TWI568702B - Humidity controlling ceramics and preparation thereof - Google Patents

Description

Humidity control ceramic and manufacturing method thereof

The invention relates to a humidity control ceramic and a preparation method thereof, in particular to a humidity control ceramic prepared by using incinerator boiler ash, waste glass and palygorskite and a preparation method thereof.

As the population grows, the amount of garbage generated has become a problem that countries need to solve. Since incineration can greatly reduce the volume of garbage, it is an important method of garbage disposal. However, the large incineration of boiler ash from waste incineration still requires further landfill disposal, which in turn creates new environmental impacts.

On the other hand, with the rise of environmental awareness, a large amount of glass has been collected. At present, these glasses are mainly placed in a stacked manner, and thus require a large accommodation space, so how to deal with the large amount of discarded glass recovered is also a problem that needs to be solved at present.

As mentioned above, how to deal with the large amount of incineration boiler ash generated by waste incineration and the recycled waste glass has become a problem that researchers need to solve.

In order to solve the large amount of incineration boiler ash and waste glass recovered by waste incineration in the prior art, the present invention provides a humidity control ceramic prepared by using incinerator boiler ash, waste glass and palygorskite and a manufacturing method thereof for effectively utilizing incineration Boiler ash and waste glass, and a humidity-conditioning ceramic with better moisture absorption effect.

According to an embodiment of the present invention, the humidity-regulating ceramic is prepared by mixing and sintering according to the following ratios: an incineration boiler ash, the amount of incineration boiler ash is 5 to 60 wt%; and a waste glass, the amount of waste glass is 10 -85 wt%; and a palygorskite, the amount of palygorskite is 10-60% by weight.

In one embodiment, the amount of incineration boiler ash is 10% by weight, the amount of waste glass is 70% by weight, and the amount of palygorskite is 20% by weight.

A method for manufacturing a humidity-controlling ceramic according to an embodiment of the present invention comprises: performing a pre-treatment step comprising: collecting incineration boiler ash, performing water extraction treatment on the incinerator boiler ash, and incineration boiler ash solidification after water extraction treatment Separating the liquid to form an incinerator boiler ash; performing a waste glass mashing and sieving to provide a waste glass; and providing a palygorskite; mixing the incineration boiler ash, the waste glass and the palygorskite to form a green embryo, Wherein, the amount of the incinerator boiler ash is 5 to 60% by weight, the amount of the waste glass is 10 to 85% by weight, and the amount of the palygorskite is 10 to 60% by weight; and the sintering process is performed on the green embryo.

In one embodiment, the amount of incineration boiler ash is 10% by weight, the amount of waste glass is 70% by weight, and the amount of palygorskite is 20% by weight.

In one embodiment, in the step of forming a green embryo, the moisture content of the green body is 10 to 20% by weight, and the moisture content of the green body is based on the total weight of the green embryo.

In one embodiment, in the step of forming a green embryo, the moisture content of the green body is 15% by weight, and the moisture content of the green body is based on the total weight of the green embryo.

In one embodiment, in the step of making a green embryo, the green embryo is press molded at a pressure of 2000 psi and the pressing time is 1 minute.

In one embodiment, the sintering temperature of the sintering process is from 700 ° C to 1000 ° C.

In one embodiment, the sintering process has a ramp rate of between 1 and 30 ° C/min.

According to the embodiment of the present invention disclosed above, since the invention utilizes incineration boiler ash, waste glass and palygorskite to make a humidity-control ceramic, the hazardous waste can be successfully recycled, and the humidity-control ceramic has better suction. The moisture content, the moisture release rate, and the avoidance of heavy metals flowing out during the process are environmentally-friendly high-performance humidity-control ceramics with high economic value.

The above description of the present invention and the following description of the embodiments of the present invention are intended to illustrate and explain the principles of the invention.

1 is a flow chart showing a method of fabricating a humidity-conditioning ceramic prepared according to an embodiment of the present invention.

Figure 2 is a detailed flow chart of the processing steps before Figure 1.

Figure 3 is a graph showing the moisture absorption and desorption test of the humidity-conditioning ceramics at different sintering temperatures according to an embodiment of the present invention.

4A to 4C are respectively SEM analysis results of the humidity-conditioning ceramics at different sintering temperatures according to an embodiment of the present invention.

Fig. 4D is a SEM analysis result of sintering of the humidity-conditioning ceramic of Comparative Example of the present invention at 850 ° C, respectively.

Fig. 5 is a graph showing the absorption and desorption of the humidity-regulating ceramics in different sintering atmospheres according to an embodiment of the present invention.

Figure 6 is a graph showing the solid phase solidification rate of heavy metals sintered at 750 °C in different sintering atmospheres according to an embodiment of the present invention.

The detailed features and advantages of the present invention are described in detail below in the embodiments. The content is sufficient for any skilled person to understand the technical content of the present invention and to implement the same, and according to the content, the patent scope and the drawings disclosed in the specification, the relevant objects of the present invention can be easily understood by those skilled in the art and advantage. The following examples are intended to describe the present invention in further detail, but do not limit the scope of the invention in any way.

Please refer to FIG. 1 and FIG. 2 . FIG. 1 is a flow chart of a method for fabricating a humidity-conditioning ceramic prepared according to an embodiment of the present invention, and FIG. 2 is a detailed flowchart of a processing step before the first embodiment.

First, a pre-processing step (A) is performed. In detail, the pre-processing step (A) comprises the following three steps.

In the pre-processing step (A), the three steps can be further distinguished (as shown in Fig. 2). In the present embodiment, the incineration boiler ash is first collected, the incineration boiler ash is subjected to water extraction treatment, and the incineration boiler ash after the water extraction treatment is separated by solid-liquid separation to form an incineration boiler ash (A1). In the present embodiment, the pretreatment of the water extraction is first performed to remove salts which are detrimental to the stability of the heavy metal and the durability of the sintered body. In detail, the ratio of the liquid to the solid at the time of performing the water extraction is, for example, 5:1, the extraction time is, for example, 5 minutes, and the number of times is, for example, 2 times. After the water extraction is completed, the incinerator boiler ash solid liquid is separated.

Among them, the incineration boiler ash refers to the boiler ash obtained after the combustion treatment by the incinerator. The incineration boiler ash includes, for example, 22.25 wt% of calcium, 6.23 wt% of rhodium, 2.55 wt% of aluminum, 1.91 wt% of iron, 1.76 wt% of magnesium, 3.71 wt% of sodium, 3.91 wt% of potassium, and trace amounts of Lead, zinc, cadmium, copper, chromium (measurement results of elemental analysis after melting the incineration boiler ash into a liquid at a high temperature). In general, incineration boiler ash is also a hazardous waste because it also contains heavy metals. Therefore, the incineration boiler ash needs to meet many restrictions in its use. For example, the dissolution test results of these heavy metals should comply with relevant regulations. It should be noted that the elemental composition of the incineration boiler ash described above is for illustrative purposes only and is not intended to limit the invention.

A waste glass recycling procedure is performed to provide a waste glass (A2). In this embodiment, a brown glass bottle is used, and after collecting, the label is removed, washed, dried, and then crushed, and then the glass is broken into smaller fine powder by a masher, and finally filtered by 200.

Wherein, the waste glass contains, for example, 4.79 wt% of calcium, 22.10 wt% of rhodium, 1.03 wt% of aluminum, 0.20 wt% of iron, 0.62 wt% of magnesium, 6.58 wt% of sodium, 0.41 wt% of potassium, and trace amount. Lead, copper, and chromium (measurement results of elemental analysis after the flux is melted into a liquid at a high temperature). It should be noted that the elemental composition of the above waste glass is for illustrative purposes only and is not intended to limit the invention.

Provide a rock (A3). In the present embodiment, the use of industrial grade palygorskite is used.

In detail, palygorskite is an ore belonging to the sepiolite family. Palygorskite is converted from montmorillonite. The palygorskite is composed of an aqueous layered magnesium silicate, that is, the palygorskite belongs to the magnesia silicate mineral. The composition of palygorskite comprises, for example, 1.19 wt% calcium, 12.48 wt% rhodium, 2.6 wt% aluminum, 1.15 wt% iron, 3.13 wt% magnesium, 0.24 wt% sodium, 1.01 wt% potassium ( The measurement result of the elemental analysis after the flux melts the palygorskite into a liquid at a high temperature. It should be noted that the elemental composition of the palygorskite described above is for illustrative purposes only and is not intended to limit the invention.

It should be noted that the order of the above steps (A1), (A2), and (A3) is not intended to limit the present invention, and the user may select the appropriate order of steps (A1), (A2), and (A3) according to their needs. . For example, the user may perform step (A3) first, and then perform steps (A1) and (A2) in sequence.

After the pre-treatment step (A), the incineration boiler ash, the waste glass, and the palygorskite are mixed to form a green embryo (B).

In the embodiment of the present invention, the amount of the incinerator boiler ash is 5 to 60 wt%, and the waste glass is discarded. The amount of the glass is from 10 to 85% by weight, and the amount of the palygorskite is from 10 to 60% by weight, whereby the prepared humidity-conditioning ceramic has a better humidity control effect.

In some embodiments of the present invention, the incineration boiler ash is used in an amount of 10 to 30% by weight, the waste glass is used in an amount of 50 to 80% by weight, and the palygorskite is used in an amount of 10 to 30% by weight. In some embodiments of the present invention, the amount of incineration boiler ash is 10-20 wt%, the amount of waste glass is 60-75 wt%, and the amount of palygorskite is 15-25 wt%.

Users can choose the appropriate weight ratio of incineration boiler ash, waste glass, and palygorskite according to their needs. For example, the amount of incineration boiler ash is, for example, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%; The amount is, for example, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%; The amount of stone used is, for example, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, thereby improving the humidity control effect of the humidity control ceramic. In this embodiment and some other embodiments, the amount of the incinerator boiler ash is 10% by weight, the amount of waste glass is 70% by weight, and the amount of palygorskite is 20% by weight, whereby the prepared humidity-conditioning ceramic has better adjustment. Wet effect.

In this and some other embodiments, the green embryos were compression molded at a pressure of 2000 psi and the pressing time was 1 minute. After being pressed and molded, it was placed in an oven at 105 ° C for 24 hours to ensure the shape integrity of the green body.

In this embodiment, the green size produced is: 10 cm in length, 5 cm in width, and 0.5 cm in thickness.

It should be noted that in the above step (B), the moisture content of the green body 10~20wt%, the water content is based on the total weight of the raw embryo. If the moisture content is too high, the green body will not be formed, and if the moisture content is too low, the green body will be broken.

In this and some other embodiments, the green body has a moisture content of 15% by weight. Thereby, a better molding effect is achieved.

Finally, the firing process is performed on the green embryo (C). Thereby, the humidity-conditioning ceramic is formed by sintering. In the embodiment of the invention, the sintering temperature of the sintering process is 700 to 1000 °C. In this embodiment and some other embodiments, the sintering temperature of the sintering process is 700 to 800 °C. In this and some other embodiments, the sintering temperature of the sintering procedure was 750 °C. The user can select the appropriate sintering temperature according to the requirements of the humidity-conditioning ceramic. In detail, the user can adjust the sintering temperature to change the humidity control ability and mechanical strength of the prepared humidity control ceramic. When the sintering temperature is lower, the prepared humidity-conditioning ceramic has better humidity control ability, and when the sintering temperature is higher, the prepared humidity-conditioning ceramic has better mechanical strength. Among them, the heating rate of the sintering process is between 1 and 30 ° C / min. When the temperature reached 750 ° C, it was naturally cooled to room temperature after holding for 20 minutes. Among them, the sintering process may be oxidative sintering (high temperature rectangular furnace, air atmosphere sintering, aerobic environment), reduction sintering (tubular furnace, nitrogen atmosphere sintering, oxygen-free environment). Thereby, the humidity-tuned ceramic produced by sintering has both excellent humidity control ability and mechanical strength.

In the embodiment of the present invention, the amount of the incineration boiler ash of the humidity-control ceramic is 5 to 60 wt%, and the amount of the waste glass is 10 to 85 wt%, and the amount of the palygorskite is 10 to 60 wt%. In some embodiments of the present invention, the incineration boiler ash is used in an amount of 10 to 30% by weight, the waste glass is used in an amount of 50 to 80% by weight, and the palygorskite is used in an amount of 10 to 30% by weight. In some embodiments of the present invention, the amount of incineration boiler ash is 10-20 wt%, the amount of waste glass is 60-75 wt%, and the amount of palygorskite is 15-25 wt%. Users can choose incineration boiler ash, waste glass, palygorskite according to their needs. The weight ratio is not repeated here.

As described above, since the incineration boiler used in the present case has foaming characteristics and porous characteristics, and through the waste glass as a cementing agent, it is possible to successfully prepare a humidity control having a better humidity control effect while maintaining the mechanical strength of the humidity control ceramic. ceramics.

The humidity-conditioning ceramics of the examples of the present invention were tested as follows.

First, the humidity conditioning performance evaluation benchmark

In the present invention, the moisture absorption and desorption test method is tested in accordance with JIS A 1470-1, and in accordance with Japan's moisture conditioning performance evaluation benchmark for building materials (Guidelines for Conditioning Building Materials Evaluation, 2006), medium wet field (50) ~70%) The moisture absorption and desorption test, in the 24-hour continuous test, is rated as different grade according to the first 12 hours of moisture absorption, and the amount of moisture removal after the last 12 hours needs to be more than 70% of the moisture absorption. The evaluation criteria for Japanese humidity control materials.

Please refer to FIG. 3, which is a moisture absorption and desorption test of the humidity-conditioning ceramics at different sintering temperatures according to an embodiment of the present invention. As shown, the amount of moisture release are in compliance with the requirements of the evaluation criteria (moisture content of 70% or more) of the humidity-ceramic according to embodiments of the present invention, the amount of moisture absorption were ^{85.22g / m 2, 65.26g / m} 2 ^{, 42.38g / m 2, 23.16g /} m 2, the graph shows the amount of moisture up to 700 deg.] C, up to the highest level (third level) of the standard. Please refer to FIG. 4A to FIG. 4D , and FIG. 4A to FIG. 4C are respectively SEM analysis results of the humidity-control ceramics at different sintering temperatures according to an embodiment of the present invention, and FIG. 4D is a humidity-conditioning ceramic of a comparative example of the present invention, respectively. SEM analysis results of sintering at 850 °C. As shown in Fig. 4A, at 700 ° C, the sintering temperature is lower, the arrangement of the particles is looser, and more open pores are formed, so that the moisture absorption effect is better. As shown in Fig. 4B, at 750 ° C, part of the glass begins to melt to cause the particles to begin to bond, causing some of the pores to begin to shrink, so that the amount of humidity control is slightly lowered, but still reaches the second-stage humidity-conditioning material. As shown in Fig. 4C, at 800 ° C, the glass is in a molten state, and the open pores in the sintered body are initially filled and partially turned into closed pores. As shown in Fig. 4D, at 850 ° C, the sintering temperature is increased, so that the waste glass has a long time to form a molten state to form a densification, thereby blocking the pore structure and causing the water vapor adsorption property to disappear, and the moisture permeability of the prepared humidity control ceramic is eliminated. The amount drops.

Second, mechanical characteristics

Please refer to the table below. Table 1 shows the mechanical properties of the sintered body of the humidity-control ceramics of the examples and comparative examples of the present invention. As shown in Table 1, the sintering temperature is proportional to the shrinkage rate and the flexural strength, and inversely proportional to the apparent porosity and water absorption. Among them, the apparent porosity and water absorption are related to the humidity control ability, and can be used as a preliminary indicator of the humidity control ability, especially the moisture absorption capacity.

As shown in Table 1, the humidity control ability of 700 °C humidity control ceramics is the best, but the average bending strength is low; the average bending strength of 750 °C humidity control ceramics has reached 6.12 MPa, and can meet CNS3299-4 Ceramic tile strength requirements, and humidity control capacity is the second level of evaluation benchmark; 800 ° C humidity control ceramics bending strength can meet the CNS requirements, and can maintain the humidity control capacity in the first level of evaluation criteria.

Third, the comparison of oxidation and reduction sintering

In the present invention, the rectangular furnace and the tubular furnace are respectively oxidized and sintered in an air atmosphere and reduced and sintered in a nitrogen atmosphere, and the humidity control ability, mechanical properties (bending strength), and heavy metal volatilization and sintered body in the sintering process are analyzed. Heavy metal stability.

Referring to FIG. 5, FIG. 5 is a moisture absorption and desorption curve (sintering temperature of 750 ° C) of the humidity-conditioning ceramics sintered in different sintering atmospheres according to an embodiment of the present invention. As shown in Fig. 5, the two sintering atmospheres have similar humidity control capabilities to the prepared humidity-conditioning ceramics, and all meet the second-level requirements of the Japanese evaluation standard.

Please refer to Table 2 and Table 2 for the mechanical properties of the humidity-conditioning ceramics of the embodiment of the present invention sintered in different sintering atmospheres.

As shown in Table 2, the two sintering atmospheres have similar effects on the mechanical properties such as bulk density, shrinkage ratio, apparent porosity and water absorption of the prepared humidity-control ceramics; among them, the humidity-regulating ceramics sintered with nitrogen have better resistance. Bending strength, its bending strength has been clearly higher than the CNS3299-4 ceramic tile strength requirements.

As shown in Fig. 5 and Table 2, the two sintering atmospheres have similar humidity control capabilities and mechanical properties to the prepared humidity control ceramics.

Fourth, heavy metal dissolution

The amount of heavy metal eluted from the humidity-conditioning ceramics of the examples of the present invention was tested below. Please refer to Table 3, Table 3 for the results of the toxic dissolution test of the humidity-control ceramics at 750 ° C in different sintering atmospheres according to the embodiment of the present invention.

As shown in Table 3, the dissolution concentrations of Pb, Zn, Cu, and Cd are far lower than the reuse standards, that is, the heavy metals of the humidity-conditioning ceramics of the present invention are very difficult to dissolve in the environment. On the other hand, the dissolution concentration of the heavy metal Cr is lower than the recycling standard, and is a stable and safe environmentally friendly product. If the sintering is performed using a nitrogen atmosphere, the elution value of the heavy metal Cr can be further reduced to less than one tenth. Therefore, the present invention can effectively control the elution amount of heavy metals in the sintering process, and the reduction and sintering in a nitrogen atmosphere can further improve the environmental performance of the prepared humidity-conditioning ceramics.

Five, heavy metal solid phase stability rate

The heavy metal solid phase stability of the humidity-conditioning ceramics of the examples of the present invention was tested as follows. Please refer to FIG. 6. FIG. 6 is a solid phase solidification rate of heavy metals sintered at 750 ° C in different sintering atmospheres according to an embodiment of the present invention.

As shown in Fig. 6, the heavy metal Pb remains 75% in the solid phase in both sintering atmospheres, and Zn, Cu, and Cr remain in the solid phase in more than 75% under the two sintering atmospheres. Therefore, the present invention can effectively control secondary pollution caused by volatilization of heavy metals during sintering.

According to the embodiment of the invention disclosed above, since the invention utilizes incineration boiler ash, waste glass and palygorskite to make a humidity-conditioning ceramic, the following technical effects can be achieved:

(1) In this case, the ceramic material with high humidity control effect is prepared by using incinerator boiler ash, waste glass and palygorskite, and the ceramic material has sufficient mechanical strength to be used, so the case can effectively solve the disposal of incinerator boiler ash and waste glass. The problem, in turn, achieves effective reuse of materials, and has multiple functions such as environmental protection and high economic value.

(2) In this case, the incineration boiler ash and waste glass waste were used to prepare the humidity control pottery. Porcelain, by virtue of this, has considerable cost advantages in commercial implementation.

(3) The humidity-control ceramics in this case can reach a maximum moisture absorption of 200g/m ² in 12 hours, which far exceeds the highest level (71g/m ² ) of Japan's humidity-control building materials evaluation benchmark. Wet ceramics. At the same time, in this case, due to the appropriate proportion of incineration boiler ash, waste glass and palygorskite, the sintered body with a moisture absorption of 65.26g/m ² and a moisture release rate of 75.32% can be fired at 750 °C, which meets the Japanese evaluation criteria. The second level is specified, and the mechanical strength is determined by the strength of the ceramic tile (6.12 MPa).

(4) The proper material composition and sintering temperature of the case can effectively ensure that the heavy metal stays in the prepared humidity-regulating ceramic, so that the prepared humidity-regulating ceramic is quite stable and safe in the internal environment.

Although the embodiments of the present invention are disclosed above, it is not intended to limit the present invention, and those skilled in the art can devise shapes, structures, and features according to the scope of the present application without departing from the spirit and scope of the present invention. And the spirit of the invention is subject to change. Therefore, the scope of patent protection of the present invention is subject to the scope of the patent application attached to the specification.

Claims (8)

A humidity-controlling ceramic prepared by mixing and sintering according to the following ratio: an incineration boiler ash, the incineration boiler ash is used in an amount of 5 to 60% by weight; and a waste glass is used in an amount of 10 to 85% by weight; and The palygorskite is used in an amount of 10 to 60% by weight. The humidity-conditioning ceramic according to claim 1, wherein the incineration boiler ash is used in an amount of 10% by weight, the waste glass is used in an amount of 70% by weight, and the palygorskite is used in an amount of 20% by weight. The invention relates to a method for preparing a humidity-controlling ceramic, comprising: performing a pre-treatment step, comprising: collecting incineration boiler ash, performing water extraction treatment on the incinerator boiler ash, and separating the incineration boiler ash by a solid-liquid separation, filtering and drying after the water extraction treatment Drying, cooling, and crushing treatment to form an incineration boiler ash; performing a waste glass recovery procedure to provide a waste glass; and providing a palygorskite; mixing the incineration boiler ash, the waste glass, and the palygorskite To produce a raw embryo, wherein the amount of the incinerator boiler ash is 5 to 60 wt%, the amount of the waste glass is 10 to 85 wt%, and the amount of the palygorskite is 10 to 60 wt%; and the raw embryo is subjected to a sintering process, The sintering temperature of the sintering process is 700 ° C to 1000 ° C. The method for producing a humidity-controlling ceramic according to claim 3, wherein the incineration boiler ash is used in an amount of 10% by weight, the waste glass is used in an amount of 70% by weight, and the palygorskite is used in an amount of 20% by weight. The method for producing a humidity-controlling ceramic according to claim 3, wherein in the step of preparing a raw embryo, The green body has a water content of 10 to 20% by weight, and the moisture content of the green body is based on the total weight of the green embryo. The method for preparing a humidity-controlling ceramic according to claim 3, wherein in the step of forming a green embryo, the green matter has a water content of 15% by weight, and the moisture content of the green body is the total weight of the green embryo. Benchmark. The method for producing a humidity-conditioning ceramic according to claim 3, wherein in the step of forming a green embryo, the green embryo is press-molded at a pressure of 2000 psi, and the pressing time is 1 minute. The method for preparing a humidity-conditioning ceramic according to claim 3, wherein the sintering process has a heating rate of 1 to 30 ° C/min.