BCT-31: ALCOHOL TECHNOLOGY

Green Chemistry
 Green Chemistry
 Green chemistry, also called sustainable chemistry, is an area of chemistry and chemical engineering
focused on the design of products and processes that minimize or eliminate the use and generation of
hazardous substances.
 The goals of green chemistry: more resource-efficient and inherently safer design of molecules, materials,
products, and processes—can be pursued in a wide range of contexts.
 The principles cover following concepts:
 The design of processes to maximize the amount of raw material that ends up in the product;
 The use of renewable material feed-stocks and energy sources;
 The use of safe, environment friendly substances, including solvents, whenever possible;
 The design of energy efficient processes;
 Avoiding the production of waste, which is viewed as the ideal form of waste management.
3
Syllabus Unit 4: Chemicals from alcohol

1. Acetaldehyde, Acetic acid, Acetic- Production and

Anhydride, Butanol, Ethyl acetate, Butyl Industrial Practices
acetate, acetone, Ethyl ether, Diethyl
oxalate etc.
Acetaldehyde
Part of Unit 4: Chemicals from alcohol
Acetaldehyde (CH3CHO)
IUPAC Name Ethanal Chemical properties Property Value
Common names Ethyl Aldehyde Molecular Weight 44.05
Acetic Aldehyde Melting Point - 123.370 C (decomposes at 1640 C
into CO2 and H2O)
Acetylaldehyde
Boiling Point 20.20 C
CAS Number 75-07-0 Density 0.784 gm.cm-3
(Chemical Abstract Service
Color Colorless (Gasseous, Liquid phase)
Registry Number)
Grades CP (Commercial Pure) Odor Pungent, Fruity smell

50% aqueous Flash point -400 C

Explosive Limits 4-60 vol% in air
Solubility Water, alcohol, organic solvents and
polar solvents
Slightly soluble in chloroform

Toxicity Carcinogenic, flammable

6
Commercial applications of Acetaldehyde

7
Acetaldehyde (CH3CHO): Production
 Most acetaldehyde is produced industrially by the direct oxidation of Ethylene and is used as a raw
material to make acetic acid, 1-butanol, ethyl acetate, 1-butanal, and many other products.
 But alternatively, Bio-based acetaldehyde can be produced by Bioethanol Dehydrogenation and could
be used to make a variety of eco-friendly, bio-based chemicals.
 The main products in ethanol dehydrogenation are acetaldehyde and ethyl acetate.

Ethanol Acetaldehyde

Ethyl acetate

Butanol

8
Acetic Acid
Acetaldehyde (CH3CHO): Production

9
Acetaldehyde (CH3CHO): Process description
1. Ethanol, an 85-wt.% solution in water, pumped to 100 psi and heated to 626°F (330 0C).
2. Resultant stream then fed to an isothermal, catalytic (Cu or/and CaSiO2), packed-bed reactor, where
the ethanol is dehydrogenated to form acetaldehyde.
3. The reactor effluent is then cooled and resultant two phase stream (vapor and liquid), is then
separated.
4. The vapor stream is then sent to a absorbing column where it is contacted with water which absorbs
the acetaldehyde and ethanol from the vapor stream.
5. Resulting vapor effluent is then sent for further processing and recovery of valuable hydrogen.
6. Liquid stream after point 3 separation is then sent to the distillation column where light by products
and water heavy products are getting separated.
7. Light bi products then distilled again and resulting ethanol as bottom product recycled back to the
feed stream. 10
Acetic Acid
Part of Unit 4: Chemicals from alcohol
Acetic Acid (CH3COOH)
IUPAC Name Ethanoic Acid Chemical properties Property Value
Common names Vinegar (In dilute form) Molecular Weight 60.05
Hydrogen Acetate Melting Point 16-170 C
Ethylic Acid
Boiling Point 118-1190 C
Glacial
Density 1.049 gm.cm-3
CAS Number 64-19-7 Color Colorless (Liquid phase)
(Chemical Abstract Service
Registry Number) Odor Vinegar smell
Grades CP (Commercial Pure) Flash point 400 C

50% aqueous Explosive Limits 4-16 vol% in air

Solubility Water, alcohol, organic solvents

Toxicity Hazardeous
12
Commercial applications of Acetic Acid
Various production routes
of Acetic Acid
• Methanol carboxylation
(Most used route)
• Acetaldehyde oxidation
• Ethanol
dehydrogenation/oxidation
• Butane/naphtha oxidation

13
Acetic Acid (CH3COOH): Production
 Commercially, acetic acid are produced by the methanol carbonylation reaction. Methanol is synthesized
from natural gas, a fossil fuel raw material.
 Alternatively, It is possible to obtain acetic acid by the selective oxidation of ethanol, a renewable
feedstock.
 Acetic acid could be synthesized from ethanol using a Cu/SiO2 catalyst and H2O as the oxidizing agent.
 Acetaldehyde, which is generated by the dehydrogenation of ethanol, is oxidized to acetic acid by the
oxygen from the H2O dissociation.
 For acetic acid fermentation, 10% ethanol concentration, 30°C temperature and 4.5 pH are considered as
optimum conditions.
 The feed stream composition was N2:H2O:C2H5OH = 89:10:1 mol%.
 Ethanol and H2O vapor was generated by passing N2 through two saturators, one at 4.6 0C and the other at
60.5 0C. Isothermal reactor temperature would be 250 0C. 14
Acetic Acid (CH3COOH): Production

(Acetic Acid)

15
Butanol and Acetone
Part of Unit 4: Chemicals from alcohol
Butanol (C4H9OH)
IUPAC Name Butan-1-ol Chemical properties Property Value
Common names n-Butanol Molecular Weight 74.123 g·mol−1

n-Butyl alcohol Melting Point −89.8 °C

n-Butyl hydroxide Boiling Point 117.7 °C

Methylolpropane Density 0.81 g/cm3
CAS Number 71-36-3 Color Colorless (Liquid phase)
(Chemical Abstract Service
Odor alcoholic and sweet
Registry Number)
Flash point 35 °C
Explosive Limits 1.45–11.25%
Solubility 73 g/L at 25 °C

Toxicity Flammable

17
Acetone (CH3COCH3)
IUPAC Name Propan-2-one Chemical properties Property Value
Common names Acetonum Molecular Weight 58.080 g·mol−1
Dimethyl ketone Melting Point −94.7 °C
Ketone propane
Boiling Point 56.05 °C
Pyroacetic spirit (archaic)
Density 0.7845 g/cm3 (25 °C)
CAS Number 67-64-1 Color Colorless (Liquid phase)
(Chemical Abstract Service
Registry Number) Odor Pungent, irritating
Flash point 400 C
Explosive Limits 4-16 vol% in air
Solubility Miscible in benzene, diethyl ether,
methanol, chloroform, ethano

Toxicity Flammable, irritating

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Butanol and Acetone
 Butanol is today considered a promising biofuel alternative based on several advantages compared to the
more established biofuels ethanol and methanol.
 A longer carbon chain length and thus a higher heating value, as well as lower volatility, polarity,
corrosivity and heat of vaporization, leading to lesser ignition problems.
 Moreover, diesel engines can run on pure butanol or diesel blends without any modifications and apparent
damage.
 Biological production of butanol under anaerobic conditions is typically referred to in literature as a part of
‘ABE fermentation’, since acetone, butanol and ethanol are usually produced simultaneously in this
process.
 Louis Pasteur was the first to report about microbial butanol production in 1862.
 Later in 1916, the first industrial-scale ABE fermentation began operation due to a high demand for acetone
during World War I, and after the armistice in November 1918, most of the plants were shut down 19
Butanol and Acetone
 In 1945, two-thirds of the butanol and one tenth of the acetone in the U.S. were produced by ABE
fermentation processes.
 However, their share in the total output declined rapidly during the 1950s mainly because of the acute
competition with the expanding petrochemical industry and decreasing feedstock availability. ABE
fermentation became popular again in the 1970s after the oil crisis.

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Butanol and Acetone: Production
A typical conversion process from biomass to butanol involves three major steps: pretreatment,
detoxification and fermentation.

Pre-treatment: Detoxification: Fermentation:

21
Butanol and Acetone: Production
 ABE fermentation is biphasic; first, acetic acid and butyric acid (C3H7COOH) are produced in the acido-
genesis phase, then the acids are re-assimilated to yield the solvents acetone, butanol and ethanol.
 Batch fermentation is the most studied mode due to simple operation and low risk of contamination, and
readers can access numerous original studies of batch fermentations of lingo-cellulosic biomass to produce
butanol.
 Fed-batch mode is beneficial to tackle substrate inhibition by gradually adding the substrate, thus keeping
the substrate concentration below toxic levels

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Ethyl Acetate
Part of Unit 4: Chemicals from alcohol
Ethyl Acetate [CH3COOC2H5]
IUPAC Name Ethyl Ethanoate Chemical properties Property Value
Common names Acetic Ester Molecular Weight 88.106 g·mol−1
Acetic Ether Melting Point −83.6 °C

Acetyl Oxide
Boiling Point 77.1 °C
Ethyl ester of acetic acid
CAS Number 141-78-6 Density 0.902 g/cm3
(Chemical Abstract Service Colour Colourless
Registry Number) Odor Ether-like, fruity
Flash point −4 °C
Explosive Limits 2.0–11.5 vol% in air
Solubility Water, Ethanol, Acetone, Benzene

Toxicity Flammable, Irritant

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Ethyl Acetate
 Ethyl Acetate stands out as one of the most important small volatile ester compounds for industries.
 It is used as a chemical solvent and is applied in the synthesis of biodiesels, paints, adhesives, herbicides
and resins. Its annual production total production exceeding 3.7 MMT annually in 2017.
 Apart from its broad application range, ethyl acetate is also popular because it is relatively non-toxic and
fully biodegradable.
 These advantageous features caused a significant increase in the market demand for this product of
“green chemistry”.
 However, the sustainability of the ethyl acetate industry is severely hampered by the current, energy
intensive production processes that are based exclusively on petrochemical resources.
 Ethyl acetate in the chemical industry is obtained mainly by the classic Fischer esterification reaction
(FER), where the substrates are ethanol and acetic acid, and water is a by-product of the reaction

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Ethyl Acetate: Production
 Apart from classical synthesis method, there are also other methods of synthesis, such as ethanol
dehydrogenation, and synthesis from ethylene and acetic acid.
 Many yeasts are able to convert sugar into ethyl acetate and most famous for alcohol production
Saccharomyces cerevisiae, however, produces only trace amounts of ethyl acetate.
 Other yeasts are significantly better ethyl acetate producers.
 Wickerhamomyces anomalus and Kluyveromyces marxianus are the most studied and produce 0.18 and
0.29 g ethyl acetate/g sugar, respectively.
 W. anomalus produces ethyl acetate under oxygen limitation and K. marxianus under iron limitation.

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Fischer esterification reaction (FER)
 Fischer esterification or Fischer–Speier esterification is a special type of esterification by refluxing a
carboxylic acid and an alcohol in the presence of an acid catalyst.
 The reaction was first described by Emil Fischer and Arthur Speier in 1895.
 Commonly used catalysts for a Fischer esterification include sulfuric acid, p-toluenesulfonic acid, and
Lewis acids such as scandium(III) triflate.
 Typical reaction times vary from 1–10 hours at temperatures of 60-110 °C.
 Fischer esterification is an example of nucleophilic acyl substitution based on the electrophilicity of the
carbonyl carbon and the nucleophilicity of an alcohol.
 Synthesis of ethyl acetate using Fischer esterification reaction are as follows

27
Ethyl Acetate: Production (FER)
 The Fischer reaction of esterification of alcohols with carboxylic acids is carried out at elevated
temperatures, in the presence of catalysts.
 Both homogenous (inorganic acids such as sulfuric and phosphoric acid, and hydrochloric acid) and
heterogeneous catalysts (acidic ion exchange resins) are employed.
 In the presence of the mentioned catalysts, the ethyl acetate synthesis is carried out under the temperature
ranging between 70–90 0C.
 The temperature of the reaction mixture is controlled at a level assuring efficient removal of the vapors of
the lighter key product in the esterification reaction.
 The reaction of liquid phase esterification is reversible and insignificantly exothermic.
 The value of the equilibrium constant of the reaction depends primarily on the structure of alcohol and
acid.

28
Ethyl Acetate: Production (FER)
 In the reaction of acetic acid with ethyl alcohol, the equilibrium constant may vary in the range of 4–4.5,
which corresponds to a conversion of 66–68% at a stoichiometric ratio of substrates.
 In the case of ethyl acetate, the conversion rate of the reactants can be as high as 100%; however,
depending on the catalyst used, by-products may be formed.

29
Ethyl Acetate: Recovery (FER)
 Distillation is one of the most common methods of separating components of liquid mixtures. However, it
is not always possible to separate a liquid mixture by simple distillation.
 Ethyl acetate cannot be separated from water and ethanol by simple distillation, because a ternary
azeotrope consisting of: 83.1% ethyl acetate, 8.7% ethanol and 8.2% water, is formed.
 The classic method of purifying the reaction mixture is a three-stage distillation in combination with a
water extraction process.
 There are also other methods used to purify the reaction mixture such as extractive distillation and
membrane methods.
 The purification process in classical technology can be divided into three stages:
a. Reaction mixture rectification
b. Extraction process
c. Product rectification 30
Ethyl Acetate: Recovery
1. Stage 1 of recovery: Reaction mixture rectification
 First is the process of rectifying the reaction mixture, i.e., stripping acetic acid by a rectification
column and distilling the ethyl acetate–ethanol–water (EA–ET–W) ternary azeotrope. In order
to generate an azeotrope by the distillation of reaction products, and to avoid accumulating
water in the reactor, an azeotropic agent should be fed to the column. By esterification of the
acetic acid with ethanol, some excess water is released (approximately 17%) [29] which is more
than contained in the azeotrope mixture (approximately 7.8%). Therefore, the azeotropic agent
is the organic phase in the extraction process, recycled to the column. This fraction is richer in
ethyl acetate than the azeotrope (>93%) [8], so it binds the excess water.

31
Ethyl Acetate: Recovery
2. Stage 2 of recovery: Extraction process
 After azeotropic distillation, there is an extraction process. To obtain enriched phase of ethyl
acetate from the distillation product, it is necessary to wash it with water and extract ethanol. The
ethanol content of the organic mixture affects the solubility of water in this phase. The higher is
the content of alcohol, the greater the water content in the organic phase. By extracting ethanol,
water is also removed from the organic phase.
3. Stage 3 of recovery: Product rectification
 The final stage is the process of product rectification. Enriched phase of ethyl acetate is fed to the
rectification column, where, by distilling the triple azeotrope, a pure ethyl acetate is obtained as
the bottom product.

32
Ethyl Acetate: Extractive Distillation
 Extractive distillation is a partial vaporization process in the presence of a non-volatile separating agent
with a high boiling point, which is generally called solvent or entrainer, and which is added to the
azeotropic mixture to alter the relative volatility of the key component with no additional formation of
azeotropes.
 The principle driving extractive distillation is based on the introduction of a selective solvent that
interacts differently with each of the components of the original mixture and which generally shows a
strong affinity with one of the key components.
 The extraction agent after extractive distillation is purified in the recovery column and recycled to the
process.
 Typical examples of effective agents used in extractive distillation in the purification of ethyl acetate are:
dimethyl sulfoxide, glycerine and diethyl glycol, 1-naphthol, hydroquinone and N,N-dimethyl
formamide. 33
Ethyl Acetate: Membrane separation process
 Membrane processes belong to a large group of techniques for separating the components of liquid and
gas mixtures. The membrane technique used to separate azeotropic mixtures is called pervaporation.
 Pervaporation membranes can be used to selectively separate water and ethyl acetate to break down any
azeotrope present. The energy consumption in this case is lower than in the case of classical extraction
with water.
 Complete dehydration with membranes does not require a lot of energy, but leaves a waste stream of 17
wt% ethyl acetate on the permeate side. This waste stream requires additional treatment of extractive
distillation.
 Combination of both membrane methods and extractive distillation produce a high purity product Ethyl
Acetate.

34
Ethyl Acetate: Process flow diagram

35
Ethyl Acetate: Process Description
 Acetic acid and ethanol are mixed (MIX 1), heated up (HTXR 2) and directed to the reactor. The
esterification reaction takes place in the reactor–evaporator (KREA 4) at a temperature of about 90 0C,
under atmospheric pressure.
 The vapors from the reactor (Stream 6) are directed to the column (SCDS 5), in which unreacted acetic acid
is separated from the product by azeotropic distillation—the first stage of EA purification.
 The bottom product (Stream 7) is recycled to the reactor–evaporator. The distillate (Stream 9) is a triple
EA–ET– W azeotrope.
 The azeotrope is washed with water (EXTR 8) to extract ethanol—the second stage of EA purification.
 In case of the improved approach, the extractor feed is cooled down to enhance extraction—advantageous
shift of extraction equilibrium (HTXR 6).
 The organic phase from the extraction process is partly recycled (Stream 26) to the azeotropic column
(SCDS 5) as reflux, while the remainder (Stream 12) is directed to the product rectification column (SCDS
36
11)—final product distillation.
Ethyl Acetate: Process Description
 In this column, pure ethyl acetate is obtained as the bottom product (Stream 16), and the subcooled distillate
(triple azeotrope) is recycled to the extraction process (EXTR 8).
 The aqueous phase after extraction (Stream 20), containing ethanol and ethyl acetate is directed to the
wastewater column (SCDS 15), where ethyl acetate and ethanol are recovered.
 The distillate (Stream 21) is recycled to the reactor and the bottom product (Stream 22) is recycled as a
washing water to the extraction process, partially refreshed with a fresh portion of water (Stream 17).

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Butyl Acetate
Part of Unit 4: Chemicals from alcohol
Butyl Acetate [CH3COOC4H9]
IUPAC Name Butyl Ethanoate Chemical properties Property Value
Common names n-Butyl acetate Molecular Weight 116.160 g·mol−1
Acetic acid n-butyl ester Melting Point −78 °C

Butile
Boiling Point 126.1 °C
CAS Number 123-86-4
(Chemical Abstract Service Density 0.8825 g/cm3 (20 °C)
Registry Number) Colour Colorless liquid
Odor Fruity
Flash point 22 °C
Solubility alcohols, esters and glycols

Toxicity Flammable, Irritating

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Butyl Acetate
 Butyl Acetate is an ester that is a colorless, flammable liquid at room temperature.
 It is found in many types of fruit, where along with other chemicals, it imparts characteristic flavors and
has a sweet smell of banana or apple.
 Butyl acetate has shown wide applications in food, cosmetics (nail polish), medicine, and biofuel sectors.
 When butyl acetate is mixed with biodiesel, the combustion heat and cetane number of biodiesel are not
affected but the emission of soot and greenhouse gases is significantly reduced.
 Meanwhile, owning to its lower freezing point, the addition of butyl acetate will improve the fluidity of
biodiesel at low temperature, which indicates promising potentials in aviation sectors.
 Butyl acetate is often used as a high-boiling solvent of moderate polarity.
 The other three isomers of butyl acetate are isobutyl acetate, tert-butyl acetate, and sec-butyl acetate.

40
Butyl Acetate
 Butyl acetate has a variety of industry and consumer uses with its main end-user markets including
paints/lacquers, coatings, cosmetics, leather, cleaning and the pharmaceutical industries.
 Industry uses
 Normal butyl acetate’s most common industry use is in the production of lacquers and paints
(due to its low volatility) as a solvent. Additionally, it has uses in the manufacturing of artificial
leather, plastics adhesives and hardened coatings and topcoats.
 It is commonly used in the pharmaceutical industry as a solvent or an extraction agent for
processing oils and coatings. Other industry uses include lubricants, intermediaries, fruit
flouring and various additives.
 Consumer uses
 Butyl acetate is found in several cosmetic products including as a flavoring solvent in perfumes,
in fabrics and leather, in cleaning and care products for vehicles, air, and personal use and as an
anticorrosive agent. 41
Butyl Acetate: Production
 These short-chain fatty acid esters can be produced by either chemical or biological synthetic process
with corresponding alcohols and acids.
 Butyl acetate is commonly manufactured by the Fischer esterification of butanol (or its isomer to make an
isomer of butyl acetate) and acetic acid with the presence of catalytic sulfuric acid under reflux
conditions with this reaction:

 If an isomer of butanol is used instead, you will form an isomer of butyl acetate.
 Biological conversion of butanol and acetic acid to butyl acetate under the catalysis of lipases has
attracted more attentions owning to its mild reaction conditions and environmentally friendly properties,
which also provides an energy-saving route for the esters production.
 With the catalysis of exogenous lipases, acid and alcohol can be converted to their relevant short-chain
fatty acid esters. 42
Butyl Acetate: Biological Production
 Currently, two strategies were mainly adopted for short chain fatty acid esters biological synthesis:
i. Microbial monoculture fermentation (microbe can synthesize one precursor, such as acid, and the
other precursor, such as alcohol, can be externally supplemented)
ii. Co-culture fermentation (strain members can be specifically designed to synthesize alcohol and
acid, respectively, with the elimination of exogenous addition of acid or alcohol)
 Lipase is well known about its directly catalyzing acetic acid and butanol to butyl acetate.
 Lipase is added in fermentation chamber with all other ingredients.
 Lipase is an enzyme the body uses to break down fats in food so they can be absorbed in the intestines.
 There are mainly two kinds of microbe used for the production of Butyl Acetate using biological
monoculture synthesis method. These are
1. A. succinogenes 130z
2. C. acetobutylicum NJ4
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Butyl Acetate: Biological Production
Biosynthesis of butyl acetate by using microbial monoculture of C. acetobutylicum NJ4 with the
supplementation of exogenous acetic acid
 C. acetobutylicum NJ4 is a hyper butanol producer, which shows great potential for butyl acetate
synthesis through the supplementation of acetic acid.
 The optimized conditions were as follows: fermentation pH at 5.5, acetic acid concentration at 15
g/L, and acetic acid addition time at 120 h.
 The maximum production of butyl acetate is 7.30 g/L after 96 h, representing the highest butyl
acetate production through microbial fermentation process.

44
Butyl Acetate: Biological Production
Biosynthesis of butyl acetate by using microbial monoculture of A. succinogenes 130z with the
supplementation of exogenous butanol
 A. succinogenes 130z was genetically constructed, which can be used for acetic acid production due
to the deletion of pyruvate formate-lyase activating enzyme. Pyruvate formate-lyase activating
enzyme forces microbe to produce Pyruvic acid (CH3COCOOH), a simplest form of the alpha-keto
acids, with a carboxylic acid and a ketone functional group.
 During the fermentation process of A. succinogenes 130z butanol and lipases were exogenously
supplemented for butyl acetate synthesis.
 Meanwhile, butyl acetate was also simultaneously extracted into the organic phase of dodecane (oily
liquid n-alkane hydrocarbon C12H26) to increase the final titer.
 Production rate of Butyl Acetate depends upon the microbes ability to produce acetic acid. Microbe
stated above varies its production of Acetic acid depending upon the aeration in the fermentation
45
chamber favoring aerobic fermentation conditions.
Butyl Acetate: Biological Production
Biosynthesis of butyl acetate by using microbial co-culture composed of C. acetobutylicum NJ4 and A.
succinogenes 130z
 Different from the above investigated two examples, microbial co-culture system can eliminate the supplementation
of exogenous acid or alcohol during the butyl acetate synthesis process, which will reduce the production cost
especially at the large scale.
 Based on their growth and metabolic characteristics, this microbial co-culture system can be divided into two stages.
 In the first one, butanol can be specifically synthesized by C. acetobutylicum NJ4, while in the second one, A.
succinogenes 130z can be inoculated, which was mainly responsible for the synthesis of acetic acid.
 Both butanol and acetic acid can be simultaneously converted into butyl acetate under the esterification of lipases.
 The inoculation time of A. succinogenes 130z (Δ pflA) showed significant effects on the final butyl acetate
production.
 The highest 2.86 g/L of butyl acetate was produced by using microbial co-culture system composed of C.
acetobutylicum NJ4 and A. succinogenes 130z with the elimination of butanol and acetic acid
46
supplementation.
Butyl Acetate: Production (Fischer esterification
reaction)
 The Fischer reaction of esterification of alcohols with carboxylic acids is carried out at elevated
temperatures, in the presence of catalysts.
 Both homogenous (inorganic acids such as sulfuric and phosphoric acid, and hydrochloric acid) and
heterogeneous catalysts (acidic ion exchange resins) are employed.
 In the presence of the mentioned catalysts, the ethyl acetate synthesis is carried out under the temperature
ranging between 70–90 0C.
 The temperature of the reaction mixture is controlled at a level assuring efficient removal of the vapors of
the lighter key product in the esterification reaction.
 The reaction of liquid phase esterification is reversible and insignificantly exothermic.
 The value of the equilibrium constant of the reaction depends primarily on the structure of alcohol and
acid.

47
Butyl Acetate: Production (FER)
 The esterification reaction of Acetic acid with n-Butanol in a continuous catalytic distillation system will
be studied.
 The products of esterification reactions viz, water and butyl acetates are separated by distillation during
the course of the reaction.
 This strategy of continuous separation of products during the course of reaction using distillation
technique is known as Reactive Distillation (RD).
 Reactive distillation (RD) is the combination of reaction and distillation in a single vessel; therefore, it
enjoys many specific advantages over the conventional sequential approach of reaction followed by
distillation or other separation techniques.
 The introduction of an in situ separation process in the reaction zone, or vice versa, leads to complex
interactions between vapor-liquid equilibrium, mass-transfer rates, and diffusion and chemical kinetics,
which presents a great challenge for the design and synthesis of these systems.
48
Butyl Acetate: Production (FER)
Advantages of Reactive Distillation
Column:
1. Improved selectivity
2. Increased conversion
3. Better temperature control
4. Effective utilization of reaction
heat
5. Scope for difficult separations
6. Avoidance of azeotropes
Disadvantages:
1. Complex Design
2. Expensive catalysts/packings
3. Possible high pressure drop
across reactive zone
4. Temperature gap between
reaction and distillation section

49
Butyl Acetate: Recovery (FER)
 Distillation is one of the most common methods of separating components of liquid mixtures. However, it
is not always possible to separate a liquid mixture by simple distillation.
 Butyl acetate cannot be separated from water and Butanol by simple distillation, because formation of a
ternary azeotrope consisting of: 63 wt. % butyl acetate, 8 wt. % butanol and 29 wt. % water..
 The classic method of purifying the reaction mixture is a three-stage distillation in combination with a
water extraction process.
 There are also other methods used to purify the reaction mixture such as extractive distillation and
membrane methods.
 The purification process in classical technology can be divided into three stages:
a. Reaction mixture rectification
b. Extraction process
c. Product rectification 50
Butyl Acetate: Recovery
1. Stage 1 of recovery: Reaction mixture rectification
 Stripping acetic acid by a rectification column and distilling the Butyl acetate–butanol–water
ternary azeotrope is the first step. In order to generate an azeotrope by the distillation of
reaction products, and to avoid accumulating water in the reactor, an azeotropic agent should be
fed to the column. By esterification of the acetic acid with butanol, some excess water is
released which is more than the contained in the azeotrope mixture. Therefore, the azeotropic
agent is the organic phase in the extraction process, recycled to the column. This fraction is
richer in butyl acetate than the azeotrope, so it binds the excess water.
 Typical examples of effective agents for butyl acetate extraction are N,N-dimethylacetamide,
dimethylsulfoxide and acetamide, ethylene glycol, propylene glycol, dimethylsulfoxide and
acetamide.
51
Butyl Acetate: Recovery
2. Stage 2 of recovery: Extraction process
 After azeotropic distillation, there is an extraction process. To obtain enriched phase of butyl
acetate from the distillation product, it is necessary to wash it with water and extract butanol. The
butanol content of the organic mixture affects the solubility of water in this phase. The higher is
the content of alcohol, the greater the water content in the organic phase. By extracting butanol,
water is also removed from the organic phase.
3. Stage 3 of recovery: Product rectification
 The final stage is the process of product rectification. Enriched phase of Butyl acetate is fed to the
rectification column, where, by distilling the triple azeotrope, a pure Butyl acetate is obtained as
the bottom product.

52
Butyl Acetate: Membrane separation process
 Membrane processes belong to a large group of techniques for separating the components of liquid and
gas mixtures. The membrane technique used to separate azeotropic mixtures is called pervaporation.
 Pervaporation membranes can be used to selectively separate water and butyl acetate to break down any
azeotrope present. The energy consumption in this case is lower than in the case of classical extraction
with water.
 Complete dehydration with membranes does not require a lot of energy, but leaves a waste stream of 17
wt% butyl acetate on the permeate side. This waste stream requires additional treatment of extractive
distillation.
 Combination of both membrane methods and extractive distillation produce a high purity product butyl
Acetate.

53
Membrane Overview
A membrane is a selective barrier; it allows some things to pass through but
stops others.
Membranes can be generally classified into synthetic membranes and
biological membranes.
Biological membranes include cell membranes, nuclear membranes, and
tissue membranes, such as mucosae and serosae.
The degree of selectivity of a membrane depends on the membrane pore
size.
Depending on the pore size, they can be classified as microfiltration (MF),
ultrafiltration (UF), nanofiltration (NF) and reverse osmosis (RO)
membranes.
Membranes can also be of various thickness, with homogeneous or
heterogeneous structure.
Membrane Overview
Membrane Overview

Molecular weight cut-off or MWCO refers to the lowest

molecular weight solute in which 90% of the solute is retained
by the membrane, or the molecular weight of the molecule that
is 90% retained by the membrane.
Membrane Overview
 Pervaporation principles
 Pervaporation = per(meation) + (e)vaporation = Evaporation on the model of Permeation
= Pervaporation is a processing method for the separation of mixtures of liquids by partial vaporization
through a non-porous or porous membrane.

58
 Pervaporation principles
 There are 4 factors which do effect this type of separation process, mentioned as following:
i. Feed Concentration
ii. Membrane Thickness
iii. Permeate pressure
iv. Temperature

59
Separation through Pervaporation process
Assumptions:
1. Mass flux through the membrane (J) is a linear function of the solute mass
fraction (x) in the liquid phase
2. J exhibits an Arrhenius dependence on temperature (T)
3. There is a complete separation of solute through membrane (y = 1)
 Then local mass flux J at given temp T can be:
J = mass flux through membrane 𝑱 = 𝒙𝑱𝟎 𝒆−𝑬𝑱 /𝑹𝑻 ..(1)
J0 = maximum possible mass flux
through membrane at T  infinity  Then the differential mass balance for the liquid phase (retentate) can be written
x = local liquid composition (mass
𝒅𝒎
fraction) at a given temperature = −𝑱 (where dA is the differential area of membrane) ..(2)
𝒅𝑨
EJ = activation energy
R = ideal gas constant  Then total area will be
T = absolute local temperature 𝒎𝑭 𝒅𝒎
m = local mass flow rate at temp T 𝑨 = ‫𝒎׬‬ ..(3)
𝑹 𝑱
y = solute mass fraction at permeate where mR denotes the mass flowrate of the retentate and mF is the mass flowrate
side of the feed.
z = liquid feed composition 60
Separation through Pervaporation process
 From equations 1 and 3 total area of membrane will be:

𝒎𝑭 𝒅𝒎
𝑨= ‫𝒎׬‬ −𝑬 /𝑹𝑻 ..(4)
𝑹 𝒙𝑱𝟎 𝒆 𝑱

 Now doing mass balance on solutes

𝒅(𝒙𝒎)
= −𝑱𝒚 ..(5)
𝒅𝑨
y = mass fraction of the permeate, which should be 1 as we are collecting pure
J = mass flux through membrane solute at permeate side.
J0 = maximum possible mass flux
through membrane at T  infinity  Now if equations 2 and 5 get combined then
x = local liquid composition (mass 𝒅(𝒙𝒎) 𝒅𝒎
fraction) at a given temperature =
𝒅𝑨 𝒅𝑨
EJ = activation energy
𝒅𝒙 𝒅𝒎
R = ideal gas constant  = ..(6)
T = absolute local temperature 𝟏−𝒙 𝒎
m = local mass flow rate at temp T  Integrating eqn. 6 to the respective limiting conditions i.e. z  x and mF  m
y = solute mass fraction at permeate
side 𝒙 𝒅𝒙 𝒎 𝒅𝒎
z = liquid feed composition ‫𝟏 𝒛׬‬−𝒙 = ‫𝒎׬‬ ..(7)
𝑭 𝒎 61
Separation through Pervaporation process
 Definite integral of eqn. 7 gives local feed composition x at temp T
𝒎𝑭
x= 𝟏 − (𝟏 − 𝒛) ..(8)
𝒎
 Now, doing a heat balance on the system

𝑑(𝑚𝑐𝑝 𝑇) = −𝐽ℎ𝑣 𝑑𝐴 ..(9)

cp is the specific heat capacity of the liquid (considering it constant) and hv is the
specific enthalpy of the vapor (constant).
m = local mass flow rate at temp T
 Combining equation 2 and 9, local temp T can be calculated as following
y = solute mass fraction at permeate
side 𝑑𝑇
z = liquid feed composition 𝑐𝑝 𝑇 + 𝑚𝑐𝑝 = ℎ𝑣
𝑑𝑚
cp= specific heat capacity of the liquid
hv = the specific enthalpy of the vapor
𝑇 𝑐𝑝 𝑑𝑇 𝑚𝐹 𝑑𝑚
TF = Feed temperature  ‫ 𝑇׬‬ℎ −𝑐 𝑇 = ‫𝑚 𝑚׬‬
mP = Permeate side mass flow rate 𝐹 𝑣 𝑝
mF = Feed side mass flow rate
mR = Retentate side mass flow rate 𝒉𝒗 𝒉𝒗 𝒎𝑭
 𝑻= −( − 𝑻𝑭 ) ..(10)
𝒄𝒑 𝒄𝒑 𝒎
62
Separation through Pervaporation process
 The final expression for the membrane area becomes after combining
expressions for x (eqn. 8), local temp T (eqn. 10) and total area A (eqn. 4) as
following:
𝒎𝑭
𝒅𝒎
𝑨= න ..(11)
𝒎 𝑬𝑱
𝒎𝑹 (𝟏 − 𝟏 − 𝒛 𝒎𝑭 )𝑱𝟎 𝒆𝒙𝒑{− }
𝒉𝒗 𝒉𝒗 𝒎𝑭
𝑹 𝒄 − 𝒄 − 𝑻𝑭 𝒎
𝒑 𝒑

m = local mass flow rate at temp T  Now defining s = m/mF and p (known as the “cut”) = mP/mF, where mP is the
y = mass fraction of the permeate permeate mass flowrate, then eqn. 11 can be briefed as following:
z = liquid feed composition
cp= specific heat capacity of the liquid 𝒂
𝒆𝒙𝒑{ 𝒃−𝟏
}
hv = the specific enthalpy of the vapor 𝒎𝑭 𝟏 𝒃−( 𝒔 )
TF = Feed temperature 𝑨= ‫׬‬ 𝟏−𝒛 𝒅𝒔 ..(12)
𝑱𝟎 𝟏−𝒑 (𝟏− 𝒔 )
mP = Permeate side mass flow rate
mF = Feed side mass flow rate Or, as the dimensionless membrane area
Where, a = (EJ/RTF)
mR = Retentate side mass flow rate 𝒂
𝒆𝒙𝒑{ 𝒃−𝟏}
s = m/mF, p = mP/mF b = (hv/cpTF) 𝑨𝑱𝟎 𝟏 𝒃−
𝒔
 Â= = ‫𝟏׬‬−𝒑 𝟏−𝒛 𝒅𝒔
𝒎𝑭 (𝟏− )
𝒔
Water
Water
 4197.5
1844.1

(𝒛 + 𝒙𝑹 ) 𝟏 − 𝒛 + (𝟏 − 𝒙𝑹 )
𝒄𝒑𝒂𝒗𝒈 = 𝒄𝒑𝒘𝒂𝒕𝒆𝒓 + 𝒄𝒑𝑬𝑨
𝟐 𝟐

337.08 K

9892440/J0 2.355

16.06
3.8134
Acetic Anhydride
Part of Unit 4: Chemicals from alcohol
Acetic Anhydride [(CH3CO)2O]
IUPAC Name Ethanoic anhydride Chemical properties Property Value
Common names Acetic acid anhydride Molecular Weight 102.09 g·mol−1
Acetyl acetate Melting Point -73.1 0C

Acetyl Oxide
Boiling Point 139.8 0C
Acetic Oxide
CAS Number 108-24-7 Density 1.082 gm.cm-3
(Chemical Abstract Service Colour Colourless
Registry Number) Odor Strong vinegar like smell
Flash point 49 0C
Explosive Limits 2.7-10.3 vol% in air
Solubility Low solubility in water forming Acetic
acid (2.6 gm/100 ml water). Forming
ethyl acetate with alcohol. Soluble in
Chloroform, Ether.
Toxicity Flammable 74
Acetic Anhydride [(CH3CO)2O]
 A low cost, commonly abbreviated Ac2O, it is the simplest isolable anhydride of a carboxylic acid (acetic
acid here) and is widely used as a reagent in organic synthesis.
 It is a colorless liquid that smells strongly of acetic acid, which is formed by its reaction with moisture in
the air.
 Acetic anhydride is extensively used in the cellulose acetate industry. It also finds application in the
manufacture of aspirin, phenacetin, and other drugs, perfumery chemicals, dye intermediates, flavor
bases, explosives, and plastics.
 Acetic anhydride was first synthesized in 1852 by the French chemist Charles Frédéric Gerhardt (1816-
1856) by heating potassium acetate with benzoyl chloride.
 Acetic anhydride is not stable in water, the conversion is conducted under anhydrous conditions.
 Aqueous solutions have limited stability because, like most acid anhydrides, acetic anhydride hydrolyses
to give carboxylic acids. (CH3CO)2O + H2O → 2CH3COOH (acetic acid)
75
 Acetic Anhydride [(CH3CO)2O]
 Acetic anhydride generally produced by carbonylation of methyl acetate i.e.
CH3COOCH3 + CO → (CH3CO)2O
 Carbonylation refers to reactions that introduce carbon monoxide into organic and inorganic substrates.
 Carbon monoxide is abundantly available and conveniently reactive, so it is widely used as a reactant in industrial
chemistry.
 Acetic anhydride is also prepared by the reaction of ketene (ethenone) with acetic acid known as “ketene
process” at 45–55 °C and low pressure (0.05–0.2 bar).
H2C=C=O + CH3COOH → (CH3CO)2O (ΔH = −63 kJ/mol)
 The route from acetic acid to acetic anhydride via ketene was developed by Wacker Chemie in 1922, when the
demand for acetic anhydride increased due to the production of cellulose acetate.
 Acetic acid is a by-product of acetylation in the cellulose acetate industry and at the same time about 75% of the
acetic anhydride produced is used cellulose acetate production.
76
 Acetic Anhydride [(CH3CO)2O]
 Acetic anhydride is a versatile reagent for acetylation (Acetylation reagents such as Acetyl chloride etc.) the
introduction of acetyl groups to organic substrates. In these conversions, acetic anhydride is viewed as a source of
CH3CO+ (acetyl group).
 Acetylation is an organic esterification reaction with acetic acid. It introduces an acetyl functional group into a
chemical compound.
 De-acetylation is the opposite reaction, the removal of an acetyl group from a chemical compound.

77
[(CH3CO)2O]: Production (Ketene process)

78
[(CH3CO)2O]: Production (Ketene process)

79
[(CH3CO)2O]: Production (Ketene process)

80
[(CH3CO)2O]: Production (Ketene process)
 Acetic acid is vaporized and fed together with a catalyst to a cracking furnace operating under vacuum
where ketene is produced together with water at high temperature (900oC).
 Various phosphate salts are effectively used as catalysts mostly Triethyl phosphate, since it is in liquid form,
can be added to the feed itself, is easy to handle, and is selective.
 The reaction mixture is rapidly cooled to avoid the reversing of the reaction.
 The condensed dilute acetic acid is separated and the gases then pass through two absorption towers in
which they are scrubbed by acetic acid/ acetic anhydride of various concentrations.
 Glacial acetic acid is added to the second absorption tower. Ketene is reacting with acetic acid to form acetic
anhydride.
 In following washing towers the gases are further scrubbed before released to the atmosphere.
 In a distillation column the crude acetic anhydride is distilled and recovered as the bottom product.
 The top product is acetic acid which is recycled to the process.
81
Ethyl Ether
Part of Unit 4: Chemicals from alcohol
Ethyl Ether [C2H5OC2H5]
IUPAC Name Ethoxyethane Chemical properties Property Value
Common names Diethyl ether Molecular Weight 74.123 g·mol−1
Dether Melting Point −116.3 °C

Ethyl oxide
Boiling Point 34.6 °C
Sweet oil of vitriol
CAS Number 60-29-7 Density 0.7134 g/cm3
(Chemical Abstract Service Colour Colourless
Registry Number) Odor sweetish odor
Flash point −45 °C
Explosive Limits 1.9–48.0 vol% in air
Solubility Water, Organic solvents

Toxicity Extremely flammable, harmful to

skin, decomposes to explosive
peroxides in air and light 83
Diethyl Oxalate
Part of Unit 4: Chemicals from alcohol
Diethyl Oxalate [C6H10O4]
IUPAC Name Diethyl Oxalate Chemical properties Property Value
Common names Ethyl oxalate Molecular Weight 146.14 g.mol-1
Ethanedioic acid Melting Point -40.6 °C

Diethyl ester Boiling Point 76 °C

Diethyl ethanedioate
Density 1.0785 gm.cm-3
CAS Number 95-92-1
(Chemical Abstract Service Colour Colourless, Oily Liquid
Registry Number) Odor AROMATIC ODOR
Flash point 49 0C
Solubility ALCOHOL, ETHER, ACETONE

Toxicity Irritating

85