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Reducing the release rate of urea can increase its efficiency of use and reduce nitrogen
Article history:
pollution. A slow-release urea (S-urea) was produced using a new method; a bentonite and
organic polymer (OP) were used to form a three-dimensional lattice structure by melting urea
directly. The structure affected the recrystallisation of urea and increased its stacking density.
28 September 2012
The specific surface area of S-urea was 0.046 m2 g1, much lower than that of common urea
(1.698 m2 g1). The static release experiment showed that 75% of 12 g sample of S-urea was
released in 1 l water for about 14 h, much longer than that of common urea (<0.5 h). The kinetic
simulation results showed that the release of S-urea was not based on Fickian diffusion but
underwent anomalous diffusion with its release rate was mainly affected by the dissolvingeroding process of the medium which was controlled by the compactness of the lattice
structure. This process may be strengthened by increasing the amount of bentonite.
2013 IAgrE. Published by Elsevier Ltd. All rights reserved.
1.
Introduction
b i o s y s t e m s e n g i n e e r i n g 1 1 5 ( 2 0 1 3 ) 2 7 4 e2 8 2
Nomenclature
Symbols
A
Absorbency value
C
Constant incorporating the characteristics of the
adsorption of N2
Ct
Concentration of urea at time t (mg ml1)
k
Constant of the carrier-active agent system
Diffusion constant
k1
Dissolving-erosion constant
k2
m
Diffusion exponent
n
Diffusion exponent
P
Partial pressure of N2 (Pa)
Saturated vapour pressure of liquid N2 (Pa)
P0
Fraction of active agent released at time t
Qt
Coefficient of determination
R2
developing countries consume more and more nitrogen fertiliser and yet have only 20e35% efficiency of nitrogen use
(Fan & Liao, 1998; Jiang, Hu, Sun, & Huang, 2010).
In this study a novel slow-release urea (S-urea) is presented whose structure and release mechanism is quite
different from that of coated urea. The formulation forms a
three-dimensional lattice structure in the urea solution that
could influence its release process (Cai et al., 2009; Chinese
Patent Specification ZL200610040631.1, 2006). The method of
production is developed by melting urea directly and using
bentonite which is a cheap and safe material as a main
substrate (Chinese Patent Specification CN201110003090.6,
2011). This new type of urea can reduce costs greatly since
it increases cost only by about 30e50U t1 above common
urea and it is much cheaper than coated urea
(200e2000U t1). This improvement should make this new
technique popular, particularly in developing countries. In
order to investigate the slow-release mechanism of this
new type of urea, its structure was analysed using infrared
spectra (IR), scanning electron microscopy (SEM), X-ray
diffraction (XRD) techniques and a static release experiment
designed mainly according to the model of Higuchi (1963).
The affect of the proportion of additives was tested using
the release kinetics data and the results simulated using the
equation of Peppas (Lenaerts, Dumoulin, & Mateescu, 1991;
Peppas, 1985) and the double-exponent equation (Kaunisto,
Marucci, Borgquist, & Axelsson, 2011; Peppas & Sahlin,
1989).
2.
2.1.
Materials
t
V
Vm
275
Time (h)
Total gas volume adsorbed by sample (ml)
Gas volume adsorbed by monolayer of sample (ml)
Abbreviations
BET
Brunauer, Emmett, & Teller equation to calculate
specific surface area B-urea Urea added with
bentonite
IR
Infrared spectra
OP
Organic polymer
P-urea Urea added with organic polymer.
SEM
Scanning electron microscopy
S-urea Slow-release urea added with bentonite and
organic polymer
XRD
X-ray diffraction
2.2.
Preparation of bentonite-urea (B-urea), organic
polymer-urea (P-urea) and slow-release urea (S-urea)
A quantity of bentonite (5%) was prepared and mixed equally in
the melting urea according to the method in Chinese Patent
Specification (CN201110003090.6). The admixture was taken
into a mould and recrystallised at room temperature; the final
product (B-urea) was dried at 80 C for 8 h before use. Using a
quantity of OP (0.15%) to replace the bentonite and the final
product (P-urea) was also dried at 80 C for 8 h before use.
OP with a proportion of bentonite (from 1% to 5%) was added
to the urea and mixed according to the same method. The final
product of S-urea was dried at 80 C for 8 h before use.
2.3.
VP0 P Vm C Vm C P0
where P is partial pressure of N2 (Pa); P0 is saturated vapour
pressure of liquid N2 (Pa); Vm is the gas volume adsorbed by
monolayer of sample (ml); V is the total gas volume adsorbed
by sample (ml); C is a constant incorporating the characteristics of the adsorption.
2.4.
276
b i o s y s t e m s e n g i n e e r i n g 1 1 5 ( 2 0 1 3 ) 2 7 4 e2 8 2
(2)
2.6.
different types of urea (common urea, P-urea, B-urea and Surea) were poured into a pipe which was 100 mm long and
10 mm inside diameter with one end closed. After the urea
recrystallised at room temperature the pipe was placed horizontally with 1 l water in the apparatus.
The components of the apparatus were assembled
together according to Fig. 1. The speed of magnetic stirrer was
10 revolutions s1 that should have ensured that the concentration of the solution was uniform and not affecting
diffusion. At given time intervals the concentration of urea at
3 different positions in the centre of the vessel was determined. The water temperature was controlled at 25 C and the
pipe was turned 90 every 15 min to keep the area of the
interface constant. All the results were based on three
replicates.
2.5.
(1)
2.7.
Ct 3:7487 A 0:0171 mg ml
2.8.
Statistical method
The statistical results and the nonlinear fit of Eq. (1) and Eq. (2)
were calculated using Origin software (Origin 8.725, Originlab
Company, USA).
3.
3.1.
b i o s y s t e m s e n g i n e e r i n g 1 1 5 ( 2 0 1 3 ) 2 7 4 e2 8 2
277
Fig. 2 e SEM images of the morphology and physical structure. (A and B) the surface of common urea, (C and D) the surface of
S-urea.
3.2.
Analysis of the physical and chemical character of
S-urea
The IR spectra of S-urea sample were similar to that of common urea (Fig. 3A). The peaks at 3447 and 3343 cm1 of common urea as well as of S-urea could be assigned to asymmetric
and symmetric stretching vibration of NH2. The peak at
3250 cm1 of both the two types of urea can be assigned to
OeH vibration of absorbed water. The peak at 1688 cm1 can
be assigned to carbonyl (C]O) and 1613 cm1 peak can be
assigned to NeH bending vibration and CeH stretching vibration (mainly NeH bending vibration domain) of O]CeNH2
(He et al., 2007; Xie et al., 2011). In the finger print zone of
1500e400 cm1, all the peaks were similar.
The peaks of 3430 and 1641 cm1 for bentonite can be
assigned to OeH vibration of absorbed water. The peak at
1041 cm1 can be assigned to SieO vibration (Chen, Yang, Luo,
& Lu, 2002). It showed that there might be no chemical reaction during the mixing process and the mixture of molecules
could connect with each other mainly by some physical
attraction such as the Van der Waals force, hydrogen bond
and electrostatic attraction.
The results from X-ray diffraction of common urea and Surea samples are shown in Fig. 3B. Both the samples had the
similar diffraction angle (2q). S-urea had a sharp peak at
22.28 , it was a little less intense than that of common urea at
22.33 , it showed that S-urea had a tighter arrangement of
molecules than common urea using the Bragg calculation
(Ding & Liu, 1998; Zheng, Zhang, Cai, Fu, & Wang, 2005). That
might be because the bentonite was inserted between the gap
in the urea crystals and this influenced its process of
recrystallisation.
The pore size distribution of common urea and S-urea were
obtained by N2 adsorption and desorption experiment and the
specific surface area was calculated using BET equation. As
shown in Fig. 4A, the shaded area indicates the final volume of N2
adsorbed by the sample, the larger shaded area the larger the
surface area. The surface area of common urea was much larger
than that of S-urea. With increasing N2 pressures more gas
comes into contact with the smaller pores and is adsorbed, the
shaded area under the differential relative pressure indicates the
amount of the pore sizes and their proportion. It indicates that
the pore size of S-urea is distributed mainly in a smaller size
range. The specific surface areas of the two forms of urea were
calculated and this is shown in Fig. 4B; common urea was
1.698 m2 g1 and S-urea was 0.046 m2 g1. This result shows that
S-urea has a more compact structure. This reinforces the conclusions that the two additives occupy the potential space inside
urea and form a compact lattice structure with network connections that should greatly decrease the specific surface area.
3.3.
The static release experiment was carried out with the samples of common urea, P-urea, B-urea and S-urea respectively
using the apparatus shown in Fig. 1. The releasing process of
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b i o s y s t e m s e n g i n e e r i n g 1 1 5 ( 2 0 1 3 ) 2 7 4 e2 8 2
3.4.
Bentonite was the main additive that could influence the release
rate of S-urea, the static release experiment was carried out with
b i o s y s t e m s e n g i n e e r i n g 1 1 5 ( 2 0 1 3 ) 2 7 4 e2 8 2
3.5.
279
(Fig. 6A) and Eq. (2) (Fig. 6B). The parameters of Eq. (1) were
characterised by the values of k was 7.5939 and n was 0.8687
(with R2 0.9988), indicating that the release of S-urea did not
agree with the Higuchi model. That suggests that the release
of S-urea should not vary with the square root of time, as with
Fickian diffusion, but as with anomalous diffusion (Peppas,
1985; Peppas & Sahlin, 1989). Using Eq. (2) supported this
point and differentiated the mechanism from the Fickian
diffusion and dissolving-erosion diffusion by the values of
k1 0.5650, k2 7.1202 and m 0.4421 (with R2 0.9988). The
ratio k2t2m divided k1tm was 39.52 at 13 h (75% of the total
amount of urea), this showed that the dissolution of the
auxiliary frame eroded by water was the main factor controlling the release (Kaunisto et al., 2011; Peppas & Sahlin,
1989).
The data for all the types of urea shown in Fig. 5A were
correlated using Eq. (1) and Eq. (2). The kinetic parameters are
shown in Table. 1.
The correlation results of Eq. (1) showed that the release
mode of all the types of urea tested was not Fickian diffusion
but anomalous diffusion. It indicated that, even including the
sample of common urea, all of the release process was
controlled not only by the concentration diffusion but also by
some other mechanism that may be associated with the
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b i o s y s t e m s e n g i n e e r i n g 1 1 5 ( 2 0 1 3 ) 2 7 4 e2 8 2
Urea
P-urea
B-urea
S-urea
Kinetic parameters
for Equation (1)
Kinetic parameters
for Equation (2)
R2
Ratioa
R2
0.8245
0.9104
0.9647
0.8687
0.9472
0.9955
0.9954
0.9988
0.37b
2.62b
8.93c
39.52c
0.9968
0.9988
0.9952
0.9988
3.6.
Slow-release effect of S-urea under practical
conditions
The result of Fig. 7 shows that during the first 4 days, the
quantity of urea and total N in leaching solution of S-urea
was much less than that of common urea; it was about only
half of the latter. Also the remaining nutrition in soil of Surea provided a steady release velocity during the next 10
days as common urea did. This result shows that S-urea
might have some slow release effect under practical conditions and this affect may last longer in soil than it does in
water. It greatly increases the feasibility of using S-urea in
agricultural production. The reason might be that OP can
connect between the soil particles during the release process
as it did with bentonite, in this way the local circumstances
in the soil around the fertiliser might be changed and it could
affect the diffusion of water and change the process of
nutrition.
Urea
SeU(1%)
SeU(3%)
SeU(5%)
Kinetic parameters
for Equation (1)
Kinetic parameters
for Equation (2)
R2
Ratioa
R2
0.8245
0.9979
0.7548
0.8687
0.9472
0.9928
0.9976
0.9988
0.37b
0.60c
7.41c
39.52c
0.9968
0.9936
0.9976
0.9988
b i o s y s t e m s e n g i n e e r i n g 1 1 5 ( 2 0 1 3 ) 2 7 4 e2 8 2
4.
Conclusions
Acknowledgement
We thank Dr. Fanghua Li for his valuable discussions and careful
revisions. This work was supported by the National Agriculture
Transformation Fund of China (No. 2010GB2C300185) and the
Directional Project of Chinese Academy of Sciences.
references
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