KR100716059B1 - A continuous hydrothermal synthesizing equipment using microwave - Google Patents

Abstract

The present invention relates to a continuous microwave hydrothermal synthesis apparatus, and more particularly, to a catalyst production apparatus for continuous microwave hydrothermal synthesis, comprising: a catalyst-generating reactant feeder; A screw-type closed reaction tube of one end connected to the catalyst generating reactant feeder and made of a material that is inert to microwaves; A series of microwave irradiation chambers in which communication holes are formed in portions of both side walls to mount the reaction tubes, and magnetrons are mounted and electromagnetic waves are shielded to irradiate microwaves; A catalyst collector connected to the other end of the reaction tube; And it provides a continuous microwave hydrothermal synthesis apparatus including a control means for controlling them. The apparatus of the present invention is used to manufacture and develop various catalyst materials such as the preparation of hydrothermal synthesis catalyst by microwave, the preparation of sol-gel metal oxide by using microwave, the double metal oxide system, and the high dispersion of the prepared catalyst. In addition, it leaps forward as an eco-friendly process to reduce the amount of organic precursors and furthermore, it is used for mass production of organic compounds using microwaves.

Conventional hydrothermal reactors consume 1100W of power per second, and the reaction should be continued for at least 3 days to 5 days, while the continuous microwave hydrothermal apparatus of the present invention can shorten the reaction time by 10 minutes to 2 hours. This provides high productivity, energy efficiency, and easy maintenance of the manufacturing equipment, thereby increasing the competitiveness of catalyst production.

Microwave Lab, Magnetron

Description

A continuous hydrothermal synthesizing equipment using microwave

1 is a schematic cross-sectional view of a continuous microwave catalyst production apparatus according to the present invention.

* Description of Signs of Main Parts of Drawings *

① Foundry ② ② Hopper ③ Magnetron

④ Microwave irradiation chamber ⑤ Reaction tube motor ⑥ Teflon reaction tube

⑧ Take off catalyst product tank ⑨ Relief valve ⑩ Temperature sensor

The present invention relates to a continuous microwave hydrothermal synthesis apparatus. The present invention relates in particular to nanopore catalysts, bimetal oxide systems, highly dispersed catalysts, nanoparticles, various nanomaterial catalysts, and devices for producing organic compounds using the same using a continuous microwave hydrothermal synthesis method. As the amount of the catalyst is gradually increased due to the development of the petrochemical and fine chemical industries, the necessity of the synthesis technology for effectively preparing these nanocatalysts is gradually increasing.

On the other hand, the microwave used for microwave heating is a non-ionized radiant energy in the frequency range of 300-30000 MHz, and among these, four frequencies (915, 2450, 5800, 22125 MHz), especially 2450 MHz, are the most widely used. The typical energy output of a microwave system is 600-700 Watts, with about 43,000 cal applied to heating the sample within 5 minutes. The principle of microwaves is that polarization and interfacial polarization occur in the microwave region, and the dipole changes with time delay in the change of microwave electric field, and the heat generated is a kind of frictional heat. The heating of borne liquids mainly follows this mechanism. The polar molecules are rotated by the electric component of the microwave. When the polar molecules collide with other neighboring molecules, they get kinetic energy and the temperature rises.

The advantages of microwaves include time and energy cost savings and rapid manufacturing, the synthesis of selective crystalline materials due to temperature control in a short time, the overall uniform heating and improved properties of the material. Improved synthesis of nanomaterials is possible through catalyst development and optional introduction of microwaves.

In the case of hydrothermal synthesis, which is a conventional method for preparing a catalyst, the reaction time is long and excessive environmental pollutants are caused by the excess organic template and the washing process after the reaction, whereas the microwave consumes only about one in 200 energy. It is possible to reduce contaminants such as cleaning agents including organic template materials used by selective heating.

For the preparation of nanopore catalysts using microwaves, the international team of Mobil researchers in 1988 first synthesized microwave-based zeolites NaA and ZSM-5 for the first time, suggesting that microwaves are effective heat transfer agents. Bekkum and colleagues in the Netherlands found that microwaves synthesized zeolite Y and ZSM-5 in microwaves within 30 minutes to prevent the decomposition of organic template materials and optionally form only the desired crystals. The British company, Cohndi, synthesized zeolite beta, ZSM-5 and zeolite Y (EMT), and for the first time successfully synthesized zeolite beta with seed nuclei in 14 hours. Caro (Caro) party was synthesized AlPO ₄ -5 material is a cobalt substituted with microwave. A group of vanes suggested that it is possible to rapidly produce mesoporous Si and Al-MCM-41 within 1 hour by using microwave for the catalytic synthesis of mesoporous. Sun group synthesized MCM-41 within 1-30 minutes via several reaction routes. A recent report by Komarneni researchers reported the manufacture of a thermally stable SBA-15 within 2 hours, and various nanoporous materials using microwaves are being developed worldwide.

Domestically, Ahn reported a method of synthesizing NaA, NaY, ZSM-5 and zeolite beta in a short time under microwave conditions.

The inventors of the present invention Park Sang-un and his colleagues introduced microwave synthesis technology to prepare various microporous structural materials ZSM-5, Beta, porous nickel phosphate, zeolite Y, etc. using microwave, and various synthetic routes and transition metals were substituted. ZSM-5 was successfully synthesized within 5 minutes. Korean Patent No. 411194 discloses a continuous microwave device. It was confirmed that the physical properties of the synthesized ZSM-5 did not show a significant difference from conventional commercial zeolites.

General microwave synthesis has an internal structure similar to that of hydrothermal reactors, and depends on whether microwaves are used for heating or generally heated heat. In the case of ZSM-5 synthesis, a precursor made of TPAOH, an aluminum source, a silica source, and water is prepared and placed in a high-temperature, high-pressure Teflon container and heated for 10 minutes using an output of 300W. This is faster than conventional hydrothermal synthesis, but due to the small amount of synthesis, there is still much to be improved for mass production.

In Korean Patent No. 411194 of Park Sang-un, the inventor of the present invention, a continuous type was used for the synthesis of ZSM-5, and a tube-shaped reaction tube was mounted in a zigzag form as shown in the figure. The speed was adjusted to have continuity. However, because it is inevitable to wind the tube of the reaction tube like a coil, the Teflon tube is thin and the deposition of ZSM-5 generated inside the reaction tube has a problem that it is difficult to manufacture and manage the reaction tube. In addition, the catalyst production amount is small.

The present invention is to provide a continuous microwave hydrothermal synthesis apparatus capable of cost reduction and mass production.

It is another object of the present invention to provide a continuous microwave catalyst production apparatus which is low in cost and easy to maintain.

In another aspect, the present invention is to provide a continuous microwave catalyst production apparatus that can be expected to reduce the generation of contaminants, resource saving, energy saving at the same time.

The present invention provides a catalyst generating reactant feeder; A hermetic reaction tube having one end connected to the catalyst generating reactant supply and made of a microwave inert material; A series of microwave irradiation chambers in which communication holes are formed in portions of both side walls to mount the reaction tubes, and magnetrons are mounted and electromagnetic waves are shielded to irradiate microwaves; A catalyst product collector connected to the other end of the reaction tube; Provided is a continuous microwave hydrothermal synthesis apparatus comprising control means for controlling them.

The hermetic reaction tube is generally made of a tube made of Teflon and a worm gear or screw. In order to facilitate the reactivity of the introduced precursor, the reactor is preferably a pipe having an outer diameter of about 50 to 100 mm, which is durable even at high temperature and high pressure.

The magnetron may use, for example, 0.5 to 2.0 kw single mode magnetron. Most preferably a general purpose 1kw single mode magnetron is used. Preferably 3 to 6 sets of magnetrons are used and 3 to 6 sets of microwave irradiation chambers are connected to each other.

The catalyst generating reactant feeder is preferably provided with a constant pressure pump that can be adjusted from 10bar to 50bar, and a relief valve that is adjustable from 10bar to 50bar is installed at the other end of the stirring feeder to adjust the amount of the reactant taken out.

In order to prepare a nanoporous catalyst or a nanoparticle catalyst, a solution containing an organic precursor, a solvent, and various inorganic skeletal sources is supplied to a reaction tube through a semen pump, and the reaction tube is transferred to a series of microwave irradiation chambers. The microwaves are continuously irradiated with magnetron and heated to adjust the reaction rate at an appropriate pumping speed so that the reactants can sufficiently absorb the microwaves. Since this reaction is a high temperature and high pressure reaction, it is preferable to attach a pressure sensor and a temperature sensor inside the reactor in order to detect the danger of the reaction in advance and to achieve appropriate reaction conditions. The catalyst reactant is not significantly affected by acidity but is preferably a basic or neutral solution.

The reaction tube is connected to a motor to provide power for mixing and conveying for smooth catalyst production. The microwave irradiation chamber is provided with an electromagnetic wave shielding plate on the front surface except for the side reaction tube communication hole to block the microwaves that are not absorbed by the reactants.

It is advisable to install a casting table as a control means to detect the temperature of the raw material semen pump and the temperature and pressure of the reactants in the reaction tube and to easily adjust the heating intensity of the microwave.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. These descriptions are intended to illustrate the invention and should not be construed as limiting the protection scope of the invention.

The design criterion was to apply a pressure of 0 ~ 20Kg per cm, and the temperature by microwave was designed from room temperature, which is a general nanocatalyst production temperature, to 200 ° C, and the amount of catalyst injected was 4 Kg per hour. The diameter of the reaction tube was 70 mm and the chamber size of the microwave irradiation chamber was 340 mm × 340 mm × 210 mm, and the array of chambers was placed 4 mm with a 50 mm clearance. In addition, the 50mm part was fitted with a teflon pipe expansion prevention ring and a temperature sensor was attached for stability.

In order to prepare a nanoparticle catalyst, a solution containing an organic precursor, a solvent, and an inorganic skeletal source is supplied to a reaction tube ⑥ through a sperm pump, and the reaction tube ⑥ is transferred to a microwave irradiation chamber ④ to produce a 1 Kw single-mode magnetron. 3. Irradiate the microwave continuously by ③, and heat the reaction rate to adjust the proper pumping speed so that the reactant can absorb the microwave sufficiently. Since this reaction is a high temperature and high pressure reaction, a pressure sensor and a temperature sensor 에 are attached to the reaction tube ⑥ in order to detect the danger of the reaction in advance and to achieve appropriate reaction conditions. By installing the casting board ①, the pressure of the constant pressure pump 의 of the raw material and the temperature and pressure of the reactants in the reaction tube ⑥ were detected so that the heating intensity of the microwave could be easily adjusted. A positive pressure pump 이 adjustable from 10 bar to 50 bar is installed in the catalyst-producing reactant feeder ②, and the other end of the stirring feeder is provided with a relief valve ⑨ adjustable from 10 bar to 50 bar to take out the catalyst reactant discharged to the catalyst collector ⑧. Adjust the amount.

The continuous microwave hydrothermal synthesis apparatus according to the present invention has higher productivity and energy efficiency than the conventional hydrothermal method, and the production apparatus is simple, which saves prototype cost and energy, thereby increasing the competitiveness of the catalyst production price. The product crystallized before and after the reaction of the precursors before the reaction, the product smoothly moves through the semen pump and reaction tube, and it is possible to secure the stability of the operation by attaching the temperature sensor and the pressure sensor, respectively, by installing a casting board The convenience of operation can be achieved by enabling the control of.

Claims (4)

Catalyst generating reactant feeder; A screw-type closed reaction tube of one end connected to the catalyst generating reactant feeder and made of a microwave inert material; A series of microwave irradiation chambers in which communication holes are formed in portions of both side walls to mount the reaction tubes, and magnetrons are mounted and electromagnetic waves are shielded to irradiate microwaves; A catalyst product collector connected to the other end of the reaction tube; And a hydrothermal synthesis apparatus including control means The continuous microwave hydrothermal synthesis apparatus according to claim 1, wherein the screw-type hermetic reaction tube comprises a tube made of Teflon and a screw or a gear. The continuous microwave hydrothermal apparatus according to claim 2, wherein the catalyst is a nanoporous catalyst or a nanoparticulate catalyst. According to claim 3, wherein the magnetron is 3 to 6 sets of 0.5 to 2.0 KW magnetron and the microwave irradiation chamber is composed of 3 to 6 sets, the catalyst generating reactant feeder is adjustable from 10 bar to 50 bar is installed in the reaction tube Continuous microwave hydrothermal synthesis apparatus is attached to the pressure sensor and temperature sensor and the other end of the reaction tube is provided with a relief valve that can be adjusted from 10bar to 50bar

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