MANUFACTURE OF TRIFLURALIN

A PROJECT REPORT

Submitted by S.ARUN SRIKANTH (41502203003) T.PRABHU ( 41502203011) H. SHEIK DAWOOD MARICAR (41502203014) VENKAT HARIHARAN (41502203020)

In partial fulfillment for the award of the degree Of BACHELOR OF TECHNOLOGY In CHEMICAL ENGINEERING

S.R.M. ENGINEERING COLLEGE, KATTANKULATHUR-603 203, KANCHEEPURAM DISTRICT. ANNA UNIVERSITY: CHENNAI-600 025 MAY 2006

BONAFIDE CERTIFICATE

Certified that this project report MANUFACTURE OF TRIFLURALIN is the bonafide work of S.ARUN SRIKANTH (41502203003), T.PRABHU ( 41502203011), H. SHEIK DAWOOD MARICAR (41502203014) and VENKAT HARIHARAN (41502203020) who carried out the project work under our supervision.

Dr. R . KARTHIKEYAN PROFESSOR HEAD OF THE DEPARTMENT

CHEMICAL ENGINEERING S.R.M. Engineering College Kattankulathur - 603 203 Kancheepuram District.

ACKNOWLEDGEMENT

Our heartfelt thanks to our Principal Prof. R. Venkataramani, B.E., M.Tech. F.I.E., and Director Dr. T.P.Ganesan, B.E.,(Lhons).,M.Sc.,(Engg.), for their constant support. We thank our HOD Prof. Dr. R Karthikeyan, B.E., Ph.D., who provided guidance and was a constant source of encouragement through the course of this project. Special thanks to the Mr.D.Balaji M.Tech., Mr.D.Bojarajan, M.Tech., who gave us valuable inputs and advice and motivated us to complete the project successfully. 2

We would also to take this opportunity to express our sincere thanks to the members

of the review committee.

Last but not least we would like to thank the faculty members of our, department, friends and our parents for their suggestions and guidance towards the completion of this project. iii

ABSTRACT

This project essentially deals with the manufacture of trifluralin, which is used for selective premergence control of annual grasses in cotton, Soya cans and other situations. Trifluralin is manufactured by action of nitric acid and parachlorobenzene trifluride with sulphuric acid as catalyst. The reaction is carried out in three steps. The three steps are the formation of mononitro intermediate, dinitro intermediate and amination reaction. The dinitro intermediate is filtered and stored in chloroform. It is then subjected to amination with di isopropyl amine. The resulting product is a mixture of Trifluralin and chloroform. The mixture is separated by distillation, where trifluralin is collected as the bottom product. The yield is about 96% trifluralin.

iv TABLE OF CONTENTS TITLE

CHAPTER ABSTRACT

PAGE NO iv vi vii

LIST OF TABLES LIST OF SYMBOLS AND ABBREVATIONS 1 INTRODUCTION 1.1 HISTORY OF TRIFLURALIN 1.2 PROPERTIES OF TRIFLURALIN 1.3 CHEMICAL STRUCTURE 1.4 APPLICATIONS 2 PROCESS 2.1 PROCESS DESCRIPTION 2.2 MASS BALANCE 2.3 ENERGY BALANCE 2.4 DESIGN 2.5 PROCESS CONTROL AND INSTRUMENTATION 2.6 PLANT LAYOUT 2.7 COST ESTIMATION 2.8 PROCESS SAFETY 3 CONCLUSION BIBILIOGRAPHY

1 3 4 5

6 8 16 19 24 28 34 40 50 51

LIST OF TABLES TABLE NUMBER 1.1 1.2 Notation ? HR Ta Tb ?T M t ? ?P Rm a A V ? ? D v H ?L ?G V0 TABLEHEADING General information about Trifluralin Physical and Chemical properties LIST OF SYMBOLS AND ABBREVATIONS Units Heat of reactions Temperature of feed entering the reactor Temperature leaving from the reactor Change in temperature Mass flowrate Filteration time Viscosity Pressure drop Filter medium resistance Specific cake resistance Cross sectional area Volume Density Latent heat of vapouraisation Diameter Volumitric flow rate Height Density of liquid chloroform Density of gas chloroform Alowable vapour velocity 5 KJ/mol Kelvin Kelvin Kelvin Kg/s hr Kg/ms N/m m- m/Kg m m Kg/m KJ/kg m m/s m Kg/m Kg/m m/s PAGE NO 2 4

INTRODUCTION 1.1 HISTORY OF TRIFLURALIN

One of the best known substituted dinitro aniline herbicides is a, a, a- trifiuro-2,6-dinitro-N, N-din-propyl-p- toludine is called Trifluralin. The herbicidal use of this compound was first reported in 1960. a number of other anilines shoe herbicidal activity. Of these, the 2, 6 dinitro- substituted compounds are most effective. Trifluralin and nitralin have been used for selective preemergence control of annal grasses in cotton, soybeans and other situations. Trifluralin should be incorporated into the soil by mechanical means within 24 hours of application. Granular formulations may be incorporated by overhead irrigation. Trifluralin is available in granular and emulsifiable concentrate formulations. It is recommended that applicators wear full protective clothing when spraying trifluralin. This gear should be include neoprene gloves, rubber workshoes, rubber apron, goggles to protect the eyes and a respirator inhalation of fumes or mists. A sensitive method of the determination for trifluralin in soil is the gas chromatography of extracts after cleanup on a florisil column.

1.1 GENERAL INFORMATION ABOUT TRIFLURALIN CAS NO SYNONYMS 1582-09-8 Treflan p-Toludine, ? -trifluoro-2, 6-dinitro-N,N-dipropyl C13H16F3N3O4 335.29 1959 First registered in the US in 1963 Patented by Eli Lily No appreciable odor

FORMULA MOLECULAR WEIGHT ENTRY YEAR INVENTING COMPANY ODOR

APPARENT COLOR USE SENSITIVITY DATA

Yellow crystals,Yellow-Orange prisms Herbicide Cause eye irritation, may cause skin sensitization reactions in certain individuals Dow Agro Makhteshim-Agan Industria Prodotti chimici Tri Corporation Albaugh Inc No occupational exposure limits have been established for Trifluralin by OSHA,NIOSH or ACGIH.

MANUFACTURERS

OCCUPATIONAL EXPOSURE LIMITS

1.2 PROPERTIES OF TRIFLURALIN Trifluralin is an odorless, yellow-orange crystalline solid. Trifluralin will decompose in both sunlight and artificial light.Trifluralin is stable under normal temperatures and pressures, but it may pose a slight fire hazard if exposed to heat or flame. It poses a fire and explosion hazard in the presence of strong oxidizers. Thermal decomposers of trifluralin will release corrosive fumes of hydrogen fluoride and toxic oxides of nitrogen. Technical trifluralin is not flammable, but emulsifiable concentrate formulations containing trifluralin may be flammable. The product Treflan EC is classified as a combustible liquid. Closed containers of this product may explode to excessive heat or intense fire. They may be prepared by reactions of a 4-chloro-3, 5-dinitrotoluidine derivative with an appropriate amine as follows.

O2N

Cl NO2 + NHRR CF3

NRR O2N

NO2 + HCL CF3

where R and R = alkyl. These products are typically substituted 2, 6-nitroaniline derivatives and are deep orange in color. Trifluralin(di-n-propyl)is extremely insoluble in water but soluble in organic solvents; it is slightly volatile. Trifluralin is susceptible to photodecomposition in the solid state and in solution. Atleast ten compounds were obtained by photolysis of trifluralin in methanol and two of the products were identified as ? ,? ,? -trifluoro-2, 6-dinitro-N-propyl-p-toludine and ? ,? ,? -trifluoro-2, 6dinitro-p-toludine. 1.2 PHYSICAL AND CHEMICAL PROPERTIES PHYSICAL STATE MELTING POINT BOILING POINT Odourless Orange Crystals 48.5 - 49? C 139 140? C at 4.2 mmHg 96 - 97? C at 0.18 mmHg 1.294 at 25? C Practically Insoluble 7.0 (50% Suspension) Pa at 25? C : 0.014 Technical Material Not Flammable. However, emulsifiable concentrate formulation may be flammable.

SPECIFIC GRAVITY SOLUBILITY OF WATER pH VAPOUR PRESSURE FLASH POINT

SOIL HALF LIFE

60 Days

1.3 CHEMICAL STRUCTURE One of the best known substituted dinitroaniline herbicides is a, a, a- trifluro-2, 6-dinitro-N, N-din-propyl-p-toluidine ( TRIFLURALIN ). N(C3H7)2 O2N NO2

1.4 APPLICATIONS METABOLISM: Trifluralin prevents development and growth of plant roots and shoots. Cell division is inhibited in trifluralin treated plants. The nuclei divide but the cell enlarges without separating into daughter cells. Schultz and Funderburk found that DNA, total RNA, and protein decreased in root tips of corn following trifluralin treatment but there is no clear explanation for the mode of action. Plants vary in their susceptibility to trifluralin but selectivity may be achieved by limiting the depth of soil incorporation so that the crop root remains outside of the region of chemical control. APPLICATIONS METHODS: Trifluralin is a pre emergence herbicide which must be soil incorporated within 24 hours after application using equipment that breaks up large clods and mixes the soil thoroughly; e.g., ? PTO-driven cultivators ? Hoes are tillers ? Double disc ? Rolling cultivator ? Field cultivator Application and incorporation can be preplant (PPI), postplant (PoPI), or layby (PoPI). Trifluralin may be applied by ground or aerial equipment. 9

CF3

ENVIRONMENTAL DATA This substance may be hazardous to the environment; special attention should be given to aquatic organism, honey bees. Bioaccumulation of this chemical may occur along the food chain, for example in fish. The substance may cause long-term effects in the aquatic environment.

2. PROCESS 2.1 PROCESS DESCRIPTION BASIS: 1640 Kg Of PCBT Basic raw material required for the manufacture of Trifluralin is para chloro benzene trifluride. About 1640 kg of para chloro benzene trifluride is used. It is made to react with Nitric acid with sulphuric acid as catalyst. The reaction is carried out in a Batch reactor ( mononitrator ). The reaction is moderately exothermic, the temperature is usually maintained around 40?C. it is achieved by means of cooling jacket. The flow rate of water is controlled by a pneumatic valve. The reaction takes places is as follows,

Cl HNO3 H2SO4 CF3

Cl NO2

CF3

The yield of the reaction is about 95%. The spent acid from the reactor is then sent to a waste treatment. The product mononitro intermediate is then stored under proper conditions. A part of mononitro intermediate from storage is then subjected to nitration. Oleum is also added. The temperature of the reactor is maintained around 120?C. The reaction takes place as follows.

10

Cl NO2 HNO3 H2SO4 Oleum CF3

Cl NO2

NO2

CF3

This reaction is also exothermic, the yield about 83%. The temperature is maintained by a cooling jacket. The product contains dinitro intermediate as a slurry. It is then subjected to filtration. The filtrate which contains a mixture of nitric acid and sulphuric acid is utilized in the previous reaction. The wash water is sent to waste. The residue which contains dinitro intermediate is stored under chloroform. The dinitro intermediate is then subjected to amination reaction, where it is made to react with diisopropyl amine and soda ash with excess water. The reaction is as follows, NO2 Cl NO2 NH ( C3H7 )2 Na2CO3 CF3 CF3 N(C3H7) NO2 NO2

The yield of reaction is about 96% the output product contains a mixture of trifluralin and chloroform. It is then subjected to filteration, the filtrate is then sent to the decanter, where the salt water layer is sent to waste. Trifluralin and chloroform is then subjected to distillation, where Trifluralin is collected as the bottom product. Chloroform is condensed and stored, it is then stored under proper condition.

11

dinitro in chloroform dipropylamine Fuming nitric acid storage Nitric acid PCBT Cycle acid Soda ash Water

Mononitrator PCBT storage

Dinitro storage (in chlorofor

Amination reactor

dipropyla mine storage

Yield
Spent acid to waste treatment

Filter press

Mono storage Nitric acid Sulfuric acid Mono oleum

Cycle acid storage

Aromatic naptha storage

Emulsifying agents Excess cycle acid to waste decanter chloroform Distillate Wash water

cond

sulfuric acid

Oleum storage

Chlorof
Closed s.s. nutch filter Dinitrator Trifluralin emulsifia ble conc storage Yield slurry Mononitrator

orm

Wash

chloroform

Recycled

chloroform

12

MONONITRATOR (figures in brackets denotes the number of kilo moles of the component)

INPUT

OUTPUT

1640 kg PCBT (9.0858)

1946.40 kg PCBNO2 (8.63151) 82 kg Unreacted PCBT(0.4542)

1327.2 kg H2SO4 (13.5428) 587.34 kg Unreacted HNO3 (9.322) 155.36 kg H2O formed (8.6315) 1131.13 kg HNO3 (17.9544) 1327.2 kg H2SO4 (13.5428)

13

DINITRATOR (figures in brackets denotes the number of kilo moles of the component) INPUT OUTPUT

909 kg PCBNO2 (4.0132)

414 kg HNO3 (6.5714)

905.01 kg PCB(NO)2 formed (3.3309) 60.22 kg H2O formed (3.3309)

203.217 kg Unreacted HNO3 (3.2402) 154.50 kg Unreacted PCBNO2 (068224) 1636 kg Oleum (76.057) 1636 kg Oleum (76.057) 1000 kg H2 SO4 (10.2040) 1000 kg H2SO4 (10.2040)

14

AMINATION REACTOR INPUT OUTPUT

154.50 kg PCBNO2 (0.6851) 907.68 kg PCB(NO2)2 (3.321) 3800 kg H2O (3.3455)

1078.96 kg Trifluralin (3.217) 117.5592 kg Hcl (3.2208) 36.3011 kg Unreacted PCB(NO2)2 (0.1332)

714 kg Iso Propyi Amine(7.069) 795 kg Soda Ash (7.5)

388.6682 kg Unreacted Iso Propyl Amine(3.8482) 795 kg soda Ash (7.5) 154.50 kg PCBNO2 (0.6851)

755.5 kg Chloroform (6.324)

755.818 kg Chloroform (6.324) 3800 kg H2O (3.3455)

15

FILTRATION

INPUT

OUTPUT

905.01 kg PCB(NO2)2 (3.321) 154.50 kg PCBNO2 (0.6851) 905.01 kg PCB(NO2)2 60.22 kg H2O (3.3455) (3.3211)

1000 kg H2SO4 (10.2040) 1636 kg Oleum (76.057) 203.217 kg HNO3 (3.2256)

154.50 kg PCBNO2 (0.6851)

OUTPUT 60 kg H2O (3.345) 1000 kg H2SO4 (10.2040) 1636 kg Oleum (76.057) 203.217 kg HNO3 (3.2256)

16

FILTER PRESS INPUT OUTPUT

1078.96 kg Trifluralin (3.2169) 755.8 kg Chloroform (6.3246) 117.5592 kg Hcl (3.2208) 3800 kg H2O (211.11) 154.50 kg PCBNO2 (0.6852) 36.3011 kg PCB(NO2)2 (0.1332) 795 kg Soda Ash (7.5) 388.6682 kg Iso Propyl Amine (3.8482) OUTPUT 1078.96 kg Trifluralin (3.2169 ) 117.5592 kg Hcl (3.2208) 3800 kg H2O (211.11) 755.8 kg Chloroform (6.3246) 795 kg Soda Ash (7.5) 388.6682 kg Iso Propyl Amine (3.8482) 36.3011 kg PCB(NO2)2 (0.1332) 154.50 kg PCBNO2 (0.6852)

17

DECANTER INPUT OUTPUT

1078.96 kg Trifluralin (3.2169) 755.8 kg Chloroform (6.3246) 117.5592 kg Hcl (3.2208) 1078.96 kg Trifluralin (3.2169 ) 755.8 kg Chloroform (6.3246)

3800 kg H2O (211.11) 795 kg Soda Ash (7.5) 388.6682 kg Iso Propyl Amine (3.8482) OUTPUT 795 kg Soda Ash (7.5) 388.6682 kg Iso Propyl Amine (3.8482) 117.5592 kg Hcl (3.2208) 3800 kg H2O (211.11)

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REBOILER The feed is liquid and at its boiling point Therefore q= 1 V = D ( R + 1) = 6.523 ( 1.525 +1 ) = 16.470 ( Kmol / s) Vapour flow rate in the reboiler: v = V ( 1 q ) F = V =16.470 (Kmol /s)

CONDENSER The feed is liquid and at its boiling point Therefore q= 1 V = D ( R + 1) = 6.523 ( 1.525 +1 ) = 16.470 ( Kmol / s) Vapour flow rate in the condenser : V = v + ( 1 q ) F = V =16.470 (Kmol /s)

19

VACCUM STILL (figures in brackets denotes the number of kilomole/min of the component) FEED ( 9.57 ) Chloroform : 0.6635 Trifluralin : 0.3364 DISTILLATE (6.523) Chloform : 0.95 Trifluralin : 0.05

BOTTOM PDT

(3.046)

Chloroform : 0.05 Trifluralin : 0.95 F = D+ B F Xf = D XD + B XB 6.35 = D (0.95) + B (0.05) .. (1) 9.57 = D + B (2)

Solving the above equaction we get, D = 6.523 kmol / min B = 3.046 kmol / min
2.3 ENERGY BALANCE 20

MONO NITRATOR

Temperature of feed entering the reactor Temperature leaving from the reactor Change in temperature ? HR = 3183.3 KJ/hr mol ? HR = 17.636 x 1640 = 28923.05 KJ/hr ? HR = 8.034 KJ/S ? HR = M Cp ? T M = 8.034 / (4.2 x 10) = 0.19128 Kg /S

Ta = 30C Tb = 40C ?T = 10C

Therefore mass Flow rate of colling water required = 0.19128 Kg/S DI NITRATOR Temperature of feed entering the reactor Temperature leaving from the reactor Change in temperature ? HR = 1429297 KJ/hr mol ? HR / mol Wt = 1429297 / 225.5 = 6338.35 KJ/hr = 1.76065 KJ/S ? HR = M Cp ? T M = 1.76065 / (4.2 x 20) = 0.0209 Kg /S Therefore mass Flow rate of Cooling Water required = 0.0209 Kg/S AMINATION REACTOR Ta = 30C Tb = 50C ?T = 20C

21

Temperature of feed entering the reactor Temperature leaving from the reactor Change in temperature ? HR = 797253 KJ/ mol hr

Ta = 30C Tb = 40C ?T = 10C

? HR = 797253 / 270.5 = 2947.330 KJ/hr ? HR = 0.8187 KJ/S ? HR = M Cp ? T M = 0.8187 / (4.2 x 10) = 0.0194 Kg /S

Therefore mass flow rate of water required = 0.0194 Kg/S CONDENSER Inlet water temperature T1 = 30 C

Outlet water temperature T2 = 40C Change in temperature ? T = 10C ?avg = 32498.23 kj/kg mol Cp = 4.2 kj/kg V = 16.470 kmol/min = 0.2745 kmol/ sec Amount of cooling water required : Mw = (V x ?avg ) / Cp ( T2 T1 ) = (0.2745 x 32498.23) / (4.2 (4030)) = 212.4 kg/sec REBOILER

Saturated Steam is supplied at 107.13 C ( 1.3 bar ) 22

?S = 2687 kj/kg Latent heat of Chloroform = 32221.61 kj/kg mol Latent heat of Trifluralin = 33326.92 kj/kg mol ?avg = (0.6635 x 32221.61) + (0.3364 x 33326.92) = 32498.23 kj/kg mol Mass flow rate of steam required: v = 16.470 kmol/ min =0.2745 kmol/sec Ms = ( v x ?avg ) / ?S = 3.32 kg/sec

2.4 DESIGN DESIGN OF DISTILLATION COLUMN Realative Volatility a = 2.5 Y = a x / ( 1+( a -1 )x ) X Y From Graph, XD / Rm + 1 = 0.59 0.95 = 0.59 (Rm + 1) Rm = 0.610 R = 2.5 Rm = 1.525 XD / R + 1 = 0.95 /(1.525+1) = 0.3762 No of ideal plates = 9-1 = 8 Column Efficiency = 75% 23 0 0 0.2 0.3846 0.4 0.625 0.6 0.789 0.8 0.909 1 1

Therefore Actual number of Plates = 8/ 0.75 = 10.66 11 plates COLUMN HEIGHT Plate Spacing = 450 mm = 0.45 m Column Height = 10 x 0.45 + 2 x 0.45 = 5.4 m

EQUILIBRIUM DIAGRAM

24

COLUMN DIAMETER Cv for spacing of 450 mm = 0.14 Chloroform liquid density ? L = 1.489 Chloroform vapour density ? G = P / RT = 101.3 / ( 8.314 x (273 +80) ) = 4.1255 kg/m Alowable vapour velocity = V0 = 0.14 ? ( ( ? L ? ? G ) / ? G ) = 0.14? ( ( 1489 ? 4.1255) / 4.1255) = 2.65 m/s Volumetric flow rate V = n R T / P = ( 0.2745 x 8.314 x 353 ) / 101.32 = 7.95 m /s Q=AxV A=Q/V A = ? D/4 ? D =1.95 m

DESIGN OF FILTER PRESS Mono nitrator density = 2.32 Dinitrator density = 2.70 Total mass of the cake = 190.8211 kg Average Density of cake = 2.51 Area of each frame = 30m x 30m Spacing between the frame = 5 cm Volume of cake = 4500 cm Mass of cake = 11.295 kg No of spacing = ( 190.8211 / 11.295 ) = 16.89 17 No of frames = 18 25

To Find The Time Of Filtration Constant Pressure Filtration The equation for constant pressure filtration t/v = (Kc/2)V + (1/q0 ) kc = ( C a / A?P ) 1/q0 = ( Rm / A ? P) = 0.001 Kg/ms ? P = 5 x 10^4 N/m Rm = 12.05 x 10^10 m- a = 10 x 10 ^11 m/ kg A = 30 cm x 30cm = 0.09 Kc = (0.001 x 25.10 x 10 x 10 ^ 11) / ( 0.09 x 5 x 10 ^4 ) = 61.975 x 10^ 6 1/q0 = ( 0.001 x 12.05 x10^10 ) / (0.09 x 5 x 10^4 ) = 26.77 x 10^3 t = (Kc /v) + (v/q0) = 1789.84 + 203.51 = 1993.35 (S) = 0.55 (S)

MONONITRATOR To find the volume of the reactor: Density of HNO3 = 1354 kg/m Density of H2SO4 = 1706.9 kg/m Density of PCB Volume of HNO3 = 1236 kg/m = 1131.13 / 1354 = 0.8353 m

Volume of H2SO4 = 1327.2 / 1706.9 = 0.7775 m Volume of PCB = 1640 / 1236 = 1.3269 m 26

Therefore Volume of Reactor = 0.8353 + 0.7775 + 1.3269 = 2.9397 ? 3 m DINITRATOR Density of HNO3 Density of H2SO4 = 1354 kg/m = 1706.9 kg/m

Density of PCBNO2 = 1320 kg/m Density of Oleum Volume of HNO3 Volume of H2SO4 = 1127.5 kg/ m = 414 / 1354 = 0.3057 m

= 1000 / 1706.9 = 0.5858 m = 0.6886 m

Volume of PCB NO2 = 909 / 1320 Volume of Oleum Therefore

= 1636 / 1127.5 = 1.450 m

Volume of Reactor = 0.3057+ 0.5858 +0.6886 +1.450 = 3.031 ? 3 m AMINATION REACTOR Density of Water = 1000 kg/m Density of Soda ash = 2533 kg/m Density of PCBNO2 = 1320 kg/m Density of PCB(NO2)2 = 1430 kg/m Density of chloroform = 1489 kg/ m Density of Iso propyl amine = 694 kg/m Volume of Water = 3800 / 1000 = 3.8 m Volume of Soda ash = 795 / 2533 = 0.3138 m Volume of PCB NO2 = 154.5 / 1320 = 0.1170 m Volume of PCB(NO2)2 = 907.68 / 1430 = 0.6347 m 27

Volume of chloroform = 755.8 / 1489 = 0.5075 Volume of Iso propyl amine = 714 / 694 = 1.0288 Therefore Volume of Reactor = 3.8 + 1.0288 + 0.5075 + 0.6347 + 0.1170 + 0.3138 = 6.41 ? 6.5 m

2.5 INSTRUMENTATION AND PROCESS CONTROL The primary objectives of the designer when specifying instrumentation and control schemes are: 1. Safe Plant Operation: a. To keep the process variables within known safe operating limits b. To detect dangerous situations as they develop and to provide alarms and automatic shutdown systems. c. To provide interlocks and alarms to prevent dangerous operation procedures.

2. Production rate: To achieve the designed output. 3. Product quality: To maintain the product composition within specified quality standards. 4. Cost: To operate at the lowest production cost, commensurate with the other objectives.

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BATCH REACTOR Batch processes are used extensively in the manufacture of relatively small volume products with relatively high value. These processes are frequently carried out in production facilities intended for multi-purpose use. The achievement of stable and reproducible operating conditions is important in order to achieve the required product purity, yield and cycle times to satisfy the commercial requirements and relevant regulatory authorities. Batch processes are inherently transient in nature and the capability to demonstrate dynamically the adequacy of the equipment design and performance provides a powerful design tool. Dynamic modelling can prevent costly mistakes prior to start up. Once a process model signature has been validated against real plant performance the dynamic model can be used as a diagnostic tool to identify operating problems. This paper reviews the basic techniques for dynamic modelling the process and control of batch reactors and batch distillation systems using the Chemstations integrated range of software which is supported by an extensive component physical property database and thermodynamic options. FEED FORWARD CONTROL Feed forward control is becoming widely used. Process disturbances are measured and compensated for without waiting for change in the controlled variable to indicate that a disturbance has occurred. Feed forward control is also controlled when the final controlled variable cannot be measured. The equation solved by the controller relating input-liquid heat content, steam flow and outputliquid temperature is usually designated as the process model. Perfect models and controllers are rare, so a combination of feedback and feed forward control is desirable. The arrangement of a controller supplying the set point for another controller is known as cascade control and it is commonly called Feed back control. CONTROL VALVE The control valve is a pneumatic device that moves the valve stem as the pressure on a springloaded diaphragm changes. The stem positions a plug I the orifice of the valve body. As the pressure increases, the plug moves downward and restricts the flow of fluid through the valve. The action is referred to as air-to-close. The valve may also be constructed to have air-to-open action. Valve motors are often constructed so that valve stem is proportional to the valve-top pressure. Most commercial valves move from fully open to fully close as the valve-top pressure changes from 3 to 15 psi. CONTROLLER The controller hardware is required to control the temperature of a stream leaving at refrigeration. This hardware, available from manufacturers of such equipment, consists of the following components listed here along with their respective conversions: 29

1. Transducer (temperature to current) 2. Controller-recorder (current to current) 3. Converter (current to pressure) 4. Control valve (pressure to flow rate)

Thermocouple is used to measure the temperature, the signal from the thermocouple is sent to the transducer, which produces an output range of 4-20mAv , which is a linear function of the input. The output of the transducers enters the controller where it is compared to a set point to produce an error signal. The controller converts the error to an output in the range of 4-20mA according to the control law we have considered so far has been proportional. The output of the controller enters the converter, which produces an output the range of 3-15 psig, which is a linear function of the input. Finally, the output of the converter is sent to the top of the control valve, which adjusts the flow of the cooling water to the heat exchanger. We shall assume that the valve is linear and the pressure-to-open type. Electricity is needed for transducer, controller and converter. A source of 20 psig air is needed for the converter. This concludes our brief introduction to valves and controllers. We know present transfer function for such devices. These transfer functions, especially for controllers are based on ideal devices that can be only approximated in practice. The degree of approximation is sufficiently good to warrant use of these transfer functions to describe the dynamic behavior of controller mechanism for ordinary design purpose.

INSTRUMENTATION TEMPERATURE MEASUREMENT The temperature measuring element in a control system for jacketed tank is generally a thermocouple. The five most commonly used thermocouples are copper constantan, iron constantan, chromel alumel, platinum platinum 13% rhodium, platinum platinum 10% rhodium. LEVEL MESUREMENT The float- shaft type is employed either in open vessels. This method is suitable for a wide range of liquids and semi-liquids. Difficulties are sometimes encountered when the liquid deposits on the float and when the liquid level is foaming or turbulent.

30

FLOW RATE MEASURING The industrial devices for flow rate estimation are common orifice meter, venturimeter, pilot tube and the Rota meter. The piping system must be made of special corrosion resistant material when corrosive fluids are used. pH MEASUREMENT In this process we use the digital pH meters, these pH meters can measure the pH of the solution accurately for two decimal places. These pH meters can be used over wide range temperatures. These pH meters dont require additional current for the working once they are dipped in the solution they measure the pH of the solution on the display. 2.6 PLANT LAYOUT: PLANT LOCATION AND SITE LAYOUT The location of the plant can have a crucial effect on the profitability of a project, and the scope for the future expansion. There are many factors must be considered while selecting a suitable site. Some of the principal factors while selecting a suitable site. Some of the principal factors which must be considered for the selection of chemical process site are: 1. Area of development favored by the government and the incentives, which are available. 2. The likelihood of finding suitable employees in the area and of wage subsides. 3. The peculiarities of climate. 4. Sources of electricity gas and water. 5. Area of at least 100 acres of level ground on good boulder clay free from any danger of flooding. 6. Not sensitive environmental area. 7. Besides fresh water, adequate water must be available for cooling purposes. 8. Readily linked railway system. 9. Besides readily linked road system. 10. Near a responsible population centre. 11. Local community considerations. 12. Environmental impact and effluent disposal.

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13. Political and strategic considerations. 14. Climate. 15. Expansion possibilities. SITE LAYOUT The process units and ancillary building should be laid out to give the most economical flow of materials and personal around site. Hazardous process must be located at a safe distance from other buildings. Considerations must also be given to future expansion of the site. The ancillary buildings and services required on site, in addition to the main processing units(buildings),will include : 1. Storages for raw material and products : Tank farms and warehouse 2. Maintenance workshops. 3. Store for maintenance and operating supplies. 4. Laboratories for process control. 5. Fire stations and other emergency services. 6. Utilities : steam boilers , compressed air , power generation , Transformer station. 7. Effluent disposal plant. 8. Offices for general administration. 9. Canteens and other amenity buildings, such as medical centers. 10. Regulatory laws. 11. Taxes. 12. Car parks. RAW MATERIALS SOURCES Careful considerations should be given to the sources of raw materials to be used, method of delivery and storage facilities of raw materials. WASTE PRODUCT DISPOSAL

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Another aspect, which is gaining importance these days, is the environmental considerations. Careful attention should be given to the nature of products to be wasted, their quantity, available methods of disposal and the legislations governing the disposal. Location can be an important factor for cost. If the bearing quality of the land is low, considerable amount may be spent in piling support for heavy equipments or multi-storied buildings. If the land is uneven and the site needs even level, the cost of leveling may be considerable. Sometimes advantage can be taken of uneven levels so a s to use gravity as a means of transportation of materials. When planning the preliminary site layout, the process units will normally be sited first and arranged to give a smooth flow of materials through various processing steps, from raw material to final product storage. Process units are normally spaced at least 30 meters apart. administration offices and laboratories, in which a relatively large number people will be working, should be located well away from potentially hazardous process control rooms. The siting of the main process units will determine the layout of the plant roads, pipes, alleys and drains. Access roads will also be constructed for operation and maintenance purpose. Utility building should be sited to give the most economical run of the processing units. The main storage areas should be placed between the loading and unloading facilities and the process units they serve. Storage tanks containing hazardous materials should be sited at least 70 meter from site boundary. PLANT LAYOUT: The economic construction and efficient operation of a process unit will depend on how well the plant and equipment specified on the process flow sheet is laid out . The major principal factor that has to be considered while designing a plant layout are as follows : 1. Economic considerations : Constructions and operating cost 2. Damage to person and property an case of fire , explosion and 3. toxic release 4. The process requirements 5. Convenience of maintenance. 6. Safety. 7. Future expansion. 8. Modular constructions. 33

The usual practice in extraction engineering is to have the fermentation section and the extraction separated into two portions , one be arranged into two neat rows with interconnecting piping in between , preferably through trenches by the side of the fermentors. The main instruments can be brought to the instruments panel and other (such as indicating thermometer) are left mounted on the equipment at convenient point for visual observations. Excise regulations generally specify three days production capacity for the receivers. Storage tanks can be located outside buildings. Fermentors also could be kept in the open, providing also protection for the operator from rain and sun In preparing the plant layout one has to satisfy various regulations acts and considerations are: 1. Factories act 2. The explosives act 3. Excise rules 4. Health rules 5. The boilers act 6. Electricity regulations It is also advisable to check up the insurance regulations from the view of getting the best coverage at minimum cost for plant building and inventory. Adjacent to fermentors a separate house can be provided for pumps, compressors, molasses weighing system etc. MAINTENANCE Maintenance costs are high in the penicillin industry. In some case, the cost of maintenance exceeds the companys profit. The engineer must design to reduce these costs. The easiest way to reduce maintenance costs is to allow lots of extra space and to construct everything at ground level for easy access. However, this may increase construction and operating expenses and decrease the ease of operatibility. Adequate space must be left around all equipment so that it can be easily serviced and operated. STORE AND WAREHOUSES The engineer must decide whether the warehouses must be at ground level or dock level. The latter facilitates loading trains and trucks, but costs 15-20% more than one placed on the ground. It is usually difficult 34

to justify the added expenses of a dock-high warehouse To size the amount of space needed, it must be determined how much is to be stored in what size containers. The container sizes that will be used are obtained from the scope. Liquids are generally stored in bulk containers. No more than a weeks supply of liquid stored in drums should be planned. Solids, on the other hand, are frequently stored in smaller containers or in a pile on the ground.

Fire Station

Training Academy Entrance

Health Club

Canteen

Water Treatment Area

Batch Batch
Reactor Reactor

Filter Batch
Reactor

Exit

S E C U R I T Y check post

Filter Press P A R K I N G

Administrative Block

Hospital

Decantor

Vaccum Still

Store House

Quality Control

Prod and control limit

Lab and testing area

Work shop

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Figure: 2.2 2.7 COST ESTIMATION ESTIMATION OF THE TOTAL CAPITAL INVESTMENT The total capital investment I involves the following: A. The fixed capital investment in the process area, IF. B. The capital investment in the auxiliary services, IA. C. The capital investment as working capital, IW. i.e., I = IF + IA + IW

A. FIXED CAPITAL INVESTMENT IN THE PROCESS AREA, IF. This is the investment in all processing equipment within the processing area. Fixed capital investment in the process area, IF = Direct plant cost + Indirect plant cost The approximate delivered cost of major equipments used in the proposed TRIFLURALIN manufacturing plant are furnished below: S.No. 1 2 3 3 4 Equipment Condenser Distillation column Carbon disulfide reactor Storage tank sealed Miscellaneous TOTAL Units 2 1 3 2 Cost in lakhs/unit 200 420 1800 50 Cost in lakhs 400 420 5400 500 2000 8720 lakhs

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Direct cost factor S.No 1 2 3 4 5 6 7 8 9 Items Delivered cost of major equipments Equipment installation Insulation Instrumentation Piping Land & building Foundation Electrical Clean up Total direct cost factor Direct cost factor 100 15 15 15 75 30 10 15 5 280

Direct plant cost = (Delivered cost of major equipments) (Total direct cost factor) / 100 Direct plant cost = (8720* 280) / 100 = 24416 lakhs Indirect cost factor S.No. Item 1 2 3 Overhead contractor etc. Engineering fee Contingency Total indirect cost factor Indirect cost factor 30 13 13 56

Indirect plant cost = (Direct plant cost) ( Total indirect cost factor) / 100 = (24416* 56) / 100 = 13672.96 lakhs Fixed capital investment in the process area, IF = Direct plant cost + Indirect plant cost = 24416+ 13672.96 = 38088.96lakhs 37

B. THE CAPITAL INVESTMENT IN THE AUXILLARY SERVICES, IA . Such items as steam generators, fuel stations and fire protection facilities are commonly stationed outside the process area and serve the system under consideration. S.No. 1 2 3 4 5 6 7 8 9 10 Items Auxiliary buildings Water supply Electric Main Sub station Process waste system Raw material storage Fire protection system Roads Sanitary and waste disposal Communication Yard and fence lighting Total Auxiliary services cost factor 5 2 1.5 1 1 0.7 0.5 0.2 0.2 0.2 12.3

Capital investment in the auxillary services = (Fixed capital investment in the process area) ( Auxiliary services cost factor) / 100 = (38088.96 * 12.3) / 100 = 4684.9421 lakhs Installed cost = Fixed capital investment in the process area + Capital investment in the auxiliary services = 38088.96 + 4684.9421 = 42773.9021 lakhs C. THE CAPITAL INVESTMENT AS WORKING CAPITAL, IW. This is the capital invested in the form of cash to meet day-to-day operational expenses, inventories of raw materials and products. The working capital may be assumed as 15% of the total capital investment made in the plant ( I ). 38

Capital investment as working capital, IW = ((38088.96+ 4684.9421)* 15) / 85 = (42773.381* 15) / 85 = 7548.33 lakhs Total capital investment, I = IF+ IA+ IW = 7548.33 + 38088.96 + 4684.9421 = 50322.2378 lakhs

ESTIMATION OF MANUFACTURING COST The manufacturing cost may be divided into three items, as follows: A. Cost Proportional to total investment B. Cost proportional to production rate C. Cost proportional to labour requirement A. COST PROPORTIONAL TO TOTAL INVESTMENT This includes the factors, which are independent of production rate and proportional to the fixed investment such as - Maintenance-labour and material - Property taxes - Insurance - Safety expenses - Protection, security and first aid - General services, laboratory, roads, etc. - Administrative services For this purpose we shall charge 15% of the installed cost of the plant = (Installed cost * 15) / 100 = (42773.9021 * 15) / 100 = 6416.0853 lakhs B. COST PROPORTIONAL TO PRODUCTION RATE The factors proportional to production rate are - Raw material costs - Utilities cost power, fuel, water. Steam, etc. - Maintenance cost - Chemical, warehouse, shipping expenses Assuming that the cost proportional to production rate is nearly 60% of total capital investment, Cost proportional to production rate = (Total capital investment * 60) / 100 = (50322.2378 * .6) = 30193.3427 lakhs C. COST PROPORTIONAL TO LABOUR REQUIREMENT The cost proportional to labour requirement might amount to 10% of total manufacturing cost. Cost proportional to labour requirement = (6416.92 + 30193.3427)(0.1) / (0.9) = 4067.7142 lakhs 39

Therefore, manufacturing cost

= (6416.92+ 30193.3427 +4067.7142) = 40677.1422 lakhs

SALES PRICE OF PRODUCT Market price of Trifluralin Production rate Total sales income = Rs.30/kg =1.9*10 5 TPA = 30* 1.9 *10 5 *1000 = 57350 lakhs

PROFITABILITY ANALYSIS A. DEPRECIATION According to sinking fund method: R = (V-VS) I / (1+ I) n R = Uniform annual payments made at the end of each year V = Installed cost of the plant VS = Salvage value of the plant after n years N = life period (assumed to be 15 years) I = Annual interest rate (taken as 15%) R = (42773.902* .15) / (1+0.15) 15-1 = 898.9814 lakhs B. GROSS PROFIT Gross profit = Total sales income - manufacturing cost = 57350 40677.1422 =16672.85 lakhs C. NET PROFIT It is defined as the annual return on the investment made after deducting depreciation and taxes. Tax rate is assumed to be 40%. Net profit = Gross profit-Depreciation-(Gross profit*Tax rate) = 16672.85-898.9814-(16672.85*0.4) = 9104.7364 lakhs D. ANNUAL RATE OF RETURN Rate of return = (100*Net profit/Installed cost) = (100*9104.7364) / 42773.9021) = 21.2857% E. PAYOUT PERIOD 40

Payout period = Depreciable fixed investment / ((profit)+(depreciation)) = 42773.9021 / (9104.7364 + 898.9814) = 4.215 years 2.8 PROCESS SAFETY

Introduction: In recent years there has been an increased emphasis on process safety as a result of number of serious accidents. This is due in part to the worldwide attention to issues in the chemical industry brought on by several dramatic accidents involving gas releases, major explosions and several environmental Accidents. Public awareness of these and other accidents has provided a driving force for industry to improve its safety record. Local and national governments are taking a hard look at safety in the industry as a whole and the chemical industry in particular. There has been an increasing amount of government regulations. For many reasons, the public often associates chemical industry with environmental and safety problems. It is vital for the future of the chemical industry that process safety has a higher priority in the design and operation of chemical process facilities. Industrial accidents: An accident has been defined as an unplanned or unexpected event, which causes or is likely to cause an injury. An accident occurs as a result of unsafe action or exposure to an unsafe environment. Unsafe actions or unsafe mechanical or physical conditions exist only because of faults of a particular person. Faults of persons are inherited from the environment and reasons for the faults are: 41

? Improper attitude ? Lack of knowledge or skill ? Physical unsuitability ? Improper mechanical or physical environment

Accident prevention: From the foregoing, it will be seen that the occurrence of an injury is the culmination of a series of events circumstances that invariably occur in a fused and logical order. Knowledge of the factors in the accident sequence guides and assists in selecting the point of attack in prevention work. It permits simplification without sacrifice of effectiveness. The most important point is that unsafe condition or actions are the immediate cause of accidents. The supervisions and management can control the action of employed persons and so prevent unsafe acts and also guard or remove unsafe conditions, even though previous events or circumstances in the sequence are unfavorable.

The four factors that converge to cause accidents are: ? Personal factor ? Hazard factor ? Unsafe factor ? Proximate casual factor

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The solution under the four factors would also lead to the steps. These are planning and organizing to

1. 2.

Prevent unsafe mechanical or physical conditions. Prevent unsafe action being committed.

Unsafe condition examples : ? ? ? ? ? ? ? ? ? Operating without securing, warning etc. Operating or working at unsafe speed. Making safety devices inoperative. Using unsafe equipment. Unsafe loading, placing, mixing etc. Taking unsafe position or posture. Working on moving or dangerous equipment. Unsafe mechanical and physical conditions. Inadequately guarded.

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? ? ? ? ? ? ?

Unguarded. Defective condition (rough, delayed etc ). Unsafe design or construction. Hazardous arrangement or process. Inadequate or improperly distributed ventilation. Unsafe dress or apparel. Unsafe method, process, planning etc.

The most important means of accident prevention are: ? ? ? ? ? Engineering revision. Instruction. Persuasion. Personal adjustment. Discipline.

Industrial ventilation and lighting The main functions of ventilation in an industry are: ? ? To prevent harmful concentration of aerosols. To maintain reasonable condition of comfort for operators at workplace. 44

? ? enable 1. 2.

It maintains the body heat balance and to provide reasonable conditions of comfort. Ventilation should aim at Keeping the air temperature of the workroom low enough to

Body heat to be dissipated by convection Preventing excessive humidity so as to assist body heat loss by

evaporation. 3. Regulating the rate of air movement so that loss of body heat by convection is

facilitated. The amount of ventilation generally depends on the following factors: 1. 2. 3. 4. 5. Size and type of room or building and its usage. Duration and type of occupants and their activities. Heat gains from sun, hot manufacturing. Temperature conditions. The operators of the ventilating system.

Types of ventilation 1. Natural ventilation

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2.

Mechanical ventilation

Natural ventilation Forces, which operate to induce natural ventilation in building, arc due to : ? ? Pressure exerted by outside wind. The temperature differences of the air within and without the building.

Types of Natural ventilation 1. 2. 3. Cross ventilation. Roofed ventilation. Cool type roof ventilation.

Mechanical ventilation It is brought out by their one or both of the following two methods: ? Ventilation through windows or other openings owing to the suction created by the

exhaust of air. ? Positive ventilation by means of a fan or blower.

Types of mechanical ventilation ? Exhaust ventilation 46

? ?

Combined plenum and extraction system Mechanical roof ventilators.

Personal protective devices: Protective devices are required by regulation; the employers are required to provide it free of cost and also should be responsible to ensure its usage maintenance and renewal. Once it is decided to use personal protective devices, we must select the proper type of devices. Make sure that the employees use and maintain these correctly. For selection of device, two criteria should be used: 1. The degree of protection. 2. The ease with which it may be used. Protective devices are divided into two groups: 1. Respiratory devices 2. Non-respiratory devices Safety appliances: Helmets: Every employee inside the factory should always wear the safety helmet to avoid head injuries. No worker will be allowed to enter any plant without a helmet. Safety goggles:

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The goggles must be worn while entering the process areas. Special geoggles must be worn for gas and grinding operations. Safety shoes: All the employees working inside a factory should wear safety shoes and gumboots should be used while handling acids and alkalis.

Hand gloves: While operating any valve or equipment and also while executing any maintenance work including electrical maintenance work, the employees should wear appropriate type of safety gloves. Dust mask: While working in a dusty atmosphere, the employees must wear dust masks to prevent dust and fumes entering the sensitive respiratory organs, which can cause a lot of irritation and in the long run painful and incurable diseases. Plastic aprons: This along with the hood gives protection to the operation and maintenance staff while handling dangerous acids and other hazardous chemicals particularly when there is possible leakage. In spite of safety appliances, the companys medical center is equipped to meet any emergency and any employee coming in contact with acids or any hazardous chemicals must be treated at the medical center immediately.

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3. CONCLUSION

Trifluralin is manufactured by the action of para-chloro-benzene trifluride and nitric acid with sulphuric acid as catalyst. It was simple in concept and has the virtue of being a single product technology an important consideration for a production of such enormous volumes.

In this project we have dealt with energy and design aspects connected with the process. The feasibility of the process and the cost estimation details have also been discussed. BIBILIOGRAPHY

Coughanour .D.R.(1991), process System Analysis and Control , 2 nd Edn., McGraw Hill, New York. Coulson & Richardson (1999), Chemical engineering , 3rd Edition, BH Publications , 6th volume. Donald .Q. Kern (1982), Process Heat Transfer, McGraw Hill,International student edn, 3rd Edition. Kirk & Othmer (2004), Encyclopedia of Chemical Technology, 4th edition, Vol 18, John Wiley and sons. Robert .E. Treybal (1968), Mass Transfer Operations, McGraw Hill, 2 nd Edn. Stephanopopulous. G (1998), Chemical Process Control ,1st Edn, Prentice Hall, New Delhi.

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