1. Introduction
As of 2022, methane is the second largest contributor to global greenhouse gas emissions at 11.1% of total emissions, ahead of nitrous oxide (6.1%), and behind carbon dioxide (79.7%). Since the Industrial Revolution, methane is estimated to have contributed about a third of net global warming. On a 20-year time scale, methane has proven to have a warming impact 86 times greater than carbon dioxide. Projections have estimated that removing a total of 0.3–1.0 Gt CH
4 by 2050 will slow global warming by 0.22 °C [
1].
Technologies exist to remove methane from the environment, but each technology comes with its own set of limitations. Thermal oxidation operates at more than 1400 °F, demanding high energy consumption [
2], so this strategy is typically only employed for point sources of high-concentration methane streams. This is a major disadvantage, and catalytic oxidation was developed as a means of mitigating these requirements [
3]. Catalytic oxidation can operate at lower temperatures (~1000 °F) by making use of a catalyst to aid the reaction. While still suffering from high energy consumption, catalytic oxidation is also vulnerable to catalyst poisoning. The catalysts used are often made from precious metals and are expensive to replace [
4]. An assessment of methane oxidation methods reports that, even with a 99% efficient heat exchanger capturing the thermal energy from catalytic oxidation, the remaining energy demand would result in 4 °C of global warming, defeating the purpose of the application [
5]. Photocatalytic oxidation utilizes catalysts that react to light, which aid in oxidizing methane. However, it suffers from slow rates of methane conversion; even if the rooftops of every building on Earth were covered with photocatalytic paint, the annual methane removal would not outpace the rate of increasing emissions [
5]. As with other catalytic oxidation methods, photocatalysis also suffers from catalyst poisoning [
6].
Biotrickling filtration already makes use of methanotrophs to oxidize methane. However, current methanotroph biofilters are designed for those bacterial strains that thrive in the 1–5 v% CH
4 range [
7], and not for low concentrations such as the 500 ppmv (0.05 v%) value used in this work. Previous work by researchers in this space has identified
Methylotuvimicrobium buryatense 5GB1C as a methanotroph strain that is able to consume 500 ppmv CH
4 at greater rates compared to others [
8].
As this biotrickling process requires external resource inputs, the environmental and economic impacts of those inputs will also need to be assessed. The inputs include, but are not limited to the electricity, water, and natural gas utility demands, the cellular nutrient medium, and the trucking services used for shipping. This is an important aspect to consider, as unintended adverse environmental impacts must be avoided. It also must be demonstrated that this process is not prohibitively expensive.
Ref. [
9] conducted a techno-economic assessment (TEA) study on a variety of methane mitigation technologies. Thermocatalytic oxidation has an estimated removal cost of EUR 10,000/tCH
4 at a concentration of 500 ppmv. Most of the cost is a result of the energy required to heat the air for combustion. Photocatalytic oxidation has an estimated removal cost of EUR 6500/tCH
4 at a concentration of 500 ppmv. The largest cost associated with this method is the capital cost of enabling the process, such as painting an existing rooftop with photocatalytic paint. Biofiltration has an estimated removal cost of EUR 24,000/tCH
4 when heating is necessary, and EUR 13,000/tCH
4 when heating is unneeded, at a concentration of 500 ppmv. This cost per ton is derived using the method of calculating the levelized capture cost defined in [
9]. The conclusion is that these removal technologies, in their current states, are unlikely to compete due to a low CH
4 oxidation rate or oxidation being too costly as a direct consequence of the low availability of sufficiently high methane concentrations [
9].
This work is part of an overall project which aims to develop a reactor which can remove methane at concentrations of 500 ppmv utilizing the metabolic processes of methanotrophs and additionally determine the feasibility of pilot-phase testing. Work has been performed by project partners [
10] to select and develop a suitable strain of bacteria which thrives in this 500 ppmv CH
4 environment and achieves significant methane removal per gram of biomass. A bench-scale bioreactor has also been developed with the purpose of characterizing the methane removal capacity of such a system under varying conditions such as differing packing mediums, operating temperatures, and input air flow rates. These experimental results have been used to develop an integrated modeling framework, which includes process simulation, environmental and economic impact assessments, for bioreactor assessment under several scenarios. The associated techno-economic and environmental life cycle assessments will serve to highlight several key process conditions and climatic conditions and their influence on the overall results using a detailed scenario analysis, and to highlight the areas for future research and development to increase the environmental and economic benefits of the process.
2. Materials and Methods
This CH
4 capture process will utilize packed-bed reactor (PBR) technology in conjunction with methanotrophic bacteria, to produce biotrickling filters capable of removing a significant percentage of CH
4 present in ambient air, which is to be injected into the process. The target removal goal is 1 Mt CH
4/year using the minimum number of reactors needed. A decentralized approach will be taken, and individual reactors will be deployed across numerous sites where ambient air contains at least 500 ppmv CH
4. As a value-added product, bacterial biomass will be harvested routinely from the bioreactors and de-watered on-site. Then, the de-watered biomass will be transported to a more central location to undergo further drying, resulting in the final product. Methanotroph biomass can be further refined to produce supplementary feed for ruminant livestock and salmonids, single-cell protein production, and biofuel production [
11,
12,
13].
The following biological reaction (1) is required for understanding the yields of biomass, CO
2, water, and energy produced by the consumption of CH
4 within the methanotrophic bacteria being used in this bioreactor system [
14]:
The yields of both CO
2 and biomass have been determined experimentally, and so the equation above has been modified to yield approximately the same as the experimental results. Specifically, the reaction stoichiometry has been adjusted most closely to the CO
2 yield, such as to not underestimate the amount of carbon that will be released by the system. It has been determined that the bounds for the reacting O
2 are 1–2 mol, with a typical range of values between 1.4 and 1.8 mol [
14]. Additionally, the water and heat generated via this reaction are significant enough to impact the utility usage and thus will not be ignored in subsequent calculations. The modified stoichiometry for the metabolic reaction is listed below in (2), and detailed calculations can be found in
Supplementary Materials, Section S1.
The values of constant parameters for this modeling study can be found below in
Table 1. Variable parameters that are used to generate various scenarios analyzing the effects of these conditions can be seen in
Table 2, alongside the ranges of values used for each parameter.
Analysis of three locations, Seattle, WA, Knoxville, TN, and Marquette, MI, under 10 different combinations of experimental variable values were performed. These locations were chosen as they represent different climatic classifications that comprise a large portion of the continental U.S. Under the Köppen climate classifications [
15], Seattle is located within a warm-summer Mediterranean climate, Knoxville is within a humid subtropical, and Marquette is in a humid continental mild summer, wet all-year region.
A total of 10 unique scenarios have been generated, adjusting one parameter from the baseline conditions of scenario A. These scenarios and their respective variable values can be found below in
Table 3. In scenario J, the operating temperature is allowed to fluctuate between 15 and 30 °C, and heating or cooling is only utilized if the reactor temperature is anticipated to move outside of that range.
A diagram representing the biomass production process is shown in
Figure 1. The process begins with the intake of the surrounding air, driven by a fan through the necessary heater and/or air conditioning unit to add or remove heat. This brings the air temperature within the desired operating range. The air is then injected into the bottom of the reactor and is bubbled through diffusers, where it is allowed to pass up through the BioBall (Aquascape, Chicago, IL, USA) packing medium. Attached to the BioBalls is the biofilm, which strips CH
4 from the air as it passes to the top of the reactor. The air, now saturated with water vapor, is vented off the top of the reactor, released freely back into the surrounding environment. The biomass is allowed to grow until it is harvested at regular intervals, currently at a baseline of 2 weeks, where it is dewatered via a centrifuge on-site, reaching a concentration of approximately 25% solid biomass. Based upon experimental data collected by research colleagues, approximately 80% of the biomass can be dislodged from the packing medium via vortexing; at least 3 iterations are necessary to remove this percentage [
10]. It is necessary to leave some of the biofilm present so that the reactor may continue to operate and regrow for the next harvest, so it is not necessary nor desirable to try to harvest 100% of the biomass. The dewatered biomass is then transported via semi-truck to a central location where multiple reactors’ harvests can be processed via a drum dryer. The dryer achieves product concentrations of approximately 85% solid biomass, which is then transported to be sold as the final product of the process.
Table 4 contains information for single-reactor inputs, outputs, and residence times, along with the minimum total reactors required per scenario to achieve the annual 1 Mt CH
4 removal goal. The detailed process of calculating all of these operational characteristics can be found in the
Supplementary Materials Document, Sections S1 and S2.
A notable takeaway from
Table 4 is the low gas residence times in the reactor. Recent research in this area has suggested that reactor times of 7–10 min provide optimal methane removal [
10], and the residence times found here are between 0.7 and 3.4 min. This could limit the methane elimination capacity of each reactor, which could require building larger reactors, or fundamentally altering the design or operations of the reactor to reduce the residence time requirement. As is, the modeling work presented here relies on the methane elimination capacities presented in
Table 4, and should be interpreted as a theoretical maximum for the given reactor configuration. Future research and development in this area to overcome this issue will be addressed below.
Ambient air is driven by a fan through a natural gas-powered heater and/or an air conditioning unit. Whether both the heater and air conditioning unit are needed depends on the operating temperature of the reactor, and the climate of the location where the reactor is operating. Ambient air is assumed to be at the average monthly temperature for the location.
The heat flux across the reactor vessel accounts for the heat generated by the bacterial metabolic reaction, the heat added/removed via the airstream-reactor temperature difference, and the heat lost via the evaporation of water from the reactor. The equation for determining the net heat flux in a particular month for one of the locations is shown in (3).
The heating/cooling demands for scenario J are calculated differently than the other scenarios, as scenario J operates between a range of temperature (15–30 °C) as opposed to a single temperature. Each month, scenario J assumes each reactor starts at the average of the temperature range (22.5 °C).
Net heat flux data from scenario H data can be used to show the necessary heating requirements if the reactor reaches 15 °C. Similarly, scenario I data can be used to show the cooling requirements when the reactor reaches 30 °C. In instances where scenario H (15 °C) has a positive heat flow and scenario I (30 °C) has a negative heat flow, there must be an operating temperature value between the two temperatures where the reactor will reach equilibrium, and the net heat flow will be zero. In these instances, it can be assumed that operating a heating or cooling unit will be unnecessary. For example, during April in Seattle, scenario H shows that if the reactor began at 15 °C, it would begin gaining heat; in scenario I, beginning at 30 °C, the reactor would start losing heat. Scenario J also shows that starting from the average temperature of 22.5 °C, it would still decrease in temperature. Between the operating temperatures of 15–22.5 °C, the rate of heat flow changes from positive to negative, indicating there must be a temperature where the heat flow is zero. The Solver function in Excel was used in conjunction with (3) to determine what operating temperature between 15 and 30 °C would result in a net flow of zero.
Table 5 presents examples of instances where this equilibrium occurs.
AC units are chosen for each scenario for each location; units provide a maximum number of tons of cooling (equal to 12,000 BTU/h), but a suitable unit in this case is not chosen based upon the tons of cooling it can supply but is instead chosen based upon the amount of CFM of air it is capable of processing. This amount is determined using a rule of thumb used by HVAC technicians and is equal to approximately 412.5 CFM per ton of cooling [
16]. This ensures that the air receives the proper amount of cooling desired. The natural gas heaters for each scenario and location are determined similarly to the AC units but are now sized based upon whatever month demands the greatest number of BTUs per location. Additional details on all equipment sizing can be found in
Supplementary Materials, Section S3.
Capital expenses associated with this part of the process are the axial fan, AC unit, and natural gas heater. Electricity consumption by the three pieces of equipment, as well as natural gas use by the heater comprise the operating expenses for this section.
The biotrickling filter reactor modeled here is multi-phase. This consists of the temperature-adjusted air, which is injected below the BioBall packing media. The air passes through diffusers which adjust the airflow into fine bubbles that rise through the column. These bubbles are assumed to spread evenly across the cross-sectional area of the reactor. Aeration is accomplished with minimal compression required due to the high air void spaces (>70%) that are typically seen in packed-bed reactors of this type [
17,
18].
The liquid phase consists of the thin water film that covers the BioBalls, which is generated via the recirculating spray, which is ejected downward from above the BioBalls. As the water evaporates, it is renewed constantly via the spray. Due to the low flow rate of water required to be recirculated, the pump that would be needed was not considered in the capital costs of this model.
BioBalls are used to fill the column and are not expected to need replacement over the course of the reactor lifetime. The amount of BioBalls required varies only with reactor volume. The solid phase consists of the BioBalls themselves, on which the methanotrophs grow, forming the biofilm. The CH4 dissolves into the liquid phase, which contacts the methanotrophs that are then able to metabolize it. Once the air reaches the exit at the top of the reactor, it is assumed to be saturated with water vapor. This has ramifications for all the utilities: water, natural gas, and electricity. A non-negligible amount of water is evaporated and must be refreshed into the system regularly, and the cooling effect from the evaporation increases the amount of natural gas used required to keep the reactor temperature high enough. The cooling effect also reduces the amount of necessary AC use, which keeps a significant source of electricity consumption down. The air exits the top of the reactor freely and returns to the surrounding environment. To effectively supply the air to the reactor vessel, it is necessary to equip the bottom of the column with fine bubble diffusers through which the airstream is injected.
Capital costs associated with this section of the process are the reactor vessel, the BioBall packing, and the diffusers. Water consumption and cellular medium nutrients are the operating expenses for this section.
Table 6 displays the attributes of reactor equipment for each scenario, such as cost, dimensions, and quantity of equipment pieces.
NMS2 cellular medium is used to fill each reactor, and it comprises several compounds, which are shown along with their respective concentrations in
Table 7. KNO
3, KH
2PO
4, and NaHPO
4 * H
2O are currently unique in that although they are present in the medium initially, they are not replenished over time; other chemical products are used as alternative sources of elemental nitrogen and phosphorus, which the initial medium compounds provide. Urea and organic fertilizer are being used as more cost-effective alternatives to provide nitrogen and phosphorus to the bacteria, respectively. The necessary quantity of urea and fertilizer are determined as a function of the amount of biomass produced, rather than just as the ratio of the compound present in the medium recipe. Additional details can be found in
Supplementary Materials, Section S4.
Nutrients are replenished at every reactor harvest, and based upon laboratory experiments conducted by research colleagues [
10], adding 10% of the initial nutrient mass every 2 weeks was sufficient for the bacteria to thrive.
Experiments were conducted by research colleagues to determine a feasible method of dislodging the biofilm from the packing media, and it was found that vortex mixing the packing media (cellulose beads used at the time as opposed to the BioBalls assumed in this model) removed up to 78% of the biofilm in a single treatment, with successive treatments improving removal further. It is assumed that this same method would achieve similar results with BioBalls.
The total amount of biomass accumulated per harvest is not equal to the amount that is harvested, as only approximately 80% of the biomass is able to be liberated from the packing medium. This is acceptable because sufficient biomass must be left in the reactor to allow the regrowth of the bacteria and ensure the continual operation of the system. No capital or operating expenses are associated with this part of the process.
Per harvest, water removed from the solution is assumed to be recycled back into the bioreactor, saving on resource use and utility costs. The dewatered intermediate biomass product is then moved on to the transportation steps. At the known yield of 0.78 g biomass/g CH4 reacted, approximately 218.4 g of biomass accumulates each week. After collecting 80% of the biomass present at each harvest interval, the percentage of solids (biomass) in the solution increases by 0.14–0.15% per week between harvests. At the baseline assumption of 2 weeks between harvests, the accumulated solids percent is 0.29%. Once processed by the centrifuge, the intermediate biomass product contains 25% solids. Recycled water/medium has been factored into the cost of total monthly water demand of each scenario. The centrifuge is the only capital expense for this process section, along with its electricity use being the only operating expense.
Once the on-site centrifuge has removed as much water as possible from the biomass solution, it is prepared to be shipped via semi-truck. It is assumed that a shipping service will be hired to transport the intermediate product to a central regional facility, which can further dry the biomass solution to its final, saleable form. The shipping service is assumed to cost USD 2.86 per mile traveled, and that each truck will travel an average distance of 100 miles per shipment [
19].
The annual cost of shipping the intermediate product to the drying facility is calculated using the average distance per trip, the trucking rate, and the number of harvests per year. No capital expenses are associated with this section, and the annual shipping cost is the only operating expense. Final transportation of the finished product to the consumer is not considered in both emissions and economic calculations in this study, but rather only the intermediate transportation from reactor to drying location.
A rotary drum dryer will be used to process the biomass solution to its final stage, achieving stable dry biomass (85% solids content) once complete. It is assumed that the rotary drum dryer at each central facility will be able to service multiple shipping truck loads in succession, thus there is no need to equip each reactor site with a dryer. Due to this stage of the process demanding >25 kW, the Marquette, MI electric utility is adjusted to USD 8.17/kW per month plus USD 0.16047/kWh. Additional information on all utility demand calculations and related economic and environmental impacts for each stage of the process can be found in
Supplementary Materials, Sections S4, S6, and S13.
The centralized drying locations are assumed to require the rental of commercial space; for the bare minimum facility area required, it is assumed that enough space for five 20 ft semi trailers’ worth of product to be stored on-site at any one time is needed. An annual rate of USD 8.43/ft
2 was assumed for the rental space [
20], an area of 159 ft
2 was used for a single 20 ft trailer based upon the given internal dimensions [
21], and the dryer takes up 75 ft
2 of space as based upon manufacturer specifications [
22]. With five trailers and the dryer, the facility has a minimum area of 870 ft
2. At USD 8.43/ft
2, the annual facility rent is USD 7334.10. As this facility serves 10 reactors, the facility rent costs can be split over each, giving an annual facility rent of USD 733.41 per reactor.
An average of 10 reactors are assumed to be operating within a 100-mile radius of every necessary facility. Shown in
Figure 2 are four examples of regions across the U.S. near our scenario locations where a combination of landfills and dairy feedlots are present, demonstrating the viability of this 100-mile radius assumption. As of 2021, a combined total of 13,000 inactive and active landfills were present in the U.S. [
23]. Total cattle farms in 2022 were estimated at 732,123, with approximately 12,000 of those being >1000 head farms [
24,
25]. Stripper wells (oil and natural gas) were estimated at 759,905 in total for 2021 [
26]. In 2025 there are currently 14,800 wastewater treatment sites in the U.S. [
27]. In most parts of the country, more than 10 potential bioreactor sites would presumably exist within this baseline 100-mile shipping radius being currently assumed in this study.
Like the assumption that the drum dryer can serve multiple reactors’ intermediate product shipments, it is assumed that personnel that operate the reactors and drying facilities are able to serve multiple locations. A process engineer is not required to be hands-on with any system to the degree that an operator needs to and is likely only to inspect each location briefly outside of special cases. As a result, it is assumed that the engineer can serve double the number of locations an operator is able to. Labor costs do not change per scenario or location (the US average is used), and the values presented in
Table 8 represent the labor expenses after being spread across the appropriate reactors serviced.
The drum dryer is the only capital expense associated with this part of the process, and the operating expenses consist of the facility rent and the electricity consumption by the dryer.
One value-added product generated by the process includes the dried, 85% biomass product in 15% moisture, which can be used for multiple purposes, such as a single-cell protein for consumption by both humans and livestock, undergoing further processing to create biofuels, or serve as fertilizer for crops. For this study, biomass is valued at USD 1600/ton [
28], which assumes a 1:1 replacement for dried, stable fishmeal based on the protein content of the animal feed. The biomass product generated by this process offers a suitable replacement for fishmeal, which typically contains 50–60% protein by mass. Methanotrophs and methanotroph-based single cell protein have been found to contain 59–81% crude protein content [
11,
29], so the protein content of the product here is assumed to be sufficient for fishmeal replacement. There may be other incidental costs associated with packaging and regulatory approval, but it is assumed that those costs would be minor and roughly equivalent between conventional fishmeal and this new animal food substitute product.
The annual revenue generated by the production of biomass is calculated via (4). The other source of revenue assumes the existence of and access to a market of carbon credits. Since there is no nation-wide market, the value of removing 1 tCO
2e from California’s cap-and-trade market is being used to estimate the revenue stream. As of August 2024, that market value was USD 34/tCO
2e, but this price has recently fluctuated between USD 25 and USD 40 [
30]. The theoretical revenue from carbon credits is calculated using (5).
The environmental life cycle assessment studies being conducted in this work have been completed in accordance with ISO [
31,
32] guidance. The goal of the LCA work was to understand the greenhouse gas emissions associated with the bioreactor process, and the system boundary utilized for this work is consistent with the techno-economic work as described in prior sections and
Figure 1. The functional unit of concern is 1 ton of CO
2e emission removal performed by the bioreactor system, to which the environmental impacts are scaled. Additional details are to be found in
Section 2 and
Section 4 of the work, along with
Supplementary Materials Sections S5 and S13.