WO2017007315A1 - Granulation of urea products - Google Patents
Granulation of urea products Download PDFInfo
- Publication number
- WO2017007315A1 WO2017007315A1 PCT/NL2016/050486 NL2016050486W WO2017007315A1 WO 2017007315 A1 WO2017007315 A1 WO 2017007315A1 NL 2016050486 W NL2016050486 W NL 2016050486W WO 2017007315 A1 WO2017007315 A1 WO 2017007315A1
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- WO
- WIPO (PCT)
- Prior art keywords
- urea
- ammonium sulfate
- granulation
- salt
- liquid
- Prior art date
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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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
- B01J2/16—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by suspending the powder material in a gas, e.g. in fluidised beds or as a falling curtain
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C9/00—Fertilisers containing urea or urea compounds
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C9/00—Fertilisers containing urea or urea compounds
- C05C9/005—Post-treatment
-
- 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 invention relates to a method for the production of granules of urea products comprising an insoluble amount of a salt, such as ammonium sulfate (AS) or potassium chloride.
- a salt such as ammonium sulfate (AS) or potassium chloride.
- AS ammonium sulfate
- UAS ammonium sulfate
- Urea products are products comprising urea and, preferably, also another component generally suitable for fertilizing purposes.
- such components are, e.g., ammonium sulfate, ammonium nitrate, potassium chloride, or other salts based on sulfur, calcium salts, magnesium salts, zinc-salts (e.g. zinc oxide, zinc sulphate) and further salts of B, Cu, Fe, CI, Mn, Mo.
- UAS urea ammonium sulfate
- Urea granules are typically produced in a fluid bed granulator, wherein particles are kept in motion by an air stream. Onto these particles liquid urea is sprayed, in the form of droplets or as a film, thereby causing particle growth. The resulting granulate has excellent strength allowing it to be transported by ship or over land over large distances.
- Ammonium sulfate is a salt which is generally produced by reacting ammonia with sulfuric acid. The resulting solution is concentrated and converted into solid particles or a slurry.
- Ammonium sulfate (AS) is soluble in urea (such as a urea melt) up to a concentration of about 20% and then forms a solution, i.e., a homogeneous liquid. This homogeneous liquid can be processed in a fluid bed granulator in essentially the same way as a standard urea solution.
- a background reference relating to such a granulation process is US2013/0319060.
- a method is disclosed for recycling ammonium salts, obtained from a scrubbing system for the removal of ammonia from the off-gas of a urea granulator, by mixing these salts homogeneously in the urea granulator.
- Both UAS (a urea/ammonium salt stream) and a urea solution are added to a granulator. Thereby the amount of UAS is the highest in the first compartment of the granulator, and decreased in downstream direction along the axis of the granulator.
- the highest amount of the urea solution is sprayed into the granulator at the granule flow outlet side, and the amount of urea solution is decreased in upstream direction along the axis of the granulator.
- the amount of ammonia salt is lower than 20% by weight. The method is disclosed to have the advantage that the moisture uptake of the resulting urea ammonium salt granules is similar to the moisture uptake of urea granulate.
- the dust for the major part consists of Ammonium Sulfate, which puts extra constraints and demands to the rework/recycle of it.
- dust is scrubbed leading to a diluted UAS aqueous stream.
- the stream is reworked by concentrating in one or more evaporators.
- extra measures have to be taken to prevent that the solubility of ammonium sulfate in urea will be exceeded in these cases.
- the increased dust-release /increased dust-content of the product will also lead to an increased tendency for fouling/scaling product build up at the inner walls of all process-equipment in the granulation process. This fouling will lead to an increased risk of choking/blocking and hence an increased necessity of cleaning, etc. This will lead to an increase of down time of the granulation plant.
- the invention provides a method for producing granules of a urea product comprising urea and at least one salt, the method comprising providing a slurry comprising urea and, relative to the urea, an amount of the salt exceeding the solubility limit of the salt in the urea; subjecting said slurry to a fluidized bed granulation process, thereby forming a Urea Product Granulate
- the invention provides a method for producing UAS granules, the method comprising providing a slurry comprising urea and, relative to the urea, more than 20 wt.% of ammonium sulfate; subjecting said slurry to a fluidized bed granulation process, thereby forming a UAS granulate intermediate; providing a liquid comprising urea and, relative to the urea, an amount of 0 wt.% to 20 wt.% of ammonium sulfate, said ammonium sulfate being dissolved in the urea; presenting said liquid as a final granulation liquid to the UAS granulate intermediate, thereby obtaining a urea ammonium sulfate granulate having more than 20% by weight of ammonium sulfate.
- the invention presents a urea product granulate obtainable by the method according to any one of the preceding claims.
- the invention concerns a urea ammonium sulfate granulate obtainable by the method identified in the preceding paragraph, said granulate comprising granules having more than 20% by weight of ammonium sulfate, and having a skin corresponding to a weight fraction of from 3 wt.% to 40 wt.% of the granule, said skin
- FIG. 1 is a block diagram schematically showing a conventional granulation set-up for urea products.
- Fig. 2 is a block diagram schematically showing a granulation setup for urea products in accordance with an embodiment of the invention.
- the invention concerns making granules of a urea product comprising urea and at least one salt, comprising an amount of the salt exceeding the solubility limit of the salt in the urea.
- the invention particularly pertains to a method of making granules of urea ammonium sulfate (UAS) having a higher than soluble concentration of ammonium sulfate (AS).
- UAS ammonium sulfate
- the inventors believe that the generation of excess dust is related to the fact that in making such granules, one no longer can present a homogeneous liquid to the fluid bed granulator. Rather, part of the UAS is present in the form of a slurry (i.e., a suspension) comprising solid ammonium sulfate particles in a UAS melt.
- a slurry i.e., a suspension
- this slurry is fed to the fluid bed the formed granules have an irregular surface caused by AS particles protruding from the surface. It is believed that due to this irregular surface, friction and attrition will lead to more dust being generated than during handling of smooth granulate.
- the non-smooth surface of the UAS-granules may also adversely affect the flowing properties of these granules in comparison with smooth urea granules.
- These UAS granules will therefore have a lower flowability- index, a higher Angle of repose, lower bulk density, a higher internal friction, etc.
- the worsening of these properties of UAS granules can/will lead to some issues .E.g., a smaller flow rate during gravity flow from
- the inventors in seeking to solve the aforementioned problem of dust generation, therefore have judiciously considered to solve the problem of making UAS granules having a high AS concentration, yet without the drawbacks of a non-smooth surface. This presents a technical challenge, since granules having a high salt content as mentioned above, are
- slurry a suspension
- UAS slurry a suspension
- the feed of the slurry to the granulation process is adapted by distinguishing early stage granulation of a highly concentrated slurry, and final stage granulation of a homogenous urea liquid comprising an amount of salt below the solubility limit, or in the absence of the salt. Mixtures of salts are included in the invention.
- the invention is based on the judicious insight to obtain the desired high concentration in the granules by securing that an inner portion of the granulate has a relatively high proportion of the salt (such as AS or potassium chloride), whilst an outer portion of the granulate has a proportion of said salt expressly below the solubility limit of the salt in urea.
- the manner in which the problem of a non- smooth surface of highly concentrated UAS granules is solved can also be applied to urea products having insoluble amounts of other salts, such as potassium chloride.
- the granulation process of the invention comprises presenting at least two liquid streams to the granulation process.
- One, as a non-final liquid is a slurry comprising urea and an amount of salt above the solubility limit of the salt in urea.
- this means that the non-final liquid comprises, relative to its total composition, more than 20 wt.% of ammonium sulfate.
- the other liquid stream, as a final liquid is a solution comprising urea, either without salt or comprising only dissolved amounts of salt.
- the final granulation liquid comprises, relative to its total composition, an amount of 0-20 wt.% of ammonium sulfate.
- the non-final liquid is a slurry comprising undissolved AS, while the final liquid is a homogenous urea liquid comprising either no AS, or only dissolved AS.
- the skilled person will be aware of the applicable solubility limits.
- the final liquid of relatively low (soluble) salt concentration
- the non-final liquid of relatively high (insoluble) salt concentration, will be fed to the same granulation process prior to said final liquid.
- the number of stages of the granulation process is not critical.
- the process just requires the availability of granulation equipment allowing a plurality of subsequent feeds of granulation liquid.
- Such equipment can be a system comprising a plurality of granulators in series.
- the equipment is a single granulator provided with multiple feeding sections in series.
- a combination of the aforementioned types of granulators can be used.
- more granulation liquids can be used upstream of the aforementioned final granulation liquid.
- a plurality of granulation liquids of high and low salt concentration can be used. It will be understood that in the event that a liquid of low (soluble) salt concentration is used also upstream of said final liquid, the amount of salt provided by one or more non-final liquids of high concentration will have to be proportionally higher, in order to secure an overall salt concentration in the granules of the desired high value of greater than the solubility limit of the salt in urea.
- the aforementioned salt is AS, and the applicable solubility limit is 20% by weight. This is illustrated with reference to the following, non-limiting computation examples CE 1 to CE5.
- CE 1 Two granulation liquids are used in a ratio of 1: 1, with the final liquid having 10% by weight of AS.
- the non- final granulation liquid will have more than 30% by weight of AS in order to end up with granules having more than 20% by weight of AS.
- CE2 Two granulation liquids are used, viz. a non-final liquid (a) having 25% by weight of AS and a final liquid (b) having 15% by weight of AS.
- a non-final liquid (a) having 25% by weight of AS
- a final liquid (b) having 15% by weight of AS.
- the relative proportion of the two liquids will be such that the ratio of (a) : (b) is to exceed
- CE3 Three granulation liquids are used: a first non-final liquid (c) having 10% of AS, a second non-final liquid (d) having 25% of AS, and a final liquid (e) having 5 % of AS.
- the proportion of the second non-final liquid will have to be a relatively high majority (such as more than about 75% by weight) of the total of the granulation liquids, in order to secure an overall percentage of more than 20% of AS in the final granulate.
- CE5 Five granulation liquids are used, whereby four subsequent non-final granulation liquids all have 25% of AS, and are all used in the same proportion.
- the final granulation liquid having less than 20% by weight of AS, will then comprise at least a minimal amount of AS, e.g., at least 1% by weight, such as at least 5% by weight, such as at least 10% by weight.
- the skilled person will have no difficulty whatsoever to determine the amounts and relative proportions needed for any number and type of granulation liquid applied. Thereby the skilled person will be sufficiently guided by the required overall percentage (more than 20% of AS), and by the required percentage in the final liquid (less than 20% of AS). Also, for other salts, the skilled person will be able to adjust the amounts and relative proportions needed, taking into account the solubility limit of the salt.
- the number of granulation liquids that are subsequently presented to the granulation process is in a range of from two to six. Preferably this number is three to four.
- the core of the granules is provided by seed particles onto which granulation liquid is applied.
- these seed particles are generally provide from powdered (typically coarse) urea or UAS granulate.
- powder can generally be obtained by suitable size reduction techniques such as crushing, grinding, milling, or other methods of pulverizing a granulate.
- the seeds can have a wide variety in composition. Particularly, they can originate from either or both of a part of the granule with high AS -concentration or from a part of the granule with low AS concentration.
- the seed particles are provided by crushing the granulate produced according to the invention.
- the average AS -concentration in the seed-particles will generally be equal to the average AS-concentration in the granules produced in the fluid bed granulator. It is, however, also possible (both as initial seed particles and throughout the process) to employ pure urea particles as seeds, or pure AS-particles. The foregoing correspondingly applies to salts other than AS, or to mixtures of salts.
- the smoothness of the granulate obtainable by the method of the invention is better secured in the event that the final granulation hquid is applied as a layer of a desirable minimum thickness. It will also be understood that this requirement for the final liquid will be less stringent if the directly preceding non-final liquid also has a percentage of salt, such as AS, of below the solubility limit.
- the relative proportion of the final liquid having 0-20% by weight of ammonium sulfate is at least 3 wt.%, preferably at least 5%, and more preferably at least 10%.
- a non-final granulation liquid having also a salt percentage below the solubility limit, such as 0-20% by weight of AS is applied directly upstream of said final liquid (i.e., without a granulation hquid having more than 20% of AS, or the applicable insoluble
- the final granulation liquid preferably comprises of from 10 wt.% to 20 wt.% of ammonium sulfate. More preferably, the final
- granulation liquid comprises of from 15 wt.% to 20 wt.%, and most preferably it comprises the maximum soluble amount, generally 20 wt.%.
- granulation liquids having more than 20% by weight of AS will preferably have an AS concentration up to approximately 50% by weight, preferably up to 40% by weight, and more preferably higher than 20% by weight and up to 30% by weight.
- the urea comprising the dissolved amount of salt can be considered to be the continuous phase of the slurry.
- urea will generally be highly concentrated, in the sense that it is present as a urea liquid containing at most a small amount of water and dissolved salt, such as AS.
- the amount of water will not exceed 10%.
- the urea liquid comprises at least 95% by weight of urea and biuret, and more preferably at least 98.5% by weight of urea and biuret.
- biuret this is a regular component of urea, resulting as a by-product of urea synthesis.
- the amount of biuret is not particularly critical, although generally below 5 wt.% and preferably not exceeding 1- 1.3 wt.%.
- the biuret content is at most 1% by weight, and for some application more preferably below 0.3% by weight.
- the urea for use in the present invention can be produced in any manner.
- the skilled person is familiar with various processes that exist for the production of urea.
- a frequently used process for the preparation of urea according to a stripping process is the carbon dioxide stripping process as for example described in Ullmann's Encyclopedia of Industrial Chemistry, Vol. A27, 1996, p 333-350.
- the synthesis section is followed by one or more recovery sections.
- the synthesis section comprises a reactor, a stripper, a condenser and a scrubber in which the operating pressure is in between 12 and 18 MPa and preferably in between 13 and 16 MPa.
- the urea solution leaving the urea reactor is fed to a stripper in which a large amount of non-converted ammonia and carbon dioxide is separated from the aqueous urea solution.
- Such a stripper can be a shell and tube heat exchanger in which the urea solution is fed to the top part at the tube side and a carbon dioxide feed to the synthesis is added to the bottom part of the stripper. At the shell side, steam is added to heat the solution. The urea solution leaves the heat exchanger at the bottom part, while the vapor phase leaves the stripper at the top part. The vapor leaving said stripper contains ammonia, carbon dioxide and a small amount of water. Said vapor is condensed in a falling film type heat exchanger or a submerged type of condenser that can be a horizontal type or a vertical type. A horizontal type submerged heat exchanger is described in Ullmann's Encyclopedia of Industrial Chemistry, Vol.
- the heat released by the exothermic carbamate condensation reaction in said condenser is usually used to produce steam that is used in a downstream urea processing section for heating and concentrating the urea solution. Since a certain liquid residence time is created in a submerged type condenser, a part of the urea reaction takes already place in said condenser.
- the formed solution, containing condensed ammonia, carbon dioxide, water and urea together with the non-condensed ammonia, carbon dioxide and inert vapor is sent to the reactor.
- the ammonia to carbon dioxide molar ratio in the urea solution leaving the reactor is generally in between 2.5 and 4 mol/mol. It is also possible that the
- condenser and the reactor are combined in one piece of equipment.
- An example of this piece of equipment as described in Ullmann's Encyclopedia of Industrial Chemistry, Vol. A27, 1996, pp 333-350.
- the formed urea solution leaving the urea reactor is supplied to the stripper and the inert vapor containing non-condensed ammonia and carbon dioxide is sent to a scrubbing section operating at a similar pressure as the reactor. In that scrubbing section the ammonia and carbon dioxide is scrubbed from the inert vapor.
- the formed carbamate solution from the downstream recovery system is used as absorbent in that scrubbing section.
- the urea solution leaving the stripper in this synthesis section requires a urea concentration of at least 45 % by weight and preferably at least 50 % by weight to be treated in one single recovery system downstream the stripper.
- the recovery section comprises a heater, a liquid/gas separator and a condenser.
- the pressure in this recovery section is between 200 to 600 kPa.
- the heater of the recovery section the bulk of ammonia and carbon dioxide is separated from the urea and water phase by heating the urea solution. Usually steam is used as heating agent.
- the urea and water phase contains a small amount of dissolved ammonia and carbon dioxide that leaves the recovery section and is sent to a downstream urea processing section where the urea solution is concentrated by evaporating the water from said solution.
- the invention is not limited to any particular urea production process.
- Other processes and plants include those that are based on technology such as the HEC process developed by Urea Casale, the ACES process developed by Toyo Engineering Corporation and the process developed by Snamprogetti. All of these processes, and others, may be used preceding the urea finishing method of the invention.
- Urea production generally involves a finishing step in which a urea melt is brought into the desired particulate form, generally involving any one of prilling, granulation, and pelletizing.
- a urea melt is brought into the desired particulate form, generally involving any one of prilling, granulation, and pelletizing.
- AS prilling, granulation, and pelletizing.
- AS granulation of urea products
- a preferred urea finishing method, and preferably used in the present invention for granulation of urea products such as UAS as well, is fluidized bed granulation. Therein a urea melt is sprayed on granules that grow in size as the process continues.
- urea melt is known in the art, and is applied to urea having less than 10% of water, such as less than 5% of water and preferably up to 1.5 % of water (and generally including biuret, as mentioned above).
- concentration of urea takes usually place at high temperatures and sub -atmospheric pressures.
- concentration of the urea solution to the desired moisture content in the anhydrous urea melt takes place in a concentration section comprising one or a sequence of one or more concentrators in series.
- the urea melt leaving the concentration section is usually conveyed by a pump to the urea finishing section.
- the urea finishing sections usually used in urea plants for producing the urea end product are urea granulation finishing and urea prilling finishing.
- For urea granulation finishing the desired urea concentration in the urea melt to the granulator is in between 95 and 99 % by weight.
- urea including biuret, water and small amounts of ammonia.
- the ammonia concentration in the urea melt sent to said urea finishing section amounts in between 100 and 900 ppm by weight.
- Granulation is preferably conducted in a fluidized bed granulator.
- a fluidized bed granulator typically comprises an inlet for seed particles, an outlet for granule products, a perforated bottom plate for distributing fluidizing air, and a gas outlet.
- a preferred granulator further comprises a plurality of compartments configured between said inlet for seed particles and outlet for granule products.
- Each compartment contains at least one or a plurality of nozzles for feeding a slurry or a melt of urea, UAS, or another applicable urea product granulation liquid. Different types of nozzles can be employed.
- one type generates droplets
- another type serves to feed the slurry or the melt to the fluidized bed in the form of a film.
- the granulator is configured to move the particles from the inlet to the outlet whereby the particle size increases from the inlet to the outlet.
- the first feed stream i.e., nearest to the inlet
- the last stream i.e., nearest to the outlet, will be a homogeneous liquid.
- the first compartment closest to the inlet i.e., the first upstream compartment
- a slurry stream of UAS This slurry has a concentration of AS greater than 20 wt.%, preferably greater than 22 wt.%, and most preferably greater than 25 wt.%.
- the last compartment (downstream) is fed with a final granulation liquid as mentioned above, i.e., with a melt stream of urea or UAS, with a
- the granulator comprises a plurality of compartments upstream of the final granulation compartment. This accommodates feeding to the granulation process a corresponding plurality of non-final granulation hquids as discussed above. It will be understood that, downstream of the final granulation compartment, a granulator used in the invention may comprise one or more additional compartments, not used for feeding granulation liquid. This typically includes a cooling compartment.
- the ammonium sulfate (AS) can be from any source.
- the AS is formed by neutralizing ammonia obtained from urea finishing.
- reference is made to US 2013/0319060.
- Another background reference on neutralizing NH3 off-gas with sulfuric acid, followed by UAS formation, is US 2012/0240649.
- the AS is provided as a by-product or another process, such as from the production of caprolactam or from the desulfurization of coal.
- the off-gases and condensates from the urea- evaporation section are transported to further processing steps (in the urea melt-plant), and need to be treated/reworked at great effort, and with a relatively high energy consumption.
- the off-gases and condensates from the UAS- evaporation section containing a high amount of NH3 are preferably transported to a dust- and NH3-washing section. There the NH3 is simply neutralized so as to form AS, i.e., converted by reaction with sulfuric acid to ammonium sulfate.
- the granulation liquid can be applied in various ways. Generally, this liquid will be provided in the form of atomized droplets, or as a sprayed film. See, e.g., Ullmann's Encyclopedia of Industrial Chemistry, Urea by Jozef H. Meessen,
- the granulation fluids are provided at a sufficiently high temperature to be actually in a liquid state.
- the temperature of the granulation liquid is in a range of 132 - 140°C. Since presence of ammonium sulfate reduces the crystallization temperature of the granulation liquid, typical temperatures for UAS granulation of the granulation liquid are in a range of 118 - 140 °C. For other salts, the skilled person will be able to adjust the temperatures as necessary.
- the invention also pertains to a urea ammonium sulfate granulate obtainable by the method identified above, in all of its embodiments.
- the granulate of the invention comprises granules having more than 20% by weight of ammonium sulfate, and having a skin comprising less than 20% by weight of ammonium sulfate.
- Said skin corresponds to a weight fraction of from 3 wt.% to 40 wt.% of the granule, preferably of from 5 wt.% to 20 wt.%.
- skin here does not necessarily refer to a single applied layer, but can also comprise a plurality of subsequently applied layers.
- Fig. 1 a block diagram is presented that schematically shows a conventional granulation set-up for urea products, such as UAS.
- the following process streams and granulator equipment parts are shown:
- a feed stream of granulation liquid is fed to the three granulation compartment, resulting in granules built-up, at each
- Fig. 2 is a block diagram schematically showing a granulation set-up for urea products in accordance with an embodiment of the invention.
- the feed stream (1) of granulation liquid is fed only, as a non-final granulation liquid, to the non-final granulation compartments (2) and (3).
- the invention in an embodiment wherein another component is added to the granules via one or more of the feed streams.
- This refers to, e.g., formaldehyde as well as other granulation additives and/or adjuvants, as well as to sulfur and/or other micronutrients.
- the invention includes a method of making a granulate of a urea product comprising urea and a salt, such as urea ammonium sulfate, having a high content of the salt.
- the high content is such as to provide an amount of the salt above the limit of solubility of the salt in urea.
- the granulate of the invention is characterized by having a smooth surface, which, e.g. in the event of urea ammonium sulfate, is not normally the case for granulate having the aforementioned high ammonium sulfate content. According to the invention this is realized by dividing the feed liquids to granulation. This division is based on non-final granulation liquids of a sufficiently high content of the salt, and a final granulation liquid
- the non-final granulation liquids possibly are a slurry of urea and more than 20 wt.% of ammonium sulfate.
- the final granulation liquid then has 0-20 wt.% of ammonium sulfate, i.e. below the solubility limit.
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Abstract
Description
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Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA2991280A CA2991280C (en) | 2015-07-06 | 2016-07-06 | Granulation of urea products |
EA201890215A EA032243B1 (en) | 2015-07-06 | 2016-07-06 | Granulation of urea products |
CN201680039947.0A CN107848903B (en) | 2015-07-06 | 2016-07-06 | Granulation of urea products |
AU2016291068A AU2016291068B2 (en) | 2015-07-06 | 2016-07-06 | Granulation of urea products |
US15/742,488 US10227265B2 (en) | 2015-07-06 | 2016-07-06 | Granulation of urea products |
PL16745535T PL3319925T3 (en) | 2015-07-06 | 2016-07-06 | Granulation of urea products |
EP16745535.1A EP3319925B1 (en) | 2015-07-06 | 2016-07-06 | Granulation of urea products |
SA518390686A SA518390686B1 (en) | 2015-07-06 | 2018-01-03 | Granulation of Urea Products |
HRP20192214TT HRP20192214T1 (en) | 2015-07-06 | 2019-12-10 | Granulation of urea products |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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EP15175476.9 | 2015-07-06 | ||
EP15175476 | 2015-07-06 |
Publications (1)
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WO2017007315A1 true WO2017007315A1 (en) | 2017-01-12 |
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PCT/NL2016/050486 WO2017007315A1 (en) | 2015-07-06 | 2016-07-06 | Granulation of urea products |
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US (1) | US10227265B2 (en) |
EP (1) | EP3319925B1 (en) |
CN (1) | CN107848903B (en) |
AU (1) | AU2016291068B2 (en) |
CA (1) | CA2991280C (en) |
EA (1) | EA032243B1 (en) |
GE (1) | GEP20207124B (en) |
HR (1) | HRP20192214T1 (en) |
PL (1) | PL3319925T3 (en) |
SA (1) | SA518390686B1 (en) |
WO (1) | WO2017007315A1 (en) |
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EP4029601A1 (en) | 2021-01-13 | 2022-07-20 | Green Granulation Ltd. | Plant and process of granulating urea ammonia sulphate |
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WO2023018351A3 (en) * | 2021-08-11 | 2023-03-09 | Private Company Limited By Shares Innovation Agro Group Limited | Composition for granular urea-based fertilizer |
RU2800070C2 (en) * | 2018-10-18 | 2023-07-17 | Яра Интернейшнл Аса | Method and granulator with fluidized bed for obtaining granules from suspension |
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- 2016-07-06 CN CN201680039947.0A patent/CN107848903B/en active Active
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WO2019013639A1 (en) | 2017-07-14 | 2019-01-17 | Stamicarbon B.V. | Urea finishing and off-gas treatment plant and process |
US10829444B2 (en) | 2017-07-14 | 2020-11-10 | Stamicarbon B.V. | Urea finishing and off-gas treatment plant and process |
EP3639916A1 (en) | 2018-10-18 | 2020-04-22 | Yara International ASA | Method and fluidized bed granulator for the production of granules from a slurry |
WO2020079204A1 (en) | 2018-10-18 | 2020-04-23 | Yara International Asa | Method and fluidized bed granulator for the production of granules from a slurry |
RU2800070C2 (en) * | 2018-10-18 | 2023-07-17 | Яра Интернейшнл Аса | Method and granulator with fluidized bed for obtaining granules from suspension |
EP3907208A1 (en) | 2020-05-08 | 2021-11-10 | Yara International ASA | Urea ammonium sulfate-based composition |
WO2021224461A1 (en) | 2020-05-08 | 2021-11-11 | Yara International Asa | Urea ammonium sulfate-based composition |
EP4029601A1 (en) | 2021-01-13 | 2022-07-20 | Green Granulation Ltd. | Plant and process of granulating urea ammonia sulphate |
WO2022152704A1 (en) | 2021-01-13 | 2022-07-21 | Green Granulation Ltd. | Plant and process of granulating urea ammonia sulphate |
EP4067324A1 (en) | 2021-03-31 | 2022-10-05 | SKW STICKSTOFFWERKE PIESTERITZ GmbH | Granulated ph-neutral urea ammonium sulfate fertilizer with urease inhibitor |
DE102021108187A1 (en) | 2021-03-31 | 2022-10-06 | Skw Stickstoffwerke Piesteritz Gmbh | Granulated pH neutral urea ammonium sulphate fertilizer with urease inhibitor |
WO2023018351A3 (en) * | 2021-08-11 | 2023-03-09 | Private Company Limited By Shares Innovation Agro Group Limited | Composition for granular urea-based fertilizer |
Also Published As
Publication number | Publication date |
---|---|
GEP20207124B (en) | 2020-06-25 |
HRP20192214T1 (en) | 2020-02-21 |
AU2016291068B2 (en) | 2019-11-28 |
CA2991280A1 (en) | 2017-01-12 |
US20180201551A1 (en) | 2018-07-19 |
CA2991280C (en) | 2019-11-12 |
US10227265B2 (en) | 2019-03-12 |
EP3319925B1 (en) | 2019-11-27 |
CN107848903B (en) | 2021-09-21 |
CN107848903A (en) | 2018-03-27 |
EA201890215A1 (en) | 2018-04-30 |
EP3319925A1 (en) | 2018-05-16 |
EA032243B1 (en) | 2019-04-30 |
AU2016291068A1 (en) | 2018-01-25 |
PL3319925T3 (en) | 2020-04-30 |
SA518390686B1 (en) | 2021-10-06 |
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