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File: Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx
Page: 7
Context: tone 1.2 Complete Analysis of Geothermal Fluids
The performance of any collection process depends upon both the nature of the extraction chemistry as well as the capture chemistry. The Geothermal Program Office did not have a “standard” solution to test separation technology performance against so efforts were undertaken to ascertain appropriate conditions (and obtain geothermal solutions to test REE collection material against). Further, this program suggested to the Geothermal Program Office that a standard solution, as wells as test and evaluation conditions, be established for consistent assessment of the mineral collection technology. To enable completion of program goals (both for this project’s specific objectives as well overall DOE programmatic efforts) this effort:
-- Performed a literature review for the solution chemistry and concentration of REEs and other metals in geothermal fluids.
-- Identified promising regions in the United States for the value added recovery of minerals from geothermal fluids
-- Collected geothermal waters for test and evaluation from a promising site for REE enrichment. (test solutions were collected from Sharkey Hot Springs Idaho, which is in a region with known REE deposits. See Appendix B)
To capture the accumulated relevant information and make it available for future efforts a review article entitled “A Review of Rare Earths in Geothermal Fluids; the chemistry, abundance, distribution, analysis, and economic potential” is presently being assembled in a manuscript for publication in the peer reviewed journal Hydrogeology.
A key and critical factor that became apparent upon review of literature and available data was the variability in the water chemistry of the geothermal fluids in its impact probably on geothermal mineral extraction technology. As expected that concentrations of dissolved minerals vary sustainably site to site. More significantly to the development of mineral recovery technology was that the concentrations of dissolved solids and anions (such as carbonate, sulfide and chloride) are highly variable and present at much higher concentrations than the trace minerals. These anions determine the chemical form of the trace minerals in geothermal solution and will significantly impact extraction efficacy for any mineral recovery technology. Hence mineral recovery technology may need to be optimized for solution chemistry of specific geothermal sites where valuable minerals exist in viable concentrations. An advantage of the solid state sorbent technology proposed is the ability to tune the sorbent material composition for the site specific application (mineral type, solution composition, etc.)
####################
File: Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx
Page: 5
Context: jective of this program is to evaluate, develop and demonstrate flexible, scalable mineral extraction technology for geothermal brines based upon solid phase sorbent materials with a specific focus upon rare earth elements (REEs). The process is based upon proven industrial methods (solid state sorbent technology) and will provide a valuable secondary product stream to reduce the cost of geothermal energy while providing a domestic, environmentally benevolent, source of critical minerals. Further, the technology will be scalable and flexible to accommodate the different mineralogy of geothermal sites and plant sizes. Initial FY15 work consisted of the development, evaluation and demonstration of sorbent materials that can effectively perform mineral extraction in the extraordinarily harsh geothermal solution conditions. This project is DOE sponsored and the discussions of the works are related to the milestones of the project which were agreed upon with DOE.
Program Structure and summary results by Task:
Summary of Results for Task 1: Program Initiation and Analysis of Geothermal Fluids
Task 1 Summary:
This task provided a programmatic kickoff and supported extensive critical discussions among the diverse multidisciplinary team members (academic, industrial, national laboratory) to refine keys issues that need to be resolved to make the technology viable. The effort also involved an initial analysis to determine the composition of geothermal waters and define the appropriate solution test conditions. Specific results from this effort are discussed in context with specific milestones.
Milestone 1.1 Assemble Core List of Critical Challenges for Solid State Sorbent Technology for Geothermal Mineral Extraction.
PNNL hosted a kickoff meeting upon receipt of funds to facilitate immediate interactions, information sharing and coordination for the entire project. The team meeting provided a valuable face to face cohesive interaction for the diverse team members. In addition to the group orientation/coordination on the diverse technologies involved in this effort a specific outcome of this meeting was to refine a list of critical challenges for the application of solid state sorbent technology for the economically viable extraction of geothermal minerals. The key critical parameters were found to be:
####################
File: 0MB%20Singh%20et%20al.%202017%20Ecol%20Modell%20Supp%20Data.docx
Page: 1
Context: | Manure | | | | | |
Stock Changes | Beg Stocks | | | | | |
| End Stocks | | | | | |
Emissions to Nature | Air Emissions | -1.67E+00 | | | | |
| Water Emissions | -1.12E+03 | | | | |
| Land Emissions | -1.84E+01 | | | | |
| Total N Inputs to Each Sector | 2.64E+04 | 1.01E+04 | 1.24E+05 | 2.20E+02 | 3.28E+03 |
Table 2: Full N PIOT Continued…. |
| | Animal Prod. (Except Cattle & Poultry Eggs) | Poultry & Egg Prod. | Poultry Process. | Animal (Except Poultry) Slaughtering & Processing | Nitrogenous Fertilizer Manu. |
Soybean Farming & Processing | Oilseed Farming | | | | | |
| Soybean & Other Oil Seed Processing | | | | | |
Corn Farming & Processing | Corn Farming | | | | | |
| Wet Corn Milling | | | | | |
| Dry Corn Milling | | | | | |
Wheat Farming & Processing | Wheat Farming | | | | | |
| Flour Milling & Malt Manu. | | | | | |
Animal Food Manu. | Other Animal Food Manu. | 4.40E+04 | 2.82E+03 | | | |
| Dog & Cat Food Manu. | | | | | |
Livestock & Poultry Farming | Cattle Ranching & Farming | | | | 3.28E+03 | |
####################
File: Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx
Page: 9
Context: ry of Results for Task 2: Evaluation of Solid-State Sorbent Technology
Task 2 Summary:
The purpose of this task is to evaluate solid state sorbent materials for the extraction of valuable minerals from geothermal solutions. The work was conducted in two subtasks to separately evaluate sorbent chemistry and sorbent structure. The results of this task will enable the selection of preferred sorbent chemistries and structures for integration, optimization and demonstration of metal recovery from geothermal fluids in year 2. Specific results from this effort are discussed in context with specific milestones with additional information provided in appendices C and D).
Subtask 2.1 Evaluate and Select Effective Surface Chemistry
Two types of surface chemistries have been evaluated for REE collection; a) Organic functional groups, and b) Inorganic (metal oxides) surface chemistries. To cover the range of water chemistries encountered in geothermal solutions, initial screening work was done in fresh water (river), seawater (brine) and moderately acidic solutions. Final sorbent assessment work and reusability of preferred sorbents (details provided in appendix C) were done with geothermal waters (Sharkley Hot Springs in Idaho which are near proven REE mineral deposits under assessment/development—see appendix B).
We demonstrate greater than 75% extraction of selected metals (including Ag, Eu, Zn) from geothermal brines by preferred/particularly effective sorbents, as summarized in Table 1. Many sorbent materials were explored (see Appendix C for more information) and the preferred sorbent chemistries were found to be:
####################
File: Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx
Page: 12
Context: Appendix A
Assemble Core List of Critical Challenges for Solid State Sorbent Technology for Geothermal Mineral Extraction
As planned, PNNL hosted a kickoff meeting to facilitate immediate interactions, information sharing and coordination for the entire project. The meeting was very positive with excellent input by all program participants. A specific outcome of this meeting was the assembly of a list of critical challenges for the application of solid state sorbent technology for the extraction of geothermal minerals. The top challenges for producing an economically viable technology were identified enabling the program to address during subsequent efforts.
The key critical parameters for the economically viable utilization of Solid State Sorbent Technology for Geothermal Mineral Extraction where found to be:
-- Sorbent affinity and capacity
-- Must be improved over existing materials
-- Must be balanced with regeneration/recovery capability, cost and kinetics
-- Sorbent kinetics
-- Faster kinetics enable higher process rates, smaller equipment foot print and better economics
-- Must balance kinetics vs efficiency (in particular for collection)
-- Strongly dependent of form factor of separation media
-- Sorbent lifetime
-- Thermally and chemically stable
-- Fouling-biological and chemical (iron, silica, carbonate, etc.).
-- Physical/mechanical stability
-- Sorbent form factor
-- Low pressure drop and easily integrated into process
-- Function with suspended solids and surface fouling
-- Mineral recovery from sorbents and sorbent regeneration
-- Minerals could be anionic, cationic, or on suspended solids
-- Chemically and physically regenerate sorbent
-- Acid stripping SOP but not ideal
-- Carbonate and peroxide
-- Cost effectiveness (materials, recovery process, space, installation and operation)
All of these parameters must be achieved and successfully coordinated for an effective chemical extraction process to be created. Performance priorities and specific requirements will be situationally dependent.
Appendix B
Complete Analysis of Geothermal Fluids: Location and Chemistry of Sharkley Hot Springs
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File: 0MB%20Singh%20et%20al.%202017%20Ecol%20Modell%20Supp%20Data.docx
Page: 1
Context: | | Table 2: Full N PIOT Continued…. |
| -------- | -------- |
| | Frozen Food Manu. | Vegetable & Fruit Canning & drying | Exports | Consumption | Imports | Total Outputs |
Soybean Farming & Processing | Oilseed Farming | | | 2.81E+05 | | 1.79E+05 | 5.30E+05 |
| Soybean & Other Oil Seed Processing | | | 4.04E+05 | | | 4.60E+05 |
Corn Farming & Processing | Corn Farming | 2.55E+02 | 2.14E+02 | 5.28E+05 | 2.47E+02 | | 6.04E+05 |
| Wet Corn Milling | | | | | | 2.42E+04 |
| Dry Corn Milling | | | | | | 4.33E+04 |
Wheat Farming & Processing | Wheat Farming | | | 2.78E+04 | 1.61E+04 | 2.91E+04 | 2.64E+04 |
| Flour Milling & Malt Manu. | | | 4.64E+03 | 2.70E-01 | 2.15E+01 | 1.01E+04 |
Animal Food Manu. | Other Animal Food Manu. | | | 7.38E+04 | | | 1.24E+05 |
| Dog & Cat Food Manu. | | | | 2.20E+02 | | 2.20E+02 |
Livestock & Poultry Farming | Cattle Ranching & Farming | | | | | | 3.28E+03 |
| Animal Prod. Except Cattle & Poultry Eggs | | | | | | 4.40E+04 |
####################
File: 0MB%20Singh%20et%20al.%202017%20Ecol%20Modell%20Supp%20Data.docx
Page: 1
Context: | Flow Number | From | To | Description | Data Source | Values (Original Unit) | Values (N) (Metric tons) |
| -------- | -------- | -------- | -------- | -------- | -------- | -------- |
1 | Oilseed Farming | Oilseed Farming | Soybean Used for Seed | Calculated | 12.607 million bushels | 1.89E+04 |
2 | Oilseed Farming | Soybean & Other Oilseed Processing | Soybean Bushels Processed for feed and fuel | Soy-Illinois Report | 273 million bushel | 4.15E+05 |
3 | Soybean & Other Oilseed Processing | Other Animal Food Manu. | Soymeal for animal food manu. | Calculated based on Soy-Illinois Report | 792 thousand tons | 5.58E+04 |
4 | Other animal food manu. | Cattle ranching & farming | Manufactured feed for cattle | Calculated | 46.63 (1000 tons) | 3.26E+03 |
5 | Other animal food manu. | Poultry & Egg Production | Manufactured feed for poultry | Calculated | 40.074 (1000 tons) | 2.82E+03 |
6 | Other animal food manu | Animal Production except cattle, poultry & eggs | Manufactured feed for hogs etc | Calculated | 624.0072 (1000 tons) | 4.40E+04 |
7 | Animal production except cattle, poultry & eggs | Animal (except poultry) slaughtering & processing | Processing of hog etc for food | Assumed equal to Flow # 6 | Assumption | 4.40E+04 |
8 | Poultry & egg production | Poultry processing | Processing of poultry for food | Assumed equal to Flow # 5 | Assumption | 2.82E+03 |
9 | Cattle ranching & Farming | Animal (except poultry) slaughtering & processing | Processing of cattle for food | Assumed equal to Flow # 4 | Assumption | 3.28E+03 |
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File: 0MB%20Singh%20et%20al.%202017%20Ecol%20Modell%20Supp%20Data.docx
Page: 1
Context: | Food Residuals | | | | | | |
| Packaging Residuals | | | | | | |
| Sewage | | | | | | |
| Manure | | | | | | |
Use of Residuals | Plant Residuals | | | | | | |
| Food Residuals | | | | | | |
| Sewage | | | | | | |
| Manure | | | | | | |
Stock Changes | Beg Stocks | | | | | | |
| End Stocks | | | | | | |
Emissions to Nature | Air Emissions | | | | | | |
| Water Emissions | | | | | | |
| Land Emissions | | | | | | |
| Total N Inputs to Each Sector | 2.55E+02 | 2.14E+02 | | | | |
ReferencesAlexander, Richard B., Richard A. Smith, Gregory E. Schwarz, Elizabeth W. Boyer, Jacqueline V. Nolan, and John W. Brakebill. 2008. "Difference in Phoshphorus and Nitrogen Delivery to The Gulf of Mexico from the Mississippi River Basin." Environmental Science and Technology 42: 822-830.
Clay, D.E., and C.G. Carlson. 2011. "Estimating nutrient removal in wheat grain and straw." In iGrow Wheat : Beast Management Practices for Wheat Production in South Dakota, by D.E. Clay, C.G. Carlson and K. Dalsted. Brookins: South Dakota Cooperative Extension Service.
David, Mark B., Laurie E. Drinkwater, and Gregory F. McIsaac. 2010. "Sources of Nitrate Yields in the Mississippi River Basin." J. Environ. Qual. 39: 1657-1667.
####################
File: 0MB%20Singh%20et%20al.%202017%20Ecol%20Modell%20Supp%20Data.docx
Page: 1
Context: (New N Input)Nr fixation by SoybeanIndustrial Nr fixationFree Soil Microorganisms Nr fixationSupply of ResidualsPlant ResidualsFood ResidualsPackaging ResidualsSewage ManureUse of ResidualsPlant ResidualsFood ResidualsSewageManureStock ChangesBeg StocksEnd StocksEmissions to NatureAir EmissionsWater EmissionsLand EmissionsTotal N Inputs to Each Sector2.89E+039.64E+021.47E+031.82E+021.86E+02
####################
File: 0MB%20Singh%20et%20al.%202017%20Ecol%20Modell%20Supp%20Data.docx
Page: 1
Context: | Sewage | | | | | |
| Manure | | | | | |
Stock Changes | Beg Stocks | | | | | |
| End Stocks | | | | | |
Emissions to Nature | Air Emissions | | | | | |
| Water Emissions | | | | | |
| Land Emissions | | | | | |
| Total N Inputs to Each Sector | 4.40E+04 | 2.82E+03 | 2.82E+03 | 4.73E+04 | 0 |
Table 2: Full N PIOT Continued….Bread, Bakery & Product Manu.Cookie, Cracker & Pasta Manu.Snack Food Manu.Tortilla Manu.Breakfast Cereal Manu.Soybean Farming & ProcessingOilseed FarmingSoybean & Other Oil Seed ProcessingCorn Farming & ProcessingCorn Farming Wet Corn MillingDry Corn MillingWheat Farming & ProcessingWheat Farming1.86E+02Flour Milling & Malt Manu.2.89E+039.64E+021.47E+031.82E+02Animal Food Manu.Other Animal Food Manu.Dog & Cat Food Manu.Livestock & Poultry FarmingCattle Ranching & FarmingAnimal Prod. Except Cattle & Poultry EggsPoultry & Egg ProductionMeat Production (Food Processing)Poultry ProcessingAnimal (Except Poultry) Slaughtering & ProcessingChemical Manu.Nitrogenous Fertilizer Manu.Food ManufacturingBread, Bakery & Product Manu.Cookie, Cracker & Pasta Manu.Snack Food Manu.Tortilla Manu.Breakfast Cereal Manu.Frozen food manu.Vegetable & fruit canning dryingRam Materials
####################
File: 0MB%20Singh%20et%20al.%202017%20Ecol%20Modell%20Supp%20Data.docx
Page: 4
Context: Evalu
####################
File: 0MB%20Singh%20et%20al.%202017%20Ecol%20Modell%20Supp%20Data.docx
Page: 1
Context: Emissions to Nature | Air Emissions | -1.57E+00 | -4.66E+02 | -4.17E+04 | | |
| Water Emissions | -8.71E+03 | | -1.27E+05 | | |
| Land Emissions | -1.38E+02 | | | | |
| Total N Inputs to Each Sector | 5.30E+05 | 4.60E+05 | 6.04E+05 | 2.42E+04 | 4.33E+04 |
| | | | | | |
Table 2: Full N PIOT Continued…. |
| | Wheat Farming | Flour Milling & Malt Manu. | Other Animal Food Manu. | Dog & Cat Food Manu. | Cattle Ranching & Farming |
Soybean Farming & Processing | Oilseed Farming | | | | | |
| Soybean & Other Oil Seed Processing | | | 5.58E+04 | | |
Corn Farming & Processing | Corn Farming | | | | | |
| Wet Corn Milling | | | 2.42E+04 | | |
| Dry Corn Milling | | | 4.33E+04 | | |
Wheat Farming & Processing | Wheat Farming | 4.20E+02 | 1.01E+04 | 5.80E+02 | 2.20E+02 | |
| Flour Milling & Malt Manu. | | | | | |
Animal Food Manu. | Other Animal Food Manu. | | | | | 3.28E+03 |
| Dog & Cat Food Manu. | | | | | |
Livestock & Poultry Farming | Cattle Ranching & Farming | | | | | |
####################
File: 0MB%20Singh%20et%20al.%202017%20Ecol%20Modell%20Supp%20Data.docx
Page: 1
Context: | Animal Prod. Except Cattle & Poultry Eggs | | | | 4.40E+04 | |
| Poultry & Egg Production | | | 2.82E+03 | | |
Meat Production (Food Processing) | Poultry Processing | | | | | |
| Animal (Except Poultry) Slaughtering & Processing | | | | | |
Chemical Manu. | Nitrogenous Fertilizer Manu. | | | | | |
Food Manufacturing | Bread, Bakery & Product Manu. | | | | | |
| Cookie, Cracker & Pasta Manu. | | | | | |
| Snack Food Manu. | | | | | |
| Tortilla Manu. | | | | | |
| Breakfast Cereal Manu. | | | | | |
| Frozen food manu. | | | | | |
| Vegetable & fruit canning drying | | | | | |
Ram Materials
(New N Input) | Nr fixation by Soybean | | | | | |
| Industrial Nr fixation | | | | | 8.95E+05 |
| Free Soil Microorganisms Nr fixation | | | | | |
Supply of Residuals | Plant Residuals | | | | | |
| Food Residuals | | | | | |
| Packaging Residuals | | | | | |
| Sewage | | | | | |
| Manure | | | | | |
Use of Residuals | Plant Residuals | | | | | |
| Food Residuals | | | | | |
| Sewage | | | | | |
####################
File: 0MB%20Singh%20et%20al.%202017%20Ecol%20Modell%20Supp%20Data.docx
Page: 1
Context: | Animal Prod. Except Cattle & Poultry Eggs | | | | | |
| Poultry & Egg Production | | | | | |
Meat Production (Food Processing) | Poultry Processing | | | | | |
| Animal (Except Poultry) Slaughtering & Processing | | | | | |
Chemical Manu. | Nitrogenous Fertilizer Manu. | 2.71E+04 | | | | |
Food Manufacturing | Bread, Bakery & Product Manu. | | | | | |
| Cookie, Cracker & Pasta Manu. | | | | | |
| Snack Food Manu. | | | | | |
| Tortilla Manu. | | | | | |
| Breakfast Cereal Manu. | | | | | |
| Frozen food manu. | | | | | |
| Vegetable & fruit canning drying | | | | | |
Ram Materials
(New N Input) | Nr fixation by Soybean | | | | | |
| Industrial Nr fixation | | | | | |
| Free Soil Microorganisms Nr fixation | | | | | |
Supply of Residuals | Plant Residuals | | | | | |
| Food Residuals | | | | | |
| Packaging Residuals | | | | | |
| Sewage | | | | | |
| Manure | | | | | |
Use of Residuals | Plant Residuals | | | | | |
| Food Residuals | | | | | |
| Sewage | | | | | |
| Manure | | | | | |
####################
File: Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx
Page: 8
Context: utcomes from the literature review and solution analysis have been integrated and applied to the sorbent evaluation and development in Task 2. It was interesting to note that many (but not all) REE and other valuable mineral deposits occur in areas of geothermal activity and potential for geothermal activity. This strongly supports the concept that recovery of valuable minerals from geothermal brines with new technology could be viable—at select locations with sufficient mineral content in the geothermal solutions to provide a value added process. Further, like any other mining location the mineralization is going to be the site specific—suggesting a flexible, adaptable and scalable technology would be preferred for extraction of value added minerals from geothermal (or hydrothermal) brines.
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File: 0MB%20Singh%20et%20al.%202017%20Ecol%20Modell%20Supp%20Data.docx
Page: 1
Context: 9 | Grain Farming | Other animal food manu. | Wheat for other animal food manu. | Calculated | 8.52E+05 (bushels) | 5.80E+02 |
10 | Nitrogenous Fertilizer Manu. | Grain Farming | Nitrogen fertilizer applied to wheat farming | ERS USDA | 5.97E+07
(pounds) | 2.71E+04 |
11 | Flour milling & malt manu. | Human Consumption | Flour being consumed instate | | 2.72E+04 (grounds of flour) | 2.70E+01 |
12 | Flour Milling & Malt Manu. | Other Animal Food manu | Byproducts such as Millfeed, Wheat mill run and wheat midlings being used for livestock food manu | This has not been included in the PIOT as the data was not available. | NA | |
13 | Flour Milling & Malt Manu. | Cattle Ranching & Farming | Wheat milling byproducts used for livestock feed without further processing | This has not been included in the PIOT as the data was not available | | |
14 | Grain farming | Exports | Export of wheat grains out f state | | 1450.4 (thousand tons) | 2.78E+04 |
15 | Grain farming | Imports | Import of wheat grain from other regions (cross trading commodity) | | 1515.8 (thousand tons) | 2.91E+04 |
16 | Flour milling and manufacturing | Exports | Export of flour from the state | | 1057.275 (thousand tons) | 2.32E+01 |
17 | Flour milling and manufacturing | Consumption | Consumption of wheat flour within state | | 2.72E+04 (pounds of flour) | 2.70E-01 |
18 | Flour milling and manu. | Imports | Import of flour from other regions | | 979.402 (thousand tons) | 2.15E+01 |
####################
File: Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx
Page: 12
Context: Analysis is presently in progress. Appendix D shows some of the analysis that was conducted on alternative sorbent structures. Presently, the three most promising approaches are listed below, with a brief description for each:
-- Fluidized bed
-- Advantages: low pressure drop, resistance to fouling, relatively compact, facile sorbent processing, known industrial technology
-- Challenges: attrition of sorbent material
-- Moving slurry bed of magnetic media
-- Advantages: low pressure drop, resistance to fouling, relatively compact/small foot print, accelerated sorbent processing
-- Challenges: durability of sorbent material and novelty of large volume magnetic separation technology
-- Polymer sorbent composite coating and surfaces
-- Advantages: low pressure drop, resistance to fouling, manufacturability and flexible configuration
-- Challenges: potentially lower contact/collection efficiency
References
####################
File: 0MB%20Singh%20et%20al.%202017%20Ecol%20Modell%20Supp%20Data.docx
Page: 1
Context: A Nitrogen Physical Input-Output Model for Illinois
Shweta Singh, Jana Compton, Troy Hawkins, Daniel Sobota and Ellen Cooter
Supplementary Information
1) Flow Diagram for Steps in Development of PIOT for a Region
----Image alt text---->N-PIOT-Flow-Diagram.png<----media/image1.png----
Figure 1 : Steps in Developing the N-PIOT ModelFigure 1 : Steps in Developing the N-PIOT Model
2) Material Flow Analysis (MFA) Diagram for Major N flows in Illinois
Step 2 in development of PIOT involves tracking N flows driven by major commodities in the region. This tracking is done by developing material flow diagrams for each commodity separately. Table 1 shows the major crop area in Illinois. The top 3 crop commodities are corn, soybean and wheat. Hence to develop the PIOT for N flows in the Illinois the processing of these 3 commodities are included. To develop the PIOT, MFA for each of these crops are developed and each flows are estimated by using empirical data or calculated. Last, each of the flows are mapped to corresponding economic sectors in the region. To see the process of each flow estimation corresponding to each of these crops refer to specific sections on Soybean, Corn and Wheat below.
| Major Crop | Area (Acres) |
| -------- | -------- |
Corn for Grain | 10,742,787 |
Corn for Silage | 109,847 |
Wheat for Grain | 581,084 |
Soybean for Beans | 10,505,989 |
Alfalfa (hay) | 416,997 |
Total of Above | 22,356,704 |
Total Cropland in Illinois : 24,171,260 Acres |
Harvested Cropland in Illinois : 22,562,904 Acres |
Major Crops (Corn, Soybean, Wheat & Alfalfa) form 99 % of Harvested Cropland. |
Table 1 : Major Crop Areas In Illinois (2002) USDA NASS
The order of description of each flow estimation is: MFA diagram for the crop, Table that shows relevant flows from the MFA diagram with values and method of calculation or estimation and details of all flow estimations along with assumptions.
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File: 0MB%20Singh%20et%20al.%202017%20Ecol%20Modell%20Supp%20Data.docx
Page: 1
Context: N content for Flow # 3 = 792 x (10^3) x (0.44) x (0.16) = 5.58E+04 metric tons
2.2 Corn Flow Calculations
Corn Flow Diagram
----Image alt text---->corn-fig.png<----media/image3.png----
Figure 3 : Material Flow Analysis for Corn in Agro-Based Industries
Table 6 : Flows for Corn PIOT | Flow Number | From | To | Description | Data Source | Values (Original Unit) | Values (N) Metric tons |
| -------- | -------- | -------- | -------- | -------- | -------- | -------- |
1 | Corn Farming | Wet Milling | Flow of corn bushels for | Calculated | 80.97 million bushels | 3.03E+04 |
2 | Corn Farming | Dry Milling | Flow of corn bushels mainly for Ethyl Alcohol Manu. | Calculated | 121.46 million bushels | 4.53E+04 |
3 | Corn Farming | Cattle ranching & farming | Flow of corn bushels for direct consumption by livestock | Not available | - | - |
4 | Wet Milling | Other animal food manu. | Flow of byproducts from wet milling of corn that is used for animal food manu. | Calculated | 1.09E+09 Corn gluten feed and 2.02E+08 lb of Corn gluten mean | 2.42E+04 |
5 | Dry Milling | Other animal food manu. | Flow of byproducts/co-products from dry milling of corn that is used for animal food manu. | Calculated | 2.13E+09 lbs of DDGS | 4.33E+04 |
6 | Dry milling | Poultry & Egg production | Flow of byproducts/coproducts from corn dry milling that is directly used as feed for poultry. | | | |
7 | Other animal food manu | Cattle ranching & farming | Flow of manufactured animal food to livestock farming industry | Data for consumption of DDGS not available. |
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Context: 3) Beginning Stock of Soybean (Flow # 14) = 34 million bushels = 5.10E+04 metric tons
Conversion to N is done using the same process as in 5
4) End Stock of Soybean (Flow # 15) = 27 million bushels = 4.05E+04 metric tons
5) Soymeal flow out of state (Flow # 13) = 5736 thousand tons
Conversion to N:
% of Protein in Soymeal = 44 – 48 % [Source: Cromwell]
Assumed 44 % in non dehulled soybean meal
% of N in Protein = 16 %
N in Soymeal flowing out of state = 5736 *1000 * 0.44 * 0.16 = 4.04E+05 metric tons
1) 9 Calculation of Soybean meal Consumed Within State
Table 5 : Calculation of Domestic (Illinois) Consumption of Soybean Meal| IL | Production | Total Production Yield | SBM Domestic Use |
| -------- | -------- | -------- | -------- |
2002 | Mil lbs | Yield/lb | mil lbs | Protein meal/unit of production | SBM as share of Protein meal | Mil lbs | 1000s s. tons | 1000 tons |
Beef | 594.35 | 0.63 | 376.66 | 0.97 | 0.15 | 53.58 | 26.79 | 24.30 |
Pork | 2495.63 | 0.74 | 1836.02 | 0.99 | 0.76 | 1377.24 | 688.62 | 624.70 |
Broilers | 0.13 | 0.74 | 0.10 | 0.81 | 0.76 | 0.06 | 0.03 | 0.03 |
Turkeys | 89.90 | 0.78 | 70.30 | 0.88 | 0.76 | 47.02 | 23.51 | 21.33 |
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Context: Chemical Manu. | Nitrogenous Fertilizer Manu. | 9.53E+04 | | 7.73E+05 | | |
Food Manufacturing | Bread, Bakery & Product Manu. | | | | | |
| Cookie, Cracker & Pasta Manu. | | | | | |
| Snack Food Manu. | | | | | |
| Tortilla Manu. | | | | | |
| Breakfast Cereal Manu. | | | | | |
| Frozen food manu. | | | | | |
| Vegetable & fruit canning drying | | | | | |
Ram Materials
(New N Input) | Nr fixation by Soybean | 3.49E+05 | | | | |
| Industrial Nr fixation | | | | | |
| Free Soil Microorganisms Nr fixation | | | | | |
Supply of Residuals | Plant Residuals | | | | | |
| Food Residuals | | | | -6.08E+03 | -1.98E+03 |
| Packaging Residuals | | | | | |
| Sewage | | | | | |
| Manure | | | | | |
Use of Residuals | Plant Residuals | | | | | |
| Food Residuals | | | | | |
| Sewage | | | | | |
| Manure | 6.56E+04 | | | | |
Stock Changes | Beg Stocks | 5.10E+04 | 4.98E+04 | | | |
| End Stocks | -4.05E+04 | | | | |
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Context: We have begun relative qualitative ranking the selected structures for the various critical parameters and the initial results are shown in Table D1. The potential sorbent structures are compared to the critical parameters and have been given initial rankings (1-5, 5 being most favorable).
As the project progresses, this data will become a defined database that compares the substrates on a quantitative rather than qualitative basis. We will be assigning weights to the various parameters, since some are much more likely to determine applicability than others. As we develop the techno-economic model for the system, the category weights and relative merits or each parameter will become clearer. Based on the techno-economics and the laboratory trials, those substrates that appear to be unfavorable/unacceptable in one or more areas will be removed and efforts will focus on viable candidates.
A primary barrier to mineral production from geothermal brine has historically been high TDS and bulk precipitation of low value minerals such as silicon and iron. A key technical challenge that this effort will be to address for the successful utilization of solid state sorbents (advanced or otherwise) for mineral recovery (REEs or otherwise) from geothermal waters will be resistance to fouling/plugging with silica and iron precipitates. This is one of the most important assessment parameters and will be weighted very heavily in the techno-economic assessment. Sorbent structures selected for further evaluation will be resistant to plugging/fouling by heavy precipitation (i.e., fluidized bed, mesh screen, moving/slurry bed, membrane systems, polymer braids, and composite structures)
Table D1. An Initial Assessment of Sorbent Structures with
Key Parameters for Trace Mineral Extraction from Geothermal Waters
----media/image7.emf----
Appendix E
Experimental Details for Sorbent Testing in Geothermal Waters
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Context: Flow # 4
a) Flow of Corn Gluten Feed from “Wet Milling to Other Animal Food Manu.” = 1.09E+09 lb = 1.09E+09 x 0.195 x 0.16 = 3.40E+07 lb N = 1.54E+04 metric tons of N
b) Flow of Corn Gluten meal from “Wet Milling to Other Animal Food Manu.” = 2.02E+08 lb = 2.02E+08 x 0.60 x 0.16 = 1.94E+07 lb N = 8.80E+03 tons of N
Total Flow # 4 = (1.54 + 0.880) E+04 = 2.42E+04 metric tons of N
3) Flow # 5: Flow of Byproducts from Dry Milling of Corn to “Other Animal Food Manufacturing”
The products of dry milling process of corn involves ethyl alcohol, distillers wet grains, distillers dried grains with solubles and condensate distillers solubles.
Among these, Corn Distillers Dried Grains with Solubles (DDGS) mainly has all the nutrients after extraction of starch in the alcohol. Typical composition of DDGS includes – 27 % protein, 11 % fat and 9 % fiber.
Other report mentioned the protein content of DDGS to be 29 %. So, an average value of 28 % protein content was used for DDGS.
Production of DDGS in Illinois for the year 2002.
Corn Bushels in Dry Milling = 121.459 million bushels
Assumption: 1 bushel corn = 17.5 pounds of DDGS
DDGS produced = 121.459 x (10^6) x 17.5 pounds = 2.125E+09 pounds of DDGS
N in DDGS produced = (2.125E+09) x 0.28 x 0.16 = 9.54E+07 lbs of N = 4.33E+04 metric tons of N
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Context: | Poultry & Egg Production | | | | | | 2.82E+03 |
Meat Production (Food Processing) | Poultry Processing | | | | 2.82E+03 | | 2.82E+03 |
| Animal (Except Poultry) Slaughtering & Processing | | | | 4.73E+04 | | 4.73E+04 |
Chemical Manu. | Nitrogenous Fertilizer Manu. | | | | | | 8.95E+05 |
Food Manufacturing | Bread, Bakery & Product Manu. | | | | 2.89E+03 | | 2.89E+03 |
| Cookie, Cracker & Pasta Manu. | | | | 9.64E+02 | | 9.64E+02 |
| Snack Food Manu. | | | | 1.47E+03 | | 1.47E+03 |
| Tortilla Manu. | | | | 1.82E+02 | | 1.82E+02 |
| Breakfast Cereal Manu. | | | | 1.86E+02 | | 1.86E+02 |
| Frozen food manu. | | | | 2.55E+02 | | 2.55E+02 |
| Vegetable & fruit canning drying | | | | 2.14E+02 | | 2.14E+02 |
Ram Materials
(New N Input) | Nr fixation by Soybean | | | | | | |
| Industrial Nr fixation | | | | | | |
| Free Soil Microorganisms Nr fixation | | | | | | |
Supply of Residuals | Plant Residuals | | | | | | |
| Food Residuals | | | | | | |
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Context: 8 | Cattle ranching & farming | Animal (except poultry) slaughtering & processing | Flow of N as cattle from livestock farming to animal slaughtering & processing that converts it for human consumption. | Data not available |
9 | Animal (Except poultry) slaughtering & processing | Human Consumption | Flow of N final to human consumption within state in form of meat except poultry meat. | | | |
10 | Poultry & Egg production | Human Consumption | N flow associated with egg consumption by humans | | | |
11 | Nitrogen in Atmospheric pool | Nitrogenous fertilizer manufacturing | Nitrogen fixation by Haber Bosch process from atmosphere by the Nitrogenous fertilizer manu. industry | Assumed to be equal to the N fertilizer consumption in corn farming | 7.73E+05 metric tons of N | 7.73E+05 |
12 | Nitrogenous Fertilizer manu. | Corn Farming | Flow of N in form of nitrogenous fertilizer to corn farming. | Calculated (See Below) | 7.73E+05
(metric tons of N) | 7.73E+05 metric tons of Nr |
13 | Corn farming | Corn farming | Use of seeds produced in the same sector for farming | Calculated | 1.70E+08 gm of Corn Seeds | 16.037 metric tons of Nr |
|
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Context: Import Estimation for State of Illinois: By Calculation| Commodity | Unit | Value | Year | Source | Scale |
| -------- | -------- | -------- | -------- | -------- | -------- |
Beef | million pounds | 1.50E+02 | 2002 | Estimated | Illinois State |
Pork | million pounds | 4.98E+01 | 2002 | Estimated | Illinois State |
Broilers | million pounds | 1.55E+01 | 2002 | Estimated | Illinois State |
Turkeys | million pounds | 4.65E-02 | 2002 | Estimated | Illinois State |
| Commodity | Unit | Value | Year | Source | Scale |
| -------- | -------- | -------- | -------- | -------- | -------- |
Fresh Sweet Corn | pounds | 2.42E+06 | 2002 | Estimated | Illinois State |
Canned Sweet Corn | pounds | 1.95E+06 | 2002 | Estimated | Illinois State |
Frozen Sweet Corn | pounds | 1.38E+06 | 2002 | Estimated | Illinois State |
4: Emissions Data
The emissions data included in the PIOT are mainly farm scale emissions for corn, soybean and wheat corresponding to the major feedstocks included in development of PIOT. The soybean and wheat emissions data were obtained from EPIC model using FEST-C v1 for Illinois. The variables included in the model output for emissions are YON, Q-NO3 and AVOL with explanations provided in table below. | Variable | Explanation/Interpretations |
| -------- | -------- |
YON (Kg-N) | Rate of Organic N Sediment loss (Kg/ha). It was processed to get total organic sediment loss for the crops included in PIOT. |
Q-NO3 | Amount of NO3-N lost from the soil profile by run-off and leaching (Kg/ha). It was also processed to get total NO3-N lost for each of the crop based on the area planted. |
AVOL | Mass of N volatilized (Kg-N). This value was directly provided from the model run by Cooter et al. |
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Context: Harwood, Joy L., Mack N. Leath, and Walter G. Heid. 2010. The U.S. Milling and Baking Industries. Agricultural Economic Report Number 611, USDA, Economic Research Service.
Ogle, Stephen M, Stephen J Del Grosso, Paul R Adler, and William J. Parton. 2008. "Soil Nitrous Oxide Emissions with Crop Production for Biofuel: Implications for Greenhouse Gas Mitigation." Edited by Joe L. Outlaw and David P Ernstes. The Life Cycle Carbon Footprint of Biofuels. Florida.
Salvagiotti, F., K.G. Cassman, J.E. Specht, D.T Walters, and A. Weiss. 2008. Nitrogen Update, fixation and response to fertilizer N in soybeans : A review . Faculty Publications, University of Nebraska, Agronomy & Horticulture. http://www.mssoy.org/uploads/files/nebraska-n-review-2008-ok.pdf.
Smika, D.E., and B.W. Greb. 1973. "Protein Content of Winter WHeat Grain as Related to Soil and Climatic Factors in the Semiarid Central Great Plains." Agronomy 65: 433-436.
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Context: Table 14: Full Balanced PIOT for N Flows in Illinois (Metric Tons of N)
Note: Grey Cells represent flows in between sectors, i.e. the structural N flows between sectors in Illinois Economy
Red cells represent assumed flow for balancing. Notice that the assumed flows are out of structural flows within the economy| | | | | | | |
| -------- | -------- | -------- | -------- | -------- | -------- | -------- |
| | Oilseed Farming | Soybean & Other Oil-Seed Processing | Corn Farming | Wet Corn Milling | Dry Corn Milling |
Soybean Farming & Processing | Oilseed Farming | 1.89E+04 | 4.10E+05 | | | |
| Soybean & Other Oil Seed Processing | | | | | |
Corn Farming & Processing | Corn Farming | | | 1.60E+01 | 3.03E+04 | 4.53E+04 |
| Wet Corn Milling | | | | | |
| Dry Corn Milling | | | | | |
Wheat Farming & Processing | Wheat Farming | | | | | |
| Flour Milling & Malt Manu. | | | | | |
Animal Food Manu. | Other Animal Food Manu. | | | | | |
| Dog & Cat Food Manu. | | | | | |
Livestock & Poultry Farming | Cattle Ranching & Farming | | | | | |
| Animal Prod. Except Cattle & Poultry Eggs | | | | | |
| Poultry & Egg Production | | | | | |
Meat Production (Food Processing) | Poultry Processing | | | | | |
| Animal (Except Poultry) Slaughtering & Processing | | | | | |
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Context: 2.1 Soybean Flow Diagram
Figure 2 : Material Flow Analysis for Soybean in Agro-Based Industries
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Context: Thiol groups | |
SH cabosil | 1 | 0 | 99 | 1 | 5 | 5 | 96 | 100 | 98 | 91 | 84 |
SH davisil | 2 | 1 | 99 | 2 | 4 | 5 | 96 | 100 | 98 | 91 | 99 |
SH SAMMS | 1 | 0 | 99 | 1 | 8 | 9 | 96 | 92 | 97 | 91 | 74 |
GT74 | 3 | 2 | 53 | 3 | 13 | 7 | 40 | 0 | 14 | 86 | 26 |
Amidoxime group |
Purolite®S910 | 4 | 1 | 21 | 1 | 12 | 52 | 31 | 0 | 19 | 21 | 0 |
Amidoxime fiberglass AF1L2R1* | 0 | 0 | 77 | 0 | 9 | 31 | 96 | 0 | 61 | 82 | 55 |
Amidoxime fiberglass 3495 - A18L2R2.1* | 0 | 6 | 92 | 0 | 9 | 41 | 96 | 0 | 42 | 90 | 49 |
Other materials and controls |
RE resin | 2 | 1 | 0 | 3 | 2 | 0 | 10 | 0 | 0 | 5 | 7 |
Activated Carbon | 5 | 2 | 16 | 4 | 7 | 22 | 82 | 0 | 1 | 69 | 35 |
AGMP 100-200 (SAX) | 4 | 2 | 29 | 0 | 54 | 95 | 96 | 6 | 71 | 64 | 30 |
CG50 (WAX) | 2 | 0 | 14 | 1 | 45 | 75 | 94 | 44 | 78 | 30 | 66 |
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Context: Cabosil | 4 | 1 | 17 | 0 | 8 | 0 | 36 | 100 | 4 | 23 | 61 |
Davisil -646 | 0 | 0 | 9 | 0 | 5 | 0 | 19 | 70 | 0 | 25 | 31 |
MCM-41 | 3 | 0 | 9 | 5 | 8 | 6 | 49 | 72 | 2 | 30 | 61 |
Each metal concentration ~50-100 ppb, Equilibrium pH~7.7, L/S 50000 mL/g, contact time for 2 hours, *L/S =5000
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Context: Specific details on the performance test of selected surface chemistries evaluated are provided below. Final evaluation testing was done in geothermal water collected from Sharkley Hot springs in Idaho which are near proven REE mineral deposits under assessment and development.
Appendix D
Evaluation of Solid-State Sorbent Technology: Down-Select to the Most Effective Sorbent Structures
To date we have identified 7 sorbent structures that could be utilized in recovering metals from geothermal brines.
-- Conventional Packed Bed
-- Fluidized Bed
-- Mesh Screen
-- Moving/Slurry Bed
-- Modified Membrane system
-- Polymer Braid/Rope
-- Polymer Composites
Each structure is being explored in terms of important system parameters such as:
-- Resistance to fouling/plugging with precipitates,
-- Pressure drop,
-- Contact efficiency,
-- Durability,
-- Regeneration,
-- Manufacturability,
-- The need for specialized equipment.
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Context: -- Challenges: d
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Context: 3 : Import and Export Calculations:
State scale import and export data were not directly reported, however reliable data for national scale export and import of commodities was available. To scale the national scale import to state scale we made an assumption that the share of import are in proportion to disposable income of states. This data is available from Bureau of Economic Analysis (BEA).| FIPS | Area | Description | 2002 |
| -------- | -------- | -------- | -------- |
00000 | US | Disposable personal income (thousands of dollars) | 8.01E+09 |
00000 | US | Population | 2.88E+08 |
00000 | US | Per capita disposable personal income (dollars) | 2.78E+04 |
17000 | Illinois | Disposable personal income (thousands of dollars) | 3.72E+08 |
17000 | Illinois | Population | 1.25E+07 |
17000 | Illinois | Per capita disposable personal income (dollars) | 2.97E+04 |
Source: BEA , https://www.bea.gov/iTable/
Import of Commodities to Illinois: The import to a state is calculated by using the ratio of disposable income of state population to the disposable income of the whole country.
Food ImportState = Total ImportUS × Disposable IncomeStateDisposable IncomeUS| Commodity | Unit | Value | Year | Source | Scale |
| -------- | -------- | -------- | -------- | -------- | -------- |
Source : http://usda01.library.cornell.edu/usda/waob/wasde//2000s/2002/wasde-12-10-2002.pdf |
Beef | million pounds | 3218 | 2002 | WASDE /1 | US |
Pork | million pounds | 1070 | 2002 | WASDE /2 | US |
Broilers | million pounds | 12 | 2002 | WASDE /3 | US |
Turkeys | million pounds | 1 | 2002 | WASDE /4 | US |
| Commodity | Unit | Value | Year | Source | Scale |
| -------- | -------- | -------- | -------- | -------- | -------- |
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Context: Table 11 : Conversion Factors to Convert Flows to Nitrogen| Variable | Value | Unit | Source |
| -------- | -------- | -------- | -------- |
N Harvested in Soybean | 1.52 * (# of bushels) | kgN/bushel | (David, Drinkwater and McIsaac 2010) |
Protein Concentration of Hybrid Corn in 1985 | 10 % | | |
Protein Concentration of Hybrid Corn in 2006 | 8.50 % | | |
% N Content of Corn Grain | 6.34 % | | (Salvagiotti, et al. 2008) |
Moisture Content of Bushel of Soybean (at weight 60 lb) | 13 % | | http://ohioline.osu.edu/agf-fact/0502.html |
Soybean meal for swine – regular : protein concentration | 44 % | | Soybeanmeal-thegoldstandard.pdf, by Gary L. Cromwell, Professor, Swine Nutrition (Published in The Farmer’s Pride, KPPA News, Vol.11, No. 20, 1999) |
Dehulled Soybean meal : protein concentration | 48 % | | Soybeanmeal-thegoldstandard.pdf, by Gary L. Cromwell, Professor, Swine Nutrition (Published in The Farmer’s Pride, KPPA News, Vol.11, No. 20, 1999) |
Wheat-flour, whole grain | 13.7 | Gm protein/100 gm of wheat | http://en.wikipedia.org/wiki/Wheat_flour
|
Bushel of Wheat | 1.5 | lbsN/bushel | (Clay and Carlson 2011) |
Wheat grain used as seed | 12 | % protein | (Smika and Greb 1973) |
Table 12 : N Fertilizer Input to Major Crops (Calculations Shown Earlier)| Crop | N Fertilizer Input |
| -------- | -------- |
Corn | 7.73E+05 |
Wheat | 2.71E+04 |
Soybean | 9.53E+04 |
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Context: b) N flow in Soybean Meal consumed by other animal such as hogs (Flow # 6) : Manufactured feed Utilizing Soybean meal feed for Hog food = 624.70 thousand tons. This flow is for pork production and mapped as the flow from “Other animal food manufacturing” to “Animal production except cattle, poultry & eggs”.
N content = 624.70 x (10^3) x (0.44) x (0.16) = 4.40E+04 metric tons
c) N flow in Soybean meal consumed by cattle such as cattle raised for beef and milk production (Flow # 4) : Manufactured feed Utilizing soybean meal feed for Beef food and milk production = 46.30 thousand tons. This flow is for beef production and mapped as the flow from “Other animal food manufacturing” to “Cattle ranching & farming”.
N content: 46.30 x (10^3) x (0.44) x (0.16) = 3.26E+03 metric tons
2.1.10 Calculation of Soybean Mean Consumed in Animal Food manu. Within State
Total Soybean meal produced = 6528 thousand tons [Soy-Illinois Report]
Export of Soybean meal = 5736 thousand tons [Soy-Illinois Report]
Assumption: The soybean meal produced within state is utilized fully and the amount not exported outside state is sent to animal food manufacturing to be converted into useful product.
Hence, Soybean mean sent to animal food manufacturing (Flow # 3) : Flow from sector “Soybean & Other Oilseed processing” to “Other Animal Food manu” = 6528 – 5736 = 792 thousand tons
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Context: Table 7 : Flows for Wheat PIOT | Flow Number | From | To | Description | Data Source | Values (Original Unit) | Values (N) (Metric tons) |
| -------- | -------- | -------- | -------- | -------- | -------- | -------- |
1 | Grain farming | Grain farming | Seed for Wheat farming (Produced in Grain farming sector) | Calculated Bases on
Economic Research Service, USDA Dataset (\cite{USDASeedReport}) | 4.82E+07 pound | 4.20E+02 |
2 | Grain farming | Flour Milling & Malt Manu. | Wheat for Milling | Calculated | 1.49E+07 bushels | 1.01E+04 |
3 | Flour Milling & Malt Manu. | Bread Bakery & Product Manu. | Wheat Flour for Bread Manu. | Calculated | 2.91E+08 (pounds of floor) | 2.89E+03 |
4 | Flour Milling & Malt Manu. | Cookie, Cracker & Past Manu. | Wheat for Product Manu. | Calculated | 9.70E+07 (pounds of flour) | 9.64E+02 |
5 | Flour Milling & Malt Manu. | Snack food manu. | Wheat flour for Snack Manu. | Calculated | 1.48E+08 (pounds of flour) | 1.47E+03 |
6 | Flour Milling & Malt Manu. | Tortilla Manu. | Wheat flour for Tortilla Manu. | Calculated | 1.83E+07
(pounds of flour) | 1.82E+02 |
7 | Grain Farming | Breakfast Cereal Manu. | Wheat grains used for breakfast cereal | Calculated | 2.73E+05 (bushels) | 1.86E+02 |
8 | Grain Farming | Dog & Cat food manu. | Wheat for Dog & Food Manu. | Calculated | 3.24E+05 (bushels) | 2.20E+02 |
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Context: Emissions from Corn Farming : The corn farming emissions were obtained from literature source [ (Ogle, et al. 2008)] and SPARROW model (Alexander, et al. 2008). The nitrous oxide (N2O) emissions from land is directly based on field observations. The water run-off from the applied fertilizer
5 : Miscellaneous Data
Table 10 : Conversion of Flows in PIOT to N (Only Soybean Shown for Example)| Variable | Flow From Sector | Flow to Sector | Original Value | Original Unit | N Flow Value | Unit |
| -------- | -------- | -------- | -------- | -------- | -------- | -------- |
Soybean Used for Crushing | Oilseed Farming | Soybean and other oilseed processing | 273 | Million Bushels | 9.03E+08 | Lbs of N |
Soybean Used for Seeds | Oilseed Farming | Oilseed farming | 12.607 | Million Bushels | 4.17E+07 | Lbs of N |
Soybean export | Oilseed farming | | 187 | | | |
Beg Stocks | | | | | | |
End Stocks | | | | | | |
Soybean Meal Production | Soybean and other oilseed processing sector | | 12121.2 | Million lbs | 8.53E+08 | Lbs of N |
Soybean meal consumption by Beef Production | Other animal food manu. | Cattle Ranching | 24.30172 | 1000 tons | 1.71E+00 | 1000 tons of N |
Soybean meal consumption by milk production cattle | Other animal food manu. | Cattle ranching | 22.32751 | 1000 tons | 1.57E+00 | 1000 tons of N |
Soybean meal consumption by pork producing hogs | Other animal food manu. | Hog & Pig farming | 624.7002 | 1000 tons | 4.40E+01 | 1000 tons of N |
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Context: (7) Guo, C.; Stetzenbach, K. J.; Hodge, V. F., Determination of 56 trace elements in three aquifer-type rocks by ICP-MS and approximation of the relative solubilities for these elements in a carbonate system by water-rock concentration ratios. In Water Science and Technology Library: RARE EARTH ELEMENTS IN GROUNDWATER FLOW SYSTEMS, Johannesson, K. H., Ed. Springer: Dordrecht, The Netherlands, 2005; Vol. 51, pp 39-65.
(8) Fryxell, G. E.; Zemanian, T. S.; Addleman, R. S.; Aardahl, C. L.; Zheng, F.; Busche, B.; Egorov, O. B. Backfilled, self-assembled monolayers and methods of making same. US 7553547 B2, 2009.
(9) Addleman, R. S.; Bays, J. T.; Carter, T. G.; Fontenot, S. A.; Fryxell, G. E.; Johsnson, D. W. Renewable sorbent material and method of use. US2010/0147768 A1, 2010.
(10) Addleman, R. S.; Chouyyok, W.; Li, X. S.; D.Cinson, A.; Gerasimenko, A. Porous multi-component material for the capture and separation of species of interest. Publication No.: US2014/0322518 A1, 2014.
(11) Chouyyok, W.; Warner, C. L.; Pittman, J. W.; Mackie, K. E.; Nell, K. M.; Clubb, D. C.; Addleman*, R. S., Aqueous Collection and Recovery of Rare Earths with Nanostructured Sorbents. In preparation for submission to ChemsusChem. 2016.
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Context: 5) Flow from Grain Farming to Sectors other than “Flour Milling and Manufacturing”:
It is assumed that about 90 % of wheat grain bushels used in domestic markets are used in “Flour Milling and Manufacturing” sectors [1]. The rest 10 % are distributed among sectors such as: “Breakfast Cereal Manufacturing”, “Dog & Cat Food Manufacturing” and “Other Animal Food Manufacturing”. The distribution of 10 % of bushels of grain that are consumed within the state to these 3 sectors are based on % used in various industries obtained from report [1]. This was the best data available to calculate the distribution of wheat in other sectors, however this data is a bit old.
a) Wheat grains Used in State = 1.49E+07/0.9 = 1.65E+07 bushels of wheat
b) Wheat grains used for Breakfast Cereal : (1.65/100) x 1.65E+07 = 2.73E+05 bushels of wheat
c) Wheat grains used for Dog & Cat Food Manu. : (1.96/100) x 1.65E+07 = 3.24E+05 bushels of wheat
d) Wheat grains used for “Other Animal Food Manu.” : (5.15/100) x 1.65E+07 = 8.52E+05 bushels of wheat
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Context: Appendix E
Experimental Details for Sorbent Testing in Geothermal Waters
Adsorption measurement
Percent adsorption of REEs and other trace metals by sorbents were performed in geothermal water (from Sharkley Hot springs, Idaho). The geothermal water was spiked with metal ions of La, Eu, Ho, and other trace metals at ~ 50 ppb for each metal. A 4.9mL of the metal solution was placed in a polypropylene bottle and spiked with 0.1mL sorbent suspended in DI water to obtain a liquid-to-solid ratio of 50000 (L/S in mL liquid/g sorbent). The tubes were shaken for 2 hours at 200 rpm on an orbital shaker. Then the magnetic materials were separated from the solution using a 1.2 T NdFeB magnet. The nonmagnetic materials were collected by filtering the solution thru 0.45-µm syringe Nylon-membrane filters. The removed supernatants were stored in 2% (v/v) HNO3 prior to metal analysis. The metal ion concentrations in the control (no sorbent), with and without filtration were analyzed in order to check for precipitation of metal ions and confirm concentrations. These sample solutions were analyzed using an inductively coupled plasma mass spectrometer (ICP-MS, Agilent 7500ce, Agilent Technologies, CA). All batch experiments were performed in triplicate and the averaged values were reported.
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Context: Data From EPIC Model (produced using FEST-C v1, Cooter et al, 2012)
Table 9 : Average Annul Emissions Soybean and Winter Wheat Farming in Illinois| Soybean | YON (Kg-N) | Q-NO3 (Kg-N) | AVOL (Kg-N) |
| -------- | -------- | -------- | -------- |
Soybean_Irrigated | 6.77E+02 | 5.95E+04 | 3.42E+02 |
Soybean_RainFed | 1.38E+05 | 8.65E+06 | 1.23E+03 |
| | | |
Total (Kg-N) | 1.38E+05 | 8.71E+06 | 1.57E+03 |
Total (metric tons) | 1.38E+02 | 8.71E+03 | 1.57E+00 |
| Winter-Wheat | YON (Kg-N) | Q-NO3 (Kg-N) | AVOL (Kg-N) |
| -------- | -------- | -------- | -------- |
Winter-Wheat_Rainfed | 1.84E+04 | 1.12E+06 | 1.63E+03 |
Winter_Wheat_Irrigated | 5.02E-01 | 1.28E+02 | 3.94E+01 |
| | | |
Total (Kg-N) | 1.84E+04 | 1.1E+06 | 1.7E+03 |
Total (metric tons) | 1.84E+01 | 1.12E+03 | 1.67E+00 |
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Context: Assumptions and Calculations of Corn Flows:
N Flow from Nitrogenous Fertilizer consumption to Corn Farming (Flow # 12): This flow consists of Nitrogen fertilizer being applied for corn and sweet corn farming.
N fertilizer for Sweet Corn
Sweet corn is used in the economy as fresh sweet corn and processed form.
Fresh sweet corn Farming Data
Source: USDA NASS
Link: http://usda.mannlib.cornell.edu/MannUsda/viewDocumentInfo.do?documentID=1564
| Illinois | Source : NASS tables 18,19 in PDF |
| -------- | -------- |
Sweet Corn : Fresh (2002) |
| Acreage (Acres) | Yield per acre |
| Planted | Harvested | Unit : cwt |
2001 | 6200 | 5700 | 98 |
2002 | 6200 | 5600 | 100 |
Sweet Corn : Processed (Freezing and Canning) (2002)Acreage (Acre)Yield per acrePlantedHarvestedUnit : Short ton200118400175006.66200216100138005.8
Fertilization rate for Sweet Corn Production [Source: John R Teasdale et al, 2008] = 174 KgN/ha or 70.415364 Kg-N/acre | Fertilizer for fresh sweet corn | 436575.2568 | kg-N = (6200*70.415364) |
| -------- | -------- | -------- |
Fertilizer for Processing Sweet Corn | 1133687.36 | kg-N = (16100*70.415364) |
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Context: Table B2. Trace elements concentration (µg/L, ppb) in Sharkey Hot Springs, ID| Element | Concentration | Element | Concentration |
| -------- | -------- | -------- | -------- |
Li
B
Al
Cr
Co
Ni
Cu
Zn
Ge
Rb
As
Se
Sr
Y
Zr
Rh
Mo | 596.67
1787.78
ND
0.78
0.03
0.39
5.55
2.71
7.57
90.84
19.55
0.96
443.89
0.02
0.09
0.01
13.59 | Pd
In
Sn
Te
Ru
Ag
Cd
Sb
Ba
Cs
W
Pt
Hg
Pb
Th
U | 0.21
0.01
0.14
0.02
0.33
0.04
0.03
1.79
23.72
32.57
47.59
<0.006
2.54
0.11
0.003
0.24 |
Appendix C
Evaluation of Solid-State Sorbent Technology: Down-Select to the Most Effective Sorbent Chemistries
Specific details on the performance test of selected surface chemistries evaluated are provided below. Final evaluation testing was done in geothermal water collected from Sharkley Hot springs in Idaho which are near proven REE mineral deposits under assessment and development.
a) Organic functional groups
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Context: rbent affinity and capacity
-- Sorbent kinetics
-- Sorbent lifetime
-- Sorbent form factor
-- Mineral recovery from sorbents and sorbent regeneration
-- Cost effectiveness (materials, recovery process, space, installation and operation)
All of these material performance parameters must be achieved and successfully coordinated for an effective chemical extraction process to be achieved. Some additional details are available in Appendix A.
The critical challenges for successful application of solid state sorbent technology for geothermal mineral extraction will be addressed in detail in multiple upcoming publications. The results of the effort will have application to this and other projects (or future efforts) for low temperature mineral recovery.
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Context: Bare substrate materials |
Fe3O4 (8nm) | 21 | 1 | 36 | 3 | 31 | 80 | 96 | 73 | 86 | 57 | 79 |
Fe3O4 (25nm) | 5 | 0 | 34 | 3 | 7 | 20 | 96 | 55 | 32 | 29 | 77 |
Core Fe3O4 (cluster) | 13 | 0 | 39 | 3 | 16 | 9 | 86 | 63 | 66 | 40 | 52 |
Cabosil SiO2 | 0 | 1 | 31 | 6 | 2 | 5 | 19 | 53 | 10 | 28 | 21 |
Nanopore SiO2 (Davisil 635) | 0 | 0 | 29 | 6 | 1 | 6 | 7 | 44 | 9 | 29 | 0 |
Each metal concentration ~50-100 ppb, Equilibrium pH~7.7, L/S 50000 mL/g, contact time for 7 hours
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Context: Soybean meal consumption by poultry | Other animal food manu. | Poultry & Egg Production. | 40.07408 | 1000 tons | 2.82E+00 | 1000 tons of N |
Export of Soybean meal | Soybean processing | | 5736 | 1000 tons | 4.04E+02 | 1000 tons of N |
Soybean meal sent to animal food manu. Within state | Soybean processing | Other animal food manu. | 792 | 1000 tons | 5.58E+01 | 1000 tons of N |
Export of Soymeal from animal food manu. | Other animal food manu. | | 80.59 | | 5.67 | |
Nr fertilizer input to soybean farming | Nitrogenous fertilizer manu. | Oilseed farming | 2.10E+08 | Pounds of Nr | 2.10E+08 | Pounds of Nr |
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Context: 10 | Soybean & other Oilseed processing | Dog & Cat food manu. | Soy processing byproducts for pet food manu. | _ | _ | Not available |
11 | Animal production except cattle, poultry & eggs | Seafood product preparation & packaging | Processing of seafood | _ | _ | Not available |
12 | Oilseed farming | Exports | Flow going out of state | Soy-Illinois Report | 187 million bushels | 2.81E+05 |
13 | Oilseed processing | Exports | Flows of soymeal out of state | Soy-Illinois Report | 5736 thousand tons of soymeal | 4.04E+05 |
14 | Oilseed farming | Beg Stocks | Original stock of soybean bushels | Soy-Illinois Report | 34 million bushels | 5.10E+04 |
15 | Oilseed farming | End Stocks | Left Over stock of soybean bushels | Soy-Illinois Report | 27 million bushels | 4.05E+04 |
16 | Nitrogenous fert. Manu. | Oilseed Farming | Nitrogen fertilizer used for soybean farming | Calculated (See 2.1.1) | 2.10E+08 pound of Nr | 9.53E+04 |
17 | Natural N fixation | Oilseed farming | Nitrogen fixation by soybean | Daniel Sobota (Personal communication) | 3.49E+08 kg-N | 3.49E+05 |
Table 2 : Flows for Soybean in N- PIOT (Figure 2 shows the Soybean Flows)
Assumptions and Calculations of Soybean Flows: The description for calculation of flows depicted in the material flow diagram for soybean is discussed below. Flow numbers mentioned refer to the number shown on arrows in the material flow diagram, Figure 2.
1) Flow # 16 : Nitrogenous fertilizer input to Soybean farming (Oilseed farming sector)
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Context: igh affinity) capture chemistries installed at high densities. The excellent affinity, selectivity, capacity, and reusablility of the PNNL composite sorbent materials provide multiplicative benefits. The high affinity enables capture of ultra-trace level metals from solutions where recovery was not previously possible. For select applications environmentally benign methods have been developed for cost effective recovery (stripping) of the collected metal and for regeneration of the sorbent material which provides multiple reuse cycles. These optimizations further reduce costs and improve process viability. All sorbents can be stripped and regenerated with standard acid processes. The organic chelator based sorbents are stable up to 250-350oC depending upon composition. The modified metal oxide sorbents are believed to be stable to over 400oC.
Work to date has shown the sorbent material to be easily integrated with a wide range of metal, ceramic, and polymeric support structures that can be optimized for different applications including traditional packed beds, various filter structures, and novel membranes. Rapid kinetics, demonstrated with the composite thin film and fiber configuration of these sorbents, may also provide lower process cost as well as reduced biofouling issues. Patents have been granted or are pending and manuscripts are in preparation.8-13
Other organizations have been developing new commercial off the shelf (COTS) sorbent materials that merit comparative and competitive evaluation in this effort. Promising new COTS sorbent materials are available from a number of companies including; Eichrom Technologies, Steward Advanced Materials, IBC, Silicyle, IntelliMet, Rohm and Hass, and others. Novel separation materials may also be available from DOE funded effort at the Critical Materials Hub as well as the DOE-NE efforts for uranium recovery from seawater. Materials made available from commercial sources and government sources will be evaluated and their expertise will be collaboratively engaged as these companies choose to interact.
Project Summary and Status
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Context: Table 13 : Sectors in N-PIOT And Description| Sectors (NAICS) | Description of Sector Activities |
| -------- | -------- |
Oilseed farming | Soybean farming and other oilseed crop farming. For Illinois, Soybean farming dominates in this sector. |
Soybean and Other Oil Seed Processing | Industrial activity involved in processing soybean and other oilseed for conversion into products like soymeal, soyoil, animal feed etc. |
Corn Farming | Mostly corn farming. |
Wet Corn Milling | Industrial establishments that produce mostly starch, syrup, oil and byproducts such as gluten feed and meal by wet milling of corn and sorghum. In Illinois, it was mainly corn wet milling. |
Dry Corn Milling | Dry corn milling is mainly used to produce ethanol. |
Wheat Farming | Farming activities growing wheat. |
Flour Milling & Malt Manu. | Industries involved in processing wheat for conversion to other products or sale to food manufacturing industry. |
Other Animal Food Manu. | Industries involved in food manufacturing for cattle, hogs etc. |
Dog & Cat Food Manu. | Industries involved in food manufacturing for pets. |
Cattle Ranching & Farming | Livestock farming industry. |
Animal Production Except Cattle & Poultry Eggs | Hog, Pig, Sheep, Goat farming industry. |
Poultry & Egg Production | Poultry farming industry. |
Poultry Processing | Industry engaged in poultry slaughtering and preparing processed poultry and small game meat/meat byproducts. |
Animal (Except Poultry) Slaughtering & Processing | Industry engaged in slaughtering and preparing processed meat from hog, pig, cow etc. |
Nitrogenous Fertilizer Manu. | Fertilizer manufacturing industry |
Bread, bakery and product manu. | Food manufacturing industry of bread etc. |
Cookie, cracker and pasta manu. | Food manu. |
Snack food manu. | Snack food. |
Tortilla manu. | Tortilla manufacturing from wheat flour, corn flour etc. |
Breakfast cereal manu. | Cereal manufacturing industry |
Frozen food manu. | Industry involved in freezing food such as sweet corn, meat etc. |
Vegetable and fruit canning & drying | Industries involved in preparing canned and dried food for distribution. |
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Context: | -------- | -------- | -------- | -------- | -------- | -------- |
Source : http://usda.mannlib.cornell.edu/MannUsda/viewDocumentInfo.do?documentID=1564 |
Fresh Sweet Corn | pounds | 52,106,295 | 2002 | ERS/USDA | US |
Canned Sweet Corn | pounds | 42,014,881 | 2002 | ERS/USDA | US |
Frozen Sweet Corn | pounds | 29557470.00 | 2002 | ERS/USDA | US |
Sweet corn planting seed | pounds | 614,902 | 2002 | ERS/USDA | US |
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Context: rines of potential interest that could supply essential metals for clean-energy technologies and other industries. The developed and demonstrated technology and economic analysis will have applications to other industries where recovery of trace minerals from solutions (i.e., low grade sources, recycling processes, industrial by product flows and tailings/waste streams) would provide a value-added price.
Background
The Promise and Abundance of Critical Minerals in Geothermal Resources
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Context: Protein Content of Corn = 9.42 %
[Source: http://ndb.nal.usda.gov/ndb/foods/show/6432?fgcd=&manu=&lfacet=&format=&count=&max=35&offset=&sort=&qlookup=Corn]
N content in Seed = (9.42/100) x (1.70E+08) = 16.037 metric tons of N
5) Consumption of Sweet Corn directly by Human : Corn farming sector also represents “sweet corn farming” that is directly consumed by humans either as canned, frozen or fresh sweet corn.
a) Consumption as Frozen Sweet corn: This flow is represented by the flow of N from “Corn Farming” sector to the “Frozen Food Manu.” Sector.
b) Consumption as Canned Sweet Corn : This flow is represented by the flow of N from “Corn Farming” sector to the “Vegetable and Fruit Canning & Drying”
c) Consumption as Fresh Sweet Corn: This flow is represented by the direct flow of N from “Corn Farming” to Human Consumption.
US Sweet Corn : Per capita domestic consumption (2002)Unit : pounds per personFreezingCanningFresh9.37.89.0Sweet Corn Domestic Consumption in Illinois (2002)FreezingCanningFreshPounds1.17E+089.83E+071.13E+08grams5.32E+104.46E+105.14E+10gram of proteins1.59E+091.34E+091.54E+09Gram of nitrogen2.55E+082.14E+082.47E+08
1) ----media/image4.png----Wheat Flow CalculationsFigure 4: Wheat Flow DiagramFigure 4: Wheat Flow Diagram
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Context: Eggs | 112.18 | 1.00 | 112.18 | 0.48 | 0.76 | 41.27 | 20.64 | 18.72 |
Milk | 2051.00 | 1.00 | 2051.00 | 0.08 | 0.30 | 49.22 | 24.61 | 22.33 |
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Context: a) Organic functional groups
The sorbents contained organic surface chemistries as shown in Figure C1 were chosen for evaluating the collection of REE and other metals from geothermal fluids. The functional groups were installed on different structures of substrates such as Cabosil (nonporous sorbent, particle size of ~0.2-0.3 µm, easily to form composite thin film with polymer), Davisil (Porous column with size particle ~250-500 µm ) and MCM41 (nanoporous materials with particle size of 1-5µm) The experiments were performed through batch contact experiment, at ~40 ppb of REE, solution’s pH ~7.7, liquid to sorbent ratio (L/S) of 50000 mL/g, and 2 hours of contact time. La, Eu and Ho were chosen to represent of light, middle and heavy REEs. The performances of the sorbents are categorized according to their surface chemistries, as results shown in Tables C1 and C2;
----Image alt text---->G:\active ligands for GTO-Q3 report.tif<----media/image1.tiff----
Figure C1. Chemical structure of organic ligands/surface chemistries
Diphosphonic and mono phosphonic groups installed sorbents provided the best performance for collection of REE from geothermal water. IDAA and SH groups installed silica materials show outstanding performance for adsorption of valuable metals (Ag), base metals and toxic materials from geothermal water.
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Context: -- Diphos-Cabosil shows a very high affinity for REEs and Ag, over 95% of these metals were collected. It offers only moderate affinity for base and toxic metals (except, the Hg). Similar performance for REE collection also can be seen from Actinide Resin; which is a commercial sorbent material and also contains diphosphonic group; however, this sorbent doesn’t show a good sorption of valuable and other metals.
-- PropPhos shows outstanding performance for REE collection, over 98% of the REE were collected. It also offers excellent sorption of base metals (i.e., Cu, Zn) and some toxic metals. The slightly lower performance can be seen from Ln Resin for REE collection. While Uteva resin shows no affinity for REE collection at this solution pH.
-- Styrene IDAA provides low to moderate binding for REEs, lower than we expected, lower than 50% of REEs were adsorbed. While it offers excellent adsorption for Ag and most of the base and toxic metals. On other hand, very poor performance can be seen from Chelex100.
-- SH shows very low affinity for REEs, but has very high affinity for Ag, Cu, Zn and toxic metals. GT-74 provides much lower performance than SH functionalized silica base substrates.
-- Amidoxime installed sorbent materials show very low performance for REE collection even though the amidoxime based fiberglass were performed at lower L/S. Both types of Amidoxime functionalized polymer fibers offer excellent adsorption of Ag, Cu and Hg.
-- Activated carbon and Ion exchange resins (SAX and WAX) show low to moderate affinity for REEs and other metals (except for Cu)
-- The Diphos-Cabosil and styrene IDAA show excellent performance in capturing the soft metals (i.e., Ag, Hg) due to it also containing SH groups as a linker on their ligands during the surface installation.
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Context: 2) Fresh Nr Fixation by SoybeanN fixation data in Soybean for 2002 - Illinois.
Source : Dan Sobota (Personal Communication, manuscript in Prep)VariableValueUnitMin4.32E+06Kg-N1st quartile2.04E+08Kg-NMedian3.49E+08Kg-NMean3.89E+08Kg-N3rd quartile5.32E+08Kg-NMax1.82E+09Kg-NTable 3 : N Fixation Data in Soybean - Illinois (2002)
2.1.3 Nr Input to Soybean farming sector as Seeds : Calculation of Seed requirement for Soybean Plantation (Flow # 1)
This data was not found. So, communication was established with Soybean expert at USDA NASS, Travis Thorson. (travis_thorson@nass.usda.gov)
It was suggested that Bushels of Soybean for Seed = Acres X 1.16
This data was supported with existing data on use of Soybean bushels for seeds and Acres Harvested. [Data Source: WASDE Report, http://usda.mannlib.cornell.edu/MannUsda/viewDocumentInfo.do?documentID=1194]
From WASDE Report, | Year | Seeds (Million Bushels) | Acres Harvested | Ratio (Seeds in Million Bushels/ Million Acres Harvested )
Unit : Million Bushel/ Million Acres |
| -------- | -------- | -------- | -------- |
2000/2001 | 91 | 72.4 | 1.25 |
2001/2002 | 89 | 73 | 1.21 |
Table 4 : WASDE Report Data (Estimating Seeds Input for Soybean Farming)
From the table, an approximate ratio of 1.21 was used for the state of Illinois. The ratio from the WASDE report was at national scale.
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Context: Eu was selected to represent REEs for recycle/recovery studies of the sorbents due to its central position in the f-block elemental sequence and its economic impact as one of the top 3 priced REE’s. HCl was chosen as a stripping agent due to previous positive results using this acid to recover minerals from high affinity sorbents and effective stabilization of the extracted REEs in solutions. Recovery chemistry is a function of both the sorbent material and the mineral of interest. Effective mineral stripping/recovery solutions for the Diphos sorbent are still under examination (1 M HCl was found to be insufficient). Processed geothermal brine will be available for reinjection with minimal change in chemistry.
A subtle but significant finding is the selective separation/removal of the soluble natural radioactive minerals that will likely be collected in the process of REE collection from geothermal brine by the sorbents. We have found that U can be selectively removed from the preferred sorbents in advance of other minerals (avoiding subsequent contamination and separation issues) with a simple 1 molar sodium carbonate rinse. Solutions for addressing the challenges with selective separation of Ra and Th are under consideration.
Subtask 2.2
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Context: Recovery of Rare Earths, Precious Metals and other Critical Materials from Geothermal Waters with Advanced Sorbent Structures
R. Shane Addlemana*, Wilaiwan Chouyyoka, Daniel Palob, Brad M. Dunnb, Gary Billingsleyc, Darren Johnsond, Kara M Nelld
a Pacific Northwest National Laboratory, Richland, Washington, 99352, 509-375-6824, raymond.addleman@pnnl.gov
b Barr Engineering Co., Minneapolis, Minnesota 55435
c Star Minerals Group Ltd., Saskatchewan, Canada S7L5x5
d University of Oregon, Eugene, Oregon, 97403
Abstract
We develop and demonstrate high value strategic mineral extraction technology for geothermal solutions to provide additional revenue for geothermal operations. This is accomplished with high performance solid state sorbent materials. The best industrial materials as well as new PNNL patented technology, which has demonstrated unequalled chemical affinity for trace element collection. The high performance collection materials will enable superior performance and will enable low cost capture of high value materials creating a secondary revenue stream for geothermal projects. The sorbent materials are configured for collection of trace levels of rare earths (REEs), precious metals (PMs), and other critical/strategically valuable materials (CMs) such as zinc, manganese, copper, and uranium. Sorbent performance is determined in actual geothermal water of Sharkey Hot Springs, Idaho. We develop and demonstrate reusable sorbent materials capable of high efficiency collection of trace levels of REE from geothermal waters. A technoeconomic analysis is conducted to determine the viability of the sorbent technology in general, and the new high performance materials in particular, as a value added extraction process for geothermal energy systems. The project measures and provides the information of the concentration of REEs, PMs, and CMs at established geothermal sites and at hot springs in the vicinity of relevant mineral deposits, to identify
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Context: 2) Flow # 4: Flow of Byproducts from Wet Milling of Corn to “Other Animal Food Manufacturing”
The wet milling of corn produces by products like “Corn Gluten feed” and “Corn gluten meal” that are used in animal feed manufacturing.Co-product formation in Wet Milling of Corn per bushel of cornCo-ProductValueUnitCorn Starch31.5poundsCorn Gluten Feed13.5poundsCorn gluten meal2.5poundsCorn Oil1.1poundsSource: Corn Milling, Processing and Generation of Co-products (Minnesota Nutrition Conference, Minnesota Corn Growers Association Report)
Co-Product Formation by Wet Milling of Corn in Illinois (2002)Co-ProductValue (pounds)Corn Starch2.55E+09Corn Gluten Feed1.09E+09Corn Gluten Meal2.02E+08Corn Oil8.91E+07
Calculation of N flowing in Corn Wet Milling Byproducts
To convert the flow of byproducts from corn wet milling to the “Other Animal food manu” in the units of N flows the % of protein in each byproduct was used.
Source: Kelly S. Davis, Corn Milling, Processing and Generation of Co-Products, Minnesota Nutrition Conference, Minnesota Corn Growers Association.Products of Corn Wet MillingProteinFatFibersCorn Condensed Distillers Solubles (CDS)29 %9 %4 %Condensed Corn Fermented Extractives (or Corn Steep Liquor)25 % on a 50 % solids basis--Corn Germ Meal20 %2 %9.5 %Corn Gluten Feed21 % (16 % - 23 %)2.5 %8 %Corn Gluten Meal60 %2.5 %1 %
For Corn Gluten Feed = 19.5 % (Assumed as average)
For Corn Gluten meal = 60 % (Assumed as reported, max)
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Context: ganic surface chemistries had to be installed on nanostructured supports. Data not shown demonstrates that thiol surface chemistry was extremely effective for “softer” heavy metals such as Au, Ag, Cu, and Zn. These metals are known to have higher solubility and more abundance than REEs in geothermal waters. Work is underway to combine thiol chemistries with the other preferred sorbent chemistries (e.g., Diphos and PropPhos that have been shown to be effective for REEs) to provide a single polyfunctional sorbent material that is as collecting a wide range of valuable minerals from geothermal solutions.
----Image alt text---->G:\active ligands for GTO-Q3 report.tif<----media/image1.tiff----
Figure 1. Chemical structure of preferred organic ligands/surface chemistries for collection of REE and other valuable minerals from geothermal waters
The reusability of preferred sorbents is shown in Table 2. The sorbent’s ability to provide many collection and mineral recovery cycles is a key capability to enable economic viability in the evaluation operation and applications. High collection and recovery (stripping of adsorbed Eu for sorbent) efficiencies were maintained for 10 cycles for several preferred materials with trending indicating many more effective processing cycles were possible. Effective recovery of adsorbed Eu from one of the more promising materials was not achieved (Diphos on silica supports). Additional work is needed to determine a viable stripping recovery solution from this very promising sorbent material. Processing details are provided below the data tables and in appendix E.
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File: 0MB%20Singh%20et%20al.%202017%20Ecol%20Modell%20Supp%20Data.docx
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Context: 4) Flow # 13: Flow of N from Corn farming to Corn farming in form of “corn seeds” – This flow is calculated by calculating the seed requirement for corn plantations based on acres harvested in Illinois for 2002.
Seeding Rate = Plant population per acre at harvest / (Seed germination x Expected Survival)
Average seed germination rate for corn = 95 %
Expected survival = 85 % - 95 %
[Source: http://corn.osu.edu/newsletters/2010/2010-08-4-13/corn-seeding-rates-vs.-final-stands]
| State | Plant population per acre at harvest (bushel/acre) | Seeding Rate (seed/acre) | Acres harvested (Corn for grain) | Total Seeds |
| -------- | -------- | -------- | -------- | -------- |
Illinois | 135.5 | 158.479 | 10742787 | 1.70E+09 |
Seeding rate for Illinois = 135.5/ (0.95 x 0.90) = 158.479 seeds/acre
Total Corn Seeds Used in Illinois in 2002 = 10742787 x 158.479 = 1.70E+09
Weight of Seed = 1.70E+09 *(1/10) = 1.70E+08 gm
[Source of Weight: http://www.harvesttotable.com/2011/05/vegetable_seeds_per_ounce_per/]
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File: Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx
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Context: Background
The Promise and Abundance of Critical Minerals in Geothermal Resources
Geothermal brines represent a potential new source for strategic materials but the abundance of minerals and cost effective technology for separation from geothermal brines are unknown. Recent GTO partnering efforts have demonstrated effective extraction of lithium, manganese, and zinc from geothermal brines, providing proof of principle that additional revenue streams may be realized from mineral recovery in geothermal power operations (and potentially from other low concentration sources).
The rare earth (RE) elements occur at generally low concentration in geothermal fluids in the range from a few hundred picograms to several micrograms per liter.1-3 For example, at a thermal spring associated with Idaho batholith, in unfiltered samples1, total REs content varies from ~0.05-3.24 µg/L, with an average ~0.63 µg/L. The most abundant REs in these geothermal fluids are lanthanum (La), cerium (Ce) and neodymium (Nd) with average concentration of ~0.14, 0.26 and 0.35 µg/L, respectively. It should to be noted that unfiltered samples often contain much higher concentration of RE than filtered samples. At acidic hot springs in the Kusatsu-shirane volcano region of Japan2, total RE concentrations range from ~15.0-718.5 µg/L, and average ~210.7 µg/L. The most abundant REs in these geothermal fluids are La, Ce and Nd with average concentrations of ~31.9, 75.4 and 33.8 µg/L, respectively. Although La, Ce and Nd display higher concentration than other REs in many hydrothermal fluids, Eu content in hydrothermal fluids from the Mid-Atlantic Ridge was slightly higher than Nd, the average concentration of these metals was 0.26, 0.33, 0.17 and 0.19 µg/L, respectively.3 The variation in concentration and the fractionation of REs are results of the location, source rocks and
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File: 0MB%20Singh%20et%20al.%202017%20Ecol%20Modell%20Supp%20Data.docx
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Context: Assumptions for Calculation of Flows
1) Wheat Seed Consumption: The rate of seed used in 2002 was assumed same as rate of seed used in 1997 since the yields of these years were not very different and data for 2002 was not available.
Seeding Rate = 73 pounds/acre
Acres planted = 660,000 acres (NASS)
Total Seed Used = 4.82E+07 pounds
2) Wheat Fertilizer Consumption
Pounds/acre of N Fertilizer in 2002 = 90.5 (Source: ERS USDA by interpolation of 2001 and 2003 data)
Acres Planted in 2002 in Illinois = 660,000 (Source: NASS)
Total Fertilizer Used in Illinois for Wheat (2002) = 5.97E+07 pounds of N
3) Total Wheat Consumption in Illinois (2002) : 1.72E+09 pounds
4) Flow from Grain Farming to “Flour Milling & Malt Manu” in Illinois: This flow value was calculated by scaling down the flow of national scale Flour Milling by the share of Illinois.
-- Total Wheat Milled in US for Flour (2002): 212,609 of 1000 grain-equivalent bushels (Source : \cite{ERSWheatFlourConsumption}, USDA ERS Datasheet on Wheat Food Use by Component.
-- % of Wheat Milling for Flour activity Allocated to Illinois = 7 %
The calculation is based on the total cost of materials that goes to the Flour Miiling sector at the national scale or state of Illinois. The data in the table below is from Manufacturing Industry Survey series.
Economic Data Comparison For NAICS Sector (Flour Milling) for Illinois vs US2002Geographic Area Name2002 NAICS CodeMeaning of 2002 NAICS CodeTotal Cost of materials ($1,000)Production Workers hourse ($1,000)Number of employeesIllinois311211Flour Milling377,0331,441912United States311211Flour Milling4,922,50918,37511,636Ratio0.0760.0780.078
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File: Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx
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Context: Table 2. Sequential collection and release performance for selected sorbent materials for Eu from geothermal water throughout 10 process cycles| Sorbent | Collection Efficiency (%)a | Recovery Efficiency (%)b |
| -------- | -------- | -------- |
Diphos on silica supports | 99.8±0.3 | Work in progressc |
PropPhos on silica supports | 98.5±0.9 | 93.5±5d |
Mn doped on Fe3O4 supports | 97.5±1.0 | 82.6±9.8e |
a Values are average from 10 process cycles, Initial concentrations of Eu was ~50 ppb spiked into geothermal solution for Sharkley Hot springs in Idaho, solution’s pH~7.7, 1 hour batch contact with gentle agitation.
b Values were average from 10 stripping/recovery cycles, 1 hour batch contact with gentle agitation.
c1M HCl was used for stripping solution. More aggressive stripping solutions are being explored.
d 0.1M HCl was used for stripping solution
e 0.01M HCl was used for stripping solution
Additional experimental details available in appendix E. Location of Sharkley hot springs and mineralogy shown in appendix B.
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File: Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx
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Context: Complete Analysis of Geothermal Fluids: Location and Chemistry of Sharkley Hot Springs
----Image alt text---->Idahomap4<----media/image2.png----
Figure B1. Map of Minerals and Hot Spring Occurrence in the Lemhi Pass area in Idaho
The Lemhi Pass area is highly mineralized and has large number of sites with REE and thorium, Co and other mineral occurrences. The region also has significant hydrothermal hot spring activity and has some geothermal energy potential. However the region is remote and not near any major metropolitan energy grid.
Source: http://www.idahogeologry.org
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File: Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx
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Context: (12) Nell, K. M.; Chouyyok, W.; Pittman, J. W.; Warner, M. G.; Johnson, D. W.; Addleman*, R. S., Assembly of Polyfunctional Surface Chemistry Installation of Hard, Soft and Chelating Components for the Creation of High Performance Sorbents. in preparation for submission to Langmuir. 2016.
(13) Chouyyok, W.; Pittman, J. W.; Warner, M. G.; Nell, K. M.; Clubb, D. C.; Gill, G. A.; Addleman*, R. S., Application of functionalized nanostructured ceramic sorbents for the collection and recovery of Uranium from sea water. Dalton transcation.submitted 2015.
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File: Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx
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Context: REE collection and sorbent recycling/reuse evaluation
The sorbents demonstrating high REE collection performance (>90% REE uptake) were selected for Eu collection and stripping study. The sorbent materials were Diphos on Silica supports, PropPhos on silica supports, and Mn doped on Fe3O4 supports. The collection of REEs from geothermal water (from Sharkley Hot springs, Idaho) and recovery of adsorbed REEs from the selected sorbent materials were obtained through batch sorption experiment. The geothermal water was spiked with Eu to approximately 50 ppb to provide sufficient concentration to enable determination of high adsorption. The pH of the geothermal water after adding Eu was 7.71. Then, 1 mL of the Eu spiked geothermal water was added in a plastic vial that contained 0.010 g sorbent material to obtain L/S ratio of 100. The vial then was placed on a shaker table for agitation at 200 rpm until contact was completed (in this study, it was completed within 1 hour). The Eu adsorbed the functional groups modified silica supports were removed from solution by centrifugation at 13000 rpm for 10 minutes. The Eu adsorbed magnetic nanoparticles were separated from the geothermal water using a 1.2T NdFeB magnet. Then, the relevant volume of stripping solution (1 mL of HCl) was added to the vial containing a sorbent to maintain the L/S of 100. The stripping solutions were separated from sorbents after they were continually shaken for 1 hour using the same technique as the collection step. The adsorption and stripping solutions were collected and stored in 2%(v/v) HNO3 for ICP-MS analysis. Note, HCl with concentrations of 1 M, 0.1 M, and 0.01 M were used as stripping solutions for removal of Eu from Diphos on Silica supports, PropPhos on silica supports, and Mn doped on Fe3O4 supports, respectively. For stripping studies a100 L/S ratio was chose to assure no limitation in recovery solution chemistry (ratio can likely be substantially reduced for preferred processing solutions). All batch experiments, adsorption and stripping steps, were performed in triplicate.
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File: 0MB%20Singh%20et%20al.%202017%20Ecol%20Modell%20Supp%20Data.docx
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Context: The soybean meal consumption within State of Illinois is calculated based on the production data for various cattle, poultry and dairy products. The production data shown in Table 2, is obtained from USDA NASS dataset.
Yield/lb : This is the final yield of product that is obtained for consumption from the original product. This data was assumed to be same for national yield and yield for Illinois. For example, for 1 lb of beef cattle the actual production of beef for consumption is 0.63 lb. The rest of the mass is waste or reused for other filler products.
The yield data is combined with the information on the protein meal required for per unit of production for consumption. For example, 0.97 lb of protein meal is required to generate 1 lb of beef for consumption and out of this protein meal requirement only 15 % comes from soybean meal. These data for meal consumption were obtained from United Soybean Board dataset [] and available here
Source: http://www.unitedsoybean.org/category/topics/animal-ag/#animalAgToolWrap
This was the best information available for calculation of soybean meal consumption within the state. Thus, the soybean meal consumption for producing each of the animal based product (beef, pork, dairy, egg, turkey and broilers) was calculated based on USDA NASS data for these in Illinois in 2002. Each of these flows were then converted into specific inter-sectoral flows based on the mapping of products with sectors.
a) N flow in Soybean Meal Consumed by Poultry Within State (Flow # 5): Manufactured feed utilizing Soybean meal for Poultry food. = 40.074 thousand tons. This flow is calculated as sum of soybean meal consumed for production of broilers, turkeys and eggs. These three products are mapped to the sector of “Poultry & Egg Production” which raises poultry (chicken and turkey).
N content = 40.074 x (10^3) x (0.44) x (0.16) = 2.82E+03 metric tons
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File: Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx
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Context: ate and Select Effective Sorbent Structures
Given the very high volumetric flow rates and high potential for fouling by suspended solids and dissolved minerals, the sorbent structure used in this application must be carefully chosen and evaluated. Bulk precipitation of low value minerals such as silicon and iron, as well as deposition of suspended solids can act to foul the sorbent and render it ineffective in capturing the target minerals. At the same time, a sorbent system must be deployed that provides the kinetics, capacity, and durability to render it effective, efficient, and economical in capturing high-value trace minerals from this source. Addressing these various technical challenges will enable the successful utilization of solid state sorbents (advanced or otherwise) for mineral recovery (REEs or other value added products). Consequently this program explored several alternative sorbent structures for application to high-volume trace mineral collection from geothermal fluids. Operational and economic factors are major criteria for selecting the sorbent structures to operate in the collection of REEs and valuable trace metals from geothermal fluids. The team has conducted a survey and analysis of solid sorbent structures for this high-volume application based upon experience in the areas of municipal water treatment, industrial chemical processing, and mineral extraction technology. Various structures were considered based upon important system parameters such as:
-- Resistance to fouling/plugging with precipitates,
-- Pressure drop,
-- Contact efficiency,
-- Durability,
-- Regenerability,
-- Manufacturability,
-- The need for specialized equipment.
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File: Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx
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Context: Table C1. The performance of organic sorbent materials
for REE collection from geothermal water| Sorbent | Adsorption of REEs in geothermal water (%) |
| -------- | -------- |
| La | Eu | Ho |
Diphosphonic group |
Diphos Cabosil | 96 | 99 | 99 |
Diphonix Resin | 32 | 49 | 45 |
Actinide Resin | 100 | 100 | 99 |
MonoPhosphonic group |
PropPhos MCM41 | 98 | 99 | 100 |
Ln Resin | 42 | 93 | 99 |
Uteva Resin | 0 | 0 | 0 |
EDTA groups |
styrene IDAA cab | 28 | 40 | 35 |
styrene IDAA Davisil | 46 | 51 | 40 |
Chelex 100 | 1 | 2 | 3 |
Thiol groups |
SH Cabosil | 0 | 4 | 7 |
SH Davisil | 0 | 2 | 3 |
SH MCM41 | 16 | 22 | 14 |
GT74 | 8 | 8 | 4 |
Amidoxime group |
Purolite®S910 | 0 | 6 | 7 |
Amidoxime fiberglass AF1L2R1* | 18 | 31 | 22 |
Amidoxime fiberglass 3495 - A18L2R2.1* | 0 | 2 | 6 |
Other materials and controls |
RE resin | 1 | 0 | 0 |
Activated Carbon | 32 | 15 | 8 |
AGMP 100-200 (SAX) | 21 | 41 | 36 |
CG50 (WAX) | 47 | 69 | 67 |
Cabosil | 7 | 22 | 23 |
Davisil -646 | 0 | 4 | 5 |
MCM-41 | 0 | 29 | 48 |
REE concentration ~40 ppb, Equilibrium pH~7.7, L/S 50000 mL/g, contact time for 2 hours with gentle agitation, *L/S =5000
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File: 0MB%20Singh%20et%20al.%202017%20Ecol%20Modell%20Supp%20Data.docx
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Context: | Fl
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File: 0MB%20Singh%20et%20al.%202017%20Ecol%20Modell%20Supp%20Data.docx
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Context: N Fertilizer for Corn
Area planted for Corn (Illinois, 2002; Source: USDA NASS): 1.11E+07 Acres
Total N applied to Corn plants = 1.70E+09 lb of N (Source : NASS QuickDataSets)
= 771,103 metric tons of N
Total N Consumption in Corn Plantation for Illinois, 2002 = 771,103 + (436575.2568 x 0.001) + (1133687.36 x 0.001) = 772,673.26 metric tons N = 7.73E+05 metric tons of N
1) Flow of Corn to Wet Milling Plants in Illinois (Flow # 1): This is the flow of corn bushels from corn farming to Wet Milling plants. The data for bushels of corn being milled by wet milling process is not available by each state. So, this flow is calculated based on the average Corn-ethanol being produced per bushel as explained below.
The assumption made is that each state will produce corn-ethanol based on the capacity. So, if capacity of a state is known, then it is assumed that the states are producing corn-ethanol at its full capacity.
Total Corn Ethanol Production in US (2002) = 2130 million gallons
[Source: http://www.ethanolrfa.org/pages/statistics#A ]
Process for Corn-Ethanol Production: Corn-ethanol is produced both in dry milling and wet milling of corn process.
Share of Each process
Dry Milling Process = 60 % of US Ethanol Production
Wet Milling Process = 40 % of US Ethanol Production
Source: US Corn-Ethanol Industry Statistics (Renewable Fuel Association)
http://www.ethanolrfa.org/page/-/objects/pdf/outlook/outlook_2003.pdf?nocdn=1
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File: 0MB%20Singh%20et%20al.%202017%20Ecol%20Modell%20Supp%20Data.docx
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Context: Calculation of Wheat Going to Other Sectors for IllinoisAssumption = 90 % of Wheat grain Used in Domestic Markets is Used in “Flour Milling and Malt Manu.”Wheat Grains Used in “Breakfast Cereal Manufacturing” 2.73E+05 bushelsWheat Grains Used in “Dog & Cat Food Manu.”3.24E+05 bushelsWheat Grains Used in “Other Animal Food Manu.”8.52E+05 bushels 6) Flow from “Flour Milling & Malt Manu” to Other sectors:
These flow values are calculated based on distribution of flour being processed for different use. This is described in the report on “The U.S. Milling and Baking Industries” (Harwood, Leath and Heid 2010). About 15 % of the flour being produced in Illinois is sold directly to consumers whereas, 85 % is being used in industries to produce consumer goods such as bakery, tortilla etc.
Flour Sold Directly to Consumers: (15/100) X 6.52E+08 = 9.78E+07 Pounds of flour
Flour Processed in Industries: (85/100) x 6.52E+08 = 5.54E+08 pounds of flour
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File: Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx
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Context: rature.1, 2, 4, 5 Speciation of REs in geothermal fluids depends on the types and relative concentration of ligands/complexing agents, as well as pH.
The precious metals (PMs) silver (Ag), gold (Au), palladium (Pd) and platinum (Pt) can be present in geothermal fluids at trace level in ppb range.6, 7 The geothermal fluids typically contain PMs below 20 ppb (µg/kg), however, Ag has been reported at levels 10-100 times higher than other precious metals in the Salton Sea and Raft River, USA.6 Similar to REs, PMs occur in varying degrees, depending on the concentration of complexing materials in the local geothermal fluids.6
Base metals occur in geothermal fluids in trace concentration in the ppm range (mg/kg).6 The abundant base metals and their concentrations in geothermal fluids are variable, and are found to depend on the geothermal systems and conditions. For examples, manganese (Mn), Zinc (Zn), and lead (Pb) were reported as the primary ions in geothermal brines and in greater concentrations than copper 6 , but different compositions of metals were found in spring waters.1, 2, 7 The concentrations of Mn and Zn were found to be ~500-1500 ppm in geothermal brines of Salton Sea, USA, ~1-2 ppm of Mn were reported in Bandaiko hot string water 2, and only < 1 ppb of both metals was detected in carbonate spring water7. The geothermal fluids also contain other metals, such as antimony, chromium, iron, nickel, arsenic, and tellurium at varying trace concentrations.1-3, 6, 7
Advanced Separation Materials
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File: Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx
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Context: The preferred sorbents materials in Table 1 significantly outperformed other custom and commercial sorbent materials evaluated. The organic surface phase sorbents have the advantages of faster kinetics whiles the inorganic materials have higher thermal stability (over 400oC). Note that to provide sufficient chemical affinity and capacity both inorganic
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File: Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx
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Context: Table B1. Chemical composition of geothermal fluids in Sharkey Hot Spring, Idaho | Chemical | Concentration
(mg/L, ppm) | REE | Concentration
(ng/L, ppt) |
| -------- | -------- | -------- | -------- |
pH
Temp
HCO3-
F-
Cl-
PO4-
SO42-
SiO2
Na
Mg
K
Ca | 8.01
37.5
NA
10.6
50.9
ND
151.8
38.2
288.2
0.9
14.5
0.6
| La
Ce
Pr
Nd
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu | 5.0
18.3
13.0
10.3
12.7
13.0
11.0
<12
13.0
<12
8.7
<12
8.3
<16 |
NA= not available, ND = none detected
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File: Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx
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Context: (1) Middlesworth, P. E. v.; Wood, S. A., The aqueous geochemistry of the rare earth elements and yttrium. Part 7. REE, Th and U contents in thermal springs associated with the Idaho batholith. Applied Geochemistry 1998, 13, 861-884.
(2) Kikawada, Y.; OI, T.; Honda, T.; Ossaka, T.; Kakihana, H., lanthanoid abundances of acidic hot spring and crater lake waters in the Kusatsu-shirane volcano region, Japan. Geochemical Journal 1993, 27, 19-33.
(3) Bau, M.; Dulski, P., Comparing yttrium and rare earths in hydrothermal fluids from the Mid-Atlantic Ridge: implications for Y and REE behaviour during near-vent mixing and for the Y/Ho ratio of Proterozoic seawater. Chemical Geology 1999, 155, 77-90.
(4) Hannigan, R. E., Rare earth, major, and trace element geochemistry of surface and geothermal waters from the Taupo Volcanic Zone, North Island New Zealand. In Water Science and Technology Library: RARE EARTH ELEMENTS IN GROUNDWATER FLOW SYSTEMS, Johannesson, K. H., Ed. Springer: Dordrecht, The Netherlands, 2005; Vol. 51, pp 67-87.
(5) Tang, J.; Johannesson, K. H., Rare earth element concentrations, speciation, and fractionation along groundwater flow paths: The Carrizo Sand (Texas) and Upper Floridan aquifers. In Water Science and Technology Library: RARE EARTH ELEMENTS IN GROUNDWATER FLOW SYSTEMS, Johannesson, K. H., Ed. Springer: Dordrecht, The Netherlands, 2005; Vol. 51, pp 223-251.
(6) Gallup, D., Geochemistry of geothermal fluids and well scales, and potential for mineral recovery. Ore Geology Reviews 1998, 12, 225-236.
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File: Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx
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Context: Table C2. The performance of organic sorbent materials for
valuable, base and toxic metals collection from geothermal water
| Sorbent | Adsorption of other metals in geothermal water (%) |
| -------- | -------- |
| Valuable metals | Base metals | Toxic metals |
| Ge | Mo | Ag | Li | Mn | Ni | Cu | Zn | Cd | Hg | Pb |
Diphosphonic group |
Diphos Cabosil | 0 | 0 | 97 | 0 | 2 | 0 | 51 | 62 | 20 | 91 | 27 |
Diphonix Resin | 2 | 0 | 12 | 3 | 42 | 0 | 65 | 19 | 45 | 27 | 45 |
Actinide Resin | 4 | 26 | 4 | 0 | 28 | 37 | 6 | 0 | 42 | 0 | 0 |
MonoPhosphonic group |
PropPhos SAMMS | 4 | 1 | 23 | 2 | 53 | 0 | 93 | 100 | 89 | 25 | 88 |
Ln Resin | 4 | 0 | 0 | 0 | 3 | 6 | 5 | 0 | 0 | 2 | 6 |
Uteva Resin | 2 | 1 | 0 | 0 | 1 | 37 | 0 | 0 | 6 | 0 | 0 |
EDTA groups |
styrene IDAA cab | 2 | 0 | 82 | 3 | 21 | 89 | 96 | 97 | 82 | 91 | 82 |
styrene IDAA davisil | 4 | 2 | 71 | 2 | 60 | 89 | 96 | 94 | 96 | 91 | 84 |
Chelex 100 | 9 | 9 | 17 | 4 | 3 | 0 | 15 | 0 | 0 | 45 | 5 |
Thiol groups | |
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File: Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx
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Context: b) Inorganic surface/metal oxide chemistries
The inorganic metal oxides surface chemistries as the structure of the sorbents shown in Figure C2 were chosen for evaluating the collection of REEs and other metals from geothermal fluids. The experiments were performed under the same condition as the organic surface chemistry sorbent but the contact time was increased up to 2 hours due to the fact that metal oxide sorbents normally take at least 4-6 hours to reach equilibrium. The results are shown in Tables C3 and C4;
| ----Image alt text---->C:\Users\h8906560\Desktop\SiO2FeMnO2.tif<----media/image3.png---- | ----Image alt text---->C:\Users\h8906560\Desktop\SiO2MnO2.tif<----media/image4.png---- |
| -------- | -------- |
A | B |
----Image alt text---->C:\Users\h8906560\Desktop\Mn_Meso.tif<----media/image5.png---- | ----Image alt text---->C:\Users\h8906560\Desktop\MnFe3O4(8nm).tif<----media/image6.png---- |
C | D |
Figure C2. Image of selected inorganic metals oxides; SEM of Fe/MnO2-SiO2(A), SEM of MnO2-SiO2composite (B), SEM of Mn doped Fe3O4 cluster (C), and TEM of Mn doped Fe3O4 nanoparticles (D)
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File: Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx
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Context: Table C4. The performance of inorganic metal oxide sorbents
for valuable, base and toxic metals collection from geothermal water
| Sorbent | Adsorption of other metals in geothermal water (%) |
| -------- | -------- |
| Valuable metals | Base metals | Toxic metals |
| Ge | Mo | Ag | Li | Mn | Ni | Cu | Zn | Cd | Hg | Pb |
Magnetic particles |
Mn doped Fe3O4 (8nm) | 16 | 0 | 30 | 3 | 0 | 66 | 96 | 99 | 98 | 73 | 96 |
Mn doped Fe3O4 (25nm) | 5 | 0 | 28 | 3 | 0 | 27 | 96 | 93 | 58 | 41 | 96 |
Mn doped Fe3O4 (cluster) | 0 | 0 | 80 | 2 | 69 | 63 | 96 | 99 | 98 | 65 | 96 |
None-magnetic particles |
MnO2-SiO2 composite | 1 | 1 | 47 | 5 | 40 | 40 | 96 | 95 | 90 | 45 | 96 |
MnO2-SiO2 composite (calcined) | 2 | 1 | 89 | 5 | 78 | 68 | 96 | 84 | 98 | 82 | 87 |
MnO2 Cabosil | 7 | 4 | 81 | 6 | 0 | 79 | 96 | 61 | 98 | 83 | 79 |
Fe/MnO2-SiO2 | 6 | 3 | 89 | 4 | 58 | 90 | 96 | 73 | 98 | 91 | 80 |
MnO2 Eichrom | 2 | 6 | 43 | 8 | 3 | 1 | 96 | 7 | 22 | 45 | 53 |
Bare substrate materials |
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File: 0MB%20Singh%20et%20al.%202017%20Ecol%20Modell%20Supp%20Data.docx
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Context: Use of Soybean in Crushing = 273 million bushels [Source: Soy Illinois Report]
% N in Soybean grain [Source: (Salvagiotti, et al. 2008)] = 6.34 %
Moisture in Soybean Bushel = 13 %
Weight of Soybean bushel = 60 lb
2) Flow of Soybean Bushels Outside State (Flow # 12) = 187 Million Bushels
Conversion to N:
% N in Soybean grain [Source: (Salvagiotti, et al. 2008) ] = 6.34 %
Moisture in Soybean Bushel = 13 %
Weight of Soybean bushel = 60 lb
N flow as exports outside of state = 187 x (10^6) x (1 - 0.13) x 60 x 0.0634 = 6.19E+08 lb of N = 2.81E+05 metric tons of N
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File: 0MB%20Singh%20et%20al.%202017%20Ecol%20Modell%20Supp%20Data.docx
Page: 1
Context: Further, about 70 % of flour being used in Industries is used by the “Wholesale Bakery” sector ad 30 % is used in “Breakfast Cereal and Other Producers”. Distribution of Flour Processes to Different Product CategoriesIndustry Sector Use of Flour% of UseAmount Used (Pounds of Flour)Wholesale Bakery Use703.88E+08Breakfast Cereal/Other Producers301.66E+08Distribution of Flour Used in Wholesale Bakery UseIndustrial UsePounds of FlourBread and Cake Manufacturing2.91E+08Cookie & cracker Manufacturing9.70E+07Distribution of Flour Processed in Breakfast, Cereal etc.SectorTotal cost of materials ($1,000)% of total input as materials (assuming same price of flour for both)Flour Input (pounds of flour)Tortilla manufacturing35,7890.111.83E+07Snack food manufacturing289,5040.891.48E+08Table 8: Wheat Data and Sources| Data | Source | Year | Use in PIOT | Value |
| -------- | -------- | -------- | -------- | -------- |
Wheat production in Illinois (Bushels) | NASS Census | 2002 | Not directly used | 2.79E+07 |
Wheat Acres Planted | NASS Census | 2002 | Used for calculation of N fertilizer inputs | 660,000 |
Per capita Wheat Consumption | Economic Research Service (USDA) – Wheat Supply & Use Data | 2002 | Used for calculation of Wheat consumption in Illinois | 136.9 pounds/person |
Illinois State Population in 2002 | | 2002 | Use for calculation of total wheat consumption in Illinois | 12,586,447 |
Seeding Rate | USDA-ERS Seed Report | 2002 | Used for calculation of seed used in Illinois | 73 pounds/acre (The seeding rate is for winter wheat since Illinois mainly grows winter wheat) |
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File: 0MB%20Singh%20et%20al.%202017%20Ecol%20Modell%20Supp%20Data.docx
Page: 1
Context: Assumption 2. Each stats has approximately the same distribution of wet mill and dry mill processes as the National Average (ie 60 % in dry mill and 40 % in Wet Mill)
How much Corn-Ethanol is produced in Illinois for 2002 ?
Total US Ethanol Production Capacity (2002) = 2738 million gallons/year
Ethanol Production Capacity for Illinois in 2002 = 726 million gallons/year
Source: http://www.ethanolrfa.org/page/-/objects/pdf/outlook/outlook_2002.pdf?nocdn=1
% of US Ethanol Produced in Illinois: 26.515 %
Therefore, Ethanol Produced in Illinois (2002)
= .26515 x (2130) million gallons = 564.769 million gallons
Ethanol Produced by Dry Milling vs Wet Milling in Illinois
Wet Milling = 40 % of total production = 0.40 x 564.769 = 225.91 million gallons
Dry Milling = 60 % of total production = 0.60 x 564.769 = 338.86 million gallons
Conversion of Corn-Ethanol Produced to Bushels of Corn
Assumption: 1 bushel = 2.79 gallons of ethanol [Source: RFA]
Corn Bushels Used in Dry Mills = 121.459 million bushels [= 338.86/2.79]
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File: 0MB%20Singh%20et%20al.%202017%20Ecol%20Modell%20Supp%20Data.docx
Page: 2
Context: The o
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File: Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx
Page: 12
Context: Table C3. The performance of inorganic metal oxide sorbents
for REE collection from geothermal water | Sorbent | Adsorption of REEs in geothermal water (%) |
| -------- | -------- |
| La | Eu | Ho |
Magnetic particles | |
Mn doped Fe3O4 (8nm) | 99 | 100 | 99 |
Mn doped Fe3O4 (25nm) | 98 | 94 | 80 |
Mn doped Fe3O4 (cluster) | 99 | 100 | 95 |
None-magnetic particles | |
MnO2-SiO2 composite | 99 | 100 | 94 |
MnO2-SiO2 composite (calcined) | 99 | 100 | 99 |
MnO2-Cabosil | 99 | 99 | 95 |
Fe/MnO2-SiO2 | 99 | 100 | 96 |
MnO2 Eichrom | 16 | 51 | 58 |
Bare substrates materials |
Fe3O4 (8nm) | 99 | 98 | 87 |
Fe3O4 (25nm) | 66 | 62 | 37 |
Core Fe3O4 (cluster) | 93 | 83 | 64 |
Cabosil SiO2 | 0 | 1 | 13 |
Nanopore SiO2 (Davisil 635) | 0 | 0 | 1 |
REE concentration of ~40 ppb, Equilibrium pH~7.7, L/S 50000 mL/g, contact time for 7 hours.
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File: 0MB%20Singh%20et%20al.%202017%20Ecol%20Modell%20Supp%20Data.docx
Page: 1
Context: -- Wheat Milled in Illinois = 0.07 * 212,609 = 14882.63 (1000 grain-equivalent bushels) = 1.49E+07 bushels
-- Conversion to Pounds of Flour :
-- 1 bushel = 43.8 pounds of floor
-- Wheat Milled in Illinois = 6.52E+08 pounds of floor being produced
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File: 0MB%20Singh%20et%20al.%202017%20Ecol%20Modell%20Supp%20Data.docx
Page: 1
Context: Soybean used for seeds in Million Bushels = 1.21 x (Area Harvested in Illinois)
= (1.21 x 1.05E+07) bushels
= 12.607 million bushels
1) Flow of Soybean Bushels for Crushing in Soybean & Other Oilseed Processing Sector (Flow # 2)
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File: Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx
Page: 10
Context: iol (sulfur): based surface chemistry has no efficacy for the collection of REEs. However, this ligand shows very high affinity for valuable “soft” metals such as Au, Ag, Cu, and Zn as well as secondary metals such as (Pb, Cd, Hg and other toxic heavy metals) that are more soluble/potentially present at higher concentrations than REEs in geothermal waters.
-- Manganese oxides and doped manganese oxides: these inorganic materials are relatively inexpensive, stable over a high temperature range and we have shown them to be effective for collection of REEs and other metals. However, they lack selectivity and have slower kinetics than organic surface chemistries. These materials may enable effective collection of Li and Mn.
Table 1. The performance of organic and inorganic sorbent materials
for collection of REEs and selected metals from geothermal water| Sorbent | Adsorption of REEs and other trace metals
In geothermal water (%) |
| -------- | -------- |
| La | Eu | Ho | Ag | Zn | Cu |
Organic sorbent chemistries | | | |
Diphos on silica supports | 96 | 99 | 99 | 97 | 62 | 51 |
PropPhos on silica supports | 98 | 99 | 100 | 23 | 100 | 93 |
Inorganic sorbent materials | | | |
Mn doped on Fe3O4 supports | 99 | 100 | 95 | 80 | 99 | 96 |
MnO2 on silica supports | 99 | 100 | 99 | 89 | 84 | 96 |
Initial concentrations of REEs, Ag and Zn were ~40, ~19 and 80 ppb respectively. Test solution was geothermal solution from Sharkley hot spring in Idaho—a region with rich mineralization, including REEs. pH~7.7, liquid to sorbent ratio of 50,000 mL/g, 2 hour batch contact adsorption with gentle agitation.
Additional experimental details available in appendix E. Location Sharkley hot springs and mineralogy shown in appendix B.
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File: 0MB%20Singh%20et%20al.%202017%20Ecol%20Modell%20Supp%20Data.docx
Page: 1
Context: Total Area of Land Harvested for Soybean (2002) = 1.05E+07 [Source: NASS, USDA]
Total fertilizer consumed for Soybean in Illinois: 2.10E+08 pounds of Nr
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File: Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx
Page: 3
Context: Advanced Separation Materials
PNNL has recently developed collection materials and green extraction methods that enable recovery of critical resources, such as PMs and REs, from previously nonviable low grade sources. Collection of valuable resources from dilute industrial waste streams and other low concentration sources reduces emission of toxic metals into the environment while providing a value added process for recovery and recycling of metals. PNNL’s novel sorbent materials significantly outperform other sorbents in the extraction (and subsequent release) of low levels of valuable metals from various acidic and high salt solutions. As shown in Tables 1 and 2 below, the PNNL materials have demonstrated unequalled chemical affinity for trace element collection relevant to geothermal mineral extraction, typically 10-1000x better than comparable sorbents while allowing for facile release of captured material and subsequent regeneration of the sorbent. This superior sorbent performance results from careful integration of inexpensive polymers, high surface area ceramics, and novel selective (and
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File: Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx
Page: 12
Context: Mn modified surfaces of magnetic particles and non-magnetic particles show the outstanding performance for collection of REEs from geothermal water, over 99% adsorption of REEs were observed from Mn-doped Fe3O4 (8nm) and MnO2-SiO2 composite (calcine). They also show excellent uptake for some base and toxic metals. The MnO2-SiO2 composite (calcine) also shows high affinity for Ag.
-- Mn modified magnetic particles show excellent uptake for REEs from geothermal water. Different sizes and structures of magnetic particle offer similar performance for REE uptake.
-- Mn doped Fe3O4 (8nm) and Mn doped Fe3O4 clusters also show excellent uptake for Cu, Zn and toxic metals. But significantly increase in uptake of Ag and Mn can be seen when compared to Mn doped Fe3O4 (8nm).
-- Interesting uptake of Ge, which is significantly higher that other sorbent materials including the organic sorbent materials, can be seen from Mn doped Fe3O4 (8nm) as well as Fe3O4 (8nm)
-- Mn modified non-magnetic sorbents provide similar performances; over 94% of REE adsorption can be seen. Their performances are much higher than a commercial sorbent (MnO2 Eichrom) that has the same surface chemistry and similar particle size.
-- While they have similar performance for REE collection, MnO2-SiO2 composite (calcined) and Fe/MnO2-SiO2 also show good uptake for valuable metals, (Ag), most of base metals and toxic metals from geothermal water.
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File: Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx
Page: 9
Context: -- Diphosphonic acid: this surface chemistry has a ligand that contains two phosphonic acid groups (shown in Figure 1). It is stable in a wide pH range and has shown high affinity for hard Lewis acid metals such as REEs and harder transition metals. However the high chemical affinity can make stripping of the mineral for the sorbent challenging.
-- Phosphonic acids: this surface chemistry contains single phosphonic acid groups (shown in Figure 1). It is stable in a wide pH range (0-8.5) and has shown good affinity for hard Lewis acid metals such as REEs, uranium and “harder” transition metals. The synthesis of the materials is simpler than diphosphonic acid. Further, recovery of collected materials from phosphonic acid based sorbents is typically easier (when compared to diphosphonic acid) supporting more economical processing and longer sorbent life times.
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File: 0MB%20Singh%20et%20al.%202017%20Ecol%20Modell%20Supp%20Data.docx
Page: 1
Context: Rate of Nitrogenous fertilizer use on Soybean in Illinois (2002) = 20 pounds/acre [Source: USDA http://www.ers.usda.gov/data-products/fertilizer-use-and-price.aspx#26744]
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Final Files Sources: Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx - Page 7, Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx - Page 5, 0MB%20Singh%20et%20al.%202017%20Ecol%20Modell%20Supp%20Data.docx - Page 1, Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx - Page 9, Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx - Page 12, 0MB%20Singh%20et%20al.%202017%20Ecol%20Modell%20Supp%20Data.docx - Page 4, Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx - Page 8, Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx - Page 13, Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx - Page 6, Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx - Page 4, Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx - Page 2, Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx - Page 11, Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx - Page 1, 0MB%20Singh%20et%20al.%202017%20Ecol%20Modell%20Supp%20Data.docx - Page 3, Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx - Page 3, Recovery%20of%20REEs%20from%20Geothermal%20Waters%20with%20Advanced%20Sorbents%20.docx - Page 10, 0MB%20Singh%20et%20al.%202017%20Ecol%20Modell%20Supp%20Data.docx - Page 2
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FINAL ANSWER
Answer: The provided context consists of two files: "Recovery of REEs from Geothermal Waters with Advanced Sorbents.docx" and "0MB Singh et al. 2017 Ecol Modell Supp Data.docx".
**"Recovery of REEs from Geothermal Waters with Advanced Sorbents.docx"**
This file describes a research project focused on developing and demonstrating a technology for extracting rare earth elements (REEs), precious metals (PMs), and other critical materials from geothermal waters. The project aims to provide additional revenue for geothermal operations by utilizing high-performance solid-state sorbent materials. The file details the project's objectives, program structure, and key milestones. It also discusses the challenges associated with solid-state sorbent technology for geothermal mineral extraction, including sorbent affinity and capacity, kinetics, lifetime, form factor, mineral recovery, and cost effectiveness. The file includes appendices that provide detailed information on the analysis of geothermal fluids, the evaluation of sorbent chemistries and structures, and experimental details for sorbent testing.
**"0MB Singh et al. 2017 Ecol Modell Supp Data.docx"**
This file presents supplementary information for a research paper titled "A Nitrogen Physical Input-Output Model for Illinois". The file describes the development of a nitrogen physical input-output model (N-PIOT) for Illinois, which tracks nitrogen flows driven by major commodities in the region. The file includes a flow diagram for the development of the N-PIOT model, a material flow analysis (MFA) diagram for major nitrogen flows in Illinois, and detailed calculations for each flow. The file also provides information on the conversion factors used to convert flows to nitrogen, the sectors included in the N-PIOT model, and the data sources used for the analysis.
In summary, the context provides information on a research project focused on extracting valuable minerals from geothermal waters and a supplementary data file for a research paper on nitrogen flows in Illinois.
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