STUDY OF MANUFACTURING OF FORMIC

ACID
A PROJECT REPORT

SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENT FOR THE

AWARD OF DEGREE OF
BACHELOR OF ENGINEERING
(CHEMICAL ENGINEERING)

SUBMITTED BY
AMARSINH P. GHATGE
SHREYAS M. GHODINDE
SAGAR V. PATIL

UNDER THE GUIDANCE OF

Prof. G. B. KUMBHAR

DEPARTMENT OF CHEMICAL ENGINEERING

BHARATI VIDYAPEETH COLLEGE OF ENGINEERING

(Affiliated to University of Mumbai)
SECTOR- 7, C.B.D BELPADA, NAVI MUMBAI 400614.

(2018-2019)

i|Page
 BHARATI VIDYAPEETH COLLEGE OF ENGINEERING,
NAVI MUMBAI

Certificate
This is to certify that AMARSINH P. GHATGE SHREYAS M. GHODINDE &
SAGAR V. PATIL has successfully completed the PROJECT work entitled
“STUDY OF MANUFACTURING OF FORMIC ACID” during the prescribed period in
the academic year 2018-19. This Seminar Report is submitted in the partial
fulfillment of the requirement for the Award of Degree of
BACHELOR OF ENGINEERING
IN
CHEMICAL ENGINEERING

Prof. G. B. Kumbhar Prof. (Dr.) M. V. Bagal

Seminar Guide Seminar Coordinator

Prof. (Dr.) S. P. Shingare Principal

Head B.V.C.O.E., Navi Mumbai
Department of Chemical Engineering

Examiner 1_________________________

Examiner 2_________________________

Date:

ii | P a g e
 Acknowledgement

At the outset, I would like to express mygratitude toDr. M.Z Shaikh, Principal
BharatiVidyapeethCollege of Engineering , Navi Mumbai and Dr.S.P Shingare, Head of the
Department , Department of Chemical Engineering for allowing us to carry out this project and
also for sanctioning computer lab and other facilities when needed.

The utmost credit in the completion of this project and for providing us with the most sought
spiritual light which guided us in moments of disarray and confusion and also for rendering
constant support goes to none other than Prof G.B, KUMBHAR , our project guide, whose name
itself spelt for success.

Last but not least, we would like to thank our friends for their constant feedback and necessary
support from time to time.

-Amarsinh P. Ghatge
-Shreyas Ghodinde
-Sagar Patil

iii | P a g e
 BHARATI VIDYAPEETH COLLEGE OF ENGINEERING,
NAVI MUMBAI

INSTITUTE VISION
“Social Transformation through Dynamic Education”

INSTITUTE MISSION
“To impart quality education to meet the needs of industry, profession and society;
and to achieve excellence in teaching, learning and research”

DEPARTMENT OF CHEMICAL ENGINEERING

VISION
The chemical engineering department seeks to prepare chemical engineers to pursue their goals as
successful careers of Entrepreneurs and Eminent Researchers which benefits the public welfare
through its service that is rigorous and challenging.

MISSION

1. To think critically and creatively, especially about the use of technology to address local and
global Chemical Engineering Problems.
2. To create and convert successful students as Entrepreneurs with leadership qualities.
3. To expands the knowledge through its scholarly pursuits.
4. To excel in Chemical Engineering practice, research, and management.
5. To develop technology to serve social needs in area of Chemical Engineering.

iv | P a g e
 CONTENTS
Page No
ABSTRACT i
LIST OF FIGURES ii
LIST OF TABLES iii

CHAPTER 1: INTRODUCTION
1.1 Introduction 2
1.2 Physical Properties 3
1.3 Chemical Properties 4
1.4 Industrial Importance and it uses 6
1.5 Global Scenario 8
1.6 Leading Manufactures 10
1.7 Justification for Selection of Topic 10
CHAPTER 2: LITERATURE REVIEW 13

CHAPTER 3: VARIOUS PROCESS DESCRIPTION

3.1 Process 19
3.2 Production of Formic Acid From Sodium Formates by reacting 20
With Inorganic acid
3.3 Hydrolysis of Foramide 21
3.4 Methyl Formate hydrolysis 23
3.5 Concentration of Formic acid 26
3.6 Oxidation of Hydrocarbon to formic acid 27

CHAPTER 4: JUSTIFICATION
4.1 Justification for selection of process 28
4.2 Advantages of selected process 32

v|Page
CHAPTER 5: SELECTED PROCESS DETAILS
5.1 Process Description 32
5.2 Process Block Diagram 33
5.3 Process Flow Diagram 34
CHAPTER 6: REACTION MECHANISM AND KINECTICS
6.1. Reaction Mechanism 36
6.2. Kinetic of reaction 38
6.3 Thermodynamic Feasibility 39
CHAPTER 7: CONCLUSION 42

REFERENCES

vi | P a g e
 ABSTRACT

Formic acid has a place in organic processes comparable to sulfuric acid in the mineral chemical
industries and its movements mirror the industry.
Methanol carbonylation has become the technology of choice in the world market. Production from
synthesis gas is increasing and the development of alternative raw materials is under serious
consideration. Research on conventional routes and catalytic reduction of CO2 routes to Formic acid
is also being pursued.
The main objective of the project is to discuss the design of a chemical plant for manufacture of
Formic acid, this project will shows the industrialized processes employed in manufacturing of the
Formic acid.
The objective of the development of new Formic acid processes has been to reduce raw material
Consumption, energy requirements, and investment costs. Significant cost advantages resulted
from the use of carbon monoxide and of low-priced methanol as feedstock’s. At present, industrial
processes (commercial process) for the production of Formic acid is dominated by methanol
carbonylation route followed by hydrolysis of methyl formate.

This is the basic and outlined scope of the project that is needed to be carried out:
 Literature review on the new methods for manufacturing of formic acid.
 Market survey
 Constructing a process flow diagram of the entire process
 Calculating mass and energy balances
 Equipment design and sizing
 Industry safety and hazard management
 Plant location
 Plant layout plans
 Project investment and costs

vii | P a g e
LIST OF FIGURES

TITLE Page No.

Figure 1.1 Dimeric Structure of formic acid 3

Figure 1.2 Global Application of formic acid 7

Figure 1.3 Demand and supply of formic acid 8
Figure 1.4 World Consumption Of formic acid in 2016 9
Figure 3.1 Manufacturing of formic acid from sodium formate 20
Figure 3.2 Process Block Dia. Of Formamide to formic acid 22
Figure 3.3 BASF process 24
Figure 3.4 USSR process 26
Figure 3.5 Block Dai. Oxidation of Hydrocarbons to Formic acid 27
Figure 5.1 Process Block Daigram 33
Figure 5.2 Process Flow Daigram 34

viii | P a g e
LIST OF TABLES

TITLE PAGE NO.

Table 1.1 Physical Properties 3

Table 6.1 Enthalpy and Gibbs free Energy data 40

ix | P a g e
 CHAPTER 1

INTRODUCTION

Page | 1
1.1 INTRODUCTION
Formic acid (HCOOH) is the first, or single carbon atom, homolog of the fatty acid series, It is
an industrial chemical of moderate importance, with world consumption in 1980 estimated at 200
million lb/yr and an anticipated growth rate of 4%/yr.

Formic acid, is a corrosive organic acid having a

Formic acid HCOOH is completely miscible with water and many polar solvents but only
partially miscible with hydrocarbons. It is an important intermediate in chemical synthesis and it
derived its name from the red ant, Formica rufa, in which itwas discovered around 1670. Formic
acid has been detected in the poison or defense systems of ants, bees, and other insects and also of
cnidarians.
Formic acid is used primarily in dyeing, in the textile and leather industries; in rubber
production; and as an intermediate in the chemical and pharmaceutical industries. The use of formic
acid as an aid in the ensilage of green forage has increased sharply.
The worldwide production of formic acid is about 260 000 t/a in 1987 and 390 000 t/a in 1995[1].
Formic acid is produced by hydrolysis ofmethyl formate or formamide or from its salts.In addition,
formic acid is a byproduct of Formicacid production by liquid-phase oxidation of hydrocarbons.
Historically, formic acid has been produced as a by-product of the manufacture of Acetic acid
by butane oxidation, or as a co product in the manufacture of formamide. However, both of these
processes are becoming obsolete and uneconomical, and a primary formic acid process is
considered likely to become the predominant source of formic acid in the future.
In hydrocarbons and in the vapor phase, it consists of hydrogen-bonded dimers rather than
individual molecules[2]. Owing to its tendency to hydrogen-bond, gaseous formic acid does not
obey the ideal gas law. Solid formic acid (two polymorphs) consists of an effectively endless
network of hydrogen-bonded formic acid molecules.

2|Page
 Fig 1.1 Dimeric Structure of formic acid

1.2 PHYSICAL PROPERTIES:

SRNO Property Unit

1 Heat of fusion 276kJ/mol
2 Heat of vaporization (at BP) 483 kJ/mol
3 Flash point 1560F

4 Surface Tension
 at 20 ◦C 37.67x10-3 N/m
 at 40 ◦C 35.48x10-3 N/m
 at 60 ◦C 33.28x10-3 N/m
 at 80 ◦C 31.09x10-3 N/m

5 Density 1.22 g/cm3

6 Boiling point 1010C at 760 mmHg
7 Melting point 8.30C at NTP
8 Auto Ignition Temperature 52 0C

9 Heat of Combustion 254.6 kJ/mol

10 Heat of formation Δ H
 Liquid (at 25 ◦C) -425.0 kJ/mol
 Vapor (at 25 ◦C) −378.57 kJ/mol

11 Heat of neutralization 56.9 kJ/mol

Critical data
12  P critical 7.279 MPa
 Tcriticak 581 K
 VOl.crit 0.392 g/cm3

3|Page
 13 Entropy S0
 Liquid (at 25 ◦C) [10] 129.0 JK−1 mol−1
 Vapor (at 25 ◦C) 248.88 JK−1 mol−1
14 Electrical conductivity (at 25 ◦C) 6.08×10−5 Ω−1 cm−1

1.3 CHEMICAL PROPERTIES :

Formic acid is the strongest of the unsubstitutedalkanoic monoacids. It has a pK, of 3.77 as
compared with 4.77 for acetic acid. Its relatively high acidity is due to the lack of alkyl groups and
their attendant electron release by an inductive effect. This electron release causes destabilization of
the carboxylate anions resulting from ionization of the higher monocarboxylic acids.

1. Esterification
Reaction: - HCOOH + ROH HCOOR
The high acidity of formic acid makes use of a mineral acid catalyst unnecessary for
esterification of many alcohols. The rate of esterification in neat formic acid was found to be
15000-20000 times that in neat acetic acid.

2. Amidation Reactions
Because of the acidity of formic acid, formylation of most amines occurs readily to yield the
expected derivatives. Consider an example:

R1

R2 NCHO

For N-Methyl formamilide where R1 CH3 & R2 C6H5

3. Addition to Olefins
Formic acid will undergo Markovnikov addition to olefins to yield formate ester with greater
ease than its homologs.

4|Page
 Reaction: HCOOH + C = C H – C – C – OOCH
Olefins Formate Ester

4. Auto Protolysis
Formic acid has a large autoprotolysis constant, that is, the equilibrium constant for
formation of its derivative.
OH
Reaction: 2HCOOH HCOO– + H–C
OH

5. Decomposition
Heat & especially acids causes formic acid to decompose to carbon-monoxide & water
treatment of formic acid with surfic acid is a convenient laboratory source of Co.

Reaction: HCOOH + H2SO4 CO + H2SO. H2O

In the presence of platinum, it decomposes with a release of hydrogen &carbondioxide[3].

Reaction: CH2O2 H2 + CO2

5|Page
1.4 Industrial Uses of Formic Acid in Different Industries

Formic acid is one of the top ingredients in many of the industrial products and needs. Here are
some ways in which it is used. One of the most commonly used chemical in the industry is Formic
acid. While formic acid is commonly found in nature that is not enough for all the uses it has been
put to by the industries which means that most of it is chemically created as well for synthetic uses.
While formic acid is found as the cause of irritation thanks to bee stings or ant bites, in high
concentration, it can be quite hazardous to your health.
It is used in a lot of industries namely rubber, chemical pharmaceutical and more. It is also widely
used in pesticides and food products but as a preservative though it is watered down to a nontoxic
level beforehand. With its major uses being in the commercial front however, here are few ways in
which it is used in the industry:

 Clothing industry
Formic acid is very high in acidic concentration which is it is watered down heavily before used for
pesticides and food preservatives but this highly acidic property has found a use for itself in the
clothing industry. Its acidic properties help in the production and making of leather as well as
contributing to the textile industry.
The textile industry is large on creating and dying cloth which is where formic acid is most
commonly used. With both of the products being extremely important, it is highly useful in the
textile industry.
 Rubber industry
The rubber industry has a big use for formic acid. Since the rubber you normally find are half
congealed and needs to be treated, it is melted and cleaned out before it is reformed again into
different shapes and products. In order for it to congeal again, formic acid is used as a coagulant for
the same making it an important factor in the creation of rubber and rubber products.
 Civil industry
Another area where formic acid helps is in the building of roads. While the acid isn’t used in its
natural form, the formates which are salts derived from it, are used to make the roads safer and less
slippery. The work better than normal salts in providing more grip and they are better for the
environment too. They also help to make sure that the road doesn’t get eroded by the heavy flow of
traffic.

6|Page
  Feed industry
While it is used as a preservative and in pesticides, this is because it has very high antibacterial
properties. It is also used as a food additive and is added in animal feed in order to give additional
antibacterial support while increasing the time for the finished produce and adding nutritional value.
With so many important uses in the industry, it is safe to say that formic acid is in high demand.
When you are looking to get into any of these industries, it is necessary for the same to be a part of
your plans. With many formic acid suppliers in the business, you need to see which supplier can
work the best for you.

Fig1.1 Global applications of formic acid

7|Page
1.5 GLOBAL SCENARIO:

A market study on formic acid discloses a large gap between its demand and supply. The production of
acetic acid is sound globally but recent data shows a decreasing producing capacity of Asia worldwide. Most
of Acetic acid produced in Asia is consumed internally and the excess is being imported due to its cheapness
in the process involved.

Fig 1.2. a Formic acid global demand

Fig 1.2 b Formic acid supply

8|Page
A comparison of the demand and supply chart from the 2013 data supports the fact that with the
demand of 12%, Europe producers are able to supply only 8% of it. The rest of the demand is
being imported from producers from other continents.
A study of world consumption of acetic acid in the year 2016 also reveals similar facts
with china being the greatest consumer of formic acid in the market and western Europe being the
second most consumer[4].

Figure 1.4 world consumption of formic acid in 2016

The Global Formic Acid Market is primarily driven by growing usage of formic acid as
antibacterial agent in animal feed coupled with usage as silage preservative in agriculture industry.
Formic Acid helps to reduce pH and lower the depletion of decay process thereby, causing
prolonged retain of nutritional value. Thus, supportive government policies and increased middle-
class spending in agriculture industry is expected to drive the formic acid market. Apart from
mentioned application, formic acid is used in pharmaceutical industry as local stimulation drug and

9|Page
astringent. Ban on antibiotics as growth promoters in animal feedstock is expected to drive the
demand of Formic Acid over the forecast period. The global formic market is expected to reach
USD 878.7 million by the end of forecasted period i.e. 2027. Asia Pacific is dominating region
followed by Europe and North America. Countries like China, India, Thailand and Indonesia are
expected to grow at rapid pace due to increased spending on R&D facility along with economic
development. Comparatively, China dominated the market for Formic Acid over other countries in
the region accounting over 40% of the consumption of formic acid in the Asia Pacific market.
North America and European regions are facing huge competition from emerging markets.

1.6 Leading Manufacturers of formic acid.

Some of the prominent players at the forefront of competition in the Global Formic Acid Market
and are profiled in MRFR Analysis:
 BASF SE (Germany)
 Perstorp AB (Sweden)
 Eastman Chemical Company (U.S)
 Gujarat Narmada Valley Fertilizers & Chemicals Limited (India)
 Feicheng Acid Chemical (China)
 Chongqing Chuandong Chemical (Group) Co., Ltd (China)
 LUXI Group CO LTD (China)
 Alfa Aesar (United States)
 Helm Italia S.R.L (Italy)
 Shanxiyuanping Chemicals Co. Ltd. (China)

1.7 Justification for selection of topic

Formic acid finds its applications in textile, pharmaceuticals & food chemicals, due to its strong
acidic nature &reducing properties. Traditionally the lather & tanning industry has been the biggest
consumer of FA, accounting in 2009for 30% of its global application.in 2013 the global demand for
FA was 579kt of which 34% was attributed to animal feed. Lather tanning accounting for 32% of
textile dyeing for 12%. Global production is expected to be more than 760kt in 2019

10 | P a g e
The global market is expected to grow with an average annual grow with an average annual growth
rate of 3.8% up to 2019. India’s market. The major procedure of formic acid in India are RCF plant
located at Alibag Thal & Gujrat Narmada valley fertilizer & chemical limited in order to increase
the growth rate for production of formic acid within India , plants similar to formic acid plants in
RCF & Gujarat Narmada valley fertilizer should be set-up
Formic acid can be found in the market at concentration of 85, 90, 95, 98& 99 wt. % with 85%
being the most common formic acid is a high valued product, with low rise of substitution.
Thus formic acid is not a risk from large scale substitution by competitive products in most
applications. Word consumption of formic acid is expected to be significant during 2016-21;
average annual growth is expected at 3.7% china, India others Asian (expected japan) and Africa
are forecast to exhibit strong demand growth, increases in population & living standards are
expected to result in greater consumption of formic acid
Hence looking at the world’s consumption rate & demand rate of formic acid , it seems a wise
decision to study the design of a chemical plant for manufacturing of formic acid in case if there is
need to start the manufacturing of it with country like India

11 | P a g e
CHAPTER 2: LITERATURE REVIEW

12 | P a g e
OverView

1. Direct synthesis of formic acid from carbon dioxide by hydrogenation in acidic media ,Walter
leithner ,Chemical engineering world Dec 2017
The chemical transformation of carbon dioxide into useful products becomes
increasinglyimportant as carbon dioxide levels in the atmosphere continue to rise as a consequence
of human activities. In this there direct hydrogenation of CO2 into formic acid using ahomogeneous
ruthenium catalyst, in aqueous solution and in dimethyl sulphoxide (DMSO),without any additives.
In water, at 40 C, 0.2M formic acid can be obtained under 200 bar,however, in DMSO the same
catalyst affords 1.9M formic acid. In both solvents the catalystscan be reused multiple times
without a decrease in activity. Worldwide demand for formicacid continues to grow, especially in
the context of a renewable energy hydrogen carrier, andits production from CO2 without base, via
the direct catalytic carbon dioxide hydrogenation,is considerably more sustainable than the existing
routes.

2. Formic acid production by hydrothermal oxidation of biomass derived carbohydrate

H.wang,chemical weekly may2016

In the cases of the oxidation of hydrothermal starch and cellulose, the addition of alkaline can
improved the yield of formic acid. The formic acid yields from glucose, starch and cellulose were
glucose>starch> cellulose in the both cases of the presence and absence of alkaline. Ca(OH)2 can
also improve the yield of formic acid from the oxidation of glucose, however, the yield of formic
acid in the presence of Ca(OH)2 was lower than that in Na OH and KOH. The investigation of the
mix effect of NaOH, KOH and Ca(OH)2 on the yield of formic acid showed that there is no
significant change when mixing NaOH and KOH, however, the yield decreased greatly when
blending Ca(OH)2 with NaOH or KOH. Further study on increasing the yield of formic acid from
starch and cellulose is now in progress.

3.Formation of acetic and formic acid in unmodified andmodified papers during accelarated ageing.
A.weekowski,chemical industry digest,april2014,(78-86)

 The direct determination of the concentrationof carboxylic acids in situ shows increased
13 | P a g e
  contents of acetic and formic acids duringaccelerated ageing.
 The increased content of the Mg2+ ions in thepaper structure leads to increased contents
ofacetic and formic acids (respectively, acetateand formate) during accelerated ageing,
incomparison with unmodified papers. The
 reason for this behaviour might be the strongpromoting role of Mg2+ ions in the
formationof organic acids.
 With the increase of the content of Mg2+ ions,the ratio of acetic/formic acids decreases
inmodified samples, compared to unmodifiedpapers.

4. Investigation of secondary formation of formic acid: urban environment vs oil and gas producing
region C.fletcher,R.amal, Chemical age of india,june2014 vol11

Formic acid concentrations are at comparable levels in two different environments: (1) an urban
downwind site and (2) a site in an oil and gas producing region, even though the VOC composition
is completely different. A box model constrained by measurements will be used to simulate the
secondary formation of formic acid and to evaluate the recently proposed formation pathways of
formic acid.

5. Formic acid synthesis using CO2 as raw material:Techno-economic and environmental

evaluation and market potential A.reis,S.mert,hydrocarbon processing2015 vol8 issue5

The future of carbon dioxide utilisation (CDU) processes, depend on : the future demandof
synthesised products with CO2, the availability of captured and anthropogenic CO2, the overall
CO2 not emitted because of the use of the CDU process, and the economics of theplant. The
current work analyses the mentioned statements throughdifferent technological, economic and
environmental key performance indicators to produce formic acid from CO2 the process saves CO2
emissions when compared to itscorresponding conventional process, under specific conditions. The
success or effectiveness of the CDU process will also depend on other technologies and/or
developments, like the availability of renewable electricity and steam
6.Formic acid as additive for the preparation of high-performance FePO4 materials by spray drying
method Fan Yanga, He Zhanga,chemical weekly dec15 vol9,issue5

14 | P a g e
High-performance ferric phosphate (FePO4), with well-defined ellipsoid morphology and uniform
particle size distribution, is successfully fabricated via a green spray drying method with formicacid
asadditive.It is found that the added formicacid plays a crucial role for the formation of the well
distributed FePO4 particles. Benefited by the outstanding structure and properties of ferric
phosphate prepared above, a high performance of lithium iron phosphate (LiFePO 4) has been
prepared. It exhibits high capacity, especially at high charging/discharging rate (158.4 mAh g−1 at
0.2 C and 107.3 mAh g−1 at 10 C), and excellent cycling stability (without capacity fading after
cycling for 200cycles at 1 C). All these impressive electrochemical performance could be ascribed
to the FePO4 precursor, and further attributed to the addition of formic acid, which may play as a
template, resulting in the well-defined morphology, uniform particles size distribution, hierarchical
pore structure, and high surface area of the ferric phosphate

7. Selective Oxidation of Glycerol to Formic Acid Catalyzed by Iron Salts,E. Farnettia and C.
Crottib,hydrocarbon processing, vol5 dec2011

Glycerol was oxidized by hydrogen peroxide to formic acid with excellent selectivity in the
presence of iron salts; the only byproduct present in the final reaction mixture was glycolic acid.
The reaction was carried out at r.t. either in acetonitrile/water or in water; at the end of the reaction
the catalytic system was still active and oxidation of another glycerol load took place with
comparable reaction rate and selectivity. The catalytic reactions here described fully comply the
requirements for a green process, from the point of view of metal, oxidant, reaction medium,
experimental conditions as well as excellent selectivity and overall high atom efficiency.

8. Pretreatment with formic acid enhances the production of small peptides from highly cross-
linked collagen of spent hens. Hui Hong, Bimol C. Roy,chemical engineering
world,issue5,march2013

Small collagen peptides are associated with various benefits, such as bone and skin health.
however, preparation of small collagen peptides from terrestrial vertebrate origins remains a
challenge. Here, we show that pretreatment with formic acid enhanced the production of small
collagen peptides from spent hen skin. After pretreatment with formic acid, the percentage of small
peptides below 2 kDa increased to 48.92% and 43.34% from 33.79% and 36.32% for heatsoluble

15 | P a g e
collagen (HSC) and pepsin-soluble collagen (PSC), respectively. Pretreatment with formic acid
degraded telopeptides and released the cross-links (pyrrole and pyridinoline), which made hen
collagen more susceptible to papain hydrolysis. LC-MS/MS results revealed that none of the
peptides identified from HSC-FA (formic acid)-Papain and PSC-FA-Papain were derived from
cross-linked telopeptides. These results demonstrated that formic acid assisted the hydrolysis of
highly cross-linked collagen of spent hens, and it might also be used to produce small collagen
peptides from other aged, vertebrate collagens.

9.A rapid and efficient hydrothermal conversion of coconut husk into formic acid and acetic acid
Kefan Ding, Yi Le, Guodong Yao,chemical weekly,vol8,june2013

Coconut husk is an abundant cellulose/lignin-rich biomass waste in tropic and subtropical zone.
Although the resource utilization of coconut husk has aroused considerable concerns, highly-
efficient and selective conversion of coconut husk into chemicals is difficult due to its stable
coexistence structure of cellulose and lignin components. Herein, a facile and high selectively
conversion of coconut husk into value-added organic acids of formic and acetic under mild
hydrothermal conditions was proposed for the first time. It was found that a simple acidic
pretreatmentis efficient for obtaining high yield of formic and aceticacids. The highest yield of total
acids can reach up to 50.2%, which is the reported highest yield of formic acid and acetic acid from
ligno-cellulosic biomass. This work exemplifies the possibility of complex coconut husk waste
valorization to value-added chemicals, which is not only solve the problems of coconut husk waste
pollution, but also provide an alternative route for fuel production from renewable resources.

10. A Catalytic Study Of formic acid oxidation on preferentially oriented platinum electrodes, l.
palaikis and a. wieckows, encyclopedia of chemical prossesing, vol 8, 2013

The oxidation of formic acid was examined by cyclic voltammetry and chronoamperometry in order
to determine the rate of catalytic activity (reaction turnover) as a function of surface crystallography
on preferentially oriented (electrochemically modified) platinum electrodes. The resulting turnover
rates indicated a maximum fourfold current enhancement for an approximately 60%oriented surface
versus a polycrystalline surface, suggesting that preferentially oriented electrodes are of potential
practical significance he fourfold enhancement in reaction turnover for a -faceted surface is

16 | P a g e
significant and optimistic with respect to the applicability of preferentially oriented surfaces in real-
life electrocatalysis, and we emphasize that the turnover results are consistent with those for formic
acid electrocatalysis on ordered platinum electrodes These results indicate that the Pt(lll) surface is
the most highly resistant to poison formation not only when long-range order, but also when short-
range surface order is produced and preserved upon electrolysis. This is an encouraging results
which should activate more research on polycrystal- line platinum catalysts modified to display
preferential crystallographic specificity, that is, without the need for faceting expensive single
crystal materials. The search for catalytically enhancing, crystallographically modified, rough Pt
black-type surfaces is particularly challenging in this regard.

17 | P a g e
 Chapter 3

Various Process Description

18 | P a g e
3.1 PROCESS
The 85% pure Methanoic Acid, sold in the name of Formic acid can be manufactured by
various processes. Each process is discussed in detail in the following sections.
The worldwide installed capacity for producing formic acid was about 330 000 t/a in 1988. The
installed formic acid processes can be classified in four groups:
1. The Reaction of Sodium Formate with an inorganic Acid.
2. The Acidolysis of Formamide with Sulfuric acid.
3. Hydrolysis Of Methyl Formate.
4. Oxidation of Hydrocarbons

While in the Indian scenario Methanol Carbonylation process takes the majority of Formic
acid production.Synthesis gas and Methanol are used to produce methyl Formate.

Formic acid is produced by this route using a two-step process.

1. Methyl Formate Synthesis

CO + CH3OH HCOOCH3
Carbon Monoxide + Methanol Methyl Formate

2. Hydrolysis/Purification
HCOOCH3 + H2O HCOOH + CH3OH
Methyl Formate + Water Formic Acid + Methanol

3.2 Sodium Formates by reacting with inorganic acid.

Raw material used are:
• Sodium Hydroxide
• Carbon monoxide
• Sulfuric acid

19 | P a g e
 Reactions Involved:
1. NaOH + CO HCOONa
2. 2HCOONa + H2S04 HCOOH + Na2S04

Block Diagram

Fig. 3.1 a Block Diagram of Manufacturing of formic acid from sodium formate

Flowsheet:

Fig. 3.1 b Flow sheet of Manufacturing of formic acid from sodium formate
Process Description:
• Sodium hydroxide (97 to 98 %) is charged into a reactor equipped with agitator a packed
tower. Carbon monoxide, free from carbon dioxide which is obtained is reacted with the
caustic soda at 150 – 200 C temperature under a pressure of 100 – 150 psi. The resulting
reaction product is crude sodium formate.
• Crude sodium formate was acidified with dilute sulfuric acid, resulting formic acid distilled
off. Due to the proximity of the formic acid and water boiling points, only dilute formic acid

20 | P a g e
 (below 75%) can be obtained by distillation. 85 – 90% formic acid is obtained by separating
it from Na2SO4 by distillation. The yield is 90 – 95 %.
Companies having access to by-product salt may continue to use this process, but in the absence of
an inexpensive source of sodium formate, this process is not competitive because it requires the
consumption of CO, caustic and sulfuric acid, with the need to dispose of byproduct sodium sulfate.
Also The addition of concentrated sulfuric acid to dry sodium formate results in quite extensive
decomposition with formation of carbon monoxide[5].
The disadvantages are of a chemical nature in so far as decomposition phenomena which can not
completely be avoided during the reaction of solid formates with concentrated sulphuric acid and
necessarily lead to losses of formic acid.

3.3 Hydrolysis of Formamide

Raw Material used:
• Ammonia

• Carbon Monoxide

• Sulfuric Acid

Reactions:

• CO + CH3OH HCOOCH3
• NH3 + HCOOCH3 HCONH2 + CH3OH

• 2 HCONH2 + H2S04 + 2H20 2 HCOOH + (NH4)2S04

Process:
 Formic acid is produced this way in a three stage process. In the first stage, methanol is
carbonylated to yield methyl formate.
 In the second stage, formamide is produced by ammonolysis of ethyl formate.

21 | P a g e
 In the third stage, sulfuric acid is used to hydrolyze formamide to formic acid and
ammonium sulfate.
This reaction is carried out preferably in stirred containers and provides the heat for the
distillation of formic acid. A hot slurry consisting essentially of ammonium sulfate and formic
acid flows out of the stirred container into a rotary kiln where the residual formic acid is
distilled so that dry, pure ammonium sulfate is produced at the kiln end. The yield of formic
acid exceeds 90 %. The economic efficiency of this process is determined by the commercial
value of ammonium sulfate.
This process has been practiced on an industrial scale in Europe, where formamide is also used
to manufacture HCN. The future of this route in Europe will, therefore, be affected by the
hydrogen cyanide demand and a significant factor will be the demand for HCN in the
production of acrylonitrile[6]. Generally, the high price of formamide as obtained from the small
scale plants currently available and the need of an outlet for byproduct sulfate, makes this route
anything but attractive. Also, the recently reported teratogenicity of formamide calls for
stringent environmental and safety precautions.

Fig 3.2 Process Block Dia. Of Formamide to formic acid

22 | P a g e
3.4 Methyl Formate Hydrolysis Route
Raw material
• Methanol
• Water
• Carbon Monoxide
Synthesis of formic acid by hydrolysis of methyl formate is based on a two-stage process: in the
first stage, methanol is carbonylated with carbon monoxide; in the second stage, methyl formate is
hydrolyzed to formic acid and methanol. The methanol is returned to the first stage.
Reactions:
CH3OH + CO HCOOCH3
CH3OOCH + H2O CH3OH + HCOOH
CO + H2O HCOOH
Although the carbonylation of methanol is relatively problem-free and has been carried out
[4]
industrially for a long time , only recently has the hydrolysis of methyl formate been developed
into an economically feasible process. The main problems are associated with work-up of the
hydrolysis mixture. Because of the unfavorable position of the equilibrium, reesterification of
methanol and formic acid to methyl formate occurs rapidly during the separation of unreacted
methyl formate. Problems also arise in the selection of sufficiently corrosion-resistant materials.
Industrial methods involving carbonylation of methanol and hydrolysis of methyl formate, followed
by isolation of the formic acid, were developed by (1) the Leonard Process Company (United
States), (2) BASF (Federal Republic of Germany), (3) Halcon – Scientific Design – Bethlehem
Steel (United States), and (4) the Scientific Research Institute for the Chlorine Industry of the
Ministry of the Chemical Industry (former Soviet Union).[]

3.4.1 BASF Process

A 100 000-t/a formic acid plant began operating in Ludwigshafen (Federal Republic of Germany)
in 1981. In this plant, a technology for the hydrolysis and dehydration was used for the first time.
The production of methyl formate by carbonylation of methanol has been carried out on a large
scale for many years at BASF [7]. In the BASF process, hydrolysis is carried out with a large excess

23 | P a g e
of water (about 5 mol of water per mole of methyl formate) to shift the equilibrium in the direction
of formic acid. Much of the water is separated by liquid – liquid extraction with a secondary amide.
Process Description: (Fig. 3.3) Carbon monoxide and methanol react in the methyl formate reactor
(a) in the presence of sodium methoxide. Methyl formate is fed, as a distillate, from the methyl
formate column (b) into the formic acid reactor (c) together with recycled methyl formate.
Methanol and dissolved catalyst are drawn off from the bottom of column (b) and returned to
reactor (a); catalyst decomposition products are discharged by crystallization. In reactor (c), methyl
formate is hydrolyzed with excess water at elevated temperature and increased pressure. The
reaction product is flashed into the low-boiler column (d). Methyl formate is removed as the
distillate, with methanol as a side stream, and dilute aqueous formic acid is drawn off from the
bottom into the extraction unit (e). Here, the formic acid and some of the water are extracted by the
secondary amide. Most of the water (largely free of formic acid) is recycled to reactor (c). The
extract–a mixture of extractant, formic acid, and some water–is distilled in the dehydration column
(f). Enough water is distilled via the head for the required formic acid concentration to be obtained
in the pure acid column (g). This column is operated in vacum. The extraction agent is recycled
from the bottom of column (g) to the extraction unit.

Fig. 3.3 Production of formic acid (BASF process)

a) Methyl formate reactor; b) Methyl formate column; c) Hydrolysis reactor; d) Low-boiler column,
e) Extraction unit; f) Dehydration column; g) Pure acid column

24 | P a g e
3.4.2 USSR Process
A 40 000-t/a formic acid plant based on a process developed in the former Soviet Union is being
built in Saratov (Ukraine) [62] and is expected to be operational in 1989. According to published
[8]
material, this formic acid process differs from the above-mentioned processes , in the hydrolysis
stage. Hydrolysis is carried out at 80◦C and 0.6MP a in a fixed-bed reactor equipped with bubble-
cap trays in the upper section. Reesterification is prevented by decompressing and cooling to about
45 ◦C. Formic acid is produced in a pressure column as an azeotropic mixture with water which
contains 85 wt% formic acid.
Process Description (Fig. 3.6). Carbonmonoxide reacts with methanol in column reactor (a), in the
presence of the catalyst and a stabilizer, at about 3MPa, to yield methyl formate. Separation into
methyl formate (distillate) and methanol plus catalyst takes place in the methyl formate column (b)
at 0.2MPa. The exhaust gas produced is partially recycled. In reactor (c), methyl formate is
hydrolyzed with water in two stages; in the first stage, packed acidic cation exchanger is used as
catalyst (f), which partially hydrolyzes the methyl formate. In the second stage, hydrolysis is
carried out with autocatalysis by the formic acid produced in stage one. Methanol and methyl
formate are distilled from the hydrolysis product in the lowboiler column (d); these compounds are
separated, along with the carbonylation reaction mixture, in the methyl formate column (b).
Aqueousformic acid is drawn off the bottom of column (d) and further dehydrated in the formic
acid column (e) under pressure. Formic acid with a content of 85 wt% is drawn off in the side
stream, and the concentration can be increased to about98 wt% in the column situated downstream.

25 | P a g e
 Figure 3.4 Production of formic acid (USSR process)
a) Methyl formate reactor; b) Methyl formate column; c) Hydrolysis reactor; d) Low-boiler column;
e) Formic acid column; f) Fixed-bed catalyst

3.4.3 Concentration of Formic Acid

Formic acid –water mixtures cannot be concentrated to more than the azeotropic composition by
simple distillation (→Distillation and Rectification). Further dehydration is carried out by ternary
azeotropic distillation, extractive distillation, or extraction. Additional concentration can then be
achieved by simple distillation. Through suitable choice of distillation conditions, formic acid with
a content exceeding 99 wt% can be drawn off as distillate.

Azeotropic Distillation. Propyl and butyl formats have been proposed as entrainers for azeotropic
[4]
distillation . A particularly economical separation of water from the water – formic acid – acetic
acid mixture obtained by oxidizing butane is achieved by azeotropic distillation with ethyl n-butyl
[9]
ether .
Extractive Distillation. In extractive distillation, formic acid is extracted in a distillation columnby
means of a basic extracting agent introduced countercurrently and fed into the bottom of the

26 | P a g e
column. If this mixture is heated in a columndownstream, the formic acid is liberated from the salt-
like compound and distilled. NFormylmorpholine has been suggested as extractant [10], and various
sulfones have been described as auxiliary liquids for extractive distillation [11].
[12]
Extraction. A number of extractants have been proposed for extracting acetic and formic acids .
According to BASF, secondary amides are efficient extracting agents; Huls recommends
compounds in the series tri-noctylamine to tri-n-dodecylamine.

3.5 Oxidation of Hydrocarbons to Formic acid

Formic acid is produced as a byproduct in the liquid-phase oxidation of hydrocarbons to acetic acid
In the United States, butane is used as the hydrocarbon, and ca. 50 kg of formic acid is produced per
ton of acetic acid. In Europe, the oxidation of naphtha is preferred, and up to 250 kg of formic acid
is produced per ton of acetic acid in this process. For the mechanism of formic acid production, see
[13]
. Unreacted hydrocarbons, volatile neutral constituents, and water are separated first from the
oxidation product. Formic acid is separated in the next column; azeotropic distillation is generally
used for this purpose. The entrainers preferred in this process are benzene or chlorinated
[13]
hydrocarbons. The formic acid contains about 2wt%acetic acid, 5wt%water, and 3wt%benzene .
Formic acid with a content of about 98 wt% can be produced by further distillation.

Figure 3.5 Block Dai. Oxidation of Hydrocarbons to Formic acid

27 | P a g e
 Chapter 4
Justification for Selection of Process

28 | P a g e
 4.1 Justification for selection of process
Undoubtedly the methanol carbonization route followed by the hydrolysis of methyl -formateto be
formic acid has a greater production percentage. When compared to any other process this process
technology holds 49% of the world'stotal formic acid production. Before development of methyl
formate hydrolysis process production was done by the process of acidolysis of alkali formats
which can accounts around 26% of which production capacity. In this process high concentrated
acids like HCL and H2SO4 are used to convert format to formic acid this process is carried out
at 180 degree Celsius temperature and ac 1.5 to 1.8 MPa. The economic feasibility of producing
formic acid from its salt suffers because one equivalent of low value inorganic salt (i.e. sodium
sulphate) is produced per mole of formic acid.
Henry Defyus at British Celanse developed a methanol carbonylation plant as early as 1925 .The
first 100000 metric tons formic acid plant began operating in Germany in 1981 where German
company developed a process where carbonation of methanol and hydrolysis of methyl formate to
formic acid was started. In this BASF plant hydrolysis and dehydration to place where water was
used in the ratio of 5:1 so as to put the reaction on the product side. Much of the water is separated
by liquid-liquid extract with secondaryamine. A very similar process is being used in RCF Thal for
manufacturing purpose but the advancement in the Rcf process made it more better and efficient
than any other process in the market for the production of formic acid. Pressure and temperature
conditions are used to handle azeotropic condition between water and formic acid.

4.2 Advantages of selected process:

1. our operation is cheaper than any other process as cheaper raw materials like CO, methanol
and water are used
2. Methanol used as the feed is cheaper and unreacted methanol in the reactors is recycle back
to make it use again as this process reduces raw material cost, thereby reducing production
cos.
3. Process flow simplicity with minimum number of technological steps
4. The liquid phase reaction is easy to control as it is maintained at 1250C range rather than
at 2500C range
5. Amount of salt produced is significantly less than other processes where corrosive salts are
formed in this process

29 | P a g e
6. The azeotrope formed between formic acid and water is distillated using pressure and
temperature conditions rather than using entertainers like secondary or tertiary amines or
benzene
7. Desired concentration of formic acid can be manufactured but mostly 85%wt grade of
formic acid is produced
8. Cheaper catalyst that is sodium methoxide and potassium methylate is used rather than
expensive Platinum plate based catalyst
9. Number of distillation columns have been reduced
10. Low cost of final product
11. High quality of final product
12. Since concentrated acids are not use the risk of corrosion has reduced.
13. All emissions from process are purified at gas cleaning system.
14. Formic acid is not produced as a byproduct but it is produced as a main product in this
process.

30 | P a g e
 Chapter 5
Selected Process Details

31 | P a g e
 5.1 Process Description
The carbonylation process of methanol is carried out in a continuous stirred tank reactor. The
methanol and carbon monoxide is fed to the reactor from the bottom as feed. The carbon
monoxide is compressed in a compressor to 30 bar before inlet to the reactor to ensure the
reaction is occurs in the liquid phase. The reaction is highly exothermic and hence a cooling
jacket is provided outside the reactor to ensure that the proper temperature of 150oC is
maintained in the reactor. The initial heat required to ignite the reaction is mainly rough age of
steam through the jacket. As the reaction starts, the heat of reaction is used to continue the
reaction and excess heat is removed.
The product stream from the CSTR, is rich in Methyl Formate solution contains catalyst
potassium methylate and unreacted CO and Methanol is made to pass through the throttling
valve to the flash tank where the product is flashed to a reduced pressure of 1 atm. The product
(Methyl Formate) from the flash tank is fed to the Methyl Formate Batch Tank. A recycle stream
is pumped from the bottom of the flash tank back to the CSTR.
The Second step towards formation of formic acid is hydrolysis of product formed in pervious
step that is Methyl Formate. Measured quantity of MF and water are fed to Formic Acid Reactor,
which operates at 11 kg/cm2 g, and 110 0C temperature. The liquid mixture of formic acid,
methanol , water are passed onto 1st distillation column so that mixtures distilled to separate
light ends ( methanol and methyl formate) from the bottom stream containing Formic(36%) and
water(64%). The light end products are transferred back to their respective column. For further
purification of formic acid it is passed onto another distillation where excess water is removed as
top product and transferred back to Formic Acid Reactor. From the bottom of 2 nd column 80%
Formic Acid is taken to the 3rdcolumn, which operates under vacuum 150 mmHg. (87-88)%
Formic Acid is taken out from the top of the 3rd column and mixed with bottom liquid of 2 nd
column in a mixer to make 85% Formic Acid and transferred to batch tank. The bottom liquid of
3rd column is recycled back to 2nd column. Then after complete analysis of batch tank Formic
acid is transferred to two main storage tanks.

32 | P a g e
5.2 Process Block Diagram

Fig. 5.1 Process Block diagram for selected process

33 | P a g e
34 | P a g e
 Chapter 6
REACTION MECHANISM AND
KINECTICS

35 | P a g e
6.1 Reaction Mechanism
Carbonylation of Methanol
The synthesis of methyl formate by carbonylation of methanol is well known chemistry. The
methanol carbonylation occurs through two step mechanism the methoxide ion reacts with CO to
─
form CH3OCO which then reacts with methanol producing methyl formate and restoring the
active catalyst. This is achieved by using an alkali metal methoxide catalyst as in our case it
potassium methylate, dissolved in methanol at 90-110◦C and with 20-70 bar of CO. [14, 15]. There are
3 side reactions occurring, the product of these side reaction are salts like trimethoxymethane and
dimethyl ether

36 | P a g e
The overall reaction is given below

CH3OH + CO HCOOCH3

The nucleophilic attack of methoxide ion on carbon monoxide was proposed by Christansen [16] in
1942 and the kinetic studied by Tonner et.al.[17]. Unlike other processes where catalyst system like
homogeneous ruthenium [14,15], platinum [18] and tungsten [19] complexes which require the
activation of carbon-oxygen bonds, transition metal complex catalysts do not need halide promoters
to form methyl formate by activation of the oxygen-hydrogen bond of methanol. These catalytic
systems, however, are either in the stage of fundamental research or not as efficient as the current
homogeneous sodium or potassium methoxide catalyst system.

37 | P a g e
Hydrolysis of Methyl Formate:

This reaction is reversible reaction. In order to push the reaction in side of formic acid excess water
is used in molar ratio of 5:1 (water /Methyl Formate). The conversion of methyl formate is up to 60
% as compared to 30% when used in ratio of 1:1. However dilute aqueous solution of formic acid
is obtained this way, and excess water must be removed from the formic acid with the expenditure
of as little energy as possible. Another problem is that Formic acid and water form azeotrop to
separate it more number of distillation columns are used which operate at low pressure in order to
reduce concentration of water in mixture.

Overall Reaction :

H2O + CO → CO2H2

6.2 Kinetics Of reaction:

r = C X a X e−(E/RT) X c X pCO

Where
r = reaction rate,
C = proportionality coefficient,
a = interface between gas and liquid,
E = activation energy,
R = molar gas constant,
c = catalyst concentration in solution, and
pCO =CO partial pressure in the gas phase.

38 | P a g e
The reaction rate can be raised by increasing the temperature, the carbon monoxide partial pressure,
the catalyst concentration, and the interface between gas and liquid.

The above equation reveals the dependence of reaction rate on the partial pressure of carbon
monoxide. Therefore, to synthesize methyl formate, gas mixtures with a low proportion of carbon
monoxide must first be concentrated; this can be achieved by low temperature distillation, pressure-
swing adsorption, prism separators (Monsanto), or the Cosorb process (Tenneco).

6.3 Thermodynamic Feasibility:

Table 6.1 Enthalpy and Gibbs free Energy data

Compound ∆H0 R(KJ/Mol) ∆G0 R(KJ/Mol)

CO -110.5 -137.23
H2O -241.82 -237.14
CH2O2 -425 -361.4

Calculations:
Heat of Enthalpy
∆H0 R (298) = Product – Reactant
= - 425 – (-241 + 110.5)
= - 294.5 KJ/Mol

Gibbs free energy

∆G0 R(298) = Product – Reactant
= - 361.4 – (-237.14 + 137.23)
= - 261.49 KJ/Mol
We know that,
∆G1 = - R T ln K1
-261.49 = -8.314 *10-3 X 298 X ln K
K298 = 6.865 X 1048

39 | P a g e
 Reaction Temperature: 1250C

By Van’t Hoff Equation

Ln ( K2 /K1) = (-∆H R/R) X (1/T2 -1/T1)
Ln ( K2 /6.865*1048) = (294.5/8.314) X (1/398 -1/298)
K2 = 6.66 X 1045

∆G2 = - R T2 ln K2
= - 8.314 X 398 X ln (6.66 X 1045)
= -349.137 KJ/Mol

Since the Gibbs Free Energy Value is negative the reaction is Feasible and negative change in
entropy signifies that the reaction is spontaneous.

40 | P a g e
CHAPTER 7
CONCLUSION

41 | P a g e
CONCLUSION

The demand of formic acid is growing in many industrial market particularly in leather, and
fertilizer industries. This compound is not only used in paint industry but also component in
production of hydrogen for fuel cell,pharmaceuticals,dyes,pigments and it is also a basic
insecticide being a source of methanol. Formic acid is still widely used in the rubber industry also
The global market of formic acid is respected to grow with an average annual growth rate of
3.8%upto 2019. India’s market for formic acid is only 3.7% of total worlds market. The major
producer of formic acid in India are RCF plant located at Thal Alibag.& Narmada valley
fertilizers located in Gujrat. In order to increase the growth rate for production of formic acid
within India more plants are needed to set up in India
It’s been viewed in literature survey that the manufacturing process carried in RCF for formic
acid is economically efficient as well as in term of product quality and yield. Since the process is
carried out in two steps it terminates the problem incurred at various parameters. The process is
also environment friendly as it produce very less CO 2 emission and the best part for economical
aspect is the space required for plant setup is very less. The best part of RCF process is formic
acid of concentration upto 98% is achieved which is not possible in other process.

42 | P a g e
REFRENCES:

1. K. Weissermel, H.-J. Arpe: Industrielle Organische Chemie, Wiley-VCH, Weinheim 1998.

2. R. J. Jakobsen, Y. Mikawa, J. W. Brasch, Spectrochim. Acta Part A: 23 A (1967) 2199 –
2209
3. The chemistry of formic acid and its simple derivatives Harry w. Gibson chemicals and
plastics division, Tarrytown, New York 10591
4. Jukka Hietelaand Werner Reutemann,Formic Acid, Asia- Pacific Journal of Chemical
Engineering,2016,5-10.
5. Formic Acid [online] Available : https://nptel.ac.in/courses/103106109/7.
6. Richard G. Herman, Springer US , Catalytic Conversation of Synthesis Gas&Alcohols to
Chemicals ,1984, 249-260
7. Bethlehem Steel Corp., US 3 907 884, 1973 (J. B. Lynn, O. A. Homberg, A. H. Singleton).
8. Salzgitter Industriebau GmbH: Technical Information Formic Acid, 1982.
9. W. Hunsmann, K. H. Simmrock, Chem. Ing. Tech. (1966) no. 10, 1053 – 1059.
10. BASF US 4 076594, 1978 (H. Bulow, H. ¨ Hohenschutz, W. Sachsze, J. E. Schmidt).
11. L. Berg, An-I Yeh, US 4 642 166, 1986.
12. P. Eaglesfield, B. K. Kelly, J. F. Short, Ind. Chem. (1953) April, 147 – 151; (1953) June,
243 – 250
13. A. Aguilo, Th. Horlenko, Hydrocarbon Process. (1980) no. 11, 120 – 130
14. G. Braca, G. Sbrana, G. Valentini, G. Andrich , G. Gregorio 1979 Carbonylation and
Homologation of Methanol, Methyl Ethers and Esters in the presence of Ruthenium
Catalysts, in M. Tsutsui (Ed.), Fundamental Research in Homogeneous Catalysis, Plenum
Press, New York, vol 3, 221-238.
15. G. Jenner, G. Bitsi (1988.) Ruthenium-catalyzed carbonylation of alcohols to alkyl formate
, Journal of Molecular Catalysis, A: Chemical, vol 45, Issue 2, 235-246.
16. J. A. Christiansen and J. C. Gjaldbaek (1942) On the reaction between Carbon monoxide
and alcohol catalyzed by alcoholate” Det kgl.Danske Videnskabernes Selskab, vol XX, 3.
17. S. P. Tonner, D. L. Trimm, M. S. Wainwright, N. W. Cant (1983) The Base Catalyzed
Carbonylation of Higher Alcohols, Journal of .Molecular Catalysis, A:Chemical, vol 18,
Issue 2, 215-222.

43 | P a g e
18. R. A. Head and M.I. Tabb (1984) Platinum–catalyzed carbonylation of methanol to methyl
formate, Journal of Molecular Catalysis, A: Chemical, vol 26, Issue 1, 149-158
19. D. J. Darensbourg, R. L. Gray, C. Ovalles and M. Pala J (1985) Homogeneous Catalysis of
Methyl Formate production from Carbon Monoxide and Methanol in presence of Metal
Carbonyl Catalysts, Journal of Molecular Catalysis, A: Chemical, vol 29, Issue 2, 285-290.

44 | P a g e
I. Program Educational Objectives(PEO):

A. Fundamental Knowledge: Graduates of the program will be skilled in the fundamental

concepts of chemical engineering necessary for success in industry or in engineering
practices as well as advanced study.
B. Design Skills: Graduates of the program will be prepared with problem solving skills,
laboratory skills, and design skills for technical careers in solving critical problems.
C. Professional Skills: Graduates of the program will be prepared an effective team member
with communication and teamwork skills as well as an appreciation for ethical behavior
necessary to thrive in their careers.
D. Specialization: Graduates of the program will be prepared to pursue career choices in
chemical engineering, energy and environment engineering, bioengineering, or related
interdisciplinary fields that benefit from a strong background in applied sciences or
engineering.
E. Self Learning: Graduates of the program will be prepared to continue their professional
development through continuing education and personal development experiences based on
their awareness of library resources and professional societies, journals, and meetings,
conferences, seminars, workshops, industrial visits, expert talks, industry interactions, etc.

45 | P a g e
II. Program Outcomes (PO):

PO1. Engineering knowledge: Apply the knowledge of mathematics, science, engineering

fundamentals, and an engineering specialization to the solution of complex engineering
problems.
PO2. Problem analysis: Identify, formulate, review research literature, and analyze complex
engineering problems reaching substantiated conclusions using first principles of
mathematics, natural sciences, and engineering sciences.
PO3. Design/development of solutions: Design solutions for complex engineering problems and
design system components or processes that meet the specified needs with appropriate
consideration for the public health and safety, and the cultural, societal, and environmental
considerations.
PO4. Conduct investigations of complex problems: Use research-based knowledge and research
methods including design of experiments, analysis and interpretation of data, and synthesis
of the information to provide valid conclusions.
PO5. Modern tool usage: Create, select, and apply appropriate techniques, resources, and
modern engineering and IT tools including prediction and modeling to complex engineering
activities with an understanding of the limitations.
PO6. The engineer and society: Apply reasoning informed by the contextual knowledge to
assess societal, health, safety, legal and cultural issues and the consequent responsibilities
relevant to the professional engineering practice.
PO7. Environment and sustainability: Understand the impact of the professional engineering
solutions in societal and environmental contexts, and demonstrate the knowledge of, and
need for sustainable development.
PO8. Ethics: Apply ethical principles and commit to professional ethics and responsibilities and
norms of the engineering practice.
PO9. Individual and team work: Function effectively as an individual, and as a member or
leader in diverse teams, and in multidisciplinary settings.
PO10. Communication: Communicate effectively on complex engineering activities with the
engineering community and with society at large, such as, being able to comprehend and
write effective reports and design documentation, make effective presentations, and give and
receive clear instructions.
PO11. Project management and finance: Demonstrate knowledge and understanding of the
engineering and management principles and apply these to one’s own work, as a member
and leader in a team, to manage projects and in multidisciplinary environments.
PO12. Life-long learning: Recognize the need for, and have the preparation and ability to
engage in independent and life-long learning in the broadest context of technologicalchange.

46 | P a g e
III. PROGRAM SPECIFIC OUTCOMES (PSO)

PSO1 :At the end of the programme students should have Knowledge of mathematical
calculations, Numerical methods, material and energy balances, thermodynamics, Unit operations,
chemical reaction engineering, Project and process management applied to chemical industries
including safety, health, ethics and environmental aspects,.

PSO2: At the end of the programme students should have Knowledge of Instrumentation,
process dynamics and control, process design, Modeling and simulation, use of modern
experimental and computing techniques.

PSO 3 :At the end of the programme students should Excel in careers in the chemical,
petroleum, petrochemical, pharmaceutical, food, biotechnology, energy, materials processing or
other related industries and organizations.

47 | P a g e