TWI408015B - Humidity adjusting material and method for producing the same - Google Patents

Abstract

The present invention relates to a humidity adjusting material, comprising waste glass and waste catalyst to achieve the object of recycling waste glass and waste catalyst. The present invention also relates to a method for producing a humidity adjusting material, comprising the following steps: (a) providing a row material, comprising waste glass and waste catalyst; (b) grinding the row material and sieving the same; (c) compression molding the row material processed by the step (b); and (d) sintering the molded material.

Description

Humidity control material and manufacturing method thereof

The invention relates to a humidity-controlling material, in particular to a humidity-controlling material with excellent humidity control property and strong folding resistance.

Taiwan's flat panel display industry has been manufacturing large-area film-type LCD panel panels since 1998. According to the data released by the Department of Health of the Executive Yuan, 6,000 to 600,000 metric tons of waste glass waste is buried each year, including 6,000. The metric tons are waste glass of Thin Film Transistor Liquid (TFT-LCD); today, the way to recycle and reuse waste glass in Taiwan is to divide the glass into color separation glass and mixed color glass first, and then re-melt it. The glass is re-formed, and the color separation glass is reused as a glass container, and the mixed color glass is reused in civil engineering, building aggregates, secondary product manufacturing, landscape gardening, etc., but the glass component used in the TFT-LCD industry is special. Most of them are alkali-free borosilicate glass. After recycling, it is impossible to enter the melting and re-manufacturing of glass in the traditional industry. Therefore, how to use such waste glass is a problem to be developed.

At present, Taiwan's relatively mature TFT-LCD industry waste glass resource technology technology is to control waste glass through classification, impurity removal, crush screening, washing, and vibration screening, and then control the conditions such as particle size and color sorting. Glass broken sand. Glass crushed sand can be used as "recycled glass sand" or as "green building material". Reclaimed glass sand can be used to manufacture glass art, glass glaze factory and fired ceramic floor tiles, tiles and building materials. Green building materials are often referred to as environmentally-friendly building materials, and can be used as building materials and decorative materials, including bright colored glass, glass floor tiles, glass marble, etc., and can also be used as cement product additives, including lightweight aggregates, high-pressure floor tiles, and cement interlocking bricks. And glass red bricks, etc., can also be used for public works, including glass asphalt paving, lightweight aggregates.

On the other hand, in the petroleum industry, oil products will be produced or upgraded in different processes. In the process of oil refining, the catalyst will cause its activity to decrease due to surface accumulation of impurities. In order to maintain the reaction efficiency of the catalyst in the system, It will supplement the new catalyst and remove the catalyst whose catalytic function is lost after use. The catalyst for the loss of these catalytic functions is the waste catalyst. At present, the recycling of waste catalysts is mostly for the recovery of valuable metals such as vanadium and molybdenum, bricks or pavement grades, etc., but the treated nickel-containing residue (commonly known as blue mud) is buried and is currently buried every year. The amount of waste catalyst is about 10,000 tons, which is an environmental problem to be solved.

In summary, the disposal of waste glass or melt remanufacturing is not the most effective way to use resources. Today, when environmental protection becomes more and more important, there is an urgent need to recycle waste glass with increasing annual output. Waste catalyst.

In view of the lack of prior art, the main object of the present invention is to provide a humidity-controlling material which uses waste glass and waste catalyst as main materials to achieve the goal of resource recovery.

Another object of the present invention is to provide a method for producing a humidity-controlling material which uses waste glass and a waste catalyst as main materials to obtain a humidity-controlling material having excellent humidity control property and high folding resistance.

To achieve the above object, the present invention relates to a humidity-conditioning type material comprising 1 wt% to 60 wt% waste glass and 40 wt% to 99 wt% waste catalyst.

Preferably, the waste glass is a waste glass of a liquid crystal screen, a solar panel or a container.

Preferably, the aforementioned waste catalyst is a spent catalyst that is inactive.

Preferably, the aforementioned inactive activated waste catalyst is a waste catalyst of a refinery.

Preferably, the aforementioned material size area ranges from 0.0016 to 10.00 m 2 .

Preferably, when it is placed at room temperature and the humidity is 10% to 95% RH, the equilibrium moisture content after 24 hours is 0.01 to 5 kg/kg.

Preferably, when the flexural strength of the aforementioned material is more than 61.2 kgf/cm ² , it is used for building materials.

The present invention further provides a method of manufacturing a humidity-conditioning material comprising:

(a) providing a raw material comprising waste glass and waste catalyst;

(b) grinding and sieving the aforementioned raw materials;

(c) press molding the raw material after the treatment of the above step (b); and

(d) Sintering the material subjected to the aforementioned press molding.

Preferably, the aforementioned step (a) further comprises drying the aforementioned raw materials.

Preferably, the particle size of the previously pulverized and sieved waste glass or waste catalyst is: 300 to 1400 m 2 /kg.

Preferably, the relative proportions of the waste glass and the aforementioned spent catalyst can be further adjusted before the foregoing step (c).

Preferably, the pressure of the aforementioned step (c) is from 20 to 250 kgf/cm ² .

Preferably, the heating rate of the aforementioned step (d) is 5 to 20 ° C / min.

Preferably, the sintering temperature of the aforementioned step (d) is 600 to 1400 °C.

Preferably, the sintering temperature is 900 ° C to 950 ° C.

Preferably, the sintering time is from 0.1 to 6 hours.

Preferably, the sintering method is a high temperature furnace sintering.

Preferably, the sintering furnace of the foregoing high temperature furnace is an electric kiln, a gas kiln or a material kiln.

In summary, the humidity-controlling material of the present invention uses waste glass and waste catalyst as main materials, and achieves the purpose of waste recycling, and the manufacturing method uses waste glass as a main raw material, and uses different proportions of waste. The medium replaces the waste glass, and then is sintered and pressurized to obtain the humidity-controlling material of the present invention.

The humidity-control material refers to a material that can absorb moisture and resist, and can be used as an environmental moisture absorption product, a building material or a filler material for building materials, etc., wherein the content of heavy metal, equilibrium moisture content, moisture absorption property and resistance The folding strength must meet the standards before it can be used as building materials.

The invention relates to a humidity-controlling material obtained by recovering and processing waste glass and a waste catalyst, wherein the waste glass is used as a main component, and the characteristics of the sintered body are changed by replacing with a waste catalyst to obtain good hygroscopicity. And a moisture-reducing material having strong folding resistance; wherein the ratio of the waste glass to the waste catalyst is: 1 wt% to 60 wt% waste glass and 40 wt% to 99 wt% waste catalyst; in a preferred embodiment, The aforementioned waste glass system contains 60% by weight of waste glass and 40% by weight of waste catalyst.

The humidity-controlling material of the present invention preferably has a moisture absorption amount of 12 hours according to the standard (according to the Japanese Standard for Determination of Humidity Building Materials) of at least 29 g/m 2 or more; and an equilibrium moisture content value measurement system of the humidity-conditioning material of the present invention. In order to test the finished product at room temperature for 10 hours at a humidity of 10% to 95% RH, the obtained equilibrium moisture content is 0.01 to 5 kg/kg; when placed in a wet environment at room temperature (humidity is 53) %～75%RH,) When tested, the equilibrium moisture content measured by the preferred embodiment is 0.5～2kg/kg (Taiwan climate belongs to the medium-humidity environment, please refer to this value); when placed in high humidity area Under the environment (humidity of about 75% to 95% RH), the equilibrium moisture content measured by the preferred embodiment is 2 to 5 kg/kg.

CNS3298 R2064 specification ceramic wall brick has a folding standard of at least 61.2kg f/cm ² or more. When the humidity-conditioning material of the present invention meets the standard, it can be used as a building material.

The size range of the humidity-controlling material of the present invention is adjusted according to requirements, and is suitable for use in various building materials for building materials, and is preferably 0.0016 to 10.00 m 2 .

The term "waste glass" as used in the present invention means a glass containing a component of cerium oxide, calcium oxide, aluminum oxide, sodium oxide, iron oxide, magnesium oxide, sulfur oxide, potassium oxide or a combination thereof, and further indicates that glass is generally used. In the industry of products, the waste by-products produced by the finished products are glass shearing scraps or scraps produced by the operation of the machinery; for example, but not limited to the manufacture of liquid crystal screens, solar panels or containers. Waste glass; in the preferred embodiment of the present invention, the waste by-product produced by the manufacture of TFT-LCD waste glass is mainly composed of cerium oxide (SiO ₂ ) and calcium oxide (CaO).

The term "waste catalyst" as used in the present invention means a catalyst containing components of alumina, ceria, potassium oxide, calcium oxide or a combination thereof, and is further represented as an inactive catalyst; for example, but not limited to refining The waste catalyst of the factory; in the preferred embodiment of the present invention, the waste catalyst which reduces the activity of the catalyst when the refinery refines the crude oil process, and loses its activity, the main component of which is alumina (Al ₂ O ₃ ) And cerium oxide (SiO ₂ ).

The invention also provides a method for manufacturing a humidity-controlling material, which is referred to in the second figure, which comprises the steps of: first obtaining the required raw materials (waste glass and waste catalyst), and drying and grinding the aforementioned raw materials, the aforementioned grinding A conventional grinding method can be employed without limitation, and is preferably ball milling. Next, the ground raw material is sieved, and the purpose of sieving is to use the average particle size of the raw material particles, which will contribute to the strengthening and stability of the humidity-regulating material structure in the subsequent sintering process, so there is no need to limit in principle. The screen used may be as long as it can screen raw material particles having a similar particle size, for example, a sieve of 60 to 400 mesh; preferably, a mesh No. 100 is used; preferably, after the aforementioned screening step, The fineness of the raw material particles to be screened is 300 to 1400 m 2 /kg.

Then, adjusting the ratio of waste glass and waste catalyst in the raw material, the waste glass is the main component of the invention, and the proportion thereof is from 1 wt% to 60 wt%; the waste catalyst provides the adsorption function of the humidity-control material of the present invention, The proportion is from 40% by weight to 99% by weight; in the preferred embodiment, the waste glass content is 60% by weight and the waste catalyst content is 40% by weight.

After selecting an appropriate ratio, the above-mentioned raw materials are press-formed at a pressure of 20 to 250 kgf/cm ² , but those having ordinary knowledge in the art may use a suitable pressure to fix the aforementioned raw materials into a desired shape as the case may be. . The foregoing shape is not limited, and may be pressurized to any geometric shape, including: rectangular, rectangular or circular, depending on the application requirements of the humidity-conditioning material of the present invention.

Then, the raw material after the press molding described above is sintered. The high temperature sintering will make the sintered body tend to densify, and will close the pore structure in the sintered body, causing the pore closure to affect its adsorption performance, so the temperature of the above sintering will affect the equilibrium moisture content of the humidity-conditioning material of the present invention, when sintering The higher the temperature, the lower the equilibrium moisture content; and the densification of the aforementioned sintering causes the mechanical strength of the sintered body. The sintering step of the present invention can be carried out in any high temperature sintering manner known in the art including, but not limited to, an electric kiln, a gas kiln or a material kiln. The sintering temperature is 600 to 1400 ° C; in the preferred embodiment, the sintering temperature is 900 ° C to 950 ° C; the heating rate is 5 to 20 ° C / min, and the sintering residence time is about 0.1 to 6 hours, and It is then naturally cooled to room temperature.

After the sintering, the humidity-conditioning material of the present invention is completed, and the area of the finished product may be different in size depending on the demand, and is preferably 0.0016 to 10.00 m 2 .

The following examples are intended to further understand the advantages of the present invention, and are not intended to limit the scope of the patent application of the present invention; each of which is sintered and pressurized in different proportions of TFT-LCD waste glass and waste catalyst. Various performance tests of materials.

Example 1: Analysis of the composition and characteristics of the raw materials of the humidity-controlling material of the present invention

First, the components of the TFT-LCD waste glass and the waste catalyst of the present invention were analyzed by X-ray Fluorescence Spectrometer (XRF). The results are shown in the following table:

The results show that the main component of TFT-LCD waste glass is cerium oxide (SiO ₂ ), accounting for 67.84wt%, the secondary component is calcium oxide (CaO), accounting for about 20.06wt%, while the waste catalyst is mainly alumina. (Al ₂ O ₃ ) is mostly associated with cerium oxide (SiO ₂ ). The crystal phase species of the humidity-conditioning material of the present invention was analyzed by X-ray diffraction analyzer (XRD). Please refer to the first figure for the XRD pattern of the TFT-LCD waste glass and waste catalyst of the present invention, wherein the peak 1 represents cerium oxide (SiO ₂ ) and the peak 2 represents bismuth iron (Fe ₂ Si). The TFT-LCD waste glass has no amorphous structure, so the XRD analysis results in no obvious diffraction peaks and more noise. The crystal phases of the spent catalyst are cerium oxide (SiO ₂ ) and iron hydride (Fe ₂ Si).

Next, according to the NIEA R208.03C standard method announced by the Environmental Protection Institute, the pH value of the TFT-LCD waste glass and the waste catalyst used in the present invention (pH value, solid-liquid ratio mixed with distilled water in a ratio of 1:10) was tested. Physical properties such as density, moisture, and loss of ignition. The results are summarized in Table 2 below:

The results showed that the pH of the TFT-LCD waste glass was 8.92, and the specific gravity of the TFT-LCD in kerosene was 2.97.

Finally, the total amount of heavy metals and heavy metals TCLP of the TFT-LCD waste glass and waste catalyst used in the present invention were determined by atomic absorption spectrometry (FLAA) according to the standard methods of NIEA R317.10C and NIEA R201.13C published by the Environmental Protection Institute. (Toxicity characteristic leaching procedure) dissolution concentration, the results of which are listed in Table 3 below:

It can be seen from the above Table 3 that the total amount of heavy metals in the TFT-LCD waste glass has the highest zinc (Zn) content of 173.33 mg/kg, followed by the nickel (Ni) content of 38.33 mg/kg, and the TCLP dissolution test results show that The concentration of heavy metal dissolution is lower than the regulatory value. In general, the raw materials of the humidity-controlling materials of the present invention have no doubts that are harmful to the environment.

Example 2: Preparation of the humidity-controlling material of the present invention

Referring to the second drawing, after obtaining the TFT-LCD waste glass and the waste catalyst required for the raw materials, the raw materials were dried at a temperature of 105 ° C, and then the raw materials were ground by ball milling for 3 hours to uniformly pulverize the raw materials. The ground raw material is passed through a sieve of a No. 100 mesh to obtain an average particle size of the powder particles. Then adjust the distribution of raw materials as shown in the following table four:

Table 4: Ratio of the TFT-LCD waste glass and the waste catalyst of the present embodiment (weight percent concentration)

The samples A to D prepared in the above ratio were pressure-molded at a pressure of 50 kgf/cm ² and placed in an electric kiln, and each of the above samples was sintered at temperatures of 800 ° C, 850 ° C, 900 ° C, and 950 ° C, respectively. The heating rate was 5 ° C / min. The humidity-conditioning material of this embodiment is obtained after the sintering is completed.

Example 3: Analysis of the properties of the humidity-conditioning material of the present invention Balanced moisture content

Firstly, according to the method for determining the equilibrium moisture content of the building material of JIS A1475, the finished product in the room at the sintering temperature of 800 ° C, 850 ° C, 900 ° C and 950 ° C of the humidity-control material samples A to D of the second embodiment of the present invention is determined. The equilibrium moisture content after 24 hours of various humidity environments (10% to 95% RH) under temperature is as shown in the third A to third D graphs according to the temperature, and the results are known The moisture absorption curve of the humidity-controlling material of the present invention.

In the figure, the X-axis is the relative humidity (%), which indicates the test done under different humidity conditions. The Y-axis is the equilibrium moisture content (kg/kg). It can be seen from the data in the figure that no matter the sintering temperature, The trend of balancing the water content is: the higher the amount of waste catalyst replacement with the raw material, the higher the equilibrium moisture content. Among them, the sample D (that is, the amount of waste catalyst replacement is 40%), the best equilibrium moisture content of 3.99 kg / kg at the sintering temperature of 800 ° C (as shown in Figure 3A). When the sample temperature is 850 ° C, the equilibrium moisture content decreases to 3.62 kg / kg (as shown in Figure B). When the sintering temperature is 950 ° C, the equilibrium moisture content drops to 1.93 kg / kg (such as The three D figure shows).

2. Humidity control performance

Next, according to the moisture absorption and desorption test method of JIS A1470-1 humidity-regulating building material, the finished products prepared by the samples A to D of the second embodiment of the present invention at 800 ° C, 850 ° C, 900 ° C and 950 ° C were prepared. The humidity control performance in the medium wet zone (53-75% RH).

According to the Japanese benchmark for the determination of building materials, the moisture absorption after 12 hours should be more than 29g/m2, which is suitable for use as a humidity-control building material. The X-axis is the test time (hours), and the Y-axis is the amount of water to be released (g/m2). The samples A (◆), B (■), C (▲), and D (×) are displayed at 800 ° C and 850 ° C. The amount of water absorbed and discharged in the finished product at 900 ° C and 950 ° C sintering temperature was as shown in the fourth to fourth D drawings according to the temperature.

From the data in the figure, it can be seen that the sample A (that is, the amount of waste catalyst substitution is 10%) is prepared at 800 ° C, 850 ° C, 900 ° C and 950 ° C and the sintering temperature of sample B at 950 ° C. For wet materials, the humidity control performance does not meet the 12-hour moisture absorption specified by Japanese Building Materials, while other samples are in compliance with regulations and can be applied to building materials.

3. Flexural strength

Finally, the flexural strengths of the humidity-control material samples A to D of the second embodiment of the present invention were tested, and the results are shown in the fifth row.

The X-axis is sample A to D, and the Y-axis is the flexural strength (kg f/cm ² ). Each sample is displayed at 950 ° C (◆), 900 ° C (■), 850 ° C (▲), and 800 ° C (×). The bending strength of the obtained humidity-controlling material is sintered.

According to CNS3298 R2064, the ceramic bricks have a folding standard of 61.2kg f/cm ² or more. As can be seen from the data in the figure, the flexural strength increases substantially as the sintering temperature increases. The results show that at the 950 ° C sintering temperature, in addition to the sample A does not meet the standard, other samples are in line with the standard, and can be used as building materials.

Combined with the above test data, the equilibrium moisture content of the humidity-conditioning material decreases with the increase of the sintering temperature, which is due to the phenomenon that the sintered body tends to densify due to high-temperature sintering, and the pore structure in the sintered body is closed, which causes the pore to be closed. Its adsorption properties. Sintering densification causes the mechanical strength of the sintered body to grow, so it has a high flexural strength at a sintering temperature of 950 °C.

From the results, it is understood that, in terms of use as a building material, the preferred operating conditions of the present invention are the substitution of 30 wt% or 40 wt% of the spent catalyst at the sintering temperature of 950 ° C (ie, the sample C and D). Wet type material; optimally, it is replaced by 40wt% waste catalyst at 950 °C sintering temperature, because 40wt% catalyst content has better moisture absorption performance, so it is the best operating condition. In the present invention, it does not conform to the standard of building materials, and can also be used for other purposes, such as: environmental moisture absorption products or filler materials for building materials.

It will be apparent to those skilled in the art that various changes can be made in accordance with the embodiments of the present invention without departing from the spirit of the invention. Therefore, it is to be understood that the invention is not limited by the scope of the invention, and is intended to cover the modifications of the spirit and scope of the invention.

The first figure shows the XRD pattern of the TFT-LCD waste glass and waste catalyst.

The second figure shows the preparation process of the humidity-conditioning material of the second embodiment of the present invention.

The third A graph shows the equilibrium moisture content of the humidity-conditioning material of the second embodiment of the present invention sintered at 800 °C.

The third B graph shows the equilibrium moisture content of the humidity-conditioning material of the second embodiment of the present invention sintered at 850 °C.

The third C graph shows the equilibrium moisture content of the humidity-conditioning material of the second embodiment of the present invention sintered at 900 °C.

The third D graph shows the equilibrium moisture content of the humidity-conditioning material of the second embodiment of the present invention sintered at 950 °C.

Fig. 4A shows the humidity control performance of the humidity-conditioning material of the second embodiment of the present invention sintered at 800 °C.

Fig. 4B shows the humidity control performance of the humidity-conditioning material of the second embodiment of the present invention sintered at 850 °C.

The fourth C diagram shows the humidity control performance of the humidity-conditioning material of the second embodiment of the present invention sintered at 900 °C.

The fourth D pattern shows the humidity control performance of the humidity-conditioning material of the second embodiment of the present invention sintered at 950 °C.

The fifth figure shows the flexural strength of the humidity-conditioning material of the second embodiment of the present invention.

Claims (18)

A humidity-controlling material comprising: 60 wt% to 99 wt% waste glass; and 1 wt% to 40 wt% of a waste catalyst, wherein the waste catalyst comprises alumina (Al ₂ O ₃ ) and Cerium oxide (SiO ₂ ). The material of claim 1, wherein the waste glass is a waste glass of a liquid crystal screen, a solar panel or a container. The material of claim 1, wherein the waste catalyst is an inactive waste catalyst. For example, the material described in claim 3, wherein the aforementioned inactive activated waste catalyst is a waste catalyst of a refinery. For the material described in item 1 of the patent application, the material size area ranges from 0.0016 to 10.00 m ² . For example, if the material described in claim 1 is placed at room temperature and the humidity is 10% to 95% RH, the equilibrium moisture content after 24 hours is 0.01 to 5 kg/kg. For example, the material described in claim 1 is used for building materials when its flexural strength is greater than 61.2 kgf/cm ² . A method of manufacturing a humidity-conditioning material comprising: (a) providing a raw material comprising waste glass and a waste catalyst; (b) grinding and sieving the raw material; (c) treating the aforementioned step (b) Thereafter, the raw material is press-formed; and (d) the material subjected to the aforementioned press molding is sintered. The method of claim 8, wherein the aforementioned step (a) further comprises drying the aforementioned raw material. The method of claim 8, wherein the particle size of the ground and sifted waste glass or waste catalyst is 300 to 1400 m ² /kg. The method of claim 8, wherein the relative proportions of the waste glass and the aforementioned spent catalyst are further adjusted before the step (c). The method of claim 8, wherein the pressure of the aforementioned step (c) is 20 to 250 kgf/cm ² . The method of claim 8, wherein the heating rate of the foregoing step (d) is 5 to 20 ° C / min. The method of claim 8, wherein the sintering temperature of the aforementioned step (d) is from 600 ° C to 1400 ° C. The method of claim 14, wherein the sintering temperature is from 900 ° C to 950 ° C. The method of claim 8, wherein the sintering time is 0.1 to 6 hours. The method of claim 8, wherein the sintering method is a high temperature furnace sintering. The method of claim 17, wherein the sintering of the high temperature furnace is an electric kiln, a gas kiln or a material kiln.