RU2618274C1 - Solid fraction of product of oxidative cracking of vegetable raw material waste as water-accumulating nutrition additive for soil - Google Patents

Abstract

FIELD: agriculture.

SUBSTANCE: water-accumulating nutritional additive for soil represents a solid fraction of the product of oxidative cracking of vegetable raw material waste, obtained by the treatment of vegetable raw material waste in water at room temperature with hydrogen peroxide in the presence of a catalyst based on trivalent iron oxide. The mass ratio of hydrogen peroxide to vegetable raw material waste is 0.5-1.0:1. The amount of the catalyst is 0.1-0.3% by weight with respect to the vegetable raw material waste in terms of Fe³⁺. The catalyst is obtained by heating at 60-70°C the mixture of FeCl₃⋅6H₂O, Na₂CO₃ and 0.5-1.0% aqueous ethanol with the following component ratio, wt %: FeCl₃⋅6H₂O - 0.1-0.2; Na₂CO₃ - 0.05-0.1; 0.5-1.0% aqueous ethanol - the rest. The additive for soil is characterized by the iron content of 0.03-0.04 wt %.

EFFECT: additive is provided, having high water-accumulating properties, which is sterile and environmentally safe.

2 cl, 7 tbl, 11 ex

Description

The invention relates to agriculture and soil science, in particular to substances that improve the condition of the soil, and can be used in crop production both in closed ground and in open areas.

Currently, there are serious contradictions between the growth of the achievements of technical civilization and the rapid depletion of soils. Humanity is in absolute dependence on the state of soils (Zhirmunskaya N.M. Secrets of fertile soil. M., Dilya, 2010). The problem of improving the condition of the soil and enriching it with useful additives for the successful cultivation of plants has existed for a long time, they are trying to solve it by different methods. The oldest way is to introduce manure and wood ash into the soil. In modern conditions, due to the shortage of these components for large areas, the method is not available.

A large number of various modifying additives are known, both of natural origin and synthetic, used to improve the structural and nutritional properties of the soil.

There is a method of increasing the fertility of sandy soils described in patent RU 2265980, A01B 79/02, A01C 21/00, 20.12.2005, which consists in plowing clay in the soil at a dose of 25-50 t / ha. This method is simple and low cost, can increase the clay content in the soil, but is ineffective for improving the nutritional regime of the soil.

A method is proposed for reclamation of sandy soils in the semi-desert zone by introducing into the soil to the depth of the seed layer a nutrient moisture-accumulating additive in the form of an aqueous mixture containing moisture-accumulating plant residues (straw, wood waste, peat) and nutrient filler (humus, biocompost, sapropel, clay and mineral fertilizers and / or trace elements) (RU 2557618, C09K 17/00, 07/27/2015). The method provides increased moisture and soil fertility, but requires the preparation of a multicomponent mixture, therefore, it is rather complicated and expensive.

Modern agriculture consumes almost 2/3 of the world's water consumption, so a lot of researchers pay attention to the development of additives with moisture-accumulating properties.

Known methods for increasing the water resistance of the soil structure by introducing a modifier - polyoxyethylene (20) sorbitan monostearate (RU 2430953, C09K 17/14, 10/10/2011; RU 2527784, C09K 17/42, 09/10/2014). These methods are not effective enough.

Polymers are known that are capable of preserving large amounts of water and its subsequent gradual release. Such polymers include ultra-absorbent polymers, the so-called SAP, which are, for example, crosslinked acrylic acid / acrylamide-based copolymers with salt-forming groups. The size of polymer particles should be less than 1-3 mm, since their absorption of water increases proportionally with decreasing particle size, but the use of such a fine powder is extremely difficult, both in greenhouses and in the open air.

In the patent RU 2531607, C05G 3/00, 10.27.2014, an agrotechnical composition in the form of granules is proposed as a moisture storage additive for soil based on ultra-absorbent polymer (SAP) (crosslinked acrylic acid / acrylamide copolymer) - prototype. The composition also contains hygroscopic material of plant origin (cereal fibers, peat and / or rice husk, core of the corncob) and natural plasticizer of mineral (bentonite, zeolite, stone flour) or vegetable (starch, flour, corncob core) origin. The composition may contain water in an amount not exceeding 20-30%.

The main disadvantage of the composition of the prototype is the complex composition and complexity of the technology for producing additives in the form of granules. In addition, the use of polymers in growing agricultural plants over large areas is undesirable for environmental reasons.

The objective of the invention is the creation of an effective moisture-accumulating nutrient additive for soil based on a product of plant origin, simpler in composition and production technology and environmentally friendly both at the application stage and upon receipt, thanks to environmentally friendly technology.

The solution to this problem is achieved by the proposed moisture-accumulating nutrient additive for the soil, which is a solid fraction of the product of oxidative cracking of plant waste products obtained by treating plant waste products in water at room temperature with hydrogen peroxide at a mass ratio of hydrogen peroxide to plant waste products of 0.5-1.0 : 1 in the presence of a catalyst based on ferric oxide in an amount of 0.1-0.3 wt.% In relation to the waste of plant materials in terms of Fe ³⁺ , the catalyst obtained by heating at 60-70 ° C a mixture of FeCl ₃ ⋅ 6H ₂ O, Na ₂ CO ₃ and 0.5-1.0% aqueous ethanol in the following ratio, wt.%:

FeCl ₃ ⋅ 6H ₂ O 0.1-0.2 Na ₂ CO ₃ 0.05-0.1 0.1-1.0% aqueous ethanol rest

and isolated by centrifugation, while the moisture-accumulating nutrient additive for the soil is characterized by an iron content of 0.03-0.04 wt.%.

Treatment of waste plant materials in water with hydrogen peroxide in the presence of a catalyst can be carried out in a 12-20-fold mass excess of water relative to waste plant materials.

The oxidation of organic materials in the presence of a ferric oxide catalyst was the subject of earlier studies of the authors of the present invention (RU 2425715, B01J 37/04, 08/10/2011; RU 2488445, B01J 37/04, 07/27/2013; RU 2515319, D21C 3 / 00, B01J 37/04, 05/10/2014). It was found (RU 2425715) that the catalyst used is a suspension of colloidal solid particles of iron oxides containing organic impurities (in particular ethyl alcohol).

When creating the present invention, detailed studies were carried out on the effect of various parameters of the process of oxidative cracking of plant waste products (sawdust, straw, flax fire, husk of rice seeds, buckwheat and sunflower, pulp, etc.) on the yield and properties of the solid fraction of the reaction product.

As a result, it was found that in order to achieve the maximum yield of the solid fraction, deep cracking of plant materials is not required (accompanied by an increase in the yield of the liquid fraction), which significantly reduced the amount of reagents used and developed the technology for producing the proposed moisture-accumulating nutritional supplement for the soil.

The proposed moisture-accumulating nutrient additive for the soil — the solid fraction of the product of the soft catalytic oxidation of plant waste products — is cellulose enriched in iron, poly- and oligosaccharides, mixed with lignin and organic substances from the liquid fraction of oxidative cracking (a mixture of organic acids, their esters, polyphenols and sugars )

The high sorption properties of cellulose, which is the basis of the proposed moisture-accumulating nutrient additives (CDs) for the soil, allow soil moisture to be stored and trace elements to accumulate, which leads to an increase in soil fertility. The above substances contained in the proposed CD for soils also contribute to a more efficient development of plants. Iron is vital for the development of all living things, plants need iron for the formation of chlorophyll and photosynthesis, it is absorbed by plants and contained in plant tissues in the greatest amount compared to other metals, in the soil iron forms organomineral complexes with humic acids, which contributes to the formation of water-resistant soil structures (L.A. Krasilnikova, O.A. Avksentieva, V.V. Zhmurko et al. Plant biochemistry. Rostov n / A, Phoenix, 2004, 224 p.). Poly- and oligosaccharides have growth-promoting properties (RU 2110177, A01N 65/00, С07Н 1/08, 05/10/1998).

Unlike most natural additives for the soil (manure, humus, sapropel), the proposed CD is sterile, since the process of its production takes place in an aqueous solution of hydrogen peroxide, which has disinfecting properties.

It should be noted that upon receipt of the proposed soil supplement, the problem of disposing of waste from the agricultural and forest processing industries is simultaneously solved.

The proposed CD for the soil is obtained as follows.

At a temperature of 60-70 ° C, a mixture of FeCl ₃ ⋅ 6H ₂ O, Na ₂ CO ₃ and 0.1-1% aqueous ethanol is stirred. Leave the mixture until the colloidal catalyst is completely precipitated, mix again, add the waste from plant materials, add water and add perhydrol (30% aqueous solution of hydrogen peroxide). Stir the resulting mixture at room temperature until the hydrogen peroxide is completely consumed, and CD — the solid fraction of the oxidation product — is isolated by centrifugation. To determine the iron content and yield, the CD is dried to constant weight.

Iron was determined spectrophotometrically by the following procedure.

. Содержание железа в мас.% рассчитывают по формуле:

.A portion of m (0.05-0.50 g) of dried CD is mixed with 5 ml of (V ₁ ) 0.2 M hydrochloric acid, incubated for 30-40 minutes in an ultrasonic disperser and the aqueous extract is separated, (V _x ) ml (0.18-0.25 ml) of the resulting solution, containing iron, is added to a 2 ml (V ₀ ) 2 M solution of potassium thiocyanate in 0.2 M hydrochloric acid and the absorbance (D) is measured in a 1-centimeter cuvette at the absorption maximum at 480 nm of the complex compound of Fe ³⁺ ions formed in the reaction with potassium thiocyanate, extinction coefficient

. The iron content in wt.% Is calculated by the formula:

.

We give examples of the synthesis of the claimed moisture-accumulating nutrient additives for the soil and examples confirming its moisture-accumulating properties and the effectiveness of the effect on plant development.

Example 1

A mixture of 1.5 g of FeCl ₃ ⋅ 6H ₂ O, 0.75 g of Na ₂ CO ₃ and 1500 ml of 0.5% aqueous ethanol is stirred at 70 ° C for 10 minutes. Leave the mixture until the colloidal catalyst is completely precipitated, then mix again, add 120 g of pine sawdust with constant stirring (particle sizes 1-3 mm); the amount of catalyst relative to sawdust in terms of Fe ³⁺ is 0.25 wt.%), 420 ml of perhydrol and 180 ml of water are added (mass ratio of hydrogen peroxide: sawdust = 1: 1, mass ratio of water: sawdust = 17.5 ); stirring is continued at room temperature until the hydrogen peroxide is completely consumed and centrifugation is isolated from the aqueous reaction mixture. Dried CD to constant weight, the weight of the obtained precipitate 36 g, yield 30%. The iron content of 0.030 wt.%.

Example 2. (on a pilot installation)

A mixture of 11 g of FeCl ₃ ⋅ 6H ₂ O, 4.4 g of Na ₂ CO ₃ and 15 l of 1.0% aqueous ethanol was stirred at 70 ° C for 10 minutes. Leave the mixture until the colloidal catalyst is completely precipitated, then mix again, add 1600 g of pine sawdust and 5.5 l of perhydrol with constant stirring (weight ratio hydrogen peroxide: sawdust = 1: 1, weight ratio water: sawdust = 12, amount of catalyst in relation to to sawdust in terms of Fe ³⁺ is 0.14 wt.%), stirring is continued at room temperature until the hydrogen peroxide is completely consumed, then CD is isolated by centrifugation. Dry the CD to constant weight, the weight of the resulting precipitate is 480 g, yield 30%. The iron content in the sediment is 0.032 wt.%.

Example 3

A mixture of 0.7 g of FeCl ₃ ⋅ 6H ₂ O, 0.4 g of Na ₂ CO ₃ and 1000 ml of 1% aqueous ethanol was stirred at 70 ° C for 10 minutes. Leave the mixture until the colloidal catalyst is completely precipitated, then mix again, add 60 g of oat straw with constant stirring (the amount of catalyst relative to the straw in terms of Fe ³⁺ is 0.24 wt.%), 200 ml of perhydrol is added (mass ratio of peroxide hydrogen: straw = 1: 1, mass ratio of water: straw = 20); stirring is continued at room temperature until the hydrogen peroxide is completely consumed, then CD is isolated by centrifugation. Dry the CD to constant weight, the weight of the obtained precipitate 16.8 g, yield 28%. The iron content in the precipitate is 0.027 wt.%.

Example 4

A mixture of 0.38 g of FeCl ₃ ⋅ 6H ₂ O, 0.20 g of Na ₂ CO ₃ and 500 ml of 1% aqueous ethanol was stirred at 60 ° C for 10 minutes. Leave the mixture until the catalyst is completely precipitated, then mix again, add 28 g of flax fire with constant stirring (the amount of catalyst relative to the fire in terms of Fe ³⁺ is 0.28 wt.%), 50 ml of perhydrol and 25 ml of water are added ( mass ratio of hydrogen peroxide: campfire = 0.5: 1, mass ratio of water: campfire = 20); stirring is continued at room temperature until the hydrogen peroxide is completely consumed, then CD is isolated by centrifugation. Dried CD to constant weight, the weight of the obtained precipitate 15.9 g, yield 56.8%. The iron content in the sediment 0,037 wt.%.

The moisture storage properties of the proposed CD for the soil were investigated by drought simulation. With a single wetting of the experimental soil, in the control: sand, in the experiment: sand combined with the CD obtained in Example 2, the number of surviving plants by the 19th day of the experiment was taken into account. The results are shown in examples 4 and 5 and in tables 1 and 2.

Example 5. Modeling of drought in the cultivation of peas cultivar Sugar.

We studied the effect of various amounts of CD obtained in Example 2 on the moisture preservation in soils by 19 days of the experiment with a single moistening of the soil using the example of Sugar pea. The culture media were: in the control, sand, once moistened with water, in the experiment, sand combined with CD and once moistened with water. In Experiment 1, the weight ratio of sand: CD was 10: 1; in Experiment 2, it was 5: 1. The effect of CD was estimated by the number of surviving pea plants on the 19th day of the experiment.

At the same time, the effect of various amounts of CD on the germination of pea seeds of the Sugar variety was studied.

Example 6. Modeling of drought during the cultivation of plants of cucumber Nezhinsky.

We studied the effect of CD on the development of plants of the Nezhinsky cucumber cultivated on media prepared according to Example 5. The effect of moisture preservation was evaluated: a) by the average height of plants on the 7th day; b) by the number of plants that formed this leaf on the 13th day; c) by the number of living plants on the 19th day.

The study of the influence of CD on the development of plants was carried out by various methods with CD obtained in example 2. The effect of CD was evaluated:

- the air-dry weight of the aerial parts of plants on the example of oats and sorghum;

- the rate of germination of potato tubers;

- the root formation of etiolated tuberous potato cuttings;

- on the development of green potato cuttings;

- the amount of chlorophyll in the green cuttings of potatoes.

The results are shown in examples 7-11 and in tables 3-7; in example 5 and table 1 shows the results on the effect of CD on the germination of seeds of peas cultivar Sugar.

Example 7. The effect of CD on the air-dry weight of the aerial parts of plants of oats and sorghum. The seeds of oats (cultivar Fodder) and sorghum (cultivar Pischevoy) were sown on culture media maintained in a wet state. In control it was sand, in experience - sand with the addition of CD ,. The mass ratio of sand: CD = 5: 1. After 20 days, the air-dry weight of the aerial parts of the plants was evaluated. The weight of the control is taken as 100%. The results are shown in table 3.

Example 8. The effect of CD on the rate of germination of potato tubers.

Potato tubers Luck was laid for germination: in the control variant, in sand moistened with water; in the experiment - in a mixture of sand and CD moistened with water. On the 30th day, the number of sprouted potato tubers was estimated. The results are shown in table 4.

Example 9. The effect of CD on the root formation of white etiolated tuberous potato cuttings.

White tuber etiolated cuttings were separated from potato tubers sprouted in the dark (cuttings length 5-6 cm, diameter ~ 0.5 cm) and placed into culture vessels of 30 pieces each with moist soil prepared according to Example 5. Vessels with cuttings were installed in a luminostat with rhythm of lighting light / dark 12/12. On the 15th day, the number of cuttings (%) that formed a pronounced root system was estimated. The results are shown in table 5.

Example 10. The effect of CD on the development of green potato cuttings.

Green potato plants were grown. Good luck, cut green cuttings with unopened leaves of 10-11 cm in size and placed in culture vessels 30 pieces each with moist soil prepared according to Example 5 and for control with wet sand. After 10 days, the number of plants (%) in which leaf plates were fully opened was estimated. The results are shown in table 6.

Example 11. Evaluation of the effect of CD on the content of chlorophyll in green potato cuttings.

From green cuttings grown in Example 10, on the 15th day, 4 cm of the upper part of cuttings with developed leaves was separated. Cuttings with leaves were ground in a porcelain mortar, extracts were prepared according to the standard method (VERNON, L. P. Spectrophotometric determination of chlorophylls and pheophytins in plant extracts. Anal. Chem., 1960, 32, pp. 1144-1150) and the absorbance was measured on wavelengths λ = 662 and 644 nm (using a Hach DR 4000V USA spectrophotometer) to calculate the chlorophyll content. The results are shown in table 7.

Thus, as can be seen from the above examples, the proposed CD is a highly effective moisture-accumulating nutritional supplement for the soil, simple in composition and production technology, as well as environmentally friendly. In addition, upon receipt of the proposed additives for the soil along the way, the problem of waste disposal of the agricultural and forest processing industries is solved.

Claims (4)

1. A moisture-accumulating nutrient additive for soil, which is a solid fraction of the product of oxidative cracking of plant waste products, obtained by treating waste plant materials in water at room temperature with hydrogen peroxide at a mass ratio of hydrogen peroxide to plant waste products of 0.5-1.0: 1 in the presence of a catalyst based on ferric oxide in an amount of 0.1-0.3 wt.% with respect to the waste vegetable materials based on Fe ^3+, wherein the catalyst is obtained by heating at 60-70 ° mixture of FeCl ₃ ⋅6H ₂ O, Na ₂ CO ₃ and 0.5-1.0% aqueous ethanol at the following component ratio, wt.%: FeCl ₃ ⋅ 6H ₂ O 0.1-0.2 Na ₂ CO ₃ 0.05-0.1 0.5-1.0% aqueous ethanol rest and isolated by centrifugation, while the moisture-accumulating nutrient additive for the soil is characterized by an iron content of 0.03-0.04 wt.%. 2. The soil additive according to claim 1, characterized in that the treatment of the waste of plant materials in water with hydrogen peroxide in the presence of a catalyst is carried out in a 12-20-fold mass excess of water relative to the waste of plant materials.