CN216972005U - Hydrogen recovery system using gas as raw material gas - Google Patents
Hydrogen recovery system using gas as raw material gas Download PDFInfo
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- CN216972005U CN216972005U CN202121053476.3U CN202121053476U CN216972005U CN 216972005 U CN216972005 U CN 216972005U CN 202121053476 U CN202121053476 U CN 202121053476U CN 216972005 U CN216972005 U CN 216972005U
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Abstract
A hydrogen recovery system taking gas as raw material gas comprises a compression cooling and gas-liquid separation device, a membrane separation device and a pressure swing adsorption device, and also comprises a temperature swing adsorption device arranged between the compression cooling and gas-liquid separation device and the membrane separation device; the temperature swing adsorption device is a temperature swing adsorption device which adopts a redundant design and at least comprises two adsorption towers. The temperature swing adsorption with a redundant design is adopted, so that the dew point temperature is reduced by effectively utilizing lower energy consumption, the adverse effect of excessive high-boiling-point components in the gas with complicated and changeable components on the filtering membrane is reduced, and the subsequent membrane separation device is protected to the maximum extent. The membrane separation of at least two polyimide hollow fiber membranes in series/parallel combination with reasonable separation area and working pressure difference is adopted, so that the dew point temperature of the residual gas permeating the membrane separation device is effectively controlled to rise, and is at least 15 ℃ lower than the working temperature of the membrane separation device, so that the unification of hydrogen separation efficiency and safety is realized, and the service life of the separation membrane of the membrane separation device is prolonged.
Description
Technical Field
The utility model relates to hydrogen recovery, in particular to a hydrogen recovery system taking gas as raw material gas.
Background
Gas is a general term for gaseous fuel by the general public. The gas with complicated and changeable components is gas with complicated components and relatively large variation of the content of each component, wherein the content of hydrogen and methane can fluctuate within a range of +/-10% at any time, and the content of more than three of carbon monoxide, carbon dioxide and carbon can fluctuate within a range of +/-50% or even more. The existing hydrogen recovery method taking gas as raw material gas mainly comprises a membrane separation adsorption method, a pressure swing adsorption method and a freezing separation method, and for the gas with the hydrogen component content of less than 50 percent, complicated and variable components and difficult recovery, the membrane separation adsorption method has the defects that components with high dew point temperature can be gradually deposited in a separation membrane, the property of the separation membrane is changed, the membrane separation effect is influenced, and the operation period is short; the pressure swing adsorption method has the disadvantages of relatively low recovery ratio and poor economical efficiency; the freezing separation method has large equipment investment, the raw material gas needs deep pretreatment and the energy consumption is high.
Disclosure of Invention
The utility model aims to solve the technical problem of making up the defects in the prior art and provides a hydrogen recovery system taking gas as raw material gas.
The technical problem of the hydrogen recovery system using gas as raw material gas is solved by the following technical scheme.
The hydrogen recovery system using gas as raw material gas comprises a compression cooling and gas-liquid separation device, a membrane separation device and a pressure swing adsorption device, wherein the compression cooling and gas-liquid separation device is used for preparing high-pressure gas phase gas, the membrane separation device is used for obtaining high-hydrogen-content permeation gas, namely hydrogen-rich gas, at a low-pressure side, and obtaining low-hydrogen-content permeation residual gas at a high-pressure side, and the pressure swing adsorption device is used for carrying out pressure swing adsorption on the hydrogen-rich gas to prepare finished product hydrogen.
The hydrogen recovery system taking gas as raw material gas is characterized in that:
the temperature swing adsorption device is used for selectively adsorbing and removing part of components with higher boiling points and part of water from high-pressure gas phase, and effectively utilizes lower energy consumption to reduce the dew point temperature of the feed gas.
The technical problem of the hydrogen recovery system using gas as raw material gas is solved by the following further technical scheme.
The temperature swing adsorption device is a temperature swing adsorption device which is provided with at least two adsorption towers in a redundant design, so that the adverse effect of excessive components with higher boiling points in the gas with complicated and polytropic components on the filtering membrane is reduced.
Preferably, the temperature swing adsorption device is a double-tower temperature swing adsorption device, one adsorption tower is used for adsorption until saturation, the other adsorption tower is used for regeneration, the two adsorption towers are controlled and switched once by a valve every 3-8 hours, and a large residual adsorption capacity is reserved when the adsorption towers are switched every time so as to respond to the complex components of gas and the large content change of each component, so that the system has time to adjust and operate, the subsequent membrane separation device is protected to the maximum extent, the quality of product gas is kept stable, and the gas pressure in the temperature swing adsorption device is reduced to 0.02-0.10 Mpa.
The compression cooling and gas-liquid separation device is formed by sequentially connecting a gas-liquid separation front compressor, a gas-liquid separation front water cooler and a gas-liquid separation tank, wherein the gas-liquid separation front compressor is used for pressurizing feed gas to high-pressure gas-phase gas higher than 2.0MPa from an external system pressure, the gas-liquid separation front water cooler is used for cooling the high-pressure gas-phase gas to normal temperature or low temperature acceptable for measurement and calculation economy, the low temperature acceptable for measurement and calculation economy is 5-33 ℃, the gas-liquid separation tank is used for condensing, separating and separating out liquid drops with higher boiling points carried in the high-pressure gas-phase gas to prevent the liquid from entering a temperature-variable adsorption device, and the components with higher boiling points in the feed gas comprise more than three carbon components C3+And alcohols, ethers, the higher the boiling point of the component, the easier it is to adsorb.
The pre-gas-liquid separation compressor is at least a two-stage reciprocating compressor.
The water cooler before gas-liquid separation is a water-cooled heat exchanger which adopts 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 gas and a condensation surface, so that droplets with higher boiling points carried in high-pressure gas phase gas are enhanced to be condensed and separated out.
The membrane separation device comprises a temperature swing adsorption device, a membrane separation device and a pre-membrane separation heater, wherein the temperature swing adsorption device is used for outputting high-pressure gas to the membrane separation device, the pre-membrane separation heater is used for heating the high-pressure gas output by the temperature swing adsorption device to a working temperature required by the membrane separation device, and the precision filter is used for removing solid particles possibly contained in the heated high-pressure gas output by the temperature swing adsorption device.
The pre-membrane separation heater is one of a steam heater, a hot water heater, a hot oil heater and an electric heater.
The precision filter is a filter for filtering solid particles with the precision of 0.1 mu m.
The membrane separation device adopts at least two polyimide hollow fiber membrane strings/parallel combination membrane separation devices with reasonable design separation area and working pressure difference, effectively controls the rising of the dew point temperature of the residual gas permeating of the membrane separation device, and the dew point temperature of the residual gas permeating is at least 15 ℃ lower than the working temperature of the membrane separation device so as to realize the unification of hydrogen separation efficiency and safety and prolong the service life of the separation membrane of the membrane separation device.
The membrane separation device with be equipped with water cooler before membrane separation back water cooler, the pressure swing adsorption before compressor and the pressure swing adsorption in proper order between the pressure swing adsorption device, water cooler is used for the permeate gas with high hydrogenous behind the membrane separation, and the hydrogen-rich gas that prepares promptly cools off to the ordinary temperature for the first time, the compressor is used for cooling to the hydrogen-rich gas lifting pressure of ordinary temperature before the pressure swing adsorption, water cooler is used for cooling the hydrogen-rich gas of lifting pressure to the ordinary temperature once more before the pressure swing adsorption.
The water cooler after membrane separation is a water-cooled heat exchanger which adopts circulating water or chilled water as a cooling medium.
The pressure swing adsorption pre-compressor is one of at least two-stage reciprocating compressor and screw compressor.
The pressure swing adsorption front water cooler is a water-cooled heat exchanger which adopts circulating water or chilled water as a cooling medium.
The pressure swing adsorption device is a pressure swing adsorption device which is composed of at least two pressure swing adsorption towers and at least one buffer tank and can continuously run, hydrogen-rich gas sequentially enters the buffer tanks and then enters the pressure swing adsorption towers, an adsorbent in the pressure swing adsorption towers adsorbs part of gas including methane, carbon monoxide and carbon dioxide in raw material gas, the concentration of the hydrogen-rich gas flowing out is 90.0-99.9 mol%, the concentrations of the carbon monoxide and the carbon dioxide meet the requirements of downstream users, the mass percentage of the rest impurities which do not influence the downstream use is 0.1-10.0%, the finished product hydrogen flowing out from the outlet of the pressure swing adsorption towers enters a finished product gas buffer tank and finally is discharged out of a hydrogen recovery system and enters a hydrogen pipe network, after one pressure swing adsorption tower is saturated by adsorption, the raw material gas is introduced into the other regenerated pressure swing adsorption tower through a control valve, and a valve between the pressure swing adsorption tower which is saturated by adsorption and a downstream gas release tank is opened, the pressure in the pressure swing adsorption tower begins to gradually drop to 1.0MPa +/-0.1 MPa, then a valve between the pressure swing adsorption tower and the desorption gas buffer tank is opened, the pressure in the pressure swing adsorption tower is further reduced until the pressure in the pressure swing adsorption tower is close to atmospheric pressure, then the pressure is increased to be higher than 2.0MPa by utilizing the hydrogen-rich gas produced by the pressure swing adsorption tower which is adsorbing, the desorption regeneration of the adsorbent is completed, the desorption tail gas is discharged to an emptying pipeline after pressure swing adsorption, one pressure swing adsorption tower is always adsorbing, and the rest pressure swing adsorption towers are respectively in different stages of desorption regeneration.
The technical problem of the hydrogen recovery system using gas as raw material gas is solved by the following further technical scheme.
The hydrogen recovery method of the hydrogen recovery system using gas as raw material gas comprises the steps of preparing high-pressure gas phase gas by compression cooling and gas-liquid separation, preparing hydrogen-rich gas by membrane separation, and pressure swing adsorption to prepare the finished product hydrogen, and also comprises the steps of removing components with higher boiling points and part of water by the high-pressure gas phase gas through temperature swing adsorption, effectively utilizing lower energy consumption to reduce the dew point temperature, leading the proportion of the components with higher molecular weight to be subjected to temperature swing adsorption to be higher, then sequentially feeding the high-pressure gas phase gas subjected to temperature swing adsorption into a pre-membrane separation heater and a precision filter to be heated and finely filtered, so that the dew point temperature of the gas before being sent into the membrane separation device is far lower than the working temperature of the membrane separation device, the heavy hydrocarbon components and part of water subjected to temperature swing adsorption are discharged through a regeneration process of temperature swing adsorption treatment, and directly enter a fuel gas pipe network for other use or enter a liquefied gas absorption stabilizing system.
The temperature swing adsorption adopts the temperature swing adsorption of at least two adsorption towers with redundant design to reduce the adverse effect of excessive high-boiling-point components in the gas with complicated and changeable components on a filtering membrane, wherein one adsorption tower is used for adsorption, the other adsorption towers are used for regeneration, and a larger adsorption residual capacity is reserved during switching so as to deal with the complicated components of the gas and the large relative change of the content of each component, so that the system has time for adjusting operation, and the subsequent membrane separation device is protected to the maximum extent.
The heating and precise filtering are carried out by heating high-pressure gas phase gas to 50-90 ℃, precisely filtering by adopting a precise filter, and filtering out particle impurities in the gas and then feeding the gas into a membrane separation device.
The compression cooling and gas-liquid separation are used for preparing the high-pressure gas-phase gas, and the raw material gas is compressed into the high-pressure gas-phase gas and cooled, and then enters a gas-liquid separation tank to condense and separate out liquid drops with higher boiling points carried in the high-pressure gas-phase gas.
The raw material gas is compressed into high-pressure gas phase gas, and the raw material gas is pressurized to be higher than 2.0Mpa from the external system pressure by adopting a compressor before gas-liquid separation.
The high-pressure gas phase gas is cooled to normal temperature or low temperature acceptable for the calculation economy by adopting a water-cooled heat exchanger taking circulating water or chilled water as a cooling medium, wherein the low temperature acceptable for the calculation economy is 5-33 ℃.
The gas-liquid separation is carried out by adopting a gas-liquid separation tank with large contact area between gas and a condensing surface, so that the condensation and separation of liquid drops with higher boiling points carried in high-pressure gas phase are enhanced.
The membrane separation is used for preparing the hydrogen-rich gas, high-pressure gas phase gas subjected to temperature rise and gas-liquid separation is sent to a membrane separation device to be subjected to primary concentration through a separation membrane, and the hydrogen content output at the low-pressure side is 60mol percent
And (3) outputting low-hydrogen-content residual gas at a high-pressure side, sending the hydrogen-rich gas into a water cooler for cooling to normal temperature after membrane separation, and directly sending the residual gas into a fuel gas pipe network for other use or into a temperature swing adsorption device as regenerated gas.
The membrane separation is the membrane separation of at least two polyimide hollow fiber membrane series/parallel combination adopting reasonable design separation area and working pressure difference, the dew point temperature of the residual gas permeating of the membrane separation device is effectively controlled to rise, and the dew point temperature of the residual gas permeating is at least 15 ℃ lower than the working temperature of the membrane separation device, so that the unification of hydrogen separation efficiency and safety is realized, and the service life of the separation membrane of the membrane separation device is prolonged.
The pressure swing adsorption is used for preparing the finished product hydrogen, high-hydrogen-content permeation gas, namely hydrogen-rich gas is pressurized by a compressor before pressure swing adsorption, the pressure is increased to high-pressure hydrogen-rich gas, the high-pressure hydrogen-rich gas is sent into a water cooler before pressure swing adsorption to be cooled to normal temperature and then sent into a pressure swing adsorption device to be purified and concentrated again to the finished product hydrogen, the finished product hydrogen is refined to meet the subsequent production quality requirement, and low-pressure low-hydrogen-content analytic gas is pressurized by a tail gas compressor and then is discharged into a fuel gas pipe network for other use.
The compressor before pressure swing adsorption is used for pressurizing hydrogen-rich gas flowing out of the membrane separation device from 0.01-0.50 MPa to 1.8-6.0 MPa by adopting the compressor before pressure swing adsorption, and the outlet temperature of the compressor before pressure swing adsorption is 50 +/-30 ℃.
The water cooler before pressure swing adsorption is used for cooling high-pressure hydrogen-rich gas to normal temperature by adopting a water-cooled heat exchanger taking circulating water or chilled water as a cooling medium;
the pressure swing adsorption is pressure swing adsorption which is composed of at least two pressure swing adsorption towers and at least one buffer tank and can continuously operate, and after one pressure swing adsorption tower is saturated in adsorption, the feed gas is introduced into the other pressure swing adsorption tower after regeneration through a control valve. The valve between the pressure swing adsorption tower and the cis-venting tank which are saturated in adsorption is opened, the pressure in the pressure swing adsorption tower begins to gradually drop to 1.0MPa +/-0.1 MPa, then the valve between the pressure swing adsorption tower and the desorption gas buffer tank is opened, the pressure in the pressure swing adsorption tower is further reduced until the pressure in the pressure swing adsorption tower is close to the atmospheric pressure, then the pressure of the hydrogen-rich gas produced by the pressure swing adsorption tower which is adsorbing is increased to be higher than 2.0MPa, the desorption regeneration of the adsorbent is completed, the desorption tail gas is discharged to the venting pipeline after the pressure swing adsorption, one pressure swing adsorption tower is always adsorbing, and the rest pressure swing adsorption towers are respectively in the desorption regeneration in different stages.
The hydrogen recovery method is applied to the recovery of hydrogen by taking gas with complicated and changeful components as raw material gas, wherein the gas with complicated and changeful components comprises hydrogen, carbon monoxide, carbon dioxide and hydrocarbon compounds with relatively high boiling points, and the gas with complicated and changeful components comprises one of the hydrogen, the carbon monoxide, the carbon dioxide, the hydrocarbon compounds with relatively high boiling points, oxygen, nitrogen, water, alcohol and aldehyde oxide.
Compared with the prior art, the utility model has the beneficial effects that:
aiming at the gas with complicated and changeable components, the temperature swing adsorption with redundant design is adopted to remove the components with higher boiling points and part of water, the dew point temperature is effectively reduced by utilizing lower energy consumption, the adverse effect of excessive high-boiling-point components in the gas with complicated and changeable components on a filtering membrane is reduced, and the subsequent membrane separation device is protected to the maximum extent. By adopting the membrane separation of at least two polyimide hollow fiber membranes which are reasonably designed in separation area and working pressure difference and combined in series/in parallel, the dew point temperature of the residual gas permeating the membrane separation device is effectively increased, and is at least 15 ℃ lower than the working temperature of the membrane separation device, so that the unification of hydrogen separation efficiency and safety is realized, and the service life of the separation membrane of the membrane separation device is prolonged.
Drawings
FIG. 1 is a schematic composition diagram of an embodiment of the present invention.
The reference numerals of fig. 1 are as follows:
1-a gas-liquid separation pre-compressor; 2-a water cooler before gas-liquid separation; 3-a gas-liquid separation tank; 4-temperature swing adsorption device; 5-a pre-membrane separation heater; 6-precision filter; 7-a membrane separation device; 8-water cooler after membrane separation; 9-pressure swing adsorption front compressor; 10-a pressure swing adsorption front water cooler; 11-a pressure swing adsorption unit;
q1-gas input by compressor before gas-liquid separation; q2-output gas of compressor before gas-liquid separation; q3-output gas of the knockout drum; q4-high pressure gas phase gas output by the temperature swing adsorption device;
q5-desorbing the tail gas output by the temperature swing adsorption device; q6-output gas of heater before membrane separation; q7 — output gas of the precision filter; q8-residual gas output by the water cooler after membrane separation; q9-first enriched hydrogen-rich gas at the output of the membrane separation unit; q10-output gas of water cooler after membrane separation; q11-compressor output gas before pressure swing adsorption; q12-output gas of water cooler before pressure swing adsorption; q13-desorption tail gas output by the pressure swing adsorption device; q14-finished product hydrogen from the pressure swing adsorption unit.
Detailed Description
The present invention will be described in further detail with reference to the following detailed description and accompanying drawings. It should be emphasized that the following description is merely exemplary in nature and is not intended to limit the scope of the utility model or its application.
With reference to fig. 1, a non-limiting and non-exclusive embodiment will be described.
A hydrogen recovery system using gas as raw material gas for petrochemical enterprises in an attempt, the raw material gas is gas with hydrogen component content less than 50%, complex and variable components and difficult recovery, and the total gas quantity is 10000Nm3The components and the contents thereof are as follows:
hydrogen 40mol% (the content is unstable, and fluctuation of +/-10% can occur at any time);
30mol% of methane (the content is unstable, and fluctuation of +/-10% can occur at any time);
CO+CO25mol% (content is unstable, and + -50% or more amplitude may occurWave);
C3+ 5mol% (content is unstable, fluctuations of + -50% or even more can occur);
the other 20mol% (content is unstable, and fluctuation of + -10% occurs at any time).
The hydrogen recovery system according to the present embodiment is composed of, as shown in fig. 1, a compressor before gas-liquid separation 1, a water cooler before gas-liquid separation 2, a gas-liquid separation tank 3, a temperature swing adsorption device 4, a heater before membrane separation 5, a precision filter 6, a membrane separation device 7, a water cooler after membrane separation 8, a compressor before pressure swing adsorption 9, a water cooler before pressure swing adsorption 10, and a pressure swing adsorption device 11, which are connected in this order from left to right.
The method comprises the following steps that raw gas is pressurized to high-pressure gas phase gas higher than 2.8Mpa from an external system pressure through a gas-liquid separation front compressor 1, the gas-liquid separation front compressor 1 is a two-stage reciprocating compressor, then the temperature of the gas-liquid separation front water cooler 2 is reduced to normal temperature, at the moment, part of heavy hydrocarbon components are condensed into liquid, liquid drops with higher boiling points carried in the high-pressure gas phase gas are condensed and separated out through a gas-liquid separation tank 3, and the component C3 is separated out+The content of (b) is reduced from 5mol% to about 2.8mol% under the influence of equilibrium partial pressure, the temperature is normal temperature, and then the mixture is sent into a temperature swing adsorption device 4 for temperature swing adsorption.
The temperature swing adsorption device 4 is a double-tower adsorption type temperature swing adsorption device, when one temperature swing adsorption tower performs adsorption, the other temperature swing adsorption tower performs regeneration, the switching of the two temperature swing adsorption towers is controlled by a valve, the switching is performed every 5 hours, the product gas quality is kept stable, and C3 of the gas subjected to temperature swing adsorption+The further reduction in the content, in particular the higher the molecular weight component, the higher the proportion of temperature swing adsorption, the pressure drop being about 0.03 MPa. The temperature swing adsorption tower carries out analysis regeneration on the adsorbent by utilizing the high-temperature tail gas generated by the membrane separation device 7, the generated analysis temperature is about 70 ℃, the temperature can be raised by a reheater to enhance the regeneration capacity, and the gas flow is about 6000Nm at the moment3And the regenerated tail gas is subjected to temperature swing adsorption, and is decompressed to enter a gas pipe network. The high-pressure gas phase gas output by the temperature swing adsorption device 4 is heated by a heater 5 before membrane separationWhen the temperature reaches 75 ℃, the output high-temperature high-pressure gas phase enters a precision filter 6, and enters a membrane separation device 7 after particulate impurities in the gas are filtered.
The membrane separation device 7 adopts 10 polyimide hollow fiber membrane series/parallel combined membrane separation, the membrane wall of the polyimide hollow fiber membrane is provided with a microporous supporting layer and a compact layer with a separation function, the mixed gas is separated, the selectivity is high, the purity and the recovery rate are high, the corrosion resistance and the heat resistance are good, and the preparation method is that biphenyl tetracarboxylic dianhydride and aromatic diamine are subjected to polycondensation and are subjected to dry-wet spinning to obtain the composite material. The concentration of the primarily concentrated hydrogen-rich gas output after separation by the membrane separation device 7 is increased to 60-97 mol%, the concentration of methane is reduced to 5-20 mol%, and the concentrations of carbon monoxide and carbon dioxide are reduced to 1-97 mol%
2mol percent. The pressure of the hydrogen-rich gas is reduced to 0.1-0.5 MPa under the influence of membrane separation, and the flow rate is about 4000Nm3~5000Nm3After membrane separation, the water cooler 8 is cooled to normal temperature, low-temperature hydrogen-rich gas is obtained after cooling, the pressure of the compressor 9 is increased to 1.8 MPa-2.5 MPa before pressure swing adsorption, the compressor 9 is a two-stage reciprocating compressor before pressure swing adsorption, the outlet temperature of the compressor 9 before pressure swing adsorption reaches 70 ℃, and high-pressure hydrogen-rich gas is cooled to normal temperature by the water cooler 10 before pressure swing adsorption and then enters the pressure swing adsorption device 11 for further concentration. The pressure swing adsorption device 11 is a pressure swing adsorption device composed of six pressure swing adsorption towers and four buffer tanks, hydrogen-rich gas at normal temperature and high pressure sequentially enters the buffer tanks and then enters the pressure swing adsorption towers, and an adsorbent in the pressure swing adsorption towers adsorbs methane, carbon monoxide and other partial gases of carbon dioxide in the hydrogen-rich gas at normal temperature and high pressure.
The hydrogen concentration of the output finished product hydrogen is 90-99.9 mol%, the concentrations of carbon monoxide and carbon dioxide meet the requirements of downstream users, the mass percentage of the rest impurities which do not influence the downstream use is 0.1-10.0%, the finished product hydrogen flowing out of the outlet of the pressure swing adsorption tower enters a finished product gas buffer tank, and finally the finished product hydrogen is discharged from a hydrogen recovery system and enters a hydrogen pipe network.
When the pressure swing adsorption tower is saturated in adsorption, the raw material gas is introduced into the other regenerated pressure swing adsorption tower through the control valve. The valve between the pressure swing adsorption tower with saturated adsorption and the cis-venting gas tank is opened, the pressure in the pressure swing adsorption tower begins to gradually drop to 1.0MPa +/-0.1 MPa, then the valve between the pressure swing adsorption tower and the desorption gas buffer tank is opened, the pressure in the pressure swing adsorption tower is further reduced until the pressure in the pressure swing adsorption tower is close to the atmospheric pressure, then the pressure of the hydrogen-rich gas produced by the pressure swing adsorption tower which is adsorbing is increased to be higher than 2.0MPa, the desorption regeneration of the adsorbent is completed, the desorption tail gas output by the pressure swing adsorption device 11 is discharged to the venting pipeline, one pressure swing adsorption tower is always adsorbing in six pressure swing adsorption towers, one pressure swing adsorption tower completes the desorption regeneration, and other four pressure swing adsorption towers are respectively in the desorption regeneration in different stages.
The hydrogen recovery method of the embodiment comprises the following steps in sequence:
1) preparing high-pressure gas-phase gas by compressing and cooling feed gas and separating gas from liquid
The method comprises the steps of pressurizing feed gas into high-pressure gas-phase gas with the pressure higher than 2.0Mpa from an external system by a compressor before gas-liquid separation, cooling the high-pressure gas-phase gas to normal temperature by a water-cooled heat exchanger taking circulating water as a cooling medium, and finally performing gas-liquid separation by a gas-liquid separation tank with large contact area between gas and a condensation surface to condense and separate out liquid drops with higher boiling points carried in the high-pressure gas-phase gas;
2) removing components with higher boiling points and part of water by temperature swing adsorption of high-pressure gas phase gas
The method comprises the following steps of (1) adsorbing and removing components with higher boiling points and part of water in high-pressure gas phase by adopting an adsorbent in a temperature swing adsorption device, wherein the components with higher molecular weights are higher in the temperature swing adsorption proportion, the high-pressure gas phase subjected to temperature swing adsorption treatment is sequentially sent to a pre-membrane separation heater and a precision filter for heating and fine filtration, the content of the components with higher boiling points in raw material gas and the dew point temperature of the raw material gas are further reduced, so that the dew point temperature of the gas before being sent to a membrane separation device is far lower than the working temperature of the membrane separation device, and adsorbed heavy hydrocarbon components, namely desorption tail gas subjected to temperature swing adsorption and part of water are discharged through a regeneration process subjected to temperature swing adsorption treatment and directly enter a fuel gas pipe network for other use or enter a liquefied gas adsorption stabilizing system;
3) the high-pressure gas phase gas is subjected to membrane separation to prepare hydrogen-rich gas
Sending the high-pressure gas phase gas subjected to temperature rise and gas-liquid separation into a membrane separation device, carrying out primary concentration by a filter membrane, outputting high-hydrogen-containing permeation gas, namely hydrogen-rich gas, at a low-pressure side, outputting low-hydrogen-containing residual gas at a high-pressure side, sending the hydrogen-rich gas into a water cooler for cooling to normal temperature after membrane separation, and directly sending the residual gas into a fuel gas pipe network for other use or into a temperature swing adsorption device as regeneration gas;
4) the hydrogen-rich gas is subjected to pressure swing adsorption to prepare finished product hydrogen
The high-hydrogen-content permeation gas, namely hydrogen-rich gas, is pressurized by a compressor before pressure swing adsorption, the pressure is raised to high-pressure hydrogen-rich gas, the high-pressure hydrogen-rich gas is sent into a water cooler before pressure swing adsorption to be cooled to normal temperature and then sent into a pressure swing adsorption device to be purified and concentrated again to be finished hydrogen, the finished hydrogen is refined to meet the requirement of subsequent production quality, the hydrogen is boosted again and merged into a hydrogen pipe network, and low-pressure low-hydrogen-content analytic gas is pressurized by a tail gas compressor and then is discharged into a fuel gas pipe network for other use.
The raw material gas of the embodiment is gas with hydrogen component content less than 50%, complex and variable components and difficult recovery, the concentration of the recovered finished product hydrogen is 90.0-99.9 mol%, the concentrations of carbon monoxide and carbon dioxide meet the requirements of downstream users, and the hydrogen recovery rate exceeds 80%. The final hydrogen flow rate of the finished product discharged from the hydrogen recovery system and entering the hydrogen pipe network is about 4000Nm3。
The main energy consumption of the embodiment is steam and electric energy, the total electric energy consumption of the system is 1200 kilowatts, the low-pressure steam consumption is 0.3 ton/hour, the running cost of 100 percent pure hydrogen per 1 ton is about 2700 yuan/ton, and compared with the price of directly purchasing hydrogen to convert pure hydrogen to 20000 yuan/ton, the equivalent heat value benefit of reducing the hydrogen to be used as gas is deducted to 6000 yuan/ton, and the economic benefit of recovering hydrogen by the method and the system of the embodiment is about 13000 yuan/ton, according to the calculation of the electric charge of 0.69 yuan/kilowatt hour and the low-pressure steam of 240 yuan/ton and in consideration of other consumption of instrument gas and the like.
The trial working condition shows that the method and the system of the embodiment can stably and effectively recover the hydrogen in the gas with complex components for a long time, and realize low energy consumption and high yield.
The foregoing is a more detailed description of the utility model in connection with specific preferred embodiments and it is not intended that the utility model be limited to these specific details. For those skilled in the art to which the utility model pertains, several equivalent substitutions or obvious modifications, which are equivalent in performance or use, without departing from the inventive concept, should be considered as falling within the scope of the present invention as defined by the appended claims.
Claims (9)
1. The utility model provides an use hydrogen recovery system of gas as feed gas, includes compression cooling and gas-liquid separation device, membrane separation device and pressure swing adsorption equipment, its characterized in that:
the temperature swing adsorption device is arranged between the compression cooling and gas-liquid separation device and the membrane separation device;
the temperature swing adsorption device is a temperature swing adsorption device which is in a redundant design and at least comprises two adsorption towers.
2. A hydrogen recovery system as defined in claim 1, wherein:
the compression cooling and gas-liquid separation device is formed by sequentially connecting a gas-liquid separation front compressor, a gas-liquid separation front water cooler and a gas-liquid separation tank.
3. A hydrogen recovery system using a gas as a feed gas according to claim 2, wherein:
the gas-liquid separation front compressor is at least a two-stage reciprocating compressor;
the gas-liquid separation front water cooler is a water-cooled heat exchanger which adopts circulating water or chilled water as a cooling medium;
the gas-liquid separation tank is a gas-liquid separation tank with large contact area between gas and a condensation surface.
4. A hydrogen recovery system as defined in claim 1, wherein:
a pre-membrane separation heater and a precision filter are sequentially arranged between the temperature swing adsorption device and the membrane separation device.
5. A hydrogen recovery system as defined in claim 4 using gas as a feed gas, wherein:
the pre-membrane separation heater is one of a steam heater, a hot water heater, a hot oil heater and an electric heater;
the precision filter is a filter for filtering solid particles with the precision of 0.1 mu m.
6. A system for recovering hydrogen from a gas-fed gas as claimed in claim 1, wherein:
the membrane separation device is a membrane separation device which adopts at least two polyimide hollow fiber membranes with reasonably designed separation area and working pressure difference and is combined in series/in parallel.
7. A hydrogen recovery system as defined in claim 1, wherein:
and a water cooler after membrane separation, a compressor before pressure swing adsorption and a water cooler before pressure swing adsorption are sequentially arranged between the membrane separation device and the pressure swing adsorption device.
8. A hydrogen recovery system as defined in claim 7, wherein:
the water cooler after membrane separation is a water-cooled heat exchanger which adopts circulating water or chilled water as a cooling medium;
the pressure swing adsorption pre-compressor is one of at least two-stage reciprocating compressor and screw compressor;
the pressure swing adsorption front water cooler is a water-cooled heat exchanger which adopts circulating water or chilled water as a cooling medium.
9. A hydrogen recovery system as defined in claim 1, wherein:
the pressure swing adsorption device is a pressure swing adsorption device which consists of at least two pressure swing adsorption towers and at least one buffer tank and can continuously run.
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| CN113247861A (en) * | 2021-05-17 | 2021-08-13 | 广东赛瑞新能源有限公司 | Hydrogen recovery system using gas as raw material gas and recovery method and application thereof |
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2021
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113247861A (en) * | 2021-05-17 | 2021-08-13 | 广东赛瑞新能源有限公司 | Hydrogen recovery system using gas as raw material gas and recovery method and application thereof |
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