Citric Acid Production from Pineapple Waste

through Solid-State Fermentation

E.J. Battung, W.F. Mangaccat, H.A. Talaro

Department of Chemical Engineering, College of Engineering
University of the Philippines Diliman, Quezon City, Philippines

Abstract
Citric acid is a naturally occurring organic acid widely used in the food, beverage and pharmaceutical industries as an acidulant
or a mild preservative. It has a worldwide annual demand of about three million tons and a local demand of 22 000 tons. At
present, the local demand in the country is supplied by imports. This study aims to develop an economically feasible and
environment-friendly process flow for the first citric acid plant in the country with an annual capacity of 4400 tons. Pineapple
waste has been chosen as raw material due to its abundance in the country. The process for the plant may be divided into three
parts: raw material preparation, solid state fermentation, and purification. Downstream processes include the use of a new
technology, the Simulated Moving Bed (SMB). The use of SMB was selected because of its reduced waste and water
requirement and higher productivity. The designed plant has total capital investment of 17.4 million USD. It has an attractive
internal rate of return of 20.7 % and a net present value of $15.6 million. It has a simple payback of 4.3 years and a discounted
payback period of 5.3 years.

Keywords: Citric Acid; Pineapple waste; Solid-State Fermentation

1. Introduction plant in the Philippines. The global supply and demand

and shown in Figure 2.
 Citric acid is a weak organic acid, naturally occurring in  Conventionally, citric acid is produced industrially
citrus fruits. It has the chemical formula C 6H8O7 and through submerged microbial fermentation of molasses.
chemical name 2-hydroxypropane-1,2,3-tricarboxylic (Kumar & Jain, 2008) Submerged fermentation accounts
acid. It exists in two forms: colorless crystals in the for about 80 % of the world production of citric acid. It
monohydrate form and white crystalline powder in generally produces higher yields, lower labor costs and
anhydrous state. It has a refractive index of 1.493 to lower risk of contamination. However, it employs more
1.509 and sinks in water with a specific gravity of sophisticated installations and rigorous process control.
1.5420. It melts at 153°C, but decomposes at 175°C It also requires a large volume of waste water and higher
before it reaches vapor state. It is freely soluble in water media cost. Fermentation time is normally between five
and has relatively low dissociation constants. It may be to twelve days, depending on the process conditions.
rapidly degraded in sewage works, surface water and (Soccol, Vandenberghe, Pandey, & Rodrigues, 2006)
soil. It is also readily biodegradable. It may also be  Surface fermentation or liquid surface culture was the
oxidized by common oxidizing agents such as hydrogen first to be developed for the industrial production of citric
peroxide. Presently, it is not judged as a potentially acid. Small- to medium-scale plants usually employ this
hazardous substance to the environment. (IPCS, 2001) process due to its lower operational skill requirement
 Citric acid is a natural preservative and a mild acidulant and lower installation and energy costs. In this process,
which makes it useful in various industries. It gives the fungus develops as mycelial mat on the surface of the
characteristic sour taste of beverages and is also used medium held in shallow trays. The fermentation chamber
as flavoring agent in other foods. Citric acid also acts as which houses the trays is aerated to control the humidity
an anti-oxidant and bacterial inhabitant. It is also used, and temperature. Air entering is passed through a
in a much smaller scale, as citrate buffering of whole bacteriological filter in order to maintain the aseptic
blood samples for transfusion. It acts as an condition inside the chamber. Contamination by
anticoagulant in glucose solution to prevent blood penicillia, other aspergilli, yeasts and lactic bacteria is a
clotting. (IPCS, 2001) Moreover, it is a strong chelating problem in surface fermentation. Fermentation generally
agent which it makes it useful in cleaning boilers, takes eight to twelve days. (Soccol, Vandenberghe,
evaporators and other plant equipment. (Majumder, et Pandey, & Rodrigues, 2006)
al., 2010) Its applications are summarized in Figure 1.  Solid-state fermentation or Koji process is the simplest
 In 2012, global citric acid production was at 2 million method for citric acid production. It was developed in
metric tons while demand reached 2.8 million tons. Year Japan where raw materials such as rice bran and fruit
after year, the gap between citric acid demand and wastes were abundant. These were used as carbon
production widens. It was reported in a study of sources for fermentation, an innovative deviation from
fermentation chemical markets by Business the usual sugar molasses. In this process,
Communications Co. (BCC) that China accounts for 35– microorganisms are cultured in a medium which acts as
40 % of worldwide citric acid production. A local annual physical support and source of nutrients. The medium is
demand of about 22 million tons is currently supplied by solid and has roughly about 70 % moisture. It is adjusted
imports. At present, there is no citric acid production to an initial acidic pH of about 4.5 to 6.0 and the
1
 temperature is maintained at about 28-30°C. Under
optimal conditions, solid-state fermentation may be
completed in four days. Different strains of Aspergillus 4

Metric Tons (million)

niger and yeast have been proven to be effective in solid-
state fermentation. An advantage of solid-state 3
fermentation over the other methods is its low sensitivity
to trace elements, which significantly affects submerged 2 Demand
fermentation. This eliminates the need for rigorous pre-
treatment. Usually, autoclaving is enough to 1 Supply
decontaminate the culture medium. Solid-state
fermentation also opens the possibility of large-scale 0
citric acid production using fruit wastes as the primary
raw material. (Soccol, Vandenberghe, Pandey, & 2008 2009 2010 2011 2012
Rodrigues, 2006) As this study focuses on the use of
pineapple waste as raw material for citric acid Figure 2. Global Supply and Demand of Citric Acid
production, solid-state fermentation is the best choice
for the fermentation process.
 Precipitation is the most frequently used downstream
process. Precipitation of calcium citrate (Ca3(C6H5O7)2) is 2. The Proposed Plant
done by the addition of calcium carbonate (CaCO3), after
which the calcium citrate precipitate is separated from  Pineapple has the 12th highest production among fruits
the fermentation liquor. Sulfuric acid (H2SO4) is added to worldwide. An estimated average of 70 % is consumed
the filter cake containing calcium citrate to regenerate as fresh pineapple in its country of origin while the rest is
citric acid. Precipitation and isolation of calcium sulfate processed, canned or juiced. The Philippines alone
(CaSO4) precipitate are repeated several times to supplied more than 2.3 million tons of the global
remove the readily carbonizable substances (RCS). Anion pineapple demand. Meanwhile, an estimated third of a
and cation exchangers are used to purify the citric acid. fresh pineapple’s weight is waste. The main raw material
Citric acid is then produced through crystallization and for the proposed plant is pineapple waste because of the
drying. (Soccol, Vandenberghe, Pandey, & Rodrigues, abundant local supply of pineapple in the country. The
2006) Though widely used, this process has some raw material to be used for the plant, the pineapple
noticeable disadvantages. It is laborious and it has a waste, is sourced from the Del Monte Pineapple
high energy and water requirement. It also produces Plantation which is about 93 km away from the proposed
large volumes of carbon dioxide and waste liquor, aside plant location.
from gypsum, which has little or no commercial value.  The plant’s target market is the local food and beverage
(Wu, Peng, Arlt, & Minceva, 2009) industry. The selling price for citric acid is pegged at
 Another way to separate and purify citric acid from the 1500 US$/ ton, which is approximated by the average
medium is through liquid-liquid extraction, which price the Philippines, pays for its imports of citric acid (in
significantly produces less waste. It also eliminates the its two forms) in a year from 2004 to 2012.
need for Ca(OH)2 and H2SO4. The organic chemicals  The plant has an annual production capacity of 4,400
used are toxic, however, and may not be used in tons. The plant is to be built inside the economic zone in
producing food-grade citric acid. PHIVIDEC Industrial Authority in the Municipalities of
 In the proposed plant, a simulated moving bed (SMB) is Tagaloan and Villanueva, Province of Misamis Oriental. It
proposed, instead. Packed columns with automatic is a strategic location considering that the neighboring
valves are used to mimic moving beds in the removal of barangays have seaports and within the economic zone
RCS. The advantages of SMB technology include is the Mindanao Container Terminal (MCT). The range of
enhanced mass transfer rate resulting in lower eluent ambient temperatures (23-32 0C) is ideal for reaction
consumption and higher productivity per unit time and temperatures.
mass. It also reduces solvent requirement to up to 50%.  The utilities plant is outside the scope of the study and
Furthermore, SMB technology provides good separation the utility prices have been assumed based on the
performance even at low selectivity values. (Wu, Peng, current prices in the plant location for the economic
Arlt, & Minceva, 2009) analysis.
 This paper aims to study the feasibility and profitability
of putting up a plant in the country which produces citric
acid from pineapple waste. 3. The Process
Pharmac Pineapple waste containing about 65 % moisture is first
uetical,, ground in a double runner mill at an optimum particle size of
etc
2mm. It is then mixed with 3% methanol and 5ppm ferrous
Deterge 10% sulfate heptahydrate crystals. This comprise the fermentation
nt
medium. Meanwhile, the microorganism, Aspergillus niger
20% Beverag ACM 4992, is cultured with potato dextrose agar in an
Other es
50%
inoculation tank, R-101, an anaerobic bioreactor. The
food germination of the microorganism increase with increasing
(preserv
atives,
temperature at a range of 23-30oC and the optimum pH for
sour the process is at 4.5.
flavor)
20% The A.niger is allowed to react with the fermentation medium
in a reactor for four days through solid-state fermentation at a
temperature controlled within the range of 28-300C. Inside R-
Figure 1. Applications of Citric Acid 102, the following reactions occur:
2
Breakdown of sucrose to fructose and glucose: The proposed plant has a total capital investment (TCI) of US
C12H22O11+ H2O-->2C6H12O6 [1] $ 17.4 M. It can be broken down into a working capital of US
Citric Acid Production: $ 2.6 M and fixed capital of US $ 14.8 M. The method given
C6H12O6 + 1.5 O2 --> C6H8O7 + 2H2O [2] by Peters, et al (2nd edition) was used in estimating the
Metabolic Respiration: capital investments. The breakdown is given in Table 1.
C6H12O6 + 6 O2 --> 6CO2 + 6H2O [3]
Weight Cost, USD
The biomass is separated from the solution containing citric Purchased equipment 25.8% 3818825.191
acid, unreacted sugar and other impurities in a rotary drum
Purchased equipment installation 11.6% 1718471.336
vacuum filter. The fermentation broth from the filter is stored
in a buffer tank to make sure that the following downstream Instrumentation and controls 2.3% 343694.2672
processes may be operated continuously. From the buffer Piping 4.1% 611012.0306
tank, the fermentation broth loses much of its water when it Electrical 2.6% 381882.5191
undergoes evaporation in a triple-effect evaporator. After this, Buildings 6.5% 954706.2978
it goes through an SMB unit where it is stripped of sugar and Yard improvements 3.4% 496447.2749
other impurities.
Service facilities 10.3% 1527530.077

Deionized water supplied using four columns packed with Land 1.6% 229129.5115
different kinds of resins and heated by a shell-and-tube-heat
exchanger is used as adsorbent in the SMB. The packing Tot al di rec t pl an t c os t 10081698.5
material used is a tertiary poly(4-vinylpyridine, PVP) resin. It is
a uniform, water-insoluble, reticular with weakly acid and Engineering and supervision 8.5% 1260212.313
basic functional groups, amphoteric ion-exchange resin
Construction expenses 10.1% 1489341.825
(Peng, 2005). The resin was prepared by the conventional
suspension polymerization technique (Li & K, 1994). The
copolymer structure was modified to obtain the desired Tot al di rec t an d i n di rec t pl an t c os t s 12831252.64
functionality, so that it has a high selectivity to citric acid,
while weakly retaining the impurities (Peng, He, Liu, Yang, & Contractor's fee 4.4% 649200.2825
Zhang, 1998). In order to minimize the pressure drop in the
Contingency 8.8% 1298400.565
SMB unit, the resin with particle size of 300±50μm is used as
packing material in the SMB columns.
Fi xed Capi t al In ves t m en t 14778853.49
The clarified fermentation broth is then cooled and allowed to Worki n g c api t al 2596801.13
crystallize in a forced circulation crystallizer. The temperature
is maintained at 550C to induce the formation of anhydrous Tot al c api t al i n ves t m en t 17375654.62
crystals. The crystallized mixture is separated into its
Table 1. Breakdown of Total Capital Investment
components, crystals and mother liquor in a peeler
centrifuge. The crystals are dried in a rotary drier using
The purchased equipment cost accounts for about 40% of the
heated air as drying medium, previously heated using steam
direct plant cost. It was estimated using approximations given
in a shell-and-tube-heat exchanger. From here, the dry citric
by Towler, et al. and Peters, et al. The breakdown of the
acid crystals are transported to packaging. purchased equipment cost may be seen in Table 2.

4. Optimization Studies Equipment Cost (US $)

Innoculation Tank 16,960.10
The fungal strain used, the additives tot he substrate and the
operating conditions used were based on a study by Tran, et Heat Exchanger DI 8,652.36
al which aimed to check for the operating conditions which Blower 13,902.99
produced the highest yield from pineapple waste. To optimize
the production of citric acid from pineapple waste, several Heat Exchanger Air 5,865.17
strains of A. niger were tested. The strains were narrowed
Deionizer 60,664.50
down to three candidates, ACM 4992), ACM 4993 , and ACM
4994. Knowing the strain with the highest yield, the Crusher 169,767.50
experiment continued with the optimization of the
fermentation condition and medium composition. The effects Pre-mixer 416,452.34
of methanol, pH, culture method, particle size, metal ions, Fermentor 1,108,440.00
and time, were considered. Methanol addition contributed to
the increase of citric acid yield with A. niger strains. Methanol Filter 360,744.92
is not used up by the microorganism but it helps with cell
permeability and citric acid excretion. It also suppresses the Evaporator 142,510.01
production of oxalic acid, a by-product of Krebb’s cycle. Iron SMB 270,675.49
(II) ions help reduce trace metals and this in turn stimulates
the production of citric acid. For A. niger ACM 4992 only Fe2+ Crystallizer 832.89
gave significant increase to the citric acid production, Mn2+ Centrifuge 109,457.65
and Mg2+ had no effect, Zn2+ and Cu2+ slightly decreased the
production. (Tran, L.I., & D.A., 1998) Dryer 1,053.35
Compressor 158,920.58
5. Economic Analysis and Profitability Study Raw Materials Storage 158,920.58

3
 Cake storage 392,035.86
15.00

Cash Flow, USMillions

Product storage 71,514.26
10.00
Buffer Tank 204,806.25

$
5.00
Pumps 146,648.38 -
Total cost 3,818,825.19 (5.00)
Table 2. Purhased Equipment Breakdown (10.00)

The citric acid will be sold at a price of US $ 1500 per ton, as (15.00)
dictated by the current citric acid market, while the by-
(20.00)
product, pineapple waste biomass will be sold at a price of US
$ 50 per ton. The price of the biomass was based on the - 1 2 3 4 5 6 7 8 9 10
biomass market with almost the same property as that of the Operating Year
produced in the plant. This will amount to an annual sales
value of approximately US $ 7.8M. Operating costs include
labor, electricity, raw materials and utilities. The breakdown Figure 3. Cumulative Cash Flow for Discounted Payback
of the operating costs is shown in the table below.

Cost (US $)
The plant has a 10 year IRR of 20.74%, greater than the
Raw Material minimum acceptable rate of return (MARR) which is 8%, and
a NPV of US $ 12.6 M.
Pineapple Waste 154,043.83
Methanol 387.82
6. Conclusions and Recommendations
FeSO4 7H2O 32.39
Utilities It has been determined that the best location for the plant is
in Misamis Oriental, Mindanao. The chosen location is near
Cooling Water 11,322.32 the source of raw material and a power plant from where
Steam (MP) 854,781.36 electricity and steam will be outsourced. The temperature in
Misamis Oriental ranges from 22oC – 31oC, which is
Electricity convenient as the temperature requirements of the reactor is
Equipment 417,677.87 within 28-30oC. The plant is also to be built within an
economic zone, PHIVIDEC Industrial Authority.
Site 664.39
Based on the market study, the plant will have an annual
Miscellaneous target production capacity of 4,400 tons. The beverage and
SMB resin 750,905.19 food industries in the Philippines are the target consumers of
the product.
Labor
The process for the plant may be divided into three parts: the
211,855.16
raw material preparation, fermentation, and purification.
TOTAL 2,401,670.31 Solid-state fermentation has been selected because it has
low sensitivity to trace elements eliminating the need for
Table 3. Operating Costs Breakdown
rigorous pre-treatment. It also has the shortest fermentation
period among other methods. Downstream processes include
It is assumed that 70% of the capital will come from bank
filtration, evaporation, simulated moving bed (SMB)
loans with an annual interest rate of 8% compounded
purification, crystallization, centrifugation, and drying. The
annually. The rest is equity. The breakdown of the loan and
use of SMB technology has been selected because of its
equity is based on the usual bank agreements. The bank loan
reduced waste and water requirement and higher productivity
is to be paid over a period of four years.
per mass and feed and per unit time.
The internal rate of return and net present value were
The proposed plant has an internal rate of return of 20.74%,
computed on a basis of a lifetime of 10 years. The figure
2.5 times higher than that of the MARR, and a net present
below shows the payback period of the citric acid plant. It has
value of $15.6 million or 244 million Php. It has a simple
a simple payback period of 4.3 years and a discounted
payback period of 3.7 years and a discounted payback period
payback period of 5.3 years after the start of operations.
of 4.1 years.

7. Main References
7.1. Books and Articles
Euromonitor International. (2012). FRUIT/VEGETABLE
JUICE IN THE PHILIPPINES. Passport , 4-9.

Euromonitor International. (2011). Pineapple Market

Holds Steady in Face of Recession. Euromonitor , 2-

4
Heuzé, V., Tran, G., & Giger-Reverdin, S. (2013). Soccol, C. R., Vandenberghe, L. P., Pandey, A., &
Pineapple by-products. A programme by INRA, CIRAD, Rodrigues, C. (2006). New Perspectives for Citric Acid
AFZ and FAO. Production and Application. Food Technol. Biotechnol. ,
141-149.
International Society for Horticultural Sciences. (2010).
Pineapple News. Johor Baru, Malaysia. Verhoff, F. H. (2005). Citric Acid. In F. Ullmann, Ullmann's
Encyclopedia of Industrial Chemistry. Weinheim: Wiley-
IPCS. (2001). Citric Acid. Orlando, Florida: International VC.
Programme on Chemical Safety. Wu, J., Peng, Q., Arlt, W., & Minceva, M. (2009). Recovery
Kumar, A., & Jain, V. K. (2008). Solid state fermentation of Citric Acid from Fermentation Broth Using Simulated
studies of citric acid production. African Journal of Moving Bed Technology. Separation Science and
Biotechnology , 644-650. Technology .

Li, N., & K, L. (1994). Patent No. US5288763;. Porous

polymer beads and their preparation by template 7.2. Internet Sources
polymerization. Food and Agriculture Organization of the United Nations.
(1977). Lectures Presented at the Fifth FAO/SIDA
Majumder, L., Khalil, I., Munshi, M. K., Alam, K., Rashid, Workshop on Aquatic Pollution in relation to Protection
H.-O., Begum, R., et al. (2010). Citric Acid Production by of Living Resources. Manila,Philippines.
Aspergillus niger Using Molasses and Pumpkin as
Substrates. European Journal of Biological Sciences , 1- United Nations Commodity Trade Statistics Database.
8. (2012). Philippines Yearly Imports in US Dollars - Citric
Peng, Q. (2005). Patent No. CN1733680. Method for acid. Retrieved June 17, 2013, from Index Mundi:
purifying organic acid by separating residual sugars from http://www.indexmundi.com/trade/imports/?country=p
organic acid fermentation broth and corresponding h&commodity=291814
mother liquor of organic acid products.
Peng, Q., He, R., Liu, X., Yang, L., & Zhang, J. (1998).
Function and modification of poly(vinylpyridine) resins.
Jingxi Huagong , 5-9.

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