Matrikulasi Rev

8/14/2019 Matrikulasi Rev

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Matrikulasi Azas Teknologi Proses

(Principles Process Technology)

Suprihastuti Sri Rahayu Aswati Mindaryani


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Processes

(phase change,

composition change,energy content change)

Raw materials Products

Typical Industrial Process


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examples :

F resh milk (90% water content)

Milk powder (3% water content)

cane Sugar cane

limestone,clay, sandgypsum

cement


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Agro products(flower, nut, leaf, wood, root)

Essential oil/ethereal oil( crude )

Essential oil( purified / absolute )

fine chemicals


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C omparation of the Essential oil price (2005)

Name Plant used Specification price ($/kg)

patchouli oil Pogostemon cablin(nilam)

Crude 35

Absolute patchoulialcohol

1275($255/240mL)

clove oil Eugenia caryophyllata Crude 18

Purified 40 Absolute eugenol 190

Minyak pala(nutmeg oil )

Biji pala Crude 35

Absolute trimyristin 600

Minyak kenanga(cananga oil, ylang-ylang oil)

Bunga kenanga(Cananga odorata )

Crude 29

Purified 3563($28.5/10mL)

Minyak jahe

(ginger oil )

Rimpang jahe Crude 95


Minyak sereh(citronella oil )

Daun sereh Crude 5



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Chemicalprocess

Rawmaterial

PreparationProcess

Finishing/purifyingProcess

Products

By products


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Chemicalprocess

Rawmaterial

PreparationProcess

Finishing/purifyingProcess

Products

By productsPhisical steps Chemical

sepsPhisical steps

recycle


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Physical treatments steps For preparation of raw material For finishing/purifying of the products

Chemical treatment step(s) for processingthe prepared material chemically theheart of almost every chemical industrial

operation


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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 thefundamental knowledge of unit processes andunit operations in a coordinated pattern for

succesful commercialization of chemicalprocesses and products


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The unit operations ; for handlingproblems of physical changes will begiven Bu Aswati

The unit processes : chemical processesHow to get the process efficiently will be

given now (bu Tuti)


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11/9/2009 suprihastuti sr 11

Important Chemical Processes Oxidation

Hydrogenation/dehydrogenation

PolymerizationHydrolysis (water is added to compounds). Hydrolysisoften 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

NitrationSulfonation

Amination Esterification / transesterification, etc


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Raw material Air (oxygen and nitrogen resource): plentiful, readily available danmurah

*Oxygen - oxidation reaction (mis untuk membakar fuel pembangkitpanas 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 bakuinorganic chemical industries, misal salt chlor alkali industryFossil 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


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Since costs are most strongly affected bymaterial use and distribution, a materialbalance , a study showing the origin andultimate disposion of all materials used , isan essential first step in any processingstudy

Much effort is currently being spent onreducing energy use energy/heatbalance


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st

stu ar

I putflstr a s

Outputflstr a s

Mat rial ala c :

!

stithi

Con su pti o

Sy stithin

Gene ration

Sy temfr omOutput

Sy stemtoInput

Sy stemwithin

on Accu mulati

Re act or Sy stem Mate rialBala nce


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Material balance on a system can be for : y otal mass

y otal molesy Mass of a c emical com o ny Moles of a c emical com o ny Mass of an atomic s eciesy Moles of an atomic s ecies


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Sy st em

Sy st embo und ar y

In putflowstr e a m s

Outputflowstr e a m s

e at bala nce:

!

Systemwithin

nConsumptio

SystemwithinGeneration

SytemfromOutput

SystemtoInput

Systemwithin

on Accumulati

Heat balance


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Mode of operationTwo ways : How streams enter and leave a process unitand their time dependenceBatch process: input streams enter the process unit all atonce, and at some later time output streams areremoved from the process unit all at once. Input andoutput streams are quantified in dimensions of mass or

moles Continuous process :input and output streams eachenter and leave the process unit continuously. Input andoutput streams are quantified in dimensions of mass or mole flowratesSemibatch process : combination of batch andcontinuous


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Batch or Continuous Early, chemical processing was usually done in

batches, and much continues to be done in thatwayBatch

small scaleproduction of expensive products (e.g.pharmacy)high labor costs per batch

Continuousfor large-scale production


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System Performance SpecificationReactor

Fractional conversion

Selectivity

Yield


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for series or paralel reaction

consumedAreactantof molesP productdesiredtoconvertedAreactantof moles

!p P AS

Aof y selectivit fractional

fedAreactantof molesP productdesiredtoconvertedAreactantof moles

!p P AY

Aof yield fractional


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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 berapakg steam diperlukan?

Diketahui :Panas penguapan air 80 kcal/kgDensitas jus segar dianggap sama dengandensitas air = 1 kg/L


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Continuous process A gas mixture of H 2 and N2 is fed to areactor, where they react to form NH3. TheN2 flow rate is 150 gmol/h and the H 2 isfed at a ratio of 4 gmol H 2 per gmol N2. Of the N2 fed to the reactor, 30 % isconsumed by reaction. Reactor operate atsteady state. What is the flow rate (gmol/h)of N2, H2 and NH3 in the reactor outlet ?


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Contoh lain We want to make 1000 kgmol NH3/h, fromN2 dan H2. The feed to steady statecontinuous flow process at stoichimetricratio. To save money, we purchase N2with 2 % (mole) Argon. Fractionalconversion of H2 within the reactor 0,2

How much the feed rate ?


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Batch reactor It has neither inflow nor outflow of reactants or products which the reaction isbeing carried out.


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Typical Commercial Batch Reactor


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Selection of ReactorsBatch

small scale

production of expensive products (e.g. pharmacy)high labor costs per batchdifficult for large-scale production

CSTR : most homogeneous liquid-phase flow reactorswhen intense agitation is required

relatively easy to maintain good temperature controlthe conversion of reactant per volume of reactor is the smallest of the flow reactors - very large reactors are necessary to obtain highconversions

etc


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Rate of accumulation of reactant A in reactor

Rate of reactant A loss by reaction in reactor = -

(1) (4)

Material Balance - Batch Reactor No material enters or leaves the reactor.

No flow in or out of reactor.Terms (2) and (3) = 0.


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Types and the rate of Reactions Homogeneo us sin gle phase

? A

? A? Avo lumetime

Aof cedisapperanmo l.! Ar

Heterogeneous multi-phase

? A? A? Aa r e ainte rf a cetime

Aof ced isapp e r a nmo l.! Ar

Irreversible reaction in one direction

A p B

Reversible reaction in either direction until equilibrium reached

A m B at equilibrium A

Beq C

C K !


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Rate constant

Rate depen ds on rate constant ( k ) an d s pecies concentrations

-r A k f(C A , C B , ) (rate la w)

k can de pen d on:te mperat re ( T )catal yst concentration ( o mo eneo s)total press re

k sol vent t ype

pH ionic stren ttype of catal yst

bu t te mperat ure most i mportant

Rate constant or s pecific reaction rate


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Arr en ius equ a tion r e la te s T to k

!R T

E A k Aex p

A - p r eex ponen tia l f a ctor E

A - a ctiva tion ene r y R - a s c on sta n tT - a bso lu te tem pe r a tur e

Tr ue ove r a lim ited tem pe r a tur e r a nge


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T 0 , k 0

T ~, k AA 10 13

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)


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Reaction : a A + b B cC + d D


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How to maximize the reaction product

TemperaturePressureTotal molesReactant ratio


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Reaction rate eqn :r= k1[A]a[B]b k2[C]c[D]d

Keadaan seimbang : r = 0k1[A]a[B]b = k2[C]c[D]d

KC = k1/k2= [C]c

[D]d

/[A]a

[B]b

Fase gas :Kp=pCcpDd/p AapBb ; p i : tekanan parsial iKp = (ycP) c (yDP) d/ (y AP) a (yBP) b

Kp = (n cc nDd/ n Aa nBb)(n t/P) a+b-c-d


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Hasil C : nCc = Kp(n Aa nBb/nDd)(P/n t)a+b-c-d

Supaya hasil C lebih banyak :1. Kp diperbesar.

Kp = exp (- H/RT)Reaksi eksotermis H bernilai negatif suhu yang lebih rendahakan memperbesar Kp.Bila reaksi endotermis, suhu yang lebih tinggi akan memperbesar Kp

2. Bila (= a+b-c-d)>0, P yang diperbesar akan menggeser reaksike kanan.

Azas Le Chatelier : P yang lebih tinggi menggeser keseimbanganke arah jumlah mole yang lebih kecil.3. Perbandingan pereaksi yang diperbesar akan menggeser reaksi

ke kanan.4. Nt 0

Nt diperkecil dengan cara meminimalkan inert


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Usaha untuk mempercepat reaksi :

Ditinjau reaksi ke kanan : r = k 1[A]a[B]batau (-r A)= k C Aa CBb

Menurut Arrhenius : k = k o exp(- E /RT) Supaya (-r A) menjadi lebihcepat :

1. Koefisien reaksi k >2. Konsentrasi pereaksi C A 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 kananb. Tenaga pengaktif E < (pereaksi sdh aktif, memakai katalisator)c. Faktor frekuensi k o yang > (turbulensi, pengadukan >)

Katalisator memegang peran penting dalam mempercepat reaksi.Katalisator umumnya berujud cair maupun padat. Ada saatnyakatalisator mengalami deaktivasi (keaktifan katalisator menurun).

A d Al h k l


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Rea ksi l ambat digun a ka n k ata lis ator ya ngber up a a s am ata u s e ny awa ya ng ber sif at a s ammam pu member i i o n H +

Kata lis ator a s am m in era l H2SO4 d a p at berea ksidgn a lkoho l

Co

ntoh

: isob

util

alk

ohol d

eng

an

as

amsulf

at p a d a e s ter ifik a si is ob u t il p a lm itat

R OH + H2SO4 mo n o is o b u t il sulf at D g a d a ny a kata lis ator su h u t dk p er lu t inggi

Jik a su h u t inggi : z at p erea ksi r us a k, e n er gi, p e ng e nd a lia n d a n k e s e lamata n

As am d a n Al ho ko l

RCOOH + HOR RCOOR + H2O


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U saha untu k memperbanya k hasil

r = k1[ R COOH][ R OH] k2 [ R COO R ][H2O]

Pd k ea d aa n si mba ng r = 0k1[ R COOH][ R OH] = k2 [ R COO R ][H2O]

D ilihat d ar i k e s e imba ng a n, sup a ya rea ksi ber g e s er ke ka n a n- a s am d a n a lk oho l s em u r ni m ungkin-k = A ex p(-E/ R T)- a lk oho l/ a s am >1

Alkoho l lbh m u rahAlkoho l t dk k oro sif

Alkoho l >> , sis a ya ng t dk berea ksi dipuli h ka nr = k1[ R COOH][ R OH] r = k[ R COOH]

? A? A? A? A

K OH R RCOOH

O H RCOOR

k

k !!

'

2'

2

1


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Pe ng h ila ng a n s a lah s at u ha sil P e nyuling a n b ia s a p a d a te ka n a n atmo sf er is b ila t it ik

didi h a s am , a lk oho l d a n e s ter >> t d a ir M is. e s ter ifik a si a s am lema k dg glis ero l T >100 o C zat

or g a nik m ud ah r us a k P e nyuling a n ham p a a ir me ndidi h p a d a su h u


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Su h u t dk ba ny a k ber p e ng ar u h

P > 1 atm t dk un t uk me ngg e s er rea ksiTa pi un t uk me nj a g a zat p erea ksi teta p dl m kea d a n c a ir

E te n a g a a k t iva si Ra n ta i C aba ng Ik ata n ra ngk a p Unsu r /gugus l a in


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