KR100541777B1 - Manufacturing method of artificial allophanic clay minerals from the fly ash and incinerator's ash - Google Patents

Abstract

The present invention utilizes fly ash or industrial waste generated from coal-fired power plants or steel mills as incinerators after incineration to remove nitrogen, phosphorus, rust and red tide treatment agents. The purpose of the present invention is to propose an artificially safe method for manufacturing high quality Allophane vaginal clay mineral.

To this end, hydrochloric acid (HCl) is heated by heating anhydrous amorphous aluminum silicate salt produced after combustion in a coal-fired power plant, steel mill or incinerator to 90-180 ° C in an aqueous solution. Product is treated at a pH of about 4 to produce allophosphorus clay mineral, an aluminum silicate salt of amorphous water, which is hygienic and safe by washing with harmful heavy metals in an acidic state. To make.

Of particular note, because allophosphorus clay minerals have a cation exchange capacity (CEC) and anion exchange capacity (AEC), they are excellent in removing nitrogen and phosphorus. It is expected to be widely used for phosphorus remover, green / red tide treatment and microbial culture process.

Fly ash, incineration ash, allophane, clay mineral, aluminum silicate, cation exchange capacity, anion exchange capacity

Description

Manufacturing method of artificial allophanic clay minerals from the fly ash and incinerator's ash}

1 is a process chart for manufacturing artificial allotropin clay mineral from coal ash or incineration ash

In the present invention, nitrogen, phosphorus remover, rust / red tide treatment agent and organic substances in sewage and wastewater are discharged from incineration ash discharged from an incinerator for burning coal ash or industrial waste generated from a coal-fired power plant or steel mill. The present invention relates to an artificial manufacturing method of allophane clay minerals used as a mineral supply to soil microorganisms in converting corrosive reactions.

Naturally allophosphorus clay minerals are present in the volcanic acid volcanic soil, and the silica ratio (SiO ₂ / Al ₂ O ₃ ) is 0.3 _~ 2.0 wide, mainly silicon (Si) and aluminum (Al). ), Oxygen (O), hydrogen (H) is chemically the site of the Al (OH) H ₂ O group consisting of a silanol group (Si-OH) and activated aluminum to a number of Si-O-Al bonds Clay minerals of aluminum silicate salts with condensation (dehydration-bonding) of silicic acid, each hollow spherical particle has a certain form. It is also called non-crystalline clay because silicon, aluminum, oxygen, and hydrogen are randomly combined and appear to be amorphous by X-ray diffraction.

Because of the large amount of active aluminum and active minerals, allophyllin clay minerals have high anion exchange capacity (AEC), which is very effective in fixing phosphate, and in soils, it contains large amounts of corrosive substances (organic soils). It exists as aggregated humus soil, and also has a cation exchange capacity (CEC), so it also has the ability to fix cations such as K ⁺ , Na ⁺ and NH ₄ ⁺ . Allophyllin minerals contain many active minerals (water-soluble minerals), and because of their low binding strength, they are characterized by physical and chemical weathering and soil microorganisms caused by wind and water in nature. It is excellent in the function of supplying minerals to soil microorganisms and plants by receiving biological weathering which is eroded by metabolites.

Therefore, it is widely used in the process of treating organic pollutants by biological corrosive reaction of sewage and wastewater treatment, odor treatment process, and drinking water treatment of livestock.

Mechanism in which allotropin clay mineral is produced naturally is the early volcanic ash from which siliceous minerals are energized by geothermal heat and molten lava is released into the atmosphere by volcanic activity. It was deposited in the state of amorphous aluminum silicate (non-water) and acidified by reaction with water by rainwater, etc. The reaction mechanism is as follows.

Other activated minerals (M ^{n +} ) were also acidified while releasing hydrogen ions (H ⁺ ) by the same reactions as those of the above ① to ④.

M ^{n +} nH ₂ O --- → nM (OH) _{n (aq)} + n H ⁺ _(aq) ･ ･ ･ ･ ･ ･ ⑤

Anhydrous amorphous aluminum silicate salt in the state of weakly acidic pH of 4 ~ 6 became an allophospholipid clay mineral, an amorphous aluminum silicate salt of Hwasu, and when the pH becomes strong acid less than 2, it is a crystalline aluminum silicate salt of Hwasu. It was converted to an imogolite vaginal clay mineral.

On the other hand, when there are relatively large amounts of free alkali oxides (Na ₂ O, K ₂ O, etc.) or alkaline earth metal oxides (CaO, MgO, BaO, etc.) of volcanic eruptions, geothermal heating reactions occur in alkali state. Zeolite was formed in.

Fly ash is a non-combustible clay mineral in coal. When it is burned (1,400 ~ 1,700 ℃), it is not burned and is energized to be melted. It is then scattered with the exhaust gas and cooled by recovering heat from the boiler. Collected and discharged in the electrostatic precipitator in the form of particulate spherical particles, about 70wt% of silicic acid (SiO ₂ ) and alumina (Alumina; Al ₂ O ₃ ), about 5wt% of iron oxide (Fe ₂ O ₃ ), etc. It is composed of MnO, TiO ₂ , P ₂ O _5, etc., and has anhydrous amorphous aluminum silicate salt as the main component like the initial state of volcanic eruption.

Therefore, when coal ash or incineration is heated at weak acidity (pH = 4 ~ 6), allophane, an amorphous aluminum silicate salt, is heated, and when warmed at strong acidity of 2 or less pH, Imogolite, which is a crystalline aluminum silicate of, is produced, and zeolite, which has a high cation exchange capacity, is formed by heating in an alkali state.

Using the above-mentioned principle of the production of allophosphorus clay minerals in Korea Patent Publication No. 2001-0089935, coal ashes and incineration ashes are heated in an acidic state to produce artificial allopein minerals. When minerals are burned and energized, there are a large amount of water-soluble minerals activated. Among them, trace metals such as copper (Cu), cadmium (Cd), and chromium (Cr) are harmful to the human body. It is a problem that it is not widely used because the harmful heavy metal component can cause harmful action to human body by the food chain when spraying it in rivers or sea areas for rust and red tide treatment as a product in the state. In Korea Patent Publication No. 2002-0039292 Coal ash or incineration ash is stabilized in alkaline state and warmed in acidic state. It presented a method for producing mineral quality to the campaign, but also do not have the heavy metals contained in fly ash or incinerated once removed there is a usability problem.

It is an object of the present invention to propose a method for producing artificial allotropin clay minerals of hygienic and safe oil value while solving the problems of the prior art incineration ash discharged from coal ash or industrial waste incinerator, which is mostly treated as waste.

In order to achieve the above object, coal ash or incineration ash is stabilized by heating to 90-180 ° C in alkaline aqueous solution, and then heated (90-180 ° C) after adjusting the pH to 4 by adding hydrochloric acid (HCl). After agitating in the state, it is converted to allotropin clay mineral, which is an aluminum silicate salt of amorphous water, sent to a dehydrator and washed with water to remove harmful heavy metals. Make

Hereinafter, with reference to the accompanying drawings in detail as follows.

Alkaline metal oxides (Na ₂ O, K ₂ O, etc.) and alkaline earth metal oxides (CaO, MgO, etc.) are present in coal ashes and incineration ashes, which are particulate spherical particle powders containing anhydrous amorphous aluminum silicate salts. pH shows alkalinity in the range of 12-13.

To improve the reaction efficiency of coal ash or incineration ash with allophosphorus clay mineral, which is an aluminum silicate salt of Hwahwa, zeolite (heat treatment is performed in alkali state rather than acid in aqueous solution and heat treatment in acidic state). After stabilizing with zeolite, adjusting the pH to 4 by adding hydrochloric acid (HCl) in a heated state and then stirring the reaction, coal ash or incineration ash contains an alkali component, but a small amount Since it contains 4 ~ 5wt% of caustic soda (NaOH) and salt (NaCl), the mixture is heated to 90 ~ 180 ° C and stirred for more than 4 hours to stabilize with zeolite, and then hydrochloric acid is added to adjust pH to 4. Then, the mixture is stirred for 4 hours or more in a heated (90 to 180 ° C.) state, and is converted into an allophosphorus clay mineral, which is an amorphous aluminum silicate salt.

However, coal ash or incineration ash is not an oil-based substance, so when it is used as nitrogen, phosphorus remover or rust / red tide treatment agent for sewage and wastewater treatment, it is considered to be economical, such as caustic soda and salt. Since there is no need to use oil-based materials, even if the reaction efficiency decreases, the alkali stabilization reaction is carried out using only alkali components in coal ash or incineration ash.

When the reaction is completed with allophyllin clay mineral, it is sent to the dehydrator for dehydration, and the water is washed with an allophosphorus clay mineral dehydrated with a spray nozzle to remove water-soluble harmful heavy metal components.

The weakly acidic allotropin clay mineral, which is washed with water, and dehydrated with harmful heavy metals, is commercialized as nitrogen, phosphorus remover, or rust and red tide treatment in sewage and wastewater treatment.

If necessary, dehydrated allophosphorus clay mineral is added to caustic soda in an aqueous solution, neutralized to pH 7, and dehydrated.

In addition, when used for supplying minerals to microorganisms, animals and plants, etc. in a bio-reactor of animal drinking water treatment or wastewater treatment, they are molded and processed into pellets.

Molding process of pellets is 5wt% of bentonite with inorganic binder and alginic acid with inorganic binder on the basis of dry weight of allophosphorous clay minerals to allotropin clay minerals that have been removed and dehydrated from harmful heavy metals. Sodium (Sodium alginate) or cellulose (Cellulose) resin is mixed with 10wt%, ammonium chloride (NH ₄ Cl) is mixed with 10wt% and water is added to them to facilitate the molding process to pellet form of the whole mixture After adjusting the water content in the range of 38-43wt%, stirring and mixing, forming and processing into rod-shaped pellets and drying them naturally at room temperature, and then heating them to 1,000 ℃ or higher in an electric furnace or a heating furnace, Process a variety of dried pellets.

The dehydration liquid and the flushing water containing the harmful heavy metal components are sent to the neutralization tank to adjust the pH to 7-8 with neutralizing agents (NaOH, Ca (OH) _2, etc.) to convert the water-soluble heavy metal components into solid metal hydroxides, Flock is formed by injecting flocculant to facilitate sedimentation in the sedimentation tank, and then sent to the sedimentation tank to settle the solids, and the supernatant is sent to the treatment tank to be reused or discharged as flushing water, and slurries are deposited. Sent to the dehydrator for dehydration.

As will be apparent from the above description, the present invention has the effect of self-cycling waste resources from pellets of allophospholipid clay minerals from coal ashes and incineration ashes generated as wastes, and this is a microbial culture process or drinking water for livestock. It is expected to be widely used for mineral supply because of its superior performance compared to natural pumice which has been used mainly until now when used for mineral supply in processing processes.

Claims (3)

In order to improve the reaction efficiency in the production of allophane vaginal clay minerals, which are aluminum silicate salts of amorphous water from fly ash or incineration ash, NaOH) and salt (NaCl) were added to 4-5 wt% alkaline aqueous solution and heated at 90-180 ° C for stirring for at least 4 hours to stabilize with zeolite, and then heated to the same temperature. After hydrochloric acid (HCl) was added, the pH was adjusted to 4, followed by stirring for at least 4 hours to convert allophospholipid clay mineral, which is an amorphous aluminum silicate salt, to remove harmful heavy metals by washing with water. To manufacture artificially safe hyaluronic clay minerals According to claim 1, since coal ash and incineration ash are not oily substances, the reaction efficiency is somewhat reduced when considering the economic problems when using nitrogen, phosphorus remover or rust / red tide treatment agent in sewage and wastewater treatment. Even if the alkaline stabilization reaction does not use valuable materials such as caustic soda or salt, alkali stabilization reaction is carried out using only alkali components in coal ash or incineration ash, and then hydrochloric acid (HCl) is added at the same temperature. Is adjusted to 4 and stirred for at least 4 hours to convert allotropin clay mineral, which is an amorphous aluminum silicate salt, to remove detrimental heavy metals by washing with water. How to make clay minerals According to claim 1, 5% by weight of bentonite (Bentonite) in an inorganic binder (organic binder) on the basis of the dry weight of the allopein clay mineral in the powdered allophosphorus clay mineral, which has been removed from the harmful heavy metal components and dehydrated Furnace is mixed with 10 wt% of Alginic acid Soda or Cellulose, 10 wt% of ammonium chloride (NH ₄ Cl), and is easily molded into pellets. Water was added to them to adjust the water content of the entire mixture to 38 to 43 wt%, followed by stirring and mixing to form spherical or rod-shaped pellets, followed by natural drying at room temperature. A method for producing artificial allopine-like clay minerals on porous dried pellets by heating to 1,000 ° C. or higher in a heating furnace.

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