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Project Proposal and Feasibility Study

Team 14: GRE-cycle


Hannah Albers, Ben Guilfoyle, Melanie Thelen, and Cole Walker

ENGR 339--Senior Design Project


December 8, 2014

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Executive Summary
The Senior Design team is designing a biodiesel production plant that uses triglyceride-containing
restaurant waste 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, sulfuric acid, methanol,
sodium hydroxide, and a batch reactor will be used. There are three main process sections: pretreatment,
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
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 preliminary cost estimates predict a yearly profit of $1.8 million 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 ............................................................................................................................................ 6
Table of Tables ............................................................................................................................................. 7
1. Introduction ............................................................................................................................................... 8
1.1 Background Information ..................................................................................................................... 8
1.2 Objective ............................................................................................................................................. 9
1.3 Scope ................................................................................................................................................... 9
1.4 Past Project Teams ............................................................................................................................ 10
1.5 Feasibility.......................................................................................................................................... 10
1.5 Comparing Biodiesel and Petroleum Diesel ..................................................................................... 11
1.5.1 Differences in Chemistry ........................................................................................................... 11
1.5.2 Engine Modification .................................................................................................................. 12
1.5.1 Engine Performance ................................................................................................................... 12
2. Design Norms ......................................................................................................................................... 13
2.1 Stewardship ....................................................................................................................................... 13
2.2 Caring................................................................................................................................................ 14
2.3 Transparency ..................................................................................................................................... 14
3. Team Organization.................................................................................................................................. 15
Team Responsibilities ......................................................................................................................... 15
Hannah Albers .................................................................................................................................... 16
Ben Guilfoyle ...................................................................................................................................... 16
Melanie Thelen ................................................................................................................................... 16
Cole Walker ........................................................................................................................................ 16
4. Process Overview.................................................................................................................................... 17
4.1 Process Research ............................................................................................................................... 17
4.1.1 Block Flow Diagram .................................................................................................................. 17
4.1.2 Reaction Chemistry .................................................................................................................... 17
4.1.3 Key Variables............................................................................................................................. 19
4.1.4 Design Alternatives .................................................................................................................... 21
4.2 Material Research ............................................................................................................................. 22
4.2.1 Feed Sources .............................................................................................................................. 22
4.2.2 Feed Composition Research....................................................................................................... 23
4.2.2 Product ....................................................................................................................................... 25

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5. Preliminary Design ................................................................................................................................. 26
5.1 Transesterification Reactor ............................................................................................................... 26
5.1.1 Mass Transfer Limitations ......................................................................................................... 26
5.1.2 Design Alternatives .................................................................................................................... 27
5.2 Catalyst ............................................................................................................................................. 32
5.2.1 Design Criteria ........................................................................................................................... 32
5.2.3 Design Alternatives .................................................................................................................... 32
5.2.4 Past Design Teams ..................................................................................................................... 33
5.2.5 Design Decision ......................................................................................................................... 34
5.3 Pre-Treatment Section ...................................................................................................................... 34
5.3.1 Filter ........................................................................................................................................... 34
5.3.2 Acid Treatment .......................................................................................................................... 36
5.3.3 Waste Separation........................................................................................................................ 38
5.4 Post-Treatment Section ..................................................................................................................... 38
5.4.1 Glycerin Separation.................................................................................................................... 38
5.4.2 Methanol Recovery .................................................................................................................... 41
6. Equipment ............................................................................................................................................... 43
6.1 Equipment Listing............................................................................................................................. 43
7. Safety Considerations ............................................................................................................................. 45
7.1 Chemicals.......................................................................................................................................... 45
7.2 Operating........................................................................................................................................... 46
8. Business Plan .......................................................................................................................................... 47
8.1 Market Study..................................................................................................................................... 47
8.1.1 Customer .................................................................................................................................... 48
8.1.2 Competition................................................................................................................................ 49
8.2 Tax Information ................................................................................................................................ 50
8.3 Costs.................................................................................................................................................. 51
8.3.1 Capital Costs .............................................................................................................................. 51
8.3.2 Operating Costs .......................................................................................................................... 51
8.4 Profitability ....................................................................................................................................... 52
9. Conclusion .............................................................................................................................................. 54
References ................................................................................................................................................... 55
Appendix ..................................................................................................................................................... 58
1. Overall Process Mass Balance ............................................................................................................ 58
2. Filter Calculations ............................................................................................................................... 59

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3. Settler Calculations ............................................................................................................................. 60
4. Competing Biodiesel Plants in Florida ............................................................................................... 61
5. Material Safety Data Sheets (MSDS) ................................................................................................. 61

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Table of Figures

Figure 1: Biodiesel molecule ...................................................................................................................... 11


Figure 2: Petroleum Diesel Molecule ......................................................................................................... 11
Figure 3:Work Breakdown Schedule Organized as Critically Linked Tasks ............................................. 15
Figure 4: Overall Process Block Flow Diagram ......................................................................................... 17
Figure 5: Triglyceride Molecule ................................................................................................................. 18
Figure 6: Overall Biodiesel Reaction .......................................................................................................... 19
Figure 7: Saponification of Free Fatty Acids to form soap ......................................................................... 20
Figure 8:Water formation in an acid catalyst reaction to convert Fatty acids to biodiesel ......................... 20
Figure 9: Standard Curve of Linoleic Acid ................................................................................................. 24
Figure 10: TLC Plate of Butter, Linoleic Acid and Grease Extract ............................................................ 24
Figure 11:Transesterification of triglycerides to form biodiesel (methyl esters) ........................................ 26
Figure 12:Levenspiel Plot of the Pre-Treatment Reaction .......................................................................... 37
Figure 13:Materials of Construction for Handling Caustic Solution .......................................................... 44
Figure 14: Million barrels of biodiesel produced in the United States from January 2012 to May 2014 ... 48
Figure 15: Cash flow diagram for the plant lifespan................................................................................... 54

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Table of Tables

Table 1: EPA Biodiesel Specifications ....................................................................................................... 25


Table 2: Relative densities of effluent stream components ........................................................................ 39
Table 3: Equipment and Materials of Construction .................................................................................... 44
Table 4: Storage Vessel Volumes based on Storage Density Contents ...................................................... 45
Table 5: Current market value and anticpicated costs of process materials................................................ 52

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1. Introduction

1.1 Background Information

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 cannot be

ignored. The demand for crude oil has caused wars, damaged the atmosphere, and eventually must be

replaced by more sustainable energy sources.

Used restaurant grease 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 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 by instead converting this grease to fuel.

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, which makes it a viable and promising option as an alternative to crude oil.

1
Ron, Barnett. "Restaurants' Grease a Hot Item for Thieves." USA Today
2
Beer, T, T Grant, and PK Campbell. "Biodiesel could reduce greenhouse gas emissions." CSIRO. CSIRO, 27 Nov. 2007.

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1.2 Objective

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, which

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

feedstock will be available.

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 economical 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 answer for a

more sustainable future.

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 the 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, 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 purified

biodiesel that can be blended elsewhere.

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1.4 Past Project Teams

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

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

Crew was interested in designing a continuous system.

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 directly using other team projects by scaling up the past designs, but will

instead take into consideration their design decisions while evaluating alternatives.

1.5 Feasibility

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

otherwise useless waste as its feedstock.

3
"How Much Does Biodiesel Reduce Air Pollutants?" AllegroBiodiesel.

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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

efficient than normal diesel. It has been found that fuel efficiency is reduced by 10% compared to regular

diesel4. Despite these drawbacks, the team feels that the economic and environmental considerations

make the proposed process a valuable and feasible project to pursue.

1.5 Comparing Biodiesel and Petroleum Diesel

1.5.1 Differences in Chemistry

Figure 1 depicts a typical biodiesel molecule. It is composed of a long carbon atom chain

(average of 16-20 carbons) with an ester functional group, shown in blue, on one end.

Figure 1: Biodiesel molecule

A typical petroleum diesel molecule looks very similar, except it does not have the same ester

functional group attached to one end.

Figure 2: Petroleum Diesel Molecule

The ester group on the biodiesel molecule makes the fuel much less toxic and more biodegradable

than petroleum diesel. Enzymes such as esterase recognize the ester group on the biodiesel and begin fatty

acid degradation7. This process breaks the molecule down to generate acetyl-CoA, which can be

4
"Biodiesel." fueleconomy.gov. US Department of Energy
5
”The Chemistry of Biodiesel”. Goshen College
6
”The Chemistry of Biodiesel”. Goshen College
7
McKay, DB, “Degradation of triglycerides by a pseudomonad isolated from milk”

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metabolized and thus is biodegradable and non-toxic. Biodiesel is safer for both the environment and

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.

1.5.2 Engine Modification

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 a mechanic should examine the engine

before switching to biodiesel.

Also, biodiesel is more viscous than petroleum diesel so it may gel, causing engine issues while

trying to start the car9. In cool climates, engines may have to be modified by adding a fuel heating system

or using a fuel additive that will lower the viscosity. Viscosity lowering fuel additives are available

commercially, such as Wintron®, a Biodiesel Cold Flow Additive10.

1.5.1 Engine Performance

Overall the engine performance using biodiesel is comparable to using petroleum diesel;

however, some discrepancies occur in fuel efficiency and engine power. The energy content of biodiesel

is slightly less than petroleum diesel, so the overall fuel efficiency is approximately 10% less. Also,

engine power is reduced by 3 to 5% while using biodiesel since it has less energy per unit volume than

petroleum diesel.11

8
“Using Biodiesel Fuel in Your Engine” Penn State Extension.
9
“Engine Modification,” University of Strathclyde Engineering
10
”Biodiesel Cold Fuel Additives,” Biofuel Systems Group LTD
11
“Using Biodiesel Fuel in Your Engine” Penn State Extension.

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Engine clogging can occur if low-quality biodiesel is used since it will contain more deposits and

viscous materials. However, this should not be an engine performance concern if high quality biodiesel is

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 in 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 carbon emissions

so beneficial that the slight increase in NOx is negligible.

2. Design Norms

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

norms should be integrated into early planning stages of the plant and throughout the detailed design

work, construction, and daily operation to ensure the health, well-being, and integrity of employees and

customers alike.

2.1 Stewardship

From its conception, the biodiesel plant proposal is centered on the importance of environmental

stewardship. The proposed biodiesel plant would lower total emissions, generate less hazardous waste,

and draw from a readily available and constant feed source of grease and turn something originally

considered waste into a desirable product. Furthermore, it becomes increasingly vital in a world of

12
“Using Biodiesel Fuel in Your Engine” Penn State Extension.
13
“Biodiesel Emissions,” Biodiesel: America’s Advanced Biofuel.
14
”Nitrogen Oxide,” U.S. National Library of Medicine.

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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.

2.2 Caring

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

the design without taking proper safety measures.

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

profitability of the design over the quality.

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3. Team Organization

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 3, the project could be divided into three sections with research integrated

throughout the process: the main reaction with pretreatment, the main reaction without pretreatment, and

post-treatment. This schedule illustrates the team’s method of approach for choosing the most profitable

design.

Figure 3: Work Breakdown Schedule Organized as Critically Linked Tasks

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

to be familiar with all aspects of the project in order to validate and constructively critique each other’s

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work. Deliverables for class deadlines such as the team poster and executive summary were produced

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

during regular meetings.

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

keep the team’s website up to date throughout the year.

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

met and deliverables were submitted on time.

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

profitability. Melanie and Cole are also working in the lab with grease samples to help the team better

understand typical compositions of restaurant grease for the design.

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4. Process Overview

4.1 Process Research

4.1.1 Block Flow Diagram

Figure 4: Overall Process Block Flow Diagram

4.1.2 Reaction Chemistry

The precursor to biodiesel molecules is a triglyceride, seen below

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Figure 5: Triglyceride Molecule15

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

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

molecules will lower the viscosity.

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 1, the final biodiesel molecule will have a long

carbon chain with an ester group, formed by the addition of the methoxy group. The overall reaction is

shown in Figure 6.

15
”The Chemistry of Biodiesel”. Goshen College

18
Figure 6: Overall Biodiesel Reaction16

where R1, R2, R3 are alkyl groups which can be the same or different. When methanol breaks the carbon-

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

depth in section BLANK.

4.1.3 Key Variables

The feedstock to be used in the process will be trap grease—that is food waste grease that is

unable to be processed as wastewater. The oil portion of the grease may or may not be solid at room

temperature but it will contain solid food particles that need to be filtered out. Within trap grease, there

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,

which can be directly converted to biodiesel, as seen in Figure 3.

The majority of processes involve a pre-treatment of high FFA feedstock with an acid catalyst.

An acid catalyst, like sulfuric acid or hydrochloric acid, will convert the FFAs to esters, increasing the

16
Lasry, Sophie, “Renewable Energy”

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overall conversion and product quality. It has been found that feed 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 formation process, as seen in

Figure 7.

Figure 7: Saponification of Free Fatty Acids to form soap17

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 8, needs to be removed.

Figure 8: Water formation in an acid catalyst reaction to convert Fatty acids to biodiesel 18

17
”Biotechnology Trends,” Best Biotech
18 ”Water Formation in Biodiesel Production,” Intech Journals

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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:

· Number of pre-treatment cycles (0, 1, or 2)


· Acid catalyst used in pre-treatment (sulfuric , hydrochloric , or other)
· Alcohol used in pre-treatment (methanol or ethanol)
· Ratio of acid catalyst to alcohol
· Temperature
· Alkaline catalyst (NaOH, KOH, NaOCH3, metallic Na, or other)
· Ratio of alkaline catalyst to alcohol
· Agitator time
· Settling Time

It is important to note that this process assumes a given feedstock where the initial composition

cannot be predicted or manipulated with accuracy.

4.1.4 Design Alternatives

In addition to the process described above, there are many alternative processes to convert used

grease to biodiesel under development. One option is using a supercritical reactor for processing grease

with high FFA compositions. This process operates at high temperature (275°C to 325°C), high pressure,

and therefore must take place in pressure-rated reaction vessels. This reactor does not require a catalyst

because of the high temperature and pressure, 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

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affect the process. However, the capital and operating costs are very high. This is not a feasible option for

a start-up plant of this scope. It would be better implemented as part of a revamp for a current facility

since capital costs associated with pressure-rated vessels are higher.

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

much more glycerin produced in glycerolysis.

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.

4.2 Material Research

4.2.1 Feed Sources

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

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, it is not

feasible to expect every restaurant to contribute to the plant’s feed stock, so it was estimated that the plant

19 Knight, Lauren. "How Many Restaurants and Bars are there in Miami?"
20 Rosinski, Alan. "How Much Grease Fast Food Places Put Out." greener ideal

22
could collect approximately 75% of this waste grease. This leads to the estimation the plant will operate

with a feed of 130,000 kg of waste restaurant grease per day.

4.2.2 Feed Composition Research

In conjunction with BIOL383L, research was done to analyze the average composition of a

sample of restaurant waste grease. The grease was obtained from Johnny's Café where they make both

vegetable and animal products in the fryer.

4.2.2.1 Methods

First, the waste grease was heated until homogenous and filtered through a cheesecloth to remove

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

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

correlates to the concentration of the sample.

23
4.2.2.2 Results

The area of the samples were calculated using a program called ImageJ, which counts the number

of pixels in a traced area. Standard curves were generated which compared the known concentration to

the number of pixels in the spot.

Figure 9: Standard Curve of Linoleic Acid

Then the extract was run and the area of the triglyceride spot and FFA spot were compared to the

standard curves.

Figure 10: TLC Plate of Butter, Linoleic Acid and Grease Extract

24
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 (). 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 for adequate conversion).

4.2.2 Product

Table 1 features the federal EPA specifications for 100% biodiesel stock fuel that will be met.

Table 1: EPA Biodiesel Specifications

All of these specifications will be met via separation techniques.

21 ”Brown Grease Feedstock for Biodiesel.” National Renewable Energy Laboratory

25
5. Preliminary Design

5.1 Transesterification Reactor

For the main reactor, three parts methanol and one part triglycerides are sent to a reactor for the

transesterification of triglycerides to methyl esters according to the reaction presented below:

Figure 11: Transesterification of triglycerides to form biodiesel (methyl esters)

The catalyst in the reaction is typically a 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 is considered to ensure

maximum conversion.

5.1.1 Mass Transfer Limitations

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

highly viscous triglycerides impede diffusion into methanol.

Increasing 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

26
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.

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-treatment, as smaller droplets are

more stable when dispersed than larger droplets. Both mass transfer and subsequent separation must be

considered in selecting a reactor.

5.1.2 Design Alternatives

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

most commonly used to produce methyl esters.

5.1.2.1 Batch Reactors

Individuals who independently make biodiesel for personal use most commonly use batch reactors.

They are easy to build for a small, garage-scale operation and have a low capital cost. Batch reactors can

convert a wide variety of feedstocks into methyl esters, which is favorable when restaurant grease that, by

nature, has a variable composition is used.

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. Research shows that adding

27
an agitator or series of agitators increases conversion up to 99% while decreasing reaction time. 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

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 Continuous Reactors

5.1.2.2.1 Plug-Flow Reactors (PFRs)

In a PFR, the reaction takes place inside a simple tube or pipe. PFRs are used in continuous

processes with liquid or gas reactants and catalysts. Conversion increases with increasing residence time

and volume. PFRs are rarely used in biodiesel production, according to the literature, because the length

of the reactor necessary to achieve the desired conversion is often impractical

5.1.2.2.2 Packed Bed Reactors

Packed bed reactors are essentially plug-flow reactors containing a solid catalyst. These reactors

ensure an even mixing of reactants throughout the reaction tube to provide higher conversions than batch

reactors but require several hours for this conversion. Activated carbon is typically the solid of choice

coupled with oxides or alcohols. Long tube lengths for PBRs also tend to disqualify them as feasible

reaction vessels.

5.1.2.2.3 Continuous Stirred Tank Reactors (CSTRs)

CSTRs are vessels with agitation used in continuous processes. While a single CSTR does not

outperform a batch reactor in terms of conversion when used in biodiesel production22, CSTRs in series

22 Mazubert, Alex, et al. Intensified processes for FAME production from waste cooking oil: A technological review

28
can approach high conversions. The expense of additional multiple reaction vessels tends to exclude

CSTRs from popular usage.

5.1.2.2.4 Membrane Reactors

Membrane reactors utilize a selectively permeable membrane for methyl ester conversion.

Triglycerides enter the reactor on one side of the membrane while the methanol enters on the other.

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

conversion, similar to a batch reaction, is approximately 1-2 hours.

5.1.2.2.5 Micro-reactors

Micro-reactors that consist of many small, parallel micro-channels have also been used in

biodiesel production. A liquid catalyst such as sodium hydroxide is used to drive the transesterification

that takes place simultaneously in all the channels. The reaction in a micro-reactor would take place near

room temperature so there would be lower energy requirements than at elevated temperatures. Corrosion

issues are avoided by constructing micro-reactors out of plastic resins such as polysulfone and

polytetrafluoroethylene. Use of micro-reactors drastically decreases reaction time in comparison to batch

reactions and other continuous reactors, but the pretreatment step cannot be avoided. High FFA content

can cause plugging in the micro-channels.

5.1.2.2.6 Microwave Reactors

Microwave reactors are used in batch and continuous processes. This type of reactor heats the

reactants through microwave irradiation, which provides all the necessary heating and mixing.

29
Conversion with this heat effect can be over 97% with a residence time of less than one minute. The

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

grease and thus utilize their personal microwaves.

5.1.2.2.7 Cavitational Reactors

There are two different types of cavitational reactors—acoustic and hydrodynamic—that promote

the biodiesel transesterification reaction by generating gaseous cavities that create high energy densities

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

Oscillatory baffled reactors are essentially PFRs with baffles spaced evenly throughout the tube

with an oscillating throughput flow rate. This flow rate facilitates recirculation of the reactants for

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

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.

30
5.1.2.2.9 Reactive Distillation

In reactive distillation, the reaction and separation steps take place simultaneously in a single

distillation column. Methanol and the triglycerides are combined in a single feed stream and drive the

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

Team FAME purposed to design a continuous process for their customers and selected two plug-

flow reactors with a glycerol separation following each. They assumed that this configuration would give

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

microwave reactor

5.1.4 Preliminary Design Decision

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

preferred over continuous processes when a larger degree of control over the system is required, but

biodiesel production does not require this.

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

31
quantity of the desired product. 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.

5.2 Catalyst

5.2.1 Design Criteria

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

energy efficient manner to further cut costs.

5.2.3 Design Alternatives

Catalysts used for transesterification include acids, bases, clays, and enzymes. Bases are most

commonly used largely because they are less expensive than clays and enzymes, and they promote faster

reaction rates than acids.

5.2.3.1 Homogeneous Bases

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.

32
5.2.3.2 Heterogeneous Bases

Heterogeneous catalysts such as MgO, CaO, and NaOH on AlCl3 are easily separated from

products. While homogeneous catalysts must either be disposed of or recycled after separation, a solid

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

time and added expenses.

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.

5.2.4 Past Design Teams

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.

33
5.2.5 Design Decision

The team is leaning towards using NaOH because it is inexpensive, readily available, and most

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.

5.3 Pre-Treatment Section

5.3.1 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.

5.3.1.1 Leaf Filter:

Vertical pressure leaf filters are applied for liquids with low solid content (roughly 1% to 7%).

The vessel of the leaf filter can be suited with a steam jacket to control the temperature in the filter for

liquids that require higher operating temperatures. Vertical pressure leaf filters can be used, rather than

horizontal filters, in cases where light/fine particles are removed to minimize floor space. Vertical

pressure leaf filters 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 noted, 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.

5.3.1.2 Centrifuge:

Centrifuges are commonly used to separate solids from liquids. It uses centripetal acceleration to

separate a mixture based on density; the denser substance moving farther from the axis of rotation, while

34
the lesser dense substance is being pushed toward the axis. Large industrial centrifuges are used to

separate waste grease into white, yellow, and brown grease based on fatty acid concentration. It is also

used in the biofuel industry for fuel purification.

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.

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.

5.3.1.3 Preliminary Design:

Vertical leaf filters were selected to separate out the solids from the waste grease feed. This

comes from the fact that the leaf filters are able to handle the expected solid content of the feed (3 wt %)

as well as its wide use in filtering fatty acid mixtures. The vertical leaf filter can also be fitted with a

steam jacket, which is necessary to maintain high temperature in the filter vessel and minimize grease

viscosity. In order to size the filters needed the following equation was employed.

LA(1-𝜀)𝜀p = cs(V+𝜀LA)

In the above equation, L is the cake thickness, epsilon is the porosity of the cake, rho is the

density of the solid particles in the cake, cs is the weight of solids per volume of filtrate, and V is the

volume of filtrate. These are used to solve for A, or the filter area needed in the process. A complete

calculation and the values used for the above properties can be found in Appendix 2. From this, it was

35
determined that 225 m2 of filter area would be needed for the process. As the maximum filter area of a

vertical leaf filter is 100 m2, it was decided that 3-75 m2 vertical leaf filters will be used in the process.

5.3.2 Acid Treatment

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,

will not be needed in some scenarios.

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

not be sufficient to meet regulations.

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

selection of the PFR.

Knowing the intended flow rates of each component in the plant through the process flow

diagram, a preliminary volume of the pretreatment reactor was determined based on a simplified rate law.

23
"Ethanol and Unleaded Gasoline Average Rack Prices." State of Nebraska. 2014.
24
Abbas, Ammar S., and Sura M. Abbas. "Kinetic Study and Simulation of Oleic Acid Esterification in Different Type of Reactors." IASJ.

36
For the preliminary design, it was assumed that the reaction follows an elementary rate law. This was

modeled as follows;

-rFFA = kCFFACMeOH.

Further modifications were made to this rate law in order to express it in terms of conversion. The

derivation led to the rate law being expressed as,

-rFFA = kC2FFA,0(1-X)(𝜀-X).

Here, 𝜀 refers to the ratio of methanol concentration to free fatty acid concentration entering the

reactor. These initial concentrations were found by using molar masses and densities with initial molar

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

types of reactions average about 0.0833 L/mol hr25.

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.

This plot can be seen below:

Figure 12: Levenspiel Plot of the Pre-Treatment Reaction

25
Barrios, M, J Siles, and A Martin. "A kinetic study of the esterification of free fatty acids (FFA) in sunflower oil."

37
Using the process flow diagram it was determined that a conversion of 97% in the pre-treatment

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

fitting a polynomial equation to the Levenspiel plot. This polynomial was then integrated and solved

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 reactor.

5.3.3 Waste Separation

The stream leaving the pretreatment reactor is comprised of waste water, methanol,

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 stream after

pretreatment accounts for less than 1% of the total volume, so another distillation column would not be

necessary to separate water and methanol.

5.4 Post-Treatment Section

The products leaving the main reactor are primarily methyl esters, excess methanol, and glycerin.

The objective of the post-treatment section is two-fold: the methyl esters must be purified to meet

government specifications, and the excess methanol must be recovered and fed back to the main reactors.

5.4.1 Glycerin Separation

The EPA specifies that up to 0.24 wt% glycerin can be present in biodiesel product. Even with a

rigorous pretreatment process to mitigate soap generation, glycerin in the reactor effluent must be

38
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 2, and the product flowing out of the tank would have only trace amounts of

glycerin.

Table 2: Relative densities of effluent stream components

Effluent Stream Density (g/L)

Glycerin 1.26

Methanol 0.792

Methyl Esters <1

Triglycerides (unreacted) <1

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

example of a biodiesel and glycerin mixture was examined. The methanol was neglected because it has

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

39
is employed. Here, Q refers to volumetric flow rates, which are gathered from the process flow diagram, ρ

refers to fluid densities and µ refers to fluid viscosities. The subscript l is a reference to the light phase

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

temperature ensures liquid phase is maintained.

After determining the dispersed phase, it is necessary to decide which settling law applies. The

following equation was used to do this.

Above, subscript f refers to the biodiesel and subscript p refers to the glycerin. The variable dp is

the average droplet size of the dispersed phase, glycerin, which forms as it falls out of mixture. It was

determined from literature research that this diameter is best approximated as 70 µm27. 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 be maintained when the

piping is designed in detail.

26
Seader, Henley, and Roper. Separation Process Principles. 3rd ed. 795.
27
Abeynaike, A, AJ Sederman, Y Khan, ML Johns, and JF Davidson. "The experimental measurement and modelling of sedimentation and
creaming for glycerol/biodiesel droplet dispersions." Malcolm Mackley. Chemical Engineering Science
28
Seader, Henley, and Roper. Separation Process Principles. 3rd ed. 793.

40
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

From this equation, the settling velocity, ut was calculated to 4.19 x 10-4 m/s. This value must be

equal to or larger than the quotient of biodiesel volumetric flow and interface area. The interface area is

estimated as the diameter of the tank times its length. A ratio for length to diameter of 5 is used, which is

taken as a guideline from references29. This leads to the derivation of the equation

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

dimensions of the settling tank are 5 meter long by 1 meter in diameter.

5.4.2 Methanol Recovery

5.4.2.1 Design Criteria

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

distillation, centrifugation, and pervaporation. Centrifugation is discussed in the pretreatment section of

this report and will not be described in detail here.

29
Seader, Henley, and Roper. Separation Process Principles. 3rd ed. 794.

41
5.4.2.2 Design Alternatives

5.4.2.2.1 Distillation

Methanol and water are commonly separated by distillation. The Diesel Crew utilized Team

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.

5.4.2.2.2 Pervaporation

Pervaporation is a technology that is commonly used to separate water from organic solvents.

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

a centrifuge will be required following pervaporation, it may be more worthwhile to use the budget for

one very effective column or centrifuge.

5.4.2.2.3 Design Decision

A distillation column 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.

42
6. Equipment

6.1 Equipment Listing

The Table 3 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 contain 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 13 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 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 suitable material for the mixer and transesterification

reactor.

43
Figure 13: Materials of Construction for Handling Caustic Solution30

Table 3: Equipment and Materials of Construction

Equipment Material Of
Construction
Vertical Leaf Filters (3) Carbon Steel
Esterification Plug Flow Reactor Stainless Steel coating
Pre-Treatment Distillation Column Stainless Steel coating
Mixer Carbon Steel
Transesterification Reactor Carbon Steel
Post-Treatment Distillation Column Carbon Steel
Settling Tank Carbon Steel

Further equipment will be necessary to ensure necessary energy is supplied and removed from the

system to achieve the desired volume of product. This equipment will include, but is not limited to, heat

exchangers, pumps, valves, and vessels. The number of vessels and respective volumes are shown in

30
"Caustic Soda Solution Storage Tank Lining." Dow Answer Center. The Dow Chemical Company, 6 Nov. 2014. Web. 07 Dec. 2014.

44
Table 4. The appropriate quantity and energy requirements of other necessary equipment will be

determined once additional design decisions are made, the most important of which is the main reactor.

Table 4: Storage Vessel Volumes based on Storage Density Contents *denotes vessels that are incorporated into the process but
are not represented in the process flow diagram

Vessel Contents Volume (m3) Material of Construction


Feed Grease 5 Carbon Steel
Methanol 5 Carbon Steel
50
Sulfuric Acid 0.5 Stainless Steel
Post Pre-Treatment* 150 Carbon Steel
Glycerin 15 Carbon Steel
Biodiesel 150 Carbon Steel
Wastewater* 3 Carbon Steel
KOH 0.5 Stainless Steel

7. Safety Considerations

7.1 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

hydroxide and methanol will be used. The Material Safety Data Sheets for these chemicals can be found

in Appendix 5.

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

lung damage, vitamin deficiency and potentially cancer.

Potassium Hydroxide is a caustic base and 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 secondary

burns, as the decomposition reaction is highly exothermic. Aqueous potassium hydroxide is more

dangerous than solid, although solid KOH will also exhibit some corrosive behavior if there is any water

45
present (including sweat or humid air). There are no known long-term exposure effects of KOH; 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, 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 nervous

system. Methanol is highly flammable and easily ignites.

7.2 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 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

hydroxide, the same PPE should be worn as for sulfuric acid. If an operator needs to create the potassium

hydroxide solution, a respirator should also be worn. The same procedure as for the sulfuric acid should

also be followed if potassium hydroxide contacts skin.

46
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.

All three chemicals are considered hazardous waste and need to be properly disposed of

according to OSHA standards.

8. Business Plan

8.1 Market Study

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.

depicts the amount of biofuel produced monthly. It can be see that the volume steadily increases overall

as more biodiesel plants are built every year.

47
Figure 14: Million barrels of biodiesel produced in the United States from January 2012 to May 2014

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.

8.1.1 Customer

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.

48
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

spraying. Ultimately, any company interested in biodiesel would be interested from an

environmental standpoint or out of a desire to promote themselves as an energy-conscious company.

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

biodiesel themselves or interest in a similar process.

8.1.2 Competition

The competition in the biodiesel market comes from inside the biodiesel industry and the

alternate fuel industries.

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

product is what will be sold to the public as biodiesel at the pump.

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

49
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

life is only 20 years.

8.2 Tax Information

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.

50
“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

toward taxes; no rebates will be issued.

8.3 Costs

8.3.1 Capital Costs

An efficient way to estimate the capital cost of the plant this early into the design process was put

forward by Don Hofstrand of Iowa State University32. The cost including working capital is 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

building the plant will be $14.8 million.

8.3.2 Operating Costs

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.

32
Hofstrand, Don. "Tracking Biodiesel Profitability." Iowa State University.

51
8.4 Profitability

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

potassium hydroxide will be used instead of sodium hydroxide due to its 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 5: Current market value and anticipated costs of process materials

Material Cost/Unit Capacity $/yr

Waste Grease $0.40/gal 58,987,500 gal/yr $ 23,595,000.00

Methanol33 $0.22/lb 8,895,893.74 lb/yr $ 2,490,850.25

Potassium Hydroxide34 $0.185/lb 393,250 lb/yr $ 72,751.25

Sulfuric Acid (95%)36 $0.18/lb 523,809 lb/yr $ 94,285.71

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

33 Methanex, 2014. https://www.methanex.com/our-business/pricing


34
"Caustic Potash." ICIS. ICIS Chemical Business, 2006.
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/
39
Ahmad, S, D Papadias, and Rick Farmer. "Hydrogen From Glycerol: A Feasibility Study." Hydrogen Energy.

52
at this point until the cash flow diagram is created. This process will described next and allows for a

biodiesel selling price to be calculated.

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

equivalent cost was found with,

$14.8E6(1+0.10)1.

Similarly the salvage and working capital were brought to present value using the 10% rate of

return and the equation,

$2.8E6(1+0.10)-20.

The yearly profit can be solved for with the following equation and Microsoft Excel Solver,

Yearly Profit((1+0.10)20-1)/(0.10(1+0.10)20) = $2.8E6(1+0.10)-20 - $14.8E6(1+0.10)1.

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

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

previously can be seen below.

53
Figure 15: Cash flow diagram for the plant lifespan

9. Conclusion

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,

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 work.

54
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57
Appendix
1. Overall Process Mass Balance

58
2. Filter Calculations

LA(1 - ε)ρp = cs (V + εLA)

Cake thickness (L): estimated to 1cm

Porosity (ε): estimated at 0.5

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

59
3. Settler Calculations
First, determine the dispersed phase using:
𝑄𝑙 𝜌 𝜇
𝜃 = ( ) [ 𝑙 ℎ⁄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

𝜌ℎ – Glycerin Density - 1260 kg/m3


𝜇𝑙 – Biodiesel Viscosity – 4.5x10-3 Pa.s
𝜇ℎ – Glycerin Viscosity – 1.0x10-3 Pa.s
It was determined from this that θ = 7.83, meaning glycerin is dispersed. Next the settling law to be used
was determined with:

(𝜌𝑓 )(𝜌𝑝 − 𝜌𝑓 ) (1)


𝐾𝑐 = 34.81𝑑𝑝 [ ]3
𝜇𝑓2

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,

60
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
5𝐷 2
Minimum D is found to be 0.77 m.
Design suggested: D = 1m & L = 5m

4. Competing Biodiesel Plants in Florida

5. Material Safety Data Sheets (MSDS)

See attached

61

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