SVKMs

NARSEE MONJEE INSTITUTE OF MANAGEMENT STUDIES

MUKESH PATEL SCHOOL OF TECHNOLOGY MANAGEMENT & ENGINEERING


DESIGN REPORT
ON

OXALIC ACID


BY

HIMA SAMHITA KANCHARLA

(ROLL NO L-014 & SAP ID 71114110003)

&

VIKEN SHAH
(ROLL NO L-023 & SAP ID 71114110010)


FACULTY MENTOR

PROF. RAHUL PALIWAL

TABLE OF CONTENTS


Sr. No.

PARTICULARS

PAGE No.

1.

Introduction

2.

Oxalic acid from Sodium Formate

3.

Oxalic acid from Propylene

4.

Oxalic acid using Dimethyl Oxalate

5.

Oxalic acid from Molasses using Nitric

acid

10

6.

Engineering aspects & Technology

Selection

12

INTRODUCTION
Oxalic acid, H2C2O4 is a colorless crystalline dicarboxylic acid gives colorless solution
upon dissolved in water. In terms of acid strength, it is much stronger than acetic acid.
Oxalic acid is a reducing agent and its conjugate base, known as oxalate (C2O42-), is a
chelating agent for metal cations. Typically, oxalic acid occurs as the dihydrate with the
formula H2C2O4.2H2O. Ingestion of oxalic acid through skin contact or orally is
dangerous.
The oxalic acid was discovered by Scheele in 1776. Scheele was produced oxalic acid by
the oxidation of sugar using nitric acid and called it saccharic acid. Artificial synthesis
can be affected in various ways. Sugar and starch was boiled with nitric acid, which
produces oxalic acid as a penultimate product of oxidation.
Mostly commercial oxalic acid is contaminated with sulfuric acid and alkali where alkali
cannot be removed by recrystallization method using water, but it can be removed by
recrystallization using 10 - 15% hydrochloric acid.
MANUFACTURE
1. Oxalic acid from sodium formate
RAW MATERIALS
Basis: 1000kg oxalic acid dihydrate from sodium formate
Sodium formate 1325kg
Calcium hydroxide 650kg
Sulfuric acid 950kg

Module:2

Lecture:10
Oxalic acid
REACTION
Reaction

Dr. N. K. Pat

Manufacture process
MANUFACTURE PROCESS

Sodium
formate wformate
as obtained was
by the robtained
eaction of solid
(97 of
- 98%)
and sodiu
Sodium
bysodium
the hydroxide
reaction
solid
carbon monoxide at 200C temperature and 150psi pressure in a0n autoclave.

hydroxide (97 - 98%) and carbon monoxide at 200 C temperature and 150p
Sodium oxalate
was obtained, at the completion of above reaction by reducing the
pressure
in an autoclave.
pressure in autoclave and increasing the temperature to 400C. Reaction was completed
after the evolution of hydrogen was ceased.

Sodium oxalate was obtained, at the completion of above reaction b

The reaction mixture was transferred to precipitator and calcium hydroxide was added
reducing
the pressure
in autoclave
and
increasing
the temperature
to 4000
under stirring.
The calcium
oxalate was
filtered
and sodium
hydroxide was
concentrated
for completed
reuse. Filter cake
crude
calcium oxalate
run to an was
acidifier
with
Reaction
was
afterof the
evolution
of hydrogen
ceased.
small amount of calcium carbonate and treated with dilute sulfuric acid. Calcium
Calciumsulphate dihydrate
Dilute (CaSO4.2H2O). Mother liquor was run to
Hydrogen
precipitated
out as calcium
hydroxide
sulfuric acid
a crystallizer and concentrated to specific gravity of 300Be. Crystallize oxalic acid in the
Sodium
formate of dehydrate was washed and dried.
form
The yield of oxalic acid dehydrate was about 80% by weight based on sodium formate.
It is generally sold and used, as the dihydrate, but heating the dihydrate to 100C where
Crystallizer
it loses 2 molecules of water may form anhydrous oxalic acid.
Precipitator

Acidifier

The sodium oxalate may be acidified directly to oxalic acid by mixing 1 part sodium
Autoclave
oxalate with
3 parts of methanol and 0.8 parts of concentrated sulfuric acid. Separate
insoluble sodium sulfate, from the methyloxallate- methanol-sulfuric acid solution.
Filter sodium sulfate and hydrolyze the mother liquor by the addition of 3.5 pHot
arts
air water
in

Dryer
Filter

Filter

Filter

Col
i


to form oxalic acid and methanol. Distilled the methanol and recycled to the process.
Concentrate the crude oxalic acid solution and crystallized the oxalic acid.
Oxalic acid is also manufactured by the oxidation of molasses with nitric acid. Similarly,
oxalic acid can be obtained from many other organic compounds like glycol, alcohol,
fats, oat hulls saw dust and other cellulosic materials by oxidation with nitric acid.

BLOCK DIAGRAM:

2. Oxalic acid from propylene

RAW MATERIALS
Basis: 1000kg oxalic acid from propylene
Propylene 460kg
Nitric acid 1375kg
Oxygen 870kg

Module:2
Lecture:10 Oxalic acid

REACTION

Reaction

Dr. N. K. Patel

Second
reactor

MANUFACTURING
PROCESS
Manufacture process

In this process oxalic acid was obtained by oxidation of propylene with nitric acid. It is
Inpthis
process
oxalic
was obtained
by oxidation
of propyleneacid
withand
the two-step
rocess,
in first
step acid
propylene
was converted
into -nitratolactic
nitric
acid.
the
two-step
in firstacid
step
converted into
second
step
leads Ittis
o o
xidation
of process,
-nitratolactic
to propylene
oxalic acid.was

-nitratolactic acid and second step leads to oxidation of -nitratolactic acid
In the first reactor, propylene was introduced where it was reacted with nitric acid.
to oxalic acid.
Propylene to nitric acid molar ratio is kept at 0.01 - 0.5. The mixture from first reactor
Nitric acid
was run into second reactor where it was reacted with oxygen. In this reactor vapor of
Nitric acid
recovery
nitric acid was continuously evolved from the top of the vessel. The stream from vessel
contains intermediate and trace amount of nitric acid was run into reservoir tank where
acid was evolved. -nitratolactic acid from reservoir was then run into autoclave where
Firstat 45 - 1000C in the presence of mixed acid as catalyst. In this step -
it was oxidized
reactor
nitratolactic
acid is converted into oxalic acid dihydrate. The crude product was then
Propylene
transfer into a crystallizer where oxalic acid crystals obtained. The slurry from
crystallizer is filtered and sent for drying operation where dried oxalic acid is obtained.

Oxygen

Oxygen

Intermediate
reservoir
Nitric acid



BLOCK DIAGRAM

Nitric acid

Carbon
monoxide

Nitric acid
recovery

First
reactor

Second
reactor

Oxygen

Catalyst

Intermediate
reservoir

Autoclave
Nitric acid
Crystallizer

Filter

Dryer

Oxalic acid

Mother
liquor
Figure: Manufacture of Oxalic acid from Propylene

oxidized at 45 - 100 C in the presence of mixed acid as catalyst. In th

-nitratolactic acid is converted into oxalic acid dihydrate. The
product was then transfer into a crystallizer where oxalic acid c
3. Oxalic
acid dimethyl
oxalate

obtained.
The slurry
fromprocess
crystallizer
is filtered and sent for drying ope
where dried oxalic acid is obtained.

RAW MATERIALS
acid dimethyl oxalate process
3. Oxalic
Basis: 1000kg oxalic acid from methyl nitrite and carbon monoxide
Raw materials
Carbon monoxide 957kg

Methyl nitrite Basis:

1000kg
1330kg oxalic acid from methyl nitrite and carbon monoxide
Carbon monoxide
957kg
Water 395kg
Methyl nitrite
1330kg

Water
395kg
REACTION
Reaction

Manufacture process
MANUFACTRING PROCESS

In this process,
gas containing
CO gas
and containing
regenerated CO
methyl
nitrite
from
Incirculating
this process,
circulating
and
regenerated
m
regeneration column was pressurized and fed to the reactor. In this vessel dimethyl
nitrite from regeneration column was pressurized and fed to the reac
oxalate was produced while methyl nitrite is mostly consumed. The dimethyl oxalate
this vessel
dimethyl
oxalate
produced
while methyl
nitrite is
and unconverted
mixture
was run
into the was
condenser
where methanol
was added.
Uncondensed
vapor contains
methyl oxalate
nitrite, water
and methanol was
drawn
to run in
consumed.
The dimethyl
and unconverted
mixture
was
regeneration
column wwhere
here NOx
and oxygen awas
re added
to regenerate
the methyl nvapour
itrite
condenser
methanol
added.
Uncondensed
co
which is to be recycled.

methyl nitrite, water and methanol was drawn to regeneration column

Condensed
oxalate from
ondenser to
was
run into the dthe
istillation
column
where
NOdx imethyl
and oxygen
are cadded
regenerate
methyl
nitrite
which is
water vapors were removed while dimethyl oxalate was sent for hydrolysis where
recycled.
water is added. After the hydrolysis of oxalate, slurry was sent to the crystallizer where
a crystal of oxalic acid is obtained. The slurry is then filtered and passed from dryer and
dried oxalic acid stored.

NPTEL



BLOCK DIAGRAM

4. Oxalic Acid from Molasses using Nitric Acid:

RAW MATERIALS:

1. Nitric Acid
2. Sulphuric Acid
3. Water
4. Molasses
5. Vanadium Pentoxide (Catalyst)


REACTION

C6H12O6 + HNO3
3 [COOH]2. 2H2O + 6NO


MANUFACTURING PROCESS:

MOLASSES& ITS PROPERTIES

Molasses is a viscous by-product of the refining of sugarcane, grapes, or sugar beets into
sugar. The word comes from the Portuguesemelao, ultimately derived from Mel, the
Latin word for "honey. The quality of molasses depends on the maturity of the source
plant, the amount of sugar extracted, and the method employed. Molasses are of various
type based on plant material from which it is produced. So different type of molasses
produced base upon on various raw material are cane molasses from sugarcane, beet
molasses from sugar beet, grape molasses from grapes .Its major constituents are-
1) Glucose35.9% 2) Fructose-5.6% 3) Sucrose2.6% 4) Water-23.5%
Initially molasses was preheated & temperature of it was increased from 37oC to 65.5oC.
After that it was fed into a CSTR. Simultaneously Nitric acid was also fed into the CSTR
along with Vanadium Pentoxide, which act as a catalyst. This mixture was mixed thoroughly
& was allowed to react for 2-3 hours. After 2-3 hours, Oxalic acid, un-reacted molasses, unreacted Nitric acid, Nitrogen Oxide was formed. Oxalic acid along with un-reacted molasses,
unreacted Nitric acid and Vanadium Pentoxide comes out from the bottom section of CSTR
and undergoes further separation process. During this process Vanadium Pentoxide gets first
get separated out with help of a filter. Oxalic acid & mother liquor (unreacted Nitric acid &
molasses) is separated in a 2-stage process. In the first stage, solution that has been filtered is
fed into a crystallizer in which oxalic acid crystals along with mother liquor comes out and
further these are separated with help of a centrifuge. After Oxalic acid gets separated, to
remove inclusion ( process by which a solvent particles get trapped inside a crystal) ,it is recrystallized by adding hot water inside a crystallizer containing these Oxalic acid crystals.

10

After separating out the mother liquor again, Oxalic acid crystals are sent into drier to remove
the moisture present on the surface of the crystals. Nitrogen Oxide gas which comes out from
the top surface of CSTR cannot be discharged directly to the atmosphere, as it can cause air
pollution, so this gas was sent into a compressor to increase the pressure & to a steam heater
to increase the temperature. After that this gas was sent to fluidized-bed reactor & in presence
of Al203catalyst, Nitrogen dioxide gas is formed. Al203after this get separated by cyclone
separator. After this process, in an absorber, Nitrogen dioxide gas was allowed to react with
water sprayed inside the absorber to produce Nitric acid & Nitrogen oxide gas. Nitric acid
(20%)obtained which is less concentrated than the Nitric acid (95%)which was used as a fed
can further be used in other industrial process and Nitrogen oxide gas can be recycled back to
stream leading to fluidized bed reactor.

BLOCK DIAGRAM

V2O5#

NO"

CS#

HNO3#

NO"
MOLASSES#

NO"

R1#

T#

S"

F#
S"

NO"

R2#
NO+NO2"

HNO3"(20%)"

FILTER"

HOT#WATER#

N1#

C1#

N2#

C2#

TD#

OXALIC"ACID"CRYSTALS"

Figure: Manufacture of oxalic acid using Molasses & Nitric Acid

11



S STEAM HEATER
R1 CSTR
T COMPRESSOR
F FLUIDIZED BED REACTOR
R2 ABSORBER
CS- CYCLONE SEPARATOR
N1 & N2 CRYSTALLIZERS
C1 & C2 CENTRIFUGE
TD- TUNNEL DRYER

ENGINEERING ASPECTS & TECHNOLOGY SELECTION

In propylene process, sulfuric acid is used which results into corrosion problem at
the oxidation step.
Oxidation reaction can be made speedy by using large reactor, thus increase in
capital investment.
Possibility of unstable by-product formation along with -nitratolactic acid leads
to explosion or decomposition.
In dimethyl oxalate process, the manufacturing process is complex, time
consuming and requires highest capital investment.
In the sodium formate process, the temperature pressure conditions are quite
high which might lead to safety issues and high equipment cost.
Thus, considering the above drawbacks of the first three processes used in
manufacturing oxalic acid, we choose the 4th process i.e., Manufacture of oxalic
acid using molasses & nitric acid.
Reasons for selecting the 4th process are as follows:
1. Abundance of raw materials
2. Good yield of oxalic acid
3. Low cost of operation
4. No pollution caused during the process
5. Simplicity of operation

12