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CO 2 extraction from seawater using bipolar membrane electrodialysis
Abstract
An efficient method for extracting the dissolved CO 2 in the oceans would effectively enable the separation of CO 2 from the atmosphere without the need to process large volumes of air, and could provide a key step in the synthesis of renewable, carbon-neutral liquid fuels. While the extraction of CO 2 from seawater has been previously demonstrated, many challenges remain, including slow extraction rates and poor CO 2 selectivity, among others. Here we describe a novel solution to these challenges – efficient CO 2 extraction from seawater using bipolar membrane electrodialysis (BPMED). We characterize the performance of a custom designed and built CO 2 -from-seawater prototype, demonstrating the ability to extract 59% of the total dissolved inorganic carbon from seawater as CO 2 gas with an electrochemical energy consumption of 242 kJ mol À1 (CO 2).
... However, the application of NaOH still leads to the pressing challenge of the CO 2 desorption from the absorbing solution for the following CO 2 sequestration step or its reuse as sodium carbonate. Bipolar membrane electrodialysis (BMED) is a likely option to regenerate CO 2 from carbonate and bicarbonate solutions192021. Furthermore, an integrated membrane-based approach proposed in a previous work also presents a promising candidate for mitigating CO 2 emissions [22, 23]., In this technology, CO 2 is captured as carbonate by means of reaction with NaOH and is further recovered as Na 2 CO 3 ·10H 2 O crystals in a membrane crystallizer. ...
Post-combustion CO2 capture by reaction with a strong alkali such as NaOH appears a promising strategy to mitigate CO2 emission. This study proposes bipolar membrane electrodialysis (BMED) as a technology for the reclamation of NaOH from glyphosate neutralization liquor and its subsequent use as an absorbent for CO2 capture. The proposed method produces a NaOH solution for further reaction with CO2 while recovering the glyphosate from the wastewater.
A NaOH solution with a concentration of ∼1.45 mol·L-1 and purity of ∼96.5% was obtained. Accordingly, a current efficiency of 80.8%, 76.2%, 68.7% and 69.0% at current densities of 30, 40, 50 and 60 mA·cm-2 was observed, respectively. In addition, the lowest energy utilization recorded as 2.15 kWh·kg-1 was obtained by the BMED process at a low current density of 30 mA·cm-2, resulting in a better performance in view of energy saving. A glyphosate recovery of ca. 98.2% was also achieved.
The environmental impact of the BMED process was evaluated in terms of the amount of CO2 emissions produced and the total amount of CO2 captured taking into account of the CO2 production through BMED process. The results demonstrate that a promising CO2 capture (up to 530.65 g CO2·kg-1 NaOH) can be only achieved if the electricity resources originate from renewable sources such as wind, hydroelectric, as well as solar photovoltaics or nuclear energy. However, the utilization of non-renewable energy resources for NaOH production by BMED process imposes a risk on producing a significant emission of CO2, which makes the application of BMED unviable for a CO2 capture scenario.
An environment friendly and cost-effective process has been developed for production of LiOH from spent LFP cathode material. By using a suspension electrolysis system comprising an electrodialysis process, the spent LFP cathode material was oxidized and released lithium ion in the anode chamber, which is similar to that in the charging of an LFP battery. More than 95% of Li was leached and the current efficiency can reach up to 85.81%. And then the resulting lithium ion was migrated through the cation-exchange membrane and generated LiOH with OH − in the cathode chamber. High purity LiOH solution could be obtained due to the impurities in anode chamber being insulated by the monovalent permselectivity cation-exchange membrane. Kinetics analysis indicates that the delithiation process on the anode electrode was divided into two stages. In the first stage, the reaction rate was limited by the electrochemistry. Thereafter, it was controlled by the diffusion in the second stage. Finally, LiOH·H 2 O can be directly produced after evaporative crystallization via vacuum evaporation. A green close-loop process was then proposed, in which very little solid waste or wastewater is generated. Compared with other recovery processes, the proposed process has the highest profit due to the production of LiOH·H 2 O which is more valuable and no chemical regents being consumed.
The ocean moderates anthropogenic climate change at the cost of profound alterations of its physics, chemistry, ecology, and services. Here, we evaluate and compare the risks of impacts on marine and coastal ecosystems-and the goods and services they provide-for growing cumulative carbon emissions under two contrasting emissions scenarios. The current emissions trajectory would rapidly and significantly alter many ecosystems and the associated services on which humans heavily depend. A reduced emissions scenario-consistent with the Copenhagen Accord's goal of a global temperature increase of less than 2°C-is much more favorable to the ocean but still substantially alters important marine ecosystems and associated goods and services. The management options to address ocean impacts narrow as the ocean warms and acidifies. Consequently, any new climate regime that fails to minimize ocean impacts would be incomplete and inadequate.
Copyright © 2015, American Association for the Advancement of Science.
To investigate the feasibility of a novel method to produce LiOH from lithium contained brine, A lab-scale electro–electrodialysis with bipolar membrane (EEDBM) was installed with an arrangement of bipolar membrane–cation exchange membrane–bipolar membrane–cation exchange membrane in series. Conventional electrodialysis (CED) stack configured with repeat-arranged five cation exchange membranes and four anion exchange membranes was installed as a pretreatment process. After preconcentrating and precipitating brine with CED and Na2CO3, a high purity of ca. 98% Li2CO3 powder was obtained. The influence of current density and feed concentration on the production of LiOH was investigated. EEDBM Process cost is estimated to 2.59 $/kg at current density of 30 mA/cm2 and feed concentration of 0.18 M. It can be inferred that lower energy consumption would be obtained at the case of scaling up. Considering the environmental aspects, the corporate process for LiOH production is also mutually beneficial.
The relationship between the level of atmospheric CO2 (carbon dioxide) and the impacts of climate change is uncertain, but a safe concentration may be surpassed this century. Therefore, it is necessary to develop technologies that can accelerate CO2 removal from the atmosphere. This paper explores the engineering challenges of a technology that manipulates the carbonate system in seawater by the addition of calcium oxide powder (CaO; lime), resulting in a net sequestration of atmospheric CO2 into the ocean (ocean liming; OL). Every tonne of CO2 sequestered requires between 1.4 and 1.7 t of limestone to be crushed, calcined, and distributed. Approximately 1 t of CO2 would be created from this activity, of which >80% is a high purity gas (pCO2 > 98%) amenable to geological storage. It is estimated that the thermal and electrical energy requirements for OL would be 0.6–5.6 and 0.1–1.2 GJ tCO2−1 captured respectively. A preliminary economic assessment suggests that OL could cost approximately US$72–159 t−1 of CO2. The additional CO2 burden of OL makes it a poor alternative to point source mitigation. However, it may provide a means to mitigate some diffuse emissions and reduce atmospheric concentrations.
To produce Morpholine (Mp) in an environmental friendly manner, bipolar membrane electrodialysis was used to convert Mp sulfate into Mp with 0.3 mol/L Na2SO4 as electrode supporting solution. The result indicated that a high current efficiency and low energy consumption can be obtained when Mp sulfate solution concentration is at the range of 0.15–0.22 mol/L, current density at the range of 20–30 mA/cm2 with BP-A-C-BP cell configuration. Product yield rate was increased with the increasing current density and feed concentration. At the same time, BP-A-BP and BP-C-BP cell configurations were also examined. A lowest process cost of 1.20 $/kg and energy consumption of 4.27 kW h/kg was obtained through BP-A-BP configuration compared with other types. This process was not only cost-effective, but also environmental benignity.
We experimentally demonstrate the direct coupling of silicate mineral dissolution with saline water electrolysis and H2 production to effect significant air CO2 absorption, chemical conversion, and storage in solution. In particular, we observed as much as a 10(5)-fold increase in OH(-) concentration (pH increase of up to 5.3 units) relative to experimental controls following the electrolysis of 0.25 M Na2SO4 solutions when the anode was encased in powdered silicate mineral, either wollastonite or an ultramafic mineral. After electrolysis, full equilibration of the alkalized solution with air led to a significant pH reduction and as much as a 45-fold increase in dissolved inorganic carbon concentration. This demonstrated significant spontaneous air CO2 capture, chemical conversion, and storage as a bicarbonate, predominantly as NaHCO3. The excess OH(-) initially formed in these experiments apparently resulted via neutralization of the anolyte acid, H2SO4, by reaction with the base mineral silicate at the anode, producing mineral sulfate and silica. This allowed the NaOH, normally generated at the cathode, to go unneutralized and to accumulate in the bulk electrolyte, ultimately reacting with atmospheric CO2 to form dissolved bicarbonate. Using nongrid or nonpeak renewable electricity, optimized systems at large scale might allow relatively high-capacity, energy-efficient (<300 kJ/mol of CO2 captured), and inexpensive (<$100 per tonne of CO2 mitigated) removal of excess air CO2 with production of carbon-negative H2. Furthermore, when added to the ocean, the produced hydroxide and/or (bi)carbonate could be useful in reducing sea-to-air CO2 emissions and in neutralizing or offsetting the effects of ongoing ocean acidification.
An electrochemical acidification cell is developed and tested as a method for extracting large quantities of carbon dioxide from seawater for use as a feedstock for jet-fuel synthesis at sea. The electrolytic regeneration of cation exchange resin was demonstrated, allowing simultaneous and continuous ion exchange and regeneration to occur within the cell along with control of the seawater pH. The CO2 in the seawater was readily removed at pHs of less than 6.0. In addition, the cell produced a portion of the hydrogen needed for jet-fuel synthesis without additional energy penalties.
A comparative cost/benefit and energy balance analysis addresses the critical scientific and technical challenges that impact the economic feasibility of synthesizing up to 100 000 gal per day of jet fuel at sea using carbon dioxide (CO2) and hydrogen (H-2) from the sea. Included in this analysis are the capital cost, operation and maintenance, and electrical generation cost for synthesizing jet fuel at sea using either ocean thermal energy conversion or nuclear power processes as the energy source. The results suggest that jet fuel could be produced at sea for $3 to $6/gal. Comparing these costs with current and historical prices of fuel purchased by the Department of Defense provides insight into the economic and operational benefits of a sea-based fuel synthesis process for the Navy. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4719723]
Strong base anion exchange resins were studied to determine if they could be used as a feasible and practical method for sequestering carbon dioxide from seawater for use as a carbon feedstock in a sea-based fuel production process. Static and dynamic flow experiments to determine the resin bicarbonate and chloride selectivity and the effect of ionic strength on bicarbonate selectivity and capacity are reported. These data are used to determine the scaled up feasibility of a carbon capture process by this approach.
Celgard 2400 gas permeable membranes were in contact with a model sodium bicarbonate solution on a closed system at elevated water pressures. When gaseous carbon dioxide was removed from the water by diffusion through the membrane, the bicarbonate disproportionated to carbon dioxide and carbonate. The carbon dioxide permeance rate and effect of ionic strength on disproportionation is reported.
A new type of CO2 separation process from flue gas stream was developed. The system is composed of the absorption step with an alkaline (e.g., sodium hydroxide) solution, and the recovery step with electrodialysis. The absorption step is a conventional gas absorption tower, where the flue gas containing CO2 is contacted with a stream of alkaline solution. The CO2 is captured in the form of carbonate ions and bicarbonate ions with alkaline metal ions as the counter cation. The solution is then moved to the electrodialysis unit, where a unit cell is composed of a sheet of cation exchange membrane sandwiched with two sheets of bipolar membrane. The carbonate solution is fed to the one room of the cell and then transported to the other room. In the electrodialysis cell, the pH of the carbonate solution was reduced by the protons supplied from one side of the bipolar membrane. At the same time, sodium ions were transported to the other room through the cation exchange membrane. And sodium hydroxide is recovered with hydroxyl ions supplied from the bipolar membrane. Optimization of the CO2 separation process with the presents system was conducted based on the experimental results on the electrodialysis and literature data on the CO2 absorption processes. An optimization was performed on the basis of minimization of power consumption or operation cost based on the degree of carbonation.
The book considers innovative methods to curtail CO emissions. It collects the latest research and actual applied techniques for reducing carbon dioxide, and utilizing waste CO as a feedstock; outlines newer, more effective ways to separate CO from waste-stream gases; explores the utilization of fossil fuels with reduced CO emissions; and presents up-to-date research into CO capture, and disposal, storage and sequestration of pressurized CO in the ocean and underground aquifers.
This invention relates to the use of a three compartment electrolytic cell in the production of synthetic carbonaceous fuels and chemical feedstocks such as gasoline, methane and methanol by electrolyzing an aqueous sodium carbonate/bicarbonate solution, obtained from scrubbing atmospheric carbon dioxide with an aqueous sodium hydroxide solution, whereby the hydrogen generated at the cathode and the carbon dioxide liberated in the center compartment are combined thermocatalytically into methanol and gasoline blends. The oxygen generated at the anode is preferably vented into the atmosphere, and the regenerated sodium hydroxide produced at the cathode is reused for scrubbing the CO[sub 2] from the atmosphere. 1 fig.
Past research with high temperature molten carbonate electrochemical cells has shown that carbon dioxide can be separated from flue gas streams produced by pulverized coal combustion for power generation. However, the presence of trace contaminants, i.e., sulfur dioxide and nitric oxides, will impact the electrolyte within the cell. If a lower temperature cell could be devised that would utilize the benefits of commercially-available, upstream desulfurization and denitrification in the power plant, then this CO2 separation technique can approach more viability in the carbon sequestration area. Recent work has led to the assembly and successful operation of a low temperature electrochemical cell. In the proof-of-concept testing with this cell, an anion exchange membrane was sandwiched between gas-diffusion electrodes consisting of nickel-based anode electrocatalysts on carbon paper. When a potential was applied across the cell and a mixture of oxygen and carbon dioxide was flowed over the wetted electrolyte on the cathode side, a stream of CO2 to O2 was produced on the anode side, suggesting that carbonate/bicarbonate ions are the CO2 carrier in the membrane. Since a mixture of CO2 and O2 is produced, the possibility exists to use this stream in oxy-firing of additional fuel.From this research, a novel concept for efficiently producing a carbon dioxide rich effluent from combustion of a fossil fuel was proposed. Carbon dioxide and oxygen are captured from the flue gas of a fossil-fuel combustor by one or more electrochemical cells or cell stacks. The separated stream is then transferred to an oxy-fired combustor which uses the gas stream for ancillary combustion, ultimately resulting in an effluent rich in carbon dioxide. A portion of the resulting flow produced by the oxy-fired combustor may be continuously recycled back into the oxy-fired combustor for temperature control and an optimal carbon dioxide rich effluent.
This report includes the development of the core ideas behind the making of liquid hydrocarbons at sea from environmental sources such as carbon dioxide and water as early as the fall of 2001. It also details the formal NRL documents that established projects specifically dealing with this topic beginning in the spring of 2004. Finally, it includes some of the unpublished results of work done on recovering carbon dioxide from seawater as a source of carbon for fuel synthesis beginning in the fall of 2004. These results are interpreted in the light of current understanding of the total carbon burden of the ocean and the exchange over time between atmosphere and ocean. The status of the project as of the fall of 2006 and plans for 2007 are also included. All subsequent NRL work beginning in FY07 on this topic will be published separately in a timely fashion as it is completed.
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