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ES2579352T3 - Producción simultánea de componentes de aceite de base y de combustible a partir de materias primas renovables - Google Patents

Producción simultánea de componentes de aceite de base y de combustible a partir de materias primas renovables Download PDF

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Publication number
ES2579352T3
ES2579352T3 ES12795014.5T ES12795014T ES2579352T3 ES 2579352 T3 ES2579352 T3 ES 2579352T3 ES 12795014 T ES12795014 T ES 12795014T ES 2579352 T3 ES2579352 T3 ES 2579352T3
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Prior art keywords
reaction
base oil
ketonization
metal
eniso3405
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Mika Kettunen
Jukka Myllyoja
Rami Piilola
Göran SANDSTRÖM
Pekka Aalto
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Neste Oyj
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Neste Oyj
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
    • C11C3/123—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation using catalysts based principally on nickel or derivates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • B01J27/051—Molybdenum
    • B01J27/0515—Molybdenum with iron group metals or platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B01J23/04—Alkali metals
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
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    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
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Abstract

Un método para la producción simultánea de componentes adecuados para la producción de componentes de aceite de base y de combustible, que comprende las etapas de: a) introducir con un caudal de 0,1 a 10 h-1 una materia prima que comprende ácidos grasos y/o ésteres de ácidos grasos en una zona de reacción que tiene un intervalo de temperatura de 200 a 450 ºC y b) someter dicha materia prima a una reacción de cetonización en dicha zona de reacción a una presión de hidrógeno de menos de 10 MPa, en presencia de un sistema de catalizador doble configurado para realizar una reacción de cetonización y una reacción de hidrotratamiento, sistema de catalizador que comprende un catalizador de cetonización de óxido metálico en el que el metal se selecciona del grupo que consiste en Na, Mg, K, Ca, Sc, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr, Ti, Y, Zr, Mo, Rh, Cd, Sn, La, Pb, Bi, Ti, V y otros metales de tierras raras y cualquier combinación de los mismos; y un catalizador de hidrotratamiento metálico en el que el metal se selecciona del grupo que consiste en Fe, Pd, Pt, Ni, Mo, Co, Ru, Rh, W y cualquier combinación de los mismos, y c) obtener cetonas a partir de dicha reacción de cetonización, además de hidrocarburos lineales, a partir de dichos ácidos grasos y/o ésteres de ácidos grasos.

Description

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ENISO3405
FBP ºC 320
ASTMD7346 M
Punto de fluidez ºC 15
ASTMD7039
Azufre mg / kg 11,4
ASTMD976
Índice de cetano 75,4
Los resultados muestran que se obtienen excelentes componentes de aceite de base a partir de una mezcla de ácidos grasos (ácidos grasos de aceite de palma) y el material principalmente triglicerídico (aceite de palma). Los componentes de aceite de base se obtienen sin sacrificar la calidad de los componentes de combustible.
5
Ejemplo 4
El aceite de palma (100 %) se sometió a un proceso de cetonización e hidrotratamiento combinado. El proceso se llevó a cabo en presencia de un sistema de catalizador doble K2O/TiO2NiMo sulfurado preparado como en el
10 Ejemplo 1. La proporción entre K2O/TiO2 y NiMo sobre el soporte de alúmina era de 50:50 % en peso. Las condiciones del proceso fueron las siguientes
− Temperatura de 365 ºC, − Presión de 4 MPa
15 − Proporción entre hidrógeno e hidrocarburo (H2/HC) de 500 NI/I y − Velocidad espacial horaria en peso (WHSV) de 1,0 1/h.
Los rendimientos de la distribución de hidrocarburos y los rendimientos de agua se presentan en la Tabla 8.
20 Tabla 8. Distribución del producto
Gas + H2O
Gasolina Diésel Aceite de base
C14
C510 C1123 ≥C24
15,2
0,3 80,2 4,3
El producto obtenido se destiló a presión reducida en dos fracciones separadas, y se analizó. Las propiedades de los componentes del aceite de base y de los componentes de la fracción de combustible producidos se presentan en las Tablas 9 y 10.
Tabla 9. Componente de aceite de base (componente lubricante) del proceso, antes de la isomerización
ENISO3104
Viscosidad 40 ºC mm2/s 27,69
ENISO3104
Viscosidad 80 ºC mm2/s 9,058
ENISO3104
Viscosidad 100 ºC mm2/s 6,054
ASTMD2270
VI 175
ASTMD7346 M
Punto de fluidez ºC >45ºC
Tabla 10. Componente de combustible (diésel, queroseno, nafta) del proceso, antes de la isomerización
ENISO12185
Densidad kg/m3 784,6
NM473
Punto de turbidez ºC 19,6
ENISO3104
Viscosidad 40 ºC mm2/s 3,324
ENISO4264
Índice de cetano >>56,5
ENISO3405
IBP ºC 266,4
ENISO3405
5 ºC 280
ENISO3405
10 ºC 281,5
ENISO3405
15 ºC 282,9
ENISO3405
20 ºC 283,8
ENISO3405
30 ºC 285,4
ENISO3405
40 ºC 287
ENISO3405
50 ºC 288,8
ENISO3405
60 ºC 290,7
ENISO3405
70 ºC 293,2
ENISO3405
80 ºC 296,4
ENISO3405
85 ºC 298,6
ENISO3405
90 ºC 301,7
ENISO3405
95 ºC na
ENISO3405
FBP ºC 320,9
ASTMD7346 M
Punto de fluidez ºC 18
ASTMD7039
Azufre mg/kg <2
ASTMD976
Índice de cetano 76
13
imagen12
imagen13
imagen14

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