WO1997045382A1 - Calcium nitrate based fertilizer - Google Patents

Calcium nitrate based fertilizer Download PDF

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Publication number
WO1997045382A1
WO1997045382A1 PCT/NO1997/000126 NO9700126W WO9745382A1 WO 1997045382 A1 WO1997045382 A1 WO 1997045382A1 NO 9700126 W NO9700126 W NO 9700126W WO 9745382 A1 WO9745382 A1 WO 9745382A1
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WIPO (PCT)
Prior art keywords
fertilizer
weight
calcium nitrate
gypsum
temperature
Prior art date
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Ceased
Application number
PCT/NO1997/000126
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French (fr)
Inventor
Torstein Obrestad
Johanne RØDSVIK
Torbjørn LEGARD
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Norsk Hydro ASA
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Norsk Hydro ASA
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Filing date
Publication date
Application filed by Norsk Hydro ASA filed Critical Norsk Hydro ASA
Priority to IL12720397A priority Critical patent/IL127203A/en
Priority to US09/180,869 priority patent/US6171358B1/en
Priority to EP97922215A priority patent/EP0904257B1/en
Priority to DE69702760T priority patent/DE69702760D1/en
Priority to AT97922215T priority patent/ATE195309T1/en
Priority to PL97330231A priority patent/PL185085B1/en
Priority to AU27946/97A priority patent/AU2794697A/en
Priority to RO98-01608A priority patent/RO117909B1/en
Publication of WO1997045382A1 publication Critical patent/WO1997045382A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C5/00—Fertilisers containing other nitrates
    • C05C5/04—Fertilisers containing other nitrates containing calcium nitrate

Definitions

  • the present invention relates to calcium nitrate based fertilizers containing sulphur and a process for making such fertilizers.
  • Calcium nitrate is widely used within horticulture and as a dry product on open fields.
  • the latter normally contains 75-81 weight% Ca(NO 3 ) 2 , 5-9 weight% NH 4 NO 3 and 12-14 weight% water of crystallization.
  • This type is usually called NH-CN (Norsk Hydro Calcium Nitrate).
  • CN will be used for both these types of fertilizer.
  • the main object of the present invention was to arrive at a homogeneous CN-based fertilizer containing sulphur and optionally magnesium, selenium, cobalt and micronut ⁇ ents Another object was to arrive at a cost effective continuous process for making homogeneous sulphur containing CN-based fertilizers which could be par- ticulated.
  • a further object was to arrive at a process for making homogeneous sulphur containing CN-based fertilizers containing magnesium and optionally selenium, cobalt and micronutrients.
  • gypsum consumes calcium nitrate and the melt loses its ability to solidify due to less power to tie up water of crystallization. Accordingly, the two S-sources were found to be too difficult to apply in CN-based fertilizers.
  • Gypsum (CaSO 4 1/2 H 2 O) was expected to not react with CN melt and should therefore constitute a cheap S-source. Even though gypsum is not water soluble, several agronomical examinations have shown that gypsum is readily available to plants. Different gypsum sources can be utilized, such as dead burned gypsum and gypsum with hydrate water up to dihydrate, the hemi hydrate form is however preferred.
  • Kieserite (MgSO 4 H 2 O) is both a Mg- and S-source which is considered to be water soluble. By mixing this salt into a CN melt the following reaction was found to take place:
  • reaction no. 3 did not take place at a significant rate.
  • kieserite was thoroughly mixed into CN melt for several minutes it was confirmed that said reaction did not result in solidification problems.
  • the investigations also showed that reaction 3 indeed did take place at the surface of each kieserite crystal, but the gypsum formed a thin coating that protected the crystals from further attack by the CN melt.
  • solid gypsum and/or a slow reacting sulphate mineral could be mixed with melted calcium nitrate fertilizer at a temperature of 90-110°C and kept at this temperature for 3-15 minutes and subsequently particulated at a temperature of 80-110°C.
  • the particulation by prilling should be performed at 95-110°C and the granulation at 90-110°C.
  • Microamounts of Co and/or Se and/or micronutrients like Mn, Cu, B, and Zn could be added as solutions of their salts to the mixture prior to particulation.
  • One preferred method comprises mixing 4-23 weight% gypsum, based on the total composition, with a melted calcium nitrate fertilizer at 103-106°C during stirring and keeping the mixture at this temperature for 5-10 minutes and then particulate the thus formed slurry.
  • Another preferred method comprises mixing 4-23 weight% kieserite during stirring with a melted calcium nitrate fertilizer for 6-12 minutes and subsequently particulate the thus formed slurry.
  • Fertilizers according to the invention comprise a homogeneous composition of a calcium nitrate fertilizer and gypsum and/or a slow reacting sulphate mineral comprising 0.1-5.0 weight% SO 4 -S, 14-19 weight% water soluble calcium and 16-21 weight% total calcium and 0-3.0 weight% water soluble magnesium
  • said new fertilizer contains 1.0-3.0 weight% SO 4 -S.
  • the preferred content of magnesium is 0.1-4.0 weight%.
  • This example relates to formation of prilled homogeneous CN-based fertilizer by mixing 12 weight% kieserite crystals into NH-CN melt at 105°C during stirring at this temperature for about 10 minutes and then spraying the slurry through a nozzle. The formed droplets solidified as they fell through cooling air.
  • the product thus formed had a homogeneous composition and had the following analysis:
  • This example shows drum granulation of a homogeneous CN-based fertilizer.
  • 7 weight% kieserite crystals were mixed into 93 weight% NH-CN melt at 105°C and stirred for about 6 minutes.
  • the slurry was then sprayed into a drum containing fines from example 1.
  • Hard homogeneous granules were formed with the following composition:
  • This example shows granulation of homogeneous CN-based fertilizer containing sulphur 11 5 we ⁇ ght% calcium sulphate hemi hydrate (22 1 %S) was mixed with 88 5 we ⁇ ght% NH-CN melt at about 105°C and stirred for about 5 minutes and subsequently sprayed into a rotating drum containing NH-CN fines
  • the thereby formed product had the following analysis
  • This example shows preparation of homogeneous CN-based fertilizer containing sulphur and magnesium and in addition selenium 7 we ⁇ ght% kieserite and some droplets of a 25 we ⁇ ght% Na 2 SeO 4 solution were mixed into a NH-CN melt at about 105°C and stirred for about 5 minutes The melt was solidified as in example 2
  • the formed product had the following analysis
  • This example shows preparation of homogeneous CN-based fertilizer containing both sulphur and magnesium 4 we ⁇ ght% gypsum (calcium sulphate hemi hydrate) and 6 we ⁇ ght% kieserite were thoroughly mixed into 90 we ⁇ ght% of NH-CN melt at about 105°C for about 4 minutes The thereby formed slurry was then sprayed into a granulating drum containing fines Hard, homogeneous granules were formed with the following composition
  • gypsum is a cheaper sulphur source than kieserite and that the product is somewhat less hygroscopic than a product using only kieserite as sulphur and magnesium source.
  • Mg (w.s) 0-4.0 weight% preferably: 0-2.3
  • Ca (w.s) 14-19 weight% preferably: 16-19
  • fertilizers of the above type can contain microamounts of cobalt and selenium, and the usual fertilizer micronutrients like manganese, copper zinc, boron etc.
  • a new type of fertilizer being a homogeneous fertilizer based on calcium nitrate and containing the required amount of sulphur.
  • Said new fertilizer may also contain magnesium and microamounts of Se and Co and micronutrients like Mn, Cu, B, Zn etc.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Fertilizers (AREA)
  • Cosmetics (AREA)
  • Catalysts (AREA)
  • Micro-Organisms Or Cultivation Processes Thereof (AREA)

Abstract

Homogeneous calcium nitrate based fertilizers containing sulphur, and method for their preparations. Solid gypsum and/or a slow reacting sulphate mineral is mixed with melted calcium nitrate fertilizer at a temperature of 90-110 °C and kept at this temperature for 3-15 minutes and subsequently particulated at a temperature of 80-110 °C. The particulation by prilling is performed at 95-110 °C and the particulation by granulation is performed at 90-110 °C. The fertilizer is a homogeneous composition of a calcium nitrate fertilizer and gypsum and/or a slow reacting sulphate mineral comprising 0.1-5.0 weight % SO4-S, 14-19 weight % water soluble calcium and 16-21 weight % total calcium, and 0-3.0 weight % water soluble magnesium. The fertilizer may contain microamounts of Se and/or Co, and/or micronutrients like Mn, Cu, B and Zn.

Description

Calcium nitrate based fertilizer
The present invention relates to calcium nitrate based fertilizers containing sulphur and a process for making such fertilizers.
Calcium nitrate is widely used within horticulture and as a dry product on open fields. There are two major types of calcium nitrate, one made from acidulation of calcium carbonate by nitric acid and one obtained as a by-product from nitrophosphate fertilizer processes. The latter normally contains 75-81 weight% Ca(NO3)2, 5-9 weight% NH4NO3 and 12-14 weight% water of crystallization. This type is usually called NH-CN (Norsk Hydro Calcium Nitrate). In the following the abbreviation CN will be used for both these types of fertilizer.
Over the last years there has been an ever increasing demand for sulphur in fertilizers in general, even for special applications of CN-fertilizers sulphur has been required. For some markets and crops there has also been a demand for CN-fertilizers containing Mg, Se, Co and some micronutrients in addition to sulphur.
In order to meet the demands for new fertilizers the simplest solution seemed to be blending various S-containing fertilizers like ammonium sulphate or potassium sulphate, but when other ingredients like Mg, Se etc. should be added, segregation problems would inherently arise. Another criteria will of course be the price of the various components and it would be advantageous to use cheap sulphur sources like gypsum, kieserite and langbeinite, but again segregation problems were experienced. Preparation of homogeneous CN-based fertilizers by particulation of melts or solutions of CN and sulphur sources like ammonium- or potassium sulphate did however prove to be most difficult due to the low ability to tie up water of crystallization possessed by these two sulphur sources Possible application of gypsum and/or kiesente for making homogeneous fertilizers was then investigated
From Japanese patent application J54085957 it is known preparation of a fertilizer comprising mixing calcium nitrate, gypsum and superphosphate of lime and then granulating the mixture Mixing is performed at 100-120°C and the molten mixture is extruded, cut to a size of 2-3 mm and cooled and dried The amount of superphosphate of lime is 50-70% of the calcium nitrate Firstly, this fertilizer contains large amounts of phosphate and no magnesium Secondly, the particulation process is most uneconomical
Further it is known from J53027564 to coat CN-fertilizers with gypsum during the spraying of CN melt in cooling air containing gypsum powder This fertilizer is stated to have a prolonged effect Its sulphur content will however be far too low to meet the requirements which the present invention has to meet
It is also known to add minor amounts of CN to granulated ammonium sulphate as a binder and to add minor amounts of ammonium sulphate and calcium nitrate to ammonium nitrate to improve its crushing strength, but none of these publications solve the problems related to making homogeneous CN-based fertilizers
The main object of the present invention was to arrive at a homogeneous CN-based fertilizer containing sulphur and optionally magnesium, selenium, cobalt and micronutπents Another object was to arrive at a cost effective continuous process for making homogeneous sulphur containing CN-based fertilizers which could be par- ticulated.
A further object was to arrive at a process for making homogeneous sulphur containing CN-based fertilizers containing magnesium and optionally selenium, cobalt and micronutrients.
Application of normal S-sources like ammonium sulphate and potassium sulphate were first investigated. It was then found that when these sources are mixed with CN melt the following reactions will take place:
1. (NH4)2SO4 + Ca(NO3)2 => CaSO4 + NH4NO3
2. K2SO4 + Ca(NO3)2 => KNO3 + CaSO4
The formation of gypsum consumes calcium nitrate and the melt loses its ability to solidify due to less power to tie up water of crystallization. Accordingly, the two S-sources were found to be too difficult to apply in CN-based fertilizers.
Gypsum (CaSO4 1/2 H2O) was expected to not react with CN melt and should therefore constitute a cheap S-source. Even though gypsum is not water soluble, several agronomical examinations have shown that gypsum is readily available to plants. Different gypsum sources can be utilized, such as dead burned gypsum and gypsum with hydrate water up to dihydrate, the hemi hydrate form is however preferred. Kieserite (MgSO4 H2O) is both a Mg- and S-source which is considered to be water soluble. By mixing this salt into a CN melt the following reaction was found to take place:
3. MgSO4H2O + Ca(NO3)2 => CaSO4 + Mg(NO3)2 + H2O
It was further found that if the Mg(NO3)2 content became too high, solidification problems would occur. However, trials carried out revealed surprisingly that reaction no. 3 did not take place at a significant rate. During further laboratory tests at which kieserite was thoroughly mixed into CN melt for several minutes it was confirmed that said reaction did not result in solidification problems. The investigations also showed that reaction 3 indeed did take place at the surface of each kieserite crystal, but the gypsum formed a thin coating that protected the crystals from further attack by the CN melt. This formation of gypsum coating and the slow dissolving time of the kieserite mineral in general seemed to give possibilities for homogeneous distribution of fine kieserite crystals in the CN melt prior to solidification and thereby make it possible to utilize this for making a homogeneous CN-based fertilizer containing both sulphur and magnesium.
Based on the results from the above investigations, several tests were performed in a pilot plant. It was then confirmed that by using gypsum and slow reacting sulphate minerals like kieserite, langbeinite etc. together with a CN melt it would be possible to make homogeneous S-containing fertilizers which met the above stated objects of the invention.
Thus, according to the invention, solid gypsum and/or a slow reacting sulphate mineral could be mixed with melted calcium nitrate fertilizer at a temperature of 90-110°C and kept at this temperature for 3-15 minutes and subsequently particulated at a temperature of 80-110°C. The particulation by prilling should be performed at 95-110°C and the granulation at 90-110°C.
Microamounts of Co and/or Se and/or micronutrients like Mn, Cu, B, and Zn could be added as solutions of their salts to the mixture prior to particulation.
One preferred method comprises mixing 4-23 weight% gypsum, based on the total composition, with a melted calcium nitrate fertilizer at 103-106°C during stirring and keeping the mixture at this temperature for 5-10 minutes and then particulate the thus formed slurry.
Another preferred method comprises mixing 4-23 weight% kieserite during stirring with a melted calcium nitrate fertilizer for 6-12 minutes and subsequently particulate the thus formed slurry.
Fertilizers according to the invention comprise a homogeneous composition of a calcium nitrate fertilizer and gypsum and/or a slow reacting sulphate mineral comprising 0.1-5.0 weight% SO4-S, 14-19 weight% water soluble calcium and 16-21 weight% total calcium and 0-3.0 weight% water soluble magnesium Preferably said new fertilizer contains 1.0-3.0 weight% SO4-S. The preferred content of magnesium is 0.1-4.0 weight%.
The scope and special features of the invention are as stated in the attached claims.
The invention is further explained by the following examples and the comments to these examples: Example 1
This example relates to formation of prilled homogeneous CN-based fertilizer by mixing 12 weight% kieserite crystals into NH-CN melt at 105°C during stirring at this temperature for about 10 minutes and then spraying the slurry through a nozzle. The formed droplets solidified as they fell through cooling air.
The product thus formed had a homogeneous composition and had the following analysis:
15.0 % N
2.6 % SO4-S
2.0 % Mg (water soluble) 16.8 % Ca (water soluble)
Example 2
This example shows drum granulation of a homogeneous CN-based fertilizer. 7 weight% kieserite crystals were mixed into 93 weight% NH-CN melt at 105°C and stirred for about 6 minutes. The slurry was then sprayed into a drum containing fines from example 1. Hard homogeneous granules were formed with the following composition:
15.2% N
1.5% NH4-N
13.7% NO3-N
1.5% SO4-S
1.1 % Mg (water soluble)
17.5% Ca (water soluble) Example 3
This example shows granulation of homogeneous CN-based fertilizer containing sulphur 11 5 weιght% calcium sulphate hemi hydrate (22 1 %S) was mixed with 88 5 weιght% NH-CN melt at about 105°C and stirred for about 5 minutes and subsequently sprayed into a rotating drum containing NH-CN fines
The thereby formed product had the following analysis
15 0% N
2 5% SO4-S
16 8% Ca (water soluble) 20 0% total Ca
Example 4
This example shows preparation of homogeneous CN-based fertilizer containing sulphur and magnesium and in addition selenium 7 weιght% kieserite and some droplets of a 25 weιght% Na2SeO4 solution were mixed into a NH-CN melt at about 105°C and stirred for about 5 minutes The melt was solidified as in example 2
The formed product had the following analysis
15 2% N
1 5% NH4-N
13 7% NO3-N
1 5% SO4-S
1 1 % Mg (water soluble)
17 5% Ca (water soluble)
25 ppm Se Cobalt can be incorporated in the same way as selenium by addition of droplets of a CoSO4 solution giving 0 02% of Co
Example 5
This example shows preparation of homogeneous CN-based fertilizer containing both sulphur and magnesium 4 weιght% gypsum (calcium sulphate hemi hydrate) and 6 weιght% kieserite were thoroughly mixed into 90 weιght% of NH-CN melt at about 105°C for about 4 minutes The thereby formed slurry was then sprayed into a granulating drum containing fines Hard, homogeneous granules were formed with the following composition
15.1 % N
2.2% SO4-S
1.0% Mg
16.7% water soluble Ca
17.8% total Ca
The main advantages attained by using both gypsum and kieserite for making such fertilizers are that gypsum is a cheaper sulphur source than kieserite and that the product is somewhat less hygroscopic than a product using only kieserite as sulphur and magnesium source.
From the above examples it can be seen that it is possible to prepare homogeneous S-contaming fertilizers based on CN-fertilizers and a S-source The new fertilizer can be particulated, for instance by prilling or granulation, both pan granulation and drum granulation Further tests showed that a rather wide range of such fertilizers could be prepared It was then found that the various components should be within the following ranges SO4-S 0.1-5.0 weight% preferably: 1.0-3.0 weight%
Mg (w.s) 0-4.0 weight% preferably: 0-2.3
Ca (w.s) 14-19 weight% preferably: 16-19
Ca (total) 16-21 weight%
In addition fertilizers of the above type can contain microamounts of cobalt and selenium, and the usual fertilizer micronutrients like manganese, copper zinc, boron etc.
Preparations of the above new fertilizers can be performed at the following conditions:
Recommended mixing temperature: 90-110°C Recommended retention time : 3-15 minutes
Recommended particulation temperatures Prilling 100-110°C
Granulation: 80-100°C
The products of examples 1 and 2 were bagged and stored at a pressure of 1 kg/cm2 for three months and there were no signs of caking. Also the rate of water absorption was tested for these new fertilizers and compared with conventional CN-fertilizers. The rate of absorption was measured at 60% relative humidity and 25°C. The recorded values are listed in the below table: Table 1
Figure imgf000012_0001
From these data it can be seen that fertilizers based on CN and kieserite had somewhat higher hygroscopicity compared to pure CN-fertilizer. The increase is very modest and due to the formation of some Mg(NO3)2. The increase of water absorption can be compensated by increasing the amount of coating applied.
By the present invention the inventors have managed to arrive at a method for making a new type of fertilizer being a homogeneous fertilizer based on calcium nitrate and containing the required amount of sulphur. Said new fertilizer may also contain magnesium and microamounts of Se and Co and micronutrients like Mn, Cu, B, Zn etc.

Claims

Claims
1. A method for making calcium nitrate based fertilizers containing sulphur, characterized in that solid gypsum and/or a slow reacting sulphate mineral is mixed with melted calcium nitrate fertilizer at a temperature of 90-110°C and kept at this temperature for 3-15 minutes and subsequently particulated at a temperature of 80-110°C.
2. A method according to claim 1 , characterized in that
4-23 weight% gypsum, based on the total composition, is mixed with a melted calcium nitrate fertilizer at 103-106°C during stirring and kept at this temperature for 5-10 minutes and that the thus formed slurry is particulated by prilling or granulation.
3. A method according to claim 1 , characterized in that
4-23 weight% solid kieserite is mixed during stirring with a melted calcium nitrate fertilizer for 6-12 minutes and that the thus formed slurry is subsequently particulated.
4. A method according to claim 1 , characterized in that the particulation by prilling is performed at 95-110°C and that the particulation by granulation is performed at 90-110°C.
5. A method according to claim 1 , characterized in that selenium, cobalt, and the micronutrients like manganese are added as solutions of their salts into the mixture prior to particulation.
6. A calcium nitrate based fertilizer containing sulphur, characterized in that the fertilizer is a homogeneous composition of a calcium nitrate fertilizer and gypsum and/or a slow reacting sulphate mineral comprising 0.1-5.0 weight% SO4-S, 14-19 weight% water soluble calcium and 16-21 weight% total calcium, and 0-3.0 weight% water soluble magnesium.
7. A fertilizer according to claim 6, characterized in that the fertilizer contains 1.0-3.0 weight% SO4-S.
8. A fertilizer according to claim 6, characterized in that the fertilizer contains 0.1-4.0 weight% water soluble magnesium.
9. A fertilizer according to claim 6, characterized in that the fertilizer contains microamounts of Se and/or Co, and/or micro¬ nutrients like Mn, Cu, B and Zn.
PCT/NO1997/000126 1996-05-24 1997-05-14 Calcium nitrate based fertilizer Ceased WO1997045382A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
IL12720397A IL127203A (en) 1996-05-24 1997-05-14 Calcium nitrate based fertilizer containing sulphur
US09/180,869 US6171358B1 (en) 1996-05-24 1997-05-14 Calcium nitrate based fertilizer
EP97922215A EP0904257B1 (en) 1996-05-24 1997-05-14 Calcium nitrate based fertilizer
DE69702760T DE69702760D1 (en) 1996-05-24 1997-05-14 CALCIUM NITRATE FERTILIZER
AT97922215T ATE195309T1 (en) 1996-05-24 1997-05-14 CALCIUM NITRATE FERTILIZER
PL97330231A PL185085B1 (en) 1996-05-24 1997-05-14 Fertilizer and method of producing artificial fertilizer
AU27946/97A AU2794697A (en) 1996-05-24 1997-05-14 Calcium nitrate based fertilizer
RO98-01608A RO117909B1 (en) 1996-05-24 1997-05-14 Calcium nitrate-based fertilizer and process for preparing the same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NO962119 1996-05-24
NO962119A NO305939B1 (en) 1996-05-24 1996-05-24 Method for the preparation of calcium nitrate-based yeast containing sulfur, and such yeast

Publications (1)

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WO1997045382A1 true WO1997045382A1 (en) 1997-12-04

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US (1) US6171358B1 (en)
EP (1) EP0904257B1 (en)
AT (1) ATE195309T1 (en)
AU (1) AU2794697A (en)
CZ (1) CZ292236B6 (en)
DE (1) DE69702760D1 (en)
IL (1) IL127203A (en)
NO (1) NO305939B1 (en)
PL (1) PL185085B1 (en)
PT (1) PT904257E (en)
RO (1) RO117909B1 (en)
RU (1) RU2162073C2 (en)
WO (1) WO1997045382A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20020008486A (en) * 2000-07-20 2002-01-31 강준구 Fertilizer for agriculture
WO2006031139A1 (en) * 2004-09-16 2006-03-23 Adam Nawrocki Method of calcium nitrate production
WO2017178342A1 (en) 2016-04-14 2017-10-19 Yara International Asa Particulate calcium nitrate composition for fertigation comprising nitrate-based micronutrients and method for production thereof

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US6319156B1 (en) * 1999-12-13 2001-11-20 John Marshall Biodegradable golf tee
DE102004055648A1 (en) * 2004-11-12 2006-05-18 Ami-Agrolinz Melamine International Gmbh Process and apparatus for obtaining sulfur-containing nitrogen fertilizer
UA93890C2 (en) * 2005-11-08 2011-03-25 Ами Агролинц Меламин Интернациональ Гмбх Process for producing of sulphurous nitrogen fertilizer in tubular reactor
PE20121674A1 (en) * 2009-10-05 2012-12-13 Specialty Fertilizer Pro Llc FERTILIZING PRODUCTS ENHANCED WITH POLYMER ADJUVANTS
CN103254002A (en) * 2012-02-21 2013-08-21 吴兴国 Selenium-rich biological organic fertilizer containing ferment and medical stone
CA2968257C (en) * 2017-05-24 2022-05-24 Inotel Inc. Potassium magnesium fertilizer

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE203085C (en) *
DE397937C (en) * 1920-03-09 1924-07-03 Hoechst Ag Process for the production of a readily spreadable, non-water-attracting potash-nitrogen mixture
GB1311065A (en) * 1969-08-09 1973-03-21 Basf Ag Calcium nitrate-urea double salts capable of being scattered and stored
GB1382870A (en) * 1971-03-29 1975-02-05 Chemie Linz Ag Fertilisers

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5327564A (en) 1976-08-25 1978-03-14 Kawasaki Heavy Ind Ltd Calcium nitrate fertilizer difficult to deliquesce and process for producing same
JPS5485957A (en) 1977-12-19 1979-07-09 Shimohiro Shiyuku Production of composite fertilizer
US4240818A (en) * 1979-03-12 1980-12-23 Andreeva Nina K Procedure for preparing nitrogen-potassium fertilizer
US5698002A (en) * 1994-11-21 1997-12-16 Lesco Inc. Controlled release fertilizers utilizing an epoxy polymer primer coat and methods of production

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE203085C (en) *
DE397937C (en) * 1920-03-09 1924-07-03 Hoechst Ag Process for the production of a readily spreadable, non-water-attracting potash-nitrogen mixture
GB1311065A (en) * 1969-08-09 1973-03-21 Basf Ag Calcium nitrate-urea double salts capable of being scattered and stored
GB1382870A (en) * 1971-03-29 1975-02-05 Chemie Linz Ag Fertilisers

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WPI/DERWENT'S ABSTRACT, No. 79-60872B, Week 7933; & JP,A,54 085 957 (SHIMOHIRO I), 9 July 1979. *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20020008486A (en) * 2000-07-20 2002-01-31 강준구 Fertilizer for agriculture
WO2006031139A1 (en) * 2004-09-16 2006-03-23 Adam Nawrocki Method of calcium nitrate production
NO343458B1 (en) * 2004-09-16 2019-03-18 Adam Nawrocki Method of production of calcium nitrate
WO2017178342A1 (en) 2016-04-14 2017-10-19 Yara International Asa Particulate calcium nitrate composition for fertigation comprising nitrate-based micronutrients and method for production thereof
CN109153618A (en) * 2016-04-14 2019-01-04 亚拉国际有限公司 Granular calcium nitrate composition containing nitrate-based micronutrients for fertigation and method of making the same
RU2728859C2 (en) * 2016-04-14 2020-07-31 Яра Интернейшнл Аса Composition of powdered calcium nitrate for fertilizer reflux, which includes nutritional microorganisms based on nitrates, and a method for production thereof
CN114874041A (en) * 2016-04-14 2022-08-09 亚拉国际有限公司 Granular calcium nitrate composition comprising nitrate-based micronutrients for fertigation and method for preparing same
CN114874041B (en) * 2016-04-14 2023-11-07 亚拉国际有限公司 Granular calcium nitrate composition for fertigation comprising nitrate-based micronutrients and method of making same

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US6171358B1 (en) 2001-01-09
CZ292236B6 (en) 2003-08-13
EP0904257A1 (en) 1999-03-31
PL330231A1 (en) 1999-05-10
AU2794697A (en) 1998-01-05
CZ375998A3 (en) 1999-04-14
DE69702760D1 (en) 2000-09-14
RO117909B1 (en) 2002-09-30
IL127203A0 (en) 1999-09-22
IL127203A (en) 2001-09-13
NO962119D0 (en) 1996-05-24
ATE195309T1 (en) 2000-08-15
NO962119L (en) 1997-11-25
PT904257E (en) 2001-01-31
RU2162073C2 (en) 2001-01-20
EP0904257B1 (en) 2000-08-09
NO305939B1 (en) 1999-08-23
PL185085B1 (en) 2003-02-28

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