CN115178196A - Miniaturized reactor for preparing methanol by carbon dioxide hydrogenation - Google Patents

Abstract

The present application relates to a miniaturized carbon dioxide hydrogenation to methanol reactor, comprising a main reactor, a compressor, a methanol separator, a methanol storage system, and a temperature control system. The main reactor is in the structure of a plate heat exchanger. The carbon dioxide hydrogenation to methanol catalyst is sprayed on the plate surface of the reactant side, and carbon dioxide and hydrogen of 0.5-4 MPa are introduced. The temperature of the heat exchange medium side is 50 ℃. ~400°C heat exchange medium. The plate surface on one side of the reactant is to deposit the catalyst on the surface of the heat exchange plate by ultrasonic spraying, and the repetition times of ultrasonic spraying are 2 to 4 times. The invention has the advantages of portability, miniaturization, high reaction efficiency, strong expansibility, etc., and can be adapted to miniaturized application scenarios and meet application requirements such as distributed energy.

Description

A miniaturized carbon dioxide hydrogenation to methanol reactor

technical field

The application belongs to the technical field of methanol preparation, and in particular relates to a miniaturized carbon dioxide hydrogenation reactor for methanol production.

Background technique

The carbon dioxide hydrogenation to methanol technology is still in the primary application stage and lacks the application scope of commercial promotion. Carbon dioxide hydrogenation to methanol technology can provide a cleaner feedstock than coal, reducing local air and water pollution while reducing global greenhouse gas emissions. Recover hydrogen and syngas from industrial production, increasing product value and reducing carbon emissions.

At present, the research on carbon dioxide hydrogenation to methanol technology at home and abroad mainly focuses on large-scale, high conversion and so on. For the distributed electrolysis of water for hydrogen production and the further synthesis of methanol, there is still a lack of mature carbon dioxide hydrogenation to methanol reactors and reaction systems.

The patent with the application number CN202111411313.2 discloses a method and system for the direct hydrogenation of flue gas, including compressing and boosting the flue gas after desulfurization and refining, so that the boosted flue gas enters a methanol synthesis reactor And react with the green hydrogen produced by electrolysis of water to synthesize methanol. After the reaction, the obtained mixed gas is cooled and separated to obtain liquid methanol and water. The hydrogen is used for ammonia synthesis reaction. After the reaction is completed, the obtained mixed gas is cooled and separated to obtain liquid ammonia and gas components. However, this method cannot adapt to miniaturized application scenarios.

The patent with the application number of CN200920114816.1 discloses a central water-cooled synthetic methanol reactor, including a body, and the body is provided with a cooling water inlet, a synthesis gas inlet, a cooling water outlet, and a product outlet; a catalyst bed support is installed in the body. The catalyst bed support is provided with a catalyst bed; the outer wall of the reactor body, the inner wall of the catalyst bed, above the catalyst bed, and four thermocouples are installed in the center of the catalyst bed; a central cooling water pipe is installed in the body, which One end is located at the cooling water inlet, and the other end is located at the cooling water outlet; a heating jacket is installed outside the body. However, the cooling effect of this invention cannot guarantee a uniform temperature inside the reactor.

The patent with application number CN89106273.4 discloses an improved system of methanol synthesis reactor and the reactor obtained therefrom. The catalyst material is divided into several connected beds, and each bed has a bottom plate and a conical partition, which separates the The space between the plate and the free surface of the next catalyst bed allows the quenching gas to enter its outer circumference, where it is optimally mixed with the part of the reaction gas that passes axially through the upper bed. A tube is introduced into the lower center of the upper bed to define the catalyst of the lower bed from the inside; by introducing two cylindrical walls drilled with holes and concentric with the tube to form a gap with the inner wall of the shell and the outer wall of the tube, the lower The bed or the bed with the greatest pressure differential becomes a bed with substantially radial flow. However, this reactor also cannot achieve a miniaturized design.

SUMMARY OF THE INVENTION

The technical problem to be solved by the present invention is: in order to solve the deficiencies in the prior art that the internal temperature of the reactor is not uniform and the reaction device cannot be miniaturized, a miniaturized carbon dioxide hydrogenation to methanol reactor is provided to meet the requirements of distributed carbon dioxide hydrogenation. Application scenarios of hydrogen to methanol, and ensure high reaction efficiency and methanol selectivity.

The technical solution adopted by the present invention to solve the technical problem is as follows: a miniaturized carbon dioxide hydrogenation reactor for methanol production, including a main reactor, the main reactor is configured as a plate heat exchanger structure, and the plate heat exchanger structure A heat exchange medium is arranged on one side of the plate, and a reactant is arranged on the other side of the plate;

a compressor, the air inlet of the compressor is connected to the reactant outlet side of the main reactor;

a methanol separator, the inlet end of the methanol separator is connected to the outlet side of the compressor for separating methanol;

A methanol storage system is connected to the methanol separator, and the methanol storage system is used for storing the methanol product separated by the methanol separator.

Preferably, in a miniaturized carbon dioxide hydrogenation to methanol reactor of the present invention, the plate surface of the plate heat exchanger structure on the side where the reactants are disposed is sprayed with a carbon dioxide hydrogenation to methanol catalyst for catalyzing carbon dioxide hydrogenation to produce methanol Methanol, to speed up the rate of methanol production.

Preferably, in a miniaturized carbon dioxide hydrogenation to methanol reactor of the present invention, the plate surface of the plate heat exchanger structure on the side where the reactants are arranged is also provided with carbon dioxide and hydrogen, and reacts with the reactants to produce methanol products.

Preferably, in a miniaturized carbon dioxide hydrogenation-to-methanol reactor of the present invention, the pressure values of the carbon dioxide and hydrogen are set at 0.5 to 4 MPa, and in a pressurized state, it is beneficial to speed up the reaction speed and improve the methanol production speed, The working pressure is lower than that of large industrial carbon dioxide hydrogenation reactors.

Preferably, in a miniaturized carbon dioxide hydrogenation to methanol reactor of the present invention, the temperature of the heat exchange medium is set to 50-400°C, and carbon dioxide hydrogenation to methanol releases heat to provide a temperature environment required for the reaction.

Preferably, in a miniaturized carbon dioxide hydrogenation-to-methanol reactor of the present invention, the plate surface of the reactant side of the main reactor adopts the method of ultrasonic spraying to deposit the catalyst on the surface of the heat exchange plate, so that the catalyst and the reactant are formed. more contact.

Preferably, in a miniaturized carbon dioxide hydrogenation-to-methanol reactor of the present invention, the plate surface on the reactant side of the main reactor adopts ultrasonic spraying of the catalyst for 2 to 4 repetitions, and the repeated times of spraying the catalyst is 2 to 4 times. The reactants are fully contacted to speed up the reaction.

Preferably, in a miniaturized carbon dioxide hydrogenation to methanol reactor of the present invention, pure water, or an aqueous ethylene glycol solution with a mass fraction of no more than 50%, pure water or The ethylene glycol aqueous solution with a mass fraction of no more than 50% has a large specific heat capacity, and as a heat exchange medium, it can well provide the heat required for the reaction, and the ethylene glycol aqueous solution can avoid the freezing of the pipeline during shutdown in winter.

Preferably, a miniaturized carbon dioxide hydrogenation to methanol reactor of the present invention further comprises a temperature control system, and the temperature control system is used to control the temperature of the heat exchange medium flowing into the main reactor.

Preferably, in a miniaturized carbon dioxide hydrogenation to methanol reactor of the present invention, the temperature control system is provided with two modes of electric heating and refrigeration, and the two temperature modes are switched to maintain the heat exchange medium at the inlet of the main reactor. The temperature is within ±5°C of the set value.

The beneficial effects of the present invention are:

1. The carbon dioxide hydrogenation to methanol reactor proposed in the present invention has the advantages of portability, miniaturization, and high reaction efficiency, and can be adapted to miniaturized application scenarios to meet application requirements such as distributed energy.

2. The present invention adopts the structure of plate heat exchanger as the main reactor, which has the advantages of strong expansibility and high heat exchange efficiency, and can be designed and assembled according to different capacity requirements, and the temperature fluctuation of the reactor is small, which can maintain a high reaction rate Efficiency and methanol selectivity.

3. The present invention uses ultrasonic spraying to deposit the catalyst on the surface of the plate heat exchanger, which can reduce energy loss and improve overall energy utilization while maintaining high reaction efficiency.

Description of drawings

The technical solutions of the present application will be further described below with reference to the accompanying drawings and embodiments.

FIG. 1 is a schematic diagram of a functional workflow of an embodiment of the present application.

Detailed ways

It should be noted that the embodiments in the present application and the features of the embodiments may be combined with each other in the case of no conflict.

In the description of this application, it should be understood that the terms "center", "portrait", "horizontal", "top", "bottom", "front", "rear", "left", "right", " The orientations or positional relationships indicated by vertical, horizontal, top, bottom, inner, and outer are based on the orientations or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present application and The description is simplified rather than indicating or implying that the referred device or element must have a specific orientation, be constructed and operate in a specific orientation, and therefore should not be construed as limiting the scope of protection of the present application. In addition, the terms "first", "second", etc. are used for descriptive purposes only, and should not be construed as indicating or implying relative importance or implying the number of indicated technical features. Thus, a feature defined as "first", "second", etc., may expressly or implicitly include one or more of that feature. In the description of the present invention, unless otherwise specified, "plurality" means two or more.

In the description of this application, it should be noted that, unless otherwise expressly specified and limited, the terms "installed", "connected" and "connected" should be understood in a broad sense, for example, it may be a fixed connection or a detachable connection Connection, or integral connection; can be mechanical connection, can also be electrical connection; can be directly connected, can also be indirectly connected through an intermediate medium, can be internal communication between two elements. For those of ordinary skill in the art, the specific meanings of the above terms in the present application can be understood through specific situations.

The technical solutions of the present application will be described in detail below with reference to the accompanying drawings and in conjunction with the embodiments.

Example 1

This embodiment provides a miniaturized carbon dioxide hydrogenation to methanol reactor. Referring to FIG. 1 , it includes a main reactor, a compressor, a methanol separator, a methanol storage system, and a temperature control system. The main reactor is configured as a plate heat exchanger structure. , one side of the plate heat exchanger structure is provided with a heat exchange medium, and the other side is provided with a reactant; the carbon dioxide hydrogenation to methanol catalyst is sprayed on the plate surface of one side of the reactant to catalyze carbon dioxide hydrogenation to produce methanol Methanol, accelerate the speed of methanol production, and introduce carbon dioxide and hydrogen at a certain pressure, and pure water with a temperature of 200 °C is introduced into one side of the heat exchange medium as the heat exchange medium. The air inlet of the compressor reacts with the main reactor The outlet side of the methanol separator is connected to the outlet side for compressing the methanol mixture; the inlet end of the methanol separator is connected to the outlet side of the compressor for separating methanol; the methanol storage system is connected to the methanol separator, and the methanol storage system is used to store methanol For the methanol product separated by the separator, the temperature control system is used to control the temperature of the heat exchange medium flowing into the main reactor. The temperature control system is provided with two modes of electric heating and refrigeration, and the two temperature modes are switched to maintain the change of the inlet of the main reactor. The heat medium temperature is within ±5°C of the set value.

In this embodiment, a plate heat exchanger with a cross-sectional size of 1920mm×630mm and a total plate thickness of 700mm is used as the main reactor, and the plate surface on the reactant side adopts the method of ultrasonic spraying to deposit the catalyst on the heat exchange. On the surface of the plate, the number of repetitions of ultrasonic spraying is 3 times, and pure water is introduced into the side of the heat exchange medium for heat exchange. The working pressure of the main reactor is 2MPa and the working temperature is 200℃. Under this working condition, the carbon dioxide hydrogenation to methanol reactor produces an average of 80kg of methanol per hour.

Example 2

The difference from Example 1 is that in this example, a plate heat exchanger with a cross-sectional size of 1115mm × 410mm and a total plate thickness of 500mm is used as the main reactor, and the plate surface on one side of the reactant adopts the method of ultrasonic spraying to deposit the catalyst. On the surface of the heat exchange plate, the ultrasonic spraying is repeated twice, and a 10% ethylene glycol aqueous solution is introduced into one side of the heat exchange medium for heat exchange. The working pressure of the main reactor is 1.5MPa, and the working temperature is 150°C. In this embodiment, the carbon dioxide hydrogenation to methanol reactor produces an average of 45kg of methanol product per hour.

Example 3

Different from Embodiment 1 and Embodiment 2, this embodiment adopts a plate heat exchanger with a cross-sectional size of 580 mm × 228 mm and a total plate thickness of 400 mm as the main reactor, and the plate surface on one side of the reactant adopts ultrasonic spraying. Method The catalyst is deposited on the surface of the heat exchange plate, the repetition times of ultrasonic spraying is 4 times, and pure water is passed through the side of the heat exchange medium for heat exchange. The working pressure of the main reactor is 1MPa, the working temperature is 250℃, and the average production of methanol is 20kg per hour.

Taking the above ideal embodiments according to the present application as inspiration, and through the above descriptions, relevant personnel can make various changes and modifications without departing from the technical idea of the present application. The technical scope of the present application is not limited to the content in the description, and the technical scope must be determined according to the scope of the claims.

Claims (10)

1. a miniaturized carbon dioxide hydrogenation to methanol reactor, is characterized in that: comprise main reactor, and described main reactor is arranged as plate heat exchanger structure, and the side plate surface of described plate heat exchanger structure is provided with The heat exchange medium is provided with reactants on the other side of the plate; a compressor, the air inlet of the compressor is connected to the reactant outlet side of the main reactor; a methanol separator, the inlet end of the methanol separator is connected to the outlet side of the compressor for separating methanol; A methanol storage system is connected to the methanol separator, and the methanol storage system is used for storing the methanol product separated by the methanol separator. 2 . A miniaturized carbon dioxide hydrogenation to methanol reactor according to claim 1 , wherein the plate surface of the plate heat exchanger structure on the side where the reactants are arranged is sprayed with a carbon dioxide hydrogenation to methanol catalyst. 3 . 3 . A miniaturized carbon dioxide hydrogenation to methanol reactor according to claim 2 , characterized in that: the plate surface on the side where the reactants are arranged in the plate heat exchanger structure is also provided with carbon dioxide and hydrogen. 4 . 4 . The miniaturized carbon dioxide hydrogenation-to-methanol reactor according to claim 3 , wherein the pressure values of the carbon dioxide and hydrogen are set to 0.5-4 MPa. 5 . 5 . The miniaturized carbon dioxide hydrogenation to methanol reactor according to claim 2 , wherein the temperature of the heat exchange medium is set at 50-400° C. 6 . 6. A kind of miniaturized carbon dioxide hydrogenation to methanol reactor according to claim 1 is characterized in that: the plate surface of the reactant side of the main reactor adopts the method of ultrasonic spraying to deposit the catalyst on the heat exchange plate surface. 7. A miniaturized carbon dioxide hydrogenation-to-methanol reactor according to claim 6, characterized in that: the number of repetitions of ultrasonic spraying catalyst on the plate surface of the reactant side of the main reactor is 2 to 4 times . 8. A miniaturized carbon dioxide hydrogenation-to-methanol reactor according to any one of claims 1, characterized in that: one side of the heat exchange medium of the main reactor is fed with pure water, or the mass fraction is not more than 50 % ethylene glycol in water. 9. A miniaturized carbon dioxide hydrogenation to methanol reactor according to any one of claims 1, characterized in that: further comprising a temperature control system, the temperature control system is used to control the exchange rate flowing into the main reactor heat medium temperature. 10. A miniaturized carbon dioxide hydrogenation-to-methanol reactor according to claim 9, characterized in that: the temperature control system is provided with two modes of electric heating and refrigeration, switching between the two temperature modes, and maintaining the main The temperature of the heat exchange medium at the inlet of the reactor is within ±5°C of the set value.

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