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Bulk Chemical

Industri Methanol
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Plastics, electronics, materials, fibers, Specialty

Consumer products solvents, detergents, insecticides,
(ca.30,000) chemicals
pharmaceuticals

Intermediates
Acetic acid, formaldehyde, urea,
(ca.300) ethene oxide, acrylonitrile,
acetaldehyde, terephtalic acid
Bulk
Ethene, prophene, butene, benzene, chemicals
Base chemicals
synthesis gas, ammonia, methanol,
(ca.20)
sulfuric acid, chlorine
Fuels
(ca.10) LPG, gasoline, diesel, kerosene

Oil, natural gas, coal, biomass,

Raw materials (ca.10)
rock, salt, sulfur, air, water
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Metanol = metil alkohol = alkohol kayu.

• CH3OH, MeOH
• Light, volatile, colorless, flammable, distinctive odor
that is very similar to ethanol
• Zat kimia organik yang merupakan zat kimia dasar,
bahan petrokimia utama, dan sekaligus bahan bakar
• Toxic !
• As an antifreeze, solvent, and as a denaturant for
ethanol.
• It is also used for producing biodiesel via
transesterification reaction.
• 25 = 786,6 kg/m3. Tb = -97,88 oC. Td,n = 64,70 oC.
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• Disebut alkohol kayu karena dahulunya diproduksi dari

distilasi kering (pirolisis) kayu
• Bahan mentah : kayu-keras (hardwood)  kayu pohon
berdaun lebar (tak berdaun jarum seperti pinus dan
cemara).
• Disebut juga distilasi destruktif.
• Potongan/serpihan/serbuk kayu dipanaskan tanpa udara di
dalam bejana besi sampai 400 – 500 oC dan campuran gas +
uap hasil dekomposisinya diembunkan dalam sebuah
kondensor.
• Kondensat ( cairan pirolignous) ditampung, disingkirkan
tér-nya dan kemudian didistilasi utk memperoleh metanol,
asam asetat, aseton, dll.
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• Perolehan tipikal distilasi-kering kayu : arang 34,7 %; ter 13 %;

asam asetat 7 %; metanol 1 %; (aseton + metil asetat +
asetaldehid + alil alkohol) 1,1 %; gas 19,2 %; air 24 %.

• Perolehan metanol meningkat 50 % jika kayu umpan dibubuhi

0,5 – 1,5 % Na2CO3

• Dahulu pernah “berjaya”; sekarang tidak lagi demikian

• Tahun 1930 di A.S., 50 % produksi metanol berasal dari

pirolisis kayu; tahun 1950 hanya tinggal 3 %

• Sekarang diproduksi dari syngas

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Methanol Production
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Thermodynamics
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CO and CO2 equilibrium data

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Product from CO and H2 ; change of free energy of formation (∆Go) as a

function of temperature
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• Catalyst needs to be very selective !!!

• The original catalysts (katalis pada proses lama) (ZnO-CrO3) were only
active at high temperature  Pressure had to be high (250-350 bar)

• Were used until the end of 1960s

• More active catalysts were known, but were not resistant to

impurities (e.g. sulfur)

• Modern catalysts (Cu/ZnO/Al2O3) have selectivity over 99%

• This led to  Low-Pressure Plants

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Equilibrium CO conversion to methanol; feed H2/CO = 2

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Catalyst deactivation
• Catalyst deactivation akan selalu terjadi

• To restore activity  increasing the temperature

• This is to maintain the rate of reaction

• Increased T  increased P

• T yang dipilih tidak boleh melampaui 570 K, karena

dapat menimbulkan terjadinya sintering pada katalis
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Sintering
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Methanol Synthesis

Simplified flow scheme of classical methanol process

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Simplified flow scheme of the ICI low-pressure process

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Lurgi Process

Schematic of Lurgi reactor

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Simplified flow scheme of the reaction section of the Haldor Topsøe methanol process
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Simplified flow scheme Chem Systems three-phase methanol process

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Application of Methanol
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Formaldehyde
• One of the largest application (25 % of methanol
consumptions)

• Reactions :
CH3OH CH2O + H2 ∆Ho298= 85 kJ/mol
CH3OH + ½ O2 CH2O + H2O ∆Ho298= -158 kJ/mol

• Produced by dehydrogenations or by partial oxidation

• In industrial practice, both are carried out in a single

reactor
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MTBE
• MTBE has high octane number
• Used as an octane booster in gasoline
• Leakage and spills enters the groundwater and is
well miscible with water
• Banned in US
• Growing production (still ?) in the other part of
the world
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DME
• DME  dimetil eter (CH3-O-CH3), dapat dibuat via dehidrasi
metanol dengan bantuan katalis homogen (H2SO4) maupun
heterogen :

• 2 CH3OH  CH3-O-CH3 + H2O

• DME : tak beracun; Td,n = - 23,7 oC; cair di kondisi kamar pada
tekanan 10 bar [mirip elpiji]

• Kegunaan DME : pembersit (propellant) kosmetik, refrigerant,

bahan bakar otomotif pengganti solar (ADO) [angka setan 55 –
60 (solar  45) nilai kalor netto cairan per liter  ½ x solar]
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Thank you for your attention

Question(s) ???