Method of environmentally friendly bioconversion of superfine metallurgical industry wastes containing heavy metals

FIELD: agriculture.

SUBSTANCE: invention relates to agriculture. The method of environmentally friendly bioconversion of superfine metallurgical industry wastes containing heavy metals comprises creation of mixtures based on sand, metallurgical sludge, peat and calcium carbonate for growing plants, and for bioconversion the plants of fodder beet (Beta vulgaris L.), large-flowered flax (Linum grandiflorum), sweet corn (Zea Mays) and rapeseed (Brassica napus) are used.

EFFECT: invention enables to simplify the technology of obtaining organo-mineral fertilisers for agriculture in the process of biological recovery of metal production wastes.

4 ex

 

The invention relates to the field of integrated waste processing and metallurgical industry to ensure non-waste technology and utilization of products of processing, namely, the development of techniques for biological utilization of complex composition slurry waste metallurgical industry, containing heavy metals (Fe, Zn, Ti, Ni and others). The invention relates also to a complex organic-mineral fertilizer and the method of their derivation from products industrial utilization and can be used in agriculture and gardening.

The sludge is called a two-phase system consisting of a solid dispersed particles of waste suspended in a liquid medium. When the main metallurgical units produce large quantities of fine dust, consisting of the oxides of the various elements. The latter is captured gas cleaning ducts structures and then served in the slum. The main characteristics of sludge are chemical and granulometric composition, however, when preparing sludge for disposal, it is necessary to know parameters such as density, moisture content, etc. it Should be noted that the sludge metallurgical enterprises of the chemical (and partly particle size) composition differ from each other. Sludge dust collecting device of the blast furnace are formed in the cleaning gas, out, usually in scrubbers or Venturi tubes. Before them are radial or tangential dry dust collectors that capture the largest, so-called flue dust that returns to agricultural production, as a component of the charge. Currently, these slurries are used as the sintering additive to the charge. Relatively low levels of use due to the relatively low share of iron in them (Fe <50%), and higher zinc content (>1%), which requires prior obenzinivanie sludge.

Currently, the most common methods of pretreatment sludges are pyrometallurgical and hydrometallurgical processing. These methods differ in the environment and processing temperatures. Often by-products formed during these trials are substances also have a negative impact on the environment. So when pyrometallurgical extraction of zinc by-products are carbon monoxide and carbon dioxide, causing global warming. At the same time, the formation of large quantities of wastewater that accompanies the hydrometallurgical processing confronts researchers additional tasks for recycling or disposal of the latter.

The imperfection of the used the used treatment technologies leads to an annual accumulation of millions of tons of sludge in teloslogenia, which has a negative impact on the environment.

Thus, development of more advanced, environmentally friendly methods of sludge processing and metallurgical production is an important task. One of the promising ways of utilization of fine waste steel production is their biological and biochemical processing.

The main purpose of the object - method of processing finely dispersed metal-containing SalesLogix waste is the reduction of the environmental, toxic and economic burden on the environment, as well as the development of cost-effective and environmentally friendly ways of recycling steel production.

The method of processing is the process of translation components of the sludge in a bioavailable form in the soil environment with subsequent inclusion in the physiological processes of plant organisms as essential micronutrients, taking into account the need for compliance with environmental safety.

The main purpose of biological treatment of highly dispersed metal-containing ash wastes is the reduction of environmental, toxic and economic burden on the environment, as well as the development of cost-effective ways of recycling metallurgical about what svoystv.

In scientific literature there are examples of studies on phytoremediation of industrial pollution. It is noted that currently the most common technology for the purification of soil from pollution with heavy metals is the removal of contaminated soil, transportation of soil to the landfill and replaced with clean soil. This technology does not solve the problem, but merely transfers it from one area to another costly and cumbersome way. The use of specialized plants that are able to accumulate high concentrations of heavy metals in the tissues, with the subsequent removal of these plants from contaminated sites. Phytoremediation is positioned as a new strategy for removing toxic metals from the environment using plants. Describes that when the incubation water plants hornwort Ceratophyllum demersum high concentrations of heavy metals Cu, Zn, Cd, Pb in the incubation medium decreased faster than in the control environment. It is noted that these data contribute to the scientific basis of innovative phytotechnologies (phytoremediation) purification from heavy metals. It is shown that algae can also serve for bioaccumulation of heavy metals.

The problem of processing various technogenic and anthropogenic pollution widely covered in local and foreign who atentos literature. However, it should be noted that mainly for processing superfine waste (sludge), containing heavy metals, are used physico-chemical (primarily pyrometallurgical methods and, more rarely, biotechnological methods.

One of the most toxic waste today are a waste of electrochemical productions. Slurries of these industries are characterized by large (up to 90%) amount of water with dissolved ions of heavy metals. The authors of the patent application EN 2010150213 has developed a unit for processing galanello, allowing hydrometallurgical method to remove heavy metals from waste in the form of sulfides of the respective metals. Unique installation scheme allows to achieve more complete in comparison with existing analogues, removal of heavy metals from sludge.

The authors of the patent RU 2404270 has developed a method of processing galanello, combining elements of hydro - and pyrometallurgy. A distinctive feature of the proposed technology is the intensification of the process by processing sludge with additives in the form of chloride and sulfide ions by the method of Mechanochemistry. The technical result of this technology is the reduction of the annealing temperature and removing heavy metals.

Loved ones are development-related processing tailing the metallurgical, the main problem is the high content of zinc. The authors of the patent RU 2091341 has developed a production line processing of zinc-containing raw material pyrometallurgical method to implement waste processing circuit high efficiency. It uses an additive in the form of silica and seachnasaigh component of a certain number, and production line includes the raw material preparation area and an oven with a remover liquid slag.

Known to offer improvements pyrometallurgical processing of zinc-containing slurry sintering and blast furnace production (EN 2280087). The advantage of this technology is to obtain at the output of metal zinc and iron, as well as increase the speed of the process. The technical result is achieved by use of rotating at a certain speed, as well as being at the optimal angle, the tube furnace.

The well-known scheme of processing of zinc-containing waste sinter, blast furnace, rolling and steelmaking (EN 2404271). The development is aimed at the intensification of the processes of recovery of iron and zinc, as well as savings reductant.

The disadvantages of pyrometallurgical methods are high energy consumption and pollution side p is the FL in the form of carbon monoxide and carbon dioxide. On the other hand low-cost and environmentally friendly technology based on the use of contained in the metallurgical slurries of minerals and digestible nitrogenous compounds, taking into account accumulated huge stocks of such waste may have an important social value, and at the same time will improve the efficiency of agriculture.

The biological conversion of metallurgical pollution and other anthropogenic origin in the wastewater and sediments examined in a number of domestic and foreign patents. The main area of use of plants as applied to the contamination of this kind is a method of phytoremediation of soils (US 5927005, US 5785735). The use of biological methods allows cleaning of soils from heavy metals, it is noted that the mechanisms of uptake, processing and the effect of particles of heavy metals in metallurgical wastes currently are not completely clarified.

Quite extensively in the patent literature considers the problem of bioutilization anthropogenic pollutants, including heavy metals in the wastewater. In this area it can be noted patents describing the fractionation of sewage sludge and their subsequent processing by microorganisms (EN 2057725, EN 2414444, EN 2463280, EN 2229200).

In Pat is NTE EN 2324730 describes the design of the bioreactor, which can be used for biological wastewater treatment and recycling organic waste.

An example of the processing of industrial waste described in patent RU 2153262 shows the possibility of bioconversion of organic wastes into valuable feed additive due to the enrichment of the initial mixture of biologically active substances, which also leads to the intensification bioconversion process.

Similar solutions in the field of conversion of metallurgical wastes bacterial method described in EN 2418870, EP 0489258. It is important to note that the use of biological treatment method allows you to translate in digestible form of pollution, containing elements such as arsenic or mercury, for instance, WO 2000078402 describes methods bacterial biological conversion of arsenic contamination of obtaining non-lethal intermediates.

The authors of the patent RU 2290270 has developed a technology biological remediation of oil-contaminated soils, which is in the tillage of backpropagate followed by inoculation of a mixture of seeds of leguminous and cereal crops previously treated with a plant growth regulator.

A prototype of the selected patent WO 2012140623, which shows that biological remediation can be successfully used to restore soils contaminated industrial is diversified waste. The authors propose a method of reclamation, based on the use of endemic plant species, able to grow on substrates containing heavy metals accumulating in their stems and leaves. This patent is an example of modern technology bioconversion of industrial waste containing heavy metals.

The disadvantage of the prototype is used as remediaton American plants-endemics. In addition, the prototype is recommended incineration plants remediate with subsequent disposal, which implies new environmental problems.

Unlike the prototype in the present invention remediate will serve as a common culture of Central Russia. An additional advantage is the possibility of economic use (primarily for technical purposes) in these plants. Thus, the level and efficiency of the developed technology will be higher.

The technical result is to simplify the technology of production of organic fertilizers for agriculture in the process of biological sludge disposal metallurgical production.

The technical result is achieved due to the fact that the eco-friendly way of bioconversion fine waste metallurgical industry, containing their heavy metals, includes the creation of mixtures of sand, metallurgical sludge, peat and calcium carbonate for growing fodder beet plants (Beta vulgaris L.), large-flowered flax (Linum grandiflorum), corn sugar (Zea Mays) and canola (Brassica napus). For mixing use a large laboratory mixer with a displacement of not less than 10 HP Mixer must quickly and uniformly mix the materials of different grain size, moisture content and specific gravity. The drum speed is not less than 100 rpm, the shape of the drum is conical. Loading capacity of the drum should not exceed half of the volume to ensure uniform mixing. Using weights weigh the sand with the previously entered him in metallurgical sludge (69%), kaolin clay (20%), neutral peat (10%) and calcium carbonate (about 1%). The sample is placed in a mixer. Include food mixer, the processing time of 15 minutes. Off the mixer, pour in the capacity for germination, mixer dried and sterilized. After 7 days of creating their mixtures are used as the substrate for planting in the greenhouse. For the cultivation of plants used capacity the following amounts:

for beet - 7 liters (length 0.7 m, width 0.3 m) at 30 plants;

- flax - 5 liters (length - 0.5 m, width 0.2 m) at 30 plants;

for corn - 10 liters (bucket) on 1 Rast is s;

- rape - 5 liters (length - 0.5 m, width 0.2 m) at 30 plants.

When growing beets is used in 0.01% aqueous solution of sludge for flax is used, the concentration of 1%, for corn - 0,001%, rape - 0,1%. In what is a watering with tap water as needed.

In terms of the mass of the soil the quantity of sludge should be:

Beet - 0.02 g/kg

Len - 2 g/kg

Corn - 0.002 g/kg

Rape - 0.2 g/kg

Growing plants in a greenhouse is not less than 3 months. Requirements for the growing conditions are determined on the basis of the recommendations for each of the crops. In the process of bioconversion of residual quantities of heavy metals in artificial soil after harvest should not exceed the maximum permissible concentrations (MPC) according to Mr. 2.1.7.2041-06 from 1.04.2006. Analytical methods assessment of bioaccumulation of heavy metals in different plant parts (roots, leaves, seeds). If the amount of heavy metals meets the requirements of SanPiN 42-123-4089-86, bioconversion may be found to be safe and successful.

Example 1

As an additive in the research was used sludge gas purification furnace shop (GODS) OAO Cherepovets steel mill, Severstal (, Cherepovets). The quantitative composition of the sludge:

Ti0.22 wt.%.
Cr0.08 wt.%.
Fe62.17 wt.%.
Ni0.48 wt.%.
Zn9.71% wt. and other

The sludge was mixed with the components of the artificial soil according to the above method. For growing fodder beet plants (Beta vulgaris L.) varieties "Record" was used containers of a capacity of 7 liters (length 0.7 m, width 0.3 m). In terms of the mass of the soil the quantity of sludge amounted to 0.02 g/kg

Growing plants in the greenhouse were conducted not less than 3 months. Requirements for the growing conditions were determined on the basis of the recommendations for this crop. The marked increase in 4,46 times development indicators beet (mass of roots) compared with plants grown on the same soil without sludge. In the process of bioconversion of residual quantities of heavy metals in artificial soil after harvest did not exceed maximum permissible concentrations (MPC) according to Mr. 2.1.7.2041-06 from 1.04.2006. Analytical methods were used to assess the bioaccumulation of heavy metals in different plant parts. In the result, it was found that the content of heavy metals appropriate to esthet the requirements of SanPiN 42-123-4089-86, thus, the bioconversion may be found to be safe and successful.

Example 2

As an additive in the research was used sludge gas purification furnace shop (GODS) OAO Cherepovets steel mill, Severstal (, Cherepovets). The quantitative composition of the sludge:

Ti0.22 wt.%.
Cr0.08 wt.%.
Fe62.17 wt.%.
Ni0.48 wt.%.
Zn9.71% wt. and other

The sludge was mixed with the components of the artificial soil according to the above method. For growing plants large-flowered flax (Linum grandiflorum) varieties "Clear eyes" was used in a volume of 5 liters (length - 0.5 m, width 0.2 m). In terms of the mass of the soil the quantity of sludge was 2 g/kg

Growing plants in the greenhouse were conducted not less than 3 months. Requirements for the growing conditions were determined on the basis of the recommendations for this crop. The marked increase of 65% development indicators flax (number of flowers) compared with plants grown on the same soil without sludge. In the process of bioconversion is quite a number of heavy metals in artificial soil after harvest did not exceed maximum permissible concentrations (MPC) according to Mr. 2.1.7.2041-06 from 1.04.2006. Analytical methods were used to assess the bioaccumulation of heavy metals in different plant parts. In the result, it was found that the content of heavy metals meets the requirements of SanPiN 42-123-4089-86 thus, the bioconversion may be found to be safe and successful.

Example 3

As an additive in the research was used sludge gas purification furnace shop (GODS) OAO Cherepovets steel mill, Severstal (, Cherepovets). The quantitative composition of the sludge:

Ti0.22 wt.%.
Cr0.08 wt.%.
Fe62.17 wt.%.
Ni0.48 wt.%.
Zn9.71% wt. and other

The sludge was mixed with the components of the artificial soil according to the above method. For growing plants corn sugar (Zea Mays) varieties "Kuban canned 148" used capacity of 10 liters (bucket). In terms of the mass of the soil the quantity of sludge amounted to 0.002 g/kg

Growing plants in the greenhouse were conducted not less than 3 months. Requirements for the growing conditions were determined based on recommendations gladney culture. The marked increase of 37% development indicators corn (weight of cobs) compared with plants grown on the same soil without sludge. In the process of bioconversion of residual quantities of heavy metals in artificial soil after harvest did not exceed maximum permissible concentrations (MPC) according to Mr. 2.1.7.2041-06 from 1.04.2006. Analytical methods were used to assess the bioaccumulation of heavy metals in different plant parts. As a result, it was found that the content of heavy metals meets the requirements of SanPiN 42-123-4089-86 thus, the bioconversion may be found to be safe and successful.

Example 4

As an additive in the research was used sludge gas purification furnace shop (GODS) OAO Cherepovets steel mill, Severstal (, Cherepovets). The quantitative composition of the sludge:

Ti0.22 wt.%.
Cr0.08 wt.%.
Fe62.17 wt.%.
Ni0.48 wt.%.
Zn9.71% wt. and other

The sludge was mixed with the components of the artificial soil according to the above methods is E. For the cultivation of rape plants (Brassica napus) varieties "Lipetsk" was used in a volume of 5 liters (length - 0.5 m, width 0.2 m). In terms of the mass of the soil the quantity of sludge amounted to 0.2 g/kg

Growing plants in the greenhouse were conducted not less than 3 months. Requirements for the growing conditions were determined on the basis of the recommendations for this crop. The marked increase of 50% development indicators rape (mass pods) compared with plants grown on the same soil without sludge. In the process of bioconversion of residual quantities of heavy metals in artificial soil after harvest did not exceed maximum permissible concentrations (MPC) according to Mr. 2.1.7.2041-06 from 1.04.2006. Analytical methods were used to assess the bioaccumulation of heavy metals in different plant parts. In the result, it was found that the content of heavy metals meets the requirements of SanPiN 42-123-4089-86 thus, the bioconversion may be found to be safe and successful.

Experimental data confirmed the possibility of using biological utilization of metallurgical sludge containing heavy metals, as biomineral complex to stimulate the growth of higher plants.

An eco-friendly way of bioconversion fine waste metallurgical Indus is striae, containing heavy metals, including the creation of mixtures of sand, metallurgical sludge, peat and calcium carbonate for growing plants and characterized in that for the bioconversion of used plants fodder beet (Beta vulgaris L.), large-flowered flax (Linum grandiflorum), corn sugar (Zea Mays) and canola (Brassica napus).



 

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SUBSTANCE: for biorecycling of oil sludge and oil production and processing waste by means of soil populating with natural black-soil-forming organisms a mixture is prepared with an initial composition of 26-30% of oil sludge, 26-30% of liquid oil sludge and the remaining part of organic domestic waste and/or saw dust, the mixture is infused within 20-24 hours at a temperature of 20-25C for further populating with earthworms of the first generation, the mixture is withhold within 17-30 days till the earthworms of the second and third generations appear for the purpose of the sludge-contaminated soil treatment. The earthworms of the second and third generations grown in a hothouse conditions by adaption of the earthworms of the first generation to the above mixture are introduced to the contaminated soil. At that introduction of the earthworms of the second and third generations is made at a volume ratio of soil and the mixture equal to 10-15:1.

EFFECT: improving efficiency of the contaminated soils treatment.

4 cl

FIELD: chemistry.

SUBSTANCE: soil-sludge mixture is obtained by thermal treatment and contains a mixture of components obtained by processing wastes in the UZG-1MGZH apparatus for treating oil-contaminated soil in amount of 30-40 wt %, peat 20-35 wt % and sand 20-50 wt %, wherein the mixture of components contains, wt %: vanadium oxide 32.5; carbon 31.4; aluminium oxide 7.5; silicon oxide 7.5; nitrogen oxide 6.8; iron oxide 5.3; hydrogen 4.4; magnesium oxide 1.5; manganese oxide 0.8; lead oxide 0.4; chromium oxide 0.4; zinc oxide 0.4; nitrogen 0.4 and related impurities 0.7.

EFFECT: improving environmental conditions, restoring fertility of oil-contaminated and disturbed lands, higher fertility as a result of enrichment of contaminated soil with oxygen and mineral fertilisers during treatment and reducing oil-contaminated areas.

3 cl, 3 tbl

FIELD: chemistry.

SUBSTANCE: soil-sludge mixture for reclamation of oil-contaminated and disturbed lands contains a mixture obtained by treating a composition consisting of oil sludge, peat, sand and water, with the following ratio of components, wt %: vanadium oxide 32.5; carbon 31.4; aluminium oxide 7.5; silicon oxide 7.5; nitrogen oxide 6.8; iron oxide 5.3; hydrogen 4.4; magnesium oxide 1.5; manganese oxide 0.8; lead oxide 0.4; chromium oxide 0.4; zinc oxide 0.4; nitrogen 0.4; related impurities 0.7. Components of the composition of oil sludge, peat, sand and water are in the following ratio, wt %: oil sludge 30-40%; peat 30-35%; sand 30-35%; water - the balance. The related impurities include a proppant which contains ceramic spheres, a cut of the oil-contaminated soil layer containing crushed stone, and fine wastes of ferrous and nonferrous metals. Treatment involves mixing the composition of oil sludge, peat, sand and water in a hopper of an UZN-1MGZH apparatus.

EFFECT: improving environmental conditions, restoring fertility of oil-contaminated and disturbed lands, higher fertility as a result of enrichment of contaminated soil with oxygen and mineral fertilisers during treatment and reducing oil-contaminated areas.

4 cl, 1 tbl

FIELD: soil restoration from formation fluid contaminants in oil recovery and transportation regions.

SUBSTANCE: claimed composition contains (mass %): chemical ameliorant 3.5-5.7; organic fertilizer 15.7-29.0; adsorbent 67.5-78.6. Method for sectioning soil treatment includes application of composition onto soil layer with 30 cm of depth. Then treated layer is shifted out of spot boundary. Opened surface is covered with composition of present invention. Then mole drainage of 60-65 cm in depth is made in soil by using mole plow or chisel plow, followed by plowing of 58-51 cm in depth and returning of sheared soil into spot.

EFFECT: effective soil restoration from formation fluid contaminants.

5 cl, 2 dwg, 1 tbl

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