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An assessment of gas-side fouling in cement plants

The cement industry is the most energy-intensive industry in the United States in terms of energy cost as a percentage of the total product cost. An assessment of gas-side fouling in cement plants with special emphasis on heat recovery applications is provided. In the present context, fouling is defined as the buildup of scale on a heat-transfer surface which retards the transfer of heat and includes the related problems of erosion and corrosion. Exhaust gases in the cement industry which are suitable for heat recovery range in temperature from about 100 to 1300 K, are generally dusty, may be highly abrasive, and are often heavily laden with alkalies, sulfates, and chlorides. Particulates in the exhaust streams range in size from molecular to about 100 micrometers in diameter and come from both the raw feed as well as the ash in the coal which is the primary fuel used in the cement industry. The major types of heat-transfer equipment used in the cement industry include preheaters, gas-to-air heat exchangers, waste heat boilers, and clinker coolers. At the present time, the trend in this country is toward suspension preheater systems, in which the raw feed is heated by direct contact with the hot kiln exit gases, and away from waste heat boilers as the principal method of heat recovery. The most important gas-side fouling mechanisms in the cement industry are those due to particulate, chemical reaction, and corrosion fouling.

Marner, W. J.

Field Validation of Thermoelectric Generation System at Holcim Cement Plant in Alpena, Michigan

Executive Summary Project Background The Industrial Technology Validation (ITV) program aims to identify and demonstrate the performance of new, emerging, and underutilized energy-saving technologies in the industrial sector to help inform decisions to help accelerate their commercialization and deployment, as well as to help make industries more competitive. This ITV demonstration evaluated a thermoelectric generation (TEG) technology at a cement plant, aiming to reduce energy demand in the cement industry. A median cement plant consumes 5.73 million British thermal units per ton of clinker production (resulting in 0.838 metric tons of carbon dioxide [CO₂] emissions per ton of clinker) (Boyd and Zhang 2011, EPA 2021), equivalent to approximately 6.9 trillion British thermal units (TBtu) per year in energy consumption at a cement plant producing 3,300 tons of clinker per day.¹ Collaborating with Holcim, Advanced Thermovoltaic Systems (ATS) developed and deployed a pilot-scale thermoelectric power system to efficiently capture and convert waste heat to electricity. The system leverages the Seebeck effect to convert temperature differences on two sides of semiconductor cartridges into electrical power (ScienceDirect, n.d.). This generation is realized with minimal moving parts compared to existing waste-heat-to-generation solutions and allows capture from heat sources with temperatures as low as 150°C. This project aimed to validate a scalable solution applicable for capturing medium-temperature waste heat, including ambient losses from other high-temperature processes, and high-temperature sources less suitable for other waste-heat-to-power solutions. By recovering this otherwise wasted heat, this project intends to validate improvements to overall process efficiency through reduction in purchased electricity, thereby reducing operational costs while enhancing resiliency and competitiveness. Description and Scope This study evaluated the performance of a TEG system from ATS as a solution to convert waste heat into useful power at a Holcim cement plant in Alpena, Michigan. This plant is a fully integrated cement plant that has been operating since 1907. The facility operates continuously (24/7/365) with approximately 250 employees and five long dry kilns, yielding a total production capacity of 7,852 tons of cement per day (EPA 2023). Currently, the Alpena plant uses waste heat boilers to convert waste heat from the exhaust of each kiln into steam, which drives steam turbine generators. The ATS TEG is being evaluated for its potential to supplement the steam turbines by capturing the remaining lower grade heat. This technology is also being considered for other Holcim plants where steam turbines are not a viable option. ATS installed a pilot-scale TEG unit with an array of 582 individual thermoelectric semiconductor cartridges, of which 573 were operational. The cartridges are sandwiched between 48 hot plates and 49 cold plates. Each cartridge is designed to generate 20 watts (W) of gross power at a hot-side temperature of 240°C and cold-side temperature of 20°C. As such, the total gross generation capacity of the installed system is 11.5 kilowatts (kW) at design conditions. The system configuration for the evaluation was designed to prioritize convenience of installation and minimize disruption to production at the site, while ensuring that the heat required can be obtained for evaluating the TEG system at various operational conditions. To accomplish this, a portion of the steam supplied to Alpena’s steam turbine generation system was diverted to be used as the heat source for the TEG system, while water was supplied to the cold side of the system from nearby Lake Huron. This configuration was designed for the evaluation of the pilot-scale system to assess the performance at different conditions. A commercial-scale system will likely vary from the pilot system depending on typical configurations, including both scale and application. Future commercial applications of the ATS system would involve integrating the system into the exhaust from kiln preheaters, clinker coolers, or radiant heat capture from kiln shells for the heat source. For the cold source, a range of cooling solutions can be considered, including a mechanical cooling system, depending on the location and the application. To increase the generation capacity for commercial applications, the technology provider is working toward developing a commercial-scale TEG system, which would combine multiple TEG units (each similar in design to the pilot system) together. The scope of this evaluation includes the pilot-scale TEG system and all impacted equipment including pumps, controllers, and power handling equipment. Study Objectives The evaluation's goal was to assess the potential of the ATS TEG system to generate useful electrical power by capturing waste heat from cement production kilns. The objectives of this study are to evaluate and verify the following claims made by ATS regarding the pilot-scale system installed at the Holcim Alpena plant. The following design parameters and claims are also outlined in Table ES- 1 and Table ES- 2: • Gross Power: The thermoelectric system converts heat into power to create gross power, the total measured power generated by the system. The 573 active cartridge pilot-scale system is expected to generate 11.5 kW of gross power at the designed hot-side temperature of 240°C and cold-side temperature of 20°C. Power production is dependent on the temperature difference between the heat source (ultimately from the waste heat) and cold temperature supply source. • Net Power: The net power is the total usable power provided to the site by the TEG system after deducting parasitic power loads from the gross generated power. Supplementary equipment is required to operate the TEG system including pumps, controllers, and, in certain anticipated applications, mechanical cooling, which introduce parasitic loads to system operation. After deducting the parasitic loads from the gross power generation, ATS anticipates achieving a net power generation of 7.5 kW from the pilot-scale system. • Thermal Efficiency: The thermal efficiency is the percent of the total heat transferred to the TEG system that is converted to gross power. Historically, TEGs have a thermal efficiency of 2%–5% (DOE 2008). Prior industrial-scale TEG systems, such as the E1 TEG offered by Alphabet Energy, operated at an efficiency of 2.5% (Lamonica, 2014). ATS anticipates achieving an average efficiency of 4.8% or higher in converting heat energy to usable electricity. • Cartridge Performance: The TEG system comprises 573 active individual semiconductor cartridges, each of which generates a portion of the total power. Cartridge optimization and selection is an important design consideration for potential future TEG system design performance. Therefore, understanding the distribution of gross power and efficiency within the pilot system is vital to understanding what is achievable. At a design hot-side temperature of 240°C and cold-side temperature of 20°C, ATS anticipates a cartridge performance of 20 W of gross power per cartridge at an efficiency of 4.8% per cartridge. In addition to evaluating the claimed performance of the TEG pilot-scale unit, the study estimated the potential annual impacts of a scaled-up commercial system used to capture kiln waste heat over annual operations. The evaluation estimated the gross and net annual electric generation achievable by capturing heat from the two proposed tap-in points: the kiln exhaust and the clinker cooler exhaust; see Section 2.1 for details. Two use cases were examined: • Holcim Alpena: The Holcim Alpena site consists of long dry kilns with superheater boilers, which differs from the rest of Holcim’s cement plant portfolio and results in lower waste heat temperatures. The study estimates gross and net annual generation using the superheater boiler exhaust and clinker cooler exhaust, based on 2023 operational data. • Typical Installation: Common cement plants have preheater kilns with higher exhaust temperatures than Holcim Alpena across a range of production rates. The study estimates gross and net annual generation using the preheater exhaust and clinker cooler exhaust, with a sensitivity analysis to account for the typical range of preheater exhaust temperatures, clinker cooler exhaust temperatures, and clinker production rates. Methodology The evaluation methodology followed a measurement and verification (M&V) strategy based on the International Performance Measurement and Verification Protocol Option B through comprehensive measurements and analyses of the affected systems. Evaluation data was collected from March 9 to March 11, 2024, the test period of the pilot TEG system. During the test period, in coordination with the ITV team, the ATS team adjusted system operations to capture the range of variability expected for each of the variables pertinent to performance of the system. The methodology consisted of two parts: evaluating the performance of the pilot unit's TEG system and estimating the annual TEG impact in terms of gross and net power based on a given waste heat profile. First, the evaluation of the thermoelectric generation performance of the pilot unit relative to the claims was performed by analyzing the collected test data. Gross power of the pilot TEG system was directly measured. Net power was determined by deducting the measured parasitic power from the gross power. The gross power generation was compared to heat transferred to the system by the working fluid (which was heated by steam generated from the kiln waste heat) to calculate the thermal efficiency achieved by the system. Performance of individual semiconductor cartridges within the pilot array was also assessed in terms of measured gross cartridge power and calculated cartridge thermal efficiency. The second part of the evaluation estimated the annual TEG impacts in terms of gross power and net power (calculated from the difference between gross power and parasitic power). This analysis comprised development of mathematical regression models for gross power and parasitic power, with assessment of each model’s goodness-of-fit characteristics to ensure satisfaction of statistical requirements. The models predicted the gross power generation, the parasitic load based on the temperature difference between the hot working fluid and the cold-side fluid (cold water from Lake Huron) entering the system, the volumetric flow rate of the cold-side fluid at the inlet, and the volumetric flow rate of the hot working fluid at the inlet. The annual impact analysis considered a theoretical commercial-scale system sized to capture the available waste heat at a cement plant, consisting of linked pilot-scale units that receive heat from a theoretical gas-to-working-fluid heat exchanger. To estimate annual impacts at the Alpena plant, the gross power and parasitic power regression models were applied to the arrays in the theoretical commercial-scale system. The heat supplied to the unit was calculated based on the kiln run time, annual production, kiln exhaust waste heat, and clinker cooler waste heat derived from 2023 Holcim Alpena kiln operational data. Net power impacts were calculated by deducting the resulting parasitic power from the estimated gross power. Inputs for the model were generated from a combination of hourly data, assumed design considerations for TEG system scale-up from the pilot-scale unit, and assumptions regarding TEG system operations. This analysis was then used as the basis for estimating annual impacts of typical TEG installation at cement plants, by applying sensitivity analyses to key kiln operational characteristics including kiln preheater exhaust temperatures, cooler clinker exhaust temperatures, and plant daily production rates across a range of expected values. Project Results/Findings Table ES- 2 and Table ES- 2 provide a summary of the operating conditions and evaluation results compared to the stated claims from the technology provider. Key takeaways include: • Gross Power: The peak gross power achieved during the testing period was 10.0 kW, compared to the 11.5 kW expected for 573 active cartridges. The claimed gross power was associated with a target hot side of 240°C; however, the system only received a maximum hot-side mean plate temperature of 212°C during the testing period. • Net Power: The pilot-scale unit exceeded the claims for net power, achieving a peak of 7.7 kW net compared to a claim of 7.5 kW. One factor contributing to the higher achieved net power is the relatively high water pressure available through Lake Huron. The pilot TEG system did not require cold-side pumps during the test, whereas most installations would. This reduced the parasitic loads on the system, ultimately contributing to higher net power relative to the gross power. • Thermal Efficiency: The pilot-scale unit outperformed the claimed efficiency, achieving a peak system efficiency of 5.0% thermal efficiency compared to the stated 4.8%. • Cartridge Performance: To compare cartridge performance against claims, the study focused on the third day of testing, which aimed for conditions closest to the design specifications, with a hot side of 240°C and cold-side exit temperature of 6.4°–30°C. On this day, the mean gross power observed in the cartridges within the TEG array was 18.1 W/cartridge, and the peak performance was 34.7 W/cartridge. The estimated mean cartridge efficiency was 5.2%, and the estimated efficiency at peak gross cartridge power was 10%. The regression models developed for gross power generation and parasitic loads were used to estimate the generation impact for given heat input to the TEG from the working fluid (captured from the waste heat) and from the cold loop (Lake Huron) on an hourly basis for a year of operation. Based on this analysis, installation of a commercial-scale TEG system at the Holcim cement plant in Alpena, Michigan, with a waste heat exchanger of 0.85 effectiveness, would generate up to 391 kW of net power, translating to between 920,000 and 1,800,000 kilowatt-hours (kWh) in net electricity per year. Based on typical grid emissions for Alpena, this would avoid estimated net emissions by 752 metric tons of CO₂ annually.² The sensitivity analysis estimated that typical TEG system installations at cement plants could generate an average of 56–1,040 kW of net power, or between 488,000 and 9,110,000 kWh of net energy. This generation potential is most significantly affected by plant production rates and also influenced by preheater and clinker cooler exhaust temperatures. Applying the national average emission rate, typical commercial-scale installations at Holcim plants are projected to avoid between 182 and 3,401 metric tons of CO₂ annually per site. Table ES- 3 shows a summary of the estimated annual impacts.³ While parasitic loads are significant and vary by application, this analysis assumed the use of heating loop pumps and access to Lake Huron as a cold sink. This setup assumed no need for cooling loop pumps due to the available water pressure at the test site. Applications that require cooling towers or additional equipment are likely to experience higher parasitic loads. Therefore, the study’s estimates are most applicable to scenarios with similar parasitic load configurations—namely, access to a high-pressure cold sink. Applicability to other locations may be limited, as differing conditions could necessitate additional pumps and cooling systems, potentially impacting performance significantly.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI

Cement Plant TEA/LCA

This presentation was prepared for the 2024 Carbon Management Project Review Meeting. The slides summerize recent NETL systems analysis work examining the application of carbon capture systems at cement plants. This includes a 2023 NETL report titled "Analysis of Carbon Capture Retrofits for Cement Plants" and a 2024 NETL authored journal article titled “The Impact of Cement Plant Air Ingress on Membrane-Based CO2 Capture Retrofit Cost”. The slide deck also highlights ongoing NETL techno-economic analysis and lifecycle assessment work on capture from cement plants & other industrial capture projects.

Homsy, Sally

The Impact of Cement Plant Air Ingress on Membrane-Based CO2 Capture Retrofit Cost

This PowerPoint presentation summarizes the cost and performance results of the techno-economic analysis of membrane-based carbon capture retrofits at cement plants, published in June 2024, titled “The Impact of Cement Plant Air Ingress on Membrane-Based CO2 Capture Retrofit Cost.” The analysis report used as a basis for slide contents was developed by NETL for publication in the scientific journal Carbon Capture Science and Technology.

Hughes, Sydney

The Impact of Cement Plant Air Ingress on Membrane-Based CO2 Capture Retrofit Cost

This PowerPoint presentation summarizes the cost and performance results of the techno-economic analysis of membrane-based carbon capture retrofits at cement plants, published in June 2024, titled “The Impact of Cement Plant Air Ingress on Membrane-Based CO2 Capture Retrofit Cost.” The analysis report used as a basis for slide contents was developed by NETL for publication in the scientific journal Carbon Capture Science and Technology.

Hughes, Sydney

Retrofitting Holcim Ste. Genevieve Cement Plant with CO2 Capture Plant Using Air Liquide Cryocap™ FG Technology

The global cement manufacturing industry is a major contributor to carbon dioxide emissions. The International Energy Agency's "Net Zero Emissions by 2050 Scenario" identifies CCS as a major strategy for meeting that goal. This project is among the first attempts to transfer capture technology developed at coal-fired power plants to the cement industry. The main objective of the project is to execute and complete a front-end engineering and design (FEED) studies for commercial-scale, carbon capture projects that separates 95% of the total CO2 emissions at the Holcim (US) Ste. Genevieve cement manufacturing facility using Air Liquide’s Pressure Swing Adsorption system (PSA) assisted Cryocap™ technology. The Holcim Ste. Genevieve cement plant in Missouri, US, boasts one of the largest single cement production lines in the world, with a capacity of approximately 12,000 t/day. The plant currently uses traditional fuels, namely coal and petcoke. The captured CO2 will be pipeline and geological storage grade. The industrial host site emits approximately 3.0 million tonne CO2/yr. Air Liquide’s Cryocap™ technology has been developed over the last 18+ years for CO2 capture applications. It has been shown to be applicable to a variety of industrial applications (e.g., steel, cement, SMR, Fluidized Catalytic Crackers (FCCs)). Cryocap™ FG consists of a Pressure Swing Adsorption (PSA) unit coupled with a Cryogenic System. The PSA pre-concentrates the CO2 from the flue gas, while the cryogenic unit enables the CO2 purity to be increased to the desired level. The project team is led by the Prairie Research Institute at the University of Illinois at Urbana-Champaign. The tasks include: complete FEED study for retrofitting the industrial facility with a carbon capture system to support developing a detailed cost estimate; business case analysis outlining the anticipated revenue and credits if projects was built and operated; technoeconomic analysis (TEA) outlining how capture system achieves DOE capture goals; and life cycle (LCA) analysis demonstrating zero net carbon emissions. The FEED study was successfully completed. This includes completing the process basis of design; preliminary engineering; outside battery limits (OSBL) detailed engineering including a Zero Liquid Discharge (ZLD) wastewater treatment system; inside battery limits (ISBL) detailed engineering [1]. An overall project capital cost estimate within a -20%/+30% accuracy was developed. The major contributors to the Total Plant Cost (TPC), by system, are the costs associated with the Outside Battery Limit (OSBL) section of the plant which includes a new river water intake structure and a Zero Liquid Discharge (ZLD) system. By cost category, the major contributors to the TPC are equipment and subcontractor costs, followed closely by engineering, construction management, home office and contractor fees. The TEA has been created to reflect the findings of the project. It analyzes the economic performance of the Cryocap™ technology by reviewing the estimated capital costs, operating cost, and revenue. The Cost of Capture (COC) associated with the Cryocap™ technology for 95% CO2 capture, when considering NETL 2018 economic assumptions (42/58 debt/equity ratio, 5.15% interest on debt and 1.42% return on equity in real dollars) and 2022 economic assumptions (42/58 debt/equity ratio, 8.82% interest on debt and 4.90% return on equity in real dollars) was found to be much lower than that for the DOE-NETL’s base-line cases. The highest contributors to the COC are annualized capital expenditures (CAPEX) and electricity consumption which can be offset by using lower cost renewable sources. The LCA was conducted using OpenLCA which is an open-source software that is recommended by NETL. The database utilized for this study was a modified version of TRACI 2.1 (developed by the US. Environmental Protection Agency’s National Risk Management Research Laboratory and modified by NETL). The Cryocap™ FG technology does not consume fuels in significant quantities and does not utilize specialized chemical solvents subject to decomposition, such as those utilized in amine-based carbon capture systems. The Cryocap™ FG technology mainly utilizes electricity as its energy input; hence, its calculated emissions are mainly associated with the generation of electricity offsite and are dependent on the energy matrix of the grid at the time of project implementation. The water consumption impact of the Cryocap™ FG is mostly for makeup of the water lost by evaporation in the cooling tower; however, the carbon capture plant will be equipped with a ZLD system to avoid effluent streams and minimize water consumption. The successful construction and operation of this plant based on this study results will provide a means to demonstrate an economically attractive and transformational capture technology that can be used to retrofit existing plants and be deployed at new plants.

01 COAL, LIGNITE, AND PEAT

Characterization of Most Promising Sequestration Formations in the Rocky Mountain Region

The project Characterization of Most Promising Sequestration Formations in the Rocky Mountain Region is one of 9 site characterization projects that were implemented as part of ARRA (American Recovery and Reinvestment Act). Data from this project was used to improve resolution of data in NATCARB in the area of study. Data related to this study has already been incorporated in NATCARB Atlas. The Rocky Mountain Carbon Capture and Storage (RMCCS) project investigated multiple geologic formations and characterized a local site on the Colorado Plateau for future CCS opportunities. The RMCCS project focused on the Cretaceous Dakota, Jurassic Entrada, and Pennsylvanian Weber Sandstones, the three largest regional formations. All formations in this project are potential CO2 storage resources for future power plants, natural gas processing plants, cement plants, and oil shale development projects. The area adjacent to Craig, Colorado, (Sand Wash Basin) was the area selected for detailed geologic characterization on the RMCCS project. The basin was selected in part because the geology can be extrapolated to other sites on the Colorado Plateau. Field mapping and seismic surveys were conducted to identify and evaluate the basin's structural configuration. A 9,745-foot deep characterization well was drilled to collect 131 feet of core and a suite of geophysical well log data. Petrophysical tests on samples of core were used to calibrate geophysical log data, which can be used to obtain storage resource estimates and evaluate associated uncertainty as well as simulate the hydrologic behavior of injected CO2. A detailed analysis of the primary formations (Dakota, Entrada and Weber sandstones) yielded a more accurate CO2 storage resource assessment for these formations within the Colorado Plateau; RMCCS estimates indicate a total CO2 storage resource of more than 38,000 million metric tons. The characterization of the Sand Wash Basin (2-D seismic surveys, multiple well logs and lithological, petrophysical and geochemical analyses) allowed for a detailed 3-D model to be constructed. The model served as the framework for analyses ranging from CO2 storage resource, injectivity, and subsurface flow to uncertainty estimates to evaluation of risk.

2-D seismic

Implementing Large-Scale CCS in Complex Geologic Reservoirs: Insights from Three Appalachian Basin Case Studies

This paper presents three design case studies for implementing large-scale geologic carbon storage in the Appalachian Basin region of the midwestern United States. While the Appalachian Basin has a challenging setting for carbon storage, the three case studies detailed in this article demonstrate that there are realistic options for implementing carbon storage in the basin. Carbonate rock formations, depleted hydrocarbon reservoirs, and moderate-porosity sandstones can be utilized as carbon-storage reservoirs in the Appalachian Basin. While these are not typical concepts for CO2 storage, the storage zones have advantages such as defined trapping mechanisms, multiple caprocks, and defined boundaries that are not always present in thick, permeable sandstones being targeted for many carbon-storage projects. The geologic setting, geotechnical parameters, and hydrologic setting for the three case studies are provided, along with the results of reservoir simulations of the CO2 injection-deployment strategies. The geological rock formations available for CO2 storage in the Appalachian Basin are more localized reservoirs with defined boundaries and finite storage capacities. Simulation results showed that accessing carbon-storage resources in these fields may require wellfields with 2–10 injection wells. However, these fields would have the capacity to inject 1–3 million metric tons of CO2 per year and up to 90 million metric tons of CO2 in total. The CO2 storage resources would fulfill decarbonization goals for many of the natural-gas power plants, cement plants, hydrogen plants, and refineries in the Appalachian Basin region.

Sminchak, Joel

Carbon Capture Plant Front-End Engineering Design Study for Cement Manufacturing

The objective of this project was to conduct a Front-End Engineering Design (FEED) study for capturing carbon dioxide (CO₂) from cement plant flue gas using non-aqueous solvents (NAS) with a 95% capture efficiency. The study aimed to develop AACE (Association for the Advancement of Cost Engineering) Class 3 cost estimates for a commercial-scale CO₂ capture system with a capacity of 2.4 million tonnes of CO₂ per year (t-CO₂/yr). The results will provide Cemex and the U.S. Department of Energy with reliable data to support investment decisions, evaluate economic feasibility, and guide future project development and implementation.

20 FOSSIL-FUELED POWER PLANTS

Economic and Jobs Impacts of Point-Source Carbon Capture in Cement Industry – Case Study

The cement industry accounts for an estimated 8% of global CO2 emissions, which surpasses that of the entire aviation sector. In contrast with other industries, where CO2 emissions can be drastically reduced via electrification or fuels substitution, cement production releases CO2 as part of its process, during the calcination of carbonates to yield oxides. Thus, point-source carbon capture has become a key technology in the cement industry’s decarbonization. Apart from the expected environmental benefits, point-source carbon capture in the cement industry can yield important economic benefits and create jobs. The objective of this study was to perform a preliminary assessment of the economic and workforce impacts associated with the construction and operation of a point-source carbon capture retrofit of an existing cement production facility, using as a basis the data from a front-end engineering design (FEED) study to install a 3.9 million metric tons per year (Mtpy) CO2 capture facility at Holcim Ste Genevieve cement plant in Missouri, United States of America. The advanced carbon capture technology used in this FEED study was Air Liquide’s Cryocap™ FG carbon capture technology. The study evaluated the direct, indirect, and induced economic impacts of the construction, operation, and maintenance activities of the project over its lifespan. It also covered how the project will generate new jobs, their nature, and quantity, along with strategies to prepare the workforce. To perform this study, construction, operation, and maintenance cost estimates, as well as construction and operation staffing plans from the FEED study were input into IMPLAN version 7.5 software, licensed by IMPLAN Group LLC (Huntersville, VC), to predict the direct, indirect and induced economic impacts of the project using industry multipliers from the software. Additionally, recruitment strategies were developed for hiring individuals who belong to groups that are historically underserved or underrepresented, as well as anticipated recruitment of workers from the local community (whether training will be required or if the skills are associated with an existing labor force). The analysis estimated that the construction and operation of the carbon capture at Holcim Ste. Genevive will result in over 24 thousand work-years of job opportunities, close to USD 10 billion of economic impacts, including over USD 460 million of tax revenue. These results encompass the direct, indirect, and induced effects. A strategy to maximize hiring from the project and neighboring counties was developed, leveraging training agreements with local trade groups and universities. The result of this study can be used for a strategic preliminary assessment of the potential regional economic and job impacts of retrofitting existing cement plants with point source carbon systems, and its methodology can be replicated to individual projects to aid in planning and workforce development.

01 COAL, LIGNITE, AND PEAT

Applications of thermal energy storage in the cement industry

In the manufacture of cement, literally trillions of Btu's are rejected to the environment each year. The purpose of this feasibility study program was to determine whether thermal energy storage could be used to conserve or allow alternative uses of this rejected energy. This study identifies and quantifies the sources of rejected energy in the cement manufacturing process, established use of this energy, investigates various storage system concepts, and selects energy conservation systems for further study. Thermal performance and economic analyses are performed on candidate storage systems for four typical cement plants representing various methods of manufacturing cement. Through the use of thermal energy storage in conjunction with waste heat electric power generation units, an estimated 2.4 x 10 to the 13th power Btu/year, or an equivalent on investment of the proposed systems are an incentive for further development.

Jaeger, F. A.

Mitchell FEED Study Summary Report (Unlimited Rights Version) (Rev. D)

Heidelberg Materials (HM), Sargent & Lundy (S&L), and Mitsubishi Heavy Industries (MHI) completed a Front End Engineering Design (FEED) study for deployment of an amine-based CO 2 capture system at the Mitchell Cement Plant in Indiana. The project includes compression of captured CO 2 to a supercritical state for geological sequestration. The flue gases from 7,000 mtpd clinker plant combined with auxiliary boiler flue gases into the capture system. Auxiliary boiler supplies steam for solvent regeneration. The study developed an AACE Class 3 capital cost estimate (+30%/-20%) at approximately 30% design completion to evaluate the technical and economic feasibility of capturing up to 2 million tonnes of CO 2 per year.

42 ENGINEERING

Scalable electrified cementitious materials production and recycling

The production of Portland cement, the industry-standard cement, contributes ~8% of global CO 2 emissions through fossil-fuel heating and decomposition of limestone (the primary cement raw material). Decarbonization, e.g., via direct electrification, of this 200-year-old liming routine is extremely challenging at the industry scale. We propose a scalable electrochemical decarbonization approach to circumvent the limestone use by switching to carbon-free calcium silicates from abundant minerals and recycled concrete. Water electrolysis produces protons and hydroxides to drive a pH gradient that accelerates Ca 2+ ion leaching from calcium silicates and captures atmospheric CO 2 to form carbon-negative CaCO 3 , which serves as the feedstock for cement manufacturing or as the carbon-mineralized product for cement substitution with permanent carbon storage. Value-added co-products amorphous silica and green H 2 further enhance cement performance and supplant fossil fuels for net-zero transition, respectively. The products readily meet present-day regulatory standards and demands, and the approach readily synergizes with business-as-usual cement manufacturing and concrete construction, which are important for upscaling and structural safety, promising ready reception by the public and industries. Blended Portland cement produced through our approach with carbon-negative CaCO 3 and silica demonstrates enhanced resilience and achieves carbon neutrality or negativity when incorporating storage or circulation of CO 2 from cement plant flue gas, respectively. This low-cost, electrochemical cement production approach using abundant ubiquitous raw materials enables electrification, transition to clean fuel, and decarbonization at a gigaton scale.

36 MATERIALS SCIENCE

Air Emissions Impacts of Fuel Substitution in the United States Cement Industry

High-heat industrial processes cannot be easily electrified, often rely on comparatively high-emitting solid fuels, and are essential for economic growth. Cement production in particular is critical to supporting construction and the expansion and maintenance of infrastructure systems in countries around the world. Fuels for cement production include petcoke, coal, and waste solvents, and their combustion contributes approximately 40% of the CO 2 emissions from global cement production. Broadening the fuel resources to include agricultural residues and other wastes can reduce emissions and divert waste from landfills. We assess the potential to use 16 different alternative fuels across the 88 integrated cement plants in the United States. The share of alternative fuels in the cement production sector could increase from the current level of 17% to as high as 73%. Fuel substitution can reduce the current fuel-related life-cycle emissions (28.6 ± 5.7 Mton CO 2 /year) by 19–45%. The greatest national-scale human health cobenefits occur when alternative fuels are prioritized at facilities currently using coal and petcoke. NO x emissions outcomes from this strategy are mixed, but SO x and particulate matter emissions reductions drive net human health benefits. These results suggest that targeted fuel substitution in heavy industries can yield outsized emissions benefits.

alternative fuels

ZeroCAL: Eliminating Carbon Dioxide Emissions from Limestone’s Decomposition to Decarbonize Cement Production

Limestone (calcite, CaCO 3 ) is an abundant and cost-effective source of calcium oxide (CaO) for cement and lime production. However, the thermochemical decomposition of limestone (~800 °C, 1 bar) to produce lime (CaO) results in substantial carbon dioxide (CO 2(g) ) emissions and energy use, i.e., ~1 tonne [t] of CO 2 and ~1.4 MWh per t of CaO produced. Here, we describe a new pathway to use CaCO 3 as a Ca source to make hydrated lime (portlandite, Ca(OH) 2 ) at ambient conditions (p, T) while nearly eliminating process CO 2(g) emissions (as low as 1.5 mol. % of the CO 2 in the precursor CaCO 3 , equivalent to 9 kg of CO 2(g) per t of Ca(OH) 2 ) within an aqueous flowelectrolysis/ pH-swing process that coproduces hydrogen (H 2(g) ) and oxygen (O 2(g) ). Because Ca(OH) 2 is a zero-carbon precursor for cement and lime production, this approach represents a significant advancement in the production of zero-carbon cement. The Zero CArbon Lime (ZeroCAL) process includes dissolution, separation/recovery, and electrolysis stages according to the following steps: (Step 1) chelator (e.g., ethylenediaminetetraacetic acid, EDTA)-promoted dissolution of CaCO 3 and complexation of Ca 2+ under basic (>pH 9) conditions, (Step 2a) Ca enrichment and separation using nanofiltration (NF), which allows separation of the Ca-EDTA complex from the accompanying bicarbonate (HCO 3 – ) species, (Step 2b) acidity-promoted decomplexation of Ca from EDTA, which allows near-complete chelator recovery and the formation of a Ca-enriched stream, and (Step 3) rapid precipitation of Ca(OH) 2 from the Ca-enriched stream using electrolytically produced alkalinity. These reactions can be conducted in a seawater matrix yielding coproducts including hydrochloric acid (HCl) and sodium bicarbonate (NaHCO 3 ), resulting from electrolysis and limestone dissolution, respectively. Careful analysis of the reaction stoichiometries and energy balances indicates that approximately 1.35 t of CaCO 3 , 1.09 t of water, 0.79 t of sodium chloride (NaCl), and ~2 MWh of electrical energy are required to produce 1 t of Ca(OH) 2 , with significant opportunity for process intensification. This approach has major implications for decarbonizing cement production within a paradigm that emphasizes the use of existing cement plants and electrification of industrial operations, while also creating approaches for alkalinity production that enable cost-effective and scalable CO 2 mineralization via Ca(OH) 2 carbonation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Optimization of Membrane-based Carbon Capture using Dimensional Analysis, CFD and Process System Engineering

Carbon capture is a promising option to mitigate CO2 emissions from existing coal-fired power plants, cement and steel industries, and petrochemical complexes. Among the available technologies, membrane-based carbon capture presents the lowest energy consumption, operating costs, and carbon footprint. In addition, membrane processes have important operational flexibil-ity and response times. On the other hand, the major challenges to widespread application of this technology are related to reducing capital costs and improving membrane stability and durability.To upscale the technology into stacked flat sheet configurations, high fidelity computational fluid dynamics (CFD) that describes the separation process accurately are required. High fidelity simulations have been shown to be effective in studying the complex transport phenomena in membrane systems. In addition, obtaining high CO2 recovery percentages and product purity requires a multi-stage membrane process, where the optimal network configuration of the membrane modules must be studied in a systematic way. In order to address the design problem at process scale, we formulate a superstructure for the membrane-based carbon capture, including up to three separation stages. In the formulation of the optimization problem, we include reduced models, based on rigorous CFD simulations of the membrane modules. Numerical results indicate that the optimal design includes three membrane stages, and the capture cost is 45.4 $/t-CO2.

Pedrozo, Hector A.

Membrane-based Carbon Capture Process Optimization using CFD Modeling

Carbon capture is a promising option to mitigate CO2 emissions from existing coal-fired power plants, cement and steel industries, and petrochemical complexes. Among the available technologies, membrane-based carbon capture presents the lowest energy consumption, operating costs, and carbon footprint. In addition, membrane processes have important operational flexibility and response times. On the other hand, the major challenges to widespread application of this technology are related to reducing capital costs and improving membrane stability and durability. To upscale the technology into stacked flat sheet configurations, high fidelity computational fluid dynamics (CFD) that describes the separation process accurately are required. High fidelity simulations have been shown to be effective in studying the complex transport phenomena in membrane systems. In addition, obtaining high CO2 recovery percentages and product purity re-quires a multi-stage membrane process, where the optimal network configuration of the mem-brane modules must be studied in a systematic way. In order to address the design problem at process scale, we formulate a superstructure for the membrane-based carbon capture, including up to three separation stages. In the formulation of the optimization problem, we include reduced models, based on rigorous CFD simulations of the membrane modules.

Pedrozo, Hector A.