A process for hydrogen production by full-temperature simulated rotating moving bed pressure swing adsorption enhanced reaction of shift gas

Abstract

The invention discloses a process for producing hydrogen by a full-temperature range simulated rotating moving bed pressure swing adsorption (FTrSRMPSA) of a shift gas, wherein an axial flow fixed bed adsorption reactor having a plurality of mixed medium and low temperature shift catalysts and adsorbents placed in the center of a multi-channel rotary valve and arranged on a circular rotating tray around the reactor is connected through a pipeline and the rotating direction and speed (ω1) of the rotary valve and the rotating direction and speed (ω2) of the circular rotating tray are regulated, so that the gas flowing through the adsorption reaction bed layer continuously passes through the positions of the inlet and outlet of each adsorption reactor and each adsorption reaction bed layer completes the mass transfer and heat transfer of the respective reaction-adsorption and desorption regeneration steps while rotating, thereby realizing a simulated rotating moving bed pressure swing adsorption enhanced reaction process based on the axial flow fixed bed pressure swing adsorption, and directly obtaining hydrogen (H2) product gas with a purity greater than or equal to 99.9-99.99% and a yield greater than or equal to 92-95%, and simultaneously producing high-purity carbon dioxide (CO2) as a byproduct.

Description

Technical Field

[0001] The present invention relates to the field of hydrocarbon reforming and conversion to produce hydrogen (H2), and more specifically to a process for producing hydrogen by a pressure swing adsorption enhanced reaction of a conversion gas full-temperature simulated rotating moving bed. Background Art

[0002] Shift gas mainly refers to a mixed gas composed of 30~60% H2 (volume ratio, the same below), 10~20% CO, 10~20% CO2, unreacted water, hydrocarbons and other hydrocarbons or organic by-products and other impurities generated by the catalytic reforming of light hydrocarbon mixtures, alcohols and other oxygen-containing gases with water vapor under a certain temperature, pressure and reforming catalyst. The CO therein further undergoes a medium-temperature or low-temperature shift reaction with water vapor under a certain temperature, pressure and shift catalyst to generate H2 and CO2, and then undergoes organic amine absorption or pressure swing adsorption (PSA) decarbonization and pressure swing adsorption (PSA) H2 purification process to obtain a high-purity H2 product. Typical light hydrocarbon feedstock catalytic reforming and conversion hydrogen production processes are mostly to first reform and convert the reaction to generate conversion gas, and then to generate conversion gas rich in H2 and CO2 through a conversion reaction, and then go through organic amine absorption or PSA decarbonization and PSA purification steps to finally obtain H2 products. Although this hydrogen production process is mature, it has a long process, a large footprint, high energy consumption, high equipment investment and cost. As a result, technical transformation and upgrading have been carried out at home and abroad to further simplify the process and reduce the footprint and cost.

[0003] One method is to develop a dual-functional composite catalyst and its supporting integrated reactor and process. The core is to integrate the catalytic reforming reaction and the shift reaction in one reactor. This method has been applied in industrial devices. For example, in the process of methanol hydrogen production, because the temperature and pressure of methanol steam catalytic reforming (cracking) are relatively mild, the catalysts used are mostly copper-based, which is equivalent to the reaction temperature and pressure of the iron-based catalyst in the shift reaction. The thermal equilibrium process of the two reactions is relatively similar, and the effect of achieving a dual-functional catalyst is relatively ideal. For the catalysts used in the catalytic reforming reaction of methane, most of them are high-temperature catalysts, such as nickel-based catalysts, and the reaction temperature is mostly 700~900℃, which is much higher than the 100~300℃ reaction temperature required for medium and low temperature shift catalysts, resulting in a significant increase in the difficulty of developing dual-functional catalysts.

[0004] Another method is the "Sorption Enhanced Reaction Process" (SERP), first invented by Air Products Chemicals (APCI) in the United States. It is to load the catalyst required for the reaction and the adsorbent required for adsorption separation into the same container, so that the reactor and the adsorber are combined into one to form an organically coupled adsorption enhanced reactor for chemical reaction and adsorption separation process. It is completely different from the chemical reaction and adsorption separation in two independent containers, the reactor and the adsorber. The basic principle of adsorption enhancement reaction is to use Le Chatelier's thermodynamic principle, that is, when the system reaches (chemical) equilibrium, if any of the conditions of the equilibrium state, such as concentration, temperature, pressure, etc., are changed, the equilibrium will move in the direction that can weaken its change. For the catalytic reforming reaction and shift reaction system of producing H2 by steam reforming of light hydrocarbons, when the concentration of reactants and products is in a state that does not change with time, the chemical (reaction) equilibrium is reached. However, if an adsorbent that selectively adsorbs the product CO2 is added to the reaction system, the product CO2 will be immediately adsorbed during the reaction, resulting in the breaking of the chemical equilibrium, and the reaction will proceed in a direction that is conducive to the production of H2, making the reaction close to complete. The advantage of the adsorption enhanced reaction process is that improving the operating conditions can increase the reaction conversion rate and product yield or purity, and simplifying the process can reduce energy consumption and costs.The SERP process for pressure swing regeneration of hydrogen supply for fuel cells first developed by APCI is used for hydrogen production from methane steam reforming, wherein the adsorbent used is a high temperature and water resistant reversible chemical adsorbent (K2CO3-hydrotalcite), which is used to selectively adsorb and remove CO2 from the reaction zone with a reaction temperature of 400-550°C. The adsorbent saturated with adsorption is regenerated through PSA cycle operation, and the conversion catalyst of the nickel active component supported on alumina is mixed with the CO2 chemical adsorbent and filled in a pressure swing adsorption enhanced reactor to form a PSA enhanced reaction process with two axial flow fixed beds, wherein one adsorption reactor performs the reaction-adsorption step, and the other performs the desorption and regeneration step of reverse depressurization, vacuum flushing and reverse pressurization. The operating pressure of the reaction-adsorption step is 7 0~350kPa, normal pressure inversion and vacuum flushing, the flushing gas is 5~10% H2 steam, the desorbed gas containing H2, methane (CH4), CO2 and water is condensed to remove water and then output as fuel gas, the charging gas is the raw gas of methane and steam mixture, the obtained H2 product purity is 94.4%, among which the CH4 content is 5.6%, CO2 is 40ppmv, CO is 30ppmv, and the methane conversion rate is as high as 73%, which is much higher than the 50~55% conversion rate of the conversion gas obtained by the two-step method of catalytic conversion and shift reaction of traditional methane steam catalytic reforming (SMR). It not only increases the H2 concentration in the conversion gas, but also reduces the subsequent PSA hydrogen extraction load, while simplifying the hydrogen production process and saving investment, equipment and operating costs.However, the SERP process developed by APCI has some obvious disadvantages. First, the process cannot directly produce high-purity H2 products, and still needs to be further extracted through PSA to obtain high-purity H2. Second, the selected adsorbent is relatively special and needs to be resistant to high temperatures and water. It is difficult to use general commercial adsorbents. Third, the reaction temperature is too high. Even if the nickel-based catalyst in APCI's SERP process can be reduced to about 500°C with the help of de-CO2 adsorbent, it is much lower than the 700~900°C required by the conventional two-stage catalytic reforming nickel-based catalyst, and the energy consumption is small, but the high temperature is very unfavorable for the pressure swing adsorption process of CO2, and under low-pressure adsorption, CO2 is very easy to be adsorbed unsaturated and escape into the non-adsorbed phase gas, causing the CO2 in the conversion gas to exceed the standard seriously. Fourth, S In the ERP process, PSA is actually adsorbed only at a relatively low pressure. Desorption and regeneration are first reversed at normal pressure. The obtained reversed gas is returned as raw gas to another adsorption reactor in the reaction-adsorption step, and then the bed is reversely flushed with steam containing 5-10% H2 and lower than the reaction temperature. The flushing waste gas obtained is used as fuel gas after condensation and dehydration. The H2 yield has a certain loss. At the same time, since the adsorbent used is a chemical adsorbent, it is a consumable adsorbent. Not only is the consumption large, it cannot be recycled like traditional adsorbents, but also under high temperature and water vapor content, it is affected by the temperature difference stress during adsorption and desorption regeneration, which will have a greater impact on the thermal stability of the adsorbent itself; Fifth, since the adsorption reactor in the SERP system has a relatively small height-to-diameter ratio, it is also very unfavorable for the diffusion path of CO2 adsorption. Therefore, APCI's SERP process for hydrogen production by methane steam reforming is difficult to replace the traditional SMR process. To this end, APCI has developed another process called "Temperature Swing Adsorption Enhanced Reaction Process (TSSER)" that uses temperature swing adsorption for hydrogen production from water gas (shift gas). Since the iron-based catalyst of the shift reaction has a relatively low operating temperature, the temperature of the reaction-adsorption step is 300~400℃, which is lower than the 400~550℃ temperature of SERP. This is conducive to the adsorption of CO2, thereby further improving the purity of the produced H2. However, the desorption and regeneration temperature of the adsorbent reaches 500~550℃. At higher temperatures and water vapor content, the adsorbent will be more affected by the temperature difference stress during the adsorption and desorption regeneration process, and the negative impact on the thermal stability of the adsorbent itself is greater than that of the SERP process. Therefore, the frequency of adsorbent replacement in the TSSER process is higher than that in the SERP process, and the cost increases accordingly.

[0005] Whether it is the SERP or TSSER process, the key technology is the selection of adsorbents and their corresponding processes. Since the methane catalytic reforming reaction and the shift reaction are relatively fast, and the endothermic and exothermic processes of the reaction itself are different, the thermodynamic and kinetic adsorption rates of CO2 will also be greatly affected, which will lead to whether the reaction-adsorption steps can be completed simultaneously and change the chemical reaction equilibrium to move in the direction that is conducive to the generation of H2. Therefore, APCI has to use chemical adsorbents that are both temperature-resistant and water-resistant and have extremely fast adsorption rates to match the movement of the reaction-adsorption equilibrium system, but the cost is that the adsorbent has a short service life, high cost, and relatively low purity and yield of the H2 product, but other factors that affect the adsorption efficiency are ignored, such as gas flow distribution, CO2 adsorption mass transfer path, adsorbent and catalyst selection and corresponding filling methods or the solid shape of the adsorbent / catalyst itself, adsorption and desorption cycle operation mode, etc. Summary of the invention

[0006] In view of the problems of the existing adsorption enhancement reaction process in the process of hydrogen production by catalytic reforming / conversion of methane or methanol as raw materials, the present invention proposes a full temperature range simulated rotated moving pressure swing adsorption (FullTemperature range Simulated Rotated Moving The new process of PSA-FTrSRMPSA is used for the pressure swing adsorption enhanced reaction of shift gas to remove CO2 and purify H2. This process is based on pressure swing adsorption enhanced reaction (PSA-ERP), which makes full use of the temperature and pressure of the shift gas, the properties of medium and low temperature shift catalyst / adsorbent, the adsorption separation coefficient and physical and chemical properties of the product H2 and CO2 components in the temperature range of 90~150℃ and the pressure range of 0.2~1.0MPa. An axial flow fixed bed adsorption reactor with multiple mixed medium and low temperature shift catalysts and adsorbents is placed in the center of a multi-channel rotary valve and arranged on a circular rotating tray around it, and is connected through pipes and the rotation direction and rotation speed (ω1) of the rotary valve and the rotation direction and rotation speed (ω2) of the circular rotating tray are regulated, so that the pipes flowing through the rotary valve channel and the channel inlet and outlet ends are connected to the inlet and outlet ends of the adsorption reactor on the circular rotating tray. The gas in the adsorption reaction bed layer rotating in the adsorption tower continuously passes through the inlet and outlet positions of each adsorption reactor and each adsorption reaction bed layer completes the mass transfer and heat transfer of its own reaction-adsorption and desorption regeneration steps while rotating, so that the reaction balance of the conversion gas tends to move toward the direction of complete reaction, thereby forming a "simulated rotating moving bed" pressure swing adsorption enhanced reaction process, realizing a simulated rotating moving bed pressure swing adsorption enhanced reaction process based on axial flow fixed bed pressure swing adsorption, while achieving "double high" yield and purity and avoiding deep adsorption, it is suitable for the corresponding flow rate, component concentration, pressure or temperature fluctuation conditions of the conversion gas, and fully utilizes the various advantages of axial flow fixed bed pressure swing adsorption and existing technologies including fixed bed pressure swing adsorption enhanced reaction (SERP), fixed bed temperature swing adsorption enhanced reaction (TSSER), rotating wheel adsorption and simulated moving bed, and overcomes the defects of the existing technology process. The specific scheme is as follows:

[0007] A full-temperature range simulated rotating moving bed pressure swing adsorption enhanced reaction hydrogen production process for shift gas, the full-temperature range simulated rotating moving bed pressure swing adsorption enhanced reaction (FTrSRMPSA-ERP) system comprises n (a natural integer of 2≤n≤10) axial flow fixed bed adsorption reactors (towers) loaded with a catalyst / adsorbent mixed in a certain proportion of a medium-low temperature shift catalyst and a composite adsorbent and having a certain height-to-diameter ratio and arranged on an annular rotating tray with a rotation speed (ω2, in seconds (s) / cycle), a rotary valve with m (a natural integer of 5≤m≤36) channels and arranged in the center of the annular rotating tray and rotating at a rotation speed (ω1, in seconds (s) / cycle), a rotary valve, and a rotary valve. The rotary valve and the material pipeline for the inlet and outlet of the material gas outside the system, and the process pipeline connected to the upper and lower parts of the adsorption reactor (tower) and the rotary valve through the built-in pipeline of the annular tray, as well as the corresponding driving mechanism for driving the rotation direction of the annular rotating tray and the rotary valve and regulating its rotation speed (ω1 and ω2), the buffer tank, the condenser / or the heat exchanger / or the superheater / or the booster / or the vacuum pump form a FTrSRMPSA-ERP system, characterized in that the pipeline connecting the inlet and outlet of the adsorption reactor (tower) and the inlet and outlet of the m-channel rotary valve is connected through the built-in pipeline preset in the annular rotating tray to form a process pipeline and is the same as the number of channels m of the rotary valve. The position of the material gas entering and exiting the FTrSRMPSA-ERP system It is fixed by the distribution of the rotating channel of the m-channel rotary valve, and its material gas includes the raw gas (F) of the conversion gas, H2 product gas (H2PG), flushing gas (P) outside the system, final charging gas (FR) outside the system, and desorption gas (D) composed of reverse venting gas (D) or / and vacuum air (V) or / and flushing waste gas (PW), and is correspondingly connected to equipment including buffer tank / condenser / or heat exchanger / or superheater / or booster / or vacuum pump. The position of the process gas flow in the process pipeline connected between the inlet and outlet of the m-channel rotary valve and the inlet and outlet of the adsorption reactor (tower) through the built-in pipeline in the circular rotating tray is moved and changed alternately. The process gas flows in the FTrSRMPSA-ERP system, including The raw gas (F), forward discharge gas (PP), flushing gas (P) inside and outside the system, pressure-equalizing gas (ED), reverse discharge gas (D) or / and vacuum air (V) or / and flushing waste gas (PW) composed of desorption gas (D), pressure-equalizing gas (ER), final charging gas (FR) and product hydrogen (H2PG). The specific adsorption and desorption cycle process is that the raw material conversion gas (F) from outside the FTrSRMPSA-ERP system enters the raw material gas (F) inlet of the multi-channel rotary valve, and passes through the raw material gas (F) channel and outlet of the rotary valve, the built-in pipeline of the annular rotating tray and the process pipeline connected to the inlet of one or more axial flow fixed bed adsorption reactors (towers) in the reaction-adsorption (CR-A) state on the annular rotating tray.It enters from the bottom of the adsorption reactor (tower) to carry out the reaction-adsorption (CR-A) step. After the rotation direction and rotation speed (ω1) of the m-channel rotary valve are regulated and matched with the rotation direction and rotation speed (ω2) of the annular rotary tray, the non-adsorbed phase gas flowing out from the top of the adsorption reactor (tower) just enters the H2 product gas (H2PG) channel of the m-channel rotary valve through the process pipeline, and flows out from the H2 product gas (H2PG) channel of the rotary valve to form H2 product gas (H2PG), enters the H2 product gas buffer tank and is output. After the adsorption reactor (tower) in the reaction-adsorption (CR-A) state completes the reaction-adsorption (CR-A) step, as The m-channel rotary valve and the annular rotating tray continue to rotate and step, or / and the adsorption reactor (tower) that has completed the reaction-adsorption (CR-A) performs the forward release (PP) or pressure drop (ED) step on another or several adsorption reactors (towers) that are in the flushing (P) or pressure rise (ER) state through the process pipeline in the system. The adsorption reactor (tower) that has completed the forward release (PP) or pressure drop (ED) step enters the reverse release (D) or / and vacuum (V) or / and flushing (P) step as the m-channel rotary valve and the annular rotating tray continue to rotate and step. The reverse release gas (D) or / and vacuum air (V) or / and flushing waste gas (PW) flowing out of the adsorption tower forms The desorbed gas (D) is produced, or flows through the internal or external pipeline of the annular rotating tray and the reverse venting (D) / vacuuming (V) / flushing waste gas (PW) channel of the rotary valve and its outlet and flows through the desorbed gas (D) buffer tank. The desorbed gas (D) is CO2-enriched gas, or directly enters the condenser for water removal to produce high-concentration CO2 as a by-product, or enters the decarbonization and H2 recovery process, or is returned to the natural gas / light hydrocarbon steam reforming reaction to prepare conversion gas or raw gas process as a carbon-hydrogen ratio adjustment, and the adsorption reactor (tower) that ends the reverse venting (D) or / and vacuuming (V) or / and flushing (P) step is continuously rotated by the m-channel rotary valve and the annular rotating tray. Then, the gas enters the pressure equalization step (ER) or / and the waiting area (-) step, flows out of the adsorption reactor (tower) in the pressure equalization step (ED) and enters the adsorption reactor (tower) in the pressure equalization step (ER) through the built-in pipeline of the annular rotating tray and the pressure equalization gas (ED) channel of the rotary valve for pressure equalization, so that the pressure in the adsorption reactor (tower) in the pressure equalization step (ER) is equal to the pressure in the adsorption reactor (tower) in the pressure equalization step (ED), and ends the pressure equalization step (ER) or / and the waiting area (-) step of the adsorption reactor (tower). As the m-channel rotary valve and the annular rotating tray continue to rotate, the gas enters the final filling step (FR).The H2 product gas (H2PG) or the raw material conversion gas (F) as the final charging gas (FR) flows through the final charging gas (FR) channel of the m-channel rotary valve and the built-in pipeline of the annular rotating tray to enter the adsorption reactor (tower) for pressurization until the pressure in the adsorption reactor (tower) reaches the reaction-adsorption pressure required for the reaction-adsorption (CR-A) step, and prepares for the next round of reaction-adsorption and desorption cycle operation, wherein each adsorption reactor (tower) performs one step or multiple steps and each step is performed through the regulation and matching between the rotation direction and rotation speed (ω1) of the m-channel rotary valve and the rotation direction and rotation speed (ω2) of the annular rotating tray, so that the timing table of the reaction-adsorption and desorption cycle operation of the m channels in the rotating m-channel rotary valve and the n adsorption reactors (towers) in the rotating annular rotating tray are connected end to end into a circle, and the operational cyclicity of the reaction-adsorption and desorption process of the pressure swing adsorption (PSA) enhanced reaction is completely formed, and all the material gases and process gases are evenly and alternately distributed in the m channels in the system. The m circular (groove) channels in the rotary valve and the built-in pipelines in the annular rotating tray and each adsorption reactor (tower), and a cycle of pressure swing adsorption (PSA) enhanced reaction process is carried out simultaneously through the rotating m-channel rotary valve (ω1) and the adsorption reactor (tower) on the corresponding rotating annular rotating tray (ω2), and the position of the process gas entering and leaving the adsorption reactor (tower) is continuously changed by matching the rotation direction and rotation speed (ω1) of the m-channel rotary valve with the rotation direction and rotation speed (ω2) of the annular rotating tray, so that each adsorption reactor (tower) repeats the reaction-adsorption and desorption steps, which is equivalent to each fixed bed adsorption reactor (tower) completing its own reaction-adsorption and desorption steps while the m-channel rotary valve and the annular rotating tray rotate, thereby forming a "simulated rotating moving bed" pressure swing adsorption enhanced reaction process, thereby, the product H2 product gas (H2PG) obtained from the shift gas has a purity greater than or equal to 99.99% and a yield greater than or equal to 92%. ,

[0008] Furthermore, the described conversion gas full-temperature range simulated rotating moving bed pressure swing adsorption enhanced reaction hydrogen production process is characterized in that the rotation direction of the m-channel rotary valve and the annular rotating tray and the regulation and matching between their rotation speeds (ω1 and ω2) include: 1) synchronous in the same direction, rotating in the same direction in a clockwise or counterclockwise direction, and ω1=ω2 / ≠0, 2) asynchronous in the same direction, rotating in the same direction in a clockwise or counterclockwise direction, and ω1>ω2 or ω1<ω2 or ω1≠0 / ω2=0 or ω1=0 / ω2≠0, 3) Asynchronous rotation, clockwise / counterclockwise or counterclockwise / clockwise rotation, and ω1=ω2 / ≠0, 4) Asynchronous rotation, clockwise / counterclockwise or counterclockwise / clockwise rotation, and ω1>ω2 or ω1<ω2 or ω1≠0 / ω2=0 or ω1=0 / ω2≠0, preferably, synchronous rotation, clockwise or counterclockwise rotation in asynchronous rotation, ω1≠0 / ω2=0 or ω1=0 / ω2≠0.

[0009] Furthermore, the described process for producing hydrogen by a full-temperature range simulated rotating moving bed pressure swing adsorption enhanced reaction of a shifted gas is characterized in that the combination of the closed cycle operation steps of reaction-adsorption and desorption of the described full-temperature range simulated rotating moving bed pressure swing adsorption enhanced reaction (FTrSRMPSA-ERP) system also includes 1 to 2 times of pressure equalization, 1 to 2 batches of flushing, 1 time of vacuuming, 1 to 2 times of heating and cooling heat exchange temperature swing pressure swing adsorption, 1 time of mutual staggering of the order of sequential release and pressure drop equalization, 1 waiting area step, and the adsorption reactor (tower) When the number (n) of channels and the corresponding number of channels (m) of the m-channel rotary valve increase, the height (radius) ratio (h / r) of the adsorption tower decreases, and the rotation speed of the m-channel rotary valve or the annular rotary tray is fast enough or the rotation period is short enough, the separation effect of the product H2 and CO2 in the shift gas adsorption enhanced reaction system is infinitely close to the "steady-state" mass transfer separation process of the moving bed, and the shift gas reaction equilibrium tends to move towards the direction of complete reaction, and the purity of the final H2 product gas (H2PG) is greater than or equal to 99.999%, and the product gas yield is greater than or equal to 95%.

[0010] Furthermore, the above-mentioned conversion gas full-temperature range simulated rotating moving bed pressure swing adsorption enhanced reaction hydrogen production process is characterized in that the conversion gas (F) as a raw material is a mixed gas composed of 30~60% H2 (v), 10~20% CO (v), 10~20% CO2 (v), unreacted water, hydrocarbons and other hydrocarbons or organic by-product impurities obtained by steam catalytic reforming or thermal cracking of methane or methanol or other hydrocarbons, with a temperature of 90~150°C, a pressure of 0.2~1.0MPa, and a flow rate of 100~20,000Nm 3 / h.

[0011] Furthermore, the described conversion gas full-temperature range simulated rotating moving bed pressure swing adsorption enhanced reaction hydrogen production process is characterized in that the described flushing gas (P), or the venting gas (PP) from the system, or the H2 product gas (H2PG) from outside the system, is flushed in batches through one or more openings in the m-channel rotary valve channel (groove), and the number of openings is at most 4. Preferably, the venting gas (PP) from the system is used as the flushing gas (P), and the yield of the H2 product gas (H2PG) reaches more than 93%.

[0012] Furthermore, the described conversion gas full-temperature range simulated rotating moving bed pressure swing adsorption enhanced reaction hydrogen production process is characterized in that the described inversion (D) step adopts a vacuuming method for desorption, and the additional vacuum pump is either connected to the logistics pipeline of the desorbed gas outflow m channel rotary valve, or is directly connected to the external pipeline connected to the outlet end of the adsorption tower on the annular rotating tray and a control valve is provided on the external pipeline, preferably directly connected to the external pipeline connected to the outlet end of the adsorption tower on the annular rotating tray and a control valve is provided on the external pipeline.

[0013] Furthermore, the described conversion gas full-temperature range simulated rotating moving bed pressure swing adsorption enhanced reaction hydrogen production process is characterized in that the described final charge (FR), or the conversion gas raw material (F) or H2 product gas (H2PG) from outside the system, when the purity of the H2 product gas (H2PG) is required to be greater than or equal to 99.99%, preferably uses H2 product gas (H2PG) as the final charge (FR).

[0014] Furthermore, the described full-temperature range simulated rotating moving bed pressure swing adsorption enhanced reaction process for shift gas is characterized in that the n loaded mixed catalysts / adsorbents in the described full-temperature range simulated rotating moving bed pressure swing adsorption enhanced reaction (FTrSRMPSA-ERP) system are either composed of an iron-based medium-temperature shift catalyst and lithium carbon molecular sieve / activated carbon particles stacked at a ratio of 1:1~1.5, or are composed of composite catalytic adsorbent particles of carbon nanotubes (CNTs) or carbon fibers (CNFs) / activated carbon (AC) / aluminum oxide loaded with iron active components, or are honeycomb and bundled regular composite catalytic adsorbents made of polymer organic matter or carbon nanotubes or carbon fibers or silicate fibers as substrates and loaded with iron-based active components. Preferably, or are composed of iron-based medium-temperature shift catalysts and lithium carbon molecular sieve / activated carbon particles stacked at a ratio of 1:1.1, or are bundled and honeycomb regular composite adsorbents made of silicate fibers (containing silicon fluoride, ceramics and glass fibers) as substrates and loaded with iron / lithium-based active components.

[0015] The beneficial effects of the present invention are:

[0016] (1) Through the present invention, the fixed bed shift reaction and the fixed bed PSA separation process in the production of hydrogen from hydrocarbon (oxygen) compounds can be coupled and simulated to become a full-temperature rotary wheel moving bed pressure swing adsorption enhanced reaction hydrogen production process, and under medium and low temperature (90-150°C) and low pressure (0.2-1.0MPa) operating conditions, H2 product gas can be directly obtained with high purity and high yield, with a purity greater than or equal to 99.99% and a yield greater than or equal to 92-95%, breaking through the limitation of the existing adsorption enhanced reaction hydrogen production process that cannot directly obtain high-purity and high-yield H2 product gas, and further reducing investment and cost.

[0017] (2) The present invention can realize a multi-combination and multi-step PSA cycle operation of adsorption and desorption in a traditional fixed bed adsorption reactor (tower) process by regulating and matching the rotation direction and rotation speed (ω1 and ω2) of the multi-channel rotary valve and the annular rotating tray, so that the conversion gas reaction equilibrium tends to move towards the direction of complete reaction, thereby forming a "simulated rotating moving bed" pressure swing adsorption enhanced reaction process, realizing a simulated rotating moving bed pressure swing adsorption enhanced reaction process based on the axial flow fixed bed pressure swing adsorption enhanced reaction, and can be flexibly adjusted according to the technical index requirements of the product H2, and covers existing moving bed PSA processes including a combination process of a multi-channel rotary valve and a traditional fixed bed PSA and a moving bed process of a typical fan-shaped adsorption chamber rotating wheel PSA or fast wheel PSA.

[0018] (3) The present invention significantly reduces the number of program control valves and regulating valves in the traditional fixed-bed PSA enhanced reaction hydrogen production device, while also reducing the complexity of manufacturing the fast-wheel PSA device and being able to replace foreign imports, further reducing investment and production costs.

[0019] (4) The present invention adapts to the working conditions where the raw gas has large fluctuations, including fluctuations in components, concentration, pressure, flow rate, etc., by regulating and matching the rotation direction and rotation speed (ω1 and ω2) of the multi-channel rotary valve and the annular rotating tray. The operation flexibility is large, and the catalyst / adsorbent mixing forms are diverse, the service life is long, and the production cost is low.

[0020] (5) According to the requirements of the raw gas and its fluctuating operating conditions and the technical indicators of the product H2, the present invention adjusts and designs the height-to-diameter ratio of the adsorption reactor (tower) by adjusting the rotation direction of the rotary valve and the annular rotating tray and the matching of the rotation speeds ω1 and ω2 as well as the adsorption pressure and temperature, so that the radial diffusion in the axial flow fixed bed is negligible and the mature mass transfer model of the axial flow fixed bed is satisfied. The influence of the axial flow diffusion becomes smaller and smaller as ω2 increases and the height-to-diameter ratio decreases, thereby making the mass transfer process in the adsorption tower closer to the "steady-state" effect of a moving bed represented by a circulating bed, and the purity and yield of the H2 product tend to be "double high". BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is a schematic diagram of the process of Example 1 of the present invention.

[0022] Figure 2 This is a schematic diagram of the process of Example 2 of the present invention. DETAILED DESCRIPTION

[0023] In order to enable those skilled in the art to better understand the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention.

[0024] Example 1 Figure 1As shown, a full-temperature range simulated rotating moving bed pressure swing adsorption enhanced hydrogen production process for shift gas is described, wherein the full-temperature range simulated rotating moving bed is loaded with an iron-based medium-temperature shift catalyst and a lithium carbon molecular sieve / activated carbon mixed adsorbent in a ratio of 1:1.The adsorption reaction tower (n=4) and the corresponding driving mechanism are arranged on a circular rotating tray with a rotation speed of ω2 = 400~600s, and there are 7 channels (m=7) and are arranged in the center of the circular tray with a rotation speed of ω1 = A FTrSRMPSA-ERP system is formed by a 7-channel rotary valve with a rotation speed of 400~600s, a material pipeline for the inlet and outlet of the 7-channel rotary valve and the desorption gas (D) composed of H2 product gas (H2PG), raw gas (F), reverse venting gas (D) and flushing waste gas (PW) outside the system, and a process pipeline connected to the upper and lower adsorption reaction towers and the inlet and outlet of the 7-channel rotary valve through the built-in pipeline of the annular rotating tray, as well as a H2 product gas (H2PG) / desorption gas (D) buffer tank, a compressor, a superheater, a heat exchanger 1 / heat exchanger 2, a condenser, a steam boiler and a CO2 absorption tower. The rotation speed of the 7-channel rotary valve is ω1 The rotation speed ω2 of the annular rotating tray is equal to 400~600s and the rotation direction is counterclockwise, that is, the rotation control mode of the two is synchronous in the same direction. The functions of the 7 channels in the 7-channel rotary valve are respectively, 4 channels supply the desorption gas (D) composed of raw gas (F) (such as m=1), H2 product gas (H2PG) (such as m=2), reverse venting (D) (such as m=5), and flushing waste gas (PW) (such as m=6) and the raw gas (F) as the final charging gas (FR) (such as m=7) The material gas channel, 1 (such as m=3) supplies the process gas channel for the equal pressure reduction gas (ED) and the equal pressure increase gas (ER) to flow, and 1 (such as m=4) supplies the process gas channel for the forward venting (PP) as the flushing gas (P). A compressor, a raw gas (F) buffer tank, The desorbed gas (D) composed of the reverse bleed gas (D) and the flushing waste gas (PW) flows out of the material pipeline at the outlet of the 7-channel rotary valve, which is successively connected to the heat exchanger 2, the desorbed gas (D) buffer tank, the condenser, the non-condensable gas 1 and the CO2 absorption tower, the non-condensable gas 2 and the raw gas (F) material pipeline, and the condensed water is connected to the steam boiler, the water vapor is connected to the heat exchanger 1 and the superheater, and the H2 product gas (H2PG) material pipeline flowing out of the outlet of the 7-channel rotary valve is connected to the H2 product gas (H2PG) buffer tank. The raw gas (F) is a hydrogen-containing conversion gas obtained from natural gas by steam catalytic reforming. Its typical components are hydrogen (H2) concentration 55% (v / v), carbon monoxide (CO) concentration 15%, carbon dioxide (CO2) 5%, water vapor 15%, methane (CH4) 8%, and light hydrocarbon components 2%, which are pressurized to 0.6~0.8MPa and the temperature after being superheated by the raw gas (F) buffer tank and the superheater is 120~130℃, and enters the material channel of the raw gas (F) (such as m=1) through the material pipeline connected to the inlet through hole of the 7-channel rotary valve channel, and enters the adsorption reaction tower 1 through the process pipeline formed by the built-in pipeline of the annular rotating tray and the inlet end of the adsorption reaction tower 1, and performs the reaction adsorption (CR-A) step of conversion reaction (CR) and adsorption (A), and the non-adsorbed phase gas flows out from the outlet end of the adsorption reaction tower 1 through the process pipeline connected to the adsorption reaction tower 1. The process pipeline consists of the through holes of the built-in pipeline of the annular rotating tray and the material channel of the 7-channel rotary valve (e.g. m=2). The hydrogen (H2) purity of the H2 product gas (H2PG) with a purity greater than or equal to 99.99% (v / v) flows out from the product gas (PG) material pipeline connected to the 7-channel rotary valve and the H2 product gas (H2PG) buffer tank, enters the H2 product gas (H2PG) buffer tank and is directly transported to the outside. After the reaction adsorption (CR-A) step is completed, as the 7-channel rotary valve and the annular rotating tray rotate synchronously in the same direction in the counterclockwise direction, the adsorption reaction tower 1 rotates to. Figure 1 The pressure equalization (ED) and forward release (PP) operation steps are performed at the position of the adsorption reaction tower 2. The pressure equalization gas (ED) flowing out of the adsorption reaction tower 1 flows through the built-in pipeline of the annular rotating tray and the pressure equalization gas (ED) channel of the 7-channel rotary valve (such as m=3), and its outlet end is connected to the built-in pipeline of the annular rotating tray and the inlet end of the adsorption reaction tower 4 which is in the pressure equalization (ER) step. The process pipeline is connected to the adsorption reaction tower 4 (at this time, the position of the tower has stepped to the initial position of the adsorption reaction tower 1) for pressure equalization, so that the pressure in the adsorption reaction tower 1 and the adsorption reaction tower 4 is equal to 0.2~0.3MPa, and then, the annular rotating tray and the 7-channel rotary valve continue to be in the same direction. During the synchronous rotation process, the adsorption reaction tower 1 that has finished the equalizing pressure drop (ED) step enters the PP step, and the PP gas flowing out of it flows as the flushing gas (P) through the built-in pipeline of the annular rotating tray and the PP channel (such as m=4) of the 7-channel rotary valve, and its outlet end is connected to the built-in pipeline of the annular rotating tray and the inlet end of the adsorption reaction tower 3 that is in the flushing (P) step, and then enters the adsorption reaction tower 3 (at this time, the position of the tower has stepped to the initial position of the adsorption reaction tower 4) for flushing (P). As the annular rotating tray and the 7-channel rotary valve continue to rotate synchronously in the same direction, the position of the adsorption reaction tower 1 that has finished the PP step moves to Figure 1The initial position of the adsorption reaction tower 3 enters the reverse discharge (D) step, and the pressure is reversely reduced from the adsorption reaction tower 1 to normal pressure, and the reverse discharge gas (D) flows out as the desorption gas (D) through the built-in pipeline of the annular rotating tray and the reverse discharge gas (D) channel (such as m=5) of the 7-channel rotary valve and its outlet, and flows out through the desorption gas (D) buffer tank after being cooled by the heat exchanger 2 to enter the condenser. The non-condensable gas 1 generated from the condenser directly enters the CO2 absorption tower with organic amine as the absorbent for decarbonization, thereby producing high-concentration rich product CO2. The non-condensable gas 2 generated thereby is directly returned to the raw gas (F) after heat exchange and heating with the reverse discharge gas (D) in the heat exchanger 2, and the H2 and CO therein are further recovered. The condensate generated from the condenser is water, which forms water vapor after entering the steam boiler and enters the superheater after heat exchange in the heat exchanger 1, and forms superheated raw gas together with the raw gas (F) to enter the FTrSRMPSA-ERP system, wherein the ratio of the circulating water vapor to the newly added water (steam) is The ratio of H (H2O): C (CO) in the raw gas (F) can be adjusted according to the ratio requirements of the shift reaction, so that the shift reaction and CO2 adsorption reach a complete dynamic balance. As the annular rotating tray and the 7-channel rotary valve continue to rotate synchronously in the same direction, the adsorption reaction tower 1 that has completed the reverse release (D) step enters the flushing (P) step during continuous movement, and the forward release gas (PP) flowing out of the adsorption reaction tower 4 that is in the forward release (PP) step enters the adsorption reaction tower 1 as the flushing gas (P) for flushing (P). The flushing waste gas (PW) generated therefrom flows through the built-in pipeline of the annular rotating tray and the flushing waste gas (PW) channel (such as m=6) of the 7-channel rotary valve and its outlet end and flows out as the desorbed gas (D) and is cooled by the heat exchanger 2. After flowing through the desorbed gas (D) buffer tank and processed according to the desorbed gas (D) processing flow, as the annular rotating tray and the 7-channel rotary valve continue to rotate synchronously in the same direction, the position of the adsorption reaction tower 1 that has completed the flushing (P) step moves to Figure 1The initial position of the adsorption reaction tower 4 enters the equalizing pressure rise (ER) and final filling (FR) steps, and the equalizing pressure reduction gas (ED) flowing out of the adsorption reaction tower 3 which is in the equalizing pressure drop (ED) step flows through the built-in pipeline of the annular rotating tray and the common channel (such as m=3) of the equalizing pressure drop (ED) / equalizing pressure rise (ER) of the 7-channel rotary valve and its outlet and flows through the built-in pipeline of the annular rotating tray into the adsorption reaction tower 1 for equalizing pressure rise (ER), so that the pressure in the adsorption reaction tower 1 is increased from normal pressure to the pressure equal to that in the adsorption reaction tower 3 which is in the equalizing pressure drop (ED) step, both of which are 0.2~0.3MPa. As the annular rotating tray and the 7-channel rotate, the pressure in the adsorption reaction tower 1 is increased from normal pressure to the pressure equal to that in the adsorption reaction tower 3 which is in the equalizing pressure drop (ED) step, both of which are 0.2~0.3MPa. The valve rotates continuously and synchronously in the same direction. The adsorption reaction tower 1 that has finished the equalizing pressure rise (ER) step receives the raw gas (F) from outside the system as the final charging (FR) during the rotation process, and flows through the final charging (FR) channel of the 7-channel rotary valve (e.g., m=7) and the built-in pipeline of the annular rotating tray and the inlet of the adsorption reaction tower 1 for pressurization, so that the pressure in the adsorption reaction tower 1 rises to the pressure of 0.6~0.8MPa required for the reaction-adsorption (CR-A) step, thereby forming a complete pressure swing adsorption (PSA) enhanced reaction closed-loop cycle operation of the adsorption reaction tower 1, that is, reaction adsorption (CR-A)-equalizing pressure drop (ED) / forward release (PP)-reverse release ( D) / flushing (P)-equalizing pressure rise (ER) / final filling (FR) steps, and then the adsorption reaction tower 1 enters the next closed-loop cycle operation process of reaction adsorption and desorption, and the corresponding material gas and process gas entering and leaving the adsorption reaction towers 2, 3 and 4 also rotate synchronously in the same direction during the closed-loop cycle operation process of reaction adsorption and desorption of the adsorption reaction tower 1 through the annular rotating tray and the 7-channel rotary valve, and the 7-channel rotary valve regularly switches the 7 channels to synchronously and regularly switch the material or process gas inlet and outlet positions of each adsorption reaction tower to perform the corresponding closed-loop cycle operation steps of reaction adsorption and desorption, and each adsorption reaction tower has a closed-loop cycle. The closed-loop cycle operation steps all correspond to the closed-loop cycle operation steps of the other three adsorption towers. Thus, high-purity hydrogen (H2) product gas with a hydrogen purity greater than or equal to 99.99% is directly and continuously produced from the conversion gas with a hydrogen (H2) concentration of 55% (v / v), carbon monoxide (CO) concentration of 15%, carbon dioxide (CO2) of 5%, water vapor of 15%, methane (CH4) of 8% and light hydrocarbon components of 2% as the raw gas, and the yield is greater than or equal to 92%, realizing the "double highs" of high purity and high yield of the simulated rotary PSA process based on the axial flow fixed bed of the adsorption enhanced reaction (SERP) process.

[0025] Example 2 Figure 2As shown, on the basis of Example 1, the conversion gas is the raw gas that is not pressurized by a compressor but is pressurized to 0.2MPa by a blower or directly comes from the 0.2MPa conversion gas produced by the natural gas catalytic reforming reaction unit and enters the FTrSRMPSA-ERP system, and a vacuum pumping system is added in which the outlet of the adsorption reaction tower is connected to the vacuum pump by an external pipeline, and the CO2 absorption tower is omitted, wherein the rotation speed ω2 of the annular rotating tray in the system is adjusted to 0, that is, it does not rotate, and the rotation direction of the 7-channel rotary valve is still maintained in the counterclockwise direction, and its rotation speed ω1 is adjusted to 200~300s level, and the initial positions of the 4 adsorption reaction towers are consistent with Example 1, but are fixed. The 7-channel rotary valve is periodically (speed) counterclockwise rotated and stepped and periodically (speed) alternately switched so that each adsorption reaction tower undergoes the closed cycle operation steps of reaction-adsorption (CR-A)-reverse release (D) / vacuuming (V)-vacuum flushing (VP)-final filling (FR) reaction-adsorption and desorption. Among them, the flushing gas (P) comes from the pressurized superheated steam outside the system with a temperature of 140~150℃. After the vacuum desorption of the adsorption reaction tower is completed, vacuum flushing (VP) is carried out. The vacuum flushing waste gas (VPW) formed is used as the desorption gas (D) together with the reverse release gas (D) and the vacuum desorption gas (VD). After heat exchange and cooling in the heat exchanger 2, it enters the desorption gas (D) buffer tank. After that, it enters the condenser for condensation. The generated condensed water is heated by heat exchange with H2 product gas (H2PG) in heat exchanger 1 and then enters the steam boiler. The formed water vapor enters the system together with the raw gas through the heat exchanger for reaction-adsorption and desorption regeneration closed cycle operation. One channel (such as m=4) of the 7-channel rotary valve is an empty channel, which is used in the vacuum step. All material gases and process gases are evenly and alternately distributed in the 7 circular channels of the rotary valve in the system and the built-in pipes in the annular rotating tray and each adsorption reaction tower, and a cycle of pressure swing adsorption (PSA) is connected through the rotating rotary valve (ω1) and the corresponding static annular rotating tray (ω2). 2=0) on the adsorption reaction tower respectively carries out each step of the reaction adsorption and desorption process simultaneously, and the position of the process gas entering and leaving the adsorption reaction tower is constantly changed by the rotation direction and rotation speed (ω1) of the 7-channel rotary valve, so that each adsorption reaction tower can repeat the reaction-adsorption and desorption steps, which is equivalent to each fixed-bed adsorption reaction tower completing its own reaction-adsorption and desorption steps during the rotation of the 7-channel rotary valve without rotating, thereby forming a "simulated rotating moving bed" pressure swing adsorption enhanced reaction process, thereby, the product H2 obtained from the shift gas containing H2 / CO / CO2 / H2O / CH4 has a purity greater than or equal to 99.9%, and a yield greater than or equal to 92%.

[0026] Obviously, the above-described embodiments are only a part of the embodiments of the present invention, but not all of them. Based on the embodiments recorded in the present invention, all other embodiments obtained by those skilled in the art without creative work, or structural changes made under the enlightenment of the present invention, all of which have the same or similar technical solutions as the present invention, fall within the protection scope of the present invention.

Claims

1. A full-temperature range simulated rotating moving bed pressure swing adsorption enhanced reaction hydrogen production process for shifted gas, wherein the full-temperature range simulated rotating moving bed pressure swing adsorption enhanced reaction system is denoted as "FTrSRMPSA-ERP" system, which is composed of n natural integers of 2 to 10 and denoted as n, which are loaded with a medium-low temperature shift catalyst and a composite adsorbent mixed in a certain proportion of catalyst and adsorbent and have a certain height-to-diameter ratio of axial flow fixed bed adsorption reaction towers and are arranged on an annular rotating tray with a rotation speed denoted as "ω2" and a unit of "seconds / cycle", and n natural integers of 5 to 36 and denoted as n. A FTrSRMPSA-ERP system is formed by m channels denoted as m and arranged in the center of a circular rotating tray, a rotary valve rotating at a speed denoted as "ω1" and in units of "seconds / cycle", a material pipeline for the rotary valve and material gas outside the system to enter and exit, and a process pipeline connected to the upper and lower adsorption reaction towers and the rotary valve through the built-in pipeline of the circular rotating tray, and a corresponding driving mechanism for driving the rotation direction of the circular rotating tray and the rotary valve and regulating its rotation speed ω1 and ω2, a buffer tank, and a condenser or a heat exchanger or a superheater or a booster or a vacuum pump, characterized in that: The pipelines connecting the inlet and outlet of the adsorption reaction tower and the inlet and outlet of the m-channel rotary valve are connected through the built-in pipeline preset in the circular rotating tray to form a process pipeline and are the same as the number of channels m of the rotary valve. The positions of the material gases entering and leaving the FTrSRMPSA-ERP system are fixed by the distribution of the rotating channels of the m-channel rotary valve. The material gases include the conversion gas, which is the raw gas marked as "F", the H2 product gas marked as "H2PG", the flushing gas outside the system marked as "P", the final charging gas outside the system marked as "FR" and the final charging gas marked as D D The desorption gas denoted as "D" is composed of the reverse bleed gas or / and the vacuum air denoted as "V" or / and the flushing waste gas denoted as "PW", and is connected accordingly to equipment including a buffer tank, a condenser or a heat exchanger or a superheater or a booster or a vacuum pump. The position of the process gas flow in the process pipeline connected between the inlet and outlet of the m-channel rotary valve and the inlet and outlet of the adsorption reaction tower through the built-in pipeline in the circular rotating tray is moved and changed alternately. The process gas flows in the FTrSRMPSA-ERP system, including the raw gas F, the forward bleed gas denoted as "PP", the flushing gas P inside and outside the system, the pressure-equalizing gas denoted as "ED", and the reverse bleed gas D D Or / and the desorption gas D composed of the vacuum air V or / and the flushing waste gas PW, the equalized pressure rising gas recorded as "ER", the final charging gas FR and the product hydrogen H2PG. The specific reaction-adsorption and desorption cycle process is that the raw material conversion gas F from outside the FTrSRMPSA-ERP system enters the raw material gas F inlet of the multi-channel rotary valve, and passes through the raw material gas F channel and outlet of the rotary valve, the built-in pipeline of the annular rotating tray and the process pipeline connected to the inlet of one or more axial flow fixed bed adsorption reaction towers in the reaction-adsorption state recorded as "CR-A" on the annular rotating tray, and enters from the bottom of the adsorption reaction tower to perform the reaction-adsorption CR-A step, and is continuously stepped through the regulation and matching between the rotation direction and rotation speed ω1 of the m-channel rotary valve and the rotation direction and rotation speed ω2 of the annular rotating tray, from the adsorption reaction The non-adsorbed phase gas flowing out of the top of the tower just enters the H2 product gas H2PG channel of the m-channel rotary valve through the process pipeline, and flows out from the H2 product gas H2PG channel of the rotary valve to form H2 product gas H2PG, and then enters the H2 product gas buffer tank for output. After the adsorption reaction tower in the reaction-adsorption CR-A state completes the reaction-adsorption CR-A step, as the m-channel rotary valve and the annular rotating tray continue to rotate and step, or / and the adsorption reaction tower that ends the reaction-adsorption CR-A performs a forward release or an equal pressure drop step on another or several adsorption reaction towers in the flushing or equal pressure increase state through the process pipeline in the system. The adsorption reaction tower that ends the forward release or equal pressure drop step enters the reverse release or / and vacuumization or / and flushing step as the m-channel rotary valve and the annular rotating tray continue to rotate and step, and the reverse release gas D flowing out of the adsorption tower D or / with the desorbed gas D formed by the vacuum air V or / with the flushing waste gas PW, or through the internal or external pipeline of the annular rotating tray and the reverse exhaust gas D of the rotary valve D / Evacuate air V / flush the waste gas PW channel and its outlet end and flow out and flow through the desorbed gas D buffer tank, the desorbed gas D is CO2-enriched gas, or directly enters the condenser to remove water and produce high-concentration CO2 as a by-product, or enters the decarbonization and H2 recovery process, or returns to the natural gas / light hydrocarbon steam reforming reaction to prepare conversion gas or raw gas process as a carbon-hydrogen ratio adjustment, and ends the adsorption reaction tower in the inversion or / and vacuumization or / and flushing steps, and as the m channel rotary valve and the annular rotating tray continuously rotate and step, it enters the equalization pressure increase or / and the waiting area step marked as "-", flows out from the adsorption reaction tower in the equalization pressure drop step and enters the adsorption reaction tower in the equalization pressure increase step through the built-in pipeline of the annular rotating tray and the rotary valve equalization pressure drop gas ED channel to carry out The pressure is equalized until the pressure in the adsorption reaction tower in the equalization pressure increase step is equal to the pressure in the adsorption reaction tower in the equalization pressure drop step, and the pressure equalization and / or waiting area step of the adsorption reaction tower are terminated. As the m-channel rotary valve and the annular rotating tray further rotate continuously, the final charging step is entered, and the H2 product gas H2PG or the raw material conversion gas F flows as the final charging gas FR through the m-channel rotary valve final charging gas FR channel and the built-in pipeline of the annular rotating tray into the adsorption reaction tower for pressurization until the pressure in the adsorption reaction tower reaches the reaction-adsorption pressure required for the reaction-adsorption CR-A step, and prepares for the next round of reaction-adsorption and desorption cycle operation, wherein each adsorption reaction tower performs one step or multiple steps and each step is performed equally. By regulating and matching the rotation direction and rotation speed ω1 of the m-channel rotary valve with the rotation direction and rotation speed ω2 of the annular rotating tray, the timing table of the cyclic operation of the reaction-adsorption and desorption of the m channels in the rotating m-channel rotary valve and the n adsorption reaction towers in the rotating annular rotating tray is connected end to end into a circle, and the operational cyclicity of the reaction-adsorption and desorption process of the pressure swing adsorption enhanced reaction recorded as "PSA" is completely formed, all the material gases and process gases are evenly and alternately distributed in the m circular channels of the m-channel rotary valve in the system and the built-in pipelines in the annular rotating tray and each adsorption reaction tower, and a cycle of the pressure swing adsorption PSA enhanced reaction process is connected through the rotating m-channel rotary valve ω1 and the corresponding connected The adsorption reaction towers on the rotating annular rotating tray ω2 respectively carry out various steps in the reaction-adsorption and desorption process simultaneously, and the position of the process gas entering and exiting the adsorption reaction tower is constantly changed by matching the rotation direction and rotation speed ω1 of the m-channel rotary valve with the rotation direction and rotation speed ω2 of the annular rotating tray, so that each adsorption reaction tower repeats the reaction-adsorption and desorption steps, which is equivalent to each fixed-bed adsorption reaction tower completing its own reaction-adsorption and desorption steps while the m-channel rotary valve and the annular rotating tray rotate, thereby forming a "simulated rotating moving bed" pressure swing adsorption enhanced reaction process, thereby, the product H2 product gas H2PG obtained from the conversion gas has a purity greater than or equal to 99.99%, and a yield greater than or equal to 92%.

2. A process for producing hydrogen by a full-temperature range simulated rotating moving bed pressure swing adsorption enhanced reaction of a shift gas as claimed in claim 1, characterized in that: The rotation direction of the m-channel rotary valve and the annular rotating tray and the regulation and matching between their rotation speeds ω1 and ω2 include: 1) same-direction synchronization, same-direction rotation in clockwise or counterclockwise direction, ω1 and ω2 are equal, and both ω1 and ω2 are not 0; 2) same-direction asynchronism, same-direction rotation in clockwise or counterclockwise direction, and ω1>ω2 or ω1<ω2, and ω1 or ω2 is 0; 3) different-direction synchronization, different-direction rotation, ω1 and ω2 are equal, and both ω1 and ω2 are not 0; 4) different-direction asynchronism, different-direction rotation, and ω1>ω2 or ω1<ω2, and ω1 or ω2 is 0.

3. A process for producing hydrogen by a full-temperature range simulated rotating moving bed pressure swing adsorption enhanced reaction of a shift gas as claimed in claim 1, characterized in that: The combination of closed-cycle operation steps of reaction-adsorption and desorption of the full-temperature simulation rotating moving bed pressure swing adsorption enhanced reaction FTrSRMPSA-ERP system also includes 1 to 2 times of pressure equalization, 1 to 2 batch flushing, 1 time of vacuuming, 1 to 2 times of heating and cooling heat exchange temperature swing adsorption, 1 time of sequential placement and pressure drop equalization sequence offset, 1 waiting area step, and the number of adsorption reaction towers n and the corresponding number of channels m of the m-channel rotary valve increase, the height-to-diameter ratio of the adsorption tower recorded as "h / r" decreases, and the rotation speed of the m-channel rotary valve or the annular rotary tray is fast enough or the rotation cycle is short enough. The separation effect of the product H2 and CO2 in the shift gas adsorption enhanced reaction system is infinitely close to the "steady-state" mass transfer separation process of the moving bed, and the shift gas reaction equilibrium tends to move towards the direction of complete reaction, and the purity of the H2 product gas H2PG finally obtained is greater than or equal to 99.999%, and the product gas yield is greater than or equal to 95%.

4. A process for producing hydrogen by a full-temperature range simulated rotating moving bed pressure swing adsorption enhanced reaction of shift gas as claimed in claim 1, characterized in that: The raw material conversion gas F is a mixed gas obtained by steam catalytic reforming or thermal cracking of methane, methanol or other hydrocarbons, containing 30-60% H2(V), 10-20% CO(V), 10-20% CO2(V), unreacted water, hydrocarbons and other hydrocarbons or organic by-product impurities, with a temperature of 90-150°C, a pressure of 0.2-1.0MPa, and a flow rate of 100-20,000Nm 3 / h.

5. The process for producing hydrogen by a full-temperature range simulated rotating moving bed pressure swing adsorption enhanced reaction of a shift gas according to claim 1, characterized in that: The flushing gas P, or the vent gas PP from the system, or the H2 product gas H2PG from outside the system, is flushed in batches through one or more openings in the m-channel rotary valve channel, and the number of openings is at most 4.

6. A process for producing hydrogen by a full-temperature range simulated rotating moving bed pressure swing adsorption enhanced reaction of shifted gas as claimed in claim 1, characterized in that: The reverse placement step adopts a vacuuming method for desorption, and the additional vacuum pump is either connected to the logistics pipeline of the desorbed gas outflowing the m-channel rotary valve, or directly connected to the external pipeline connected to the outlet end of the adsorption tower on the annular rotating tray and a control valve is provided on the external pipeline.

7. A process for producing hydrogen by a full-temperature range simulated rotating moving bed pressure swing adsorption enhanced reaction of a shifted gas as claimed in claim 1, characterized in that: The final charge FR may be the conversion gas raw material F or H2 product gas H2PG from outside the system.

8. The process for producing hydrogen by a full-temperature range simulated rotating moving bed pressure swing adsorption enhanced reaction of a shift gas as claimed in claim 1, characterized in that: The n mixed catalysts and adsorbents loaded in the full-temperature simulated rotating moving bed pressure swing adsorption enhanced reaction FTrSRMPSA-ERP system are either composed of iron-based medium-temperature shift catalysts and lithium-carbon molecular sieves stacked at a ratio of 1:1 to 1.5, or iron-based medium-temperature shift catalysts and activated carbon particles stacked at a ratio of 1:1 to 1.

5.

9. A process for producing hydrogen by a full-temperature range simulated rotating moving bed pressure swing adsorption enhanced reaction of shifted gas as claimed in claim 1, characterized in that: The n loaded mixed catalysts and adsorbents in the full-temperature simulated rotating moving bed pressure swing adsorption enhanced reaction FTrSRMPSA-ERP system are composed of carbon nanotube composite catalytic adsorbent particles marked as "CNTs" loaded with iron active components, or carbon fibers marked as "CNFs" loaded with iron active components, or activated carbon marked as "AC" loaded with iron active components, or composite catalytic adsorbent particles of aluminum oxide loaded with iron active components.

10. The process for producing hydrogen by a full-temperature range simulated rotating moving bed pressure swing adsorption enhanced reaction of shift gas according to claim 1, characterized in that: The n mixed catalysts and adsorbents loaded in the full-temperature range simulated rotating moving bed pressure swing adsorption enhanced reaction FTrSRMPSA-ERP system are composed of honeycomb and bundled regular composite catalytic adsorbents made of high molecular organic matter as the substrate, carbon nanotubes as the substrate, carbon fiber as the substrate, or silicate fiber as the substrate, and loaded with iron-based active components.

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