Fertilizer Research 34: 197-202, 1993.

© 1993 Kluwer Academic Publishers. Printed in the Netherlands.

Obtaining NPK fertilizers using decomposition of phosphate rock by

sulphuric acid

E. Aasam/ie, J. Kudryavtseva & M. Einard

Tallinn Technical University, Laboratory of Inorganic Technology, E E 0108, Estonia

Received 22 May 1992; accepted in revised form 30 March 1993

Key words: NPK fertilizers, Kola apatite, Baltic phosphorite, sulphuric acid treatment, neutralization,
granulation

Abstract

In this study a method for obtaining granular NPK fertilizers of various grades has been established.
Kola apatite or Baltic phosphorites were dissolved in 57% H2SO4; the resulting slurries were then
ammoniated, evaporated and mixed with urea or ammonium nitrate and potassium salts. In some
experiments micronutrients (B, Cu, Mo, Co or Mn) were added. The mixtures were dried and
granulated. When using urea, granulation was carried out by heating the mixture until partial melting
occurred, but the mixtures with ammonium nitrate had to be granulated with the addition of water. The
products contained 29-38% fertilizer nutrients (N soluble in water, P205 soluble in citric acid and K20
soluble in water) and had a ratio of over 90% of P205 soluble in citric acid to the P205 total. The
granules were hygroscopic, but little caking occurred. The urea-containing materials produced better
granules. Adding micronutrients usually resulted in an improvement in the product quality (an increase
in the granule hardness and phosphorus solubility).

Introduction develop new processes for manufacturing NPK

According to recommendations by agrochemists,
Estonian agriculture must be provided with
granular NPK fertilizers having various
N : P 2 O s : K 2 0 grade ratio (1:0.5:0.9, 1:0.7:0.7,
1 : 1 : 1 and 1 : 1.5 : 2) and partly enriched with
microelements (B, Cu, Mo, Co, Mn). Professor
M. Veiderma has suggested that manufacture of
such fertilizers be organized in Estonia, using
granulation of the mixture of single superphos-
phate, ammonium nitrate and potassium chlo-
ride. This process has been studied in the USA
by TVA [131 and has been used in the Ukraine
[5]. The possibility of using urea in-
stead of ammonium nitrate has been proved too
[11.
The present study includes tests made to
fertilizers of the above grades by a method
without the production of single superphosphate
in an intermediate state, i.e. the slurry obtained
by digesting phosphate rock with sulphuric acid
is being used directly. According to some earlier
studies [11, 12], by using sulphuric acid concen-
tration of about 57% and a greater acidulation
ratio than for producing single superphosphate,
it is possible to obtain from apatite or phosphor-
ite free-flowing slurries with a high phosphorus
conversion of over 90%.
The main objective of this study was to work
out the main characteristics of the process with
using apatite or phosphorite, urea or ammonium
nitrate, and to give chief data on the chemical
composition and physico-chemical properties of
the fertilizers obtained.
198
Materials and methods
In this work standard flotation concentrates of
Kola apatite and Baltic phosphorite were used as
phosphate raw materials. The apatite contained
39.4% P205, the phosphorite of pyritic type from
the Maardu deposit (Estonia) 28.8% PaOs, 2.8%
Fe20 3 total (among this 0.36% Fe20 3 soluble in
sulphuric acid), 0.57% A1203, 1.1% MgO and
3.4% CO2, the phosphorite of dolomitic type
from the Kingissepp deposit (Leningrad district)
28.5% P205, 0.98% Fe20 3 soluble in sulphuric
acid, 0.57% A1203, 3.1% MgO and 7.5% CO 2.
The phosphorites were ground to 90% minus 180
microns and the a p a t i t e - t o 96.3% minus 180
microns. Three different processes of obtaining
NPK fertilizers were studied in which, besides
sulphuric acid and potassium salt (chloride or
sulphate), the following components were used;
(a) in the first process apatite and urea,
(b) in the second process apatite and ammo-
nium nitrate,
(c) in the third process phosphorite and urea.
Urea and ammonium nitrate were added
chiefly as solutions containing 5-15% free am-
monia and about 40% CO(NH2) 2 or NH4NO 3,
but partly also as solids.
Fertilizers with N : P 2 0 5 :K20 grade ratios of
1:0.5:0.9, 1:0.7:0.7, 1:1:1 and 1:1.5:1.5 were
obtained both with and without micronutrients,
using boric acid, sulphates of copper and cobalt,
a molybdenum containing waste product and
manganese chloride as micronutrient sources.
The theoretical acidulation ratio A / R
(kg HzSO 4 per 100 kg of phosphate rock) was
calculated by the composition of rock samples:
a) for apatite by the formula
A / R = 1.61 P205
b) and for the phosphorites by the formula
A / R = 1.61 P205 + 2.23 CO 2 + 0.61
Fe20 3 + 0.96 A120 3 [3] .
In the experiments acidulation ratio for de-
composition of apatite and phosphorite was
maintained at 125 and 110%, respectively, of the
theoretical one, and was 79.2kg for apatite,
60.2 kg for Maardu phosphorite and 70.2 kg for
Kingissepp phosphorite.
The experiments were made as follows. Sul-
phuric acid of 57% concentration was heated in a
porcelain reactor to 80°C, prior to addition of
phosphate concentrate and the slurry mixed for
1.5 hours at 90°C. After that the ammoniating
solution was fed into the reactor. The neutral-
ized slurry with a pH of 4-5.5 was transferred
into an evaporating vessel and, after potassium
and nitrogen salts and micronutrients had been
added, evaporated to dryness at 80-90°C within
0.5-1.5 hours. The powdered product was
granulated on a pan granulator by heating it with
a flameless gas-burner for the formation of melt.
In some experiments it was necessary to add
water to promote granulation and subsequently
to dry the granules at 80°C. The product was
screened to pass a 4 mm sieve and stored in
plastic bags. Fertilizer samples were analyzed for
various forms of P205: total, soluble in 2% citric
acid as proposed in [1] and water-soluble. For
this purpose a spectrophotometric method with
formation of the blue complex was used. Nitro-
gen was determined by using distillation and
titration of ammonia [2] after decomposing the
urea (when it existed) with the help of sulphuric
acid [10], potassium by the flame photometric
method, moisture by drying the samples at 65-
70°C [9]. Some physical properties of the
granules, such as the crushing strength, the
critical relative humidity by Pestov's method and
the caking tendency were measured [7].
Results and discussion
Investigations of the first process in which apatite
and urea were used showed that granulation of
an NPK mixture occurred within 6-30 minutes at
80-85°C (Table 1). In the experiments for ob-
taining fertilizers of 1:0.5:0.9 ratio granulation
took place as a result of forming the liquid phase
from the melting urea; in other tests it was
necessary to add also water.
The products contained 30-38% fertilizer
nutrients*, had the ratio of P205 soluble in citric
acid to the P205 total 90-99%, the ratio of the
water-soluble P205 to the P205 soluble in citric
acid more than 75% and the pH of the 10%-
* Sum of N soluble in water, P205 soluble in citric acid and
K20 soluble in water.
 199

Table i. NPK-fertilizers on the basis of apatite and urea

Characteristics Sample
1 2a 3 4a 5 6a 7 8~'c
N :P2Os :K20 ratio 1:0.5:0.9 1:0.7:0.7 1:1:1 1:1.5:1.5
Granulation time, rain. 16 30 30 18 21 6 19 16
Product analysis, %
W.S. N 15.8 15.7 14.4 14.5 11.1 10.9 7.5 7.4
P205 soluble in citric acid 8.3 8.3 10.3 10.2 10.7 11.2 11.7 12.2
W.S. P205 6.4 6.5 7.7 9.2 9.5 9.7 10.3 11.0
W.S. K20 13.9 13.8 10.6 10.6 10.7 10.6 11.0 11.0
HzO 0.5 0.5 1.2 0.6 2.5 2.1 0.8 0.5
Sum of fertilizer nutrients
(W.S. N + P205 soluble in
citric acid + W.S. K20 ) 38.0 37.8 35.3 35.3 32.5 32.7 30.2 30.6
The ratio of P205 soluble in
citric acid to the P2Os total 94 92 92 93 90 91 95 99
The ratio of W.S. P205 to the
P~O5soluble in citric acid 77 78 75 90 89 87 88 90
pH of 10% solution 4.9 5.1 4.9 4.1 4.3 4.2 4.7 4.5
Critical relative humidity, % 52 54 54 51 54b 56b 59b 60b
Caking tendencyd, kPa 3.0 0.9 1.7 3.4 17.3b 12.0b 0b 0b
Granule hardness, MPa:
after I week 6.2 5.8 4.7 4.7 1.2 1.5 0.6 1.8
1.5 months - - 5.6 5.3 2.8 b 3.1 b 3.6b 3.6 u
3 months 5.2 5.2 4.9 5.6 4.0b 3.8b 0b 0b
6 months 4.8 4.9 3.5 5.7 4.3 b 2.5 b - -
a Samples with addition of micronutrients (%):
sample 2 . . . 0.03 B, 0.015 Mo, 0.001 Co;
sample 4 . . . 0.15 Cu, 0.03 B;
sample 6 . . . 0.15 Cu;
sample 8...0.20Cu, 0.15Mn, 0.03 B;
b Additionally dried samples (moisture content 0.1-0.2%);
° Samples with the use of potassium sulphate;
d Hardness of the caked samples.

s o l u t i o n s a b o u t 4 - 5 . T h e loss of a m m o n i a in the times. T h e g r a n u l e s of the fertilizer f o r m u l a t i o n

process did n o t e x c e e d 4 % .
T h e g r a n u l e s of N P K fertilizers o b t a i n e d were
r a t h e r hygroscopic, h a v i n g critical relative
h u m i d i t y of 5 1 - 6 0 % , b u t little caking o c c u r r e d
i n c o m p a r i s o n with the e v a l u a t i o n p r e s e n t e d in
[8]. T o g u a r a n t e e satisfactory h a n d l i n g , trans-
p o r t , s t o r a g e a n d a p p l i c a t i o n such fertilizers
m u s t h a v e g r a n u l e h a r d n e s s n o t less t h a n 2 . 0 -
2.5 M P a [7]. A s regards the h a r d n e s s of the
g r a n u l e s in the c o u r s e of storing in o u r w o r k , the
h i g h e s t v a l u e s were o b s e r v e d with the p r o d u c t s
of 1 : 0.5 : 0.9 a n d 1 : 0.7 : 0.7 grade ratios: 4 . 7 -
7.7 M P a after o n e w e e k a n d 3 . 5 - 5 . 7 M P a after 6
m o n t h s . T h e h a r d n e s s of the g r a n u l e s of p r o d u c t
1 : 1 : 1 was c o n s i d e r a b l y lower ( 1 . 2 - 1 . 5 M P a ) .
This l a t t e r effect was p r o b a b l y caused b y the
h i g h e r m o i s t u r e c o n t e n t [7], as after a d d i t i o n a l
d r y i n g the g r a n u l e s t r e n g t h i n c r e a s e d a b o u t 2 - 3
1:1.5:1.5, o b t a i n e d with p o t a s s i u m s u l p h a t e ,
h a d a satisfactory h a r d n e s s o n l y d u r i n g 1.5-
m o n t h s ' storage w h e n dried a d d i t i o n a l l y . T h e
a d d i t i o n of m i c r o n u t r i e n t s c o p p e r , m a n g a n e s e
a n d b o r o n b r o u g h t a b o u t a n i n c r e a s e i n the
p h o s p h o r u s solubility, while in o t h e r experi-
m e n t s a d d i t i o n of c o p p e r b y itself c a u s e d accele-
r a t i o n of g r a n u l a t i o n , a n d c o p p e r a n d b o r o n
t o g e t h e r c a u s e d a n i n c r e a s e in the w a t e r - s o l u b l e
P205 c o n t e n t in the p r o d u c t .
I n the s e c o n d process a p a t i t e a n d a m m o n i u m
n i t r a t e were used. T h e results of the e x p e r i m e n t s
s h o w e d that a d d i n g w a t e r was n e c e s s a r y for the
g r a n u l a t i o n of the N P K m i x t u r e s ( T a b l e 2).
G r a n u l a t i o n o c c u r r e d w i t h i n 1 0 - 3 0 m i n u t e s at
4 0 - 5 0 ° C . T h e dried p r o d u c t s of v a r i o u s grades
c o n t a i n e d a b o u t 2 9 - 3 5 % fertilizer n u t r i e n t s , h a d
the ratio of P205 s o l u b l e in citric acid to the P205
200

Table 2. NPK-fertilizers on the basis of apatite and ammonium nitrate

Characteristics Sample
9 10a 11 12a 13 14a 15 16a'c
N : P205 : K20 ratio 1 : 0.5 : 0.9 1 : 0.7 : 0.7 1:1:1 1:1.5:1.5
Granulation time, min. 9 9 11 10 30 14 24 19
Loss of ammonia, % of total N 6 7 1 2 9 10 2 1
Product analysis, %:
W.S. N 14.2 14.0 13.6 13.4 10.3 10.1 7.1 7.2
P205 soluble in citric acid 7.4 7.7 9.6 9.6 11.0 11.2 10.8 11.0
W.S. 17205 5.7 6.7 7.0 8.8 8.9 9.1 8.9 8.8
W.S. K20 13.6 13.5 9.8 9.8 10.7 10.5 10.8 10.7
H20 0.7 1.6 1.1 1.0 0.9 1.0 2.7 1.5
Sum of fertilizer nutrients 35.2 35.2 33.0 32.8 32.0 31.8 28.7 28.9
The ratio of P205 soluble in
citric acid to the P~O5 total 90 94 92 92 93 96 92 92
The ratio of W.S. PzO5 to the
P205 soluble in citric acid 77 87 73 92 81 81 82 80
pH of 10% solution 4.9 4.6 5.1 5.2 5.1 4.9 4.5 5.0
Critical relative humidity, % 55 57b 56 57 51 54 54b 64b
Caking tendency, kPa 15.4 7.0 b 4.3 0 0 4.8 0b 0b
Granule hardness, MPa:
after 1 week 2.1 1.5 2.1 2.4 2.5 3.5 0.8 0.5
1.5 months - 4.0 b - - 2.0 2.1 3.8 ~ 4,6 b
3 months 2.5 5.6 b 2.5 1.9 0 0 0b 0b
a Samples with addition of micronutrients, (%):
sample 10... 0.03 B, 0.015 Mo, 0.001 Co;
sample 12... 0.15 Cu, 0.03 B;
sample 14... 0.15 Cu;
sample 16... 0.20 Cu, 0.15 Mn, 0.03 B;
b Additionally dried samples (moisture content 0.1-0.2%);
c Samples with the use of potassium sulphate.

t o t a l 9 0 - 9 6 % a n d t h e r a t i o o f w a t e r - s o l u b l e P205 3). I n t h e s e e x p e r i m e n t s f o a m i n g o f slurries f r o m

to t h e P205 s o l u b l e in citric acid was m o r e t h a n
7 7 % . T h e loss o f a m m o n i a in t h e p r o c e s s o f
p r o d u c i n g fertilizers of 1 : 0 . 5 : 0 . 9 a n d 1 : 1 : 1
r a t i o was c o m p a r a t i v e l y high ( 6 - 1 0 % ) , b e i n g
c o n s i d e r a b l y l o w e r in o t h e r cases. T h e s e p h e -
nomena are conditioned by the various composi-
tion and the different granulation time of the
f e r t i l i z e r s a m p l e s . I n [13] t h e h i g h e s t losses o f
a m m o n i a w e r e o b s e r v e d b y p r o d u c i n g t h e fertil-
izer of 1 : 1 : 1 ratio, too.
T h e a d d i t i o n of t h e m i c r o n u t r i e n t s u s u a l l y
i n c r e a s e d p h o s p h o r u s s o l u b i l i t y (see s a m p l e s 10,
12 a n d 14) a n d s t r e n g t h o f t h e g r a n u l e s if d r i e d
t o t h e m o i s t u r e c o n t e n t n o m o r e t h a n 1 % . I n test
14 a d m i x t u r e o f c o p p e r c a u s e d significant de-
creasing of the granulation time.
I n t h e t h i r d p r o c e s s o b t a i n i n g fertilizers of
g r a d e 1 : 0.7 : 0.7 was s t u d i e d with p h o s p h o r i t e ,
urea and potassium chloride being used (Table
t h e r e a c t i o n o f p h o s p h a t e r o c k with s u l p h u r i c
acid was o b s e r v e d . W i t h K i n g i s s e p p p h o s p h o r i t e ,
a d d i n g o f a d e f o a m e r was n e c e s s a r y . G r a n u l a -
tion of NPK-mixtures occurred within 5-19 min-
u t e s at 8 0 - 9 0 ° C w i t h o u t a d d i n g w a t e r . T h e
products contained about 36-37% fertilizer nu-
t r i e n t s , h a d a h i g h r a t i o o f P205 s o l u b l e in citric
acid to t h e P205 t o t a l ( 9 4 - 9 9 % ) a n d a sufficient
r a t i o o f w a t e r - s o l u b l e PzO5 to t h e a v a i l a b l e o n e
( o v e r 6 6 % ) . T h e loss o f a m m o n i a was n o t m o r e
than 2%. The granules were hygroscopic, but no
c a k i n g o c c u r r e d a n d a high g r a n u l e s t r e n g t h
resulted even after 12-months' storing (over
3.6 M P a ) .
The addition of the micronutrients increased
phosphorus solubility and the granule hardness.
I n t h e e x p e r i m e n t s with M a a r d u p h o s p h o r i t e
micronutrients decreased granulation time.
W h e n K i n g i s s e p p p h o s p h o r i t e was u s e d , a d m i x -
 201

Table 3. NPK-fertilizers of 1:0.5:0.9 ratio on the basis of phosphorite and urea

Characteristics Sample
17 182 19 20a
Deposit of phosphorite Maardu Kingissepp
Granulation time, rain. 19 9 5 16
Product analysis, %:
W.S. N 15.2 15.2 14.8 14.8
P205 soluble in citric acid 8.0 8.2 7.7 8.3
W.S. P205 5.3 6.5 5.8 5.9
W.S. K20 13.6 13.6 13.3 13.0
H20 0.3 0.5 0.3 0.3
Sum of fertilizer nutrients 36.8 37.0 35.8 36.1
The ratio of P2Os soluble in
citric acid to the P205 total 96.0 98.0 94.0 99.0
The ratio of W.S. P2Os to the
P205 soluble in citric acid 66.0 79.0 75.0 71.0
pH of 10% solution 5.3 5.1 5.5 5.6
Critical relative humidity, % 59.0 53.0 51.0 53.0
Caking tendency, kPa 0 1.9 2.0 3.3
Granule hardness, MPa:
after 1 week 4.2 9.4 7.3 7.9
1 month 4.3 7.0 4.6 6.0
3 months 4.5 8.0 5.3 8.8
6 months 4.9 7.4 5.3 7.0
12 months 3.6 8.9 5.6 6.8
a Samples with addition of micronutrients (%):
0.03 B, 0.015 Mo, 0.001 Co.

ture of the micronutrients lead to the decelerat-
ing of granulation, probably due to the high
magnesium content in the phosphorite sample.
The present laboratory investigations, based
on the reaction of phosphorite rock with sul-
phuric acid, resulted in the demonstration of
conditions, that yielded N P K fertilizer of various
grades and of good quality. The possibility of
realizing three processes without the production
of superphosphate in an intermediate state has
been established. When using Kola apatite, the
products containing urea had a somewhat higher
sum of N + P 2 O s + K 2 0 and usually higher
granule hardness in comparison with the samples
containing a m m o n i u m nitrate. The possibility of
using low quality phosphorite instead of apatite,
has been proved.
Further investigations should be carried out to
get more data for statistical evaluation of trends
observed in this work and to explain relation-
ships between granule hardness, caking and
moisture, as well as the influence of micronut-
rients on the rate of granulation and on fertilizer
quality. Results of small-scale tests ought to be
verified at a continuous pilot plant to elaborate
technology and equipment, including product
finishing techniques, for manufacture of N P K
fertilizers by the above processes.
The processes studied in this work ought to be
preferred to the processes of producing similar
compound fertilizers from the mixtures of single
superphosphate with nitrogen and potassium
salts [4, 13] as more compact, environmentally
more friendly and having no difficulties b o u n d
with the mixing of superphosphate and urea [6].
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