A device and method for testing and evaluating gas permeability of membrane carbon capture

Abstract

The present invention discloses a membrane carbon capture gas permeability test and evaluation device and method, which relates to the field of membrane separation test technology, including a vacuum pump and at least two membrane pool units, each membrane pool unit is arranged in parallel in sequence, and the upstream of each membrane pool unit is connected in parallel to the downstream of the upstream gas storage tank; the membrane pool unit is provided with a membrane pool structure for separating mixed gases, the downstream of the membrane pool structure in the previous membrane pool unit is connected to the upstream of the membrane pool structure in the next membrane pool unit, the vacuum pump inlet of the vacuum pump is respectively connected to the downstream of the upstream gas storage tank and the downstream of each membrane pool unit, and the inlet and outlet of the gas chromatograph are respectively connected to the downstream of each membrane pool unit and the vacuum pump inlet. The present invention can simply and quickly obtain transmission performance test and evaluation of multiple groups of membrane samples for multiple gases in a wide temperature range and high pressure environment, as well as simultaneously test the separation effect of multiple membrane materials or multi-stage membrane processes on mixed gases, and the test results are highly accurate and repeatable.

Description

Technical Field

[0001] The present invention relates to the technical field of membrane separation testing, and in particular to a device and method for testing and evaluating membrane separation performance. Background Art

[0002] Membrane carbon capture technology is a promising energy-saving separation and purification process with the advantages of low energy consumption, high efficiency, low cost, environmental friendliness, small footprint, and easy operation. It is widely used in flue gas carbon capture of carbon dioxide, natural gas decarbonization and upgrading, natural gas purification of electronic specialty gases helium, separation and purification of hydrogen, and separation of hydrocarbon substances and other gas separation and purification related fields.

[0003] The transmission and separation performance of gas separation membranes determines their industrial application value. The devices involved in detecting the permeability, selectivity and other gas transmission-related properties of the membrane are crucial to the development of gas separation membranes and the realization of their industrial applications. At present, the permeability performance test of gas separation membranes mainly adopts the constant volume-variable pressure method and the constant pressure-variable volume method. The constant pressure-variable volume method maintains a constant pressure higher than the downstream permeate side on the upstream feed side of the membrane, and detects the permeate gas flow rate on the downstream side through a flow meter or chromatograph driven by the pressure difference. However, the gas pipeline sealing of the related device is not high and is not suitable for the extraction of high-purity gas. The constant volume-variable pressure method calculates the permeate gas flow rate according to the ideal gas state equation by measuring the change of the permeate side pressure over time.

[0004] Through prior art search, the following known technical solutions exist:

[0005] Prior art 1: a gas permeameter

[0006] Application number: CN201821545278.7, application date: September 21, 2018, publication (announcement) date: August 16, 2019.

[0007] Prior art 1 discloses a gas permeability meter, which includes a computer, a data acquisition module, a gas cylinder, a buffer tank, a pressure transmitter, a vacuum gauge, a membrane assembly, a ball valve, a temperature control box stainless steel pipeline, and a vacuum pump. The gas cylinder (3), the ball valve 1 (5), the buffer tank 1 (4), and the ball valve 2 (7) are connected in sequence, and the outlet of the ball valve 2 (7) is connected to the air inlet of the membrane assembly (10); the air outlet of the membrane assembly (10) is connected to the vacuum gauge (11), the buffer tank 2 (12), and the ball valve 5 (13); a ball valve 3 (8) is provided between the ball valve 2 (7) and the membrane assembly (10); a ball valve 4 (9) and a vacuum pump (11) are provided between the ball valve 3 (8) and the ball valve 5 (13). The pressure transmitter (6) and the vacuum gauge (11) are connected to the computer (1) through the data acquisition module. The utility model is suitable for evaluating the permeability of single-component or multi-component gases, and has simple operation and accurate measurement.

[0008] Prior Art 2: A method for improving a gas separation membrane permeameter

[0009] Application number: CN200510200792.8, application date: 2005.12.13, publication (announcement) date: 2006.09.13.

[0010] Prior art 2 belongs to the field of chemical engineering technology and relates to an improved method for a gas separation membrane permeameter. It is characterized in that in the process of measuring the gas permeability of the membrane using the constant pressure variable volume method, a vacuum method is used upstream and downstream of the membrane pool to promptly remove the gas adsorbed (inorganic membrane) or dissolved (organic membrane) in the gas pipeline and the membrane; in addition, a capillary soap film flowmeter isolated from the air is used downstream to measure the gas permeability rate, which can effectively prevent air back diffusion. The effect and benefit of the present invention is to solve the problems existing in the existing constant pressure variable volume method for measuring the gas permeability of the membrane, save the transition time for the conversion of the two measuring gases, and prevent and avoid the influence of air back diffusion on the accuracy of the measurement results.

[0011] Prior Art 3: A fully automatic gas separation membrane permeability testing device and method

[0012] Application number: CN202011269845.2, application date: 2020.11.13, publication (announcement) date: 2021.03.05.

[0013] Prior art 3 relates to a fully automatic gas separation membrane permeability testing device and method, which belongs to the field of chemical engineering technology. The device includes an air intake container for accommodating intake gas, the inlet end of the air intake container is connected to a plurality of gas sources of the gas to be tested; the outlet end of the air intake container is connected to the upper chambers of a plurality of test membrane pools through an air intake pipeline, and at the same time, the upper chambers of the test membrane pools are all connected to the residual gas exhaust pipeline; the lower chambers of the test membrane pools are respectively connected to the permeate gas detection pipeline, the ends of the permeate gas detection pipelines are connected to a gas chromatograph, and at the same time, the lower chambers of the test membrane pools are all connected to the permeate gas exhaust pipeline and the purge pipeline; the carrier gas inlet of the gas chromatograph is connected to the carrier gas pipeline. The testing device described in the present invention operates fully automatically, continuously and efficiently, and can obtain multiple gas permeability properties of multiple groups of membrane samples at one time, which can not only ensure the accuracy and repeatability of the test data, but also save test time and reduce labor costs.

[0014] However, existing technologies 1, 2 and 3 cannot realize testing under complex conditions such as high pressure and high and low temperatures.

[0015] Prior Art 4: A method for improving a gas separation membrane permeameter

[0016] Application number: CN202010242214.5, application date: 2020.03.31, publication (announcement) date: 2020.06.12.

[0017] Prior art 4 discloses a constant volume variable pressure method test system for gas permeability, comprising a computer, a data acquisition module, a vacuum pump, a gas cylinder, a pressure transmitter, an upstream gas storage tank, a downstream gas storage tank, a membrane cell assembly, and a pressure sensor. A pressure sensor is provided at the inlet of each of the upstream and downstream gas storage tanks. An upstream vacuum valve, a tee, and a downstream vacuum valve are sequentially provided on the pipeline between the upstream and downstream gas storage tanks. The third end of the tee is connected to the vacuum pump. The membrane cell assembly is connected in parallel to the pipeline between the upstream and downstream gas storage tanks. The pressure transmitter, pressure sensor, and temperature control box are respectively connected to the data acquisition module. The data acquisition module and vacuum pump are respectively electrically connected to the computer. The present invention reduces the number of valves, is simple and convenient to operate, greatly reduces the leakage rate and error of the test system, and uses organic glass and aluminum profiles as a frame to reduce the weight and volume of the equipment, thereby reducing costs.

[0018] However, the existing technology 4 cannot achieve simultaneous measurement of the separation effects of multiple membrane materials on mixed gases.

[0019] The above search revealed that most existing separation instruments can only test the separation performance of a single membrane material, making it difficult to perform multi-stage separation tests on a mixed gas, and thus increasingly unable to meet modern experimental requirements. The above technical solutions do not affect the novelty of the present invention; and the combination of the above existing technologies does not undermine the inventiveness of the present invention. Summary of the Invention

[0020] In order to overcome the above-mentioned deficiencies in the prior art, the present invention provides a device and method for testing and evaluating the gas permeability of membrane carbon capture.

[0021] The present invention adopts the following technical solution to solve the technical problem: a membrane carbon capture gas permeability test and evaluation device, comprising a gas cylinder, a pressure transmitter, a gas cylinder inlet valve, a gas cylinder pressure sensor, an upstream gas storage tank, a gas chromatograph and a data acquisition and analysis module connected in sequence, and also comprising a vacuum pump and at least two membrane cell units;

[0022] The membrane pool units are sequentially arranged in parallel, and the upstream of each membrane pool unit is connected in parallel to the downstream of the upstream gas storage tank, and an upstream air inlet valve is provided between the upstream of each membrane pool unit and the downstream of the upstream gas storage tank;

[0023] The membrane pool unit is provided with a membrane pool structure for separating mixed gases, the downstream of the membrane pool structure in the previous level membrane pool unit is connected to the upstream of the membrane pool structure in the next level membrane pool unit, and a series valve is provided between the two;

[0024] The vacuum pump inlet of the vacuum pump is respectively connected to the downstream of the upstream gas storage tank and the downstream of each membrane pool unit, and an upstream vacuum valve and a downstream vacuum valve are respectively connected between the two;

[0025] The inlet of the gas chromatograph is in communication with the downstream of each membrane pool unit, and a gas chromatograph air inlet valve is provided between the inlet of the gas chromatograph and the downstream of each membrane pool unit; the outlet of the gas chromatograph is in communication with the inlet of the vacuum pump;

[0026] The data acquisition and analysis module is in data communication with the gas cylinder pressure sensor, the measurement module of the membrane pool unit and the gas chromatograph.

[0027] Furthermore, the membrane pool unit includes a membrane pool air inlet valve, a membrane pool structure, a membrane pool pressure sensor and a membrane pool air outlet valve which are sequentially connected from upstream to downstream. The membrane pool pressure sensor serves as a measurement module of the membrane pool unit and is data-connected to the data acquisition and analysis module.

[0028] Furthermore, the membrane pool structure includes a membrane pool upper sheet, a membrane pool lower sheet, a membrane, a filter screen, a membrane pool air inlet pipe and a membrane pool air outlet pipe;

[0029] The upper membrane pool sheet and the lower membrane pool sheet can be detachably installed and fixed.

[0030] The bottom of the upper membrane pool sheet and / or the top of the lower membrane pool sheet are grooved to form a cavity, the filter screen is fixedly installed in the cavity, and the membrane is covered on the filter screen to separate the cavity into an upper cavity portion and a lower cavity portion that are not directly connected;

[0031] The membrane pool air inlet pipe is connected to the upper part of the cavity, and its inlet serves as the upstream of the membrane pool unit; the membrane pool air outlet pipe is connected to the lower part of the cavity, and its outlet serves as the downstream of the membrane pool unit.

[0032] Furthermore, an annular sealing groove for sealing and fitting a sealing ring is provided at the bottom of the upper membrane pool sheet and / or the top of the lower membrane pool sheet on the periphery of the cavity.

[0033] Furthermore, the membrane pool structure also includes a membrane pool exhaust pipe;

[0034] One end of the membrane pool exhaust pipe is communicated with the upper part of the cavity, and the other end is emptied and communicated with an exhaust valve.

[0035] Furthermore, it also includes a temperature control device;

[0036] The temperature control device acts on the membrane pool structure of each membrane pool unit to adjust the ambient temperature of the membrane pool structure.

[0037] Furthermore, the temperature control device has a temperature adjustment range of -30°C to 150°C and a testable pressure range of 0-30atm.

[0038] Furthermore, the gas cylinder, the pressure transmitter, the gas cylinder air inlet valve, the gas cylinder pressure sensor, the upstream gas storage tank, the membrane pool unit, the vacuum pump and the gas chromatograph are connected by a stainless steel pipe.

[0039] A membrane carbon capture gas permeability test and evaluation method, using the membrane carbon capture gas permeability test and evaluation device to simultaneously perform multiple gas separation tests, includes the following steps:

[0040] In the first step, according to the number of membrane pool units and the number of membrane materials to be measured in the experiment, a corresponding number of membranes with a radius r1 are punched out with a puncher, and the thickness l (cm) of the membrane is measured. Subsequently, a corresponding number of aluminum tapes with a radius r2 and an inner hole radius r3 are punched out with a puncher. The effective permeation area S of the membrane is π·r3 2 ;

[0041] Among them, the radius r2 of the aluminum tape and the inner hole radius r3 should satisfy r3<r1, r4<r2, and r4 is the outer diameter of the sealing ring;

[0042] The second step is to install each membrane pool structure. The installation process of a single membrane pool structure is as follows: laying filter paper on the filter screen, starting the vacuum pump and opening the downstream vacuum valve and the membrane pool outlet valve of each membrane pool structure to make the filter paper close to the filter screen; laying the membrane and the aluminum tape on the filter paper from bottom to top in sequence to make the membrane and the filter paper completely cover the inner hole area of ​​the aluminum tape, and sealing the membrane and the filter paper with the aluminum tape;

[0043] Subsequently, the upper and lower membrane pool sheets are installed and fixed, so that the filter paper, the membrane and the aluminum tape are limited and pressed between the upper and lower membrane pool sheets, and the inner hole of the aluminum tape is completely located in the cavity of the membrane pool structure;

[0044] The third step is to keep the vacuum pump in working state until the readings of the pressure sensors of each membrane tank no longer decrease;

[0045] Then, open the upstream air inlet valve, the air inlet valves of each membrane tank, and the upstream vacuum valve in sequence, keep the vacuum pump working for T0 to exhaust the gas in the pipeline of the test and evaluation device, and then close all valves;

[0046] Among them, T0 is the preset exhaust time;

[0047] Open the gas cylinder inlet valve and adjust the upstream pressure through the pressure transmitter until the reading of the gas cylinder pressure sensor reaches the preset upstream pressure P0 (atm);

[0048] Subsequently, the gas cylinder inlet valve is closed, the upstream inlet valve and the inlet valves of each membrane pool are opened, and the pressure of each membrane pool measured by the pressure sensor of each membrane pool is continuously recorded to obtain the change of the pressure of each membrane pool over time;

[0049] According to formula 1, the gas permeability P of the membrane in each membrane pool unit corresponding to the gas stored in the gas cylinder at this time is obtained:

[0050] (Formula 1);

[0051] Where V is the sum of the gas volumes in the pipeline from the downstream end of the membrane pool to the membrane pool outlet valve (cm 3 ), T is the test temperature (K), P2 is the preset upstream pressure P0, and dp / dt is the slope of the curve of the change of each membrane tank pressure with time (torr / s);

[0052] In the fourth step, the gas permeability of the membrane corresponding to various gases to be tested is obtained according to the method in the third step. Let the various gases to be tested be gas A, gas B, etc., then the gas permeability of the membrane corresponding to various gases to be tested is P A 、P B ...;

[0053] The gas separation performance α of the membrane corresponding to any two gases i and j is calculated as follows: i / j :

[0054] (Formula 2)

[0055] Where i and j are any two gases from A, B, etc., P i and P j The corresponding gas permeabilities are the gas permeabilities of the two gases.

[0056] A membrane carbon capture gas permeability test and evaluation method, using the membrane carbon capture gas permeability test and evaluation device to perform a multi-stage membrane separation test on a set of mixed gases of known components, includes the following steps:

[0057] In the first step, according to the number of membrane pool units and the membrane material to be measured in the experiment, a corresponding number of membranes with a radius r1 are punched out of the same membrane material using a puncher, and the thickness l (cm) of the membrane is measured. Subsequently, a corresponding number of aluminum tapes with a radius r2 and an inner hole radius r3 are punched out using a puncher. The effective permeation area S of the membrane is π·r3 2 ;

[0058] Among them, the radius r2 of the aluminum tape and the inner hole radius r3 should satisfy r3<r1, r4<r2, and r4 is the outer diameter of the sealing ring;

[0059] The second step is to install each membrane pool structure. The installation process of a single membrane pool structure is as follows: laying filter paper on the filter screen, starting the vacuum pump and opening the downstream vacuum valve and the membrane pool outlet valve of each membrane pool structure to make the filter paper close to the filter screen; laying the membrane and the aluminum tape on the filter paper from bottom to top in sequence to make the membrane and the filter paper completely cover the inner hole area of ​​the aluminum tape, and sealing the membrane and the filter paper with the aluminum tape;

[0060] Subsequently, the upper and lower membrane pool sheets are installed and fixed, so that the filter paper, the membrane and the aluminum tape are limited and pressed between the upper and lower membrane pool sheets, and the inner hole of the aluminum tape is completely located in the cavity of the membrane pool structure;

[0061] The third step is to keep the vacuum pump in working state until the readings of the pressure sensors of each membrane tank no longer decrease;

[0062] Then, open the upstream air inlet valve, the air inlet valves of each membrane tank, and the upstream vacuum valve in sequence, keep the vacuum pump working for T0 to exhaust the gas in the pipeline of the test and evaluation device, and then close all valves;

[0063] Among them, T0 is the preset exhaust time;

[0064] Open the gas cylinder inlet valve and adjust the upstream pressure through the pressure transmitter until the reading of the gas cylinder pressure sensor reaches the preset upstream pressure P0;

[0065] Subsequently, the gas cylinder inlet valve is closed, the upstream inlet valve and the membrane pool inlet valve of the first-stage membrane pool unit (3) are opened, and the gas permeability P and gas separation performance α of the membrane in the first-stage membrane pool unit are tested;

[0066] Step 4: The reading of the membrane pool pressure sensor in the first-stage membrane pool unit reaches the preset membrane pool unit pressure P M ;

[0067] The fifth step is to open the membrane pool outlet valve and the gas chromatograph inlet valve in the first-stage membrane pool unit, and close the membrane pool outlet valve after the gas in the first-stage membrane pool unit enters the gas chromatograph. The gas chromatograph is then used for analysis, and the gas permeability P of the gas passing through the membrane in the first-stage membrane pool unit is calculated according to the following formulas 3 and 4:

[0068] (Formula 3);

[0069] P B = 273 × 10 10 760 ( 1 − yA ) Vl AT ( 76 / 14 . 7 )[( 1 − x A ) P 2 ] ( dp dt ) (Formula 4);

[0070] Among them, P A and PB are the permeabilities P (Barrer) of gas A and gas B respectively, V is the sum of the gas volumes in the pipeline between the downstream end of the membrane pool and the membrane pool outlet valve (cm 3 ), T is the test temperature (K), x is the mole fraction in the inlet gas, y is the mole fraction in the permeate, dp / dt is the slope of the pressure change curve of each membrane cell over time (torr / s), and P2 is the preset upstream pressure P0;

[0071] The gas separation performance α of the gas passing through the membrane in the first-stage membrane pool unit is calculated according to Formula 5:

[0072] (Formula 5);

[0073] Among them, S A and S B Refers to the peak area of ​​gas A and gas B respectively, α 标 Refers to the peak area ratio of gas chromatograph with known ratios of standard gas A and gas B;

[0074] The sixth step is to test the gas permeability P and gas separation performance α of the membrane in the next-stage membrane pool unit: the above-mentioned next-stage membrane pool unit is used as the membrane pool unit to be tested, and the membrane pool unit of the previous stage of the membrane pool unit to be tested is used as the upper membrane pool unit;

[0075] Step 7: After the previous level test is completed, close the previous level membrane pool air inlet valve and the previous level membrane pool air outlet valve to put the previous level membrane pool unit in a disconnected state; then, open the downstream vacuum valve, the membrane pool air outlet valve in the membrane pool unit to be tested, and the gas chromatograph air inlet valve, and keep the vacuum pump in the working state for T to exhaust the gas in the pipeline in the test evaluation device, where T0 is the preset exhaust time; then close the downstream vacuum valve, the membrane pool air outlet valve in the membrane pool unit to be tested, and the gas chromatograph air inlet valve;

[0076] In the eighth step, each of the series valves is closed, and the series valve between the membrane pool unit to be tested and the upper membrane pool unit is opened to start testing the gas permeability P and gas separation performance α of the membrane in the membrane pool unit;

[0077] Wait for the reading of the membrane pool pressure sensor in the membrane pool unit to reach the preset membrane pool unit pressure P M , opening the membrane pool outlet valve in the membrane pool unit to be tested, closing the membrane pool outlet valve after the gas in the membrane pool unit to be tested enters the gas chromatograph, and then using the gas chromatograph for analysis, and calculating the gas permeability P of each membrane in the membrane pool unit to be tested continuously through the first-stage membrane pool unit according to formula 4;

[0078] Among them, P2 takes the preset membrane pool unit pressure P M ;

[0079] The gas separation performance α of each membrane in the membrane pool unit to be tested is calculated according to formula 4;

[0080] Step 9, repeat steps 6 to 8 until the gas is continuously passed through the membrane pool unit of the first stage to the membrane pool unit of the last stage, and the gas permeability P and gas separation performance α of each membrane are obtained.

[0081] The present invention provides a device and method for testing and evaluating the gas permeability of membrane carbon capture, which has the following beneficial effects:

[0082] The present invention provides a gas separation membrane permeability testing device using a constant volume and pressure-swing method, comprising multiple membrane cells. By controlling the series and parallel connection of multiple membrane cells through valves, the device enables simultaneous testing of multiple membrane samples and multiple gases, or multi-stage separation of mixed gases, over a wide temperature range and under high pressure. This ensures the accuracy of acquired data and improves testing efficiency, resolving the issues of conventional gas permeability testing and evaluation devices, such as mild testing conditions, long test cycles, low accuracy, and low efficiency. The present invention also utilizes multiple membrane materials to perform multi-stage separation of a mixed gas, yielding high-purity gases unattainable by existing gas separation devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0083] Figure 1 It is a schematic diagram of the principle of the present invention;

[0084] Figure 2 This is a schematic diagram of a half-section structure of the membrane pool structure of the present invention;

[0085] Figure 3 This is a schematic diagram of the axonometric partial cross-sectional structure of the membrane pool structure of the present invention.

[0086] In the picture:

[0087] 1. Gas cylinder, 11. Pressure transmitter, 12. Gas cylinder inlet valve, 13. Gas cylinder pressure sensor; 2. Upstream gas storage tank, 21. Upstream inlet valve; 3. Membrane pool unit, 31. Membrane pool inlet valve, 32. Membrane pool structure, 321. Membrane pool upper piece, 322. Membrane pool lower piece, 323. Membrane, 324. Filter, 325. Membrane pool inlet pipe, 326. Membrane pool outlet pipe, 327. Sealing ring, 328. Membrane pool exhaust pipe; 33. Membrane pool pressure sensor, 34. Membrane pool outlet valve; 4. Series valve; 5. Vacuum pump, 51. Upstream vacuum valve, 52. Downstream vacuum valve; 6. Gas chromatograph, 61. Gas chromatograph inlet valve; 7. Temperature control device; 8. Receipt collection module; 9. Computer. DETAILED DESCRIPTION

[0088] To make the objectives, technical solutions, and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts shall fall within the scope of protection of the present invention.

[0089] A membrane carbon capture gas permeability test and evaluation device, such as Figures 1 to 3 As shown, its structural relationship is as follows: it includes a gas cylinder 1, a pressure transmitter 11, a gas cylinder inlet valve 12, a gas cylinder pressure sensor 13, an upstream gas storage tank 2, a gas chromatograph 6 and a data acquisition and analysis module that are connected in sequence, and also includes a vacuum pump 7 and at least two membrane pool units 3;

[0090] The membrane pool units 3 are sequentially arranged in parallel, and the upstream of each membrane pool unit 3 is connected in parallel to the downstream of the upstream gas storage tank 2, and an upstream air inlet valve 21 is provided between the upstream of each membrane pool unit 3 and the downstream of the upstream gas storage tank 2;

[0091] The membrane pool unit 3 is provided with a membrane pool structure 32 for separating mixed gases. The downstream of the membrane pool structure 32 in the previous membrane pool unit 3 is connected with the upstream of the membrane pool structure 32 in the next membrane pool unit 3, and a series valve 4 is provided between the two.

[0092] The vacuum pump inlet of the vacuum pump 5 is respectively connected to the downstream of the upstream gas storage tank 2 and the downstream of each membrane pool unit 3, and an upstream vacuum valve 51 and a downstream vacuum valve 52 are respectively connected between the two;

[0093] The inlet of the gas chromatograph 6 is connected to the downstream of each membrane pool unit 3, and a gas chromatograph air inlet valve 61 is provided between the inlet of the gas chromatograph 6 and the downstream of each membrane pool unit 3; the outlet of the gas chromatograph 6 is connected to the inlet of the vacuum pump;

[0094] The data acquisition and analysis module is in data communication with the gas cylinder pressure sensor 13 , the measurement module of the membrane pool unit 3 and the gas chromatograph 6 .

[0095] In actual settings, the data acquisition and analysis module may include a data-connected computer 9 and a data acquisition module 8, and the data acquisition module may preferably be an RBM350 transmitter.

[0096] Preferably, the membrane pool unit 3 includes a membrane pool air inlet valve 31, a membrane pool structure 32, a membrane pool pressure sensor 33 and a membrane pool air outlet valve 34 which are connected in sequence from upstream to downstream. The membrane pool pressure sensor 33 serves as a measurement module of the membrane pool unit 3 and is connected to the data acquisition and analysis module.

[0097] Preferably, the membrane pool structure 32 includes a membrane pool upper sheet 321, a membrane pool lower sheet 322, a membrane 323, a filter screen 324, a membrane pool air inlet pipe 325 and a membrane pool air outlet pipe 326;

[0098] The upper membrane pool piece 321 and the lower membrane pool piece 322 can be detachably installed and fixed.

[0099] In actual setting, the membrane pool upper piece 321 and the membrane pool lower piece 322 can be detachably installed and fixed by threaded connectors evenly distributed around the circumference;

[0100] The bottom of the membrane pool upper sheet 321 and / or the top of the membrane pool lower sheet 322 are grooved to form a cavity, a filter screen 324 is fixedly installed in the cavity, and the membrane 323 is covered on the filter screen 324 to separate the cavity into an upper cavity portion and a lower cavity portion that are not directly connected;

[0101] The membrane pool air inlet pipe 325 is connected to the upper part of the cavity, and its inlet serves as the upstream of the membrane pool unit 3; the membrane pool air outlet pipe 326 is connected to the lower part of the cavity, and its outlet serves as the downstream of the membrane pool unit 3.

[0102] Preferably, an annular sealing groove for sealing and fitting the sealing ring 327 is provided at the bottom of the membrane pool upper piece 321 and / or the top of the membrane pool lower piece 322 on the periphery of the cavity.

[0103] Preferably, the membrane pool structure 32 further includes a membrane pool exhaust pipe 328;

[0104] One end of the membrane pool exhaust pipe 328 is connected to the upper part of the chamber, and the other end is emptied and connected to a drain valve.

[0105] Preferably, it also includes a temperature control device 7;

[0106] The temperature control device 7 acts on the membrane pool structure 32 of each membrane pool unit 3 to adjust the ambient temperature of the membrane pool structure 32.

[0107] In actual setting, the temperature control device 7 is preferably a temperature control box, and each membrane pool structure 32 is set in the temperature control box.

[0108] Preferably, the temperature control device 7 has a temperature adjustment range of -30°C to 150°C and a testable pressure range of 0-30 atm.

[0109] Preferably, the gas cylinder 1, the pressure transmitter 11, the gas cylinder inlet valve 12, the gas cylinder pressure sensor 13, the upstream gas storage tank 2, the membrane pool unit 3, the vacuum pump 5 and the gas chromatograph 6 are connected by a stainless steel pipe.

[0110] In actual settings, the pipeline branch locations are connected through tees.

[0111] A membrane carbon capture gas permeability test and evaluation method, using the membrane carbon capture gas permeability test and evaluation device to simultaneously perform multiple gas separation tests of the same gas using a membrane material, includes the following steps:

[0112] In the first step, according to the number of membrane pool units 3 and the number of membrane materials to be measured in the experiment, a punch is used to punch out a corresponding number of membranes 323 with a radius r1 of the same membrane material, and the thickness l (cm) of the membrane 323 is measured. Subsequently, a punch is used to punch out a corresponding number of aluminum tapes with a radius r2 and an inner hole radius r3. The effective permeation area S of the membrane 323 is π·r3 2 ;

[0113] Among them, the radius r2 of the aluminum tape and the inner hole radius r3 should satisfy r3<r1, r4<r2, and r4 is the outer diameter of the sealing ring;

[0114] In actual configuration, if a plurality of sealing rings are provided in sequence in the membrane pool structure 32, then r4 is the outer diameter of the outermost sealing ring 327;

[0115] The second step is to install each membrane pool structure 32. The installation process of a single membrane pool structure 32 is as follows: the filter paper is laid on the filter screen 324, the vacuum pump 5 is started and the downstream vacuum valve 52 and the membrane pool outlet valve 34 of each membrane pool structure 32 are opened, so that the filter paper is close to the filter screen 324; the membrane 323 and the aluminum tape are laid on the filter paper from bottom to top, so that the membrane 323 and the filter paper completely cover the inner hole area of ​​the aluminum tape, and the membrane 323 and the filter paper are sealed with the aluminum tape;

[0116] Then, install and fix the membrane pool upper sheet 321 and the membrane pool lower sheet 322, so that the filter paper, membrane 323 and aluminum tape are limited and pressed between the membrane pool upper sheet 321 and the membrane pool lower sheet 322, and the inner hole of the aluminum tape should be completely located in the cavity of the membrane pool structure 32;

[0117] The third step is to keep the vacuum pump 5 in working state until the reading of each membrane tank pressure sensor 33 stops decreasing;

[0118] Subsequently, the upstream air inlet valve 21, the air inlet valves 31 of each membrane tank, and the upstream vacuum valve 51 are opened in sequence, and the vacuum pump 5 is kept in the working state for T0 to exhaust the gas in the pipeline of the test and evaluation device, and then all valves are closed;

[0119] Among them, T0 is the preset exhaust time;

[0120] Open the gas cylinder inlet valve 12 and adjust the upstream pressure through the pressure transmitter 11 until the reading of the gas cylinder pressure sensor 13 reaches the preset upstream pressure P0 (atm);

[0121] Subsequently, the gas cylinder inlet valve 12 is closed, the upstream inlet valve 21 and the inlet valves 31 of each membrane pool are opened, and the pressure of each membrane pool measured by the pressure sensor 33 of each membrane pool is continuously recorded to obtain the change of the pressure of each membrane pool over time;

[0122] The gas permeability P of the membrane 323 in each membrane pool unit 3 corresponding to a gas stored in the gas cylinder 1 at this time is calculated using the following formula:

[0123] (Formula 1);

[0124] Where V is the sum of the gas volumes in the pipeline between the downstream end of the membrane pool and the membrane pool outlet valve 34 (cm 3 ), T is the test temperature (K), P2 is the preset upstream pressure P0, and dp / dt is the slope of the curve of the change of each membrane tank pressure with time (torr / s);

[0125] In the fourth step, the gas permeability of the membrane 323 corresponding to various gases to be tested is obtained according to the method in the third step. Let the various gases to be tested be gas A, gas B, etc., then the gas permeability of the membrane 323 corresponding to various gases to be tested is P A 、P B ...;

[0126] The gas separation performance α of membrane 323 corresponding to any two gases i and j is calculated as follows: i / j :

[0127] (Formula 2)

[0128] Where i and j are any two gases from A, B, etc., P i and P j The corresponding gas permeabilities are the gas permeabilities of the two gases.

[0129] A membrane carbon capture gas permeability test and evaluation method, using the membrane carbon capture gas permeability test and evaluation device to perform a multi-stage membrane separation test on a set of mixed gases of known components, includes the following steps:

[0130] In the first step, according to the number of membrane pool units 3 and the number of membrane materials to be measured in the experiment, a punch is used to punch out a corresponding number of membranes 323 with a radius r1 of the same membrane material, and the thickness l (cm) of the membrane 323 is measured. Subsequently, a punch is used to punch out a corresponding number of aluminum tapes with a radius r2 and an inner hole radius r3. The effective permeation area S of the membrane 323 is π·r3 2 ;

[0131] Among them, the radius r2 of the aluminum tape and the inner hole radius r3 should satisfy r3<r1, r4<r2, and r4 is the outer diameter of the sealing ring;

[0132] In actual configuration, if a plurality of sealing rings are provided in sequence in the membrane pool structure 32, then r4 is the outer diameter of the outermost sealing ring 327;

[0133] The second step is to install each membrane pool structure 32. The installation process of a single membrane pool structure 32 is as follows: the filter paper is laid on the filter screen 324, the vacuum pump 5 is started and the downstream vacuum valve 52 and the membrane pool outlet valve 34 of each membrane pool structure 32 are opened, so that the filter paper is close to the filter screen 324; the membrane 323 and the aluminum tape are laid on the filter paper from bottom to top, so that the membrane 323 and the filter paper completely cover the inner hole area of ​​the aluminum tape, and the membrane 323 and the filter paper are sealed with the aluminum tape;

[0134] Then, install and fix the membrane pool upper sheet 321 and the membrane pool lower sheet 322, so that the filter paper, membrane 323 and aluminum tape are limited and pressed between the membrane pool upper sheet 321 and the membrane pool lower sheet 322, and the inner hole of the aluminum tape should be completely located in the cavity of the membrane pool structure 32;

[0135] The third step is to keep the vacuum pump 5 in working state until the reading of each membrane tank pressure sensor 33 stops decreasing;

[0136] Subsequently, the upstream air inlet valve 21, the air inlet valves 31 of each membrane tank, and the upstream vacuum valve 51 are opened in sequence, and the vacuum pump 5 is kept in the working state for T0 to exhaust the gas in the pipeline of the test and evaluation device, and then all valves are closed;

[0137] Among them, T0 is the preset exhaust time;

[0138] Open the gas cylinder inlet valve 12 and adjust the upstream pressure through the pressure transmitter 11 until the reading of the gas cylinder pressure sensor 13 reaches the preset upstream pressure P0;

[0139] Subsequently, the gas cylinder inlet valve 12 is closed, the upstream inlet valve 21 and the membrane pool inlet valve 31 of the first-stage membrane pool unit (3) are opened, and the gas permeability P and gas separation performance α test of the membrane 323 in the first-stage membrane pool unit 3 are started;

[0140] Step 4: The reading of the membrane pool pressure sensor 33 in the first-stage membrane pool unit 3 reaches the preset membrane pool unit pressure P M ;

[0141] In the fifth step, the membrane pool outlet valve 34 and the gas chromatograph inlet valve 61 in the first-stage membrane pool unit 3 are opened. After the gas in the first-stage membrane pool unit 3 enters the gas chromatograph 6, the membrane pool outlet valve 34 is closed. The gas chromatograph 6 is then used for analysis. The gas permeability P of the gas passing through the membrane 323 in the first-stage membrane pool unit 3 is calculated according to the following formulas 3 and 4:

[0142] (Formula 3);

[0143] P B = 273 × 10 10 760 ( 1 − y A ) Vl AT ( 76 / 14 . 7 )[( 1 − x A ) P 2 ] ( dp dt ) (Formula 4);

[0144] Among them, P A and P B are the permeabilities P (Barrer) of gas A and gas B respectively, V is the sum of the gas volumes in the pipeline between the downstream end of the membrane pool and the membrane pool outlet valve 34 (cm 3 ), T is the test temperature (K), x is the mole fraction in the inlet gas, y is the mole fraction in the permeate, dp / dt is the slope of the pressure change curve of each membrane cell over time (torr / s), and P2 is the preset upstream pressure P0;

[0145] The gas separation performance α of the gas passing through the membrane 323 in the first-stage membrane pool unit 3 is calculated according to Formula 5:

[0146] (Formula 5);

[0147] Among them, A A and A B Refers to the peak area of ​​gas A and gas B respectively, α 标 Refers to the peak area ratio of gas chromatograph with known ratios of standard gas A and gas B;

[0148] Step 6: Test the gas permeability P and gas separation performance α of the membrane 323 in the next membrane pool unit 3: the next membrane pool unit 3 is used as the membrane pool unit to be tested, and the previous membrane pool unit 3 of the membrane pool unit to be tested is used as the upper membrane pool unit;

[0149] Step 7: After the previous level test is completed, the previous level membrane pool air inlet valve 31 and the previous level membrane pool air outlet valve 34 are closed to put the previous level membrane pool unit in a disconnected state; then, the downstream vacuum valve 52, the membrane pool air outlet valve 34 in the membrane pool unit to be tested, and the gas chromatograph air inlet valve 61 are opened, and the working state of the vacuum pump 5 is maintained for T0 to exhaust the gas in the pipeline of the test evaluation device, wherein T0 is a preset exhaust time; then, the downstream vacuum valve 52, the membrane pool air outlet valve 34 in the membrane pool unit to be tested, and the gas chromatograph air inlet valve 61 are closed;

[0150] In the eighth step, each series valve 4 is closed, and the series valve 4 between the membrane pool unit to be tested and the upper membrane pool unit is opened to start testing the gas permeability P and gas separation performance α of the membrane 323 in the membrane pool unit 3;

[0151] Wait for the reading of the membrane pool pressure sensor 33 in the membrane pool unit 3 to reach the preset membrane pool unit pressure P M, open the membrane pool outlet valve 34 in the membrane pool unit to be tested, close the membrane pool outlet valve 34 after the gas in the membrane pool unit to be tested enters the gas chromatograph 6, and then use the gas chromatograph 6 to analyze, and calculate the gas permeability P of the gas continuously passing through the first-stage membrane pool unit 3 to each membrane 323 in the membrane pool unit to be tested according to formula 4;

[0152] Among them, P2 takes the preset membrane pool unit pressure P M ;

[0153] The gas separation performance α of each membrane 323 in the membrane pool unit to be tested is calculated according to formula 4;

[0154] In the ninth step, steps six to eight are repeated until the gas is continuously passed through the first-stage membrane pool unit 3 and the gas permeability P and gas separation performance α of each membrane 323 in the last-stage membrane pool unit 3 are obtained.

[0155] The working method of the present application is described by taking the above-mentioned membrane carbon capture gas permeability testing and evaluation device provided with three membrane pool units 3 as an example.

[0156] In the above membrane carbon capture gas permeability test and evaluation device:

[0157] The gas in gas cylinder 1 is a single gas selected from helium, hydrogen, carbon dioxide, oxygen, nitrogen, methane, ethylene, ethane, propylene, and propane, as well as a mixture of carbon dioxide and nitrogen (v:v = 50:50), a mixture of carbon dioxide and nitrogen (v:v = 15:85), and a mixture of carbon dioxide and methane (v:v = 50:50).

[0158] A groove with a diameter of 3 cm and a depth of 0.5 cm is provided at the bottom of the upper sheet 321 of the membrane pool.

[0159] Annular sealing grooves with diameters of 3.5 cm and 4.0 cm are concentrically formed outside the groove, and sealing rings are provided in the annular sealing grooves for sealing. The aforementioned sealing rings deform when the membrane pool structure 32 is vacuumed, and the sealing effect is improved at the same time.

[0160] The top of the membrane pool lower sheet 322 is provided with a groove with a diameter of 3 cm, which is matched with the filter screen 324. The filter screen 324 is embedded in the groove, and its upper surface is flush with the upper surface of the membrane pool lower sheet 322. The membrane 323 is made of flat membrane material with a thickness of 1 μm-2 mm.

[0161] The upper piece 321 of the membrane pool and the lower piece 322 of the membrane pool are detachably installed and fixed by six bolts evenly distributed around the circumference. The aforementioned bolts are set through the upper piece 321 of the membrane pool and are threadedly sealed with the screw holes opened on the upper piece 321 of the membrane pool. At the same time, the bottom end thread of the aforementioned bolts is threadedly sealed and installed in the non-through screw hole opened on the top of the lower piece 322 of the membrane pool.

[0162] Example 1

[0163] Using the aforementioned membrane carbon capture gas permeability test and evaluation device, utilizing the first-stage membrane cell unit, the polyimide (Matrimid) membrane material was tested for permeability P and gas separation performance α at a temperature of 25°C and a pressure of 1 atm, following the method of testing multiple gas separations of the same gas using one membrane material.

[0164] Install the test and evaluation device according to the first and second steps above;

[0165] The number of aluminum tapes punched out by the puncher is one piece, the radius of the aluminum tape is R3 = 2.0 cm, the inner hole radius is R2 = 0.5 cm, the thickness of the membrane to be tested is l = 0.050 cm, and the effective permeation area of ​​the membrane is S = π·r3 2 =0.785cm 3 ;

[0166] The sum of the gas volumes (cm2) in the pipeline between the downstream end of the membrane pool and the membrane pool outlet valve 34 of the test evaluation device 3 ) is calibrated to obtain V=20.1cm 3 .

[0167] He, H2, CO2, N2 and CH4 were used as the test gases, and the permeability P of the polyimide (Matrimid) membrane material to the above gases was measured according to the third step and is shown in Table 1 below;

[0168] The preset exhaust time T0 is 10 hours, the preset upstream pressure P0 (atm) is 1 atm, and the test temperature T is 25°C.

[0169] Then, the gas separation performance α of the polyimide (Matrimid) membrane material for the aforementioned gases is calculated according to the fourth step and is shown in Table 1 below.

[0170]

[0171] Table 1 Gas permeability and gas separation performance of polyimide membrane materials

[0172] Example 2

[0173] Using the aforementioned membrane carbon capture gas permeability test and evaluation device, and utilizing the first-stage membrane pool unit, the permeability P and gas separation performance α of polyimide-type mixed-matrix membranes (Matrimid-SC mixed-matrix membranes) were tested at a pressure of 1 atm and different temperatures, using the method of testing multiple gas separations of the same gas using one membrane material.

[0174] Install the test and evaluation device according to the first and second steps above;

[0175] The number of aluminum tapes punched out by the puncher is one piece, the radius of the aluminum tape is r2 = 2.0 cm, the inner hole radius is r3 = 0.5 cm, the thickness of the membrane to be tested is l = 0.051 cm, and the effective permeation area of ​​the membrane is S = π·r3 2 =0.785cm 3 ;

[0176] The sum of the gas volumes (cm2) in the pipeline between the downstream end of the membrane pool and the membrane pool outlet valve 34 of the test evaluation device 3 ) is calibrated to obtain V=20.1cm 3 .

[0177] Using CO2 and N2 as the test gases, the permeability P of the polyimide mixed matrix membrane (Matrimid-SC mixed-matrix membranes) material to the aforementioned gases at various preset test temperatures was measured according to the third step and is shown in Table 2 below.

[0178] The preset exhaust time T0 is 10 hours, the preset upstream pressure P0 (atm) is 1 atm, and the test temperature T is 25°C as a gradient, and the experiments are carried out from -25°C (inclusive) to 150°C (inclusive).

[0179] Then, the gas separation performance α of the polyimide mixed matrix membrane (Matrimid-SC mixed-matrix membranes) material for the aforementioned gases at each preset test temperature is calculated according to the fourth step and is shown in Table 2 below.

[0180]

[0181] Table 2 High and low temperature permeability and gas separation performance of polyimide mixed matrix membrane materials

[0182] Example 3

[0183] Using the aforementioned membrane carbon capture gas permeability test and evaluation device, and utilizing the first-stage membrane pool unit, the permeability P and gas separation performance α of the polyamide ether (Pebax) membrane material were tested at a temperature of 25°C and different pressure conditions, using the method of testing multiple gas separations of the same gas using one membrane material.

[0184] Install the test and evaluation device according to the first and second steps above;

[0185] The number of aluminum tapes punched out by the puncher is one piece, the radius of the aluminum tape is r2 = 2.0 cm, the inner hole radius is r3 = 0.5 cm, the thickness of the membrane to be tested is l = 0.052 cm, and the effective permeation area of ​​the membrane is S = π·r32 =0.785cm 3 ;

[0186] The sum of the gas volumes (cm2) in the pipeline between the downstream end of the membrane pool and the membrane pool outlet valve 34 of the test evaluation device 3 ) is calibrated to obtain V=20.1cm 3 .

[0187] Using CO2 and N2 as the test gases, the permeability P of the polyamide ether (Pebax) membrane material to the aforementioned gases at various preset upstream pressures was measured according to the third step and is shown in Table 3 below.

[0188] The preset exhaust time T0 is 10 hours, the test temperature T is 25°C, the preset upstream pressure P0 (atm) is 1 atm, and the experiment is performed with a gradient of 5 atm, with 5 atm (inclusive) to 30 atm (inclusive).

[0189] Then, the gas separation performance α of the polyamide ether (Pebax) membrane material for the aforementioned gases at each preset upstream pressure is calculated according to the fourth step and is shown in Table 3 below.

[0190]

[0191] Table 3 High and low pressure permeability and gas separation performance of polyamide ether membrane materials

[0192] Example 4

[0193] Using the aforementioned membrane carbon capture gas permeability test and evaluation device, utilizing the first to third membrane cell units, three identical polyimide (Matrimid) membranes were tested for permeability P and gas separation performance α at 25°C and 1 atm, following the method of testing multiple gas separations of the same gas using one membrane material.

[0194] Install the test and evaluation device according to the first and second steps above;

[0195] The number of aluminum tapes punched out by the puncher is three, the radius of the aluminum tape is r2 = 2.0 cm, the inner hole radius is r3 = 0.5 cm, the thickness of the membrane to be tested is l = 0.05 ± 0.003 cm, and the effective permeation area of ​​the membrane is S = π·r3 2 =0.785cm 3 ;

[0196] The sum of the gas volumes (cm2) in the pipeline between the downstream end of the membrane pool and the membrane pool outlet valve 34 of the test evaluation device 3 ) is calibrated to obtain V1=20.1cm 3 , V2=19.8cm 3 , V3=19.4cm3 .

[0197] He, H2, CO2, N2, and CH4 were used as the test gases, and the permeabilities P of three polyimide (Matrimid) membrane materials to the aforementioned gases were measured in the first to third membrane pool units according to the third step. The results are shown in Table 4 below.

[0198] The preset exhaust time T0 is 10 hours, the preset upstream pressure P0 (atm) is 1 atm, and the test temperature T is 25°C.

[0199] Then, the gas separation performance α of the three polyimide (Matrimid) membrane materials for the aforementioned gases was calculated according to the fourth step and is shown in Table 4 below.

[0200]

[0201] Table 4 Gas permeability and gas separation performance of three polyimide (Matrimid) membrane materials tested simultaneously

[0202] Example 5

[0203] The above-mentioned membrane carbon capture gas permeability test and evaluation device was used, utilizing first- to third-stage membrane pool units, and according to the method for conducting multi-stage membrane separation tests on a mixed gas of known components, to test the multi-stage membrane separation permeability P and gas separation performance α of the self-microporous polymer (PIM) membrane material, polyamide ether (Pebax) membrane material, and polyimide (Matrimid) membrane material sequentially arranged in the first- to third-stage membrane pool units at a temperature of 25°C and a pressure of 1 atm:

[0204] Install the test and evaluation device according to the first and second steps above;

[0205] Among them, the self-contained microporous polymer (PIM) membrane material, polyamide ether (Pebax) membrane material and polyimide (Matrimid) membrane material were installed in the first to third membrane pool units in sequence. The number of aluminum tapes punched out by a puncher was three, the aluminum tape radius r2 = 2.0 cm, the inner hole radius r3 = 0.5 cm, the thickness of the membrane to be tested l = 0.05 ± 0.003 cm, and the effective permeation area of ​​the membrane S = π·r3 2 =0.785cm 3 ;

[0206] The sum of the gas volumes (cm2) in the pipeline between the downstream end of the membrane pool and the membrane pool outlet valve 34 of the test evaluation device 3 ) is calibrated to obtain V1=20.1cm 3 , V2=19.8cm 3 , V3=19.4cm 3 .

[0207] Using CO2 and N2 as the test gases, respectively, in the first-stage membrane pool unit, the permeability P and gas separation performance α of the polymer with microporous (PIM) membrane material for the aforementioned gases were measured according to steps 3 to 5, as shown in Table 5 below;

[0208] The preset exhaust time T0 is 10 hours, the preset upstream pressure P0 (atm) is 1 atm, and the test temperature T is 25°C.

[0209] Subsequently, in the second-stage membrane pool unit, the gas to be tested is sequentially passed through the polymer with microporous structure (PIM) membrane material and the polyamide ether (Pebax) membrane material according to steps 6 to 8. The permeability P and gas separation performance α are shown in Table 5 below;

[0210] The preset exhaust time T0 is 10h, and the preset membrane pool unit pressure P M Take 100psi, test temperature T take 25℃;

[0211] Finally, in the third-stage membrane pool unit, the permeability P and gas separation performance α of the gas to be tested obtained in step 9 passing through the self-microporous polymer (PIM) membrane material, polyamide ether (Pebax) membrane material and polyimide (Matrimid) membrane material in sequence are shown in Table 5 below.

[0212]

[0213] Table 5 Gas permeability and gas separation performance of multi-stage membrane separation materials made of self-microporous polymer, polyamide ether and polyimide membranes

[0214] For CO2 and N2 gases, compared with the separation using only polyimide (Matrimid) membrane materials, the gas separation performance α of multi-stage separation using microporous polymer (PIM) membrane materials, polyamide ether (Pebax) membrane materials and polyimide (Matrimid) membrane materials in sequence was improved from 35.79 to 215.36.

[0215] It should be noted that, in this document, relational terms such as first and second, etc., are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply the existence of any such actual relationship or order between these entities or operations. Moreover, the terms "comprises," "comprising," or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article, or device comprising a series of elements includes not only those elements, but also other elements not explicitly listed, or elements inherent to such process, method, article, or device. In the absence of further limitations, an element defined by the phrase "comprising a ..." does not exclude the presence of other identical elements in the process, method, article, or device comprising the element.

[0216] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A membrane carbon capture gas permeability test and evaluation device, comprising a gas cylinder (1), a pressure transmitter (11), a gas cylinder inlet valve (12), a gas cylinder pressure sensor (13), an upstream gas storage tank (2), a gas chromatograph (6), and a data acquisition and analysis module, which are connected in sequence, and characterized by: It also includes a vacuum pump (5) and at least two membrane pool units (3); The membrane pool units (3) are sequentially arranged in parallel, and the upstream of each membrane pool unit (3) is connected in parallel to the downstream of the upstream gas storage tank (2), and an upstream air inlet valve (21) is provided between the upstream of each membrane pool unit (3) and the downstream of the upstream gas storage tank (2); The membrane pool unit (3) is provided with a membrane pool structure (32) for separating mixed gases, the downstream of the membrane pool structure (32) in the previous membrane pool unit (3) is connected to the upstream of the membrane pool structure (32) in the next membrane pool unit (3), and a series valve (4) is provided between the two. The vacuum pump inlet of the vacuum pump (5) is respectively connected to the downstream of the upstream gas storage tank (2) and the downstream of each membrane pool unit (3), and an upstream vacuum valve (51) and a downstream vacuum valve (52) are respectively connected between the two. The inlet of the gas chromatograph (6) is in communication with the downstream of each membrane pool unit (3), and a gas chromatograph air inlet valve (61) is provided between the inlet of the gas chromatograph and the downstream of each membrane pool unit (3); the outlet of the gas chromatograph (6) is in communication with the inlet of the vacuum pump; The data acquisition and analysis module is in data communication with the gas cylinder pressure sensor (13), the measurement module of the membrane pool unit (3), and the gas chromatograph (6).

2. The gas permeability testing and evaluation device for membrane carbon capture according to claim 1, characterized in that: The membrane pool unit (3) comprises a membrane pool air inlet valve (31), a membrane pool structure (32), a membrane pool pressure sensor (33) and a membrane pool air outlet valve (34) which are sequentially connected from upstream to downstream. The membrane pool pressure sensor (33) serves as a measurement module of the membrane pool unit (3) and is in data communication with the data acquisition and analysis module.

3. The gas permeability testing and evaluation device for membrane carbon capture according to claim 2, characterized in that: The membrane pool structure (32) includes a membrane pool upper sheet (321), a membrane pool lower sheet (322), a membrane (323), a filter screen (324), a membrane pool air inlet pipe (325), and a membrane pool air outlet pipe (326); The membrane pool upper piece (321) and the membrane pool lower piece (322) are detachably mounted and fixed. The bottom of the membrane pool upper sheet (321) and / or the top of the membrane pool lower sheet (322) are grooved to form a cavity, the filter screen (324) is fixedly installed in the cavity, and the membrane (323) is covered on the filter screen (324) to separate the cavity into an upper cavity portion and a lower cavity portion that are not directly connected; The membrane pool air inlet pipe (325) is communicated with the upper part of the chamber, and its inlet serves as the upstream of the membrane pool unit (3); the membrane pool air outlet pipe (326) is communicated with the lower part of the chamber, and its outlet serves as the downstream of the membrane pool unit (3).

4. The gas permeability testing and evaluation device for membrane carbon capture according to claim 3, characterized in that: The bottom of the membrane pool upper plate (321) and / or the top of the membrane pool lower plate (322) are also provided with an annular sealing groove for sealing and fitting a sealing ring (327) on the periphery of the cavity.

5. The gas permeability testing and evaluation device for membrane carbon capture according to claim 3, characterized in that: The membrane pool structure (32) further includes a membrane pool exhaust pipe (328); One end of the membrane pool exhaust pipe (328) is connected to the upper part of the chamber, and the other end is emptied and connected to a drain valve.

6. The gas permeability testing and evaluation device for membrane carbon capture according to claim 4, characterized in that: Also included is a temperature control device (7); The temperature control device (7) acts on the membrane pool structure (32) of each membrane pool unit (3) to adjust the ambient temperature of the membrane pool structure (32).

7. The gas permeability testing and evaluation device for membrane carbon capture according to claim 6, characterized in that: The temperature control device (7) has a temperature adjustment range of -30°C to 150°C and a testable pressure range of 0 to 30 atm.

8. The gas permeability testing and evaluation device for membrane carbon capture according to claim 1, characterized in that: The gas cylinder (1), the pressure transmitter (11), the gas cylinder inlet valve (12), the gas cylinder pressure sensor (13), the upstream gas storage tank (2), the membrane pool unit (3), the vacuum pump (5) and the gas chromatograph (6) are connected by a stainless steel pipe.

9. A membrane carbon capture gas permeability test and evaluation method, using the membrane carbon capture gas permeability test and evaluation device as claimed in claim 6 to simultaneously perform multiple gas separation tests, characterized in that: The following processes are included: In the first step, according to the number of membrane pool units (3) and the number of membrane materials to be measured in the experiment, a corresponding number of membranes (323) with a radius r1 are punched out using a puncher, and the thickness of the membrane (323) is measured. l (cm); Then, a puncher is used to punch out a corresponding number of aluminum tapes with a radius r2 and an inner hole radius r3, and the effective permeation area S of the membrane (323) is π·r3 2 ; The radius r2 of the aluminum tape and the inner hole radius r3 should satisfy r3<r1, r4<r2, and r4 is the outer diameter of the sealing ring (327); The second step is to install each membrane pool structure (32). The installation process of a single membrane pool structure (32) is as follows: laying filter paper on the filter screen (324), starting the vacuum pump (5) and opening the downstream vacuum valve (52) and the membrane pool outlet valve (34) of each membrane pool structure (32) so that the filter paper is close to the filter screen (324); laying the membrane (323) and the aluminum tape on the filter paper in sequence from bottom to top so that the membrane (323) and the filter paper completely cover the inner hole area of ​​the aluminum tape, and sealing the membrane (323) and the filter paper by the aluminum tape; Subsequently, the membrane pool upper sheet (321) and the membrane pool lower sheet (322) are installed and fixed, so that the filter paper, the membrane (323) and the aluminum tape are limited and pressed between the membrane pool upper sheet (321) and the membrane pool lower sheet (322), and the inner hole of the aluminum tape is completely located in the cavity of the membrane pool structure (32); The third step is to maintain the working state of the vacuum pump (5) until the reading of each membrane tank pressure sensor (33) no longer decreases; Subsequently, the upstream air inlet valve (21), the air inlet valves (31) of each membrane tank and the upstream vacuum valve (51) are opened in sequence, and the working state of the vacuum pump (5) is maintained for T0 to discharge the gas in the pipeline of the test evaluation device, and then all valves are closed; Among them, T0 is the preset exhaust time; Open the gas cylinder inlet valve (12) and adjust the upstream pressure through the pressure transmitter (11) until the reading of the gas cylinder pressure sensor (13) reaches the preset upstream pressure P0 (atm); Subsequently, the gas cylinder air inlet valve (12) is closed, the upstream air inlet valve (21) and the air inlet valves (31) of each membrane pool are opened, and the pressure of each membrane pool measured by the pressure sensor (33) of each membrane pool is continuously recorded to obtain the change of the pressure of each membrane pool over time; According to formula 1, the gas permeability P of the membrane (323) in each membrane pool unit (3) corresponding to the gas stored in the gas cylinder (1) at this time is obtained: (Equation 1); in, V The sum of the gas volumes in the pipeline between the downstream end of the membrane pool and the membrane pool outlet valve (34) (cm 3 ), T is the test temperature (K), P 2 is the preset upstream pressure P0, dp / dt is the slope of the curve of each membrane pool pressure changing with time (torr / s); In the fourth step, the gas permeability of the membrane (323) corresponding to various gases to be measured is obtained according to the method of the third step. Let the various gases to be measured be gas A, gas B, etc., then the gas permeability of the membrane (323) corresponding to various gases to be measured is P A 、P B ...; The gas separation performance α of the membrane (323) corresponding to any two gases i and j is calculated by following formula 2: i / j : (Formula 2); Where i and j are any two gases from A, B, etc., P i and P j The corresponding gas permeabilities are the gas permeabilities of the two gases.

10. A membrane carbon capture gas permeability test and evaluation method, comprising: using the membrane carbon capture gas permeability test and evaluation device as claimed in claim 6 to perform a multi-stage membrane separation test on a mixed gas, characterized in that: The following processes are included: In the first step, according to the number of membrane pool units (3) and the number of membrane materials to be measured in the experiment, a corresponding number of membranes (323) with a radius r1 are punched out using a puncher, and the thickness of the membrane (323) is measured. l (cm); then, a punch is used to punch out a corresponding number of aluminum tapes with a radius r2 and an inner hole radius r3, and the effective membrane permeation area S of the membrane (323) is π·r3 2 ; The radius r2 of the aluminum tape and the inner hole radius r3 should satisfy r3<r1, r4<r2, and r4 is the outer diameter of the sealing ring (327); The second step is to install each membrane pool structure (32). The installation process of a single membrane pool structure (32) is as follows: laying filter paper on the filter screen (324), starting the vacuum pump (5) and opening the downstream vacuum valve (52) and the membrane pool outlet valve (34) of each membrane pool structure (32) so that the filter paper is closely attached to the filter screen (324); laying the membrane (323) and the aluminum tape on the filter paper from bottom to top so that the membrane (323) and the filter paper completely cover the inner hole area of ​​the aluminum tape, and sealing the membrane (323) and the filter paper by the aluminum tape; Subsequently, the membrane pool upper sheet (321) and the membrane pool lower sheet (322) are installed and fixed, so that the filter paper, the membrane (323) and the aluminum tape are limited and pressed between the membrane pool upper sheet (321) and the membrane pool lower sheet (322), and the inner hole of the aluminum tape is completely located in the cavity of the membrane pool structure (32); The third step is to maintain the working state of the vacuum pump (5) until the reading of each membrane tank pressure sensor (33) no longer decreases; Subsequently, the upstream air inlet valve (21), the air inlet valves (31) of each membrane tank and the upstream vacuum valve (51) are opened in sequence, and the working state of the vacuum pump (5) is maintained for T0 to discharge the gas in the pipeline of the test evaluation device, and then all valves are closed; Among them, T0 is the preset exhaust time; Open the gas cylinder inlet valve (12) and adjust the upstream pressure through the pressure transmitter (11) until the reading of the gas cylinder pressure sensor (13) reaches the preset upstream pressure P0; Subsequently, the gas cylinder air inlet valve (12) is closed, the upstream air inlet valve (21) and the membrane pool air inlet valve (31) of the first-stage membrane pool unit (3) are opened, and the gas permeability P and gas separation performance α test of the membrane (323) in the first-stage membrane pool unit (3) are started; In the fourth step, the reading of the membrane pool pressure sensor (33) in the first-stage membrane pool unit (3) reaches the preset membrane pool unit pressure P M ; The fifth step is to open the membrane pool outlet valve (34) and the gas chromatograph inlet valve (61) in the first-stage membrane pool unit (3), and close the membrane pool outlet valve (34) after the gas in the first-stage membrane pool unit (3) enters the gas chromatograph (6). The gas chromatograph (6) is then used for analysis, and the gas permeability P of the gas passing through the membrane (323) in the first-stage membrane pool unit (3) is calculated according to the following formulas 3 and 4: (Formula 3); (Formula 4); Among them, P A and P B are the permeabilities P (Barrer) of gas A and gas B respectively, and V is the sum of the gas volumes in the pipeline between the downstream end of the membrane pool and the membrane pool outlet valve (34) (cm 3 ), T is the test temperature (K), x is the mole fraction in the inlet gas, y is the mole fraction in the permeate, dp / dt is the slope of the pressure change curve of each membrane cell over time (torr / s), and P2 is the preset upstream pressure P0; The gas separation performance α of the gas passing through the membrane (323) in the first-stage membrane pool unit (3) is calculated according to Formula 5: (Formula 5); Among them, S A and S B Refers to the peak area of ​​gas A and gas B respectively, α 标 Refers to the peak area ratio of gas chromatograph with known ratios of standard gas A and gas B; The sixth step is to test the gas permeability P and gas separation performance α of the membrane (323) in the membrane pool unit (3) of the next level: the membrane pool unit (3) of the next level is used as the membrane pool unit to be tested, and the membrane pool unit (3) of the previous level of the membrane pool unit to be tested is used as the upper level membrane pool unit; Step 7: After the previous level test is completed, the previous level membrane pool air inlet valve (31) and the previous level membrane pool air outlet valve (34) are closed to put the previous level membrane pool unit in a disconnected state; then, the downstream vacuum valve (52), the membrane pool air outlet valve (34) in the membrane pool unit to be tested, and the gas chromatograph air inlet valve (61) are opened, and the working state of the vacuum pump (5) is maintained for T0 to exhaust the gas in the pipeline of the test evaluation device, wherein T0 is a preset exhaust time; then, the downstream vacuum valve (52), the membrane pool air outlet valve (34) in the membrane pool unit to be tested, and the gas chromatograph air inlet valve (61) are closed; In the eighth step, each of the series valves (4) is closed, and the series valve (4) between the membrane pool unit to be tested and the upper membrane pool unit is opened to start testing the gas permeability P and gas separation performance α of the membrane (323) in the membrane pool unit (3); Wait for the reading of the membrane pool pressure sensor (33) in the membrane pool unit (3) to reach the preset membrane pool unit pressure P M , opening the membrane pool outlet valve (34) in the membrane pool unit to be tested, closing the membrane pool outlet valve (34) after the gas in the membrane pool unit to be tested enters the gas chromatograph (6), and then using the gas chromatograph (6) for analysis, and calculating the gas permeability P of the gas continuously passing through the first-stage membrane pool unit (3) to each membrane (323) in the membrane pool unit to be tested according to formula 4; Among them, P2 takes the preset membrane pool unit pressure P M ; The gas separation performance α of each membrane (323) in the membrane pool unit to be tested is calculated according to formula 4 when the gas continuously passes through the first-stage membrane pool unit (3); In the ninth step, steps six to eight are repeated until the gas is continuously passed through the first-stage membrane pool unit (3) and the gas permeability P and the gas separation performance α of each membrane (323) in the last-stage membrane pool unit (3) are obtained.

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