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DOI 10.1007/s40093-016-0139-1
ORIGINAL RESEARCH
Received: 28 June 2016 / Accepted: 21 September 2016 / Published online: 30 September 2016
The Author(s) 2016. This article is published with open access at Springerlink.com
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pollution involves the use of controlled release urea in slow release and decrease the solubility of urea. In one of
which a physical barrier is used to reduce its dissolution these, urea was entrapped in a lignosulfonate-acrylonitrile
rate (Shavit et al. 2003). Controlled release urea is com- graft copolymer matrix (Detroit 1988). Combinations of
monly prepared by coating of granular urea with low per- lignin and ethyl-cellulose were described as controlled
meability hydrophobic material. Suitable coating must release formulations of urea (Fernandez-Perez et al. 2008).
have four properties, including low prices, being The lignosulfonates, Kraft, and Soda lignins were used as
biodegradable, non-toxicity, and high availability. It could coating material for production of coating urea. The
effectively resolve and improve nutrient efficiency while nitrogen release through these coatings was measured and
reducing the environmental hazards (Shavit et al. 1997; compared with uncoated urea granules. To reduce nitrogen
Tomaszewska et al. 2002). Many materials have been release, hydrophobic compounds and crosslinkers were
reported to be used as coatings, such as sulfur, poly- added to the soda flax lignin dispersions. However, com-
ethylene, polysulfone, polyvinyl chloride, polystyrene, plete release of nitrogen still occurred within 1 h (Mulder
polyacrylic acid latex, chitosan, starch, polyvinyl alcohol, et al. 2011).
mixture of gypsum, limestone, cement, sulfur, and zeolite The objective of this work was to develop an econom-
(Blouin et al. 1971; Salman 1989; Al-Zahrani 2000; Hanafi ically feasible and biodegradable layer as coating material
et al. 2000; Jarosiewicz and Tomaszewska 2003; Liang and for urea fertilizer. For this purpose, lignin obtained from
Liu 2006; Lan et al. 2011; Mohd Ibrahim et al. 2014; Kraft and Sulfite black liquor of pulp and paper industries
Eghbali Babadi et al. 2015). The sulfur layer is friable and was selected as raw material. The lignin with interesting
many works have reported the improvement of the coating functional properties was extracted and acetylated by acetic
quality using costly sealants and conditioners (Cole and acid, and then served as coating layer.
Simmons 1992; Choi and Meisen 1997; Liu et al. 2008).
Some of polymeric materials are non-biodegradable, toxic
to the plants, and change the soils pH, which is undesir- Materials and methods
able (Azeem et al. 2014). Recently, the development of
bio-composite-based coating materials obtained from To improve the hydrophobicity property, acetylation
renewable sources has been investigated to obviate the reaction with acetic acid was used to modify sulfate and
disadvantages of non-biodegradability of certain polymer sulfite lignin. This approach is an environmentally friendly
coatings and to offset higher operational costs (Calabria and cost-effective process with the advantages of using
et al. 2012). wastewater of pulp and paper mills. Figure 1 shows a
Lignin is a complex chemical compound and the only schematic description of the experimental procedure.
aromatic polymer present in wood and it is one of the most
abundant biopolymers in nature (Glennie and McCarthy Material
1962). It is an amorphous polymer with a chemical struc-
ture that distinctly differs from the other macromolecular Black liquors from Kraft pulping of spruce (Choka Com-
constituents of wood. Its chemical structure contains phe- pany. Anzali/Iran) and Sulfite process (Chokam Company,
nyl propane units, originating from three aromatic alcohol Mazandaran/Iran) were used as sources of sulfate and
precursors (monolignols), p-coumaryl, coniferyl, and sulfite lignins, respectively. The granular urea was obtained
sinapyl alcohols (Dorrestijn et al. 2000; Boerjan et al. from the Kermanshah Petrochemical Industries Company
2003). During the chemical pulping processes (Kraft, Soda (Iran) which has a nitrogen content of 46.6 % and a particle
and Sulphite), the partially degraded lignin is dissolved in size range of 24 mm (Table 1). Aqueous solution of
the black liquor, from which it can be later isolated by acetic acid (5 %) containing sodium metabisulfite (0.2 %)
different methods. Moreover, the molecular structure and was used as acetylating agents. Dichloromethane and
function groups differ for the various types of lignin ethanol (96 %) were used as the solvents for coating
(Laurichesse and Averous 2014). Lignin is a waste material solution preparation. All chemicals were analytical grade
that may be ideal for application to soil and is one of the (Merck; Germany) and used without further purification.
most slowly decomposing components of dead vegetation,
contributing a major fraction of the material that becomes Methods
humus as it decomposes. The resulting soil humus, in
general, increases the photosynthetic productivity of plant. Extraction and chemical modification of lignin
Moreover, this waste product, when embodied into soil,
reduces the nitrification rate of urea (Stevenson 1982; Flaig Ultra-filtration of black liquor for the extraction of lignin
1984). Several systems, including urea and lignin, that used has been studied in several previous investigations (Wall-
matrix method have been described for the formulation of berg et al. 2003; Wallberg and Jonsson 2003; Holmqvist
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Int J Recycl Org Waste Agricult (2016) 5:289299 291
Table 1 Characterizations of raw materials used for preparation of deionized water and dried at 3540 8C in an oven. The
controlled release urea modified lignin was characterized through FTIR
Materials Amount Unit spectroscopy.
Acetic acid/sodium metabisulfite Two necked flask with a condenser 18 h 80 8C Four times, 60 min, 4000 rpm Brown powder
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292 Int J Recycl Org Waste Agricult (2016) 5:289299
Temperature Thermocouple
Indicator and Controllers Belt heater
Nozzle
Solid particles Air supply
Fluidized bed
Condenser
Hot air in
Air blower
Thermometer
Manual Flask
flow regulator
Oil bath
Electric heater
Flow meter
Heater
Switzerland). Surface morphology of granular urea and of soil, mixed, and kept at the room temperature of
modified lignin coated urea was analyzed by scanning 25 5 8C for 2 months. The humidity of pots soil was
electron microscopy (SEM) and petrographic microscopy controlled around field capacity by weighting method. Soil
(Leica 200M, USA). SEM images were obtained at the samples were collected from three different points in a
required magnification at room temperature. 2 day interval by a narrow glass pipe with a diameter of
4 mm and height of 30 cm and subjected to nitrogen
Nitrogen release test release test. The sampling points were isolated by the
small-opening grid in the way that the samples only con-
To measure the amount of nitrogen release in soil, syn- tained soil and none of synthesized slow release fertilizer
thesized fertilizer (3 g) was added to pot containing 900 g beads.
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The nitrogen release rate of coated urea was measured To measure the nitrogen release from fertilizer, a mass
by the Kjeldahl method using Gerhardt apparatus (James of 10 g coated urea was poured in deionized water
1995). The Kjeldahl digestion converts nitrogen com- (200 ml). Samples (10 ml) were withdrawn during inter-
pounds into ammonia. One gram of sample (soil) is first vals and subjected to the Kjeldahl method concluding the
digested in 10 ml strong sulfuric acid in the presence of 8 g amount of nitrogen released from the fertilizer.
catalyst (containing 96 % potassium sulfate, 3.5 % copper
sulfate, and 0.5 % selenium dioxide) which helps in the
conversion of the nitrogen to ammonium ions. This process Results and discussion
was conducted at 250 C for 30 min then at 410 C for
50 min followed by the addition of water (100 ml) to the Lignin macromolecule contains various functional groups,
solution after settling the temperature to an ambient value. such as methoxyl, hydroxyl, and benzyl alcohol groups,
Ammonium ions were converted to ammonia by raising the and few terminal aldehyde groups (Nikitin 1961). The
temperature to boiling point and the ammonia was trapped hydroxyl functional groups, mainly phenolic and alcoholic
in a solution of 10 ml Boric acid and Bromocresol green hydroxyl groups, may result in an increase hydrophilicity
indicator. Then, nitrogen content was determined by of lignin.
titrating the ammonia solution with a standard solution of FTIR spectra of unmodified lignin extracted from black
sodium hydroxide (0.05 N). liquor and modified lignin are shown in Fig. 3. Some
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characteristic peaks in lignin spectrum can be ascribed as of hydrogen atoms of the hydroxyl groups by acetyl
follows: The distinct band appearing at 640 cm-1 in the groups. The new bond at 1195, 1213, and 1320 cm-1 in
spectra of sulfite lignin (Fig. 3 a) was assigned to the sul- FTIR spectra of acetylated lignin is characteristic of CO
phonic groups formed from the reaction of sodium sulphite stretching vibration of esters and acidic groups. Mean-
with the secondary OH of the aliphatic side chain of lignin while, the peak at 31003500 cm-1 of absorption is
which is not the case in Kraft lignin spectrum. The bond at weakened after acetylation. Therefore, it can be concluded
10431200 cm-1 might be caused by vibration of CO that hydroxyl groups in lignin were acetylated and replaced
bonds in phenolic, alcoholic groups, and by vibration of C by acetyl groups. The absorption at 2934 cm-1, predomi-
OC in ethers groups. The absorption bonds around 1050 nantly, is due to CH stretching in aromatic methoxyl
and 1100 cm-1 are referred to primary and secondary groups. Increase of this peak intensity after modification by
alcoholic groups, respectively. The peaks at 1562 and acetic acid is probably due to addition of methyl and
1640 cm-1 are related to the aromatic structural vibrations. methylene groups to side chains of acetylated lignin.
The bond at 1650 cm-1 is due to stretching vibration of Figure 4 shows the proposed mechanism of acetylation
C=C in alkenes groups. The absorption bonds located in reaction with acetic acid/sodium metabisulfite. A reaction
2916 and 2845 cm-1 wave numbers are caused by CH involving the replacement of the hydrogen atom of a
stretching vibration of the methoxyl groups. The strong hydroxyl group with an acetyl group (CH3CO) yields a
wide absorption bond between 3100 and 3500 cm-1 is specific ester. Acetylation of the lignin leads to a partial or
ascribed to OH stretching vibration, which indicates the full OH bond loss, since OH groups were replaced by ester
presence of alcoholic and phenolic hydroxyl groups groups (CH3COO).
involved in hydrogen bonds. The result of FTIR spectra Figure 5a, b presents graphs and micrographs of the
confirmed that the precipitated material is extracted lignin surface of uncoated urea and lignin coated urea (10 %
which was hydrophilic because of existence many hydroxyl coating) obtained by petrographic microscope and SEM.
groups in its structure. Lower absorption intensity was Lignin coated urea did not show a smooth surface, con-
observed for Kraft Lignin than for Sulfite lignin which is taining irregularities. In addition, crystal structure was
attributed to the high oxidation and degradation power observed on the particle surfaces of lignin coated urea. The
during the two pulping processes (Fig. 3a, b). formation of this crystal structure can be ascribed to phe-
The FTIR spectra of extracted lignin and modified lignin nolate salt crystal. Figure 5c shows the geological images
(Fig. 3c, d) show structural differences between them. The (left) of acetylated lignins and SEM images (right) of urea
acetylation reaction has changed the structure of lignin coated with various percentage of acetylated Kraft lignin
when the main absorption bands (C=O) of acetyl groups layer. Pinholes were clearly seen in samples with 5.0 %
have been appeared distinctly at 17001750 cm-1 that coating. These relatively large pinholes are the principal
related to carboxylic acid group that formed by substitution path for the water diffusion into coated granule and nitrogen
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Fig. 5 Petrographic microscope and SEM images of urea, urea coated with lignin, and modified lignin with acetic acid. a Uncoated urea granule,
b lignin coated urea, and c acetylated lignin coated urea
release. Nutrients become available when the coating spots in the coating are covered by the sealant to moderate
degrades to expose them or when nutrients diffuse through the release rate. The surface of the coated urea became more
small pores in the coating. Particles with thin or imperfect uniform and the pores sizes became smaller as the coating
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percentage increased. Although the surface of the urea coated urea with acetylated Kraft lignin and Sulfite lignin,
coated with 15.0 % coating was not perfectly uniform and the dissolution rate of 88 and 97 % was obtained after 24 h
smooth, it is quite free from visible defects like cracks and for the sample with 5.0 % coating, respectively, whereas
pinholes. The longest delay in release comes from the the corresponding value was 43 and 72 % for the sample
thicker coated particles with no imperfections. Thus, it is with 15.0 % coating. This fact is associated with the
the variability in the particles that provides the sustained reduction in the number of pinholes which are the primary
release of nutrients from coated urea. path for nitrogen release from coated urea. It is important
Complete release of urea coated with Kraft and Sulfite to note that higher the percentage content of coated layer
lignin still occurred within 1 h in water. This can be results in lower release of nitrogen. For all experimental
explained by partly dissolution of urea in the aqueous range, the nitrogen release for urea coated with acetylated
lignin layer during coating process. The reaction of urea Sulfite lignin was more than that of urea coated with
with phenolic hydroxyl groups of lignin results in the acetylated Kraft lignin.
formation of phenolate salt in the coating layer; therefore, To achieve more practical results, the release rate of
the coating layer has a low resistance to water diffusion. nitrogen was investigated in soil collected from agricultural
Release of nitrogen is governed by the thickness of farm in Kermanshah province/Iran (Fig. 7). The release
coating and imperfections in coating surface. Figure 6 rate of nitrogen was more slowly in soil than in water.
shows nitrogen release rate of coated urea with modified However, the same trend was observed for acetylated
lignin for three different coating percentages and in water Sulfite and Kraft lignin. Some of the physical and chemical
medium. The release rate could be controlled by varying properties of the soil are shown in Table 4.
the total amount of coating layer. The dissolution rate To compare the quality of synthesized fertilizer with
decreases with the increase in coating percentage. For available commercial one, an experimental run was
60 60
40 40
5.0 % Coating 5.0 % Coating
20 10.0 % Coating 20 10.0 % Coating
15.0 % Coating 15.0 % Coating
0 0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (h) Time (h)
(a) Sulfite lignin (b) Kraft lignin
lignin
Release rate (%)
60 60
40 40
5.0 % Coating 5.0 % Coating
20 10.0 % Coating 20 10.0 % Coating
15.0 % Coating 15.0 % Coating
0 0
0 4 8 12 16 20 0 4 8 12 16 20
Time (day) Time (day)
(a) Sulfite lignin (b) Kraft lignin
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Table 4 Properties of soil used for release rate of coated urea part is easily broken and increases water penetration into
Parameter Value
granules that cause rapid dissolution of nitrogen.
For the application as a controlled release coating, the
pH 7.20 water resistance is an important feature. The dissolution
Electrical conductivity (ds/m) 0.40 rate of nitrogen reduced significantly for urea coated with
Organic materials (%) 2.11 modified lignin. Probably, acetylation increases the
Nitrogen (%) 0.24 hydrophobicity and thereby reduces the water-sensitivity of
Calcium carbonate equivalent (%) 9.35 lignin coating which results in a decrease of nitrogen
Silt (%) 55.17 release. In this coating layer, only some parts of the alco-
Sand (%) 19.27 holic and phenolic groups were acetylated and the others
Clay (%) 25.56 remained non-acetylated. Acetylated groups are charac-
Texture Silt loam terized by hydrophobicity, while non-acetylated groups
have the ability to establish hydrogen bonds with the
coating surface, and thus, it can enhance the surface
conducted with sulfur coated urea (SCU) synthesized in our
adhesion. FTIR spectra showed that Sulfite lignin is more
laboratory. Figure 8 illustrates the nitrogen release rate for
hydrophilic than Kraft lignin. Due to its hydrophobic nat-
SCU (without using conditioner and sealant) and urea ure and adhesion to the surface, Kraft lignin modified with
coated by modified lignin for three different coating per-
acetic acid/sodium metabisulfite showed the high perfor-
centages. After 7 days, the nitrogen release of SCU in soil
mance as coating material (Fig. 9). Besides the
was more than urea coated with acetylated lignin. The hydrophobicity, the coating quality has the major influence
nitrogen content of SCU has been released almost com-
on the release of urea. The fluidization is a suitable tech-
pletely, after 11 days, whereas this value was 70 % (after
nique to produce a quality product with the uniform coating
18 days) for the urea coated with acetylated Kraft lignin.
layer.
This is probably due to complete coating of urea by
acetylated lignin that prolonged the release time of nitro-
gen. The sulfur coating process is highly temperature
dependent. A small change in coating temperature changes Conclusions
the morphology of sulfur. The sulfur cannot create a per-
fect-uniform coating on the surface of urea and some crack Extracted lignin from Kraft and Sulfite black liquor has the
might be observed on the surface, which makes nitrogen potential to be developed as a coating layer. Urea has been
release un-controllable. Moreover, some regions of the successfully coated with modified lignin to obtain granular
coating are thick and some regions are thin. The thinner coated urea. The key findings of this work are:
100
80
Release rate (%)
60
40
20
0
5 10 15
Coating percentage (%)
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