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At least 37 records · Page 2

Wet Waste Hydrothermal Liquefaction and Biocrude Upgrading to Hydrocarbon Fuels: 2022 State of Technology

Data from Pacific Northwest National Laboratory’s (PNNL) conversion hydrothermal liquefaction (HTL) program for wet waste was used to update the pathway techno-economic analysis (TEA) for the fiscal year 2022 State of Technology (2022 SOT). Figure S.1 shows the modeled minimum fuel selling price (MFSP) for the 2022 SOT, along with the previous years’ SOTs (Snowden-Swan et al. 2020, 2021, 2022). These costs are for a HTL plant scale of 110 dry ton/day sludge feed and a larger centralized upgrading plant scale of 38 million gallons/year biocrude feed, commensurate with the design case. All costs were updated to 2020 dollars. Corresponding cost breakdowns and technical parameters for each case are given in Appendix B. In previous years’ analyses options with and without ammonia (NH 3 ) stripping treatment of the HTL aqueous phase recycle stream were included in the analysis to account for cases with direct recycle of untreated HTL aqueous phase back to the wastewater treatment plant. In the FY21 SOT assessment however, system boundaries for the analysis were adjusted to reflect separate ownership/operatorship for the HTL plant and with that, nutrient surcharge fees associated with disposal of the aqueous phase wastewater to a municipal sewer system were incorporated to provide an improved accounting of true disposal costs for a standalone plant. With these changes, there is no significant cost difference between the case including ammonia removal and the case excluding ammonia removal and therefore the “no NH3 removal” options will not be included in the 2022 and future SOTs.

09 BIOMASS FUELS↗

Spent Crystalline Silicotitanate Storage Study—Post AP-105DF Processing

A Tank-Side Cesium Removal (TSCR) system is under development by Washington River Protection Solutions to support initial production of immobilized low-activity waste (LAW) by feeding Hanford tank supernate from tank farms to the Hanford Waste Treatment and Immobilization Plant (WTP) LAW Facility. Tank waste supernate is filtered to remove suspended solids and then Cs is removed by processing it through crystalline silicotitanate (CST) ion exchange media manufactured by Honeywell UOP, LLC. The Cs-loaded CST columns will be stored indefinitely, with a goal of eventual CST removal and treatment. Thus, the spent CST needs to be recoverable after undetermined storage time. Previous testing with AP-105 simulant showed that rinsing the CST bed with 3 bed volumes (1.4 apparatus volumes [AVs]) of 0.1 M NaOH resulted in a dried bed that maintained flow characteristics indicative of ease of recovery. This study explored the intermediate conditions (between feed dried in place and the 1.4 AVs of 0.1 M NaOH rinse) to evaluate CST bed properties.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Glass formulation and lab-scale testing of glasses designed for in-can Melter and in-container Vitrification of high-assay low-enriched uranium aqueous polishing Raffinate waste

Glasses were designed for processing a nuclear waste from aqueous polishing of high-assay low-enriched uranium using either In-Can Melter (ICM) or GeoMelt® In-Container Vitrification™ (ICV) technologies, which operate at temperatures of T p ≤ 1100 °C and T p ≤ 1450 °C, respectively. Due to the different operating conditions, the melt and glass properties were optimized differently for each technology. Each glass was designed to optimize for maximum waste loading while simultaneously satisfying processing (e.g., crystallization, viscosity, and conductivity) and product quality (e.g., durability, hazard characteristic, and crystal content) constraints. Here, the raffinate waste contains high nitric acid (4 M) and low total solids (9 g·L -1 ) concentrations. Feed preparation processes were tested to facilitate concentration and nitrate destruction/removal while controlling redox of the melter feed. A successful feed process including sugar addition and spray-drying was performed to generate an adequate melter feed for ICV processing.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Effect of water vapor and thermal history on nuclear waste feed conversion to glass

Water affects the glass melting process by interacting with the foam layer at the glass melt surface and by influencing the batch conversion reactions. Water vapor from the nuclear waste slurry feed maintains a high water vapor pressure in the melter atmosphere. To investigate to what extent water vapor affects the vitrification of nuclear waste in joule-heated, cold-top melters, a series of feed expansion experiments were performed under humid and dry atmospheres using samples of low-activity waste (LAW) melter feed simulants. Melting of feed pellets in the presence of water vapor slightly decreased the temperature of primary foam onset, but did not significantly affect the feed volume expansion by foaming or the foam-collapse temperature. Sets of feed expansion experiments and evolved gas analyses were also performed to check the effect of thermal history on LAW feed samples tested as direct slurry, loose powder, and slow- and fast-dried pellets.

Marcial, Jose↗

Spent Crystalline Silicotitanate Storage Study

Washington River Protection Solutions is working to support initial production of immobilized low-activity waste (LAW) by feeding Hanford tank supernate from tank farms to the Hanford Waste Treatment and Immobilization Plant (WTP) LAW Facility. This goal incorporates the design of a Tank-Side Cesium Removal (TSCR) system, which filters tank waste supernate to remove suspended solids and then removes Cs by processing it through crystalline silicotitanate (CST) ion exchange media manufactured by Honeywell UOP, LLC. The 137 Cs-depleted product is intended to be sent to the WTP for vitrification. The Cs-loaded CST columns will be stored indefinitely, with a goal of eventual CST removal and treatment. Thus, the spent CST needs to be recoverable. The testing described herein looks to potential upset process conditions where CST storage may be required before various rinse steps are completed. This study evaluated upset conditions at three sequential processing steps envisioned for TSCR (feed, 0.1 M NaOH rinse, water rinse), and in-column drying with compressed air (normal end step) to assess impacts on the nature of the CST bed. Testing was conducted at the small scale (12-mL bed volume); simulated AP-105 tank waste was used as the feed. Following process disruption, the CST bed was dried in place at 70 °C. Post-dried CST bed physical properties (angle of repose, penetration depth, particle morphological changes) were measured to evaluate how CST moved and flowed. The testing is intended to provide a preliminary assessment of issues that may arise from desiccation of CST with the indicated salt solutions in place. Since these were small-scale tests, the processing conditions will not match full scale conditions exactly; however, the tests do provide insight into the impact of stopping processing at an earlier step than normal. Except for the feed that was dried in-place, all other process stop-conditions showed the CST bed flowed well after drying. At this small scale, CST beds would not present an issue for retrievability. The feed that was dried in place had solidified into a rock-hard monolith with no movement possible. Samples had to be chipped from the surface.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Physical Properties of Moist, Fermented Corn Grain after Processing by Grinding or Milling

A novel biomass production system, integrating the co-harvesting and co-storage of moist corn grain and stover, promises a reduction in delivered feedstock costs. In this innovative method, the dry grain traditionally utilized for feed or biofuel production will now be processed at a considerably greater moisture content. The adoption of this approach may necessitate a substantial redesign of existing material handling infrastructure to effectively accommodate the handling and storage of moist grain after processing by milling or grinding. A comprehensive study was conducted to quantify the physical properties of this grain after processing with a knife processor or a hammermill. The geometric mean particle size, bulk and tapped density, sliding angle, material coefficient of friction, and discharged angle of repose were quantified. Five grain treatments, either fermented or unfermented, and having different moisture contents, were used. After processing, the moist, fermented ground grain exhibited a significantly smaller particle size compared to the dry grain. Additionally, both moist processed grains resulted in a decreased bulk density and increased material sliding angle, friction coefficient, and angle of repose. The examined metrics collectively suggest that handling, mixing, and storing moist ground grain will pose significant challenges compared to conventional dry ground grain. This increased difficulty may lead to substantially higher costs, a crucial factor that must be carefully considered when evaluating the overall economics of implementing this new biomass production system using combined harvesting and storage of corn grain and stover.

Blazer, Keagan J.↗

Development of an enzyme cocktail to bioconvert untapped starch in sweet sorghum processing by-products: Part II. Application and economic potential

Demand for bioethanol and other biochemicals produced from agricultural crops has increased. Sweet sorghum has been identified as a promising bioenergy crop as it can produce starch, sugar, and fibrous biomass. During processing, starch accumulates in the juice sediments and clarification mud. And, while currently not recovered, it can be made accessible for fermentation by enzymatic hydrolysis. The enzymatic hydrolysis of starch in sweet sorghum processing streams was investigated, followed by fermentation of the resulting glucose to ethanol. The juice sediment contained sufficient starch to increase fermentable sugars by 127%, allowing a final ethanol titer of 11.1 vol%. The economics for fermentation of only dissolved sugars (Scenario 1) versus dissolved sugars and hydrolyzed starch (Scenario 2) were compared using a technoeconomic model. Fixed capital cost was found to be similar for both scenarios. For a set harvest period, Scenario 2 could produce 20% more ethanol; however, if the distillation by-product was dried and marketed as animal feed, Scenario 1 was more cost effective. A plant producing 5.6–5.7 Mkg of fuel ethanol per year had a minimum selling price of $0.67/kg of ethanol with concurrent production of animal feed and zero cost sweet sorghum processing. Finally, even with these optimistic assumptions, the estimated production cost was higher than the current wholesale price of fuel ethanol.

09 BIOMASS FUELS↗

Dynamic Life-Cycle Analysis of Fast Pyrolysis Biorefineries: Impacts of Feedstock Moisture Content and Particle Size

The commercialization of biorefineries has been met with significant obstacles due to the technical difficulties of handling solid biomass feedstocks, which are highly variable in physical properties and chemical compositions. An understanding of the principles of unit operations along the supply chain is key to the success of the biofuel industry. This study applies a dynamic life-cycle analysis (DLCA) methodology by developing quantitative relationships between the inputs and outputs for each unit operation based on scientific understanding of the causal effects. Using the DLCA, we assessed system sustainability of drop-in fuel production from fast pyrolysis of pine residues followed by hydro-processing. Life-cycle greenhouse gas (GHG) emissions were calculated for 4641 runs involving two key feedstock parameters: moisture content after field drying and particle size of the feed to pyrolyzer. Moisture contents varied between 25% and 35%, while particle sizes varied between 0.5 and 5 mm in these runs. The life-cycle GHG emissions of these cases vary from 22 to 40 g/MJ. Close examination of each unit operation's contribution to the total GHG emissions reveals that low moisture content after field drying produces savings in energy consumption during feedstock transportation and on-site drying. However, although small particle size leads to overall higher fuel yield, it also requires a significant amount of energy for feedstock size reduction and fuel production. The energy penalty outweighs the benefit of increased fuel yields, especially when fine particles (<1 mm) are used for pyrolysis; thus, small particle size leads to increased GHG emissions overall. The results highlight the trade-offs between the energy demand for preprocessing and the conversion yields, which can be addressed with DLCA.

09 BIOMASS FUELS↗

Grafted nickel-promoter catalysts for dry reforming of methane identified through high-throughput experimentation

High-throughput synthesis of a series of monometallic and bimetallic catalysts (45 bimetallic and 50 monometallic samples) consisting of nickel and one of nine different metal promoters (B, Co, Cu, Fe, Mg, Mn, Sn, V and Zn) supported on one of six different metal oxides alumina, ceria, magnesia, silica and titania) is carried out via organometallic grafting using a robotic platform. The catalysts are evaluated for their activity and selectivity for the dry reforming of methane at a feed ratio of CH 4 :CO 2 of 1 at 650–800 °C in a parallel flow reactor system. The type of oxide support prevails over the type of additive for both catalyst activity and stability. On Al 2 O 3 and MgO, Fe was found to be the best promoter; on SiO 2 , Cu is the best promoter at 700 °C and higher, while on TiO 2 , Mn is found to enhance the conversion at 800 °C. On CeO 2 , all additives except Fe have beneficial effects. Twenty-five catalysts show > 90% methane conversion with ten catalysts showing > 95% conversion at 800 °C with the H 2 :CO ratios ranging from 0.8 to 1.2. Amongst the ten highest performers, NiFe/Al 2 O 3 and NiFe/MgO are more active than Ni/Al 2 O 3 and Ni/MgO, respectively and were stable over a period of 25 h at 800 °C. Characterization on the as-prepared samples reveals highly dispersed phase, while after reduction in H 2 , highly dispersed and reduced nickel particles up to 10 nm are formed. The particles do not increase in size under dry reforming reaction conditions at 800 °C. An increased hydrogen consumption observed during H 2 -TPR of the nickel particles is positively correlated with methane conversion for Al 2 O 3 -based catalysts. The resistance to deactivation by coking and variation in coke structure are investigated by spectroscopic and microscopic methods to identify the relationship between metal promoters, alloy formation, and type of surface carbon deposits. Carbon whiskers were observed on the ten selected spent samples and are preferentially deposited on Ni rather than on the promoters. Carbon nanotube formation and metal particle removal from support were not observed to cause deactivation while amorphous carbon formation was clearly linked to catalyst deactivation, as amorphous carbon could encapsulate nickel, either on the support or at the end of the carbon nanotube. Furthermore, the organometallic grafting technique is an efficient and suitable technique for synthesizing highly dispersed and homogeneous phases which lead to high conversion and high durability for dry reforming of methane.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Increasing the Electrolyte Salinity to Improve the Performance of Anion Exchange Membrane Water Electrolyzers

Direct operation of anion exchange membrane water electrolyzers (AEMWEs) with near-neutral pH feeds avoids the use of highly alkaline and corrosive solutions. However, using neutral pH solutions currently faces fundamental operational challenges that diminish performance and reduce long-term stability due to poor solution conductivity and low hydroxide ion concentration. Here, we showed that amending near-neutral pH solutions with low concentrations of alkali metal salts in a dry-cathode configuration substantially improved performance and stability. Adding NaClO 4 (10 mM) to the anolyte reduced the operating voltage by 0.19 to 2.58 V at 500 mA/cm 2 compared to non-saline solutions (2.77 V). However, further increases in the feed salt concentration (100 mM NaClO 4 ) reduced performance (2.64 V) due to a greater co-ion diffusion through the anion exchange membrane. Electrolyzer performance was further improved by utilizing salts with high conductivity such as KNO 3 . Using a saline anolyte reduced ohmic resistance, resulting in smaller applied voltage and energy consumption for hydrogen generation, while the combined effect of the membrane charge and the electric field direction in the dry-cathode feed configuration minimized ion crossover. Thus, increasing the salinity of near-neutral pH solutions represents a cost-effective strategy to improve the performance of AEMWE compared to ultrapure electrolytes, minimizing risks and costs associated with recirculating highly alkaline solutions.

anion exchange membrane water electrolyzer↗

Water as a gas separation membrane

Efficient gas separation membranes are essential for carbon capture, biogas upgrading, and hydrogen purification. Inspired by how plants absorb CO 2 through water, we present a membrane platform that uses liquid water as the selective layer. Hydrophilic sub-100-nm pores stabilize water through strong capillary forces, enabling operation at feed pressures above 72 bar under dry and humid conditions. Selectivity is governed by gas solubility in water, while permeance is tuned by adjusting the water layer thickness. Reducing this thickness below 200 nm yields CO 2 permeances up to 11,600 gas permeation units with CO 2 :N 2 , CO 2 :CH 4 , and CO 2 :H 2 selectivities of 40, 26, and 31, respectively, surpassing the performance of state-of-the-art membranes. Operation is sustained for over a week without water loss, and performance scales using commercially available porous polymer supports under mixed-gas crossflow conditions. Water’s dissolution-based transport avoids saturation and reaction-rate limits, enabling a robust, high-performance, and environmentally benign gas separation platform.

08 HYDROGEN↗

A Comparison of Multiple Macroalgae Cultivation Systems and End-Use Strategies of Saccharina latissima and Gracilaria tikvahiae Based on Techno-Economic Analysis and Life Cycle Assessment

Macroalgae can be processed into various products with the potential to substitute land-based crops; their cultivation can bioextract nutrients from coastal waters. This study investigated the economic cost and environmental impacts of multiple seaweed cultivation platforms, cultivation strategies, and processing/end-use strategies through techno-economic analysis (TEA) and life cycle assessment (LCA) with a focus on Saccharina latissima and Gracilaria tikvahiae. Cultivation platforms included single-layer longline, dual-layer longline, single-layer strip, and dual-layer strip systems. Processing/end-use products included seaweed to biofuel, dried sea vegetables, marketable commercial fertilizer, and animal feed. Economic and environmental costs decreased with dual-layer and strip cultivation systems. Cultivation costs were highest using the common single-layer longline system ($4.44 kg−1 dry weight (dw) S. latissima and $6.73 kg−1 dw G. tikvahiae when cultivated on rotation). The use of the dual-layer strip system reduced cultivation costs to $2.19 kg−1 dw for S. latissima and $3.43 kg−1 dw for G. tikvahiae. Seaweed drying was the major contributor to economic and environmental costs for macroalgae processing. Yet, all scenarios achieved environmental benefits for marine eutrophication. The best environmental performance was observed when biomass was processed to dry sea vegetables, assuming the offset of land-based vegetable production, or used as biofeedstock for anaerobic digestion for combined heat and power.

Wu, Jingjing (ORCID:0000000305311353)↗

Brief Update on Advancements by Commercial Vendors/Options for Feeding and Pumping Biomass Slurries for Hydrothermal Liquefaction

In 2011, Pacific Northwest National Laboratory (PNNL), working as a partner in the National Advanced Biofuels Consortium, issued a report assessing the viable industrial feed system and pump options for a 2000 dry metric tons per day production-scale hydrothermal liquefaction (HTL) plant (Berglin et al. 2012). This report was issued as PNNL-21981, Review and Assessment of Commercial Vendors/Options for Feeding and Pumping Biomass Slurries for Hydrothermal Liquefaction, and will be referred to as “Pump Survey” for reference. It had the following scope: • Identify relevant applications and industries operating at comparable scales • Interact with commercial vendors and pursue integration between vendors • Take advantage of commercial off-the-shelf (COTS) technology • Supply and support vendor needs for biomass feedstock rheology characterization • Provide vendors with process requirements to support selection of conceptual design for feedstock handing and pump system • Obtain cost data to the extent possible from equipment vendors to support the technical economic analysis (TEA) • Identify issues associated scale-up. The current document represents an update to the prior report in order to: 1. Identify advancements in vendor-reported technologies 2. List reports of new experience or trials with biomass pumping applications 3. Determine if technology/application gaps identified in the prior report have been filled 4. Capture ideas on future research.

09 BIOMASS FUELS↗

Cesium Ion Exchange Testing Using Crystalline Silicotitanate with Hanford Tank Waste 241-AP-107

At the time of this testing, the Low-Activity Waste Pretreatment System (LAWPS) was to provide for the initial production of immobilized low-activity waste by feeding Hanford tank supernate from tank farms to the Hanford Tank Waste Treatment and Immobilization Plant (WTP) Low-Activity Waste (LAW) Facility for immobilization. Washington River Protection Solutions requested that Hanford tank waste collected from tank 241-AP-107 (hereafter called AP-107) be processed using conceived pretreatment steps (suspended solids removal by filtration, Cs removal by ion exchange) then vitrified. A small-scale test platform to demonstrate the solids filtration, Cs removal, and LAW vitrification was constructed and installed at Pacific Northwest National Laboratory. Bench-scale ion exchange testing with approximately 9 L of AP-107 supernate was conducted using crystalline silicotitanate (CST) ion exchange media. The IONSIV R9140-B CST was provided by Honeywell UOP, LLC in 2018 (Batch 2081000057). The ion exchange media was first tested with simulant and was previously described. This report describes the Cs ion exchange batch contact and column test results with the AP-107 tank waste. Batch contact testing helps to evaluate CST performance on tank waste supernate prior to processing it in the ion exchange columns. Batch contacts were performed with the waste at four Cs concentrations at a phase ratio of 200 (liquid volume to exchanger mass) with AP-107. The distribution coefficient (K d ) at the equilibrium condition of 8.57 µg Cs/mL (AP-107 feed condition) was determined to be 669 mL AP-107/g CST. With a CST bed density of 1.00 g/mL, this K d corresponded to a predicted 50% Cs breakthrough of 669 bed volumes (BVs). The Cs load capacity at the equilibrium feed condition was determined to be 7.5 mg Cs/g dry CST. The column testing was prototypic to the intended LAWPS operations in a lead-lag column format, although on a small-scale basis with 10-mL CST beds. The feed was processed downflow through the lead column and then through the lag column at ~2.2 BV/h. Loading continued until the lag column reached the WTP waste acceptance criteria (WAC) for receiving supernatant waste for vitrification (a function of the Na and 137 Cs concentrations). For AP-107, the WAC is 0.114% of the influent 137 Cs concentration; this required a Cs decontamination factor of 876. The Cs effluent from the lag column reached the WAC after processing ~410 BVs. To keep the subsequent product effluent below the WAC, a replacement lag column was prepared, the lead column was removed from service (after processing a total of 471 BVs), the lag column was put into the lead column position, and the replacement lag column was installed. Feed processing continued and after another ~290 BVs the Cs effluent from the lag column again exceeded the WAC. In both cases, the lead columns only reached 25% Cs breakthrough before removal. Although 50% Cs breakthrough was not reached, this value was estimated and averaged based on extrapolation of the loading curves (640 BVs) and agreed within 4% of the predicted 50% Cs breakthrough from batch contact test results (669 BVs). Table ES.1 summarizes the observed column performance and relevant Cs loading characteristics.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

The Sensitivity of PBX 9502 to Drilling Operations

Polymer-bonded explosive (PBX) 9502 (95% TATB, 5% Kel-F 800 by weight) is dry-drilled on a CNC milling machine and its thermomechanical response to varying feed rates, drilling speeds, and peck depths with 4 mm and 5 mm diameter drill bits is investigated. The tested samples are affixed to a force sensor that enables recording temporally resolved cutting forces and torques, and a drill-embedded thermocouple yields local temperature data. From the data, an empirical relationship between temperature changes and feed per revolution is developed, which reveals reduced temperatures in higher feed per revolution regimes for PBX 9502. The observed relationship allows extrapolating to temperatures for other hole diameters, indicating increased temperature for smaller diameter drilling across the board. Additional testing was performed with PBX 9501 (95% HMX, 2.5% Estane®, 2.5% BDNPA/BDNPF by weight), albeit over a reduced parameter space, which revealed the opposite behavior for the feed per revolution temperature dependence. It is concluded that both PBX 9502 and PBX 9501 can be dry-drilled efficiently beyond the limits of presently applicable US-DOE standards, where cutting interface temperatures remain far below material critical temperatures. Finally, data reveals that coolant usage in the drilling process for these materials provides a wide safety margin.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

PERFORMANCE ANALYSIS OF AN ENGINEERING SCALE HYDROTHERMAL LIQUEFACTION SYSTEM

This work evaluates the Modular Hydrothermal Liquefaction System (MHTLS), an engineering-scale, integrated continuous HTL plant operated at the Pacific Northwest National Laboratory (PNNL), for converting realistic wet wastes into energy-dense biocrudes. The production campaigns discussed here processed algae, sewage sludges, lignocellulosic blends, Industrial food waste, and engineered food-waste slurries at 350?°C and around 200?bar, with nominal feed rates of ~12?L?h?¹. We report biocrude yields and composition, establish mass and elemental (C, N) balances, and quantify energy performance via heater duties, heat-exchanger behavior, and system-level efficiencies. Biocrudes contained 76–80?wt?% C (dry, ash-free) with HHVs of 38-41?MJ?kg?¹, substantially higher than feed materials HHVs of 16.6–26.1?MJ?kg?¹ and approaching petroleum fuels. Dry, ash-free biocrude yields of 32–53?wt?% corresponded to 43–71?wt?% carbon yields, with 18–40?wt?% of feed carbon routed to the aqueous phase. Thermal efficiencies were 50-65%, and total energy efficiencies, including reactor heat input, were 35-55%. A counter-current tube-in-tube heat exchanger delivered U values of 200–450?W?m?²?K?¹, with fouling-induced declines impacting heat recovery and heater duty. The analysis highlights three priorities for the process intensification of HTL: robust, fouling-resistant heat recovery, hydrodynamically suitable reactor and heat-exchanger designs, simplified and predictable solids management, and biocrude-water separation.

Biocrude production↗

Process Considerations for the Production of Hydrogen via Steam Reforming of Oxygenated Gases from Biomass Pyrolysis and Other Conversion Processes

Abstract In 2021, average CO 2 emissions was 9.7 g CO 2 /g H 2 produced, primarily based on steam methane reforming (SMR) technology that currently dominates hydrogen production. The substitution of natural gas (NG) and other fossil feedstocks in SMRs with renewable gases may be considered as an option for reducing greenhouse gas emissions. This analysis explores process impacts and constraints associated with the potential introduction of biogenic gases into SMRs. The results indicate that replacing NG in the fuel train of the SMR, followed by partial replacement of NG in the feed train may be a feasible approach. For the CO‐ and CO 2 ‐rich gas compositions assumed in this analysis the results indicate that feed train may accommodate up to 25 mole % of biogenic gases using allowances in existing designs and/or with small modifications, while maintaining similar hydrogen output. NG substitution in higher proportions require more major changes because of increased flow rates and heat exchange requirements in the system. Biogenic gases with lower CO 2 and higher calorific values are advantageous for NG substitution, and dry reforming using the CO 2 present in the feed gas can reduce steam consumption and increase process efficiency within limits where coking does not become a new constraint.

08 HYDROGEN↗

Use of a Pressurized Water Treatment to Prevent Cracking of Internal Gelation Sol-Gel Microspheres

Pressurized water treatments were investigated as a means to prevent cracking of internal gelation sol-gel microspheres upon drying and heating. A batch of gelled cerium oxide microspheres was prepared, split into two samples that were processed with and without a pressurized water treatment, and dried in air at room temperature. Thermal gravimetric analysis was used to compare the mass loss profiles between the two samples and to understand volatile emissions from cerium oxide microspheres during heat treatments up to 600 °C. Microspheres that were processed without a pressurized water treatment lost approximately 4.6 times more mass upon heating than microspheres that were subjected to a pressurized water treatment. Comparison of the cracking behavior of microspheres prepared with and without a pressurized water treatment indicated that microspheres subjected to a pressurized water treatment were virtually crack-free after heat treatments. Conversely, microspheres processed without a pressurized water treatment, which is typical of traditional washing processes, exhibited extensive cracking. Analysis of residues dried from pressurized water treatment effluents indicated that hexamethylenetetramine and urea, which are excess reactants from the internal gelation process, were removed from gelled microspheres during the pressurized water treatment step. Traditional processing methods for preparing internal gelation microspheres use specific feed solution and gelation parameters to reduce subsequent cracking upon drying and heating. Results from this study indicate that more aggressive gel-forming conditions may be used to produce crack-free microspheres, if a pressurized water treatment step is included after washing and before air-drying.

cerium oxide, internal gelation, microsphere, TRIS↗