RU2426722C1 - Method of conducting mechanochemical reactions and reactor for realising said method - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: method of conducting mechanochemical reactions during compression, temperature, pressure and ultrasonic treatment of starting material in a reactor involves processing the mass with an auger. The processed mass in volume of 10-90% reversibly enters through reactor channels into a multiple compression zone and ultrasonic treatment carried out using a double-frequency annular ultrasonic concentrator the frequency of which differs from each other by 0.01-15%. The mechanochemical reactor includes a housing 1, a shaft 5 rotated by a drive, a starting material receiving container 4, an auger 2, a mouthpiece 9 and an ultrasonic generator. The reactor housing 1 is in form of a polyhedron with channels 12 along the axis of the housing 1, with combs 11 in the channels. The ultrasonic generator is an annular ultrasonic concentrator 8. The reactor enables to obtain salts of humic acids from a mixture of peat and alkali which makes up 10-20% of the weight of peat in the dry equivalent.

EFFECT: method and apparatus enable to obtain a homogenised product in a reactor in which an efficient mechanochemical reaction takes place to obtain natural ecologically clean fertiliser.

3 cl, 4 dwg, 1 ex

Description

The technical solution relates to the conduct of mechanochemical reactions of various masses and mixtures, the manufacture, for example, organo-mineral fertilizers, in particular salts of humic acids based on peat, feed additives for farm animals.

The use of humic preparations is characterized by a harmonious combination of resource-saving technologies, obtaining stable yields of quality products and respect for nature.

Currently, worldwide interest in humate fertilizers has increased sharply. Humic compounds, being physiologically active substances, regulate and intensify metabolic processes in plants and soil. It was found that humic substances not only increase productivity, fruit weight and accelerate ripening, but also improve product quality by increasing the content of sugars and vitamins in it, while reducing the amount of nitrates. In 1981, it was decided to establish the International Society for the Study of Humic Substances (IHSS). The first president of the society was elected R.L. Malcolm (R.L. Malcolm) USA. The first International Conference was held in 1983 in the state of Colorado (USA). At IHSS conferences it was stated that the priority in research on technologies for producing humic fertilizers belongs to scientists of the Soviet Union and, above all, L.A. Khristova (Dnepropetrovsk). Then these works were continued by other Soviet and Russian scientists. However, the boom in the development of industrial technologies for the production of humates nevertheless began in Europe and other countries of the world in the 80-90s of the 20th century. In Russia, the active release of industrial humic preparations began only in the late 90s. The accumulated scientific experience has made it possible to ensure the production of drugs that are not inferior in quality to foreign developments.

Humates are a group of naturally occurring high molecular weight substances that, due to their structural features and physicochemical properties, are characterized by high physiological activity. The mechanism of action of humic substances is to stimulate all biochemical processes in the body of the plant, not only at the initial stage of seed germination and the formation of the root system, but also the further growth and development of the plant. They change the permeability of cell membranes, increase the activity of enzymes, the content of chlorophyll and the productivity of photosynthesis, and also stimulate respiration, the synthesis of proteins, sugars, amino acids and vitamins. Along with this, humates are non-toxic, non-carcinogenic and do not have a mutagenic effect, which in turn creates the prerequisites for environmentally friendly products. Humates have a significant effect on the water-physical and physico-chemical properties of the soil:

- increase the moisture capacity of light soils (on average by 30%), contributing to the formation of an agronomically valuable lumpy-granular structure;

- improve the porosity and water permeability of heavy soils, preventing the formation of cracks, crusts, cementation of the arable layer and the formation of a sub sole;

- contribute to aeration and breathability of the soil profile, optimizing the root respiration of plants and the redox regime of the soil as a whole;

- regulate the reaction of ion exchange between the soil and aqueous solutions;

- affect the buffer capacity of soils, thereby contributing to the maintenance of a natural pH level even with excessive intake of acidic or alkaline agents.

An important aspect is the interaction of humates with various kinds of pesticides and organic ecotoxicants (oil products, aldehydes, phenols, etc.). Humates irreversibly bind them into sedentary complexes that are removed from the soil cycle, preventing the entry of ecotoxicants into agricultural products and, as a result, into the human body.

When using humates in agriculture, the following is noted:

- increases the yield of grain, fodder and vegetable crops by an average of 30-40%;

- increases the germination of seeds and their germination;

- the metabolism of plants improves, the absorption of mineral substances increases, root formation increases;

- improves the survival rate of seedlings and plants during transplantation;

- increases the resistance of plants to diseases, frosts and droughts due to increased activity of the enzyme nitrate reductase;

- the content of nitrates, pesticides, heavy metal ions and radionuclides is reduced, which suggests the possibility of using humates for soil remediation and disinfection.

The usual method of applying humates is pre-sowing seed treatment, spraying of vegetative plants, root dressing. Perhaps the combined use of humates with pesticides in the processing of crops and seeds.

Currently, industrial humates are widely used in South and North America, China, Australia, Africa, the southern and central countries of Europe and of course in Russia. In this case, mainly three types of humates are used: sodium humate, potassium humate and ammonium humate. The main raw materials for the industrial production of humic substances to date is peat or special varieties of brown coal. The advantage of this raw material is its availability in various regions of the world.

Humic acids in such raw materials are presented in the form of high molecular weight water-insoluble fractions. The extraction of humic acids occurs with monovalent cations of sodium, potassium or ammonium in an alkaline environment. In this case, dilute solutions of salts of humic acids are obtained, which are concentrated by evaporation to 2-8% of solutions. This technology determines both the good technological properties of the drug and its high cost in terms of the content of the active substance. Nevertheless, such preparations are convenient for dissolution and have found their market niche. The so-called “dry brown coal processing” with obtaining dry humic preparations is economically more promising. Due to its low cost, this technology is used by most of the leading manufacturers in the world. At the same time, the resulting preparations have several disadvantages, which include:

- incomplete solubility and content of ballast insoluble components: resins, bitumen, fossils, etc .;

- the difficulty of ensuring a stable composition of the drug, including heavy metals, due to the variability of raw materials in the field;

- a small amount or absence of fulvic and low molecular weight acids.

However, due to the relatively low price, these humic preparations are most widely represented both on the global and Russian markets. In the 80s of the last century, Leningrad scientists developed a new technology for producing environmentally friendly concentrated salts of humic acids. A feature of this technology is the imitation of natural processes of humification of lignin-containing organic substances. In nature, the process of humification of wood lignin lasts for centuries, and the developed technological process provides a result in 1-2 hours. At the same time, a wide complex of high and low molecular weight humic compounds, including fulvic acid salts, is obtained. Since 1999, a wide range of scientific and technological studies of this technology has made it possible to offer consumers a new generation of industrial humic preparation - Lignohumat ^® (1).

It is also known in the industry to manufacture salts of humic acids from a mixture of peat and alkali NaOH, KaOH.

Known designs of screw presses.

For example, a device for preparing briquettes is known.

At the exit of the press, a forming unit is installed, made in the form of a closed belt conveyor and forming chambers, as well as in the form of a pressing element that is pivotally mounted at the exit of the rectangular nozzle. The forming chambers are formed by transverse partitions with a pointed end edge. The pressing element is made in the form of a plate and spring-loaded relative to the frame. The auger mixes and moves the manure. The liquid fraction is removed through the perforations of the housing. The seal is completed in a rectangular nozzle. The conveyor compresses the dung mass with transverse partitions, and the plate interacts with the edges of the partitions and grinds the fibrous inclusions (2).

The screw press for processing polymer wastes "SHPPO" is intended primarily for the separate processing of polymer wastes in the form of bags, film packages, pieces of films and the like into polymeric, mainly tubular products and differs from those known for the use of a loading box with a rotary wall forming an opening for supplying waste, as well as equipped with an elastic element, for example rubber, which creates a sealed cavity with a duct cover with compressed air supplied to the last and from the bottom of which a shovel plate forcing waste into the tubular housing of a screw shaft provided with gear knives in the waste feeding area fixed along a helical line between the screw turns, while the screw shaft housing and its heat-insulated casing form a saturated steam cavity with a temperature of 110-120 ° C, which is communicated with an adjacent annular cavity of sharp steam with a temperature of 130-150 ° C through openings with diameters of 0.002-0.005 m in the dividing wall and heating the molding cylinder-conical mouthpiece, and the resulting polymer melt, sold which is drawn through the gaps between the mouthpiece and the cylindrical conical end of the screw shaft, it is formed into a polymer product of predominantly tubular type, cooled at the outlet of the mouthpiece and externally by supplying cold water “to the passage” by means of valves into the annular cavity washing the end portion of the mouthpiece, and from the inside by supplying compressed air the valve through the through central hole in the auger shaft, rotated at a given speed with the help of a driving pulley-flywheel and V-belt transmission by, for example, a gear motor (3) .

The closest analogue to the claimed technical solution - the method and the mechanochemical reactor - is a screw press, comprising a housing, a shaft rotating from the drive, a receiving container of the starting material, a screw, a mouthpiece equipped with ultrasonic emitters (4).

The device is used in coke-chemical engineering, in particular in devices for briquetting coal mass.

However, these methods and designs of analogues, including the closest analogue, cannot provide a sufficient quality of the products obtained, in particular salts of humic acids.

The objective of the proposed solution is to develop a method and a reactor for carrying out mechanochemical reactions of various starting materials and mixtures using a screw, in particular the production of salts of humic acids.

The technical result is to obtain a homogenized product in a reactor in which mechanochemical reactions proceed efficiently, in particular, to obtain a natural environmentally friendly fertilizer.

A method for carrying out mechanochemical reactions and a reactor for the implementation of this goal are proposed.

The method of carrying out mechanochemical reactions under compression, temperature, pressure and ultrasonic treatment of the starting material in the reactor, while processing the mass with the help of a screw, is characterized in that the processed mass in the amount of 10-90% is reversed through the channels of the reactor into the multiple compression zone, and processing ultrasound occurs using a two-frequency ring ultrasonic concentrator, the frequencies of which differ from each other by 0.01-15%.

The method of producing salts of humic acids from a mixture of peat and alkali in a mechanochemical reactor is characterized in that the alkali is 10-20% by weight of peat by weight in dry equivalent.

A mechanochemical reactor, including a housing, a shaft rotating from the drive, a receiving container of the starting material, a screw, a mouthpiece and an ultrasonic generator, is characterized in that the reactor vessel is made in the form of a polyhedron with channels along the axis of the vessel, with combs located in the channels, and the ultrasonic generator a ring ultrasonic concentrator.

The mechanochemical reactor is characterized in that said polyhedron has six or more faces, and the comb is triangular.

The mechanochemical reactor is characterized in that the dimensions of the comb are 0.01-0.5 of the height of these channels relative to the circumference of the mechanochemical reactor.

The mechanochemical reactor is characterized in that the ratio of the diameter of the mouthpiece and the reactor vessel is in the range 1: 10-1: 2.

The mechanochemical reactor is characterized in that the ultrasonic concentrator is located in the zone of greatest compression of the treated mass.

The mechanochemical reactor is characterized in that the mouthpiece is made adjustable in diameter of the mass outlet or removable. The output reactor in front of the mouthpiece is equipped with an annular ultrasonic concentrator made with ultrasonic emitters in the zone of greatest compression of the processed mass. However, the greatest compression can be created in other zones of the reactor.

The mechanochemical reactor is illustrated in the figures: FIG. 1 is a diagram of a reactor, FIG. 2, B is a leader in FIG. 1, a comb in a channel, FIG. 3 is a section through FIG. - a diagram of the frequency addition (by the beat frequency) of the ultrasonic vibrations of the concentrator.

The positions in the figures indicate: 1 - reactor vessel, 2 - screw, 3 - screw turns, 4 receiving tank, 5 - shaft, 6 - gearbox, 7 - electric motor, 8 - ultrasonic concentrator, 9 - mouthpiece, 10 - source materials, for example a mixture of peat and alkali, 11 - comb, 12 - channels, 13 - face of the reactor vessel.

The reactor operates as follows.

The electric motor 7 rotates the shaft 5 through the gearbox 6 (figure 1). Pre-mixed in a mixer (not shown in the drawing), the starting materials are loaded into a receiving tank 4, from where they are moved along the screw 2 to the compression and mixing (grinding) zones, in which a pressure of 1 to 300 atm and a temperature of 20 to 120 ° C are formed. The processed mass passes through channels 12 having combs 11, for example, of a triangular shape, with a height H (pos. B of FIG. 2 and FIG. 3). The mass is repeatedly subjected to mechanochemical treatment due to compression, grinding, temperature and pressure in the channels 12 (up to 90% of the mass is returned to reprocessing). The reactor polyhedron in body 1 (Fig. 3) has six or more faces 13, and the comb is triangular, and the size of the comb is 0.01-0.5 height of the indicated channels relative to the circumference of the mechanochemical reactor.

The ratio of the diameter of the mouthpiece and the reactor vessel is in the range 1: 10-1: 2.

Before the mouthpiece 9, the mass is affected by two-part ultrasound of the ring concentrator 8 (Fig. 4 shows the frequency and amplitude of the beat of ultrasound, U - amplitude, t - time); the frequencies of the ultrasonic concentrator differ from each other by 0.01-15%.

At the outlet of the reactor, the treated mass is subjected to ultrasound to homogenize the mass and obtain a high-quality product.

Instead of a ring ultrasonic concentrator, a different concentrator can be used in the mechanochemical reactor, but its location is advisable in the zone of the greatest compression of the treated mass, i.e. at the outlet of the reactor - in front of the mouthpiece or in the mouthpiece itself.

The design of the mouthpiece provides a forced return of the processed mass through the channels of the reactor to the multiple compression zones (the mouthpiece is made adjustable in diameter or removable).

Upon receipt of the salts of humic acids from a mixture of peat and alkali in a mechanochemical reactor, the alkali makes up 10-20% of the mass of peat by weight in dry equivalent.

The liquid fraction and the resulting gases in the reactor during processing of the mass contribute to the intensification of the process and improve product quality. The method and reactor under consideration can also be successfully used for activation and proportional distribution of nanosupplements over the volume, for example, in multicomponent construction (concrete, plaster, and others) and other mixtures. It is possible to use various catalysts in the reactor.

The speed of rotation of the screw shaft depends on a number of factors, one of which is the qualitative characteristics of the processed mass. The material from which the screw press is made is high-strength steel.

The shape of the finished product in the form of a workpiece continuously emerging from the mouthpiece is determined by the contour and dimensions of the cross section of the mouthpiece itself, which is mainly a replaceable element of the reactor.

The advantages of the proposed solution are:

- the proposed method and mechanochemical reactor are universal and can be used in various sectors of the economy;

- processing the mass in a reactor of this type provides the intensification of the process and increase productivity and product quality;

- the reactor can also be used for the production of various fertilizers, for example organo-mineral fertilizers, in particular salts of humic acids based on peat, feed additives for farm animals, etc .;

- the considered method and reactor can also be successfully used for activation and proportional distribution by volume of nano-additives.

Information sources

1. Internet: www.humate.spb.ru.

2. USSR patent No. 1768052, А01С 3/00, publ. 10/15/1992.

3. Application for the invention of the Russian Federation No. 2001129679 A, publ. 10/27/2003.

4. Copyright certificate of the USSR No. 405717, publ. 11/05/1973.

Claims (8)

1. The method of carrying out mechanochemical reactions during compression, temperature, pressure and ultrasonic treatment of the source material in the reactor, while processing the mass using a screw, characterized in that the treated mass in a volume of 10-90% reversely flows through the channels of the reactor into the multiple compression zone, and ultrasonic treatment occurs using a two-frequency ring ultrasonic concentrator, the frequencies of which differ from each other by 0.01-15%. 2. A method of producing salts of humic acids from a mixture of peat and alkali in a mechanochemical reactor, characterized in that a mechanochemical reactor is used, including a housing rotating from the drive shaft, a receiving container of the starting material, a screw, a mouthpiece and an ultrasonic generator, the reactor vessel is made in the form of a polyhedron with channels along the axis of the casing, the combs are located in the channels, and the ultrasonic generator is a ring ultrasonic concentrator, and the alkali is 10-20% of the mass of peat by weight in dry equivalent. 3. Mechanochemical reactor, comprising a housing, a shaft rotating from the drive, a receiving container of the source material, a screw, a mouthpiece and an ultrasonic generator, characterized in that the reactor vessel is made in the form of a polyhedron with channels along the axis of the vessel, with combs located in the channels and an ultrasonic the generator is a ring ultrasonic concentrator. 4. The mechanochemical reactor according to claim 3, characterized in that said polyhedron has six or more faces, and the comb is triangular. 5. The mechanochemical reactor according to claim 3 or 4, characterized in that the dimensions of the comb are 0.01-0.5 of the height of these channels relative to the circumference of the mechanochemical reactor. 6. The mechanochemical reactor according to claim 3 or 4, characterized in that the ratio of the diameter of the mouthpiece and the reactor vessel is in the range 1: 10-1: 2. 7. The mechanochemical reactor according to claim 3, characterized in that the annular ultrasonic concentrator is located in the zone of greatest compression of the processed mass. 8. The mechanochemical reactor according to any one of claims 3 to 7, characterized in that the mouthpiece is made adjustable in diameter of the mass outlet or removable.

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