CN117658072A - Natural gas vapor combined conversion and proton exchange membrane water electrolysis coupling hybrid hydrogen production system - Google Patents
Natural gas vapor combined conversion and proton exchange membrane water electrolysis coupling hybrid hydrogen production system Download PDFInfo
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- Hydrogen, Water And Hydrids (AREA)
Abstract
The invention discloses a mixed motion hydrogen production system with combined conversion of natural gas and water vapor and hydrolytic coupling of proton exchange membrane, which consists of an energy source raw material module, a combined conversion (SUR) hydrogen production module, a proton exchange membrane water electrolysis (PEM) hydrogen production module and a Pressure Swing Adsorption (PSA) hydrogen extraction module, and is characterized in that energy transfer, conversion efficiency and energy efficiency are balanced in the process of preparing hydrogen with purity of 99.995% or more from natural gas and water (steam) serving as raw materials, and hydrogen production modularization can be automatically switched according to resource supply conditions.
Description
Technical Field
The invention belongs to the technical field of hydrogen preparation in hydrogen energy, and particularly relates to a hybrid hydrogen production system by combining natural gas and water vapor conversion and proton exchange membrane water electrolysis coupling.
Background
Hydrogen energy is one of the most promising clean energy sources at present, but is classified into "ash hydrogen" and "green hydrogen" according to whether pollutant is discharged in the process of obtaining or preparing hydrogen, wherein the process of preparing "ash hydrogen" mainly obtains and discharges CO from fossil raw materials containing hydrocarbon elements through catalytic thermal cracking reforming conversion and hydrocarbon separation 2 Or CO or other pollutants, including natural gas, methanol, coal, heavy oil, biogas and other raw materials; the preparation of "green hydrogen" is most typically water-splitting hydrogen production, the whole process is basically zero-emission except by-product oxygen, but water-splitting hydrogen production itself requires higher energy consumption (electric energy) resulting in higher hydrogen production cost and is only suitable for small-scale production.
The method for preparing 'ash hydrogen' by using natural gas as raw material mainly comprises the steps of steam reforming conversion (SMR), partial Oxidation Reforming (POR), oxygen-enriched combustion conversion (OECR), autothermal reforming (ATR), plasma reforming and the like, wherein SMR is the most mature and common traditional hydrogen production method, and the key technology is a reformer or a reforming reactor, generally a radiant chamber (section) provides heat to enable the conversion temperature required by catalytic reforming conversion reaction of methane and steam in a tube in the furnace to be up to 700-850 ℃, and the tube type reformer is limited by a radiation heat transfer mode, so that the miniaturization difficulty of the device is increased, a certain amount of natural gas is consumed as fuel gas to generate a large amount of surplus steam, and further, the consumption of the natural gas and the emission of smoke are increased, and H is reduced at the same time 2 Yield rate. Therefore, how to completely replace or partially replace the radiation section in the SMR process at home and abroad is to provide a plurality of new processes, wherein the natural gas steam is converted into gas forAmong the synthesis gas processes of methanol and the like, there is a so-called "combined reforming process (SUR)", i.e. the core of the combined process is to couple oxygen purged autothermal reforming (ATR) with the traditional SMR process, which has the biggest advantage of being able to produce synthesis gas with high H/C ratio at high pressure, so that the CO content in the reformed gas is controlled to reduce the load of the subsequent shift reaction, even under the action of a suitable catalyst, the shift step can be omitted and more CO can be directly fed through the PSA hydrogen extraction section 2 With less CO removal to purify H 2 . The reaction of the combined conversion process is endothermic, so that the reaction heat is required to be externally supplied, and the energy consumption is high. However, the process reformer adopts multi-tube arrangement, so that the number of burners is reduced, heat loss is reduced, and meanwhile, fuel and combustion-supporting oxygen enrichment among the burners are more uniform and accurate, so that less NOx is formed. Compared with the traditional SMR process, the USR process has the advantages that the size of the SMR converter is only 1/4, only about 30% of methane is converted in the SMR converter, the rest of methane is converted in the ATR, the operating pressure and the temperature of the ATR are not as strict as those of the SMR process, and further, the total investment and the overall equipment size of the combined process are greatly reduced. Thus, the conversion of methane reaches 100%. However, the combined process still has several significant drawbacks: first, although only 30% of methane is converted in the SMR reformer, the consumption of natural gas fuel is much reduced compared with the traditional SMR reforming process, the subsequent 70% of methane is converted in the autothermal ATR, the ATR reforming is a gas (hydrogen or synthesis gas) making process formed by combining the non-catalytic partial oxidation of highly exothermic methane with the highly endothermic steam reforming, the required heat for gasification is generated by combusting the partial raw materials to be converted in the reactor, thus oxygen-enriched or pure oxygen needs to be added, and the oxygen intake directly relates to the reaction temperature and efficiency of the subsequent 70% of methane in the SMR reformer, and the conversion temperature and efficiency of the preceding 30% of methane in the SMR are also affected, and the heat between the two needs to be balanced, so that the increase of air separation oxygen production or PSA (oxygen-enriched) devices can result in the increase of investment and cost; second, the integrated process is easier for producing synthesis gas of suitable hydrocarbon ratio such as methanol, but for the specific manufacture of H 2 For the main and CO-less synthesis gas, the gas needs to be introducedInto extra H 2 To adjust the H/C ratio in the synthesis gas, thereby using high purity product H 2 Regulating, H 2 The yield of product gas is affected; thirdly, the combined process has higher energy consumption and low waste heat utilization rate, and part of waste heat is still used as waste heat to generate steam for output; fourth, the combined process also typically uses purge air to replace oxygen enrichment or pure oxygen for combustion reactions during conventional gas making processes, but in the production of H 2 The main and CO-less conversion synthesis gas can be introduced into a large amount of H 2 Inert gas components having a relatively small separation coefficient, e.g. N 2 Ar, etc., such that subsequent PSA purification separates H 2 The load of (2) increases substantially.
The green hydrogen is produced by renewable energy sources (such as geothermal energy, biomass, ocean energy, wind power, photovoltaic solar energy and solid waste) and the like, and the hydrogen production process has no carbon emission at all, wherein water electrolysis is a main way for preparing the green hydrogen, and is an important support for realizing the aim of double carbon by a necessary technology for developing hydrogen energy. The hydrogen production by water electrolysis is a method for decomposing water into hydrogen (H) 2 ) And oxygen (O) 2 ) Is a chemical process. Currently, hydrogen production by water electrolysis is classified into alkaline water electrolysis hydrogen production technology (ALK or AWE, alkaline Electrolysis), proton exchange membrane hydrogen production technology (PEM, proton Exchange Membrane Electrolysis) and solid oxide water electrolysis hydrogen production technology (SOEC, solid Oxide Electrolysis) according to the difference of electrolysis membranes, wherein the proton exchange membrane water electrolysis technology (PEM) is also called "solid polymer water electrolysis (SPEWE) water electrolysis", the working temperature of an electrolysis cell is generally 60-100 ℃, and the structure is the same as that of a fuel cell, and the proton exchange membrane water electrolysis technology (PEM) consists of an electrolyte membrane/electrode assembly (MEA). The electrolyte membrane generally uses a cation exchange membrane (such as Nafion, flemion) with 100-300 μm, has excellent gas separation function, and can obtain hydrogen with the pressure of 2-5 MPa and the purity of more than 99.99%. In addition, steam-resistant proton exchange membranes have been developed abroad, the working medium is steam, the operating temperature is 100-120 ℃, and the produced H 2 The purity and the pressure are higher, and the energy consumption is higher. PEM hydrogen production has a higher current density than ALK under the same conditions because the MEA structure shortens the distance between the electrodes, allowing electrolysisOhmic losses of the mass become small, so that a high current density can be achieved, leading to a greater hydrogen production energy consumption than ALK. The PEM water electrolysis hydrogen production is one of the development directions of PEM water electrolysis technology, and the hydrogen production capacity of single equipment for PEM hydrogen production at home and abroad can reach 1000-2000 Nm 3 And/or more. The PEM water electrolysis hydrogen production method is different from alkaline water electrolysis hydrogen production, and the PEM water electrolysis hydrogen production method adopts the proton exchange membrane which is composed of perfluorosulfonic acid or other composite materials and has good chemical stability, proton conductivity and gas separation as a solid electrolyte to replace an asbestos membrane, so that electron transfer can be effectively prevented, and the safety of an electrolytic cell is improved. The main components of the PEM water electrolyzer are a proton exchange membrane, a cathode-anode catalytic layer, a cathode-anode gas diffusion layer, a cathode-anode end plate and the like from inside to outside. The diffusion layer, the catalytic layer and the proton exchange membrane form a membrane electrode, which is a main place for material transmission and electrochemical reaction of the whole water electrolysis cell, and the characteristics and the structure of the membrane electrode directly influence the performance and the service life of the PEM water electrolysis cell. Compared with alkaline water electrolyzer, the PEM water electrolyzer has higher working current density >2A/cm 2 ) The overall efficiency is high (74% -87%), and the purity of the separated hydrogen is higher>99.99 percent) and higher gas production pressure (more than 5 MPa), has higher dynamic response speed, can adapt to the fluctuation of renewable energy power generation, and is considered as a water electrolysis hydrogen production technology with great development prospect. At present, PEM water electrolysis hydrogen production technology has been applied to the fields of hydrogen production on site in a hydrogen station, renewable energy source water electrolysis hydrogen production such as wind power, energy storage and the like, and gradually popularized. However, PEM water electrolysis hydrogen production has several significant disadvantages: first, although the PEM electrolysis efficiency can reach 74-87%, which is much higher than alkaline water electrolysis hydrogen production, the overall hydrogen production efficiency is not very high, typically 35-50%, and most of the useful efficiency is still used to produce byproduct O 2 The total hydrogen production efficiency is between the hydrogen production by alkaline water electrolysis and the hydrogen production by solid oxide. Thus, the byproduct O of the hydrogen production by the water electrolysis is fully utilized 2 Is one of the factors related to the cost of PEM hydrogen production; second, because the hydrogen production current density is higher, the energy consumption is higher, the hydrogen production cost is high, and the unit energy consumption (electricity) of the electrolysis tank is higher than that of the whole natural gas water vapor SMR conversion hydrogen production systemThe energy consumption and the area close to the hydrogenation market are generally in tension, the electricity price is higher, and the hydrogen production cost is higher; thirdly, the operation temperature of the electrolytic tank with the working medium being water is 60-100 ℃, the temperature of the working medium being water vapor is 100-120 ℃, the heat energy is consumed by preheating water or high-temperature vapor, the electric energy is used for heating, the response time of the hydrogen production system is slow, and the electric energy is further consumed. Thus, the solution to the heat source of PEM hydrogen production is also one of the key cores of PEM hydrogen production and affects the cost of PEM hydrogen production. Although the PEM electrolyzer yielded H with a purity of 99.99% 2 Can be directly used for industrial grade hydrogen, but the proton membrane often has unstable input current or voltage or short circuit of proton membrane layer in the PEM water electrolysis hydrogen production process, and the like, which leads to O 2 H and H 2 O penetrates to H 2 In which subsequent deoxidation, drying and further purification of H are required 2 Further, the energy consumption and the energy waste are increased, and the energy consumption of the water electrolysis hydrogen production system is high. The short service life of the proton membrane and cathode materials is also one of the important reasons of high cost; fourth, alkaline water electrolysis (ALK) hydrogen production has a certain scale effect, and PEM water electrolysis hydrogen production has a current technical bottleneck in large-scale, small scale effect, resulting in a hydrogen production cost greater than that of alkaline water electrolysis hydrogen production. While the water electrolysis hydrogen production needed in the hydrogenation station is small-sized skid-mounted and is easy, but less than 100Nm 3 And the hydrogen production scale device has larger energy consumption and higher hydrogen production cost. Fifth, the core cost of PEM water electrolysis hydrogen production is the cost of proton membrane and cathode and anode materials, the cost of the core material of PEM hydrogen production is high, and the cost of the core material which is distributed to a miniaturized device is high, which is also the main reason that the water electrolysis hydrogen production in a hydrogen station can not be fully popularized at home and abroad at present.
Disclosure of Invention
To solve the problems of the pure natural gas vapor combined reforming (SUR) hydrogen production and proton exchange membrane water electrolysis (PEM) hydrogen production technology, the primary aim of the invention is to provide a compact and efficient hydrogen production device which has energy transmission, conversion efficiency and energy balance and can be based on nearby H 2 Market natural gas pipe network and power grid resource supply condition selfThe mixed hydrogen production system is characterized in that the mixed hydrogen production system is formed by high-efficiency coupling of SUR hydrogen production and PEM hydrogen production, namely, the mixed hydrogen production system is formed by combining natural gas steam conversion and proton exchange membrane water electrolysis coupling, the respective energy requirements and advantages of natural gas steam SUR conversion hydrogen production and PEM water electrolysis hydrogen production are fully utilized, the hydrogen production raw material structure and the hydrogen supply mode in a hydrogenation station and centralized hydrogen supply mode are regulated and controlled, the energy balance and material balance of the mixed hydrogen production system are realized, the defects that oxygen is needed for SUR hydrogen production, a heat source is needed for PEM hydrogen production and the defects are generated are overcome, the defects are converted into a combined advantage, the hydrogen production cost is reduced, and the green hydrogen output is increased to reduce the gray hydrogen proportion. The mixed hydrogen production system is characterized by comprising an energy source raw material module, a proton exchange membrane water electrolysis (PEM) hydrogen production module, a natural gas water vapor combined conversion (SUR) hydrogen production module, a Pressure Swing Adsorption (PSA) hydrogen extraction module, and pipelines, valves and heat exchangers among the modules, wherein the energy source raw material module is used for preprocessing natural gas raw materials, electric energy, processing water and boiler water and steam, optimizing the components and energy of the raw materials to adapt to the requirements of a downstream module, and comprises natural gas serving as fuel gas of the SUR hydrogen production module, desorption gas generated by the PSA hydrogen extraction module, normal temperature or a heat exchanger or a normal pressure or a booster serving as supplementary air outside the mixed hydrogen production system, preprocessing of natural gas water and process water mixed steam and the preprocessing gas, a natural gas generator or other power supply, preprocessing water, a preprocessing water and boiler water, a heat exchange pipeline, a desalination water and a water inlet and outlet control pipeline, a desalination water and a power pipeline, and an inlet and an outlet control process water and a power storage tank; the PEM hydrogen production module mainly comprises a one-stage or multi-stage serial/parallel proton exchange membrane water electrolysis tank, a water storage tank, a gas-liquid processor, a rectifier, an electric heater, a control system, a throttle valve, a bypass valve and hydrogen (H) 2 ) With oxygen (O) 2 ) Gas cooler, H 2 Catalytic deoxidizer and moduleInternal and external connected power, H 2 、O 2 The gas pipeline and the process (hot/cold) water pipeline and the control valve are formed; the SUR hydrogen production module mainly comprises a preheating converter of mixed steam, an SMR converter/reactor provided with convection and radiation sections, a self-heating steam ATR converter/reactor provided with a combustion chamber at the top, a medium-high temperature shift reactor, a gas-liquid separator, a heat exchanger, a steam drum, a waste heat boiler, and mixed steam, pre-converted gas, middle converted gas, fuel gas, PSA stripping hydrogen suction gas pipelines and desalted water, boiler water supply, a steam storage tank, a circulating water pipeline, a deaerator, a conveying and circulating pump and a control valve which are connected inside and outside the module; the PSA hydrogen extracting module consists of a plurality of adsorption towers connected in series/parallel, a desorption gas buffer tank, and electric power and H connected inside and outside the module 2 Product gas/stripping gas, H flowing out of PEM hydrogen production module 2 The process comprises the following steps of,
(1) The energy source raw material module takes city gas or industrial natural gas as raw material gas, is pressurized to 0.3-5.0 MPa by a compressor and preheated to 250-380 ℃ and enters hydrodesulfurization, and H from the PEM hydrogen production module 2 As hydrogenation source, the desulphurized purified feed gas is mixed with desalted water vapor from a water vapor storage tank bypass valve and medium-low pressure vapor as process vapor flowing out from the SUR hydrogen production module to form natural gas water vapor mixed vapor, and enters the SUR hydrogen production module, and the rest of raw gas except the feed gas is taken as fuel gas from city gas or industrial natural gas and flows out from the PEM hydrogen production module to form O 2 And desorption gas from the PSA hydrogen extraction module or air outside the system is mixed into the SUR hydrogen production module to burn and supplement fuel, so as to burn combustion chambers positioned at the top of the SMR reformer and the top of the ATR reformer in the convection and radiation section in the SUR hydrogen production module, provide heat for conversion of the SMR reformer and the ATR reformer/reactor, come from city tap water or industrial water, and after desalination, part of desalted water is used as cooling water to perform water jet cooling on the ATR reformer/reactor in the SUR hydrogen production module, flows out from a cooling water jacket and is recycled as process circulating waterA part of the process steam is preheated to 70-90 ℃ by desalted water and is used as process water to enter a deaerator of an SUR hydrogen production module and is regulated by a hot water pump, wherein a part of the preheated desalted water is used as a working medium to be input into a PEM hydrogen production module, a part of the preheated desalted water is used as fresh desalted water steam formed by a steam boiler and an SMR converter convection section of the SUR hydrogen production module to form process steam, the process steam as an energy source raw material module enters a steam storage tank, wherein a part of the process steam which flows out is regulated and controlled by a bypass valve to be mixed with purified and desulfurized and is used as raw material natural gas to form mixed steam and then enters the SUR hydrogen production module, or/and a part of the process steam which flows out is used as a steam working medium of PEM hydrogen production flows into the PEM hydrogen production module through a throttle valve, the exhausted flue gas from the SUR hydrogen production module and the PEM hydrogen production module is subjected to cold-heat exchange and gas-liquid separation, water in the PEM hydrogen production module returns to pretreatment, gas is discharged, and the power from an urban power grid or an industrial power grid is directly connected to a control system of the PEM module to provide power required by water and electric heater for starting or independent operation, or a field device or peak power generation is adopted, and comprises a methane power generation station, a natural gas power station and a power generation station is provided for hydrogen production station, and a thermoelectric power station;
(2) The PEM hydrogen production module is characterized in that the power input from an energy source raw material module is connected with a control system consisting of a transformer and a control cabinet, direct-current voltage is input, meanwhile, or when working medium is liquid water, preheated desalted water at 70-90 ℃ flowing out of a water storage tank passes through a regulating valve, or when working medium is desalted water vapor, water vapor flowing out of a water vapor storage tank passes through a throttling injection valve, and the obtained water vapor is cooled to 100-120 ℃ and is removed of liquid water, and then flows into an electrolytic tank, wherein the operating temperature of the electrolytic tank is 70-100 ℃ or 100-120 ℃, the separation concentration of O from an anode of an exchange membrane of the electrolytic tank is 98.5-99.5%, and the pressure of O is 0.3-5.0 MPa 2 Cooling the mixture by a cooler, then entering an oxygen storage tank, and outputting the mixture as fuel gas to enter an SUR hydrogen production module, wherein the concentration of the separated out cathode of the electrolytic tank is
99.0 to 99.99 percent, H with the pressure of 0.3 to 5.0MPa 2 After the water is removed by the water-gas separator, a part of the water is directly deoxidized or is subjected to heat exchange by catalysisAfter cooling, or directly as technical grade H 2 Product gas output, a portion of the H as a feed natural gas hydrodesulfurization for an energy feed module 2 Source, or/and enter
PSA hydrogen extraction module H 2 Purifying and preparing product gas;
(3) SUR hydrogen production module, natural gas steam mixed steam from energy source raw material module is preheated by convection type preheater to form pre-converted gas, then the pre-converted gas enters SMR reformer/reactor of SUR module loaded with nickel/nickel series steam reforming conversion catalyst to make primary catalytic reforming conversion reaction, the reaction temperature is 700-850 deg.C, the reaction pressure is 0.3-5.0 MPa, the heat required by the reformer/reactor reaction is H-contained from urban fuel gas or industrial natural gas and from PSA hydrogen extraction module, the rest of energy source raw material module except raw material gas 2 The air outside the stripping gas and the module is fuel gas, supplementary fuel gas and high-temperature flue gas which flows through the outside of the tube array and is obtained by the radiation heat transfer and is obtained by burning the fuel gas, supplementary fuel gas and combustion-supporting burned gas at the top part, the lower part or the burners at the two sides of the reformer, the discharged high-temperature flue gas is used as a heat source of a preheater, a steam drum, a steam boiler and a reforming waste boiler, and is used as flue gas for emission after heat exchange, temperature reduction and treatment, the methane content in the middle reformed gas is that flows out from the reformer/the reactor
20-40% of the total oxygen enters a combustion chamber arranged at the upper part of an ATR reformer/reactor in the SUR module and 98.5-99.5% O from the PEM hydrogen production module 2 The combustion reaction of non-catalytic partial oxidation and complete oxidation is carried out, the generated combustion heat is directly carried by reactants to form high-temperature gas which is positioned at the lower part of a combustion chamber and is loaded with a nickel/nickel reforming conversion catalyst bed layer to carry out deep reforming conversion reaction, the conversion reaction temperature is 800-950 ℃, the conversion reaction pressure is 0.3-5.0 MPa, the methane conversion rate reaches 100%, a part of desalted water is taken as cooling water to carry out water jet cooling on an ATR converter/reactor, and flows out from a cooling water jacket to be recycled as process circulating water, and the discharged converted gas is subjected to medium-high temperature conversion reaction after being cooled, a steam drum and a waste heat boiler exchange heat supply to desalted process steam, the conversion reaction temperature is 260-450 ℃, and the reaction temperature is reversedThe pressure is 0.3-5.0 MPa, the converted gas forms converted gas after medium-high temperature conversion reaction,
80～90％H 2 carbon dioxide (CO) 9-19% 2 ) Carbon monoxide (CO) less than 1% and residual trace hydrocarbon impurities, and the converted gas enters a PSA hydrogen extraction module for hydrogen extraction after heat exchange with boiler feed water and desalted water;
(4) PSA hydrogen extraction module, purity from PEM hydrogen production module is 99.0-99.99% and H after direct or catalytic deoxidation 2 H-containing with modules from SUR hydrogen production 2 The converted gas with the concentration of 80-90% is respectively or mixed into a Pressure Swing Adsorption (PSA) system formed by at least 3 or more composite bed adsorption towers/devices loaded with adsorbent, pipelines between the adsorption towers/devices, a program control valve and a regulating valve group, wherein the adsorption pressure is 0.3-5.0 MPa, the adsorption temperature is 20-80 ℃, the adsorption towers/devices are alternately switched to perform adsorption and desorption cycle operations comprising adsorption, pressure equalizing, forward discharge, reverse discharge, vacuum/flushing and final filling steps, and the purity of the product is more than or equal to
99.995% of H 2 Product gas enters H 2 The desorption gas obtained from the product gas tank enters the buffer tank and then returns to the SUR hydrogen production plate as the supplementary fuel gas for recycling, thereby H 2 The total yield of the product gas is more than or equal to 90 percent.
Furthermore, the hybrid hydrogen production system with the combined conversion of natural gas and water vapor and the water electrolysis coupling of the proton exchange membrane is characterized in that the purity of the hydrogen production module generated by the PEM is 99.0-99.99 percent and H is directly or catalytically deoxidized 2 H-containing produced with SUR hydrogen production module 2 The ratio of the converted gas with the concentration of 80-90% is 2-4:6-8, and the ratio is prepared by desalted water/process steam, raw material natural gas/fuel gas, process conversion gas and O of a PEM hydrogen production module 2 And the control of the usage amount of desorption gas which flows out of the PSA hydrogen extraction module and is used as the supplementary fuel gas is obtained, wherein, the water supply pump outlet or/and the bypass steam section for controlling the flow of preheated desalted water or/and process steam required by the SUR hydrogen production module through the outlet of the desalted water or/and steam storage tankThe flow valve opening or the high-temperature steam throttle valve opening of the linked PEM hydrogen production module is controlled to regulate and control the flow distribution of the process steam entering the SUR hydrogen production module and the preheated desalted water entering the PEM hydrogen production module or/and the high-temperature steam, and the O from the PEM hydrogen production module 2 With H-containing from PSA hydrogen-stripping module 2 Desorbing H from gas 2 The concentration and flow rate are mainly controlled by the combustion reaction and the reaction temperature in the combustion chamber of the ATR reformer/reactor in the SUR hydrogen production module.
Furthermore, the hybrid hydrogen production system with the combined conversion of natural gas and water vapor and the water electrolysis coupling of the proton exchange membrane is characterized in that the PEM hydrogen production module and the SUR hydrogen production module preheat desalted water/process steam, raw material/fuel natural gas and O of the PEM hydrogen production module by switching and closing 2 The connection between the stripping gas pipeline and the material flow pipeline of the PSA hydrogen extracting module is independently operated, wherein, the H of the PSA hydrogen extracting plate block 2 The gas flow rate of the product is respectively dependent on the purity of 99.0-99.99% H produced by the PEM hydrogen production module and the SUR hydrogen production module 2 And contain H 2 The concentration is 80-90% of the maximum capacity of the change gas.
Furthermore, the hybrid hydrogen production system with the combined conversion of natural gas and water vapor and the water electrolysis coupling of the proton exchange membrane is characterized in that H produced by the hybrid hydrogen production system 2 The gas capacity of the product is 100-20,000 Nm 3 And/h, wherein the hydrogen production capacity of the PEM hydrogen production module is 20-5,000 Nm 3 And/h, the operation elasticity is 10-120%, and the SUR hydrogen production module is 80-15,000 Nm 3 And/h, the operation elasticity is 50-100%, and the PSA hydrogen extraction module is 20-20,000 Nm 3 And/h, the operation elasticity is 30-110%.
Furthermore, the natural gas water vapor combined conversion and proton exchange membrane water electrolysis coupled hybrid hydrogen production system is characterized in that the working medium of the PEM hydrogen production module is liquid desalted water with the temperature of 70-90 ℃, a process steam tank, a throttling injection valve and a high-temperature steam cooler pipeline are closed, preheated desalted water with the temperature of 70-90 ℃ input by a circulating pump from an energy source raw material module directly enters through a pipeline connected with a liquid water inlet of the PEM water electrolyzerPEM water electrolyzer is electrolyzed and O flows out from diaphragm anode 2 The purity is 98.5-99.2%, the pressure is 0.3-3.0 MPa, and the hydrogen is taken as fuel gas to enter SUR hydrogen production module after entering the oxygen storage tank, and H flows out from the diaphragm cathode 2 The purity is 99.0-99.8%, the pressure is 0.3-3.0 MPa, and after gas-liquid separation and catalytic deoxidation, a part of the hydrogen is used as the hydrogen desulfurization H of the raw material natural gas of the energy raw material module 2 Part of the hydrogen is directly or after being pressurized enters a PSA hydrogen extraction module to further obtain H 2 Product gas.
Furthermore, the hybrid hydrogen production system with the combined conversion of natural gas and water vapor and the water electrolysis coupling of the proton exchange membrane is characterized in that on the premise that the pre-conversion gas flow is unchanged in the SUR hydrogen production module, the O from the PEM hydrogen production module is regulated and controlled 2 Flow and new addition of H from PEM hydrogen production module without gas-liquid separation and catalytic deoxygenation 2 The flow rate of the combustion chamber of the ATR reformer/reactor entering the SUR hydrogen production module changes the composition of the outgoing high temperature reformed gas for producing synthesis gas and H 2 A hydrocarbon ratio of conversion gas required downstream, wherein, with O 2 H and H 2 Flow rate is increased to convert H in gas 2 The higher the concentration is, the stability is achieved after 90%, and the methane content in the converted gas is less than 0.1-0.3%.
Furthermore, the natural gas and water vapor combined conversion and proton exchange membrane water electrolysis coupled hybrid hydrogen production system is characterized in that the pre-conversion gas flow entering the SUR hydrogen production module can be divided into two flows, one flow directly enters a convection and radiation section SMR converter/reactor of the SUR hydrogen production module to react, and the other flow directly enters a self-heating ATR converter/reactor of the SUR hydrogen production module to react, so that the load of the radiation section SMR converter/reactor of the SUR hydrogen production module and the natural gas fuel consumption are further reduced, and the O from the PEM hydrogen production module is increased at the same time 2 Flow is introduced into the combustion chamber of the ATR reformer/reactor, thereby adjusting the H of the SUR hydrogen production module 2 Yield and H with PEM hydrogen production module 2 The ratio of the output and the conversion of the final methane reaches 100%.
Furthermore, the natural gas steam combined conversion and proton exchange membrane water electrolysis coupled hybrid hydrogen production system is characterized in that the original reforming conversion catalyst bed layer in the radiant section SMR converter/reactor of the SUR hydrogen production module is changed into a low-temperature catalytic reforming conversion catalyst, the catalyst comprises a catalyst containing nickel/cobalt or rare earth metal active components on a Carbon Nano Tube (CNTs), the initial conversion temperature is 450-600 ℃, the reaction pressure is unchanged, the consumption of natural gas fuel required by conversion reaction of the convection and radiant section SMR converter/reactor is further reduced, and the H-containing of the PSA hydrogen extraction module is adopted 2 Desorption air and air outside the module or O of PEM hydrogen production module 2 As fuel gas, all substitute natural gas fuel, while the low-temperature intermediate reformed gas has a methane content of less than 30%, and enters the ATR reformer/reactor loaded with nickel/nickel-based catalyst of the SUR hydrogen production module for further deep reforming while increasing O from the PEM hydrogen production module 2 The reaction temperature of the deep conversion is 800-960 ℃, the reaction pressure is unchanged, and the methane content in the flowing converted gas is less than 0.1-0.3%.
Furthermore, the natural gas steam combined reforming and proton exchange membrane water electrolysis coupled hybrid hydrogen production system is characterized in that a low-temperature reforming catalyst is filled in a convection and radiation section SMR reformer/reactor of the SUR hydrogen production module, a nickel/nickel reforming catalyst is filled in a self-heating ATR reformer/reactor, and simultaneously, H from a PEM hydrogen production module is introduced into low-temperature intermediate reformed gas from the convection and radiation section SMR reformer/reactor 2 Therefore, the CO content of the converted gas flowing out of the ATR converter/reactor is less than 3-5%, the converted gas directly enters the PSA hydrogen extraction module after heat exchange without medium-high temperature conversion reaction, and the special CO molecular sieve filling amount is required to be increased in the composite adsorbent filled in the PSA adsorption tower/reactor.
Furthermore, the hybrid hydrogen production system with the combined conversion of natural gas and water vapor and the water electrolysis coupling of the proton exchange membrane is characterized in that the purity of the PEM hydrogen production module is 99.0-99.99 percentAnd H either directly or after catalytic deoxygenation 2 H-containing produced with SUR hydrogen production module 2 When the concentration of the converted gas is 80-90%, or the converted gas is mixed and then enters the same one or a plurality of adsorption towers/devices in the PSA hydrogen extraction module, or the adsorption towers/devices in the PSA hydrogen extraction module adopt two-stage adsorption, the converted gas from the SUR hydrogen production module firstly enters a stage of PSA decarburization (CO) consisting of at least three adsorption towers/devices 2 ) The decarbonized and converted gas flowing out of the hydrogen production module and the PEM hydrogen production module produce H with the purity of 99.0-99.99 percent after catalytic deoxidation 2 Mixing and feeding into two-stage PSA refining composed of at least four adsorption towers/devices to obtain H 2 The product gas, the first desorption gas flowing out from the first PSA decarbonization is directly used as flue gas to be discharged, and the second desorption gas flowing out from the second PSA refining is used as supplementary fuel gas to be returned to the SUR hydrogen production module for recycling.
Furthermore, the natural gas water vapor combined conversion and proton exchange membrane water electrolysis coupled hybrid hydrogen production system is characterized in that a program control valve and a regulating valve group which are connected with each adsorption tower/device in the PSA hydrogen extraction module are replaced by a multi-channel rotary valve, wherein an inlet and an outlet of each adsorption tower/device are connected with an inlet and an outlet of an upper disc and a lower disc of the multi-channel rotary valve, and the inlet and the outlet of each adsorption tower/device are connected with an inlet and an outlet of a lower disc of the multi-channel rotary valve, and the inlet and the outlet of each adsorption tower/device in the PSA hydrogen extraction module comprise H which is generated by the PEM hydrogen production module and has purity of 99.0-99.99 percent or is directly or after catalytic deoxidation 2 With H-containing produced from SUR hydrogen production module 2 80-90% concentration of shift gas and H flowing out of PSA hydrogen extraction module 2 The product gas and the desorption gas, the flushing gas, the vacuum pumping gas and the process gas including the uniform pressure gas, the sequential deflation gas, the final inflation gas and the flushing gas in the system in the PSA hydrogen extraction module flow into and out of each adsorption tower/device through the corresponding channels and pipelines in the multi-channel rotary valve, so that the PSA hydrogen extraction module is suitable for miniaturized skid-mounting.
The beneficial effects of the invention are as follows:
(1) The invention can reduce the consumption of natural gas and fuel gas as much as possible on the premise of ensuring the energy supply of the SUR hydrogen production module, and the surplus steam and energy generated by the hydrogen production module provide the needed preheating process water/steam and heat for the PEM hydrogen production module, thereby making up PEThe original defects of electric heating power consumption and long heating time of the M hydrogen production module solve the heat source problem of PEM hydrogen production, and simultaneously, the SUR hydrogen production module can fully utilize the byproduct pure oxygen (O) generated by PEM hydrogen production 2 ) H-containing produced by hydrogen extraction with process gas or with PSA 2 The desorption gas is combusted in a combustion chamber at the top of a reformer/reactor in the SUR hydrogen production module, and the generated reaction heat provides enough energy for the primary conversion and deep conversion reaction and the subsequent medium-high temperature conversion reaction carried out by the two-stage reformer/reactor of the SUR hydrogen production module, thereby greatly reducing the consumption and flue gas emission of raw material fuel gas caused by the traditional hydrogen production fuel gas by reforming and converting natural gas Steam (SMR), simultaneously preheating process water or generating steam by the surplus heat to provide working medium and operation temperature required by the PEM hydrogen production module, reducing the energy consumption and waste gas emission of the whole hydrogen production system, and greatly increasing H 2 The yield of the product gas makes up the problems of high cost and low conversion rate of PEM water electrolysis hydrogen production and H 2 The total yield of the product gas is more than 92%;
(2) According to the invention, through coupling of PEM water electrolysis hydrogen production and SUR natural gas steam combined conversion hydrogen production, two hydrogen production modes can be flexibly switched and adjusted according to the price and price market conditions of natural gas in a hydrogen market area, so that the operation cost is further reduced, for example, when the price of electricity is relatively low in the evening, the flow of preheated desalted water or steam entering a PEM hydrogen production module is increased through a steam control valve, and meanwhile, the flow of steam matched with the raw material natural gas is reduced, and the hydrogen production proportion of water electrolysis is improved; the hydrogen production proportion of natural gas can be improved in turn in electricity deficiency seasons; the hydrogen production proportion of natural gas is reduced and the hydrogen production proportion of water electrolysis is increased in places with higher requirements on environment. In addition, the invention can independently operate water electrolysis hydrogen production or natural gas hydrogen production for a period of time so as to cope with fluctuation of natural gas and electric power markets.
(3) The invention reduces the load of the traditional natural gas steam SMR conversion by adopting the combined conversion hydrogen production process, and the material between the SMR conversion and the self-heating ATR converter/reactor is converted through convection and radiation sections in the SUR hydrogen production system The adjustment of flow rate and operation temperature, including the separation of the pre-reforming gas into two flows, etc., is used for the optimal matching of the load and the energy of two reforming modes, for example, 30% of the primary reforming is completed, and most of the reforming is completed in a self-heating reformer/reactor, thus reducing the volume of the SMR reformer by approximately 60-70%, and being particularly suitable for the miniaturized skid-mounted of a hybrid hydrogen production system with the scale of 10-1000 Nm 3 And/h, the hydrogen production layout and the distributed hydrogen production in the hydrogen station are used for hydrogen production.
(4) The invention can utilize the higher purity H generated by the PEM hydrogen production module 2 Lower H generated with SUR hydrogen production module 2 Different concentrations of the concentration conversion gas respectively enter different adsorption towers/devices in the PSA hydrogen extraction module to realize PSA separation and purification of H 2 Efficiency is maximized.
(5) The invention can utilize diversified energy sources, including clean energy sources such as water power, thermoelectric power, photoelectrical power, wind power, nuclear power and the like, and natural gas power generation, biomass biogas, solid waste thermoelectric power and the like which are recycled by low carbon and waste resources, especially biomass biogas, can be used as raw material gas and fuel gas of SUR hydrogen production modules, can also be used for power generation to provide partial power for water electrolysis hydrogen production, and further improves the environment-friendly effect of hydrogen production.
Drawings
Fig. 1 is a schematic flow chart of embodiment 1 of the present invention.
Fig. 2 is a schematic flow chart of embodiment 5 of the present invention.
Detailed Description
In order to enable those skilled in the art to better understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
Example 1
As shown in fig. 1, a hybrid hydrogen production system with combined conversion of natural gas and water vapor and water electrolysis coupling of proton exchange membrane is composed of an energy source raw material module, a proton exchange membrane water electrolysis (PEM) hydrogen production module, a natural gas and water vapor combined conversion (SUR) hydrogen production module, a Pressure Swing Adsorption (PSA) hydrogen extraction module, and pipelines, valves and heat exchangers among the modules, wherein each module and the specific flow of the hybrid hydrogen production system are as follows:
(1) Energy source raw material module, from industrial natural gas with temperature of normal temperature and pressure of 0.3MPa, flow rate of 1,000 standard square/hr (Nm) 3 And/h), 85% is used as raw material gas, and is pressurized by a compressor to
2.8-3.0 MPa and preheating to 240-320 ℃, then entering into hydrodesulfurization, wherein 1-5% of H from PEM hydrogen production module has purity of 99.5-99.9%, and is subjected to gas-liquid separation and catalytic deoxidation 2 As hydrogenation source, the purified raw gas after hydrodesulfurization by using zinc oxide as catalyst is mixed with middle-low pressure steam which is taken as process steam from a steam storage tank and through a bypass throttle valve to form natural gas steam mixed steam, and the natural gas steam mixed steam enters into a SUR hydrogen production module, 15% of industrial natural gas and O flowing out from the PEM hydrogen production module 2 The combustion gas and the desorption gas from the PSA hydrogen extraction module are used as fuel gas and supplementary fuel gas, the combustion chamber and the process conversion gas at the top of the SMR reformer and the self-heating ATR reformer in the convection and radiation section in the SUR hydrogen production module or/and the desorption gas containing hydrogen are used as combustion gas to carry out combustion reaction, the generated reaction heat is heat provided by the ATR reformer, the preheating reformer, desalted water vapor, the steam drum, the waste heat boiler and the medium-high temperature shift reaction in the SUR hydrogen production module, desalted water from city tap water or industrial water is desalted by about 5 to 10 percent
The method is characterized in that cooling water enters an ATR reformer in an SUR hydrogen production module for water injection cooling, flows out of a reformer jacket and returns to city tap water or industrial water for recycling through heat exchange, 90-95% of desalted water enters an deaerator of the SUR hydrogen production module as preheated desalted water (process water) after being preheated to 70-90 ℃ and enters an outlet flow rate of the deaerator through a hot water pump, 20-40% of the desalted water is used as a working medium and is input into a PEM hydrogen production module, 60-80% of the cooling water enters a fresh desalted water vapor formed by a steam boiler and an SMR reformer convection section of the SUR hydrogen production module to form process vapor, the process vapor enters a steam storage tank as process vapor of an energy source raw material module, the process vapor flowing out of the process vapor and purified raw material gas are mixed to form mixed vapor and then enter the SUR hydrogen production module, meanwhile, a throttle injection valve connected with an outlet of the steam storage tank is closed state, high-temperature flue gas discharged from a combustion chamber of the SUR hydrogen production module and cold and hot water in the PEM module are subjected to heat exchange and gas-liquid separation, water returns to the pretreatment circulation, and gas is discharged as waste gas, and is connected to an electric heater of an electric power grid or an electric power grid for directly starting the hydrogen production system, and an electric power supply system for the electric power system for the hydrogen production is required to be started up and an electric power supply system for the electric power system for the hydrogen production module is required to be used for the hydrogen production and the electrolysis;
(2) The PEM hydrogen production module is characterized in that when the power input from the energy source raw material module is connected with a control system consisting of a transformer and a control cabinet, under the working condition that working medium is liquid water, preheated desalted water with the temperature of 70-90 ℃ flowing out of a water storage tank is input into an electrolytic tank of the PEM hydrogen production module through a regulating valve, the operation temperature of the electrolytic tank is 70-90 ℃, the precipitation concentration of the anode of an exchange membrane of the electrolytic tank is 99%, and the pressure is
2.8-3.0 MPa of O 2 Cooling the mixture by a cooler, then entering an oxygen storage tank, outputting the cooled mixture as fuel gas, entering an SUR hydrogen production module, and separating out the mixture with the concentration of 99.2-99.9% and the pressure of 99.2% from the cathode of the electrolytic tank
H of 2.8-3.0 MPa 2 After water is removed by a water-gas separator, 3 to 5 percent of H is used as the hydrogen desulfurization of the raw material natural gas of the energy raw material module 2 The source and the rest directly enter a PSA hydrogen extraction module for H 2 Purifying and preparing product gas;
(3) SUR hydrogen production module, natural gas steam mixed steam from energy source raw material module is preheated by convection type preheater to form pre-converted gas, then the pre-converted gas enters SMR reformer/reactor of SUR module loaded with nickel/nickel series steam reforming conversion catalyst to make primary catalytic reforming conversion reaction, the reaction temperature is 700-850 deg.C, the reaction pressure is 2.8-3.0 MPa, the heat required by reformer/reactor reaction is the energy source raw material module, the rest fuel natural gas except raw material gas and H-containing gas from PSA hydrogen extraction module 2 Desorption gas and small amounts of O from PEM hydrogen production modules 2 The high-temperature flue gas which is obtained by burning fuel gas, supplementary fuel gas and combustion-supporting combustion gas in a burner at the top of a reformer and flows through the outside of a tube array is obtained by radiation heat transferThe high temperature flue gas is used as a heat source of a desalted water preheater, a steam drum, a steam boiler and a conversion waste boiler, is discharged as flue gas after heat exchange, temperature reduction and treatment, and the middle conversion gas flowing out of the reformer/reactor, wherein the methane content is 30-35%, enters a combustion chamber arranged at the upper part of the ATR reformer/reactor in the SUR module, and is mixed with 99.0% O from the PEM hydrogen production module 2 The combustion reaction of non-catalytic partial oxidation and complete oxidation is carried out, the generated combustion heat directly enters the high-temperature gas formed by the reactants and is positioned at the lower part of the combustion chamber and is loaded with nickel ∈ -
The nickel-based reforming conversion catalyst bed layer is used for deep reforming conversion reaction, and the conversion reaction temperature is
The conversion reaction pressure is 2.8-3.0 MPa at 850-920 ℃, the methane conversion rate reaches 100%, a part of desalted water after desalination is used as cooling water to carry out water jet cooling on the ATR reformer/reactor, and flows out from a cooling water jacket to be recycled as process circulating water, the converted gas is subjected to heat exchange through a cooling drum and a waste heat boiler to supply heat to desalted process steam and then enters a medium-high temperature shift reaction,
The conversion reaction temperature is 260-450 ℃, the reaction pressure is 2.8-3.0 MPa, and the converted gas forms converted gas after medium-high temperature conversion reaction, and the converted gas has the composition of 84-86% H 2 13-15% carbon dioxide (CO) 2 ) Carbon monoxide (CO) less than 1% and residual trace hydrocarbon impurities, and the converted gas enters a PSA hydrogen extraction module for hydrogen extraction after heat exchange with boiler feed water and desalted water;
(4) PSA hydrogen extraction module, purity from PEM hydrogen production module is 99.2-99.9%, pressure is
H of 2.8-3.0 MPa 2 H after catalytic deoxidation 2 H-containing with modules from SUR hydrogen production 2 The concentration is
84 to 86 percent of the conversion gas is mixed and enters a Pressure Swing Adsorption (PSA) system which is formed by 5 composite adsorbent beds which are connected in series and are loaded with aluminum oxide, silica gel, active carbon and molecular sieve and by pipelines among adsorption towers, a program control valve and a regulating valve group, the adsorption pressure is 2.8 to 3.0MPa, the adsorption temperature is 20 to 60 ℃, and 5 adsorption towers are alternately switched to compriseAdsorption and desorption cyclic operation of adsorption, sequential discharge, 2 times of pressure equalizing drop, reverse discharge, vacuumizing flushing, 2 times of pressure equalizing rise and final charging steps, and adopting a slow equalizing mode, wherein flushing gas adopts H 2 Product gas, while final aeration is from PEM
H of hydrogen production module after catalytic deoxidation 2 From this, H with a purity of 99.9995% was obtained 2 The pressure of the product gas is 2.8-3.0 MPa, the temperature is 20-60 ℃ and the flow is 1900-2000 Nm 3 /H, enter H 2 The desorption gas obtained from the product gas tank enters the buffer tank and then returns to the SUR hydrogen production module as the supplementary fuel gas for recycling, thereby H 2 The total yield of the product gas is more than or equal to 92 percent.
Example 2
As shown in FIG. 1, in the energy source material module of example 1, the flow rate of the industrial natural gas from the normal temperature and the pressure of 0.3MPa was 1,000Nm 3 The/h is adjusted to 500Nm 3 And/h, all raw material gas and O produced by PEM hydrogen production module 2 And the desorption gas produced by the PSA hydrogen extraction module is used as fuel gas and supplementary fuel gas, the corresponding desalted water and steam amount is only adjusted to 60-70% of the original amount, wherein the ratio of the preheated desalted water and steam entering the PEM hydrogen production module to the preheated desalted water and steam entering the SUR hydrogen production module is 3:7, the water-carbon ratio of the reaction of the radiation SMR and the self-heating ATR reformer in the SUR hydrogen production module is increased, the conversion reaction temperature is 800-950 ℃, the operation temperature of the electrolytic tank in the hydrogen production module is 70-90 ℃,
the hydrogen evolution amount is unchanged, and the hydrogen is mixed with the shift gas from the SUR hydrogen production module to enter the PSA hydrogen extraction module for hydrogen extraction after gas-liquid separation and catalytic deoxidation, so that the purity of the H produced from the PSA hydrogen extraction module is 99.9995 percent 2 The flow rate of the product gas is 1100-1300 Nm 3 and/H, wherein H is produced by the PEM hydrogen production module 2 The product gas accounts for 25-35%, which is improved by 30-40% compared with the embodiment 1, and the proportion adjustment of the hydrogen production by the combined conversion of the proton exchange membrane water electrolysis and the natural gas steam in the mixed motion hydrogen production system is realized.
Example 3
Based on the embodiment 1, the electricity price is lowIn the low-cost stage, switching/cutting off pipeline connection between the energy source raw material module and SUR hydrogen production and PSA hydrogen extraction module, reserving preheating and heating of a desalted water preheater, independently starting pipeline connection between the energy source raw material module and the PEM hydrogen production module and pipeline connection between the PEM hydrogen production module and the PSA hydrogen extraction module, inputting electric power in the energy source raw material module into the PEM hydrogen production module and the PSA hydrogen extraction module and the desalted water preheater to carry out PEM water electrolysis hydrogen production, wherein the purity of the water flowing out is 99.2-99.8%, the pressure is 1.8-2.2 MPa, and the flow is 250-350 Nm 3 H of/H 2 After water and catalytic deoxidization are removed by a water-gas separator, all the water enters a PSA hydrogen extraction module for H 2 The preparation of the product gas omits a part of H which is returned to the hydrogen desulfurization of the raw gas in the energy raw material module and is consumed by the oxyhydrogen combustion of the self-heating ATR reformer in the SUR module 2 At this time, the 5 adsorption towers in the PSA hydrogen extraction module sequentially perform cyclic operations of adsorption, sequential discharge, 2 times of pressure equalization drop, reverse discharge, flushing, 2 times of pressure equalization rise and final charging, wherein the vacuumizing step of the embodiment 1 is omitted, flushing gas adopts sequential discharge gas, final charging gas adopts H from the PEM hydrogen production module and subjected to gas-water separation and catalytic deoxidation 2 Thus, H is produced from the PSA hydrogen module 2 The yield of the product gas is more than or equal to 92 percent.
Example 4
Based on example 1, in the SUR hydrogen production module, the pre-conversion gas flow is unchanged by increasing O from the PEM hydrogen production module 2 5-8% of the original flow and newly adding about 5% of H from the PEM hydrogen production module without gas-liquid separation and catalytic deoxidation 2 The flow rates of the convection and radiation SMR and the combustion chamber of the self-heating ATR reformer/reactor respectively entering the SUR hydrogen production module are changed to change the composition of the high-temperature reformed gas flowing out, so that H in the reformed gas 2 Concentration increases, ultimately leading to H in the shift gas 2 The concentration is 86-90%, and the product is stable after reaching 90%.
Example 5
As shown in fig. 2, on the basis of example 1, the pre-converted gas from the energy source raw material module is divided into two streams, the ratio of which is 7-8:2-3, and one more stream enters the SUR hydrogen production moduleThe convection and radiation SMR reformer of SUR hydrogen production module, and the less one enters the self-heating ATR reformer in SUR hydrogen production module to carry out deep reforming, thereby further reducing the load of the convection and radiation section SMR reformer/reactor of SUR hydrogen production module and the natural gas fuel consumption to below 10-15%, and increasing the O from PEM hydrogen production module 2 2 to 5 percent of flow is introduced into the combustion chamber of the ATR reformer/reactor, thereby adjusting the H of the SUR hydrogen production module 2 Yield and H with PEM hydrogen production module 2 The ratio of yields was 8:2 and brought to 100% conversion of the final methane, ultimately resulting in H in the shift gas 2 The concentration is 86-90%, and the product is stable after reaching 90%.
It will be apparent that the embodiments described above are only some, but not all, of the embodiments of the present invention. All other embodiments, or structural changes made by those skilled in the art without inventive effort, based on the embodiments described herein, are intended to be within the scope of the invention, as long as the same or similar technical solutions as the invention are provided.
Claims (10)
1. The mixed hydrogen production system is characterized by comprising an energy source raw material module, a proton exchange membrane water electrolysis (PEM) hydrogen production module, a natural gas water vapor combined conversion (SUR) hydrogen production module, a Pressure Swing Adsorption (PSA) hydrogen extraction module and pipelines, valves and heat exchangers among the modules, wherein the energy source raw material module is used for preprocessing natural gas raw materials, processing electric energy, process water, boiler water and steam, optimizing the raw material components and energy to adapt to the requirements of a downstream module, and comprises natural gas serving as fuel gas and raw material gas of the SUR hydrogen production module, desorption gas generated by the PSA hydrogen extraction module serving as fuel gas, pure oxygen gas generated by the PEM hydrogen production module and preprocessing of normal temperature or a heater or a heat exchanger serving as combustion-supporting supplementary air outside the mixed hydrogen production system, normal pressure or a booster, raw material natural gas desulfurization and desalination process water mixed steam and pre-converted gas, and a natural gas generator or other electric power Force supply, process water and boiler water desalination pretreatment, heat exchange, desalted water preheating and steam storage tanks, and process raw materials, fuel and power pipe network inlet and outlet pipelines and control valves inside and outside the module; the PEM hydrogen production module mainly comprises a one-stage or multi-stage serial/parallel proton exchange membrane water electrolysis tank, a water storage tank, a gas-liquid processor, a rectifier, an electric heater, a control system, a throttle valve, a bypass valve and hydrogen (H) 2 ) With oxygen (O) 2 ) Gas cooler, H 2 Catalytic deoxidizer, and power and H connected inside and outside module 2 、O 2 The gas pipeline and the process (hot/cold) water pipeline and the control valve are formed; the SUR hydrogen production module mainly comprises a preheating converter of mixed steam, an SMR converter/reactor provided with convection and radiation sections, a self-heating steam ATR converter/reactor provided with a combustion chamber at the top, a medium-high temperature shift reactor, a gas-liquid separator, a heat exchanger, a steam drum, a waste heat boiler, and mixed steam, pre-converted gas, middle converted gas, fuel gas, PSA stripping hydrogen suction gas pipelines and desalted water, boiler water supply, a steam storage tank, a circulating water pipeline, a deaerator, a conveying and circulating pump and a control valve which are connected inside and outside the module; the PSA hydrogen extracting module consists of a plurality of adsorption towers connected in series/parallel, a desorption gas buffer tank, and electric power and H connected inside and outside the module 2 Product gas/stripping gas, H flowing out of PEM hydrogen production module 2 The process comprises the following steps of,
(1) The energy source raw material module takes city gas or industrial natural gas as raw material gas, is pressurized to 0.3-5.0 MPa by a compressor and preheated to 250-380 ℃ and enters hydrodesulfurization, and H from the PEM hydrogen production module 2 As hydrogenation source, the desulphurized purified feed gas is mixed with desalted water vapor from a water vapor storage tank bypass valve and medium-low pressure vapor as process vapor flowing out from the SUR hydrogen production module to form natural gas water vapor mixed vapor, and enters the SUR hydrogen production module, and the rest of raw gas except the feed gas is taken as fuel gas from city gas or industrial natural gas and flows out from the PEM hydrogen production module to form O 2 And stripping gas from PSA hydrogen-stripping module, or outside the systemThe method comprises the steps of (1) mixing air, entering a SUR hydrogen production module for combustion and supplementing fuel, combusting combustion chambers positioned at the top of an SMR reformer and the top of an ATR reformer in a convection and radiation section, providing heat for conversion of SMR and ATR reformer/reactor, supplying process steam from city tap water or industrial water, desalting, taking part of desalted water as cooling water to perform water injection cooling on the ATR reformer/reactor in the SUR hydrogen production module, flowing out of a cooling water jacket and returning to be used as process circulating water for recycling, preheating part of desalted water to 70-90 ℃ as process water to enter a deaerator of the SUR hydrogen production module and be regulated by a hot water pump, inputting part of preheated desalted water as a working medium into the PEM hydrogen production module, and forming process steam by fresh desalted water steam formed by a steam boiler and the SMR reformer convection section of the SUR hydrogen production module, taking part of process steam flowing out of the process steam as an energy raw material module to enter a steam storage tank, mixing and forming PEM mixed PEM as raw material gas after being desalted by a bypass valve, flowing out of the process steam and purified PEM as natural gas, flowing out of the PEM and then flowing out of the SUR PEM, taking part of the PEM as a natural gas to be used for circulating, and directly flowing into a hydrogen production system, or an electric power grid, or directly flowing into a power grid through an electric power grid, or directly providing a power supply system for the electric power generation system, or directly supplying the electric power to the electric power system, and a hydrogen production system, or directly supplying the electric power to the electric power system, and a power system, or directly supplying the electric power system, and a power system, or a power system, and a power system, supplying the electric system, and a power system, and a power, and a solar energy, hydropower station, thermoelectric, provide the electric power for PEM hydrogen manufacturing module;
(2) The PEM hydrogen production module is characterized in that the power input from the energy source raw material module is connected with a control system consisting of a transformer and a control cabinet, direct-current voltage is input, or when working medium is liquid water, preheated desalted water at 70-90 ℃ flowing out of a water storage tank passes through a regulating valve, or when working medium is desalted water vapor, water vapor flowing out of the water vapor storage tank passes through a throttling injection valve to obtain high-temperature water vapor, and the high-temperature water vapor is cooled to 100-120 ℃ and is subjected to liquid water removal, and then flowsPutting the mixture into an electrolytic tank, wherein the operation temperature of the electrolytic tank is 70-100 ℃ or 100-120 ℃ respectively, and O with the concentration of 98.5-99.5% and the pressure of 0.3-5.0 MPa is separated out from the anode of an exchange membrane of the electrolytic tank 2 Cooling the mixture by a cooler, then entering an oxygen storage tank, outputting the cooled mixture as fuel gas, entering an SUR hydrogen production module, and separating out H with the concentration of 99.0-99.99% and the pressure of 0.3-5.0 MPa from the cathode of an electrolytic tank 2 After the water is removed by the water-gas separator, a part of the water is directly or after catalytic deoxidation, heat exchange and cooling, or is directly used as industrial grade H 2 Product gas output, a portion of the H as a feed natural gas hydrodesulfurization for an energy feed module 2 Source, or/and enter PSA hydrogen extraction module for H 2 Purifying and preparing product gas; (3) SUR hydrogen production module, natural gas steam mixed steam from energy source raw material module is preheated by convection type preheater to form pre-converted gas, then the pre-converted gas enters SMR reformer/reactor of SUR module loaded with nickel/nickel series steam reforming conversion catalyst to make primary catalytic reforming conversion reaction, the reaction temperature is 700-850 deg.C, the reaction pressure is 0.3-5.0 MPa, the heat required by the reformer/reactor reaction is H-contained from urban fuel gas or industrial natural gas and from PSA hydrogen extraction module, the rest of energy source raw material module except raw material gas 2 The air outside the stripping gas and the modules is fuel gas, supplementary fuel gas and high-temperature flue gas flowing through the outside of the tube array and obtained by burning the fuel gas, supplementary fuel gas and combustion-supporting combustion gas at the top or the lower part or the two sides of the reformer through radiation heat transfer, the discharged high-temperature flue gas is used as a heat source of a preheater, a steam drum, a steam boiler and a reforming waste boiler, and is used as flue gas discharge after heat exchange, temperature reduction and treatment, the middle reformed gas flows out of the reformer/reactor, wherein the methane content is 20-40%, enters a combustion chamber at the upper part of the ATR reformer/reactor arranged in the SUR module, and 98.5-99.5% O from the PEM hydrogen production module 2 The combustion reaction of non-catalytic partial oxidation and complete oxidation is carried out, the generated combustion heat is directly carried by the reactant to form high-temperature gas which enters the lower part of the combustion chamber and is loaded with a nickel/nickel series reforming conversion catalyst bed layer for deep reforming conversion reaction, the conversion reaction temperature is 800-950 ℃, the conversion reaction pressure is 0.3-5.0 MPa, the methane conversion rate reaches 100%,part of desalted water is used as cooling water to spray and cool the ATR reformer/reactor, and flows out of the cooling water jacket and returns to be used as process circulating water for recycling, the discharged converted gas is subjected to cooling, steam drum and waste heat boiler heat exchange to supply heat to desalted process steam, then enters into medium-high temperature conversion reaction, the conversion reaction temperature is 260-450 ℃, the reaction pressure is 0.3-5.0 MPa, the converted gas forms converted gas after the medium-high temperature conversion reaction, and the converted gas comprises 80-90% H 2 Carbon dioxide (CO) 9-19% 2 ) Carbon monoxide (CO) less than 1% and residual trace hydrocarbon impurities, and the converted gas enters a PSA hydrogen extraction module for hydrogen extraction after heat exchange with boiler feed water and desalted water;
(4) PSA hydrogen extraction module, purity from PEM hydrogen production module is 99.0-99.99% and H after direct or catalytic deoxidation 2 H-containing with modules from SUR hydrogen production 2 The converted gas with the concentration of 80-90% is respectively or mixed into a Pressure Swing Adsorption (PSA) system formed by at least 3 or more composite bed adsorption towers/devices loaded with adsorbent, pipelines between the adsorption towers/devices, a program control valve and a regulating valve group, wherein the adsorption pressure is 0.3-5.0 MPa, the adsorption temperature is 20-80 ℃, the adsorption towers/devices are alternately switched to perform adsorption and desorption cycle operations comprising adsorption, pressure equalizing, forward discharge, reverse discharge, vacuum/flushing and final filling steps, and the purity of H is more than or equal to 99.995% is obtained 2 Product gas enters H 2 The desorption gas obtained from the product gas tank enters the buffer tank and then returns to the SUR hydrogen production plate as the supplementary fuel gas for recycling, thereby,
H 2 the total yield of the product gas is more than or equal to 90 percent.
2. A hybrid hydrogen production system employing combined natural gas and water vapor reforming and proton exchange membrane water electrolysis coupling as claimed in claim 1, wherein said PEM hydrogen production module produces H having a purity of 99.0 to 99.99% and either directly or catalytically deoxygenated 2 H-containing produced with SUR hydrogen production module 2 The ratio of the converted gases with the concentration of 80-90% is 2-4:6-8, and the proportion is prepared by desalted water/processSteam, raw natural gas/fuel gas, process conversion gas and O of PEM hydrogen production module 2 And the control of the usage amount of desorption gas which flows out of the PSA hydrogen extraction module and is used as supplementary fuel gas is obtained, wherein the distribution of the flow of process steam entering the SUR hydrogen production module and the flow of preheated desalted water or/and high-temperature steam entering the PEM hydrogen production module and O from the PEM hydrogen production module are controlled by controlling the opening of a feed pump outlet or/and a bypass steam throttle valve or controlling the opening of a high-temperature steam throttle valve linked with the PEM hydrogen production module of the flow of preheated desalted water or/and high-temperature steam needed by the SUR hydrogen production module at the outlet of a desalted water or/and steam storage tank 2 With H-containing from PSA hydrogen-stripping module 2 Desorbing H from gas 2 The concentration and flow rate are mainly controlled by the combustion reaction and the reaction temperature in the combustion chamber of the ATR reformer/reactor in the SUR hydrogen production module.
3. A natural gas vapor combined reforming and proton exchange membrane water electrolysis coupled hybrid hydrogen production system as in claim 1, wherein said PEM hydrogen production module and SUR hydrogen production module are configured to preheat desalted water/process vapor, feed/fuel natural gas and O of PEM hydrogen production module by switching and switching off said modules 2 The connection between the stripping gas pipeline and the material flow pipeline of the PSA hydrogen extracting module is independently operated, wherein, the H of the PSA hydrogen extracting plate block 2 The gas flow rate of the product is respectively dependent on the purity of 99.0-99.99% H produced by the PEM hydrogen production module and the SUR hydrogen production module 2 And contain H 2 The concentration is 80-90% of the maximum capacity of the change gas.
4. A hybrid hydrogen production system for combining natural gas and water vapor reforming with proton exchange membrane water electrolysis coupling as claimed in claim 1, wherein said hybrid hydrogen production system produces H 2 The gas capacity of the product is 100-20,000 Nm 3 And/h, wherein the hydrogen production capacity of the PEM hydrogen production module is 20-5,000 Nm 3 And/h, the operation elasticity is 10-120%, and the SUR hydrogen production module is 80-15,000 Nm 3 And/h, the operation elasticity is 50-100%,
the PSA hydrogen extraction module is 20-20,000 Nm 3 And/h, the operation elasticity is 30-110%。
5. The hybrid hydrogen production system of natural gas water vapor combined conversion and proton exchange membrane water electrolysis coupling as claimed in claim 1, wherein the working medium of the PEM hydrogen production module is liquid desalted water with the temperature of 70-90 ℃, a process steam tank, a throttle jet valve and a high-temperature steam cooler pipeline are closed, preheated desalted water with the temperature of 70-90 ℃ input by a circulating pump from an energy source raw material module directly enters the PEM water electrolyzer for electrolysis through a pipeline connected with a liquid water inlet of the PEM water electrolyzer, and O flowing out from a diaphragm anode 2 The purity is 98.5-99.2%, the pressure is 0.3-3.0 MPa, and the hydrogen is taken as fuel gas to enter SUR hydrogen production module after entering the oxygen storage tank, and H flows out from the diaphragm cathode 2 The purity is 99.0-99.8%, the pressure is 0.3-3.0 MPa, and after gas-liquid separation and catalytic deoxidation, a part of the hydrogen is used as the hydrogen desulfurization H of the raw material natural gas of the energy raw material module 2 Part of the hydrogen is directly or after being pressurized enters a PSA hydrogen extraction module to further obtain H 2 Product gas.
6. The hybrid hydrogen production system of claim 1, wherein in the SUR hydrogen production module, O from the PEM hydrogen production module is regulated and controlled by the pre-conversion gas flow rate without changing the co-conversion gas flow rate 2 Flow and new addition of H from PEM hydrogen production module without gas-liquid separation and catalytic deoxygenation 2 The flow rate of the combustion chamber of the ATR reformer/reactor entering the SUR hydrogen production module changes the composition of the outgoing high temperature reformed gas for producing synthesis gas and H 2 A hydrocarbon ratio of conversion gas required downstream, wherein, with O 2 H and H 2 Flow rate is increased to convert H in gas 2 The higher the concentration is, the stability is achieved after 90%, and the methane content in the converted gas is less than 0.1-0.3%.
7. A hybrid hydrogen production system combining natural gas and water vapor reforming with proton exchange membrane water electrolysis coupling as claimed in claim 1, wherein,the pre-conversion gas flow entering the SUR hydrogen production module can be divided into two flows, one flow directly enters the convection and radiation section SMR reformer/reactor of the SUR hydrogen production module to react, and the other flow directly enters the self-heating ATR reformer/reactor of the SUR hydrogen production module to react, so that the load of the radiation section SMR reformer/reactor of the SUR hydrogen production module and the natural gas fuel consumption are further reduced, and the O from the PEM hydrogen production module is increased 2 Flow is introduced into the combustion chamber of the ATR reformer/reactor, thereby adjusting the H of the SUR hydrogen production module 2 Yield and H with PEM hydrogen production module 2 The ratio of the output and the conversion of the final methane reaches 100%.
8. The hybrid hydrogen production system combining natural gas and water vapor reforming and proton exchange membrane water electrolysis coupling as claimed in claim 1, wherein the original reforming catalyst bed layer in the radiant section SMR reformer/reactor of the SUR hydrogen production module is changed into a low-temperature catalytic reforming catalyst, and the catalyst comprises a catalyst containing nickel/cobalt or rare earth metal active components on Carbon Nanotubes (CNTs) with the initial reforming temperature of 450-600 ℃, the reaction pressure is unchanged, and the consumption of natural gas fuel required by the conversion reaction of convection and radiant section SMR reformer/reactor is further reduced, and the H-containing of the PSA hydrogen extraction module is adopted 2 Desorption air and air outside the module or O of PEM hydrogen production module 2 As fuel gas, all substitute natural gas fuel, while the low-temperature intermediate reformed gas has a methane content of less than 30%, and enters the ATR reformer/reactor loaded with nickel/nickel-based catalyst of the SUR hydrogen production module for further deep reforming while increasing O from the PEM hydrogen production module 2 The reaction temperature of the deep conversion is 800-960 ℃, the reaction pressure is unchanged, and the methane content in the flowing converted gas is less than 0.1-0.3%.
9. A natural gas vapor combined reforming and proton exchange membrane water electrolysis coupled hybrid hydrogen production system as claimed in claim 1, wherein said SUR hydrogen production module convection and radiation section SMR reformer/reactor is filled with a low temperature reforming catalystA catalyst, while the autothermal ATR reformer/reactor is loaded with a nickel/nickel based reforming catalyst, and simultaneously feeding low temperature intermediate reformed gas from the convection and radiant section SMR reformer/reactor with H from the PEM hydrogen production module 2 Therefore, the CO content of the converted gas flowing out of the ATR converter/reactor is less than 3-5%, the converted gas directly enters the PSA hydrogen extraction module after heat exchange without medium-high temperature conversion reaction, and the special CO molecular sieve filling amount is required to be increased in the composite adsorbent filled in the PSA adsorption tower/reactor.
10. A hybrid hydrogen production system combining natural gas and water vapor reforming with proton exchange membrane water electrolysis coupling as recited in claim 1, wherein said PEM hydrogen production module produces H having a purity of 99.0-99.99% and either directly or after catalytic deoxygenation 2 H-containing produced with SUR hydrogen production module 2 When the concentration of the converted gas is 80-90%, or the converted gas is mixed and then enters the same one or a plurality of adsorption towers/devices in the PSA hydrogen extraction module, or the adsorption towers/devices in the PSA hydrogen extraction module adopt two-stage adsorption, the converted gas from the SUR hydrogen production module firstly enters a stage of PSA decarburization (CO) consisting of at least three adsorption towers/devices 2 ) The decarbonized and converted gas flowing out of the hydrogen production module and the PEM hydrogen production module produce H with the purity of 99.0-99.99 percent after catalytic deoxidation 2 Mixing and feeding into two-stage PSA refining composed of at least four adsorption towers/devices to obtain H 2 The product gas, the first desorption gas flowing out from the first PSA decarbonization is directly used as flue gas to be discharged, and the second desorption gas flowing out from the second PSA refining is used as supplementary fuel gas to be returned to the SUR hydrogen production module for recycling.
A natural gas vapor combined reforming and proton exchange membrane water electrolysis coupled hybrid hydrogen production system as claimed in claim 1, wherein said PSA hydrogen extraction modules are replaced by a multi-channel rotary valve with program control valves and regulating valve groups connected to each adsorption tower/vessel, wherein each adsorption tower/vessel inlet and outlet is connected to the inlet and outlet of the upper and lower trays of the multi-channel rotary valve, and the inlet and outlet PSA hydrogen extraction modules comprise H produced from PEM hydrogen production modules with purity of 99.0-99.99% and directly or after catalytic deoxygenation 2 With H-containing produced from SUR hydrogen production module 2 80-90% concentration of shift gas and H flowing out of PSA hydrogen extraction module 2 The product gas and the desorption gas, the flushing gas, the vacuum pumping gas and the process gas including the uniform pressure gas, the sequential deflation gas, the final inflation gas and the flushing gas in the system in the PSA hydrogen extraction module flow into and out of each adsorption tower/device through the corresponding channels and pipelines in the multi-channel rotary valve, so that the PSA hydrogen extraction module is suitable for miniaturized skid-mounting.
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