production of aniline from ammonolysis of phenol- 2010-ch-09,61,65,87

8/10/2019 Production of Aniline From Ammonolysis of Phenol- 2010-CH-09,61,65,87

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Mini project- Production of Aniline from ammonolysis of Phenol

PROJECT TITLE:

A N I L I N E P R O D U C T I O N[By The Ammonolysis Of Phenol]

5TH

SEMESTER [SECTION A]

SESSION [2010-2014]

SUBMITTED TO:

SIRASIF AKHTAR

SUBMISSION DATE

Nov 21st

, 2012

DEPARTMENT OF CHEMICAL ENGINEERING

UNIVERSITY OF ENGINEERING &TECHNOLOGY,LAHORE


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If you have knowledge, let others light their candles at it.

Margaret Fuller


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CONTENTS |

CONTENTS

GROUP MEMBERS --------------------------------------------------------------------------------------------------------------------------------------- I

ABSTRACT ------------------------------------------------------------------------------------------------------------------------------------------------- II

PREFACE -------------------------------------------------------------------------------------------------------------------------------------------------- III

ANILINE

AN ORGANIC COMPOUND ------------------------------------------------------------------------------------------------------------- 4

PROPERTIES OF ANILINE[1]

------------------------------------------------------------------------------------------------------------------------------ 4

PRACTICAL APPLICATIONSOF ANILINE ----------------------------------------------------------------------------------------------------------------- 4

PROCESS SELECTION ----------------------------------------------------------------------------------------------------------------------------------- 5

EXISTING PROCESSES[3]

---------------------------------------------------------------------------------------------------------------------------------- 5

Hydrogenation of Nitrobenzene ------------------------------------------------------------------------------------------------------------- 5

By Ammonolysis of Chlorobenzene --------------------------------------------------------------------------------------------------------- 6

By Ammonolysis Of Benzene ----------------------------------------------------------------------------------------------------------------- 6

By Ammonolysis Of Phenol[4 ]

----------------------------------------------------------------------------------------------------------------- 7

SUMMARY ----------------------------------------------------------------------------------------------------------------------------------------------- 7

ANILINE PRODUCTION

BY THE AMMONOLYSIS OF PHENOL ----------------------------------------------------------------------------- 7

CAPACITY SELECTION: ----------------------------------------------------------------------------------------------------------------------------------- 8

Industrial Aspect[5 ]

------------------------------------------------------------------------------------------------------------------------------ 8

Global Supply And Demand ------------------------------------------------------------------------------------------------------------------- 8

Our Goal ------------------------------------------------------------------------------------------------------------------------------------------- 8

PROCESS DESCRIPTION ---------------------------------------------------------------------------------------------------------------------------------- 9

Fresh Feed: -------------------------------------------------------------------------------------------------------------------------------------- 10

Surge Tank: -------------------------------------------------------------------------------------------------------------------------------------- 10

Chemical Reactor: ----------------------------------------------------------------------------------------------------------------------------- 10

Distillation Column: --------------------------------------------------------------------------------------------------------------------------- 10

Ammonia Recycle: ----------------------------------------------------------------------------------------------------------------------------- 10

Drying column: --------------------------------------------------------------------------------------------------------------------------------- 10

Purification column: -------------------------------------------------------------------------------------------------------------------------- 10

APPENDIXI -------------------------------------------------------------------------------------------------------------------------------------------- IV

REFERENCES ---------------------------------------------------------------------------------------------------------------------------------------------- 1


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GROUP MEMBERS |I

GROUP MEMBERS

2010CHEM09

[K]A L I M [U]L L A H

2010CHEM61

[Z]A I D [M]A S O O D

2010CHEM65

[A]H M A D [I]J A Z

2010CHEM87

[S]H I R A Z [D]A U D


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ABSTRACT |II

ABSTRACT

This report is been written under the supervision of a group of fourmembers. Data included in this

literature is authentic and accurate, mostly taken from reliable sources.

We would like to thank a number of people who encouraged and helped us in writing and compiling

this report including, Seniors from University of Engineering & Technology, Lahore, who enable us

to do so. We can assure the reader that this may be our first report of its own kind, because we have

put a bit of "heart and soul" into it! Therefore, we hope that you will find this report immensely

educative & informative.

AUTHORS


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PREFACE |III

PREFACE

This project simply talks about the Production Of Aniline By Ammonolysis Of Phenol. We have

tried our best to gather as much information as we can and to present our research in the form of

completely arranged booklet.

As far as its contents are concerned, it includes the necessary introduction to the topic and the basic

knowledge about our topic i.e. Production of Aniline by ammonolysis of Phenol .The technique

which is our topic of concern is a very unique process that is being utilize mostly in middle east and

western Europe for the production of Aniline.

During completing this assignment it was our intention to cover all major information regarding to

our process, its benefits, and its other features.

In presenting a good deal of information concerning the topic of this mini project, every group

member did different jobs in order to divide the bulk of this assignment. We collectively gathered

information from the internet and various books to present the data in the complete form.

In the end, we would like to thank again all the people who helped us. We hope that our assignment

will prove beneficial to our class mates as well as the others seeking information about the Aniline

Production and about this contemporary technique.


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PREFACE |4

ANILINEAN ORGANIC COMPOUND[A brief review]

Aniline, phenyl-amine or amino-benzene is an organic compound with the formula C6H5NH2.

Consisting of a phenyl group attached to an amino group, aniline is the prototypical aromatic amine.

Being a precursor to many industrial chemicals, its main use is in the manufacture of precursors topolyurethane. Like most volatile amines, it possesses the somewhat unpleasant odor of rotten fish. It

ignites readily, burning with a smoky flame relating it to aromatic compounds. Aniline is colorless,

but it slowly oxidizes and revivifies in air, giving a red-brown tint to aged samples.

In commerce, three brands of aniline are distinguished: aniline oil for blue, which is pure aniline;aniline oil for red, a mixture of equimolecular quantities of aniline and ortho- and para-toluidines;

and aniline oil for safranine, which contains aniline and ortho-toluidine, and is obtained from the

distillate of the fuchsine fusion.

PROPERTIES OF ANILINE[1]

Aniline when freshly prepared is a colorless oily liquid. It has a characteristic unpleasant odor and is

not poisonous in nature. It is heavier than water and is only slightly soluble. It is soluble in alcohol,

ether and benzene. Its color changes to dark brown on standing.

Aniline in solution adsorbs strongly to colloidal organic matter, which effectively increases itssolubility and movement into ground water. It is also moderately adsorbed to organic material in the

soil; adsorption is dependent upon soil pH (pKa of 4.596). It will slowly volatilize from soil and

surface water (vapor pressure 0.67 mm Hg @ 25 C) and is subject to biodegradation. Although

rapidly degraded in the atmosphere, aniline can be deposited in the soil by wet and dry deposition,

and by adsorption on aerosol particles.

Aniline reacts with any free radicals produced by sunlight in the atmosphere.This radical scavenging

reactivity has been shown to inhibit the production of Photochemical smog by sunlight. Aniline

apparently undergoes direct photolysis and has considerable absorption of wavelengths above 290

nanometers. Photoproducts formed from aniline in the atmosphere include N-methylaniline, N, N-dimethylaniline, Isomeric hydroxyanilines and phenols. The half-life of atmospheric Aniline due to

photo degradation has been estimated at 3.3 hours.

PRACTICAL APPLICATIONS OF ANILNE

Aniline is an important organic compound which is used mainly used in the preparation of other

chemicals, industrial as well as on laboratory scale. These applications are given below:

It is used in the preparation of diazonium compounds which are used in dye industry.

Anils (Schiff's bases from aniline) are used as antioxidants in rubber industry.

It is used for the manufacture of its some derivatives such as acetamide, sulphanilic acid and

sulpha drugs, etc.

It is used as an accelerator in vulcanizing rubber.


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PREFACE |5

The largest application of aniline is for the preparation of methylene diphenyl di-isocyanate

(MDI).

Other uses include rubber processing chemicals (9%),herbicides (2%), and dyes and pigments

(2%)

As additives to rubber, aniline derivatives such as phenylenediamines and diphenylaminesare

antioxidants.

Illustrative of the drugs prepared from aniline isparacetamol (acetaminophen,Tylenol).

The principal use of aniline in the dye industry is as a precursor toindigo,the blue ofblue jeans.

Aniline is also used at a smaller scale in the production of theintrinsically conducting polymer

polyaniline.

Aniline is also used to produce medicinal and pharmaceuticals, resins, varnishes, perfumes, shoe

blacks, photographic chemicals (hydroquinone), explosives.

PROCESS SELECTION[Choice Of A Prefect Method]

Combination of steps is known as a process, while A chemical process is a method or mean of

somehow changing one or more chemicals or chemical compounds into a useful product.

The process selection is also based on the fact that in Pakistan the production of nitrobenzene

[important constituent] is very less and hence not abundantly available in the market and hence is

expensive similar to the case in Western Europe. But in some countries such as United States of

America where nitrobenzene is abundantly available in the market at a very cheap price the first

process is mostly used.

More than a few methods are there for the production of Aniline. Selection of a particular method

depends upon many factors which are characterizing that specific area. Like:

Climatic conditions

Cost of Raw Material

Government subsidy scheme

Capital Cost

Payback period etc.

EXISTING PROCESSES[3]

Following processes are currently being used all over the world for the production of aniline,

depending upon the various factors mentioned above. These processes are:

Hydrogenation of nitrobenzene

Ammonolysis of chlorobenzene

By ammonolysis of Benzene

Ammonolysis of Phenol

HYDROGENATION OFNITROBENZENE

Nitrobenzene is the classical feedstock for Aniline manufacture. Recently less chlorobenzene and

Phenol are being used in aniline manufacturing processes in several countries. The reduction of

nitrobenzene with iron turnings and water in the presence of small amounts of hydrochloric acid is

the oldest form of industrial aniline manufacture. It would certainly have been replaced much earlier

by more economical reduction methods if it had not been possible to obtain valuable iron oxidepigments from the resulting iron oxide sludge. However, the increasing demand for aniline has far
http://en.wikipedia.org/wiki/Methylene_diphenyl_diisocyanatehttp://en.wikipedia.org/wiki/Rubberhttp://en.wikipedia.org/wiki/Herbicideshttp://en.wikipedia.org/wiki/Paracetamolhttp://en.wikipedia.org/wiki/Tylenolhttp://en.wikipedia.org/wiki/Indigo_dyehttp://en.wikipedia.org/wiki/Jeanshttp://en.wikipedia.org/wiki/Conducting_polymerhttp://en.wikipedia.org/wiki/Polyanilinehttp://www.lookchem.com/Aniline/http://www.lookchem.com/Phenol/http://www.lookchem.com/Phenol/http://www.lookchem.com/Aniline/http://en.wikipedia.org/wiki/Polyanilinehttp://en.wikipedia.org/wiki/Conducting_polymerhttp://en.wikipedia.org/wiki/Jeanshttp://en.wikipedia.org/wiki/Indigo_dyehttp://en.wikipedia.org/wiki/Tylenolhttp://en.wikipedia.org/wiki/Paracetamolhttp://en.wikipedia.org/wiki/Herbicideshttp://en.wikipedia.org/wiki/Rubberhttp://en.wikipedia.org/wiki/Methylene_diphenyl_diisocyanate


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PREFACE |6

surpassed the market for the pigments, so that not only catalytic hydrogenation processes (both

liquid- and gas-phase) but also other feed stocks have been used for aniline production.

The modern catalytic gas-phase hydrogenation processes for nitrobenzene can be carried out using a

fixed-bed or a fluidized-bed reactor.

Rayer and Allied work with nickel sulfide catalysts at 300-475 C in a fixed bed. The activation of

the hydrogenation catalysts with Cu or Cr, and the use of different supports and catalyst

sulfurization methods with sulfate, H2S or CS2 all belong to the expertise of the corresponding

firms. The selectivity to aniline is more than 99%. The catalytic activity slowly decreases due to

carbon deposition. However, the catalyst can be regenerated with air at 250-350C and subsequent

H2 treatment. Similar processes are operated by Lonza with Cu on pumice, by ICI with Cu, Mn, or

Fe catalysts with various modifications involving other metals, and by Sumitomo with a Cu-Crsystem.

The gas-phase hydrogenation of nitrobenzene with a fluidized-bed catalyst is used in processes

from BASF, Cyanamid and Lonza. The BASF catalyst consists of Cu, Cr, Ba, and Zn oxides on a

SiO2 support; the Cyanamid catalyst consists of Cu/SiO2. The hydrogenation is conducted at 270-

290 C and 1-5 bar in the presence of a large excess of hydrogen (H2:nitrobenzene=ca. 9:1). The

high heat of reaction is removed by a cooling system which is built into the fluidized bed. The

selectivity to aniline is 99.5%; the nitrobenzene conversion is quantitative. The catalyst must be

regenerated with air periodically.

BY AMMONOLYSIS OF CHLOROBENZENE

An alternate manufacturing route for aniline is the ammonolysis of chlorobenzene or of phenol. For

example, in the Kanto Electrochemical Co. process, chlorobenzene is ammonolyzed to aniline with

aqueous NH3 at 180-220 C and 60-75 bar in the presence of CuCl and NH3Cl ("Niewland catalyst")

Aniline can be isolated with 91 % selectivity from the organic phase of the two-phase reaction

product.

BY AMMONOLYSIS OF BENZENE

Du Pont has developed an interesting new manufacturing process for aniline. Benzene and ammonia

can be reacted over a NiO/Ni catalyst containing promoters including zirconium oxide at 350C and

300 bar to give a 97% selectivity to aniline with a benzene conversion of 13%

Since the hydrogen formed in the reaction reduces the NiO part of the catalyst, catalyst regeneration

(partial oxidation) is necessary. Despite inexpensive feed stocks, industrial implementation is still

thwarted by the low benzene conversion and the necessary catalyst re-oxidation.


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PREFACE |7

BY AMMONOLYSIS OF PHENOL[4]

As an alternative, aniline is also prepared fromphenoland ammonia, the phenol being derived from

thecumene process.Dow stopped operation of a similar process for aniline in 1966. Phenol can also

be subjected to gas-phase ammonolysis with the Halcon/Scientific Design process at 200 bar and

425C

Al2O3.SiO2(possible as zeolite) and oxide mixtures of Mg, B, Al, and Ti are used as catalysts; these

can be combined with additional co-catalysts such as Ce, V, or W. The catalyst regeneration required

previously is not necessary with the newly developed catalyst. With a large excess of NH3, the

selectivity to aniline is 87-90% at a phenol conversion of 98%. The byproducts are diphenylamine

and carbazole. This process has been operated since 1970 by Mitsui Petrochemical in a plant which

has since been expanded to 45 000 tons per year. A second plant with a capacity of 90000 tons per

year was started up by US Steel Corp. (now Aristech) in 1982.

In 1977, Mitsui Petrochemical started production of m-toluidine by the reaction of m-cresol with

ammonia in a 2000 ton-per-year plant, analogous to the phenol ammonolysis. Thus, there is another

manufacturing path besides the conventional route (nitration of toluene and hydrogenation of m-

nitrotoluene).

SUMMARY

Each process carries its own importance regarding purity, cost, future demands. There are mainly

two processes which are mostly applied at the industrial scale for the preparation of aniline.

By hydrogenation of nitrobenzene

By ammonolysis of Phenol

The other two processes are economically not efficient (Their drawbacks are briefly explained

above) and hence are mostly not used.

But we are interested in the formation of aniline by the ammonolysis of phenol because of the

following few reasons & keeping other steps in consideration.

Capital costs of the process are lower than for processes based on the conventional nitrobenzene

raw material.

Yields are nearly quantitative at high conversions.

Efficient and easy separation of phenol from aniline.

Phenol as a raw material is cheaper than nitrobenzene.

ANILINE PRODUCTIONBY THE AMMONOLYSIS OF PHENOL[Comprehensive Discussion on The Subject Of Process]

Initiation of a process based on its output i-e desired quality and amount. Quality in terms of its

purity has already been discussed in the previous section, while capacity selection is an important

criterion which will be discussed here:
http://en.wikipedia.org/wiki/Phenolhttp://en.wikipedia.org/wiki/Phenolhttp://en.wikipedia.org/wiki/Cumene_processhttp://en.wikipedia.org/wiki/Cumene_processhttp://en.wikipedia.org/wiki/Phenol


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PREFACE |8

CAPACITY SELECTION:

Capacity selection is a very important topic in plant design. Capacity selection involves detail market

survey about the demand of the product in the market and what will be its trend after few years, in

future. Capacity selection to some extent also tells us that how long it will take us to clear our debt as

greater the capacity more quickly the debt can be cleared.

The raw materials and intermediates are derived from various organic and inorganic chemicals. The

raw materials such as resorcinol, Phenol, benzyl alcohol are not being manufactured in Pakistan, due

to economy of scale and lack of feed stocks. Since in Pakistan the petrochemical industries are not

established and we know that phenol (which is mainly produced from benzene through Cumene

process about 80-85%) so if we are to produce aniline from raw materials such as phenol and

ammonia we would have to mostly import phenol.

INDUSTRIAL ASPECT[5]

Sardar Chemical Industries Limited imports 2000kg aniline for 2 months for the manufacture of

direct dyes, leather dyes etc. suppose our target is to supply them 2000kg aniline/per2months.According to our rough calculation the monthly requirement of aniline for the production of

dyes is 200,000kg/month.

GLOBAL SUPPLY AND DEMAND

Global capacity was 4.98m tons/year in 2006, with

1.62m tons/year in Western Europe, 1.38m tons/year in

the US, 1.15m tons/year in Asia-Pacific (excluding

Japan), 474,000 tons/year in Japan, 316,500 tons/year in

Eastern Europe, 70,000 tons/year in Latin America and

64,000 tons/year in Asia/Middle East.

Western Europe is the largest consumer, at about 1.32m

tons/year, followed by the US at 1.19m tons/year and

Asia-Pacific at 717,860 tons/year. Japan, Asia/Middle East

and Latin America consume 319,190 tons/year, 98,360

tons/year and 73,130 tons/year, respectively. Global

demand in 2006 was 3.95m tons/year.

OUR GOAL

Besides considering increasing demands of aniline we select the capacity of our plant as250,000kganiline/month so that we can sell our products to other dyes and rubber producer

companies in considering their increasing demands. Also annual increase in usage of aniline is

increasing in Pakistan by 6-7% per year. We have selected a very low capacity of our plant because

in Pakistan phenol is not readily available due to the lack of establishment of petrochemical

industries and we will have to import 40-60% phenol for fulfilling our requirements. This import will

increase its price a bit but still it is a lot cheaper than importing aniline. Our main goal is to supply

aniline to the dyes and rubber producing companies in Pakistan.


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PREFACE |9

PROCESS DESCRIPTION


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PREFACE |10

Various unit operations including in this process are explained comprehensively below.

FRESH FEED:

Fresh feed containing phenol and ammonia is pressurized to 260 psig before entering into surge tank.

SURGE TANK:

It is a special kind of storage reservoir which reduces the fluctuations in temperature and pressure.

Feed enters in surge tank at 1000F and 260psig. So it reduces the chances of damaging pipelines and

heat exchangers. Then this combined stream enters into heat exchanger in which it exchanges heat

with the stream coming from the reactor. Then it is heated to 6700F before entering into chemical

reactor.

CHEMICAL REACTOR:

An exothermic reaction takes place in between Ammonia and phenol in fixed bed adiabatic reactor.

Conversion of phenol into aniline is 98%. Rest of the phenol is converted into di-phenylamine by

this side reaction.

C6H5NH2 + C6H5OH (C6H5)2NH + H2O

Al2O3.SiO2(possible as zeolites) and oxide mixtures of Mg, B, Al, and Ti are used as catalysts; these

can be combined with additional co-catalysts such as Ce, V, or W.

Stream leaving the reactor which contains aniline, di-phenylamine, water and un-reacted ammonia

passes through the heat exchanger where it exchanges heat with the stream entering in the reactor.

Then this combined stream is cooled further before entering into distillation column.

DISTILLATION COLUMN:

Stream enters into distillation column at the temperature of 2480F and 220psig. Ammonia is

separated from the mixture in distillation column. Two streams leave the distillation column, one is

top stream which is ammonia recycle stream while the remaining components are removed from the

bottom stream which passes through the hydraulic turbine and then it goes to drying column.

AMMONIA RECYCLE:

Conversion of ammonia in the chemical reactor is 87-90%. So rest of the ammonia is recycled

overhead through a compressor to surge tank. In compressor recycled ammonia is pressurized from

220psig to 260psig, correspondingly temperature varies from 2480F to 1000F

DRYING COLUMN:

Drying column is maintained at very low pressure. Water and traces of ammonia are separated from

the top of drying column. Bottom stream containing aniline and di-phenylamine moved towards

purification column.

PURIFICATION COLUMN:


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PREFACE |11

Distillation is carried out in this column where aniline due to its lesser boiling point than di-

phenylamine. So, aniline which is our actual product is separated from top of purification column

while di-phenylamine which is by product leaves the column from bottom. Aniline product formed

by this process is 99% pure.


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APPENDIX |IV

APPENDIXI

PHYSICAL PROPERTIES OF ANILINE [8]

PROPERTY VALUE PROPERTY VALUE

Molecular Weight 93.12 g/gmol Boiling Point 184.4 [1 atm]

Melting point -6.15 oC Density at 20/4 oC 1.02173

Viscosity at 20oC 4.42334.435 cP

Dissociation ConstantpKa at 20

oC

4.60

Enthalpy dissociation 21.7 kJ/mol Heat of combustion 3389.72 kJ/mol

Specific Heat [20-25]

o

C 0.518 Jkg

-1

K

-1

Latent heat of

vaporization 476.3 J/g

Flash Point [closed cup] 76oC Auto ignition 615

oC

Flammable Limits in air(% by Volume)

LEL = 1.3UEL = 11.0

Vapor Density 3.22

Solubility 3.5 g in 100g water Odor threshold, ppm 1.1


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ANILINE PRODUCTIONBy Ammonolysis of Phenol|1

REFERENCES

[1] http://www.epa.gov/chemfact/anali-sd.pdf

[2] http://www.icis.com/Articles/2008/01/07/9089893/chemical-profile-aniline.html

[3] Kent and Riegel's Handbook Of Industrial Chemistry And Biotechnology

[4] http://books.google.com.pk/Synthetic Nitrogen Products: A Practical Guide to the Products and

Processes by Gary Maxwell/production of aniline by ammonolysis of phenol.

[5] http://www.lookchem.com/Chempedia/Chemical-Technology/Organic-Chemical-

Technology/7791.html.

[6] http://pubs.acs.org/doi/abs/10.1021/cen-v047n014.p044

[7] http://onlinelibrary.wiley.com/doi/10.1002/0471238961.0114091201130914.a01.pub2/abstract

[8] http://www.tutorskingdom.com/.../properties-and-uses-of-aniline/ - United States.


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REFERENCES |

production of aniline from ammonolysis of phenol- 2010-ch-09,61,65,87

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