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Mustard WasteDesign Midterm Report
http://www.howiamlosingweight.com/wp-content/uploads/2013/09/Mustard-forms.jpg
The “Second Most Ethical” BE Team:Matt Rosen, Ian Melville, Cahner Jennice, Matt Rimer, Kira Bartlett
The Company
Olds Products
Located in Pleasant Prairie, Wisconsin
http://www.oldsproducts.com
Mustard Production
Batch system (seasonal emphasis) - 9000 gallon limit
Two shifts a day (20-24 hours)
Ingredients: mustard seed, vinegar, brine, spices and water
Automatically metered into batch with minor ingredients sometimes added by operator
Slurry is agitated accordingly then pulverized into mustard paste which is then pumped to storage tank to await packaging
Waste Production
Olds Products is subject to the FDA’s cleaning regulations
Machines are cleaned with each flavor change, which is multiple times per day
-Cleaning water must be at least 120 °F
End of week extensive cleaning with hot water and caustic wash
All waste pumped into 6,000 gallon reservoir
The Problem
The Problem
Wastewater cannot be discharged through the sewer system to the Pleasant Prairie municipal treatment plant.
-pH is too acidic (3.3)
-Required pH range: 5.5-9 pH (Kenosha)
-Problems with high salinity and discharge amount
Current Solution - land application method via a third party company
-Expensive! $0.07 per gallon ($200,000 annually)
http://www.wrc.org.za
Land Application
Labor Intensive
Seasonal - Can’t apply to snow or frozen land
Potential Odor near residential areas
Excess nutrient runoff contaminate surrounding water
Needs strict monitoring and precise application
Adds nutrients to depleted soil
Simplest design
Project Goals
Solve immediate problem of waste disposal
-On site treatment
-Make water suitable for off-site treatment
Create/obtain a usable and harvestable byproduct
Create Economic and Sustainable viability
Project Goals
Bioprocess
-Avoid use of chemical reagent to neutralize pH by using a bio-treatment
-Biological treatment of water for recycling throughout facility
Structural
-Incorporate current wastewater reservoir (6,000 gallon tank)
-Design simply & maximize economy of space
Mechanical
-Simplicity and efficiency of design
-Minimize energy usage - strive to be energy neutral
Consideration
Safety
-Working with chemicals and reagents
-Industrial food plant - certain regulations
Ecological
-Impact of treated water products on environment
-Distinct seasonal change in Wisconsin
Ethical
-Company contact is the relative of a team member
Constraints
Geographic: Pleasant Prairie, WI v. Clemson, SC
Budget
Municipal Codes (Wastewater treatment guidelines)
Current operating procedures
Limited information - NO PREVIOUS WASTE ANALYSIS
Overall lack of team experience
FDA regulations
Design Questions
User Perspective:How does it work?
What do I need to do to run it?What is the maintenance/upkeep needed?
Client Perspective:How much will it cost?
What is the system's size?Can it be easily incorporated into other facilities?
Designer Perspective:What is the problem with the waste?
How much waste needs to be processed? At what rate?Is there a maximum start up cost or ROI timeframe?
LITERATURE REVIEW/THEORY/
PRELIMINARY DATA
Separation
Possible Filtration Methods
Gravity Filtration
Pressure Filtration
Centrifugation
http://industrial.centrifugemachinery.com/industrial_centrifuge.jpg
Harrison 120
Gravity Filtration w/o membrane
500mL Waste
Insert mixed waste into conical vessel
24 hours settling time
Settling speed from
Stokes Law
K. Bartlett
Imhoff Cone Separation
70% aqueous solution30% solids
Pressure Filtration
Modeled with vacuum filtration 0.45um filters and 11um filters
Have to backwash a physical filter
dictated by Darcy’s law
K. Bartlett
Centrifugation
Multiple levels of separation - Solids - Oils - Water
Faster separation speed
No filter build-up (no filter)
More advanced build, more energy
http://3.bp.blogspot.com/_xW3FQUQ2DYI/Rp4DF1r_0HI/AAAAAAAAAhY/B5MzdxVSV6I/s400/centrifugation.png
http://www.sigmaaldrich.com/technical-documents/articles/biofiles/centrifugation-basics.html
Coagulation and Flocculation
Assembles smaller suspended particles into larger particles
Easier and faster to separate or filter
Inorganic Coagulants require alkalinity
Organic = Polyamines
Remove salinity and
neutralize pH
http://image.slidesharecdn.com/typesofcoagulants-131004100124-phpapp01/95/types-of-coagulants-3-638.jpg?cb=1380881416
Lab Testing
Electrolysis
http://energy.gov/eere
Zoulias, E., Varkaraki, E., Lymberopoulos, N., Christodoulou C., Karagiorgis, G. (2012) A Review on Water Electrolysis. Centre for Renewable Energy Sources and Energy Efficiency.
Kargi, F. and Arikan, S. 2013. “Electrohydrolysis of Vinegar Fermentation Wastewater for Hydrogen Gas Production Using Different Types of Electrodes.” J. Environ. Eng., 139(6), 881–886.
Uses an electric current to dissociate water into hydrogen and oxygen gases.
The electric potential shifts positive ions ( H+) towards the cathode and the negative ions (OH-) towards the anode.
2 H2O(l) --> O2(g) + 4 H+(aq) + 4 e-
2 H2O(l) + 2 e- --> H2(g) + 2 OH-(aq)
2 H2O(l) --> O2(g) + 2 H2(g)
Negative Energy balance
Electrolysis
Graphite Electrode Gas Production at Cathode
Collected the gas produced at cathode
Future testing using Gas Chromatography
pH change from 3.24 to 3.14
K. BartlettK. Bartlett
Component/Property Analysis
Total Suspended Solids
Testing by the Clemson Agriculture Lab
High Performance Liquid Chromatography (HPLC)
Titration
TSS Testing
Unfiltered Solution
– 19.5 g/L
Filtered Solutions
– Gravity Separated
• 0.335 g/L
Unfiltered, Mixed
Gravity Separated, Aqueous
K. Bartlett
Clemson Agriculture LabOriginal Solution
(ppm)Filtered Solution
(ppm)Percent
Reduction (%)Phosphorous 581.82 158.82 72.7
Potassium 335.89 231.2 31.17
Calcium 214.73 104.4 51.38
Magnesium 129.56 92.3 28.76
Zinc 2.56 1.06 58.59
Copper 0.32 0.07 78.13
Manganese 0.85 0.54 36.47
Sulfur 359.889 259.08 28.01
Sodium 2749.7 1118 59.34
HPLC
Nitric Acid (0.9%)
Acetic Acid(0.43%)
Sinapic Acid???
Acetic Acid
Nitric Acid
Lab Solution Comparison
Solution of known acidic components created in lab to determine accuracy of results and compare pure solution to wastewater
Peaks of lab solution coincided with peaks from wastewater
pH of Lab solution was 1.2 significantly lower than the wastewater (3.3)
-Possible Buffers:
Nutrients?
Solids?
Other Acid?
Neutralization (pH increase)pH of original solution: 3.3
Target pH: Between 5.5 and 6.5
Titrations
Used Sodium Hydroxide (NaOH) with both filtered and unfiltered water
Compared use of Sodium Hydroxide to Sodium Bicarbonate (NaHCO3)
Titration Testing
-Titrated with 0.1 Molar Sodium Hydroxide in 50 mL of WasteWater
Non-Filtered Vs. Filtered
51 mL to raise pH to 6= 0.0051 moles and 0.204 grams of NaOH
32 mL to raise pH to 6= 0.0032 moles and 0.127 grams of NaOH
Titration Testing
Titration Comparison using filtered water
-0.5 M Sodium Bicarbonate vs . 0.1 M Sodium Hydroxide
10.5 mL to raise pH to 6= 0.0053 mols and 0.44 grams of NaHCO3
32 mL to raise pH to 6= 0.0032 moles and 0.127 grams of NaOH
Antimicrobial Potential
Sinapic Acid
-Phenolic antioxidant: effective against many gram positive and gram negative bacteria
Yellow Mustard
-Sinalbin (4-hydroxybenzyl glucosinolate) --> Benzyl isothiocyanate
->354.77 mg/g freeze dried mustard powder
Oriental Brown Mustard
-Sinigrin (2-propenyl glucosinolate)--> Allyl isothiocyanate
->548.16 mg/g freeze dried mustard powder
Herzalleh and Holley (2012) “Determination of sinigrin, sinalbin, allyl- and benzyl isothiocyanates by RP-HPLC in mustard powder extracts.”
John Abercrombie (Clemson Microbiology Department)
Wastewater Samples:
-Gravity separation (solid & aqueous components)
Original pH and adjusted pH
-Filtered solids from .45 μm membrane
Washed and Unwashed
-TSS solids from 11 μm membrane
Bacteria: P. aeruginosa, P. vulgaris, S. aureus, E. aerogenes, B. subtilis, M. luteus, E. coli, E. faecalis
Antimicrobial Testing
DESIGN METHODOLOGY & MATERIALS
MUSTARD FACTORY WASTEWATER
SEPARATION
AQUEOUS
SOLIDS
ELECTROLYSIS
ANTIMICROBIAL
DISPOSAL VIA TREATMENT PLANT
LAND APPLICATION
BIOLOGICAL TREATMENT
pH ADJUSTMENT
TO MUNICIPAL FACILITY
RECOVERY OF PRODUCTS
GREYWATERRECYCLED
WATER
BIOPESTICIDE
pH NEUTRALIZATION
Preliminary Design
Basic solution
-A pH neutralization system that adjusts the pH of the wastewater to an acceptable level so it can be sent to the municipal treatment facility
Preferred Solution
-Chain of reactor subsystems
-Each branch in the design tree represents a different sub-system that may be implemented into the overall design
-Overall design options vary through multiple possible pathways.
Separation
Gravity Filtration
2-3 10,000 Gallon Tanks
24-Hour Settling Time
Within estimated EPA limits
Gravity Filtration 98% reduction
http://www.industrial-equipment.biz/assets/images/Cone-Tank-Separator.jpg
– Pre-Filter 737 kg solids / day
– Post- Filter 12.7 kg solids/ day
– 724 kg solids filtered off / day
MUSTARD FACTORY WASTEWATER
SEPARATION
AQUEOUS
SOLIDS
ELECTROLYSIS
ANTIMICROBIAL
DISPOSAL VIA TREATMENT PLANT
LAND APPLICATION
BIOLOGICAL TREATMENT
pH ADJUSTMENT
TO MUNICIPAL FACILITY
RECOVERY OF PRODUCTS
GREYWATERRECYCLED
WATER
BIOPESTICIDE
pH NEUTRALIZATION
Aqueous
pH Adjustment
Need to decide when to adjust pH
Depends on selected design components
Currently modeling to adjust to pH 6
Chemical Adjustment
Cost
By-products
Chemical pH adjustment
NaOH: Sodium Hydroxide
Acetic Acid Reaction:
CH3COOH + NaOH H20 + CH3COONa (Sodium Acetate)
Nitric Acid Reaction:
HNO3 + NaOH H20 + NaNO3 (Sodium Nitrate)
Chemical pH adjustment
NaHCO3: Sodium Bicarbonate
Acetic Acid Reaction:
CH3COOH + NaHCO3 H20 + CO2 + CH3COONa (Sodium Acetate)
Nitric Acid Reaction:
NaHCO3 + HNO3 H2O + CO2 + NaNO3 (Sodium Nitrate)
Neutralization Cost Analysis
Biological Treatment
Adjust pH and then use biological methods to further treat the water
Could be used to reduce C.O.D, B.O.D, and other inorganic constituents
Biomass production → possible harvestable co-product
Electrolysis
Gas Production at Cathode
Potentially hydrogen gas per theory of electrolysis
Need to test the gas using Gas Chromatography
Potential for slight pH increase
Would need subsequent neutralization
Sample tested reduced pH by 0.1
Acid Extraction and Recovery
Sinapic Acid (>98%: $49.30/g)
Acetic Acid (ACS grade: $0.035/mL) (0.43% of waste solution)
Nitric Acid (ACS grade: $0.224/mL) (0.9% of waste solution)
Extraction Method
Recovery of Products
Pricing from VWR
Water Capture and ReuseGreywater
-Toilets, irrigation
Water Recycling
-Cleaning Production Tanks
Rinsing between flavor changes
End of the week cleaning
Currently using potable city water
-Majority of water usage is for batch making
Currently updating piping & pumps
Reduces amount of wastewater produced
MUSTARD FACTORY WASTEWATER
SEPARATION
AQUEOUS
SOLIDS
ELECTROLYSIS
ANTIMICROBIAL
DISPOSAL VIA TREATMENT PLANT
LAND APPLICATION
BIOLOGICAL TREATMENT
pH ADJUSTMENT
TO MUNICIPAL FACILITY
RECOVERY OF PRODUCTS
GREYWATERRECYCLED
WATER
BIOPESTICIDE
pH NEUTRALIZATION
Solids
Antimicrobial/Biopesticide
Antimicrobial or Biopesticide AgentCollect solids to re-sell
Potential Issues with ApplicationNutrient content, SalinityPresence of cleaning agentsOrganic Regulations
Processing, Storage, and Transportation requirements
Further Testing
publish.illinois.edu
Sustainability Measures
On-site treatment
-Eliminate the cost of outsourcing wastewater
-Minimize resources used for disposal/treatment
Biological treatment methods
-Less expensive than chemical treatment
-Naturally occurring process, non toxic
Sustainability Measures
Recycling water back through facility
-Cost effective
-Reduce fresh water used and amount of treatment necessary
Generate coproducts
-Economic sustainability from additional revenue
-Antimicrobial benefits (possibly a more organic/natural option)
Sustainability Measures
Social sustainability
-Recycling/reuse of materials, decrease pollutants
Ethical sustainability
-Meet all guidelines/requirements
Efficiency
-Practical, eco-friendly, cost efficient
Societal issues
-not restricted to specific population http://www.aiche.org
Sustainability Measures
Carbon Footprint
-Minimal fossil fuel carbon emissions
Water Footprint
-Reduce need/use of freshwater
ecology110fra.wordpress.com
Schedule
ReferencesCheng, S. and Logan, B. (2007). Sustainable and Efficient Biohydrogen Production via Electrohydrogenesis. Proceedings of the National Academy of Sciences of the United States of America. vol. 104. no. 47. 18871-18873
Engels, C., Schieber, A., Ganzle, M. (2011). “Sinapic acid derivatives in defatted Oriental mustard (Brassica juncea L.) seed meal extracts using UHPLC-DAD-ESI-MS and identification of compounds with antibacterial activity.” Eur Food Res Technol. 234, 535-542
Harrison, R., Todd, P., Rudge, S., Petrides, D. 2003. Bioseparations Science and Engineering. New York, N.Y.: Oxford University Press.
Herzallah, S. and Holley, R. (2012) “Determination of sinigrin, sinalbin, allyl- and benzyl isothiocyanates by RP-HPLC in mustard powder extracts.” LWT - Food Science and Technology 47, 293-299.
Kargi, F. and Arikan, S. (2013). ”Electrohydrolysis of Vinegar Fermentation Wastewater for Hydrogen Gas Production Using Different Types of Electrodes.” J. Environ. Eng., 139(6), 881–886.
Niciforovic, N. and Abramovic, H. (2014) “Sinapic Acid and Its Derivatives: Natural Sources and Bioactivity” Comprehensive Reviews in Food Science and Food Safety 13, 34-51.
Popova, I. and Morra, M. (2014). “Simultaneous Quantification of Sinigrin, Sinalbin, and Anionic Glucosinolate Hydrolysis Products in Brassica juncea and Sinapis alba Seed Extracts Using Ion Chromatography.” Journal of Agricultural and Food Chemistry 62, 10687-10693.
Zoulias, E., Varkaraki, E., Lymberopoulos, N., Christodoulou C., Karagiorgis, G. (2012) A Review on Water Electrolysis. Centre for Renewable Energy Sources and Energy Efficiency. Available at: http://www.cres.gr/kape/publications/papers/dimosieyseis/ydrogen/A%20REVIEW%20ON%20WATER%20ELECTROLYSIS.pdf. Accessed 9 September 2015
Thank you!
Questions?