EP1340070A1 - Methode d'analyse par chromatographie en ligne pour la polymerisation d'olefines - Google Patents

Methode d'analyse par chromatographie en ligne pour la polymerisation d'olefines

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Publication number
EP1340070A1
EP1340070A1 EP01990632A EP01990632A EP1340070A1 EP 1340070 A1 EP1340070 A1 EP 1340070A1 EP 01990632 A EP01990632 A EP 01990632A EP 01990632 A EP01990632 A EP 01990632A EP 1340070 A1 EP1340070 A1 EP 1340070A1
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EP
European Patent Office
Prior art keywords
ppm
weight
nitrogen
hydrogen
less
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP01990632A
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German (de)
French (fr)
Inventor
Eric Cassisa
Marc Herzog
Christophe Ordan
Myung J. Shin
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PetroIneos Europe Ltd
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BP Chemicals Ltd
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Application filed by BP Chemicals Ltd filed Critical BP Chemicals Ltd
Priority to EP01990632A priority Critical patent/EP1340070A1/en
Publication of EP1340070A1 publication Critical patent/EP1340070A1/en
Withdrawn legal-status Critical Current

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/26—Conditioning of the fluid carrier; Flow patterns
    • G01N30/28—Control of physical parameters of the fluid carrier
    • G01N30/34—Control of physical parameters of the fluid carrier of fluid composition, e.g. gradient
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N2030/022—Column chromatography characterised by the kind of separation mechanism
    • G01N2030/025—Gas chromatography
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/901—Monomer polymerized in vapor state in presence of transition metal containing catalyst
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/21—Hydrocarbon
    • Y10T436/214—Acyclic [e.g., methane, octane, isoparaffin, etc.]
    • Y10T436/216—Unsaturated [e.g., ethylene, diene, etc.]

Definitions

  • the present invention relates to an improvement in the method of analysis by on-line gas chromatography of an essentially gaseous phase originating from an industrial olefin polymerization workshop.
  • the present invention relates to a method of in-line gas chromatographic analysis of an essentially gaseous phase originating from an industrial olefin polymerization workshop, the said chromatographic analysis being carried out by means of carrier gases essentially comprising hydrogen and / or nitrogen, characterized in that the oxygen and water content of the hydrogen and nitrogen is less than 5 ppm by weight, preferably less than 1 ppm by weight.
  • the polymerization of olefins is preferably carried out in the gas phase, preferably by means of a fluidized bed reactor.
  • the Applicant has found that the reliability thus obtained according to the present invention was also accompanied by better control of the polymerization of olefins in the gas phase in an industrial fluidized bed reactor, and in particular that this made it possible to prevent and advantageously avoid the risks of agglomeration (crusts, leaves, etc.) well known to those skilled in the art.
  • the oxygen and water content of hydrogen and nitrogen is less than 5 ppm by weight, preferably less than 1 ppm by weight.
  • the oxygen content of the hydrogen is less than 0.7 ppm by weight, more preferably less than 0.3 ppm by weight.
  • the water content of the hydrogen is less than 0.5 ppm by weight, more preferably less than 0.1 ppm by weight.
  • the oxygen content of the nitrogen is less than 0.5 ppm by weight, more preferably less than 0.1 ppm by weight.
  • the water content of the nitrogen is less than 0.5 ppm by weight, more preferably less than 0.05 ppm by weight.
  • the respective CO and CO 2 content of the hydrogen is less than 5 ppm by weight, preferably less than 1 ppm by weight, preferably less than 0.7 ppm by weight, more preferably less than 0.3 ppm weight.
  • the respective CO and CO 2 content of the nitrogen is less than 5 ppm by weight, preferably less than 1 ppm by weight, preferably less than 0.5 ppm by weight, more preferably less than 0.1 ppm weight.
  • the impurities present in the carrier gases can be measured by any suitable method. By way of example, mention will be made of that using analyzers comprising probes based on aluminum oxide.
  • This improved chromatographic analysis is particularly important because its increased reliability and efficiency now allow it, when used directly in industrial workshops, to instantly consider corrective operating measures in the event of deviation from the analysis values obtained.
  • the present invention also relates to a process for the continuous production of polymer in an industrial workshop comprising an olefin polymerization reactor in the presence of a catalytic polymerization system, process during which at least one operating parameter of the workshop by means of an analysis by online chromatography of a phase essentially gas from the said industrial workshop, the said chromatographic analysis being carried out by means of carrier gases essentially comprising hydrogen and / or nitrogen, characterized in that the oxygen and water content of the hydrogen and l nitrogen is less than 5 ppm by weight, preferably less than 1 ppm by weight.
  • the polymerization of olefins is preferably carried out in the gas phase, preferably by means of a fluidized bed reactor.
  • the catalytic system comprises an organoaluminium compound, preferably an alkylaluminium compound such as triethylaluminium or triisobutylaluminium.
  • SBR butadiene polymer copolymerized with styrene
  • ABS acrylonitrile, butadiene and styrene polymer
  • nitrile butadiene polymer copolymerized with acrylonitrile
  • butyl isobutylene polymer copolymerized with isoprene
  • EPDM etylene polymer copolymerized with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene norborene
  • copolymer of ethylene and vinyltrimethoxy silane copolymer of ethylene and of one or more compounds chosen from Pacrylonitrile, esters of maleic acid, vinyl acetate, esters of acrylic and methacrylic acid and their counterparts.
  • polymers which are preferably polyolefins, in particular copolymers of ethylene and / or propylene and / or butene.
  • the preferred alpha-olefins which are used in combination with ethylene and / or propylene and / or butene are those having 4 to 8 carbon atoms.
  • the invention applies to the production of polyethylene, for example linear low density polyethylene (LLDPE) based for example on copolymers of ethylene with 1-butene, 4-methylpentene or hexene, or high density polyethylene (HDPE) based for example on ethylene homopolymers or ethylene copolymers with low proportions of higher alpha olefins, for example 1-butene, 1-pentene, hexene or 4-methyl-1-pentene.
  • LLDPE linear low density polyethylene
  • HDPE high density polyethylene
  • the present invention relates to the production of polyethylene powder continuously in an industrial workshop comprising a gas phase polymerization reactor of the vertical fluidized bed reactor type.
  • this polymerization is carried out at an absolute pressure between 0.5 and 6 MPa and at a temperature between 60 ° C and 130 ° C.
  • the polymerization temperature is preferably between 75 and 100 ° C. and for HDPE it is generally between 80 and 110 ° C. depending on the activity of the catalyst used and the properties desired. polymer.
  • the continuous polymerization is carried out in a vertical fluidized bed reactor in accordance with what is described in (patent applications) EP-0 855 411. FR No. 2,207,145 or FRNo. 2335526.
  • the present invention therefore applies to workshops of industrial size, namely, by way of example, to fluidized bed polymerization reactors whose annual polymer production is at least one hundred thousand tonnes, preferably at least two hundred thousand tonnes.
  • this polymerization is carried out in the presence of a catalytic system of the Ziegler-Natta type which generally consists of a solid catalyst essentially comprising a compound of a transition metal and a cocatalyst comprising an organic compound of a metal (by example, an organometallic compound, for example an alkylaluminum compound).
  • a catalytic system of the Ziegler-Natta type which generally consists of a solid catalyst essentially comprising a compound of a transition metal and a cocatalyst comprising an organic compound of a metal (by example, an organometallic compound, for example an alkylaluminum compound).
  • High activity catalytic systems of this type generally include a solid catalyst which consists essentially of transition metal, magnesium and halogen atoms.
  • metallocene type catalysts as well as complex iron catalysts. and / or cobalt, for example those described in WO98 / 27124 or in the application filed under the number WOGB98 / 2638. It is also possible to use catalysts based on chromium oxide supported on a refractory oxide. The catalysts can be used directly or in the form of prepolymers prepared beforehand during a prepolymerization step.

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  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Polymerisation Methods In General (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne une amélioration de la méthode d'analyse par chromatographie en phase gazeuse en ligne d'une phase essentiellement gazeuse provenant d'un atelier industriel de polymérisation d'oléfines.

Description

Méthode d'analyse par chromato raphie en ligne pour la polymérisation d'oléfines On-line chromatographic analysis method for the polymerization of olefins
La présente invention concerne une amélioration de la méthode d'analyse par chromatographie en phase gazeuse en ligne d'une phase essentiellement gazeuse provenant d'un atelier industriel de polymérisation d'oléfines.The present invention relates to an improvement in the method of analysis by on-line gas chromatography of an essentially gaseous phase originating from an industrial olefin polymerization workshop.
La littérature décrit des méthodes d'analyse par chromatographie. A titre d'exemple, on citera BOMBAUGH Karl J. Chromatography, Gas and Liquid. MacKetta Encyclopedia of Chemical Processing and Design. 1979, Nol. 8, pages 270-285.The literature describes methods of analysis by chromatography. Examples include BOMBAUGH Karl J. Chromatography, Gas and Liquid. MacKetta Encyclopedia of Chemical Processing and Design. 1979, Nol. 8, pages 270-285.
Le problème majeur rencontré avec ces méthodes connues réside dans la difficulté de mise en oeuvre de la méthode en ligne à l'échelle industrielle ainsi que sur la fiabilité des analyses résultantes au cours du temps.The major problem encountered with these known methods lies in the difficulty of implementing the online method on an industrial scale as well as on the reliability of the resulting analyzes over time.
Ainsi, à titre d'exemple, il est fréquent de devoir affronter des dérives des analyses de la phase gaz dues en partie à des blocages partiels des lignes d'analyse par chromatographie utilisées sur les ateliers industriels de production de polyéthylène en phase gaz dans un réacteur à lit fluidisé.Thus, by way of example, it is frequent to have to deal with drifts in the analyzes of the gas phase due in part to partial blockages of the analysis lines by chromatography used on industrial workshops for the production of polyethylene in the gas phase in a fluidized bed reactor.
La présente invention concerne une méthode d'analyse par chromatographie en phase gazeuse en ligne d'une phase essentiellement gazeuse provenant d'un atelier industriel de polymérisation d'oléfines, la dite analyse chromatographique étant effectuée au moyen de gaz vecteurs comprenant essentiellement de l'hydrogène et/ou de l'azote, caractérisé en ce que la teneur en oxygène et en eau de l'hydrogène et de l'azote est inférieure à 5 ppm poids, de préférence inférieure à 1 ppm poids. La polymérisation d'oléfines est de préférence effectuée en phase gazeuse, de préférence au moyen d'un réacteur à lit fluidisé La Demanderesse a trouvé de manière totalement inattendue que les problèmes susmentionnés liés aux analyses chromatographiques en ligne sur les ateliers industriels pouvaient être résolus en contrôlant sévèrement la teneur en eau et en oxygène de l'hydrogène et de l'azote qui servent de gaz vecteurs dans ces analyses chromatographiques.The present invention relates to a method of in-line gas chromatographic analysis of an essentially gaseous phase originating from an industrial olefin polymerization workshop, the said chromatographic analysis being carried out by means of carrier gases essentially comprising hydrogen and / or nitrogen, characterized in that the oxygen and water content of the hydrogen and nitrogen is less than 5 ppm by weight, preferably less than 1 ppm by weight. The polymerization of olefins is preferably carried out in the gas phase, preferably by means of a fluidized bed reactor The Applicant has unexpectedly found that the above-mentioned problems associated with on-line chromatographic analyzes in industrial workshops can be resolved by severely controlling the water and oxygen content of the hydrogen and nitrogen which serve as carrier gases in these chromatographic analyzes.
De plus, la Demanderesse a trouvé que la fiabilité ainsi obtenue selon la présente invention était également accompagnée d'un meilleur contrôle de la polymérisation d'oléfines en phase gazeuse dans un réacteur à lit fluidisé industriel, et en particulier que cela permettait de prévenir et d'éviter avantageusement les risques d'agglomération (croûtes, feuilles, etc ..) bien connus de l'homme de l'art.In addition, the Applicant has found that the reliability thus obtained according to the present invention was also accompanied by better control of the polymerization of olefins in the gas phase in an industrial fluidized bed reactor, and in particular that this made it possible to prevent and advantageously avoid the risks of agglomeration (crusts, leaves, etc.) well known to those skilled in the art.
Selon la présente invention, la teneur en oxygène et en eau de l'hydrogène et de l'azote est inférieure à 5 ppm poids, de préférence inférieure à 1 ppm poids. De préférence, la teneur en oxygène de l'hydrogène est inférieure à 0,7 ppm poids, plus préférentiellement inférieure à 0,3 ppm poids. De préférence, la teneur en eau de l'hydrogène est inférieure à 0,5 ppm poids, plus préférentiellement inférieure à 0,1 ppm poids. De préférence, la teneur en oxygène de l'azote est inférieure à 0,5 ppm poids, plus préférentiellement inférieure à 0,1 ppm poids. De préférence, la teneur en eau de l'azote est inférieure à 0,5 ppm poids, plus préférentiellement inférieure à 0,05 ppm poids.According to the present invention, the oxygen and water content of hydrogen and nitrogen is less than 5 ppm by weight, preferably less than 1 ppm by weight. Preferably, the oxygen content of the hydrogen is less than 0.7 ppm by weight, more preferably less than 0.3 ppm by weight. Preferably, the water content of the hydrogen is less than 0.5 ppm by weight, more preferably less than 0.1 ppm by weight. Preferably, the oxygen content of the nitrogen is less than 0.5 ppm by weight, more preferably less than 0.1 ppm by weight. Preferably, the water content of the nitrogen is less than 0.5 ppm by weight, more preferably less than 0.05 ppm by weight.
Il est également préféré selon la présente invention de veiller à ce que la teneur en CO et en CO2 de l'azote et de l'hydrogène soit également bien contrôlée. Ainsi, de préférence, la teneur respective en CO et en CO2 de l'hydrogène est inférieure à 5 ppm poids, de préférence inférieure à 1 ppm poids, de préférence inférieure à 0,7 ppm poids, plus préférentiellement inférieure à 0,3 ppm poids. Ainsi, de préférence, la teneur respective en CO et en CO2 de l'azote est inférieure à 5 ppm poids, de préférence inférieure à 1 ppm poids, de préférence inférieure à 0,5 ppm poids, plus préférentiellement inférieure à 0,1 ppm poids. Les impuretés présentes dans les gaz vecteurs peuvent être mesurées au moyen de toute méthode appropriée. On citera, à titre d'exemple, celle utilisant des analyseurs comprenant des sondes à base d'oxyde d'aluminium.It is also preferred according to the present invention to ensure that the CO and CO 2 content of nitrogen and hydrogen is also well controlled. Thus, preferably, the respective CO and CO 2 content of the hydrogen is less than 5 ppm by weight, preferably less than 1 ppm by weight, preferably less than 0.7 ppm by weight, more preferably less than 0.3 ppm weight. Thus, preferably, the respective CO and CO 2 content of the nitrogen is less than 5 ppm by weight, preferably less than 1 ppm by weight, preferably less than 0.5 ppm by weight, more preferably less than 0.1 ppm weight. The impurities present in the carrier gases can be measured by any suitable method. By way of example, mention will be made of that using analyzers comprising probes based on aluminum oxide.
Cette analyse chromatographique améliorée est particulièrement importante car sa fiabilité et son efficacité accrues permettent à présent lors de son utilisation directement sur les ateliers industriels d'envisager instantanément des mesures opératoires correctives en cas de déviation des valeurs d'analyse obtenues.This improved chromatographic analysis is particularly important because its increased reliability and efficiency now allow it, when used directly in industrial workshops, to instantly consider corrective operating measures in the event of deviation from the analysis values obtained.
Quoique ne désirant pas être lié à cette explication, la Demanderesse pense que le problèmes rencontrés par le passé avec les analyses chromatographiques et leur manque de fiabilité étaient liés à la présence des produits de réaction entre les impuretés telles l'eau et/ou l'oxygène des gaz vecteurs avec les produits participants à la polymérisation des oléfines, plus particulièrement avec les composantes catalytiques des dits produits.Although not wishing to be linked to this explanation, the Applicant thinks that the problems encountered in the past with chromatographic analyzes and their unreliability were linked to the presence of the reaction products between the impurities such as water and / or the oxygen of the carrier gases with the products participating in the polymerization of olefins, more particularly with the catalytic components of said products.
Ainsi, à titre d'exemple, dans le cas d'une polymérisation d'oléfines en phase gaz dans un réacteur à lit fluidisé qui utilise un système catalytique comprenant un composé organoaluminique, le Demanderesse pense que ce sont les produits de la réaction de l' organoaluminique avec les impuretés qui induisent la non fiabilité des mesures chromatographiques et les problèmes déjà susmentionnés.Thus, by way of example, in the case of polymerization of olefins in the gas phase in a fluidized bed reactor which uses a catalytic system comprising an organoaluminum compound, the Applicant thinks that these are the products of the reaction of organoaluminum with impurities which induce unreliability of chromatographic measurements and the problems already mentioned.
De plus, pour des raisons ancestrales et de facilité, il est bien connu de l'homme de l'art que les gaz vecteurs utilisés sur ce type d'ateliers industriels sont des gaz de pureté dite "industrielle", c'est-à-dire des gaz qui n'ont pas subi de traitement particulier pour en éliminer les impuretés (et qui ne sont donc pas soumis à des règles strictes de pureté telles que ceux correspondant à la présente invention), ce qui expliquerait les problèmes rencontrés susmentionnés.In addition, for ancestral reasons and ease, it is well known to those skilled in the art that the carrier gases used in this type of industrial workshop are gases of purity called "industrial", that is to say -to say gases which have not undergone any particular treatment to remove impurities (and which are therefore not subject to strict rules of purity such as those corresponding to the present invention), which would explain the problems encountered above.
Ainsi, la présente invention concerne également un procédé de production de polymère en continu dans un atelier industriel comprenant un réacteur de polymérisation d'oléfines en présence d'un système catalytique de polymérisation, procédé lors duquel on contrôle au moins un paramètre opératoire de l'atelier au moyen d'une analyse par chromatographie en ligne d'une phase essentiellement gazeuse provenant du dit atelier industriel, la dite analyse chromatographique étant effectuée au moyen de gaz vecteurs comprenant essentiellement de l'hydrogène et/ou de l'azote, caractérisé en ce que la teneur en oxygène et en eau de l'hydrogène et de l'azote est inférieure à 5 ppm poids, de préférence inférieure à 1 ppm poids. La polymérisation d'oléfines est de préférence effectuée en phase gazeuse, de préférence au moyen d'un réacteur à lit fluidisé.Thus, the present invention also relates to a process for the continuous production of polymer in an industrial workshop comprising an olefin polymerization reactor in the presence of a catalytic polymerization system, process during which at least one operating parameter of the workshop by means of an analysis by online chromatography of a phase essentially gas from the said industrial workshop, the said chromatographic analysis being carried out by means of carrier gases essentially comprising hydrogen and / or nitrogen, characterized in that the oxygen and water content of the hydrogen and l nitrogen is less than 5 ppm by weight, preferably less than 1 ppm by weight. The polymerization of olefins is preferably carried out in the gas phase, preferably by means of a fluidized bed reactor.
De préférence, le système catalytique comprend un composé organoaluminique, de préférence un composé alkylaluminium tel le triethylaluminium ou le triisobutylaluminium.Preferably, the catalytic system comprises an organoaluminium compound, preferably an alkylaluminium compound such as triethylaluminium or triisobutylaluminium.
A titre d'illustration des poudres de polymère concernées par la présente invention, on citera :By way of illustration of the polymer powders concerned by the present invention, there may be mentioned:
PP (polymère de propylène),PP (propylene polymer),
SBR (polymère de butadiène copolymérisé avec du styrène), ABS (polymère d'acrylonitrile, de butadiène et de styrène), nitrile (polymère de butadiène copolymérisé avec de acrylonitrile), butyl (polymère d'isobutylène copolymérisé avec de l'isoprène),SBR (butadiene polymer copolymerized with styrene), ABS (acrylonitrile, butadiene and styrene polymer), nitrile (butadiene polymer copolymerized with acrylonitrile), butyl (isobutylene polymer copolymerized with isoprene),
EPR (polymère d'éthylène et de propylène),EPR (ethylene and propylene polymer),
EPDM (polymère d'étylène copolymérisé avec du propylène et un diène tel que l'hexadiène, le dicyclopentadiène ou Péthylidène norborène), copolymère d'éthylène et de vinyltriméthoxy silane, copolymère d'éthylène et d'un ou plusieurs composés choisis parmi Pacrylonitrile, les esters d'acide maléique, l'acétate de vinyle, les esters d'acide acrylique et méthacrylique et leurs homologues.EPDM (etylene polymer copolymerized with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene norborene), copolymer of ethylene and vinyltrimethoxy silane, copolymer of ethylene and of one or more compounds chosen from Pacrylonitrile, esters of maleic acid, vinyl acetate, esters of acrylic and methacrylic acid and their counterparts.
Selon un mode d'exécution préféré de la présente invention, elle s'applique à des polymères qui sont de préférence des polyoléfines, en particulier des copolymères d'éthylène et/ou de propylène et/ou de butène. Les alpha-oléfines préférées qui sont utilisées en combinaison avec l'éthylène et/ou le propylène et/ou le butène sont celles ayant de 4 à 8 atomes de carbone. Cependant, on peut également utiliser de petites quantités d'alpha oléfînes ayant plus de 8 atomes de carbone, par exemple de 9 à 40 atomes de carbone (par exemple, un diène conjugué). De préférence, l'invention s'applique à la production de polyéthylène, par exemple de polyéthylène basse densité linéaire (PEBDL) basé par exemple sur des copolymères d'éthylène avec du 1-butène, du 4-méthylpentène ou de l'hexène, ou du polyéthylène haute densité (PEHD) basé par exemple sur des homopolymères d'éthylène ou des copolymères d'éthylène avec de faibles proportions d'alpha oléfînes supérieures, par exemple du 1 -butène, du 1-pentène, de l'hexène ou du 4-méthyl-l-pentène.According to a preferred embodiment of the present invention, it applies to polymers which are preferably polyolefins, in particular copolymers of ethylene and / or propylene and / or butene. The preferred alpha-olefins which are used in combination with ethylene and / or propylene and / or butene are those having 4 to 8 carbon atoms. However, it is also possible to use small amounts of alpha olefins having more than 8 carbon atoms, for example from 9 to 40 carbon atoms (for example, a conjugated diene). Preferably, the invention applies to the production of polyethylene, for example linear low density polyethylene (LLDPE) based for example on copolymers of ethylene with 1-butene, 4-methylpentene or hexene, or high density polyethylene (HDPE) based for example on ethylene homopolymers or ethylene copolymers with low proportions of higher alpha olefins, for example 1-butene, 1-pentene, hexene or 4-methyl-1-pentene.
De préférence, la présente invention concerne la production de poudre de polyéthylène en continu dans un atelier industriel comprenant un réacteur de polymérisation en phase gazeuse de type réacteur vertical à lit fluidisé. De préférence, cette polymérisation s'effectue à une pression absolue comprise entre 0,5 et 6 MPa et à une température comprise entre 60°C et 130°C. Par exemple, pour la production de PEBDL la température de polymérisation est de préférence comprise entre 75 et 100°C aet pour le PEHD elle est généralement comprise entre 80 et 110°C en fonction de l'activité du catalyseur utilisé et des propriétés désirées du polymère.Preferably, the present invention relates to the production of polyethylene powder continuously in an industrial workshop comprising a gas phase polymerization reactor of the vertical fluidized bed reactor type. Preferably, this polymerization is carried out at an absolute pressure between 0.5 and 6 MPa and at a temperature between 60 ° C and 130 ° C. For example, for the production of LDPE, the polymerization temperature is preferably between 75 and 100 ° C. and for HDPE it is generally between 80 and 110 ° C. depending on the activity of the catalyst used and the properties desired. polymer.
De préférence, la polymérisation en continu s'effectue dans un réacteur vertical à lit fluidisé conformément à ce qui est décrit dans les (demandes) de brevet EP-0 855 411. FR No. 2,207,145 ou FRNo. 2,335,526.Preferably, the continuous polymerization is carried out in a vertical fluidized bed reactor in accordance with what is described in (patent applications) EP-0 855 411. FR No. 2,207,145 or FRNo. 2335526.
La présente invention s'applique donc aux ateliers de taille industrielle, à savoir, à titre d'exemple, aux réacteurs de polymérisation à lit fluidisé dont la production annuelle de polymère est d'au moins cent mille tonnes, de préférence au moins deux cent mille tonnes. De préférence, cette polymérisation s'effectue en présence d'un système catalytique de type Ziegler-Natta qui consiste généralement en un catalyseur solide comprenant essentiellement un composé d'un métal de transition et un cocatalyseur comprenant un composé organique d'un métal (par exemple, un composé organométallique, par exemple un composé alkylaluminium). Les systèmes catalytiques à haute activité de ce type comprennent en général un catalyseur solide qui consiste essentiellement en atomes de métal de transition, de magnésium et d'halogène. Des catalyseurs Ziegler supportés sur silice sont également appropriés. En particulier, on peut également utiliser des catalyseurs de type métallocène ainsi que des catalyseurs complexes de fer et/ ou de cobalt, par exemple ceux décrits dans WO98/27124 ou dans la demande déposée sous le numéro WOGB98/2638. Il est également possible d'utiliser des catalyseurs à base d'oxyde de chrome supporté sur un oxyde réfractaire. Les catalyseurs peuvent être utilisés sous directement ou sous la forme de prépolymère préparés au préalable lors d'une étape de prépolymérisation.The present invention therefore applies to workshops of industrial size, namely, by way of example, to fluidized bed polymerization reactors whose annual polymer production is at least one hundred thousand tonnes, preferably at least two hundred thousand tonnes. Preferably, this polymerization is carried out in the presence of a catalytic system of the Ziegler-Natta type which generally consists of a solid catalyst essentially comprising a compound of a transition metal and a cocatalyst comprising an organic compound of a metal (by example, an organometallic compound, for example an alkylaluminum compound). High activity catalytic systems of this type generally include a solid catalyst which consists essentially of transition metal, magnesium and halogen atoms. Ziegler catalysts supported on silica are also suitable. In particular, it is also possible to use metallocene type catalysts as well as complex iron catalysts. and / or cobalt, for example those described in WO98 / 27124 or in the application filed under the number WOGB98 / 2638. It is also possible to use catalysts based on chromium oxide supported on a refractory oxide. The catalysts can be used directly or in the form of prepolymers prepared beforehand during a prepolymerization step.
La Demanderesse a également trouvé de manière tout à fait surprenante qu'il était à présent possible d'éviter des situations de crise sur ses ateliers industriels en utilisant comme outil de contrôle l'analyse chromatographique selon la présente invention. The Applicant has also found, quite surprisingly, that it is now possible to avoid crisis situations in its industrial workshops by using as a control tool the chromatographic analysis according to the present invention.

Claims

Revendications claims
1. Méthode d'analyse par chromatographie en phase gazeuse en ligne d'une phase essentiellement gazeuse provenant d'un atelier industriel de polymérisation d'oléfines, la dite analyse chromatographique étant effectuée au moyen de gaz vecteurs comprenant essentiellement de l'hydrogène et/ou de l'azote, caractérisé en ce que la teneur en oxygène et en eau de l'hydrogène et de l'azote est inférieure à 5 ppm poids.1. Method for analysis by on-line gas chromatography of an essentially gaseous phase coming from an industrial olefin polymerization workshop, the said chromatographic analysis being carried out by means of carrier gases essentially comprising hydrogen and / or nitrogen, characterized in that the oxygen and water content of the hydrogen and nitrogen is less than 5 ppm by weight.
2. Méthode selon la revendication 1 caractérisé en ce que la teneur en oxygène et en eau de l'hydrogène et de l'azote est inférieure à 1 ppm poids.2. Method according to claim 1 characterized in that the oxygen and water content of hydrogen and nitrogen is less than 1 ppm by weight.
3. Méthode selon l'une quelconque des revendication précédentes caractérisé en ce que la polymérisation d'oléfines est effectuée en phase gazeuse.3. Method according to any one of the preceding claims, characterized in that the polymerization of olefins is carried out in the gas phase.
4. Méthode selon l'une quelconque des revendication précédentes caractérisé en ce que la polymérisation d'oléfines est effectuée au moyen d'un réacteur à lit fluidisé.4. Method according to any one of the preceding claims, characterized in that the polymerization of olefins is carried out by means of a fluidized bed reactor.
5. Méthode selon l'une quelconque des revendication précédentes caractérisé en ce que la teneur en oxygène de l'hydrogène est inférieure à 0J ppm poids.5. Method according to any one of the preceding claims, characterized in that the oxygen content of the hydrogen is less than 0J ppm by weight.
6. Méthode selon l'une quelconque des revendication précédentes caractérisé en ce que la teneur en oxygène de l'azote est inférieure à 0,5 ppm poids.6. Method according to any one of the preceding claims, characterized in that the oxygen content of the nitrogen is less than 0.5 ppm by weight.
7. Méthode selon l'une quelconque des revendication précédentes caractérisé en ce que la teneur en CO et en CO2 de l'hydrogène et de l'azote est inférieure à 1 ppm poids.7. Method according to any one of the preceding claims, characterized in that the CO and CO 2 content of the hydrogen and of the nitrogen is less than 1 ppm by weight.
8. Procédé de production de polymère en continu dans un atelier industriel comprenant un réacteur de polymérisation d'oléfines en présence d'un système catalytique de polymérisation, procédé lors duquel on contrôle au moins un paramètre opératoire de l'atelier au moyen d'une analyse par chromatographie en ligne d'une phase essentiellement gazeuse provenant du dit atelier industriel, la dite analyse chromatographique étant effectuée au moyen de gaz vecteurs comprenant essentiellement de l'hydrogène et/ou de l'azote, caractérisé en ce que la teneur en oxygène et en eau de l'hydrogène et de l'azote est inférieure à 5 ppm poids.8. Process for the continuous production of polymer in an industrial workshop comprising an olefin polymerization reactor in the presence of a system catalytic polymerization, process in which at least one operating parameter of the workshop is checked by means of an analysis by online chromatography of an essentially gaseous phase originating from said industrial workshop, said chromatographic analysis being carried out using gases vectors essentially comprising hydrogen and / or nitrogen, characterized in that the oxygen and water content of the hydrogen and nitrogen is less than 5 ppm by weight.
9. Procédé selon la revendication 8 caractérisé en ce que la teneur en oxygène et en eau de l'hydrogène et de l'azote est inférieure à 1 ppm poids.9. Method according to claim 8 characterized in that the oxygen and water content of hydrogen and nitrogen is less than 1 ppm by weight.
10._Procédé selon l'une quelconque des revendications 8 à 9 caractérisé en ce que la polymérisation d'oléfines est effectuée en phase gazeuse au moyen d'un réacteur à lit fluidisé.10._Procédé according to any one of claims 8 to 9 characterized in that the polymerization of olefins is carried out in gas phase by means of a fluidized bed reactor.
11. Procédé selon l'une quelconque des revendications 8 à 10 caractérisé en ce que le système catalytique comprend un composé organoaluminique. 11. Method according to any one of claims 8 to 10 characterized in that the catalytic system comprises an organoaluminum compound.
EP01990632A 2000-12-07 2001-11-30 Methode d'analyse par chromatographie en ligne pour la polymerisation d'olefines Withdrawn EP1340070A1 (en)

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