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Executive Summary
The Senior Design team is designing a biodiesel production plant that uses triglyceride-containing
restaurant waste vegetable oil and grease as its feed source. The proposed plant will use waste vegetable
oil collected from local restaurants in Miami, FL and convert it to biodiesel. The main chemical reaction
in this process is called transesterification. This reaction converts triglycerides in the feed to methyl esters
(biodiesel) in the presence of an alcohol and a basic catalyst. The biodiesel produced will be compatible
with current diesel engines. The demand for alternative energy sources is increasing as the demand for
energy increases and global supply of fossil fuels decreases. Furthermore, restaurant grease is a waste
product with no further applications, which makes it an ideal feedstock for biodiesel production.
This design process prioritizes stewardship by recycling a waste product, caring by focusing on
safety, and transparency by adhering to all government regulations on product quality. Many variables
will be considered when designing this plant including: acid catalyst type, alcohol type, alkaline catalyst
type and reactor type. For the purpose of this preliminary feasibility study, the sulfuric acid, methanol,
sodium hydroxide, and a batch reactor will be used. There are three main process sections: pre-treatment,
post- treatment and settling, with waste product distillation in between each.
With these variables chosen, the project was found to be economically feasible. The initial
upfront construction costs were estimated to be $14.8 million. It was determined that a 10% rate of
return is obtained when the selling price for biodiesel is $3.41. This falls in line with current
biodiesel plant pricing. Rough Ppreliminary cost estimates predict aA yearly profit of $1.8 million
will would occur at this selling price, with a plant lifespan of 20 years. The customer will be fuel
distributors with existing infrastructure to provide the public with blended biodiesel. Infinite demand
will be assumed with potential competition coming from the diesel market.
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Table of Contents
Executive Summary ................................................................................................................................ 2
Table of Contents .................................................................................................................................... 3
Table of Figures .................................................................................................................................. 106
Table of Tables.................................................................................................................................... 117
1. Introduction ..................................................................................................................................... 128
1.1 Background Information ............................................................................................................ 128
1.2 Objective ................................................................................................................................... 139
1.3 Scope......................................................................................................................................... 149
1.4 Past Project Teams ................................................................................................................... 1410
1.5 Feasibility ................................................................................................................................ 1510
1.5 Comparing Biodiesel and Petroleum Diesel.............................................................................. 1611
1.5.1 Differences in Chemistry ................................................................................................... 1611
1.5.2 Engine Modification.......................................................................................................... 1712
1.5.1 Engine Performance .......................................................................................................... 1712
2. Design Norms................................................................................................................................ 1813
2.1 Stewardship ............................................................................................................................. 1814
2.2 Caring...................................................................................................................................... 1914
2.3 Transparency ........................................................................................................................... 1914
3. Team Organization ........................................................................................................................ 2015
Team Responsibilities ................................................................................................................ 2016
Hannah Albers ........................................................................................................................... 2116
Ben Guilfoyle ............................................................................................................................ 2116
Melanie Thelen .......................................................................................................................... 2116
Cole Walker .............................................................................................................................. 2117
4. Process Overview .......................................................................................................................... 2217
4.1 Process Research ..................................................................................................................... 2317
4.1.1 Block Flow Diagram ......................................................................................................... 2317
4.1.2 Reaction Chemistry ........................................................................................................... 2418
4.1.3 Key Variables ................................................................................................................... 2619
4.1.4 Design Alternatives ........................................................................................................... 2821
4.2 Material Research .................................................................................................................... 3022
4.2.1 Feed Sources ..................................................................................................................... 3022
4.2.2 Feed Composition Research .............................................................................................. 3023
4.2.2 Product ............................................................................................................................. 3325
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5. Preliminary Design ........................................................................................................................ 3426
5.1 Transesterification Reactor ...................................................................................................... 3426
5.1.1 Mass Transfer Limitations ................................................................................................. 3526
5.1.2 Design Alternatives ........................................................................................................... 3627
5.2 Catalyst ................................................................................................................................... 4132
5.2.1 Design Criteria .................................................................................................................. 4132
5.2.3 Design Alternatives ........................................................................................................... 4132
5.2.4 Past Design Teams ............................................................................................................ 4333
5.2.5 Design Decision ................................................................................................................ 4334
5.3 Pre-Treatment Section ............................................................................................................. 4334
5.3.1 Filter ................................................................................................................................. 4334
5.3.2 Acid Treatment ................................................................................................................. 4536
5.3.3 Waste Separation .............................................................................................................. 4838
5.4 Post-Treatment Section ............................................................................................................ 4839
5.4.1 Glycerin Separation ........................................................................................................... 4939
5.4.2 Methanol Recovery ........................................................................................................... 5242
6. Equipment ..................................................................................................................................... 5343
6.1 Equipment Listing ................................................................................................................... 5343
7. Safety Considerations .................................................................................................................... 5645
7.1 Chemicals ................................................................................................................................ 5645
7.2 Operating ................................................................................................................................. 5746
8. Business Plan ................................................................................................................................ 5847
8.1 Market Study ........................................................................................................................... 5847
8.1.1 Customer .......................................................................................................................... 5948
8.1.2 Competition ...................................................................................................................... 6049
8.2 Tax Information ....................................................................................................................... 6150
8.3 Costs ....................................................................................................................................... 6151
8.3.1 Capital Costs ..................................................................................................................... 6151
8.3.2 Operating Costs................................................................................................................. 6251
8.4 Profitability ............................................................................................................................. 6252
9. Conclusion .................................................................................................................................... 6554
References......................................................................................................................................... 6655
Appendix .......................................................................................................................................... 7158
1. Overall Process Mass Balance.................................................................................................... 7158
2. Filter Calculations...................................................................................................................... 7259
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3. Settler Calculations .................................................................................................................... 7360
4. Competing Biodiesel Plants in Florida ....................................................................................... 7561
5. Material Safety Data Sheets (MSDS) ......................................................................................... 7561
Executive Summary ..................................................................................................................................
Table of Contents ......................................................................................................................................
Table of Figures ...................................................................................................................................... 5
Table of Tables........................................................................................................................................ 6
1. Introduction ......................................................................................................................................... 7
1.1 Background Information ................................................................................................................ 7
1.2 Objective ....................................................................................................................................... 8
1.3 Scope...............................................................................................................................................
1.4 Past Project Teams ......................................................................................................................... 9
1.5 Feasibility ........................................................................................................................................
1.5 Comparing Biodiesel and Petroleum Diesel......................................................................................
1.5.1 Differences in Chemistry ...........................................................................................................
1.5.2 Engine Modification.............................................................................................................. 11
1.5.1 Engine Performance ..................................................................................................................
2. Design Norms........................................................................................................................................
2.1 Stewardship ................................................................................................................................. 13
2.2 Caring.......................................................................................................................................... 13
2.3 Transparency ...................................................................................................................................
3. Team Organization ............................................................................................................................ 14
Team Responsibilities .................................................................................................................... 15
Hannah Albers ............................................................................................................................... 15
Ben Guilfoyle ................................................................................................................................ 15
Melanie Thelen ..................................................................................................................................
Cole Walker .................................................................................................................................. 16
4. Process Overview .............................................................................................................................. 16
4.1 Process Research ......................................................................................................................... 16
4.1.1 Block Flow Diagram ............................................................................................................. 16
4.1.2 Reaction Chemistry ............................................................................................................... 16
4.1.3 Key Variables ....................................................................................................................... 18
4.1.4 Design Alternatives ............................................................................................................... 20
4.2 Material Research ........................................................................................................................ 21
4.2.1 Feed Sources ......................................................................................................................... 21
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4.2.2 Feed Composition Research .................................................................................................. 22
4.2.2 Product ................................................................................................................................. 24
5. Preliminary Design ............................................................................................................................ 24
5.1 Transesterification Reactor .......................................................................................................... 24
5.1.1 Mass Transfer Limitations ..................................................................................................... 25
5.1.2 Design Alternatives ............................................................................................................... 26
5.2 Catalyst .................................................................................................................................... 31
5.3 Pre-Treatment Section ................................................................................................................. 33
5.3.1 Filter ..................................................................................................................................... 33
5.3.2 Acid Treatment ..................................................................................................................... 34
5.3.3 Waste Separation .................................................................................................................. 37
5.4 Post-Treatment Section ................................................................................................................ 37
5.4.1 Glycerin Separation ............................................................................................................... 37
5.4.2 Methanol Recovery ............................................................................................................... 40
6. Equipment ......................................................................................................................................... 41
6.1 Equipment Listing ....................................................................................................................... 41
7. Safety Considerations ........................................................................................................................ 43
7.1 Chemicals .................................................................................................................................... 43
7.2 Operating ..................................................................................................................................... 44
8. Business Plan .................................................................................................................................... 45
8.1 Market Study ............................................................................................................................... 45
8.1.1 Customer .............................................................................................................................. 46
8.1.2 Competition .......................................................................................................................... 47
8.2 Tax Information ........................................................................................................................... 48
8.3 Costs ........................................................................................................................................... 49
8.3.1 Capital Costs ......................................................................................................................... 49
8.3.2 Operating Costs..................................................................................................................... 49
8.4 Profitability ................................................................................................................................. 50
9. Conclusion ........................................................................................................................................ 52
References............................................................................................................................................. 53
Appendix .............................................................................................................................................. 56
1. Overall Process Mass Balance........................................................................................................ 56
2. Filter Calculations.......................................................................................................................... 57
3. Settler Calculations ........................................................................................................................ 58
4. Competing Biodiesel Plants in Florida ........................................................................................... 59
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5. Material Safety Data Sheets (MSDS) ............................................................................................. 59
Executive Summary ................................................................................................................................. 2
Table of Contents .................................................................................................................................... 3
Table of Figures ....................................................................................................................................... 3
Table of Tables ........................................................................................................................................ 6
1. Introduction ........................................................................................................................................ 7
1.1 Background Information ................................................................................................................ 7
1.2 Objective ....................................................................................................................................... 7
1.3 Scope ............................................................................................................................................. 8
1.4 Past Project Teams......................................................................................................................... 8
1.5 Feasibility ...................................................................................................................................... 8
1.5 Comparing Biodiesel and Petroleum Diesel .................................................................................... 9
1.5.1 Differences in Chemistry ......................................................................................................... 9
1.5.2 Engine Modification .............................................................................................................. 10
1.5.1 Engine Performance .............................................................................................................. 10
2. Design Norms .................................................................................................................................... 10
2.1 Stewardship ................................................................................................................................. 11
2.2 Caring .......................................................................................................................................... 11
2.3 Transparency ............................................................................................................................... 11
3. Team Organization ............................................................................................................................ 11
Team Responsibilities .................................................................................................................... 12
Hannah Albers ............................................................................................................................... 12
Ben Guilfoyle ................................................................................................................................. 12
Melanie Thelen .............................................................................................................................. 12
Cole Walker ................................................................................................................................... 13
4. Process Overview .............................................................................................................................. 13
4.1 Process Research ......................................................................................................................... 14
4.1.1 Block Flow Diagram ............................................................................................................... 14
4.1.2 Reaction Chemistry ............................................................................................................... 15
4.1.3 Key Variables......................................................................................................................... 16
4.1.4 Design Alternatives ............................................................................................................... 18
4.2 Material Research ........................................................................................................................ 19
4.2.1 Feed Sources ......................................................................................................................... 19
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4.2.2 Feed Composition Research .................................................................................................. 19
4.2.2 Product ................................................................................................................................. 21
5. Preliminary Design ............................................................................................................................. 22
5.1 Transesterification Reactor .......................................................................................................... 22
5.1.1 Mass Transfer Limitations ..................................................................................................... 22
5.1.2 Design Alternatives ............................................................................................................... 23
5.2 Catalyst .................................................................................................................................... 26
5.3 Pre-Treatment Section ................................................................................................................. 27
5.3.1 Filter ..................................................................................................................................... 27
5.3.2 Acid Treatment ..................................................................................................................... 28
5.3.3 Waste Separation .................................................................................................................. 30
5.4 Post-Treatment Section ............................................................................................................... 31
5.4.1 Glycerin Separation ............................................................................................................... 31
5.4.2 Methanol Recovery ............................................................................................................... 33
6. Equipment ......................................................................................................................................... 33
6.1 Equipment Listing ........................................................................................................................ 33
7. Safety Considerations ........................................................................................................................ 36
7.1 Chemicals .................................................................................................................................... 36
7.2 Operating .................................................................................................................................... 37
8. Business Plan ..................................................................................................................................... 37
8.1 Market Study ............................................................................................................................... 37
8.1.1 Customer .............................................................................................................................. 38
8.1.2 Competition .......................................................................................................................... 39
8.2 Tax Information ........................................................................................................................... 39
8.3 Costs ............................................................................................................................................ 40
8.3.1 Capital Costs ......................................................................................................................... 40
8.3.2 Operating Costs..................................................................................................................... 40
8.4 Profitability .................................................................................................................................. 40
9. Conclusion ......................................................................................................................................... 43
References ............................................................................................................................................ 44
Appendix ............................................................................................................................................... 49
1. Overall Process Mass Balance ........................................................................................................ 49
2. Filter Calculations .......................................................................................................................... 50
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3. Settler Calculations ........................................................................................................................ 50
4. Competing Biodiesel Plants in Florida ............................................................................................ 51
5. Material Safety Data Sheets (MSDS)............................................................................................... 51
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TTable of Figures Formatted: Font: 16 pt, No underline, Font color:
Custom Color(RGB(68,116,160))
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Table of Tables
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1. Introduction Formatted: Line spacing: Double
Fossil fuels account for approximately 82% of the United States’ energy supply. Though
geologists estimate that less than half the total volume of crude in below-ground reserves will be depleted
by 2030, it remains a fact that the supply of crude oil continues to decrease as the energy demand
necessary to support the rapidly advancing lifestyles around the world increases. Oil has done well to
advance human technology to the point where it is today, but the drawbacks of crude oil cast a shadow
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across the benefitscannot be ignored. The demand for crude oil has caused wars, damaged the
Used restaurant grease was recently found to contains high levels of triglycerides, which store
large amounts of energy. According to USA Today1, approximately 3 billion pounds of grease are
produced in the United States each year. The average fast food restaurant produces about 150 - 200
pounds of grease every week, says the New York Times. The disposal of waste grease has been a large
burden on restaurants, since grease cannot be processed in a wastewater treatment plant. It must be
collected in a grease trap and disposed of in alternative ways. Restaurants recently have been selling their
used grease in recent days to recycling companies that convert the used grease into fresh cooking oil.
Rather than recycling the grease for consumption, the burden of grease waste disposal can be alleviated
Also, in contrast to fossil fuels, biofuels are produced from renewable plant and animal material
such as vegetable oils, grease, or animal fats. Over the past decade, interest in producing biodiesel from
oils and grease has grown into a marginally successful industry as the future availability of fossil fuels
became uncertain. Additionally, burning biodiesel produces 56-87% less greenhouse gas emissions than
conventional diesel2, according to the EPA, which makes it a viable and promising option as an
The main objective of this project is to design a biodiesel production plant that will provide a
clean alternative to diesel. Petroleum production is unsustainable whereas the supply of restaurant grease
is readily available. Obtaining feedstock for the plant will require the participation of restaurants,
whowhich currently have to pay an outside source to dispose of the grease they generate on a daily basis.
By establishing the plant in a populous area with a lot of restaurants, a significant amount of biodiesel
1
Ron, Barnett. "Restaurants' Grease a Hot Item for Thieves." USA Today
2 Formatted: Font: (Default) Times New Roman
Beer, T, T Grant, and PK Campbell. "Biodiesel could reduce greenhouse gas emissions." CSIRO. CSIRO, 27 Nov. 2007.
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feedstock will be able to be producedavailable. . As stated previously, current fuel production is
Secondly, the team purposes to make the plant profitable. Biodiesel production will not increase
unless there is money to be made in the industry. Despite its environmental implications, production will
be limited if it continues to be more economicalprofitable to use fossil fuels to run our vehicles. By
designing a profitable biodiesel plant, the team hopes to prove that biodiesel production is part of the
1.3 Scope
The team plans to design a production plant in the Miami area that will buy used grease from
surrounding restaurants and convert it into pure biodiesel. The size of the Miami area will allow
significant grease collection for the production of a substantial amount of biodiesel. Based on the number
of restaurants in the area and keeping in mindthe fact that grease will not be obtained from every one of
these sources, the production of biodiesel is anticipated to be in the hundreds of barrels per day range.
This comes from the estimation of available feed at 130,000 kg/day. This calculation can be found in
section 4.3.1.
Biodiesel is commonly blended with conventional diesel in 50:1, 20:1, and or 5:1 diesel to
biodiesel ratios. The team assessed the possibility of blending the produced biodiesel at the plant but
determined that this was outside the scope of the project. The plant will be used exclusively to produce
Several senior design teams have completed projects pertaining to biodiesel production. In 2001,
Team FAME designed a plant that produced biodiesel in a continuous process for missionary
transportation services in third world countries. In 2008, Team Rinnova designed a small scale biodiesel
reactor for home users using feedstock from Calvin College Dining Services. Rinnova met their project
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goals but included recommendations for a second prototype. Suggested changes included adding a
completely electronic control system, using better materials for piping, and installing a coarser filter. The
Diesel Crew took these recommendations in 2013-2014 and designed a second prototype for home users.
Their design utilized a microwave reactor, unlike the batch reactor designed by Rinnova, as the Diesel
Though the scope of this report includes a full-scale plant design, references to these project
groups are found scattered throughout this report, particularly in the design alternatives for each plant
section. The team will not be building offdirectly using of other team projects by scaling up the past
designs, but will instead take into consideration their design decisions whileen making evaluating
The use of biodiesel compared to currently available diesel has both advantages and
disadvantages. For one, restaurant grease can be obtained inexpensively, which makes the plant more
economically feasible by lowering operating costs. See section BLANK for differences in operating costs
between a petroleum plant and a biodiesel plant. Additionally, biodiesel has positive environmental
implications as it produces less hydrocarbons and carbon monoxide than regular diesel when burned3. The
proposed process is more sustainable by helping the environment and eliminating waste. The traditional
diesel process requires a depletion of Earth’s natural resources to produce the fuel, while biodiesel uses
Despite these advantages, the use of biodiesel instead of traditional diesel does pose some
challenges, most notably gelling. In colder weather, some biodiesels solidify into a gel that renders them
unusable. This is one reason the plant will be placed in Florida. Considering the warm climate in the state,
gelling should not be a concern. Though biodiesel significantly decreases carbon emissions, it is less
3
"How Much Does Biodiesel Reduce Air Pollutants?" AllegroBiodiesel.
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efficient than normal diesel. It has been found that fuel efficiency is reduced by 10% compared to regular
diesel4. Despite these consdrawbacks, the team feels that the economic and environmental considerations
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Formatted: Font: Times New Roman
Formatted: Font: Times New Roman, 8 pt, Font color:
Figure 111: Biodiesel molecule Auto
A typical petroleum diesel molecule looks very similar, except it does not have the same ester Formatted: Font: Times New Roman, 8 pt, Font color:
Auto
functional group attached to one end. Formatted: Font: (Default) Times New Roman, 8 pt,
Font color: Auto
than petroleum diesel. Enzymes such as esterase recognize the ester group on the biodiesel and begin fatty Formatted: Font: (Default) Times New Roman, 8 pt,
Font color: Auto
acid degradation7. This process breaks the molecule down to generate acetyl-CoA whichCoA, which can Formatted: Heading 1, Line spacing: At least 13.5 pt,
Pattern: Clear (White)
be metabolized and thus is biodegradable and non-toxic. Biodiesel is safer for both the environment and Formatted: Font: (Default) Times New Roman, 8 pt,
Font color: Auto, Not Superscript/ Subscript
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human contact due to these characteristics. A biodiesel spill would be much less concerning than a
petroleum diesel spill and since biodiesel can be metabolized, it is not as toxic to humans.
Due to the similarity in chemical structure, a diesel engine can run on biodiesel fuel with minor
modification. Diesel engines manufactured pre-1993 may contain rubber tubing that may soften with
biodiesel fuel and should be replaced with biodiesel-rated components. These are typically made of
fluoro-elastomers like Teflon and will not degrade with biodiesel8. If the biodiesel fuel is a blend with less
than 20% pure biodiesel, there is no need to replace the rubber tubing. There is most likely no need to
replace the tubing on a car manufactured post-1993 either, but the engine should be examined by a
Also, biodiesel is more viscous than petroleum diesel so it may gel, causing engine issues while Formatted: No underline, Font color: Black
Formatted: Not Superscript/ Subscript
trying to start the car9. In cool climates, engines may have to be modified by adding a fuel heating system Formatted: Line spacing: Double
or using a fuel additive that will lower the viscosity. Viscosity lowering fuel additives are available Formatted: Font: (Default) Times New Roman, 8 pt,
Font color: Auto
commercially, such as Wintron®, a Biodiesel Cold Flow Additive10. Formatted: No underline, Font color: Auto
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1.5.1 Engine Performance
Formatted: Font: (Default) Times New Roman, 8 pt,
Overall the engine performance using biodiesel is comparable to using petroleum diesel; Font color: Auto
engine power is reduced by 3 to 5% while using biodiesel since it has less energy per unit volume than Formatted: Font: (Default) Times New Roman, 8 pt,
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petroleum diesel.11 Formatted: Font: (Default) Times New Roman, 8 pt,
Font color: Auto
Engine clogging can occur if low-quality biodiesel is used since it will contain more deposits and Formatted: Font color: Auto
Formatted: Font: Times New Roman, 8 pt, Font color:
viscous materials. However, this should not be an engine performance concern if high quality biodiesel is Auto
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used. Also, care should be taken that the biodiesel does not oxidize and thus polymerize before it is
burned, since this may clog a standard diesel engine. As long as the biodiesel is stored properly before
being distributed, this should not be a major concern. Proper storage includes storing at moderate
temperatures and not allowing the biodiesel to sit for extensive amounts of time before use.12
As mentioned in the introduction, engine emissions are also significantly reduced using biodiesel.
Sulfur emissions are essentiallyin effect non-existent and hydrocarbon emissions are reduced by an
average of 50%13. The only trade-off is a slight increase in nitrogen oxide emissions. Nitrogen oxide
(NOx) is a greenhouse gas and can cause smog and acid rain14. Overall though, the reduction in the
Crucial to the sustainability of the proposed plant from both business and ethical standpoints is
the promotion and prioritization of certain design norms, three of which are detailed in this report. These Formatted: Line spacing: Double
norms should be integrated into early planning stages of the plant and throughout the detailed design Formatted: Font: Times New Roman, 8 pt
Formatted: Font: Times New Roman, 8 pt, Not
work, construction, and daily operation to ensure the health, well-being, and integrity of employees and Superscript/ Subscript
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considered waste into a desirable product. Furthermore, it becomes increasingly vital in a world of
unlimited demand and limited resources to think forward to a time when the nonrenewable resources
currently used for energy generation are no longer a feasible option. Additionally, exercising stewardship
requires examining the consequences of energy consumption and making every effort to mitigate the
problems (greenhouse gas emissions or high volumes of dangerous waste material) faced by the energy
industry.
Once built, the proposed plant would require employees to operate the plant equipment. Caring,
one of the design norms, becomes an important attribute of the design engineers for the safety of all
employees. From the reactor catalyst selection to the layout of the plant units, caring must be exercised to
ensure employees aren’t required to put themselves in harm’s way as part of their job description and to
ensure safety procedures are established for routine and non-routine tasks. This design norm will be
practiced when designing the controls used in the plant and by not introducing dangerous chemicals into
2.3 Transparency
The potential for dangerous situations extending beyond the plant property are necessary to
internally evaluate and communicate to local government and local citizens who could be negatively
affected by the plant. Transparent business practices require full disclosure to employees and citizens of
potential hazards, Furthermore, since the final product must meet certain governmental standards to be
used in diesel engines, it is important to the team to ensure that the plant meet or even go beyond these
standards. No shortcuts or half-measures will be taken in the design process in an attempt to promote the
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3. Team Organization Formatted: Line spacing: Double
TIn order to To meet the team goal of designing a profitable plant, it was necessary to plan ahead.
Task deadlines were assigned based on both class and team-specific deadlines. Professor Jeremy
VanAntwerp was assigned to the team as a project advisor, and he met with the team every other week to
discuss progress and design challenges. Professor VanAntwerp connected the team with Randy Elenbaas,
who served as an industrial consultant. Randy Elenbaas is a chemical engineer employed at Vertellus
Specialties, Inc. in Zeeland, Michigan with valuable knowledge of process design and project
management.
As seen in Figure 3Figure 3Figure 3Figure 1, the project could be divided into three sections with Formatted: Font: Times New Roman, Not Italic
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research interlaced integrated throughout the process: the main reaction with pretreatment, the main
Formatted: Font: Times New Roman, Not Italic
reaction without pretreatment, and post-treatment. This schedule illustrates the team’s method of Formatted: Font: Times New Roman
Figure 1: Work breakdown schedule organized as critically linked tasks Formatted: Line spacing: Double
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Team Responsibilities
In addition to the tasks specified below, each team member was responsible for ongoing research
about their section of the design and biodiesel production in general. This approach enabled all members
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to be familiar with all aspects of the project in order to validate and constructively critique each other’s
work. Deliverables for class deadlines such as the team poster and executive summary were produced
compiled collectively to ensure all team members were aligned on the objectives and scope of the project
as these elements became more specific. Additionally, each team member was responsible for
communicating their section of the design verbally and in writing relevant documents.
Hannah Albers
Hannah was tasked with the preliminary transesterification reactor design including catalyst
aspects such as catalyst selection, reactor type, and preliminary sizing. She was also responsible for post-
treatment research and recording the team’s weekly progress to be reported to Professor VanAntwerp
Ben Guilfoyle
Ben was tasked with preliminary pretreatment design including esterification reaction kinetics,
sizing, and design alternatives, and he was also responsible for feedstock research in the Miami area. Ben
also worked in cost estimation and proving the plant’s profitability. He is the team’s webmaster and will
Melanie Thelen
Melanie was also tasked with preliminary transesterification reactor design such as reaction
kinetics, sizing, and design alternatives. She headed research pertaining to governmental biodiesel
standards and regulations and safety, and she kept the team organized by ensuring all class deadlines were
Cole Walker
Cole was also tasked with the preliminary pretreatment design including filter selection and
design alternatives. He was also responsible for financial research pertaining to market trends and plant
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profitability. Melanie and Cole are also working in the lab with grease samples to help the team better
4. Process Overview
22
4.11 Process Research
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Figure 444: Overall Process Block Flow Diagram
Figure 4:Overall Process Block Flow Diagram Formatted: Line spacing: Double
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4.11.2 Chemistry OverviewReaction Chemistry Formatted: Font: Not Superscript/ Subscript
Formatted: Font: Not Superscript/ Subscript
A triglyceride is an ester composed of three fatty acids connected with a glycerol backbone. The
fatty acids in waste grease can either be saturated (animal fat derivative) or unsaturated (vegetable oil
derivative). A glycerol molecule consists of three hydroxyl (HO-) groups, which form ester bonds with
24
the carboxyl (-COOH) groups in the fatty acids. Triglycerides can be burned on their own in diesel
engines but the three “tails” can become tangled, increasing the viscosity. A highly viscous fuel could
congest fuel injectors and other engine internals. Instead, transforming triglycerides into biodiesel
The main reaction that converts a triglyceride to biodiesel is called transesterification. In this
process, triglycerides are contacted with methanol, which causes the single carbon-oxygen bonds to
break. The methanol then reacts with the free end of the fatty acid to form a methoxy group, creating a
biodiesel molecule. Since one triglyceride molecule “frees” 3 fatty acids, 3 molecules of biodiesel are
produced for every one triglyceride. As shown in Figure 1Figure 1Figure 1, the final biodiesel molecule Formatted: Font: Times New Roman
Formatted: Font: Times New Roman
will have a long carbon chain with an ester group, formed by the addition of the methoxy group. The
Formatted: Font: Times New Roman
overall reaction is shown in Figure 6Figure 6Figure 6. Formatted: Font: (Default) Times New Roman, Not
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where R1, R2, R3 are alkyl groups which can be the same or different. When methanol breaks the carbon- Formatted: Keep with next
Formatted: Font: Times New Roman
oxygen bonds in the triglyceride, the entire backbone molecule remains intact and becomes glycerol or
soap. As seen in the chemical mechanism, a base catalyst is used this reaction and will be discussed in
The overall chemistry for the reaction of grease to biodiesel can be seen below in Figure 3.
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Figure 3: Reaction mechanism for transesterification of triglycerides following an acid pre-treatment: Formatted: Not Superscript/ Subscript
Formatted: Normal, Indent: First line: 0", Line
spacing: Double
Where the triglycerides are grease (with low FFA content) and methyl esters are biodiesel.
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Formatted: Font: Times New Roman
4.11.32 Key Variables Formatted: Font: (Default) Times New Roman, Not
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The feedstock to be used in the process will be trap grease—that is food waste grease that is Formatted: Font: (Default) Times New Roman, Not
Superscript/ Subscript
unable to be processed as wastewater. The oil portion of the grease may or may not be solid at room
Formatted: Font: (Default) Times New Roman
temperature but it will contain solid food particles that need to be filtered out. Within trap grease, there Formatted: Heading 3, Line spacing: Double
are two main types of grease: brown grease and yellow grease. Brown grease is essentially rotten food oil
while yellow grease is rendered animal fat and used vegetable frying oil. The most significant difference
in regard to biodiesel production is the free fatty acid (FFA) content of the grease. Brown grease contains
more than 15% FFA while yellow grease has less than 15%. An increased amount of FFA is undesirable
since it decreases the amount of triglycerides that can be turned into biodiesel. However, there are
methods of turning FFAs into esters, which will be discussed later. Yellow and brown grease can either
be processed simultaneously or separated beforehand. The rest of the grease is composed of triglycerides
The most promisingThe majority of processes involves a pre-treatment of high FFA feedstock
with high FFA with an acid catalyst. An acid catalyst, like sulfuric acid or hydrochloric acid, will convert
26
the FFAs to esters, increasing the overall conversion and product quality. It has been found that feed Commented [JV2]: Give citation
Formatted: Font: (Default) Times New Roman
stocks need to have approximately 1% FFAs or less to provide acceptable product quality. One problem
with pre-treatment is the formation of water as a byproduct of the FFA to ester reaction. This water needs
to be removed using a separation technique since it would otherwise contaminate the final product.
Another issue with the acid pre-treatment is potential damage to vessels, so an appropriate material needs
to be selected for the vessels. This acid pretreatment can be repeated to lower the FFA level to less than
1% since a lower FFA content indicates a higher overall process conversion to biodiesel. Additionally,
FFAs can cause undesirable side reactions in the reactor, such as saponification. Saponification is a soap
Figure 4: Saponification of Free Fatty Acids to form soap Formatted: Line spacing: Double
Field Code Changed
The FFA needs to be removed or converted before contacting with NaOH base to prevent the soap
formation. The saponification reaction needs to occur in the presence of water, so the water formed in the
acid catalyst reaction, seen in Figure 8Figure 8Figure 8Figure 5, needs to be removed.
Figure 888: Water formation in an acid catalyst reaction to convert Fatty acids to biodiesel
27
Figure 5: Water formation in an acid catalyst reaction to convert Fatty acids to biodiesel 18 Formatted: Line spacing: Double
Field Code Changed
Despite pretreatment, some soap (glycerin, in this case) will inevitably form and pass through to
the main reactor. Glycerin separation techniques will be discussed later in this report.
Upon completing the pretreatment, the feed is transferred to the main reactor where it is heated to
between 50°C and 60°C. The temperature must remain below the boiling point of the chosen alcohol so it
remains in the liquid phase without pressurizing the reactor. A solution of alcohol and alkaline catalyst is
prepared separately and added to the reactor. The alkaline catalyst is present to speed the reaction of
triglycerides to methyl esters and convert any remaining FFA to soap. An agitator is used for up to one
hour to ensure proper mixing, and the new solution settles. After proper separation, there will be a layer
of biodiesel at the top of the reactor, and any soap formed will settle at the bottom. Once these layers are
separated, biodiesel is ready for use. The variables to be manipulated in this process are:
It is important to note that this process assumes a given feedstock where the initial composition
In addition to the process described above, there are many alternative processes to convert used
Formatted: Font: 8 pt
grease to biodiesel under development. One such option is using a supercritical reactor for processing Formatted: Font: 8 pt, Not Superscript/ Subscript
Formatted: Font: (Default) Calibri, 8 pt, Font color:
Black, Not Superscript/ Subscript
Formatted: Font: 8 pt
28
grease with high FFA compositions. This process operates at high temperature (275°C to 325°C), high
pressure, and therefore must take place in heavy-dutypressure-rated reaction vessels. This reactor does not
require a catalyst because of the high temperature and pressure used, so some separation steps are no
longer necessary to purify the downstream product. Furthermore, side-reactions are less of a concern
with no catalyst present. Initial FFA content, water formation and subsequent glycerol formation due to
the high operating conditions less affect the process. However, the capital and operating costs are
astronomicalvery high. This is not a feasible option for a start-up plant of this scope., and It would be
better implemented as part of a revamp for a current facility since capital costs associated with pressure-
Another process is glycerolysis, a process that can handle feed stocks with greater than 10% FFA.
Glycerin is heated to 400F and reacted with the FFAs in the feed to form monoglycerides. These
monoglycerides can be processed as normal with the triglycerides by using an alkaline catalyst to form
biodiesel. Problems with this process include high operating costs due to the high heat, a high-pressure
boiler to keep the process in liquid phase, and a vacuum to remove any formed water. Glycerolysis is
similar to the process mentioned earlier because the glycerin must be separated at the end, but there is
Finally, the use of solid acid catalyst is an emerging option for processing grease. Solid acid
catalyst is packed into a packed bed reactor and the mixture of grease and alcohol flows through the
reactor. Water is still formed during the reaction though, so the alcohol/water solution separated the end
must be distilled to recycle the alcohol. Also, contaminants in the oil like phosphorus and water can foul
the catalyst.
29
4.22 Material Research Formatted: Font: 13 pt
Formatted: Line spacing: Double
4.22.1 Feed Sources Formatted: Font: 12 pt
The feed grease will be collected from restaurants in the Miami area. In the Miami greater area, it
was found that there are approximately 10,750 restaurants19. It was also found that an average restaurant
produces about 35 lbs of grease per day20. This means that about 375,000 lbs of waste restaurant grease is
used produced per day in the Miami area. The greater Miami area is 6,137 square miles, which is well
within reason to expect the plant’s trucks to be able to collect from the entire area. At the same time, Itit is
not feasible to expect every restaurant to contribute to the plant’s feed stock, so it was estimated that the
plant could collect approximately 75% of this waste grease. This leads to the estimation the plant will
First, the waste grease was heated until homogenous and filtered through a cheesecloth to remove Formatted: Heading 4, Line spacing: Double
Formatted: Font: (Default) Times New Roman
any suspended particles. Then, the grease was washed to reveal a lipid extract phase. A separatory funnel
was used along with a chloroform-methanol solution to separate the lipid phase.
Thin liquid chromatography (TLC) was used to analyze the lipid phase. This method uses a high-
polarity silica coated plate and a low-polarity solvent that travels up the plate. A dot of the sample to be
analyzed is placed at the bottom of the plate, and the plate is placed in a beaker with a small amount of
Formatted: Font: 8 pt
Formatted: Font: 8 pt, Not Superscript/ Subscript
Formatted: Font: 8 pt
19
Knight, Lauren. "How Many Restaurants and Bars are there in Miami?" Formatted: Font: 8 pt
20
Rosinski, Alan. "How Much Grease Fast Food Places Put Out." greener ideal Formatted: Font: 8 pt, Not Superscript/ Subscript
30
solvent on the bottom. As the solvent travels up the plate, the movement of the sample depends on its
polarity.
Standards were created to compare the lipid sample movement to known compounds. Butter was
used to simulate triglycerides and linoleic acid was used to simulate free fatty acids. Known
concentrations of each of the standards and the lipid extract were run on a TLC column. Then the plates
were stained with iodine chips to reveal the spots of sample. The area of the sample spot directly
The area of the samples were calculated using a program called ImageJ, which counts the number Formatted: Heading 4, Line spacing: Double
Formatted: Font: (Default) Times New Roman
of pixels in a traced area. Standard curves were generated which compared the known concentration to
Then the extract was run and the area of the triglyceride spot and FFA spot were compared to the
standard curves.
31
Formatted: Font: (Default) Times New Roman, Not
Superscript/ Subscript
Figure 101010: TLC Plate of Butter, Linoleic Acid and Grease Extract
It was determined that this grease contains 29% FFAs. This agrees with literature values, which
say that yellow grease contains 4-15% FFAs and brown grease contains 50-100% FFAs21
(http://www.nrbp.org/pdfs/pub32.pdf). Yellow grease comes from vegetable oil and brown grease comes
from animal fat. Since our sample contains both, 29% is a reasonable result and representative of waste
grease from many restaurants that serve both animal and vegetable fried products. This value will be used
to determine the amount of pre-treatment needed to reduce the FFA content to less than 1% (the standard
32
4.22.3 Product
4.22.2 Product
Table 1Table 1Table 1 features the federal EPA specifications for 100% biodiesel stock fuel Field Code Changed
33
Table 1: EPA Biodiesel Specifications Field Code Changed
For the main reactor, three parts methanol and one part triglycerides are sent to a reactor for the
34
Figure 6: Transesterification of triglycerides to form biodiesel (methyl esters) Formatted: Left
Field Code Changed
The catalyst in the reaction is typically aa salt (typically sodium hydroxide or potassium
hydroxide), which assumes that the waste vegetable oil has been pretreated to decrease the amount of
FFAs by a processed described below. A broader range of catalysts types areA broader range of catalysts
Mass transfer primarily limits the yield and purity of the biodiesel product. Triglycerides and
methanol form two immiscible phases when combined, and the rate of reaction is directly influenced by
the degree of mass transfer between phases. According to the Wilke-Change empirical model for
diffusivity, the diffusivity coefficient between two liquid phases decreases with increasing viscosities, and
Mass transfer limitations can be mitigated by increasing the interfacial area between
phasesIncreasing the interfacial area between phases can mitigate mass transfer limitations. Most reactors
have some form of agitation such as impellers or baffles that use shear force to decrease the droplet size
of methanol and triglycerides, increase the interfacial area of both phases. Mass transfer is greater in
turbulent flow, which agitation promotes. Other methods include acoustic cavitation, or the rapid growth
and collapse of cavities in the reactor. When the cavities collapse, the liquid rushing into the preoccupied
space creates shear forces that are capable of breaking chemical bonds of the triglyceride molecules and
thus reducing droplet size. Alternatively, running the reaction above the supercritical temperature of
methanol forces it to form a homogeneous phase with the triglycerides, but high energy costs to heat the
reactor feed accompany this scenario. The use of multiple micro-reactors also promotes mass transfer.
Interfacial area in micro-channels increases with decreasing micro-channel reactors, which promotes high
conversion.
35
All biodiesel reactor types either contain or can be modified to contain mass transfer promoting
elements, but these characteristics also contribute to more difficult post-treatmenttreatment, as smaller
droplets are more stable when dispersed than larger droplets. Both mass transfer and subsequent
Selecting a reactor for optimal biodiesel production requires tradeoffs between high capital costs,
reaction times, energy requirements, and conversion. Batch, semi continuous, and continuous reactors are
Individuals who independently make biodiesel for personal use most commonly use batch reactors.
They are easy to build on for a small, garage- operation scale operation and have a low capital cost for
plant use. Batch reactors can convert a wide variety of feedstocks into methyl esters, which is favorable
The downsides to batch reactors are low conversion, high energy requirements, and long total
reaction time. Batch reactions typically take place with either sodium or potassium hydroxide as a
catalyst for transesterification, which is inefficient and leads to low yields. However, researchResearch
shows that adding an agitator or series of agitators increases conversion up to 99% while decreasing
reaction time..[3] Agitator speeds typically range from 200-900 rpm, with higher speeds promoting
greater conversion.
Despite lowering reaction time, the combined time of heating, reacting, cooling, and preparing for
subsequent runs makes the batch reactor time inefficient. Waste cooking oil must pass through a
36
pretreatment step to lower FFA content in order to decrease the amount of glycerol formed as a side
reaction during transesterification. This side reaction lowers methyl ester selectivity, and glycerol must
be later separated from the methyl esters in order to meet production standards.
5.1.2.2.1 Continuous reactors may be favored over batch reactors for several reasons. The alcohol catalysts utilized for
batch operations form glycerol soaps as a side product that have to be separated from the methyl esters in a pretreatment process.
This pretreatment requires an acid such as sulfuric acid that can be corrosive or difficult to dispose of in an environmentally
friendly way. Continuous reactors do not require this pretreatment step since they use solid catalysts such as ion-exchange resin
catalysts, clays, or solid bases such as sodium and potassium hydroxide on activated carbon. These catalysts do not react with
FFAs to form soaps. Clays are particularly suitable because they are low cost, have low environmental impact, promote high
selectivity, and are reusable.[4] The primary drawback to solid catalysts is deactivation. The catalysts used can absorb some of
the reactants and increasingly render catalytic sites useless. When this happens, the catalyst must either be regenerated or
replaced with fresh catalyst, and both of these alternatives require time and added expenses.
Plug-Flow Reactors (PFRs) Formatted: Font: Times New Roman, Not Superscript/
Subscript
In a PFR, the reaction takes place inside a simple tube or pipe. PFRs are used in continuous Formatted: Font: 9 pt
processes with liquid or gas reactants and catalysts. Conversion increases with increasing residence time Formatted: Heading 6, Line spacing: Double
and volume. PFRs are rarely used in biodiesel production, according to the literature, because the length
5.1.2.2.2 Packed Bed Reactors Formatted: Font: 10 pt, Not Superscript/ Subscript
Formatted: Line spacing: Double
Packed bed reactors are essentially plug-flow reactors containing a solid catalyst. These reactors
Formatted: Font: Times New Roman, Not Superscript/
Subscript
ensure an even mixing of reactants throughout the reaction tube to provide higher conversions than batch
Formatted: Font: 10 pt, Not Superscript/ Subscript
reactors but require several hours for this conversion. Activated carbon is typically the solid of choice
Formatted: Font: 10 pt
coupled with oxides or alcohols. Long tube lengths for PBRs also tend to disqualify them as feasible
reaction vessels.
37
5.1.2.2.3 Continuous Stirred Tank Reactors (CSTRs) Formatted: Font: 10 pt, Not Superscript/ Subscript
Formatted: Font: Times New Roman, Not Superscript/
CSTRs are vessels with agitation used in continuous processes. While a single CSTR does not Subscript
outperform a batch reactor in terms of conversion (source) when used in biodiesel production22, CSTRs Formatted: Font: 10 pt, Not Superscript/ Subscript
Formatted: Font: Times New Roman, Not Superscript/
in series can approach high conversions. The expense of additional multiple reaction vessels tends to Subscript
Formatted: Font: 10 pt
exclude CSTRs from popular usage.
5.1.2.2.4 Membrane Reactors Formatted: Font: (Default) Times New Roman, Not
Superscript/ Subscript
Membrane reactors utilize a selectively permeable membrane for methyl ester conversion. Formatted: Font: 10 pt, Not Superscript/ Subscript
Triglycerides enter the reactor on one side of the membrane while the methanol enters on the other. Formatted: Font: 10 pt
Unreacted mono-, di-, and triglycerides are contained on one side of the membrane as the reactants come
into contact, which facilitates a simpler separation of triglycerides downstream of the reactor.
Additionally, the membrane reactor can be designed to retain glycerols so that triglycerides with higher
FFA content could be used. Most membranes are made out of carbon for low cost and ease of production,
but they are also made of ceramic, polymers, silica, and zeolites. Membrane reactors have low capital
and operating costs and can be used in continuous processes, however the time required for high
biodiesel production. A liquid catalyst such as sodium hydroxide is used to drive the transesterification Formatted: Font: 10 pt
that takes place simultaneously in all the channels. The reactionThe reaction in a A micro-reactor would
take place near room temperature so there would have abe lower energy requirements than at elevated
temperatures since the reaction takes place as low as room temperature, which decreases energy
requirements. Corrosion issues are avoided by constructing micro-reactors out of plastic resins such as
38
comparison to batch reactions and other continuous reactors, but the pretreatment step cannot be avoided.
Diesel Crew built a microwave reactor for their small-scale biodiesel process, but it would be difficult to
scale this process up to an industrial level since most home users aren’t converting high volumes of
the biodiesel transesterification reaction by generating gaseous cavities that create high energy densities Formatted: Font: 10 pt
as the cavities grow and collapse. Cavities are created with pressure in acoustic cavitational reactors and
a change in geometry in hydrodynamic cavitational reactors. These cavities also result in fine emulsions
that increase mass transfer. When acoustic cavitational reactors were studied, residence times of less than
one minute resulted in over 80-100% yields for transesterification at room temperature. Further
separations are easier due to lower operating temperatures and smaller methanol-oil ratios. The difficulty
with these reactors is similar to microwave reactors; they are troublesome to scale up for plant operations.
5.1.2.2.8 Oscillatory Baffled Reactor Formatted: Font: 10 pt, Not Superscript/ Subscript
Formatted: Font: Times New Roman, 10 pt, Not
Oscillatory baffled reactors are essentially PFRs with baffles spaced evenly throughout the tube Superscript/ Subscript
with an oscillating throughput flow rate. This flow rate facilitates recirculation of the reactants for Formatted: Font: 10 pt
increased residence time and greater mass and heat transfer while still maintaining liquids entering and
exiting the reactor at steady state. OBRs can achieve 99% conversion in approximately 10 minutes, are
39
compatible with homogeneous and heterogeneous catalysts, and are designed to recycle unreacted
methanol. Methanol recovery is facilitated by larger droplet sizes leaving the reactor because adequate
conversion can be achieved without adding extra agitation or other means to decrease the reactant droplet
sizes.
distillation column. Methanol and the triglycerides are combined in a single feed stream and drive the Formatted: Font: 10 pt
reversible reaction in favor of methyl ester conversion. Unreacted methanol exits from the top of the
column while the methyl esters leave as bottoms products with a conversion of nearly 95%. The energy
requirements for this process are high and the pretreatment step still necessary, but reactive distillation
may be favorable if a distillation column is already necessary to separate waste water and methanol.
5.1.3 Past Design Teams Formatted: Add space between paragraphs of the
same style, Line spacing: Double
Team FAME purposed to design a continuous process for their customers and selected two plug- Formatted: Font: Not Bold, Not Superscript/ Subscript
Formatted: Indent: First line: 0.5", Add space
flow reactors with a glycerol separation following each. They assumed that this configuration would give between paragraphs of the same style, Line spacing:
Double
a 98.2% yield of methyl esters. Team Rinnova designed a batch process that was accompanied with
recommendations for a second prototype. The control system for the labor-intensive batch process
required modifications. In light of this, the Diesel Crew designed a continuous process using a
A continuous process is desired over a batch process for multiple reasons. Batch processes
require down time for the system to heat, cool, be cleaned, and prepared for the next reaction, which
involves more controls and manpower to accomplish. If employees are required to assist with cleaning
and loading the reactor, an additional safety risk is imposed on the overall system. Additionally, all the
downtime steps introduced with batch systems present more opportunities for error. Batch processes are
40
preferred over continuous processes when a larger degree of control over the system is required, but
While evaluating advantages and disadvantages of alternative reactors, the team narrowed the
focus of the reactor design to only include design variables that most significantly increase the quality and
quantity of the desired product. Currently, a batch reactor is the most attractive because the reaction rates
are high, catalysts are inexpensive, and any conversion deficiencies can be mitigated with agitation.
Several batch reactors would be required in parallel to simulate a continuous process and accommodate
the feedstock volumes. The greatest limitation of the process is mass transfer, and the selected reactor
must be equipped to mitigate this limitation without influencing the overall costs. The team will continue
to research other reactor types to ensure that the best type is selected for our objectives.
The catalyst selected to promote transesterification must meet certain criteria, and one of the most
important factors is cost. If, from the beginning, biodiesel is less profitable than diesel, lowering the cost
of materials used will help increase profit margins and make the plant a worthwhile venture.
Furthermore, the faster the transesterification proceeds, the more grease can be processed and sold. The
catalyst should minimize undesirable side reactions, and a significant portion must be recycled in an
commonly used largely because they are less expensive than clays and enzymes, and they promote faster
41
5.2.3.1 Homogeneous Bases Formatted: Not Superscript/ Subscript
Formatted: Heading 4, Line spacing: Double
Homogeneous bases such as NaOH, KOH, and methoxides (reacting alkali bases with an alcohol
such as methanol) are the most commonly used catalysts because they are inexpensive, promote high
reaction rates, and are not accompanied by high energy requirements. However, these bases also react
with FFAs to produce soaps, which decreases overall methyl ester yields and create emulsions that make
product purification difficult. Alkali catalysts are also known to form soaps with water. Homogeneous
catalysts tend to be less expensive and easier to use than heterogeneous catalysts.
products. While homogeneous catalysts must either be disposed of or recycled after separation, a solid Formatted: Not Superscript/ Subscript
catalyst like CaO can be regenerated and reused easily. FFAs still react with heterogeneous catalysts to
form soaps, and catalyst leaching becomes a further issue. Most heterogeneous bases are rendered
ineffective when used at room temperature, so higher energy costs are necessary to protect the catalysts
from degenerating. The primary drawback to solid catalysts is deactivation. The catalysts used can
absorb some of the reactants and increasingly render catalytic sites useless. When this happens, the
catalyst must either be regenerated or replaced with fresh catalyst, and both of these alternatives require
Recent studies indicate that strontium oxide (SrO), or SrO doped SiO2, as a catalyst promotes
yields over 90% in approximately 10 minutes and has a FFA tolerance above the typical 3 wt%. SrO
catalysts can tolerate between 3 and 3.5 wt% FFAs. However, SrO is more expensive than typical alcohol
catalysts.
42
Clays Formatted: Font: Times New Roman, Not Superscript/
Subscript
Clays are particularly suitable because they are low cost, have low environmental impact, Formatted: Heading 3, Line spacing: Double
Formatted: Font: 11 pt
promote high selectivity, and are reusable.[4]
Team Rinnova’s design utilized KOH over NaOH for transesterification because it mixes well
with methanol. Once mixed with methanol, NaOH required a full day to dissolve, whereas KOH
dissolves much faster. Liquid catalysts are ideal for batch reactions because the amount of catalyst
needed is essentially the amount necessary for one batch. Team FAME also used KOH for the same
reasons and also found that using KOH makes downstream separation easier.
The Diesel Crew used CaO, a solid commonly sold by cement supply companies. One of their
objectives was to design a continuous process, and solid catalysts lend themselves to this type of system.
compatible with a batch reaction system. The cost difference between KOH and NaOH is marginal since
the catalyst is already one of the least costly aspects of the design. The catalyst choice may be revisited in
the future.
5.32.1 Filter
The waste vegetable oil (WVO) contains food debris and particulates that must be removed to
prevent waste build up in the pumps and pipes and to control the quality of the feed entering the acid
treatment. The pre-treatment filter must be able to remove the roughly 3% solids from the feed.
43
5.3.1.1 Leaf Filter: Formatted: Font: (Default) Times New Roman, Not
Superscript/ Subscript
Vertical Ppressure Lleaf Ffilters are applied for liquids with low solid content (roughly 1% to Formatted: Font color: Black, Not Superscript/
Subscript
7%). The vessel of the leaf filter can be suited with a steam jacket to control the temperature in the filter Formatted: Font: Times New Roman
for liquids that require higher operating temperatures. Vertical pressure leaf filters can be used, rather Formatted: Heading 4, Line spacing: Double
than horizontal filters, in cases where light/fine particles are removed to minimize floor space. Vertical
pPressure lLeaf fFilters have applications in the fuel and biofuel industry to filter crude oil and fatty acids.
The fact that these filters have been used in the industry previously ensures they would be a good choice
for the plant. Also, the maximum filter area in a vertical leaf filter is approximately 100 m2. This should
be notednoted, as multiple vertical leaf filters would be needed in this process to achieve the necessary
filtration. The steam jacket capability of the vertical pressure leaf filter is essential to maintain a low
viscosity of grease, meaning if this filter is chosen the steam jacket will most likely be necessary.
Centrifuges are commonly used to separate solids from liquids. It uses centripetal acceleration to Formatted: Heading 4, Line spacing: Double
Formatted: Font color: Black, Not Superscript/
separate a mixture based on density; the denser substance moving farther from the axis of rotation, while Subscript
the lesser dense substance is being pushed toward the axis. Large industrial centrifuges are used to Formatted: Font: Times New Roman
separate waste grease into white, yellow, and brown grease based on fatty acid concentration. It is also
Using a centrifuge for the pretreatment would not only separate the solids from the grease, but
also separate the grease into a heterogeneous mixture; yellow and brown grease. The centrifuge would
most likely result in four separate phases: solids, brown grease, yellow grease, and water. The separation
of the liquid phase would complicate the system. The different phases would have to be treated separately
and the system would have to include two processes; a process to treat the yellow grease and a separate
process to treat the brown grease. This would involve multiple pretreatments stages and reactors.
44
To simplify the system and reduce capital costs, the team wishes to have a single homogeneous
liquid phase for the grease feed. Therefore, the centrifuge would not be a desirable filtering method for
the system.
It has been decided that preliminarily Vvertical leaf filters were selected will be used to separate Formatted: Font color: Black, Not Superscript/
Subscript
out the solids from the waste grease feed. This comes from the fact that the leaf filters are able to handle Formatted: Font: Times New Roman
the expected solid content of the feed (3 wt %) as well as its wide use in filtering fatty acid mixtures. The Formatted: Heading 4, Line spacing: Double
Formatted: Font: Times New Roman
vertical leaf filter can also be fitted with a steam jacket whichjacket, which is necessary to maintain high
temperature in the filter vessel and minimize grease viscosity. In order to size the filters needed the
In the above equation, L is the cake thickness, epsilon is the porosity of the cake, rho is the Formatted: Spanish (Mexico), Not Superscript/
Subscript
density of the solid particles in the cake, cs is the weight of solids per volume of filtrate, and V is the Formatted: Spanish (Mexico)
Formatted: Spanish (Mexico), Not Superscript/
volume of filtrate. These are used to solve for A, or the filter area needed in the process. A complete Subscript
calculation and the values used for the above properties can be found in Appendix 2. From this, it was Formatted: Spanish (Mexico)
Formatted: Spanish (Mexico), Not Superscript/
determined that 225 m2 of filter area would be needed for the process. As the maximum filter area of a Subscript
If a batch or micro-reactor is chosen to produce biodiesel, an acid treatment must proceed the
transesterification reaction to lower the FFA content in the feed to less than 1%. However, this is not true
if the catalyst used for transesterification is not an alcohol and thus will not form glycerol soaps in an
undesirable side reaction. The design for this pre-treatment reactor will be covered, but, as stated above,
45
In the treatment reactor, sulfuric acid is used as an acid catalyst. Methanol, in the presence of this
acid, esterifies the FFAs . Methanol was chosen over ethanol as the pretreatment alcohol because it is
more commonly used and is significantly cheaper than ethanol23. This not only increases the overall
conversion in the main reactor, but also improves the quality of the biodiesel product by removing
impurities. If the FFA content is above the 1% mark mentioned previously, the quality of the product will
It was determined that this acid treatment will take place in an isothermal PFR. This was selected
by analyzing results from an experiment found in the Iraqi Journal of Chemical Engineering24. The
isothermal PFR provides higher ester formation than an isothermal CSTR of the same volume. It is also is
more efficient than any reactors run adiabatically. An isothermal batch system could provide the needed
conversion will similar efficiency, however the drawbacks of a long set up and cleaning time leads to the
Knowing the intended flow rates of each component in the plant through the process flow
Formatted: German (Germany), Not Superscript/
diagram, a preliminary volume of the pretreatment reactor was able to be calculatedetermined. First a rate Subscript
46
flow rates. From this, it was found that the initial concentration of FFAs is 1.046 mol/L and the initial
concentration of methanol is 24.71 mol/L. Through research it was found that typical k values in these
Using the values and equations outlined above, a Levenspiel plot was made which plotted
conversion on the x-axis and the value of FFA molar flow rate divided by the reaction rate on the y-axis.
Figure 10: Levenspiel Plot of the Pre-Treatment Reaction Formatted: Font: Times New Roman, Not Italic
Formatted: Font: Times New Roman
Figure 7: Levenspiel plot of the pre-treatment reaction.
Formatted: Caption, Centered, Indent: First line: 0",
Don't keep with next
Using the process flow diagram it was determined that a conversion of 97% in the pre-treatment Formatted: Line spacing: Double
Field Code Changed
is needed to keep the FFA content entering the main reactor under 1%. The volume of the PFR needed is
then equal to the area under the curve in from a conversion of 0 to 0.97. This area was calculated by first Field Code Changed
fitting a polynomial equation to the Levenspiel plot. This polynomial was then integrated and solved
47
using the above limits to find the necessary volume of 460 L. The preliminary recommendation is then to
use a 460 liter PFR to produce the needed FFA concentration entering the main reactortion.
5.3.3 Waste Separation Formatted: Font: (Default) Times New Roman, Not
Superscript/ Subscript
The stream leaving the pretreatment reactor is comprised of waste water, methanol, Formatted: Heading 3, Indent: First line: 0"
triglycerides, and trace amounts of FFAs. Water must be removed from the stream before it enters the
transesterification reactor. Otherwise, the water and FFAs will react to form glycerin and lower biodiesel
selectivity. The most effective separation technique is distillation. The difference in volatility between
water and triglycerides make distillation an effective separation technique. Though distillation is
accompanied with high energy requirements, this rigorous separation will ensure the water leaves the
stream accompanied by methanol (which has a higher volatility) and does not interfere with the
transesterification process. A system mass balance shows that methanol in the water streamseparated
after pretreatment accounts for less than 1% of the total volume, so another distillation column would not
be necessary to separate water and methanol. 95% of the methanol required for the 12% of the total
methanol required for the entire process, so another distillation column would be necessary to separate
water and methanol so that the maximum amount of methanol would be recovered. The added cost of the
distillation column will pay for itself in decreased methanol and waste treatment costs as the water
48
5.34.1 Glycerin Separation Formatted: Line spacing: Double
The EPA specifies that up to 0.24 wt% glycerin can be present in biodiesel product. Even with a Formatted: Indent: First line: 0.5"
rigorous pretreatment process to mitigate soap generation, glycerin in the reactor effluent must be
separated from the biodiesel, and one way to accomplish this is adding a large settling tank downstream
of the reactor. The glycerin will enter the tank with the liquid products, and settle to the bottom. A
settling tank would be simple and effective because other components in the effluent stream are much less
dense, as shown in Table 2Table 2Table 2, and the product flowing out of the tank would have only trace Field Code Changed
amounts of glycerin.
Table 222: Relative densities of effluent stream components Field Code Changed
The team was advised to avoid a solid-liquid separation. Solids are usually avoided in industry as
they are harder to work with than liquids. The glycerin is a liquid when leaving the reactors, but has a
melting point near room temperature (64 F). As this is still a lower temperature, the team finds it wise to
add some form of heat exchange to ensure glycerin remains a liquid. The most obvious alternative is to
heat the stream entering the settling tank. This could take the form of a heat exchanger immediately after
the reactors, or reactors operating at elevated temperatures. Keeping this heating precaution in mind, a
large tank is the most likely settling device used to remove glycerin.
A preliminary sizing of this settling tank was conducted. For these calculations, a more simplified Formatted: Indent: First line: 0.5", Line spacing:
Double
example of a biodiesel and glycerin mixture was examined. The methanol was neglected because it has
49
the lowest density and therefore is not expected to interfere with the separation between the methyl esters
and glycerin.
The first step in sizing the tank is to determine the dispersed phase. To do this, the equation
is employed. Here, Q refers to volumetric flow rates, which are gathered from the process flow diagram, ρ Formatted: Font: Times New Roman
Formatted: Font: Times New Roman
refers to fluid densities and µ refers to fluid viscosities. The subscript l is a reference to the light phase
Formatted: Font: Times New Roman
and h is to the heavy phase. As indicated previously, in this case the biodiesel is the light phase and
glycerin is the heavy phase. This equation produces a θ of 7.83, which means the heavy phase, or
glycerin, is dispersed26. Precise values for these variables can be found in Appendix 3 ?, along with a full
calculation of the settling tank sizing. Viscosities were taken at 25 degrees Celsius as this slightly raised
After determining the dispersed phase, it is necessary to decide which settling law applies. The
(𝜀𝜀 )(𝜀𝜀 −𝜀𝜀 ) (1) Formatted: Centered, Line spacing: Multiple 1.15 li
𝜀𝜀 = 34.81𝜀𝜀 [ ]3
𝜀2𝜀
Formatted: Font: Times New Roman
Formatted: Font: Times New Roman
Formatted: Font: Times New Roman
Formatted: Font: Times New Roman
Formatted: Font: Times New Roman
Above, subscript f refers to the biodiesel and subscript p refers to the glycerin. The variable dp is
Formatted: Font: Times New Roman
the average droplet size of the dispersed phase, glycerin, thatglycerin, which forms as it falls out of Formatted: Font: Times New Roman
Formatted: Font: Times New Roman
mixture. It was determined from literature research that this diameter is best approximated as 70 µm27.
Formatted: Font: Times New Roman
Formatted: Font: Times New Roman, 8 pt
26
Seader, Henley, and Roper. Separation Process Principles. 3rd ed. 795.
Formatted: Font: Times New Roman, 8 pt
27
Abeynaike, A, AJ Sederman, Y Khan, ML Johns, and JF Davidson. "The experimental measurement and modelling of sedimentation and Formatted: Font: Times New Roman, 8 pt
creaming for glycerol/biodiesel droplet dispersions." Malcolm Mackley. Chemical Engineering Science
Formatted: Font: Times New Roman, 8 pt
50
When this value is used in the above equation, Kc is found to be equal to 0.38. For Kc values less than 3.3
and droplet sizes between 3-100 µm, Stoke’s Law is used to find the settling velocity28. It is also
important to know that flow into the settler must be laminar to utilize Stoke’s Law, a condition that will
As mentioned above, Stoke’s Law allows for the calculation of the settling velocity of the
mixture. This can then be used to size the tank. Stoke’s Law expresses
taken as a guideline from references29. This leads to the derivation of the equation
Formatted: Centered
𝜀𝜀𝜀𝜀𝜀𝜀𝜀𝜀𝜀𝜀 Formatted: Font: Times New Roman
5𝜀2
≥ 𝜀𝜀
Formatted: Font: Times New Roman
Formatted: Font: Times New Roman
The minimum diameter is then calculated to 0.77 m. A safety factor is added, resulting in the
preliminary design of a 1 m tank diameter. Using the length to diameter ratio, the final preliminary
51
5.34.2 Methanol Recovery
The EPA specification for methanol is less than 0.2 vol% in the finished biodiesel product. The
team is currently researching different methods of separating methanol and methyl esters, which include
discussed in the pretreatment section of this report and therefore will not be described in detail here.
Rinnova’s vacuum distillation design, which requires an operating pressure below 1 atm, and found it
effective for their purposes. There is over a 60° F difference between the boiling points of water and
methanol, which makes distillation an attractive and effective choice. However, distillation is the
generally the most energy intensive separation technique, and the added energy costs of operating a
vacuum tower in a plant may make a different separation technique more feasible.
The process takes advantage of differences in polarity and molecular size to pass a smaller and more polar
molecule through a selective membrane that is aided by a vacuum. The membrane used is inert, and the
only energy requirements are heating the incoming stream (the process is more effective at high
temperature) and running the vacuum. Since methanol and water are similar in their polarity, the
membrane selection would be particularly important. One downside to pervaporation is that it is usually
precedes a distillation column and may not be effective as the only method of separation. If distillation or
52
a centrifuge will be required following pervaporation, it may be more worthwhile to use the budget for
will ensure maximum separation of methanol and water and is the best alternative. Equilibrium data for
this binary mixture is readily available in the literature at several different temperatures, and UNISIM
simulation software will be used in the future to model the characteristics and energy requirements of the
column.
6.1 Equipment Listing Formatted: Font: (Default) Times New Roman, Not
Superscript/ Subscript
The Table 3following table describes the equipment and materials of construction
necessary for the process. Carbon steel is a standard material of construction because of its affordability
and commonality in the chemical industry. In units where corrosion is a concern due to acids or bases,
such as the sulfuric acid and potassium hydroxide in our process, more corrosive resistant materials must
be considered. The esterification plug flow reactor and pre-treatment distillation column will containis
sufficient for several vessels, but the basic nature of potassium and acidity of sulfuric acid make corrosion
an issue in the mixer and esterification reactors significant amounts of sulfuric acid.. For these vessels,
carbon steel coated with stainless steel inner coating was selected as the best material. The mixer and
transesterification reactor come into contact with small amounts of potassium hydroxide. Figure 131 was
used to determine the materials of construction for the mixer and transesterification reactor. The figure
uses the sodium hydroxide as a base, which is more basic that potassium hydroxide. Therefore, any
material suitable for sodium hydroxide would also be suitable for potassium hydroxide, using the same
53
concentration and temperature conditions. No more than 4% potassium hydroxide is expected to exist
within the vessels at any point of the process and the temperature of the solution will be about 60°C.
Under these conditions, the solution is located in Area A using the figure, indicating that carbon steel is a
Figure 11: Materials of Construction for Handling Caustic Solution31 Formatted: Font: Times New Roman
Formatted: Font: Times New Roman
Table 333: Equipment and Materials of Construction Formatted: Font: Times New Roman
Formatted: Font: Times New Roman
Equipment Material Of
Construction Formatted: Centered, Space After: 0 pt, Line
spacing: single
Vertical Leaf Filters (3) Carbon Steel
Formatted Table
30
"Caustic Soda Solution Storage Tank Lining." Dow Answer Center. The Dow Chemical Company, 6 Nov. 2014. Web. 07 Dec. 2014. Formatted: Font: Times New Roman, 8 pt
31
"Caustic Soda Solution Storage Tank Lining." Dow Answer Center. The Dow Chemical Company, 6 Nov. 2014.
Web. 07 Dec. 2014. Formatted: Font: Times New Roman, 8 pt
54
Formatted ...
Formatted ...
Formatted ...
Formatted ...
Esterification Plug Flow Reactor Stainless Steel coating Formatted ...
Pre-Treatment Distillation Stainless Steel coating Formatted Table ...
ColumnDistillation Columns (2)
MixerEsterification Plug Flow Carbon SteelCarbon Formatted ...
Reactor steel coated with Formatted ...
stainless steel
Formatted ...
Transesterification Reactor Carbon Steel
Post-Treatment Distillation Column Carbon Steel Formatted ...
Settling Tank Carbon Steel Formatted ...
Formatted ...
Formatted ...
Further equipment will be necessary to ensure necessary energy is supplied and removed from the Formatted Table ...
Formatted ...
system to achieve the desired volume of product. This equipment will include, but is not limited to, heat Formatted ...
exchangers, pumps, valves, vesselsand vessels. The number of vessels and respective volumes are shown Formatted ...
Formatted ...
in Table 4. The appropriate quantity and energy requirements of other necessarythis equipment will be
Formatted ...
determined once additional design decisions are made, the most important of which is the main reactor. Formatted ...
Formatted ...
Table 444: Storage Vessel Volumes based on Storage Density Contents *denotes vessels that are incorporated into the process Formatted ...
but are not represented in the process flow diagram
Formatted ...
Vessel Contents Volume (m3) Material of ConsturctionConstruction Formatted ...
Feed Grease 5 Carbon Steel
Formatted ...
Methanol 5 Carbon Steel
50 Formatted ...
Sulfuric Acid 0.5 Stainless Steel Formatted ...
Post Pre-Treatment* 150 Carbon Steel
Formatted ...
Glycerin 15 Carbon Steel
Biodiesel 150 Carbon Steel Formatted ...
Wastewater* 3 Carbon Steel Formatted ...
KOH 0.5 Stainless Steel
Formatted ...
Formatted
6. Safety Considerations ...
Formatted ...
Formatted ...
Formatted ...
Formatted ...
Formatted ...
Formatted ...
Formatted ...
Formatted ...
Formatted ...
Formatted ...
55 Formatted ...
Formatted ...
Formatted ...
Formatted ...
Formatted ...
Formatted ...
Formatted ...
Formatted ...
7. Safety Considerations
76.1 Chemicals
The main chemicals used in this process that present safety concerns are the acid catalyst, the
base catalyst and the alcohol. For this preliminary design and safety evaluation sulfuric acid, potassium
sodium hydroxide and methanol will be used. The Material Safety Data Sheets for these chemicals can be
Sulfuric Acid is a colorless, odorless, and highly-corrosive material. The main acute exposure
hazard is severe burns to skin and eyes. It is more harmful than other strong acids due to the dehydrating
nature of the chemical, which releases extra heat, causing secondary burns. It will cause temporary or
permanent blindness if contacted with eyes in either liquid or vapor form. Long term exposure also causes
PotassiumSodium Hydroxide is a caustic base and that is white solid, that is typically available in
flakes or pellets. It is a highly corrosive alkali that will decompose living tissue on contact. It also causes
hydroxide is more dangerous than solid, although solid KNaOH will also exhibit some corrosive behavior
if there is any water present (including sweat or humid air). There are no known long-term exposure
effects of KNaOH; all of the health effects are acute effects due to corrosivity.
Methanol is a colorless, flammable liquid with a distinct odor. If ingested, methanol will be
metabolized to formic acid whichacid, which damages the central nervous system and causes blindness,
coma or death. The adverse health effects associated with methanol all occur internally. While contact
with skin will not cause external damage, it may provide a route for the chemical to enter one’s central
56
76.2 Operating
Sulfuric acid must be stored in a vessel made of a non-reactive reactive material, such as glass.
Great care should be taken that the acid does not contact the operator’s skin. Proper personal protective
equipment (PPE) for handling sulfuric acid includes: safety goggles, face shield, boots, gloves and aprons
made from a suitable material (see MSDS for more information). Sulfuric acid will be pumped directly
from the storage vessel to the pre-treatment vessel, limiting the amount of operator contact needed. If
sulfuric acid does contact the skin though, any contaminated clothing must be removed and the affected
person must wash the acid off under a safety shower for at least 15 minutes. Then seek medical attention
immediately. Also, when diluting the sulfuric acid the acid must be added to the water instead of water
added to the acid. This way, the high heat capacity of water will absorb the heat released as the two
chemicals mix.
Potassium Sodium hydroxide must also be stored in a non-reactive vessel, preferably the
container in which it was delivered. Keep sealed tightly in a cool, dry, well-ventilated area. When
handling potassium sodium hydroxide, the same PPE should be worn as for sulfuric acid. If an operator
needs to create the potasssodium hydroxide solution, a respirator should also be worn. The same
procedure as for the sulfuric acid should also be followed if potasssodium hydroxide contacts skin.
Methanol must be stored in a cool, dry, well-ventilated area away from any potential sparks. If
the methanol does ignite, water will not extinguish the fire. A fire extinguisher will be necessary.
Methanol will be pumped directly from a storage container to the various vessels, so operator contact with
methanol is limited. If an operator must come into contact with the methanol, the same PPE as for sulfuric
acid must be worn. If the area is not well ventilated, a respirator must also be worn. If methanol is
ingested, drink two glasses of water and seek medical attention immediately. If methanol contacts any
part of the body, follow the same procedure as for sulfuric acid.
57
All three chemicals are considered hazardous waste and need to be properly disposed of
Despite being a relatively new energy source with oldest plants dating back to the mid-2000s,
biodiesel is a growing market in the United States. According to the US Energy Information
Administration, approximately 100 million gallons of biodiesel per month are produced in 96 US plants
that have a combined capacity of 2 billion barrels every year. Biofuels provide nearly 6% of the energy
supplied annually, and as of 2009 the United States produces the second largest volume of biofuels. Field Code Changed
depicts the amount of biofuel produced monthly. It can be see that the volume steadily increases overall
Figure 141414: Million barrels of biodiesel produced in the United States from January 2012 to May 2014
58
Figure 1211: Million barrels of biodiesel produced in the United States from January 2012 to May 2014 Formatted: Font: Times New Roman, Not Italic
Formatted: Font: Times New Roman
Figure 8: Million barrels of biodiesel produced in the United States from January 2012 to May 2014
Formatted: Line spacing: Double
Field Code Changed
Producing biodiesel is profitable due to a $1 per barrel tax credit for blenders. Without this
incentive, expensive feed and raw materials prevent biodiesel from competing with conventional diesel
prices. Some states provide further benefits to biodiesel producers, as detailed in a following report
section.
The final product will be marketed and sold to blenders who have the capacity to blend large
volumes of purified product and who will ultimately supply the blended fuel to consumers with diesel
engines. These customers would potentially be community leaders, retail gas station owners, who value
sustainability and desire to promote alternative energy sources. In keeping with the project objective of
introducing a competitive product into the market, the target customer is one who would benefit from
cheaper diesel.
The customer can further be expanded to include any industry using equipment powered by
diesel that desires to use a greener energy source for their operations. Several such industries are
power companies that use diesel for electricity generation, the sugar industry that uses diesel to fuel
sugar boiler vessels, paint companies for wood preservatives, and the agricultural industry for aerial
The plant will be designed to operate for 20 years. At the end of the period the team will decide,
depending on the market, to either sell the plant or specific pieces of equipment at salvage value for
further profits or refurbish the equipment to continue biodiesel production for an extended period. In the
scenario of retiring the plant, future customers would include those who have interest in producing
59
87.1.2 Competition Formatted: Line spacing: Double
The competition in the biodiesel market comes from inside the biodiesel industry and the
The competition from the biodiesel industry comes from similar biodiesel production plants in the
area. For the team, this competition pertains to the biodiesel production plants in Florida, who will
compete for the business of the diesel blenders. According to the plants listing section of biodiesel.org,
there are currently five companies in Florida that produce biodiesel. These business will need to sell their
product to blenders who will then blend the biodiesel with diesel made from crude oil. The blended
There is also competition from the industries creating fuel other than biodiesel. The most
comparative competition comes from the diesel industry because, biodiesel is compatible with diesel
engines. If there is a large discrepancy between the price of biodiesel and diesel, the environmental
benefits of biodiesel will not be enough to overcome the financial burden. This would result in the public
being unwilling to buy biodiesel versus regular diesel at the pump and consequently blenders will lose
interest in purchasing biodiesel from the production businesses. This is unlikely because crude oil is a
limited resource and trends show the price of diesel only increasing in the future. Therefore, the cost
difference of biodiesel and diesel will continue to decrease until biodiesel becomes more cost effective
than diesel.
A more likely source of competition comes from the alternative fuel industry. There is a large
effort to find alternative fuels such as electricity, wind, water, etc. Today vehicles either run on
combustion engines, electric engines, or a combination of both. The biodiesel industry depends on the
continual use of combustion engines. However, as electric motors become more efficient, combustion
engines might eventually become obsolete. With so much research invested into alternative fuels, it is
difficult to tell how the market will change in the future which is a main reason why the expected plant
60
87.2 Tax Information Formatted: Line spacing: Double
Under federal law, a $1 per-gallon tax credit will be applied for the production of biodiesel that
complies with fuel standards and Clean Air Act requirements. This credit will be increased to $1.10 for
the first 15 million gallons produced (approximately BLANK years of production). It is estimated that the
production facility will receive tax credit for 100% of taxes with the 75% state rebate and $1.10/gallon
rebate from the federal government. This credit is valid through 2017 and is expected to be renewed
further.
A major factor in determining the location of the plant was the tax credits available in certain
states beyond the standard $1-per-barrel credit. Overall, Florida is the most helpful for renewable fuel
plant start-ups and provides the proposed plant with the greatest chance of being competitive with diesel
providers.
“An income tax credit is available for 75% of all capital, operation, maintenance, and research
and development costs incurred in connection with an investment in the production, storage, and
distribution of biodiesel (B10-B100), ethanol (E10-E100), or other renewable fuel in the state, up to $1
million annually per taxpayer and $10 million annually for all taxpayers combined.”
This tax credit makes biodiesel production possible, since the process is not efficient enough to
make a profit on its own. This credit is good through December 31, 2018. The credit may only be applied
61
estimated by $1.57 of the nameplate capacity, or the gallons per year output of the plant. From the process
flow diagram, it was found that an estimated 9.5 million gallons per year of biodiesel will be produced.
After multiplying by the above cost factor, it can be preliminarily estimated that the total upfront cost of
In a similar fashion to estimating capital costs, a rough estimate for operating costs can be made.
Fixed costs can be estimated as $0.25 of the nameplate capacity and variable costs can be estimated as
$0.26 of the nameplate capacity. Using the yearly production of 9.5 gallons per year as detailed
previously it was calculated that the overall operating costs are preliminarily estimated at $4.8 million
per year.
In order to determine the profitability of the proposed plant, a selling price for the biodiesel
product to produce a rate of return of 10% was calculated. At a 10% return rate, the project becomes
economically feasible.
The first step in doing this was to calculate the costs of the needed chemical inputs. The costs for
each of the process materials used can be found in the table below. It was determined, preliminarily, that
sodium potassium hydroxide will be used instead of potassiumsodium hydroxide due to ease of
availabilityits lower cost. A very small percentage of hydroxide is used compared to the feed stock,
however, so the price difference becomes insignificant. If it is determined later that sodium hydroxide
will be more beneficial to the process this switch can be easily made with minimal impact to the plant’s
yearly costs.
Table 555: Current market value for and anticpicatedanticipated costs of process materials
Material $/lbCost/U Capacity $/yr Formatted: Centered, Line spacing: Multiple 1.15 li
nit Formatted Table
Formatted: Centered
62
Formatted ...
Formatted ...
Formatted ...
Formatted ...
Formatted ...
Waste Grease $0.40/gal 58,987,500 gal/yr $ 23,595,000.00
Formatted ...
Methanol33 $0.228 $/lb 8,895,893.74 lb/yr $ 2,490,850.25 Formatted ...
Formatted ...
Formatted ...
Potassium Hydroxide34 $0.185 393,250 lb/yr $ 72,751.25 Formatted ...
Sodium Hydroxide35 $/lb0.23 Formatted ...
Sulfuric Acid $0.18 523,809 lb/yr $ 94,285.71 Formatted ...
(95%)36Potassium $/lb0.185 Formatted ...
Hydroxide37 Formatted ...
38 Formatted ...
Sulfuric Acid (95%) 0.18
Formatted ...
Formatted ...
In addition to the above prices, it was found that currently the restaurant grease needed can be Formatted ...
purchased for approximately $0.25 per gallon. Using these prices along with the flow rates in the PFD,
Formatted ...
the following input costs were calculated.
Field Code Changed ...
Formatted ...
Table 5: Cost of input materials per year Formatted ...
Formatted ...
Input Costs ($/yr)
Formatted ...
waste grease $ 23,595,000.00 Formatted ...
Formatted ...
MeOH $ 2,490,850.25
Formatted ...
H2SO4 $ 94,285.71 Formatted ...
Formatted ...
NaOH $ 90,447.50
Formatted ...
Formatted ...
Formatted ...
Formatted ...
Formatted ...
Formatted ...
Formatted ...
33
Methanex, 2014. https://www.methanex.com/our-business/pricing Formatted ...
34
"Caustic Potash." ICIS. ICIS Chemical Business, 2006.
35
ICIS, 2006. http://www.icis.com/chemicals/channel-info-chemicals-a-z/ Formatted ...
36
ICIS Chemical Business, Sulfuric acid market seeks balance, 2010. http://www.icis.com/resources/news/2010/09/06/9390780/sulfuric-acid-
market-seeks-balance/ Formatted ...
37
"Caustic Potash." ICIS. ICIS Chemical Business, 2006.
38
ICIS Chemical Business, Sulfuric acid market seeks balance, 2010. http://www.icis.com/resources/news/2010/09/06/9390780/sulfuric-acid- Formatted ...
market-seeks-balance/
Formatted ...
Formatted ...
63 Formatted ...
Formatted ...
The totals costs per year then, including operating costs calculated previously, are $31.1 million.
The total revenue of the plant comes from the sale of biodiesel and the side product glycerin. The glycerin
can be sold for $0.10 per pound39, or a total of $0.74 million. The revenue of the biodiesel is not known
at this point until the cash flow diagram is created. This process will described next and allows for a
The cash flow diagram was created assuming a construction time of one year. For this reason the
entire capital cost was placed in year -1 of the diagram. As stated above a 20 year life span was assumed
as this is a typical plant life. So, the salvage price of the plant, 10% of the capital costs, and the working
capital was added to year 20 of the cash flow diagram. Using this knowledge equations were used to bring
all costs back to present value. For the plant construction cost using the necessary 10% return, the
$14.8E6(1+0.10)1.
Similarly the salvage and working capital were brought to present value using the 10% rate of
$2.8E6(1+0.10)-20.
The yearly profit was then solved for using the equation,The yearly profit can be solved for with the
Using the above equation it was found that the plant would need a yearly profit of $1.9 million in
order to achieve the needed rate of return. This value was used with the prices of the other materials in the
system detailed above to find a needed yearly biodiesel revenue of $32.2 million. Knowing the yearly Formatted: Footnote Reference
Formatted: Footnote Text
Formatted: Font: (Default) Times New Roman, 8 pt,
Font color: Auto
39 Formatted: apple-converted-space, Font: (Default)
Ahmad, S, D Papadias, and Rick Farmer. "Hydrogen From Glycerol: A Feasibility Study." Hydrogen Energy.
Times New Roman, 8 pt, Font color: Auto
64
output of biodiesel (9.5 million gallons), this can be converted to a selling price per gallon. In order for
the plant to be economically feasible, then, the biodiesel will need to be sold for $3.41 per gallon.
According to research this falls well within the reasonable selling price for biodiesel plants, meaning that
the proposed process will be profitable. The complete cash flow diagram that had been described
Figure 1312: Cash flow diagram for the plant lifespan Formatted: Caption, Centered, Don't keep with next
Figure 9: Cash flow diagram for the plant lifespan Formatted: Line spacing: Multiple 1.15 li
Field Code Changed
In conclusion, it is feasible to open a 9.5 million gallon per year biodiesel production plant. While
this plant alone will not solve the energy crisis, it can be used to demonstrate profitability for others
looking to open biodiesel production plants. With preliminary estimates, the plant will produce a 10% rate
of return over a 20 year lifespan. Many specific decisions still need to be made, such as the reactor type
65
and catalyst, but this report clearly outlines the main design criteria and options. Decision matrices will
need to be formed to determine the best variable choices for this plant. These decisions should be made to
further increase the overall rate of return while not infringing on any of the selected design norms. As
these specific decisions are made next semester, the team will focus on more rigorous design workhe
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Appendix
1. Overall Process Mass Balance
71
2. Filter Calculations
Volume of filtrate (V): used PFD and molar flows/density to find a volumetric flow of 145 m^3/day
Weight of solids per volume of filtrate (cs): weight of solids = (3 wt %)(130,000 kg/day)
cs=26.85 kg/m^3
Density of Solid Particles in Cake: used an average cake density of 3500 kg/m^3
Used in above equation to find Area of Filtration Needed per Day: 225 m^2
72
3. Settler Calculations
First, determine the dispersed phase using:
𝑄𝑙 𝜌𝑙 𝜇ℎ
𝜃=( )[ ⁄𝜌ℎ 𝜇𝑙 ]0.3
𝑄ℎ
Ql – Biodiesel Volumetric Flow Rate – 1.255x10-3 m3/s from PFD
Qh – Glycerin Volumetric Flow Rate – 9.144x10-5 m3/s from PFD
𝜌𝑙 – Biodiesel Density - 875 kg/m3
73
dp – glycerin droplet size falling from mixture – 70 µm from Literature
(Densities and viscosities are same as above with subscript f referring to biodiesel and p to glycerin.)
These values were converted to American Engineering Units, which are needed for the equation, resulting
in a Kc value of 0.385. This means the Stoke’s Equation is applicable. The Stoke’s equation is,
𝑔𝑑𝑝2 (𝜌𝑝 − 𝜌𝑓 )
𝑢𝑡 =
18𝜇𝑓
All values are the same as ones used above. These are used to solve for ut, or settling velocity.
𝑢𝑡 = 4.19𝑥10−4 𝑚/𝑠
Setting a constraint of L/D=5, and knowing interface area (A) = DL, the following equation was derived,
𝑄𝑏𝑖𝑜𝑑𝑖𝑒𝑠𝑒𝑙
≥ 𝑢𝑡
5𝐷2
Minimum D is found to be 0.77 m.
Design suggested: D = 1m & L = 5m
It was determined from this that θ = 7.83, meaning glycerin is dispersed. Next the settling law to be used
was determined with:
(𝜃𝜃 )(𝜃𝜃 − 𝜃𝜃 ) (1) Formatted ...
𝜃𝜃 = 34.81𝜃𝜃 [ ]3
𝜃2𝜃
74
𝜃𝜃2𝜃 (𝜃𝜃 − 𝜃𝜃 ) Formatted: Font: Times New Roman
𝜃𝜃 =
18𝜃𝜃 Formatted: Font: Times New Roman
All values are the same as ones used above. These are used to solve for ut, or settling velocity. Formatted: Font: Times New Roman
Formatted: Font: Times New Roman
𝜃𝜃 = 4.19𝜃10−4 𝜃/𝜃
Formatted: Font: Times New Roman
Setting a constraint of L/D=5, and knowing interface area (A) = DL, the following equation was derived, Formatted: Font: Times New Roman
𝜃𝜃𝜃𝜃𝜃𝜃𝜃𝜃𝜃𝜃 Formatted: Font: Times New Roman
≥ 𝜃𝜃
5𝜃2 Formatted: Font: Times New Roman
Minimum D is found to be 0.77 m. Formatted: Font: Times New Roman
75