TWI565662B - Environmental mesoporous molecular sieve hygroscopic material and the preparation methof thereof - Google Patents

Description

Environmentally friendly mesoporous molecular sieve humidity-regulating material and preparation method thereof

The invention relates to a humidity control material, in particular to an environmentally friendly medium pore molecular sieve humidity control material prepared by using waste glass and sludge and a preparation method thereof.

At present, Taiwan is one of the major producers of Thin Film Transistor-Liquid Crystal Display (TFT-LCD) panels. With the rapid development of technology, Internet and communication technologies, 3C products have been born, which has led to a significant increase in the demand for TFT-LCD panels in the information market. According to Digitimes Research statistics, in 2010, large-size TFT-LCD panel shipments increased by 25.6% compared with 2009, and its shipments reached 164.8 Mm2. At that time, 3 million tons of TFT-LCD waste glass will be disposed of; In addition, in the TFT-LCD manufacturing industry, the waste recycling rate is only 69%, and according to the statistics of the 102-year national waste waste declaration by the Environmental Protection Agency of the Executive Yuan, the TFT-LCD waste glass is 3,643 metric tons. If it can be fully resourced and reused, it will be the best way to deconstruct the pipeline.

In addition, Silicon Carbide Sludge (SiC) is used in the production of LED sapphire substrates. When diamond wire is cut, a small amount of diamond chips and debris will flow into the waste collection line, and the double-side grinding process will be used to grind the grain. In the case of micro-plastic cutting, the process is carried out with tantalum carbide powder, and water is used as the medium and the polishing liquid is added. When the grinding, a large amount of sapphire substrate is removed, so that a little Al ₂ O _{3 is} mixed into the tantalum carbide, and the waste water is produced. After the treatment, a large amount of carbonized sludge was derived. According to the statistics of the 102-year national waste waste declaration species published by the Environmental Protection Agency of the Executive Yuan, it has increased from 33 metric tons in 2010 to 1,074 metric tons in 2013. As the production of LED sapphire substrates grows year by year, a large amount of SiC pollution will be generated. Mud, if it fails to establish the best treatment and disposal methods, has a considerable impact on the environmental impact.

In summary, the disposal of TFT-LCD waste glass or tantalum carbide sludge is not the most effective way to use resources. Today, environmental protection is becoming more and more important, and there is an urgent need for a better way to recycle the year. TFT-LCD waste glass and tantalum carbide sludge with increased production.

In view of the lack of prior art, the main object of the present invention is to provide an environmentally-friendly medium-porosity molecular sieve humidity-regulating material, which uses TFT-LCD waste glass and silicon carbide sludge as main materials to achieve resource recovery.

Another object of the present invention is to provide a method for preparing an environmentally-friendly mesoporous molecular sieve humidity-regulating material, which uses TFT-LCD waste glass and strontium carbide sludge as main materials to obtain an excellent moisture absorption amount and an equilibrium moisture content. It can be reused as a humidity-control coating material for green building materials.

To achieve the above object, the present invention provides an environmentally-friendly mesoporous molecular sieve humidity-conditioning material comprising 10 wt% to 90 wt% of TFT-LCD waste glass; and 10 wt% to 90 wt% of niobium carbide sludge (SiC); wherein the TFT-LCD The waste glass contains cerium oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), and calcium oxide (CaO), and the SiC sludge contains cerium oxide (SiO ₂ ).

Preferably, the ratio of the aforementioned TFT-LCD waste glass to the strontium carbide sludge is 20 wt%: 80 wt%, 10 wt%: 90 wt% or 87.5 wt%: 12.5% wt%.

Preferably, the aforementioned TFT-LCD waste glass is waste glass which is produced as a side material, a scrap or a defective product when the liquid crystal panel is manufactured.

Preferably, the tantalum carbide sludge is used in the production process of the LED sapphire substrate, using tantalum carbide as the abrasive material, and using water as the grinding medium or adding the grinding liquid to remove the waste sludge generated by the sapphire substrate.

Preferably, when the humidity-conditioning material is placed in an environment having a relative humidity of 53 to 75%, the moisture absorption amount after 12 hours is more than 29 g/m ² .

Preferably, when the humidity-conditioning material is placed in an environment having a relative humidity of 53 to 75%, the moisture absorption amount after 12 hours is more than 71 g/m ² .

Preferably, when the humidity-conditioning material is placed at room temperature and the relative humidity is 10 to 95%, the equilibrium moisture content after 24 hours is more than 5 kg/m ³ .

The invention further provides a preparation method of an environmentally-friendly mesoporous molecular sieve humidity-regulating material, the method steps comprising:

Material extraction step: providing TFT-LCD waste glass and silicon carbide sludge as a raw material for preparing a medium pore molecular sieve humidity-control material, the raw material composition comprising 10 wt% to 90 wt% of TFT-LCD waste glass, and 10 wt% to 90 wt% Tantalum carbide sludge;

Alkali melting step: adding an alkali agent to the raw material at a mass ratio of 1.25 to 1.75, and performing an alkali melting process at a temperature of 450 to 650 ° C to obtain an alkali fusion product;

The bismuth aluminum extraction step: extracting the lanthanum source and the aluminum source in the alkali fusion product, and preparing a sodium strontium aluminate solution having a liquid-solid ratio (L/S) of 5-15;

Forming step: providing a CTAB aqueous solution, adding the sodium strontium aluminate solution to the CTAB aqueous solution to prepare a gel solution;

Hydrothermal synthesis step: the gel is dissolved in a high temperature autoclave and subjected to a hydrothermal reaction at a temperature of 90 to 120 ° C;

Template removal step: the solid product after the hydrothermal reaction is filtered and washed, and dried to be calcined to remove the CTAB template to obtain an environmentally-friendly mesoporous molecular sieve humidity-regulating material.

Preferably, in the step of taking the material, the weight ratio of the TFT-LCD waste glass to the strontium carbide sludge is 1:4, 1:9 or 7:1; in the alkali melting step, the alkali fusion process adds the alkali agent to The ingot is pressed in the raw material, and then placed in a high temperature furnace, and calcined at 450 ° C, 550 ° C or 650 ° C, wherein the alkali agent is selected from sodium hydroxide (NaOH), potassium hydroxide (KOH) or sodium carbonate (Na ₂ CO _{3 ).} And the mass ratio of the alkali agent to the raw material is 1.25, 1.5 or 1.75; in the foregoing bismuth aluminum extraction step, the alkali fusion product is obtained by using a liquid-solid ratio of 5, 10 or 15, to extract the cerium source and the aluminum source; In the step, the CTAB aqueous solution comprises CTAB and 30 mL of deionized water and 1.5 mL of ammonia water, and the sodium citrate solution is added to the CTAB aqueous solution, and the gel solution is prepared by adjusting the pH value and vigorously stirring the reaction; the hydrothermal synthesis In the step, the hydrothermal reaction is carried out at a hydrothermal reaction temperature of 90 ° C, 105 ° C or 120 ° C for 24 to 48 hours; in the template removal step, the solid product is filtered, washed with deionized water, and Drying in an oven at 105 ° C, followed by continuous calcination at 550 ° C for 5 hours to completely remove CTA The B template is used to prepare the environmentally-friendly mesoporous molecular sieve humidity-regulating material.

Preferably, the foregoing TFT-LCD waste glass and the cerium carbide sludge are pretreated as raw materials by the raw material, wherein the pretreatment comprises:

The collected TFT-LCD waste glass and the silicon carbide sludge are respectively dried at a temperature of 105 ° C for 24 hours;

The dried TFT-LCD waste glass and the silicon carbide sludge are respectively placed in a ball mill and ground for 24 hours;

The ground TFT-LCD waste glass and the silicon carbide sludge are respectively sieved by a 40-600 mesh sieve to have an average particle diameter;

The TFT-LCD waste glass having an average particle diameter is sufficiently mixed with the cerium carbide sludge to form the raw material.

In summary, the environmentally-friendly mesoporous molecular sieve humidity-regulating material of the present invention achieves the purpose of recycling and recycling TFT-LCD waste glass and carbonized sludge by using TFT-LCD waste glass and silicon carbide sludge as main materials. The preparation method comprises the following steps: using TFT-LCD waste glass as the main raw material, replacing TFT-LCD waste glass with different proportions of silicon carbide sludge, and performing alkali fusion, bismuth aluminum extraction, template formation, hydrothermal synthesis and template removal. The environmentally friendly medium pore molecular sieve humidity-regulating material of the invention.

The preferred embodiments of the present invention are described in detail with reference to the accompanying drawings.

The pore molecular sieve humidity-regulating material of the invention refers to a material which can adjust the humidity of the environment. The principle of humidity control is that when the relative humidity of the environment is high, the equilibrium moisture content will increase rapidly, and the humidity-control material absorbs the moisture in the environment to prevent The relative humidity of the environment increases; conversely, when the relative humidity in the environment is low, the equilibrium moisture content decreases rapidly, and the humidity-control material releases moisture to humidify in the air to prevent the relative humidity of the environment from decreasing. Therefore, the pore molecular sieve humidity-regulating material of the invention can be used as an environment moisture absorption product, a building material or a coating material for building materials, etc., wherein the total amount of heavy metals, TCLP dissolution concentration, equilibrium moisture content and humidity control performance are required. In line with the standard, it can be used as building materials.

The invention relates to recovering and processing a TFT-LCD waste glass and a cerium carbide sludge to obtain a mesoporous molecular sieve humidity-regulating material (hereinafter referred to as a humidity-conditioning material), wherein the TFT-LCD waste glass is used as a main component and the bismuth carbide is used. The sludge is substituted to change the characteristics of the mesoporous molecular sieve to obtain a humidity-controlling material having excellent moisture absorption and equilibrium moisture content; wherein the content ratio of the TFT-LCD waste glass and the tantalum carbide sludge is: 10 wt% to 90 wt. % TFT-LCD waste glass and 10 wt% to 90 wt% of cerium carbide (SiC) sludge, wherein the TFT-LCD waste glass comprises cerium oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), calcium oxide ( CaO), the SiC sludge contains cerium oxide (SiO ₂ ). In a preferred embodiment, the ratio of TFT-LCD waste glass to tantalum carbide sludge is 20 wt%: 80 wt% (1:4), 10 wt%: 90 wt% (1:9) or 87.5 wt%: 12.5% wt% ( 7:1); again, the optimum is 87.5 wt%: 12.5 wt% (7:1).

The humidity-conditioning material of the present invention preferably has an equilibrium moisture content of more than 5 kg/m ³ (>5 kg/m ³ ) in an environment of room temperature and a relative humidity of 10 to 95% (according to Japanese Industrial Standard JIS) A 1475 building material equilibrium moisture content and its determination method).

The humidity-controlling material of the present invention preferably has a hygroscopic content of more than 29 g/m ² (>29 g/m ² ) for 12 hours (according to Japanese Industrial Standards, the third grade of the JIS A 1470-1 regulation and its humidity. Response method).

The "TFT-LCD waste glass" as used in the present invention means containing cerium oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), iron oxide (Fe ₂ O ₃ ), calcium oxide (CaO), magnesium oxide ( A glass of a composition of MgO), titanium oxide (TiO ₂ ), or a combination thereof; further represents a waste glass of a side material, a scrap or a defective product produced at the time of manufacture of a liquid crystal panel. In a preferred embodiment of the present invention, the main components of the TFT-LCD waste glass are cerium oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), and calcium oxide (CaO).

The "carbonized sludge" according to the present invention means containing cerium oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), iron oxide (Fe ₂ O ₃ ), magnesium oxide (MgO), and sulfur oxide (SO). ₃ ) glass of potassium oxide (K ₂ O), titanium dioxide (TiO ₂ ) or a combination thereof; further indicating that in the production process of the LED sapphire substrate, tantalum carbide is used as the abrasive material, and water is used as the grinding medium or the grinding is added. The liquid removes waste sludge from the sapphire substrate. In a preferred embodiment of the invention, the main component of the niobium carbide sludge is ceria (SiO ₂ ).

The invention also provides a preparation method of the environmentally-friendly mesoporous molecular sieve humidity-regulating material, wherein the TFT-LCD waste glass and the tantalum carbide sludge are pretreated as raw materials, and the pretreatment comprises a large amount of sampling (collecting 100 kg) Above), dried at 105 ° C for 24 hours, placed in a ball mill for 24 hours, sieved through a 40-200 mesh sieve, the average particle size, and mixed thoroughly, as a synthetic mesoporous molecular sieve Raw material for wet materials. Referring to FIG. 4, the manufacturing process of the pore molecular sieve moisture regulating material of the present invention comprises a material taking step S1, an alkali melting step S2, a bismuth aluminum extraction step S3, a template forming step S4, a hydrothermal synthesis step S5, and a template removing step S6. among them:

Step S1: providing TFT-LCD waste glass and tantalum carbide sludge as a raw material for preparing a medium pore molecular sieve humidity-controlling material, the raw material composition comprising 10 wt% to 90 wt% of TFT-LCD waste glass, and 10 wt% to 90 wt% The strontium carbide sludge; wherein the weight ratio of the TFT-LCD waste glass to the strontium carbide sludge is preferably 1:4, 1:9 or 7:1, and most preferably 7:1.

Alkali melting step S2: adding an alkali agent to the raw material at a mass ratio of 1.25 to 1.75 (alkaline agent (g): raw material (g) = 1.25 to 1.75:1), followed by an alkali fusion process at a temperature of 450 to 650 ° C, An alkali fusion product is obtained; the alkali fusion process is performed by adding an alkali agent to the raw material for ingot pressing, and then placing it in a high temperature furnace and calcining at 450 ° C, 550 ° C or 650 ° C, wherein the alkali agent is selected from sodium hydroxide (NaOH). ), potassium hydroxide (KOH) or sodium carbonate (Na ₂ CO ₃ ), and the mass ratio of the alkali agent to the raw material is 1.25, 1.5 or 1.75; preferably, the alkali agent is sodium hydroxide and the mass ratio to the raw material is 1.5.

矽 aluminum extraction step S3: extracting the lanthanum source and the aluminum source in the alkali fusion product to obtain a sodium strontium aluminate solution having a liquid-solid ratio (L/S) of 5 to 15; preferably, the alkali fusion product is liquid The solid ratio is 5, 10 or 15, and the source of germanium and aluminum is extracted; optimally, the liquid-solid ratio is 10.

Template forming step S4: providing a CTAB (cetyltrimethylammonium bromide) aqueous solution, adding the sodium strontium aluminate solution to the CTAB aqueous solution to prepare a gel solution; wherein the CTAB aqueous solution comprises CTAB and 30 mL After the ionized water and 1.5 mL of ammonia water were added to the CTAB aqueous solution, the gel solution was prepared by adjusting the pH value and vigorously stirring the reaction. Among them, the CTAB system in the CTAB aqueous solution was added at a ratio of molar ratio CTAB:SiO ₂ =1:0.15 (opposite should be 0.15:1).

Hydrothermal synthesis step S5: The gel is dissolved in a high temperature autoclave and subjected to a hydrothermal reaction at a temperature of 90 to 120 ° C; preferably, the hydrothermal reaction temperature is 90 ° C, 105 ° C or 120 ° C. 24-60 hours of hydrothermal reaction.

Template removal step S6: filtering the solid product after the hydrothermal reaction to be washed, drying and calcining to remove the CTAB template, thereby preparing an environmentally-friendly mesoporous molecular sieve humidity-regulating material; wherein, after filtering the solid product, The environmentally friendly mesoporous molecular sieve humidity-conditioning material was prepared by washing with deionized water and drying in an oven at 105 ° C, followed by continuous calcination at 550 ° C for 5 hours to completely remove the CTAB template.

The following examples are used 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; the individual preparations are made in the environmental protection according to the different ratios of the TFT-LCD waste glass and the strontium carbide sludge. Various performance tests of pore molecular sieve conditioning materials.

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

The basic physical properties of the TFT-LCD waste glass and the niobium carbide sludge of the present invention are shown in Table 1 below. Among them, the pH values of TFT-LCD waste glass and tantalum carbide sludge are 8.44 and 7.55, indicating that both TFT-LCD waste glass and tantalum carbide sludge are alkaline materials; and TFT-LCD waste glass and SiC sludge The specific gravity is 2.15 and 2.15 respectively.

<TABLE border="1" borderColor="#000000" width="_0003"><TBODY><tr><td> Table 1 </td></tr><tr><td> Raw material</td> <td> pH (1:10) </td><td> Specific Gravity</td><td> Density (g/cm³) </td><td> Moisture (% </td><td> Fineness (m³/kg) </td></tr><tr><td> TFT-LCD waste glass</td><td> 9.09 </td><td> 3.06 </td><td> 2.33 </td><td> 0.01 </td><td> 253 </td></tr><tr><td> Carbide sludge </td><td> 7.85 </td><td> 3.38 </td><td> 2.54 </td><td> 7.23 </td><td> 279 </td></tr></ TBODY></TABLE>

Please refer to FIG. 1 and Table 2 below for the results of particle size distribution analysis and chemical composition analysis of the raw materials of the present invention. Figure 1 shows that the particle size of the TFT-LCD waste glass is mainly distributed in the range of 19-105 μm, which is about 99.8% of the whole; the particle size of the tantalum carbide sludge is mainly distributed in the range of 19-149 μm, which is about 84.05 of the whole. %. Table 2 shows that the main components of TFT-LCD waste glass are SiO ₂ , Al ₂ O ₃ and CaO, accounting for 69.7 %, 15.3% and 8.45% respectively; while the main composition of strontium carbide sludge is mainly SiO ₂ , accounting for 98.4 %. . Among them, the TFT-LCD waste glass is mainly from the cutting material of the glass substrate, and SiO ₂ and Al ₂ O ₃ are the main body of the glass network structure, and therefore, contain a high content of Al ₂ O ₃ , so the research by TFT - LCD waste glass contains Al ₂ O ₃ and tantalum carbide sludge for quenching and tempering, so that there is sufficient source and aluminum source to synthesize mesoporous molecular sieve to adjust the moisture content, and at the same time, it has the advantages of low cost and resource reuse.

<TABLE border="1" borderColor="#000000" width="_0004"><TBODY><tr><td> Table 2 </td></tr><tr><td> Chemical composition (%) < /td><td> TFT-LCD waste glass</td><td> carbonized sludge</td></tr><tr><td> SiO₂</td>< Td> 69.7 </td><td> 98.4 </td></tr><tr><td> Al₂O₃</td><td> 15.3 </td><td> 0.80 </td></tr><tr><td> Fe₂O₃</td><td> 0.18 < /td><td> 0.58 </td></tr><tr><td> CaO </td><td> 8.45 </td><td> 0.09 </td></tr><tr>< Td> MgO </td><td> 0.77 </td><td> - </td></tr><tr><td> SO₃</td><td> - </td><td> 0.06 </td></tr><tr><td> K₂O </td><td> - </td><td> 0.01 </ Td></tr><tr><td> TiO₂</td><td> 0.22 </td><td> 0.01 </td></tr></TBODY>< /TABLE>

Figure 2 is an XRD pattern of the starting material of the present invention. 2 shows that the TFT-LCD waste glass is melted into a liquid phase by using a large amount of flux in the process, and the crystal lattice is not regularly arranged and solidified during the condensation process, so the inside of the glass is amorphous, and there is no XRD analysis. Any significant diffraction peaks are produced. In addition, the tantalum carbide sludge exhibits a typical amorphous broad peak in the range of 16-30° of 2θ, confirming the absence of an ordered crystal structure, and since there is no peak, the purity of the cerium oxide is confirmed, and the main diffraction The peaks at 34.18°, 35.72°, 38.23°, 60.15°, and 71.96° indicate that tantalum carbide is 6H-SiC, and the crystal phase species are consistent with the literature (Ding et al., 2015).

Please refer to Table 3 below to show the total amount of heavy metals in the raw materials of the present invention and the TCLP heavy metal dissolution concentration. The results of total heavy metal analysis showed that the total amount of heavy metals in TFT-LCD waste glass was mainly Zn, and its content was 160 mg/kg. The source should be the wire in the panel etching tank. The heavy metal dissolution of the strontium carbide sludge has a Cu content of up to 1100 mg/kg and a secondary Zn content of 20 mg/kg. In the present invention, each material was subjected to a heavy metal dissolution test by the toxic characteristic dissolution procedure (TCLP) method of NIEA R201.14C, and the heavy metal dissolution concentration of each material was measured by FLAA. The results are shown in Table 3. The TCLP heavy metal dissolution results showed that the Zn elution amount of the TFT-LCD waste glass was 0.10 mg/L; the Zn dissolution amount of the strontium carbide sludge was 0.08 mg/L, the Ni dissolution amount was 0.06 mg/L, and the Cu dissolution amount was 7.4 mg. /L. According to the foregoing test results, the amount of heavy metal eluted from the TFT-LCD waste glass and the strontium carbide sludge of the present invention is in compliance with regulatory standards and has the potential to be resourced.

<TABLE border="1" borderColor="#000000" width="_0005"><TBODY><tr><td> Table 3 </td></tr><tr><td> Total amount of heavy metals (mg/ Kg) </td><td> Pb </td><td> Cr </td><td> Cu </td><td> Zn </td><td> Cd </td><td> Ni </td></tr><tr><td> TFT-LCD waste glass</td><td> ND </td><td> ND </td><td> ND </td><td> 160 </td><td> ND </td><td> ND </td></tr><tr><td> Carbide sludge</td><td> ND </td><td> ND </td><td> 1100 </td><td> 20 </td><td> ND </td><td> 10 </td></tr><tr><td> TCLP (mg /L) </td><td> Pb </td><td> Cr </td><td> Cu </td><td> Zn </td><td> Cd </td><td> Ni </td></tr><tr><td> TFT-LCD waste glass</td><td> ND </td><td> ND </td><td> ND </td><td > 0.10 </td><td> ND </td><td> ND </td></tr><tr><td> Carbide sludge</td><td> ND </td><td > ND </td><td> 7.40 </td><td> 0.08 </td><td> ND </td><td> 0.06 </td></tr><tr><td> Regulatory standards </td><td> 5.00 </td><td> 5.00 </td><td> 15.00 </td><td> - </td><td> 1.00 </td><td> - </ Td></tr><tr><td> ND: Pb<0.015 mg/L; Cr<0.009 mg/L; Cd<0.021 mg/L </t d></tr></TBODY></TABLE>

Example 2: Preparation of the pore molecular sieve moisture regulating material of the present invention

The most influential factor in the process of synthesizing medium-porosity molecular sieve humidity-regulating material by using TFT-LCD waste glass and tantalum carbide sludge is that the raw material of the precursor liquid needs sufficient source and source of aluminum, so the invention The TFT-LCD waste glass and the cerium carbide sludge are tempered in different ratios, and the ratio of SiO ₂ and Al ₂ O ₃ can be used as a basis for evaluating the characteristics of the synthetic medium pore molecular sieve humidity modulating material.

Please refer to Table 4 below to show the chemical composition of TFT-LCD waste glass and tantalum carbide sludge after quenching and tempering with different ratios. It can be seen from Table 4 that the main chemical composition of pure TFT-LCD waste glass is SiO ₂ , Al ₂ O ₃ and CaO, and the contents are 69.7 %, 15.3 % and 8.45%, respectively, so there is potential to replace the source of lanthanum and aluminum. Next, in this embodiment, the TFT-LCD waste glass and the cerium carbide sludge were tempered at a ratio of 1:4, 1:9, and 7:1, and chemical composition analysis was performed. Wherein, when the substitution amount of the strontium carbide sludge is 80% (the ratio is 1:4), the composition of the SiO ₂ and Al ₂ O ₃ is 94% and 3.09%; when the substitution amount of the strontium carbide sludge is 90% ( When the ratio is 1:9), the SiO ₂ and Al ₂ O ₃ are 95.8% and 2.29%, respectively. In addition, when the amount of tantalum carbide sludge is 12.5% (the ratio is 7:1), the SiO _{2 is used.} And Al ₂ O ₃ were 75.6 and 13.1%, respectively.

<TABLE border="1" borderColor="#000000" width="_0006"><TBODY><tr><td> Table 4 </td></tr><tr><td> Chemical Composition</td> <td> TFT-LCD waste glass</td><td> Tantalum carbide sludge</td><td> IGA(1:4) </td><td> IGA (1:9) </td>< Td> IGA (7:1) </td></tr><tr><td> SiO₂</td><td> 69.7 </td><td> 98.4 </td ><td> 94.0 </td><td> 95.8 </td><td> 75.6 </td></tr><tr><td> Al₂O_{3< /sub></td><td> 15.3 </td><td> 0.80 </td><td> 3.09 </td><td> 2.29 </td><td> 13.1 </td></tr ><tr><td> CaO </td><td> 8.45 </td><td> 0.09 </td><td> 1.50 </td><td> 0.78 </td><td> 7.06 </ Td></tr><tr><td> SO₃</td><td> - </td><td> 0.06 </td><td> 0.06 </td>< Td> 0.07 </td><td> 0.03 </td></tr><tr><td> TiO₂</td><td> 0.22 </td><td> 0.01 </td><td> 0.06 </td><td> 0.04 </td><td> 0.15 </td></tr><tr><td> Fe₂O<sub >3}</td><td> 0.18 </td><td> 0.58 </td><td> 0.52 </td><td> 0.54 </td><td> 0.26 </td> </tr><tr><td> IGA: The ratio of TFT-LCD waste glass to tantalum carbide sludge. </td></tr></TBODY></TABLE>

Referring to FIG. 3A to FIG. 3C, XRD patterns of different alkali melting temperatures (450-650 ° C) and alkali agent addition amounts (1.25 to 1.75) when the ratio of the TFT-LCD waste glass to the tantalum carbide sludge of the present invention is 7:1 are shown. . As can be seen from the figure, when the alkali melting temperature is 450 ° C, 550 ° C, 650 ° C, the crystal phase of the alkali agent added mass ratio of 1.25, 1.5 and 1.75 is free of quartz phase, which is converted into tannic acid due to the quartz phase. Sodium and strontium aluminate; and as the temperature increases, the crystal phase strength tends to increase.

Referring to FIG. 5, the ratio of the alkali melting temperature (450-650 ° C) and the amount of alkali agent added when the ratio of the TFT-LCD waste glass of the TFT-LCD waste glass and the tantalum carbide sludge of the present invention is 7:1. (1.25~1.75) cerium oxide (SiO ₂ ) extraction amount. It can be seen from the figure that when the alkali melting temperature is 650 ° C, the amount of the alkali agent added is 1.5, and the highest SiO ₂ extraction amount can be obtained, so that the optimum operating conditions are suitable for the subsequent hydrothermal synthesis test.

Example 3: Material properties of the pore molecular sieve moisture regulating material of the present invention

In this embodiment, the liquid-solid ratio is 5, 10, and 15, and the mesoporous molecular sieve humidity-regulating material is synthesized at a hydrothermal temperature of 90 ° C, 105 ° C, and 120 ° C. Please refer to FIG. 6A to FIG. 6C to illustrate the crystallinity of the mesoporous molecular sieve humidity-regulating material synthesized by the medium-porosity molecular sieve humidity-regulating material at different liquid-solid ratios and hydrothermal temperatures.

Referring to Figure 6A, the crystallinity of the mesoporous molecular sieve conditioned material synthesized at different reaction temperatures when the liquid to solid ratio is 5 is shown. As the reaction temperature increases, the characteristic peaks increase significantly and the crystallinity is stronger. According to the literature, when the reaction temperature is higher, the characteristic peak d(100) will shift to a lower value, indicating that the lattice space d(100) of the pore increases, and the temperature is too high, which will affect the mesoporous material. The sequence structure exhibits a degraded state, so when the reaction temperature is 120 ° C and the liquid-solid ratio is 5, the peak value of the medium-porosity molecular sieve humidity-conditioning material slightly decreases.

Referring to Figure 6B, the crystallinity of the mesoporous molecular sieve conditioned material synthesized at different reaction temperatures when the liquid to solid ratio is 10 is shown. Among them, when the reaction temperature is 90 °C, the characteristic peak of the synthesized mesoporous molecular sieve humidity-regulating material is obviously higher than 105 °C and 120 °C, because the micelle formed by the surfactant molecular aggregates is improved by the crystallization temperature. The deformation or partial destruction occurs, which leads to a serious decrease in the order of pore structure in the product, indicating that when the liquid-solid ratio is 10, the crystallinity tends to be better when the hydrothermal temperature is 90 °C.

Referring to Fig. 6C, the crystallinity of the mesoporous molecular sieve humidity-modulating material synthesized at different reaction temperatures is shown when the liquid-solid ratio is 15. Among them, when the hydrothermal reaction temperature is 90 ° C, 105 ° C and 120 ° C, there are obvious main characteristic front d (100). According to the literature, it is considered that the weak peaks d(110) and d(200) are less obvious, which may be caused by the introduction of aluminum (Al) in the framework, which causes the sample grains to decrease.

Example 4: Balanced moisture content and humidity control performance of the pore molecular sieve moisture regulating material of the present invention

This embodiment is based on the method for determining the equilibrium moisture content of building materials according to Japanese Industrial Standard JIS A 1475, at an ambient temperature of 23 ° C and at different ambient humidity (10%, 33%, 55%, 75%, 85% and The equilibrium moisture content moisture absorption and desorption curve of the medium pore molecular sieve humidity-regulating material was measured under the condition of 95%). The measurement results are shown in Fig. 7A to Fig. 7C, showing different liquid-solid ratio (5~15) and different hydrothermal reaction temperatures (90~120). °C) Synthetic moisture content of the mesoporous molecular sieve humidity-regulating material.

Figure 7A shows a liquid-solid ratio of 5, when the hydrothermal temperature is 90 ° C, the equilibrium moisture content is 14.18 kg / kg; as the hydrothermal temperature increases to 120 ° C, the highest equilibrium moisture content is 19.05 kg / kg; 7B shows a liquid-solid ratio of 10, when the hydrothermal temperature is 105 ° C, the highest equilibrium moisture content is 17.08 kg / kg; Figure 7C shows a liquid-solid ratio of 15, when the hydrothermal temperature is 90 ° C, the equilibrium moisture content 19.71 kg/kg. 7A to 7C and the foregoing description, the equilibrium moisture content of the mesoporous molecular sieve humidity-regulating material synthesized in the liquid-solid ratio of 5, 10, 15 and different hydrothermal temperatures is higher than 5 kg/m ³ , That is, the pore molecular sieve humidity-conditioning material of the present invention conforms to the standard of building materials of JIS A 1475.

This example tests the moisture absorption and desorption rate of the pore molecular sieve moisture regulating material of the present invention at a relative humidity of 53-75% according to the Japanese Industrial Standard JIS A 1470 humidity response method. The system firstly saturates the medium-porosity molecular sieve humidity-control material into a relative humidity of 53%; then the medium-porosity molecular sieve humidity-control material is placed in an environment relative humidity of 75%, continuously monitored for 24 hours; and finally placed in the environment. When the relative humidity is 53%, the monitoring is carried out for 24 hours. Finally, the adsorption and desorption curves of the unit area at different times are obtained. The results are shown in Fig. 8A to Fig. 8C, showing different liquid-solid ratio (5~15) and different water. The 48-hour continuous moisture absorption and desorption test of the mesoporous molecular sieve humidity-regulating material was synthesized at a thermal reaction temperature (90 to 120 ° C).

8A shows a liquid-solid ratio of 5, and when the hydrothermal temperature is 90 ° C, the 24-hour moisture absorption of the synthesized mesoporous molecular sieve humidity-conditioning material is 48.08 g/m ² ; and FIG. 8B shows a liquid-solid ratio of 10, When the hydrothermal temperature is 90 ° C, the 24-hour moisture absorption of the synthetic mesoporous molecular sieve humidity-control material is 85.75 g / m ² ; in addition, Figure 8C shows a liquid-solid ratio of 15, when the hydrothermal temperature is 105 ° C At the time, the 24-hour moisture absorption of the medium pore molecular sieve humidity-control material was 76 g/m ² . 8A to 8C and the foregoing description, when the liquid-solid ratio is 5, the optimal moisture absorption amount of the synthesized mesoporous molecular sieve humidity-regulating material is more than 29 g/m ² , which conforms to the Japanese industrial standard humidity-control building material JIS A. The standard for the 12-hour moisture absorption of the third grade of the 1470-1 regulation; when the liquid-solid ratio is 10 and 15, the optimal moisture absorption of the synthetic mesoporous molecular sieve humidity-regulating material is greater than 71 g/m ² , which is in accordance with the A standard of 12 hours of moisture absorption.

Referring to Figures 9A to 9C, TEM images of mesoporous molecular sieve humidity-conditioning materials synthesized at different liquid-solid ratios (5-15) and hydrothermal reaction temperatures of 90 °C are shown. As can be seen from the figure, when the liquid-solid ratio is 5, 10 and 15, the synthesized mesoporous molecular sieve humidity-regulating material exhibits a hexagonal array of ordered mesopores and a uniform pore size, and the spacing between the mesopores is good. .

The above results show that the TFT-LCD waste glass and the strontium carbide sludge are tempered in a ratio of 7:1, and the desired citrate and yttrium aluminate can be effectively extracted by the alkali fusion procedure. When the hydrothermal reaction temperature is 90 °C, the low-cost and environmentally-friendly mesoporous molecular sieve humidity-regulating materials synthesized meet the hygroscopicity of the Japanese Industrial Standards JIS A 1470 and 1475 humidity-control building materials (>29 g/m). ² ) and the average equilibrium moisture content specification (>5 kg/m ³ ), so the TFT-LCD waste glass and the strontium carbide sludge quenching and tempering hydrothermal synthesis of the mesoporous molecular sieve humidity control material do have resources for reuse and green building materials The potential of cloth materials. Further, it is possible to apply a high value-added humidity-conditioning material which is extended to other types of enamel-containing industrial waste and which can be mass-produced, and is applied to protect the environment.

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.

S1‧‧‧Material steps
S2‧‧‧ alkali melting step
S3‧‧‧矽 aluminum extraction step
S4‧‧‧ template forming steps
S5‧‧‧ Hydrothermal synthesis steps
S6‧‧‧Template removal steps

1 is a particle size distribution analysis of the TFT-LCD waste glass and the cerium carbide sludge of the present invention. 2 is an XRD pattern of the TFT-LCD waste glass and the cerium carbide sludge of the present invention. 3A to 3C are XRD patterns of different alkali melting temperatures (450-650 ° C) and alkali agent addition amounts (1.25 to 1.75) when the ratio of the TFT-LCD waste glass to the tantalum carbide sludge of the present invention is 7:1. 4 is a schematic flow chart showing the steps of the preparation method of the environmentally-friendly mesoporous molecular sieve humidity-regulating material of the present invention. 5 is a different alkali melting temperature (450-650 ° C) and an alkali agent addition amount (NaOH) when the ratio of the TFT-LCD waste glass of the TFT-LCD waste glass and the tantalum carbide sludge of the present invention is 7:1. , 1.25~1.75) of cerium oxide (SiO ₂ ) extraction amount. 6A to 6C show the crystallinity of the mesoporous molecular sieve humidity-regulating material synthesized by the present invention in different liquid-solid ratios (5-15) and different hydrothermal reaction temperatures (90-120 °C). 7A to 7C show the equilibrium moisture content absorption and desorption curves of the mesoporous molecular sieve humidity-regulating material synthesized in different liquid-solid ratios (5-15) and different hydrothermal reaction temperatures (90-120 °C). 8A to 8C show a 48-hour continuous moisture absorption and desorption test of a mesoporous molecular sieve humidity-modulating material synthesized in different liquid-solid ratios (5-15) and different hydrothermal reaction temperatures (90-120 °C). 9A to 9C are TEM images of the mesoporous molecular sieve humidity-conditioning material synthesized by the present invention at different liquid-solid ratios (5-15) and hydrothermal reaction temperature of 90 °C.

S1‧‧‧Material steps

S2‧‧‧ alkali melting step

S3‧‧‧矽 aluminum extraction step

S4‧‧‧ template forming steps

S5‧‧‧ Hydrothermal synthesis steps

S6‧‧‧Template removal steps

Claims (3)

The invention relates to a method for preparing an environmentally-friendly medium-porosity molecular sieve humidity-regulating material, the method steps comprising the steps of: obtaining a TFT-LCD waste glass and a silicon carbide sludge as a raw material for preparing a medium-porosity molecular sieve humidity-controlling material, the raw material composition comprising 87.5wt % TFT-LCD waste glass, and 12.5wt% strontium carbide sludge; alkali fusion step: adding alkali agent to the raw material at a mass ratio of 1.25~1.75, and performing alkali sintering process at temperature 450~650°C Alkali fusion product; bismuth aluminum extraction step: extracting lanthanum source and aluminum source in alkali fusion product, preparing sodium strontium aluminate solution having liquid-solid ratio (L/S) of 5-15; template forming step: providing a CTAB aqueous solution Adding the sodium citrate solution to the CTAB aqueous solution to prepare a gel solution; hydrothermal synthesis step: placing the gel in a high temperature autoclave overnight, and performing a hydrothermal reaction at a temperature of 90 to 120 ° C; Removal step: the solid product after the hydrothermal reaction is filtered and washed, dried and then calcined to remove the CTAB template to obtain an environmentally-friendly mesoporous molecular sieve humidity-regulating material. The method for preparing an environmentally-friendly mesoporous molecular sieve humidity-regulating material according to claim 2, wherein: in the obtaining step, the weight ratio of the TFT-LCD waste glass to the niobium carbide sludge is 7:1; the alkali melting step In the alkali fusion process, an alkali agent is added to the raw material for ingot pressing, and then placed in a high temperature furnace, and calcined at 450 ° C, 550 ° C or 650 ° C, wherein the alkali agent is selected from the group consisting of sodium hydroxide (NaOH) and potassium hydroxide. (KOH) or sodium carbonate (Na ₂ CO ₃ ), and the mass ratio of the alkali agent to the raw material is 1.25, 1.5 or 1.75; in the bismuth aluminum extraction step, the alkali fusion product is liquid to solid ratio of 5, 10 or 15 Extracting a cerium source and an aluminum source; in the template forming step, the CTAB aqueous solution comprises CTAB and 30 mL of deionized water and 1.5 mL of ammonia water, and the sodium strontium aluminate solution is added to the CTAB aqueous solution, and after adjusting the pH value and vigorously stirring the reaction, Preparing the gel solution; in the hydrothermal synthesis step, performing a hydrothermal reaction at a hydrothermal reaction temperature of 90 ° C, 105 ° C or 120 ° C for 24 to 48 hours; in the template removal step, the solid product filtration After washing out, it was washed with deionized water and dried in an oven at 105 ° C, followed by 550 The environmentally-friendly mesoporous molecular sieve humidity-conditioning material was prepared by continuously calcining at ° C for 5 hours to completely remove the CTAB template. The method for preparing an environmentally-friendly mesoporous molecular sieve humidity-regulating material according to claim 1 or 2, wherein the TFT-LCD waste glass and the tantalum carbide sludge are pretreated as raw materials, wherein the pretreatment The method comprises the following steps: drying the collected TFT-LCD waste glass and the silicon carbide sludge at a temperature of 105 ° C for 24 hours; and drying the dried TFT-LCD waste glass and the carbonized tantalum sludge into a ball mill for 24 hours; The polished TFT-LCD waste glass and the silicon carbide sludge are respectively sieved by a sieve of 100 to 200 mesh to have an average particle diameter; the TFT-LCD waste glass after the average particle diameter is thoroughly mixed with the silicon carbide sludge to form the raw material. .