WO2013098404A1 - Procédés de préparation de compositions contenant du soufre et de compositions d'engrais contenant du soufre - Google Patents

Procédés de préparation de compositions contenant du soufre et de compositions d'engrais contenant du soufre Download PDF

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Publication number
WO2013098404A1
WO2013098404A1 PCT/EP2012/077074 EP2012077074W WO2013098404A1 WO 2013098404 A1 WO2013098404 A1 WO 2013098404A1 EP 2012077074 W EP2012077074 W EP 2012077074W WO 2013098404 A1 WO2013098404 A1 WO 2013098404A1
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Prior art keywords
sulphur
fertilizer
containing composition
composition
molten
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PCT/EP2012/077074
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English (en)
Inventor
Klaas Jan HUTTER
Charles James INGOLDSBY
Rafael Alberto Garcia Martinez
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Shell Internationale Research Maatschappij B.V.
Shell Oil Company
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Publication of WO2013098404A1 publication Critical patent/WO2013098404A1/fr

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    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05DINORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D9/00Other inorganic fertilisers
    • C05D9/02Other inorganic fertilisers containing trace elements

Definitions

  • the present invention relates to processes for the manufacture of sulphur-containing compositions and sulphur-containing fertilizer compositions.
  • Canola is an important cash crop in Alberta, Canada, and has high sulphur requirements at any growth stage. A shortage of sulphur can cause serious reductions in crop yield and quality, Manufacturing processes for sulphur-containing
  • fertilizers of the ammonium phosphate type often involve the use or incorporation of sulphates, see e.g. US
  • Elemental sulphur is not leached out of the soil, as sulphates are. Instead, micron sized elemental sulphur particles are oxidized to sulphate sulphur, which is the form utilized by the plants, by soil bacteria during the cropping season. Elemental sulphur is, thus, considered a slow release form of plant nutrient sulphur that is less prone to leaching out of the crops root zone. It is, therefore, advantageous to have a large proportion of the sulphur in fertilizers present as elemental sulphur present as small particles. Furthermore, elemental sulphur offers some additional benefits in agriculture, including acting as a fungicide against certain micro organisms, acting as a pesticide against certain soil and plant pests, assisting the decomposition of plant
  • US 3,333,939 describes the coating of ammonium phosphate granules with molten sulphur.
  • the granules are coated in a separate coating unit into which the sulphur is fed, by contacting the granules with molten sulphur or with a solution of ammonium polysulphide . Subsequently, the coated granules are dried.
  • US 3,333,939 describes the coating of ammonium phosphate granules with molten sulphur.
  • the granules are coated in a separate coating unit into which the sulphur is fed, by contacting the granules with molten sulphur or with a solution of ammonium polysulphide . Subsequently, the coated granules are dried.
  • US 3,333,939 describes the coating of ammonium phosphate granules with molten sulphur.
  • the granules are coated in
  • 3,333,939 teaches a process for preparing sulphur- containing fertilizer particles in which the sulphur is interspersed throughout the particles.
  • ammonia and phosphoric acid are allowed to react to form ammonium phosphate.
  • the ammonium phosphate formed is fed into a granulator in which it is mixed with urea and dry sulphur.
  • the granules obtained are dried in a dryer.
  • 3,333,939 is that the coating prevents a uniform
  • WO 2010/086395 and WO 2010/086396 disclose processes for the manufacture of sulphur-containing fertilizer compositions wherein a slurry of at least one phosphate- based fertilizer material is brought into contact with a surfactant and elemental sulphur.
  • the incorporation of the surfactant can help to reduce elemental sulphur concentration in the dusts generated during fertilizer manufacture .
  • the aim of the present invention is to provide sulphur-containing compositions which can be attractively used as a feedstock for the fertilizer manufacturing processes in which the above-mentioned safety problems are diminished or prevented.
  • Another aim is to use contaminated sulphur as a feedstock component in the manufacture of sulphur-containing fertilizer
  • compositions are provided.
  • step (d) subjecting the molten sulphur mixture as obtained in step (c) to an agitation treatment to form the sulphur- containing composition.
  • sulphur namely a first source of elemental sulphur and a second source of contaminated sulphur.
  • the elemental sulphur to be used in the process of the present invention can be obtained from any suitable source.
  • the elemental sulphur is obtained from an industrial process, such as the removal of unwanted sulphur components from natural gas.
  • the elemental sulphur used is high purity (> 99.9% S)
  • chemical sulphur for example high purity (>99.9% S) chemical sulphur as obtained from the Claus process.
  • the contaminated sulphur to be used in the process of the present process of the present invention has less purity than the elemental sulphur to be used.
  • the contaminated sulphur will usually be of significantly less purity than the elemental sulphur to be used.
  • the contaminated sulphur is sulphur filter cake. Sulphur filter cake is obtained from sulphur melting and filtration operations such as Frasch sulphur mining or other mining operations,
  • the contaminated sulphur contains anywhere in the range of from 30 to 99.9 wt.%, preferably from 50 to 99.5 wt.%, more preferably from 50 to 80 wt.%, elemental sulphur with the balance comprising lime, gypsum, silica, iron and other trace materials.
  • Sulphur filter cake will, in addition to sulphur, contain insoluble components such as lime, gypsum, silicon and iron.
  • Step (d) of the process according to the present invention ensures that these insoluble components are in a unique manner homogenously dispersed in the sulphur- containing composition.
  • the use of the sulphur-containing compositions according to the invention for use as a feedstock for the production of fertilizer materials has the advantage that these insoluble components will be homogenously dispersed as filler material in the
  • the present invention also relates to a sulphur-containing composition obtainable by the process according to the present invention.
  • step (a) both the elemental sulphur provided in step (a) and the
  • contaminated sulphur provided in step (b) can be in molten or solid form.
  • both the elemental sulphur and the contaminated sulphur are provided in molten form.
  • both the elemental sulphur and contaminated sulphur are provided in solid form.
  • the elemental sulphur is provided in molten form and the contaminated sulphur as provided in solid form, and in a fourth embodiment the elemental sulphur is provided in solid form and the contaminated sulphur is provided in molten form.
  • the elemental sulphur provided in step (a) is in molten form or in solid form and the
  • contaminated sulphur as provided in step (b) is in solid form.
  • the elemental sulphur provided in step (a) is in molten form and the contaminated sulphur provided in step (b) is in solid form.
  • the use of the source of contaminated sulphur has the further advantage that it reduces the melting energy of the sulphur mixture when compared to the melting energy of elemental sulphur as such.
  • the use of both a source of elemental sulphur and a source of contaminated sulphur allows the molten sulphur mixture to have a reduced viscosity.
  • the sulphur-containing composition as obtained in step (d) is also in molten form and the reduced viscosity of this composition allows the immediate pumping of the molten sulphur mixture into a manufacturing plant for
  • the sulphur composition in molten form is first collected in a container which can suitably be transported to a plant for fertilizer manufacture.
  • sulphur filter cake consists preferably of
  • Step (d) Energy input and the type of agitation in Step (d) will depend on heat transfer rate and the ratio between contaminated sulphur and elemental sulphur.
  • the agitation is carried with less than 25 kWh/m 3 .
  • step (d) is carried out using an energy of at least 4 kWh/m 3 ,
  • the agitation treatment can suitably be carried out by means known by a skilled person.
  • the agitation device to be used is selected from the group consisting of mechanical agitators, fluid recirculation, forced or natural convection, jet mixers, gas burbling, and the like.
  • use is made of a combination of a mechanical agitator and pump recirculation as the agitation device.
  • the contaminated sulphur is suitably first subjected to a preprocessing step in which the contaminated sulphur is formed into particles having an average particle size of less than 250 mm, preferably in the range of from 10-150 mm, more preferably in the range of from 10-50 mm.
  • the elemental sulphur can suitably be present in an amount of 1-99 wt . % and the contaminated sulphur can be present in an amount of 1-99 wt.%, based on the total weight of the molten mixture.
  • the elemental sulphur is preferably present in an amount of 10-90 wt.% and the contaminated sulphur is preferably present in an amount of 10-90 wt.%, based on the total weight of the molten mixture.
  • the weight ratio of elemental sulphur to contaminated sulphur is at least 0.40 preferably at least 0.50.
  • the weight ratio of elemental sulphur to contaminated sulphur is in the range of from 0.5-95.
  • the molten sulphur mixture as obtained in step (c) preferably contains elemental sulphur in an amount of 25-50 wt% and
  • steps (c) and (d) are suitably carried out at a
  • steps (c) and (d) are carried out at a temperature in the range of from 120-150 °C, more preferably in the range of from 125-140 °C.
  • the sulphur-containing composition as obtained in step (d) is allowed to solidify. In that way the sulphur-containing composition is obtained in solid form.
  • the manufactured in accordance with the process of the present invention is in solid form it can be transported as a solid to a plant for fertilizer manufacture.
  • the solid sulphur-containing composition may be in any solid form.
  • the solid sulphur-containing composition may be subjected to any conventional forming techniques before it is transported to the fertilizer manufacture plant. Such forming techniques include for instance prilling, rotoforming, granulation, and slating.
  • the sulphur-containing compositions as manufactured in accordance with the process according to the present invention can attractively be used in the manufacture of sulphur-containing fertilizer compositions.
  • the present invention also relates to a process for the manufacture of a sulphur-containing fertilizer composition, wherein the sulphur-containing composition as obtained in step (d) of the present process, in molten form or solidified form, is
  • the present invention therefore also relates to a process for manufacturing a sulphur-containing fertilizer composition, said process comprising the steps of:
  • step (d) subjecting the molten sulphur mixture as obtained in step (c) to an agitation treatment to form the sulphur- containing composition;
  • step (e) incorporating the sulphur-containing composition as obtained in step (d) , in molten form or solidified form, into a fertilizer material feedstock to obtain the sulphur-containing fertilizer composition.
  • both the sulphur-containing composition as obtained in step (d) and the fertilizer material feedstock can be in molten or solid form.
  • the fertilizer material feedstock is in molten form.
  • both the sulphur-containing composition and the fertilizer material feedstock are provided in molten form.
  • the sulphur-containing composition is provided in molten form and the fertilizer material feedstock is provided in solid form
  • the sulphur-containing composition is provided in solid form and the fertilizer material feedstock is provided in molten form.
  • the fertilizer material feedstock to be used in accordance with the present invention may be any known fertilizer material.
  • the fertilizer material feedstock comprises a phosphate-based fertilizer material feedstock, a urea-based fertilizer material feedstock, a potassium-based fertilizer material feedstock and/or a sulphur bentonite fertilizer material feedstock.
  • the present invention also relates to a sulphur- containing fertilizer composition obtainable by the process as described hereinabove.
  • the present invention also provides a sulphur- containing fertilizer composition
  • a sulphur- containing fertilizer composition comprising a fertilizer material feedstock and a sulphur-containing composition, which sulphur-containing composition contains elemental sulphur and contaminated sulphur.
  • fertilizer material feedstock to be used in accordance with the present invention comprises a
  • the fertilizer material feedstock will be present in an amount of at least 70 wt%, preferably at least 85 wt%, and the sulphur- containing composition will be present in an amount of less than 30 wt%, preferably less than 15 wt%, based on the total weight of the sulphur-containing fertilizer compositions .
  • the bentonite fertilizer material feedstock comprises sulphur bentonite fertilizer material feedstock
  • the bentonite fertilizer material feedstock is present in an amount of less than 20 wt%, preferably less than 15 wt%
  • the sulphur-containing composition is present in an amount of at least 80 wt%, preferably at least 85 wt%, based on the total weight of the sulphur-containing fertilizer compositions.
  • the phosphate-based fertilizer material to be used in accordance with the invention can suitably be selected from the group consisting of ammonium phosphates,
  • ammonium phosphate-based nitrogen-phosphorus-potassium (NPK) compounds super phosphates and partially
  • ammonium phosphates are monoammonium phosphates and diammonium phosphates.
  • Suitable super phosphates include, but are not limited to, normal superphosphates and triple
  • a phosphate-based fertilizer material which comprises at least one ammonium phosphate.
  • the fertilizer material is present in an amount of at least 50 wt.%, preferably in a range of from 50 to 99 wt.%, based on the total weight of the sulphur- containing fertilizer composition.
  • the urea-based fertilizer material to be used in accordance with the invention is suitably urea.
  • the potassium-based fertilizer material to be used in accordance with the invention can suitably be muriate of potash or potassium sulphate.
  • the sulphur-containing composition is added to a high shear dispersion mill wherein it is mixed with phosphoric acid or molten urea and the mixture so
  • the sulphur-containing composition is added to a preneutralizer or a pipe cross reactor wherein it is mixed with ammonia and phosphoric acid and other fertilizer feedstocks and the mixture so obtained is used in the production of monoammonium phosphate (MAP) or diammonium phosphate (DAP) .
  • MAP monoammonium phosphate
  • DAP diammonium phosphate
  • the mixing of the sulphur-containing compositions and the phosphoric acid or molten urea, or MAP or DAP feedstocks are preferably carried out in the presence of a surfactant.
  • the sulphur- containing composition is added to a potassium based fertilizer material such as potash.
  • the sulphur- containing composition is used to make a sulphur
  • bentonite fertilizer in which the pure elemental sulphur material typically used for sulphur bentonite production is substituted with the sulphur-containing composition.
  • bentonite is mixed with the
  • the process for manufacturing the sulphur-containing composition according to the process of the present invention is preferably carried out in the presence of at least one surfactant.
  • containing composition can be incorporated into in the fertilizer material in a number of especially attractive ways .
  • the sulphur containing composition is incorporated into the fertilizer material by (A) providing a slurry of at least one phosphate-based fertilizer material selected from the group consisting of ammonium phosphates, ammonium phosphate based nitrogen- phosphorus-potassium (NPK) compounds, super phosphates and partially acidulated phosphate rocks; (B) bringing said slurry into contact with at least one surfactant and (preferably a liquid phase of) the sulphur-containing composition; and (C) introducing the mixture obtained in step (B) into a granulator unit in order to obtain granules of the fertilizer composition, wherein the at least one phosphate-based fertilizer material is present in an amount of at least 50 wt .
  • A providing a slurry of at least one phosphate-based fertilizer material selected from the group consisting of ammonium phosphates, ammonium phosphate based nitrogen- phosphorus-potassium (NPK) compounds, super phosphat
  • the sulfur-containing composition is present in an amount in the range of from 1 to 25 wt.% and the at least one surfactant is present in an amount in the range of from 0.001 to 3 wt.% based on the overall weight of the fertilizer composition.
  • the present invention also provides a sulphur- containing fertilizer composition
  • a sulphur- containing fertilizer composition comprising: (A) the sulphur-containing composition in an amount in the range of from 1 to 25 wt.%, based on the total weight of the sulphur-containing fertilizer composition; (B) at least one phosphate-based fertilizer material selected from the group consisting of ammonium phosphates, ammonium
  • NPK nitrogen- phosphorus-potassium
  • the slurry of at least one phosphate-based fertilizer material is typically a slurry in water. This may be formed by the mixing of the required phosphate-based fertilizer material or materials and water or may be formed by the in-situ production of the phosphate-based fertilizer material in an aqueous medium.
  • An example of the latter is the production of an ammonium phosphate or other phosphate-base NPK compound by reacting ammonia, phosphoric acid and water in a reactor unit. Typically, the reaction takes place at atmospheric pressure and at temperatures in the range of from 100 °C to 150 °C.
  • water or sulphuric acid is added to the reactor unit to control the temperature of the mixture.
  • water may be added when a temperature reduction is needed and sulphuric acid may be added to when a temperature increase is needed and/or when some sulphate sulphur is desirable in the final fertilizer composition.
  • sulphuric acid may be added to when a temperature increase is needed and/or when some sulphate sulphur is desirable in the final fertilizer composition.
  • the liquid phase may be added when a temperature reduction is needed and sulphuric acid may be added to when a temperature increase is needed and/or when some sulphate sulphur is desirable in the final fertilizer composition.
  • the particles of the sulphur-containing composition are dispersed or suspended in the slurry.
  • the particles of the sulphur-containing composition have a size of at least 0.5 microns, preferably at least 5.0 microns, more preferably at least 10 microns, even more preferably at least 30 microns.
  • the particles of the sulphur-containing composition have a size of at most 250 microns, preferably at most 200 microns, more preferably at most 150 microns, most preferably at most
  • the water content in the slurry of the sulphur-containing composition is typically kept as low as possible, preferably in the range of from 10 to 40 wt.%, based on the total weight of the mixture, more preferably in the range of from 15 to 30 wt.%, based on the total weight of the slurry.
  • the slurry of the sulphur- containing composition is preferably stirred or mixed in a suitable apparatus (e.g. a high shear milling device) to homogenise the slurry prior to introducing it into the manufacturing process.
  • a suitable apparatus e.g. a high shear milling device
  • the slurry of the sulphur-containing composition contains particles of the sulphur-containing composition which are dispersed in the aqueous medium (such as water and the like) .
  • aqueous medium such as water and the like
  • dispersed particles of the sulphur-containing composition in an aqueous medium, preferably dispersed micron-sized particles of the sulphur-containing
  • compositions in the aqueous medium are suitably kept in dispersion through the addition of a suitable emulsifier and/or viscosity modifier to obtain a pumpable slurry.
  • a suitable emulsifier and/or viscosity modifier are known in the art and are not critical to the invention.
  • liquid phase comprising the sulphur-containing composition comprises the sulphur- containing composition in molten form.
  • Molten sulphur-containing composition can be obtained from the sulphur- containing composition in solidified form, by melting in a suitable melting apparatus, for instance a tube melter. The use of molten sulphur-containing composition is advantageous when the sulphur-containing composition is obtained in the molten state from an industrial process.
  • the temperature of the sulphur-containing mixture so obtained is preferably kept above the melting point of sulphur, preferably at temperatures in the range of from 115 °C to 150 °C.
  • the molten sulphur-containing composition is added into a reactor at this temperature, before the reaction mixture is introduced into a granulator.
  • the surfactant may be provided in any form suitable for mixing with the sulphur in a liquid phase and/or the slurry of at least one phosphate- based fertilizer material.
  • the surfactant may be added to the sulphur- containing composition in a liquid phase, before it is brought into contact with the at least one phosphate- based fertilizer material.
  • the surfactant may be added directly to the slurry of at least one phosphate-based fertilizer material before or after it is brought into contact with the sulphur-containing
  • the surfactant is added as a liquid directly to the slurry of at least one phosphate-based fertilizer material.
  • the surfactant is dispersed throughout the sulphur- containing fertilizer composition. That is, the
  • surfactant is incorporated throughout the granules and does not exist merely in a surface layer.
  • Reference herein to granules is to discrete particles. These particles comprise the at least one phosphate-based fertilizer material, the surfactant and the sulphur- containing composition.
  • water and steam can also be fed to the granulator to control the temperature of the granulation process as needed.
  • the granules of the sulphur-containing fertilizer compositions obtained after the granulation step are optionally dried in a drying unit.
  • a drying unit In a preferred
  • the granules are air-dried in the drying unit, thereby avoiding the need for additional drying equipment.
  • drying units wherein heat transfer for drying is accomplished by direct contact between the wet solid and hot gases are used, thereby enabling a faster drying step.
  • the drying unit is a rotary dryer.
  • the granules are sorted on their size in a sorting (screening) unit to achieve a more uniform size distribution.
  • oversized granules are crushed to less than 1 mm and along with undersized granules are returned to the granulator as so-called recycle material (or "off-spec fines") .
  • a preferred size range for the granules is in the range of from 1.5 to 5.0 mm, more preferably in the range of from 2 to 4 mm, expressed as the average diameter of the granules.
  • the use of granules which fall within this range is more likely to enable a more even distribution of the fertilizer ingredients in the soil after applying the granules to the soil.
  • the surfactant to be used in accordance with the present process for the manufacture of the sulphur- containing fertilizer composition can be selected from the group consisting of anionic surfactants, cationic surfactants and amphoteric surfactants.
  • Suitable anionic surfactants include, but are not limited to, lignin derivatives such as lignosulphonates , aromatic sulphonates and aliphatic sulphonates and their formaldehyde condensates and derivatives, fatty acids
  • Lignosulphonates are known and are defined, for example, in Chemielexikon [Dictionary of Chemistry] , 9th Edition, Volume 3, Georg-Thieme Verlag, Stuttgart, N. Y. 1990, page 2511. Particularly suitable
  • lignosulphonates are the alkali metal salts and/or alkaline earth metal salts and/or ammonium salts, for example the ammonium, sodium, potassium, calcium or magnesium salts of lignosulphonic acid.
  • the sodium, potassium or calcium salts are preferably used, and the sodium and/or calcium salts are very particularly
  • lignosulphonates also encompasses mixed salts of different ions such as potassium/sodium lignosulphonate, potassium/calcium lignosulphonate or the like, in particular sodium/calcium lignosulphonate.
  • Preferred aromatic sulphonates are alkylnaphthalene sulphonates and condensates thereof;
  • alkyl group preferably contains 1 to 10 carbon atoms.
  • Typical counter-ions are: proton, sodium, potassium, calcium, isopropropyl animonium, ammonium, alkanolamine etc.
  • Exemplary alkylnaphthalene sulfonates include metal salts and organic salts of alkylnaphthalene sulfonates such as sodium diisopropylnaphthalene sulfonate,
  • alkylbenzene sulphonates are preferred, in particular wherein the alkyl contains 1 to 12 carbon atoms.
  • the anionic surfactant can be present in an amount in the range of from 0.001 to 3 wt.%, based on the total weight of the sulphur-containing fertilizer composition.
  • the at least one anionic surfactant is present in an amount of at least 0.01 wt.%, preferably at least 0.05 wt.%, more preferably at least 0.08 wt.%, even more preferably at least 0.1 wt.%, most preferably at least 0.15 wt.%, based on the total weight of the
  • the at least one anionic surfactant is present in an amount of at most 2 wt.%, more preferably at most 1 wt.%, even more preferably at most 0.9 wt.%, most preferably at most 0.5 wt.%, based on the total weight of the sulphur- containing fertilizer composition.
  • amphoteric surfactant' refer to compounds present in their cationic or amphoteric form as well as those that will be converted into their cationic or amphoteric form (e.g. by protonation or alkylation) in situ.
  • Suitable cationic surfactants include, but are not limited to, nitrogen-containing cationic surfactants.
  • Nitrogen-containing cationic surfactants will generally be selected from the group of aliphatic nitriles (RCN) , aliphatic amides (RCONH2) , aliphatic amines (e.g. RNH2, RRNH, R(CH 3 ) 2 N, R(CH 3 ) 3 N + , RR(CH 3 )N), R 3 N) , aliphatic polyamines ((RNHR') n NH 2 ) , beta primary aliphatic amines (e.g.
  • RCH (NH 2 ) CH 3 ) beta aliphatic polyamines aryl aliphatic amines (e.g. R(C 6 H 5 ) H 2 include the benzyl derivatives e.g. RN (CH 3 ) 2 CH 2 C 6 H 5 ) , etheramines (e.g.
  • ROR'NH2 non-aromatic cyclic amines
  • non-aromatic cyclic amines e.g.
  • alkylimidazolines and alkyl morpholines ) , or derivatives of any of compounds listed above, such as their salts, ethylene or propylene oxide adducts or quaternary
  • ammonium salts are fatty amine alkoxylates represented by the general formula R 1 NR 2 R 3 , wherein R 1 is an aliphatic moiety
  • R 2 and R 3 are each independently aliphatic moieties containing from 2 to 25 ethoxy/propoxy units.
  • R 2 and R 3 are identical.
  • Suitable amphoteric surfactants include, but are not limited to, nitrogen-containing amphoteric surfactants. These may be selected from the group
  • amine oxides RNH 2 0, RNH(CH 3 )0, RN(CH 3 ) 2 0
  • betaine derivatives e.g. RNH(CH 2 C0 2 ), RN (CH 3 ) (CH 2 C0 2 ) or R (CH 3 ) 2 (CH2CO2)
  • alkylamido-propylbetaines e.g.
  • RCONHR'N (CH 3 ) 2 (CH2CO2) ) RCONHR'N (CH 3 ) 2 (CH2CO2)
  • sultaines e.g. RN (CH 3 ) 2 R' S0 3 or RCONHR'N (CH 3 ) 2 CH 2 CH (OH) CH 2 S0 3 )
  • Lecithins e.g.
  • R represents substituted or unsubstituted
  • R' represents an alkyl radical of from 2 to 4 carbon atoms and n
  • the at least one surfactant is selected from aliphatic amines (e.g. RNH 2 , RRNH, R(CH 3 ) 2 N, R(CH 3 ) 3 N + , RR(CH 3 )N, R 3 N) and their ethylene or propylene oxide adducts.
  • aliphatic amines e.g. RNH 2 , RRNH, R(CH 3 ) 2 N, R(CH 3 ) 3 N + , RR(CH 3 )N, R 3 N
  • their ethylene or propylene oxide adducts e.g. RNH 2 , RRNH, R(CH 3 ) 2 N, R(CH 3 ) 3 N + , RR(CH 3 )N, R 3 N
  • the at least one surfactant is a ethylene or propylene oxide adduct of an aliphatic amine, wherein R is an aliphatic radical containing in the range of from 12 to 20 carbon atoms, more preferably from 16 to 20 carbon atoms.
  • R is an aliphatic radical containing in the range of from 12 to 20 carbon atoms, more preferably from 16 to 20 carbon atoms.
  • propylene oxide adduct of an aliphatic amine is more preferably the ethylene or propylene oxide adduct of a tallow amine.
  • At least one cationic or amphoteric surfactant is present in an amount of at least 0.0001 wt.%, preferably at least 0.001 wt.%, more preferably at least 0.005 wt.%, even more preferably at least 0.008 wt.%, yet even more preferably at least 0.01 wt.%, based on the total weight of the sulphur-containing fertilizer composition.
  • at least one cationic or amphoteric surfactant is present in an amount of at least 0.0001 wt.%, preferably at least 0.001 wt.%, more preferably at least 0.005 wt.%, even more preferably at least 0.008 wt.%, yet even more preferably at least 0.01 wt.%, based on the total weight of the sulphur-containing fertilizer composition.
  • at least one cationic or amphoteric surfactant is present in an amount of at least 0.0001 wt.%, preferably at least 0.001
  • amphoretic surfactant is present in an amount of at most
  • composition is incorporated into the fertilizer material by (i) using a dispersion mill, wherein a rotor turns within a slotted stator, to wet mill the sulphur- containing composition in solidified form in a liquid, thereby providing a dispersion of milled sulphur- containing composition in the liquid; (ii) combining the dispersion of milled sulphur-containing composition with the fertilizer material components to provide a mixture of the sulphur-containing composition and the fertilizer material; and (iii) granulating the mixture in a
  • sulphur- containing composition is effectively incorporated into fertilizer material in a surprising simple way. Low amounts of sulphur dust are created within the
  • An important advantage of the process according to the present invention is that it enables to select and closely control (or manage) the size and size
  • the actual size and size distribution of the particles of the sulphur-containing composition in the sulphur-containing fertilizer composition can be selected for example dependent on the agricultural environments (e.g. soil and climatic conditions) for which the fertilizer is intended.
  • step (i) the sulphur-containing composition in a liquid
  • dispersion mill wherein a rotor turns within a slotted stator, thereby providing a dispersion of milled sulphur- containing composition in the liquid.
  • the liquid and the sulphur-containing composition are drawn by the rotation of the rotor into the rotor/stator assembly, and are accelerated and expelled radially through the openings in the slotted stator. With each pass through the
  • the sulphur-containing composition is subjected to a combination of mechanical and hydraulic shear such that the particles of elemental sulphur are reduced in size.
  • the rotor turns at very high speeds, preferably such that the tip speed is from 1500 to 3500 metres per minute, more preferably from 2000 to 3000 metres per minute. Higher tip speeds result in a higher energy input in the dispersion mill and result in a smaller average particle size. The speed should be sufficiently high to achieve the required particle size.
  • a preferred dispersion mill has a slotted rotor inside a slotted stator. When the rotor and stator slots come into alignment, the liquid and the sulphur- containing composition are ejected from the rotor slots into the stator slots.
  • Suitable dispersion mills are described in US 5,522,553 and are available from Kady International, USA.
  • the sulphur-containing composition may be added to the dispersion mill in molten form or in solidified form, but is preferably added in solidified form because this avoids having to keep the sulphur- containing composition at a high temperature (sulphur is molten above 120 °C) .
  • the sulphur-containing composition is preferably added as pellets, e.g.
  • the liquid in step (i) may be chosen from a broad variety of liquids but is preferably an aqueous liquid.
  • the aqueous liquid may be an acidic aqueous solution such as an aqueous solution of phosphoric acid or sulphuric acid, and is most preferably selected from an aqueous solution of phosphoric acid, an aqueous solution of ammonium phosphate, an aqueous solution of ammonium sulphate and a combination thereof.
  • the phosphoric acid preferably has a strength corresponding to from 1 to 60% of P 2 O 5 in water, more preferably from 5 to 50%.
  • the aqueous liquid contains as little water as possible to avoid the introduction of excess process water; any excess water that is introduced into the fertilizer production process is to be eliminated at a later stage and thereby leads to a more complex and more energy intensive process.
  • the weight percentage of the sulphur-containing composition based upon the combined weight of the
  • sulphur-containing composition and the aqueous liquid in step (i) is preferably from 10 to 70 wt.%, more
  • one or more surfactants are added during step (i) or step (ii) .
  • the surfactant ( s ) may be added to the liquid before the sulphur-containing composition is wet milled, or may be added to the dispersion of milled sulphur-containing composition before or during the combination with further components.
  • the surfactants may help to further reduce the production of sulphur dust during fertilizer
  • step (iii) may aid the granulation of the fertilizer in step (iii) and may reduce the viscosity of the dispersion of the sulphur-containing composition produced in step
  • the surfactants could include cationic surfactants such as the ethylene oxide or propylene oxide adduct of an aliphatic amine, or could include anionic surfactants such as a lignosulphonate .
  • the one or more surfactants are added in such an amount that the granulated elemental sulphur- containing fertilizer composition as produced in step (iii) comprises from 0.001 to 5.0 wt . % surfactant, preferably from 0.10 wt . % to 1.5 wt.%, based on the total weight of the granulated sulphur-containing fertilizer composition .
  • the liquid is added to the dispersion mill first, the mill is started and then the sulphur-containing composition is added over a relatively short period of time.
  • the addition rate for the sulphur-containing composition is preferably as fast as possible without overloading the mill.
  • the energy input during the milling can be expressed as power per volume or mass of sulphur- containing composition processed, e.g. kWh/m 3 sulphur- containing composition processed or kWh/ton sulphur- containing composition processed.
  • the energy input affects the size of the milled particles of the sulphur- containing composition in the resulting dispersion, so is chosen according to the required particle size. Higher energy input provides smaller particle sizes.
  • higher energy input can be achieved by reducing the amount of the sulphur-containing composition that is milled.
  • the energy input is from 10 (preferably above 20) to 1000 kWh/ton sulphur-containing composition processed, more preferably from 50 to 100 kWh/ton sulphur-containing composition processed, even more preferably from 65 to 85 kWh/ton sulphur-containing composition processed.
  • Part of this higher energy will be transferred to the dispersion being formed in step (i) as thermal energy thereby increasing the temperature
  • Such temperature increase can be controlled using a suitable heat exchanger (possibly incorporated in the dispersion mill) .
  • Preferred temperatures for wet milling of the sulphur-containing composition are between 0 and 120 °C, more preferably between 15 and 80 °C. In some embodiments, this temperature increase avoids any additional heating steps thereby saving energy and equipment costs.
  • step (i) controlling the parameters in step (i), specifically the size of slots in the stator and optionally the rotor, the tip speed of the rotor and the energy input, and/or the physical-chemical properties of the liquid ⁇ composition, temperature, viscosity) , it is possible to control the particle size and particle size distribution of the resulting dispersion. It is important to be able to control the particle size of the sulphur-containing fertilizer composition because the particle size affects the effectiveness (rate of release) of the sulphur- containing fertilizer. For different agricultural
  • the present invention enables the skilled person to produce elemental sulphur-containing fertilizer compositions with a
  • the present invention also provides sulphur- containing fertilizer particles with a shape that has a higher surface area to volume ratio than the
  • substantially spherical particles produced in other processes such as (wet) prilling processes.
  • Particles with a high surface area to volume ratio are preferred because oxidation of the sulphur-containing composition will be faster with a higher surface area (see Watkinson et al, Fertilizer Research 35, 115-126, 1993).
  • fertilizer particles with a high surface area to volume ratio may also have better
  • the elemental sulphur-containing fertilizer composition is a sulphur - triple super phosphate fertilizer composition
  • the liquid is an aqueous solution of phosphoric acid
  • the dispersion of milled sulphur- containing composition in phosphoric acid solution is mixed and reacted with phosphate rock, thereby providing a mixture of the sulphur-containing composition and soluble calcium phosphate.
  • the phosphoric acid preferably has a strength of from 5 to 60 wt .
  • % P 2 O 5 more preferably from 10 to 50 wt . % P 2 O 5 and the resulting dispersion of milled sulphur-containing composition in phosphoric acid preferably comprises from 1 to 60 wt . % sulphur-containing composition and from 5 to 55 wt . % P 2 O 5 based upon the weight of the dispersion, more preferably from 20 to 40 wt . % sulphur-containing composition and from 10 to 50 wt . % P 2 O 5 .
  • the relative amounts of the phosphate rock and the dispersion of the sulphur-containing composition in phosphoric acid are preferably set such that the R ratio (the ratio of P 2 O 5 from the phosphate rock to P 2 O 5 from phosphoric acid) is from 2.0 to 2.8 (this will vary with the quality of the phosphate rock and phosphoric acid) .
  • the dispersion of milled sulphur-containing composition is combined with phosphate rock using methods known to the skilled person.
  • non-granular triple super phosphate which is used as an intermediate for production of compound fertilizer by granulation processes
  • the dispersion of milled sulphur-containing composition can be combined with phosphate rock in a suitable mixer such as a cone mixer.
  • finely ground phosphate rock e.g. 80% passing 200 mesh
  • the sulphur-containing fertilizer composition is a sulphur monoammonium
  • step (ii) the dispersion of milled sulphur-containing composition in liquid is mixed and reacted with ammonia, thereby providing a mixture of sulphur-containing composition and ammonium phosphate.
  • an aqueous solution of phosphoric acid is used as the liquid and preferably has a strength of from 5 to 60 wt . % P 2 O 5 , more preferably from 10 to 50 wt. % P 2 O 5 and the resulting dispersion of milled sulphur-containing composition in phosphoric acid preferably comprises from 1 to 60 wt .
  • step (ii) the amount of ammonia is determined by the required product.
  • the molar ratio of ammonia and phosphoric acid is typically kept between values of from
  • sulphur diammonium phosphate the molar ratio of ammonia and phosphoric acid is typically kept between values of from 1.2 to 2.0.
  • sulphur - nitrogen/phosphorus/potassium fertilizer composition the molar ratio of ammonia and phosphoric acid is typically kept between values of from 0.7 to 1.7.
  • composition and the ammonia are preferably mixed in step (ii) in a pre-neutraliser or a pipe cross reactor.
  • the ammonia is preferably supplied as anhydrous ammonia.
  • the reaction of the phosphoric acid and the ammonia is exothermic and typically results in vigorous mixing in a pre-neutraliser or pipe cross reactor such that no further agitation is required.
  • Residence time in a pipe cross reactor is preferably just a few seconds, e.g. 1-5 seconds. Residence time in a pre- neutraliser is likely to be longer, e.g. from 30 to 60 minutes. For the production of sulphur - nitrogen/phosphorus/potassium fertilizer it is necessary to incorporate potassium into the fertilizer.
  • step (ii) can be achieved by mixing the dispersion of milled sulphur-containing composition in phosphoric acid with ammonia and with a potassium salt.
  • step (iii) can be achieved in step (iii) by adding a potassium salt to the granulator unit.
  • step (iii) of the process of the invention the mixture of sulphur-containing
  • composition and fertilizer material is granulated in a granulator unit to provide granulated sulphur-containing fertilizer composition.
  • Other ingredients may be added during the manufacturing process to tailor the fertilizer products to their intended end-use. Examples include plant micro- nutrients such as boron, potassium, sodium, zinc, manganese, iron, copper, molybdenum, cobalt, calcium, magnesium and combinations thereof. These nutrients may be supplied in elemental form or in the form of salts, for examples as sulphates, nitrates or halides.
  • the amount of plant micronutrients depends on the type of fertilizer needed and is typically in the range of between 0.1 to 5%, based on the total weight of the granules.
  • composition as obtained in step (iii) is preferably dried in a drying unit.
  • the drying unit In a preferred embodiment, the
  • fertilizer is air-dried in the drying unit, thereby avoiding the need for additional drying equipment.
  • drying units wherein heat transfer for drying is accomplished by direct contact between the wet solid and hot gases are used, thereby enabling a faster drying step.
  • the drying unit is a rotary dryer .
  • fertilizer granules are sorted on their size in a sorting unit to achieve a more uniform size distribution.
  • oversized granules are crushed and returned to the sorting unit while undersized granules are returned to the granulator as so-called off-spec fines.
  • preferred size range for the fertilizer granules is from 1.5 to 5.0 mm, more preferably from 2 to 4 mm, expressed as the average diameter of the granules. The use of granules which fall within this range is more likely to enable a more even distribution of the fertilizer
  • the particle size and particle size distribution are controlled by controlling one or more of: the size of slots in the stator, the size of slots in the rotor, the tip speed of the rotor, the energy input, and the physical-chemical properties (composition, temperature, viscosity) of the liquid .
  • the sulphur-containing composition is incorporated into the fertilizer material by (1) mixing ammonia, phosphoric acid and water in a reactor unit to obtain an ammonium phosphate mixture ;
  • step (2) introducing the mixture obtained in step (1) into a granulator unit to obtain granules, wherein a liquid phase comprising the sulphur-containing composition is brought into contact with ammonia, phosphoric acid and water in the reactor unit in step (1) or is introduced in the granulator unit in step (2) .
  • step (1) of this embodiment ammonia, phosphoric acid and water are contacted in a reactor unit to obtain an ammonium phosphate mixture.
  • the water content in the ammonium phosphate mixture is kept as low as possible, preferably between approximately 10 and 20% based on the total weight of the mixture, more preferably between 12 and 15% based on the total weight of the mixture.
  • the mixing takes place at atmospheric pressure and at temperatures between about 100 °C and about 130 °C.
  • water or sulphuric acid is added to the reactor unit to control the temperature of the mixture.
  • water is added when a temperature reduction is needed, sulphuric acid is added to when a temperature increase is needed.
  • a liquid phase comprising the sulphur-containing composition is brought into contact with ammonia, phosphoric acid and water in the reactor unit in step (1) .
  • ammonia, phosphoric acid and water are mixed in a reactor unit to obtain an ammonium phosphate mixture; this mixture is then introduced into a granulator unit to obtain
  • the sulphur-containing composition is introduced into the reactor unit in step (1) substantially at the same time as the other
  • the crushing strength of the granules can be improved if the sulphur is added into the reactor unit in step (1) .
  • the sulphur-containing composition is introduced as a slurry of water and particles of the sulphur-containing composition.
  • the particles of the sulphur-containing composition are dispersed or suspended in the slurry.
  • the particles have a size ranging from between about 0.5 to about 150 microns, preferably between about 1.0 and about 100 microns.
  • the water content in the slurry of the sulphur-containing composition is typically kept as low as possible,
  • the slurry of the sulphur-containing composition is preferably stirred or mixed in a suitable apparatus to homogenise the slurry prior to introducing it into the manufacturing process.
  • the slurry of the sulphur-containing composition is preferably stirred or mixed in a suitable apparatus to homogenise the slurry prior to introducing it into the manufacturing process.
  • the slurry of the sulphur-containing composition is preferably stirred or mixed in a suitable apparatus to homogenise the slurry prior to introducing it into the manufacturing process.
  • composition contains particles of the sulphur-containing compositon which are dispersed in the water.
  • This type of slurry comprises dispersed particles of the sulphur- containing composition in water, preferably dispersed micron-sized particles in water.
  • the particles of the sulphur-containing composition are suitably kept in dispersion through the addition of a suitable emulsifier.
  • Suitable emulsifiers are known in the art and are not critical to the invention. An advantage of using
  • dispersed particles of the sulphur-containing composition is that the precipitation of particles of the sulphur- containing composition is kept to a minimum and the sulphur-containing composition is distributed more homogeneously throughout the water.
  • the need for stirring or mixing prior to introducing the slurry of the sulphur-containing composition into the reactor unit is reduced.
  • the slurry is introduced by pumping the slurry of the sulphur-containing composition from a slurry reservoir unit into the reactor unit.
  • the sulphur- containing composition is introduced into the reactor unit in step (1) in molten form.
  • the molten sulphur- containing composition can be obtained from the sulphur- containing composition in solidified form, by melting in a suitable melting apparatus, for instance a tube melter.
  • a suitable melting apparatus for instance a tube melter.
  • the molten composition can directly be passed in the fertilizer manufacturing process according to the
  • the temperature of the mixture of the sulphur-containing composition is preferably kept above the melting point of sulphur, preferably between temperatures of 115 °C and 121 °C.
  • ingredients may be incorporated into the sulphur-containing fertilizer composition of the present invention, in order to tailor the fertilizer composition to its intended end-use.
  • examples include plant
  • micronutrients such as boron, selenium, sodium, zinc, manganese, iron, copper, molybdenum, cobalt, calcium, magnesium and combinations thereof. These nutrients may be supplied in elemental form or in the form of salts, for examples as sulphates, nitrates, oxides or halides. In this way, granules enriched in plant nutrients are obtained.
  • the amount of plant micronutrients depends on the type of fertilizer needed and is typically in the range of from 0.1 to 5 wt.%, based on the total weight of the granules.
  • the present invention further relates to the use of a sulphur-containing fertilizer composition according to the present invention to grow agricultural products from soil, wherein the fertilizer composition is used on sulphur-deficient soil.
  • the present invention can also suitably be used in respect of hydroponical applications.
  • the viscosity of the mixture is such that at different temperatures and or blend compositions the fluid becomes pumpable and is suitable for incorporation into the fertilizer manufacturing process.
  • a prototype melter is fed with equal amounts of solid elemental sulphur pastilles and solid filter cake, from sulphuric acid production ( ⁇ 2.5mm), containing 60% sulphur. The melt is mixed and subjected to agitation (2kWh/m 3 ), then fed using a dosing pump to an ammonium phosphate complete-mix agitated reactor (pre- neutralizer) , together with defined quantities of gaseous ammonia, phosphoric acid and sulphuric acid.
  • pre- neutralizer ammonium phosphate complete-mix agitated reactor
  • a surfactant is used to help the dispersion of the sulphur containing material to disperse into the
  • fertilizer slurry Such slurry is then pumped to a granulator unit to produce granules, which are further dried and classified to obtain a valuable sulphur- containing fertilizer based on waste filter cake. The off-size fraction is recycled to the granulator.

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  • Fertilizers (AREA)

Abstract

Cette invention concerne un procédé de préparation d'une composition contenant du soufre, ledit procédé comprenant les étapes suivantes : (a) utilisation d'une source de soufre élémentaire ; (b) utilisation d'une source de soufre contaminé ; (c) mélange de la source de soufre élémentaire et de la source de soufre contaminé dans des conditions permettant d'obtenir une mélange de soufre à l'état fondu ; et (d) soumission du mélange de soufre à l'état fondu obtenu à l'étape (c) à un traitement d'agitation pour former la composition contenant du soufre selon l'invention. Cette invention concerne en outre un procédé de préparation d'une composition d'engrais contenant du soufre, ladite composition d'engrais contenant du soufre pouvant être obtenue par ledit procédé, et l'utilisation de ladite composition d'engrais contenant du soufre pour faire pousser des produits agricoles dans le sol.
PCT/EP2012/077074 2011-12-29 2012-12-28 Procédés de préparation de compositions contenant du soufre et de compositions d'engrais contenant du soufre WO2013098404A1 (fr)

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WO2014009326A1 (fr) * 2012-07-09 2014-01-16 Shell Internationale Research Maatschappij B.V. Procédé pour la préparation d'une émulsion de particules de soufre élémentaire
WO2015104286A1 (fr) * 2014-01-09 2015-07-16 Shell Internationale Research Maatschappij B.V. Procédé de préparation d'un engrais à base du'rée et de soufre
WO2015104293A1 (fr) * 2014-01-09 2015-07-16 Shell Internationale Research Maatschappij B.V. Engrais à teneur réduite en biuret
WO2015104296A1 (fr) * 2014-01-09 2015-07-16 Shell Internationale Research Maatschappij B.V. Engrais à base d'urée présentant une dureté améliorée
WO2016016150A1 (fr) * 2014-07-28 2016-02-04 Shell Internationale Research Maatschappij B.V. Procédé de préparation d'un engrais à base d'urée et de soufre
WO2016097378A1 (fr) * 2014-12-19 2016-06-23 Shell Internationale Research Maatschappij B.V. Procédé de préparation d'un agent d'amélioration de sol contenant du soufre
WO2017005695A1 (fr) * 2015-07-07 2017-01-12 Yara International Asa Procédé de fabrication de matériau particulaire à base d'urée contenant du soufre élémentaire
WO2017037262A1 (fr) * 2015-09-04 2017-03-09 Shell Internationale Research Maatschappij B.V. Engrais à base d'urée-nitrate d'ammonium

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