KR20090115085A - Hydraulic hardened complex forms comprising paper-making sludge incineration ash as main material, and method for preparing the same - Google Patents

Abstract

PURPOSE: Hydraulic hardened complex forms comprising paper-making sludge incineration ash, and a preparation method thereof are provided to exhibit excellent dimensional stability for use as construction materials. CONSTITUTION: Hydraulic hardened complex forms are composed of paper-making sludge incineration ash, gypsum dihydrate, organic emulsion, reinforcing fiber, and water. A method for preparing the hydraulic hardened complex forms comprises the following steps of: mixing all those ingredients to make mixed slurry; molding the mixed slurry; curing the molded forms; and drying the cured forms.

Description

HYDRAULIC HARDENED COMPLEX FORMS COMPRISING PAPER-MAKING SLUDGE INCINERATION ASH AS MAIN MATERIAL, AND METHOD FOR PREPARING THE SAME}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite water-curing molded article having a high specific strength and shrinkage expansion as a main component of paper sludge incineration ash, and having a fire and heat resistance stability, and a method for producing the same.

It is known that paper sludge incineration can be used as a raw material for building materials. Usually used in combination with cement, using a curing method such as cement or autoclave curing method, etc. to manufacture from building materials such as boards. However, building materials by the formation of ethringite, such as cement, has a large contraction and expansion, so when used for external use, there is a limit to the control of the rate of change of length by absorption even if the autoclave is cured.

On the other hand, the present inventors have already made paper sludge incineration ash as a main raw material in Korean Patent Publication No. 10-2005-0008417, Korean Patent Publication No. 10-2006-0002643, and Korean Patent Publication No. 10-2006-0040434. Disclosed is a method of manufacturing from building materials. However, these patents use only a part of the manufactured material properties, and anyone can recognize that they can be developed into building materials having better properties.

On the other hand, conventional artificial wood is recycled construction materials mainly known as waste wood and waste plastics are known. As waste wood, wood-based raw materials such as waste wood discharged at the time of house dismantling are used. As waste plastics, plastic-based raw materials that crush polyethylene, polypropylene trays, sheets, and the like into flakes are used as industrial wastes. Artificial wood is made by kneading and heating molding several hundred microns of crushed wood and thermoplastic resin, and it is a structure that plastic fills the gap of wood powder to protect the surface, so it has excellent water resistance and no damage by bacteria, ants, etc. May have In addition, since preservatives and the like are unnecessary, toxicity to humans or animals can be excluded. In addition, instead of preservative treatment by adding preservatives to general wood, artificial wood is manufactured by a method of forcibly injecting plastic sol.

However, they are similar in appearance to wood, but are vulnerable to heat and fire because their main components are organic, and they are difficult to contain pores, so they do not have the same humidity control as natural wood, and are substantially press-molded or forced to inject organic matter into wood. Because of its high specific gravity, it is difficult to handle like wood, and it is difficult to process nailing, planer, cutting, and finishing.

Calcium silicate artificial wood is known as a ceramic artificial wood in comparison with artificial wood using such wood and plastic. Calcium silicate system has many advantages due to its high specific strength, but uses a large amount of water in production, and it is difficult to select and use raw materials. Therefore, productivity is low compared to other materials. There is a problem that is difficult to supply as building materials.

In view of the problems of the prior art, an object of the present invention is to provide a composite hydrocuring molded article mainly comprising paper sludge incineration ash, which is excellent in dimensional stability and easy to use as a building material, and a method of manufacturing the same.

It is still another object of the present invention to provide a composite water-curing molded article based on paper sludge incineration ash having fire resistance and heat resistance stability and a method for producing the same.

Still another object of the present invention is to provide a composite hydrocuring molded article mainly containing paper sludge incineration ash having excellent processability, such as nailing, planer, and filament, as well as humidity, such as wood, and a manufacturing method thereof.

Another object of the present invention is to provide a composite hydrocuring molded article mainly comprising paper sludge incineration ash, which exhibits high strength against specific gravity, and a method of manufacturing the same.

It is still another object of the present invention to provide a composite hydrocuring molded article having a ceramic-based and brittle paper sludge incineration ash as a main component and a method for producing the same.

The present invention to achieve the above object,

On a solid basis

a) 100 parts by weight of paper sludge incineration ash;

b) 5 to 40 parts by weight of hydrated gypsum;

c) 1 to 100 parts by weight of an organic emulsion; And

d) 0.1 to 30 parts by weight of reinforcing fibers

It provides a composite hydrocuring molded article having a length change rate of 0.10% or less due to absorption.

In addition, the present invention

a) iii) paper sludge incineration ash;

   Ii) gypsum;

   Viii) organic emulsions;

   Iii) reinforcing fibers; And

   Iii) water

   Mixing to prepare a mixed slurry;

b) forming the mixed slurry of step a) by yeosu;

c) curing the molding of step b); And

d) drying the sheep of step c)

It provides a method for producing a composite hydrocuring molded article having a length change rate of 0.10% or less due to absorption.

In addition, the present invention

a) iii) paper sludge incineration ash;

   Ii) gypsum;

   Viii) organic emulsions;

   Iii) reinforcing fibers;

   V) methylcellulose as extrusion modifier; And

   Iii) water

   Mixing to prepare a kneaded product;

b) extruding the kneaded product of step a) into an extruder;

c) curing the extrudate of step b); And

d) drying the sheep of step c);

It provides a method for producing a composite hydrocuring molded article having a length change rate of 0.10% or less due to absorption.

The composite water-curing molded article of the present invention exhibits excellent physical properties over cement secondary products without using cement, and has a very low rate of change in length due to absorption, and has processability and humidity control properties such as nails, planers, and filaments, such as wood. Due to its low oscillation property, it can be used as artificial wood. In addition, industrial waste is used as the main raw material, and the manufacturing process is simple and very economical, and it is easy to control the strength and lightness.

The inventors of the present invention, based on the Korean Patent Publication No. 10-2005-0008417, the inorganic binder produced from paper sludge incineration ash and waste gypsum (the main component is hydrated gypsum) is an additive of reinforcing fibers, lightening agents, fillers, organic emulsions, etc. Even when mixed and molded, a composite water-curing molded body is formed within a short time, and the composite molded body has found that the shrinkage and expansion is extremely small, and thus, the present invention has been completed.

In addition, the mixed slurry of the paper sludge incineration ash and waste gypsum was found to be excellent in filtration and filtrate in the gold mesh, and to exhibit a high strength against the specific gravity of the molding and completed the present invention.

In addition, the mixture of papermaking sludge incineration ash and waste gypsum has been found to have the ability to hold an organic emulsion so that pressure dewatering molding is possible without using a special flocculant and completed the present invention.

In addition, the mixture of paper sludge incineration ash and waste gypsum was found that only a slight thixotrope was generated so that extrusion was possible and completed the present invention.

Hereinafter, the present invention will be described in more detail.

The composition of the molded article of the present invention is

a) 100 parts by weight of paper sludge incineration ash;

b) 5 to 40 parts by weight of hydrated gypsum;

c) 1 to 100 parts by weight of an organic emulsion; And

d) 0.1 to 30 parts by weight of reinforcing fibers

It is preferable to include.

The paper sludge incineration ash used in the present invention is different in composition and particle size depending on the production process of the paper sludge and the state of incinerator, but is usually SiO ₂ 40 to 46% by weight, Al ₂ O ₃ 25 to 35% by weight, Fe ₂ O ₃ 0.5 To 2.5 wt%, TiO ₂ 1-3 wt%, CaO 5-20 wt%, MgO 3-8 wt%, Na ₂ O 0.5-2.5 wt%, K ₂ O 0.1-0.8 wt%, P ₂ O ₅ 0.1 X-ray diffraction (XRD) analysis shows crystal phases of silica, talc, and titanium oxide (rutile or anatase). , Powder having an average particle size of 50 to 200 mesh.

The hardener for hydrocuring the paper sludge incineration ash of the present invention is dihydrate gypsum, particularly by-product gypsum produced in an acid treatment process treated with waste. As such gypsum, phosphate phosphate, phosphate phosphate, titanium phosphate gypsum, flue gas desulfurization gypsum and the like can all be used. The use of such hydrated gypsum is distinguished from the gypsum use system which is conventionally calcined and converted to anhydrous or semi-hydrated gypsum and then hydrocured.

This can be used as a curing agent of paper sludge incineration ash, which is formed by the complex network by amorphous calcium silicate hydrate formation, calcium aluminate hydrate formation, recrystallization of gypsum hydrate by the transfer of calcium ions of the dihydrate gypsum Is deduced. In fact, X-ray diffraction (XRD) analysis of these hardeners revealed high peaks of calcium aluminate hydrate and gypsum hydrate that could not be identified in composition comparison, and the peaks of silica decreased significantly.

In addition, the burning loss showed a larger loss than the theoretical loss of raw materials, and it was confirmed that more water molecules participated in curing. It is inferred that such water molecules contribute to the fire resistance of the molded body and add fire resistance and heat resistance to the matrix even though many organic substances are in the hardened body. Actually, the cured product obtained from the mixture or kneaded mixture of paper sludge incineration ash and dihydrate gypsum was charged at a temperature of 700 ° C. and 800 ° C. in a furnace for 3 hours, and the rate of hot length change was 0.8% or less, respectively. In addition, the cured product formed by adding 10 to 50% by weight of an organic emulsion also exhibited 1.0% or less as a result of measuring the change in hot length in the state where only the burn loss was increased by the amount of the organic material added.

Therefore, it is preferable that dihydrate gypsum is mixed with 5-40 weight part with respect to 100 weight part of papermaking sludge incineration ashes of this invention. If it is less than 5 parts by weight or more than 40 parts by weight, a large amount of uncured material is produced, thereby reducing the adjustment of the bulk density, strength, and heat resistance of the molded body.

The molded article of the present invention may have various compounding forms depending on the molding method and the desired physical properties. Organic emulsion and reinforcing fibers are added to the curing system of paper sludge incineration ash and Isu gypsum as the basic cured body.

The organic emulsion imparts processability such as elasticity, nailing, planer, and finishing to the hardened body of paper sludge incineration ash and hydrated gypsum, and gives humidity by not filling the pores of the molded body. This is because the particle size of the organic emulsion is larger than the pores of the molded matrix, and thus acts as a binder at the outer side of the hardened body particles, thereby providing a cause of low oscillation properties. In addition, the organic emulsion may impart a capping effect to the matrix to prevent the leaching of heavy metals that may be contained in paper sludge incineration ash and waste gypsum.

Preferred organic emulsions are acrylic, latex, vinyl acetate, and the like, and organic emulsions that can act as most binders may be used.

The amount of the organic emulsion is preferably 1 to 100 parts by weight based on 100 parts by weight of paper sludge incineration ash. If it is less than 1 part by weight, the effect of adding the organic emulsion does not appear, and if it is more than 100 parts by weight, the fire resistance is poor and it may explode in the flame, which is uneconomical.

Such organic emulsions are preferred to reduce the loss of organic emulsions by agglomerating slurries using conventional flocculants, especially when forming the composition by means of yeast, particularly in the case of superforming using a large amount of water. In pressurized dewatering molding using a general mold press, an organic emulsion can be used without using a coagulant, because the paper sludge incineration ash and the slurry of the gypsum hold the organic emulsion.

In addition to the organic emulsion, a water-soluble organic binder may also be used. Preferred are polyvinyl alcohol, polyacrylamide, methyl cellulose, ethyl cellulose, carboxymethyl cellulose and the like.

The reinforcing fibers contribute to formability and retaining force (holding force) of the particles, to impart strength to the matrix, and various reinforcing fibers can be selected according to the molding method. It is obvious that the reinforcing fibers can be used alone or in combination of two or more.

Inorganic fibers include sepiolite, rock-wool, glass-wool, glass-fiber, silica-alumina fiber, alumina fiber, silica Fiber (silica fiber), carbon-fiber (carbon-fiber) and the like can be used, in particular, fibers lacking alkali resistance, such as glass fibers can also be used as reinforcing fibers of the molded article of the present invention. The slurry of the present invention shows alkalinity, but since curing is performed within a short time even without autoclave curing, etc., it can act as a reinforcing fiber without deterioration of durability. It is preferable to include a pulverized stone in consideration of the super-elasticity in the ring network initial molding.

As the organic fiber, polyacrylonitrile fiber, polyvinyl alcohol, polyethylene fiber, polypropylene fiber, pulp, paper and the like can be used. In particular, the use of highland may be the same color as wood, so a small amount is also preferable.

The amount of the reinforcing fiber added varies depending on the molding method, but is preferably 0.05 to 30 parts by weight based on 100 parts by weight of the paper sludge incineration ash, and the method of use may be a conventional molding method for cement secondary products. If it is less than 0.05 part by weight, the effect of reinforcing fiber is insignificant, and if it exceeds 30 parts by weight, it is difficult to obtain a smooth molded body due to the fiber curling phenomenon. In particular, when the added amount of the organic fiber exceeds 20 parts by weight, the fire resistance is lowered, so that the flame can not endure for a long time and burst.

The composite water-curing molded article of the present invention may further include at least one lightening agent for weight reduction. Preferred lightweighting agents are inorganic, perlite, shirasu balloon, calcium silicate hydrate and the like, and organic foaming resins such as superabsorbent resins, styrofoam, urethane foam, and the like, and pulverized products thereof. It is preferable to set the amount in a range in which the strength of the molded article does not significantly decrease. The inorganic material is preferably 1 to 200 parts by weight and the organic material is 0.1 to 20 parts by weight based on 100 parts by weight of the paper sludge incineration ash. Outside these ranges, there may be no weight reduction effect or the strength may be significantly lowered.

The composite water-curing molded article of the present invention may contain a usual filler in addition to that. The filler is preferably an inorganic filler having a low specific gravity. As the filler, calcium carbonate (hard coal, bicarbonate), talc, wollastonite and the like can be used. In particular, the crushed product of the composite water-curing molded article of the present invention can be used, and the amount of the compound can be used without deterioration of physical properties within 10% by weight of the total solids. In addition, layered materials such as vermiculite and mica are preferred to further reduce the length change rate due to absorption when additionally added to about 1% by weight of the total solids.

The composite hydrocuring molded article may further include a coupling agent such as a silane compound or a titanate. The coupling agent helps to bond the inorganic and organic materials, and the amount of the coupling agent is preferably 0.001 to 10 parts by weight based on 100 parts by weight of the total solids. If the amount is less than 0.001 part by weight, the effect of injecting is insignificant. If it exceeds 10 parts by weight, the effect of excess amount does not appear and it is uneconomical.

The composite water-curable molded article of the present invention can be molded by two molding methods, and follows the manufacturing method described above. However, these methods are not limited only.

Specifically, one method is forming by means of yeosu, super forming and mold press pressure dewatering molding. Particularly, a thin molded product is obtained by using a large amount of water in ultra-molding, for example, a circular net, a long net, a pod linear and a Magnig net. Mold press dewatering molding is suitable for forming large objects such as solid wood.

Another method is extrusion by using a small amount of water. In extrusion, it is preferable to use methyl cellulose within 3% by weight of the total solids for the purpose of thickening and extruding the mixture.

The composite hydrocuring molded article produced by such a molding method has a rate of change in length due to very low absorption. In the present invention it represents 0.01% or less, which is a very good physical property that cement secondary products are difficult to exhibit.

The composite water-curing molded article of the present invention has workability such as nail, planer, and filament, such as wood, and has small and numerous pores, depending on the molding specific gravity, and has humidity like wood, and low oscillation property as ceramic. Therefore, it is suitable for use as artificial wood.

In addition, it is easy to color the surface of the composite cured molded article of the present invention, it is easy to decorate decorations such as paint coating and film adhesion.

The present invention will be described in more detail with reference to the following examples. However, an Example is for illustrating this invention and is not limited only to these.

Example  One

100 parts by weight of paper sludge incineration ash, 700 parts by weight of titanium butyrate gypsum, 30 parts by weight of ethyl vinyl acetate copolymer emulsion, 100 parts by weight of perlite with 80 mesh particle size, 3 parts by weight of paper, and 12 mm long polyvinyl A slurry was prepared by mixing 1 part by weight of alcohol fibers, and the slurry was put into a mold (1200 mm x 2400 mm) equipped with a 60 mesh plastic net, and pressurized and dehydrated at a molding pressure of 4 kgf / cm 2 to form a molded article having a thickness of 50 mm. Got it. The molded product was cured for 24 hours under a condition of 95% humidity and a temperature of 40 ° C, followed by constant drying with a moisture content of 5% or less in a dryer at 120 ° C to prepare a panel.

The panel had a specific gravity of 0.5 and a bending strength of 80 kgf / cm 2, and were capable of nailing, planer, and paper finishing. Humidity was not more than 2 wt% with 5 wt% moisture content at 20 ~ 90% change in humidity at 25 ℃. Also, the length change rate by absorption based on KS L 5509 was 0.047%.

Example  2

100 parts by weight of paper sludge incineration ash, 20 parts by weight of phosphate gypsum, 30 parts by weight of acryl-butadiene copolymer emulsion, 15 parts by weight of fibrous pulverized stone, 0.12 parts by weight of 6 mm polyacrylonitrile fiber, wollastonite 2 parts by weight of NBKP (Needle branched kraft pulp) was mixed to prepare a slurry.

The panel had a specific gravity of 0.78 and a bending strength of 121 kgf / cm 2. Nailing, planer, and paper finishing were possible. Humidity was not more than 1.5 wt.% At 5 wt.% Moisture content with 20 ~ 90% change in humidity at 25 ℃. In addition, the length change rate by absorption based on KS L 5509 was 0.051%.

Example  3

100 parts by weight of paper sludge incineration ash, 200 parts by weight of titanium butyrate gypsum, 30 parts by weight of ethyl vinyl acetate copolymer emulsion, 50 parts by weight of perlite with 80 mesh particle size, 2 parts by weight of paper, polyvinyl alcohol of 12 mm length 0.5 part by weight of fiber, 0.5 part by weight of polypropylene fiber having a length of 6 mm, and 1.5 parts by weight of methyl cellulose were mixed and kneaded in a kneader for 5 minutes to prepare a kneaded material, which was then introduced into a vacuum twin screw extruder through a conveyor. (w) Extruded through a die of 455 mm x (t) 12 mm at a rate of 1,100 mm / min, cured in a tray for 24 hours under a condition of 95% humidity and a temperature of 40 ° C. By weight drying to below%, an extruded panel having a thickness of 12 mm and a length of 3,600 mm was prepared.

The panel had a specific gravity of 0.98 and a bending strength of 155 kgf / cm 2, and were capable of nailing, planer, and paper finishing. Humidity was not more than 1.0 wt.% At 5 wt.% Moisture content panel with 20 ~ 90% change in humidity at 25 ℃. In addition, the length change rate by absorption based on KS L 5509 was 0.048%.

Claims (6)

On a solid basis a) 100 parts by weight of paper sludge incineration ash; b) 5 to 40 parts by weight of hydrated gypsum; c) 1 to 100 parts by weight of an organic emulsion; And d) 0.1 to 30 parts by weight of reinforcing fibers Composite water-curing molded article has a length change rate of 0.10% or less due to absorption. The method of claim 1, e) 0.1 to 200 parts by weight of lightening agent Composite hydrocuring molded article having a length change rate of 0.10% or less due to absorption further comprising. a) iii) paper sludge incineration ash;    Ii) gypsum;    Viii) organic emulsions;    Iii) reinforcing fibers; And    Iii) water    Mixing to prepare a mixed slurry; b) forming the mixed slurry of step a) by yeosu; c) curing the molding of step b); And d) drying the sheep of step c) Method of producing a composite hydrocuring molded article having a length change rate of 0.10% or less due to absorption. The method of claim 3, wherein The mixing slurry of step a) is a method for producing a composite hydrocuring molded article having a length change rate of 0.10% or less due to absorption further comprising 0.1 to 200 parts by weight of the lightweighting agent. a) iii) paper sludge incineration ash;    Ii) gypsum;    Viii) organic emulsions;    Iii) reinforcing fibers;    V) methylcellulose as extrusion modifier; And    Iii) water    Mixing to prepare a kneaded product; b) extruding the kneaded product of step a) into an extruder; c) curing the extrudate of step b); And d) drying the sheep of step c); Method of producing a composite hydrocuring molded article having a length change rate of 0.10% or less due to absorption. The method of claim 5, wherein The kneaded product of step a) is a method for producing a composite hydrocuring molded article having a length change rate of 0.10% or less due to absorption further comprising 0.1 to 200 parts by weight of a light weighting agent.