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BIODIESEL PRODUCTION

FROM SPENT COFFEE GROUNDS:


A PLANT DESIGN
Feasibility Report
Alyana S. Barrinuevo
Antonette Joyce C. Bonifacio
Johanna Martinne E. Canlas
Ariane Victoria M. Dantes

This feasibility study entitled BIODIESEL PRODUCTION FROM SPENT COFFEE


GROUNDS: A PLANT DESIGN, submitted by ALYANA S. BARRINUEVO,
ANTONETTE JOYCE C. BONIFACIO, JOHANNA MARTINNE E. CANLAS and
ARIANE VICTORIA M. DANTES on this 16th day of December, 2015, is hereby accepted
by the University of the Philippines-Diliman Department of Chemical Engineering in partial
fulfillment of the requirements for the degree of BACHELOR OF SCIENCE IN
CHEMICAL ENGINEERING.

ANALIZA P. ROLLON, PhD


ChE 141 Plant Design Adviser

RIZALINDA L. DE LEON, PhD


Chairperson
Department of Chemical Engineering

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University of the Philippines Diliman


College of Engineering
Department of Chemical Engineering

Analiza P. Rollon, PhD


Plant Design Adviser
Chemical Engineering Department

Dear Maam:
We submit herewith a feasibility study report entitled Biodiesel Production from Spent
Coffee Grounds: A Plant Design in partial fulfillment of the requirements of ChE 141
Chemical Process Development and Plant Economics.

Sincerely,

Alyana S. Barrinuevo (2011-01076)


Antonette Joyce C. Bonifacio (2011-42586)
Johanna Martinne E. Canlas (2011-57319)
Ariane Victoria M. Dantes (2011-10377)

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Department of Chemical Engineering


University of the Philippines-Diliman
Quezon City

BIODIESEL PRODUCTION
FROM SPENT COFFEE GROUNDS:
A Plant Design

Alyana S. Barrinuevo
Antonette Joyce C. Bonifacio
Johanna Martinne E. Canlas
Ariane Victoria M. Dantes

In Partial Fulfillment
Of the Requirements in ChE 141:
Chemical Process Development and Plant Economics

Submitted to:
Analiza P. Rollon, Ph. D.
Adviser

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TABLE OF CONTENTS

LETTER OF TRANSMITTAL

! .

EXECUTIVE SUMMARY

1. INTRODUCTION

1.1. Background of the Study


1.2. Opportunity
1.3. Objectives of the Study
1.4. Significance of the Study
1.5. Scope and Limitations

2. MARKET STUDY
2.1. Product Specifications, Supply, and Demand
2.2. Product Growth Rate and Price
2.3. Raw Material Specifications, Supply, and Demand
2.4. Plant Location
2.5. Scale and Mode of Operations

3. GENERAL DESIGN CONSIDERATIONS


3.1. HSE Considerations on Products
3.2. HSE Considerations on Raw Materials
3.3. HSE Considerations on Other Chemicals

4. PROCESS SYNTHESIS & DEVELOPMENT


4.1. Input-Output Structure
4.2. Recycle Structure
4.3. Separation Structure
4.4. Heat Exchanger Network

5. THE PROCESS
5.1. Process Flow Diagram
5.2. Process Description
5.3. Heat and Material Balance
5.4. Equipment List
5.5. Utility List

6. COST ESTIMATION
6.1. Cost Estimation of Purchased Equipment

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7. PROFITABILITY ANALYSIS
7.1. Generation of Cash Flow Diagram
7.2. Profitability Analysis
7.3. Sensitivity and Scenario Analysis

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8. CONCLUSIONS & RECOMMENDATIONS

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ACKNOWLEDGEMENT

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BIBLIOGRAPHY

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APPENDICES

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Design Basis Sheet


Material Safety Data Sheets
Physico-Chemical Property Database & Sample Calculations

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EXECUTIVE SUMMARY
The continuous growth of coffee beverage production entails an increase in the
generation of spent coffee grounds (SCG). Consequently, numerous problems with regards to
waste disposal arise. Thus, devising a process which will use SCG as a potential raw material
is deemed necessary to eventually mitigate the aforementioned environmental concern.

Meanwhile, recent studies have already presented various raw materials for biodiesel
production both in the local and global scenes. Some tapped into the potential of rapeseed,
sunflower as biodiesel feedstock mainly because of the inherently high oil content of these
materials. However, this results in an inevitable competition with food production so there
lies the search for a non-edible source of lipids such as wastes like SCG.

With this opportunity to consider, this study aimed to determine the feasibility of
setting up a profitable and eco-friendly manufacturing plant that utilizes spent coffee grounds
to produce a biodiesel blend within the local standards for biofuel.
Upon completion of the process design, an eco-friendly manufacturing plant has been
successfully set up. First, the food-versus-fuel dilemma encountered in the production of
biofuel was solved since the main feedstock in this feasibility study, spent coffee grounds, is
practically considered a waste material. Second, the direct SCG disposal has been avoided.
SCG is organic in nature and would, thus, require a relatively high oxygen demand to
degrade; if not treated prior to land filling then it may cause environmental hazards.

After a thorough economic and profitability analysis, this investment would seem to
be worth pursuing further based on a payback period of 2.89 years from the start of
operations, a net present value of 12.98 million US, and an IRR of 31% over 10 years of
operation. It should be noted that this analysis was based on a class 4 estimate of the capital
cost (30%). For technical improvement of the profitability analysis, a more detailed estimate
should be used to increase the certainty in the values of economic parameters.

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1. INTRODUCTION
1.1. Background of the Study
As of 2015, the Philippines has experienced its third wave of coffee shop boom. There
has been an increase in the number of units or outlets of specialist coffee shops in the
country. From 581 units in 2009, the number grew to 823 by 2014. With this data, it can be
assumed that wastes like spent coffee grounds (SCG) also increased within this period.
However, SCG is not only produced in specialist coffee shops. It is also produced during the
manufacture of instant coffee. To produce the coffee extract in instant coffee, roasted and
grounded beans are processed with hot water and this process generates SCG. Mussatto et al.
cited Pfulgars paper in his work Production, Composition, and Application of Coffee and Its
Industrial Uses and stated that every ton of green coffee generates about 650 kg of SCG and
1 kg of soluble coffee is associated with 2 kg of SCG. By 2014, the Philippines has recorded
128,000 MT of coffees retail volume. Therefore, approximately 256,000 MT of SCG was
produced last year and this value would only increase since the retail sales volume of instant
coffee is expected to increase by 4.2% CAGR from 2014-2019 (Euromonitor International,
2015).
With large volumes of SCG generated per year, instant coffee manufacturers sought
ways of utilizing SCG in their manufacturing plant. NESCAF claims that they are using
SCG as fuel to their boiler. Different studies show that SCG has a great potential as fuel since
its higher heating value was determined to range from 5000-7000 kcal/kg on a dry basis
(Silva, Nerba, Machado-Silva, & Sanchez, 1998). However, using untreated SCG as a fuel
for boilers may cause dust particles that would still require treatment to meet the standards of
the state for emissions. That being said, the conversion of SCG to other products were studied
and it was found out that it can be a raw material for biodiesel production since it has high
lipid contentapproximately 15 wt. % on a dry basis (Mussatto et al., 2011). Biodiesel
production from SCG produces defatted SCG as by-products and Vardon et al. (2013)
discovered that this by-product can further undergo slow pyrolysis to obtain biochar.

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1.2. Opportunity
With the continuous growth of coffee beverage production, its associated spent coffee
ground generation poses numerous problems with regards to waste disposal because of the
high oxygen demand necessary for decomposition and the probable release of caffeine,
tannin, and polyphenol contaminant residues that may harm the environment (Silva et al.,
1998). In this case, it has been deemed imperative to devise a process which will use SCG as
a potential raw material and eventually mitigate the previously mentioned environmental
concern.
Moreover, recent studies have already presented various raw materials for biodiesel
production both in the local and global scenes. Some tapped into the potential of rapeseed
(Lin, Cunshan, Vittayapadung, Xiangqian, & Mingdong, 2011), sunflower (You, Shie,
Chang, Huang, Pai, Yu, & Chang, 2007), and jatropha (Pahl, 2005) as biodiesel feedstock
mainly because of the inherently high oil content of the aforementioned materials. This,
however, results in an inevitable competition with food production because attempts at
manufacture would definitely entail agricultural cropland occupancy so there lies the search
for a non-edible source of lipids such as wastes, e.g. SCG.

1.3. Objectives of the Study


This study aims to determine the feasibility of setting up a profitable and eco-friendly
manufacturing plant that utilizes spent coffee grounds to produce a biodiesel blend within the
local standards for biofuel.

1.4. Significance of the Study


Upon confirmation of the feasibility of this plant design, two problems are expected to
be solved. First is the food-versus-fuel dilemma encountered in the production of biofuel
since the main feedstock in this feasibility study, spent coffee grounds, is practically
considered a waste material. Second is the problem on SCG disposal. SCG is organic in
nature and would, thus, require a relatively high oxygen demand to degrade; if not treated
prior to land filling then it may cause environmental hazards. Finally, the biodiesel
production section of this prospective chemical plant will save instant coffee manufacturers
the trouble of treating SCG.
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1.5. Scope and Limitations


This plant design would only focus on the feasibility of the commercial scale
production of neat biodiesel from spent coffee grounds in the Philippine setting. The product
and raw material specification would depend on what is present and/or acceptable in the
Philippines. The supply of raw materials and utilities would also be localized.

2. MARKET STUDY
2.1. Product Specifications, Supply, and Demand

2.1.1. Biodiesel
2.1.1.1. Local
The clamor for the shift to alternative fuels has greatly affected the petroleum
industry. Since the passing of the Biofuels Act in the Philippines, renewable energy sources
have become a significant aspect in the countrys energy supply. The Biofuels Act originally
mandated a one percent mix of biofuels in the existing gasoline and fuels last 2007, and it
pushed for the increase of such blend. During the whole year of 2014, every petroleum
product had a two percent biodiesel blend. Thus, every petroleum company in the country has
a market share on the consumption of biodiesel, which also affects the total production of
biodiesel in the country.

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Figure 1. Biodiesel Market Share of Petroleum Companies in the Philippines


(Source: Philippine Department of Energy)

Figure 1 shows the market share of the petroleum companies in the Philippines, with
Petron having the biggest share of 35.4% and Eastern having the smallest share of 0.2% in
the total petroleum products in the country. Because of the blend mandated by the
government, the market share of the petroleum companies in the Philippines in the total
petroleum products will dictate their amount of biodiesel consumption.

Figure 2. Biodiesel Consumption of Petroleum Companies in the Philippines in 2014


(Source: Philippine Department of Energy)

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The actual crudes and petroleum products inventory for the month of December in the
year of 2014 amounted to 2371.40 million liters. Thus, Petron shares 839.48 million liters
while Eastern only shares 47.43 million liters of the total petroleum products produced. The
2% biodiesel blend shows that the total biodiesel consumption of the petroleum companies in
the Philippines was 54.63 million liters. Figure 2 shows the biodiesel consumption of
petroleum companies in the Philippines. Petron has the largest share with 16.79 million liters
of biodiesel, while Eastern has smallest with 0.11 million liters only in 2014. This goes to
show that the biodiesel market greatly depends on the major players, Petron, Shell, and
Chevron having a share of 19.34 million liters, 13.93 million liters, and 4.42 million liters,
respectively.
However, the production of biodiesel does not solely depend on the consumption of
the different petroleum companies in the country, but is determined by the demand,
importation, and production of diesel. These are greatly affected by different factors, but
mainly under transportation and non-transportation. The demand for diesel by vehicles is
influenced by driver behavior, government policy, relative economics between different
drivetrain technologies, vehicle purchase, retirement patterns, and demographics. Other
means of transportation, such as trucking, rail, and shipping, all have their own evolving
demand patterns over time. Meanwhile, non-transportation fuel demand is influenced by
relative fuel costs, including substitutes like natural gas, composition of the economy,
efficiency improvements, and fuel delivery infrastructure. Many of these said factors
influence one another, as well.

Figure 3. Local Biodiesel Production and Consumption from 2009 to 2014


(Source: Euromonitor International)

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Figure 3 shows that the biodiesel production in the Philippines is relatively stable and
has continually increased; in particular, it reached an average of 139.75 million liters from
2010 to 2014. The graph also shows that the lowest production recorded for the past six years
is 117.97 million liters in 2010, while the highest recorded production is 178.95 million liters
in 2014. The decrease in production in 2010 was due to the price surge of coconut oil by 33
percent during the first quarter of the year.
The same figure also exhibits the consumption of biodiesel from 2009 to 2014, which
has also continually increased and has reached an average of 144.49 million liters. According
to the graph, the biodiesel in the country is mostly consumed by the local market and only a
small portion of the total production is exported. The highest recorded consumption is 167.37
million liters in 2014, while the lowest is 129 million liters in 2010. The trend in the biodiesel
production can also be observed in the biodiesel consumption, which will continue to
increase as the mandated biodiesel blend increases in the years to come.

Figure 4. Projected Demand for Coco-Biodiesel, 2014-2030.

Figure 4 shows that the demand for diesel will continue to increase in the years to
come. From this, and with the assumption that the percent blend will be implemented, the
demand for coco-biodiesel will continue to increase, as well. According to the Department of
Energy (DoE), the 2% blend will increase to 5% in mid-2015, giving an average percent

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blend of 3.4 for the entire 2015. The 5% blend was originally targeted for implementation in
2013. It was put off due to the typhoon which occurred during the same year, causing
considerable damage to the coconut-producing regions. Furthermore, this led to higher
coconut prices due to tighter supply. The gradual increase of percent blend can be attributed
to many factors such as the lack of investors needed to reach government mandates. Other
factors that were considered include coconut oil price and availability, environmental impact,
financial impacts, engine fuel compatibility, production benefits for farmers, and most
importantly, production cost. However, the graph shows that the percent blend will again
increase to 10% by 2020 and to 20% by 2025. With the increasing demand for cocobiodiesel, ten refineries would be required with a capacity of 44 million liters per plant by
2020 and 20 refineries by 2025.
2.1.1.2. Global
The demand for renewable fuels worldwide is also growing rapidly with the mandated
usage levels and new legislation under development in the field. In addition to that, the
growing demand for petroleum products also play a part in shaping the biodiesel demand, as
the amounts of biodiesel will depend on the total amount of petroleum consumed, as well as
on other factors mentioned.

Figure 5. Global Biodiesel Production and Consumption, 2008-2012.


(Source: U.S. Energy Information Administration)

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According to Figure 5, the global production and consumption of biodiesel has


steadily increased from 15,210 million liters to 25,026 million liters and 14,054 million liters
to 24,328 million liters in 2008 and 2012, respectively. This phenomenon may be attributed
to the increasing mandatory blend of biodiesel in regular diesel for different countries around
the world, together with the considerable advantages over regular diesel in terms of (i) fuel
efficiency, (ii) emission, and (iii) power.
2.1.2. Glycerol
Glycerol is a by-product of the transesterification reaction for biodiesel production. It
is formed when the alkoxy group of the triglyceride combines with the hydroxyl group of the
alcohol. However, it is difficult and expensive to purify the glycerol produced by the
biodiesel industry, hence, it is being sold to other industries since it has many uses in the
food, cosmetics, and pharmaceutical industry.

Figure 6. Global Import and Export Quantity of Glycerol, 2010-2014.


(Source: ITC Trademap)

Figure 6 shows the global export and import amounts of glycerol to and from different
countries. The export quantities denote part of the glycerol production in the country in 2010
to 2014 which, as seen on the graph, are very far from the import quantities in the same years.
It shows that the trend of export quantity of glycerol is fluctuating with an average of 6.32
million liters in the past five years. The highest recorded export quantity is 11.02 million
liters in 2014. However in 2013, the biodiesel production began to increase worldwide. With

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so many producers of biodiesel with glycerol as the, the country decreased the quantity for
export, and thus, the lowest recorded export quantity is 3.08 million liters in 2013.
Meanwhile, the trend of import is relatively stable with a decrease in 2010 to 2012 and an
increase in 2013 to 2014. The average import quantity is around 0.91 million liters in the past
5 years with 1.32 million liters as the highest recorded import quantity in 2014 and 0.46
million liters as the lowest in 2011.

2.2. Product Growth Rate and Price


2.2.1. Biodiesel

Figure 7. Annual growth rate in the global biodiesel industry, 2008-2012.

The annual growth rate in production and consumption of biodiesel shown in Figure 7
was calculated from the values presented in Figure 5. Generally, the industry has experienced
a sharp slowdown in terms of growth rate. The decline is due to the significant industry
transition to novel fuels and feedstock in order to allow long-term growth in the face of
impediments like the food versus fuel debate and imminent blend regulations for biodiesel
and ethanol. According to Andrew Soare, next-generation feedstock like waste oils and
cellulosic biomass are not tied up in the food supply and could unlock significant economic
advantages, assuming novel conversions commercialize (Jacques, 2013).

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Globally, the price of biodiesel varies because of different reasons. According to the
US Department of Energy (2011), it is mainly dependent on market price formation based on
the sum of the diesel price on Platts and a premium price and on the blend considered; the
greater the amount of biodiesel in the blend, the higher the cost, with B100 (or 100%
biodiesel) being the most expensive (Ferrari, 2013).
Based on Figure 8, biodiesel prices are expected to remain firm after 2011. The prices
are projected to be on average 45% higher than the previous decade, reaching USD 1623 per
ton by 2020. Increased competitiveness of biodiesel in the market is expected over the course
of the projection period since the prices should increase less rapidly than crude oil prices
(Ferrari, 2013).

Figure 8. Evolution and projection of biodiesel prices in $/ton (1996-2020).

2.2.2. Glycerol

Figure 9. Global Import and Export Value of Glycerol, 2010-2014.


(Source: ITC Trademap)

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According to the above graph (Figure 9), the trend of the import price continually
increased with the highest recorded price of approximately 968,000 USD per million liters in
2014. This is because the sales of the oleochemical products, such as fatty acid and fatty
alcohol, has stagnated because of the European financial crisis, Chinese business dormancy,
etc. The glycerol output volume decreased globally, which resulted in the increase in import
price. The lowest recorded import price is around 470,000 USD per million liters in 2010
because the demand for biodiesel and oleochemical products has been good in early 2011,
and glycerol production has increased sharply together with the production of biodiesel fuel
(Green Chemical, 2012).
Meanwhile, the trend of the export price of glycerol increased from 2010 to 2013 but
decreased in 2014. The highest recorded export price is around 469,000 USD per million
liters in 2013 because of the lowest export quantity during this year. The lowest is
approximately 317,000 USD per million liters in 2010 also because of the increase in the
production of glycerol in early 2011 as already stated above.

2.3. Raw Material Specifications, Supply, and Demand


2.3.1 Spent Coffee Grounds

2.3.1.1. Global Supply


Spent coffee grounds (SCG) offer a viable feedstock for biodiesel production. For
every gram of coffee produced, 0.91 gram of waste grounds is generated (Dugmore, 2013).
With this information, the annual global supply of SCG, which is shown in Figure 10, was
calculated using the gathered production data (US Department of Agriculture, 2015). It can
be seen that there is a relatively steady supply of about 8 million tons of SCG every year.
These SCG are not sold at any value and are currently disposed of as solid wastes or, in few
cases, used as fertilizers or even burned. Studies show that averagely, SCG contain around
15% oil. Using SCG on biodiesel production is economical, eco-friendly, and can potentially
contribute 340 million gallons of biodiesel to the worlds supply (Ng, n.d.).

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Figure 10. Annual global supply of spent coffee grounds from 2010 to 2014.
(U.S. Department of Agriculture)

2.3.1.2. Local Supply

Figure 11. 2014 Coffee Retail Sales in Volume (Euromonitor International, 2015).

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Figure 12. SCG Production and Consumption (Euromonitor International, 2015).

From the first figure (Figure 11), it can be seen that instant coffee sells better than
fresh coffee in the Philippines. According to the Euromonitor Journals, this can be accounted
to the fact that instant coffee is more affordable than fresh coffee and that instant coffee is
easier to prepare; whereas, fresh coffee requires a coffee machine which only a few
households have. For the sake of this feasibility study, the data for instant coffee was used
since it is practically almost 100% of the coffee consumed in the Philippines.
It was also mentioned earlier that for every kilogram of instant coffee produced, two
kilograms of spent coffee grounds is generated. In line with this, the data for SCG production
was based from instant coffee retail sales due to lack of other pertinent and actual data. It has
been assumed that the volume of SCG generated is just approximately double the volume of
the instant coffee retail sales. From Figure 12, it can be seen that coffee retail sales has
increased with a growth rate of 14.8% (CAGR). This increase is not only because of the
population increase in the country but also because of the innovations with instant coffee
production. The number of 3-in-1 coffee flavors increased and, recently, white coffee was
released in the market. These products cater to the sweet tooth of the Filipino, making them
more popular. With this popularity, the volume of SCG generated increased accordingly as
production of instant coffee increased.
No consumption data are available since SCG from manufacturing plants are just used
as landfill or burned in the reboiler. Import and export values are also not available since
SCG is never imported or exported.

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Figure 13. NBO Company Share: % Retail Value 2014 (Euromonitor International).

From the figure above (Figure 13), it can be seen that Nestl Philippines Inc. has the
highest market share in the coffee industry. However, its Cagayan de Oro factory uses spent
coffee grounds as fuel to generate steam. The next option to be considered is the Universal
Robina Corporation (URC), which has no previous record of burning their SCGs.

2.3.2. Methanol
2.3.2.1. Global Supply and Demand

Figure 14. Global Methanol Supply and Demand Balance.


Source: Methanol Market Services Asia

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The global methanol supply had a great boom from 2008 to 2013 with an annual
growth rate of 9.9% CAGR. This increase can be attributed to the rise of alternative fuels
produced with the use of methanol, specifically blended gasoline, dimethyl ether, and
biodiesel with annual growth rates of 24.4%, 21.0% and 6.0% (CAGR), respectively. This
shows how the world tends to shift to clean and green technology because of global warming.
Another interesting derivative of methanol that boomed was olefins. Olefins derived from
methanol became popular because countries with high oil price can now produce olefins that
are not derived from naphtha. In fact, the demand for methanol in MTO increased from 7000
MT in 2008 to 5.886 million metric tons in 2013. Other products derived from methanol that
affected its global demand are formaldehyde, acetic acid, methyl tert-butyl ether, methyl
methacrylate, dimethyl terephthalate, methanethiol, methylamines, methyl chloride, and fuel
cells.
It can be seen in Figure 14 that the total supply was always close in quantity to the
total demand. In fact, the highest deficit and surplus during these years were 0.168 MMT and
0.019 MMT, respectively. This is an effort to keep methanols global price constant.
2.3.2.2. Local Supply and Demand

Figure 15. Local Methanol Market Data.


Source: International Trade Commission Trade Map

There is no available data concerning the local production of alcohol in the country so
it has been assumed that the Philippines only relies on imports. There was a decline in

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imports in 2013 mainly because of an all-time high price of methanol on the said year within
the featured time range. It increased from $295/MT in 2008 to $377/MT in 2013 (Figure 15).
2.3.2.3. Current Posted Price
Methanex Corporation is the worlds largest producer and supplier of methanol to
major international markets in North America, Asia Pacific, Europe and South America.
According to the regional contract prices posted on their website last August 30, 2015,
methanol in Asia Pacific is being sold at USD 315/MT (Methanex, 2015). It should be noted
that their price sheets are updated at the end of each month.

2.4. Plant Location


Knowing that URC does not recycle their SCG for steam generation, it has been
decided to build this biodiesel plant in San Pedro, Laguna, where the largest coffee
manufacturing plant is located. By doing so, the said plant will be closer to the source of the
main raw material. Aside from this, there are also other factors which were considered, such
as availability of necessary utility like electricity, water, fuel, and communication;
availability of skilled and unskilled labor; availability of sewage and/or waterways for
wastewater disposal; accessibility of transportation vehicles; and the fact that the chosen
location lies in an industrial zone.

2.5. Scale and Mode of Operations


From Euromonitor, it has been found out that the country will be needing ten
biodiesel plants by 2020 whose individual capacity should be 44 million liters per year. As a
starting plant, the authors initially decided to operate with less than half of the
aforementioned capacity and ended up with a capacity of 18 million liters per year requiring a
supply of around 128,000 MT of spent coffee grounds per year. With this high amount of
capacity, the plants biodiesel production is expected to be a continuous process

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3. GENERAL DESIGN CONSIDERATIONS


3.1. HSE Considerations on Products
PRODUCT

Biodiesel

HEALTH AND
ENVIRONMENTA
SAFETY HAZARD
L HAZARD

INHALATION:

Negligible in liquid
form but vapors may
cause mucus
membrane irritation,
dizziness and
nausea.

EYE CONTACT:

May cause eye


irritation

SKIN CONTACT:

Product does not


cause skin irritation
upon prolonged or
repeated contact.

INGESTION:

FIRE AND
EXPLOSION
HAZARD

Glycerol, a
byproduct of the
biodiesel must
not be disposed
on the ground or
any surface water.
Any stream
containing
glycerol should
be treated in a
wastewater
facility first
before disposal. If
left untreated,
glycerol may
solidify and clog
sewage system.
Foul odors
produced from
the reaction step
in the process
may offend
neighbors.
Disposal of a bad
batch of biodiesel
should also be
taken into
consideration

No hazards
anticipated from
ingestion incidental
to industrial
exposure.

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Glycerin (CAS #
56-81-5)

Potential Acute
Health Effects:

Ecotoxicity:

Ecotoxicity in water
Slightly hazardous in (LC50): 58.5 ppm 96
case of skin contact
hours [Trout].
(irritant, permeator),
of eye contact
(irritant), of
BOD5 and COD:
ingestion, of
inhalation.

Flammability of the
Product:

May be combustible
at high temperature.

Auto-Ignition
Temperature:

Not available.
Potential Chronic
Health Effects:
Products of
Biodegradation:
CARCINOGENIC
EFFECTS: Not
available.

MUTAGENIC
EFFECTS: Not
available.

TERATOGENIC
EFFECTS: Not
available.

DEVELOPMENTA
L TOXICITY: Not
available. The
substance may be
toxic to kidneys.
Repeated or
prolonged exposure
to the substance can
produce target
organs damage.

370C
(698F)(NFPA Fire
Protection Guide to
Hazardous Materials,
13th ed., 2002;
NIOSH ICSC, 2001;
CHRIS, 2001) 392 C
(739 F) (Lewis,
1997)

Possibly hazardous
short term
degradation products
are not likely.
However, long term
degradation products Flash Points:
may arise.

CLOSED CUP:
160C (320F).
Toxicity of the
(Chemical Hazard
Products of
Response
Biodegradation:
Information System,
2001; Lewis, 1997).
OPEN CUP: 177C
The products of
(350.6F) (Budavari,
degradation are less 2000; Chemical
toxic than the
Response
product itself.
Information System,
2001; NIOSH ICSC,
2001) OPEN CUP:
Special Remarks on 199 C(390 F)
(National Fire
the Products of
Protection
Biodegradation:
Association, Fire
Protection Guide to

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25

Not available.

Hazardous Materials,
13 ed., 2002)

Flammable Limits:

LOWER: 0.9%

Products of
Combustion:

These products are


carbon oxides (CO,
CO2), irritating and
toxic fumes.

Fire Hazards in
Presence of Various
Substances:

Slightly flammable
to flammable in
presence of open
flames and sparks, of
heat, of oxidizing
materials. Nonflammable in
presence of shocks.

Explosion Hazards
in Presence of
Various
Substances:

Risks of explosion of
the product in

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26

presence of
mechanical impact:
Not available. Risks
of explosion of the
product in presence
of static discharge:
Not available.
Explosive in
presence of
oxidizing materials.

Fire Fighting
Media and
Instructions:

SMALL FIRE: Use


DRY chemical
powder. LARGE
FIRE: Use water
spray, fog or foam.
Do not use water jet.

Special Remarks on
Fire Hazards:

Not available.

Special Remarks on
Explosion Hazards:

Glycerin is
incompatible with
strong oxidizers such
as chromium
trioxide, potassium
chlorate, or
potassium
permanganate and
may explode on
contact with these

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27

compounds.
Explosive glyceryl
nitrate is formed
from a mixture of
glycerin and nitric
and sulfuric acids.
Perchloric acid , lead
oxide + glycerin
form perchloric
esters which may be
explosive. Glycerin
and chlorine may
explode if heated
and confined.

3.2. HSE Considerations on Raw Materials


RAW MATERIAL

Coffee Grounds

HEALTH AND
SAFETY HAZARD

INHALATION:

ENVIRONMENTAL
HAZARD

None.

FIRE AND
EXPLOSION
HAZARD
Autoignition
Temperature: 1697 F
(925 C)

None.

EYE CONTACT:

May cause irritation.


Wash eyes for 15
minutes.

SKIN CONTACT:

May cause irritation.


Could stain skin a dark
color.

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28

INGESTION:

May cause
hyperacidity if too
much is taken.

Methanol (CAS # 6756-1)

Potential Acute
Health Effects:

Hazardous in case of
skin contact (irritant),
of eye contact
(irritant), of ingestion,
of inhalation. Slightly
hazardous in case of
skin contact
(permeator). Severe
over-exposure can
result in death.

Potential Chronic
Health Effects:

Slightly hazardous in
case of skin contact
(sensitizer).

CARCINOGENIC
EFFECTS: Not
available.

MUTAGENIC
EFFECTS: Mutagenic
for mammalian
somatic cells.
Mutagenic for bacteria
and/or yeast.

Ecotoxicity:

Flammability of the
Product:

Ecotoxicity in water
(LC50): 29400 mg/l 96 Flammable.
hours [Fathead
Minnow].
Auto-Ignition
Temperature:
BOD5 and COD:
464C (867.2F)
Not available.
Flash Points:
Products of
Biodegradation:

Possibly hazardous
short term degradation
products are not likely.
However, long term
degradation products
may arise.

Toxicity of the
Products of
Biodegradation:

CLOSED CUP: 12C


(53.6F). OPEN CUP:
16C (60.8F).

Flammable Limits:

LOWER: 6% UPPER:
36.5%

Products of
Combustion:
The products of
degradation are less
toxic than the product
itself.

These products are


carbon oxides (CO,
CO2).

TERATOGENIC

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29

EFFECTS: Classified
POSSIBLE for human.

DEVELOPMENTAL
TOXICITY: Not
available.

Special Remarks on
the Products of
Biodegradation:

Methanol in water is
rapidly biodegraded
and volatilized.
The substance is toxic Aquatic hydrolysis,
to eyes. The substance oxidation, photolysis,
may be toxic to blood, adsorption to
kidneys, liver, brain,
sediment, and
peripheral nervous
bioconcentration are
system, upper
not significant fate
respiratory tract, skin, processes. The halfcentral nervous system life of methanol in
(CNS), optic nerve.
surfact water ranges
Repeated or prolonged from 24 hrs. to 168
exposure to the
hrs. Based on its vapor
substance can produce pressure, methanol
target organs damage. exists almost entirely
Repeated exposure to a in the vapor phase in
highly toxic material
the ambient
may produce general
atmosphere. It is
deterioration of health degraded by reaction
by an accumulation in with photochemically
one or many human
produced hydroxyl
organs.
radicals and has an
estimated half-life of
17.8 days. Methanol is
physically removed
from air by rain due to
its solubility. Methanol
can react with NO2 in
pollulted to form
methyl nitrate. The
half-life of methanol in
air ranges from 71 hrs.
(3 days) to 713 hrs.
(29.7 days) based on
photooxidation halflife in air.

Fire Hazards in
Presence of Various
Substances:

Highly flammable in
presence of open
flames and sparks, of
heat. Non-flammable
in presence of shocks.

Explosion Hazards in
Presence of Various
Substances:

Risks of explosion of
the product in presence
of mechanical impact:
Not available.
Explosive in presence
of open flames and
sparks, of heat.

Fire Fighting Media


and Instructions:

Flammable liquid,
soluble or dispersed in
water. SMALL FIRE:
Use DRY chemical
powder. LARGE
FIRE: Use alcohol
foam, water spray or
fog.

Special Remarks on
Fire Hazards:

Explosive in the form


of vapor when exposed

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30

to heat or flame. Vapor


may travel
considerable distance
to source of ignition
and flash back. When
heated to
decomposition, it
emits acrid smoke and
irritating fumes.
CAUTION: MAY
BURN WITH NEAR
INVISIBLE FLAME

Special Remarks on
Explosion Hazards:

Forms an explosive
mixture with air due to
its low flash point.
Explosive when mixed
with Choroform +
sodium methoxide and
diethyl zinc. It boils
violently and explodes.

3.3. HSE Considerations on Other Chemicals


CHEMICAL

Sulfuric acid (CAS #


7664-93-9)

HEALTH AND
SAFETY HAZARD

Potential Acute
Health Effects:

ENVIRONMENTAL
HAZARD

Ecotoxicity:

Ecotoxicity in water
Very hazardous in case (LC50): 49 mg/l 48
of skin contact
hours
(corrosive, irritant,
[bluegill/sunfish].
permeator), of eye
contact (irritant,
corrosive), of
BOD5 and COD:
ingestion, of
inhalation. Liquid or
spray mist may

FIRE AND
EXPLOSION
HAZARD
Flammability of the
Product:

Non-flammable.

Auto-Ignition
Temperature:

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31

produce tissue damage


particularly on mucous
membranes of eyes,
mouth and respiratory
tract. Skin contact may
produce burns.
Inhalation of the spray
mist may produce
severe irritation of
respiratory tract,
characterized by
coughing, choking, or
shortness of breath.
Severe over-exposure
can result in death.
Inflammation of the
eye is characterized by
redness, watering, and
itching. Skin
inflammation is
characterized by
itching, scaling,
reddening, or,
occasionally,
blistering.

Potential Chronic
Health Effects:

CARCINOGENIC
EFFECTS: Classified
1 (Proven for human.)
by IARC, + (Proven.)
by OSHA. Classified
A2 (Suspected for
human.) by ACGIH.

MUTAGENIC
EFFECTS: Not
available.

TERATOGENIC
EFFECTS: Not
available.

Not available.

Not applicable.

Products of
Biodegradation:

Flash Points:

Not applicable.
Possibly hazardous
short term degradation
products are not likely.
However, long term
degradation products
may arise.

Flammable Limits:

Not applicable.
Toxicity of the
Products of
Biodegradation:

The products of
degradation are less
toxic than the product
itself.

Special Remarks on
the Products of
Biodegradation:

Not available.

Products of
Combustion:

Products of
combustion are not
available since
material is nonflammable. However,
products of
decompostion include
fumes of oxides of
sulfur. Will react with
water or steam to
produce toxic and
corrosive fumes.
Reacts with carbonates
to generate carbon
dioxide gas. Reacts
with cyanides and
sulfides to form
poisonous hydrogen
cyanide and hydrogen
sulfide respectively.

Fire Hazards in
Presence of Various
Substances:

Combustible materials

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32

DEVELOPMENTAL
TOXICITY: Not
available. The
substance may be toxic
to kidneys, lungs,
heart, cardiovascular
system, upper
respiratory tract, eyes,
teeth. Repeated or
prolonged exposure to
the substance can
produce target organs
damage. Repeated or
prolonged contact with
spray mist may
produce chronic eye
irritation and severe
skin irritation.
Repeated or prolonged
exposure to spray mist
may produce
respiratory tract
irritation leading to
frequent attacks of
bronchial infection.
Repeated exposure to a
highly toxic material
may produce general
deterioration of health
by an accumulation in
one or many human
organs.

Explosion Hazards in
Presence of Various
Substances:

Risks of explosion of
the product in presence
of mechanical impact:
Not available. Risks of
explosion of the
product in presence of
static discharge: Not
available. Slightly
explosive in presence
of oxidizing materials.

Fire Fighting Media


and Instructions:

Not applicable.

Special Remarks on
Fire Hazards:

Metal acetylides
(Monocesium and
Monorubidium), and
carbides ignite with
concentrated sulfuric
acid. White
Phosphorous + boiling
Sulfuric acid or its
vapor ignites on
contact. May ignite
other combustible
materials. May cause
fire when sulfuric acid
is mixed with
Cyclopentadiene,
cyclopentanone oxime,
nitroaryl amines,
hexalithium disilicide,
phorphorous (III)

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33

oxide, and oxidizing


agents such as
chlorates, halogens,
permanganates.

Special Remarks on
Explosion Hazards:

Mixtures of sulfuric
acid and any of the
following can explode:
p-nitrotoluene,
pentasilver
trihydroxydiaminopho
sphate, perchlorates,
alcohols with strong
hydrogen peroxide,
ammonium
tetraperoxychromate,
mercuric nitrite,
potassium chlorate,
potassium
permanganate with
potassium chloride,
carbides, nitro
compounds, nitrates,
carbides, phosphorous,
iodides, picratres,
fulminats, dienes,
alcohols (when heated)
Nitramide decomposes
explosively on contact
with concentrated
sulfuric acid. 1,3,5Trinitrosohexahydro1,3,5-triazine +
sulfuric acid causes
explosive
decompositon.
Sodium methoxide
(CAS # 124-41-4)

Potential Acute
Health Effects:

Ecotoxicity:

Flammability of the
Product:

Not available.
Hazardous in case of
skin contact
(corrosive, irritant,
sensitizer, permeator),

Flammable.
BOD5 and COD:

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34

of eye contact (irritant,


corrosive), of
ingestion, of
inhalation. The amount
of tissue damage
depends on length of
contact. Eye contact
can result in corneal
damage or blindness.
Skin contact can
produce inflammation
and blistering.
Inhalation of dust will
produce irritation to
gastro-intestinal or
respiratory tract,
characterized by
burning, sneezing and
coughing. Severe overexposure can produce
lung damage, choking,
unconsciousness or
death.

Potential Chronic
Health Effects:

Slightly hazardous in
case of skin contact
(sensitizer).

CARCINOGENIC
EFFECTS: Not
available.

MUTAGENIC
EFFECTS: Not
available.

TERATOGENIC
EFFECTS: Not
available.

Auto-Ignition
Temperature:
Not available.
88C (190.4F)
Products of
Biodegradation:
Flash Points:
Possibly hazardous
short term degradation
products are not likely.
However, long term
degradation products
may arise.

CLOSED CUP: 33C


(91.4F).

Flammable Limits:
Toxicity of the
Products of
Biodegradation:

The product itself and


its products of
degradation are not
toxic.

Special Remarks on
the Products of
Biodegradation:

Not available.

LOWER: 7.3%
UPPER: 36%

Products of
Combustion:

These products are


carbon oxides (CO,
CO2).

Fire Hazards in
Presence of Various
Substances:

Highly flammable in
presence of moisture.
Flammable in presence
of open flames and
sparks, of heat.

Explosion Hazards in
Presence of Various
Substances:

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35

DEVELOPMENTAL
TOXICITY: Not
available. Repeated
exposure of the eyes to
a low level of dust can
produce eye irritation.
Repeated skin
exposure can produce
local skin destruction,
or dermatitis. Repeated
inhalation of dust can
produce varying
degree of respiratory
irritation or lung
damage.

Risks of explosion of
the product in presence
of mechanical impact:
Not available. Risks of
explosion of the
product in presence of
static discharge: Not
available. Fire

Fighting Media and


Instructions:

Flammable solid.
Moisture reactive
material. SMALL
FIRE: Obtain advice
on use of water. Use
DRY chemical
powder. LARGE
FIRE: Use water spray
or fog. Do not use
water jet.

Special Remarks on
Fire Hazards:

Dangerous. It ignites
spontaneously in moist
air. This material is
pyrophoric (ignites
spontaneously in air)
at temperatures
approximately 50 deg.
C and above.

Special Remarks on
Explosion Hazards:

Material in powder
form, capable of
creating a dust

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36

explosion. Sodium
methylate and Methyl
azide + Dimethyl
Malonate may cause
an explosion. Sodium
Methylate and
Perchloryl Fluoride +
Methyl alcohol may
cause an explosion. To
rapid of an addition of
Sodium Methylate to a
mixture of chloroform
and methanol may
cause an explosion.

4. PROCESS SYNTHESIS & DEVELOPMENT


4.1. Input-Output Structure
Table 1. Comparison of Transesterification Processes for Biodiesel Production.
(Abbaszaadeh et al., 2012; Helwani et al., 2009)
HoBC

HoAC

Biocatalytic

HetSBC

HetAC

SAT

Biox
Cosolvent

40-60

60-100

30-40

75-250

75-250

250-400

30

Soap
formation

No influence

No influence

No influence

No influence

Tolerable

No
influence

Water in raw
mats

Inhibitor

No influence

At low content,
maximum activity of
lipase

Inhibitor

No influence

Tolerable

No
influence

Product
yield

Normal

High

Depends on enzyme

Normal

Normal

High

High

Glycerol
recovery

Difficult

Comparatively
easy

Easy

Comparatively
Easy

Comparatively
Easy

Easy

Easya

Biodiesel
purification

Water
washing

Water
washing

None

Water
washing

None

Easy

Easy

Catalyst cost

Cheap

Cheap

Expensive

Cheap

Expensive

NA

Expensive

Rate of
reaction

Faster
comparatively

Slower than
HOBC

Relatively slower than


HoBC and HoAC

Slow

Slower than
HetSBC

Very
Fast

Fast

Reaction
Temperature
(0F)
FFA in
feedstock

HoBC Homogeneous Base Catalytic Transesterification


HoAC - Homogeneous Acid Catalytic Transesterification
HetSBC Heterogenous Solid-base Catalytic Transesterification
HetSAC Heterogenous Solid-acid Catalytic Transesterification
SAT Supercritical Alcohol Transesterification

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37

The proponents decided to use homogeneous catalytic transesterification because of


its high reaction rate, low temperature requirement, and cheap catalyst. Despite having
additional costs

for product

separation and purification, homogeneous

catalytic

transesterification still proved to be more competitive compared to other transesterification


processes. Though heterogeneous solid base catalyst shows promise because it does not
require much product purification, it has relatively slow reaction rate. The HetSBC, with
reaction rate faster than HetSAC, is said to be relatively cheaper than its homogeneous
counterpart especially if cheap catalysts like metal oxides are used. However, CaO, a
common metal hydroxide used in the industry for HetSBC, can leach into the reaction
mixture thus requiring product separation and purification which defeats the purpose of
HetSBC. Aside from that, its reaction rate is slow.
As for the supercritical alcohol transesterification, it is downright expensive. Aside
from high utility cost needed because of its high temperature and pressure requirement, its
alcohol to oil ratio is 42:1. This ratio is very high compared to 6:1 for homogenous catalysts
thus accounting to high raw material cost. Biocatalytic transesterification also proves to be
expensive because of the price of lipases, not to mention that its reaction rate is slow. BIOX
Co-solvent transesterification is a relatively new technology which uses tetrahydrofuran or
methyl tertiary butyl ether that is soluble to both oil and methanol to speed up the reaction
rate. However, intensive product purification needs to be employed because of the possible
hazardous or toxic properties of the co-solvents.

4.2. Recycle Structure


Methanol is the excess reactant and thus is the only reactant that is being recycled in
the process flow diagram. Coffee oil is not recycled since homogenous catalytic
transesterification offer high fatty acid methyl ester yield with a conversion of greater than
98% thus making it unreasonable to recycle a very small amount of coffee oil back to the
reactor. The stream of methanol to be recycled (Figure 16, S-145) comes from the overhead
of the alcohol recovery distillation column (Figure 16, P-32/C-103). Stream 145 (Figure 16)
will then be recycled to the methanol storage tank (Figure 1, P-3/V-104).

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38

Water is also recycled and is used in the biodiesel washing section of the process.
Stream 146 (Figure 16), water to be recycled, comes from the overhead of the glycerol
recovery distillation column (Figure 16, P-33/C-104).

4.3. Separation Structure


In general, availability of technology and practicality were used as the main basis for
choosing the process.
The extraction of coffee oil can be carried out by traditional methods like
hydrodistillation (HD) and newer methods like Supercritical Fluid Extraction (SCFE) and
Improved Microwave Assisted Extraction (IMAE) technique. However, there are certain
disadvantages in using HD and IMAE such as losses of some volatile compounds, low
extraction efficiency, degradation of unsaturated or ester compounds through thermal or
hydrolytic effects, toxic solvent residue in the extract, etc. These kind of disadvantages have
led to the consideration of the use of the new eco-friendly technique in oil extraction which
use less solvent and energy, such as SCFE (Patel et al., 2012).

4.4. Heat Exchanger Network


Due to the low temperature difference between heated or cooled streams, it would be
more economical to stick with the use of utilities. The cost to manufacture the heat
exchangers would outweigh the use of an ordinary heater or cooler.

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39

5. THE PROCESS
5.1. Process Flow Diagram

Figure 15. FFA Esterification & Coffee Oil Transesterification Sections.

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40

Figure 16. Biodiesel Purification and Methanol-Water-Glycerol Separation Sections.

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41

Figure 17. Coffee Oil Extraction (S(Supercritical CO2) Section.

Barrinuevo | Bonifacio | Canlas | Dantes

42

5.2. Process Description


Production of biodiesel from spent coffee grounds (SCG) involves these major
processes: supercritical fluid extraction, free fatty acid (FFA) esterification, coffee oil
transesterification, biodiesel purification, and methanol-water-glycerol separation.
In supercritical fluid extraction, carbon dioxide is used to extract coffee oil from the
dried spent coffee grounds. The extracted oil then undergoes a two-step biodiesel production
involving the esterification of fatty acids and transesterification of triglycerides present in the
aforementioned coffee oil. The resulting methyl esters after these procedure will then be
subjected to a necessary purification process to meet the set biodiesel standard in terms of
purity. Methanol, water, and glycerol pass through a series of distillation processes to allow
for material recycle (methanol) and by-product acquisition (glycerol). The entire process is
assumed to operate at steady state.

5.2.1. Supercritical Fluid Extraction


The stored liquid carbon dioxide (at 250C) is cooled to 150C to maintain its liquid
state. It is then enters a high pressure pump to raise its pressure to 300 bar. Then it is reheated
to 310C to obtain a supercritical (SC) fluid. SC-CO2 is used as solvent to extract the coffee oil
without denaturing it. After extraction, the pressure is lowered using a regulating valve and
the CO2 will return to a gaseous state. This will allow the efficient separation of the extract
from CO2. The mixture temperature is maintained at 300C before separation. Flash drum will
be used for the separation and 10% of the CO2 will be vented to avoid the accumulation of
impurities. Before entering the storage tank, the recycled CO2 is first cooled again to return to
liquid state.

5.2.2. Esterification of Coffee Oil Free Fatty Acids (FFA)


Since coffee oil has a relatively high FFA content, reacting FFA directly with
methanol using a base catalyst will result to the formation of soap and water, especially for
this type of feedstock containing more than 5% FFA. The soap formed inhibits the separation
of glycerol or glycerin from the methyl esters in the latter parts of the process. Moreover, this
phenomenon may also contribute to the formation of unwarranted emulsion during the
washing process involved with biodiesel purification. To avert this, Van Gerpen (n.d.)
presented a means to reduce soap formation to a minimum and utilize free fatty acids as

Barrinuevo | Bonifacio | Canlas | Dantes

43

potential reactants for methyl ester formation. His suggestion essentially involves reacting the
FFA-containing oil to methanol, but with the aid of an acid catalyst which, for the purpose of
this feasibility study, is sulfuric acid. By doing so, FFA reacts with methanol to yield
products, fatty acid methyl esters (FAME) and water.
In this case, coffee oil (Figure 15, S-114) is heated to 600C before reacting it with
methanol (Figure 15, S-111) in a plug flow reactor, together with the acid catalyst, sulfuric
acid (Figure 1, S-116). The reaction runs at a residence time of 1 hour at 600C. The exiting
stream (Figure 15, S-118) containing the formed FAME and water, residual FFA, remaining
methanol, sulfuric acid, and coffee oil triglycerides pass through a decanter centrifuge (Figure
15, P-14/DC-101), set at 30% sedimentation efficiency, to separate water from the rest of the
stream. This is necessary to avoid the hydrolysis of triglycerides to fatty acids. The water-rich
stream (Figure 15, S-123) will then be delivered to the methanol-water-glycerol separation
section (Figure 16); whereas, the triglyceride-rich stream (Figure 15, S-119) will be
transported to the base-catalyzed plug flow reactor (Figure 15, P-17/PFR-103) for
transesterification.

5.2.3. Transesterification of Coffee Oil Triglycerides


Unlike the previous process which is sometimes referred to as the pretreatment of
FFA (Van Gerpen, n.d.), the transesterification of coffee oil triglycerides is the heart of the
entire biodiesel production. Essentially, coffee oil triglycerides (Figure 15, S-119) which are
mainly composed of linolein and palmitin, are reacted with methanol, but this time aided by
sodium methoxide (Figure 15, S-106) as the alkali catalyst. Sodium methoxide was used
instead of sodium hydroxide or potassium hydroxide because the handling of hydroxide
pellets or flakes can be hazardous to plant operators (Van Gerpen, n.d.). Before reacting the
triglycerides with methanol, however, the oil-containing stream should first be heated to
600C. The reactor (Figure 15, P-17/PFR-103) operates at a residence time of 1 hour, as well.
The assumed extent of the reaction for this process is 96%. The products formed are methyl
esters and glycerol. Similar to the esterification process, the effluent stream (Figure 15, S122) enters a decanter centrifuge (Figure 15, P-18/DC-102). This is done to separate glycerol
(Figure 15, S-125) prior to biodiesel purification.

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44

5.2.4. Biodiesel Purification


The stream that is rich in methyl esters formed from triglycerides (Figure 16, S-124)
will be neutralized with hydrochloric acid (Figure 16, S-131) to split formed soaps and
eventually washed with softened, hot water at 600C (Figure 16, S-129) in a mixing tank
(Figure 16, P-23/R-101) for the removal of contaminants such as residual methanol, free
glycerin, catalysts, and soap. The tank effluent (Figure 16, S-132) will pass through a
decanter centrifuge (Figure 16, P-24/DC-101) to separate it into two streams. The first one
(Figure 16, S-133) shall comprise primarily of the desired biodiesel and some miniscule
amount of water that will subsequently be removed in an adiabatic flash drum operating at 1
bar (Figure 16, P-27/V-102). The purified biodiesel will then be stored in a storage tank
(Figure 16, P-28/V-101).
On the other hand, the second one (Figure 16, S-137) will proceed to the methanolwater-glycerol separation section. This stream will be processed together with the water
(Figure 15, S-123) and glycerol (Figure 15, S-125) that were isolated in the reaction sections.

5.2.5. Methanol-Water-Glycerol Separation


Before entering the first distillation column (Figure 16, P-32/C-103), the influent must
first be heated to around 800C for ease of separation. The operating conditions (R/Rmin,
column pressure, vapor linear velocity, and stage efficiency) employed for both columns of
this entire section were mostly based on the process simulation presented by SuperPro
Designer for biodiesel production from soybean oil. For the first column, methanol is
retrieved as the distillate. This stream (Figure 16, S-145) is recycled to the methanol storage
tank. Meanwhile, the bottoms (Figure 16, S-141) containing water and glycerol shall proceed
to the second distillation column (Figure 16, P-33/C-104) for further separation. The distillate
shall be composed chiefly of water, while the bottoms shall be composed of glycerol
(approximately 87% purity) which is to be stored in a tank (Figure 16, P-34/V-105) before
selling it as a secondary product.

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45

5.3. Heat and Material Balance


The following material balances are generated using SuperPro Designer.

Table 2. Overall material balance (kg/yr) in esterification and transesterification section.

Table 3. Overall material balance (kg/yr) in purification and separation section.

Table 4. Overall material balance (kg/yr) in extraction section.

5.4. Equipment List


Using SuperPro Designer, the following are the generated list of equipment for all
sections. It is imperative to note that costing and equipment sizing have not been performed
yet. The purchase costs indicated here are default 2015 prices that are built-in the said process
simulation software used and are still subject to change.

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46

Table 5. Equipment Summary for the FFA Esterification & Coffee Oil Transesterification Sections

Table 6. Equipment Summary for the Biodiesel Purification and Methanol-Water-Glycerol Separation Sections

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47

Table 7. Equipment Summary for the Coffee Oil Extraction (Supercritical CO2) Section

5.5. Utility List


Also with the aid of SuperPro Designer, the following are the generated list of utilities
(power and heating/cooling agents) for all sections.
Table 8. Power Demand Breakdown for the FFA Esterification & Coffee Oil Transesterification Sections

Table 9. Heat Transfer Agent Demand Breakdown for the FFA Esterification & Coffee Oil Transesterification
Sections

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48

Table 10. Power Demand Breakdown for the Biodiesel Purification and Methanol-Water-Glycerol Separation
Sections

Table 11. Heat Transfer Agent Demand Breakdown for the Biodiesel Purification and Methanol-WaterGlycerol Separation Sections

Table 12. Power Demand Breakdown for the Coffee Oil Extraction (Supercritical CO2) Section

Table 13. Heat Transfer Agent Demand Breakdown for the Coffee Oil Extraction (Supercritical CO2) Section

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49

6. COST ESTIMATION
6.1. Cost Estimation of Purchased Equipment
Table 14. Purchased equipment cost for esterification and transesterification section.
Equipment

Quantity

Capacity

Purchase Cost
(USD)

Vertical-On-Legs-Tank

0.01329 m

5734.006781

1.18517 m3

6488.39615

5706.280308

0.31018 m

6008.480484

0.2963 L/s

3311.151139

0.000297222

3300.002812

0.00119 m

Centrifugal Pump

L/s
0.038775 L/s

3300.971636

0.038775 L/s

3300.971636

0.003322222

3300.050928

L/s
Centrifugal Pump Motor

Heat Exchanger

0.15 kW

1079.006593

0 kW

920

0.02 kW

958.8036204

0.02 kW

958.8036204

0 kW

920
2

10019.36

10001.76

0.22 m
0.02 m

Mixer

Plug Flow Reactor

1.54896 m3

34919.38259

33229.57991

1.37336 m
Decanter Centrifuge

Total

133457.0082

Table 15. Purchased equipment cost for purification and separation section.
Equipment

Quantity

Capacity

Purchase Cost
(USD)

Vertical-On-Legs-Tank

2.15386 m

6897.706123

1 m3

6400

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50

Centrifugal Pump

0.21333 m3

5937.374681

0.017591667

3300.376365

L/s
0.248608333

3309.033583

L/s

Centrifugal Pump Motor

Heat Exchanger

0.53855 L/s

3322.840861

0.01 kW

943.8864302

0.06 kW

1003.72538

0.31 kW

1184.304426

10001.76

10045.76

0.49 m

10043.12

0.22 m2

24193.10802

0.02 m
0.52 m

Stirred Reactor

Distillation Column

Mixer

Decanter Centrifuge

Total

86582.99587

Table 16. Purchased equipment cost for extraction section.

Equipment

Quantity Capacity

Purchase
Cost (USD)

Vertical-On-Legs-Tank

1 m3

6400

Centrifugal Pump

3766.220003 L/s

941570.496

0 kW

920

Centrifugal Pump Motor 1


Heat Exchanger

Mixer

Rotary Dryer

Total

3.18 m

10279.84

0 m2

10000

7.94 m2

10698.72

1.17 m2

10102.96

140.65 m2

365691.2122
1359963.228

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51

Tables 14, 15, and 16 shows the calculated purchase cost of each equipment for each
of the process flow diagrams by using the capacity of each equipment, the correlations in
Table 6.6 (Towler) and Equation 6.15 (Towler).
= +
Where

(6.15)

Ce

= purchased equipment cost on a U.S. Gulf Coast basis, January 2006;

a, b

= cost constants in Table 6.6;

= size parameter, units given in Table 6.6;

= exponent for that type of equipment

Table 17. Summary of purchased equipment cost.

Total Purchased Equipment Cost

1580003.232

Total Purchased Equipment Cost on South East 1675284.919


Asia Basis
Total Escalated Purchased Equipment Cost

2006071.431

The total purchased equipment cost, as shown in Table 17, was calculated by adding
the purchased equipment cost of the three process flow diagrams. However, the resulting
value was on a U.S. Gulf Coast basis. Thus, a location factor was used to convert the value on
a South East Asia basis, which was calculated using the location factors in Table 6.7
(Towler).

, . 2006 = , . 2003

2006
2003

The Total Purchased Equipment Cost on South East Asia basis was calculated by
multiplying the location factor to the total purchased equipment cost. Lastly, cost escalation
was done by using the Cost Estimate Indices in 2006 and 2015.

, . 2015 = , . 2006

2015
2006

The values are listed in Table 17. As shown, the Total Escalated Purchased
Equipment Cost amounts to 2,006,071 USD.

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7. PROFITABILITY ANALYSIS
7.1. Generation of Cash Flow Diagram

7.1.1. Capital Costs


Based on the purchased equipment cost determined in the previous section, the fixed
capital investment (FCI) is calculated using the ranges of process-plant component cost
outlined in Table 18 (Peters & Timmerhaus, 1991).

Table 18. Estimation of fixed capital investment using process-plant component costs.

Components

Range,

Selected

% of FCI

Cost, USD

Ratioed
%

Direct Costs
Purchased equipment

15-40

30

2,006,071

31.9

6-14

10

668,690

10.6

2-8

267,476

4.3

Piping (installed)

3-20

401,214

6.4

Electrical (installed)

2-10

334,345

5.3

Buildings (including services)

3-18

401,214

6.4

2-5

133,738

2.1

8-20

10

668,690

10.6

1-2

Engineering and supervision

4-21

267,476

4.3

Construction expense

4-16

267,476

4.3

Legal expense

1-3

66,869

1.1

Contractors fee

2-6

133,738

2.1

5-15

10

668,690

10.6

Purchased equipment installation


Instrumentation and controls (installed)

Yard improvements
Service facilities (installed)
Land
Indirect Costs

Contingency

Selected percentages are based on the typical cost of other types of biodiesel plants
and on the location and condition of the site. Biodiesel plants are relatively not capital

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53

intensive so the purchased equipment cost can be assumed to be about the average value of
the range. A traditional stick-built construction will be employed where process equipment
are shipped individually and installed incrementally at the manufacturing site so an average
value is chosen. Instrumentation and controls, and piping are assumed to be readily available
from nearby suppliers. Motor control panels are within the customers scope of supply. In the
site, one-story structures will be built. Furthermore, since the plant will be located on an
industrial area, yard improvements will generally be lower. Also, simple yet functional
facilities will be constructed and the land occupied by the plant is leased. All other indirect
costs were assumed to be at the minimum except the cost for contingency. Since the use of
spent coffee grounds for large-scale biodiesel production is a relatively new process, an
average value is selected to account for uncertainty in estimates. FCI is the sum of direct and
indirect costs.
The total capital investment (TCI) is the sum of FCI and working capital (WC) which
is approximately 10-20% of the TCI. Using this relationship, the values of WC and TCI are
calculated and shown, together with FCI, in Table 19.

Table 19. Summary of capital costs.

USD
Fixed Capital Investment (FCI)
-Without construction interest

6,285,689

Working Capital (WC)

1,109,239

Total Capital Investment (TCI)

7,394,928

7.1.2. Production Costs and Revenues

Variable costs of production (VCOP) are proportional to the plant output or operation
rate. The components of VCOP for the biodiesel plant are summarized in Table 20. Utilities
were calculated later as 10% of the total product cost.

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54

Table 20. Variable costs of production components for the biodiesel plant.
MT/yr

Price, USD/MT

USD/yr

Revenue: Biodiesel

13660

1,623

22,170,180

By-product: Glycerol

1728

330

570,240

Effluent disposal
Wastewater

50,000

Inert solid wastes

50,000
100,000

Raw Materials
Spent coffee grounds

250,000

51.3

12,825,000

Liquid CO2

20,000

150

3,000,000

Hydrochloric acid

21

132

2,772

NaOCH3

181

980

177,380

Methanol

533

315

167,895

Sulfuric acid

16

300

4,800
16,177,847

Utilities

1,938,591

On the other hand, fixed costs of production (FCOP) are incurred regardless of the
plant operation rate or output. Even if the plant cuts back its production, these costs are not
reduced. The components of FCOP are summarized in Table 21 below.

Table 21. Fixed costs of production components for the biodiesel plant.
Components

Estimated as

USD/yr

15,000 USD/yr each

540,000

Supervision

25% of operating labor

135,000

Direct overhead

45% of labor and supervision

243,000

3% of ISBL investment

60,182

Plant overhead

65% of labor and maintenance

635,818

Tax and insurance

2% of fixed investment

125,714

LABOR
9 Operators per shift
(4 shift positions)

MAINTENANCE
OVERHEAD EXPENSE

Annualized capital charges (ACC) are assumed to be zero. As a result, the TCOP is
calculated as the sum of FCOP and VCOP (Table 22).

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55

Table 22. Total cost of production for the biodiesel plant.

USD/yr
Variable costs of production (VCOP)

17,646,198

Fixed costs of production (FCOP)

1,739,714

Total Cost of Production (TCOP)

19,385,913

7.1.3. Cash Flow Table

Few large projects are completed in a single year and immediately begin production at
full capacity. However, the startup schedule given in Table 23 is used for cash flow
generation.

Table 23. Startup schedule for the biodiesel plant.


Year

Costs

Revenues

Explanation

40% of FCI

Engineering + long lead-time items

60% of FCI +

Procurement and construction

100% WC
3

50% of design basis revenue

Initial production

75% of design basis revenue

Shake-down of plant

5+

100% of design basis revenue

Full production at design basis

FCI = fixed capital investment; WC = working capital

To finance this project, the capital contributed by the stockholders (equity) is assumed
to be 30% and the rest will come from bank loans at an interest rate of 5% every year. The
assumption used is that the cash needed to finance the cash outflows in the quarter is
withdrawn at the beginning of the quarter (Table 24). This reflects a more realistic approach
as most banks would prefer draw downs on loans on a less frequent basis for the year. In this
case the amount drawn for the quarter earns interest for the same quarter for the bank, a cash
outflow for the project owner. The biodiesel plant will be built with 40% of the FCI in year 1
and 60% in year 2.

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56

Table 24. Cash outflow during the construction phase.


Construction Year 1

Construction Year 2

Q1

Q2

Q3

Q4

Q1

Q2

Q3

Q4

30

2.5

2.5

40

10

2.5

2.5

1,885,707

157,142

157,142

314,284

2,514,276

628,569

157,142

157,142

Bank Loan

157,142

157,142

314,284

2,514,276

628,569

157,142

157,142

Cumulative

157,142

314,284

628,569

3,142,845

3,771,413

3,928,556

4,085,698

1,964

3,929

7,857

39,286

47,143

49,107

51,071

% of
plant cost
Construction
cost

Bank Loan
Construction
Interest
Cash outflow

2,528,026

Total FCI

3,643,735
6,171,761

The plant is depreciated by the straight-line method over 10 years and profits can be
assume to be taxed at 30% per year, payable the next year. The value of annual depreciation
is assumed to be 10% of the total FCI (Table 25). Present values are calculated using i=8%.
Table 25. Cash flow table for the biodiesel plant (all figures in million USD).
Construction

Operation

10

11

12

2.53

3.64

0.93

0.00

0.00

0.00

0.00

0.00

0.00

0.00

0.00

0.00

Revenue

0.00

0.00

11.09

16.63

22.17

22.17

22.17

22.17

22.17

22.17

22.17

22.17

TCOP

0.00

0.00

9.69

14.54

19.39

19.39

19.39

19.39

19.39

19.39

19.39

19.39

Gross profit

0.00

0.00

1.39

2.09

2.78

2.78

2.78

2.78

2.78

2.78

2.78

2.78

Depreciation

0.00

0.00

0.62

0.62

0.62

0.62

0.62

0.62

0.62

0.62

0.62

0.62

Taxable

0.00

0.00

0.77

1.47

2.17

2.17

2.17

2.17

2.17

2.17

2.17

2.17

Tax Paid

0.00

0.00

0.00

0.23

0.44

0.65

0.65

0.65

0.65

0.65

0.65

0.65

Cash Flow

-2.53

-3.64

1.08

2.47

2.96

2.75

2.75

2.75

2.75

2.75

2.75

2.75

PV of CF

-2.41

-3.30

0.94

2.03

2.32

2.05

1.96

1.86

1.77

1.69

1.61

1.53

NPV

-2.41

-5.71

-4.78

-2.74

-0.42

1.63

3.59

5.45

7.22

8.91

10.52

12.05

Capital
Expense

Income

TCOP = total cost of production; CF = cash flow; PV = present value; NPV = net present value

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57

The cash flow diagram shown in Figure 18 represents the steady-state situation for
cash flow. The time period chosen, 10 years, is the estimated life period of the project, and
the time value of money is neglected. The zero point on the abscissa represents that time at
which the plant has been completely constructed and is ready for operation. The cash position
is negative by an amount equivalent to the total capital investment at zero time. Cash flow to
the company starts to accumulate and gradually pays off the full capital investment. At the
end of 10 years, the project theoretically shuts down and ceases operation.

Cumulative cash flow, million USD

25
20
15
10
5
0
-1

-5

-10

10

Time, years

Figure 18. Cumulative cash position neglecting the time value of money.

7.2. Profitability Analysis

7.2.1. Payback Time


As a recall, it has been assumed that the investments are spead over the first two
years, and revenues will not reach 100% of the design basis until the third year of operation.
Taxes and depreciation were also taken into account. Payback time is when the full capital
investment is paid off. Therefore, based on the cash flow diagram (Figure _________) the
payback time is 2.89 years from the start of operation.

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7.2.2. Net Present Value (NPV)


The net present value with a 5% cost of capital after 10 years of production is the
NPV at the end of year 12. This can be looked up in the cash flow table and is 12.05 million
USD. When the plant closes after 10 years of production , the working capital is released and
there would be an additional cash flow of 0.93 million USD in year 12, increasing the NPV to
12.98 million USD.

7.2.3. Internal Rate of Return (IRR)


The IRR of the project after 10 years of production can be found by either adjusting
the interest rate (manually or using the goal seek function) until the NPV at the end of year 12
is equal to zero, or by using the IRR function in the spreadsheet over the range year 1 to year
12. The working capital should be included as a recovered cost in year 12. For this project,
the maximum interest rate at which this project can be financed to break even in 10 years of
production is 31%.

7.3. Sensitivity and Scenario Analysis


To have an idea on the degree of risk involved in making judgments on the forecasr
performance of the project, a sensitivity analysis must be made. The results are usually
presented as plots of an economic criterion vs. the parameter studied. For this project, we aim
to identify which of the capital cost and revenue will have a significant impact on the project
viability over a variation of 20% of base. It can be seen from Figure 19 that payback time is
more sensitive to changes in revenue because payback remained stable over the range of
variation in capital expenses.

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59

14

Payback time, years

12
10
8
6

Capital

Revenue

2
0
-30%

-20%

-10%

0%

10%

20%

30%

Parameter variation

Figure 19. Effect of varying capital and revenue on payback time.

8. CONCLUSIONS & RECOMMENDATIONS

This project fulfilled the objective to design an eco-friendly manufacturing plant that
utilizes spent coffee grounds to produce a biodiesel blend within the local standards for
biofuel.
Based on the short payback period, positive net present value and attractive IRR, this
investment would seem to be worth pursuing further. The implementation would then depend
on the hurdle rate set for investments by the company. However, it should be noted that this
analysis was based on a class 4 estimate of the capital cost (30%). For technical
improvement of the profitability analysis, a more detailed estimate should be used to increase
the certainty in the values of economic parameters.

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60

ACKNOWLEDGEMENT

The proponents would like to convey their most cordial gratitude to all the people
directly and indirectly involved in the completion of this requirement.

First of all, to their adviser, Dr. Analiza P. Rollon, for her constant guidance all
throughout the process of coming up with this feasibility study.

To their ChE 141 lecturers, Engr. Kenneth Robert de Guzman, Dr. Rizalinda de Leon,
Engr. Carmelita Villanueva, and Engr. Antonio Rivera, for giving their time to impart
valuable knowledge in achieving the goals of this course.

To their friends and seniors, for supplying the necessary boost in accomplishing all
deliverables.

To their beloved families, for their unwavering love and support throughout this
academic pursuit.

Above everyone, the authors would like to thank Almighty God for blessing them
with knowledge and enough resources; without Him, all these would not be possible.

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61

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Policy. Agricultural and Environmental Sustainability (p. 36). Italy: Franco Angeli
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New York State Department of Environmental Conservation. (n.d.) "Biodiesel Fact Sheet."
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from http://www.educypedia.karadimov.info/library/01.pdf
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63

APPENDICES
Design Basis Sheet
Department of Chemical Engineering, University of the Philippines Diliman
ChE 141: Chemical Process Development and Plant Economics

REV

DATE

BY

APVD

DESIGN BASIS SHEET


General Information
Kemrez Incorporated
Biodiesel Production from Spent Coffee Grounds
San Pedro, Laguna

Company Name
Process Name
Plant Location

Measurement System
Length
Mass
Moles
Volume
Time

m, km
kg
kmol
m3 , L
hr, s

Pressure
Temperature
Energy
Heat Rate
Power

kPag
C
kJ
kW
hp

Density
Specific Heat
Viscosity
Thermal Conductivity
Surface Tension

kg/m3
kJ/kg-C
cP
W/m-C
dyne/cm

Filters
Heaters
Ejectors
Motors
Pumps

F
H
J
M
P

Reactors
Towers
Tanks
Vessels

R
T
TK
V

Equipment Numbering System


Agitators
Blowers
Compressors
Dryers
Heat exchangers

A
B
C
D
E

Products
Product Name
Product Grade
MSDS Form Number
Production Rate (kg/hr)
Product Price (USD/kg)
Product Impurities

biodiesel
95%
68476-34-6
1725
0.1623
Name

(ppm)

glycerin
87%
56-81-5
190
0.33
Name

(ppm)

Name

(ppm)

methanol
98% technical grade
67-56-1
220
0.315
Name
(ppm)

Name

(ppm)

Raw Materials
Raw Material Name
Raw Material Grade
MSDS Form Number
Consumption Rate (kg/hr)
Raw Material Price (USD/kg)
Raw Material Impurities

spent coffee grounds (SCG)


NA
8001-67-0
31566
0.0513
Name
(ppm)

Site Information
Ambient Temperature

Dew Point Temperature


Ambient Relative Humidity

Precipitation

Wind Velocity
Site Elevation above Sea Level (m)

Daily Average (C)


Minimum Recorded (C)
Maximum Recorded (C)
Maximum Recorded (C)
Daily Average (%)
Minimum Recorded (%)
Maximum Recorded (%)
Daily Average (mm)
Minimum Recorded (mm)
Maximum Recorded (mm)
Maximum (m/s)

27
12
38
23
78.8
83 (morning) | 59 (evening)
90 (morning) | 79 (evening)

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Material Safety Data Sheets

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69

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70

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Physico-Chemical Property Database & Sample Calculations


Component
Tripalmitin
Tristearin
Triolein
Trilinolein
Trilinolenin
Triarachidin
Methyl
Palmitate
Methyl
Stearate
Methyl
Oleate
Methyl
Linoleate
Methyl
Linoleate
Methy
Arachidate
Palmitic
Acid
Stearic Acid
Oleic Acid
Linoleic
Acid
Linolenic
Acid
Arachidic
Acid

MW

Hf (J/mol)

Tb (0C)

Tf (0C)

Tc (0C)

Pc (bars)

Omega

Cp(J/molK)

807.335
891.499
885.452
879.404
873.357
975.66
270.456

-2061217.022
-2185879.528
-1851257.403
-1516637.604
-1182017.806
-2310539.707
-710714.6815

670.6666667
700.4166667
702.1666667
703.9055556
705.6333333
727.4277778
342.3961111

128.2083333
138.9188889
137.7183333
136.5038889
135.2744444
148.6144444
14.01522222

781.86
805.39
810.59
816.00
821.64
826.89
508.49

5.147147644
4.635454157
4.784435803
4.941698038
5.107888967
4.216239882
13.80617493

1.56769
1.62471
1.59871
1.57057
1.54023
1.66968
0.801684

1597.742203
1822.045656
1780.818849
1768.655126
1756.493415
2057.17911
590.14

298.51

-752268.8502

369.5927778

24.89227778

531.57

12.56574139

0.859527

646.44

296.495

-640727.3666

371.2116667

23.67388889

537.50

12.94405604

0.837339

631.8021978

294.479

-529188.2091

373.2277778

22.44122222

543.62

13.34215861

0.814568

628.2527473

292.463

-417649.0516

374.4266667

21.19338889

549.97

13.76156593

0.791199

624.7032967

326.564

-793823.0188

394.8355556

34.72427778

552.75

11.52966809

0.914562

722.28

256.43

-725001.0349

351

62.8

502.85

15.10045643

1.0611

482.9713328

284.48
282.46
280.45

-764001.2446
-671800.5342
-539999.5036

375.2
359.85
354.85

69.6
13.38
-5

530.85
507.85
501.85

13.59995312
13.89870241
14.09933948

1.036
1.1872
1.1762

624.92426
533.05896
553.836

278.435

-405000.2092

358.85

-11.1

506.85

14.39995036

1.1855

487.6434

312.536

-812400.8607

397

75.3

547.85

12.39999173

1.0856

700.570852

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Density (g/L)
Component
Tripalmitin
Tristearin
Triolein
Trilinolein
Trilinolenin
Triarachidin
Methyl
Palmitate
Methyl
Stearate
Methyl
Oleate
Methyl
Linoleate
Methyl
Linoleate
Methy
Arachidate
Palmitic
Acid
Stearic Acid
Oleic Acid
Linoleic
Acid
Linolenic
Acid
Arachidic
Acid

Heat capacity (J/mol K)


b
c

Hvap (J/mol)
d

2051.58517
2119.491326
2097.204868
2063.533211
2044.129904
2182.369296
1209.691991

-1.153391074
-1.147953546
-1.122605561
-1.08987469
-1.066441677
-1.170385475
-0.786057826

31.1143909
25.6580331
-16.906279
-59.470591
-102.03474
20.2016754
12.8585265

469.1779504
526.2011038
532.203541
538.2059782
544.2084154
583.228443
156.4513909

-24.71061915
-27.97604545
-30.50313848
-33.03023152
-35.55728269
-31.24142989
-8.067459772

42.4084327
49.5515004
63.77736028
78.00363874
92.22949862
56.6945681
13.40577794

621671
707859
686733
665772
644979
796957
167366

0.3775
0.3775
0.3775
0.3775
0.3775
0.3775
0.3775

1234.582633

-0.783787756

11.9491614

165.9552498

-8.611697488

14.59626132

177541

0.3775

1231.130259

-0.771183495

-52.387798

208.426888

-16.43780403

76.0936582

183010

0.3775

1227.786019

-0.758577904

-17.336453

179.461152

-10.84067785

25.27088848

178202

0.3775

1225.335156

-0.746438692

-31.524557

181.4619644

-11.68302824

30.01289759

173428

0.3775

1262.441997

-0.787046454

9.22098254

194.4676636

-10.24441064

18.16783703

208905

0.3775

1286.483667

-1.293534854

-52.02782

179.0224802

-12.47958598

40.6425274

126470

0.4176

1266.322686
1108.081433
1139.588762

-1.228081503
-0.744588645
-0.809575798

-27.400707
-54.543904
13.0700768

190.8980134
197.2646152
122.4417659

-13.45847717
-14.8004865
7.23201595

50.28443398
55.37311104
-248.6407058

174100
134700
133870

0.63436
0.3943
0.3987

1278.691608

-1.305349746

-56.566483

169.0439516

-6.789451316

-68.67097906

136800

0.4054

1256.634164

-1.192233909

-28.328574

211.9998869

-16.13236621

86.94492612

135930

0.419

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The fatty acid analysis used for the plant design was from the journal article, Supercritical fluid extraction of spent coffee grounds:
Measurement of extraction curves, oil characterization and economic analysis, by Melo, et. al. Below is the fatty acid profile by the
aforementioned authors.
Fattty Acid
Palmitic Acid
Stearic Acid
Oleic Acid
Linoleic Acid
Linolenic Acid
Arachidic Acid

Composition
37.37
7.07
8.31
44.67
1.42
1.62

To estimate the original mass composition in terms of triglycerides and free fatty acids, the SCG oil was assumed to be 99.5%
triglyceride and 0.5% free fatty acid since the free fatty acid content of SCG oil was supposed to be 0.5% or less. Also, the triglycerides were
assumed to be homogenous, that is, only one kind of fatty acid makes up one triglyceride. To calculate the mass of each triglyceride, a 100 g
basis of total fatty acid was set. Each fatty acid had its mass composition multiplied by the basis before dividing by its molecular weight. The
resulting value was in moles fatty acid. A stoichiometric ratio of 1 mole of triglyceride per 3 moles of fatty acid was used. The output was in
moles triglyceride. This value was then multiplied by its respective mass in triglyceride form. Five-tenths percent of this mass was noted as the
mass of its free fatty acid counterpart. The total mass of the triglycerides and free fatty acids was set as the divisor to get the theoretical
composition of SCG oil.
Sample Calculations
1

Tripalmitin: = % 100 3

= 0.05
= 0.3737



1

100 256

807.335

3

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= 39.21812184
= 0.05 39.21812184 = 0.196091
= 105.7827202
% =

39.21812184
100% = 37.0742232%
105.7827202

% =

0.196091
100% = 0.1853711%
105.7827202

Below is the summary of the theoretical composition of SCG oil.


Component
Palmitin
Stearin
Olein
Linolein
Linolenin
Arachidin
Palmitic
Stearic
Oleic
Linoleic
Linolenic
Arachidic

Composition
0.370742232
0.069814516
0.087670533
0.441350671
0.014035133
0.011411791
0.001853711
0.000349073
0.000438353
0.002206753
7.01757E-05
5.7059E-05

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The pysico-chemical properties required by SuperPro Designer were molecular weight, heat of formation, normal boiling point, normal
freezing point, accentric factor, density, Antoine coefficients, heat capacity and heat of vaporization. All properties except Antoine coeffecients
were derived from ChemCad 6.3.
ChemCad computes critical properties, normal boiling and freezing points and thermochemical properties using the Elliott or UNIFAC
Method if the user input a new component in terms of UNIFAC group contribution. Below is a table showing UNIFAC group contributions in
estimating the physical properties. The second table contains the equations for estimating the physical properties and its corresponding % error.

Group ID
1
2
3
6
23
43

Formula
CH3CH2<
CH
CH=CH
CH2COO
COOH

Property
Tc
Pc
Tb

Unit
K
Bar
K

Hf298

kJ/mol

Tc
0.135
0.131
0.073
0.169
0.453
0.615

Pc
0.232
0.224
0.186
0.360
0.704
0.511

Equation
[1 + (1.28 + )1 ]
(0.346 + Pc )2
1000
35.7
1000
0.5 +
+
(Tb )0.5 142 + Tb
10.835 + Hf298

Tb
123
121
97
257
573
858

H298
-45.947
-20.763
-3.766
69.939
-359.258
-396.242

% error
0.934
6.112
4.67

8.3

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Sample Calculation for Palmitic Acid with 1 CH3, 14 CH2 and 1 COOH
Tb = 1 123 + 14 121 + 1 858 = 2675
=

1000
= 647.1497
35.7
1000
0.5 +
+
(2675)0.5 142 + 2675

Tc = 1 0.135 + 14 0.131 + 1 0.615 = 2.584


= [1 + 1.28 + 2.584)1 = 778.2856
Pc = 1 0.232 + 14 0.224 + 1 0.511 = 3.879
Pc = 256.43(0.346 + 3.879)2 = 14.36
Hf298 = 1 45.947 + 14 20.763 + 1 396.242 = 695.887
Hf298 = 10.835 695.887 = 685.052

kJ
mol

The coefficients for the ideal gas heat capacity were estimated using Joback /Lyderson Method. Below is a table showing Joback group
contributions for ideal gas heat capacity coefficients.

Groups
-CH3
>CH2
>CH=CH-COOH
-COO-

a
1.95E+1
-9.09E-1
-2.30E+1
-8.00
2.41E+1
2.45E-2

b
-8.08E-3
9.50E-2
2.04E-1
1.05E-1
4.27E-2
4.02E-2

c
1.53E-4
-5.44E-5
-2.65E-4
-9.63E-5
8.04E-5
4.02E-5

d
-9.67E-8
1.19E-8
1.20E-7
3.56E-8
-6.87E-8
-4.52E-8

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The formula for estimating ideal gas heat capacity using Joback method is as follows:
0 = + + 2 + 3
where:
=

37.93

+ 0.210

3.91104

+ 2.06107

And nj is the number of the jth group present in the species.


Sample Calculation for Palmitic Acid with 1 CH3, 14 CH2 and 1 COOH
= 1.9510 + 14 9.09101 + 2.4110 = 3.0910

= 8.08103 + 14 9.50102 + 4.27102 = 1.36

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= 1.53104 + 14 5.44105 + 8.04105 = 5.28104

= 9.67108 + 14 1.19108 6.87108 = 1.20109

= 3.0910 37.93 = 7.06


= 1.36 + 0.210 = 1.57
= 5.28104 3.91104 = 9.19104
= 1.20109 + 2.06107 = 2.07107
Lastly, for the acentric factor, the Lee-Kesler method was used. The acentric factor, , was set as the ratio of two quantities which are
dependent to a species critical properties.
=

= [] 5.97214 + 6.09648 1 + 1.28862 0.169374 6


= 15.2518 15.6875 1 13.4721 + 0.43577 6
=

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