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Bioethanol,
Bioplastic and
Biofertilizer from
Rice Straw
Graham Walker, Madison Socha, Ashton
Guest
BE 4380
The Problem
● High levels of greenhouse gas emissions
○ Fossil fuel for automotive industry
○ Production of plastics
○ Production of fertilizer
● Need for renewable fuel source and products
○ Oil industry
○ Green energy
Objectives of the Project
● Bioprocessing
○ Biofuel
○ Bioplastic
○ Biofertilizer
● Structural
○ Fermentation equipment
○ Centrifuge equipment
○ Grinding equipment
● Mechanical
○ Bulk movement of rice in
○ Production material movement out
● Questions of each component:
○ User: How do bio products compare to
other products? What are the benefits?
○ Client: What are the cost analyses? Is it
mass distributable?
○ Designer: How can I make a sustainable
product? A fuel, plastic, or fertilizer? What
processes exist? How can I make the
process more efficient?
Constraints and Considerations
● Skills: Understanding of
SuperPro, thermodynamics,
bioprocessing
● Budget: startup cost and cost of
operation
● Space: Industrial sized
bioethanol production facility
● Logistics: Access to input
resources
● Time: 72 Hours
● Safety: Non toxic products that can be useful
for consumers.
● Ethical: Determine if our products are better for
people and the environment.
● Ecological: Product formation, advancement,
and research should work hand and hand with
caring for the environment.
● Ultimate uses: Create bio products that can
help reduce the amount of conventional
products used.
Governing Equations
(1) Acid Pretreatment
3 Rice Straw → H2SO4→ 0.16 Lignin + 0.4 Hemicellulose + 0.8 Cellulose
(2) Acid/Base Neutralization
H2SO4 + 2KOH → K2SO4 + 2 H2O
(3) Centrifuge
→ K2SO4
→ Lignin
→ Hemicellulose + Cellulose
(4) Hydrolysis
8 Biomass (hemi/cell) → 0.2 xylose + 0.9 glucose + 0.27 H2O
(5) Fermentation for Bioethanol Production
Glucose + Ammonia → Bacteria + CO2 + Ethanol
Xylose + Ammonia → Bacteria + CO2 + Ethanol
Possible solutions
● Renewable energy sources
○ PV and passive solar
○ Hydroelectric
○ Wind
○ Biofuels (ethanol and diesel)
● Sustainable transportation
○ Bicycles
○ Walking
○ Mass transit
○ Electric Vehicles
● Sustainable polymers
○ Compostable Plastics (LAPs)
○ Recycling
○ Wood fiber / lignin feedstock in
synthesis of plastics (sustainable)
● Sustainable fertilizers
○ Manure waste from meat farms
○ Biofertilizer from lignin
Why Bioethanol?
● Opposition to bioethanol:
○ Fundamental input yield
■ Corn ethanol requires 70% more energy than
what is stored in ethanol. (Cornell)
○ Not competitive in market
■ Gasoline gallon cost 95 cents (Cornell)
■ Corn Ethanol cost $1.74 (Cornell)
■ Difficulty of using cellulose and lignin
● Advocating for bioethanol:
○ Corn ethanol reduces GHG emissions by 34%. (afdc)
○ Cellulosic ethanol reduces GHG emissions anywhere
from 51 - 88% compared to gasoline. (afdc)
● Prior knowledge
○ Corn bioethanol is expensive and
competes with the food industry.
○ Does not come from oil reserves
○ Cellulosic ethanol:
■ Non food based (residue)
■ Feedstock includes cellulose,
hemicellulose, and lignin
○ Land use
■ Food vs. Energy
■ Infrastructure vs. Energy
○ Enzyme usages are the most
expensive component of bioethanol
production.(EDIS)
Analysis of Information
Cellulosic bioethanol:
● Corn ethanol
○ Expensive
○ Unsustainable
● Cellulosic bioethanol
○ Less expensive substrates
○ Does not compete with food industry
○ Syngas vs. Sugar platform
■ Syngas is much more expensive
■ Tars presence
● Inhibit enzyme growth
● Filtration and bioseparations
(biofuel journal)
Lignin waste:
● Can be used as a high value product with
ligninolytic bacteria
○ Feedstock for plastics
○ Fertilizer
○ Feedstock for bioethanol
● If too expensive to process
○ Send lignin to companies forming
these products above
○ Burn lignin for heating the fermenter
to save on costs
Design Options
Unit Operations
● Pretreatment
○ Grinding
○ Mixing
○ Acid/Base
● Centrifugation
○ Decanter
● Hydrolysis
○ Enzymes
● Fermentation Process
○ Distillation
■ Storage
● Cellulosic Bioethanol
○ Syngas vs. Sugar platform
■ Syngas is much more expensive
■ Tars presence
● Inhibit enzyme growth
● Filtration and bioseparations (biofuel journal)
○ Waste products
■ Bioethanol
● Back to fermentor
■ Bioplastics
● Feedstock sale
● Bioplastic synthesis (science direct)
■ Biofertilizer
● Microbial compost(science direct)
○ Three stage inoculum (science direct)
Synthesis of Design
Evaluation of Design
Strategic Components:
● Rice Straw Substrate
○ 650-975 million tons/yr produced
○ High cellulose/hemicellulose levels
○ Slow degradation in soil
○ Rice stem diseases
○ Waste of high mineral content
● Acid Pretreatment
○ Acid dilution to low concentration
● Neutralization
○ Sulfuric acid for substrate breakdown
○ Potassium hydroxide for neutralization
Strategic Components:
● B - glucosidase
○ Gives larger glucose yield (Drapcho)
● Bioethanol Sugar Platform
● Enzyme
○ Cellulase
● User: How do bio products compare to other
products? What are the benefits?
● Client: What are the cost analyses? Is it mass
distributable?
● Designer: How can I make a sustainable
product? A fuel, plastic, or fertilizer? What
processes exist? How can I make the process
more efficient?
Sustainability Highlights
● Product utilization
● Bioethanol 50 - 80% GPG reduction
compared to gasoline
● Contribute bioplastics to the 70 % of
plastic production that can be
sustainable
● Microbial biofertilizer
● Bioethanol sugar platform
Conclusions
Initial Reactant: 23,000 kg rice straw
Final Product: 4,800 L 95% pure bioethanol
Patents:
● Lignin to plastic
○ impregnate wood with a taxogen
liquid to form pre-polymer
○ burn off all excess and unwanted
taxogen remains
○ heating impregnated wood to form
co-polmer or plastic
References
Drapcho, Caye M. & Nhuan, Nghiem Phu., & Walker, Terry H. (2008). Ethanol Production. In Biofuels
Engineering Process Technology (pp. 133-158). The McGraw-Hill Companies, Inc.
(2001). Ethanol fuel from corn faulted as ‘unsustainable subsidized food burning’ in analysis by Cornell
scientist. Cornell University., http://news.cornell.edu/stories/2001/08/ethanol-corn-faulted-energy-waster-
scientist-says
Ethanol Feedstocks. Alternative Fuels Data Center, U.S. Dept. of Energy .
https://afdc.energy.gov/fuels/ethanol_feedstocks.html
Ethanol Vehicle Emissions. Alternative Fuels Data Center, U.S. Dept. of Energy.
https://afdc.energy.gov/vehicles/flexible_fuel_emissions.html
Rong Xu, Kai Zhang, Pu Liu, Huawen Han, Shuai Zhao, Apurva Kakade, Aman Khan, Daolin Du, Xiangkai Li,.
(2018). Lignin depolymerization and utilization by bacteria. Bioresource Technology, 269, 557-566.
https://www.sciencedirect.com/science/article/pii/S0960852418312227
Mamatha Devarapalli, Hasan K. Atiyeh,. (2015). A review of conversion processes for bioethanol production
with a focus on syngas fermentation. Biofuel Research Journal., 268-280.
https://www.biofueljournal.com/article_10157_cdea43a9e3c0102a0da7eaf903ebd5c0.pdf
● Lignin to Biofertilizer
○ Use plant slag and mushroom residue
○ Bacteria production of antibiotics and fertilizer
○ This process fights bacterial resistance
○ Creates good fertilizer as a byproduct
Talebnia, Farid & Karakashev, Dimitar & Angelidaki, Irini. (2010). Production of Bioethanol From Wheat Straw:
An Overview on Pretreatment, Hydrolysis and Fermentation. Bioresource technology. 101. 4744-53.
https://www.researchgate.net/publication/40766884_Production_of_Bioethanol_From_Wheat_Straw_An_Overv
iew_on_Pretreatment_Hydrolysis_and_Fermentation
Zhaohui Tong, Pratap Pullammanappallil, Arthur A. Teixeira. (2012). How Ethanol Is Made from Cellulosic
Biomass. IFAS extension, University of Florida. AE493, 1-4. http://edis.ifas.ufl.edu/pdffiles/AE/AE49300.pdf
Why sustainable plastics?. Green dot Bioplastics. https://www.greendotbioplastics.com/why-sustainable-
plastics/
Dolly Kumari, Radhika Singha. (2018). Pretreatment of lignocellulosic wastes for biofuel production: A critical
review. Renewable and Sustainable Energy Reviews. 90, 877-891.
https://www.sciencedirect.com/science/article/pii/S1364032118302041
Patents
Rodolfo Ripa, Alberto Garcia. (1975). Method of partially converting wood into a lignin
plastic polymer. US4026847A, USPTO. 1975-05-13.
https://patents.google.com/patent/US4026847A/en?q=lignin&q=plastics&oq=lignin+plastics
段得振, 吴力克, 边聪聪, 何菁. (2015). Microbial fertilizer production methods, and
obtained biofertilizer Compound Microorganisms. CN105110826B, Global Dossier. 2015-09-15.
https://patents.google.com/patent/CN105110826B/en?q=lignin&q=bacteria&q=biofertilizer&oq=lignin+bacteria+
biofertilizer
Appendix

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Bioprocess engineering biofuel project

  • 1. Bioethanol, Bioplastic and Biofertilizer from Rice Straw Graham Walker, Madison Socha, Ashton Guest BE 4380
  • 2. The Problem ● High levels of greenhouse gas emissions ○ Fossil fuel for automotive industry ○ Production of plastics ○ Production of fertilizer ● Need for renewable fuel source and products ○ Oil industry ○ Green energy
  • 3. Objectives of the Project ● Bioprocessing ○ Biofuel ○ Bioplastic ○ Biofertilizer ● Structural ○ Fermentation equipment ○ Centrifuge equipment ○ Grinding equipment ● Mechanical ○ Bulk movement of rice in ○ Production material movement out ● Questions of each component: ○ User: How do bio products compare to other products? What are the benefits? ○ Client: What are the cost analyses? Is it mass distributable? ○ Designer: How can I make a sustainable product? A fuel, plastic, or fertilizer? What processes exist? How can I make the process more efficient?
  • 4. Constraints and Considerations ● Skills: Understanding of SuperPro, thermodynamics, bioprocessing ● Budget: startup cost and cost of operation ● Space: Industrial sized bioethanol production facility ● Logistics: Access to input resources ● Time: 72 Hours ● Safety: Non toxic products that can be useful for consumers. ● Ethical: Determine if our products are better for people and the environment. ● Ecological: Product formation, advancement, and research should work hand and hand with caring for the environment. ● Ultimate uses: Create bio products that can help reduce the amount of conventional products used.
  • 5. Governing Equations (1) Acid Pretreatment 3 Rice Straw → H2SO4→ 0.16 Lignin + 0.4 Hemicellulose + 0.8 Cellulose (2) Acid/Base Neutralization H2SO4 + 2KOH → K2SO4 + 2 H2O (3) Centrifuge → K2SO4 → Lignin → Hemicellulose + Cellulose (4) Hydrolysis 8 Biomass (hemi/cell) → 0.2 xylose + 0.9 glucose + 0.27 H2O (5) Fermentation for Bioethanol Production Glucose + Ammonia → Bacteria + CO2 + Ethanol Xylose + Ammonia → Bacteria + CO2 + Ethanol
  • 6. Possible solutions ● Renewable energy sources ○ PV and passive solar ○ Hydroelectric ○ Wind ○ Biofuels (ethanol and diesel) ● Sustainable transportation ○ Bicycles ○ Walking ○ Mass transit ○ Electric Vehicles ● Sustainable polymers ○ Compostable Plastics (LAPs) ○ Recycling ○ Wood fiber / lignin feedstock in synthesis of plastics (sustainable) ● Sustainable fertilizers ○ Manure waste from meat farms ○ Biofertilizer from lignin
  • 7. Why Bioethanol? ● Opposition to bioethanol: ○ Fundamental input yield ■ Corn ethanol requires 70% more energy than what is stored in ethanol. (Cornell) ○ Not competitive in market ■ Gasoline gallon cost 95 cents (Cornell) ■ Corn Ethanol cost $1.74 (Cornell) ■ Difficulty of using cellulose and lignin ● Advocating for bioethanol: ○ Corn ethanol reduces GHG emissions by 34%. (afdc) ○ Cellulosic ethanol reduces GHG emissions anywhere from 51 - 88% compared to gasoline. (afdc) ● Prior knowledge ○ Corn bioethanol is expensive and competes with the food industry. ○ Does not come from oil reserves ○ Cellulosic ethanol: ■ Non food based (residue) ■ Feedstock includes cellulose, hemicellulose, and lignin ○ Land use ■ Food vs. Energy ■ Infrastructure vs. Energy ○ Enzyme usages are the most expensive component of bioethanol production.(EDIS)
  • 8. Analysis of Information Cellulosic bioethanol: ● Corn ethanol ○ Expensive ○ Unsustainable ● Cellulosic bioethanol ○ Less expensive substrates ○ Does not compete with food industry ○ Syngas vs. Sugar platform ■ Syngas is much more expensive ■ Tars presence ● Inhibit enzyme growth ● Filtration and bioseparations (biofuel journal) Lignin waste: ● Can be used as a high value product with ligninolytic bacteria ○ Feedstock for plastics ○ Fertilizer ○ Feedstock for bioethanol ● If too expensive to process ○ Send lignin to companies forming these products above ○ Burn lignin for heating the fermenter to save on costs
  • 9. Design Options Unit Operations ● Pretreatment ○ Grinding ○ Mixing ○ Acid/Base ● Centrifugation ○ Decanter ● Hydrolysis ○ Enzymes ● Fermentation Process ○ Distillation ■ Storage ● Cellulosic Bioethanol ○ Syngas vs. Sugar platform ■ Syngas is much more expensive ■ Tars presence ● Inhibit enzyme growth ● Filtration and bioseparations (biofuel journal) ○ Waste products ■ Bioethanol ● Back to fermentor ■ Bioplastics ● Feedstock sale ● Bioplastic synthesis (science direct) ■ Biofertilizer ● Microbial compost(science direct) ○ Three stage inoculum (science direct)
  • 11. Evaluation of Design Strategic Components: ● Rice Straw Substrate ○ 650-975 million tons/yr produced ○ High cellulose/hemicellulose levels ○ Slow degradation in soil ○ Rice stem diseases ○ Waste of high mineral content ● Acid Pretreatment ○ Acid dilution to low concentration ● Neutralization ○ Sulfuric acid for substrate breakdown ○ Potassium hydroxide for neutralization Strategic Components: ● B - glucosidase ○ Gives larger glucose yield (Drapcho) ● Bioethanol Sugar Platform ● Enzyme ○ Cellulase ● User: How do bio products compare to other products? What are the benefits? ● Client: What are the cost analyses? Is it mass distributable? ● Designer: How can I make a sustainable product? A fuel, plastic, or fertilizer? What processes exist? How can I make the process more efficient?
  • 12. Sustainability Highlights ● Product utilization ● Bioethanol 50 - 80% GPG reduction compared to gasoline ● Contribute bioplastics to the 70 % of plastic production that can be sustainable ● Microbial biofertilizer ● Bioethanol sugar platform
  • 13. Conclusions Initial Reactant: 23,000 kg rice straw Final Product: 4,800 L 95% pure bioethanol
  • 14. Patents: ● Lignin to plastic ○ impregnate wood with a taxogen liquid to form pre-polymer ○ burn off all excess and unwanted taxogen remains ○ heating impregnated wood to form co-polmer or plastic References Drapcho, Caye M. & Nhuan, Nghiem Phu., & Walker, Terry H. (2008). Ethanol Production. In Biofuels Engineering Process Technology (pp. 133-158). The McGraw-Hill Companies, Inc. (2001). Ethanol fuel from corn faulted as ‘unsustainable subsidized food burning’ in analysis by Cornell scientist. Cornell University., http://news.cornell.edu/stories/2001/08/ethanol-corn-faulted-energy-waster- scientist-says Ethanol Feedstocks. Alternative Fuels Data Center, U.S. Dept. of Energy . https://afdc.energy.gov/fuels/ethanol_feedstocks.html Ethanol Vehicle Emissions. Alternative Fuels Data Center, U.S. Dept. of Energy. https://afdc.energy.gov/vehicles/flexible_fuel_emissions.html Rong Xu, Kai Zhang, Pu Liu, Huawen Han, Shuai Zhao, Apurva Kakade, Aman Khan, Daolin Du, Xiangkai Li,. (2018). Lignin depolymerization and utilization by bacteria. Bioresource Technology, 269, 557-566. https://www.sciencedirect.com/science/article/pii/S0960852418312227 Mamatha Devarapalli, Hasan K. Atiyeh,. (2015). A review of conversion processes for bioethanol production with a focus on syngas fermentation. Biofuel Research Journal., 268-280. https://www.biofueljournal.com/article_10157_cdea43a9e3c0102a0da7eaf903ebd5c0.pdf ● Lignin to Biofertilizer ○ Use plant slag and mushroom residue ○ Bacteria production of antibiotics and fertilizer ○ This process fights bacterial resistance ○ Creates good fertilizer as a byproduct Talebnia, Farid & Karakashev, Dimitar & Angelidaki, Irini. (2010). Production of Bioethanol From Wheat Straw: An Overview on Pretreatment, Hydrolysis and Fermentation. Bioresource technology. 101. 4744-53. https://www.researchgate.net/publication/40766884_Production_of_Bioethanol_From_Wheat_Straw_An_Overv iew_on_Pretreatment_Hydrolysis_and_Fermentation Zhaohui Tong, Pratap Pullammanappallil, Arthur A. Teixeira. (2012). How Ethanol Is Made from Cellulosic Biomass. IFAS extension, University of Florida. AE493, 1-4. http://edis.ifas.ufl.edu/pdffiles/AE/AE49300.pdf Why sustainable plastics?. Green dot Bioplastics. https://www.greendotbioplastics.com/why-sustainable- plastics/ Dolly Kumari, Radhika Singha. (2018). Pretreatment of lignocellulosic wastes for biofuel production: A critical review. Renewable and Sustainable Energy Reviews. 90, 877-891. https://www.sciencedirect.com/science/article/pii/S1364032118302041 Patents Rodolfo Ripa, Alberto Garcia. (1975). Method of partially converting wood into a lignin plastic polymer. US4026847A, USPTO. 1975-05-13. https://patents.google.com/patent/US4026847A/en?q=lignin&q=plastics&oq=lignin+plastics 段得振, 吴力克, 边聪聪, 何菁. (2015). Microbial fertilizer production methods, and obtained biofertilizer Compound Microorganisms. CN105110826B, Global Dossier. 2015-09-15. https://patents.google.com/patent/CN105110826B/en?q=lignin&q=bacteria&q=biofertilizer&oq=lignin+bacteria+ biofertilizer

Editor's Notes

  1. Conventional fossil fuel industry in non-renewable, deplenishing, and causing negative environmental impacts. Current pertochemical plastics are produced with oil and have around a 800 year half life and remain and persist in the environment as microplastics even after they’ve begun to break down. Conventional fertilizer production produces nitrous oxide, a potent green house gas
  2. Safety: no toxins produced Ethical: renewable energy Ecological: ghg reduction and lignin production Potassium hydroxide Sulfuric acid Potassium sulfate
  3. Rice Straw and Biomass the superpro designer automatically gave us a MW
  4. Biofuels are unsustainable when the input energy BTUs are greater than the potential energy in the ethanol when using corn. A cornell scientist reported that 131,000 BTUs were needed to make one gallon of ethanol at an energy value of 77,000 BTUs. Ethanol from corn costs about $1.74 per gallon to produce, compared with about 95 cents to produce a gallon of gasoline. corn-based ethanol in place of gasoline reduces life cycle GHG emissions on average by 34%, depending on the source of energy used during ethanol production. Using cellulosic ethanol provides an even greater benefit. Depending on the feedstock, emissions reductions of cellulosic ethanol compared to conventional gasoline range from 51% to 88% when land-use change emissions are considered. Cellulosic feedstocks are non-food based and include crop residues, wood residues, dedicated energy crops, and industrial and other wastes. These feedstocks are composed of cellulose, hemicellulose, and lignin. Lignin is usually separated out and converted to heat and electricity for the conversion process. It's more challenging to release the sugars in these feedstocks for conversion to ethanol.
  5. For biofertilizers Hydrolytic aerobic and anaerobic bacteria (photosynthetic, lactic-acid, and nitrogen fixing bacteria), made an efficient compost for lignin The more lignin you have the faster the process
  6. Acid pretreatment Rice Straw → Biomass + lignin + Sulfuric Acid Acid/Base Neutralization Sulfuric Acid + potassium hydroxide → Lignin + Potassium Sulfate + Biomass Centrifuge separates them Hydrolysis Biomass breaks down into hemi/cell Fermentation glucose → bioethanol xylose → bioethanol Distillation
  7. Rice straw is largest biomass feedstock in the world B-gluc to hydrolysis phase
  8. Utilities cost is extremely high Reason: Large amount of rice stalk, Large amount of diluted acid, Large amount water, 100,000L/hr has to be heated and cooled during Fermentation and Hydrolysis Selling lignan at only 50 cent/kg Other options: Steam explosion is the most cost effective pretreatment process when using agricultural residues
  9. Plastics: three steps acquire wood and impregnate it with a taxogen liquid which forms a pre-polymer and when heated to the desired temperature will react to the lignin that is located in the wood. heat the impregnated wood to a desired temperature to burn off all excess and unwanted taxogen remains in order to form the pre-polymer. heating the impregnated wood long enough to form a co-polymer that attaches and links the lignin and the pre-polymer together in order to form the desired lignin plastic polymer product. Biofertilizer making microbial fertilizer, mushroom residue antibiotics as the base material, material comprises a bacteria-rich waste slag and antibiotics plant fibers; cellulolytic bacteria and Bacillus natto (Bacillus natto), one or more of beer yeast (Saccharomyces cereviseae) and Lactobacillus (Lactobacillus plantarum) in The present invention can solve the problem of refractory pharmaceutical antibiotics of fermentation bacteria slag, progressively, which may also take advantage of the beneficial ingredients into microbial fertilizer, to address the current soil compaction, fertility decrease.