controlled releasecontrolled release technologies
TRANSCRIPT
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CONTROLLED RELEASECONTROLLED RELEASECONTROLLED RELEASE CONTROLLED RELEASE
TECHNOLOGIESTECHNOLOGIES
Thomas P. Murray, Ph. D.Thomas P. Murray, Ph. D.
Southern Environmental Testing, Inc.Southern Environmental Testing, Inc.Florence, AlabamaFlorence, Alabama
TFI/Fertilizer Industry Roundtable October 30, 2009TFI/Fertilizer Industry Roundtable October 30, 2009
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INTRODUCTIONINTRODUCTIONINTRODUCTIONINTRODUCTION
SLOW AND CONTROLLED RELEASESLOW AND CONTROLLED RELEASESLOW AND CONTROLLED RELEASE SLOW AND CONTROLLED RELEASE NITROGEN FERTILIZERS DERIVED NITROGEN FERTILIZERS DERIVED FROM UREAFROM UREAFROM UREAFROM UREA
SOLIDSSOLIDS–– SOLIDSSOLIDS
–– LIQUIDSLIQUIDS
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COATED PRODUCTSCOATED PRODUCTSCOATED PRODUCTSCOATED PRODUCTS
SULFUR COATED UREASULFUR COATED UREASULFUR COATED UREASULFUR COATED UREA–– Poly SPoly S®® (Scotts)(Scotts)
XCUXCU®® (Agrium)(Agrium)–– XCUXCU® ® (Agrium)(Agrium)RESIN COATINGSRESIN COATINGS
®® ( )( )–– PolyonPolyon® ® (Agrium)(Agrium)–– ESNESN®® (Agrium)(Agrium)–– DurationDuration®® (Agrium)(Agrium)–– OsmocoatOsmocoat®® (Scotts)(Scotts)
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SOLID UREAFORMSSOLID UREAFORMSSOLID UREAFORMSSOLID UREAFORMS
TURFBUILDERTURFBUILDER®® 4141--00--0 (Scotts)0 (Scotts)NITROFORMNITROFORM®® 3838--00--0 (Nu0 (Nu--Gro America Corp.)Gro America Corp.)NUTRALENENUTRALENE®® 4040--00--0 (Nu0 (Nu--Gro America Corp.)Gro America Corp.)UFUF--3838® ® (Morral Companies~SROF)(Morral Companies~SROF)MUMU--4040® ® (Morral Companies~SROF)(Morral Companies~SROF)( p )( p )MethMeth--Ex 40Ex 40®® (Lebanon Seaboard)(Lebanon Seaboard)
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UREAFORM CHEMISTRYUREAFORM CHEMISTRYC C S SC C S SACID CATALYSISACID CATALYSIS
O O
OO
H2N N N NH2
H H
H H
O
+H2N NH2
H+
+
MDU
O O O
H2N N N N
H H
N NH2
HH
DMTU
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SOLIDSSOLIDSFrom Urea and Higher AldehydesFrom Urea and Higher Aldehydes
IBDUIBDUIBDUIBDU–– ParPar--ExEx®® (Lebanon Seaboard)(Lebanon Seaboard)–– IB NitrogenIB Nitrogen® ® (Nu(Nu--Gro)Gro)
CDUCDU–– Chisso, CorpChisso, CorpChisso, CorpChisso, Corp
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ISOBUTYLIDENEDIUREAISOBUTYLIDENEDIUREA32% N32% N
O
OO N NH2
H
H+
H
+H2N NH2
2N
H
NH2O
IBDUIBDU
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CROTONYLIDENEDIUREACROTONYLIDENEDIUREA33%33%33% N33% N
O
N NHH
O
+H N NH
O
2OH+
HH2N NH2
N NH2
H
H3C
CDUCDU
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CLEAR LIQUID UREAFORM CLEAR LIQUID UREAFORM O C SO C SPRODUCTSPRODUCTS
MORRAL COMPANIESMORRAL COMPANIES–– NBNNBN--3030®®
TESSENDERLO KERLEY TESSENDERLO KERLEY –– NSURENSURE®® 2828--00--00NSURENSURE 2828 00 00–– FormoleneFormolene®® PlusPlus
GEORGIA PACIFICGEORGIA PACIFICNN F iF i ®® 2222 00 00–– NN--FusionFusion®® 2222--00--00
–– NitaminNitamin®® 3030--00--00HELENA HELENA –– CoRoNCoRoN®® 2828--00--0 0
GROWTH PRODUCTS GROWTH PRODUCTS –– Nitro 30Nitro 30®® SRNSRNt o 30t o 30 SS
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UREAFORM COMPONENTSUREAFORM COMPONENTSS C S SS C S SBASE CATALYSISBASE CATALYSIS
O
HN N OH
H H
O
+
O
Basic pH
H H
METHYLOLUREA
+H2N NH2 H H
OUREA FORMALDEHYDE+
HO N N OH
H H
DIMETHYLOLUREADIMETHYLOLUREA
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TRIAZONETRIAZONETRIAZONETRIAZONE
First proposed by Ed Hawkins (U. S. PatentFirst proposed by Ed Hawkins (U. S. PatentFirst proposed by Ed Hawkins (U. S. Patent First proposed by Ed Hawkins (U. S. Patent 4,554,005) 1985.4,554,005) 1985.
O
HHN N
HH
N
H
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OTHER PROPOSED TRIAZONE OTHER PROPOSED TRIAZONE S C O SS C O SSTRUCTURAL FORMULAS STRUCTURAL FORMULAS
OO
N NHH
N N N N N N
O
HH
N
OH
N NO OH H
HHOH HH
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CHEMICAL STRUCTURECHEMICAL STRUCTUREOOTRIAZONETRIAZONE
The triazone molecule shown The triazone molecule shown (40% N) was isolated from (40% N) was isolated from Morral Companies NBNMorral Companies NBN 3030®®
O
HHMorral Companies NBNMorral Companies NBN--3030®®..
The structural formula was The structural formula was l id t d i NMR dl id t d i NMR d
N NHH
elucidated using NMR and elucidated using NMR and MS data.MS data.
T P M 204T P M 204thth ACSACS
N O
T. P. Murray, 204T. P. Murray, 204thth ACS ACS National Meeting, August 27, National Meeting, August 27, 1992. Division of Fertilizer 1992. Division of Fertilizer and Soil Chemistryand Soil Chemistry
N NH2and Soil Chemistry.and Soil Chemistry.
H
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TRIAZONE CHEMISTRYTRIAZONE CHEMISTRYTRIAZONE CHEMISTRYTRIAZONE CHEMISTRY
OH
+ 3H H N
CH2OHHOH2C
O HN
H H
Ammonia FormaldehydeCH2OH
+
y
O
H2N NH2
ON
N
NH
O
H
Urea
N
N NH2
O
H
TRIAZONE
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ADVANTAGES OFADVANTAGES OFADVANTAGES OF ADVANTAGES OF UREAFORM FERTILIZERSUREAFORM FERTILIZERS
CONTROLLED RELEASE OF NITROGENCONTROLLED RELEASE OF NITROGEN
FOLIAR BURN PROTECTIONFOLIAR BURN PROTECTIONFOLIAR BURN PROTECTION FOLIAR BURN PROTECTION
SEEDLING INJURY PROTECTIONSEEDLING INJURY PROTECTIONSEEDLING INJURY PROTECTIONSEEDLING INJURY PROTECTION
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BURN POTENTIALBURN POTENTIALBURN POTENTIALBURN POTENTIALSALT INDEX SALT INDEX -- An index that relates the extent to An index that relates the extent to which a given amount of various fertilizers which a given amount of various fertilizers increase the osmotic pressure of the soil increase the osmotic pressure of the soil solution (Rader 1943) Modern determinationssolution (Rader 1943) Modern determinationssolution. (Rader, 1943). Modern determinations solution. (Rader, 1943). Modern determinations are made using conductivity (Jackson, 1958).are made using conductivity (Jackson, 1958).
OSMOLALITY OSMOLALITY –– Osmolality (mm/Kg) determined Osmolality (mm/Kg) determined for 3% nitrogen solutions and correlated to leaf for 3% nitrogen solutions and correlated to leaf burn. (Murray, Darrah, Clapp, Communications burn. (Murray, Darrah, Clapp, Communications in Soil Science and Plant Analysis, 38: 337in Soil Science and Plant Analysis, 38: 337--346, 346, 2007)2007)2007)2007)
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SALT INDEXSALT INDEXSALT INDEXSALT INDEX
The “Salt Index” is used to compare theThe “Salt Index” is used to compare theThe Salt Index is used to compare the The Salt Index is used to compare the increase in osmotic pressure for 45 increase in osmotic pressure for 45 fertilizer materials against the same weight fertilizer materials against the same weight g gg gof sodium nitrate.of sodium nitrate.
The “Salt Index” is useful only for The “Salt Index” is useful only for comparing one fertilizer with another and comparing one fertilizer with another and p gp gwas never meant to correlate to leaf burn was never meant to correlate to leaf burn or seedling injury.or seedling injury.
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OSMOLALITYOSMOLALITYOSMOLALITYOSMOLALITY
Determined using a Vapor Pressure Determined using a Vapor Pressure OsmometerOsmometerOsmometer.Osmometer.Determinations made using dilute Determinations made using dilute solutions.solutions.Nitrogen fertilizers diluted to 3 % N.Nitrogen fertilizers diluted to 3 % N.Osmolality reported in mmol/KgOsmolality reported in mmol/Kg
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OSMOLALITY VALUESOSMOLALITY VALUESFertilizer ComponentsFertilizer Components
COMPOUNDCOMPOUND %N%N OsmolalityOsmolalityl Kl K 11 (3% N)(3% N)mmol Kgmmol Kg--11 (3% N)(3% N)
UREAUREA 4646 10181018IBDUIBDU 3232 4040Ammonium NitrateAmmonium Nitrate 3535 18041804Ammonium NitrateAmmonium Nitrate 3535 18041804UANUAN 2828 14391439
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OSMOLALITY VALUESOSMOLALITY VALUESSolid Ureaform ComponentsSolid Ureaform Components
COMPOUNDCOMPOUND%N%N
OsmolalityOsmolalitymmol Kgmmol Kg--11 (3% N)(3% N)
MethylenediureaMethylenediurea 4242 298298
DimethylenetriureaDimethylenetriurea 4141 129129
Triazone ConcentrateTriazone Concentrate 3636 270270
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OSMOLALITY VALUESOSMOLALITY VALUESOSMOLALITY VALUESOSMOLALITY VALUESDRY SLOW RELEASE DRY SLOW RELEASE
%N%NOsmolalityOsmolality
l Kl K 11 (3% N)(3% N)PRODUCTSPRODUCTS %N%N mmol Kgmmol Kg--11 (3% N)(3% N)
UFUF 3838®® (Morral)(Morral) 3838 303303UFUF--3838® ® (Morral)(Morral) 3838 303303
MUMU--4040® ® (Morral)(Morral) 4040 321321UU 00 ( o a )( o a ) 00 33
NITROFORMNITROFORM®® (Nu(Nu--Gro)Gro) 3838 220220
NUTRALENENUTRALENE® ® (Nu(Nu--Gro)Gro) 4040 312312
TURFBUILDERTURFBUILDER®® (Scotts)(Scotts) 4141 557557TURFBUILDERTURFBUILDER (Scotts)(Scotts) 4141 557557
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OSMOLALITY VALUESOSMOLALITY VALUESLiquid Ureaform ComponentsLiquid Ureaform Components
COMPOUNDCOMPOUND%N%N
OsmolalityOsmolalitymmol Kgmmol Kg--11 (3% N)(3% N)
MonomethylolureaMonomethylolurea 3131 906906
DimethylolureaDimethylolurea 2323 825825
DimethylolmethylenediureaDimethylolmethylenediurea 2929 542542
Triazone ConcentrateTriazone Concentrate 3636 270270Triazone ConcentrateTriazone Concentrate 3636 270270
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OSMOLALITY VALUESOSMOLALITY VALUESOSMOLALITY VALUESOSMOLALITY VALUESLIQUID CONTROLLED LIQUID CONTROLLED RELEASE PRODUCTSRELEASE PRODUCTS %N%N
OsmolalityOsmolalityl Kl K 11 (3% N)(3% N)RELEASE PRODUCTSRELEASE PRODUCTS %N%N mmol Kgmmol Kg--11 (3% N)(3% N)
NBNNBN® ® (Morral)(Morral) 3030 698698( )( )
NN--SURESURE®® (TKI)(TKI) 2828 513513CoRoNCoRoN®® (Helena)(Helena) 2828 685685CoRoNCoRoN®® (Helena)(Helena) 2828 685685FORMOLENEFORMOLENE®® (TKI)(TKI) 3030 745745NITAMINNITAMIN®® (G i P ifi )(G i P ifi ) 3030 634634NITAMINNITAMIN®® (Georgia Pacific)(Georgia Pacific) 3030 634634NFUSIONNFUSION®® (Georgia Pacific)(Georgia Pacific) 2222 399399NITRO 30NITRO 30®® (Growth Product)(Growth Product) 3030 796796
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Osmolality and Salt IndexOsmolality and Salt Index
COMPOUNDCOMPOUND %N%N SaltSalt OsmolalityOsmolalityCOMPOUNDCOMPOUND %N%NIndex Index mmol Kgmmol Kg--11 (3% N)(3% N)
Sodium NitrateSodium Nitrate 1616 100.0100.0 40924092
Ammonium NitrateAmmonium Nitrate 3535 104.7104.7 18041804
UANUAN 2828 64 664 6 14391439UANUAN 2828 64.664.6 14391439
Ammonium SulfateAmmonium Sulfate 2121 69.069.0 23142314Ammonium SulfateAmmonium Sulfate 2121 69.069.0 23142314
DAPDAP 1818 34.234.2 20542054
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Osmolality vs Salt Index
SodiumNitrate
R2 = 0.05174000
4500
R 0.0517
3000
3500
/Kg)
DAPAmmonium
Nit t
2000
2500
mol
ality
(mm
/
UAN
Urea
Nitrate
1000
1500Osm
0
500
0 20 40 60 80 100 1200 20 40 60 80 100 120
Salt Index (Rader, 1943)
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Osmolality vs Leaf burnTall FescueTall Fescue
2500
Ammonium Nitrate2000
g)
UAN-32
UreaR2 = 0.90231000
1500
olal
ity (m
m/K
g
Nitro 30NBN
N-Sure500
1000
Osm
o
00.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0
Burn Rating (1-9)
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NITRIFICATION INHIBITORSNITRIFICATION INHIBITORSNITRIFICATION INHIBITORSNITRIFICATION INHIBITORS
DCD (Dicyandiamide).DCD (Dicyandiamide).GUARDIANGUARDIAN®® (Conklin)(Conklin)–– GUARDIANGUARDIAN®® (Conklin)(Conklin)
–– GUARDIAN DLGUARDIAN DL®® (Conklin) (Conklin) Nit i (2Nit i (2 hlhl 66 (t i hl th l)(t i hl th l)Nitrapyrin (2Nitrapyrin (2--chlorochloro--66--(trichloromethyl)(trichloromethyl)--pyridine). Npyridine). N--ServeServe®® (Dow Agrosciences)(Dow Agrosciences)DMPP (3,4DMPP (3,4--Dimethylpyrazone phosphate).Dimethylpyrazone phosphate).–– ENTEC ENTEC ® ® (K+S Nitrogen)(K+S Nitrogen)
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UREASE INHIBITORSUREASE INHIBITORSUREASE INHIBITORSUREASE INHIBITORS
Agrotain NAgrotain N--(n(n--butyl)butyl)--triphosphoric triamidetriphosphoric triamideAgrotain NAgrotain N (n(n butyl)butyl) triphosphoric triamide triphosphoric triamide (NBPT)(NBPT)
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ACKNOWLEDGMENTACKNOWLEDGMENTACKNOWLEDGMENTACKNOWLEDGMENT
MORRAL COMPANIESMORRAL COMPANIESMORRAL COMPANIESMORRAL COMPANIES
UNIVERSITY OF NORTH ALABAMAUNIVERSITY OF NORTH ALABAMA