EP0080919A1 - Lubricant composition used in a high-pressure ethylene polymerisation process - Google Patents

Lubricant composition used in a high-pressure ethylene polymerisation process Download PDF

Info

Publication number
EP0080919A1
EP0080919A1 EP82402095A EP82402095A EP0080919A1 EP 0080919 A1 EP0080919 A1 EP 0080919A1 EP 82402095 A EP82402095 A EP 82402095A EP 82402095 A EP82402095 A EP 82402095A EP 0080919 A1 EP0080919 A1 EP 0080919A1
Authority
EP
European Patent Office
Prior art keywords
lubricating composition
ethylene
composition according
reactor
compressor
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.)
Withdrawn
Application number
EP82402095A
Other languages
German (de)
French (fr)
Inventor
Pierre Gloriod
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Orkem SA
Original Assignee
Chimique des Charbonnages SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Chimique des Charbonnages SA filed Critical Chimique des Charbonnages SA
Publication of EP0080919A1 publication Critical patent/EP0080919A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • C10M101/02—Petroleum fractions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • C10M107/08—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation containing butene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/04—Hydroxy compounds
    • C10M129/10—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/24—Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/20—Thiols; Sulfides; Polysulfides
    • C10M135/22—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M135/26—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing carboxyl groups; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/104—Aromatic fractions
    • C10M2203/1045—Aromatic fractions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/106—Naphthenic fractions
    • C10M2203/1065—Naphthenic fractions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/108—Residual fractions, e.g. bright stocks
    • C10M2203/1085—Residual fractions, e.g. bright stocks used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/026—Butene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/026—Butene
    • C10M2205/0265—Butene used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/027—Neutral salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/08—Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/062—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups bound to the aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/085—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing carboxyl groups; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/042—Metal salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/049—Phosphite
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/10—Phosphatides, e.g. lecithin, cephalin

Definitions

  • the present invention relates on the one hand to an improved lubricating composition and on the other hand to the application of said composition to the lubrication of ethylene compressors involved in a high pressure polymerization process.
  • the double problem facing this process consists firstly in the fact that the free radical generators recycled with the gaseous ethylene phase coming from the separator risk initiating the polymerization of ethylene in the recycling line and d '' foul this line by polymer formation, and secondly in the fact that a parasitic polymerization can also occur - by the same mechanism - on the discharge of the compressor and consequently can clog the connection pipe between compressor and reactor.
  • These drawbacks inevitably oblige the operators of polymerization units to periodically clean, either after dismantling the pipes or otherwise, the parts of the unit where the parasitic phenomena described above occur.
  • the present invention proposes to remedy the aforementioned drawbacks by modifying the lubrication mode of the compressor responsible for recompressing the ethylene gas from the separator to the pressure level of the reactor.
  • French Patent No. 1,353,328 describes a lubricating composition for high temperatures comprising from 0.5 to 10 by weight of an antioxidant, the latter being able to be an organic phosphite or a product of phenolic type. Used at such concentrations, these products have the function of protecting the lubricant against oxidation.
  • French Patent No. 1,353,328 describes a lubricating composition for high temperatures comprising from 0.5 to 10 by weight of an antioxidant, the latter being able to be an organic phosphite or a product of phenolic type. Used at such concentrations, these products have the function of protecting the lubricant against oxidation.
  • 1,404,773 describes mixtures comprising from 95 to 5% by weight of a paraffinic wax and from 5 to 95 by weight of a polyolefin, (polyethylene or polybutene-1), stabilized against degradation by oxidation by the incorporation of 0.05 to 1 part by weight per 100 parts of polyolefin of a certain type of polyolefinic phenol and 0.05 to 1 part by weight per 100 parts of polyolefin of a certain type of phosphite.
  • a polyolefin polyethylene or polybutene-1
  • the present invention firstly relates to an improved lubricating composition
  • an oil consisting for example of a mixture of paraffins and of polyisobutylene, and where appropriate a lubricating additive, characterized in that it also comprises 0.05 at 0.25% by weight of a radical polymerization inhibitor chosen from quinones, phenol derivatives, phosphites and alkyl thiodicarboxylates.
  • the lubricant composition according to the invention preferably comprises paraffins to the exclusion of any hydro-refined aromatic constituent.
  • Non-limiting examples of inhibitors which can be used according to the invention including di-terbutylparacresol, lauryl thiodipropionate, N-octadecyl (4 'hydroxy-3', 5 'diterbutylphenol) propionate, etc.
  • lubricating composition according to the invention it is possible to use any usual lubrication additive such as for example lecithin as well as, if necessary, a usual corrosion inhibitor.
  • the composition according to the invention is produced by simple mixing of the various constituents.
  • a second object of the present invention is a process for the polymerization of ethylene and for the copolymerization of ethylene with at least one comonomer, in a reactor under pressure of between 1000 and 5000 bars and in the presence of at least one compound generating free radicals, according to which the mixture of unconverted ethylene and of polymer coming from the reactor is expanded to a pressure between 100 and 500 bars then sent to a separator from where the gas phase of ethylene and, if necessary , comonomer is recycled to at least one compressor capable of recompressing it to the pressure of the reactor, characterized in that said compressor is lubricated by means of the improved lubricating composition described above.
  • Compounds generating free radicals used in such a process are in particular peroxides and peresters.
  • the comonomers which can be used in such a process are on the one hand the olefins having from 3 to 8 carbon atoms such as in particular propylene, butene-1, methyl-4 pentene-1, hexene-1, octene-1 and on the other hand polar comonomers such as carbon monoxide, maleic anhydride, alkyl acrylates and methacrylates, alkyl monomaleates and dialkyl maleates, vinyl acetate, etc.
  • the method according to the invention has the effect of eliminating or considerably reducing the fouling of the connecting pipes between compressor and reactor on the one hand, and between separator and compressor on the other hand.
  • the cleaning operations of the installation can be carried out much less frequently than in conventional methods, which makes it possible to considerably limit the economic losses due to the lowering of the operating rate of the installation.
  • the ethylene polymerization installation comprises a 2,150 bar pressure reactor, a 300 bar pressure separator and a compressor capable of recompressing the ethylene gas from the pressure level of the separator to that of the reactor.
  • the discharge pipes of said compressor are fitted with double-shells in which cold water circulates in order to cool the ethylene gas to a temperature of 40 ° C.
  • the compressor is lubricated by means of an ordinary lubricating composition, comprising an oil based on a mixture of paraffins and polyisobutylene.
  • an ordinary lubricating composition comprising an oil based on a mixture of paraffins and polyisobutylene.
  • the ethylene polymerization installation used is identical to that of the previous example.
  • the compressor is lubricated by means of an improved lubricating composition according to the invention, that is to say the lubricating composition of the previous example to which 0.1% by weight of di-terbutylparacresol is added.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Lubricants (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

The composition comprises an oil based on paraffins and, additionally, from 0.05 to 0.25% by weight of at least one radical polymerisation inhibitor chosen from quinones, phenol derivatives, phosphites and alkyl thiodicarboxylates. It is employed for lubricating the compressor of a high-pressure ethylene polymerisation plant.

Description

La présente invention se rapporte d'une part à une composition lubrifiante améliorée et d'autre part à l'application de ladite composition à la lubrification de compresseurs d'éthylène intervenant dans un procédé de polymérisation sous haute pression.The present invention relates on the one hand to an improved lubricating composition and on the other hand to the application of said composition to the lubrication of ethylene compressors involved in a high pressure polymerization process.

Il est connu de polymériser l'éthylène, le cas échéant en présence d'autres monomères, dans un réacteur sous haute pression (généralement de 1000 à 3000 bars) et en présence de composés générateurs de radicaux libres tels que des peroxydes ou des peresters. Dans un tel procédé, le mélange d'éthylène non converti et de polymère issu du réacteur est détendu jusqu'à un niveau intermédiaire de pression, de l'ordre de 150 à 500 bars, puis envoyé dans un séparateur d'où la phase gazeuse d'éthylène et, le cas échéant, de comonomère est recyclée vers un compresseur capable de la recomprimer jusqu'au niveau de pression du réacteur.It is known to polymerize ethylene, if necessary in the presence of other monomers, in a reactor under high pressure (generally from 1000 to 3000 bars) and in the presence of compounds generating free radicals such as peroxides or peresters. In such a process, the mixture of unconverted ethylene and polymer from the reactor is expanded to an intermediate pressure level, of the order of 150 to 500 bars, then sent to a separator, hence the gas phase. ethylene and, where appropriate, comonomer is recycled to a compressor capable of recompressing it to the pressure level of the reactor.

Le double problème auquel est confronté ce procédé consiste d'une part dans le fait que les générateurs de radicaux libres recyclés avec la phase gazeuse d'éthylène provenant du séparateur risquent d'initier la polymérisation de l'éthylène dans la conduite de recyclage et d'encrasser cette conduite par formation de polymère, et d'autre part dans le fait qu'une polymérisation parasite peut également se produire - par le même mécanisme - au refoulement du compresseur et par voie de conséquence peut encrasser la conduite de liaison entre compresseur et réacteur. Ces inconvénients obligent inévitablement les exploitants d'unités de polymérisation à nettoyer périodiquement, soit après démontage des conduites soit autrement, les parties de l'unité où se produisent les phénomènes parasites décrits ci-dessus.The double problem facing this process consists firstly in the fact that the free radical generators recycled with the gaseous ethylene phase coming from the separator risk initiating the polymerization of ethylene in the recycling line and d '' foul this line by polymer formation, and secondly in the fact that a parasitic polymerization can also occur - by the same mechanism - on the discharge of the compressor and consequently can clog the connection pipe between compressor and reactor. These drawbacks inevitably oblige the operators of polymerization units to periodically clean, either after dismantling the pipes or otherwise, the parts of the unit where the parasitic phenomena described above occur.

Ces opérations de nettoyage sont extrêmement coûteuses puisqu'- elles obligent à l'arrêt momentané de la fabrication puis, une fois l'opération achevée, au redémarrage de l'unité. Elles se traduisent donc par un-abaissement du taux de marche et par une perte économique considérable.These cleaning operations are extremely costly since they require a temporary cessation of production and, once the operation is completed, the restart of the unit. They therefore translate into a lowering of the market rate and a considerable economic loss.

La présente invention se propose d'apporter remède aux inconvénients précités en modifiant le mode de lubrification du compresseur chargé de recomprimer l'éthylène gazeux provenant du séparateur jusqu'au niveau de pression du réacteur.The present invention proposes to remedy the aforementioned drawbacks by modifying the lubrication mode of the compressor responsible for recompressing the ethylene gas from the separator to the pressure level of the reactor.

Le brevet français n° 1.353.328 décrit une composition lubrifiante pour hautes températures comprenant de 0,5 à 10 en poids d'un antioxydant, celui-ci pouvant être un phosphite organique ou un produit de type phénolique. Employés à de telles concentrations, ces produits ont pour fonction de protéger le lubrifiant contre l'oxydation. Le brevet français n° 1.404.773 décrit des mélanges comprenant de 95 à 5 % en poids d'une cire paraffinique et de 5 à 95 en poids d'une polyoléfine, (polyéthylène ou polybutène-1), stabilisés contre la dégradation par oxydation par l'incorporation de 0,05 à 1 partie en poids pour 100 parties de polyoléfine d'un certain type de phénol polyoléfinique et de 0,05 à 1 partie en poids pour 100 parties de polyoléfine d'un certain type de phosphite.French Patent No. 1,353,328 describes a lubricating composition for high temperatures comprising from 0.5 to 10 by weight of an antioxidant, the latter being able to be an organic phosphite or a product of phenolic type. Used at such concentrations, these products have the function of protecting the lubricant against oxidation. French Patent No. 1,404,773 describes mixtures comprising from 95 to 5% by weight of a paraffinic wax and from 5 to 95 by weight of a polyolefin, (polyethylene or polybutene-1), stabilized against degradation by oxidation by the incorporation of 0.05 to 1 part by weight per 100 parts of polyolefin of a certain type of polyolefinic phenol and 0.05 to 1 part by weight per 100 parts of polyolefin of a certain type of phosphite.

La présente invention a pour premier objet une composition lubrifiante améliorée comprenant une huile, constituée par exemple d'un mélange de paraffines et de polyisobutylène, et le cas échéant un additif de lubrification, caractérisée en ce qu'elle comprend en outre de 0,05 à 0,25 % en poids d'un inhibiteur de polymérisation radicalaire choisi parmi les quinones, les dérivés du phénol, les phosphites et les thiodicarboxylates d'alkyle. La composition lubrifiante selon l'invention comprend de préférence des paraffines à l'exclusion de tout constituant aromatique hydro- raffiné. Des exemples non limitatifs d'inhibiteurs utilisables selon l'invention dont le di-terbutylparacrésol, le thiodipropionate de lauryle, le N-octadécyl (4' hydroxy-3', 5' diterbutylphénol) propionate, etc.The present invention firstly relates to an improved lubricating composition comprising an oil, consisting for example of a mixture of paraffins and of polyisobutylene, and where appropriate a lubricating additive, characterized in that it also comprises 0.05 at 0.25% by weight of a radical polymerization inhibitor chosen from quinones, phenol derivatives, phosphites and alkyl thiodicarboxylates. The lubricant composition according to the invention preferably comprises paraffins to the exclusion of any hydro-refined aromatic constituent. Non-limiting examples of inhibitors which can be used according to the invention, including di-terbutylparacresol, lauryl thiodipropionate, N-octadecyl (4 'hydroxy-3', 5 'diterbutylphenol) propionate, etc.

Dans la composition lubrifiante selon l'invention, on peut utiliser tout additif de lubrification usuel tel que par exemple la lécithine ainsi que, le cas échéant, un inhibiteur de corrosion usuel. La fabrication de la composition selon l'invention s'effectue par simple mélange des différents constituants.In the lubricating composition according to the invention, it is possible to use any usual lubrication additive such as for example lecithin as well as, if necessary, a usual corrosion inhibitor. The composition according to the invention is produced by simple mixing of the various constituents.

La présente invention a pour second objet un procédé de polymérisation de l'éthylène et de copolymérisation de l'éthylène avec au moins un comonomère, dans un réacteur sous pression comprise entre 1000 et 5000 bars et en présence d'au moins un composé générateur de radicaux libres, selon lequel le mélange d'éthylène non converti et de polymère issu du réacteur est détendu jusqu'à une pression comprise entre 100 et 500 bars puis envoyé dans un séparateur d'où la phase gazeuse d'éthylène et, le cas échéant, de comonomère est recyclée vers au moins un compresseur capable de la recomprimer jusqu'à la pression du réacteur, caractérisé en ce que ledit compresseur est lubrifié au moyen de la composition lubrifiante améliorée décrite précédemment. Les composés générateurs de radicaux libres utilisés dans un tel procédé sont notamment les peroxydes et les peresters. Les comonomères utilisables dans un tel procédé sont d'une part les oléfines ayant de 3 à 8 atomes de carbone telles que notamment propylène, butène-1, méthyl-4 pentène-1, hexène-1, octène-1 et d'autre part les comonomères polaires tels que le monoxyde de carbone, l'anhydride maléique, les acrylates et méthacrylates d'alkyle, les monomaléates d'alkyle et les maléates de dialkyle, l'acétate de vinyle, etc.A second object of the present invention is a process for the polymerization of ethylene and for the copolymerization of ethylene with at least one comonomer, in a reactor under pressure of between 1000 and 5000 bars and in the presence of at least one compound generating free radicals, according to which the mixture of unconverted ethylene and of polymer coming from the reactor is expanded to a pressure between 100 and 500 bars then sent to a separator from where the gas phase of ethylene and, if necessary , comonomer is recycled to at least one compressor capable of recompressing it to the pressure of the reactor, characterized in that said compressor is lubricated by means of the improved lubricating composition described above. Compounds generating free radicals used in such a process are in particular peroxides and peresters. The comonomers which can be used in such a process are on the one hand the olefins having from 3 to 8 carbon atoms such as in particular propylene, butene-1, methyl-4 pentene-1, hexene-1, octene-1 and on the other hand polar comonomers such as carbon monoxide, maleic anhydride, alkyl acrylates and methacrylates, alkyl monomaleates and dialkyl maleates, vinyl acetate, etc.

Le procédé selon l'invention a pour effet de supprimer ou de diminuer considérablement l'encrassement des conduites de liaison entre compresseur et réacteur d'une part, entre séparateur et compresseur d'autre part. Ainsi les opérations de nettoyage de l'installation peuvent être effectuées beaucoup moins fréquemment que dans les procédés conventionnels, ce qui permet de limiter considérablement les pertes économiques dues à l'abaissement du taux de marche de l'installation.The method according to the invention has the effect of eliminating or considerably reducing the fouling of the connecting pipes between compressor and reactor on the one hand, and between separator and compressor on the other hand. Thus the cleaning operations of the installation can be carried out much less frequently than in conventional methods, which makes it possible to considerably limit the economic losses due to the lowering of the operating rate of the installation.

Les exemples suivants sont donnés à titre illustratif et non limitatif.The following examples are given by way of illustration and not by way of limitation.

EXEMPLE 1 (comparatif)EXAMPLE 1 (comparative)

L'installation de polymérisation de l'éthylène comprend un réacteur sous pression de 2 150 bars, un séparateur sous pression de 300 bars et un compresseur capable de recomprimer l'éthylène gazeux du niveau de pression du séparateur jusqu'à celui du réacteur. Les tuyauteries de refoulement dudit compresseur sont équipées de doubles-enveloppes dans lesquelles circule de l'eau froide en vue de refroidir l'éthylène gazeux jusqu'à une température de 40°C. En fonction d'une part des températures d'entrée et sortie de l'éthylène et de l'eau, d'autre part de la surface intérieure totale des tuyauteries de gaz soumises au refroidissement, on calcule le coefficient global d'échange thermique K. Au début de l'opération de polymérisation, ce coefficient a une valeur relative K = 100. En opération normale, ce coefficient diminue régulièrement dans le temps. Dans cet exemple, le compresseur est lubrifié au moyen d'une composition lubrifiante ordinaire, comprenant une huile à base d'un mélange de paraffines et de polyisobutylène. Après une semaine d'opération continue, le coefficient global d'échange thermique a pris la valeur relative K = 80.The ethylene polymerization installation comprises a 2,150 bar pressure reactor, a 300 bar pressure separator and a compressor capable of recompressing the ethylene gas from the pressure level of the separator to that of the reactor. The discharge pipes of said compressor are fitted with double-shells in which cold water circulates in order to cool the ethylene gas to a temperature of 40 ° C. As a function of the inlet and outlet temperatures of ethylene and water on the one hand, and the total internal surface area of the gas pipes subjected to cooling on the other hand, the overall heat exchange coefficient K is calculated. At the start of the polymerization operation, this coefficient has a relative value K = 100. In normal operation, this coefficient decreases regularly over time. In this example, the compressor is lubricated by means of an ordinary lubricating composition, comprising an oil based on a mixture of paraffins and polyisobutylene. After a week of continuous operation, the overall heat exchange coefficient has taken the relative value K = 80.

EXEMPLE 2EXAMPLE 2

L'installation de polymérisation de l'éthylène utilisée est identique à celle de l'exemple précédent. Cependant le compresseur est lubrifié au moyen d'une composition lubrifiante améliorée selon l'invention, c'est-à-dire la composition lubrifiante de l'exemple précédent à laquelle est ajouté 0,1 % en poids de di-terbutylparacrésol. Dans ces conditions, le coefficient global d'échange thermique n'a pris la valeur relative K = 80 qu'après quatre semaines d'opération continue.The ethylene polymerization installation used is identical to that of the previous example. However, the compressor is lubricated by means of an improved lubricating composition according to the invention, that is to say the lubricating composition of the previous example to which 0.1% by weight of di-terbutylparacresol is added. Under these conditions, the overall heat exchange coefficient did not take the relative value K = 80 until after four weeks of continuous operation.

Claims (7)

1. Composition lubrifiante améliorée comprenant une huile à base de paraffines, caractérisée en ce qu'elle comprend en outre de 0,05 à 0,25 % en poids d'au moins un inhibiteur de polymérisation radicalaire choisi parmi les quinones, les dérivés du phénol et les phosphites.1. Improved lubricating composition comprising an oil based on paraffins, characterized in that it also comprises from 0.05 to 0.25% by weight of at least one radical polymerization inhibitor chosen from quinones, derivatives of phenol and phosphites. 2. Composition lubrifiante selon la revendication 1, caractérisée en ce que l'huile est constituée d'un mélange de paraffines et de polyisobutylène.2. Lubricating composition according to claim 1, characterized in that the oil consists of a mixture of paraffins and polyisobutylene. 3. Composition lubrifiante selon l'une des revendications 1 et 2, caractérisée en ce qu'elle comprend en outre un additif de lubrification.3. Lubricating composition according to one of claims 1 and 2, characterized in that it further comprises a lubrication additive. 4. Composition lubrifiante selon l'une des revendications 1 à 3, caractérisée en ce que l'inhibiteur de polymérisation radicalaire est le di-terbutylparacrésol.4. Lubricating composition according to one of claims 1 to 3, characterized in that the radical polymerization inhibitor is di-terbutylparacresol. 5. Composition lubrifiante selon l'une des revendications 1 à 3, caractérisée en ce que l'inhibiteur de polymérisation radicalaire est le thiodipropionate de lauryle.5. Lubricating composition according to one of claims 1 to 3, characterized in that the radical polymerization inhibitor is lauryl thiodipropionate. 6. Composition lubrifiante selon l'une des revendications 1 à 3, caractérisée en ce que l'inhibiteur de polymérisation radicalaire est le N-octadécyl (4' hydroxy-3', 5' diterbutylphénol) propionate.6. Lubricating composition according to one of claims 1 to 3, characterized in that the radical polymerization inhibitor is N-octadecyl (4 'hydroxy-3', 5 'diterbutylphenol) propionate. 7. Procédé de polymérisation de l'éthylène et de copolymérisation de l'éthylène avec au moins un comonomère, dans un réacteur sous pression comprise entre 1000 et 3000 bars et en présence d'au moins un composé générateur de radicaux libres, selon lequel le mélange d'éthylène non converti et de polymère issu du réacteur est détendu jusqu'à une pression comprise entre 150 et 500 bars puis envoyé dans un séparateur d'où la phase gazeuse d'éthylène et, le cas échéant, de comonomère est recyclée vers au moins un compresseur capable de la recomprimer jusqu'à la pression du réacteur, caractérisé en ce que ledit compresseur est lubrifié au moyen d'une composition lubrifiante selon l'une des revendications 1 à 6.7. Process for the polymerization of ethylene and copolymerization of ethylene with at least one comonomer, in a reactor under pressure of between 1000 and 3000 bars and in the presence of at least one compound generating free radicals, according to which the mixture of unconverted ethylene and polymer from the reactor is expanded to a pressure between 150 and 500 bars and then sent to a separator from which the gaseous phase of ethylene and, where appropriate, of comonomer is recycled to at least one compressor capable of recompressing it to the pressure of the reactor, characterized in that said compressor is lubricated by means of a lubricating composition according to one of claims 1 to 6.
EP82402095A 1981-11-30 1982-11-17 Lubricant composition used in a high-pressure ethylene polymerisation process Withdrawn EP0080919A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8122389A FR2517322A1 (en) 1981-11-30 1981-11-30 IMPROVED LUBRICANT COMPOSITION FOR USE IN HIGH-PRESSURE ETHYLENE POLYMERIZATION PROCESS
FR8122389 1981-11-30

Publications (1)

Publication Number Publication Date
EP0080919A1 true EP0080919A1 (en) 1983-06-08

Family

ID=9264491

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82402095A Withdrawn EP0080919A1 (en) 1981-11-30 1982-11-17 Lubricant composition used in a high-pressure ethylene polymerisation process

Country Status (4)

Country Link
EP (1) EP0080919A1 (en)
JP (1) JPS58103593A (en)
CA (1) CA1207316A (en)
FR (1) FR2517322A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2533638A1 (en) * 1982-09-29 1984-03-30 El Paso Polyolefins METHOD FOR REDUCING THE GAS LEAKAGE OF A COMPRESSOR IN A POLYMERIZATION PROCESS

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2525445B2 (en) * 1988-01-29 1996-08-21 出光興産株式会社 Lubricating oil composition

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2028349A (en) * 1932-07-01 1936-01-21 Ig Farbenindustrie Ag Lubricant and process of making same
FR1353328A (en) * 1962-04-09 1964-02-21 Acheson Ind Inc Lubricants for high temperatures
FR1404773A (en) * 1963-07-08 1965-07-02 Allied Chem Mixtures of paraffinic waxes and polyolefins, stabilized against degradation by oxidation
DE2019381A1 (en) * 1969-05-19 1970-11-26 Mol En Corp Mixture resistant to sudden pressure and yields under constant pressure
FR2313399A1 (en) * 1975-06-03 1976-12-31 Charbonnages Ste Chimique ETHYLENE POLYMERIZATION AND COPOLYMERIZATION PROCESS USING A GAS INJECTION DEVICE

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2028349A (en) * 1932-07-01 1936-01-21 Ig Farbenindustrie Ag Lubricant and process of making same
FR1353328A (en) * 1962-04-09 1964-02-21 Acheson Ind Inc Lubricants for high temperatures
FR1404773A (en) * 1963-07-08 1965-07-02 Allied Chem Mixtures of paraffinic waxes and polyolefins, stabilized against degradation by oxidation
DE2019381A1 (en) * 1969-05-19 1970-11-26 Mol En Corp Mixture resistant to sudden pressure and yields under constant pressure
FR2313399A1 (en) * 1975-06-03 1976-12-31 Charbonnages Ste Chimique ETHYLENE POLYMERIZATION AND COPOLYMERIZATION PROCESS USING A GAS INJECTION DEVICE

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2533638A1 (en) * 1982-09-29 1984-03-30 El Paso Polyolefins METHOD FOR REDUCING THE GAS LEAKAGE OF A COMPRESSOR IN A POLYMERIZATION PROCESS

Also Published As

Publication number Publication date
FR2517322A1 (en) 1983-06-03
FR2517322B1 (en) 1985-05-10
JPS58103593A (en) 1983-06-20
CA1207316A (en) 1986-07-08

Similar Documents

Publication Publication Date Title
EP0908474B1 (en) Process for the polymerization of olefins
US6844408B2 (en) Preparation of polyethylene
CN103906773B (en) Polymerization or the method for combined polymerization ethylenically unsaturated monomer in the presence of radical polymerization initiator
FR2640273A1 (en) METHOD FOR GAS PHASE POLYMERIZATION OF ETHYLENE FOR MANUFACTURING LINEAR POLYETHYLENE WITH CLOSE DISTRIBUTION OF MOLECULAR WEIGHT
KR20170125804A (en) Process to control output and quality of ethylene-based polymer formed by high pressure free radical polymerization
KR102000869B1 (en) Control of Fouling in High Pressure Polyethylene Production
FR2542319A1 (en) PROCESS FOR THE POLYMERIZATION IN AN AQUEOUS MEDIUM OF SUSPENDING VINYLIDENE FLUORIDE
JPH0413703A (en) Method for reducing deposition of polymer in heat exchanger during polymerization of alpha-olefin
EP0102860B1 (en) Process for producing homo and copolymers of ethylene
CA1207316A (en) Improved lubricating compound for use in a high pressure ethylene polymerisation process
KR100245204B1 (en) Activation of catalyst in ethylene polymerization at high temperature
CA2332493C (en) Procedure for the controlled radical polymerisation of ethylene under high pressure in the presence of free radical initiators and indolinic nitroxide terminating radicals
EP0116248B1 (en) Continuous process for producing homo- and copolymers of ethylene
CA2267098A1 (en) Lubricant for supercharger and method for obtaining same
FR2842203A1 (en) PROCESS FOR THE MANUFACTURE OF VINYLIDENE FLUORIDE POLYMER
EP0116797B1 (en) Continuous process for producing homo- and copolymers of ethylene
CA2266128A1 (en) Improved method for purifying acrylic acid
EP1119585A1 (en) Method for controlled free radical polymerisation or copolymerisation of ethylene under high pressure in the presence of an initiator-controller
EP3559056B1 (en) Use of at least one phenolic compound to stabilise ethylene copolymerisation reactions
EP0143716B2 (en) Process for the polymerisation and the copolymerisation of ethylene at high pressure and temperature in the presence of ziegler-type catalysts
FR2540502A1 (en) PROCESS FOR PRODUCING LOW DENSITY LINEAR POLYETHYLENE
US11912951B2 (en) Polybutene-free lubricating composition
EP0554139B1 (en) Process for polymerising ethylene to obtain a polymer with broad molecular weight distribution and process for preparing the catalyst component
JPS5884839A (en) Poly-1-butene resin composition for (hot) water supply
WO2021202273A1 (en) Antifoulant and process

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): AT BE CH DE GB IT LI LU NL SE

17P Request for examination filed

Effective date: 19830415

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 19840829

RIN1 Information on inventor provided before grant (corrected)

Inventor name: GLORIOD, PIERRE