1070-4272/05/7808-1306 + 2005 Pleiades Publishing, Inc.
Russian Journal of Applied Chemistry, Vol. 78, No. 8, 2005, pp. 1306!1308. Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 8, 2005,
Original Russian Text Copyright + 2005 by Efanov, Dudkin, Galochkin.
AND INDUSTRIAL ORGANIC CHEMISTRY
Mechanochemical Synthesis of Nitrogen-containing
Derivatives of Flax Boon
M. V. Efanov, D. V. Dudkin, and A. I. Galochkin
Altai State University, Barnaul, Russia
Received March 10, 2005; in final form, May 14, 2005
Abstract-The influence exerted by the conditions of the mechanochemical synthesis [time (1003100 min),
air pressure (139 atm), temperature (30390oC), amount of ammonia (0.533.0 g g
raw material)] on the con-
tent of nitrogen and functional groups in the products of oxidative ammonolysis of flax boon was studied.
The resulting products were tested as nitrogen-containing ion exchangers in sorption of heavy metals.
In processing of plant raw materials, the modern
trends are toward integrated chemical processing of
the whole biomass to obtain polymeric compounds
with prescribed properties. One of the ways of utiliz-
ing plant wastes is their use as raw materials for pre-
paring fertilizers and sorbents [1, 2].
To obtain a nitrogen-containing fertilizer from
wood bark, Deineko et al. suggested a process involv-
ing chemical treatment of the plant raw material with
oxygen in aqueous ammonia (oxidative ammonolysis)
. The main disadvantages of this process are high
temperature (753200oC), high oxygen pressure (up to
8 MPa), and relatively low nitrogen content in the
resulting fertilizer (1.033.5%).
Oxidation of lignocarbohydrate materials with
ammonium persulfate in ammonia under mild condi-
tions yielded valuable nitrogen-containing derivatives
suitable as nitrogen-containing organic fertilizers and
ion exchangers . However, commercial use of this
process is restricted by the high cost of ammonium
persulfate and its large consumption. We have devel-
oped a new mechanochemical procedure for preparing
nitrogen-containing derivatives of lignocarbohydrate
materials by oxidation with atmospheric oxygen in
aqueous ammonia .
Flax boon is a fairly valuable plant raw material;
it is available in large amounts as a waste from flax
processing in Altai krai and finds no proper use today.
The possibility of using flax boon oxidation products
as nitrogen-containing organic fertilizers was shown
In this study, we examined how the conditions of
flax boon oxidation with atmospheric oxygen in aque-
ous ammonia affect the composition and properties of
the resulting nitrogen-containing derivatives.
As the raw material we used finely cut flax boon
from the Biisk Flax Joint-Stock Company as air-dry
particles ~0.5 mm in size.
According to chemical analysis , the raw mate-
rial contained 37.2% cellulose, 25.6% hemicellulose,
and 35.8% lignin.
The oxidative ammonolysis was performed as fol-
lows. A 5.0-g sample of air-dry flax boon was placed
in a 300 cm
cylindrical reactor of a vibration mill
(IV-98B vibrator, frequency 2800 cm
) with 15 steel
rods (10 0 100 mm).
The temperature-controlled reactor was charged
with 25% aqueous ammonia in an amount of 0.53
3.0 g of NH
per gram of the raw material, air was
pumped in with a compressor to the final pressure of
139 atm, and the mixture was vigorously milled for
103100 min. The temperature in the reaction chamber
was 30390oC. After the process completion, the prod-
ucts were unloaded, separated from the rods, washed
with water to neutral reaction, and dried in a desic-
cator to constant weight.
The products were analyzed for the content of fixed
nitrogen by the Kjeldahl method , for the content of
carboxy groups by conductometric back-titration, and
for the content of phenolic hydroxy groups by a chem-
isorption method as described in . The sorption
power of the nitrogen-containing flax boon derivatives