CO2 CAPTURE AND CONVERSION USING A NOVEL MEMBRANE SYSTEM
20230405520 ยท 2023-12-21
Inventors
Cpc classification
B01D2311/2603
PERFORMING OPERATIONS; TRANSPORTING
B01D61/52
PERFORMING OPERATIONS; TRANSPORTING
B01D53/228
PERFORMING OPERATIONS; TRANSPORTING
B01D53/229
PERFORMING OPERATIONS; TRANSPORTING
B01D2315/06
PERFORMING OPERATIONS; TRANSPORTING
International classification
B01D61/52
PERFORMING OPERATIONS; TRANSPORTING
Abstract
An apparatus for capturing carbon dioxide has a membrane separator with a gas inlet, a gas outlet, a channel that extends between the gas inlet and the gas outlet, and pores configured to permit carbon dioxide to pass therethrough, the gas inlet being connected to receive a mixed gas that contains carbon dioxide, wherein carbon dioxide in the mixed gas exits the membrane via the pores, and a remainder of the mixed gas exits the membrane separator via the gas outlet. The pores may be functionalized with nano-particles. A container is filled with an aqueous solution includes a carbon capturing agent and the membrane separator is submerged within the aqueous solution. The carbon capturing agent may be produced by a membrane reactor upstream of the membrane separator. Carbon dioxide exiting the membrane separator via the functional pores reacts with the carbon capturing agent to produce a carbon negative compound.
Claims
1. An apparatus for capturing carbon dioxide, comprising: A membrane separator having a gas inlet, a gas outlet, a channel that extends between the gas inlet and the gas outlet, and pores configured to permit carbon dioxide to pass therethrough, the gas inlet being connected to receive a mixed gas that contains carbon dioxide, wherein carbon dioxide in the mixed gas exits the membrane via the pores, and a remainder of the mixed gas exits the membrane separator via the gas outlet; and a container filled with an aqueous solution that comprises a carbon capturing agent, the membrane separator is submerged within the aqueous solution, wherein carbon dioxide exiting the membrane separator via the functional pores reacts with the carbon capturing agent to produce a carbon negative compound.
2. The apparatus of claim 1, wherein the pores comprise nanoparticles that functionalize the pores.
3. The apparatus of claim 1, wherein the carbon capturing agent comprises sodium ions, hydroxide ions, sodium compounds, hydroxide compounds, or combinations thereof.
4. The apparatus of claim 1, wherein the container comprises first and second compartments separated by a baffle, wherein the membrane separator is submerged in the first compartment and a second membrane separator is submerged in the second compartment, wherein an outlet of the second separator being connected to the inlet of the membrane separator.
5. The apparatus of claim 1, wherein the carbon dioxide comprises between 5 and 70 wt % of the mixed gas, the mixed gas further comprising one or more of: nitrogen, oxygen, methane, and hydrogen.
6. The apparatus of claim 1, further comprising a primary membrane separator positioned within a primary container, the primary membrane separator defining a first volume and a second volume within the primary container, the primary membrane separator having pores configured to permit sodium and hydrogen to pass therethrough, the first volume receiving a mixture of sodium chloride, water, and a caustic agent, wherein an applied potential voltage causes sodium and hydrogen to pass through the primary membrane separator, the primary container having an outlet in fluid communication with the container.
7. The apparatus of claim 6, wherein the pores of the primary membrane separator comprise nanoparticles that functionalize the pores.
8. The apparatus of claim 6, wherein the container comprises a preconditioner that receives sodium from the outlet of the primary container, the sodium being conditioned in the preconditioner to form the carbon capturing agent prior to being transferred to the container.
9. The apparatus of claim 6, wherein chlorine gas exits the first volume of the primary container, and hydrogen gas exists the second volume of the primary container.
10. The apparatus of claim 9, wherein the primary container further produces chloroacetic acid, CaCl.sub.2, or both chloroacetic acid and CaCl.sub.2.
11. The apparatus of claim 6, wherein the applied voltage comprises a cell voltage of 3.8 V or less and a current density of 7000 A/m.sup.2 or less.
12. The apparatus of claim 1, wherein the carbon capturing agent reacts with the carbon dioxide to produce at least one of: NaHCO.sub.3, Na.sub.2CO.sub.3, (NH.sub.4).sub.2CO.sub.3, and (NH.sub.4)HCO.sub.3.
13. The apparatus of claim 1, wherein the membrane comprises a PTFE-based material.
14. The apparatus of claim 1, wherein the membrane separator has an effective selectivity of between 57 and 109, and a flux in the range of between 328 and 394 GPU.
15. The apparatus of claim 1, wherein a pressure of the mixed gas in the membrane separator is between 15 and 25 psi.
16. The apparatus of claim 1, further comprising an operating system that is programmed to control an operation of the membrane separator.
17. The apparatus of claim 16, wherein the operating system comprises a wireless communication link.
18. The apparatus of claim 16, wherein the operating system comprises a plurality of control modules.
19. The apparatus of claim 1, wherein the membrane separator comprises a plurality of membrane modules.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0031] These and other features will become more apparent from the following description in which reference is made to the appended drawings, the drawings are for the purposes of illustration only and are not intended to be in any way limiting, wherein:
[0032]
[0033]
[0034]
[0035]
[0036]
[0037]
[0038]
DETAILED DESCRIPTION
[0039] There will now be described a process and integrated membrane system, identified generally by reference number 10, that captures CO.sub.2 and converts some or all of the CO.sub.2 into various carbon-negative industrial chemicals.
[0040] Referring to
[0041] Referring to
[0042] As noted above, the components are mixed together in first conditioner 108 to form a conditioned feed solution 112. The mixing time may be about 1 to 3 minutes of continuous mixing prior to adding conditioned feed solution 112 into an SMA tank 114 or other suitable container using a pump 116. When an appropriate current is applied to electrodes 118, sodium and hydrogen pass through a membrane 120 in SMA tank 114, while chlorine and other components do not. A capturing agent or capturing agent precursor 30 is produced for use in Carbon Capture and Conversion (CCC) System 200 depicted in
[0043] SMA system 100 may include a system of asymmetric SIF membranes and electrodes that is controlled with the operating system 14. As SIF membranes may be relatively thin and fragile, they may be reinforced with polytetrafluoroethylene (PTFE) to increase their mechanical strength for wide industrial applications. In a traditional electromembrane process, the voltage efficiency of the process is mainly caused by activation overpotential of the anode reaction and ohmic drop on the membrane. Using such an SIF membrane, the current efficiency loss mainly accounts for the transport of hydroxyl ions from the cathode to the anode compartment due to joint diffusion and migration. When enhanced with PTFE, the SIF technologies may form a strong ion charged surface film on top of the PTFE, thus reducing the flow of hydroxyl and chloride ions, improving the energy efficiency while producing a CO.sub.2 capturing agent with relatively high purity.
[0044] The SIF membranes with dense ion surface may be used to provide a selective pathway for sodium (Na.sup.+) ions, minimize anions such as chloride (CI.sup.) or other anions from diffusing across SIF and decrease in hydroxyl ion flow back to the anode inside the cathode chamber, and decrease the membrane resistivity; in other words, the SIF membrane may be designed to keep the OH.sup. and Cl.sup. ions away from the membrane surface to reduce the potential polarization on the SIF surface, and enhance the flux of sodium (Na.sup.+) ion selectivity that increases the purity and concentration of the capturing agent in an energy-efficient manner.
[0045] The conditioned solution from conditioner 108 is then fed into an anode chamber 122 inside the SMA tank 114. To avoid concentration polarization around an anode 124, conditioned solution 112 may be uniformly distributed around anode 124 in anode chamber 122. The ionic contact between the SIF membrane 120 and the electrode results in the formation of a three-dimensional active layer, providing a contacting surface and ionically conductive pathways among the electrodes 118, SIF membrane 120 and the electrolyte. This may improve the electric efficiency and life of anode 124.
[0046] Depending on the requirements and operation from the down stream process, the voltage applied to electrodes 118 may vary, such as from 1.5V to 3.8V, and which may be continuously optimized with an operating system 14 during the operations. As a result, the Cl.sup. ion in anode chamber 122 is converted into Cl.sub.2 gas 126 and collected from the top of Anode chamber 122. The quality of chlorine gas 126 may be sufficient to be liquified as liquid chlorine product. If desired, chlorine gas 126 may also be converted into various carbon negative chemicals, such as hypochloric acid, chloroacetic acid, or dissolved into a CaO solution to form CaCl.sub.2. Any residue from anode chamber 122 may be continuously removed and properly disposed of. Carbon negative compounds (or chemicals) include those compounds that are produced from carbon dioxide and stable under normal temperature and pressure conditions.
[0047] A cathode compartment 130 inside SMA container 114 may be initially fed with a 0.1% wt water solution of sodium hydroxide, with a pH of about 14. Under the applied voltage, the water solution is initially reduced to gaseous hydrogen and hydroxyl ions simultaneously at a cathode 132:
2H.sub.2O+2e.sup.=H.sub.22OH.sup.E.sup.O.sub.(H2O/H2)=0.828 V
[0048] Hydrogen gas 134 generated in the Cathode chamber 130 may be collected from the top of cathode chamber 130, then compressed or liquified for industrial use. In some examples, the purity of hydrogen gas 134 may exceed 99.95%.
[0049] With the applied voltage, the Na.sup.+ ion in anode chamber 122 is pulled to SIF membrane 120, driven through SIF membrane 120 and into cathode chamber 130, where the Na.sup.+ ion is reacted with OH.sup. ions in the conditioned agent to form CO.sub.2 capturing agent 30. An optimum concentration of capturing agent 30 in cathode chamber 103 may be controlled by operating system 14, depending on the requirements from the CCC system 200 operation. Inside SMA tank 114, an appropriate design of SIF 120 helps produce a high quality of CO.sub.2 capturing agent 30 in an energy efficient manner.
[0050]
[0051] The sEO and eAi systems 20 and 22 may also enable the SMA 100 and the CCC system 200 to be operated remotely, which may allow the operator to remotely diagnose the system problems and fine tune the operation to improve the operation efficiency and reliability.
[0052]
[0053] With the optimization from operating system 14, the energy efficiency of SMA system 100 may be improved relative to electrolysis with a conventional process such as a porous diaphragm. Safety improvement in SMA system 100 represents an additional important aspect.
[0054]
[0055] In the depicted example, CO.sub.2 capturing agent 30 from first stage 12 is conditioned with a second conditioning agent 44 in feed conditioner 32, and then fed into first SMR 34, while the mixed CO.sub.2 gas from second SMR 36 with the lowered CO.sub.2 concentration flows through the membrane in first SMR 34 along the membrane's internal channel (not shown). Second conditioning agent 44 may be based on sodium and hydroxide ions or related compounds obtained from SMA 100. Second conditioning agent 44 may also include other additives that improve stability, improve efficiency, or improve the life expectancy of the membrane. In some examples, NaHCO.sub.3 may be included as a seeding compound. Water may be added as needed. While the number of reactors may vary, the depicted example includes first and second SMRs 34 and 36 separated by a baffle 50, and a weir 52 adjacent to the outlet of second SMR 36. Baffle 50 and weir 52 may be provided to control the fluid flow and therefore the reaction as the mixed capturing agent from first SMR 34 flows into second SMR 36 at the bottom by the gravity. As the CO.sub.2 exits membrane 46, it reacts with the capturing agent to produce a recoverable compound, such as NaHCO.sub.3. The membrane maintenance and recovery cleaning systems 40 may be automatically operated and controlled by the operating system. The number of SMR stages may be increased or decreased, depending on the materials available and the desired results. It will also be recognized that, if an alternative carbon capturing agent is obtained, CCC system 200 may be operated without SMA 100.
[0056] Depending on the overall operation, the concentration of CO.sub.2 in the mixed gas from second SMR B may vary from 1 to 18.5%. In case of the flue gas from a power plant, an example of a typical composition of the raw flue gas may be as follows: [0057] 1) CO.sub.2.fwdarw.8.5-13.8%, [0058] 2) N.sub.2.fwdarw.76-77% [0059] 3) O.sub.2.fwdarw.4.4-4.8% [0060] 4) H.sub.2O.fwdarw.6.2-6.5%, [0061] 5) CO<50 ppm, [0062] 6) SO.sub.2<420 ppm and [0063] 7) NO.sub.x<420 ppm.
[0064] With the CO.sub.2 concentration varying from 8.5% to 13.8% in the raw mixed gas, the feeding CO.sub.2 concentration to SMR A may vary from 3.1 to 6.9% and the recovery rate may be greater than 99.9%. this may be achieved through optimization of the operating parameters, and/or by recycling the mixed gas, such as from first SMR 34 back to second SMR 36.
[0065] When the CO.sub.2 mixed gas flows through the internal channel of the membranes of SMRs 34 and 36, the CO.sub.2 is selectively permeated through the membranes from the inside to the outside surface of the membranes. The CO.sub.2 at the surface of the membranes reacts rapidly with the high concentration of the fresh CO.sub.2 capturing agent. The large reacting surface provided by the membranes and fast chemical reactions may allow the capturing agent to capture more than 99.9% CO.sub.2 permeated through the membrane. Under the control of the operating system 14 (as shown in
[0066] The partially-used CO.sub.2 capturing agent 30 from first SMR 34 flows into second SMR 36 at the bottom by the gravity and continues to capture CO.sub.2 at the surface of the membranes inside second SMR 36 while the raw CO.sub.2 mixed gas such as the flue gas from the power plant flows through the membranes from second SMR 36 to first SMR 34.
[0067] SMR uses HNF membranes, which are hybrid nano-fibre membranes containing specially engineered nano-particles and employing an asymmetric structure formed with an advanced polymeric formula. Compared to many traditional polymeric membranes, the specially engineered nano-particles, the enhanced compatible polymeric formula, and advanced engineering process allows novel structures to be formed that have better selectivity and increased permeability for CO.sub.2 in a CO.sub.2/N.sub.2/O.sub.2 gas mixture, while maintaining the advantages of mechanical stability of PVDF polymeric membranes and the possibility of large-scale production.
[0068] Depending on the composition of the raw mixed gas and operation conditions, the ratio of membranes in second SMR 36 to that in first SMR 34 may be engineered to vary from 0.8 to 3.8 based on final process requirements. The membranes in SMRs 34 and 36 may be functionalized to enhance the separation of CO.sub.2 from the mixed gas using the nano-particles with specific functional groups, such as the functional groups shown in
[0069] The selective membrane reactors 34 and 36 in CCC system 200 may contain membrane modules, cassettes with 24 to 64 modules, any may be connected to, or include, online analyzing and monitoring systems, and integrated maintenance and recovery systems 40 that may be controlled and operated by the operating system 14. The membrane cassettes (not shown) may be designed as a basic modular element, and engineered into an independent train. In some examples, between 2 and 16 independent trains may be used in CCC system 200 depending on the mass flow of a CO.sub.2 mixed gas. Therefore, the modular engineering design may be easily applied for various industrial scales. Furthermore, using a modular engineering design and the operating system, CCC system 200 allows rapid startup and each train may be easily isolated from the system for troubleshooting and repairing. In some examples, CCC system 200 engineering may allow various membranes besides the HNF membranes to be utilized for CO.sub.2 capturing and conversion.
[0070] The membranes used in SMRs 34 and 36 may be manufactured with an enhanced thick PVDF layer that support the strength and rigidity of the membrane. Nano particles may be embedded into the matrix with the intrinsic micropores forming a flexible polymeric structure that may be regulated with operational pressure and other operational parameters. The pores of the membrane may also be referred to as void volumes, and may be functionalized with nano-particles. This approach may be used to increase the amount of the free volume in the membrane matrix. As a result, the CO.sub.2 gas flux is increased and may be regulated according to the operation and feeding mass flow of CO.sub.2 mixed gas.
[0071]
[0072] As shown in
[0073] The two-stages of CCC system 200 discussed herein may be used to effectively capture CO.sub.2 from various gas mixtures that may then be converted into carbon negative chemicals for various industrial applications. CCC system 200 may include one or more of the following aspects. [0074] A. With the advanced PVDF formula, HNF membranes may be used that have high strength, strong resistance to various chemicals, aging and plasticization as well as being easily and economically manufactured into different sizes and shapes of membrane modules. [0075] B. The operating system 14 may be configured into five modular blocks that communicate using a wireless link, such as by 5G, where each block may be operated independently or with other modules depending on the process requirements. The operating system 14 may be expanded with more modular blocks depending on the process and operation requirements. [0076] C. The HNF membrane may be designed to operate with optimal flux and selectivity when the operation pressure is within the pressure range of 15 to 25 psi. When the pressure is over the critical range, the flux may increase, such as by more than 20%, at the price of decreasing selectivity. This feature allows the membrane system to manage the peaking conditions when the CO.sub.2 capturing rate is allowed to vary or an emergency repair is required while keeping continuous operation. On the other hand, when at low demand, CCC system 200 with the modular engineering design may also be operated with the minimum amount of the membranes while the rest of CCC system 200 may be properly maintained and reserved to save the energy and operation cost, as well as extend the membrane life. In other words, combining operating system 14 with the modular engineering design allows CCC system 200 to operate at the higher (up to 200%) designed capacity or at lower (down to 5 or 10%) design capacity when desired. [0077] D. The operating system 14 may be programmed to control the process operational parameters, such as the pressure, membrane flux, pH and other parameters, to improve the process operation including the productivity and quality of the final products. For example, the operational pressure and/or temperature may be controlled to manage the flux, permselectivity, and energy efficiency. Depending on the composition of the mixed gas and desired final chemicals, the MO module may be used to improve the operation pressure within the range of 5 to 50 psi. Moreover, The MO and CT modules in the operating system can also carry out automatic maintenance and recovery cleaning of the membrane systems, thus, it improves the productivity while maintaining the membrane performance and to minimize membrane fouling and extend the membrane operation life. [0078] E. The operating system 14 may allow for the remote control and diagnoses of the process operation so that operation issues may be resolved by experts, remotely if needed. This may result in an improved or optimized start-up, and enhance troubleshooting capabilities. [0079] F. CCC system 200 may employ a modular membrane design. The modular design allows the system to scale up, such as up to 16 trains for various industrial applications. [0080] G. CCC system 200 may be engineered to operate in a relatively low-pressure range. The low operation pressure may reduce energy consumption and may improve reliability and safety. Furthermore, by producing valuable carbon negative chemicals, CCC system 200 can be profitable for capturing CO.sub.2 from various CO.sub.2 gas mixture. [0081] H. By properly managing a high flux and peaking factor using the operating system, CCC system 200 may be designed with reduced membrane area requirements, which may also reduce the capital cost. This may make CCC system 200 more practical and economical for large scale industrial application. [0082] I. Using a two-stage engineering design, CCC system 200 may have an improved energy efficiency, reliability and flexibility, and in some examples, may be used to achieve a CO.sub.2 capturing rate of better than 99.9%. Operating system 14 may be used to improve the tolerance of CCC system 200 to variations of CO.sub.2 concentration in the feeding mixed gas. In some examples, operating system 14 may accommodate variations in CO.sub.2 concentrations from 5 to 70%. [0083] J. With operating system 14 and SMA system 100, CCC system 200 may use different raw materials such as sea water and other form of brines, and the final products may be various valuable carbon negative industrial chemicals such as NaHCO.sub.3, Na.sub.2CO.sub.3, Cl.sub.2 gas, chloroacetic acid, CaCl.sub.2, liquid H.sub.2 etc. For example, various concentrations of NaHCO.sub.3 solution ranging from 50% to 99.5% saturated solution may be obtained as the final products to meet various industrial requirements. If desired, the NaHCO.sub.3 in the saturated solution may be simply crystalized into solid NaHCO.sub.3 or Na.sub.2CO.sub.3 products that meet the standard of membrane grade of NaHCO.sub.3/Na.sub.2CO.sub.3.
[0084] In this patent document, the word comprising is used in its non-limiting sense to mean that items following the word are included, but items not specifically mentioned are not excluded. A reference to an element by the indefinite article a does not exclude the possibility that more than one of the elements is present, unless the context requires that there be one and only one of the elements.
[0085] The scope of the following claims should not be limited by the preferred embodiments set forth in the examples above and in the drawings but should be given the broadest interpretation consistent with the description as a whole.