International Journal of Agriculture and Environmental Research

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International Journal of Agriculture and Environmental Research

ISSN: 2455-6939

Volume:03, Issue:04 "July-August 2017"

www.ijaer.in

Page 3429

CATALYTIC PROCESSING OF PLANT WASTE RESULTS

IN PULP AND LIQUID PRODUCTS CAPABLE OF REGULATING

THE GROWTH OF PLANTS

Irina F. Rusina*, Zoya S. Kartasheva, Leonid M. Pisarenko, Olga T. Kasaikina., Ludmila M.

Apasheva, Natalia A. Rubtsova, Anton V. Lobanov.

N.N. Semenov Institute of Chemical Physics RAS, Kosygin str., 4, 119991 Moscow, Russia

*Corresponding author

ABSTRACT

We previously developed a simple biomimetic model of the enzyme complex for the catalytic

decomposition of organic plant waste. The catalyst is based on iron (III) oxides, obtained by

hydrolysis of Fe (III) salts in water in the presence of a surfactant. It decomposes H2O2 actively

and catalyzes the oxidative destruction of lignobiomass under atmospheric pressure in water

media at mild temperature (60-70° C). The oxidative destruction of biomass results in dissolved

in liquid phase low molecular oxidation products derived from lignin, hemicellulose, lipoproteins

and sugars and the solid residue which represent mainly cellulose. The influence of liquid phase

products (LPP) on the growth and development of plants was studied оn the following crops:

sorghum (Sorghum сaffrorum Beauv., Jakuschev), oat (Avéna sativa L), wheat Inna (Tríticum

aestivum L), pea (Pisum sativum L) and potatoes (Solánum tuberósum L). The treatment of

agriculture plants by the liquid fraction of the products of catalytic oxidation of lignobiomass

was found to have a positive effect on the development of plants and can be used as a growth-

stimulating factor in crop production.

Keywords: catalytic oxidation, lignobiomass, iron(III) oxides, plant growth stimulation

1. INTRODUCTION

Recycling of organic wastes and biomasses is a significant scientific and technical problem

(Kuznetsov and Gradova, 2006; Michel, 2012). Currently, direct combustion is used, but, at the

same time, technologies of thermochemical processing of biomasses, such as gasification and

pyrolysis are being developed. In recent decades considerable attention has been paid to the

International Journal of Agriculture and Environmental Research

ISSN: 2455-6939

Volume:03, Issue:04 "July-August 2017"

www.ijaer.in

Page 3430

chemical processing of biomasses to biofuels. This trend is developing, despite the reasonable

objection that the production of biofuels from biomasses is fundamentally uneconomic. It

requires a lot of energy and increases, in the end, the production of CO2; therefore, it is

preferable to recycle the biomass by direct combustion or processing in the chemical and

pharmaceutical production of commercial products, (Michel, 2012).

In nature, lignin-containing biomass is processed by microorganisms, for their development,

reproduction and functioning water, containing metal ions is necessary (Kirk, 1984; Boerjan and

Ralph, 2003).

We have developed a simple biomimetic model of the enzyme complex for the catalytic

oxidative decomposition of organic plant waste with the use of H

and/or oxygen as the

oxidant. The catalyst is a fine dispersion of iron (III) oxide and hydroxide with inclusions of

silicon and carbon (Kasaikina et al., 2012; Kasaikina et al., 2013; .Kasaikina et al., 2014; Lesin

et al., 2011; Pisarenko et, al., 2014). The catalyst, adsorbed on the waste surface, actively

decomposes H

O

2

into free radicals and destroys the solid waste via catalytic oxidation.

2. MATERIALS AND METHODS

The catalyst was prepared by hydrolysis of iron (III) chloride in water (Kasaikina et al., 2014).

The processing of wood shavings and other plant materials was carried out in a stainless steel

reaction vessel filled with 3 liters of a water solution containing



1M H

. During the reaction,

samples were taken, in which the concentrations of H

O

2

and acids were determined by the

iodometric method and titration with alcoholic KOH solution accordingly. The escape of ions

Fe(III) and Fe(II) to the volume of aqueous phase was controlled by specific qualitative reactions

with potassium thiocyanates, red and yellow blood salts respectively. The IR spectra of the

reaction products were recorded on a Perkin-Elmer FTIR-1725 spectrometer, equipped with a

special attachment for the recording of spectra of diffuse reflection.

3. RESULTS AND DISCUSSION

3.1. Catalytic process and products description

Using H

as the oxidizing agent, catalyst, located on the surface of the biomass, sharply

increases the rate of generation of radicals which react with macromolecules of biomass and

initiate their degradation. The ability of hydrogen peroxide to form oxo- and peroxo-complexes

with iron and copper, and to hydroxylate organic compounds is well known (Carvalho and Horn,

2006; Elizarova et al., 2000; Kozlov et al., 2003). Catalytic oxidation of biomacromolecules

facilitates their biodegradation.

International Journal of Agriculture and Environmental Research

ISSN: 2455-6939

Volume:03, Issue:04 "July-August 2017"

www.ijaer.in

Page 3431

As a result of the oxidative degradation of wooden biomass, first of all, lignin and hemicellulose

are oxidized and washed away from the surface. During this process cellulose also partially

oxidizes, supplying the solution with polyols, hydroxy acids, oligosaccharides, and esters

(Harmsen et al., 2010; Pisarenko et al., 2014; Zhao et al., 2012).

After all H

O

2

had been consumed, the solid residue was separated from the aqueous solution by

filtration and then centrifugation, followed by drying in flowing air. For qualitied (by FTIR) and

quantitative analysis of content, water-soluble non-volatile products of oxidative degradation

were isolated from the aliquot of liquid phase by evaporation in a current of warm air.

The catalytic process of thermo-oxidative treatment of biomasses leads to the formation of low

molecular oxidation products of hemicellulose, lignin, and lipoproteins. The solid residue

contains mainly cellulose and its derivatives. The yield of solid residue depends on the nature of

the biomasses (see Table 1), the ratio biomass: H

O

2

: catalyst and the processing time. In the

presence of adequate concentrations of hydrogen peroxide, pure cellulose with a qualification E-

460 is produced via the processing of fir and pine wood shavings that is suitable for the food and

pharmaceutical industries. Water phase contains low molecular oxidation products.

Fig.1. IR spectra of products of processing of pine shavings: upper blue graph - the solid

product: red lower graph - water-soluble product obtained after evaporation of the water.

The results of catalytic processing of vegetable raw materials of a different nature are given in

Table 1.

International Journal of Agriculture and Environmental Research

ISSN: 2455-6939

Volume:03, Issue:04 "July-August 2017"

www.ijaer.in

Page 3432

Table 1. The influence of biomass nature on the yield of main products

Biomass

Cellulose(%)*

Water-soluble products (%)*

Acid, mmol/g**

Pine sawdust

Eucalyptus chips

Oat straw

Rice straw

Waste of flax treatment

*In the ratio to amount of the initial biomass; ** the ratio of total acid content in water phase (mmol) to the

amount of biomass (g)

At the end of processing, water phase contains various acids pH



2-2.5. We have found that after

neutralization to a pH 5-6, products of wooden biomass (solid and water-soluble products) can

be applied as a useful nutritional additive to soils and stimulant for plant growth. In experiments

on plants, liquid phase products (LPP) were used, neutralized to a pH 6 by treatment with sodium

or potassium bicarbonate.

3.2 The effect of catalytic processing products on the growth and development of plants

The effect of catalytic processing products on the growth and development of plants was studied

on the following crops: sorghum Pischevoe-614 (Sorghum сaffrorum Beauv., Jakuschev), oat

Kormovoy (Avéna sativa L), wheat Inna(Tríticum aestivum L), pea Sakharny (Pisum sativum L)

and potatoes Udacha (Solánum tuberósum L).

3.2.1 Oats and sorghum

Table 2 shows the results of the influence of the liquid fraction of processed products of wooden

biomass on the growth of green masses in cultures of oats and sorghum. Seeds of sorghum and

oats were soaked in water (control) and in an aqueous solution of the liquid fraction at a dilution

of (1:10) before seedlings emerged. Sprouted seeds were sown in an environment of “Agronom”,

a peat soil used for the cultivation of seedlings, with pH 5,0 – 6,5. In the control, there was peat

soil moistened with water, but in the experiment, the soil was moistened with a solution of the

liquid fraction diluted with water at a ratio of (1:10). On the 22-nd day of cultivation all green

mass was weighed, and after was dried in a current of warm air until there was a constant weight.

International Journal of Agriculture and Environmental Research

ISSN: 2455-6939

Volume:03, Issue:04 "July-August 2017"

www.ijaer.in

Page 3433

Table 2. The influence of the liquid fraction of catalytic oxidation products of wooden

biomass on the growth of green masses of cereals.

Cereals

Green weight

control, g

Green mass

of experience,

Gain (relative

to control), %

Dry mass,

control, g

Dry mass,

experiment, g

Gain (relative

to control), %

Oats

9,83

14,8

151

0,92

1,45

157

Sorghum

6,22

7,96

128

0,74

0,98

132

The Table 2. shows, that the growth of both green and dried mass of plant stems treated with

10% LPP water solution is 157% for oat and 132% for sorghum.

3.2.2 Potatoes tubers and etiolated tuberous cuttings

For the experiment, potato tubers Udacha of a specific size were selected: 3 to 4 cm in mах.

dimension, which were then planted in the cultivation medium. The control tubers were planted

in sand moistened with water, while the experiment tubers were planted in sand moistened with

LPP water solution. The tubers were then placed in a dark chamber with the temperature of 10 –

12° C. In 45 days the sprouted tubers were counted.

Each experiment involved the planting of 20 tubers. The tubers were counted if their sprouts

were at least 1 mm. long. The results are shown in Table 3.

Table 3. The effect of LPP on the sprouting of potato tubers

Variant of the experiment

Number of sprouted tubers, (%)

Control tubers (moistened with water)

Experiment tubers (moistened with LPP 1:0)

None

Experiment tubers (moistened with 1:1 LPP: water solution)

Experiment tubers (moistened with 1:10 LPP water solution)

Table 3 shows that the treatment with 10% LPP water solution leads to a six-fold increase in the

number of sprouted potato tubers as against control tubers. The use of more concentrated

solutions (1:1) and (1:0) has led to a dramatic inhibition of potato sprouting.

International Journal of Agriculture and Environmental Research

ISSN: 2455-6939

Volume:03, Issue:04 "July-August 2017"

www.ijaer.in

Page 3434

In order to produce etiolated tuberous cuttings, the tubers of potatoes Udacha were placed in a

dark chamber until the sprouts were 6 to 8 cm long and 0.5 cm in diameter. Then they were

separated from tubers and, by 30 pieces each, were placed in cultivation media. Control sprouts

were planted in vessels filled with water, while the experiment sprouts were placed in vessels

filled with LPP solutions. The vessels were placed in a luminostat with a light-darkness mode set

to 12:12 hours. In 15 days, the cuttings that had formed a developed root system were counted.

The results are presented in Table 4.

Table 4. The effect of LPP on the formation of root system of etiolated tuberous cuttings

Variant of the experiment

Number of etiolated cuttings that formed roots, %

Control tubers (planted in water)

Experiment tubers (planted in undiluted LPP)

Experiment tubers (planted in 1:10 LPP water solution)

Table 4 shows that the placement of tubers into 10% LPP water solution leads to a four-fold

increase in the number of etiolated cuttings that have formed root system, as against control

cuttings. The cultivation tubers in the undiluted LPP medium resulted in a sharp inhibition of the

root formation (five-fold decrease as against control sprouts).

3.2.3 Wheat and pea

Germination of Inna wheat seeds and Sakharny pea has been studied as follows. The wheat and

pea seeds were placed in a growing medium. Control seeds were planted in sand moistened with

water, while experiment seeds were planted in sand moistened with original undiluted LPP and

(1:10) LPP water solution. The results are shown in Table 5.

Table 5. The effect of treatment with undiluted LPP and (1:10) LPP solution on the

germination of wheat and pea seeds.

Variant of the experiment

Number of sprouted wheat

seeds, (%)

Number of sprouted pea seeds,

(%)

Control seeds (planted in sand

moistened with water)

Experiment seeds (planted in

sand moistened with (1:10)

LPP solution)

Experiment seeds (planted in

sand moistened with undiluted

LPP)

International Journal of Agriculture and Environmental Research

ISSN: 2455-6939

Volume:03, Issue:04 "July-August 2017"

www.ijaer.in

Page 3435

Table 5 shows that the treatment with 10% LPP solution leads to a 1.75 increase in the number

of wheat germs and 1.8 increase in the number of pea seedlings, as against control seeds. The use

of original LPP without dilution has led to a sharp inhibition of seed germination in both

examined cultures.

4. CONCLUSIONS

Thus, the data obtained show that neutralized to pH 6 liquid water-soluble products resulted from

catalytic oxidative processing of plant biomass can be used in agriculture for a growth

stimulation.

It is known, growth stimulation or inhibition properties of most growth regulators are determined

by the concentrations used. In our experiments, the maximum stimulation effect on the

germination and subsequent development of plants was obtained in diluted solutions using 1:10

and 1:20 solutions of LPP diluted with tap water. The use of more concentrated LPP solutions —

1:5 and 1:1 — has led to inhibition of both seed germination and further development of plants.

This latter effect also appears important, as long as more concentrated LPP solutions can be used

for the treatment of vegetable crops and plant intended for long-term storage. It is well

understood for potato tuber treatment: the acceleration of potato tuber germination occurs at low

doses (10%) LPP, and inhibition of germination at higher LPP concentrations (>50%), which is

useful for a long storage of potatoes.

Thus, the application of catalytic oxidative treatment of waste biomass facilitates the solution of

two problems: the utilization of agricultural wastes and the improvement of the agricultural, and

greenhouse soils by returning to the soil the chemicals needed by the plants.

REFERENCES

Boerjan, W., Ralph, J. and Baucher, M. (2003), “Lignin biosynthesis”, Annual Review of plant

Biology, 54, pp.519-546.

Carvalho, N.M.F., Horn, A. Jr. and Antunes, O.A.C. (2006),“Cyclohexane oxidation catalyzed

by mononuclear iron (III) complexes.” Applied Catalysis A, V. 305, № 2, pp. 140-145.

Elizarova, G.L., Matvienko, L.G. and Parmon, V.N. (2000), “Iron Hydroxides. New Catalysts for

Oxidation Reactions in Aqueous Solutions”. Kinetics and Catalysis, V. 41, N. 6, pp.760-

766.

International Journal of Agriculture and Environmental Research

ISSN: 2455-6939

Volume:03, Issue:04 "July-August 2017"

www.ijaer.in

Page 3436

Harmsen, P.F.H., Huijgen, W.J., Bermudez, L.M. and Bakker, X R.S. (2010), Literature review

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