Development of process model of CESAR1 solvent system and validation with large pilot data
Presented at the 16th International Conference on Greenhouse Gas Control Technologie in Lyons, France.
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Presented at the 16th International Conference on Greenhouse Gas Control Technologie in Lyons, France.
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Abstract Black liquor (BL) dewatering by multi‐effect evaporation in the kraft papermaking process is highly energy‐intensive. It was previously shown that graphene oxide (GO) nanofiltration membranes can remove lignin, other organics, and inorganic salts from BL while exhibiting stability in caustic BL conditions. Here, we design and simulate several candidate dewatering processes and evaluate their technoeconomic characteristics. All processes concentrate BL from 15 to 30 wt% solutes while producing aqueous permeate. Two process options were analyzed—option A including “last‐mile” permeate treatment to reduce solutes to 0.2 wt%, and option B excluding this treatment and producing a 3–4 wt% solutes stream. These processes were simulated in custom‐built ASPEN Plus flowsheets interfaced with Microsoft Excel and MATLAB. All processes deliver large (>40%) energy savings. Detailed technoeconomic analysis showed that option A processes are profitable in mills equipped with condensing turbines, but unprofitable with only purchased fuel savings. Option B processes are profitable in both situations, but require the caustic permeate to be utilized in other kraft process units. They are also profitable with electricity generation when operated at smaller scales matching the requirements of other process units. Monte‐Carlo sensitivity analysis shows that Option A can yield median 20‐year NPVs up to ~$10MM and Option B up to ~$25MM. Overall, GO membrane‐based BL dewatering is economically promising, assuming successful slipstream piloting and scale‐up campaigns. It would have immediate sustainability benefits from large energy savings, and broader implications for biorefinery processes due to the ability to fractionate biomass feedstock components under harsh conditions.
In this work, we have been developing a three-step conversion of biomass-derived syngas to methanol to dimethyl-ether (DME) to non-aromatic hydrocarbons for use as high-octane gasoline and sustainable aviation fuel. This process produces branched alkanes from DME using a Cu/BEA catalyst and is a promising alternative to other syngas conversion processes such as Fischer-Tropsch to linear alkanes and traditional ZSM-5 catalyzed methanol to aromatic gasoline. In this short article we describe some advances in our understanding related to separations and purification via the use of more detailed experimental speciation in an updated process model involving multiple phase equilibrium-based separation steps. Primary modeled reactor outlet constituents (and weight %) are: C3 and lighter hydrocarbon gases (11.1%), C4s (54.5%), H 2 (1.2%), CO 2 (2.9%), water (5.0%), unreacted DME (16.5%), methanol (2.3%), and C5+ hydrocarbons (6.4%). DME (the primary reactant) and H 2 recycle and reuse are important for the overall process efficiency, and the recycle of C4s is important to increase the C5+ yield via reactivation and homologation. Thus H 2 , C4s, and DME are targeted for recycle, while methanol and water need to be removed from the product to conform with fuel specifications. Model predictions from Aspen Plus using the NRTL-RK property method indicate a fuel composition with C5+ content of 97.1 wt%, with minor constituents: 2.4 wt% C4s, 0.3 wt% methanol, 0.1 wt% DME, 0.03 wt% water, and 0.01 wt% C3s. These ranges of minor components conform with fuel quality requirements, and the modeled product is amenable for unconstrained blending to boost gasoline octane ratings.
Existing literature lacks detailed techno-economic and environmental life cycle analyses (TEA-LCA) focused on supercritical biodiesel production pathways produced via waste products. Therefore, in this work, the TEA-LCA was conducted to generate supercritical biodiesel from waste cooking oil for plants located in the Midwest region of USA having annual production capacities of 10,600 and 128,000 t using Aspen Plus and GREET softwares. Here, two plant production capacities were chosen to capture the economies of scale impact on biodiesel manufacture cost. In the supercritical process, methanol and propane were used as a cosolvent to synthesize biodiesel from waste cooking oil (WCO) at 280 °C and 128 bar at a residence time of 8.4 min and a WCO conversion rate of 97%. Economic analysis revealed that the supercritical process was an economically attractive pathway with a 2-year payback period for the 10,600 t/year capacity along with a break-even selling price of $\$$ 2.42/gal of diesel. In case of the larger plant (128,000 t/year capacity), the payback period and the breakeven selling price were considerably lower at values of 0.4 years and $1.31/gal of diesel, respectively, due to economies of scale impact. The generated biodiesel from supercritical process for the both the plant capacities met European (EN14214) and US (ASTM D6751) fuel quality standards while the obtained commercially valuable side product, i.e., glycerol, adhered to a pharmaceutical grade of 99.7%. Cradle to gate life cycle analysis using GREET revealed that supercritical process possessed 17% lower CO2 emissions than alkali-catalyzed process and 4% lower CO2 emissions than the conventional diesel production process. Other biodiesel production pathways in the literature were also compared to the results of the TEA-LCA of supercritical biodiesel production pathway.
This work explores the prospective techno-economic performance of facilities that produce low- and net-negative-carbon liquid transportation fuels and electricity with CO 2 capture for enhanced oil recovery. The lignite and biomass-to-jet fuel process is based on KBR’s TRIG gasifier, Rectisol (for sulfur removal and CO 2 capture), fixed-bed low temperature Fischer-Tropsch synthesis of liquid fuels, and Brayton/Rankine combined cycles to convert synthesis/refining off-gases and waste heat to electricity. This work leverages a recent, highly-detailed assessment of a prospective first-of-a-kind (FOAK) demonstration facility to develop highly detailed Aspen Plus process simulations for nine prospective N th -of-a-kind (NOAK) plant equipment configurations. Component-level capital costs from the FOAK study are scaled and adjusted to reflective prospective learning-by-doing to estimate capital costs for the NOAK designs. NOAK plant economic performance is found to be largely insensitive to variations in plant configurations and electricity output fraction, but biomass input fraction significantly affects profitability. Facilities that consume only carbon–neutral biomass, with no lignite co-feed, have significantly net-negative carbon emissions and the most favorable prospective economics when carbon emissions are priced. For these facilities, the crude oil price required for plant economic viability falls rapidly from $\$$100/bbl as carbon emission prices increase above $\$$120/tonne CO 2eq . In general, plants that co-fire lignite with biomass are less profitable (than 100% biomass plants) due to their higher net greenhouse gas emissions.
Captured carbon dioxide (CO 2 ) streams contain impurities that must be removed to meet specifications for safe transport, storage, and utilization. Among these impurities, oxygen poses challenges due to its high reactivity and potential to cause corrosion, motivating stringent purity limits below 10 ppmv. Building on recent experimental demonstrations of catalytic oxygen removal using hydrogen (H 2 ), carbon monoxide (CO), methanol (CH 3 OH), and methane (CH 4 ) as reducing agents, this study presents a technoeconomic (TEA) and life cycle assessment (LCA) of these four catalytic purification pathways. Process flowsheets were developed and simulated in Aspen Plus for CO 2 streams representative of both low-temperature and high-temperature capture processes, with integrated heat recovery and energy optimization. Results showed that total purification costs were dominated by feedstock procurement and electricity consumption. Among the studied reducing agents, the CH 4 -assisted route achieved the lowest purification cost and highest CO 2 recovery. Sensitivity analyses showed that the H 2 route became competitive at H 2 prices below $\$$0.56/kg to $\$$0.84/kg, depending on the CO 2 feed temperature conditions. In conclusion, environmental impacts were primarily driven by indirect CO 2 emissions from raw material production and utility consumption.
Tackling climate change goals requires widespread deployment of process technology variants across many decentralized sites with different geographical, environmental, and operational requirements. Conventional engineering approaches focus on unique designs for each installation (process variant), while missing opportunities for manufacturing standardization. Here, instead we seek to optimize a process platform of common unit designs while simultaneously designing an entire family of process variants that make use of that platform. This reduces engineering effort, deployment timelines, and manufacturing costs. We propose a nonlinear generalized disjunctive programming formulation and convert this to an efficient mixed-integer linear programming (MILP) formulation through discretization of the design space. We formulate our optimization in Pyomo with costing from IDAES, and we demonstrate the computational performance and solution quality on a water treatment desalination system from the PARETO framework and a carbon capture system built in Aspen Plus as part of CCSI2.
The rapid integration of intermittent renewable sources into the electricity grid is driving the need for more flexible, low-carbon fossil-fuel plants with lower capital costs. This then drives the need to improve the cryogenic air separation unit (ASU). To address this changing landscape, we explore a Praxair single-column ASU (PSC-ASU) design with the goal of reducing costs and improving flexibility, compared to a conventional double-column ASU. The PSC-ASU incorporates partial air condensation and air pre-separation in the bottom reboiler with a phase separator as well as N 2 -enriched vapor condensation in the upper reboiler to decrease energy consumption, as compared to Linde’s single-column ASU. All three of the above-mentioned ASU designs are simulated in Aspen Plus and analyzed. An economic analysis is applied to evaluate the relative cost savings of the PSC-ASU compared to the double-column ASU. Results suggest that the specific energy consumption of the PSC-ASU is significantly lower than that of Linde’s single-column ASU due to a drastically improved oxygen recovery rate. Although this improved oxygen recovery rate is still lower than that of the double-column ASU, the required pressure ratio of the main air compressor is 21% lower than that of the double-column ASU. As a result, the specific energy consumption of the PSC-ASU is only 1.9% greater than that of the double-column ASU for producing 95.1 mol% O 2 . However, the PSC-ASU reduces the hourly capital cost by 19% due to the elimination of a high-pressure column. This would effectively decrease the total hourly cost of the ASU, and thus the total hourly cost of low-carbon, fossil-fuel power plants that require oxygen.
The study focuses on achieving energy self-sufficiency in Wastewater Treatment Plants by proposing a comprehensive model for integrating, sizing, and optimizing an Organic Rankine Cycle system. The Organic Rankine Cycle system is designed to utilize waste heat from the gensets at As Samra Wastewater Treatment Plant in Jordan, where it will contribute to the overall electrical energy supply of the plant. Real data from As Samra Wastewater Treatment Plant is used to model and calculate the available waste heat using TRNSYS® software. The Organic Rankine Cycle model is then developed using ASPEN PLUS® software to explore the impact of operational parameters and determine their optimal values for maximizing the plant's energy profile. An economic analysis is conducted to assess the feasibility of the proposed model, considering system components, installation, operation, and maintenance costs. To optimize the Organic Rankine Cycle system, the study employs the Multi-Output Support Vector Regression technique to capture nonlinear relationships between independent variables (fluid type, turbine inlet pressure, turbine inlet temperature, turbine outlet pressure, and mass flow rate) and dependent variables (pump power input, waste heat input, and turbine specific work). The Osprey optimization algorithm is used to address the multi-objective optimization problem, with the proposed Pareto-based Osprey Optimization Algorithm and the Multi-Objective Particle Swarm Optimization technique being employed to evaluate critical performance and economic parameters such as system thermal efficiency, net power output, and the levelized cost of electricity. The results of the optimization strategies indicate that the M-SVR model's prediction accuracy is significantly improved after parameter optimization, with the model returning high R 2 and low Mean Square Error values of 0.991 and 0.00216, respectively. The Pareto-Based Osprey Optimization Algorithm optimizer identifies the best working fluid as Isobutane/Isopentane in a ratio of 66:34, with optimal turbine inlet pressure and temperature of 15 bars and 218 °C, respectively. In conclusion, the Organic Rankine Cycle model at these optimal conditions achieves a cycle efficiency of 19.93% and an Levelized Cost of Electricity value of 0.0353 USD/kWh.
Recognizing the benefits of pressurization and fuel staging on the efficiency of oxy-combustion, the staged, pressurized oxy-combustion (SPOC) process was introduced in 2012. The combination of fuel staging and pressurized oxy-combustion results in a more compact plant, a higher plant efficiency and reduced costs for pollutant and greenhouse gas removal compared with plants equipped with conventional carbon capture. This approach to power generation enables a modular boiler design and optimizes the plant for flexible operation, which is essential to meet the demands of the modern grid when it contains intermittent power sources. Originally designed to burn coal, the SPOC process is well-suited for biomass because the combustion of biomass leads to a high moisture content in the flue gas and the SPOC process is able to recover the latent heat of this moisture, enhancing system performance over that of traditional biomass combustion at atmospheric pressure. The present work is focused on evaluating the potential for utilizing the SPOC process in retrofit applications wherein the boilers of an existing plant are replaced with the SPOC process, and woody biomass is used as the fuel to yield carbon-negative power. Two applications are considered: power generation and cogeneration (heat and power). Modeling these systems in Aspen Plus demonstrates that the SPOC process surpasses the performance of baseline plants with post-combustion capture (PCC) for both power generation and cogeneration. Specifically, compared to a PCC equipped plant, the SPOC power plant has 33% higher efficiency, and the SPOC cogeneration plant reaches 42% higher net energy. Experimentally, the existing SPOC facility was fired for the first time with 100% biomass and after minor improvements were made to the feeding system, the facility demonstrated excellent performance during startup, steady-state operation and turndown.
To allow for accurate calculations of calcium carbonate scaling in highly saline produced waters, we present a comprehensive thermodynamic model based on the electrolyte nonrandom two-liquid (eNRTL) activity coefficient equation for the aqueous Na ⁺ -Ca ²⁺ -Cl – -HCO 3 – -CO 3 ²– -CO 2 system. The eNRTL binary interaction parameters for the H 2 O:(Na ⁺ -CO 3 2– ) pair, the H 2 O:(Na ⁺ -HCO 3 – ) pair, the (Na⁺-Cl–):(Na ⁺ -CO 3 2– ) pair, and the (Na ⁺ -Cl – ):(Na ⁺ -HCO 3 – ) pair are identified in this work via the regression of thermodynamic, calorimetric, and phase equilibria experimental data. The binary interaction parameters associated with the H 2 O:(Na ⁺ -Cl – ) pair, the CO 2 :(Na ⁺ -Cl – ) pair, the H 2 O:(Ca ²⁺ -Cl – ) pair, and the (Na ⁺ -Cl – ):(Ca ²⁺ -Cl – ) pair are retrieved from the literature. The remaining binary interaction parameters are retrieved from Aspen Plus or set to zero. In addition, the solubility product constants are identified for Na 2 CO 3 ·10H 2 O (s) , Na 2 CO 3 · 7H 2 O (s) , Na 2 CO 3 ·H 2 O (s) , Na 2 CO 3 ·NaHCO 3 2H 2 O (s) , Na 2 CO 3 ·3NaHCO 3 (s) , and CaCO 3(s) via regression of solubility data. Here, the model is capable of accurately calculating all phase equilibria and calorimetric properties at temperatures up to 473.15 K and salt concentrations up to saturation.
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Steam methane reforming of natural gas is the primary method of producing hydrogen in the United States, accounting for 95% of all hydrogen produced there. Methane pyrolysis, an alternative production pathway that decomposes natural gas into solid carbon and hydrogen, both eliminates CO 2 emissions associated with methane reforming and allows for additional income from carbon black. A life-cycle inventory of this process has been developed using ASPEN Plus to model the methane pyrolysis (plasma arc) process. From well to gate, hydrogen production via methane pyrolysis produces 2.78 kg CO 2 e/kg H 2 of greenhouse gas emissions using mass allocation of emissions between hydrogen and carbon black coproducts. The well-to-gate emissions are mainly driven by electricity consumption (∼38 kW h/kg H 2 ), which accounts for 81% of the emissions; if renewable electricity is used, well-to-gate emissions can be reduced to −0.448 kg CO 2 e/kg H 2 .
Aqueous amines, as the most mature carbon capture technology, are subject to high energy and cost penalties due to the large water content in their formulations. Emerging technologies are in demand to enable a transition to a low-carbon global economy. However, rigorous process modeling and techno-economic analyses are limited for emerging carbon capture technologies. Here, four CO 2 -Binding Organic Liquids (CO 2 BOLs), all water-lean solvents were presented as promising options towards energy-effective and low-cost carbon capture from point sources. Rigorous solvent property and process models were developed in Aspen Plus for a coal-fired power plant with CO 2 BOL-based carbon capture unit. Techno-economic analyses were conducted in 2018 US pricing basis. The results suggest that water-lean formulations can minimize water condensation and vaporization, leading to a 36% energy saving compared with aqueous amines. Indeed, these CO 2 BOLs can capture up to 97–99% CO 2 from coal fired plant. The estimated carbon capture cost is about $40/tonne CO 2 at 90–97% carbon capture rate, about 12–23% less expensive than the conventional aqueous amine technology. The comparison between these CO 2 BOLs showed that in addition to vapor liquid equilibrium and kinetics (key properties for aqueous solvents), viscosity, volatility, and hydrophobicity, also have strong impacts on the performance of water-lean solvents. The methods presented in this work can be used to evaluate other emerging carbon capture technologies, while the results linking costs and performance of carbon capture solvents with their properties. Additionally, this work identifies research directions and targets for further reductions in total costs of capture from either cost or energy perspectives for these leading water-lean solvents.
Synthetic natural gas (SNG) is of great interest in reducing fossil energy consumption while maintaining compatibility with existing NG infrastructure and end-use applications equipment. SNG can be produced using clean H 2 generated from renewable or nuclear energy and CO 2 captured from stationary sources or the atmosphere. In this study, we develop an engineering process model of SNG production using Aspen Plus® and production scales reported by the industry. We examine the levelized cost and life cycle greenhouse gas (GHG) emissions of SNG production under various CO 2 supply scenarios. Considering the higher cost of H 2 transportation compared with CO 2 transportation, we assume that CO 2 feedstock is transported via pipeline to the H 2 production location, which is collocated with the SNG plant. We also evaluate the cost of CO 2 captured from the atmosphere, assuming the direct air capture process can occur near the SNG facility. Depending on the CO 2 supply chain, the levelized cost of SNG is estimated to be in the range of $\$45–76$ per million British thermal units (MMBtu) on a higher heating value (HHV) basis. The SNG production cost may be reduced to $\$27–57$/MMBtu-HHV by applying a tax credit available in the United States for low-carbon H 2 production (45V). With a lower electricity price of 3¢/kWh for water electrolysis and accounting for a 45V tax credit, the SNG cost reaches parity with the cost of fossil NG. Depending on the CO 2 supply chain, SNG can reduce life cycle GHG emissions by 52–88% compared with fossil NG.
Membrane technology for CO 2 capture has become an attractive strategy due to its cost and energy efficiency and low materials costs. In the past decade, membrane-based process designs for post-combustion power plant CO 2 capture have been developed, utilizing existing highly CO 2 -permeable membranes with relatively low CO 2 /N 2 selectivity (<50), and have obtained reasonably economic carbon capture. However, few membrane-based process designs were proposed for moderate to highly CO 2 -selective membranes (CO 2 /N 2 selectivity of 50–300, and >300, respectively), which have vastly emerged in recent years, such as various facilitated transport membranes (FTMs). Herein, we proposed a two-stage membrane-base process design targeting economic carbon capture from coal-fired flue gas. This process design features the utilization of highly CO 2 -selective membranes for one-stage CO 2 enrichment to 95% dry-base purity in the first stage and recycle of the remaining CO 2 by a highly CO 2 -permeable membrane in the second stage, in order to achieve economic CO 2 capture with 90% capture rate and >95% CO 2 product purity. Through an integration-iteration membrane model and the Aspen Plus process simulation, a sensitivity study of operating pressures (feed and permeate pressures) and membrane properties (CO 2 permeance and CO 2 /N 2 selectivity) was conducted. Critical CO 2 /N 2 selectivity of 300–400 was found for the highly CO 2 -selctive membranes to meet the demand for cost and energy efficient results. The lowest possible membrane area of 4.8 × 10 5 m 2 and fractional energy of 19.3% were obtained, which is comparable to or even more attractive than reported membrane-based process designs. Here, this work provides a new membrane process design option for highly CO 2 -selective membranes and gives insights on the influence of membrane performance and operation condition.
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