6.0 6.

ENERGY BALANCE General Manual for Energy Balance

Heat of formation : f = P R Heat of reaction : =[

] T

The first law of thermodynamics says that energy be neither created nor destroyed. The following is a systematic energy balance performed for each unit of the process. The datum temperature for calculation is taken as 25 OC. The pressure is taken to be 1 atm throughout the process. The physical properties such as density, specific heat, heat of reaction, and heat of formation were assumed as constant over the temperature range.

Component

) 52.30 0 -399.40 -94.12 (solid) 0 -92.30 -169.70 -867.10 0 0.05450 0.03394 0.03832 0.05363 0.02884 0.02910 0.12900 0.12310 0.91776

Ethylene Chlorine Ferric chloride Vinyl chloride Hydrogen Hydrogen chloride Dichloroethane Acetic acid Oxygen

Table 1 : Heat Capacity and Enthalpy Data

6.2

Energy Balance Calculations

Nomenclature used

Enthalpy heat reaction of reactant Enthalpy heat of formation Enthalpy heat reaction of product Cp Specific heat capacity Enthalpy heat reaction )

6.2.1 6.2.1.1

Energy balance for direct chlorination Mixer

Stream involved: Stream 1 Stream 2 Stream 3

Enthalpy of formation of reaction at 25C @ 298K: +

= = (-169.7 52.3- 0) =( )

Enthalpy of reactants: Reactants are added at 25C.

=[

] T

=[ 0.05450 1 + 0.03394 1 ](393-298) = 8.4018

Enthalpy of products:

Products leave at 25 C.

T =[0.129 x 1 ](393-298)

= 12.255

Enthalpy of reaction:

The negative sign in the above calculation

indicates that the reaction is exothermic.

Enters at 25 C and leaves at 120 C.

6.2.1.2

Energy balances at Reactor

Stream involved: Stream 1 Stream 2 Stream 6

Main Reaction:

Table 3 : Direct chlorination reactor parameter Reactor temperature (C) Reactor pressure (kpa) Reactor volume ( Tube diameter (in) Tube length (ft) Residence time (hr) 180 350 90 2 112 0.018

Direct chlorination :

(1)

Ethylene and chlorine combine in a homogeneous catalytic reaction to form EDC. Normally, the reaction rate is controlled by mass transfer, with absorption of ethylene as the limiting factor. Due to high selectivity, ferric chloride is the common catalyst of choice for chlorination of ethylene. The catalytic reaction utilizes an electrophilic addition mechanism. The catalyst polarizes chlorine (Eqn. 2) and then the polarized chlorine molecule acts as an electrophilic reagent to add Cl- to the double bond of ethylene. + For oxychlorination EDC pyrolysis 2 Overall reaction 2 +

(2) (3) (4) (5) (6)

Enthalpy of formation of reaction at 180C @ 453K:

= = (-169.7 52.3- 0) =( )

Enthalpy of reactants:

Reactants are added in reactor.

Stream 1 R1 =[ ] T

=[ 0.05450 1](453-323) = 7.085

Stream 2 R2

=[

] T

=[ 0.03394 1 ]( 453-323) = 4.4122

= 7.085 + 4.4122 = 11.4872

Enthalpy of products:

Products leave at 180 C.

= =[(0.1231 x = 10.1232

Enthalpy of reaction:

The negative sign in the above calculation

indicates that the reaction is exothermic.

6.2.2

Energy balances at oxychlorination

Table 3 : Oxychlorination reactor parameter Reactor temperature (C) Reactor pressure (psig) Reactor volume ( Tube diameter (in) Tube length (ft) Residence time (hr) 120 15 461 2 1320 0.05

Since the value of oxygen is small thus, it assume to be neglected. O2 at T 305 = 0.9964 ( )

Enthalpy of formation :

 = = [0 + (-169.7) ( =( 6.2.2.1 ) + 2( -92.30) + (52.3) )]

Energy balances in mixer

Stream involved: Stream 1 Stream 2 Stream 3

Enthalpy of formation of reaction at 25C @ 298K: +

= = (-169.7 52.3- 0) =( )

Enthalpy of reactants: Reactants are added at 25C.

Enthalpy of products:

Products leave at 25 C.

= [

] T

=[ 0.05450 0.4413 + 0.03394 0.5587 ](393-298) = 4.0862

Enthalpy of reaction:

The negative sign in the above calculation

indicates that the reaction is exothermic.

Enters at 25 C and leaves at 120 C.

6.2.2.2

Energy balances at heat exchanger

Stream involved: Stream 3 Stream 5

Enthalpy of formation of reaction at heat exchanger :

Since it is heat exchanger, thus there is no formation occur. There is just flow of component inside the heat exchanger to increase temperature to 180 .

Enthalpy of formation:

Enthalpy of products:

= =[ = 4.0862

Enthalpy of reactant:

= Enthalpy of reaction:

6.3

Energy balances at the separator

Stream involved : Stream 6 Stream 7 Stream 8

Separator is to separate the components into two streams; one for HCl recycle (stream 6) and one for vinyl chloride(stream 8).

Enthalpy of formation of reaction at 50C @ 323 K:

= = (-92.12 +(-94.12) 52.3- 0) =( )

Enthalpy of reactants: Reactants are added at 50C. Stream 6

Enthalpy of products:

Products leave at 50 C.

= [

=[ 0.05363 x 1 ](393-298) = 5.09485

Enthalpy of reaction: