Petrochemical Developments

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Use new economics for

purification on a small scale
For smaller methanol units, new designs balance energy
cost against capital cost for long-term profitability
K. Patwardhan, G. Satishbabu, S. Rajyalashmi and P. Balaramkrishna, Larsen and
Toubro, Powai, Mumbai, India

C rude methanol (MeOH) distillation is an energy intensive

separation process and contributes significantly to the total production
summarizes a typical composition of the crude MeOH
cost of this alcohol. It is very important to choose the right distillation obtained through commercial processes. US federal-grade
configuration columns for MeOH purification.
specification OM-232e identifies three grades of MeOH.
In the presented study, a two-column configuration is compared
with three-column configuration with forward- and backward-heat Grade “C” is for wood alcohol used in denaturing. Grade “A”
integration schemes. Reduction of approximately 64% in low- covers methanol gen-erally used as a solvent. Federal-grade
pressure (LP) steam consumption is observed in a three-column “AA” is the purest product and it is used for
configuration case as compared to the base case of two-column case petrochemical/chemical applications in which high-purity
for a small capacity plant (about 23,000 metric tpy). Further reduc-
and low-ethanol content are required, such as for MTBE,
tion in specific energy consumption for a three-column configura-
tion is possible with a backward-heat integration scheme. methyl amines manufacture, etc. The general standard
observed by the chemical industry for MeOH product purity
is US federal -grade “AA”. Another known methanol grade is
the fuel-grade; it is used as a blending component for
gasoline.
Purification schemes. Crude MeOH is purified by distil-
KEY PETROCHEMICAL lation with one- or two- or three- or four-column configuration.
Methanol is one of the most important petrochemicals pro- Fuel-grade methanol is normally produced with a single distillation
duced globally. It is extensively used as feedstock in the production tower. But to produce federal-grade AA methanol, two-, three-,
of chemicals such as formaldehyde, methyl tertiary-butyl ether and sometimes, even four -tower distillation systems are used. The
(MTBE), tertiary amyl methyl ether (TAME) and acetic acid, and amount of distillation required depends on the byproduct forma-
also as a hydrogen source in the fuel cells used in automobiles. The tion of the MeOH synthesis catalyst and plant capacity.
majority of MEOH is produced via natural gas through steam The economics of the purification scheme involves the complex
reforming; other processing methods include use of petroleum relationship of plant capacity, heat available in the plant, the energy
fraction and process offgas. The MeOH-manufacturing process export requirement and customer requirements, etc. For example,
can be divided into three major sections: feedstock purification the four-column configuration is justified only at large capacities
and syngas generation, compression and MeOH synthesis, and such as 5,000 metric tpd of MeOH production where as choice
MeOH purification. Fig. 1 is a general flow diagram of a MeOH of two- or three-column configuration depends very much on
facility using natural gas as the feedstock. customer’s requirements and energy availability in the front end.
In this design, three process sections may be considered inde-
pendently, and the technology may be selected and optimized Single-column configuration. For fuel-grade MeOH as a
separately for each section. The normal criteria for technology blending component (for gasoline), the major demands regard-
selection are capital cost and plant efficiency. ing quality are the water content and dissolved gases. Fuel-grade
In a conventional natural gas-based
+
MeOH plant with a capacity of 2,500 Natural
metric tpd, syngas generation accounts for gas
Desulfurization
Syngas
Compression
MeOH MeOH MeOH
55%, distillation accounts for 12%, com- production synthesis distillation
pression and MeOH synthesis accounts
for 12% and utilities and other services Reforming Reactor Distillation
account for 24% of the total capital cost. technologies technologies technologies
1. Steam 1. Isothermal 1. Single column
Methanol purification. Crude 2. Combined 2. Adiabatic 2. Multicolumn
MeOH, as removed from the MeOH 3. Autothermal
synthesis section, contains water, higher Fig. 1 General flow diagram for a natural-gas based MeOH facility.
alcohols, impurities and light ends. Table 1

HYDROCARBON PROCESSING January 2012 I1

Petrochemical Developments

MeOH should be dissolved-gas free and preferably should not 2–8

tives to this standard two-column arrangement. A double-
contain more than 500 wt-ppm of water. The limitation on water effect three-column scheme was developed and it is widely
4
content is due to its immiscibility with gasoline (Fig. 2). applied in industry. A number of these alternative schemes
involve split-ting the refining column into two separate columns
Multi-column configuration. The condensate from the syn-thesis operating at different pressures, such that the overheads of the
loop is generally purified in two stages using conventional dis- higher pressure column can be used to reboil the lower pressure
tillation columns operating at pressures slightly above atmospheric column. Several novel energy-saving three-column distillation
9
pressure. The first distillation stage is for light ends removal, and is configurations have been explored in the literature.
carried out in a single-distillation column known as the topping col- The capital cost of the three-column schemes is significantly
umn. This column acts as a refluxed stripper. The liquid feed enters greater than the standard two-column arrangement. The three-
near the top stage and MeOH vapor generated in the reboiler strips column distillation unit consists of a topping column and two
the light ends—such as di-methyl ether (DME), methyl formate and refining columns. Refining column II operates at normal pressure.
acetone—and residual dissolved gases from the crude MeOH. Refining column I operates at a higher pressure, thus utilizing the
The main area of investigation is the second stage of MeOH condensation duty of this column as the reboiler duty of refining
purification. This is the MeOH refining stage, where MeOH is column II. This substantially reduces the LP steam consumption of
recovered as the overhead product from one or more distillation the distillation section. Another configuration of three-column
columns. Water is withdrawn as the bottoms product. Middle systems is operating refining column I at atmospheric pressure and
boiling impurities (principally ethanol, but also higher alcohols, refining column II at high pressure (HP).
ketones and esters), referred to as fusel oil are withdrawn as a Federal-grade “AA” MeOH is withdrawn close to the top of both
side stream below the feed stage. refining columns. Although the three-column system is more costly,
Provision of this side stream enables the MeOH production it can reduce the required distillation heat input by 30%–40%.
to US federal specification O-M- 232K Grade ‘‘AA’’. In typical Multi-column systems (three or more columns) can generally only
two-column MeOH purification scheme, as shown in Fig. 3, be justified when energy costs are prohibitively high. The design of
about 20% of the total heat for purification is associated with the the MeOH distillation unit primarily depends on the energy
topping column. The remainder is required to separate methanol situation in the front end. The two-column distil-lation unit
from ethanol and water. This basic arrangement is widely represents the low-cost unit, and the three-column distillation unit is
1,2
reported in the literature. the low-energy system. Multi-column design maximizes the yield
With the sharp rise in energy costs, MeOH technology licen-sors and minimizes LP steam consumption.
and operators have focused considerable attention on alterna- The four-column design (Fig. 4) includes the three columns
described previously as well as an additional recovery column.
Table 1. Typical crude MeOH composition to The fusel oil purge from refining column II is processed in the
MeOH purification section recovery column to minimize MeOH losses even further. The
Component Wt% distillation unit can be designed to limit the MeOH content in
the process water to a maximum of 10 wt-ppm. Furthermore, the
CO, CO2, H2, CH4, N2, DME, aldehydes, ketones 0.5–0.8
heat available from the front end (syngas generation) at a low
Methanol 88–90
temperature is efficiently used to minimize steam consump-tion.
Ethanol, higher alcohols (propanol, butanol, etc.) 0.1–0.6
As we go higher up in the column configuration, MeOH
Water 9–11 recovery increases but specific steam consumption decreases. In

Tail gas Condenser 1 Condenser 2

Stripped gas

Liquid off Product

Fuel-grade
Reflux steam Reflux MeOH
product
drum 1 drum 2

Raw MeOH Crude

MeOH Higher alcohols

Stabilizer Concentration
column column

Process LP
Process gas
gas steam
Recycle water
LP steam
Stabilizer MeoH pump
Fig. 2 Single-column configuration for an MeOH plant.
Fig. 3 Two-column configuration for an MeOH plant.

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 Petrochemical Developments

four-column configurations, as high as 60% savings in the In backward-heat integration, the second and third
steam consumption can be achieved when compared to the columns are exchanged. In this scheme, the overheads from
base case of a two-column configuration. third column (HP) supply heat for the second-column
reboiler. The material and heat flows in the opposite
Simulation study direction. The basic assumptions made are:
An analysis was conducted for purifying “AA” grade MeOH •  All trays behave ideally (tray efficiency is 100%).
from crude MeOH through a two-column and three-column •  Liquid reflux from the condenser is saturated at
configuration using a commercially available process simulator. calculated conditions.
2
The results were validated with the reference data available for •  Pressure drop/ tray is 0.01 kg/cm .
the two-column scheme. The simulations were extended for the •  Negligible pressure drop in reboiler and condenser.
three-column configuration. As in three-column configuration, •  Reductions or increases in the pressure between the
due to higher degree of freedom, one extra case is generated for columns are achieved by the reduction valve and pump respectively.
the reboiler coupling. In forward heat integration, out of the •  A 15°C approach (∆ temperature difference) is maintained
three columns, the first column is the topping column, as in the between LP column reboiling liquid and HP column overheads.
two-column case; the second is a HP refining column; and the Table 2 summarizes the simulation results for the base
third is LP refining column. case of two-column, three-column schemes with forward-
Total heat required for the HP-column reboilers is and backward-heat integration configuration.
provided by LP steam. Instead of using a cooling water heat The LP steam consumption in the two-column configuration is
exchanger to chill overheads of the HP column, heat is used much greater than the three-column configuration. This is because
to run the LP column reboiler. This is called the forward-heat
integration because heat integration is in the direction of Condenser 1 Condenser 2 Product
material flow. The HP column is operated at a pressure of 7 MeOH
to 10 atmospheres depending on the feed composition. The Stripped
LP column is operated near to atmospheric pressure. gas Reflux Reflux
Reflux
drum 1 drum 2 drum 3
Table 2. Simulation results for column schemes
Two-column scheme Liquid
Crude off Higher alcohols
Stabilizer column Concentration column MeOH steam
No. of stages 38 80 Topping HP LP
Reboiler duty, Gcal/hr 5.20 25.53 column column column

Condenser duty, Gcal/hr 6.26 25.22 Process LP

Diameter, m 1.84 4.10 gas steam
Reflux ratio 132 2.21 Reboiler Reboiler Reboiler
Boil-up ratio 0.64 13.27 1 2 3
LP steam consumption 1.3384
Stabilizer Recycle water
(metric ton/metric ton of MeOH) MeOH pump
Three-column (forward integration) scheme Fig. 4A Three-column configuration (forward integration)
Stabilizer column HP column LP column for an MeOH plant.
No. of stages 38 58 53
Reboiler duty, Gcal/hr 5.20 19.47 17.98
Condenser duty, Gcal/hr 6.26 17.98 19.09 Condenser 1 Condenser 2
Product MeOH
Diameter, m 1.84 2.61 3.51 Stripped Reflux
Reflux ratio 132 5.64 2.96 gas Reflux drum 3
Reflux
Boil-up ratio 0.64 3.45 9.44 drum 1 drum 2
LP steam consumption 0.934
(metric ton/metric ton of MeOH) Liquid
Crude off
Three-column (backward integration) scheme MeOH steam Higher
Stabilizer column HP column LP column Topping HP alcohols
No. of stages 38 55 58 column column LP
column
Reboiler duty, Gcal/hr 5.20 17.46 17.85 Process
Condenser duty, Gcal/hr 6.26 17.67 17.46 gas LP
steam Reboiler
Diameter, m 1.84 3.36 2.62
Reboiler 3
Reflux ratio 132 2.70 5.00 1 Reboiler
Boil-up ratio 0.64 3.83 9.92 2
Recycle water
LP steam consumption 0.8265
(metric ton/metric ton of MeOH)
Fig. 4B Three-column configuration (forward integration)
for an MeOH plant.

HYDROCARBON PROCESSING January 2012 I3

Petrochemical Developments

the heat required for the concentration column is supplied by LP lation setup under consideration. The cost contribution is higher
steam. In a three-column configuration, there is a possibility to for instrumentation in three-column backward configuration
couple the reboiler of one column with the condenser of another. than for a forward design due to the complex control system.
Temperature differences between utility (LP steam) and The capital cost in the case of the three-column configuration
reboiler temperature decrease with increasing column pressure. is more (12%–17%) than that of two-column configuration due
Thus, the reboiler requires a higher area for the same duty when to the additional column and associated equipment. It is very
compared to base two-column configuration. important that before adopting any of the listed schemes, a bal-
In the backward-heat integration scheme, due to altered ance between the fixed and operating cost is done.
col-umn sequencing (i.e., LP column preceding the HP
column), around 60% of MeOH product is recovered in the Operating cost. The operating cost for the distillation
first stage. This offers advantages in two ways: column scheme under consideration includes cost for cooling
1) Ease of separation (characterized by the relative water in the overhead condenser and steam in the reboiler.
volatilities) increases with decreasing operating pressure for The operating cost of cooling water is governed by various
a constant feed composition factors such as ambi-ent conditions, electrical consumption
2) Altered composition as compared to a forward-heat in fans and cooling water pumps, water cost and chemical
3
inte-grated scheme distillation can be done at lower pressure treatment. The cost of cooling water is taken as $0.2/m .
in HP column. The three-column configuration saves energy consumption in
This reduces the heat duty on the HP column reboiler. The terms of LP steam supplying heat to the reboiler. The steam
reverse heat integration results in more energy savings. required is the operating cost, and it can be expressed in terms
of natural gas consumption. The steam costs can be determined
Economics of methanol distillation assuming water at available temperature is heated in boiler by
For capital cost, an MeOH distillation complex involves dis- burning natural gas, and it can be expressed by:
tillation column, reboiler, condenser, reflux tank, pump and
associated column controls. The cost for each units depends on M Cp T −T
( w ( Bref )
+λ
)
(NG unit price)
various operating and design parameters. Fig. 5 summarizes the
Cost of steam, $ =

(LHVNG )×ηBoiler
contribution of the individual costs to the total cost for the distil-

2.56% 0.34% 2.58% 4.23% 84.69%

5.61% 3B-column
configuration
Operating cost
(a)
Capital cost
3F-column
configuration

3.15% 0.28% 4.27% 7.75% 77.52%

7.04% 2-column
configuration

(b) 0 20 40 60 80 100 120 140

Relative cost
Fig. 6 Relative capital/operating cost for column configuration.

7.18% 0.27% 3.36% 9.58% 76.68%

2.93%
3B-column
configuration
(c) LP steam

CW
3F-column
configuration
Column Condenser
Reboiler Pump
Condenser drum Instrumentation 2-column
configuration
Fig. 5 Cost contribution to the capital cost of equipments for
various configuration—A: two-column configuration, B: 0 20 40 60 80 100 120
three-column forward integration configuration and C: Relative cost
three-column forward integration configuration.
Fig. 7 Operating cost contributions.

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 Petrochemical Developments
IMTOF, London, 1993.
The three-column configuration saves energy. Thus, less nat- 5 Chiang, T. P. and W. L. Luyben, Comparison of energy consumption in
ural gas is consumed via lesser steam demand by the reboiler. five integrated distillation column configurations, Industrial Engineering
Almost 30%–40% savings can be realized by adopting either Chemical Process Des. Dev., No. 22, 1983, pp. 175–179.
6 Wu, J. and L. Chen, Simulation of novel process of distillation with heat inte-
three-column forward configuration or three- column backward gration and water integration for purification of synthetic methanol, Journal
configuration. But a higher coolant flowrate is required in the Chemical Industrial Engineering, China, No. 58, 2007, pp. 3210–3214.
7 Liu, B. Z., Y. C. Zhang, P. Chen, and K. J. Yao, Research on energy
additional condenser in the three-column configuration; accord- sav-ing process of methanol distillation, Chemical Industry Engineering
ingly operating costs increased. Fig. 6 illustrates the combined Progress, China, Vol. 27, 2008, pp. 1659–1662.
8 Douglas, A. P. and A. F. A. Hoadley, A process integration approach to the
effect, where it can be seen that operating cost is high for a design of the two- and three- column methanol distillation schemes,
three-column configuration with forward integration, while, in Applied Thermodynamics Engineering 26, 2006, pp. 338–349.
others, marginal savings can be seen. Fig. 7 shows the split.

New thinking. A techno-commercial comparison of the two-

column and three-column schemes for medium capacity MeOH
plant is presented here. The three-column scheme with
backward -heat integration offers approximately 60% saving in
LP steam as compared to two-column scheme. It can provide as
an option where LP steam costs are higher compared to cooling
water. Although, in the three-column scheme, backward integra-
tion offers higher savings as compared to forward integration
scheme the column control will be complicated, and it needs to
be provided more attention during operation. HP

LITERATURE CITED
1 Pinto, “Methanol distillation process,” US patent 4,210,495, 1980.
2 Fiedler, E., G. Grossmann, D. B. Kersebohm, G. Weiss, and C. White,
Ullmann’s Encyclopedia of Industrial Chemistry, Wiley-VCH Verlag/
GMbH & Co., Weinheim, 2002.
3 Meyers, R. A., Handbook of SynfuelsTechnology, McGraw Hill, New York,
1984.
4 M. Harvey, “Methanol Distillation-Two and Three Column Schemes,”

HYDROCARBON PROCESSING January 2012 I5