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      Using aluminum and water to make clean hydrogen fuel — when and where it’s needed

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      As the world works to move away from fossil fuels, many researchers are investigating whether clean hydrogen fuel can play an expanded role in sectors from transportation and industry to buildings and power generation. It could be used in fuel cell vehicles, heat-producing boilers, electricity-generating gas turbines, systems for storing renewable energy, and more.

      But while using hydrogen doesn’t generate carbon emissions, making it typically does. Today, almost all hydrogen is produced using fossil fuel-based processes that together generate more than 2 percent of all global greenhouse gas emissions. In addition, hydrogen is often produced in one location and consumed in another, which means its use also presents logistical challenges.

      A promising reaction

      Another option for producing hydrogen comes from a perhaps surprising source: reacting aluminum with water. Aluminum metal will readily react with water at room temperature to form aluminum hydroxide and hydrogen. That reaction doesn’t typically take place because a layer of aluminum oxide naturally coats the raw metal, preventing it from coming directly into contact with water.

      Using the aluminum-water reaction to generate hydrogen doesn’t produce any greenhouse gas emissions, and it promises to solve the transportation problem for any location with available water. Simply move the aluminum and then react it with water on-site. “Fundamentally, the aluminum becomes a mechanism for storing hydrogen — and a very effective one,” says Douglas P. Hart, professor of mechanical engineering at MIT. “Using aluminum as our source, we can ‘store’ hydrogen at a density that’s 10 times greater than if we just store it as a compressed gas.”

      Two problems have kept aluminum from being employed as a safe, economical source for hydrogen generation. The first problem is ensuring that the aluminum surface is clean and available to react with water. To that end, a practical system must include a means of first modifying the oxide layer and then keeping it from re-forming as the reaction proceeds.

      The second problem is that pure aluminum is energy-intensive to mine and produce, so any practical approach needs to use scrap aluminum from various sources. But scrap aluminum is not an easy starting material. It typically occurs in an alloyed form, meaning that it contains other elements that are added to change the properties or characteristics of the aluminum for different uses. For example, adding magnesium increases strength and corrosion-resistance, adding silicon lowers the melting point, and adding a little of both makes an alloy that’s moderately strong and corrosion-resistant.

      Despite considerable research on aluminum as a source of hydrogen, two key questions remain: What’s the best way to prevent the adherence of an oxide layer on the aluminum surface, and how do alloying elements in a piece of scrap aluminum affect the total amount of hydrogen generated and the rate at which it is generated?

      “If we’re going to use scrap aluminum for hydrogen generation in a practical application, we need to be able to better predict what hydrogen generation characteristics we’re going to observe from the aluminum-water reaction,” says Laureen Meroueh PhD ’20, who earned her doctorate in mechanical engineering.

      Since the fundamental steps in the reaction aren’t well understood, it’s been hard to predict the rate and volume at which hydrogen forms from scrap aluminum, which can contain varying types and concentrations of alloying elements. So Hart, Meroueh, and Thomas W. Eagar, a professor of materials engineering and engineering management in the MIT Department of Materials Science and Engineering, decided to examine — in a systematic fashion — the impacts of those alloying elements on the aluminum-water reaction and on a promising technique for preventing the formation of the interfering oxide layer.

      To prepare, they had experts at Novelis Inc. fabricate samples of pure aluminum and of specific aluminum alloys made of commercially pure aluminum combined with either 0.6 percent silicon (by weight), 1 percent magnesium, or both — compositions that are typical of scrap aluminum from a variety of sources. Using those samples, the MIT researchers performed a series of tests to explore different aspects of the aluminum-water reaction.

      Pre-treating the aluminum

      The first step was to demonstrate an effective means of penetrating the oxide layer that forms on aluminum in the air. Solid aluminum is made up of tiny grains that are packed together with occasional boundaries where they don’t line up perfectly. To maximize hydrogen production, researchers would need to prevent the formation of the oxide layer on all those interior grain surfaces.

      Research groups have already tried various ways of keeping the aluminum grains “activated” for reaction with water. Some have crushed scrap samples into particles so tiny that the oxide layer doesn’t adhere. But aluminum powders are dangerous, as they can react with humidity and explode. Another approach calls for grinding up scrap samples and adding liquid metals to prevent oxide deposition. But grinding is a costly and energy-intensive process.

      To Hart, Meroueh, and Eagar, the most promising approach — first introduced by Jonathan Slocum ScD ’18 while he was working in Hart’s research group — involved pre-treating the solid aluminum by painting liquid metals on top and allowing them to permeate through the grain boundaries.

      To determine the effectiveness of that approach, the researchers needed to confirm that the liquid metals would reach the internal grain surfaces, with and without alloying elements present. And they had to establish how long it would take for the liquid metal to coat all of the grains in pure aluminum and its alloys.

      They started by combining two metals — gallium and indium — in specific proportions to create a “eutectic” mixture; that is, a mixture that would remain in liquid form at room temperature. They coated their samples with the eutectic and allowed it to penetrate for time periods ranging from 48 to 96 hours. They then exposed the samples to water and monitored the hydrogen yield (the amount formed) and flow rate for 250 minutes. After 48 hours, they also took high-magnification scanning electron microscope (SEM) images so they could observe the boundaries between adjacent aluminum grains.

      Based on the hydrogen yield measurements and the SEM images, the MIT team concluded that the gallium-indium eutectic does naturally permeate and reach the interior grain surfaces. However, the rate and extent of penetration vary with the alloy. The permeation rate was the same in silicon-doped aluminum samples as in pure aluminum samples but slower in magnesium-doped samples.

      Perhaps most interesting were the results from samples doped with both silicon and magnesium — an aluminum alloy often found in recycling streams. Silicon and magnesium chemically bond to form magnesium silicide, which occurs as solid deposits on the internal grain surfaces. Meroueh hypothesized that when both silicon and magnesium are present in scrap aluminum, those deposits can act as barriers that impede the flow of the gallium-indium eutectic.

      The experiments and images confirmed her hypothesis: The solid deposits did act as barriers, and images of samples pre-treated for 48 hours showed that permeation wasn’t complete. Clearly, a lengthy pre-treatment period would be critical for maximizing the hydrogen yield from scraps of aluminum containing both silicon and magnesium.

      Meroueh cites several benefits to the process they used. “You don’t have to apply any energy for the gallium-indium eutectic to work its magic on aluminum and get rid of that oxide layer,” she says. “Once you’ve activated your aluminum, you can drop it in water, and it’ll generate hydrogen — no energy input required.” Even better, the eutectic doesn’t chemically react with the aluminum. “It just physically moves around in between the grains,” she says. “At the end of the process, I could recover all of the gallium and indium I put in and use it again” — a valuable feature as gallium and (especially) indium are costly and in relatively short supply.

      Impacts of alloying elements on hydrogen generation

      The researchers next investigated how the presence of alloying elements affects hydrogen generation. They tested samples that had been treated with the eutectic for 96 hours; by then, the hydrogen yield and flow rates had leveled off in all the samples.

      The presence of 0.6 percent silicon increased the hydrogen yield for a given weight of aluminum by 20 percent compared to pure aluminum — even though the silicon-containing sample had less aluminum than the pure aluminum sample. In contrast, the presence of 1 percent magnesium produced far less hydrogen, while adding both silicon and magnesium pushed the yield up, but not to the level of pure aluminum.

      The presence of silicon also greatly accelerated the reaction rate, producing a far higher peak in the flow rate but cutting short the duration of hydrogen output. The presence of magnesium produced a lower flow rate but allowed the hydrogen output to remain fairly steady over time. And once again, aluminum with both alloying elements produced a flow rate between that of magnesium-doped and pure aluminum.

      Those results provide practical guidance on how to adjust the hydrogen output to match the operating needs of a hydrogen-consuming device. If the starting material is commercially pure aluminum, adding small amounts of carefully selected alloying elements can tailor the hydrogen yield and flow rate. If the starting material is scrap aluminum, careful choice of the source can be key. For high, brief bursts of hydrogen, pieces of silicon-containing aluminum from an auto junkyard could work well. For lower but longer flows, magnesium-containing scraps from the frame of a demolished building might be better. For results somewhere in between, aluminum containing both silicon and magnesium should work well; such material is abundantly available from scrapped cars and motorcycles, yachts, bicycle frames, and even smartphone cases.

      It should also be possible to combine scraps of different aluminum alloys to tune the outcome, notes Meroueh. “If I have a sample of activated aluminum that contains just silicon and another sample that contains just magnesium, I can put them both into a container of water and let them react,” she says. “So I get the fast ramp-up in hydrogen production from the silicon and then the magnesium takes over and has that steady output.”

      Another opportunity for tuning: Reducing grain size

      Another practical way to affect hydrogen production could be to reduce the size of the aluminum grains — a change that should increase the total surface area available for reactions to occur.

      To investigate that approach, the researchers requested specially customized samples from their supplier. Using standard industrial procedures, the Novelis experts first fed each sample through two rollers, squeezing it from the top and bottom so that the internal grains were flattened. They then heated each sample until the long, flat grains had reorganized and shrunk to a targeted size.

      In a series of carefully designed experiments, the MIT team found that reducing the grain size increased the efficiency and decreased the duration of the reaction to varying degrees in the different samples. Again, the presence of particular alloying elements had a major effect on the outcome.

      Needed: A revised theory that explains observations

      Throughout their experiments, the researchers encountered some unexpected results. For example, standard corrosion theory predicts that pure aluminum will generate more hydrogen than silicon-doped aluminum will — the opposite of what they observed in their experiments.

      To shed light on the underlying chemical reactions, Hart, Meroueh, and Eagar investigated hydrogen “flux,” that is, the volume of hydrogen generated over time on each square centimeter of aluminum surface, including the interior grains. They examined three grain sizes for each of their four compositions and collected thousands of data points measuring hydrogen flux.

      Their results show that reducing grain size has significant effects. It increases the peak hydrogen flux from silicon-doped aluminum as much as 100 times and from the other three compositions by 10 times. With both pure aluminum and silicon-containing aluminum, reducing grain size also decreases the delay before the peak flux and increases the rate of decline afterward. With magnesium-containing aluminum, reducing the grain size brings about an increase in peak hydrogen flux and results in a slightly faster decline in the rate of hydrogen output. With both silicon and magnesium present, the hydrogen flux over time resembles that of magnesium-containing aluminum when the grain size is not manipulated. When the grain size is reduced, the hydrogen output characteristics begin to resemble behavior observed in silicon-containing aluminum. That outcome was unexpected because when silicon and magnesium are both present, they react to form magnesium silicide, resulting in a new type of aluminum alloy with its own properties.

      The researchers stress the benefits of developing a better fundamental understanding of the underlying chemical reactions involved. In addition to guiding the design of practical systems, it might help them find a replacement for the expensive indium in their pre-treatment mixture. Other work has shown that gallium will naturally permeate through the grain boundaries of aluminum. “At this point, we know that the indium in our eutectic is important, but we don’t really understand what it does, so we don’t know how to replace it,” says Hart.

      But already Hart, Meroueh, and Eagar have demonstrated two practical ways of tuning the hydrogen reaction rate: by adding certain elements to the aluminum and by manipulating the size of the interior aluminum grains. In combination, those approaches can deliver significant results. “If you go from magnesium-containing aluminum with the largest grain size to silicon-containing aluminum with the smallest grain size, you get a hydrogen reaction rate that differs by two orders of magnitude,” says Meroueh. “That’s huge if you’re trying to design a real system that would use this reaction.”

      This research was supported through the MIT Energy Initiative by ExxonMobil-MIT Energy Fellowships awarded to Laureen Meroueh PhD ’20 from 2018 to 2020.

      This article appears in the Spring 2021 issue of Energy Futures, the magazine of the MIT Energy Initiative.  More

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      Cleaning up industrial filtration

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      If you wanted to get pasta out of a pot of water, would you boil off the water, or use a strainer? While home cooks would choose the strainer, many industries continue to use energy-intensive thermal methods of separating out liquids. In some cases, that’s because it’s difficult to make a filtration system for chemical separation, which requires pores small enough to separate atoms.

      In other cases, membranes exist to separate liquids, but they are made of fragile polymers, which can break down or gum up in industrial use.

      Via Separations, a startup that emerged from MIT in 2017, has set out to address these challenges with a membrane that is cost-effective and robust. Made of graphene oxide (a “cousin” of pencil lead), the membrane can reduce the amount of energy used in industrial separations by 90 percent, according to Shreya Dave PhD ’16, company co-founder and CEO.

      This is valuable because separation processes account for about 22 percent of all in-plant energy use in the United States, according to Oak Ridge National Laboratory. By making such processes significantly more efficient, Via Separations plans to both save energy and address the significant emissions produced by thermal processes. “Our goal is eliminating 500 megatons of carbon dioxide emissions by 2050,” Dave says.

      Play video

      What do our passions for pasta and decarbonizing the Earth have in common? MIT alumna Shreya Dave PhD ’16 explains how she and her team at Via Separations are building the equivalent of a pasta strainer to separate chemical compounds for industry.

      Via Separations began piloting its technology this year at a U.S. paper company and expects to deploy a full commercial system there in the spring of 2022. “Our vision is to help manufacturers slow carbon dioxide emissions next year,” Dave says.

      MITEI Seed Grant

      The story of Via Separations begins in 2012, when the MIT Energy Initiative (MITEI) awarded a Seed Fund grant to Professor Jeffrey Grossman, who is now the Morton and Claire Goulder and Family Professor in Environmental Systems and head of MIT’s Department of Materials Science and Engineering. Grossman was pursuing research into nanoporous membranes for water desalination. “We thought we could bring down the cost of desalination and improve access to clean water,” says Dave, who worked on the project as a graduate student in Grossman’s lab.

      There, she teamed up with Brent Keller PhD ’16, another Grossman graduate student and a 2016-17 ExxonMobil-MIT Energy Fellow, who was developing lab experiments to fabricate and test new materials. “We were early comrades in figuring out how to debug experiments or fix equipment,” says Keller, Via Separations’ co-founder and chief technology officer. “We were fast friends who spent a lot of time talking about science over burritos.”

      Dave went on to write her doctoral thesis on using graphene oxide for water desalination, but that turned out to be the wrong application of the technology from a business perspective, she says. “The cost of desalination doesn’t lie in the membrane materials,” she explains.

      So, after Dave and Keller graduated from MIT in 2016, they spent a lot of time talking to customers to learn more about the needs and opportunities for their new separation technology. This research led them to target the paper industry, because the environmental benefits of improving paper processing are enormous, Dave says. “The paper industry is particularly exciting because separation processes just in that industry account for more than 2 percent of U.S. energy consumption,” she says. “It’s a very concentrated, high-energy-use industry.”

      Most paper today is made by breaking down the chemical bonds in wood to create wood pulp, the primary ingredient of paper. This process generates a byproduct called black liquor, a toxic solution that was once simply dumped into waterways. To clean up this process, paper mills turned to boiling off the water from black liquor and recovering both water and chemicals for reuse in the pulping process. (Today, the most valuable way to use the liquor is as biomass feedstock to generate energy.) Via Separations plans to accomplish this same separation work by filtering black liquor through its graphene oxide membrane.

      “The advantage of graphene oxide is that it’s very robust,” Dave says. “It’s got carbon double bonds that hold together in a lot of environments, including at different pH levels and temperatures that are typically unfriendly to materials.”

      Such properties should also make the company’s membranes attractive to other industries that use membrane separation, Keller says, because today’s polymer membranes have drawbacks. “For most of the things we make — from plastics to paper and gasoline — those polymers will swell or react or degrade,” he says.

      Graphene oxide is significantly more durable, and Via Separations can customize the pores in the material to suit each industry’s application. “That’s our secret sauce,” Dave says, “modulating pore size while retaining robustness to operate in challenging environments.”

      “We’re building a catalog of products to serve different applications,” Keller says, noting that the next target market could be the food and beverage industry. “In that industry, instead of separating different corrosive paper chemicals from water, we’re trying to separate particular sugars and food ingredients from other things.”

      Future target customers include pharmaceutical companies, oil refineries, and semiconductor manufacturers, or even carbon capture businesses.

      Scaling up

      Dave, Keller, and Grossman launched Via Separations in 2017 — with a lot of help from MIT. After the seed grant, in 2015, the founders received a year of funding and support from the J-WAFS Solutions program to explore markets and to develop their business plans. The company’s first capital investment came from The Engine, a venture firm founded by MIT to support “tough tech” companies (tech businesses with transformative potential but long and challenging paths to success). They also received advice and support from MIT’s Deshpande Center for Technological Innovation, Venture Mentoring Service, and Technology Licensing Office. In addition, Grossman continues to serve the company as chief scientist.

      “We were incredibly fortunate to be starting a company in the MIT entrepreneurial ecosystem,” Keller says, noting that The Engine support alone “probably shaved years off our progress.”

      Already, Via Separations has grown to employ 17 people, while significantly scaling up its product. “Our customers are producing thousands of gallons per minute,” Keller explains. “To process that much liquid, we need huge areas of membrane.”

      Via Separations’ manufacturing process, which is now capable of making more than 10,000 square feet of membrane in one production run, is a key competitive advantage, Dave says. The company rolls 300-400 square feet of membrane into a module, and modules can be combined as needed to increase filtration capacity.

      The goal, Dave says, is to contribute to a more sustainable world by making an environmentally beneficial product that makes good business sense. “What we do is make manufacturing things more energy-efficient,” she says. “We allow a paper mill or chemical facility to make more product using less energy and with lower costs. So, there is a bottom-line benefit that’s significant on an industrial scale.”

      Keller says he shares Dave’s goal of building a more sustainable future. “Climate change and energy are central challenges of our time,” he says. “Working on something that has a chance to make a meaningful impact on something so important to everyone is really fulfilling.”

      This article appears in the Spring 2021 issue of Energy Futures, the magazine of the MIT Energy Initiative.  More

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      Reducing emissions by decarbonizing industry

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      A critical challenge in meeting the Paris Agreement’s long-term goal of keeping global warming well below 2 degrees Celsius is to vastly reduce carbon dioxide (CO2) and other greenhouse gas emissions generated by the most energy-intensive industries. According to a recent report by the International Energy Agency, these industries — cement, iron and steel, chemicals — account for about 20 percent of global CO2 emissions. Emissions from these industries are notoriously difficult to abate because, in addition to emissions associated with energy use, a significant portion of industrial emissions come from the process itself.

      For example, in the cement industry, about half the emissions come from the decomposition of limestone into lime and CO2. While a shift to zero-carbon energy sources such as solar or wind-powered electricity could lower CO2 emissions in the power sector, there are no easy substitutes for emissions-intensive industrial processes.

      Enter industrial carbon capture and storage (CCS). This technology, which extracts point-source carbon emissions and sequesters them underground, has the potential to remove up to 90-99 percent of CO2 emissions from an industrial facility, including both energy-related and process emissions. And that begs the question: Might CCS alone enable hard-to-abate industries to continue to grow while eliminating nearly all of the CO2 emissions they generate from the atmosphere?

      The answer is an unequivocal yes in a new study in the journal Applied Energy co-authored by researchers at the MIT Joint Program on the Science and Policy of Global Change, MIT Energy Initiative, and ExxonMobil.

      Using an enhanced version of the MIT Economic Projection and Policy Analysis (EPPA) model that represents different industrial CCS technology choices — and assuming that CCS is the only greenhouse gas emissions mitigation option available to hard-to-abate industries — the study assesses the long-term economic and environmental impacts of CCS deployment under a climate policy aimed at capping the rise in average global surface temperature at 2 C above preindustrial levels.

      The researchers find that absent industrial CCS deployment, the global costs of implementing the 2 C policy are higher by 12 percent in 2075 and 71 percent in 2100, relative to policy costs with CCS. They conclude that industrial CCS enables continued growth in the production and consumption of energy-intensive goods from hard-to-abate industries, along with dramatic reductions in the CO2 emissions they generate. Their projections show that as industrial CCS gains traction mid-century, this growth occurs globally as well as within geographical regions (primarily in China, Europe, and the United States) and the cement, iron and steel, and chemical sectors.

      “Because it can enable deep reductions in industrial emissions, industrial CCS is an essential mitigation option in the successful implementation of policies aligned with the Paris Agreement’s long-term climate targets,” says Sergey Paltsev, the study’s lead author and a deputy director of the MIT Joint Program and senior research scientist at the MIT Energy Initiative. “As the technology advances, our modeling approach offers decision-makers a pathway for projecting the deployment of industrial CCS across industries and regions.”

      But such advances will not take place without substantial, ongoing funding.

      “Sustained government policy support across decades will be needed if CCS is to realize its potential to promote the growth of energy-intensive industries and a stable climate,” says Howard Herzog, a co-author of the study and senior research engineer at the MIT Energy Initiative.

      The researchers also find that advanced CCS options such as cryogenic carbon capture (CCC), in which extracted CO2 is cooled to solid form using far less power than conventional coal- and gas-fired CCS technologies, could help expand the use of CCS in industrial settings through further production cost and emissions reductions.

      The study was supported by sponsors of the MIT Joint Program and by ExxonMobil through its membership in the MIT Energy Initiative. More