CHAPTER 1

INTRODUCTION

1.1 PRODUCT INFORMATION

A. Product Description
Citric acid was first isolated by Karls Scheels in 1874, in England, from the lemon juice
imported from Italy. Italian manufacturers had monopoly for its production for almost 100
years, and it was sold at high cost. This led extensive attempts all over the world to find
alternatives way for its production, which included chemical and microbial techniques
(Vandenberghe, et al., 1999). However, experimental trials using different types of culture
media to assist the production of citric acid did not succeed due to contamination problems
and long duration of fermentation hours. In 1917, Currie found out that Aspergillus niger
had the capacity to accumulate significant amounts of citric acid is sugar based medium.
Starting from this, the citric acid production progressed exponentially.

Currently, citric acid is the most produced organic acid measured in tonnage. Its
production has now reached 1.4 million tonnes per year and continues to increase more
each year. The main reason for constant increase is the large number of applications that
can be found for citric acid, mainly in the food and pharmaceutical industries. Traditional
processes, such as the submerged fermentation using the fungus Aspergillus niger,
dominate the global production. However, different techniques of production are
continuously being studied showing new perspectives for the production of citric acid. In
this context, solid-state fermentation appears where agro-industrial residues specifically
orange peel can be used as substrate-supports to the filamentous fungi Aspergillus niger.
With this process, the orange peel wastes can be utilized as raw material in producing citric
acid. The problem of solid waste can thus be solved while manufacturing the required
compound. Hence, by applying this in orange processing companies, the wastes generated
can be minimized and turned into additional income.
B. Product Properties
Citric acid (2-hydroxy-propane-1,2,3-tricarboxylic acid) derives its name from the
Latin word citrus, a tree whose fruit is like the lemon. Citric acid is a tricarboxylic acid
(Figure 1) with a molecular weight of 210.14 g/mol, which contains three carboxylic
functional groups with three different values of pKa (3.1, 4.7, and 6.4). It is a primary
metabolic product formed in the tricarboxylic acid (or Krebs) cycle and is found in small
quantities in virtually all plants and animals, being isolated from lemon juice in 1784.

Figure 1: Citric Acid Chemical Structure

Citric acid, with a molecular formula of C6H8O7, is a natural preservative and is also
used to add an acidic (sour) taste to foods and soft drinks. In biochemistry, it is important
as an intermediate in the citric acid cycle and therefore occurs in the metabolism of almost
all living things. It also serves as an environmentally benign cleaning agent and acts as an
antioxidant. Citric acid exists in a variety of fruits and vegetables, but it is most
concentrated in lemons and limes, where it can comprise as much as 8 percent of the dry
weight of the fruit.

C. Local Production of the Product

Currently, there are only four companies manufacturing and supplying citric acid here
in the Philippines. As per data, Himmel Industries Incorporation, Cleveland Industries
Incorporation, Obetech Pacific Philippines, and Toplinechem Marketing Corporation are
registered as the major suppliers of citric acid here in the Philippines.

D. Role of the Product in the Industry

Citric acid is a versatile and innocuous alimentary additive. It is accepted worldwide as
GRAS (generally recognized as safe), approved by the Joint FAO/WHO Expert Committee
on Food Additives. The food and pharmaceutical industries utilize citric acid extensively
because of its general recognition of safety, pleasant acid taste, high water solubility and
chelating and buffering properties. Citric acid is used in cosmetics and toiletries as buffer,
and in a wide variety of industrial applications as a buffering and chelating agent. Citric
 acid is also a reactive intermediate in chemical synthesis. In addition, its carboxyl and
hydroxyl groups permit the formation of a variety of complex molecules and reactive
products of commercial interest.

Table 1: Industrial Applications of Citric Acid

Applications Industry Functions
Prevents browning in some white wines. Prevents
Wines and ciders
turbidity of wines and ciders. Used in pH adjustment
Beverages
Soft drinks and Provides tartness. Stimulates natural fruit flavour. As
syrups acidulant in carbonated and sucrose based beverages.
Used in pH adjustment. Acts as acidulant. Provides the
Jellies, jams and
desired degree of tartness, tang and flavour. Increases
preservatives
the effectiveness of antimicrobial preservatives
As emulsifier in ice creams and processed cheese.
Dairy products Acidifying agent and antioxidant in many cheese
products.
Acts as acidulant. Provides tartness. Minimizes sucrose
Food
Candies inversion. Produces dark colour in hard candies.
Prevents crystallization of sucrose.
Protects ascorbic acid by inactivating trace metals.
Frozen fruit
Lowers pH to inactivate oxidative enzymes.
Synergist for other antioxidants, as sequestrant.
Fats and oils
Stabilizing action.
Animal Feed Feed complementation
Micronutrient evaluation in fertilizers. Enhances P
Agriculture
availability in plants.
As effervescent in powders and tablets in combination
with bicarbonates. Anticoagulant. Provides rapid
Pharmaceuticals
dissolution of active ingredients. Acidulant in mildly
astringent formulation.
Pharmaceutics
Cosmetics and Buffering agent. pH adjustment. Antioxidant as a
toiletries metallic–ion chelator.
Industrial Acts as buffer agent. Sequestring metal ions.
Other
applications Neutralizes bases. Used in nontoxic, noncorrosive and
 biodegradable processes that meet current ecological
and safety standards.
Removes metal oxides from the surface of ferrous and
nonferrous metals, for operational cleaning of iron and
copper oxides. In electroplating, copper plating, metal
cleaning, leather tanning, printing inks, bottle washing
Metal cleaning compounds, floor cement, textiles, photographic
reagents, concrete, plaster, refractories and moulds,
adhesives, paper, polymers, tobacco, waste treatment,
chemical conditioner on teeth surface, ion
complexation in ceramic manufacture.

1.2 SURVEY METHODS USED IN CITRIC ACID PRODUCTION

Review of Alternative Designs
1.2.1 Submerged Fermentation

Figure 2: Process flow diagram for Submerged fermentation

The submerged process is used extensively and accounts for approximately 80% of world
production. The process offers high productivity, reduced labour costs, reduced space
requirements, and lower risk of contamination (Kristiansen et al., 1999; Soccol et al., 2006).
The bioreaction is performed using both conventional stirred tank reactors and air-lift reactors.
The air-lift reactor is increasingly preferred due to its lower cost, larger capacity, simple
operation, reduced risk of contamination and improved conditions for working with suspended
solids. The vessels are typically constructed from stainless steel and coated with a protective
layer to avoid corrosion and presence of trace metals in the fermentation medium. Although
batch, fed-batch or continuous mode can be used, batch mode is most common.

Figure 3: Process flow diagram for Surface fermentation

Surface fermentation, also known as liquid surface culture, was the original citric acid
industrial production technique. Even though in recent years submerged fermentation has
gained popularity, there are still small- and medium-scale industries that make use of this
method. Surface fermentation offers advantages such as lower installation and energy costs (as
it does not require energy for aeration and agitation), and is also foam free. However, it is
labour intensive and sensitive to changes in composition of the media. This method consists of
two phases, both of which are characterized by a rapid uptake of carbohydrates. The first phase
is the development of the fungus as mycelial mat on the surface of the medium and the second
phase utilizes carbohydrates by converting them to citric acid. The process is conventionally
performed in fermentation chambers, using trays made from materials such as special-grade
steel, high-purity aluminium or polyethylene. However, stainless steel trays are preferred, as
they are resistant to deformation with prolonged use (Oladele, et al., 2015).
1.3 MODIFIED PRODUCTION METHOD
The production method to be adapted in this study will be based on the generic and modified
to eliminate and minimized the number of equipment used. In doing so, the process will be
optimized and lessen the capital and maintenance cost of the plant.

Stage 1: Raw Material Preparation

The raw materials will include the preparation of the orange peel and Aspergillus niger
inoculum as well.

i. Orange Peel
The orange peel collected will be sundried to reach a moisture content lower than
10%. The feed will be fed to a miller using a belt conveyor and achieve a particle size
less than 2 millimeters. By maintaining the orange peel size will result to a more
homogenized output and create a uniform surface area for the reaction of the fungi and
the waste peel to produce citric acid.
ii. Aspergillus niger
The strain of Aspergillus niger used in the solid state fermentation in this study is
strain CA16. The strain CA16 will be used as the original parent strain which was a
natural isolate from soil. The strain will be collected in locally and will be revived in a
onto a potato broth medium for 7-8 days at 30-31℃ and 200 rpm. The fungi will be
maintained onto a Potato Dextrose Agar plates for 96 hours and will be stored at 4℃
for the inoculation with the orange peel substrate.

Stage 2: Product Preparation

The production of citric acid will focus mainly on the solid-state fermentation of orange
peel using Aspergillus niger. After the raw materials preparation, they will be fed to a
continuous stirred tank fermenter and will be allowed to react for four days. During this
stage, sufficient amount of nutrient as ammonium nitrate will be added to supply the
requirement needed for the growth of the fungi. The reaction will take place as follows:

C12 H22O11  4.95O2  0.133 NH4 NO3  1.56CH1.72O0.55 N0.17  3.54CO2  5.32H2O  1.15C6 H8O7

The process can be summarized in the diagram below.

 Off Gas

Orange Peel Biomass

FERMENTER
Nutrients Citric Acid

Air
Figure 4: Schematic diagram for fermentation

Stage 3: Product Purification

In most fermentation process, many rely on a purification scheme to purify its product-
fermentation broth. Once the citric acid is made in the production fermenter, the broth is
still highly contaminated. Among many options for citric acid purification, precipitation
with lime and sulfuric acid and filtration to produce free citric acid. Finally, a crystallization
process is carried out to produce anhydrous citric acid.

i. Reaction with Hydrated Lime

The citric acid broth from the production fermenter is highly contaminated by
leftover biomass, salts, sucrose, and water. First, the citric acid must be reacted with
calcium carbonate to neutralize the broth and form the insoluble precipitate calcium
citrate. Calcium citrate contains about 74% citric acid. The stoichiometric equation is
as follows:
3Ca(OH)2 + 2C6H8O7∙H2O → H2O+ Ca3(C6H5O7)2
The process can be summarized in the diagram below.

Hydrated Lime
CSTR Calcium Citrate and
Contaminated Citric Contaminants
Acid

Figure 5: Schematic diagram for reaction with lime

 ii. Filtration of Precipitate
The calcium citrate precipitate is then washed, heated and filtered to remove any
number of contaminants. Using this filter, larger contaminants such as sucrose and salts
will be removed.
The process is shown in the diagram below.

Calcium Citrate and FILTER Calcium Citrate,

Contaminants Biomass and Water

Figure 6: Schematic diagram for Filter 1

iii. Reaction of Precipitate with Sulfuric acid

To crack the calcium citrate precipitate, sulfuric acid is needed. The temperature of
this reaction should stay below 60ºC. The reaction will produce free citric acid and as
a new precipitate, calcium sulfate, which is needed to be removed in the next filter.

The process diagram is shown below.

Sulfuric Acid

Calcium Citrate, Calcium Sulfate, Free

CSTR Citric Acid, Biomass
Biomass and Water
and Water

Figure 7: Schematic diagram for reaction Sulfuric Acid

iv. Filtration of Precipitate

In this secondary filter, the calcium sulfate is washed away from the citric acid and
leftover biomass is also removed. The filter will remove all remaining contaminants
and will exit as citric acid and water solution.
The process diagram is shown below.
 Calcium Sulfate, Free
Citric Acid, Biomass FILTER Citric Acid and Water
and Water

Figure 8: Schematic diagram for Filter 2

v. Crystallization

In order to produce the desired anhydrous citric acid, the resulting solution from
filter 2 will be fed to a crystallizer. Commonly, crystallized citric acid finds more
economic value in the market.

The process is shown in the diagram below.

Anhydrous Citric Acid

Citric Acid and CRYSTALLIZER
Water
Saturated Solution

1.4 AUXILARY MATERIALS AND EQUIPMENT

A. Materials
i. Hydrated Lime
Lime-sulfuric process method is commonly applied in industrial applications.
Precipitation by hydrated lime is employed in large scale processes. This classical
recovery is well suited for impure liquors. The spent culture contains the bulk of
impurities found in the raw materials and direct crystallization of product is not feasible.
The mycelial biomass is removed from the spent culture by vacuum or belt discharge
filtration. Calcium hydroxide is then added to the product stream, to neutralize the broth
and form an insoluble calcium citrate precipitate. , proposed an optimum procedure for
the recovery of calcium citrate at 50 °C for 20 minutes. Although the rate of
precipitation is relatively slow, the reaction shown below, goes to completion at 50 °C.

3Ca(OH)2 + 2C6H8O7∙H2O → H2O+ Ca3(C6H5O7)2

The lime is added to ensure that sufficiently large crystals of high purity are
obtained. The lime is added at an empirically determined rate at about 90℃ at pH 7.0.
 ii. Sulfuric Acid

The precipitate coming from the filter 1 is consequently treated with 60-70% in
slight excess of 1-2 g/L in acidulator to ensure complete recovery of citric acid. The
reaction scheme is shown below. The product solution is filtered to remove the calcium
sulphate (gypsum) precipitate.

H2SO4 + Ca3(C6H5O7)2→3CaSO4+2C6H8O7

B. Equipment
i. Conveyor
In transferring the orange peel to the fermenter, a belt conveyor is used. A belt
consists of two or more pulleys (sometimes referred to as drums), with an endless loop
of carrying medium that rotates about them. One or both of the pulleys are powered,
moving the belt and the material on the belt forward. The powered pulley is called the
drive pulley while the unpowered pulley is called the idler pulley. There are two main
industrial classes of belt conveyors; Those in general material handling such as those
moving boxes along inside a factory and bulk material handling such as those used to
transport large volumes of resources and agricultural materials, such as grain, salt, coal,
ore, sand, overburden and more. Thus, the choice of using such is justified.
ii. Tanks
The choice of tank type will be critical in this study. In the production of citric acid
adapted in this study, unit steps are commonly reactor types that must handle high or
low pH conditions. It is a must therefore, that the selection of tank type fulfill the design
criteria for each equipment.
iii. Control Valves

The type of control valve used mainly in citric acid production ranges from
pneumatic and butterfly valves.

iv. Heat Exchangers

Due to risks of contamination, the feed and exit streams are sterilized by heat
exchange with saturated steam. Plate type and shell-and-tube exchanger find wide range
of applications in industrial productions such as citric acid.
 v. Pumps

The utilities and materials for the production are pumped to the succeeding
equipment using centrifugal pumps. Pump selection will be based on the required
suction head for transferring the liquids.

1.5 REASONS FOR ENTERING THE MARKET AT THIS TIME

Currently, Philippines is known for its wide variety of resources, ranging from grains, fruits
and vegetables. Some of these are citrus fruits like mandarin and orange. On this paper, the
main raw material used is orange peel. This is due to the area's distinctive climate and culture
contribution. These fruits are mostly used or food consumption and industrial processes which
are commonly limited in using the meat of the fruit. To widen the scope of products
manufactured from orange as raw material, industrial production of citric acid using orange
peel, a non-consumable part of the fruit. If the proposed plant is realized, it will not only be a
gateway for recycling a waste but also offers possible employment opportunities for Filipinos.

1.6 ENVIRONMENTAL ISSUES

Environmental and safety problems that can be encountered during the operation of
production of citric acid from orange peels are wastewater outputs from washing, fruit residues
from crushing, waste or sediments from filtering and clarifying and chemical toxicities. For the
wastewater outputs, the addition of a wastewater treatment facility in the operation of the
upstream process can be address. Fruit residues from crushing can be further recycled as
fertilizers or biomass. The toxicity of acids from fermentation process can cause irritation to
the respiratory tract and severe damage that can results breathing difficulties and redness and
pain when subjected to skin contact. This affects the personnel in the fermentation and product
purification sections in the plant. Therefore, personal protective equipment (PPE) must be
strictly observed at all times.
 CHAPTER 2
REVIEW OF RELATED LITERATURES

2.1 ORANGE
Orange is the fruit of the citrus species Citrus sinensis in the family Rutaceae. It is also
called sweet orange, to distinguish it from the related Citrus aurantium, referred to as bitter
orange. The sweet orange reproduces asexually (apomixis through nucellar embryony);
varieties of sweet orange arise through mutations. The orange is a hybrid between pomelo
(Citrus maxima) and mandarin (Citrus reticulata). The chloroplast genome, and therefore the
maternal line, is that of pomelo. The sweet orange has had its full genome sequenced.

Sweet oranges were mentioned in Chinese literature in 314 BC. As of 1987, orange trees
were found to be the most cultivated fruit tree in the world. Orange trees are widely grown in
tropical and subtropical climates for their sweet fruit. The fruit of the orange tree can be eaten
fresh, or processed for its juice or fragrant peel. As of 2012, sweet oranges accounted for
approximately 70% of citrus production.

In 2014, 70.9 million tonnes of oranges were grown worldwide, with Brazil producing 24%
of the world total followed by China and India.

Like most citrus plants, oranges do well under moderate temperatures—between 15.5 and
29 °C (59.9 and 84.2 °F)—and require considerable amounts of sunshine and water. It has been
suggested the use of water resources by the citrus industry in the Middle East is a contributing
factor to the desiccation of the region. Another significant element in the full development of
the fruit is the temperature variation between summer and winter and, between day and night.
In cooler climates, oranges can be grown indoors.

2.2 ORANGE PEEL COMPOSITION

Orange peel contains soluble sugars and pectin as the main components. According to
Rivas et al. (42), the orange peel is in fact constituted by soluble sugars, 16.9 % wt; starch, 3.75
% wt; fiber (cellulose, 9.21 % wt; hemicelluloses, 10.5 % wt; lignin 0.84 % wt; and pectins,
42.5 % wt), ashes, 3.50 % wt; fats, 1.95 % wt; and proteins, 6.50 % wt.

The total sugar content of orange peel varies between 29 and 44 %, soluble and insoluble
carbohydrates being the most abundant and economically interesting constituents of this
residue. Approximately 50 % of the dry weight of orange is soluble in alcohol, and soluble
sugars are the major components also of this fraction. Glucose, fructose and sucrose are the
main sugars, although xylose can also be found in small quantities in orange peel. Insoluble
polysaccharides in orange peel are composed of pectin, cellulose and hemicelluloses. Pectin
and hemicelluloses are rich in galacturonic acid, arabinose and galactose, but they also contain
small amounts of xylose, glucose, and perhaps rhamnose. Glucose is the dominant sugar in the
cellulosic fraction, which also contains some quantities of xylose and arabinose, traces of
galactose and uronic acids, and in some instances mannose. On the other hand, lignin seems to
be absent in these tissues. Consequently, a mixture of cellulases and pectinases is needed to
complete the conversion of all polysaccharides to monosaccharides.

2.3 MICROBIAL PRODUCTION OF CITRIC ACID

2.3.1 Microorganisms
Fungi, yeasts and bacteria have been used for the production of citric acid. An extensive
review of microorganisms used for citric acid production can be found in literature (Rohr
& Kubicek, 1987; Krishnan, 1999; Soccol et al., 2006). Currie (1917) showed that certain
strains of A. niger are able to produce large amounts of citric acid in a nutrient medium,
with a high sugar and mineral salts concentration. This established the basis for commercial
production of citric acid. Commercial production of citric acid using yeasts was
predominant during the 1960‘s and 1970‘s, when raw materials such as hydrocarbons were
relatively cheap. Although various carbon sources can be used with yeasts, a substantial
quantity of unwanted isocitric acid is produced. Aspergillus niger thus remains the
preferred organism for commercial production due to its ease of use, high yields and ability
to ferment a variety of raw materials (de Beer, 2011).

2.3.2 Substrates
Substrates including molasses, starchy materials and hydrocarbons have been used for
commercial citric acid production (Grewal & Kalra, 1995). In a study conducted by Hang
and Woodams, the potential of food processing solid residues as a substrate for citric acid
production by solid state fermentation using Aspergillus niger was determined. Yields of
citric acid varied considerably and were found to depend significantly on the strain of
Aspergillus niger used and the following factors: the type of raw material fermented, the
initial moisture content of the substrate, the amount of methyl alcohol present, and the
fermentation time and temperature.
2.3.3 Culture Conditions
The culture conditions for improved production of citric acid have been reported
extensively in literature and patents. To achieve a high production rate and yield of citric
acid, essential nutrients such as carbon, nitrogen, phosphorus, growth factors are required.
Aeration, pH and temperature need to be tightly controlled to attain optimal production
conditions.

2.3.3.1 Carbon Source

The type and concentration of the carbon source strongly influences the production
of citric acid (Hossain & Ahmed, 1992), (Kristainsen, et al., 1999), (Soccol, et al.,
2006), (Papagianni, 1995). Generally, only sugars, rapidly taken up by the
microorganism, are suitable for a high yield production. Polysaccharides need to first
be hydrolysed before being used as a carbon source due the slow rate of uptake relative
to the rate of sugar catabolism. The use of sucrose is preferred over glucose, fructose
and lactose due to A. niger’s ability to rapidly hydrolyze the sugar with an extracellular
mycelium bound invertase. A. niger can also readily utilise mannose, xylose and
arabinose and produce citric acid, but at lower yields than from glucose (Maddox, et
al., 1985). Careful consideration should be given in selecting the carbon source due to
factors such as costs or the need for pre-treatment (Soccol, et al., 2006).

2.3.3.2 Nitrogen Source

High purity media are usually supplemented with nitrogen in the form of
ammonium sulphate or ammonium nitrate. It is generally preferred that ammonium
salts are used, since their consumption results in a decrease in pH, a prerequisite for
citric acid production (Grewal & Kalra, 1995) (Papagianni, 1995). Ammonium sulphate
has been shown to prolong the growth phase, while a shorter growth period is associated
with the addition of ammonium nitrate (Grewal & Kalra, 1995). The nitrogen
concentration required for the production is typically 0.1 to 0.4 g/L (Soccol, et al.,
2006). A high concentration of nitrogen favours fungal growth and sugar consumption,
but decreases the amount of citric acid formed (Soccol, et al., 2006).

2.3.3.3 Phosphorus Source

Increased fungal growth and reduced citric acid production is promoted with a
higher phosphorous concentration. Phosphate concentration is cited as an important
factor in morphological development and process productivity (Ali, 2004), however
contradiction exists in the literature (Papagianni, 1995). Shu and Johnson (1948)
concluded that phosphate limitation is not required for acid accumulation, while
Kubicek and Rohr (1987) showed that citric acid accumulation is achieved by
phosphate limitation. Conversely, excess phosphorous results in decreased carbon
dioxide fixation and hence the stimulation of mycelium growth (Soccol, et al., 2006).
Potassium dihydrogen phosphate has been reported as the most suitable phosphorous
source. A phosphorous concentration of between 0.5 and 5 g/L is required for maximum
citric acid production (Grewal & Kalra, 1995).

2.3.3.4 Aeration
The rate of oxygen supply to the aerobic process has a major effect on the
productivity and yield of citric acid. Improved product yields and reduced process times
are achieved with higher aeration rates. The oxygen concentration should be maintained
above 25% of saturation (Soccol, et al., 2006). Critical dissolved oxygen tension (DOT)
of 8-12% and 10-15% of air saturation should be maintained for the respective growth
and product phases (Grewal & Kalra, 1995). Although high aeration rates are typically
required for improved product yields, a study by Prado et al. (2004) showed that citric
acid production using solid-state techniques (SSF) is favoured at low aeration rates
(0.18 m3 /kg dry carbon source) due to limited biomass growth. It was observed that
strongly aerated mediums increased sporulation, in turn reducing acid accumulation.
Aeration rates in industrial operations are typically between 0.1 vvm and 1 vvm,
increasing as demand increases with biomass growth (Grewal & Kalra, 1995).

2.3.3.5 pH
To maximise the production of citric acid, a low pH is essential. The working pH is
typically pH 2.2 to 2.6 (Rohr & Kubicek, 1987), but is dependent on the carbon source.
Above pH 4, the production of oxalic acid is accelerated, reducing the yield of citric
acid. The pH should be well defined and optimized according to the microorganism,
substrate and production technique (Soccol, et al., 2006).
 CHAPTER 3
MARKET STUDY

Market analysis is also known as a documented investigation of a market that is used to

inform a firm’s planning activities, particularly around decisions of inventory, purchase, work
force expansion or contraction, facility expansion, purchases of capital equipment, promotional
activities, and many other aspects of a company. Market study is a critical step in the
development of a plant. The market study shows the demand and supply of citric acid for the
past years and the demand and supply in the future.

3.1 DEMAND OF CITRIC ACID

Citric acid is one of the most important organic acids which have an ever ending demand
in the world. Citric acid is the most important organic acid produced in tonnage by
fermentation. Global production of citric acid in 2004 was about 1.4 million ton estimated by
Business Communications Co. (BCC) in a recent study of fermentation chemical markets
(Graf, 2005). The production of citric acid has increased rapidly, reaching about 1.7 million
tons per annum in 2008 with 5% predicted annual increase in the rate of production in order to
meet the growing needs of the global market (Dhillon et al., 2011). Although according to
Carlos (2006), the production rate of citric acid has growth is of 3.5 to 4.0% per year.

3.5

3
Metric tonnes (millions)

2.5

Demand
1.5
Supply
1

0.5

0
2007 2008 2009 2010 2011 2012
Year

Figure 9: Citric Acid Global Demand and Supply

 The high demand in citric acid is the wide usage as acidulent in food and beverage industry.
In the 1980’s, U.S.A has been the leading country in producing citric acid. But, in the year of
1995, the Chinese production volume of citric acid has surpassed that of United States (Connor
2008) due to the lower cost of raw materials and the lower price of citric acid.

3.2 SUPPLY OF ORANGE PEEL

On the other hand, Figure 3 relates to the total domestic production of orange peels, whether
inside or outside the agricultural sector, i.e. it includes non-commercial production and
production from kitchen gardens. Unless otherwise indicated, production is reported at the farm
level.

Figure 10: Production quantity of Oranges in the Philippines (FOASTAT)

At the same time, the local production of orange in the Philippines from 2014 to 2016,
averaged to 3.135 thousand metric-ton and an import of 19.945 thousand metric-ton. From the
total of 21.695 metric-ton, 4.5559 metric-ton or 21% of which is net food disposable
(Authority, 2014-2016)

3.3 PRODUCT PRICE

About 19.3% of the net food disposable could be converted into citric acid (Torrado, et al.,
2011) by solid-state fermentation of orange peels. With the current cost of citric acid of ₱ 6450
per 25 kg, a high profit could be obtained. Citric acid from orange peel using solid state
fermentation is therefore a viable production.
 INPUT PROCESS OUTPUT

Orange
Mill
Peel Milled
Orange Peel
Milled
Orange Peel
CO2
Aspergillus Niger
Ammonium Nitrate Fermenter
Water
Biomass
Air C6H507•H2o

Water
CSTR 1
Lime Calcium Citrate
Biomass

Water
Filter 1 Biomass
Water
Calcium Citrate
Water
Water
Calcium Citrate
CSTR 2 Calcium Citrate
Sulfuric Acid Citric Acid
Water

Calcium Sulfate
Filter 2
Citric Acid
Water
Citric Acid
Water Water
Crystallizer
Anhydrous
Citric Acid
QUALITATIVE FLOWSHEET
 MATERIAL BALANCE
A. Crystallizer
Assume:
Estimated Basis of operation is two months. Within this timeframe, the target product,
anhydrous citric acid, is 1 ton. Converting this to kilogram per hour, the product would be 0.70
kg/hr.

H2O Vapor
4.51 kg/h

FEED Product
7.3339 kg/h 0.70 kg/h
CRYSTALLIZER
= 0.2639 = 0.98
= 0.736 = 0.02

Liquor
2.1339 kg/h
=0.5858
= 0.414

Let F = Feed
V = vapor
L = Liquid stream out
C = Product
Assume 65% efficiency
Over Mass Balance:
Input=Output

F V  L C
L  F - C -V
L  7.3339 - 0.70 - 4.5
L=2.1339 kg/h
Component Mass Balance: H2O
Input=Output

( 1  xF )F  V  ( 1  xL )L  ( 1  xc )C
( 0.736 )( 7.3339 )  4.5  ( xH O )  2.1339   ( 0.20 )( 0.70 )
2
x H O =0.414
2

xC H O   2.1339   ( 0.20 )( 0.70 )

6 8 7
x =0.414
C6 H 8 O7

B. Filter 2
Assumption: The solid content in the filtrate is negligible.

FEED FILTER CAKE

8.319 kg/h 0.1851 kg/h
FILTER 2
XSOLID= 0.0212 = 0.9528
XLIQUID= 0.9788
= 0.0477

FILTRATE
7.3339 kg/h

Let A = Filter Cake

B = Filtrate
S = Solids
M = Moisture

Over Mass Balance around RDVF 2:

Input = Output
F  A B
8.319  A  7.3339
A  0.1851 kg / h
Component Mass Balance:
Input=Output
 X FS F  X AS A  X BS
(0.0212)(8.319)  X AS (0.1851)
X AS  0.9528

X AM  1  0.9528
X AM  0.0477

C. Continuously Stirred Tank Reactor 2

Assumptions:
A 99.8% conversion of calcium citrate to citric acid.
The system is in a steady-state.
Only 70% sulfuric acid was employed.
24% of the calcium citrate is citric acid.

FEED
7.5181 kg/h
=0.3347
OUTLET
= 0.6653 7.5181 kg/h
CSTR 2
H2SO4
0.003 kg/h
= 0.70
= 0.30

Overall Mass Balance around CSTR 2:

Input = Output
F3  F1  F2
7.5181  F1  0.003
F1  7.5151kg / h

MW nfinal Ffinal (g/h)

Compound Fo (g/h) no (mol/h) ∆x
(g/mol) (mol/h)
Ca3(C6H5O7)2 2515.1 498.46 5.0457 -nAox 0.01 0.00498
C6H8O7 0 192.2 - +2nAox 10.071 1.9357
CaSO4 0 136.14 - +3nAox 15.113 2.0566
H2O 5.0009 18 - - - -
n final  n0  x

nCa3 (C6 H 5o7 ) 2  5.0457  5.0457(0.998)  0.01

nC6 H 8O7  0  2(5.0457)(0.998)  10.071
nCaSO4  0  3(5.0457)(0.998)  15.113

F final  n final MW

FCa3 (C6 H 5O7 ) 2  0.01(498.46) / 1000  0.00498kg / h

FC6 H 8O7  10.071(192.2) / 1000  1.9357kg / h
FCaSO4  15.113(136.14) / 1000  2.0566kg / h

k
Ca3( C6 H 5O7 )2  3H 2 SO4  2C6 H8O7  3CaSO4
rC H O  2k[ Ca ( C H O ) ][ H SO ]
6 8 7 3 6 8 7 2 2 4

Account to literature: k = 1.8x10-5 at T=18⁰C

D. FILTER 1
Assumption: Filter has 99.7% efficiency in water removal

Water
5.373 kg/h

FEED
8. 5829 kg/h
solids=2.5749 kg/h
Ca3(C6H5O7)=2.5151 kg/h FILTER Filter Cake Washing Ca3(C6H5O7)2
Biomass=0.05977kg/h 1 2.5151 kg/h
Liquid=6.008kg/h Ca(C6H5O7)=2.5151 kg/h
excess C6H8O7·H2O=0.02559kg/h H2O=0.18024 kg/h
Biomass=0.05997 kg/h

Filtrate Washed out

H2O=5.82776 kg/h Water=5.373 kg/h
excess C6H8O7·H2O=0.02559kg/h Biomass=0.05977 kg/h
 Let A = Filter Cake
B = Filtrate
C = Water in
D = Washed Out
E = exit Ca(C6H5O7)2

Overall Mass Balance around the Filter:

Input=Output

F  A B

Component Balance: H2O in Filter Cake

H 2O in Filter Cake  (0.03)(6.008)

H 2O in Filter Cake  0.18024 kg/h

8.5829  2.75501  B
B  5.8277kg / h

Overall Mass Balance around Washing:

Input=Output

AC  D E
2.75501  5.373  D  2.5151
D  5.6129kg / h
E. CSTR 1
Assumptions:
The system is in a steady-state.
The line is heated to 90⁰C.

Ca(OH)2
1.024 kg/h

OUTLET
FEED 8.5829 kg/h
C6H8O7·H2O =7.5 kg/h CSTR 1 Ca3(C6H5O7)2=2.5151 kg/h
Biomass=0.05977 kg/h Biomass=0.05977 kg/h
H2O=6.008 kg/h

2C6 H8O7  H 2O  3CaOH 2  Ca3 C6 H 5O7 2  8H 2O

Over Mass Balance around CSTR 1:

Input=Output
F3  F1  F2
8.5829  F1  1.024
F1  7.5589kg / h

C6 H 8O7  H 2O  7.5589  0.05977

C6 H 8O7  H 2O  7.4991  7.5kg / h

MW
Compound Fo (g/h) no (mol/h) ∆x
(g/mol)
C6H8O7·H2O 7.4991 210.2 35.676 -2nAox
Ca3(C6H5O7)2 2515.1 498.46 - +nAox
H2O 6.008 18 - +8nAox
Biomass 0.05977 - - -
 Conversion of C6H8O7·H2O to Ca3(C6H5O7)2:
g  mol    498.46 g 
  35.676  X 
h    mol 
2515.1
h 
x  0.1414
Excess C6H8O7·H2O:
X C6 H 8O7  H 2 O , out  nAo  2nAo MW

X C6 H 8O7  H 2 O , out  35.676  2(35.676)(0.1414)

210.2 g
mol
25.59 g 1kg
X C6 H 8O7  H 2 O , out  
h 1000 g
X C6 H 8O7  H 2 O , out  0.02559kg / h

F. FERMENTER

CO2
0.528 kg/h

Orange Peel (FEED) Fermented Broth

5.8945 kg/h 7.5589 kg/h
FERMENTER
Sucrose=1.1603 kg/h C6H8O7·H2O=7.4991 kg/h
Water=4.734 kg/h C6H8O7=0.74991 kg/h
NH4NO3=0.0361 kg/h H2O=6.74919 kg/h
Biomass=0.05977 kg/h
H2O=0.34289 kg/h

Air
2.559 kg/h
O2=0.5374 kg/h

C12 H 22O11  4.95O2  0.133NH 4 NO3  1.56CH1.72O0.55 N0.17  3.54CO2  5.32H 2O  1.15C6 H8O7

749.91g / h
Mols of C6 H 8O7   3.9017mol / h
192.2 g / mol

1molC12 H 22O11 3.9017molC6 H 8O7 342 g

Sucrose consumed     1160.33g / h
1.5molC6 H 8O7 h molC12 H 22O11
 4.95molO2 3.9017 molC6 H 8O7 32 g
Oxygen consumed     537.417 g / h
1.5molC6 H 8O7 h molC12 H 22O11

1160.33gC12 H 22O11
Moles of biomass  h  3.3928molC12 H 22O11 / h
342 g
molC12 H 22O11

1.56mol biomass molC12 H 22O11 mol biomass

Amount of biomass produced    3.3928  5.2927
1molC12 H 22O11 h h
mol biomass 11g g
Amount of biomass produced  5.2927   59.779  0.059779kg / h
h mol h

0.133molNH 4 NO3 3.9017molC6 H 8O7 80 g

Amount of NH4 NO3 produced     36.1g / h
1.15molC6 H 8O7 h molNH 4 NO3

3.54molCO2 3.3928molC12 H 22O11 44 gCO2

Amount of CO2 produced     528 g / h
1molC12 H 22O11 h molCO2

5.32molH 2O 3.3928molC12 H 22O11 18 gH 2O

Amount of H 2O produced     342.89 g / h
1molC12 H 22O11 h molH 2O

0.5374
Air   2.559kg / h
0.21

Overall Mass Balance around the Fermenter:

Input=Output
Feed  Air  Fermented broth  CO2
Feed  2.559  (7.5589  0.05977  0.34289)  0.528
Feed  5.9306kg / h

Water in Orange Peel  5.9306 - 0.0361 - 1.1603

Water in Orange Peel  4.734kg / h
 Orange Peel  1.1603  4.734
Orange Peel  5.8945kg / h

G. Mill
Assumptions:
η=95⁰C
CR=4

WF
qF=5.8945 kg/h

q
MILL

CLASSIFIER
qR

R=q/qR 1.5 mm
CR=R-1
WP
qP=qF=5.8945 kg/h

Overall Mass Balance:

Input=Output
WF qF  Wp qP
WF (5.8945)  0.95(5.8945)
kg unmilled orange peels
WF  0.95
kg mix orange peels

(1  WF )  (1  0.95)
kg milled orange peels
(1  WF )  0.05
kg mix orange peels

CR in kg
CR  R  1
4  R 1
R5

q
R
qR
5.8945
qR 
5
qR  1.1789kg / h

q  qF  q R
q  5.8945  1.1789
q  7.0734kg / h
QUANTITATIVE FLOWSHEET

Orange Peel =5.8945 kg/h

MILL

Milled Orange Peel=5.8945 kg/h

H2O=4.734 kg/h
Air=2.559 kg/h FERMENTER CO2=0.528 kg/h

Fermented Broth=7.5589 kg/h

Biomass=0.05977 kg/h

Ca(OH)2=1.204 kg/h CSTR 1

Ca3(C6H5O7)2= 2.5151kg/h
Biomass = 0.05977 kg/h
H2O=6.008 kg/h

Biomass=0.05977
H2O=5.373 kg/h FILTER 1 kg/h
H2O=11.35541 kg/h

Ca3(C6H5O7)2=2.5151 kg/h
H2O=5.0 kg/h
70% H2SO4= CSTR 2
0.003kg/h

C6H5O7= 1.9357 kg/h

CaSO4=2.0566 kg/h
H2O=5.0009 kg/h

CaSO4= 2.0566
FILTER 2 kg/h

C6H8O7= 1.9357 kg/h

H2O=5.0009 kg/h

H2O(vapor)= 4.51 kg/h CRYSTALLIZE

Liquor=2.1339 kg/h
R

98% anhydrous
C6H8O7 0.70 kg/h