Date :- 27-01- 2014.

ISSN: 2321-8134

IJFEAT
INTERNATIONALJOURNALFORENGINEERINGAPPLICATIONSAND TECHNOLOGY

NEW TECHNIQUE FOR ACID GAS REMOVAL BY RECTISOL WASH

PROCESS
Author1 Swapnil Suryawanshi
1

Author Final Year Student, College of Engg and Technology, Akola, Maharashtra,
India,sasuryawanshi1992@gmail.com

Author2 Prof Sanjay Bhagat

AuthorAssist Prof, Department of Chemical Engg, College of Engg and Technology, Akola, Maharashtra, India
Abstract
Coal and petroleum coke gasification is increasing in high demand due to the increased cost of conventional fissile

fuel like gas and oil. The cost of imported natural gas is increasing beyond expectation and this is making the gasification process
more and more costly. The gasification exit gas need to be purified of impurities like H 2S, CO2, CO. The Rectisol wash process offers
excellent solution to the gas treatment in downstream of any gasification complex.
Rectisol wash unit is physical absorption process. The Rectisol wash unit is used to selectively absorb and removal of
acid gases using methanol as solvent in which at 40 0 C, it absorbs acid gases from feed gases at relatively high pressure. The rich
solvent containing acid gas is led down in pressure to release and recover the acid gases. Methanol has high solubility of acid gas and
low solubility of main gas component. Since selective removal of CO, H 2S and CO2 as a separate stream is possible with this
technique due to high absorption capacity of methanol with low energy consumption. Treated gas can be utilized as fuel to existing
gas turbines, fuel for existing heaters, producing value added product like hydrogen, Carbon monoxide.
Keywords: Rectisole, Gasification, Methanol.

1. INTRODUCTION
The first Rectisol installation was started up in Sasolburg,
Republic of South Africa, in 1955. In the following decades
Rectisol paved the way for huge-scale ammonia and Fischer
Tropsch Synthesis. In the 1970s and 80s, oil residue
gasification proved to be another field of application. The
impressive success of this technology is visualized above.
Nowadays, more than half a century later, Rectisol is still
unique reaching synthesis gas quality in one single process.
Meanwhile, a bunch of alternative technologies appeared on
the market for the simple removal of sulfur compounds and
CO2. However, Rectisol is still the only process taking care of
all other raw gas contaminants specific for coal and oil
gasification, sometimes only present in parts per billion (ppB)
in the raw syngas. Because of this, the comeback of the coal
gasification technology experienced in the first decade of the
millennium comes along with an impressive boost in the track
record of Rectisol plants: Nearly each of the coal gasification
units for production of ammonia, methanol, hydrogen or
synfuels is or will be equipped with a Rectisol gas purification

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system. This will result in another sharp increase in the curve

depicted above when the plants are in operation. In the new
millennium, the purification of syngas produced by
gasification of heavy oil residue from recovery from oil shale
or oil sands are a new field of application adding to the
classics, coal, lignite and refinery residue gasification.
Various separation processes are used in the
chemical industries for purification of one or multi
components. The basic processes are absorption, adsorption,
cryogenic separation, membrane separation etc. Depending on
the specific requirement of separation, a particular process is
selected. In case of Acid Gas Removal which is popularly
known as AGR, there are mainly two types of processes i.e.
physical wash and chemical wash. The Rectisol process is an
example of physical wash process. Coal and petroleum coke
(petcoke) gasification is becoming increasingly in high
demand due to increased cost of conventional fossil fuels like
gas and oil. The cost of imported natural gas is increasing
beyond expectations and this is making the gasification
projects more and more viable. The gasification exit gas needs
to be purified of all the impurities like H2S, CO2, COS, etc.

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The Rectisol wash process offers an excellent solution to the

gas treatment in the downstream of any gasification complex.
Treated gas can be utilized for co-gen (as fuel to existing gas
turbines), fuel for existing heaters, producing value added
products like hydrogen, substitute natural gas (SNG), carbon
monoxide (CO), synthesis gas, etc.

1.1 PERFORMANCE
The principal useful components of a raw syngas gas produced
by heavy oil or coal gasification are H2 and CO. Dependent on
the feedstock and type of gasification process this raw gas can
contain 340% CO2 as well as smaller fractions of CH4, H2O,
N2 and Ar. Trace contaminants present may be H2S, COS,
HCN, NH3, nickel and iron carbonyls, gum formers, CS2,
mercaptans, naphthalene, thiophenes, organic sulfides, and
higher hydrocarbons. In order to obtain the gas quality needed
for its usage as a feedstock for a synthesis, as e.g. ammonia
synthesis, methanol synthesis, Fischer Tropsch Synthesis, oxoalcohol synthesis or simply as hydrogen product, reduction gas
or town gas, these impurities must be removed. This especially
holds true for the trace contaminants which usually have to be
eradicated.
Typical purity requirements for synthesis gas:
Total sulfur less than 0.1 ppm by volume
CO2 2 ppm to 3% by volume
Depending on the type of synthesis Sulfur compounds, HCN
and NH3 should be discharged in a stream as concentrated as
possible so as to improve the economics of subsequent
treatment. The CO2 must be sufficiently clean to allow it to be
discharged directly to atmosphere or even used as a product.
The CO2 separated from the gas can be a mixture with
nitrogen when it is vented to the atmosphere. If the CO 2 is
used as a feedstock for another process (e.g. in a urea
synthesis or for production of food grade CO 2) the CO2 has to
be partially or completely recovered as a highly concentrated,
pure and dry product stream. The allowable residual H 2S
content for both cases typically varies in a range of 525
ppmV.
To summarize, the following functions have to be
fulfilled by the gas purification system:
Trace contaminant removal
Deep de-sulfurization
Drying
Bulk CO2 removal
CO2 purification Acid gas enrichment
Where other approaches may end up with up to six separate
processes, the Rectisol technology provides an excellent
option to stick with only one integrated technology and plant,
yielding excellent results with respect to performance and
reliability. For example Rectisol absorbs also COS so that a
separate COS hydrolysis process upstream of the gas wash is
not needed.

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2. GENERAL INFORMATION OF RECTISOL

PROCESS:
Rectisol was developed jointly by Linde and Lurgi in the
late 1950s
Rectisol is a physical wash system
Methanol is used as wash solvent
The process operates best at low temperatures and high
pressures
Possible selective removal of H2S, COS and CO2.
Linde is well experienced in handling of trace impurities
2.1 Rectisol has been successfully applied for purifying
syngas produced by:
Sasol/Lurgi Fixed Bed Dry Bottom Coal and Lignite
Gasification
Lurgi British Gas BGL Coal gasification
Shell Oil or Coal Gasification
GE Oil & TAR Gasification
GE Petcoke Gasification
Reformed gas from natural gas reformers

3. INTRODUCTION OF METHANOL
High solubility of the acid gas
Low solubility of the main gas components (like H2, CO,
etc.)
Economical and readily available (non-proprietary bulk
chemical)
Low corrosiveness
No foaming tendency
Low solvent losses

4. GASIFICATION PROCESS
Gasification is a process where carbon containing materials
such as wood, coal or biomass are heated to high temperatures
and allowed to decompose into a mixture called synthesis gas
or syngas. This syngas is a reactive mixture of mainly carbon
monoxide and hydrogen, which we can later convert to other
fuel products. For the purpose of this report biomass,
specifically Miscanthus Giganteus is the target reactant due to
reasons discussed in earlier sections of this report. The type of
physical equipment to be used and process must be modeled
uniquely depending on the feedstock to be used. In the case of
biomass, this consists of four steps: Feed processing and
handling: discussed in the feed handling section of this report.
Pyrolysis: A pyrolysis is a decomposition of
biomass, where the biomass fed to the system decomposes into
a variety of hydrocarbons, olefins and aromatic compounds.
We modeled this via correlations since no accurate
understanding of the kinetics has been found in literature.
Secondary Kinetics determine the reactor effluent

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composition: The pyrolysis product mixture is converted to a

synthesis gas mixture through a series of kinetically controlled
reactions. These vary by reactor technology and feedstock.
These kinetics consume the larger hydrocarbons generated
through the pyrolysis to produce a carbon monoxide and
hydrogen-rich synthesis gas. This process also produces a nonignorable amount of char. Char oxidation: Char, carbon
compounds with a similar chemical make-up to coal, is
removed from the main reaction vessel and is combusted for
energy and to ensure that the char does not contaminate later
processes.

4.1 GAS ABSORPTION PROCESS

There are two types of gas absorption process which classified
as
A) Physical Absorption
1. Solvent does not react with acid gas.
2. Each component in gas absorb required proportion of gas
according to their solubility.
3. This solubility acts as driving force for the gases.
B) Chemical Absorption
1. Acid gas react with solvent and produced new solvent .
2. Generally Amine used as solvent.

4.2 ACID GAS REMOVAL PROCESSES

There are numerous commercial acid gas removal (AGR)
processes available to treat a variety of gas streams. These
range from throwaway regenerable adsorbent-type to
regenerable solvent type processes. The solvent-type processes
are the primary ones of interest for acid gas removal from
synthesis gases.
The solvent-type processes can be subdivided into three
generic types:
Chemical solvent
Physical solvent
Mixed chemical/physical
There are many commercial installations of each
type, treating a variety of natural and synthesis gases. For
synthesis gas treating, the principal chemical-type solvents of
primary interest are aqueous amines, MDEA (methyl diethanol
amine) being the current favourite. Amine-based solvents have
been preferred by the natural gas industry over the physical
solvents. The physical solvents co-absorb hydrocarbons to a
much greater extent than the amines, causing loss of valuable
hydrocarbons. However, since synthesis gas does not contain
appreciable quantities of hydrocarbons, physical solvents are
also used for synthesis gas clean up.
The currently favoured physical solvents are
methanol and dimethyl ether of polyethylene glycol, as
represented by the Rectisol and the Selexol processes,

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respectively. The mixed chemical/physical processes usually

employ mixtures of an amine and a physical solvent in an
effort to capture the best characteristics of each solvent. The
best known example of the mixed/chemical solvent process is
Sulfinol, a mixture of sulfolane (tetra hydrothiophene dioxide)
and an aqueous solution of an amine, either DIPA (diisopropanol amine) or MDEA. The principal challenge of the
AGR processes is to remove the sulfur compounds from the
synthesis gas to as low a level as possible, consistent with the
prevailing emission regulations, and as economically as
possible. As SOx emissions regulations become more stringent
in the future, very high percentages of sulfur removal will be
required.
For example, to meet better than 99.3% sulfur
removal from the syngas will be required in the case of IGCC
based on coal containing 3.0% sulfur. To meet SO 2 target of
0.01 lb/MMBtu, better than 99.83% sulfur removal would be
required. The total sulfur content of the treated synthesis gas
has to be less than about 80 ppmV in order to achieve the 0.04
lb/MMBtu limit. This would not be a problem if only H 2S
were present, since H2S is easily removed by most AGR
processes down to very low levels. However, the presence of
COS in synthesis gas complicates the task, since its solubility
is much lower than that of H2S in both types of solvents
making it more difficult to remove. For the sulfur recovery
unit (SRU), usually based on the Claus process, to operate
properly, it requires an H2S-rich acid gas feed, meaning that
H2S has to be removed preferentially to CO2 in the AGR.
Thus, the AGR process has to show some level of selectivity
for H2S over CO2. On the other hand, if CO2 sequestration
becomes desirable, then the AGR process should also have the
capability for bulk removal of CO2. Although these two goals
seem un-reconcilable at first glance, the task can usually be
accomplished by staging acid gas absorption into separate
tasks. For CO2 capture, the capability of the process to achieve
these two tasks in an efficient manner becomes very
important. The capabilities of the various solvent-based AGR
processes to remove H2S, CO2, and COS are discussed below.
Particular issues addressed are relative performance and cost
factors, COS absorption and the retention of H2S/CO2
selectivity while also removing CO2.

5.0 RECTISOL PROCESS

Licensed by LindeAG and Lurgi AG, the Rectisol process is
an acid gas removal process that separates mainly hydrogen
sulfide and carbon dioxide using methanol as a solvent. Trace
contaminants such as ammonia, mercury, and hydrogen
cyanide are also removed. Cold methanol at approximately -60
F absorbs the acid gases at a pressure between 400 to 1000
psia. The pressure is then reduced to release and recover the
gases. The hydrogen sulfide is sent to a Claus unit, an industry
standard patented by Carl Friedrich Claus, for conversion to
elemental sulfur. A typical flow process is pictured in Figure
1. Rectisol processes have been operated reliably for decades
behind many types of gasification processes. There are about
59 gasification facilities world-wide that have been operating
Rectisol processes, and about seventy-five percent of the

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worlds syngas produced form oil residue, coal, and wastes is

purified by the Rectisol process .

applications. The block flow diagram shows one possible

arrangement starting with the gasification of heavy oil using
the Lurgi Multi Purpose Gasification Process (MPG). The
example focuses on the production of methanol. However,
additional possibilities for other products are indicated by
dotted lines. We show a simplified process flow diagram for
this scheme. In this example, the gas train is equipped with a
clean gas shift, integrated in the Rectisol system. Schemes
where a raw gas shift is installed upstream of the Rectisol unit
are also possible and demonstrated.

5.2 PURIFICATION PROCESS SELECTION

Fig .1 PFD of Rectisole unit for H2S absorption

5.1 PROCESS PRINCIPLE
Rectisol uses refrigerated methanol as the solvent
for physical absorption. The undesired components of the raw
gas, such as CO2, H2S, COS and the remaining sulfur
compounds, HCN, NH3, as well as nickel and iron carbonyls
are physically absorbed from the raw gas by the solvent. These
components are then desorbed by reducing the pressure of the
solvent, stripping and, if required, reboiling the solvent. The
absorbed higher hydrocarbons are recovered in an additional
extraction stage, if necessary. The solubility of the different
components to be removed varies considerably. This also
applies to H2S and CO2 and allows selective removal of these
components.
Since the solubility data of H2S and the organic
sulfur compounds are appreciably higher than that of CO2, the
H2S concentration in the Claus gas can be increased to
acceptable levels even if the H2S to CO2 ratio in the raw gas is
unfavourable. The solubility of the trace components HCN,
NH3 and sulfur compounds like mercaptans are much higher
than those of H2S. This makes it possible to remove them
separately using a very small solvent rate in a prewash stage.
The rich methanol from this prewash stage is regenerated by
integrating this loop into the H2S hot regeneration system so
that these trace components are routed directly to the Claus
gas. Rectisol also provides excellent performance in separating
big amounts of CO2 from the gas. At CO2 partial pressures
due to high concentration in the feed gas and/or due to high
gasification pressure the absorption capacity of low
temperature methanol exceeds the one of each alternative
solvent.
The process is extremely flexible, a feature which allows it to
be tailored to a large number of different individual

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The Rectisol Process was chosen from the separation

alternatives because it has the ability to remove H2S and COS
to sulfur concentration criteria and to reduce the CO2
concentration without destroying the solvent. This process is
widely used on an industrial scale and has been proven to be
economical. Methanol as a solvent is inexpensive compared to
the Selexol solvents and it requires less steam energy for
regeneration. Although the capital costs are higher to maintain
the low temperatures and high pressures, the purity of the
cleaned gas is higher because methanol as a physical solvent
can remove greater percentages of acid gas components. The
process is flexible and can be suited to separate the gas into
various components based on the final product desired. The
decision is supported by the decision matrix shown below. The
weight column indicates the relative importance of the given
design criteria, with 1 being least important and 10 being most
important. Each separation process was given a number, with
a weak score of 1 and a strong score of 10 in each design
category. The score for each category was then multiplied by
the weight and summed for each separation process.

Table1. Purification Process Decision Matrix

Process Product Purity: Rectisol is capable of reducing the
acid gas to 0.1 ppm H2S while Selexol can reduce it to 1 ppm.
Amine processes typically reduce H2S to between 5-10 ppm,
and the hybrid processes reduce the H2S to about 20 ppm
(NREL, 36). The hybrid processes were given a low score
because they are on the boundary of the 10-20 ppm H2S
content requirement. Because all of the processes will bring
the acid gas to the required H2S content, the weight of this
category is low.

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Process Simplicity: The Rectisol is slightly more complicated

than the Selexol process because refrigeration is required. The
amine and hybrid processes were given a low score because
simulating the reactions taking place in the absorber would be
much more complicated and outside the scope of our
knowledge and experience. For this same reason, the weight of
this category is large.
Minimum Solvent Degradation: The amine and hybrid
processes were given a lower score than the physical
absorption processes because the amine solvent reacts with
impurities like COS.
Commercial Experience: All of the processes are
commercially available on an industrial scale, so the weight of
this category is low. Amine solvents have not been used with
biomass-derived syngas, so these processes received a lower
score.
Selectivity of H2S vs. CO2: Physical absorption processes
have this capability while chemical absorption processes do
not because of simultaneous reactions. Selexol would require
an additional absorber to remove CO2, so its score is slightly
lower than Rectisol.
Minimum Loss of Product: Absorption of CO and
hydrocarbons is expected to be greater for physical absorption
than chemical absorption due to the higher solubility of these
compounds in a physical solvent. Thus, the physical processes
were given a lower score. Selexol was given a slightly lower
score than Rectisol because hydrocarbon losses can be
significant when treating hydrocarbon-rich gas streams.
Minimal Cost: The hybrid processes would be most
expensive because of royalty costs and higher solvent costs. It
is difficult to determine the costs associated with the other
three processes without doing a complete analysis. Selexol
solvent is more expensive, but does not have the high cost of
refrigeration as of Rectisol. The physical solvents can be
regenerated by pressure reduction, inert gas stripping, or
thermal regeneration, which require little energy compared to
that of chemical due to the lower heat of desorption of acid
gases. Amine solvents are more expensive to input and
regenerate but dont have cost of high pressure and
temperature.
The raw gas entering the plant is cooled. The trace
components like HCN and NH3 are removed in the prewash
stage with cold methanol. Thereafter, the sulfur is removed
from the gas using CO2- laden solvent to a residual sulfur
content of below 0.1 ppm. The solvent from the H 2S absorber
is regenerated first by flashing at medium pressure to recover
the useful gases (H2 and CO) and then by heating to boiling
temperature and stripping with methanol vapor. In cases where
there is sufficient H2S in the raw gas, hot regeneration
produces a Claus gas with adequate H2S content for further
treatment without any special measures needing to be taken.
Where the H2S content of the raw gas is lower or the CO2
content higher an additional stage, stripping and re-absorption,
must be provided.

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5.3 PRODUCTION OF GASES FROM PARTIAL

OXIDATION OF HEAVY OIL
The flashed CO2 is free of sulfur and can be discharged
directly to atmosphere. Under certain circumstances a water
wash system may be necessary to further reduce the residual
content of methanol in the CO2 for environmental reasons. The
refrigeration balance of the system is maintained by the
refrigeration plant. As the raw gas usually is saturated with
water, a small portion of water is fed to the plant, which is also
completely absorbed by the solvent. The water content of the
solvent is kept at the desirable low level by continuously
distilling a small side stream of the solvent circulation in a
methanol/ water distillation column which due to simplicity is
not depicted in the schemes. An important feature of Rectisol
is that this water leaves the distillation as the bottom product,
carrying heavy boiling trace contaminants, and salts, other
trace contaminants and/or even Ni and Fe sulfides formed in
through decomposition of the carbonyls, if present in the raw
gas. Nevertheless, as the concentration of such components is
small, the water can be routed directly to a biological water
treatment for work-up.

5.4 RECTISOL PROCESS DESCRIPTIONS AND

SIMULATION
A summary of our design of the Rectisol
process is described in figure 2. Approximately 1.377 * 106
lb/hr of raw gas from the syngas coolers enters an H2S
absorber where H2S, COS, HCN, and NH3 is removed. Most
of the methanol is recovered in a hot regenerator and methanol
stripper. About 64 lb/hr of fresh methanol is required. The raw
gas is first washed with methanol in the bottom section of the
absorber before entering the main section by a chimney tray.
The laden methanol leaving the bottom of the absorber enters
a sour flash; the sour flash generates sour gas sent to the Claus
plant and liquid sent to the methanol stripper. The laden
methanol that leaves the main section of the absorber is fed to
a flash regenerator, along with tail gas from the Claus unit.
The gas that leaves the regenerator is directed to the
hydrogenation reactor in the Claus unit. The methanol leaving
the bottom undergoes a final regeneration by stripping with
methanol which has been vaporized via low pressure stream in
a reboiler. After the exiting acid gas is cooled, some of the gas
is recycled back to the regenerator while the rest is transported
to the Claus unit for sulfur recovery. A refrigeration system
requiring about 34,000 kW of electrical power supplies the
refrigerant for cooling the various streams. Pumping power
requirements total about 517.3 hp. About 1.307*106 lb/hr of
clean syngas is produced, resulting in an efficiency of about
95%. About 600 lb/hr of elemental sulfur is produced in the
Claus unit, which is further described below. The H2S content
is reduced from approximately 260 ppm in the feed to about
15 ppm in the exiting gas. The process recovers sulfur from
the acid gases composed mainly of hydrogen sulfide. The
overall main reaction is:
2 H2S + O2 S2 + 2 H2O

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According to the 2006 United States Geological Survey, the

majority of the 64,000,000 metric tons of sulfur produced
worldwide was by product sulfur from refineries and other
hydrocarbon processing plants. Sulfur is used for
manufacturing medicine, cosmetics, sulfuric acid, fertilizers,
pesticides, and rubber products. The process involves a Claus
furnace and two to three catalytic stages which recover about
99% of the sulfur from the acid and sour gases from the
Rectisol process. The feed streams are preheated with steam
before entering the furnace, where H2S is reacted to SO2. The
exhaust is sent to a boiler to generate the steam. In the
catalytic stages, the SO2 and any remaining H2S in the exhaust
is then reacted to sulfur and water, typically with an activated
aluminium or titanium oxide. Tail gas is recycled to the
Rectisol process while the sulfur is condensed and collected in
a sulfur pit to be transported to a sulfur storage area.

Figure 2. Rectisol Process Flow Diagram

5.5 OPTIMIZATION
When optimizing the separation process, tradeoffs had to be
made. In order to lower the amount of methanol needed in the
absorber from both the fresh feed and recycle feed, the
pressure in the absorber needed to be increased, so that the
H2S content would still remain within limits. The tower
pressure was increased from 330 psia to 520 psia, still within
the suggested range of 330-1000 psi. This pressure allowed the
methanol recycle to be reduced from 8,00,000 lbmol/hr to
172,300 lbmol/hr while the methanol fresh feed was reduced
from 50,000 lbmol/hr to 2 lbmol/hr, allowing the methanol
input to be economically feasible. At 450 psia or less, the H 2S
content does not meet the catalyst specifications.

Optimizing pressure in the absorber with an input of 2

lbmol/hr of fresh methanol .At a pressure of 520 psia,
increasing the fresh methanol input does not decrease the H2S
content of the exiting gas significantly, where the H2S does
not change by more than 0.01 ppm with a ten-fold increase in
methanol input. The H2S removal improved as more trays
were added to the absorber .The H2S removal did not improve
significantly. The most H2S was removed when the treated
methanol entered and the side draw exited near the bottom of
the absorber. The temperature of the methanol feed to the sour
flash needed to be set at 210F or higher in order for any of the
methanol to separate from the H2S. The heat exchanger
between the absorber bottoms and the treated methanol was
designed to achieve the maximum cross temperature. The heat
exchanger requires 10 shells in series and one tube pass per
shell with one counter-flow shell pass and only one shell in
parallel. Even with this design, another heat exchanger is
required to reduce the temperature of the treated methanol
from -8.7F to -60F and a heat exchanger to increase the
temperature of the absorber bottoms from 179F to 210F.The
heat exchanger between the raw syngas and the treated syngas
has a similar design with 10 shells in series and one tube pass
per shell with one counter-flow shell pass and one shell in
parallel. The amount of H2S removed does not change much
when the syngas is cooled past the minimum temperature,
170F, achieved in the heat exchanger, so a second heat
exchanger is not needed before the syngas is fed to the
absorber. That the required purity of the exiting syngas is
achieved when the methanol stripper removes at least 90% of
the H2S from the incoming methanol before it is recycled to
the absorber. The separation improves when the pressure is
decreased, so a pressure of approximately 60 psia is the
highest pressure that will allow 90% removal. Thus, the
methanol stripper pressure was set just below that at 55 psia.

Fig .4 Applications of untraced gases

5.6 VESSEL SPECIFICATION

Figure 3. Solubility of various gases in methanol

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Sizing and material specifications are listed. The size was

determined using suggested parameters for the Rectisol
process. These values were confirmed by first calculating the
abscissa ratio from the liquid and vapour flow rates, densities,
and molecular weights was then used to find the CF in order to
calculate a capacity parameter. After using the Oliver
correlation, a diameter could be calculated. Carbon steel was
specified for most of the vessels, but stainless steel was
indicated for vessels that are more susceptible to corrosion
with water and H2S. Stainless steel contains more chromium

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than carbon steel, so it can form a passive film which prevents

rusting and flaking from spreading internally.

5.7 EFFECT OF THE TRACE COMPONENTS

The feed gas to AGR unit comes normally from a gasifier in
the upstream. Hence there is every possibility that the feed gas
will contain trace level of impurities like NH3, HCN,
carbonyls etc. The AGR process can be designed by Linde to
handle all possible impurities originating from gasification of
even difficult feedstocks. However, as selection of gasifier
technology has an impact on impurities in the raw gas to AGR
/ sour shift, careful optimisation of the entire front end
(gasification, shift, AGR) needs to be done to reach to an
optimum of CAPEX and OPEX. Linde, with a massive
background experience in design and operation of Rectisol
units can offer optimization services to owners / investors of
new or existing gasification complexes. Even small amounts
of trace components can have a negative effect on product,
equipment and environment. Product streams can be wasted
and will not meet the product specification l Product streams
can be wasted and will not meet the environment regulation
Equipment can be plugged and can cause shut down and may
not achieve equipment specifications Trace components can
cause corrosion and therefore cause plant to shut down and
exchange of equipment People can be harmed. The first aim
should be to prevent any trace components from entering into
the Rectisol process and harm the process, environment or
people.

5.8 CONTROL AND SAFETY

The presence of hydrogen sulfide gas is a
safety concern for the Rectisol process. Hydrogen sulfide is a
toxic and irritating gas which can cause fatalities without the
proper training and monitoring equipment. Deadly exposures
to employees must be prevented by early recognition and
detection. For employees working in an area with the potential
to contain hydrogen sulfide, training must include learning
how to recognize the signs and symptoms of exposure, how to
monitor for hydrogen sulfide, and how to take protective
measures. Instrumentation must continuously monitor the
atmosphere, particularly in confined spaces, for hydrogen
sulfide and oxygen deficiencies. Hydrogen sulfide has a
permissible exposure limit of 20 ppm ceiling concentration
and a peak exposure limit of 50 ppm for no more than 10
minutes70. Inhaling low concentrations can cause headache,
dizziness, and upset stomach. A strong odour of rotten eggs at
low concentrations and a sweetish odour at higher
concentrations serve as a warning signal.
At concentrations higher than 30 ppm,
hydrogen sulfide may deaden the sense of smell. If
concentrations of 500-1000 ppm are inhaled, rapid
unconsciousness and death through respiratory paralysis will
most likely result. Respiratory protection such as the supplied
airline respirator should be used as a backup to the engineering
controls implemented in the plant. At the highest level of
plant-wide control, corporate management uses market
forecasts, raw material, and product prices to make production

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decisions. On the next level, operating conditions for each

process unit, such as the syngas purification stage, in the plant
are decided based on these current and future gasoline
production goals. Set points for each unit operation, such as
the absorber, are determined based on product quality and
temperature. Finally, at the unit operations level, process flow
rates are set, and each controller determines, for example, the
pressure to the control valves.
As the feed stream is under flow control.
Three controlled outputs result from the two-product column:
pressure, distillate receiver level, and bottoms level. Five
manipulated inputs include cooling water flow, distillate
product flow, bottoms flow, reflux flow, and steam-toreboiler. Because the bottoms product of the hot regenerator is
recycled back to the absorber after entering the methanol
stripper, the composition must meet a hydrogen sulfide limit.
Thus, a dual composition specification, where overhead and
bottoms composition are measured and controlled, is assumed
for the control strategy. There are no degrees of freedom since
each of the measured outputs is paired with a manipulated
input. The bottoms composition controller manipulates the
steam input while the level controller of the tower manipulates
the flow rate of the bottoms product. The pressure controller
manipulates the amount of cooling water used in the distillate
receiver while the reflux composition controller manipulates
the reflux Flowrate. Finally, the level controller of the
distillate receiver. Manipulates the distillate product.

6. SYNTHESIS OF METHANOL REACTOR

Optimization of the synthesis gas to
methanol reactor was completed in three stages, with each
stage eliminating a previously made assumption. In the first
stage, the simulation assumed an isothermal reactor design by
forcing the feed and effluent streams to the same temperature.
In this stage, reactor sizing was examined by looking at the
effect of reactor length and diameter on the rate laws and on
methanol yield in the effluent stream. The second stage
assumed a non-isothermal model, using the Nussult number
correlation for heat transfer in pipes. A final optimization was
completed which fully considered the effect of changing
temperature on the reverse reaction rate constant, k. The
methanol to gasoline design required extensive literature
research. Attempts were made to model this design by
examining the reaction heats of formation for various large
aromatics and long-chain hydrocarbons. After these attempts
were unsuccessful in accurately modelling these reactions, a
Polymath model was created to better understand the design.
The design process, as well as the results, is
described below. The process of converting synthesis gas to
the product: large chain hydrocarbons takes place in two
phases, the first phase consists of a plug flow reactor operating
at 200 kPa and 4000 C. The reactor uses synthesis gas
(CO/CO2/H2) under high temperatures and pressures to
commercially produce methanol from synthesis gas. The
catalyst used in this reactor is a Copper/Zinc-based oxide
work done by Panahi et al, the methanol synthesis kinetic data
provided by Vanden Bussche and Froment (1996), adequately

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describes this system. Heat and mass transfer, as well as

diffusion within the catalyst pellet were incorporated into the
rate constants. Catalytic activity was assumed to be constant in
this model as data was not available for more extensive
process modeling. This assumption is likely inaccurate as the
catalyst pellet activity would vary as more synthesis gas is
converted to product, varying with both time and reactor
length.
It is also assumed that the reactor operates in a single
phase. Optimization of the synthesis gas to methanol reactor
was completed in three stages, with each stage eliminating a
previously made assumption. In the first stage, the simulation
assumed an isothermal reactor design by forcing the feed and
effluent streams to the same temperature. In this stage, reactor
sizing was examined by looking at the effect of reactor length
and diameter on the rate laws and on methanol yield in the
effluent stream. The second stage assumed a non-isothermal
model, using the Nussult number correlation for heat transfer
in pipes. A final optimization was completed which fully
considered the effect of changing temperature on the reverse
reaction rate constant, k. The production of these larger
compounds is endothermic, and is driven by the release of
energy from the formation of stable compounds such as
carbon dioxide and water. Several trends can be seen from this
data: (1) The yield of larger products increases with spacetime, (2) the yield of smaller components decreases with
increased space-time, (3) water production increases with
space-time and temperature and (4) the yield of larger
products increases with temperature. These are all in support
of what is known about this reaction mechanism.
If this system could be modeled as isothermal, this data
would be sufficient for operation. This is not an adequate
assumption as the reaction is exothermic due to the large
amounts of carbon dioxide and water formed during the
process. Another isothermal option would be to utilize a CSTR
set up for this system, but this is difficult to implement due to
the catalyst and gas phase reactions. The next option was to
develop pseudo-kinetics from this data to model this system in
polymath.
This consisted of four steps:
(1) Creating a rate law to determine the consumption of
methanol,
(2) Developing individual product correlations,
(3) Developing enthalpy of reaction, and heat capacity
correlations, and
(4) Implementing the previous three steps in a detailed
polymath model.

7. THERMODYNAMIC STUDY
7.1 REACTION ENTHALPY
CAPACITY CORELATIONS

AND

HEAT

The last necessary component was a model for reaction

enthalpy and heat capacity. This was performed utilizing
UNISIM and the following technique. As enthalpy of reaction
data is available most commonly at 298 K, it was used to
calculate the enthalpy of reaction. That being calculating the

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energy to bring the reactants down to 298 K (H1), the

enthalpy of reaction at 298 K (25 oC, 1 atm)), and finally the
energy to heat the reactants to the reaction temperature (H 2).
These can then be added up to determine the enthalpy of
reaction at your specified reaction temperature.

Figure 5: Theoretical model for calculating the

enthalpy of reaction at any temperature
This is made more complicated by the fact that our product
composition varies with temperature and position in the
reactor, and that phase changes are involved. A basis stream of
methanol was passed through a heat exchanger, cooling the
methanol from the desired reaction temperature to 25 oC to
calculate H1. Assuming the maximum conversion at any
temperature, (25 oC, 1 atm) was calculated using enthalpies of
formation and the product composition at the reaction
temperature. Finally a stream of the product composition was
passed through a second heat exchanger, raising its
temperature and pressure to that of the reaction. These three
values were added, and average to obtain the average energy
released per kilogram of methanol consumed. This was
performed for each temperature (635, 653, and 673 K), and
these three points where fit with a quadratic equation. This
yielded:
Hrxn = 0.1819*T2-234.75*T+75400 (kJ/kg MeOH
consumed)
The heat capacities were also modeled using UNISIM. Heat
capacity of methanol was obtained from the properties table of
UNISIM, for a methanol stream at various temperatures over
the range of 635-673 K.
Cp (MeOH) = 0.0021*T+0.8181 kJ/ (kgMeOH*C)
The product stream heat capacity was determined in a similar
manner from UNISIM. A stream with the correct product
composition for that of 635, 653, and 673 K was set up and the
heat capacity was obtained on a per kilogram basis. This was
then fit with a quadratic equation to give:
Cp (pdt) = 0.0018*T+1.0595 kJ/ (kgpdt*C)
This all relies on the assumption that the final product
composition is approximately proportional to the product
composition at any point in the reactor. The effect of this
assumption on heat capacity is minimal as it has a small range
over all temperatures and conversions tested. This is more of a
concern for the enthalpy of reaction correlation. If this were
representative of composition at any point in the reactor, we

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would expect the reaction to be more exothermic initially, due

to the formation of small products, carbon dioxide and water.
The enthalpy of reaction would then decrease down the length
of the reactor as more endothermic products are formed, such
as the larger aromatics and alkanes. As is, the polymath model
negates the early temperature spike, causing the temperature to
be well within our set operating limits. Unfortunately, our
method of solving is not currently sophisticated enough to
vary enthalpy of reaction with temperature and composition
changing over the length of the reactor. While we are limited
by the programs available to us, we do believe that this
temperature cushion evident in the polymath model should be
sufficient to account for this initially more exothermic
reaction. If this does prove to be the case suggested solutions
include lowering the reactor feed temperature, decreasing the
initial temperature of the coolant, increasing the flow rate of
the coolant, and investigating the effects of increasing the
number of tubes (heat exchange area) present in the reactor.

other feedstock such as corn and switch grass. The amount of

utilities, such as steam and electricity, required was calculated
based on UNISIM model outputs. The sulfur credit is based on
the estimated amount of sulfur that can be produced in a Claus
unit from the amount of hydrogen sulfide leaving the Rectisol
process.
In order to calculate operating costs, 310 days of operation per
year was assumed. One can requires 37,000 $ for establishing
plant for H2S and CO. A typical replacement period of 3 years
is assumed for the zeolite catalysts. As, utilities, labour, and
other costs were estimated at about $182 million using
operating cost information presented of Product and Process
Design Principles.

8. COMPARATIVE PROCESS:

7.2 METHANOL TO GASOLINE CONTROL

LOOPS:
A total of five control loops must be implemented us to
control the methanol to gasoline reactor system. Three of these
directly affect the flow of Dowtherm A in the coolant system,
and the last will impact the flow of methanol through the
reactor. All controlling effects will be implemented with PID
control, and SPC.
1. The pressure of the Dowtherm A immediately after the
compressor will be measured and used to control the energy
into the compressor. This will ensure that the pressure drops
throughout the cooling system are accounted for by
recompressing our coolant.
2. The Dowtherm A temperature will be measured as it leaves
the reactor jacket. If the temperature is too high or too low, the
flow of Dowtherm A will be regulated accordingly.
3. The temperature of Dowtherm A will be measured as it
leaves the steam generation heat exchanger. This will allow us
to increase/decrease the flow of saturated water or steam
through this heat exchanger to return the coolant to the
temperature required by the reactor. The final control loop
impacts the flow of methanol and products through the reactor.
4. The flow rate of methanol into the reactor will be measured,
and used to control the flow. This will enable us to regulate
the flow through the reactor.

7.3 VAIRABLE COSTS

Comparison between various processes

8.1 THE SELEXOL PROCESS
The Selexol process is a well-known and widely used process
that uses dimethyl ether (DME) of polyethylene glycol as the
solvent. It has been used for natural gas processing, ammonia
and hydrogen production, and petroleum and coal gasification.
The solvent has chemical and thermal stability, a favourable
solubility for acid gases, and a low vapour pressure,
minimizing solvent losses, figure illustrates the Selexol
process. The feed gas enters the absorber at a high pressure
and low temperature so that the acid gases are absorbed by the
solvent. The solvent is regenerated by pressure reduction
through flash drums followed by thermal regeneration. Before
returning to the top of the absorber, the lean solution is either
cooled or chilled .However, the BTX that is contained in the
synthesis feed gas would dissolve in the Selexol solvent and
come out with the acid gas, making it unacceptable for the
Claus unit. The paraffins and olefins would mostly dissolve in
the solvent as well, contaminating the acid gas for the Claus
unit. Selexol will not remove COS from the raw gas, so a COS
Hydrolysis Unit would be required, adding complexity and
increased costs.

Variable costs were calculated as shown in order to calculate

these costs, the cost of Miscanthus pellets was estimated at
$54.50 per short ton, based on the price and relative density of

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Date :- 27-01- 2014.

ISSN: 2321-8134
Thermal regeneration usually only for a smaller portion of
the solvent, flash regeneration and stripping for the rest. Acid
gas enrichment: A suitable Claus gas can be produced even
with a CO2/H2S ratio up to 700 in the raw feed gas
a pure CO2 product stream, ready for Enhanced Oil
Recovery, underground storage or chemical usage can be
produced
Inexpensive, thermally and chemically stable solvent
available worldwide anywhere. No degradation, no corrosion,
no disposal problems.

Fig 6. PFD OF THE SELEXOL PROCESS

8.2 AMINE PROCESSES
The three basic amines commercially available include
primary amines like MEA or DGA, secondary amines like
DEA or DIPA, and tertiary amines like MDEA. Primary and
secondary amines react as follows:

H2+RNH2 RNH3 HS
CO2 +RNH2 +H2O RNH3 HCO3

10. APPLICATION OF VARIOUS

COMPONENTS
Uses of H2S
1. The separation of heavy water (water containing deuterium
hydrogen atoms) also requires the use of hydrogen sulfide as
part of the process.
2. It is also useful in laboratory chemistry and chemical
experimentation.

Selective recovery of H2S and CO2 is difficult because most

often these reactions occur simultaneously. The cost of an
amine process depends largely on energy requirements of the
solvent regeneration and the solution circulation rate, which
is based on the solution capacity and concentration knock-out
drum removes any condensate from the feed gas, which then
enters an absorber and reacts with the amine solution flowing
down the top. The sweet gas exits the top, and the amine
solution exits the bottom. A flash drum is used to remove from
the amine any dissolved hydrocarbons, which are then used as
plant fuel. The amine solution is heated before entering the
stripper where acid gases are removed. Water is recovered
from the stripped acid gas by cooling the gas before sending it
to a sulfur recovery unit. The amine solution exiting the
stripper is cooled before being recycled to the top of the
absorber.

9. ADVANTAGES:

3. Several organosulfur compounds are produced using

hydrogen sulfide.

Uses of CO2
1. High concentration of CO2 used to kill the pest such as
moth
2. It is used in carbonated water such as soft drinks and cold
drinks
3. It can be used as refrigerant in food industry
4. Used to extinguishes the fire
5. It can also be used as raw material for production of urea

Uses of CO

Removal of all impurities and trace contaminants in on

single absorption process

1. CO is used in modified atmosphere packaging systems in

the US, mainly with fresh meat products such as beef, pork,
and fish to keep them looking fresh.

Ultra-pure product gas: e.g. total sulfur <0.1 ppmV CO2 <2
ppmV

2. CO has been conducted in many laboratories throughout the

world for its anti- inflammatory and cytoprotective properties.

Tailor-made stoichiometric for any kind of synthesis either

with raw gas shift or integrated clean gas shifts
Multi-product application possible in one single unit, e.g.
methanol-syngas plus ammonia syngas plus hydrogen plus
IGCC fuel gas
All gaseous products are completely dry

3. CO has also been used as a lasing medium in high-powered

infrared lasers.

11. CONCLUSION
1.
2.

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Rectisol is best suited gas treatment downstream

coal and coke gasification processes
Suitable for all combinations of feedstock and
gasification technology

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Date :- 27-01- 2014.

3.

4.
5.
6.
7.
8.
9.

ISSN: 2321-8134

Can be designed for all impurity levels ,well

understood interaction of wash agent and trace
impurities
Lowest combination of OPEX / CAPEX compared to
other wash processes
No proprietary wash agent
Proven technology
Low tendency of fouling
No foaming tendency
Easy to operate, very reliable, extremely high on
stream factor.

REFERENCES:
1. Rectisol Article in Chemical Industry Digest June 2013
2. World CTL 2012 India Summit Linde-WorleyParsons paper
presentation-Integrated Rectisol
3. Process Screening Analysis of Alternative Gas Treating and
Sulfur Removal for Gasification Revised Final Report;
December 2002; Nick Korens, Dale R. Simbeck, Donald J.
Wilhelm; SFA Pacific, Inc. Mountain View, California
4. SFA Pacific Process Screening Analysis Dec 2002 pg.no.
23-37
5. Report of Rectisol wash unit of South Africa journal 2007
Page no. 39-71
6. Kohl, A, and Nielsen, R. (1997). Gas Purification (Fifth
edition Ed.). Gulf Publishing Company. Page no. 137-183

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