Methanol-desalted water vaporization reaction system and method based on dynamic proportion control

Abstract

The invention discloses a methanol-desalted water vaporization reaction system and method based on dynamic proportion control, and relates to the technical field of energy utilization, and the method comprises the following steps: based on mutation detection of methanol-desalted water real-time mixing proportion parameters, triggering a cold energy phase change enhancement mechanism, and generating high-temperature vaporized mixed gas; performing catalytic cracking reaction based on the high-temperature vaporized mixed gas to generate hydrogen-containing converted gas, and identifying the state of the catalyst according to the pressure difference and the activity attenuation coefficient of a catalyst bed; condensing the hydrogen-containing converted gas, purifying by adopting a five-tower PSA (Pressure Swing Adsorption) process, and carrying out online monitoring through a laser gas analyzer to generate ultra-high-purity hydrogen and a hydrogen purity analysis report; based on the catalyst state and the hydrogen purity analysis report, a dynamic proportion control instruction is generated through a multivariable coupling feedback algorithm; a whole-process closed-loop optimization system is constructed by combining a cold energy phase change strengthening mechanism, near infrared spectrum proportion verification and laser-pressure cross validation, and the cold energy utilization rate, the hydrogen purity and the equipment service life are increased in a three-in-one mode.

Description

Technical Field

[0001] This invention relates to a natural gas pretreatment and liquefaction system, and more specifically to the field of energy utilization technology, particularly a methanol-demineralized water vaporization reaction system and method based on dynamic proportion control. Background Technology

[0002] In the field of methanol-to-hydrogen technology, traditional vaporization reaction systems generally employ a fixed-ratio mixing method to control the methanol-deionized water feed ratio. In existing technologies, LNG cold energy utilization mainly focuses on single-refrigerant heat exchange, while cold energy coupling control for vaporization reaction systems often utilizes a PID temperature feedback mechanism. In the hydrogen purification stage, the five-tower pressure swing adsorption process has been widely applied to crude hydrogen purification, while near-infrared spectroscopy is used for online monitoring of component concentrations. Regarding catalyst status monitoring, the scheme based on inferring the activity decay coefficient from the bed pressure difference and outlet components is gradually becoming the mainstream.

[0003] The static mixing ratio cannot respond to the dynamic fluctuations in the cold energy of liquefied natural gas. Localized supercooling due to the temperature difference between the phase transitions of methanol and water within the titanium alloy heat exchanger leads to ice crystal formation and blockage of the flow channels. The hysteresis feedback mechanism of traditional temperature control algorithms is insufficient for real-time correction of the mixing ratio, resulting in incomplete vaporization of the cold energy carrier, inducing metastable liquid phase accumulation, and reducing cold energy transfer efficiency. The catalyst activity decay trend is not transmitted to the front-end proportional control system, causing improper maintenance of the mixing ratio under the critical state of carbon deposition, and an abnormally high concentration of catalytic cracking byproducts. Simultaneously, the pressure characteristics associated with the adsorption tower's breakthrough phase transition point are not involved in the proportional parameter correction, and the decreased impurity retention efficiency leads to the residual oxygen content in the crude hydrogen exceeding the process threshold. Summary of the Invention

[0004] In view of the aforementioned existing problems, the present invention is proposed.

[0005] Therefore, this invention provides a methanol-deionized water vaporization reaction method based on dynamic proportional control to solve the problems of phase change instability and multi-stage control islands under dynamic fluctuations of cold energy through an Internet of Things-based multivariate collaborative mechanism.

[0006] To solve the above-mentioned technical problems, the present invention provides the following technical solution:

[0007] In a first aspect, the present invention provides a methanol-demineralized water vaporization reaction method based on dynamic ratio control, which includes generating optimized real-time mixing ratio parameters of methanol-demineralized water by precooling the mixture with LNG cold energy and combining it with a temperature dynamic compensation algorithm.

[0008] Based on the abrupt detection of the real-time mixing ratio parameter of methanol-deionized water, a cold energy phase change enhancement mechanism is triggered to generate a high-temperature vaporized mixture.

[0009] The catalyst is converted into hydrogen-containing gas by catalytic cracking reaction based on high-temperature vaporized mixed gas, and the catalyst state is identified based on the catalyst bed pressure difference and activity decay coefficient.

[0010] The hydrogen-containing converted gas is condensed and purified using a five-tower PSA process, and then ultra-high purity hydrogen and a hydrogen purity analysis report are generated through online monitoring by a laser gas analyzer.

[0011] Based on the catalyst state and hydrogen purity analysis report, a dynamic proportional control command is generated through a multivariate coupled feedback algorithm.

[0012] As a preferred embodiment of the methanol-demineralized water vaporization reaction method based on dynamic proportion control described in this invention, the steps for generating optimized real-time mixing ratio parameters of methanol-demineralized water by pre-cooling the mixture with LNG cold energy and combining it with a dynamic temperature compensation algorithm are as follows.

[0013] The methanol and demineralized water are pre-cooled according to the initial ratio using LNG cold energy through a titanium alloy heat exchanger, and the temperature data of the mixture is collected in real time.

[0014] Based on the mixed liquid temperature data and combined with a temperature dynamic compensation algorithm, the optimized dynamic ratio parameters of methanol-deionized water are generated.

[0015] Based on the optimized dynamic ratio parameters of methanol-deionized water, the real-time mixing ratio parameters of methanol-deionized water are generated by scanning the characteristic absorption peaks of methanol and water using an online near-infrared spectrometer.

[0016] As a preferred embodiment of the methanol-demineralized water vaporization reaction method based on dynamic proportion control described in this invention, the steps for triggering the cold energy phase change enhancement mechanism to generate a high-temperature vaporized mixture are as follows:

[0017] Based on the real-time mixing ratio parameter of methanol-deionized water, the ratio fluctuation amplitude is monitored through a sliding time window to generate a ratio mutation verification report;

[0018] Based on the proportional mutation verification report, a three-stage cold energy phase change enhancement method was used to perform LNG cold energy pressurization injection, ultrasonic nucleation and phase change point coordinated control. When the phase change conditions were reached, a low temperature and high pressure liquid mixed phase was generated.

[0019] The low-temperature, high-pressure liquid mixture is introduced into the titanium-zirconium alloy vaporization tower, and then heated by a nested electric heating unit and the LNG waste heat recovery pipeline to generate a high-temperature vaporized mixture.

[0020] As a preferred embodiment of the methanol-demineralized water vaporization reaction method based on dynamic proportion control described in this invention, the steps for generating hydrogen-containing conversion gas through catalytic cracking of the high-temperature vaporized mixture are as follows:

[0021] The high-temperature vaporized mixture is introduced into a fixed-bed reactor filled with a nickel-based catalyst, where the mixture undergoes a catalytic cracking reaction on the catalyst surface to generate hydrogen-containing conversion gas.

[0022] As a preferred embodiment of the methanol-demineralized water vaporization reaction method based on dynamic proportion control described in this invention, the step of identifying the catalyst state based on the catalyst bed pressure difference and activity decay coefficient is as follows:

[0023] During the catalytic cracking reaction, the catalyst bed pressure difference is monitored in real time, and the activity decay coefficient is obtained by back-calculation based on the changes in the concentration of the outlet gas components and the thermodynamic equilibrium formula of the cracking reaction.

[0024] By combining the catalyst bed pressure difference and activity decay coefficient, the micropore blockage evolution analysis method is used to predict the catalyst deactivation risk index and identify the catalyst state.

[0025] As a preferred embodiment of the methanol-demineralized water vaporization reaction method based on dynamic proportion control described in this invention, the steps of condensing the hydrogen-containing conversion gas and purifying it using a five-tower PSA process, followed by online monitoring using a laser gas analyzer to generate ultra-high purity hydrogen and a hydrogen purity analysis report, are as follows.

[0026] Based on the process of separating heavy hydrocarbon components from hydrogen-containing converted gas by passing it through a stainless steel corrugated pipe condenser and a titanium alloy cryogenic tower, saturated wet hydrogen gas is generated.

[0027] Saturated wet hydrogen gas is fed into a five-tower pressure swing adsorption (PSA) equipment for five-tower PSA process purification. At the same time, pressure transmitters are used to monitor the phase change point of the adsorption towers to generate crude and refined hydrogen gas and the dynamic pressure parameters of each tower.

[0028] The crude and refined hydrogen gas is introduced into a quartz sampling cell, and a laser gas analyzer is used to scan the characteristic peaks of key components for hydrogen purity. The results are then cross-validated with the dynamic pressure parameters of each tower to generate ultra-high purity hydrogen gas and a hydrogen purity analysis report.

[0029] As a preferred embodiment of the methanol-deionized water vaporization reaction method based on dynamic proportional control described in this invention, the steps for generating dynamic proportional control commands through a multivariate coupled feedback algorithm are as follows:

[0030] Based on the catalyst state and hydrogen purity analysis report, a multivariate coupled feedback algorithm is used to synchronously match the catalyst state and hydrogen purity according to the time window to generate a multivariate coupled input matrix.

[0031] The multivariable coupled input matrix is ​​subjected to three-channel joint operation, and the data from the three channels are weighted and fused to generate the initial dynamic proportional control command.

[0032] The initial dynamic proportional control instruction is subjected to dual security verification through hardware security gate groups and instruction timing self-test, and is converted into a dynamic proportional control instruction based on the verification results.

[0033] Secondly, the present invention provides a methanol-deionized water vaporization reaction system based on dynamic proportion control, comprising,

[0034] The mixing ratio calculation module is used to generate optimized real-time mixing ratio parameters of methanol-deionized water by precooling the mixture with LNG cold energy and combining it with a dynamic temperature compensation algorithm.

[0035] The cold energy phase change enhancement module is used to detect abrupt changes in the real-time mixing ratio parameters of methanol-deionized water, triggering a cold energy phase change enhancement mechanism to generate a high-temperature vaporized mixture.

[0036] The catalytic cracking identification module is used to generate hydrogen-containing conversion gas through catalytic cracking reaction based on high-temperature vaporized mixed gas, and to identify the catalyst state based on the catalyst bed pressure difference and activity decay coefficient.

[0037] The condensation and purification analysis module is used to condense hydrogen-containing conversion gas and purify it using a five-tower PSA process. Then, it generates ultra-high purity hydrogen and a hydrogen purity analysis report through online monitoring by a laser gas analyzer.

[0038] The control command generation module is used to generate dynamic proportional control commands based on catalyst state and hydrogen purity analysis reports through a multivariable coupled feedback algorithm.

[0039] Thirdly, the present invention provides a computer device including a memory and a processor, wherein the memory stores a computer program, wherein: when the computer program is executed by the processor, it implements any step of the methanol-deionized water vaporization reaction method based on dynamic proportion control as described in the first aspect of the present invention.

[0040] Fourthly, the present invention provides a computer-readable storage medium having a computer program stored thereon, wherein: when the computer program is executed by a processor, it implements any step of the methanol-deionized water vaporization reaction method based on dynamic proportion control as described in the first aspect of the present invention.

[0041] The beneficial effects of this invention are as follows: By dynamically adjusting the methanol-deionized water ratio in real time through a temperature compensation algorithm, the anti-icing and efficient cold energy transfer of the titanium alloy cryogenic tower are simultaneously achieved, solving the problem of cold energy fluctuation and phase transition instability; by using a multivariate coupled feedback algorithm to connect catalyst state and hydrogen purity parameters, the control island of catalytic cracking-adsorption purification is eliminated; and by combining the cold energy phase transition enhancement mechanism, near-infrared spectroscopy ratio verification, and laser-pressure cross-verification, a closed-loop optimization system for the entire process is constructed, achieving a three-in-one leap in cold energy utilization, hydrogen purity, and equipment lifespan. Attached Figure Description

[0042] To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the following description of the embodiments will be briefly introduced. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0043] Figure 1 This is a flowchart of a methanol-deionized water vaporization reaction method based on dynamic proportion control.

[0044] Figure 2 This is a schematic diagram illustrating the interaction between system modules.

[0045] Figure 3 This is a flowchart of the temperature dynamic compensation algorithm.

[0046] Figure 4 A flowchart illustrating the cold energy phase transition enhancement mechanism. Detailed Implementation

[0047] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

[0048] Many specific details are set forth in the following description in order to provide a full understanding of the invention. However, the invention may also be practiced in other ways different from those described herein, and those skilled in the art can make similar extensions without departing from the spirit of the invention. Therefore, the invention is not limited to the specific embodiments disclosed below.

[0049] Secondly, the term "an embodiment" or "embodiment" as used herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The phrase "in one embodiment" appearing in different places in this specification does not necessarily refer to the same embodiment, nor is it a single or selective embodiment that is mutually exclusive with other embodiments.

[0050] Reference Figures 1-4 This is one embodiment of the present invention, which provides a methanol-deionized water vaporization reaction method based on dynamic proportion control, comprising the following steps:

[0051] S1: Optimized real-time mixing ratio parameters of methanol-deionized water are generated by precooling the mixture with LNG cold energy and combining it with a dynamic temperature compensation algorithm;

[0052] S1.1: The methanol and demineralized water are pre-cooled according to the initial ratio using the cold energy of LNG through a titanium alloy heat exchanger, and the temperature data of the mixture is collected in real time.

[0053] The titanium alloy heat exchanger uses liquefied natural gas (LNG) cold energy to pre-cool a mixture of methanol and demineralized water in an initial ratio. The mixture undergoes counter-current heat transfer with the LNG cold energy carrier within the spiral flow channel of the titanium alloy heat exchanger, and the temperature continuously decreases from ambient conditions to the target pre-cooling range. A platinum resistance temperature sensor embedded in the outlet flange of the titanium alloy heat exchanger continuously monitors the temperature field distribution of the mixture and outputs temperature data to the central database at a frequency of 10 times per second.

[0054] S1.2: Based on the mixed liquid temperature data and combined with the temperature dynamic compensation algorithm, the optimized dynamic ratio parameters of methanol-deionized water are generated;

[0055] Based on the mixed liquid temperature data collected by the platinum resistance temperature sensor, the temperature dynamic compensation algorithm is started: First, the deviation between the actual temperature and the target pre-cooling temperature range is compared, and the preset compensation coefficient lookup table is called to match the methanol volume ratio correction amount corresponding to the temperature deviation; The temperature dynamic compensation algorithm performs arithmetic superposition of the temperature compensation amount and the initial ratio to generate a methanol-deionized water dynamic ratio parameter containing a dynamic compensation term; The dynamic ratio parameter immediately takes effect on the proportional control valve control signal to maintain the optimal cold energy exchange efficiency of the mixed liquid.

[0056] The temperature dynamic compensation algorithm refers to a dedicated logic that executes three-step closed-loop control based on real-time temperature data of the mixed solution collected by a platinum resistance temperature sensor: First, calculate the deviation between the actual temperature and the target pre-cooling temperature range; second, map the temperature deviation to the methanol volume ratio correction amount through a preset compensation coefficient lookup table; third, perform an arithmetic superposition operation on the compensation coefficient and the initial ratio to finally generate a dynamic ratio parameter for methanol-deionized water containing a dynamic compensation term. This algorithm is essentially an empirically solidified model of the nonlinear coupling relationship between temperature and concentration, maintaining a highly efficient cold energy exchange state of the mixed solution within the titanium alloy cryogenic tower through real-time compensation.

[0057] The methanol-demineralized water dynamic ratio parameter refers to the real-time mixing ratio command output after optimization by a temperature dynamic compensation algorithm. Its mathematical form is the volume ratio of methanol to demineralized water. The methanol-demineralized water dynamic ratio parameter has two core characteristics: First, the dynamic compensation term carries the response to temperature deviations, allowing the ratio value to adaptively adjust with temperature fluctuations in the mixture; second, it immediately takes effect on the proportional control valve signal, directly converting it into a valve opening command, forcing the mixture components to always match the current cold energy exchange requirements during condensation. The core value of this parameter lies in achieving the dual goals of preventing ice blockage and efficiently transferring cold energy through precise control of the methanol ratio.

[0058] S1.3: Based on the optimized dynamic ratio parameters of methanol-deionized water, the real-time mixing ratio parameters of methanol-deionized water are generated by scanning the characteristic absorption peaks of methanol and water using an online near-infrared spectrometer.

[0059] Based on the optimized dynamic ratio parameters of methanol-deionized water, an online near-infrared spectrometer simultaneously captures the third harmonic absorption peak of methanol CH bonds and the combination frequency absorption peak of water OH bonds at a scanning frequency of 5 scans per second in the mixing pipe section downstream of the dynamic ratio regulating valve. According to the ratio of the area integral values ​​of the two characteristic peaks, combined with the concentration correction coefficient of Lambert-Beer law, the calculation unit of the online near-infrared spectrometer executes the conversion formula to generate the instantaneous value of the actual proportion of methanol. After comparing this value with the set dynamic ratio parameters, the real-time mixing ratio parameters are output, and this parameter is immediately fed back to the ratio regulating valve to form a closed-loop control.

[0060] The conversion formula is:

[0061]

[0062] Where V represents the volume percentage of methanol, that is, the volume ratio of methanol in the mixture; k represents the concentration correction factor (value range: 0.84~1.00); and r represents the peak area ratio.

[0063] The water characteristic absorption peak, specifically the OH bond frequency absorption peak, is a characteristic broad band captured by the online near-infrared spectrometer. Essentially, it represents the asymmetric stretching vibration and rotational energy level coupling transition signal formed by the OH bond in water molecules under specific near-infrared photon energy excitation. This absorption peak exhibits a broadened shape due to the influence of the hydrogen bond network in liquid water, and its absorption intensity maintains a strictly linear response relationship with the water molecule concentration. The characteristic broad band, together with the methanol CH bond characteristic absorption peak, forms the basis for the quantitative analysis of the two components. Real-time concentration inversion of the mixture is achieved through the analysis of the characteristic peak area ratio, providing core optical sensing basis for closed-loop proportional control.

[0064] S2: Based on the abrupt detection of the real-time mixing ratio parameter of methanol-deionized water, a cold energy phase change enhancement mechanism is triggered to generate a high-temperature vaporized mixture;

[0065] S2.1: Based on the real-time mixing ratio parameter of methanol-deionized water, the ratio fluctuation amplitude is monitored through a sliding time window to generate a ratio mutation verification report;

[0066] Based on the real-time mixing ratio parameter, the numerical sequence of the real-time mixing ratio parameter is continuously updated by a sliding time window; the standard deviation of the real-time mixing ratio parameter is calculated within the sliding time window to quantify the ratio fluctuation amplitude; the ratio fluctuation amplitude is compared with a preset threshold to determine abrupt events, and a ratio mutation verification report containing the current fluctuation amplitude value and the mutation status is generated.

[0067] The proportional fluctuation amplitude threshold serves as the activation criterion for the cold energy phase change enhancement mechanism. Its setting is based on triple constraints: thermodynamic stability, material safety boundaries, and process control requirements. The lower limit of the threshold is determined by the minimum subcooling required to prevent ice blockage in the mixture. When the real-time proportional fluctuation amplitude falls below the lower limit, the phase change process enters the solid-liquid coexistence danger zone, and the ice crystal nucleation rate within the titanium alloy heat exchanger channels increases exponentially, causing the channel blockage risk to exceed the process allowable limit. The upper limit of the threshold is constrained by the titanium alloy coil's resistance to pulsating impact. If the fluctuation amplitude exceeds the upper limit, the transient stress induced by high-pressure injection of liquefied natural gas will break through the critical yield strength of the titanium alloy material, inducing high-frequency fatigue cracks in the coil and threatening the structural integrity of the cryogenic tower.

[0068] S2.2: Based on the proportional mutation verification report, a three-stage cold energy phase change enhancement method is used to perform LNG cold energy pressurization injection, ultrasonic nucleation and phase change point coordinated control. When the phase change conditions are reached, a low temperature and high pressure liquid mixed phase is generated.

[0069] Based on the proportional mutation verification report, a three-stage cold energy phase change enhancement method was initiated, including: LNG cold energy pressurization injection: The output power of the booster pump was linearly increased according to the fluctuation amplitude value recorded in the proportional mutation verification report, driving LNG cold energy to be injected into the titanium alloy cryogenic tower coil at high pressure. The liquefied natural gas underwent a forced phase change in the coil, releasing the cold energy carrier; Ultrasonic nucleation: A pulse width modulated ultrasonic generator excited the surface nucleation frequency on the inner wall of the titanium alloy cryogenic tower. The ultrasonic cavitation effect caused uniform microbubble nuclei to be generated inside the mixture, reducing the phase change energy barrier; Phase change point collaborative control: Data from the pressure transmitter and the platinum resistance temperature sensor were compared in real time. When the pressure and temperature parameters synchronously crossed the preset phase change point threshold, the phase change program was triggered to generate a low-temperature, high-pressure liquid mixed phase.

[0070] The phase change conditions are essentially based on a dual constraint of thermodynamic equilibrium and material safety operating boundaries. The core requirement is that both pressure and temperature thresholds must be met simultaneously. Specifically, the pressure threshold corresponds to the critical compression state of the liquefied natural gas (LNG) cold energy carrier. Its core function is to ensure complete phase change vaporization of LNG within the titanium alloy cryogenic tower coil, releasing all latent heat of condensation. Failure risk: If the actual pressure is below the threshold, the cold energy carrier remains in the metastable liquid phase region, and insufficient vaporization leads to a supercritical decrease in cold energy transfer efficiency. Material constraint: The lower pressure limit is limited by the yield strength of the titanium alloy coil, preventing fatigue cracks caused by high-pressure pulsation. The physical basis of the temperature threshold: The temperature threshold is tied to the safety margin of the mixture's supercooling. Its core function is to maintain the phase change process of the mixture within a stable nucleation region, avoiding entry into the dangerous zone of solid phase formation near the eutectic point. Failure risk: If the actual temperature is above the threshold, insufficient supercooling of the mixture prevents the continuous growth of ultrasonically induced microbubble nuclei, leading to nucleation failure. Thermodynamic constraint: The upper temperature limit is determined by the inflection point of the liquid-gas equilibrium line in the methanol-water phase diagram. Necessity of dual-parameter synchronization: The mandatory requirement for pressure and temperature to be synchronized within an extremely short time difference; Phase change kinetic requirements: Pressure compliance drives the release of potential energy from the cold energy carrier, and temperature compliance ensures the nucleation activity of the mixture; neither can be lacking; Metastable state avoidance: Compliance of a single parameter will trigger a gas-liquid two-phase oscillating flow state (sudden increase in droplet diameter and high-frequency pressure pulsation), causing resonance failure of the cryogenic tower; Steady-state phase generation: Only when pressure triggers complete vaporization, temperature maintains nucleation activity, and the two parameters are spatiotemporally aligned, can a uniform and stable low-temperature high-pressure liquid mixture (gas-liquid interfacial tension ≤ critical value) be generated.

[0071] The phase transition point thresholds include pressure and temperature thresholds. The pressure threshold is set based on the thermodynamic requirements for complete phase change vaporization of liquefied natural gas within the titanium alloy cryogenic tower coil, while also being limited by the material strength of the titanium alloy coil. This threshold must ensure that the cold energy carrier breaks through the metastable liquid phase range and fully releases the latent heat of condensation; insufficient pressure will lead to a precipitous decrease in cold energy transfer efficiency. Its upper limit strictly corresponds to the yield strength boundary of the coil's resistance to pulsating impacts, preventing fatigue cracks induced by high-pressure conditions. The temperature threshold is determined based on the nucleation kinetics of the mixed liquid phase and the requirements for phase safety. Its lower limit avoids the dangerous zone of solid-liquid coexistence to prevent ice crystal formation, while its upper limit is tied to the liquid-gas equilibrium inflection point temperature of the methanol-water phase diagram, ensuring the continuous growth activity of ultrasonically induced microbubble nuclei. Temperature deviations from the threshold will directly trigger nucleation failure, causing the mixed liquid to remain in a metastable state.

[0072] S2.3: The low-temperature, high-pressure liquid mixed phase is introduced into the titanium-zirconium alloy vaporization tower and heated by a nested electric heating unit and the LNG waste heat recovery pipeline to generate a high-temperature vaporized mixed gas.

[0073] After the low-temperature, high-pressure liquid mixed phase is introduced into the titanium-zirconium alloy vaporization tower, a dual heating process is initiated: First, the nested electric heating unit uses platinum-rhodium alloy resistance wire to implement gradient heating, driving the mixed phase to achieve phase infiltration from the wall to the central region; second, the LNG waste heat recovery pipeline releases heat energy through the vaporization of liquefied natural gas, which is then directionally transferred to the core region of the mixed phase via the copper-aluminum composite fin structure; finally, the nested electric heating unit and the LNG waste heat recovery pipeline work together to achieve the superposition of heat flow, enabling the mixed phase to break through the vaporization critical point and generate a high-temperature vaporized mixed gas that meets the temperature requirements, maintains the pressure specifications, and has a methanol-to-water vapor ratio within the allowable fluctuation range.

[0074] S3: Based on the high-temperature vaporized mixed gas, a catalytic cracking reaction is carried out to generate hydrogen-containing conversion gas, and the catalyst state is identified according to the catalyst bed pressure difference and the activity decay coefficient.

[0075] S3.1: The high-temperature vaporized mixed gas is introduced into a fixed-bed reactor filled with nickel-based catalyst, and the mixed gas undergoes catalytic cracking reaction on the catalyst surface to generate hydrogen-containing conversion gas;

[0076] The high-temperature vaporized mixture is introduced into the internal space of the fixed-bed reactor filled with nickel-based catalyst through the inlet distribution structure. On the surface of the microporous channels of the nickel-based catalyst, the high-temperature vaporized mixture undergoes a catalytic cracking reaction: first, methanol molecules complete the chemical adsorption process at the active sites of the nickel-based catalyst, followed by carbon-oxygen bond breaking and free radical recombination reactions, and finally hydrogen molecules desorb from the catalyst surface and diffuse into the main gas flow. The reaction follows the main reaction equilibrium relationship of methanol and steam reforming, and the product components of the hydrogen-containing reforming gas include hydrogen, residual carbon dioxide, trace amounts of carbon monoxide and water vapor, with hydrogen occupying the main proportion of the reforming gas volume.

[0077] S3.2: During the catalytic cracking reaction, the pressure difference of the catalyst bed is monitored in real time, and the activity decay coefficient is obtained by back-calculation based on the change of the concentration of the outlet gas components and the thermodynamic equilibrium formula of the cracking reaction.

[0078] A continuous monitoring and calculation process is implemented during the catalytic cracking reaction: a differential pressure transmitter mounted axially in the fixed-bed reactor continuously collects pressure gradient data between the catalyst bed inlet and outlet; a gas chromatography analyzer simultaneously detects the partial pressure values ​​of hydrogen, carbon monoxide, carbon dioxide, methanol, and water vapor in the reactor outlet gas stream; the thermodynamic equilibrium formula for the cracking reaction is called, and the real-time acquired component partial pressures and reaction temperature are substituted into the right side of the formula to deduce the activity term value; the activity term value is output as an activity decay coefficient in the form of a continuous variable, and its physical meaning characterizes the percentage deviation between the actual catalytic efficiency of the catalyst and the theoretical ideal state.

[0079] S3.3: Combining the catalyst bed pressure difference and activity decay coefficient, the micropore blockage evolution analysis method is used to predict the catalyst deactivation risk index and identify the catalyst state.

[0080] Combining time-series data of catalyst bed pressure difference and dynamic evolution characteristics of activity decay coefficient, the micropore blockage evolution analysis method is implemented as follows: The pressure difference signal is separated into low-frequency physical blockage component and high-frequency chemical deactivation component through variational mode decomposition; a differential state space model is constructed to describe the micropore evolution dynamics of the catalyst; the statistical characteristics of the second derivative of pressure difference and the rate of change of activity decay are integrated to generate a deactivation risk index value; based on the continuous value range distribution of the risk index, it is mapped to a predefined set of deactivation state labels, including health status labels, transitional physical blockage warning labels, and chemical deactivation critical labels. This state label directly characterizes the instantaneous health of the catalyst.

[0081] S4: The hydrogen-containing converted gas is condensed and purified using a five-tower PSA process, and then ultra-high purity hydrogen and hydrogen purity analysis report are generated through online monitoring by a laser gas analyzer.

[0082] S4.1: Based on the hydrogen-containing conversion gas passing through a stainless steel corrugated pipe condenser and a titanium alloy cryogenic tower, heavy component hydrocarbons are separated to generate saturated wet hydrogen gas;

[0083] The process flow based on hydrogen-containing converted gas is as follows: First, the hydrogen-containing converted gas enters a stainless steel corrugated tube condenser tower. Within a longitudinal temperature gradient field constructed by circulating cooling water, it undergoes a gradual cooling process from a high-temperature inlet to a low-temperature outlet. This causes heavy hydrocarbon components with boiling points higher than the cooling water outlet temperature to undergo phase change and condense in the gaps between the corrugated tube fins. The intermediate gas phase, after preliminary removal of heavy components, is then fed into a titanium alloy cryogenic tower. Deep cooling is achieved using liquefied natural gas as a cold energy carrier, allowing residual trace amounts of long-chain alkanes with boiling points higher than the cryogenic temperature to be condensed and removed a second time on the surface of the tower fins. Finally, the uncondensed gas phase passes through a wire mesh demister at the top of the titanium alloy cryogenic tower to trap residual droplets exceeding the particle size limit. The output is saturated wet hydrogen gas with a temperature meeting cryogenic standards, humidity reaching saturation requirements, and a heavy component removal rate exceeding the process threshold, strictly meeting the inlet gas indicators for subsequent processes.

[0084] The process of separating heavy hydrocarbons refers to the selective phase transition of heavy hydrocarbons with boiling points higher than the cooling medium temperature in hydrogen-containing conversion gas into a liquid phase through the temperature gradient field of a stainless steel corrugated pipe condenser and the deep cooling of a titanium alloy cryogenic tower, ultimately achieving a qualified removal rate of heavy hydrocarbons.

[0085] S4.2: Saturated wet hydrogen gas is fed into a five-tower pressure swing adsorption equipment for five-tower PSA process circulation purification. At the same time, pressure transmitters are used to monitor the phase change point of the adsorption towers to generate crude and refined hydrogen gas and dynamic pressure parameters of each tower.

[0086] Saturated wet hydrogen gas enters the five-tower pressure swing adsorption (PSA) unit to start the five-tower PSA process cycle. The pressure transmitter continuously monitors the pressure change inflection point of the phase transition point of the adsorption tower to identify the saturation state of the adsorbent. The adsorption towers alternately switch to perform the processes of pressurization adsorption, forward depressurization, reverse desorption, flushing regeneration, and pressure equalization. The pressure transmitter simultaneously captures the complete pressure curve data of the pressurization and depressurization process of each adsorption tower to generate a dynamic pressure parameter matrix for each tower. Finally, the crude and refined hydrogen product with hydrogen purity meeting the specifications and impurity content meeting the standards is output from the outlet of the adsorption tower that has completed the final pressurization and transmitted downstream along with the real-time recorded dynamic pressure parameter matrix of each adsorption tower.

[0087] The phase transition point of the adsorption tower refers to the thermodynamic critical point at which the adsorbent abruptly changes from a highly efficient adsorption state to a saturated failure state in the five-tower PSA process cycle. Its physical essence is as follows: when the micropores of the activated carbon / molecular sieve composite adsorbent in the adsorption tower are saturated and covered by impurity gas, the pressure drop rate of the pressure-time curve increases sharply, forming an inflection point. This point represents the adsorbent's penetration deactivation, triggering the switching of the forward pressure reduction process. The pressure transmitter captures the tower number and instantaneous pressure value corresponding to this inflection point, driving the five-tower time sequence rearrangement.

[0088] The tower pressure dynamic parameters are a dataset of pressure characteristics of the adsorption tower throughout its entire cycle, recorded by the pressure transmitter at a millisecond sampling frequency. The time-series characteristics include: pressure change rate during the pressurization phase and pressure valley value during the depressurization phase; process state characteristics include: frequency of flushing and regeneration flow fluctuations and pressure difference when pressure equalization is completed; engineering applications include: the parameter matrix outputs 20 sets of multi-dimensional vectors per second, which are directly related to the remaining lifespan of the adsorbent and support closed-loop control of the purity of crude and refined hydrogen.

[0089] S4.3: The crude and refined hydrogen gas is introduced into a quartz sampling cell, and the characteristic peaks of key components of hydrogen purity are scanned using a laser gas analyzer. The results are then cross-validated with the dynamic pressure parameters of each tower to generate ultra-high purity hydrogen gas and a hydrogen purity analysis report.

[0090] The refined hydrogen gas is introduced into a quartz sampling cell at a constant flow rate. The laser gas analyzer activates a 532nm laser beam to scan the characteristic peaks of key components for hydrogen purity (including hydrogen elementarys, oxygen impurities, water vapor, and carbon monoxide), and simultaneously acquires the absorbance data of the characteristic peaks. The laser gas analyzer's computing unit calls the dynamic pressure parameters of each tower to establish a time window correlation function, and cross-validates the phase alignment accuracy between the characteristic peak sequence and the adsorption pressure curve. Finally, an ultra-high purity hydrogen gas with a purity ≥99.999% and impurity concentration meeting the standards is generated, along with a hydrogen purity analysis report containing quantified values ​​of four types of characteristic peaks and pressure correlation verification conclusions.

[0091] S5: Based on the catalyst state and hydrogen purity analysis report, a dynamic proportional control command is generated through a multivariate coupled feedback algorithm.

[0092] S5.1: Based on the catalyst state and hydrogen purity analysis report, a multivariate coupling feedback algorithm is used to synchronously match the catalyst state and hydrogen purity according to the time window to generate a multivariate coupling input matrix;

[0093] The multivariate coupled feedback algorithm establishes a time window data mapping based on timestamp-aligned catalyst state data and hydrogen purity analysis reports. Multiple parameters from the catalyst state data, such as activity value and carbon deposit thickness, are integrated with the hydrogen purity and impurity indicators from the hydrogen purity analysis report according to synchronous timescales to form a three-dimensional feature set. The fused data is then constructed into a multivariate coupled input matrix where row vectors correspond to time points, column vectors contain all parameters from both catalyst state data and hydrogen purity analysis reports, and numerical units are normalized according to physical dimensions.

[0094] S5.2: Perform three-channel joint operation on the multivariable coupled input matrix, and generate the initial dynamic proportional control command after weighted fusion of the data from the three channels;

[0095] The multivariable coupled input matrix is ​​decomposed according to the three-channel joint operation rule: Channel 1 extracts the row vector of catalyst state data and performs differential enhancement operation; Channel 2 extracts the row vector of hydrogen purity analysis report and performs normalization and dimensionality reduction processing; Channel 3 binds process timing parameters and runs Fourier phase filtering; the output data of the three channels are weighted and fused after being assigned preset weights.

[0096] The three channels of data refer to the catalyst state data row vector separated from the multivariate coupling input matrix, which includes dynamic parameters such as catalyst activity decay coefficient and carbon deposition thickness; the hydrogen purity analysis report row vector extracted from the multivariate coupling input matrix, which covers purity quantification indicators such as residual oxygen concentration and water vapor content; and the process time series parameters bound from the multivariate coupling input matrix, including time series operating parameters such as cryogenic tower pressure fluctuation frequency and PSA adsorption tower pressure equalization time interval.

[0097] S5.3: The initial dynamic proportional control instruction is subjected to dual security verification through hardware security gate group and instruction timing self-test, and is converted into a dynamic proportional control instruction based on the verification result.

[0098] The hardware security gate group and instruction timing self-test program perform a dual verification process: First, they search the proportional adjustment coefficient contained in the initial dynamic proportional control instruction and compare it with the predefined process limit range boundary value for compliance; second, they scan whether the catalyst health status label provided by the catalyst status identification module matches the preset red alarm trigger condition identifier; if the proportional adjustment coefficient meets the process limit range constraint and the catalyst health status label does not trigger the red alarm condition, the initial dynamic proportional control instruction is converted into the final effective dynamic proportional control instruction output; otherwise, it enters the instruction maintenance state to lock the current control parameters.

[0099] This embodiment also provides a methanol-demineralized water vaporization reaction system based on dynamic proportion control, including:

[0100] The mixing ratio calculation module is used to generate optimized real-time mixing ratio parameters of methanol-deionized water by precooling the mixture with LNG cold energy and combining it with a dynamic temperature compensation algorithm.

[0101] The cold energy phase change enhancement module is used to detect abrupt changes in the real-time mixing ratio parameters of methanol-deionized water, triggering a cold energy phase change enhancement mechanism to generate a high-temperature vaporized mixture.

[0102] The catalytic cracking identification module is used to generate hydrogen-containing conversion gas through catalytic cracking reaction based on high-temperature vaporized mixed gas, and to identify the catalyst state based on the catalyst bed pressure difference and activity decay coefficient.

[0103] The condensation and purification analysis module is used to condense hydrogen-containing conversion gas and purify it using a five-tower PSA process. Then, it generates ultra-high purity hydrogen and a hydrogen purity analysis report through online monitoring by a laser gas analyzer.

[0104] The control command generation module is used to generate dynamic proportional control commands based on catalyst state and hydrogen purity analysis reports through a multivariable coupled feedback algorithm.

[0105] This embodiment also provides a computer device applicable to the methanol-demineralized water vaporization reaction method based on dynamic proportion control, including: a memory and a processor; the memory is used to store computer-executable instructions, and the processor is used to execute the computer-executable instructions to realize the methanol-demineralized water vaporization reaction method based on dynamic proportion control as proposed in the above embodiment.

[0106] The computer device can be a terminal, comprising a processor, memory, communication interface, display screen, and input devices connected via a system bus. The processor provides computing and control capabilities. The memory includes non-volatile storage media and internal memory. The non-volatile storage media stores the operating system and computer programs. The internal memory provides an environment for the operation of the operating system and computer programs stored in the non-volatile storage media. The communication interface is used for wired or wireless communication with external terminals; wireless communication can be achieved through Wi-Fi, carrier networks, NFC (Near Field Communication), or other technologies. The display screen can be an LCD screen or an e-ink screen. The input devices can be a touch layer covering the display screen, buttons, a trackball, or a touchpad on the computer device's casing, or an external keyboard, touchpad, or mouse.

[0107] This embodiment also provides a storage medium storing a computer program that, when executed by a processor, implements the methanol-desalinated water vaporization reaction method based on dynamic proportional control as proposed in the above embodiments. The storage medium can be implemented by any type of volatile or non-volatile storage device or a combination thereof, such as Static Random Access Memory (SRAM), Electrically Erasable Programmable Read-Only Memory (EEPROM), Erasable Programmable Read Only Memory (EPROM), Programmable Red-Only Memory (PROM), Read-Only Memory (ROM), magnetic storage, flash memory, magnetic disk, or optical disk.

[0108] In summary, this invention solves the problem of cold energy fluctuation and phase transition instability by: using a temperature dynamic compensation algorithm to regulate the methanol-deionized water ratio in real time, simultaneously achieving anti-icing and efficient cold energy transfer in the titanium alloy cryogenic tower; using a multivariate coupled feedback algorithm to connect catalyst state and hydrogen purity parameters, eliminating the control island of catalytic cracking-adsorption purification; and combining the cold energy phase transition enhancement mechanism, near-infrared spectroscopy ratio verification, and laser-pressure cross-verification to construct a closed-loop optimization system for the entire process, achieving a three-in-one leap in cold energy utilization, hydrogen purity, and equipment lifespan.

[0109] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention.

Claims

1. A methanol-deionized water vaporization reaction method based on dynamic proportion control, characterized in that: include, The optimized real-time mixing ratio parameters of methanol-deionized water are generated by precooling the mixture with LNG cold energy and combining it with a dynamic temperature compensation algorithm. Based on the abrupt detection of the real-time mixing ratio parameter of methanol-deionized water, a cold energy phase change enhancement mechanism is triggered to generate a high-temperature vaporized mixture. The catalyst is converted into hydrogen-containing gas by catalytic cracking reaction based on high-temperature vaporized mixed gas, and the catalyst state is identified based on the catalyst bed pressure difference and activity decay coefficient. The hydrogen-containing converted gas is condensed and purified using a five-tower PSA process, and then ultra-high purity hydrogen and a hydrogen purity analysis report are generated through online monitoring by a laser gas analyzer. Based on the catalyst state and hydrogen purity analysis report, a dynamic proportional control command is generated through a multivariate coupled feedback algorithm.

2. The methanol-deionized water vaporization reaction method based on dynamic proportion control as described in claim 1, characterized in that: The process of precooling the mixture with LNG cold energy and combining it with a dynamic temperature compensation algorithm to generate optimized real-time mixing ratio parameters for methanol-demineralized water is as follows: The methanol and demineralized water are pre-cooled according to the initial ratio using LNG cold energy through a titanium alloy heat exchanger, and the temperature data of the mixture is collected in real time. Based on the mixed liquid temperature data and combined with a temperature dynamic compensation algorithm, the optimized dynamic ratio parameters of methanol-deionized water are generated. Based on the optimized dynamic ratio parameters of methanol-deionized water, the real-time mixing ratio parameters of methanol-deionized water are generated by scanning the characteristic absorption peaks of methanol and water using an online near-infrared spectrometer.

3. The methanol-deionized water vaporization reaction method based on dynamic proportion control as described in claim 2, characterized in that: The steps for triggering the cold energy phase change enhancement mechanism to generate a high-temperature vaporized mixture are as follows. Based on the real-time mixing ratio parameter of methanol-deionized water, the ratio fluctuation amplitude is monitored through a sliding time window to generate a ratio mutation verification report; Based on the proportional mutation verification report, a three-stage cold energy phase change enhancement method was used to perform LNG cold energy pressurization injection, ultrasonic nucleation and phase change point coordinated control. When the phase change conditions were reached, a low temperature and high pressure liquid mixed phase was generated. The low-temperature, high-pressure liquid mixture is introduced into the titanium-zirconium alloy vaporization tower, and then heated by a nested electric heating unit and the LNG waste heat recovery pipeline to generate a high-temperature vaporized mixture.

4. The methanol-deionized water vaporization reaction method based on dynamic proportion control as described in claim 3, characterized in that: The process of generating hydrogen-containing converted gas through catalytic cracking of a high-temperature vaporized mixture involves the following steps. The high-temperature vaporized mixture is introduced into a fixed-bed reactor filled with a nickel-based catalyst, where the mixture undergoes a catalytic cracking reaction on the catalyst surface to generate hydrogen-containing conversion gas.

5. The methanol-deionized water vaporization reaction method based on dynamic proportion control as described in claim 4, characterized in that: The steps for identifying the catalyst state based on the catalyst bed pressure difference and activity decay coefficient are as follows: During the catalytic cracking reaction, the catalyst bed pressure difference is monitored in real time, and the activity decay coefficient is obtained by back-calculation based on the changes in the concentration of the outlet gas components and the thermodynamic equilibrium formula of the cracking reaction. By combining the catalyst bed pressure difference and activity decay coefficient, the micropore blockage evolution analysis method is used to predict the catalyst deactivation risk index and identify the catalyst state.

6. The methanol-deionized water vaporization reaction method based on dynamic proportion control as described in claim 5, characterized in that: The process involves condensing the hydrogen-containing converted gas and purifying it using a five-tower PSA process, followed by online monitoring with a laser gas analyzer to generate ultra-high purity hydrogen and a hydrogen purity analysis report. The steps are as follows: Based on the process of separating heavy hydrocarbon components from hydrogen-containing converted gas by passing it through a stainless steel corrugated pipe condenser and a titanium alloy cryogenic tower, saturated wet hydrogen gas is generated. Saturated wet hydrogen gas is fed into a five-tower pressure swing adsorption (PSA) equipment for five-tower PSA process purification. At the same time, pressure transmitters are used to monitor the phase change point of the adsorption towers to generate crude and refined hydrogen gas and the dynamic pressure parameters of each tower. The crude and refined hydrogen gas is introduced into a quartz sampling cell, and a laser gas analyzer is used to scan the characteristic peaks of key components for hydrogen purity. The results are then cross-validated with the dynamic pressure parameters of each tower to generate ultra-high purity hydrogen gas and a hydrogen purity analysis report.

7. The methanol-deionized water vaporization reaction method based on dynamic proportion control as described in claim 6, characterized in that: The steps for generating dynamic proportional control commands using a multivariable coupled feedback algorithm are as follows: Based on the catalyst state and hydrogen purity analysis report, a multivariate coupled feedback algorithm is used to synchronously match the catalyst state and hydrogen purity according to the time window to generate a multivariate coupled input matrix. The multivariable coupled input matrix is ​​subjected to three-channel joint operation, and the data from the three channels are weighted and fused to generate the initial dynamic proportional control command. The initial dynamic proportional control instruction is subjected to dual security verification through hardware security gate groups and instruction timing self-test, and is converted into a dynamic proportional control instruction based on the verification results.

8. A methanol-demineralized water vaporization reaction system based on dynamic proportion control, based on the methanol-demineralized water vaporization reaction method based on dynamic proportion control according to any one of claims 1 to 7, characterized in that: include, The mixing ratio calculation module is used to generate optimized real-time mixing ratio parameters of methanol-deionized water by precooling the mixture with LNG cold energy and combining it with a dynamic temperature compensation algorithm. The cold energy phase change enhancement module is used to detect abrupt changes in the real-time mixing ratio parameters of methanol-deionized water, triggering a cold energy phase change enhancement mechanism to generate a high-temperature vaporized mixture. The catalytic cracking identification module is used to generate hydrogen-containing conversion gas through catalytic cracking reaction based on high-temperature vaporized mixed gas, and to identify the catalyst state based on the catalyst bed pressure difference and activity decay coefficient. The condensation and purification analysis module is used to condense hydrogen-containing conversion gas and purify it using a five-tower PSA process. Then, it generates ultra-high purity hydrogen and a hydrogen purity analysis report through online monitoring by a laser gas analyzer. The control command generation module is used to generate dynamic proportional control commands based on catalyst state and hydrogen purity analysis reports through a multivariable coupled feedback algorithm.

9. A computer device comprising a memory and a processor, wherein the memory stores a computer program, characterized in that: When the processor executes the computer program, it implements the steps of the methanol-deionized water vaporization reaction method based on dynamic ratio control as described in any one of claims 1 to 7.

10. A computer-readable storage medium having a computer program stored thereon, characterized in that: When the computer program is executed by the processor, it implements the steps of the methanol-deionized water vaporization reaction method based on dynamic ratio control as described in any one of claims 1 to 7.

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