Classifications

• • 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
• • 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
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
  • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
  • C01C1/00—Ammonia; Compounds thereof
  • C01C1/24—Sulfates of ammonium
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
  • C01F7/00—Compounds of aluminium
  • C01F7/68—Aluminium compounds containing sulfur
  • C01F7/74—Sulfates
  • C01F7/746—After-treatment, e.g. dehydration or stabilisation
• • 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
• • C—CHEMISTRY; METALLURGY
  • C05—FERTILISERS; MANUFACTURE THEREOF
  • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
  • C05D9/00—Other inorganic fertilisers
  • C05D9/02—Other inorganic fertilisers containing trace elements
• • C—CHEMISTRY; METALLURGY
  • C05—FERTILISERS; MANUFACTURE THEREOF
  • 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
• • 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
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00049—Controlling or regulating processes
  • B01J2219/00051—Controlling the temperature
• • 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
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
  • B01J2219/00277—Apparatus
  • B01J2219/00351—Means for dispensing and evacuation of reagents
  • B01J2219/0036—Nozzles
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size

Definitions

• the invention relates to a method and apparatus for granulating ammonium sulfate.
• Ammonium sulfate finds a variety of uses. For example, ammonium sulfate is used as fertilizer or fertilizer additive. Ammonium sulfate is a source of both nitrogen and sulfur, which are important plant nutrients. There is a lack of sulfur worldwide in many soils, which can be at least partially compensated by the targeted addition of ammonium sulfate.
• ammonium sulfate can be formed by introducing ammonia into sulfuric acid.
• Industrial ammonium sulfate is often crystallized from solutions which are obtained as a by-product, for example, in coal stoves or plants for the production of caprolactam.
• the crystallization of ammonium sulfate usually produces angular crystals, which usually have a diameter of 1 to 2 mm.
• Ammonium sulfate is usually not the only component of a fertilizer; rather, fertilizers include combinations of various plant nutrients (such as nitrogen, phosphorus, potassium or sulfur). Ammonium sulfate is therefore often mixed in use with granulated fertilizers to produce a balanced fertilizer mixture.
• crystalline ammonium sulfate has some disadvantages that make it difficult to incorporate into granulated fertilizer mixtures.
• the particles of ammonium sulfate formed in the crystallization are relatively small, on the other hand, the particles often vary greatly in size due to abrasion and dust formation. These properties make it difficult to prepare physically homogeneous fertilizer mixtures with ammonium sulfate.
• a uniform mixing and particle size distribution of the individual components is essential. Too large a width of the particle size distribution can also lead to mechanical problems in the uniform discharge of the fertilizer mixture.
• Granulated ammonium sulfate is ideally spherical and the individual particles of the granules have, for example, a diameter of 2 to 4 mm. This size is based on the urea granules, which is the world's most widely used fertilizer.
• US Pat. No. 4,589,904 describes the granulation of ammonium sulfate in a drum dryer with downstream dryer, the solution being produced in a pre-neutralizer.
• US 2012/0231277 relates to the production of build-up granules by fluidized bed or jet bed granulation.
• granulation cores (nuclei), which were previously prepared separately, sprayed with an ammonium sulfate-containing solution and then dried.
• a problem with the granulation of ammonium sulfate is the formation of dust, which is understood to mean particles with a diameter of less than 0.5 mm.
• the formation of dust is mainly due to three sources.
• the nozzles that spray the material to be granulated each produce droplets having a certain distribution of diameters, with some of the finest droplets solidifying before they strike the ammonium sulfate particles, so that the dust so formed leaves the pelletizer with the exhaust air again.
• the abrasion of the granules due to movements and collisions of the particles is to be mentioned as a dust source, for example in a fluidized bed, wherein the amount of the resulting dust depends significantly on the mechanical properties of the granules.
• the dust resulting from the comminution to large granular particles should be mentioned, which is usually transferred directly back into the granulator in the methods and systems according to the prior art.
• granulation additives are often used to reduce this dust formation.
• the addition of these additives causes the granules particles and in particular their surface remain plastic, so that due to their rolling motions and collisions predominantly round particles with a smooth surface and a good mechanical stability can be obtained. Therefore, the granules thus obtained has a high pressure and impact resistance, a low tendency to dust formation by abrasion and beyond even a prolonged storage only a slight tendency to clumping.
• Corresponding granulation additives find their application not only in fluid bed granulation, but also in other processes, such as, for example, prilling or drum granulation.
• a first aspect of the invention relates to a process for producing granules comprising ammonium sulfate, the process comprising the following steps: (a) providing a composition comprising ammonium sulfate and aluminum sulfate; and
• Granules preferably comprise particles which are uniformly shaped and homogeneously structured and whose nature and physical behavior are known to a person skilled in the art.
• the granules of a granulate can assume different sizes, wherein the width of the particle size distribution is a criterion for the quality of a granulate.
• the granules according to the invention preferably have a narrow particle size distribution, wherein the largest and smallest particle diameters preferably deviate from one another by at most 10 mm, more preferably at most 8 mm, at most 6 mm, at most 4 mm, at most 3 mm or at most 2 mm.
• the granules of the invention have a size in the range of 2 to 5 mm, more preferably in the range of 2 to 4.5 mm, even more preferably in the range of 2 to 4 mm and most preferably in the range of 2.5 to 4 mm.
• a composition comprising ammonium sulfate and aluminum sulfate is prepared.
• the composition further comprises water.
• ammonium sulfate, aluminum sulfate and water are mixed together in a mixing device.
• a composition of ammonium sulfate and water and a second composition of aluminum sulfate and water are used, which are mixed in a corresponding ratio liquid.
• a composition of crystalline ammonium sulfate and water and a second composition of crystalline aluminum sulfate and water are prepared, which are mixed in a corresponding ratio liquid.
• a composition of crystalline ammonium sulfate and water are prepared and a second composition of aluminum sulfate and water are used, which are mixed in a corresponding ratio liquid.
• a composition of ammonium sulfate and water are used and a second composition of aluminum sulfate and water are prepared, which are liquid mixed / metered in appropriate proportion.
• a composition of ammonium sulfate and water is used in the crystalline aluminum sulfate is added in a corresponding ratio.
• a composition of ammonium sulfate and water is prepared in which crystalline aluminum sulfate is added in an appropriate ratio. Suitable mixing devices are known to a person skilled in the art.
• Aluminum sulphate exists both as a pure compound without water of crystallization and with different proportions of water of crystallization. In all preferred embodiments, which are described below, the proportions and concentrations of aluminum sulfate, the crystal water, which occurs in the commercial crystalline product (usually stoichiometric 42.4 wt .-%) are disregarded.
• the content of ammonium sulfate in the composition is in the range of 30% by weight to at most the saturated solution about 50% by weight, more preferably in the range of 31 to 49% by weight, in the range of 32 to 48% by weight, in the range of 33 to 47 wt .-%, in the range of 34 to 46 wt .-% or in the range of 35 to 45 wt .-%, each based on the total mass of the composition, always below the temperature-dependent crystallization limit.
• the content of pure aluminum sulfate in the solids fractions of the composition is in the range of 0.5 to 2.5 wt%, more preferably in the range of 0.55 to 2.3 wt%, in the range of 0 , 6 to 2.1% by weight, in the range of 0.65 to 1, 9% by weight, in the range of 0.7 to 1.7% by weight, in the range of 0.75 to 1, 5 wt .-%, in the range of 0.8 to 1, 3 wt .-%, in the range of 0.85 to 1, 2 wt .-% or in the range of 0.9 to 1, 1 wt .-% , in each case based on the total mass of the dry, granulated product.
• the content of pure aluminum sulfate in the composition is at most 2.5% by weight, more preferably at most 2.3% by weight, at most 2.1% by weight, at most 1.9% by weight. , at most 1, 7 wt .-%, at most 1, 5 wt .-%, at most 1, 3 wt .-%, at most 1, 2 wt .-%, at most 1, 1 wt .-% or at most 1, 0 Wt .-%, each based on the total mass of the dry, granulated product.
• the mass ratio of ammonium sulfate to aluminum sulfate in the composition is in the range of 50: 1 to 10: 1, more preferably in the range of 48: 1 to 15: 1, in the range of 46: 1 to 20: 1, in the range of 44: 1 to 25: 1, in the range of 43: 1 to 30: 1, or in the range of 42: 1 to 35: 1.
• the composition is preferably in the form of a mixture, wherein the mixture may be in the form of a solution, for example.
• step (b) of the process according to the invention the granulation of the composition takes place.
• the granulation of the composition can be carried out by customary methods known to the person skilled in the art, for example by means of prilling or fluid bed granulation.
• the granulation of the composition is by fluid bed granulation.
• the preparation of the granules is preferably carried out by drying the solidifying droplets of the composition, but can also be done by abrasion of already existing, already solidified granules. By wetting such granular particles with other droplets, the particles grow and preferably form a homogeneous granules.
• the granulation of the composition provided in step (a) in step (b) is carried out by means of fluid bed granulation, comprising the steps:
• step (b 3 ) spraying the composition provided in step (a) on the germs.
• ammonium sulfate-containing microorganisms are preferably provided.
• the germs are preferably produced by sieving and / or crushing granulated ammonium sulfate.
• the germs according to the invention preferably have a narrow size distribution, wherein the largest and the smallest germ diameter preferably differ from each other by more than 4 mm, more preferably at most 2 mm, at most 1 mm or at most 0.5 mm. Methods for determining a germ diameter are known to a person skilled in the art.
• the diameter of the ammonium sulfate-containing nuclei is in the range of 0.1 to 4.0 mm, more preferably in the range of 0.1 to 2.0 mm and most preferably in the range of 0.5 to 2.0 mm ,
• the ammonium sulfate-containing seeds are preferably fluidized in a fluidized bed.
• a fluidized bed is suitable for a variety of process engineering processes for the treatment of solids and liquids and its construction is known to a person skilled in the art.
• the fluidized bed according to the invention is preferably formed by the ammonium sulfate-containing nuclei.
• the fluidized bed is traversed by a fluid.
• the ammonium sulphate containing germs are preferably offset by an upward flow of the fluid in a fluidized state. In this case, a liquid-like state of the germs is generated, which is also referred to as "fluidized bed".
• the fluid comprises air.
• the so-called empty tube velocity of the fluid used to fluidize the ammonium sulfate-containing nuclei is in the range of 1-5 m / s, more preferably in the range of 1.5-4.5 m / s, in the range of 2 - 4 m / s or in the range of 2.5 - 3.5 m / s.
• the temperature of the fluidized bed is in the range of 50 ° C to 100 ° C, more preferably in the range of 60 ° C to 90 ° C, or in the range of 70 ° C to 80 ° C.
• the fluid is preheated accordingly to adjust the fluidized bed temperature.
• step (b 3 ) of the process according to the invention the composition provided in step (a) is preferably sprayed onto the germs.
• the droplets formed during the spraying of the composition provided in step (a) preferably pass into the fluidized bed of fluidized, ammonium sulfate-containing germs.
• the droplets are preferably flowed around from the fluid, preferably from the air, from the bottom up, whereby the fluid causes the droplets to dry and predominantly solidify on the germs, thereby contributing to the growth of the germs.
• the spraying of the composition provided in step (a) is preferably carried out below or within the fluidized bed, so that the droplets formed during the spraying are sprayed from bottom to top in the fluidized bed, whereby the sprayed composition is transferred to the particles in the fluidized bed and dried.
• spraying of the composition provided in step (a) in step (b 3 ) is effected via nozzles, wherein at least 150 ml of the composition are sprayed via each nozzle per minute, more preferably at least 250 ml per minute, at least 500 ml per minute , at least 1000 ml per minute, at least 1500 ml per minute or at least 2000 ml per minute.
• air is used to spray the composition provided in step (a) in step (b 3 ).
• the reduced pressure is preferably at most 10 mbar, more preferably at most 5 mbar or at most 2 mbar.
• the negative pressure ensures that as little as possible, preferably no dust leaves the fluidized bed.
• the flow rate of the air used in step (b 3 ) to spray the composition across each nozzle is in the range of 10 to 200m 3 per hour, more preferably in the range of 20 to 180m 3 per hour, in the range of 40 to 160m 3 per hour, in the range of 60 to 140m 3 per hour or in the range of 80 to 120m 3 per hour.
• the droplets preferably wet the ammonium sulphate-containing nuclei or the already present, already solidified granulate particles, so that they grow uniformly and form a homogeneous granulate.
• the granules leave the fluidized bed and are preferably transferred to a sorter.
• Suitable measures for transferring granulate particles from a fluidized bed to another device are known to a person skilled in the art. For example, by using specially designed distribution plates, the granular particles can be added in the fluidized state not only in vertical movement, but also in horizontal movement and thus gradually leave the fluidized bed.
• At least a portion of the air used for fluidizing in step (b 2 ) is purified in a purification step.
• the air is discharged and fed to the purification stage.
• the air is preferably cleaned in the purification stage, ie freed in particular of solid particles and droplets.
• the cleaning step is a wet scrubber.
• the granules are divided after their preparation into three fractions, wherein
• a fraction (F 2 ) contains particles of a size above the desired target size
• a fraction (F 3 ) contains particles of size below the desired target size.
• the fraction (Fi), which contains particles having the desired target size is further processed after leaving the fluidized bed.
• the fraction (F 2 ) containing particles having a size above the desired target size is fed to a comminution device, which is preferably configured is to crush granule particles.
• the particles of the fraction (F 2 ) are comminuted in the comminution device and the comminuted particles are preferably fed again to the fluidized bed.
• fraction (F 3 ) containing particles of size below the desired target size is recycled to the fluidized bed.
• the finished granules comprise at least 95% by weight of the amount of ammonium sulfate and aluminum sulfate sprayed in step (b 3 ), more preferably at least 95.5% by weight, at least 96% by weight, more preferably at least 96.5% Wt .-%, at least 97 wt .-%, at least 97.5 wt .-% or at least 98 wt .-%.
• the amount of ammonium sulfate and aluminum sulfate which do not contribute to the mass of the finished granules and form, for example, dust is at most 5 wt%, more preferably at most 4.5 wt%, at most 4 wt%, at most 3.5% by weight, at most 3% by weight, at most 2.5% by weight, at most 2% by weight, at most 1.5% by weight, at most 1% by weight or at most 0, 5 wt .-%, each based on the dry total mass of sprayed ammonium sulfate and aluminum sulfate.
• Another aspect of the invention relates to a granulate comprising ammonium sulfate and aluminum sulfate, wherein all particles of the granules have a comparable composition and wherein the content of pure aluminum sulfate in the granules in the range of 0.5 to 2.5 wt .-% is.
• Comparable composition in the sense of the invention means that the molar amounts of the individual components of the granules according to the invention in the individual granules differ by more than 2% from the average of the molar amounts of the respective component in the total granules, more preferably at most 1, 5% or at most 1%.
• Methods for determining the molar amounts of a granulate are known to a person skilled in the art.
• the content of ammonium sulfate in the granules is at least 97.5 wt .-%, more preferably at least 98 wt .-%, at least 98.5 wt .-%, or at least 99 wt .-%, each based on the total mass of the granules.
• the content of pure aluminum sulfate in the granules is in the range from 0.5 to 2.5% by weight, more preferably in the range from 0.6 to 2% by weight, in the range from 0.7 to 1 , 5 wt .-%, or in the range of 0.8 to 1, 0 wt .-%, each based on the total mass of the granules.
• the granules may optionally comprise further constituents.
• the particulate composition comprises water as residual moisture.
• the content of water in the granules is at most 1, 0 wt .-%, more preferably at most 0.8 wt .-%, at most 0.6 wt .-%, at most 0.4 wt .-%, or at most 0.2 Wt .-%, each based on the total mass of the granules.
• a further aspect of the invention relates to a device for producing granules comprising ammonium sulfate, wherein the device comprises the components which are at least temporarily in active connection with one another:
• (C) a fluidized bed arranged after the mixing device configured to produce the granules.
• the components of the device according to the invention are in operative connection with each other, i. are connected to each other by suitable piping etc. in a manner which ensures the general functioning of the device.
• the necessary measures are known to a person skilled in the art.
• the mixing device according to the invention is preferably configured to produce a composition comprising ammonium sulfate and aluminum sulfate.
• the structure and operation of such a mixing device are known to a person skilled in the art.
• the composition which is produced in the mixing device according to the invention is preferably sprayed.
• the spraying device is before, more preferably below or within the fluidized bed arranged and sprayed the composition from bottom to top of the fluidized bed.
• the spraying device is configured such that the droplets formed during spraying have a narrow size distribution and are evenly distributed.
• the fluidized bed is preferably configured to fluidize the ammonium sulfate nuclei and the resulting granule particles.
• the device comprises the components additionally in operative connection with the device:
• the partitioning device is preferably arranged downstream of the fluidized bed and configured to divide the granules into fractions of different particle size.
• those particles which have the desired target size are preferably further processed after leaving the fluidized bed.
• Particles with a size above the desired target size, possibly also a small part of the product stream, are preferably fed to a comminuting device and comminuted there.
• the comminuted particles are again fed to the fluidized bed as nuclei.
• Particles having a size below the desired target size are again fed to the fluidized bed as nuclei.
• the purification step is preferably configured to purify the air that has flowed through the fluidized bed, i. in particular free of solid particles and droplets.
• the cleaning step is a wet scrubber.
• the device according to the invention is used in the method according to the invention.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Inorganic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Pest Control & Pesticides (AREA)
• Geology (AREA)
• Engineering & Computer Science (AREA)
• Combustion & Propulsion (AREA)
• Fertilizers (AREA)
• Glanulating (AREA)
• Curing Cements, Concrete, And Artificial Stone (AREA)
• Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
• Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)

Applications Claiming Priority (2)

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• 2015
  • 2015-05-27 DE DE102015108344.2A patent/DE102015108344A1/de not_active Ceased
• 2016
  • 2016-05-13 TW TW105114965A patent/TW201718407A/zh unknown
  • 2016-05-25 WO PCT/EP2016/061810 patent/WO2016189036A1/de active Application Filing
  • 2016-05-25 US US15/574,686 patent/US10512886B2/en not_active Expired - Fee Related
  • 2016-05-25 JP JP2017558465A patent/JP6722197B2/ja not_active Expired - Fee Related
  • 2016-05-25 KR KR1020177028793A patent/KR20170127537A/ko not_active IP Right Cessation
  • 2016-05-25 CA CA2980409A patent/CA2980409C/en not_active Expired - Fee Related
  • 2016-05-25 EP EP16724673.5A patent/EP3302777A1/de not_active Withdrawn
  • 2016-05-25 AU AU2016269056A patent/AU2016269056B2/en not_active Ceased
  • 2016-05-25 BR BR112017018302-1A patent/BR112017018302A2/pt active Search and Examination
  • 2016-05-25 CN CN201680023328.2A patent/CN107531583A/zh active Pending

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