and the like and employment of the principle of water imbibition.
• the swelling agents upon absorption of water make the shaped articles swell up to a great extent; thereby resulting in dispersion of very fine sulfur particles.
• the rate of oxidation of fine particles is greater than that of larger particles, more quantity of sulfur is available to plants in their desired form, thereby improving the quality and yield of the plants.
• the pH of the product upon dispersion into soil ranges from 7.4 to 8.5, which is suitable for plants, soil and soil microbes.
• the fertilizer product of the present disclosure does not use additives such as fillers, surfactants, wetting agents and the like which is in contrast to the conventional products.
• the characteristic combination of ingredients, especially inclusion of both the swelling and binding agents leads to the fertilizer products having optimum crushing strength, swelling and dispersion indices.
• the fertilizer product of the present disclosure has mechanical strength in the range of 1.5 to 6 Kgf which is essential to give a dust-free product with the required dispersity.
• Example 1 Preparation of the fertilizer product - Process Optimization
• Example 1A Sulfur + Binding agent
• micronized elemental sulfur was mixed with 30 g of carboxymethyl cellulose (CMC) as a binding agent.
• CMC carboxymethyl cellulose
• a sufficient quantity of water was added on dry weight basis to form the first mixture.
• the first mixture was pugged and kneaded and half of the resultant dough was mechanically converted into extrudates in the size range (diameter x length) of 1.5 x 5 - 7 mm using an extruder. The remaining half was agglomerated into spherical beads of the size of 3 to 4 mm using a pan or drum granulator.
• the formed extrudates and spherical beads were air dried to have less than 0.5 wt% of moisture content on dry weight basis.
• Methods of drying of formed bodies included vacuum or microwave drying - methods apparent to those skilled in the art. Swelling and dispersion properties of the formed extrudates and beads were measured by taking 10 ml of formed extrudates in a 100 ml measuring cylinder filled with water. After 60 minutes, the volume of the formed extrudates was found to increase by 70% and completely disperse into less than 30 micron size after 20 hours. The extrudates of the present disclosure had a crushing strength of 4.4 Kgf.
• micronized elemental sulfur was mixed with 2 g of carboxymethyl cellulose as a binding agent and 1 g potassium salt of polyacrylamide grafted cellulose as a swelling agent. A sufficient quantity of water was added on dry weight basis to obtain the first mixture.
• the mixture was pugged and kneaded and half of the resultant dough was mechanically converted into extrudates in the size range (diameter x length) of 1.5 x 4-7 mm using an extruder. The remaining half was agglomerated into spherical beads of the size of 3 to 4 mm using a pan or drum granulator.
• the formed extrudates and spherical beads were air dried to have less than 0.5 wt% of moisture content on dry weight basis. Methods of drying of formed bodies included vacuum or microwave drying - methods apparent to those skilled in the art.
• Swelling and dispersion properties of the formed extrudates and beads were measured by taking 10 ml of formed extrudates in a 100 ml measuring cylinder filled with water. After 60 minutes, the volume of the formed extrudates was found to increase by 89% and completely disperse into less than 30 micron size after 12 hours.
• the extrudates of the present disclosure had a crushing strength of 1.9 Kgf.
• Poly A Potassium salt of polyacrylamide grafted cellulose
• Poly B Polyacrylic Acid
• CMC Carboxy methyl cellulose
• EC Ethyl cellulose
• HPMC Hydroxy propyl methylcellulose
• PVA Polyvinyl alcohol
• Example 1C Sulfur + Binding agent + Swelling agent + Plant Growth Regulators
• micronized elemental sulfur was mixed with 1.995 g carboxymethyl cellulose as a binding agent, 2 g potassium salt of polyacrylamide grafted cellulose as a swelling agent and 0.005 g of GA as a plant growth hormone.
• a sufficient quantity of water was added on dry weight basis to obtain the first mixture.
• the mixture was pugged and kneaded and half of the resultant dough was mechanically converted into extrudates in the size range (diameter x length) of 1.5 x 5-7 mm using an extruder. The remaining half was agglomerated into spherical beads of the size of 3 to 4 mm using a pan or drum granulator.
• the formed extrudates and spherical beads were air dried to have less than 0.5 wt% of moisture content on dry weight basis. Methods of drying of formed bodies included vacuum or microwave drying - methods apparent to those skilled in the art.
• Swelling and dispersion properties of the formed extrudates and beads were measured by taking 10 ml of formed extrudates in a 100 ml measuring cylinder filled with water. After 60 minutes, the volume of the formed extrudates was found to increase by 120% and completely disperse into less than 30 micron size after 4 hours.
• the extrudates of the present disclosure had a crushing strength of 1.8 Kgf.
• Poly A Potassium salt of polyacrylamide grafted cellulose
• CMC Carboxy methyl cellulose
• GA Gibbereillic acid
• BA 6-Benzyl adenine
• ABA Abscisic acid
• IAA Indole-3 -acetic acid
• micronized elemental sulfur 80 g was mixed with 10 g of zeolite X powder, 8 g of potassium salt of polyacrylamide grafted cellulose as a swelling agent and 2 g of carboxymethyl cellulose (CMC) as a binding agent.
• CMC carboxymethyl cellulose
• a sufficient quantity of water was added on dry weight basis to obtain the first mixture.
• the mixture was pugged and kneaded and half of the resultant dough was mechanically converted into extrudates in the size range (diameter x length) of 1.5 x 5-7 mm of using an extruder. The remaining half was agglomerated into spherical beads of the size of 3 to 4 mm using a pan or drum granulator.
• the formed extrudates and spherical beads were air dried to have less than 0.5 wt% of moisture content on dry weight basis. Methods of drying of formed bodies included vacuum or microwave drying - methods apparent to those skilled in the art.
• Swelling and dispersion properties of the formed extrudates and beads were measured by taking 10 ml of formed extrudates in a 100 ml measuring cylinder filled with water. After 60 minutes, the volume of the formed extrudates was found to increase by 230% and completely disperse into less than 30 micron size after 20 hours.
• the extrudates of the present disclosure had a crushing strength of 3.5 Kgf.
• Poly A Potassium salt of polyacrylamide grafted cellulose
• CMC Carboxy methyl cellulose
• PVA Poly vinyl alcohol
• HPMC Hydroxy propylmethyl cellulose
• EC Ethyl cellulose
• Spent MS Spent molecular sieve used for air drying unit
• the results indicate that when the product contains sulfur, binding agent, swelling agent and inorganic solids the crushing strength ranges from 1.5 to 4.5 Kgf; the % swelling ranges from 2 to 280 and the dispersion time is 20 hours.
• Example IE Sulfur + Binding agent + Swelling agent + Inorganic solids + Plant growth regulators
• micronized elemental sulfur 80 g was mixed with 10 g of zeolite A powder, 8 g of potassium salt of polyacrylamide grafted cellulose as a swelling agent, 1.995 g of carboxymethyl cellulose (CMC) as a binding agent and 0.005 g of gibberellic acid (GA) as a plant growth constituent.
• CMC carboxymethyl cellulose
• GA gibberellic acid
• the remaining half was agglomerated into spherical beads of the size of 3 to 4 mm using a pan or drum granulator.
• the formed extrudates and spherical beads were air dried to have less than 0.5 wt% of moisture content on dry weight basis.
• Methods of drying of formed bodies included vacuum or microwave drying - methods apparent to those skilled in the art.
• Swelling and dispersion properties of the formed extrudates and beads were measured by taking 10 ml of formed extrudates in a 100 ml measuring cylinder filled with water. After 60 minutes, the volume of the formed extrudates was found to increase by 200% and completely disperse into less than 30 micron size after 20 hours.
• the extrudates of the present disclosure had a crushing strength of 2.1 Kgf.
• Poly A Potassium salt of polyacrylamide grafted cellulose
• CMC Carboxy methyl cellulose
• GA Gibbereillic acid
• BA 6-benzyl adenine
• ABA abscisic acid
• Spent MS Spent molecular sieve used for air drying unit
• the results indicate that when the product contains sulfur, binding agent, swelling agent, inorganic solids and plant growth regulators the crushing strength ranges from 2.1 to 4.5 Kgf; the % swelling ranges from 2 to 280 and the dispersion time is 20 hours.
• Swelling and dispersion properties of the shaped articles were measured by taking 10 ml of the shaped articles in a 100 ml measuring cylinder filled with water. After 60 minutes, the volume of the formed extrudates was found to increase by 5% and they were found to completely disperse into less than 30 micron size after 72 hours.
• the shaped articles of the present disclosure had a crushing strength of 3.0 Kgf.
• the fertilizer product is of multi-functional nature as it has higher sulfur content, higher water holding capacities and slow release of plant nutrients into the soil.
• the present disclosure provides a dust-free, economical, toxic metal-free elemental sulfur containing fertilizer product as the feed for horticultural purposes.
• the present disclosure not only provides a fertilizer product containing higher percentage of sulfur for plant nourishment, but also a product for the protection of plants by exhibiting antifungal activities against certain soil pests and microorganisms.
• the present disclosure provides a fertilizer product having lower Na content and pH in the range of 7.5 to 8.5 to lower the salinity of the soil. • The present disclosure also provides a simple, effective and economic process for the preparation of a fertilizer product with desired mechanical strength.
• the present disclosure provides an effective way of reutilizing spent catalysts such as molecular sieves, Fluid catalytic cracking (FCC) catalyst and the like.
• spent catalysts such as molecular sieves, Fluid catalytic cracking (FCC) catalyst and the like.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Inorganic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Botany (AREA)
• Fertilizers (AREA)
• Pest Control & Pesticides (AREA)

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• 2015
  • 2015-01-15 IN IN350MU2014 patent/IN2014MU00350A/en unknown
  • 2015-01-15 WO PCT/IN2015/000022 patent/WO2015114651A2/en active Application Filing
  • 2015-01-15 TR TR2016/07901T patent/TR201607901T1/tr unknown

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