WO2010117751A2 - Pastillation of ammonium sulfate nitrate - Google Patents
Pastillation of ammonium sulfate nitrate Download PDFInfo
- Publication number
- WO2010117751A2 WO2010117751A2 PCT/US2010/029136 US2010029136W WO2010117751A2 WO 2010117751 A2 WO2010117751 A2 WO 2010117751A2 US 2010029136 W US2010029136 W US 2010029136W WO 2010117751 A2 WO2010117751 A2 WO 2010117751A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ammonium sulfate
- slurry melt
- melt
- slurry
- nitrate
- Prior art date
Links
- KKEOZWYTZSNYLJ-UHFFFAOYSA-O triazanium;nitrate;sulfate Chemical compound [NH4+].[NH4+].[NH4+].[O-][N+]([O-])=O.[O-]S([O-])(=O)=O KKEOZWYTZSNYLJ-UHFFFAOYSA-O 0.000 title claims abstract description 22
- 239000002002 slurry Substances 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 35
- 230000008569 process Effects 0.000 claims abstract description 29
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 16
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims description 34
- 239000007787 solid Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 102100022089 Acyl-[acyl-carrier-protein] hydrolase Human genes 0.000 abstract 1
- 101000824278 Homo sapiens Acyl-[acyl-carrier-protein] hydrolase Proteins 0.000 abstract 1
- 239000003337 fertilizer Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- 235000015097 nutrients Nutrition 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 238000013019 agitation Methods 0.000 description 5
- 238000005469 granulation Methods 0.000 description 5
- 230000003179 granulation Effects 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000012530 fluid Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012958 reprocessing Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- DVARTQFDIMZBAA-UHFFFAOYSA-O ammonium nitrate Chemical class [NH4+].[O-][N+]([O-])=O DVARTQFDIMZBAA-UHFFFAOYSA-O 0.000 description 1
- NGLMYMJASOJOJY-UHFFFAOYSA-O azanium;calcium;nitrate Chemical compound [NH4+].[Ca].[O-][N+]([O-])=O NGLMYMJASOJOJY-UHFFFAOYSA-O 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000000112 cooling gas Substances 0.000 description 1
- 238000005474 detonation Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000013529 heat transfer fluid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000289 melt material Substances 0.000 description 1
- 235000010603 pastilles Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- -1 steam Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C1/00—Ammonium nitrate fertilisers
- C05C1/02—Granulation; Pelletisation; Stabilisation; Colouring
-
- 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
- B01J2/20—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by expressing the material, e.g. through sieves and fragmenting the extruded length
-
- 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
- B01J2/26—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic on endless conveyor belts
Definitions
- This invention relates to a process for the production of uniform sized particles of fertilizer. More particularly it is directed to the production of a solid material used for fertilizer from a mixture of a solid and liquid.
- the production of mixed fertilizer products has been performed by mixing and/or reacting of the individual fertilizer components and forming the components/products into particles of the desired size range.
- the particles can comprise a range of sizes, representing a less-preferred product, and are screened, with off-size material separated and collected for reprocessing or to be sold as a less valuable product.
- Blended fertilizers are also common where the fertilizer components are mixed but not formed into particles containing all of the components, or nutrients. This leads to non-homogeneous particles with differing component content, in particular the amount of nitrogen can vary throughout the mixture. The nonuniformity leads to a nonuniformity in the spreading, time-release rates and effectiveness of the nutrients.
- Fertilizers that have been formed into pellets or granules containing mixtures of the nutrients can also include trace compounds that are added for the enhancement of the fertilizer for a particular use.
- fertilizers that are formed into uniform particles can have more control over the release of nutrients into the soil over which the fertilizers are spread. The rates of release of the nutrients and the control of the composition can reduce the loss of the nutrients before plants have the ability to absorb them.
- Prilling is one method of the production of small spherical pellets, wherein the melted material is passed through an apparatus called a prill head which generates streams of liquid droplets. The droplets have little or no volatile matter, and contain no solvents to be removed.
- the droplets are cooled with a continuous stream of cooling gas, typically air to solidify the droplets.
- Granulation is another method, whereby melted material is discharged through spray nozzles to create particles of the fertilizer that are mixed and agglomerated in a rotating drum.
- a process for the production of ammonium sulfate nitrate.
- the process comprises forming a slurry melt by reacting ammonium nitrate and an excess of ammonium sulfate to form a slurry melt comprising ammonium sulfate nitrate.
- the slurry melt is continuously mixed to maintain it in a shear thinned state and to keep solids suspended in the slurry melt.
- the slurry melt is passed to a heated stator, where the slurry melt is continuously mixed as the slurry melt passes through the heated stator.
- a portion of the slurry melt is passed through a channel in the heated stator, and the slurry melt is extruded through a grid that moves over the channel.
- the slurry melt is extruded as droplets from the moving grid where the droplets drop to a cooled moving belt.
- Figure 1 is a diagram of the process
- Figure 2 is a diagram of a modified rotary forming pastillation device.
- Basic components for many fertilizers include a nitrogen source, and usually include a source of sulfur.
- Ammonium sulfate nitrate is common in the industry and generally refers to a mixture of double salts of ammonium sulfate with ammonium nitrate, and includes small amounts of the single salts.
- One ammonium sulfate nitrate product is a solid product known as fusion ammonium sulfate nitrate (FASN).
- FASN addresses many of the concerns of the fertilizer market for the production of solid particulate fertilizers such as ammonium nitrate, urea-ammonium nitrate, and calcium ammonium nitrate.
- One objective is the production of uniform size particles such that further processing, such as screening, grinding, remelting, fattening or further agglomeration is not needed.
- the particles When referring to the particles as uniform, the particles have a generally uniform semi-ellipsoidal shape, with a flattened side, and a narrow size, or diameter, range of the particles.
- Ammonium sulfate nitrate is a desirable fertilizer in that it has improved properties of stability and safety against detonation over other ammonium nitrate compounds. While ammonium sulfate nitrate (ASN) is a known compound, the process presented here is for the production of Honeywell's patented formulation, found in U.S. Patent No. 6,689,181, and hereinafter, the use of ASN, or fusion ammonium sulfate nitrate (FASN) refers to this formulation. In addition, ammonium nitrate sulfate has superior resistance to moisture, to slow the delivery of the nutrients to plants and to limit the losses due to rain.
- the present invention is to produce a substantially uniform sized particle for FASN, in the size range required by its users.
- FASN comprises a uniform mixture of ammonium sulfate nitrate (ASN) double salts and unreacted ammonium sulfate (AS) with a small amount of unreacted ammonium nitrate (AN).
- the desired product is one which is predominantly the double salt has a 2:1 ratio of ammonium nitrate to ammonium sulfate, or (AN)2AS.
- a small amount of the 3: 1 ratio double salt is formed, or (AN) 3 AS .
- the process uses an excess of ammonium sulfate which favors the production of the 2:1 double salt over the 3 : 1 double salt.
- Table 1 The desired ranges for the FASN composition, on a dry basis is shown in Table 1.
- the formation of FASN using traditional methods involves considerable uncertainty with regards to equipment performance, suitability, on-stream performance, product quality, emissions, and capital and operating cost.
- the starting material for FASN is a molten slurry melt and has a shear-thinning property.
- the melt which is formed in a reactor, comprises a molten ammonium sulfate nitrate in an amount between 60 and 70 wt. % and finely-ground, undissolved ammonium sulfate in an amount between 30 and 40 wt. %.
- the slurry melt must be kept moving, or under a shearing condition to prevent the viscosity from increasing and to prevent the separation of the solids. An increasing viscosity, or thickening of the melt, and/or a separation of the solids can lead to plugging of the lines and equipment. This can lead to non-uniformity in the size of the FASN particles.
- One method of production of FASN is prilling, where the slurry melt must be elevated to, typically, between 150 to 250 feet above grade for the particles to be cooled and solidified sufficiently. Control over the size of the particles, including coalescence of several particles during cooling, and the production of sub-micrometer sized particles requires screening, recycling and remelting of a portion of the FASN.
- the present invention provides for the use of existing downstream assets, with few if any modifications, and provides for a low intensity, solid particle formation to produce a highly uniform size and shaped product.
- the process uses pastillation to form substantially uniform semi-ellipsoidal particles by solidification of a liquid melt on a cooling surface. There are several commercial manufacturers of pastillation equipment, however, the process needs to be modified to produce a uniform FASN product.
- the process as shown in Figure 1 , comprises forming a slurry melt of ammonium sulfate nitrate and ammonium sulfate in a reactor 10.
- the slurry melt is passed to a heated stator 20, where the slurry melt is continuously agitated, and extruded as droplets onto a moving belt 30 that is cooled to form solid semi-ellipsoidal particles in the 1 to 3 mm range.
- the droplets will form into particles in the 2 to 3 mm range, and more preferably to have a nominal diameter of 2.5 mm necessary to meet a size guide number (SGN) from 220 to 280.
- SGN size guide number
- the preferred more narrow size range is highly uniform product.
- the slurry melt as shown in Figure 2, is passed through a channel 22 in the stator 20 and extruded through a moving grid 24 that slides over the channel 22.
- the channel 22 is part of a larger cylindrical passage 26 through which the slurry melt is transported.
- the slurry melt is continuously agitated to prevent an increase in the viscosity.
- the heated stator 20 is comprised of a hollow, partially closed, cylindrical passage 26 within the heated stator 20, where the cylindrical passage 26 spans the length of the stator 20.
- the heating medium can be any suitable fluid, such as heated water, steam, heat transfer fluid or other compatible process fluid.
- the slurry melt enters under a small, less than 0.8 MPa, but controlled pressure that is sufficient to pass the slurry melt through the heated stator 20. The flow is kept to a level sufficient to maintain the suspension of solids and to keep the slurry melt free-moving. A portion of the slurry melt is passed out of the stator 20 and returned to the reactor 10.
- the slurry melt passes from the cylindrical passage 26 to a channel 22 located at the bottom of the stator 20.
- a perforated cylindrical drum 40 rotates around the heated stator 20.
- the holes 42 in the drum 40 pass across the bottom of the channel 22 where the slurry melt is extruded.
- the extruded slurry melt falls as drops onto a moving belt 30 that is cooled, and the cooled slurry melt solidifies to form the product particles, also known as pastilles of the desired diameter.
- the holes are sufficiently spaced to prevent neighboring drops from agglomerating with other drops on the cooling belt 30, and the holes 42 are sized sufficiently large to freely allow the passage of solid particles at or smaller than 300 micrometers in the maximum particle dimension.
- the stator 20 and rotary drum 40 assembly will be horizontally oriented above and perpendicular to the direction of movement of the cooling belt 30, with the stator 20 and drum 40 spanning the width of the moving belt 30.
- the stator 20 and rotary drum 40 assembly is located at the inlet end of the cooled section of the belt 30 in a manner typical for such belt-coolers.
- the agitation system comprises an axially aligned, rotating, multi-bladed, wall- wiping paddle system 44.
- the paddle system 44 is rotated at a low speed of between approximately 200 rpm and 600 rpm, and preferably between 200 rpm and 400 rpm or at approximately 300 rpm.
- the slurry melt comprises liquid ammonium sulfate nitrate in an amount between 60 and 80 % by weight with a preferred amount between 60 and 70 % by weight.
- the slurry melt also includes solid ammonium sulfate in an amount between 40 and 20 % by weight with a preferred amount between 30 and 20 % by weight.
- the solid ammonium sulfate is finely ground and it is preferred that when the slurry melt leaves the reactor 10, the solid particles are less than 300 micrometers in the maximum dimension.
- the solid particles partially react and partially dissolve in the slurry melt.
- the slurry melt is agitated in the reactor 10 to create and maintain the suspension of solids in the melt.
- the process entails significant temperature control over the entire process, including the stirred reactor 10 and the heated stator 20, to maintain the slurry melt at a temperature between 180 0 C and 200 0 C.
- the process is controlled to heat the reactor 10 and the heated stator 20 to a temperature between 185°C and 190 0 C.
- the process is controlled to prevent the temperature from falling below 178°C, where the slurry melt can begin to solidify, and to prevent the temperature from exceeding 210 0 C, where the ammonium nitrate begins to decompose.
- the process is further controlled to maintain any pressures in the system below 1.14 MPa (150 psig), and preferably to maintain any pressures in the system below 0.8 MPa (100 psig).
- This includes operating the reactor at or near atmospheric pressure, and keeping the pressure in the piping and the heated stator at low operating pressures, typically less than 0.8 MPa, and preferably at pressures below 0.2 MPa.
- the maintenance of the slurry melt in a heated and stirred, or agitated, state to maintain a lower viscosity contributes to operating at lower pressures.
- the agitation is provided by a multi-bladed wall wiping paddle system
- the invention is intended to cover other agitation systems.
- One example is an auger type system that mixes and moves the slurry melt though the cylindrical passage 26 in the heated stator 20.
- the holes 42 in the moving drum 40 are kept free from buildup of solidified material or agglomerated solids. This includes the removal of residual slurry melt material that might adhere to the holes 42 or the drum 40 near the holes 42.
- the process further comprises passing a hot fluid, such as hot water or steam through the moving grid holes 42 after the slurry melt has dropped from the moving drum 40 to the moving belt 30.
- the apparatus can include an additional channel 50 through the heated stator 20.
- the additional channel 50 extends a length at least as long as the span of the moving drum 40. In a practical consideration, the additional channel 50 extends the entire length of the stator 20.
- a collection system surrounding the stator 20 and moving drum 40 can be included to recover any residual material blown out of the grid holes 42.
- the collection system can be incorporated into the surrounding heated shroud 60, and designed to prevent any residual material from falling to the moving belt 30.
- the system can include a scraper 52 for mechanically scraping of material around the edges of the holes 42.
- the spring-loaded scraper device 52 spans the entire length of the rotating drum 40. The positioning of the scraper 52 can be at different locations around the drum. One location is after blowing out residual material, and an alternate location is at a point just prior to the alignment of the drum's holes 42 with the channel 22 of the stator 20. It is preferred that the scraper 52 be made of a softer material than the drum to minimize wear on the rotating drum 40.
- the system can also include a second moving belt system 54 for collecting and removing residual material from the environment inside the heated shroud 60.
- An alternate system can include a sloped and heated trough to collect the material as a liquid and channel the material to a heated sump for return to the reactor 10 for re-use.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Fertilizers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012503587A JP6046489B2 (en) | 2009-03-31 | 2010-03-30 | Tableting ammonium sulfate |
BRPI1013631-2A BRPI1013631B1 (en) | 2009-03-31 | 2010-03-30 | PROCESS FOR THE PRODUCTION OF AMMONIUM SULFATE NITRATE |
CN201080023931.3A CN102448911B (en) | 2009-03-31 | 2010-03-30 | Pastillation of ammonium sulfate nitrate |
ES10762164T ES2768238T3 (en) | 2009-03-31 | 2010-03-30 | Formation of ammonium sulfate nitrate pellets |
UAA201112680A UA104172C2 (en) | 2009-03-31 | 2010-03-30 | Process for preparation of ammonium sulfate nitrate |
EP10762164.1A EP2414307B1 (en) | 2009-03-31 | 2010-03-30 | Pastillation of ammonium sulfate nitrate |
AU2010234908A AU2010234908B2 (en) | 2009-03-31 | 2010-03-30 | Pastillation of ammonium sulfate nitrate |
RU2011142093/13A RU2537810C2 (en) | 2009-03-31 | 2010-03-30 | Tablettng ammonium sulphate-nitrate |
CA2757445A CA2757445C (en) | 2009-03-31 | 2010-03-30 | Pastillation of ammonium sulfate nitrate |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/415,312 | 2009-03-31 | ||
US12/415,312 US7985393B2 (en) | 2009-03-31 | 2009-03-31 | Pastillation of ammonium sulfate nitrate |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2010117751A2 true WO2010117751A2 (en) | 2010-10-14 |
WO2010117751A3 WO2010117751A3 (en) | 2011-03-03 |
Family
ID=42782465
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2010/029136 WO2010117751A2 (en) | 2009-03-31 | 2010-03-30 | Pastillation of ammonium sulfate nitrate |
Country Status (11)
Country | Link |
---|---|
US (2) | US7985393B2 (en) |
EP (1) | EP2414307B1 (en) |
JP (1) | JP6046489B2 (en) |
CN (1) | CN102448911B (en) |
AU (1) | AU2010234908B2 (en) |
BR (1) | BRPI1013631B1 (en) |
CA (1) | CA2757445C (en) |
ES (1) | ES2768238T3 (en) |
RU (1) | RU2537810C2 (en) |
UA (1) | UA104172C2 (en) |
WO (1) | WO2010117751A2 (en) |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2013035106A1 (en) * | 2011-09-07 | 2013-03-14 | Indo Gulf Fertilizers | A process for manufacturing a composite fertilizer |
US9464008B2 (en) * | 2012-02-01 | 2016-10-11 | Honeywell International Inc. | Process for preparing ammonium sulfate nitrate |
US9932278B2 (en) * | 2015-03-12 | 2018-04-03 | Advansix Resins & Chemicals Llc | Granulator feed apparatus |
CN104926374B (en) * | 2015-06-30 | 2017-12-19 | 河北冀衡赛瑞化工有限公司 | A kind of production method of sulfenyl nitrate fertilizer |
DE102015212353B3 (en) * | 2015-07-01 | 2016-07-07 | Sandvik Materials Technology Deutschland Gmbh | Apparatus and method for dripping a flowable product |
DE102016221501B3 (en) * | 2016-11-02 | 2017-12-21 | Sandvik Materials Technology Deutschland Gmbh | Device for dripping a flowable product and method for operating such a device |
CZ2017279A3 (en) * | 2017-05-18 | 2018-11-21 | Lovochemie, A.S. | A method of preparation of a nitrogen-sulphur granulated fertilizer and a device for implementing this method |
CN110090597A (en) * | 2018-01-30 | 2019-08-06 | 徐州市禾协肥业有限公司 | A kind of discharging device and prilling granulator for inclined-plane cooling granulation |
CN110090592A (en) * | 2018-01-30 | 2019-08-06 | 徐州市禾协肥业有限公司 | A kind of device for squeezing slurry and forming drop |
CN110092673A (en) * | 2018-01-30 | 2019-08-06 | 徐州市禾协肥业有限公司 | The floating grain system of intelligence, granulated fertilizer and the floating grain method of intelligence |
CN110090600B (en) * | 2018-01-30 | 2023-01-31 | 徐州市禾协肥业有限公司 | Method for extruding fertilizer slurry into liquid drops and granular fertilizer |
CN110404479A (en) * | 2018-04-28 | 2019-11-05 | 徐州市禾协肥业有限公司 | Prepare system and method, the coronal fertiliser granulates of coronal fertiliser granulates |
CN110404475A (en) * | 2018-04-28 | 2019-11-05 | 徐州市禾协肥业有限公司 | A kind of drop forming device of strip gab |
CN109796029B (en) * | 2019-03-06 | 2021-01-15 | 湖北三宁化工股份有限公司 | Preparation method of ammonium nitrate sulfate |
CN111558332A (en) * | 2020-03-27 | 2020-08-21 | 浙江三圣科技有限公司 | Granulation forming device for large-particle compound fertilizer |
CN111569756A (en) * | 2020-03-27 | 2020-08-25 | 浙江三圣科技有限公司 | Equalizer anti-precipitation device |
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2009
- 2009-03-31 US US12/415,312 patent/US7985393B2/en active Active
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2010
- 2010-03-30 ES ES10762164T patent/ES2768238T3/en active Active
- 2010-03-30 UA UAA201112680A patent/UA104172C2/en unknown
- 2010-03-30 RU RU2011142093/13A patent/RU2537810C2/en active
- 2010-03-30 EP EP10762164.1A patent/EP2414307B1/en active Active
- 2010-03-30 AU AU2010234908A patent/AU2010234908B2/en active Active
- 2010-03-30 WO PCT/US2010/029136 patent/WO2010117751A2/en active Application Filing
- 2010-03-30 CA CA2757445A patent/CA2757445C/en active Active
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WO2010117751A3 (en) | 2011-03-03 |
EP2414307B1 (en) | 2019-11-06 |
US7985393B2 (en) | 2011-07-26 |
BRPI1013631A2 (en) | 2016-04-19 |
JP6046489B2 (en) | 2016-12-14 |
UA104172C2 (en) | 2014-01-10 |
CN102448911A (en) | 2012-05-09 |
US20100242556A1 (en) | 2010-09-30 |
ES2768238T3 (en) | 2020-06-22 |
CA2757445A1 (en) | 2010-10-14 |
US8268279B2 (en) | 2012-09-18 |
RU2011142093A (en) | 2013-05-10 |
CA2757445C (en) | 2017-10-17 |
AU2010234908A1 (en) | 2011-10-27 |
BRPI1013631B1 (en) | 2021-07-20 |
AU2010234908B2 (en) | 2014-06-26 |
US20110277522A1 (en) | 2011-11-17 |
EP2414307A4 (en) | 2017-05-03 |
RU2537810C2 (en) | 2015-01-10 |
EP2414307A2 (en) | 2012-02-08 |
JP2012521959A (en) | 2012-09-20 |
CN102448911B (en) | 2015-06-17 |
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