WO2022241593A1 - Hydrogen recovery system using gas as raw material gas, recovery method therefor and use thereof - Google Patents

Hydrogen recovery system using gas as raw material gas, recovery method therefor and use thereof Download PDF

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WO2022241593A1
WO2022241593A1 PCT/CN2021/093997 CN2021093997W WO2022241593A1 WO 2022241593 A1 WO2022241593 A1 WO 2022241593A1 CN 2021093997 W CN2021093997 W CN 2021093997W WO 2022241593 A1 WO2022241593 A1 WO 2022241593A1
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gas
pressure
swing adsorption
hydrogen
temperature
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PCT/CN2021/093997
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French (fr)
Chinese (zh)
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唐全红
舒程
田雪
倪伟权
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广东赛瑞新能源有限公司
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Priority to PCT/CN2021/093997 priority Critical patent/WO2022241593A1/en
Publication of WO2022241593A1 publication Critical patent/WO2022241593A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids

Definitions

  • the invention relates to hydrogen recovery, in particular to a hydrogen recovery system using gas as raw material gas, a recovery method and application thereof.
  • Gas is a general term for gaseous fuels by ordinary people.
  • Gas with complex and variable components is a gas with complex components and relatively large changes in the content of each component, in which the content of hydrogen and methane may fluctuate by ⁇ 10% at any time, and the content of carbon monoxide, carbon dioxide and carbon three or more may occur ⁇ 50% or even greater fluctuations.
  • Existing hydrogen recovery methods that use gas as raw material gas mainly include membrane separation and adsorption, pressure swing adsorption and freeze separation.
  • the method has the defects of high dew point temperature components will gradually deposit in the separation membrane, change the properties of the separation membrane, affect the separation effect of the membrane and short operation period; the disadvantage of the pressure swing adsorption method is that the recovery rate is relatively low and the economy is not good; However, the equipment investment of the freeze separation method is large, the raw material gas needs advanced pretreatment, and the energy consumption is high.
  • a technical problem to be solved by the present invention is to remedy the defects of the prior art and provide a hydrogen recovery system using gas as raw material gas.
  • Another technical problem to be solved by the present invention is to make up for the defects existing in the prior art, and to provide a hydrogen recovery method using the system.
  • Another technical problem to be solved by the present invention is to make up for the defects existing in the prior art, and to provide a method for recovering hydrogen using gas with complex and variable components as raw material gas.
  • This hydrogen recovery system using gas as raw material gas includes compression cooling and gas-liquid separation device, membrane separation device and pressure swing adsorption device.
  • the compression cooling and gas-liquid separation device is used to prepare high-pressure gas phase gas.
  • the membrane separation device The device is used to obtain high-hydrogen-containing permeate gas, that is, hydrogen-rich gas at the low-pressure side, and low-hydrogen-containing retentate gas at the high-pressure side.
  • the pressure swing adsorption device is used to perform pressure swing adsorption on the hydrogen-rich gas to prepare hydrogen gas.
  • this hydrogen recovery system using gas as raw material gas is: it also includes a temperature swing adsorption device arranged between the compression cooling and gas-liquid separation device and the membrane separation device, and the temperature swing adsorption device is used to extract the gas from the high-pressure gas phase Selective adsorption removes some components with higher boiling points and some water in the gas, and effectively uses lower energy consumption to reduce the dew point temperature of the raw gas.
  • the temperature swing adsorption device is a redundantly designed temperature swing adsorption device with at least two adsorption towers to reduce the adverse effects of too many components with high boiling points in the gas with complex and variable components on the filter membrane.
  • the temperature-swing adsorption device is a double-tower temperature-swing adsorption device, wherein one adsorption tower is adsorbed until saturated, and the other adsorption tower is regenerated, and the operation of the two adsorption towers is switched once by valve control every 3 hours to 8 hours.
  • a large residual adsorption capacity is reserved to deal with the complex components of the gas and the relatively large changes in the content of each component, so that the system has time to adjust the operation, protect the subsequent membrane separation device to the greatest extent, and maintain
  • the product gas quality is stable, and the gas pressure in the temperature swing adsorption device drops to 0.02 Mpa ⁇ 0.10Mpa.
  • the compression cooling and gas-liquid separation device is composed of a compressor before gas-liquid separation, a water cooler before gas-liquid separation, and a gas-liquid separation tank, and the compressor before gas-liquid separation is used to pressurize the raw material gas from the external system pressure
  • the water cooler before gas-liquid separation is used to cool the high-pressure gas-phase gas to normal temperature or to an economically acceptable low temperature, and the economically acceptable low temperature is 5°C to 33°C
  • the gas-liquid separation tank is used to condense and separate the liquid droplets with higher boiling points entrained in the high-pressure gas phase gas, so as to prevent the liquid from entering the temperature swing adsorption device.
  • C3 + as well as alcohols and ethers, the components with higher boiling points are easier to be adsorbed.
  • the compressor before the gas-liquid separation is at least a two-stage reciprocating compressor.
  • the water cooler before gas-liquid separation is a water-cooled heat exchanger using circulating water or chilled water as a cooling medium.
  • the gas-liquid separation tank is a gas-liquid separation tank with a large contact area between the gas and the condensation surface, so as to enhance the condensation and separation of liquid droplets with higher boiling points entrained in the high-pressure gas phase gas .
  • a pre-membrane separation heater and a precision filter are arranged sequentially, and the pre-membrane separation heater is used to heat the high-pressure gas output from the temperature swing adsorption device to the required temperature of the membrane separation device.
  • the precision filter is used to remove the solid particles that may be contained in the heated high-pressure gas output from the temperature swing adsorption device.
  • the heater before membrane separation is one of steam heater, hot water heater, thermal oil heater and electric heater.
  • the precision filter is a filter that filters solid particles with a precision of 0.1 ⁇ m.
  • the membrane separation device is a membrane separation device that adopts at least two polyimide hollow fiber membrane strings/parallel combinations with reasonable design of separation area and working pressure difference to effectively control the dew point temperature rise of the retentate gas of the membrane separation device,
  • the dew point temperature of the retentate gas is at least 15°C lower than the working temperature of the membrane separation device to achieve the unity of hydrogen separation efficiency and safety and prolong the service life of the separation membrane of the membrane separation device.
  • a water cooler after membrane separation Between the membrane separation device and the pressure swing adsorption device, a water cooler after membrane separation, a compressor before pressure swing adsorption, and a water cooler before pressure swing adsorption are arranged in sequence, and the water cooler after membrane separation is used to convert the The permeated gas, that is, the prepared hydrogen-rich gas is cooled to normal temperature for the first time, the compressor before the pressure swing adsorption is used to raise the pressure of the hydrogen-rich gas cooled to normal temperature, and the water cooler before the pressure swing adsorption is used to raise the pressure of the hydrogen-rich gas Cool to room temperature again.
  • the water cooler after membrane separation is a water-cooled heat exchanger using circulating water or chilled water as a cooling medium.
  • the pre-pressure swing adsorption compressor is at least one of two-stage reciprocating compressors and screw compressors.
  • the water cooler before the pressure swing adsorption is a water-cooled heat exchanger using circulating water or chilled water as a cooling medium.
  • the pressure swing adsorption device is a continuously operating pressure swing adsorption device composed of at least two pressure swing adsorption towers and at least one buffer tank.
  • the hydrogen-rich gas enters the buffer tanks in sequence, and then enters the pressure swing adsorption tower.
  • the adsorbent in the adsorption tower absorbs part of the gas including methane, carbon monoxide and carbon dioxide in the raw material gas.
  • the hydrogen concentration of the hydrogen-rich gas flowing out is 90.0mol% ⁇ 99.9mol%, and the concentration of carbon monoxide and carbon dioxide meets the requirements of downstream users, and the rest will not affect
  • the mass percentage of impurities used in the downstream is 0.1% ⁇ 10.0%.
  • the finished hydrogen gas flowing out from the outlet of the pressure swing adsorption tower enters the product gas buffer tank, and finally exits the hydrogen recovery system and enters the hydrogen pipeline network.
  • a pressure swing adsorption tower is saturated
  • the feed gas is introduced into another regenerated PSA tower through the control valve, the valve between the saturated PSA tower and the Shun vent tank is opened, and the pressure in the PSA tower begins to gradually drop to 1.0MPa ⁇ 0.1 MPa, then open the valve between the pressure swing adsorption tower and the desorption gas buffer tank, further reduce the pressure in the pressure swing adsorption tower until the pressure in the pressure swing adsorption tower is close to atmospheric pressure, and then use the output of the pressure swing adsorption tower being adsorbed
  • the hydrogen-rich gas is boosted to a pressure higher than 2.0MPa to complete the desorption and regeneration of the adsorbent. After the pressure swing adsorption, the desorption tail gas is discharged to the vent pipeline.
  • This hydrogen recovery method using gas as raw material gas includes compression cooling and gas-liquid separation to prepare high-pressure gas-phase gas, membrane separation to prepare hydrogen-rich gas, and pressure swing adsorption to prepare finished hydrogen.
  • this hydrogen recovery method using gas as the raw material gas includes high-pressure gas-phase temperature-swing adsorption to remove components with higher boiling points and some water, and effectively utilizes lower energy consumption to reduce dew point temperature and components with larger molecular weights , the higher the ratio of temperature swing adsorption, then the high-pressure gas phase gas that has been treated by temperature swing adsorption is sent to the heater before the membrane separation, and the precision filter is heated up and finely filtered, so that the dew point temperature of the gas before being sent to the membrane separation device Far lower than the working temperature of the membrane separation device, the heavy hydrocarbon components adsorbed by temperature swing and part of the water are discharged through the regeneration process of temperature swing adsorption, and directly enter the fuel gas pipeline network for other uses or enter the liquefied gas absorption and stabilization system .
  • the temperature swing adsorption is a temperature swing adsorption with at least two adsorption towers with redundant design to reduce the adverse effects of too many high boiling point components in the gas with complex and variable components on the filter membrane.
  • One of the adsorption towers is Adsorption, the rest of the adsorption towers are regenerated, and a large residual adsorption capacity is reserved when switching to deal with the complex components of the gas and the relatively large changes in the content of each component, so that the system has time to adjust the operation and protect the subsequent membrane separation to the greatest extent. device.
  • the heating and precision filtration is to raise the temperature of the high-pressure gas phase gas to 50°C ⁇ 90°C and use a precision filter to filter it precisely, and filter out the particulate impurities in the gas before entering the membrane separation device.
  • the compression cooling and gas-liquid separation to prepare high-pressure gas-phase gas is to compress the raw material gas into high-pressure gas-phase gas and cool it, then enter the gas-liquid separation tank to condense and separate the liquid droplets with higher boiling points entrained in the high-pressure gas-phase gas.
  • the compression of raw material gas into high-pressure gas phase gas is to use the compressor before gas-liquid separation to pressurize the raw material gas from the external system pressure to higher than 2.0Mpa.
  • the cooling of the high-pressure gas-phase gas is to cool the high-pressure gas-phase gas to normal temperature or an economically acceptable low temperature by using a water-cooled heat exchanger using circulating water or chilled water as the cooling medium.
  • the economically acceptable low temperature is 5°C ⁇ 33°C.
  • the gas-liquid separation uses a gas-liquid separation tank with a large contact area between the gas and the condensing surface for gas-liquid separation, so as to enhance the condensation and separation of liquid droplets with higher boiling points entrained in the high-pressure gas phase gas.
  • the preparation of hydrogen-rich gas by membrane separation is to send the high-pressure gas-phase gas that has been heated and separated from gas to liquid into the membrane separation device for initial enrichment through the separation membrane, and the output hydrogen content on the low-pressure side is 60 mol% ⁇ 97mol% permeate gas with high hydrogen content is hydrogen-rich gas, output low hydrogen-containing retentate gas at the high pressure side, hydrogen-rich gas is sent to membrane separation, and then the water cooler cools down to normal temperature, and the retentate gas directly enters the fuel gas pipe The net is used for other purposes or enters the temperature swing adsorption device as regeneration gas.
  • the membrane separation is a membrane separation of at least two polyimide hollow fiber membrane strings/parallel combinations with reasonable design of separation area and working pressure difference, which can effectively control the rise of the dew point temperature of the retentate gas in the membrane separation device, and the retentate
  • the dew point temperature of the gas is at least 15°C lower than the working temperature of the membrane separation device to achieve the unity of hydrogen separation efficiency and safety and prolong the service life of the separation membrane of the membrane separation device.
  • the preparation of finished hydrogen by pressure swing adsorption is to pressurize the high-hydrogen-containing permeated gas, that is, hydrogen-rich gas, through a compressor before PSA to increase the pressure to high-pressure hydrogen-rich gas, and then send it to the water cooler before PSA to cool down to normal temperature. It is sent to the pressure swing adsorption unit for further purification and enrichment into finished hydrogen, refined to meet the quality requirements of subsequent production, and the low-pressure and low-hydrogen-containing analyte gas is pressurized by the tail gas compressor and discharged into the fuel gas pipeline network for other uses.
  • the high-hydrogen-containing permeated gas that is, hydrogen-rich gas
  • the pressurization of the compressor before the pressure swing adsorption is to use the compressor before the pressure swing adsorption to pressurize the hydrogen-rich gas flowing out of the membrane separation device from 0.01Mpa ⁇ 0.50MPa to 1.8Mpa ⁇ 6.0Mpa, and the outlet temperature of the compressor before the pressure swing adsorption 50°C ⁇ 30°C.
  • the cooling of the water cooler before the pressure swing adsorption is a water-cooled heat exchanger using circulating water or chilled water as the cooling medium to cool the high-pressure hydrogen-rich gas to normal temperature;
  • the pressure swing adsorption is at least two pressure swing adsorption towers and at least A pressure swing adsorption composed of a buffer tank can be operated continuously.
  • a pressure swing adsorption tower is saturated, the raw material gas is introduced into another regenerated pressure swing adsorption tower through a control valve.
  • the valve between the saturated pressure swing adsorption tower and the degassing tank is opened, the pressure in the pressure swing adsorption tower begins to gradually drop to 1.0MPa ⁇ 0.1MPa, and then the valve between the pressure swing adsorption tower and the desorption gas buffer tank is opened , further reduce the pressure in the pressure swing adsorption tower until the pressure in the pressure swing adsorption tower is close to the atmospheric pressure, and then use the hydrogen-rich gas produced by the pressure swing adsorption tower being adsorbed to increase the pressure to higher than 2.0MPa to complete the analytical regeneration of the adsorbent.
  • the desorption tail gas is discharged to the vent pipeline. There is always one pressure swing adsorption tower being adsorbed, and the other pressure swing adsorption towers are in different stages of desorption regeneration.
  • the feature of using the above hydrogen recovery method in recovering hydrogen from gas with complex and variable components as raw material gas is that the gas with complex and variable components includes hydrogen, carbon monoxide, carbon dioxide and gas with a relatively high boiling point.
  • Hydrocarbon gas, and its components include hydrogen, carbon monoxide, carbon dioxide, and hydrocarbons with relatively high boiling points, as well as oxygen, nitrogen, water, alcohol, and aldehyde oxides.
  • the beneficial effect of the present invention compared with the prior art is: for gas with complex and changeable components, redundantly designed temperature swing adsorption is used to remove components with higher boiling points and part of the water, effectively utilizing lower energy consumption to reduce the dew point temperature, Reduce the adverse effect of excessive high boiling point components in the gas with complex and variable components on the filter membrane, and protect the subsequent membrane separation device to the greatest extent.
  • the membrane separation of at least two polyimide hollow fiber membrane strings/parallel combinations with reasonable design of separation area and working pressure difference can effectively control the dew point temperature rise of the retentate gas in the membrane separation device, and the dew point temperature of the retentate gas and the membrane
  • the operating temperature of the separation device is at least 15°C lower than that to achieve the unity of hydrogen separation efficiency and safety and prolong the service life of the separation membrane of the membrane separation device.
  • Fig. 1 is a schematic composition diagram of a specific embodiment of the present invention.
  • Fig. 1 The reference signs of Fig. 1 are as follows: 1-compressor before gas-liquid separation; 2-water cooler before gas-liquid separation; 3-gas-liquid separation tank; 4-temperature swing adsorption device; 5-heater before membrane separation; 6-precision Filter; 7-membrane separation device; 8-water cooler after membrane separation; 9-compressor before pressure swing adsorption; 10-water cooler before pressure swing adsorption; 11-pressure swing adsorption device; Q1-compressor before gas-liquid separation Input gas; Q2- output gas from compressor before gas-liquid separation; Q3- output gas from gas-liquid separation tank; Q4- high-pressure gas phase gas output from temperature swing adsorption device; Q5- desorption tail gas output from temperature swing adsorption device; Q6 -The output gas of the heater before the membrane separation; Q7-the output gas of the precision filter; Q8-the retentate gas output from the water cooler after the membrane separation; Q9-the first enriched hydrogen-rich gas output from the membrane separation device
  • the raw material gas is gas with a hydrogen component content of less than 50% and complex and variable components that are difficult to recover.
  • the total gas volume is 10,000Nm 3 , and its components And its content is as follows: hydrogen 40mol% (the content is unstable, fluctuating by ⁇ 10% at any time); methane 30mol% (the content is unstable, fluctuating by ⁇ 10% at any time); CO+CO 2 5mol% (the content is not stable stable, may fluctuate by ⁇ 50% or more); C 3 + 5mol% (unstable content, may fluctuate by ⁇ 50% or more); other 20mol% (unstable content, fluctuate by ⁇ 10% at any time) % fluctuation).
  • the composition of the hydrogen recovery system of this specific embodiment is shown in Figure 1, and what are connected sequentially from left to right are the compressor 1 before the gas-liquid separation, the water cooler 2 before the gas-liquid separation, the gas-liquid separation tank 3, and the temperature swing adsorption device 4 , heater 5 before membrane separation, precision filter 6, membrane separation device 7, water cooler 8 after membrane separation, compressor 9 before pressure swing adsorption, water cooler 10 before pressure swing adsorption and pressure swing adsorption device 11.
  • Raw gas gas is pressurized from the external system pressure by compressor 1 before gas-liquid separation to high-pressure gas-phase gas higher than 2.8Mpa.
  • Compressor 1 before gas-liquid separation is a two-stage reciprocating compressor, and then passes through the water cooler before gas-liquid separation 2. Cool down to normal temperature. At this time, some heavy hydrocarbon components condense into a liquid state, and then pass through the gas-liquid separation tank 3 to condense and separate out the liquid droplets with higher boiling points entrained in the high-pressure gas phase gas.
  • the content of the component C3 + is affected by the The influence of the equilibrium partial pressure is reduced from 5 mol% to about 2.8 mol%, and the temperature is normal temperature, and then sent to the temperature swing adsorption device 4 for temperature swing adsorption.
  • the temperature swing adsorption device 4 is a double-tower adsorption temperature swing adsorption device. When one temperature swing adsorption tower is adsorbing, the other temperature swing adsorption tower is regenerated. The switch between the two temperature swing adsorption towers is controlled by a valve, and the switch is made every 5 hours to keep the product The gas quality is stable, and the C3 + content of the gas after temperature swing adsorption is further reduced, especially the components with higher molecular weight, the higher the ratio of being adsorbed by temperature swing, the pressure drops to about 0.03Mpa.
  • the temperature swing adsorption tower uses the high-temperature tail gas generated by the membrane separation device 7 to analyze and regenerate the adsorbent.
  • the temperature of the generated desorbed gas is about 70°C. It can also be heated by a reheater to enhance the regeneration capacity.
  • the gas flow rate is about 6000Nm 3
  • the tail gas regenerated by temperature swing adsorption is decompressed and enters the gas pipe network.
  • the high-pressure gas-phase gas output from the temperature-swing adsorption device 4 is heated to 75°C by the heater 5 before membrane separation, and the output high-temperature and high-pressure gas-phase gas enters the precision filter 6 to filter out particulate impurities in the gas and then enters the membrane separation device 7 .
  • Membrane separation device 7 adopts the membrane separation of 10 pieces of polyimide hollow fiber membrane series/parallel combination.
  • the membrane wall of polyimide hollow fiber membrane has a microporous support layer and a tight layer with separation function. High selectivity, high purity and recovery rate, good corrosion resistance and heat resistance, the preparation method is polycondensation of biphenyl tetracarboxylic dianhydride and aromatic diamine and dry-wet spinning.
  • the concentration of the hydrogen-enriched gas initially enriched is increased to 60mol% ⁇ 97mol%, the concentration of methane is reduced to 5mol% ⁇ 20mol%, and the concentration of carbon monoxide and carbon dioxide is reduced to 1mol% ⁇ 2mol%.
  • the pressure of hydrogen-rich gas drops to 0.1Mpa ⁇ 0.5MPa, and the flow rate is about 4000Nm 3 ⁇ 5000Nm 3 .
  • the water cooler 8 cools down to normal temperature. After cooling, it becomes low-temperature hydrogen-rich gas.
  • Compressor 9 boosts the pressure to 1.8MPa ⁇ 2.5MPa.
  • compressor 9 is a two-stage reciprocating compressor. Before PSA, the outlet temperature of compressor 9 is as high as 70°C. After the water cooler 10 is cooled to normal temperature, it enters the pressure swing adsorption device 11 for further enrichment.
  • the pressure swing adsorption device 11 is a pressure swing adsorption device composed of six pressure swing adsorption towers and four buffer tanks.
  • the hydrogen-rich gas at normal temperature and high pressure enters the buffer tanks in sequence, and then enters the pressure swing adsorption tower.
  • the adsorption in the pressure swing adsorption tower The agent adsorbs methane, carbon monoxide and other parts of carbon dioxide in hydrogen-rich gas at normal temperature and high pressure.
  • the hydrogen concentration of the output product hydrogen is 90mol% ⁇ 99.9mol%, the concentration of carbon monoxide and carbon dioxide meets the requirements of downstream users, and the mass percentage of other impurities that do not affect downstream use is 0.1% ⁇ 10.0%.
  • the finished product flowing out from the outlet of the pressure swing adsorption tower The hydrogen enters the product gas buffer tank, and finally exits the hydrogen recovery system and enters the hydrogen pipeline network.
  • the feed gas is introduced into another regenerated pressure swing adsorption tower through the control valve.
  • the valve between the saturated pressure swing adsorption tower and the degassing tank is opened, the pressure in the pressure swing adsorption tower begins to gradually drop to 1.0MPa ⁇ 0.1MPa, and then the valve between the pressure swing adsorption tower and the desorption gas buffer tank is opened , further reduce the pressure in the pressure swing adsorption tower until the pressure in the pressure swing adsorption tower is close to the atmospheric pressure, and then use the hydrogen-rich gas produced by the pressure swing adsorption tower being adsorbed to increase the pressure to higher than 2.0MPa to complete the analytical regeneration of the adsorbent.
  • the desorbed tail gas output by PSA unit 11 is discharged to the venting pipeline.
  • one PSA tower is always adsorbing, one PSA tower completes desorption and regeneration, and the other four PSA towers are in the Analytical regeneration at different stages.
  • the hydrogen recovery method in this specific embodiment has the following steps in sequence: 1) compressing and cooling the raw gas gas and separating gas-liquid to prepare high-pressure gas-phase gas; using a compressor before gas-liquid separation to pressurize the raw gas gas from the external system pressure to high At 2.0Mpa high-pressure gas-phase gas, the high-pressure gas-phase gas is cooled to normal temperature by using a water-cooled heat exchanger with circulating water as the cooling medium, and finally the gas-liquid separation tank with a large contact area between the gas and the condensation surface is used for gas-liquid separation, and the high-pressure The liquid droplets with higher boiling point entrained in the gas phase coalesce and separate out.
  • the components with higher molecular weight The higher the ratio of temperature swing adsorption, the higher the temperature swing adsorption treatment, the high-pressure gas phase gas will be sequentially sent to the pre-membrane separation heater and precision filter for heating and fine filtration, further reducing the content of components with higher boiling points in the raw gas and the raw materials
  • the dew point temperature of the gas makes the dew point temperature of the gas before being sent into the membrane separation device far lower than the working temperature of the membrane separation device, and the adsorbed heavy hydrocarbon components are the desorbed tail gas and part of the water after the temperature swing adsorption.
  • the discharge from the regeneration process of temperature swing adsorption treatment directly enters the fuel gas pipeline network for other uses or enters the liquefied gas absorption and stabilization system.
  • the hydrogen-rich gas is subjected to pressure swing adsorption to prepare finished hydrogen gas: the permeated gas with high hydrogen content, that is, the hydrogen-rich gas, is pressurized by the compressor before the pressure swing adsorption, and the pressure is raised to a high-pressure hydrogen-rich gas, and then sent to the water cooler before the pressure swing adsorption to cool down After reaching normal temperature, it is sent to the pressure swing adsorption device for further purification and enrichment into finished hydrogen, which is refined to meet the quality requirements of subsequent production. After being boosted again, it is incorporated into the hydrogen pipeline network, and the low-pressure and low-hydrogen-containing analyte gas is pressurized by the tail gas compressor. Discharged into the fuel gas pipeline network for other uses.
  • the raw material gas in this specific embodiment is a gas whose hydrogen component content is less than 50% and the components are complex and changeable, and it is difficult to recover, while the hydrogen concentration of the recovered product is 90.0mol% ⁇ 99.9mol%, and the concentration of carbon monoxide and carbon dioxide meets the requirements of the downstream gas.
  • the hydrogen recovery rate exceeds 80%.
  • the flow rate of the finished hydrogen gas that finally exits the hydrogen recovery system and enters the hydrogen pipeline network is about 4000Nm 3 .
  • the main energy consumption of this specific embodiment is steam and electric energy.
  • the total power consumption of the system electric energy is 1200 kilowatts, and the consumption of low-pressure steam is 0.3 tons/hour, calculated according to the electricity cost of 0.69 yuan/kWh and the low-pressure steam of 240 yuan/ton.
  • Gas and other consumption, the operating cost of recovering 1 ton of 100% pure hydrogen is about 2,700 yuan/ton, compared with the direct purchase of hydrogen at a price of about 20,000 yuan/ton, deducting the income from reducing the equivalent calorific value of hydrogen used as gas 6,000 yuan/ton, the economic benefit of recovering hydrogen by the method and system of this embodiment is about 13,000 yuan/ton.
  • Trial working conditions show that the method and system of this specific embodiment can recover hydrogen in gas with complex components stably and effectively for a long time, and realize low energy consumption and high income.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Inorganic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
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Abstract

A hydrogen recovery system using gas as a raw material gas, a recovery method therefor and the use thereof. The system comprises a compression cooling and gas-liquid separation device, a membrane separation device, a pressure swing adsorption device and a temperature swing adsorption device; and the method comprises the steps of compression cooling and gas-liquid separation, membrane separation and pressure swing adsorption, and also comprises the step of temperature swing adsorption of a high-pressure gas phase gas. The solution of the invention, by using the temperature swing adsorption of a redundant design, can enable the effective use of the low energy consumption to decrease the dew point temperature, reduce the adverse effects of excessive high-boiling-point components in gas with complex and changeable components on a filtering membrane, and maximize the protection of a subsequent membrane separation device. Membrane separation executed by combining at least two polyimide hollow fiber membranes which are reasonably designed in a separation area and in working pressure difference in series/in parallel is used, the increase in the dew-point temperature of retentate gas of the membrane separation device is effectively controlled, and the dew-point temperature of the retentate gas is at least 15ºC lower than the working temperature of the membrane separation device, such that the uniformity in the hydrogen separation efficiency and safety is realized, and the service life of the separation membrane of the membrane separation device is prolonged.

Description

一种以瓦斯为原料气的氢气回收系统及其回收方法和应用A hydrogen recovery system using gas as raw material gas and its recovery method and application 技术领域technical field
本发明涉及氢气回收，特别是涉及一种以瓦斯为原料气的氢气回收系统及其回收方法和应用。The invention relates to hydrogen recovery, in particular to a hydrogen recovery system using gas as raw material gas, a recovery method and application thereof.
背景技术Background technique
瓦斯是一般民众对气体燃料的通称。复杂多变组分的瓦斯是组分复杂且各个组分的含量相对变化大的瓦斯，其中氢气、甲烷的含量会随时发生±10%幅度的波动，一氧化碳、二氧化碳以及碳三以上的含量可能发生±50%甚至更大幅度的波动。现有以瓦斯为原料气的氢气回收方法主要有膜分离吸附法、变压吸附法和冷冻分离法，对于氢组分含量小于50%且组分复杂多变、难以回收的瓦斯，膜分离吸附法存在高露点温度组分会逐步沉积在分离膜中，改变分离膜性质，影响膜分离效果以及运行周期短的缺陷；变压吸附法的不足之处是回收率相对比较低，经济性不佳；而冷冻分离法的设备投资大，原料气需要深度预处理，能耗高。Gas is a general term for gaseous fuels by ordinary people. Gas with complex and variable components is a gas with complex components and relatively large changes in the content of each component, in which the content of hydrogen and methane may fluctuate by ±10% at any time, and the content of carbon monoxide, carbon dioxide and carbon three or more may occur ±50% or even greater fluctuations. Existing hydrogen recovery methods that use gas as raw material gas mainly include membrane separation and adsorption, pressure swing adsorption and freeze separation. The method has the defects of high dew point temperature components will gradually deposit in the separation membrane, change the properties of the separation membrane, affect the separation effect of the membrane and short operation period; the disadvantage of the pressure swing adsorption method is that the recovery rate is relatively low and the economy is not good; However, the equipment investment of the freeze separation method is large, the raw material gas needs advanced pretreatment, and the energy consumption is high.
技术问题technical problem
本发明所要解决的一个技术问题是弥补现有技术存在的缺陷，提供一种以瓦斯为原料气的氢气回收系统。A technical problem to be solved by the present invention is to remedy the defects of the prior art and provide a hydrogen recovery system using gas as raw material gas.
本发明所要解决的另一个技术问题是弥补现有技术存在的缺陷，提供一种采用该系统的氢气回收方法。Another technical problem to be solved by the present invention is to make up for the defects existing in the prior art, and to provide a hydrogen recovery method using the system.
本发明所要解决的再一个技术问题是弥补现有技术存在的缺陷，提供一种采用该回收方法在以复杂多变组分的瓦斯为原料气回收氢气中应用。Another technical problem to be solved by the present invention is to make up for the defects existing in the prior art, and to provide a method for recovering hydrogen using gas with complex and variable components as raw material gas.
技术解决方案technical solution
本发明以瓦斯为原料气的氢气回收系统的技术问题通过以下技术方案予以解决。The technical problems of the hydrogen recovery system using gas as raw material gas in the present invention are solved by the following technical solutions.
这种以瓦斯为原料气的氢气回收系统，包括压缩冷却与气液分离装置、膜分离装置和变压吸附装置，所述压缩冷却与气液分离装置用于制备高压气相瓦斯，所述膜分离装置用于在低压侧得到高含氢的渗透气即富氢气，在高压侧得到低含氢的渗余气，所述变压吸附装置用于将富氢气进行变压吸附制备成品氢气。This hydrogen recovery system using gas as raw material gas includes compression cooling and gas-liquid separation device, membrane separation device and pressure swing adsorption device. The compression cooling and gas-liquid separation device is used to prepare high-pressure gas phase gas. The membrane separation device The device is used to obtain high-hydrogen-containing permeate gas, that is, hydrogen-rich gas at the low-pressure side, and low-hydrogen-containing retentate gas at the high-pressure side. The pressure swing adsorption device is used to perform pressure swing adsorption on the hydrogen-rich gas to prepare hydrogen gas.
这种以瓦斯为原料气的氢气回收系统的特点是：还包括设置在所述压缩冷却与气液分离装置与所述膜分离装置中间的变温吸附装置，所述变温吸附装置用于从高压气相瓦斯中选择性吸附除去部分沸点较高的组分以及部分水，有效利用较低能耗降低原料气的露点温度。The feature of this hydrogen recovery system using gas as raw material gas is: it also includes a temperature swing adsorption device arranged between the compression cooling and gas-liquid separation device and the membrane separation device, and the temperature swing adsorption device is used to extract the gas from the high-pressure gas phase Selective adsorption removes some components with higher boiling points and some water in the gas, and effectively uses lower energy consumption to reduce the dew point temperature of the raw gas.
本发明以瓦斯为原料气的氢气回收系统的技术问题通过以下进一步的技术方案予以解决。The technical problems of the hydrogen recovery system using gas as raw material gas in the present invention are solved by the following further technical solutions.
所述变温吸附装置，是采用冗余设计的至少有两个吸附塔的变温吸附装置，以减少复杂多变组分的瓦斯中过多的沸点较高的组分对过滤膜的不利影响。The temperature swing adsorption device is a redundantly designed temperature swing adsorption device with at least two adsorption towers to reduce the adverse effects of too many components with high boiling points in the gas with complex and variable components on the filter membrane.
优选的是，所述变温吸附装置是双塔变温吸附装置，其中一个吸附塔进行吸附直至饱和，另一个吸附塔进行再生，两个吸附塔的运行每3小时~8小时由阀门控制切换一次，每次在切换吸附塔时预留较大的吸附剩余能力，以应对瓦斯的组分复杂且各个组分的含量相对变化大，以便系统有时间调整操作，最大限度保护后续的膜分离装置，保持产品气质量平稳，变温吸附装置中的气体压力下降为0.02 Mpa ~0.10Mpa。Preferably, the temperature-swing adsorption device is a double-tower temperature-swing adsorption device, wherein one adsorption tower is adsorbed until saturated, and the other adsorption tower is regenerated, and the operation of the two adsorption towers is switched once by valve control every 3 hours to 8 hours. Each time when the adsorption tower is switched, a large residual adsorption capacity is reserved to deal with the complex components of the gas and the relatively large changes in the content of each component, so that the system has time to adjust the operation, protect the subsequent membrane separation device to the greatest extent, and maintain The product gas quality is stable, and the gas pressure in the temperature swing adsorption device drops to 0.02 Mpa ~0.10Mpa.
所述压缩冷却与气液分离装置由气液分离前压缩机、气液分离前水冷器和气液分离罐依次连接组成，所述气液分离前压缩机用于将原料气从外部系统压力加压到高于2.0MPa的高压气相瓦斯，所述气液分离前水冷器用于将高压气相瓦斯冷却至常温或测算经济性可接受的低温，所述测算经济性可接受的低温是5℃~33℃，所述气液分离罐用于将高压气相瓦斯中夹带的沸点较高的液滴凝聚并分离析出，防止液体进入变温吸附装置，所述原料气中沸点较高的组分包括碳三以上组分C3 +，以及醇类、醚，沸点越高的组分，越容易被吸附。 The compression cooling and gas-liquid separation device is composed of a compressor before gas-liquid separation, a water cooler before gas-liquid separation, and a gas-liquid separation tank, and the compressor before gas-liquid separation is used to pressurize the raw material gas from the external system pressure For high-pressure gas-phase gas higher than 2.0MPa, the water cooler before gas-liquid separation is used to cool the high-pressure gas-phase gas to normal temperature or to an economically acceptable low temperature, and the economically acceptable low temperature is 5°C to 33°C , the gas-liquid separation tank is used to condense and separate the liquid droplets with higher boiling points entrained in the high-pressure gas phase gas, so as to prevent the liquid from entering the temperature swing adsorption device. C3 + , as well as alcohols and ethers, the components with higher boiling points are easier to be adsorbed.
所述气液分离前压缩机是至少两级往复式压缩机。The compressor before the gas-liquid separation is at least a two-stage reciprocating compressor.
所述气液分离前水冷器是采用循环水或冷冻水为降温介质的水冷式换热器。The water cooler before gas-liquid separation is a water-cooled heat exchanger using circulating water or chilled water as a cooling medium.
所述气液分离罐是气体与冷凝面接触面积大的气液分离罐，以增强高压气相瓦斯气中夹带的沸点较高的液滴凝聚并分离析出 。 The gas-liquid separation tank is a gas-liquid separation tank with a large contact area between the gas and the condensation surface, so as to enhance the condensation and separation of liquid droplets with higher boiling points entrained in the high-pressure gas phase gas .
在所述变温吸附装置与所述膜分离装置之间依次设有膜分离前加热器和精密过滤器，所述膜分离前加热器用于将变温吸附装置输出的高压瓦斯加热到膜分离装置需要的工作温度，所述精密过滤器用于将变温吸附装置输出经过加热的高压瓦斯脱除可能含有的固体颗粒。Between the temperature swing adsorption device and the membrane separation device, a pre-membrane separation heater and a precision filter are arranged sequentially, and the pre-membrane separation heater is used to heat the high-pressure gas output from the temperature swing adsorption device to the required temperature of the membrane separation device. Working temperature, the precision filter is used to remove the solid particles that may be contained in the heated high-pressure gas output from the temperature swing adsorption device.
所述膜分离前加热器是蒸汽加热器、热水加热器、热油加热器以及电加热器中的一种。The heater before membrane separation is one of steam heater, hot water heater, thermal oil heater and electric heater.
所述精密过滤器是过滤固体颗粒精度达到0.1μm的过滤器。The precision filter is a filter that filters solid particles with a precision of 0.1 μm.
所述膜分离装置，是采用合理设计分离面积、工作压差的至少两片聚酰亚胺中空纤维膜串/并列组合的膜分离装置，有效控制膜分离装置的渗余气的露点温度上升，渗余气的露点温度相比膜分离装置的工作温度低至少15℃，以实现氢分离效率和安全性的统一，延长膜分离装置的分离膜的使用寿命。The membrane separation device is a membrane separation device that adopts at least two polyimide hollow fiber membrane strings/parallel combinations with reasonable design of separation area and working pressure difference to effectively control the dew point temperature rise of the retentate gas of the membrane separation device, The dew point temperature of the retentate gas is at least 15°C lower than the working temperature of the membrane separation device to achieve the unity of hydrogen separation efficiency and safety and prolong the service life of the separation membrane of the membrane separation device.
在所述膜分离装置与所述变压吸附装置之间依次设有膜分离后水冷器、变压吸附前压缩机和变压吸附前水冷器，所述膜分离后水冷器用于将高含氢的渗透气，即所制备的富氢气初次冷却到常温，所述变压吸附前压缩机用于将冷却到常温的富氢气提升压力，所述变压吸附前水冷器用于将提升压力的富氢气再次冷却到常温。Between the membrane separation device and the pressure swing adsorption device, a water cooler after membrane separation, a compressor before pressure swing adsorption, and a water cooler before pressure swing adsorption are arranged in sequence, and the water cooler after membrane separation is used to convert the The permeated gas, that is, the prepared hydrogen-rich gas is cooled to normal temperature for the first time, the compressor before the pressure swing adsorption is used to raise the pressure of the hydrogen-rich gas cooled to normal temperature, and the water cooler before the pressure swing adsorption is used to raise the pressure of the hydrogen-rich gas Cool to room temperature again.
所述膜分离后水冷器是采用循环水或冷冻水为降温介质的水冷式换热器。The water cooler after membrane separation is a water-cooled heat exchanger using circulating water or chilled water as a cooling medium.
所述变压吸附前压缩机，是至少两级往复式压缩机和螺杆式压缩机中的一种。The pre-pressure swing adsorption compressor is at least one of two-stage reciprocating compressors and screw compressors.
所述变压吸附前水冷器是采用循环水或冷冻水为降温介质的水冷式换热器。The water cooler before the pressure swing adsorption is a water-cooled heat exchanger using circulating water or chilled water as a cooling medium.
所述变压吸附装置，是至少两个变压吸附塔和至少一个缓冲罐组成的可连续运行的变压吸附装置，富氢气即按顺序进入缓冲罐，然后进入变压吸附塔中，变压吸附塔内的吸附剂将原料气中包括甲烷、一氧化碳、二氧化碳的部分气体吸附，流出的富氢气的氢气浓度为90.0mol%~99.9mol%、一氧化碳和二氧化碳的浓度满足下游用户要求，其余不影响下游使用的杂质的质量百分比为0.1%~10.0%，从变压吸附塔出口流出的成品氢气进入成品气缓冲罐，最终排出氢气回收系统进入氢气管网，当一个变压吸附塔吸附饱和后，通过控制阀将原料气引入另一个再生后的变压吸附塔，吸附饱和的变压吸附塔与顺放气罐之间的阀门打开，变压吸附塔内的压力开始逐渐下降到1.0MPa±0.1MPa，然后打开变压吸附塔与解析气缓冲罐之间的阀门，进一步降低变压吸附塔内压力，直至变压吸附塔内压力接近大气压力，之后利用正在吸附的变压吸附塔产出的富氢气升压到高于2.0MPa，完成吸附剂的解析再生，变压吸附后脱附尾气排放到放空管线，始终有一个变压吸附塔正在吸附，其余变压吸附塔分别处于不同阶段的解析再生。The pressure swing adsorption device is a continuously operating pressure swing adsorption device composed of at least two pressure swing adsorption towers and at least one buffer tank. The hydrogen-rich gas enters the buffer tanks in sequence, and then enters the pressure swing adsorption tower. The adsorbent in the adsorption tower absorbs part of the gas including methane, carbon monoxide and carbon dioxide in the raw material gas. The hydrogen concentration of the hydrogen-rich gas flowing out is 90.0mol%~99.9mol%, and the concentration of carbon monoxide and carbon dioxide meets the requirements of downstream users, and the rest will not affect The mass percentage of impurities used in the downstream is 0.1%~10.0%. The finished hydrogen gas flowing out from the outlet of the pressure swing adsorption tower enters the product gas buffer tank, and finally exits the hydrogen recovery system and enters the hydrogen pipeline network. When a pressure swing adsorption tower is saturated, The feed gas is introduced into another regenerated PSA tower through the control valve, the valve between the saturated PSA tower and the Shun vent tank is opened, and the pressure in the PSA tower begins to gradually drop to 1.0MPa±0.1 MPa, then open the valve between the pressure swing adsorption tower and the desorption gas buffer tank, further reduce the pressure in the pressure swing adsorption tower until the pressure in the pressure swing adsorption tower is close to atmospheric pressure, and then use the output of the pressure swing adsorption tower being adsorbed The hydrogen-rich gas is boosted to a pressure higher than 2.0MPa to complete the desorption and regeneration of the adsorbent. After the pressure swing adsorption, the desorption tail gas is discharged to the vent pipeline. There is always one PSA tower being adsorbed, and the other PSA towers are in different stages of desorption. regeneration.
本发明以瓦斯为原料气的氢气回收方法的技术问题通过以下技术方案予以解决。The technical problems of the hydrogen recovery method using gas as raw material gas in the present invention are solved by the following technical solutions.
这种以瓦斯为原料气的氢气回收方法，包括压缩冷却与气液分离制备高压气相瓦斯、膜分离制备富氢气，以及变压吸附制备成品氢气。This hydrogen recovery method using gas as raw material gas includes compression cooling and gas-liquid separation to prepare high-pressure gas-phase gas, membrane separation to prepare hydrogen-rich gas, and pressure swing adsorption to prepare finished hydrogen.
这种以瓦斯为原料气的氢气回收方法的特点是：还包括将高压气相瓦斯变温吸附除去沸点较高的组分以及部分水，有效利用较低能耗降低露点温度，分子量越大的组分，被变温吸附的比例越高，再将经过变温吸附处理的高压气相瓦斯依次送入膜分离前加热器、精密过滤器进行升温并精细过滤，使得在送入膜分离装置前的瓦斯的露点温度远远低于了膜分离装置的工作温度，而被变温吸附的重烃组分以及部分水经过变温吸附处理的再生流程排出，直接进入燃料瓦斯管网供作它用或进入液化气吸收稳定系统。The characteristics of this hydrogen recovery method using gas as the raw material gas are: it also includes high-pressure gas-phase temperature-swing adsorption to remove components with higher boiling points and some water, and effectively utilizes lower energy consumption to reduce dew point temperature and components with larger molecular weights , the higher the ratio of temperature swing adsorption, then the high-pressure gas phase gas that has been treated by temperature swing adsorption is sent to the heater before the membrane separation, and the precision filter is heated up and finely filtered, so that the dew point temperature of the gas before being sent to the membrane separation device Far lower than the working temperature of the membrane separation device, the heavy hydrocarbon components adsorbed by temperature swing and part of the water are discharged through the regeneration process of temperature swing adsorption, and directly enter the fuel gas pipeline network for other uses or enter the liquefied gas absorption and stabilization system .
所述变温吸附，是采用冗余设计的至少有两个吸附塔的变温吸附，以减少复杂多变组分的瓦斯中过多的高沸点组分对过滤膜的不利影响，其中一个吸附塔进行吸附，其余吸附塔进行再生，切换时预留较大的吸附剩余能力，以应对瓦斯的组分复杂且各个组分的含量相对变化大，以便系统有时间调整操作，最大限度保护后续的膜分离装置。The temperature swing adsorption is a temperature swing adsorption with at least two adsorption towers with redundant design to reduce the adverse effects of too many high boiling point components in the gas with complex and variable components on the filter membrane. One of the adsorption towers is Adsorption, the rest of the adsorption towers are regenerated, and a large residual adsorption capacity is reserved when switching to deal with the complex components of the gas and the relatively large changes in the content of each component, so that the system has time to adjust the operation and protect the subsequent membrane separation to the greatest extent. device.
所述升温并精密过滤，是将高压气相瓦斯升温至50℃~90℃并采用精密过滤器精密过滤，滤除气体中颗粒杂质后进入膜分离装置。The heating and precision filtration is to raise the temperature of the high-pressure gas phase gas to 50°C~90°C and use a precision filter to filter it precisely, and filter out the particulate impurities in the gas before entering the membrane separation device.
本发明以瓦斯为原料气的氢气回收方法的技术问题通过以下进一步的技术方案予以解决。The technical problems of the hydrogen recovery method using gas as raw material gas in the present invention are solved by the following further technical solutions.
所述压缩冷却与气液分离制备高压气相瓦斯，是将原料气压缩为高压气相瓦斯并冷却后，进入气液分离罐将高压气相瓦斯中夹带的沸点较高的液滴凝聚并分离析出。The compression cooling and gas-liquid separation to prepare high-pressure gas-phase gas is to compress the raw material gas into high-pressure gas-phase gas and cool it, then enter the gas-liquid separation tank to condense and separate the liquid droplets with higher boiling points entrained in the high-pressure gas-phase gas.
所述将原料气压缩为高压气相瓦斯，是采用气液分离前压缩机将原料气从外部系统压力加压到高于2.0Mpa。The compression of raw material gas into high-pressure gas phase gas is to use the compressor before gas-liquid separation to pressurize the raw material gas from the external system pressure to higher than 2.0Mpa.
所述将高压气相瓦斯冷却，是采用循环水或冷冻水为降温介质的水冷式换热器将高压气相瓦斯冷却至常温或测算经济性可接受的低温，所述测算经济性可接受的低温是5℃~33℃。The cooling of the high-pressure gas-phase gas is to cool the high-pressure gas-phase gas to normal temperature or an economically acceptable low temperature by using a water-cooled heat exchanger using circulating water or chilled water as the cooling medium. The economically acceptable low temperature is 5°C~33°C.
所述气液分离，是采用气体与冷凝面接触面积大的气液分离罐进行气液分离，以增强高压气相瓦斯中夹带的沸点较高的液滴凝聚并分离析出。The gas-liquid separation uses a gas-liquid separation tank with a large contact area between the gas and the condensing surface for gas-liquid separation, so as to enhance the condensation and separation of liquid droplets with higher boiling points entrained in the high-pressure gas phase gas.
所述膜分离制备富氢气，是将经过升温并气液分离的高压气相瓦斯送入膜分离装置通过分离膜进行初次提浓，在低压侧输出氢含量为60 mol%~97mol%的高含氢的渗透气即富氢气，在高压侧输出低含氢的渗余气，富氢气再送入膜分离后水冷器冷却降温到常温，渗余气直接进入燃料瓦斯管网供作它用或进入变温吸附装置作为再生气。The preparation of hydrogen-rich gas by membrane separation is to send the high-pressure gas-phase gas that has been heated and separated from gas to liquid into the membrane separation device for initial enrichment through the separation membrane, and the output hydrogen content on the low-pressure side is 60 mol%~97mol% permeate gas with high hydrogen content is hydrogen-rich gas, output low hydrogen-containing retentate gas at the high pressure side, hydrogen-rich gas is sent to membrane separation, and then the water cooler cools down to normal temperature, and the retentate gas directly enters the fuel gas pipe The net is used for other purposes or enters the temperature swing adsorption device as regeneration gas.
所述膜分离，是采用合理设计分离面积、工作压差的至少两片聚酰亚胺中空纤维膜串/并列组合的膜分离，有效控制膜分离装置的渗余气的露点温度上升，渗余气的露点温度相比膜分离装置的工作温度低至少15℃，以实现氢分离效率和安全性的统一，延长膜分离装置的分离膜的使用寿命。The membrane separation is a membrane separation of at least two polyimide hollow fiber membrane strings/parallel combinations with reasonable design of separation area and working pressure difference, which can effectively control the rise of the dew point temperature of the retentate gas in the membrane separation device, and the retentate The dew point temperature of the gas is at least 15°C lower than the working temperature of the membrane separation device to achieve the unity of hydrogen separation efficiency and safety and prolong the service life of the separation membrane of the membrane separation device.
所述变压吸附制备成品氢气，是将高含氢的渗透气即富氢气经过变压吸附前压缩机加压，提升压力为高压富氢气，再送入变压吸附前水冷器冷却降温到常温后送入变压吸附装置再次提纯提浓为成品氢气，精制到满足后续生产质量要求，而低压低含氢的解析气经过尾气压缩机加压后排入燃料瓦斯管网供作它用。The preparation of finished hydrogen by pressure swing adsorption is to pressurize the high-hydrogen-containing permeated gas, that is, hydrogen-rich gas, through a compressor before PSA to increase the pressure to high-pressure hydrogen-rich gas, and then send it to the water cooler before PSA to cool down to normal temperature. It is sent to the pressure swing adsorption unit for further purification and enrichment into finished hydrogen, refined to meet the quality requirements of subsequent production, and the low-pressure and low-hydrogen-containing analyte gas is pressurized by the tail gas compressor and discharged into the fuel gas pipeline network for other uses.
所述变压吸附前压缩机加压，是采用变压吸附前压缩机将膜分离装置流出的富氢气从0.01Mpa~0.50MPa加压到1.8Mpa~6.0Mpa，变压吸附前压缩机出口温度为50℃±30℃。The pressurization of the compressor before the pressure swing adsorption is to use the compressor before the pressure swing adsorption to pressurize the hydrogen-rich gas flowing out of the membrane separation device from 0.01Mpa~0.50MPa to 1.8Mpa~6.0Mpa, and the outlet temperature of the compressor before the pressure swing adsorption 50℃±30℃.
所述变压吸附前水冷器冷却，是采用循环水或冷冻水为降温介质的水冷式换热器将高压富氢气冷却至常温；所述变压吸附，是至少两个变压吸附塔和至少一个缓冲罐组成的可连续运行的变压吸附，当一个变压吸附塔吸附饱和后，通过控制阀将原料气引入另一个再生后的变压吸附塔。吸附饱和的变压吸附塔与顺放气罐之间的阀门打开，变压吸附塔内的压力开始逐渐下降到1.0MPa±0.1MPa，然后打开变压吸附塔与解析气缓冲罐之间的阀门，进一步降低变压吸附塔内压力，直至变压吸附塔内压力接近大气压力，之后利用正在吸附的变压吸附塔产出的富氢气升压到高于2.0MPa，完成吸附剂的解析再生，变压吸附后脱附尾气排放到放空管线，始终有一个变压吸附塔正在吸附，其余变压吸附塔分别处于不同阶段的解析再生。The cooling of the water cooler before the pressure swing adsorption is a water-cooled heat exchanger using circulating water or chilled water as the cooling medium to cool the high-pressure hydrogen-rich gas to normal temperature; the pressure swing adsorption is at least two pressure swing adsorption towers and at least A pressure swing adsorption composed of a buffer tank can be operated continuously. When a pressure swing adsorption tower is saturated, the raw material gas is introduced into another regenerated pressure swing adsorption tower through a control valve. The valve between the saturated pressure swing adsorption tower and the degassing tank is opened, the pressure in the pressure swing adsorption tower begins to gradually drop to 1.0MPa±0.1MPa, and then the valve between the pressure swing adsorption tower and the desorption gas buffer tank is opened , further reduce the pressure in the pressure swing adsorption tower until the pressure in the pressure swing adsorption tower is close to the atmospheric pressure, and then use the hydrogen-rich gas produced by the pressure swing adsorption tower being adsorbed to increase the pressure to higher than 2.0MPa to complete the analytical regeneration of the adsorbent. After the pressure swing adsorption, the desorption tail gas is discharged to the vent pipeline. There is always one pressure swing adsorption tower being adsorbed, and the other pressure swing adsorption towers are in different stages of desorption regeneration.
本发明在以复杂多变组分的瓦斯为原料气回收氢气中应用的技术问题通过以下技术方案予以解决。The technical problems in the application of the present invention in recovering hydrogen from gas with complex and variable components are solved by the following technical solutions.
采用上述氢气回收方法在以复杂多变组分的瓦斯为原料气回收氢气中应用的特点是：所述复杂多变组分的瓦斯，是其组分包括氢、一氧化碳、二氧化碳和沸点相对高的碳氢类化合物的瓦斯，与其组分包括氢、一氧化碳、二氧化碳和沸点相对高的碳氢类化合物以及氧、氮和水、醇、醛氧化物的瓦斯中的一种。The feature of using the above hydrogen recovery method in recovering hydrogen from gas with complex and variable components as raw material gas is that the gas with complex and variable components includes hydrogen, carbon monoxide, carbon dioxide and gas with a relatively high boiling point. Hydrocarbon gas, and its components include hydrogen, carbon monoxide, carbon dioxide, and hydrocarbons with relatively high boiling points, as well as oxygen, nitrogen, water, alcohol, and aldehyde oxides.
有益效果Beneficial effect
本发明与现有技术相比的有益效果是：针对复杂多变组分的瓦斯，采用冗余设计的变温吸附除去沸点较高的组分以及部分水，有效利用较低能耗降低露点温度，减少复杂多变组分的瓦斯中过多的高沸点组分对过滤膜的不利影响，最大限度保护后续的膜分离装置。采用合理设计分离面积、工作压差的至少两片聚酰亚胺中空纤维膜串/并列组合的膜分离，有效控制膜分离装置的渗余气的露点温度上升，渗余气的露点温度与膜分离装置的工作温度相比至少低15℃，以实现氢分离效率和安全性的统一，延长膜分离装置的分离膜的使用寿命。The beneficial effect of the present invention compared with the prior art is: for gas with complex and changeable components, redundantly designed temperature swing adsorption is used to remove components with higher boiling points and part of the water, effectively utilizing lower energy consumption to reduce the dew point temperature, Reduce the adverse effect of excessive high boiling point components in the gas with complex and variable components on the filter membrane, and protect the subsequent membrane separation device to the greatest extent. The membrane separation of at least two polyimide hollow fiber membrane strings/parallel combinations with reasonable design of separation area and working pressure difference can effectively control the dew point temperature rise of the retentate gas in the membrane separation device, and the dew point temperature of the retentate gas and the membrane The operating temperature of the separation device is at least 15°C lower than that to achieve the unity of hydrogen separation efficiency and safety and prolong the service life of the separation membrane of the membrane separation device.
附图说明Description of drawings
图1是本发明具体实施方式的组成示意图。Fig. 1 is a schematic composition diagram of a specific embodiment of the present invention.
图1的附图标记如下：1-气液分离前压缩机；2-气液分离前水冷器； 3-气液分离罐；4-变温吸附装置；5-膜分离前加热器；6-精密过滤器；7-膜分离装置；8-膜分离后水冷器；9-变压吸附前压缩机；10-变压吸附前水冷器；11-变压吸附装置；Q1-气液分离前压缩机输入的瓦斯；Q2-气液分离前压缩机的输出气体；Q3-气液分离罐的输出气体；Q4-变温吸附装置的输出的高压气相瓦斯；Q5-变温吸附装置输出的脱附尾气；Q6-膜分离前加热器的输出气体；Q7-精密过滤器的输出气体；Q8-膜分离后水冷器输出的渗余气；Q9-膜分离装置的输出的初次提浓的富氢气；Q10-膜分离后水冷器的输出气体；Q11-变压吸附前压缩机的输出气体；Q12-变压吸附前水冷器的输出气体；Q13-变压吸附装置输出的脱附尾气；Q14-变压吸附装置输出的成品氢气。The reference signs of Fig. 1 are as follows: 1-compressor before gas-liquid separation; 2-water cooler before gas-liquid separation; 3-gas-liquid separation tank; 4-temperature swing adsorption device; 5-heater before membrane separation; 6-precision Filter; 7-membrane separation device; 8-water cooler after membrane separation; 9-compressor before pressure swing adsorption; 10-water cooler before pressure swing adsorption; 11-pressure swing adsorption device; Q1-compressor before gas-liquid separation Input gas; Q2- output gas from compressor before gas-liquid separation; Q3- output gas from gas-liquid separation tank; Q4- high-pressure gas phase gas output from temperature swing adsorption device; Q5- desorption tail gas output from temperature swing adsorption device; Q6 -The output gas of the heater before the membrane separation; Q7-the output gas of the precision filter; Q8-the retentate gas output from the water cooler after the membrane separation; Q9-the first enriched hydrogen-rich gas output from the membrane separation device; Q10-the membrane Output gas of water cooler after separation; Q11- output gas of compressor before PSA; Q12- output gas of water cooler before PSA; Q13- desorption tail gas output from PSA device; Q14- PSA device Output of finished hydrogen.
本发明的实施方式Embodiments of the present invention
下面结合具体实施方式并对照附图对本发明作进一步详细说明。应该强调的是，下述说明仅仅是示例性的，而不是为了限制本发明的范围及其应用。The present invention will be further described in detail below in combination with specific embodiments and with reference to the accompanying drawings. It should be emphasized that the following description is only exemplary and not intended to limit the scope of the invention and its application.
参照图1，将描述非限制性和非排他性的实施例。Referring to Figure 1, a non-limiting and non-exclusive example will be described.
试用于某石化企业的一种以瓦斯为原料气的氢气回收系统，原料气是氢气组分含量小于50%且组分复杂多变、难以回收的瓦斯，总气体量为10000Nm 3，其组分及其含量如下：氢气  40mol%  （含量不稳定，随时发生±10%幅度的波动）；甲烷  30mol%  （含量不稳定，随时发生±10%幅度的波动）；CO+CO 2 5mol%（含量不稳定，可能发生±50%甚至更大幅度的波动）；C 3+   5mol%  （含量不稳定，可能发生±50%甚至更大幅度的波动）；其他  20mol% （含量不稳定，随时发生±10%幅度的波动）。 A hydrogen recovery system using gas as the raw material gas was tried out in a petrochemical enterprise. The raw material gas is gas with a hydrogen component content of less than 50% and complex and variable components that are difficult to recover. The total gas volume is 10,000Nm 3 , and its components And its content is as follows: hydrogen 40mol% (the content is unstable, fluctuating by ±10% at any time); methane 30mol% (the content is unstable, fluctuating by ±10% at any time); CO+CO 2 5mol% (the content is not stable stable, may fluctuate by ±50% or more); C 3 + 5mol% (unstable content, may fluctuate by ±50% or more); other 20mol% (unstable content, fluctuate by ±10% at any time) % fluctuation).
本具体实施方式的氢气回收系统的组成如图1所示，从左到右依次连接的是气液分离前压缩机1、气液分离前水冷器2、气液分离罐3、变温吸附装置4、膜分离前加热器5、精密过滤器6、膜分离装置7、膜分离后水冷器8、变压吸附前压缩机9、变压吸附前水冷器10和变压吸附装置11。The composition of the hydrogen recovery system of this specific embodiment is shown in Figure 1, and what are connected sequentially from left to right are the compressor 1 before the gas-liquid separation, the water cooler 2 before the gas-liquid separation, the gas-liquid separation tank 3, and the temperature swing adsorption device 4 , heater 5 before membrane separation, precision filter 6, membrane separation device 7, water cooler 8 after membrane separation, compressor 9 before pressure swing adsorption, water cooler 10 before pressure swing adsorption and pressure swing adsorption device 11.
原料气瓦斯通过气液分离前压缩机1 从外部系统压力加压为高于2.8Mpa的高压气相瓦斯，气液分离前压缩机1是二级往复式压缩机，然后经过气液分离前水冷器2降温到常温，此时有部分重烃组分凝结成液态，再经过气液分离罐3将高压气相瓦斯中夹带的沸点较高的液滴凝聚并分离析出，其中组分C3 +的含量受平衡分压的影响由5mol%降低到约2.8mol%，温度为常温，再送入变温吸附装置4进行变温吸附。 Raw gas gas is pressurized from the external system pressure by compressor 1 before gas-liquid separation to high-pressure gas-phase gas higher than 2.8Mpa. Compressor 1 before gas-liquid separation is a two-stage reciprocating compressor, and then passes through the water cooler before gas-liquid separation 2. Cool down to normal temperature. At this time, some heavy hydrocarbon components condense into a liquid state, and then pass through the gas-liquid separation tank 3 to condense and separate out the liquid droplets with higher boiling points entrained in the high-pressure gas phase gas. The content of the component C3 + is affected by the The influence of the equilibrium partial pressure is reduced from 5 mol% to about 2.8 mol%, and the temperature is normal temperature, and then sent to the temperature swing adsorption device 4 for temperature swing adsorption.
变温吸附装置4是双塔吸附式变温吸附装置，当一个变温吸附塔进行吸附时，另一个变温吸附塔进行再生，通过阀门控制两个变温吸附塔的切换，每5个小时切换一次，保持产品气质量平稳，经过变温吸附后的瓦斯的C3 +含量进一步降低，尤其是分子量越大的组分，被变温吸附的比例就越高，压力下降为约0.03Mpa。变温吸附塔利用膜分离装置7产生的高温尾气对吸附剂进行解析再生，产生的解析气温度约为70℃，也可通过再加热器进行提温，以增强再生能力，此时气体流量约为6000Nm 3，通过变温吸附再生后的尾气，减压进入瓦斯管网。变温吸附装置4输出的高压气相瓦斯经过膜分离前加热器5升温至75℃，输出的高温高压气相瓦斯进入精密过滤器6，滤除气体中颗粒杂质后进入膜分离装置7。 The temperature swing adsorption device 4 is a double-tower adsorption temperature swing adsorption device. When one temperature swing adsorption tower is adsorbing, the other temperature swing adsorption tower is regenerated. The switch between the two temperature swing adsorption towers is controlled by a valve, and the switch is made every 5 hours to keep the product The gas quality is stable, and the C3 + content of the gas after temperature swing adsorption is further reduced, especially the components with higher molecular weight, the higher the ratio of being adsorbed by temperature swing, the pressure drops to about 0.03Mpa. The temperature swing adsorption tower uses the high-temperature tail gas generated by the membrane separation device 7 to analyze and regenerate the adsorbent. The temperature of the generated desorbed gas is about 70°C. It can also be heated by a reheater to enhance the regeneration capacity. At this time, the gas flow rate is about 6000Nm 3 , the tail gas regenerated by temperature swing adsorption is decompressed and enters the gas pipe network. The high-pressure gas-phase gas output from the temperature-swing adsorption device 4 is heated to 75°C by the heater 5 before membrane separation, and the output high-temperature and high-pressure gas-phase gas enters the precision filter 6 to filter out particulate impurities in the gas and then enters the membrane separation device 7 .
膜分离装置7采用10片聚酰亚胺中空纤维膜串/并列组合的膜分离，聚酰亚胺中空纤维膜的膜壁具有多微孔支撑层和分离功能的紧密层，分离混合气体时有高选择性，纯度和回收率高，本身耐腐蚀性和耐热性好，制法是将联苯四甲酸二酐和芳族二胺缩聚并进行干-湿纺而得。膜分离装置7分离后输出的初次提浓的富氢气的浓度提高到60mol%~97mol%、甲烷的浓度降低到5mol%~20mol%、一氧化碳和二氧化碳的浓度降低到1mol%~2mol%。受膜过滤影响，富氢气的压力下降到0.1Mpa~0.5MPa，流量约为4000Nm 3~5000Nm 3，通过膜分离后水冷器8降温到常温，冷却后为低温富氢气，再经过变压吸附前压缩机9升压到1.8MPa ~2.5MPa，变压吸附前压缩机9是二级往复式压缩机，变压吸附前压缩机9的出口温度高达70℃，高压富氢气又经过变压吸附前水冷器10冷却到常温后进入变压吸附装置11进行进一步提浓。变压吸附装置11是采用六个变压吸附塔与四个缓冲罐组成的变压吸附装置，常温高压富氢气按顺序进入缓冲罐，然后进入变压吸附塔中，变压吸附塔内的吸附剂将常温高压富氢气中的甲烷、一氧化碳和二氧化碳其他部分气体吸附。 Membrane separation device 7 adopts the membrane separation of 10 pieces of polyimide hollow fiber membrane series/parallel combination. The membrane wall of polyimide hollow fiber membrane has a microporous support layer and a tight layer with separation function. High selectivity, high purity and recovery rate, good corrosion resistance and heat resistance, the preparation method is polycondensation of biphenyl tetracarboxylic dianhydride and aromatic diamine and dry-wet spinning. After separation by the membrane separation device 7, the concentration of the hydrogen-enriched gas initially enriched is increased to 60mol%~97mol%, the concentration of methane is reduced to 5mol%~20mol%, and the concentration of carbon monoxide and carbon dioxide is reduced to 1mol%~2mol%. Affected by membrane filtration, the pressure of hydrogen-rich gas drops to 0.1Mpa~0.5MPa, and the flow rate is about 4000Nm 3 ~5000Nm 3 . After membrane separation, the water cooler 8 cools down to normal temperature. After cooling, it becomes low-temperature hydrogen-rich gas. Compressor 9 boosts the pressure to 1.8MPa ~ 2.5MPa. Before PSA, compressor 9 is a two-stage reciprocating compressor. Before PSA, the outlet temperature of compressor 9 is as high as 70°C. After the water cooler 10 is cooled to normal temperature, it enters the pressure swing adsorption device 11 for further enrichment. The pressure swing adsorption device 11 is a pressure swing adsorption device composed of six pressure swing adsorption towers and four buffer tanks. The hydrogen-rich gas at normal temperature and high pressure enters the buffer tanks in sequence, and then enters the pressure swing adsorption tower. The adsorption in the pressure swing adsorption tower The agent adsorbs methane, carbon monoxide and other parts of carbon dioxide in hydrogen-rich gas at normal temperature and high pressure.
输出成品氢气的氢气浓度为90mol%~99.9mol%、一氧化碳和二氧化碳的浓度满足下游用户要求，其余不影响下游使用的杂质的质量百分比为0.1%~10.0%，从变压吸附塔出口流出的成品氢气进入成品气缓冲罐，最终排出氢气回收系统进入氢气管网。The hydrogen concentration of the output product hydrogen is 90mol%~99.9mol%, the concentration of carbon monoxide and carbon dioxide meets the requirements of downstream users, and the mass percentage of other impurities that do not affect downstream use is 0.1%~10.0%. The finished product flowing out from the outlet of the pressure swing adsorption tower The hydrogen enters the product gas buffer tank, and finally exits the hydrogen recovery system and enters the hydrogen pipeline network.
当变压吸附塔吸附饱和后，通过控制阀将原料气引入另一个再生后的变压吸附塔。吸附饱和的变压吸附塔与顺放气罐之间的阀门打开，变压吸附塔内的压力开始逐渐下降到1.0MPa±0.1MPa，然后打开变压吸附塔与解析气缓冲罐之间的阀门，进一步降低变压吸附塔内压力，直至变压吸附塔内压力接近大气压力，之后利用正在吸附的变压吸附塔产出的富氢气升压到高于2.0MPa，完成吸附剂的解析再生，变压吸附装置11输出的脱附尾气排放到放空管线，六个变压吸附塔中始终有一个变压吸附塔正在吸附，一个变压吸附塔完成解析再生，其他四个变压吸附塔分别处于不同阶段的解析再生。When the pressure swing adsorption tower is saturated, the feed gas is introduced into another regenerated pressure swing adsorption tower through the control valve. The valve between the saturated pressure swing adsorption tower and the degassing tank is opened, the pressure in the pressure swing adsorption tower begins to gradually drop to 1.0MPa±0.1MPa, and then the valve between the pressure swing adsorption tower and the desorption gas buffer tank is opened , further reduce the pressure in the pressure swing adsorption tower until the pressure in the pressure swing adsorption tower is close to the atmospheric pressure, and then use the hydrogen-rich gas produced by the pressure swing adsorption tower being adsorbed to increase the pressure to higher than 2.0MPa to complete the analytical regeneration of the adsorbent. The desorbed tail gas output by PSA unit 11 is discharged to the venting pipeline. Among the six PSA towers, one PSA tower is always adsorbing, one PSA tower completes desorption and regeneration, and the other four PSA towers are in the Analytical regeneration at different stages.
本具体实施方式的氢气回收方法依次有以下步骤：1）将原料气瓦斯进行压缩冷却与气液分离制备高压气相瓦斯；采用气液分离前压缩机将原料气瓦斯从外部系统压力加压为高于2.0Mpa的高压气相瓦斯，再采用循环水为降温介质的水冷式换热器将高压气相瓦斯冷却至常温，最后采用气体与冷凝面接触面积大的气液分离罐进行气液分离，将高压气相瓦斯中夹带的沸点较高的液滴凝聚并分离析出。The hydrogen recovery method in this specific embodiment has the following steps in sequence: 1) compressing and cooling the raw gas gas and separating gas-liquid to prepare high-pressure gas-phase gas; using a compressor before gas-liquid separation to pressurize the raw gas gas from the external system pressure to high At 2.0Mpa high-pressure gas-phase gas, the high-pressure gas-phase gas is cooled to normal temperature by using a water-cooled heat exchanger with circulating water as the cooling medium, and finally the gas-liquid separation tank with a large contact area between the gas and the condensation surface is used for gas-liquid separation, and the high-pressure The liquid droplets with higher boiling point entrained in the gas phase coalesce and separate out.
2）将高压气相瓦斯变温吸附除去沸点较高的组分以及部分水采用变温吸附装置中的吸附剂吸附除去高压气相瓦斯中的沸点较高的组分以及部分水，分子量越大的组分，被变温吸附的比例越高，将经过变温吸附处理的高压气相瓦斯依次送入膜分离前加热器、精密过滤器进行升温并精细过滤，进一步降低原料气中沸点较高组分的含量以及的原料气的露点温度，使得在送入膜分离装置前的瓦斯的露点温度远远低于了膜分离装置的工作温度，而被吸附的重烃组分即变温吸附后的脱附尾气以及部分水经过变温吸附处理的再生流程排出，直接进入燃料瓦斯管网供作它用或进入液化气吸收稳定系统。2) Remove components with higher boiling points and part of water by temperature swing adsorption of high-pressure gas phase gas. Use the adsorbent in the temperature swing adsorption device to adsorb and remove components with higher boiling points and part of water in high-pressure gas phase gas. The components with higher molecular weight, The higher the ratio of temperature swing adsorption, the higher the temperature swing adsorption treatment, the high-pressure gas phase gas will be sequentially sent to the pre-membrane separation heater and precision filter for heating and fine filtration, further reducing the content of components with higher boiling points in the raw gas and the raw materials The dew point temperature of the gas makes the dew point temperature of the gas before being sent into the membrane separation device far lower than the working temperature of the membrane separation device, and the adsorbed heavy hydrocarbon components are the desorbed tail gas and part of the water after the temperature swing adsorption. The discharge from the regeneration process of temperature swing adsorption treatment directly enters the fuel gas pipeline network for other uses or enters the liquefied gas absorption and stabilization system.
3）将高压气相瓦斯进行膜分离制备富氢气将经过升温并气液分离的高压气相瓦斯送入膜分离装置通过过滤膜进行初次提浓，在低压侧输出高含氢的渗透气即富氢气，在高压侧输出低含氢的渗余气，富氢气再送入膜分离后水冷器冷却降温到常温，渗余气直接进入燃料瓦斯管网供作它用或进入变温吸附装置作为再生气。3) Membrane separation of high-pressure gas-phase gas to prepare hydrogen-rich gas. The high-pressure gas-phase gas that has been heated and separated from gas and liquid is sent to the membrane separation device for initial concentration through the filter membrane, and the permeate gas with high hydrogen content is output at the low-pressure side, namely hydrogen-rich gas. The retentate gas with low hydrogen content is output on the high-pressure side, and the hydrogen-rich gas is sent to the water cooler after membrane separation to cool down to normal temperature. The retentate gas directly enters the fuel gas pipeline network for other uses or enters the temperature swing adsorption device as regeneration gas.
4）将富氢气进行变压吸附制备成品氢气：将高含氢的渗透气即富氢气经过变压吸附前压缩机加压，提升压力为高压富氢气，再送入变压吸附前水冷器冷却降温到常温后送入变压吸附装置再次提纯提浓为成品氢气，精制到满足后续生产质量要求，经过再次升压并入氢气管网，而低压低含氢的解析气经过尾气压缩机加压后排入燃料瓦斯管网供作它用。4) The hydrogen-rich gas is subjected to pressure swing adsorption to prepare finished hydrogen gas: the permeated gas with high hydrogen content, that is, the hydrogen-rich gas, is pressurized by the compressor before the pressure swing adsorption, and the pressure is raised to a high-pressure hydrogen-rich gas, and then sent to the water cooler before the pressure swing adsorption to cool down After reaching normal temperature, it is sent to the pressure swing adsorption device for further purification and enrichment into finished hydrogen, which is refined to meet the quality requirements of subsequent production. After being boosted again, it is incorporated into the hydrogen pipeline network, and the low-pressure and low-hydrogen-containing analyte gas is pressurized by the tail gas compressor. Discharged into the fuel gas pipeline network for other uses.
本具体实施方式的原料气是氢气组分含量小于50%且组分复杂多变、难以回收的瓦斯，而回收的成品氢气的浓度为90.0mol%~99.9mol%、一氧化碳和二氧化碳的浓度满足下游用户要求、氢气回收率超过80%。最终排出氢气回收系统进入氢气管网的成品氢气流量约为4000Nm 3。 The raw material gas in this specific embodiment is a gas whose hydrogen component content is less than 50% and the components are complex and changeable, and it is difficult to recover, while the hydrogen concentration of the recovered product is 90.0mol%~99.9mol%, and the concentration of carbon monoxide and carbon dioxide meets the requirements of the downstream gas. User requirements, the hydrogen recovery rate exceeds 80%. The flow rate of the finished hydrogen gas that finally exits the hydrogen recovery system and enters the hydrogen pipeline network is about 4000Nm 3 .
本具体实施方式的主要能耗是蒸汽和电能，系统电能消耗总功率为1200千瓦，低压蒸汽消耗量为0.3吨/小时，按电费0.69元/千瓦时、低压蒸汽240元/吨计算，考虑仪表气等其他消耗，每回收1吨100%纯氢气的运行费用约为2700元/吨，与直接购买氢气折纯的价格约为20000元/吨比较，扣除减少氢气做瓦斯用的等热值收益6000元/吨，本具体实施方式的方法和系统回收氢气的经济收益约为13000元/吨。The main energy consumption of this specific embodiment is steam and electric energy. The total power consumption of the system electric energy is 1200 kilowatts, and the consumption of low-pressure steam is 0.3 tons/hour, calculated according to the electricity cost of 0.69 yuan/kWh and the low-pressure steam of 240 yuan/ton. Gas and other consumption, the operating cost of recovering 1 ton of 100% pure hydrogen is about 2,700 yuan/ton, compared with the direct purchase of hydrogen at a price of about 20,000 yuan/ton, deducting the income from reducing the equivalent calorific value of hydrogen used as gas 6,000 yuan/ton, the economic benefit of recovering hydrogen by the method and system of this embodiment is about 13,000 yuan/ton.
试用工况表明，本具体实施方式的方法和系统能长期稳定有效的回收复杂组分瓦斯中的氢气，实现低能耗和高收益。Trial working conditions show that the method and system of this specific embodiment can recover hydrogen in gas with complex components stably and effectively for a long time, and realize low energy consumption and high income.
以上内容是结合具体的优选实施方式对本发明所作的进一步详细说明，不能认定本发明的具体实施只局限于这些说明。对于本发明所属技术领域的普通技术人员来说，在不脱离本发明构思的前提下做出若干等同替代或明显变型，而且性能或用途相同，都应当视为属于本发明由所提交的权利要求书确定的专利保护范围。The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be assumed that the specific implementation of the present invention is limited to these descriptions. For those of ordinary skill in the technical field to which the present invention belongs, several equivalent substitutions or obvious modifications are made without departing from the concept of the present invention, and the performance or use is the same, all should be regarded as belonging to the present invention by the submitted claims The scope of patent protection determined by the book.

Claims (10)

  1. 一种以瓦斯为原料气的氢气回收系统，包括压缩冷却与气液分离装置、膜分离装置和变压吸附装置，所述压缩冷却与气液分离装置用于制备高压气相瓦斯，所述膜分离装置用于在低压侧得到高含氢的渗透气即富氢气，在高压侧得到低含氢的渗余气，所述变压吸附装置用于将富氢气进行变压吸附制备成品氢气，其特征在于：A hydrogen recovery system using gas as raw material gas, including a compression cooling and gas-liquid separation device, a membrane separation device and a pressure swing adsorption device, the compression cooling and gas-liquid separation device is used to prepare high-pressure gas phase gas, and the membrane separation device The device is used to obtain high-hydrogen-containing permeate gas, that is, hydrogen-rich gas at the low-pressure side, and low-hydrogen-containing retentate gas at the high-pressure side. The pressure swing adsorption device is used to perform pressure swing adsorption on hydrogen-rich gas to prepare hydrogen gas. Its characteristics in:
    还包括设置在所述压缩冷却与气液分离装置与所述膜分离装置中间的变温吸附装置，所述变温吸附装置用于从高压气相瓦斯中选择性吸附除去部分沸点较高的组分以及部分水，有效利用较低能耗降低原料气的露点温度；It also includes a temperature swing adsorption device arranged between the compression cooling and gas-liquid separation device and the membrane separation device, and the temperature swing adsorption device is used to selectively adsorb and remove some components with higher boiling points and some Water, effective use of lower energy consumption to reduce the dew point temperature of raw gas;
    所述变温吸附装置，是采用冗余设计的至少有两个吸附塔的变温吸附装置，以减少复杂多变组分的瓦斯中过多的沸点较高的组分对过滤膜的不利影响。The temperature swing adsorption device is a redundantly designed temperature swing adsorption device with at least two adsorption towers to reduce the adverse effects of too many components with high boiling points in the gas with complex and variable components on the filter membrane.
  2. 如权利要求1所述的以瓦斯为原料气的氢气回收系统，其特征在于：The hydrogen recovery system using gas as raw material gas according to claim 1, characterized in that:
    所述压缩冷却与气液分离装置由气液分离前压缩机、气液分离前水冷器和气液分离罐依次连接组成，所述气液分离前压缩机用于将原料气从外部系统压力加压到高于2.0MPa的高压气相瓦斯，所述气液分离前水冷器用于将高压气相瓦斯冷却至常温或测算经济性可接受的低温，所述测算经济性可接受的低温是5℃~33℃，所述气液分离罐用于将高压气相瓦斯中夹带的沸点较高的液滴凝聚并分离析出，防止液体进入变温吸附装置；The compression cooling and gas-liquid separation device is composed of a compressor before gas-liquid separation, a water cooler before gas-liquid separation, and a gas-liquid separation tank, and the compressor before gas-liquid separation is used to pressurize the raw material gas from the external system pressure For high-pressure gas-phase gas higher than 2.0MPa, the water cooler before gas-liquid separation is used to cool the high-pressure gas-phase gas to normal temperature or to an economically acceptable low temperature, and the economically acceptable low temperature is 5°C to 33°C , the gas-liquid separation tank is used to condense and separate liquid droplets with higher boiling points entrained in the high-pressure gas phase gas, so as to prevent the liquid from entering the temperature swing adsorption device;
    所述气液分离前压缩机是至少两级往复式压缩机；The compressor before the gas-liquid separation is at least a two-stage reciprocating compressor;
    所述气液分离前水冷器是采用循环水或冷冻水为降温介质的水冷式换热器；The water cooler before the gas-liquid separation is a water-cooled heat exchanger using circulating water or chilled water as the cooling medium;
    所述气液分离罐是气体与冷凝面接触面积大的气液分离罐，以增强高压气相瓦斯中夹带的沸点较高的液滴凝聚并分离析出。The gas-liquid separation tank is a gas-liquid separation tank with a large contact area between the gas and the condensation surface, so as to enhance the condensation and separation of liquid droplets with higher boiling points entrained in the high-pressure gas phase gas.
  3. 如权利要求1所述的以瓦斯为原料气的氢气回收系统，其特征在于：The hydrogen recovery system using gas as raw material gas according to claim 1, characterized in that:
    在所述变温吸附装置与所述膜分离装置之间依次设有膜分离前加热器和精密过滤器，所述膜分离前加热器用于将变温吸附装置输出的高压瓦斯加热到膜分离装置需要的工作温度，所述精密过滤器用于将变温吸附装置输出经过加热的高压瓦斯脱除可能含有的固体颗粒；Between the temperature swing adsorption device and the membrane separation device, a pre-membrane separation heater and a precision filter are arranged sequentially, and the pre-membrane separation heater is used to heat the high-pressure gas output from the temperature swing adsorption device to the required temperature of the membrane separation device. Working temperature, the precision filter is used to remove the solid particles that may be contained in the heated high-pressure gas output by the temperature swing adsorption device;
    所述膜分离前加热器是蒸汽加热器、热水加热器、热油加热器以及电加热器中的一种；The heater before the membrane separation is one of a steam heater, a hot water heater, a thermal oil heater and an electric heater;
    所述精密过滤器是过滤固体颗粒精度达到0.1μm的过滤器。The precision filter is a filter that filters solid particles with a precision of 0.1 μm.
  4. 如权利要求1所述的以瓦斯为原料气的氢气回收系统，其特征在于：所述膜分离装置，是采用合理设计分离面积、工作压差的至少两片聚酰亚胺中空纤维膜串/并列组合的膜分离装置，有效控制膜分离装置的渗余气的露点温度上升，渗余气的露点温度与膜分离装置的工作温度相比至少低15℃，以实现氢分离效率和安全性的统一，延长膜分离装置的分离膜的使用寿命。The hydrogen recovery system using gas as raw material gas according to claim 1, characterized in that: said membrane separation device adopts at least two polyimide hollow fiber membrane strings/ The parallel combination of membrane separation devices can effectively control the rise of the dew point temperature of the retentate gas of the membrane separation device. The dew point temperature of the retentate gas is at least 15°C lower than the working temperature of the membrane separation device to achieve the best hydrogen separation efficiency and safety. Unified, prolong the service life of the separation membrane of the membrane separation device.
  5. 如权利要求1所述的氢气回收系统的氢气回收系统，其特征在于：在所述膜分离装置与所述变压吸附装置之间依次设有膜分离后水冷器、变压吸附前压缩机和变压吸附前水冷器，所述膜分离后水冷器用于将高含氢的渗透气即所制备的富氢气初次冷却到常温，所述变压吸附前压缩机用于将冷却到常温的富氢气提升压力，所述变压吸附前水冷器用于将提升压力的富氢气再次冷却到常温；The hydrogen recovery system of the hydrogen recovery system according to claim 1, characterized in that: between the membrane separation device and the pressure swing adsorption device, a water cooler after membrane separation, a compressor before pressure swing adsorption and The water cooler before the pressure swing adsorption, the water cooler after the membrane separation is used to cool the permeated gas with high hydrogen content, that is, the prepared hydrogen-rich gas to normal temperature for the first time, and the compressor before the pressure swing adsorption is used to cool the hydrogen-rich gas cooled to normal temperature Boosting the pressure, the water cooler before the pressure swing adsorption is used to cool the hydrogen-rich gas with the boosting pressure to normal temperature again;
    所述膜分离后水冷器是采用循环水或冷冻水为降温介质的水冷式换热器；The water cooler after membrane separation is a water-cooled heat exchanger using circulating water or chilled water as the cooling medium;
    所述变压吸附前压缩机是至少两级往复式压缩机和螺杆式压缩机中的一种；The compressor before the PSA is at least one of two-stage reciprocating compressor and screw compressor;
    所述变压吸附前水冷器是采用循环水或冷冻水为降温介质的水冷式换热器。The water cooler before the pressure swing adsorption is a water-cooled heat exchanger using circulating water or chilled water as a cooling medium.
  6. 如权利要求1所述的以瓦斯为原料气的氢气回收系统，其特征在于：所述变压吸附装置，是至少两个变压吸附塔和至少一个缓冲罐组成的可连续运行的变压吸附装置，富氢气按顺序进入缓冲罐，然后进入变压吸附塔中，变压吸附塔内的吸附剂将原料气中包括甲烷、一氧化碳、二氧化碳的部分气体吸附，流出的富氢气的氢气浓度为90.0mol%~99.9mol%、一氧化碳和二氧化碳的浓度满足下游用户要求，其余不影响下游使用的杂质的质量百分比为0.1%~10.0%，从变压吸附塔出口流出的成品氢气进入成品气缓冲罐，最终排出氢气回收系统进入氢气管网，当一个变压吸附塔吸附饱和后，通过控制阀将原料气引入另一个再生后的变压吸附塔，吸附饱和的变压吸附塔与顺放气罐之间的阀门打开，变压吸附塔内的压力开始逐渐下降到1.0MPa±0.1MPa，然后打开变压吸附塔与解析气缓冲罐之间的阀门，进一步降低变压吸附塔内压力，直至变压吸附塔内压力接近大气压力，之后利用正在吸附的变压吸附塔产出的富氢气升压到高于2.0MPa，完成吸附剂的解析再生，变压吸附后脱附尾气排放到放空管线，始终有一个变压吸附塔正在吸附，其余变压吸附塔分别处于不同阶段的解析再生。The hydrogen recovery system using gas as raw material gas according to claim 1, characterized in that: said pressure swing adsorption device is a continuously operable pressure swing adsorption composed of at least two pressure swing adsorption towers and at least one buffer tank device, the hydrogen-rich gas enters the buffer tank in sequence, and then enters the pressure swing adsorption tower. The adsorbent in the pressure swing adsorption tower absorbs part of the gas including methane, carbon monoxide, and carbon dioxide in the raw material gas, and the hydrogen concentration of the hydrogen-rich gas flowing out is 90.0 mol%~99.9mol%, the concentration of carbon monoxide and carbon dioxide meets the requirements of downstream users, and the mass percentage of other impurities that do not affect downstream use is 0.1%~10.0%. The finished hydrogen gas flowing out from the outlet of the PSA tower enters the finished gas buffer tank, Finally, the exhausted hydrogen recovery system enters the hydrogen pipeline network. When one pressure swing adsorption tower is saturated, the raw material gas is introduced into another regenerated pressure swing adsorption tower through the control valve. Open the valve between the pressure swing adsorption tower, the pressure in the pressure swing adsorption tower begins to drop gradually to 1.0MPa±0.1MPa, and then open the valve between the pressure swing adsorption tower and the desorption gas buffer tank to further reduce the pressure in the pressure swing adsorption tower until the pressure swing The pressure inside the adsorption tower is close to atmospheric pressure, and then the hydrogen-rich gas produced by the adsorbing PSA tower is used to boost the pressure to higher than 2.0MPa to complete the desorption regeneration of the adsorbent. One pressure swing adsorption tower is adsorbing, and the rest of the pressure swing adsorption towers are in different stages of analytical regeneration.
  7. 一种采用权利要求1~6中任意一项所述的以瓦斯为原料气的氢气回收系统的氢气回收方法，包括压缩冷却与气液分离制备高压气相瓦斯、膜分离制备富氢气，以及变压吸附制备成品氢气，其特征在于：  A hydrogen recovery method using the hydrogen recovery system using gas as raw material gas according to any one of claims 1 to 6, comprising compression cooling and gas-liquid separation to prepare high-pressure gas-phase gas, membrane separation to prepare hydrogen-rich gas, and variable pressure Preparation of finished product hydrogen by adsorption, characterized in that:
    还包括将高压气相瓦斯变温吸附除去沸点较高的组分以及部分水，有效利用较低能耗降低露点温度，分子量越大的组分，被变温吸附的比例越高，再将经过变温吸附处理的高压气相瓦斯依次送入膜分离前加热器、精密过滤器进行升温并精细过滤，使得在送入膜分离装置前的瓦斯的露点温度远远低于了膜分离装置的工作温度，而被变温吸附的重烃组分以及部分水经过变温吸附处理的再生流程排出，直接进入燃料瓦斯管网供作它用或进入液化气吸收稳定系统；It also includes removing components with higher boiling points and part of the water by high-pressure gas-phase gas temperature swing adsorption, effectively using lower energy consumption to reduce the dew point temperature, and components with larger molecular weights have a higher proportion of temperature swing adsorption, and then undergo temperature swing adsorption treatment The high-pressure gas-phase gas is sequentially sent to the pre-membrane separation heater and precision filter for heating and fine filtration, so that the dew point temperature of the gas before being sent to the membrane separation device is far lower than the working temperature of the membrane separation device, and the temperature is changed. The adsorbed heavy hydrocarbon components and part of the water are discharged through the regeneration process of temperature swing adsorption treatment, and directly enter the fuel gas pipeline network for other uses or enter the liquefied gas absorption and stabilization system;
    所述变温吸附，是采用冗余设计的至少有两个吸附塔的变温吸附，以减少复杂多变组分的瓦斯中过多的高沸点组分对过滤膜的不利影响，其中一个吸附塔进行吸附，其余吸附塔进行再生，切换时预留较大的吸附剩余能力，以应对瓦斯的组分复杂且各个组分的含量相对变化大，以便系统有时间调整操作，最大限度保护后续的膜分离装置；The temperature swing adsorption is a temperature swing adsorption with at least two adsorption towers with redundant design to reduce the adverse effects of too many high boiling point components in the gas with complex and variable components on the filter membrane. One of the adsorption towers is Adsorption, the rest of the adsorption towers are regenerated, and a large residual adsorption capacity is reserved when switching to deal with the complex components of the gas and the relatively large changes in the content of each component, so that the system has time to adjust the operation and protect the subsequent membrane separation to the greatest extent. device;
    所述升温并精密过滤，是将高压气相瓦斯升温至50℃~90℃并采用精密过滤器精密过滤，滤除气体中颗粒杂质后进入膜分离装置。The heating and precision filtration is to raise the temperature of the high-pressure gas phase gas to 50°C~90°C and use a precision filter to filter it precisely, and filter out the particulate impurities in the gas before entering the membrane separation device.
  8. 如权利要求7所述的氢气回收方法，其特征在于：The hydrogen recovery method as claimed in claim 7, characterized in that:
    所述压缩冷却与气液分离制备高压气相瓦斯，是将原料气压缩为高压气相瓦斯并冷却后，进入气液分离罐将高压气相瓦斯中夹带的沸点较高的液滴凝聚并分离析出；The compression cooling and gas-liquid separation to prepare high-pressure gas-phase gas is to compress the raw material gas into high-pressure gas-phase gas and cool it, and then enter the gas-liquid separation tank to condense and separate the liquid droplets with higher boiling points entrained in the high-pressure gas-phase gas;
    所述膜分离制备富氢气，是将经过升温并气液分离的高压气相瓦斯送入膜分离装置通过分离膜进行初次提浓，在低压侧输出氢含量为60 mol%The preparation of hydrogen-rich gas by membrane separation is to send the high-pressure gas-phase gas that has been heated and separated from gas to liquid into the membrane separation device for initial enrichment through the separation membrane, and the output hydrogen content on the low-pressure side is 60 mol%
    ~97mol%的高含氢的渗透气即富氢气，在高压侧输出低含氢的渗余气，富氢气再送入膜分离后水冷器冷却降温到常温，渗余气直接进入燃料瓦斯管网供作它用或进入变温吸附装置作为再生气；The permeate gas with ~97mol% high hydrogen content is hydrogen-rich gas, and the retentate gas with low hydrogen content is output at the high pressure side, and the hydrogen-rich gas is sent to the membrane separation, and the water cooler cools down to normal temperature, and the retentate gas directly enters the fuel gas pipeline network for supply Used for other purposes or enter the temperature swing adsorption device as regeneration gas;
    所述变压吸附制备成品氢气，是将高含氢的渗透气即富氢气经过变压吸附前压缩机加压，提升压力为高压富氢气，再送入变压吸附前水冷器冷却降温到常温后送入变压吸附装置再次提纯提浓为成品氢气，精制到满足后续生产质量要求，而低压低含氢的解析气经过尾气压缩机加压后排入燃料瓦斯管网供作它用。The preparation of finished hydrogen by pressure swing adsorption is to pressurize the high-hydrogen-containing permeated gas, that is, hydrogen-rich gas, through a compressor before PSA to increase the pressure to high-pressure hydrogen-rich gas, and then send it to the water cooler before PSA to cool down to normal temperature. It is sent to the pressure swing adsorption unit for further purification and enrichment into finished hydrogen, refined to meet the quality requirements of subsequent production, and the low-pressure and low-hydrogen-containing analyte gas is pressurized by the tail gas compressor and discharged into the fuel gas pipeline network for other uses.
  9. 如权利要求7所述的氢气回收方法，其特征在于：The hydrogen recovery method as claimed in claim 7, characterized in that:
    所述将原料气压缩为高压气相瓦斯，是采用气液分离前压缩机将原料气从外部系统压力加压到高于2.0Mpa；The compression of raw material gas into high-pressure gas phase gas is to use the compressor before gas-liquid separation to pressurize the raw material gas from the external system pressure to higher than 2.0Mpa;
    所述将高压气相瓦斯冷却，是采用循环水或冷冻水为降温介质的水冷式换热器将高压气相瓦斯冷却至常温或测算经济性可接受的低温，所述测算经济性可接受的低温是5℃~33℃；The cooling of the high-pressure gas-phase gas is to cool the high-pressure gas-phase gas to normal temperature or an economically acceptable low temperature by using a water-cooled heat exchanger using circulating water or chilled water as the cooling medium. The economically acceptable low temperature is 5°C~33°C;
    所述气液分离，是采用气体与冷凝面接触面积大的气液分离罐进行气液分离，以增强高压气相瓦斯中夹带的沸点较高的液滴凝聚并分离析出；The gas-liquid separation is to use a gas-liquid separation tank with a large contact area between the gas and the condensing surface for gas-liquid separation, so as to enhance the condensation and separation of liquid droplets with higher boiling points entrained in the high-pressure gas phase gas;
    所述膜分离，是采用合理设计分离面积、工作压差的至少两片聚酰亚胺中空纤维膜串/并列组合的膜分离，通过有效控制膜分离装置的渗余气的露点温度上升，渗余气的露点温度相比膜分离装置的工作温度低至少15℃，以实现氢分离效率和安全性的统一，延长膜分离装置的分离膜的使用寿命；The membrane separation is the membrane separation of at least two polyimide hollow fiber membrane series/parallel combination with reasonable design of separation area and working pressure difference. By effectively controlling the dew point temperature rise of the retentate gas in the membrane separation device, the retentate The dew point temperature of the residual gas is at least 15°C lower than the working temperature of the membrane separation device, so as to achieve the unity of hydrogen separation efficiency and safety, and prolong the service life of the separation membrane of the membrane separation device;
    所述变压吸附前压缩机加压，是采用变压吸附前压缩机将膜分离装置流出的富氢气从0.01Mpa~0.50MPa加压到1.8Mpa~6.0Mpa，变压吸附前压缩机出口温度为50℃±30℃；The pressurization of the compressor before the pressure swing adsorption is to use the compressor before the pressure swing adsorption to pressurize the hydrogen-rich gas flowing out of the membrane separation device from 0.01Mpa~0.50MPa to 1.8Mpa~6.0Mpa, and the outlet temperature of the compressor before the pressure swing adsorption 50℃±30℃;
    所述变压吸附前水冷器冷却，是采用循环水或冷冻水为降温介质的水冷式换热器将高压富氢气冷却至常温；The water cooler before the pressure swing adsorption is cooled by a water-cooled heat exchanger using circulating water or chilled water as the cooling medium to cool the high-pressure hydrogen-enriched gas to normal temperature;
    所述变压吸附，是至少两个变压吸附塔和至少一个缓冲罐组成的可连续运行的变压吸附，当一个变压吸附塔吸附饱和后，通过控制阀将原料气引入另一个再生后的变压吸附塔。吸附饱和的变压吸附塔与顺放气罐之间的阀门打开，变压吸附塔内的压力开始逐渐下降到1.0MPa±0.1MPa，然后打开变压吸附塔与解析气缓冲罐之间的阀门，进一步降低变压吸附塔内压力，直至变压吸附塔内压力接近大气压力，之后利用正在吸附的变压吸附塔产出的富氢气升压到高于2.0MPa，完成吸附剂的解析再生，变压吸附后脱附尾气排放到放空管线，始终有一个变压吸附塔正在吸附，其余变压吸附塔分别处于不同阶段的解析再生 。 The pressure swing adsorption is a continuously operating pressure swing adsorption composed of at least two pressure swing adsorption towers and at least one buffer tank. pressure swing adsorption tower. The valve between the saturated pressure swing adsorption tower and the degassing tank is opened, the pressure in the pressure swing adsorption tower begins to gradually drop to 1.0MPa±0.1MPa, and then the valve between the pressure swing adsorption tower and the desorption gas buffer tank is opened , further reduce the pressure in the pressure swing adsorption tower until the pressure in the pressure swing adsorption tower is close to the atmospheric pressure, and then use the hydrogen-rich gas produced by the pressure swing adsorption tower being adsorbed to increase the pressure to higher than 2.0MPa to complete the analytical regeneration of the adsorbent. After the pressure swing adsorption, the desorption tail gas is discharged to the vent pipeline. There is always one pressure swing adsorption tower being adsorbed, and the other pressure swing adsorption towers are in different stages of desorption regeneration .
  10. 如权利要求7~9所述的氢气回收方法在以复杂多变组分的瓦斯为原料气回收氢气中应用，其特征在于：所述复杂多变组分的瓦斯，是其组分包括氢、一氧化碳、二氧化碳和沸点相对高的碳氢类化合物的瓦斯，与其组分包括氢、一氧化碳、二氧化碳和沸点相对高的碳氢类化合物以及氧、氮和水、醇、醛氧化物的瓦斯中的一种。The method for recovering hydrogen as claimed in claims 7 to 9 is used in the recovery of hydrogen using gas with complex and variable components as raw material gas, characterized in that: the gas with complex and variable components is composed of hydrogen, Gases of carbon monoxide, carbon dioxide and hydrocarbons with relatively high boiling points, and one of the gas whose components include hydrogen, carbon monoxide, carbon dioxide and hydrocarbons with relatively high boiling points, oxygen, nitrogen and water, alcohols and aldehyde oxides kind.
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