2.

Variables operacionales

En el cracking térmico, las principales variables dependientes son la conversión

y la selectividad. La conversión es una medida del grado de cracking, es decir,
el porcentaje de consumo del compuesto alimentado mientras que la
selectividad indica el aprovechamiento de la carga en producto deseado. La
conversión y la selectividad responden a la temperatura de reacción, el tiempo
de residencia, la composición de la carga y la presión parcial de los
hidrocarburos. La selectividad es más sensible a la caída de presión en el
serpentín que la conversión; de ese modo, cuando el serpentín del horno
acumula coque, la selectividad se reduce significativamente.
2.1

Carga al horno reactor.

El tipo de alimento afecta la conversión de la carga en olefinas, así mismo, el

tiempo de operación y el diseño del reactor. Las principales variables
asociadas a la carga son la composición y el flujo de carga.
2.2

Temperatura de reacción.

La temperatura de reacción es la variable manipulada que afecta, de manera

directa e inmediata, la conversión e, inversamente, el tiempo de residencia. En
reacciones endotérmicas, como es el caso de la pirólisis, la velocidad
de reacción directa es mayor que la velocidad de reacción inversa cuando la
temperatura es más alta, favoreciendo la formación del producto del lado
derecho de la ecuación. La temperatura varía a lo largo del serpentín con un
perfil característico de los hornos de pirólisis, el rango normal de temperatura
va desde 973 K hasta 1173 K, dependiendo del tipo de carga al horno. Para el
caso de la pirólisis del etano, la temperatura varía entre 1073 K y 1123 K
2
.
2.3

Presión parcial del hidrocarburo y la función del vapor.

Desde el punto de vista termodinámico, las reacciones de pirólisis para la

producción de olefinas livianas avanzan más cuando tienen lugar a bajas
presiones y, por ello, a la salida del serpentín, se opera a presiones cercanas a
la atmosférica

Efecto de la temperatura

El craqueo es una reacción endotérmica, y además requiere de energía

continua para iniciar la reacción inmediatamente activada.

Ethylene yields are favored by low pressure, high temperature and

low residence time in the coil. The residence time can be reduced by
shortening the length of the coils but this would lead to higher heat
fluxes through the tube walls and hence higher wall temperatures. This
would obviously mean that better and more expensive coil materials
would be needed to for the same furnace capacity. Moreover, higher wall
temperatures would also result in more coke deposition. Therefore, any
technology that can improve heat transfer rates without raising tube wall
temperatures would be a great advantage. Technip’s Swirl Flow Tube
(SFT®) technology does precisely that.

SFT® is shaped by bending a straight tube in such a way that the

tube's centerline traces a helix in three dimensional space. These
tubes are characterized by small amplitudes and pitches of varying
lengths. The maximum amplitude of the helix is less than the radius of
the tube and provides a line of sight through the tube. The shape
contributes to the optimization of the cracking process by changing the
flow profile from 2D to 3D.

The SFT® geometry induces a swirl and promotes circumferential

mixing and convective heat transfer inside the coil. This swirl flow
enhances the heat transfer by a more intense mixing in the circumference
compared to the classical straight tubes. This carries a small penalty in
the form of higher coil pressure drop. SFT® tubes give 35 to 90% higher
heat transfer rates compared to straight tubes, at the cost of 40 to 90%
higher pressure drop. Research has shown that its pressure drop
increases approximately
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linearly in SFT® whereas alternative technologies have a higher penalty.

As a result of the above, SFT® have a significant advantage over other
coils with special attributes implemented in them.

Technip developed the equipment to transform a two dimensional

induction bending machine into a three dimensional one. The latter is
required to create the helical shape of SFT® tubes. This process can
bend all types of radiant coils –for example: 25Cr35NiNb or
35Cr45NiNb– from all coil suppliers. The maintenance of SFT® tubes is
not different from straight tubes. Should there be a partial blockage in a
tube, it is possible to replace only a small part, as can be done for a
straight tube. This requires the availability of spare SFT® tubes.
SFT® Client Advantages are: By using SFT® tubes, the run length of
a furnace can easily be 20 to 50 days longer, at the same capacity. This
will result in lower NOx emissions as well. Another advantage of SFT®
tubes is the capacity increase, typically 10 to 30% at similar or same
ethylene yield. SFT® tubes allow an increased selectivity by decreasing
the residence time at the same capacity. Finally, another advantage of
SFT® tubes is the increase in steam dilution ratio to enhance yields and
reduce coke formation. The SFT® technology is best applied in tubes
with the highest tube metal temperatures. It can be applied in existing
furnaces of any supplier and grassroots furnaces.

For more information about our SFT Technology please call 0031-
79-3293816 or sent an email towards jdejager@technip.com.

The selectivity towards ethylene is lower, confirming the general trends

described in the literature. This amounts to a considerable 1% lower
ethylene yield when comparing a bare tube with the tube with small
fins and short pitch length. Higher mass fractions of the heavier
components are obtained as the increased pressure drop leads to
higher hydrocarbon partial pressures, promoting bimolecular reactions.
Also the yield of components typically formed through recombination
reactions such as methane and ethane increases with increased
pressure drop.

After 9 days however a considerable layer of coke was deposited,

leading to slightly altered product yields. These are shown in Table 4.

Especies para mecanismos de radicales libres

Para etano:

i: H2, CH4 C2H2 C2H4 C2H6 C3H6 C3H8 C4H6 C4H8 C4H10 C5+ H CH3 C2H3
C2H5 C3H5 1-C3H7 C4H7 1-C4H9 C5H11 C

Para propano:

i: H2 CH4 C2H2 C2H4 C2H6 C3H6 C3H8 C4H6 C4H8 C4H10 C5+ H CH3 C2H3,
C2H5 C3H5 1-C3H7 2-C3H7 C4H7 1-C4H9 2-C4H9 C5H11 C

Mecanismo por Planta de Olefinas

radicales libres existente
Simulador Ansys (Industrial)
Fluent
(tubos rectos)
 % %
H2 3.73 3.75
CH4 2.83 3.45
C2H2 0.03 N/R
C2H4 50.44 48
C2H6 39.90 N/R
C3H6 0.89 N/R
C3H8 0.00 N/R
C4H6 0.84 N/R
C4H8 0.01 N/R
C4H10 0.14 N/R
Conversión 60.4 60.4
T salida(ºC) 836.6 836.6
Presión sallida 1.75
1.74
(bar)

Table 4: Simulated product yields [%w] after 9 days for various reactor
geometries.

Tubos
Componentes rectos SFT M SFT H

Presión de entrada [bara] 3.44 3.05 3.13

1190.3 1185.0 1180.3

Temperatura de salida [K]

Productos [wt%]

Hidrógeno 1.46 1.45 1.44

Metano 17.02 17.13 17.24

Acetileno 0.37 0.35 0.33

Etileno 30.74 30.63 30.52

Etano 2.92 2.91 2.91

Propino 0.78 0.76 0.74

Propadieno 0.19 0.18 0.18

Propileno 20.21 20.20 20.17

Propano 22.25 22.25 22.25

1,3-Butadieno 0.94 0.96 0.97

1-Buteno 0.63 0.63 0.63

2-Buteno 0.21 0.21 0.21

iso-Buteno 0.14 0.15 0.14

1,3-Pentadieno 0.16 0.16 0.17

1,4-Pentadieno 0.10 0.10 0.11

1,3-Ciclopentadieno 0.96 0.97 0.98

metil-1,3-Ciclopentadieno 0.10 0.10 0.11

Benceno 0.38 0.41 0.44

Tolueno