CN213679818U - Liquid carbon dioxide deep-cooling type pressure swing adsorption hydrogen purification system - Google Patents
Liquid carbon dioxide deep-cooling type pressure swing adsorption hydrogen purification system Download PDFInfo
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- CN213679818U CN213679818U CN202022579379.XU CN202022579379U CN213679818U CN 213679818 U CN213679818 U CN 213679818U CN 202022579379 U CN202022579379 U CN 202022579379U CN 213679818 U CN213679818 U CN 213679818U
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Abstract
The utility model relates to the technical field of gas purification, and discloses a liquid carbon dioxide deep-cooling pressure swing adsorption hydrogen purification system, which comprises a pretreatment unit, a carbon dioxide circulation unit, a product gas collection pipeline and a gas purification unit; the pretreatment unit comprises a filtering device, a first heat exchanger and a first hydrogen purity online analyzer which are sequentially connected; the gas purification unit comprises a pressure swing adsorption tower, a second heat exchanger and a second hydrogen purity online analyzer which are connected in sequence; the outlet end of the second hydrogen purity online analyzer of the previous gas purification unit is connected with the inlet end of the pressure swing adsorption tower of the next gas purification unit, and the outlet end of each second hydrogen purity online analyzer is connected with a product gas collecting pipeline. The beneficial effects are that: the nitrogen, carbon monoxide, carbon dioxide, methane, ethylene and the like in the industrial tail gas can be deeply removed in the pressure swing adsorption tower, and the product hydrogen with gradually increased purity is obtained.
Description
Technical Field
The utility model relates to a gas purification technical field, concretely relates to liquid carbon dioxide dark cold type pressure swing adsorption purification hydrogen system.
Background
A large amount of industrial tail gas rich in hydrogen is generated in the production processes of modern coal chemical industry, metallurgical industry, petroleum refining, sulfuric acid industry and the like. The industrial tail gas is directly discharged into the atmosphere, so that the atmosphere is polluted, and the hydrogen in the tail gas is wasted as high-quality clean energy. Therefore, the method for recovering and purifying the hydrogen in the industrial tail gas has important environmental protection value and economic value.
At present, the process for purifying hydrogen from industrial tail gas rich in hydrogen mainly comprises two processes, namely a cryogenic separation method and a pressure swing adsorption method. Based on different separation principles, the process characteristics of the raw materials are different remarkably, and the purity of the final product is also different greatly. The cryogenic separation method is characterized in that the separation is carried out by utilizing the difference of relative volatility of each component under the condition of low temperature, the process is simple, the treatment capacity is large, the product purity is high, and the cryogenic separation method is suitable for large-scale production, but water and carbon dioxide in feed gas must be removed to ensure that the content of the water and the carbon dioxide is less than 1ppm (volume ratio), otherwise, a guide pipe is easy to block at the low temperature. The pressure swing adsorption method is a new gas separation technology and widely applied, and the principle is that the adsorbent is used for selectively adsorbing gas impurities in industrial tail gas within a certain time to realize the enrichment of hydrogen in a gas phase, and the purification of the hydrogen is completed by combining the cyclic processes of pressure adsorption and reduced pressure desorption. The pressure swing adsorption process has the advantages of simple device, low energy consumption, large operation flexibility, high product hydrogen purity, complex flow in industrial application, large quantity of equipment, short service life of an adsorbent and a switching valve, high failure rate, poor reliability and low hydrogen recovery rate.
The two separation and purification processes have own characteristics and applicable raw materials, but for industrial tail gas rich in hydrogen, the pressure is low (0.4-0.7 MPa), the components are complex, the tail gas contains nitrogen, nitric oxide, nitrogen dioxide, methane, ethylene and the like, and the effect finally achieved by only adopting a single gas separation method has defects no matter cryogenic separation or pressure swing adsorption. If the two processes are combined according to the process characteristics and the specific engineering requirements, greater benefits can be obtained. The combined mode is practically applied in recent years, but the application examples are not many, and the combined mode mainly comprises cryogenic separation and pressure swing adsorption step-by-step treatment, and does not solve the problem of high investment of a cryogenic separation device when the raw material gas is directly subjected to cryogenic separation treatment.
SUMMERY OF THE UTILITY MODEL
The utility model aims at overcoming the not enough of above prior art existence, provide an adopt liquid carbon dioxide of productization to pressure swing adsorption bed and heat exchanger evaporation refrigeration, carry out the degree of depth desorption to nitrogen gas, carbon monoxide, carbon dioxide, methane and ethylene etc. in the industrial tail gas in the pressure swing adsorption tower, obtain the product hydrogen that the purity increases progressively step by step, reduce exhaust emission's liquid carbon dioxide cryrogenic formula pressure swing adsorption purification hydrogen system.
The purpose of the utility model is realized through the following technical scheme: a liquid carbon dioxide deep-cooling type pressure swing adsorption hydrogen purification system comprises a pretreatment unit, a carbon dioxide circulation unit, a product gas collection pipeline and a plurality of gas purification units; the pretreatment unit comprises a filtering device, a first heat exchanger and a first hydrogen purity online analyzer which are sequentially connected; the gas purification unit comprises a pressure swing adsorption tower, a second heat exchanger and a second hydrogen purity online analyzer which are connected in sequence; the outlet end of the first hydrogen purity online analyzer is connected with the inlet end of the pressure swing adsorption tower of the first gas purification unit, the outlet end of the second hydrogen purity online analyzer of the previous gas purification unit is connected with the inlet end of the pressure swing adsorption tower of the next gas purification unit, the outlet end of each second hydrogen purity online analyzer is connected with a product gas collection pipeline, and the carbon dioxide circulation unit is connected with the first heat exchanger, the pressure swing adsorption tower and the second heat exchanger.
Further, the device also comprises a desorption gas pipeline, a unit decompression pump, a maintenance control valve and a desorption control valve; the outlet end of the first hydrogen purity online analyzer, the outlet end of the second hydrogen purity online analyzer and the inlet end of the pressure swing adsorption tower are connected with a desorption gas pipeline, the unit pressure reduction pump is installed between the inlet end of the pressure swing adsorption tower and the desorption gas pipeline, the maintenance control valve is installed between the unit pressure reduction pump and the desorption gas pipeline, and the desorption control valve is installed between the unit pressure reduction pump and the inlet end of the pressure swing adsorption tower.
Furthermore, the system also comprises a program control three-way valve and a maintenance three-way valve; the outlet end of the first hydrogen purity online analyzer is connected with the inlet end of the pressure swing adsorption tower of the first gas purification unit and a desorption gas pipeline through a program-controlled three-way valve, a maintenance three-way valve is installed on the desorption gas pipeline, and the outlet end of the second hydrogen purity online analyzer in the previous gas purification unit is connected with the inlet end of the pressure swing adsorption tower in the next gas purification unit and the maintenance three-way valve through the program-controlled three-way valve.
Further, the system also comprises a main valve, a main decompression pump, a pressure gauge, a flowmeter, a raw material gas decompression valve and a product gas collection valve; the main valve and the main decompression pump are both arranged at the outlet end of the desorption gas pipeline; a pressure gauge and a flowmeter are arranged between the first heat exchanger and the first hydrogen purity online analyzer, and the pressure gauge is arranged at the inlet end of the pressure swing adsorption tower; a feed gas pressure reducing valve is arranged between the outlet end of the pressure swing adsorption tower and the inlet end of the second heat exchanger, and a product gas collecting valve is arranged on the product gas collecting pipeline.
Further, the carbon dioxide circulation unit comprises a carbon dioxide gas buffer tank, a carbon dioxide compressor, a liquid carbon dioxide pipeline, a gas carbon dioxide pipeline and a reflux carbon dioxide pipeline; the outlet end of the carbon dioxide gas buffer tank is respectively connected with the inlet ends of a reflux carbon dioxide pipeline and a carbon dioxide compressor, reflux carbon dioxide inlets of the first heat exchanger, the pressure swing adsorption tower and the second heat exchanger are respectively connected with the reflux carbon dioxide pipeline, the outlet end of the carbon dioxide compressor is connected with a liquid carbon dioxide pipeline, liquid carbon dioxide inlets of the first heat exchanger, the pressure swing adsorption tower and the second heat exchanger are respectively connected with the liquid carbon dioxide pipeline, and gaseous carbon dioxide outlets of the first heat exchanger, the pressure swing adsorption tower and the second heat exchanger are respectively connected with the inlet ends of the carbon dioxide gas buffer tank through a gas carbon dioxide pipeline.
Further, the device also comprises a liquid carbon dioxide pump, a liquid carbon dioxide control valve, a backflow carbon dioxide flowmeter and a carbon dioxide gas pressure reducing valve; the liquid carbon dioxide pump is arranged between the liquid carbon dioxide pipeline and the liquid carbon dioxide inlets of the first heat exchanger, each pressure swing adsorption tower and each second heat exchanger, and the liquid carbon dioxide control valve is arranged at the inlet end of each liquid carbon dioxide pump; the backflow carbon dioxide control valve and the backflow carbon dioxide flow meter are arranged among backflow carbon dioxide gas inlets of the first heat exchanger, the pressure swing adsorption towers and the second heat exchangers and backflow carbon dioxide pipelines; the carbon dioxide gas pressure reducing valve is arranged among the gaseous carbon dioxide outlets of the first heat exchanger, the pressure swing adsorption towers and the second heat exchangers and the gaseous carbon dioxide pipeline.
And the first heat exchanger, the second heat exchanger and a liquid carbon dioxide inlet of the pressure swing adsorption tower are connected with a liquid carbon dioxide pipeline through the pressure control unit.
Further, the first heat exchanger comprises a shell, a heat exchange unit and a first spraying unit; the heat exchange unit comprises a heat exchange tube and a fixed tube plate; the shell is internally provided with a first evaporation cavity, the fixed tube plates are respectively arranged at the upper end and the lower end of the first evaporation cavity and fixed on the shell, the heat exchange tube is arranged in the first evaporation cavity along the horizontal direction, and the two ends of the heat exchange tube are respectively connected with the two fixed tube plates; the first spraying unit comprises a first spraying main pipe and a first spraying pipe; the first spraying header pipe is fixed on the inner wall of the first evaporation cavity, the first spraying pipe is arranged in the horizontal direction and matched with the heat exchange pipe, one end of the first spraying pipe is connected with the first spraying header pipe, the other end of the first spraying pipe is sealed, and the first spraying pipe is provided with a plurality of first spraying holes facing the heat exchange pipe.
Further, the housing includes a case, a first cover plate, and a second cover plate; the area that the casing encloses is first evaporation chamber, fixed tube sheet is installed in the both ends of casing, first apron and second apron are detained and are located the both ends of casing to accompany the gasket between with fixed tube sheet, and realize sealedly through the bolt, first spray header near first apron setting, first apron open has the air inlet, and the second apron is opened there is the gas outlet, and the casing is opened has liquid carbon dioxide import, gaseous carbon dioxide export and backward flow carbon dioxide gas entry, liquid carbon dioxide import and first spray header intercommunication, the entry direction of backward flow carbon dioxide gas entry is tangent with the casing.
Further, the first spray header pipe comprises a main inlet pipe and a shunt pipe; the total vertical diameter setting of advancing the pipe along the shell is in first evaporation chamber, the one end of always advancing the pipe communicates with the liquid carbon dioxide import of shell, the total other end that advances the pipe seals, the axial symmetry parallel distribution of reposition of redundant personnel along always advancing the pipe is in the both sides of always advancing the pipe, and interval between two adjacent shunt tubes is corresponding with the heat exchange tube, the one end and the total pipe intercommunication of advancing of shunt tubes, its other end seal, first shower sets up along the horizontal direction, the one end and the total pipe or shunt tubes of advancing of first shower are connected, the other end of first shower seals.
Further, the pressure swing adsorption tower comprises a tower body, a second spraying unit and an adsorption unit; the interior of the tower body is provided with a second evaporation cavity, and the adsorption unit comprises an adsorption bed and an adsorption bed fixing plate; the adsorption bed fixing plates are fixed at the upper end and the lower end of the second evaporation cavity, the adsorption beds are distributed in the second evaporation cavity at intervals in parallel along the vertical direction, and the two ends of each adsorption bed are connected with the adsorption bed fixing plates; the second spraying unit comprises a second spraying main pipe, spraying branch pipes and a second spraying pipe; the second sprays the house steward and is the annular, the second sprays the house steward and is fixed in the second evaporation chamber to be located the below of top adsorption bed fixed plate, the second sprays the house steward and communicates with the liquid carbon dioxide entry of tower body, spray branch equidistant parallel distribution is in the second sprays house steward's annular region, and both ends all communicate with the second sprays the house steward, interval between the spray branch and the thickness one-to-one of adsorption bed, the second shower sets up along vertical direction, the one end and the second of second shower or spray branch intercommunication, its other end seal, the pipe shaft of second shower is opened has a plurality of second towards adsorption bed to spray the hole.
Furthermore, the second spraying unit also comprises a backflow carbon dioxide gas shunting device, and the backflow carbon dioxide gas shunting device comprises a shunting branch pipe and an annular shunting main pipe; the reposition of redundant personnel is responsible for and is fixed in the second evaporation chamber to be located between top adsorption bed fixed plate and the second spray header, equidistant parallel distribution of reposition of redundant personnel branch pipe is in the annular region that the reposition of redundant personnel was responsible for, and both ends all are responsible for the intercommunication with the reposition of redundant personnel, interval and adsorption bed's thickness one-to-one between the reposition of redundant personnel branch pipe, the reposition of redundant personnel is responsible for and the reposition of redundant personnel branch pipe has all opened a plurality of shunting hole.
Further, the tower body comprises a tower shell, an upper cover plate and a lower cover plate; the inner area of the tower shell is a second evaporation cavity, the adsorption bed fixing plates are respectively fixed at the upper end and the lower end of the tower shell, the upper cover plate and the lower cover plate are respectively buckled at the upper end and the lower end of the tower shell, gaskets are clamped between the upper cover plate and the corresponding adsorption bed fixing plates, sealing is realized through bolts, the lower cover plate is provided with a gas inlet, the upper cover plate is provided with a gas outlet, and the tower shell is provided with a liquid carbon dioxide inlet, a gaseous carbon dioxide outlet and a backflow carbon dioxide gas inlet; the liquid carbon dioxide inlet is communicated with the second spraying header pipe, the backflow carbon dioxide gas inlet is communicated with the flow dividing main pipe, and the gaseous carbon dioxide outlet is positioned at the bottom of the tower shell.
Compared with the prior art, the utility model have following advantage:
1. the utility model discloses be provided with preprocessing unit, a plurality of gaseous purification unit and carbon dioxide circulation unit, among the gaseous purification unit, the feed gas is after the purification of pressure swing adsorption tower, and again through the heat exchanger cooling processing, has improved the purification efficiency and the hydrogen purity of next purification unit. Liquid carbon dioxide is used for evaporation to cool the heat exchanger and the pressure swing adsorption tower, and the gas purification efficiency is effectively improved.
2. The adsorption bed in the pressure swing adsorption tower is cooled by liquid carbon dioxide evaporation, so that the adsorption capacity of the adsorbent to the non-hydrogen gas in the gas source is improved, and the service life of the adsorbent is prolonged; in the pressure swing adsorption tower, liquid carbon dioxide is sprayed to the outer surface of an adsorption bed, the temperature of the adsorption bed is adjusted to a set temperature during evaporation, in a heat exchanger, the liquid carbon dioxide is sprayed to the outer surface of a heat exchange tube and is vaporized under a set evaporation pressure, and the evaporation temperature is controllable, so that the temperature of the heat exchange tube is regulated and controlled, and gas is cooled; the gaseous carbon dioxide evaporated in the pressure swing adsorption tower and the heat exchanger passes through a reflux carbon dioxide gas pipeline, is regulated and controlled by a reflux carbon dioxide gas control valve and a flowmeter, and finally flows back to the pressure swing adsorption tower and the heat exchanger so as to promote the flow of the carbon dioxide gas in the tower and the heat exchanger and increase the heat transfer efficiency; the gas purification units are mutually independent and can be combined, increased and decreased according to needs, and partial unit adsorption purification, partial unit maintenance or partial unit desorption can be realized through the combination of the program control system, the program control three-way valve, the maintenance program control system, the maintenance three-way valve, the desorption control valve and the maintenance control valve; the purity of the hydrogen product after passing through the gas purification unit is gradually increased, and the purity can reach 99.9-99.9999%.
Drawings
The accompanying drawings, which form a part of the present application, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows a process flow diagram of a cryogenic pressure swing adsorption hydrogen purification system for liquid carbon dioxide according to the present invention;
FIG. 2 shows a process flow diagram of the pretreatment unit of FIG. 1;
FIG. 3 shows a process flow diagram for the pretreatment unit and the first three gas purification units of FIG. 1;
FIG. 4 shows a process flow diagram of the last gas purification unit and carbon dioxide recycle unit of FIG. 1;
fig. 5 shows a schematic structural diagram of a first heat exchanger according to the present invention;
FIG. 6 shows a schematic structural view of the fixed tube sheet of FIG. 5;
FIG. 7 shows a schematic view of the first shower header of FIG. 5;
FIG. 8 shows a cross-sectional view of the inlet for the return carbon dioxide gas of FIG. 5;
FIG. 9 shows a schematic diagram of a PSA column according to the present invention;
FIG. 10 is a schematic view showing the structure of the fixed plate of the adsorbent bed of FIG. 9;
FIG. 11 shows a schematic cross-sectional view of FIG. 9 at the liquid carbon dioxide inlet;
FIG. 12 shows a top view of the second spray unit of FIG. 9;
a cross-sectional view at the reflux carbon dioxide gas split device of fig. 9 is shown in fig. 13;
in the figure, 1 is a pretreatment unit; 101 is a filtering device; 102 is a first heat exchanger; 103 is a first hydrogen purity on-line analyzer; 2 is a gas purification unit; 201 is a pressure swing adsorption tower; 202 is a second heat exchanger; 203 is a second hydrogen purity on-line analyzer; 3 is a carbon dioxide circulating unit; 301 is a carbon dioxide buffer tank; 302 is a carbon dioxide compressor; 303 is a liquid carbon dioxide pipeline; 304 is a gaseous carbon dioxide pipeline; 305 is a return carbon dioxide line; 4 is a pressure control unit; 401 is a pressure sensor; 402 is a pressure sensing transmitter; 403 is a pressure controller; 404 is an electromagnetic valve; 7 is a desorption gas pipeline; 8 is a unit decompression pump; 9 is a maintenance control valve; 10 is a desorption control valve; 11 is a program control three-way valve; 12 is a maintenance three-way valve; 13 is a main valve; 14 is a total reduced pressure pump; 15 is a pressure gauge; 16 is a flow meter; 17 is a raw material gas pressure reducing valve; 18 is a product gas collection valve; 19 is a liquid carbon dioxide pump; 20 is a liquid carbon dioxide control valve; 21 is a reflux carbon dioxide control valve; 22 is a reflux carbon dioxide flowmeter; 23 is a carbon dioxide gas pressure reducing valve; 24 is a shell; 2401 is a first evaporation cavity; 2402 is a shell; 2403 is a first cover plate; 2404 is a second cover plate; 2405 is an air inlet; 2406 is an air outlet; 2407 is a half moon shaped plate; 25 is a heat exchange tube; 26 is a fixed tube plate; 2601 is a heat exchange tube mounting position; 27 is a first spray header; 2701 is a main inlet pipe; 2702 is a shunt tube; 28 is a first spray pipe; 29 is a liquid carbon dioxide inlet; 30 is a gaseous carbon dioxide outlet; 31 is a reflux carbon dioxide gas inlet; 32 is a tower body; 3201 is a second evaporation cavity; 3202 is a tower shell; 3203 is an upper cover plate; 3204 is a lower cover plate; 3205 is a gas inlet; 3206 is a gas outlet; 33 is an adsorption bed; 34 is an adsorption bed fixing plate; 35 is a second spray header; 36 is a spray branch pipe; 37 is a second spray pipe; 38 is a reflux carbon dioxide gas shunting device; 3801 is a shunt branch; 3802 is a main shunt tube.
Detailed Description
The present invention will be further explained with reference to the drawings and examples.
The liquid carbon dioxide deep-cooling pressure swing adsorption hydrogen purification system shown in fig. 1-4 comprises a pretreatment unit 1, a carbon dioxide circulation unit 3, a product gas collection pipeline and a plurality of gas purification units 2; the pretreatment unit 1 comprises a filtering device 101, a first heat exchanger 102 and a first hydrogen purity online analyzer 103 which are connected in sequence; the gas purification unit 2 comprises a pressure swing adsorption tower 201, a second heat exchanger 202 and a second hydrogen purity online analyzer 203 which are connected in sequence; the outlet end of the first hydrogen purity online analyzer 103 is connected with the inlet end of the pressure swing adsorption tower 201 of the first gas purification unit 2, the outlet end of the second hydrogen purity online analyzer 203 of the previous gas purification unit 2 is connected with the inlet end of the pressure swing adsorption tower 201 of the next gas purification unit 2, the outlet end of each second hydrogen purity online analyzer 203 is connected with a product gas collection pipeline, and the carbon dioxide circulation unit 3 is connected with the first heat exchanger 102, the pressure swing adsorption tower 201 and the second heat exchanger 202.
The feed gas optionally contains small amounts of nitrogen, carbon monoxide, and dioxygenA hydrogen-rich stream G0 of carbon, methane and ethylene; solid particles and water are removed from a hydrogen-rich gas flow G0 in a pretreatment unit 1 through a filtering device 101, the hydrogen-rich gas flow G0 is preliminarily pre-cooled in a first heat exchanger 102, after the change of the hydrogen purity in the gas is analyzed in real time through a first hydrogen purity online analyzer 103, the hydrogen-rich gas flow G0 enters a first gas purification unit 2, impurities in the hydrogen-rich gas flow are deeply removed in a pressure swing adsorption tower 201, the adsorbed hydrogen-rich gas flows through a raw gas pressure reducing valve 17 to be decompressed, enters a second heat exchanger 202, is cooled again, and is subjected to real-time analysis of the change of the hydrogen purity in the gas through a second hydrogen purity online analyzer 203 to obtain a hydrogen product, and the hydrogen product can also continue to enter a next gas purification unit for further purification treatment as in. Wherein, the filtering device 101 is an industrial filter, and can filter particle dust and suspended matters within the range of 1-5 μm. After the raw material gas is purified by the pressure swing adsorption tower 201, the temperature of the raw material gas is reduced by the second heat exchanger 202, so that the purification efficiency and the hydrogen purity of the next purification unit are improved. The first and second hydrogen purity on-line analyzers are mainly used for analyzing the hydrogen purity change in gas in real time, and the analysis precision is required to reach the volume percentage not less than 10-6. One or more adsorbents are filled in the pressure swing adsorption tower 201; the adsorbent can adopt silica gel, active carbon, zeolite, 5A molecular sieve, 13X type molecular sieve, alkaline earth metal modified molecular sieve and the like, and the filling amount of each tower is 1000 kg-5000 kg. The adsorbent in the adsorption tower is cooled by liquid carbon dioxide evaporation, so that the adsorption capacity of the adsorbent to the non-hydrogen gas in the gas source is improved, and the service life of the adsorbent is prolonged.
The device also comprises a desorption gas pipeline 7, a unit decompression pump 8, a maintenance control valve 9 and a desorption control valve 10; the outlet end of the first hydrogen purity online analyzer 103, the outlet end of the second hydrogen purity online analyzer 203 and the inlet end of the pressure swing adsorption tower 201 are all connected with a desorption gas pipeline 7, the unit pressure reducing pump 8 is installed between the inlet end of the pressure swing adsorption tower 201 and the desorption gas pipeline 7, the maintenance control valve 9 is installed between the unit pressure reducing pump 8 and the desorption gas pipeline 7, and the desorption control valve 10 is installed between the inlet ends of the unit pressure reducing pump 8 and the pressure swing adsorption tower 201.
The system also comprises a program control three-way valve 11 and a maintenance three-way valve 12; the outlet end of the first online hydrogen purity analyzer 103 is connected with the inlet end of the pressure swing adsorption tower 201 and the desorption gas pipeline 7 of the first gas purification unit 2 through a program-controlled three-way valve 11, a maintenance three-way valve 12 is installed in the desorption gas pipeline 7, and the outlet end of the second online hydrogen purity analyzer 203 in the previous gas purification unit is connected with the inlet end of the pressure swing adsorption tower 201 and the maintenance three-way valve 12 in the next gas purification unit through the program-controlled three-way valve 11.
The system also comprises a main valve 13, a main decompression pump 14, a pressure gauge 15, a flowmeter 16, a raw material gas decompression valve 17 and a product gas collection valve 18; the main valve 13 and the main decompression pump 14 are both arranged at the outlet end of the desorption gas pipeline; a pressure gauge 15 and a flowmeter 16 are arranged between the first heat exchanger 102 and the first hydrogen purity online analyzer 103, and the pressure gauge 15 is arranged at the inlet end of the pressure swing adsorption tower 201; a raw gas pressure reducing valve 17 is arranged between the outlet end of the pressure swing adsorption tower 201 and the inlet end of the second heat exchanger 202, and a product gas collecting valve 18 is arranged on a product gas collecting pipeline.
After the valves and the pipelines are arranged, the six gas purification units in the embodiment can be divided into independent modules, and the six gas purification units can be increased and decreased in a combined mode according to the process purification requirements. The pressure swing adsorption tower 201 controls the change of the pressure in the tower by the unit pressure reduction pump 8 by opening the desorption control valve 10 to promote the desorption and regeneration of the adsorbent, and the total pressure reduction pump 14 and the total valve 13 are opened only when the number of desorption adsorption towers is large. The six gas purification units 2 are in the working states of partial unit adsorption purification, partial unit overhaul or partial unit desorption and are controlled by a program control system and program control three-way valve 11, a maintenance program control system and maintenance three-way valve 12, a desorption control valve 10 and a maintenance control valve 9 in a combined mode.
When the six gas purification units normally operate, the desorption control valve 10 and the maintenance control valve 9 are both in a closed state, and the direction of the channel of the maintenance three-way valve 12 is the same as the direction of the desorption gas pipeline 7. When one unit in the gas purification unit 2 is desorbed or overhauled, other units can normally run, taking the desorption of the second gas purification unit as an example, a desorption control valve 10 in the second gas purification unit is opened, a maintenance control valve 9 is kept closed, and a unit decompression pump 8 is opened to desorb the pressure swing adsorption bed; and adjusting the channel directions of the program-controlled three-way valve 11 and the maintenance three-way valve 12 in the second and third gas purification units, wherein the product hydrogen of the first gas purification unit is used as a hydrogen-rich gas flow and enters a desorption gas pipeline through the program-controlled three-way valve 11 and the maintenance three-way valve 12 of the second gas purification unit, and then enters the third gas purification unit for further purification through the maintenance three-way valve 12 and the program-controlled three-way valve 11 of the third gas purification unit.
In the embodiment, six gas purification units 2 are arranged, and the purity of the hydrogen product after passing through the gas purification units is gradually increased, and can reach 99.9% -99.9999%: only the first gas purification unit is started, and the purity of the product hydrogen is 99.9%; starting the first two gas purification units, wherein the purity of the product hydrogen is 99.99%; starting the first four gas purification units, wherein the purity of the hydrogen product is 99.999%; all gas purification units are started, and the purity of the product hydrogen is 99.9999%.
As shown in fig. 1 and 4, the carbon dioxide circulation unit 3 includes a carbon dioxide gas buffer tank 301, a carbon dioxide compressor 302, a liquid carbon dioxide pipe 303, a gaseous carbon dioxide pipe 304, and a return carbon dioxide pipe 305; the outlet end of the carbon dioxide buffer tank 301 is respectively connected with the inlet ends of a reflux carbon dioxide pipeline 305 and a carbon dioxide compressor 302, reflux carbon dioxide inlets 31 of the first heat exchanger 102, the pressure swing adsorption tower 201 and the second heat exchanger 202 are all connected with the reflux carbon dioxide pipeline 305, the outlet end of the carbon dioxide compressor 302 is connected with a liquid carbon dioxide pipeline 303, liquid carbon dioxide inlets 29 of the first heat exchanger 102, the pressure swing adsorption tower 201 and the second heat exchanger 202 are all connected with the liquid carbon dioxide pipeline 303, and gaseous carbon dioxide outlets 30 of the first heat exchanger 102, the pressure swing adsorption tower 201 and the second heat exchanger 202 are all connected with the inlet end of the carbon dioxide buffer tank 301 through a gaseous carbon dioxide pipeline 304.
The device also comprises a liquid carbon dioxide pump 19, a liquid carbon dioxide control valve 20, a backflow carbon dioxide control valve 21, a backflow carbon dioxide flow meter 22 and a carbon dioxide gas pressure reducing valve 23; the liquid carbon dioxide pump 19 is arranged between the liquid carbon dioxide pipeline 303 and the liquid carbon dioxide inlet 29 of the first heat exchanger 102, each pressure swing adsorption tower 201 and each second heat exchanger 202, and the liquid carbon dioxide control valve 20 is arranged at the inlet end of each liquid carbon dioxide pump 19; the reflux carbon dioxide control valve 21 and the reflux carbon dioxide flow meter 22 are installed between the reflux carbon dioxide gas inlet 31 of the first heat exchanger 102, each pressure swing adsorption tower 201, each second heat exchanger 202 and the reflux carbon dioxide pipeline 305; the carbon dioxide gas pressure reducing valve 23 is installed between the gaseous carbon dioxide outlet 30 of the first heat exchanger 102, each pressure swing adsorption tower 201, each second heat exchanger 202, and the gaseous carbon dioxide pipeline 304.
The liquid carbon dioxide is derived from an existing cryogenic carbon dioxide product. The first heat exchanger, the second heat exchanger and the pressure swing adsorption tower 201 use liquid carbon dioxide for evaporation to provide cold energy; to reduce carbon dioxide emissions, all of the carbon dioxide is recycled in the carbon dioxide recycle unit 3. Liquid carbon dioxide is shunted in the carbon dioxide circulating unit 3 through a liquid carbon dioxide pipeline 303 and enters each gas purification unit through a liquid carbon dioxide control valve 20, and a liquid carbon dioxide pump 19 is arranged in the flow to promote the flow of the liquid carbon dioxide; the flow of the gaseous carbon dioxide generated after evaporation is as follows: gaseous carbon dioxide is regulated and decompressed by a carbon dioxide pressure reducing valve 23, and then enters a carbon dioxide buffer tank 301 through a gas carbon dioxide pipeline 304, wherein a part of carbon dioxide gas reflows to the pressure swing adsorption tower 201 and the first and second heat exchangers through a reflowing carbon dioxide gas pipeline 305, the other part of carbon dioxide gas reflows to a carbon dioxide compressor 302 through a pipeline, liquid carbon dioxide can be obtained after compression and cooling, and the part of liquid carbon dioxide reenters and circulates to provide cold energy through evaporation. The carbon dioxide gas of backward flow can promote the interior of tower and the interior carbon dioxide gas flow of heat exchanger, increases heat transfer efficiency.
The system also comprises a pressure control unit 4, and the first heat exchanger 102, the second heat exchanger 202 and the liquid carbon dioxide inlet 29 of the pressure swing adsorption tower 201 are all connected with a liquid carbon dioxide pipeline 303 through the pressure control unit 4. The pressure control unit 4 comprises a pressure sensor 401, a pressure sensor transmitter 402, a pressure controller 403 and an electromagnetic valve 404 which are connected in sequence; the electromagnetic valves 404 are respectively and correspondingly arranged at the liquid carbon dioxide inlets 29 of the first heat exchanger 102, the second heat exchanger 202 and the pressure swing adsorption tower 201, the pressure sensors 401 are arranged in the cavities of the first heat exchanger 102, the second heat exchanger 202 and the pressure swing adsorption tower 201, the opening degree of the electromagnetic valves 404 is determined by control signals sent by the pressure controller 403, and the control and measurement of the pressure controller 403 adopt proportional-derivative-integral control (PID). The pressure sensing transducer 402 is connected to a solenoid valve 404 through a pressure controller 403. Through setting up pressure control unit 4, can set up the gas pressure in heat exchanger and the pressure swing adsorption tower, regulate and control the evaporating temperature of liquid carbon dioxide, and then adjust the refrigeration temperature of heat exchanger, the temperature of adsorption bed.
As shown in fig. 5-8, the first heat exchanger 102 includes a housing 24, a heat exchange unit, and a first spray unit; the heat exchange unit comprises a heat exchange tube 25 and a fixed tube plate 26; the shell 24 is internally provided with a first evaporation cavity 2401, the fixed tube plates 25 are respectively fixed at the left end and the right end of the first evaporation cavity 2401 and are fixed on the shell 24, the heat exchange tubes 25 are arranged in the first evaporation cavity 2401 along the horizontal direction, and two ends of the heat exchange tubes 25 are respectively connected with the fixed tube plates 26; the first spray unit comprises a first spray header 27 and a first spray pipe 28; the first spraying header pipe 28 is fixed on the inner wall of the first evaporation cavity 2401, the first spraying pipe 28 is arranged along the horizontal direction and is matched with the heat exchange pipe 25, one end of the first spraying pipe 28 is connected with the first spraying header pipe 27, the other end of the first spraying pipe is sealed, and the first spraying pipe 28 is provided with a plurality of first spraying holes facing the heat exchange pipe 25. In the present embodiment, the second heat exchanger 202 has the same structure as the first heat exchanger 102. Liquid carbon dioxide is introduced into the heat exchanger to cool the heat exchange pipe, and the liquid carbon dioxide after absorbing heat is converted into gas to be discharged without being corroded or deposited in the heat exchanger.
The housing 24 includes a housing 2402, a first cover plate 2403, and a second cover plate 2404; the area enclosed by the shell 2402 is a first evaporation cavity 2401, the fixed tube plate 26 is installed at two ends of the shell 2402, the first cover plate 2403 and the second cover plate 2404 are buckled at two ends of the shell 2402, a gasket is clamped between the first cover plate 2403 and the fixed tube plate 26, locking and sealing are achieved through bolts, the area enclosed by the first cover plate 2403, the second cover plate 2404 and the fixed tube plate 26 is respectively communicated with two ends of the heat exchange tube 25, the first spray header 27 is arranged close to the first cover plate 2403, the first cover plate 2403 is provided with an air inlet 2405, the second cover plate is provided with an air outlet 2406, the shell 2402 is provided with a liquid carbon dioxide inlet 29, a gaseous carbon dioxide outlet 30 and a backflow carbon dioxide gas inlet 31, and the inlet direction of the backflow carbon dioxide gas inlet 31 is tangential to the shell 2402. The return carbon dioxide gas inlet is arranged close to the gas inlet 2405 and is positioned between the fixed tube plate 26 and the first spray header 27, and the distance between the fixed tube plate 26 and the inlet is 200 mm. By arranging the backflow carbon dioxide gas inlet 31 tangent to the shell 2402, the carbon dioxide gas flowing into the first evaporation cavity 2401 can form a spiral airflow in the first evaporation cavity 2401, fully disturb the gas flow in the first evaporation cavity 2401, disturb the heat exchange coefficient of the carbon dioxide gas side, strengthen heat transfer and improve heat transfer efficiency. The shell 2402 comprises two half-moon plates 2407 which are buckled up and down, the two half-moon plates 2407 are sealed through an outer pipe flange and a sealing gasket, an area enclosed by the two half-moon plates 2407 is a first evaporation cavity 2401, the half-moon plate 2407 positioned above is provided with a liquid carbon dioxide inlet 29, the half-moon plate 2407 positioned below is provided with a gaseous carbon dioxide outlet 30 and a backflow carbon dioxide inlet 31, the backflow carbon dioxide inlet 31 and the liquid carbon dioxide inlet 29 are close to a first cover plate 2403, the inlet direction of the backflow carbon dioxide inlet 31 is tangent to the half-moon plates 2407, and the gaseous carbon dioxide outlet 30 is close to a second cover plate 2404.
As shown in fig. 6, a plurality of heat exchange tube mounting positions 2601 are arranged on the plate surface of the fixed tube plate 26, the heat exchange tube mounting positions 2601 are arranged in layers along the vertical direction, in this embodiment, the distance between straight lines where the centers of circles of two adjacent layers of heat exchange tube mounting positions 2601 are located is 140mm, and the heat exchange tube mounting positions 2601 of the same layer are symmetrically distributed along the vertical diameter of the shell 24. The heat exchange tubes 25 are horizontally provided with 5-11 layers, the distance between straight lines where circle centers of the upper and lower adjacent layers of heat exchange tubes 25 are located is 140-160 mm, and the minimum distance between the outer walls of the adjacent tubes in the layers is 10-20 mm. In this embodiment: the heat exchange tubes 25 are horizontally provided with five layers, the heat exchange tubes 25 in the layers are symmetrically distributed by taking the vertical diameter of the shell 24 as a symmetry axis, the minimum distance between the outer walls of the left and right tubes is 210mm, and an installation space is reserved for the main inlet tube 2701 of the first spray header 27. The heat exchange tube 25 has an inner diameter of 60mm and a wall thickness of 3 mm.
The first spray header 27 comprises a main inlet pipe 2701 and a shunt pipe 2702; the main inlet pipe 2701 is arranged in the first evaporation cavity 2401 along the vertical diameter of the shell 24, one end of the main inlet pipe 2701 is communicated with the liquid carbon dioxide inlet 29 of the shell 24, the other end of the main inlet pipe 2701 is closed, the shunt pipes 2702 are symmetrically distributed on two sides of the main inlet pipe 2701 in parallel along the axial direction of the main inlet pipe 2701, the interval between two adjacent shunt pipes 2702 corresponds to the heat exchange pipe 25, one end of the shunt pipe 2702 is communicated with the main inlet pipe 2701, the other end of the shunt pipe is closed, the first spray pipe 28 is arranged along the horizontal direction, one end of the first spray pipe 28 is connected with the main inlet pipe 2701 or the shunt pipe 2702, and the other end of the first spray pipe 28 is closed. In this embodiment, the diameter of the inlet pipe 2701 is 90mm, the diameter of the branch pipe 2702 is 50mm, and the diameter of the first spray pipe 28 is 20 mm. The pipe body of the first spraying pipe 28 is opposite to one side of the heat exchange pipe 25, first spraying holes are uniformly distributed in a 120-degree range, and waste of liquid carbon dioxide can be reduced while sufficient heat exchange is achieved.
The flow of the hydrogen-rich gas to be cooled in the heat exchanger is as follows: the hydrogen-rich gas to be cooled enters the heat exchange tube 25 of the heat exchanger through the gas inlet 2405, and after heat exchange is carried out between the hydrogen-rich gas and liquid carbon dioxide on the outer surface of the heat exchange tube 25, the temperature is reduced, and the hydrogen-rich gas leaves the heat exchanger through the gas outlet 2406 and enters the hydrogen purity online analyzer 203. The flow of the carbon dioxide in the heat exchanger is as follows: liquid carbon dioxide enters the heat exchanger through the liquid carbon dioxide inlet 29, the flow rate of the liquid carbon dioxide is controlled by the pressure control unit 4, the liquid carbon dioxide is shunted to the first sprinkling pipe 28 through the main inlet pipe 2701 and the shunt pipe 2702 in the heat exchanger, first sprinkling holes are distributed on the first sprinkling pipe 28, the liquid carbon dioxide is evenly sprinkled on the outer surface of the heat exchange pipe 25 through the first sprinkling holes, and the heat of hydrogen-rich gas in the heat exchange pipe 25 is absorbed in the evaporation process. In the process, the left end of the first evaporation cavity 2401 is provided with a backflow carbon dioxide gas inlet 31 pipeline which is tangent to the heat exchanger shell 2402, gaseous carbon dioxide generated by evaporation flows back into the heat exchanger through the backflow carbon dioxide gas inlet 31, and the airflow can form rotary airflow in the first evaporation cavity 2401 to promote the flow of the gaseous carbon dioxide in the first evaporation cavity 2401, so that the evaporation speed of the liquid carbon dioxide is improved; the gaseous carbon dioxide produced by the evaporation and reflux exits the heat exchanger through gaseous carbon dioxide outlet 30.
As shown in fig. 9-13, the pressure swing adsorption tower 201 includes a tower body 32, a second spray unit, and an adsorption unit; the tower body 32 is internally provided with a second evaporation cavity 3201, and the adsorption unit comprises an adsorption bed 33 and an adsorption bed fixing plate 34; the adsorption bed fixing plates 34 are fixed at the upper end and the lower end of the second evaporation cavity 3201, the adsorption beds 33 are distributed in the second evaporation cavity 3201 at intervals in the vertical direction in parallel, and the two ends of the adsorption beds 33 are connected with the adsorption bed fixing plates 34; the second spraying unit comprises a second spraying header pipe 35, spraying branch pipes 36 and a second spraying pipe 37; the second spray header 35 is the annular, the second spray header 35 is fixed in the second evaporation chamber 3401 to be located the below of top adsorption bed fixed plate 34, the second spray header 35 communicates with the liquid carbon dioxide entry 29 of tower body 32, spray branch 36 equidistant parallel distribution is in the annular region of second spray header 35, and both ends all communicate with second spray header 35, and interval between spray branch 36 and adsorption bed 33's thickness one-to-one, and the adsorption bed 33 correspondence that the interval was arranged passes the interval between spray branch 36, second spray header 37 sets up along vertical direction, the one end and the second spray header 35 of second spray header 37 or spray branch 36 intercommunication, and its other end is sealed, second spray header 37's pipe shaft is opened a plurality of second spray holes towards adsorption bed 33. The pipe body of the second spraying pipe 37 is opposite to the side of the adsorption bed, and second spraying holes are uniformly distributed in a 120-degree range, and the diameter of each second spraying hole is 1 mm.
The second spraying unit further comprises a backflow carbon dioxide gas shunting device 38, and the backflow carbon dioxide gas shunting device 38 comprises a shunting branch pipe 3801 and an annular shunting main pipe 3802; the main shunting pipe 3802 is fixed in the second evaporation cavity 3201 and is positioned between the upper adsorption bed fixing plate 34 and the second spraying header 35, the shunting branch pipes 3801 are equidistantly and parallelly distributed in an annular area of the main shunting pipe 3802, both ends of each shunting branch pipe 3802 are communicated with the main shunting pipe 3802, the intervals between the shunting branch pipes 3801 correspond to the thicknesses of the adsorption beds 33 one by one, a plurality of shunting holes are respectively formed in the lower half parts of the main shunting pipe 3802 and the shunting branch pipes 3801, and the diameters of the shunting holes are 0.5 mm. The returned carbon dioxide gas flows into the second evaporation chamber 3201 through the diversion holes to promote the evaporation heat transfer of the liquid carbon dioxide.
The tower body 32 includes a tower casing 3202, an upper cover plate 3203, and a lower cover plate 3204; the inner area of the tower casing 3202 is a second evaporation chamber 3201, the adsorption bed fixing plates 34 are respectively fixed at the upper and lower ends of the tower casing 32, the upper cover plate 3203 and the lower cover plate 3204 are respectively buckled at the upper and lower ends of the tower casing 3202, and a gasket is clamped between the adsorption bed fixing plates 34 and the corresponding adsorption bed fixing plates to realize sealing through bolt connection, the lower cover plate 3204 is provided with a gas inlet 3205, the upper cover plate 3203 is provided with a gas outlet 3206, and the tower casing 3202 is provided with a liquid carbon dioxide inlet 29, a gaseous carbon dioxide outlet 30 and a reflux carbon dioxide gas inlet 31; the liquid carbon dioxide inlet 29 is communicated with the second spraying header pipe 35, the electromagnetic valve 404 of the pressure control unit 4 is installed on a pipeline of the liquid carbon dioxide inlet 29, the pressure sensor 401 is connected with the second evaporation cavity 3201, the backflow carbon dioxide gas inlet 31 is communicated with the diversion main pipe 3802, and the gaseous carbon dioxide outlet 30 is located at the bottom of the tower shell 3202.
The tower further comprises a liquid carbon dioxide pump 19, a liquid carbon dioxide return port is formed in the bottom end of the tower casing 3202 and is communicated with the liquid carbon dioxide inlet 29 through a pipeline, and the liquid carbon dioxide pump 19 is installed on the pipeline. Through this setting, the liquid carbon dioxide that does not evaporate is recycled, and when resources are saved, cleanness in the adsorption tower can also be guaranteed.
The pressure control unit 4 may set an evaporation pressure value of the carbon dioxide gas in the second evaporation cavity 3201, so that the liquid carbon dioxide is evaporated under a set pressure, and an evaporation temperature of the liquid carbon dioxide is controlled, thereby controlling a refrigeration temperature of the pressure swing adsorption bed.
The flow of the hydrogen-rich gas to be adsorbed and purified in the pressure swing adsorption tower 201 is as follows: the hydrogen-rich gas to be adsorbed and purified enters the pressure swing adsorption tower 201 through the gas inlet 3205, and is adsorbed and purified in each adsorption bed 33, and the hydrogen-rich gas after adsorption leaves the pressure swing adsorption tower 201 through the gas outlet 3206. The flow of carbon dioxide in the pressure swing adsorption tower 201 is as follows: liquid carbon dioxide enters the pressure swing adsorption tower 201 through the liquid carbon dioxide inlet 29, the flow rate of the liquid carbon dioxide is controlled by the pressure control unit 4, in the pressure swing adsorption tower 201, the liquid carbon dioxide flows in through the second spraying header pipe 35, one part of the liquid carbon dioxide directly enters the second spraying pipe 37, the other part of the liquid carbon dioxide is dispersed into the spraying branch pipe 36 and then enters the second spraying pipe 37, the second spraying pipe 37 is provided with second spraying holes, the liquid carbon dioxide is uniformly sprayed on the outer surface of the adsorption bed 33 through the second spraying holes, the heat emitted in the adsorption process in the adsorption bed 33 is absorbed in the evaporation process, the heat exchange is realized, and the temperature of the adsorbent in the adsorption bed 33 is reduced. In this process, the gaseous carbon dioxide generated by evaporation flows back into the tower through the reflux carbon dioxide gas inlet 31 and then is dispersed into the second evaporation chamber 3201 from the reflux carbon dioxide splitter plate 38, and this gas flow can promote the flow of the gaseous carbon dioxide in the second evaporation chamber 3201, thereby increasing the evaporation rate of the liquid carbon dioxide. The gaseous carbon dioxide produced by the evaporation and reflux exits the pressure swing adsorption bed 201 from the gaseous carbon dioxide outlet 30; the liquid carbon dioxide droplets which are not evaporated fall to the bottom of the second evaporation cavity 3201, and are pumped to the liquid carbon dioxide inlet 29 by the liquid carbon dioxide pump 19 for recycling.
The utility model discloses the scheme adopts liquid carbon dioxide evaporation to refrigerate pressure swing adsorption bed and heat exchanger, and raw materials sources is wide, and the heat loss is few, and air pollution is little, and the product hydrogen purity that obtains is controllable and various. Compared with the traditional pressure swing adsorption hydrogen purification method, the scheme adds the liquid carbon dioxide evaporation to provide cold energy, and improves the adsorption capacity of the adsorbent to the non-hydrogen part gas in the gas sourceThe hydrogen recovery rate reaches more than 95 percent. Taking a refinery tail gas as an example, the hydrogen in the tail gas is directly purified by using the traditional pressure swing adsorption method, and the recovered waste gas is about 28000Nm3At/h, about 6385Nm of product hydrogen can be obtained3The maximum purity can only reach 97.71 percent in the hydrogen recovery rate of 70 percent, and the product hydrogen can be obtained by about 8848Nm when the process scheme is used for recovering purified hydrogen3The hydrogen recovery rate can reach 97 percent, the purity can reach 99.9999 percent, and the hydrogen recovery amount is increased by about 2463Nm3The annual operating time is 7000h, and the annual recovered hydrogen amount is increased by about 1724.1 ten thousand Nm3At 1.75 yuan/Nm3The cost of hydrogen gas is calculated, and the economic benefit is about 3017.2 ten thousand yuan per year. Therefore, the process is effectively and secondarily utilizes a large amount of industrial hydrogen-rich tail gas, improves the recovery efficiency of hydrogen in the tail gas, saves hydrogen resources, reduces environmental pollution, generates better economic benefit and social benefit, and has good application prospect.
The above-mentioned specific implementation is the preferred embodiment of the present invention, can not be right the utility model discloses the limit, any other does not deviate from the technical scheme of the utility model and the change or other equivalent replacement modes of doing all contain within the scope of protection of the utility model.
Claims (10)
1. The utility model provides a liquid carbon dioxide deep-cooling formula pressure swing adsorption purification hydrogen system which characterized in that: the system comprises a pretreatment unit, a carbon dioxide circulation unit, a product gas collection pipeline and a plurality of gas purification units; the pretreatment unit comprises a filtering device, a first heat exchanger and a first hydrogen purity online analyzer which are sequentially connected; the gas purification unit comprises a pressure swing adsorption tower, a second heat exchanger and a second hydrogen purity online analyzer which are connected in sequence; the outlet end of the first hydrogen purity online analyzer is connected with the inlet end of the pressure swing adsorption tower of the first gas purification unit, the outlet end of the second hydrogen purity online analyzer of the previous gas purification unit is connected with the inlet end of the pressure swing adsorption tower of the next gas purification unit, the outlet end of each second hydrogen purity online analyzer is connected with a product gas collection pipeline, and the carbon dioxide circulation unit is connected with the first heat exchanger, the pressure swing adsorption tower and the second heat exchanger.
2. The liquid carbon dioxide deep-cooling pressure swing adsorption purification hydrogen system of claim 1, characterized in that: the device also comprises a desorption gas pipeline, a unit decompression pump, a maintenance control valve and a desorption control valve; the outlet end of the first hydrogen purity online analyzer, the outlet end of the second hydrogen purity online analyzer and the inlet end of the pressure swing adsorption tower are connected with a desorption gas pipeline, the unit pressure reduction pump is installed between the inlet end of the pressure swing adsorption tower and the desorption gas pipeline, the maintenance control valve is installed between the unit pressure reduction pump and the desorption gas pipeline, and the desorption control valve is installed between the unit pressure reduction pump and the inlet end of the pressure swing adsorption tower.
3. The liquid carbon dioxide deep-cooling pressure swing adsorption purification hydrogen system of claim 1, characterized in that: the carbon dioxide circulating unit comprises a carbon dioxide gas buffer tank, a carbon dioxide compressor, a liquid carbon dioxide pipeline, a gas carbon dioxide pipeline and a backflow carbon dioxide pipeline; the outlet end of the carbon dioxide gas buffer tank is respectively connected with the inlet ends of a reflux carbon dioxide pipeline and a carbon dioxide compressor, reflux carbon dioxide inlets of the first heat exchanger, the pressure swing adsorption tower and the second heat exchanger are respectively connected with the reflux carbon dioxide pipeline, the outlet end of the carbon dioxide compressor is connected with a liquid carbon dioxide pipeline, liquid carbon dioxide inlets of the first heat exchanger, the pressure swing adsorption tower and the second heat exchanger are respectively connected with the liquid carbon dioxide pipeline, and gaseous carbon dioxide outlets of the first heat exchanger, the pressure swing adsorption tower and the second heat exchanger are respectively connected with the inlet ends of the carbon dioxide gas buffer tank through a gas carbon dioxide pipeline.
4. The liquid carbon dioxide deep-cooling pressure swing adsorption purification hydrogen system of claim 1, characterized in that: the first heat exchanger, the second heat exchanger and the liquid carbon dioxide inlet of the pressure swing adsorption tower are all connected with a liquid carbon dioxide pipeline through the pressure control unit.
5. The liquid carbon dioxide deep-cooling pressure swing adsorption purification hydrogen system of claim 1, characterized in that: the first heat exchanger comprises a shell, a heat exchange unit and a first spraying unit; the heat exchange unit comprises a heat exchange tube and a fixed tube plate; the shell is internally provided with a first evaporation cavity, the fixed tube plates are respectively arranged at two ends of the evaporation cavity and fixed on the shell, the heat exchange tube is arranged in the first evaporation cavity along the horizontal direction, and two ends of the heat exchange tube are respectively connected with the two fixed tube plates; the first spraying unit comprises a first spraying main pipe and a first spraying pipe; the first spraying header pipe is fixed on the inner wall of the first evaporation cavity, the first spraying pipe is arranged in the horizontal direction and matched with the heat exchange pipe, one end of the first spraying pipe is connected with the first spraying header pipe, the other end of the first spraying pipe is sealed, and the first spraying pipe is provided with a plurality of first spraying holes facing the heat exchange pipe.
6. The cryogenic pressure swing adsorption hydrogen purification system for liquid carbon dioxide according to claim 5, characterized in that: the shell comprises a shell body, a first cover plate and a second cover plate; the region that the casing encloses is first evaporation chamber, fixed tube sheet is installed in the both ends of casing, first apron and second apron are detained respectively and are located the casing both ends of controlling to accompany the gasket between with fixed tube sheet, realize sealedly through the bolt, first spray header near first apron setting, first apron open has the air inlet, and second apron opens there is the gas outlet, and the casing is opened there is liquid carbon dioxide import, gaseous carbon dioxide export and backward flow carbon dioxide gas entry, liquid carbon dioxide import and first spray header intercommunication, the entry direction of backward flow carbon dioxide gas entry is tangent with the casing.
7. The cryogenic pressure swing adsorption hydrogen purification system for liquid carbon dioxide according to claim 5, characterized in that: the first spray header pipe comprises a main inlet pipe and a shunt pipe; the total vertical diameter setting of advancing the pipe along the shell is in the evaporation chamber, the total one end of advancing the pipe communicates with the liquid carbon dioxide import of shell, the total other end that advances the pipe seals, the axial symmetry parallel distribution that the shunt tubes advances the pipe along the total both sides of advancing the pipe, and interval between two upper and lower adjacent shunt tubes is corresponding with the heat exchange tube, the one end and the total pipe intercommunication of advancing of shunt tubes, its other end seal, first shower sets up along the horizontal direction, the one end and the total pipe or shunt tubes of advancing of first shower are connected, the other end of first shower seals.
8. The liquid carbon dioxide deep-cooling pressure swing adsorption purification hydrogen system of claim 1, characterized in that: the pressure swing adsorption tower comprises a tower body, a second spraying unit and an adsorption unit; the interior of the tower body is provided with a second evaporation cavity, and the adsorption unit comprises an adsorption bed and an adsorption bed fixing plate; the adsorption bed fixing plates are fixed at the upper end and the lower end of the second evaporation cavity, the adsorption beds are distributed in the second evaporation cavity at equal intervals in the vertical direction in parallel, and the two ends of each adsorption bed are connected with the adsorption bed fixing plates; the second spraying unit comprises a second spraying main pipe, spraying branch pipes and a second spraying pipe; the second sprays the house steward and is the annular, the second sprays in house steward is fixed in the second evaporation chamber to be located the below of top adsorption bed fixed plate, spray branch pipe equidistant parallel distribution sprays the house steward in the second annular region, and both ends all spray house steward intercommunication with the second, interval and the thickness one-to-one of adsorption bed between the spray branch pipe, the second shower sets up along vertical direction, the one end and the second of second shower spray house steward or spray branch pipe intercommunication, its other end is sealed, the pipe shaft of second shower is opened has a plurality of second towards the adsorption bed and is sprayed the hole.
9. The cryogenic pressure swing adsorption hydrogen purification system for liquid carbon dioxide according to claim 8, wherein: the second spraying unit also comprises a backflow carbon dioxide gas shunting device, and the backflow carbon dioxide gas shunting device comprises a shunting branch pipe and an annular shunting main pipe; the reposition of redundant personnel is responsible for and is fixed in the second evaporation chamber to be located between top adsorption bed fixed plate and the second spray header, equidistant parallel distribution of reposition of redundant personnel branch pipe is in the annular region that the reposition of redundant personnel was responsible for, and both ends all are responsible for the intercommunication with the reposition of redundant personnel, interval and adsorption bed's thickness one-to-one between the reposition of redundant personnel branch pipe, the reposition of redundant personnel is responsible for and the reposition of redundant personnel branch pipe has all opened a plurality of shunting hole.
10. The cryogenic pressure swing adsorption hydrogen purification system for liquid carbon dioxide according to claim 8, wherein: the tower body comprises a tower shell, an upper cover plate and a lower cover plate; the inner area of the tower shell is a second evaporation cavity, the adsorption bed fixing plates are respectively fixed at the upper end and the lower end of the tower shell, the upper cover plate and the lower cover plate are respectively buckled at the upper end and the lower end of the tower shell, gaskets are clamped between the upper cover plate and the corresponding adsorption bed fixing plates, sealing is realized through bolts, the lower cover plate is provided with a gas inlet, the upper cover plate is provided with a gas outlet, and the tower shell is provided with a liquid carbon dioxide inlet, a gaseous carbon dioxide outlet and a backflow carbon dioxide gas inlet; the liquid carbon dioxide inlet is communicated with the second spraying header pipe, the backflow carbon dioxide gas inlet is communicated with the flow dividing main pipe, and the gaseous carbon dioxide outlet is positioned at the bottom of the tower shell.
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| CN112239197A (en) * | 2020-11-10 | 2021-01-19 | 惠州市华达通气体制造股份有限公司 | Liquid carbon dioxide deep-cooling type pressure swing adsorption hydrogen purification system |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112239197A (en) * | 2020-11-10 | 2021-01-19 | 惠州市华达通气体制造股份有限公司 | Liquid carbon dioxide deep-cooling type pressure swing adsorption hydrogen purification system |
| CN112239197B (en) * | 2020-11-10 | 2024-04-12 | 惠州市华达通气体制造股份有限公司 | Liquid carbon dioxide deep-cooling pressure swing adsorption hydrogen purification system |
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