Enhancing Methanol Production by CO2

Injection

BY:
ABDULATIF M. AL-MUSABBEH
Saudi Methanol Co., Jubail, K.S.A.
SAYER M. AL-SHAMMARI
Saudi Methanol Co., Jubail, K.S.A.

Date
15 APRIL 2006
th

Page 1 of 13

ABSTRACT
Ar-Razi had conducted a feasibility study about enhancing the methanol
production by 20% via CO2 injection. This injected CO2 will be recovered from
existing Reformer Flue Gas. The advantage of CO2 injection had resulted in
attractive economical cost for methanol production as well as high contribution
to reduce the emission of CO2 to atmosphere.
However, the remarkable achievement in this study is not only the production
increase that will reach 20%, but also the CO2 source, which will be recovered
from existing steam reformer Flue Gas. Recovery of CO2 from flue gas and
use it in boosting methanol production can make Ar-Razi Pioneer in the
industries.
ARRAZI own the largest methanol complex in the world within one fence
through 4 independent plants, with nameplate capacity equivalent to 3.1
million Metric Tons per Year. Methanol is produced through well-known
conventional technology, which consists of steam reformer, methanol
Converter, and distillation. ARRAZI steam reformers can approximately emit
1880 KNM3/h of flue gas from which CO2 can be recovered.
In conventional Methanol process CO2, CO and H2 (SynGas) are produced by
reforming natural gas and then react together on synthesis catalyst to produce
crude methanol. Since the H2 exists in excess quantity, injecting CO2 to
SynGas can increase methanol production.
Brief description about the project is as follow: flue gas will be pulled from two
reformer stacks via blower, and then cooled down by direct contact with cold
water. Next, flue gas will be treated in two-column absorption technology
using amine-based solvent to capture CO2. Purified CO2 will be pressurized
and then injected in the methanol process.
The technical evaluation showed that de-bottlenecking the methanol plants is
feasible from operation and maintenance point view. In addition, Economical
evaluation had showed attractive return and payback period.

Page 2 of 13

Introduction:
Feasibility study had been conducted to de-bottleneck Ar-Razi methanol
plants. The purpose of de-bottleneck study was to inject the methanol plants
by CO2 in order to increase the production considering methanol demand
growth, improve the production cost and sustain against the impact of Natural
Gas change.
Three methanol plants were considered in CO2 injection which will result in
20% overall production increase; approximately 1515 Ton/day.
CO2 source will be the flue gas emitted by two existing steam reformers,
which will be recovered through Amine-Based Chemical Absorption process.
As result of recovering CO2, AR-RAZI will contribute in reduction of CO2
emission, which is one of the worldwide environment concerns.
This paper will focus on the CO2 source since it was found the major subject
in the de-bottlenecking the plants.

De-bottleneck Configuration:
Production of three plants will be increased by injecting CO2 to upstream of
the reformer section, which will increase the Methanol production by 20% as
overall. The incremental crude methanol will be treated in additional distillation
unit with design capacity of 1515 ton/day.
The CO2 source will be the flue gas emitted by two steam reformers that will
be treated in chemical absorption recovery process to capture the CO2 from
flue gas; the capture solvent will be amine based solution. The design
capacity of the CO2 recovery process will be 3000 ton/day of CO2.
Beside the process changes, it had been found that an additional cooling duty
is necessary mainly to quench the flue gas and cool the additional crude
methanol. In addition, electrical substation is required to supply additional
power requirement.

Page 3 of 13

Configuration of Debottleneck Methanol Plants

Plant-4

Note: Green Filled Blocks Will Be The New Units.

NG

NG

SYNTHESIS
REACTOR

DISTILLATION

PMA

FULE GAS

CO2

Plant-3

SYN GAS
COMPRESSOR

REFORMER

REFORMER

SYN GAS
COMPRESSOR

SYNTHESIS
REACTOR

DISTILLATION

PMA

FULE GAS
CO2
CO2
COMPRESSOR

CO2 RECOVERY
UNIT

DISTILLATION

PMA
1515
T/DAY

Plant-2

CO2

NG
REFORMER

SYN GAS
COMPRESSOR

SYNTHESIS
REACTOR

DISTILLATION

PMA

Legend: PMA is Pure Methanol Product

Page 4 of 13

So, the de-bottlenecking of three plants will require the following additional
facilities:
1. Distillation unit
2. CO2 recovery unit.
3. Cooling system
4. Additional Electrical station

Background of CO2 Source:

Carbon dioxide is used in the food industry in carbonated beverages, brewing,
and flash drying. Its industrial uses include enhanced oil recovery (EOR),
welding, chemical feedstock, inert gas, firefighting, and solvent extraction as a
supercritical fluid. It is an essential ingredient in medical oxygen, where in low
concentrations it acts as a breathing stimulant.
The largest potential market for CO2 is EOR and chemical Industries. The
major CO2 sources that can be considered for industrial market are (1):
1. Natural sources
a. CO2 wells
2. Industrial byproducts
a. Natural gas sweetening
b. Synthesis gas production
3. Flue gases
a. Fossil fuel-fired power plants
b. Industrial furnaces
c. Cement plants
d. Engine exhausts
e. Lime kiln exhausts
The most economical sources of carbon dioxide are CO2 wells and natural
gas sweetening or synthesis gas purification byproducts. However, the price
of methanol justifies the recovery of CO2 from flue gas sources (1).
Flue gases have long been important sources of CO2 for the merchant CO2
market, especially in remote locations or when by-product CO2 sources are
unavailable or insufficient. In the simplest case, fuel is combusted to produce
flue gas then CO2 is extracted from the flue gas.

Page 5 of 13

CO2 Recovery from Flue Gas

There are several methods to capture CO2 beside the amine based chemical
absorption technology, which is well known since long time. Some of these
are not practically economic for capturing CO2 from flue gas, while some are
not yet proven or technically not applicable for capturing CO2 from flue gas.
Below is brief description about theses methods (1 & 2).
1. Higher Pressure Absorption Process:

Absorption at atmospheric

pressure severely handicaps processes that rely on higher pressures.

For these process, the driving force for CO2 absorption and the cyclic
loading between absorption and de-sorption will be insufficient for
economical CO2 recovery. Alternately, compression costs to put the
flue gas into the operational range of these processes are prohibitive.
2. Hot Potassium Carbonate: Hot potassium carbonate (HPC) or Hot
Pot is effectively used in many ammonia, hydrogen, ethylene oxide
and natural gas plants. The most widely licensed of these are the
Benfield process. This process was proposed for treating flue gases
but optimum operating pressure for the process found to be 7.0 Bar (g),
which will be uneconomical for large scale flue gas recovery.
3. Membranes: Membranes suffer from both the cost of compression,
heat exchange and flue gas components to obtain high pressure feed
and in that they produce an impure CO2 product. There are currently no
commercial applications of membranes for recovery of CO2 from flue
gases, though they have been used in large EOR projects to recycle
CO2 from the associated gas.
4. Cryogenic Liquid Purification: Cryogenic methods for CO2 capture
options are considered for only Integrated Gasification Combined Cycle
(IGCC) and the combustion in pure O2 / CO2, since the low
concentration of CO2 in the flue gas makes this uneconomical for other
cases like steam reformer.
5. Adsorption: Consideration of the gas-solid adsorption options
concentrated on the use of molecular sieves in fixed beds. Adsorption
may not be an attractive option for CO2 capture mainly because the
Page 6 of 13

capacity of solids to absorb gas and the selectivity are relatively low.
The removal of CO2 from gas streams by an adsorbent is most
effective when the CO2 content is between 400ppm and 1.5 % by
volume.
As result of above survey, chemical absorption using amine-based solvent
was concluded to be the most reliable option for CO2 recovery from flue gas;
especially that flue gas is low-pressure environment. It is commercially
available, proven, being significantly improved and routinely used for small
plant and skid mounted units for chemical and food industries.

Provider of Amine-Based CO2 Recovery Process

Among the chemical absorption of CO2 recovery process the following
chemical companies were found involved in this field:
1. ABB

(Jointly by Kerr-McGee & ABB Lummus)

2. Flour Daniel (Econamine FGTM)

3. MHI

(jointly by MHI&KEPCO)

4. Wittcold
In next page, table can show the contribution of those engineering companies
about the CO2 recovery process:
ABB, Flour Daniel and MHI have own propriety CO2 recovery process. All of
them had built CO2 Recovery plant at small scale.
In addition, ABB, Fluor Daniel and MHI had conducted feasibility study for
large CO2 recovery from flue gas; these studies had concluded that the CO2
recovery from flue gas is technically feasible.

Page 7 of 13

CO2 Recovery Process Provider

References
(Built
&
Commissioned
Plant)
Maximum
Capacity built

Conducted
Feasibility
Study for Large
Unit?1

Solvent

Absorption
Contactor

ABB

Flour Daniel

MHI

4 Plant + 1 Pilot
plant

Over 21 plants

2 Plants + 1 Pilot
Plant

400 t/d

350 t/d

160 t/d

(Fired with Coal)

(Gas turbine exhaust)

(Fired with natural

gas)

Yes

Yes

Yes

15~20 % MEA +
Inhibitor

30% MEA + Inhibitor

Strictly Hindered
Amine (KS-1)

MEA

Random or
Structural Packing

Random Packing

Low pressure
packing

Wittcold
8 Plants

50 t/d

Structural
Packing

(KP-1)

Defined Criteria for large scale is a minimum 2400 t/d of CO2 if flue gas result of NG firing and 4600
t/d if flue gas result of firing of Coal.
Page 8 of 13

Proven CO2 Recovery on Gas Turbine Exhaust; Bellingham

Plant, USA - Aerial View (350 t/d)

(Fluor Daniel)

CO2 Recovery plant in Kedah, Malaysia

(160 t/d) (MHI/KEPCO)

Page 9 of 13

Process Description of CO2 Recovery Unit:

The flue gas contains approximately 9.8% (vol. %, dry basis) of CO2 and at
200oC will be pulled from two reformer stacks by blower through rectangular
duct. The flue gas from the stack is slightly pressurized by the Flue Gas
Blower and sent to the Flue Gas Water Cooler. In the Flue Gas Water Cooler,
the flue gas is quenched by direct countercurrent contact with circulating
cooling water
Then, the flue gas leaving the Flue Gas Water Cooler enters the bottom of
CO2 Absorber and flows upwards, countercurrent to the lean solution. CO2 in
the flue gas will be absorbed into the amine-based solution through direct
contact. Packing is installed within the absorption section in order to increase
surface area where the absorption reaction between the solvent and the CO2
in flue gas takes place. The treated flue gas exits the top of the Absorber at
low temperature.
The CO2 absorbed in the rich solution is removed from solution by steam
stripping in the CO2 Stripper. The rich solution containing CO2 contacts with
steam from the reboiler through the packing to receive heat from the steam in
order to dissociate the CO2 from the solution. The CO2 and steam rise to the
top through the CO2 Stripper and contact with the reflux water where the
solution vapor is recovered. The overhead vapor is cooled to in the Stripper
Condenser. The condensate accumulates in the Stripper Reflux, and is
pumped by the Stripper Reflux Pump to be retuned to the top of the CO2
Stripper.
The recovered CO2 is sent to the suction drum of the CO2 Compressor, and
the mist is separated. The recovered CO2 is then pressurized by centrifugal
compressor and sent to the three methanol plants.
Next page, simple diagram for the CO2 recovery can be shown.

Page 10 of 13

Simple Diagram for

CO2 Recovery System from Flue Gas

Page 11 of 13

Technical Concerns
This section will discuss the concerns that had been identified to design large
CO2 recovery unit. No Carbon Dioxide recovery unit had been built more than
400 ton/day, while the target in this study is 3000 ton/day, however many
studies have been conducted to prove that large scale is feasible. The
limitation is the maximum diameter of absorption column and cooling vessel
for the flue gas. The largest economic single train is 2400 t/d (based on the
maximum column diameter is 12.8m). For very large vessel it will be more
cost effective if constructed with rectangular cross section.
In addition, at certain level of study it had been found that large single blower
should be adopted to pull the flue gas from two steam reformers, however,
similar operating condition was identified in power plant, which was visited,
and its operability and reliability had been confirmed.
Moreover, flue gas distribution and flow pattern through the cooling vessel
and absorption column was also an important issue since the flue gas quantity
is huge and shall flow through big duct and large cooling vessel and
absorption column. It had been concluded that, careful fluid dynamic shall be
performed at detail design stage and necessary countermeasure shall be
taken.
Economical Evaluation Result:
The economical part of the project was executed in very molecules way
covering all realistic data and information, several analysis process in terms of
data authenticity and history. The results achieved were tested further and
sensitivity analyses session identified final IRR, ROI, NPV and payback
period.
Conclusion:
De-bottleneck of AR-RAZI methanol plant was found technically and
economically feasible. The general concern about the CO2 recovery from flue
gas was identified with recommendations, the technology is commercially
available, mature and being significantly improved. The de-bottleneck study
can be brought to further level of project phases.

Page 12 of 13

References
1. Chapel Dan G. and Mariz Carl L., Recovery of CO2 from Flue Gases:
Commercial Trends, 1999.
2. IEA Greenhouse Gas R&D program, carbon dioxide capture from
power station.

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