WO1994003267A1 - Process for the production of urea granules - Google Patents
Process for the production of urea granules Download PDFInfo
- Publication number
- WO1994003267A1 WO1994003267A1 PCT/NL1993/000167 NL9300167W WO9403267A1 WO 1994003267 A1 WO1994003267 A1 WO 1994003267A1 NL 9300167 W NL9300167 W NL 9300167W WO 9403267 A1 WO9403267 A1 WO 9403267A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- urea
- solution
- granulation
- granules
- melt
- Prior art date
Links
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
- 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
- B01J2/28—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic using special binding agents
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C9/00—Fertilisers containing urea or urea compounds
- C05C9/005—Post-treatment
Definitions
- urea granules For the production of urea granules various methods are known. In the past prilling was the predominant method, wherein a substantially anhydrous urea melt ( having a water content of no more than 0.1 to 0.3% by weight) is sprayed from the top of a prilling column in a rising stream of air of ambient temperature in which the droplets solidify to form so-called prills. These prills have a relatively small maximum diameter and are mechanically rather weak.
- Urea granules having larger dimensions and better mechanical properties are presently being produced by the granulation of a substantially anhydrous urea melt or of an aqueous urea solution in a fluidized bed, for example as described in US patent specification 4,219,589.
- an aqueous urea solution having a urea concentration of 70 - 99.9 % by weight, preferably 85 - 96 % by weight is sprayed in the form of very fine droplets having an average diameter of 20 - 120 ⁇ into a fluidized bed of urea particles at a temperature at which the water evaporates from the solution sprayed onto the particles, and urea solidifies on the particles to form granules having a desired size which may be 2.5 mm and more.
- the urea solution used as the starting material contains more than 5% by weight of water, in particular more than 10 % by weight of water, preferably a crystallization retarder or granulation additive for the urea, in particular a water-soluble addition or condensation product of formaldehyde and urea, is added to the urea solution, whereby the formation of fly dust is considerably lower, or even suppressed.
- a crystallization retarder or granulation additive for the urea in particular a water-soluble addition or condensation product of formaldehyde and urea
- the result of the presence of the granulation additive is that the granules remain plastic as they are being formed, so that owing to rolling and/or impacts during the formation mechanically strong, smooth and round granules may be formed.
- the resulting granules have a high crushing strength, a high i ⁇ pact resistance, and little tendency of forming fly dust through abrasion, and moreover do not cake together, not even upon prolonged storage, although urea exhibits a strong natural tendency of caking together.
- the object of the present invention is to provide a process for the production of urea granules by a granulation technique, preferably as described in US patent specification No. 4.219,589, wherein the amount of dust formed during granulation is reduced, as well as the amount of fly dust of the end product.
- the invention is directed to a process for the production of urea granules from a melt or solution of urea by spraying the urea melt or solution, which also contains as granulation additive formaldehyde, methylolureum, formurea, or hexamethyleentetramine, in the form of very fine droplets into a fluidized bed or urea particles in which process the granulation additive is added prior to the granulation at such a stage, that the mixture of the said granulation additive and the urea melt or solution has a contact time of at least 20 s, but not more than 20 min.
- the optimum value for the contact time depends on various factors, such as the water content of the urea melt or solution, the temperature, the amount of granulation additive and the chemical formulation of the additive. More in particular it is observed that with shorter contact times the effect of reduced dust formation and fly dust is not obtained, ith residence times longer than 20 in the amounts of biuret and triuret tend to become prohibitively high.
- the contact time is between 25 s and 20 min, as within this range the optimim results are obtained.
- Preferred granulation additives are formaldehyde and water-soluble addition and/or condensation products of formaldehyde and urea.
- the production of water-soluble addition products of formaldehyde and urea is known, for example, from US patent 3,067,177 and the production of water-soluble condensation products of formaldehyde and urea is disclosed in US patent 3,112,343. It is also possible to use addition products of formaldehyde and urea produced in the first place in an alkaline medium and then condensed in an acid medium to form thin-liquid to syruppy liquids, such as the liquid adhesives used in the chipboard industry.
- the process of the present invention can be applied in a conventional urea production and granulation unit, for example such as described in US patent specification No. 4,219,859.
- a synthesis solution of urea is obtained from a urea plant, which synthesis solution, optionally after concentration to the required water content, is mixed with the granulation additive, preferably in an amount of 0,3 to 0.8 wt.%, calculated as formaldehyde, based upon the weight of the final granules.
- This mixing can be done at any stage of the process, provided care is taken that the required contact time is provided. If necessary it is possible to include a separate, buffer vessel after a mixing device and prior to the fluidized bed. Alternatively the granulation additive can be added prior to the evaporation of water from the urea solution, provided that care is taken to remain within the ranges of the contact time.
- the additive is used in a quantity corresponding to 0.3 - 0.8 % by weight of formaldehyde, calculated on the final product. If desired, higher ratios may be used, but this does not offer any particular advantages.
- the additive may be added in any suitable form, but preferably as a concentrated aqueous solutions, whereby the concentration ranges from 30 to 85 wt.%.
- the granules are cooled to a temperature compatible with the ambient air conditions, e.g. to about 40-45°C for tropical or to about 30°C for moderate climatic conditions, for example by means of a stream of air, the moisture content of which has preferably been reduced to such an extent that during the cooling process the granules do not absorb moisture from the cool air.
- a temperature compatible with the ambient air conditions e.g. to about 40-45°C for tropical or to about 30°C for moderate climatic conditions, for example by means of a stream of air, the moisture content of which has preferably been reduced to such an extent that during the cooling process the granules do not absorb moisture from the cool air.
- urea granules produced in accordance with the present invention can advantageously be used in combination with superphosphate and triple superphosphate.
- other components can be combined therewith, such as a potassium fertilizer (usually KC1) .
- the granulation of urea can be carried out by spraying an aqueous solution on to fluidized urea nuclei, said solution having urea concentration of 70-99.9% by weight.
- the urea solution is sprayed with a gas, such as air.
- a gas such as air.
- the solution is sprayed within the fluidized bed of urea nuclei, as spraying on to the bed involves the risk of the sprayed droplets being entrained by the fluidization air issuing from the bed.
- the pressure of the spraying air is preferably 118-392 kPa (1.2-4 ata) . This pressure has a highly important effect on the size of the sprayed droplets. The higher the pressure, the smaller are the sprayed droplets.
- the mean drop diameter is preferably between 25 and 250 ⁇ m.
- the size of the urea nuclei supplied to the fluidized bed in which the granulation takes place generally ranges between 0.2 and 3 mm, but may be larger when larger urea granules are to be made.
- the te ⁇ perature of the fluidized bed of urea nuclei generally range between 70° and 115°C, preferably between 80° and 110°C. Within these limits, the temperature may be lower according as the urea concentration the solution sprayed on to the nuclei is higher.
- the te ⁇ perature of the fluidized bed can be controlled by a suitable selection of the temperature of the fluidization air and of the concentration of the urea solution being sprayed.
- the urea solution is sprayed over the urea nuclei in the form of very fine droplets. Under the influence of the temperature prevailing in the fluidized bed, the water is evaporated from the solution and the urea crystallizes on the surface of the urea nucleus.
- the product produced by the process according to the present invention contains only small quantities of free NH 3 . C0 2 , moisture and biuret and has such mechanical properties that it is suitable for pneumatic transportation, and remains free flowing even after prolonged storage.
- a particular advantage of the process according to the invention is that the formation of biuret during the granulation is prevented almost entirely.
- a urea solution having a urea content of for example, 75-85% by weight and a biuret content of less than 0.1% urea granules with a biuret content of less than 0.1% can be obtained.
- the urea granules produced by the process of this invention are highly suitable for being coated with, for example, sulphur, to form slow-release granules, as, owing to their excellent sphericity and their closed surface, the required amount of coating material is minimized.
- the process according to the present invention can be carried out in any type of fluid-bed granulator.
- a granulator 1 divided into a plurality of compartments 2, 3 and 4 for the granulation, and subsequet compartments 5 and 6 for the subsequent cooling and drying of the urea granules.
- Granulator 1 comprises a grid 7 , which supports the fluidized bed and transmits the.- air of fluidization, optionally preheated in one or more heaters not shown and supplied through conduit 8.
- the space below the grid can be divided in the same way as the space above it, into compartments, in which case the air of fluidization is supplied to each of these compartments.
- Granulator 1 is further provided at the bottom with pneumatic sprayer systems 9, 10 and 11, which extend to a level above grid 7. It is also possible to use two or more sprayer systems in each compartment. Through these sprayers, the urea solution supplied through conduit 13, to which a granulation additive has been added, is sprayed with the atomization air supplied through conduit 14 into the granulation compartments 2, 3 an 4. The urea solution is introduced into buffer vessel 13 c via line.13 a . At the same time the granulation additive is introduced in the buffer vessel via line 13 b . The dimensions of the buffer vessel are such that a sufficient contact time is guaranteed.
- the fluidized bed is constituted by urea nuclei. For the subsequent conditioning, cooling and optional drying of the granules in compartments 5 and 6, granulator 1 is equipped with a conduit 16 for supplying air.
- granulator 1 For the removal of air and possibly entrained dust particles, granulator 1 has discharge conduits 17 and 18, which are connected to a scrubber 19, in which the air is washed with a dilute urea solution to remove fine dust and possibly remaining very small granules.
- a scrubber 19 In order that a high washing efficiency may be achieved, water may be sprayed into the air through a sprayer 23. The air stripped of dust can escape through discharge conduit 24, and the dilute urea solution formed is discharged through conduit 25.
- Granulator 1 further comprises a bottom outlet 26 for urea granules, terminating over a vibratory chute 27, whence the granules are transported to a screening device 28, in which they are separated into a number of fractions, namely into an undersize fraction, a fraction having the desired sizes, and an oversize fraction.
- the fraction having the desired sizes is optionally passed through a cooler 29 to a storage site, where further separation into fractions for different purposes can be effected. If desired, the cooler may be arranged upstream of the sieving device.
- the fraction of oversize granules separated in sieving device 28 is transported to a crusher 30 in which this fraction is crushed to the required size to serve as fresh nuclei.
- the undersize fraction separated in sieving device 28 is passed through conduit 32 to conduit 31, together with the fraction from crusher 30 to be returned to the granulator 1.
- the quantity of urea granules removed from the system to the storage is replaced by fresh urea nuclei from the crusher.
- the size of the product granules depends on a number of factors, such as the number of urea nuclei in the fluidized bed, the size of these nuclei, the quantity of urea solution sprayed per unit of time, and the residence time of the nuclei in the bed. Thus, for example, larger product granules will be obtained, if the number of nuclei in the fluidized bed is reduced and the residence time is prolonged. In order that a predetermined particle size distribution of the product may be maintained, it is necessary for the bed contents to be kept as constant as possible als regards both the particle size distribution and the number of nuclei.
- crusher 30 should be properly controlled: if the broken product is too fine, too much dust is supplied to the fluidized bed, where it either entrained by the fluidization gas, or causes agglomaration; if the broken product is too coarse, too few nuclei are supplied to the fluidized bed.
- t/d urea was granulated.
- a granulation additive based on a urea/formaldehyde condensate was added in an amount corresponding to 0.50 wt.% of CH 2 0, calculated on the final product.
- the contact time of the granulation additive and the urea melt was varied. In the table the results of the various experiments is reported.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Fertilizers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Glanulating (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Steroid Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
Claims
Priority Applications (13)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
UA95028114A UA26359C2 (en) | 1992-08-07 | 1993-08-05 | METHOD OF PRODUCTION OF UREA GRAGUL |
RO95-00196A RO113007B1 (en) | 1992-08-07 | 1993-08-05 | Process for producing urea granules |
DE69303284T DE69303284T2 (en) | 1992-08-07 | 1993-08-05 | METHOD FOR PRODUCING UREA GRANULES |
CA002141874A CA2141874C (en) | 1992-08-07 | 1993-08-05 | Process for the production of urea granules |
KR1019950700438A KR100299404B1 (en) | 1992-08-07 | 1993-08-05 | Manufacturing method of urea granule |
PL93307334A PL307334A1 (en) | 1992-08-07 | 1993-08-05 | Method of obtaining carbamide pellets |
EP93921123A EP0653961B1 (en) | 1992-08-07 | 1993-08-05 | Process for the production of urea granules |
RU95106645/25A RU2104258C1 (en) | 1992-08-07 | 1993-08-05 | Method of granulated urea production |
AU48354/93A AU666404B2 (en) | 1992-08-07 | 1993-08-05 | Process for the production of urea granules |
US08/381,851 US5653781A (en) | 1992-08-07 | 1993-08-05 | Process for the production of urea granules |
GEAP19932405A GEP19981292B (en) | 1992-08-07 | 1993-08-05 | Process for the Production of Urea Granules |
JP50519894A JP3388743B2 (en) | 1992-08-07 | 1993-08-05 | Method for producing urea granules |
BG99405A BG61332B1 (en) | 1992-08-07 | 1995-02-07 | Method for the preparation of granular urea |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ID924539 | 1992-08-07 | ||
IDP-004539 | 1992-08-07 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1994003267A1 true WO1994003267A1 (en) | 1994-02-17 |
Family
ID=11004968
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/NL1993/000167 WO1994003267A1 (en) | 1992-08-07 | 1993-08-05 | Process for the production of urea granules |
Country Status (17)
Country | Link |
---|---|
US (1) | US5653781A (en) |
EP (1) | EP0653961B1 (en) |
JP (1) | JP3388743B2 (en) |
KR (1) | KR100299404B1 (en) |
AT (1) | ATE139463T1 (en) |
AU (1) | AU666404B2 (en) |
BG (1) | BG61332B1 (en) |
CA (1) | CA2141874C (en) |
DE (1) | DE69303284T2 (en) |
ES (1) | ES2091037T3 (en) |
GE (1) | GEP19981292B (en) |
NZ (1) | NZ256137A (en) |
PL (1) | PL307334A1 (en) |
RO (1) | RO113007B1 (en) |
RU (1) | RU2104258C1 (en) |
UA (1) | UA26359C2 (en) |
WO (1) | WO1994003267A1 (en) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998058046A1 (en) * | 1997-06-16 | 1998-12-23 | Unilever Plc | Production of detergent granulates |
EP0900589A1 (en) * | 1997-09-04 | 1999-03-10 | Toyo Engineering Corporation | Method for granulation and granulator |
US6133223A (en) * | 1997-06-27 | 2000-10-17 | Lever Brothers Company, Division Of Conopco, Inc. | Production of detergent granulates |
US6274544B1 (en) | 1997-06-16 | 2001-08-14 | Lever Brothers Company, Division Of Conopco, Inc. | Production of detergent granulates |
NL1023941C2 (en) * | 2003-07-17 | 2005-01-18 | Dsm Ip Assets Bv | Process for the preparation of urea granules. |
US7862642B2 (en) | 2006-12-14 | 2011-01-04 | Georgia-Pacific Chemicals Llc | Extended-release urea-based granular fertilizer |
WO2011029682A1 (en) * | 2009-09-10 | 2011-03-17 | Dsm Ip Assets B.V. | Process for producing granules |
CN102438739A (en) * | 2009-05-20 | 2012-05-02 | 斯塔米卡本公司 | Process for producing granules |
EP2489429A1 (en) * | 2011-02-21 | 2012-08-22 | Urea Casale S.A. | Fluid bed granulation of urea and related apparatus |
EP2497567A1 (en) * | 2011-03-10 | 2012-09-12 | Urea Casale S.A. | Process and apparatus for production of a granular urea product |
DE102017108842A1 (en) | 2017-04-25 | 2018-10-25 | Thyssenkrupp Ag | Process and apparatus for the production of urea |
EP3508465A1 (en) | 2018-01-08 | 2019-07-10 | thyssenkrupp Fertilizer Technology GmbH | Internal baffles in fluidised bed cooler |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5917110A (en) * | 1996-10-18 | 1999-06-29 | Tetra Technologies, Inc. | Moisture-resistant calcium containing particles |
CN1087723C (en) * | 1998-10-15 | 2002-07-17 | 王长山 | Urea fused-salt granulating process to produce urea-base composite fertilizer |
JP2002095952A (en) * | 2000-09-22 | 2002-04-02 | Freunt Ind Co Ltd | Fluidized bed granulation coating device and fluidized bed granulation coating method |
JP2002037689A (en) * | 2000-07-24 | 2002-02-06 | Chisso Corp | Coated covering granular fertilizer |
ES2242121T3 (en) * | 2003-05-07 | 2005-11-01 | Degussa Ag | COVERED GRADS OF SODIUM PERCARBONATE WITH IMPROVED STORAGE STABILITY. |
CN100434152C (en) * | 2003-11-10 | 2008-11-19 | 帝斯曼知识产权资产管理有限公司 | Process for the preparation of urea granules |
EP1694613A2 (en) * | 2003-12-18 | 2006-08-30 | Georgia-Pacific Resins, Inc. | Extended-release nitrogen-containing granular fertilizer |
ATE468176T1 (en) * | 2003-12-23 | 2010-06-15 | Yara Int Asa | SPRAY DEVICE AND METHOD FOR FLUID BED GRANULATION |
US20050163911A1 (en) * | 2004-01-28 | 2005-07-28 | Cargill, Inc. | Animal feed product containing crushed urea |
NL1025805C2 (en) * | 2004-03-25 | 2005-09-27 | Dsm Ip Assets Bv | Process for the granulation of urea. |
NL1025954C2 (en) * | 2004-04-15 | 2005-10-18 | Dsm Ip Assets Bv | Method for optimizing a fluid bed granulator. |
JP4852270B2 (en) * | 2005-07-13 | 2012-01-11 | 東洋エンジニアリング株式会社 | Method for producing granular urea product |
JP2009161367A (en) * | 2007-12-28 | 2009-07-23 | Mitsubishi Chemical Agri Inc | Granular slow-release nitrogenous fertilizer |
NO330729B1 (en) * | 2008-04-28 | 2011-06-27 | Yara Int Asa | Process and granulator for the production of granules |
EP2192099A1 (en) * | 2008-11-28 | 2010-06-02 | Uhde Fertilizer Technology B.V. | Urea granulation process with an acidic scrubbing system and the subsequent integration of ammonium salt into urea granules |
CN102674905A (en) * | 2012-05-14 | 2012-09-19 | 山西省霍州市化学工业有限责任公司 | Method and device for recycling dust in urea granules |
US9868098B2 (en) * | 2014-02-05 | 2018-01-16 | Green Granulation Technology Limited | Fluidized bed granulation |
CN104496566B (en) * | 2014-09-12 | 2017-05-31 | 山东茂施生态肥料有限公司 | A kind of granular urea resurfacing method |
CN107428680B (en) | 2015-04-01 | 2021-01-05 | 东洋工程株式会社 | Process for the production of urea |
EP3384980A1 (en) * | 2017-04-06 | 2018-10-10 | SASOL Germany GmbH | Process for production of attrition stable granulated material |
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US4219589A (en) * | 1977-06-09 | 1980-08-26 | Compagnie Neerlandaise De L'azote | Process for urea granulation |
EP0212714A1 (en) * | 1985-07-26 | 1987-03-04 | Stamicarbon B.V. | Process for the preparation of granules and granules obtained by this process |
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US3067177A (en) * | 1957-10-30 | 1962-12-04 | Montedison Spa | Process for producing concentrated urea-formaldehyde solutions by absorbing gaseous formaldehyde in aqueous urea solutions |
US3112343A (en) * | 1959-08-20 | 1963-11-26 | Chemie Linz Ag | Free-flowing, storage stable granular or pelletized urea |
JPS6034517B2 (en) * | 1978-03-03 | 1985-08-09 | 宇部興産株式会社 | How to granulate urea in a fluidized bed |
SU998446A1 (en) * | 1981-01-09 | 1983-02-23 | Ивановский Химико-Технологический Институт | Process for producing non-caking granulated nitrogen fertilizer |
NL8302999A (en) * | 1983-08-27 | 1985-03-18 | Unie Van Kunstmestfab Bv | METHOD FOR PREPARING GRANULES |
NL8303000A (en) * | 1983-08-27 | 1985-03-18 | Unie Van Kunstmestfab Bv | METHOD FOR PREPARING GRANULES |
-
1993
- 1993-08-05 DE DE69303284T patent/DE69303284T2/en not_active Expired - Lifetime
- 1993-08-05 RU RU95106645/25A patent/RU2104258C1/en active
- 1993-08-05 EP EP93921123A patent/EP0653961B1/en not_active Expired - Lifetime
- 1993-08-05 KR KR1019950700438A patent/KR100299404B1/en not_active IP Right Cessation
- 1993-08-05 GE GEAP19932405A patent/GEP19981292B/en unknown
- 1993-08-05 RO RO95-00196A patent/RO113007B1/en unknown
- 1993-08-05 ES ES93921123T patent/ES2091037T3/en not_active Expired - Lifetime
- 1993-08-05 AT AT93921123T patent/ATE139463T1/en active
- 1993-08-05 WO PCT/NL1993/000167 patent/WO1994003267A1/en active IP Right Grant
- 1993-08-05 US US08/381,851 patent/US5653781A/en not_active Expired - Lifetime
- 1993-08-05 JP JP50519894A patent/JP3388743B2/en not_active Expired - Lifetime
- 1993-08-05 PL PL93307334A patent/PL307334A1/en unknown
- 1993-08-05 AU AU48354/93A patent/AU666404B2/en not_active Expired
- 1993-08-05 CA CA002141874A patent/CA2141874C/en not_active Expired - Lifetime
- 1993-08-05 NZ NZ256137A patent/NZ256137A/en not_active IP Right Cessation
- 1993-08-05 UA UA95028114A patent/UA26359C2/en unknown
-
1995
- 1995-02-07 BG BG99405A patent/BG61332B1/en unknown
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EP0212714A1 (en) * | 1985-07-26 | 1987-03-04 | Stamicarbon B.V. | Process for the preparation of granules and granules obtained by this process |
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Cited By (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998058046A1 (en) * | 1997-06-16 | 1998-12-23 | Unilever Plc | Production of detergent granulates |
US6056905A (en) * | 1997-06-16 | 2000-05-02 | Lever Brothers Company Division Of Conopco, Inc. | Production of detergent granulates |
US6274544B1 (en) | 1997-06-16 | 2001-08-14 | Lever Brothers Company, Division Of Conopco, Inc. | Production of detergent granulates |
AU743403B2 (en) * | 1997-06-16 | 2002-01-24 | Unilever Plc | Production of detergent granulates |
US6429184B1 (en) | 1997-06-16 | 2002-08-06 | Lever & Brothers Company, Division Of Conopco, Inc. | Production of detergent granulates |
US6133223A (en) * | 1997-06-27 | 2000-10-17 | Lever Brothers Company, Division Of Conopco, Inc. | Production of detergent granulates |
EP0900589A1 (en) * | 1997-09-04 | 1999-03-10 | Toyo Engineering Corporation | Method for granulation and granulator |
US6203730B1 (en) | 1997-09-04 | 2001-03-20 | Toyo Engineering Corporation | Method for granulation and granulator |
NL1023941C2 (en) * | 2003-07-17 | 2005-01-18 | Dsm Ip Assets Bv | Process for the preparation of urea granules. |
WO2005007619A1 (en) * | 2003-07-17 | 2005-01-27 | Dsm Ip Assets B.V. | Process for the preparation of urea granules |
EA008450B1 (en) * | 2003-07-17 | 2007-06-29 | ДСМ Ай Пи ЭССЕТС Б.В. | Process for the preparation of urea granules |
CN100390142C (en) * | 2003-07-17 | 2008-05-28 | 帝斯曼知识产权资产管理有限公司 | Process for the preparation of urea granules |
AU2004257110B2 (en) * | 2003-07-17 | 2009-08-27 | Stamicarbon B.V. | Process for the preparation of urea granules |
US7704419B2 (en) | 2003-07-17 | 2010-04-27 | Dsm Ip Assets B.V. | Process for the preparation of urea granules |
US7862642B2 (en) | 2006-12-14 | 2011-01-04 | Georgia-Pacific Chemicals Llc | Extended-release urea-based granular fertilizer |
CN102438739B (en) * | 2009-05-20 | 2014-12-17 | 斯塔米卡本公司 | Process for producing granules |
CN102438739A (en) * | 2009-05-20 | 2012-05-02 | 斯塔米卡本公司 | Process for producing granules |
EP2305371A1 (en) * | 2009-09-10 | 2011-04-06 | Stamicarbon B.V. | Process for producing granules |
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Also Published As
Publication number | Publication date |
---|---|
EP0653961B1 (en) | 1996-06-19 |
RO113007B1 (en) | 1998-03-30 |
BG61332B1 (en) | 1997-06-30 |
DE69303284T2 (en) | 1997-02-06 |
US5653781A (en) | 1997-08-05 |
AU666404B2 (en) | 1996-02-08 |
EP0653961A1 (en) | 1995-05-24 |
JP3388743B2 (en) | 2003-03-24 |
RU2104258C1 (en) | 1998-02-10 |
KR100299404B1 (en) | 2002-04-24 |
AU4835493A (en) | 1994-03-03 |
JPH09500608A (en) | 1997-01-21 |
PL307334A1 (en) | 1995-05-15 |
ES2091037T3 (en) | 1996-10-16 |
NZ256137A (en) | 1995-12-21 |
CA2141874C (en) | 2003-04-22 |
KR950702864A (en) | 1995-08-23 |
DE69303284D1 (en) | 1996-07-25 |
BG99405A (en) | 1995-09-29 |
CA2141874A1 (en) | 1994-02-17 |
GEP19981292B (en) | 1998-05-01 |
UA26359C2 (en) | 1999-08-30 |
ATE139463T1 (en) | 1996-07-15 |
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