TWI524937B - Method for manufacturing silicate mesoporous material by recycling waste colored glasses - Google Patents

Description

Hole material in citrate prepared by recycling waste colored glass and preparation method thereof

The invention relates to a medium pore material and a preparation method thereof, in particular to a pore material in a tantalate prepared by recycling waste colored glass and a preparation method thereof.

According to the daily production of waste glass, there are glass containers, flat glass, automobile glass, lighting tubes, image tubes, etc., and the number of flat glass and glass containers is mostly; currently there is only metal or special The transparent waste glass container of the additive can be directly recovered by the glass manufacturer, and 50% of transparent waste glass is used as a raw material for further production of other glass products, and other waste glass is mostly treated by landfill.

In recent years, glass containers have been difficult to react with their contents due to their stable materials, and they have been easily shaped to have an improved design. Therefore, many beverages use colored glass as a container to increase the number of colored waste glass containers; however, Glass has the characteristics of heavy weight and non-corrosion. Long-term treatment by landfill not only occupies landfill space but also shortens its service life. Instead, it is treated by incineration method, which also increases the load of incinerator and shortens its service life.

It is worth noting that in 1992, Mobil Oil proposed a pore-like zeolite material with adjustable and uniform pores ranging from 1.5 to 10.0 nanometers (nm), especially with hexagonal shape. MCM-41 medium hole material with stacked and uniform tunnel holes is used as catalyst and suction The application of the attached agent is the most attractive.

In view of the fact that MCM-41 is a mesoporous zeolite with cerium oxide (SiO ₂ ) as the aggregate, the general colored glass container component and the transparent glass container component only differ in the presence or absence of pigmentation and contain a large amount of cerium oxide (SiO _{2 ).} In view of this, the inventors of the present invention considered that it is necessary to propose a void material which is prepared by recycling waste colored glass and a preparation method thereof to further solve the above-mentioned problem of disposal of waste glass.

The object of the present invention is to provide a strontium silicate material prepared by recycling waste colored glass and a preparation method thereof, which mainly comprises using a waste colored glass as a bismuth source to obtain a sulphate hole material, thereby disposing the colored glass. The processing resources are turned into medium-hole materials to solve the impact of the buried waste glass on the environment, and at the same time achieve the purpose of sustainable use of resources and economic benefits.

In order to achieve the above object, in accordance with the present invention, a method for preparing a hole material in a phthalate prepared by recycling waste colored glass is provided, the method steps comprising: (a) a source providing step: providing 60 to 80 wt Dissolving colored glass in one of % cerium oxide (SiO ₂ ), pulverizing the waste colored glass into a glass powder to serve as a cerium source, and dissolving 1 to 20 gram of glass powder in a sodium hydroxide solution to form a cerium source solution; (b) taking cetyltrimethylammonium bromide (CTMABr) dissolved in ammonium hydroxide (NH ₄ OH) to form a template of CTMABr:NH ₄ OH molar ratio of 0.25:1.5 to 0.3:3.13 (c) pH adjustment step: the solution of the ruthenium source is added dropwise to the templating agent and the pH of the mixture is adjusted to 9 to 12, and a mixture is formed after stirring; (d) a filtration drying step: The mixture is filtered to obtain an intermediate product, and the intermediate product is washed to dry the intermediate product at a temperature of 100 ± 5 ° C; (e) calcination step: placing the intermediate product in a high temperature furnace at 450 to 600 The intermediate product is calcined at a temperature of °C for 4 to 6 hours to remove the mold on the intermediate product. Agent, to obtain a preparation of the silicate waste material colored glass in the holes.

According to the present invention, there is provided a hole material in a silicate according to the above preparation method, wherein the medium pore material has a specific surface area of 900 to 1300 m 2 /g (m ² /g) and an average pore volume of 0.7 to 1.0. Cubic centimeters per gram (cm ³ /g).

According to the present invention, there is provided a hole material in a citrate prepared by the above preparation method, wherein the medium hole material is subjected to an X-ray diffraction test, and the angle of 2 θ of the 100 crystal plane is 2.50°, and 2 θ of the 110 crystal plane The angle is 4.33° and the mesoporous material has a d-spacing of 3.53 and 2.04 nanometers (nm) and a lattice parameter (a ₀ ) of 4.08 nanometers (nm).

According to the present invention, there is provided a sulphate void material obtained by the above preparation method for adsorbing volatile organic compounds.

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

In order to enable your review committee to have a better understanding and understanding of the purpose, features and effects of the present invention, please follow the [simplified description of the drawings] as follows: First, please refer to Figure 1 to explain this The invention provides a preferred embodiment of a method for preparing a void material in a waste colored glass recovery process. The method steps mainly include: a source supply step S1, a template preparation step S2, a pH adjustment step S3, and a filter drying. Step S4 and calcination step S5, wherein: (a) the source of the source is provided with the step S1: providing a waste colored glass containing 60 to 80% by weight of cerium oxide (SiO ₂ ), and pulverizing the waste colored glass into a glass powder As a source of lanthanum, 1 to 10 grams of glass powder is dissolved in a sodium hydroxide solution to form a ruthenium source solution; in the present embodiment, the glass powder has a particle diameter of 0.1 to 0.8 mm, and the ruthenium source solution The glass powder and the sodium hydroxide solution are continuously stirred at a stirring speed of 600 rpm for 10 to 24 hours at a temperature of 150±5° C., and preferably continuously stirred for more than 24 hours; )template Preparation Step S2: Take cetyltrimethylammonium bromide (CTMABr) was dissolved in ammonium hydroxide (NH ₄ OH), to form CTMABr: NH ₄ OH molar ratio was 0.25: one 3.13: 1.5 to 0.3 a templating agent; in the present embodiment, the templating agent is dissolved in 125 ml of deionized water by 2.5 g of cetyltrimethylammonium bromide (CTMABr), and then 10 ml of ammonium hydroxide (NH ₄ OH) is added. , obtained by stirring until the cetyltrimethylammonium bromide (CTMABr) is completely dissolved; (c) pH adjustment step S3: adding the lanthanum solution dropwise to the templating agent, and adding Adjusting the pH of the mixture to 9 to 12 with sulfuric acid (H ₂ SO ₄ ) at a concentration of 4N, and then stirring the mixture for 6 to 8 hours at room temperature with a magnetizer to obtain a mixture; (d) filtering Drying step S4: filtering the mixture to obtain an intermediate product, washing the intermediate product and drying the intermediate product at a temperature of 100 ± 5 ° C; (e) calcining step S5: placing the intermediate product in a high temperature furnace, And calcining the intermediate product at a temperature of 450 to 600 ° C for 4 to 6 hours, removing the template agent on the intermediate product, and preparing a tannic acid prepared by disposing colored glass. The hole material in the salt; in the present embodiment, the intermediate product is preferably calcined at a temperature of 550 ° C for 6 hours.

The above is the main steps and components of the embodiment of the present invention. In the preferred embodiment of the present invention, the hole material in the citrate made of discarded colored glass (hereinafter referred to as G-MCM) and the conventional MCM- The material properties of the 41-hole material (hereinafter referred to as MCM-41) are as follows.

Please refer to Table 1 for the analysis results of the waste colored glass composition, MCM-41 composition and G-MCM composition taken in the embodiment of the present invention; it shows that the discarded colored glass contains 69.7% by weight. The cerium oxide (SiO ₂ ), the G-MCM made of the waste colored glass has 98.9% by weight of cerium oxide, which is very close to the cerium oxide content of MCM-41, which proves that the color can be discarded. The glass replaces the lanthanum source prepared by the MCM-41, effectively reuses the waste colored glass, and provides a low-cost citrate hole material.

Please refer to FIG. 2A and FIG. 2B for the analysis of the results of the analysis of the nitrogen isothermal adsorption/desorption apparatus (BET) of the G-MCM prepared in the embodiment of the present invention and the aforementioned MCM-41. The 2A graphs are nitrogen isotherm adsorption/desorption curves of MCM-41 and G-MCM, respectively. After observation, the isothermal adsorption/desorption curves belong to the Type IV (medium hole) curve of the six types. It can also be seen from the figure that the adsorption/desorption behavior has four stages: the first stage is that when the relative pressure is low, the nitrogen adsorption amount is slowly increased, which is consistent with the pore wall single layer-multilayer adsorption; the second stage is the relative pressure rise. When high, the nitrogen adsorption amount increases sharply, indicating that the capillary in the middle hole has condensation phenomenon; when the relative pressure is increased in the third stage, the nitrogen adsorption amount increases slowly again, indicating that the outside of the crystal has multiple layers of adsorption. The fourth stage is characterized by a pressure increase near saturation (P/P ₀ = 1.0) and a large increase in nitrogen adsorption, at which point the nitrogen fills all other holes.

It can be seen from Table 2 that the specific surface areas of MCM-41 and G-MCM are 1480 and 1328 m ² g ^-1 , respectively; the average pore volume is 0.987 and 0.818 cm ³ g ^{-1 , respectively} ; the other MCM-41 and G- The pore distribution curve of MCM is shown in Fig. 2B, and the pore distribution is concentrated at 3.37 and 2.62 nm, respectively.

Please refer to FIG. 3 for the purpose of explaining the X-ray diffraction analysis results of the G-MCM and the MCM-41 prepared by the embodiment of the present invention, wherein (100) and (110) of the MCM-41. The 2θ diffraction angle positions of the crystal planes are 2.59° and 4.38°, respectively, and the lattice spacing of MCM-41 is known by the Bragg's law nλ=2dsin θ(n=1) and the lattice parameter a ₀ . -spacing) are 3.41 and 2.02 nm, respectively, and the lattice parameter a ₀ = 3.94 nm. In addition, in the XRD pattern, the 2θ angles of the G-MCM (100) and (110) crystal faces are 2.50° and 4.33°, respectively, and the calculated d-spacing values are 3.53 and 2.04 nm, respectively. The lattice parameter a ₀ of the crystal plane (100) was calculated by the lattice parameter formula to be 4.08 nm.

Please refer to the 4A to 4D drawings to illustrate the SEM analysis results of the embodiments of the present invention. In order to understand the appearance and chemical composition of the materials, the structure and principle of the scanning electron microscope and the construction of the energy scattering spectrometer are used. The two materials were analyzed by the principle (Scanning Electron Microscopy & Energy Dispersive Spectrometer, SEM-EDS). It can be found from Fig. 4A and Fig. 4C that after the calcination, the outer surfaces of the MCM-41 and G-MCM materials have a regular structure, and their appearances are mostly spherical. Since the MCM-41 material carrier is a mesoporous material composed of SiO ₂ , the qualitative analysis of the chemical element composition by EDS is also used in this study. It can be clearly confirmed from Fig. 4B and 4C that the structure is composed of SiO ₂ . composition. In addition, it is also known from the EDS spectrum of G-MCM that the formation of an element containing Al by G-MCM is caused by the dissolution of Al ₂ O ₃ contained in the composition of the waste glass.

Please refer to the results of TEM analysis of the examples of the present invention with reference to the 5A to 5D drawings. The MCM-41 material prepared by the sol-gel method can be observed by MCM-41 after calcination at 550 °C. Its structure has The obvious pores exist and clearly show a uniform pipe size, which proves that MCM-41 has a consistent arrangement and a good degree of crystallization. In addition, the pore arrangement can be clearly observed by the analysis results of G-MCM, and the result is similar to the analysis result of MCM-41. It can be seen from the figure that the lattice spacing between MCM-41 and G-MCM is 3.41 and 3.53 nm, respectively.

Please refer to FIG. 6 for the NMR analysis results of the examples of the present invention; as shown in the figure, the ruthenium atom has a peak and a shoulder at a chemical shift tensor (δ) of -110 and -100. The system is derived from the two structures of Si(OSi) ₃ (OH) and Si(OSi) ₄ present in the yttrium atom, and the chemical shift tensor (δ) of the two structures is defined as a Q ₃ value and a Q ₄ The value, wherein the ratio of Q ₄ /Q ₃ represents the degree to which the ruthenium atoms are bonded to each other in the skeleton of the material in the formation, and the smaller the ratio of Q ₄ /Q ₃ , the higher the degree of bonding, the hydrazine-based The smaller the number, the less the skeleton defects are. In the present embodiment, the G-MCM of the present invention has a Q ₄ /Q ₃ ratio of 1.52, and the MCM-41 is 1.57, which proves the G of the present invention. -MCM's skeleton structure is better than MCM-41.

In addition, the present invention is a method for treating volatile organic compounds in a bismuth silicate material made of waste colored glass. The following is a method for adsorbing toluene components in a gas by the G-MCM of the present invention, which is mainly The gas flow rate is adjusted by the mass flow meter, the gas is introduced into a gas mixing tank for uniform mixing, and then introduced into the catalytic reactor system to perform a catalyst adsorption reaction with the G-MCM.

The reaction condition of the G-MCM of the invention for adsorbing toluene is at normal temperature Pressing is carried out by placing 0.5 g of the citrate hole material G-MCM into the catalyst reactor system, and then introducing a gas containing 250 to 1500 ppm of toluene into the catalyst reaction at a flow rate of 138 ml per minute. The reaction is carried out in the system, wherein, as shown in Fig. 7, the concentration change of the G-MCM of the present invention and the gas having a toluene concentration of 250, 500, 1000 and 1500 ppm is shown, and the tannic acid prepared by the present invention is known from the figure. When the G-MCM in the salt material corresponds to the above toluene concentration in sequence, the adsorption amount is 62, 106, 195 and 268 mg/g (mg/g), and the adsorption time is 5 to 50 min. The efficiency is about 85 to 88%. It can be seen from the above test results that the adsorption amount of G-MCM increases with the increase of toluene influx concentration; and the G-MCM of the present invention sequentially corresponds to the toluene concentration, and the penetration time is 360. 420, 480 and 510 minutes.

In addition, please refer to Fig. 8 to show the actual adsorption amount of the pore material S-MCM in the citrate of the present invention at different toluene concentrations compared with the Freundlich and Langmuir modes, wherein, as shown in Fig. 8, the Langmuir mode is shown. The calculated value is close to the actual value. Therefore, the Langmuir model can be considered to have good applicability to the single-component adsorption system. It is more suitable for describing the adsorption behavior of G-MCM materials, and its maximum adsorption capacity is 252 mg g ^-1 .

In summary, the hole material in the citrate prepared by the waste colored glass recycling and the preparation method thereof are not only innovative in the configuration method, but also can improve the efficiency compared with the conventional application, and should be filled with the patent novelty and progress. The statutory invention patent requirements for sex, and apply in accordance with the law.

S1‧‧‧Source supply steps

S2‧‧‧ template preparation steps

S3‧‧‧ pH adjustment steps

S4‧‧‧Filter drying step

S5‧‧‧ calcination step

Fig. 1 is a schematic flow chart showing the steps of preparing a pore material in a citrate prepared by recycling colored glass.

2A, 2B The present invention is a nitrogen isothermal adsorption/desorption apparatus (BET) analysis pattern of a hole material in a citrate prepared by discarding colored glass and MCM-41.

Fig. 3 The X-ray diffraction analysis (XRD) of the pore material of the citrate prepared by the waste colored glass recovery and the MCM-41.

4A to 4D The present invention is a scanning electron microscope (SEM) analysis pattern of a hole material (Fig. 4A, 4B) and MCM-41 (Fig. 4C, 4D) of a citrate prepared by discarding colored glass.

5A to 5D The present invention is a transmission electron microscope (TEM) analysis pattern of a hole material (Fig. 5A, 5B) and MCM-51 (Fig. 5C, 5D) of a citrate prepared by discarding a colored glass.

Fig. 6 is a nuclear magnetic resonance spectrum (NMR) of the pore material of the citrate prepared by the waste colored glass recovery and MCM-41.

Fig. 7 The hole material in the citrate prepared by recycling the waste colored glass is used for adsorbing the concentration change of toluene.

Fig. 8 The Langmuir model curve and the Freundlich model curve for adsorbing toluene in the strontium sulphate material prepared by recycling the colored glass.

S1‧‧‧Source supply steps

S2‧‧‧ template preparation steps

S3‧‧‧ pH adjustment steps

S4‧‧‧Filter drying step

S5‧‧‧ calcination step

Claims (10)

A method for preparing a pore material in a tantalate prepared by recycling waste colored glass, the method steps comprising: (a) a source providing step: providing an abandoned colored glass containing 60 to 80% by weight of cerium oxide (SiO ₂ ), The waste colored glass is pulverized into one glass powder having a particle diameter of 0.1 to 0.9 mm (mm) as a cerium source, and 1 to 20 gram of glass powder is dissolved in a sodium hydroxide solution to form a lanthanum source solution; (b The templating agent preparation step: taking cetyltrimethylammonium bromide (CTMABr) dissolved in ammonium hydroxide (NH ₄ OH) to prepare a CTMABr:NH ₄ OH molar ratio of 0.25:1.5 to 0.3:3.13 a templating agent; (c) a pH adjustment step: adding the lanthanum solution dropwise to the templating agent and adjusting the pH of the mixed solution to 9 to 12, and stirring to form a mixture; (d) filtering Drying step: filtering the mixture to obtain an intermediate product, washing the intermediate product and drying the intermediate product at a temperature of 100 ± 5 ° C; (e) calcining step: placing the intermediate product in a high temperature furnace, and The intermediate product is calcined at a temperature of 450 to 600 ° C for 4 to 6 hours to remove the template on the intermediate product. The agent is used to prepare a hole material in the silicate which is prepared by discarding colored glass. The method for preparing a void material in a waste colored glass recycling preparation according to the first aspect of the invention, wherein the source of the ruthenium source is the solution of the glass powder and the sodium hydroxide solution at 150±5° C. It is prepared by stirring at a temperature of 10 to 24 hours. The method for preparing a void material in a waste colored glass recycling preparation according to the first aspect of the invention, wherein the cerium source solution is a mixture of the glass powder and the sodium hydroxide solution, and is passed through a magnet stirrer at 600 rpm. The stirring speed was continuously stirred for 24 hours. The method for preparing a void material in a waste colored glass recycling preparation according to the first aspect of the patent application, wherein the template agent in the template addition step is 2.5 g of cetyltrimethylammonium bromide (CTMABr) was dissolved in 125 ml of deionized water, and further added with 10 ml of ammonium hydroxide (NH ₄ OH), and stirred until the cetyltrimethylammonium bromide (CTMABr) was completely dissolved. The method for preparing a void material in a waste colored glass recycling preparation according to the first aspect of the patent application, wherein the pH adjustment step is performed by adding a sulfuric acid (H ₂ SO ₄ ) having a concentration of 4N to adjust the pH value. The mixture was further stirred at room temperature for 6 to 8 hours with a magnetic stirrer to prepare the mixture. The method for preparing a void material in a waste colored glass recovery preparation according to the first aspect of the patent application, wherein the calcining step is preferably calcined at a temperature of 550 ° C for 6 hours. A hole material in a citrate prepared by recycling waste colored glass, which is produced by the manufacturing method described in any one of claims 1 to 6, and the medium-pore material has a specific surface area of 900 to 1300 square Metric/gram (m ² /g), the average pore volume is 0.7 to 1.0 cubic centimeters per gram (cm ³ /g). The void material in the tantalate prepared by recycling the waste colored glass according to the seventh aspect of the patent application, wherein the medium hole material is subjected to an X-ray diffraction test, and the angle of 2 θ of the 100 crystal plane is 2.50 ° The 2 θ angle of the 110 crystal plane is 4.33°, and the mesoporous material has a d-spacing of 3.53 and 2.04 nanometers (nm), and a lattice parameter (a0) of 4.08 nm (nm). A void material in a phthalate prepared by recycling waste colored glass as described in claim 7 of the patent application, which is used for adsorbing volatile organic compounds. A void material in a citrate prepared by recycling waste colored glass as described in claim 7 of the patent application, which is used for adsorbing toluene.