A Project Report on

PRODUCTION OF ANILINE

SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIRMENTS FOR THE AWARD OF THE DEGRE OF

BACHELOR OF TECHNOLOGY IN CHEMICAL ENGINEERING

Submitted By Tejaswi Pothuganti (9626) V. Blessystella (9632) Mallikarjun Reddy G (9647) Mohith Nigam (9671) Under the Guidance of Mrs. Srivani, Associate Professor DEPARTMENT OF CHEMICAL ENGINEERING NATIONAL INSTITUTE OF TECHNOLOGY WARANGAL-506004 (A.P)

2012-2013

DEPARTMENT OF CHEMICAL ENGINEERING NATIONAL INSTITUTE OF TECHNOLOGY WARANGAL-506004

CERTIFICATE

This is to certify that the project entitled Production of ANILINE carried out by Ms. Tejaswi Pothuganti (9626), Ms. V. Blessystella (9632), Mr. Mallikarjun Reddy G (9647), Mr. Mohith Nigam (9671) of final year B.Tech Chemical Engineering during the year 20122013 is a bonafide work submitted to the National Institute of Technology, Warangal in partial fulfilment of requirements for the award of degree of Bachelor of Technology.

Project Guide Mrs. Srivani

AssociateProfessor Dept. of Chemical Engineering NIT Warangal

Head of the Department

Prof. Y Pydi Setty Professor Dept. Of Chemical Engineering NIT-Warangal

ACKNOWLEDGEMENT
We would like to express our deep sense of respect and gratitude toward our supervisor Mrs. K. Srivani, Associate Professor, Department of Electronics and Communication Engineering, National Institute of Technology, Warangal who not only guided the academic project work but also stood as a teacher. Her presence and optimism have provided an invaluable influence on my career and outlook for the future. We consider it as our good fortune to have got an opportunity to work with such a wonderful person. We express my gratitude to Prof. Y.Pydisetty, Head of Department of Chemical Engineering, Mr. Srinu Naik, Project In charge, Department of Chemical Engineering and its faculty members and staff for extending all possible help in carrying out the dissertation work directly or indirectly. They have been great source of inspiration to us and we thank them from bottom of my heart. We would like to acknowledge our institute, National Institute of Technology, Warangal, for providing good facilities to complete our thesis work. We would also like to take this opportunity to acknowledge our friends for their support and encouragement. We are especially indebted to our parents for their love, sacrifice and support.

Tejaswi Pothuganti (09626) V. Blessystella (09632) G. Mallikarjuna Reddy (09647) Mohit Nigam (09671)

INDEX

Chapter No 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Introduction Market Analysis Uses

Page no Chapter name 1 2 6 8 14 17 18 22 35 50 80 84 89 94

Physical & Chemical Properties Different Manufacturing Process Selection of Process Process Description Mass balance Energy balance Design of major Equipment Cost estimation Plant layout and location Pollution control and Safety Bibliography

1. INTRODUCTION:
Aniline, phenylamine or aminobenzene 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 odour of rotten fish. It ignites readily, burning with a smoky flame characteristic of aromatic compounds. Aniline is colourless, but it slowly oxidizes and resinifies in air, giving a red-brown tint to aged samples.

From a historical perspective, aniline is perhaps one of the more important synthetic organic chemicals ever manufactured. In 1856, Sir William Henry Perkin, a student at the Royal College of Chemistry in London, discovered and isolated a purple dye during the oxidation of impure aniline. The discovery of this dye, known as mauve, created quite a stir and Perkin, seeing the value of his discovery, proceeded to scale up the synthetic process for the production of mauve, which included the synthesis of aniline. This process was to become one of the first commercial processes to generate a synthetic organic chemical. During the last three decades, polyurethane plastics have emerged as a growth industry and aniline once again plays a key role as an industrial intermediate used in the manufacture of MDI, 4,4-diphenylmethane diisocyanate, a key commercial monomer in the manufacture of polyurethane plastics.

Aniline is produced by the reduction of nitrobenzene, which is produced from the nitration of benzene in a mixture of sulphuric and nitric acid.

2. MARKET ANALYSIS:
MDI (Methylene Diphenyl Diisocyanate) production accounts for over 75% of world aniline consumption; other large applications include use as a chemical intermediate for rubberprocessing chemicals, dyes and pigments. Since most MDI producers are captive in aniline and its precursor nitrobenzene, typically in integrated units, nearly all MDI expansions result in increased production and consumption of nitrobenzene/aniline. MDI has been the driving force behind world growth in aniline demand since 1982. Future demand for aniline will continue to depend largely on MDI requirements.

MDI is consumed in polyurethane (PU) foam, both rigid and flexible. Most rigid PU foam is used in construction and appliances while flexible PU foam is used primarily in furniture and transportation. As a result, consumption of nitrobenzene/aniline/MDI largely follows the patterns of the leading world economies and depends heavily on construction/remodelling activity (residential and non-residential), automotive production and original equipment manufacturer. MDI growth has been driven by "green" initiatives, sustainability and lowering CO2 emissions. World consumption of aniline grew at an average annual rate of 3% during 20062010, the result of a growing global economy during 20012008, declines during the economic recession in 2009 and the recovery in 2010, and growth due to increased MDI capacity. Strong Asian demand for all applications of MDI boosted world demand during 20062010. World consumption of aniline is forecast to grow at an average annual rate of 3.8% during 20102015. Continuing rapid demand growth in some regions, particularly in China, Other
6

Asia

and

Europe,

mainly

the

result

of

continued

expansion

of

integrated

nitrobenzene/aniline/MDI units, will balance out moderate growth in markets such as the Americas. The aniline industry is a concentrated one, with most producers integrated into MDI production. BASF, Huntsman, Bayer and DuPont are the four dominant players, with about 17%, 12%, 12% and 10% of the world's capacity, respectively; only DuPont is not an MDI producer. BASF, Huntsman and Bayer each have plants in several world regions. 2.1. Supply/demand: Global capacity was 4.98m tonnes/year in 2006, with 1.62m tonnes/year in Western Europe, 1.38m tonnes/year in the US, 1.15m tonnes/year in Asia-Pacific (excluding Japan), 474,000 tonnes/year in Japan, 316,500 tonnes/year in Eastern Europe, 70,000 tonnes/year in Latin America and 64,000 tonnes/year in Asia/Middle East. Western Europe is the largest consumer, at about 1.32m tonnes/year, followed by the US at 1.19m tonnes/year and Asia-Pacific at 717,860 tonnes/year. Japan, Asia/Middle East and Latin America consume 319,190 tonnes/year, 98,360 tonnes/year and 73,130 tonnes/year, respectively. Global demand in 2006 was 3.95m tonnes/year. 2.2. Prices: There is a small merchant market and prices typically track benzene. European prices in the fourth quarter were 0.98-1.06/kg. November contracts in the US and Asia-Pacific were $0.62-0.68/lb and $1.29-1.40/kg, respectively. 2.3. Technology Most production is based on the catalytic hydrogenation of nitrobenzene, where benzene is mixed with a solution of nitric acid, hydrogenated and then purified by distillation. Another route, by SABIC/Sud-Chemie partnership Scientific Design, is the vapour phase ammonolysis ofphenol using excess ammonia and a silica-alumina catalyst, but this is now only used by Mitsui. 2.4. Outlook Global demand growth is put at 6%/year to 2010. Annual consumption will rise by 10.5% in Asia-Pacific, 6.5% in Asia/Middle East, 5.6% in Western Europe, 5.1% in the US, and 1.5% in Japan, respectively. Other world regions will grow by 3-4%/year. There is plenty of capacity until 2012. In China, Bayer will build a 247,000 tonne/year unit for 2009 and Yantai Wanhua's hike to 95,000 tonnes/year was due by late 2007. South

Korea's Kumho Mitsui will double output to 90,000 tonnes/year in 2009. Japan's Tosoh will expand to 300,000 tonnes/year by 2008. Karun Petrochemical plans a 30,000 tonne/year unit in Iran, for 2009. India's Hindustan Organic Chemicals may restart a 60,000 tonne/year unit by 2008 or later.

2.4. MAJOR GLOBAL ANILINE CAPACITY '000 TONNES/YEAR(Table-1) Company BASF Location Antwerp, Belgium Geismar, Louisiana, US Yeocheon, South Korea Yeosu, South Korea Bayer Antwerp, Belgium Brunsbuttel, Germany Krefeld, Germany Sao Paulo, Brazil Borsodchem Dow Chemical Ostrava, Czech Republic Bohlen, Germany Estarreja, Portugal DuPont Baytown, Texas, US Beaumont, Texas, US Capacity 430 264 60 140 140 180 166 60 150 130 125 250 150

Pascagoula, Mississippi, US 240 Huntsman Geismar, Louisiana, US 460

Wilton, UK Lanzhou Chemical Industry Shandong Haihua Shanghai Lianheng Isocyanate Shanxi Tianji Coal Singpu Chemicals Sinopec Nanjing Chemical Sumitomo Mitsui Chemical Sumitomo-Bayer Tosoh Volzhskiy Orgsintez * excludes units under 50,000 tonnes/year SOURCE: CHEMPLAN BY TRANTECH CONSULTANTS Lanzhou, China Weifang, China Caojing, China Tianji, China Yancheng, China Nanjing, China Chiba, Japan Kurosaki, Japan Nanyo, Japan Novomoskovsk, Russia

450 106 50 177 130 90 135 124 100 150 50

3. USES OF ANILINE:
Aniline, an organic base used to make dyes, drugs, explosives, plastics, and photographic and rubber chemicals. Aniline, a primary aromatic amine, is a weak base and forms salts with mineral acids. In acidic solution, nitrous acid converts aniline into a diazonium salt that is an intermediate in the preparation of a great number of dyes and other organic compounds of commercial interest. When aniline is heated with organic acids, it gives amides, called Anilides, such as acetanilide from aniline and acetic acid. Monomethylaniline and dimethylaniline can be prepared from aniline and methyl alcohol. Catalytic reduction of aniline yields cyclohexylamine. Various oxidizing agents convert aniline to quinone, azobenzene, nitrosobenzene, p-aminophenol, and the phenazine dye aniline black. The great commercial value of aniline was due to the readiness with which it yields, directly or indirectly, dyestuffs. The discovery of mauve in 1856 by William Henry Perkin was the first of a series of dyestuffs that are now to be numbered by hundreds. Reference should be made to the articles dyeing, fuchsine, safranine, indulines, for more details on this subject. In addition to its use as a precursor to dyestuffs, it is a starting-product for the manufacture of many drugs, such as paracetamol (acetaminophen, Tylenol).It is used to stain neural RNA blue in the Nissl stain. At the present time, the largest market for aniline is preparation of methylene diphenyl diisocyanate (MDI), some 85% of aniline serving this market. Other uses include rubber processing chemicals (9%), herbicides (2%), and dyes and pigments (2%). When polymerized, aniline can be used as a type of nanowire for use as a semiconducting electrode bridge, most recently used for nano-scale devices such as biosensors. These polyanilineg nanowires can be doped with a dopant accordingly in order to achieve certain semiconducting properties. 3.1. Developments in medicine In the late 19th century, aniline emerged as an analgesic drug, its cardiac-suppressive side effects countered with caffeine.[11] In the 20th century's first decade, modifying synthetic dyes to treatsleeping sickness, Paul Ehrlichwho had coined the term chemotherapy for his magic bullet approach to medicinefailed and switched to modifying Bchamp's atoxyl,
10

the first organic arsenicaldrug, and serendipitously attained the syphilis treatment salvarsan, the first successful chemotherapy. Salvarsan's targeted microorganism, not yet recognized as bacteria, was still thought a parasite, however, and medical bacteriologists, believing bacteria not susceptible to the chemotherapeutic approach, overlooked Alexander Fleming's 1929 report on the in vitro effect ofpenicillin.[12] In 1932, Bayer sought medical applications of its dyes. Gerhard Domagk identified as antibacterial a red azo dye, introduced in 1935 as the first antibacterial drug, prontosil, rapidly found atPasteur Institute to be a prodrug degraded in vivo to sulfanilamidea colorless intermediate for many, highly colorfast azo dyesalready off patent, synthesized in 1908 in Vienna by Paul Gelmofor his doctoral thesis.[12] By the 1940s, over 500 related sulfa drugs were produced.[12] In high demand via World War II (193945), these first miracle drugs, chemotherapy of wide effectiveness, propelled the American pharmaceutics industry.[13] In 1939, at Oxford University, seeking an alternative to sulfa drugs, Howard Florey developed Fleming's penicillin into the first systemicantibiotic drug, penicillin G. (Gramicidin, developed by Ren Dubos at Rockefeller Institute in 1939, was the first antibiotic, yet its toxicity restricted it to topical use.) After WWII, Cornelius P. Rhoads introduced the chemotherapeutic approach to cancer treatment.[14]

11

4. PHYSICAL& CHEMICAL PROPERTIES:

4.1. PHYSICAL PROPERTIES[1}:(Table-2) PROPERTY Molecular Formula Molecular Weight Boiling point, 0C 101.3 K Pa 4.4 K Pa 1.2 K Pa Freezing Point C Density,liquid,g/mL Density,Vapor,(at bp,air=1) Refractive Index Viscosity, mPa.s(=cP) 20 0C 60 Enthalpy of dissociation, kJ/mole Heat of combustion, kJ/mole Ionisation potential, eV Dielectric constant, at 25 C Dipole moment at 250C,C.m Specific heat at 250C,J/(g.K) Heat of vaporization, J/g Flash point,0C Closed cup Open cup Ignition Temperature, 0C Lower flammable limit, vol % Odour Threshold,ppm 70 75.5 615 1.3 2.4
0 0

VALUE C6H7N 93.129

184.4 92 71 -6.03 1.02173 3.30 1.5863

4.35 1.62 21.7 3394 7.70 6.89 5.20*10-30 2.06 478.5

Physical state and appearance

Liquid. (Oily liquid.)

12

Odour:

Aromatic. Amine like.

Taste:

Burning.

Water/Oil Dist. Coeff.

The product is more soluble in oil; log(oil/water) = 0.9

Critical Temperature

425.6C (798.1F)

4.2. CHEMICAL PROPERTIES[1]: Aromatic amines are usually weaker bases than aliphatic amines by the difference in P ka of the conjugate acids of aniline. Pka of Aniline is 4.63 and Pka of cyclo hexyl amine is 10.66. This is due to resonance effect. Aniline is stabilized by sharing its lone-pair electrons with the aromatic ring. Aromatic amines form addition compounds and complexes with many inorganic substances, such as Zinc chloride,copper chloride, Uranium Tetrachloride, or Boron Trifloride.Various metals react with amino group to form metal anilides; Hydrochloric, sulphuric, or Phosphoric acid salts of aniline are important intermediates in the dye industry. 4.2.1 N-alkylation[1]: A number of methods are available for preparation of N-alkyl and N,N-dialkyl derivatives of aromatic amines. Passing a mixture of aniline and methanol over a copper-zinc oxide catalyst at 2500C and 101 kPa reportedly gives N-methylaniline. Heating aniline with methanol under pressure or with excess methanol produces N,N-dimethylaniline. In the presence of sulphuric acid, aniline reacts with methanol to form N-methyl and N,N-dimethyl aniline. This is a two step process as shown. C6H5NH2 + CH3OH C6H5NHCH3 + H2O C6H5NHCH3 + CH3OH C6H5NH(CH3)2 + H2O

13

4.2.2. Ring Alkylation [1]: The aromatic ring undergoes alkylation under certain conditions. For example,2-ethylaniline, 2-6-diethylaniline, or mixture of the two are obtained in high yield when aniline is heated with ethylene in the presence of aluminium-anilide catalyst(formed by heating aluminium and aniline) at 3300 C and 4-5 MPa. 4.2.3. Acylation [1]: Aromatic amines react with acids, acid chlorides, anhydrides, and esters to form amides.In general,acid chlorides give the best yield of the pure product. The reaction with acetic,propionic,butanoic, or benzoic acid can be catalysed with phosphorous oxychloride or trichloride. N-Phenylsuccinimide (succanil) is obtained in essentially quantitative yield by heating equivalent amounts of succinic acid and aniline at 140-1500C. the reaction of a primary aromatic amine with phosgene leads to formation of an arylcarbamoyl chloride, that when heated loses hydrogen chloride to form isocyanate. Commercially important isocyanates are obtained from aromatic primary diamines. Conversion of aniline to acetanilide, by reaction with acetic anhydride, is a convenient method for protecting the amino group. The acetyl group can later be removed by acid or base hydrolysis. 4.2.4. Condensation [1]: Depending on the reaction conditions, a variety of condensation products are obtained from the reaction of aromatic amines with aldehydes, ketones, acetals, and orthoformates. Primary aromatic amines react with aldehydes to form Schiff bases. Schiff bases formed from the reaction of lower aliphatic aldehydes, such as formaldehyde and acetaldehyde, with primary aromatic amines are often unstable and polymerize readily. Aniline reacts with formaldehyde in aqueous acid solutions to yield mixtures of a crystalline trimer of the Schiff base, methylenedianilines, and polymers.

14

4.2.5. Cyclization [1]: Aniline, nitrobenzene, and glycerol react under acid catalysis (Skraup synthesis) to form quinolone. The Skraup synthesis is a chemical reaction used to synthesize quinolines. It is named after the Czech chemist Zdenko Hans Skraup (1850-1910). In the archetypal Skraup, aniline is heated with sulfuric acid, glycerol, and an oxidizing agent,likenitrobenzene to yield quinoline.

In this example, nitrobenzene serves as both the solvent and the oxidizing agent. The reaction, which otherwise has a reputation for being violent ("the Chemical Inquisition"), is typically conducted in the presence of ferrous sulphate.Arsenic acid may be used instead of nitrobenzene and the former is better since the reaction is less violent.

15

4.2.6. Halogenation [1]: The presence of the amino group activates the ortho and para positions of the aromatic ring and, as a result, aniline reacts readily with bromine or chlorine. Under mild conditions, bromination yields 2,4,6- tribromoaniline.

4.2.7. Oxidation [1]: Aniline was selectively converted into the corresponding nitrosobenzene and nitrobenzene by oxidation with 30% aqueous hydrogen peroxide. The reaction was catalyzed by various heteropolyoxometalates, at room temperature, in dichloromethane under two-phase conditions. Findings show that H3PW12O40 is the best catalyst in the oxidation of aniline. Na3PW9Mo3O40 and K4SiW9Mo2O39 also displayed high reactivity in the oxygenation system. Phase transfer agents and temperature increase also contribute to the efficiency of the oxidation 4.2.8.ReactivityProfile[1]: Aniline is a heat sensitive base. Combines with acids to form salts. Dissolves alkali metals or alkaline earth metals with evolution of hydrogen. Incompatible with albumin, solutions of iron, zinc and aluminum, and acids. Couples readily with phenols and aromatic amines. Easily acylated and alkylated. Corrosive to copper and copper alloys. Can react vigorously with oxidizing materials (including perchloric acid, fuming nitric acid, sodium peroxide and ozone). Reacts violently with BCl3. Mixtures with toluene diisocyanate may ignite. Undergoes explosive reactions with benzenediazonium-2-carboxylate, dibenzoyl peroxide, fluorine nitrate, nitrosyl perchlorate, peroxodisulfuric acid and tetranitromethane. Violent reactions may occur with peroxyformic acid, diisopropyl peroxydicarbonate, fluorine, trichloronitromethane (293 F), acetic anhydride, chlorosulfonic acid, hexachloromelamine, (HNO3 + N2O4 + H2SO4), (nitrobenzene + glycerin), oleum, (HCHO + HClO4), perchromates, K2O2, beta-propiolactone, AgClO4, Na2O2, H2SO4, trichloromelamine, acids, FO3Cl, diisopropyl peroxy-dicarbonate, n-haloimides and trichloronitromethane.
16

Ignites on contact with sodium peroxide + water. Forms heat or shock sensitive explosive mixtures with anilinium chloride (detonates at 464 F/7.6 bar), nitromethane, hydrogen peroxide, 1-chloro-2,3-epoxypropane and peroxomonosulfuric acid. It reacts with perchloryl fluoride form explosive products. .

17

5. DIFFERENT WAYS OF PRODUCTION:

5.1. From Nitrobenzene: 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 oxide pigments from the resulting iron oxide sludge. However, the increasing demand for aniline has far 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 sulfidization 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-Cr system. 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
18

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. 5.2. From 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 ammonolyred 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-phasereaction product. 5.3.From Phenol: 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 425 C:

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. 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 tonnes per year. A second plant with a capacity of 90000 tonnes per year was started up by US Steel Corp. (now Aristech) in 1982. 5.4. From Benzene: Du Pont has developed an interesting manufacturing process for aniline. Benzene and NH3 can be reacted over a NiO/Ni catalyst containing promoters including zirconium oxide at

19

350C & 300 bar to give a 97% selectivity to aniline with benzene conversion of 13%

Since the hydrogen formed in the reaction reduces the NiO part of the catalyst, a catalyst regeneration (partial oxidation) is necessary. Despite inexpensive feedstocks, industrial implementation is still thwarted by the low benzene conversion and the necessary catalyst re-oxidation.

20

6. CHOICE OF PROCESS:
The catalytic Hydrogenation of Nitrobenzene to Aniline gives selectivity more than 99%, better than other manufacturing processes. Nitrobenzene is the classical feedstock for Aniline manufacture. The method process is simple, inexpensive catalysts, long life, from product quality, After preheating the hydrogen and nitrobenzene, hydrogenation reaction occurs. Fixed bed gas phase catalytic hydrogenation process has a matured technology, the reaction temperature is lower, equipment has easy operation, low maintenance costs, less investment, without separation of catalyst, good product quality; deficiency is, the reaction pressure is more prone to occurrence of local side effects caused by overheating and catalyst deactivation, the catalyst must be periodically replaced. Currently, most foreign manufacturers of fixed-bed use gas phase aniline hydrogenation process.

21

7. PROCESS DESCRIPTION
Rayer and Allied work with nickel sulphide 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 sulfidization methods with sulphate, 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-Cr system.

Table 3: Physical properties for aniline and water [2] Aniline Chemical Formula (Mw) (g/mol) Tb(K) Tm(K) Antoine A Antoine B(C) Antoine C(C) Vapor pressure A Vapor pressure B(K) Vapor pressure C Vapor pressure D C6H7N 93.128 457.15 267.13 7.43481 1813.917 213.709 66.287 -8207.1 -6.0132 2.84 1018 Vapor pressure E Density A(kmol) Density B(m3) Density C(K) Density D 6 1.0405 0.2807 699.0 0.29236 Water H2O 18.015 373.15 273.15 8.02927 1713.681 232.633 73.649 -7258.2 -7.3037 4.17 106 2 5.459 0.30542 647.13 0.081

22

23

Antoine equation: Liquidliquid Properties If liquidliquid extraction is to be performed, the liquidliquid equilibrium behaviour must be known. An important liquidliquid temperature dependent property is the solubility. From Srensen et al. (14) mol percents representing aniline dissolved in water and water dissolved in aniline are shown in table. Table 4: Solubility of aniline in water and water in aniline[2] Temperature(C) 20.0 25.0 Mol percent aniline 0.674 0.679 Weight percent aniline 20.0 25.0 3.39 3.41 Mol percent water 21.3 21.8 Weight percent water 4.98 5.12

The solubility of aniline dissolved in water from table 2.2 show that water is more soluble in aniline than aniline is in water VaporLiquid Properties : If distillation separation is to be used to separate the mixture, the vaporliquid behaviour must be known, and because the anilinewater system does not behave ideally, the activity coefficients are of interest. From Gmehling et al (2) the Margules, van Laar, Wilson, NRTL and UNIQUAC model parameters are listed in table 2.3.

24

Table 5: Model Parameters and i for different models[2] A12 Margules Van Laar Wilson NRTL 1.0041 1.2006 1608.4375 A21 3.1217 8.3006 2513.9461 2.73 22.68

3.32 4026.37 3.11 3.68 229.00 104.01

6945.2299 2651.2199

UNIQUAC 1439.0048

-379.5945

3.49

554.62

In table 5 index 1 represents water and index 2 aniline. All the methods show that , which is consistent with table 2.2, which shows that

aniline is less soluble in water than water is in aniline. The large 2 found by the Van Laar model is not a typing error, and therefore a strong confirmation of the low solubility of aniline in water. Investigations of a VLEdiagram show that an azeotrope exists for the anilinewater binary system. Horyna et al (16) have found the azeotrope to be at a water weight fraction of x1 = 0.808 (water mol fraction of 0.956) and a temperature of 98.6C, at a pressure of 742mmHg. A VLEdiagram estimated using the VLE UNIFAC model at 760mmHg in SMSWIN is shown in figure 2.1 to the right. It is similar to the proportional diagram from Gmehling et al (2), the diagram to the left. Both diagrams show an azeotrope at the weight fraction x1 0.96, corresponding to the one determined by Horyna et al, indicating that the VLE UNIFAC model is a good approximating for the vaporliquid behaviour of a anilinewater binary system.

Figure 1: VLE diagrams for the binary aniline/water system at 1atm. The left diagram is experimentally determined, and the right is estimated using the VLE UNIFAC model[2].
25

An estimated number of the distillation stages needed to perform the distillations in figure 1 can be found using the Margules equations from Smith et al. (13). The Margules equations represent a commonly used empirical model of solution behaviour and are defined as ln1 = x22 [A12 + 2(A21 A12)x1] ln2 = x21 [A21 + 2(A12 A21)x2] (3.2)

From the values of A12 and A21 given in table 2.3, the activity coefficients can be determined, and in relation to the vapor pressures, the relative volatility can be determined as done by King (4)

26

27

8. MASS BALANCE:
Basis: Production of Aniline (99.5% purity) is 218788.529 tons/year. Assumptions: No of plant working days=300 days 100% conversion of Nitrobenzene. 200% excess of Hydrogen is used. Reactants are pure.

Average molecular weight=0.995*93.1262+0.005*18.0152=92.7506. So, 218788.529 tons per year =30387.29578 kg/hr =327.623 kmol/hr. Based amount of Nitrobenzene required is =326.632 kmol/hr, =326.632*123.1092, =40211.40421 kg/hr. The ratio of Hydrogen to Nitrobenzene is= 9:1 Amount of hydrogen required =9*326.632 =2939.688 kmol/hr =5925.82307 kg/hr. Hydrogen from recycle =6*326.632 =1959.792 kmol/hr Fresh feed of Hydrogen= 3*326.632 =979.896 kmol/hr Mass balance for Vaporiser: Stream1A: Pure Nitrobenzene feed in liquid phase=326.632 kmol/hr Stream1B: Nitrobenzene from vaporizer in vapor phase=326.632 kmol/hr =40211.40421 kg/hr =40211.40421 kg/hr =3950.548714 kg/hr. =1975.274356 kg/hr.

28

Mass balance for the reactor:

Stream1B: Nitrobenzene from vaporizer in vapor phase=326.632 kmol/hr =40211.40421 kg/hr

29

Stream2: Fresh Hydrogen feed=979.896 kmol/hr = 1975.27436 kg/hr. Stream3: Makeup Hydrogen or recycle=1959.792 kmol/hr = 3950.54871 kg/hr. Stream4: Total amount of Hydrogen Stream5: Nitrobenzene vapor stream=40211.40421 kg/hr Total Hydrogen feed to the reactor=5925.82307 kg/hr Total feed to Fluidized bed reactor =46137.22728 kg/hr Stream6: Product stream consists of Aniline, water and unreacted Hydrogen, all in vapor phase. Aniline=326.632 kmol/hr = 30417.99696 kg/hr Water=653.264 kmol/hr = 11768.68161 kg/hr Unreacted Hydrogen = 1959.792 kmol/hr = 3950.54871 kg/hr. Table 6: Flow Component Nitrobenzene Hydrogen Water Aniline TOTAL(kg/hr) TOTAL(kg/hr) IN Stream 1B(kg/hr) Stream 2(kg/hr) Stream 4(kg/hr) 40211.40421 ------40211.40421 --1975.27436 ----1975.274356 --3950.54871 ----3950.548714 OUT Stream 6(kg/hr) --3950.54871 11768.68161 30417.99696 46137.22728 46137.22728 =2939.688 kmol/hr = 5925.82307 kg/hr.

46137.22728

30

Mass Balance for the condenser:

Stream6: Reactor Product stream consists of Aniline, water and unreacted Hydrogen, all in vapor phase. Aniline=326.632 kmol/hr Water=653.264 kmol/hr =30417.99696 kg/hr =11768.68161 kg/hr =3950.54871 kg/hr.

Unreacted Hydrogen=1959.792 kmol/hr Stream3:

Makeup or unreacted Hydrogen or recycle=1959.792 kmol/hr Stream7: Consists of condensed Water and Aniline. Aniline=326.632 kmol/hr Water=653.264 kmol/hr =30417.99696 kg/hr =11768.68161 kg/hr

=3950.54871kg/hr.

31

Table 7: Flow Component Nitrobenzene Hydrogen Water Aniline Total (kg/hr) IN Stream 6(kg/hr) --3950.548714 11768.68161 30417.99696 46137.22728 OUT Stream 3(kg/hr) --3950.54871 ----3950.54871 OUT Stream 7(kg/hr) ----11768.68161 30417.99696 42186.67857

Mass balance for the Decanter:

Stream7: Consists of condensed Water and Aniline. Aniline=326.632 kmol/hr =30417.99696 kg/hr Water=653.264 kmol/hr =11768.68161 kg/hr Stream 12: Water=32698.53348 kg/hr

32

Aniline=7042.02739 kg/hr Stream13: Water=5117.73724 kg/hr Aniline=1392.55056kg/hr Stream9: Water=44437.73942 kg/hr Aniline=7102.20424kg/hr Stream 10: Water =5147.21291kg/hr Aniline=31750.37067kg/hr Table 7 Flow Stream Component Nitrobenzene Hydrogen 7(kg/hr) ----IN Stream 12(kg/hr) ----Stream 13(kg/hr) ----OUT Stream 9(kg/hr) ----OUT Stream 10(kg/hr) ----5147.21291 Water 11768.68161 32698.53348 5117.73724 44437.73942 31750.37067 Aniline TOTAL(kg/hr) TOTAL(kg/hr) 30417.99696 7042.02739 1392.55056 6510.28780 7102.20424 51539.94366 88437.52724 36897.58358

42186.67857 39740.56087 88437.52724

Mass balance for the distillation column 1:

33

Stream9: Water=44437.73942 kg/hr Aniline=7102.20424kg/hr Stream 11: Water =11739.20594 kg/hr Aniline=60.17685 kg/hr Stream 12: Water =32698.53348 kg/hr. Aniline=7042.02739 kg/hr

34

Table 8: Flow Component Nitrobenzene Hydrogen Water Aniline Total (kg/hr) IN Stream 9(kg/hr) ----44437.73942 7102.20424 51539.94366 OUT OUT

Stream 11(kg/hr) Stream 12(kg/hr) ----11739.20594 60.17685 11799.38279 ----32698.53348 7042.02739 39740.56087

Mass balance for Distillation column2:

Stream 10: Water =5147.21291 kg/hr Aniline=31750.37067 kg/hr Stream13: Distillate stream enriched with water Aniline=1392.55056kg/hr
35

Water=5117.73724 kg/hr Stream14: Bottom stream enriched with Aniline Aniline=30387.29578 kg/hr Water=29.47567 kg/hr Table 9: Flow Component Nitrobenzene Hydrogen Water Aniline Total (kg/hr) IN Stream 10(kg/hr) ----5147.21291 31750.37067 36897.58358 OUT OUT

Stream 13(kg/hr) Stream 14(kg/hr) ----5117.73724 1392.55056 6510.28780 ----29.47567 30387.29578 30387.29578

36

37

9. DETAILED ENERGY BALANCE

Heat capacity data: Nitrobenzene = 1.4 kj/kg.K Hydrogen[5] = 6.62+ 0.00081T(K) cal/mol.K = 13.727+0.00168T kj/kg.K Aniline[5] =1.4155 + 1.7122T j/kmol.K Water in liquid phase[6] = (8.712 +1.25*10-3T -0.18*10-6T2)*R Water in gas phase[6] = (3.470 + 1.45*10-3T+0.121/T2)*R Energy balance for the Nitrobenzene vaporizer:

Heat in:

38

Nitrobenzene is at room temperature of 298 K. So enthalpy in =0 Heat out: Nitrobenzene is heated from 298 to 553.15 K Enthalpy associated with Nitrobenzene = m + m Hv + Enthalpy of vaporization of Nitrobenzene Hv =33 kj/kg. Enthalpy associated with Nitrobenzene +40211.40421*33 + kj/hr = 40211.40421*

=19631609.7 kj/hr Heat supplied by the Vaporizer=enthalpy out-enthalpy in =15690892.1+3940717.6 =19631609.7 kj/hr Table 10: Flow IN IN Heat supplied Component Nitrobenzene Hydrogen Water Aniline Total (kg/hr) Stream1A (kj/hr) 0 ------0 (kj/hr) 19631609.7 ------19631609.7 Stream1B (kj/hr) 19631609.7 --0 0 19631609.7 OUT

39

Energy balance for the reactor:

Heat in: Enthalpy in with Nitrobenzene=19631609.7kj/hr Enthalpy in with Hydrogen= =5925.82307* =27939805.8 kj/hr Total enthalpy in=19631609.7 +27939805.8 =47571415.5 kj/hr Heat Generated : kj/hr

Heat generated by reaction = 443 kj/mol=443000 kj/kmol Total heat generated = 443000*326.632 = 144697976 kj/hr
40

Heat removed by Coolant : The temperature in the reactor reaches an average peak temperature of 700 K due to exothermic reaction. Hf0298 of Aniline=31.3 kj/mol=31300 kj/kmol Heat with Aniline =m + m Hv )*m

= (42440+10-3 =14718691 kj/hr Heat with Water= m + m Hv =m =979.896*(40680+ + =979.896*(40680+5692.6+11543.7) =979.896*57916.3 = 56751950.7 kj/hr Heat with Hydrogen= m =3950.54871* =26697609.23 kj/hr Total enthalpy out due to products=14718691+56751950.7 +26697609.23 =98168250.93 kj/hr Total heat removed by the Coolant = Total enthalpy in-total enthalpy out+total heat generated by the reaction = 47571415.5 -98168250.93 +144697976 = 94101140.57 kj/kg ) +m + m Hv

41

Table 11: Flow IN OUT Heat removed Component Nitrobenzene Hydrogen Water Aniline TOTAL(kg/hr) TOTAL(kg/hr) Stream1B (kj/hr) 19631609.7 ------19631609.7 Stream4 (kj/hr) --27939805.8 ----27939805.8 Stream6 (kj/hr) --26697609.23 56751950.7 14718691 98168250.93 98168250.93 94101140.57 Stream (kj/hr) ---

47571415.5

Energy Balance for the condenser:

Enthalpy in: Heat with Aniline =14718691 kj/hr Heat with Water= 56751950.7 kj/hr Heat with Hydrogen= 26697609.23 kj/hr Total enthalpy in due to products = 14718691+56751950.7 +26697609.23 =98168250.93 kj/hr Enthalpy out: As condenser removes the latent heat and sensible heat in gas phase, all streams are cooled to bubble point of Aniline and Water mixture which is 371.69 K.
42

So, Enthalpy with aniline=326.632*10-3* =107008.6 kj/hr Enthalpy with water =979.896 *( )

=5469289.4 kj/hr Enthalpy with Hydrogen= m =3950.54871* =4159912.7 kj/hr Total enthalpy out=107008.6+5469289.4+4159912.7=9736210.7 kj/hr Heat removed by condenser=387779355.3-98168250.93 =289611104.4 kj/hr.

Table 12: Flow IN OUT Heat Removed Component Nitrobenzene Hydrogen Water Aniline Total (kg/hr) Stream6 (kj/hr) --14718691 56751950.7 26697609.23 98168250.93 Stream (kj/hr) --------289611104.4 Stream7 (kj/hr) --4159912.7 5469289.4 107008.6 9736210.7 OUT

Energy balance for the pre-cooler: This heat exchanger removes heat such that temperature of the stream is reduced to 303.15 K from 371.69 K. Enthalpy in: Enthalpy with aniline = 107008.6 kj/hr Enthalpy with water Total enthalpy out = 5469289.4 kj/hr = 107008.6+5469289.4 = 5576298 kj/hr
43

Enthalpy out: So, enthalpy with aniline = 326.632*10-3* = 6947.3 kj/hr Enthalpy with water = 979.896 = 380604.8 kj/hr Total enthalpy out = 6947.3 +380604.8 = 387552.1 kj/hr Heat removed by the heat exchanger = 5576298-387552.1 = 5188745.9 kj/hr *( )

Energy balance for the decanter:

So, stream 7: enthalpy with aniline = 6947.3 kj/hr Enthalpy with water =380604.8 kj/hr Total enthalpy in=6947.3 +380604.8 =387552.1 kj/hr Stream 12: Water=32698.53348 kg/hr =1815.052 kmol/hr Aniline=7042.02739 kg/hr =75.62 kmol/hr Enthalpy with aniline = 75.62 *10-3* =1562.56 kj/hr Enthalpy with water = *(
44

= 704990.6 kj/hr Total enthalpy =1562.56+704990.6=706553.16 kj/hr Stream13: Water=5117.73724 kg/hr =284.08 kmol/hr Aniline=1392.55056kg/hr =14.95 kmol/hr Enthalpy with aniline =14.95 *10-3* =308.92 kj/hr Enthalpy with water =(284.08) *(

=110340.49 kj/hr Total enthalpy=308.92+110340.49=110649.41 kj/hr Enthalpy out: Stream9: Water = 44437.73942 kg/hr = 2466.68 kmol/hr Aniline =7102.20424kg/hr =76.26 kmol/hr Enthalpy with aniline = 76.26 *10-3* = 1575.79 kj/hr Enthalpy with water =2466.68 * =958091.68 kj/hr Total enthalpy=1575.79+958091.68=959666.79 kj/hr Stream 10: Water =5147.21291kg/hr =285.72 kmol/hr Aniline =31750.37067kg/hr =340.94 kmol/hr Enthalpy with aniline =340.94 *10-3* *(

45

=7044.96 kj/hr Enthalpy with water =285.72 * =110977.49 Total enthalpy = 7044.96+110977.49 =118022.45 kj/hr Table 13: *(

Flow

IN

IN

IN

OUT

OUT

Component

Stream 7(kj/hr)

Stream 12(kj/hr) ----704990.6 1562.56 706553.16

Stream 13(kj/hr) ----110340.49 308.92 110649.41

Stream 9(kj/hr) ----958091.68 1575.79 959666.79

Stream 10(kj/hr) ----110977.49 7044.96 118022.45

Nitrobenzene Hydrogen Water Aniline Total (kg/hr)

----380604.8 6947.3 387552.1

Energy balance for distillation column-1:

46

Enthalpy in: Stream9: Water =44437.73942 kg/hr =2466.68 kmol/hr Aniline =7102.20424kg/hr =76.26 kmol/hr

Enthalpy with aniline =76.26 *10-3* =26474.61 kj/hr Enthalpy with water =2466.68 * *(

=14511181.32 kj/hr Total enthalpy=26474.61 +14511181.32 =14537655.93 kj/hr Enthalpy out: Stream 11: Water =11739.20594 kg/hr =651.628 kmol/hr Aniline =60.17685 kg/hr =0.646 kmol/hr Enthalpy with aniline =0.646 *10-3* =216.6 kj/hr Enthalpy with water = 651.628 * *(

=3714415.04 kj/hr Total enthalpy=216.6+3714415.04=3714631.64 kj/hr Stream 12: Water =32698.53348 kg/hr =1815.052 kmol/hr Aniline =7042.02739 kg/hr =75.618 kmol/hr Enthalpy with aniline =75.618 *10-3* =26589.81 kj/hr Enthalpy with water

47

=1815.052 *

*(

=10802091.76 kj/hr Total enthalpy =26589.81+10802091.76 = 10828681.57 kj/hr Total enthalpy out=3714631.64+10828681.57=14543313.21 kj/hr Heat supplied by the distillation column=14543313.21-14537655.93=5657.28 kj/hr Table 14: Flow IN OUT OUT

Component Nitrobenzene Hydrogen Water Aniline Total (kg/hr)

Stream (kj/hr) ----14511181.32 26474.61 14537655.93 14537655.93

Stream (kj/hr) ----3714415.04 216.6 3714631.64

Stream (kj/hr) ----10802091.76 26589.81 10828681.57

14543313.21

Energy balance for distillation column-2:

48

Enthalpy in: Stream 10: Water = 5147.21291kg/hr =285.72 kmol/hr Aniline=31750.37067kg/hr=340.94 kmol/hr Enthalpy with aniline =340.94 *10-3* =195845.11 kj/hr Enthalpy with water =285.72 * *(

=2627299.22 kj/hr Total enthalpy=195845.11+2627299.22 =2823144.33 kj/hr Enthalpy out: Stream13: Distillate stream enriched with water Aniline = 1392.55056kg/hr=14.953 kmol/hr Water = 5117.73724 kg/hr=284.079 kmol/hr Enthalpy with aniline=14.953 *10-3* =5317.53 kj/hr Enthalpy with water =284.079 * =1707969.4 kj/hr Total enthalpy=5317.53+1707969.4=1713286.93 kj/hr Stream14: Bottom stream enriched with Aniline Aniline=30387.29578 kg/hr=326.302 kmol/hr Water=29.47567 kg/hr=1.636 kmol/hr *(

49

Enthalpy with aniline= 326.302 *10-3* = 259532.9 kj/hr Enthalpy with water =1.636 * =9836.13 kj/hr Total enthalpy = 259532.9 +9836.13 = 269369.03 kj/hr Total enthalpy out from distillation column=1713286.93+269369.03 =1982655.96 kj/hr Total heat removed by distillation column =1982655.96-2823144.33 =-840488.37 kj/hr Table 15: Flow IN OUT OUT *(

Component Nitrobenzene Hydrogen Water Aniline Total (kg/hr)

Stream (kj/hr) ----2627299.22 195845.11 2823144.33 2823144.33

Stream (kj/hr) ----1707969.4 5317.53 1713286.93

Stream (kj/hr) ----9836.13 259532.9 269369.03

1982655.96

50

10. DESIGN OF EQUIPMENTS

Symbols used in design of Shell and Tube heat exchanger:
A - heat transfer area, m2 or ft2 B - baffle spacing, in cp - specific heat at constant pressure, J/g oC or Btu/lb oF C- clearance, in hi -heat-transfer coefficient for inside of tube ,W/m2 oC or Btu/ft2 oF h hio -heat-transfer coefficient for outside of tube, W/m2 oC or Btu/ft2 oF h ho - shell side heat-transfer coefficient, W/m2 oC or Btu/ft2 oF h G - mass velocity, kg/m2 s or lb/ft2h K -thermal conductivity , W/m oC LMTD -logarithmic mean temperature difference PT tube pitch, in Q - quantity of heat, J or Btu Re Reynolds number U - overall heat-transfer coefficient, W/m2 oC or Btu/ft2 oF h

51

10.1 DESIGN OF SHELL AND TUBE HEAT EXCHANGER

Cold Fluid Data: Inlet Temperature t1=21 oC =69.8 oF Outlet Temperature t2=210 oC =410 oF Weight flow w=40211.4021 kg/hr Calculation of Heat load: Qh= m Cp T = 40211.4021*1.4*(210-25) =10414753.14 kg/hr Qc= m Cp T m= Qc/(Cp T) = 10414753.14/(H) =10414753.14/(2801.5-2643.7) =65999.7 Kg Hot Fluid data: Inlet Temperature T1=250oC Outlet Temperature T2=80oF Weight flow W=65999.7 kg/hr Calculation of TLMTD: TLMTD= T1-T2 / ln(T1/T2) TLMTD= 47.10oF Calculation of R and S values: R= (T2-T1)/(t2-t1)
52

= 0.918 S = (t2-t1)/(T2-t1) = 0.822 Calculation of Correction Factor: FT is found using LMTD correction factor curves From Graph we get, FT=0.845 The values of R and S satisfy with Correction factor value for 4-8 shell and tube heat exchanger. This may be met by four 1-2 exchangers in series or two 2-4 exchangers in series. tln= TLMTD*FT = 47.1*0.845 = 39.79F Calculation of ud From the literature the UD value of Nitrobenzene ranges from 60-90 W/m2K Assume a value of UD Let the value of UD be 80 Calculation of heat transfer area A= Q/ UD*t = 9871279.951/(80*39.79) = 3101.05 ft2 Length of the tube L=160(3/4 in.OD,16BWG)-Square pitch From the table, Flow area per tube at=0.302in2 Outside area per linear ft a=0.1963 ft2 Tube inside diameter D=0.62 in (Obtained from tables)
53

No. of tubes per shell, Nt= Heat transfer area/(No. of shell side passes* total surface area) Nt= 3101.05/(2*16*0.1963) = 493.67 = 494 tubes For 4 passes, 3/4in.OD on 1-in. Square pitch (from the table),Nearest count(from 494 tubes): 480 tubes in a 29in.ID shell Calculation of corrected UD: Ud,corr = Q/A* T LMTD. A= No. of passes * No. of tubes * Length of the tube * Outside area = 2* 480* 16* 0.1963 =3015.16 ft2 UD= Q/(A*T) =9871279.951/(3015.16*39.79) =82.27 Tube side Calculation: at = Nt * at/(144n) =480* 0.302/(144*4) = 0.252 ft2 Mass velocity: Gt = w/ at = 65999.7/(0454*0.252) =576880.11 lb/ hr ft2 At Tavg= 180C
54

Ret = D*Gt / Tube inside diameter = D = 0.62in = 0.62/12 =0.0517 Ret = 0.0517*576880.11/(0.0375) =795325.37 J factor for heat transfer curve jH At L/D = 16/0.0517 jH = 750 Cp = 0.47 btu/lb K = 0.0187 btu/ hr.ft2. F hi = jH *(K/D)*(C/K)1/3 = 750*(0.187/0.0517)*(0.47*0.0375/0.187)1/3 = 265.975 = 266 hio= hi * ID/OD = 265.97 * 0.62/0.75 =220 btu/hr. ft2.F At Re = 7,95,325.37 F= 0.0001, S= 0.7 Tube side pressure drop (Pt) = f Gt2 Ln/(5.22*1010*D *S) Pt= 0.0001*576880.112*16*4/(5.22*1010*0.0517*0.7) =1.125 Psi Gt = 576880.11 v2/2g = 0.037 Pr = 4n/ S*(v2/2g)
55

= 4*4*(0.037)/0.7 =0.84 Total pressure drop (PT) = Pt +Pr = 1.125+ 0.84 =1.965 Psi Shell side Calculations: B= 12in C = 0.25in PT= C + Tube OD = 0.25+0.75 =1 in Flow area as = ID* C*B/(144PT) = (29*0.25*12)/(144*2) = 0.302 ft2 Mass velocity : Gs= W/as = 40211.4021/(0.454*0.302) = 293282.68 lb/ hr.ft2 T avg= 117.5C = 0.4 Cp = 0.4*2.42 = 0.968 lb/ft. hr Res = De* Gs/ = 23985.75 JH =80 K = 0.16 W/ m.K = 0.16*6.93 btu/hr. ft2.F =1.1088 btu/hr. ft2.F ho = jH* K/ D*(C/K)1/3 = 80*1.1088/0.792*(0.968*0.334/1.1088)1/3 = 742.68 btu/hr. ft2.F f = 0.0018, S= 0.76 No. of Crosses N+1 = 12L/ B
56

= 12*4*16/12 =64 Shell diameter Ds= 29/12 = 2.41 ft Shell side pressure drop Ps = f Gs2Ds(N+1)/(5.22*1010*0..079*0.76) = 7.619 Psi Clean overall Coefficient Uc: Uc = hio* ho/(hio+ho) = 95.87 btu/hr.ft2.F Rd = UC- UD/( UC*UD) = 95.87-82.27/(95.87*82.27) =1.72*10-3 hr.ft2.F/ btu

57

Specification sheet of heat exchanger Item Type Heat Exchanger Two 2-4 shell & tube heat exchangers in series Operation Inlet temp. processing stream Outlet temp. processing temp. LMTD UC UD No.of tubes Pressure drop shell side Pressure drop tube side Heat transfer area Length of the tube Tube inner dia Tube outer dia Shell inner dia Pitch Baffle spacing No of baffles Continuous 69.8 F 410 F 47.10F 95.87 Btu /hr. ft2.F 82.27 Btu /hr. ft2.F 480 7.619 psi 1.965 psi 3015.16 ft2 16 ft 0.0517 ft 0.0625 ft 1.9375 ft 1 inch (square) 1 ft 16

58

Symbols used in the Design of the Reactor design: P1 , P2 = pressure of the gas T1 , T2 = temperature of gas V1 , V2 = volume of gas do=tube of outside diameter di =Inside diameter of tube TR =Residence time Vg = volumetric flow rate of gas through reactor V= volume of reactor N= be no. of tubes, A= Heat transfer area Pt=Triangular tube pitch Db = Bundle diameter Di = shell Internal Diameter J = weld joint efficiency factor t =thickness of dome q =Total Heat removed U Heat transfer coefficient: B=baffle spacing

59

10.2 DESIGN OF FIXED BED REACTOR 10.2.1. Estimation of volume of Reacting mixture: 1 kmol : 22.414 m3( at STP) P1V1/T1=P2V2/T2 1*22.414/273= 3* V2/593 V2=17.05 m3 1 kmol of hydrogen at 3 atm and 350 C =17.05 m3 1 kmol of reactant mixture =123.1092*0.1+2.0158*0.9=14.152 gm 46137.22728kg/hr of reactants =3260.12kmol/hr =55585.046m3/hr=15.44 m3/s 10.2.2. Estimation of volume of products mixture: P1V1/T1=P2V2/T2 1*22.414/273 =2*V2/600 V2=24.63 m3 1 kmol of products at 2 atm and 600 K =24.63 m3 1 kmol of product mixture =15.69gm, 46137.22728kg/hr of product mixture =2940.55 kmol/hr = 65909.49 m3/hr=18.31 m3/s Basis: 16.875 m3/s of gas Use 1.5 tubes of outside diameter (BWG 10no) and length =4m Wall thickness for BWG 10 no tube =0.134 Therefore, Inside diameter of tube =1.5-2*0.134=1.232=31.3 mm Volume of each tube = /4 * d2*L= /4 (31.2928*10-3)2*4=3.0764*10-3m3 Assumption:Residence time with in reactor =0.4 sec

60

T =volume of reactor/volumetric flow rate of gas through reactor,so volume of reactor is V=Residence time * Volumetric flowrate= 0.4*16.875=6.75 m3. Let N be no.of tubes, N (3.0764*10-3) = 6.75 N = 2194.12 = 2194 tubes (approx.) Heat transfer area =N (*do*h) = 2194**38.1*10-3* 4= 1050.44 m2 Triangular pitch is used to accommodate 2194 no of tubes. Triangular tube pitch, Pt=1.25do =1.25 *38.1=47.625 mm Bundle diameter:Db =do (Nt/K1)1/n1,Where K1, n1 are obtained from the table below based on
the type of tube arrangement.

=38.1(2194/0.319)1/2.142=2358 mm Graph: Shell inside diametervs. bundle diameter By extrapolating the bundle diameter to 2.358 m,we have Shell ID Bundle dia = 20 + (2010)*(5.41-1.2)/ (1.2-0.2) =31.58 mm Therefore shell ID =Bundle diameter + 31.58 mm= 2358 +31.58=5545.83 mm =2389.58 mm Height of a reactor = 10m Volume of a reactor = (/4)*D2*H= (/4) (2.38958)2 *10=44.85 m3 10.2.3. Shell Material of Construction: The preferred construction material for reactor is low alloy steel (IS: 3609) From Code IS 2825, f=12.6 kgf/mm2=1260 kgf/cm2 This is a Class-I vessel. Therefore, J = weld joint efficiency factor = 1
61

Here t = P*Di/(200fJ-P) +CA Where P=3 atm= (3.04*10-2*2389.58)/ (200*1*12.6-3.04 *10-2) + 1=1.029 mm Since t< 12 mm, Use t =12 mm (including corrosion allowance) in order to withstand its own weight. 10.2.4. ellipsoidal dome end: Calculation of Dome end Thickness:t = PDoC/200f J +CA +TA Assume t=10 mm hi =Di/4 =2389.58/4 =597.395 mm ho =hi+ t =597.395 +10 =607.395 mm Ro=0.82Di+ t =0.82 *2389.58 +10 =1969.46 mm ro= 0.15 Di+T =0.15*2389.58 +10=368.437 mm Do=Di+2t =2389.58 +2*12 =2413.58 mm Do2/4Ro= 2413.582/(4*1969.46) = 739.46 mm Sqrt(Do* ro /2)=Sqrt (2413.58*368.437/2)=666.8 mm ho= 668.8 mm ho is least. Therefore hE=ho=668.8 mm hE/Do=668.8/2413.58 =0.277; t/Do=10/2413.5 =4.14*10-3. From graph hE/Do vs C, we have C=1.35t = =PDoC/200f J= (3.04*10-2*2413.58*1.35)/(200*1*12.6)= 0.091 mm So, thickness of dome = 0.067mm Shell side fluid is water. Total Heat removed = 94101140.57 kj/hr
62

Heat removed per tube = (94101140.57*103)/(3600*2194)= 11913.95 W q = UAT, Substituting A=1050.44 m2,T=370-298 = 72K, q = 94101140.57 kj/hr We have U = 1244.25 W/m2 C Internal diameter of vessel = 2413.5 mm We know that Ds/5 < baffle spacing < Ds i.e., 482.7< baffle spacing<2413.5 Use Baffle spacing = 1360 mm Number of baffles = 4 10.2.5. Design Specifications: Tubes: Number of tubes: 2194 Length: 4m Catalyst filled height: 3.8 m Inside diameter: 31.3 mm Outside diameter: 38.1 mm Gauge: BWG 10 number Heat transfer area: 1050.44 m2 Passes: 1 (flow in upward direction) Tube Pattern: Triangular Tube Pitch: 47.6 mm Inlet temperature: 350 C Outlet temperature: 426.85 C 10.2.6. Shell: Fluid: water94101140.57 kj/hr=m*4.198*(370-298)
63

Flow: 311.33 Tons/hr Inlet temperature: 25 C Outlet temperature: 96.85 C Heat removed per tube: 11913.95W Heat transfer coefficient: U = 55.29 W/m2 C Inside Diameter: 2389.58 mm Passes: 1 Baffles: 4 Baffle spacing: 1360 mm 10.2.7. Details about construction material: Type of material: Low alloy steel Material specification: IS: 3609Grade or designation: 2.5% Cr, 1% Mo Tensile strength (min): 49 Kg/mm2 Yield stress (min): 25 Kg/mm2 10.2.8. Reactor specifications: Orientation: Vertical Operation mode: Continuous Height: 10 m Outside diameter: 5498 mm Class: I Design Pressure: 3 atm Wall thickness: 12 mm Type of Ends: Ellipsoid, 2.5:1
64

End thickness: 10 mm Man holes: 2 * 450 mm * 400 mm Catalyst weight: From literature, wt% of the catalyst=0.05% of Nitrobenzene[7] Therefore,weight of catalyst=0.0005*40211.40421=20.10 kg of catalyst.

65

Symbols used in design of Cooler:

A - heat transfer area, m2 or ft2 B - baffle spacing, in cp - specific heat at constant pressure, J/g oC or Btu/lb oF C- clearance, in hi -heat-transfer coefficient for inside of tube ,W/m2 oC or Btu/ft2 oF h hio -heat-transfer coefficient for outside of tube, W/m2 oC or Btu/ft2 oF h ho - shell side heat-transfer coefficient, W/m2 oC or Btu/ft2 oF h G - mass velocity, kg/m2 s or lb/ft2h K -thermal conductivity , W/m oC LMTD -logarithmic mean temperature difference PT tube pitch, in Q - quantity of heat, J or Btu Re Reynolds number U - overall heat-transfer coefficient, W/m2 oC or Btu/ft2 oF h

66

10.3 DESIGN OF COOLER

Cold Fluid Data: Inlet Temperature t1=25oC =77oF Outlet Temperature t2=131o F Weight flow w=19035.82kg/hr Hot Fluid data: Inlet Temperature T1=371.69oK = 209.12oF Outlet Temperature T2=303.15oK =86o F Weight flow W=42186.67 kg/hr i.e 11786.68 kg/hr of water + 30417.99696 kg/hr of aniline Calculation of TLMTD: T1= 209.12-86 =123.12o F T2= 86-71 =15oF TLMTD = T1-T2 / ln(T1/T2) = 17.79oF Calculation of R and S values: R= (T1-T2)/(t2-t1) = 2.28 S = (t2-t1)/(T2-t1) = 0.4

67

Calculation of Correction Factor: FT is found using LMTD correction factor curves From Graph we get, FT=0.94 The values of R and S satisfy with Correction factor value for 2-4 shell and tube heat exchanger. tln = TLMTD*FT = 17.79*0.94 = 16.72F Calculation of UD From the literature the UD value of middle and heavy organics ranges from 60-90 W/m2K Assume a value of UD Let the value of UD be 70 btu/hr ft2 Calculation of heat transfer area A= Q/ UD*t = 51881745.9/(1.055*70*16.72) = 4433.3 ft2 Length of the tube L=160(3/4 in.OD,16BWG)-Square pitch From the table, Flow area per tube at=0.302in2 Outside area per linear ft a=0.1963 ft2 Tube inside diameter D=0.62 in (Obtained from tables) No. of tubes per shell, Nt= Heat transfer area/(No. of shell side passes* total surface area) Nt= 4433.3/(2*16*0.1963)

68

= 705.76 = 706 tubes For 3/4in.OD on 1-in. Square pitch (from the table),Nearest count(from 706 tubes): 688 tubes in a 33in.ID shell Calculation of corrected UD: Ud,corr = Q/A* T LMTD. A= No. of passes * No. of tubes * Length of the tube * Outside area = 2* 688* 16* 0.1963 =4321.74 ft2 UD = Q/(A*T) =51881745.9/(1.055*4321.74*16.72) =68.06 Tube side Calculation: at = Nt * at /(144n) =688* 0.302/(144*4) = 0.36 ft2 Mass velocity: Gt = w/ at = 42186.67/(0.454*0.36) = 258117.2 lb/ hr ft2 At Tavg= 64.25C for aniline water mixture =3.46lb/ft hr Ret = D*Gt /
69

Tube inside diameter = D = 0.62in = 0.62/12 =0.0517 ft Ret = 0.0517*258117.2/(3.46) = 3856.83 j factor for heat transfer curve jH At L/D = 16/0.0517 =25.8 jH = 4.2 (from graph) Cp = 0.65 Btu/lb K = 0.17 Btu/ hr.ft2. F hi = jH *(K/D)*(C/K)1/3 = 4.2*(0.17/0.0517)*(0.65*3.46/0.17)1/3 = 32.66 hio= hi * ID/OD = 32.66 * 0.62/0.75 =27 Btu/hr. ft2.F At Re = 3856.83 f= 0.00036, S= 0.7 Tube side pressure drop (Pt) = f Gt2 Ln/(5.22*1010*D *S) Pt= 0.00036*258117.22*16*4/(5.22*1010*0.0517*0.7) =0.81 Psi For Gt = 258117.2 ,v2/2g = 0.012 Return pressure drop (Pr) = 4n/ S*(v2/2g) = 4*4*(0.012)/0.7 =0.274 psi
70

Total pressure drop (PT) = Pt +Pr =1.084 Psi Shell side Calculations: B= 12in C = 0.25in PT = C + Tube OD = 0.25+0.75 =1 in Flow area as = ID* C*B/(144PT) = (33*0.25*12)/(2*144*1) = 0.343 ft2 Mass velocity : Gs= W/as = 19035.82/(0.454*0.343) = 121975.61 lb/ hr.ft2 T avg= 40C = 0.7 Cp = 1.6933 lb/ft. hr Res = De* Gs/ De =0.95/12 = 0.0792 ft Re = (0.0792*121975.61)/1.6933 =5705.11 jH =37 K = 0.609 W/ m.K = 0.352 btu/hr. ft2.F ho = jH* K/ D*(C/K)1/3 = 37*0.352/0.0792*(1*1.6933/0.609)1/3 = 231.23 btu/hr. ft2.F f = 0.0026, S= 0.72 No. of Crosses N+1 = 12L/ B = 12*16*2/12 = 32
71

Shell diameter Ds= 33/12 = 2.75 ft Shell side pressure drop Ps = f Gs2Ds(N+1)/(5.22*1010*0.079*0.72) = 1.14 Psi Clean overall Coefficient Uc: Uc = hi0* h0/(hi0+h0) = 80.4 btu/hr.ft2.F Dirt Factor Rd : Rd = UC- UD/( UC*UD) =2.255*10-3 hr.ft2.F/ btu

72

Specification sheet of Cooler Item Type Operation Inlet temp. processing stream Outlet temp. processing temp. LMTD UC UD No.of tubes Pressure drop shell side Pressure drop tube side Heat transfer area Length of the tube Tube inner dia Tube outer dia Shell inner dia Pitch Baffle spacing No of baffles Heat Exchanger 2-4 shell & tube Continuous 209.12 F 86 F 17,79 F 68.06 Btu /hr. ft2.F 80.4 Btu /hr. ft2.F 688 1.14 psi 1.084 psi 4321.74 ft2 16 ft 0.0517 ft 0.0625 ft 1.9375 ft 1 inch (square) 1 ft 16

73

Symbols used in the design of the Distillation column:

x = mole fraction of water in liquid phase y = mole fraction of water in gas phase 1 =activity coefficient of water in liquid phase xD = mole fraction of water in distillate R = reflux ratio Rm =minimum reflux ratio. Roptimum= optimum reflux ratio v1= density of the vapour L1, L2 =Density of the liquid M1 =average molecular weight T =Boiling temperature S1, S2 =Cross sectional area Q =vapour rate q =Liquid rate An =Net tower cross sectional area W=Weir length Aw =tray area used by one downspout T =Tower diameter Ad =Downspout cross sectional area h1 =Weir crest hw =weir height hD =Dry pressure drop
74

A0=area of one sieve V0= velocity through orifice G =Viscosity of gas NRo =Sieve Hole Reynolds number f =fanning friction factor hL =Hydraulic head: hR =Residual pressure drop hG =Total gas pressure drop h2=Pressure loss at liquid entrance Ada =the area for liquid flow under apron t = tray spacing

75

10.4 DESIGN OF DISTILLATION COLUMN - 2

Feed to the distillation column: Water = 5147.21291 kg/hr Aniline=31750.37067 kg/hr Top product from Distillation column consists of 78.61 wt% of water. Bottom product from Distillation column consists of 0.097 wt% of water. 10.4.1. Material balance: Feed: Moles of water in feed=5147.21291/18.0152=285.715 kmol/hr Moles of Aniline in feed=31750.37067/93.1262=340.939 kmol/hr Mole fraction of Water in feed=285.715/(285.715+340.939)=0.456 Total moles of feed=626.654 kmol/hr Distillate: Aniline in top product =1392.55056kg/hr Water in top product=5117.73724 kg/hr Moles of water in distillate=5117.73724/18.0152=284.079 kmol/hr Moles of Aniline in distillate=1392.55056/93.1262=14.953 kmol/hr Mole fraction of water=77.299/(77.299+54.955)=0.95 Total moles of distillate=299.032 Bottom: Aniline=30387.29578 kg/hr Water=29.47567 kg/hr Moles of aniline in bottom product=30387.29578/93.1262=326.302 kmol/hr Moles of water in bottom product=29.47567/18.0152=1.636 kmol/hr
76

Mole fraction of water in bottom product=1.636/ (1.636+326.302) =0.005 Total moles in bottom=327.938 kmol/hr 10.4.2. Vapour-liquid equilibrium data: Equilibrium data for Water and Aniline mixture at 743mm of HgTable 16: T0C P1sat(mm of Hg) 100 105 110 115 120 125 130 135 140 145 150 155 160 165 170 175 180 754.05 898.87 1066.02 1258.05 1477.74 1727.98 2011.91 2332.81 2694.18 3099.68 3553.18 4058.68 4620.43 5242.82 5930.4 6687.9 7520.23 P2sat(mm of Hg) 44.94 55.38 67.81 82.51 99.81 120.03 143.65 171.0 202.58 238.79 280.24 327.46 381.05 441.64 509.9 586.53 672.29 0.314 0.236 0.197 0.1599 0.136 0.1128 0.0948 0.0795 0.0663 0.0548 0.0446 0.0357 0.0277 0.0207 0.0143 0.00862 0.00348 2.999 3.220 3.272 3.275 3.253 3.21 3.164 3.115 3.065 3.017 2.971 2.928 2.887 2.849 2.814 2.781 2.750 0.957 0.935 0.96 0.888 0.881 0.843 0.814 0.779 0.738 0.691 0.635 0.572 0.498 0.147 0.322 0.216 0.097 X 1 y

10.4.3. Ideal stages using Mc-Cabe-Thieles method Feed is vapour at its dew point: So, q-line is passing through x=y=0.456 with slope zero i.e is horizontal. q-line meets equilibrium curve at y=0.46 & x=0.02. Operating line for the enriching section pass through x=xD= y=0.95 and y=0.46 & x=0.02.
77

It intersects the Y-axis at y=0.45 So, xD/(Rm+1)=0.45,Rm=1.11 where Rm is minimum reflux ratio. Roptimumis 1.2 to 1.5 times of Rm. R=1.5*1.11=1.665 Then, Y-intercept for enriching section operating line=xD/(R+1) = 0.35 And this operating line meets the q-line at x=0.165 and y=0.46 The operating line for stripping section is drawn from above point to x=y=xD= 0.005. So, no of ideal or theoretical stages=3. 10.4.4. Actual trays using efficiency of tray Viscosity of water = 0.282 cP Viscosity of Aniline = 1.5 cP Average viscosity=0.282*0.46+1.5*.54=0.9397=18.66% So, efficiency =18.66% No. of ideal stages/no. of real stages = efficiency No. of real stages= 2/0.1866 = 10.71 = 11. 10.4.5. Ideal feed tray location using Mc-Cabe-Thiele diagram Feed is introduced between 1 and 2 tray. From the diagram, feed plate is the 1.18th plate 10.4.6. Actual feed tray location using efficiency of plate Feed location=1.18/.1866=6.32, so feed is introduced between 6 and 7. No. of real stages in stripping section=5 No. of real stages in enriching section=6

78

10.4.7. The height of the column using thumb rule of plate spacing and the number of actual plates Plate spacing=60 cm No. of total stages=11 With one extra plate spacing at feed tray and One each above the topmost and Below the bottom-most tray. Column height=13*60=7.8 m. Moles of vapour at the top of the column: R= L/D so L=R*D; V1= L+D = R*D+D = (R+1)*D = (1.665+1)*299.092=797.08 kmol/hr Moles of vapor at the bottom of the column: V2=797.08-626.654=170.426 kmol/hr. 10.4.10. Boiling temperature, average molecular weight, density of the vapour and density of the liquid at the top and the bottom of the column Top: T1=x*T=(184.4*0.05+100*.95)=95.92 C=369.07 K M1= x*M=(93.1262*0.05+18.0152*0.95)=21.77 v1=PM/RT=743821.77/(760*0.08205*369.07)=0.703 kg/m3=0.0323 kmol/m3 Bottom: T2=x*T=(184.4*0.995+100*.005)=183.978C=457.13K M2=x*M=(93.1262*.995+18.0152*.005)=92.75 v2=PM/RT=2.4175 kg/m3=0.026 kmol/m3 Density of the liquid = (x1* L1 )+ ( x2* L2) =0.995*1021.7+0.005*971.8=1021.45 kg/m3.
79

Density of the liquid=L1=L2=1021.45 kg/m3(assume density of the liquid does not change much with temperature as that of vapor). 10.4.11. Vapour velocity & Cross sectional area of the column at the top and the bottom Vapour velocity

Where Kv=0.05 Mass flow rate(m)=us s=(/4)D2 =m/u Top: (u1)=K1*(( L- v1)/ v1)0.5=1.905m/sec=6858 m/hr S1=V1/ (u1* v1)= 797.08/(6858*0.0323)=3.6 m2. Bottom: (u2)=K2*(( L- v2)/ v2)0.5=1.027 m/sec=3697.2 m/hr S2=V2/ (u2* v2)= 170.426/(3697.2*0.026)=1.772 m2 So, higher cross sectional area S1 is used for further calculations. 10.4.12.Diameter of the column Enriching section [4]: v1=0.703 kg/m3=0.0323 kmol/m3 Vapor rate Q=V1/molar density=797.08/(0.0323*3600)=6.855 m3/s. L2=1021.45 kg/m3 Liquid rate q=327.938 kmol/hr*92.75/1021.45=8.3*10-3 m3/s Net tower cross sectional area An=3.6 m2

80

Tentatively choose a weir length W=0.7T. Table 6.1[4]:the tray area used by one downspout=8.8% At=3.6/(1-0.088)=3.947 m2 Tower diameter T=(4*At/)0.5=(4*3.947/)0.5=2.242 m, say 2.24 m Corrected At = T2/4 = 2.242/4 = 3.94 m2. W = 0.7*T = 0.7*2.24 = 1.568 m Downspout cross sectional area Ad=0.088*3.94=0.3467 m2 For the design area taken by tray support + disengaging and distributing zones [4]=0.222m2. Active perforated area Aa=At-2*Ad-0.222=3.94-2*0.3467-0.222=3.0246 m2 q/W=6.26*10-3 m3/m.s is ok. Weir crest h1 and weir height hw: Let h1=25mm=0.025 m.h1/T=0.025/2.24=0.011 T/W=1/0.7=1.429 Eq:6.34[4]:Weff/W=(1.4292-((1.4292-1)0.5+2*0.011*1.429)2)0.5=0.967 Eq.6.33 [4]:h1=0.666(6.26*10-3*0.967)2/3=0.0207m So take h1=0.0207m, h1/T=0.0207/2.24=0.0092 T/W=1/0.7=1.429 Eq:6.34[4]:Weff/W=(1.4292-((1.4292-1)0.5+2*0.0092*1.429)2)0.5=0.972 Eq.6.33 [4]:h1=0.666(6.26*10-3*0.972)2/3=0.0206m.is ok So, final h1=0.0207m. Set weir height haw=50mm=0.05m. Dry pressure drop hD: Eq.6.37 [4]c0=1.09*(d0/l)0.25=1.09*(0.0045/0.002)0.25=1.335
81

A0=0.0555*Aa=0.0555*3.0246=0.1679 m2. V0=Q/A0=6.855/0.1679=40.83 m/s. Viscosity of gas is taken as G=0.012cP=1.25*10-5 kg/m.s Hole Reynolds number [4] =d0*V0* v1/ G=0.0045*40.83*0.703/1.25*10-5=10333.5 So, fanning friction factor for NRe=10333.5 is f=0.0075,g=9.807 m2/s,l=.002l.Eq.6.36, hD=0.1096 Hydraulic head hL: Va=Q/Aa=6.855/3.0246=2.266 m/s. Z=(T+W)/2=(2.24+1.568)/2=1.904 m Eq 6.38:hL=0.0209 m Residual pressure drop hR Eq.6.42 [4]:hR=(6*0.04*1)/(1021.42*0.0045*9.807)=0.00532 m Total gas pressure drop hG: Eq.6.35 [4]:hG=hD+hL+hR=0.1096+0.0209+0.00532=0.13582 m Pressure loss at liquid entrance h2: The area for liquid flow under apron =0.025*W=0.025*1.568=0.0392 m2. Since this is smaller than Ad,Ada=0.0392 m2. Eq. 6.43[4]:h2= (q/Ada) 2*1.5/g= (0.00827/0.0392)2*1.5/9.807=0.00681 m. Backup in downspout: Eq.6.44 [4]; h3=hG+h2=0.13582+0.00681=0.14263 m. Check on flooding: hW+h1+h3=0.05+0.025+0.14263=0.21763 m For tower diameter T between 1 and 3 m, tray spacing t=0.60m. hW+h1+h3=0.21763, which is well below t/2=0.30m. Therefore the chosen t is satisfactory.

82

Weeping velocity: for W/T=0.7, the weir is set 0.3296T=0.738 m from the centre of the tower. Therefore Z=2*0.738=1.476 m. All other quantities in Eq 6.46 have been evaluated and then the equation yields VOW=7.47 m/s. The tray will not weep excessively until the gas velocity through the holes V0 is reduced ti close to this value. Entrainment: v1=0.703 kg/m3=0.0323 kmol/m3 vapour rate Q=V1/molar density=797.08/(0.0323*3600)=6.855 m3/s. L2=1021.45 kg/m3 Liquid rate q=327.938 kmol/hr*92.75/1021.45=8.3*10-3 m3/s L=q* L=0.0083*1021.45=8.478 kg/s G=Q* v1=6.855*0.703=4.819 kg/s V/VF=0.8, ( v1/ L)0.5*L/G=0.046 Fig 6.17: E=0.07.The recycling of liquid resulting from such entrainment is too small to influence the tray hydraulics appreciably. Stripping Section: v2=PM/RT=2.4175 kg/m3=0.026 kmol/m3 M2=x*M=(93.1262*.995+18.0152*.005)=92.75 V2=797.08-626.654=170.426 kmol/hr. Q=170.126/(3600*0.026)=1.82 m3/s L2=1021.45 kg/m3 Liquid rate q=327.938 kmol/hr*92.75/1021.45=8.3*10-3 m3/s

83

Net tower cross sectional area An=1.772m2 Tentatively choose a weir length W=0.7T. Table 6.1[4]:the tray area used by one downspout=8.8% At=1.772/(1-0.088)=1.943 m2 Tower diameter T=(4*At/) 0.5=(4*1.943/)0.5=1.573 m, say 1.57 m Corrected At=T2/4= 1.572/4=1.936 m2. W=0.7*T=0.7*1.57=1.099 m Downspout cross sectional area Ad=0.088*1.936=0.1704 m2 For the design area taken by tray support + disengaging and distributing zones=0.222m2. Active perforated area [4] Aa=At-2*Ad-0.222=1.936-2*0.1704-0.222=1.3732 m2 q/W=7.55*10-3 m3/m.s is ok. Weir crest h1 and weir height hw: Let h1=25mm=0.025 m.h1/T=0.025/1.57=0.016 T/W=1/0.7=1.429 Eq:6.34[4]:Weff/W=(1.4292-((1.4292-1)0.5+2*0.011*1.429)2)0.5=0.951 Eq.6.33 [4]:h1=0.666(7.55*10-3*0.951)2/3=0.0265m So take h1=0.0265 m, h1/T=0.0265/1.57=0.0169 T/W=1/0.7=1.429 Eq:6.34[4]:Weff/W=(1.4292-((1.4292-1)0.5+2*0.0169*1.429)2)0.5=0.948 Eq.6.33 [4]:h1=0.666(7.55*10-3*0.972)2/3=0.0266m.is ok So, final h1=0.0265m.

Set weir height hw=50mm=0.05m.

84

Dry pressure drop hD: Eq.6.37 [4]c0=1.09*(d0/l)0.25=1.09*(0.0045/0.002)0.25=1.335 A0=0.0555*Aa=0.0555*1.3732=0.0762 m2. V0=Q/A0=1.82/0.0762=23.88 m/s. Viscosity of gas is taken as G=0.012cP=1.25*10-5 kg/m.s Hole Reynolds number=d0*V0* v1/ G=0.0045*23.88 *2.4175 /1.25*10-5=18473.57 So, fanning friction factor for NRe=10333.5 is f=0.0065,g=9.807 m2/s,l=.002l.Eq.6.36[4], hD= 0.133 m Hydraulic head hL: Va=Q/Aa=1.82/1.3732=1.333 m/s. Z= (T+W)/2= (2.24+1.568)/2=1.3345 m Eq.6.38:hL=0.0253 m Residual pressure drop hR Eq.6.42 [4]:hR= (6*0.04*1)/(1021.42*0.0045*9.807)=0.00532 m Total gas pressure drop hG: Eq.6.35 [4]:hG=hD+hL+hR=0.133+0.0253+0.00532=0.16362 m Pressure loss at liquid entrance h2: The area for liquid flow under apron =0.025*W=0.025*1.568=0.0275 m2. Since this is smaller than Ad,Ada=0.0275 m2. Eq. 6.43[4]:h2= (q/Ada) 2*1.5/g= (0.00827/0.0275)2*1.5/9.807=.0139 m. Backup in downspout: Eq.6.44; h3=hG+h2=0.16362 +.0139 =0.1775 m. Check on flooding: hW+h1+h3=0.05+0.0265+0.1775 =0.254 m For tower diameter T between 1 and 3 m, tray spacing t=0.60m. hW+h1+h3=0.254, which is well below t/2=0.30m.
85

Therefore the chosen t is satisfactory. Weeping velocity: for W/T=0.7, the weir is set 0.3296T=0.517 m from the centre of the tower. Therefore Z=2*0.517=1.034 m. All other quantities in Eq.6.46 have been evaluated and then the equation yields VOW=2.901 m/s. The tray will not weep excessively until the gas velocity through the holes V0 is reduced ti close to this value. Entrainment: v2=PM/RT=2.4175 kg/m3=0.026 kmol/m3 M2=xM=(93.1262*.995+18.0152*.005) =92.75 V2=797.08-626.654=170.426 kmol/hr. Q=170.126/(3600*0.026) =1.82 m3/s L2=1021.45 kg/m3 Liquid rate q=327.938 kmol/hr*92.75/1021.45=8.3*10-3 m3/s L=q* L=0.0083*1021.45=8.478 kg/s G=Q* v1=1.82*2.4175=4.4 kg/s V/VF=0.8, (v2/ L)0.5*L/G=0.094 Fig 6.17: E=0.042.The recycling of liquid resulting from such entrainment is too small to influence the tray hydraulics appreciably. The minimum column diameter for tray columns is typically 0.75 m; otherwise, packed columns are used. The maximum diameter of the column can be quite large up to 5 m although it may be decided to operate 2 or more separate columns in place of an otherwise large diameter single column.

86

As the column diameter decreases, the vapour velocity increases for a given vapour flow rate.

The minimum column diameter is based upon the maximum vapour velocity that causes excessive entrainment and flooding.

The maximum column diameter is based upon maintaining a high enough velocity to prevent excess weeping.

The operating vapour velocity, and hence actual column diameter, is specified as a fraction of the flooding vapour velocity typically 0.65 to 0.90.

The final consideration is column cost a larger diameter column is more expensive than a smaller diameter column, although economies of scale enter

87

11. COST ESTIMATION AND ECONOMICS

An acceptable design must present a process that is capable of operating under conditions which yields profit. Capital must be allocated for the direct plant expenses such as those for raw materials, labour and equipment. Besides direct expenses many other indirect expenses are also incurred e.g. administration, salaries, product distribution cost, cost for interplant communications. A capital investment is required for any industrial process and determination of necessary investment for any process consists of fixed capital investment for physical equipment and facilities in the plant plus working capital which must be available to pay the salaries keep raw materials and products on the hand and handle other specified items required a direct cash outlay. Thus in analysis of cost in industrial processes, capital investment cost, manufacturing costs and general expenses including income taxes must be taken into consideration. Here method chosen is the annual cost method because of the following advantages: 1. Effects of seasonal variations are soothed out. 2. Plant on stream time or equipment operating factor is considered. 3. It permits more rapid calculation of operating cost at less than full capacity. 4. It provides a convenient way of considering infrequently occurring but large expenses such as annual turn around cost. Cost of producing aniline per annum in 2002 = $ 5.5x106 Chemical plant index for the year 2002 = 76.2 Chemical plant index for the year 2012 = 402 Therefore cost of plant in 2012 = Cost in 2002x {(cost index in 2012)/ (cost index in 2002)} = 5.5x106 (402/76.2) = $ 29.016x106 Or Rs. 143.63 crores (1$ = 49.5 Rs) Therefore fixed capital cost = FCC = Rs 143.63 crores Total capital investment = TCI = FCC + Working capital Working capital = 25% of TCITherefore working capital = Rs 179.54 crores

88

DISTRIBUTION OF CAPITAL COST Table 17:

INDIRECT COST % Of FCC COST (crores of Rs.) Table-18:

ESTIMATION OF TOTAL PRODUCT COST Let X be the total product cost Distribution of total product cost

89

DIRECT PRODUCTION COST COST (In Crores) Table-19:

FIXED CHARGES COST (In Crores) Table-20:

Fixed charge = 16% of TPC (let) 20.1082 + 0.07125X = 0.16X X = 226.57 crores

GENERAL EXPENSES Table-21:

90

Total product cost = manufacturing cost + general expenses = (30.1082 + 0.76875X) + 0.2375X = 30.1082 + 1.00625X X = 226.57 crores Therefore general expenses = 53.4 crores Therefore manufacturing cost = 204.2 crores or Direct production cost

BREAKEVEN ANALYSIS: Breakeven point occurs when the total annual product cost equals the total annual sales. The total annual product cost is the sum of the fixed cost (including fixed charges, Overhead and general expenses) and direct production cost for n units per year. The total annual sale is the product of the number of units and the selling price per unit. Cost price of aniline per kg = 226.57x107/1x107 = 226.57 or Rs. 227 Assuming a profit margin of 10% so selling price of the product = Rs. 250 Gross annual earnings = total annual sales total annual product cost = Rs. 23 crores Net annual earnings = gross annual earnings income tax = 23 40% of 23 =Rs. 13.8 crores Pay back period = Total capital investment / Net annual earnings = 179.54/ 13.8 = 13 years (approx) Rate of return = Net profit / FCC = 13.8/143.6 = 9.6%

91

12. PLANT LOCATION AND LAYOUT

PLANT LOCATION AND SITE SELECTION: The location of the plant can have a crucial effect on the profitability of a project and the scope for future expansion. Many factors must be considered must be considered when selecting a suitable site. The factors to be considered are: 1. Raw Material Supply 2. Location with respect to the marketing area

3. Transport facilities 4. Availability of Labour 5. Availability of Utilities: Water, fuel an Power 6. Availability of Land 7. Environmental Impact and Effluent Disposal 8. Climate 9. Taxation and legal restrictions 10. Flood and Fire Protection 11. Local Community Considerations RAW MATERIALS: The availability and price of suitable raw material often determine the site of location of the plant.In this project nitrobenzene is the major raw material and produced in major quantities by nitration of benzene Approximately 95% of nitrobenzene is consumed in the production of aniline which is a precursor to rubber chemicals, pesticides, dyes,explosives, and pharmaceuticals.Nitrobenzene is also used in shoe and floor polishes, leather dressings, paint solvents, and other materials to mask unpleasant odours. Redistilled, as oil of mirbane, nitrobenzene has been used as an inexpensive perfume for soaps. A significant merchant market for nitrobenzene is its use in the production of the analgesic paracetamol MARKETING AREA: The location of market or intermediate distribution centres affects the cost of product distribution and the time required for shipping. Proximity to the major markets is an important consideration in the selection of plant site, because the buyer usually finds it it

92

advantage to purchase from nearby sources. The closer the market, The lesser will be the transportation cost and the easier will be the access to the products by the buyers. TRANSPORTATION FACILITIES : The transport of material and product to and from the plant will be an overriding consideration in the site selection .Here the site should be chosen so as to be closed to at least two major forms of transport : road, rail, waterway (canal and river ) or a sea port. Road and rail transport is being increasingly used, and is suitable for long distance transport of bulk chemicals like aniline Air transport is convenient and efficient for the movement of personnel and essential equipment and supplies and the proximity od the site airpot should be considered. AVAILABILITY OF LABOUR: Labour will be needed for construction of the plant and its operation. Skilled construction workers will be usually be brought in from outside the site area, but there should be an adequate pool of unskilled labour available locally and labour suitable for the training to operate the plant. Skilled tradesman will be needed for plant maintenance. Local trade union customs and restrictive practices will have to be considered when assessing the availability and suitability of the local labour for recruitment and training. Apart from this consideration should be given to the pay rates, restrictions on the number of hours, raial problems and variations in the skills and intelligence of the workers. UTILITIES (SEVICES): Chemical processes invariably require large quantities of water for cooling and general process use and therefore, the plant must be located near a source of water of suitable quantity. Process water may also be drawn from river, from wells, or purchased from a local authorities. In some sites the cooling water required can be taken from a river or lake, or from the sea: at other location cooling tower will be needed. Hence , the plant should be located near a lake, or sea. Apart from this electrical power is also needed in large quantities and hence, location of plant near hydroelectric installations should be considered. A competitive priced fuel should also be looked for near or on site for steam and power generation.

93

LAND (SITE SELECTION): The plant location should be chosen such that sufficient suitable land is available for the proposed plant and also for future expansions. The land should be ideally flat, well drained and have suitable load bearing characteristics. A full site evaluation should be made be taken into consideration in order to determine the need of piling or other special formations. ENVIRONMENT IMPACT AND DISPOSAL: All industrial processes produce waste products and full consideration must give to the difficulties and cost of their disposal. The disposal of toxic and harmful effluent should be done following the local waste disposals regulation and also, the appropriate authorities must be consulted during the initial site survey to determine the standards that must be met. CLIMATE: Adverse climate conditions at a site will increase cost. Abnormally low temperatures will required the provision of additional insulation and special heating for equipment and pipes runs. Stronger structure will be needed at locations which are subjected to high winds (cyclone and hurricanes areas) or earthquake. Hence, the effect of humidity and temperatures at the site must be taken into consideration because it affects the economics evaluations of the projects. TAXATION AND LEGAL RESTRICTIONS: Capital grants, tax concession and other inducement are often given by government to direct renewed investment to preferred locations, such as areas of high unemployment. The availability of such grants can be the overriding consideration in site selection. FLOOD AND FIRE PROTECTION: Before choosing be examined. The regional history of natural events like floods and hurricane damage should be examined. In case of major fire they should be provision for fire assistance from outside the fire department. LOCAL COMMUNITY CONSIDERATION:

94

Cultural facilities foe the communities are the important for the sound growth. The proposed plant must fit in with and be acceptable to the local community. Full consideration must be given to the safe location of the plant so that it does not impose a significant additional rest to the community. On a new site , the local community must be able to provide adequate facilities for the plant personnel; school, banks, housing and recreational and cultural facilities. Considering all the above factors the aniline plant should be located at a place where: 1. 2. The road and the rail transport system is easily available. Since Nitrobenzene does not occur naturally in the environment. It is produced industrially by reacting benzene with sulphuric acid, nitric acid and water. As it is major raw material for production of aniline . So, plant site should be nearer to a industries which produce nitrobenzene in order to avail the raw material cheaply. 3. Aniline used in a variety of applications; rubber processing chemicals (9%), herbicides (2%), and dyes and pigments (2%).[5]As additives to rubber, aniline derivatives. Hence plant should be located to a place where aniline can be easily consumed.

1 1 1

95

8 1 3 2 10 0 9 5

7 2 4

11

1. TANK FARM 2. PLANT AREA 3. EXPANSION 4. PLANT UTILITIES 5. STORES 6. FIRE STATION 7. CANTEEN 8. EMERGENCY WATER 9. LABORATORY 10. WORK SHOP 11. OFFICE

96

13. POLLUTION CONTROL AND SAFETY

Aniline: Aniline is a clear to slightly yellow liquid with a characteristic odour. It does not readily evaporate at room temperature. Aniline is slightly soluble in water and mixes readily with most organic solvents .Aniline is used to make a wide variety of products such as polyurethane foam, agricultural chemicals, synthetic dyes, antioxidants, stabilizers for the rubber industry, herbicides, varnishes and explosives.

Potential health effects: Aniline can be toxic if ingested, inhaled, or by skin contact. Aniline damages haemoglobin , a protein that normally transports oxygen in the blood. The damaged haemoglobin cannot carry oxygen. This condition is known as met hemoglobinemia and its severity depends on how much you are exposed to and for how long. Met haemoglobinemia is the most prominent symptom of aniline poisoning in humans, resulting in cyanosis (a purplish blue skin color) following acute high exposure to aniline. Dizziness, headaches, irregular heart beat, convulsions, coma, and death may also occur. Direct contact with aniline can also produce skin and eye irritation. Long-term exposure to lower levels of aniline may cause symptoms similar to those experienced in acute high-level exposure. There is no reliable information on whether aniline has adverse reproductive effects in humans. Studies in animals have not demonstrated reproductive toxicity for aniline. The available studies in humans are inadequate to determine whether exposure to aniline can increase the risk of developing cancer in people. Rats that ate food contaminated with aniline for life developed cancer of the spleen. The International Agency for Research on Cancer (IARC) determined that aniline is not classifiable as to its carcinogenicity to humans. The EPA has determined that aniline is a probable human carcinogen.

97

SAFETY DATA SHEET OF ANILINE:

This Product Safety Summary is intended to provide a general overview of the chemical substance. The information on the Summary is basic information and is not intended to provide emergency response information, medical information or treatment information. Product Overview : Pure aniline is a highly poisonous, oily, colorless liquid with a somewhat unpleasant odor of rotten fish and also has a burning aromatic taste. Aniline is of great importance in the dye industry, being used as the starting substance in the manufacture of many dyes-e.g., indigo-and as an aid in the manufacture of others. It is also used to make chemicals used in producing rubber, urethane foams, explosives, herbicides and fungicides. Aniline is prepared commercially by the reduction of nitrobenzene, a product of coal tar, or by heating chlorobenzene with ammonia in the presence of a copper catalyst. May be fatal if swallowed, inhaled or absorbed through skin. Causes irritation to the skin, eyes and respiratory tract. Combustible liquid and vapor. May cause methemoglobinemia. Affects blood, cardiovascular system, central nervous system, liver and kidneys. Airborne limits have been established for aniline in the work environment. The American Conference of Governmental Hygienist (ACGIH) has a threshold limit value (TLV) of 5 ppm for an eight hour time weighted average basis with a skin notation. The Occupational Health and Safety Administration (OSHA) has established a permissible exposure limit (PEL) of 2 ppm for an eight hour time weighted average basis with a skin notation, also. For further safety and health information, the current Material Safety Data Sheet (MSDS) should be used for this substance Health Information : Aniline is a potentially hazardous material. A through knowledge of potential dangers, with strict adherence to recommended safety practices, is essential before aniline products are handled, stored or used. Workers must be properly instructed and supervised in the handling of aniline. Limits have been established for allowable concentrations in the work environment. ACGIH has a threshold limit value (TLV) of 2 ppm for an eight hour timeweighted average basis with a skin notation, while OSHA has set a permissible exposure limit (PEL) of 5 ppm for an eight hour time-weighted average basis with a skin notation, also. Effects on the Respiratory System:

98

Exposures to mists or vapor at levels above the recommended exposure limits can produce eye, nose or lung irritation. Symptoms may include bluish discoloration of lips and tongue, severe headache, nausea, confusion, dizziness, shock, respiratory paralysis, death. Aniline affects the ability of the blood to carry oxygen. Effects on the Skin: Aniline may be absorbed through the skin. Symptoms of skin absorption parallel those from inhalation exposure. May cause skin irritation and local contact may cause dermatitis. Effects on the Eyes: Aniline vapor is an eye irritant. May cause tearing and blurred vision. Splashes may cause corneal damage. Effects of Ingestion: Aniline is toxic. Lethal doses may be as little as one gram. Symptoms of ingestion parallel those of inhalation exposure. Chronic Hazards: Aniline is a blood toxin, causing hemoglobin to convert to methemoglobin, resulting in cyanosis. Lengthy or repeated exposures may result in decreased appetite, anemia, weight loss, nervous system affects, and kidney, liver and bone marrow damage. Any exposure may cause an allergic skin reaction.

Environmental Information : When released into the soil, this material is expected to readily biodegrade. When released into the soil, this material may leach into the groundwater but may evaporate to a moderate extent. When released into the water, this material is expected to readily biodegrade and have a half life between 10 and 30 days. Aniline has been experimentally-determined bioconcentration factor (BCF) of less than 100. It is not expected to significantly bioaccumulate. When released into the air, aniline is expected to readily degrade by reaction with photo chemically produced hydroxyl radicals and expected to degrade by photolysis. The half life of aniline in air is less than one day. Aniline is expected to be very toxic to terrestrial and aquatic life. The LC50/96 hour values for fish are between 10 and 100 mg/l. The EC50/48 hour values for daphnia are less than 1 mg/l. The inhibition of the degradation activity of activated sludge is not anticipated when introduced to biological treatment plants in appropriate low concentrations.

99

FIRE AND EXPLOSION DATA: Flammability of the Product: Combustible. Auto-Ignition Temperature: 615C (1139F) Flash Points: CLOSED CUP: 70C (158F). Flammable Limits: LOWER: 1.3% UPPER: 23% Products of Combustion: These products are carbon oxides (CO, CO2), nitrogen oxides (NO, NO2...). Fire Hazards in Presence of Various Substances: Flammable in presence of open flames and sparks, of heat. Non-flammable in presence of shocks. Explosion Hazards in Presence of Various Substances: Risks of explosion of the product in presence of mechanical impact: Not available. Risks of explosion of the product in presence of static discharge: Not available. Fire Fighting Media and Instructions: SMALL FIRE: Use DRY chemical powder. LARGE FIRE: Use water spray, fog or foam. Do not use water jet. Special Remarks on Fire Hazards: Ignites on contact with sodium peroxide + water. Aniline ignites spontaneously in presence of red fuming nitric acid. Sodium peroxide or potassium peroxide is spontaneouly flammable with aniline. When heated to decomposition it emits toxic fumes. Special Remarks on Explosion Hazards: Spontaneously explosive reactions occur with benzenediazonium -2-carboxylate, dibenzoyl peroxide, fluorine nitrate, nitrosyl perchlorate, red fuming nitric acid, peroxodisulfuric acid, and tetranitromethane. Addition of a drop of aniline to 1 gram of dibenzoyl peroxide leads to mildly explosive decompostion after a short delay. Addition of aniline to nitromethane renders it susceptible to initiation by a detonator. Anililne reacts with perchloric acid, and then formaldehyde to produce explosive and combustible condensed resin.

100

14. BIBLIOGRAPHY
1. Kirk Othmer Chemical Engineering Encyclopaedia Vol 02. 2. Reactant Separation from a Pharmaceutical Waste Stream Written by Larke Jo Ernlund Nielsen, c971547, Department of Chemical Engineering Technical University of Denmark July 4th 2003 3. Process Heat Transfer by Donald Q. Kern,1965. 4. Mass transfer operations, Third Edition, Robert E.Treybal,1981. 5. Perrys Chemical Engineers Handbook, Robert H. Perry, Don W. Green, James O. Maloney, Seventh Edition 1997. 6. Introduction to Chemical Engineering Thermodynamic Smith sixth edition. 7. Fundamentals of Mass Transfer and Kinetics for the Hydrogenation of Nitrobenzene to Aniline by Reinaldo M. Machado, Air Products and Chemicals, Inc. No. 01-2007.

101