BIOETHANOL PRODUCTION USING STARFRUIT (Averrhoa Carambola)

HONEY LYN T. VILLAMOR

THESIS OUTLINE SUBMITTED TO THE FACULTY OF THE INSTITUTE OF

COMPUTING ENGINEERING AND TECHNOLOGY, DAVAO DEL
SUR STATE COLLEGE, DIGOS CAMPUS,
MATTI, DIGOS CITY,
IN PARTIAL FULFILLMENT OF
THE REQUIREMENT FOR
THE DEGREE OF

BACHELOR OF SCIENCE IN AGRICULTURAL ENGINEERING

JANUARY 2020
 CHAPTER I

THE PROBLEM AND ITS BACKGROUND

Introduction

It is a known fact that the Philippines are mainly an agricultural country with a

land area of 30 million hectares, 47 percent of which is agricultural. The total area

devoted to agricultural crops is 13 million hectares distributed among food grains, food

crops, and non-food crops. Among the crops grown, rice, coconut, and sugarcane are

major contributors to biomass energy resources (Salman, zafar).

Fossil fuel energy consumption (% of total) in Philippines was 62.43 as of 2014.

Its highest value over the past 43 years was 62.43 in 2014, while its lowest value was

34.60 in 1984. According to Ong et al. (2011), Global energy consumption in 2009 is

expected to slightly increase to about 11428.1 Millions of tonnes of oil equivalent

(Mtoe) and around 88% are from fossil fuels. Fossil fuel will become rare and a serious

shortage in the near future has triggered the awareness to find alternative energy as

their sustainable energy sources.

In the past decade, along with the rise of the middle class and fast economic

growth in China, different varieties of fruits produced in China and other countries are

increasingly consumed. Due to the high consumption and industrial processing of the

edible parts of fruit, fruit wastes such as citrus fruit skins, pineapple residues,

sugarcane bagasse and other fruit residues (principally peels and seeds) are generated
in large quantities in big cities. Fruit waste has become one of the main sources of

municipal solid wastes (MSW), which have been an increasingly tough environmental

issue. At present, the two main techniques to dispose MSW are landfill and incineration.

However, inappropriate management of landfill will result in emissions of methane and

carbon dioxide (Qdais H.A., Abdulla F., Qrenawi L.), and incineration involves the

subsequent formation and releases of pollutants and secondary wastes such as dioxins,

furans, acid gases as well as particulates (Buekens A., Huang H. J. Hazard

Mater. 1998), which pose serious environmental and health risks. For these reasons,

there is an urgent need to seek resource and value-added use for fruit wastes. In fact,

inexpensive and readily available use of agri-food industry waste is highly cost-effective

and minimizes environmental impact. One of the most beneficial approaches is to

recover the bioactive constituents, especially the phenolic compounds, making full use

of them in the food, pharmaceutical as well as cosmetics industry (Makris DP, Boskou

G, Andrikopoulos NK 2007 Nov; 98). Thus, utilization of the fruit wastes as sources of

bioactive compounds may be of considerable economic benefits and has become

increasingly attractive.

Starfruit is the local name of Averrhoa carambola which belongs to the

Oxalidaceae family. The Food and Agriculture Organization of the United Nations (FAO)

reports that the fruit crop is known to have originated in Ceylon and in the Moluccas,

but has been grown mostly in Asia because of the advantageous tropical climate

suitable to the growing of the plant. Having reached a number of countries, this gave

rise to the fruit’s different names. In English, it is known as starfruit, carambola, and
five corners. The Indonesians and Malay call it belimbing manis, while it is referred to

as ma fueang among the Thais and khe among the Vietnamese.

Starfruit is an edible fruit which, though known to many, has not been fully

utilized despite its good economic potentials. In fact, it has been included in the book of

Dr. Roberto E. Coronel entitled “Important and Underutilized Edible Fruits of the

Philippines”. In the book, balimbing is described as a small tree reaching up to 6-9

meters in height. It is characterized by its dark-green colored leaflets and reddish

purple flowers clustered in leaf axils. The fruit turns greenish yellow to yellow when ripe

and has a sweet to sour taste. It has an oblong to ellipsoidal shape with a translucent,

soft, and waxy skin. About 6-9 centimeters long, it presents itself as a five-cornered

fruit with its five prominent longitudinal, angular wings. When cut across, it resembles a

star hence the name starfruit.

Starfruit is one among the under-utilized waste substances proximate analysis

showed that starfruit contains the amount of carbohydrates, fiber, protein and starch.

Thus, this study is conducted to produce bioethanol from starfruit (Averrhoa

Carambola) that has been rendered as wastes and not to be sold by local fruit stores in

Digos City.

Statement of the Problem

This study aimed to produce ethanol from the starfruit that has been rendered as

wastes and not to be sold by local fruit stores in Digos City.

Specifically, the following questions are answered:

• What is the bioethanol yield in different fermentation process and

duration?

• Is there significant difference in distilling duration of the bioethanol

produced in different fermentation process and duration?

• What is the distilling rate of the bioethanol produced in different

fermentation process and duration?

• Is there significant difference in the bioethanol yield in different

fermentation process and duration?

Significance of the Study

• The result of this study will serve as information for the farmers who will

engage in utilizing the starfruit as another source of income.

• This study will serve as basis for other students who will study on how to

utilize other wastes from agricultural products.

• To the Agricultural Society, this study will lead to a new gateway of

another source of ethanol aside from sugarcane, corn, cassava and sweet

sorghum that has been commonly utilized as producer of bioethanol.

• To the private sectors, this study will help them as another source of

ethanol that has been used as additive for gasoline.

 Scope and Limitations

This study is only limited to the production of bioethanol from starfruit

that has been rendered as wastes and not to be sold by local fruit stores in Digos

City. Starfruit is collected at the local places of Digos City. The following

parameters that will use in this study are the distilling duration, distilling rate,

percent alcohol content, bioethanol yield and bioethanol recovery. The laboratory

apparatus is limited on the following: beaker, distilling flask, hot plate,

thermometer, graduated cylinder, vacuum pump, rubber stopper and receiving

flask. The study is conducted at the Chemistry Laboratory of Davao del Sur State

College – Digos Campus.

Definition of Terms

Alcohol Meter An instrument used to determine the

aaaaaaaaamount of alcohol in a liquid.

Distillation Is the process of separating the components or

substances from a liquid mixture by using selective

boiling and condensation.

Distilling Flask Apparatus use for separating a mixture of liquids with

different boiling points through evaporation and

condensation.

Fermentation Is the process of converting sugar or starch into

alcohol.

Starfruit Itself as a five-cornered fruit with its five prominent

longitudinal, angular wings. When cut across, it

resembles a star

Washed Refers to the solution from fermented jackfruit peel.

Yeast microorganisms responsible for turning

sugar into ethanol.

CHAPTER II

REVIEW OF RELATED LITERATURE

THE STARFRUIT

A carambola is a small, fruit-bearing tree possibly native to the Old World

tropics that has been widely cultivated for its edible fruits. Despite being reported as

‘extinct in the wild’ (Missouri Botanical Garden, 2015), A. carambola is also listed in the

Global Compendium of Weeds as “cultivation escape, naturalised, weed” (Randall,

2012), was included in a list of potential invasive species threats in the Caribbean

Region (Kairo et al., 2003), and is naturalized in Puerto Rico, Belize, Micronesia, and

Paraguay (Liogier and Martorell, 2000; Randall, 2012). Although currently a low risk

species, further evaluation of the invasive potential of A. carambola may be necessary

in the future, especially for areas surrounding fields and gardens where the species is

grown.

The fruit is about 5 to 15 centimetres (2 to 6 inches) in length and is an oval

shape. It usually has five prominent longitudinal ridges, but in rare instances it can have

as few as four or as many as eight. In cross section, it resembles a star (CABI. 27

September 2018. Retrieved 5 October 2018). The skin is thin, smooth, and waxy and

turns a light to dark yellow when ripe. The flesh is translucent and light yellow to yellow

in color. Each fruit can have 10 to 12 flat light brown seeds about 6 to 13 mm (0.25 to

0.5 in) in width and enclosed in gelatinous aril. Once removed from the fruit, they lose

viability within a few days (Jonathan H. Crane, 1994).

Ethanol

Ethanol is a low cost oxygenates which contains 34% higher oxygen content by

weight. Ethanol can be produced from a variety of feedstocks such as sugarcane,

bagasse, miscanthus, sugar beet, sorghum, rain, switch grass, barely, hemp, kenaf,

potatoes, cassava, sunflower, fruit, molasses, corn, stover, grain, wheat, straw, cotton,

other biomass, as well as many types of cellulose waste and harvesting, whichever has

the best well-to-wheel assessment. The basic steps for large-scale production of

ethanol are: microbial (yeast) fermentation of sugars, distillation, dehydration and

denaturing. Prior to fermentation, some crops require saccharification or hydrolysis of

carbohydrates such as cellulose and starch into sugars. Saccharification of cellulose is

called cellulolysis. Enzymes are used to convert starch into sugar (Mofijur et al., 2015).

Production of Biofuel

In recent years, production of biofuel around the world raised drastically. For

example, in 2010, increasing by 17 % from 2009, worldwide biofuel production reached

105 billion liters (28 billion gallons US), and 2.7 % of world′s fuels for road transport

are largely contributed from ethanol and biodiesel. This is driven primarily by the

government’s pursuit of energy security, economic development (particularly,

improvement of trade balances and expansion of the agriculture sector), and poverty

alleviation. Biofuel strategies of the most Asian countries are focused around the

country’s main agricultural product and new business opportunities (Rasul, et al., 2015).

World Demand

Dating back to antiquity when alcohol was only used as an alcohol beverage, the

importance of ethanol to man has continued to rise. As a result of the myriad of use

that ethanol could be put to, the demand for ethanol has increasingly gained

prominence most especially in the process industries. The wide array of raw materials

from which ethanol can be produce emphasizes the special role ethanol plays in the

technological scheme of things. Efforts have been made to improve already established

methods of producing ethanol for optimum yield and efficiency and more drives are on

to open up new areas of study. With increasing global warming and desire of man to
expand the supply of motor fuel and reduce pressure on world crude oil supplies

needed to refine gasoline has led to the increasing world demand for ethanol

(Inderwildi, 2009).

Ethanol Production in Philippines

The Philippines filed an annual biofuels report with the USDA Foreign Agricultural

Service’s Global Agricultural Information Network, noting ethanol production is expected

to increase through next year due to the buildup of capacity. There are eight ethanol

plants operating in the Philippines in the year 2014 with a combined capacity of 222

million liters (58.65 million gallons). The nation produced 168 million liters of ethanol in

the year 2015, up 46 percent when compared to the 115 million liters produced in

2014. Three additional ethanol plants began operations in the year 2016 and 2017

(Voegele, 2016).

Sugarcane and molasses are used in Philippine ethanol production, while coconut

oil (CNO) is the preferred biodiesel feedstock. The current official blend mandates are

10 percent and five percent for ethanol and biodiesel, respectively. However, the actual

rates are lower, particularly for biodiesel. The Biofuels Act gives priority to local ethanol

over imports, but the mandated blend historically has largely been met through the

latter. Biodiesel imports are not allowed under the Biofuels Act (Corpuz, 2017).

Benefits of Bioethanol

Bioethanol Reduces Greenhouse Gas Emissions

 Ethanol in general reduces greenhouse emissions by up to 46% compared to

gasoline, and the added bonus of bioethanol not relying on harmful chemical processing

means it further minimizes the harmful effects of gasoline use. The use of ethanol-

blended fuels such as E85 (85% ethanol and 15% gasoline) can reduce the net

emissions of greenhouse gases by as much as 37.1%, which is a significant amount

(Gable, et al., 2017).

Bioethanol is entirely comprised of biological products, and hence the

combustion of bioethanol results in cleaner emissions (carbon dioxide, steam and heat).

Carbon dioxide is absorbed by plants and processed via photosynthesis to help the plant

grow. This cycle of creation and energy combustion means bioethanol could potentially

be a carbon neutral fuel source (Perolini, 2015).

Lesser Risks to Human Health

An active research area is the impact of bioethanol and its blends on human

health.PM (Particulate matter) and hydrocarbon emissions from diesel engines may be

toxic and/or carcinogenic. In 2011, The Mining Safety and Health Administration found

that switching from petroleum diesel fuels to high blend levels of bioethanol significantly

reduced PM emissions from underground diesel vehicles and substantially reduced

worker exposure. Nonetheless, even low concentrations of bioethanol reduce PM

emissions and provide significant health and compliance benefits wherever humans

receive higher levels of exposure to diesel exhaust (Chen, et al., 2015).

 The use of biodiesel leads to the substantial reduction in PM, HC and CO

emissions accompanying with the imperceptible power loss, the increase in fuel

consumption and the increase in NOx emission on conventional diesel engines with no

or fewer modification. And it favors to reduce carbon deposit and wear of the key

engine parts. Therefore, the blends of biodiesel with small content in place of petroleum

diesel can help in controlling air pollution and easing the pressure on scarce resources

without significantly sacrificing engine power and economy (Xue, et al., 2011).

Impact of Biofuel on Engine Operation

The increasing industrialization and modernization of the world has to a step up

for the demand of petroleum derived fuel which is viable to human health as well as

environment due to emitting greenhouse gases. The use of biodiesel in diesel engines

produces lower CO and smoke opacity and NOx emissions compared to diesel fuel at

full load condition. Low concentration blends in terms of performance efficiency and

environmentally friendly emissions could be recognized as the potential candidates to

be certified for full scale usage in unmodified diesel engines (Ekrem, 2015).

Jojoba methyl ester (JME) increase 14 % and 16 % NOx emission at 1600 rpm

and 1200 rpm respectively compared to fossil diesel fuel. At lower engine speed JME

produce higher HC and CO emissions but at higher engine speed, there is no significant

difference between HC and diesel fuel while CO is lower than diesel. The results also

showed that when the exhaust gas recirculation (EGR) rate is increased, the NOx

emissions decreased (Saleh, 2015).

 The use of biodiesel-diesel-ethanol blends helps to reduce particulate matter

emissions by 30 % and a general reduction in total hydrocarbon but slightly (5.6–

11.4%) increase the NOx emissions in average. In case of unregulated emission such as

acetaldehyde and acetone increased a bit when biodiesel-diesel-ethanol blended fuel

used (Shi, et al., 2015). Diesel engine with 0 %, 5 %, 10 %, 15 % ethanol blends and

found reduction in HC and increase in NOx emission with ethanol-biodiesel blends

compared to diesel and biodiesel fuels (Banapurmath and Tewari, 2015). Euro V diesel

fuel and ethanol-biodiesel blends in a four-cylinder direct injection diesel engine. It was

found that the addition of 5 % ethanol in biodiesel improves engine performance

slightly. It also could reduce NOx, PM, CO and HC emissions compared to diesel fuel

(Zhu, et al., 2015).

Bioethanol Production Process

Yeasts (Saccharomyces cerevisiae)

Saccharomyces cerevisiae is consider as the world’s premier industrial

microorganisms being the best studied and exploited microorganism in terms of both

old and new biotechnologies .Saccharomyces cerevisiae is being use for long for

industrial production of ethanol due to its ability to produce high concentrations of

ethanol from hexoses and to tolerate high concentration of ethanol and other inhibitory

compounds. Bioethanol that can be produced from renewable biomass, such as

molasses, starch or lignocellulosic materials, is the most promising and sustainable

alternative energy resources (Somda, et al., 2011).

Fermentation

Alcohol fermentation, also known as ethanol fermentation, is the anaerobic

pathway carried out by yeasts in which simple sugars are converted to ethanol and

carbon dioxide. Yeasts typically function under aerobic conditions, or in the presence of

oxygen, but are also capable of functioning under anaerobic conditions, or in the

absence of oxygen. When no oxygen is readily available, alcohol fermentation occurs in

the cytosol of yeast cells (Mikell, 2015).

Distillation

Distillation is a widely used method for separating mixtures based on differences

in the conditions required to change the phase of components of the mixture. To

separate a mixture of liquids, the liquid can be heated to force components, which have

different boiling points, into the gas phase. The gas is then condensed back into liquid

form and collected. Distillation is used for many commercial processes, such as the

production of gasoline, distilled water, xylene, alcohol, paraffin, kerosene, and many

other liquids.

In ethanol production, the water-ethanol solution is heated in a flask. Ethanol

has a lower boiling point than water so it evaporates first. The boiling point of alcohol

depends on which type of alcohol you're using. Here is a look at the boiling point of

different types of alcohol. The boiling point of ethanol or grain alcohol (C2H5OH) is

78.37 °C. Methanol (methyl alcohol, wood alcohol) is 66°C. Isopropyl Alcohol is 80.3°C

(Helmenstine, 2017).
 Sugarcane molasses are the most common producer of bioethanol and the

distillery process yields molasses that can also be used in animal feeding. In every

200ml of molasses the flasks were distilled using simple distillation method at 78ºC for

3 hours (Bakhiet, et al., 2015).

Production of Bioethanol with Different Commodities

Fruit Wine and Ethanol Production as Influenced by Selected Fermentation

Techniques of Balimbing (Averrhoa Carambola)

The widely used fermentation technique such as pressing and crushing is not as

efficient as the tested techniques because it requires the juices extraction and some of

the fruit juice are lost in this process. All of the fermentations are done in equal

conditions and all the additives added in each run are equally ratioed to the weight of

the balimbing used in the sample. The slicing fermentation technique yielded 75.6

ml/kg, a much more higher ethanol than all the other technique used, however it is just

as efficient compared to the mashed fermentation with an efficiency of 21% and 19%

respectively. Direct fermentation such as sliced and mashed techniques are not only

more convenient but also produced more ethanol than both the ensiled techniques

tested. It was also determined that fruit wine was the most feasible product of

balimbing fermentation with the highest BCR of 1.54. Ethanol production from

balimbing fermentation cannot be feasible because the fruit has low sugar content

therefore its ethanol yield was also low (Taño, 2018).

Extraction of Ethanol from Saba Banana (Musa saba) Peels by Hydrolysis,

Yeast Fermentation and Duration.

The saba banana peels was processed and hydrolyzed to convert the starch from

the peels into sugar. It was done by mixing the grinded banana peels with distilled

water and then heated up approximately 80º C. The hydrolyzed solution was then

transferred into the glass bottles and was added with yeast and sugar. Fermentation

varies from 3 to 5 weeks. Lastly, after fermenting the mixture for weeks, the solutions

were distillated to extract the ethanol. It was heated to let the ethanol evaporate and

condense into liquid form.

The results shows that the highest amount of percentage ethanol is treatment

W1S2 (3 weeks with 20 grams of sugar) and treatment W2S2 (4weeks with 20 grams of

sugar) since both of them showed no significant different as the highest and the best

treatment to choose to get the highest volume of distillate should be treatment W 3S2 (5

weeks with 20 grams of sugar) (Dela Cruz, 2018).

Extraction of Ethanol From Marang (Artocarpus odoratissimus) Peels

The collected distillates from solutions with 20 g of sugar yielded higher percent

ethanol compared to the solutions with no amount of sugar. Solutions with no sugar

produced an average of 10.52 %, 22.8 %, and 22.21 % for 3, 4, and 5 weeks length of

fermentation, respectively. Meanwhile, solutions with 20 g sugar produced an average

of 75.98 %, 76.87 % mL, and 79.18 % mL for 3, 4, and 5 weeks length of

fermentation, respectively. It can be incurred that it is more feasible to produce ethanol

using marang peels with 20 g sugar and the highest percent ethanol can be produced

with 5 weeks length of fermentation (De Dios, 2018).

Conceptual Framework

LIGNOCELLULOSIC
BIOMASS

MILLING

PRETREATMENT

HYDROLYSIS

FERMENTATION

PRODUCT
PURIFICATION

ETHANOL
 Hypotheses

 There is no significant difference in the distilling duration in different

fermentation process and duration.

 There is no significant difference in the distilling rate of the bioethanol

produced in different fermentation process and duration.

 There is no significant difference in the percent alcohol content produced in

different fermentation process and duration.

 There is no significant difference in the bioethanol yield in different

fermentation process and duration.

CHAPTER III

METHODOLOGY

Research Local

This study is conducted at the Chemistry Laboratory of Davao del Sur State

College – Digos Campus.

 Research Design

This study use Randomized Complete Block Design (RCBD). There is 2 factors

with 3 replications:

Factor A Factor B

A1 – 10 grams of yeast B1 – 7 days

135 mg. Of grinded starfruit

250 mL. distilled water

A2 – 13 grams of yeast B2 – 14 days

135 mg. Of grinded starfruit

250 mL. of distilled water

A3 – 15 grams of yeast B3 – 21 days

135 mg. Of grinded starfruit

250 mL. of distilled water

Materials Used

The materials needed to produce ethanol from starfruit are inexpensive and

locally available in the market. Most laboratory apparatus is lended from chemistry

laboratory of Davao del Sur State College – Digos Campus. The materials needed for

this study are:

  500 mL container

 Beaker

 Knife/Cutter

 Digital Weighing Scale

 1 liters of distilled water

 Blender

 Baker’s yeast (80 g)

 Clean Cloth

 Distilling flask

 Hot plate

 Thermometer

 Graduated cylinder

 Rubber stopper

 Water pump

Bioethanol Production

Preparation of Samples

Starfruit is collected at the local market of Digos City. Starfruit is putted in sack

and weighted for about 3 kgs. Starfruit is clean and cut. Starfruit is grinded using

blender until all starfruits are uniform in size.

 The containers and other equipment in contact with the sample is properly

cleaned before conducting test.

Fermentation Process

The juices that is extracted from starfruit are subjected in fermentation process.

Twenty-seven (27) bottles of 500 mL water container is prepared for this process.

Container is properly cleaned. Bottle one (1) has 10 grams of yeast, 90 grams 0f

grinded starfruit and 100 mL of distilled water in a 500 mL empty water container.

Bottle two (2) has 15 grams of yeast, 90 grams of grinded starfruit and 100 mL of

distilled water in a 500 mL empty water container. Bottle three (3) has 20 grams of

yeast, 90 grams of grinded starfruit and 100 mL of distilled water in a 500 mL empty

water container. Each bottle is subjected to different fermentation duration: B1 – 7

days, B2 – 14 days, B2 – days and shaken every 6 hours. Before subjecting to

distillation process, each washed solutions is submerged by alcoholmeter to get its

alcohol content by volume.

Distillation Setup and Pre-Testing

Distillation process is conducted at the chemistry laboratory of Davao del Sur

State College – Digos Campus. Pre-testing is done before conducting the study. All of

the laboratory apparatuses are supplied in the laboratory.

Distillation Process

After fermentation process, the washed is subjected to distillation. Washed is

filtered with cotton cloth to obtain its clear juice. Washed is boiled in 78 degree Celsius

(Bakhiet and Mahmoud, 2015). Temperature is carefully observed and maintain in 78

degrees Celsius. Water pump is used to mimic the function of vacuum pump. If the

temperature will rise above 78 degree Celsius hot plate will be reduced.

Data Gathered

Distilling Duration

Distilling duration is recorded when there is no more alcohol poured on the

receiving flask. Five (5) minutes is added if there alcohol that has poured on the

receiving flask.

Distilling Rate

Distilling rate is calculated using the equation:

DR= EP/DT Equation 1.

Where:

DR= Distilling rate (mL/min.)

EP= Ethanol Production (mL)

DT= Distillation Time (min.)

Percent Alcohol Content

Alcohol content of the ethanol is determined using alcoholmeter. Alcoholmeter is

submerged in the ethanol and its proof is recorded.

Bioethanol Yield

Bioethanol yield is determined by recording its volume of the bioethanol produced in

different fermentation process.

Statistical Tool

Data gathered is analyzed using the Analysis of Variance (ANOVA) for

Randomized Complete Block Design (RCBD) at 1 % and 5 % level. Significant treatment

means is further analyzed using Least Significant Difference (LSD).