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FACULTY OF CHEMICAL ENGINEERING

UNIVERSITI TEKNOLOGI MARA


TITLE:
MINI DESIGN PROJECT
(PRODUCTION OF METHANOL)
PREPARED BY:
AHMAD SHAHRUL AZROI B CHE RANI 2008403464
AFIFAH BT DZULKIFLI 2008403564
BALQIS BT ZAINAL ABIDIN 2008403518
MOHD FAREED B MOHD RASHIDI 2008403446
MOHAMAD ASYRAF B PAHMI 2008403542
MUHAMMAD ARIF B CHE RAHI 2008403562
NOOR HAYATI BT KAMARUDIN 2008403494
NOOR ELYZAWERNI BT SALIM 2008403532
NOR SURAYA BT MOHD KAMILAN 2008403488

DATE OF SUBMISSION:
5
TH
APRIL 2011
NAME OF LECTURER:
EN. AMMAR BIN MOHD AKHIR

TABLE OF CONTENT
INTRODUCTION
PART 1
1.0 History and General Information On Methanol 15
1.1 History 15
1.1.1 Methanol 16
1.1.2 Production of Methanol Synthesis 8
1.2 General Description 19
1.3 Usage 20

PART 2
2.0 Process in Producing Methanol 25
2.1 Process Selected and Selection Criteria
2.2 Process Description
2.3 Input and Output Structure 26
2.3.1 Overall 29
2.3.2 Conversion Reactor (Crv-100) 33
2.3.3 Conversion Reactor (Crv-102) 36

PART 3
3.0 Market Analysis 42
3.1 List of Equipment Supplier 42

PART 4
4.0 Site selection 49
4.1 Potential Site Location 49
4.2 Transport 49
4.3 Availability of Labor 50
4.4 Utilities and Facilities 50
4.5 Land 51
4.6 Climate 51

PART 5
5.0 Material safety data sheets 62
5.1 Methanol 62
5.1.1 Product identification 62
5.1.2 Hazards Identification 62
5.1.3 First Aid Measures 63
5.1.4 Fire fighting measure 63
5.1.5 Accidental Release Measure 64
5.1.6 Storage and Handling 64
5.1.7 Exposure Controls / Personal Protection 64
5.1.8 Physical and Chemical Properties 65
5.1.9 Stability and Reactivity Data 65
5.1.10 Toxicological Information 66
5.1.11 Ecological Information 66
5.1.12 Disposal Consideration 66
5.2 Methane
5.2.1 Product identification 62
5.2.2 Hazards Identification 62
5.2.3 First Aid Measures 63
5.2.4 Fire fighting measure 63
5.2.5 Accidental Release Measure 64
5.2.6 Storage and Handling 64
5.2.7 Exposure Controls / Personal Protection 64
5.2.8 Physical and Chemical Properties 65
5.2.9 Stability and Reactivity Data 65
5.2.10 Toxicological Information 66
5.2.11 Ecological Information 66
5.2.12 Disposal Consideration
5.3 Carbon Monoxide
5.3.1 Product identification 62
5.3.2 Hazards Identification 62
5.3.3 First Aid Measures 63
5.3.4 Fire fighting measure 63
5.3.5 Accidental Release Measure 64
5.3.6 Storage and Handling 64
5.3.7 Exposure Controls / Personal Protection 64
5.3.8 Physical and Chemical Properties 65
5.3.9 Stability and Reactivity Data 65
5.3.10 Toxicological Information 66
5.3.11 Ecological Information 66
5.3.12 Disposal Consideration 78
5.4 Carbon Dioxide
5.4.1 Product identification 62
5.4.2 Hazards Identification 62
5.4.3 First Aid Measures 63
5.4.4 Fire fighting measure 63
5.4.5 Accidental Release Measure 64
5.4.6 Storage and Handling 64
5.4.7 Exposure Controls / Personal Protection 64
5.4.8 Physical and Chemical Properties 65
5.4.9 Stability and Reactivity Data 65
5.4.10 Toxicological Information 66
5.4.11 Ecological Information 66
5.4.12 Disposal Consideration

5.5 Water
5.5.1 Product identification 62
5.5.2 Hazards Identification 62
5.5.3 First Aid Measures 63
5.5.4 Fire fighting measure 63
5.5.5 Accidental Release Measure 64
5.5.6 Storage and Handling 64
5.5.7 Exposure Controls / Personal Protection 64
5.5.8 Physical and Chemical Properties 65
5.5.9 Stability and Reactivity Data 65
5.5.10 Toxicological Information 66
5.5.11 Ecological Information 66
5.5.12 Disposal Consideration
5.6 Hydrogen
5.6.1 Product identification 62
5.6.2 Hazards Identification 62
5.6.3 First Aid Measures 63
5.6.4 Fire fighting measure 63
5.6.5 Accidental Release Measure 64
5.6.6 Storage and Handling 64
5.6.7 Exposure Controls / Personal Protection 64
5.6.8 Physical and Chemical Properties 65
5.6.9 Stability and Reactivity Data 65
5.6.10 Toxicological Information 66
5.6.11 Ecological Information 66
5.6.12 Disposal Consideration

PART 6
6.0 Environmental analysis 113
6.1 Project activity and data 118
6.1.1 Faith and Transport 119
6.2 Environmental Monitoring 120
6.3 Human and Aquatic Toxicity

PART 7
7.0 Mass Balance
7.1 Mass Balance of Mixer 130
7.2 Mass Balance of Reforming Reactor
7.3 Mass balance of Reactor and Seperator

PART 8
8.0 Energy balance 152

PART 9
9.0 Pinch temperature analysis 192

PART 10
10.0 Conclusion 196

PART 11
11.0 References 198










Introduction

The annual production of methanol exceeds 40 million tons and continues to grow by 4%
per year. Methanol has traditionally been used as feed for production of a range of chemicals
including acetic acid and formaldehyde. In recent years methanol has also been used for other
markets such as production of DME (Di-methyl-ether) and olefins by the so-called methanol-to-
olefins process (MTO) or as blend stock for motor fuels.
The production of methanol from coal is increasing in locations where natural gas is not
available or expensive. However, most methanol are produced from natural gas. Several new
plants have been constructed in areas where natural gas is available and cheap such as in the
Middle East. There is little doubt that (cheap) natural gas will remain the predominant feed for
methanol production for many years to come.
The capacity of methanol plants has increased significantly only during the last decade.
In 1996 a world scale methanol plant with a capacity of 2500 MTPD was started up in
Tjeldbergodden, Norway [1]. Today several plants are in operation with the double of this
capacity e.g. [2].
Plants with capacities of 10,000 MTPD or more are considered and planned for example
for the production of methanol for the MTO process [3]. Given the substantial investment in such
large scale plants there is considerable incentive to maximize single line capacity to take
advantage of economy of scale. This design project will describes the state of the art methanol
synthesis technology with focus on very large plants with a capacity of 00000 MTPD or more.
All commercial methanol technologies feature three process sections and a utility section
as listed below:

Synthesis gas preparation (reforming)
Methanol synthesis
Methanol purification
Utilities

In the design of a methanol plant the three process sections may be considered
independently, and the technology may be selected and optimized separately for each section.
The normal criteria for the selection of technology are capital cost and plant efficiency. The
synthesis gas preparation and compression typically accounts for about 60% of the investment,
and almost all energy is consumed in this process section. Therefore, the selection of reforming
technology is of paramount importance, regardless of the site.
Methanol synthesis gas is characterized by the stoichiometric ratio (H2 CO2) / (CO +
CO2), often referred to as the module M. A module of 2 defines a stoichiometric synthesis gas
for formation of methanol. Other important properties of the synthesis gas are the CO to CO2
ratio and the concentration of inert. A high CO to CO2 ratio will increase the reaction rate and
the achievable per pass conversion. In addition, the formation of water will decrease, reducing
the catalyst deactivation rate. High concentration of inerts will lower the partial pressure of the
active reactants. Inert in the methanol synthesis are typically methane, argon and nitrogen.
A comprehensive survey of methanol production technology is given in [4]. In the
following a brief description is given covering technologies available for the three process
sections.










PART 1

1.0 History and General Information on Methanol

1.1 History

1.1.1 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,
when he produced it via the distillation of boxwood. It later became known as
pyroxylic spirit. In 1834, the French chemists Jean-Baptiste Dumas and
Eugene Peligot determined its elemental composition.

They also introduced the word methylene to organic chemistry, forming it
from Greek methy = "wine" + hl = wood (patch of trees). Its intended origin
was "alcohol made from wood (substance)", but it has Greek language errors:
wrong Greek word used for the French word bois = "wood"; wrong Greek
word combining order influenced by French usage.
[dubious discuss]
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. The suffix -yl used in organic chemistry to form names of
carbon groups, was extracted from the word "methyl."

In 1923 the German chemists Alwin Mittasch and Mathias Pier, working
for BASF, developed a means to convert synthesis gas (a mixture of carbon
monoxide, carbon dioxide, and hydrogen) into methanol. A patent was filed
Jan 12 1926 (reference no. 1,569,775). This process used a chromium and
manganese oxide catalyst, and required extremely vigorous conditions
pressures ranging from 50 to 220 atm, and temperatures up to 450 C. Modern
methanol production has been made more efficient through use of catalysts
(commonly copper) capable of operating at lower pressures, the modern low
pressure methanol (LPM) was developed by ICI in the late 1960s with the
technology now owned
[citation needed]
by Johnson Matthey who is a leading
licensor of methanol technology.

The use of methanol as a motor fuel received attention during the oil crises
of the 1970s due to its availability, low cost, and environmental benefits. By
the mid-1990s, over 20,000 methanol "flexible fuel vehicles" capable of
operating on methanol or gasoline were introduced in the U.S. In addition,
low levels of methanol were blending in gasoline fuels sold in Europe during
much of the 1980s and early-1990s. Automakers stopped building methanol
FFVs by the late-1990s, switching their attention to ethanol fueled vehicles.
While the Methanol FFV program was a technical success, rising methanol
pricing in the mid- to late-1990s during a period of slumping gasoline pump
prices diminished the interest in methanol fuels. Additionally, methanol is
highly corrosive to rubber and many synthetic polymers used in the
automotive industry, whereas ethanol is not.
[5]


In 2006 astronomers using the MERLIN array of radio telescopes at
Jodrell Bank Observatory discovered a large cloud of methanol in space, 288
billion miles across.
[6][7]






1.1.2 The Production of Methanol Synthesis

Supp (1990) and Olah et al. (2006) present good overviews on the
characteristics of methanol and its production methods. This section is largely
based on these reference books. Another source may be found at wikipedia.

Methanol has a history extending back to about 1661, when Boyle
succeeded for the first time in recovering methanol from crude wood vinegar.
The component was re-discovered in 1822 by Taylor, after which in 1835 Von
Liebig succeeded in clarifying the chemical structure of methanol. In the
hundred years following this, methanol was recovered to an increasing degree
as wood alcohol by distilling wood.

In 1923, Mittasch and his staff succeeded in first producing methanol from
carbon monoxide and hydrogen (synthesis gas or syngas) using a catalyst.
Methanol was recovered together with a whole series of other components
containing oxygen, and the catalyst only had very short cycle times. Patart
then described a methanol synthesis process using hydrogenation active
metals, and metal oxides stated to be the catalyst. This led to a first
commercial plant. This process required vigorous conditionspressures
ranging from 3001000 atm, and temperatures of about 400 C. Modern
methanol production has been made more efficient through use of catalysts
(commonly containing copper) capable of operating at lower pressures.

At the beginning of the thirties, a series of commercial plants went into
operation in the USA, with capacities per plant of 100 to 500 tons/day, using
chromic acid activated zinc oxide catalyst. As early as 1935, it was recognized
that copper-based catalysts provided considerable advantages for methanol
synthesis, permitting considerably lower pressures and, above all, lower
temperatures. But these catalysts were extremely sensitive to sulphur
components. After development of suitable syngas purification systems,
mainly to remove sulphur, the first Low-Pressure Methanol process was
brought onto the market by Imperial Chemical Industries Ltd (ICI), Great
Britain. At that time, Lurgi Gesellschaft fr Wrme und Chemoteknik from
Germany also developed a low-pressure methanol process, which, contrary to
the ICI quench reactor, applied a tubular reactor cooled with boiling water.
Most of the methanol plants in the last 20 years operate according to the ICI
or Lurgi processes, while numerous high-pressure units have been converted
to the low-pressure system in the second half of the last century.

1.2 General Description

Methanol is also known as methyl alcohol, wood alcohol, wood naphtha or wood
spirits. It is a chemical with formula CH
3
OH. It is the simplest alcohol, and has a
characteristic of light, volatile, colorless, flammable, liquid with a distinctive odor
that is very similar to but slightly sweeter than ethanol. Methanol can be used as an
antifreeze, solvent fuel and also as a denaturant for ethanol as it is a polar liquid at
room temperature. In anaerobic metabolism of many varieties of bacteria and in
ubiquitos condition, methanol produced naturally. Therefore, that is why there are
small amount of methanol vapour in the atmosphere. In atmosphere, Methanol burns
in air forming carbon dioxide and water:


2 CH
3
OH + 3 O
2
2 CO
2
+ 4 H
2
O






Methanol flame is almost colorless in bright sunlight because of its toxic properties.

Methanol






1.3 Usage




The three largest derivatives of methanol are formaldehyde, methyl tertiary butyl
ether (MTBE) and acetic acid. However, methanol is seeing growing demand in fuel
application such as dimethyl ether (DME), biodiesel and direct blending into
gasoline.

Formaldehyde is used mainly to make amino and phenolic resins which are
employed in the manufacture of wood-based products such as panels, flooring and
furniture.

The main use for MTBE is an octane booster and oxygenate in gasoline.
However, it has been phased out following its contamination of underground water
supplies and the removal of the oxygenate mandate and liability protection. MTBE
will continue to be vital for fuel quality and cleaner emissions. As countries look to
remove sulphur and lead and reduce aromatic content in the gasoline pool, MTBE
will make a significant contribution to improve fuel quality.

Acetic acid has a number of outlets of which the two largest are vinyl acetate
monomer and purified terephtalic acid. Global demand for acetic acid has been
growing at a steady 4%/ year with PTA sector growth at double this rate driven by
polyester demand. In the area of petrochemical feedstocks, there has been
considerable interest in methanol-to-olefins(MTO) and methanol-to-propylene(MTP)
technologies with projects underway in China. The first MTO units in China were
started up in August 2010.

Methanol is also used for the basis of many other chemical products:
- The largest solvent use for methanol is as a component of windscreen wash
antifreeze. It can also be used to extract, wash, dry and crystallise pharmaceutical
and agricultural chemicals.
- Methlamines are used as intermediates in a range of speciality chemicals with
applications in water treatment chemicals, shampoos, liquid detergents and animal
feeds.
- Methyl methacrylate is employed in the production of acrylic polymers.
- Dimethyl terephthalate is used to make polysters although PTA is preferred
feedstock.
- Methanol and sodium chlorate are used to produce chlorine dioxide, a bleaching
agent for the pulp and paper industry.
- Glycol esthers are solvents used in acrylic coatings and newer high-solids and
waterborne coatings.
- Methyl mercaptan is used an intermediate in the production of DL-methionine, an
amino acid supplement in animal feeds.
Fuel uses to grow:
The use of methanol in fuel applications is expected to have a big impact on
future demand. Methanol can be used in biodiesel plants have been built, there has
been uncertainty in the biodiesel industry. Methanol is increasingly being used to
make DME , which can be employed as an alternative to diesel, a supplement to
liquiefied petroleum gas (LPG) and in power generation. The largest DME market in
China where it is blended into LPG. The DME industry in China is suffering from
capacity.









PART 2

2.0 Process in Producing Methanol

2.1 Process Selected and Selection Criteria

This section will explain the reason why the selected process has been chosen and
the disadvantages of the unselected processes.

Nowadays, there are several ways of producing methanol (CH
3
OH) in this world.
All of the processes have their own advantages and disadvantages. It is important to
choose the most efficient process in order to have a good and almost perfect
production of methanol. Here are the lists of the processes or step in producing the
methanol.
1. Synthesis Gas
2. Synthesis Methanol
3. Catalytic Conversion of Methanol
4. Methyl Alcohol

For this mini design project, we have decided to choose synthesis gas process for
producing the methanol. The synthesis gas is so far the best way in producing
methanol because it has more advantages compared to the other processes and it is
also being used commercially by many plants worldwide. Most methanols are
produced using either a high-pressure process or a low-pressure process. In the high-
pressure process (above 275 bars), synthesis gas is made by reforming natural gas and
forming carbon dioxide to balance the excess hydrogen by the equation
CO
2
+ 3H
2
CH
3
OH + H
2
O
This, in effect, produces more methanols. In the low-pressure (50 to 100 bars)
methanol processes, the excess hydrogen is purged from synthesis loop and is not
used to produce methanol. In this method, a large reformer must be built in order to
produce the equivalent amount of methanol. Commercially available cu-ZnO-Al
2
O
3

catalyst permits production of the desired product with high selectivity. The main
advantages of the low-pressure process are lower investment and production cost,
improved operational reliability and greater flexibility in the choice of plant size.
Stand-alone Auto Thermal Reforming (ATR) at low steam to carbon (S/C) ratio is the
preferred technology for large scale plants by maximizing the single line capacity and
minimizing the investment. The ATR produces a synthesis gas well suited for
production of both fuel grade and high purity methanol.


Here are the disadvantages of the other processes that have not been selected.
a) Synthesis Methanol

Synthesis methanol will produced three unwanted reaction which need a
further consideration and eventually will cause a high capital cost. Under this
reaction, CO will reacts with the walls of the reactor and produces iron
carbonyl which deposits on the catalyst and accelerates its deactivation which
is not good for a plant. This and the other disadvantages of the high pressure
operation led to the development of the low pressure process using copper as a
component of the catalyst.

b) Catalytic Conversion of Methanol

For catalytic conversion of methanol, there are too many flaws and
disadvantages that lead to the inefficient production. By using this process to
produce methanol, it will eventually produce several by-product which is
paraffins, olefins and aromatics. The extra separation or procedure needed to
set up to in order to deal with undesired by-product. Olefins are intermediates
in the conversion of methanol to aromatic hydrocarbons over zeolite. This
process is basically focusing on how to increase the olefin production instead
of methanol.

c) Methyl Alcohol

Basically methyl alcohol was produced from synthesis gas and it is also
obtained by the oxidation of methane using natural gas as the feedstock.
However, by using this process, only 60 percent of methanol produced which
the natural gas not fully converted. This means this process are quite similar
with synthesis gas but the fact that it is not being practiced by many company
in this world is a major disadvantage. This process also not focusing on
producing methanol but it is mainly on the production of methyl alcohol.
However methanol can be produced by purified with distillation.

2.2 Process Descriptions

Autothermal reforming (ATR) features a stand-alone, oxygen-fired reformer.
The autothermal reformer design features a burner, a combustion zone, and a catalyst
bed in a refractory lined pressure vessel as shown in Figure 3

Figure 3. Autothermal Reformer
The burner provides mixing of the feed and the oxidant. In the combustion zone,
the feed and oxygen react by sub-stoichiometric combustion in a turbulent diffusion
flame. The catalyst bed brings the steam reforming and shift conversion reactions to
equilibrium in the synthesis gas and destroys soot precursors, so that the operation of
the ATR is soot-free. The catalyst loading is optimized with respect to activity and
particle shape and size to ensure low pressure drop and compact reactor design.

The synthesis gas produced by autothermal reforming is rich in carbon monoxide,
resulting in high reactivity of the gas. The synthesis gas has a module of 1.7 to 1.8
and is thus deficient in hydrogen. The module must be adjusted to a value of about 2
before the synthesis gas is suitable for methanol production. The adjustment can be
done either by removing carbon dioxide from the synthesis gas or by recovering
hydrogen from the synthesis loop purge gas and recycling the recovered hydrogen to
the synthesis gas [6]. When the adjustment is done by CO2 removal, a synthesis gas
with very high CO/CO2 ratio is produced. This gas resembles the synthesis gas in
methanol plants based on coal gasification. Several synthesis units based on gas
produced from coal are in operation, this proves the feasibility of methanol synthesis
from very aggressive synthesis gas. Adjustment by hydrogen recovery can be done
either by a membrane or a PSA unit. Both concepts are well proven in the industry.
The synthesis gas produced by this type of module adjustment is less aggressive and
may be preferred for production of high purity methanol.


Methanol Synthesis and Purification

In the methanol synthesis conversion of synthesis gas into raw methanol takes
place. Raw methanol is a mixture of methanol, a small amount of water, dissolved
gases, and traces of by-products.

The methanol synthesis catalyst and process are highly selective. A selectivity of
99.9% is not uncommon. This is remarkable when it is considered that the by-
products are thermodynamically more favored than methanol. Typical byproducts
include DME, higher alcohols, other oxygenates and minor amounts of acids and
aldehydes.

The conversion of hydrogen and carbon oxides to methanol is described by the
following reactions:

CO2 + 3 H2 CH3OH + H2O (-H298K, 50Bar = 40.9 kJ/mol) (1)
CO + 2 H2 CH3OH (-H298K, 50Bar = 90.7 kJ/mol) (2)
CO2 + H2 CO + H2O (-H298K, 50Bar = 49.8 kJ/mol) (3)

The methanol synthesis is exothermic and the maximum conversion is obtained at
low temperature and high pressure. Thermodynamics, reaction mechanism, kinetics,
and catalyst properties are discussed in [9].

A challenge in the design of a methanol synthesis is to remove the heat of reaction
efficiently and economically - i.e. at high temperature - and at the same time to
equilibrate the synthesis reaction at low temperature, ensuring high conversion per
pass.

Different designs of methanol synthesis reactors have been used:

Quench reactor
Adiabatic reactors in series
Boiling water reactors (BWR)

A quench reactor consists of a number of adiabatic catalyst beds installed in
series in one pressure shell. In practice, up to five catalyst beds have been used. The
reactor feed is split into several fractions and distributed to the synthesis reactor
between the individual catalyst beds. The quench reactor design is today considered
obsolete and not suitable for large capacity plants.
A synthesis loop with adiabatic reactors normally comprises a number (2-4) of
fixed bed reactors placed in series with cooling between the reactors. The cooling
may be by preheat of high pressure boiler feed water, generation of medium pressure
steam, and/or by preheat of feed to the first reactor.

The adiabatic reactor system features good economy of scale. Mechanical
simplicity contributes to low investment cost. The design can be scaled up to single-
line capacities of 10,000 MTPD or more.

The BWR is in principle a shell and tube heat exchanger with catalyst on the tube
side. Cooling of the reactor is provided by circulating boiling water on the shell side.
By controlling the pressure of the circulating boiling water the reaction temperature is
controlled and optimized. The steam produced may be used as process steam, either
direct or via a falling film saturator.

The isothermal nature of the BWR gives a high conversion compared to the
amount of catalyst installed. However, to ensure a proper reaction rate the reactor will
operate at intermediate temperatures - say between 240C and 260C - and
consequently the recycle ratio may still be significant.

Complex mechanical design of the BWR results in relatively high investment cost
and limits the maximum size of the reactors. Thus, for very large scale plants several
boiling water reactors must be installed in parallel.

An adiabatic catalyst bed may be installed before the cooled part of the BWR
either in a separate vessel or preferably on top of the upper tube sheet. One effect of
the adiabatic catalyst bed is to rapidly increase the inlet temperature to the boiling
water part. This ensures optimum use of this relatively expensive unit, as the tubes are
now used only for removal of reaction heat, not for preheat of the feed gas. This is
illustrated in Figure 5, which compares the operating lines in identical service for
BWRs with and without adiabatic top layer.

Figure 5: Temperature and methanol concentration profiles in BWR reactors with and without
adiabatic top layer

The installation of the adiabatic top layer in the BWR reduces the total catalyst
volume and the cost of the synthesis reactor by about 15-25%. The maximum
capacity of one reactor may increase by about 20%.

A boiling water reactor with adiabatic top layer will be installed in a 1000 MTPD
methanol plant in China.

The last section of the plant is purification of the raw methanol. The design of this
unit depends on the desired end product. Grade AA methanol requires removal of
essentially all water and byproducts while the requirements for fuel grade methanol
are more relaxed. In all cases the purification can be handled by 1-3 columns, where
the first is a stabilizer for removal of dissolved gases.



2.3 Input and Output Structure


2.3.1 Overall

















2.3.2 Conversion Reactor (CRV-100)












2.3.2 Conversion Reactor (CRV-100)
































F
liq
=0 lb/hr
T=662F
P=435.1 psia
F
water
=7.943x10
4
lb/hr
T=1562F
P=435.1 psia
X
H20
= 1
F
1
= 7.074x10
4

lb/hr
T=1562 F
P=435.1 psia
CH
4
=1
2.3.3 Conversion Reactor (CRV-102)



























11,
4

=0

11,
2

= 0.0011

11,
= 0

11,
2

= 0.0002

11,
3

=0.9987


10,
4

= 0.0009

10,
2

= 0.0001

10,
= 0

10,
2

= 0.8593

10,
3

=0.1398


F
11
=0 lb/hr
T=127.6F
P=14.7 psia
F
10
= 3.722x10
6
lb/hr
T=127.6 F
P=14.7 psia

F
9
= 3.722x10
6
lb/hr
T=88.41 F
P=14.7 psia

9,
4

= 0.0008

9,
2

= 0.0001

9,
= 0.0073

9,
2

= 0.8613

9,
3

=0.1305
PART 3

3.0 Market Analysis

3.1 Supply and Demand

The objective of market analysis is to provide the pleasant appearance of methanol
market. It is also important to provide opportunities for the world market which it can be
categorize into two categories. The first categories is to attract many investors to invest in
the plant that is going to be build and the second one is to provide the a wide range of
possible site to market for the products and also to find the potential target client to market
their products.

There are few countries that produce methanol in the world. The country that produces
larger scale of methanol is The United States of America and China. The demand of
methanol especially in Asia countries such China is expected to increase as well as for the
demand for the world. From late August 2010, in just two months, the domestic Methanol
Market prices rose about 50%. At present, East and South China methanol market prices
rose or as high as 50% to 53%.

Methanol is widely consumed by many countries around the world. Hence, there is no
surprising to know that many countries imported methanol for domestic used such as
Malaysia, Thailand and many more.





3.2 Economic data

3.2.1 Raw Material Cost Estimation

The production is to achieve 387260 metric tonnes per annum. The raw
materials used are:
Raw material Cost estimation per year (RM)
Natural gas 207633

Water 6472200

The cost estimation of raw material:
= 207633+6472200 = RM 6679833
3.2.2 Equipment Cost Estimation

Equipment Quantity Cost per unit(RM)
Reactor 2 683009
Heat Exchanger 7 35000
Separator 2 233463
Mixer 1 711295
Vessel 3 7497
Compressor 1 293000
Pump 1 8690

The cost estimation of equipment:

= (2x 683009) + (7 x 35000 ) + (2 x 233463) + (1x711295) + (3 x 7497) +
(1x 293000) + (1x8690)
= RM 3113420

3.2.3 Operating Labor Cost Estimation

05

N
OL
= Number of operating labour operating per shift.
P
2
= Particulate processing steps.
N
np
= Non-particulate processing steps.










Equipment Quantity N
np

Reactor 2 2
Distillation column 2 2
Heat Exchanger 7 7
Separator 2 2
Compressor 3 3
Condenser 1 1
Total 17
A single operator will work on average of 49 weeks per year (3 weeks work
off) with 8 hours per shift and 5 shift per week.
Usually a chemical plant is operate 24 hours so it requires 3 shifts per day.
(49 weeks/year) x (5 shifts/week) = 245 shifts / year.
(330 days/year) x (3 shifts/day) = 990 shifts/year.
(990 shifts/year) x (operator.year/245 shifts) = 4 operators.

05

05


Number of operator needed:
(3.19) x 4 =13 operator
For all equipment:
Cost of operating labour per year:
(RM 2/hour.operator) x (8 hours/day) x ( 330 days/ year) x (13 operator)
= RM 68640/ year






3.2.4 Land Cost Estimation

By considering the plant site and extra site for future build up, the
estimation of land to buy is 3.5 acres which is approximate 14164 m
2
.








Figure: Plant estimation

Price per meter square of land
2
73 . 27
m
RM
=

Land cost
( ) 72 . 392767
73 . 27
14164
2
2
RM
m
RM
m = |
.
|

\
|








120 m

100 m



3.2.5 Utilities Cost Estimation

Estimated service requirement:

Steam : 2000 kg/hr
Cooling water : 1000 kg/hr
Electrical power : 10000 kW/d 0.59DOLLAR MW/h 2.5fen/ kw/h


Steam
year
RM
kg
tonne
hour
kg
year
hours
tonne
RM 1608
1000
1 2000 8040 10 . 0
=
|
|
.
|

\
|
|
.
|

\
|

|
|
.
|

\
|
|
.
|

\
|


Cooling water
year
RM
kg
tonne
hour
kg
year
hours
tonne
RM 8 . 155332
1000
1 2000 8040 66 . 9
=
|
|
.
|

\
|
|
.
|

\
|

|
|
.
|

\
|
|
.
|

\
|


Electrical power
year
RM
hours
day
day
kW
year
hours
kW
RM 4 . 99240
24
1 23000 8040 01288 . 0
=
|
|
.
|

\
|

|
|
.
|

\
|

|
|
.
|

\
|
|
.
|

\
|


Total utilities cost
year
RM
year
RM
year
RM
year
RM 20 . 256181 4 . 99240 8 . 155332 1608
=
|
|
.
|

\
|
+
|
|
.
|

\
|
+
|
|
.
|

\
|




3.2.6 Estimation of Fixed Capital Cost, Working Capital Cost, and
Variables Cost


Description
Cost
(RM)
Land 392767.72
Raw Material 6679833
Utilities 256181.20
Labor 68640
Equipment 3113420
Engineering &
Supervision
2500000
Construction expenses 2550000
Contractors Fee 1500000
Maintenance 1500000
Installation 5000000
Building 1000000
Total 24560842


Product profit estimation:
(143333 kg/hr) x (24 hr/d) x (335 d/y) / (RM 0.80 /kg) = RM 1440496650
Gross profit:
RM 1440496650 RM 24560842 = RM 1,415,935,808

Net Present Value Data


Discounted Payback Period Data


Cumulative Cash Position Data



Rate of Return On Investment Data


Payback Period Data













3.3 List of Equipments Supplier:

a) Shanghai Ger-Tech Compressor Co., Ltd.


Centrifugal Air Compressor

Quick Details

Place of Origin: Shanghai
China (Mainland)
Brand Name: Ger-Tech Model Number: SM-2075
Type: Centrifugal Configuration: Stationary
Power Source: DC Power or
AC Power
Lubrication Style: Oil-free Mute: No
Atmospheric
Pressure:: 1.013 bar A
Relative Humidity:: 80%





Packaging & Delivery

Packaging
Detail:
WOODEN CASE; DIMENSION: 2115 mm x 1455 mm x 1831
mm
Delivery Detail IN STORE OR 6~10 MONTHS

Specifications
- New Technologies applied to Micro-TM.
- Performance Enhancement, Safe and Easy.
- Versatile Controller.
- Long lifetime.

Advantages:
- Advanced technology assures the best performance in its components.
- High-performance turbo air compressor utilizes modern aircraft enginer
technology.
- It is safe and easy to operate our products.
- It has versatile controller, and intellect control system.
- New technologies are applied to Micro-TM.

Technical specification:
- Air compressor capacity: 800~1600 m
3
/ hr
- Air compressor discharge pressure: 6~10 bar A
- Air compressor intake pressure: 0.983 bar A
- Air feeding temperature: 35C
- Motor power: 175 HP
- Dimension: 2100 mm x 1440 mm x 1816 mm
- Weight: 2500 kg
- Cooling water temperature: 32C
- Protection Level: IP 55
b) Shandong Qingneng Power Co., Ltd.


Back Pressure Steam Turbine (B6-4.90/0.981)
Product Details:
Model NO.: B6-4.90/0.981
Standard: 4380&Times;2805&Times;2615
Trademark: QNP
Origin: China(Main Land)
Power(Mw): 6
Rated Speed: 3000r/Min
Steam
Rate(Kg/Kw.
H):
13
Exhaust
Pressure(Mpa):
0.981
Weight(T): 21.2
Press(Mpa): 4.9
Temp: 435
Flow(T/H): 78.15
Export Markets:
North America, South America,
Eastern Europe, Southeast Asia,
Africa, Oceania, Mid East, Eastern
Asia, Western Europe
Product Description
- Single-stage and multistage are all fittings selection.
- Power is between 100KW to 100MW, it can meet the needs of various industries
and conditions uses.
- Operating reliably and it is easy to operate.
- Single-stage has a simple structure, therefore it is convenient to install and the
adaptability is well.
- Adopt DEH or full hydraulic governing system.
- Protective system with complete functions.

c) Yueyang City Zhongda Mechanical & Electrical Co., Ltd.


Shell & Tube Heat Exchanger
Product Details:
Place of Origin Hunan, China (Mainland)
Brand Name Fulida
Model Number ZD-A003
Type Fin Tube
Application Heater Parts
Certification ISO9001
Eco-friendly Yes
Patent product Yes
Maximum Working Pressure 60pa
Product Description:

- The high Thermal Capacity with strong adaptability.
- High quality , reasonable price
- Unique quality
- High effect Heat exchanger, the structure is simple, easy install, maintenance
is convenient; Product technology is advanced, quality is stable.


Model Power
Air
flow (m3/h)
Output
static
pressure(Pa)
Temperature
efficiency(%)
Enthalpy
efficiency
Rated
power
(W)
Noise dB(A)*
Chill
room
Warm
room
ALH-
30BX
3

220 /50Hz
300 60 70-82
54-
59
73-81 130 28
ALH-
35BX
3

350 75 78-80
53-
57
72-79 180 31
ALH-
50BX
3

500 80 65-76
52-
57
71-78 240 33








PART 4

4.0 Site Selection

4.1 Potential Site Location

Several sites in China have been taken into consideration. These locations are
industrial site for various kinds of industries. These sites are located close to the
source of raw materials and also close to major forms of transport, which are road,
rail, sea ports and airports.

Xu Dong Da Jie 303

Xu Dong Da Jie 303 is located at Wuchang District in Wuhan City. Wuhan
City is a major transportation hub, with dozens of railways, roads and
expressways passing through the city. Wuchang was one of the three cities that
merged into modern-day Wuhan, the capital of the Hubei province, China. It
stood on the right (south-eastern) bank of the Yangtze River, opposite the mouth
of the Han River. The historic center of Wuchang lies within the
modern Wuchang District, which has an area of 82.4 square kilometers and a
population of 1,003,400.

Xu Dong Da Jie is located 11.2 km from Wuhan Port and only takes 18
minutes to reach there. Wuhan Port is located centrally between Beijing
and Guangzhou (Canton) and between Shanghai and Chongging, it is called the
thoroughfare of nine provinces. It is an important hub for transportation, with
many roads and railways meeting here. Wuhan Tianhe International Airport
situated 19.2 km from the port. Furthermore, the chosen location is located
27.5km from Xian Xilan Natural Gas Co.Ltd Hubei Branch which was the main
supplier for the methanols plant.
Xu Dong Da Jie is the most potential location for plant site because it is
located in the Wuhan City which is an important center for economy, trade,
finance, transportation, information technology, and education in Central China.
Wuhan has currently attracted about 50 French companies, representing over one
third of French investment in China, and the highest level of French investment in
any Chinese city. Therefore it is easier for our plant to develop and enter Frenchs
market.

Distance from:
- Wuhan port : 11.2km
- Xian Xilan Natural Gas Co.Ltd Hubei Branch : 27.5 km
- Zhongnan Hospital of Wuhan University: 3 km
- Bank of China 24-hour Self- service Bank : 4.4 km

4.2 Transport

The location Xu Dong Da Jie 303 is convenient and efficient because of easy
access to the rest of the world due to its closeness to the international shipping
lane and its connectivity with other modes of transport. Designation of Wuhan
Port as the most important port in the Wuhan City with an area of more than
70,000 sq km will become a convenient logistics hub of the Yangtze River and
Central China, a modern base for a variety of industries and an ecologically
friendly home for urban dwellers by 2020. The aim in china of making the Wuhan
Port the largest port in Asia make it more accessible and vibrant place in the near
future.


4.3 Availability of Labor
The current population estimation for Wuchang is 1,003,400 people. It is clear
that it will be plenty of labors available in that area. The forecasted benefits are
increase in business and employment opportunities.

4.4 Utilities and Facilities
Infrastructural facilities such as road accesses, electricity supply, water
supply, gas supply and telecommunications are readily available at Xu Dong Da
Jie 303. There also have availability of ancillary services and facilities such as
banking, hospital and fresh water supply.

In CNY In MYR
Cooling water : 21yuan/m
3
RM 9.72/m
3

Electrical power : 2.5fen kW/h RM 0.12 kW/hr

4.5 Land

Sufficient suitable land must be available for the proposed plant and for future
expansion. The land should be ideally flat, well drained and have suitable load
bearing characteristics. A full site evaluation should be made to determine the
need for piling or other special foundations. Particular care must be taken when
building plants on reclaimed land near the ocean in earthquake zones because of
the poor seismic character of such land.


Plants location:
Xu Dong Da Jie 303

Source: Google maps (Satellite view)


Source: Google maps (Map view)



Location from Xian Xilan Natural Gas Co. Ltd Hubei Branch (A) to Site Plant (B)

27.5 km (40 mins)

Location from Site Plant (B) to Wuhan Port (A)

11.2 km (18 mins)

Location from Site Plant(B) to Bank of China 24-hour Self- Service Bank(A)
4.4 km (7.07 mins)

Location from plant site(B) to Zhongnan Hospital of Wuhan University (A)

3.0 km (5 mins)
Land Cost Estimation
By considering the plant site and extra site for future build up, the estimation of
land to buy is 3.5 acres which is approximate 14164 m
2
.






Figure: Plant estimation

4.6 Climate

Adverse climatic conditions at a site will increase cost. Abnormally low
temperatures require the provision of additional insulation and special heating for
equipment and pipe runs. Stronger structures are needed at locations subject to
high wind, snow or earthquakes.

Wuhan's climate is humid subtropical with abundant rainfall and four
distinctive seasons. Wuhan is known for its oppressively humid summers, when
dew points can often reach 26 C (79 F) or more. Because of its hot summer
weather, Wuhan is commonly known as one of the Three Furnaces of China,
along with Nanjing and Chongqing. Spring and autumn are generally mild, while
winter is cool with occasional snow. In the recent thirty years, the average annual
rainfall is 1269 mm, mainly from June to August; annual temperature is 15.8-
17.5, annual frost free period lasts 211 to 272 days and annual sunlight duration
120 m

100 m



is 1810 to 2100 hours. Extreme temperatures have ranged from 18.1 C (1 F)
to 42.0 C (108 F).

Recently according to the China Earthquake Network Center a strong
earthquake with a 7.2 magnitude, struck eastern Burma (20.8 Degrees North and
99.8 Degrees East) at 21:55 on March 24 (Beijing Time), Tremors were felt in
many parts of Yunnan Province. Because the epicenter was very close to the
borders between Burma and China, people in some areas of Yunnan felt strong
tremors.

From March 31st to April 3
rd
2011, a strong cold air will sweep across eastern
parts of China, Inner Mongolia, north and northeast China, areas north of the
Yellow River and Huai River, Jianghan Area and other areas which is nearby
Wuhan City, causing a substantial drop in temperature (an average drop of 8
10 and 1214 in some areas). Moreover, a moderate gale will sweep over
eastern Inner Mongolia, northeast China, north China and other places.












PART 5

5.0 MATERIAL SAFETY DATA SHEET

5.1 METHANOL

5.1.1 PRODUCT IDENTIFICATION

Product Name: Methanol
Formula: CH
3
OH
Synonyms or Generic ID for Methanol: Carbinol; Methyl alcohol; Methyl
hydroxide;
Monohydroxymethane; Wood alcohol; Wood naptha; Wood spirits;
Columbian spirits; Methanol

5.1.2 HAZARD IDENTIFICATION

1. Appearance: Colorless liquid, Flash Point: 12C, 53.6F.
2. Danger! Poison! May be fatal or cause blindness if swallowed. Vapor
harmful.
3. Flammable liquid and vapour: Harmful if swallowed, inhaled, or
absorbed through the skin. Causes eye, skin, and respiratory tract irritation.
May cause central nervous system depression. Cannot be made non-
poisonous.
4. Target Organs: Eyes, nervous system, optic nerve.
5. Potential Health Effects:
- Eye: May cause painful sensitization to light. Methanol is a mild to
moderate eye irritant. Inhalation, ingestion or skin absorption of methanol
can cause significant disturbance in vision, including blindness.
- Skin: Causes moderate skin irritation. May be absorbed through the skin
in harmful amounts. Prolonged and or repeated contact may cause
defatting of skin and dermatitis. Methanol can be absorbed through the
skin, producing systemic effects that include visual disturbances.
- Ingestion: May be fatal or cause blindness if swallowed. Aspiration
hazard. Cannot be made nonpoisonous. May cause gastrointestinal
irritation with nausea, vomiting and diarrhea. May cause systematic
toxicity with acidosis. May cause central nervous system depression,
characterized by excitement, followed by headache, dizziness, drowsiness,
and nausea. Advanced stages may cause collapse, unconsciousness, coma,
and possible death due to failed respiratory failure. May cause
cardiopulmonary system effects.
- Inhalation: Methanol is toxic and can very readily form extremely high
vapour concentrations at room temperature. Inhalation is the most
common route of occupational exposure. At first, methanol causes CNS
depression with nausea, headache, vomiting, dizziness and incoordination.
A time period with no obvious symptoms follows (typically 8-24 hrs).
This latent period is followed by metabolic acidosis and severe visual
effects which may include reduced reactivity and/or increased sensitivity
to light, blurred, doubt and/or snowy vision, and blindness. Depending on
the severity of exposure and the promptness of treatment, survivors may
recover completely or may have permanent blindness, vision disturbances
and/or nervous system effects.
- Chronic: Prolonged or repeated skin contact may cause dermatitis.
Chronic exposure may cause effects similar to those of acute
exposure. Methanol is only very slowly eliminated from the body.
Because of this slow elimination, methanol should be regarded as a
cumulative poison. Though a single exposure may cause no effect, daily
exposures may result in the accumulation of a harmful amount. Methanol
has produced fetotoxicity in rats and teratogenicity in mice exposed by
inhalation to high concentrations that did not produce significant maternal
toxicity.

5.1.3 FIRST AID MEASURES

1. Eyes: In case of contact, immediately flush eyes with plenty of water for a t
least 15 minutes. Get medical aid.
2. Skin: In case of contact, immediately flush skin with plenty of water for at
least 15 minutes while removing contaminated clothing and shoes. Get
medical aid immediately. Wash clothing before reuse.
3. Ingestion: Potential for aspiration if swallowed. Get medical aid
immediately. Do not induce vomiting unless directed to do so by medical
personnel. Never give anything by mouth to an unconscious person. If
vomiting occurs naturally, have victim lean forward.
4. Inhalation: If inhaled, remove to fresh air. If not breathing, give artificial
respiration. If breathing is difficult, give oxygen. Get medical aid.
5. Notes to Physician: Effects may be delayed.
6. Antidote: Ethanol may inhibit methanol metabolism.


5.1.4 FIRE FIGHTING MEASURES

FLASH POINT: AUTOIGNITION FLAMMABLE RANGE:
12 deg C ( 53.60 deg F)) 455 deg C ( 851.00 deg F)) 6.0 vol %- 31.00 vol %

1. General Information: Ethanol may inhibit methanol metabolism. As in any
fire, wear a self-contained breathing apparatus in pressure-demand,
MSHA/NIOSH (approved or equivalent), and full protective gear. During a
fire, irritating and highly toxic gases may be generated by thermal
decomposition or combustion. Use water spray to keep fire-exposed
containers cool. Water may be ineffective. Material is lighter than water and
a fire may be spread by the use of water. Vapors are heavier than air and
may travel to a source of ignition and flash back. Vapors can spread along
the ground and collect in low or confined areas.
2. Extinguishing Media: For small fires, use dry chemical, carbon dioxide,
water spray or alcohol-resistant foam. Water may be ineffective. For large
fires, use water spray, fog or alcohol-resistant foam. Do NOT use straight
streams of water.


5.1.5 ACCIDENTAL RELEASE MEASURES

1. Spills/Leaks: Use water spray to disperse the gas/vapor. Remove all sources
of ignition. Absorb spill using an absorbent, non-combustible material such
as earth, sand, or vermiculite. Do not use combustible materials such as
sawdust. Use a spark-proof tool. Provide ventilation. A vapor suppressing
foam may be used to reduce vapors. Water spray may reduce vapor but may
not prevent ignition in closed spaces


5.1.6 STORAGE AND HANDLING

1. HANDLING: Wash thoroughly after handling. Remove contaminated
clothing and wash before reuse. Ground and bond containers when
transferring material. Use spark-proof tools and explosion proof equipment.
Avoid contact with eyes, skin, and clothing. Empty containers retain product
residue, (liquid and/or vapor), and can be dangerous. Keep container tightly
closed. Do not ingest or inhale. Do not pressurize, cut, weld, braze, solder,
drill, grind, or expose empty containers to heat, sparks or open flames. Use
only with
2. STORAGE: Keep away from heat, sparks, and flame. Keep away from
sources of ignition. Store in a cool, dry, well-ventilated area away from
incompatible substances. Flammables-area. Keep containers tightly


5.1.7 EXPOSURE CONTROLS/PERSONAL PROTECTION

1. Engineering Controls: Use explosion-proof ventilation equipment. Facilities
storing or utilizing this material should be equipped with an eyewash facility
and a safety shower. Use adequate general or local exhaust ventilation to
keep airborne concentrations below the permissible exposure limits. OSHA
Vacated PELs: Methanol: 200 ppm TWA; 260 mg/m3 TWA
2. Personal Protective Equipment;
Eyes: Wear chemical splash goggles.
Skin: Wear butyl rubber gloves, apron, and/or clothing
Clothing: Wear appropriate protective clothing to prevent skin exposure.
Respirators: Follow the OSHA respirator regulations found in 29 CFR
1910.134 or European Standard EN 149. Use a NIOSH/MSHA or
European Standard EN 149 approved respirator if exposure limits are
exceeded or if irritation or other symptoms are experienced.

5.1.8 PHYSICAL AND CHEMICAL PROPERTIES

1. Appearance, odor and state: clear, colorless - APHA: 10 max
2. Molecular weight: 32.04
3. Boiling point(1 atm): 64.7 deg C @ 760 mmHg
4. Specific gravity: 7910 g/cm3 @ 20C
5. Freezing point/Melting point: 98C)
6. Vapor pressure(At 20
0
C): 128mm Hg
7. Gas density: 1.11 (Air=1)
8. Solubility in water: miscible

5.1.9 STABILITY AND REACTIVITY

1) Chemical stability: Stable under normal temperatures and pressures
2) Conditions to avoid: High temperatures, ignition sources, confined spaces.
3) Incompability (Materials to Avoid): Oxidizing agents, reducing agents,
acids, alkali metals, potassium, sodium, metals as powders (e.g. hafnium,
raney nickel), acid anhydrides, acid chlorides, powdered aluminum,
powdered magnesium.
4) Hazardous decomposition products: Carbon monoxide, irritating and
toxic fumes and gases, carbon dioxide, formaldehyde.
5) Hazardous polymerization: Will not occur

5.1.10 TOXICOLOGICAL INFORMATION

LD50/LC50:
Draize test, rabbit, eye: 40 mg Moderate;
Draize test, rabbit, eye: 100 mg/24H Moderate;
Draize test, rabbit, skin: 20 mg/24H Moderate;
Inhalation, rabbit: LC50 = 81000 mg/m3/14H;
Inhalation, rat: LC50 = 64000 ppm/4H;
Oral, mouse: LD50 = 7300 mg/kg;
Oral, rabbit: LD50 = 14200 mg/kg;
Oral, rat: LD50 = 5600 mg/kg;
Skin, rabbit: LD50 = 15800 mg/kg;

1. Teratogenicity: There is no human information available. Methanol is
considered to be a potential developmental hazard based on animal data. In
animal experiments, methanol has caused fetotoxic or teratogenic effects
without maternal toxicity.
2. Reproductive Effects: See actual entry in RTECS for complete
information.
3. Mutagenicity: See actual entry in RTECS for complete information.
4. Neurotoxicity: ACGIH cites neuropathy, vision and CNS under TLV basis.


5.1.11 ECOLOGICAL INFORMATION

1. Ecotoxicity: Fish: Fathead Minnow: 29.4 g/L; 96 Hr; LC50
(unspecified)Fish: Goldfish: 250 ppm; 11 Hr; resulted in deathFish:
Rainbow trout: 8000 mg/L; 48 Hr; LC50 (unspecified)Fish: Rainbow trout:
LC50 = 13-68 mg/L; 96 Hr.; 12 degrees CFish: Fathead Minnow: LC50 =
29400 mg/L; 96 Hr.; 25 degrees C, pH 7.63Fish: Rainbow trout: LC50 =
8000 mg/L; 48 Hr.; UnspecifiedBacteria: Phytobacterium phosphoreum:
EC50 = 51,000-320,000 mg/L; 30 minutes; Microtox test No data available.
2. Environmental: Dangerous to aquatic life in high concentrations. Aquatic
toxicity rating: TLm 96>1000 ppm. May be dangerous if it enters water
intakes. Methyl alcohol is expected to biodegrade in soil and water very
rapidly. This product will show high soil mobility and will be degraded from
the ambient atmosphere by the reaction with photochemically produced
hyroxyl radicals with an estimated half-life of 17.8 days. Bioconcentration
factor for fish (golden ide) < 10. Based on a log Kow of -0.77, the BCF
value for methanol can be estimated to be 0.2.
3. Physical: No information available.
4. Other: No information available.

5.1.12 DISPOSAL CONSIDERATIONS

US EPA guidelines for the classification determination are listed in 40 CFR
Parts 261.3. Additionally, waste generators must consult state and local
hazardous waste regulations to ensure complete and accurate
classification.
1. RCRA P-Series: None listed.
2. RCRA U-Series:
CAS# 67-56-1: waste number U154 (Ignitable waste).

5.2 METHANE

5.2.1 PRODUCT IDENTIFICATION

Product Name: Methane
Formula: CH
4

Chemical name: Methane, Saturated Alphatic Hydrocarbon, Alkane
Synonyms: Methyl Hydride, Marsh Gas, Fire Damp

5.2.2 HAZARD IDENTIFICATION

1. Emergency overview
Methane is a flammable, colorless, odorless, compressed gas packaged in
cylinders under high pressure. It poses an immediate fire and explosion
hazard when mixed with air at concentrations exceeding 5.0%. High
concentrations that can cause rapid suffocation are within the flammable
range and should not be entered.

2. Acute potential health effects:
Route of exposures
Eye contact: No harmful affect.
Ingestion: Not applicable
Inhalation: Methane is nontoxic. It can, however, reduce the amount of
oxygen in the air necessary to support life. Exposure to oxygen-deficient
atmospheres (less than 19.5 %) may produce dizziness, nausea, vomiting,
loss of consciousness, and death. At very low oxygen concentrations (less
than 12 %) unconsciousness and death may occur without warning. It
should be noted that before suffocation could occur, the lower flammable
limit for Methane in air will be exceeded; causing both oxygen deficient and
an explosive atmosphere.
Skin contact: No harmful affect.
3. Potential health effects of repeated exposure:
Route of entry: None
Symtomps: None
Target organs: None
Medical conditions aggravated by exposure: None
Carcinigenicity: Methane is not listed as a carcinogen or potential
carcinogen by NTP, IARC, or OSHA Subpart Z.

5.2.3 FIRST AID MEASURES

1. Eye contact: No treatment necessary.
2. Ingestion: Not applicable
3. Inhalation: Remove person to fresh air. If not breathing, administer
artificial respiration. If breathing is difficult, administer oxygen.
Obtain prompt medical attention.
4. Skin contact: No treatment necessary.
5. Notes to physician: Treatment of overexposure should be directed at the
control of symptoms and the clinical condition.

5.2.4 FIRE FIGHTING MEASURES

FLASH POINT: AUTOIGNITION: FLAMMABLE RANGE:
-306 F (-187.8 C) 999 F (537 C) 5.0% - 15%

1. Extinguishing media: Dry chemical, carbon dioxide, or water.
2. Special firefighting instructions: Evacuate all personnel from area. If
possible, without risk, shut off source of methane, then fight fire according
to types of materials burning. Extinguish fire only if gas flow can be
stopped. This will avoid possible accumulation and re-ignition of a
flammable gas mixture. Keep adjacent cylinders cool by spraying with large
amounts of water until the fire burns itself out. Self-contained breathing
apparatus (SCBA) may be required.
3. Unusual fire and hazards explosion: Most cylinders are designed to vent
contents when exposed to elevated temperatures. Pressure in a cylinder can
build up due to heat and it may rupture if pressure relief devices should fail
to function.
4. Hazardous combustion products: Carbon monoxide

5.2.5 ACCIDENTAL RELEASE MEASURES

Steps to be taken if material released or spilled: Evacuate immediate
area. Eliminate any possible sources of ignition, and provide maximum
explosion-proof ventilation. Use a flammable gas meter (explosimeter)
calibrated for Methane to monitor concentration. Never enter an area where
Methane concentration is greater than 1.0% (which is 20% of the lower
flammable limit). An immediate fire and explosion hazard exists when
atmospheric Methane concentration exceeds 5.0%. Use appropriate
protective equipment (SCBA and fire resistant suit). Shut off source of leak
if possible. Isolate any leaking cylinder. If leak is from container, pressure
relief device or its valve, contact your supplier. If the leak is in the users
system, close the cylinder valve, safely vent the pressure, and purge with an
inert gas before attempting repairs.

5.2.6 STORAGE AND HANDLING

1. Storage: Store cylinders in a well-ventilated, secure area, protected from the
weather. Cylinders should be stored upright with valve outlet seals and
valve protection caps in place. There should be no sources of ignition. All
electrical equipment should be explosion-proof in the storage areas. Storage
areas must meet National Electrical Codes for class 1 hazardous areas.
Flammable storage areas must be separated from oxygen and other oxidizers
by a minimum distance of 20 ft. or by a barrier of non-combustible material
at least 5 ft. high having a fire resistance rating of at least _ hour. Post No
Smoking or Open Flames signs in the storage or use areas. Do not allow
storage temperature to exceed 125 F (52 C). Storage should be away from
heavily travelled areas and emergency exits. Full and empty cylinders
should be segregated. Use a first-in first-out inventory system to prevent full
containers from being stored for long periods of time.
2. Handling: Do not drag, roll, slide or drop cylinder. Use a suitable hand
truck designed for cylinder movement. Never attempt to lift a cylinder by its
cap. Secure cylinders at all times while in use. Use a pressure reducing
regulator to safely discharge gas from cylinder. Use a check valve to prevent
reverse flow into cylinder. Never apply flame or localized heat directly to
any part of the cylinder. Do not allow any part of the cylinder to exceed 125
F (52C). Use piping and equipment adequately designed to withstand
pressures to be encountered. Once cylinder has been connected to properly
purged and inerted process, open cylinder valve slowly and carefully. If user
experiences any difficulty operating cylinder valve, discontinue use and
contact supplier. Never insert an object (e.g., wrench, screwdriver, etc.) into
valve cap openings. Doing so may damage valve causing a leak to occur.
Use an adjustable strap-wrench to remove over-tight or rusted caps. All
piped systems and associated equipment must be grounded. Electrical
equipment should be non-sparking or explosion-proof.
3. Special precautions: Always store and handle compressed gas cylinders in
accordance with

5.2.7 EXPOSURE CONTROLS/PERSONAL PROTECTION

1. Engineering controls:
-Ventilation: Provide adequate natural or explosion-proof ventilation to
prevent accumulation of gas concentrations above 1.0% Methane (20% of
LEL).
-Respiratory inspections: Emergency Use: Do not enter areas where Methane
concentration is greater than 1.0% (20% of the LEL). Exposure to
concentrations below 1.0% does not require respiratory protection.
-Eye protection: Safety glasses and/or face shield.
-Skin protection: Leather gloves for handling cylinders. Fire resistant suit and
gloves in emergency situations.
-Other protective equipment: Safety shoes are recommended when handling
cylinders.

5.2.8 PHYSICAL AND CHEMICAL PROPERTIES


1. Appearence, odor and state: Colorless, odorless, flammable gas.
2. Molecular weight: 16.04
3. Boiling point (1 atm): -258.7 F (-161.5 C)
4. Specific gravity (Air = 1): 0.554
5. Freezing point/Melting point: -296. 5 F (-182.5 C)
6. Vapor pressure (At 70 F (21.1 C): Permanent, noncondensable gas.
7. Gas density (At 70 F (21.1 C) and 1 atm: 0.042 lb/ft
3

8. Solubility in water (vol/vol): 3.3 ml gas / 100 ml

5.2.9 STABILITY AND REACTIVITY


1. Chemical stability: Stable
2. Condition to avoid: Cylinders should not be exposed to temperatures in
excess of 125 F (52 C).
3. Incompability (Materials to Avoid): Oxygen, Halogens and Oxidizers
4. Reactivity:
A) HAZARDOUS DECOMPOSITION PRODUCTS: None
B) HAZARDOUS POLYMERIZATION: Will not occur


5.2.10 TOXICOLOGICAL INFORMATION


LC50 (Inhalation): Not applicable. Simple asphyxiant.
LD50 (Oral): Not applicable
LD50 (Dermal): Not applicable
Skin corrosivity: Methane is not corrosive to the skin.

5.2.11 ECOLOGICAL INFORMATION


1. Aquatic toxicity: Not determined
2. Mobility: Not determined
3. Persistence and Biodegradability: Not determined
4. Potential to accumulate: Not determined
5. Remarks: This product does not contain any Class I or Class II ozone
depleting chemicals.

5.2.12 DISPOSAL CONSIDERATIONS

1. Unused product/empty container: Return container and unused product to
supplier. Do not attempt to dispose of residual or unused quantities.
2. Disposal information: Residual product in the system may be burned if a
suitable burning unit (flair incinerator) is available on site. This shall be
done in accordance with federal, state, and local regulations. Wastes
containing this material may be classified by EPA as hazardous waste by
characteristic (i.e., Ignitability, Corrosivity, Toxicity, Reactivity). Waste
streams must be characterized by the user to meet federal, state, and local
requirements.


5.3 CARBON MONOXIDE

5.3.1 PRODUCT IDENTIFICATION

Product Name: Carbon Monoxide
Formula: CO
Synonyms or Generic ID for Methanol: Carbon oxide (CO); CO; Exhaust
Gas; Flue gas; Carbonic oxide; Carbon oxide; Carbone; Carbonio;
Kohlenmonoxid; Kohlenoxyd; Koolmonoxyde; NA 9202; Oxyde de carbone;
UN 1016; Wegla tlenek; Flue gasnide; Carbon monoxide

5.3.2 HAZARD IDENTIFICATION


1. Appearance: Colorless gas [may be liquid at low temperature or high
pressure]
2. Emergency overview : WARNING!
FLAMMABLE GAS.
MAY CAUSE FLASH FIRE.
MAY BE FATAL IF INHALED.
MAY CAUSE TARGET ORGAN DAMAGE,
BASED ON ANIMAL DATA, CONTENTS
UNDER PRESSURE.
Keep away from heat, sparks and flame. Do not
puncture or incinerate container. Avoid breathing
gas. May cause target organ damage, based on
animal data. Use only with adequate ventilation.
Keep container closed. Contact with rapidly
expanding gases can cause frostbite
3. Target organs : May cause damage to the following organs:
blood, lungs, cardiovascular system, central
nervous system (CNS).
4. Route of entry : Inhalation
5. Potential acute health effects
Eyes: Contact with rapidly expanding gas may cause burns or frostbite.
Skin: Contact with rapidly expanding gas may cause burns or frostbite.
Inhalation: Toxic by inhalation.
Ingestion: Ingestion is not a normal route of exposure for gases
6. Potential chronic health effect:
CARCINOGENIC EFFECTS: Not available.
MUTAGENIC EFFECTS: Not available.
TERATOGENIC EFFECTS: Classified 1 by European Union.
7. Medical conditions aggravated by overexposure:
Pre-existing disorders involving any target organs mentioned in this
MSDS as being at risk may be aggravated by over-exposure to this product.

5.3.3 FIRST AID MEASURES

No action shall be taken involving any personal risk or without suitable training.
If it is suspected that fumes are still present, the rescuer should wear an
appropriate mask or self-contained breathing apparatus. It may be dangerous to
the person providing aid to give mouth-to-mouth resuscitation.
1. Eye contact : Check for and remove any contact lenses. Immediately
flush eyes with plenty of water for at least 15 minutes,
occasionally lifting the upper and lower eyelids. Get
medical attention immediately
2. Skin contact : In case of contact, immediately flush skin with plenty of
water for at least 15 minutes while removing
contaminated clothing and shoes. To avoid the risk of
static discharges and gas ignition, soak contaminated
clothing thoroughly with water before removing it.
Wash clothing before reuse. Clean shoes
thoroughly before reuse. Get medical attention
immediately.
3. Frostible : Try to warm up the frozen tissue and seek medical
attention.
4. Inhalation : Move exposed person to fresh air. If not breathing, if
breathing is irregular or if respiratory arrest occurs,
provide artificial respiration or oxygen by trained
personnel. Loosen tight clothing such as a collar, tie, belt
or waistband. Get medical attention immediately.
5. Ingestion : As this product is a gas, refer to the inhalation section.

5.3.4 FIRE FIGHTING MEASURES

FLASH POINT: AUTOIGNITION: FLAMMABLE RANGE:
12 deg C ( 53.60 deg F)) 608.89 deg C 12.5 vol %- 74.00 vol %

1. Products of combustion: Decomposition products may include the
following materials: carbon dioxide & carbon monoxide.
2. Fire hazards in presence
of various substances : Extremely flammable in the presence of the
following materials or conditions: open flames, sparks and static discharge
and oxidizing materials.
3. Fire- fighting media & instructions : In case of fire, use water spray
(fog), foam or dry chemical. A safe distance to cool container and protect
surrounding area. If involved in fire, shut off flow immediately if it can be
done without risk. Contain gas under pressure. Flammable gas. In a fire or if
heated, a pressure increase will occur and the container may burst, with the
risk of a subsequent explosion.

5.3.5 ACCIDENTAL RELEASE MEASURES

1. Personal precautions : Immediately contact emergency personnel. Keep
unnecessary personnel away. Use suitable protective equipment (section 8).
Shut off gas supply if this can be done safely. Isolate area until gas has
dispersed.
2. Environmental Precautions : Avoid dispersal of spilled material and
runoff and contact with soil, waterways, drains and sewers.
3. Method for cleaning up: Immediately contact emergency personnel. Stop
leak if without risk. Use spark-proof tools and explosion proof equipment.
Note: see section 1 for emergency contact information and section 13 for
waste disposal.

5.3.6 STORAGE AND HANDLING


1. Handling: Use only with adequate ventilation. Use explosion-proof
electrical (ventilating, lighting and material handling) equipment. High
pressure gas. Do not puncture or incinerate container. Use equipment rated
for cylinder pressure. Close valve after each use and when empty. Keep
container closed. Keep away from heat, sparks and flame. To avoid fire,
eliminate ignition sources. Protect cylinders from physical damage; do not
drag, roll, slide, or drop. Use a suitable hand truck for cylinder movement.
2. Storage: Keep container in a cool, well-ventilated area. Keep container
tightly closed and sealed until ready for use. Avoid all possible sources of
ignition (spark or flame). Segregate from oxidizing materials. Cylinders
should be stored upright, with valve protection cap in place, and firmly
secured to prevent falling or being knocked over. Cylinder temperatures
should not exceed 52 C (125 F).


5.3.7 EXPOSURE CONTROLS/PERSONAL PROTECTION


1. Engineering Controls: Use only with adequate ventilation. Use process
enclosures, local exhaust ventilation or other engineering controls to keep
worker exposure to airborne contaminants below any recommended or
statutory limits. The engineering controls also need to keep gas, vapour or
dust concentrations below any lower explosive limits. Use explosion-proof
ventilation equipment.
2. Personal Protective Equipment;
Eyes: Safety eyewear complying with an approved standard should be used
when a risk assessment indicates this is necessary to avoid exposure to
liquid splashes, mists or dusts.
Skin: Personal protective equipment for the body should be selected based
on the task being performed and the risks involved and should be
approved by a specialist before handling this product.
Respirators: Use a properly fitted, air-purifying or air-fed respirator
complying with an approved standard if a risk assessment indicates this is
necessary. Respirator selection must be based on known or anticipated
exposure levels, the hazards of the product and the safe working limits
of the selected respirator
Hands: Chemical-resistant, impervious gloves complying with an approved
standard should be worn at all times when handling chemical products if a
risk assessment indicates this is necessary.
In case of large spill: Self-contained breathing apparatus (SCBA) should be
used to avoid inhalation of the product. Full chemical-resistant suit and
self-contained breathing apparatus should be worn only by trained and
authorized persons.



5.3.8 PHYSICAL AND CHEMICAL PROPERTIES

1. Molecular weight: 28.01
2. Boiling point : -191.7C (-313.1F)
3. Specific volume: 13.8889 ft
3
/lb
4. Freezing point/melting point: -198.9C (-326F)
5. Vapor density : 0.97 (Air=1)
6. Gas density: 0.072 lb/ft
3

7. Critical tenperature: -140.1C (-220.2F)

5.3.9 STABILITY AND REACTIVITY

1. Chemical stability: Stable under normal temperatures and pressures
2. Incompability (Materials to Avoid): Oxidizing agents
3. Hazardous decomposition products: Under normal conditions of storage
and use, hazardous decomposition products should not be produced.
4. Hazardous polymerization: Will not occur

5.3.10 TOXICOLOGICAL INFORMATION



1. IDLH : 1200 ppm
2. Chronic effects on humans : TERATOGENIC EFFECTS: Classified 1
by European Union. May cause damage to the following organs: blood,
lungs, cardiovascular system, central nervous system (CNS).
3. Other toxic effects on humans: No specific information is available in our
database regarding the other toxic effects of this material to humans.
4. Carcinogenic: no known significant effects or critical hazards
5. Reproductive Effects: No known significant effect or critical hazard.
6. Mutagenicity: No known significant effect or critical hazard.

5.3.11 ECOLOGICAL INFORMATION

Aquatic ecotoxicity : Not available.
Products of degradation : carbon oxides (CO, CO
2
)
Environmental fate : Not available
Environmental hazards : No known significant effects or critical hazards
Toxicity to the environment : Not available

5.3.12 DISPOSAL CONSIDERATIONS

Product removed from the cylinder must be disposed of in accordance with
appropriate Federal, State, local regulation. Return cylinders with residual
product to Airgas, Inc.Do not dispose of locally.








5.4 CARBON DIOXIDE

5.4.1 PRODUCT IDENTIFICATION

Material name :Carbon dioxide
Chemical formula: CO
2
)

5.4.2 HAZARD IDENTIFICATION

Appearance, Odor & State: At room temperature and atmospheric pressure,
carbon dioxide is a colorless, odorless, slightly acidic gas. Carbon Dioxide is
shipped as a liquefied gas under its own vapor pressure.

5.4.3 FIRST AID MEASURE

No action shall be taken involving any personal risk or without suitable
training.If fumes are still suspected to be present, the rescuer should wear an
appropriate mask or a self-contained breathing apparatus. It may be dangerous
to the person providing aid to give mouth-to-mouth resuscitation.
Eye contact : In case of contact, immediately flush eyes with plenty of water
for at least 15 minutes. Get medical attentions immediately.
Skin contact: In case of contact, immediately flush skin with plenty of water.
Remove contaminated clothing and shoes. Wash clothing before
reuse. Thoroughly clean shoes before reuse. Get medical
attention.
Frostbite : Try to warm up the frozen tissues and seek medical attention.
Inhalation : If inhaled, remove to fresh air. If not breathing, give artificial
respiration. If breathing is difficult, give oxygen. Get medical
attention.


5.4.4 FIRE FIGHTING MEASURE

Flammability of the product
Firefighting media and instructions. If involved in fire, shut off flow
immediately if it can be done without risk. Apply water from a safe distance to
cool container and protect surrounding area.No specific hazard.

Special protective equipment for fire-fighters
Fire fighters should wear appropriate protective equipment and self-contained
breathing apparatus (SCBA) with a full face piece operated in positive pressure
mode.


5.4.5 ACCIDENTIAL RELEASE MEASURE


Personal precautions : Immediately contact emergency personnel. Keep
unnecessary personnel away. Use suitable
protective equipment (Section 8). Shut off gas
supply if this can be done safely. Isolate area until
gas has dispersed.
Environmental precautions : Avoid dispersal of spilled material and runoff and
contact with soil, waterways, drains and sewers.


5.4.6 STORAGE AND HANDLING

Storage : Keep container tightly closed. Keep container in a cool,
well-ventilated area. Cylinders should be stored upright,
with valve protection cap in place, and firmly secured to
prevent falling or being knocked over. Cylinder temperatures
should not exceed 52 C (125 F).
Handling : Avoid contact with eyes, skin and clothing. Keep container
closed. Use only with adequate ventilation. Do not puncture or
incinerate container. Wash thoroughly after handling. High
pressure gas. Use equipment rated for cylinder pressure. Close
valve after each use and when empty. Protect cylinders from
physical damage; do not drag, roll, slide, or drop. Use a suitable
hand truck for cylinder movement. Never allow any unprotected
part of the body to touch insulated pipes or vessels that contain
cryogenic liquids. Prevent entrapment of liquid in closed
systems or piping without pressure relief devices. Some materials
may become brittle at low temperatures and will easily fracture.

5.4.7 EXPOSURE CONTROLS/PERSONAL PROTECTION

Engineering controls: Use only with adequate ventilation. Use process
enclosures, local exhaust ventilation, or other engineering controls to keep
airborne levels below recommended exposure limits.
Personal protection
Eyes : Safety eyewear complying with an approved standard
should be used when a risk assessment indicates this is
necessary to avoid exposure to liquid splashes, mists or
dusts.
Skin : Personal protective equipment for the body should be
selected based on the task being performed and the risks
involved and should be approved by a specialist before
handling this product.
Respiratory : Use a properly fitted, air-purifying or air-fed respirator
complying with an approved standard if a risk assessment
indicates this is necessary. Respirator selection must be
based on known or anticipated exposure levels, the hazards of the
product and the safe working limits of the selected respirator.
Hand : Chemical-resistant, impervious gloves or gauntlets complying
with an approved standard should be worn at all times when
handling chemical products if a risk assessment indicates this is
necessary.

5.4.8 PHYSICAL AND CHEMICAL PROPERTIES

Molecular weight : 44.01 g/mole
Molecular formula : CO
2

Boiling/condensation point : -78.55C (-109.4F)
Melting/freezing point : Sublimation temperature: -78.5C (-
109.3F)
Critical temperature : 30.9C (87.6F)
Vapor pressure : 830 psig
Vapor density : 1.53 (Air = 1)
Physical chemical comments : Not available.

5.4.9 STABILITY AND REACTIVITY

The product is stable.

5.4.10 TOXICOLOGY INFORMATION

Toxicity data
IDLH : 40000 ppm
Chronic effects on humans : Causes damage to the following organs:
lungs, cardiovascular system, skin, eyes,
central nervous system (CNS), eye, lens or
cornea.
Other toxic effects on humans : No specific information is available in our
database regarding the other toxic effects
of this material for humans.
Specific effects
Carcinogenic effects: No known significant effects or critical hazards.
Mutagenic effects: No known significant effects or critical hazards.
Reproduction toxicity: No known significant effects or critical hazards.


5.4.11 ECOLOGICAL INFORMATION

Products of degradation : These products are carbon
oxides (CO, CO 2).
Toxicity of the products of biodegradation : The product itself and its
products of degradation are
not toxic.
Environmental fate : Not available
Environmental hazards : No known significant
effects or critical hazards
Toxicity to the environment : Not available


5.4.12 DISPOSABLE CONSIDERATION

Product removed from the cylinder must be disposed of in accordance with
appropriate Federal, State, local regulation.Return cylinders with residual
product to Airgas, Inc. Do not dispose of locally.




5.5 WATER

5.5.1 PRODUCT IDENTIFICATION

Material name : Water
Synonyms : Dehydrogenase Monoxide; H
2
0


5.5.2 HAZARD IDENTIFICATION
Inhalation
Acute over exposure: Inhalation can result in asphyxiation and is often fatal.
Chronic overexposure: Chronic inhalation overexposure not encountered.
Skin Contact
Acute overexposure: Prolonged but constant contact with liquid may cause a
mild dermatitis. Chronic overexposure: Mild to severe dermatitis.
Skin Absorption
Acute overexposure: No effects noted. Chronic overexposure: No effects
noted.
Eye Contact
Acute overexposure: No effects noted. Chronic overexposure: No effects
noted.
Ingestion
Acute overexposure: Excessive ingestion of liquid form can cause gastric
distress and mild diarrhea.
Chronic overexposure: No effects noted.


5.5.3 FIRST AID MEASURES
Eyes : None
Skin : None
Inhalation : Remove to fresh air; provide artificial respiration; Provide
oxygen.
Ingestion : None
5.5.4 FIRE FIGHTING MEASURES
Small Spill: Mop up, or abnsorb with an inert dry material and place in an
appropriate waste disposal container.
Large Spill: Absorb with an inert material and put the spilled material in an
appropriate waste disposal.
Conditions contributing to instability: Exposure to direct current electricity.
Incompatibility: Strong acids and bases can cause rapid heating. Reaction with
sodium metal can result in explosion.
Hazardous decomposition products: Hydrogen - Explosive gas Oxygen -
Supports rapid combustion
Conditions contributing to hazardous polymerization: None
5.5.4 ACCIDENTAL RELEASE MEASURES

Flammability of the product

Firefighting media and instructions
If involved in fire, shut off flow immediately if it can be done without risk.
Apply water from a safe distance to cool container and protect surrounding area.
No specific hazard.
Special protective equipment for fire-fighters
Fire fighters should wear appropriate protective equipment and self-contained
breathing apparatus (SCBA) with a full facepiece operated in positive pressure
mode.

5.5.5 STORAGE AND HANDLING


Storage : Keep container tightly closed. Keep container in a cool, well-
ventilated area. Cylinders should be stored upright, with valve
protection cap in place, and firmly secured to prevent falling or
being knocked over. Cylinder temperatures should not exceed
52C.
Handling : Avoid contact with eyes, skin and clothing. Keep container
closed. Use only with adequate ventilation. Do not puncture or
incinerate container. Wash thoroughly after handling. High
pressure gas. Use equipment rated for cylinder pressure. Close
valve after each use and when empty. Protect cylinders from
physical damage; do not drag, roll, slide, or drop. Use a suitable
hand truck for cylinder movement. Never allow any unprotected
part of the body to touch insulated pipes or vessels that contain
cryogenic liquids. Prevent entrapment of liquid in closed systems
or piping without pressure relief devices. Some materials may
become brittle at low temperatures and will easily fracture.

5.5.6 EXPOSURE CONTROLS/PERSONAL PROTECTION

Eyes : Safety eyewear complying with an approved standard should be
used when a risk assessment indicates this is necessary to avoid
exposure to liquid splashes, mists or dusts. When working with
cryogenic liquids, wear a full face shield.
Skin : Personal protective equipment for the body should be selected
based on the task being performed and the risks involved and
should be approved by a specialist before handling this product.
Respiratory : Use a properly fitted, air-purifying or air-fed respirator
complying with an approved standard if a risk assessment
indicates this is necessary. Respirator selection must be based on
known or anticipated exposure levels, the hazards of the product
and the safe working limits of the selected respirator.
Hands : Chemical-resistant, impervious gloves or gauntlets complying
with an approved standard should be worn at all times when
handling chemical products if a risk assessment indicates this is
necessary. Insulated gloves suitable for low temperatures.

5.5.7 PHYSICAL AND CHEMICAL PROPERTIES

Physical state and appearance: Liquid.p. 3
Odor: Odorless.
Taste: Not available.
Molecular Weight: 18.02 g/mole
Color: Colorless.
pH (1% soln/water): 7 [Neutral.]
Boiling Point: 100C (212F)
Melting Point: Not available.
Critical Temperature: Not available.
Specific Gravity: 1 (Water = 1)
Vapor Pressure: 2.3 kPa (@ 20C)
Vapor Density: 0.62 (Air = 1)
Volatility: Not available.
Odor Threshold: Not available.
Water/Oil Dist. Coeff.: Not available.
Ionicity (in Water): Not available.
Dispersion Properties: Not applicable
Solubility: Not Applicable

5.5.8 STABILITY AND REACTIVITY

Stability: The product is stable.
Instability Temperature: Not available.
Conditions of Instability: Not available.
Incompatibility with various substances: Not available.
Corrosivity: Not available.
Special Remarks on Reactivity: Not available.
Special Remarks on Corrosivity: Not available.
Polymerization: Will not occur.

5.5.9 TOXICOLOGICAL INFORMATION

Toxicity data
IDLH : 40000 ppm
Chronic effects on humans: Causes damage to the following organs: lungs,
cardiovascular system, skin, eyes, central nervous
system (CNS), eye, lens or cornea.
Other toxic effects on humans: No specific information is available in our
database regarding the other toxic effects of this
material for humans.
Specific effects
Carcinogenic effects : No known significant effects or critical hazards.
Mutagenic effects : No known significant effects or critical hazards.
Reproduction toxicity : No known significant effects or critical hazards.



5.5.10 ECOLOGICAL INFORMATION

Ecotoxicity: Not available.
BOD5 and COD: Not available.
Products of Biodegradation:
Possibly hazardous short term degradation products are not likely. However,
long term degradation products may arise.
Toxicity of the Products of Biodegradation: The product itself and its products
of degradation are not toxic.
Special Remarks on the Products of Biodegradation: Not available.

5.5.11 DISPOSAL CONSIDERATIONS

Product removed from the cylinder must be disposed of in accordance with
appropriate Federal, State, local regulation.Return cylinders with residual
product to Airgas, Inc. Do not dispose of locally.


5.6 HYDROGEN

5.6.1 PRODUCT IDENTIFICATION

Product name : Hydrogen, compressed
Chemical name : Hydrogen formula: H
2

Synonyms : none

5.6.2 HAZARD IDENTIFICATION

Hydrogen is a flammable, colorless, odorless, compressed gas packaged in
cylinders at high pressure. It poses an immediate fire and explosive hazard when
concentrations exceed 4%. It is much lighter than air and burns with an invisible
flame. High concentrations that will cause suffocation are within the flammable
range and must not be centered.

5.6.3 FIRST AID MEASURE

Inhalation : Persons suffering from lack of oxygen should be removed
to fresh air. If victim is not breathing, administer artificial
respiration. If breathing is difficult, administer oxygen.
Obtain prompt medical attention.
Skin contact : None
Eye contact : None
Ingestion : None
Notes to physician : None

5.6.4 FIRE FIGHTING MEASURES

Flammable gas 565.5c (1050f) Lower: 4% Upper: 74%
Extinguishing media: CO
2
, dry chemical water spray or fog for surrounding
area. Do not extinguish until hydrogen source is shut off.
Hazardous combustion products: none
Special fire fighting instructions: evacuate all personnel from danger area.
Immediately
Cool container with water spray from maximum distance, taking care not to
extinguish flames. If flames are accidentally extinguished, explosive re-ignition
may occur. Stop flow of gas if without risk while continuing cooling water
spray.
Unusual fire and explosion hazards: burns with a pale blue, nearly invisible
flame.
Hydrogen is easily ignited with low-ignition energy, including static electricity.
Hydrogen is lighter than air and can accumulate in the upper sections of
enclosed spaces. Pressure in a container can build up due to heat, and it may
rupture if pressure relief devices should fail to function.

5.6.5 ACCIDENTAL RELEASE MEASURES

Evacuate immediate area. Eliminate any possible sources of ignition, and
provide maximum explosion proof ventilation. Shut off source of hydrogen, if
possible. If leaking from cylinder, or valve, call the Air Products' emergency
phone number. The presence of a hydrogen flame can be detected by
approaching cautiously with an outstretched straw broom to make the flame
visible.

5.6.7 STORAGE AND HANDLING

STORAGE : Specific requirements are listed in NFPA 50A. Cylinder
storage locations should be wellprotected, well-ventilated,
dry, and separated from combustible materials. Cylinders
should never knowingly be allowed to reach a temperature
exceeding 125 _F (52 _C). Cylinders of hydrogen should
be separated from oxygen cylinders or other oxidizers by
a minimum distance of 20 ft., or by a barrier of
noncombustible material at least 5 ft. Cylinders should be
stored upright with valve protection cap in place and
firmly secured to prevent falling or being knocked over.
Protect cylinders from physical damage; do not drag, roll,
slide or drop. Use a suitable hand truck for cylinder
movement. Post "No Smoking or Open Flames" signs in
the storage areas. There should be no sources of ignition.
All electrical equipment should be explosion proof in the
storage and use areas. Storage areas must meet national
electric codes for class 1 hazardous areas.

HANDLING : Do not "open" hydrogen cylinder valve before connecting
it, since self-ignition may occur. Hydrogen is the lightest
gas known and may collect in the top of buildings without
proper ventilation. It may leak out of a system which is
gas-tight for air or other gases. Leak check system with
leak detection solution, never with flame. If user
experiences difficulty operating cylinder valve,
discontinue use and contact supplier. Use only approved
CGA connections. DO NOT USE ADAPTERS. Never
insert an object (e.g., wrench, screwdriver, pry bar, etc.)
into valve cap openings. Doing so may damage valve,
causing a leak to occur. Use an adjustable strap wrench to
remove over-tight or rusted caps. Never strike an arc on a
compressed gas cylinder or make a cylinder a part of an
electrical circuit.

5.6.6 EXPOSURE CONTROLS/PERSONAL PROTECTION

Engineering controls: Provide natural or explosion-proof ventilation adequate to
ensure Hydrogen does not reach its lower explosive limit of 4%.
Respiratory protection:
General Use: None
Emergency Use: Air supplied respirators are required in oxygen-deficient
atmospheres. Before entering area you must check for flammable or oxygen-
deficient atmospheres.
Protective gloves: Work gloves are recommended when handling cylinders.
Eye protection: Safety glasses are recommended when handling cylinders.
Other protective equipment: Safety shoes are recommended when handling
cylinders.

5.6.8 PHYSICAL AND CHEMICAL PROPERTIES

Appearance and state : Colorless gas at normal temperature and pressure.
Odor : Odorless
Molecular weight : 2.016
Boiling point (1 atm) : -423.0 _F (-252.8 _C)
Specific gravity(Air =1) : 0.06960
Freezing point/melting point : -434.5 F (-259.2 _C)
Vapor pressure (at 70 F) : Not applicable
Gas density (At 70F (21.1C) and 1 atm): 0.00521 lb/ft3 (0.08342 kg/m3)
Solubility in water (Vol/Vol at 60F (15.6C)): 0.019
Specific volume (At70 F (21.1C) and 1 atm): 192 ft3/lb (11.99m3/kg)

5.6.9 STABILITY AND REACTIVITY

Chemical stability : Stable
Conditions to avoid : None
Incompatibility (Materials to Avoid): Oxidizing agents. Some steels are
susceptible to hydrogen embrittlement at high pressures and temperatures.
Reactivity:
A) hazardous decomposition products: None
B) hazardous polymerization: Will not occur.


5.6.10 TOXICOLOGICAL INFORMATION

Hydrogen is a simple asphyxiant.




5.6.11 ECOLOGICAL INFORMATION

No adverse ecological effects are expected. Hydrogen does not contain any
Class I or Class II ozone depleting chemicals (40 CFR Part 82). Hydrogen is
not listed as a marine pollutant by DOT (49 CFR Part 171).

5.6.12 DISPOSAL CONSIDERATIONS

Waste disposal method: Do not attempt to dispose of residual or unused
product in the cylinder. Return to supplier for safe disposal. Residual product
within process system may be vented at a controlled rate, to the atmosphere
through a vent stack that discharges to an elevated point. This stack should be
in an isolated area away from ignition sources.










5.7 HAZOP study
Project name: HAZOP study on Methanol Manufacturing Plant Date: 16/3/2011 Page 1of 3 Completed:
Process: Reactor No action:
Section: Reactor shown in Figure 1 Reference drawing: Fig 1 Reply date:



Item Study
node
Process
parameters
Deviations
(guide
words)

Possible causes

Possible consequences

Action required
Assigned
to:

1A
















1B




Cooling
coils




















Flow No
















High





1. Control valve
fails closed
2. Plugged cooling
coils





3. Cooling water
services failure

4. Controller fails
and closes valve

5. Air pressure fails,
closing valve
1. Control valve
fails open


2. Controller fails
and opens valves
1. Loss of cooling,
possible runaway
2.






3.


4.


5.

1.Reactor cools,
reactant concentration
build, possible runaway
on heating
2.
1. Select valve to fail
open
2. Install filter with
maintenance procedure
Install cooling water
flow meter and low flow
alarm
Install high temperature
alarm to alert operator
3. Check and monitor
reliability of water
services
4. Place controller on
critical instrumentation
list
5. See 1A.1

1. Instruct operators
and update procedures


2. See 1A.4


Project name: HAZOP study on Methanol Manufacturing Plant Date: 16/3/2011 Page 2of 3 Completed:
Process: Reactor No action:
Section: Reactor shown in Figure 1 Reference drawing: Fig 1 Reply date:



Item Study
node
Process
parameters
Deviations
(guide
words)

Possible causes

Possible consequences

Action required
Assigned
to:

1C





1D

1E
1F




1G

1H

1I


1J








































Low





As well as,

Part of,
Reverse




Other
than,
Sooner
than,
Later than


Where
else
1. Partially plugged
cooling line
2. Partial water
sources failure
3. Control valve
fails to respond
1. contamination of
water supply
1. Covered under 1C
1. Failure of water
source resulting in
backflow
2. Backflow due to
high backpressure
1. Not considered
possible
1. Cooling normally
started early
1. Operator error


1.Not considerable
possible
1. Diminish cooling,
possible runaway
2.

3.

1. Not possible here


1.Loss of cooling,
possible runaway

2.



1. None

1.Temperature rises,
possible runaway

1. See 1A.4

2. See 1A.2

3. Place valve on critical
instrumentation list
1. None


1. See 1A.2


2. Install check valve





1.Interlock between
cooling flow and reactor
feed




Project name: HAZOP study on Methanol Manufacturing Plant Date: 16/3/2011 Page 3of 3 Completed:
Process: Reactor No action:
Section: Reactor shown in Figure 1 Reference drawing: Fig 1 Reply date:



Item Study
node
Process
parameters
Deviations
(guide
words)

Possible causes

Possible consequences

Action required
Assigned
to:

1K

1L


2A






2B





Stirrer
Temp.




Agitation
Low

High


No






More

1. Low water
supply temperature
1. High water
supply temperature

1.Stirrer motor
malfunction

2. Power failure



1. Stirrer motor
controller fails
1. None-controller
handles
1. Cooling system
capacity limited, temp.
increases
1.No mixing, possible
accumulation of
unreacted materials
2. Monomer feed
continues, possible
accumulation of
unreacted materials
1. uneven mixing
1.None

1.Install high flow alarm
and/or cooling water
high temp. alarm
1.Interlock with feed
line

2.Monomer feed valve
must fail closed on
power loss

1.Low purity of the
product







Hazards and Operability Review
Project name: HAZOP study on Ethanol Manufacturing Plant Date: 16/3/2011 Page 1of 3 Completed:
Process: Fired Heater No action:
Section: Fired heater shown in Figure 1 Reference drawing: Fig 1 Reply date:



Item Study
node
Process
paramet
ers
Deviations
(guide
words)

Possible causes

Possible consequences

Action required
Assigned
to:

1A
















1B



Cooling coil

















Flow No
















High






1. Control valve
fails closed
2. Plugged cooling
coils

3. Cooling water
services failure

4. Controller fails
and closes valve

5. Air pressure fails,
closing valve




1. Control valve
fails open


2. Controller fails
and opens valves

1. Loss of cooling,
possible runaway
2.


3.


4.


5.





1.Reactor cools,
reactant concentration
build, possible runaway
on heating
2.

1. Select valve to fail
open
2. Install filter with
maintenance procedure
Install cooling water
flow meter and low flow
alarm
Install high temperature
alarm to alert operator
3. Check and monitor
reliability of water
services
4. Place controller on
critical instrumentation
list
5. See 1A.1

1. Instruct operators
and update procedures


2. See 1A.




Project name: HAZOP study on Methanol Manufacturing Plant Date: 16/3/2011 Page 2of 3 Completed:
Process: Fired Heater No action:
Section: Fired Heater shown in Figure Reference drawing: Fig Reply date:



Item Study
node
Process
parameters
Deviations
(guide
words)

Possible causes

Possible consequences

Action required
Assigned
to:

1C





1D

1E
1F




1G

1H

1I


1J


























Low





As well as,

Part of,
Reverse




Other
than,
Sooner
than,
Later than


Where
else

1. Partially plugged
cooling line
2. Partial water
sources failure
3. Control valve
fails to respond
1. contamination of
water supply
1. Covered under 1C
1. Failure of water
source resulting in
backflow
2. Backflow due to
high backpressure
1. Not considered
possible
1. Cooling normally
started early
1. Operator error


1.Not considerable
possible

1. Diminish cooling,
possible runaway
2.

3.

1. Not possible here


1.Loss of cooling,
possible runaway

2.



1. None

1.Temperature rises,
possible runaway


1. See 1A.4

2. See 1A.2

3. Place valve on critical
instrumentation list
1. None


1. See 1A.2


2. Install check valve





1.Interlock between
cooling flow and reactor
feed




Project name: HAZOP study on Methanol Manufacturing Plant Date: 16/3/2011 Page 3of 3 Completed:
Process: Fired Heater No action:
Section: Fired Heater shown in Figure 1 Reference drawing: Fig 1 Reply date:



Item Study
node
Process
parameters
Deviations
(guide
words)

Possible causes

Possible consequences

Action required
Assigned
to:

1K

1L


2A












Air pipe
after
compre
ssor
and
valve
Temp.




Pressure
Low

High


Low
1. Low water
supply temperature
1. High water
supply temperature

1.Stoppage of
power to motor or
turbine turning the
compressor
2. Break the
coupling between
motor and
compressor
3.Compressor
failure, e.g:
breakage of blade
4.Closure of air
valve due to failure



5.Closure of air
valve due to poor
decision by
operator
1. None-controller
handles
1. Cooling system
capacity limited, temp.
increases
1.Uncombusted fuel in
the fire box-danger of
explosion, wasted fuel

2.



3. (plus danger
from flying material)

4.




5.
1.None

1.Install high flow alarm
and/or cooling water
high temp. alarm
1. Monitor and do
regular inspection on
the fired heater

2.



3.


4. Install flow indicator
to measure the flow of
air after the pipe and
actives the shutdown if
the flow too low
5.Install air flow
controller


Project name: HAZOP study on Ethanol Manufacturing Plant Date: 16/3/2011 Page 1 of 5 Completed:
Process: Flash Vessel No action:
Section: Flash Vessel shown in Figure 1 Reference drawing: Figure 1 Reply date:



Item Study
node
Process
parameters
Deviations
(guide
words)

Possible causes

Possible consequences

Action required
Assigned
to:

1A



1B





1C



1D


1E


1F

1G

Mixture of
hydrogen,
methanol
and
methane
into flash
vessel















Flow























No



High





Low



As well as


Reverse


Other
than
Sooner
than
1.Pipe rupture

2. Control valve fail
close
1. Pipeline leakage

2. Control valve
fails open
3. Controller fails
and open valve
1.Pipeline partially
plugged
2. Control valve
fails to respond
1. Contamination of
the hydrolysis
mixture
1. Backflow of the
mixture due to high
pressure
1. Not considered
possible
1. Not considered
possible
1. No flow into the
flash vessel
2. No flow into the
flash vessel
1. Flow entering the
column slow
2. Over pressurized in
the vessel
3. Over pressurized in
the vessel
1. Leakage

2. Temperature rise,
possible runaway
1. Prohibit of using
polluted water

1.High pressure in the
flash vessel




1. Monitor and regular
inspection for pipeline
2. Install valve fails close

1. Monitor and regular
inspection for pipeline
2. Install valve fails to
close
3. install valve fails to
close
1. Do regular inspection

2. Install valve fails to
open
1. Install filter with
maintenance process

1.Install check valve







Project name: HAZOP study on Ethanol Manufacturing Plant Date: 16/3/2011 Page 2 of 5 Completed:
Process: Flash Vessel No action:
Section: Flash Vessel shown in Figure 1 Reference drawing: Figure 1 Reply date:



Item Study
node
Process
parameters
Deviations
(guide
words)

Possible causes

Possible consequences

Action required
Assigned
to:

1H


1I


1J


1J


1K

2A


2B















Product
outlet
(Methan
ol at
bottom,



Temp.





Pressure




Flow




Later than


High


Low


High


Low

No


More


1. Operator Error


1.High inlet
temperature
1.Low hydrolysis
mixture
temperature

1. Tank
overpressure

1.Low pressure in
stripping column
1. Pipe rupture


1.High flow of the
product
1. Temperature
rise,Possible runaway

1. Overpressure in the
vessel (explosion)

1. The mixture cannot
be separated

1.Explosion
1. Reduce ethylene
flow
1. No flow at outlet

1.High pressure in the
outlet

1.Increase the pressure
at the outlet stream
1. Install temperature
alarm high to alert
operator
1. Install of temperature
indicator controller,
alarm
1. Install temperature
alarm high, control
valve
1. Install pressure
indicator controller

1.Install control valve

1.Do full monitoring and
supervision to the
pipeline
1. Install control valve
Install flow indicator





Project name: HAZOP study on Methanol Manufacturing Plant Date: 16/3/2011 Page 3 of 5 Completed:
Process: Flash Vessel No action:
Section: Flash Vessel shown in Figure 1 Reference drawing: Fig 1 Reply date:



Item Study
node
Process
parameters
Deviations
(guide
words)

Possible causes

Possible consequences

Action required
Assigned
to:

2D


2E



2F


2G

2H




2I




2J
Hydroge
n at top)
















Temp.









Pressure

Less



As well as


Part of


Other
than
High





Low



High


1. Low flow of the
product


1.Contamination of
the product

1. Concentration


1. Not considered
as possible
1. High pressure of
the gaseous
mixture



1.Low pressure of
the mixture


1.Overpressure at
the outlet

1.Precipitation of the
product


1. Reduce the purity of
the product

1. Low rate of
evaporation of the
product


1.Methanol may
evaporate together
with the gaseous
product
2. Explosion

1. Gaseous product will
condense


1.Leakage occur

1. Install pump
Install pressure
indicator controller
Install control valve
1. Modify the stripping
column to a better
distillation
1. Monitor and check
constantly the vacuum
evaporation system


1.Install temperature
controller


2.Install temperature
controller
1. Install temperature
control valve


1. Install pressure relief
valve



Project name: HAZOP study on Ethanol Manufacturing Plant Date: 16/3/2011 Page 4 of 5 Completed:
Process: Flash Vessel No action:
Section: Flash Vessel shown in Figure 1 Reference drawing: Fig 1 Reply date:



Item Study
node
Process
parameters
Deviations
(guide
words)

Possible causes

Possible consequences

Action required
Assigned
to:



2K





3A

3B



3C















Inside
flash
vessel








Level


Low





No

High



Low









1.Vessel may
rupture
(surrounding
pressure higher)


1.Vessel defects

1. Tank overflow



1. Leakage of
column
2. Fouling of the
column








1. Explosion occur





1.Separation process
cannot be completed
1. Increase of pressure
inside the stripping
column

1. Mixture level inside
column dropped
2. Product cannot be
separated





1. Install pressure
indicator controller
1.Do regular inspection
and monitoring


1. Install flow meter

1. Install level indicator
controller


1. Do regular
monitoring and
inspection of the
column


Project name: HAZOP study on Methanol Manufacturing Plant Date: 16/3/2011 Page 5 of 5 Completed:
Process: Flash Vessel No action:
Section: Flash Vessel shown in Figure 1 Reference drawing: Fig 1 Reply date:



Item Study
node
Process
parameters
Deviations
(guide
words)

Possible causes

Possible consequences

Action required
Assigned
to:

3D


3E

3F


3G


As well as


Other
than
Sooner
than

Later than
1. Contamination
occur inside vessel

1.Not considered

1.Corrosion of the
column

1. Operator error
1. Prohibit of using
polluted water

1. Decreasing the yield
of product
1. Temperature rise,
possible runaway

1.Explosion
1. Install filter with
maintenance process

1. Use special material
of construction
1.Install temperature
alarm high to alert
operator
1. Do regular
monitoring and
inspection








PART 6

6.0 Environmental Analysis
Our main waste to environment is hydrogen and methanol. In normal conditions
its a colourless, odourless and insipid gas, formed by diatomic molecules, H
2
. The
hydrogen atom, symbol H, is formed by a nucleus with one unit of positive charge
and one electron. Its atomic number is 1 and its atomic weight 1,00797 g/mol. Its
one of the main compounds of water and of all organic matter, and its widely spread
not only in The Earth but also in the entire Universe. There are three hydrogen
isotopes: protium, mass 1, found in more than 99,985% of the natural element;
deuterium, mass 2, found in nature in 0.015% approximately, and tritium, mass 3,
which appears in small quantities in nature, but can be artificially produced by
various nuclear reactions.
Common hydrogen has a molecular weight of 2,01594 g. As a gas it has a
density of 0.071 g/l at 0C and 1 atm. Its relative density, compared with that of the
air, is 0.0695. Hydrogen is the most flammable of all the known substances.
Hydrogen is slightly more soluble in organic solvents than in water. Many metals
absorb hydrogen. Hydrogen absorption by steel can result in brittle steel, which leads
to fails in the chemical process equipment. At normal temperature hydrogen is a not
very reactive substance, unless it has been activated somehow; for instance, by an
appropriate catalyser. At high temperatures its highly reactive. Although in general
its diatomic, molecular hydrogen dissociates into free atoms at high temperatures.
Atomic hydrogen is a powerful reductive agent, even at ambient temperature. It
reacts with the oxides and chlorides of many metals,
like silver, copper, lead, bismuth and mercury, to produce free metals. It reduces
some salts to their metallic state, like nitrates, nitrites and sodium and potassium
cyanide. It reacts with a number of elements, metals and non-metals, to produce
hydrides, like NAH, KH, H
2
S and PH
3
. Atomic hydrogen produces hydrogen
peroxide, H
2
O
2
, with oxygen. Atomic hydrogen reacts with organic compounds to
form a complex mixture of products; with etilene, C
2
H
4
, for instance, the products
are ethane, C
2
H
6
, and butane, C
4
H
10
. The heat released when the hydrogen atoms
recombine to form the hydrogen molecules is used to obtain high temperatures in
atomic hydrogen welding. Hydrogen reacts with oxygen to form water and this
reaction is extraordinarily slow at ambient temperature; but if its accelerated by a
catalyser, like platinum, or an electric spark, its made with explosive violence.
Health effects of hydrogen
A. Effects of exposure to hydrogen:
- Fire: Extremely flammable. Many reactions may cause fire or explosion.
- Explosion: Gas/air mixtures are explosive.
- Routes of exposure: The substance can be absorbed into the body by inhalation.
- Inhalation: High concentrations of this gas can cause an oxygen-deficient
environment. Individuals breathing such an atmosphere may experience symptoms
which include headaches, ringing in ears, dizziness, drowsiness, unconsciousness,
nausea, vomiting and depression of all the senses. The skin of a victim may have a
blue color. Under some circumstances, death may occur. Hydrogen is not expected
to cause mutagenicity, embryotoxicity, teratogenicity or reproductive toxicity. Pre-
existing respiratory conditions may be aggravated by overexposure to hydrogen.
- Inhalation risk: On loss of containment, a harmful concentration of this gas in the
air will be reached very quickly.

B. Physical dangers:
The gas mixes well with air, explosive mixtures are easily formed. The gas is lighter
than air.

C. Chemical dangers:
Heating may cause violent combustion or explosion. Reacts violently with air,
oxygen, halogens and strong oxidants causing fire and explosion hazard. Metal
catalysts, such as platinum and nickel, greatly enhance these reactions. High
concentrations in the air cause a deficiency of oxygen with the risk of
unconsciousness or death. Check oxygen content before entering area. No odor
warning if toxic concentrations are present. Measure hydrogen concentrations with
suitable gas detector (a normal flammable gas detector is not suited for the purpose).
D. First aid

- Fire: Shut off supply; if not possible and no risk to surroundings, let the fire burn
itself out; in other cases extinguish with water spray, powder, carbon dioxide.
- Explosion: In case of fire: keep cylinder cool by spraying with water. Combat fire
from a sheltered position.
- Inhalation: Fresh air, rest. Artificial respiration may be needed. Refer for medical
attention.
- Skin: Refer for medical attention.

Environmental effects of hydrogen
A. Hydrogen in the environment:
Hydrogen forms 0.15 % of the earth's crust; it is the major constituent of water. 0.5
ppm of hydrogen H
2
and varial proportions as water vapour are present in the
atmosphere. Hydrogen is also a major component of biomass, constituting the 14%
by weight.
B. Environmental stability:
Hydrogen occurs naturally in the atmosphere. The gas will be dissipated rapidly in
well-ventilated areas.
C. Effect on plants or animals:
Any effect on animals would be related to oxygen deficient environments. No
adverse effect is anticipated to occur to plant life, except for frost produced in the
presence of rapidly expanding gases.
D. Effect on aquatic life:
No evidence is currently available on the effect of hydrogen on aquatic life.
Table 1 China Methane Emissions by Source (TgCO
2
Equivalents)
Source Category 1990 1995 2000 2005 2006 2007 2008
Enteric Fermentation 132.4 143.7 136.8 136.7 139.0 141.2 140.8
Landfills 149.3 144.1 120.7 125.6 127.1 126.5 126.3
Natural Gas Systems 129.5 132.6 130.7 103.6 103.1 99.5 96.4
Coal Mining 84.1 67.1 60.4 56.9 58.3 58.1 67.6
Manure Management 29.3 33.9 38.6 42.2 42.3 45.9 45.0
Forest Land Remaining Forest
Land
3.2 4.3 14.3 9.8 21.6 20.0 11.9
Petroleum Systems 33.9 32.0 30.2 28.2 28.2 28.8 29.1
Wastewater Treatment 23.5 24.8 25.2 24.3 24.5 24.4 24.3
Stationary Combustion 7.4 7.1 6.6 6.6 6.2 6.5 6.7
Rice Cultivation 7.1 7.6 7.5 6.8 5.9 6.2 7.2
Abandoned Underground Coal
Mines
6.0 8.2 7.4 5.6 5.5 5.7 5.9
Mobile Combustion 4.7 4.3 3.4 2.5 2.4 2.2 2.0
Composting 0.3 0.7 1.3 1.6 1.6 1.7 1.7
Petrochemical Production 0.9 1.1 1.2 1.1 1.0 1.0 0.9
Field Burning of Agricultural
Residue
0.8 0.7 0.9 0.9 0.9 1.0 1.0
Iron and Steel Production &
Metallurgical Coke Production
1.0 1.0 0.9 0.7 0.7 0.7 0.6
Ferroalloy Production + + + + + + +
Silicon Carbide Production and
Consumption
+ + + + + + +
International Bunker Fuels + + + + + + +
Total for China 613.4 613.2 586.0 553.2 568.2 569.2 567.6
Source: EPA Methane and Nitrous Oxide Emissions From Natural Sources, April 2010 (PDF)

6.1 Project Activity and Data
The expected exponential growth in the demand for methanol will result in
increased transportation by barge and rail, as well as an increased number of
storage and distribution facilities. Given this expected increase in production,
transportation, storage and use of methanol, methanol, the potential for accidental
releases to the environment will increase. In 1992, methanol ranked third
amongst all chemicals reportedly released by industry to the environment as noted
in annual Toxics Release Inventory (TRI) reports required by the U.S.
Environmental Protection Agency (USEPA). As shown in Table ES-2, U.S.
methanol releases are primarily to the atmosphere; however, approximately 20%
of the methanol is directly discharged to the soil, groundwater, or surface water
(total mass released represents approximately 1% of the total mass of methanol
produced). Three conceptual release models or scenarios were considered as part
of this study. These include: tank truck or rail car release, barge release, and
release from underground storage tanks (USTs) at a refueling facility. A release
from a tank truck or rail car could take place in a variety of settings. A rail tank
car accident could potentially release up to 34,500 gallons of methanol. In
addition to transport of methanol in the U.S. by rail, the U.S. obtains some of its
methanol demand from overseas, all of which is transported by ships or barges.
Thus, releases to ocean, estuary, or river environments are possible. A typical
barge tanker carries 45,000 tons of product (13.6 million gallons) and in 1999, a
96,000 ton (29.1 million gallons) vessel will be introduced for dedicated methanol
transport. The third release scenario involves methanol losses at a fueling or
storage facility from an UST. A typical UST could allow a fuel release into the
subsurface at a rate of 0.5 gallons per minute (gpm) before the leak detection
devices are activated. Although continuous releases of this size are uncommon,
the potential for significant methanol losses from USTs cannot be overlooked.
Because the CAA, CWA, and SDWA do not require monitoring of methanol in
groundwater, surface water, or the atmosphere, national monitoring data sets on
methanol occurrence in air or water are not available. However, the behavior of
methanol within environmental compartmentssoil, air, surface water, and
ground watercan be predicted based on its chemical and physical properties.
Methanol is a clear, colorless, volatile liquid with a faint alcohol-like odor, though
it is difficult to detect in the air at low concentration(<10 part per million by
volume(ppm
v
)). per million by volume (ppmv)). Methanol is the simplest
alcohol, having only one carbon atom, and is capable of being completely mixed
in water. It easily dissolves in other alcohols and chlorinated hydrocarbons, but
has limited solubility in diesel fuel, vegetables oils, and aliphatic hydrocarbons.
The chemical and physical properties of methanol have been used to describe the
fate and transport of methanol in the environment in the event that accidental
releases were to occur.
6.1.1 Fate and Transport
Although methanol occurs naturally in the environment as a result of
various biological processes in vegetation, microorganisms, and other
living species, a large release of concentrated methanol to ground water,
surface water, or soil has the potential to adversely impact the affected
environment. Once released, the half-life of methanol (the time required
for 50% reduction in the mass released or present) depends on numerous
factors including: the nature of the release, quantity of the release, and
physical, chemical and microbiological characteristics of the impacted
media. Table ES-3 is a summary of the estimates of the range of probable
methanol half-lives in various environmental media as documented from
various reports, in comparison with the probable half-lives of benzene, a
common gasoline constituent. Based on these data, regardless of the
release scenario, methanol appears unlikely to accumulate in the
groundwater, surface water, air, or soil.
The physical and chemical properties of methanol help to further
define the fate and transport of this chemical in the various environmental
media in the context of each of the conceptual release scenarios. The
dominant mechanisms of methanol loss from subsurface soil and
groundwater are expected to be biodegradation and advection (dispersion
and diffusion) with little loss from adsorption on soils due to its high
solubility and low retardation factor. In surface water, surface water, the
infinite solubility of methanol will result in rapid wave-, wind-, and tide
enhanced dilution to low concentrations (< 1%). Once concentrations
have been diluted below toxic levels the dominant mechanism of methanol
loss is expected to be biodegradation. Compared to other loss mechanisms
identified, including volatilization and chemical degradation,
biodegradation is expected to be the dominant process controlling the fate
of methanol in the soil, groundwater, and surface water environments. In
addition, the biodegradation of methanol can occur under both aerobic
(oxygen present) and anaerobic (oxygen absent) conditions. Therefore,
following any of the three conceptual release scenarios presented,
methanol is not likely to persist in soil or water due to its rapid
biodegradation. Methanol is miscible in water and consequently will
dissolve quickly and be diluted to low concentrations in the event of a
surface water spill. In groundwater, methanol concentrations are highly
dependent on the nature and the magnitude of the release, but will likely
fall to low concentrations once complete dissolution has occurred. In both
surface and ground waters, methanol will likely be easily biodegraded
under a wide range of possible water quality conditions. Relative to
conventional gasoline and diesel fuel (and many of their constituent
elements such as benzene), methanol is a safer and more environmentally
benign fuel. Thus, hazards caused by gasoline releases will be more
serious than those due to methanol releases, and these hazards will persist
longer in the environment.

6.2 Environmental Monitoring
Following a release of methanol to the subsurface as a result of any of the three
release scenarios, remediation of soil and ground water may be required if natural
biodegradation is not sufficient to meet potential cleanup standards in a reasonable time
frame. Methanol wills quickly biodegrade and, therefore, natural attenuation is likely
to be an effective and inexpensive remediation strategy for both soil and water. If
biodegradation is not sufficient to meet cleanup objectives and an alternative
remediation strategy is required, the high vapor pressure of methanol suggests that soil
vapor extraction will effectively remove any residual methanol from the soil. Once
extracted from the subsurface, the methanol vapors can be biodegraded using
appropriate technologies such as vapor phase biofilters. It is unlikely that elevated
levels of methanol will persist in either groundwater or surface water due to the rapid
rate of biodegradation. However, if drinking water sources experienced a methanol
release, treatment would likely be required before distribution to the public. Most
treatment technologies that remove gasoline components from water, including air
stripping and granular activated carbon, are not effective at removing methanol due to
its low volatility and high solubility. Reverse osmosis or nanofiltration is also
ineffective at removing methanol because of its small size and low molecular weight.
Advance oxidation processes such as ozonation with ultraviolet light are expected
to be effective, but the feasibility and cost of treatment is site specific. Biological
treatment processes are effective at removing methanol from drinking water, and are
increasingly being accepted by the drinking water community for drinking water
applications. However, biological treatment in drinking water applications is still not
extensively used and, therefore, would require broader regulatory acceptance. In
conclusion, in the unlikely event that methanol contaminates source waters; methanol
can be removed in both a remediation and drinking water treatment context using
biological processes. However, the effectiveness, cost and public acceptance will be
site specific.

6.3 Human and Aquatic Toxicity
Methanols properties and toxicity are well understood. According to the
extensive literature reviewed for this study, methanol is neither mutagenic nor
carcinogenic. Human exposure to methanol can occur via the inhalation, ingestion, or
dermal contact pathways. Inhalation of methanol vapors can cause irritation of the
mucus membranes, dizziness, nausea, headaches, and blurred vision if exposure at high
levels occurs. While inhalation is the most common route of exposure to the body,
ingestion represents the most serious acute health hazard due to the much higher
volume of methanol which can be ingested relative to the volume which can be inhaled.
The effects of ingestion follow the same pattern described for inhalation. With respect
to dermal contact, methanol readily absorbs into the dermal layer with repeated
exposure causing eczema, redness, and scaling. However, the current evidence shows
that acute toxic effects on humans and some animals from methanol only occur at high
doses (> 10 mg/l). The U.S. Department of Energy considers gasoline to be overall
more hazardous to human health than neat methanol. Methanol is significantly less
toxic to marine life than crude oil or gasoline, and many of the effects of short term
exposure are temporary and reversible. The Office of Pollution Prevention and Toxics
indicated that methanol is essentially non-toxic to the four aquatic fish species that were
tested. A large methanol spill into surface water would have some immediate impacts
to the biota in the direct vicinity of the spill. However, because of its properties (i.e,
methanol readily mixes with water and evaporates quickly in the atmosphere) methanol
would rapidly dissipate into the environment, and within fairly short distances from the
spill would reach levels where biodegrading would rapidly occur.

























PART 7

7.0 Mass Balance
Methane feed = 770.1 tonne/day




7

4

2

2


2

2

2

1 mol CH4 reacts with 1 mol
2



7.1 Mixer







Overall balance
F
1
+F
2
=F
3

5192 + 5324 = F3
F
3
=10516 kmol/hr

2 2

1
4

1

3
4

3
2







H
2
O balance;
3,
2

3
=
2,
2

2


3
2

=

2
2

3
= =
15324

10516


3
2

= 0.506

CH
4
balance;
3,
4

F
3
=
1,
4

F
1


3,
4

=

3
=
015192

10516


3,
4

= 0.494


7.2 Reforming reactor (12)

Catalyze reactor (Nickel catalyst)

4

2

2
conversion CH
4
= 99.90%,


3
2

= 0.506

3,
4

= 0.494



4


4,
2


4,
2

4,

4,

4,
2


4,
2

4,
4


4,
4








= 5194
1

4,
2

= 5321-
1

4,
=
1

4,
2

= 3
1



CH
4
conversion;


=
10999
4

x
5194
4


= 5.194 kmol CH
4
/hr
5.194 = 5194 -
1

1
= 5188.81 kmol/hr
Substituting
1


into equation

,
= 5188.81 kmol CO/hr

4,
2

= 5321 5188.81
= 132.19 kmol/hr

4,
2

= 3x5188.81
= 15566.43 kmol/hr


F
4
= 5.194+5188.81+132.19+15566.43
= 20892.62 kmol/hr

Thus;
4,
2

= 0.006

4,
= 0.248

4,
2

= 0.745

4,
4

= 0.0002



7.3 Reactor 26 and separator















Reactor 26

2

3
40% conversion, limiting CO and CO
2


Total balance

4

10

5


5




Reactor 26

Separator
F
5
F
4
= 20892.62kmol/hr

4,
2

44

4
2


F
6

8
3

8
2

8
4

8
2


F
10
4400 kmol/hr Purge

10
4

10

10
2

10
2

=0.0015

9
3

=0.13

F
8
= 31
F
9
F
7

9
3

9
2

9
2

9
2

9

F
4

5


CH
4
balance

5
4

4

4
4

10

10
4

5
4

5
4


CO balance

5

4

10

10




H
2
balance

5
2

4

4
2

10

10
2

5
2


76
H
2
O balance

52

4

4
2

10

10
2

5
2


0052


4

5

5
4

2

5

52

2

5

52

6

1

6
2

1

6
3

6
2

52
=

6
4

5

5
4

6

1


1

6
2

1



6
3


1
=

6
3

6
2

6
4

6
2

10

8

9


9


9

9

6

7


7



CH
4
balance

6
4

7

7
4

9
4

7
4


CO balance

7

6

7


H
2
balance

7
2

6

6
2

9
2

7
2

H
2
O balance

72

6

6
2

9
2

7
2

balance

7
3

6
3

9
3

7
3










PART 8

8.0 Energy Balance

8.1 Reactor 1













Energy balance
Q = mH
f
mH
i
Substance H
in liquid
phase

H
in
gases
phase
H
out liquid
phase

H
out

gases
phase
H
2
- - H
3
H
7
CO - - H
4
H
8
H
2
O - H
1
H
5
H
9

CH
4
- H
2
H
6
H
10




99.9% conversion
CH
4
+ H
2
O

CO

+ 3H
2


T=350
0
C
P=3000kPa
T =850
o
C
P=3000kPa
Kp


CH
4
H
2
O
CH
4

CO
H
2

H
2
O

INLET
H
1
= CH
4
(L, 25
O
C, 101.325kPa)


CH
4
(L, 165
0
C, 101.325kPa)


CH
4
(L, 165
O
C, 1200kPa)

H
a
=
850
25

=
9

165
25

3

2

= -3200 kJ/kg

H
b
= (1200-101.325)x10
3
Pa 8.314J/mol.K 1m
3
1kJ
8.314m
3
Pa/mol.K 781.83kg 1000J
= 1.405 kJ/kg
So H
1
= h
a
+ h
b

= (-3200+1.405) kJ/kg
= -3198

kJ/kg






h
a

h
b

H
2
= O
2
(g, 25
O
C, 101.325kPa)


O
2
(g, 165
0
C, 101.325kPa)


O
2
(g, 165
O
C, 1200kPa)

H
a
=
165
25

=
1

4

2
165
25

= 11922kJ/kg

H
b
= (1200-101.325)x10
3
Pa 8.314J/mol.K 1m
3
1kJ___
8.314m
3
Pa/mol.K 1137.68kg 1000J
= 0.966 kJ/kg
So H
2
= h
a
+ h
b

= (11922+0.966) kJ/kg
= 11922.966

kJ/kg







h
a

h
b

H
3
= (L, 25
O
C, 101.325kPa)


(L, 193.2
0
C, 101.325kPa)


(L, 193.2
O
C, 1200kPa)

H
a
=
1932
25

=
1

3

2
1932
25

= -1536.36kJ/kg

H
b
= (1200-101.325)x10
3
Pa 8.314J/mol.K 1m
3
1kJ__
8.314m
3
Pa/mol.K 961.93kg 1000J
= 1.142 kJ/kg
So H
3
= h
a
+ h
b

= (-1536.36+1.142) kJ/kg
= -1535.22

kJ/kg







h
a

h
b

H
4
=(L, 25
O
C, 101.325kPa)


(L, 193.2
0
C, 101.325kPa)


(L, 193.2
O
C, 1200kPa)

H
a
=
1932
25

=
1

3

2
1932
25

= -300.51kJ/kg

H
b
= (1200-101.325)x10
3
Pa 8.314J/mol.K 1m
3
1kJ_
8.314m
3
Pa/mol.K 950.33kg 1000J
= 1.156 kJ/kg
So H
4
= h
a
+ h
b

= (-300.51+1.156) kJ/kg
= -299.35

kJ/kg







h
a

h
b

H
5
(L, 25
O
C, 101.325kPa)


(L, 193.2
0
C, 101.325kPa)



2
(L, 193.2
O
C, 1200kPa)

H
a
=
1932
25

=
9

1932
25

2

= -3181.32kJ/kg

H
b
= (1200-101.325)x10
3
Pa 8.314J/mol.K 1m
3
1kJ__
8.314m
3
Pa/mol.K 781.83kg 1000J
= 0.9657kJ/kg
So H
5
= h
a
+ h
b

= (-3181.32+0.9657) kJ/kg
= -3180.35

kJ/kg







h
a

h
b

OUTLET
H
6
= H
2
O

(L, 25
O
C, 101.325kPa)


H
2
O (L, 193.2
0
C, 101.325kPa)


H
2
O (L, 193.2
O
C, 1200kPa)

H
a
=
1932
25

=
0

4

2
1932
25

3

= 33524.42685 kJ/kg

H
b
= (1200-101.325)x10
3
Pa 8.314J/mol.K 1m
3
1kJ___
8.314m
3
Pa/mol.K 997.99kg 1000J
= -0.012 kJ/kg
So H
6
= h
a
+ h
b

= (33524.42685 0.012) kJ/kg
= 33524.4149kJ/kg





h
a

h
b

H
7
= (g, 25
O
C, 101.325kPa)


(g, 193.2
0
C, 101.325kPa)


(g, 193.2
O
C, 1200kPa)

H
a
=
1932
25

=

1

3

2

1932
25

3

= 8169.5417 kJ/kg

H
b
= (1200-101.325)x10
3
Pa 8.314J/mol.K 1m
3
1kJ___
8.314m
3
Pa/mol.K 961.93kg 1000J
= 1.142 kJ/kg
So H
7
= h
a
+ h
b

= (8169.5417 +1.142) kJ/kg
= 8170.6837 kJ/kg






h
a

h
b

H
8
= (g, 25
O
C, 101.325kPa)


(g, 193.2
0
C, 101.325kPa)


(g, 193.2
O
C, 1200kPa)

H
a
=
1932
25

=
1

3

1932
25

3

= -532.833 kJ/kg

H
b
= (1200-101.325)x10
3
Pa 8.314J/mol.K 1m
3
1kJ___
8.314m
3
Pa/mol.K 950.33kg 1000J
= 1.156 kJ/kg
So H
8
= h
a
+ h
b

= (-532.833 +1.156) kJ/kg
= -531.677 kJ/kg







h
a

h
b

H
9
(g, 25
O
C, 101.325kPa)


(g, 193.2
0
C, 101.325kPa)


(g, 193.2
O
C, 1200kPa)

H
a
=
1932
25

=
9

1

3

1932
25

7

3

= -4189.58525 kJ/kg

H
b
= (1200-101.325)x10
3
Pa 8.314J/mol.K 1m
3
1kJ__
8.314m
3
Pa/mol.K 781.82 kg 1000J
=1.4053kJ/kg
So H
9
= h
a
+ h
b

= (-4189.58525 +1.4053) kJ/kg
= -4188.179 kJ/kg






h
a

h
b

H
10
= H
2
O (g, 25
O
C, 101.325kPa)


H
2
O (g, 193.2
0
C, 101.325kPa)


H
2
O (g, 193.2
O
C, 1200kPa)

H
a
=
1932
25

=

4

1932
25

3

= -36661.985 kJ/kg

H
b
= (1200-101.325)x10
3
Pa 8.314J/mol.K 1m
3
1kJ
8.314m
3
Pa/mol.K 997.99 kg 1000J
=1.10088kJ/kg
So H
10
= h
a
+ h
b

= =(-36661.985 +1.10088)kJ/kg
=-36660.884 kJ/kg





h
a

h
b

substance
H
in liquid
phase

H
ingasesphase
H
out liquidphase
H
outgasesphase

CO - - -1535.22kJ/kg

8170.68kJ/kg

H
2
- - -299.35kJ/kg -531.68kJ/kg

H
2
O - 3198kJ/kg -3180.35kJ/kg -4188.18kJ/kg
CH
4
4356kJ/kg 33524.41kJ/kg
-
36660.88kJ/kg

substance
n
in
liquidphase

n
ingasesphase
n
out liquidphase
n
outgasesphase

CO - - 1725.42kg/hr

193.128kg/hr

H
2
- - 1829.64kg/hr 84.184kg/hr

H
2
O - 1239kg/hr 1991.78kg/hr 212.936kg/hr
CH
4
- 1099kg/hr - -

Energy balance
Q = n
out
Hf

n
in
H
i

6

6

8

7


8
kJ/hr
Q = 0.793x10
8
kJ 1hr 1kW = 22027.78 kW
hr 3600s 1kJ/s




8.2 Reactor 2













Energy balance
Q = mH
f
mH
i
Substance H
in liquid
phase

H
in
gases
phase
H
out liquid
phase

H
out

gases
phase
H
2
- H
1
H
3
H
7
CO - H
2
H
4
H
8
CH
3
OH - -

H
5
H
9










99.9% conversion
CH
4
+ H
2
O

CO

+ 3H
2


T=40
0
C
P=101.3kPa
T =28
o
C
P=101.3kPa
Kp


CO
H
2

CH
4

CO
H
2

H
2
O

INLET
H
1
=

(L, 25
O
C, 101.325kPa)


(L, 28
0
C, 101.325kPa)


(L, 28
O
C, 1200kPa)

H
a
=
28
25

=
9

28
25

3

2

= -800 kJ/kg

H
b
= (1200-101.325)x10
3
Pa 8.314J/mol.K 1m
3
1kJ
8.314m
3
Pa/mol.K 781.83kg 1000J
= 1.405 kJ/kg
So H
1
= h
a
+ h
b

= (-800+1.405) kJ/kg
= -801.45

kJ/kg






h
a

h
b

H
2
=

(g, 25
O
C, 101.325kPa)


(g, 28
0
C, 101.325kPa)


(g, 28
O
C, 1200kPa)

H
a
=
28
25

=
1

4

2
28
25

= 5233kJ/kg

H
b
= (1200-101.325)x10
3
Pa 8.314J/mol.K 1m
3
1kJ___
8.314m
3
Pa/mol.K 1137.68kg 1000J
= 0.966 kJ/kg
So H
2
= h
a
+ h
b

= (5233+0.966) kJ/kg
= 5233.966

kJ/kg







h
a

h
b

H
3
= (L, 25
O
C, 101.325kPa)


(L, 50
0
C, 101.325kPa)


(L, 50
O
C, 1200kPa)

H
a
=
50
25

=
1

3

2
50
25

= -1536.36kJ/kg

H
b
= (1200-101.325)x10
3
Pa 8.314J/mol.K 1m
3
1kJ__
8.314m
3
Pa/mol.K 961.93kg 1000J
= 1.142 kJ/kg
So H
3
= h
a
+ h
b

= (-1536.36+1.142) kJ/kg
= -1535.22

kJ/kg







h
a

h
b

H
4
=(L, 50
O
C, 101.325kPa)


(L, 50
0
C, 101.325kPa)


(L, 50
O
C, 1200kPa)

H
a
=
50
25

=
1

3

2
50
25

= -300.51kJ/kg

H
b
= (1200-101.325)x10
3
Pa 8.314J/mol.K 1m
3
1kJ_
8.314m
3
Pa/mol.K 950.33kg 1000J
= 1.156 kJ/kg
So H
4
= h
a
+ h
b

= (-300.51+1.156) kJ/kg
= -299.35

kJ/kg







h
a

h
b

H
5
(L, 25
O
C, 101.325kPa)


(L, 50
0
C, 101.325kPa)


(L, 50
O
C, 1200kPa)

H
a
=
50
25

=
9

50
25

2

= -2133kJ/kg

H
b
= (1200-101.325)x10
3
Pa 8.314J/mol.K 1m
3
1kJ__
8.314m
3
Pa/mol.K 781.83kg 1000J
= 0.9657kJ/kg
So H
5
= h
a
+ h
b

= (-2133+0.9657) kJ/kg
= -2132.35

kJ/kg







h
a

h
b

OUTLET
H
6
=

(L, 25
O
C, 101.325kPa)


(L, 50
0
C, 101.325kPa)


(L, 50
O
C, 1200kPa)

H
a
=
50
25


=
0

4

2
50
25

7

3

= 2813.21 kJ/kg

H
b
= (1200-101.325)x10
3
Pa 8.314J/mol.K 1m
3
1kJ___
8.314m
3
Pa/mol.K 997.99kg 1000J
= -0.012 kJ/kg
So H
6
= h
a
+ h
b

= (2813.21 0.012) kJ/kg
= 2814.31kJ/kg





h
a

h
b

H
7
= (g, 25
O
C, 101.325kPa)


(g, 50
0
C, 101.325kPa)


(g, 50
O
C, 1200kPa)

H
a
=
50
25

=
1

3

50
25

3

= 4196 kJ/kg

H
b
= (1200-101.325)x10
3
Pa 8.314J/mol.K 1m
3
1kJ___
8.314m
3
Pa/mol.K 961.93kg 1000J
= 1.142 kJ/kg
So H
7
= h
a
+ h
b

= (4196 +1.142) kJ/kg
= 4197.142 kJ/kg







h
a

h
b

H
8
= (g, 25
O
C, 101.325kPa)


(g, 50
0
C, 101.325kPa)


(g, 50
O
C, 1200kPa)

H
a
=
50
25

=
1

3

50
25

3

= -532.833 kJ/kg

H
b
= (1200-101.325)x10
3
Pa 8.314J/mol.K 1m
3
1kJ___
8.314m
3
Pa/mol.K 950.33kg 1000J
= 1.156 kJ/kg
So H
8
= h
a
+ h
b

= (-532.833 +1.156) kJ/kg
= -531.677 kJ/kg







h
a

h
b

H
9
(g, 25
O
C, 101.325kPa)


(g, 50
0
C, 101.325kPa)


(g, 50
O
C, 1200kPa)

H
a
=
50
25

=
9

1

3

50
25

7

3

= -4189.58525 kJ/kg

H
b
= (1200-101.325)x10
3
Pa 8.314J/mol.K 1m
3
1kJ__
8.314m
3
Pa/mol.K 781.82 kg 1000J
=1.4053kJ/kg
So H
9
= h
a
+ h
b

= (-4189.58525 +1.4053) kJ/kg
= -4188.179 kJ/kg






h
a

h
b

H
10
= (g, 25
O
C, 101.325kPa)


(g, 50
0
C, 101.325kPa)


H
2
O (g, 50
O
C, 1200kPa)

H
a
=
50
25

=

4

2

50
25

3

= -36661.985 kJ/kg

H
b
= (1200-101.325)x10
3
Pa 8.314J/mol.K 1m
3
1kJ
8.314m
3
Pa/mol.K 997.99 kg 1000J
=1.10088kJ/kg
So H
10
= h
a
+ h
b

= =(-36661.985 +1.10088)kJ/kg
=-36660.884 kJ/kg





h
a

h
b

substance
H
in liquid
phase

H
ingasesphase
H
out liquidphase
H
outgasesphase

CO - 3198kJ/kg -2535.22kJ/kg

8170.68kJ/kg

H
2
- 2513kJ/kg -3001.35kJ/kg -531.68kJ/kg

CH
3
OH - - -3680.35kJ/kg -4188.18kJ/kg

substance
n
in
liquidphase

n
ingasesphase
n
out liquidphase
n
outgasesphase

CO - 1239kg/hr 1725.42kg/hr

193.128kg/hr

H
2
- 1239kg/hr 1829.64kg/hr 84.184kg/hr

CH
3
OH - - 1991.78kg/hr 212.936kg/hr

Energy balance
Q = n
out
Hf

n
in
H
i

6

6

8

7


8
kJ/hr
Q = 0.99816x10
8
kJ 1hr 1kW = 43845.31 kW
hr 3600s 1kJ/s







PART 9

9.0 Heat Exchanger Network
9.1 Table of utilities


9.2 Composite Curve


9.3 Heat Exchanger Network











3
C
6
5
H
4
H
82500
362.82
17676.6
11404.29 1500 12976.17
23361.82
663.6
351
1780
717.97
PART 10
10.1 REACTOR 1
3.13 m
8.1m
Packed Bed Reactor Volume : 250.09 m
3

Reactor 1

, residence time =



Methane:
Volumemetric flowrate :
3.209x10
4
kg/hr 5.109 kg/m
3
= 6281.07 m3/hr
Water:
Volumemetric flowrate ;
3.269x10
4
kg/hr 5.808 kg/m
3
= 5628.44 m3/hr
Total flowrate ;
6281.07 m3/hr + 5628.44 m3/hr = 11909.51 m
3
/hr

Assume , residence time = 1.26 min
Total volumetric flowrate = 11909.51 m3/hr 60
= 198.49 m
3
/min

V = , residence time x

, Total volumetric flowrate,


= 250.09 m
3

Reactor volume =
2

Assume length = 8.1m
250.09 m
3
= R
2
(8.1m)
R = 3.13 m

10.2 REACTOR 2
6.5m
3.03 m
Packed Bed Reactor Volume : 200.0 m
3

Reactor 2

, residence time =



Mixture:
Volumemetric flowrate ;
4.263x10
6
kg/hr 0.2692 kg/m
3
= 15835809.81 m3/hr

Assume , residence time = 0.000758 min
Volumetric flowrate = 15835809.81 m3/hr 60
= 263930 m
3
/min

V = , residence time x

,Total volumetric flowrate,


= 200.0m
3


Reactor volume =
2

Assume length = 6.5m
200.0m
3
= R
2
(6.9 m)
R = 3.03 m






10.3 FLASH SEPARATOR
2.525 m
5.1m
Flash Separator Volume : 102.15 m
3


Flash Separator Column

dV = 0.876 kg/m3
dL = 786 kg/m3
V = 0.107 m/s [(786 kg/m3 0.876 kg/m3) / 0.876 kg/m3 ]
0.5

= 3.203 m/sec
Mass flow rate of vapor = 2.02x10
5
kg /hr
thus to convert to volumetric flow rate, we divide the mass flow rate of vapor with vapor density
Volumetric flow rate = (2.02x10
5
kg /hr) / 0.876 kg/m3
= 230688 m3/hr
= 64.08 m3/sec
A, the cross-sectional area of the drum, in m
2
;
= (vapor flow rate, in m
3
/s) / (vapor velocity V, in m/s)

Vapor flow rate coming out from flash separator = 64.08 m3/sec
A = (64.08 m3/sec) / 3.203 m/sec
= 20 m
2
D, diameter, in m = (4 (20 m
2
) / 3.1416)
0.5
= 5.05 m
Height = 5.1m
Thus the volume = x R
2
x L
= x (2.525 m)
2
x 5.1m
= 102.15 m
3



10.4 HEAT EXCHANGER

































[1] Gedde-Dahl, A. and Holm-Larsen, H., Start-up and Initial Operation of a 2,400 MTPD
Methanol Plant, Ammonia Plant Saf. 39, 1999, 14/23.
[2] http://www.topsoe.com/site.nsf/all/CHAP-6N4GR6?opendocument
[3] Petroleum Technology Quaterly, Q2, 2008, 133
[4] Aasberg-Petersen, K. et al., Synthesis Gas Production for FT Synthesis, Stud. Surf. Sci.
Cat. 152, 2004, 258/405.
[5] Holm-Larsen, H., Alternative Process Routes to Low Cost Methanol, World Methanol
Conference 2000, Copenhagen, Denmark.
[6] Haugaard, J. and Holm-Larsen, H., Recent Advances in Autothermal Reforming Technology
- Reducing Production Cost to Prosper in a Depressed Market, World Methanol
Conference 1999, San Diego, USA.
[7] Dybkjr, I., "Synthesis Gas Technology" Hydrocarbon Engineering, July 2006, 33
[8] Halstead, K., "Oryx GTL from Conception to Reality", Nitrogen and Syngas 292, March-
April 2008, 43
[9] Hansen, J.B. and Nielsen, P.E.H., Methanol Synthesis, in: Ertl, G., Knzinger, H., Schth,
F., Weitkamp, J., Handbook of Heterogeneous Catalysis, Second Edition 2008, Vol. 6, p. 2920,
Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
http://www.uhde.eu/cgi-bin/byteserver.pl/archive/upload/uhde_brochures_pdf_en_6.00.pdf