WO2011096604A1 - Calcium aluminate clinker using waste material and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a calcium aluminate clinker using waste material and a manufacturing method thereof. More specifically, the calcium aluminate clinker is manufactured by mixing at an appropriate ratio asbestos waste, ash of incinerated domestic waste, sludge from purified water, plaster, fluorite and silicon carbide, and then calcinating the mixture to produce an environmentally friendly and low-cost calcium aluminate clinker. According to the present invention, carbon dioxide emissions can be reduced during a process of manufacturing a calcium aluminate clinker by virtue of reduced calcinating temperature and by using waste material and a resultant calcium aluminate clinker is environmentally friendly and has low production cost. Further, quality degradation of a clinker itself due to alkali components can be prevented since alkali components can be neutralized, the asbestos components of harmful asbestos wastes can be removed, and high quality cement having rapid hardening properties, high strength, high liquidity, and high expansibility can be manufactured.

Description

Calcium Aluminate-based Clinker Using Waste and Manufacturing Method Thereof

The present invention relates to a calcium aluminate-based clinker using a waste and a method for producing the same, more specifically, asbestos waste, municipal waste incinerator, purified sludge, gypsum, fluorspar and silicon carbide in an appropriate ratio, and then the mixture The present invention relates to a calcium aluminate-based clinker which is environmentally friendly and inexpensive by firing and manufacturing the same.

Clinker (clinker) is a cement material, will the source material is fired into small chunks by a rotary kiln (rotary kiln), a main component is a _{3CaO · SiO 2, 3CaO · Al} 2 O 3, 2CaO · SiO 2, 4CaO · Al 2 O of ₃ · Fe ₂ O ₃ is in four species.

Calcium aluminate-based clinker, which is one of the conventional clinkers, is composed of CaO, Al ₂ O ₃ , SiO ₂ , SO ₃ , prepared by mixing alumina minerals such as bauxite with limestone and gypsum. By mixing an appropriate amount of anhydrous gypsum (CaSO ₄ ) and quicklime (CaO) to the prepared calcium aluminate-based clinker serves as a special cement to have expansion, fastness and roughness.

In addition, in case of calcium aluminate clinker, the firing temperature is around 1,200 ~ 1,300 ℃, and it is not only energy saving type cement which has a firing temperature of 100 ~ 200 ℃ lower than that of ordinary portland cement (OPC). It can be used in various special cement fields because of its properties such as expandability, and can compensate for the defects of traditional cement.

Further, the needle and the main phase by a hydration reaction with water eth- ring ZUID _{(C 3 A · 3CaSO 4 ·} 32H 2 O), mono-sulphate _{(C 3 A · CaSO 4 ·} 12H 2 O) and Ca (OH) ₂ It shows the expansion effect due to the generation of hydrates, and can prevent the hardening of the hardened body due to dry shrinkage, which is a disadvantage of the existing Portland cement clinker, and can improve the low tensile strength.

However, since these clinkers use natural resources as raw materials, as the natural resources are gradually depleted, the supply and demand inevitably arises in the near future, and development of alternative resources is urgently needed, and the cost of purchasing raw materials is high.

On the other hand, pollution of air, soil and water is becoming a serious social problem in the process of industrialization of society, and these wastes are collected in the form of separate collection and reclamation due to various types of wastes generated at home or various industrial sites. It is rapidly polluting soil, water quality and air environment.

In recent years, disposal of asbestos used in building materials, automobile parts, textile products, etc., such as waste asbestos or asbestos-containing waste, has become a serious social problem. Only stabilization and solidification using cement are carried out in some places, and most of them are buried in designated waste landfills operated by the Environmental Management Corporation because there is no place to melt or lack recycling technology.

Moreover, even in the case of sewage sludge, the treatment method has been dependent only on ocean dumping or landfilling until recently, and the facilities generating sewage sludge are gradually increasing, and it is required to derive new treatment methods in addition to the landfill treatment.

Thus, the present inventors have made efforts to solve the problems of the prior art, as a result of mixing asbestos, fluorite and silicon carbide in wastes such as asbestos waste, municipal waste incineration, water purification sludge in an appropriate ratio, and then fired to manufacture, The present invention was completed to confirm that it is possible to manufacture an eco-friendly and inexpensive calcium aluminate-based clinker.

Summary of the Invention

The present invention is to provide a method for producing calcium aluminate clinker which is environmentally friendly at the same time using waste, and has excellent fastness, high strength, high flowability and expandability at a low price, and a calcium aluminate clinker produced by the method. .

 The present invention (a) 30 to 70 parts by weight of purified water sludge, 10 to 40 parts by weight of asbestos waste, 1 to 5 parts by weight of silicon carbide, 5 to 15 parts by weight of gypsum and 2 to 10 parts by weight of 100% by weight of household waste incineration Mixing parts by weight; And (b) provides a method for producing calcium aluminate-based clinker using waste comprising the step of firing the mixture in a sealed space for a temperature increase rate of 10 ℃ / min to 1000 ~ 1300 ℃ for 1 to 2 hours.

The present invention also provides 30 to 70 parts by weight of purified water sludge, 10 to 40 parts by weight of asbestos waste, 1 to 5 parts by weight of silicon carbide, and 5 to 15 parts by weight of gypsum, which is produced by the above method. It provides a clinker comprising a portion and 2 to 10 parts by weight of fluorspar.

1 is a flow chart illustrating a method of manufacturing a clinker according to the present invention.

Figure 2 is an image of the XRD of the clinker prepared by the manufacturing method according to the present invention.

Detailed Description of the Invention and Specific Embodiments

Other features and embodiments of the invention will be apparent from the following detailed description and the appended claims.

In accordance with one aspect of the present invention, (a) 30 to 70 parts by weight of purified water sludge, 10 to 40 parts by weight of asbestos waste, 1 to 5 parts by weight of silicon carbide, 5 to 15 parts by weight of gypsum, and 100 parts by weight of household waste incinerator Mixing 2 to 10 parts by weight of fluorspar; And (b) relates to a method for producing calcium aluminate-based clinker using waste comprising the step of firing the mixture in a closed space for a temperature increase rate of 1000 ℃ to 1300 ℃ for 1 to 2 hours at 10 ℃ / min.

More specifically, the present invention is environmentally friendly and inexpensive by mixing silicon carbide, gypsum and formation in municipal waste incinerator, water purification sludge and asbestos waste, which are wastes, and firing at high temperature, as well as excellent fastness, high strength, high flowability, and expandability. It relates to a method for producing a clinker.

In the present invention, the municipal waste incineration means a by-product that has been used after incineration of materials other than industrial waste that has been used in all human life but lost its use without being used.

The municipal waste incinerator according to the present invention uses a CaO content of 25 wt% or more, and a Cl content of 15 wt% or more, because the use of municipal waste incinerators as CaO and Cl sources of calcium aluminate clinker.

The municipal waste incinerator according to the present invention is injected into the incinerator generated from the municipal waste incinerator to be used as a raw material of cement while injecting carbonic acid ions into a fly ash: water ratio of 1:10 to 1: 1 in water, in a temperature range of 5 to 50 ° C. 1 It may be used to remove the harmful components of the chlorine component and heavy metal by washing more than once.

In this process, the toxic substances are stabilized during the incineration process, and due to the large amount of chlorine, the calcination temperature is 100 ~ 200 ° C lower than that of general portland cement, and the fastness of the calcium chloride is excellent and the expansion rate is good. It can be used as a raw material for cement clinker containing nate.

In the present invention, the purified sludge is generally cake sludge generated after the waste water is purified, and when fired with a chemical composition of SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , SO ₃ , CaO, etc. Since it is similar to the component of, it is possible to produce a clinker for cement using the purified sludge to be discarded.

The purified sludge according to the present invention has an Al ₂ O ₃ content of 40 wt% or more and an SO ₃ content of 5 wt% or more, which is used as Al ₂ O ₃ and SO ₃ sources of calcium aluminate clinker. Because.

In addition, in this invention, a thing whose water content is 15% or less can be used for purified water sludge. This is because when the water content of the purified sludge exceeds 15%, it is stuck to the sintering machine and the calcination process cannot be carried out effectively.

In the present invention, asbestos waste is excellent in durability, heat resistance, chemical resistance, electrical insulation, and the like, and inexpensive asbestos is a waste which is dismantled after being used as a building material, fireproof material, electrical insulation material, and fireproof coating material. As a result, asbestos fibers floating in the air are extremely harmful to the human body, causing asbestosis and the like, and the treatment process is strictly limited. Accordingly, in the present invention, by treating the asbestos waste to produce asbestos clinker, to prevent environmental pollution due to asbestos, and to recycle the waste asbestos by producing an environmentally friendly material with excellent strength and porosity without detecting asbestos components The cost of processing can be reduced.

In the present invention, the silicon carbide is a silicon carbide of formula SiC. Very hard, clean, greenish crystalline compound of silicon and carbon, molecular weight: 40.1, specific gravity: 3.21, decompose at 2500 ℃ It is a material that attracts attention as a high temperature structural material due to its high temperature strength, excellent wear resistance, oxidation resistance, corrosion resistance, crack resistance, etc., and now mechanical seals, bearings, various nozzles, high temperature cutting tools, fireproof plates, abrasives, steelmaking It is a material widely used in reducing materials and lightning arresters, etc. In actual production, silicon carbide expands the interior of the pores formed during foaming and is not affected by thermal changes, thus shrinking the foamed pores during cooling. It keeps it unchanged.

In addition, when the silicon carbide is mixed with asbestos waste and rises above 900 ° C., asbestos components begin to melt at 900 ° C., and silicon carbide is melted at 1150 ° C., thereby exchanging physical properties of the asbestos waste. You can.

In the present invention, asbestos non-asbestos refers to the change of harmful components into harmless components. As described above, after asbestos waste is treated by non-asbestos treatment, metal ions such as calcium fluoride, Al, and Fe are generated, and calcium fluoroaluminate is produced. It can be used as a clinker raw material.

In the present invention. Gypsum and fluorspar are used to neutralize alkali components in the raw materials used in the present invention.Alkali components such as K ₂ 0 and Na ₂ O contained in wastes increase the viscosity of the liquid phase during clinker firing to improve the quality of clinker. In addition, the alkali component causes volatilization and condensation inside the calcination machine to become unstable. Therefore, in consideration of this point, gypsum and fluorspar are added to the clinker raw material which can neutralize the alkali component. In addition, the fluorspar has the effect of reducing the firing temperature of the mixture, as containing CaF ₂ as a main component.

In the present invention, the gypsum may be selected from the group consisting of desulfurized gypsum, phosphate gypsum, hydrofluoric acid gypsum and mixtures thereof.

In the present invention, 30 parts by weight to 70 parts by weight of purified water sludge, 10 parts by weight to 40 parts by weight of asbestos waste, 1 part by weight to 5 parts by weight of silicon carbide, and 5 parts by weight to 15 parts by weight of gypsum waste It can be characterized by mixing 2 parts by weight to 10 parts by weight of fluorite and fluorspar.

When 100 parts by weight of household waste incineration is added to less than 30 parts by weight of purified water sludge, the efficiency of water purification sludge is insignificant, and when it exceeds 70 parts by weight, it cannot be properly pressed and pressed to the calcination machine. , There is a problem that the firing temperature is increased.

In addition, with respect to 100 parts by weight of domestic waste incinerator, when asbestos waste is added less than 10 parts by weight, the efficiency of asbestos disposal is low, and when it exceeds 40 parts by weight, it is difficult to be non-asbestosated.

In addition, with respect to 100 parts by weight of municipal waste incineration, less than 1 part by weight of silicon carbide is difficult to be non-asbestosized, and when it is added in excess of 5 parts by weight, excessive bubbles may occur and the strength of the clinker may be weakened. have.

If it is added to less than 5 parts by weight of gypsum or 2 parts by weight of fluorspar, the quality of the clinker may not be neutralized due to 100 parts by weight of household waste incinerators, and the quality of the clinker may exceed 15 parts by weight or 10 parts by weight of fluorspar. In this case, there is a disadvantage that the manufacturing cost increases.

As described above, the mixture mixed at the mixing ratio may be further dried such that the water content of the mixture is 10% or less before firing. This is because when the water content of the mixture exceeds 10%, it sticks to the inner wall of the calcination machine and the calcination does not proceed smoothly.

The mixture thus mixed is calcined for 1 to 2 hours at a temperature of 900 ℃ to 1300 ℃ in a closed space. In addition, when the firing process is performed in an open space, asbestos components may be scattered during the firing process, or chlorine may be volatilized, thereby degrading the quality of the clinker.

Calcium aluminate-based clinker manufacturing method according to the present invention is environmentally friendly and low cost by manufacturing by using waste while reducing the amount of fuel consumption and carbon dioxide generated by performing the firing process at a temperature lower than the firing temperature when manufacturing the conventional clinker In addition, it is possible to neutralize the alkali component to prevent the deterioration of the quality of the clinker itself due to the alkali component and to reduce the firing temperature, and to non-asbestosize harmful asbestos wastes, and to have excellent spalling rigidity, high strength, high flowability, and expandability. Cement can be prepared.

In another aspect, the present invention is produced by the above production method, with respect to 100 parts by weight of domestic waste incinerator, water purification sludge 30 to 70 parts by weight, asbestos waste 10 to 40 parts by weight, silicon carbide 1 to 5 parts by weight, gypsum 5 ~ It relates to a clinker comprising 15 parts by weight and 2 to 10 parts by weight of fluorspar.

Calcium aluminate-based clinker according to the present invention by containing the domestic waste incinerator, purified sludge, asbestos waste, calcium aluminate-based clinker is prepared based on the main components contained in the waste, so that the firing temperature is conventional Portland It is 100 ~ 300 ℃ lower than cement and has fast stiffness and good expansion rate, so it does not cause cracks.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention, it will be apparent to those skilled in the art that the scope of the present invention is not to be construed as being limited by these examples.

Example 1

7.5 parts by weight of purified water sludge (tantan) having a chemical composition of Table 2, and a chrysotile asbestos waste having an chemical composition of Table 3 with respect to 100 parts by weight of household waste incineration ash having a chemical composition of Table 1 (DS Industry, Korea) , Korea) 20 parts by weight, 10 parts by weight of gypsum and 7 parts by weight of fluorspar and 3 parts by weight of silicon carbide were mixed, and then the kiln was sealed and calcined at 1000 to 1300 ° C. at a heating rate of 10 ° C./min for 1 hour. It was.

Table 1

TABLE 2

TABLE 3

As a result, the clinker prepared as shown in Figure 2 showed a tendency of mineral crystal phase by firing temperature, the main crystalline phase of the material calcined at 1000 ℃ is calcium chloroaluminate crystal phase and Anhydrite (CaSO ₄ ) , KCl, NaCl were found. In particular, it can be seen that calcium chloroaluminate (11CaO.7Al ₂ O ₃ .CaCl ₂ ), NaCl and KCl crystal phases are many in the closed kiln. When calcined in an enclosed kiln, chlorine (Cl ⁻ ) component was present without volatilization, and thus many calcium chloroaluminate crystal phases were generated.

In addition, the crystalline phase at 1100 ℃ is almost the same as the crystalline phase of 1000 ℃ calcium chloro aluminate is the main crystalline phase, gehlenite (CaAlSiO ₇ ) is formed as CaSO ₄ decreases, KCl, NaCl also decreases. The main crystal phase at 1200 ° C is gehlenite, and the crystal phase of calcium chloroaluminate disappears gradually, and there are trace amounts of NaCl and KCl. Even at 1300 ° C, the main crystal phase was gehlenite and a new crystal phase of calcium sulfoaluminate (Calciumsulfoaluminate-4CaO · 3Al ₂ O ₃ · SO ₄ ) was newly formed.

As described above in detail specific parts of the present invention, it will be apparent to those skilled in the art that these specific descriptions are merely preferred embodiments, and thus the scope of the present invention is not limited thereto. will be.

Calcium aluminate-based clinker according to the present invention reduces the generation of carbon dioxide generated during the manufacturing process due to the reduction of the firing temperature, is manufactured by using waste, eco-friendly and inexpensive, and can also neutralize the alkali component to the alkaline component It is possible to prevent the deterioration of the clinker itself due to the non-asbestos, as well as to produce the high-quality cement excellent in fast hardness, high strength, high fluidity, expandability and the like asbestos waste.

Claims (5)

1. Calcium aluminate clinker manufacturing method using the waste comprising the following steps:

   (a) 30 to 70 parts by weight of purified water sludge, 10 to 40 parts by weight of asbestos waste, 1 to 5 parts by weight of silicon carbide, 5 to 15 parts by weight of gypsum and 2 to 10 parts by weight of fluorspar, per 100 parts by weight of municipal waste incineration Making a step; And

   (b) baking the mixture in a closed space at a rate of temperature increase of 10 ° C./min to 1000 ° C. to 1300 ° C. for 1 to 2 hours.
2. The method of claim 1, wherein the gypsum is selected from the group consisting of desulfurized gypsum, phosphate gypsum, hydrofluoric acid gypsum and mixtures thereof.
3. According to claim 1, The municipal waste incinerator has a content of CaO of 25wt% or more, Cl content of 15wt% or more, The purified sludge is Al ₂ O ₃ or more 40wt%, SO ₃ content At least 5wt%.
4. The method of claim 1, wherein step (b) further comprises drying the mixture so that the moisture content of the mixture is 10% or less before firing the mixture.
5. It is produced by the production method according to any one of claims 1 to 4, 30 to 70 parts by weight of purified water sludge, 10 to 40 parts by weight of asbestos waste, 1 to 5 parts by weight of silicon carbide, Calcium aluminate-based clinker comprising 5 to 15 parts by weight of gypsum and 2 to 10 parts by weight of fluorite.

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