Matrikulasi

Azas Teknologi Proses

(Principles Process Technology)

Suprihastuti Sri Rahayu

Aswati Mindaryani
Typical Industrial Process

Raw materials Processes Products

(phase change,
composition change,
energy content change)
examples :

Fresh milk Milk powder

(90% water (3% water
content) content)
cane Sugar cane

limestone,
clay, sand cement
gypsum
 fine chemicals

Essential oil
(purified / absolute)

Essential oil/ethereal oil

(crude)

Agro products
(flower, nut, leaf, wood, root)
 Comparation of the Essential oil price (2005)

Name Plant used Specification price ($/kg)

Crude 35
patchouli oil Pogostemon cablin
Absolute patchouli 1275
(nilam)
alcohol ($255/240mL)
clove oil Eugenia caryophyllata Crude 18
Purified 40
Absolute eugenol 190
Minyak pala Biji pala Crude 35
(nutmeg oil)
Absolute trimyristin 600
Minyak kenanga Bunga kenanga Crude 29
(cananga oil, ylang-ylang oil) (Cananga odorata)
Purified 3563
($28.5/10mL)
Minyak jahe Rimpang jahe Crude 95
(ginger oil)
Purified 1938
($15.5/10mL)
Minyak sereh Daun sereh Crude 5
(citronella oil)
Purified 725
($5.8/10mL)
 Products
Raw Preparation Chemical Finishing/purifying
material Process process Process By products
 Products
Raw Preparation Chemical Finishing/purifying
material Process process Process By products
Phisical steps Chemical Phisical steps
seps

recycle
• Physical treatments steps
– For preparation of raw material
– For finishing/purifying of the products
• Chemical treatment step(s) for processing
the prepared material chemically → the
heart of almost every chemical industrial
operation
• A formula for succesful chemical industries
production can be expressed as the equation :
commercial production = f(chemical changes +
physical changes)
• For solving this equation we need to apply the
fundamental knowledge of unit processes and
unit operations in a coordinated pattern for
succesful commercialization of chemical
processes and products
• The unit operations ; for handling
problems of physical changes  will be
given Bu Aswati

• The unit processes : chemical processes

 How to get the process efficiently  will
be given now (bu Tuti)
 Important Chemical Processes
• Oxidation
• Hydrogenation/dehydrogenation
• Polymerization
• Hydrolysis (water is added to compounds). Hydrolysis
often leads to breakdown of larger molecul to smaller
(exp hydrolysis starch to produce sugars)
• dehydrolysis (water is removed to compounds)
• Halogenation and other substitution reaction
• Nitration
• Sulfonation
• Amination
• Esterification /transesterification, etc

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 Raw material
• Air (oxygen and nitrogen resource): plentiful, readily available dan
murah
*Oxygen - oxidation reaction (mis untuk membakar fuel  pembangkit
panas dan electricity)
* Nitrogen – ammonia production (fertilizer industry)
• Water as
– reactant
– solvent (industri biotek : beer making, antibiotik, insulin, dsb)
– Hydrogen resource( clean fuel too expensive with current technology)
• Mineral (solid inorganic elements or compound) bahan baku
inorganic chemical industries, misal salt  chlor alkali industry
• Fossil Fuel (natural gas, crude oil, coal)
– Heat, light, electricity
– Raw material for the synthesis of carbon base products (plastik, botol,
serat pakaian, obat2an, pestisida, dsb)
• Agricultural and forest products
• Since costs are most strongly affected by
material use and distribution, a material
balance, a study showing the origin and
ultimate disposion of all materials used, is
an essential first step in any processing
study
• Much effort is currently being spent on
reducing energy use  energy/heat
balance
 Reactor System Material
Balance

In p u t O u tp u t
flo w S y s te m flo w
s tre a m s s tr e a m s

S y s te m
b o u n d a ry
Material balance:

 Accumulati on   Input   Output   Generation   Consumptio n 

         
 within 
  to 
  from 
  within 
  within 
 System   System   Sytem   System   System 
         

11/02/2021 suprihastuti sr 14
Material balance on a system can be for :

 Total mass
 Total moles
 Mass of a chemical compound
 Moles of a chemical compound
 Mass of an atomic species
 Moles of an atomic species
 Heat balance

In p u t O u tp u t
flo w S y s te m flo w
s tre a m s s tr e a m s

S y s te m
b o u n d a ry
Heat balance:

 Accumulation  Input   Output  Generation  Consumption 

         
 within    to    from    within    within 
 System   System  Sytem   System   System 
         

11/02/2021 suprihastuti sr 16
 Mode of operation
• Two ways : How streams enter and leave a process unit
and their time dependence
• Batch process: input streams enter the process unit all at
once, and at some later time output streams are
removed from the process unit all at once. Input and
output streams are quantified in dimensions of mass or
moles
• Continuous process :input and output streams each
enter and leave the process unit continuously. Input and
output streams are quantified in dimensions of mass or
mole flowrates
• Semibatch process : combination of batch and
continuous
 Batch or Continuous
• Early, chemical processing was usually done in
batches, and much continues to be done in that
way
• Batch
• small scale
• production of expensive products (e.g.
pharmacy)
• high labor costs per batch
• Continuous
• for large-scale production
System Performance Specification
• Reactor
– Fractional conversion

– Selectivity
– Yield
 Fractional Conversion
• Conversion is defined to answer the
questions:
– How can we quantify how far a reaction has
progressed?
– How many moles of product C are formed for every
mole reactant A consumed?
• The conversion XA is the number of moles of
A that have reacted per mole of A fed to the
system: molesof A reacted
XA 
molesof A fed
 for series or paralel reaction

fractional selectivit y of A
moles of reactant A converted to desired product P
S AP 
moles of reactant A consumed

fractional yield of A
moles of reactant A converted to desired product P
YAP 
moles of reactant A fed
 Contoh (batch process)
Jus segar yang kadar airnya 80% sebanyak 300 L
akan dibuat concentrated juice dengan kadar air
67%. Berapa kg air harus diuapkan dan berapa
kg steam diperlukan?
Diketahui :
Panas penguapan air 80 kcal/kg
Densitas jus segar dianggap sama dengan
densitas air = 1 kg/L
 Continuous process
• A gas mixture of H2 and N2 is fed to a
reactor, where they react to form NH3. The
N2 flow rate is 150 gmol/h and the H2 is fed
at a ratio of 4 gmol H2 per gmol N2. Of the
N2 fed to the reactor, 30 % is consumed by
reaction. Reactor operate at steady state.
What is the flow rate (gmol/h) of N2, H2
and NH3 in the reactor outlet ?
 Contoh lain
• We want to make 1000 kgmol NH3/h, from
N2 dan H2. The feed to steady state
continuous flow process at stoichimetric
ratio. To save money, we purchase N2
with 2 % (mole) Argon. Fractional
conversion of H2 within the reactor 0,2
• How much the feed rate ?
 Batch reactor
• It has neither inflow nor outflow of
reactants or products which the reaction is
being carried out.
Typical Commercial Batch Reactor
 Selection of Reactors
• Batch
• small scale
• production of expensive products (e.g. pharmacy)
• high labor costs per batch
• difficult for large-scale production
• CSTR : most homogeneous liquid-phase flow reactors
• when intense agitation is required
• relatively easy to maintain good temperature control
• the conversion of reactant per volume of reactor is the smallest of
the flow reactors - very large reactors are necessary to obtain high
conversions
• etc
 Material Balance - Batch Reactor
• No material enters or leaves the reactor.
• No flow in or out of reactor.
• Terms (2) and (3) = 0.

Rate of accumulation of Rate of reactant A loss

reactant A in reactor = - by reaction in reactor
(1) (4)
Types and the rate of Reactions
Homogeneous –single phase

 rA 
mol. disapperance of A 
 time   volume 
Heterogeneous –multi-phase

 rA 
mol. disapperance of A 
 time  interface area
Irreversible –reaction in one direction

AB

Reversible –reaction in either direction until equilibrium reached

CB
A  B at equilibrium K eq 
CA
Rate constant

Rate depends on rate constant (k) and species concentrations

-rA = k f(CA, CB, …) (rate law)

Rate constant or
specific reaction rate

k can depend on:

temperature (T)
catalyst concentration (homogeneous)
total pressure
k solvent type
pH
ionic strength
type of catalyst

but temperature most important…

Arrhenius equation relates T to k

 E 
k  A exp   A 
 RT 
A - preexponential factor
EA - activation energy
R - gas constant
T - absolute temperature

True over a limited temperature range

 T0 , k0
T~, k  A
A≈ 1013

E = activation energy (cal/mol)

R = gas constant (cal/mol*K)
T = temperature (K)
A = frequency factor (units of A,
and k, depend on overall
    reaction order)
• Reaction : a A + b B  cC + d D
 How to maximize the reaction product

• Temperature
• Pressure
• Total moles
• Reactant ratio
 Reaction rate eqn :
r= k1[A]a[B]b – k2[C]c[D]d
Keadaan seimbang : r = 0
k1[A]a[B]b = k2[C]c[D]d
KC = k1/k2= [C]c[D]d/[A]a[B]b
Fase gas :
Kp =pCcpDd/pAapBb ; pi : tekanan parsial i
Kp = (ycP)c (yDP)d/ (yAP)a (yBP)b
Kp = (ncc nDd/ nAa nBb)(nt/P)a+b-c-d
Hasil C : nCc = Kp(nAa nBb/nDd)(P/nt)a+b-c-d

• Supaya hasil C lebih banyak :

1. Kp diperbesar.
• Kp = exp (- ΔH/RT)
• Reaksi eksotermis ΔH bernilai negatif  suhu yang lebih rendah
akan memperbesar Kp.
• Bila reaksi endotermis, suhu yang lebih tinggi akan memperbesar Kp
2. Bila Δ (= a+b-c-d)>0, P yang diperbesar akan menggeser reaksi
ke kanan.
Azas Le Chatelier : P yang lebih tinggi menggeser keseimbangan
ke arah jumlah mole yang lebih kecil.
3. Perbandingan pereaksi yang diperbesar akan menggeser reaksi
ke kanan.
4. Nt <, bila Δ (= a+b-c-d)>0
Nt diperkecil dengan cara meminimalkan inert
 Usaha untuk mempercepat reaksi :
• Ditinjau reaksi ke kanan : r = k1[A]a[B]b
atau (-rA)= k CAa CBb
Menurut Arrhenius : k = ko exp(-E/RT) Supaya (-rA) menjadi lebih
cepat :
1. Koefisien reaksi k >
2. Konsentrasi pereaksi CA atau CB > , dengan cara penggunaan
bahan yang murni
Agar tetapan reaksi k bernilai >, diperlukan :
a. Suhu tinggi, tetapi bila reaksi eksotermis harus kompromi dengan
usaha menggeser reaksi ke kanan
b. Tenaga pengaktif E < (pereaksi sdh aktif, memakai katalisator)
c. Faktor frekuensi ko yang > (turbulensi, pengadukan >)

Katalisator memegang peran penting dalam mempercepat reaksi.

Katalisator umumnya berujud cair maupun padat. Ada saatnya
katalisator mengalami deaktivasi (keaktifan katalisator menurun).
 Asam dan Alhokol

RCOOH + HOR’ RCOOR’ + H2O

• Reaksi lambat digunakan katalisator yang

berupa asam atau senyawa yang bersifat asam
mampu memberi ion H+
• Katalisator asam mineral H2SO4 dapat bereaksi
dgn alkohol
Contoh : isobutil alkohol dengan asam sulfat pada
esterifikasi isobutil palmitat
ROH + H2SO4  mono iso butil sulfat
• Dg adanya katalisator suhu tdk perlu tinggi
Jika suhu tinggi :
– zat pereaksi rusak,
– energi,
– pengendalian dan keselamatan
 Usaha untuk memperbanyak hasil
r = k1[RCOOH][R’OH] – k2 [RCOOR’][H2O]

Pd keadaan simbang r = 0
k1[RCOOH][R’OH] = k2 [RCOOR’][H2O]
k1  RCOOR' H 2O
 K
k2  RCOOH  R' OH 
Dilihat dari keseimbangan, supaya reaksi bergeser ke kanan
-asam dan alkohol semurni mungkin
-k = A exp(-E/RT)
-alkohol/asam >1
Alkohol lbh murah
Alkohol tdk korosif

Alkohol >> , sisa yang tdk bereaksi dipulihkan

r = k1[RCOOH][R’OH]  r = k[RCOOH]
• Penghilangan salah satu hasil
– Penyulingan biasa pada tekanan atmosferis bila titik
didih asam, alkohol dan ester >> td air
Mis. esterifikasi asam lemak dg gliserol T >100oC  zat
organik mudah rusak
– Penyulingan hampa  air mendidih pada suhu <100
– Penyulingan dan pengaliran gas inert
– Penyulingan azeotrop
• Air dpt membentuk campuran azeotrop dg zat hasil atau
pereaksi
• Dilakukan bila td asam dan alkohol< td air
• CH3COOH + C2H5OH  CH3COOC2H5 + H2O
• Camp azeotrop : air + ester + alkohol  td <
• Keluar dari reaktor satu fase  Didinginkan membentuk 2
lapisan, ester dan alkohol
• Pembentukan campuran azeotrop dpt dilakukan dg
penambahan zat lain, misal benzen jarang dilakukan
(kemungkinan trjadi reaksi samping)
• Suhu  tdk banyak berpengaruh
• P > 1 atm tdk untuk menggeser reaksi
Tapi untuk menjaga zat pereaksi tetap dlm keadan cair
• E tenaga aktivasi
– Rantai
– Cabang
– Ikatan rangkap
– Unsur/gugus lain
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