INDUSTRI PUPUK
Pendahuluan
Pupuk:
Material alami ataupun sintetik yang ditambahkan dalam tanah sebagai
sumber satu atau lebih nutrisi tanaman.
Material yang minimal mengandung satu jenis nutrisi yang diperlukan
oleh tanaman dalam bentuk suatu senyawa kimia.
Jika diaplikasikan pada tanah bersifat larut dalam fasa larutan tanah
dan dapat digunakan oleh akar tanaman.
Jenis Pupuk Berdasarkan Jenis Nutrisi
1. Straight fertilizers
Hanya memberikan satu nutrisi tanaman primer, Nitrogen atau fosforus
atau potassium.
Misalnya: Urea, Ammonium sulphate, Potassium chloride, Potassium
sulphate.
2. Complex fertilizers
Menggabungkan2 atau 3 nutrisi. Dua nutrisi primer. Dua nutrisi primer
berbentuk kombinasi kimia. Umumnya berbentuk granular.
Misalnya : Diammonium phosphate, Nitrophosphates dan ammonium
phosphate.
3. Mixed fertilizers
Campuran fisik dari straight fertilizer. Mengandung 2 atau 3 nutrisi
tanaman primer.Dibuat dengan pencampuran merata secara mekanik
atau manual.
Jenis Pupuk Berdasarkan Bahan Baku
1. Nitrogenous Fertilizer
Berdasarkan bentuk nitrogen, dapat diklasifikasikan menjadi :
Ammoniacal, Nitrat, Ammoniacal dan Nitrat, Amida
a. Ammoniacal → mengandung nitrogen dalam bentuk ammonia.
Ammonium sulphate (NH4)2 S04
Garam berwarna putih, larut sempurna dalam air.
Mengandung 24% Nitrogen dan 24% Sulfur.
Umumnya digunakan untuk memupuk padi dan jute.
Ammonium chloride (NH4Cl)
Garam berwarna putih mengandung 26% Nitrogen.
Tidak direkomendasikan untuk tomat, tembakau karena
mengandung klorin.
b. Nitrate→ mengandung nitrogen dalam bentuk nitrat.
Potassium nitrate (KN03)
Mengandung 13.0 % nitrogen dan 36.4 % kalium.
Calcium nitrate [Ca (NO3)2]
Padatan kristal besifat higroskopis, larut dalam air, mengandung
15,5% Nitrogen dan 19,5% kalsium.
c. Ammoniacal Nitrate → mengandung nitrogen dalam bentuk
ammonia dan nitrat.
Calcium ammonium nitrate (CAN)
Mengandung 26 % nitrogen.
50% dari total nitrogen dalam bentuk ammoniacal dan 50% dalam
bentuk nitrat.
Ammonium nitrate (NH4N03)
INDUSTRI PUPUK

Mengandung 35 % Nitrogen, ½ dalam bentuk nitrat, ½ dalam 1. Ammonium Nitrat

bentuk ammonium. Kandungan nitrogen cukup tinggi, proses pembuatan sederhana dan
2. Phosphatic Fertilizer murah.
Pupuk berbahan fosfat yang banyak digunakan adalah Super Ammonium nitrat dibuat dengan mereaksikan Asam Nitrat (dengan
phosphate [Ca (H2PO4)2) yang mengandung 16% P2O5. mengoksidasi Ammonia) dan ammonia.
Superphosphate dengan konsentrasi yang lebih tinggi disebut Triple
super phosphate, mengandung 46% P2O5.
3. Potassic Fertilizer Reaksi dapat berjalan kontinu dan menghasilkan produk
ammonium nitrat molten dengan kadar air rendah (1-5%) dengan
adanya preheater. Pembentukan granular dapat dilakukan dengan
fluidized bed.
Flow Sheet Pembuatan Ammnium Nitrat dengan Proses
Stengel

4. Complex Fertilizer

Nitrogenous Fertilizer

2. Ammonium Sulfat
Ammonium sulfat dibuat dengan reaksi antara ammonia dan asam
sulfat.
INDUSTRI PUPUK

Jika asam sulfat mahal, dapat digunakan gypsum dan karbon
dioksida dari pembakaran.
Beberapa ammonium sulfat juga dapat diperoleh dari by product
caprolactam (nylon-6).
3. UREA
• Kadar Nitrogennya paling tinggi (45%).
• Diproduksi dalam bentuk prill atau granul, mudah larut dalam
air. Merupakan produk intermediate dalam pembuatan
ammonium sulfamate, asam sulfamat.
• Reaksi pembentukan urea :
a. Pembentukan ammonium carbamat
thermal decomposition of ammonium cyanate, which is
in chemical equilibrium with urea.
NH2CONH2 → NH4NCO → HNCO + NH3
• Dekomposisi karbamat → lambat dan endotermis.
• Kecepatan Dekomposisi Carbamat meningkat dgn kenaikan
temperatur. Kecepatan rendah pada T< 150 deg C (NH3:CO2
stoikiometri). Temperatur optimum 180-210 deg C.
• Tekanan 140-250 atm, NH3: CO2 = 3 : 1 (3.1-4.1)
• Pertimbangan desain bertujuan untuk :
- Memisahkan urea dari komponen lain
- Recovery ekses NH3
- Dekomposisi karbamat untuk recycle
• Blok diagram sintesis urea

b. Dekomposisi ammonium carbamat

• Undesirable Reaction in Urea Production

a. BIURET Formation
Two molecules of urea combine with the loss of a molecule of
ammonia.
2 NH2CONH2 → H2NCONHCONH2 + NH3
This reaction is suppressed in the synthesis reactor by
maintaining an excess of ammonia, but after the stripper, it
occurs until the temperature is reduced.

b. ISOCYANIC ACID Formation

INDUSTRI PUPUK

• Reaksi samping dalam pembentukan urea : - Total Recycle : Stamicarbon, Snamprogretti, Mitsui-
Toatsu, Advanced Cost and Energy Saving (ACES)
• Semua NH3 dan CO2 yang tidak terkonversi
direcycle ke reaktor (99% konversi)
• Proses produksi urea: • Proses ditentukan oleh suplai NH3dan CO2
- Once Through Process • Paling mahal dalam investasi dan biaya operasi

- Partial Recycle
• Sebagian off gas direcycle ke reaktor.
• Jumlah ammonia digunakan 15% lebih kecil
dibandingkan once-through process

Klasifikasi Proses Total Recycle

• Luaran reaktor terdiri dari Urea, NH3, CO2, H2O dan carbamat, yang
harus didekomposisi sebelum direcycle
INDUSTRI PUPUK

2. SNAM-Progretti → stripping agent : heat thermal/self stripping

Terdiri dari 6 bagian:

Plant Urea Berbasis Stripping

1. STAMICARBON → stripping agent : counter current CO2 dan larutan
urea.
INDUSTRI PUPUK

Pembuatan Urea dgn SNAM Progretti Thermal Stripping Flow Sheet Pembuatan Urea dgn Proses Mitsui Toatsu

3. Toyo Engineering Corpora (TEC) ACES → stripping agent CO2

Terdiri dari 5 bagian:

Pembuatan Urea dengan Proses ACES

INDUSTRI PUPUK

Phosphatic Fertilizer
1. Superphosphate Flowsheet Pembentukan Superfosfat
Pupuk superphosphate terdiri dari : normal superphosphate dan
triplesuperphosphate.
Pembentukan superphosphate terdiri dari :
a. Phosphate rock blending & grinding
b. Pembentukan superphosphate
c. Granulation

Reaksi Pembentukan Fosfat

Dasar reaksi adalah reaksi batuan fosfat yang insoluble dengan asam
sulfat untuk membentuk kalsium dihidrogen fosfat yang soluble,
Ca(H2PO4)2.

Reaksi pembentukan superfosfat :

Reaksi overall : 2. Triple SuperPhosphate

Triple superphosphat mengandung 45-46% P2O5.
Dibuat dari reaksi asamfosfat dan batuanfosfat.atau :
Skematik Diagram Pembentukan Superfosfat

Atau
INDUSTRI PUPUK

Flowsheet Pembentukan Triple Superfosfat 4. Phosphate Rock Blending & Grinding

• Batuan phosphat dari berbagai jenis dicampur dalam blending plant
sehingga menghasilkan produk dengan konsentrasi fosfat 15%.
• Campuran masuk ke hammer mill sehingga ukuran partikel keluar
dari mill : 0.5cm atau lebih kecil.
• Kemudian dimasukkan lagi ke dalam air swept roller mill (Bradley
Mill) sehingga menghasilkan ukuran powder kurang dari 75
microns.

3. Phosphate Rock
• Batuan phosphat mengandung fluoroapatite, calsium,
besi,aluminimum dan silika.
• Rumus kimia : CaF2.3 Ca3(PO4)2 atau Ca10F2(PO4)6, bersifat
insoluble in water atau Ca5(PO4)3F.
• Dalam pembentukan pupuk → soluble in water dalam bentuk P2O5.
Dilakukan dengan proses kalsinasi pada temperatur 1400-1500 deg
C dengan silika atau asam phosphat.
FAT AND OIL

Introduction
 Beda minyak dan lemak? 2. Tall Oil
 Komponen dalam minyak dan lemak : Campuran senyawa asam dari getah kayu pinus yang menjadi by
Komponen utama : Trigliserida produk dari industri pulp.
Komponen lain :
- Turunan trigliserida : glyserol, asam lemak, mono dan
digliserida
- Turunan non gliserida : fosfolipid, sterol, pigmen, vitamin, dll.

Kegunaan Minyak dan Lemak dalam Industri

Derivative Minyak dan Lemak

Jenis Minyak
1. Tung Oil
Berasal dari Pohon Tung (Aleurites Fordii)
FAT AND OIL

Produksi Edible Oil di Dunia Yield Vegetable Oil

Ekstraksi dan Pemurnian Minyak dan Lemak

Jenis Edible Oil Komponen utama minyak dan lemak : trigliserida, dengan minor komponen
1. Corn oil lipida yang lain.
2. Flaxseed/Linseed oil

3. Sesame seed oil

FAT AND OIL

Ekstraksi Edible Minyak dan Lemak

Tahapan Proses Ekstrasksi dan Pemurnian Minyak dari Biji-bijian

 Penyiapan biji
 Ekstraksi
 Refining → Degumming dan nutralization
 Bleaching
 Deodorization
 Winterization
1. Seed Preparation
Oil Refining Process  Proses ini meliputi pembersihan biji menggunakan magnet, screen
atau aspirator system.
 Pengupasan biji dari kulitnya dgn menggunakan corrugated roll mill
atau ball mill, kulit dipisahkan dari bagian biji dengan screening dan
klarifikasi udara.
2. Extraction
 Rendering → digunakan untuk ekstraksi lemak, tulang, minyak
ikan paus, minyak kelapa sawit dari buah sawit segar.
Jaringan lemak dipotong kecil2, dimasukkan dalam digester. Lemak
akan terapung di permukaan air, diambil dengan skimming.
FAT AND OIL

 Pressing dengan mechanical press  Degumming juga bisa dilakukan dengan enzim phospholipase
o Penyiapan biji dan penghilangan kulit dan impuritas A2 (menghilangkan asam lemak pada posisi C-2 gliserol).
o Size reduction dengan grinding
o Cooking dan pressing dengan hydraulic atau screw

 Ekstraksi dengan solvent

o Ekstraksi dilakukan pada cake (sisa pengepresan, mengandung
3-15% minyak) dengan menggunakan solvent.
o Jenis solvent utk edible oil : hexane atau heptane, (petroleum
ethers), TD 63.3 - 68.9°C).
3. Refining
a. Refining: Degumming
 Degumming bertujuan untuk mengurangi phospatida dan
kandungan logam dari crude edible oil dengan mencampur crude
oil dengan asam dan air.
 Phosphatides berbentuk hidrat bebas (HP) atau non hidrat bebas
(NHP) ,dengan kombinasi dengan Ca++, Mg++, or Fe++.
 Degumming dilakukan dengan menambahkan 0.05% asam fosfat
pekat dan air.
FAT AND OIL

b. Refining: Neutralization  Flow sheet of a double batch bleaching process with acid pretreatment
 Dalam proses degumming, NHP yang masih ada dan asam lemak
yang terbentuk pada proses hidrolisis HP (lipolisis) dihilangkan
dengan alkali refining.
 Minyak ditambah dengan larutan 0,1 % caustic soda ekses dan
dipanaskan dengan temperatur 75°C utk memecahkan emulsi
yang terbentuk.
 Emulsi dipisahkan dengan centrifuge atau settling tank.

4. Bleaching
 Refined oil berwarna gelap karena masih mengandung pigmen  Two-stage counter-current bleaching with prefiltration
(klorofil dan karotenoid), sisa fosfolipid, logam, dll.
 Bleaching bertujuan untuk menghilangkan warna dengan bleaching
earth (bentonite clay) (0,1-2%) atau arang aktif atau kombinasi
keduanya.
FAT AND OIL
5. Deodorization
 Minyak masih mengandung 0.2-0.5% senyawa yang menimbulkan
bau yang tidak diinginkan.
 Deodorization dilakukan pada temperatur antara 220-2600C, tekanan
2 dan 4 mbar, dan dengan injeksi 0.5-3 % steam dalam stainless steel
vessel.
 Flowsheet Batch Deodorization Process
 Flowsheet Continuous Deodorization Process
6. Winterization
 Proses untuk menghilangkan material yang akan menjadi padatan
pada temperatur refrigerasi.
 Dilakukan dengan mendinginkan minyak pada temperatur 5deg C
dan menyaring padatan yang terbentuk.
 Umumnya dilakukan untuk minyak bunga matahari, olive, dedak,
dan partially hydrogenated soybean oils.
 Flowsheet Cottonseed Oil
FAT AND OIL

 Flowsheet untuk Soya Oil

SODA INDUSTRY

SODA ASH (NA2CO3) a. Kalsinasi trona → impure soda ash → purification → pure soda
Bentuk hidrat : Sodium carbonat mohonidrat, sodium carbonat heptahidrat, ash (MONOHIDRATE PROCESS)
sodium carbonat decahidrat ➢ The trona ore is cursed and then calcined in a rotary kiln
 Monohidrat : Na2CO3.H2O → 85.48 % Na2CO3 +14,52 % air 150-300 deg C → sodium sesquicarbonat decomposition
 Heptahidrat : Na2CO3.7H2O → 45.7 Na2CO3 + 45.3% air (Na2CO3.NaHCO3.2H2O) → Na2CO3, H2O, CO2
 Decahidrat : Na2CO3.10H2O(‘sal soda’ atau ‘washing soda’) → 37,06
Na2CO3 + 62,94 % air
➢ The calcined material, which is impure soda ash, is agitated
Proses Pembuatan Soda Ash in tanks with water or weak soda ash liquors to dissolve the
1. Le Blanc Process soda ash and soluble impurities, such as sodium chloride
Le Blanc → roasting salt cake + carbon + limestone dalam rotary and sodium sulphate.
furnace, leaching the product with water → SODA ASH (Na2CO3) ➢ Insoluble material, consisting of shale, clay, and complex
salts containing calcium carbonate, is separated from the
hot, near-saturated soda ash solution.
➢ Crystallization is carried out in multiple effect evaporators
at a maximum temperature of about 100 deg C, which is
below the transition temperature of monohydrate to
anhydrous soda ash
b. Kalsinasi purified sesquicarbonat dari trona (SODIUM
Reaksi Pembentukan Soda Ash pd Le Blanc Process : SESQUICARBONATE PROCESS)
2NaCl+H2SO4 → Na2SO4+2HCL ➢ Crushed trona → dissolve → saturated mother liquor.
4C+Na2SO4 → Na2S+4CO ➢ Ssaturated mother liqour → evaporated in vaccum
Na2S+CaCO3 → Na2CO3+CaS crystrallizers, cooled to 40 deg C → kristal sodium
Treatment of CaS : sesquicarbonate → centrifuge → kristal sesquicarbonate
CaS + H2S → Ca(SH)2 ➢ Kristal sesquicarbonate → kalsiner 200 deg C → soda ash
Ca(SH)2 + CO2 + H2O → CaCO3 + 2 H2S 3. SOLVAY Process atau Ammonia-Soda Process
H2S + ½ O2 → H2O + S  Bahan Baku :
2. Trona Purification Process - Brine (NaCl), komposisi 28% w/w
 TRONA: Mineral karbonat dengan rumus kimia - Batu kapur (CaCO3)
Na3(CO3)(HCO3)•2H2O - Ammonia
 Ada 2 jenis proses :
SODA INDUSTRY

 Reaksi overall :

 Konsep proses :
Ammonia is dissolved in a salt solution and then ammoniate brine
solution is allowed to react with CO2 obtain by calcining lime
stone with coke. A precipitate of NaHCO3, thus obtain is then
calcined to produce high purity Na2CO3.

• Block diagram Solvay Process

4. Dual Process
Processing Stage:
1) Preparation and purification of brine
2) Ammoniation of Brine (AMMONIA TOWER)
3) Lime kiln
4) Carbonation of ammonium brine (CARBONATION TOWER or
SOLVAY TOWER)
5) Filtration
6) Calcination
7) Ammonia Recovery
SODA INDUSTRY
• Tahap proses (1)
a. Ammonia absorber
The purified brine is allowed to percolate down the strong
ammonia tower in which ammonia gas is passed through the
bottom. The brine and ammonia thus meet in a counter current
fashion. The brine solution thus takes up the necessary amount
of ammonia
Reaksi:
2NH3 + H2O + CO2 → (NH4)2 CO3
Adanya kandungan Ca dan Mg pada larutan brine :
CaCI2 + (NH4)2 CO3 → CaCO3 ↓ + 2NH4CI
MgCI2 + (NH4)2 CO3 → MgCO3 ↓ + 2NH4CI
Tambahan reaksi:
NaCl + H2O + NH3 → NaCl + NH4OH
NaCl + NH4OH + CO2 → NaCl + NH4HCO3
NH3 + H2O → NH4OH
b. Carbonation Tower (SOLVAY TOWER)
Carbon dioxide obtained from the lime kiln is first compressed
and then passed through the bottom of carbonating tower
down which ammoniated brine percolates.
The sodium bicarbonate with ammoniated brine formed a
solution of ammonium carbonate. This ammonium carbonate
solution with some unconverted NaHCO3 is allowed to fall
down a second tower, called making tower, along with
ammoniated brine (which was previously washed) and rich
carbon dioxide (90-95%) gas from the bicarbonate calciner is
recompressed and pumped to the bottom of the making tower.
The ammonium carbonate first reacts with CO2 to form
ammonium bicarbonate and the latter reacting with salt, forms
sodium bicarbonate.
Carbonating towers are about 22-25 m height, 1.6-2.5 m in
diameter and constructed of cast iron.
Reaksi:
(NH4)2CO3 + CO2 + H2O → 2 NH4HCO3
NH3 + H2O + CO2 → NH4HCO3
NaCI + NH4HCO3 → NaHCO3 ↓ + NH4CI
• Tahap Proses (2)
a. Filtration
The slurry from carbonation tower filtered on a rotary vacuum
filter. The filtrate containing NaCl, NH4Cl, and NH4HCO3 is
treated with lime obtained from lime kiln to recover NH3 and
CO2. The solution containing crystals of NaHCO3 is drawn off
from the base of the carbonation tower and filtered to get
NaHCO3.
b. The NaHCO3 obtained from the above step is heated strongly
in kiln to covert it into sodium carbonate (Na2CO3)
2NaHCO3 → Na2CO3 + CO2 + H2O
The carbon dioxide produced here is sent to carbonation tower.
• Tahap Proses (3)
a. Ammonia recovery tower
The ammonia is recovered in a distillation column. The filtrate
of rotary filter cocntaining NaCl, NH4Cl, and NH4HCO3 is fed
into tower where free ammonia and carbon dioxide are driven
off by distillation.
Dry lime or milk of lime (slaked lime) obtained from lime kiln
is fed through the lime inlet and mixed with the liquor from the
upper part or heater. As the liquor flows down the column,
calcium chloride and calcium sulfate are formed and NH3 gas
is released.
SODA INDUSTRY

Reaksi: - Sodium carbonate (can be manufactured by Solvay‘s process, dual

NH4HCO3 → NH3 + H2O + CO2 process or electrolytic process
2NH4CI + Ca (OH)2 → 2NH3 + 2H2O + CaCI2 - Lime stone is obtained from mineral calcite or aragonite, which
b. Lime kiln can be used after removal of clay, slit and sand (silica).
T 1300 K Reaction :
CaCO3 → CaO + CO2

SODA CAUSTIC (NaOH) Block diagram:

• Sodium hydroxide (NaOH), also known as lye and caustic soda is a
highly caustic metallic base which is a white solid available in pellets,
flakes, granules, and as 50% saturated solution.ses
• It is used in soap, rayon, dyes, paper, drugs, foods, rubber, textiles,
chemicals, bleaching, metallurgy and petroleum industries.
• Caustic soda and chlorine are produced as co-products by the electrolysis
of brine.

Manufacture of Caustic Soda (NaOH)

• Sodium Chloride solution (brine) is electrolytically decomposed to
elemental chlorine (in the anode compartment), and sodium hydroxide
solution and elemental hydrogen (in the cathode compartment) in all the
processes
• Overall reaction :

• Method of Manufacture:
1. Kimia : Lime-Soda Process
Sources of raw material:
SODA INDUSTRY
Process Description:
• Series of causticizer tank or agitator are added with 20% solution
of soda ash and milk of lime or slaked lime. The causticizer tanks
containing steam line to heat the mixture to 80–90 deg C are either
fitted with mechanical stirrer or compressed air as substitute of
agitator.
• After the equilibrium the liquid is allowed to settle for 2-3hour.
The clear liquid containing about 10% NaOH is drawn by a swing
pipe. The sludge is washed in counter current manner with the
washing of the previous operation. The causticising process is
completed in the series of three agitators.
• The mixture of NaOH and CaCO3 from the last agitator is charged
to the first Door thickener, which consist of a large shallow
cylindrical tank into which the slurry is fed at the center. The over
flow liquid from the first thickener is filtered and filtrate
containing 10-11% NaOH is evaporated to 50 % solution in a
triple effect vacuum evaporator
2. Elektrokimia : Chloro Alkali Process
a. Diaphragm Cell
Two types of diagprahm cell :
1) Submerged Cells
Cathodes remain submerged in this type of cell. Graphite is
universally used as anode. The liquid in the cathode
compartment is at low-level in order to prevent the back
flow of OH¯ ions by diffusion. E. g. Hooker and Townsend
cell
The cathode assembly has hydrogen and caustic off takes
and the cathode connection. The cathode is directly covered
with asbestos and forms the diaphragm, which is
completely submerged.
Diaphragm is applied by dipping the cathode into a bath of
asbestos slurry and the asbestos is drawn into the screen by
applying a vacuum to the hydrogen outlet.
SODA INDUSTRY
2) Dry/Porous Diaphragm Cells
The diaphragm cells contain a porous asbestos diaphragm
which permits a flow of brine from the anode to cathode and
prevents the mixing of anode product and cathode products.
Graphite is used as an anode. Electrolysis starts with dry or
empty cathode compartment. E. g. Nelson, Gibbs and Vorce
cells
Sources of raw material:
- Common salt can be obtained from sea water, saltlake
and sub –soil water
- Sodium carbonate
- Sulphuric Acid → for Chlorine Drying
Manufacture of Dry Diaphragm Cells:
1. Brine purification
2. Brine electrolysis:
10 to 15% caustic soda solution along with some
unconverted NaCl is obtained after electrolysis.
3. Evaporation and salt separation :
The liquid obtained from the salt separator is 50%
caustic soda solution containing 2% NaCl and 0.1 to
0.5% NaCl on a dry basis.
4. Final evaporation :
99% of water from caustic soda solution and molten
caustic soda is formed at 500 deg C to 600 deg C.
Another method of dehydrating 50% caustic soda is
the precipitation of NaOH.H2O by adding ammonia
which also succor to purify the caustic soda.
5. Purification of caustic soda
Impurities of 50% caustic soda solution : colloidal
iron, NaCl and NaClO. Iron is removed by treating
caustic with 1% by weight of 300mesh CaCO3 and
filtering the resulting mixture through a filter on
CaCO3 per coat. Sodium chloride and hypochlorite are
removed by dropping the 50% caustic solution through
a column of 50% NH4OH.
6. Chlorine Drying
SODA INDUSTRY

b. Mercury Cell Process 3. Caustic soda dengan Elecrolitic Process

c. Membrane Cell Process
SUGAR AND SWEETENER

Introduction
 Sugar → sugar cane sugar beet/ beet sugar (gula bit).
 Sugar → raw sugar and refined sugar

Block Diagram of Raw Sugar Production from Sugar cane

Refining Raw Sugar

 Raw sugar is light to dark brown in color, slightly sticky, and contains
about 1-2 % of ash, starch, and coloring matter.
 The purpose of refining raw sugar is to remove impurities and produce
refined sugar of nearly 100% purity.
SUGAR AND SWEETENER

Production of Sugar Beet

SUGAR AND SWEETENER
Different Types of Granulated Sugar and Their Special Characteristics
Other Sweetener
 High Fructose Syrup (prepared from starch), sugar alcohol (Sorbitol,
mannitol, xylitol) → prepared from fruits and manufactured by chemical
reduction of the parent sugars, fruktosa → hydrolysis of sucrose and
isomerization of glucose, sugar substitutes (artificial sweeteners)
Affination
 A process to remove the adhering film of molasses from the crystals of
raw sugar by a washing process
 By mixing the raw sugar with hot raw syrup. The raw syrup dissolving
some of the adherent molasses film from the crystal faces, then the
residual sugar is washed with a jet of hot water to remove residual syrup.
Melter
 The washed sugar is melted in hot water in the melter tank where it meets
a stream of hot sweet waters from the process.
 The melter is adjusted to a density of about 65 degrees Brix, then it is
strained through a plain screen to remove insoluble debris.
Clarification
 The raw washed sugar liquor from the melter contains particulate matter
such as, fiber, yeast, gums, colloids, etc. The object of clarification is the
complete removal of these contaminant. One of three processes is then
used: carbonation, phosphatation, or filtration.
 Carbonation → high density sugar liquor at 60-80oC and pH 10. The
carbon dioxide gas added until the pH drops to between 8,4-9
 Phosphatation → using phosphoric acid to bring the pH to 7,2 to 7,8
 Filtration → using plate and frame filter.
 Milling → preesing sugar cane between rollers.
Extraction of sucrose from sugarcane in juice form, and to make the final
bagasse (fibrous residue from the cane) as dry as possible.
SUGAR AND SWEETENER

 Diffuser → leaching by water to extract the sugar Kristalisasi

 Diffusion systems: diffusion of cane or diffusion of bagasse (30%  The clarified juice (syrup) is transferred to a vacuum pan (a vessel to boil
residual juice in the bagasse). Diffusion by immersion with of hot water the syrup under vacuum to form a heavy mixture of crystals and the
(65-75oC) mother liquor, called massecuite). The function of the vacuum pan is to
produce sugar crystals.
Clarifier/Purification
 The raw juice leaving the mill is slightly acidic (pH 5,5 to 6,5), turbid,
and colored. It carries in suspension of cane fiber, field soil, protein, fats,
waxes, gums, coloring matter, and soluble salts.
 Under slightly acidic conditions, the sucrose in the juice is gradually
hydrolyzing to glucose and fructose (under the influence of the native
inverter's enzyme).
 The process to stop inversion and remove impurities is called
clarification or defecation, by adding lime to the cold juice to raise the
pH to 7,5-8,5.
 Phosphoric acid is added to helps clarification
 The clarification process divides the whole juice into two portions: (1)
the clarified juice dan (2) the precipitated settlings (mud waters).

Evaporation
 Clarified juice contains about 85% water and requires evaporation to
yield a final crystalline product. The evaporation is carried on to a final
65-68% sugar concentrate (syrup), which very dark brown and turbid.
Evaporaton using multiple effect evaporator.
CEMENT INDUSTRY

Introduction 2. Type II : Moderate heat of hardening and sulfate resisting

 Cement is a material with adhesive and cohesive properties which make
it capable of bonding minerals fragments into a compact whole.
 Cement is a hydraulic mineral binding material. Blended with water, the
pulverous cement can generate the plastic paste which will turn into hard
cement block and bind granulated (or block) materials together after a
series of physical and chemical effects.
• For construction having high sulphate resistance (0,10%-0,20%) eq.
Swamp, sea side, structure of dam and bridges.
• Use where moderate heat of hydration is required, or for general
concrete construction exposed to moderate sulfate action. The heat
evolved from these cements should not exceed 70 and 80 cal. per
gm. after 7 and 28 days, respectively.

Portland Cement
 ‘Portland’ Cement → patented in1824. The name "Portland cement"
given originally due to the resemblance of the color and quality of the
hardened cement to Portland stone – Portland island in England.
 The first cement1871 di USA.
 Portland Cement → product from pulverizing clinker consisting of more
than one type of Calcium Silicate.
 Raw materials of Portland cement are Calcerous (Calcium containing
3. Type III : High Early strength (HES) Portland Cement
materials) and Argillaceous (silica cotaining materials)
• High-early-strength (H.E.S.) cements are made from a raw material
with a high lime-to-silica ratio, frequently burned twice and very
Types of Portland Cement
finely ground. They contain a higher proportion of tricalcium
1. Type 1 : Reguler Portland Cement
silicate, CaS, than regular portland cements and hence harden much
• Regular portland cements are the usual products for general
more quickly and with greater evolution of heat. Roads constructed
concrete construction does not require specific consideration on
from H.E.S. cement can be put into service more quickly than if
hydration heat, Sulphate content in water/land : 0,0% - 0,10%.
regular cement had been employed.
• There are other types of this cement such as white, which contains
less ferric oxide, oilwell cel,lent, quick-setting cement, and others
for special uses.
CEMENT INDUSTRY

4. Type IV : Low Heat Portland Cement Chemical Composition of Portland Cement

• Low-heat: portland cements contain a higher percentage of
tetracalcium aluminoferrate, C4F, and dicalcium silicate, C2S, and
hence set with the evolution of much less heat
• The tricalcium silicate, CaS, and the tricalcium aluminate, CaA, are
lower. Actually the heat evolved should not exceed 60 and 70 cal.
per gm. after 7 and 28 days, respectively, and is 15 to 35 per cent
less than the heat of hyd:o-ation of regular or H.E.S. cements.
5. Type V : Sulfate Resisting Portland Cement
• Sulfate-resisting portland cements are those which by their
composition or processing resist chemicals better than the other four
types.
• These cements are higher in tetracalcium aluminoferrite, C4AF, and
lower in tricalcium aluminate, CaA, than the regular cements.

Major Composition of Portland Cement

Raw Materials
• Calcareous material – such as limestone or chalk, as a source of lime
(CaO).
Where each oxide symbol with one letter:
• Clayey material – such as clay or shale (soft clayey stones), as a source
of silica and alumina.
• Iron Ore, Fly ash, gypsum, bauxite
CEMENT INDUSTRY

Block Diagram Of Cement Manufacture

Flowsheet of Portland Cement Manufacture

CEMENT INDUSTRY

Grinding and Blending

There 2 types of process in Grinding and Blending :
1. Wet Proses → grinding and mixing of the raw materials in the existence
of water.
 After crushing, powders are mixed with water (35-50% by mass)
 Wet process kilns can be up to 8m in diameter and as long as 230
m. Long kiln is required in order to evaporate water, Heat transfer
is not efficient.

# Principal of WET PROCESS-KILN

Example of Raw Material Composition
CEMENT INDUSTRY

2. Dry Proses → grinding and mixing of the raw materials in their dry
state.
 Blended raw material enter into kiln through a pre-heater tower.
Hot gas from kiln is used for heating kiln feed and hence the kiln
feed having high temperature before entering the kiln.
 The dry process comprise of kiln dan preheater.
 Length of kiln in dry proses is 70 m with diameter of 3-6 m.

KILN dan KLINKER

 In the kiln, there is a burning of raw material and produce clinker.
The clinker compositon :

CLINKERING : Dry vs Wet Process

 There is a water evaporation in the kiln depending on kiln zone

temperature
 Skema dari Kiln Temperature
CEMENT INDUSTRY

Reactions during Clinker Formation  Zone 4: 50-60 minutes, 1300-1000 oC

Cooling and crystalization.

Portland Cement Composition

C3S → early strength (7-8 hari)

C2S dan C3S → final strength (1tahun)
C3A → causes set but needs retardation by gypsum
Kiln Zoning Reaction
PORTLAND CEMENT : clinker + ~ 5% gypsum (CaSO4.2H2O) (prevent
 Zone 1: 0-35menit, 800-1100 oC
’flash set’ of cement → C3A.3CaSO4.31H2O (tricalcium aluminate
Decarbonation. Formation of 3 CaO.Al2O3 at temperature of > 900 oC.
tricalcium sulfate hydrate)
Component melting of Al2O3 and Fe2O3.

Portland Pozzolant Cement

 Zone 2: 35-40 menit, 1100-1300 oC
Exothermic reaction and secondary phase formation of silica :
 Portland Pozzolan Cement : clinker + gypsum + fly ash
 Portland Pozzolan Cement : made by grinding two to 4 parts of a
pozzolana with 1 part of hydrated lime.
 A "Pozzolana” is a material which is not cementitious in itself but which
becomes so upon admixture with lime. The natural pozzuolanas are
volcanic stuffs; the artificial ones are burnt clays and shales.

Zoning Reaksi Pembentukan Semen

 Zone 3: 40-50 minutes, 1300-1450-1300 oC
Sintering and melting reaction to form tertier silica and tetracalcium
aluminoferrates:
CHEMICAL INDUSTRY PROCESS INTODUCTION

Syllabus Classification of Chemical Industry

• Introduction to chemical industry North American Industry Classification System (NAICS).
• Reaction or process in Chemical industry: Alcoholysis, hydrolisis,
oxidation, polimerization, sulfonation, sulfatation, nitration,
halogenation, esterification, calcination, Fischer-Tropsch.
• Food industry (Edible Oil and Sugar)
• Pharmacy industry
• Basic Chemical Industry (cement, fertilizer, soda, sulfuric acids, etc.)

References
• Austin, R., Shreve’s Chemical Process Industries,
• Ali et al., Handbook of Industrial Chemistry – Organic Chemicals,
2005, Mc Graw Hill Book
• Kent, Riegel’s Handbook of Industrial Chemistry and Biotechnology,
2007, Springer

Definition of Chemical Industry

• Early in the 20th century → two parts: the discovery, synthesis, and
manufacture of inorganic and organic chemicals
• 1997 Standard Industrial Classification (SIC)→ "Chemical and Allied
Products“: Three general classes :
1. Basic inorganic chemicals : acids, alkalis, and salts and basic
Organic chemicals.
2. Chemicals to be used in further manufacture: synthetic fibers,
plastic materials, dry colors, pigments.
3. Finished chemical products to be used for ultimate consumer
consumption: architectural, paints, cosmetics, drugs, and soaps or # The chemical process industry includes those manufacturing facilities
to be used as materials or supplies in other industries such as whose products result from
industrial paints and coatings, adhesives, fertilizers, and explosives a. chemical reactions between organic materials, or inorganic
materials, or both;
CHEMICAL INDUSTRY PROCESS INTODUCTION
b. extraction, separation, or purification of a natural product, with or
without the aid of chemical reactions;
c. the preparation of specifically formulated mixtures of materials,
either natural or synthetic.
Characteristics of Chemical Industry
• Investment Trends
Chemical industries is high investment business. Capital investment in
the chemical industry is spent for facilities to produce major chemicals
in enormous quantities.
• Commercial Development and Competition Factors
Earlier period : Production oriented → pollution. With the grown of
Chemical Industry: Sizeable proportion. Low cost material selection.
The necessity for higher efficiency, lower cost processes
Raw Material
• Industrial chemistry procures raw materials from natural environments
to convert them into intermediates, which subsequently serve as base
materials to every other kind of industry.
• Source of natural environment :
 The earth's crust (lithosphere)
 The marine and oceanic environment (hydrosphere)
 The air (atmosphere)
 The plants (biosphere)
• Source of natural environment → renewable (agricultural materials) or
non renewable (fossil fuels)
Manufacturing and Engineering
• Industrial chemical process is designed to economically produce a
desired product from a variety of raw materials.
• The raw materials may undergo a number of steps involving physical
treatment, chemical reactions, separation, and purification before their
conversion into a desired product.
• The two major steps in chemical manufacturing are (1) the chemical
reaction and (2) the purification of reaction products.
• The primary types of chemical reactions are either batch or continuous.
1. Batch Reaction
➢ In batch reactions, the reactant chemicals are added to the
reactor (reaction vessel) at the same time and products are
emptied completely when the reaction is finished.
➢ The reactors are made of stainless steel or glass-lined carbon
steel and range in size from 200 to several thousand liters.
Batch reactors are provided with a stirrer to mix the reactants,
an insulating jacket, and the appropriate pipes and valves to
control the reaction conditions .
➢ Batch processes generally are used for small-scale production.
These processes are easier to operate, maintain, and repair. The
batch equipment can be adapted to multiple uses.
CHEMICAL INDUSTRY PROCESS INTODUCTION

2. Continuous Reaction  The chemical industry is one of the most highly regulated of all
➢ In continuous processes, the reactants are added and products industries.
are removed at a constant rate from the reactor, so that the
 The regulations are intended to protect and improve the health,
volume of reacting material in the reactor (reaction vessel)
safety, and environment of the public as well as the worker.
remains constant.
➢ Two types of reactors: (1) a continuous stirred tank or (2) a  The best way to reduce pollution is to study ways of preventing it
pipe reactor. at the research and development stage. At this stage, all possible
➢ A pipe reactor typically is a piece of tubing arranged in a coil reaction pathways for producing the desired product can be
or helix shape that is jacketed in a heat-transfer fluid. Reactants examined.
enter one end of the pipe, and the materials are mixed under
the turbulent flow and react as they pass through the system.
Because continuous processes require a substantial amount of
automation and capital expenditure, this type of process is used
primarily for large-scale productions.

Environmental Aspect

 The chemical industry uses and generates both large numbers and
large quantities of a wide variety of solvents, metal particulates,
acid vapors, and unreacted monomers. These chemicals are released
to all media including air, water, and land.
INDUSTRI ASAM SULFAT

Karakteristik Asam Sulfat
 Asam sulfat murni : berwarna seperti air, oily, larutan sedikit
viscous dengan TL 10,4 oC dan TD 270.6 oC
 Larut dalam air membentuk larutan asam sulfat yang dikarakterisasi
dengan % w H2SO4.
 Oleum : melarutkan SO3 dalam asam sulfat untuk memperoleh
asam sulfat yang konsentrasinya lebih besar dari 100 % H2SO4.
Kegunaan Asam Sulfat
 Pembuatan pupuk fosfat, pengilangan minyak bumi, leaching pasir
tembaga, plastik dan karet sintetis, pabrik pulp dan kertas.
 Asam sulfat digunakan sebagai solvent, dehydrating agent, katalis,
absorbent, tetapi tidak ada kandungan Asam sulfat dalam produk.
• Energy recovery – steam production, electrical power generation
• Net energy producer
 Acid Regeneration
• Regeneration furnace that decomposed H2SO4 into SO2 and
H2O
• Fuel is burned to provide the energy to decompose acid
• Waste heat boiler to recover energy from gas leaving furnace
• Wet gas cleaning system

Bahan Baku
 Bahan baku asam sulfat adalah gas SO2 yang kering dan bersih
dengan kadar 8-12% dalam gas O2, O2, N2, SO2, CO2, SO3.
 Gas tersebut dapat diperoleh dari :  Metallurgical
 Burning molten waste elemental sulfur (~70% dari • SO2 gas comes from a wide variety of pyrometallurgical
produksi dunia) processes
 Dari off gas metallurgical yang mempunyai kadar SO2 • Wet gas cleaning system to remove impurities from the gas
tinggi (~20%) • Both high and low SO2 gas strengths
 Dari dekomposisi katalis asam sulfat bekas (~10%) • Variable operation (flow and SO2 concentration)
• Treatment of wet gas cleaning system effluent
Type of Acid Plants
Three basic types of sulphuric acid plants :
 Sulphur Burning
Karakteristik:
• Elemental sulphur is a raw material
• Sulphur handling systems
• Sulphur furnace
INDUSTRI ASAM SULFAT
• Metallurgical Acid Plants
Proses Pembuatan Asam Sulfat
A. Lead chamber Process
 Menggunakan Nitrogen Oksida sebagai katalis pembawa oksigen
yang digunakan untuk konversi Sulfur dioksida menjadi sulfur
trioksida.
 Reaksi yang menghasilkan sulfur trioksida dan asam sulfat
dilakukan dalam suatu chamber yang besar atau packed tower yang
akan menggantikan chamber. Konsentrasi Asam sulfat < 80%
 Sulfur dioksida diabsorbsi dlm fase encer dan dioksidasi dengan
Nitrosyl hidrogensulfat (NOHSO4) (Asam Nitrosulfat) dalam
media 70% asam sulfat
 Reaksi pada Lead Chamber Process:
 Kelemahan Lead Chamber Process: Keterbatasan dalam luaran,
kualitas dan konsentrasi asam sulfat yang dihasilkan.
B. Contact Process
 Prinsip: Sulfur dioksida dikonversi menjadi sulfur trioksida dengan
katalis metal oksida (Platina, Vanadium Oksida).
 Tahap proses dalam contact process :
1. Pembentukan sulfur dioksida
2. Pendinginan dan untuk smelter, pembersihan gas proses
3. Konversi sulfur dioksida menjadi sulfur trioksida
4. Pendinginan gas sulfur trioksida
5. Absorbsi sulfur trioksida
 Blok Diagram Proses Pembuatan H2SO4
INDUSTRI ASAM SULFAT

ditambahkan untuk mengurangi keasaman molten sulfur

(mengurangi sifat korosivitas).
- Proses pembentukan SO2 : LURGI, DORR-OLIVER, BASF,
MONSANTO, dll.
c. Contact Process : Pembentukan SO2 (3)
- Gas yang keluar sulfur burner dapat mengandung karbon
dioksida, nitrogen, impuritas seperti halogen, arsenik, mercury
dan debu. → diperlukan unit gas cleaning
- Unit gas cleaning terdiri dari :(1) hot-gas dedusting; (2) wet
scrubbing; (3) gas cooling; (4) mist removal; and, (5) mercury
removal.
d. Contact Process : Konversi SO2→ SO3
- Konversi SO2 → SO3 dilakukan dalam suatu konverter
multistage, fixed-bed catalytic yang dilengkapi dengan
interstage boiler atau heat exchanger.

- Dalam industri : ketebalan bed 0.8 m dengan diameter 10 m.

a. Contact Process : Pembentukan SO2 (1)
Sulfur dikonversi menjadi sulfur dioksida dengan membakar
molten sulfur dengan udara kering pada SULFUR BURNER
untuk memperoleh gas dengan temperatur 1000-1200°C yang
mengandung 10-12 % SO2. Gas diturunkan temperaturnya
sampai 440-420 oC.

b. Contact Process : Pembentukan SO2 (2)

- Molten sulfur difilter untuk menghilangkan impuritas
(umumnya besi atau senyawa organik). Batu kapur juga
INDUSTRI ASAM SULFAT
 Katalis pada konversi SO2 → SO3
o Katalis yang digunakan adalah Vanadium pentaoksida (V2O5)
dengan K sebagai promotor pada suatu substrat silica porous.
o Mekanisme reaksi konversi SO2 katalis
Reaksi total :
o Reaksi SO2 → SO3
o Reaksi reversibel eksotermis.
o Konstanta keseimbangan reaksi :
o
o Kp ditentukan secara eksperimental berdasarkan tekanan
(atm).
o Konversi SO3 dipengaruhi oleh : temperatur, tekanan,
konsentrasi Reaktan dan Produk (Prinsip Le Catelier)
# Prinsip Le Catelier
• Temperature
Because heat is generated in the reaction, removing heat
will result in more SO3 formation
• Pressure
SO2 and O2 represent 1½ volumes of reactants while SO3 is
only 1 volume Therefore increasing the pressure at which
the reaction occurs will result in more SO3 formation.
• Concentration of Products and Reactants
Removing reaction products will result in the formation of
more products
# Grafik Konversi SO2 vs Temperatur dan Konsentrasi SO2
INDUSTRI ASAM SULFAT

 Kondisi Operasi Konversi SO2 pada Proses Kontak o Grafik Konversi SO2 vs Temperatur:
o Pengaruh temperatur terhadap konversi keseimbangan dan
kecepatan reaksi sangat bertentangan.
o Dalam proses kontak, pada awalnya gas masuk bed katalis pada
temperatur sekitar 425-440 oC dan selanjutnya temperatur
meningkat secara adiabatis selama reaksi.
o Kecepatan reaksi meningkat dengan peningkatan temperatur,
tetapi kemudian menurun setelah terjadinya kesetimbangan.
o Reaksi berhenti ketika 60-70 % SO2 telah terkonversi, dengan
temperatur 900 oC, selanjutnya gas didinginkan.
o Grafik Operasi Adiabatis dan Isotermal:

o Single Bed Katalis untuk Konversi SO2 :

INDUSTRI ASAM SULFAT

o Multi Bed Katalis untuk Konversi SO2 : o GAS COOLING:

Absorbsi Sulfur trioksida

o Multi Bed Katalis untuk Konversi SO2
 Sulfur trioksida dari konverter diabsorbsi dalam 98-99% H2SO4 pada
temperatur 60-80°C.

 Absorbsi bisa secara single dan double absorbtion.

 Faktor yang mempengaruhi absobsi : konsentrasi asam, temperatur

asam, desain tower (jenis dan tinggi packing), distribusi gas-cair, aliran
gas, aliran asam, konsentrasi SO3 dalam gas.

A. SINGLE ABSORBTION/ SINGLE CONTACT

- Mempunyai 1 tower absorbsi SO3
- Didesain dgn 3-4 bed katalis
INDUSTRI ASAM SULFAT

B. DOUBLE ABSORBTION/ DOUBLE CONTACT

- Ada 2 tower absorbsi SO3
- Desain dapat disesuaikan untuk menghasilkan recovery energy - Simple flowsheet : Dual Absorbtion
dan handling gas.
- Memenuhi standar emisi
- Plant lebih mahal
- Recovery energi lebih kecil
INDUSTRI ASAM SULFAT

- Flowsheet sulphur-burning double absorbtion plant (Monsanto) SULFUR

 Sulfur pada proses kontak dapat diperoleh dari :

1. Penambangan Sulfur (Frasch Proses)

Sulphuric Acid Plants in Indonesia

 PT Indonesian Acids Industry Limited (IAI)

 PT Mahkota Indonesia

Location : Bekasi. Type of Plant: Sulpur Burning.

Gas Source: Elemental Sulphur.

Products: 98% Sulphuric Acid, 20 to 30% Oleum

 PT Petro Jordan Abadi

Location : Gresik. Gas Source: Elemental Sulphur. 2. Flue gas (dengan Claus Proses)

 PT Timur Raya • Ada 2 tahap proses :

Location : Karawang. Product : Sulfuric Acid: 98.2% Min.

INDUSTRI ASAM SULFAT

o Thermal Step. H2S dioksidasi parsial dengan udara.

Dilakukan dalam furnace dengan temperatur tinggi
(1000-1400 deg C). Diperoleh Sulfur, tetapi sebagian
H2S tdk bereaksi.

o Catalytic Step. Sisa H2S direaksikan dgn SO2

temperatur rendah (200-350 deg C) dengan katalis
Fe2O3.

 Oksidasi senyawa sulfida disebut dengan roasting process.

Gambar fluid bed roasting :

3. Sulfur juga dapat diperoleh dalam bentuk sulfida misalnya ZnS

atau pyrite (FeS2)

Roasting Process

• Roasting ZnS

• Roasting Pyrite