CERTIFICAMOS:
Que Dña. DESEADA BERENGUER MUÑOZ, Licenciada en Químicas,
ha realizado bajo nuestra dirección, en el Departamento de Ingeniería
Química de la Facultad de Ciencias de la Universidad de Alicante, el
trabajo que con el título “CRAQUEO CATALÍTICO DE POLÍMEROS;
ESTUDIO DE DIFERENTES SISTEMAS
POLÍMERO/CATALIZADOR” constituye su memoria para aspirar al
Grado de Doctor, reuniendo a nuestro juicio, las condiciones necesarias
para ser presentada y defendida ante el Tribunal correspondiente.
i
Este trabajo no hubiera sido posible sin la colaboración de muchas
personas, a las que me gustaría agradecérselo con estas palabras.
iii
Lista de Publicaciones
v
Otras publicaciones del autor relacionadas con la Tesis.
4 - Marcilla A., Odjo A. O., Garcia-Qeusada J. C., Gómez-Siurana A., Martinez R. N.,
Berenguer D. M., Design and Construction of a Fluid Catalytic Cracking Pilot Plant for
Vacuum Gas Oil-Plastic Wastes Blends Co-Processing, (Chemical Reactor Engineering
Conference), Agosto 2007, Poster.
5 - Marcilla A., Odjo A. O., Garcia-Quesada J. C., Gomez-Siurana A., Berenguer D.,
Martinez R. N., Flow Behaviour of Blends of Vacuum Gas Oil and Low Density
Polyethylene Blends, (Chemical Reactor Engineering Conference), Agosto 2007,
Poster.
6 - Marcilla A., Odjo A.O., García-Quesada J.C., Gómez A., Martínez R.N., Berenguer
D., Flow Properties of Vacuum Gas Oil–Low Density Polyethylene Blends, Fuel
Processing Technology, (2007), pp. 0378-3820.
vi
8 - Odjo A.O., Marcilla-Gomis A., Martinez R.N., Gómez-Siurana A., García-Quesada
J.C., Berenguer Muñoz D., García-Cortés A.N., Prediction of the Viscosity of Vacuum
Gas Oil-Low Density Polyethylene Blends under Varying Shear Rates, Concentrations
and Temperaturas, International Journal of Chemical Reactor Engineering: Vol. 6
(2008) pp.1542-6580.
vii
Índice
ÍNDICE
Agradecimientos……………………………………………………………………….iii
Lista de publicaciones………………………………………………………………….v
Otras comunicaciones…………………………………………………………………vi
Índice…………………………………………………………..…………...…………..ix
Índice de tablas……………………………………………………………….……….xii
Índice de figuras……………………………………………………………………...xiii
1. RESUMEN…………………………………………………………………………...1
2. INTRODUCCIÓN…………………………………………………………………...7
2.1. Reciclado de residuos plásticos……………………………………………11
2.1.1. Reciclado mecánico………….…………………………………..12
2.1.2. Reciclado químico……………………………………………….15
2.1.2.1. Degradación térmica…………………………………...16
2.1.2.2. Pirólisis catalítica………………………………………18
2.1.2.3. Gasificación…………………………………………….21
2.1.2.4. Hidrogenación………………………………………….22
2.1.3. Recuperación de energía…………………………………………23
2.1.4. Problemas y perspectivas actuales del reciclado…………………25
2.2. Estructura y propiedades de los catalizadores utilizados en el reciclado
químico de los plásticos………………………………………………………………...28
2.2.1. Estructura de las zeolitas…………………………………………29
2.2.2. Características de las zeolitas…………………………………….31
2.2.2.1. Propiedades físicas……………………………………..31
2.2.2.2. Propiedades químicas…………………………………..32
2.2.2.3. Propiedades catalíticas…………………………………33
2.2.2.4. Desactivación de los materiales zeolíticos……………..35
2.3. Principales materiales de SiO2-Al2O3 utilizados como catalizadores…..….37
2.3.1. Zeolita HZSM-5………………………………………………….37
2.3.2. Material MCM-41………………………………………………..39
2.3.3. Zeolita USY……………………………………………………...40
ix
Índice
3. OBJETIVOS………………………………………………………………………..59
4. MATERIALES Y MÉTODOS…………………………………………………….63
4.1. Catalizadores seleccionados……………………………………………….63
4.1.1. Catalizadores sintetizados en este trabajo………………………..63
4.1.1.1. Preparación de la zeolita HZSM-5…………………….63
4.1.1.2. Preparación del material MCM-41……………………..64
4.1.1.3. Zeolitas comerciales……………………………………67
4.2. Técnicas de caracterización de los materiales sólidos
ácidos…………………………………………………………………………………. 67
4.2.1. Difracción de Rayos X (DRX)…………………………………..68
4.2.2. Microscopia electrónica de transmisión (TEM)…………………69
4.2.3. Microscopia electrónica de barrido (SEM)……………………...70
4.2.4. Isotermas de adsorción de nitrógeno…………………………….72
4.2.5. Fluorescencia de Rayos X (FRX)………………………………..77
4.2.6. Deserción térmica programada (DTP) de amoniaco…………….78
x
Índice
5. CONCLUSIONES………………………………………………………………….99
6. BIBLIOGRAFÍA…………………………………………………………….……107
xi
Índice
ÍNDICE DE TABLAS
xii
Índice
ÍNDICE DE FIGURAS
xiii
Índice
xiv
RESUMEN
Resumen
• HZSM-5
• MCM-41(47)
• MCM-41(7)
1
Resumen
2
Resumen
Para estudiar este efecto en mayor profundidad se molió y tamizó una muestra
de HIPS, con la finalidad de obtener fracciones con diferente tamaño de partícula, y se
estudio el comportamiento de dichas fracciones en presencia del catalizador MCM-
41(7) mediante termogravimetria. Como resultado de este estudio se presenta la
publicación III donde se comprueba la influencia del grado de contacto entre el
polímero y el catalizador “Characterization of high-impact polystyrene by catalytic
pyrolysis over Al-MCM-41: Study of the influence of the contact between polymer and
catalyst”.
Los trabajos descritos en los párrafos precedentes surgen como consecuencia del
estudio sistemático realizado para cubrir el objetivo general planteado inicialmente de
estudiar el reciclado de residuos plásticos mediante el proceso de pirólisis catalítica.
Con este mismo objetivo, se consideró la posibilidad de llevar a cabo el proceso
utilizando unidades similares a las de craqueo catalítico en lecho fluidizado (FCC) de
las refinerías, y disolviendo el material plástico en un gasóleo de vacío similar al que se
3
Resumen
suele usar como alimento para obtener productos dentro del rango de las gasolinas. Con
el fin de evaluar esta posibilidad, se prepararon muestras con diferentes relaciones
VGO/Polietileno, y se realizaron diferentes estudios. En primer lugar, se analizó en
termobalanza el comportamiento de las mezclas frente a diferentes catalizadores,
utilizando tanto los sintetizados en el laboratorio como con otros sólidos ácidos
comerciales, así como también un catalizador de FCC de equilibrio. Se trabajo con
diferentes relaciones muestra:catalizador. También se determinó mediante
termogravimetria en atmósfera oxidante, la cantidad de coque depositado sobre cada
catalizador. Los resultados de este estudio aparecen reflejados en la publicación V que
lleva por título “Characterization of vacuum gas oil–low density polyethylene blends by
thermogravimetric analisis”
4
INTRODUCCIÓN
7
Introducción
reducción de 1,8 millones de toneladas. Además se ha calculado que, sin el uso de los
plásticos, el peso promedio de los envases aumentaría en un 291% (APME, 2006).
Mobiliario
5,9%
Envasado Construcción
Electrónica
46,8% 15,1%
3,8%
Sin embargo, los productos plásticos derivados de cada una de estas aplicaciones
no tienen el mismo tiempo de vida media, es decir, no se convierten en residuos al
mismo tiempo. Unas aplicaciones generan los residuos al año de su uso (envases, por
ejemplo) y otras al cabo de cincuenta años o más (construcción, por ejemplo). El resto
de aplicaciones presentan valores intermedios. Este es, por ejemplo, el caso de un
ordenador, un electrodoméstico, un coche, muebles o los plásticos agrícolas utilizados
8
Introducción
para varias campañas. Así en la figura 2.2 se han representado de una forma
esquemática las diferentes etapas que integran el ciclo de vida para los plásticos, que
van desde su fabricación y uso, hasta las posibles vías de reciclado, sobre las que se
incidirá con mayor detalle más adelante.
Hidrólisis
Despolimeración
Reciclado Glicólisis
Química
Directo Monomeros Otros
Despolímeración
Térmica
Materias Material de Reciclado
Producción Gas de Síntesis Gasificación Pirólisis
Primas Desecho Químico
Vía Térmica Termólisis
Corriente
Craqueo
Envasado Uso Hidrocarburos
Craqueo
Incineración Energía
Distribución Vía Catalítica Hidrocraqueo
Hidrogenación
Vertedero
RECICLADO
RECICLADO
CICLO DE VIDA
Reciclado Producto Proceso
Está claro que todo consumo genera un residuo. Los plásticos representan un
recurso muy valioso y apreciado como para convertirse en productos de desecho y ser
tirados a la basura directamente. Sin embargo, actualmente muchos de estos residuos
acaban en vertederos, cuando realmente se podrían aprovechar como materias primas de
nuevos materiales (reciclado) o como fuente de energía (valorización energética).
9
Introducción
La otra cara de este proceso está relacionada con las cuestiones ambientales,
económicas y sociales que plantea el crecimiento de los residuos sólidos en general y
que incluyen:
10
Introducción
Cuando se habla del tratamiento de los residuos plásticos, las opciones que
existen son las mismas que para el resto de residuos, y están basadas en la aplicación de
las tres "erres": reducir, reutilizar y recuperar, aunque con algunas particularidades
debidas a las características propias de estos materiales.
Por otra parte, hay que tener en cuenta que los plásticos presentan una serie de
características que los hace materiales idóneos para ser reutilizados, ya que son
duraderos, lavables, resistentes, esterilizables, etc. Con el desarrollo de envases ligeros
de recambio, este concepto está cada vez más vigente, tanto en el sector de la
distribución (cajas, pallets, bidones industriales y otros) como en el hogar.
Una vez que han sido agotadas las vías anteriores, los plásticos pasan a
convertirse en residuos. En este momento se propone su recuperación, que se puede
realizar esencialmente de tres maneras alternativas: el reciclado mecánico, el reciclado
químico y la recuperación energética.
11
Introducción
Hoy en día, en la mayor parte de las zonas donde se utilizan plásticos se están
desarrollando infraestructuras para el reciclado mecánico, para poder utilizar los
residuos como material para la fabricación de los nuevos productos plásticos.
Por ello, los residuos plásticos ideales para el reciclado mecánico son aquellos
objetos de mayor tamaño, por ejemplo botellas, parachoques y depósitos de gasolina de
los automóviles fuera de uso, o residuos recogidos en grandes cantidades como es el
caso del film procedente de invernaderos.
12
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13
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14
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15
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Una vez resueltos los mayores problemas tecnológicos de estos métodos, el reto
es hacer interesante la economía de estos tratamientos, cuya competitividad dependerá
siempre del precio del barril de petróleo, ya que suponen la mezcla del residuo plástico
con el crudo que se alimenta a la refinería.
16
Introducción
17
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Los catalizadores sólidos ácidos, tales como las zeolitas, favorecen las
reacciones de transferencia de hidrógeno en dichos centros ácidos. Además, el acceso de
las moléculas a los centros reactivos del catalizador, así como el desarrollo de los
productos finales en el interior de los poros está limitado por su tamaño. Por tanto, la
18
Introducción
preferencia por el uso de las zeolitas en este tipo de procesos se debe a su gran acidez y
al efecto estérico que presentan, factores que controlan la calidad de los productos
aportando selectividad en la forma y el tamaño (Pinto y col., 1999, Onu y col., 1999).
En la actualidad, la relación entre la calidad y la fuerza de los centros ácidos del
catalizador y la composición de los productos de la pirólisis constituye un tema de
investigación que está recibiendo mucha atención dentro de la literatura científica. Los
sólidos ácidos más utilizados como catalizadores son: zeolitas sintéticas, sílice-alúmina,
zeolitas naturales y otros aluminosilicatos con estructura porosa adecuada.
Parte de los trabajos que se están llevando a cabo en este campo se centran en el
estudio de la formación de coque durante el proceso de craqueo (Benito y col., 1996,
Lin y col., 1997, Guisnet y col., 1996, 2001, Arandes y col., 1999, Pater y col., 1999),
que se deposita en la superficie del catalizador haciendo que éste se desactive
gradualmente y que requiera procesos de regeneración en los que se elimina total o
parcialmente el coque formado. En general, los problemas que se presentan son
similares a los que se plantean en las operaciones de refino catalítico de la industria del
refino de petróleo.
19
Introducción
En general, el proceso consiste en una operación cíclica, donde las partículas del
catalizador, de un tamaño promedio de 70 μm, circulan en un reactor de lecho
fluidizado, donde se desactiva por deposición carbonosa en el reducido tiempo de
contacto con los hidrocarburos reactivos (típicamente menor a 10 segundos), y pasan
20
Introducción
2.1.2.3. Gasificación
21
Introducción
como materia prima para la fabricación de metano o amoníaco o incluso como agente
reductor para la producción de acero en altos hornos. Esta técnica presenta la ventaja,
frente a otros procedimientos de reciclado químico, de poder admitir como alimentación
toda la corriente de residuos municipales, sin necesidad de separar previamente los
plásticos.
Son muchas las compañías que están investigando esta opción de reciclado,
entre ellas Shell Oil (Reinink, A. y col., 1993), pero es Thermoselec, S.A. (Locarno,
Suiza) quien lidera esta tecnología. En su planta piloto instalada en Verbania (Italia) se
tratan 4,2 t/h de residuos sólidos municipales, que producen 500 kg de gas de síntesis,
220 kg de escoria, 23 kg de metales y 18 kg de sales por cada tonelada de residuo
tratado. En el proceso, los residuos, previamente compactados y desgasificados, se
pirolizan a 600 ºC y alimentan al gasificador a 2.000 ºC. El gas de síntesis obtenido, una
vez limpio, se quema en una turbina de gas para producir 300 kw de electricidad. Está
prevista la puesta en marcha en Alemania de una planta de 20 t/h.
2.1.2.4. Hidrogenación
22
Introducción
pueden emplear como depresores del punto de congelación o para mejorar el índice de
viscosidad de aceites lubricantes. Así, el proceso Kurata (Dawans, F. 1994),
desarrollado a escala piloto, y basado en el craqueo catalítico en presencia de un
catalizador polimetálico, permite tratar mezclas de polímeros con contenidos en PVC de
hasta un 20%, originado como producto principal un aceite hidrocarbonado con menos
de 100 ppm de cloro. La reacción tiene lugar a baja temperatura (200 - 250 ºC), presión
atmosférica y en ausencia de oxígeno para evitar la formación de dioxinas.
Los plásticos usados pueden ser aprovechados como combustible por su elevado
poder calorífico; por ejemplo, un kilogramo de polietileno produce la misma energía
que un kilogramo de fuel o de gas natural y mucha más que el carbón (tabla 2.2). Por
ello se hace útil, en los casos en los que no sea viable el reciclado mecánico o químico,
aprovechar este potencial de los residuos plásticos como fuente de electricidad o calor.
Esta alternativa está especialmente indicada para aquellos residuos que presentan
deterioro o suciedad, como es el caso de una parte de los plásticos que proceden de la
agricultura o en determinados casos de residuos sólidos urbanos. En la Figura 2.5 se
muestra de forma esquemática el proceso de recuperación energética.
23
Introducción
Se ha determinado que los residuos plásticos generados por una familia y que
acaban en los vertederos en Europa en un año contienen energía suficiente para calentar
agua para 500 baños o para que un televisor funcione durante 5.000 horas. Un ejemplo
más: un envase de yogur de 0,3 litros contiene la energía necesaria para mantener una
bombilla encendida durante una hora.
24
Introducción
como por ejemplo, el film agrícola y ciertos residuos plásticos del comercio e
industria y recortes industriales.
25
Introducción
A modo de resumen en la Tabla 2.3 se muestra una comparación entre las tres
principales vías de reciclado y se analizan las principales ventajas e inconvenientes que
presenta cada método. En general, el reciclado mecánico es el más extendido debido, a
que en es un proceso sencillo, aunque presenta una serie de inconvenientes como la
necesidad de separación, ya que solo se puede aplicar a un tipo de plásticos a la vez, y
solo a plásticos que no sean termoestables. Además el material resultante es de menor
calidad (deficiencias en color y en propiedades plásticas) lo cual limita la demanda en el
mercado.
26
Introducción
necesidad de depurar los gases que como ya se ha dicho presentan sustancias muy
toxicas a bajas concentraciones, y se generan cenizas.
27
Introducción
Los catalizadores sólidos ácidos, tales como las zeolitas, favorecen las
reacciones de transferencia de hidrógeno debido a la presencia de numerosos centros
ácidos que, junto a la limitaciones que presentan sus tamaños de poro, permite controlar
la calidad de los productos, aportando selectividad en la forma y el tamaño (Pinto y col.,
1999, Onu y col., 1999).
Las zeolitas fueron descritas por primera vez por el minerólogo sueco Cronstedt
(1756), al descubrir un mineral (Estilbita) que perdía agua cuando se calentaba, un
proceso ahora conocido como intumescencia. Él denominó a este mineral zeolite, del
griego zeo (hervir) y lithos (piedra), piedra que hierve. A partir de entonces, las zeolitas
se han considerado como un grupo de minerales especifico compuesto por unas 50
especies (Fleischer y Mandarino, 1991).
28
Introducción
29
Introducción
Las propiedades físicas de las zeolitas las proveen de aspectos únicos para una
variedad amplia de aplicaciones prácticas. Según Breck (1974) las zeolitas se
caracterizan por las siguientes propiedades:
30
Introducción
31
Introducción
Un ejemplo típico del primer tipo son las zeolitas naturales como la mordenita,
la erionita y las zeolitas sintéticas como lo son la A y la X, las cuales son térmicamente
estables hasta 700-800ºC. Durante la deshidratación, las zeolitas del segundo grupo,
32
Introducción
sufren una pérdida reversible de agua a bajas temperaturas, pero si se sigue elevando la
temperatura sufren un mayor cambio estructural que les hace perder su carácter
zeolítico.
B+2L = Constante
33
Introducción
hace que sea posible obtener una gran variedad de propiedades ácidas dentro de una
misma zeolita.
A pesar de todo, los sólidos ácidos no se suelen sintetizar en su forma ácida, sino
que, generalmente, es necesario un tratamiento de intercambio iónico con una sal
amoniacal, seguido de una calcinación que permite eliminar el amoniaco intercambiado,
generándose así los centros ácidos:
NH 4 X + MZ → NH 4 Z + MX ⎯⎯ ⎯→ NH 3 + HZ + MX
500 º C
34
Introducción
- Selectividad en los reactivos: los centros ácidos internos solo son accesible a
unas moléculas de reactivo determinadas, generalmente debido a que el resto de
los reactivos no caben en los poros.
- Selectividad en los productos: se origina por las diferencias en las velocidades
de difusión de las distintas moléculas formadas en el interior de la zeolita.
Aquellas que permanezcan más tiempo en el interior de la zeolita podrán sufrir
reacciones secundarias
- Selectividad en el estado de transición: la obtención de determinados productos
se encuentra obstaculizada porque sus estados de transición no se pueden formar
en el interior de la zeolita por impedimentos estéricos.
- Control del tráfico molecular: El tamaño y la forma de los canales ejerce una
gran influencia en la difusión tanto de los reactivos como de los productos, así
por ejemplo la difusión en la zeolita ZSM-5 es cinco veces más rápida en los
canales rectos que en los sinuosidales.
35
Introducción
36
Introducción
Las zeolitas no son una familia de sólidos cristalinos fácilmente definible. Hoy
en día se conocen cerca de 140 estructuras de zeolitas de las cuales, cerca de 40 son
zeolitas naturales. La nomenclatura de zeolitas es algo confusa puesto que cada
fabricante ha utilizando sus propios nombres y abreviaturas. Para superar este problema
se creó un sistema de código formado por tres letras. Estos códigos se han asignado a
cada tipo de estructura independientemente de su composición química real. Así por
ejemplo, en la Tabla 2.5 se muestra el código de seis familias de zeolitas, junto con la
abreviatura de la que procede el código y el nombre completo que lo originó. A
continuación se describen las principales características de los materiales estudiados en
este trabajo.
37
Introducción
La HZSM-5 es una zeolita con una alta relación Si/Al, donde la sustitución de un
ion silicio (carga 4+) por un ion de aluminio (carga 3+) requiere la presencia adicional
de un protón. Este protón es el que proporciona a la zeolita su alto nivel de acidez. La
zeolita HZSM-5 es un material altamente poroso y presenta dos tipos de poros, ambos
formados por anillos de oxígeno de 10 miembros. El primer tipo de poro es recto y con
la sección transversal elíptica, en el segundo tipo los poros rectos se intersecan
perpendicularmente, dando lugar un patrón en zigzag. Las dimensiones de las aberturas
de los poros para esta zeolita son 5.3 x 5.6 Å en el plano [010] y 5.1 x 5.5 Å en el plano
[100] (véase la Figura 2.7)
38
Introducción
39
Introducción
individuales, que se combinan para dar una estructura cristalina. En la figura 2.9 se
presenta un esquema del proceso de obtención del MCM-41.
Silicato Calcinación
MCM-41
40
Introducción
observó que su estructura era más rica en Si que la HY y que se había aumentado la
acidez del material.
La zeolita Beta es un material rico en silicio, con un tamaño de poro grande que
fue sintetizada por primera vez por Wadlinger y col. en 1967. La estructura de la zeolita
Beta fue descrita por primera vez por Treacy y col. (1988) como un híbrido entre dos
estructuras distintas pero similares, que presentan simetría tetragonal y monoclínica.
Ambos sistemas están constituidos por anillos de 12 átomos de oxígeno, que dan
lugar a canales tridimensionales interconectados, y presentan tres direcciones
cristalográficas; dos morfológicamente idénticas de canales lineales perpendiculares al
plano [00l] que corren en dos direcciones diferentes, a y b, y una tercera dirección
paralela al eje de c, de forma sinusoidal. Los canales sinusoidales presentan aberturas
circulares (5.6 Å × 5.6 Å), y los canales rectos tienen aberturas elípticas. La única
diferencia entre los dos organismos polimorfos está en la dimensión del poro de los
41
Introducción
canales rectos. En el sistema tetragonal, los canales rectos tienen aberturas de 6.0 x 7.3
Å (politipo A), mientras que en el sistema monoclínico tiene una abertura de 6.8 x 7.3 Å
(politipo B) (Corma y col., 1996). En la Figura 2.11 se puede ver la estructura
tridimensional de la zeolita Beta, así como un ejemplo de los poros en el plano [100] y
en el plano [001], y la disposición de los dos politipos A y B.
42
Introducción
• Estándar: HY
• Ultraestable: HUSY
Los polímeros naturales, por ejemplo la lana, la seda, la celulosa, etc., se han
empleado profundamente y han tenido mucha importancia a lo largo de la historia. Sin
embargo, hasta finales del siglo XIX no aparecieron los primeros polímeros sintéticos,
como por ejemplo el celuloide.
43
Introducción
44
Introducción
Figura 2.12. Polimerización del estireno para dar poliestireno; n indica el grado de
polimerización
Por otra parte, los polímeros pueden ser lineales, formados por una única cadena
de monómeros, como el polietileno de alta densidad (HDPE) o bien esta cadena puede
presentar ramificaciones de mayor o menor tamaño, como el polietileno de baja
densidad LDPE (Figura 2.13). También se pueden formar entrecruzamientos
provocados por el enlace entre átomos de distintas cadenas.
45
Introducción
46
Introducción
2.4.1. Clasificación
Existen varias formas posibles de clasificar los polímeros, sin que éstas sean
excluyentes entre sí:
47
Introducción
48
Introducción
49
Introducción
50
Introducción
enlaces C-C en la posición β al centro radicalario (Ahlstrom, 1976; Tsuge y col., 1980).
Esta reacción forma especies olefínicas y fragmentos poliméricos. Además, también se
pueden formar radicales secundarios a partir de la transferencia de hidrógeno
intermolecular entre un radical primario y un fragmento polimérico.
Terminación: esta última fase puede ocurrir a través del modo bimolecular, entre
dos radicales primarios, o por desproporción de radicales primarios.
Unión bimolecular:
• •
∼ CHX − C H + C HX − CH ∼ ⎯⎯→ ∼ CHX − CH − CHX − CH ∼
2 2 2 2
Desproporción:
• •
∼ CH − CHX − C H + C HX − CH − CH ∼ ⎯⎯→
2 2 2 2
∼ C H − CHX − CH + CHX = CH − CH ∼
2 3 2
51
Introducción
Figura 2.15. Fuerza relativa cualitativa de los centros ácidos necesarios en las
reacciones de iones carbenio.
52
Introducción
1. Isomerización de carga
La isomerización de los iones carbenio (iones formados por la adición de un
protón a una olefina o por la eliminación de un ion hidruro de una parafina) ocurre por
transferencia de hidrógeno a lo largo de la cadena hidrocarbonada. Un ejemplo de
reacción de este tipo:
H H
| |
CH − C − CH ←⎯→ CH − C − C H
3 3 3 2
+ | +
H
53
Introducción
3. Transferencia de hidruro
Las reacciones de transferencia de hidruro entre alcanos e iones carbenio son
importantes en las reacciones de craqueo catalítico de hidrocarburos ya que son las
responsables del proceso de reacción en cadena que ocurre una vez que se ha formado el
primer ion carbenio sobre la superficie del catalizador.
R −H + R+ ←⎯→ R + + R −H
1 2 1 2
R+ + R −R ←⎯→ R − R + R+
1 2 3 1 2 3
54
Introducción
55
OBJETIVOS
Objetivos
59
MATERIALES
Y MÉTODOS
63
Materiales y Métodos
64
Materiales y Métodos
65
Materiales y Métodos
en peso, gota a gota, bajo agitación y se deja a la mezcla resultante envejecer durante
una hora, con agitación. En total se agregan 37 g de disolución amoniacal.
66
Materiales y Métodos
- Difracción de Rayos X
- Microscopía Electrónica de Transmisión
- Microscopía Electrónica de Barrido
- Isotermas de Adsorción de Nitrógeno
- Fluorescencia de Rayos X
- Desorción Térmica Programada de Amoniaco
- Resonancia Magnética Nuclear de Al27 y Si29
67
Materiales y Métodos
68
Materiales y Métodos
69
Materiales y Métodos
70
Materiales y Métodos
71
Materiales y Métodos
El equipo utilizado para realizar las microfotografías fue un JEOL modelo JSM-
840, con una magnificación máxima de 300.000. En la figura 4.3 se puede observar una
imagen obtenida por SEM de la zeolita USY comercial utilizada en este trabajo.
72
Materiales y Métodos
73
Materiales y Métodos
Figura 4.5. Isoterma de N2 a 77 K típica de una zeolita HZSM-5 (García y col, 2003)
74
Materiales y Métodos
(P/P0<0.35). La idea central del método BET consiste en que, conocida la cantidad de
gas adsorbido necesaria para formar una monocapa y el área que ocupa cada una de las
moléculas adsorbidas, es posible estimar el área superficial del sólido. Para estimar la
cantidad de gas adsorbido necesario para la formación de una monocapa se utiliza la
siguiente ecuación:
1 1 C −1⎛ P ⎞
= + ⎜ ⎟ (1)
W (( P0 / P ) − 1) Wm C Wm C ⎜⎝ P0 ⎟⎠
donde C es una constante que está relacionada con la energía de adsorción de la primera
monocapa, Wm es el peso del adsorbato en la monocapa y P/P0 es la presión relativa. De
1
la presentación gráfica de W (( P0 / P ) − 1) frente a P/P0 se puede obtener el valor de
Wm. A partir de este valor se puede calcular el valor de la superficie total mediante la
ecuación:
⎛ W NA ⎞
S t = ⎜ m CS ⎟ (2)
⎝ M ⎠
S= St /w (3)
P − 2γVL
Ln ≥ (4)
P0 RTrc
75
Materiales y Métodos
donde rc es el radio de curvatura del poro, r es el tamaño real del poro, y t(P) es el
espesor de la capa adsorbida en el poro antes de que haya tenido lugar la condensación
capilar (rc = r – t(P) ), T la temperatura de trabajo, R la constante de los gases, VL es el
volumen molecular del líquido y γ su tensión superficial. El método BJH supone la
representación gráfica de la distribución de tamaño de poro frente a dV/dlog(r) estimada
mediante la aplicación de la ecuación de Kelvin para las diferentes presiones.
Vads * 15.47
St = (5)
t
⎛P ⎞
A = RTLn⎜ 0 ⎟ = −ΔG (7)
⎝P⎠
76
Materiales y Métodos
⎡ ⎛ A ⎞
2
⎤
W = W0 exp ⎢ − ⎜⎜ ⎟⎟ ⎥ (8)
⎢⎣ ⎝ βE 0 ⎠ ⎥⎦
77
Materiales y Métodos
78
Materiales y Métodos
Desgasificación:
- Caudal de 45 mL/min de N2
- Rampa de calentamiento de 20 ºC a 500 ºC a 10 ºC/min
- Isoterma a 500 ºC durante 30 min
- Enfriamiento hasta 100 ºC a una velocidad de 10 ºC/min
Fisidesorción de NH3 :
- Caudal de 45 mL/min de N2
- Desorción: isoterma a 100ºC durante 60 min
79
Materiales y Métodos
100 0,014
99,5 %w 0,012
DTG
0,01
99
0,008
DTG
%w
98,5
0,006
98
0,004
97,5 0,002
97 0
100 200 300 400 500 600
T (ºC)
Figura 4.6. Curva DTG obtenida a partir de la DTP de NH3 para un material ZSM-5
80
Materiales y Métodos
81
Materiales y Métodos
presenta dos picos, resultado de los dos entornos en que puede encontrarse el Al en la
estructura de la zeolita, tetraédrico y octaédrico. En general, el aluminio hexacoordinado
presenta un pico a 0 ppm, mientras que el aluminio tetraédrico aparece a 54 ppm
(Corma y col., 2000).
54.976
-0.476
4.3.1. Polímeros
82
Materiales y Métodos
83
Materiales y Métodos
4.3.2 Catalizadores
Area BET (m2/g) 334 1136 956 341 614 510 268
Area Externa
67 383 126 38 28 183 77
(m2/g)
Volumen de Poro
0.27 1.34 1.00 0.18 0.35 0.17 0.18
(cm3/g)
Relación
24 47 7 22 4.8 25 0.97
SiO2/AlO2
Acidez Total
1.4 0.7 2.1 2.0 2.1 2.1 1.9
(mmol/g)
Acidez débil
0.8 0.7 1.4 1.2 2.1 1.1 1.3
(mmol/g)
Acidez fuerte
0.6 ----- 0.7 0.8 ----- 1.0 0.6
(mmol/g)
T desorcion NH3
165-385 138 155-550 166-466 154 190-370 156-632
(ºC)
A, B, C,
Estudio A A E E E E, F
D, E
A. Estudio de la actividad catalítica de los diferentes catalizadores sintetizados
B. Estudio del efecto de la elevada área externa del MCM-41.
C. Estudio de la influencia del contacto entre polímero/catalizador en la descomposición
de HIPS en presencia de MCM-41
D. Desarrollo de un modelo pseudocinético
E. Estudio de la descomposición de mezclas VGO/PE en termobalanza
F. Estudio de la evolución de los compuestos generados en el proceso de
descomposición de mezclas VGO-PE
84
Materiales y Métodos
85
Materiales y Métodos
86
Materiales y Métodos
87
Materiales y Métodos
88
Materiales y Métodos
ÁreaxFR
mi = xVtotal
Vinyectado
89
Materiales y Métodos
volumen total de la bolsa fue determinado a partir del volumen de agua desplazado por
ese gas en una bureta invertida, despreciandose el error asociado al gas que puede
quedar disuelto en el agua.
2,E+07
5
2,E+07 PE Térmico
8 PE Catalítico
1,E+07
1,E+07
Abundance
1,E+07
3
8,E+06
6,E+06 4 6
7
4,E+06 1
2
2,E+06
0,E+00
0 5 10 15 20 25 30 35 40
t (min)
Figura 4.10. Cromatograma de gases obtenido en la descomposición del polietileno
mediante pirolisis térmica y catalítica.
90
Materiales y Métodos
91
Materiales y Métodos
92
Materiales y Métodos
observadas en presencia de los otros sólidos ácidos con menor tamaño de poro, y que
podría estar relacionada con la presencia de dos tipos de dominios en el copolímero,
dominios de poliestireno, y dominios de polibutadieno.
93
Materiales y Métodos
94
Materiales y Métodos
Como se mencionó anteriormente, hoy en día cada vez cobra más importancia
una posibilidad alternativa de reciclado terciario, que se basa en el hecho de que es
posible disolver algunos polímeros en corrientes de gasóleo de alto vacío (VGO) y usar
las unidades convencionales de FCC de las refinerías para convertirlos en productos que
se encuentren en el rango de la gasolina. Como un estudio inicial, se analizó en una
termobalanza el comportamiento durante la descomposición térmica y catalítica de
diferentes mezclas de VGO/PE, en la que se modificó la proporción del PE.
95
Materiales y Métodos
96
CONCLUSIONES
Conclusiones
99
Conclusiones
100
Conclusiones
101
Conclusiones
102
Conclusiones
103
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112
PUBLICACIONES
Abstract
In this work, three catalysts with different chemical and physical properties were synthesized (one HZSM-5 zeolite and two ordered
mesoporous aluminosilicates—MCM-41a and MCM-41b) and tested for the pyrolysis of four samples of commercial polymers (LDPE, PP, PS and
EVA copolymer), using a thermobalance under nitrogen atmosphere at a heating rate of 10 8C/min. The catalysts were characterized using X-ray
powder diffraction, nitrogen adsorption at 77 K and 27Al and 29Si solid state nuclear magnetic resonance (NMR). The HZSM-5 zeolite showed the
lowest activity in the catalytic pyrolysis of the four polymers. The two mesoporous catalysts, with a greater pore size, were the most active
materials in the catalytic pyrolysis of the polymers, and the MCM-41b sample, with higher acidity, was the most active. The presence of MCM-41
samples during the pyrolysis of the high impact PS sample permits us to distinguish between different decomposition steps which are probably
related to the pyrolysis of PS and polybutadiene domains. This processes separation was not observed in absence of the catalyst. Thus, catalytic
pyrolysis of such samples in the presence of MCM-41 and other catalysts could be a promising technique to characterize this type of polymers.
# 2005 Elsevier B.V. All rights reserved.
Table 1 Table 2
Characteristics of the commercial polymers Results of the characterization of the catalysts synthesized in this work
Material Density Melt index Vicat Tensile Property HZSM-5 MCM-41a MCM-41b
(g/cm3) (g/10 min) point (8C) modulus a
Pore size (nm) 0.51 0.55 2.4 1.7
(Mpa)
d100 (nm)b 3.39 3.25
LDPE 780R 0.923 20 (190/16)a 93 115 a0 (Å) c 3.92 3.77
PP Novolen 0.910 8 (230/2.2) 70 1500 Wall thickness (nm)d 1.52 2.07
1100L BET area (m2/g) e 334 1136 956
PS Polystyrol 1.050 9.5 (200/5) 90 2000 External surface area (m2/g) f 67 383 126
495F-SB Pore volume (cm3/g) g 0.27 1.34 1.00
EVA Escorene 0.950 150 (125/0.3) 64 13 Si/Al ratioh 24 47 7
UL15028CC Acidity (mmol/g)i 1.36 0.60 2.08
a T desorption NH3 (8C)j 165–385 138 155–550
8C/kg.
Aloct/Altetra j 0.12 0.37 0.70
a
BJH (for MCM-41a, MCM-41b).
b
The first peak of the TGA derivate curve (DTG) identifies XDR. pffiffiffi
c
2d100/ 3.
the temperature of desorption from weak acid sites and the d
a0-pore size.
second peak of desorption identifies strong acid sites (see e
N2 adsorption isotherms; BET method.
Fig. 5, as an example). f
N2 adsorption isotherms; t method.
g
N2 adsorption isotherms; measured at P/P0 = 0.995.
h
2.3. Catalyst testing XRF.
i
TPD of NH3.
j
NMR.
The catalytic activity of the three acid solids synthesized in
this work in the catalytic pyrolysis of polymers, was
investigated using thermogravimetric analysis (TGA) as fact has also observed in the bibliography, and according to
described in [17,18]. The equipment employed was a Luan et al. [19], when different MCM-41 samples were
Perkin-Elmer Pyris 1 Thermobalance. The balance and the prepared by the same experimental procedure, but using
oven thermocouple of the equipment were calibrated following different amounts of the aluminium source in order to obtain
the manufacturer’s instructions. Table 1 shows the main materials with different Si/Al content, the (1 0 0) peak was the
characteristics of the four commercial polymers selected for more intensive in all the cases, but the intensity of the other
testing the catalyst activity. peak decrease when the Si/Al ratio decreases, being practically
Pure polymers as well as mixtures of powdered polymers unappreciable when Si/Al = 2.5.
and catalyst of around 4 mg (3.2 mg of the polymer with 0.8 mg The coordination of the Al atoms in the materials was
of the catalyst) were pyrolyzed. The temperature was raised to investigated by 27Al NMR spectroscopy. The 27Al NMR spectra
550 8C with a heating rate of 10 8C/min. During the (Fig. 2) contain two peaks: one at around 54 ppm, correspond-
experiments, nitrogen flowed through the oven at a rate of ing to Al tetrahedrally coordinated, and another near 0 ppm,
57 STP ml/min. For the PS and PS + catalyst systems, the corresponding to octahedral Al species. The relatively low
qualitative composition of the volatile products formed in the intensity of the octahedral Al peak of HZSM-5 (Fig. 2c)
thermobalance furnace were analysed using a Bruker Tensor 27 suggests that only a small part of the Al atoms are released from
FT-IR spectrometer connected to the TGA (TGA/FT-IR) the zeolite framework, so this is a very crystalline material.
through a transfer line heated to 200 8C to prevent condensation
of the decomposition products.
Fig. 2. 27Al NMR spectra of the three catalysts studied in this work: (a) MCM-
41a; (b) MCM-41b and (c) HZSM-5.
Fig. 4. Nitrogen adsorption isotherms at 77 K and pore size distributions of the
three catalysts studied in this work: (a) MCM-41a; (b) MCM-41b and (c)
HZSM-5.
Fig. 3 shows the 29Si NMR spectra obtained for the three the microporous materials. On the other hand, the adsorption
acid solids. As can be seen, peaks at 109 ppm (MCM-41a and isotherms corresponding to HZSM-5, indicate a lower
MCM-41b) and at 115 ppm (HZSM-5) appear. In general, the adsorption capacity. Likewise, the isotherm for the HZSM-5
peaks at around 110 ppm can be assigned to the Si(OAl) units sample does not show any trace of capillary condensation in the
in the amorphous MCM-41 framework, whereas the peaks at mesopores, only a mono-multilayer adsorption or micropore
around 115 ppm can be assigned to the crystallographically filling is observed. These isotherm seem to be of type I in the
orientated Si–O–Si bonds in the crystalline Si(OAl) units. IUPAC classification and are typical for microporous materials.
The nitrogen adsorption isotherms at 77 K for the three The observed evolution of the isotherms is also reflected in
calcined samples of the synthesized acid solids are shown in the main textural properties derived from them: the BET
Fig. 4. The samples MCM-41a and MCM-41b presents a type surface area, the external surface area, and specific pore volume
IV isotherm, according the IUPAC classification, and this is and the average pore size (see Table 2). Thus, the BET surface
typical for a mesoporous material. It possesses a mono- area values dropped from 1136 m2/g (MCM-41a) to 334 m2/g
multilayer adsorption zone at low relative pressures, a distinct (HZSM-5), the total pore volumes (measured at P/P0 = 0.995)
jump of capillary condensation in mesopores at P/P0 = 0.1–0.4 from 1.34 cm3/g (MCM-41a) to 0.27 cm3/g (HZSM-5). There-
and an almost constant adsorption zone at high relative fore, an increase in the aluminium content of the acid solid in
pressures due to multilayer adsorption on the particle surface. the case of MCM-41, has a strong influence on the textural
Actually, MCM-41b presents a pore size in the range of properties of the material finally obtained. The pore size results
micropores (1.7 nm), but very near to the border between the are especially remarkable, since they indicate a change from
micropores and mesopores ranges (2 nm), and around three mesoporous materials (MCM-41a) to microporous ones
times the corresponding the microporous HZM-5 zeolite. (Dp < 2.0 nm, IUPAC) in the case of the (MCM-41b), despite
Therofore, would not be strange the fact that this material that, as has been above-mentioned, MCM-41b shows the
exhibits a N2 adsorption isotherm closer to the mesoporous than typical behaviour of mesoporous materials. Fig. 4 also shows
the pore size distribution obtained from the corresponding
adsorption isotherm, applying the BJH method.
It is worth to comment that the results showed in Table 2 for
the external surface area of the materials by application of the t-
method would be influenced by the mesoporous nature of the
MCM-41 and, therefore, part of the mesoporous surface would
be accounted as external surface area, allowing values
abnormally high. In spite of this observation, the external
surface areas reported by the t-method have a valuable
comparative value and, on the other hand, this part of the
mesoporous surface would also be a ‘‘very accessible surface’’,
as in the external surface case, as compared to the microporous
area.
According to [20], the ammonia TDP spectra of MCM-41
would present at least three different peaks: at low-, medium-
Fig. 3. 29Si NMR spectra of the three catalysts studied in this work: (a) MCM- and high-temperature (around 217, 280–4501 and 600 8C,
41a; (b) MCM-41b and (c) HZSM-5. respectively), which are attributed to weak Brönsted and Lewis
226 A. Marcilla et al. / Applied Catalysis A: General 301 (2006) 222–231
Table 3
Difference between temperature of maximum speed of decomposition observed
in thermal and catalytic process, for different systems polymer + catalyst
Polymer DTHZSM-5 DTMCM-41a DTMCM-41b
LDPE 85 96 116
PP 61 109 122
PS 0 13 12
EVA 18 30 64
Fig. 8. (a) TGA and (b) DTG curves obtained in the thermal pyrolysis of PS and in the catalytic pyrolysis in the presence of the different catalysts. (c) FT-IR
spectrogram corresponding to the gas generated at the temperature of maximum decomposition rate in the thermal pyrolysis of PS. (d) FT-IR spectrogram
corresponding to the gas generated in the thermal and catalytic pyrolysis of PS in the region between 3200 and 2300 cm1: (A) PS; (B) PS + MCM-41a; (C)
PS + MCM-41b and (D) PS + HZSM-5. (e) FT-IR spectrogram corresponding to the gas generated in the thermal and catalytic pyrolysis of PS in the region between
880 and 600 cm1: (A) PS; (B) PS + MCM-41a; (C) PS + MCM-41b and (D) PS + HZSM-5.
In agreement with [25], the above-mentioned steric sensibly inferior to the values obtained for the LDPE and the
hindrance is high enough to block the access of macro- PP cases, has been observed in the presence of the materials
molecules to the interior of the pores, thus reducing the with greater pore size (Table 2), i.e. those containing
potential catalytic effect of the porous solid. In this work, MCM-41 structures. This fact is, obviously, related to the
only a slight reduction of the temperature of decomposition, possibility of these materials of drastically reduce the steric
A. Marcilla et al. / Applied Catalysis A: General 301 (2006) 222–231 229
hindrances which limits the access of the polymers to the the t-method in the case of the mesoporous MCM-41 samples
inner of pores [26]. would also include some part of the mesoporous surface.
Nevertheless, in spite of the low activity of the catalysts Therefore, the differences in the external surface area are not at
studied, Fig. 8b shows that the presence of the catalyst has a all conclusive. The higher surface (i.e. N2 adsorption capacity,
marked role. Up to three different processes can be observed in see Fig. 4 and Table 2) of the MCM-41a is counteracted by the
the presence of the MCM-41 materials, and the process begins higher acidity of the MCM-41b. According to Fig. 5, the
at lower temperatures than in the thermal pyrolysis. This ammonia TPD peaks reflects that, in addition to the presence of
premature beginning can also be observed in the previous cases the high temperature peak observed for MCM-41b, the two
(LDPE, Fig. 6b and PP, Fig. 7b) and gives rise to a widening of MCM-41 samples contain similar strength acid sites, being
the corresponding DTG curves. It seems, therefore, that the slightly weaker for MCM-41a (in Fig. 5, peaks at 138 and
premature beginning of the decomposition’s reactions may be 150 8C for MCM-41a and MCM-41b, respectively). However,
related to the acid sites located on the surface of the material the acidity of the MCM-41b sample is noticeably higher, thus
[14,24]. In fact, according to [27], the influence of the acid sites revealing the existence of ‘‘higher number of acid sites’’.
located on the external surface and in the pore mouth region of Therefore, the combination of both parameters is required to
zeolites cannot be ignored, although the concentration of these explain the behaviour observed. This type of behaviour has
acid sites is assumed to be smaller, generally 3–5% of the total been previously reported by other authors [25], that observed
acid sites. the highest activities for the pyrolysis of a mixture of PP and PE
It must be observed that the PS sample used in this work for zeolites having a higher proportion of external acid sites.
corresponds to a high impact PS (HIPS), composed by PS In order to assess with more detail the influence of the
domains and polybutadiene (PB) domains. Therefore, the different catalysts in the pyrolysis of PS, the gases generated at
existence of different reaction steps, at around 420 and 450 8C, the temperature of the maximum decomposition rate have been
respectively, in the pyrolysis of HIPS in the presence of MCM- qualitatively analysed using TGA/FT-IR.
41a and MCM-41b reveals that probably these catalysts permit Fig. 8c shows the FT-IR spectrum corresponding to the gas
a distinction between the pyrolysis of PS and PB domains. The generated at the temperature of maximum decomposition rate
main decomposition step (at around 420 8C) can be related to in the thermal pyrolysis of PS. The absorption band at
the PS domains decomposition, whereas the last decomposition 3074 cm1 reveals the presence of a high number of aromatic
step (at around 450 8C) can be related to the decomposition of compounds and the bands at 771 and 695 cm1, corresponding
the PB domains. The small size of the narrow pores of the to the substitution of aromatic rings, indicate the presence of a
HZSM-5 zeolite can be responsible of the almost absence of monosustituted aromatic compound (styrene). On the other
catalytic effect with the voluminous molecules of PS, being, for hand, the band at 3024 cm1 is related to the presence of
the same reason, this material incapable of distinguish between olefins, whereas the bands at 2964–2873 cm1 correspond to
the PB and PS fractions in the HIPS sample studied in this work. the asymmetrical and symmetrical tension of alkanes, being
Considering the hypothesis that the external surface acid these bands those of smaller intensity. According with [25,28],
sites are responsible for the premature start of the decomposi- the products evolved in the pyrolysis of PS include a high
tion process, it is possible to justify the catalytic behaviour of number of aromatic hydrocarbons, as well as different alkanes
the different materials. Thus, MCM-41b is the material that and olefins, being more abundant the aromatic compounds and
allows the degradation to begin at lower temperatures (259 8C). olefins. Moreover, according to Serrano et al. [25], in the
This can be due to the fact that, despite MCM-41a presents area thermal pyrolysis exists a selectivity towards aromatic
noticeably higher than the rest of catalysts (see Table 2), MCM- hydrocarbons, especially towards styrene, whereas in the
41b maintains high values of the external mesoporous surface catalytic pyrolysis a selectivity exists towards benzene.
area together with the highest acidity. The following catalyst, in The comparison among the FT-IR spectra corresponding to
decreasing activity order, is MCM-41a, which displays an the gas evolved in the thermal and catalytic process reveals the
external surface area six times higher than that of the HZSM-5 existence of a noticeable level of similarity, but also some
zeolite (Table 2). Thus, the premature beginning of the process interesting differences. Fig. 8d shows a magnification of the
in the presence of HZSM-5 is noticeably lower as compared 3200–2300 cm1 region of the FT-IR spectra obtained in the
with the other materials. The surface area of HZSM-5 is much thermal pyrolysis of PS and in the pyrolysis in the presence of
lower than that of the other catalysts, its weak acid sites strength the different catalysts. It is possible to observe that the catalytic
is similar to that of the MCM-41 samples, and shows a process, shows, in comparison with the thermal pyrolysis, a
noticeable acidity of strong acid sites (i.e. ammonia TDP peak clear decrease of the bands corresponding to aromatic
at higher temperature in Fig. 5). Therefore, the absence of the compounds (3074 cm1) and olefins (3024 cm1) and an
premature beginning of the process in presence of HZSM-5 increase of the bands of tension of alkanes (2964–2873 cm1).
suggests the relevance of the accessibility of the acid sites for The same tendency can be seen in Fig. 8e, where a
the preliminary steps of the catalytic pyrolysis. magnification of the region of 900–600 cm1 is shown: the
For PP, the broad decomposition region at the initial spectra corresponding to the gas evolved in the catalytic process
decomposition stage has been observed for MCM-41b, but not shows a notable decrease of the bands corresponding to
in the presence of MCM-41a. As has been commented monosustituted aromatic rings (771 and 695 cm1), whereas
previously, the values of the external surface area obtained from the bands of absorption of benzene increase (671 and
230 A. Marcilla et al. / Applied Catalysis A: General 301 (2006) 222–231
653 cm1), being the more intense of the spectrum. Thus, it can of acetic acid, followed by a second step, which involves the
be concluded that, in good agreement to [25], the presence of degradation of the main chain, with little evidence of
the acid solid changes the selectivity of the process toward interaction between the ethylene and VA units.
benzene instead of styrene, but also decrease the olefins yield As Marcilla et al. [30] observed, the temperature of
and increase the alkanes formation. The case of the HZSM-5 maximum weight loss for the first decomposition step
zeolite is worth to emphasizing, that in spite of not modifying undergoes almost no modification, and appears approximately
the temperature of maximum decomposition rate of PS, clearly at the same temperature despite the presence of the catalyst,
modifies the composition of the gases. Thus, as with the rest of whereas the second decomposition step is clearly affected by
the catalysts, notably diminishes the bands of absorption of the presence of acid catalysts. However, the presence of
aromatic and olefins (Fig. 8d) and shows more selectivity catalysts clearly modifies the behaviour of the first process,
towards benzene (Fig. 8e). However, it maintains some that starts earlier and proceeds over a wider temperature
similarity to the thermal process, as in the case of the alkanes range. This behaviour has been already described in [31,32].
formation (Fig. 8d). According to Fig. 9a, the most effective catalysts in this step
are MCM-41b and MCM-41a. As has been described in the
3.2.4. Catalytic pyrolysis of EVA PS case, this premature initiation of the decomposition may
Ethylene vinyl acetate (EVA) copolymers are formed by be related to the presence of the acid sites in the external
structural units from ethylene and vinyl acetate (VA). There- surface of the catalyst.
fore, some steric hindrances, related to the presence of the On the other hand, the second weight loss, corresponding to
acetoxi groups, which appear as substituents of the polymeric the decomposition of PE domains and of the polyene residue
chains, can be expected. Fig. 9a shows the TGA curves obtained after the evolution of VA groups, is affected by the presence of
for the thermal and catalytic pyrolysis of EVA and Fig. 9b each catalyst and a shift to lower temperatures can be observed.
shows the corresponding DTG curves. According to [30], when increasing the vinyl acetate content,
According to [29], the thermal degradation of EVA the polymer becomes less susceptible to the catalytic action of
copolymers shows an initial step, which involves the formation acid solids. The EVA selected for this work contains 27.5% of
VA and, coherently, the catalysts studied exercise an influence
noticeably lower than that obtained for LDPE cracking.
Table 3 shows the differences observed between the
temperatures of maximum decomposition rate in the thermal
and catalytic process. As can be seen, the catalysts with a
greater pore size are the most active (MCM-41b and MCM-
41a), being the MCM-41b, which presents higher acidity, the
most active.
4. Conclusions
According to the previous statements, the activity order [7] C. Vasile, H. Pakdel, B. Mihai, P. Onu, H. Darie, J. Anal. Appl. Pyrol. 57
(2001) 287.
found for the different polymer + catalyst systems is the
[8] G. Manos, A. Garforth, J. Dwyer, J. Ind. Eng. Chem. Res. 39 (2000) 1198.
following: [9] J.S. Beck, J.C. Vartuli, G.J. Kennedy, C.T. Kresge, S.E. Schramm, Chem.
Mater. 6 (1994) 1816.
LDPE, PP, PS, EVA: MCM-41b > MCM-41a > HZSM-5. [10] K.M. Reddy, Ch. Song, Catal. Lett. 36 (1996) 103.
MCM-41: PP > LDPE > EVA > PS. [11] W. Kolodzieski, A. Corma, M.-T. Navarro, J. Pérez, Solid State Nucl.
Al-MCM-41: PP > LDPE > EVA > PS. Reson. 2 (1993) 256.
[12] J. Schirmer, J.S. Kim, E. Klemm, J. Anal. Appl. Pyrol. 60 (2001)
HZSM-5: LDPE > PP > EVA > PS. 205.
[13] A. Gonzalez, L. Hirsuta, M.J. Fernández-Berridi, M. Iriarte, J.J. Iruin,
Finally, the results obtained in this work, demonstrate the Polym. Deg. Stab. 87 (2005) 347.
[14] A. Gartforth, S. Fiddy, Y.-H. Lin, N. Sharratt, J. Dwyer, Thermochim. Acta
effectiveness of use of the catalytic pyrolysis of polymers using
294 (1997) 65.
TGA, not only as a technique for studying this type of [15] IZA, International Zeolite Association, http://www.iza-synthesis.org.
processes, but also as a powerful tool for characterising [16] D.P. Serrano, J. Aguado, J.M. Escola, Micropor. Mesopor. Mater. 34
polymers and catalyst. In this way, it appears as a promising (2000) 43.
procedure for the determination of the polybutadiene (PB) [17] A. Marcilla, M.I. Beltran, F. Hernandez, R. Navarro, Appl. Catal. A Gen.
content in high impact PS samples, which cannot be easily 278–1 (2004) 37.
[18] A. Marcilla, J.C. Garcia-Quesada, S. Sanchez, R. Ruiz, J. Anal. Appl.
know by other analytical techniques. Pyrol. 74 (1–2) (2005) 387.
[19] Z. Luan, C.F. Cheng, W. Zhou, J. Phys. Chem. 99 (1995) 1018.
Acknowledgements [20] H. Kosslick, G. Lischke, B. Parlitz, W. Storek, R. Fricke, Appl. Catal. A
Gen. 184 (1999) 49.
Financial support for this investigation has been provided [21] A. Marcilla, M.I. Beltrán, F. Hernández, R. Navarro, Appl. Catal. A Gen.
278 (2004) 37.
by the Spanish ‘‘Comisión de Investigación Cientı́fica y [22] F. Lónyi, J. Valyon, Thermochim. Acta 373 (2001) 53.
Tecnológica’’ de la Secretarı́a de Estado de Educación, [23] H. Bockhorn, A. Hornung, U. Hornung, J. Anal. Appl. Pyrol. 50 (1999)
Universidades, Investigación y Desarrollo and the European 77.
Community (FEDER refunds) (CICYT PPQ2004-02187) and [24] A. Marcilla, A. Gómez, A. Garcı́a, M. Olaya, J. Anal. Appl. Pyrol. 64
(2002) 85.
by the Generalitat Valenciana (project GRUPOS03/159).
[25] D.P. Serrano, J. Aguado, J.M. Escola, Ind. Eng. Chem. Res. 39 (2000)
1177.
References [26] D.P. Serrano, J. Aguado, J.M. Escola, Appl. Catl. B Environ. 25 (2000)
181.
[1] Association of Plastics Manufacturers in Europe (APME), Summary [27] S. Zheng, Surface Modification of HZSM-5 Zeolites, Tesis Doctoral,
Report, Brussels, 2003. Universität München, 2002.
[2] SOFRES Conseil for APME, Plastics, A Material of Choice for the 21st [28] P. Willians, J. Anal. Appl. Pyrol. 40–41 (1997) 347.
Century, APME, Brussels, 1998. [29] N.S. Allen, M. Edge, M. Rodrigues, C.M. Liauw, E. Fontan, Polym.
[3] R. Bagri, P.T. Williams, J. Anal. Appl. Pyrol. 63 (2002) 29. Degrad. Stab. 71 (2001) 1.
[4] P.D. Osborn, Handbook of Energy Data and Calculations, Butterworths, [30] A. Marcilla, A. Gómez, J.A. Reyes-Labarta, Polymer 42 (2001) 8103.
London, 1985. [31] A. Marcilla, A. Gómez, S. Menargues, Polym. Degrad. Stab. 89 (1) (2001)
[5] K. Obin, D. Koumantaropoulus, G. Manos, Stud. Surf. Sci. Catal. 135 145.
(2001) 4989. [32] A. Marcilla, A. Gómez, S. Menargues, J. Analt. Appl Pyrol. 68–69 (2003)
[6] J. Aguado, D.P. Serrano, J.M. Escola, Polym. Deg. Stab. 69 (2000) 11. 495.
Publicación II: Study of the early deactivation in pyrolysis of polymers in the
presence of catalysts, A. Marcilla, A. Gómez-Siurana and D. Berenguer, Journal of
Analytical and Applied Pyrolysis, Volume 79, Issues 1-2, (2007), Pages 443-449
o Estudio del papel que juega el área superficial externa en materiales con
elevada superficie específica, como el catalizador MCM-41, en la pirólisis de
polímeros. Estudio de la influencia de los procesos de desactivación de los
centros ácidos superficiales durante el proceso de pirólisis.
J. Anal. Appl. Pyrolysis 79 (2007) 443–449
www.elsevier.com/locate/jaap
Abstract
In this work, the early degradation step of the pyrolysis of some polymers in the presence of certain catalysts has been studied using
thermogravimetric analysis (TGA). Three commercial polymers (PE, PP and EVA) and three catalysts were studied (ZSM-5, MCM-41a, and
MCM-41b), and the MCM-41a catalyst has been selected for the analysis of the earlier steps of the pyrolysis process carried out in the presence of
catalysts. Several cycles of heating–cooling were performed using a thermobalance, in order to analyze the influence of the first stages of
decomposition on the activity of the more accessible active sites involved. In this way, the behaviour of the polymer–catalyst mixtures (20% (w/w)
of catalyst) was studied and compared with that observed in the corresponding thermal degradation as well as in the pyrolysis in the presence of
catalysts, in a single heating cycle.
The results obtained clearly show the existence of an early degradation step. For a polymer–catalyst system with low steric hindrances such as
PE-MCM-41, this early degradation step causes a noticeable decrease of the catalyst activity for the main decomposition step (i.e., cracking of the
chain). The decrease of the catalytic activity is lower for a polymer–catalyst system with higher steric restrictions, as occurs in the EVA-MCM-41
degradation process. However, in this case, the catalyst activity in the first decomposition step (i.e., the loss of the acetoxi groups) is noticeable
decreased after one pyrolysis run, thus reflecting that the active sites involved are mainly the most accessible ones.
# 2007 Elsevier B.V. All rights reserved.
0165-2370/$ – see front matter # 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jaap.2007.02.002
444 A. Marcilla et al. / J. Anal. Appl. Pyrolysis 79 (2007) 443–449
deposition [7]. Both coking rate and coke composition depend 2. Experimental
on a variety of parameters such as the characteristics of
the catalyst pore structure, the characteristics of the acid 2.1. Materials
sites, the nature of the reactant and the operating conditions
[8,9]. Table 1 shows the main characteristics of the commercial
The study of the pyrolysis of polymers in the presence of polymers (polyethylene, PE, polypropylene, PP, and an
catalysts using thermogravimetric analysis (TGA) shows a ethylene-vinyl acetate copolymer, EVA) selected in this work.
early degradation step of the process for some polymer–catalyst The nominal vinyl acetate (VA) content of the EVA copolymer
systems. This process causes a widening of the corresponding was 27% (w/w). The catalysts used were ZSM-5, MCM-41a
peaks in the derivative of TGA curves (DTG curves), and in and MCM-41b, prepared in accordance with the method
some cases, the appearance of a shoulder [10]. This early reported in literature [15,16]. The main characteristics of these
degradation step of the decomposition reactions is related to the catalysts are summarized in Table 2. As can be seen, in the case
acid sites located on the surface of the material [11,12]. In fact, of the MCM-41a, the low value of the Si/Al ratio produces a
according to bibliography [13], the influence of the acid sites material with high acidity. This material also presents a high
located on the external surface and in the pore mouth region of pore size and a large surface area, typical of this type of material
zeolites cannot be ignored, although the concentration of these [10].
acid sites is assumed to be smaller, generally 3–5% of the total Pure polymer or copolymer samples as well as the
acid sites. corresponding mixtures with 20% (w/w) catalyst were
As an example, previous works on the pyrolysis of EVA in pyrolysed under the experimental conditions described in the
the presence of catalysts [12,14] showed that, despite the next section.
presence of some catalyst advances noticeably at the beginning
of the pyrolysis of the first step of EVA pyrolysis, the 2.2. Equipment and experimental conditions
corresponding temperature of maximum reaction rate – i.e., the
peak temperature in the DTG curves – remains almost The pyrolysis experiments were carried out in a Netzsch TG
unaltered, thus suggesting a possible simultaneous deactivation 209 thermobalance controlled by a PC under the Windows
of the active sites involved in the early degradation step, and operating system. The atmosphere used was nitrogen with a
consequently the overall process ends at the same temperature flow rate of 45 STPml/min. The balance and the oven
as in the absence of catalyst. thermocouple of the equipment were calibrated following the
In a previous work [10], a comparative study of the manufacturer’s instructions. Pure polymers as well as mixtures
behaviour of different solid acid catalysts in the pyrolysis of of powdered polymers and a catalyst of around 4 mg (3.2 mg of
different polymers was performed. In that work, a possible the polymer with 0.8 mg of the catalyst) were pyrolysed.
influence of some catalysts in the initial degradation steps of In the pyrolysis in the absence of catalyst as well as in the
some polymers was observed. A hypothesis was suggested pyrolysis runs in the presence of catalyst in a single heating
that the active sites located on the external surface of the cycle, the temperature was raised to 550 8C with a heating rate
catalyst or, in the case of mesoporous materials, the more of 10 8C/min. On the other hand, for studying the influence of
easily accessible active sites, would be involved in these the initial decomposition steps in the overall process, four
processes. On the other hand, as previously mentioned, some cycles of heating–cooling were applied to the polymer + ca-
studies about the pyrolysis of EVA over different catalysts talyst system studied. The heating–cooling cycles have been
[12,14] also suggested that these active sites would undergo performed under N2 atmosphere, in the thermobalance
deactivation processes simultaneous with their participation equipment, which is provided with a cooling system, and
in the above-mentioned earlier degradation steps. Therefore, involve a heating rate of 10 8C/min and a cooling rate of 50 8C/
this work is focused on the study of the initial stages of the min. The initial and final temperatures were 50–300 8C for the
pyrolysis in the presence of catalysts of three selected PE mixtures, 50–245 8C for the PP mixtures, and 50–235 8C for
polymers, with the main objective of validating the the EVA mixtures, respectively. In each heating run,
hypothesis previously suggested. In this way, TGA studies temperature was raised to a value below the temperature
were carried out, and four cycles of heating–cooling were corresponding to the apparent beginning of the thermal
performed in order to analyze the influence of the first stages decomposition of each polymer. All the heating–cooling runs
of decomposition on the activity of the active sites involved.
Three polymers (Polyethylene, PE, polypropylene, PP and an Table 1
ethylene–vinyl acetate copolymer, EVA) were selected, and Characteristics of the commercial polymers
three catalysts were studied (ZSM-5, MCM-41a, and MCM- Material Density Melt index Vicat Tensile
41b). Then, MCM-41a was selected to study this phenom- (g/cm3) (g/10 min)a point modulus
enon in more detail. The behaviour of polymer-catalyst (8C) (MPa)
mixtures (20% (w/w) of catalyst) was studied and compared LDPE 780R 0.923 20 (190/16) 93 115
with that observed in the corresponding thermal degradation PP Novolen 1100L 0.910 8 (230/2.2) 70 1500
as well as in the pyrolysis in the presence of catalysts, in a EVA Escorene UL15028CC 0.950 150 (125/0.3) 64 13
a
single heating cycle. 8C/kg.
A. Marcilla et al. / J. Anal. Appl. Pyrolysis 79 (2007) 443–449 445
Table 2
Characteristics of the three catalysts used
Property HZSM-5 MCM-41a MCM-41b
a
Pore size (nm) 0.51 0.55 1.7 2.4
BET area (m2/g) b 334 956 1136
External surface area (m2/g) c 67 126 383
Pore volume (cm3/g) d 0.27 1.00 1.34
Si/Al ratioe 24 7 47
Acidity (mmol/g)f 1.36 2.08 0.60
Acidity weak acid sites f 0.82 1.39 0.60
Acidity strong acid sitef 0.54 0.69 –
Tdesorption NH3 (8C)f weak 165 155 138
acid sites
Tdesorption NH3 (8C)f strong 385 550 –
acid sites Fig. 1. TGA and DTG curves obtained in the pyrolysis of PP in the absence of
Aloct/Altetra g 0.12 0.70 0.37 catalyst and in the pyrolysis in the presence of the different catalysts [10].
a
BJH.
b
N2 adsorption isotherms; BET method.
c
N2 adsorption isotherms; t method. of 1.7 and 2.4 nm, respectively) and the acidity (2.08 and
d
N2 adsorption isotherms; measured at P/P0 = 0.995. 0.60 mmol/g, respectively). The main characteristics of the
e
XRF. HZSM-5 sample were BET area of 334 m2/g, pore size of
f
TPD of NH3. 0.51 nm 0.55 nm and acidity of 1.36 mmol/g [10]. Accord-
g
NMR.
ing to these values, the higher specific surface and pore size of
MCM-41b favours the increase of the activity of this sample,
have been performed under the same experimental conditions but the higher acidity of MCM-41a results in a higher activity,
above described. as can be seen in Fig. 1, and as discussed elsewhere [10]. On the
In order to evaluate the influence of the heating–cooling other hand, the lower specific surface of HZSM-5 leads as a
cycles on the activity of the catalyst, an experiment was consequence to the lower activity of this material in comparison
performed, where the pyrolysis run was stopped when the with the two MCM-41 samples.
fourth cycle was ended and more fresh polymer was added in According to the results of Fig. 1, the tail appearing at
order to once more achieve a 20% (w/w) catalyst mixture; then temperatures below the peak temperature would suggest, for the
the pyrolysis in the presence of catalysts was carried out in the three catalysts, the existence of an initial step, and this is
thermobalance, from 50 to 550 8C at 10 8C/min. specially marked in the presence of MCM-41a. This behaviour
reflects a clear influence of the catalyst characteristics, and
3. Results and discussion suggests that this can be only clearly observed if the catalyst
possesses a certain combination of pore size, specific surface
According to bibliography [17,18], the first step in the and acidity which lead to the existence of a high enough number
pyrolysis of a polymer in the presence of catalysts consists in of very accessible active sites with also high enough acidity.
the cracking of the polymeric chains over the catalyst surface, Fig. 2 shows the TGA and DTG curves obtained in programmed
leading to oligomers, with higher possibilities for access to the thermal desorption of NH3, in the conditions described
active sites located in the inner part of the catalyst pores, where elsewhere [10] for the catalysts reported in Fig. 1. The first
the complete degradation of the oligomers occurs. However, peak – i.e., the peak at lower temperatures – corresponds to the
most articles – referring to [17,19] or not referring to [18,20,21] NH3 desorption from the weak acid sites, whereas the second
this initial step – do not report any noticeable loss of weight
associated to the oligomer formation, and the references are few
where a two-step process is considered [22]. In fact, according
to the results obtained in the present work, the existence of an
initial step involving the formation of volatile compounds
seems to be very dependent on the chemical and structural
characteristics of the polymer and the catalyst.
Fig. 1 shows the TGA and DTG curves obtained for the
pyrolysis of PP in the presence of the two different MCM-41
samples as well all in the presence of HZSM-5 zeolite. The
behaviour of these systems was discussed and compared
elsewhere [10], and here only the relative importance of the
initial decomposition step is emphasised. According to Table 2,
the main differences between the two MCM-41 samples
(MCM-41a and MCM-41b) are related to the respective BET Fig. 2. DTG and TGA curves from NH3 TPD of the three catalysts studied by
area and pore size (BET area 956 and 1136 m2/g and pore size [10].
446 A. Marcilla et al. / J. Anal. Appl. Pyrolysis 79 (2007) 443–449
and the cracking of the polymeric chain resulting from the cases of PE and PP. In other words, the weight loss observed
previous step. These two steps are reflected in the weight loss of before the DTG peak related to the first step of EVA
the TGA curves and in the peaks of the corresponding DTG decomposition is a result of the same chemical reactions in
curves of Fig. 3c. According to bibliography [12], a shift of the both cases. However, this hypothesis does not seem very
second decomposition step towards lower temperatures appears feasible, because it implies that the catalytic cracking of the
as a consequence of the presence of the catalyst, whereas no shift chain could start before the VA groups loss, and this is not
in the temperature peak of the first decomposition step can be supported by experience [14,27,29].
observed (see Table 3). As in the cases of PE and PP, the early (b) The active sites of the catalyst are also involved in the step
beginning also appears in the degradation of EVA in the presence of VA groups loss. Therefore, the catalytic phenomenon
of catalysts. However, in this case, the reaction step affected by observed in this case is somewhat different than those
the early beginning is not the cracking of the chain, but the loss of involved in the cases of PE and PP, not corresponding to the
VA groups. Therefore, it can be concluded that the catalyst also cracking reactions of the main chain, but also involving the
acts in the first step of EVA degradation, provoking a widening of availability of very accessible active sites with enough
the corresponding interval of reaction temperature. Moreover, acidity. According to the bibliography, this seems to be the
the temperature of maximum rate for the first step results almost more probable hypothesis, as shown by the composition of
unchanged, thus suggesting that the active sites involved in the the gas evolved during the first step of EVA pyrolysis (i.e.,
process undergo some deactivation process. Nevertheless, mainly acetic acid). Therefore, the results obtained show
despite this eventual deactivation, related to the participation that the process of loss of the VA group’s loss also
of the catalyst in the VA groups loss, the catalyst maintains undergoes the early degradation step.
enough activity to reduce the temperature of the second
decomposition step, where the polymeric chain is cracked 3.2. Eventual deactivation of the active sites in the early
(see Table 3). Considering the voluminous nature of the VA beginning of the pyrolysis process in the presence of
groups, the hypothesis that the active sites involved are the more catalysts
accessible ones can be suggested.
Therefore, there are two aspects to be studied and assessed: Fig. 4 shows the TGA curves obtained in the heating–
(a) the influence of the external active sites in the early cooling cycles performed for each polymer + catalyst system.
beginning of the decomposition process and (b) the eventual For each polymer, the final temperature of the heating cycles is
deactivation of these active sites. The first question will be different (300 8C for the PE mixture, 245 8C for the PP mixture,
clarified through the comparison among the behaviours of and 235 8C for the EVA mixture), and has been selected below
different polymer + catalyst systems, and applying the meth- the temperature where the pyrolysis in the absence of catalyst
odology described in the previous section for performing starts, in order to ensure that the weight loss observed could
several consecutive heating–cooling cycles. The second only be attributed to the catalyst presence. As can be seen, for
question will be solved considering the behaviour during these the three polymers, the weight loss obtained in the first heating
cycles together with the study of the case where fresh polymer cycle is higher than that obtained in the next cycles. This fact
was added, and then the pyrolysis is continued until 500 8C, in can be explained considering that the active sites involved in
comparison with the pyrolysis runs in the presence of catalyst, this process deactivate quickly, resulting in a material with less
in a single heating cycle. capacity for its catalytic role in the following cycles. In other
words, considering that the existence of deactivation simulta-
3.1. Influence of the external active sites in the early neous to the initial step occurs.
beginning of the decomposition process The analysis of the different heating–cooling cycles shown
in Fig. 4 indicates that the weight loss associated to the initial
The comparison between Fig. 3a and b shows that the initial step starts at lower temperatures in the first cycle than in those
degradation step in the pyrolysis in the presence of catalysts is following. Table 4 shows the temperatures of the starting point
more pronounced for the PP decomposition than in the case of of the weight loss associated to the first and to the following
PE. This fact could be related to the high number of tertiary heating cycles. Despite the fact that the low temperature
carbon atoms in the PP chains, which results in a more reactive observed for the first cycle could be related to the elimination
polymer [10,30]. However, the case of the pyrolysis of EVA in of some adsorbed water on the catalyst, a clear decrease of the
the presence of catalysts, also with high number of tertiary starting temperature for the degradation process can be
carbons, deserves a separate discussion. Unlike PE and PP, observed, thus suggesting that deactivation readily occurs.
whose degradation occurs in a main single step, as mentioned Moreover, the weight loss observed in each cycle is noticeably
above, the EVA pyrolysis involves two steps. Moreover, lower in the case of EVA than in the cases of PE and PP. This
according to bibliography [12], the peak temperature of the first behaviour is in good agreement with the fact that the
step is almost not affected by the presence of the acid solid. degradation step affected by the early degradation step
Therefore, there are two possibilities: involves lower weight loss in the case of EVA, where only
the 27% corresponding to the VA groups is pyrolysed, in
(a) The chemical processes involved in the early degradation contrast to the case of PE and PP, where 100% of polymer may
step of EVA pyrolysis are similar to those occurring in the react.
448 A. Marcilla et al. / J. Anal. Appl. Pyrolysis 79 (2007) 443–449
Fig. 5. TGA and DTG curves corresponding to the pyrolysis in the absence and
in the presence of catalyst experiments performed in different conditions for (a)
PE, (b) PP and (c) EVA.
Fig. 4. TGA curves corresponding to the heating–cooling cycles of (a) Fig. 5 shows the DTG curves corresponding to the following
PE + MCM-41, (b) PP + MCM-41 and (c) EVA + MCM-41. pyrolysis runs: (i) pyrolysis in the presence of catalysts, in a
single heating cycle, (ii) pyrolysis in the presence of catalysts
Table 4 after the four heating–cooling cycles, with addition of fresh
Temperatures corresponding to the starting point of the weight loss in the first polymer, and (iii) pyrolysis in the absence of catalyst, performed
and in the following heating cycles for the different polymers studied as described in Section 2. As can be seen, for the three polymers,
Polymer T (8C) the shoulder appearing before the peak of the DTG curves (the
only peak in the cases of PE and PP and the first peak in the case of
Cycle 1 Cycle 2 Cycle 3 Cycle 4
EVA), which has been related to the early degradation step, is
PE 89 208 217 225 clearly diminished after the heating cycles. This behaviour again
PP 90 174 176 181
indicates that simultaneous deactivation processes occur,
EVA 70 162 167 175
provoking a noticeably loss of the activity of the catalyst after
A. Marcilla et al. / J. Anal. Appl. Pyrolysis 79 (2007) 443–449 449
the heating–cooling cycles, when the fresh polymer is added and resulting in a noticeable effect in the activity of the catalyst
the pyrolysis process is completed. versus the main decomposition step. On the other hand, the role
In the cases of PE and PP, when the pyrolysis in the presence of these active sites, as well as the corresponding deactivation
of catalysts is completed until the complete degradation of the process seems to be increased as the steric hindrances
polymer, the catalyst losses part of its activity after the heating– associated to the polymer structure decreases.
cooling cycles, as compared with the pyrolysis in a single
heating cycle (see the corresponding peak temperatures in Acknowledgements
Table 3), thus corroborating the previous comments. However,
in the case of EVA, the capacity of the catalyst to decrease the Financial support for this investigation has been provided by
temperature of the second decomposition step results almost the Spanish ‘‘Comisión de Investigación Cientı́fica y Tecno-
unmodified by the successive heating–cooling cycles. PE and lógica’’ de la Secretarı́a de Estado de Educación, Universi-
PP could access the most of the active sites, i.e. those located on dades, Investigación y Desarrollo and the European
the external surface, as well as those located at the opening of Community (FEDER refunds) (CICYT CTQ2004-02187),
the pores or mesopores and in the inner parts of the catalyst. and by the Generalitat Valenciana (project ACOMP06/162).
However, before the VA group loss, the EVA chains can only
access the more accessible active sites (simplifying, the References
‘‘external’’ active sites), but leaving unaltered the less
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(2001) 4989.
the main decomposition step.
[2] J. Aguado, D.P. Serrano, J.M. Escola, Polym. Deg. Stab. 69 (2000) 11.
In good agreement with the previous comments, the [3] C. Vasile, H. Pakdel, B. Mihai, P. Onu, H. Darie, J. Anal. Appl. Pyrol. 57
decrease of the activity, or in other words, the importance of (2001) 287.
the deactivation process, is noticeably higher for PE than for PP. [4] V. Ramdas, J.-S. Kim, S.-B. Lee, M.-J. Choi, J. Mol. Catal. A: Chem. 222
As has been previously suggested, this behaviour can be (2004) 133.
[5] J. Weitkamp, Sol. Stat. Ionics 131 (2000) 175.
explained considering that the lower steric hindrances
[6] J.S. Beck, J.C. Vartuli, G.J. Kennedy, C.T. Kresge, S.E. Schramm, Chem.
associated to the PE chains could favour the access to the Mater. 6 (1994) 1816.
polymer chains to less accessible active sites, perhaps some [7] P.D. Hopkins, J.T. Miller, B.L. Meyers, G.J. Ray, R.T. Roginski, M.A.
located in the inner part of pores, thus resulting in an increase of Kuehne, H.H. Kung, Appl. Catal. A: Gen. 136 (1996) 29.
the deactivation of these acid sites. On the other hand, in the [8] M. Guisnet, P. Magnoux, in: E.G. Derouane, F. Lemos, C. Naccache, F.R.
Ribeiro (Eds.), Zeolite Microporous Solids. Synthesis, Structure and
case of EVA the higher steric hindrances associated to the VA
Reactivity, NATO ASI Series, p. 437.
groups make access to the ‘‘less exposed’’ of the more [9] M. Guisnet, P. Magnoux, Stud. Surf. Sci. Catal. 88 (1994) 53.
accessible active sites more difficult, resulting in a lower loss of [10] A. Marcilla, A. Gómez-Siurana, D. Berenguer, Appl. Catal. A: Gen. 301
activity. For the second decomposition step, (which according (2) (2006) 222.
to bibliography [12,14], and in agreement with Figs. 3c and 5c [11] A. Gartforth, S. Fiddy, Y.-H. Lin, P.N. Sharratt, J. Dwyer, Thermochim.
Acta 294 (1997) 65.
and Table 3, proceeds through a catalytic mechanism), these
[12] A. Marcilla, A. Gómez, S. Menargues, J. Garcı́a-Martı́nez, D. Cazorla-
steric effects would be enhanced by the crosslinking Amorós, J. Anal. Appl. Pyrol. 68–69 (2003) 495.
phenomena, suggested by some authors [31], occurring before [13] S. Zheng, Tesis Doctoral, Universität München, 2002.
the second step of EVA decomposition. [14] A. Marcilla, A. Gómez, S. Menargues, Pol. Degr. Stab. 89 (2005) 454.
[15] IZA, International Zeolite Association. http://www.iza-synthesis.org/.
[16] D.P. Serrano, J. Aguado, J.M. Escola, Micropor. Mesopor. Mater. 34
4. Conclusions
(2000) 43.
[17] D.P. Serrano, J. Aguado, J.M. Escola, Ind. Eng. Chem. Res. 39 (2000) 1177.
The pyrolysis of polymers in the presence of catalysts could [18] K. Gobin, G. Manos, Polym. Degrad. Stab. 86 (2004) 225.
involve the existence of an initial degradation step, depending [19] G. Manos, A. Garforth, J. Dwyer, J. Ind. Eng. Chem. Res. 39 (2000) 1198.
on the chemical and structural characteristics of the polymer [20] J. Schirmer, J.S. Kim, E. Klemm, J. Anal. Appl. Pyrol. 60 (2001) 205.
[21] G.J.T. Fernandes, V.J. Fernández, A.S. Arujo, Catal. Today 75 (2002) 233.
and the catalyst. The behaviour observed suggests that this step
[22] J. Aguado, D. Serrano, Spain (1999) 140.
can only be clearly observed if the catalysts possesses a certain [23] A. Marcilla, A. Gómez, A.N. Garcı́a, M.M.J. Olaya, Anal. Appl. Pyrol. 64
combination of pore size, specific surface and acidity which (2002) 85.
leads to the existence of a high enough number of very [24] A. Marcilla, A. Gómez, J.A. Reyes-Labarta, Kinetic Model. Polym. 42
accessible active sites and with a high enough acidity. On the (2001) 8103.
[25] A. Marcilla, A. Gómez, J.A. Reyes-Labarta, A. Giner, Polym. Degrad.
other hand, the relative importance of the early beginning of the
Stab. 80 (2) (2003) 233.
process seems to be increased as the reactivity of the polymer [26] H. Bockhorn, A. Hornung, U. Hornung, J. Anal. Appl. Pyrol. 50 (1999) 77.
chains increase: i.e., when the number of tertiary carbon atoms [27] B.J. McGrattan, Appl. Spectrosc. 48 (12) (1993) 1472.
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catalysts, the active sites of the catalyst seem to be also involved (2005) 224.
[29] A. Marcilla, A. Gómez, S. Menargues, Polym. Degrad. Stab. 89 (1) (2005)
in the VA groups loss process.
145.
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occur simultaneously to the initial step. The more accessible (3) (2005) 456.
active sites, involved in such processes, are quickly deactivated, [31] B.-A. Sultan, E. Sörvik, J. Appl. Polym. Sci. 43 (1991) 1761.
Publicación III: Characterization of high-impact polystyrene by catalytic pyrolysis
over Al-MCM-41: Study of the influence of the contact between polymer and
catalyst, A. Marcilla, A. Gómez-Siurana, J.C. García Quesada and D. Berenguer,
Polymer Degradation and Stability, Volume 92, Issue 10, (2007), Pages 1867-1872
Abstract
In this work, the particular behaviour of a commercial high-impact polystyrene (HIPS) during the catalytic pyrolysis over Al-MCM-41 has
been studied. The results obtained in a thermobalance showed differences in the number and/or the relative importance of the reaction steps
involved in the pyrolysis, depending on the polymer particle size, which can be related to the differences in the nature of the polymeric phase
being decomposed in each stage. Moreover, the relative importance of each step is very dependent on the particle size, revealing differences in
the distribution of the different copolymer domains (i.e., styrene and butadiene domains) when the different particle size samples are mixed with
the catalyst. The type of contact of the pure PS and PB polymers has also been studied revealing that, contrary to other results in literature, the
catalyst may have an important effect both on the PS and PB pyrolysis. The results obtained showed that catalytic pyrolysis of these polymers
could be a powerful tool for providing a fast and simple method for the characterization of copolymers of styrene and butadiene units.
Ó 2007 Elsevier Ltd. All rights reserved.
0141-3910/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymdegradstab.2007.06.016
1868 A. Marcilla et al. / Polymer Degradation and Stability 92 (2007) 1867e1872
study the decomposition of polymers for years. The informa- state nuclear magnetic resonance spectra (NMR), N2 adsorp-
tion provided by this technique has allowed kinetic data to tion isotherms at 77 K, and temperature-programmed desorp-
be obtained, and the effect of the polymer structure, composi- tion (TPD) of ammonia, using the equipment and
tion and operating variables on the pyrolysis process to be experimental conditions described elsewhere [7]. Table 2
studied [7e9]. In a previous work [7], the pyrolysis of HIPS shows the physicochemical and structural characteristics of
in the presence of Al-MCM-41 showed an unexpected behav- Al-MCM-41.
iour, with three different decomposition steps. In this work, the
influence of the polymer particle size and the effectiveness of
the intimate contact between the polymer and the catalyst is
2.2. Experimental equipment
demonstrated.
Some authors study the catalytic pyrolysis process focusing
Thermogravimetric runs were performed in a Netzsch TG
on the influence of the nature of the contact of the catalyst and
209 thermobalance. The sample temperature was measured
the polymer, however, this factor has not been extensively
with a thermocouple directly at the crucible, i.e., very close
studied [10,11]. Due to the bulky nature of the polymer mol-
to the sample. A temperature calibration procedure was
ecules, a determinant factor in the catalytic pyrolysis is the
performed, in accordance with the equipment recommenda-
type of catalystepolymer contact. The dispersion phenomena
tions, and the different samples were pyrolyzed through exper-
in the catalystepolymer mixtures could lead to mass transfer
iments in dynamic conditions carried out from 30 to 550 C at
limitations that are characteristic of the heterogeneous cataly-
10 C min1 under a nitrogen flow of 30 ml min1 (STP).
sis. In this way, a procedure to ensure that the catalyst is
Samples of around 4 mg were pyrolyzed in the TGA equip-
uniformly dispersed and that therefore a good contact exists
ment. For the catalystepolymer mixtures, the polymer was
between the polymer and the catalyst, consists in mixing
thoroughly mixed with around 20% of powdered Al-MCM-
solutions of the polymer in an adequate solvent with the solid
41 (i.e., 3.2 mg of the polymer with 0.8 mg of the catalyst).
catalyst, and after evaporating the solvent, to obtain very
In order to analyse the influence of the particle size in the
homogeneous solid mixtures with a very effective contact
thermal and catalytic pyrolysis, a HIPS sample was powdered
between both solids.
using a IKA M20 grinder. Liquid nitrogen was used to cool the
In order to assess the nature of the phases being decom-
material, facilitating its grinding and avoiding the thermal deg-
posed in each degradation step of a HIPS copolymer, in this
radation of the polymer. Size fractions in the range of 0.6e0.5,
work, dynamic pyrolysis runs of mixtures of Al-MCM-41
0.5e0.4, 0.4e0.3, 0.3e0.2 mm and less than 0.2 mm were
and different polymers and copolymers involving styrene
collected.
and butadiene as monomers have been performed in a TGA
For the study of the influence of the contact between the
equipment. The results obtained permitted the nature of the
catalyst and the polymer, different samples were prepared dis-
processes involved in each step of decomposition to be better
solving the pure polymer (PS or PB) in xylene. Afterwards, the
known, and suggest the possibility of using TGA as a fast tool
catalyst was added and mixed with this solution, and finally
in order to characterize different styreneebutadiene copoly-
the solvent was eliminated by evaporation.
mers, such as HIPS.
Table 2
2. Experimental Characteristics of AleMCM-41
Property MCM-41
2.1. Materials Pore size (nm)a 1.7
d100 (nm)b 3.25
Three commercial polymers were selected: High-Impact a0 (Å)c 3.77
Polystyrene 473 D and crystal Polystyrene 143E, both sup- Wall thickness (nm)d 2.07
plied by BASF, and Polybutadiene 830 JSRRB supplied by BET area (m2/g)e 956
External surface area (m2/g)f 126
Dynasol. The corresponding characteristics, as provided by Pore volume (cm3/g)g 1.00
the supplier, are shown in Table 1. Si/Al ratioh 7
Al-MCM-41 was prepared according to a method reported Acidity (mmol/g)i 2.08
in the literature [12], and was characterized by X-ray diffrac- T desorption NH3 ( C)j 155e550
tion (XRD), X-ray fluorescence (XRF), 27Al and 29Si solid Aloct/Altetraj 0.70
a
BJH.
b
XDR. pffiffiffi
Table 1 c
a0 ¼ 2d100 = 3.
Characteristics of the commercial polymers d
a0 e pore size.
e
Material Density Melt index Tensile modulus N2 adsorption isotherms: BET method.
f
(g/cm3) (g/10 min) (MPa) N2 adsorption isotherms: t method.
g
N2 adsorption isotherms: measured at P/P0 ¼ 0.995.
HIPS Polystyrol 473D 1.05 12 1700 h
XRF.
PS Crystal Polystyrol 143E 1.043 10 3300 i
TPD of NH3.
PB Polybutadiene JSR 830RB 0.909 3 7.8 j
NMR.
A. Marcilla et al. / Polymer Degradation and Stability 92 (2007) 1867e1872 1869
3. Result and discussion low activity of the zeolites and related materials in the pyrol-
ysis of PS [13,14]. Surprisingly, a very different behaviour was
Fig. 1 shows the normalized weight loss curves (NTGA observed when the polymer was powdered, and the single peak
curves), as well as the corresponding derivative curves observed in the DNTG curve for the Al-MCM-41 catalytic
(DNTG curves) for the thermal and Al-MCM-41 catalytic pyrolysis of the commercial HIPS form turns into a three-
pyrolysis of HIPS, as provided by the supplier, and for the peak curve (i.e., a three-step process), with different relative
Al-MCM-41 catalytic pyrolysis of the different size fractions importance depending on the size of the HIPS particles. Con-
obtained after being powdered and sieved. The NTGA curves sidering, as an example, the DNTG curve corresponding to the
show the representation of (w wc)/(w0 wc) versus the tem- catalytic pyrolysis of the 0.6e0.5 mm fraction of HIPS
perature, where w ¼ weight of sample at time t, w0 ¼ weight of (Fig. 1b), a main peak at a temperature slightly lower than
sample at t ¼ 0, and wc ¼ weight of catalyst, obtained in the that corresponding to the commercial sample, a wide tail at
thermobalance as the weight of the residue at the final temper- lower temperatures, and a marked shoulder at a higher temper-
ature. All the NTGA curves corresponding to the thermal ature can be observed. In a previous work [7], the comparison
pyrolysis of the different size fractions are completely coinci- of the respective peak temperatures with those corresponding
dent, and also coincide with that obtained for the material in to the decomposition of the pure polymers [15,16] suggested
pellets, as provided by the supplier. Therefore, only one case the possibility that the main peak is related to the PS domain
(the pelletised material) is shown. However, in the presence decomposition, whereas the shoulder is related to the decom-
of Al-MCM-41 as a catalyst, important differences can be position of the PB domain. With respect to the series of HIPS
observed. samples pyrolyzed, it can be observed that the small peak (or
The comparison between the NTGA and DNTG curves shoulder) at high temperatures shifts to lower temperatures as
corresponding to the thermal and catalytic pyrolysis of the the particle size decreases, and its relative intensity decreases.
non-powdered sample, i.e., in its pelletised commercial The second peaks (i.e. the intermediate temperature peaks)
form, shows curves almost coincident, thus suggesting that clearly show an evolution similar to that described for the
there is almost no effect of the catalyst on the pyrolysis small peak at the higher temperatures. The peak at the lowest
process. This behaviour is in good agreement with the bibliog- temperature appears at the same temperature, regardless of the
raphy, where the steric hindrances related to the voluminous particle size, but its intensity increases with decreasing particle
phenyl groups of PS are considered as the reason for the size.
In order to obtain more insight into the observed behaviour,
different experiments were run with pure PS and pure PB, as
(a) 1 well as with samples of both polymers varying the type of cat-
0,9 alyst/polymer contact.
0,8 Fig. 2 shows the NTGA and DNTG curves corresponding
0,7 to the thermal and Al-MCM-41 catalytic pyrolysis of a pure
(w-wc)/(w0-wc)
Thermal HIPS
liography [13,14] that there is not any influence of the catalyst
0,01
in the PS pyrolysis. However, as Fig. 2b reflects, when using
a catalyst such as that studied in this work, the shape of the
0,005 DNTG peaks for both processes are quite different: the curve
corresponding to the catalytic process shows a shoulder at low
0 temperatures and occurs in a wider temperature interval,
200 250 300 350 400 450 500
whereas the curve corresponding to the thermal pyrolysis is
T (ºC)
very symmetrical and occurs in a narrow interval of tempera-
Fig. 1. (a) NTGA curves and (b) DNTG curves obtained in the thermal and ture. These differences indicate that, despite the fact that the
Al-MCM-41 catalytic pyrolysis of the different size fractions of HIPS. peak temperatures are very similar the catalyst plays a certain
1870 A. Marcilla et al. / Polymer Degradation and Stability 92 (2007) 1867e1872
0,015
whereas the rest of the polymer decomposes in a thermal
0,01
way, at higher temperatures. This behaviour can be explained
considering that, when the catalyst surface is covered with the
0,005 polymer, under certain conditions where very effective contact
degree is possible, the more accessible catalytic active sites
0
50 150 250 350 450 550 could permit the catalytic effect on a certain part of the poly-
T (ºC) mer. However, the fraction of polymer which is not in direct
contact with the catalyst evolves through a thermal pathway.
Fig. 2. (a) NTGA curves and (b) DNTG curves corresponding to the thermal
and Al-MCM-41 catalytic pyrolysis of a pure PS sample. The two catalytic
runs correspond to a PSeAleMCM-41 physical mixture and a PSeAle (a) 1
MCM-41 mixture prepared from a PSexylene solution. 0,9
0,8
0,7
(w-wc)/(w0-wc)
polymer and the catalyst is allowed, and if the catalyst struc- T (ºC)
tural characteristics are appropriate, the catalyst has a marked (b) 0,05
effect on the pyrolysis of PS, despite the steric hindrances re- 0,045 Thermal PB
Catalytic PB in Pellets
lated to the phenyl groups. In this case, the relatively high pore 0,04 Catalytic PB in Xylene
size and BET area of Al-MCM-41 guarantees good possibili- 0,035
ties for its acting as a catalyst, and the sample preparation pro- 0,03
cedure permits the excellent contact between the polymer and
DNTG
0,025
the catalyst. 0,02
Therefore, in accordance with the previous comments, the 0,015
comparison among the curves shown in Figs. 1 and 2 suggests 0,01
that the first DNTG peak corresponding to the catalytic pyrol- 0,005
ysis of the powdered HIPS samples could correspond to the 0
catalytic pyrolysis of the PS fraction. This peak approaches 50 150 250 350 450 550
the thermal pyrolysis peak as the particle size of the sample T (ºC)
increases, becoming the limiting case of the pelletised sample,
Fig. 3. (a) NTGA curves and (b) DNTG curves corresponding to the thermal
which shows a single peak, almost coincident with the thermal and Al-MCM-41 catalytic pyrolysis of a pure PB sample. The two catalytic
peak. Thus it seems that, as the particle size decreases, the runs correspond to a PB-MCM-41 physical mixture and a PBeAleMCM-41
quality of the polymerecatalyst contact increases, and mixture prepared from a PBexylene solution.
A. Marcilla et al. / Polymer Degradation and Stability 92 (2007) 1867e1872 1871
Nevertheless, another explanation for this behaviour could be But, to ascribe the intermediate peak other considerations
the catalyst deactivation. PB pyrolysis yields high amount of must be taken into account. The flow properties of the two
coke [17,18], that may block the access to the rest of the poly- polymers and their behaviour in the grinding process have
mer to the active sites of the MCM-41. an important role in the pyrolysis behaviour of the different
The thermal and catalytic pyrolysis of a mixture containing particle size samples. PS is a brittle thermoplastic polymer
90% of pure PS and 10% of pure PB (w/w), prepared from with a relative high facility of flow (see Table 1) as compared
a solution of both polymers in xylene has been performed, to the elastomer PB. During the grinding it is likely that the PS
and compared to the thermal decomposition of a physical mix- (easier to grind) concentrates in the smaller particle size frac-
ture of both polymers. The corresponding NTGA and DNTG tions, whereas the PB domains (combined with PS) are likely
curves are shown in Fig. 4. As can be seen, the thermal pyrol- to remain in the larger particles (i.e. those more resistant to the
ysis of the pellet mixture shows two decomposition stages, grinding). The small PS and HIPS and PB particles may inter-
corresponding to the independent decomposition of each poly- act more intensely with the catalyst as their particle size is re-
mer, but the thermal pyrolysis of the sample prepared from the duced. Accordingly, the behaviour of the HIPS samples as
xylene solution shows a single peak with a shoulder at high a function of the particle size is now clearer. The observed in-
temperatures, corresponding to overlapping of the simulta- crease of the intensity of the first peak agrees with the increas-
neous degradation of both fractions. The DNTG curve corre- ing amount of PS in the small particle size fractions. The
sponding to the catalytic decomposition of the PSePB second decomposition step can be related to the catalytic py-
mixture prepared in xylene shows the presence of two peaks, rolysis of the PS fraction of the HIPS particles, despite the
clearly separated, at temperatures of 340 and 445 C, which fact that part of the PB fraction of these particles can also de-
can be related to the above-mentioned catalytic pyrolysis of compose through this step. Therefore, the shift of the second
the PS fraction (with eventually some contribution of the peak to lower temperatures and the decrease in its intensity
part of the PB) and the rest of the PB fraction, respectively. is consistent with its higher content of PS (although it also
From these results, it is clear that the first peak observed in contains some PB), and the flow properties of this fraction still
the curves of Fig. 1 can be ascribed to the catalytic pyrolysis containing PB (consequently flowing with higher difficulty
of the PS present in the HIPS, and the third peak to the PB. than the PS fraction). This fraction decreases as the particle
size decreases. Finally the third peak corresponds to the PB
domains, and is more apparent in the larger particles, as a con-
(a) 1
sequence of the above-mentioned processes.
0,9
0,8
4. Conclusions
0,7
(w-wc)/(w0-wc)
0,6
The results obtained in this work have proved that when the
0,5
polymer/catalyst contact is good enough the MCM-41 has an
0,4
important effect on the decomposition of both PS and PB. An
0,3
assignment of the different processes involved in the Al-
0,2 Thermal PSPB in Xylene
Thermal PSPB in Pellets MCM-41 catalytic pyrolysis of a powered HIPS sample to
0,1
Catalytic PSPB in Xylene the different decomposition steps observed by TGA has been
0
50 150 250 350 450 550 suggested. The first decomposition step seems to be related
T (ºC) to the cracking of PS particles segregated from the HIPS dur-
ing the grinding. The second step is the main decomposition
(b) 0,025
Thermal PSPB in Xylene and seems to be related to the catalytic pyrolysis of the PS
Thermal PSPB in Pellets fraction and part of the PB of the HIPS particles. Finally,
0,02 Catalytic PSPB in Xylene
the third decomposition step seems to be associated with the
pyrolysis of the fraction not yet decomposed, and correspond-
0,015
DNTG
Acknowledgement
0
50 150 250 350 450 550
T (ºC) Financial support for this investigation has been provided
by the Spanish ‘‘Comisión de Investigación Cientı́fica y Tec-
Fig. 4. (a) NTGA curves and (b) DNTG curves corresponding to the thermal
nológica’’ de la Secretarı́a de Estado de Educación, Universi-
and Al-MCM-41 catalytic pyrolysis of a mixture of pure PS and PB. Two ther-
mal runs are shown: for the physical PS and PB mixture and for the mixture dades, Investigación y Desarrollo and the European
prepared from the corresponding solutions in xylene. The catalytic run corre- Community (FEDER refunds) (CICYT PPQ2004-02187) and
sponds to the mixture prepared from the respective solutions. by the Generalitat Valenciana (project GRUPOS03/159).
1872 A. Marcilla et al. / Polymer Degradation and Stability 92 (2007) 1867e1872
A R T I C L E I N F O A B S T R A C T
Article history: In this work, the Al-MCM-41 catalytic pyrolysis of styrene–butadiene copolymers in a thermobalance has
Received 5 May 2008 been studied. The behaviour of such copolymers and the corresponding to high impact polystyrene
Accepted 18 August 2008 (HIPS), physical blend of PS and PB with a given grafting degree, has been compared, and the importance
Available online xxx
of the degree of contact between the catalyst and the different polymer domains has been pointed out.
Different particle size copolymer particles have been mixed with the catalyst, and in addition, samples
Keywords:
have been prepared by solving the copolymer and mixing it with the catalyst, thus assuring an intimate
Catalytic pyrolysis
contact. Different decomposition steps which can be related to the degradation of the different domains
Al-MCM-41
Styrene–butadiene copolymers
of the copolymer (polystyrene (PS) and polybutadiene (PB)) have been observed, despite the
Characterization decomposition processes of the PB and PS domains are not completely independent, showing certain
TGA interaction. The importance of to carefully controlling, defining and characterizing the experimental
conditions of catalytic pyrolysis of PS–PB experiments in order to generalize or to extend the results
obtained in such experiments is clearly demonstrated, and pseudokinetic models capable of reproducing
the amount of material evolving trough each decomposition step have been suggested. The possibility of
combining the two criteria: (1) the assignment of each decomposition step and (2) the application of a
pseudokinetic model is suggested as a potential tool for the characterization of the composition of
commercial copolymers or mixtures of PB and PS, once the adequate calibration runs have been
performed.
ß 2008 Elsevier B.V. All rights reserved.
0165-2370/$ – see front matter ß 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jaap.2008.08.010
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network to be formed and thus provide the reinforced properties copolymer with 30% of styrene content, most of this forming a
typical of chemically cross-linked rubbers. These types of products polystyrene block which gives the polymer a thermoplastic
are widely used in adhesive applications and as compatiblizers. behaviour. It develops properties of vulcanised rubber yet does
Different catalysts can be used in the pyrolysis of polymers and not require vulcanisation.
may cause an important reduction in the decomposition tempera- Al-MCM-41 was selected as a catalyst for the pyrolysis process,
ture thus yielding more valuable gaseous products [6]. The most and was prepared according to the method reported in the
habitual catalysts employed in polymer catalytic pyrolysis are literature [11], and characterized by X-ray diffraction (XRD), X-ray
zeolites and aluminosilicates as MCM-41 due to their specific size fluorescence (XRF), 27Al and 29Si solid state nuclear magnetic
porous structure and their acidity. On the other hand, thermogravi- resonance spectra (NMR), N2 adsorption isotherms at 77 K, and
metric analysis (TGA) has been extensively used to study the temperature-programmed desorption (TPD) of ammonia, using the
decomposition processes of polymers for years. The information equipment and experimental conditions described elsewhere [7].
provided by this technique has allowed kinetic data to be obtained, Table 2 shows the physicochemical and structural characteristics
and the effect of the polymer structure, composition and operating of Al-MCM-41.
variables on the pyrolysis process to be studied [7–9].
In a previous work [10] the catalytic pyrolysis of HIPS was 2.2. Experimental equipment
studied. In that work, a peculiar behaviour was observed when the
polymer was pyrolized in the presence of Al-MCM-41, showing the Thermogravimetric runs were performed in a Netzsch TG 209
existence of a three-step process, each one with different relative thermobalance swept with nitrogen with a flow rate of
importance depending on the size of the HIPS particles. An 30 ml min1 (STP). The sample temperature was measured with
assignment of the different reaction steps involved in the process a thermocouple directly at the crucible, i.e., very close to the
was suggested, and the first decomposition step was related to the sample. A calibration procedure was performed each day using
cracking of PS particles segregated from the HIPS during the internal standards (aluminium, nickel and perkalloy). Experiments
grinding of the samples. The second step is the main decomposi- in dynamic conditions were carried out from 30 to 550 8C at
tion step and seems to be related to the catalytic pyrolysis of the PS 10 8C min1. In the catalytic experiments, HIPS was mixed with
fraction and perhaps of some part of the PB of the HIPS particles. powdered Al-MCM-41, and samples of around 4 mg (3.2 mg of the
Finally, the third decomposition step could be associated with the polymer with 0.8 mg of the catalyst) were pyrolized.
pyrolysis of the fraction not yet decomposed, corresponding to the It is important to take in consideration the fact that, despite the
remaining undecomposed PB fraction, which would correspond overall shape of the TGA and DTG curves will be similar, certain
with the major part of the initial PB fraction. shift is expected towards higher temperatures when the catalyst is
In this work, dynamic pyrolysis runs of mixtures of Al-MCM-41 reused (and therefore partially deactivated), and towards lower
and different polymers and copolymers involving PS and PB have temperatures when the catalyst amount increases. Moreover,
been performed in TGA equipment. The main objective of the some details of the TGA curves may be modified as the catalysts are
present paper has been focused on the comparison between the deactivated [12], and a saturating effect could appear up to high
HIPS behaviour, which has been extensively studied elsewhere loads of catalysts [13]. Therefore, the experimental conditions
[10], and the SBS copolymers behaviour. The great effect of the must be carefully controlled in order to ensure the reproducibility
catalyst/copolymer contact degree has been studied, and the of the results.
importance of the methodology for the preparation of the catalyst-
copolymer mixture used as sample in the TGA run has been 3. Result and discussion
demonstrated.
3.1. Analysis of the HIPS behaviour
2. Experimental
Fig. 1 shows the normalized weight loss curves (NTGA curves)
2.1. Materials obtained in the thermobalance and the corresponding derivative
curves (DNTG curves) for the thermal and catalytic pyrolysis of
Three commercial polymers were selected: High-Impact HIPS, as provided by the supplier, and for the catalytic pyrolysis of
Polystyrene 473 D (HIPS) supplied by Basf and two SBSs, Calprene the different size fractions obtained after powdering and sieving
416 and Calprene 487, supplied by Dynasol. The corresponding
characteristics, as provided by the supplier, are shown in Table 1. Table 2
Characteristics of the catalyst used
Calprene1 487 is a thermoplastic copolymer butadiene/styrene
(45/55), polymerized in solution. It has a radial structure and is Property Al-MCM-41
extended with 40 phr (parts per hundred parts of resin) of Pore size (nm)a 1.7
paraffinic oil. This product is presented in pellet form and has very BET area (m2/g)b 956
adequate flow properties for compounding articles intended for External surface area (m2/g)c 126
injection. Calprene1 416 is a radial styrene–butadiene block Pore volume (cm3/g)d 1.00
Si/Al ratioe 7
Acidity (mmol/g)f 2.08
Table 1 Acidity weak acid sitesf 1.39
Characteristics of the commercial polymers Acidity strong acid sitef 0.69
Tdesorption NH3 (8C) acid sitesf 155–550
Material Density Melt index Tensile modulus Aloct/Altetrag 0.70
(g/cm3) (g/10 min) (MPa) a
BJH.
b
HIPS Polystyrol 473D 1.05 12 1700 N2 adsorption isotherms; BET method.
c
SBS Calprene 416 0.94 0.5a 2.7 N2 adsorption isotherms; t method.
d
SBS Calprene 487 0.96 14b N2 adsorption isotherms; measured at P/P0 = 0.995.
e
XRF.
a f
At 200 8C. TPD of NH3.
b g
At 190 8C. NMR.
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K C2
P !a2 GC2 þ ð1 a2 ÞPC2
(R-2)
Fig. 1. (a) NTGA and (b) DNTG curves obtained in the thermal and Al-MCM-41
KT
catalytic pyrolysis of the different size fractions of HIPS. PC2 !G2 (R-3)
where (R-1) and (R-2) represent the first and the second reaction
step respectively, corresponding to two successive processes
the samples. The NTGA curves show the representation of ðw where the catalytic pyrolysis of the PS fraction occurs, and (R-3)
wc Þ=ðw0 wc Þ versus the temperature, where w ¼ weight of represents the third stage, corresponding to the thermal pyrolysis
sample at time t (or temperature T), w0 ¼ weight of sample at
of the PB fraction. PC1
and PC2 are the materials resulting after the
T = 100 8C, when the major part of the water adsorbed in the (R-1) and (R-2) processes, respectively. PC2
represents the
catalyst has been removed, and wc ¼ weight of catalyst, obtained copolymer, once the main part of the PS domains have already
in the thermobalance. wc has been considered as the weight of the reacted. GC1 and GC2 represent the volatile compounds evolved in
residue at the final temperature. In this way, the amount of coke (R-1) and (R-2), respectively, and KC1 and KC2 are the respective
formed over the catalyst at the end of the process has been specific rate constants. a1 and a2 are the stoichometric coefficients
considered as negligible [14]. The DNTG curves correspond to the (in mass units) for the formation of GC1 and GC2 from P and PC2
,
derivate of the NTGA curves. All the TGA curves corresponding to respectively, and can be related to the PS content of HIPS. a1
the thermal pyrolysis of the different size fractions are completely indicates the fraction of P which evolves through (R-1) and a2 is the
coincident, and also coincide with that obtained for the material in fraction of PC1
which evolves through (R-2). G2 represents
pellet form, as provided by the supplier. the volatile compounds evolved in (R-3), and corresponds to the
As can be seen in Fig. 1, a noticeable influence of the HIPS overall mass of PC2, which decomposes without any solid residue
particle size in the Al-MCM-41-catalytic pyrolysis behaviour can formation.
be observed. This influence has been studied in a previous work According to (R-1), (R-2) and (R-3), the following differential
[10], where a detailed analysis of this behaviour was performed equations can be written:
and compared with the behaviour of the pure PS and PB polymers.
As a conclusion, the following assignment of each reaction step dX P
¼ K C1 XPn1 (1)
was proposed: dt
The first step, at around 325 8C, corresponds to the catalytic dX PC1
¼ ð1 a1 ÞK C1 XPn1 K C2 XPC1
n2
(2)
cracking of the lower size particles of PS segregated during the dt
grinding process.
dX PC2 n2 n3
The second step, at temperatures between 350 and 425 8C, would ¼ ð1 a2 ÞK C2 XPC1 K T XPC2 (3)
correspond to the catalytic cracking of larger HIPS particles and dt
may include the PS domains of the grafted chains. where XP, XPC1* and XPC2* represent the mass fraction of P, PC1 and
The third decomposition step (i.e. the shoulder at around 440 8C)
PC2 , respectively, in the mixture being decomposed, expressed in
has been related to the thermal cracking of the rest of material, catalyst-free basis. Therefore, at the initial time, t = 0, XP = 1 and
not decomposed in the previous steps, and mainly corresponds XPC1* = XPC2* = 0, and the evolution with the time of the mass
to the thermal pyrolysis of the PB domains. fraction of the mixture, w, calculated as w ¼ X P þ X PC1 þ X PC2 can
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Fig. 2. Comparison between the experimental and calculated DNTG curves for the
catalytic pyrolysis of the different particle size samples of HIPS.
be calculated once Eqs. (1), (2) and (3) are solved. n1, n2 and n3 are
the reaction orders of (R-1), (R-2) and (R-3), respectively. The
respective rate constants, KC1, KC2 and KT, can be modelled in
accordance with the Arrhenius law:
E
K i ¼ K i0 exp i (4)
RT
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Fig. 4. NTGA and DNTG curves obtained in the Al-MCM-41 catalytic pyrolysis of a
mixture prepared from a xylene-solution of Calprene 487. Fig. 5. Comparison between the experimental and calculated DNTG curves for the
catalytic pyrolysis of the 0.6–0.5 mm particle size fraction of Calprene 487 and for
the sample prepared from a xylene-solution of this copolymer.
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Fig. 8. Comparison between the experimental and calculated DNTG curves for the
catalytic pyrolysis of the 0.6–0.5 mm particle size fraction of Calprene 416 and for
the sample prepared from a xylene-solution of this copolymer.
Table 5
Calculated values for the stoichometric parameters corresponding to the
application of the reaction scheme (R-5) and (R-6) to the 0.6–0.5 mm size fraction
of Calprene 416 and to the sample prepared from the xylene-solution of this
copolymer
Sample a
0.6–0.5 mm 0.164
Fig. 7. NTGA and DNTG curves obtained in the Al-MCM-41 catalytic pyrolysis of a Xylene-solution 0.596
mixture prepared from a xylene-solution of Calprene 416.
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4. Conclusions Acknowledgements
The results obtained in this work clearly indicate the importance Financial support for this investigation has been provided by
of variables as the structure of the copolymer, the flow character- the Spanish ‘‘Comisión de Investigación Cientı́fica y Tecnológica’’
istics and the contact of the different domains with the pore de la Secretarı́a de Estado de Educación, Universidades, Investiga-
structure and the active sites of the catalyst in the particular ción y Desarrollo and the European Community (FEDER refunds)
behaviour of the catalytic pyrolysis of PS–PB copolymers. The coarse (CICYT PPQ2004-02187), Generalitat Valenciana (ACOMP06/162
assignment of the reaction steps carried out suggests that the and ACOMP/2007/094), and University of de Alicante; Grupo de
amount of material decomposed through each decomposition step Procesado y Pirólisis de Polı́meros (VIGROB099).
not only depends on the percentage of each monomer in the
copolymer. The existence of certain interface where the decom-
References
position of both types of domains occurs simultaneously has been
pointed out. In this way, it is very important to control the [1] S.J. Lee, H.G. Jeoung, K.H. Ahn, J. Appl. Polym. Sci. 89 (2003) 3672–3679.
experimental conditions used to carry out the catalytic pyrolysis [2] S.G. Turley, H. Keskkula, Polymer 21 (1980) 466–468.
experiments of such systems in order to ensure the reproducibility of [3] F.M. Peng, J. Appl. Polym. Sci. 40 (1990) 1289–1302.
[4] M. Fisher, G.P. Hellman, Macromolecules 29 (1996) 2498–2509.
the results and to permit to valuable conclusions. [5] L. Rios-Guerrero, H. Keskkula, D.R. Paul, Polymer 41 (2000) 5415–5421.
In the particular case of the SBS copolymers, noticeable [6] D.P. Serrano, J. Aguado, J.M. Escola, E. Garagorri, J.M. Rodrı́guez, L. Morselli, G.
differences in the behaviour have been observed when the Palazzi, R. Orsi, Appl. Catal. 49 (2004) 257–265.
[7] A. Marcilla, A. Gómez-Siurana, D. Berenguer, Appl. Catal. A: Gene. 301 (2) (2006)
polymer and the catalyst were physically mixed as compared to 222–231.
the case when a sample from a suspension of the catalyst in a [8] A. Marcilla, M. Beltrán, J.A. Conesa, Anal. Appl. Pyrol. 58–59 (2001) 117–226.
xylene solution of the polymer is prepared. In fact, in this case, [9] A. Marcilla, A. Gómez, S. Menargues, J. Anal. Appl. Pyrol. 68–69 (2003) 507–526.
[10] A. Marcilla, A. Gómez-Siurana, J.C. Garcı́a Quesada, D. Berenguer, Polym. Degradat.
where the contact degree is improved, the differences among the
Stab. 92 (10) (2007) 1867–1872.
reactions steps are noticeably increased. [11] D.P. Serrano, J. Aguado, J.M. Escola, Micropor. Mesopor. Mater. 34 (2000) 43–54.
Finally, the possibility of exploiting the Al-MCM-41 catalytic [12] A. Marcilla, A. Gómez-Siurana, D. Berenguer, J. Anal. Appl. Pyrol. 7 (1–2) (2007)
pyrolysis of styrene–butadiene copolymers as a procedure for the 443–449.
[13] A. Marcilla, M. Beltran, J.A. Conesa, J. Anal. Appl. Pyrol. 58–59 (2001) 117–126.
approximate determination of the composition of such copolymers [14] A. Marcilla, A. Gómez-Siurana, A.O. Odjo, R. Navarro, D. Berenguer, Polym.
could be considered, but with the aid of adequate standards. Degradat. Stab. 93 (3) (2008) 723–730.
Please cite this article in press as: A. Marcilla, et al., J. Anal. Appl. Pyrol. (2008), doi:10.1016/j.jaap.2008.08.010
Publicación V: Characterization of vacuum gas oil–low density polyethylene
blends by thermogravimetric analysis, A. Marcilla, A. Gómez-Siurana, A.O. Odjo,
R. Navarro and D. Berenguer, Polymer Degradation and Stability, Volume 93, Issue
3, (2008), Pages 723-730
V
Los resultados obtenidos en este estudio permiten cubrir los siguientes
objetivos específicos:
Abstract
The study of the catalytic pyrolysis of mixtures of fuel and polymers is interesting in order to explore the possibility of using commercial
fluid catalytic cracking (FCC) units or similar processes for recycling plastic wastes. In this work, different samples of vacuum gas oil (VGO),
polyethylene (PE) and vacuum gas oilepolyethylene blends (VGOePE) have been studied by thermogravimetric analysis. Vacuum gas oile
polyethylene blends with 1, 2.5, 5, 7.5 and 10% w/w of PE were prepared by continuously stirring for 120 min, at 60 rpm at 120 C, and
afterwards, the effect of different catalysts (HZSM-5, HUSY, HBeta zeolites, FCC catalysts and Al-MCM-41) on the decomposition of these
mixtures was studied. Moreover, the deposition of coke over each catalyst was studied by thermogravimetric analysis in an oxidant atmosphere.
The catalytic pyrolysis behaviour of the VGOePE mixtures indicates a two-step process, the degradation of the VGO and the PE fraction being
almost independent. The degradation or evaporation of the VGO fraction is only slightly affected by the presence of the catalyst, whereas the
PE fraction showed similar behaviour as that already described in the literature for the pure polymer. The results show that the HBeta zeolite is
the most active catalyst for the decomposition of the mixtures, and that the ZSM-5 zeolite is the catalyst with the lowest amount of coke
formation. These results are in very good agreement with the structural characteristics of the different catalysts studied, i.e., with their pore
size and acidity.
Ó 2008 Elsevier Ltd. All rights reserved.
Keywords: Vacuum gas oil (VGO); LDPE; Blends; TGA; Coke; Catalytic pyrolysis
1. Introduction than that of fresh materials [2]. In the secondary recycling, in-
cineration, calorific energy is generated. The calorific value of
Since 1970, the production and consumption of plastics plastics is comparable to that of fuels, around 46 MJ/kg [3],
have increased drastically with an increase of 98.1 kg per cap- but uncontrolled incineration can produce different pollutants
ita consumption of virgin plastics in 2003 [1]. This noticeable which are toxic at very low concentration. Finally, pyrolysis is
increase in the use of these materials has caused an important a tertiary recycling process, where the polymer sample is
environmental problem due to the accumulation of plastics in heated in an inert atmosphere causing the cracking of the poly-
municipal solid waste (MSW). mer backbone to convert these wastes into gas and liquid
Different alternatives are currently beginning to be consid- hydrocarbons [4e6]. Moreover, the addition of catalysts im-
ered for reducing the environmental impact of plastic wastes. proves the thermal process [7] because it permits more valu-
Primary or mechanical recycling consists of grinding the plas- able products to be obtained at lower temperatures and at
tics and producing new goods with the resulting recycled ma- lower reaction time.
terial, however, the quality of the recovered material is lower An alternative approach, of the tertiary recycling, that is re-
ceiving increasingly more attention, is based on the fact that it
is possible to mix olefinic (polyethylene, polypropylene) and
* Corresponding author. Tel.: þ34 96 590 2953; fax: þ34 96 590 3826. styrenic polymers (polystyrene, polystyreneepolybutadiene)
E-mail address: antonio.marcilla@ua.es (A. Marcilla). in the usual feed of the process of catalytic cracking of
0141-3910/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymdegradstab.2007.12.010
724 A. Marcilla et al. / Polymer Degradation and Stability 93 (2008) 723e730
hydrocarbons (FCC) in the refineries, i.e., in the vacuum gas 2. Experimental procedure
oils (VGO), and to turn them into products in the range of gas-
oline [8]. This approach would be feasible in the present units 2.1. Materials
of FCC since it does not involve important changes in the fa-
cilities given its versatility [9]. In this way, Ng [8] studied the A low density polyethylene (LDPE) (200e500 mm particle
conversion of polyethylene (PE) dissolved in a commercial size) supplied by Dow Chemicals, with a density of 0.918 g/
VGO, and observed that for a certain relation of catalyst/ cm3 (ASTM D 792) and melt flow index of 7.7 g/min (ISO
feed it was possible to significantly increase the production 1133) has been used in this work. The vacuum gas oil
of gasoline. (VGO) and the commercial equilibrium FCC catalyst were
Zeolites and mesoporous materials are the most important supplied by Repsol YPF (Spain). The VGO has a boiling range
materials used as catalysts in the pyrolysis of plastics of 240e560 C and a density of 0.920 g/cm3. The physico-
[10e12], due to their porous structure and acid properties chemical and structural characteristics of the equilibrium
[13]. An important application of these materials is in the fluid FCC catalyst are shown in Table 1.
catalytic cracking of hydrocarbons’ process (FCC), that is one A HUSY zeolite and a HZSM-5 zeolite were supplied by
of the key processes in refineries, aimed at the conversion of Grace Davison, and a HBeta zeolite was supplied by Süd-
heavy feedstocks into lighter, more valuable products such Chemie Inc. (HBeta 25). Al-MCM-41 was prepared according
as light olefins, liquefied petroleum gas (LPG), gasoline and to the method reported in literature [22]. All the catalysts were
diesel fuel [14]. characterized by X-ray diffraction (XRD), X-ray fluorescence
The catalyst used in a commercial FCC unit (FCC catalyst) (XRF), N2 adsorption isotherms at 77 K, using the equipment
is a very complex composite, where the main active compo- and experimental conditions described elsewhere [23] and
nent, the zeolite, is deposited on a matrix. Moreover, binders temperature-programmed desorption (TPD) of ammonia. Tem-
and various additives are also present [15]. Matrices are of dif- perature-programmed desorption (TPD) of ammonia was per-
ferent types and they can be classified according to different formed in a Netzsch TG 209 thermobalance. The samples
criteria: the chemical composition, the origin of their compo- were previously outgassed in a N2 flow of 45 ml/min by heat-
nents (synthetic, semi-synthetic or natural), or the catalytic ing to 500 C with a rate of 10 C/min, retaining at this tem-
role they play (inactive, or with low, medium or high activity). perature for 30 min. After cooling to 100 C, the acid sites
Most commercial catalysts have semi-synthetic matrices, were saturated by treatment with an ammonia flow of 35 ml/
consisting of a synthetic compound, usually amorphous silica, min for 30 min. The physisorbed ammonia was removed by
alumina or silica/alumina, and a natural component, usually passing a N2 flow of 45 ml/min for 60 min at 100 C. Finally,
clay [16]. the TPD measurements were carried out by heating the sample
The effects of several zeolites and other catalysts on the de- in the N2 flow at a rate of 10 C/min up to 900 C. The acidity
composition of different polymers have been extensively stud- of the materials was calculated using the weight loss observed
ied using thermogravimetric analysis (TGA) in dynamic in the thermobalance at each TPD stage.
conditions [10,17e19]. Moreover, some authors used TGA
analysis to develop kinetic models for polymer decomposition
and to study the deactivation of the catalysts by coke deposi- Table 1
tion [12,20,21]. As an example, Manos et al. [12] studied the Characteristics of the catalysts studied in this work
catalytic decomposition of three polymers, LLDPE, PP and Property FCC ZSM-5 USY HBeta Al-MCM-41
LDPE, using several catalysts such as USY, HZSM-5, FCC Pore size (nm) a
e 0.51 0.55 0.74 0.66 0.67 1.75
and a clay catalyst in thermobalance equipment. In this study, 0.56 0.56
the authors conclude that the USY catalyst was the most active BET area (m2/g)b 268 341 614 510 956
External surface 77 38 28 183 126
but produced the highest amount of coke, due to its strong
area (m2/g)c
acidity. Pore volume 0.18 0.18 0.35 0.17 1.00
In this work, different samples of vacuum gas oil (VGO), (cm3/g)d
polyethylene (PE) and vacuum gas oilepolyethylene blends Si/Al ratioe 0.97 22 4.8 25 7
(VGOePE) have been characterized using thermogravimetric Acidity/weak 0.13 1.2 2.1 1.1 1.4
acid (mmol/g)f
analysis to study their behaviour in the thermal and catalytic
Acidity/strong 0.06 0.8 0 1.0 0.7
pyrolysis process, and to analyze the possibility of recycling acid (mmol/g)f
plastics by mixing them with the vacuum gas oil in refineries. Total acidity 0.19 2.0 2.1 2.1 2.1
Thus, different catalysts were used, three commercial zeolites, (mmol/g)f
HZSM-5, HBeta and HUSY, a commercial equilibrium FCC T desorption 156e632 166e466 154 190e370 155e550
NH3 ( C)f
catalyst, and a mesoporous material, Al-MCM-41. Moreover,
a
considering that the deposition of coke is one of the principal BJH.
b
N2 adsorption isotherms; BET method.
factors in the deactivation of catalysts, thermogravimetric c
N2 adsorption isotherms; t method.
analysis of the coked zeolites in an oxidant atmosphere was d
N2 adsorption isotherms; measured at P/P0 ¼ 0.995.
performed to estimate the proportion of coke over each e
XRF.
f
catalyst. TPD of NH3.
A. Marcilla et al. / Polymer Degradation and Stability 93 (2008) 723e730 725
The first peak of the TGA derivative curve (DTG) identifies behaviour for decomposition of polymers. Later, a 7:1 ratio
the temperature of desorption from weak acid sites and the of catalyst/sample was used, which is a typical ratio used in
second peak of desorption identifies strong acid sites. Table 1 the refineries in the fluidized catalytic cracking processes.
shows the physicochemical and structural characteristics of the Fig. 1 shows the weight loss curves (TGA) and the deriva-
different catalysts studied in this work. tives of the weight loss curves (DTG) obtained in the thermal
The VGOePE blends were prepared using a Jankel & Kun- decomposition of the different samples of vacuum gas oil,
kel IKAVISC MR-F12 mixer by continuously stirring for polyethylene, and the different blends of vacuum gas oilePE.
120 min, at 60 rpm and at temperatures of 120 C, mixtures Table 2 shows the temperatures of maximum decomposition
of the base components (LDPE and VGO) with different rate corresponding to each reaction step, i.e., the temperatures
weight fractions (1, 2.5, 5, 7.5 and 10%) of the polymer. of each DTG peak. As it is possible to see, the comparison be-
This temperature was selected for the sample preparation be- tween the curves corresponding to VGO, pure PE and their
cause at 120 C the LDPE is completely melted, thus permit- blends show the existence of a single decomposition step in
ting a good mixing degree with the VGO. the cases of VGO and PE, but two decomposition steps in
the case of the blends. As can be seen in Table 2, the temper-
2.2. Experimental equipment ature of the first peak of the blends is very close to that of
the VGO peak, whereas the temperature of the second peak
Thermogravimetric runs were performed in a Netzsch TG of the blends is very close to that of the PE. Therefore, the first
209 thermobalance. The sample temperature was measured stage can be clearly associated with the decomposition of the
with a thermocouple directly at the crucible, i.e., very close vacuum gas oil, although the weight loss associated with
to the sample. A temperature calibration procedure was per- VGO may also be related to the evaporation of the different
formed, in accordance with the equipment recommendations, components of VGO, whereas the second one can be related
and the different samples were pyrolyzed in dynamic condi- to the PE decomposition. Moreover, both stages seem to pro-
tions from 30 to 550 C at 10 C/min under a nitrogen flow ceed independently, despite the fact that some shift towards
of 30 ml/min (STP). Samples of around 4 mg were pyrolyzed higher temperatures of the peak associated to the VGO, when
in the thermogravimetric analysis (TGA) equipment. For the the proportion of PE in the mixture increases, can be observed.
catalysteLDPE, catalysteVGO and catalysteVGOePE mix- This increase seems to relate to the addition of the first 2.5% of
tures, the sample of LDPE, VGO or VGOePE mixture, re-
spectively, were thoroughly mixed with around 20% of
powdered catalysts (i.e., 3.2 mg of the sample with 0.8 mg a 100
of the catalyst). 90
For estimating the amount of coke formed over each cata- 80
lyst, thermogravimetric runs in oxidizing atmosphere, with 70 VGO
a ratio helium/oxygen of 80:20, were performed in a Mettler PE
60
Toledo thermobalance, TGA/SDTA851e/LF/1600 model, cali- VGO-PE10
%w
50
VGO-PE7.5
brated in accordance with the equipment recommendations, 40 VGO-PE5
from 25 to 850 C at 10 C/min. 30 VGO-PE2.5
20 VGO-PE1
3. Result and discussion
10
0
3.1. Study of the decomposition of VGOeLDPE blends in 100 200 300 400 500
the presence of an equilibrium FCC catalyst T (°C)
30
A mother blend of vacuum gas oil (VGO) and low density b
polyethylene (PE) with 10% w/w of polyethylene was pre- VGO
25
pared as described in the previous section. From this mother PE
blend, other mixtures, lowering the percentage of polyethyl- 20 VGO-PE10
ene, were prepared, with 1% (VGOePE1), 2.5% (VGOe VGO-PE7.5
DTG
Table 2
Temperature of maximum decomposition rate for each reaction step of the
a 1
0.9
thermal and equilibrium FCC catalyst-catalytic pyrolysis of VGOePE
mixtures 0.8
0.7
(w-wc)/(wo-wc)
Sample T ( C) VGO peak T ( C) PE peak
0.6 VGO
Thermal pyrolysis PE
0.5
VGOePE10 320.3 478.1 VGO-PE10
VGOePE7.5 324.9 477.6 0.4
VGO-PE7.5
VGOePE5 322.2 477.5 0.3
VGO-PE5
VGOePE2.5 320.1 472.4 0.2 VGO-PE2.5
VGOePE1 301.4 466.4 0.1 VGO-PE1
PE 475.2
0
VGO 291.1 100 200 300 400 500
Catalytic pyrolysis (20% of FCC catalyst) T (°C)
VGOePE10 313.1 462.1
VGOePE7.5
VGOePE5
306.4
315.7
454.4
444.8
b 0.02
0.018 VGO
VGOePE2.5 299.9 444.1 PE
VGOePE1 295.6 438.1 0.016
VGO-PE10
PE 439.9 0.014
VGO-PE7.5
VGO 282.7 0.012 VGO-PE5
DNTG
0.01 VGO-PE2.5
0.008 VGO-PE1
0.006
PE and further addition does not cause any additional increase. 0.004
The peak related to the decomposition of the PE fraction al- 0.002
ways appears at very close temperatures, except in the case 0
of the blend with 1% of PE, that approaches the pure PE tem- 100 200 300 400 500
perature. Therefore, it seems that when the percentage of VGO T (°C)
is high enough (<2.5% of PE in the blend) some tendency of Fig. 2. (a) NTGA and (b) DNTG curves obtained for the catalytic pyrolysis in
the peak associated to the PE to approach to the peak of the presence of 20% w/w of equilibrium FCC catalyst for different VGOePE
VGO can be observed. blends.
Fig. 2 shows the normalized weight loss curves (NTGA)
and the corresponding normalized derivatives of weight curves
(DNTG) for the catalytic pyrolysis in the presence of the FCC process occurs in a wider range of temperature than the ther-
equilibrium catalyst with a relation of 20% in weight. The mal process. When the proportion of polymer diminishes,
NTGA curves show (w wc)/(w0 wc) versus the tempera- the VGO and PE peaks tend to shift to lower temperatures.
ture, where w ¼ weight of sample at time t, w0 ¼ weight of This behaviour can be observed in the 0e5% PE range for
sample at t ¼ 0, and wc ¼ weight of catalyst, obtained in the the VGO peak, and in the overall range of composition studied
thermobalance as the weight of the residue at the final temper- for the PE peak. In good agreement with the bibliography [24],
ature. As can be seen, as in the case of the thermal process, the when increasing the catalyst:polymer relation, the difference
VGOePE blends decompose through two decomposition between the temperatures corresponding to the thermal and
steps, the first related to the degradation or evaporation of catalytic process increases. In this case, the relation cata-
the vacuum gas oil, and the second related to the PE decom- lyst:PE increases when the percentage of PE in the mixture di-
position. As in the previous case, when the proportion of PE minishes, whereas the relation catalyst:VGO increases when
diminishes, the temperature of maximum decomposition rate increasing the percentage of PE in the mixture. Therefore,
of the process associated with the pyrolysis of the VGO frac- the PE peak shows the expected behaviour, shifting towards
tion tends to be closer to that of the VGO (Table 2), whereas lower temperatures when the catalyst:PE ratio increases. How-
the temperature of maximum reaction rate associated with the ever, in the case of the VGO peak, the effect of the catalyst is
PE decomposition step increases when the proportion of PE less important, and is only noticeable from 1 to 5% of PE.
increases, so this temperature, in all the cases, is higher than In order to clearly assess the effect of the concentration of
the pure PE peak temperature (Fig. 2b). On the other hand, the catalyst on the behaviour of the blends, Fig. 3 shows the
the effect due to the presence of the catalyst can also be DNTG for the catalytic pyrolysis using a 7:1 catalyst:VGOe
observed. In fact, both decomposition steps occur at a lower PE blend ratio. This ratio is very often used in the commercial
temperature than that observed in the thermal process units of FCC. In this case, for all the samples, and indepen-
(Table 2), despite the fact that in the presence of VGO, the cat- dently of the proportion of polymer, three peaks in the
alytic pyrolysis of the PE fraction occurs at slightly higher DNTG curve are observed. The first step has been associated
temperatures than those corresponding to the catalytic pyroly- to the elimination of the water contained in the catalyst which,
sis of the pure PE. For the case of the VGO peak, the catalytic considering the high proportion of catalyst used, represents
A. Marcilla et al. / Polymer Degradation and Stability 93 (2008) 723e730 727
a 1
VGO
corresponding peak temperatures. As can be seen, two decom-
0.9 position peaks are observed in the presence of all the catalysts
PE
0.8 VGO-PE10 studied, associated to the decomposition of the VGO and the
0.7 VGO-PE7.5 PE fractions, respectively. In the case of the peak associated
(w-wc)/(wo-wc)
0.01 VGO-PE1
accordance with the results shown in Fig. 4 and in Table 3,
0.008 in this case the order of activity is: HBeta > Al-MCM-
0.006
41 > HUSY > HZSM-5 > FCC. This behaviour can be ex-
0.004
plained considering the physicochemical properties of the
0.002
catalysts (Table 1). In accordance with the bibliography
[23,26], the catalytic activity increases when the pore size,
0
25 125 225 325 425 525 the surface area and the external surface area, and the acidity
T (°C) of the material increase. In this way, the most active catalyst is
the HBeta zeolite that, in comparison with the rest of
Fig. 3. (a) NTGA and (b) DNTG curves obtained for the catalytic pyrolysis in
the presence of a 7:1 ratio of equilibrium FCC catalyst:VGOePE blends.
over, both, the second peak of decomposition (VGO) and the HUSY
0.6 HZSM-5
third peak of decomposition (PE), appear at approximately 0.5
the same temperature for all the samples, independently of 0.4
the amount of polymer in the blend. This behaviour seems 0.3
to indicate that the catalyst, which is in a clear excess with 0.2
respect to the sample, has developed the maximum catalytic 0.1
effect for both decomposition steps. As can be seen in 0
Fig. 3b, the VGO fraction decomposes in a very wide range 50 150 250 350 450 550
0.005
In this section, the effect of other catalysts different to the 0.004
FCC catalyst on the process of degradation of VGOePE 0.003
blends is studied. In this case we have related the VGOePE 0.002
blend with 10% (w/w) of PE, and the effect of three commer- 0.001
cial zeolites (HZSM-5, HUSY and HBeta) and a mesoporous 0
material (Al-MCM-41), has been studied. The pyrolysis exper- 25 125 225 325 425 525
lower temperature of coke oxidation obtained when using The study of the decomposition of VGOePE blends in the
HUSY zeolite and Al-MCM-41 could be related to the high presence of different catalysts indicates that the effect of these
BET area and the relatively high pore size of both materials materials on the decomposition of the VGO fraction is very
that can favour the diffusion of the oxygen and facilitate the similar for all the catalysts studied in this work, whereas in
oxidation [28]. the case of the decomposition of the PE fraction, the catalytic
With respect to the amount of coke formed in each case effect of each material depends strongly on the physicochem-
(Table 5), the smaller amounts are obtained on the HZSM-5 ical and structural characteristics of the catalysts, and the ac-
zeolite and on the FCC catalyst. Despite the deactivation of tivity increases with the acidity, the BET area, the external
the catalyst not only depends on the amount of coke, but surface area and the pore size.
also depends on its nature and location, a first approximation The composition of the coke formed as a consequence of
to the resistance of deactivation can be assessed from the the pyrolysis process depends on the type of pyrolyzed mix-
amount of coke [20,29], and this fact indicates that these are ture and the catalyst. Among the materials studied in this
the most resistant materials to the deactivation by coke forma- work, the catalysts showing the lower tendency to coke forma-
tion. Nevertheless, these catalysts also presented the lower ac- tion are HZSM-5 and FCC, next are the HBeta zeolite and Al-
tivity (Table 4). The HUSY zeolite, with an intermediate MCM-41 and the material that most favours coke formation is
activity, presents the higher coke amount, and is the material the HUSY zeolite. On the other hand, the coke formed on the
that favours the coke deposition more among the five catalysts HUSY and MCM-41 materials presents a lower temperature of
studied, possibly due to the high acidity associated to weak oxidation, whereas that formed on FCC and ZSM-5 displays
acid sites (Table 1). The high tendency of the HUSY zeolite higher temperatures of oxidation. In the case of the coke
to the deactivation by coke in the PE pyrolysis has also been formed on HBeta, the temperature of oxidation clearly de-
pointed out by other authors [20]. Finally, Al-MCM-41 and pends on the composition of the pyrolyzed material.
the HBeta zeolite present a relatively high formation of As a conclusion, the results obtained in this work indicate
coke, but lower than in the case of the HUSY zeolite. There- the feasibility of the treatment of the VGOePE blends in
fore, both materials show a tendency to the deactivation by a conventional FCC process as an alternative way for plastic
coke deposition similar to each other, and intermediate be- recycling. Moreover, considering a criterion based exclusively
tween HZSM-5 and the FCC catalyst. Both materials also on the catalytic activity and the ‘‘expectable’’ deactivation be-
present a high catalytic activity, but the temperature of oxida- haviour, the material showing the best characteristics for the
tion of the coke obtained on the Al-MCM-41 is lower than that pyrolysis of VGOePE blends in a FCC conventional process
corresponding to the coke obtained for the HUSY zeolite. is the Al-MCM-41, because this presents high catalytic activ-
Therefore, the conditions of regeneration will be more favour- ity, a low tendency to the formation of coke deposits and low
able for Al-MCM-41. Thus, excluding any other type of eco- temperature of regeneration by oxidation of the coke.
nomic considerations, stability of the material or commercial
interest of pyrolysis products, the Al-MCM-41 can be consid-
ered a good choice to carry out the recycling of plastic residue Acknowledgements
process by means of fluidized catalytic cracking of VGOePE
blends. Financial support for this investigation has been provided by
the Spanish ‘‘Comisión de Investigación Cientı́fica y Tecnológ-
4. Conclusions ica’’ de la Secretarı́a de Estado de Educación, Universidades, In-
vestigación y Desarrollo and the European Community (FEDER
The results obtained in this work indicate that the thermal refunds) (CICYT PPQ2004-02187) and by the Generalitat
and the catalytic pyrolysis of VGOePE blends proceeds Valenciana (ACOMP06/162 and ACOMP/2007/094).
through two decomposition steps, the first related to the degra-
dation or evaporation of the VGO fraction and the second
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Publicación VI: Study of the decomposition of Vacuum Gas Oils-Low Density
Polyethylene blends: evolution of the gases, A. Marcilla, A. Gómez-Siurana, D.
Berenguer, Polymer Degradation and Stability, Available online 24 July 2008.
a r t i c l e i n f o a b s t r a c t
Article history: Previous studies focused on the behaviour of different samples of vacuum gas oil (VGO), polyethylene
Received 19 May 2008 (PE) and vacuum gas oil–polyethylene blends (VGO–PE) in thermal and catalytic pyrolysis, showed that
Accepted 8 July 2008 the pyrolysis of the blends goes through two decomposition steps, where the first is related to the
Available online xxx
elimination of the VGO fraction, and the second to the pyrolysis of PE. Moreover, the presence of catalyst
mainly affects the PE decomposition. In this work, the evolution of the composition of the gases evolved
Keywords:
in the thermal and catalytic pyrolysis decomposition of VGO, PE and VGO–PE blend with temperature (or
Catalytic pyrolysis
time) has been studied by GC/MS. The results agree with the previous studies and allow the behaviour of
Dynamic pyrolysis
GC/MS such systems to be better understood, yielding valuable information for designing processes of plastic
VGO recycling by mixing with VGO and the mixture being treated in a unit similar to the industrial fluid
PE catalytic cracking unit.
VGO–PE blends Ó 2008 Elsevier Ltd. All rights reserved.
0141-3910/$ – see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymdegradstab.2008.07.019
Please cite this article in press as: Marcilla A et al., Study of the decomposition of low density polyethylene blends with vacuum gas oils:
Evolution of the gases, Polym Degrad Stab (2008), doi:10.1016/j.polymdegradstab.2008.07.019
ARTICLE IN PRESS
different catalysts (HZSM5, HUSY, HBeta zeolites, FCC catalyst and was selected for the sample preparation because at 120 C the LDPE
Al-MCM-41). The results obtained showed, considering a criterion is completely melted, thus permitting a good mixing degree with
based exclusively on the catalytic activity and the deactivation the VGO.
behaviour, that the material with the best characteristics for the
pyrolysis of VGO–PE blends in a FCC conventional process was Al- 2.2. Experimental equipment
MCM-41, because it presents high catalytic activity, low tendency to
the formation of coke deposits and low temperature of regenera- Thermogravimetric experiments were performed in a Netzsch
tion by oxidation of the coke. Moreover, the results indicated that TG 209 thermobalance. The sample temperature was measured
the thermal and the catalytic pyrolysis of VGO–PE blends goes with a thermocouple directly at the crucible, i.e., very close to the
through two decomposition steps, the first related to the degra- sample. A temperature calibration procedure was performed, in
dation of the VGO fraction and the second related to the decom- accordance with the equipment recommendations, and the
position of PE fraction. Both degradation steps seem to be affected different samples were pyrolyzed in dynamic conditions from 30 to
by the presence of the catalyst, being displaced towards lower 550 C at 5 C/min under a nitrogen flow of 30 mL/min (STP).
temperatures, and the effect of the catalyst is more noticeable for A vertical batch reactor was used for the pyrolysis in order to
the decomposition of the PE fraction than for the degradation of the analyze the evolution of the composition of gases and condensed
VGO fraction. products evolved. This disposition, as well as the carrier gas inlet
In this work, dynamic pyrolysis of different samples of vacuum from the bottom of the reactor, facilitates the generated gas outlet
gas oil (VGO), polyethylene (PE) and vacuum gas oil–polyethylene to the top. The reactor outlet was heated at 300 C to prevent
blend with 10% PE (VGO–PE) has been performed in a vertical condensation of the less volatile compounds. The reactor was
reactor in order to study the thermal and the catalytic pyrolysis heated by an electric furnace, which was connected to a program-
using an equilibrium FCC catalyst. In contrast to most studies of the mable temperature controller. The sample was placed in a crucible
composition of the products evolved in the pyrolysis process, which which was leaned against a rod in the middle of the reactor. A
analyze the overall gaseous or liquid product collected through the thermocouple in direct contact with the sample was used in order
complete degradation of a given polymer [18–20], in this case, the to monitor the actual temperature of the process (Fig. 1). In the
evolution with the temperature (or the time) of the composition of catalytic experiments, the ratio of catalyst:sample was 7:1, and
the gases evolved has been studied by GC/MS. The results obtained sample amounts of around 300 mg (VGO, PE or VGO–PE) were
permit the nature of the processes involved in each step of used. Prior to the experiment, the system was purged with
decomposition to be better understood and to analyze the possi- a nitrogen stream at room temperature for 30 min to ensure an
bility of recycling plastics by mixing them with the vacuum gas oil inert atmosphere. The nitrogen flow rate used was 150 mL/min
in refineries. (STP). Experiments were carried out from 30 to 550 C at 5 C/min.
In each experiment, the non-condensed products (gas fraction)
and the condensed products (liquid fraction) were collected at
2. Experimental
intervals of 50 C. The successive gas fractions evolved from the
reactor were collected every 10 min in different Tedlar bags of 2 L
2.1. Materials
capacity, and their composition was analyzed by gas chromatog-
raphy in a gas chromatograph coupled to a mass spectrometer (GC/
A low density polyethylene (LDPE) (200–500 mm particle size)
MS) (Agilent 6890 N GC-MD 5973N), using a GS-GasPro column
supplied by Dow Chemicals, with a density of 0.918 g/cm3 (ASTM D
(30 m 0.32 mm I.D.). The column program was: injector temper-
792) and melt flow index of 7.7 g/min (ISO 1133) was used. The
ature, 200 C; initial column temperature, 35 C; initial time, 5 min;
vacuum gas oil (VGO) and the commercial equilibrium FCC catalyst
heating rate, 5 C/min; final temperature, 170 C; final time,
were supplied by Repsol YPF (Spain). The VGO has a boiling range of
20 min; run time, 52 min; carrier gas, He.
240–560 C and a density of 0.920 g/cm3.
Glass traps with stainless steel Dixon rings were used to collect
An FCC catalyst was characterized by X-ray fluorescence (XRF),
the liquid fractions using a water/ice bath. The evolution of the
N2 adsorption isotherms at 77 K, and temperature-programmed
composition of the liquid fractions has not been studied in this
desorption (TPD) of ammonia, using the equipment and experi-
work.
mental conditions described elsewhere [21]. Table 1 shows the
physicochemical and structural characteristics of the equilibrium
2.3. Product analysis
FCC catalyst.
The VGO–PE blend was prepared using a Jankel and Kunkel
The volatile compounds were analyzed by GC/MS in the
IKAVISC MR-F12 mixer by continuously stirring mixtures of the
conditions specified in the previous section, and the compounds
base components (LDPE and VGO) with a weight fraction of 10% of
generated were identified using the library Wiley 275, that comes
the polymer for 120 min, at 60 rpm and120 C. This temperature
with the analysis program. Moreover, standard gaseous hydrocar-
bons (from Scott Speciality Gases) were used to identify and
Table 1 quantify the volatile compounds.
Characteristics of the catalyst
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VGO–PE samples. The thermal and catalytic pyrolysis of PE has near to the initial boiling point of this VGO, and a shoulder that
been widely studied [21–23] and occurs in a single stage of appears at around 280 C. This shoulder was not observed in
decomposition. In accordance with Fig. 2b, at the heating rate used previous work, where the heating rate used was 10 C/min [17].
in this work, the degradation of pure PE shows a single decompo- Actually, the separation among the different stages of decomposition
sition step, which occurs in a relatively narrow interval (375– of a complex process is improved as the heating rate decreases. In
488 C), showing the temperature of maximum decomposition rate accordance with these results, the interval of temperature selected
at 463 C. Therefore, the interval of temperature selected for the for the study of the decomposition of the VGO was 100–550 C.
study of the degradation of PE was 350–550 C. In the case of the VGO–PE blend, two decomposition steps
In the case of the vacuum gas oil, the decomposition and/or appear. According to Fig. 2b, the comparison with the DTG curves
evaporation of the sample occurs in the range of 150–350 C, and corresponding to the cases of PE and VGO clearly indicates that the
goes through two decomposition steps, one at 243 C, a value that is first stage is associated with the decomposition or evaporation of
the vacuum gas oil, whereas the second one is related to the PE
decomposition. Moreover, both stages seem to proceed indepen-
a 100 dently, despite the fact that both steps occur at high temperatures
90 as in the case of the pure samples, i.e. 290 and 465 C, respectively
80 (see Table 2). The differences between the behaviour observed for
70 the pure samples (i.e., PE and VGO) and the mixtures have been
60
discussed elsewhere [17]. According to these results, the interval of
temperatures selected to collect the gas samples in the case of
%w
50
VGO–PE was 100–550 C.
40
Fig. 3 shows the normalized weight loss curves (NTGA) and their
30 corresponding normalized derivatives (DNTG) for the catalytic
VGO
20 VGO-PE10 pyrolysis in the presence of the equilibrium FCC catalyst, with
10 PE a ratio of catalyst:sample of 7:1. The NTGA curves show the
0 representation of (w wc)/(w0 wc) versus the temperature,
25 125 225 325 425 525 where w ¼ weight of sample at time t, w0 ¼ weight of sample at
T (ºC) t ¼ 0, and wc ¼ weight of catalyst, obtained in the thermobalance as
b 3
the weight of the residue at the final temperature. The assignment
of the different reaction steps was studied elsewhere [17], and as
VGO
2,5 VGO-PE10
PE
Table 2
2 Temperature of maximum decomposition rate for each reaction step of the thermal
and catalytic pyrolysis of VGO–PE mixtures
DTG
1,5
Sample T ( C)
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a 100
9,E+06
8,E+06
90
80 7,E+06
70 6,E+06
60 5,E+06
DNTG
50
4,E+06
40 500-550 °C
3,E+06
30 450-500 °C
VGO 2,E+06
20 VGO-PE 10% 400-450 °C
10 PE 1,E+06
350-400 °C
0 0,E+00
25 125 225 325 425 525 0 10 20 30 40
T (ºC) t (min)
b 1,6 Fig. 4. Chromatograms corresponding to the gases obtained at each interval of
VGO temperature in the thermal pyrolysis of PE.
1,4
VGO-PE 10%
1,2 PE indicating, in good agreement with previous work [17], the exis-
1
tence of some catalytic effect of the equilibrium FCC catalyst. In
accordance with the previous statements, the interval of temper-
DNTG
0
25 125 225 325 425 525
3.2. Study of the effect of temperature in the composition of the
gases evolved in the degradation of VGO–PE
T(ºC)
Fig. 3. (a) NTGA and (b) DNTG curves obtained for the catalytic pyrolysis of VGO, PE The study of the effect of temperature in the composition of the
and VGO–PE blend. gases evolved in the thermal and catalytic pyrolysis of the VGO, PE,
and VGO–PE samples was performed collecting the gases evolved
can be seen, in the case of the VGO sample, two decomposition in intervals of 50 C, in the experiments carried out in the reactor,
steps appear, the first being related to the loss of the water adsor- and in the range of temperature selected according to the consid-
bed over the catalyst, that, considering the high proportion of erations pointed out in the previous section.
catalyst used, represents a considerable percentage of the mixture.
The second step is related to the decomposition or evaporation of 3.2.1. Thermal pyrolysis
the VGO. In the case of the PE sample, Fig. 3b indicates two The thermal pyrolysis of the VGO does not yield any gaseous
decomposition steps, the first related to the loss of the adsorbed product, thus indicating that during the heating process, the VGO
water in the equilibrium FCC catalyst, and the second due to the
degradation of PE, that occurs in a ‘‘narrow’’ interval. Finally, in the
Table 4
case of the VGO–PE blend, three decomposition peaks in the DNTG Composition of the non-condensed products (mg compound/g sample pyrolyzed) at
curve are observed. As in the previous cases, the first peak has been each interval of temperature in the thermal pyrolysis of the different samples
associated with the elimination of the adsorbed water contained in studied
the catalyst. The second step has been related to the decomposition NC T ( C)
of the VGO fraction and the third step has been related to the
PE VGO–PE 10%
degradation of the PE fraction. As can be seen, in the VGO–PE blend
decomposition, the temperature of the maximum reaction rate 350–400 400–450 450–500 500–550 400–450 450–500 500–550
associated with the VGO loss occurs at around 215 C, slightly lower Alkanes
than the value observed in the absence of catalyst (see Table 2), and C2 0.02 0.16 1.96 0.54 0.08 0.36 0.05
C3 0.04 0.44 3.62 0.43 0.12 0.48 0.02
C4 0.06 0.61 3.89 0.30 0.13 0.53 0.02
C5 0.03 0.37 3.33 0.34 0.13 0.34 0.00
Table 3 C6 0.00 0.25 3.06 0.40 0.19 0.34 0.00
Yield of fraction distribution in thermal and catalytic pyrolysis (wt%) C7 0.04 0.44 3.04 0.48 0.11 0.37 0.02
C8 0.00 0.11 1.02 0.54 0.00 0.09 0.20
VGO PE VGO–PE 10% C9 0.00 0.00 0.18 0.13 0.00 0.00 0.00
Thermal pyrolysis
Gases 0.0 18.7 3.0 Alkenes
Condensables 98.0 80.6 97.2 C2 0.00 0.14 4.83 2.35 0.08 1.08 0.25
C3 0.04 0.72 15.71 4.67 0.33 2.58 0.41
Catalytic pyrolysis C4 0.20 2.05 20.38 4.92 0.42 3.49 0.36
Gases 41.4 71.9 34.9 C5 0.08 1.22 21.59 6.57 0.22 3.17 0.38
Condensables 66.4 31.7 65.1 C6 0.19 1.89 31.93 9.75 0.43 3.93 0.67
Cokea 5.6 4.9 5.8 C7 0.00 0.99 15.69 6.32 0.00 1.73 0.33
a C8 0.14 0.67 4.27 2.45 0.00 0.87 0.00
Coke calculated with the TGA curves obtained in oxidation experiments at 10 C/
C9 0.00 0.00 0.55 0.78 0.00 0.00 0.00
min.
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18 140
a 250 2
VGO-PE mg comp/ g pol
PE mg comp/ g pol
14
Alkanes PE 100 200 Alkenes VGO 1,6
mg comp/ g sample
Alkenes, Aromatics
12 Alkenes PE Aromatics VGO 1,4
10 80
150 1,2
8 60
1
6
40 100 0,8
4
0,6
2 20
50 0,4
0 0
0,2
°C
°C
°C
°C
°C
°C
°C
°C
°C
0 0
5
5
12
17
22
27
32
37
42
47
52
°C
°C
°C
°C
°C
°C
°C
°C
°C
T (°C)
75
5
12
17
22
27
32
37
42
47
Fig. 5. Changes with the temperature of the composition of alkanes and alkenes in the T (°C)
gases obtained in the thermal pyrolysis of PE. b 400 12
mg comp/ g sample
Alkenes, Aromatics
was not degraded, but a process similar to fractional distillation Alkenes PE
300
occurs. Therefore, the composition of the condensed product Aromatics PE
8
250
obtained at the exit of the reactor must be equal to that corre-
sponding to the original VGO, which is mainly evaporated as the 200 6
temperature increases, condensing in the cold trap placed at the 150
4
exit of the reactor. Table 3 shows the mass balance obtained for
100
the different cases studied in this work. As can be seen, in the case 2
of the thermal decomposition of VGO, 98.0% of liquids were 50
collected, and in the cases of the thermal decomposition of the PE 0 0
and the blend, the sum of gases and condensable products is very
°C
°C
°C
°C
°C
°C
°C
°C
°C
75
5
12
17
22
27
32
37
42
47
close to the expected value of 100%.
In contrast to the case of the VGO, the thermal pyrolysis of PE T (°C)
yields a gaseous fraction and a liquid fraction (see Table 3). Fig. 4 c 140 7
Alkanes mg comp/ g sample
mg comp/ g sample
Alkenes, Aromatics
Aromatics VGO-PE
be seen, the chromatograms are very similar, and the main differ-
100 Alkenes VGO-PE 5
ences can be found in the relative abundance of each compound.
Table 4 shows the composition obtained at each temperature. The 80 4
different compounds have been grouped as alkanes or alkenes
60 3
(aromatics have not been detected) and by the number of carbon
atoms. Fig. 5a shows the evolution with the temperature of the 40 2
composition of the gases obtained in the thermal pyrolysis of PE. As
20 1
can be seen, the main generation of products has been obtained in
the 450–500 C range. This result is in good agreement with the 0 0
data reported in Table 2. In all the studied intervals, alkenes are
°C
°C
°C
°C
°C
°C
°C
°C
°C
75
5
12
17
22
27
32
37
42
47
35
30 C2
temperatures (350–450 C), the major compounds generated are
mg comp/ g sample
C3
25 C4
C4 and C6, being slightly higher the C4 yield (Table 4). Nevertheless
C5 at higher temperatures (450–550 C), although C4 compounds
20 continue to be abundant, the tendency changes, and C6 compounds
C6
15 C7 predominate and 1-hexene is the major compound generated in
C8 the main interval of degradation. Moreover, a noticeable increase of
10 C9 C5 alkenes can be also observed.
5 As indicated in the previous section, the pyrolysis of the VGO–PE
blend shows two decomposition steps. The first is associated with
0 the evaporation of the VGO and the second with the degradation of
°C
°C
°C
°C
°C
°C
°C
°C
52
12
17
22
27
32
37
42
47
indicates that, unlike the case of the pure VGO, gaseous compounds
T (°C) were generated, but only in the range of temperatures corre-
Fig. 6. Changes with the temperature in the composition of alkenes in the non-
sponding to the PE decomposition. As in the case of PE, the range of
condensed products in the gases obtained in the thermal pyrolysis of PE (the temperature showing the main generation of non-condensed
temperature axis indicates the middle of each interval). products is the 450–500 C interval, where n-alkenes are the more
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abundant compounds (Table 4). These results indicate, as suggested time where they were collected, but is also due to secondary
elsewhere [17] and in Section 3.1, that PE and VGO evolve in reactions undergone by the pyrolysis products inside the reactor,
practically independent steps. The chromatograms corresponding favoured by the high temperature and the high time of residence of
to the gas fraction obtained in the four intervals where the gener- these products inside the reactor.
ation of non-condensed products has been observed are very Tables 5 and 6 show the composition of the non-condensed
similar to those shown in Fig. 4, and the change of the composition fraction obtained in the catalytic pyrolysis of the different samples
of this fraction (Fig. 5b) is also very similar to that corresponding to studied in this work, and the evolution with the temperature of
the pure PE (see Fig. 5a), where 1-hexene is also the major alkanes and alkenes in the case of VGO is shown in Fig. 8. As can be
compound in the range of temperatures corresponding to the seen in Fig. 8a, for the VGO samples, the first interval showing
maximum decomposition rate. As can be expected, the yield of generation of non-condensed compounds is between 200 and
gases is noticeably lower than in the case of pure PE, thus reflecting 250 C, where alkanes with seven carbon atoms are the favoured
the fact that the sample only contains 10% PE. compounds. The major compound of the C7 alkanes group was
iso-heptane. Nevertheless, as the temperature increases, the
3.2.2. Catalytic pyrolysis selectivity changes towards compounds with a lower number of
In agreement with the literature [25], the yield of non- carbon atoms. In this way, in the 250–300 C interval, corre-
condensed products obtained in the pyrolysis carried out in the sponding to the maximum non-condensed product generation,
presence of the catalyst increases noticeably with respect to the the more abundant are C6 alkanes, although the major compound
thermal pyrolysis case (Table 3). Fig. 7a shows the evolution of collected in this interval is iso-pentane. In the 300–450 C interval,
the gases generated during the catalytic decomposition of the the favoured compounds are alkanes with four carbon atoms, iso-
VGO sample. As it can be seen, unlike the thermal process, non-- butane being the major compound. Finally, at higher temperatures
condensed products have been generated along the different (400–450 C), the formation of C3 alkanes is favoured, iso-propane
intervals of temperature considered (200–500 C), where the being the major compound. According to Table 6 and Fig. 8b, in the
maximum yield is in the 250–300 C interval. This behaviour case of alkenes, the formation of C5 was favoured at low
indicates that the catalyst interacts to some extent with the VGO temperatures (200–250 C), 1-pentene being the major compo-
fraction, causing the degradation of a part of this fraction and the nent of this group, whereas as the temperature increases (250–
corresponding generation of volatile compounds, despite the fact 400 C), the selectivity changes towards C3 alkenes (i.e., propene).
that some delay of temperature (or time) with respect to the values Finally at higher temperatures (450–500 C) ethylene is the
of maximum reaction rate observed in the TGA experiments can be favoured alkene. With respect to the generation of aromatic
noted, related to the residence time of the products evolved in the compounds, at low temperatures (200–300 C) benzene is fav-
reaction system. oured, whereas at high temperatures (300–500 C) toluene is
This catalytic activity in such a system is also reflected in the favoured.
DNTG curves of Figs. 2 and 3, and in Table 2, which shows Fig. 9a shows the evolution with the temperature of the yield of
a decrease of the temperature of maximum decomposition rate of alkanes, alkenes and aromatics in the non-condensed products
the VGO, as a consequence of the presence of the equilibrium FCC obtained in the catalytic pyrolysis of PE. As can be seen, alkanes are
catalyst. The generation of volatile products at temperatures higher the major compounds obtained in all the intervals of temperature
than that observed in TGA curves of Fig. 3 can be explained by the studied. This behaviour is similar to that observed in the decom-
delay between the time when the gases were produced and the position of PE in the presence of FCC catalysts in a fixed bed reactor,
Table 5
Composition (mg compound/g sample pyrolyzed) of alkanes present in the non-condensed products at each interval of temperature in the catalytic pyrolysis of the different
samples studied
Alkanes NC T ( C)
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Table 6
Composition (mg compound/g sample pyrolyzed) of alkenes and aromatics present in the non-condensed products at each interval of temperature in the catalytic pyrolysis of
the different samples studied
Alkenes NC T ( C)
Aromatics
where mainly iso-alkanes, were obtained, whereas the formation of the case of the thermal pyrolysis and a mechanism based on the
n-alkenes in the thermal process is favoured [26]. This behaviour formation of carbonium ions on the catalyst surface in the case of
can be related to the different mechanisms of reaction of the catalytic pyrolysis, where bond scissions, isomerisation and
thermal and catalytic pyrolysis (i.e., a free-radical mechanism in hydrogen exchange reactions occur which favour the formation of
iso-compounds) [13].
a 50
As seen in Fig. 9b, the interval of maximum generation of
non-condensed products in the catalytic degradation of PE is 400–
45 C2
450 C. Catalytic pyrolysis yields a narrower distribution of prod-
mg comp/ g sample
40 C3
C4 ucts, due to the molecular sieve character of the catalyst [7].
35
30 C5 According to Table 5 and Fig. 9, in all the intervals of temperature
C6 studied the formation of C4 alkanes is favoured, and iso-butane is
25
C7 the major compound in all the cases. In the case of the formation of
20
C8 alkenes (Table 6), in the 350–400 C interval the formation of C4 is
15 C9
10
favoured, although the major component is propene. At higher
5
temperatures, the selectivity of alkenes changes towards C3, and
0
propene is also the major compound. Finally, in the 450–500 C
range, the formation of ethene was favoured. The formation of
°C
°C
°C
°C
°C
°C
°C
°C
°C
5
12
17
22
27
32
37
42
47
C3
VGO and PE has been studied, the case of the catalytic pyrolysis of
1 C4
C5 the VGO–PE blend, which is the main objective of this work, must
0,8 be considered, and compared with the previous results. In accor-
0,6
dance with Fig. 3, in this case, two decomposition stages occur,
corresponding to the VGO and PE decomposition, respectively. In
0,4 agreement with the composition of the blend, the highest yield
0,2 must correspond to the first decomposition step, i.e., to the VGO
evolution. Fig. 7c shows the yields obtained in this case. The
0 comparison with the results shown in Fig. 7a reflects a higher
°C
°C
°C
°C
°C
°C
°C
°C
°C
5
12
17
22
27
32
37
42
47
the case of pure VGO, whereas the comparison with the results
T (°C) shown in Fig. 7b indicates a higher generation of products in the
Fig. 8. Changes with the temperature of (a) alkanes and (b) alkenes in the non-
range of lower temperatures than in the case of pure PE. However,
condensed products obtained in the catalytic pyrolysis of VGO (the temperature axis despite some deviation, that can be observed related with the
indicates the middle of each interval). overlapping of the processes, the composition of the gases obtained
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a 180 a 30
160 C2 C2
25
mg comp/ g sample
mg comp / g sample
140 C3 C3
C4 C4
120 20
C5 C5
100 C6 C6
15
80 C7 C7
C8 C8
60 10
C9
40 5
20
0
0
°C
°C
°C
°C
°C
°C
°C
°C
°C
°C
°C
°C
°C
°C
°C
°C
°C
°C
75
5
12
17
22
27
32
37
42
47
75
5
12
17
22
27
32
37
42
47
T (°C)
T (°C)
b b 3
25
C2
C2 2,5
mg comp/ g sample
C3
mg comp / g sample
20 C3
C4
C4 2
C5
15 C5
C6 1,5
10 1
5 0,5
0
0 °C
°C
°C
°C
°C
°C
°C
°C
°C
75
°C
°C
°C
°C
°C
°C
°C
°C
°C
5
12
17
22
27
32
37
42
47
75
5
12
17
22
27
32
37
42
47
T (°C)
T (°C)
Fig. 10. Changes with the temperature of (a) alkanes and (b) alkenes in the non-
Fig. 9. Changes with the temperature of (a) alkanes and (b) alkenes in the non- condensed products obtained in the catalytic pyrolysis of VGO–PE (the temperature
condensed products obtained in the catalytic pyrolysis of PE (the temperature axis axis indicates the middle of each interval).
indicates the middle of each interval).
in each interval of temperature seems to be related to a linear systems studied in this work: 450–500 C for the thermal decom-
combination of the composition of the gases corresponding to pure position of PE and for the VGO–PE blend, 250–300 C for the
VGO and PE, according to their corresponding mass fraction. catalytic degradation of the pure VGO and for the first step of the
Therefore, the results obtained suggest that both decomposition catalytic decomposition of the VGO–PE blend, and 400–450 C for
steps occur in an independent way. the catalytic degradation of the pure PE and the second decom-
According to Table 5 and Fig. 10, at low temperatures (200– position step of the VGO–PE blend.
250 C) the more abundant alkanes are the C7s, as in the catalytic As can be seen and in good agreement with the results discussed
decomposition of the VGO, whereas when the temperature in the previous sections, in the thermal decomposition of PE, the
increases, the formation of C4 alkanes is favoured, iso-butane more abundant compounds are the n-alkenes. The major
being the major compound. Moreover, the amount of alkanes of compound is 1-hexene (14.58%), followed by propene (11.63%). 1-
four carbon atoms generated between 150 and 500 C is higher butene and 1-pentene are in very similar proportions (10.54% and
than in the case of VGO. This clear increase can be related to the 10.20%, respectively). The VGO–PE blend, only yields non-
fact that, in this interval of temperature, the decomposition of PE condensed products in the range of decomposition corresponding
also occurs, favouring the formation of iso-butane in all the ranges to PE, and these products show a very similar distribution to that
of temperature. The evolution of alkenes and aromatic compounds corresponding to the case of pure PE: the major compound is 1-
(Table 6 and Fig. 10) generated in the degradation of the VGO–PE hexene (14.68%) followed by propene (13.33%), and 1-butene and
blend shows that in the interval of 200–350 C, where the 1-pentene (11.46%, and 10.07%, respectively). As was indicated in
decomposition of VGO occurs, the alkene favoured is propene, Section 3.2, this reveals that the behaviour of the decomposition of
whereas in the interval where the decomposition of PE occurs the VGO and PE fractions in the blend is independent, and the non-
(350–500 C), the major compounds are C3 alkenes (propene), condensed products obtained in the thermal pyrolysis have their
although an important growth of C4 compounds has also been origin in the PE fraction pyrolysis.
observed, clearly due to the catalytic pyrolysis of PE. Finally, The non-condensed products obtained in the catalytic pyrolysis
toluene is the major aromatic compound in the whole interval of of the different samples (Table 7), show a change of selectivity
decomposition. towards iso-alkanes. In the case of VGO, the major compound is iso-
pentane (19.9%) followed by iso-butane (15.48%), and iso-hexane,
and iso-heptane (10.91% and 7.23%, respectively). The comparison
3.3. Comparison of the non-condensed products generated during of these results with that corresponding to the decomposition of
the main interval of decomposition the VGO–PE blend in the range 250–300 C (i.e., decomposition of
the VGO fraction) reflects a very similar composition. On the other
Table 7 shows the composition of the non-condensed products hand, the catalytic decomposition of PE also yields iso-alkanes as
generated in the main interval of decomposition of the different the major compounds, whereas, in this case, iso-butane is the main
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Table 7
Composition (mass percentage) of the non-condensed products generated in the main interval of decomposition of the different systems studied
Thermal Catalytic
PE, 450–500 C VGO–PE, 450–500 C VGO, 250–300 C PE, 400–450 C VGO–PE, 250–300 C VGO–PE, 400–450 C
Ethane 1.45 1.87 0.00 0.67 0.00 1.57
Ethene 3.58 5.56 0.04 1.62 0.06 3.55
Propane 2.68 2.45 2.20 7.26 2.51 11.36
Propene 11.63 13.33 0.25 5.33 0.33 5.32
Iso-butane 0.03 0.00 15.48 32.42 16.07 24.86
Butane 2.85 2.72 3.06 4.87 3.24 5.77
1-Butene 10.54 11.46 0.00 0.71 0.00 0.44
1.3-Butadiene 0.07 0.00 0.00 0.00 0.00 0.00
Trans-2-butene 3.41 3.84 0.00 0.00 0.00 2.45
2-Methyl-propene 0.00 1.79 0.00 0.00 0.00 0.00
Iso-butene 1.14 0.94 0.00 0.00 0.00 1.57
Iso-pentane 0.00 0.00 19.90 24.42 19.83 15.20
Pentane 2.39 1.76 1.09 2.01 1.12 2.06
1-Penteno 10.20 10.07 0.00 0.00 0.00 0.00
Trans-2-pentene 0.95 1.60 0.00 0.00 0.00 0.00
Iso-hexane 0.12 0.14 10.91 0.00 10.20 2.55
Iso-pentene 2.18 2.76 0.00 1.23 0.00 0.80
1,3-Pentadiene 0.35 0.00 0.00 0.00 0.00 0.00
Hexane 1.69 1.35 0.65 1.02 0.61 0.77
1,3-Cyclopentadiene 0.29 0.00 0.00 1.12 0.00 0.00
1-Hexene 14.58 14.68 0.00 0.00 0.00 0.00
Iso-heptane 2.27 2.13 7.23 4.32 12.65 2.02
Heptane 2.00 1.72 0.31 0.29 0.33 0.26
1-Heptene 6.48 6.64 0.00 0.00 0.00 0.00
Octane 0.75 0.48 4.91 0.31 4.55 0.90
1-Octene 1.75 2.09 0.00 0.00 0.00 0.00
Nonane 0.13 0.00 0.00 0.00 0.00 0.00
1-Nonene 0.40 0.00 0.00 0.00 0.00 0.00
Benzene 0.00 0.00 0.00 0.05 0.03 0.34
Toluene 0.00 0.00 0.00 0.23 0.05 1.57
Remaining products 16.08 10.61 33.96 12.13 28.41 16.63
component of the mixture (32.42%) followed by iso-pentane iso-alkanes. The behaviour of the VGO–PE blend suggests that the
(24.42%), and in a lesser proportion appears propane at around two processes involved in the catalytic pyrolysis process occur
4.5%, and butane (at around 4.5%). The comparison with the mainly in independent ways.
composition of the products obtained in the range of temperatures The study of the composition of non-condensable products
where the pyrolysis of the PE fraction of the VGO–PE blend occurs, obtained in the main interval of decomposition of the different
also shows a very similar behaviour (24.86% of iso-butane and systems shows, that during the thermal decomposition of PE
15.20% of iso-pentane), despite some differences related to the the major non-condensed compound is 1-hexene, whereas in the
overlapping with the products evolved in the VGO fraction pyrol- catalytic decomposition it is iso-butane. In case of the VGO, the
ysis and to the possibility of some interaction between the two major non-condensed compound observed in the catalytic pyrol-
decomposition steps. ysis is iso-pentane. Finally, the behaviour of the blend indicates that
in the interval of temperature associated with the decomposition of
4. Conclusions the VGO the major compound is iso-pentane, whereas in the
interval associated with the decomposition of PE, it is iso-butane.
The results obtained in this work indicate that in the thermal Therefore, despite the fact that some interaction between both
pyrolysis, VGO is not degraded, and only a fractional distillation reactions steps could be considered, the catalytic decomposition of
occurs. Nevertheless, during the thermal decomposition of poly- the VGO and PE fractions also seems to occur through independent
ethylene, gases are generated in the whole interval of temperature processes.
studied, where n-alkenes are favoured. In the thermal decompo- As a conclusion, the results obtained in this work indicate the
sition of the VGO–PE blend, non-condensed products were only ability of the treatment of the VGO–PE blends in a conventional FCC
collected in the interval of decomposition associated with the process as an alternative way of plastic recycling, since the presence
degradation of the PE, where n-alkenes were also the major of polyethylene does not significantly affect the composition of the
compounds. gases with respect to the VGO, adding an additional decomposition
The catalytic decomposition of the VGO yields non-condensed step at higher temperatures. Moreover, its presence favours the
products in the range of 200–500 C, with a maximum in the 250– formation of iso-butane, propane, and butane, which form part of
300 C range. This fact reveals the existence of some catalytic liquefied petroleum gas (LP).
activity of the FCC catalyst on the VGO decomposition. In this case,
the compounds favoured in the overall range of temperature are Acknowledgement
the iso-alkanes. The catalytic pyrolysis of the PE reflects a higher
yield of gases than in the thermal process, changing the selectivity Financial support for this investigation has been provided by the
from n-alkenes towards iso-alkanes. Finally, the catalytic pyrolysis Spanish ‘‘Comisión de Investigación Cientı́fica y Tecnológica’’ de la
of the VGO–PE blend shows generation of non-condensed products Secretarı́a de Estado de Educación, Universidades, Investigación y
in the 150–500 C range, where 250–300 C is the main interval of Desarrollo and the European Community (FEDER refunds) (CICYT
decomposition. As in the previous cases, selectivity exists towards PPQ2004-02187), Generalitat Valenciana (ACOMP06/162 and
Please cite this article in press as: Marcilla A et al., Study of the decomposition of low density polyethylene blends with vacuum gas oils:
Evolution of the gases, Polym Degrad Stab (2008), doi:10.1016/j.polymdegradstab.2008.07.019
ARTICLE IN PRESS
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Evolution of the gases, Polym Degrad Stab (2008), doi:10.1016/j.polymdegradstab.2008.07.019