A process report on

EXTRACTION OF FURFURAL FROM

CORN COBS

By:
Shahid Sarfaraz

CE09-10E32

Ziad Akram

CE09-10E33

H.M. Usman Saeed

CE09-10E34

Umar Farooq

CE09-10E35

Supervised by: Prof. Dr. Amir Shafeeq

Institute of chemical Engineering and Technology

University of the Punjab

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Approval Certificate

The process report entitled EXTRACTION OF FURFURAL FROM CORN COBS is

prepared by:

Shahid Sarfaraz

CE09-10E32

Ziad Akram

CE09-10E33

H.M. Usman Saeed

CE09-10E34

Umar Farooq

CE09-10E35

Under my supervision and guidance is here by approved for submission

Prof. Dr. Amir Shafeeq

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Acknowledgement

All praises to almighty ALLAH who gave us light in darkness and

gave us ability and strength to complete our research project.
We would like to thank our supervisor, Professor Dr. Amir Shafeeq
for his support and much needed direction also his perseverance with
some of our wild ideas and his motivation, guidance and kind words
always encouraged us to work with commitment.
We are also grateful to our worthy director Prof. Dr. Amir Ijaz
whos moral support always encouraged us to work dedicatedly.
We are grateful to our parents for their special prayers that helped
us achieve this tedious task from performance of practical to the
compilation of this process report.

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Abstract

Furfural was prepared from corn cobs in this study. The preparation
process consisted of crushed corn cobs, sulfuric acid and salt mixture. The
mixture was heated to about 120C for about 2 hours to extract furfural
water solution from the mixture. From the furfural water system was
furfural was extracted by using ether. Ether extract furfural from the
furfural water system. As ether has low boiling point so furfural is
recovered from ether by simply heating the solution to about 33C. Results
suggest that percentage yield of furfural increases by increasing the
concentration of sulfuric acid.
Different test were performed for the identification of furfural.
Molischs test
Bials test

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Table of Contents:
Chapter #

Contents

Introduction

Page #
1

1.1 Discovery of Furfural

1.2 Industrial development of furfural

1.3 Industrial Application of Furfural

Literature Review

2.1 Furfural

2.2 Important Raw Materials for Furfural Production

2.3 Natural Sources of Furfural

2.4 Yield of Furfural on Selected Raw Material

2.5 Different processes for the production of furfural

2.6 Chemistry of formation of Furfural

2.7 Manufacturing steps for Furfural

2.8 Properties of Furfural

10

2.9 Furfural and their derivatives

12

Experimental Work

13

3.1 Apparatus

13

3.2 Raw Material

13

3.3 Procedure

13

3.4 Observation and Calculation

14

3.5 Results

16

3.6 Identification Tests

17

Conclusion

18

Bibliography

19

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Chapter 1: INTRODUCTION
1.1 Discovery of Furfural:
In 1821 the German scientist Dobereiner first discover furfural. In 1832 Emmett
observed that furfural can be obtained from most vegetable substances.
In 1840 Stenhous assigned the correct empirical formula, C5H4O2 of furfural and
recognized the resin-forming tendency of furfural. In 1845 Fownes proposed the name
"furfurol" (furfur - bran; oleum - oil). In the US the suffix "ol" has been changed to "al" due
to the aldehyde function. The product describe by him was almost colourless when freshly
prepared, but was observed to darken on standing. The boiling point was reported to be 168C
and specific gravity 1.1006 at 27C. Somewhat later, Stenhous speculated on the nature of
vegetative materials which give rise to the furfural on treatment with sulphuric acid. He
proposed that, under these conditions, all plant materials would produce furfural or some
related product. [1]

1.2 Industrial development of furfural:

In 1915 researchers of the National Bureau of Chemistry (US) investigated
corncobs as feedstock for the manufacture of furfural. During a research project on the
digestibility of oat hulls for use in cattle feed, Brownlee demonstrated that the huge Quaker
Oats stockpiles of cereal waste were a potential source of furfural. In 1922 Furfural came
available in quantities of several tons per month from the Quaker Oats Company cereal mill
in Cedar Rapids (Iowa, USA).
In 1923 Durite Plastics Inc. is the first manufacturer of phenol-furfural resins as
long-flowing fast-curing phenolics for production of molding compounds. In 1925 cold-molding
of resin-bonded abrasive wheels with furfural. In 1926 wood rosin purification with furfural by
an extractive distillation technique was developed.
In 1933 first refining unit for lubricating oils with furfural built by a subsidiary of the
Texas Company (Texaco), the Indian Refining Company. In 1942 separation and
purification of C4 hydrocarbons by extractive distillation with furfural. For the manufacture of
synthetic rubber enormous quantities of pure 1,3-butadiene were needed. Corncobs and
cottonseed hulls based plants were added as feedstocks to raise the furfural capacity.

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Du Pont starts the production of adiponitrile for the manufacture of nylon 6-6 from
furfural. Furan, tetrahydrofuran and dichlorobutane are the chemical intermediates in this four
step synthesis. This route was instrumental in the development of Polytetramethylene ether
glycol in 1949.In 1951 Du Pont expand the use of furfural was responsible for the construction
of a new facility in Omaha Nebraska. In 1961 du Pont abandons the adiponitrile process from
furfural for the butadiene hydrocyanation route. Du Pont starts up a tetrahydrofuran capacity
based on the Reppe synthesis using acetylene and formaldehyde.
In 1953 furfuryl alcohol was commercially available. Today it is the largest volume
derivative of furfural. Tetrahydrofuran available from C4 hydrocarbons (butadiene), available
from petroleum.
In mid-50, during a joint venture between Quaker Oats and a Dominican sugar mill,
nowadays owned by the Central Romana Corporation (1983) FF production was started
up outside the US based on sugarcane bagasse.
In 1958 furan resins as binders in the foundry industry with the furan NO-BAKE process
(furan - urea resins) was developed. Quaker's chemical division has built an additional furfuryl
alcohol production facility in Geel, nearby Antwerp (Belgium) in 1972 and it was expanded in
1975 for furfuryl alcohol. In 1980 furfural or furfuryl alcohol modified phenolic resins as binders
in the refractory and carbon industry was introduced.
In 1994 Incorporation of International Furan Chemicals B.V. in the Netherlands
by a group of people who have been involved with the highly specialized market of furfural,
furfuryl alcohol and its derivatives for many years. International Furan Chemicals USA
was incorporated in recognition of the North American market in 1995. In 1998 The Belgian
Furfuryl alcohol production facility becomes an independent entity - The name of the new
company is Trans Furans Chemicals. Trans Furans Chemicals is leader in furfuryl alcohol
production worldwide. [1]

1.3 Industrial Application of Furfural:

Refining of lubricating oils & decolorizing agent:

Furfural thanks several large scale applications to its solubility characteristics and its

easy recuperation by steam distillation. Furfural has the unique property to dissolve aromatics
and other unsaturated olefins. Today all major oil companies use furfural as selective solvent
in the refining of lubricating oils. The first refining unit was built by a subsidiary of Texaco,
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the Indian Refining Company. This technology lead to production of high quality motor oil with
improved temperature-viscosity properties. Aromatics, polar components, mercaptans are
removed from petroleum by means of furfural extraction. Furfural can also be used as
decolorizing agent to refine crude wood resin. [1]
In Pakistan, furfural extraction unit is present in National Refinery Limited,
Karachi. Lube oil (de asphalted oil) enters the rotating disc column from two points lower
than the entrance points of the solvent .The solvent (furfural) is heavier than the feed
therefore solvent moves downward and the feed moves upward the column is completely
filled. As the solvent moves downward it absorbs about 80% of the aromatics and these moves
to the bottom and leaves as extract. The paraffin along with the solvent leaves the rotating
disc column from the top and is called raffinate. [2] [4]

Other minerals oils can be treated with furfural to improve their quality. Diesel fuel can
be frequently refined with furfural, Feed stocks for carbon black plants are also treated with
furfural, vegetable, animals and fish liver oil can also be refined through technology in which
furfural is used as a solvent. For instance a concentration of vitamin A and D from fish liver
oils is achieved by using furfural in this way.

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Purification technology for C4 and C5 hydrocarbons:

During the Second World War the purification technology of butadiene was developed

in the United States for the manufacture of synthetic rubber. By extractive distillation with
furfural butadiene or isoprene can be separated from other C4 and C5 hydrocarbons,
respectively.

Reactive solvent and good wetting agent:

Furfural is unusually effective as a solvent for phenolic resins. In the manufacture of

abrasive wheels, brake linings and refractory products for the steel industry furfural is known
as a reactive solvent and excellent wetting agent.

Unique chemical feedstock for other furan derivatives:

However, the main outlet of furfural is as chemical feedstock for the production of

furfuryl alcohol and for other 5-membered oxygen-containing heterocyclic, i.e. furan, methyl
furan, acetyl furan, furfurylamine and furoic acid. [1]

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Chapter 2: Literature Review

During the preparation of acid by Dobereiner process, a considerable quantity of
vegetable oil which, at first, might be considered as arising from the excess of hydrogen and
carbon in the process; but a special inquiry has convinced me that this is not the case,
although the oil is so abundant that it may actually be observed floating in drops down the
neck of retort. When the sulfuric acid is so far diluted as not to carbonize the mixture, at the
heat of boiling water, little else than this spicy oil passes over by distillation; but as soon as
the matter become, black, its formation ceases, and if we begin at once with sulfuric acid
about one half diluted it does not appear at all; but instead of it, strong formic add, without
any foreign odour and quite colourless this volatile would not be regarded as objectionable by
many, since it imparts an aroma like that of cassis of cinnamon, and a taste somewhat similar
to that produced by hydro cyanic acid.
When free from water, and freshly rectified it is nearly colourless but after a few hours
standing it acquires brownish tint which eventually deepens almost to blackness, when in
contact with water or when not properly rendered anhydrous, it is less subject to change and
merely assumes a yellow colour, its odour resembles that of a mixture a bitter almond oil and
oil of cassia, but has less fragrance, its specific gravity is 1.168 at 60F and its boiling point is
323F.It distils at that temperature without alteration, it dissolve to a large extent in cold water
and also in alcohol, its solution in conc. sulfuric add has a magnificent purple colour and it
decompose by water .nitric add with the aid of heat attacks the oil with prodigious violence,
evolving copious red fumes and generating oxalic acid which appears to be sole product. It
dissolved in a solution of KOH forming a deep brown liquid from which acid precipitates a
resinous mass with slight heat, it explodes when acted upon by metallic potassium.

2.1 Furfural:
Furfural also known as (2-furfural aldehydes, furfural, 2-Furan Carboxaldehyde,
furfuraldehyde, fural) is the principal member of five membered heterocyclic compounds
called furans which are characterized by an unsaturated ring of four carbon atom and one
oxygen atom. Its chemical formula is OC4H3CHO:

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2.2 Important Raw Materials for Furfural Production:

Raw Material

Average Furfural Content % Huaxia

Furfural Technology

Corncobs

11.0

Wood

6.0

Cottonseed hull bran

9.5

Bagasse
Rice hulls

8-11
6.5
[11]

2.3 Natural Sources of Furfural:

1. Rice Hush
Paddy consists of 30% husk and 70% rice 5 tons per day furfural requires 80-tons/day
rice husk, which corresponds to 270-tons/day, and 190 tons per day rice. Rice husk is available
at Rs. 7090 per ton, depending upon the location of the source. Most of the Mills are willing
to provide free of charge, but considering the low derivity of material, the transportation and
storage cost over a large portion of the delivered price. An ideal arrangement should be to
locate the plant next to the modem rice mill.
2. Corn Cobs
The yield of furfural from corncob is the highest and this makes corncob a desirable
raw material. Rafhan maize products had indicated willing to sell corncobs. The quality of cobs
available from Rafhan is five thousand tons In April December season. This quantity is
sufficient for the production of 1500 tons furfural per year.
3. Bagasse
Bagasse is used as fuel in sugar mills, and in some cases for the manufacture of paper
and hard board. As sugar cane production in Pakistan is large so bagasse is available in
abundant quantity moreover, the availability of bagasse as a raw material for the product of
furfural can be increased by using gas fired boiler in sugar mills. As storage of bagasse is
difficult and expensive so the furfural unit should be located near a sugar mill. Five-tons/day
furfural production requires 30-tons/day bagasse, which is available from 200-tons/day sugar
cane. There are about 70 sugar mills in Pakistan and almost of these mill's bagasse is used as
boiler fuel. Using the bagasse as a raw material for the production of furfural, which is high
cost organic chemical we can earn a lot.
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2.4 Yield of Furfural on Selected Raw Material:

This yield is reported on the basis of % weight of Raw Material per day.
Raw Material

Pentosanes Content

Furfural yield in
Industrial operation

Corn cobs

30-32

10

Rice husk

16-18

Bagasse

25-27

8-9

Cotton husk

27

8-9

Oat husk

Minimum 32

10

Almond husk

Minimum 30

9-10

Olive press cake

21-23

5-6
[7]

2.5 Different processes for the production of furfural:

The conventional processes for the production of furfural are as follow:

1. Agrifurnace Process:
This process requires super phosphate or phosphoric acid or a catalyst.
2. Quaker Oats process:
This process requires sulphuric acid as a catalyst.
3. SAVO process:
This process does not require a separate catalyst.
All of the above process react at elevated pressures and involved digestion of the
catalyst when heated by few materials with super heat steam. Thus furfural flashes out from
the sector with steam. Then this product of furfural and steam is condensed to produce dilute
solution, from which furfural may be recovered fractional or vacuum distillation. The usual
raw material can be used in all above processes. The savo purpose have has comparatively
simple technology less maintenance problem and trouble free operation characteristics.

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2.6 Chemistry of formation of Furfural:

There are two materials used in the formation of Furfural:
1. Non Pentosanes
2. Pentosanes
1. Non Pentosanes:
Cellulose and polyuronic acids can be converted to furfural under suitable
conditions. These are non pentosanes material.
In the case of cellulose the conversion to furfural takes place via glucouronis acid.
Pectin which is now regarded as poly uronic acid also produced furfural under similar
conditions. The uronic acid is readily decarboxiated on boiling, pentose, xylon or rabinose are
formed.
Another material that can be converted into furfural is ascorbic acid boiled with
hydrochloric ascorbic acid gives a quantitative determination of furfural. [6]
2. Pentosanes:
The conversion of pentosanes to furfural in two steps
Hydrolysis of Pentosanes to Pentoses:
Pentosanes in hemicelluloses is hydrolysed with dilute mineral acids at relatively low
temperature to pentosanes liquor. A major 75% of these pentosanes is readily hydrolysable
to pentoses.
(C5H8O4)n +nH2O

nC5H10O5

Conversion of Pentosanes to Furfural:

The formation of furfural from pentoses is an ordinary process of dehydration with the
elimination of three molecules of water.
The following three step change has been purposed for the conversion of a pentose to
furfural and it is supported by spectroscopic evidence. [6]

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2.7 Manufacturing steps for Furfural:

There are seven essential steps for the manufacturing of furfural:

1. Pressure cooking of raw material with dilute acid

2. Condensation of cooker vapours
3. Azothropic distillation of furfural
4. Condensation of two layers and decantation of water layers
5. Distillation water layer to recover methanol
6. Drying of furfural
7. Colouring and filtration

2.8 Properties of Furfural:

General Properties
Molecular weight

96.08

Boiling point (1 atm),C

161.7

Freezing point ,C

-36.5

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Refractive Index
At 20 C

1.5621

At 25C

1.5231

Density at 20 C, g/cm3

1.1598

Vapor density

3.3

Critical Pressure , Mpa

5.502

Critical temperature ,C

397

Solubility in , wt%
Water

8.3

Ether

Thermodynamic Properties
Heat of Vaporization(liq),kJ/mol

42.8

Heat capacity (liq), j/(g.K)

20-100 C

1.74

Heat of Combustion(liq),kJ/mol

2344

Enthalpy of formation ,kJ/mol

-151

Fluid Properties
Visocosity,mpa.s,25 C

1.49

Surface Tension, (dyn/cm)

At 29.9 C

40.7

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Electrical Properties
Dielectric Constant 20C

41.9

Flammability Properties
Explosion limits (in air),vol %

2.1-19.3

Flash point,C,tag closed cup

61.7

Auto ignition Temperature,C

315
[3]

Thermal Stability:
Furfural has rather high order of stability towards heat in the absence of catalyst and
oxygen. The initial decomposition temperature has been found to be 565 C for a contact
period of 20 seconds. [5]

Storage and Transportation:

Furfural is not corrosive to metal and can be shipped mild steel tank car or trucks or
drums. Storage in either aboveground or underground installations is satisfactory. For
extended storage with maximum stability, cool storage conditions and nitrogen blanketing are
recommended. Because furfural is an excellent and penetrant, care must be taken that all
joints are secure and that the pump and valve packing are in good condition. Unopened drums
may be stored in cool locations for months without appreciable change in physical properties.
[5]

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2.9 Furfural and their Derivatives:

In commercial terms, the most important intermediary derived from furfural is furfural
alcohol (FA). This Furfural alcohol primarily used to make furan resins, but it may also be
converted into tetra hydro furfuryl alcohol (THFA).

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CHAPTER 3: Experiment Work

3.1 Apparatus:
Apparatus consist of following parts
1) Reaction Flask
2) Long Glass Tube
3) Condenser
4) Collecting Flask
5) Heating media
6) Stand

3.2 Raw Materials:

1) Salts
2) Corncobs
3) H2SO4
4) Ether
5) Water

3.3 Procedure:
Corn cobs (+40 mesh size), H2SO4 & Salt was put in to the Reaction flask.
Reaction flask was connected to long vertical tube that was provided so as to provide sufficient
length of vapors of Furfural so as to enhance the concentration of Furfural. This long tube
was then connected to the condenser so that water flows continuously so as to condense the
vapors of Furfural which are then collected in a collecting flask. Heating media which was
used is electric heater and temperature was set 1200C so that reaction was started. For all the
samples the weight (Corn cobs) to volume (H2SO4) ratio is set to be 1:5. Volume of the
solution is set to be 750ml. The time of heating is fixed as 125 min. [7]

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Apparatus diagram

Extraction
Furfural can be extracted from water by using solvent extraction employing ether as a
solvent. After extraction the upper layer will contain furfural and ether and the lower layer
consists of water. Furfural can be separated from the upper layer by evaporating ether.

3.4 Observation and Calculation:

Sample 1:
Weight of corn cobs=150g
Percentage of H2SO4=5%
Volume of H2SO4=38 ml
Volume of water=712 ml
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Salt taken=150g
Total sample collected=120 ml
Addition of Ether=120 ml
Upper layer=78 ml
Lower layer=162 ml
After evaporation the weight of furfural obtained=
Sample 2:

100=2.3%

Weight of corn cobs=150g

Percentage of H2SO4=10%
Volume of H2SO4=77 ml
Volume of water=673 ml
Salt taken=150g
Total sample collected=150 ml
Addition of Ether=120 ml
Upper layer=110 ml
Lower layer=160 ml
After evaporation the weight of furfural obtained=
Sample 3:

100=4.6%

Weight of corn cobs=150g

Percentage of H2SO4=15%
Volume of H2SO4=115 ml
Volume of water=635 ml
Salt taken=150g
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Total sample collected=210 ml

Addition of Ether=120 ml
Upper layer=130 ml
Lower layer=200 ml
After evaporation the weight of furfural obtained=

100=7.6%

100=8.3%

Sample 4:
Weight of corn cobs=150g
Percentage of H2SO4=20%
Volume of H2SO4=153 ml
Volume of water=597 ml
Salt taken=150g
Total sample collected=425 ml
Addition of Ether=120 ml
Upper layer=190 ml
Lower layer=355 ml
After evaporation the weight of furfural obtained=

3.5 Results:
Sr No.

Acid Conc. Used

Yield of furfural

(%)

(%)

2.3

10

4.6

15

7.6

20

8.3

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%AGE YIELD OF FURFURAL

Acid Concenteration Used Vs Yield

of Furfural

9
8
7
6
5
4
3
2
1
0
0

10

15

20

25

% ACID(H2SO4) CONCENTERATION USED

3.6 Identification Test:

We have conducted following tests for the confirmation of the sample of furfural prepared.
Molischs test
Molischs reagent consists of 10% -Napthol in ethanol. In the presence of furfural this
reagent will show Purple color.

Bials test
In this test the reagent used is orcinol, HCL & Ferric chloride. In the presence of this
reagent furfural will show blue green color.

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Chapter 4: Conclusion
After performing the experiment and research we observed that furfural formed in
digestion flask might be much more in quantity but is destroyed through auto polymerization
in the presence of acid (H2SO4 as catalyst). Actually during the formation of furfural two
chemical reactions occur in digestion flask. Firstly the formation of furfural through hydrolysis
and dehydration, Secondly the formation of furfural in to its polymer producing furfural tan.
Furfural yield Increases rapidly as we increased the concentration of acid up to
15%.When acid concentration is increased to 20% the yield trend slightly decreases because
it is very difficult to isolate furfural produce in liquid phase by the standard method of
laboratory separation i.e. by solvent extraction using Ether.
The Factors upon which the yield of furfural depends are as following:

Acid/Solid (volume to weight Ratio)

Temperature

Time of digestion

Pressure

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Bibliography:
1. International Furan Chemicals B.V. 2013 .Design by Mindwarp Internet Solutions.
2. Petroleum Refining V.2: Separation Processes by Jean-Pierre Wauquier
3. Tetra furans chemicals, Physical Properties of furfural 1st version 12/22/200
4. Private Communication (National Refinery Ltd Karachi, Pakistan)
5. Kirk, .R.E. and Othmer. D.F. Encyclopedia of Chemical Technology: Inter Science
Publishers, N. York, 1st Ed.
6. Dunlop, A.P. and Peters. FN: The Furans American Chemical Society, Monograph
series. Reinhold publishing Corporation, N. York 1953.
7. K.J Zeitsch, The chemistry & technology of furfural & its many by product, Elsevier
science (1st edition) 2000.
8. Making and Marketing furfural Geneva 1978.
9. Dunning, J.W. & Lathrop, E.C. md. Engg. Chem. 37, 24 (1945)
10. Dunlop, A.P. and Peters, F.N. md. Eng. Chem. 32, 1639 (1940)
11. Furfural Gold from Garbage David Tin Win Faculty of Science and Technology,
Assumption University Bangkok, Thailand

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