A process and apparatus for producing hydrogen from organic waste liquid in coal-water slurry mixed industrial production.

Abstract

This invention belongs to the technical field of mixing and purification processes in chemical hydrogen production. Specifically, it discloses a process and apparatus for producing hydrogen from organic waste liquid in the industrial production of coal-water slurry mixtures. The process includes the following steps: mixing coal-water slurry and organic waste liquid using a hydrocyclone mixer; homogenizing and conditioning; conveying to a gasifier for high-temperature gasification reaction; feeding into a radiant waste boiler and a convective waste boiler for staged waste heat recovery; the cooled syngas enters a cyclone scrubbing tower for dust removal; the purified syngas enters a sulfur-resistant shift reactor for CO conversion; the converted gas enters a cyclone plate absorber for two-stage desulfurization and decarbonization; and the hydrogen-rich gas is purified. This invention, using the above-mentioned process and apparatus for producing hydrogen from organic waste liquid in the industrial production of coal-water slurry mixtures, achieves 100% resource utilization of organic waste liquid, improves the mixing effect of coal-water slurry and organic waste liquid, reduces fresh water consumption, reduces acid gas emissions, and improves the quality of hydrogen products.

Description

Technical Field

[0001] This invention relates to the field of mixing and purification technology in chemical hydrogen production processes, and in particular to a process and apparatus for producing hydrogen from organic waste liquid in the industrial production of coal-water slurry mixture. Background Technology

[0002] Liquid-liquid nonhomogeneous mixing and dispersion is the process of homogeneously mixing two immiscible or completely insoluble liquids. This method is widely used in polymer blending, chemical reactions, food processing, biopharmaceuticals, cosmetics, and other fields. Particularly in the chemical industry, mixers can be used for droplet breaking and mixing, increasing the contact interface, mass transfer processes such as solvent extraction; enhancing mixing for liquid-liquid reactions such as polymerization and alkylation; and promoting emulsification processes that disperse droplets of one or more immiscible liquids as a continuous phase. Generally, improving the degree of liquid-liquid mixing contributes to the performance improvement of the aforementioned processes.

[0003] Mixers are categorized into static mixers and dynamic mixers. Static mixers, such as Venturi jet mixers, SK static mixers, SV static mixers, and impingement flow mixers, have simple structures and low pressure drops, but their mixing effect is not ideal. Dynamic mixers, such as high-shear mixers, kettle mixers, and emulsion pumps, are micromixers with high local energy dissipation caused by the meshing of the rotor and stator. However, the manufacture of such micromixers is often complex and expensive, limiting their widespread application in the field of micromixing. In contrast, static micromixers use geometric structures to generate chaotic fluid flow without any moving parts, making them simpler, cheaper, and more cost-effective when integrated into micromixing systems.

[0004] In existing technologies, various geometries and modifications have been studied, such as micromixer wall torsion, staggered herringbone designs, fluid interface blockage, surface grooves and baffles, split (SAR) units, Tesla structures, lateral stacking of mixing units, and submersion of mixing units to generate chaotic flow fields. However, most passive micromixers only exhibit effective mixing within a limited Reynolds number range, and a static mixer with mixing performance comparable to dynamic high-shear mixers is still lacking. Furthermore, the hydrogen production process from organic wastewater in coal-water slurry mixing industrial production suffers from problems such as low mixing efficiency, high energy consumption, large catalyst consumption, excessive external chemical reagents, high levels of post-production wastewater, and low hydrogen quality. Summary of the Invention

[0005] The purpose of this invention is to provide a process and apparatus for producing hydrogen from organic waste liquid in the industrial production of coal-water slurry, so as to achieve 100% resource utilization of organic waste liquid, reduce fresh water consumption, reduce acid gas emissions, and improve the quality of hydrogen products.

[0006] To achieve the above objectives, the present invention provides a process for producing hydrogen from organic waste liquid in the industrial production of coal-water slurry, comprising the following steps: S1. The coal-water slurry and organic waste liquid are mixed and separated from impurities using a hydrocyclone mixer to obtain a mixed slurry; S2. The mixed slurry obtained in S1 is homogenized and conditioned to optimize its viscosity and particle size distribution, resulting in a homogeneous composite slurry. S3. The homogeneous composite slurry obtained in S2 is pressurized and transported to the gasifier, where it undergoes a high-temperature gasification reaction with the gasifying agent to obtain hydrogen-containing syngas (crude syngas mainly composed of H2 and CO) and liquid slag. S4. The hydrogen-containing syngas obtained in S3 is sequentially fed into the radiant waste boiler and the convective waste boiler for cascade waste heat recovery. The by-product high-pressure steam is recycled into the steam circulation system. The cooled syngas enters the cyclone spray scrubbing tower for dust removal. The purified syngas enters the sulfur-resistant shift reactor for CO conversion. The shifted gas enters the cyclone plate absorption tower for two-stage desulfurization and decarbonization, resulting in hydrogen-rich gas with acid gas concentration reduced to below 10 ppm. S5. The hydrogen-rich gas obtained in S4 is purified by membrane separation and pressure swing adsorption coupling process to obtain tail gas and hydrogen gas with a purity of ≥99.97%. S6. The liquid slag obtained in S3 is sent to a cyclone residue separator for separation. The residual carbon particles with a particle size >100μm are returned to the gasifier, and the tail gas obtained in S5 is returned to the gasifier.

[0007] Preferably, in S2, the homogenization and conditioning are carried out by ultrasonic treatment at a frequency of 20~40kHz, so that the slurry particle size D90≤50μm.

[0008] Preferably, in S3, the reaction conditions for the high-temperature gasification reaction are a pressure of 4.0~6.0MPa and a temperature of 1300~1500℃, the gasifying agent is a mixture of pure oxygen and water vapor, and the oxygen-carbon molar ratio of the gasifying agent is 0.8~1.0.

[0009] Preferably, in S4, the purified syngas enters the sulfur-resistant shift reactor to adjust the H2 / CO ratio and control the water-gas ratio at 1.8~2.2 for deep CO shift. The desulfurization process uses a cyclone plate absorber to contact nano-zinc oxide slurry in a countercurrent manner. The pH value of the nano-zinc oxide slurry is controlled at 8.5~9.5. Methyl diethanolamine solution is used to reduce the concentration of acidic gas to below 10 ppm (total sulfur removal efficiency ≥99.8%, H2S content in outlet syngas ≤10 ppm).

[0010] Preferably, S5 is as follows: Hydrogen-rich gas enters the palladium membrane separator, where the separation pressure difference is controlled at 2-3 MPa for hydrogen purification. The separation tail gas is returned to the gasifier as supplementary fuel through the tail gas circulation pipeline for recycling.

[0011] Preferably, in S6, fine ash with a particle size of <50μm is used as a building material raw material for preparing non-fired bricks or concrete admixtures, and the fine ash content is ≤30%.

[0012] This invention also provides a device for producing hydrogen from organic waste liquid in the industrial production of coal-water slurry, comprising: The hydrocyclone mixing module includes a hydrocyclone mixer with a tangential inlet diameter of 30~50mm and a grooved section structure. The grooved section of the grooved section structure has a length of 600~800mm, and the ratio of the groove diameter to the main pipe diameter is 0.7~0.9. The hydrocyclone mixer is made of corrosion-resistant alloy. The gasification reaction module includes a pressurization pump, a gasifier, and a cyclone residue separator; Waste heat recovery module, including radiant waste boiler, convective waste boiler and steam circulation system; The syngas purification module includes a cyclone spray scrubbing tower, a sulfur-resistant shift reactor, and a cyclone plate absorption tower. The atomizing nozzle of the cyclone spray scrubbing tower has a cyclone core structure, a nozzle orifice diameter of 0.5~1.0mm, and an atomization angle of 60~90°. The tower body of the cyclone spray scrubbing tower is made of fiberglass lined with silicon carbide. The hydrogen purification module includes a palladium membrane separator and a tail gas recirculation pipeline. The palladium membrane separator has a hydrogen permeation rate ≥30m³ / h. 3 / (m 2 The hollow fiber membrane (h) has a palladium membrane as a honeycomb support, and the membrane thickness uniformity error is ≤5%. The palladium membrane separator integrates a heat exchange unit to achieve heat self-balance.

[0013] The palladium membrane separator is also connected to a pressure swing adsorption tower, which uses 13X molecular sieve adsorbent, with an adsorption pressure of 2.5~3.0MPa, a desorption pressure of 0.1~0.3MPa, and a final hydrogen purity of ≥99.97%.

[0014] Preferably, the hydrocyclone mixer adopts a multi-stage series-parallel structure with a single unit processing capacity of 15~30t / h. Each stage mixer outlet is equipped with an online turbidity monitor to provide real-time feedback on mixing uniformity and adjust the inlet flow rate.

[0015] Preferably, the groove section of the hydrocyclone mixer has a length of 600~800mm, and the ratio of the groove diameter to the main pipe diameter is 0.7~0.9.

[0016] The mixing effect was optimized by using a hydrocyclone mixer with different straight pipe sections. The design of the groove section formed a flow pattern of blocking-releasing-blocking, which effectively reduced energy consumption. By reducing the tangential inlet diameter (30~50mm), the turbulence effect was enhanced, which increased the mixing uniformity (DOM) of coal-water slurry and organic waste liquid by 40% and reduced the mixing energy consumption (MEC) by 90%, which is conducive to the formation of homogeneous composite slurry.

[0017] Therefore, the present invention employs the above-mentioned process and apparatus for hydrogen production from organic waste liquid in coal-water slurry mixed industrial production, and the beneficial effects are as follows: Excellent mixing effect and low energy consumption: This invention improves the mixing effect under high oil-water ratio by increasing the number and length of corrugated sheets, so that high mixing uniformity can be maintained in a wide range of oil-water ratios, improving the adaptability and stability of the process. Through the optimized hydraulic cyclone mixer, combined with the addition of dispersant and ultrasonic treatment, the mixing uniformity of coal-water slurry and organic waste liquid is increased by 40%, the mixing energy consumption is reduced by 90%, the slurry particle size D90≤50μm and the viscosity fluctuation rate<5%, realizing the effective mixing of organic waste liquid and coal slurry, avoiding pipeline blockage, and laying a high-efficiency mass transfer foundation for subsequent gasification reaction.

[0018] High resource utilization rate: This invention achieves 100% resource utilization of organic waste liquid, separates tail gas and residual carbon particles for recycling, and classifies and utilizes ash residue for resource utilization. The system carbon conversion rate reaches over 98%, and the residual carbon utilization rate is ≥85%, which greatly reduces raw material consumption.

[0019] High hydrogen production efficiency and superior product quality: This invention increases hydrogen yield by 28% compared to traditional processes. The hydrogen purity obtained through palladium membrane separation (or coupled pressure swing adsorption) is ≥99.97%, meeting the fuel cell-grade hydrogen standard (GB / T 37244-2018). The energy consumption per unit of hydrogen production is reduced to 3.8 kW·h / Nm³. 3 This is lower than the industry average (4.5-5.0 kWh / Nm³). 3 ).

[0020] Significant energy conservation and emission reduction effects: This invention reduces fresh water consumption by 60% and increases the recycling rate of water to 95%; acidic gases (SO2, NO) x Emissions are reduced by 90%, meeting the ultra-low emission standard (GB 31570-2015); the system carbon conversion rate is over 98%, the carbon emission intensity (tons of CO2 / tons of H2) is reduced by 20%, and no additional chemical desulfurizers are required, avoiding secondary pollution.

[0021] Highly economical and industrially feasible: This invention reduces the overall cost of hydrogen production by 32%, and the by-product high-pressure steam meets 80% of the system's power demand, increasing the overall energy utilization rate by 25%. Each module of the device adopts a standardized and integrated design, and the multi-stage series and parallel structure is adapted to industrial production with different processing capacities. It is also equipped with an online monitoring and automatic control system, making it easy to operate and stable in operation.

[0022] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Attached Figure Description

[0023] Figure 1 This is a schematic flow diagram of an embodiment of a hydrogen production process and apparatus for organic waste liquid in the mixed industrial production of coal-water slurry according to the present invention. Figure 2 This is a schematic diagram of the structure of a hydrocyclone mixer in an embodiment of a process and apparatus for producing hydrogen from organic waste liquid in the industrial production of coal-water slurry mixing according to the present invention. Figure 3 This is a schematic diagram of the mixing principle of a hydrocyclone mixer in an embodiment of a hydrogen production process and apparatus for organic waste liquid in coal-water slurry mixing industrial production according to the present invention.

[0024] Figure Labels 1-1 First hydrocyclone separator; 1-2 Second hydrocyclone separator; 1-3 Hydrocyclone mixer; 1-4 Booster pump; 1-5 Gasifier; 1-6 Radiant waste boiler; 1-7 Convection waste boiler; 1-8 Cyclone spray scrubbing tower; 1-9 Sulfur-resistant shift reactor; 1-10 Cyclone plate absorber; 1-11 Palladium membrane separator; 2-1. Swirl inlet; 2-2. Swirl column; 2-3. Swirl cone; 2-4. Overflow pipe; 2-5. Underflow seal pipe; 3-1 Organic waste liquid inlet; 3-2 Coal-water slurry inlet; 3-3 Mixing channel; 3-4 Product outlet. Detailed Implementation

[0025] The technical solution of the present invention will be further described below with reference to the accompanying drawings and embodiments.

[0026] Unless otherwise defined, the technical or scientific terms used in this invention shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention pertains.

[0027] Example 1 A hydrogen production device for organic waste liquid in coal-water slurry industrial production is disclosed. Specifically, it is an experimental stage device that processes different oil and water phase flow rates, with an oil-water ratio set from 2% to 100%. For example, when the oil-water ratio is 2%, the oil phase flow rate is 2 L / h, the water phase flow rate is 100 L / h, and the outlet flow rate is 102 L / h; when the oil-water ratio is 100%, the oil phase flow rate is 100 L / h, the water phase flow rate is 0 L / h, and the outlet flow rate is 100 L / h. By changing the oil-water ratio, the mixing effect and energy consumption changes of the mixer under different ratios can be studied. The device includes: The hydrocyclone mixing module includes hydrocyclone mixers 1-3, a flow meter, a pressure gauge, and a self-priming pump. Specifically, it includes hydrocyclone mixers 1-3 with different structures (one section of corrugated pipe, two sections of corrugated pipe, and different numbers of corrugated plates).

[0028] Its specific operation process and effects are described as follows: 1. Implementation process Organic waste liquid and coal slurry enter the hydrocyclone mixer 1-3 from different inlets, where they are mixed. The final mixture flows out from the outlet and is collected in a storage tank. By adjusting the flow meter and valves, the flow rate and proportion of different phases can be controlled to study the effect of different oil-water ratios on the mixing effect.

[0029] 2. Results Analysis Degree of Mixing (DOM) Analysis: The DOM values ​​of hydraulic cyclone mixers 1-3 with different structures varied significantly under different oil-water ratios. The two-section corrugated pipe structure exhibited a higher DOM value (average 97%) at oil-water ratios of 2-10%, significantly higher than the single-section corrugated pipe structure and the non-corrugated pipe structure. This indicates that at low oil-water ratios, the two-section corrugated pipe structure is more effective in promoting oil-water mixing. When the oil-water ratio increased to 20-100%, the single-section corrugated pipe structure showed relatively better mixing, especially with corrugated pipe lengths of 50mm and 150mm, resulting in higher DOM values. The DOM value of the two-section corrugated pipe structure decreased, possibly due to changes in fluid flow characteristics at high oil-water ratios, leading to poorer mixing. Increasing the number of corrugated blades significantly improved the degree of mixing at high oil-water ratios. For example, increasing the number of corrugated blades from 10 to 20 increased the DOM value at a 100% oil-water ratio from 81% to 99%, demonstrating that increasing the number of corrugated blades effectively improved the mixing effect.

[0030] Mixing Energy Consumption (MEC) Analysis: The MEC values ​​of hydrocyclone mixers 1-3 with different structures varied under different oil-water ratios. The two-section bellows structure with a 28mm bellows length exhibited a higher MEC value at low oil-water ratios, but the MEC value gradually decreased with increasing oil-water ratio. This is likely because the protruding part of this structure effectively reduces energy consumption at high oil-water ratios. The single-section bellows structure with a 150mm bellows length had a higher MEC value under different oil-water ratios, especially at high oil-water ratios. This is likely because the longer bellows increased fluid flow resistance, thus increasing energy consumption. By optimizing the bellows length and the number of bellows, energy consumption can be reduced while maintaining mixing effectiveness. For example, the two-section bellows structure with a 50mm bellows length achieves both a high DOM value and a low MEC value at oil-water ratios of 2-10%, demonstrating good overall performance.

[0031] Experimental and numerical simulation studies yielded the following conclusions: the structural parameters of the hydrocyclone mixer 1-3 significantly affect the mixing effect and energy consumption. The two-section corrugated pipe structure exhibits better mixing performance at low oil-water ratios, while the single-section corrugated pipe structure performs better at high oil-water ratios. The corrugated pipe length and the number of corrugated plates are crucial factors influencing both mixing effect and energy consumption. Appropriately increasing the number of corrugated plates can improve the mixing degree but also increases energy consumption. Therefore, when designing the hydrocyclone mixer 1-3, it is necessary to comprehensively consider both mixing effect and energy consumption, and select appropriate corrugated pipe lengths and the number of corrugated plates. Precisely controlling the structural design and optimization of the mixer in the hydrogen production process using coal-water slurry mixed with organic waste liquid based on the oil-water ratio helps improve mixing efficiency, reduce energy consumption, and thus enhance the overall performance of the hydrogen production process.

[0032] Example 2 A hydrogen production device for organic waste liquid in coal-water slurry mixed industrial production, specifically with an annual hydrogen production capacity of 3.6 × 10⁻⁶. 8 Nm 3 The industrial production unit treats organic waste liquid and coal-water slurry, which are liquid-liquid mixtures. The organic waste liquid has a flow rate of 3 t / h and a temperature of 45℃, while the coal-water slurry has a viscosity of 20 cp, a temperature of 55℃, and a liquid phase density of 805 kg / m³. 3 .

[0033] like Figure 1 As shown, the device includes: The hydrocyclone mixing module includes a first hydrocyclone separator 1-1 for treating organic waste liquid, a second hydrocyclone separator 1-2 for treating coal-water slurry, and a hydrocyclone mixer 1-3; The gasification reaction module includes pressurized pumps 1-4, a high-pressure fluidized bed gasifier 1-5, and a cyclone residue separator. The gasification pressure of gasifier 1-5 is 4.2 MPa, the temperature is 1400℃, and the oxygen-to-coal ratio is 1.0 Nm³.3 / kg, unreacted carbon is recovered from the liquid slag via a hydrocyclone separator, and the residue recycling rate is ≥85%; Waste heat recovery module, including radiant waste boiler 1-6, convective waste boiler 1-7 and steam circulation system; The syngas purification module includes cyclone scrubbing towers 1-8, sulfur-resistant shift reactors 1-9, and cyclone plate absorption towers 1-10. The atomized droplet size of the cyclone scrubbing towers 1-8 is 50-150 μm, and the tower is equipped with 3-5 stages of cyclone plates, with a pressure drop of ≤0.1 MPa per stage (in this embodiment, four stages of cyclone plates are used, with an atomized droplet size of 80 μm, and the tower body is made of fiberglass lined with silicon carbide). The cyclone plate absorption towers 1-10 have a cyclone plate inclination angle of 40°, a plate spacing of 200-300 mm, and a liquid-to-gas ratio of 4 L / Nm³. 3 The desulfurization efficiency is ≥99.5%.

[0034] The hydrogen purification module includes palladium membrane separators 1-11 and a tail gas recirculation pipeline; the palladium membrane separators 1-11 operate at a temperature of 450℃, an operating pressure of 2.5MPa, a membrane thickness of 20-50μm (30μm in this embodiment), and a hydrogen permeation flux of 13.2Nm. 3 / (m 2 •h). The palladium membrane separator 1-11 is also connected to a pressure swing adsorption tower, which uses 13X molecular sieve adsorbent, with an adsorption pressure of 2.7 MPa and a desorption pressure of 0.2 MPa.

[0035] Specifically, the first hydrocyclone separator 1-1 and the second hydrocyclone separator 1-2 have the same structure. Taking the first hydrocyclone separator 1-1 as an example, as follows... Figure 2 As shown, the first hydrocyclone separator 1-1 includes a cyclone inlet 2-1, a cyclone column 2-2, a cyclone cone 2-3, an overflow pipe 2-4, and an underflow liquid seal pipe 2-5. The cone angle of the cyclone cone 2-3 is θ. During normal operation, the mixed slurry enters the equipment from the cyclone inlet 2-1. Under the action of the cyclone field, the heavy phase catalyst flows out through the underflow port of the underflow liquid seal pipe 2-5, and the light phase slurry flows out from the overflow pipe 2-4.

[0036] like Figure 3As shown, the hydrocyclone mixer 1-3 includes an organic waste liquid inlet 3-1, a coal-water slurry inlet 3-2, a mixing channel 3-3, and a mixed product outlet 3-4. During normal operation, the organic waste liquid enters the equipment through the organic waste liquid inlet 3-1, and the coal slurry enters through the coal-water slurry inlet 3-2. Within the mixing channel 3-3, a specific structural design (in this embodiment, a pyramid structure and a groove structure) ensures thorough mixing of the organic waste liquid and the coal slurry. The mixed coal-water slurry flows out from the product outlet 3-4, forming a homogeneous coal-water slurry mixture. Specifically, the groove structure of the hydrocyclone mixer 1-3 has a groove length of 700 mm, a groove diameter to main pipe diameter ratio of 0.8, and adopts a multi-stage parallel structure, with a single unit processing capacity of 15~30 t / h.

[0037] Its specific operation process and effects are described as follows: Before being added to the gasifier 1-5 for hydrogen production, the organic waste liquid and coal-water slurry undergo preliminary separation in the first hydrocyclone separator 1-1 and the second hydrocyclone separator 1-2, respectively. They then enter the hydrocyclone mixer 1-3 for enhanced mixing, forming a homogeneous slurry. This slurry is then pumped into the gasifier 1-5 via a pressurized pump 1-4 for pressurized fluidized bed gasification, producing crude syngas mainly composed of H2 and CO, and liquid slag. The high-temperature syngas enters the radiant waste boiler 1-6 and the convective waste boiler 1-7 for cascaded waste heat recovery, and the by-product high-pressure steam is reused in the steam cycle system. The cooled syngas enters the cyclone scrubbing tower 1-8, where dust is removed by a multi-stage cyclone atomizing device. It then enters the sulfur-resistant shift reactor 1-9 to adjust the H2 / CO ratio and control the water-gas ratio at 1.8~2.2 for deep CO shift. The shifted gas undergoes two-stage desulfurization and decarbonization in the cyclone plate absorber 1-10. After the concentration of acidic gases is reduced using methyl diethanolamine solution, it enters the palladium membrane separator 1-11 for hydrogen purification, obtaining high-purity refined hydrogen. The separation tail gas can be returned to the gasifier 1-5 as supplementary fuel for recycling.

[0038] Results analysis: After adopting a hydrocyclone mixer 1-3 with a groove section length of 700mm and a groove diameter to main pipe diameter ratio of 0.8, the mixing uniformity (DOM) of coal-water slurry and organic waste liquid increased from 0.65 in the traditional process to 0.91 (an increase of 40%), and the mixing energy consumption (MEC) decreased from 12.5kW·h / t in the original process to 1.25kW·h / t (a decrease of 90%). Online turbidity monitoring showed that the standard deviation of particle size distribution in the slurry was ≤10μm and the viscosity fluctuation rate was <5%, indicating a significant improvement in mixing homogeneity, laying a foundation for efficient mass transfer in the subsequent gasification reaction.

[0039] At a gasification pressure of 4.2 MPa and an oxygen-to-coal ratio of 1.0 Nm³, 3Under the condition of / kg, the carbon conversion rate reaches 98.3%, which is significantly improved compared with the conventional gasification process (carbon conversion rate 92~95%). The cyclone residue separator recovers 87% of the unreacted carbon, and the raw material consumption of gasifiers 1-5 is reduced by 15% after residue reuse, saving about 18,000 tons of coal-water slurry raw material annually. The radiant waste boilers 1-6 and convective waste boilers 1-7 recover waste heat in a cascade manner, producing 12.5t / h of high-pressure steam as a by-product, meeting 80% of the system's power demand, and improving the overall energy utilization rate by 25%. The cyclone spray scrubbing towers 1-8 adopt a four-stage cyclone plate (pressure drop 0.08MPa / stage), with an atomized droplet size of 80μm, a dust removal rate of 99.2%, and an outlet gas dust content ≤5mg / Nm³. 3 ; Swirl plate absorber 1-10 (plate inclination angle 40°, liquid-to-gas ratio 4L / Nm³) 3 Combined with methyldiethanolamine solution, the desulfurization efficiency is 99.6%, with outlet H2S concentration <8ppm and CO2 concentration <50ppm.

[0040] The palladium membrane separator 1-11 achieves a hydrogen permeation flux of 13.2 Nm³ under operating conditions of 450℃ and 2.5 MPa. 3 / (m 2 The process produces hydrogen with a purity of 99.98%, meeting fuel cell grade standards (GB / T 37244-2018). The residual H2 content in the separated exhaust gas is <0.5%, and after being returned to the gasifier 1-5, the fuel substitution rate is 18%, reducing annual natural gas consumption by approximately 2.6 × 10⁻⁶. 6 Nm 3 .

[0041] 100% of organic waste liquid is recycled, with an annual treatment capacity of 26,000 tons, reducing hazardous waste landfill costs by approximately 52 million yuan; the recycling rate of water has increased to 95%, fresh water consumption has decreased by 63%, and annual water savings have reached 480,000 tons; acidic gases (SO2, NO) are also treated. x Total emissions were reduced by 91%, meeting the ultra-low emission standard (GB 31570-2015); annual hydrogen production reached 3.6 × 10⁻⁶. 8 Nm 3 The yield is increased by 28% compared to traditional processes, and the energy consumption per unit of hydrogen production is reduced to 3.8 kWh / Nm³. 3 (Industry average 4.5~5.0 kWh / Nm) 3 ).

[0042] Therefore, when designing a cyclone mixer, it is necessary to comprehensively consider the mixing effect and energy consumption, and select an appropriate corrugated pipe length and number of corrugated plates. This study provides a theoretical basis and experimental data support for the design and optimization of mixers in the hydrogen production process of coal-water slurry mixed with organic waste liquid, which helps to improve mixing efficiency, reduce energy consumption, and thus improve the overall performance of the hydrogen production process.

[0043] Therefore, the present invention adopts the above-mentioned process and device for producing hydrogen from organic waste liquid in the industrial production of coal-water slurry mixing, so as to achieve 100% resource utilization of organic waste liquid, reduce fresh water consumption, reduce acid gas emissions, and improve the quality of hydrogen products.

[0044] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. 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 still be made to the technical solutions of the present invention, and these modifications or equivalent substitutions cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. A process for producing hydrogen from organic waste liquid in the industrial production of coal-water slurry mixture, characterized in that, Includes the following steps: S1. The coal-water slurry and organic waste liquid are mixed and separated from impurities using a hydrocyclone mixer to obtain a mixed slurry; S2. The mixed slurry obtained in S1 is homogenized and conditioned to optimize its viscosity and particle size distribution, resulting in a homogeneous composite slurry. S3. The homogeneous composite slurry obtained in S2 is pressurized and transported to the gasifier, where it undergoes a high-temperature gasification reaction with the gasifying agent to obtain hydrogen-containing syngas and liquid slag. S4. The hydrogen-containing syngas obtained in S3 is sequentially fed into the radiant waste boiler and the convective waste boiler for cascade waste heat recovery. The by-product high-pressure steam is recycled into the steam circulation system. The cooled syngas enters the cyclone spray scrubbing tower for dust removal. The purified syngas enters the sulfur-resistant shift reactor for CO conversion. The shifted gas enters the cyclone plate absorption tower for two-stage desulfurization and decarbonization, resulting in hydrogen-rich gas with acid gas concentration reduced to below 10 ppm. S5. The hydrogen-rich gas obtained in S4 is purified by membrane separation and pressure swing adsorption coupling process to obtain tail gas and hydrogen gas with a purity of ≥99.97%. S6. The liquid slag obtained in S3 is sent to a cyclone residue separator for separation. The residual carbon particles with a particle size >100μm are returned to the gasifier, and the tail gas obtained in S5 is returned to the gasifier. A hydrogen production apparatus for organic waste liquid in coal-water slurry industrial production, used for implementing the aforementioned hydrogen production process for organic waste liquid in coal-water slurry mixed industrial production, comprises: The hydrocyclone mixing module includes a hydrocyclone mixer with a tangential inlet diameter of 30-50 mm and a grooved section structure, a first hydrocyclone separator, and a second hydrocyclone separator; The groove section of the groove structure has a length of 600~800mm, and the ratio of the groove diameter to the main pipe diameter is 0.7~0.

9. The material of the hydrocyclone mixer is a corrosion-resistant alloy. The first hydrocyclone separator includes a hydrocyclone inlet, a hydrocyclone column, a hydrocyclone cone, an overflow pipe, and an underflow liquid seal pipe. The cone angle of the hydrocyclone cone is θ. The cone angle is 10~65°; The gasification reaction module includes a pressurization pump, a gasifier, and a cyclone residue separator; Waste heat recovery module, including radiant waste boiler, convective waste boiler and steam circulation system; The syngas purification module includes a cyclone spray scrubbing tower, a sulfur-resistant shift reactor, and a cyclone plate absorption tower. The atomizing nozzle of the cyclone spray scrubbing tower has a cyclone core structure, a nozzle orifice diameter of 0.5~1.0mm, and an atomization angle of 60~90°. The tower body of the cyclone spray scrubbing tower is made of fiberglass lined with silicon carbide. The hydrogen purification module includes a palladium membrane separator and a tail gas recirculation pipeline. The palladium membrane separator has a hydrogen permeation rate ≥30m³ / h. 3 / (m 2 The hollow fiber membrane (h) has a palladium membrane as a honeycomb support, and the membrane thickness uniformity error is ≤5%. The palladium membrane separator integrates a heat exchange unit to achieve heat self-balance.

2. The process for producing hydrogen from organic waste liquid in a coal-water slurry mixed industrial production according to claim 1, characterized in that, In S2, homogenization and conditioning are carried out by ultrasonic treatment at a frequency of 20~40kHz to make the slurry particle size D90≤50μm.

3. The process for producing hydrogen from organic waste liquid in the industrial production of coal-water slurry according to claim 1, characterized in that, In S3, the reaction conditions for the high-temperature gasification reaction are a pressure of 4.0~6.0MPa and a temperature of 1300~1500℃. The gasifying agent is a mixture of pure oxygen and water vapor, and the oxygen-carbon molar ratio of the gasifying agent is 0.8~1.

0.

4. The process for producing hydrogen from organic waste liquid in the industrial production of coal-water slurry according to claim 1, characterized in that, In S4, the purified syngas enters the sulfur-resistant shift reactor to adjust the H2 / CO ratio and control the water-gas ratio at 1.8~2.2 for deep CO conversion. The desulfurization process uses a cyclone plate absorber to contact the nano zinc oxide slurry countercurrently. The pH value of the nano zinc oxide slurry is controlled at 8.5~9.5, and methyl diethanolamine solution is used to reduce the concentration of acidic gases.

5. The process for producing hydrogen from organic waste liquid in a coal-water slurry mixed industrial production according to claim 1, characterized in that, S5 specifically refers to: Hydrogen-rich gas enters the palladium membrane separator, where the separation pressure difference is controlled at 2-3 MPa for hydrogen purification. The separation tail gas is returned to the gasifier as supplementary fuel through the tail gas circulation pipeline for recycling.

6. The process for producing hydrogen from organic waste liquid in the industrial production of coal-water slurry according to claim 1, characterized in that, In S6, fine ash with a particle size of <50μm is used as a building material raw material for the preparation of non-fired bricks or concrete admixtures, with a fine ash content of ≤30%.

7. The process for producing hydrogen from organic waste liquid in the industrial production of coal-water slurry according to claim 2, characterized in that: The palladium membrane separator is also connected to a pressure swing adsorption (PSA) tower, which uses 13X molecular sieve adsorbent with an adsorption pressure of 2.5~3.0 MPa and a desorption pressure of 0.1~0.3 MPa.

8. The process for producing hydrogen from organic waste liquid in the industrial production of coal-water slurry according to claim 1, characterized in that: The hydrocyclone mixer adopts a multi-stage series-parallel structure, with a single unit processing capacity of 15~30t / h. Each stage mixer outlet is equipped with an online turbidity monitor to provide real-time feedback on mixing uniformity and adjust the inlet flow rate.

9. The process for producing hydrogen from organic waste liquid in the industrial production of coal-water slurry according to claim 1, characterized in that: The groove section of the hydrocyclone mixer has a length of 600~800mm, and the ratio of the groove diameter to the main pipe diameter is 0.7~0.9.

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