ES2229423T5 - Polimerización en suspensión con alto contenido en sólidos - Google Patents
Polimerización en suspensión con alto contenido en sólidos Download PDFInfo
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- ES2229423T5 ES2229423T5 ES98113059.4T ES98113059T ES2229423T5 ES 2229423 T5 ES2229423 T5 ES 2229423T5 ES 98113059 T ES98113059 T ES 98113059T ES 2229423 T5 ES2229423 T5 ES 2229423T5
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- 239000007787 solid Substances 0.000 title claims abstract description 33
- 238000010557 suspension polymerization reaction Methods 0.000 title description 4
- 239000003085 diluting agent Substances 0.000 claims abstract description 29
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 230000006835 compression Effects 0.000 claims abstract description 4
- 238000007906 compression Methods 0.000 claims abstract description 4
- 239000000725 suspension Substances 0.000 claims description 40
- 229920000642 polymer Polymers 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 12
- 239000005977 Ethylene Substances 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 11
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 10
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical group CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 10
- 239000013067 intermediate product Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 239000012530 fluid Substances 0.000 claims description 6
- 239000001282 iso-butane Substances 0.000 claims description 5
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 abstract description 10
- 239000000178 monomer Substances 0.000 abstract description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002002 slurry Substances 0.000 abstract 3
- 238000000605 extraction Methods 0.000 description 43
- 239000000047 product Substances 0.000 description 16
- 230000007246 mechanism Effects 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- QWTDNUCVQCZILF-UHFFFAOYSA-N iso-pentane Natural products CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/005—Separating solid material from the gas/liquid stream
- B01J8/007—Separating solid material from the gas/liquid stream by sedimentation
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- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1812—Tubular reactors
- B01J19/1837—Loop-type reactors
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- 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
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/008—Feed or outlet control devices
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- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
- B01J8/003—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor in a downward flow
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- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/005—Separating solid material from the gas/liquid stream
- B01J8/0055—Separating solid material from the gas/liquid stream using cyclones
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- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/001—Removal of residual monomers by physical means
- C08F6/003—Removal of residual monomers by physical means from polymer solutions, suspensions, dispersions or emulsions without recovery of the polymer therefrom
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- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00004—Scale aspects
- B01J2219/00006—Large-scale industrial plants
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- Dispersion Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Treatment Of Sludge (AREA)
Description
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DESCRIPCION
Polimerizacion en suspension con alto contenido en solidos Antecedentes de la invencion
Esta invencion se refiere a la polimerizacion de monomeros oleffnicos en un diluyente Kquido.
Las polimerizaciones por adicion se llevan a cabo frecuentemente en un lfquido que es un disolvente del polfmero resultante. Cuando los polfmeros de etileno (lineales) de alta densidad llegaron a estar disponibles comercialmente en los anos 50, este fue el metodo utilizado. Pronto se descubrio que una forma mas eficaz de producir dichos polfmeros era llevar a cabo la polimerizacion en condiciones de suspension. Mas espedficamente, la tecnica de polimerizacion escogida fue la polimerizacion en suspension continua en un reactor tubular tipo lazo en el que el producto se extrafa mediante cangilones de deposito que funcionaban segun un principio de operacion discontinua para recuperar el producto. Esta tecnica ha disfrutado de un exito internacional con miles de millones de libras de polfmeros de etileno producidas anualmente de esta forma. Con este exito se ha considerado ventajoso construir un menor numero de reactores grandes, en contraposicion a un mayor numero de pequenos reactores para una capacidad de planta dada.
Los cangilones de deposito sin embargo, presentan dos problemas. En primer lugar, representan la imposicion de una tecnica de operacion discontinua sobre una base de un proceso continuo. Cada vez que un cangilon de deposito alcanza la etapa en la que se acumula o se inflama la suspension de polfmero acumulada, ello ocasiona una interferencia con el flujo de la suspension en el reactor tipo lazo, aguas arriba, y en el sistema de recuperacion, aguas abajo. Tambien el mecanismo de la valvula, esencial para sellar periodicamente los cangilones de deposito de la zona aguas arriba del reactor y el sistema de recuperacion aguas abajo, requiere mantenimiento frecuente debido a la dificultad para mantener un sello hermetico con las valvulas de gran diametro necesarias para sellar los cangilones.
En segundo lugar, a medida que los reactores se hacen mayores, se presentan problemas logfsticos en los cangilones de deposito. Si un diametro de tubena se dobla, el volumen del reactor sube cuatro veces. Sin embargo, debido a los mecanismos de valvula involucrados, el tamano de los cangilones de deposito no se puede incrementar mas facilmente. Por tanto, el numero de cangilones requeridos empieza a sobrepasar el espacio ffsico disponible.
A pesar de estas limitaciones, los cangilones de deposito han continuado teniendo que ser empleados donde los polfmeros olefrnicos se forman como una suspension en un diluyente lfquido. Esto es porque, a diferencia de las polimerizaciones en suspension a granel (esto es, en las que el monomero es el diluyente) donde se obtienen de forma rutinaria concentraciones de solidos mejores del 60%, las suspensiones de polfmero olefmico en un diluyente estan limitadas generalmente a no mas del 37 a 40 por ciento de solidos en peso. Por tanto, se ha crefdo que los cangilones de deposito son necesarios para dar un producto final en suspension a la salida de los cangilones de deposito mayor del 37-40 por ciento. Esto es porque, como su nombre implica, el deposito tiene lugar en los cangilones para asf incrementar la concentracion de solidos de la suspension finalmente recuperado como un producto en forma de suspension.
Otro factor que afecta al maximo practico de solidos en el reactor es la velocidad de circulacion, puesto que una mayor velocidad para un diametro de reactor dado permite mas solidos, dado que un factor limitante en la operacion es el ensuciamiento del reactor debido a la formacion de polfmero en el reactor.
El documento de patente EP A 0.432.555 muestra un proceso de polimerizacion, en el que la concentracion de solidos en volumen de la suspension de la reaccion de polimerizacion se optimiza utilizando un sistema de control espedfico. Esta referencia no dice nada sobre como se retira el producto del reactor.
El documento de patente norteamericana A 4.613.484 se refiere a un dispositivo para separar partfculas de polfmero solidas de una mezcla de polimerizacion en forma de suspension utilizando un cangilon de deposito. Igualmente, el documento de patente EP A 0.415.427 se refiere a un proceso de recuperacion de un polfmero utilizando un cangilon de deposito.
Resumen de la invencion
Es un objeto de esta invencion producir polfmeros oleffnicos como una suspension en un diluyente ffquido utilizando una extraccion de la suspension producto en continuo;
Es un objeto adicional de esta invencion proporcionar un proceso de polimerizacion de olefinas en suspension en un diluyente a una concentracion de solidos en el reactor, suficientemente alta como para hacer comercialmente viable la extraccion directa del producto en continuo.
Es un objeto adicional de esta invencion proporcionar un proceso de polimerizacion de olefinas en suspension en un diluyente a mayores velocidades de circulacion.
Es tambien un objeto adicional de esta invencion proporcionar un proceso de polimerizacion de olefinas en
suspension en un diluyente en una zona de reaccion mayor de 113,6 m3; y
Es aun otro objeto adicional de esta invencion proporcionar un dispositivo reactor tipo lazo que tiene una capacidad mayor de 113,6 m3 y que tiene un modo de extraccion en continuo.
De acuerdo con un aspecto de esta invencion, un proceso de polimerizacion de olefinas se lleva a cabo a una mayor 5 concentracion de solidos en el reactor mediante la retirada en continuo de la suspension producto.
De acuerdo con otro aspecto de esta invencion, se lleva a cabo un proceso de polimerizacion de olefinas en reactor tipo lazo operando a una velocidad de circulacion mayor para un diametro de tubena de reactor dado.
De acuerdo con otro aspecto de esta invencion, se proporciona un dispositivo de polimerizacion tipo lazo que tiene un apendice hueco alargado en un extremo aguas abajo de uno de los segmentos longitudinales del lazo, estando el 10 apendice hueco en comunicacion directa fluida con una lmea de destilacion subita calentada y estando asf adaptado para la eliminacion continua de la suspension producto.
Breve descripcion de los dibujos
En los dibujos, que forman parte de esta invencion, la Figura 1 es una vista esquematica en perspectiva de un reactor tipo lazo y un sistema de recuperacion de polfmero; la Figura 2 es una seccion transversal a lo largo la lmea 15 2-2 de la Figura 1 que muestra un apendice de extraccion en_continuo; la Figura 3 es una seccion transversal a lo
largo de la lmea 3-3 de la Figura 2 que muestra un dispositivo de valvula de corte en el ensamblaje de extraccion en continuo; la Figura 4 es una seccion transversal de una localizacion tangencial en el conjunto de extraccion en continuo; la Figura 5 es una vista lateral de un codo del reactor tipo lazo que muestra un cangilon de deposito y un ensamblaje de extraccion en continuo; la Figura 6 es una seccion transversal a lo largo de la lmea 6-6 de la Figura 5 20 que muestra la orientacion de dos de los ensamblajes de extraccion en continuo; la Figura 7 es una vista lateral que muestra otra orientacion para el ensamblaje de extraccion en continuo; la Figura 8 es una vista de la seccion transversal del mecanismo impulsor; la Figura 9 es una vista esquematica que muestra otra configuracion para los lazos en la que los segmentos superiores 14a son semicmculos de 180 grados en los que los segmentos verticales son al menos dos veces mas largos que los segmentos horizontales y la Figura 10 es una vista esquematica que 25 muestra el eje mas largo dispuesto horizontalmente.
Descripcion detallada de la invencion
Sorprendentemente, se ha encontrado que la extraccion en continuo de la suspension producto en una reaccion de polimerizacion de olefinas realizada en un reactor tipo lazo en presencia de un diluyente inerte permite la operacion del reactor a una concentracion de solidos mucho mayor. La produccion comercial de polfmeros predominantemente 30 de etileno en isobutano como diluyente, ha estado limitada generalmente a una concentracion maxima de solidos en el reactor de 37-40 por ciento en peso. Sin embargo, se ha encontrado que la extraccion en continuo permite incrementos significativos en la concentracion de solidos. Ademas, la extraccion en continuo ocasiona por sf misma, algun incremento adicional en el contenido en solidos en comparacion con el contenido en el reactor desde el cual se extrae el producto debido a la localizacion del apendice de extraccion en continuo que elimina selectivamente una 35 suspension desde un estrato en el que los solidos estan mas concentrados.
En toda esta solicitud, no se hace caso del peso de catalizador puesto que la productividad, particularmente con el oxido de cromo sobre sflice, es extremadamente alta.
Tambien sorprendentemente, se ha encontrado que se puede emplear una circulacion mas agresiva (con su correspondiente mayor concentracion en solidos). Efectivamente, con una circulacion mas agresiva en combinacion 40 con la extraccion en continuo, concentraciones de solidos mayores del 50 por ciento en peso se pueden eliminar del reactor mediante extraccion en continuo. Por ejemplo, la extraccion en continuo facilmente puede permitir operar a 5-6 puntos porcentuales por encima; esto es, el reactor se puede ajustar facilmente a incrementos de solidos del 10 por ciento; y la circulacion mas agresiva facilmente puede anadir otros 7-9 puntos porcentuales lo que situa al reactor por encima del 50 por ciento. Pero, debido a que la extraccion en continuo se posiciona para extraer 45 suspension desde un estrato en la corriente que tiene una concentracion de solidos mayor que la promedio, el producto realmente recuperado tiene una concentracion aproximadamente 3 puntos porcentuales (o mas) por encima del promedio de la suspension del reactor. Asf, la operacion puede acercarse a una concentracion de la suspension efectiva del 55 por ciento en peso o mas, esto es, un promedio de 52 por ciento en el reactor y la eliminacion de un componente que es efectivamente 55 por ciento (esto es, 3 puntos porcentuales) mas alta.
50 Se debe hacer enfasis en que en una operacion comercial, un incremento tan pequeno como de un punto porcentual en la concentracion de solidos es de la maxima importancia. Por lo tanto, pasar de un porcentaje promedio de 37-40 en la concentracion promedio de solidos en el reactor a casi 41 es importante; asf, pasar de mas de 50 es realmente notable.
La presente invencion es aplicable a la polimerizacion de olefinas en un reactor tipo lazo utilizando un diluyente tal 55 que produzca una suspension producto de polfmero y diluyente. La invencion es apropiada para la homopolimerizacion de etileno y la copolimerizacion de etileno y buteno, 1-penteno, 1-hexeno, 1-octeno o 1-deceno.
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Es especialmente preferido el etileno y de 0,01 a 10, preferiblemente de 0,01 a 5, lo mas preferiblemente de 0,1 a 4 por ciento en peso de una olefina superior sobre la base del peso total de etileno y comonomero. Alternativamente se puede utilizar suficiente comonomero para alcanzar las cantidades de incorporacion de comonomero en el polfmero, descritas anteriormente.
Diluyentes apropiados (a diferencia de disolventes o monomeros) se conocen bien en la tecnica e incluyen hidrocarburos que son inertes y lfquidos en las condiciones de reaccion. Hidrocarburos apropiados incluyen isobutano, propano, n-pentano, i-pentano, neopentano y n-hexano, siendo el isobutano especialmente preferido.
Catalizadores apropiados tambien se conocen bien en la tecnica. Particularmente apropiado es el oxido de cromo sobre un soporte como silica como se muestra en general, por ejemplo, por Hogan y Banks en el documento de patente estadounidense 2.285.721 (Marzo 1958), la descripcion del cual se incorpora aqu como referencia.
En referencia ahora a los dibujos, se muestra en la Figura 1 un reactor tipo lazo 10 que tiene segmentos verticales 12, segmentos horizontales superiores 14 y segmentos horizontales inferiores 16. Estos segmentos horizontales superiores e inferiores definen las zonas superior e inferior de flujo horizontal. El reactor se enfna por medio de dos cambiadores de calor tubulares formados por tubo 12 y camisa 18. Cada segmento esta conectado al siguiente segmento mediante un conector en curva suave o codo 20, proporcionando asf una trayectoria continua de flujo sustancialmente libre de obstrucciones internas. La mezcla de polimerizacion se hace circular por medio de un impulsor 22 (mostrado en la Figura 8) dirigido mediante un motor 24. El monomero, comonomero, si es el caso, y el diluyente se introducen a traves de las tubenas 26 y 28 respectivamente, las cuales pueden entrar en el reactor directamente por una o por una pluralidad de localizaciones o se pueden combinar con la tubena de recirculacion de diluyente condensado 30 como se muestra. El catalizador se introduce a traves de medios de introduccion del catalizador 32 que proporcionan una zona (localizacion) para la introduccion del catalizador. El apendice hueco alargado para la extraccion en continuo de una suspension producto intermedia se designa generalmente con el caracter de referencia 34. El mecanismo de extraccion en continuo 34 esta localizado en, o es contiguo al extremo aguas abajo de una de las secciones horizontales inferiores del reactor tipo lazo 16 y contiguo, o sobre un codo conector 20.
El apendice de extraccion en continuo se muestra en el extremo aguas abajo de un segmento horizontal inferior del reactor tipo lazo, que es la localizacion preferida. La localizacion esta en una region cerca del ultimo punto en el lazo donde el flujo cambia de sentido hacia arriba antes del punto de introduccion del catalizador para asf permitir al catalizador de nueva aportacion el maximo tiempo posible en el reactor antes de que pase al punto de extraccion.
Tambien, el segmento del reactor al cual esta unido el apendice de extraccion en continuo, puede ser de un diametro mayor para frenar el flujo y por lo tanto, permitir una estratificacion adicional del flujo con el fin de que el producto que se extrae pueda tener incluso una mayor concentracion de solidos.
La suspension producto intermedio retirada de manera continua se pasa mediante el conducto 36 a una camara de destilacion subita de alta presion 38. El conducto 36 incluye un conducto circundante 40 que esta provisto con un fluido caliente que proporciona calentamiento indirecto al material en suspension en el conducto de la tubena de destilacion subita 36. El diluyente vaporizado sale de la camara de destilacion subita 38 mediante el conducto 42 para un posterior procesamiento que incluye condensacion por intercambio de calor sencillo utilizando el condensador de reciclo 50, y vuelve al sistema, sin necesidad de compresion, mediante la lmea de reciclo del diluyente 30. El condensador de reciclo 50 puede utilizar cualquier fluido de intercambio de calor apropiado conocido en la tecnica en cualesquiera condiciones conocidas en la tecnica. El intervalo de temperatura para este fluido es de 4 a 54°C. Las partmulas de polfmero se retiran de la camara de destilacion subita de alta presion 38 mediante la tubena 44 para posterior procesamiento utilizando tecnicas conocidas en la tecnica. Preferiblemente se pasan a la camara de destilacion subita de baja presion 46 y despues se recuperan como polfmero producto mediante la tubena 48. El diluyente separado se pasa a traves del compresor 47 a la tubena 42. Este diseno de destilacion subita a alta presion se describe en general por Hanson y Sherk en la patente estadounidense 4.424.341 (3 de enero de 1984), incorporandose la divulgacion de la misma en el presente documento como referencia. Sorprendentemente, se ha encontrado que la extraccion en continuo no solo permite mas altas concentraciones de solidos aguas arriba en el reactor, sino que tambien permite una mejor operacion de la destilacion subita de alta presion, permitiendo asf que la mayona del diluyente retirado sea destilado y recirculado sin compresion. Efectivamente, de 70 a 90 por ciento del diluyente generalmente se puede recuperar de esta manera. Esto es debido a varios factores. El primero de todos, debido a que el flujo es continuo en vez de intermitente, los calentadores de la tubena de destilacion subita funcionan mejor. Tambien, la cafda de presion despues de la valvula de control proporcional que regula la velocidad del flujo en continuo fuera del reactor tiene una presion mas baja lo cual significa que cuando destila, la temperatura cae permitiendo un uso mas eficiente de los calentadores de la tubena de destilacion subita.
En referencia ahora a la Figura 2, se muestra el codo 20 con el mecanismo de extraccion 34 en mayor detalle. El mecanismo de extraccion en continuo comprende un cilindro de extraccion 52, una lmea de retirada de la suspension 54, una valvula de disparo de emergencia 55, una valvula proporcional accionada por motor 58 para regular el flujo y una lmea de drenaje 60. El reactor funciona “lleno de lfquido”. Debido al monomero disuelto, el lfquido tiene una ligera compresibilidad, permitiendo asf el control de presion de todo el sistema de lfquido con una
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valvula. La entrada de diluyente se mantema constante, utilizandose la valvula proporcional accionada por motor 58 para controlar la velocidad de retirada en continuo para mantener la presion total del reactor dentro de los puntos designados.
En referencia ahora a la Figura 3, que esta tomada a lo largo de la seccion de la lmea 3-3 de la Figura 2, se muestra con mayor detalle, la curva suave o el codo 20 al cual se ha asociado el mecanismo de extraccion en continuo 34, siendo asf el codo 20 un codo portador de apendice. Tal y como se muestra, el mecanismo comprende un cilindro de extraccion 52 unido, en este caso, en un angulo recto a una tangente a la superficie externa del codo. El cilindro saliente 52 es la tubena de retirada de la suspension 54. Colocada dentro del cilindro de extraccion 52 se encuentra una valvula de piston 62 que cumple dos funciones. Primero, proporciona un mecanismo de limpieza en profundidad sencillo y seguro para el cilindro de extraccion si este llegara a atascarse con polfmero. Segundo, puede servir como una sencilla y fiable valvula de corte para el ensamblaje completo de la extraccion en continuo.
La Figura 4 muestra una orientacion de la union preferida para el cilindro de extraccion 52, la cual esta unida tangencialmente a la curvatura del codo 20 y en un punto justo antes del giro ascendente del flujo de la suspension. Esta apertura es elfptica a la superficie interior. Se podna hacer un alargamiento adicional para mejorar la extraccion de solidos.
La Figura 5 muestra cuatro cosas. Primero, muestra una orientacion angular del cilindro de extraccion 52. El cilindro de extraccion se muestra en un angulo, alfa, al plano que es (1) perpendicular a la lmea central del segmento horizontal 16 y (2) esta localizada en el extremo aguas abajo del segmento horizontal 16. El angulo con este plano esta tomado en la direccion aguas abajo desde el plano. El vertice del angulo es el punto central del radio del codo tal y como se muestra en la Figura 5. El plano se puede describir como el plano transversal del segmento horizontal. El angulo representado aqm es de aproximadamente 24 grados. Segundo, muestra una pluralidad de apendices de extraccion en continuo, 34 y 34a. Tercero, muestra un apendice, 34 orientado sobre un plano vertical a la lmea central del segmento inferior 16, y el otro, 34a, localizado en un angulo a un plano como se mostrara con mas detalle en la Figura 6. Finalmente, muestra la combinacion de apendices de extraccion en continuo 34 y un cangilon de deposito convencional 64 para la eliminacion en discontinuo, si se desea.
Como se puede ver de los tamanos relativos, los cilindros de extraccion continua son mucho menores que los cangilones de deposito convencionales. Tres apendices de extraccion en continuo, de 50,8 mm de diametro interno pueden eliminar tanta suspension producto como 14 cangilones de deposito de 203 mm de diametro interno. Esto es significativo debido a que con los grandes reactores tipo lazo comerciales actuales de 56,8-68,2 m3 de capacidad, se requieren seis cangilones de deposito de 203 mm. No es deseable incrementar el tamano de los cangilones de deposito debido a la dificultad para hacer valvulas fiables de mayores diametros. Como se aprecio previamente, doblando el diametro de la tubena, se cuadruplica el volumen y sencillamente no hay espacio suficiente para que cangilones de deposito cuatro veces mayores que los actuales se posicionen facilmente. Por lo tanto, la invencion hace factible la operacion de mayores reactores mas eficientes. Reactores de 113,6 m3 o mayores son posibles gracias a esta invencion. Generalmente los cilindros de extraccion en continuo tendran un diametro interno nominal en el rango de 25,4 mm a menos de 203 mm. Preferiblemente tendran aproximadamente 50,8-76,2 mm de diametro interno.
La Figura 6 se toma a lo largo de la seccion de la lmea 6-6 de la Figura 5 y muestra el cilindro de extraccion 34a unido a un lugar que esta orientado en un angulo, beta, a un plano vertical que contiene la lmea central del reactor. Este plano se puede denominar como plano central vertical del reactor. Este angulo se puede tomar bien desde el lado del plano o bien desde ambos lados si no es cero. El vertice del angulo se localiza en la lmea central del reactor. El angulo esta contenido en un plano perpendicular a la lmea central del reactor tal como se muestra en la Figura 6.
Se observa que aqm hay tres conceptos de orientacion. El primero es la orientacion de la union, esto es, tangencial como en la Figura 4 y perpendicular como en las Figuras 2 o 7 o cualquier angulo entre estos dos lfmites de 0 a 90 grados. El segundo, es la orientacion relativa a la distancia de la curva del codo a la union, esta representada por el angulo alfa (Figura 5). Este puede ser cualquiera de 0 a 60 grados pero es preferiblemente de 0 a 40 grados, mas preferiblemente de 0 a 20 grados. El tercero es el angulo, beta, desde el plano central del segmento longitudinal (Figura 6). Este angulo puede ser de 0 a 60 grados, preferiblemente de 0 a 45 grados, mas preferiblemente de 0 a 20 grados.
La Figura 7 muestra una realizacion en la que el cilindro de extraccion en continuo 52 tiene una orientacion de la union perpendicular, una orientacion alfa de 0 (inherente al mismo ya que esta en el extremo, pero todavfa, sobre la seccion recta), y una orientacion beta de 0, es decir, esta justo sobre el plano vertical de la lmea central del segmento horizontal inferior 16.
La Figura 8 muestra en detalle el mecanismo impulsor 22 para el movimiento continuo de la suspension a lo largo de su trayectoria de flujo. Tal como se puede ver en esta realizacion, el impulsor esta en una seccion ligeramente aumentada de la tubena que sirve como zona de propulsion para los reactantes circulantes. Preferiblemente, el sistema se opera de modo que genere una presion diferencial de al menos 0,124 MPa de presion manometrica, preferiblemente al menos 0,138 MPa de presion manometrica, mas preferiblemente al menos 0,152 MPa de presion
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manometrica entre los extremos aguas arriba y aguas abajo de la zona de propulsion en un reactor de diametro nominal de 61 cm con una longitud total de trayectoria de flujo de aproximadamente 290 m utilizando isobutano para producir predominantemente poKmeros de etileno. Tanto como 0,345 MPa de presion manometrica o mas es posible. Esto se puede hacer controlando la velocidad de rotacion del impulsor, reduciendo la holgura entre el impulsor y la pared interior de la carcasa de la bomba o utilizando un diseno del impulsor mas agresivo tal como se conoce en la tecnica. Este mayor diferencial de presion tambien se puede producir mediante el uso de al menos, una bomba adicional.
Generalmente, el sistema se hace funcionar de tal manera que se genera una presion diferencial, expresada como una perdida de presion por unidad de longitud del reactor, de al menos 0,23, generalmente de 0,23 a 0,49 mm de cafda de presion por mm de longitud del reactor para un reactor de diametro nominal de 610 mm. Preferiblemente, esta cafda de presion por unidad de longitud es de 0,29 a 0,36 para un reactor de 610 mm de diametro. Para diametros mayores, se necesita una mayor velocidad de la suspension y una mayor cafda de presion por unidad de longitud del reactor. Esto supone que la densidad de la suspension sea generalmente de aproximadamente 0,5-0,6 g/cm3.
En referencia ahora a la Figura 9, los segmentos superiores se muestran como semidrculos de 180 grados, que es la configuracion preferida. Los segmentos verticales tienen al menos dos veces, generalmente alrededor de siete a ocho veces, la longitud de los segmentos horizontales. Por ejemplo, la trayectoria de flujo vertical puede ser de 57,968,6 m y los segmentos horizontales pueden tener una longitud de trayectoria de flujo de 7,6-9,1 m. Se puede emplear cualquier numero de lazos, ademas de los cuatro descritos en la presente memoria y los ocho representados en la Figura 1, pero generalmente se utilizan cuatro o seis. La referencia al diametro nominal de 61 cm quiere decir un diametro interno de aproximadamente 6,68 m. La longitud del flujo generalmente es mayor de 152 m, generalmente mayor de 274 m, siendo bastante satisfactorio aproximadamente de 287 a 411 m.
Las bombas comerciales para usos tales como la circulacion de reactantes en un reactor tipo lazo cerrado se ensayan de manera rutinaria por sus fabricantes y se determinan facil y rutinariamente las presiones necesarias para evitar la cavitacion.
Ejemplos
Se empleo un reactor de polimerizacion de cuatro tramos verticales utilizando una bomba impulsora Lawrence Pumps Inc D51795/81 de 660 mm en una carcasa M51879/FAB, para polimerizar etileno y 1-hexeno. Esta bomba se comparo con una bomba de 610 mm, la cual proporcionaba una circulacion menos agresiva (20,1 cm de perdida de carga frente a 29,9 cm). Esto se comparo a continuacion, con la misma circulacion mas agresiva y un ensamblaje de extraccion en continuo del tipo mostrado por el sfmbolo de referencia 34 de la Figura 5. Los resultados se muestran a continuacion.
- TABLA DE DATOS
- Descripcion
- 24 en bomba 26 en bomba 26 en bomba + CTO
- Fecha de realizacion
- 4-9 de Octubre de 1994 24-28 de Mayo de 1995 15-18 de Noviembre de 1996
- Concentracion Promedio de Solidos en el Reactor, % en peso
- 39 45 53
- Velocidad de Produccion de polfmero, g/h
- 18,2 18,5 18,1
- Potencia de la Bomba de Circulacion del Reactor, Kw
- 430 691 753
- Diferencial de Presion de la Bomba de Circulacion, KPa
- 98,7 154,6 163,5
- Cabeza de Bomba de Circulacion, m
- 18,8 28,2 28,2
- Velocidad de Flujo de la Suspension en el Reactor, mGPM
- 39 46 45
- Densidad de la Suspension en el Reactor, g/m3
- 0,534 0,558 0,592
- Temperatura del Reactor, °C
- 102,0 103,5 102,8
- Concentracion de etileno, % en peso
- 4,43 3,67 4,9
- Concentracion de 1-Hexeno, % en peso
- 0,22 0,17 0,14
- Coeficiente de Transferencia de Calor del Reactor
- 270 262 241
- Diametro Interior del Reactor, mm
- 560,388 560,388 560,388
- Volumen del Reactor, m3
- 70,81 70,81 70,81
- Longitud del Reactor, m
- 287 287 287
- Cafda de Presion por mm del Reactor, mm/mm
- 0,217 0,322 0,322
Aunque esta invencion se ha descrito en detalle con el proposito de ilustracion, no se debe inferir que este limitada al mismo, sino que se pretende que cubra todas las opciones dentro del esprntu y el alcance de la misma.
Claims (6)
- 5101520253035REIVINDICACIONES1. Un proceso de polimerizacion que comprende:en una zona de reaccion tipo lazo, homopolimerizar etileno o copolimerizar etileno y 1-buteno, 1-penteno, 1- hexeno, 1-octeno o 1-deceno en un diluyente Kquido para producir una suspension fluida que comprende un diluyente Kquido y partfculas solidas de poKmero olefrnico;mantener una concentracion de dichas partfculas solidas de poKmero olefrnico en dicha suspension, en dicha zona, mayor del 50 por ciento en peso en base al peso de dichas partfculas de polfmero y el peso de dicho diluyente lfquido; yretirar de manera continua una suspension que tiene un incremento en concentracion de solidos en comparacion con dicha suspension en dicha zona, comprendiendo la suspension asf retirada un diluyente lfquido retirado y partfculas solidas de polfmero retiradas como un producto intermedio de dicho proceso,en donde dicha suspension se retira de forma continua de un area proxima al ultimo punto en dicha zona de reaccion del tipo lazo donde el flujo cambia de sentido hacia arriba antes de una zona de introduccion del catalizador, yen donde dicho producto intermedio de dicho proceso se hace pasar de forma continua a traves de una zona de calentamiento en donde dicho producto intermedio se calienta para producir un producto intermedio calentado ya continuacion dicho producto intermedio calentado se expone a una cafda de presion en una zona de destilacion subita de alta presion, siendo calentado dicho producto intermedio calentado hasta un grado tal que una porcion principal de dicho diluyente lfquido retirado se evapora y asf se separa de dichas partfculas solidas de polfmero retiradas; siendo a continuacion el diluyente lfquido extrafdo, asf separado, condensado para recircular, sin compresion alguna, mediante intercambio de calor con un fluido que tiene una temperatura en el intervalo de 4 a 54°C (40 a 130 grados F).
- 2. El proceso de la reivindicacion 1, en el que dicho proceso comprende copolimerizar etileno y 0,01-5 por ciento en peso de hexeno en base al peso total de dicho etileno y dicho hexeno, y en el que dicho diluyente lfquido es isobutano.
- 3. El proceso de la reivindicacion 1 o la reivindicacion 2, en donde se mantiene un diferencial de presion de por lo menos 0,124 MPa de presion manometrica 818 (psig) en una zona de propulsion para que dicha suspension circule a traves de dicha zona de reaccion.
- 4. El proceso de la reivindicacion 1 o la reivindicacion 2, en el que se mantiene un diferencial de presion mayor de 0,07 mm/mm (0,07 pies/pie) de la longitud de la trayectoria de flujo del reactor en una zona de propulsion, en particular, en el que dicho diferencial esta en el intervalo de 0,07 a 0,15 mm/mm (0.07 a 0,15 pies/pie) por mm de dicha longitud de la trayectoria de flujo del reactor.
- 5. El proceso de cualquiera de las reivindicaciones precedentes, en el que dicha zona de reaccion se mantiene llena de lfquido.
- 6. El proceso de cualquiera de las reivindicaciones precedentes, en el que dicha zona de reaccion tiene un volumen mayor de 75,7 m3 (20.000 galones), preferiblemente mayor de 113,6 m3(30.000 galones).
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1997
- 1997-07-15 US US08/893,200 patent/US6239235B1/en not_active Expired - Lifetime
-
1998
- 1998-06-29 SG SG1998001542A patent/SG72838A1/en unknown
- 1998-07-07 KR KR1019980027296A patent/KR100513212B1/ko not_active Expired - Lifetime
- 1998-07-09 ZA ZA986097A patent/ZA986097B/xx unknown
- 1998-07-10 JP JP10195888A patent/JPH1180210A/ja active Pending
- 1998-07-14 CN CNB981160484A patent/CN1205237C/zh not_active Expired - Lifetime
- 1998-07-14 TW TW087111414A patent/TW515808B/zh not_active IP Right Cessation
- 1998-07-14 TR TR1998/01363A patent/TR199801363A2/xx unknown
- 1998-07-14 ES ES98113059.4T patent/ES2229423T5/es not_active Expired - Lifetime
- 1998-07-14 RU RU98113720/04A patent/RU2221812C2/ru active
- 1998-07-14 EP EP98113059.4A patent/EP0891990B2/en not_active Expired - Lifetime
- 1998-07-14 HU HU9801569A patent/HUP9801569A3/hu unknown
- 1998-07-14 DE DE69826190T patent/DE69826190D1/de not_active Expired - Lifetime
- 1998-07-14 YU YU29398A patent/YU49229B/sh unknown
- 1998-07-14 DK DK98113059T patent/DK0891990T3/da active
- 1998-07-14 AT AT98113059T patent/ATE276282T1/de not_active IP Right Cessation
- 1998-07-15 NO NO19983277A patent/NO319091B1/no not_active IP Right Cessation
- 1998-07-15 CA CA002243250A patent/CA2243250C/en not_active Expired - Lifetime
- 1998-12-16 BR BR9802445A patent/BR9802445A/pt not_active IP Right Cessation
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2002
- 2002-06-20 US US10/177,615 patent/US20030027944A1/en not_active Abandoned
- 2002-06-20 US US10/177,624 patent/US20030012705A1/en not_active Abandoned
- 2002-06-20 US US10/176,201 patent/US20020187081A1/en not_active Abandoned
- 2002-06-20 US US10/176,204 patent/US20030023010A1/en not_active Abandoned
- 2002-06-20 US US10/176,289 patent/US6806324B2/en not_active Expired - Lifetime
- 2002-06-20 US US10/176,247 patent/US6743869B2/en not_active Expired - Lifetime
- 2002-08-26 US US10/228,833 patent/US20030050409A1/en not_active Abandoned
- 2002-11-20 US US10/301,281 patent/US20030092856A1/en not_active Abandoned
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2004
- 2004-05-19 US US10/849,393 patent/US20040192860A1/en not_active Abandoned
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