process report (ce-32,33,34,35,)

8/20/2019 Process Report (CE-32,33,34,35,)

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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, ProfessorDr. Am ir Shaf eeq

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 Pro f . Dr . Ami r I j az

who’s 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 120⁰C 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 33⁰C. Results

suggest that percentage yield of furfural increases by increasing the

concentration of sulfuric acid.

Different test were performed for the identification of furfural.

• Molisch’s test

• Bial’s test


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Table of Contents:

Chapter # Contents Page #1 Introduction 1

1.1 Discovery of Furfural 1

1.2 Industrial development of furfural 1

1.3 Industrial Application of Furfural 2

2 Literature Review 5

2.1 Furfural 5

2.2 Important Raw Materials for Furfural Production 6

2.3 Natural Sources of Furfural 6

2.4 Yield of Furfural on Selected Raw Material 7

2.5 Different processes for the production of furfural 7

2.6 Chemistry of formation of Furfural 8

2.7 Manufacturing steps for Furfural 9

2.8 Properties of Furfural 10

2.9 Furfural and their derivatives 12

3 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

4 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 168⁰C

and specific gravity 1.1006 at 27⁰C. 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 feedstock’s 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 ReviewDuring 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 60°F and its boiling point is

323⁰F.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 8-11

Rice hulls 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. 70—90 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 6

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

At 25°C

1.5621

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

Ether

8.3

∞

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 20°C 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= .

∗ 100=2.3%

Sample 2:





Salt taken=150g



Upper layer=110 ml

Lower layer=160 ml

After evaporation the weight of furfural obtained= ∗ 100=4.6%

Sample 3:





Salt taken=150g


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Upper layer=130 ml

Lower layer=200 ml


∗ 100=7.6%

Sample 4:





Salt taken=150g



Upper layer=190 ml

Lower layer=355 ml


∗ 100=8.3%

3.5 Results:

Sr No. Acid Conc. Used

(%)

Yield of furfural

(%)

1 5 2.3

2 10 4.6

3 15 7.6

4 20 8.3


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3.6 Identification Test:

We have conducted following tests for the confirmation of the sample of furfural prepared.

Molisch’s test

Molisch’s reagent consists of 10% α-Napthol in ethanol. In the presence of furfural this

reagent will show Purple color.

Bial’s test

In this test the reagent used is orcinol, HCL & Ferric chloride. In the presence of this

reagent furfural will show blue green color.

0

1

2

3

4

5

6

7

8

9

0 5 10 15 20 25

% A G E Y I E L D O F F U R F U R A L

% ACID(H2SO4) CONCENTERATION USED

Acid Concenteration Used Vs Yield

of Furfural


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