TW508276B - Fast synthesis of zeolites from ash wastes - Google Patents

Abstract

The present invention relates to a method for fast synthesis of zeolites from ash wastes by a microwave induction. The method uses ash wastes, particularly ash of rice husks, as a silicon source, together with a frame material, to synthesize a zeolite with a high crystallinity in a high efficiency microwave-induced high pressure reactor at 100-250 DEG C for 30-120 minutes. The present invention can not only recycle ash wastes, but also produces a high economic value zeolite having a medium pore size (1.6-10 nm) and a micro pore size (0.3-0.8 nm) in a short time. The present invention provides a method and apparatus for recycling ash wastes.

Description

508276 V. Description of the invention π) The present invention relates to a method for synthesizing zeolite by gasification of ash slag with microwave-induced ash waste, especially rice husk ash and other biomass wastes containing high-purity silicon sources, especially in a very short time. Within (30 ~ 120 minutes), it can synthesize high crystallinity mesopore size (1.66 ~ 10nm) and micropore size (0 · 3 ~ 0 · 8 ηιη) zeolite, organic biomass waste gas. The volume can be greatly reduced by chemical treatment. The generated synthetic gas can be recycled and used for power generation or synthetic chemicals. The residual ash can be microwave-induced to synthesize high-value mesopore and micropore zeolites.

According to Taiwanese rice husk, the average annual waste volume is about 400,000 tons, which is usually classified as biomass waste (b i 0 m a s s w a, s t e s). Rice husks are light and bulky, which makes cleaning difficult. If they are directly burned in the open air, they are likely to cause air pollution. If the compost is converted into resources, it may be caused by poor timeliness and odor escaping, which will increase the operating cost. As the organic biomass is formed by photosynthesis of plants, the combustion application is a benign C02 cycle, and the remaining ash is used as the silicon source for synthetic zeolite (rice hull ash contains high purity Si02 (> 9 3%)). ) To achieve the goal of complete recycling.

Zeolite is an aluminum silicate compound containing alkali metals or alkaline earths. The basic unit is a tetrahedron composed of chopped or aluminum as the center and oxygen. It has a uniform pore structure with a minimum pore diameter of about 0.3 nm. ). The structure of zeolite includes three-dimensional spatial structure Si 04 and A 1 04 tetrahedron. The center of each tetrahedron contains a Shi Xi or Shao atom, and the oxygen atom is formed by adjacent tetrahedrons in various proportions and various types. Way to arrange. Industrial applications of zeolites include: heterogeneous catalysts, cation exchange (c a t i ο n e X c h a n g e

Page 4 508276 V. Description of the invention (2) c a p a c i t y) and molecular sieve shape selection ′ use the crystal structure of the phosphite catalyst to control the generation of products (shape selectivity). In addition, zeolite can change the pore structure and the properties of active groups (a c t i v e s i t e s) through water absorption, dehydration and ion exchange, and enhance the selectivity of molecular engineering (in〇1 e c u 1 a r e n g i n e r i n g). The traditional zeolite is synthesized by hydrothermal method, but it takes more than 48 hours. The invention uses microwave to induce the reaction to instantly and uniformly heat, shortening the crystallization time of the zeolite and making the crystals more uniform and fast. Microwave is a kind of non-ionic radiation electromagnetic energy, which can cause the migration of ions and the rotation of the dipole moment to make the molecules move. The frequency of the microwave energy is about 3 0 to 3 0 0, 0 0 Μ Ιί z 之In the meantime, the molecule can generate a rapid heating effect of 109 back-and-forth and oscillating shaking movements within 1 second. After the microwave is irradiated, the temperature of the substance will rise due to the movement of the molecule. The reason is that the inventors have taken this into account, and with years of academic research and practical experience, the use of microwave to induce ash residue waste, especially rice husk gasification ash residue, to generate high-value zeolites in a very short time, has become Method and equipment for reusing ash waste resources.

508276 • V. Description of the invention (3) Recycling. Microwave-induced rice husk ash waste or other ash residue waste can be converted into high-value zeolite in a short time, becoming a method and equipment capable of reusing the ash waste f source. Another object of the present invention is to provide a method for microwave induction treatment of ash waste, especially rice husk ash, the main equipment includes: gasification reactor, aggregate tank, pH adjustment tank, microwave induction reactor, · Filters and high-temperature furnaces, no acidic waste water or exhaust gas is emitted in this chemical reaction procedure. Another aspect of the present invention is to provide a method for treating microwave-induced ash waste. In a very short reaction contact time of 30 to 12 (3 minutes microwave induction converts rice husk ash or other biomass waste ash to high-value meso or micro-pore zeolite, which becomes a resource recycling of ash waste Method and equipment for use. In order to make the technical means, inventive features used in the present invention, and the purpose and effect easy to understand, the drawings and figures are described in detail below: [Illustration of the drawings] The first picture of the present invention The schematic diagram of the equipment; the second diagram of the program flow of the present invention; the third diagram of the XRD low-angle spectrum of synthetic zeolite; the fourth diagram of the microwave induced synthetic zeolite adsorption and desorption of isothermal nitrogen; XRD spectrum of synthetic pore size zeolite of ash and slag. [Refer to the drawing number] (1) Biomass waste collection tank, (2) Ash and waste collection tank, (3)

508276 V. Description of the invention (4) flow gasifier, (4) ash waste spiral conveyor, (5) adjustment tank, (6) microwave induction reactor, (7) filter, (8) dryer (9) Zeolite storage tank, (1 0) structure material storage tank. First, please refer to the first and second figures together. The implementation steps of the treatment method of the present invention are as follows: 1. Biomass waste gasification: Biomass waste, especially rice husk, is placed in a downflow gasification reactor ( 3), the organic biomass is gasified at 600 ~ 900 ° C, the produced synthetic gas can be used for power generation or synthetic chemicals, and the residual ash can be used to synthesize the Buddha of South Value. 2. Mix ash and waste with the structure solution: mix the ash and the structure solution sent from the structure substance storage tank (1 0) in the adjustment tank (4) for uniform mixing. 3. Pll value adjustment: Use the II2 S04 solution to control the pH value of the adjustment tank (5), and stir it evenly. 4. Microwave-induced zeolite synthesis: the ash / structure solution is introduced into the microwave induction reactor (6) from the adjustment tank (4), at a temperature of 100 to 250 ° C, a reaction time of 30 to 120 minutes, and pressure 0 ~ 20 atm. Microwave-induced rapid synthesis of zeolite. 5. Product treatment (recovery and reuse of zeolite and architectural solution): microwave induction

508276 V. Description of the invention (5) The zeolite solids and framework solution produced by the reaction are introduced into a filter (7), and the separated zeolite solids are dried in a dryer (8). Store in zeolite storage tank (9). The recovered framework solution can be sent to the adjustment tank (5) and mixed with ash and slag to be recycled.

In the present invention, by using a microwave-induced reaction to make ash and slag in a very short contact time (30 to 120 minutes), a large amount of high-value zeolite can be generated with high efficiency and high selectivity, and the zeolite and structural solution in the product The structure solution that can be separated and recovered and recycled can be recycled and reused, which will not cause secondary pollution problems and reduce the quality of zeolite products. Synthetic zeolites are widely used. For example, ion exchange, gas separation, adsorbent, catalyst and desiccant, etc. In addition, the gasification of biomass waste can greatly reduce its volume or weight; the synthesis gas generated can be recycled and used for power generation or chemical production to achieve The goal of recycling and reuse of high quality waste. As can be seen from the above description, the present invention does have the following advantages:

1.Using the microwave induction method, ash and slag can be converted into high-value zeolite in a short time, which has become an important method and equipment for recycling resources. It helps to reduce the volume or weight of the waste for subsequent reuse. In addition, because the reaction time is extremely short, the relative reactor size can be greatly reduced, and the space occupied by it is relatively small. In addition, compared with the traditional hydrothermal synthesis method, the time and energy consumption can also be greatly reduced.

Page 8 508276 V. Description of the invention (6) 2. Because the microwave-induced reaction is performed in a completely closed high-pressure aqueous solution, and the structural solution can be reused to avoid problems of wastewater treatment or other secondary pollution. 3. The recovered zeolite is a high-value product and can be widely used in ion exchange, gas separation, adsorbents, catalysts and desiccants. 4. Biomass waste is gasified in a stream gasification reactor with a simple design and procedure. Syngas (C0 and 112) can be generated and reused for power generation or manufacturing chemistry. Example 1 of the invention: Microwave-induced rice husk Mid-pore size zeolite for ash and residue mixing rice husk ash, silicate solution (14% NaOII, 27% S 1 02) and cationic surfactant (hexadecyltrimethylammonium) in an appropriate ratio For example, take 9.6 g of a tetrapolar ammonium salt solution (TMA0II) and 2 3.4 g of cetyltrimethylammonium (CTMABr), dissolve in deionized water and stir until clear; and add 4.7 g of rice hull ash , Stir and mix for 2 ~ 3 hours. Then use 0.2 M II2S04 to adjust the pH value between 10. 5 ~ 11.0, and finally stir for 20 ~ 30 minutes ° to induce rapid synthesis of zeolite by microwave (reaction 30 ~ 60 minutes). The first synthesized zeolite was washed and filtered in two stages of water, dried at 70 ° C for 16 hours, and finally calcined at 5 40 ° C for 10 hours. The third figure shows the traditional hydrothermal (reaction at 150 ° C, 48 hours) with microwave induction

508276 V. Description of the invention (7) The XRD low-angle spectrum of the synthetic zeolite (at 150 ° C, 30 minutes of reaction), and the low-angle spectrum of XRI has four main characteristic diffraction surfaces (() 〇〇 ), (Η 〇), (2 0 0), (2 1 0)). The fourth figure shows the isothermal nitrogen adsorption and the attachment of microwave-induced synthetic zeolite (η 11 r 〇gena cl sorpti ο-cl esorpti ο η isotherms). The analysis results of surface area, pore size, and thickness are also listed in the first table. ◦Hydrothermal method and microwave method can synthesize zeolite with high crystal size. However, the microwave-induced ash waste in the present invention can generate high-selectivity, high-yield, high-value zeolites within 30 minutes, which is more advantageous than the traditional hydrothermal method which takes at least 2 days. Example of the present invention Microwave-induced rice husk ash> Synthetic micro-apertures> The fifth figure of ephedrine shows the use of microwave-induced rice in an aqueous solution of hexamethylene diamine (1,6-diami η 〇-he X ane) Shell ash synthetic zeolite 'can produce spatial micropore zeolite with a degree of crystallinity exceeding 99% at a reaction temperature of 160 ° C and a reaction time of 60 minutes. In summary, the embodiments of the present invention can indeed achieve the expected effects, and the specific structure shown is not only not seen in similar products, nor has it been disclosed before the application. It has fully met the requirements and requirements of the Patent Law. I filed an application for an invention patent in accordance with the law, and I urge you to examine it and grant the patent.

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P.io 508276 Schematic description of the first table Synthesis method Lattice constant (a () (A)) d Pitch (di (m (A)) pore diameter (eight) Wall thickness (A )) Surface area (m2 / g) Microwave induced 47.18 40.86 33.47 13.71 1073.4 Hydrothermal 1 53.08 45.97 32.09 20.99 841.4, 'Table 2 Synthesis method Second source architecture substance reaction temperature (° C) reaction time (min) pore size Structural crystallinity microwave-induced ash hexamethylene diamine (C6DN) 160 60 3D / 5-6 A 99+

Claims (1)

508276 7. Application scope of patent 1. A method for rapidly synthesizing zeolite by using microwave-induced slag, which is characterized by placing biomass waste, especially rice husk, in a downflow gasification reactor at 60 to 9 0 0 ° C, the synthesis gas (C0 and 112) can be used for power generation or chemical synthesis, and the residual ash can be used to synthesize high-value zeolite. It has become a method of gasifying organic waste for power generation or synthetic chemicals, and using the remaining ash to synthesize high-value zeolite. 2. A method for rapidly and rapidly synthesizing zeolite by microwave induction as described in the first item of the scope of patent application, wherein the above ash residue is rapidly induced by microwave (reaction temperature 100 ~ 250 ° C, reaction time 3) 0 ~ 120 minutes) under the reaction, high crystalline mesoporous or microporous zeolite is synthesized, and the zeolite and structure solution in the product can be separated and recovered; the recovered structure solution can be recycled and reused without causing environmental pollution and reducing zeolite product quality. Lu 3. A method for rapidly synthesizing zeolite using microwave-induced slag as described in the first item of the scope of patent application, wherein the synthetic zeolite is widely used. For example, ion exchange, gas separation, adsorbents, catalysts and desiccants, etc .; microwave-induced slag waste to synthesize zeolite is completely free of secondary pollution, and has the function of waste reduction and reuse. 4. A method for rapidly synthesizing zeolite using microwave-induced ash as described in the first item of the scope of the patent application, wherein rice husk ash, silicate solution and cationic surfactant (hexadecyltrimethyl 4 'in an appropriate ratio, such as taking 9.6 g of a tetrapolar ammonium salt solution (TMAOII) and 23. 4 If 111 Page 16 508276 6. Scope of patent application g Cetyltrimethylammonium (CTMABr), dissolve in deionized water and stir until clarified; add 4.7 g of rice husk ash residue, stir and mix for 2 ~ 3 hours. Then adjust the pH between 0 · 5 ~ 1 1 · 0 with 0 · 2 M II2 SO / j, and stir for another 20 ~ 30 minutes. Microwave-induced rapid synthesis of zeolite (reaction 30 ~ 6 (1 minute). The first synthesized zeolite was washed and filtered in two stages of water, dried at 70 ° C for 16 hours, and finally calcined at 540 ° C for 10 hours. Can synthesize zeolite with high crystal size and medium pore size. However, using microwave-induced slag waste within 30 minutes can generate high selectivity, high yield and high value zeolite, which is more advantageous than the traditional hydrothermal method which takes at least 2 days. . 5. A method for rapidly synthesizing zeolite using microwave-induced slag as described in the first item of the scope of the patent application, wherein the structural substance (hexamethylene diamine (1,6-d 1 a in 1 η-he X ane)) The zeolite was synthesized from rice husk ash by microwave induction in the aqueous solution. At a reaction temperature of 160 ° C and a reaction time of 60 minutes, a micropore zeolite with a crystallinity of more than 99% can be formed. 6. —A kind of equipment for rapidly synthesizing zeolite using microwave-induced slag, including Including · Yinan efficiency microwave-induced south pressure reactor 'is composed of the body and the pressure equipment. It sends ash waste and structural substances into the reactor, and the reaction temperature is 100 ~ 250 ° C. Time 30 ~ 120 minutes, high-crystallinity mesopore or micropore zeolite is synthesized. Page 17