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Ex Report Methanol
Ex Report Methanol
TITLE:
(PRODUCTION OF METHANOL)
PREPARED BY:
DATE OF SUBMISSION:
NAME OF LECTURER:
INTRODUCTION
PART 1
1.3 Usage 20
PART 2
2.3.1 Overall 29
PART 3
4.2 Transport 49
4.5 Land 51
4.6 Climate 51
PART 5
5.1 Methanol 62
5.2 Methane
5.2.1 Product identification 62
5.5 Water
5.5.1 Product identification 62
5.6 Hydrogen
PART 6
PART 7
PART 9
PART 10
PART 11
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:
1.1 History
1.1.1 Methanol
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]
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.
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 conditions—pressures
ranging from 300–1000 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.
Methanol is also known as methyl alcohol, wood alcohol, wood naphtha or wood
spirits. It is a chemical with formula CH3OH. 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:
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.
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 (CH3OH) 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
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-Al2O3
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.
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
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.
Quench reactor
Adiabatic reactors in series
Boiling water reactors (BWR)
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 240ºC and 260ºC - 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
F1= 7.074x104
lb/hr
T=1562 °F
P=435.1 psia
CH4 =1
Fliq =0 lb/hr
T=662°F
P=435.1 psia
2.3.3 Conversion Reactor (CRV-102)
𝑋10,𝐶𝐻4 = 0.0009
𝑋10,𝐻2 𝑂 = 0.0001
F10= 3.722x106 lb/hr
𝑋10,𝐶𝑂 = 0
6 T=127.6 °F
F9= 3.722x10 lb/hr
𝑋10,𝐻2 = 0.8593
P=14.7 psia
T=88.41 °F
𝑋10,𝐶𝐻3 𝑂𝐻 =0.1398
P=14.7 psia
𝑋9,𝐶𝐻4 = 0.0008
𝑋9,𝐻2 𝑂 = 0.0001
𝑋9,𝐶𝑂 = 0.0073
𝑋11,𝐶𝐻4 =0
𝑋9,𝐻2 = 0.8613
F11 =0 lb/hr
𝑋11,𝐻2 𝑂 = 0.0011
𝑋9,𝐶𝐻3 𝑂𝐻 =0.1305 T=127.6°F
𝑋11,𝐶𝑂 = 0
P=14.7 psia
𝑋11,𝐻2 = 0.0002
𝑋11,𝐶𝐻3 𝑂𝐻 =0.9987
PART 3
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
The production is to achieve 387260 metric tonnes per annum. The raw
materials used are:
Water 6472200
= 207633+6472200 = RM 6679833
Reactor 2 683009
Separator 2 233463
Mixer 1 711295
Vessel 3 7497
Compressor 1 293000
Pump 1 8690
The cost estimation of equipment:
= RM 3113420
2 05
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.
2 05
2 05
= 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 m2.
120 m
100 m
RM 27.73
Price per meter square of land
m2
Land cost
14164 RM 27 .73
m2 RM 392767 .72
m2
3.2.5 Utilities Cost Estimation
Steam
Cooling water
Electrical power
Cost
Description
(RM)
Land 392767.72
Raw Material 6679833
Utilities 256181.20
Labor 68640
Equipment 3113420
Engineering &
2500000
Supervision
Construction expenses 2550000
Contractor‘s Fee 1500000
Maintenance 1500000
Installation 5000000
Building 1000000
Total 24560842
(143333 kg/hr) x (24 hr/d) x (335 d/y) / (RM 0.80 /kg) = RM 1440496650
Gross profit:
Quick Details
Atmospheric
Lubrication Style: Oil-free Mute: No
Pressure:: 1.013 bar A
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 m3/ hr
Air compressor discharge pressure: 6~10 bar A
Air compressor intake pressure: 0.983 bar A
Air feeding temperature: 35°C
Motor power: 175 HP
Dimension: 2100 mm x 1440 mm x 1816 mm
Weight: 2500 kg
Cooling water temperature: 32°C
Protection Level: IP 55
b) Shandong Qingneng Power Co., Ltd.
Product Details:
Model NO.: B6-4.90/0.981
Standard: 4380&Times;2805&Times;2615
Trademark: QNP
Power(Mw): 6
Press(Mpa): 4.9
Temp: 435
Flow(T/H): 78.15
North America, South America,
Eastern Europe, Southeast Asia,
Export Markets:
Africa, Oceania, Mid East, Eastern
Asia, Western Europe
Product Description
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:
Enthalpy
Output Rated
Air Temperature efficiency
Model Power static power Noise dB(A)*
flow (m3/h) efficiency(%) Chill Warm
pressure(Pa) (W)
room room
ALH- 54-
300 60 70-82 73-81 130 28
30BX3 59
ALH- 53-
220 /50Hz 350 75 78-80 72-79 180 31
35BX3 57
ALH- 52-
500 80 65-76 71-78 240 33
50BX3 57
PART 4
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 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 Xi‘an Xilan Natural Gas Co.Ltd Hubei Branch which was the main
supplier for the methanol‘s 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 French‘s
market.
Distance from:
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
In CNY In MYR
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.
Plant’s location:
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 m2.
120 m
100 m
4.6 Climate
From March 31st to April 3rd 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 12~14℃ in some areas). Moreover, a moderate gale will sweep over
eastern Inner Mongolia, northeast China, north China and other places.
PART 5
5.1 METHANOL
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.
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
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. 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.
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.
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.
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.
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
Eye Contact
Ingestion
Acute overexposure: Excessive ingestion of liquid form can cause gastric
distress and mild diarrhea.
Eyes : None
Skin : None
Inhalation : Remove to fresh air; provide artificial respiration; Provide
oxygen.
Ingestion : None
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.
Incompatibility: Strong acids and bases can cause rapid heating. Reaction with
sodium metal can result in explosion.
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
5.6 HYDROGEN
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).
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 Process Deviations Assigned
node parameters (guide Possible causes Possible consequences Action required to:
words)
1A Cooling Flow No 1. Control valve 1. Loss of cooling, 1. Select valve to fail
coils fails closed possible runaway open
2. Plugged cooling 2. ‘’ 2. Install filter with
coils maintenance procedure
Install cooling water
flow meter and low flow
alarm
Install high temperature
alarm to alert operator
3. Cooling water 3. ‘’ 3. Check and monitor
services failure reliability of water
services
4. Controller fails 4. ‘’ 4. Place controller on
and closes valve critical instrumentation
list
5. Air pressure fails, 5. ‘’ 5. See 1A.1
closing valve
1B High 1. Control valve 1.Reactor cools, 1. Instruct operators
fails open reactant concentration and update procedures
build, possible runaway
on heating
2. Controller fails 2. ‘’ 2. See 1A.4
and opens valves
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 Process Deviations Assigned
node parameters (guide Possible causes Possible consequences Action required to:
words)
1C Low 1. Partially plugged 1. Diminish cooling, 1. See 1A.4
cooling line possible runaway
2. Partial water 2. ‘’ 2. See 1A.2
sources failure
3. Control valve 3. ‘’ 3. Place valve on critical
fails to respond instrumentation list
1D As well as, 1. contamination of 1. Not possible here 1. None
water supply
1E Part of, 1. Covered under 1C
1F Reverse 1. Failure of water 1.Loss of cooling, 1. See 1A.2
source resulting in possible runaway
backflow
2. Backflow due to 2. ‘’ 2. Install check valve
high backpressure
1G Other 1. Not considered
than, possible
1H Sooner 1. Cooling normally 1. None
than, started early
1I Later than 1. Operator error 1.Temperature rises, 1.Interlock between
possible runaway cooling flow and reactor
feed
1J Where 1.Not considerable
else possible
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 Process Deviations Assigned
node parameters (guide Possible causes Possible consequences Action required to:
words)
1K Temp. Low 1. Low water 1. None-controller 1.None
supply temperature handles
1L High 1. High water 1. Cooling system 1.Install high flow alarm
supply temperature capacity limited, temp. and/or cooling water
increases high temp. alarm
2A Stirrer Agitation No 1.Stirrer motor 1.No mixing, possible 1.Interlock with feed
malfunction accumulation of line
unreacted materials
2. Power failure 2. Monomer feed 2.Monomer feed valve
continues, possible must fail closed on
accumulation of power loss
unreacted materials
2B More 1. Stirrer motor 1. uneven mixing 1.Low purity of the
controller fails 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 Process Deviations Assigned
node paramet (guide Possible causes Possible consequences Action required to:
ers words)
1A Cooling coil Flow No 1. Control valve 1. Loss of cooling, 1. Select valve to fail
fails closed possible runaway open
2. Plugged cooling 2. ‘’ 2. Install filter with
coils maintenance procedure
Install cooling water
3. Cooling water 3. ‘’ flow meter and low flow
services failure alarm
Install high temperature
4. Controller fails 4. ‘’ alarm to alert operator
and closes valve 3. Check and monitor
reliability of water
5. Air pressure fails, 5. ‘’ services
closing valve 4. Place controller on
critical instrumentation
list
5. See 1A.1
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.
Hydrogen forms 0.15 % of the earth's crust; it is the major constituent of water. 0.5
ppm of hydrogen H2 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.
Natural Gas Systems 129.5 132.6 130.7 103.6 103.1 99.5 96.4
Ferroalloy Production + + + + + + +
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)
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 compartments—soil, air, surface water, and
ground water—can 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(ppmv)). 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.
4 2 2
2 2 2
7.1 Mixer
𝐹2 𝑘𝑚𝑜𝑙 𝑟
𝑋2 𝐻2𝑂
𝐹3 𝑘𝑚𝑜𝑙 𝑟
𝐹1 𝑘𝑚𝑜𝑙 𝑟 𝑋3 𝐶𝐻4
𝑋1 𝐶𝐻4 1 𝑋3 𝐻2𝑂
Overall balance
F1+F2=F3
5192 + 5324 = F3
F3=10516 kmol/hr
H2O balance; 3, 2 3 = 2, 2 2
2 2 2 1 5324
3 2 = = = 10516
3
3 2 = 0.506
CH4 balance; 3, 4
F3 = 1, 4
F1
4
0 1 5192
3, 4
= =
3 10516
3, 4
= 0.494
𝐹3 𝑘𝑚𝑜𝑙 𝑟
𝐹4 𝑘𝑚𝑜𝑙 𝑟
3 2 = 0.506 𝐹4,𝐻2𝑂 𝑋4,𝐻2 𝑂
3, 4
= 0.494 𝐹4,𝐶𝑂 𝑋4,𝐶𝑂
𝐹4,𝐻2 𝑋4,𝐻2
𝐹4,𝐶𝐻4 𝑋4,𝐶𝐻4
, = 5194 – ξ1
4, 2 = 5321- ξ1
4, = ξ1
4, 2 = 3 ξ1
CH4 conversion;
1 0 999 4 5194 4
, = x
4
5.194 = 5194 - ξ1
ξ1 = 5188.81 kmol/hr
4, 2 = 5321 – 5188.81
= 132.19 kmol/hr
4, 2 = 3x5188.81
= 15566.43 kmol/hr
F4 = 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
𝑋10𝐶𝐻4
4400 kmol/hr Purge
𝑋10𝐶𝑂
𝑋10𝐻2 𝑂 =0.0015
F9
𝑋9𝐶𝐻3 𝑂𝐻 =0.13
F4 F5 F6
Reactor 26 Separator F7
𝑋8 𝐶𝐻3𝑂𝐻 𝑋9𝐶𝐻3 𝑂𝐻
⬚
𝑋8𝐶𝐻4 𝑋9𝐻2
𝑋4,𝐻2 𝑂
𝑋8 𝐶𝑂 𝑋9𝐶𝑂2
𝑋4𝐶𝑂
𝑋8𝐻2 𝑋9𝐶𝑂
𝑋4𝐶𝐻4
𝑋4𝐻2
Reactor 26
Total balance
4 10 5
5
5
CH4 balance
5 5 4 4 4 4 10 10 4
5 4
5 4
CO balance
5 5 4 4 10 10
H2 balance
5 5 2 4 4 2 10 10 2
5 2
76
H2O balance
5 5 2 4 4 2 10 10 2
5 2
0052
4 5 5 4
5 5
2 5 5 2
2 5 5 2
6 1
6 2 1
6 3 1
6 2 5 5 2 =
6 4 5 5 4
6 1
6 2 1
6 3 1 =
6 3
6 2
6 4
6 2
10 8 9
7 9 6
7
CH4 balance
6 6 4 7 7 4 9 9 4
7 4
CO balance
7 7 6 6 9 9
H2 balance
7 7 2 6 6 2 9 9 2
7 2
H2O balance
7 7 2 6 6 2 9 9 2
7 2
balance
7 7 3 6 6 3 9 9 3
7 3
PART 8
8.1 Reactor 1
CH4 T=3500C
T =850oC CO P=3000kPa
H2
P=3000kPa
H2O
Kp
99.9% conversion
CH4
CH4+ H2O CO + 3H2
H2O
Energy balance
Q = ΣmΔHf – ΣmΔHi
Δha
Δhb
850
ΔHa = ∫25
165 9 1 3 2
= ∫25
= -3200 kJ/kg
= 1.405 kJ/kg
So H1 = Δha + Δhb
= (-3200+1.405) kJ/kg
= -3198 kJ/kg
H2 = O2 (g, 25OC, 101.325kPa)
Δha
Δhb
165
ΔHa = ∫25
165 1 4 2
= ∫25
= 11922kJ/kg
= 0.966 kJ/kg
So H2 = Δha + Δhb
= (11922+0.966) kJ/kg
= 11922.966 kJ/kg
H3 = (L, 25OC, 101.325kPa)
Δha
Δhb
193 2
ΔHa = ∫25
193 2 1 3 2
= ∫25
= -1536.36kJ/kg
= 1.142 kJ/kg
So H3 = Δha + Δhb
= (-1536.36+1.142) kJ/kg
= -1535.22 kJ/kg
H4 =(L, 25OC, 101.325kPa)
Δha
Δhb
193 2
ΔHa = ∫25
193 2 1 3 2
= ∫25
= -300.51kJ/kg
= 1.156 kJ/kg
So H4 = Δha + Δhb
= (-300.51+1.156) kJ/kg
= -299.35 kJ/kg
H5(L, 25OC, 101.325kPa)
Δha
Δhb
193 2
ΔHa = ∫25
193 2 9 1 3 2
= ∫25
= -3181.32kJ/kg
= 0.9657kJ/kg
So H5 = Δha + Δhb
= (-3181.32+0.9657) kJ/kg
= -3180.35 kJ/kg
OUTLET
Δha
Δhb
193 2
ΔHa = ∫25
193 2 0 4 2
= ∫25
7 3
= 33524.42685 kJ/kg
= -0.012 kJ/kg
So H6 = Δha + Δhb
= 33524.4149kJ/kg
H7 = (g, 25OC, 101.325kPa)
Δha
Δhb
193 2
ΔHa = ∫25
=
193 2 1 3 2 6 3
∫25
= 8169.5417 kJ/kg
= 1.142 kJ/kg
So H7 = Δha + Δhb
= 8170.6837 kJ/kg
H8 = (g, 25OC, 101.325kPa)
Δha
Δhb
193 2
ΔHa = ∫25
193 2 1 3 2 7 3
= ∫25
= -532.833 kJ/kg
= 1.156 kJ/kg
So H8 = Δha + Δhb
= -531.677 kJ/kg
H9 (g, 25OC, 101.325kPa)
Δha
Δhb
193 2
ΔHa = ∫25
193 2 9 1 3 2
= ∫25
7 3
= -4189.58525 kJ/kg
So H9 = Δha + Δhb
= -4188.179 kJ/kg
H10 = H2O (g, 25OC, 101.325kPa)
Δha
Δhb
193 2
ΔHa = ∫25
=
193 2 4 2 7 3
∫25
= -36661.985 kJ/kg
=1.10088kJ/kg
= =(-36661.985 +1.10088)kJ/kg
=-36660.884 kJ/kg
Hin liquid
substance Hingasesphase Hout liquidphase Houtgasesphase
phase
CO - - -1535.22kJ/kg 8170.68kJ/kg
H2 - - -299.35kJ/kg -531.68kJ/kg
-
CH4 4356kJ/kg 33524.41kJ/kg
36660.88kJ/kg
nin
substance ningasesphase nout liquidphase noutgasesphase
liquidphase
CO - - 1725.42kg/hr 193.128kg/hr
H2 - - 1829.64kg/hr 84.184kg/hr
CH4 - 1099kg/hr - -
Energy balance
Q = Σn outΔHf – Σn inΔHi
6 5 8 7 6 4
7 6 8 7
8
kJ/hr
hr 3600s 1kJ/s
8.2 Reactor 2
CH4 T=400C
T =28oC CO P=101.3kPa
H2
P=101.3kPa
H2O
Kp 99.9% conversion
Energy balance
Q = ΣmΔHf – ΣmΔHi
Δha
Δhb
28
ΔHa = ∫25
28 9 1 3 2
= ∫25
= -800 kJ/kg
= 1.405 kJ/kg
So H1 = Δha + Δhb
= (-800+1.405) kJ/kg
= -801.45 kJ/kg
H2 = (g, 25OC, 101.325kPa)
Δha
Δhb
28
ΔHa = ∫25
28 1 4 2
= ∫25
= 5233kJ/kg
= 0.966 kJ/kg
So H2 = Δha + Δhb
= (5233+0.966) kJ/kg
= 5233.966 kJ/kg
H3 = (L, 25OC, 101.325kPa)
Δha
Δhb
50
ΔHa = ∫25
50 1 3 2
= ∫25
= -1536.36kJ/kg
= 1.142 kJ/kg
So H3 = Δha + Δhb
= (-1536.36+1.142) kJ/kg
= -1535.22 kJ/kg
H4 =(L, 50OC, 101.325kPa)
Δha
Δhb
50
ΔHa = ∫25
50 1 3 2
= ∫25
= -300.51kJ/kg
= 1.156 kJ/kg
So H4 = Δha + Δhb
= (-300.51+1.156) kJ/kg
= -299.35 kJ/kg
H5(L, 25OC, 101.325kPa)
Δha
Δhb
50
ΔHa = ∫25
50 9 1 3 2
= ∫25
= -2133kJ/kg
= 0.9657kJ/kg
So H5 = Δha + Δhb
= (-2133+0.9657) kJ/kg
= -2132.35 kJ/kg
OUTLET
Δha
Δhb
50
ΔHa = ∫25
50 0 4 2 7 3
= ∫25
= 2813.21 kJ/kg
= -0.012 kJ/kg
So H6 = Δha + Δhb
= 2814.31kJ/kg
H7 = (g, 25OC, 101.325kPa)
Δha
Δhb
50
ΔHa = ∫25
50 1 3 2 6 3
= ∫25
= 4196 kJ/kg
= 1.142 kJ/kg
So H7 = Δha + Δhb
= 4197.142 kJ/kg
H8 = (g, 25OC, 101.325kPa)
Δha
Δhb
50
ΔHa = ∫25
50 1 3 2 7 3
= ∫25
= -532.833 kJ/kg
= 1.156 kJ/kg
So H8 = Δha + Δhb
= -531.677 kJ/kg
H9 (g, 25OC, 101.325kPa)
Δha
Δhb
50
ΔHa = ∫25
50 9 1 3 2
= ∫25
7 3
= -4189.58525 kJ/kg
So H9 = Δha + Δhb
= -4188.179 kJ/kg
H10 = (g, 25OC, 101.325kPa)
Δha
Δhb
50
ΔHa = ∫25
=
50 4 2 7 3
∫25
= -36661.985 kJ/kg
=1.10088kJ/kg
= =(-36661.985 +1.10088)kJ/kg
=-36660.884 kJ/kg
Hin liquid
substance Hingasesphase Hout liquidphase Houtgasesphase
phase
nin
substance ningasesphase nout liquidphase noutgasesphase
liquidphase
Energy balance
Q = Σn outΔHf – Σn inΔHi
6 5 8 7 6 4
7 6 8 7
8
kJ/hr
hr 3600s 1kJ/s
PART 9
82500
717.97 362.82
H
663.6
351
H
23361.82 1780
17676.6
PART 10
10.1 REACTOR 1
3.13 m
8.1m
Reactor 1
Ʈ, residence time =
Methane:
Volumemetric flowrate :
Water:
Volumemetric flowrate ;
Total flowrate ;
= 198.49 m3/min
= 250.09 m3
2
Reactor volume =
250.09 m3 = π R2 (8.1m)
R = 3.13 m
10.2 REACTOR 2
3.03 m
6.5m
Reactor 2
Ʈ, residence time =
Mixture:
Volumemetric flowrate ;
= 263930 m3/min
= 200.0m3
2
Reactor volume =
200.0m3 = π R2 (6.9 m)
R = 3.03 m
10.3 FLASH SEPARATOR
5.1m
Flash Separator Column
dV = 0.876 kg/m3
dL = 786 kg/m3
= 3.203 m/sec
thus to convert to volumetric flow rate, we divide the mass flow rate of vapor with vapor density
= 230688 m3/hr
= 64.08 m3/sec
Vapor flow rate coming out from flash separator = 64.08 m3/sec
= 20 m2
= 5.05 m
Height = 5.1m
= 102.15 m3
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
http://www.uhde.eu/cgi-bin/byteserver.pl/archive/upload/uhde_brochures_pdf_en_6.00.pdf