5.

PROCESS DESCRIPTION
The detailed process for the batch process manufacture of 3, 5-dichloroaniline is described below. The entire plant can be split into two main sections:( I ) Deamination section. ( II ) Hydrogenation section and subsequent purification.

Section ( I ) 2, 6-dichloro-4-nitroaniline is major raw material. It is deaminated in first section to give 3, 5-dichloroaniline. Since, 2, 6-dichloro-4-nitroaniline is solid, sufficient amount of solvent is used for dissolving it. Here, we used iso-propanol as a solvent. Around 90% of solvent is recycled back. Detailed description: Initially, solid 2, 6-dichloro-4-nitroaniline is charged to R1002. Sufficient amount of solvent, iso-propanol is added to R1002 from day tank. Solid NaNO 2 is charged to R1001 and to this sufficient amount of water is added which dissolves NaNO2 and forms NaNO2 solution. Proper heat transfer arrangement is provided for removing heat of solution. This NaNO2 solution at 250C is charged toR1002. In addition to this required amount of 98% H 2SO4 and process water is added to R1002 from respective day tanks. Reaction takes place at 500 C, so it is necessary to heat all reactants to 500 C. After this constant temperature is achieved reaction takes place in around 3 hours. This reaction is exothermic so constant heat removal is carried out. Here we get one mole of 3, 5-dichloro-4-nitroaniline per mole of 2,6-dichloro-4-nitroaniline with 100% selectivity and 100% conversion of 2,6-dichloro-4-nitroaniline.

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During this deamination reaction, nitrogen is evolved which is vented out of the reactor to the atmosphere. Product, 3, 5-dichloro-4-nitroaniline, melts at 65 0 C so it will be in solid state when it comes out of reactor. Thus 3, 5-dichloro-4nitroaniline is separated by filtration in the solid form by using agitated nutsche type of filter. Mother liquor contains mainly H2O and iso-propanol and inorganic salts. Isopropanol is recovered by distillation and recycled back. Since, 3, 5-dichloro-4nitroaniline is insoluble in water, it will be absent in mother liquor.

Section ( II ) Hydrogenation is effected in a CSTR which is Gas-Inducing-Dead-End type of reactor. Since, hydrogen can form explosive mixture; Dead-End type of reactor is preferred to ensure safety. Dead-End type of reactor is that in which there is total consumption of hydrogen in the reactor and no hydrogen gas is vented out. Detailed description: 3, 5-dichloro-4-nitroaniline which is separated by filtration is heated and converted into liquid form and fed to R1003 which is hydrogenation reactor. It is simple CSTR. Sufficient quantity of 50% H2SO4 is prepared in D1004. Required amount of 50% H2SO4 is charged to R1003 from day tank. Apart from this, R1003 is charged with Raney-Nickel catalyst and hydrogen gas sparged at five bar pressure in stoichiometric amount. Hydrogenation of 3, 5-Dichloronitrobenzene is carried out at 700C for around 2.5 hours. Thus all these reactants are to be heated to reaction temperature and same temperature is maintained in the reactor. Here, all reactants are preheated and added to R1003. Hydrogenation reaction is exothermic so liberated heat need to be removed by providing proper cooling arrangement. Here we will get 100% yield as meta oriented chlorine is not get removed under such mild conditions.

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After reaction gets over, output of R1003 contains 3, 5-dichloroaniline, water formed in the reaction, suphuric acid charged and catalyst. This mixture is then filtered at more than 700C to remove catalyst. Mother liquor will contain 3, 5dichloroaniline, water formed in the reaction and sulphuric acid charged in the reactor. Mother liquor from F1002 is fed to phase separator (P1001) to separate aqueous and organic phases. Aqueous phase will contain most of water and sulphuric acid which is sent to effluent treatment plant. Solubility of 3, 5-dichloroaniline in water is very less (0.6 gm/lit) so only small amount of solid will go into water. Organic phase will mainly contain 3,5-dichloroaniline along with very less amount of sulphuric acid and water. Since we require 3, 5-dichloroaniline more than 99% pure we need to remove this associated sulphuric acid and water. 50% solution of NaOH is added for neutralizing sulphuric acid and water associated with it will dissolve salt formed and excess NaOH. After this water wash is required to remove any inorganic part associated with organic phase. Then aqueous and organic phases are separated by P1002 to obtain 3, 5-dichloroaniline in organic phase which will be more than 99% pure. Since there is not any other organic compound with 3, 5-dichloroaniline in organic phase we need not require distillation unit.

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6.1 MATERIAL BALANCE

Product: 500 TPA of 3, 5-dichloroaniline Basis: Plant operates for 328 days and hence 1525 Kg of product need to be produced per day.

Material Balances across the equipments: Mixer(R1001)

NaNO2 which is nitrosating agent is in the solid form and hence dissolved in water in this equipment. NaNO2 and water are introduced at 250 C. IN Quantity Component NaNO2 H2O Total (kg / day) 1176.4 1646.9 2823.3 Component (kg / day) NaNO2 2823.3 Solution Total 2823.3 OUT Quantity

Reactor (R1002)
2,6-Dichloro-4-nitrobenzene is added to reactor through fresh material and dissolved in iso-propanol which acts as solvent. NaNO 2 solution prepared in mixer is also added to this reactor. In addition to that 98 % H2SO4 and H2O are also added in sufficient amount. In Quantity Component (kg / day) 2,6-Dichloro-41948.1 nitrobenzene Iso-propanol Water 98% H2SO4 1694 2823.3 H2SO4-1797.5 19 3,5-Dichloronitrobenzene Iso-propanol Water Na2SO4 1806.9 1694 4507.9 1336.4 Component (kg / day) Out Quantity

H2O-37.64 NaNO2-1176.4 NaNO2 Solution H2O-1646.9 Total 11123.9 H2SO5 N2 Total 1072.8 263.5 11123.8 HNO2 442.3

Filter (F1001)
The outlet stream from Reactor (1002) enters the filter and gets separated into solid and liquid phases. Since solubility of 3,5-Dichloronitrobenzene in water is zero, we take the balance for both the phases with no 3,5-Dichloronitrobenzene in the mother liquor. We assume that 3,5-Dichloronitrobenzene is sparingly soluble in organic solvent that is iso-propanol and we consider this quantity as negligible. Thus all 3,5-Dichloronitrobenzene will be in the form of cake. We will add water, 50% by weight of cake for washing. Thus amount of water need to be added is 900 kg.

Cake Quantity Component (kg / day) 3,51806.9 Dichloronitrobenzene

Mother liquor Quantity Component (kg / day) Iso-propanol Water Na2SO4 HNO2 H2SO5 Total 1694 5407.9 1336.4 442.3 1072.8 9953.4

Total

1806.9

Distillation Column (D1001) :

Mother liquor obtained after filtration contains iso-propanol which is need to be separated. Since, iso-propanol is soluble in water we need to employ distillation to separate it. Thus after separation of iso-propanol, remaining aqueous phase is sent to

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ETP for further treatment. This iso-propanol which is separated is recycled back to main storage tank. IN Quantity Component Iso-propanol Water Na2SO4 HNO2 H2SO5 Total (kg / day) 1694 4507.9 1336.4 442.3 1072.8 9053.4 (kg / day) 1694 5.13 0 0 0 1699.13 1336.4 442.3 1072.8 7354.3 (kg / day) 0 4502.8 Distillate OUT Bottom

Reactor (R1003)
Solid product obtained after filtration is turned into liquid by heating before it is fed to this reactor. In addition to 3,5-Dichloronitrobenzene small amount 50% H2SO4 and required amount of Raney Nickel catalyst is charged into the reactor. Here, hydrogenation of 3,5-Dichloronitrobenzene is carried out which gives 3,5Dichloroaniline and water. For this process hydrogen is sparged from bottom at 5 bar pressure. Hydrogen is charged in no excess. IN Quantity Component (kg / day) 3,51806.9 Dichloronitrobenzene H2SO4-1.497 50% H2SO4 Catalyst H2 Total H2O-1.497 44.737 56.47 1911.1 H2SO4 Water Catalyst H2 Total 1.497 340.3 44.737 0 1911.1 3,5-Dichloroaniline 1524.6 Component (kg / day) OUT Quantity

Filter (F1002):
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Output stream from reactor (R1003) is filtered at reaction temperature for removing catalyst from solution. Cake Quantity Component Catalyst Total (kg / day) 44.737 44.737 Component 3,5-Dichloroaniline H2SO4 Water Total (kg / day) 1524.6 1.497 340.3 1866.4 Mother liquor Quantity

Phase separator (PS1001):

Input to this unit is nothing but the mother liquor obtained after filtration. Thus this outlet stream from filter enters into the separator and gets separated in the aqueous and organic phases. Since solubility of 3,5-Dichloroaniline in water is 0.6 gm/lit some amount of 3,5-Dichloroaniline will go in aqueous phase. But majority part of 3, 5-Dichloroaniline will be in organic phase. After separation some amount of H2SO4 along with some water will go into organic phase.

AQUEOUS Quantity Component 3,5-Dichloroaniline H2SO4 Water Total (kg / day) 0.17 1.47 333.5 335.14

ORGANIC Quantity Component 3,5-Dichloroaniline H2SO4 Water Total (kg / day) 1524.4 0.03 6.81 1531.24

Neutralizer (N1001):
Organic phase obtained from phase separation is charged into this unit for removing unwanted H2SO4. This is need to be done since we require more than 99% pure product. Here, we add 50% NaOH solution to neutralize H 2SO4 accompanying organic phase. 22

IN Quantity Component 3,5-Dichloroaniline H2SO4 Water 50% NaOH solution Total H2O-0.025 1531.3 Total (kg / day) 1524.4 0.03 6.81 NaOH-0.025 Component

OUT Quantity 3,5-Dichloroaniline Na2SO4 Water (kg / day) 1524.4 0.043 6.85

1531.3

Washing Unit (W1001):

After neutralization unit washing of product with water is done in order to remove salt formed during neutralization and also excess NaOH. Thus, 2 kg of water is added to output of neutralizer.

Phase separator (PS1002)

Input to this unit is output of neutralizer and extra 2 kg of washing water added. Organic phase and aqueous phases are separated after this to get more than 99% pure 3,5-Dichloroaniline. AQUEOUS Quantity Component 3,5-Dichloroaniline Na2SO4 Water Total Thus purity of final product is = (1524.4/1524.58) =99.98% (kg / day) 0.005 0.043 8.67 8.72 Component 3,5-Dichloroaniline Water Total (kg / day) 1524.4 0.18 1524.58 ORGANIC Quantity

100

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Amount of product formed per day =9.4099 162 1000 =1524.4 Kg/ day

6.2 ENERGY BALANCE

Product: 500 TPA of 3,5-dichloroaniline Basis: Plant operates for 328 days and hence 1525 Kg of product need to be produced per day. Energy balance across the equipments:

In all the calculations the reference temperature is taken as 250 C. The formula used for calculating the enthalpy of a stream is,
Q = m C P T

The condenser load is calculated by using the formula,

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QC = m

Where is latent heat of vaporization of the component which is to be condensed. The Reboiler load is calculated by taking overall energy balance across the distillation column as,
Q R = Q D + Q B + QC Q F

Where the subscripts R, D, B, C and F refers to Reboiler, distillate, bottoms, condenser and feed respectively.

Mixer (R1001)
NaNO2 which is nitrosating agent is in the solid form and hence dissolved in water in this equipment. NaNO2 and water are introduced at 250 C. IN Temperature Component NaNO2 H2O Total C 25 25
0

Enthalpy Component KJ 0 0 0 NaNO2

OUT Temperature
0

Enthalpy KJ 0 0

25 solution Total

Heat of solution =-256800 KJ

25

Thus heat need to be removed by cooling water so as to keep outlet stream temperature constant at 250C = 256800 KJ

Reactor (R1002)
All the reactants are charged at 25 0C. Reaction takes place at 500 C. Internal coils are used for reaction mixture to reaction temperature.

IN Temperature Component
0

OUT Enthalpy Component KJ 3,50 Temperature Enthalpy

0

KJ

NaNO2 25 solution H2O 25 0

Dichloronitrobenzene

50

66340

H2O

50

471500

98% H2SO4 2,6Dichloro-4nitroaniline Iso-

25

Na2SO4

50

32300

25

H2SO5

50

46350

25 propanol

Iso-propanol

50

64940

HNO2

50

411300

N2

50

6843

26

Total

Total

1099600

Total heat evolved during reaction=4115300 KJ Amount of heat need to be provided for heating reaction mixture to 500C = 591280 KJ Thus amount of heat need to be removed in order to keep reaction mixture temperature constant = 3608000 KJ

Distillation column (D1001):

Here we want to remove iso-propanol and water from the incoming stream. As isopropanol boils at around 790 C which is less temperature compared to temperature at which water boils. Thus we can get complete separation of iso-propanol and Water from rest of the mixture. The temperature of the incoming stream is 25 o C. thus the load on the reboiler is that of heating the mixture upto bubble point and then supplying the latent heat of vaporization. The load on the condenser is to condense the upcoming vapors using cooling water. The reboiler load is found to be 3831400 KJ/day. This heat is supplied by using saturated steam. The condenser load is found to be 3633200 KJ/day. This heat is removed by using cooling water coming in at 25 o C.

Melting operation:
During this operation 3,5- Dichloronitrobenzene is melted. Thus we need to consider heat of fusion of this compound.

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Thus heat required to melt 3,5- Dichloronitrobenzene =279690 KJ

Reactor (R1003):
In this stage 3,5- Dichloronitrobenzene in molten form is added to reactor along with sulphuric acid and catalyst. Reaction is carried out at 70 0 C. Since reaction is exothermic large amount of heat need to be removed.

IN
Temperatur Enthalpy Component 3,5dichloronitrobenzene 50% H2SO4 solution H2 Total Heat of reaction =5023100 KJ Thus amount of heat need to be removed = 4889280 KJ/day = 56590 J/s 70 70 70 13267 417.53 43993 57680 e KJ
0

OUT
Temperatur Enthalpy Component 3,5Dichloroaniline H2SO4 Solution H2O H2 Total 70 70 70 70 119960 417.53 63788 7332 191498 e KJ
0

Neutraliser:
In this stage unwanted sulphuric acid associated with 3,5- dichloroaniline is removed. Thus 50% NaOH solution is used for this. Heat of neutralization =-57.1 KJ/mole =-57.1 6.114 0.0001

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=-34.911 J Since, heat evolved in this operation is very small we do not require jacket. Also we will not try to remove that small quantity of heat.

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