TWI746307B - Continuous fluidized bed hydrothermal reaction device and method for continuous hydrothermal synthesis of porous materials - Google Patents

Abstract

Provided is a continuous fluidized bed hydrothermal reaction device, which includes: a reaction tank, which includes: a vertical cylindrical tank body; and an inverted cone-shaped bottom; a feeding port; a discharge port; a heating element; solid-liquid separation Unit; Circulation pipeline; Two-way circulation pump, which is arranged on the circulation pipeline, and is used to perform at least one of the following: make the hydrolysis reaction raw material or hydrothermal reaction guided from the top of the reaction tank The raw material is injected into the bottom of the reaction tank through the circulation line; or the liquid of the hydrolysis reaction product or the liquid of the hydrothermal reaction product separated by the solid-liquid separation unit is injected into the reaction through the circulation line The top of the groove. The continuous fluidized bed hydrothermal reaction device of the present invention achieves the effect of the fluidized bed through the design of the reaction tank, and can make full use of various resources in the hydrothermal synthesis process through the two-way circulation pump and the circulation pipeline. In order to save energy and resource consumption, reduce operating costs, and achieve the effect of continuous production and scale-up of production.

Description

Continuous fluidized bed hydrothermal reaction device and continuous hydrothermal method for synthesizing porous materials

The present invention relates to a continuous fluidized bed hydrothermal reaction device and a continuous hydrothermal synthesis method for porous materials using the continuous fluidized bed hydrothermal reaction device.

According to statistics from the Environmental Protection Agency, the amount of silicon-containing inorganic waste generated in my country is as high as tens of millions of metric tons each year, including incineration bottom slag and fly ash, waste glass, panel glass, dust collection ash, boiler ash, steelmaking slag, furnace Stone, brick ceramics, inorganic sludge, stone waste, etc., and as the treatment method of the aforementioned silicon-containing inorganic waste, it is generally solidified/stabilized and then stacked/buried in a landfill. However, due to the insufficient capacity of domestic landfills, it cannot be a long-term feasible treatment method.

In addition, since many silicon-containing inorganic wastes are rich in metal oxides such as silicon, aluminum, and calcium, and have the potential to synthesize porous materials such as zeolite, as an alternative to the aforementioned stacking/burial treatment, it has been proposed to discard silicon-containing inorganic wastes. The substance undergoes a hydrothermal reaction to synthesize zeolite.

As for the reaction equipment that hydrothermally reacts silicon-containing inorganic waste to synthesize zeolite, a small hydrothermal reactor with a cap is generally used.

However, since the aforementioned hydrothermal reactors with caps and seals belong to batch-type reaction equipment, and are usually small-scale reaction devices with limited capacity, the space for scale-up mass production and application development is limited. In addition, because batch-type reaction equipment can only be produced in batches, and cannot be produced continuously, it cannot meet the requirements of industrialization.

In addition, in the conventional method of hydrothermally reacting silicon-containing inorganic waste to synthesize zeolite, usually only a stirrer is used for stirring, and no fluidization phenomenon occurs in the reactor, so the reactants in the hydrothermal reaction There is still room for further improvement of the mixing effect.

In addition, in the process of batch production, when a batch of production is completed, it is usually necessary to remove the remaining substances in the reactor before the next batch of production can be carried out. However, if the remaining substances in the reactor are removed, the remaining substances cannot be effectively reused.

In order to solve the above-mentioned problems, a continuous fluidized bed hydrothermal reaction device according to one aspect of the present invention includes: The reaction tank includes: a vertical cylindrical tank body; and an inverted conical bottom; Feeding port, which is used to feed hydrolysis reaction raw materials or hydrothermal reaction raw materials, and it is arranged above the reaction tank and communicates with the top of the reaction tank; The discharge port is used to discharge the hydrolysis reaction product or the hydrothermal reaction product, and it is connected to the bottom of the reaction tank; Heating element, which is used to heat the reaction tank; A solid-liquid separation unit, which is used for solid-liquid separation of the hydrolysis reaction product or the hydrothermal reaction product, and is arranged below the discharge port and communicates with the discharge port; A circulation pipeline, which is in communication with the top of the reaction tank, the bottom of one side of the solid-liquid separation unit, and the discharge port; A two-way circulation pump is arranged on the circulation pipeline and is used to perform at least one of the following: make the hydrolysis reaction raw materials or hydrothermal reaction raw materials guided from the top of the reaction tank pass through the circulation pipeline It is injected into the bottom of the reaction tank; or the liquid of the hydrolysis reaction product or the liquid of the hydrothermal reaction product separated by the solid-liquid separation unit is injected into the top of the reaction tank through the circulation line.

In one embodiment, the circulation pipeline includes: a first circulation pipeline, which is arranged on one side of the reaction tank and communicates with the top of the reaction tank and the discharge port; a second circulation pipeline, which is connected to the solid The bottom of one side of the liquid separation unit communicates with the first circulation pipeline.

In one embodiment, the solid-liquid separation unit includes: a coarse filter plate with a pore size of 100 μm; and a fine filter plate with a pore size of 20 μm.

In one embodiment, the continuous fluidized bed hydrothermal reaction device further includes: a dispersing plate, which is arranged at the bottom of the reaction tank.

In one embodiment, the continuous fluidized bed hydrothermal reaction device further includes: a stirrer, which is arranged in the tank.

In one embodiment, the continuous fluidized bed hydrothermal reaction device further includes: at least any one of the group consisting of a thermocouple, a pressure gauge, and a level gauge, and the aforementioned thermocouple, pressure gauge, and level gauge It is installed in the reaction tank and used to detect the temperature, pressure and liquid level in the reaction tank.

In one embodiment, the continuous fluidized bed hydrothermal reaction device further includes: an automatic control panel, which is electrically connected with the aforementioned thermocouple, pressure gauge, and level gauge, and is electrically connected to the aforementioned thermocouple, pressure gauge, and liquid level gauge. Liquid level gauge, to monitor and automatically control the temperature, pressure and liquid level in the reaction tank.

In order to solve the above-mentioned problems, the method of continuous hydrothermal synthesis of porous materials according to one aspect of the present invention includes: (a) providing a silicon-containing inorganic waste; (b) adjusting the silicon-aluminum of the aforementioned silicon-containing inorganic waste (C) Add an alkali agent to the raw materials for the alkali fusion reaction, and carry out the alkali fusion reaction to obtain the raw materials for the hydrolysis reaction; (d) add pure water (the most appropriate ratio) to the raw materials for the hydrolysis reaction (Best liquid-solid ratio) and carry out the hydrolysis reaction, and use at least a part of the hydrothermal reaction product as the hydrothermal reaction raw material; (e) add a template to the aforementioned hydrothermal reaction raw material and adjust the pH value to perform the hydrothermal reaction, and obtain a Hydrothermal reaction product; (f) subjecting the aforementioned hydrothermal reaction product to solid-liquid separation to obtain the aforementioned hydrothermal reaction product liquid and porous material precursor solid, and recycling the aforementioned hydrothermal reaction product liquid as a hydrolysis reaction Raw materials; (g) drying and calcining the foregoing porous material precursor solid to obtain a porous material; wherein the foregoing (d) ~ (f) steps are in the continuous fluidized bed hydrothermal reaction of the present invention In-device.

In one embodiment, in step (b), the silicon-to-aluminum ratio (the molar ratio of silicon/aluminum) of the aforementioned silicon-containing inorganic waste is adjusted to 10-40.

Moreover, in one embodiment, in step (c), the weight ratio of alkali agent/alkali melting reaction raw material (alkali dosage ratio) is 1.0 to 1.5.

Furthermore, in one embodiment, in step (d), the weight ratio (liquid-solid ratio) of pure water/hydrolysis reaction raw material is adjusted to 50-200, and the hydrolysis reaction product is subjected to solid-liquid separation, and the hydrolysis reaction product is subjected to solid-liquid separation. The liquid of the reaction product is used as the raw material for the hydrothermal reaction.

In one embodiment, in step (e), the template is cetyltrimethylammonium bromide (CTAB), and the amount of the template used is 0.5 to 1.5% by weight of the raw material for the hydrothermal reaction. , And the pH of the hydrothermal reaction precursor liquid is 8-12, the hydrothermal reaction temperature is 105-150°C, and the hydrothermal reaction time is 8-16 hours.

Furthermore, in one embodiment, in step (a), the aforementioned silicon-containing inorganic waste is selected from the group consisting of incineration bottom slag, fly ash, waste glass, panel glass, dust collection ash, boiler ash, steelmaking slag , At least any one of the group consisting of hearthstone, brick ceramics, inorganic sludge and stone waste.

One aspect of the present invention is accomplished in view of the above-mentioned conventional problems, and its purpose is to provide a continuous fluidized bed hydrothermal reaction device, which achieves the effect of the fluidized bed through the design of the reaction tank , And can make full use of various resources in the hydrothermal synthesis process (such as solution after hydrolysis reaction, solution after hydrothermal reaction, template agent, silicon-containing inorganic waste (silicon source), etc.) by means of two-way circulation pump and circulation pipeline. , In order to save energy and resource consumption, reduce operating costs, and achieve the effect of continuous production and scale-up of production.

One aspect of the present invention is to provide a continuous hydrothermal method for synthesizing porous materials, which can achieve continuous hydrothermal reaction by carrying out the hydrolysis reaction and the hydrothermal reaction in the continuous fluidized bed hydrothermal reaction device of the present invention. The effect of type production and scale-up of production scale.

＜Continuous fluidized bed hydrothermal reactor＞ First, please refer to FIG. 1, which is a schematic diagram of a continuous fluidized bed hydrothermal reaction device according to an embodiment of the present invention. As shown in Figure 1, the present invention provides a continuous fluidized bed hydrothermal reaction device 100, which includes: a reaction tank 1, a feeding port 2, a discharge port 3, a heating element 4, a solid-liquid separation unit 5, and a two-way circulation Pump 6, circulation line (in this embodiment, it is the first circulation line L1 and the second circulation line L2).

Wherein, the reaction tank 1 includes: a vertical cylindrical tank body 11; and an inverted conical bottom 12. By making the reaction tank 1 into the above-mentioned shape, it can be advantageous to produce a fluidized bed effect. In addition, the volume of the reaction tank 1 can be designed according to the actual industrial demand for mass production, for example, it can be 50 liters, 100 liters, 150 liters, 200 liters, etc., and it is not limited thereto.

In addition, the feed port 2 is used to feed hydrolysis reaction raw materials or hydrothermal reaction raw materials, and it is installed above the reaction tank 1 and communicates with the top of the reaction tank 1. The feeding port 2 can be tubular to facilitate the feeding of raw materials. The raw material for the hydrolysis reaction may be, for example, the raw material that has undergone steps (a) to (c) described later. More specifically, the raw material for the hydrolysis reaction may be such that the silicon-to-aluminum ratio is adjusted to the silicon-containing inorganic waste. Obtained after alkali fusion reaction. In addition, for the hydrothermal reaction raw material, for example, at least a part of the hydrolysis reaction product (e.g., preferably a liquid of the hydrolysis reaction product) may be used as the reaction raw material, or the hydrolysis reaction product may be directly used as the reaction raw material.

Also, it should be noted that although the present invention preferably uses the aforementioned two-way circulation pump 6 and circulation lines (for example, the first circulation line L1 and the second circulation line L2) to remove a part of the hydrolysis reaction product (for example, the hydrolysis product Liquid) is used as a hydrothermal reaction raw material, and the hydrothermal reaction raw material is injected into the top inlet of the reaction tank 1 (detailed later) through the second circulation line L2 and the first circulation line L1, but it can also be A part of the hydrolysis reaction product is guided to the feed port 2 to charge the hydrolysis reaction raw material. In addition, when the hydrothermal reaction raw materials are introduced, the same as when the hydrolysis reaction raw materials are introduced, it is also possible to select from the inlet of the top of the reaction tank 1 (the on-off valve a1 in FIG. 1) or the injection port 2. In addition, the circulation line of the present invention only needs to communicate with the top of the reaction tank 1, the bottom of one side of the solid-liquid separation unit 5, and the discharge port 3. It is not limited to the first circulation line L1 and the second circulation line L2.的组合。 The combination.

Then, the discharge port 3 is used to discharge the hydrolysis reaction product or the hydrothermal reaction product after the hydrolysis reaction or the hydrothermal reaction in the reaction tank 1, and the discharge port 3 is connected to the reaction tank 1 The conical bottom 12 communicates. An on-off valve a7 can be set between the discharge port 3 and the conical bottom 12, and it is used to control the flow rate and flow rate of the hydrolysis reaction product or hydrothermal reaction product in the reaction tank 1 to the discharge port 3 .

Next, the heating element 4 is used to heat the reaction tank 1 so that the reaction tank 1 becomes a temperature suitable for the hydrolysis reaction or the hydrothermal reaction. In addition, the heating element 4 is arranged around the reaction tank 1, and in order to achieve a uniform heating effect, a plurality of heating elements 4 may be arranged around the reaction tank 1. In addition, in terms of a preferred aspect of the heating element 4, as shown in FIG. 2 described later, it can be a heating coil and a heat preservation and heat insulation material covering the circumference of the tank 11, thereby having a good heat storage and heat preservation effect. Reduce heat loss.

Next, as shown in FIG. 1, the solid-liquid separation unit 5 is arranged below the discharge port 3 and communicates with the discharge port 3. The solid-liquid separation unit 5 is used for solid-liquid separation of the aforementioned hydrolysis reaction product or hydrothermal reaction product. In addition, an on-off valve a8 can be provided between the discharge port 3 and the solid-liquid separation unit 5, and it is used to control the hydrolysis reaction product or hydrothermal reaction product passing through the discharge port 3 to be guided to the solid-liquid separation unit 5 flow, velocity, etc. In addition, with regard to a preferred aspect of the solid-liquid separation unit 5, as shown in FIG. 2 described later, it may include: a coarse filter plate 51 with a filter mesh pore size of 100 µm; and a fine filter plate 52 with a filter mesh pore size of 20 µm .

Next, as shown in FIG. 1, the first circulation line L1 is arranged on one side of the reaction tank 1 and communicates with the top of the reaction tank 1 and the discharge port 3. An on-off valve a1 can be provided at the communication place between the first circulation line L1 and the top of the reaction tank 1 to control the flow rate, the flow rate, and the like. In addition, the first circulation line L1 is used to make the substances involved in the hydrolysis reaction/hydrothermal reaction flow in the pipeline, and can change the substances involved in the hydrolysis reaction/hydrothermal reaction based on the control of the two-way circulation pump 6 The flow direction in the first circulation line L1. An on-off valve a6 can be set between the first circulation line L1 and the discharge port 3 to control the flow of substances (such as hydrolysis reaction products) involved in the hydrolysis reaction/hydrothermal reaction from the discharge port 3 toward the first circulation line L1 Flow, velocity, etc.

In addition, as shown in FIG. 1, the second circulation line L2 is connected to the bottom of one side of the solid-liquid separation unit 5 and communicates with the first circulation line L1. The first circulation line L2 is used to make the hydrolysis reaction product or hydrothermal reaction product after solid-liquid separation flow in its pipeline, and to introduce the aforementioned hydrolysis reaction product or hydrothermal reaction product into the first circulation line L1 , And then introduced to the top of the reaction tank 1 (on-off valve a1) via the first circulation line L1. An on-off valve a5 can be provided between the solid-liquid separation unit 5 and the second circulation line L2 for control, and an on-off valve a4 can also be provided between the second circulation line L2 and the first circulation line L1 for control.

In addition, as shown in FIG. 1, the continuous fluidized bed hydrothermal reaction device of the present invention further includes: a two-way circulation pump 6, which is arranged on the circulation pipeline and is used to perform at least one of the following: The hydrolysis reaction raw material or hydrothermal reaction raw material guided from the top of the reaction tank 1 is injected into the bottom 12 of the reaction tank 1 through the first circulation line L1; or it is passed through the solid-liquid separation unit 5 The separated liquid of the hydrolysis reaction product or the liquid of the hydrothermal reaction product is injected into the top of the reaction tank 1 (at the on-off valve a1) through the second circulation line L2 and the first circulation line L1. In addition, on-off valves a2 and a3 can be respectively provided upstream and downstream of the bidirectional circulation pump 6 for control. Thereby, by continuously guiding (drawing) the liquid in the reaction tank 1 from the top of the reaction tank 1 and injecting it from the bottom 12 of the reaction tank 1, the fluid in the reaction tank 1 is combined with the hydrolysis reaction raw material or hydrothermal The reaction raw materials produce fluidization phenomenon, achieve the purpose of uniform mixing, can promote the effect of hydrolysis reaction and hydrothermal reaction, and can flow and circulate continuously, so as to achieve the function of a continuous fluidized bed hydrothermal reaction device.

Next, please refer to FIG. 2, which is a schematic diagram of a continuous fluidized bed hydrothermal reaction device according to another embodiment of the present invention. As shown in FIG. 2, similar to FIG. 1, the continuous fluidized bed hydrothermal reaction device 100' of another embodiment of the present invention also includes: a reaction tank 1, a feeding port 2, a discharge port 3, a heating element 4, The solid-liquid separation unit 5, the bidirectional circulation pump 6, the first circulation line L1, the second circulation line L2, and on-off valves a1 to a8 and other components. Therefore, in FIG. 2, the same elements as those in FIG. 1 are assigned the same reference numerals, and the description thereof is omitted.

Among them, as mentioned above, FIG. 2 shows a preferable aspect of the heating element 4 and the solid-liquid separation unit 5. For example, the heating element 4 may be a heating coil and a heat preservation and heat insulation material covering the circumference of the vertical cylindrical tank 11, thereby having a good heat storage and heat preservation effect and reducing heat loss. In addition, in order to reduce the heat loss at the discharge port 3, the first circulation line L1 and the second circulation line L2, etc., the heating element 4 can also be used for the discharge port 3, the first circulation line L1 and the second circulation line L2. Heating is carried out in other places, and preferably, the heating element 4 can be a heating coil and a thermal insulation material covering the discharge port 3, the first circulation pipeline L1 and the periphery of the second circulation pipeline L2. In addition, the solid-liquid separation unit 5 may preferably be composed of a stainless steel filter mesh, and the pore size of the filter mesh is 100 µm (the coarse filter plate 51 on the upper layer) and 20 µm (the fine filter plate 52 on the lower layer) respectively. In this way, through the combination of coarse/fine filter plates, a better screening effect can be achieved, so that the solid components separated from the hydrothermal reaction product can be subjected to the calcining step described later. In addition, the above-mentioned filter screen aperture is only a preferred aspect of the present invention, which can be adjusted and changed appropriately to separate the screen according to requirements, and by designing an adjustable multi-layer separation device, it is more flexible in operation.

In addition, in FIG. 2, a stirrer 8 can also be provided in the tank 11 to increase the mixing effect of various reaction raw materials. The agitator 8 can perform agitation as needed, and its rotation speed can be designed to be between 0-100 rpm. In addition, in FIG. 2, a dispersion plate (not shown) can also be provided on the bottom 12 of the reaction tank 1. The dispersing plate can be set according to requirements, and with the dispersing plate, an upward fluid force can be generated, so that the fluid in the tank 11 and various reaction materials can be fluidized, so as to achieve the purpose of uniform mixing and continuous stirring.

In addition, in FIG. 2, a pressure gauge 7, a thermocouple thermometer 9, a pressure relief valve 10, a liquid level gauge (not shown), etc. can also be provided in the reaction tank 1 (for example, on the top of the reaction tank 1) as required. By installing the above-mentioned pressure gauge 7, thermocouple (thermocouple thermometer) 9 and liquid level gauge, etc., the pressure, temperature, liquid level, etc. during the reaction can be monitored. In addition, the pressure relief valve 10 can ensure that there is no danger due to excessive pressure during the reaction. In addition, an automatic control panel 20 can also be provided. The automatic control panel 20 is electrically connected to the aforementioned thermocouple 9, pressure gauge 7, and liquid level gauge. Monitor and automatically control the temperature, pressure and liquid level in the reaction tank to ensure that the system operation and control operation can meet the requirements of accuracy, stability and safety.

In addition, an on-off valve a9 can be provided in the charging port 2 to control the flow rate, flow rate, etc. of various raw materials when the raw materials are fed.

The above has been described for the examples and variations of the continuous fluidized bed hydrothermal reaction device of the present invention, and the foregoing examples and variations are only illustrative descriptions, and are not intended to limit the scope of the present invention. Other aspects where the examples and variations are equivalent are also included in the scope of the present invention. The method for continuously hydrothermally synthesizing porous materials of the present invention will be described below.

＜Method of continuous hydrothermal synthesis of porous materials＞ The basic principle of the continuous hydrothermal synthesis method for porous materials of the present invention is to use an alkali melting step to dissociate and dissolve silicon oxide and aluminum oxide in silicon-containing inorganic waste, and then use hydrolysis and hydrothermal reaction to remove silicon oxide. It is rearranged and combined with aluminum oxide under appropriate control conditions and nucleated, polycondensed, and crystallized into inorganic porous materials such as synthetic zeolite, so that it has good specific surface area and pore distribution characteristics; in addition, due to the above-mentioned continuity of the present invention Hydrolysis and hydrothermal reaction are performed in a fluidized bed hydrothermal reaction device to continuously synthesize porous materials, thereby completing the method of the present invention for continuous hydrothermal synthesis of porous materials.

First, please refer to FIG. 3, which is a flowchart of a method for continuous hydrothermal synthesis of porous materials according to an embodiment of the present invention. As shown in FIG. 3, the method for continuous hydrothermal synthesis of porous materials according to an embodiment of the present invention includes steps (a) to (g). The following describes each step separately.

-(a) Step- The step (a) is to provide an inorganic waste containing silicon. In step (a), the aforementioned silicon-containing inorganic waste can be selected from: incineration bottom slag, fly ash, waste glass, panel glass, dust collection ash, boiler ash, steelmaking slag, hearth stone, brick ceramics , At least any one of the group consisting of inorganic sludge and stone waste. In addition, in step (a), conventional pulverization and sieving treatments can also be performed on the aforementioned silicon-containing inorganic waste to obtain the aforementioned silicon-containing inorganic waste with a uniform shape.

-(b)Step- The step (b) is to adjust the silicon-to-aluminum ratio of the aforementioned silicon-containing inorganic waste to obtain raw materials for alkali fusion reaction (alkali fusion reaction raw materials). The silicon-to-aluminum ratio (silicon/aluminum molar ratio) of the silicon-containing inorganic waste can be adjusted according to the desired porous material. In one embodiment, it is preferable to adjust the silicon-to-aluminum ratio of the aforementioned silicon-containing inorganic waste to 10-40, and it is more preferable to adjust the silicon-to-aluminum ratio to 20. Since the aforementioned silicon-containing inorganic waste also usually contains other metals such as aluminum, it is possible to adjust the silicon-to-aluminum ratio by recycling the silicon compound and aluminum compound in the aforementioned silicon-containing inorganic waste.

-(c) Step-(c) Step is to add an alkali agent to the raw material for the alkali fusion reaction and perform an alkali fusion reaction to obtain the raw material for the hydrolysis reaction. Regarding the alkali agent used in the step (c), for example, sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate (Na ₂ CO ₃ ), or a combination thereof can be used, and it is not limited thereto. In terms of the alkali dosage ratio (weight ratio of alkali agent/alkali melting reaction raw material), it is preferably 1.0~1.5%, more preferably 1.2%. Also, as for the reaction device used in step (c), a conventional high-temperature furnace can be used, and the reaction can be carried out at 200 to 800°C for 20 to 80 minutes, and preferably at 400 to 600°C. The reaction is carried out for 40 to 60 minutes, and more preferably, the reaction is carried out at 400°C for 60 minutes. Finally, the product after the alkali fusion reaction is used as the raw material for the hydrolysis reaction.

-(d)Step- The step (d) involves adding pure water to the raw material for the hydrolysis reaction and performing the hydrolysis reaction, and using at least a part of the hydrolysis reaction product as the hydrothermal reaction raw material. The step (d) is carried out in the continuous fluidized bed hydrothermal reaction device of the present invention, that is, for example, the hydrolysis reaction raw materials and pure water are fed into the reactor 1 from the aforementioned feed port 2 to be carried out. In step (d), the weight ratio (liquid-solid ratio) of pure water to the hydrolysis reaction raw material is preferably 50-200. The hydrolysis reaction system can be performed, for example, by reacting at 105°C for 40 minutes, and cooling down after the completion of the reaction.

In addition, all of the hydrolysis reaction product after the step (d) (hydrolysis reaction) can be directly used as the hydrothermal reaction raw material, or only a part of the hydrolysis reaction product after the hydrolysis reaction (for example, the liquid part of the hydrolysis reaction product) ) Is used as a hydrothermal reaction raw material (for example, a liquid for hydrothermal reaction). Specifically, after the hydrolysis reaction, the on-off valves a7 and a8 can be opened to allow the hydrolysis reaction product to enter the solid-liquid separation unit 5, and the solid-liquid separation unit 5 performs solid-liquid separation of the hydrolysis reaction product. After that, the flow direction is controlled by the bidirectional circulation pump 6 and the on-off valves a1~a5 are opened to separate the liquid of the hydrolysis reaction product after solid-liquid separation from the bottom of the solid-liquid separation unit 5 through the second circulation line L2 and the first circulation line L1 is injected into the top of the reaction tank 1. Compared with the case where the hydrolysis reaction product is directly used as the hydrothermal reaction material, when the liquid of the hydrolysis reaction product after solid-liquid separation is used as the hydrothermal reaction material, the undesirable is removed by solid-liquid separation. The solid impurities can increase the specific surface area of the final synthesized porous material.

-(e)Step- The step (e) involves adding a template agent to the aforementioned hydrothermal reaction raw materials and adjusting the pH value to perform a hydrothermal reaction and obtain a hydrothermal reaction product. Step (e) is carried out in the continuous fluidized bed hydrothermal reaction device of the present invention, that is, for example, the template agent is injected into the reactor 1 from the aforementioned feeding port 2 and combined with the aforementioned hydrothermal reaction raw materials (for example, refluxed The liquid of the hydrolysis reaction product or the hydrolysis reaction product itself) undergoes the reaction. As for the templating agent added in step (e), for example, cetyltrimethylammonium bromide (CTAB) can be used. Regarding the addition amount of the template agent, it is preferably 0.5 to 1.5% by weight of the aforementioned hydrothermal reaction raw material, and more preferably 1.2% by weight. Furthermore, in step (e), it is preferable to adjust the pH value of the hydrothermal reaction raw material to which the template agent is added to 8-12, and more preferably to adjust the pH to 10. Regarding the method of adjusting the pH value, for example, adding an acid or a base or the like. In a specific example, a 1M sulfuric acid solution is added to adjust the pH of the hydrothermal reaction raw material to which the template is added to about 10 to complete the hydrothermal reaction precursor.

Furthermore, in step (e), for the aforementioned hydrothermal reaction precursor, it is preferable to perform the hydrothermal synthesis reaction at a temperature of 80 to 200°C for 8 to 24 hours, and more preferably to perform a hydrothermal reaction at a temperature of 105 to 150°C. 8 ~16 hours. After the hydrothermal reaction in step (e), a hydrothermal reaction product is obtained.

-(f)Step- The step (f) is to separate the hydrothermal reaction product from solid-liquid to obtain the liquid of the hydrothermal reaction product and the precursor solid of the porous material, and use the liquid of the hydrothermal reaction product as the raw material for the hydrolysis reaction (e.g., hydrolysis reaction). Liquid used). Step (f) is carried out in the continuous fluidized bed hydrothermal reaction device of the present invention, that is, for example, the liquid of the hydrothermal reaction product after the solid-liquid separation of the solid-liquid separation unit 5 is removed from the solid-liquid separation unit 5 The bottom is injected into the top of the reaction tank 1 via the second circulation line L2 and the first circulation line L1. In addition, step (g) described later is performed on the porous material precursor solid obtained in step (f).

-(g) step- The step (g) is drying and calcining the precursor solid of the porous material to obtain the porous material. Furthermore, it is preferable to dry and calcinate the porous material precursor after solid washing. In step (g), the drying reaction conditions may be, for example, 100-120°C for 3-6 hours, and calcination may be 450-650 (preferably 550°C) for 3-6 hours.

In addition, the porous material may be, for example, synthetic zeolite. The porous material can also be further processed into products such as adsorbents, filter materials, catalyst carriers, etc., which are used in environmental protection, chemical industry, materials, photoelectric, incineration, construction and other related industries.

[Example] Hereinafter, each embodiment and comparative example of the present invention will be described. The present invention is not limited by these embodiments and comparative examples.

<Experimental examples 1-16: Preparation of laboratory-grade porous materials> Use a laboratory-grade 10-liter (10L) hydrothermal reactor (hot water reactor with a lid and seal) to perform steps (d) to (f). In addition, in addition to not performing the "liquid of the aforementioned hydrothermal reaction product as the raw material for the hydrolysis reaction" in step (f) and adjusting the hydrolysis time for 2 to 24 hours, in accordance with the above steps (a) to (g), in the experiment Porous materials are synthesized at the chamber level. The specific details of steps (a)~(g) are as follows. In addition, the experimental results are shown in Table 1 below. (a) Step: Use the incineration mixed ash (a mixture of boiler ash and fly ash, etc.) from a waste incineration plant in central Taiwan (Experimental Examples 1 to 16) as silicon-containing inorganic waste. The aforementioned silicon-containing inorganic waste is crushed and sieved. (b) Step: Adjust the silicon-to-aluminum ratio of the aforementioned silicon-containing inorganic waste to Table 1 below. (c) Step: Use 1.2% by weight of sodium hydroxide (NaOH) as an alkali agent. The alkali fusion reaction was carried out in a high-temperature furnace for 1 hour. The alkali dosage ratio and alkali melting temperature are shown in Table 1. (d) Step: The hydrolysis reaction temperature is 105°C, and the hydrolysis reaction time is fixed at 24 hours. After the hydrolysis reaction, solid-liquid separation is performed, and the liquid part is taken to step (e). The liquid-solid ratio is shown in Table 1. (e) Step: Add 1.2% by weight of cetyltrimethylammonium bromide (CTAB) as a template, and the hydrothermal reaction temperature is 105°C. The pH value of the hydrothermal reaction raw material added with the template agent is adjusted to 10 using sulfuric acid solution. The hydrothermal reaction time is shown in Table 1. (f) Step: Use a double-layer sieve (upper pore size is 100 µm; lower pore size is 20 µm) for solid-liquid separation of hydrothermal reaction products. Step (g): Wash the solids separated in step (f), dry them at 110°C for 4 hours, and calcinate at 550°C for 3 hours to obtain experimental grade porous materials.

[Table 1] Test example Silicon to aluminum ratio Alkali dose ratio Alkali melting temperature (℃) Liquid-solid ratio Hydrothermal time (hours) Zeolite specific surface area (m ² /g) 1 5 1 200 50 12 91.23 2 5 1.5 400 100 twenty four 246.23 3 5 2 600 150 36 327.06 4 5 2.5 800 200 48 550.05 5 10 1 400 150 48 783.64 6 10 1.5 200 200 36 639.37 7 10 2 800 50 twenty four 254.99 8 10 2.5 600 100 12 313.27 9 20 1 600 200 twenty four 875.94 10 20 1.5 800 150 12 962.08 11 20 2 200 100 48 768.28 12 20 2.5 400 50 36 619.86 13 40 1 800 100 36 735.96 14 40 1.5 600 50 48 762.39 15 40 2 400 200 12 717.78 16 40 2.5 200 150 twenty four 650.97

From the results in Table 1, we believe that when the alkali melting temperature (℃), liquid-solid ratio and hydrothermal time are within the range of Table 1, these parameters are all acceptable, and they are not the key to affecting the specific surface area of the zeolite. factor. In addition, it can be seen from the results of Table 1 that Test Examples 1 to 4 used silicon-containing inorganic wastes with a silicon-to-aluminum ratio of 5, and none of them could obtain a zeolite ^{with a specific surface area greater than 600 m 2 /g, which was not preferable.} In addition, in Test Examples 5 to 8, although the ratio of silicon to aluminum is 10, only the alkali dosage ratio of 1 to 1.5 can obtain ^{a zeolite with a specific surface area greater than 600 m 2} /g. Therefore, we believe that the alkali dosage is compared The best series is 1~1.5, and the silicon-to-aluminum ratio needs to be 10 or more.

Next, Test Examples 9-16 used silicon-containing inorganic wastes with a silicon-to-aluminum ratio of 20 and 40. The specific surface area of the synthesized zeolite was greater than 600 m ² /g, so it can be seen that the silicon-to-aluminum ratio is preferably 10-40 between. In addition, because in Test Example 10, ^{a zeolite with a specific surface area of 962.08 m 2} /g can be obtained, it can be seen that when incineration mixed ash is used, a silica-aluminum ratio of 20 and an alkali dosage ratio of 1.5 are the best systems. Preferences. And it can be known from Table 1 that the silicon-to-aluminum ratio and the alkali dosage ratio are the key factors affecting the specific surface area of the zeolite.

<Experimental Examples 17~32: Preparation of Laboratory Grade Porous Materials> Except for using waste glass as an alternative to incineration mixed ash, the preparation of the porous material was carried out in the same manner as in Test Examples 1 to 16 described above. The experimental parameters and results are shown in Table 2.

[Table 2] Test example Silicon to aluminum ratio Alkali dose ratio Alkali melting temperature (℃) Liquid-solid ratio Hydrothermal time (hours) Yield(%) Zeolite specific surface area (m ² /g) 17 1 0.6 200 50 12 13.66 257.70 18 1 1.2 400 100 twenty four 14.07 129.41 19 1 1.8 600 150 36 26.51 233.29 20 1 2.4 800 200 48 10.57 182.98 twenty one 5 0.6 600 100 36 13.32 750.73 twenty two 5 1.2 800 50 48 14.36 89.70 twenty three 5 1.8 200 200 12 19.23 344.32 twenty four 5 2.4 400 150 twenty four 28.61 237.43 25 10 0.6 800 150 48 11.24 1002.21 26 10 1.2 600 200 36 35.89 591.97 27 10 1.8 400 50 twenty four 43.95 319.89 28 10 2.4 200 100 12 30.65 408.07 29 20 0.6 400 200 twenty four 17.70 1068.41 30 20 1.2 200 150 12 44.82 935.45 31 20 1.8 800 100 48 50.75 846.40 32 20 2.4 600 50 36 56.40 7.23

Similar to the results in Table 1, from the results in Table 2, we believe that when the alkali melting temperature (℃), liquid-to-solid ratio and hydrothermal time are within the range of Table 2, these parameters are all acceptable. It is not a key factor affecting the specific surface area and yield of zeolite. In addition, when the silicon-to-aluminum ratio is 1 and 5 (Experimental Examples 17 to 24), zeolite with a ^{specific surface area greater than 600 m 2 /g cannot be synthesized, which is not preferable.} Therefore, in the case of using waste glass as the inorganic waste containing silicon, the preferable ratio of silicon to aluminum is 10-20.

Next, although both Test Example 25 (silica-aluminum ratio 10, alkali dosage ratio 0.6) and Test Example 29 (silica-aluminum ratio 20, alkali dosage ratio 0.6) can obtain ^{zeolite with a specific surface area greater than 1000 m 2} /g, Test Example 25 And the yield of Test Example 29 is less than 20%, so it is not good. In contrast, in Test Example 30 (silica-to-aluminum ratio: 20, alkali dose ratio: 1.2) and Test Example 31 (silica-to-aluminum ratio: 20, alkali dose ratio: 1.8), the experimental results of the zeolite specific surface area and yield were more satisfactory. In the following, the conditions of the silicon-to-aluminum ratio of 20 and the alkali dosage ratio of 1.2 in Test Example 30 are used to try to expand production, and the continuous fluidized bed hydrothermal reaction device of the present invention is used to continuously synthesize porous materials.

<Example 1: Preparation of porous material of mass production grade> Steps (a) to (g) of the method for continuously synthesizing porous materials of the present invention are carried out. In steps (d) to (f), the continuous fluidized bed hydrothermal reaction device (volume 100L) of the present invention is used. And as mentioned above, by continuously guiding (drawing) the liquid in the reaction tank from the top of the reaction tank and injecting it from the bottom of the reaction tank, the fluid in the reaction tank and the hydrolysis reaction raw material or hydrothermal reaction raw material are produced. Fluidization phenomenon to achieve the purpose of uniform mixing to promote the effect of hydrolysis reaction and hydrothermal reaction.

Next, the reaction conditions of Example 1 are described as follows: In step (a), waste glass is used as silicon-containing inorganic waste. In step (b), the ratio of silicon to aluminum is set to 20. In step (c), the alkali dosage ratio is set to 1.2, the alkali melting temperature is set to 400°C, and the alkali melting reaction time is 1 hour. In step (d), the liquid-to-solid ratio is set to 100, the hydrolysis reaction temperature is set to 105°C, and the hydrolysis reaction time is set to 40 minutes; and after step (d), the hydrolysis reaction product is subjected to solid-liquid separation and hydrolysis The liquid part of the reaction product is used as a hydrothermal reaction raw material and is returned to the reaction tank 1 from the solid-liquid separation unit 5. In step (e), 1.2% CTAB template was used, and 6M sulfuric acid was added to adjust the pH to 10; and the temperature of the hydrothermal reaction was 105° C., and the time of the hydrothermal reaction was 12 hours. The solid-liquid separation unit used in step (f) includes: a coarse filter plate with a filter mesh pore size of 100 µm; and a fine filter plate with a filter mesh pore size of 20 µm; and, the liquid after the solid-liquid separation of the hydrothermal reaction product is refluxed To the top of reaction tank 1. In step (g), the solid separated in step (f) is cleaned, dried at 110°C for 4 hours, and calcined at 550°C for 3 hours to obtain a mass-produced porous material.

<Comparative example 1> The reaction conditions of each step are the same as in Example 1. However, instead of using the continuous fluidized bed hydrothermal reactor of the present invention, a laboratory-grade 10-liter (10L) hydrothermal reactor (a hot water reactor with a lid and a seal) is used. In addition, in Comparative Example 1, the reflow in the step (d) and the step (f) was not performed.

＜Comparative example 2＞ Except that the solid-liquid separation after step (d) (hydrolysis reaction) is not performed, the other conditions are the same as in Comparative Example 1. The experimental results of Example 1 and Comparative Examples 1-2 are shown in Table 3 below.

[table 3] Whether there is solid-liquid separation after the hydrolysis reaction Yield(%) Zeolite specific surface area (m ² /g) Example 1 Have 90.00% 300.00 Comparative example 1 Have 56.81% 972.24 Comparative example 2 without 68.46% 288.12

It can be seen from Table 3 that in the case of using waste glass as silicon-containing inorganic waste, although laboratory grades (the aforementioned test examples 17 to 32 and comparative example 1) can obtain zeolite with a higher specific surface area, the yield is all It does not exceed 60%, and continuous production cannot be achieved. Therefore, although the specific surface area of the zeolite (300 m ² /g) of Example 1 still has room for improvement compared with that of Comparative Example 1 (972.24 m ² /g), Example 1 can already achieve continuous production. In addition, because Example 1 makes full use of various resources in the hydrothermal synthesis process (for example, the solution after the hydrolysis reaction, the solution after the hydrothermal reaction, etc.), the yield of the zeolite can be increased to 90.00%.

In addition, it can be seen from the laboratory-level Comparative Example 1 and Comparative Example 2 that if solid-liquid separation is not performed after the hydrolysis reaction, although the yield can be slightly increased (the yield is increased from 56.81% to 68.46%), there is zeolite When the specific surface area is greatly reduced (the specific surface area decreases from 972.24 m ² /g to 288.12 m ² /g). Therefore, we expect that in the case of mass production level, if solid-liquid separation is not carried out after the hydrolysis reaction, there will be a situation in which the specific surface area of the zeolite is greatly reduced although the yield can be slightly increased. Therefore, by performing solid-liquid separation after the hydrolysis reaction to remove undesired solid impurities, the specific surface area of the final synthesized porous material can be increased.

The present invention is not limited to the above-mentioned embodiments, and various modifications can be made within the scope shown in the claims, and embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included in the present invention Within the scope of technology.

1: reaction tank

11: (upright cylindrical) tank

12: (Inverted cone-shaped) bottom

2: Feeding port

3: Discharge port

4: heating element

5: Solid-liquid separation unit

51: Coarse filter plate

52: Fine filter plate

6: Two-way circulation pump

7: Pressure gauge

8: agitator

9: Thermocouple (thermocouple thermometer)

10: Pressure relief valve

20: Automatic control panel

100,100’: Continuous fluidized bed hydrothermal reaction device

a1~a9: On-off valve

L1: The first circulation pipeline

L2: Second circulation pipeline

(a)~(g): steps

[Figure 1] is a schematic diagram of a continuous fluidized bed hydrothermal reaction device according to an embodiment of the present invention. [Figure 2] is a schematic diagram of a continuous fluidized bed hydrothermal reaction device according to another embodiment of the present invention. [Fig. 3] is a flowchart of a method for continuous hydrothermal synthesis of porous materials according to an embodiment of the present invention.

1: reaction tank

11: (upright cylindrical) tank

12: (Inverted cone-shaped) bottom

2: Feeding port

3: Discharge port

4: heating element

5: Solid-liquid separation unit

6: Two-way circulation pump

100: Continuous fluidized bed hydrothermal reaction device

a1~a8: On-off valve

L1: The first circulation pipeline

L2: Second circulation pipeline

Claims (13)

A continuous fluidized bed hydrothermal reaction device, which includes: a reaction tank, which includes: an upright cylindrical tank body; and an inverted cone-shaped bottom; a feeding port, which is used to input hydrolysis reaction raw materials or hydrothermal The reaction raw material, which is arranged above the reaction tank and communicates with the top of the reaction tank; the discharge port is used to discharge the hydrolysis reaction product or the hydrothermal reaction product, and it is connected to the bottom of the reaction tank Heating element, which is used to heat the reaction tank; solid-liquid separation unit, which is used to separate the hydrolysis reaction product or hydrothermal reaction product from solid-liquid, and which is arranged under the discharge port and connected with the The discharge port is connected; the circulation pipeline is connected with the top of the reaction tank, the bottom of one side of the solid-liquid separation unit, and the discharge port; the two-way circulation pump is arranged on the circulation pipeline and is connected It is used to perform at least one of the following: make the hydrolysis reaction raw material or hydrothermal reaction raw material guided from the top of the reaction tank be injected into the bottom of the reaction tank through the circulation line; or make the solid-liquid The liquid of the hydrolysis reaction product or the liquid of the hydrothermal reaction product separated by the separation unit is injected into the top of the reaction tank through the circulation line. The continuous fluidized bed hydrothermal reaction device according to claim 1, wherein the circulation pipeline includes: a first circulation pipeline, which is arranged on one side of the reaction tank and is connected to The top of the reaction tank is connected with the discharge port; the second circulation pipeline is connected with the bottom of one side of the solid-liquid separation unit and the first circulation pipeline. The continuous fluidized bed hydrothermal reaction device according to claim 1, wherein the solid-liquid separation unit includes: a coarse filter plate with a pore size of 100 μm; and a fine filter plate with a pore size of 20 μm. The continuous fluidized bed hydrothermal reaction device according to claim 1, further comprising: a dispersing plate, which is arranged at the bottom of the reaction tank. The continuous fluidized bed hydrothermal reaction device according to claim 1, further comprising: a stirrer, which is arranged in the tank. The continuous fluidized bed hydrothermal reaction device according to any one of claims 1 to 5, further comprising: at least any one of the group consisting of a thermocouple, a pressure gauge, and a level gauge, and the foregoing The thermocouple, pressure gauge and level gauge are arranged in the reaction tank and used to detect the temperature, pressure and liquid level in the reaction tank respectively. The continuous fluidized bed hydrothermal reaction device according to claim 6, which further comprises: an automatic control panel, which is electrically connected with the aforementioned thermocouple, pressure gauge, and level gauge, and through the aforementioned thermocouple, Pressure gauges and level gauges are used to monitor and automatically control the temperature, pressure and liquid level in the reaction tank. A method for continuous hydrothermal synthesis of porous materials, which comprises: (a) providing a silicon-containing inorganic waste; (b) adjusting the silicon/aluminum molar ratio of the aforementioned silicon-containing inorganic waste to obtain alkali fusion Reaction material (c) Add an alkali agent to the raw material for the alkali fusion reaction, and perform an alkali fusion reaction to obtain the raw material for the hydrolysis reaction; Hydrothermal reaction raw materials; (e) adding a template to the aforementioned hydrothermal reaction raw materials and adjusting the pH value to perform a hydrothermal reaction and obtain a hydrothermal reaction product; (f) subjecting the aforementioned hydrothermal reaction product to solid-liquid separation, To obtain the liquid and porous material precursor solid of the aforementioned hydrothermal reaction product, and recycle the liquid of the aforementioned hydrothermal reaction product as the raw material for the hydrolysis reaction; (g) drying and calcining the aforementioned porous material precursor solid , To obtain a porous material; wherein, the aforementioned steps (d) to (f) are carried out in the continuous fluidized bed hydrothermal reaction device as described in any one of claims 1 to 7. The method for continuous hydrothermal synthesis of a porous material according to claim 8, wherein, in step (b), the silicon/aluminum molar ratio of the aforementioned silicon-containing inorganic waste is adjusted to 10-40. The method for continuous hydrothermal synthesis of porous materials according to claim 8, wherein, in step (c), the weight ratio of alkali agent/alkali melting reaction raw material (alkali dosage ratio) is 1.0 to 1.5. The method for continuous hydrothermal synthesis of porous materials according to claim 8, wherein, in step (d), the weight ratio (liquid-solid ratio) of pure water/hydrolysis reaction raw material is adjusted to 50 to 200, and the foregoing The hydrolysis reaction product is subjected to solid-liquid separation, and the liquid of the aforementioned hydrolysis reaction product is used as a hydrothermal reaction raw material. The method for continuous hydrothermal synthesis of porous materials according to claim 8, wherein, in step (e), the template is cetyltrimethylammonium bromide (CTAB), and the amount of the template is used It is 0.5~1.5% by weight of the aforementioned hydrothermal reaction raw materials, and the pH value during the hydrothermal reaction is 8-12, the hydrothermal reaction temperature is 105-150°C, and the hydrothermal reaction time is 8-16 hours. The method for continuous hydrothermal synthesis of porous materials according to any one of claims 8 to 12, wherein, in step (a), the aforementioned silicon-containing inorganic waste is selected from the group consisting of incineration bottom slag, fly ash , At least any one of the group consisting of waste glass, hearth stone, brick ceramics, inorganic sludge and stone waste.

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