Sulfur-tolerant shift catalyst evaluation device and evaluation method

Abstract

The invention relates to the field of sulfur-tolerant shift, in particular to a sulfur-tolerant shift catalyst evaluation device and method. The device comprises a feeding system, a mixing system, a reaction system and a separation / analysis system, the feeding system comprises a raw material gas supply unit and a steam supply unit; along the material flow direction, the reaction system comprises reaction units A which are connected in series and have an isothermal mode and an adiabatic mode, and the isothermal mode and the adiabatic mode of the reaction units A can be switched; and a reaction unit B having an adiabatic mode, optionally an isothermal mode; one path of an outlet of the raw material gas supply unit is connected with an inlet of the reaction unit A through the mixing system, and the other path is connected with an inlet of the reaction unit B through the mixing system; one outlet of the steam supply unit is connected with the inlet of the reaction unit A through the mixing system, and the other outlet is connected with the inlet of the reaction unit B through the mixing system.

Description

Technical Field

[0001] The present invention relates to the field of sulfur-resistant conversion technology, and in particular to a sulfur-resistant conversion catalyst evaluation device and evaluation method. Background Art

[0002] The conversion reaction involved in the sulfur-tolerant conversion technology is the reaction of CO and water to generate CO2 and H2. Therefore, this technology can adjust the concentration of H2 and CO in the synthesis gas, provide the synthesis feed gas required by coal chemical projects such as methanol, synthetic ammonia, coal-to-oil, hydrogen production, coal-to-ethylene glycol, etc., and is an important way to efficiently utilize coal. The sulfur-tolerant conversion catalyst is the core of the sulfur-tolerant conversion technology, and the sulfur-tolerant conversion catalyst evaluation device is an important tool for screening catalysts and providing process data support for industrial devices.

[0003] The existing small-scale evaluation device for sulfur-resistant conversion mainly includes a vaporizer, a mixer and a reactor, wherein the vaporizer is used to vaporize the reactant water into water vapor, the mixer is used to achieve the mixing of the reaction gas and water vapor, and the reactor simulates the industrial reactor for conversion reaction. This type of device can simulate the activity change of the conversion catalyst under different temperature, pressure, water-gas ratio and other conditions. However, there are the following shortcomings: First, due to different gasification processes and different raw gas compositions, different raw gas needs to be prepared for each test, and it is troublesome to prepare gas separately; second, there are many types of existing reactors, such as isothermal reactors and axial radial reactors, and simulation tests require the construction of multiple different evaluation devices; third, the existing sulfur-resistant conversion process usually has 1-3 reaction sections, and the inlet process gas composition of different conversion sections is different. Using the existing evaluation device, multiple evaluation tests are required to simulate the operation of catalysts in different conversion sections under one working condition, which takes a long time to evaluate and is inefficient. Summary of the invention

[0004] The purpose of the present invention is to overcome the problems of the prior art sulfur-resistant conversion catalyst evaluation device, such as cumbersome raw gas preparation, low test evaluation efficiency, and operating condition fluctuations caused by pressurized sampling, and to provide a new sulfur-resistant conversion catalyst evaluation device and evaluation method.

[0005] In order to achieve the above-mentioned object, the first aspect of the present invention provides a sulfur-resistant shift catalyst evaluation device, which comprises: a feeding system, a mixing system, a reaction system and a separation / analysis system;

[0006] The feed system comprises: a raw gas supply unit and a steam supply unit;

[0007] Along the material flow direction, the reaction system comprises: a reaction unit A having an isothermal mode and an adiabatic mode arranged in series, the isothermal mode and the adiabatic mode of the reaction unit A being capable of switching between the operations; and a reaction unit B having an adiabatic mode and optionally an isothermal mode;

[0008] The separation / analysis system is used to separate and / or analyze the product material at the outlet of reaction unit A and / or reaction unit B;

[0009] Among them, the outlet of the raw gas supply unit is connected to the inlet of the reaction unit A through the mixing system in one way, and is connected to the inlet of the reaction unit B through the mixing system in another way; the outlet of the steam supply unit is connected to the inlet of the reaction unit A through the mixing system in one way, and is connected to the inlet of the reaction unit B through the mixing system in another way.

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

[0011] (1) The raw gas from the raw gas supply unit enters the mixing system before the reaction unit A in one way, and the other way is mixed with the product material at the outlet of the reaction unit A through the mixing system before the reaction unit B according to the needs and then enters the reaction unit B;

[0012] (2) The steam from the steam supply unit enters the mixing system before the reaction unit A in one way, and the steam from the steam supply unit enters the reaction unit B in another way after being mixed with the product material at the outlet of the reaction unit A through the mixing system before the reaction unit B as needed;

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

[0014] (4) Separating and / or analyzing the product materials at the outlet of reaction unit A and / or reaction unit B by a separation / analysis system.

[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 of the conversion processes, such as the coal-to-methanol process with two-stage adiabatic reactors ("adiabatic + adiabatic"), the coal-to-hydrogen process with isothermal reactor + adiabatic reactor ("isothermal + adiabatic"), single isothermal furnace and single adiabatic furnace, etc., and can also simulate some gas intake processes;

[0017] (2) The evaluation device of the present invention can simulate the currently commonly used single-furnace or two-stage conversion furnace reaction process, avoid the impact of raw gas configuration difficulties, heat loss, and closed system sampling pressure fluctuations on catalyst evaluation, and truly reflect the performance of the catalyst under different process conditions. The accurate simulation of the existing conversion process has positive significance for the development of conversion catalysts and the design of new conversion processes. BRIEF DESCRIPTION OF THE DRAWINGS

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

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

[0020] Figure 3 Schematic diagram of the structure of the reaction unit B in one embodiment.

[0021] Description of Reference Numerals

[0022] 1. 3 balances and water pumps 2 raw gas cylinders

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

[0024] 7. 15 mixer 8. reaction unit A

[0025] 9, 10 pressure reducer 11, 12 gas-liquid separator

[0026] 13, 14 chromatogram 16 flow meter

[0027] 17 Reaction unit B 18 Condenser

[0028] 112 heat exchange medium pump 113 external heating insulation layer A

[0029] 114 heat exchange 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 DESCRIPTION

[0033] The endpoints and any values ​​of the ranges disclosed in this article 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 each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0034] Unless otherwise indicated, directional terms such as "upper" and "lower" generally refer to the upper and lower parts of the drawings.

[0035] A and B in the present invention are only used to distinguish the structural identifiers in reaction unit A and 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. They are both conventional electric heating wires in the field and are only used for identification purposes, and are not used as words to limit their structures.

[0036] A 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 feed system comprises: a raw gas supply unit and a steam supply unit;

[0038] Along the material flow direction, the reaction system comprises: a reaction unit A having an isothermal mode and an adiabatic mode arranged in series, the isothermal mode and the adiabatic mode of the reaction unit A being capable of switching between the operations; and a reaction unit B having an adiabatic mode and optionally an isothermal mode;

[0039] The separation / analysis system is used to separate and / or analyze the product material at the outlet of reaction unit A and / or reaction unit B;

[0040] Among them, the outlet of the raw gas supply unit is connected to the inlet of the reaction unit A through the mixing system in one way, and is connected to the inlet of the reaction unit B through the mixing system in another way; the outlet of the steam supply unit is connected to the inlet of the reaction unit A through the mixing system in one way, and is connected to the inlet of the reaction unit B through the mixing system in another way.

[0041] The system described in the present invention can simulate the currently commonly used single-furnace or two-stage conversion furnace reaction processes, such as the coal-to-methanol process of the two-stage adiabatic reactor, the coal-to-hydrogen process of the isothermal reactor + adiabatic reactor, etc. The evaluation device can also realize the conversion process of the currently existing single adiabatic reactor or single isothermal reactor, avoid the problems of cumbersome raw gas preparation and low test evaluation efficiency, improve the efficiency of catalyst evaluation and screening, and realize accurate simulation of existing conversion processes, which has positive significance for the development of conversion catalysts and the design of new conversion processes.

[0042] According to one embodiment of the present invention, the reaction unit A comprises 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 arranged through the external heating and insulation layer A; the reaction tube A located in the external heating and insulation layer A is arranged from top to bottom as a preheating section A, a constant temperature section A loaded with a sulfur-resistant conversion catalyst, and a heat insulation section A; the constant temperature section A of the reaction tube A is outer-coated with at least 3 heat exchange coil sections A; the heat exchange medium supply device A is independently circulated and connected to each heat exchange coil section A.

[0043] According to a preferred embodiment of the present invention, the constant temperature section A of the reaction tube A is covered with at least 3-6 heat exchange coil sections A. The above embodiment can better control the temperature of the constant temperature section.

[0044] The preheating section A in the present invention can control the inlet temperature of the raw gas entering the reaction unit A; the insulation section A can control the outlet temperature of the raw gas flowing out of the reaction unit A.

[0045] The heating and heat-insulating layer A described in the present invention is used in conjunction with the heat exchange medium supply device A, and the reaction unit A can be set to an isothermal mode or an adiabatic mode according to the needs of the actual evaluation process; specifically, the heat exchange medium is introduced into or not introduced into each section of the heat exchange coil section A through the heat exchange medium supply device A. Preferably, the connecting pipelines between the heat exchange medium supply device A and each section of the heat exchange coil section A are each provided with a valve (including an inlet valve and an outlet valve, wherein the inlet valve refers to the connecting pipeline between the heat exchange medium supply device A and the inlet of each section of the heat exchange coil section A). The outlet valve refers to the valve installed on the connecting pipeline between the outlet of each heat exchange coil section A and the heat exchange medium supply device A). In the present invention, the flow rate of the heat exchange medium entering each heat exchange coil section A can be controlled by adjusting the valve opening, thereby controlling the temperature of each section of the catalyst bed, so that the temperature difference of each section of the catalyst bed is 0-5°C, achieving the function of the isothermal mode; or the valve is closed to make it a closed system, and the external heating insulation layer A is used to control the reaction tube A to have no heat conduction with the outside to achieve the insulation effect, so as to realize the function of the adiabatic mode.

[0046] There is no special restriction on the selection of the heat exchange coil section A described in the present invention. The material thereof can be selected from materials that are resistant to high temperatures and have fast heat transfer, such as copper, aluminum, etc., preferably copper.

[0047] The heat exchange medium supply device A described in the present invention can be set and selected according to needs. For example, the heat exchange medium supply device A includes a liquid heat exchange medium storage tank and a gas heat exchange medium storage tank arranged in parallel. The liquid heat exchange medium storage tank and the gas heat exchange medium storage tank can be selected according to the different heat exchange media required, wherein the liquid heat exchange medium storage tank is independently circulated and connected with each section of the heat exchange coil section A through a pipeline; 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 with each section of the heat exchange coil section A through a pipeline, and the liquid heat exchange medium circulating out of the heat exchange coil section A can be directly circulated back to the liquid heat exchange medium storage tank, and the gas-phase heat exchange medium circulating out of the heat exchange coil section A can be circulated back to the gas-phase heat exchange medium storage tank after flowing out through the gas-phase circulating medium outlet and then subjected to conventional treatment in the field; preferably, the outlet of the liquid heat exchange medium storage tank is provided with a heat exchange medium pump, and preferably, the gas-phase heat exchange medium inlet pipeline is provided with a valve.

[0048] According to a preferred embodiment of the present invention, the external heating and 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 passes through 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 between the inside and outside of 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 the present invention, by arranging temperature measuring components A inside and outside the reaction tube A, the purpose of monitoring the temperature difference inside and outside the reaction tube A is achieved. By arranging temperature measuring components A outside the reaction tube A at a position corresponding to the heating component A, the purpose of monitoring the temperature difference between the outside of the reaction tube A and the set temperature of the heating component A is achieved.

[0050] In the present invention, the reaction tube A is heated by the heating element A, which can provide heat for the raw gas to perform a conversion reaction in the presence of the catalyst. The temperature inside and outside the reaction tube A and the temperature outside the reaction tube A and the temperature set by the heating element A are monitored by the temperature measuring element A; the temperature measuring element A can be a conventional component in the field, and the location where the temperature measuring element A is set is called the temperature measuring point A in the present 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 outside.

[0052] In the present invention, in actual use, from top to bottom, when the constant temperature section A is filled with a sulfur-resistant conversion catalyst, each heat exchange coil section A corresponds to the sulfur-resistant conversion catalyst bed filled in the constant temperature section A, and the sulfur-resistant conversion catalyst bed can be divided into multiple catalyst beds. In the present invention, the heating element A is provided outside each heat exchange coil section A, which can realize the temperature control of each catalyst bed separately. At the same time, in the present invention, the type and flow rate of the heat exchange medium in the heat exchange coil section A can be controlled to achieve the temperature difference between the temperature measuring 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 of the constant temperature section A filled with a sulfur-resistant conversion catalyst. Bed, since the conversion reaction is an exothermic reaction, the hot spot temperature of the catalyst bed can be reduced by controlling the type and flow rate of the heat exchange medium in the heat exchange coil section A, so that the temperature difference of the temperature measuring point A corresponding to each section of the catalyst bed in the reaction tube A is 0-5°C, thereby achieving an isothermal reactor effect; the valves (including inlet valves and outlet valves) on the connecting pipelines between the heat exchange medium supply device A and each section of the heat exchange coil section A are closed to make it a closed system, and the temperature deviation between the temperature measuring point A outside the tube and the external heating element A is less than 5°C, preferably less than 3°C, by controlling the external heat of the reaction tube A. At this time, it can be considered that there is no heat conduction between the reaction tube A and the external heating element A, thereby achieving an adiabatic reactor effect.

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

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

[0055] In the present invention, the temperature at different positions of the reaction tube can be controlled by setting the heating element A at different positions outside the reaction tube A, and the temperature of the catalyst bed inside and outside the reaction tube A can be monitored by the heating element A set at the temperature measuring point A, so as to better control the temperature.

[0056] The preheating section A described in the present invention is to preheat the raw gas entering the reaction tube A, and the preheating can be performed by the heating element A. The preheating section A can be filled with inert materials, including ceramic balls, ceramic rings, silica balls, etc.; the raw gas is preheated to the reaction temperature and enters the constant temperature section A. When the constant temperature section A is filled with a sulfur-resistant conversion catalyst, the preheated raw gas undergoes a conversion reaction, and the reaction product obtained by the conversion reaction enters the insulation section A again. The temperature of the insulation section A is controlled by the heating element A outside the insulation section A, and the reaction materials coming out of the insulation section A enter the reaction unit B.

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

[0058] The constant temperature section A loaded with sulfur-resistant shift catalyst in the present invention means that the constant temperature section A is used to load the sulfur-resistant shift catalyst. In actual use, the constant temperature section A may be loaded with or not loaded with the sulfur-resistant shift catalyst according to the needs. For example, when a single adiabatic furnace shift process is used, the constant temperature section A of the reaction tube A may not be loaded with a catalyst.

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

[0060] According to the present invention, the reaction unit B is capable of realizing an adiabatic mode and optionally an isothermal mode, which means that the reaction unit B may have an isothermal mode or may not have an isothermal mode.

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

[0062] According to the present invention, when the reaction unit does not have an isothermal mode, the reaction unit B may be a conventional reactor with an adiabatic mode in the art. 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 arranged through the external heating insulation layer B; the reaction tube B located in the external heating insulation layer B is arranged 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] The preheating section B in the present invention can control the inlet temperature of the material entering the reaction unit B; the insulation 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 and insulation layer B includes a barrel B and a heating element B and a temperature measuring element B located inside the barrel B, and the reaction tube B passes through the barrel 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 between the inside and outside of 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 in the present invention achieves the purpose of monitoring the temperature difference between the inside and outside of the reaction tube B by arranging the temperature measuring element B inside and outside the reaction tube B, and achieves the purpose of monitoring the temperature difference between the outside of the reaction tube B and the set temperature of the heating element B by arranging the temperature measuring element B outside the reaction tube B at a position corresponding to the heating element B.

[0066] In the present invention, the reaction tube B is heated by the heating element B, which can provide heat for the material to undergo a transformation reaction in the presence of a catalyst. The temperature inside and outside the reaction tube B and 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 location where the temperature measuring element B is set is referred to as the temperature measuring point B in the present invention.

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

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

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

[0070] In the present invention, the temperature at different positions of the reaction tube can be controlled by a heating element B arranged at different positions outside the reaction tube B. The preheating section B is used to preheat the material entering the reaction tube B, which can be preheated by the heating element B. Inert materials can be filled in the preheating section B, including porcelain balls, porcelain rings, silicon oxide balls, etc.; the material enters the constant temperature section B after being preheated to the reaction temperature. 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 according to the difference of ±3°C between the external temperature of the reaction tube B and the temperature of the external electric heating wire B; the reaction product obtained by the conversion reaction enters the insulation section B again, and the temperature of the insulation section B is controlled by the heating element B outside the insulation section B.

[0071] According to a particularly preferred embodiment of the present invention, the preheating section, constant temperature section B and insulation section B of the reaction tube B are each provided with a heating element B, for example, the preheating section is provided with 1 heating element B, the constant temperature section B is provided with 3-6 sections (for example, 3 sections, 4 sections, 5 sections or 6 sections) of heating elements B from top to bottom, and the insulation section B is provided with 1 heating element B.

[0072] In the present invention, each section of the heating element B arranged outside the heat preservation section B corresponds to the sulfur-resistant conversion catalyst loaded in the heat preservation section B and can be divided into multiple sections of catalyst beds.

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

[0074] The constant temperature section B loaded with sulfur-resistant shift catalyst in the present invention means that the constant temperature section B is used to load the sulfur-resistant shift catalyst. In actual use, the constant temperature section B can be loaded or not loaded with the sulfur-resistant shift catalyst according to the needs. For example, when the single isothermal furnace shift process is used, the constant temperature section B of the reaction tube B can be loaded with no catalyst.

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

[0076] In the present invention, according to the process characteristics, if the reaction unit A selects the adiabatic mode or the isothermal mode, the second reactor is in the adiabatic mode, which can simulate the "isothermal + adiabatic" and "adiabatic + adiabatic" transformation processes; if no catalyst is loaded in the first reactor, the adiabatic transformation process of a single reactor can be simulated; if no catalyst is loaded in the second reactor, the isothermal transformation process of a single reactor can be simulated.

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

[0078] According to one embodiment of the present invention, along the material flow direction, the separation / analysis system includes an optional condenser, a gas-liquid separator, a pressure reducer and an analysis device arranged in series. That is, the outlets of reaction unit A and reaction unit B are respectively provided with a set of optional condensers, gas-liquid separators, pressure reducers and analysis devices arranged in series.

[0079] The optional condenser in the present invention means that the condenser can be provided or not provided according to the needs.

[0080] The separation / analysis system of the present invention can realize an online segmented sampling method, and can avoid the influence of sampling and analysis of the two-stage reaction unit evaluation device on the evaluation result; after the pressure is reduced by a pressure reducer, the 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 the reaction unit A, preferably along the material flow direction, and the separation system includes a gas-liquid separator, a pressure reducer and an analysis device arranged in series.

[0082] In the present invention, the outlet material of the reaction unit A can be analyzed online by a separation / analysis system, and the material entering the reaction unit B for the conversion reaction can be adjusted as needed based on the result of the online analysis.

[0083] In the present invention, the product material passing through the outlet of the reaction unit A is separated into gas and liquid by a gas-liquid separator, and then is decompressed by a pressure reducer, and the gas phase material can enter the analysis equipment for analysis. After the pressure is reduced by the pressure reducer, the water vapor separation is fast, the pressure and the sampling amount are controllable, which is conducive to accurate analysis, and the influence on the subsequent reaction can be ignored.

[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 analysis device arranged in series.

[0085] In the present invention, the product material coming out of the 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 discharged after alkali washing. The liquid phase product is collected and centrally processed. Part of the gas phase product can be taken and enters an analysis device for analysis.

[0086] The structures of the condenser, gas-liquid separator, pressure reducer and analysis equipment in the present invention are conventional structures in the field. The present invention has no special restrictions on this and will not be elaborated here. Among them, the analysis equipment can be a gas chromatography analysis, 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 an outlet of the raw gas storage tank.

[0088] In the present invention, the raw gas introduced into the reaction system from the raw gas storage is metered and controlled by the flowmeter at the outlet of the raw gas storage, wherein the structure of the raw gas storage is a conventional structure in the art, such as a raw gas cylinder, and the present invention has no special limitation on this, and the flowmeter can be a mass flowmeter. According to a preferred embodiment of the present invention, the steam supply unit includes a liquid water supply subunit, two liquid water quantitative feeding devices independently connected to the liquid water supply subunit, and a vaporizer arranged at the outlet of the liquid water quantitative feeding device.

[0089] In the present invention, liquid water is supplied through a liquid water supply subunit, and the water intake is controlled by a liquid water quantitative feeding device, and then the liquid water is vaporized by a corresponding vaporizer to obtain steam.

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

[0091] The liquid water quantitative feeding device in the invention adopts a water pump and a balance to control the water intake.

[0092] The mixing system described in the present 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 the 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 the reaction unit A with the steam from another outlet of the steam supply unit. For example, if the water-gas ratio needs to be adjusted, the product material coming out of the 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 and then enters the reaction unit B.

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

[0094] In the present invention, each system, unit and device are connected / communicated through pipelines. Pumps can be set on each pipeline as needed, such as a pump set at the outlet of the liquid water quantitative feeding device, so that the material can be better transported; valves can be set on each pipeline as needed, such as valves are set on the connecting pipeline of the raw gas supply unit outlet and the mixing system, and on the connecting pipeline of the steam supply unit outlet and the mixing system; insulation (such as electric insulation) can also be set on the connecting pipeline as needed, for example, insulation (called pipeline heating) is set on the connecting pipeline of the reaction unit A and the reaction unit B, and insulation (called pipeline heating) is set on the connecting pipeline of the steam supply unit outlet and the reaction unit A to prevent condensation of water vapor in the gas; each device in the evaluation device of the present invention can also be set with a separate heating device as needed, and the temperature of the corresponding device can be controlled separately, such as a separate heating device for the vaporizer and the mixer, so that the liquid water entering the vaporizer can be vaporized into steam, and the material entering the reaction unit A and / or the reaction unit B is not condensed. The above are only some exemplary descriptions of the present invention, but the present invention is not limited thereto.

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

[0096] (1) The raw gas from the raw gas supply unit enters the mixing system before the reaction unit A in one way, and the other way is mixed with the product material at the outlet of the reaction unit A through the mixing system before the reaction unit B according to the needs and then enters the reaction unit B;

[0097] (2) The steam from the steam supply unit enters the mixing system before the reaction unit A in one way, and the steam from the steam supply unit enters the reaction unit B in another way after being mixed with the product material at the outlet of the reaction unit A through the mixing system before the reaction unit B as needed;

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

[0099] (4) Separating and / or analyzing the product materials at the outlet of reaction unit A and / or reaction unit B by a separation / analysis system.

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

[0101] In the present invention, the reaction tube A of the reaction unit A and / or the reaction tube B of the reaction unit B may be loaded with a sulfur-resistant shift catalyst according to the specific simulated process.

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

[0103] In the present invention, when evaluating the sulfur-tolerant shift catalyst, the raw gas undergoes a shift reaction in the presence of the sulfur-tolerant shift catalyst, and the temperature of the catalyst bed is preferably 0-600°C, preferably 200-450°C.

[0104] The catalyst bed in the present invention can be divided into multiple stages from top to bottom according to the heating elements outside the corresponding reaction tubes.

[0105] According to one embodiment of the present invention, when simulating a single isothermal mode to evaluate a sulfur-resistant shift catalyst, the method for evaluating the sulfur-resistant shift catalyst includes: loading a sulfur-resistant shift catalyst into reaction tube A of reaction unit A, and not loading a sulfur-resistant shift catalyst into reaction tube B of reaction unit B; and introducing heat exchange medium into heat exchange coil section A arranged outside constant temperature section A of reaction tube A through the opening of a valve by heat exchange medium supply device A so that the temperature difference of the temperature measuring points corresponding to each section of the catalyst bed in reaction tube A is 0-5°C to achieve an isothermal mode.

[0106] According to one embodiment of the present invention, when simulating a single adiabatic mode to evaluate a sulfur-resistant shift catalyst, the method for evaluating the sulfur-resistant shift catalyst includes: no sulfur-resistant shift catalyst is loaded in reaction tube A of reaction unit A, and a sulfur-resistant shift catalyst is loaded in reaction tube B of reaction tube B; the constant temperature section B of reaction tube B is controlled according to a temperature difference of ±3°C between the external temperature of reaction tube B and the temperature of the corresponding external heating component B to achieve an adiabatic mode.

[0107] According to one embodiment of the present invention, when simulating two-stage furnace hydrogen production to evaluate sulfur-resistant conversion catalysts, the sulfur-resistant conversion catalyst evaluation method includes: loading a sulfur-resistant conversion catalyst into reaction tube A of reaction unit A, and loading a sulfur-resistant conversion catalyst into reaction tube B of reaction unit B; heat exchange medium supply device A introduces heat exchange medium into heat exchange coil section A arranged outside constant temperature section A of reaction tube A through the opening of the valve so that the temperature difference of the temperature measuring points corresponding to each section of the catalyst bed in reaction tube A is 0-5°C to achieve an isothermal mode; constant temperature section B of reaction tube B is controlled according to the difference of ±3°C between the external temperature of reaction tube B and the temperature of the corresponding external heating element B to achieve an adiabatic mode.

[0108] According to one embodiment of the present invention, when simulating a two-stage furnace mode for producing methanol or synthesis gas to evaluate a sulfur-resistant conversion catalyst, the sulfur-resistant conversion catalyst evaluation method includes: loading a sulfur-resistant conversion catalyst into a reaction tube A of a reaction unit A, and loading a sulfur-resistant conversion catalyst into a reaction tube B of a reaction unit B; closing the valve between a heat exchange medium supply device A and a reaction unit A, so that a heating and insulation layer A of a reaction unit A is a closed system, and the external heat of the reaction tube A is controlled to achieve a temperature deviation of less than 5°C between a temperature measuring point outside the reaction tube A and a corresponding external heating component A, thereby achieving an adiabatic mode; and controlling a constant temperature section B of the reaction tube B according to a temperature difference of ±3°C between the external temperature of the reaction tube B and the corresponding external heating component B to achieve an adiabatic mode.

[0109] According to one embodiment of the present invention, when simulating a two-stage furnace to produce methanol or synthesis gas and adjusting the water-gas ratio temperature control mode to evaluate the sulfur-resistant conversion catalyst, the sulfur-resistant conversion catalyst evaluation method includes: loading a sulfur-resistant conversion catalyst in the reaction tube A of the reaction unit A, and loading a sulfur-resistant conversion catalyst in the reaction tube B of the reaction unit B; closing 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, and the external heat of the reaction tube A is controlled to achieve a temperature deviation of less than 5°C between the temperature measuring point outside the reaction tube A and the corresponding heating element A, thereby achieving an adiabatic mode; a pipeline connected to the outlet of the steam supply unit and the reaction unit A is used to supply steam to the inlet of the reaction unit B to adjust the water-gas ratio entering the reaction unit B to achieve control of the water-gas ratio in the material entering the reaction unit B; the constant temperature section B of the reaction tube B is controlled according to the difference of ±3°C between the external temperature of the reaction tube B and the temperature of the corresponding external heating element B to achieve an adiabatic mode.

[0110] According to one embodiment of the present invention, when simulating the CO content adjustment mode in the raw gas to evaluate the sulfur-resistant conversion catalyst, the sulfur-resistant conversion catalyst evaluation method includes: loading the sulfur-resistant conversion catalyst in the reaction tube A of the reaction unit A, and loading the sulfur-resistant conversion catalyst in the reaction tube B of the reaction unit B; the heat exchange medium supply device A passes the heat exchange medium into the heat exchange coil section A arranged outside the constant temperature section A of the reaction tube A through the opening of the valve so that the temperature difference of the temperature measuring points corresponding to each section of the catalyst bed in the reaction tube A is 0-5°C to achieve the isothermal mode; the steam supply unit is connected to the outlet of the reaction unit A through a pipeline to supply steam to the inlet of the reaction unit B to adjust the water-gas ratio entering the reaction unit B and / or adjust the space velocity in the reaction unit A to control the CO content in the material entering the reaction unit B; the constant temperature section B of the reaction tube B is controlled according to the difference of ±3°C between the external temperature of the reaction tube B and the temperature of the corresponding external heating component B to achieve the adiabatic mode.

[0111] In the present invention, when 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, and the present invention has no special restrictions on this. For example, the space velocity of the feed gas can be 2000-5000h -1 , the vaporizer temperature can be 230-280°C, the mass flow rate between the raw gas reservoir and the reaction unit A can be 200-300L / h, the delivery flow rate of the water pump between the raw gas reservoir and the reaction unit A can be 2.5-5g / min, the delivery flow rate of the water pump between the raw gas reservoir and the inlet of the reaction unit B can be 1-2g / min, the reaction pressure can be 3-5MPa, and the pipeline heating can be 230-250°C. The above are all exemplary descriptions of the present invention, but the present invention is not limited to this.

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

[0113] The "water-gas ratio" mentioned in the present invention refers to the ratio of the volume flow rate of steam to the volume flow rate of dry-basis raw gas, and the water-gas ratio can be set according to the specific process of simulation.

[0114] The heat exchange medium in the present invention can be water, carbon dioxide, air, etc., preferably cheap and easily available air, preferably compressed air.

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

[0116] Specifically, the sulfur-resistant conversion catalyst evaluation device includes: a feeding system, a mixing system, a reaction system and a separation / analysis system; the feeding system includes a raw gas supply unit and a steam supply unit; along the material flow direction, the reaction system includes: a reaction unit A8 with an isothermal mode and an adiabatic mode arranged in series, the isothermal mode and the adiabatic mode of the 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 provided with an inlet of the reaction unit A8 and an inlet of the reaction unit B17, and the mixers 7 and 15 are provided with separate heating equipment (not shown); the raw gas supply unit includes a raw gas cylinder 2 and a flow meter 16 arranged at the outlet of the raw gas cylinder 2; the raw gas supply unit is connected to the inlet of the reaction unit A8 through the mixer 7 in the mixing system, and is connected to the inlet of the reaction unit B17 through the mixer 15 on the other side. 8; the steam supply unit includes a liquid water supply subunit (not shown), two liquid water quantitative feeding devices (water pump and balance 1, 3) independently connected to the liquid water supply subunit, and vaporizers 4, 5 arranged at the outlet of the liquid water quantitative feeding device, and vaporizers 4, 5 are provided with separate heating equipment (not shown); the steam supply unit is connected to the inlet of reaction unit A 8 through the mixer 7 in the mixing system, and is connected to the inlet of reaction unit B 8 through the mixer 15;

[0117] The reaction unit A8 comprises an external heating and heat-insulating layer A113, a reaction tube A116, and a heat exchange medium supply device A; the reaction tube A116 is arranged through the external heating and heat-insulating layer A113; the reaction tube A116 located in the external heating and heat-insulating layer A113 is arranged from top to bottom as a preheating section A, a constant temperature section A filled with a sulfur-resistant conversion catalyst, and a heat-insulating section A, and the constant temperature section A of the reaction tube A116 is outer-coated with four sections of copper heat exchange coil sections A114; the heat exchange medium supply device A is independently circulated and connected with the four sections of heat exchange coil sections A114; the heat exchange medium supply device A comprises a liquid-phase heat exchange medium storage tank 6 and a gas-phase heat exchange medium inlet pipeline 117 arranged in parallel; a heat exchange medium pump 112 is arranged 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 section of the heat exchange coil sections A114 through a pipeline 114 is independently circulated and connected; 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 and connected with the four sections of heat exchange coil sections A 114 through the gas-phase heat exchange medium pipeline, and the liquid-phase heat exchange circulating 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 circulating out of the heat exchange coil section A 114 flows out through the gas-phase circulating medium outlet 118 and then undergoes conventional treatment in the art and can be circulated back to the gas-phase heat exchange medium storage tank (not shown); the external heating and heat-insulating 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 a temperature measuring point A (not shown); the reaction tube A 116 passes through the cylinder A; each section of the heat exchange coil section A 114 is provided with an electric heating wire A 115; the reaction tube A The constant temperature section A and the heat preservation section A of the reactor 116 are provided with an electric heating wire A 115; the temperature measuring points A are provided inside and outside the reactor 116 corresponding to the electric heating wire A 115; the inner diameter of the reactor 116 is 30 mm and the height is 170 mm;

[0118] The reaction unit B 17 includes an external heating and heat-insulating layer B 213 and a reaction tube B 211; the reaction tube B 211 is arranged through the external heating and heat-insulating layer B 213; the reaction tube B 211 located in the external heating and heat-insulating layer B 213 is arranged from top to bottom as a preheating section B, a constant temperature section B filled with a sulfur-resistant conversion catalyst, and a heat-insulating section B; the external heating and heat-insulating layer B 213 includes a barrel B and an electric heating wire B 212 and a temperature measuring component B located in the barrel B; the reaction tube B 211 penetrates the barrel B; the reaction tube B 211 penetrates the barrel A; a section of electric heating wire B 212 is arranged outside the preheating section and the constant temperature section B of the reaction tube B211; 4 sections of electric heating wire B212 are arranged outside the heat-insulating section B; the position where the temperature measuring component B is arranged is called a temperature measuring point B (not shown); temperature measuring points B are arranged inside and outside the reaction tube B corresponding to the position of the electric heating wire B 212; the reaction tube B The inner diameter of 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 arranged 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 arranged in series at the outlet of reaction unit B 17.

[0120] According to a preferred embodiment of the present invention, Figure 1-3 As shown, the sulfur-tolerant shift catalyst evaluation method includes:

[0121] The raw gas from the raw gas cylinder 2 is decompressed and stabilized, and then the flow rate is controlled by the mass flow meter 16 and then enters the mixer 7 before the reaction unit A 8 for mixing. The other path can be measured by the mass flow meter 16 and the flow rate is controlled according to the needs, and then mixed with the product material at the outlet of the reaction unit A 8 in the mixer 15 and enters the reaction unit B17;

[0122] The raw water from the liquid water supply subunit enters the vaporizer 4 after being metered by a balance and a water pump 3 to control the water flow rate. After the water is converted into steam in the vaporizer 4, it enters the mixer 7 to be evenly mixed with the raw gas and heated to a certain temperature. The other way is metered by a balance and a water pump 1 as needed and enters the vaporizer 5. After being vaporized in the vaporizer 5, it enters the mixer 15 to be evenly mixed with the product material at the outlet of the reaction unit A8 and heated to a certain temperature before entering the reaction unit B17.

[0123] The mixed gas from the mixer 7 enters the reaction unit A 8, and the product material from the reaction unit A 8 enters the reaction unit B17 through the insulation pipeline. If the water-gas ratio needs to be adjusted, the product material from the reaction unit A 8 is mixed with another steam through the insulation pipeline and then enters the reaction unit A 8;

[0124] A very small amount of the product material at the outlet of reaction unit A 8 is taken and passed through the gas-liquid separator 11 and the pressure reducer 9 to obtain a gas product which enters the chromatogram 13 for analysis, so as to better control the amount of steam that needs to be added to the other channel;

[0125] The product material from the reaction unit A 8 is cooled by the condenser 18 and then enters the gas-liquid separators 11 and 12 for gas-liquid separation. The gas phase product is pressure-controlled by the back pressure valve and then emptied after alkaline washing. The liquid phase product is collected and processed centrally. A very small amount of gas phase product is taken and enters the chromatograph 14 for analysis.

[0126] The constant temperature section A of the reaction tube A 116 can be filled with or not filled with a sulfur-resistant shift catalyst according to needs; the constant temperature section B of the reaction tube B221 can be filled with or not filled with a sulfur-resistant shift catalyst according to needs;

[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 the 6-section electric heating wire A 115, and the temperature inside and outside the corresponding reaction tube A 116 is monitored by the corresponding temperature measuring point A;

[0128] When the 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, and the flow rate of the compressed air is controlled by adjusting the opening of the four valves on the connecting pipelines between the gas phase heat exchange medium inlet pipeline 117 and the four heat exchange coil sections A114, thereby controlling the temperature difference between each section of the four catalyst beds to be 0-5°C, thereby achieving the function of the isothermal mode; when the reaction unit A is in adiabatic mode, the valves on the connecting pipelines between the gas phase heat exchange medium inlet pipeline 117 and the heat exchange coil section A are closed, so that the external heating insulation layer A is a closed system, and the heating wire A is used to control the reaction tube A to have no heat conduction with the outside, thereby achieving an adiabatic effect, thereby realizing the function of the 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 the 6-section electric heating wire B 212, and the temperature inside and outside the corresponding 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, and the constant temperature section B of the reaction tube B 211 is controlled to achieve the adiabatic mode according to the difference of ±3°C 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 by way of examples. Figure 1-3 In the following embodiments:

[0132] T1-T6 are the temperatures of the corresponding temperature measuring points A in the reaction tube A from bottom to top;

[0133] t1-t6 are the temperatures of the corresponding temperature measuring points A in the reaction tube B from top to bottom.

[0134] Example 1

[0135] Method for evaluating sulfur-tolerant shift catalysts using simulated single isothermal mode:

[0136] The reaction unit A 8 simulates an isothermal reactor, the constant temperature section A of the reaction tube A 116 is filled with a sulfur-resistant shift catalyst; the constant temperature section B of the reaction tube B 221 is not filled with a sulfur-resistant shift catalyst; the simulation of a single isothermal furnace shift process is realized:

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

[0138] The constant temperature section A of the reaction tube A 116 is filled with 100 mL of sulfur-resistant shift catalyst, and the space velocity is 2000 h -1 ; Reaction tube B is not loaded with catalyst;

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

[0140] Reaction unit A 8: The inlet temperature of reaction tube A 116 is set to 230°C, the outlet temperature of reaction tube A 116 is set to 230°C, and the compressed air pressure is controlled to 0.2-0.3MPa.

[0141] The openings of the four valves on the connecting pipelines between the gas phase heat exchange medium inlet pipeline 117 and the four-stage heat exchange coil section A 114 are controlled respectively, and the catalyst bed temperature is controlled to be stable at 230±5°C. See Table 1 for details.

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

[0143] Temperature measuring point in pipe T1 T2 T3 T4 T5 T6 Temperature / ℃ 230.1 230.5 232.0 231.8 231.5 231.2 Valve opening / % / 15 50 40 30 /

[0144] Example 2

[0145] Method for evaluating sulfur-tolerant shift catalysts by simulating single adiabatic mode:

[0146] The reaction tube A 116 is not loaded with catalyst, and the reaction unit B 8 simulates adiabatic, realizing a simulated single adiabatic furnace conversion process:

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

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

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

[0150] Reaction unit A 8: The external heating temperature of the reaction tube A 116 is set to 250°C, and the four valves on the connecting pipelines between the gas phase heat exchange medium inlet pipeline 117 and the four sections of the heat exchange coil section A 114 are closed. The reaction tube A 116 is controlled to have no heat conduction with the outside through the heating wire A 115 to achieve a heat insulation effect;

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

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

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

[0154] Temperature measuring point in pipe T1 T2 T3 T4 T5 T6 Temperature / ℃ 250.1 250.5 250.3 250.8 250.5 250.1 Valve opening / % / 0 0 0 0 /

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

[0156] Temperature measuring point in pipe t1 t2 t3 t4 t5 t6 Temperature / ℃ 250.0 280.5 483.0 480.8 441.5 251.2

[0157] Example 3

[0158] Method for evaluating sulfur-tolerant shift catalysts by simulating two-stage furnace hydrogen production:

[0159] The reaction tube A 116 and the reaction tube B 211 are both loaded with sulfur-resistant shift catalysts, the reaction unit A 8 is controlled in an isothermal mode, and the adiabatic reaction unit B17 is connected in series to realize a simulated two-stage furnace hydrogen production process:

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

[0161] Reaction tube A 116 catalyst is loaded with 100 mL, space velocity: 2000 h -1 ; The reaction tube B 211 is filled with 100 mL of catalyst, and the gas space velocity can be calculated according to the inlet and outlet gas composition of the reaction unit A 8, or can be tested by simulating the actual catalyst loading of the industrial device;

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

[0163] Reaction unit A 8: The inlet temperature of reaction tube A 116 is set at 250°C, the outlet temperature of reaction tube A 116 is set at 250°C, the compressed air pressure is controlled at 0.2-0.3MPa, and the openings of the four valves on the connecting pipelines between the gas phase heat exchange medium inlet pipeline 117 and the four-section heat exchange coil section A114 are controlled according to the bed temperature to control the catalyst four-section bed temperature to be stable at 230±5°C.

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

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

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

[0167] Temperature measuring point in pipe T1 T2 T3 T4 T5 T6 Temperature / ℃ 250.0 250.1 251.2 250.1 250.5 251.4 Valve opening / % / 40 49 46 35 /

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

[0169] Temperature measuring point in pipe t1 t2 t3 t4 t5 t6 Temperature / ℃ 250.1 260.5 381.0 380.8 301.5 251.2

[0170] Example 4

[0171] Method for evaluating sulfur-tolerant shift catalysts by simulating a two-stage furnace to produce methanol or synthesis gas:

[0172] The reaction tube A 116 and the reaction tube B 211 are both loaded with sulfur-resistant shift catalysts, the reaction unit A 8 is controlled in adiabatic mode, and the adiabatic reaction unit B17 is connected in series to realize the simulation of the two-stage furnace methanol or synthesis gas process:

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

[0174] Reaction tube A 116 catalyst is loaded with 100 mL, space velocity: 2000 h -1 , reaction tube B 211 is filled with 60 mL of catalyst, and the gas space velocity can be calculated according to the inlet and outlet gas composition of reaction unit A 8;

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

[0176] Reaction unit A 8: The external heating temperature of the reaction tube A 116 is set to 250°C, and the four valves on the connecting pipelines between the gas phase heat exchange medium inlet pipeline 117 and the four sections of the heat exchange coil section A 114 are closed. The reaction tube A 116 is controlled to have no heat conduction with the outside through the heating wire A 115 to achieve a heat insulation effect;

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

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

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

[0180] Temperature measuring point in pipe T1 T2 T3 T4 T5 T6 Temperature / ℃ 230.0 291.2 420.0 402.9 361.1 230.8 Valve opening / % / 0 0 0 0 /

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

[0182] Temperature measuring point in pipe t1 t2 t3 t4 t5 t6 Temperature / ℃ 220.0 242.5 246.9 245.2 234.0 221.8

[0183] Example 5

[0184] Method for evaluating sulfur-resistant shift catalyst by simulating two-stage furnace production of methanol or synthesis gas and adjusting water-gas ratio temperature control mode:

[0185] The reaction tube A 116 and the reaction tube B 211 are both loaded with sulfur-resistant shift catalysts, the reaction unit A 8 is controlled in adiabatic mode, and the adiabatic reaction unit B17 is connected in series to realize the simulation of the two-stage furnace methanol or synthesis gas process, and the temperature is controlled by adjusting the water-gas ratio;

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

[0187] Reaction tube A 116 catalyst is loaded with 100 mL, space velocity: 2000 h -1 , simulate the low water-gas ratio gasification process to avoid methanogenic side reactions, the reaction tube B 211 is filled with 80mL of catalyst, the gas space velocity can be calculated according to the inlet and outlet gas composition of the reaction unit A 8, and the water-gas ratio entering the reaction unit B17 is adjusted by adding steam at the inlet of the reaction unit B17 to control the gas composition of the second variable outlet;

[0188] The temperature of vaporizer 4 is set at 280°C, the pipeline heating temperature is 230°C, the temperature of mixer 7 is set at 230°C, the gas volume of mass flow meter 16 between raw 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 gas cylinder 2 and reaction unit B17 is set to 1.78g / min;

[0189] Reaction unit A 8: The external heating temperature of the reaction tube A 116 is set to 250°C, and the four valves on the connecting pipelines between the gas phase heat exchange medium inlet pipeline 117 and the four sections of the heat exchange coil section A 114 are closed. The reaction tube A 116 is controlled to have no heat conduction with the outside through the heating wire A 115 to achieve a heat insulation effect;

[0190] Reaction unit B 17: The inlet and outlet temperatures of reaction tube B 211 are set at 220°C, the electric heating wire B 212 outside reaction tube B 211 is set according to the actual reaction temperature, and 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 external electric heating wire B 212 by ±3°C.

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

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

[0193] Temperature measuring point in pipe T1 T2 T3 T4 T5 T6 Temperature / ℃ 210.0 281.2 340.0 332.9 301.1 210.8 Valve opening / % / 0 0 0 0 /

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

[0195] Temperature measuring point in pipe t1 t2 t3 t4 t5 t6 Temperature / ℃ 220.0 282.5 356.9 345.2 264.0 221.8

[0196] Example 6

[0197] Method for evaluating sulfur-tolerant shift catalysts by simulating CO content adjustment mode in feed gas:

[0198] Reaction tube A 116 and reaction tube B 211 are both loaded with sulfur-resistant shift catalysts. Reaction unit A 8 controls and adjusts the raw gas ratio according to the isothermal mode. Adiabatic reaction unit B17 is connected in series. The CO content of the raw gas in the test material area is adjusted from 70% to 50% through reaction unit A 8.

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

[0200] Reaction tube A 116 catalyst is loaded with 30 mL, space velocity: 2000-5000 h -1, water-gas ratio 0.2-0.6; reaction tube B 211 is filled with 100mL of catalyst, the water-gas ratio and space velocity can be obtained by calculation, and the space velocity and gas composition entering the reaction unit B17 can be adjusted by the mass flow meter 16 and the water pump between the raw gas cylinder 2 and the reaction unit B17 as needed;

[0201] The temperature of vaporizer 4 is set at 280°C, the pipeline heating temperature is 250°C, the temperature of mixer 7 is set at 230°C, and the mass flow meter and water pump between raw gas cylinder 2 and reaction unit A 8 are set according to subsequent needs. The outlet gas composition can be reduced from 70% to 50%. The specific rule is that increasing the water-gas ratio and air velocity can increase the outlet gas composition, and the outlet gas content can be controlled at a certain value through different water-gas ratios and air velocity compositions;

[0202] Reaction unit A 8: The inlet temperature of reaction tube A 116 is set at 250°C, the outlet temperature of reaction tube A 116 is set at 250°C, the compressed air pressure is controlled at 0.2-0.3MPa, and the openings of the four valves on the connecting pipelines between the gas phase heat exchange medium inlet pipeline 117 and the four-section heat exchange coil section A114 are controlled according to the bed temperature to control the catalyst four-section bed temperature to be stable at 230±5°C.

[0203] Reaction unit B17: Set as needed.

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

[0205] Table 10 Temperature control data of 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. The evaluation conditions were: by volume, the process gas was 70% CO, 0.2% H2S, and the balance was hydrogen. The pressure was 4.0 MPa, the isothermal inlet temperature was 210°C, the water-gas ratio was 0.4, and the air velocity was 3000 h -1 The catalyst loading ratio is 1:2, the catalyst loading in the isothermal section is 30 mL, the catalyst loading in the adiabatic section is 60 mL, the isothermal section outlet and adiabatic section inlet temperatures are controlled to be consistent, the adiabatic section water-gas ratio is not adjusted, and is controlled according to the catalyst bed temperature, as shown in Tables 14 and 15. The analysis results are shown in Tables 11, 12, and 13;

[0210] Table 11 Online analysis results using Example 7

[0211]

[0212] Table 12 Sampling bag manual sampling analysis results

[0213]

[0214] Table 13 Online analysis results without pressure reducer

[0215]

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

[0217] Temperature measuring point in pipe T1 T2 T3 T4 T5 T6 Temperature / ℃ 210.1 212.2 211.5 212.8 210.1 210.8 Valve opening / % / 23 27 30 25 /

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

[0219] Temperature measuring point in pipe t1 t2 t3 t4 t5 t6 Temperature / ℃ 210.2 249.5 250.9 251.2 255.0 252.8

[0220] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A sulfur-resistant shift catalyst evaluation device, characterized in that: The device comprises: a feeding system, a mixing system, a reaction system and a separation / analysis system; The feed system comprises: a raw gas supply unit and a steam supply unit; Along the material flow direction, the reaction system comprises: a reaction unit A having an isothermal mode and an adiabatic mode arranged in series, the isothermal mode and the adiabatic mode of the reaction unit A being capable of switching between the operations; and a reaction unit B having an adiabatic mode and optionally an isothermal mode; The separation / analysis system is used to separate and / or analyze the product material at the outlet of reaction unit A and / or reaction unit B; Among them, the outlet of the raw gas supply unit is connected to the inlet of the reaction unit A through the mixing system in one way, and is connected to the inlet of the reaction unit B through the mixing system in another way; the outlet of the steam supply unit is connected to the inlet of the reaction unit A through the mixing system in one way, and is connected to the inlet of the reaction unit B through the mixing system in another way.

2. The device according to claim 1, wherein: The reaction unit A comprises 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 arranged through the external heating and insulation layer A; The reaction tube A located in the external heating insulation layer A is arranged from top to bottom as a preheating section A, a constant temperature section A filled with a sulfur-resistant shift catalyst, and a heat preservation section A; The constant temperature section A of the reaction tube A is covered with at least 3 sections of heat exchange coil sections A, preferably 3-6 sections of heat exchange coil sections A; The heat exchange medium supply device A is independently circulated and connected with each section of the heat exchange coil section A; Preferably, The connecting pipelines between the heat exchange medium supply device A and each section of the heat exchange coil section A are each provided with a valve; and / or The external heating and heat-insulating layer A comprises a cylinder A and a heating element A and a temperature measuring element A located inside the cylinder A, and the reaction tube A passes through the cylinder A; The heating element A is used to heat the reaction tube A. Preferably, each heat exchange coil section A is provided with the heating element A outside 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 outside; The temperature measuring element A is used to monitor the temperature difference between the inside and outside of the reaction tube A and / or the temperature difference between the outside of the reaction tube A and the set temperature of the heating element A.

3. The device according to claim 1 or 2, wherein: The reaction unit B is the same as the reaction unit A; or The reaction unit B comprises an external heating insulation layer B and a reaction tube B; the reaction tube B is arranged through the external heating insulation layer B; the reaction tube B located in the external heating insulation layer B is arranged from top to bottom as a preheating section B, a constant temperature section B filled with a sulfur-resistant shift catalyst, and a heat preservation section B; Preferably, the external heating and heat-insulating layer B comprises a barrel B and a heating element B and a temperature measuring element B located inside the barrel B, and the reaction tube B passes through the barrel B; The heating element B is used to heat the reaction tube B. Preferably, 3-8 sections of heating elements B are arranged outside the reaction tube B. More preferably, a heating element B is arranged outside the preheating section, the constant temperature section B and the insulation section B of the reaction tube B respectively. The temperature measuring element B is used to monitor the temperature difference between the inside and outside of the reaction tube B and / or the temperature difference between the outside of the reaction tube B and the set temperature of the heating element B.

4. The device according to any one of claims 1 to 3, wherein: Along the material flow direction, the separation / analysis system includes an optional condenser, a gas-liquid separator, a pressure reducer and an analysis device arranged in series; Preferably, The separation system is used to analyze the product material at the outlet of the reaction unit A, preferably along the material flow direction, and the separation system includes a gas-liquid separator, a pressure reducer and an analysis device arranged in series; and / or 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 analysis device arranged in series; and / or The raw gas supply unit comprises a raw gas storage tank and a flow meter arranged at the outlet of the raw gas storage tank; and / or The steam supply unit comprises a liquid water supply subunit, two liquid water quantitative feeding devices independently connected to the liquid water supply subunit, and a vaporizer arranged at the outlet of the liquid water quantitative feeding device. Preferably, the liquid water quantitative feeding device comprises a balance and a water pump.

5. A method for evaluating a sulfur-resistant shift catalyst, characterized in that: Using the sulfur-resistant shift catalyst evaluation device according to any one of claims 1 to 6, the method comprises: (1) The raw gas from the raw gas supply unit enters the mixing system before the reaction unit A in one way, and the other way is mixed with the product material at the outlet of the reaction unit A through the mixing system before the reaction unit B according to the needs and then enters the reaction unit B; (2) Steam from the steam supply unit enters the mixing system before reaction unit A in one path; the other path is mixed with the product material at the outlet of reaction unit A through the mixing system before reaction unit B as needed and then enters reaction unit B; (3) The mixed gas from the mixing system before the reaction unit A enters the reaction unit A for reaction, and the product material from the reaction unit A enters the reaction unit B; when the water-gas ratio needs to be adjusted, the product material from the reaction unit A is mixed with another steam and / or another raw material gas and then enters the reaction unit B for reaction; (4) Separating and / or analyzing the product material at the outlet of reaction unit A and / or reaction unit B by a separation / analysis system.

6. The method according to claim 5, wherein: The reaction tube A of the reaction unit A and / or the reaction tube B of the reaction unit B are filled with a sulfur-resistant shift catalyst; Preferably, the operating conditions in reaction tube A and reaction tube B respectively include: The catalyst packing height-to-diameter ratio is 4-8; and / or The amount of catalyst is 50-100mL; and / or The temperature of the catalyst bed is 0-600°C, preferably 200-450°C.

7. The method according to claim 5 or 6, wherein: When simulating a single isotherm mode to evaluate sulfur-tolerant shift catalysts: The sulfur-resistant shift catalyst evaluation method includes: a sulfur-resistant shift catalyst is loaded in a reaction tube A of a reaction unit A, and a sulfur-resistant shift catalyst is not loaded in a reaction tube B of a reaction unit B; a heat exchange medium supply device A passes heat exchange medium into a heat exchange coil section A arranged outside a constant temperature section A of the reaction tube A through the opening of a valve so that the temperature difference of the temperature measuring points corresponding to each section of the catalyst bed in the reaction tube A is 0-5°C to achieve an isothermal mode; When simulating the single adiabatic mode to evaluate the sulfur-tolerant shift catalyst: The evaluation method of the sulfur-resistant shift catalyst includes: no sulfur-resistant shift catalyst is loaded in reaction tube A of reaction unit A, and sulfur-resistant shift catalyst is loaded in reaction tube B of reaction tube B; the constant temperature section B of reaction tube B is controlled according to the difference of ±3°C between the external temperature of reaction tube B and the temperature of the corresponding external heating element B to achieve an adiabatic mode.

8. The method according to any one of claims 5 to 7, wherein: When simulating two-stage furnace hydrogen production to evaluate sulfur-tolerant shift catalysts: The sulfur-tolerant shift catalyst evaluation method includes: a reaction tube A of a reaction unit A is filled with a sulfur-tolerant shift catalyst, and a reaction tube B of a reaction unit B is filled with a sulfur-tolerant shift catalyst; The heat exchange medium supply device A passes the heat exchange medium into the heat exchange coil section A arranged outside the constant temperature section A of the reaction tube A through the opening of the valve so that the temperature difference of the temperature measuring points corresponding to each section of the catalyst bed in the reaction tube A is 0-5°C to achieve the isothermal mode; The constant temperature section B of the reaction tube B is controlled to achieve adiabatic mode according to the difference of ±3°C between the external temperature of the reaction tube B and the temperature of the corresponding external heating element B; When evaluating sulfur-tolerant shift catalysts by simulating a two-stage furnace to produce methanol or synthesis gas: The sulfur-tolerant shift catalyst evaluation method includes: a reaction tube A of a reaction unit A is filled with a sulfur-tolerant shift catalyst, and a reaction tube B of a reaction unit B is filled with a sulfur-tolerant shift catalyst; 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, and control the external heating of the reaction tube A to achieve a temperature deviation of less than 5°C between the temperature measuring point outside the reaction tube A and the corresponding external heating element A, thereby achieving an adiabatic mode; The constant temperature section B of the reaction tube B is controlled to achieve the adiabatic mode according to the difference of ±3°C between the external temperature of the reaction tube B and the temperature of the corresponding external heating element B.

9. The method according to any one of claims 5 to 8, wherein: When simulating the two-stage furnace to produce methanol or synthesis gas and adjusting the water-gas ratio temperature control mode to evaluate the sulfur-resistant shift catalyst: The sulfur-tolerant shift catalyst evaluation method includes: a reaction tube A of a reaction unit A is filled with a sulfur-tolerant shift catalyst, and a reaction tube B of a reaction unit B is filled with a sulfur-tolerant shift catalyst; 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, and control the external heating of the reaction tube A to achieve a temperature deviation of less than 5°C between the temperature measuring point outside the reaction tube A and the corresponding heating element A, thereby achieving an adiabatic mode; The pipeline connecting the steam supply unit 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 to control the water-gas ratio of the material entering reaction unit B; The constant temperature section B of the reaction tube B is controlled to achieve the adiabatic mode according to the difference of ±3°C between the external temperature of the reaction tube B and the temperature of the corresponding external heating element B.

10. The method according to any one of claims 5 to 9, wherein: When evaluating sulfur-tolerant shift catalysts by simulating the CO content adjustment mode in the feed gas: The sulfur-tolerant shift catalyst evaluation method includes: a reaction tube A of a reaction unit A is filled with a sulfur-tolerant shift catalyst, and a reaction tube B of a reaction unit B is filled with a sulfur-tolerant shift catalyst; The heat exchange medium supply device A passes the heat exchange medium into the heat exchange coil section A arranged outside the constant temperature section A of the reaction tube A through the opening of the valve so that the temperature difference of the temperature measuring points corresponding to each section of the catalyst bed in the reaction tube A is 0-5°C to achieve the isothermal mode; The pipeline connecting the steam supply unit 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 constant temperature section B of the reaction tube B is controlled to achieve the adiabatic mode according to the difference of ±3°C between the external temperature of the reaction tube B and the temperature of the corresponding external heating element B.

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