WO2012065214A1 - Composition d'engrais contenant un nutriment pour les plantes et son procédé de production - Google Patents

Composition d'engrais contenant un nutriment pour les plantes et son procédé de production Download PDF

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Publication number
WO2012065214A1
WO2012065214A1 PCT/AU2011/001467 AU2011001467W WO2012065214A1 WO 2012065214 A1 WO2012065214 A1 WO 2012065214A1 AU 2011001467 W AU2011001467 W AU 2011001467W WO 2012065214 A1 WO2012065214 A1 WO 2012065214A1
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WO
WIPO (PCT)
Prior art keywords
clay
palygorskite
granules
binder
crystalline compound
Prior art date
Application number
PCT/AU2011/001467
Other languages
English (en)
Inventor
Amanda Jayne Saunders
Original Assignee
Csbp Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from AU2010905046A external-priority patent/AU2010905046A0/en
Application filed by Csbp Limited filed Critical Csbp Limited
Publication of WO2012065214A1 publication Critical patent/WO2012065214A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
    • C05C3/005—Post-treatment

Definitions

  • the present invention relates to a fertiliser composition containing a plant nutrient and a method for producing it.
  • Ammonium sulphate is a good source of nitrogen and sulphur for agriculture and is available as a crystalline product of the nickel mining industry, for example in Western Australia, or as a by-product from caprolactam manufacture. Other ammonium sulphate preparation schemes are also available, for example through reaction of ammonia with sulphuric acid. Although ammonium sulphate crystal size varies considerably dependent on preparation method, a typical crystal size would be between 0.1 mm and 2.0 mm. For blending and application as a fertiliser, however, the ammonium sulphate is required in granular form with a size range between 2-4 mm so that segregation in blends does not occur and so that application through disk spreaders and seeders is trouble free.
  • Crystalline ammonium sulphate particles are not auto-adhesive which makes them difficult to granulate. Soft and friable granules typically result.
  • the addition of hot water to a bed of ammonium sulphate in a high shear granulator results in a slurry rather than formation of agglomerated granules.
  • An effective binding agent is needed which has enough adhesive and cohesive force to promote nucleation and growth and also impart sufficient mechanical strength to the granules.
  • Dry binders are usually mixed with ammonium sulphate (or other NPK - nitrogen, phosphorus, potassium - ingredients) prior to entering the granulator and consist of a variety of binding mechanisms.
  • a combination of reactive carbonate (calcium carbonate), reactive sulphate (longbienite), water soluble slicate (potassium silicate) and dispersant (e.g polymethacrylate) to produce a powdered binder that makes up 3-5% of the final granular ammonium sulphate is taught by Van der Walle and Smith, US Patent No. 5,078,779 Binder for the Granulation of Fertilisers such as Ammonium Sulphate, the contents of which are hereby incorporated herein by reference.
  • the binder must come into contact with an acid (sulphuric, nitric, phosphoric) to produce calcium and sulphate ions that form the reactive components of the binder while the soluble silica is specifically added as a quick setting, strengthening agent in the formulation.
  • an acid sulphuric, nitric, phosphoric
  • a mixture of dry calcium oxide and ammonium sulphate, reacted with sulphuric acid, can liberate enough free ammonia to react with the excess acid to produce a low pH (2.5) granular ammonium sulphate product with a crush strength of 1 .2-2.6 kg (2-3mm granules) - Longanathan et al, Granulation of finely crystalline ammonium sulphate using calcium oxide and sulphuric acid, Fertiliser Research, 31 :85-93 (1992)).
  • the present invention provides - in a first aspect - a fertiliser composition
  • a fertiliser composition comprising granules of a crystalline compound containing a plant nutrient and a binder for said crystalline compound wherein said binder is formed from acidified clay and binds crystals of said crystalline compound throughout said granules.
  • the invention provides a method of producing a binder for granulation of a fertiliser composition containing a crystalline compound comprising a plant nutrient wherein a clay is acidified to produce the binder for binding crystals of said crystalline compound through fertiliser granules formed during granulation.
  • the present invention provides a method for granulating a crystalline compound containing a plant nutrient wherein said crystalline compound is granulated with a binder formed by acidified clay wherein, in product granules, the binder binds crystals of said crystalline compound throughout said granules.
  • the binder may be formed during the granulation process.
  • the binder may - possibly at the same time - be formed during synthesis of the crystalline compound containing a plant nutrient.
  • the binder may be formed by action of an inorganic acid, especially sulphuric or phosphoric acid, on a clay which may be defined as an alumino-silicate typically of fine grained nature.
  • the inorganic acid is concentrated and clay acidification proceeds at a temperature of above about 100 Q C at atmospheric pressure; that is, above the boiling point of water at atmospheric pressure.
  • Clay and acid may be admixed in various proportions for acidification.
  • a desirable range is between 0 and 10 wt% clay contacted - in suspension - with an inorganic acid solution.
  • Such contacting of clay and inorganic acid should be performed with stirring or agitation.
  • Such contacting which results in acidification of the clay, may involve at least partial dissolution of the clay and formation of silicate compounds, possibly in polymeric form, which can act as a binding silicate cement for particles of the crystalline compound.
  • silicate compounds possibly in polymeric form, which can act as a binding silicate cement for particles of the crystalline compound.
  • at least some clay may remain following the dissolution process.
  • Such remaining clay may form a matrix, encapsulating the crystalline compound particles, which also assist in enhancement of mechanical strength of granules produced using the binder.
  • the binder remains in a fluid state, being in the form of a liquid or gel during granulation.
  • the crystalline compound is a compound fertiliser containing multiple plant nutrients.
  • One example is an ammonium sulphate compound which contains plant nutrients nitrogen and sulphur.
  • an ammonium sulphate compound which contains plant nutrients nitrogen and sulphur.
  • mechanical strength of ammonium sulphate has been problematic with friable or weak nature of ammonium sulphate granules leading to farmer losses.
  • an acidified clay stream is introduced during the ammonium sulphate granulation process, the acidified clay acts as a binder binding crystals of ammonium sulphate increasing mechanical strength and reducing spreading and other friability problems referred to above.
  • the clay is a palygorskite clay, a clay with fibrous and adhesive nature. While the clay may contain other minerals such as quartz, feldspar and dolomite - amongst others - palygorskite is a key component of the clay. Palygorskite may also be referred to as attapulgite or Fuller's Earth. Palygorskite has a dioctahedral ribbon structure with an ideal formula Si8O2oAl2Mg2(OH)2((OH)2) 4 .4H 2 O. X Ray Diffraction may be required to identify clays containing palygorskite. Palygorskite has diagnostic XRD peaks at 2 ⁇ about 8, 20 and 35.
  • the acidified clay binder may comprise silicate compounds, possibly in polymeric form, acting as a silicate cement binding crystals of the above described crystalline compound; and residual clay.
  • the product granules produced by granulation with the binder contain greater than about 1 wt % residual clay, preferably above about 1 .5 wt% residual clay.
  • mechanical strength enhancement is noted at palygorskite concentration in product granules greater than 1 .7 wt%, preferably in the range 3 to 10 wt% palygorskite and most preferably in the range 3.2 to 4.4 wt% palygorskite.
  • the binder may be formed during synthesis of the crystalline compound containing a plant nutrient. This is particularly convenient in production of compound fertilisers containing multiple plant nutrients such as nitrogen, sulphur, phosphorus and potassium, particularly where the required grade requires synthesis.
  • Ammonium sulphate is one example.
  • the synthesis comprises reacting concentrated sulphuric acid with ammonia.
  • at least a portion of the sulphuric acid requirement for ammonium sulphate synthesis is mixed with clay, advantageously palygorskite clay, in a concentration in the range described above.
  • This acidified clay stream is introduced to a reactor in which sulphuric acid and ammonia are being reacted to form ammonium sulphate compound.
  • Such synthesis is desirably conducted simultaneously with granulation as product ammonium sulphate as required for fertiliser applications is granular. It is to be understood that clays other than palygorskite could be used and compound fertilisers other than ammonium sulphate may be synthesised and/or granulated in accordance with the method of the invention.
  • the silicate cement is observed to solidify at fertiliser compound crystal contact points providing additional mechanical strength.
  • Residual palygorskite adheres to interfaces providing additional mechanical strength to granules.
  • the modification of ammonium sulphate crystal habit by acidified palygorskite involves decrease in crystal size and increased packing density. This enhances mechanical strength by increasing the physical contacts between neighbouring crystals and minimising internal voids. In summary, such process results in a granular ammonium sulphate product with increased mechanical strength over prior products.
  • the mechanical strength of the ammonium sulphate granules may be affected by factors such as the ammonia to sulphuric acid ratio in the ammonium sulphate synthesis, granule size and time after synthesis. In the latter regard, mechanical strength may continue to increase for a time after synthesis and perhaps to a duration of days, weeks or even a few months. Therefore, subject to economic considerations, ammonium sulphate granulated as described may be held for a curing period prior to supply to customers.
  • the acidified clay binder is formed in such a way that the nutrient components remain soluble and plant available. Therefore, the process of forming ammonium sulphate granules, in which ammonium sulphate crystals are bound by silicate binder, is compatible with the objective of producing an effective fertiliser composition.
  • Palygorskite clay was sourced from Hudson Marketing Pty Ltd under the trade name Fillerfix GR050. This clay has an average particle size of 60 microns.
  • XRD analysis it was determined that the palygorskite clay product contained quartz, feldspar and dolomite in addition to palygorskite as identified by diagnostic peaks at 2 ⁇ about 8, 20 and 35.
  • the clay was admixed to target concentration 0.0, 1 .0, 2.0, 3.0, 4.0, 5.0, 6.0 and 7.0 wt % palygorskite clay, in final ammonium sulphate granules, and contacted with AR grade 98% concentrated sulphuric acid.
  • the contacting or admixture involved controlled addition of sulphuric acid to control reaction rate and temperature as the reaction is exothermic, reaching a maximum temperature of 138 Q C during the clay acidification operation. The admixture occurred with stirring so that clay solids did not settle.
  • Partial dissolution of palygorskite occurred during the acidification to form a silicate binder to be used in granulation of crystalline ammonium sulphate as described further below.
  • Ammonia gas at pressure 30 psig (207 kPa) was bubbled through the acidified clay stream or dilute slurry at a temperature of about 120 Q C to synthesise ammonium sulphate by a process mimicking that of the ammonium sulphate production plant. The temperature dropped to about 1 10 Q C when an ammonium sulphate compound began to precipitate.
  • Crystalline ammonium sulphate obtained from Western Mining nickel operations, was stored at 55 Q C while the silicate binder, resulting from palygorskite clay acidification, was being prepared in the above described admixture/dissolution operation.
  • the crystalline ammonium sulphate was fed to a granulator pan at a controlled rate by a vibrating feeder. The rate of binder addition was based on the condition of the granules in the pan: too wet, less binder; too dry, more binder.
  • Granules from the 2.8-4.0 mm size fraction were used to determine the palygorskite concentration in the samples by analysing for cations (Mg, Al, Fe) by ICP-AES spectrometry following acid dissolution in HCI/HN0 3 solution.
  • Mg analysis was selected as basis for measurement of palygorskite concentration (noting that Mg is an important component of the palygorskite mineral).
  • XRD analysis of water insoluble residue following granule dissolution showed absence of palygorskite and dolomite peaks. However quartz peaks remained as well as small peaks for kaolinite and feldspar which could be seen at high resolution. XRD analysis also indicated presence of an amorphous material in the residue formed during acidication of palygorskite and production of the granules.
  • This feature was reflected by a broad band between 18 and 30 2 ⁇ and is consistent with formation of amorphous silica/silicate as seen with 7N HCI treatment of palygorskite (Barrios et al, Acid Activation of a Palygorskite with HCI: development of physico- chemical, textural and surface properties, Applied Clay Science, 10, 247-258, 1995).
  • the amorphous silica/silicate present within the above described adhesive gel acts as the binder or cement for crystals of the ammonium sulphate.
  • Granules in the size range of 2.36-2.80 mm were used for mechanical strength (here crushing strength) evaluation in accordance with IFDC S-1 15 ( as described in Rutland, 1993).
  • a MARK-10 EG 20 Digital Force Gauge was used to measure the peak compressive force required to break 25 single granules. Crushing strength was measured for each sample at 24 hours, 1 week and 2 months after granulation.
  • the median force required to break 2.36-2.80 mm diameter granules increased as initial palygorskite concentration in sulphuric acid increased.
  • the maximum median green granule strength observed after 24 hours was 2.5 ⁇ 0.7 kg for granules containing 3.5 wt% palygorskite. This is a 2 kg increase in granule strength compared with ammonium sulphate granules granulated without acidified palygorskite binder.
  • This increase in green granule strength is significant for storage and handling as breakage (due to compression in the heap and impact and attrition forces during manufacture and handling) will increase leading to an increase in granulated ammonium sulphate product quality.
  • the silicate cement likely solidifies at ammonium sulphate crystal contact points providing adhesion at these contact points and additional mechanical strength. Residual palygorskite adhering to interfaces provides further mechanical strength to granules. Further, the modification of ammonium sulphate crystal habit by palygorskite involves decrease in crystal size and increased packing density. This enhances mechanical strength by increasing the physical contacts between neighbouring crystals and minimising internal voids, a feature distinguishing ammonium sulphate granules from which acidified palygorskite binder is absent. In summary, the method of the invention results in a granular ammonium sulphate product with increased mechanical strength, about 2 kg improvement in crush strength over prior granulated ammonium sulphate products.
  • composition and process of the present invention may be apparent to the skilled reader of this disclosure. Such modifications and variations are deemed within the scope of the present invention.
  • crystalline compounds include potassium chloride, potassium sulphate and combinations of these with ammonium salts such as ammonium sulphate.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

La composition d'engrais ci-décrite comprend des granulés à base d'un composé cristallin contenant un nutriment pour les plantes et d'un liant pour ledit composé cristallin. Le liant est formé à partir d'une argile acidifiée, par exemple, une argile polygorskite, et lie les cristaux du composé cristallin au sein desdits granulés. Dans un mode de réalisation, un liant à base d'argile polygorskite acidifiée augmente la résistance mécanique des granulés d'un composé d'engrais à base de sulfate d'ammonium.
PCT/AU2011/001467 2010-11-15 2011-11-15 Composition d'engrais contenant un nutriment pour les plantes et son procédé de production WO2012065214A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AU2010905046A AU2010905046A0 (en) 2010-11-15 A composition containing a plant nutrient and method for producing it
AU2010905046 2010-11-15

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WO2012065214A1 true WO2012065214A1 (fr) 2012-05-24

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104496665A (zh) * 2014-12-10 2015-04-08 竺叶洪 一种多元复合肥料及其制备方法和用途
CN105315097A (zh) * 2015-03-11 2016-02-10 兰州大学 一种生物营养强化肥料的制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5749936A (en) * 1996-06-07 1998-05-12 A.J. Sackett And Sons Company Method of producing dry granular fertilizer and soil amendments using clay slurry and dry chemicals
EP1070690A2 (fr) * 1999-07-20 2001-01-24 Inabonos, S.A. Engrais azoté contenant de l'azote sous forme ureique, nitrique, d'ammoniac et organique avec une solubilité et nitrification progressive et procede pour sa preparation
CN101265128A (zh) * 2008-04-16 2008-09-17 江苏华昌化工股份有限公司 颗粒氮肥的制备方法
CN102093119A (zh) * 2009-12-09 2011-06-15 中国科学院沈阳应用生态研究所 一种具有保水及土壤改良作用大豆专用肥及其制备
CN102093118A (zh) * 2009-12-09 2011-06-15 中国科学院沈阳应用生态研究所 一种具有保水及土壤改良作用玉米专用肥及其制备

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5749936A (en) * 1996-06-07 1998-05-12 A.J. Sackett And Sons Company Method of producing dry granular fertilizer and soil amendments using clay slurry and dry chemicals
EP1070690A2 (fr) * 1999-07-20 2001-01-24 Inabonos, S.A. Engrais azoté contenant de l'azote sous forme ureique, nitrique, d'ammoniac et organique avec une solubilité et nitrification progressive et procede pour sa preparation
CN101265128A (zh) * 2008-04-16 2008-09-17 江苏华昌化工股份有限公司 颗粒氮肥的制备方法
CN102093119A (zh) * 2009-12-09 2011-06-15 中国科学院沈阳应用生态研究所 一种具有保水及土壤改良作用大豆专用肥及其制备
CN102093118A (zh) * 2009-12-09 2011-06-15 中国科学院沈阳应用生态研究所 一种具有保水及土壤改良作用玉米专用肥及其制备

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Derwent World Patents Index; AN 2008-M51898 *
DATABASE WPI Derwent World Patents Index; AN 2011-J07500 *
DATABASE WPI Derwent World Patents Index; AN 2011-J07504 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104496665A (zh) * 2014-12-10 2015-04-08 竺叶洪 一种多元复合肥料及其制备方法和用途
CN105315097A (zh) * 2015-03-11 2016-02-10 兰州大学 一种生物营养强化肥料的制备方法

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