Chemistry of inorganic compounds – Nitrogen or compound thereof – Oxygen containing
Reexamination Certificate
2001-02-23
2003-08-26
Langel, Wayne A. (Department: 1754)
Chemistry of inorganic compounds
Nitrogen or compound thereof
Oxygen containing
C023S29300R, C071S058000
Reexamination Certificate
active
06610267
ABSTRACT:
This application is a 371 application of PCT/NO99/00192 filed Jun. 11, 1999.
The present invention relates to a method for manufacturing a homogeneous and ammonium free calcium nitrate melt with high solidification temperature suitable for conventional particulation methods. The invention further comprises products of such melt.
Today pure Ca(NO
3
)
2
(abbreviated as CN) is commercially available as crystalline products, mainly Ca(NO
3
)
2
. 4H
2
O, and as aqueous solutions containing 45-50% Ca(NO
3
)
2
.
Aqueous CN products have high handling costs in addition to containing much water.
Consequently, the logistic costs on nutrient basis are rather high.
The crystalline products have poor handling properties with high caking tendency, high dust content and low melting point (43-50° C.). Thus CN crystals are not suitable for bulk handling.
Due to low solidification temperature (43-50° C.) and undercooling, it is extremely difficult to obtain pure CN particles from a CN melt by using traditional particulation methods as granulating or prilling.
To improve the solidification property and avoid undercooling NH
4
NO
3
(abbreviated as AN) has been added to the melt.
Today Norsk Hydro's solid calcium nitrate product; NH-CN, contains 6-8% by weight AN, 15% by weight of crystalline water and 77-79% by weight of Ca(NO
3
)
2
.
For some applications, however, the NH
4
-content in the calcium nitrate product is a significant disadvantage. For instance as setting accelerator in concrete where NH
4
reacts to NH
3
-gas, and for some agronomic applications.
From the Norwegian patent application NO 954336 it is known NK fertilisers containing 55-85% KNO
3
(abbreviated as KN) and 14-40% Ca(NO
3
)
2
and a method for manufacturing these fertilisers.
The product range covered in this application was intended to be a complementary fertiliser in the pure KNO
3
market. Sufficient solidification properties and particle strength were obtained by evaporating the melt to a very low water content (0.5-6%). Hence, the physical properties and the process requirements as evaporation and particulation parameters, for the melts covered in NO 954336 were quite different from those according to the present invention.
Another objective of the invention according to NO 954336 was to make a fertiliser rich in K that could be blended mechanically with NH-CN to cover the range from 0-33% K. Consequently, all the grades containing less than 21% K will be mechanical mixtures, containing NH
4
from the regular CN. Mechanical mixtures with low K-content contain almost the same amount of NH
4
as regular NH-CN, making them unsuitable for the earlier mentioned applications. The products according to the present invention are homogeneous that contain no NH
4
.
NO 954336 describes a homogeneous NK product containing 55-85% of KN contrary to the product according to the present invention which basically is a CN product containing minor amounts of KN and with no NH
4
.
The main object of the invention was to arrive at a complementary calcium nitrate product to the crystalline and liquid Ca(NO
3
)
2
product.
Another object of the invention was to arrive at a homogeneous and ammonium free calcium nitrate in granular or prilled form.
A further object of the invention was to arrive at a homogeneous and ammonium free calcium nitrate in granular form with good handling and storage properties.
The inventors have been investigating different ways of substituting the ammonium content in NH-CN without reducing the quality of the product.
Furthermore, it was important that the new CN melt had good solidification properties to utilise conventional particulation processes as granulation or prilling. This demands that the melt is not undercooling too much, and that the solidification temperature is reasonable high.
In the present invention a melt is defined to be an aqueous solution containing not more than 22% water.
The inventors found that homogeneous CN particles with excellent properties were obtained when the NH
4
-content in NH-CN was replaced with a potassium source in a certain consentration. This replacement raises the solidification temperature of the melt from 43-50° C. (for a pure CN melt) to 85-90° C. (for a (CN+K) melt) making it suitable for conventional particulation processes as granulation and prilling.
The CN melt was manufactured by mixing the potassium source with a calcium nitrate source. An aqueous Ca(NO
3
)
2
-solution is suitable as a calcium nitrate source. Potassium nitrate (KNO3) in a solid or aqueous form is suitable as a K-source. Another alternative potassium source is KOH neutralised with nitric acid.
Prior to the conventional particulation, the water content in the melt was adjusted by evaporation.
Furthermore, it was found that undercooling was avoided and particulation with conventional methods was possible when the CN melt had a certain consentration range of K, water and CN. This range is defined as follows:
1.5-5.5% by weight of K (as KNO
3)
13-18% by weight of water
70-80% by weight of Ca(NO
3
)
2
In view of these findings particulation of melts within the above mentioned ranges were performed.
Granulation tests were carried out in a pilot scale pan granulator, with good results. Layering was obtained as the dominating particle growth mechanism with a granulation temperature of 84° C. The particles from the granulator were of nice spherical shape, and the crushing strength of 2.8 mm particles were 3-5 kg. No caking or post reactions occurred during cooling of the material.
The optimal composition of the melt for granulation seemed to be 74-75% Ca(NO
3
)
2
, 15-16% water and 2.5-4.0% K.
Prilling tests were carried out with good results. Appropriate melt temperature was 90° C. and, as for regular NH-CN, 1-5% seed crystals had to be mixed into the melt before prilling. The results were good for the whole concentration range but, as for granulation, the optimal composition of the melt seemed to be about the same as for particulation by granulation.
The scope of the invention and its special features are as defined by the attached claims.
The invention will now be further explained in connection with the description of the examples and the figure.
REFERENCES:
patent: 4248644 (1981-02-01), Healy
patent: 44877 (1931-11-01), None
patent: 392531 (1933-05-01), None
patent: 1763436 (1992-09-01), None
patent: 990752 (1999-10-01), None
patent: 97/15536 (1997-05-01), None
Moland Lars Gustav
Obrestad Torstein
Langel Wayne A.
Norsk Hydro ASA
Wenderoth , Lind & Ponack, L.L.P.
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