A reaction system and method for producing methanol by carbon dioxide hydrogenation

Abstract

The application provides a reaction system and method for preparing methanol by carbon dioxide hydrogenation, and the reaction system at least comprises a reactor, wherein the reactor comprises a shell with a cavity, a plurality of reaction column tubes arranged in the shell and used for providing a reaction cavity, and a plurality of baffles arranged in the shell and used for increasing the contact area of the heating gas outside the reaction column tubes; the reaction system for preparing methanol by carbon dioxide hydrogenation utilizes product heat to heat raw material gas, utilizes heat exchange between the tube and the shell to remove heat, does not need an external heating source and a cooling medium, saves energy, and the reaction process temperature is controllable, so that the damage of temperature fluctuation to the reaction equipment is reduced.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of chemical equipment and process technology, and particularly relates to a reaction system and method for preparing methanol by carbon dioxide hydrogenation. BACKGROUND

[0002] In recent years, under the influence of factors such as the "double carbon" goal and hydrogen energy revolution, the technology of preparing methanol by CO2 and H2 has gradually become a carbon utilization approach with great market potential and high attention. The reaction of CO2 and H2 to prepare methanol is an exothermic process, and the reactor thermal management has a significant impact on the reaction results. On the one hand, a higher reaction temperature is conducive to the activation of CO2 to improve the reaction efficiency; on the other hand, since the reaction is a typical thermodynamic equilibrium limited reaction, the increase of temperature not only leads to the decrease of equilibrium conversion, but also increases the selectivity of the byproduct CO, so a moderate reaction temperature should be selected.

[0003] The conventional method adopts a fixed bed reactor with tubes, and removes the reaction heat through boiling water or a steam drum to maintain uniform temperature. Among them, the boiling water removes the reaction heat by using boiling water as a heat removal medium to remove the heat generated by the reaction. In this system, the water is heated to boiling inside or outside the reactor, and then the heat is removed by evaporation. This way has the problem of not easy temperature control, especially when the reaction exothermic amount is large, the reaction temperature may rise sharply out of control, exceeding the appropriate range, and this way also needs to add a steam recovery system, which has the problem of large equipment investment. The steam drum removes the reaction heat by generating steam in the steam drum to remove the reaction heat. In this system, the heat generated by the reactor is used to heat the water in the steam drum to generate steam, and then the heat is removed by discharging the steam. The high-pressure steam generated by the reactor is directly reduced to produce medium-pressure steam, and the energy loss in the middle is very large. The energy is not maximized, which causes energy waste and low energy efficiency. In addition, the internal results of the reactor using the steam drum to remove heat are complex, and the operation process is complex.

[0004] In view of the shortcomings of the conventional method, Poland disclosed a self-heating reactor with catalysts filled in both the tube side and the shell side as early as 1990 (patent number: B1 163570). This design uses countercurrent heat transfer between the tube side and the shell side to achieve self-heating balance. However, due to the countercurrent heat transfer, the temperature difference between the tube side and the shell side is large, which easily causes local overheating or thermal failure. In addition, the catalyst filling in the tube side and the shell side increases the fluid resistance, which leads to an increase in pressure drop. In order to maintain the normal operation of the system, the flow rate of the feed gas needs to be increased. This way not only increases the energy consumption, but also increases the difficulty of temperature distribution control, thereby reducing the operability and running stability of the reactor. SUMMARY

[0005] In view of the shortcomings of the prior art described above, the object of the present invention is to provide a reaction system and method for producing methanol by hydrogenation of carbon dioxide, which is used to solve the problems of low energy efficiency, difficult temperature control, complex process flow and high equipment investment in the reaction system and method for producing methanol by hydrogenation of carbon dioxide in the prior art.

[0006] To achieve the above-mentioned and other related objectives, the present invention provides a reaction system and method for producing methanol by hydrogenating carbon dioxide.

[0007] According to a first aspect of the present invention, there is provided a carbon dioxide hydrogenation to methanol reaction system, the reaction system comprising at least a reactor, the reactor comprising a shell having a chamber, a plurality of reaction tubes arranged in the shell for providing a reaction chamber, and a plurality of baffles arranged in the shell for increasing the contact area of ​​the reaction tubes with the heating gas outside the reaction tubes; a raw gas inlet end and a product gas outlet end are provided on the shell; a first partitioning inlet plate circumferentially fixed in the shell is provided near the raw gas inlet end; a second partitioning outlet plate circumferentially fixed in the shell is provided near the product gas outlet end; a plurality of spaced-apart air flow holes are formed on the first partitioning inlet plate and the second partitioning outlet plate, and the two ends of the plurality of reaction tubes are respectively connected to the air flow holes; one end of the plurality of baffles is fixed on the inner wall of the shell and is located between the first partitioning inlet plate and the second partitioning outlet plate; a heating gas inlet end and a heating gas outlet end are formed on the side wall of the shell, and the plurality of baffles are arranged between the heating gas inlet end and the heating gas outlet end.

[0008] Preferably, the reaction system further comprises a shell bypass pipe connected to the heating gas outlet and the raw gas inlet so as to allow the heating gas to enter the reaction chamber to participate in the reaction.

[0009] Preferably, each of the baffles extends radially inward from the inner wall of the shell to a portion of the reaction tubes passing through the baffle to limit the flow direction of the heating gas.

[0010] Preferably, there are multiple baffles, which are arranged parallel to each other to form a continuous S-shaped airflow channel.

[0011] Preferably, the aspect ratio of the reactor is 4-5; for example, it can be 4-4.2, 4.2-4.4, 4.4-4.6, 4.6-4.8, or 4.8-5.0.

[0012] The aspect ratio of the reactor of the present invention is the ratio of the longitudinal direction to the transverse direction of the reactor.

[0013] Preferably, at least one temperature indicator is provided on the housing.

[0014] Preferably, at least one pressure indicator is provided on the housing.

[0015] Preferably, the reaction system further comprises a heat exchanger for heat exchanging the raw material gas for heating, the heat exchanger comprising a tube bundle for the raw material gas to pass through, a shell layer arranged outside the tube bundle, a heat source chamber formed between the shell layer and the tube bundle for the heat source gas to pass through; the shell layer is formed with a heat source gas outlet end; the product gas outlet end is communicated with the heat source chamber through a product heat recovery channel to heat the raw material gas by using the product gas heat; the raw material gas outlet end of the tube bundle is communicated with the heating gas inlet end of the reactor through a heating gas feeding channel.

[0016] Preferably, the baffle is a 20-25% area intercept baffle.

[0017] The 20-25% area intercept baffle in the present application refers to the percentage of the intercept area of the baffle to the total baffle.

[0018] In some preferred embodiments of the present application, the baffle is 2, 3, 4 or 5.

[0019] The present application can prolong the residence time of the raw material gas in the shell by arranging the baffle, so that the raw material gas is heated more uniformly by the reaction heat generated in the reaction tube, thereby ensuring that the temperature of the raw material gas entering the reaction tube is within the range suitable for catalytic reaction.

[0020] Preferably, the reaction tubes can be arranged at multiple angles, for example, at 30°, 60°, 45° or 90°.

[0021] The arrangement angle of the reaction tube in the present application refers to the included angle between the center line of the adjacent tube and the fluid flow direction in the shell in the geometric arrangement of the reaction tube.

[0022] Preferably, a temperature indicator is arranged on the shell bypass pipeline.

[0023] Preferably, a pressure indicator is arranged on the shell bypass pipeline.

[0024] Preferably, the reaction system further comprises a raw material gas mixing tank, and the raw material gas outlet end of the raw material gas mixing tank is communicated with the raw material gas inlet end of the tube bundle through a raw material gas mixing channel.

[0025] Preferably, a pressure indicator is arranged on the heating gas feeding channel.

[0026] Preferably, a temperature indicator is arranged on the heating gas feeding channel.

[0027] Preferably, a switch valve is arranged on the heating gas feeding channel.

[0028] Preferably, a pressure indicator is arranged on the product heat recovery channel.

[0029] Preferably, the product heat recovery channel is provided with a temperature indicator.

[0030] Preferably, the product heat recovery channel is provided with an on-off valve.

[0031] Preferably, the reaction system further comprises a condenser for condensing the heat source gas and a product condensate collection channel, and the condenser is in communication with the product condensate collection channel between the feed end and the discharge end of the heat source gas.

[0032] Preferably, the reaction system further comprises a raw material gas channel, one end of which is in communication with the gas inlet end of the raw material gas mixing tank.

[0033] Preferably, the raw material gas channel is provided with a pressure gauge.

[0034] Preferably, the raw material gas channel is provided with an on-off valve.

[0035] Preferably, the raw material gas channel is provided with a temperature indicator.

[0036] Preferably, the product condensate collection channel is provided with an on-off valve.

[0037] Preferably, the raw material gas channel is provided with a gas compressor.

[0038] Preferably, the raw material gas channel is provided with an on-off valve.

[0039] Preferably, the raw material gas channel is provided with a pressure gauge.

[0040] Preferably, the gas inlet end of the raw material gas channel is independently connected with a carbon dioxide gas inlet system and a hydrogen gas inlet system.

[0041] Preferably, the carbon dioxide gas inlet system comprises a carbon dioxide gas source and a carbon dioxide gas inlet section pipeline for connecting the carbon dioxide gas source and the gas inlet end of the raw material gas channel; one or more of a first filter, a first on-off valve, a first pressure gauge, a first flow meter and a first check valve are arranged on the carbon dioxide gas inlet section pipeline; the hydrogen gas inlet system comprises a hydrogen gas source and a hydrogen gas inlet end pipeline for connecting the hydrogen gas source and the gas inlet end of the raw material gas channel; one or more of a second filter, a second on-off valve, a second pressure gauge, a second flow meter and a second check valve are arranged on the hydrogen gas inlet section pipeline.

[0042] The carbon dioxide hydrogenation methanol reaction system of the present application can monitor the pressure in the system in real time through the pressure gauge and pressure indicator, and monitor the temperature in the system in real time through the temperature indicator.

[0043] The second aspect of the present application provides a method for producing methanol by carbon dioxide hydrogenation, which is performed by the reaction system for producing methanol by carbon dioxide hydrogenation according to the first aspect of the present application. The method comprises: after the mixed gas of carbon dioxide and hydrogen is preheated, the mixed gas enters the reactor, and the reaction is performed under the action of the catalyst to obtain a reaction product.

[0044] Preferably, the molar ratio of the carbon dioxide to the hydrogen gas is 1: (1-5).

[0045] More preferably, the molar ratio of the carbon dioxide to the hydrogen gas is 1: (2-5); for example, it can be 1: (2-3), 1: (3-4), and / or 1: (4-5).

[0046] In some preferred embodiments of the present application, the molar ratio of the carbon dioxide to the hydrogen gas is 1:3.

[0047] Preferably, the reaction pressure is 60-80 bar.

[0048] Further preferably, the reaction pressure is 65-75 bar.

[0049] Preferably, the pressure drop in the reaction tube is 0.6-0.7 bar.

[0050] Preferably, the reaction catalyst is a copper-based catalyst.

[0051] Further preferably, the reaction catalyst is selected from one or more of Cu-Zn-Al2O3, Cu-ZnO-Al2O3, and Cu-ZnO-ZrO2.

[0052] Preferably, the reaction temperature is 180-280°C.

[0053] More preferably, the reaction temperature can be 180-200°C, 200-220°C, 220-230°C, 230-240°C, 240-250°C, 250-260°C, and 260-280°C.

[0054] Preferably, after the raw material gas is preheated by the heat exchanger, the raw material gas enters the shell of the reactor through the heated gas feeding channel, and then enters the reaction tube through the shell bypass pipeline to form product gas by reaction; the product gas is cooled after passing through the product heat recovery channel to the heat source chamber of the heat exchanger.

[0055] Preferably, the temperature of the mixed gas of carbon dioxide and hydrogen after passing through the heat exchanger is 180-190°C.

[0056] The application preheats the mixed gas of carbon dioxide and hydrogen by using the heat of product gas, so that the temperature of the mixed gas reaches 180-190 DEG C, which realizes the recycling of heat and the preliminary cooling of the mixed gas, and facilitates the subsequent condensation and collection of methanol.

[0057] The raw material gas is preheated by the first heat exchanger, then enters the shell of the reactor through the heated gas feeding channel, and flows between the reaction tubes in the shell. Since the carbon dioxide and hydrogen in the reaction tubes perform exothermic reaction under the action of the catalyst, the temperature in the reaction tubes rises. The gas in the reaction tubes and the gas in the shell perform heat transfer coupling while flowing in parallel, so that the mixed gas of carbon dioxide and hydrogen is further preheated, and the temperature of the mixed gas is 180-220 DEG C after the second preheating.

[0058] Preferably, the ratio of the diameter of the reaction tube to the diameter of the catalyst particle is greater than or equal to 10.

[0059] In the present application, the diameter of the reaction tube can be generally selected from 1-10 cm, including but not limited to 1 cm, 2 cm, 3 cm, 4 cm, 5 cm, 6 cm, 7 cm, 8 cm, 9 cm and 10 cm.

[0060] In the present application, if the diameter of the catalyst particle is too large, the gap between the large particle sizes will be large, which will cause the residence time of the gas in the catalyst to be too short and the reaction to be insufficient. If the diameter of the catalyst particle is too small, the gap will be too small, which will result in a decrease in the heat transfer efficiency and the inability to transfer sufficient reaction heat to the gas in the shell.

[0061] More preferably, the ratio of the diameter of the reaction tube to the diameter of the catalyst particle is 10-50; for example, it can be 10-20, 20-30, 30-40 or 40-50.

[0062] Preferably, the ratio of the gap between the catalyst particles to the total volume of the reaction tube is 0.4-0.5; for example, it can be 0.4-0.41, 0.41-0.42, 0.42-0.43, 0.43-0.44, 0.44-0.45, 0.45-0.46, 0.46-0.47, 0.47-0.48, 0.48-0.49 or 0.49-0.5.

[0063] Preferably, the residence time of the carbon dioxide and hydrogen in the catalyst is 0.5-5 s.

[0064] Further preferably, the residence time of the reaction gas in the catalyst is 0.5-3 s; for example, it can be 0.5-1 s, 1-1.5 s, 1.5-2.0 s, 2.0-2.5 s or 2.5-3 s.

[0065] In the present application, when the reaction gas stays in the catalyst for too short a time, the reaction gas cannot be fully reacted, and the reaction efficiency is low; when the reaction gas stays in the catalyst for too long a time, the local temperature in the reactor is too high, thereby causing thermal mismatch, affecting the stability of the catalyst or causing the occurrence of a side reaction.

[0066] Preferably, the feed flow rate of the carbon dioxide is 1000-10000 kg / h.

[0067] Preferably, the feed flow rate of the hydrogen is 100-1000 kg / h.

[0068] In the present application, the flow rate ratio of carbon dioxide and hydrogen can be adjusted according to the yield requirement of the target product.

[0069] As described above, the carbon dioxide hydrogenation methanol reaction system and method of the present application have the following beneficial effects:

[0070] 1. The carbon dioxide hydrogenation methanol reaction system of the present application realizes the heating of the feed stream by the direct coupling of heat transfer and reaction in the reactor, effectively utilizes the reaction heat, shortens the process, and reduces the investment cost.

[0071] 2. The carbon dioxide hydrogenation methanol reaction system of the present application can effectively utilize the reaction heat and remove the reaction heat generated by the catalytic reaction in the pipe, thereby controlling the reaction temperature distribution in the pipe within the range suitable for methanol generation, effectively avoiding the problem of local overheating caused by too large heat transfer temperature difference, making the reactor evenly heated, reducing the damage risk, and reducing the long-term operation and maintenance cost of the equipment.

[0072] 3. The carbon dioxide hydrogenation methanol reaction system of the present application recycles the heat by heat removal, saves energy consumption; the shell fluid is introduced into the tube for reaction by the transfer pipe, and the reaction heat in the tube is utilized to heat the shell fluid, realizes the in-situ utilization of the reaction heat, and heats the inlet gas by the reaction heat, thereby reducing the requirement for the temperature of the feed gas, not needing additional cooling medium, and saving energy consumption.

[0073] 4. The carbon dioxide hydrogenation methanol reaction system of the present application is simple to operate, and the reaction equipment is not prone to thermal runaway problem, and is suitable for large-scale production in industry. BRIEF DESCRIPTION OF DRAWINGS

[0074] Figure 1 The structure diagram of the reactor in the reaction system for carbon dioxide hydrogenation methanol reaction of the present application is shown.

[0075] Figure 2The structure diagram of the reaction system for the reaction of carbon dioxide hydrogenation to methanol according to the present application is shown.

[0076] Figure 3 The structure diagram of each part in the reaction system for the reaction of carbon dioxide hydrogenation to methanol according to the present application is shown.

[0077] Figure 4 The baffle plate of 25% according to the present application is shown.

[0078] Figure 5 The different arrangement states between the reaction column tubes according to the present application are shown.

[0079] Figure 6 The structure diagram of the boiling water heat removal type reactor in the prior art is shown.

[0080] Figure 1 The reference signs in the drawings are explained as follows: 1 is a reactor, 11 is a reaction column tube, 12 is a shell, 13 is a first baffle plate, 14 is a second baffle plate, 15 is a third baffle plate, 16 is a first separation gas inlet plate, 17 is a second separation gas outlet plate, a is a heating gas inlet, b is a heating gas outlet, 18 is a raw material gas inlet, 19 is a product gas outlet, 2 is a shell bypass pipeline, 21 is a third temperature indicator, 22 is a second pressure indicator, 3 is a heat exchanger, 4 is a raw material gas mixing tank, 5 is a raw material gas passage, 51 is a gas compressor, 52 is a third switch valve, 53 is a third pressure gauge, 6 is a raw material mixed gas passage, 61 is a fourth pressure gauge, 62 is a fourth switch valve, 63 is a first temperature indicator, 7 is a heating gas feeding passage, 71 is a first pressure indicator, 72 is a second temperature indicator, 73 is a fifth switch valve, 8 is a product heat recovery passage, 81 is a fourth pressure indicator, 82 is a seventh temperature indicator, 83 is a sixth switch valve, 9 is a product condensation collection passage, 91 is a seventh switch valve, 10 is a carbon dioxide gas inlet system, 101 is a carbon dioxide gas cylinder, 102 is a first filter, 103 is a first switch valve, 104 is a first pressure gauge, 105 is a first mass flowmeter, 106 is a first check valve, 110 is a hydrogen gas inlet system, 111 is a hydrogen gas cylinder, 112 is a second filter, 113 is a second switch valve, 114 is a second pressure gauge, 115 is a second mass flowmeter, 116 is a second check valve, 121 is a fourth temperature indicator, 122 is a third pressure indicator, 123 is a fifth temperature indicator, and 124 is a sixth temperature indicator.

[0081] Figure 2 The reference signs in the drawings are explained as follows: C1 is a baffle plate reserved area, C2 is a baffle plate truncated area, and C3 is a baffle plate through hole. DETAILED DESCRIPTION

[0082] The present application is herein described, by way of example only, with the assistance of the accompanying drawings in which:

[0083] It must be noted that, as the technology within the skill of the art advances, the combination of elements from different embodiments can be employed to produce further embodiments falling within the scope of the application.

[0084] It is to be understood that the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. It is to be understood that the terms "comprising," "including," "containing," and "having" are to be construed open- ended, i.e., to mean "including, but not limited to," unless explicitly stated otherwise. It is to be understood that the terms "comprise," "comprising," "comprises," "including," "include," "includes," "contain," "containing," "has," "having," or the like are not used in a restrictive sense, but for clarity are used in their open-ended, conventional sense to mean that the described subject matter can include one or more elements or steps.

[0085] Reference will now be made to the drawings, in which Figures 1 to 3 It must be noted that, as the technology within the skill of the art advances, the combination of elements from different embodiments can be employed to produce further embodiments falling within the scope of the application.

[0086] As Figures 1 to 3As shown, a specific reaction system for the hydrogenation of carbon dioxide to methanol reaction is provided, the reaction system at least comprising: a reactor 1, the reactor 1 comprising a shell 12 having a chamber, a plurality of reaction tubes 11 arranged in the shell 12 for providing a reaction chamber, and a plurality of baffles arranged in the shell 12 for increasing the contact area of ​​the outside of the reaction tubes with the hot gas; a raw gas inlet end and a product gas outlet end are provided on the shell 12; a first partitioning inlet plate 16 circumferentially fixed in the shell 12 is provided near the raw gas inlet end; a first partitioning inlet plate 16 circumferentially fixed in the shell 12 is provided near the product gas outlet end A second partitioning gas outlet plate 17 is circumferentially fixed in the shell 12; a plurality of spaced-apart air holes are formed on each of the first partitioning gas inlet plate 16 and the second partitioning gas outlet plate 17, and the two ends of the plurality of reaction tubes 11 are respectively connected to the air holes; one end of the plurality of baffles is fixed on the inner wall of the shell 12 and is located between the first partitioning gas inlet plate 16 and the second partitioning gas outlet plate 17; a heating gas inlet end and a heating gas outlet end are formed on the side wall of the shell 12, and the plurality of baffles are arranged between the heating gas inlet end and the heating gas outlet end. The provision of baffles in the reaction system of the carbon dioxide hydrogenation to methanol reaction of the present application can increase the contact area of ​​the external heat of the reaction tubes 11, and complete the reaction heat in the reaction tubes 11 to fully heat the gas in the shell 12.

[0087] In a Figure 2 and Figure 3 In the specific embodiment shown, the reaction system further includes a shell bypass pipe 2 connected to the heating gas outlet and the raw gas inlet for allowing the heating gas to enter the reaction chamber to participate in the reaction.

[0088] In a Figure 1 In the specific embodiment shown, each of the baffles extends radially inward from the inner wall of the shell to penetrate a portion of the reaction tubes to limit the flow direction of the heating gas.

[0089] In a Figure 1 In the specific embodiment shown, there are multiple baffles, which are arranged parallel to each other to form a continuous S-shaped airflow channel to extend the residence time of the gas in the shell 12 so that it is fully heated by the reaction heat in the reaction tubes 11.

[0090] In a Figure 1 In the specific embodiment shown, the aspect ratio of the reactor 1 is 4-5, so as to prolong the heating time of the reaction gas and the contact time with the catalyst to allow the reaction to proceed fully.

[0091] In a Figure 2 In the specific embodiment shown, at least one temperature indicator is provided on the housing 12 to monitor the gas temperature in the housing 12 in real time.

[0092] In one embodiment as shown in Fig. 1, the shell 12 is provided with a first temperature indicator 11, a second temperature indicator 12 and a third temperature indicator 13. Figure 2 In one embodiment as shown in Fig. 1, the shell 12 is provided with a fourth temperature indicator 121, a fifth temperature indicator 123 and a sixth temperature indicator 124.

[0093] In one embodiment as shown in Fig. 1, the shell 12 is provided with a first pressure indicator 14, a second pressure indicator 15 and a third pressure indicator 16. Figure 2 In one embodiment as shown in Fig. 1, the shell 12 is provided with at least one pressure indicator to monitor the pressure in the shell 12 in real time.

[0094] In one embodiment as shown in Fig. 1, the shell 12 is provided with a first pressure indicator 14, a second pressure indicator 15 and a third pressure indicator 16. Figure 2 In one embodiment as shown in Fig. 1, the shell 12 is provided with a third pressure indicator 122.

[0095] In one embodiment as shown in Fig. 1, the shell 12 is provided with a first pressure indicator 14, a second pressure indicator 15 and a third pressure indicator 16. Figure 2 and Figure 3 In one embodiment as shown in Fig. 1, the reaction system further comprises a heat exchanger 3 for heat exchanging the raw gas to heat the raw gas, the heat exchanger 3 comprising a tube bundle for the raw gas to pass through, a shell layer provided outside the tube bundle, a heat source chamber formed between the shell layer and the tube bundle for the heat source gas to pass through; the shell layer is formed with a heat source gas outlet end; the product gas outlet end is communicated with the heat source chamber through a product heat recovery channel 8 to heat the raw gas by the heat of the product gas; the raw gas outlet end of the tube bundle is communicated with the heating gas inlet end of the reactor through a heating gas inlet channel 7. By providing the heat exchanger 3, the raw gas flowing through the heat exchanger 3 is heated by the heat source to a suitable temperature to participate in the subsequent reaction.

[0096] In one embodiment as shown in Fig. 1, the shell 12 is provided with a first pressure indicator 14, a second pressure indicator 15 and a third pressure indicator 16. Figure 1 In one embodiment as shown in Fig. 1, the shell 12 is provided with a first pressure indicator 14, a second pressure indicator 15 and a third pressure indicator 16.

[0097] In one embodiment as shown in Fig. 1, the shell 12 is provided with a first pressure indicator 14, a second pressure indicator 15 and a third pressure indicator 16. Figure 2 In one embodiment as shown in Fig. 1, the shell 12 is provided with a third temperature indicator 122.

[0098] In one embodiment as shown in Fig. 1, the shell 12 is provided with a first pressure indicator 14, a second pressure indicator 15 and a third pressure indicator 16. Figure 2 In one embodiment as shown in Fig. 1, the shell 12 is provided with a first pressure indicator 14, a second pressure indicator 15 and a third pressure indicator 16.

[0099] In one embodiment as shown in Fig. 1, the shell 12 is provided with a first pressure indicator 14, a second pressure indicator 15 and a third pressure indicator 16. Figure 2 and Figure 3 In one embodiment as shown in Fig. 1, the reaction system further comprises a raw gas mixing tank 4, the raw gas outlet end of the raw gas mixing tank 4 is communicated with the raw gas inlet end of the tube bundle through a raw gas mixing channel 6 to deliver the raw gas mixing to the tube bundle of the heat exchanger 3.

[0100] In one embodiment as shown in Fig. 1, the shell 12 is provided with a first pressure indicator 14, a second pressure indicator 15 and a third pressure indicator 16. Figure 2In the specific embodiment shown, the heating gas feed channel 7 is provided with a first pressure indicator 71 to monitor the pressure in the heating gas feed channel 7.

[0101] In one specific embodiment as shown in FIG. 1, the reaction system further comprises a product heat recovery channel 8, which is in communication with the product outlet of the heating gas feed channel 7 and the product inlet of the product condensing collection channel 9. Figure 2 In the specific embodiment shown, the heating gas feed channel 7 is provided with a second temperature indicator 72 to monitor the temperature of the gas in the heating gas feed channel 7.

[0102] In one specific embodiment as shown in FIG. 1, the reaction system further comprises a product heat recovery channel 8, which is in communication with the product outlet of the heating gas feed channel 7 and the product inlet of the product condensing collection channel 9. Figure 2 In one specific embodiment as shown in FIG. 1, the reaction system further comprises a product heat recovery channel 8, which is in communication with the product outlet of the heating gas feed channel 7 and the product inlet of the product condensing collection channel 9.

[0103] Figure 2 In one specific embodiment as shown in FIG. 1, the reaction system further comprises a product heat recovery channel 8, which is in communication with the product outlet of the heating gas feed channel 7 and the product inlet of the product condensing collection channel 9.

[0104] In one specific embodiment as shown in FIG. 1, the reaction system further comprises a product heat recovery channel 8, which is in communication with the product outlet of the heating gas feed channel 7 and the product inlet of the product condensing collection channel 9. Figure 2 In one specific embodiment as shown in FIG. 1, the reaction system further comprises a product heat recovery channel 8, which is in communication with the product outlet of the heating gas feed channel 7 and the product inlet of the product condensing collection channel 9.

[0105] Figure 2 In one specific embodiment as shown in FIG. 1, the reaction system further comprises a product heat recovery channel 8, which is in communication with the product outlet of the heating gas feed channel 7 and the product inlet of the product condensing collection channel 9.

[0106] In one specific embodiment as shown in FIG. 1, the reaction system further comprises a product heat recovery channel 8, which is in communication with the product outlet of the heating gas feed channel 7 and the product inlet of the product condensing collection channel 9. Figure 2 and Figure 3 In one specific embodiment as shown in FIG. 1, the reaction system further comprises a condenser (not shown in the figure) for condensing the heat source gas and a product condensing collection channel 9, which is in communication between the feed end of the condenser and the product outlet of the heating gas feed channel 7. The product gas is condensed by the condenser to collect methanol.

[0107] In one specific embodiment as shown in FIG. 1, the reaction system further comprises a product heat recovery channel 8, which is in communication with the product outlet of the heating gas feed channel 7 and the product inlet of the product condensing collection channel 9. Figure 2 and Figure 3 In one specific embodiment as shown in FIG. 1, the reaction system further comprises a product heat recovery channel 8, which is in communication with the product outlet of the heating gas feed channel 7 and the product inlet of the product condensing collection channel 9.

[0108] In one specific embodiment as shown in FIG. 1, the reaction system further comprises a product heat recovery channel 8, which is in communication with the product outlet of the heating gas feed channel 7 and the product inlet of the product condensing collection channel 9. Figure 2 In one specific embodiment as shown in FIG. 1, the reaction system further comprises a product heat recovery channel 8, which is in communication with the product outlet of the heating gas feed channel 7 and the product inlet of the product condensing collection channel 9.

[0109] Figure 2 ​​​In the specific embodiment shown, the raw material mixed gas passage 6 is provided with a fourth on-off valve 62 to control the amount of gas passing through in real time by regulating the opening degree of the on-off valve.

[0110] In one specific embodiment as shown in Figure 2 In the specific embodiment shown, the raw material mixed gas passage 6 is provided with a first temperature indicator 63 to monitor the temperature of the gas in the raw material mixed gas passage 6.

[0111] In one specific embodiment as shown in Figure 2 In the specific embodiment shown, the product condensate collection passage 9 is provided with a seventh on-off valve 91 to control the amount of gas passing through in real time by regulating the opening degree of the on-off valve.

[0112] In one specific embodiment as shown in Figure 2 In the specific embodiment shown, the raw material gas passage 5 is provided with a gas compressor 51 to compress the raw material gas to a specific pressure value.

[0113] In one specific embodiment as shown in Figure 2 In the specific embodiment shown, the raw material gas passage 5 is provided with a third on-off valve 52 to control the amount of gas passing through in real time by regulating the opening degree of the on-off valve.

[0114] In one specific embodiment as shown in Figure 2 In the specific embodiment shown, the raw material gas passage 5 is provided with a third pressure gauge 53 to monitor the pressure in the raw material gas passage 5.

[0115] In one specific embodiment as shown in Figure 2 and Figure 3 In the specific embodiment shown, the gas inlet end of the raw material gas passage 5 is respectively and independently connected with a carbon dioxide gas inlet system 10 and a hydrogen gas inlet system 110 to deliver carbon dioxide and hydrogen to the raw material gas passage 5.

[0116] In one specific embodiment as shown in Figure 2 and Figure 3 In the specific embodiment shown, the carbon dioxide gas inlet system 10 includes a carbon dioxide gas source and a carbon dioxide gas inlet section pipeline for connecting the carbon dioxide gas source and the gas inlet end of the raw material gas passage 5 to deliver carbon dioxide to the raw material gas passage 5.

[0117] In one specific embodiment as shown in Figure 2 In the specific embodiment shown, the carbon dioxide gas inlet section pipeline is provided with one or more of a first filter 102, a first on-off valve 103, a first pressure gauge 104, a first flow meter 105, and a first check valve 106.

[0118] In one specific embodiment as shown in Figure 2In the specific embodiment shown, the hydrogen gas inlet system 110 includes a hydrogen gas source and a hydrogen gas inlet section pipeline for connecting the hydrogen gas source and the inlet end of the raw material gas passage 5 to deliver hydrogen gas to the raw material gas passage 5.

[0119] In one specific embodiment as shown in Figure 2 In the specific embodiment shown, one or more of a second filter 112, a second on-off valve 113, a second pressure gauge 114, a second flow meter 115 and a second check valve 116 are arranged on the hydrogen gas inlet section pipeline.

[0120] The filters on the carbon dioxide inlet section pipeline and the hydrogen gas inlet section pipeline are used to filter the raw material gas to remove impurities, the on-off valves and the flow meters are used to regulate and monitor the amount of gas, the pressure gauges are used to monitor the pressure in the pipeline, and the check valves are used to prevent backflow of gas.

[0121] The working principle of the methanol production using the carbon dioxide hydrogenation reaction system of the present application is as follows: carbon dioxide and hydrogen gas are heated and pressurized and then enter the reactor to synthesize methanol under the action of the catalyst, and the reaction equation is: CO2+3H2→CH3OH+H2O.

[0122] The specific reaction system used in the following embodiments of the present application is as shown in Figure 2 Based on the specific reaction system, the process of carbon dioxide hydrogenation to produce methanol is described as follows:

[0123] In use, first, carbon dioxide and hydrogen gas are delivered to the raw material gas passage 5 through the carbon dioxide inlet system 10 and the hydrogen gas inlet system 110, and the carbon dioxide and hydrogen gas are pressurized and compressed by the gas compressor 51 on the raw material gas passage 5 to a pressure of 60-80 bar, then enter the raw material gas mixing tank 4 to mix the carbon dioxide and hydrogen gas thoroughly; the mixed carbon dioxide and hydrogen gas is delivered to the tube layer of the heat exchanger 3 through the raw material gas passage 6, and the mixed gas of carbon dioxide and hydrogen gas is preheated to 180-190℃ using product gas, and then the preheated mixed gas of carbon dioxide and hydrogen gas is delivered to the shell 12 of the reactor through the heated gas inlet passage 7; the mixed gas of carbon dioxide and hydrogen gas is further heated to 180-220℃ by the reaction heat generated in the reaction tube 11 in the shell space, and then enters the reaction tube 11 through the shell bypass pipeline 2 to react; the product after reaction is heated by the mixed gas of carbon dioxide and hydrogen gas in the tube layer of the heat exchanger 3 through the product heat recovery passage 8, and then the product after heat recovery is condensed and collected through the product condensation and collection passage 9 to obtain methanol.

[0124] The application can preheat the mixed gas of carbon dioxide and hydrogen in the heat exchanger 3 by the product gas stream, so as to increase the temperature of the reaction raw gas and reduce the temperature of the product, reduce the energy loss and cost.

[0125] The application can preheat the mixed gas of carbon dioxide and hydrogen in the shell 12 by the heat generated in the reaction column 11, so as to further increase the temperature of the reaction raw gas and make it reach the suitable temperature for the catalytic reaction; in addition, the second preheating can effectively remove the heat generated in the reaction column 11, avoid the occurrence of side reactions due to the too high reaction temperature, and maintain the temperature in the reaction column 11 in the suitable range.

[0126] The carbon dioxide hydrogenation methanol reaction system of the application needs an external heat source to heat the heat exchanger 3 at the initial stage of the reaction, and the heat source can be removed after the reaction is stable, and the subsequent raw gas can be heated by the heat generated by the product and the reaction without an external heat source; in addition, the heat generated in the reaction column 11 can be effectively removed by heating the gas in the shell 12, so no external heat removal device is needed. Compared with the prior art, the energy consumption can be effectively reduced, the reaction temperature can be maintained in the suitable range, the conversion rate of carbon dioxide and the yield of methanol can be improved, and the equipment loss can be saved.

[0127] The carbon dioxide hydrogenation methanol reaction system and method of the application are illustrated by specific examples and comparative examples. The catalyst used in the following examples and comparative examples is Cu-Zn-Al2O3, and the calculation formula of the methanol yield in the following examples and comparative examples is: The calculation formula of the carbon dioxide conversion rate is: .

[0128] Example 1

[0129] Taking the annual output of 1000 tons of methanol as the target, the carbon dioxide hydrogenation methanol reaction system and method of the application are used to synthesize methanol by carbon dioxide hydrogenation, and the tail gas circulation is not considered in this process. The feed amount and reaction conditions of this embodiment 1 are shown in Table 1.

[0130] The specific structure and parameters of the specific carbon dioxide hydrogenation methanol reaction system are as follows: the number of reactor shell side tubes is 121, the shell side diameter is 0.5 m, the tube length is 2 m, the tube diameter is 2 cm, the catalyst particles are uniformly distributed in the tube, the catalyst particle diameter is 2 mm, the height is 4 mm, the mass is 44.5 kg, and the void fraction is 0.41; according to the above tube-shell structure, a subroutine is established to calculate the tube-shell heat transfer coefficient, and the specific heat transfer coefficient calculation can refer to literature 1 (Iordanidis AA. Mathematical Modeling of Catalytic Fixed Bed Reactors. Ph.D. thesis, University of Twente, Enschede, The Netherlands. 2002.5) and literature 2 (McAdams WH. Heat Transmission. New York: McGraw-Hill, 3rd ed. 1954.).

[0131] Comparative Example 1

[0132] Taking an annual output of 1000 tons of methanol as the target, the comparative example 1 adopts a traditional boiling water heat removal reactor. As shown in Table 1, the boiling water heat removal reactor needs to be provided with a water vapor treatment device outside, Figure 4 As shown in Table 1, the boiling water heat removal reactor needs to be provided with a water vapor treatment device outside, Figure 4 When the reactor is used, water needs to be added to the water vapor treatment device, and the water in the water vapor treatment device enters the shell of the reactor, and the water vaporization takes away the reaction heat generated by the catalytic reaction in the reaction tube. After the water vapor is discharged, it is preheated again by the water vapor treatment device, and the preheated water vapor becomes water and enters the water vapor treatment device again, thereby forming a cycle of heating and heat removal.

[0133] The feed amount and reaction conditions of the comparative example 1 are shown in Table 1.

[0134] Example 2

[0135] Taking an annual output of 5000 tons of methanol as the target, the comparative example 1 adopts a traditional boiling water heat removal reactor. As shown in Table 1, the boiling water heat removal reactor needs to be provided with a water vapor treatment device outside,

[0136] Comparative Example 2

[0137] Taking an annual output of 5000 tons of methanol as the target, the comparative example 1 adopts a traditional boiling water heat removal reactor. As shown in Table 1, the boiling water heat removal reactor needs to be provided with a water vapor treatment device outside, Figure 4 The feed amount and reaction conditions of the comparative example 2 are shown in Table 2.

[0138] All the above examples and comparative examples were simulated by Aspen Plus software to simulate the process and to balance the material and energy of the whole process. The operating conditions and material balance table of the reactor module are shown in Table 1 and Table 2.

[0139] Table 1 Operating conditions and material balance table of the examples and comparative examples with the annual output of methanol of 1000 tons

[0140] Item Example 1 Comparative Example 1 Carbon dioxide feed flow rate (kg / h) 1056.24 1056.24 Hydrogen feed flow rate (kg / h) 145.14 145.14 Pre-heating temperature of feed to heat exchanger (°C) 180 220 Temperature range in tube side of reactor (°C) 216-267 152-256 Temperature range in shell side of reactor (°C) 180-216 100-153 Reaction pressure in reactor (bar) 70 70 Flow rate of water in shell side of boiling water heat removal reactor (kg / h) - 1801.53 Temperature of water in shell side of boiling water heat removal reactor (°C) 100 Pressure of water in shell side of boiling water heat removal reactor (bar) - 5 Flow rate of gas into column tube after heating by reaction heat (kg / h) 1201.38 - Temperature of gas into column tube after heating by reaction heat (°C) 216.27 - Flow rate of product gas out of column tube (kg / h) 1201.38 - Temperature of product gas out of column tube (°C) 257.07 - Temperature of methanol in condensation recovery section (°C) 192.83 173.71 Flow rate of methanol in condensation recovery section (kg / h) 175.17 166.70 Annual methanol production (t) 1051.02 1000.2 Methanol production rate (kmol / h) (%) 22.79 21.67 CO2 conversion rate (%) 29.42 22.80

[0141] As can be seen from the data of Example 1 and Comparative Example 1, under the same conditions of feed amount and reaction conditions, when the production target is at least 1000 tons of methanol per year, the boiling water heat removal reactor needs a feed temperature of 220℃, while the feed temperature of the reaction system of the present application can be reduced to 180℃. The boiling water heat removal reactor removes heat through boiling water, resulting in a large temperature change in the tube and shell, which is not conducive to the stable progress of the reaction and is prone to cause side reactions. The reactor shell of the reaction system of the present application does not need to remove heat through boiling water, but controls the temperature distribution in the tube by in-situ heat removal of the reaction heat, so the temperature fluctuation in the tube is small, which is more conducive to the progress of the reaction, so the yield of methanol is higher. The boiling water heat removal reactor is difficult to control the uniform distribution of the tube temperature due to the large degree of shell heat removal, resulting in the conversion of CO2 to CO, so the proportion of CO converted to methanol increases, thereby affecting the conversion rate of CO2, resulting in a decrease in yield.

[0142] Table 2 Operating conditions and material balance table of the examples and comparative examples with the annual output of methanol of 5000 tons

[0143] Item Example 2 Comparative Example 2 Carbon dioxide feed flow rate (kg / h) 6337.41 6337.41 Hydrogen feed flow rate (kg / h) 870.86 870.86 Pre-heating temperature of feed to heat exchanger (°C) 180 226 Temperature range in tube side of reactor (°C) 197-256 173-251 Temperature range in shell side of reactor (°C) 180-197 100-153 Reaction pressure in reactor (bar) 70 70 Flow rate of water in shell side of boiling water heat removal reactor (kg / h) - 4503.82 Temperature of water in shell side of boiling water heat removal reactor (°C) - 100 Pressure of water in shell side of boiling water heat removal reactor (bar) - 5 Flow rate of gas into column tube after heating by reaction heat (kg / h) 7208.27 - Temperature of gas into column tube after heating by reaction heat (°C) 197.71 - Flow rate of product gas out of column tube (kg / h) 7208.27 - Temperature of product gas out of column tube (°C) 256.00 - Temperature of methanol in condensation recovery section (°C) 191.82 173.71 Flow rate of methanol in condensation recovery section (kg / h) 984.73 974.1 Annual methanol production (t) 5908.38 5844.6 Methanol production rate (kmol / h) (%) 21.34 19.94 CO2 conversion rate (%) 28.47 21.53

[0144] As can be seen from the data of Example 2 and Comparative Example 2, when the annual output of methanol is increased from 1000 tons to 5000 tons, under the condition of increased feed amount, the conventional reactor needs a feed temperature of 226℃, while the feed temperature of the reaction system of the present application can be 180℃; and the temperature distribution in the tube and shell of the reactor in the reaction system of the present application is more uniform, reducing the occurrence of the side reaction of the conversion of CO2 to CO, the conversion rate of carbon dioxide is higher, so the yield of methanol is higher.

[0145] Compared with the traditional boiling water heat removal type reactor, the temperature distribution in the tube of the reactor is more uniform, which reduces the damage of reaction overheating to the equipment, reduces the occurrence of side reactions, and improves the conversion rate of carbon dioxide and the yield of methanol. In addition, the carbon dioxide hydrogenation methanol reaction system of the present application does not need external heat source, and eliminates the additional heat transfer medium, controls the temperature distribution in the tube by in-situ heat transfer through reaction heat, promotes the sustainable use of energy, reduces the economic cost of equipment and process operation, and has huge economic benefits.

[0146] The above is only a preferred embodiment of the present application, and is not a limitation on the form and substance of the present application. It should be noted that, for those skilled in the art, without departing from the method of the present application, some improvements and supplements can also be made, which should be considered as the protection scope of the present application. For those skilled in the art, without departing from the spirit and scope of the present application, some changes, modifications and equivalent changes made by using the above disclosed technical content are equivalent embodiments of the present application; at the same time, any equivalent changes, modifications and evolution of the above-mentioned embodiments according to the essential technology of the present application are still within the scope of the technical solutions of the present application.

Claims

1. A carbon dioxide hydrogenation to methanol reaction system, characterized in that, The reaction system at least comprises a reactor (1), the reactor (1) comprises a shell (12) with a cavity, a plurality of reaction column tubes (11) arranged in the shell (12) for providing a reaction cavity, and a plurality of baffles arranged in the shell (12) for increasing the heating gas contact area outside the reaction column tube; the shell (12) is provided with a raw material gas inlet end and a product gas outlet end; a first separation gas inlet plate (16) is arranged near the raw material gas inlet end and is fixed circumferentially in the shell (12); a second separation gas outlet plate (17) is arranged near the product gas outlet end and is fixed circumferentially in the shell (12); a plurality of spaced gas flow holes are formed on the first separation gas inlet plate (16) and the second separation gas outlet plate (17), and both ends of the plurality of reaction column tubes (11) are correspondingly connected to the gas flow holes; one end of the plurality of baffles is fixed to the inner wall of the shell (12) and located between the first separation gas inlet plate (16) and the second separation gas outlet plate (17); the side wall of the shell (12) is formed with a heating gas inlet end and a heating gas outlet end, and the plurality of baffles are arranged between the heating gas inlet end and the heating gas outlet end.

2. The reaction system of claim 1, wherein, The reaction system further comprises a shell bypass pipeline (2) connected to the heating gas outlet end and the raw material gas inlet end for allowing the heating gas to enter the reaction cavity for reaction; and / or each baffle extends radially inward from the inner wall of the shell to part of the reaction column tube to limit the flow direction of the heating gas; and / or the baffles are arranged in parallel and opposite directions to form a continuous s-shaped gas flow channel; and / or the length-diameter ratio of the reactor (1) is 4-5; And / or, the shell (12) is provided with at least one temperature indicator; and / or, the shell (12) is provided with at least one pressure indicator; And / or, the reaction system further comprises a heat exchanger (3) for heat exchange of the raw material gas to heat the raw material gas, the heat exchanger (3) comprises a tube bundle for the raw material gas to pass through, a shell layer arranged outside the tube bundle, and a heat source cavity formed between the shell layer and the tube bundle for the heat source gas to pass through; the shell layer is formed with a heat source gas outlet end; the product gas outlet end is communicated with the heat source cavity through a product heat recovery channel (8) to heat the raw material gas by using the heat of the product gas; the raw material gas outlet end of the tube bundle is communicated with the heating gas inlet end of the reactor through a heating gas inlet channel (7).

3. The reaction system of claim 2, wherein, The baffle is a 20-25% area cut baffle; and / or, the shell bypass pipeline (2) is provided with a temperature indicator; and / or, the shell bypass pipeline (2) is provided with a pressure indicator; and / or, the reaction system further comprises a raw material gas mixing tank (4), a raw material gas outlet end of the raw material gas mixing tank (4) is communicated with a raw material gas inlet end of the tube bundle through a raw material mixing gas passage (6); and / or, the heating gas feeding passage (7) is provided with a pressure indicator; and / or, the heating gas feeding passage (7) is provided with a temperature indicator; and / or, the heating gas feeding passage (7) is provided with an on-off valve; and / or, the product heat recovery passage (8) is provided with a pressure indicator; and / or, the product heat recovery passage (8) is provided with a temperature indicator; and / or, the product heat recovery passage (8) is provided with an on-off valve; and / or, the reaction system further comprises a condenser for condensing the heat source gas and a product condensing and collecting passage (9), a feeding end of the condenser is communicated with a heat source gas outlet end through the product condensing and collecting passage (9).

4. The reaction system of claim 3, wherein, The reaction system further comprises a raw material gas passage (5), one end of the raw material gas passage (5) is communicated with a gas inlet end of the raw material gas mixing tank (4); and / or, the raw material mixing gas passage (6) is provided with a pressure gauge; and / or, the raw material mixing gas passage (6) is provided with an on-off valve; and / or, the raw material mixing gas passage (6) is provided with a temperature indicator; and / or, the product condensing and collecting passage (9) is provided with an on-off valve.

5. The reaction system of claim 4, wherein, The raw material gas passage (5) is provided with a gas compressor; and / or, the raw material gas passage (5) is provided with an on-off valve; and / or, the raw material gas passage (5) is provided with a pressure gauge; and / or, the raw material gas passage (5) is respectively and independently connected with a carbon dioxide gas feeding system (10) and a hydrogen gas feeding system (110).

6. The reaction system of claim 5, wherein, The carbon dioxide gas feeding system (10) comprises a carbon dioxide gas source and a carbon dioxide gas feeding section pipeline, the carbon dioxide gas feeding section pipeline is used for connecting the carbon dioxide gas source and the gas inlet end of the raw material gas passage (5); one or more of a first filter, a first on-off valve, a first pressure gauge, a first flow meter and a first check valve are arranged on the carbon dioxide gas feeding section pipeline; the hydrogen gas feeding system (110) comprises a hydrogen gas source and a hydrogen gas feeding end pipeline, the hydrogen gas feeding section pipeline is used for connecting the hydrogen gas source and the gas inlet end of the raw material gas passage (5); one or more of a second filter, a second on-off valve, a second pressure gauge, a second flow meter and a second check valve are arranged on the hydrogen gas feeding section pipeline.

7. A process for the hydrocarbon of carbon dioxide to methanol, characterized in that, The method is carried out by the carbon dioxide hydrogenation reaction system according to any one of claims 1-6, and the method comprises: after the mixed gas of carbon dioxide and hydrogen is preheated, the mixed gas enters a reactor, and a reaction is carried out under the action of a catalyst to obtain a reaction product.

8. The method of claim 7, wherein, The molar ratio of the carbon dioxide to the hydrogen gas is 1: (1-5); and / or, the reaction pressure is 60-80 bar; and / or, the pressure drop in the reaction tube is 0.6-0.7 bar; and / or, the catalyst is a copper-based catalyst; and / or, the reaction temperature is 180-280℃.

9. The method of claim 7, wherein, The raw material gas is preheated by a heat exchanger and then enters the shell of the reactor through a heated gas feeding channel (7), and then enters the reaction tube (11) through a shell bypass pipeline (2) to react to form product gas; the product gas is cooled after entering the heat source chamber of the heat exchanger (3) through a product heat recovery channel (8); the temperature of the mixed gas of carbon dioxide and hydrogen after passing through the heat exchanger (3) is 180-190℃; and / or, the catalyst is selected from one or more of Cu-Zn-Al2O3, Cu-ZnO-Al2O3, Cu-ZnO-ZrO2.

10. The method of claim 7, wherein, The carbon dioxide and hydrogen gas stay in the catalyst for 0.5-5s; and / or, the feeding flow rate of the carbon dioxide is 1000-10000 kg / h; and / or, the feeding flow rate of the hydrogen gas is 100-1000 kg / h.

Images