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FACULTY OF ENGINEERING AND BUILT ENVIRONMENT
        DEPARTMENT OF CHEMICAL AND PROCESS ENGINEERING
              KKKB2424, KKKR2034, KKKR2324, KKKR2364

              BIOCHEMICAL ENGINEERING PROGRAM

                         REPORT TITLE:

                   PRODUCTION OF CITRIC ACID


KKKB2424 :        PROF DR JAMALIAH MD JAHIM
KKKR2034:         PROF DR MEOR ZAINAH & DR MASLI IRWAN ROSLI
KKKR2324:         PROF IR DR MASTURAH MARKOM & DR DARMAN NORDIN
KKKR2364:         DR MOHD SHAHBUDIN MASDAR

                           GROUP 3
                        GROUP MEMBERS

   NAME                                           MATRIC NO.
     MUHAMMAD KHAIRIL AZIM BIN ABDULLAH            A133275
     SONIA DILIP PATEL                             A133115
     WONG MEI FANG                                 A132213
     ZURAIFAH BINTI MINHAT                         A132221
INTRODUCTION
• Citric acid
   – Citric acid is a week organic acid found in citrus fruits
   – Molecular formula is C6H8O7 and belongs to the carboxylic acids
     groups
   – Stronger acid compared to other typical carboxylic acid.Produced by
     fermentation and suitable pH is around 3-6


• Application In Industry
   –   Beverages
   –   Food
   –   Pharmaceutical
   –   Agriculture
   –   Metal Industry                     Structural Formula of Citric Acid
SOURCE OF RAW MATERIALS
Beet Molasses                         Aspergillus Niger
• the source of sugar for microbial   • filamentous ascomycete fungus
  production of citric acid           • maintained at pH 4.5 and temperature
• low cost and high sugar content       at 5 °C
• low content of trace metals         • The best strain for citric acid
• acts as carbon source of the          production
  fermentation                        • Scientific classification of A.niger
                                              Domain          Eucaryotes
Microorganism                                Kingdom            Fungi
• mycomycetes of A.niger species              Phylum         Ascomycota
  can produce high yield                     Subphylum      Pezizomycotina
• consequence of incomplete                    Class        Eurotiomycetes
  respiration                                  Order          Eurotiales
                                              Family        Trichocomaceae
                                              Genus           Aspergillus
                                              Species          A.Niger
DEMAND AND SUPPLY
                                Global Citric Acid Demand and Supply
                                                 Graph
                                                                                               •   The high demand in citric acid is the
                                                                                                   wide usage as acidulent in food and
                          3.5                                                                      beverage industry.
                           3                                                                   •   In the 1980s, U.S.A has been the
                                                                                                   leading country in producing citric
                          2.5                                                                      acid. But, in the year of 1995, the
metric tonnes (million)




                                                                                  Demand           Chinese production volume of citric
                           2
                                                                                                   acid has surpasses that of United
                          1.5                                                     Production
                                                                                                   States (Connor 2008) due to the
                                                                                                   lower cost of raw materials and the
                           1                                                                       lower price of citric acid.
                                                                                               •   In the year of 2007, worldwide
                          0.5
                                                                                                   annual production was
                           0
                                                                                                   approximately 1.7 million metric
                                 2007   2008   2009          2010   2011   2012                    tons. According to Carlos (2006), the
                                                      Year
                                                                                                   production rate of citric acid has
                                                                                                   growth of 3.5 to 4.0% per year.
PROCESS DESCRIPTION

1.   Inoculation of Aspergillus Niger
2.   Fermentation of Citric Acid
3.   Biomass Removal
4.   Liquid-liquid extraction
5.   Crystallization
6.   Drying
STOICHIOMETRY EQUATIONS




• Given the yield of product with respect to substrate, YP/S =
  0.77, the stoichiometry coefficients is solved.
MATERIAL BALANCE
                  Ci         Co         Ni          No               Fi           Fo
                 (gL-1)    ( gL-1)   ( molh-1)   ( molh-1)     (kgh-1)       (kgh-1)
Sucrose          20.0      2.157      128.5       13.78         43.95         4.71
Ammonia           0.5     0.0745      64.31        9.58             1.23      0.16
Biomass            0       3.670        0        322.046             0        8.020
Product            0      13.740        0         156.36             0        30.02
Water              0       3.570        0         433.36             0        7.80
Oxygen                               3 281.25    2 947.44           105       94.32
Carbon dioxide                          0         108.09             0        4.76

Nitrogen                             12 343.75   12 343.75     345.63        345.63
                                                             Σ Fi          Σ Fo
                                                             = 501.45      = 501.422
ENERGY BALANCE
                            Hi ( Jmol-1)                       Ho( Jmol-1)
Sucrose                      1073.55                            1789.25
Ammonia                       240.27                            401.61
Biomass                          0                              63.4655
Product                          0                               1415
Water                            0                              304.82
Oxygen                        88.42                            197.3918
Carbon dioxide                   0                              764.36
                 Ei = Σ Nik∆Hik= 443,531.06 J/hr   Ei = Σ Nok∆Hok= 166,708.454 J/hr
Q = EOUT – EIN + rΔHbr = 166 708.454 - 443 531.06 + - 153 552.6(0.0015)= -277 052.934
Mass flow rate of cooling water :
Q = mCp (T2 – T1)
m = 13256kg/hr
BIOREACTOR

                                         • Catalyst
                                            – A small quantities of iron
                                              and limited amount of
H=10.06m
                                              zinc
                                            – Copper
                                         • By Product
                                            – Biomass
                   D = 5.03m
                                            – Gluconic acid
   Advantages
   1. Flexible and adaptable                – Oxalic acid
   2. Wide range of mixing intensity
   3. Ability to handle high viscosity
      media
• Typical Batch Growth Curve                       A Graph of Substrate, Biomass and
                                                       Product over Dilution Rate




                               Substrate, Biomass and Product
                                                   20




                                     concentration (g/l)
                                                   15

                                                                                       S(g/l)
                                                                                       X(g/l)
                                                   10
                                                                                       P (g/l)



                                                        5




                                                        0



                                                                Dilution Rate (h-1)
HEAT TRANSFER

• Heat can be transferred               • Glass wool which act as a
  through                                 cooling jacket of fermenter.
   – Convection

   – Conduction


   – Radiation
• Factors influencing Heat
  Transfer                              • q = 632.94 W
   –   Temperature diffence
   –   Fluid flow rate
   –   Nature of conducting materials
   –   Surface area and length
MASS TRANSFER

• Fick’s Law of diffusion:   • Factors influencing
                               mass transfer
                                –   Concentration gradient
                                –   Temperature
• Wilke-Chang correlation:
                                –   Phase
                                –   Molecular distance
                                –   Surface area
                                –   length
SEPARATION

• Rotary filter                  • Rotary filter
   – To filter off
     mycelium(biomass)
• Sieve tray column
   – Liquid-liquid extraction
                                 • Sieve Tray Column
   – Alkyl amide as extractant
   – Water as solvent in
     stripping
DESIGN OF SIEVE TRAY COLUMN
• Smin / F = (XA)F - (XA)M /(XA)M -
  (XA)S = (0.3 – 0.22)/(0.22 – 0) =
  0.36                                DT = (4 AC/ π)1/2=0.4869 ft
• (S / F) actual = 1.5 Smin / F =
                                       HETS =6.61 ft
  (1.5)(0.36) = 0.54
• F= 495.81 kg/h                      Total height = (HETS) (No. of Stages)
                                                  = 19.83 ft= 6.04418 m
• S= (0.54) (495.81 kg/h) = 267.737
  kg/h
• Use Material balance to solve R
  and E
• F+S=E+R
COMPUTER ENGINEERING

• An approach in generating material balance into
  computer codes.
• Simple algorithm performed to check the material
  balance at the stirred tank fermentor.
M-FILE
FLOWCHART

• To simplify the
  computer codes.
• As graphical
  representation of a
  series of sequential
  steps of algorithm.
ENVIRONMENTAL & SAFETY ISSUE


• Waste generation    • Safety Precautions
   – waste water         – Production plant safety
   – Waste gas           – Personal safety
   – Biomass             – General safety for plant
• Discharge Limit          process
   – Waste water         – General safety for
                           workers
   – Carbon dioxide
CONCLUSION

•   Citric acid – major production by Aspergillus niger
•   Demand in 2012 – 2.9 metric tonnes
•   Flow rate = 501.45 kg/hr , Q = -277 053 kJ/s
•   Separation by alkyl amide
•   Bioreactor of 5.03 m width & 10.06 m height
•   Heat transfer in fermenter , q = 632.94W
•   Flux = 1.286 x 10-10 kgmol/s.m2
•   Column height, H=6.04418m

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production of citric acid.

  • 1. FACULTY OF ENGINEERING AND BUILT ENVIRONMENT DEPARTMENT OF CHEMICAL AND PROCESS ENGINEERING KKKB2424, KKKR2034, KKKR2324, KKKR2364 BIOCHEMICAL ENGINEERING PROGRAM REPORT TITLE: PRODUCTION OF CITRIC ACID KKKB2424 : PROF DR JAMALIAH MD JAHIM KKKR2034: PROF DR MEOR ZAINAH & DR MASLI IRWAN ROSLI KKKR2324: PROF IR DR MASTURAH MARKOM & DR DARMAN NORDIN KKKR2364: DR MOHD SHAHBUDIN MASDAR GROUP 3 GROUP MEMBERS NAME MATRIC NO. MUHAMMAD KHAIRIL AZIM BIN ABDULLAH A133275 SONIA DILIP PATEL A133115 WONG MEI FANG A132213 ZURAIFAH BINTI MINHAT A132221
  • 2. INTRODUCTION • Citric acid – Citric acid is a week organic acid found in citrus fruits – Molecular formula is C6H8O7 and belongs to the carboxylic acids groups – Stronger acid compared to other typical carboxylic acid.Produced by fermentation and suitable pH is around 3-6 • Application In Industry – Beverages – Food – Pharmaceutical – Agriculture – Metal Industry Structural Formula of Citric Acid
  • 3. SOURCE OF RAW MATERIALS Beet Molasses Aspergillus Niger • the source of sugar for microbial • filamentous ascomycete fungus production of citric acid • maintained at pH 4.5 and temperature • low cost and high sugar content at 5 °C • low content of trace metals • The best strain for citric acid • acts as carbon source of the production fermentation • Scientific classification of A.niger Domain Eucaryotes Microorganism Kingdom Fungi • mycomycetes of A.niger species Phylum Ascomycota can produce high yield Subphylum Pezizomycotina • consequence of incomplete Class Eurotiomycetes respiration Order Eurotiales Family Trichocomaceae Genus Aspergillus Species A.Niger
  • 4. DEMAND AND SUPPLY Global Citric Acid Demand and Supply Graph • The high demand in citric acid is the wide usage as acidulent in food and 3.5 beverage industry. 3 • In the 1980s, U.S.A has been the leading country in producing citric 2.5 acid. But, in the year of 1995, the metric tonnes (million) Demand Chinese production volume of citric 2 acid has surpasses that of United 1.5 Production States (Connor 2008) due to the lower cost of raw materials and the 1 lower price of citric acid. • In the year of 2007, worldwide 0.5 annual production was 0 approximately 1.7 million metric 2007 2008 2009 2010 2011 2012 tons. According to Carlos (2006), the Year production rate of citric acid has growth of 3.5 to 4.0% per year.
  • 5. PROCESS DESCRIPTION 1. Inoculation of Aspergillus Niger 2. Fermentation of Citric Acid 3. Biomass Removal 4. Liquid-liquid extraction 5. Crystallization 6. Drying
  • 6.
  • 7. STOICHIOMETRY EQUATIONS • Given the yield of product with respect to substrate, YP/S = 0.77, the stoichiometry coefficients is solved.
  • 8. MATERIAL BALANCE Ci Co Ni No Fi Fo (gL-1) ( gL-1) ( molh-1) ( molh-1) (kgh-1) (kgh-1) Sucrose 20.0 2.157 128.5 13.78 43.95 4.71 Ammonia 0.5 0.0745 64.31 9.58 1.23 0.16 Biomass 0 3.670 0 322.046 0 8.020 Product 0 13.740 0 156.36 0 30.02 Water 0 3.570 0 433.36 0 7.80 Oxygen 3 281.25 2 947.44 105 94.32 Carbon dioxide 0 108.09 0 4.76 Nitrogen 12 343.75 12 343.75 345.63 345.63 Σ Fi Σ Fo = 501.45 = 501.422
  • 9.
  • 10.
  • 11.
  • 12. ENERGY BALANCE Hi ( Jmol-1) Ho( Jmol-1) Sucrose 1073.55 1789.25 Ammonia 240.27 401.61 Biomass 0 63.4655 Product 0 1415 Water 0 304.82 Oxygen 88.42 197.3918 Carbon dioxide 0 764.36 Ei = Σ Nik∆Hik= 443,531.06 J/hr Ei = Σ Nok∆Hok= 166,708.454 J/hr Q = EOUT – EIN + rΔHbr = 166 708.454 - 443 531.06 + - 153 552.6(0.0015)= -277 052.934 Mass flow rate of cooling water : Q = mCp (T2 – T1) m = 13256kg/hr
  • 13. BIOREACTOR • Catalyst – A small quantities of iron and limited amount of H=10.06m zinc – Copper • By Product – Biomass D = 5.03m – Gluconic acid Advantages 1. Flexible and adaptable – Oxalic acid 2. Wide range of mixing intensity 3. Ability to handle high viscosity media
  • 14. • Typical Batch Growth Curve A Graph of Substrate, Biomass and Product over Dilution Rate Substrate, Biomass and Product 20 concentration (g/l) 15 S(g/l) X(g/l) 10 P (g/l) 5 0 Dilution Rate (h-1)
  • 15. HEAT TRANSFER • Heat can be transferred • Glass wool which act as a through cooling jacket of fermenter. – Convection – Conduction – Radiation • Factors influencing Heat Transfer • q = 632.94 W – Temperature diffence – Fluid flow rate – Nature of conducting materials – Surface area and length
  • 16. MASS TRANSFER • Fick’s Law of diffusion: • Factors influencing mass transfer – Concentration gradient – Temperature • Wilke-Chang correlation: – Phase – Molecular distance – Surface area – length
  • 17. SEPARATION • Rotary filter • Rotary filter – To filter off mycelium(biomass) • Sieve tray column – Liquid-liquid extraction • Sieve Tray Column – Alkyl amide as extractant – Water as solvent in stripping
  • 18. DESIGN OF SIEVE TRAY COLUMN • Smin / F = (XA)F - (XA)M /(XA)M - (XA)S = (0.3 – 0.22)/(0.22 – 0) = 0.36 DT = (4 AC/ π)1/2=0.4869 ft • (S / F) actual = 1.5 Smin / F = HETS =6.61 ft (1.5)(0.36) = 0.54 • F= 495.81 kg/h Total height = (HETS) (No. of Stages) = 19.83 ft= 6.04418 m • S= (0.54) (495.81 kg/h) = 267.737 kg/h • Use Material balance to solve R and E • F+S=E+R
  • 19. COMPUTER ENGINEERING • An approach in generating material balance into computer codes. • Simple algorithm performed to check the material balance at the stirred tank fermentor.
  • 21. FLOWCHART • To simplify the computer codes. • As graphical representation of a series of sequential steps of algorithm.
  • 22. ENVIRONMENTAL & SAFETY ISSUE • Waste generation • Safety Precautions – waste water – Production plant safety – Waste gas – Personal safety – Biomass – General safety for plant • Discharge Limit process – Waste water – General safety for workers – Carbon dioxide
  • 23. CONCLUSION • Citric acid – major production by Aspergillus niger • Demand in 2012 – 2.9 metric tonnes • Flow rate = 501.45 kg/hr , Q = -277 053 kJ/s • Separation by alkyl amide • Bioreactor of 5.03 m width & 10.06 m height • Heat transfer in fermenter , q = 632.94W • Flux = 1.286 x 10-10 kgmol/s.m2 • Column height, H=6.04418m