TW202222691A - Continuous fluidized bed hydrothermal reaction device and method for continuous hydrothermal synthesis of porous materials which comprises a reaction tank, a feeding port, a discharging port, a heating element, a solid-liquid separation unit, a circulating pipeline, and a two-way circulating pump - Google Patents

Abstract

A continuous fluidized bed hydrothermal reaction device is provided, which comprises a reaction tank including a vertical cylindrical tank body and an inverted conical bottom; a feeding port; a discharging port; a heating element; a solid-liquid separation unit; a circulating pipeline; and a two-way circulating pump which is arranged on the circulating pipeline and is used to perform at least one of the following: injecting the hydrolysis reaction source material or hydrothermal reaction source material guided from the top of the reaction tank into the bottom of the reaction tank through the circulating pipeline, or injecting the liquid of the hydrolysis reaction product or the liquid of the hydrothermal reaction product separated by the solid-liquid separation unit into the top of the reaction tank through the circulating pipeline. The continuous fluidized bed hydrothermal reaction device of the present invention can achieve the effect of a fluidized bed through the design of a reaction tank, and can make full use of various resources in the hydrothermal synthesis process through the two-way circulating pump and circulating pipeline to save energy and resource consumption, reduce operation cost, and achieve the effects of continuous production and scale-up of production.

Description

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

The present invention relates to a continuous fluidized bed hydrothermal reaction device and a method for continuous hydrothermal synthesis of 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 produced in my country is as high as 10 million metric tons each year, including incineration bottom slag and fly ash, waste glass, panel glass, dust collection ash, boiler ash, steelmaking ballast, furnace Stone, brick ceramics, inorganic sludge, stone waste, etc., and as the treatment method for the aforementioned silicon-containing inorganic waste, it is generally solidified/stabilized and then stacked/buried in a landfill. However, due to 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/burying treatment, some people propose to make silicon-containing inorganic wastes waste. The zeolite is synthesized by hydrothermal reaction.

As for the reaction equipment for synthesizing zeolite by hydrothermally reacting silicon-containing inorganic waste, a small-sized hydrothermal reactor with a lid is generally used.

However, because the above-mentioned hydrothermal reactors with caps and seals are batch-type reaction equipment and are usually small-scale reaction devices with limited capacity, the space for large-scale production and application development is limited. In addition, because the batch-type reaction equipment can only perform batch production and cannot be continuously produced, it cannot meet the needs of industrialization.

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

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

In order to solve the above problems, a continuous fluidized bed hydrothermal reaction device of one aspect of the present invention comprises: A reaction tank, which includes: an upright cylindrical tank body; and an inverted conical bottom; a feeding port, which is used to input hydrolysis reaction raw materials or hydrothermal reaction raw materials, and is arranged above the reaction tank and communicated with the top of the reaction tank; A discharge port, which is used to discharge the hydrolysis reaction product or the hydrothermal reaction product, and is communicated with the bottom of the reaction tank; a heating element for heating 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 communicated with the discharge port; a circulation line, which is communicated with the top of the reaction tank, the bottom of one side of the solid-liquid separation unit, and the outlet; A bidirectional circulating pump, which is arranged on the circulating line, and which is used to perform at least one of the following: the hydrolysis reaction raw material or the hydrothermal reaction raw material guided from the top of the reaction tank passes through the circulating line and 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 line system includes: a first circulation line, 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 line, which is connected with the solids. The bottom of one side of the liquid separation unit communicates with the first circulation line.

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

In one embodiment, the continuous fluidized bed hydrothermal reaction device further comprises: 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 disposed in the tank.

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

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

In order to solve the above problems, a method for continuous hydrothermal synthesis of porous materials according to an aspect of the present invention comprises: (a) providing a silicon-containing inorganic waste; (b) adjusting the silicon-alumina of the silicon-containing inorganic waste (c) adding alkali agent to the aforementioned raw materials for alkaline melting reaction, and performing alkaline melting reaction to obtain raw materials for hydrolysis reaction; (d) adding an appropriate proportion of pure water (most (e) adding a templating agent to the aforementioned hydrothermal reaction raw material and adjusting the pH value to carry out a hydrothermal reaction, and obtain a Hydrothermal reaction product; (f) carrying out solid-liquid separation of the aforementioned hydrothermal reaction product to obtain the liquid of the aforementioned hydrothermal reaction product and the solid of the porous material precursor, and recycling the aforementioned liquid of the aforementioned hydrothermal reaction product as a hydrolysis reaction raw materials; (g) drying and calcining the aforementioned porous material precursor solid to obtain a porous material; wherein, the aforementioned steps (d) to (f) are performed in the continuous fluidized bed hydrothermal reaction of the present invention carried out in the device.

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

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

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

Also, in one embodiment, in the step (e), the aforementioned templating agent is cetyltrimethylammonium bromide (CTAB), and the usage amount of the aforementioned templating agent is 0.5 to 1.5% by weight of the aforementioned hydrothermal reaction raw materials , and the pH value 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.

Also, in one embodiment, in the step (a), the 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, and steelmaking furnace slag , at least one of the group consisting of hearthstone, brick ceramics, inorganic sludge and stone waste.

One aspect of the present invention is made in view of the above-mentioned conventional problems, and an object of the present invention is to provide a continuous fluidized bed hydrothermal reaction device, which achieves the effect of a 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.) , in order to save energy and resource consumption, reduce operating costs, and can achieve the effect of continuous production and scale-up of production.

One aspect of the present invention provides a method for continuous hydrothermal synthesis of porous materials, which can achieve continuous hydrolysis and hydrothermal reactions in the continuous fluidized bed hydrothermal reaction device of the present invention. The effect of type production and scale-up of production.

<Continuous Fluidized Bed Hydrothermal Reactor> First, please refer to FIG. 1 , which is a schematic diagram of a continuous fluidized bed hydrothermal reaction apparatus according to an embodiment of the present invention. As shown in FIG. 1, the present invention provides a continuous fluidized bed hydrothermal reaction device 100, which comprises: a reaction tank 1, a feeding port 2, a discharging port 3, a heating element 4, a solid-liquid separation unit 5, a bidirectional circulation The pump 6, the circulation line (in this embodiment, it is the first circulation line L1 and the second circulation line L2).

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

In addition, the feeding port 2 is used for feeding the hydrolysis reaction raw material or the hydrothermal reaction raw material, and it is installed above the reaction tank 1 and communicated with the top of the reaction tank 1 . The feeding port 2 can be tubular to facilitate the feeding of raw materials. The raw materials for the hydrolysis reaction can be, for example, the raw materials that have undergone the steps (a) to (c) described later. Obtained after alkali fusion reaction. In addition, for the hydrothermal reaction raw material, for example, at least a part of the hydrolysis reaction product (eg, preferably a liquid of the hydrolysis reaction product) can be used as the reaction raw material, or the hydrolysis reaction product can be directly used as the reaction raw material.

Also, it should be noted that although the present invention preferably uses the aforementioned bidirectional circulating pump 6 and circulating pipelines (such as the first circulating pipeline L1 and the second circulating pipeline L2) to circulate a part of the hydrolysis reaction product (such as the hydrolysis product) liquid) as a hydrothermal reaction raw material, and the hydrothermal reaction raw material is injected into the inlet of the top of the reaction tank 1 through the second circulation line L2 and the first circulation line L1 (details will be described later), but also A part of this hydrolysis reaction product is guided to the charging port 2, and a hydrolysis reaction raw material is injected|thrown-in. In addition, when the hydrothermal reaction raw material is charged, it can be selected from the inlet of the top of the reaction tank 1 (at the opening and closing valve a1 in FIG. In addition, the circulation line of the present invention is not limited to the first circulation line L1 and the second circulation line L2 as long as it communicates 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 combination.

Next, 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 is completed in the reaction tank 1 , and the discharge port 3 is connected to the bottom of 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, flow rate, etc. of the hydrolysis reaction product or the hydrothermal reaction product in the reaction tank 1 leading to the discharge port 3 .

Next, the heating element 4 is used to heat the reaction tank 1 to 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 the effect of uniform heating, a plurality of heating elements 4 can be arranged around the reaction tank 1 . In addition, as far as the preferred form of the heating element 4 is concerned, as shown in FIG. 2 described later, it can be a heating coil and a thermal insulation material covering the surrounding of the tank body 11, thereby having a good thermal storage and thermal insulation effect. Reduce heat loss.

Next, as shown in FIG. 1 , the solid-liquid separation unit 5 is disposed 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 set between the discharge port 3 and the solid-liquid separation unit 5, and it is used to control the hydrolysis reaction product or the hydrothermal reaction product passing through the discharge port 3 to be guided to the solid-liquid separation unit 5 flow rate, flow rate, etc. In addition, in terms of 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 aperture of 100 μm; and a fine filter plate 52 with a filter mesh aperture 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 between the first circulation line L1 and the top of the reaction tank 1 to control flow rate, flow rate, and the like. In addition, the first circulation line L1 is used to flow the substance involved in the hydrolysis reaction/hydrothermal reaction in the pipeline, and can change the amount of the substance involved in the hydrolysis reaction/hydrothermal reaction based on the control of the bidirectional 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 involved in the hydrolysis reaction/hydrothermal reaction (such as a hydrolysis reaction product) from the discharge port 3 to the first circulation line L1. flow, velocity, etc.

Furthermore, as shown in FIG. 1 , the second circulation line L2 communicates with the bottom of one side of the solid-liquid separation unit 5 and with the first circulation line L1. The first circulation line L2 is used to allow the hydrolysis reaction product or hydrothermal reaction product after solid-liquid separation to 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 (at the opening and closing valve a1) via the first circulation line L1. The on-off valve a5 can be provided between the solid-liquid separation unit 5 and the second circulation line L2 for control, and the on-off valve a4 can 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 comprises: a bidirectional circulating pump 6, which is arranged on the circulating pipeline and is used to perform at least one of the following: The hydrolysis reaction raw material or the 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; 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 opening and closing valve a1) through the second circulation line L2 and the first circulation line L1. In addition, the on-off valves a2 and a3 can be provided upstream and downstream of the bidirectional circulation pump 6 for control, respectively. Thereby, by continuously guiding (pumping) 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 heated with the hydrolysis reaction raw material or hydrothermally. The reaction material is fluidized to achieve the purpose of uniform mixing, which can promote the effect of hydrolysis reaction and hydrothermal reaction, and can continuously flow and circulate, 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 apparatus 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' according to another embodiment of the present invention also includes: a reaction tank 1, a feeding port 2, a feeding 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 the on-off valves a1 to a8 are included. Therefore, in FIG. 2 , the same reference numerals are given to the same elements as those in FIG. 1 , and the description thereof is omitted.

Among them, as mentioned above, FIG. 2 shows a preferred aspect of the heating element 4 and the solid-liquid separation unit 5 . For example, the heating element 4 can be a heating coil and a thermal insulation material surrounding the upright cylindrical tank body 11 , thereby having a good thermal storage and thermal insulation 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. The heating element 4 is preferably a heating coil covering the discharge port 3, the surrounding of the first circulation line L1 and the second circulation line L2, and a thermal insulation material. In addition, the solid-liquid separation unit 5 is preferably made of stainless steel filter mesh, and the mesh size of the filter mesh is 100µm (upper layer coarse filter plate 51 ) and 20μm (lower layer fine filter plate 52 ). Thereby, through the combination of the coarse/fine filter plate, a better screening effect can be achieved, so that the solid content separated from the hydrothermal reaction product can be subjected to the calcination step and the like described later. In addition, the above-mentioned filter screen aperture is only a preferred aspect of the present invention, and the screen screen can be adjusted and changed appropriately according to requirements, and the multi-layer separation device designed to be adjustable has more operational flexibility.

In addition, in FIG. 2 , a stirrer 8 can also be arranged in the tank body 11 to increase the mixing effect of various reaction raw materials. The stirrer 8 can be stirred as needed, and the rotational speed of the stirrer 8 can be designed to be between 0 and 100 rpm. In addition, in FIG. 2, the bottom part 12 of the reaction tank 1 can also be provided with a dispersion plate (not shown). The dispersing plate can be set according to requirements, and the dispersing plate can generate upward fluid force, so that the fluid in the tank 11 and various reaction raw 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) and the like can also be provided in the reaction tank 1 (eg, on the top of the reaction tank 1 ) as required. By arranging the above-mentioned pressure gauge 7, thermocouple (thermocouple thermometer) 9, liquid level gauge, etc., the pressure, temperature, liquid level, etc. during the reaction process can be monitored. And by means of the pressure relief valve 10 , it can be ensured that there will be no danger due to excessive pressure during the reaction process. In addition, an automatic control panel 20 can also be provided. The automatic control panel 20 is electrically connected to the aforementioned thermocouple 9, the pressure gauge 7 and the liquid level gauge, and through the aforementioned thermocouple 9, the pressure gauge 7 and the liquid level gauge, the 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 velocity, flow rate, and the like at the time of charging of various raw materials.

The examples and variations of the continuous fluidized bed hydrothermal reaction device of the present invention have been described above, and the above examples and variations are only illustrative, and are not intended to limit the scope of the present invention. Other equivalents of the examples and variations are also included within the scope of the invention. The method for continuous hydrothermal synthesis of a porous material of the present invention will be described below.

<Method for continuous hydrothermal synthesis of porous material> The basic principle of the continuous hydrothermal method for synthesizing porous materials of the present invention is to dissociate and dissolve the silicon oxides and aluminum oxides in the silicon-containing inorganic waste by the alkali melting step, and then use hydrolysis and hydrothermal reaction to dissociate the silicon oxides. Rearranged and combined with aluminum oxide under appropriate control conditions, nucleated, polycondensed, and crystallized into inorganic porous materials similar to synthetic zeolite, so that it has good specific surface area and pore distribution characteristics; The hydrolysis and hydrothermal reaction are carried out in the fluidized bed hydrothermal reaction device, so that the porous material can be continuously synthesized, thereby completing the continuous hydrothermal synthesis method of the porous material of the present invention.

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). Each step is described below.

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

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

-(c) step- (c) step is to add an alkali agent to the above-mentioned alkali-melting reaction raw materials, and carry out alkali-melting reaction to obtain hydrolysis reaction raw materials. As the alkaline agent used in the (c) step, for example, sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate (Na ₂ CO ₃ ), or a combination thereof can be used, but not limited thereto. In terms of alkali dosage ratio (weight ratio of alkali agent/alkali melting reaction raw material), it is preferably 1.0 to 1.5%, more preferably 1.2%. In addition, as for the reaction apparatus used in the 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, preferably at 400° C. for 60 minutes. Finally, the product after alkali fusion reaction is used as the raw material for the hydrolysis reaction.

-(d) Step- The step (d) is to add pure water to the above-mentioned hydrolysis reaction raw materials and carry out the hydrolysis reaction, and use 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, for example, the hydrolysis reaction raw materials and pure water can be put into the reactor 1 from the above-mentioned feeding port 2 to be carried out. In the step (d), the weight ratio (liquid-solid ratio) of pure water to hydrolysis reaction raw materials is preferably 50-200. The hydrolysis reaction system can be carried out by, for example, reacting at 105° C. for 40 minutes, and cooling and cooling after the completion of the reaction.

Also, the whole 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 can be used. ) as a raw material for hydrothermal reaction (eg, liquid for hydrothermal reaction). Specifically, after the hydrolysis reaction, the on-off valves a7 and a8 can be opened, so that the hydrolysis reaction product enters the solid-liquid separation unit 5, and the solid-liquid separation unit 5 performs solid-liquid separation on the hydrolysis reaction product. Afterwards, the flow direction is controlled by the bidirectional circulating pump 6, and the on-off valves a1 to a5 are opened to separate the liquid of the hydrolysis reaction product after the 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 of directly using the hydrolysis reaction product as the raw material for the hydrothermal reaction, in the case of using the liquid of the hydrolysis reaction product after solid-liquid separation as the raw material for the hydrothermal reaction, because the solid-liquid separation removes the undesired material. Therefore, the specific surface area of the final synthesized porous material can be increased.

-(e) Step- The step (e) is to add a template agent to the above-mentioned hydrothermal reaction raw materials and adjust the pH value to conduct 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, for example, the template agent is put into the reactor 1 from the aforementioned feeding port 2, and the aforementioned hydrothermal reaction raw materials (for example, refluxed) The liquid of the hydrolysis reaction product or the hydrolysis reaction product itself) is reacted. As for the templating agent added in step (e), it can be, for example, cetyltrimethylammonium bromide (CTAB). In terms of the addition amount of the template agent, it is preferably 0.5 to 1.5 wt % of the aforementioned hydrothermal reaction raw materials, and more preferably 1.2 wt %. Moreover, in the step (e), the pH value of the hydrothermal reaction raw material to which the template agent is added is preferably adjusted to 8 to 12, more preferably 10. As a method for adjusting the pH value, for example, an acid or a base can be added. In a specific example, 1M sulfuric acid solution is added to adjust the pH value of the hydrothermal reaction raw material to which the template agent is added to be about 10, so as to complete the hydrothermal reaction precursor solution.

In addition, in the step (e), for the aforementioned hydrothermal reaction precursor solution, it is preferable to carry out the hydrothermal synthesis reaction at a temperature of 80 to 200° C. for 8 to 24 hours, and it is more preferable 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- (f) step is to carry out solid-liquid separation of the aforementioned hydrothermal reaction product to obtain the liquid of the aforementioned hydrothermal reaction product and the solid of the porous material precursor, and to use the aforementioned liquid of the aforementioned hydrothermal reaction product as a hydrolysis reaction raw material (for example, a hydrolysis reaction liquid used). The 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 separated 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, the step (g) described later is performed on the porous material precursor solid obtained in the step (f).

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

Moreover, as this porous material, synthetic zeolite can be used, for example. The porous material can also be further processed into adsorbents, filter materials, catalyst carriers and other products, which are used in environmental protection, chemical industry, materials, optoelectronics, incineration, construction and other related industries.

[Example] Examples and comparative examples of the present invention will be described below. The present invention is not limited by these Examples and Comparative Examples.

<Test Examples 1 to 16: Preparation of Laboratory Grade Porous Materials> Steps (d)-(f) were performed using a laboratory grade 10 liter (10 L) hydrothermal reactor (capped and sealed hot water reactor). In addition, except that in the step (f), "use the liquid of the aforementioned hydrothermal reaction product as the hydrolysis reaction raw material" and the hydrolysis time is adjusted for 2 to 24 hours, according to the above (a) steps to (g) steps, in the experiment Synthetic porous materials at the chamber level. The specific details of the steps (a) to (g) are as follows. In addition, the experimental results are shown in Table 1 below. (a) Step: The incineration mixed ash (a mixture of boiler ash and fly ash, etc.) from a waste incineration plant in central Taiwan (Test Examples 1 to 16) was used as the silicon-containing inorganic waste. The aforementioned silicon-containing inorganic waste is crushed and screened. (b) Step: The silicon-aluminum ratio of the aforementioned silicon-containing inorganic waste is adjusted to the following Table 1. (c) Step: 1.2% by weight of sodium hydroxide (NaOH) was used as the 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 carried out, and the liquid part is taken to carry out the step (e). The liquid-solid ratio is shown in Table 1. (e) step: adding 1.2% by weight of cetyltrimethylammonium bromide (CTAB) as a templating agent, and the hydrothermal reaction temperature is 105°C. The pH of the hydrothermal reaction raw material to which the template agent was added was adjusted to 10 using a sulfuric acid solution. The hydrothermal reaction time is shown in Table 1. (f) Step: Use a double-layer sieve (the upper layer has a pore size of 100 µm; the lower layer has a pore size of 20 µm) for solid-liquid separation of the hydrothermal reaction product. Step (g): Wash the solid separated in step (f), dry at 110° C. for 4 hours, and calcine at 550° C. for 3 hours to obtain experimental grade porous materials.

[Table 1] Test example Si/Al ratio Alkali Dose Ratio Alkali melting temperature (℃) Liquid to Solid Ratio Hot water 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 (°C), the liquid-solid ratio and the hydrothermal time are within the range of Table 1, these parameters are all acceptable levels, not the key to affecting the specific surface area of zeolite factor. In addition, as can be seen from the results in Table 1, Test Examples 1 to 4 were unsatisfactory because they could not obtain zeolite with a specific surface area larger than 600 m ² /g using silicon-containing inorganic wastes with a Si/Al ratio of 5. In addition, in Test Examples 5 to 8, although the ratio of silicon to aluminum is 10, only under the condition that the alkali dose ratio is 1 to 1.5, zeolite with a specific surface area greater than 600 m ² /g can be obtained, so we think that the alkali dose is relatively The optimal system is 1~1.5, and the silicon-aluminum ratio needs to be more than 10.

Next, in Test Examples 9-16, silicon-containing inorganic wastes with a Si-Al ratio of 20 and 40 were used, and the specific surface areas of the synthesized zeolites were all greater than 600 m ² /g, so it can be known that the Si-Al ratio is preferably 10-40 between. In addition, since the zeolite with a specific surface area of 962.08 m ² /g was obtained in Test Example 10, it can be seen that in the case of using the incineration mixed ash, the silicon-alumina ratio of 20 and the alkali dose ratio of 1.5 are optimal. Preferences. And it can be known from Table 1 that the silicon-aluminum ratio and the alkali dosage ratio are the key factors affecting the specific surface area of zeolite.

<Test Examples 17 to 32: Preparation of laboratory-grade porous materials> Preparation of porous materials was carried out in the same manner as in the above-mentioned Test Examples 1 to 16, except that waste glass was used as a substitute for the incineration mixed ash. The experimental parameters and results are shown in Table 2.

[Table 2] Test example Si/Al ratio Alkali Dose Ratio Alkali melting temperature (℃) Liquid to Solid Ratio Hot water 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 (°C), liquid-solid ratio and hydrothermal time are within the ranges of Table 2, these parameters are all acceptable. , is not a key factor affecting the specific surface area and yield of zeolite. In addition, when the silicon-alumina ratio was 1 and 5 (Test Examples 17 to 24), it was not possible to synthesize a zeolite with a specific surface area larger than 600 m ² /g, which was not good. Therefore, in the case of using waste glass as the inorganic waste containing silicon, the preferred ratio of silicon to aluminum is 10-20.

Next, although both Test Example 25 (silicon-aluminum ratio 10, alkali dosage ratio 0.6) and Test Example 29 (silicon-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 yields of Test Example 29 were both 20% or less, which was not good. On the other hand, in Test Example 30 (silicon-aluminum ratio 20, alkali dosage ratio 1.2) and Test Example 31 (silicon-aluminum ratio 20, alkali dosage ratio 1.8), the experimental results with better zeolite specific surface area and yield were obtained. Hereinafter, an attempt was made to expand production using the conditions of the silicon-alumina ratio of 20 and the alkali dose ratio of 1.2 in Test Example 30, and the continuous fluidized bed hydrothermal reaction apparatus of the present invention was used to continuously synthesize porous materials.

<Example 1: Preparation of mass production grade porous material> Steps (a) to (g) of the method for continuously synthesizing a porous material of the present invention are carried out. In the steps (d) to (f), the continuous fluidized bed hydrothermal reaction device of the present invention (with a volume of 100 L) is used. And as described above, by continuously guiding (pumping) 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 the hydrothermal reaction raw material are generated. Fluidization phenomenon, and achieve the purpose of uniform mixing, in order to promote the effect of hydrolysis reaction and hydrothermal reaction.

Next, the reaction conditions for Example 1 are explained as follows: In the step (a), waste glass is used as the silicon-containing inorganic waste. The Si/Al ratio was set to 20 in step (b). In the step (c), the alkali dose ratio was set to 1.2, the alkali melting temperature was set to 400° C., and the alkali melting reaction time was set to 1 hour. In the (d) step, the liquid-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 the (d) step, the hydrolysis reaction product is subjected to solid-liquid separation, and the hydrolysis reaction product is separated. The liquid part of the reaction product is returned to the reaction tank 1 from the solid-liquid separation unit 5 as a raw material for the hydrothermal reaction. In step (e), 1.2% CTAB templating agent was used, and 6M sulfuric acid was added to adjust the pH value 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 the step (f) includes: a coarse filter plate with a filter screen aperture of 100 μm; to the top of reaction tank 1. In step (g), the solid separated in step (f) is washed, 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 (10 L) hydrothermal reactor (capped and sealed hot water reactor) was used. In addition, in Comparative Example 1, the reflux of the step (d) and the step (f) was not performed.

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

[table 3] Whether the solid-liquid separation after the hydrolysis reaction is carried out 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 none 68.46% 288.12

As can be seen from Table 3, 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 zeolites with higher specific surface areas, the yields are all Less than 60%, and continuous production cannot be achieved. Therefore, although the zeolite specific surface area (300 m ² /g) of Example 1 still has room for improvement compared to Comparative Example 1 (972.24 m ² /g), Example 1 has been able to achieve continuous production. In addition, because Example 1 makes full use of various resources in the hydrothermal synthesis process (such as solution after hydrolysis reaction, solution after hydrothermal reaction, etc.), the yield of zeolite can be increased to 90.00%.

In addition, as can be seen from the comparative examples 1 and 2 of the laboratory grade, if the solid-liquid separation is not carried out after the hydrolysis reaction, although the yield can be slightly improved (the yield is increased from 56.81% to 68.46%), there are zeolites. The case where the specific surface area decreased significantly (the specific surface area decreased from 972.24 m ² /g to 288.12 m ² /g). Therefore, we expect that in the case of mass production, if the solid-liquid separation is not carried out after the hydrolysis reaction, there will be a situation of "although the yield can be slightly improved, but the specific surface area of zeolite is greatly reduced". 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-described embodiments, and various modifications can be made within the scope of the claims, and embodiments obtained by appropriately combining technical means disclosed in different embodiments are also included in the present invention. within the technical scope.

1: Reaction tank 11: (upright cylindrical) tank body 12: (inverted conical) bottom 2: Feeding port 3: discharge port 4: Heating element 5: Solid-liquid separation unit 51: Coarse filter plate 52: Fine filter plate 6: Bidirectional circulating pump 7: Pressure gauge 8: Blender 9: Thermocouple (thermocouple thermometer) 10: Pressure relief valve 20: Automatic control panel 100, 100': Continuous Fluidized Bed Hydrothermal Reactor a1~a9: On-off valve L1: The first circulation line L2: Second circulation line (a)~(g): Steps

Fig. 1 is a schematic diagram of a continuous fluidized bed hydrothermal reaction device according to an embodiment of the present invention. [Fig. 2] is a schematic diagram of a continuous fluidized bed hydrothermal reaction device according to another embodiment of the present invention. 3 is a flow chart 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 body

12: (inverted conical) bottom

2: Feeding port

3: discharge port

4: Heating element

5: Solid-liquid separation unit

6: Bidirectional circulating pump

100: Continuous Fluidized Bed Hydrothermal Reactor

a1~a8: On-off valve

L1: The first circulation line

L2: Second circulation line

Claims (13)

A continuous fluidized bed hydrothermal reaction device, comprising: A reaction tank, which includes: an upright cylindrical tank body; and an inverted conical bottom; a feeding port, which is used to input hydrolysis reaction raw materials or hydrothermal reaction raw materials, and is arranged above the reaction tank and communicated with the top of the reaction tank; A discharge port, which is used to discharge the hydrolysis reaction product or the hydrothermal reaction product, and is communicated with the bottom of the reaction tank; a heating element for heating 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 communicated with the discharge port; a circulation line, which is communicated with the top of the reaction tank, the bottom of one side of the solid-liquid separation unit, and the outlet; A bidirectional circulating pump, which is arranged on the circulating line, and which is used to perform at least one of the following: the hydrolysis reaction raw material or the hydrothermal reaction raw material guided from the top of the reaction tank passes through the circulating line and 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. The continuous fluidized bed hydrothermal reaction device according to claim 1, wherein the circulation line system comprises: a first circulation line, which is arranged on one side of the reaction tank and is connected with the top of the reaction tank and the discharge material The port is communicated with; the second circulation line is communicated with the bottom of one side of the solid-liquid separation unit and the first circulation line. The continuous fluidized bed hydrothermal reaction device according to claim 1, wherein the solid-liquid separation unit comprises: a coarse filter plate with a filter mesh aperture of 100 µm; and a fine filter plate with a filter mesh aperture of 20 µm. The continuous fluidized bed hydrothermal reaction device according to claim 1, further comprising: a dispersing plate arranged at the bottom of the reaction tank. The continuous fluidized bed hydrothermal reaction device according to claim 1, further comprising: a stirrer disposed 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 liquid level gauge, and the aforementioned A thermocouple, a pressure gauge and a liquid level gauge are arranged in the reaction tank and are 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, further comprising: an automatic control panel, which is electrically connected to the thermocouple, pressure gauge and liquid level gauge, and is connected to the thermocouple, pressure gauge and liquid level gauge. A pressure gauge and a liquid level gauge 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, comprising: (a) provide a silicon-containing inorganic waste; (b) adjusting the silicon-aluminum ratio of the aforementioned silicon-containing inorganic waste to obtain raw materials for alkali fusion reaction; (c) adding alkali agent to the aforementioned alkali fusion reaction raw materials, and carrying out alkali fusion reaction to obtain hydrolysis reaction raw materials; (d) adding pure water to the aforementioned hydrolysis reaction raw materials and carrying out a hydrolysis reaction, and using at least a part of the hydrolysis reaction product as a hydrothermal reaction raw material; (e) adding a template agent to the aforementioned hydrothermal reaction raw material and adjusting the pH value to carry out a hydrothermal reaction, and obtain a hydrothermal reaction product; (f) carrying out the solid-liquid separation of the aforementioned hydrothermal reaction product to obtain the liquid of the aforementioned hydrothermal reaction product and the solid of the porous material precursor, and recycling the aforementioned liquid of the aforementioned hydrothermal reaction product as a hydrolysis reaction raw material; (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 according to any one of claims 1 to 7. The method for continuous hydrothermal synthesis of porous materials according to claim 8, wherein, in the step (b), the silicon-aluminum ratio (silicon/aluminum molar ratio) of the silicon-containing inorganic waste is adjusted to 10 ~40. The method for continuous hydrothermal synthesis of porous materials according to claim 8, wherein, in the step (c), the weight ratio (alkali dosage ratio) of the alkali agent/alkali fusion reaction raw material 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 materials is adjusted to 50-200, and the aforementioned The hydrolysis reaction product is subjected to solid-liquid separation, and the liquid of the hydrolysis reaction product is used as the raw material for the hydrothermal reaction. The method for continuous hydrothermal synthesis of porous materials according to claim 8, wherein, in step (e), the templating agent is cetyltrimethylammonium bromide (CTAB), and the amount of the templating agent used is It is 0.5 to 1.5 wt % of the aforementioned hydrothermal reaction raw materials, and the pH value of the hydrothermal reaction precursor solution is 8 to 12, the hydrothermal reaction temperature is 105 to 150 ° C, and the hydrothermal reaction time is 8 to 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 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, panel glass, dust collection ash, boiler ash, steelmaking slag, furnace stone, brick ceramics, inorganic sludge and stone waste.

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