Evaluation apparatus and method for sulfur-resistant shift catalysts

Abstract

This invention relates to the field of sulfur-resistant shift conversion, specifically to an evaluation device and method for sulfur-resistant shift conversion catalysts. The device includes a feeding system, a mixing system, a reaction system, and a separation / analysis system. The feeding system includes a feed gas supply unit and a steam supply unit. Along the material flow direction, the reaction system includes a reaction unit A connected in series, having isothermal and adiabatic modes, which can be switched between each other. It also includes a reaction unit B having an adiabatic mode and optionally an isothermal mode. One outlet of the feed gas supply unit is connected to the inlet of reaction unit A via the mixing system, and the other outlet is connected to the inlet of reaction unit B via the mixing system. One outlet of the steam supply unit is connected to the inlet of reaction unit A via the mixing system, and the other outlet is connected to the inlet of reaction unit B via the mixing system.

Description

Technical Field

[0001] This invention relates to the field of sulfur-resistant conversion technology, specifically to an evaluation device and method for sulfur-resistant conversion catalysts. Background Technology

[0002] The sulfur-resistant shift conversion technology involves the reaction of CO and water to produce CO2 and H2. Therefore, this technology can adjust the H2 and CO concentrations in the syngas, providing the necessary feedstock gas for coal chemical projects such as methanol, ammonia synthesis, coal-to-oil, hydrogen production, and coal-to-ethylene glycol processes. It is an important pathway for the efficient utilization of coal. The sulfur-resistant shift conversion catalyst is the core of this technology, while the sulfur-resistant shift conversion catalyst evaluation device is a crucial tool for screening catalysts and providing process data support for industrial plants.

[0003] Existing small-scale evaluation devices for sulfur-resistant shift converters mainly consist of a vaporizer, a mixer, and a reactor. The vaporizer vaporizes the reactant water into steam, the mixer mixes the reactant gas and steam, and the reactor simulates an industrial reactor for the shift reaction. This type of device can simulate the activity changes of the shift catalyst under different conditions such as temperature, pressure, and water-to-gas ratio. However, it has the following shortcomings: First, due to different gasification processes, the composition of the feed gas varies, requiring the preparation of different feed gas for each experiment, which is cumbersome. Second, there are many types of existing reactors, such as isothermal reactors and axial-radial reactors, requiring the construction of multiple different evaluation devices for simulation testing. Third, existing sulfur-resistant shift converter processes typically have 1-3 reaction stages, with different inlet process gas compositions for each stage. Using existing evaluation devices requires multiple evaluation tests to simulate the operation of the catalyst in different shift stages under a single operating condition, resulting in long evaluation times and low efficiency. Summary of the Invention

[0004] The purpose of this invention is to overcome the problems of cumbersome raw material gas preparation, low test and evaluation efficiency, and operating condition fluctuations caused by pressurized sampling in the existing sulfur-resistant shift catalyst evaluation device, and to provide a new sulfur-resistant shift catalyst evaluation device and evaluation method.

[0005] To achieve the above objectives, the first aspect of the present invention provides a sulfur-resistant shift catalyst evaluation device, the device comprising: a feeding system, a mixing system, a reaction system, and a separation / analysis system;

[0006] The feeding system includes: a raw material gas supply unit and a steam supply unit;

[0007] Along the material flow direction, the reaction system includes: a reaction unit A connected in series with isothermal mode and adiabatic mode, wherein the isothermal mode and adiabatic mode of reaction unit A can be switched between each other; and a reaction unit B with adiabatic mode and optionally isothermal mode.

[0008] The separation / analysis system is used to separate and / or analyze the products from the outlets of reaction unit A and / or reaction unit B;

[0009] The outlet of the raw material gas supply unit is connected to the inlet of reaction unit A through a mixing system, and the outlet of the steam supply unit is connected to the inlet of reaction unit B through a mixing system.

[0010] A second aspect of the present invention provides a method for evaluating sulfur-resistant shift catalysts, using the sulfur-resistant shift catalyst evaluation apparatus described in the present invention, the method comprising:

[0011] (1) One path of the raw material gas from the raw material gas supply unit enters the mixing system before the reaction unit A, and the other path, as needed, is mixed with the product material from the outlet of the reaction unit A through the mixing system before the reaction unit B and then enters the reaction unit B.

[0012] (2) One path of steam from the steam supply unit enters the mixing system before reaction unit A, and the other path, as needed, is mixed with the product material from the outlet of reaction unit A through the mixing system before reaction unit B before entering reaction unit B.

[0013] (3) The mixed gas from the mixing system before reaction unit A enters reaction unit A for reaction, and the product material from reaction unit A enters reaction unit B; when the water-gas ratio needs to be adjusted, the product material from reaction unit A is mixed with another steam and / or another raw material gas before entering reaction unit B for reaction.

[0014] (4) The product materials at the outlet of reaction unit A and / or reaction unit B are separated and / or analyzed by the separation / analysis system, and the product materials at the outlet are analyzed.

[0015] Through the above technical solution, the present invention has at least the following beneficial effects:

[0016] (1) The evaluation device of the present invention can simulate most conversion processes, such as the coal-to-methanol process with two adiabatic reactors (“adiabatic + adiabatic”), the coal-to-hydrogen process with isothermal reactor + adiabatic reactor (“isothermal + adiabatic”), conversion processes with a single isothermal furnace and a single adiabatic furnace, and can also simulate some gas inlet processes.

[0017] (2) The evaluation device of the present invention can simulate the reaction process of the commonly used single furnace or two-stage shift furnace, avoid the influence of the difficulty in raw material gas configuration, heat loss and sampling pressure fluctuation of the closed system on the evaluation of catalyst, and truly reflect the performance of catalyst under different process conditions. The accurate simulation of the existing shift process is of positive significance for the development of shift catalysts and the design of new shift processes. Attached Figure Description

[0018] Figure 1 This is a schematic diagram of a sulfur-resistant shift catalyst evaluation device according to one embodiment;

[0019] Figure 2 This is a schematic diagram of the structural unit of reaction unit A in one embodiment;

[0020] Figure 3 This is a schematic diagram of the structure of reaction unit B in one implementation method.

[0021] Explanation of reference numerals in the attached figures

[0022] 1. Balances and water pumps; 2. Raw material gas cylinders

[0023] 4, 5. Vaporizer; 6. Liquid phase heat exchange medium storage tank

[0024] 7. Mixer 15; 8. Reaction Unit A

[0025] 9, 10 Pressure reducer; 11, 12 Gas-liquid separator

[0026] 13, 14 Chromatography Flowmeter

[0027] 17 Reaction Unit B 18 Condenser

[0028] 112 Heat exchange medium pump; 113 External heating insulation layer A

[0029] 114 Heat exchanger coil section A 115 Electric heating wire A

[0030] 116 Reaction tube A 117 Gas phase heat exchange medium inlet pipeline

[0031] 118 Gas phase circulating medium outlet 211 Reaction tube B

[0032] 212 Electric heating wire B 213 External heating insulation layer B Detailed Implementation

[0033] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0034] Unless otherwise stated, directional terms such as "above" and "below" usually refer to the upper and lower parts of the attached diagram.

[0035] In this invention, A and B are merely structural identifiers to distinguish reaction unit A from reaction unit B. For example, the electric heating wire used in reaction unit A is called electric heating wire A, and the electric heating wire used in reaction unit B is called electric heating wire B. Both are conventional electric heating wires in the art and are only used for identification purposes, not as words that limit their structure.

[0036] The first aspect of the present invention provides a sulfur-resistant shift catalyst evaluation device, the device comprising: a feeding system, a mixing system, a reaction system, and a separation and analysis system;

[0037] The feeding system includes: a raw material gas supply unit and a steam supply unit;

[0038] Along the material flow direction, the reaction system includes: a reaction unit A connected in series with isothermal mode and adiabatic mode, wherein the isothermal mode and adiabatic mode of reaction unit A can be switched between each other; and a reaction unit B with adiabatic mode and optionally isothermal mode.

[0039] The separation / analysis system is used to separate and / or analyze the products from the outlets of reaction unit A and / or reaction unit B;

[0040] The outlet of the raw material gas supply unit is connected to the inlet of reaction unit A through a mixing system, and the outlet of the steam supply unit is connected to the inlet of reaction unit B through a mixing system.

[0041] The system described in this invention can simulate commonly used single-furnace or two-stage shift reactor reaction processes, such as the coal-to-methanol process with two-stage adiabatic reactors and the coal-to-hydrogen process with an isothermal reactor and an adiabatic reactor. This evaluation device can also realize the existing shift reactor process with a single adiabatic reactor or a single isothermal reactor, avoiding the problems of complicated feed gas preparation and low experimental evaluation efficiency, improving the efficiency of catalyst evaluation and screening, and realizing accurate simulation of existing shift processes. It has positive significance for the development of shift catalysts and the design of new shift processes.

[0042] According to one embodiment of the present invention, the reaction unit A includes an external heating and insulation layer A, a reaction tube A, and a heat exchange medium supply device A; wherein, the reaction tube A is disposed through the external heating and insulation layer A; the reaction tube A located in the external heating and insulation layer A is configured from top to bottom as a preheating section A, a constant temperature section A filled with a sulfur-resistant conversion catalyst, and an insulation section A; the constant temperature section A of the reaction tube A is covered with at least three heat exchange coil sections A; the heat exchange medium supply device A is independently and circulatedly connected to each heat exchange coil section A.

[0043] According to a preferred embodiment of the present invention, the isothermal section A of the reaction tube A is fitted with at least 3-6 heat exchange coil sections A. This embodiment allows for better temperature control of the isothermal section.

[0044] In this invention, the preheating section A can control the inlet temperature of the raw material gas entering the reaction unit A; the heat preservation section A can control the outlet temperature of the raw material gas exiting the reaction unit A.

[0045] The heating and insulation layer A described in this invention is used in conjunction with the heat exchange medium supply device A. The reaction unit A can be set to isothermal or adiabatic mode according to the actual needs of the evaluation process. Specifically, the heat exchange medium supply device A may or may not supply heat exchange medium to each heat exchange coil section A. Preferably, each heat exchange medium supply device A is equipped with a valve (including an inlet valve and an outlet valve) on the connecting pipeline between the heat exchange medium supply device A and each heat exchange coil section A. The inlet valve refers to the valve installed on the connecting pipeline between the heat exchange medium supply device A and the inlet of each heat exchange coil section A. The valves (exit valves refer to the valves installed on the connecting pipeline between the outlet of each heat exchange coil section A and the heat exchange medium supply device A) can be adjusted in this invention to control the flow rate of the heat exchange medium entering each heat exchange coil section A, thereby controlling the temperature of each section of the catalyst bed and making the temperature difference between each section of the catalyst bed 0-5℃, achieving the function of isothermal mode; or the valves can be closed to make it a closed system, and the reaction tube A is controlled to have no heat conduction with the outside through the external heating insulation layer A, achieving the insulation effect and realizing the function of insulation mode.

[0046] There are no special restrictions on the selection of heat exchange coil section A in this invention. Its material can be selected from materials that are resistant to high temperature and have fast heat transfer, such as copper and aluminum, with copper being preferred.

[0047] The heat exchange medium supply device A described in this invention can be configured and selected as needed. For example, the heat exchange medium supply device A includes a liquid phase heat exchange medium storage tank and a gas phase heat exchange medium storage tank connected in parallel. The liquid phase heat exchange medium storage tank and the gas phase heat exchange medium storage tank can be selected according to the different heat exchange mediums required. The liquid phase heat exchange medium storage tank is independently circulated and connected to each heat exchange coil section A through pipelines. The gas phase heat exchange medium inlet pipeline at the outlet of the gas phase heat exchange medium storage tank is independently circulated and connected to each heat exchange coil section A through pipelines. The liquid phase heat exchange medium circulating out of the heat exchange coil section A can be directly circulated back to the liquid phase heat exchange medium storage tank. The gas phase heat exchange medium circulating out of the heat exchange coil section A flows out through the gas phase circulating medium outlet and is then circulated back to the gas phase heat exchange medium storage tank after conventional treatment in the art. Preferably, the outlet of the liquid phase heat exchange medium storage tank is equipped with a heat exchange medium pump, and preferably, the gas phase heat exchange medium inlet pipeline is equipped with a valve.

[0048] According to a preferred embodiment of the present invention, the external heating insulation layer A includes a cylinder A and a heating element A and a temperature measuring element A located inside the cylinder A, and the reaction tube A penetrates the cylinder A; the heating element A is used to heat the reaction tube A; the temperature measuring element A is used to monitor the temperature difference inside and outside the reaction tube A and / or monitor the temperature difference between the outside of the reaction tube A and the set temperature of the heating element A.

[0049] In this invention, temperature measuring elements A are installed inside and outside the reaction tube A to monitor the temperature difference between the inside and outside of the reaction tube A. Temperature measuring elements A are installed outside the reaction tube A at the corresponding position of the heating element A to monitor the temperature difference between the outside of the reaction tube A and the set temperature of the heating element A.

[0050] In this invention, the heating element A heats the reaction tube A, providing heat for the conversion reaction of the raw material gas in the presence of the catalyst. The temperature measuring element A monitors the temperature inside and outside the reaction tube A, as well as the temperature outside the reaction tube A and the temperature set by the heating element A. The temperature measuring element A can be a conventional component in the art, and the location of the temperature measuring element A is referred to as temperature measuring point A in this invention.

[0051] According to a particularly preferred embodiment of the present invention, each heat exchange coil section A is provided with the heating element A.

[0052] In this invention, during actual use, from top to bottom, when the isothermal section A is filled with a sulfur-resistant shift catalyst, each heat exchange coil section A corresponds to the sulfur-resistant shift catalyst bed in the isothermal section A. The sulfur-resistant shift catalyst bed can be divided into multiple catalyst bed sections. Each heat exchange coil section A is equipped with a heating element A, enabling individual temperature control of each catalyst bed section. Furthermore, the type and flow rate of the heat exchange medium within the heat exchange coil section A can be controlled to achieve the temperature difference between the temperature measurement points A outside each heat exchange coil section A. For example, from top to bottom, the first heat exchange coil section A corresponds to the first catalyst bed in the isothermal section A filled with the sulfur-resistant shift catalyst. Since the reaction is exothermic, the hot spot temperature of the catalyst bed can be reduced by controlling the type and flow rate of the heat exchange medium in heat exchange coil section A. This achieves a temperature difference of 0-5℃ between the temperature measuring points A corresponding to each section of the catalyst bed in reaction tube A, thus achieving the effect of an isothermal reactor. By closing the valves (including inlet and outlet valves) on the connecting pipelines between the heat exchange medium supply device A and each section of heat exchange coil A, making it a closed system, the temperature deviation between the external temperature measuring point A and the external heating element A can be controlled to be less than 5℃, preferably less than 3℃. At this point, it can be considered that there is no heat conduction between the reaction tube A and the external heating element A, achieving the effect of an adiabatic reactor.

[0053] According to a particularly preferred embodiment of the present invention, the heating element A is provided outside the constant temperature section A and the heat preservation section A of the reaction tube A.

[0054] The heating element A described in this invention can be a conventional part or device with heating function in the art, such as an electric heating wire A.

[0055] In this invention, the temperature at different locations of the reaction tube can be controlled by heating elements A set at different positions outside the reaction tube A, and the temperature inside and outside the reaction tube A and the temperature of the catalyst bed can be monitored by heating elements A set at temperature measuring point A, thereby enabling better temperature control.

[0056] The preheating section A described in this invention is for preheating the raw material gas entering the reaction tube A. Preheating can be achieved through heating element A. The preheating section A can be filled with inert materials, including ceramic balls, ceramic rings, silica balls, etc. After the raw material gas is preheated to the reaction temperature, it enters the constant temperature section A. When the constant temperature section A is filled with a sulfur-resistant shift catalyst, the preheated raw material gas undergoes a shift reaction. The reaction products obtained from the shift reaction then enter the insulation section A. The temperature of the insulation section A is controlled by heating element A. The reactants exiting the insulation section A enter the reaction unit B.

[0057] The division of reaction tube A into preheating section A, constant temperature section A, and heat preservation section A in this invention is a conventional choice in the art, and this invention will not elaborate further on this.

[0058] In this invention, the isothermal section A filled with the sulfur-resistant shift catalyst refers to the section A used for filling with the sulfur-resistant shift catalyst. In actual use, the filling or non-filling of the sulfur-resistant shift catalyst can be selected as needed. For example, in a single adiabatic furnace shift process, the isothermal section A of the reaction tube A may not be filled with catalyst.

[0059] The size of the reaction tube A in this invention can be selected according to the specific process. For example, in the pilot stage, the inner diameter of the reaction tube A is 25-35mm (e.g., 25mm, 30mm or 35mm), and the height is 150-200mm (150mm, 170mm or 200mm).

[0060] According to the present invention, reaction unit B can realize an adiabatic mode, and optionally an isothermal mode means that reaction unit B may or may not have an isothermal mode.

[0061] According to the present invention, when reaction unit B has an isothermal mode, in one embodiment, reaction unit B is the same as reaction unit A.

[0062] According to the present invention, when the reaction unit does not have an isothermal mode, the reaction unit B can be a conventional reactor with an adiabatic mode. According to a preferred embodiment of the present invention, the reaction unit B includes an external heating insulation layer B and a reaction tube B; the reaction tube B is disposed through the external heating insulation layer B; the reaction tube B located in the external heating insulation layer B is configured from top to bottom as a preheating section B, a constant temperature section B filled with a sulfur-resistant conversion catalyst, and an insulation section B.

[0063] In this invention, the preheating section B can control the inlet temperature of the material entering the reaction unit B; the heat preservation section B can control the outlet temperature of the material flowing out of the reaction unit B.

[0064] According to a preferred embodiment of the present invention, the external heating insulation layer B includes a cylinder B and a heating element B and a temperature measuring element B located inside the cylinder B, wherein the reaction tube B penetrates the cylinder B; the heating element B is used to heat the reaction tube B; and the temperature measuring element B is used to monitor the temperature difference inside and outside the reaction tube B and / or monitor the temperature difference between the outside of the reaction tube B and the set temperature of the heating element.

[0065] The temperature measuring element B described in this invention is used to monitor the temperature difference between the inside and outside of the reaction tube B by setting the temperature measuring element B inside and outside the reaction tube B, and to monitor the temperature difference between the outside of the reaction tube B and the set temperature of the heating element B by setting the temperature measuring element B outside the reaction tube B at the position of the heating element B.

[0066] In this invention, the reaction tube B is heated by the heating element B, which provides heat for the material to undergo a conversion reaction in the presence of a catalyst. The temperature inside and outside the reaction tube B, as well as the temperature outside the reaction tube B and the temperature set by the heating element B, are monitored by the temperature measuring element B. The temperature measuring element B can be a conventional component in the art, and the position of the temperature measuring element B is referred to as the temperature measuring point B in this invention.

[0067] According to a preferred embodiment of the present invention, the reaction tube B is provided with 3-8 heating elements B (e.g., 3, 4, 5, 6, 7 or 8 segments).

[0068] The heating element B described in this invention can be a conventional part or device with heating function in the art, such as an electric heating wire B.

[0069] In this invention, the temperature at different locations of the reaction tube can be controlled by heating elements B located at different positions outside the reaction tube B, and the temperature inside and outside the reaction tube B and the temperature of the catalyst bed can be monitored by temperature measuring elements B located at temperature measuring points B, so as to better control the temperature.

[0070] In this invention, the temperature at different locations in the reaction tube B can be controlled by heating elements B positioned at different locations outside the reaction tube B. The preheating section B is used to preheat the material entering the reaction tube B, and this preheating can be achieved by heating elements B. The preheating section B can be filled with inert materials, including ceramic balls, ceramic rings, silica balls, etc. After the material is preheated to the reaction temperature, it enters the constant temperature section B. When the constant temperature section B is filled with a sulfur conversion catalyst, the preheated material undergoes a conversion reaction. The constant temperature section B of the reaction tube B is controlled to achieve an adiabatic mode by maintaining a temperature difference of ±3°C between the external temperature of the reaction tube B and the external electric heating wire B. The reaction products obtained from the conversion reaction then enter the insulation section B, and the temperature of the insulation section B is controlled by heating elements B.

[0071] According to a particularly preferred embodiment of the present invention, each of the preheating section, the constant temperature section B and the heat preservation section B of the reaction tube B is provided with a heating element B. For example, the preheating section is provided with one heating element B, the constant temperature section B is provided with 3-6 heating elements B from top to bottom (e.g., 3, 4, 5 or 6), and the heat preservation section B is provided with one heating element B.

[0072] In this invention, the heating elements B installed outside the insulation section B correspond to the sulfur-resistant conversion catalysts filled inside the insulation section B, which can be divided into multiple catalyst beds.

[0073] The division of the reaction tube B into preheating section B, constant temperature section B, and heat preservation section B as described in this invention is a conventional choice in the art, and this invention will not elaborate further on this.

[0074] In this invention, the isothermal section B filled with the sulfur-resistant shift catalyst refers to the section B used for filling with the sulfur-resistant shift catalyst. In actual use, the sulfur-resistant shift catalyst can be selected to be filled or not filled as needed. For example, in a single isothermal furnace shift process, the isothermal section B of the reaction tube B may not be filled with catalyst.

[0075] The size of the reaction tube B in this invention can be selected according to the specific process. For example, in the pilot stage, the inner diameter of the reaction tube B is 30-45mm (e.g., 30mm, 38mm or 45mm), and the height is 60-150mm (60mm, 100mm or 150mm).

[0076] In this invention, depending on the process characteristics, if reaction unit A is selected as either adiabatic or isothermal, and the second reactor is in adiabatic mode, the "isothermal + adiabatic" or "adiabatic + adiabatic" conversion process can be simulated; if the first reactor is not filled with any catalyst, the adiabatic conversion process of a single reactor can be simulated; if the second reactor is not filled with any catalyst, the isothermal conversion process of a single reactor can be simulated.

[0077] The separation / analysis system described in this invention is used to separate and / or analyze the reaction materials at the outlets of reaction unit A and / or reaction unit B. This means that the separation / analysis system can, as needed, select to separate and / or analyze the product material at the outlet of reaction unit A and the product material at the outlet of reaction unit B.

[0078] According to one embodiment of the present invention, along the material flow direction, the separation / analysis system includes, optionally, a condenser, a gas-liquid separator, a pressure reducer, and an analytical device arranged in series. Specifically, reaction unit A and reaction unit B each have a set of optionally connected condensers, gas-liquid separators, pressure reducers, and analytical devices arranged in series at their respective outlets.

[0079] In this invention, the condenser is optional, meaning that the condenser can be installed or not installed as needed.

[0080] The separation / analysis system of this invention enables online segmented sampling, which avoids the influence of sampling analysis on the evaluation results of the two-stage reaction unit evaluation device; after depressurization by a pressure reducer, water vapor separation is fast, and the pressure and sampling volume are controllable, which is conducive to accurate analysis.

[0081] According to a preferred embodiment of the present invention, the separation system is used to analyze the product material at the outlet of reaction unit A, preferably along the material flow direction, and the separation system includes a gas-liquid separator, a pressure reducer and an analytical device arranged in series.

[0082] In this invention, the material exiting reaction unit A can be analyzed online using a separation / analysis system. Based on the results of the online analysis, the material entering reaction unit B for the conversion reaction can be adjusted as needed.

[0083] In this invention, the product material from the outlet of reaction unit A undergoes gas-liquid separation via a gas-liquid separator, and then passes through a pressure reducer for depressurization before entering the analytical equipment for analysis. The pressure reducer allows for rapid water-vapor separation, controllable pressure and sample volume, facilitating accurate analysis, and has negligible impact on subsequent reactions.

[0084] According to a preferred embodiment of the present invention, the separation system is used to separate and analyze the product material at the outlet of reaction unit B, preferably along the material flow direction, and the separation system includes a condenser, a gas-liquid separator, a pressure reducer and an analytical device arranged in series.

[0085] In this invention, the product material from reaction unit B is cooled by a condenser and then enters a gas-liquid separator for gas-liquid separation. The gas phase product is pressure-controlled by a pressure reducer and then vented after being washed with alkali. The liquid phase product is collected and centrally processed, and a portion of the gas phase product can be taken into an analytical device for analysis.

[0086] The structures of the condenser, gas-liquid separator, pressure reducer, and analytical device in this invention are conventional structures in the field, and this invention does not impose any special limitations on them, so they will not be described in detail here. Among them, the analytical device can be a gas chromatograph, which can realize online analysis of the gas in the product material.

[0087] According to a preferred embodiment of the present invention, the raw gas supply unit includes a raw gas storage tank and a flow meter disposed at the outlet of the raw gas storage tank.

[0088] In this invention, the feed gas introduced into the reaction system from the feed gas storage tank is metered and controlled by a flow meter at the outlet of the feed gas storage tank. The feed gas storage tank has a conventional structure in the art, such as a feed gas cylinder; this invention does not have any particular limitation on it. A mass flow meter can be selected as the flow meter. In a preferred embodiment of this invention, the steam supply unit includes a liquid water supply subunit, two independent liquid water metering feed devices connected to the liquid water supply subunit, and a vaporizer disposed at the outlet of the liquid water metering feed device.

[0089] In this invention, liquid water is supplied through a liquid water supply subunit, and the water intake is controlled by a liquid water metering feeder. Then, the liquid water is vaporized to obtain steam through a corresponding vaporizer.

[0090] According to a preferred embodiment of the present invention, the liquid water metering feeding device includes a balance pump and a water pump.

[0091] The liquid water metering device in this invention uses a water pump and a balance to control the water intake.

[0092] The mixing system described in this invention is used to mix the raw gas from one outlet of the raw gas supply unit with the steam from one outlet of the steam supply unit, and optionally mix the material from the outlet of reaction unit A with the raw gas from another outlet of the raw gas supply unit, and optionally mix the material from the outlet of reaction unit A with the steam from another outlet of the steam supply unit. For example, if it is necessary to adjust the water-to-gas ratio, the product material from reaction unit A is mixed with the raw gas from another outlet of the raw gas supply unit and / or the steam from another outlet of the steam supply unit before entering reaction unit B.

[0093] The equipment used in the mixing system described in this invention is not particularly limited and can be a conventional mixer in the art, that is, the mixing system includes a mixer with inlet A and inlet B of reaction unit.

[0094] In this invention, the various systems, units, and devices are connected / interconnected via pipelines. Pumps can be installed on each pipeline as needed, such as a pump at the outlet of the liquid water metering feed device, to improve material transport. Valves can also be installed on each pipeline as needed, such as valves on the connection pipeline between the raw material gas supply unit outlet and the mixing system, and on the connection pipeline between the steam supply unit outlet and the mixing system. Insulation (such as electric insulation) can also be installed on the connecting pipelines as needed, for example, insulation (referred to as pipeline heat tracing) is installed on the connection pipeline between reaction unit A and reaction unit B, and insulation (referred to as pipeline heat tracing) is installed on the connection pipeline between the steam supply unit outlet and reaction unit A, to prevent water vapor condensation in the gas. Each device in the evaluation device of this invention can also be equipped with separate heating devices as needed, allowing for individual temperature control of the corresponding device. For example, separate heating devices are provided for the vaporizer and mixer, ensuring that the liquid water entering the vaporizer is vaporized into steam, and that the material entering reaction unit A and / or reaction unit B is not condensed. The above are merely some exemplary descriptions of this invention, but the invention is not limited thereto.

[0095] A second aspect of the present invention provides a method for evaluating sulfur-resistant shift catalysts, using the sulfur-resistant shift catalyst evaluation apparatus described in the present invention, the method comprising:

[0096] (1) One path of the raw material gas from the raw material gas supply unit enters the mixing system before the reaction unit A, and the other path, as needed, is mixed with the product material from the outlet of the reaction unit A through the mixing system before the reaction unit B and then enters the reaction unit B.

[0097] (2) One path of steam from the steam supply unit enters the mixing system before reaction unit A, and the other path, as needed, is mixed with the product material from the outlet of reaction unit A through the mixing system before reaction unit B before entering reaction unit B.

[0098] (3) The mixed gas from the mixing system before reaction unit A enters reaction unit A for reaction, and the product material from reaction unit A enters reaction unit B; when the water-gas ratio needs to be adjusted, the product material from reaction unit A is mixed with another steam and / or another raw material gas before entering reaction unit B for reaction.

[0099] (4) The product materials at the outlet of reaction unit A and / or reaction unit B are separated and / or analyzed by the separation / analysis system, and the product materials at the outlet are analyzed.

[0100] The present invention uses the sulfur-resistant shift catalyst evaluation device to evaluate sulfur-resistant shift catalysts, which can simulate the commonly used single-furnace or two-stage shift reactor reaction process, avoid the problems of troublesome feed gas preparation and low test evaluation efficiency, improve the efficiency of catalyst evaluation and screening, and realize the accurate simulation of existing shift processes. This has positive significance for the development of shift catalysts and the design of new shift processes.

[0101] In this invention, the reaction tube A of reaction unit A and / or the reaction tube B of reaction unit B can be filled with a sulfur-resistant conversion catalyst according to the specific simulated process.

[0102] When evaluating the sulfur-resistant shift catalyst in this invention, the amount of catalyst loaded can be selected according to the actual process. For example, the height-to-diameter ratio of the sulfur-resistant shift catalyst is 4-8, or the amount of catalyst is 50-100 mL.

[0103] In this invention, when evaluating the sulfur-resistant shift catalyst, the feed gas undergoes a shift reaction in the presence of the sulfur-resistant shift catalyst. Preferably, the temperature of the catalyst bed is 0-600℃, and more preferably 200-450℃.

[0104] In this invention, the catalyst bed can be divided into multiple sections from top to bottom according to the heating element outside the corresponding reaction tube.

[0105] According to one embodiment of the present invention, when evaluating a sulfur-resistant shift catalyst in a simulated single isothermal mode, the evaluation method includes: the reaction tube A of reaction unit A is filled with a sulfur-resistant shift catalyst, while the reaction tube B of reaction unit B is not filled with a sulfur-resistant shift catalyst; the heat exchange medium supply device A, through the opening of the valves, introduces heat exchange medium into the heat exchange coil section A outside the isothermal section A of the reaction tube A, so that the temperature difference between the corresponding temperature measurement points of each section of the catalyst bed in the reaction tube A is 0-5℃, thus achieving the isothermal mode.

[0106] According to one embodiment of the present invention, when evaluating a sulfur-resistant shift catalyst in a simulated single adiabatic mode, the evaluation method for the sulfur-resistant shift catalyst includes: the reaction tube A of reaction unit A is not filled with a sulfur-resistant shift catalyst, and the reaction tube B of reaction tube B is filled with a sulfur-resistant shift catalyst; the isothermal section B of reaction tube B is controlled to achieve an adiabatic mode according to the temperature difference between the external temperature of reaction tube B and the temperature of the corresponding external heating element B being ±3℃.

[0107] According to one embodiment of the present invention, when evaluating the sulfur-resistant shift catalyst in a simulated two-stage furnace hydrogen production process, the evaluation method includes: sulfur-resistant shift catalyst is loaded into reaction tube A of reaction unit A, and sulfur-resistant shift catalyst is loaded into reaction tube B of reaction unit B; heat exchange medium supply device A supplies heat exchange medium to the heat exchange coil section A outside the isothermal section A of reaction tube A through the valve opening, so that the temperature difference between the corresponding temperature measuring points of each catalyst bed section in reaction tube A is 0-5℃, achieving an isothermal mode; the isothermal section B of reaction tube B is controlled according to the temperature difference between the external temperature of reaction tube B and the corresponding external heating element B being ±3℃, achieving an adiabatic mode.

[0108] According to one embodiment of the present invention, when evaluating a sulfur-resistant shift catalyst in a simulated two-stage methanol or syngas production mode, the evaluation method includes: loading a sulfur-resistant shift catalyst into reaction tube A of reaction unit A and loading a sulfur-resistant shift catalyst into reaction tube B of reaction unit B; closing the valve between the heat exchange medium supply device A and reaction unit A, making the heating and insulation layer A of reaction unit A a closed system; controlling the external heating amount of reaction tube A to achieve a temperature deviation of less than 5°C between the external temperature measuring point of reaction tube A and the corresponding external heating element A, thus achieving an adiabatic mode; and controlling the constant temperature section B of reaction tube B according to a temperature difference of ±3°C between the external temperature of reaction tube B and the corresponding external heating element B to achieve an adiabatic mode.

[0109] According to one embodiment of the present invention, when evaluating a sulfur-resistant shift catalyst in a simulated two-stage furnace for methanol or syngas production and a water-to-gas ratio temperature control mode, the evaluation method includes: loading a sulfur-resistant shift catalyst into reaction tube A of reaction unit A and into reaction tube B of reaction unit B; closing the valve between the heat exchange medium supply device A and reaction unit A, making the heating and insulation layer A of reaction unit A a closed system; controlling the external heating of reaction tube A to achieve a temperature deviation of less than 5°C between the external temperature measuring point of reaction tube A and the corresponding heating element A, thus achieving an adiabatic mode; introducing steam into the inlet of reaction unit B through a pipeline connected to the outlet of reaction unit A to adjust the water-to-gas ratio entering reaction unit B, thereby controlling the water-to-gas ratio in the material entering reaction unit B; and controlling the constant temperature section B of reaction tube B according to a temperature difference of ±3°C between the external temperature of reaction tube B and the corresponding external heating element B, thus achieving an adiabatic mode.

[0110] According to one embodiment of the present invention, when evaluating a sulfur-resistant shift catalyst by simulating the adjustment mode of CO content in the feed gas, the evaluation method for the sulfur-resistant shift catalyst includes: filling the reaction tube A of reaction unit A with a sulfur-resistant shift catalyst, and filling the reaction tube B of reaction unit B with a sulfur-resistant shift catalyst; the heat exchange medium supply device A, through the opening of the valves, introduces heat exchange medium into the heat exchange coil section A outside the isothermal section A of the reaction tube A, so that the temperature difference between the corresponding temperature measuring points of each section of the catalyst bed in the reaction tube A is 0-5℃, achieving an isothermal mode; the steam supply unit, connected to the outlet of reaction unit A, supplies steam to the inlet of reaction unit B to adjust the water-gas ratio entering reaction unit B and / or adjust the space velocity in reaction unit A to control the CO content in the material entering reaction unit B; the isothermal section B of reaction tube B is controlled according to the temperature difference between the external temperature of reaction tube B and the corresponding external heating element B within ±3℃ to achieve an adiabatic mode.

[0111] In evaluating the sulfur-resistant shift catalyst, those skilled in the art can set and select the reaction process and conditions according to the actual process. This invention does not impose any special limitations on this; for example, the space velocity of the feed gas can be 2000-5000 h⁻¹. -1 The vaporizer temperature can be 230-280℃, the mass flow rate from the raw gas storage tank to reaction unit A can be 200-300L / h, the water pump flow rate from the raw gas storage tank to reaction unit A can be 2.5-5g / min, the water pump flow rate from the raw gas storage tank to the inlet of reaction unit B can be 1-2g / min, the reaction pressure can be 3-5MPa, and the pipeline heating can be 230-250℃. The above are all exemplary descriptions of the present invention, but the present invention is not limited thereto.

[0112] According to the present invention, it is understood that the raw material gas described in the present invention mainly contains CO and hydrogen, and may also contain a small amount of H2S.

[0113] In this invention, the "water-gas ratio" refers to the ratio of the volumetric flow rate of steam to the volumetric flow rate of dry-based raw material gas, and the water-gas ratio can be set according to the specific process being simulated.

[0114] The heat exchange medium described in this invention can be water, carbon dioxide, air, etc., with air being the preferred and most readily available, and compressed air being the most preferred.

[0115] According to a preferred embodiment of the present invention, such as Figure 1-3 As shown, where Figure 1 This is a schematic diagram of a sulfur-resistant shift catalyst evaluation device. Figure 2 This is a structural diagram of the reaction unit A. Figure 3 This is a schematic diagram of the structure of reaction unit B;

[0116] Specifically, the sulfur-resistant shift catalyst evaluation device includes: a feeding system, a mixing system, a reaction system, and a separation / analysis system; the feeding system includes a feed gas supply unit and a steam supply unit; along the material flow direction, the reaction system includes: a reaction unit A8 with isothermal and adiabatic modes arranged in series, the isothermal and adiabatic modes of reaction unit A can be switched between each other, and a reaction unit B17 with an adiabatic mode; the mixing system includes mixers 7 and 15 with inlets of reaction unit A8 and reaction unit B17, and mixers 7 and 15 are equipped with separate heating devices (not shown); the feed gas supply unit includes a feed gas cylinder 2 and a flow meter 16 located at the outlet of feed gas cylinder 2; one path of the feed gas supply unit is connected to the inlet of reaction unit A8 through mixer 7 in the mixing system, and the other path is connected to reaction unit B17 through mixer 15. The inlet connection of 8; the steam supply unit includes a liquid water supply subunit (not shown), two independent liquid water metering feed devices (water pump and balance 1, 3) connected to the liquid water supply subunit, and vaporizers 4, 5 located at the outlet of the liquid water metering feed device. Vaporizers 4, 5 are equipped with separate heating devices (not shown); one path of the steam supply unit is connected to the inlet of reaction unit A 8 through mixer 7 in the mixing system, and the other path is connected to the inlet of reaction unit B 8 through mixer 15;

[0117] Reaction unit A8 includes an external heating insulation layer A113, a reaction tube A116, and a heat exchange medium supply device A. The reaction tube A116 is installed through the external heating insulation layer A113. The reaction tube A116 in the external heating insulation layer A113 is configured from top to bottom as a preheating section A, a constant temperature section A filled with a sulfur-resistant conversion catalyst, and an insulation section A. The constant temperature section A of the reaction tube A116 is covered with four copper heat exchange coil sections A114. The heat exchange medium supply device A is independently and circulatedly connected to the four heat exchange coil sections A114. The heat exchange medium supply device A includes a liquid phase heat exchange medium storage tank 6 and a gas phase heat exchange medium inlet pipeline 117 connected in parallel. A heat exchange medium pump 112 is installed at the outlet of the liquid phase heat exchange medium storage tank 6. The liquid phase heat exchange medium storage tank 6 is connected to each heat exchange coil section A114 through pipelines. 114 Independent circulation connection; a valve is provided on the gas phase heat exchange medium inlet pipeline 117; the gas phase heat exchange medium storage tank is independently circulated with the four heat exchange coil sections A 114 through the gas phase heat exchange medium pipeline, and the liquid phase heat exchange flowing out of the heat exchange coil section A 114 can be directly circulated back to the liquid phase heat exchange medium storage tank 6; the gas phase heat exchange medium flowing out of the heat exchange coil section A 114 flows out through the gas phase circulation medium outlet 118 and can be circulated back to the gas phase heat exchange medium storage tank (not shown) after conventional treatment in the art; the external heating insulation layer A 113 includes a cylinder A and an electric heating wire A 115 and a temperature measuring element A (not shown) located in the cylinder A; the position where the temperature measuring element A is set is called the temperature measuring point A (not shown); the reaction tube A 116 penetrates the cylinder A; each heat exchange coil section A 114 is provided with an electric heating wire A 115; the reaction tube A An electric heating wire A 115 is provided outside the constant temperature section A and the heat preservation section A of 116; the electric heating wire A 115 is provided with temperature measuring points A inside and outside the reaction tube A 116 at the corresponding position; the inner diameter of the reaction tube A 116 is 30mm and the height is 170mm;

[0118] Reaction unit B 17 includes an external heating insulation layer B 213 and a reaction tube B 211; the reaction tube B 211 is disposed through the external heating insulation layer B 213; the reaction tube B 211 located in the external heating insulation layer B 213 is configured from top to bottom as a preheating section B, a constant temperature section B filled with sulfur-resistant conversion catalyst, and an insulation section B; the external heating insulation layer B 213 includes a cylinder B and an electric heating wire B 212 and a temperature measuring element B located inside the cylinder B; the reaction tube B 211 penetrates the cylinder B; the reaction tube B 211 penetrates the cylinder A; an electric heating wire B 212 is located outside the preheating section and constant temperature section B of the reaction tube B 211; four electric heating wires B 212 are located outside the insulation section B; the position of the temperature measuring element B is called the temperature measuring point B (not shown); the electric heating wire B 212 has temperature measuring points B inside and outside the reaction tube B at the corresponding positions; the reaction tube B The inner diameter of reaction tube B 211 is 38 mm, and the height of reaction tube B 211 is 100 mm.

[0119] The separation / analysis system includes: a gas-liquid separator 11, a pressure reducer 9, and a chromatograph 13 connected in series at the outlet of reaction unit A 8; and a condenser 18, a gas-liquid separator 11, a pressure reducer 10, and a chromatograph 14 connected in series at the outlet of reaction unit B 17.

[0120] According to a preferred embodiment of the present invention, such as Figure 1-3 As shown, the evaluation methods for sulfur-resistant shift catalysts include:

[0121] After the raw material gas from the raw material gas cylinder 2 is depressurized and stabilized, the flow rate is controlled by the mass flow meter 16 and one path enters the pre-mixer 7 of the reaction unit A 8 for mixing. The other path can be mixed with the product material from the outlet of the reaction unit A 8 in the mixer 15 as needed, and then enters the reaction unit B 17.

[0122] The raw water from the liquid water supply subunit is metered and controlled by a balance and water pump 3 before entering the vaporizer 4. In the vaporizer 4, the water turns into steam and enters the mixer 7 to mix evenly with the raw gas and heat it to a certain temperature. The other stream is metered by a balance and water pump 1 as needed before entering the vaporizer 5. After vaporization in the vaporizer 5, it is mixed evenly with the product material from the outlet of reaction unit A8 and heated to a certain temperature before entering the reaction unit B17.

[0123] The mixed gas from mixer 7 enters reaction unit A8, and the product from reaction unit A8 enters reaction unit B17 through an insulated pipeline. If the water-to-gas ratio needs to be adjusted, the product from reaction unit A8 is mixed with another stream of steam through an insulated pipeline before entering reaction unit A8.

[0124] A very small amount of the product from the outlet of reaction unit A8 is passed through gas-liquid separator 11 and pressure reducer 9 to obtain gaseous product which is then analyzed in chromatograph 13 in order to better control the amount of another vapor that needs to be added.

[0125] The product material from reaction unit A8 is cooled by condenser 18 and then enters gas-liquid separators 11 and 12 for gas-liquid separation. The gas phase product is vented after pressure control by back pressure valve and alkaline washing. The liquid phase product is collected and centrally processed. A very small amount of gas phase product is taken into chromatograph 14 for analysis.

[0126] The isothermal section A of reaction tube A 116 can be filled with or not filled with sulfur-resistant shift catalyst as needed; the isothermal section B of reaction tube B 221 can be filled with or not filled with sulfur-resistant shift catalyst as needed.

[0127] The preheating section A, the constant temperature section A, and the heat preservation section A of the reaction tube A 116 are heated by six electric heating wires A 115, and the temperature inside and outside the reaction tube A 116 is monitored by the corresponding temperature measuring point A.

[0128] When reaction unit A is in isothermal mode, compressed air is introduced into the four heat exchange coil sections A114 through the gas phase heat exchange medium inlet pipeline 117. The flow rate of compressed air is controlled by adjusting the opening of the four valves on the connecting pipeline between the gas phase heat exchange medium inlet pipeline 117 and the four heat exchange coil sections A114, thereby controlling the temperature difference between the four catalyst bed sections to 0-5℃, achieving the function of isothermal mode. When reaction unit A is in adiabatic mode, the valves on the connecting pipeline between the gas phase heat exchange medium inlet pipeline 117 and the four heat exchange coil sections A114 are closed, making the external heating insulation layer A a closed system. The heating wire A controls the reaction tube A to have no heat conduction with the outside, achieving the insulation effect, thus realizing the function of adiabatic mode.

[0129] The preheating section B, the constant temperature section B, and the heat preservation section B 211 of the reaction tube B 211 are heated by six electric heating wires B 212, and the temperature inside and outside the reaction tube B 211 is monitored by the corresponding temperature measuring point B.

[0130] The external heating insulation layer B 213 is a closed system. The constant temperature section B of the reaction tube B 211 is controlled to achieve the insulation mode according to the temperature difference of ±3℃ between the external temperature of the reaction tube B 211 and the temperature of the corresponding external electric heating wire B.

[0131] The present invention will be described in detail below through embodiments. In the following embodiments, in Figure 1-3 The process is carried out within the apparatus. In the following embodiments:

[0132] T1-T6 represent the temperatures at the corresponding temperature measurement points A from top to bottom inside reaction tube A;

[0133] t1-t6 represent the temperatures at the corresponding temperature measurement points A from top to bottom within reaction tube B.

[0134] Example 1

[0135] Methods for evaluating sulfur-resistant shift catalysts using a single isothermal simulation:

[0136] Reaction unit A8 simulates an isothermal reactor. The isothermal section A of reaction tube A116 is filled with a sulfur-resistant shift catalyst; the isothermal section B of reaction tube B221 is not filled with a sulfur-resistant shift catalyst; thus simulating a single isothermal furnace shift process.

[0137] The composition of the raw gas, by volume, is: CO 70%, H2S 0.2%, and the balance hydrogen; the circulating medium is compressed air; the reaction conditions are: pressure 4.0 MPa, temperature 230℃, and water-to-gas ratio 1.0.

[0138] The isothermal section A of reaction tube A116 is filled with 100 mL of sulfur-resistant shift catalyst, with a space velocity of 2000 h⁻¹. -1 Reaction tube B is not loaded with catalyst.

[0139] The temperature of vaporizer 4 is set to 280℃, the pipeline heating temperature is set to 230℃, the temperature of mixer 7 is set to 230℃, the mass flow meter 16 between raw material gas cylinder 2 and reaction unit A 8 is set to a gas flow rate of 200L / h, and the water pump is set to 2.68g / min.

[0140] Reaction unit A8: Inlet temperature of reaction tube A116 set to 230℃, outlet temperature of reaction tube A116 set to 230℃, compressed air pressure controlled at 0.2-0.3MPa.

[0141] The opening degree of the four valves on the connecting pipeline between the gas phase heat exchange medium inlet pipeline 117 and the four heat exchange coil section A 114 is controlled according to the catalyst bed temperature. The temperature of the four catalyst bed sections is controlled to be stable at 230±5℃, as shown in Table 1.

[0142] Table 1 Temperature control data for reaction tube A

[0143] In-pipe temperature measurement point T1 T2 T3 T4 T5 T6 Temperature / °C 230.1 230.5 232.0 231.8 231.5 231.2 Valve opening degree / % / 15 50 40 30 /

[0144] Example 2

[0145] Methods for evaluating sulfur-resistant shift catalysts using a single adiabatic mode simulation:

[0146] Reactor A 116 is not loaded with catalyst, and reaction unit B 8 simulates adiabatic conditions to realize a simulated single adiabatic furnace conversion process.

[0147] The composition of the raw gas, by volume, is: CO 70%, H2S 0.2%, and the balance is hydrogen; the circulating medium is none; the reaction conditions are: pressure 4.0 MPa, temperature 250℃, and water-to-gas ratio 1.2.

[0148] Reaction tube B 211 sulfur-resistant shift catalyst loading: 100 mL catalyst, space velocity: 3000 h⁻¹ -1 Reaction tube A 116 is not loaded with catalyst.

[0149] The vaporizer 4 temperature is set to 280℃, the pipeline heating temperature is set to 250℃, the mixer 15 temperature is set to 280℃, the mass flow meter 16 between the raw material gas cylinder 2 and the reaction unit A is set to a gas flow rate of 300L / h, and the water pump is set to 4.82g / min.

[0150] Reaction Unit A8: The external heating temperature of reaction tube A116 is set to 250℃. The four valves on the connecting pipeline between the gas phase heat exchange medium inlet pipeline 117 and the four heat exchange coil tube sections A114 are closed. The reaction tube A116 is controlled to have no heat conduction with the outside through the heating wire A115 to achieve the heat insulation effect.

[0151] Reaction Unit B 17: The inlet and outlet temperatures of reaction tube B 211 are set to 250℃. The external electric heating wire B 212 of reaction tube B 211 is set according to the actual reaction temperature. The constant temperature section of reaction tube B 211 is set according to the difference of ±3℃ between the external temperature of reaction tube B 211 and the temperature of external electric heating wire B 212.

[0152] The specific temperature control data for reaction tube A and reaction tube B are shown in Tables 2 and 3.

[0153] Table 2 Temperature control data for reaction tube A

[0154] In-pipe temperature measurement point T1 T2 T3 T4 T5 T6 Temperature / °C 250.1 250.5 250.3 250.8 250.5 250.1 Valve opening degree / % / 0 0 0 0 /

[0155] Table 3 Temperature control data for reaction tube B

[0156] In-pipe temperature measurement point t1 t2 t3 t4 t5 t6 Temperature / °C 250.0 280.5 483.0 480.8 441.5 251.2

[0157] Example 3

[0158] A method for evaluating sulfur-resistant shift catalysts in a simulated two-stage hydrogen production process:

[0159] Both reaction tubes A 116 and B 211 are filled with sulfur-resistant shift catalyst. Reaction unit A 8 is controlled in isothermal mode, and the adiabatic reaction unit B17 is connected in series to simulate a two-stage furnace hydrogen production process.

[0160] The composition of the raw gas, by volume, is: CO 70%, H2S 0.2%, and the balance hydrogen; the circulating medium is compressed air; the reaction conditions are: pressure 4.0 MPa, temperature 250℃, and water-to-gas ratio 1.0.

[0161] Reaction tube A, 116 catalyst, 100 mL, space velocity: 2000 h⁻¹ -1 ; Reaction tube B 211 is filled with 100mL of catalyst. The gas space velocity can be calculated based on the gas composition at the inlet and outlet of reaction unit A 8, or it can be simulated and tested based on the actual catalyst loading of the industrial plant.

[0162] The vaporizer 4 temperature is set to 280℃, the pipeline heating temperature is set to 250℃, the mixer 7 temperature is set to 250℃, the mass flow meter 16 between the raw material gas cylinder 2 and the reaction unit A 8 is set to a gas flow rate of 200L / h, and the water pump is set to 2.68g / min.

[0163] Reaction Unit A8: The inlet temperature of reaction tube A116 is set to 250℃, the outlet temperature of reaction tube A116 is set to 250℃, the compressed air pressure is controlled at 0.2-0.3MPa, and the opening of the four valves on the connecting pipeline between the gas phase heat exchange medium inlet pipeline 117 and the four heat exchange coil sections A114 is controlled according to the bed temperature, so as to keep the catalyst four-section bed temperature stable at 230±5℃.

[0164] Reaction unit B 17: The inlet and outlet temperatures of reaction tube B 211 are set to 250℃, or can be controlled according to the required inlet temperature. The external electric heating wire B 212 of reaction tube B 211 is set according to the actual reaction temperature. The constant temperature section of reaction tube B 211 is set according to the temperature difference between the external temperature of reaction tube B 211 and the temperature of external electric heating wire B 212 of ±3℃.

[0165] The specific temperature control data for reaction tube A and reaction tube B are shown in Tables 4 and 5.

[0166] Table 4 Temperature control data for reaction tube A

[0167] In-pipe temperature measurement point T1 T2 T3 T4 T5 T6 Temperature / °C 250.0 250.1 251.2 250.1 250.5 251.4 Valve opening degree / % / 40 49 46 35 /

[0168] Table 5 Temperature control data for reaction tube B

[0169] In-pipe temperature measurement point t1 t2 t3 t4 t5 t6 Temperature / °C 250.1 260.5 381.0 380.8 301.5 251.2

[0170] Example 4

[0171] Methods for evaluating sulfur-resistant shift catalysts by simulating a two-stage furnace methanol or syngas production model:

[0172] Both reaction tubes A116 and B211 are filled with sulfur-resistant shift catalysts. Reaction unit A8 is controlled in adiabatic mode, and the adiabatic reaction unit B17 is connected in series to simulate a two-stage furnace process for producing methanol or syngas.

[0173] The composition of the raw gas, by volume, is: CO 70%, H2S 0.2%, and the balance is hydrogen; the circulating medium is none; the reaction conditions are: pressure 4.0 MPa, temperature 230℃, and water-to-gas ratio 0.8.

[0174] Reaction tube A, 116 catalyst, 100 mL, space velocity: 2000 h⁻¹ -1 The reaction tube B 211 is filled with 60 mL of catalyst, and the gas space velocity can be calculated based on the gas composition at the inlet and outlet of reaction unit A 8.

[0175] The vaporizer 4 temperature is set to 280℃, the pipeline heating temperature is set to 230℃, the mixer 7 temperature is set to 230℃, the mass flow meter 16 between the raw material gas cylinder 2 and the reaction unit A 8 is set to a gas flow rate of 200L / h, and the water pump is set to 2.68g / min.

[0176] Reaction Unit A8: The external heating temperature of reaction tube A116 is set to 250℃. The four valves on the connecting pipeline between the gas phase heat exchange medium inlet pipeline 117 and the four heat exchange coil tube sections A114 are closed. The reaction tube A116 is controlled to have no heat conduction with the outside through the heating wire A115 to achieve the heat insulation effect.

[0177] Reaction Unit B 17: The inlet and outlet temperatures of reaction tube B 211 are set to 220℃. The external electric heating of reaction tube B 211 is set according to the actual reaction temperature. The constant temperature section of reaction tube B 211 is set according to the temperature difference between the external temperature of reaction tube B 211 and the temperature of external electric heating wire B 212 by ±3℃.

[0178] The specific temperature control data for reaction tube A and reaction tube B are shown in Tables 6 and 7.

[0179] Table 6 Temperature control data for reaction tube A

[0180] In-pipe temperature measurement point T1 T2 T3 T4 T5 T6 Temperature / °C 230.0 291.2 420.0 402.9 361.1 230.8 Valve opening degree / % / 0 0 0 0 /

[0181] Table 7 Temperature control data for reaction tube B

[0182] In-pipe temperature measurement point t1 t2 t3 t4 t5 t6 Temperature / °C 220.0 242.5 246.9 245.2 234.0 221.8

[0183] Example 5

[0184] A method for evaluating sulfur-resistant shift catalysts by simulating two-stage furnace production of methanol or syngas and adjusting the water-gas ratio temperature control mode:

[0185] Both reaction tubes A 116 and B 211 are filled with sulfur-resistant shift catalysts. Reaction unit A 8 is controlled in an adiabatic mode. The adiabatic reaction unit B17 is connected in series to simulate a two-stage furnace process for producing methanol or syngas. Temperature is controlled by adjusting the water-gas ratio.

[0186] The composition of the raw gas, by volume, is: CO 70%, H2S 0.2%, and the balance is hydrogen; the circulating medium is none; the reaction conditions are: pressure 4.0 MPa, temperature 210℃, and water-to-gas ratio 0.3.

[0187] Reaction tube A, 116 catalyst, 100 mL, space velocity: 2000 h⁻¹ -1 To simulate a low water-to-gas ratio gasification process and avoid methanation side reactions, reaction tube B211 is filled with 80 mL of catalyst. The gas hourly velocity can be calculated based on the gas composition at the inlet and outlet of reaction unit A8. The water-to-gas ratio entering reaction unit B17 is adjusted by introducing steam at the inlet of reaction unit B17 to control the gas composition at the outlet of the second phase.

[0188] The vaporizer 4 temperature is set to 280℃, the pipeline heating temperature is set to 230℃, the mixer 7 temperature is set to 230℃, the mass flow meter 16 between raw material gas cylinder 2 and reaction unit A 8 is set to 200L / h, the water pump is set to 2.68g / min, and the water pump between raw material gas cylinder 2 and reaction unit B 17 is set to 1.78g / min.

[0189] Reaction Unit A8: The external heating temperature of reaction tube A116 is set to 250℃. The four valves on the connecting pipeline between the gas phase heat exchange medium inlet pipeline 117 and the four heat exchange coil tube sections A114 are closed. The reaction tube A116 is controlled to have no heat conduction with the outside through the heating wire A115 to achieve the heat insulation effect.

[0190] Reaction Unit B 17: The inlet and outlet temperatures of reaction tube B 211 are set to 220℃. The external electric heating wire B 212 of reaction tube B 211 is set according to the actual reaction temperature. The constant temperature section of reaction tube B 211 is set according to the temperature difference between the external temperature of reaction tube B 211 and the temperature of external electric heating wire B 212 of ±3℃.

[0191] The specific temperature control data for reaction tube A and reaction tube B are shown in Tables 8 and 9.

[0192] Table 8 Temperature control data for reaction tube A

[0193] In-pipe temperature measurement point T1 T2 T3 T4 T5 T6 Temperature / °C 210.0 281.2 340.0 332.9 301.1 210.8 Valve opening degree / % / 0 0 0 0 /

[0194] Table 9 Temperature control data for reaction tube B

[0195] In-pipe temperature measurement point t1 t2 t3 t4 t5 t6 Temperature / °C 220.0 282.5 356.9 345.2 264.0 221.8

[0196] Example 6

[0197] Methods for evaluating sulfur-resistant shift catalysts by simulating CO content adjustment patterns in feed gas:

[0198] Both reaction tubes A116 and B211 are filled with sulfur-resistant shift catalyst. Reaction unit A8 controls and adjusts the feed gas ratio in an isothermal mode. Adiabatic reaction unit B17 is connected in series. Through reaction unit A8, the CO content of the feed gas in the test area is adjusted from 70% to 50%.

[0199] The composition of the raw gas, by volume, is: CO 50%, H2S 0.2%, and the balance is hydrogen; the circulating medium is compressed air; the reaction conditions are: pressure 4.0 MPa and temperature 230℃.

[0200] Reaction tube A, 116 catalyst, 30 mL, space velocity: 2000-5000 h⁻¹ -1The water-to-gas ratio is 0.2-0.6; 100 mL of catalyst is loaded into reaction tube B 211. Its water-to-gas ratio and space velocity can be calculated and adjusted as needed by the mass flow meter 16 and water pump between the raw material gas cylinder 2 and reaction unit B17 to control and adjust the space velocity and gas composition entering reaction unit B17.

[0201] The vaporizer 4 temperature is set to 280℃, the pipeline heating temperature is set to 250℃, the mixer 7 temperature is set to 230℃, and the mass flow meter and water pump between the raw material gas cylinder 2 and the reaction unit A 8 are set according to subsequent needs. The composition of the outlet gas can be reduced from 70% to 50%. Specifically, increasing the water-to-gas ratio and space velocity can increase the composition of the outlet gas. The content of the outlet gas can be controlled at a certain value by using different water-to-gas ratios and space velocities.

[0202] Reaction Unit A8: The inlet temperature of reaction tube A116 is set to 250℃, the outlet temperature of reaction tube A116 is set to 250℃, the compressed air pressure is controlled at 0.2-0.3MPa, and the opening degree of the four valves on the connecting pipeline between the gas phase heat exchange medium inlet pipeline 117 and the four heat exchange coil sections A114 is controlled according to the bed temperature, so as to keep the catalyst four-section bed temperature stable at 230±5℃.

[0203] Reaction unit B17: Set as needed.

[0204] The specific temperature control data for reaction tube A is shown in Table 10.

[0205] Table 10 Temperature control data for reaction tube A

[0206]

[0207]

[0208] Example 7

[0209] The QCS-03S sulfur-resistant shift catalyst produced by Qilu Keli Chemical Research Institute Co., Ltd. was used. Evaluation conditions were as follows: by volume, process gas CO was 70%, H2S was 0.2%, and the balance was hydrogen; pressure was 4.0 MPa; isothermal inlet temperature was 210℃; water-to-gas ratio was 0.4; and space velocity was 3000 h⁻¹. -1 The catalyst loading ratio was 1:2, with 30 mL of catalyst in the isothermal section and 60 mL in the adiabatic section. The outlet temperature of the isothermal section and the inlet temperature of the adiabatic section were controlled to be the same. The water-gas ratio in the adiabatic section was not adjusted and was controlled according to the catalyst bed temperature, as detailed in Tables 14 and 15. The analytical results are shown in Tables 11, 12, and 13.

[0210] Table 11 shows the online analysis results from Example 7.

[0211]

[0212] Table 12 Analysis Results of Manual Sampling from Sampling Bags

[0213]

[0214] Table 13 Online Analysis Results Without Pressure Reducer

[0215]

[0216] Table 14 Temperature control data for reaction tube A

[0217] In-pipe temperature measurement point T1 T2 T3 T4 T5 T6 Temperature / °C 210.1 212.2 211.5 212.8 210.1 210.8 Valve opening degree / % / 23 27 30 25 /

[0218] Table 15 Temperature control data for reaction tube B

[0219] In-pipe temperature measurement point t1 t2 t3 t4 t5 t6 Temperature / °C 210.2 249.5 250.9 251.2 255.0 252.8

[0220] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combining the various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A sulfur-resistant shift catalyst evaluation device, characterized in that, The device includes: a feeding system, a mixing system, a reaction system, and a separation / analysis system; The feeding system includes: a raw material gas supply unit and a steam supply unit; Along the material flow direction, the reaction system includes: a reaction unit A connected in series with isothermal mode and adiabatic mode, wherein the isothermal mode and adiabatic mode of reaction unit A can switch between each other; and a reaction unit B with adiabatic mode and isothermal mode. The separation / analysis system is used to separate and / or analyze the products from the outlets of reaction unit A and / or reaction unit B; The raw material gas supply unit outlet is connected to the inlet of reaction unit A via a mixing system, and to the inlet of reaction unit B via a mixing system; the steam supply unit outlet is connected to the inlet of reaction unit A via a mixing system, and to the inlet of reaction unit B via a mixing system.

2. The apparatus according to claim 1, wherein, The reaction unit A includes an external heating insulation layer A, a reaction tube A, and a heat exchange medium supply device A; The reaction tube A is disposed through the external heating insulation layer A; The reaction tube A located in the external heating insulation layer A is configured from top to bottom as a preheating section A, a constant temperature section A filled with a sulfur-resistant conversion catalyst, and an insulation section A; The isothermal section A of the reaction tube A is equipped with at least three heat exchange coil sections A. The heat exchange medium supply device A is independently and circulatedly connected to each heat exchange coil section A.

3. The apparatus according to claim 2, wherein, The isothermal section A of the reaction tube A is fitted with 3-6 heat exchange coil sections A; Each heat exchange medium supply device A is equipped with a valve on the connecting pipeline between itself and each heat exchange coil section A; and / or The external heating insulation layer A includes a cylinder A and a heating element A and a temperature measuring element A located inside the cylinder A, and the reaction tube A penetrates the cylinder A; The heating element A is used to heat the reaction tube A; The temperature measuring element A is used to monitor the temperature difference inside and outside the reaction tube A and / or monitor the temperature difference between the outside of the reaction tube A and the set temperature of the heating element A.

4. The apparatus according to claim 3, wherein, Each heat exchange coil section A is provided with the heating element A and / or the constant temperature section A and the heat preservation section A of the reaction tube A are provided with the heating element A.

5. The apparatus according to claim 1, wherein, The reaction unit B is the same as the reaction unit A; or The reaction unit B includes an external heating and insulation layer B and a reaction tube B; the reaction tube B is disposed through the external heating and insulation layer B; the reaction tube B located in the external heating and insulation layer B is configured from top to bottom as a preheating section B, a constant temperature section B filled with a sulfur-resistant conversion catalyst, and an insulation section B.

6. The apparatus according to claim 5, wherein, The external heating insulation layer B includes a cylinder B and a heating element B and a temperature measuring element B located inside the cylinder B, and the reaction tube B penetrates the cylinder B; The heating element B is used to heat the reaction tube B; The temperature measuring element B is used to monitor the temperature difference inside and outside the reaction tube B and / or monitor the temperature difference between the outside of the reaction tube B and the set temperature of the heating element B.

7. The apparatus according to claim 6, wherein, The reaction tube B is equipped with 3-8 heating elements B.

8. The apparatus according to claim 7, wherein, Each of the preheating section B, the constant temperature section B, and the heat preservation section B of the reaction tube B is equipped with a heating element B.

9. The apparatus according to claim 1, wherein, Along the material flow direction, the separation / analysis system includes a gas-liquid separator, a pressure reducer, and an analytical device arranged in series.

10. The apparatus according to claim 9, wherein, Along the material flow direction, the separation / analysis system includes a condenser, a gas-liquid separator, a pressure reducer, and an analytical device arranged in series.

11. The apparatus according to claim 9 or 10, wherein, The separation / analysis system is used to analyze the product material at the outlet of reaction unit A; and / or The separation / analysis system is used to separate and analyze the product material at the outlet of reaction unit B; and / or The raw gas supply unit includes a raw gas storage tank and a flow meter located at the outlet of the raw gas storage tank; and / or The steam supply unit includes a liquid water supply subunit, two independent liquid water metering feed devices connected to the liquid water supply subunit, and a vaporizer located at the outlet of the liquid water metering feed device.

12. The apparatus according to claim 11, wherein, The separation / analysis system is used to analyze the product material at the outlet of reaction unit A. Along the material flow direction, the separation / analysis system includes a gas-liquid separator, a pressure reducer, and an analytical device arranged in series; and / or The separation / analysis system is used to separate and analyze the product material at the outlet of reaction unit B. Along the material flow direction, the separation / analysis system includes a condenser, a gas-liquid separator, a pressure reducer, and an analytical device arranged in series. and / or The liquid water metering feeder includes a balance and a water pump.

13. A method for evaluating sulfur-resistant shift catalysts, characterized in that, The method using the sulfur-resistant shift catalyst evaluation apparatus according to any one of claims 1-12 comprises: (1) One path of the raw material gas from the raw material gas supply unit enters the mixing system before the reaction unit A, and the other path, as needed, is mixed with the product material from the outlet of the reaction unit A through the mixing system before the reaction unit B before entering the reaction unit B. (2) One path of steam from the steam supply unit enters the mixing system before reaction unit A; the other path, as needed, mixes with the product material from the outlet of reaction unit A through the mixing system before reaction unit B and then enters reaction unit B. (3) The mixed gas from the mixing system before reaction unit A enters reaction unit A for reaction, and the product from reaction unit A enters reaction unit B; when the water-gas ratio needs to be adjusted, the product from reaction unit A is mixed with another steam and / or another raw material gas before entering reaction unit B for reaction. (4) Separate and / or analyze the products from the outlets of reaction unit A and / or reaction unit B using a separation / analysis system.

14. The method according to claim 13, wherein, The reaction tube A of reaction unit A and / or the reaction tube B of reaction unit B are filled with sulfur-resistant conversion catalyst.

15. The method according to claim 14, wherein, The operating conditions in reaction tube A and reaction tube B each include: The catalyst has a height-to-diameter ratio of 4-8; and / or The catalyst loading is 50-100 mL; and / or The temperature of the catalyst bed is between 0 and 600℃.

16. The method according to claim 15, wherein, The operating conditions in reaction tube A and reaction tube B each include: The temperature of the catalyst bed is 200-450℃.

17. The method according to claim 13, wherein, When evaluating sulfur-resistant shift catalysts using a simulated single isothermal mode: The evaluation method for sulfur-resistant shift catalysts includes: sulfur-resistant shift catalysts are loaded in reaction tube A of reaction unit A, and sulfur-resistant shift catalysts are not loaded in reaction tube B of reaction unit B; heat exchange medium supply device A supplies heat exchange medium to the heat exchange coil section A outside the isothermal section A of reaction tube A through the opening of the valves, so that the temperature difference between the corresponding temperature measurement points of each section of the catalyst bed in reaction tube A is 0-5℃, thus achieving the isothermal mode; When evaluating sulfur-resistant shift catalysts using a simulated single adiabatic mode: The evaluation method for sulfur-resistant shift catalysts includes: the reaction tube A of reaction unit A is not filled with sulfur-resistant shift catalyst, while the reaction tube B of reaction tube B is filled with sulfur-resistant shift catalyst; the isothermal section B of reaction tube B is controlled to achieve an adiabatic mode according to the temperature difference between the external temperature of reaction tube B and the corresponding external heating element B of ±3℃.

18. The method according to claim 13, wherein, When evaluating sulfur-resistant shift catalysts in a simulated two-stage hydrogen production process: The evaluation method for sulfur-resistant shift catalysts includes: sulfur-resistant shift catalysts are loaded into reaction tube A of reaction unit A and sulfur-resistant shift catalysts are loaded into reaction tube B of reaction unit B. The heat exchange medium supply device A supplies heat exchange medium to the heat exchange coil section A, which is installed on the outer side of the isothermal section A of the reaction tube A, through the opening of the valves, so that the temperature difference between the corresponding temperature measurement points of the catalyst bed in each section of the reaction tube A is 0-5℃, thus achieving the isothermal mode. The constant temperature section B of the reaction tube B is controlled to achieve the adiabatic mode by the difference between the external temperature of the reaction tube B and the temperature of the corresponding external heating element B by ±3℃. When evaluating sulfur-resistant shift catalysts using a simulated two-stage methanol or syngas production model: The evaluation method for sulfur-resistant shift catalysts includes: sulfur-resistant shift catalysts are loaded into reaction tube A of reaction unit A and sulfur-resistant shift catalysts are loaded into reaction tube B of reaction unit B. Close the valve between the heat exchange medium supply device A and the reaction unit A, so that the heating and insulation layer A of the reaction unit A is a closed system, control the external heating amount of the reaction tube A, and achieve a temperature deviation of less than 5°C between the external temperature measuring point of the reaction tube A and the corresponding external heating element A, thus achieving the insulation mode. The isothermal section B of the reaction tube B is controlled to achieve the adiabatic mode by keeping the external temperature of the reaction tube B within ±3℃ of the temperature of the corresponding external heating element B.

19. The method according to claim 13, wherein, When evaluating sulfur-resistant shift catalysts using a simulated two-stage furnace for methanol or syngas production and a temperature control mode with adjusted water-to-gas ratio: The evaluation method for sulfur-resistant shift catalysts includes: sulfur-resistant shift catalysts are loaded into reaction tube A of reaction unit A and sulfur-resistant shift catalysts are loaded into reaction tube B of reaction unit B. Close the valve between the heat exchange medium supply device A and the reaction unit A, so that the heating and insulation layer A of the reaction unit A is a closed system, control the external heating amount of the reaction tube A, and achieve a temperature deviation of less than 5°C between the external temperature measuring point of the reaction tube A and the corresponding heating element A, thus achieving the insulation mode. The steam supply unit is connected to the outlet of reaction unit A by a pipeline that supplies steam to the inlet of reaction unit B. This adjusts the water-to-gas ratio entering reaction unit B and controls the water-to-gas ratio in the materials entering reaction unit B. The isothermal section B of the reaction tube B is controlled to achieve the adiabatic mode by keeping the external temperature of the reaction tube B within ±3℃ of the temperature of the corresponding external heating element B.

20. The method according to claim 13, wherein, When evaluating sulfur-resistant shift catalysts by simulating CO content adjustment patterns in feed gas: The evaluation method for sulfur-resistant shift catalysts includes: sulfur-resistant shift catalysts are loaded into reaction tube A of reaction unit A and sulfur-resistant shift catalysts are loaded into reaction tube B of reaction unit B. The heat exchange medium supply device A supplies heat exchange medium to the heat exchange coil section A, which is installed on the outer side of the isothermal section A of the reaction tube A, through the opening of the valves, so that the temperature difference between the corresponding temperature measurement points of the catalyst bed in each section of the reaction tube A is 0-5℃, thus achieving the isothermal mode. The steam supply unit is connected to the outlet of reaction unit A by a pipeline that supplies steam to the inlet of reaction unit B. This adjusts the water-to-gas ratio entering reaction unit B and / or regulates the space velocity in reaction unit A to control the CO content in the material entering reaction unit B. The isothermal section B of the reaction tube B is controlled to achieve the adiabatic mode by keeping the external temperature of the reaction tube B within ±3℃ of the temperature of the corresponding external heating element B.

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