PRODUCTION OF

METHANOL FROM
GLYCEROL

By
SAJJAD KHUDHUR ABBAS P81540

A design project submitted to the Faculty of Engineering and Built Environment

in partial fulfilment of the requirements for Design of Chemical Processes
computer aided Class KKKK6014

Faculty of Engineering and Built Environment

The National University of Malaysia

DECEMBER 2015

Supervisors
PROF. DATO' IR. DR. WAN RAMLI BIN WAN DAUD

DR. NOR YULIANA BINTI YUHANA

Dr. DARMAN BIN NORDIN
 The National University of Malaysia

Faculty of Engineering and Built Environment

The undersigned certify that they have read, and recommend to the Faculty of
Chemical and Natural Resources Engineering for acceptance, a design project
entitled Production of 60,000 MTPA of Oleochemical Methyl Ester from RBD
Palm Kernel Oil submitted by

SAJJAD KHUDHUR ABBAS P81540

A design project submitted to the Faculty of Engineering and Built Environment

in partial fulfilment of the requirements for Design of Chemical Processes
computer aided Class KKKK6014

______________________________

DR. NOR YULIANA BINTI YUHANA

 CHAPTER 1
INTRODUCTION

1.1 INTRODUCTION

Methanol is an important bulk chemical in the chemical industry. The global methanol
demand was approximately 32 million metric tons in 2004 and is expected to grow .
Methanol is used mainly for the production of formaldehyde, acetic acid, and application
products including polymers and paints. Furthermore, methanol can be used as a clean and
renewable energy carrier Methanol is mainly produced from syngas, a mixture of H2, CO,
and minor quantities of CO2 and CH4. Syngas is commonly produced from fossil resources
like natural gas or coal. Biomass, however, can also be used as resource for syngas and
allows the synthesis of green methanol. Green methanol not only has environmental benefits,
but may also lead to considerable variable cost reductions if the biomass resource has a low
or even negative value The biodiesel factory is the core of the process in which vegetable oils
react with methanol in the presence of a catalyst to produce biodiesel and by-product
glycerol. The glycerol can be converted into methanol in the glycerol-to-methanol (GtM-)
process. This process is an integration of two separate processes, viz. the reforming in
supercritical water (RSCW) of glycerol to syngas, followed by the conversion of this syngas
into methanol. Additional fuel gas is produced, which can be used to generate heat for the
biodiesel production or in the GtMprocess.
 Figure 1: Outline of the Supermethanol concept.

1.2 HISTORY

In their embalming process, the ancient Egyptians used a mixture of substances, including
methanol, which they obtained from the pyrolysis of wood. Pure methanol, however, was
first isolated in 1661 by Robert Boyle, when he produced it via the distillation
of buxus (boxwood). It later became known as "pyroxylic spirit". In 1834, the French
chemists Jean-Baptiste Dumas and Eugene Peligot determined its elemental composition.
They also introduced the word "methylene" to organic chemistry, forming it
from Greek methy = "wine" + hȳlē = wood (patch of trees), with Greek language errors:
"wood (substance)" (Greek xylon) was intended, and the components are in the wrong order
for Greek. The term "methyl" was derived in about 1840 by back-formation from
"methylene", and was then applied to describe "methyl alcohol". This was shortened to
"methanol" in 1892 by the International Conference on Chemical Nomenclature. The suffix -
yl used in organic chemistry to form names of carbon groups, was extracted from the word
"methyl". In 1923, the German chemists Alwin Mittasch and Mathias Pier, working
for BASF, developed a means to convert synthesis gas (a mixture of carbon
monoxide, carbon dioxide, and hydrogen) into methanol. A patent was filed 12 January 1926
(reference no. 1,569,775). This process used achromium and manganese oxide catalyst, and
required extremely vigorous conditions—pressures ranging from 50 to 220 atm, and
temperatures up to 450 °C. Modern methanol production has been made more efficient
through use of catalysts (commonly copper) capable of operating at lower pressures. The
modern low pressure methanol (LPM) was developed by ICI in the late 1960s with the
technology now owne by Johnson Matthey, which is a leading licensor of methanol
technology.

1.3 PRODUCTION

1.3.1 From Synthesis Gas

Carbon monoxide and hydrogen react over a catalyst to produce methanol. Today, the most
widely used catalyst is a mixture of copper, zinc oxide, and alumina first used by ICI in 1966.
At 5–10 MPa (50–100 atm) and 250 °C, it can catalyze the production of methanol from
carbon monoxide and hydrogen with high selectivity (>99.8%):

CO + 2 H2 → CH3OH

It is worth noting that the production of synthesis gas from methane produces three moles of
hydrogen gas for every mole of carbon monoxide, while the methanol synthesis consumes
only two moles of hydrogen gas per mole of carbon monoxide. One way of dealing with the
excess hydrogen is to inject carbon dioxide into the methanol synthesis reactor, where it, too,
reacts to form methanol according to the equation:

CO2 + 3 H2 → CH3OH + H2O

Some chemists believe that the certain catalysts synthesize methanol using CO 2 as an
intermediary, and consuming CO only indirectly.

CO2 + 3 H2 → CH3OH + H2O

where the H2O byproduct is recycled via the water-gas shift reaction

CO + H2O → CO2 + H2

This gives an overall reaction, which is the same as listed above.

CO + 2 H2 → CH3OH

1.3.2 From Methane

The direct catalytic conversion of methane to methanol using Cu-zeolites or other catalysts is
an alternative process for the efficient production of methanol.

1.3.3 From Carbon Dioxide

Methanol has been generated directly from carbon dioxide in solution using copper oxide
(CuO) nanorods coated by cuprous oxide (Cu2O) and energy from (simulated) sunlight. The
process operated with 95% electrochemical efficiency and is claimed to be scalable to
industrial size.

1.4 QUALITY SPECIFICATIONS AND ANALYSIS

1.4.1 Methanol for Laboratory Use

Methanol is available commercially in various purity grades for fine chemicals: 1)

―Synthesis‖ quality (corresponding to normal commercial methanol) 2) Certified analytical
quality 3) Extremely pure qualities for semiconductor manufacture.
1.4.2 Commercial Methanol

In addition to laboratory grades, commercial methanol is generally classified according to

ASTM purity grades A and AA. Methanol for chemical use normally corresponds to Grade
AA. In addition to water, typical impurities include acetone (which is very difficult to
separate by distillation) and ethanol. When methanol is delivered by ships or tankers used to
transport other substances, contamination by the previous cargo must be expected.
Comparative ultraviolet spectroscopy has proved a convenient, quick test method for
deciding whether a batch can be accepted and loaded. Traces of all chemicals derived from
aromatic parent substances, as well as a large number of other compounds, can be detected.
Further tests for establishing the quality of methanol include measurements of boiling point
range, density, permanganate number, turbidity, color index, and acid number. More
comprehensive tests include water determination according to the Karl Fischer method and
gas chromatographic determination of byproducts. However, the latter is relatively expensive
and time consuming because several injections using different columns and detectors must be
made due to the variety of byproducts present.

1.5 APPLICATIONS
Methanol, a common laboratory solvent, is especially useful for HPLC, UV/VIS
spectroscopy, and LCMS due to its low UV cutoff.

1.5.1 Feedstock

The largest use of methanol by far is in making other chemicals. About 40% of methanol is
converted to formaldehyde, and from there into products as diverse as
plastics, plywood, paints,explosives, and permanent press textiles.

Also in the early 1970s, a methanol to gasoline process was developed by Mobil for
producing gasoline ready for use in vehicles. One such industrial facility was built
at Motunui in New Zealand in the 1980s. In the 1990s, large amounts of methanol were used
in the United States to produce the gasoline additive methyl tert-butyl ether (MTBE). While
MTBE is no longer marketed in the U.S., it is still widely used in other parts of the world. In
addition to direct use as a fuel, methanol (or less commonly, ethanol) is used as a component
in the transesterification of triglycerides to yield a form of biodiesel.
Other chemical derivatives of methanol include dimethyl ether, which has
replaced chlorofluorocarbons as an aerosol spray propellant, and acetic acid. Dimethyl
ether (DME) also can be blended with liquified petroleum gas (LPG) for home heating and
cooking, and can be used as a diesel replacement for transportation fuel.

Methanol-to-Olefins/Methanol-to-Propylene (MTO/MTP), among others processes such as:

Metathesis, Propane Dehydrogenation (PDH), High Severity FCC, and Olefins Cracking, is a
new and novel lower-cost chemical process for on-purpose propylene production technology
of high interest to the petrochemical marketplace, to supply the tight propylene market.
The market became tight because of the ethane prices falling in the USA, due to the
exploration of shale gas reserves. The low price ethylene produced from this raw material has
given chemical producers in North America a feedstock advantage. Such change has put
naphtha-fed steam crackers at a disadvantageous position, with many of them shutting down
or revamping to use ethaneas feedstock. Nevertheless, the propylene output rates from
ethane-fed crackers are negligible.

1.5.2 Fuel for Vehicles

Main articles: Methanol fuel and methanol economy

Methanol is used on a limited basis to fuel internal combustion engines. Pure methanol is
required by rule to be used in Champcars, Monster Trucks, USAC sprint cars (as well as
midgets, modifieds, etc.), and other dirt track series, such as World of Outlaws,
and Motorcycle Speedway. Methanol is also used, as the primary fuel ingredient since the
late 1940s, in the powerplants for radio control, control line and free flight airplanes (as
methanol is required in the engines that primarily power them), cars and trucks, from such an
engine's use of a platinum filament glow plugbeing able to ignite the methanol vapor through
a catalytic reaction. Drag racers and mud racers, as well as heavily modified tractor pullers,
also use methanol as their primary fuel source. Methanol is required with a supercharged
engine in a Top Alcohol Dragster and, until the end of the 2006 season, all vehicles in
the Indianapolis 500 had to run methanol. Mud racers have mixed methanol with gasoline
with nitrous oxide to produce more power than mixing gasoline and nitrous oxide alone.
One of the potential drawbacks of using high concentrations of methanol (and other alcohols,
such as ethanol) in fuel is the corrosivity to some metals of methanol, particularly to
aluminium. Methanol, although a weak acid, attacks the oxide coating that normally protects
the aluminum from corrosion:

6 CH3OH + Al2O3 → 2 Al(OCH3)3 + 3 H2O

The resulting methoxide salts are soluble in methanol, resulting in a clean aluminium surface,
which is readily oxidized by dissolved oxygen. Also, the methanol can act as an oxidizer:

6 CH3OH + 2 Al → 2 Al(OCH3)3 + 3 H2

This reciprocal process effectively fuels corrosion until either the metal is eaten away or the
concentration of CH3OH is negligible. Concerns with methanol's corrosivity have been
addressed by using methanol-compatible materials, and fuel additives that serve as corrosion
inhibitors.

When produced from wood or other organic materials, the resulting organic methanol
(bioalcohol) has been suggested as renewable alternative to petroleum-based hydrocarbons.
Low levels of methanol can be used in existing vehicles, with the use of proper cosolvents
and corrosion inhibitors.

Methanol fuel has been proposed for ground transportation. The chief advantage of a
methanol economy is that it could be adapted to present internal combustion engines with a
minimum of modification in both engines and infrastructure to store and deliver liquid fuel.

1.5.3 Other Applications

Methanol is a traditional denaturant for ethanol, the product being known as "denatured
alcohol" or "methylated spirit". This was commonly used during the Prohibition to
discourage consumption of bootlegged liquor, and ended up causing several deaths.

Methanol is also used as a solvent, and as an antifreeze in pipelines and windshield washer
fluid. In some wastewater treatment plants, a small amount of methanol is added
to wastewater to provide a carbon food source for the denitrifying bacteria, which
convert nitrates to nitrogen to reduce the nitrification of sensitive aquifers.
During World War II, methanol was used as a fuel in several German military rocket designs,
under the name M-Stoff, and in a roughly 50/50 mixture with hydrazine, known as C-Stoff.
Methanol was used as an automobile coolant antifreeze in the early 1900s. Methanol is used
as a denaturing agent in polyacrylamide gel electrophoresis.

Direct-methanol fuel cells are unique in their low temperature, atmospheric pressure
operation, allowing them to be miniaturized to an unprecedented degree. This, combined with
the relatively easy and safe storage and handling of methanol, may open the possibility of
fuel cell-powered consumer electronics, such as for laptop computers and mobile phones
Methanol is also a widely used fuel in camping and boating stoves. Methanol burns well in an
unpressurized burner, so alcohol stoves are often very simple, sometimes little more than a
cup to hold fuel. This lack of complexity makes them a favorite of hikers who spend
extended time in the wilderness. Similarly, the alcohol can also be gelled to reduce risk of
leaking or spilling, as with the brand "Sterno".

Methanol is mixed with water and injected into high performance diesel and gasoline engines
for an increase of power and a decrease in intake air temperature in a process known as water
methanol injection.

1.6 PROPERTIES

Methanol, also known as methyl alcohol, wood alcohol, wood naphtha or wood spirits, is a
chemical with the formula CH3OH.

Formula: CH4O
Density: 791.80 kg/m³
Boiling point: 148.5°F (64.7°C)
Molar mass: 32.04 g/mol
Vapor pressure: 13.02 kPa
Melting point: -143.7°F (-97.6°C)
Classification: Alcohol
Structure and properties:

Structure and properties

Index of refraction, nD 1.328 at 20°C

Dielectric constant, εr 32.66 at 20°C

Bond angle all 109.5°

Magnetic susceptibility 5.3×10−7 cm3·g−1

Surface tension 22.5 dyn/cm at 20°C

0.808 mPa·s at 0°C

0.690 mPa·s at 10°C
Viscosity 0.593 mPa·s at 20°C
0.449 mPa·s at 40°C
0.349 mPa·s at 60°C

Thermodynamic properties:

Phase behavior

Triple point 175.5 K (−97.7 °C)

Critical point 513 K (240 °C), 78.5 bar

Std enthalpy change of fusion, ΔfusHo 3.1773 kJ/mol

Std entropy change of fusion, ΔfusSo 18.1 J/(mol·K)

Std enthalpy change of vaporization, ΔvapHo +35.278 kJ/mol

Std entropy change of vaporization, ΔvapSo 113 J/(mol·K)

Liquid properties

Std enthalpy change of formation, ΔfHoliquid −238.4 kJ/mol

Standard molar entropy, Soliquid 127.2 J/(mol K)

Enthalpy of combustion ΔcHo –715.0 kJ/mol

Heat capacity, cp 79.5 J/(mol K)

Gas properties

Std enthalpy change of formation, ΔfHogas -201.3 kJ/mol

Standard molar entropy, Sogas 239.9 J/(mol K)

52.29 J/(mol K) at 77°C

Heat capacity, cp
61.43 J/(mol K) at 100-223°C

Heat capacity ratio, γ = cp/cv 1.203 at 77°C

a = 964.9 L2 kPa/mol2
van der Waals' constants
b = 0.06702 liter per mole
 CHAPTER 2
CONCEPTUAL DESIGN LEVELS

2.1 LEVEL 1: SELECTION OF PROCESSING MODE

In common practice, there are 2 types of plant which are normally used in chemical
processing industry namely batch plant and continuous plant. Selection of the plant is based
on the production capacity. Normally, a continuous plant is suitable for production capacity
which is more than 5000 metric tons per year; whereas a batch plant is limited to only 500
metric tons per year. Since, methanol production in this project is 100,000 metric tons per
year; therefore, it is more suitable the production is in continuous mode.

2.2 LEVEL 2: SELECTION OF INPUT-OUTPUT STRUCTURE

2.2.1 Reaction Information

The process of methanol production from glycerol consists of two main sections which are
reforming section and methanol synthesis section. In the reforming section, syngas such as
hydrogen and carbon dioxide are produced from aqueous reforming phase (APR) of glycerol.
In the methanol synthesis section, syngas from reforming section have been reacted to
produce methanol. Multiple reactions have been involved in this section.

The primary reactions in glycerol steam reforming are as follows:

C3 H 8 0 3 
 3CO  4H 2
H2 0 (1)

CO  H 2 0 
 CO2  H 2 (2)

Eq. (1) denotes glycerol decomposition in the presence of water, whereas Eq. (2) is the water-
gas shift reaction.
In this section, following equation has been considered:

3C 3 H 8O3  2H 2 0 
 7CO  2CO2  14H 2 (3)
In methanol synthesis section, there are three (2) overall reactions describe the formation of
methanol when a CO2, CO and H2O are employed. Methanol can be formed via the highly
exothermic hydrogenation of carbon monoxide and carbon dioxide.

CO  2H 2 
 CH 3OH (4)

CO2  3H 2 
 CH 3OH  H 2 0 (5)

Thus, it can be concluded that water and glycerol has been fed into reformer reactor to
produce syngas and water according to reaction equation 3. Syngas and water is further
separate by using phase separator which water and glycerol will be recycled back to the feed
inlet streams. Syngas will be fed into the Methanol reactor and multiple reaction will occur in
this reactor which have been described in reaction equation 4,5 . Then CO, CO2 and H2 will
be separated and recycled to the feed of Methanol reactor. Finally, methanol will be purified
by using distillation column.

The production of methanol from synthesis gas may take place under the low or high
pressure. The high pressure process operates typically at 200 atm and 350°C while the low
pressure process operates at 50 - 100 atm and 220 - 250°C. The low pressure process has
such economical and operational benefits that almost all the methanol plants built after year
1967 operate at the low pressure. [Klier 1982]
2.2.2 Input-Output Structure

ξ CO = ξ CO2 = ξ H2 = 1
PG
yCO
FG yCO2
REFORMER MeOH yH2
REACTOR
FW
FS PM
yCO
H2O yCO2
Glycerol yH2
PW
ξH20= 100% =1

Figure 2.1: Input-Output Structure for Methanol Production

2.2.3 Methanol Selectivity

Basis: Production of Methanol, PM is 100,000 metric tons per year = 356,735 kmol/hr
Reactions that involve in this process as follows:

In Methanol Synthesis Section

CO  2H 2 
 CH 3OH (r1)

CO2  3H 2 
 CH 3OH  H 2 0 (r2)

In Reforming Section

3C 3H8O3  2H 2 0  7CO  2CO2  14H 2 (r3)

Assumption: H2 is limiting reactant

XH2 is the conversion of the limiting reactant
SM is methanol selectivity
PM is moles of Methanol produced

PM
SM  (2.1)
.FS y H 2 . X H 2

PM
FS . y H 2  (2.2)
SM .X H 2

Mole balance on MeOH reactor

(2.3)
nco = - r1
nCO2 = -r2
nH2 = -2r1 – 3r2
nM = r1 + r2 (2.4)
nH2O = r2

From (2.3)

0 .X
nH
r1  2 H 2 - 3r2 (2.5)
2

nM (2.6)
SM 
n0 .X H 2
H2

Substitute (2.6) in (2.4)

0 .X
S M .nH 2 H 2  r1  r2 (2.7)
Substitute (2.7) into (2.5)

0
0
S M .n H 2 . X H 2 
nH 2 . X H 2  3r2  r
2
2

0
r2  nH 2 . X H 2 (1  2S M ) (2.8)

Substitute (2.8) in (2.3)

0 0
nH 2 . X H 2  2r1  3nH 2 . X H 2 (1  2S M )
0
r1 
nH 2 . X H 2 (6S M  2)
2 (2.9)

nco = n0co - r1
0
0
 nCo
nH 2 . X H 2 (6S M  2) (2.10)

2

nCO2 = n0CO2-r2
0
= n0CO2 - nH 2 . X H 2 (1  2S M ) (2.11)
0
nH2 = n H2 -2r1 – 3r2
0
= - nH 2 .X H 2 (2.12)
0
nM = n M + r1 + r2
= S .n 0 . X (2.13)
M H2 H2
nH2O = n0H2O + r2
0
= nH 2 . X H 2 (1  2S M ) (2.14)

The number of moles after the reactions take place:

nT = nCO + nH2 + nCO2 + nM + + nH20

2 . X H 2 (6S M  2)
0
nH 0 0
2 . X H 2 (1  2S M ) + n H2 -2r1 – 3r2 + S M .nH 2 . X H 2 +
0
= n co - 2 + n0CO2 - nH 0

0
nH 2 . X H 2 (1  2S M )
= n0co+ n0CO2+ n0H2 - 2 S M .nCO
0
2 . X CO2

n0 H 2 n oH2

nT n 0 co + n 0 CO2 + n 0 H2 - 2S M .n H
0
2 .X H 2
o
nco
 M1
o
nH 2
o
nCO 2  M2
o
nH 2
n0 H 2 1
 (2.15)
nT M1+ M2 + 1 - 2S M X H 2

Reaction Kinetics

From PRINSIP REKA BENTUK PROSES KIMIA

by WAN RAMLI WAN DAUD

r1  k1o exp(  E1 / RT ) PT yCO y H

2
2 (2.16)

r2  k 2o exp(  E2 / RT ) PT yCO2 (2.17)

Reaction kio (kmole/(kgcatalyst.atm.hr)) ΔE (kJ/kmole)

1 2.934 x 10-9 -9.45 x 104
2 1.940 x 105 4.94 x 104

Temperature, T = 200°C = 473.15 K

Pressure, P = 80 bar
R = 8.3144 kJ.K/kmole
Mole Balance on MeOH reactor:

1 dnCO
 r1
V dt
1 dnCO 2
  K1PyCO y H 2 (2.18)
V dt

1 dnH 2
 2r1  3r2
V dt
1 dnH 2 2
 2 K1PyCO y H 21  3K 2 Py CO2 (2.19)
V dt
1 dnCO2
 r2
V dt
1 dnCO2
  K 2 PyCO2 (2.20)
V dt

1 dn H 2O
 r2
V dt
1 dnH 2O
 K 2 PyCO2 (2.21)
V dt
1 dnCH 3OH
 r1  r2
V dt
1 dnCH 3OH 2
 K1PyCO y H 2  K 2 Py CO2 (2.22)
V dt

1 P
 (2.23)
V nT RT

n0 H 2 (1  X H 2 ) nH 2
yH 2   (2.24)
nT nT
n
yco 2  co 2 (2.25)
nT
n
yCO  CO (2.26)
nT

For CO
P dnCO 2
  K1PyCO y H 2
nT RT dt
nT dyCO 2
 nT RTK1 yCO y H 2
dt
dyCO 2
  RTK1 yCO y H 2 (2.27)
dt
For H2

P dnH 2 2
 2 K1PyCO y H 21  3K 2 Py CO2
nT RT dt
nT dy H 2
dt
 2
 nT RT  2 K1 yCO y H 21  3K 2 yCO2 
dy H 2
dt
 2
 RT  2 K1 yCO y H 2  3K 2 yCO2  (2.28)

For CO2

P dnCO2
  K 2 PyCO2
nT RT dt
dnCO2
 nT RTK 2 yCO2
dt
nT dyCO2
 nT RTK 2 yCO2
dt
dyCO2
  RTK 2 yCO2 (2.29)
dt

For H2O

dn H 2O
 nT RTK 2 yCO2
dt
nT dy H 2O
 nT RTK 2 yCO2
dt
dy H 2O
 RTK 2 yCO2 (2.30)
dt

For Methanol

dnCH 3OH
dt
 2
 nT RT K1 yCO y H 2  K 2 yCO2 
nT dyCH 3OH
dt
 2
 nT RT K1 yCO y H 2  K 2 yCO2 
dyCH 3OH
dt
 2
 RT K1 yCO y H 2  K 2 yCO2  (2.31)
 dX H 2
From (2.28) Find
dt

dy H 2
dt
 2
 RT  2 K1 yCO y H 21  3K 2 yCO2 
dn o H 2 (1  X H 2 ) / nT
dt
 2
 RT  2 K1 yCO y H 21  3K 2 yCO2 
dX H 2  0
2 n H2 2
 n

  RT  2 K1 yCO (1  X H 2 ) ( )  3K 2 yCO2  T
dt  nT  n0
  H2
dX H 2  0
2 n H2 2
 n

  RT  2 K1 yCO (1  X H 2 ) ( )  3K 2 yCO2  T (2.32)
dt  nT  n0 H 2
 

Divide eq. (2.27) by eq. (2.32)

dyCO
2
dt   RTK1 yCO y H 2
dX H 2  0 
 RT   2 K1 yCO (1  X H ) 2 ( n H 2 ) 2  3K 2 yCO2  nT
dt  2
nT  n0
  H2
2
dyCO n0 H 2 K1 yCO y H
 2 (2.33)
dX H 2 nT  0 
  2 K1 yCO (1  X H ) 2 ( n H 2 ) 2  3K 2 yCO2 
 2
nT 
 

Divide eq. (2.29) by eq. (2.32)

dyCO2 n0 H 2 K 2 yCO2
 (2.34)
dX H 2 nT  0 
  2 K1 yCO (1  X H ) 2 ( n H 2 ) 2  3K 2 yCO2 
 2
nT 
 

Divide eq. (2.28) by eq. (2.32)

dy H 2 n0 H 2 (2.35)

dX H 2 nT

Divide eq. (2.31) by eq. (2.32)

dyCH 3OH

 2
RT K1 yCO y H 2  K 2 yCO2 
dX H 2  n0 H 2 2  n
 RT   2 K1 yCO (1  X H 2 ) 2 ( )  3K 2 yCO2  T
 nT  n0
  H2
dyCH 3OH

n0 H 2  2
K1 yCO y H 2  K 2 yCO2  (2.36)
dX H 2 nT  0 
  2 K1 yCO (1  X H ) 2 ( n H 2 ) 2  3K 2 yCO2 
 2
nT 
 

Divide eq. (2.30) by eq. (2.32)

dy H 2O n0 H 2 K 2 yCO2
 (2.37)
dX H 2 nT  0 
  2 K1 yCO (1  X H ) 2 ( n H 2 ) 2  3K 2 yCO2 
 2
nT 
 

PM  yCH 3 OH )(nT ) (2.38)

FS y H 2 S  n 0 H 2 (2.39)

Sub eq’s. (2.38)and (2.39) in eq. (2.1)

yCH 3 OH nT
Sm  (2.40)
n0 H 2 .X H 2

Sub eq. (2.15) in eq. (2.40)

FS yCO  n 0CO (2.41)
(2.42)
FS yCO2  n 0CO2

According to the reforming reaction (r3):

n 0 co 7
M1    0.5
n0 H 2 14
n 0 co 2 2
M1    0.143
n0 H 2 14
Sub. Equation (2.15) in equations (2.33), (2.34), (2.35), (2.36), (2.37), (2.41) and solving by using
MATLAB ODE45.

MATLAB Program :

K1=79.416;
K2=0.6826;
n=90;
yco2=zeros(1,n);
yco=zeros(1,n);
yh2o=zeros(1,n);
yh2=zeros(1,n);
ych3oh=zeros(1,n);
Xco2=zeros(1,n);
Sm=zeros(1,n);
yco2(1)=0.1;
yco(1)=0.3;
yh2(1)=0.6;
yh2o(1)=0.1;
ych3oh(1)=0.0693;
M1=0.5;
M2=0.143;
DXco2=1/n;
Xh2(1)=0.1;
for jj=2:n
Xh2(jj)=Xh2(jj-1)+0.01;
end
Sm(1)=1;
for i=1:n-1,
yco(i+1)=yco(i)+DXco2*(K1/((M1+M2+1-2*Sm(i)*Xh2(i))*(-2*K1*yco(i)*((1-
Xh2(i))^2)*(1/(1.643-2*Sm(i)*Xh2(i))^2)-3*K2*yco2(i))))*yco(i)*yh2(i)^2;
yh2(i+1)=yh2(i)+DXco2*(-1/(M1+M2+1-2*Sm(i)*Xh2(i)));
ych3oh(i+1)=ych3oh(i)+DXco2*(-1/((M1+M2+1-2*Sm(i)*Xh2(i))*(-2*K1*yco(i)*((1-
Xh2(i))^2)*(1/(1.643-2*Sm(i)*Xh2(i))^2)-3*K2*yco2(i))))*((K1*yco(i)*yh2(i)^2)+K2*yco2(i));
yco2(i+1)=yco2(i)-DXco2*(K2/((M1+M2+1-2*Sm(i)*Xh2(i))*(-2*K1*yco(i)*((1-
Xh2(i))^2)*(1/(1.643-2*Sm(i)*Xh2(i))^2)-3*K2*yco2(i))))*yco2(i);
yh2o(i+1)=yh2o(i)+DXco2*(K2/((M1+M2+1-2*Sm(i)*Xh2(i))*(-2*K1*yco(i)*((1-
Xh2(i))^2)*(1/(1.643-2*Sm(i)*Xh2(i))^2)-3*K2*yco2(i))))*(-yco2(i));
Sm(i+1)=(M1+M2+1)*ych3oh(i+1)/(Xh2(i+1)*(1+2*ych3oh(i+1)));
a=Sm(i+1);

end
yco
yh2
yco2
ych3oh
yh2o
Sm
figure(1)
plot(Xh2,yco)
xlabel('Xh2')
ylabel('YCO')
figure(2)
plot(Xh2,yh2)
xlabel('Xh2')
ylabel('YH2')
figure(3)
plot(Xh2,ych3oh)
xlabel('Xh2')
ylabel('YCH3OH')
figure(4)
plot(Xh2,yco2)
xlabel('Xh2')
ylabel('YCO2')
figure(5)
plot(Xh2,yh2o)
xlabel('Xh2')
ylabel('Yh2o')
figure(6)
plot(Xh2,Sm)
xlabel('Xh2')
ylabel('Sm')
ss1=polyfit(Xh2',Sm',5);
yy=polyval(ss1,Xh2);
figure(7)
plot(Xh2,yy)
xlabel('XH2')
ylabel('FUNCTION')

The Final equation of Methanol selectivity is :

Table 2.1: Selectivity Values for All Hydrogen Conversion (XH2)

XH2 SM
0.1 1.00
0.2 0.74
0.3 0.58
0.4 0.48
0.5 0.42
0.6 0.38
0.7 0.33
0.8 0.30
0.9 0.29
1 0.34
 Figure 2.2 Selectivity of Methanol vs H2 conversion (XH2)

2.2.4 Economic Potential of Level 2

EP2 = Product Value + by product value – Raw Materials Costs

Prices of materials
Material Price (RM/Kmole)
Methanol 450
Glycerol 323

Table 2.2: Economic Potential of Level 2 against Hydrogen Conversion XH2

XH2 EP2
RM/yrar
0.1 -718990045.6
0.2 -59219891.29
0.3 156374673.6
0.4 285544341.3
0.5 384968560.6
0.6 452100859.2
0.7 483141536.9
0.8 499916789.4
0.9 576678844.5
1 788088688.6
Figure 2.3: Economic Potential Level 2 vs H2 Conversion
 2.3 LEVEL 3: REACTOR AND RECYCLE STREAMS

2.3.1 Recycle Streams:

1. Gas recycle – CO2, CO, H2 (RD)

2. Liquid recycle – Glycerol (RK)

Thus, the input-output structure shown in below figure.

RD (yCO)D, yCO2)D, yH2)D)

FW
Reforming FR FS FI MeOH FO FP
FG FG2 yCO)S A yCO)o
Reactor yCO)R yCO)I Reactor B PM
yCO2)R yCO2)S yCO2)I yCO2)o
yCO)p
yH2)R yH2)S yH2)I yH2)0
yCO2)p
yH2O)R yH2)p
yC3H8O3)R

RK
yH2O) K Pw
yC3H8O3) K

Figure 2.4: Input and Output Streams after Recycle Stream Decisions
Material Balance on MeOH reactor

CO  2H 2 
 CH 3OH (r1)

CO2  3H 2 
 CH 3OH  H 2 0 (r2)
Let
RD ( y H 2 ) D RD ( yco ) D RD ( yco ) D
Mr    2
(3.1)
FP ( y H 2 ) P FP ( yco ) P FP ( yco ) P
2

Mole balance at point A

FI i  FS i  RDi  FS i  M r FP ( yH 2 ) P

FI ( yH 2 ) I  FS ( yH 2 ) S  M r FP ( yH 2 ) P (3.2)

FI ( yco ) I  FS ( yco ) S  M r FP ( yco ) P (3.3)

FI ( yco 2 ) I  FS ( yco 2 ) S  M r FP ( yco 2 ) P (3.4)

Mole balance at point B

FO i  RD i  FP i  MrFP i  FP i
FO i  FP i (1  Mr )
FO i
FP i 
(1  Mr )
FO ( y H 2 )O
FP ( y H 2 ) P  (3.5)
(1  Mr )
F (y )
FP ( yco ) P  O co O (3.6)
(1  Mr )
FO ( yco 2 )O
FP ( yco 2 ) P  (3.7)
(1  Mr )
Over all mole balance on MEOH reactor

FP ( yH 2 ) P  FS ( yH 2 ) S (1  X o ) (3.8)
 1
FP ( yco ) P  FS ( yco ) S  X o FS ( y H 2 ) S (3.9)
2
1
FP ( yco 2 ) P  FS ( yco 2 ) S  X o FS ( y H 2 ) S (3.10)
3
From the reforming reaction
1
FS ( yco ) S  FS ( y H 2 ) S (3.11)
2
1
FS ( yco 2 ) S  FS ( y H 2 ) S (3.12)
7
Sub. (2.11) and (2.12) in (2.9) and (2.10)
Then the final equations of overall mole balance become
FP ( yH 2 ) P  FS ( yH 2 ) S (1  X o ) (3.13)

1
FP ( yco ) P  FS ( y H 2 ) S (1  X o ) (3.14)
2
1 1
FP ( yco 2 ) P  FS ( y H 2 ) S (  X o ) (3.15)
7 3
Single pass mole balance
FO ( y H 2 )O  FI ( y H 2 ) I (1  X S ) (3.16)

1 1
FO ( yco )O  FI ( yco ) I  X S FI ( y H 2 ) I (3.17)
2 2
1 1
FO ( yco 2 )O  FI ( yco 2 ) I  X S FI ( y H 2 ) I (3.18)
2 3
Selectivity of Methanol produced to H2 reacted
PM
SM  (3.19)
X o FS ( y H 2 ) S

PM
FS ( y H 2 ) S  (3.20)
X oSM
Sub. (2.20) in (2.13), (2.14)and (2.15)
PM
FP ( y H 2 ) P  (1  X o ) (3.21)
X oSM
PM
FP ( yco ) P  (1  X o ) (3.22)
2 X oSM
PM 1 1
FP ( yco 2 ) P  (  Xo) (3.23)
X oSM 7 3
Sub (3.21) in (3.5)
PM
FO ( y H 2 )O  (1  M r ) (1  X o ) (3.24)
X o SM
Sub (3.22) in (2.6)
PM
FO ( yco )O  (1  M r ) (1  X o ) (3.25)
2 X oSM
Sub. (3.33) in (2.7)
PM 1 1
FO ( yco 2 )O  (1  M r ) (  Xo) (3.26)
X oSM 7 3
Sub. (2.24) in (2.16)
(1  M r ) PM
(1  X o )
X oSM
FI ( y H 2 ) I  (3.27)
(1  X S )
Sub. (2.27) and (2.25) in (2.17)
(1  M r )(1  X o ) PM  XS 
FI ( yco ) I  1   (3.28)
2 X oSM  (1  X S ) 
Sub. (2.27) and (2.26) in (2.18)

(1  M r ) PM 1 1  (1  X o ) 
FI ( yco 2 ) I  (  Xo)    (3.29)
X oSM 7 3  3(1  X S ) 
Sub. (2.21), (2.22) and (2.23) in (2.1)

RD ( y H 2 ) D 
M r PM
1  X o  (3.30)
X o SM

RD ( yco ) D 
M r PM
1  X o  (3.31)
2 X oSM

M r PM 1 1 
RD ( yco 2 ) D   7  3 X o  (3.32)
X oSM

FO ( y H 2 )O  FI ( y H 2 ) I (1  X S )  FP ( y H 2 ) P  M r FP ( y H 2 ) P  FS ( y H 2 ) S (1  X o )(1  M r )

FI ( yH 2 ) I (1  X S )  FS ( yH 2 ) S (1  X o )(1  M r ) (3.33)

FI ( y H 2 ) I  FS ( y H 2 ) S  RD ( y H 2 ) D  FS ( y H 2 ) S  M r FP ( y H 2 ) P

FI ( y H 2 ) I  FS ( y H 2 ) S  M r FS ( y H 2 ) S (1  X o )

FI ( y H 2 ) I  FS ( y H 2 ) S 1  M r (1  X o ) (3.34)
Sub. (3.34) in (3.33)

Xo
XS  (3.35)
1  Mr (1  X o )

Material Balance on reforming reactor

3C 3H 8O3  2H 2 0  7CO  2CO2  14H 2 (r3)

C3H8O3 = -3 r3
H2O = -2 r3
CO= 7 r3
CO2= 2 r3
H2 = 14 r3

But C3H8O3 out =0 because all C3H8O3 will be recycled

Then over all conversion of Glycerol = 1

Mole Balance:
For C3H8O3
FG  0  (3r3 )
F
r3  G (3.36)
3
H2
0  FS y H 2 S  (14)(r3 )
PM F
0  (14)( G )
X oSM 3
3PM
FG  (3.37)
14 X o S M
For C0
0  FS yCOS  (7)(r3 )
7 FG
FS yCOS  (3.38)
3
For CO2

0  FS yCO2 S  (2)(r3 )
2 FG
FS yCO2 S  (3.39)
3
For H2O
FW  Rk yH 2Ok  (2)(r3 )
According to the stoichiometric
2 2 PM
FW  FG 
3 14 X o S M
But excess water required to get 100% conversion of limiting reactant
Let
FW  3FG (3.40)

6 PM (2) PM X G
 Rk y H 2Ok 
14 X o S M (3)14 X o S M
2 PM 1
Rk y H 2Ok  (3  X G ) (3.41)
14 X o S M 3

Glycerol in FG2 Stream:

XG is single pass conversion of Glycerol

FG 2  FG  FG 2 (1  X G )

FG 2  FG  FG 2 (1  X G )
FG
FG 2 
XG
3PM
FG 2  (3.42)
14 X o S M X G

3PM
Rk yC3 H 8O3 ) k  (1  X G ) (3.43)
14 X o S M X G
 Table 2.3: Streams Composition after Recycle Streams Decision

S Glycerol H2O CH3OH CO CO2 H2

FG - - - - -
6 PM
FW - 14X o S M
- - - -
3PM - - -
FG2 - -
14 X o S M X G
3PM 2 PM 1
(1  X G ) * (3  X G ) PM PM PM
FR 14 X o S M X G 14 X o S M 3 = 7X oSM X oSM
2X oSM
PM PM PM
FS = = = 2X oSM 7X oSM X oSM
(1  M r )(1  X o ) PM (1  M r ) PM 1 1
(  Xo) (1  M r ) PM
2X oSM X oSM 7 3 (1  X o )
FI = = = X oSM
 XS   (1  X o ) 
* 1     (1  X S )
 (1  X S )   3(1  X S ) 
PM
(1  M r ) (1  X o ) P 1 1 PM
FO = = 2 X o SM (1  M r ) M * (  X o ) (1  M r ) (1  X o )
X o SM 7 3 X oSM

PM PM 1 1 PM
FP = = (1  X o ) (  Xo) (1  X o )
2 X oSM X oSM 7 3 X oSM
PM 1 1
PW = (  Xo) = = = =
X o SM 7 3
M r PM  1 1 
RD = = =
M r PM
1  X o    Xo
M r PM
1  X o 
2 X oSM X oSM 7 3  X oSM
2 PM
3PM 14 X o S M
RK (1  X G ) = = = =
14 X o S M X G 1
* (3  X G )
3
 2.3.2 Determination of Compressor Cost

The annual compressor cost can be calculated based on the below equation which is:

I W W
K pt  MSK 8.74(2.11  Fd )( ) 0.82  C p (8150)
3I MSd  
 n 1 
nZRT1  P2  n 
W  RD    1
(n  1)  P1  
 
Where,

Kpt is the annual cost (RM) , W is power , n is polytrophic index (1.6-1.8),   0.8 , Fd = 1
,and Cp is power cost.

Table 2.4: Compressor Cost Against Hydrogen Conversion ( Xo )

Xo For Mr=1 For Mr=2 For Mr=3 For Mr=4

KPt 1 KPt 2 KPt 3 KPt 4
0.1 35465335.22 70889693.84 106301984.92 141707047.37
0.2 11255146.61 22494319.65 33728788.51 44960439.49
0.3 5027028.23 10045814.46 15062173.44 20077078.46
0.4 2626635.47 5248434.16 7868808.43 10488329.45
0.5 1473946.14 2944882.76 4414933.09 5884452.51
0.6 819621.11 1637383.74 2454599.05 3271486.50
0.7 412565.06 824072.69 1235268.92 1646278.62
0.8 157780.50 315081.03 472240.21 629314.72
0.9 5949.77 11867.17 17775.04 35514.95

2.3.2 Adiabatic Temperature Calculation

A- MeOH reactor
B-
Energy balances in reactor at adiabatic with assumption of specific heat enthalpy can be used
and the reference temperature is T m, can be defined as:

n m K
n j H r m
j
  Pi C P i (Ta  Tm)   Fk C P k (Tm  Tm)  0
j 1 i 1 k 1
with H rjm as heat of reaction at inlet temperature for the reaction j, c pi as specific heat

enthalpy for each component i include the reactant, T a as adiabatic temperature for the

 reactor, cpk as specific heat enthalpy for key component.

 n m
n j H r m
j
  Pi C P i (Ta  Tm)  0
j 1 i 1
Then the above equation can be simplified as:
n
 n j  H mr j
j 1
Ta  Tm 
m
 Pi C P i
i 1
In MeOH reactor, only these reactions are considered for the calculation of adiabatic
temperature.

where from the reactions:

PH 2  FI ( y H 2 ) I (1  X o )
1
Pco  FI ( y H 2 ) I (1  X o )
2
1
Pco 2  FI ( y H 2 ) I (1  X o )
3
1
PH 2 O  FI ( y H 2 ) I X o
3
PCH 3OH  FI ( y H 2 ) I S M X o

Component Cp
KJ/Kmole . K
CH30H 79.5
H2O 36.5
CO 29
CO2 38
H2 27
n n m
n j H r m
j
  n j  H r   Pi C P i (Tm  25)
0
j
j 1 j 1 i 1

M
 Pi c pi  PH 2
c pH 2  Pco c pco  Pco 2 c pco 2  PH 2 O c pH 2 O  PCH 3 OH C p
CH 3 OH
i 1
 n
 n j  H mr j  FI ( y H 2
) I S M X o (-90.77 - 49.57)
j 1
 1 
  
  3 FI ( y H 2 ) I X o  c pH 2 O  FI ( y H 2 ) I S M X o C p CH 3 OH 
  

  1  
  FI ( y H 2 ) I (1  X o ) c pH 2   FI ( y H 2 ) I (1  X o ) c pco  (Tm  25)
 2  
 1  
  FI ( y H 2 ) I (1  X o ) c pco 2 
 3  

 1  
  3 X o c pH 2 O  S M X o C p CH 3 OH  
n    
 n j  H r j  FI ( y H 2 ) I S M X o (-90.77 - 49.57)   (1  X o )c pH 2  2 (1  X o )c pco (Tm  25)
  
m 1
j 1   1  
  (1  X o )c pco 2  
  3  

M
1 1 1 
 Pi c pi FI ( y H 2
) I  X o c pH 2 O  S M X o C p
3 CH OH
 (1  X o )c pH 2  (1  X o )c pco  (1  X o )c pco 2 
2 3 
i 1
3

1 
 3 X o c pH 2 O  S M X o C p CH 3 OH  (1  X o )c pH 2 
S M X o (-90.77 - 49.57)    (Tm  298)
 1 (1  X )c 1 
 2 o pco  (1  X o )c pco 2
Ta  Tm   3 
1 1 1
X o c pH 2 O  S M X o C p  (1  X o )c pH 2  (1  X o )c pco  (1  X o )c pco 2
3 CH 3 OH 2 3

For Tm= 473 K

Table 2.5: Adiabatic Temperature against Hydrogen Conversion Xo

XH2 Sm Ta (k) Ta( C )
0.1 1.017742176 836.0376058 563.0376058
0.2 0.737970272 919.3009281 646.3009281
0.3 0.576843248 973.6327553 700.6327553
0.4 0.482496544 1023.970966 750.9709663
0.5 0.423575 1077.792569 804.7925689
0.6 0.377814176 1131.795498 858.7954977
0.7 0.334730272 1181.814972 908.8149719
0.8 0.298310048 1235.556081 962.5560809
0.9 0.289700744 1329.394184 1056.394184
0.99 0.339161745 1494.71152 1221.71152
 Figure 2.5: Adiabatic Temperature against H2 conversion (Xo)

From Figure 2.5, it can be seen that the adiabatic temperature is greater than the operating
temperature which is 200 oC, even at lower conversion. Thus, an adiabatic operation is not
suitable for this reaction. The reactor will need to be operated isothermally and hence the
heat load, Q need to be determined.

Isothermal heat load can be obtained from:

n n m
Q n j H r m
j
  n j  H r   Pi C P i (Tm  25)
0
j
j 1 j 1 i 1

 1  
  3 X o c pH 2 O  S M X o C p CH 3 OH  (1  X o )c pH 2  
Q  FI ( y H 2 ) I  S M X o (-90.77 - 49.57)    (Tm  25)
  1 (1  X )c 1  
  2 o pco  (1  X o )c pco 2  
3 
 Figure 2.6: Required Heat against H2 Conversion (Xo)

B. Adiabatic temperature calculation of reforming reactor

n
 n j  H mr j
j 1
Ta  Tm 
m
 Pi C P i
i 1
In reforming reactor only one reaction is considered for the calculation of adiabatic
temperature.

Where from the reactions:

PC3 H 8 O3  FG2 (1  X G )
2
PH 2 O  FG2 (1  X G )
3
7
Pco  FG2 X G
3
2
Pco 2  Pco  FG2 X G
3
 14
PH 2  FG2 X G
3
n n m
n j H r m
j
  n j  H r   Pi C P i (Tm  25)
0
j
j 1 j 1 i 1

M
 Pi c pi  PH 2
c pH 2  Pco c pco  Pco 2 c pco 2  PH 2 O c pH 2 O  PC3 H 8 O3 C p
C 3 H 8 O3
i 1
 14 7 2  
n   X G c pH 2  X G c pco  X G c pco 2  
 j Hr j
n 
m
 FG 
2 G

X (931.9)  
3 3 3
 (Tm  25) 

j 1  2
 (1  X G )c pH 2 O  (1  X G )C p 
  3 C 3 H 8 O3  

M
14 7 2 2 
 i pi 2  3 G pH 2 3 G pco 3 G pco 2 3 (1  X G )c pH 2O  (1  X G )C pC3 H 8O3 
P c  FG X c  X c  X c 
i 1

14 7 2 
 3 X G c pH 2  3 X G c pco  3 X G c pco 2 
X G (931.9)    (Tm  25)
 2 (1  X )c 
 3 G pH 2 O  (1  X G )C p C H O 
Ta  Tm   3 8 3 

14 7 2 2 
 3 X G c pH 2  3 X G c pco  3 X G c pco 2  3 (1  X G )c pH 2 O  (1  X G )C p C 3 H 8 O3 

Table 2.6: Adiabatic Temperature at Reforming Reactor against Hydrogen Conversion (Xo)

XG Ta ( K ) Ta ( C )
0.1 1162.604261 889.6043
0.2 988.0860948 715.0861
0.3 784.5069112 511.5069
0.4 578.0661801 305.0662
0.5 368.6511733 95.65117
0.6 156.1431629 -116.857
0.7 -59.58298377 -332.583
0.8 -278.6592413 -551.659
0.9 -501.2249008 -774.225
0.99 -700.8842267 -973.884
 Figure 2.7 Adiabatic Temperature against Glycerol Conversion (XG)

From Figure 2.7, it can be seen that the adiabatic temperature is less than the operating
temperature which is 800 K , even at lower conversion. Thus, an adiabatic operation is not
suitable for this reaction. The reactor will need to be operated isothermally and load, Qr need
to be applied Isothermal heat load can be determined bythe following equation:
N
Qriso   n j H rm
j 1

 14 7 2  
  3 X G c pH 2  3 X G c pco  3 X G c pco 2  
Q  FG 2  X G (931.9)    (Tm  25)
  2 (1  X )c  (1  X G )C p  
  3
G pH 2 O C 3
H 8
O 
3 


3PM
FG 2 
14 X o S M X G
 Figure 2.8: Required Heat against Glycerol Conversion (XG)

2.3.3 Determination of Reactors Volumes and Reactors Cost

A- MeOH reactor
Operation conditions:

Temperature, T = 200°C = 473.15 K

Pressure, PT = 80 bar
R = 8.3144 kJ.K/kmole

r1  k1o exp(  E1 / RT ) PT yCO yH2 2

r2  k2o exp( E2 / RT ) PT yCO2

Reaction kio (kmole/(kgcatalyst.atm.hr)) ΔE (kJ/kmole)

1 2.934 x 10-9 -9.45 x 104
2 1.940 x 105 4.94 x 104
 X
V dX
F
  (r )
0
Xo
V dX o
FI ( y H 2 ) I
  2r1  3r2
0

FI ( y H 2 ) I (1  X o )
yH 2 
 1 1 1 
FI ( y H 2 ) I (1  X o )  (1  X o )  (1  X o )  X o  S M X o 
 2 3 3 
(1  X o )
yH 2 
1.8333(1  X o )  X o (1  S M )

(1  X o )
yCO 
21.8333(1  X o )  X o (1  S M )

(1  X o )
yCO2 
31.8333(1  X o )  X o (1  S M )

FI ( y H 2 ) I X o dX o
V 
PT  (1  X o ) 3
(1  X o )
0 K  K2
1
1.8333(1  X o )  X o (1  S M ) 3 1.8333(1  X o )  X o (1  S M )
 Figure 2.9: -1/rH2 against Hydrogen Conversion (Xo) in MeOH Reactor
Solving the integration by numerical method gives:

Figure 2.10: MeOH Reactor Volume against Hydrogen Conversion (Xo)

Diameter and Length of reactor

Some assumption from (L.T.Biegler, Systematic Methods of Chem. Eng. Design; page 112)
For general costing purposes, the aspect ratio L/D = 6. So Length, L = 6D
Thus, V = π r2 L
V= D3

Table 2.7: MeOH Reactor Dimensions against Hydrogen Conversion (Xo)

M=1 M=2 M=3 M=4

Xo V D L V D L V D L V D L
(m3) (m) (m) (m3) (m) (m) (m3) (m) (m) (m3) (m) (m)
0.10 1.38 0.66 3.98 2.05 0.76 4.55 2.72 0.83 4.99 3.45 0.90 5.41
0.20 1.93 0.74 4.46 2.83 0.84 5.06 3.74 0.93 5.55 4.82 1.01 6.05
0.30 2.59 0.82 4.92 3.76 0.93 5.56 4.92 1.01 6.09 6.48 1.11 6.67
0.40 3.63 0.92 5.50 5.19 1.03 6.20 6.75 1.13 6.76 9.08 1.24 7.47
0.50 4.84 1.01 6.06 6.80 1.13 6.78 8.75 1.23 7.38 12.10 1.37 8.22
0.60 6.90 1.14 6.81 9.44 1.26 7.56 11.98 1.37 8.19 17.25 1.54 9.25
0.70 10.47 1.31 7.83 13.81 1.43 8.59 17.15 1.54 9.23 26.17 1.77 10.63
10.9
0.80 19.27 1.60 9.60 23.96 1.72 10.32 28.65 1.83 48.18
5 2.17 13.02
14.6 134.8
0.90 53.94 2.25 13.52 61.20 2.35 14.11 68.46 2.44
4 5 3.06 18.36
0.99 594.47 5.02 30.10 604.03 5.04 30.26 613.59 5.07 30.4 1486. 6.81 40.85
 2 18

The annual reactor cost can be calculated based on the below equation which is:

 I   7775.3  1.066 0.82

CRT   MSk    DR LR  2.18  Fm Fp  FI
 I MSd   3 

Where CRT is the annual reactor cost

IMSk = Marshall and Swift index now
= 1,565
IMSd = Marshall and Swift index previous
= 280
DR = Diameter of the reactor
LR = Length of reactor
Fm = Construction material factor
= 2.15
Fp = Pressure factor
= 2.5
FI = Installation factor in Malaysia
= 1.5

Table 2.8: Annual Cost of MeOH Reactor against Hydrogen Conversion (Xo)

For Mr=1 For Mr=2 For Mr=3 For Mr=4

Xo
CRT 1 CRT 2 CRT 3 CRT 4
0.1 329516.6 422556 504744.1 586204.2
0.2 406909.4 518131.3 616677.5 723884.6
0.3 489914.9 618734.7 733276.5 871549.9
0.4 606041 758295 894223.5 1078136
0.5 725867.6 898325.9 1053037 1291306
0.6 906995.9 1104568 1283088 1613530
0.7 1178843 1403010 1607703 2097140
0.8 1730037 1983927 2219888 3077705
0.9 3304010 3576958 3838112 5877775
0.99 14936873 15087403 15237052 26572435
 A- Reforming Reactor
Operation conditions:

Temperature, T = 800 K
Pressure, PT = 25 MPa
 
r glycerol  K P glycerol P steam

K  1.987 mole.m -2S-1KPa -(   )

  0.08
  0.39

X
V dX
F
  (r )
0
(1  X G )
y glycerol 
1.6667(1  X G )  7.6667 X G
(1  X G )
y glycerol 
1.6667  6 X G
0.6667(1  X G )
yH 2O 
1.6667  6 X G
XG
dX G
V  FG 2  0.08 0.39
0 0.08  (1  X G )  0.39  0.6667(1  X G ) 
P K  P T  1.6667  6 X 
T
1.6667  6 X G  G 

XG
3PM dX G
V 
0.47  0.47
14( X o )( S M )( X G )(0.8537)(P )( K ) 0  (1  X G ) 
T  
1.6667  6 X G 

XG
(0.251) PM dX G
V 
0.47  0.47
( X o )( S M )( X G ) ( P )( K ) 0  (1  X G ) 
T  
1.6667  6 X G 
 Figure 2.11: -1/r Glycerol against Glycerol Conversion (XG) in Reforming Reactor

For Xo = 0.99
Solving integration by numerical methods give
 Figure 2.12: Reforming Reactor Volume against Glycerol Conversion (XG)

For maximum conversion in reforming reactor which is (0.8)

The value of (-1/r Glycerol) will be constant and the feed will vary with hydrogen conversion
(Xo) so reforming reactor volume and dimensions will be as follows:

For general costing purposes, the aspect ratio L/D = 6. So Length, L = 6D

Thus:
3

Table 2.9: Reforming Reactor Dimensions against Hydrogen Conversion (Xo)

Xo V D L
(m3) (m) (m)
0.10 5028.20 10.22 61.32
0.20 3467.22 9.03 54.18
0.30 2957.13 8.56 51.38
0.40 2651.53 8.26 49.54
0.50 2416.29 8.01 48.03
0.60 2257.46 7.83 46.96
0.70 2184.02 7.74 46.44
0.80 2144.33 7.69 46.16
0.90 1962.72 7.47 44.82
 0.99 1524.08 6.87 41.19

The annual reactor cost can be calculated based on the below equation which is:

Note: Data from table 2.9 will be used for cost calculations

 I   7775.3  1.066 0.82

CRT   MSk    DR LR  2.18  Fm Fp  FI
 I MSd   3 
Where CRT is the annual reactor cost
IMSk = Marshall and Swift index now
= 1,565
IMSd = Marshall and Swift index previous
= 280
DR = Diameter of the reactor
LR = Length of reactor
Fm = Construction material factor
= 2.15
Fp = Pressure factor
= 2.5
FI = Installation factor in Malaysia = 1.5
Table 2.10: Reforming Reactor Cost against Hydrogen Conversion (Xo)
Xo V D L CRT
(m3) (m) (m) (RM)
0.10 5028.20 10.22 61.32 57175585.14
0.20 3467.22 9.03 54.18 45261013.26
0.30 2957.13 8.56 51.38 40952176.65
0.40 2651.53 8.26 49.54 38237881.66
0.50 2416.29 8.01 48.03 36068622.84
0.60 2257.46 7.83 46.96 34559348.93
0.70 2184.02 7.74 46.44 33848207.83
0.80 2144.33 7.69 46.16 33460193.68
0.90 1962.72 7.47 44.82 31649446.41
0.99 1524.08 6.87 41.19 26996479.00

2.3.4 Number of Reactors

A- In reforming section will be 4 packed bed reactors

B- In methanol production will be 4 packed bed reactors

2.3.5 Economic Potential of Level 3:

EP3 = EP2 – KPt – CRT (reforming) – CRT (Methanol)

Table 2.11: Economic potential of Level 3 against Hydrogen Conversion (Xo)

For Mr = 1 For Mr = 2 For Mr = 3 For Mr = 4

Xo EP 3( 1 ) EP 3( 2 ) EP 3(3 ) EP 3( 4 )
0.1 -811960482.62 -847477880.59 -882972359.77 -918458882.32
0.2 -116142960.53 -127493355.48 -138826370.57 -150165228.68
0.3 109905553.89 104757947.85 99627047.03 94473868.66
0.4 244073783.17 241299730.51 238543427.78 235739994.05
0.5 346700123.96 345056729.05 343431968.10 341724179.58
0.6 415814893.20 414799558.21 413803823.05 412656494.07
0.7 447701921.32 447066246.01 446450357.29 445549910.21
0.8 464568778.57 464157587.25 463764467.82 462749576.11
0.9 576643252.50 576619595.19 572811090.34 570783252.84
0.99 746155336.81 746004806.85 745855157.26 734519774.98

Figure 2.13 Economic Potential of Level 3 against Hydrogen Conversion (Xo)

2.4 LEVEL 4: SYNTHESIS OF CHEMICAL SEPARATION SYSTEM

Basically, effluent from reactor consists of product, by-products and un-reacted reactants. In
order to obtain the product in desired purity and recycle un-reacted reactant, separation has to
be carried out.

There will be two different separation processes for methanol production from glycerol. The
first separation process is the separator after reformer reactor to separate the syngas and
water before the methanol synthesis section. There is also one separator located after
methanol reactors to separate the unreacted gases from methanol and water. Second is the
distillation column to purify methanol as the final product. This will involve methanol-water
separation.

2.4.1 Phase Separator

The separation of the water and gas phase after the reformer section was performed in a high
pressure separator (HPS). The product from the reactor is vapor phase at high temperature
and pressure, the stream then is cooled down just before the stream entering the separator.
The liquid phase in the HPS consist water and can be recycled via a recycle pump. The gas
phase from the HPS which is syngas was directly fed to the methanol synthesis section
without upgrading or selective removal of components. It is assumed as 100% recovery of
syngas as the feed to methanol reactor. Figure 2.14 below shows the arrangement of
separation system in the high pressure separator.

CO
CO 2
H2 To Methanol synthesis
section

CO
CO 2
H2
C3H8O3
H2O
HPS
S-01

C3H8O3
H2O

Figure 2.14: Separation of syngas and water

2.4.1.1 Flash Calculation for Phase Separator

The calculation procedures are as follows:

1. Assume key component recovery,  k .

n k
2. Calculate Kk and Kn by using Antoine Equation (4.1) and Equation (4.2) and
using Equation (4.3) at known temperature T.

3. Calculate  n using Equation (4.4).

4. Recalculate mass balance and mole fraction of liquid outlet using Equations (4.5) and
(4.6).

5. If the calculated pressure using bubble-point equation (4.7) equals to the operating
pressure, then the solution is achieved.

6. If not, reassumed the recovery of key component and repeat the procedure.

Component vapor pressure Pon can be calculated from Antoine Equation given by:
Bn
ln Pno  An 
T  Cn  (4.1)
where An, Bn, and Cn are the Antoine constants and T is the temperature. Assuming ideal
condition, then
Pno
Kn 
P (4.2)
The relative volatility can be written by:
Kn
n k 
Kk (4.3)
The recovery of component n, is calculated using:
 n kk
n 
1   n k  1  k
(4.4)
The vapor and liquid streams are calculated from:
vn  n f n
(4.5)
ln  1  n  f n
(4.6)
At the known temperature T, the bubble-point pressure can be calculated using:
 o
P P T 
n k n
(4.7)
where
    n k xn
The following tables show the calculated values for both Separator 1 and Separator 2.

Table 2.12: Flash calculation for Separator 1

Top product(kgmole/hr) Bottom product(kgmole/hr)

Xo
CO CO2 H2 Glycerol Water
0.1 1752.58 500.74 3505.16 327.61 1456.06
0.2 1208.50 345.29 2417.00 163.81 728.03
0.3 1030.71 294.49 2061.42 109.20 485.35
0.4 924.19 264.05 1848.38 81.90 364.02
0.5 842.20 240.63 1684.40 65.52 291.21
0.6 786.84 224.81 1573.68 54.60 242.68
0.7 761.24 217.50 1522.48 46.80 208.01
0.8 747.41 213.55 1494.82 40.95 182.01
0.9 684.11 195.46 1368.21 36.40 161.78
0.99 531.22 151.78 1062.44 33.09 147.08
 Table 2.13: Flash calculation for Separator 2

Bottom
Xo Top product(kgmole/hr) product(kgmole/hr)
CO CO2 H2 Methanol Water
0.1 1577.32 383.90 3154.64 356.74 383.90
0.2 966.80 184.15 1933.60 356.74 184.15
0.3 721.50 88.35 1442.99 356.74 88.35
0.4 554.51 17.60 1109.03 356.74 17.60
0.5 424.68 0.00 849.36 356.74 0.00
0.6 312.92 0.00 625.84 356.74 0.00
0.7 231.64 0.00 463.29 356.74 0.00
0.8 148.64 0.00 297.28 356.74 0.00
0.9 68.41 0.00 136.82 356.74 0.00
0.99 10.60 0.00 21.20 356.74 0.00

2.4.1.2 Annual Cost of Phase Separator

Annual cost of a phase separator in RM/year can be calculated by using the following
formula:
(4.8)

Where,
D = Diameter of column
L = Length of column
Fm = Design material’s factor
Fp = Pressure factor
FI = Installation factor = 1.5
IMSk = Recent Marshall and Swift index
IMSd = Early Marshall and Swift index = 280
2.4.2 Distillation Column

In general, distillation is the least expensive means of separating mixtures of liquids. The
separation of liquids by distillation relies on relative volatilities of components. If the relative
volatility is larger the separation process becomes easier.

For methanol-water mixture, methanol is the light key, while water is the heavy key. At
atmospheric pressure (1 atm), methanol boils at 64.65°C, and water boils at 100.00°C. Thus,
the distillation separation of methanol from water is not a difficult one. The following Figure
2.15 shows the overall separation in Methanol synthesis section consists of a phase separator
and a distillation column.

CO
CO2
H2 CH3OH

CO
CO2
H2
CH3OH CH3OH DISTILLATION
H2O H2O COLUMN
SEPARATOR C-01
S-02

H2O

Figure 2.15: Overall separation in Methanol Synthesis Section

2.4.2.1 Sizing Distillation Column

Determination of Minimum Number of Stages

Using the specified flow of light key (LK) and heavy key (HK) component, the minimum
number of stages of column is calculated by using the following formula:

(4.9)

Where,
d = distillate flow rate
b = bottom flow rate
α = mean relative volatility = [(αLK,HK)N(αLK,HK)1]1/2
and Nactual = 2Nmin
Height of column is calculated by the following equation:
H = (0.69 Nactual)/Eo + 4 (4.10)
(4.11)

Where, Eo= plate efficiency

Nt - number of theoretical equilibrium stages,
Na - actual number of stage required

Minimum and Actual Reflux Ratio

Minimum reflux ratio is estimated by using Underwood Equation:

(4.12)

And actual reflux ratio for all column is set to R=1.2Rmin.

Theoretical and Actual Number of Stages

The theoretical number of stages, N is calculated by using Gilliland correlation:
(4.13)

Where,
(4.14)

Column diameter is determined by using the following equation:

(4.15)

The area of condenser is calculated by the following equation:

 (4.16)

The area of reboiler is calculated by:

(4.17)

Where,
∆Hv = Enthalpy heat of vaporization
Uc = Overall heat transfer coefficient for condenser.
UR = Overall heat transfer coefficient for reboiler.

Calculation for Distillation Column:

Feed Distillate Bottom
Component Molar Mol Molar Mol Molar Mol
flow fraction flow fraction flow fraction
Methanol (LK) 388.3 0.71673804 356.735 0.99901984 31.565 0.17092189
Water(HK) 153.41 0.28316967 0.3 0.00084014 153.11 0.82907811
Carbon Monoxide 0.05 9.2292E-05 0.05 0.00014002 0 0
SUM 541.76 1 357.085 1 184.675 1

Fenske ( Nmin)

Methanol Water
Parameter/Component (LK) (HK)
Distillate Flow Rate,
di 356.735 0.3
Bottom Flow Rate,bi 31.565 153.11
(αlk,hk)N 3.190282151
(αlk,hk)1 1.979918231
Nmin 7.530382807
 Gilliland correlation

R = k*Rmin 1 < k < 1.5

Assume k =1.5

Rmin 1.41614329
Reflux Ratio,R 2.124214935
X 0.226639863
Y 0.438114508
(N-Nmin)/(N+1) 0.438114508
N 15.01749845
Nt 15

Calculated column diameter = 1.5 m

Column Height Estimation

Tray Spacing,H (m) 0.6

Tray Thickness,s (m) 0.006
Estimated column height (m) 14.55
Estimated column head closure height (top+bottom)
(m) 3
Total column height (m) 17.55

2.4.2.2 Annual Cost of Distillation Column

Annual cost of a distillation column in RM/year can be calculated by using the following
formula:
(4.18)

Where,
D = Diameter of column
L = Length of column
 Fm = Design material’s factor
Fp = Pressure factor
FI = Installation factor = 1.5
IMSk = Recent Marshall and Swift index
IMSd = Early Marshall and Swift index = 280

2.4.3 Economy Potential Analysis of Level 4

The economy potential for level 4 is given by

fPE4=fPE3-Kmt1(S-01)-Kmt2(S-02)-Kmt3(C-01) (4.19)
By subtracting the annualized cost of the separator and distillation column from EP3, we can
calculate the economic potential at level 4 as shown in Table 4.3 and Figure 4.3. The
comparison between EP 2, 3 and 4 is shown in Figure 4.3.1.

Hence, the economy potential of level 4 is shown as following:

Table 2.14: Economic Potential Level 4

Economic Potential Level 4 (RM)

Xo
Mr = 1 Mr = 2 Mr = 3 Mr = 4
0.1 -951007767 -986525165 -1022019644 -1057506166
0.2 -253815657 -265166052 -276499067 -287837925
0.3 -27254298 -32401904 -37532805 -42685983
0.4 107240959 104466906 101710604 98907170
0.5 210115499 208472104 206847344 205139555
0.6 279438865 278423530 277427795 276280466
0.7 311436622 310800947 310185058 309284611
0.8 328439348 328028156 327635037 326620145
0.9 440580487 440556829 436748324 434720487
0.99 610265302 610114772 609965122 598629740
 Figure 2.16: Economic Potential Level 4

Figure 2.17: Comparison of EP2, EP3, and EP4

2.5 LEVEL 5: HEAT INTEGRATION

2.5.1 Heat Exchanger Network

Heating and cooling cost in the process plant is part of the important production cost. Entire
heat exchangers are assumed as one perfect network. Hot stream can be used to heat up cold
stream to minimize heating and cooling utility cost. The method to choose optimum heat
exchanger network is called heat integration. The main purpose of this selection is for
minimum heating and cooling requirement and minimum heat exchangers for minimum
capital cost.

2.5.2 Determination of Minimum Heating and Cooling Requirement

Table 2.15 shows the entire cold and hot stream in this plant:

TABLE 2.15: Hot and Cold Stream

Tout
Stream Tin (C) (C) Q(kW) FCp (kW/C)
E-1 C1 30 750 45268.13 -62.87240278
E-2 H1 312.8 45 22987.69 85.83902166
E-3 C2 120 300 8931.99 -49.62216667
E-4 H2 62.2 25 6585.98 177.0424731

Hence, total Q available is 83773.39 kW.

2.5.3 Temperature Intervals

A very simple way of incorporating second-law considerations into the energy integration
analysis was presented whereas heat only can be transferred if for the minimum driving force
of 10 oC. Table 5.2 shows a series of temperature intervals for hot and cold stream.
 TABLE 2.16: Temperature Intervals

One way we could satisfy the net heating and cooling requirements in each temperature
interval is simply to transfer any excess heat to a cold utility and to supply any heat required
from a hot utility as shown in figure 2.18 below.

Figure 2.18: Heat transfer to and from utilities for each temperature interval

From this figure, we see that we would need to supply 29573.67 kW heat and that we have to
reject 54200.1 kW heat.
 CHAPTER 3
SIMULATION
The overall process has been done using iCON Simulation. Process Flow Diagram has been developed based on this simulation. The result of simulation as
follows:
 CHAPTER 4
MATERIAL AND ENERGY BALANCE

Material and Energy Balance has been developed from iCON simulation as follows:

Table 4.1: Material Balance for Overall Process

Table 4.2: Energy Balance for Overall Process