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Production Of Methanol From Natural Gas

Production Of Methanol From Natural Gas

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 was first obtained commercially some 150 years ago
by the destructive distillation of wood. Today it is produced
mainly from the steam reforming of natural gas via a synthesis
gas intermediate. Methanol can and is , however also being
produced from such alternative feed stocks as coal and residual
fuel oil.
Methanol has been traditionally used as a chemical intermediate
for the production of formaldehyde, solvents, methyl
derivatives(chemical groups containing CH3) and increasingly acetic acid. Recently methanol
has gained importance as a clean burning fuel and fuel additive in such diverse uses as a
boiler fuel for NOx control , as an octane booster for gasoline by direct blending or as a methyl
tertiary butyl ether derivative and for fuel cell application .
1.1 Physical Properties.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
Molecular weight

32.04

Vapor pressure

97 Torr at 20C

Boiling point

64.7C

Formula

CH3OH

Refractive index

1.3284 at 20C

Freezing point
Density

-97.68C

0.7913 g/mL (6.603 lb/gal) at 20C

0.7866 g/mL (6.564 lb/gal) at 25C

Production Of Methanol From Natural Gas

Dielectric constant

32.70 at 25C

Solvent group

Dipole moment

Polarity index (P')

Eluotropic value on alumina

2.87 D at 20C

5.1

0.95

Eluotropic value on octadecylsilane

1.0

Surface tension

22.55 dyn/cm at 20C

Melting Point

-97.7 0C

Viscosity

Solubility in water
Flash point
Auto ignition temperature
Explosive limits

Heat of Formation

Gibbs Free Energy

Critical temperature
Critical pressure
Critical volume

0.59 cP at 20C

Miscible in all proportions


11 oC

455 oC

7-36 %

-201.3 MJ/kmol

-162.62 MJ/kmol
512.6 K

81 bar abs

0.118 m/kmol

Heat of Vaporization

35278 kJ/kmol

Acute effects

Poisonous by ingestion or inhalation, may


cause respiratory failure, kidney failure,
blindness.

Regulatory and Safety Data

Chronic effects
.

As acute. Skin contact can cause dermatitis.

Production Of Methanol From Natural Gas

1.2 Reactions Of Methanol

Methanol is the 1st in a series of aliphatic, monohydric alcohols and undergoes many of the
reactions typical of this class of chemical compound , Methanol is also a typical member of this
series since it contains only one carbon atom . Methanol, for example can not undergo
elimination of the hydroxyl group and hydrogen to form the analogous olefins as do many of
the higher alcohols.
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.

1.3 CHEMICAL PROPERTIES OF METHANOL: CH3OH

Combustion of Methanol:

Methanol burns with a pale-blue, non-luminous flame to form


f
carbon dioxide and steam.
2CH3OH

Oxidation of Methanol:

302 ===>

2CO2 +

4H2O

Methanol is oxidized with acidified Potassium Dichromate, K2Cr2O7, or with acidified Sodium
Dichromate, Na2Cr2O7, or with acidified Potassium Permanganate, KMnO4, to form
formaldehyde.
CH3OH

===>

Methanol
2H2 + O2 ===>

HCHO

H2

Formaldehyde
2H2O

If the oxidizing agent is in excess, the formaldehyde is further oxidized to formic acid and then
to carbon dioxide and water.
HCHO
===> HCOOH ===> CO2 + H2O
Formaldehyde
Formic
Acid

Catalytic Oxidation of Methanol:

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

Dehydrogenation of Methanol:
Methanol can also be oxidized
ed to formaldehyde by passing its vapor over copper heated to 300 C. Two
atoms of hydrogen are eliminated from each molecule to form hydrogen gas and hence this process is
termed dehydrogenation.
Cu
300C
CH3OH ===>
HCHO
+
Methanol
Formaldehyde

H2

Dehydration of Methanol:

Methanol does not undergo dehydration reactions. Instead, in reaction with sulphuric acid the
ester, dimethyl sulphate is formed.
2 CH3OH
Methanol

Conc H2SO4
===>
(CH3)2SO4
Dimethyl
Sulphate

+
H2O
Water

Esterification of Methanol

Methanol reacts with organic acids to form esters.


CH3OH
Methanol

H(+)
+
HCOOH ===>
Formic
Acid

Substitution of Methanol with Sodium

HCOOCH3
Methyl
Formate

+ H2O
Water

Methanol reacts with sodium at room temperature to liberate hydrogen. This reaction is similar
to the reaction of sodium with ethanol.
2 CH3OH +
Methanol

2 Na ===>
Sodium

2CH3ONa
Sodium
Methoxide

+ H2
Hydrogen

Substitution of Methanol with Phosphorus Pentachloride


Methanol reacts with phosphorus pentachloride at room temperature to form hydrogen
chloride, methyl chloride, (i.e. chloroethane) and phosphoryl chloride.
CH3OH

Methanol

PCl5 ===>

HCl

Phosphorus Hydrogen

CH3Cl

Methyl

POCl3

Phosphoryl

Production Of Methanol From Natural Gas


Pentachloride Chloride

Chloride

6
Chloride

Substitution of Methanol with Hydrogen Chloride

Methanol reacts with hydrogen chloride to form methyl chloride (i.e. chloromethane) and water.
A dehydrating agent (e.g. zinc chloride) is used.

CH3OH +
Methanol

HCl

ZnCl2
===>

CH3Cl
Methyl
Chloride

H2O

1.4 USES OF METHANOL:-

The major portion of the methanol produced is used for making formaldehyde and a number of
chemical derivatives. Other applications include its use as solvents extractant and air
automation antifreeze. .

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

Methanol As A Ceansing Agent:-

Methanol is used in many cleansing operations such as in washing steel surfaces before
coatings are applied , rinsing the interiors of electronic tubes before they are evacuated ,
cleaning resin sheets before further processing , It is employed as a reducing agent in the
vapor phase cleaning of copper, the bright annealing of brass and in soldering fluxes. Its is
also used in special preparation for dry cleaning leather goods, in glass cleaners and in
flushing fluids for hydraulic brake system.

Methanol As An Anti Freezing Agent

Methanol offers the advantages of low molecular weights, low costs and high efficiency when
used as an automotive or industrial antifreeze. The pressure up cap on the radiator of the
modern engine cooling system prevent losses by evaporations. Methanol-antifreeze solutions
are considered less result of internal leakage then the high boiling type. Fuel system antifreeze
and windshield washer fluid based on methanol add to the dependability and convenience of
motor transport in methyl ester of 2-4 D is a selective weed killer, methyl salicylate is used in
medicines flavorings and perfumes., dimethylpthalate is as insect repellent and a plasticizer for
cellulose acetate methyl P=hydroxyl benzoate is a mold inhibitor for aqueous preparations,
containing starch guans and oil. Methylcrylate polymerizes readily to form clear plastics.

Formaldehyde:-

Worldwide, the largest amount of formaldehyde is consumed in the production of ureaformaldehyde 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.

Methyl T-Butyl Ether:-

MTBE is used as an oxygen additive for gasoline. Production of MTBE in the United States ha
increased due to the requirements of the 1990 Clean Air Act amendments, and has surpassed
formaldehyde as the largest domestic consumer of methanol. Projection for this use of
methanol are difficult to estimate due to the varying political and environmental considerations
that promote the use of cleaner burning motor fuels.

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

Methanol As An Alternative Fuel

Utilization of methanol as alternative fuel can be done through two different ways
that is by using directly in an internal combustion engine or by implementing methanol fuel cell
powered vehicles.
Pure methanol (M100) has been used in heavy-duty trucks and transit buses equipped with
compression-ignition diesel engines. Since 1965, M100 has been the official fuel for
Indianapolis 500 race cars. (The last time gasoline was used in the Indianapolis 500 was in
1964, when the race suffered a pile-up of cars that resulted in a gasoline fire and deaths.)
Typically, a blend of 85 percent methanol and 15 percent gasoline (M85) is used in cars and
light trucks. Pure methanol can also be reformed in fuel cells into hydrogen, which is then used
to power electric vehicles. Methanol-powered vehicles have been found largely in the West,
primarily in California. They can also be seen in the fleets of the federal government and the
New York

STORAGE AND SAFETY

Because methanol is corrosive to some metals and damaging to rubber and some
plastics, fuel storage tanks and dispensing equipment must be corrosion and damage
resistant. California requires that underground storage tanks for methanol be double walled.
Because methanol is water soluble, it could be quickly diluted in large bodies of water to levels
that are safe for organisms. Environmental recovery rates for methanol spills are often faster
than for petroleum spills. As with gasoline, methanol can be fatal when ingested. Inhalation of
fumes and direct contact with skin can also be harmful. Because pure methanol flames are
nearly invisible in daylight, gasoline is added as a safety precaution to provide color to a flame.
Added gasoline also serves to add a smell to this otherwise odorless liquid. Because of its high
flash point, methanol is less volatile than gasoline. It burns more slowly and at a lower
temperature. Methanol is transported by barge, truck, or rail. In the event of an

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
higher.

sometimes lower, but are usually equal or slightly

Ground-level-ozone-forming potential: 30 to 60 percent less. (In order to take advantage of


this characteristic, vehicles must be properly adjusted.)
Nonmethane evaporative hydrocarbons: Usually less.
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

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.
Nitrogen oxides: Usually comparable or less.
Greenhouse gases: Comparable to gasoline.
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, onedegree Fahrenheit.
At ambient temperature and atmospheric pressure, liquid methanol is basically similar to
gasoline or diesel fuel. Therefore methanol is easy to be stored and transported compared to
CNG & LNG. These characteristics make the price of methanol vehicles and refueling station
lower than the price of CNG or LNG vehicles and refueling station. For a certain type,
methanol vehicle is offered at lower price than gasoline vehicles, for the purchase of certain
No. OF vehicles.
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.

1.5 A Historical Overview

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

and 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.

Baptiste Dumas

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:

2.1 SYNTHESIS GAS FROM COAL: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 24002700 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, byproduct 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.

2.2 The Koppers-Totzok (K-T):-

Gasifier is an atmospheric process with extensive commercial experience in Europe,


Asia and South Africa. It will handle all coals; make virtually no by-products operate with high
thermal efficiency and high conversion. However, there is an extra cost associated with this

Production Of Methanol From Natural Gas

13

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).

2.3 The British Gas Council Lurgi (BGC-Lurgi):-

Gasifier is another high pressure process, more efficient than LURGI DRY ASH PROCESS.
Due to reduced steam usage and higher capacity, however, it produces great amount of byproducts and has only a limited ability to handle caking coals.

The Texaco and Shell-Koppers:-

Gasifiers are two of the most promising second-generation process. Both offer many of
the similar advantages as the atmospheric gasifiers, but both are high pressure operations,
that accept all coals and make virtually no by- products.
A large number of purification steps are necessarily required to produce methanol synthesis
gas from the crude product gas leaving the gasifier since the raw gases contain no large
number of undesirable by-products.
Some or all of the following process steps may be required. Cooling with steam generation,
water washing, compression, sulfur removal, shift conversion of carbon monoxide and after
that hydrogen and carbon dioxide removal.
Kopper
Totzek
Pressure(atm) 1.4
Temp.(oC)
1500
OxygenReqd. High
Steam Reqd.
Low
Capacity
850
(tons/day)
Raw Product ---gas analysis
Vol%
Carbon
58.1
monoxide
Hydrogen
29.3
Carbon
11.0
dioxide
Methane
0.1
Hydrocarbon ---Inerts (N2, Ar) 1.5

Winkler

Lurgi

BGC Lurgi

Taxaco

1.4 2.1
930
Medium
Medium
1000

20 -27
540-590
Low
High
500

20 - 27
480-540
Low
Low
1250

21 - 83
1290
High
None
2000

Shell
Kopper
31
1480
High
Low
1000

----

----

----

----

----

35.0

24.6

60.6

46.3

67.7

40.8
22.0

39.8
24.6

27.8
2.6

35
17

29.9
1.1

1.2
Trace
1.0

8.7
1.1
1.2

7.6
0.4
1.0

0.2
---1.5

0.2
---1.1

Production Of Methanol From Natural Gas

14

2.4 SYNTHESIS GAS FROM NAPHTHA


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.

2.5 SYNTHESIS GAS FROM NATURAL GAS: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.

R-SH + H2

R.H + H2S

ZnO + H2S

ZnS + H2O

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.

CnH2n+2 + nH2O

nCO + (2n+1) H2

CnH2n+2 + 2nH2O

-1

nCO2 + (2n+1) H2

CnH2n+2 (n-1/2) H2O

-2

(3n-1)/4 CH4 + (n-1)4 CO2

-3

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:

CH4 + H2O

CO + 3H2

H298 = 206.08 KJ/g

-4

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.

CO + H2O

CO2 + H2

H298 = - 41.17 KJ/g

-5

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

CO + 2H2

C + 2H2O

-10

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.
Reforming catalysts contain from 12 to 25 % nickel as nickel oxide supported on calcium
aluminate , alumina or calcium titanate .Alkali metal compounds added to prevent carbon
formation and increase catalyst durability. The feed stream to the reformer is distributed over
hundreds of parallel catalyst filled tubes, the tubes are subjected to a temperature range of 860
to 950 oC, wit process gas exit temperature in the range of 750 to 850 oC & pressure range
from 4 to 35 atm (450 to 3550 Kpa). Gas hourly space velocities are usually on the order of
5000 to 8000 based on wet feed.
The flue gases temperatures are in the range of 980 to 1040 oC. These hot flue gases are
transferred to a convection section where they are cooled and used to super heat steam for
provide motive power for compressors and large pumps, process steam for reforminf and
reboil duty for distillation.

2.6 SELECTION OF RAW MATERIAL

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.

3.1 Methanol Imports In Pakistan

Countries

2002-2003

Asian
Countries NS
Bangladesh
China
Dubai
Germany
Indonesia
Iran
Kuwait
Laos
Malaysia
Natherland
New Zealand
Saudi Arabia
Singapore

18000

2003-2004

LTR

Rs * 10 LTR
336

210000
13040
373651
690180
254266
-

2140
200
3094
10042
213426
-

2004-2005

26800

Rs * 10 LTR

610

Rs * 103

200000
132040
450000
9751
26080
101570
100000
13040
281600
13040
31965758
440000

2700
5217
5434
534
647
1662
2892
328
11671
249
394528
11410

2309723
58612
4099556
114338
101100
27093185
13040

23752
2478
41170
1934
4481
298683
273

Production Of Methanol From Natural Gas


South
Africa 14768
Rep
Spain
Turkey
25600
Thailand
U.S.A
424633
U.K
Total (LTR)
27196520
Tons
26800

20

148

104

40

386
2863
232635

3000
33762679
36559

145
438026

79200
200000
34068859
43800

1024
2033
375831

Production Of Methanol From Natural Gas

21

Production Of Methanol From Natural Gas

22

Production Of Methanol From Natural Gas

23

Production Of Methanol From Natural Gas

24

Production Of Methanol From Natural Gas

25

Production Of Methanol From Natural Gas

26

4.1 Methanol Manufacturing Process

The Methanol Industry in Trinidad began with the construction of a 1,200 MT state-owned

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:

STEP1 FEED PURIFICATION


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.

STEP 3 : METHANOL SYNTHESIS


After removing excess he
to the methanol production stage in the synthesis reactor. Here the reactants are converted to
methanol and separated out as as crude product with a composition of methanol (68%) and
water (31%). Traces of byproducts are also formed. Methanol conversion is at a rate of 5% per
pass hence there is a continual recycling of the unreacted gases in the synthesis loop.

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.

STEP 4 : METHANOL PURIFICATION

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

4.2 Methanol Process Description

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

Natural gas is compressed to about 45 bar and sulphur removed by hyrodesulphurisation in


the purifier. The desulphurising gas is cooled and flows to the saturator where it contacts with
hot water over a bed of packing. The saturated gas leaving the vessel contains about 92% of
the steam required for reforming. Saturator make up is 90% process condensate and the
balance refining column bottoms water. Prior to leaving the saturator the gas stream is
contacted with recycled fusel oil where waste products from methanol synthesis are stripped
off. A blow down stream is required to control dissolved solids. Additional steam generated in
the boiler is made up to the gas stream to achieve 3.0:1 steam to carbon ratio for reforming.
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.

4.3 Synthesis Gas Generation

Reactions

There are three main chemical reactions which occur in this process step :
Steam reformingCH4 + H2O = CO + 3H2
Shift reaction -

CO + H2O = CO2 + H2

Production Of Methanol From Natural Gas

29

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.

4.4 LCM -The Low Cost Methanol Technology


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.

Key Success Factors

Clearly, many factors are important to an operator/investor in making a project successful. A


number of these factors is listed below.
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.

Operability of the LCM Process

The absence of steam raising and a steam system offers many benefits, but it does mean that
there is no obvious source for the process steam required for the methane steam reforming
reaction. Fortunately, this is an easy issue to address since Synetix have used a saturator
circuit for many years as a way of recovering low grade heat and turning it into process steam
without raising steam directly. Water is pumped through a set of heat exchangers and warmed
up before being contacted in a packed tower with the natural gas feed from the Purification
section. The saturator typically provides J to of the process steam required in a conventional
plant, but this concept can easily be extended to provide all of the steam needed for the
methane steam reforming reaction in the AGHR. Of course, as this is the only source of steam,
the saturator circuit assumes a greater importance than before.
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.

5.1 TYPES OF CONVERTER:-

The four basic types of converters are


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.

2. MULTIPLE ADIABATIC 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

4. STEAM RAISING CONVERTER: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.

5.2 METHANOL SYNTHESIS TECHNOLOGY TODAY

Different companies have been involved in practicing their technologies for methanol
synthesis. But the question is which company offers the most dependable and economically
viable process.
This is visualized by the percentages obtained by evaluating their practical applications as
shown below:
Company Name

Production Rate

Imperial Chemical Industry (ICI)

61%

LURGI CORP.

27%

Mitsubishi Gas Chemicals (MGS)

8%

KELLOGG

3%

5.3 ICI LOW PRESSURE METHANOL PROCESS


successfully overcome by the ICI 50atm process.

Methanol was first synthesized commercially at low pressure when ICI commissioned its 300tons/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.

5.4 LURGI LOW PRESSURE METHANOL PROCESS

At the end of fifties, Lurgi began development of a low pressure methanol process, using
highly active copper catalyst at 50 atm pressure. At that time, the space time yield and catalyst
life was not satisfactory (Sulfur Poisoning) which resulted in the suspension of further
development work.

Production Of Methanol From Natural Gas

38

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.
This reactor is similar to a vertical
and tube heat exchanger and
was a promising solution, to both
reactor design and heat recovery
problem. The tubes closed at
their lower end by the hinged grid
with boiling water, maintaining a
substantially uniform catalyst
temperature over the reactor
cross section and over the full
length of the tubes.
Early 1970 Lurgi decided to build
its own methanol plant with a
small capacity to serve mainly for
demonstration purposes and also
to study the problems which
might come up in the large scale
plants. The first commercial plant
with a capacity of 4000 tones/yr
was built at wesseting (West
Germany) in April, 1971. This plant was built in two days, was designed on the basis of a
computer programme.

5.5 ADVANTAGES OF THE LOW PRESSURE METHANOL PROCESS

Reduced by-product formation resulting in lower feed stock consumption per ton of
methanol.
Reduced compression cost due to lower operating pressure.
The ability to use steam directory compressors on small plants.
Lower steam pressure through out the plant.
The avoidance of CO2 addition in natural gas based plant without incurring large
financial penalties.
Simplicity in design and low-pressure equipment, suitable for large and small plant.
Commissioning period.
Proved in wide practical services.

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.
1) ICI low pressure
(61%)
2) Lurgi low pressure process (27%)
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)
factor we select the ICI LCM process.

Production Of Methanol From Natural Gas

40

Production Of Methanol From Natural Gas

41

6.1 DESULPHERIZER CATALYST

Hydrocarbon feeds for steam reforming must have a very low sulfur contents, since nickel
reforming catalysts are quite susceptible to poisonings even by levels as low as 0.5PPM. In
many cases, sulfur can be removed b y adsorption over a bed of activated carbon at 15-500C.
Frequent regeneration may be necessary; which can be accomplished by heating the bed and
for stripping it with steam or hot gases. The activated carbon bed adsorbs high boiling sulfur
compounds such as mercaptans, much more rapidly than low boiling compounds such as H 2S
.As a result, adsorption over a sacrificial guard bed of zinc oxide at temperature in the range of
340-370 0C. Hydrodesulphurization may be necessary for organic sulfur compounds that are
not removed by either zinc oxide or carbon bed. This is accomplished by mixing the sulfur
containing steam with hydrogen, so that the hydrogen contents are approximately 5%, the
resulting mixture is passed over a bed of cobalt or nickel molybdate catalyst at temperature of
290-370oC. Under these conditions, sulfur compounds are conditions, sulfur compounds are
converted to hydrogen sulfide, which can be removed in a zinc oxide bed. Now a days, codes
are used to represent the catalysts shown here: The KATALCO range of absorbents and
hydrogenation catalysts ensures an optimized system for meeting individual plant
requirements.
Sulfur Removal Catalysts
Hydrodesulphurization Catalyst.
KATALCO32-4
KATALCO 41-6
KATALCO 61-1
PURASPEC 2570
These catalysts are used by ICI.

6.2 STEAM REFORMING CATALYST

Reforming catalyst usually contain from 12-25% nickel oxide supported on calcium aluminate
titanate. Calcium aluminate has generally replaced calcium aluminum silicate, has support
material to avoid the problem of silica migration encountered in earlier catalyst formulation.
Alkali metal compounds added to prevent carbon formation and to increase catalyst durability
include potassium aluminum silicate, potassium carbonate and potassium poly aluminate,
sulfur chlorine and arsenic compounds. Poison the catalyst, sulfur poisoning is reversible, but
chlorine and arsenic poisonings are severe and generally irreversible.
Synetix has been associated with prekvaerner process technology recently launched the new CRGLH series of catalysts. These
have been demonstrated to be the most active and robust commercially available product for
this application.
KATALCO

25-4

KATALCO

57-4

KATALCO

23-4

KATALCO

46-Serie

KATALCO

23-4Q

KATALCO

25-4Q

Production Of Methanol From Natural Gas

42

6.3 METHANOL SYNTHESIS CATALYST

High Pressure Catalyst

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.

6.4 LOW PRESSURE CATALYST

Early in the developing methanol industry, it was recognized that to significantly improve the
high pressure methanol process, a much more active catalyst than zinc chromite was needed.
A more active catalyst would permit operation at lower temperatures and pressures, yet still
allow acceptable production rates to be mentioned. Copper based catalysts known from the
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

LEVEL OF IMPURITES PRODUCED BY MS CATALYSTS


Impurity

ZnO/Cr2O3 catalyst

Cu/ZnO catalyst

Dimethyl ether

5000-10000ppm

20-150ppm

Carbonyl compds

80-220ppm

10-35ppm

Higher alcohols

3000-5000ppm

100-2000ppm

Methane

Variable

None

6.5 SOME OTHER SALIENT FEATURES


Copper based catalyst produced no methane.
The possibility of a highly exothermic runaway methanation reaction leading to catalyst
sintering and possible converter damage was a continual threat in the high pressure process.
This improvement is selectivity for the copper based catalyst over zinc Chromite was estimated
to reduce feed stock requirements from 5-10% for the equivalent amount of methanol
produced.
Hence ICI methanol catalysts were both active and long lived and generally considered a
benchmark in industry and represented a significant achievement in heterogeneous catalysis.
Catalysts used by ICI in methanol synthesis in accordance with SYNETIX are:KATALCO 51-8 PPT for ARC-Reactors.
KATALCO 51-8 PPT for Tubular and quench type reactors.

6.6 RECENT CATALYST DEVELOPMENTS


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.
Company
Ammonia casale
BASF
DUPONT
HALDOR TOPSOPE
ICI

Catalyst
system
Cu-Zn-Al-Cr
Cu-Zn-Al
Cu-Zn-Al-CrMn
Cu-Zn-Al
Cu-Zn- Cr
Cu-Zn-Al
Cu-Zn-Al

Typaical
atomic
ratio
29:47:6:18
32:42:36
38:38:0.4:12:12
50:19:31
37:15:48
61:30:9
64:23:13

Production Of Methanol From Natural Gas


LURGI

Cu-Zn-V
Cu-Mn-V
MITSUBISHI
GAS Cu-Zn-MP
CHEMICAL
Cu-Zn- Cr
Cu-Zn-B
SHELL
Cu-Zn-Ag
Cu-Zn-Re
UNITED CATALYSTS
Cu-Zn-Al

6.7 CURRENT CATALYST COMPOSITION

44
61:30:9
48:30:22
55:43:2
55:43:2
61:38:1
61:24:15
71:24:5
62:21:17

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

Balance Around Distillation Column


Light ends (L)

A4

Distillation
Column

Distillation
Column

80% wt %
18%
0.20%
0.40%
0.40%
0.30%
0.20%
0.20%
0.30%

W
Waste Water

Basis:- One day Operation


Methanol Balance:-

CH3OH 99.85% 149.775


H2O
0.14%
0.216
HCHO 0.003%
0.0045
CH3COOH 0.003% 0.0045

(2)

(1)
CH3OH
H2O
CO2
HCHO
CH3OCH3
C2H5OH
C3H7OH
C5H11OH
CH3COOH

A = 150 Tons/day

0.8 A4 =

0.9985 A

A4

187.21

CH3OH in A4

149.775 tons

H2O in A4

33.69

CO2 in A4

0.3748 tons

HCHO in A4

0.748

tons

CH3OCH3 in A4

0.748

tons

tons
tons

Total light ends in A4

1.87

C2H5OH in A4

0.561 tons

C3H7OH in A4

0.374 tons

C5H11OH in A4

0.374 tons

CH3COOH in A4

0.561 tons

Total Heavy ends in A4 =

tons

1.872 tons

tons
tons
tons
tons

Production Of Methanol From Natural Gas

Calculation of W:-

Water in W

=
=

CH3COOH in W

= CH3COOH in A4 =
= 0.557 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

35.35 tons

So,

Now,

47

Water in A4 - Water in A
33.48 tons
CH3COOH in M

% of H2O

94.71 %

% of CH3COOH

1.57

% of C2H5OH

1.58

% of C3H7OH

1.05

% of C5H11OH

1.05

HCHO in L

=
=

HCHO in A4 - HCHO in A
0.744 tons

CO2 in L

=
=

CO2 in A4
0.374 tons

Calculation of L:-

CH3OCH3 in L

=
=

CH3OCH3 in A4
0.748 tons

Total L

= 1.86 tons

% of HCHO

39.85 %

% of CO2

= 20.04 %

% of CH3OCH3

= 40.09 %

Production Of Methanol From Natural Gas


Now as
So,

A4

A4

= 7800.78 Kg/hr

48

187.21 tons/day

Now arranging the whole data in a tabular form,

Component

Wt %

Wt

CH3OH
H2O
CO2
HCHO
CH3OCH3
C2H5OH
C3H7OH
C5H11OH
CH3COOH

80%
18%
0.2%
0.4%
0.4%
0.2%
0.3%
0.3%
0.2%

So,

A4

276.43 K.Mole/hr

Basis:-

1 hr Operation

&1 day = 24 hrs


1 ton = 1000 kg

Mol.Wt k.Mole Mole %

6240.6
1404.1
15.60
31.20
31.20
23.40
15.60
15.60
23.40

32
18
44
30
46
46
60
88
60

195.0
78.0
0.35
1.04
0.67
0.50
0.26
0.17
0.39
276.4

70.54
28.21
0.128
0.376
0.245
0.184
0.094
0.064
0.141

Balance Around Converter:-

Recycle stream
H2
75%
Mol %
CO
13% Mol %
CO2
9% Mol %
N2
3% Mol %

A6

A1
H2 76.68%
CO 13.78%
CO2 9.41%
N2 0.13%

C Balance:-

23.19% A1
23.19% A1

A2
Mol %
Mol %
Mol %
Mol %

=
=

22% A7
22% A7

Reactor

A3

Separator

A4
276.43
K.Mol /hr
CH3OH
70.54
H2O
28.21
CO2
0.128
HCHO
0.376
CH3OCH3 0.245
C2H5OH
0.184
C3H7OH 0.0940
C5H11OH 0.0641
CH3COOH 0.1410

+ 72.79611 * A4/100
+ 201.235

A7

mol %
mol %
mol %
mol %
mol %
mol %
mol %
mol %
mol %

(1)

Production Of Methanol From Natural Gas

N2 Balance:-

0.13%

A1

A1

3% A7

2307.69% A7

Putting Eq (2) in (1),


535.15% A7

513.15% A7

= 201.23

A7

So,

A1

Now,

Now suppose,

A7

+ 201.235

39.21 K.Mol /hr


=
=
=
=

= 904.96

H2 in A1
CO in A1
CO2 in A1
N2 in A1

Reactor:-

(2)

22%

H2 in A7
CO in A7
CO2 in A7
N2 in A7

So Eq(2) becomes,

49

50%

=
=
=
=

29.41
5.09
3.52
1.17

K.Mol /hr
K.Mol /hr
K.Mol /hr
K.Mol /hr

K.Mol /hr
693.93
124.70
85.15
1.176

K.Mol /hr
K.Mol /hr
K.Mol /hr
K.Mol /hr

conversion of CO & CO2 per pass

50%

* {( 124.70 + 13% * A6 )

+ ( 85.15 + 9% * A6)} = 195.0

50%

* {( 209.86 + 22% * A6 )} = 195.0


209.86 + 22% * A6 = 390.03

So,

H2 in A6
CO in A6
CO2 in A6
N2 in A6

Balance at point M:-

A=

=
=
=
=

22% * A6
A6

= 180.17
= 818.98 K.Mol /hr

614.23 K.Mol /hr


106.46 K.Mol /hr
73.70
K.Mol /hr
24.56
K.Mol /hr
=

A1 + A6

Production Of Methanol From Natural Gas

Balance at point B:-

A2

1723.95 K.Mol /hr

A5

A6 + A7

A5

858.20 K.Mol /hr

A3

A4

A3

1134.63 K.Mol /hr

Balance Around the Separator:-

50

A5

Balance Around the Separator1:D2


H2 57.42%
CO 10.32%
CO2 7.04%
N2 0.10%
H2O 25.11%

Separator
By vol
By vol
By vol
By vol
By vol

Overall Balance:H2O Balance:Putting (4) in (3),


So,

A1 = 904.96 K.Mol /hr


H2
CO
CO2
N2

W1
H2O 100%

D2
D2

=
=

W 1 + A1
W1 + 904.96

25.11% * D2

W1

D2
= 25.11% * D2 +
74.89% * D2 = 904.96
D2 = 1208.39 K.Mol /hr
H2 in D2
CO in D2
CO2 in D2
N2 in D2
H2O in D2

=
=
=
=
=

693.86 K.Mol /hr


124.70 K.Mol /hr
85.07 K.Mol /hr
1.18 K.Mol /hr
303.4 K.Mol /hr

Now putting value of D2 in Eq(4) , we get,


W1

= 303.4 K.Mol /hr

76.68%
13.78%
9.41%
0.13%

Mol %
Mol %
Mol %
Mol %

(3)
(4)
904.96