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Methanol
Methanol is an Alcohol whose chemical formula can be written as CH 3OH. It is a clear,
colourless liquid with a mild odour, and dissolves readily in most common organic solvents.
Methanol is one of the largest volume chemicals produced, with a world wide annual
production of about 13 million tons.
Methanol (CH3OH) is an alcohol fuel. Methanol is the simplest alcohol, containing one carbon
atom. It is a colorless, tasteless liquid
d with a very faint odor and is commonly known as "wood
alcohol."As engine fuels, ethanol and methanol have similar chemical and physical
characteristics. Methanol is methane with one hydrogen molecule replaced by a hydroxyl
radical (OH).
Physical Properties
Formula CH3OH
Solvent group 2
Flash point 11 oC
The reactions of the aliphatic alcohols including methanol generally involve hydroxyl group,
either through breaking of the C-O bond or O-H bond and substitution or displacement of the
H or _OH group, . the O-H and C-O bonds in alcohols are relatively strong, albeit polar and
kinetically labile. Hemolytic bond dissociation energies are in the order of 90 100 Kcal/ mole.
Because of this bond strength in alcohols, some activation of these bonds is often necessary
to achieve acceptable reaction rates.
Combustion of Methanol:
Oxidation of Methanol:
Methanol is oxidized with acidified Potassium Dichromate, K2Cr2O7, or with acidified Sodium
Dichromate, Na2Cr2O7, or with acidified Potassium Permanganate, KMnO4, to form
formaldehyde.
Methanol Formaldehyde
If the oxidizing agent is in excess, the formaldehyde is further oxidized to formic acid and then
to carbon dioxide and water.
The catalytic oxidation of methanol using platinum wire is of interest as it is used in model
aircraft engines to replace the sparking plug arrangement of the conventional petrol engine.
The heat of reaction is sufficient to spark the engine.
Production Of Methanol From Natural Gas 5
Dehydrogenation of Methanol:
Cu
300C
CH3OH ===> HCHO + H2
Methanol Formaldehyde
Dehydration of Methanol:
Methanol does not undergo dehydration reactions. Instead, in reaction with sulphuric acid the
ester, dimethyl sulphate is formed.
Conc H2SO4
2 CH3OH ===> (CH3)2SO4 + H2O
Methanol Dimethyl Water
Sulphate
Esterification of Methanol
H(+)
CH3OH + HCOOH ===> HCOOCH3 + H2O
Methanol Formic Methyl Water
Acid Formate
Methanol reacts with sodium at room temperature to liberate hydrogen. This reaction is similar
to the reaction of sodium with ethanol.
Methanol reacts with hydrogen chloride to form methyl chloride (i.e. chloromethane) and water.
A dehydrating agent (e.g. zinc chloride) is used.
ZnCl2
CH3OH + HCl ===> CH3Cl + H2O
Methanol Methyl
Chloride
Methanol As A Solvent:-
Methanol is miscible with most organic liquids and is a solvent for variety of substance like
dyes, nitro cellulose, polyvinyl, butyl ethyl cellulose, Shellac and modified resin. It is used in
the manufacturing of wood and metal polishes. Water proofing formulation, coated fabrics,
aniline, and other inks, and duplicator fluids. Its solution have lower viscosities than similar
solution, made from other alcohols, methanol is uses in combination with 5 to 10 % of
polyhydroxy alcohol as a solvent for water soluble aniline dyes in the manufacture of non-
=grain-raising wood-stain, it is also used as a solvent for aniline dyes for leather and is
especially useful where uniform colour development is essential. Other application of this
products include its addition to asphalts paints to decrease their drying time and its use in both
natural and synthetic rubber solutions to lower the viscosity during processing . Methanol does
not dissolve cellulose acetate and acetate butyrate, polystyrene, polyethene, methylcrylate
resin, polyvinyl chloride, and co-polymers.
Methanol As An Extractant:-
Methanol is employed in a large scale in many industrial chemical processes as an extractant.
In the refining of gasoline and heating oil. The unisol process use caustic methanol solutions to
remove undesirable mercaptan impurities. Methanol may also be used to extract the aromatic
potion of petroleum form other hydrocarbons and patent literature describe its use in extra
extraction
organic nitrites. From non polar hydrocarbon in the secondary recovery of crude oil by th
miscible phase method using alcohol methanol is the least expensive and most easy
recovered. A process has been developed to use a solvent of methanol and hexane in the
extraction of tars from Texas Lignite deposits.
Methanol is also uses for removing acid impurities from vegetable oils, dewaxing dimmer gum,
flash washing water soluble crystals, extracting inorganic salt such as potassium iodide and
barium and strontium halides, purifying hormones and crystallizing steroid.
Production Of Methanol From Natural Gas 7
Formaldehyde:-
Worldwide, the largest amount of formaldehyde is consumed in the production of urea-
formaldehyde resins, the primary end use of which is found in building products such as
plywood and particle board .The demand for these resins, and consequently methanol, is
greatly influenced by housing demand. In the United States, the greatest market share for
formaldehyde is again in the construction industry. However, a fast-growing market for
formaldehyde can be found in the production on acetylenic chemicals, which is driven by the
demand for 1, 4 butanediol and its subsequent downstream product, spandex fibers.
ACIDS:-
Methanol carbonylation has become the process of choice for production of this staple of the
organic chemical industry, which is used in the manufacture of acetate fibers, acetic anhydride,
and terephthalic acid, and for fermentation,
Production Of Methanol From Natural Gas 8
EMISSIONS
The methanol molecule has a simple chemical structure, which leads to clean
combustion; reports from emissions studies, however, vary more widely for methanol than for
other fuels probably because of differences among fuel blends used across the country and
because vehicles may not be optimized for using methanol. Comparisons of M100 with
gasoline and diesel have shown these results:
Carbon monoxide: Emissions vary sometimes lower, but are usually equal or slightly
higher.
Toxics: M100 contains none of the carcinogenic ingredients such as benzene, 1,3-butadiene,
and acetaldehyde. M85 (with 15 percent gasoline) has 50 percent fewer toxic air pollutants
than gasoline.
Production Of Methanol From Natural Gas 9
Formaldehyde levels: Much higher, although still low. The toxicity of formaldehyde is lower
than that of other toxics, and formaldehyde emissions can be reduced dramatically with new
technology, such as improved catalytic converters.
Particulate matter: Buses using M100 emit significantly less than diesel-fueled buses.
Internal Combustion Engines Using Methanol
Several factors effect the use and selection of any fuel. Among the important ones are
engine design, net energy per pound, net energy per gallon and the sulfur content of
alternative fuel properties.
a-Pure methane
b-Octane rating above 100 are correlated with given conc. Of tetra ethyl lead in 150 octane.
c-Natural sulfur content very low but measurable.
content. A Btu defined as the amount of heat necessary to raise one pound of water, one-
degree Fahrenheit.
Present design internal combustion engines run on liquid fuels. Methanol required few of any
engine modification to extract the maximum power from this fuel. As compared to gasoline,
methanol lowers some tailpipe emissions, namely the sulfur based HC, CO, as well as NOx.
Methanol contains only half the energy per gallon of gasoline but has a very high octane rating.
Increased compression ratios could yield 5-20 %. More power.
When methanol is used as a gasoline additive antiknock compound and fuel extender, it
becomes economical with very positive results especially from the emissions stand point. It
contains zero sulfur thereby reducing tailpipe acid significantly. Of the six most popular
attractive fuels presently available methanol has the second lowest Btu/lb, net energy yield. As
a result, fuel tanks will need to be enlarged for vehicles that run on pure methanol.
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, who called it spirit of box, because he produced it via the
distillation of boxwood. It later became known as pyroxylic spirit. In 1834, the French chemists Jean-
Production Of Methanol From Natural Gas 10
Baptiste Dumasand Eugene Peligot determined its elemental composition. They also introduced the
word methylene to organic chemistry, forming it from the Greek words methu, meaning "wine,"
and hyle, meaning "wood". 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.
In 1923, the German chemist Matthias Pier, working for BASF developed a means to convert synthesis
gas (a mixture of carbon monoxide and hydrogen derived from coke and used as the source of
hydrogen in synthetic ammonia production) into methanol. This process used a zinc chromate catalyst,
and required extremely vigorous conditions pressures ranging from 30 100 MPa (300
1000 atm), and temperatures of about 400 C. Modern methanol production has been made
more efficient through the use of catalysts capable of operating at lower pressures.
.
The first large scale commercial synthetic methanol process was introduced by BASF in 1923.
The process was based on the reaction of synthesis gas (a mixture of hydrogen and carbon
oxides) over a zinc chromite catalyst at relative high temp (300 to 400 Co) and high pressure
(250-350 atm). The synthesis gas was derived from coal via the water gas reaction.
The first synthetic methanol unit in the USA was located at Belle, West Virginia, at the
ammonia plant of Lazote, Inc, a subsidiary of Dupont and began operation in 1927. The unit
was actually installed to remove the 1 to 2 % carbon monoxide impurity in the ammonia
synthesis gas by utilizing the methanol synthesis reaction as purification step.
Up till the end of World War II, methanol was mainly produced as a co product using synthesis
gas from coke via the water gas or blue gas reactions as well as using off-gases form
fermentation, coke ovens and steel furnaces. These methanol units were relatively small (less
than 200 thousand tons per year, most in the 30 to 90 thousand tons per year range).
One of the major technological changes often overlooked in the methanol industry was
conversion from water-gas to natural gas as a source of synthesis gas for feed to the methanol
converters. Natural gas derived synthesis gas was much higher quality , contained much less
impurities and catalyst poisons , and was readily available in nearly unlimited quantity. 71% of
the carbon monoxide uses for the synthesis of methanol was obtained form coke or coal ,
where as by 1948 about 77% was derived from natural gas.
In 1966 , Imperial Chemical Industries (ICI) in England announced the second major break
through in methanol technology , the ICI low pressure process for synthesis of methanol using
a propri9etary copper based catalyst. The high activity copper based catalyst allowed the
methanol synthesis reaction to proceed at commercially acceptable levels tat relatively low
temp. (22-280 oC) thus allowing operation at significantly reduced pressure (50 atm) from that
needed for the high pressure process (350 atm ).
A number of improvements have been made in these early methanol process, principally in the
area of improved energy efficiency. Subsequent low pressure process have revolutionized the
industry and have allowed for the construction of more energy efficient and cost effective plant.
Now a days, modern low pressure methanol units have a capacity of about 400-1000 thousand
tons per year, operates at 50 to 100 atm.
Production Of Methanol From Natural Gas 11
Production Of Methanol From Natural Gas 12
RAW MATERIALS
Long-term availability energy consumption and environmental aspects are all considered in
choosing a raw material, however financial consideration are of primary importance.
Keeping above described factors in view, a fuel containing sufficient amount of hydrogen and
carbon monoxide is a possible raw material commonly known as synthesis gas for methanol
production.
Major resources from which synthesis gas be produced are
1. Natural Gas
2. Coal
3. Naphtha
4. Heavy hydrogen feed stock.
Extraction of synthesis gas from these sources is further described here:
The production of gaseous fuel from coal has been practiced for 100 of years but most of the
process
cess for gasification was gradually replaced in the 1950s and 1960s by processes based on
low cost petroleum hydrocarbons. The oil shortage of the 1970 renewed a worldwide interest in
coal as chemical feedstock. However, recent falling prices of oil in the world have moderated
that short lived interest. During gasification, falling ground coal reacts with oxygen and steam
at elevated temp. to form a synthesis gas comprised mainly of carbon monoxide and
hydrogen, with lesser amount of carbon-dioxide, methane, nitrogen, argon, hydrogen sulphide,
tar and phenols. The quantities of the lesser components depend on the amount of impurities
found in the coal and in the amount of oxygen fed to the gasifier.
The heart of the coal based partially oxidation process in the gasification step. To achieve
maximum efficiency, a gasifier should operate at an elevated pressure, have low oxygen and
steam demand, have high carbon conversions and have low heat losses. It is also desirable to
achieve high reliability, to minimize or eliminate by-product formation and to accept a wide
variety of coals. Low temperature gasifiers produce considerably more methane, oils, phenols
and tar than high temperature ones. A slagging gasifier operated at temperature above the
fusion point so that ash is removed in the molten form; that temperature is typically b/w 2400-
2700 oC.
Selecting the best gasifier for a particular operation is usually a matter of compromise, since
the designer must weigh many variables including the type of coal available, capacity, by-
product rates, and capital investment efficiency and so on. Most gasifiers fall into one of three
general categories atmospheric or low pressure, high pressure and second generation.
process
ess (Low Pressure Process), because it operates at atmospheric pressure; the product
synthesis gas must be compressed before introduction to methanol synthesis loop. THE
WINKLER GASIFIER is another low pressure process widely used in Europe, Japan and
India. However, as a low-pressure process, it has the same advantages and disadvantages as
the K-T process
A high pressure process, the LURGIDRY ASH GASIFIER is the most widely used commercial
process. It has even more disadvantages than K-T process, forms numerous by-products, has
a limited ability to handle caking coals, and produces as large amount of methane (which must
be purged from the converter loop, if the gas is used for the methanol synthesis).
During the 1950s an oversupply situation in Europe made naphtha an economical feed stock
for steam reforming. A series of alkali promoted catalyst was developed specifically for
naphtha, and by the early 1960s many European procedures where preparing synthesis gas
from light distillate naphtha. At the present time the price of the naphtha feedstock and mixing
it with a hydrogen stream so that the combined stream contain approximately 5% hydrogen
stream so that the combined stream contain nickel molybdate catalyst to convert organic
sulfur compounds to hydrogen sulfide and also to saturate alkenes. Desulphurization is then
conducted as described above for hydrogenation.
The sulfur free gas is fed to a reformer which contains catalyst specially designed for naphtha
reforming. A stream to carbon ratio as lo as 2 is used, where pressure range from 1500-4000
Kpa (200 to 575 Lb/in2g). Small amount of carbon dioxide can be added optionally to yield
synthesis gas composition similar to those obtained via hydrocarbon reforming.
The majority of methanol synthesis plants now use catalytic reforming of natural gas for the
production of synthesis gas. The process consists of two steps Desulphurization and the
steam reforming section.
a) Desulphurization:-
Natural gas contains both organic and inorganic sulfur compounds that
must be improved to protect the both reforming and down stream methanol synthesis
catalysts. They can position the catalyst even as low as 0.5 PPM. Hydrodesulphurization
across a cobalt or nickel molybdenum zinc oxide fixed bed sequence is the basis for an
effective purification system.
The temperature in the range of 340-370 0C may be necessary.
Zinc oxide is capable to reduce the H2S concentration down to 0.3 PPM.The disadvantages
are that it is non-regenaratable must eventually be replaced. To have the advance warning
before the ZnO bed is completely converted to ZnS at this point is provided at 755 of bed
depth. When the ZnO changes to ZnS at this point, it is the time to renew the bed.Chlorides
and mercury may also be found in natural gas, particularly from off shore reservoirs.Activated
alumina or carbon beds can remove these poisons.
Production Of Methanol From Natural Gas 15
b. STEAM REFORMING:-
Once the sulphur has been removed from the hydrocarbon feed stream, the gas is
mixed with steam and reform to produce methanol synthesis gas. The following reactions
occur in the reformer.
All three of these reactions are endothermic, and in full scale commercial reformer, all three
proceed essentially to completion.
The primary reforming equilibrium reaction involves methane and steam:
The equilibrium reaction of carbon monoxide with steam, often referred to as the water gas
shift reaction, is also a significant contributor in this process.
Note that the reforming reaction (4) is endothermic and the water gas shift reaction (5) is
exothermic. Undesirable reactions may occur in the reformer, resulting in deposition o carbon
on the reactor walls, on the catalyst surface, or in the pores of the catalyst. This reduces the
catalyst activity.
CnH2n+2 nC + (n 1) H2 -6
CH4 C + 2H2 -7
2CO C + CO2 -8
CO + H2 C + CO2 -9
A critical examination of the equations presented above allows one to make some preliminary
conclusions concerning reformer operation. Since reforming reaction (4) is endothermic and
the water gas shift reaction (5) is exothermic , it is obvious that less methane and more carbon
monoxide and hydrogen would be obtained at higher temperature. It is also suggested that
decreasing pressure would decrease the amount of methane in the reformer product stream.
Production Of Methanol From Natural Gas 16
In a similar manner , increasing the partial pressure of the steam would result in a decrease in
the amount of methane in the product. A set of equations , which is used to calculate the
composition of exit stream, is eq.(4),(5) and eq.(8).
Carbon composition via eq-8 can theoretically be prevented by ensuring that steam is present
in excess of some minimum amount calculated using the equilibrium equations. Any increase
in steam also has the effect of increasing methane conversion. Most Commertial reformers
operate safely with steam carbon ratio in the range of 3 to 4.5.
Natural gas is the only most convenient and economical raw material available in Pakistan.
This God gifted treasure is found in large reserves at Sui, Mari and some other areas. Natural
gas is easily available , cheap raw material , containing low impurities and there are no
transportation and storage costs involved. Hence natural gas is the most economically suitable
raw material for synthesis gas.
Coal is another source for the Sun. gas production in Pakistan. Coal available in Pakistan at
MAkerwal, Dhodak and Kalabagh but its quality is very poor. However , the largest reservoirs
of coal in world now found in Pakistan at Thar. No doubt, these reservoirs contain small
amounts of sulfur about 0.1-0.7% but there are some other factors involved in degrading the
coal selectivity for Syn. Gas production , such as high transportation cost , handling and
storage cost , further more additional equipment (gasifier etc) and process costs. Coal contains
much impurities and mineral materials (as compared to the natural gas) lead to the formation
of the various pollutants during combustion having adverse environmental impacts when
emitted into the atmosphere. The environmental aspects that are associated with the use of
coal are, the formation of pollutants such as fly ash , sulfur oxides, nitrogen oxides and other
mineral materials. Also coke formation occur and this is higher compared to the natural gas
and this reduces the activity of catalyst and may stick to the walls of steam reformer which
reduce the heat transfer rate.
Naphtha is not economically viable for Syn gas production in Pakistan, its reservoirs are limited
in Pakistan and do not meet sufficiently the other demands (motor fuels). Its costs are too
much as compared to the natural gas, hence it is not usable , same is the matter involved in
selection of heavy hydrocarbons.
Production Of Methanol From Natural Gas 17
Production Of Methanol From Natural Gas 18
Capacity Selection
As mentioned earlier that currently thee is no methanol producing plant in
Pakistan and all is being imported from other countries (see in table).Major exporters are Saudi
Arabia and Iran.
Methanol consumption in Pakistan is about 26800 tons / year (90 tons /day), report issued by
Federal Bureau of Statistics 2004-2005. Lets take a look to the international market ; methanol
production is going to increase and foreign methanol producers are extending their capacities
in order to meet the growing demand (as shown in the tables, where world methanol plants
capacities supply /demand by the year 1998- 2007 are given , which contains the previous ,
present and anticipated capacities and shows comprehensive increasing trend in demand).
Production Of Methanol From Natural Gas 19
is a matter of great
consideration for scientists.
As far as Pakistan is concerned , gasoline and diesel prices are high and
unstable. CNG and LPG are used as alternative fuels but methanol is easy to be stored and
transported compared to CNG and LPG (it is a liquid fuel. These characteristics make the
prices of methanol vehicles and refueling stations cheaper than the price of CNG and LPG
vehicles and refueling stations. These methanol based vehicles will be available by the year
2005 in foreign markets and some major motor manufacturing companies may also invest in
Pakistan,
Raw material foe methanol synthesis (N.G) is cheaper here in Pakistan, which is
al friendly. In
Pakistan , methanol is being employed in making urea formaldehyde , acetic acid and
methalated spirit for pharmaceutical and dyes etc. industries. Now a new formaldehyde plant
is being installed by Dyno chemicals at Hub Industrial And Trading Estate. Super Chemicals
(Karachi) , Wah Nobel Chemicals (Wah Cantt.) and Pakistan Resins (Azad Kashmir) are also
manufacturing urea formaldehyde.
As A result of this brief discussion , we may say that our capacity of 150 tons/
day is reasonable , where 90 tons / day is present consumption in Pakistan and remaining 60
tons/ day could be exported and If demand of Pakistani market increases , we may reduce or
stop its export to fulfill out demand.
the industry has expanded to include four larger plants with an annual production capability
close to 3 million MT of methanol.
At the MHTL Point Lisas Methanol Complex, methanol is made using the ICI Low Pressure
Methanol Synthesis Process. The two main raw materials used are natural gas (96% methane)
received from the National Gas Company (NGC) to provide the carbon and hydrogen
components and water from the Water and Sewerage Authority (WASA) to provide the oxygen
component. These raw materials undergo a series of chemical reactions to produce crude
methanol which is then purified to yield refined methanol, having a purity exceeding 99.9%.
The plants operate continuously 24 hours a day in a production process that can be divided
into four main stages: Feed Purification, Reforming, Methanol Synthesis and Methanol
Purification as shown in the flow sheet below:
The two main feed stocks, natural gas and water, both require purification before use.
Natural Gas contains low levels of sulphur compounds and undergo a desulphurization
process to reduce, the sulphur to levels of less than one part per million. Impurities in the water
are reduced to undetectable or parts per billion levels before being converted to steam and
added to the process. If not removed, these impurities can result in reduced heat efficiency
and significant damage to major pieces of equipment.
Production Of Methanol From Natural Gas 27
STEP 2: REFORMING
Reforming is the process which transforms the methane (CH4) and the steam (H2O) to
intermediate reactants of hydrogen (H2), carbon dioxide (CO2), carbon monoxide (CO). Carbon
dioxide is also added to the feed gas stream at this stage to produce a mixture of components
in the ideal ratio to efficiently produce methanol. This process is carried out in a Reformer
furnace which is heated by burning natural gas as fuel.
This continual recycling of the synthesis gas however results in a build-up of inert gases in the
system and this is continuously purged and sent to the the reformer where it is burnt as fuel.
The crude methanol formed is condensed and sent to the methanol purification step which is
the final step in the process.
The 68% methanol solution is purified in two distinct steps in tall distillation columns called the
topping column and refining column to yield a refined product with a purity of 99% methanol
classified as Grade AA refined methanol.The methanol process is tested at various stages and
the finished product is stored in a large secured tankage area off the plant until such time that
it is ready to be delivered to customers. Since
The Leading Concept Methanol process in use at the Coogee Methanol Plant has various
advantages compared to the conventional methanol processes. Some of those advantages are
that it is efficient and compact and substantially reduces waste through the internal recycling of
process effluents.
Production Of Methanol From Natural Gas 28
Natural gas feedstock is delivered to the plant via a pipeline from the main Sui to plant location
carrying Bass Strait gas. The gas is first compressed and then purified by removing sulphur
compounds. The purified natural gas is saturated with heated and recycled process waste
water. The mixed natural gas and water vapour then goes to the gas heated reformer to be
partially converted to synthesis gas, a mixture of carbon dioxide, carbon monoxide and
hydrogen. This partially converted gas is then completely converted to synthesis gas by
reaction with oxygen in the secondary reformer.
The synthesis gas is then converted to crude methanol in the catalytic synthesis converter.
The crude methanol is purified to standard quality specifications by removing water and
organic impurities through distillation. The water and organic impurities are recycled.
Process Description
The Coogee Energy plant is designed to produce 164 tones per day of methanol from about 5
TJ/day of Bass Strait natural gas.
The plant consists of four main process steps : feed gas preparation, synthesis gas generation,
methanol synthesis and distillation supported by utilities and offsite units.
Feedgas Preparation
The total feed stream is then heated in the gas heated reformer preheated. Both the preheated
and boiler are fired with a mixture of synthesis loop purge gas and natural gas.
Reactions
There are three main chemical reactions which occur in this process step :
Steam reforming-
The net effect of these reactions is the production of a synthesis gas stream which is
composed of carbon monoxide (CO), carbon dioxide (CO2) and hydrogen (H2).
Description
Preheated gas flows from the preheater to the tube side of the advanced gas heated reformer
(AGHR). The feedstock is heated from the feed temperature of 425 C as it passed down
through the catalyst and the reforming reactions start. The AGHR contains 19 reforming tubes
which contain the reforming catalyst.
Hot reformed gas exits the bottom of the reforming tubes and flows to the tube side exit of the
AGHR at about 700C. The heat required for the endothermic reforming reaction is derived
from cooling the secondary reformer effluent in the shell side of the AGHR. About one quarter
of the methane is reformed in the AGHR.
The partly formed gas flows from the AGHR to the combustor/secondary reformer where the
bulk of the reforming takes place. The heat required for the endothermic reforming in both the
AGHR and secondary reformer is provided by partially burning the AGHR effluent with pure
oxygen in the combustor located integrally at the top of the secondary reformer. Oxygen is
injected into the gas via a specially designed gun. About 0.50 tonne of oxygen per tonne of
methanol is required.
The oxygen is completely consumed and the resulting hot gas stream passes over the
secondary reforming catalyst. Reforming reactions continue and the gas leaves the secondary
reformer at up to 1000C with less than 0.5% methane slip. The secondary effluent passes to
the AGHR shell and thence through the heat recovery train to provide heat for the saturator
circuit and distillation reboilers. The process condensate which condenses out of the reformed
gas is recycled back to the saturator. After heat recovery the reformed gas is finally cooled and
then compressed to about 70 barg in the synthesis gas compressor to be fed as synthesis gas
to the synthesis loop.
Bass Strait natural gas contains about 93.6 mol% of methane, 3.5 mol% of ethane with the
balance being predominantly propane, nitrogen and carbon dioxide. On an offshore facility with
less sophisticated gas separation facilities there may be higher levels of higher hydrocarbons
such as components but the oxygen consumption would increase.
The synthesis gas joins the synthesis loop recycle gas from the circulator to pass through the
loop interchanger and be fed to the methanol converter at about 130 C. The converter is a
tubular cooled converter design where the gas is preheated to reaction temperatures inside the
tubes as it flows up through the hot catalyst bed. This type of converter maximizes catalyst
efficiency as it enables a temperature profile to be maintained inside the converter that is close
to the maximum reaction rate curve. The hot reacted gas leaves the converter and provides
heat to the saturator water circuit and the loop interchanger before finally being cooled. Crude
methanol is separated from the uncondensed gases in the loop catch pot and the gases
recirculated back to the converter via the circulator.
Production Of Methanol From Natural Gas 30
Distillation
Crude methanol from the loop catch pot is filtered to remove traces of wax, let down in
pressure and fed to the product purification section. This section consists of a topping column
and a refining column. Unlike most methanol distillation columns these columns are packed
with structured packing. Reboiler duty is provided by reformed gas. The product methanol
specification is for a water content of less that 0.10 wt %. The water bottoms from the refining
column has a specification of less than 100 ppm of methanol and is recycled back to the
saturator. Other synthesis byproducts such as higher alcohols are collected as fusel oil and
recycled back the saturator.
Introduction
The emphasis on reducing the cost of production of methanol is nothing new. Aside from a
short period after the invention and commercial introduction of the Low Pressure Methanol
Process by ICI in the mid-1960s, that pressure has always been present. ICI itself was no
stranger to this as many of its older businesses were in commodity products whose profitability
relied critically on minimizing the cost of production in order to maintain acceptable margins.
However, cost of production is not just a case of reducing capital cost, although undoubtedly
this is an important part of the total picture. Often the installed cost of the plant appears to be
given greater weighting than is justified from a simple economic assessment. It is
understandable, though, that at the time of selection of the technology vendor, everyone's
mind tends to be focused on the need to raise the money, and fixed and variable costs of
operation can recede into the distance.
Methanex and Synetix have been working together for some time to identify the optimum route
for syngas generation for the manufacture of methanol and other GTL products. Many options
were investigated, but it was determined that the Synetix Syngas Generation (SGG) process
offered the most economic route and the methanol process based on SGG, the LCM Process,
was the most attractive option at high capacities.
Historical Perspective
It was against a background of intense competitive pressure on its Fertilizer Business that ICI
mandated its Catalyst and Technology Licensing Department (now a part of Synetix) to
develop a compact reforming process to revolutionize the manufacture of ammonia. In many
Production Of Methanol From Natural Gas 31
ways, the process that was developed, LCA, was revolutionary and ahead of its time, but the
fundamental principles behind the project were similar to those operators need to adopt to
prosper in today's highly competitive methanol industry.The legacy of ICI's commitment in
building the LCA plants at its Severnside Works in the late
1980s is that the Synetix Gas Heated Reformer (GHR) can no longer be thought of as new
technology. It is well-proven now, with over 30 operating years experience spread over the 4
plants that have been built around the technology. These plants are:
Absolutely key to the successful operation of these units has been the adoption of the correct
metallurgy to withstand the conditions within the reformer. There can be no doubt whatsoever,
that metal dusting has been overcome as an issue within the range of operating conditions of
these plants. However, without detracting from the importance of the metallurgy, it is the
mechanical design of the reformer that turns concept into reality. With the introduction of the
Advanced Gas Heated Reformer (AGHR) into the Coogee Energy MRP in April 1998, Synetix
incorporated a number of novel features that significantly simplified the compact reformer in
terms of design,construction, maintenance and operation.
Selling price
Financing costs
Gas price
Import tariffs
Delivery costs
Maintenance costs
Manpower costs
Plant installed cost
Plant efficiency
Plant reliability
Items 1-3 are commercial issues over which the operating company has varying degrees of
influence. Items 4 and 5 will be very location specific, with the latter being a key factor as
methanol is transported from more remote locations to the consuming markets. Items 6-10 are
influenced by location, but it is in these aspects that choice of technology and the standard of
engineering design can have a major impact. The focus of the rest of the paper will be mainly
on these areas.
Compact Reforming
The term "Compact Reforming" implies that the main aim of the new technology is to reduce
the size. This was indeed a consideration, and it may be the only benefit offered by certain
types of compact reforming device. However, when Synetix was developing the syngas
process for the new ammonia plants for ICI, there was a much broader goal, which included
the complete elimination of steam generation and the steam system. This required a complete
Production Of Methanol From Natural Gas 32
rethink and a major simplification of the whole heat recovery scheme. The intention was to use
the hot reformed gas from the Secondary Reformer to provide the heat directly for the methane
steam reaction in a heat exchanger reformer. It was not the first time such an idea had been
proposed, but the major stumbling block was always the fact that metal dusting conditions
were present on the hot side of the heat exchanger.
Many options had been considered by others, including approaches that would avoid metal
dusting by, for example, using ceramic tubes, but none had been successful. The
breakthrough by Synetix came in first identifying materials that were resistant to metal dusting
under the conditions envisaged and then in proving that they were resistant in a full-scale,
single-tube reformer operating under real process conditions. This trial unit was built and
operated on ICI's Bellingham, UK site and provided essential process design data, but more
importantly verified the selection of metallurgy.
The first successful implementation of compact, heat exchange reforming on the industrial
scale was in the GHRs installed on the LCA plants at Severnside, UK in 1988. The first
successful deployment of the AGHR was at Laverton, Australia in 1998.
In the LCM Process, between 30 and 40% of the heat being supplied into the saturator circuit
comes from the methanol synthesis loop. So, if the synthesis loop were not running, there
would be a significant shortfall of heat that would need to be acquired from elsewhere or the
whole plant would have to shut down. Normally, whenever there is a trip on a plant, everything
is done to try to maintain flow through the reformer and firing on it in order to avoid a
temperature cycle. This is where another valuable feature of the LCM Process becomes
important, and that is the ease of start-up and shut-down, which means that a temperature
cycle on the reformer is of rather less concern. The AGHR can be thought of as simply a feed
effluent exchanger around the Secondary Reformer. Start-up then requires nothing more than
a mechanism to get the Secondary above the auto-ignition temperature of the feed gas and
the whole unit will come on stream very quickly. Following a plant trip, heat is trapped within
the Secondary by the feed effluent exchangers preventing it cooling too much. From a cold
restart, heating is achieved using a simple catalytic combustor as a start-up heater generating
hot syngas. On the LCM Process it may take up to 12 hours from introduction of feed gas
before the plant is making methanol, whereas on a warm restart (which could occur even after
several days off line) the time taken can be 6 hours or less.
Production Of Methanol From Natural Gas 33
Production Of Methanol From Natural Gas 34
METHANOL SYNTHESIS
The heart of any Methanol synthesis process is Methanol converter. The converter contains
the catalyst over which synthesis gas is converted to methanol. The main difference between
competing methanol process today lies in the converter and its method of temperature control
and heat recovery.
Quench Converter
Multiple Adiabatic Converter
Tube-cooled Converter
Steam Raising Converter
1. QUENCH CONVERTER:-
The quench converter was the basis for the initial ICI low pressure methanol
process. Quench type converters used multiple catalyst beds, typically contain three to six
catalyst beds. Bed volumes are sized to help control the exothermic methanol synthesis
reaction. Additionally, cool feed gas is injected between beds to control or quench catalyst bed
inlet temperature. Reaction heat is recovered through added heat recovery exchangers located
downstream of the converter.
The adiabatic converter system employs heat exchanger rather than quench gas for
introduce cooling. Because the beds are adiabatic, temperature profile exhibits still the same
saw tooth approach to maximum reaction rate, but catalyst productivity is somewhat improved
because all of the gas passes through the entire catalyst volume. Costs for vessels and
exchangers are generally higher than for quench converter system.
3. TUBE-COOLED CONVERTER:-
The tube cooled converter functions as interchanger, consisting of a tube filled vessel
containing catalyst on the shell side. The combined synthesis and recycle gas enters the
bottom of the reactor tubes, where it is heated by reaction taking place in the surrounding
catalyst bed. The gas turns at the top of the tubes and passes down through the catalyst bed.
The principle advantage of this reactor is in the reduced catalyst volume, since the reduction
path move closely follows the maximum rate line.
Converter performance can further be enhanced by extending the catalyst below the tube
cooled area to act as a further adiabatic reaction zone.
Production Of Methanol From Natural Gas 35
There are varieties of tubular steam raising converters available, which feature radial
or axial flow, with the catalyst on either shell or tube side. The near isotherm reaction of this
rector type is the most thermodynamically efficient of the types used, requiring the least
catalyst volume, lower catalyst peak temperatures also results in reduced by-product formation
and longer catalyst life.
Production Of Methanol From Natural Gas 36
Low pressure drop, both in converter and heat exchanger equipment, to minimize
recycle compression energy.
High conversion per pass that reduces required cycle, minimizes synthesis loop capital
cost & maximizes reaction heat recovery.
Efficient recovery of exothermic reaction heat of methanol synthesis.
Corrosion resistance to formation of iron carbonyls that can poison the catalyst and
promote formation of undesirable hydrocarbon by-products.
A high yielding, commercially proven, long life synthesis catalyst to minimize costly
catalyst replacement.
Low capital cost.
Good economy of scale, high capacity single train converter.
KELLOGG 3%
Methanol was first synthesized commercially at low pressure when ICI commissioned its 300-
tons/dayplant at Birmingham in December, 1966. a copper based catalyst, more active and
selective was used. The greater activity of this catalyst permits the synthesis of methanol from
gaseous mixture of hydrogen and carbon dioxide at much lower pressure and temperature of
the order of 50 atm and 250 oC respectively. Several innovatory features were incorporated in
the design. They include a new simple type of quench bed converters, larger in diameter then
conventional converters and easy catalyst charging and discharging procedure. The use of
rotary machine of synthesis gas compression which was significant, because it demonstrated
the concept of single stream unit, well known in large scale ammonia plant, was now a
practical proposition for small methanol production units.
Production Of Methanol From Natural Gas 37
In 1972 ICI commissioned a 1100 tons/day plant based on their latest technology. It operates
at 100 atm and uses a modified version of original low-pressure methanol synthesis catalyst.
For capacity greater than 500 tons/day, the 100 atm process plants are adopted, whereas for
smaller plants of outputs from 150-500 tons/day, the 50 atm process is used.
In 1964 research work was resumed. At that time the purification of synthesis gas (Using Lurgi
Rectisol (50 atm process) was no longer a problem. Several years of development work
required in selecting from numerous
experience in Fisher Tropsch synthesis reactor, the methanol reactor was based on a design
worked out of Fisher Tropsch Synthesis.
PROCESS SELECTION
In 1966, an Imperial Chemical Industry (ICI) is the first, which announced the low
pressure process for synthesis of methanol using proprietary copper based catalyst.
Production Of Methanol From Natural Gas 39
pressure processes and proprietary copper-based catalyst; these companies included Lurgi,
Mitsubishi etc.
Today two processes are mostly used.
ICI process used Cu-Zn-Al catalyst while Lurgi process used CU-Zn-V or Cu-Mn-V catalyst.
Besides the catalyst, these processes differ in their method of temperature control and heat
recovery.
ICI use quench type adiabatic converter with multiple catalytic beds. Bed volumes are sized to
help control the exothermic methanol synthesis reaction. Additionally, cool feed gas is injected
between beds to control or quench catalyst bed inlet temperature. Reaction heat is typically
recovered through added heat recovery exchangers located downstream of the converter.
Whereas Lurgi used shell and tube (Isothermal type) converter with boiling water for
temperature controls. Overall results of quench type converter is best than other type of
converter.
The main drawback of water cooled tubular (Isothermal) converter is that internal tube sheets
have failed in some tubular isothermal methanol converter design. The long down times
associated with a catastrophic converter failure could financially devastate most procedures. In
addition converter internal baffles, expansion joints, gas distributors and internal exchangers
can fail and cause internal leaks. These components should be extremely rugged to withstand
the operating abuse imposed by actual commercial operation.
Cost is another major factor for the selection of process. ICI process has low cost as compare
to the other processes. Therefore the ICI process is also called ICI LCM (Low Cost Methanol)
Zinc Chromite catalyst, reduced zinc oxide promoted with Chromia was the catalyst used in the
1st
The zinc Chromite catalyst with improvements over the years was only the catalyst of
consequence used for the high process methanol process, up until the high pressure process
Although BASF is credited with a 1st commercial methanol process generally attributed to G.
TART in FRANCE in 1921. He defined his methanol catalyst has being all metal, oxides and
salt active in hydrogenation. Small unit was built near Paris to test catalyst for PARTARTS
process and began operation in 1923. The unit was designed to operate at 150-200 atm
pressure. 300-6000C, with hydrogen to carbon monoxide feed gas ratio of 2:1.
The BASF high pressure methanol process was operated at 250-3500 C, similar to the
conditions purposed by PARTART. Now low pressure, process commonly called ICI low
pressure process is used because of its practical feasibility.
known to be much more susceptible to poisoning by sulfur, chlorine, etc. than zinc Chromite,
Zinc Chromite, for example, could tolerate sulfur levels of more than PPM in the feed gas,
whereas for copper based catalysts, sulfur must be kept below 1 PPM. Generally poor quality
of synthesis gas and the limited purification techniques available at that time resulted in an
unacceptably short operating life for the copper based, catalysts and precluded their
commercial use.
A second breakthrough in the methanol technology occurred in 1966 with the introduction of
-pressure process for the production of methanol. This was made possible by a major
improvement in synthesis gas quality from the introduction of hydrocarbon steam reforming
and improved purification techniques for the hydrocarbon feed stock. The synthesis gas from
steam reforming contained only trace quantities of impurities and proved ideal for methanol
synthesis with a copper catalyst. The ICI process, using a much more active copper based
catalyst could operate efficiently at 50 atm pressure and at temp. of 220-280oC.
The copper based catalyst developed by ICI was also more selective than the high pressure
zinc chromite catalyst and operated at a much lower temp. Consequently, it produced a
significantly lower of impurities than zinc Chromite as shown in following table.
Production Of Methanol From Natural Gas 43
followed with their own alternative low-press. Methanol processes and catalysts.
Companies that currently have both a methanol process and catalysts, include ICI,
Lurgi, Haldor Topsoe, BASF, Ammonia Casale and Mitsubishi Gas Chemical.
A patent survey of representative copper based methanol catalysts is shows in
following table.
All commercial low-pressure methanol catalyst contains copper and zinc oxides together with
one or more additional promoters, usually aluminum or chromium oxide. ICI, for example,
reports a standard industrial catalyst to contain copper oxide, zinc oxide and Alumina in a ratio
of 60:30:10, respectively.
Production Of Methanol From Natural Gas 45
Production Of Methanol From Natural Gas 46
CH3OH 80% wt %
H2O 18%
CO2 0.20% W
HCHO 0.40% Waste Water
CH3OCH3 0.40%
C2H5OH 0.30%
C3H7OH 0.20%
C5H11OH 0.20%
CH3COOH 0.30%
Methanol Balance:-
0.8 A4 = 0.9985 A
A4 = 187.21 tons
Calculation of W:-
Water in W = Water in A4 - Water in A
= 33.48 tons
C2H5OH in W = C2H5OH in A4
= 0.561 tons
C3H7OH in W = C3H7OH in A4
= 0.374 tons
C5H11OH in W = C5H11OH in A4
= 0.374 tons
% of CH3COOH = 1.57 %
% of C2H5OH = 1.58 %
% of C3H7OH = 1.05 %
% of C5H11OH = 1.05 %
Calculation of L:-
HCHO in L = HCHO in A4 - HCHO in A
= 0.744 tons
CO2 in L = CO2 in A4
= 0.374 tons
CH3OCH3 in L = CH3OCH3 in A4
= 0.748 tons
% of HCHO = 39.85 %
% of CO2 = 20.04 %
% of CH3OCH3 = 40.09 %
Production Of Methanol From Natural Gas 48
A2 A3
A1 Reactor Separator
M
H2 76.68% Mol %
CO 13.78% Mol %
CO2 9.41% Mol %
N2 0.13% Mol % A4
276.43 K.Mol /hr
CH3OH 70.54 mol %
H2O 28.21 mol %
CO2 0.128 mol %
HCHO 0.376 mol %
CH3OCH3 0.245 mol %
C2H5OH 0.184 mol %
C3H7OH 0.0940 mol %
C5H11OH 0.0641 mol %
C Balance:- CH3COOH 0.1410 mol %
N2 Balance:-
0.13% A1 = 3% A7
A1 = 2307.69% A7 (2)
Putting Eq (2) in (1),
513.15% A7 = 201.23
So Eq(2) becomes,
Reactor:-
Now suppose, 50% conversion of CO & CO2 per pass
22% * A6 = 180.17
A6 = 818.98 K.Mol /hr
So,
H2 in A6 = 614.23 K.Mol /hr
CO in A6 = 106.46 K.Mol /hr
CO2 in A6 = 73.70 K.Mol /hr
N2 in A6 = 24.56 K.Mol /hr
A3 = A4 + A5
D2
Separator A1 = 904.96 K.Mol /hr
H2 76.68% Mol %
H2 57.42% By vol CO 13.78% Mol %
CO 10.32% By vol CO2 9.41% Mol %
CO2 7.04% By vol N2 0.13% Mol %
N2 0.10% By vol W1
H2O 25.11% By vol H2O 100%
Overall Balance:-
D2 = W 1 + A1
D2 = W1 + 904.96 (3)
H2O Balance:-
25.11% * D2 = W1 (4)