This is a reproduction of a library book that was digitized

by Google as part of an ongoing effort to preserve the

information in books and make it universally accessible.

https://books.google.com
agi
S647
P73

Precipitated Impurities in 18-46-0. Fertilizers

Prepared from Wet-Process Phosphoric Acid
/
ABSTRACT

The use of marginal-quality phosphate rock and the

increased use of the sludge fraction from wet-process phos
phoric acid have created grade problems in the production of
18-46-0 fertilizers. Detailed chemical and crystallographic
characterizations of 26 commercial 18-46-0 fertilizers were
made, and the results were correlated with the fertilizer
properties and process parameters. These samples repre
sented a wide range of impurities from Florida, North
Carolina, and western phosphate rock sources. Several
reasons for grade problems and suggested methods for
alleviating them were identified during this research study. P. º |
Better control of wet-process acid processing variables will
decrease high calcium and sulfate levels in DAP. Eliminating º º
natural sludge from merchant-grade acids will significantly
decrease iron, aluminum, and magnesium concentrations. Pºº
Proper operating conditions for moisture removal in the
preneutralizer were established to prevent the formation
of citrate-insoluble P2 Os. The precipitation of fluoride
containing compounds was shown to be advantageous in
improving grade and lowering fluoride emissions. Adding a
small quantity of water with the ammonia to the rotary
granulator will prevent caking around the sparger and
decrease ammonia loss.

Introduction and Background . . . . . . . . . . . . . 3.

Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.

Results and Discussion . . . . . . . . . . . . . . . . . . . 6

Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . 18
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

OHIO STATE
UNIVERSITY
LIBRARIES
Prepared by

Ewell F. Dillard
A. William Frazier
Terry C. Woodis, Jr.
Frank P. Achorn

NATIONAL FERTILIZER DEVELOPMENT CENTER, MUSCLE SHOALS, ALABAMA 35660

 Precipitated Impurities in 18-46-O Fertilizers
Prepared from Wet-Process Phosphoric Acid
Introduction and Background
With the declining chemical quality of commer
cial phosphate raw materials, increasing amounts of
metal impurities, which subsequently precipitate
upon ammoniation, occur in the wet-process
phosphoric acid. The compositional form and
relative abundance of these metal salts depend
upon both acid composition and operative parame
ters during ammoniation and granulation. Conse
quently, grade problems with respect to N or P2 Os
content, or both, may have different origins,
depending upon the particular controlling precipi
tation reactions. Characterization of the solid
phase components in fertilizer products of nominal
18-46-0 grade is an important step in identification
of specific causes of grade dilution (1). Certain
solid-phase components precipitate and dilute the
grade to a value less than the nominal grade of
18-46-0.
During ammoniation the loss in acidity causes
precipitation of dissolved metal impurities. The
various types of precipitates depend on the pH,
temperature, and retention time during ammonia
tion. The solubility properties of the diammonium
phosphate fertilizer depend upon the total content
of impurity solids and their specific compositional
forms.
For many years the iron and aluminum com
pounds that precipitate above pH 2, which were
observed by optical microscopy and x-ray to be
cryptocrystalline or amorphous, were assigned the
composition (Fe,Al)PO4 'nH2O on the basis of
their recognized constituents (2). When crystal
Lº linity was observed the identified compound was
(Fe, Al)NH4 (HPO4)2 - 0.5H2O, and it was assumed
that the amorphous material had largely crystal
lized to this compound. In fact, it was determined
that high temperatures and long retention times in
a preneutralizer at pH 3 to 6 would cause sufficient
crystal development to allow for easy removal of
the impurities by filtration.
Interest in 18-46-0 grade problems and the
identification of fluorophosphates as components
of ammoniated wet-process phosphoric acids have
resulted in a refinement in the identification of the
metallic precipitates. The identification of the
components in 18-46-0 fertilizers has been com
plicated by the large number of impurities, the
poor crystallinity of the precipitates, the lack of
fundamental information, and the large number of
process variables used in production processes.
The poor crystallinity of the precipitates is some
times due to the amorphous or cryptocrystalline
nature of the original precipitates and at other
times to the fact that the crystalline phases are
decomposed to amorphous phases during drying of
the 18-46-0 fertilizer product. The identification
of these new fertilizer compounds, along with
phase system studies and the use of argon plasma
emission spectrometry for detailed chemical
analysis, have provided a more thorough under
standing of the composition of 18-46-0 grade
fertilizers. Multielement determinations can be
performed by emission spectrometry, whereas only
single, or at most dual, elements can be performed
by atomic absorption spectrometry. Also, the
cooperative effort of microscopic, x-ray, and
infrared techniques was required to confirm the
presence of these compounds.
Methods
Chemical Analysis and Component Analysis—In
order to simplify the problem, only the water
insoluble fraction from the 18-46-0 fertilizers
was initially studied and characterized, then the
results were related to the initial fertilizer. These
samples, representing the range of impurities in
different phosphate rock sources (Florida, North
Carolina, western), are shown in Table l. The
component analysis for these samples as deter
mined from chemical composition, optical micros
copy, x-ray, infrared, and phase chemistry
3
90IO “ O 9900 * O OZZO” O 89 00 * 0 / 670° O 06 º € 66 ° O€” Z 89 * 0 09 * O 68° O 8 * 947 I * 9T 9Z * ON ÆGI
Z600 * O IGOO * O 8IZO” O #9 OO.º O GA +70° O 6 7 * #7 39 ° O7° Z 89 ° 0 09 * O 18 *O I º 97 9 º 8T GZ * ON ÕIGI
ZIZO” O OTO0 * 0 OOTO” O GCIO “ O 0600 * O 68 ° € 39 ° O9° Z 97 ° 0 G8* Ö 6T * I Z * 9f7 6 */ I '7Z * ON GICI
9900°0 6800° 0 97/0°0 0680’0 00ZI’ O 60 * g / #7 “O zgºz gº * O OI º I (g * 0 0 · 97 0 º gT gz • ON āCI
9800° 0 9000' 0 Z600 * 0 09 TO “O OITO “O 6T * 7 99 º O /9 * I gſ; * O 63* 06 * T G º 97 ; * 9I ZZ * ON GIGI
79I0° O Z000 * 0 1800 * 0 09 IO "O Z 900 * 0 60 ° § €g º OG“ Z 99 ' 0 / 6° O 9 I“ I Iº gº 6° LI IZ , ， oN āCI
€GI0°0 Z9I0°0 08/0° 0 89ZI ’0 8ZGI’ O 66 ºg 9zº o 96 · I 8£ ‘o 60’I C9 º o zº 97 I • 8I oz. º oN aq
ZGI0°0 9000' 0 7800° 0 8ZIO” O 8900 º 0 677 · 7 8 /* O 98 * I 97° O g6 * 0 șT · I gº 97 z • (T 6T ， oN āCI
19I0°0 €000 * 0 7 100 * 0 ſ/ZIO ‘O 89.00° 0 60 ° § 89 * O I8 * I 77° O £5°0 șT • T I • 9，7 g * (I 3T • ON āCI
IGI0°0 7000' 0 9000' 0 / 9I0°0 89.00° 0 67 º 7 GL *O Z8* I gſ; * O 16 * 0 6I º I (* 97 z • LI LT • ON āCI
78T0°0 ZI00 * 0 0800° 0 £7IO” O 9900° 0 60 ºg 90° O II º I 99 "O 03 * O £9 * O 6 · 97 9 · 3T 9I • ON HOI
06I0°0 ST00°0' S 100° 0 67T0°0 0900’0 6I º L 90° O £O’I C*; * 0 // * O 78° O 6 * #ff 9 • 9I ÇI • ON āCI
18T0°0 9I00°0 Z800° 0 67 TO “O 6900 * 0 09 ° € 70.“ O IT” I Z 9. * O £8 * O G8 * O 6 */ $7 8 * 8T #7T • ON AICI
#70ZO” O LIOO” O £100 * O Iſ; IO * O £100 * O 6T * ? †70* 08° O Z9 * O ZA * O 10 * I £ º 147 g * 3I ȘI “ ON AICI
OZIO * O GOETO * O G 790 * O OGOT * 0 0 / 7I * O 60 * Gç* IZ * 9. 89 * 0 06° 0 09 * O 8 * #7f7 I” / I ZI • ON ÕIGI
9 #7T0 * 0 0Z 00 * 0 // ZO * 0 £OZO” O 178ZO” O 60 ° § €6 * 0#7 * I Z; *O GZ * O 17 * 0 ; * / 17 /*
3T#}Ë
0900 * O GOOO “ O Z600 * 0 9600 * 0 G600 * O 60 * 9. Tº. * OG“ Z 99. * O £7/ * 0 // * O £ º G*7 / * 8I6 " ON AICI
94700 * 0 ? 000 * O Z 800 * 0 GGIO * 0 0 100 * 0 69 ° § € £ º O# * I ſyg º O £79°0 9Z * I 8 · 97 z • 8I8 " ON AICI
08IO “ O GO00 * 0 //00 * 0 69 TO * O 8900 * 0 6/ * 47 0£” Og * I Gº * O 89 * O 6 Iº I º ‘ / 47 9. * 8I/ * ON AICI
87 TO “O Z000 * O £800 * 0 89 TO “O 0900 * 0 6/ * ſ; 0£ * 0g * I £47 * O £79 * O £9 * I 9° 9′7 Z • 8I9 ° ON AICI
I9 IO º 0 ? 000 * 0 0800 * O Iſ; IO * 0 0.800 * 0 60 º 9 07° 08 * I 19. * O £79 * O 6T“ I Z * 937 O º 8T9 ° ON AICI
OLIO “ O £000 * 0 9 100 * 0 09 TO “O G900 * 0 68 ° € Iſ7 *0#7 “Z 847 * 0 69°0#7 “I O • 947 O • 8I#7 ° ON ÕIGI
47 100 * 0 9000 * 0 Z800 * 0 647 TO “O Z 800 * 0 66 ° S IZ * OZ * I 19. * O £79 * O 9Z * I g * 937 € * 8I€ * ON AICI
£8 TO “O ZOOO “O Z 100 * 0 / 47 TO “O Z ZOO” O 6T * #7 € £ * 0#7 “Z Çț7 * 0 69°0 6T ‘ T Z * 947 Z * 8IZ * ON AICI
478 TO “ O TOOO * O £7/00 * 0 89 TO * 0 0 100 * 0 68 ° € Z9 * 09 ° Z. Zſ; * 0 69° 0Tº I gº 97 % * 3TT " ON AICI
[]pOJOAUIZºOSeoJ3īTV3. IGozaN• ONTēȚdūēS
TeņOL
ZīĀTºsȚSKTēūē Tē5Țūſēų5
Suaz!!!ņu3J 0-9#-81 go sįsÁIeue ſepļuuºuſ) º 1 914 e 1
 89 * 0I • Ig * I7I * O IZ * O 8900 * 0 8ZOO” O 9Z " ON AGI
-O* I9 ° Z.9T * 0 0Z * 0 0 100 * 0 8ZOO” O SZ * ON AICI
/Z * 06 * T-9I * O OZ. “O G6ZO” O “7IOO” O “7Z * ON AGI
IO * 0O “ Z/* Z£Z * O IZ * O 1600 * O OOTO” O £Z * ON AICI
97 '0/* Z9 ° C£I * O OZ * O 1990 * 0 GZOO * O ZZ * ON AICI
IO * 09 • ZZ * gII º O OZ * O 08ZO” O SZOO * O IZ * ON AICI
TO “O8 * T# º z60 * 0 90 ° 0 07IO * O 89IO * O OZ. “ON AGI
IZ * O/* Zſy º £SI “ O 9Z * O G8 ZO * O OZOO * O 6T ‘ ON AICI
10 * 0O “ ZI º ç6I º O LZ * O Ç Ç ÇO” O 9I00 * O 8I “ ON AICI
ZI * 0ſy º zg º £9T * 0 ?Z * O 89-90 ° 0 /I00 * 0 /I “ ON ÕIGI
10 ° 0I • Z6 * ZGO * O £0 * O IGCO” O STOO” O 9I “ ON AICI
IO * 09 ° Z.g º £90 * 0 €0 * 0 96ZO * O IZOO * O ŞI “ ON AICI
IO * 09. “ Z# * g90° O £70 “O ISSO “O GIOO” O “7I “ ON ÕIGI
ZO " O6 “ Z9 º ££0 * 0 €0 * O IZ 90° O / ZOO” O £T º ON AICI
IO * 09. “ ZI º ç#7Z * O 19. * O Z800 * O £17-IO “ O ZI • ON AGI
IȚuzº T8 * T60·0 9T-0 Itto-o ººooºo !! •lºº
OT
ºº
ON AICI
80 ° 06 * T9 ° Z60 * 0 60 * 0 0990 * O ITOO * O 6 ° ON ÕIGI
OI º O/ * I# º z60 * 0 10 * O ITCO º 0 6 TOO * O 8 ° ON AGI
478 ° 0# * I/ * IIT “ O 60 * 0 6Z 90° O OZOO * O Z * ON AICI
*70 ° 0z ºz9 ° ZII* O OI ‘O OLZO.“ O SZOO” O 9 * ON ÕIGI
8T º O© º z8° Z.ZI * O OI ‘O ZZCO” O IZOO” O 9 ° ON ÕIGI
Z9. *0O “ ZO º £II* O SI “ O #6ZO” O 6T00 * 0 ? ° ON AGI
19. *0/ * I6 * I90° O GO * O 09 00 * O ZZOO * O £ º ON AICI
90 ° 0Tº z6 * Z80 ° 0 €T * 0 699.0 ° 0 /I00 * O Z * ON AICI
10 * 03 * Ig * Z80 ° 0 60 * O Zț790 * 0 8T00 * O I “ ON AICI
SO2 aOº H 3318OºH IeņOLXIeNUWȚN°ONTēTđūēS
3TqnIosuȚ–32 eurų. ĮO
% ūſā ºsȚSKTēūē Tē5ȚūlēūO
pºnuļļu00 º 1 9|qe 1
publications is presented in Table 2; the process
parameters for several samples are listed in Table 3.
The data in Table l show that several impurity
elements occur over a wide concentration range,
indicating the potential areas for applying puri
fication treatments which will have the most effect
on the fertilizer grade. The large iron and alumi
num ranges were expected; however, calcium and
fluorine, which were previously thought to be
unimportant constituents, were sometimes highly
significant. The solid-phase identifications in
Table 2 reflect these chemical analyses and show
the fate of each impurity element associated with
the phosphoric acid. The process parameters in
Table 3 show that there are significant differences
in the operating conditions for moisture removal in
the preneutralizer.
Results and Discussion
Calcium—Calcium is present in several forms,
depending mainly on the total fluorine content.
The chukhrovite (Caa Si AlSO4 F13 - 12H2O), which
ranges up to 1.67%, is carried over from the
wet-process acid because of incomplete removal
during the acid filtration step. When fluorine is in
excess of that required by aluminum, iron, chro
mium, and vanadium, it can precipitate as CaF2,
provided that the soluble silica also has been
satisfied. This condition has been observed for
samples DP No. 25 and DP No. 26. The stable
calcium salt in diammonium phosphate solution
between pH 5.3 and 8.0 is Ca(NH4)2 (HPO4)2 --
H2O, which was used for the calculations in
Table 2 even though a direct observation of its
presence was not possible at the concentrations
shown in Table 2 (3). This salt dissolves incon
gruently in water; and its reaction product,
Cas (PO4)3OH, was detected in the water-insoluble
fraction. Investigation at several phosphoric acid
plants showed that the acids contain higher cal
cium contents; two possible sources of this are:
(1) the phosphoric acid unit was operated at high
extraction temperatures, which caused an unusu
ally large amount of calcium to be dissolved in the
product acid from the plant; and (2) the amount of
gypsum in the acid also was high because of the
type of filter used or maintenance of the filter.
Magnesium–Like calcium, the magnesium
ammonium phosphate was too poorly crystallized
to be observed directly in the fertilizer. Since
the calcium and magnesium salts shown in Table 2
could not be identified directly, it is possible that
6
these cations precipitate as other forms, such as
fluorophosphates. Ando (4) states:
Fluorine forms a previously unknown compound,
MgNH4HFPO4(MAFP), when monoammonium phosphate
made from wet-process phosphoric acid is treated with
magnesium hydroxide above about 75 C in the presence of
moisture. When preparation of MAFP was conducted at
90 to 100 C in the presence of a small amount of water
using a mixture of monoammonium and diammonium
phosphates, magnesium hydroxide reacted very slowly
releasing ammonia; the product contained MgNH4 PO4” H2O
and less MAFP in the same manner as in the test with com
mercial ammonium phosphate, indicating that only a small
part of the fluorine forms MAFP at high pH.
These results indicate that MgNH4 HFPO4 could
precipitate in the preneutralizer (lower pH), and
MgNH4 PO4· H2O could be formed in the granu
lator where the pH is high. However, TVA labora
tory tests indicate that fluorine is precipitated as
(Al,Fe)NH4 HPO4 F2 . xH2O and CaF2 before mag
nesium can react with fluorine. The compound
MgNH4 PO4· H2O should be the precipitating phase
in the preneutralizer slurry and the granulator,
which would not cause any production problems
with high magnesium acids since the MgNH4 PO4 -
H2O (5 to 10 p.) is well crystallized and would not
contribute significantly to viscosity problems. This
compound can lose ammonia and water during
drying of the product to produce an amorphous
material. If the magnesium concentration in the
DAP-grade acid (~ 40% P2 Os) is too high to make
grade (18-46-0), it can be removed effectively
from the acid by adding byproduct H2 SiF6 to
precipitate MgSiF6 to reduce the magnesium
concentration to an acceptable level.
Iron and Aluminum-Previously the gelatinous
materials from the ammoniation of wet-process
phosphoric acid were described as amorphous
iron and aluminum phosphate and given the
formula (Al,Fe)PO4 'nH2O. Chemical analyses of
the water-insoluble components from commercial
diammonium phosphate fertilizers show that the
Fe and Al precipitate is much more complex than
the (Al,Fe)PO4 nH2O formula indicates.
Akiyama and Ando (5) reported in their inves
tigation that the main constituent of the gel-like
substance is a compound having the composi
tion of (Al,Fe)NH4 HF2PO4. This compound can
be identified readily by x-ray powder diffraction
techniques when crystallized sufficiently. It
became apparent that the composition of
(Al,Fe)NHa HF2 PO4 was affected by the tempera
ture and retention time during precipitation of the
compound. This fact was confirmed by Pechkovskii
(6), who states:
 Compound
2
3
4
5
D
6
7
No.
1P
DP

fertilizers,
18-46-0
in
compounds
of
analysis
Component
2.
Table
%
wt

number
Sample (69.96
NH4)2HPO,
49
74.
75.35
28
67.
72.73
71.4l
72.78
73.42

H2PO4
NHL,
l.04
36
l.
2.14
1.
-

(NH4)2SO4
5.25
6.54
6.49
6.96
5.31
19
8.
5.7l
7.33

(HPO4)2
FeNHu
0.84
2.46
23
l.
5.22
12
3.74
71
5.
3.35 (0.12
NH4)2SiF6
1.08
64
l.
0.51
0.49
0.71
1.16
0.33

(1.64
(NH4)2
Ca
HP04).2°H2O
1.86
1.50
2.57
14
1.
29
2.43
1Cau2H20
•
0.24
0.34
0.26
0.45
0.20SiAlSO4F13
0.04
0.21
0.53
°xH2O 4.
F2
FeNHLHPO,
0.82
1.61
0.65
1.90
36
0.73
78
3.
3.15 °xH2O
F2
HPO,
AlNHL,
78
3.
11
4.18
4.52
4.24
44 °xH2O
F2
HP0,
CrNHu
0.03
°xH2O
F2
HPO,
VNHu
0.06
0.05
07
0.
0.07

*H2O
POL,
MgNHL,
2.75
2.68
2.36
07
3.
2.17
2.24

(HPO4)2
AlNHu
- 61
98.
07
98.21
98.41
Summation
99.09
98.40
98.71
98.55
POu
ZnNHL
0.02 UO2NH4
0.03
0.007
0.02
0.01 NiNHL,
PO1, 0.006
0.005
0.007 POu
MnNHL
POu 0.10
0.08
0.09
0.11 H2O
Free
2.0
1.7
2.1
1.8
2.2
2.3
1.4
NHLPO,
Cd
0.0004
0.0002
0.001 (NH4)3P0,
4.87
73
3. -
-

0.26
0.68
0.47
52
0.
0.78
0.37
57 KH2POu
NaH2PO4 0.28
0.21
0.42
0.38
0.31

CaF2
-
-
-
 DCompound
9
16
15
14
13
12
No.
DP
11
and
10
Nos.P

number
Sample

Continued
2.
Table

°xH2O
F2
A1NHaHPOu
4.44
l.26
4.91
4.15
07
4.
3.02
97
5.

•H20
MgnHuP04
2.68
30
2.
2.75
ll
2.04
2.43

H2.08
*
(HPO4)2
(NH4)2
Ca2O
4.15
0.38
0.14
0.20
0.24
5.08
CauSiAlSO4F13°12H20
0.03
0.06
0.47
67
1.
0.10
0.07
°xH2O
F2
CrNH4HPO,
0.04
0.25
0.03
0.11
exh2O
F2
HPO,
VNHa
0.06
0.42
0.08
0.04
20
exh
F2
FeNHaHPO,
2.86
2.23
20
1. -

POu
UO2NH4
0.027
0.03
0.02
0.009 (HPO4)2
FeNH4
27 AlNH4
0.74
4.08
13
4.
4.18
5.- (HPO4)2
36
2.
1.18
1.26
1.98
- (0.22
NH4)2SiF6
0.18
0.33
0.21
20
1.
50
0.
1.40 40
99.
98.01
97.21
98.73
98.93
98.83
97.47
Summation
CóNHaPOa
0.03
0.002
0.003
0.004
0.001 0.04
0.01
0.006
0.004
0.003
0.008 MnNHaPOu
NiNHaPOu 0.11
0.09
0.10
0.03 (NH4)2SO4
92
70
6.
6.98
6.99
9.87
4.94
76
5. (67.
NH4)2HP04
64
73.
66.91
61
75.
35
71.
69.94
84
73.94 H2O
Free
2.3
1.2
2.6
1.9
2.9
2.1
PO4
Zn/NHL
0.018
0.02
0.40
0.08
0.03 NHaH2PO4
2.17
- (NH4)3P04
3.31
97
4.
5.18
4.24
2.85
-
-

NaH2PO4
0.16
0.21
1.93
0.89
0.47
KH2PO4
0.84
0.30
0.31
0.17
0.10
CaF2
-
-
 Compound
23
22
No.
DP
21
19
18
17

number
Sample

Continued
2.
Table

1Cau2H2O
-
53
0.
0.20
0.04
1.06SiAlSO4F13
0.45
0.23
(3.93
(NH4)2
Ca
HPO4)2-H20
4.16
5.00
07
3.
3.15
3.48
79
1.
FeNHa
24
1.
12
2. -
- exh2O
F2
AlNHaHPOu
F2°xH2O 6.
HPO, 38
29
7.
5.78
39
6.47
6.30
5.58
CrNHaHPOuF2°xH20
0.034
0.29
0.31
0.03
0.04
20
exh
F2
HPO,
WNHu
0.05
0.055
0.35
0.06
51
0.
“H2O
MgNHaPO,
2.24
30
2.
2.43
2.94
2.81
2.88

(HPO4)2
FeNHL
35 AlNHa
5.61
5.86
4.08
3.10
9.- (HPO4)2
0.67
1.04
- (0.39
NH4)2SiF6
0.66
0.23
0.72
58
0.
0.61
30
1. (63.
NH4)2HPO,
18
68.
64.01
60
62.
69.90
38
71.
41
13 98.54
97.62
99.06
99.03
98.83
97.83
98.70
Summation
Zn/NHaPOu
0.016
0.33
0.03
0.017
0.42
0.02 PO4
UO2NH4
0.02
0.023
0.010
0.022
0.01
0.0198 0.030
0.11
0.086
0.043
0.09
0.109
0.10
MnNHaPOu (NH4)2SO4
92
6.
6.13
6.96
8.23
5.98
66
5. 2Free
H2O
2.7
2.0
2.4
2.6
1.8
7
2..0
CaMHaPO,
0.018
0.0004
0.032
0.001
0.0008 NiNHLPO,
0.049
0.006
0.029
0.005
0.007 H2PO4
NHL,
1.59
3.24
-
-
- (NH4)2P04
3.31
3.52
38
5. -
-

NaH2PO4
1.36
1.41
1.25
1.04
0.31
10
1.
KH2PO4
0.52
0.66
0.56
0.38
0.31
0.80
0.45
CaF2
-
-
 Compound
26
No.
DP
25
24

number
Sample

Continued
2.
Table

CauSiAlSO4F13
•12H2O
0.078
0.17
(4.02
(NH4)2
Ca
HP04).2°H20
2.59
exh2O
F2
FeNHLHPO,
3.23
3.54
3.31 °xH2O
F2
HPO,
CrNHu
0.09
0.039
20
exh
F2
A1NHLHP0,
5.64
1.99
20
exh
F2
HPO,
VNHu
0.054
0.02
0.01
H2O
-
MgNHaPOa
2.94
3.71

POu
ZnNHL
0.14
0.13
0.025 NiNHaPOu 0.09
(HPO4)2
FeNH4
1.18 AlNHL
- (HPO4)2
-
- (1.16
NH4)2SiF6
0.97
0.78 (67.78
NH4)2HPO,
74.92
73.25 Summation
98.41
97.92
97.36
UO2NHLPO, 0.004
0.032
0.02
0.01 0.01 0.02
MnNHuPOu (NH4)2SO4
6.17
33
5.
36 H2O
Free
1.9
1.0
1.1
PO4
NHL,
Cd
0.002
0.01 NH4H2PO4
2.43
- (NH4)2P04
3.00-

NaH2PO4
1.04
1.10
KH2PO4
0.56
0.49
CaF2
14
1.
0.92
-

3
 Table 3. Process parameters in 18-46-0 production
Sample No.: DP No. 3 DP No. 4 DP No. 5

Production Rate 37.5 tons/hour 50 tons/hour 77 tons/hour

Preneutralizer Operation
Number Used 2 1 1
Size of Each (1) 11 ft x 15-1/4 ft 12 ft x 20 ft high 14.75 ft x 22 ft high
high
(2) 12 ft x 10 ft high
Retention Time (1) 101 min; (2) 29 min 74 min 61 min

Slurry
Depth in Preneutralizer (1) 15-1/4 ft; (2) 3.5 ft 12 ft 10 ft
Mole Ratio N: P (1) 1.15; (2) 1.55 1.46 1.5
Temperature 240°F 225 °F 250°F
Specific Gravity 1.5 1.56 1.57

Granulator
Product Temperature 185°F 204 °F 205 °F

DP No. 6 DP No. 7 DP No. 8

Sample No.:

Production Rate 110 tons/hour 44 tons/hour 55 tons/hour

Preneutralizer Operation
Number Used 1 l 1
Size of Each 17 ft x 25 ft high 14 ft x 25.5 ft high 12 ft x 20 ft high
Retention Time 48 min 98 min 49 min

Slurry
8.5 ft 10 ft 9 ft
Depth in Preneutralizer
Mole Ratio N: P 1. 48 1.65 1.6
Temperature 245°F 230°F 232°F
Specific Gravity 1.56 1.625 1.52

Granulator
Product Temperature 205 °F 175°F 197°F

Sample No.: DP No. 10 and DP No. 11 DP No. 24

Production Rate 75 tons/hour 37 tons/hour

Preneutralizer Operation
Number Used 1 1
Size of Each 11 ft x 25 ft high 12 ft x 25 ft high
Retention Time 31 min 128 min

Slurry
Depth in Preneutralizer 9 ft 15 ft
Mole Ratio N:P 1.5 1.4
Temperature 23.5°F 240°F
Specific Gravity 1.56 1.58

Granulator
Product Temperature 210°F 210°F
 The chemical analysis of the product showed a lower fluorine citrate-insoluble P2 Os as percent of total P2 Os
concentration in comparison with that calculated theo
retically for the formula AlNH4HF2PO4 in that the fluorine
present in the iron ammonium phosphate was
content was not constant for specimens obtained in different necessary in order to compensate for the total
experiments, whereas the Al2O3 concentration varied within quantity of this compound in the sample. For
closer limits. This could be linked with a possible isomor
*- 1- . 1- . -
example, the weight percent citrate-insoluble P2 Os
phous replacement of a F" ion by an OH" ion in
hydrothermal treatment. x 100, divided by the weight percent P2 Os re
ported as FeNH4 (HPO4)2, provides an interaction
The compound was written as cryptocrystalline term that relates the quantity of the citrate
(Al,Fe)NHa HPO4 F2 . xH2O to denote the variable insoluble compound to its effective solubility
chemical composition of the compound due to properties.
different temperatures and retention times en The citrate-insoluble fraction also was studied in
countered in 18-46-0 production (Table 3). For a series of 18-46-0 fertilizers for which the reten
simplicity of calculations the theoretical chemical tion time in the preneutralizer stage was available.
composition of (Al,Fe)NH4 HF2PO4 was used These data are shown in Table 4 and plotted in
instead of calculating the composition of the Figure 2. Again, the citrate-insoluble P2 Os was
compound that would precipitate for each set of
16O I I I I
conditions (temperature and retention time).
Iron and aluminum also can precipitate as
(Fe, Al)NH4 (HPO4)2 when there is insufficient
fluorine in the phosphoric acid to precipitate | 20 H.
(Al,Fe)NHa HPOa F2 . xH2O. The Al end member Sº
precipitates first; the Fe end member precipitates if "E
sufficient fluorine is present. If insufficient <f
# 8 O H.
fluorine is present, the Fe end member of the «
compound (Fe, Al)NH4 (HPO4)2 precipitates first, Lll
O
with the Al end member precipitating next. When <ſ
Ul
or 40 T
(Fe, Al)NH4 (HPO4)2 precipitates in the preneu >
ow)
tralizer, it occurs as an amorphous gel which
could contribute toward viscosity problems in the
preneutralizer. This condition quickly dissipates O I | | I

O IO 2O 3O 4O 5O
with the temperature and retention times en
countered in 18-46-0 production to produce large % C.I. P2 Os: % P2O5 IN HASEMAN E
euhedral crystals of (Fe, Al)NH4 (HPO4)2. Figure 1. Effect of surface area on citrate-insoluble
In the preneutralizer, conditions of slightly phosphate in 18-46-0 fertilizers.
higher temperatures and longer retention times
have resulted in citrate-insoluble phosphate. 50 i i T I T

The citrate-insoluble phosphate problem in 18-46-0

fertilizer was found to be related to the
FeNHA (HPO4)2, but not always directly to its
total quantity in the fertilizer (7). Microscopic
observations showed that with increasing crystal
size of the iron compound, the level of citrate 3 O H.

insoluble P2 Os also increased. To relate crystal

size and citrate-insoluble P2 Os, three samples were
2O H.
chosen that differed widely in their reported
content of citrate-insoluble P2 Os but had similar
quantities of the iron ammonium phosphate.
The surface area of the three samples was
determined on the water-insoluble fraction and
compared to the citrate-insoluble P2 Os reported O l l l I I
O 25 50 75 IOO 125 150
as percent of total P2 Os in the iron ammonium
phosphate compound. These results (Figure 1) RETENTion TIME, (MIN) AT 230°-250°F
show a good correlation for surface area and Figure 2. Relationship of preneutralizer time and citrate
citrate-insoluble P2 Os content. Reporting the insoluble P2 Os in 18-46-0 fertilizers.

12
 FP20s
0%
-
(HPOu)2
it.5H2O
C%
o
ase.NHu
rate-inf
cRetention
in
time soloulbubele
No.
sample
18-46-0
0Pre.5H2O
min
- neutralizer,
(HPOu)2
FeNHL
18-46-0
in
P20s
6–0
18–4
in

freunction
a
pas
in
time
retention
ofrnteuitlriazliezresr

ll
and
10
Nos.
DP
31
0.74
0.0
nil

Citrate-insoluble
4.
Table
18-46-0
commercial
in
Os
P2

2
(HPOu)
FeNHa
Pure
145.9
22.4
50
-

35.
6
No.
DP
1.4
0.04
710 8
No.
DP
4
12
5.
3.
0.10
9 DP
6
5
No.
0.18
3.35
10.4
1 DP 4 DP
72.46
4
No.
25.2
0.32 7
No.
93.74
44.0
0.84
8 DP
128
24
No.
44.3
0.27
18
1.
C
expressed as percent of total P. Os in FeNH4
(HPO4)2. The pure sample of FeNH4 (HPO4)2 in
Table 4 was prepared in the laboratory under
similar conditions encountered in commercial
preneutralizers. These data show that crystal
growth is complete after 100 minutes at 230° to
250°F, where the citrate-insoluble P2 Os reaches a
maximum of 45% of the P2 Os present as
FeNH4 (HPO4)2. Thus, the citrate-insoluble P2 Os
can be decreased by decreasing the total quantity
of iron ammonium phosphate and by decreasing
the retention time in the preneutralizer, which
effectively decreases crystal size.
A detailed evaluation of Tables 1 and 2 indicates
that the quantity of the citrate-insoluble salt can
be decreased by maintaining a high fluorine con
tent. This favors the formation of the citrate
soluble iron-fluorophosphate and also effectively
releases a mole of H3PO4 for ammoniation to
decrease the effect of iron on the nitrogen grade.
There is no indication that the fluorophosphate
compounds become a citrate-insoluble problem
during long retention times in the preneutralizer.
For acids with insufficient fluorine values, a very
short preneutralizer period will be necessary to
prevent crystal growth of the iron ammonium
phosphate. Obviously, the preferable way to lower
the retention time in the preneutralizer is to
decrease the effective size of this tank. This
can be accomplished by one of the following:
(1) lower the depth of slurry in the existing pre
neutralizer, (2) install a smaller preneutralizer, or
(3) install a pipe-cross or pipe reactor.
Some producers fear that they will encounter
high ammonia losses and low water evaporation
from the preneutralizer if retention time is de
creased. If this is a problem, it might be preferable
to install two preneutralizers, as shown in the flow
diagram (Figure 3). The first preneutralizer is
relatively large and should be operated at a mole
ratio N:P of 0.6. Microscopic and chemical ana
lyses show that at this low degree of ammoniation
there is no reversion of the P2 Os to an unavailable
form. The exit gases from this preneutralizer may
contain fluorine; however, they will not contain
NH3. Because of the large exposed surface area of
the slurry in the first preneutralizer, there is
an excellent evaporation efficiency. The degree of
ammoniation in the second preneutralizer results in
a slurry having a mole ratio N:P of 1.4 to 1.5. The
citrate-insoluble FeNH4 (HPO4)2 forms at the
higher degrees of ammoniation (8). Since the
retention time in this preneutralizer is low, the
14
FeNH4 (HPO4)2 crystallizes as small crystals in
which the P2 Os is available.
The total retention time for sample DP No. 3
(Table 3) in two preneutralizers is relatively high
(135 minutes); the retention in the second pre
neutralizer, in which the mole ratio N:P of the
slurry is 1.45, is low (29 minutes). The citrate
insoluble P. Os in this product was relatively low
as compared with the product citrate-insoluble
P., Os of some of the other companies, which also
had relatively high slurry retention times in their
single preneutralizers. Data in Tables 1 and 3
show that the temperature of the slurry from the
preneutralizer or granulator seems to have little
effect on the citrate-insoluble P2 Os of the prod
uct, provided that the product temperatures from
the ammoniation units are less than 250°F for the
preneutralizers and 210°F for the ammoniator
granulator. Additional data are needed to deter
mine if there is an upper ammoniation temperature
limit.
Excessive quantities of iron and aluminum can
be decreased in the phosphoric acid by better
clarification of the insoluble sludge components
from merchant-grade acids. Iron and aluminum are
decreased to 0.2 to 0.3% Fe2O3 and 1.6 to 1.8%
Al2O3 in wet-process acid containing 54% P2 Os
by addition of a soluble source of potassium. This
causes precipitation of (Fe, Al)3 KH 1.4 (PO4)s -
4H2O, which settles readily and allows for decan
tation of the purified acid. The settled sludge
fraction can be recovered in superphosphate or
suspension fertilizer production where the high
analysis phosphate solid is not detrimental. The
composition of the precipitating compound shows
that addition of 0.1% K2O to merchant-grade
acid will decrease the Fe2O3 by 0.50% and the
Al2O3 by 0.32%.
Zinc, Cadmium, Nickel, Manganese, and
Uranium—The divalent trace elements (Zn, Cd, Ni,
Mn) and U" " complex ion, UO, **, most often
precipitates as M* "NH, PO, and were calculated as
this anhydrous compound. Although each divalent
trace element is relatively insignificant in quantity,
their collective effect, particularly in western acids,
is to neutralize a significant quantity of phosphoric
acid as a low-nitrogen content compound.
Chromium, Vanadium-Stability constants for
complex ion formation of fluorine with chromium
and vanadium are similar to those for fluorine
and iron. Therefore, these trivalent cations were
calculated as the fluoride compounds. Further
 …
-
·oheųdsoud unſuº
_-
londo ºd
nooº
ae gno0
lon008d 0\
038 0.1mT）
：
© T

gouwn nnwº
- Jõī£ın0www.º
|
-
-
-
-
-
ae |-
：
， …
• ſ） -l，~ ----
|-. .
|
- ----
o loſ
omaeo HdSOHd
-…--
！ Odwº
sN338 （31-v^^
0S{|a
nonok [×E
º{| tautaſ，#ſ……
characterization work is necessary to accurately
predict the correct composition of matter of the
precipitating solids.
Silica—The silica content was associated with the
water-soluble fluorine and was calculated as
(NH4)2SiF6. At first, the water-soluble fluorine
was suspected to be (NH4)3 AlF6; however, the
absence of a significant water-soluble aluminum
component eliminated this possibility.
Sulfate—Only two sulfate-containing compounds
have been detected, namely (NH4)2SO4 and
Caa Si/AlSO4 F13 - 12H2O, which is an insoluble
component carried over in the wet-process phos
phoric acid. Phase studies indicate that the metal
ammonium sulfates, M(NH4)2(SO4)2 XH2O,
formed by divalent metals are possible solid
components over a wide pH range. However,
essentially all of these double sulfate compounds
have a much higher solubility than the comparable
metallic ammonium phosphate. Thus, (NH4)2SO4
is the stable sulfate in equilibrium with the ammo
nium phosphates. Double salts comprising ammo
nium sulfate and phosphate exist only in the acid
region below pH 1 and thus are not present in
18-46-0 fertilizers (9).
Fluorine–Other than ammonia and phosphate,
fluorine is the most widely distributed element in
18-46-0 fertilizers. Fluorine occurs as Caa SiAlSO4 -
F13 - 12H2O, CaF2, (Al,Fe)NH4HPO4 F2’xH2O,
(V,Cr)NHa HPO4 F2’xH2O, and (NH4)2SiF6. Pre
cipitation of the complex metal ammonium fluoro
phosphates presents a potential method for con
verting residual fluorine derived from wet-process
phosphoric acid to an insoluble form in the
18-46-0 grade product rather than scrubbing the
fluorine by expensive pollution abatement proc
esses. Some commercial 18-46-0 producers are
using their ammonia scrubbers for fluorine scrub
bing by operating at a low mole ratio N:P; which is
effectively the same as a preneutralizer slurry, only
a little lower in pH. The producers report that the
mole ratio N:P of the slurry from the scrubber is
between 0.6 and 0.7. At this degree of ammonia
tion of the acid, most of the fluorine remains in
the acid when using a Doyle impingement-type
scrubber (Figure 4), and there is no difficulty with
loss of fluorine from the process. Usually about
one-third of the acid used in the process is added
to the scrubbers and the remaining acid is added
directly to the preneutralizer. When all of the acid
was added to the scrubbers and the mole ratio N:P
16
was something less than 0.6, there was a significant
loss of fluorine from the scrubbers. For this reason
the amount of acid added to the scrubbers was
limited.
Phosphate—The N:P adjustment can be used to
augment either the nitrogen or phosphate level in
the 18-46-0 product at the expense of the other
component by precipitating NH4H2PO4 (low N,
high P2 Os) or (NH4)3 PO4 (high N, low P2 Os).
The precipitation of (NH4)3PO4 was observed on a
recent plant trip, confirming earlier microscopic
findings. During the operation of the ammoniator
granulator, it was observed that there were several
lumps of frozen material which had stuck to the
ammonia spargers. When the material was broken
down, it contained large quantities of ammonia.
The producers were told that if they could add a
small quantity of water with the ammonia, this
caking around the sparger could be practically
eliminated and they could have less loss of ammo
nia from the ammoniator-granulator. Microscopic
analyses show that some of the 18-46-0 products
contained triammonium phosphate which was
present in these lumps off the ammonia spargers in
the ammoniator-granulator.
Water-Free water, which decreases both fer
tilizer components, is decreased by slightly higher
temperatures and much longer retention times in
the preneutralizer. Moisture can be decreased
before complete ammoniation (first-stage pre
neutralizer) if the fluorine concentration is low or
CLEAN
OUTLEF
GA s
Li QUID
SUPPLY
OvºRFLOW
system
Figure 4. Impingement-type scrubber.
in the preneutralizer if the fluorine is sufficiently
high to prevent the precipitation of FeNH4 (HPO4)2.
Grade Limitations—A few 18-46-0 products
were selected from Table 1 to represent the range
of impurities and nitrogen and phosphate values.
The effect of these impurity levels on the fertilizer
grade is shown in Figures 5 and 6, where the
7
6 H.
o
5 H-
4 H
summation of metallic oxides is compared with
the nitrogen values and the fluorine plus sulfate is
compared with phosphate. To simplify the nitro
gen curve, only the major impurities of iron,
aluminum, calcium, and magnesium oxides were
used. The same effect was observed when all the
metallic oxides were included. The data used in
Figures 5 and 6 show that the fertilizer grade is
affected to the extent that each percent increase of
impurity oxide and fluorine plus sulfate will lower
the grade level by 1%. When the average value
for hydrated and free water is added to the other
impurities, the total impurities are limited to 15%
-
in order to maintain an 18-46-0 grade. It is im
portant to recognize the fact that 18-46-0 is 85%
of the theoretical value for pure (NH4)2 HPO4.
The maximum level of impurities will require
-
close pH control to compensate for the ratio of
total cation to anion impurities. Above this level,
purification processes will be required to maintain
- 18-46-0 grade.

Pipe-Cross Reactor Production of 18-46-0–The

design shown in Figure 7 is used in the TVA pilot
plant for the production of 18-46-0 and it is TVA’s
recommended design for large plants (10). This is
a reactor with a very short slurry retention time
1 I I l
2 which produces 18-46-0 with low citrate-insoluble
15 I6 I7 18 19 2O
P2 Os. All TVA pilot-plant samples in the study
NITROGEN, 3%
(DP 13, DP 14, DP 15, DP16) proved this con
Figure 5. Effect of cation impurities on nitrogen content clusion by having citrate-insoluble P2 Os analyses
of 18-46-0 fertilizers.
of less than 0.1%, even though the quantity of
(Fe, Al)NH4 (HPO4)2 was greater than that present
I
in most of the commercial samples made by the
use of the preneutralizer.
7 H. There have been some problems encountered
with buildup of scale in pipe-cross reactors used to
produce diammonium phosphate. Microscopic
analyses reveal that there are two types of crys
6 H.
talline scale. The first is (Fe,Al)NHA (HPO4)2,
28
º, which occurs with phosphoric acids having iron
O and aluminum as the major impurities; and sec
º
+ M

ondly, MgNH4 PO4 H2O, which occurs with

* *
phosphoric acids having magnesium as the major
impurity. The formation of these compounds can
4 IT
be avoided by the addition of fluorine to the acid
used in the process to convert the scale to the
corresponding fluorophosphate compound. These
3 L 1 I 1
compounds, which precipitate as cryptocrystalline
43 44 45 46 47 48 compounds, will not form large scalar crystals like
P2O5, 3% (Fe, Al)NH4 (HPO4)2 and MgNH4 PO4 H2O, and
Figure 6. Effect of anion impurities on phosphate content their P2 Os will be completely available. The
of 18-46-0 fertilizers. following problems can be solved by using the

17
 T0 RENEW CALL
Jul 14% DATE DUE
422-3900

>RUBBER
REC

SCRUBBER LIQUOR S UBBER

OutR §§§ BED
wºn º- COSpARGE
* Po, of
NPSLU

AM Mon! A l
º

scrubaer Lloº" **
PIPE - CRO
REACTO

AMMON

CHARGE

- - HIGHSMITH 45-220
pipe-cross reactor instead -- - F:Fe2O3, it is advantageous to
------

preneutralizer tanks: have lower retention times in the preneutralizer

1. Difficulty in pumping and metering the hot
slurry from the preneutralizer.
2. Foaming and boiling over of the slurry in the
preneutralizer.
3. Difficulty in controlling the slurry level in
the preneutralizer.
4. Plugging of the ammonia sparger and poor
ammonia distribution in the preneutralizer.
5. Scarcity and high price of fuel needed for
drying the product (11).
In summary, this study identifies the main
problems in meeting DAP-grade specifications and
suggests some possible solutions to these problems.
Calcium was the major cause of grade deficiency
in the commercial samples which were investigated.
Possible solutions to this problem are to maintain
filter cloths in the phosphoric acid unit in good
condition, operate the phosphoric acid unit at as
low an acid temperature as is consistent with good
operation of this unit, and partially clarify the
acid before it is used.
In the DAP unit the amount of Fe2O3 and F in
the acid affects the content of citrate-insoluble
P2 Os in the product. If the weight ratio F: Fe2O3
in the product can be kept above 2.3:1, the citrate
insoluble P2 Os content of the product will be less
than 0.1%, even at excessive retention times. At
and ammoniator-granulator when the mole ratio
N:P is 1.4:1 or higher.
The mole ratio N:P in the slurry coming from
the preneutralizer to the granulator must be above
1.4:1 to avoid nitrogen deficiencies. At lower
ratios the product will contain some MAP; this
causes nitrogen deficiency in the product.
The Mg and Al contents of the acids have less
effect on grade deficiency than Ca and Fe.
To avoid highly viscous preneutralizer slurries
when low preneutralizer retention times are used,
ensure that there is sufficient fluorine available (wt
ratio F:Fe2O3 > 2.0:1) to combine with the
Fe2O3 to form cryptocrystalline Fe-NH4-PO4-F-
H2O instead of FeNH4 (HPO4)2 gel. An alterna
tive to this latter suggestion is to replace the
preneutralizer with a TVA pipe reactor installed so
that it discharges viscous slurry directly onto the
bed of material in the granulator.
Acknowledgment
The authors acknowledge the contributions of David G. Salladay
and Jeffrey L. Greenhill for their input of the engineering aspects of
18-46-0 production and John H. Holmes, Jr., for development of
analytical methods for determination of 18-46-0 products with
argon plasma spectrometry.

18
References
1. Achorn, F. P., E. F. Dillard, and A. W. Frazier. “Effect of
Impurities in Wet-Process Phosphoric Acid on DAP Grade,”
paper presented at the TVA-TFI Granulation Workshop.
Muscle Shoals, Alabama, October 2-3, 1979.
Frazier, A. W., J. P. Smith, and J. R. Lehr. J. Agric. Food
Chem. 14 (5), 522-529 (1966).
Frazier, A. W. J. R. Lehr, and J. P. Smith. J. Agric. Food
Chem. 12 (3), 198-201 (1964).
Ando, J., T. Akiyama, and M. Morita. Bull Chem. Soc. Jpn. 41
(7), 1716-1723 (1968).
Akiyama, T., and J. Ando. Bull Chem. Soc. Jpn. 45 (9), 2915
2920 (1972).
Pechkovskii, V. V., R. Ya Mel'nikova, M. N. Ryer, T. V.
Chadovich, and N. L. Gavrilyuk, Russ. J. Inorg Chem 24
(2), 175-179 (1979).
Hebbard, G. M. “Present Day DAP Production,” paper pre
sented at the 1979 Fertilizer Institute Round Table Meeting,
Washington, DC, October 30-November 1, 1979.
Frazier, A. W. E. F. Dillard, T. C. Woodis, Jr., and F. P.
Achorn. “Precipitated Impurities in 18-46-0. Fertilizers Pre
pared From Wet-Process Phosphoric Acid," paper presented
at the Fifth Annual TVA-TF1 Phosphate Workshop, Atlanta.
Georgia, February 19–20, 1980.
Frazier, A. W. J. F. McCullough, and R. M. Scheib. J. Agric
Food Chem. 19 (2), 213-215 (1971).
Achorn, F. P. D. G. Salladay, J. L. Greenhill, and E. F.
Dillard. “Effects of Process Parameters on Compositions of
DAP Products,” paper presented at the Fifth Annual TVA-TFI
Phosphate Workshop, Atlanta, Georgia, February 19–20, 1980.
11. Parker, B. R., M. M. Norton, L. W. McCamy, and D. G. Salladay.
"Pilot- and Demonstration-Scale Developments in Production
of Ammonium Phosphate-Based Fertilizers. Using the Pipe
and Pipe-Cross Reactors," paper presented at the 1978 Inter
national Superphosphate and Compound Manufacturer's
Association Limited Technical/Economic Conference, Orlando,
Florida, October 22–27, 1978.
 TVA is an equal opportunity employer and is committed to ensuring
that the benefits of programs receiving TVA financial assistance
are available to all eligible persons regardless of race, color, national
origin, handicap, or age.
ity
IDE POS ITEM C .
he Oh 8 02 014 6

mill.
3 243 46
º impuritiesºn. 18-46-0 *_

Bulletin Y-162 April 1981

TVA/OACD-35/12

ATIONAL FERTILIZER DEVELOPMENT CENTER TENNESSEE VALLEY AUTHORITY Muscle SHOALS, ALABAMA assed