47.

2CME 430-431
2017-2018 Academic Year
Project: Methanol from glycerol

Fatty acid methyl esters (FAMEs) make an excellent biodiesel fuel, with kinematic viscosities and Cetane
numbers comparable to conventional diesel fuels. FAMEs are made by reacting triglycerides, which are
the primary component of animal and some vegetable fats, with methanol:

𝑇𝑟𝑖𝑔𝑙𝑦𝑐𝑒𝑟𝑖𝑑𝑒 + 3 𝑀𝑒𝑡ℎ𝑎𝑛𝑜𝑙 → 3 𝐹𝐴𝑀𝐸 + 𝑔𝑙𝑦𝑐𝑒𝑟𝑜𝑙

This process has two challenges: the market for glycerol, the side product of this reaction, is small, and
methanol, which is currently made from syngas, is expensive to manufacture. However, recent
research [1] suggests that glycerol can be converted directly to methanol via a complex reaction
catalyzed by a metal oxide.

Our chemists have followed up on this work and developed a process that produces methanol from
glycerol using a proprietary metal oxide catalyst we have developed in-house. The reactions are as
follows:

𝐶3 𝐻8 𝑂3 + 𝐻2 𝑂 ⟶ 𝐶𝐻3 𝑂𝐻 + 𝐶2 𝐻4 𝑂 + 𝐻2 𝑂2 (1)

𝐶3 𝐻8 𝑂3 + 3𝐻2 𝑂 ⟶ 𝐶𝐻3 𝑂𝐻 + 𝐶2 𝐻5 𝑂𝐻 + 2𝐻2 𝑂2 (2)

𝐶3 𝐻8 𝑂3 + 4𝐻2 𝑂 ⟶ 3𝐶𝐻3 𝑂𝐻 + 2𝐻2 𝑂2 (3)

Here, 𝐶2 𝐻4 𝑂 is acetaldehyde. This is a gas phase reaction that takes place at 1 atm and 320⁰C. Our
chemists report the following:

For feeds between 10 wht% and 30 wht% glycerol, and for glycerol conversions between 10% and 40%,
the reaction rates may be approximated as

𝑚𝑜𝑙
𝑟1 ( ) = 47.2𝑃𝑔𝑙𝑦𝑐𝑒𝑟𝑜𝑙 𝑃𝐻2 𝑂
𝑘𝑔 𝑐𝑎𝑡 − ℎ

𝑚𝑜𝑙
𝑟2 ( ) = 23.6𝑃𝑔𝑙𝑦𝑐𝑒𝑟𝑜𝑙 𝑃𝐻2.8
2𝑂
𝑘𝑔 𝑐𝑎𝑡 − ℎ

𝑚𝑜𝑙
𝑟3 ( ) = 11.8𝑃𝑔𝑙𝑦𝑐𝑒𝑟𝑜𝑙 𝑃𝐻3.2
2𝑂
𝑘𝑔 𝑐𝑎𝑡 − ℎ

Here, 𝑃𝑖 is the partial pressure of species i, measured in atmospheres.

The goal of this project is to explore the economic viability of this route to methanol by designing a
production process that will produce 10,000 ton/year of methanol with this chemistry.

Feedstocks: Technical grade glycerin containing 98 wht% glycerol and 2% water may be purchased for
$0.80/lb. City water is available for $0.25/m3.

Products and Byproducts.

Your methanol product may contain no more than 500 ppm water, 100 ppm ethanol, 30 ppm
acetaldehyde, and 10 ppm glycerol, and sells for $2/gallon.

Fuel grade ethanol can be sold for $2.10/gallon. It must be no more than 0.5% methanol and1% water.

Acetaldehyde can be sold for $0.455/lb. It must be at least 99.6 wht% pure and may contain no more
than 0.15 wht% water.

A 50 wht% hydrogen peroxide solution in water sells for $0.46/lb. It may contain no more than 100 ppm
of ethanol, 50 ppm of acetaldehyde, and 10 ppm of methanol.

Catalyst. The catalyst costs $10/kg and has a bulk density of 5.3 g/cm3.