KR20120066774A - Manufacturing method of environment-friendly construction material from ferro-nickel slag by effective microorganisms treatment - Google Patents

Abstract

PURPOSE: A material manufacturing method of environmentally friendly construction materials of ferronickel slag using effective microorganisms are provided to enhance profitability, productivity, and workability by processing converter slag with effective microorganisms. CONSTITUTION: A material manufacturing method of environmentally friendly construction materials of ferronickel slag using effective microorganisms comprises the following steps: directly inserting effective microorganisms into iron making vessel slag with suitable particle sizes or pulverizing the iron making vessel slag into fine particles; activating the iron making vessel slag by chemical-mechanical pulverization; and keep stirring the activated iron making vessel slag with the effective microorganisms. The chemical composition in weight percent based iron making vessel slag is 14-19% of iron oxide(T-Fe), 40-48% of calcium oxide(CaO), 10-16% of silicon dioxide(SiO2), 1-3% of aluminium oxide(Al2O3), 5-8% of magnesium oxide(MgO), and 4-6% of manganese oxide(MnO).

Description

Manufacturing method of environment-friendly construction material from ferro-nickel slag by effective microorganisms treatment}

The present invention contains 4 to 5% of impurities such as carbon, silica, manganese, phosphorus, etc. in the steelmaking step of the steelmaking process, and since its properties are strong, there is a need for a step of removing the impurities to produce a ductile steel, What happens during this process is the steel converter slag,

Iron powder (T? Fe), calcium oxide (CaO), silicon dioxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), magnesium oxide (MgO), manganese oxide (MnO), phosphate (P ₂ O ₅ ) The present invention relates to a method for manufacturing an environmentally friendly building material using useful microorganisms in steelmaking converter slag having a component such as sulfur (S) and titanium dioxide (TiO ₂ ). In particular, when useful microorganisms are directly applied to slag treatment, It is possible to obtain eco-friendly, high value-added materials without odorless or hazardous substance dissolution. The present invention relates to a method for producing a ceramic material in place of aggregate to replace expensive environmental materials used in cement.

In general, various types of treatments are applied to apply various functionalities of useful microorganisms, and the method of directly injecting the culture solution is very inconvenient and difficult to apply.

In particular, when the culture medium containing the useful microbial group is used as it is, when the culture medium of the useful microbial group is directly injected into water or soil for the purpose of water quality, soil improvement, and sewage treatment, the culture medium flows out without being fixed in one place. Loss of effect, due to this is not only to supply a large amount of the useful microbial culture lacked, but also has the disadvantage that can not be fixed in the construction and civil engineering materials, such as cement.

In addition, when building a house or a building, volatile organic compounds (VOCs), such as benzene, toluene, chloroform, acetone, styrene, formaldehyde, etc., are emitted from the concrete, building materials, finishing materials, and adhesives used. In addition, there are also contaminants such as radon, asbestos, carbon monoxide, carbon dioxide, nitrogen oxides, ozone, fine dust and airborne bacteria, and organisms such as bacteria, mites and pets such as fungi and viruses can contaminate indoor air. If these pollutants are not discharged out of the building and accumulate indoors, they cause various health problems. Therefore, in order to reduce such damage, eco-friendly materials should be used instead of construction materials such as concrete and finishing materials containing chemical substances.

On the other hand, the useful microbial agent's effect is based on its action on the antioxidants produced by photosynthetic bacteria, lactic acid bacteria and yeasts through mixed co-culture, and when mixed with antioxidants and building adhesives, the smell disappears and the life of the material is oxidized. Because it is extended by being prevented, if it is used in various building materials, it will alleviate the sick house syndrome and delay the oxidation of the materials used to increase the lifespan. That is, it is known that enzymes produced by microorganisms operate at higher efficiency under antioxidant conditions (environment) formed by antioxidants, so that volatile organic substances are adsorbed and removed.

On the other hand, in the steelmaking process, about 100 to 150kg of steelmaking converter slag per tonne of molten steel is generated as a by-product. The steelmaking converter slag is composed of iron powder (T? Fe), calcium oxide (CaO), silicon dioxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), magnesium oxide (MgO), manganese oxide (MnO), and phosphate ( P ₂ O ₅ ), sulfur (S), titanium dioxide (TiO ₂ ) and the like. Typically, steelmaking converter slag is recycled in various ways as raw materials for cement production, civil engineering materials (for soil), soil improvement materials (for soil), aggregates for asphalt concrete, aggregates for concrete, etc. It is used as aggregate and is mostly landfilled.

An object of the present invention is to produce a material for antioxidant concrete and mortar by treating the steelmaking converter slag useful microorganisms in advance, without directly adding liquid microorganisms when producing concrete and mortar using the steelmaking converter slag. In other words, the useful microbial agent is pretreated in steelmaking converter slag, which is an industrial by-product, to reduce the amount of harmful volatile organic substances in concrete and mortar and to reduce heavy metal leaching.

Therefore, in the present invention, in order to find a way to utilize the slag generated in a large amount in the steelmaking process of steelmaking to manufacture a ceramic for environmentally-friendly microbial treatment building materials.

The present inventors intended to manufacture environmentally friendly building materials for sand substitutes using steelmaking converter slag and useful microorganisms or to use them by adding useful microorganisms to some concrete or mortar.

As described above, the present invention is conventional in the manufacture of environment-friendly mortar, since it is inconvenient and difficult to add useful microorganisms in liquid form in various ways, and while searching for a method for replacing them, by grinding the recently generated steelmaking converter slag, After activating by the method, and directly treated with useful microorganisms, after adjusting the particle size of the appropriate size, it was conceived to obtain an environment-friendly mortar and concrete material.

Therefore, the object of the present invention, by using the steelmaking converter slag useful microorganisms as a material for mortar or concrete, to improve the economics, productivity, workability, increase the added value by recycling steelmaking converter slag, stabilize the environment-friendly building materials We want to provide building materials using steelmaking converter slag loaded with useful microorganisms to ensure supply.

The present invention relates to a method for manufacturing a sand substitute dry material or a ceramic having the same action using the steelmaking converter slag, after treatment with the useful microorganisms using the steelmaking converter slag, the mortar or environmentally friendly Consists of manufacturing concrete.

In the method for producing a ceramic according to the present invention, the above-mentioned useful microorganism group is cultured in a solution state, and the cultured solution is diluted with water and added to a steelmaking converter slag directly or pulverized and stirred.

As a manufacturing method for obtaining a ceramic using a steelmaking converter slag treated with useful microorganisms is as shown in Figure 5, using a microbial group of the useful microbial stock solution or useful microbial group extract alone or mixed them It was.

The steelmaking converter slag is crushed by a hammer mill or a ball mill to a certain particle size, an activation process through mechanochemical crushing, a microorganism supporting process using useful microorganisms, and a method for producing concrete or mortar using these materials. Is done.

As such, the present invention can manufacture steel-making converter slag, which has been used as a simple subgrade material without using any useful microorganisms until now, as an odorless and antioxidant-friendly functional material for eco-friendly dry materials, and also recycles industrial by-products to add value. This will have a very beneficial effect in contributing to the national economy as well as preventing pollution.

1 is a VOC graph generated in general-mortar.
Figure 2 VOC graph generated from the antioxidant-mortar.
3 is a VOC graph generated from antioxidant concrete.
Figure 4 VOC graph generated in general concrete.
5 is a material manufacturing process for building materials using a steelmaking converter slag treated with useful microorganisms.

Hereinafter, the present invention will be described in detail by way of examples.

However, the following examples are merely illustrative of the present invention, and the content of the present invention is not limited to the following examples.

Example 1

Steelmaking converter slag used in Example 1 has a chemical composition and particle size distribution as shown in Table 1 and Table 2.

Chemical composition of steelmaking converter slag. (Unit: weight.%) Train
(T? Fe) Calcium oxide
(CaO) Silicon oxide
(SiO ₂ ) Aluminum oxide
(Al ₂ O ₃ ) Magnesium oxide
(MgO) Steelmaking
Converter slag
16.4 46.1 14.80 1.5 6.3 Manganese oxide
(MnO) Phosphorus
(P ₂ O ₅ ) brimstone
(S) Titanium dioxide
(TiO ₂ ) 5.4 1.7 0.08 1.5

Particle size distribution of steelmaking converter slag. (Particle size:%) 10 mm 5 mm 2.5 mm 1.2 mm 0.6 mm 0.3 mm 0.15 mm Assembly rate Steel converter slag 100 100 98 73 41 19 9 2.60

Steelmaking converter slag with physical properties of Table 1 and Table 2 was sprayed with a useful microbial stock solution and 1000-fold dilution, and then aged for 1 to 3 days (24 to 72 hours), followed by sieving. It was used directly as mortar or concrete fine aggregate. In addition, the steel converter slag treated this was dried, and then used for the production of existing mortar or concrete after mechanochemical grinding.

Example 2

A useful microbial agent was used directly, and steelmaking converter slag having the properties of Tables 1 and 2 was used.

For the production of ordinary mortars and concrete, cement was ordinary Portland cement, a standard product of KS L 5100, and the aggregate used was standard steel, a standard product of KS L5100 for comparison with untreated steel converter slag. .

The preparation of the specimen was based on KS L 2476, the mixing was carried out by weight ratio of cement and fine aggregate of 1: 1, and the bibimb was done by hand bibim. At this time, in order to maintain uniform workability, the use quantity was determined to be 30% by using a 170 * 5mm float.

During the preparation of the specimens, the incubation (20 ± 2 ℃, RH 80 ± 5%) for 5 days at the laboratory temperature (20 ± 2 ℃, RH 80 ± 5%), and then up to a predetermined period. .

The specimens were water / cymen with the goal of maintaining the same construction year (flow value 170 ± 5mm).

W / C was determined, and the weight loss rate test of the specimens was measured every day from demolding (day 2) to 7 days of age, and then the 7-day interval was measured until age 28, and the density of the specimens was measured. It was.

The absorption rate of 28-day specimens was measured, and the strength (compression and bending) test of environmentally friendly mortar was conducted on the 28-day specimen, and the results are shown in Table 3.

The mixing ratio was stirred by adding 20-30% by weight of water containing 1-5% by weight of the useful microbial group solution to 100% by weight of steelmaking converter slag, and then mixed with cement to prepare mortar.

Comparative Example 1

In this comparative example, cement of the same standard was used as in Example 1, and a standard yarn was used to compare physical properties such as Example 1 and compressive strength.

The preparation of the specimen was based on KS L2476, the mixing was carried out by weight ratio of cement and fine aggregates of 1: 2, and the bibimb was done by hand bibim. At this time, in order to maintain uniform workability, the flow rate was determined to be 170 ± 5mm and the usage amount was 30%.

Test items and application standards were the same as in Example 1, the results are shown in Table 3.

Example 1 and Comparative Example 1 Example 1 Comparative Example 1 Steelmaking converter slag useful microorganism treatment Steelmaking Slag
Useful Microorganisms Untreated Standard yarn Cement: Aggregate
(Weight ratio) 1: 1 1: 1 1: 1 Sand / Condensation Retardant 20 20 20 Defoamer (%) 2 2 2 Water / cement (%) 29.3 30.4 29.8 Density of specimen
(T / ㎥) 1.2 1.3 4.4 Absorption rate of specimen (%) 2.0 2.1 8.4 28 days of specimen
Compressive strength (kg / ㎠) 380 370 410 28 days of specimen
Flexural strength (kg / ㎠) 130 120 76

As can be seen from Table 3, the water cement ratio (W / C), weight loss rate, density, water absorption rate, age 28-day compressive strength, age 28-day bending strength, etc. of the specimens according to the examples were compared. It was found that the mortar produced by using the invention steelmaking converter slag as an aggregate substitute had no inferior physical properties compared to the material manufactured by the conventional standard yarn.

Example 3

After mortar and concrete were prepared by adding cement using steelmaking converter slag treated with useful microorganisms, the test material was placed in a VOCs generating container and sealed, and VOC was adsorbed on the adsorption tube by generating VOC at 60 ° C for 12 hours. Afterwards, VOCs were analyzed using gas chromatography (GC-MS). The mortar test results were as follows.

Comparison of results of experiments with useful microorganism-treated mortars and general mortars sample Occurrence VOCs
(Kinds) VOC total generation
() Total generation VOC
Reduction Rate (%) General-Mortar
(Standard yarn) 64 275.3 95.9 Antioxidant-Mortar
(Steelmaking converter slag)  9   11.3

Concrete test result according to the present invention sample Occurrence VOCs
(Kinds) VOC total generation
(Μg) Toluene Generation
(Μg) Antioxidant concrete 26 121.1 - Plain concrete 142 553.8 0.55

1.The total amount of VOC is reduced by about 78% from general concrete to antioxidant concrete (10 days).

2. Toluene production decreased> 94.5% from general concrete to antioxidant concrete (10 days).

Example 4

The heavy metal elution concentrations of ordinary mortar and antioxidant mortar were measured by heavy metal dissolution test method. The heavy metal dissolution test was performed in the following order. The eluted solution was centrifuged, pretreated with nitric acid, and then filtered and analyzed for heavy metals.

Heavy Metal Dissolution Test Process Suitable sample (100 g) Mixed at a ratio of 1:10 (W: V)
Distilled water + HCl added Solvent (pH 5.8 ~ 6.3) Shaking at room temperature and pressure
200 shakes / min 6 hours continuous shaking Filtration (0.45 μm filter) Sample (filtrate)

Heavy metal analysis results are as follows.

Heavy metal dissolution test results of the present invention Sample Name Analysis Copper
(Cu)
(ppm) arsenic
(As)
(ppm) cadmium
(CD)
(ppm) Hexavalent chrome
(Cr ^{6 +} )
(ppm) draft
(CN)
(ppm) Cation
Adsorption rate
(TCE)
(ppm) General mortar (using slag) 0.03 ND ND ND ND ND Antioxidant mortar (using slag) 0.01 ND ND ND ND ND General mortar (standard yarn) 0.19 ND ND ND ND ND Sample Name Analysis PCE
(ppm) Chlorine (Cl)
(ppm) Fe
(ppm) Pb
(ppm) Mercury (Hg)
(ppm) Organic
(ppm) General mortar (using slag) ND 1.92 0.2504 0.0376 ND ND Antioxidant mortar (using slag) ND 41.20 0.3232 0.0648 ND ND General mortar (standard yarn) ND 4.63 0.0529 0.0664 ND ND

ND = not detected

Claims (4)

The first step of directly injecting the useful microorganisms into the steelmaking converter slag of the appropriate particle size, or the first step of micronizing the steelmaking converter slag, and mechanically pulverizing and activating it, the second step, mixing and stirring it with the useful microorganisms, aging An environmentally friendly functional building material manufacturing method using steelmaking converter slag, characterized in that the production of environmentally friendly building materials in three steps.
The chemical composition of the steelmaking slag of claim 1 is in weight percent, 14 to 19% of iron (T? Fe), 40 to 48% of calcium oxide (CaO), 10 to 16% of silicon dioxide (SiO ₂ ), and oxidation Slag with aluminum (Al ₂ O ₃ ) 1-3%, magnesium oxide (MgO) 5-8%, manganese oxide (MnO) 4-6%.
Method of using the composition of claim 1 in the cement mortar, concrete, tile, plastic material and gypsum board.
Method of using a centrifugal vibration mill, vortex mill or planetary mill during the mechanochemical grinding in the second process of claim 1.

Images