Chemical Technology (CHE1004)
Module 6 Lecture 34 & 35
Petrochemicals
Dr.S.Karthika
Assistant professor (senior)
VIT, vellore
Manufacture of
methanol
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Introduction
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•It is also known as methyl alcohol, wood alcohol, wood naphtha or wood spirits. It has
chemical formula CH3OH (often abbreviated as MeOH)
• It is a light, volatile, colourless, flammable, liquid with a distinctive odour. At room
temperature it is a polar liquid.
• It forms explosive mixtures with air and burns with a nonluminous flame.
2 CH3OH + 3O2→ 2 CO2 + 4 H2O
• Boiling point : 64.96° C (148.93° F) , Freezing point : -93.9°C (-137°F) , Relative Density
: 0.8.
•Methanol is also a toxin and should not be ingested. Drinking quantities of methanol
can result in blindness and severe damage to the central nervous system.
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Uses
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(a) Polymers
The largest use for methanol is as a feedstock for the plastics industry.
(i) Plastics derived from methanal
Methanol is used to make methanal (formaldehyde) and hence a variety of plastics, based on reactions
with phenol, carbamide (urea) and melamine.
(ii) Polyesters
The production of polymers such as the polyester, Terylene use methanol as the original feedstock.
Methanol is used to make Terylene in two ways. One is as the alcohol to make the dimethyl ester of
benzene-1,4-dicarboxylic acid (terephthalic acid). The other is to make ethanoic acid (acetic acid), a
large amount of which is used in the manufacture of benzene-1,4-dicarboxylic acid. It is used as the
solvent in the liquid phase oxidation of 1,4-dimethylbenzene (p-xylene), leading to the production of
the acid.
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Uses
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(iii) Poly(methyl 2-methylpropenoate)
Poly(methyl 2-methylpropenoate) is used under trade names such as Lucite, Perspex and Altoglass.
Methanol is used to make the monomer, the methyl ester of 2-methylpropenoic acid.
(iv) Poly(ethene) and poly(propene)
A most remarkable increase is in the use of methanol to produce alkenes by the MTO and MTP processes,
from 6 million tonnes in 2015 to an expected 20 million tonnes in 2020, which will mean that a large
proportion of plastics such as poly(ethene) and poly(propene) will, in the near future, be derived from
synthesis gas.
(b) As a fuel
Methanol is destined to be a major fuel for cars, either as a liquid fuel, mixed with petrol, or in fuel cells
where it has been used to prepare, in situ in the car, hydrogen for the fuel cell.
Whereas a few years ago, only a small amount of methanol was used directly as a fuel in cars, this use is now
increasing rapidly. In China petrol is mixed with methanol (15%) without the need for engines to be
redesigned.
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Uses
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With some redesigning, more methanol (up to 85%) can be used. The advantage for China is that the
methanol can be produced from both coal and biomass via synthesis gas. This emphasis of using
methanol as a fuel is reflected in the global production figures for methanol. Thus worldwide, use of
methanol as a fuel now accounts for 10% (about 7 million tonnes a year) but is expected to increase in
the coming years.
(c) To make fuels
The MTG process
Synthesis gas can be converted into liquid fuels. One way is by using the Mobil MTG (methanol to
gasoline) process.
Methanol is converted into alkanes and aromatic hydrocarbons suitable for petrol (hydrocarbons
with 5 to 8 carbon atoms), by passing the vapour over alumina at ca 600 K. An equilibrium mixture
of methanol, dimethyl ether (DME) and steam is produced, containing about 25% methanol:
This mixture of gases is then passed over a bed of a zeolite in its acid form, HZSM-5, heated to ca 650
K, to produce the mixture of hydrocarbons (with 5-10 carbon atoms) for use as petrol.
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Uses
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Global scenario
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•Methanol find numerous applications that can be generally divided into 2 groups: chemical and transportation fuel sectors
•Asia Pacific remains the largest producing and consuming region with more than a half of global production and 65% of world
demand; Middle East and Africa come the second (in terms of output)
•Top 5 methanol producing countries include China, Saudi Arabia, Trinidad and Tobago, Iran, Russia
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Methanol via synthesis gas route
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H2 and CO adjusted to molar ratio of 2.25 . The mixture is compressed to 200 – 350
atms - Recycle gas (Unreacted feed) is also mixed and sent to the compressor
Then eventually the mixture is fed to a reactor. Steam is circulated in the heating
tubes to maintain a temperature of 300 – 375 ºC
After reaction, the exit gases are cooled - After cooling, phase separation is allowed.
In this phase separation operation methanol and other high molecular weight
compounds enter the liquid phase and unreacted feed is produced as the gas phase.
The gas phase stream is purged to remove inert components and most of the gas
stream is sent as a recycle to the reactor.
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Methanol via synthesis gas route
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The liquid stream is further depressurized to about 14 atms to enter a second phase
separator that produces fuel gas as the gaseous product and the liquid stream is rich
of the methanol component.
The liquid stream then enters a mixer fed with KMNO4 so as to remove traces of
impurities such as ketones, aldehydes etc.
Eventually, the liquid stream enters a distillation column that separates dimethyl
ether as a top product.
The bottom product from the first distillation column enters a fractionator that
produces methanol, other high molecular weight alcohols and water as three
different products.
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Reactions
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Methanol convertor
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Methanol via synthesis gas route
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References
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https://ihsmarkit.com/products/methanol-chemical-economics-
handbook.html
https://mcgroup.co.uk/researches/methanol
https://www.essentialchemicalindustry.org/chemicals/methanol.html
https://nptel.ac.in/content/storage2/courses/103103029/pdf/mod3.pdf
https://www.lookchem.com/Chempedia/Chemical-Technology/Organic-
Chemical-Technology/3060.html
https://www.bestcurrentaffairs.com/methaol-economy-india/
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Manufacture of formaldehyde
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Manufacture of formaldehyde
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Introduction
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Due to its relatively low costs compared to other materials, and its receptivity for
reaching high purities, formaldehyde is considered one of the most widely
demanded and manufactured materials in the world.
It is also the center of many chemical researches and alternative manufacture
methods.
Formaldehyde is soluble in water and some other chemical solutions. Rapid
absorption of formaldehyde in the respiratory and gastrointestinal systems is
because of its high solubility in water. Formaldehyde is generally known as formalin.
Formalin is 37% formaldehyde solution in water. For preventing polymerization of
formaldehyde, it is mixed with ten percent of methanol as a stabilizer.
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Production of formaldehyde
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Formaldehyde is the simplest aldehyde that is produced endogenously by plants,
animals, and humans, and is also made synthetically. Naturally present on Earth
and ubiquitous in the universe, formaldehyde is a major source for organic
compounds essential to life. Synthesized formaldehyde has a number of widespread
industrial and medical applications that make it nearly universal in the modern
environment and highly significant to the global economy.
The commercial production of formaldehyde was first started in Germany in the
1880s but the development of a methanol synthesis route in the 1920s gave the spur
to the development of large-scale manufacture. Today there are two main routes:
oxidation-dehydrogenation using a silver catalyst involving either the complete or
incomplete conversion of methanol; and the direct oxidation of methanol to
formaldehyde using metal oxide catalysts (Formox process).
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Production of formaldehyde
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Formaldehyde is a common molecule throughout the universe. Due to its reactivity
and abundance, researchers have theorized that interstellar formaldehyde might
have had a role in the creation of organic molecules found inside asteroids and
comets, which in turn are suspected to have been responsible for providing early
earth with essential materials such as carbon.
Most recently, research has shown that organic solids in comets and chondrites
were likely derived from a formaldehyde polymer.
The study concludes: “The origin of a significant fraction of organic solids in
primitive solar system objects can logically be attributed to formaldehyde
polymerization. Formaldehyde is relatively abundant in the galaxy and also in
comets.
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World scenario
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Uses
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A list of these applications is given below:
Oriented-strand board (OSB), Particle board, flooring materials, high-density fiber board (HDF),
Medium density fiber board (MDF), plywood, cork products, Insulation materials made of UF foam, mineral
wool, coating materials, glass wool, paper products, paints, lacquers containing formaldehyde as
preservative, textiles, cleaning, photo processing chemicals, caring products, disinfectants, preservatives,
cosmetics, etc.
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Chemical reactions
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In the above reactions, the first and third are exothermic reactions but the second
reaction is endothermic. The reactions are carried out in vapour phase. Catalyst:
Silver or zinc oxide catalysts on wire gauge are used. Operating temperature and
pressure: Near about atmospheric pressure and 500 – 600ºC
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Formaldehyde from methanol
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Air is sent for pre-heating using reactor outlet product and heat integration concept.
Eventually heated air and methanol are fed to a methanol evaporator unit which
enables the evaporation of methanol as well as mixing with air.
The reactor inlet temperature is 54ºC. The feed ratio is about 30-50 % for CH3OH:
O2 . After reaction, the product is a vapour mixture with temperature 450 – 900ºC
After reaction, the product gas is cooled with the heat integration concept and then
eventually fed to the absorption tower.
The absorbent in the absorption tower is water as well as formaldehyde rich water.
Since formaldehyde rich water is produced in the absorption, a portion of the rich
water absorbent solution from the absorber is partially recycled at a specific section
of the absorber.
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Formaldehyde from methanol
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From the absorber, HCHO + methanol rich water stream is obtained as the bottom
product. The stream is sent to a light end stripper eventually to remove any light end
compounds that got absorbed in the stream.
The vapours from the light end unit consisting of light end compounds can be fed at
the absorption unit at specific location that matches with the composition of the
vapours in the absorption column.
Eventually, the light end stripper bottom product is fed to a distillation tower that
produces methanol vapour as the top product and the bottom formaldehyde + water
product (37 % formaldehyde concentration). Methanol is recycled to the reactor
after heat exchange with reactor product stream.
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Formaldehyde from methanol
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Chloromethanes
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Chloromethanes namely methyl chloride (CH3Cl), methylene chloride (CH3Cl2),
Chloroform (CHCl3) and Carbon Tetrachloride (CCl4) are produced by direct
chlorination of Cl2 in a gas phase reaction without any catalyst.
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Manufacture of chloromethanes
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The reactions are very exothermic. - The feed molar ratio affects the product
distribution. When CH4/Cl2 is about 1.8, then more CH3Cl is produced. On the
other hand, when CH4 is chosen as a limiting reactant, more of CCl4 is produced.
Therefore, depending upon the product demand, the feed ratio is adjusted.
Process Technology
Methane and Cl2 are mixed and sent to a furnace - The furnace has a jacket or shell
and tube system to accommodate feed preheating to desired furnace inlet
temperature (about 280 – 300ºC).
To control temperature, N2 is used as a diluent at times. - Depending on the product
distribution desired, the CH4/Cl2 ratio is chosen. - The product gases enter an
integrated heat exchanger that receives separated recycle CH4 (or a mixture of CH4
+ N2) and gets cooled from the furnace exit temperature (about 400ºC).
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Chloromethanes
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Eventually, the mixture enters an absorber where water is used as an absorbent and
water absorbs the HCl to produce 32 % HCl. The trace amounts of HCl in the
vapour phase are removed in a neutralizer fed with NaOH.
The gas eventually is compressed and sent to a partial condenser followed with a
phase separator. The phase separator produces two streams namely a liquid stream
consisting of the chlorides and the unreacted CH4/N2.
The gaseous product enters a dryer to remove H2O from the vapour stream using
98% H2SO4 as the absorbent for water from the vapour.
The chloromethanes enter a distillation sequence. The distillation sequence consists
of columns that sequentially separate CH3Cl, CH2Cl2, CHCl3 and CCl4.
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Manufacture of Chloromethane
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Uses
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References
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https://pubs.rsc.org/en/content/chapterhtml/2018/bk9781782629733-00001?isbn=978-1-78262-973-
3&sercode=bk
https://faculty.kfupm.edu.sa/CHE/rshawabk/files/Production_of_Formaldehyde_from_Methanol.pdf
https://www.phxequip.com/resource-detail.40/comparing-the-different-formaldehyde-production-
processes.aspx
https://www.lookchem.com/Chempedia/Chemical-Technology/Organic-Chemical-Technology/3060.html
https://www.globenewswire.com/news-release/2020/06/26/2054302/0/en/Global-Chloromethane-
Market-By-Manufacturing-Process-By-Product-Type-By-Application-By-Region-Competition-Forecast-
Opportunities-2025.html
https://formaldehyde.americanchemistry.com/Applications/
https://www.chemicalsafetyfacts.org/wp-content/uploads/2014/09/Formaldehyde-11.21-lowres.pdf
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Thank you
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