Synthesis gas shift reactor for hydrogen production and synthesis gas hydrogen production device

Abstract

The utility model relates to the field of chemical equipment, in particular to a synthesis gas shift reactor for hydrogen production and a synthesis gas hydrogen production device. The synthesis gas shift reactor is provided with a furnace body, and a partition plate is arranged in the furnace body and divides the furnace body into an isothermal reaction chamber and a heat insulation reaction chamber; the furnace body is provided with a synthesis gas inlet and a shift gas outlet; a heat exchange unit is arranged in the isothermal reaction chamber; by arranging a partition heat exchange mode, redundant heat generated by reaction is removed in time, maximum utilization of energy is realized, and the overtemperature phenomenon is solved; by arranging a crude synthesis gas side inlet, special conditions such as different driving working conditions and load changes can be coped with.

Description

Technical Field

[0001] The utility model relates to the field of chemical equipment, in particular to a syngas conversion reactor for hydrogen production and a syngas hydrogen production device. Background Technique

[0002] The CO conversion process plays an important role in coal chemical industry. In this process, the raw syngas produced by upstream coal gasification reacts, either fully or partially, to generate hydrogen under the action of a catalyst according to the requirement of the hydrogen-carbon ratio of downstream products. For the hydrogen production process, all carbon monoxide in the raw syngas needs to be converted into hydrogen in the conversion stage, so the reaction depth is relatively large, and a higher steam-gas ratio is required to promote the forward shift of the equilibrium. Currently, the supporting conversion processes for high-concentration carbon monoxide hydrogen production are generally divided into high steam-gas ratio conversion process and low steam-gas ratio conversion process. Both of the above belong to adiabatic conversion processes. In addition, there is also an isothermal conversion process.

[0003] Among them, the high steam-gas ratio conversion process has problems such as energy waste, high equipment investment and operation costs; the low steam-gas ratio conversion process has problems such as methanation side reactions.

[0004] The high steam-gas ratio conversion process means that the content of carbon monoxide in the raw syngas produced by pulverized coal gasification is relatively high, and the steam-gas ratio is usually lower than 1.0, which is likely to cause overheating of the first conversion reactor. Therefore, a water replenishment method is usually adopted, that is, a large amount of steam is added in front of the first conversion reactor to increase the steam-gas ratio to more than 1.4. In this way, it can not only promote the forward shift of the thermodynamic equilibrium, but also avoid overheating in the reactor. However, this process also has some disadvantages. For example, excessive steam will cause energy waste; there will be a surplus of steam after the conversion reaction is completed, and the excess steam will be recovered in the form of condensate in the subsequent process sections, which will increase the equipment and operation costs; the conversion catalyst will undergo reverse sulfidation under the reaction of high steam-gas ratio, which will narrow the selection range of raw coal; the conversion catalyst reacts under the harsh conditions of high steam-gas ratio and high temperature for a long time, and its active period will be greatly shortened.

[0005] The low steam-gas ratio conversion process means that although the raw syngas produced by the pulverized coal gasification technology has a high carbon monoxide content, the steam-gas ratio is low. Therefore, the low steam-gas ratio conversion process can also be adopted. That is, the raw syngas is successively passed through multiple stages of conversion reactions. After the first conversion reactor, boiler water or a small amount of steam is added successively before the inlet of the subsequent conversion reactors to quench the converted gas and increase the steam-gas ratio. The conversion is carried out in such a reaction form until the carbon monoxide content in the converted gas at the outlet of the last conversion reactor meets the standard. However, this process also has some disadvantages. For example, the high carbon monoxide concentration in the raw syngas produced by the pulverized coal gasification technology will cause the temperature in the first conversion reactor to exceed the limit; due to the method of quenching water step by step, the reaction depth in the first conversion reactor is far less than that of the high steam-gas ratio conversion process, resulting in an increase in the subsequent conversion units and process flow, thus increasing the equipment and operation costs; at the same time, under the reaction conditions of a low steam-gas ratio, methanation reactions are also likely to occur.

[0006] In order to improve the adiabatic conversion process, an isothermal conversion process technology mainly based on an isothermal conversion furnace has been developed in recent years. That is, by setting a heat exchange unit in the catalyst bed of the conversion furnace, the heat released by the conversion reaction is removed, which well solves the problem of over-temperature in the conversion furnace. This process technology cancels the measures for controlling over-temperature such as the pre-conversion furnace and the quench line, making the process flow simple; and no steam needs to be added during the conversion process, greatly saving the equipment investment and operation costs. The "Axial Isothermal Reactor" in CN201410662794.8 proposes an axial isothermal reactor and its supporting process; the "High-Concentration Carbon Monoxide Isothermal Conversion Process and System" in CN201510107191.6 proposes an axial isothermal reactor and its supporting process. However, this process also has some disadvantages. For example, the by-product steam is saturated steam, which is usually in large surplus and has nowhere to be utilized. Its utilization range is not as wide as that of superheated steam, and condensate will precipitate when the temperature decreases subsequently, making it impossible to be transported through the pipeline network; in addition, when situations such as changes in the upstream raw syngas load, steam-gas ratio, and the need to increase the temperature at the end of the catalyst occur, the outlet temperature of the conversion furnace needs to be frequently adjusted. Therefore, it has a certain difficulty in controlling the removal of reaction heat.

[0007] At present, although the isothermal conversion process technology has improved most of the problems existing in the adiabatic conversion process, it also has some disadvantages. For example, the by-product steam of this process is saturated steam, which is usually in large surplus and has nowhere to be utilized. Its utilization range is not as wide as that of superheated steam, and condensate will precipitate when the temperature decreases subsequently, making it impossible to be transported through the pipeline network; in addition, when situations such as changes in the upstream raw syngas load, steam-gas ratio, and the need to increase the temperature at the end of the catalyst occur, the outlet temperature of the conversion furnace needs to be frequently adjusted. Therefore, it has a certain difficulty in controlling the removal of reaction heat. Utility Model Content

[0008] The utility model aims at the problems existing in the prior art, and provides a high-concentration carbon monoxide radial isothermal-axial adiabatic dual conversion coupling conversion reactor for hydrogen production, which can quickly and effectively adjust the temperature of the conversion gas, by-product superheated high-pressure steam, preheat the raw syngas, reduce the output of low-pressure saturated steam with low utilization value, and reduce the investment and operation difficulty.

[0009] To solve the problems encountered in the above isothermal conversion process, the utility model provides a high-concentration carbon monoxide radial isothermal-axial adiabatic dual conversion coupling syngas conversion reactor for hydrogen production. By setting a partition heat exchange method (gas-cooled heat exchange component and water-cooled heat exchange component) in the upper isothermal reaction zone, the excess heat generated by the reaction is removed in time to achieve the maximum utilization of energy, and the over-temperature phenomenon in the adiabatic reactor is solved; by setting an inlet for raw syngas side, different startup conditions and load changes and other special situations can be dealt with; by adding an adiabatic reaction section at the lower part of the reactor, the outlet temperature of the reactor can be maintained above 400 °C, and then superheated high-pressure saturated steam is generated to improve the energy utilization rate; the conversion gas is superheated with high-pressure saturated steam, and then passed through a conversion gas high-pressure boiler water preheater, and then introduced into an adiabatic conversion reactor (the second adiabatic conversion) to make the carbon monoxide concentration in the conversion gas reach the industrial index for hydrogen production.

[0010] The syngas conversion reactor has a furnace body, and a partition is provided in the furnace body to divide the furnace body into an isothermal reaction chamber and an adiabatic reaction chamber; the furnace body is provided with a syngas inlet and a conversion gas outlet; a heat exchange unit is provided in the isothermal reaction chamber; the heat exchange unit includes a water-cooled heat exchange component and a gas-cooled heat exchange component; the water-cooled heat exchange component is composed of a plurality of water-cooled heat exchange plates; the gas-cooled heat exchange component is composed of a plurality of gas-cooled heat exchange plates; at the center of the isothermal reaction cavity, a central tube extending axially is provided, and a plurality of air collecting holes are provided on the tube wall of the central tube. The upper end opening of the central tube is closed, and the lower end opening communicates with the adiabatic reaction chamber.

[0011] As a preferred technical solution, the gas-cooled heat exchange component is provided with a preheated gas inlet and a preheated gas outlet, and the preheated gas outlet communicates with the syngas inlet; the water-cooled heat exchange component is provided with a preheated water inlet and a preheated water outlet.

[0012] As a preferred technical solution, the syngas inlet includes a first air inlet and a second air inlet; the second air inlet communicates with the central tube; preferably, the first air inlet is located at the top of the furnace body, and the second air inlet is located in the middle of the furnace body.

[0013] As a preferred technical solution, the conversion gas outlet is located at the bottom of the furnace body.

[0014] As a preferred technical solution, the isothermal reaction chamber is sleeved in the furnace body, and a gap is left between the side wall of the isothermal reaction chamber and the inner wall of the furnace body as an air inlet channel; a plurality of air vent holes I are provided on the side wall of the isothermal reaction chamber.

[0015] As a preferred technical solution, the adiabatic reaction chamber is provided with an upper plate and a lower plate extending radially. The upper plate is provided with a plurality of vent holes II, and the lower plate is provided with a plurality of vent holes III. Both ends of the upper plate and both ends of the lower plate are hermetically connected to the inner wall of the shell, and the adiabatic reaction chamber is formed by the upper plate, the inner wall of the furnace body and the lower plate.

[0016] As a preferred technical solution, a gas distributor is provided between the lower end opening of the central tube and the adiabatic reaction chamber.

[0017] As a preferred technical solution, the heat exchange unit extends radially in the isothermal reaction chamber.

[0018] As a preferred technical solution, the single water-cooled heat exchange plate and the single air-cooled heat exchange plate are integrated into one body as a single integrated heat exchange plate; preferably, a plurality of integrated heat exchange plates are arranged in a central radial pattern with the central tube as the center; preferably, the air-cooled heat exchange plate is close to the central tube, and the water-cooled heat exchange plate is far from the central tube.

[0019] In the process of the synthesis gas shift reactor performing the shift reaction, in the synthesis gas, the dry basis volume content of carbon monoxide is 30% to 90%, and the preferred range is 40% to 60%; and / or, in the synthesis gas, the volume ratio of water to dry gas is 0.1 to 1.6; and / or, the pressure range of the synthesis gas is 1.0 to 9.0 MPaG. The gas temperature at the outlet of the preheated gas is 150 to 350 °C. The synthesis gas is composed of a first inlet gas and a second inlet gas. The inlet gas volume of the first inlet gas: the inlet gas volume of the second inlet gas = 10 to 80: 30 to 100. The inlet gas volume of the first inlet gas: the inlet gas volume of the second inlet gas = 30 to 50: 40 to 80. The first inlet gas accounts for 40% of the raw material gas: the second inlet gas accounts for 60% of the raw material gas.

[0020] The first inlet gas enters from the first inlet, flows through the inlet passage and the vent hole I in sequence to enter the isothermal reaction chamber, and after the reaction, flows through the gas collecting hole I, the central tube, the distributor and the vent hole II in sequence to enter the adiabatic reaction chamber.

[0021] The second inlet gas enters from the second inlet, flows through the central tube, the distributor and the vent hole II in sequence to enter the adiabatic reaction chamber; the synthesis gas in the adiabatic reaction chamber flows out through the vent hole III and the shift gas outlet in sequence after the reaction.

[0022] The gas temperature of the gas discharged from the outlet is ≥400 °C.

[0023] The present invention also provides a synthesis gas to hydrogen production device, including any one of the above-mentioned synthesis gas shift reactors.

[0024] As a preferred technical solution, the syngas hydrogen production device further includes a gas-liquid separator, a high-pressure steam superheater, a high-pressure steam generator, a high-pressure water preheater, an adiabatic conversion reactor, a low-pressure steam superheater, and a low-pressure steam generator; the gas outlet of the gas-liquid separator is sequentially connected to the syngas conversion reactor, the high-pressure steam superheater, the high-pressure steam generator, the high-pressure water preheater, the adiabatic conversion reactor, the low-pressure steam superheater, and the low-pressure steam generator; the high-pressure steam superheater has mutually heat-exchanging pipelines I-1 and I-2; the high-pressure steam generator has mutually heat-exchanging pipelines II-1 and II-2; the high-pressure water preheater has mutually heat-exchanging pipelines III-1 and III-2; the high-pressure water supply end is sequentially connected to III-2, pipeline II-2, and pipeline I-2; the conversion gas outlet of the syngas conversion reactor, pipeline I-1, pipeline II-1, pipeline III-1, and the inlet of the adiabatic conversion reactor are sequentially connected; the conversion gas low-pressure steam superheater has mutually heat-exchanging pipelines IV-1 and IV-2; the conversion gas low-pressure steam generator has mutually heat-exchanging pipelines V-1 and V-2; the low-pressure water supply end is sequentially connected to V-2 and pipeline IV-2; the outlet of the adiabatic conversion reactor, pipeline IV-1, and pipeline V-1 are sequentially connected. Preferably, the high-pressure water supply end is sequentially connected to III-2 and the preheated water inlet.

[0025] As a preferred technical solution, the device further includes a detoxification tank and a waste heat recovery unit; the detoxification tank is located between the gas outlet of the gas-liquid separator and the syngas conversion reactor; the low-pressure steam generator is connected to the waste heat recovery unit. The detoxification tank of the present utility model is a conventional container in the field, filled with porcelain balls or catalysts inside, and is used to purify the raw syngas. The waste heat recovery equipment included in the waste heat recovery unit are a conversion gas desalted water preheater, a conversion gas water cooler, a stripping tower, etc., which respectively utilize the waste heat multiple times to achieve multi-stage energy utilization.

[0026] The syngas enters any one of the above-mentioned syngas hydrogen production devices for the hydrogen production process. In the conversion gas obtained from the hydrogen production process, the hydrogen content > 99.6%, and the carbon monoxide content < 0.4%. The outlet temperature of the adiabatic conversion reactor is 250 - 330 °C. Inside the isothermal reaction chamber, a heat exchange reaction catalyst is filled between the side wall and the central tube; an adiabatic reaction catalyst is filled inside the adiabatic reaction chamber. The dry-base volume content of carbon monoxide in the raw syngas from the upstream gasification is 30 - 90%, the water / dry gas volume ratio is 0.1 - 1.6, and the pressure range is 1.0 - 9.0 MPaG.

[0027] The gas-liquid separator is used to separate the saturated water that may be carried in the raw syngas and to act as a buffer. There are no specific separation condition requirements, and the operating pressure of the separator is the same as the pressure range of the raw syngas, which is 1.0 - 9.0 MPaG.

[0028] The pressure range of the superheated steam by-produced by the shift gas high-pressure steam superheater and the saturated steam by-produced by the shift gas high-pressure steam generator is 2.5 - 8.0 MPaG, and the pressure range of the superheated steam by-produced by the shift gas low-pressure steam superheater and the saturated steam by-produced by the shift gas low-pressure steam generator is 0.1 - 2.5 MPaG. The outlet temperature of the raw syngas flowing out from the outlet of the raw syngas preheater is 150 - 350 °C. Superheat the high-pressure saturated steam, and the superheat range of the steam is 10 - 100 °C; superheat the low-pressure saturated steam, and the superheat range of the steam is 10 - 100 °C; the pressure of the high-pressure saturated steam is 2.5 - 6.0 MPaG; the pressure range of the low-pressure saturated steam is 0.2 - 1.5 MPaG; the shift gas high-pressure boiler water preheater preheats the high-pressure boiler water to 100 - 200 °C.

[0029] The outlet temperature of the adiabatic shift reactor is 250 - 330 °C, and the dry basis content of CO in the outlet shift gas is less than 0.4%, meeting the requirements of the product hydrogen.

[0030] The high-concentration carbon monoxide radial isothermal - axial adiabatic dual shift coupling reactor for hydrogen production provided by the present utility model has the following main purposes and advantages:

[0031] (1) By setting the raw syngas side inlet, it can cope with special situations such as different startup conditions and load changes.

[0032] (2) By setting partition heat exchange in the upper isothermal reaction zone, preheat the raw syngas (gas-cooled heat exchange component) in the second-stage partition of the catalyst, and generate high-pressure saturated steam (water-cooled heat exchange component) in the first-stage partition of the catalyst, immediately removing the excess heat generated by the shift reaction to avoid overheating; at the same time, it can also preheat the raw syngas to the activation temperature of the catalyst and by-produce high-pressure saturated steam. The former avoids the problem of tube sheet leakage caused by too large temperature difference between the shell side and the tube side of the previous raw syngas preheater, and directly removing the preheater can also reduce the process complexity and equipment investment. The latter by-produces high-pressure saturated steam to achieve the maximum utilization of energy.

[0033] (3) Set an adiabatic reaction section at the lower part of the reactor, so that the outlet temperature of the final shift gas reaches above 400 °C, by-producing superheated high-pressure steam, saving equipment investment and operating costs.

[0034] (4) After the shift gas is superheated by high-pressure saturated steam, it is introduced into the adiabatic shift reactor to make the carbon monoxide concentration in the shift gas reach the industrial index for hydrogen production.

[0035] (5) The shift gas coming out of the adiabatic shift reactor can also be used to superheat low-pressure saturated steam, reduce the output of low-pressure saturated steam with low utilization value, and achieve the maximum utilization of energy. Description of the Drawings

[0036] Figure 1 High-concentration carbon monoxide radial isothermal - axial adiabatic dual shift coupling process for hydrogen production

[0037] Figure 2 External furnace structure of the reactor

[0038] Figure 3 Internal structure of the reactor

[0039] Figure 4 Partial schematic diagram of the heat exchange component (collection ring)

[0040] Figure 5 Partial schematic diagram of the heat exchange component (collection ball)

[0041] In the figure, 1 is the gas - liquid separator, 2 is the detoxification tank, 3 is the radial isothermal - axial adiabatic dual shift coupling reactor, 4 is the shift gas high - pressure steam superheater, 5 is the shift gas high - pressure steam generator, 6 is the shift gas high - pressure boiler water preheater, 7 is the adiabatic shift reactor, 8 is the shift gas low - pressure steam superheater, 9 is the shift gas low - pressure steam generator, 10 is the waste heat recovery unit; 100 is the furnace body; 101 is the catalyst upper discharge port, 102 is the catalyst lower discharge port; 201 is the first high - pressure boiler water inlet, 202 is the second high - pressure boiler water inlet; 301 is the first high - pressure saturated steam outlet, 302 is the second high - pressure saturated steam outlet; 401 is the first pre - heated crude syngas outlet, 402 is the second pre - heated crude syngas outlet; 50 is the main inlet of the crude syngas; 70 is the main maintenance port; 90 is the side inlet of the crude syngas; 601 is the first pre - heated crude syngas inlet, 602 is the second pre - heated crude syngas inlet; 11 is the shift gas outlet, 12 is the expansion joint, 13 is the high - pressure saturated steam collection ring, 14 is the high - pressure saturated steam riser, 15 is the pre - heated crude syngas collection ring, 16 is the pre - heated crude syngas riser, 17 is the catalyst cylinder, 18 is the heat transfer enhancement plate, 19 is the central pipe, 20 is the high - pressure boiler water riser, 21 is the high - pressure boiler water collection ring, 22 is the crude syngas riser, 23 is the crude syngas collection ball, 24 is the upper maintenance port, 25 is the collection ball maintenance port, 26 is the gas distributor, 27 is the pressure grid, 28 is the lower maintenance port, 29 is the catalyst, 30 is the porcelain ball, 200 is the air - cooled heat exchange plate, 210 is the water - cooled heat exchange plate. Specific embodiments

[0042] The following are only the preferred embodiments of the present invention and do not limit the protection scope of the present invention. All technical solutions within the idea of the present invention should fall within the protection scope of the present invention. For professional technicians in the technical field, minor improvements made to the present invention without departing from the principle of the present invention should also fall within the protection scope of the present invention.

[0043] In the preparation examples, embodiments and comparative examples of the present invention, unless otherwise specified, the components and pipe fittings used are all commercially available products.

[0044] The raw synthesis gas from upstream gasification first enters the gas-liquid separator 1 to separate the excess saturated water therein. After the water is separated, the raw material enters the detoxification tank 2 (filled with porcelain balls in the container for purifying the raw synthesis gas) to remove the impurities and components that are likely to poison the catalyst. The purified raw synthesis gas is divided into two streams, 60% enters from the first raw synthesis gas preheating inlet, and 40% enters from the second raw synthesis gas preheating inlet. The raw synthesis gas enters the radial adiabatic-axial isothermal dual conversion coupling reactor 3 through the first raw synthesis gas preheating inlet and the second raw synthesis gas preheating inlet for heating. Then, the preheated raw synthesis gas (reaching the catalyst activation temperature of 197 °C) flows out from the first raw synthesis gas preheating outlet and the second raw synthesis gas preheating outlet. The preheated raw synthesis gas is divided into two streams. One stream enters the isothermal reaction chamber through the first inlet for the conversion reaction, and the other stream enters through the second inlet. After the two streams of raw synthesis gas are mixed, they enter the adiabatic reaction chamber in the lower section through the distributor for the conversion reaction to obtain the converted gas.

[0045] The high-pressure steam superheater 4 has mutually heat-exchanging pipelines I-1 and I-2; the high-pressure steam generator 5 has mutually heat-exchanging pipelines II-1 and II-2; the high-pressure water preheater 6 has mutually heat-exchanging pipelines III-1 and III-2.

[0046] The high-pressure water supply end is sequentially connected to III-2, pipeline II-2, and pipeline I-2 (a stream of high-pressure boiler water flows through the high-pressure water preheater, high-pressure steam generator, and high-pressure steam superheater in sequence).

[0047] The converted gas outlet of the synthesis gas conversion reactor 3, pipeline I-1, pipeline II-1, pipeline III-1, and the inlet of the adiabatic conversion reactor 7 are sequentially connected (the synthesis gas flows through the high-pressure steam superheater 4, high-pressure steam generator 5, and high-pressure water preheater 6 in sequence).

[0048] Preferably, the high-pressure water supply (preferably high-pressure boiler water) is sequentially connected to III-2 and the preheated water inlet; (another stream of high-pressure boiler water flows through the high-pressure water preheater 6 and the synthesis gas conversion reactor 3 in sequence).

[0049] The low-pressure steam superheater 8 has mutually heat-exchanging pipelines IV-1 and IV-2; the low-pressure steam generator 9 has mutually heat-exchanging pipelines V-1 and V-2.

[0050] The low-pressure water supply end (preferably low-pressure boiler water) is sequentially connected to V-2 and pipeline IV-2 (the low-pressure boiler water flows through the low-pressure steam generator 9 and the low-pressure steam superheater 8 in sequence).

[0051] The outlet of the adiabatic conversion reactor 7, pipeline IV-1, and pipeline V-1 are connected in sequence (the converted gas at the outlet of the adiabatic converter reactor 7 flows through the low-pressure steam superheater 8 and the low-pressure steam generator 9 in sequence).

[0052] The device further includes a detoxification tank and a waste heat recovery unit; the detoxification tank is located between the gas outlet of the gas-liquid separator and the syngas conversion reactor; the low-pressure steam generator is connected to the waste heat recovery unit (the converted gas at the outlet of the adiabatic converter reactor 7 flows through the low-pressure steam superheater 8, the low-pressure steam generator 9, and the waste heat recovery unit 10 in sequence).

[0053] The converted gas flowing out from the converted gas outlet passes through the converted gas high-pressure steam superheater 4 (superheating the high-pressure saturated steam, with a steam superheat degree of 30°C), the converted gas high-pressure steam generator 5 (exchanging heat of the high-pressure boiler water into saturated steam, with a high-pressure saturated steam pressure of 4.0 MPaG), and the converted gas high-pressure boiler water preheater 6 (preheating the high-pressure boiler water to 150°C) in sequence.

[0054] The converted gas flowing out from the converted gas high-pressure boiler water preheater 6 enters the adiabatic conversion reactor 7 for the second-stage adiabatic conversion, and the converted gas coming out passes through the converted gas low-pressure steam superheater 8 (superheating the low-pressure saturated steam by 30°C) and the converted gas low-pressure steam generator 9 (exchanging heat of the low-pressure boiler water into low-pressure saturated steam, with a low-pressure saturated steam pressure of 0.45 MPaG) in sequence.

[0055] The converted gas flowing out from the converted gas low-pressure steam generator 9 is sent to the subsequent waste heat recovery unit 10, and in this section, the heat is recycled mainly through desalted water, boiler water, and low-pressure saturated steam.

[0056] The inner part of the described radial adiabatic - axial isothermal dual conversion coupling reactor is divided into upper and lower sections. The upper section's isothermal reaction chamber (catalyst cylinder) is sleeved inside the furnace body, and a syngas inlet channel is formed between it and the furnace body. A central tube is provided at the central position inside the catalyst cylinder. Inner and outer intake annuli are respectively provided on the central tube and the side wall of the catalyst cylinder. The area between the catalyst cylinder and the central tube is called the reaction zone, and sectional catalysts are filled in this area. The catalyst can be discharged through the catalyst upper discharge port 101 at the lower end of the reaction zone. To make the upper section reaction zone in an isothermal state, while preheating the raw syngas to the catalyst activation temperature and by-product high-pressure saturated steam.

[0057] In the isothermal reaction zone of the present utility model, a heat exchange reaction unit with a plate structure is provided for sectional heat exchange. The raw syngas is preheated (air-cooled) in the second-stage section of the catalyst, and high-pressure saturated steam is generated (water-cooled) in the first-stage section of the catalyst. Therefore, a plurality of plate cooling units are provided in the two sections of the upper section reaction zone of the reactor of the present utility model.

[0058] The cooling unit described is a plate-type heat exchange unit. In the reaction zone, the plate-type cooling unit is arranged in a central radial pattern with the central tube as the axis in the reaction zone. There are multiple raised positions on the side of the plate-type cooling unit. Such an arrangement can increase the turbulence degree of the fluid, thereby improving the heat transfer coefficient. And under the same heat transfer amount, the required heat exchange area is smaller, greatly reducing the equipment investment.

[0059] The inlet of the plate-type water cooling unit in the first-stage catalyst partition is connected to the high-pressure boiler water riser. Multiple high-pressure boiler water risers converge and are connected to the high-pressure boiler water collection ring, and the high-pressure boiler water collection ring is then connected to the high-pressure boiler water inlet; the inlet of the plate-type gas cooling unit in the second-stage catalyst partition is connected to the raw syngas riser. Multiple raw syngas risers converge and are connected to the raw syngas collection sphere, and the raw syngas collection sphere is connected to the raw syngas preheating inlet. In addition, a maintenance opening is provided below the collection sphere for maintenance use.

[0060] The outlets of the plate-type water cooling units in the first-stage catalyst partition are all connected to the high-pressure saturated steam riser. Multiple high-pressure saturated steam risers converge at the high-pressure saturated steam collection ring. At the same time, the upper part of the high-pressure saturated steam collection ring is connected to the high-pressure saturated steam outlet to send out the steam; the outlets of the plate-type gas cooling units in the second-stage catalyst partition are all connected to the preheated raw syngas riser. Multiple preheated raw syngas risers converge at the preheated raw syngas collection ring. At the same time, the upper part of the preheated raw syngas collection ring is connected to the raw syngas preheating outlet to send out the preheated raw syngas.

[0061] A raw syngas side inlet (the second inlet) is provided between the upper and lower sections of the furnace body. The syngas from the bypass can be directly mixed fully with the converted gas flowing out of the central tube in the upper section, and then sequentially pass through the gas distributor and enter the lower adiabatic reaction section. By means of bypass regulation, different startup conditions and load changes and other situations can be dealt with, and the outlet temperature of the lower converted gas can be better controlled.

[0062] The lower section of the furnace body is a barrel-in mixing-axial adiabatic reactor. The reaction gas passes through the conversion catalyst bed in an axial manner for reaction, and then is discharged through the converted gas outlet. The setting of the adiabatic reaction section can make the outlet temperature of the converted gas reach above 400 °C, which can be used for superheating high-pressure saturated steam. The catalyst in the adiabatic section can be discharged through the catalyst lower discharge port.

[0063] Example 1 Synthesis Gas Conversion Reactor

[0064] As Figure 2 、 Figure 3As shown, the structure of the radial isothermal-axial adiabatic dual conversion coupling reactor 3 includes: a furnace body 100, a first high-pressure boiler water inlet 201, a second high-pressure boiler water inlet 202, a first high-pressure saturated steam outlet 301, a second high-pressure saturated steam outlet 302, a first preheated outlet of raw syngas 401, a second preheated outlet of raw syngas 402, a main inlet of raw syngas 50, a first inlet for preheating raw syngas 601, a second inlet for preheating raw syngas 602, a main maintenance port 70, a catalyst upper discharging port 101, a side inlet of raw syngas 90, a catalyst lower discharging port 102, a converted gas outlet 11, an expansion joint 12, a high-pressure saturated steam collecting ring 13, a high-pressure saturated steam riser 13, a preheated raw syngas collecting ring 15, a preheated raw syngas riser 16, a catalyst cylinder 17, a heat transfer intensifying plate 18, a central tube 19, a high-pressure boiler water riser 20, a high-pressure boiler water collecting ring 21, a raw syngas riser 22, a raw syngas collecting sphere 23, an upper maintenance port 14, a maintenance port for collecting sphere 25, a gas distributor 26, a pressure grid 27, a lower maintenance port 28, a catalyst 29, and porcelain balls 30. A partition is provided inside the furnace body to divide the furnace body into an isothermal reaction chamber and an adiabatic reaction chamber; the furnace body is provided with a syngas inlet and a converted gas outlet; a heat exchange unit is provided inside the isothermal reaction chamber; the heat exchange unit includes a water-cooled heat exchange component and an air-cooled heat exchange component; the water-cooled heat exchange component is composed of a plurality of water-cooled heat exchange plates; the air-cooled heat exchange component is composed of a plurality of air-cooled heat exchange plates; at the center of the isothermal reaction chamber, there is a central tube extending axially, and a plurality of air collecting holes are provided on the tube wall of the central tube. The upper end of the central tube is closed, and the lower end is communicated with the adiabatic reaction chamber. The air-cooled heat exchange component is provided with a preheated gas inlet and a preheated gas outlet, and the preheated gas outlet is communicated with the syngas inlet; the water-cooled heat exchange component is provided with a preheated water inlet and a preheated water outlet. The syngas inlet includes a first air inlet and a second air inlet; the second air inlet is communicated with the central tube. The first air inlet is located at the top of the furnace body, and the second air inlet is located in the middle of the furnace body; the converted gas outlet is located at the bottom of the furnace body. The isothermal reaction chamber is sleeved inside the furnace body, and there is a gap between the side wall of the isothermal reaction chamber and the inner wall of the furnace body as an air inlet passage; a plurality of ventilation holes I are provided on the side wall of the isothermal reaction chamber; the adiabatic reaction chamber is provided with an upper plate and a lower plate extending radially. The upper plate is provided with a plurality of ventilation holes II, and the lower plate is provided with a plurality of ventilation holes III. A gas distributor is provided between the lower end of the central tube and the adiabatic reaction chamber; the heat exchange unit extends radially inside the isothermal reaction chamber; a single water-cooled heat exchange plate and a single air-cooled heat exchange plate are integrated into one as a single integrated heat exchange plate; a plurality of integrated heat exchange plates are arranged in a central radial pattern with the central tube as the center; the air-cooled heat exchange plates are close to the central tube, and the water-cooled heat exchange plates are far from the central tube.

[0065] As Figure 4As shown in the figure, a heat exchange enhancement plate 18 is provided in the isothermal reaction chamber to timely remove the reaction heat in the isothermal reaction chamber. The heat exchange enhancement plate 18 is composed of a number of double-channel heat exchange plates. Each double-channel heat exchange plate is integrated by a single liquid medium heat exchange plate and a single gas medium heat exchange plate. A number of double-channel heat exchange plates are arranged in a central radial pattern. The air-cooled heat exchange plate 200 is close to the central tube 19, and the water-cooled heat exchange plate 210 is far from the central tube 19. The water-cooled heat exchange plate 210 circulates a water source (preferably boiler water) as a heat exchange medium, and the air-cooled heat exchange plate 200 circulates the to-be-preheated raw syngas as a heat exchange medium. The external high-pressure boiler water enters through the first high-pressure boiler water inlet 201 and the second high-pressure boiler water inlet 202, converges at the high-pressure boiler water collection ring 21, and then enters the water-cooled heat exchange plate 210 in the catalyst first-stage partition through the high-pressure boiler water riser 20. The high-pressure boiler water absorbs the excess heat in the water-cooled heat exchange plate 210 to avoid over-temperature in the catalyst first-stage partition; the high-pressure boiler water after absorbing heat forms high-pressure saturated steam and flows out from the outlet of the water-cooled heat exchange plate 210 and enters the high-pressure saturated steam riser 14 to converge at the high-pressure saturated steam collection ring 13, and then flows out from the first high-pressure saturated steam outlet 301 and the second high-pressure saturated steam outlet 302. The external raw syngas enters through the first raw syngas preheating inlet 601 and the second raw syngas preheating inlet 602, converges at the raw syngas collection ring 23, and then enters the air-cooled heat exchange plate 200 in the catalyst second-stage partition through the raw syngas riser 22. The raw syngas absorbs the excess heat in the air-cooled heat exchange plate 200 to avoid over-temperature in the catalyst second-stage partition; the temperature of the raw syngas after absorbing heat reaches the catalyst activation temperature, flows out from the outlet of the air-cooled heat exchange plate 200 and enters the preheated raw syngas riser 16 to converge at the preheated raw syngas collection ring 15, and then flows out from the first raw syngas preheating outlet 401 and the second raw syngas preheating outlet 402.

[0066] In addition, the high-pressure boiler water collection ring can also be replaced by a high-pressure boiler water collection sphere, as Figure 5 shown.

[0067] Example 2 Syngas-to-Hydrogen Device

[0068] As Figure 1 shown, the syngas-to-hydrogen device includes a gas-liquid separator 1, a detoxification tank 2, a radial isothermal-axial adiabatic double shift coupling reactor 3, a shift gas high-pressure steam superheater 4, a shift gas high-pressure steam generator 5, a shift gas high-pressure boiler water preheater 6, an adiabatic shift reactor 7, a shift gas low-pressure steam superheater 8, a shift gas low-pressure steam generator 9, and a waste heat recovery unit 10.

[0069] This radial isothermal-axial adiabatic double shift coupling reactor is divided into two sets of systems, namely a two-stage radial-axial double shift reaction system and a steam generation and raw syngas preheating system.

[0070] The process of the two-stage double conversion reaction system is as follows: The raw synthesis gas enters the upper head of the furnace body 100 through the main inlet 50 of the raw synthesis gas, passes through the outer intake annulus through the gas flow channel and sequentially passes through the first-stage catalyst partition (water-cooled heat exchange area) and the second-stage catalyst partition (gas-cooled heat exchange area) in a radial flow direction. The raw synthesis gas contacts and reacts with the catalyst in the reaction zone, and at the same time exchanges heat with the heat exchange enhancement plate 18. The excess heat is carried out by the high-pressure boiler water and the raw synthesis gas raw material in the heat exchange enhancement plate 18 to prevent the temperature in the reaction zone from exceeding the limit. The generated converted gas is collected through the inner intake annulus on the side wall of the central pipe 19. The converted gas flowing out of the central pipe 19 is mixed with the raw synthesis gas entering through the side inlet 9 of the raw synthesis gas, sequentially passes through the gas distributor 26, and enters the lower adiabatic reaction zone in a uniformly distributed manner, and then enters the catalyst 29 for the conversion reaction in an axial flow direction. The temperature of the converted gas after the reaction is above 400°C and is discharged from the converted gas outlet 11.

[0071] On the furnace body 100, there are a catalyst upper unloading port 101 for loading and unloading the catalyst in the upper isothermal reaction zone; a catalyst lower unloading port 102 for loading and unloading the catalyst in the lower adiabatic reaction zone. The main maintenance port 70 is for maintenance personnel to enter the interior of the reactor, and the upper maintenance port 24 and the lower maintenance port 28 are respectively for maintenance personnel to repair the upper and lower regions of the reactor. Porcelain balls 30 are also arranged in the furnace body 100 to protect and support the catalyst 29 and the catalyst bed layer in the upper isothermal reaction zone. The pressure grid 27 is used to fix the catalyst 29 and the porcelain balls 30, and the gas distributor 26 is used for the distribution and mixing of the reaction gas.

[0072] The process of the steam generation system is as follows: The external high-pressure boiler water enters through the first high-pressure boiler water inlet 201 and the second high-pressure boiler water inlet 202, converges at the high-pressure boiler water collection ring 21, and then enters the water-cooled heat exchange plate 210 in the first-stage catalyst partition through the high-pressure boiler water riser 20. The high-pressure boiler water absorbs the excess heat in the water-cooled heat exchange plate 210 to prevent the temperature in the first-stage catalyst partition from exceeding the limit; the high-pressure boiler water after absorbing the heat forms high-pressure saturated steam and flows out of the outlet of the water-cooled heat exchange plate 210 and enters the high-pressure saturated steam riser 14 to converge at the high-pressure saturated steam collection ring 13, and then flows out from the first high-pressure saturated steam outlet 301 and the second high-pressure saturated steam outlet 302.

[0073] The external raw syngas enters through the first raw syngas preheating inlet 601 and the second raw syngas preheating inlet 602, converges at the raw syngas collection sphere or collection ring 23, and then enters the gas-cooling heat exchange plate 200 in the second-stage catalyst partition through the raw syngas riser 22. The raw syngas absorbs the excess heat in the gas-cooling heat exchange plate 200 to prevent the temperature from exceeding the limit in the second-stage catalyst partition; after absorbing the heat, the temperature of the raw syngas reaches the catalyst activation temperature, flows out from the outlet of the gas-cooling heat exchange plate 200 and enters the preheated raw syngas riser 16 to converge at the preheated raw syngas collection ring 15, and then flows out from the first raw syngas preheating outlet 401 and the second raw syngas preheating outlet 402.

[0074] For pulverized coal gasification, the catalyst activation temperature is 180 - 230 °C; for water coal slurry gasification, the catalyst activation temperature is 260 - 330 °C.

[0075] The high-concentration carbon monoxide radial isothermal-axial adiabatic dual shift coupling process for hydrogen production includes the following steps: The raw syngas from upstream has a temperature of 197°C, a pressure of 3.60 MPaG, a dry-based carbon monoxide content of 70%, and a water-gas ratio of 0.93. This raw material gas first enters the gas-liquid separator 1. Process condensate flows out from the bottom outlet of the gas-liquid separator 1, and the raw syngas with excess water removed flowing out from the top enters the detoxification tank 2 to remove impurities and components that are likely to deactivate the catalyst. Then, most of the raw syngas passes through the first raw syngas preheating inlet 601 and the second raw syngas preheating inlet 602, and enters the second-stage partition of the catalyst in the upper-stage isothermal reaction zone of the radial isothermal-axial adiabatic dual shift coupling reactor 3 for preheating, and then flows out from the first raw syngas preheating outlet 401 and the second raw syngas preheating outlet 402. The preheated raw syngas enters the upper-stage isothermal reaction zone of the radial isothermal-axial adiabatic dual shift coupling reactor 3 from the main raw syngas inlet 50 for the shift reaction. The side of the radial isothermal-axial adiabatic dual shift coupling reactor 3 is provided with a first high-pressure boiler water inlet 201, a second high-pressure boiler water inlet 202, a first high-pressure saturated steam outlet 301, and a second high-pressure saturated steam outlet 302. The purpose is to use the high-pressure boiler water to remove the excess heat of the first-stage partition of the catalyst in the upper-stage isothermal reaction zone, and at the same time by-product high-pressure saturated steam. The shifted gas coming out from the upper-stage isothermal zone is mixed with a small part of the raw syngas entering from the raw syngas side inlet 90, and they enter the lower-stage adiabatic reaction zone together for the second shift reaction. The shifted gas coming out from the shifted gas outlet 11 successively passes through the shifted gas high-pressure steam superheater 4, the shifted gas high-pressure steam generator 5, and the shifted gas high-pressure boiler water preheater 6, and by-products high-pressure superheated steam at 3.75 MPaG, exchanges heat to convert the high-pressure boiler water into saturated steam, and preheats the high-pressure boiler water respectively. The shifted gas coming out from the shifted gas high-pressure boiler water preheater 6 enters the adiabatic shift reactor 7 (the second-stage adiabatic shift) for adiabatic shift. The carbon monoxide content in the shifted gas after adiabatic shift is lower than 0.4%, meeting the industrial index. Then, it successively passes through the shifted gas low-pressure steam superheater 8 and the shifted gas low-pressure steam generator 9, and by-products low-pressure superheated steam at 0.52 MPaG and exchanges heat to convert the low-pressure boiler water into low-pressure saturated steam respectively. The shifted gas flowing out from the shifted gas low-pressure steam generator A9 enters the subsequent waste heat recovery unit 10. Equipment such as a shifted gas desalted water preheater (not shown in the figure), a shifted gas water cooler (not shown in the figure), and a stripping column (not shown in the figure) are provided in the waste heat recovery unit 10 to make full use of the waste heat.

Claims

1. A synthesis gas shift reactor, characterized in that: A furnace body is provided, wherein a partition is provided in the furnace body to divide the furnace body into an isothermal reaction chamber and an adiabatic reaction chamber; the furnace body is provided with a synthesis gas inlet and a conversion gas outlet; A heat exchange unit is provided in the isothermal reaction chamber; the heat exchange unit comprises a water-cooled heat exchange component and an air-cooled heat exchange component; the water-cooled heat exchange component is composed of a plurality of water-cooled heat exchange plates; the air-cooled heat exchange component is composed of a plurality of air-cooled heat exchange plates; An axially extending central tube is arranged in the center of the isothermal reaction chamber, a plurality of air collecting holes are arranged on the tube wall of the central tube, the upper end of the central tube is closed, and the lower end is connected to the adiabatic reaction chamber.

2. The synthesis gas shift reactor according to claim 1, characterized in that: The air-cooled heat exchange component is provided with a preheating gas inlet and a preheating gas outlet, and the preheating gas outlet is communicated with the synthesis gas inlet; The water-cooled heat exchange component is provided with a preheated water inlet and a preheated water outlet.

3. The synthesis gas shift reactor according to claim 2, characterized in that: The synthesis gas inlet includes a first gas inlet and a second gas inlet; the second gas inlet is connected to the central pipe.

4. The synthesis gas shift reactor according to claim 3, characterized in that: The first air inlet is located at the top of the furnace body, and the second air inlet is located in the middle of the furnace body; And / or, the conversion gas outlet is located at the bottom of the furnace body.

5. The synthesis gas shift reactor according to claim 4, characterized in that: The isothermal reaction chamber is sleeved in the furnace body, and a gap is left between the side wall of the isothermal reaction chamber and the inner wall of the furnace body as an air inlet channel; the side wall of the isothermal reaction chamber is provided with a plurality of vent holes I; And / or, the thermal insulation reaction chamber is provided with an upper plate and a lower plate extending radially, the upper plate is provided with a plurality of vent holes II, and the lower plate is provided with a plurality of vent holes III.

6. The synthesis gas shift reactor according to claim 5, characterized in that: A gas distributor is provided between the lower end of the central tube and the adiabatic reaction chamber; And / or, the heat exchange unit extends radially in the isothermal reaction chamber; And / or, a single water-cooled heat exchange plate and a single air-cooled heat exchange plate are integrated into one as a single integrated heat exchange plate; a plurality of integrated heat exchange plates are arranged in a central radial pattern with the central tube as the center; the air-cooled heat exchange plate is close to the central tube, and the water-cooled heat exchange plate is far away from the central tube.

7. A synthesis gas hydrogen production device, characterized in that: Comprising the synthesis gas shift reactor as described in any one of claims 1-6.

8. The synthesis gas hydrogen production device according to claim 7, characterized in that: The device also includes a gas-liquid separator, a high-pressure steam superheater, a high-pressure steam generator, a high-pressure water preheater, an adiabatic shift reactor, a low-pressure steam superheater, and a low-pressure steam generator; the gas outlet of the gas-liquid separator is sequentially connected to the synthesis gas shift reactor, the high-pressure steam superheater, the high-pressure steam generator, the high-pressure water preheater, the adiabatic shift reactor, the low-pressure steam superheater, and the low-pressure steam generator; The high-pressure steam superheater has pipelines I-1 and I-2 for heat exchange with each other; the high-pressure steam generator has pipelines II-1 and II-2 for heat exchange with each other; the high-pressure water preheater has pipelines III-1 and III-2 for heat exchange with each other; The high-pressure water supply end is connected to III-2, pipeline II-2, and pipeline I-2 in sequence; The shift gas outlet of the synthesis gas shift reactor, pipeline I-1, pipeline II-1, pipeline III-1, and the inlet of the adiabatic shift reactor are connected in sequence; The conversion gas low-pressure steam superheater has a pipeline IV-1 and a pipeline IV-2 for heat exchange with each other; the conversion gas low-pressure steam generator has a pipeline V-1 and a pipeline V-2 for heat exchange with each other; The low-pressure water supply end is connected to V-2 and pipeline IV-2 in sequence; The outlet of the adiabatic shift reactor, pipeline IV-1, and pipeline V-1 are connected in sequence.

9. The synthesis gas hydrogen production device according to claim 8, characterized in that: The high-pressure water supply end is connected to III-2 and the preheated water inlet in sequence.

10. The synthesis gas hydrogen production device according to claim 9, characterized in that: The device also includes a detoxification tank and a waste heat recovery unit; the detoxification tank is located between the gas outlet of the gas-liquid separator and the synthesis gas conversion reactor; and the low-pressure steam generator is connected to the waste heat recovery unit.

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