Direct Chlorination Reactor (R-100)

In the direct chlorination of Ethylene, ethylene and chlorine are reacted in the EDC liquid phase,

gas phase chlorination is not industrially used. Low Temperature Chlorination (LTC) was chosen

instead of High Temperature Chlorination (HTC) because it has the advantage of forming lower

byproducts, and high selectivities are obtained.

• Assumptions:

- A specified amount of liquid EDC was fed to the reactor to initiate the liquid-phase

reaction, and after reaching the required conversion, the stream was removed, because there

is no industrial application where a continuous EDC flow stream exists.

- Reactants consumption and product formation are calculated based on initial reactant

parameters; no phase change occurred, and no pressure drop.

• Reactions:

- C2H4 + Cl2 → C2H4Cl2 …... (1) X = 0.986

- C2H4Cl2 + Cl2 → C2H3Cl3 + HCl …… (2) X = 0.004

• Kinetics Data:

- R1 = K1 [Cl2] [C2H4] …… K1 = 0.132 m3/ mol. s @ 120 ֯ C (Dry, et al., 2003)

- R2 = K2 [Cl2]2 [C2H4] …… K2 = 0.0239 m6/ mol2. s @ 120 ֯ C (Dry, et al., 2003)

• Initial Reactant Parameters:

- Gas Phase, 25 ֯ C, 1.5 atm.

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 - Cl2 is the limiting reactant. (Wiley-VCH Verlag GmbH & Co. KGaA, 2006)

• Volume of the reactor calculations:

For the First Reaction (C2H4 + Cl2 → C2H4Cl2)

- R1 = K1 [Cl2] [C2H4] …… K1 = 0.132 m3/ mol. s @ 120 ֯ C

- To find the value of K1 at 62 ֯ C; Arrhenius equation is used:

𝐸𝑎 1 1 𝐸𝑎1
K1 (T2) = K (T2) Exp ( * (𝑇1 - 𝑇2)) …… = 2518 K (GIOVANNI)
𝑅 𝑅

1 1
K1 (335) = 0.132 m3/ mol. s * Exp (2518 (393 - 335 ))

Assuming the value of K was constant along the reactor and was taken at the final temperature of

the reaction; 62֯ C

K1 (298) = 43.5 m3/ Kmol. s

Table 79: -Reactants Consumption and Product Formation (First Reaction)

Species Feed (Kmol/s) Change (Kmol/s) Effluent (Kmol/s)

FA = FA0 (1-x)
A FA0 = 0.098 - FA0 x = - 0.0966
FA = 0.001372

B FB0 = FA0 = 0.98 - FA0 x = - 0.0966 FB = FA = 0.001372

C Zero FA0 x = 0.0966 FC = FA0 x = 0.095

FTO = 0.196 Kmol/ s

FT = 0.097 Kmol/s

Ꜫ = YAO * δ

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 𝐹𝐴𝑂 0.098
YA0 = 𝐹𝑇𝑂 = 0.196 = 0.5

δ = 1 -1 -1 = -1

Ꜫ = - 0.5

CA0 = YAO * CT0

𝑃0
= 0.5*𝑅 𝑇0

1.5 𝑎𝑡𝑚∗𝑚𝑜𝑙.𝐾
CA0 = 0.5 * 0.08205 𝐿 .𝑎𝑡𝑚∗298 𝐾 = 0.0306 mol/L

CA0 = 0.0306 Kmol/ m3

(1−𝑋) 𝑃 𝑇0
CA = CA0
(1−0.5𝑋) 𝑃𝑜 𝑇

1−𝑋 𝑇𝑜
R1 = K1 CA02 (1−0.5𝑋 )2 * ( 𝑇 )2

- Volume of the Reactor Based on the First Reaction

𝑥 𝑑𝑥
V = FA0 ∫0 −𝑅1

𝐹𝐴0 𝑋 𝑑𝑥
V= 𝑇0 2
∫0 1−𝑥 2
𝐾 𝐶𝐴02 ∗( ) (
1−0.5𝑥
)
𝑇

0.0981 𝐾𝑚𝑜𝑙∗𝐾𝑚𝑜𝑙. 𝑠∗ 𝑚 6 0.986 𝑑𝑥

V = 2.9 * 19 = 55.1 m3

Volume of the Reactor (First Reaction) = 55.1 m 3

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For the Second Reaction (C2H4Cl2 + Cl2 → C2H3Cl3 + HCl)

- R2 = K2 [Cl2]2 [C2H4] …… K2 = 0.0239 m6/ mol2. s @ 120 ֯ C (original)

- To find the value of K2 at 62 ֯ C; Arrhenius equation is used:

𝐸𝑎 1 1 𝐸𝑎1
K2 (T2) = K (T2) Exp ( * (𝑇1 - 𝑇2)) …… = 7282.21 K (GIOVANNI)
𝑅 𝑅

1 1
K2 (335) = 0.0239 m6/ mol2. s * Exp (7282.21 (393 - 335 ))

K2 (335) = 966.3 m6/ Kmol2. s

Table 80: Reactants Consumption and Product Formation (Second Reaction)

Species Feed (Kmol/s) Change (Kmol/s) Effluent (Kmol/s)

FA = FA0 (1-x)
A FA0 = 0.098 - FA0 x = - 0.000392
FA = 0.0976

B FB0 = FA0 = 0.98 - FA0 x = - 0.000392 FB = FA = 0.097

C Zero FA0 x = 0.000392 FC = 0.000392

D Zero FA0 = 0.000392 FD = 0.000392

FTO = 0.196 Kmol/ s

FT = 0.196 Kmol/s

Ꜫ = YAO * δ

𝐹𝐴𝑂 0.098
YA0 = 𝐹𝑇𝑂 = 0.196 = 0.5

δ = 1 +1 -1 -1 = 0

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Ꜫ=0

CA0 = YAO * CT0

𝑃0
= 0.5 *𝑅 𝑇0

1.5 𝑎𝑡𝑚∗𝑚𝑜𝑙.𝐾
CA0 = 0.5 * 0.08205 𝐿 .𝑎𝑡𝑚∗298 𝐾 = 0.0306 mol/ L

CA0 = 0.0306 Kmol/ m3

(1−𝑋) 𝑃 𝑇0
CA = CA0 (1−0𝑋) 𝑃𝑜 𝑇

1−𝑋 𝑇𝑜
R2 = K2 CA03 (1−0 )3 * ( 𝑇 )3

- Volume of the Reactor Based on the Second Reaction

𝑥 𝑑𝑥
V = FA0 ∫0 −𝑅1

𝐹𝐴0 𝑋 𝑑𝑥
V = 𝐾 𝐶𝐴03 ∫0 (1−𝑥)3

0.0981 𝐾𝑚𝑜𝑙∗𝐾𝑚𝑜𝑙2 . 𝑠∗ 𝑚 9 0.986 𝑑𝑥

V = 4.8 * 0.004

Volume of the Reactor (Second Reaction) = 0.0192 m 3

Total Volume of the Reactor = 55.1 + 0.0192

Total Volume of the Reactor = 55.1192 m3

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Dimensions of the Reactor

Assume number of tubes = 500 tube

Assume diameter of one tube = 6 inches = 0.15 m

Assume length of bend between tubes = 0.25 m

Number of bends = Number of tubes – 1 = 499 bends

𝑅𝑒𝑎𝑐𝑡𝑜𝑟 𝑉𝑜𝑙𝑢𝑚𝑒
Total length (without bends) = .
𝜋∗(𝐷)2
= 3242 m
4

Total length of tubes = (3242 – (0.25 * 499) = 3117 m

𝑇𝑜𝑡𝑎𝑙 𝐿𝑒𝑛𝑔𝑡ℎ 𝑜𝑓 𝑡𝑢𝑏𝑒𝑠 3117

Amount of Needed of Cooling water

Q = m CP ΔT

𝑄 20885.6 𝐾𝑔
m = 𝐶𝑝 ∆𝑇 = 4.185∗42 = 118.8 𝑠

Assuming inlet temperature of inlet water stream = 293 K

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