EP1144725B1 - Procede pour appliquer un revetement sur des reacteurs destines a la polymerisation haute pression de 1-olefines - Google Patents

Procede pour appliquer un revetement sur des reacteurs destines a la polymerisation haute pression de 1-olefines Download PDF

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Publication number
EP1144725B1
EP1144725B1 EP99965554A EP99965554A EP1144725B1 EP 1144725 B1 EP1144725 B1 EP 1144725B1 EP 99965554 A EP99965554 A EP 99965554A EP 99965554 A EP99965554 A EP 99965554A EP 1144725 B1 EP1144725 B1 EP 1144725B1
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Prior art keywords
metal
layer
phosphorus
reactor
nickel
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EP99965554A
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German (de)
English (en)
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EP1144725A2 (fr
Inventor
Stephan Hüffer
Andreas Deckers
Wilhelm Weber
Roger Klimesch
Dieter Littmann
Jürgen STURM
Götz LERCH
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BASF SE
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BASF SE
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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F19/00—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers
    • F28F19/02—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings
    • F28F19/06—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings of metal
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F19/00—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers
    • F28F19/02—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1603—Process or apparatus coating on selected surface areas
    • C23C18/1614—Process or apparatus coating on selected surface areas plating on one side
    • C23C18/1616—Process or apparatus coating on selected surface areas plating on one side interior or inner surface
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1655—Process features
    • C23C18/1662—Use of incorporated material in the solution or dispersion, e.g. particles, whiskers, wires
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F2245/00—Coatings; Surface treatments
    • 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
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12556—Organic component
    • 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
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12944—Ni-base component
    • 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
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal

Definitions

  • the invention relates to a method for coating reactors for the high pressure polymerization of 1-olefins.
  • This invention relates to reactors and high pressure reactor plants for the polymerization or copolymerization of 1-olefins in particular Ethylene containing those coated according to the invention Reactors, and a process for the production of ethylene homound Copolymers in the reactors according to the invention.
  • the production of homopolymers and copolymers of High pressure ethylene is an industrial scale carried out process. In these procedures, pressures above 500 bar and temperatures of 150 ° C and higher used.
  • the process is generally carried out in high pressure autoclaves or carried out in tubular reactors.
  • High pressure autoclaves are in so-called compact or elongated embodiments known.
  • the well - known tubular reactors (Ullmanns Encyclopedia of technical chemistry, volume 19, p. 169 and p. 173 ff (1980), publisher Chemie Weinheim, Deerfield Beach, Basel) are characterized by simple Handling and low maintenance and are agitated against Autoclaves an advantage. The in the above equipment achievable sales are limited.
  • PTFE polytetrafluoroethylene
  • a method for coating a reactor has now been found characterized in that a metal layer or a metal-polymer dispersion layer on the inner surface of the reactor of a reactor for high pressure polymerization of ethylene without current deposit by covering the surfaces with a metal electrolyte solution contacted, in addition to the metal electrolyte, a reducing agent and optionally a halogenated to be deposited Contains polymer in dispersed form. Furthermore, were Reactors coated according to the invention for high-pressure polymerization of ethylene found. Finally, the reactors according to the invention for the high pressure polymerization of Ethylene is used and a process for high pressure polymerization of ethylene found.
  • the one with an anti-adhesive metal coating or metal-polymer dispersion layer coated reactors allow one significantly improved sales compared to non-coated Reactors.
  • This object of the invention is a method for electroless chemical deposition of metal layers or Underlying metal-polymer dispersion phases, which is known per se is (w. Riedel: Functional nickel plating, Verlag Eugen Leize, Saulgau, 1989, pages 231 to 236, ISBN 3-750480-044-x).
  • the Deposition of the metal layer or the metal-polymer dispersion phases serves to coat the inner walls of the known High-pressure reactor.
  • the according to the inventive method metal layer to be deposited comprises an alloy or an alloy-like one Mixed phase from a metal and at least one another element.
  • the metal-polymer dispersion phases according to the invention additionally comprise a polymer, in the context of Invention a halogenated polymer in the metal layer is dispersed.
  • the metal alloy is preferred a metal-boron alloy or a metal-phosphorus alloy with a boron or phosphorus content of 0.5 to 15% by weight.
  • Coatings are so-called “chemical Nickel systems” are phosphorus-containing nickel alloys a phosphorus content of 0.5 to 15% by weight; very particularly preferred are high phosphorus nickel alloys with 5 to 12 Wt .-%.
  • the electrons required for this are not through an external one Power source provided, but by chemical Reaction generated in the electrolyte itself (oxidation of a reducing agent).
  • the coating is carried out, for example, by immersion of the workpiece in a metal electrolyte solution a stabilized polymer dispersion was previously mixed.
  • metal electrolyte solutions commercially available or freshly prepared metal electrolyte solutions are usually used, to which the following components are added in addition to the electrolyte: a reducing agent such as a hypophosphite or boranate (for example NaBH 4 ), a buffer mixture for adjusting the pH, an alkali metal fluoride such as NaF, KF or LiF, carboxylic acids and a deposition moderator such as Pb 2+ .
  • a reducing agent such as a hypophosphite or boranate (for example NaBH 4 )
  • a buffer mixture for adjusting the pH for a buffer mixture for adjusting the pH
  • an alkali metal fluoride such as NaF, KF or LiF
  • carboxylic acids carboxylic acids
  • a deposition moderator such as Pb 2+
  • Ni 2+ , hypophosphite, carboxylic acids and fluoride and optionally deposition moderators such as Pb 2+ are particularly preferably used.
  • Such solutions are sold, for example, by Riedel, Galvano- und Filtertechnik GmbH, Halle, Westphalia and Atotech GmbH, Berlin. Solutions which have a pH around 5 and about 27 g / l NiSO 4 .6H 2 O and about 21 g / l NaH 2 PO 2 .H 2 O with a PTFE content of 1 to 25 g are particularly preferred / l included.
  • the optionally used halogenated polymer of the process according to the invention is preferably fluorinated.
  • suitable fluorinated polymers are polytetrafluoroethylene, perfluoroalkoxy polymers (PFA, for example with C 1 - to C 8 -alkoxy units), copolymers of tetrafluoroethylene and perfluoroalkyl vinyl ether, for example perfluorovinyl propyl ether.
  • PFA perfluoroalkoxy polymers
  • PTFE polytetrafluoroethylene
  • PFA perfluoroalkoxy polymers
  • PTFE dispersions Commercial polytetrafluoroethylene dispersions are preferred as the use form (PTFE dispersions) can be used.
  • the dispersions used a nonionic detergent (for example Polyglycols, alkylphenol ethoxylate or mixtures of the substances mentioned, 80 to 120 g neutral detergent per liter) or an ionic detergent (for example alkyl and haloalkyl sulfonates, Alkylbenzenesulfonates, alkylphenol ether sulfates, Tetraalkylammonium salts or optionally mixtures of the above Substances, 15 to 60 g ionic detergent per liter) for stabilization of the dispersion included.
  • a nonionic detergent for example Polyglycols, alkylphenol ethoxylate or mixtures of the substances mentioned, 80 to 120 g neutral detergent per liter
  • an ionic detergent for example alkyl and haloalkyl sulfonates, Alkylbenzenesulfonates, alkylphenol ether sulfates, Tetraalkylammonium salts or optionally mixtures of the above
  • Coating is carried out at a slightly elevated temperature, but which must not be so high that it destabilizes the dispersion comes. As temperatures have 40 to 95 ° C as proven suitable. Temperatures of 80 to 91 ° C. and 88 ° C. is particularly preferred.
  • the polymer portion of the dispersion coating is mainly by the amount of polymer dispersion added and the choice of detergents.
  • concentration of the Polymers the bigger role; high polymer concentrations of Immersion baths lead to a disproportionately high proportion of polymer in the metal-phosphor polymer dispersion layer or metal-boron polymer dispersion layer.
  • the surfaces treated according to the invention allow good heat transfer, although the coatings have a not inconsiderable thickness of 1 to 100 ⁇ m can. 3 to 20 ⁇ m, in particular 5 to 16 ⁇ m, are preferred.
  • the polymer content of the dispersion coating is 5 to 30 % By volume, preferably 15 to 25% by volume, 19 being particularly preferred up to 21 vol.%.
  • the surfaces treated according to the invention have excellent durability.
  • an annealing is preferably carried out at 200 to 400 °, especially at 315 to 380 ° C.
  • the tempering period is generally 5 minutes to 3 hours, preferably 35 to 60 minutes.
  • Another object of the present invention is a method for producing a coated reactor, which has a particularly adhesive, durable and heat-resistant coating and therefore solves the problem according to the invention in a special way.
  • This method is characterized in that before application the metal-polymer dispersion layer additionally a 1 to 15 microns, preferably 1 to 5 microns thick metal-phosphor layer is applied by electroless chemical deposition.
  • Electroless chemical application of a 1 to 15 ⁇ m thick metal-phosphor layer to improve adhesion is done by Metal electrolyte baths, but in this case none stabilized Polymer dispersion is added.
  • For tempering is preferably dispensed with at this time, since this is the Adhesion of the subsequent metal-polymer dispersion layer generally adversely affected.
  • the workpiece is placed in a second immersion bath, which in addition to the metal electrolyte also a stabilized one Includes polymer dispersion. This forms the metal-polymer dispersion layer.
  • An annealing at 100 to 450 ° C. is then preferably carried out, performed in particular at 315 to 400 ° C.
  • the annealing time is generally 5 minutes to 3 hours, preferably 35 to 45 minutes.
  • tubular Reactors can be particularly well by a preferred Coating variant of the method according to the invention by the metal electrolyte solution or the metal electrolyte polymer dispersion mixture pumps through the reactor to be coated.
  • the tubular reactors served, the coated tubes of the invention without problems in polymerization plants for high pressure polymerization install, replacing uncoated pipes.
  • the ethylene polymerization in the plants according to the invention, the pipes according to the invention usually take place at Temperatures from 400 to 6000 bar, preferably from 500 to 5000 bar and particularly preferably 1000 to 3500 bar.
  • the reaction temperature is 150 to 450 ° C, 160 are preferred up to 250 ° C.
  • the molecular weight regulators are hydrogen, aliphatic aldehydes, Ketones, CH-acidic compounds such as mercaptans or alcohols, Suitable for olefins and alkanes.
  • the polymerization can be carried out with oxygen-containing gases such as for example air can be started, but also with organic Peroxo compounds or with organic azo compounds such as for example AIBN (Azobisisobutyronitrile).
  • oxygen-containing gases such as for example air can be started
  • organic Peroxo compounds or with organic azo compounds such as for example AIBN (Azobisisobutyronitrile).
  • AIBN Azobisisobutyronitrile
  • benzoyl peroxide and di-tert.butyl peroxide are particularly preferred.
  • the polymers of ethylene produced by the process according to the invention can have very different molar masses depending on the reaction conditions.
  • Preferred molar masses M w are between 500 and 600,000 g.
  • Ethylene polymers are their small number of specks is usually specified in the form of a speck note, a low speck grade is usually a low one Number of specks corresponds.
  • the polymers produced according to the invention are particularly suitable for the production of moldings and sheets, such as foils or bags.
  • the removed reactor tube (length 150 m, diameter 15 mm) was contacted at a temperature of 88 ° C. with an aqueous nickel salt solution, the solution having the following composition: 27 g / l NiSO 4 .6 H 2 O, 21 g / l NaH 2 PO 2 .2 H 2 O, lactic acid CH 3 CHOHCO 2 H 20 g / l, propionic acid C 2 H 5 CO 2 H 3 g / l, Na citrate 5 g / l, NaF 1 g / l (note: Chemically electroless nickel electrolyte solutions of this and other concentrations are commercially available, for example from Riedel Galvano- und Filtertechnik GmbH, Halle, Westphalia; or from Atotech Kunststoff GmbH, Berlin)).
  • the pH was 4.8. To achieve uniform layer thicknesses, the solution was pumped through the pipe at a flow rate of 0.1 m / s. At a deposition rate of 12 ⁇ m / h, the process is finished after 75 min. The layer thickness achieved was 16 ⁇ m. The coated tube was then rinsed with water, dried and annealed at 400 ° C. for one hour.
  • the removed reactor tube (length 150 m, diameter 15 mm) was contacted at a temperature of 88 ° C. with an aqueous nickel salt solution, the solution having the following composition: 27 g / l NiSO 4 .6H 2 O, 21 g / l NaH 2 PO 2 .2H 2 O, 20 g / l lactic acid CH 3 CHOHCO 2 H, 3 g / l propionic acid C 2 H 5 CO 2 H, 5 g / l Na -Citrate, 1 g / l NaF.
  • the pH was 4.8.
  • the solution was pumped through the pipe at a flow rate of 0.1 m / s. At a deposition rate of 12 ⁇ m / h, 25 min. worked to get the achieved layer thickness of 5 microns.
  • the nickel salt solution was also added 1% by volume of a PTFE dispersion with a density of 1.5 g / ml added.
  • This PTFE dispersion contained 50% by weight solids.
  • the process was at a deposition speed of 8 ⁇ m / h finished in two hours (layer thickness 16 ⁇ m). That coated The tube was rinsed with water, dried and at 350 ° C annealed for an hour.
  • the polymerization was carried out in a total reactor 400 m. A detailed description of the reactor and the Polymerization conditions can be found in DE-A 40 10 271. The reactor was divided into 3 zones; at the beginning of each zone was initiated with peroxide solution. The dimensions of the zones are shown in Table 1.
  • the speck mark was determined by means of an automatic in-line measuring device (Brabender, Duisburg, "Autograder”). For this purpose, a small part of the polymer melt was shaped into a film using an approx. 10 cm wide slot die at 200 ° C., the thickness of which was approx. 0.5 mm. The number of specks was determined using a video camera and an automatic counting device. The number was then classified in the speck grade. Dimensions of the reaction zones of the experimental reactor Zone no. 1 2 3 Length [m] 150 150 100 diameter [Mm] 15 25 25
  • zone number 1 was coated according to the invention and the corresponding experiments were carried out. The results are shown in Table 2. It is expected that coating the other zones will further increase sales.
  • Example No. 1 2 3 (comparative example) Coating zone 1 nickel Nickel-PTFE no T max 1 [° C] 280 280 280 T min 1 [° C] 223 219 235 T max 2 [° C] 280 280 T max 3 [° C] 280 278 279

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Thermal Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Chemically Coating (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Polymerisation Methods In General (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
  • Paints Or Removers (AREA)
  • Pretreatment Of Seeds And Plants (AREA)
  • Separation By Low-Temperature Treatments (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Laminated Bodies (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (16)

  1. Procédé pour le revêtement d'un réacteur pour la polymérisation haute pression de 1-oléfines, caractérisé par le fait qu'on dépose sans courant une couche de métal ou une couche de dispersion de métal-polymère sur la surface interne du réacteur, tandis qu'on met en contact les surfaces avec une solution de électrolyte de métal, qui outre l'électrolyte de métal contient sous forme dispersée un agent réducteur, ainsi qu'en option un polymère halogéné à déposer.
  2. Procédé selon la revendication 1, caractérisé par le fait qu'on utilise comme électrolytes de métal une solution d'électrolyte de nickel ou de cuivre et comme agent réducteur un hypophosphite ou un boranate.
  3. Procédé selon la revendication 1, caractérisé par le fait qu'on ajoute à la solution d'électrolyte de métal une dispersion d'un polymère halogéné.
  4. Procédé selon la revendication 1, caractérisé par le fait qu'on utilise comme électrolyte de métal une solution de sel de nickel, que l'on réduit in situ avec un hypophosphite alcalin, et à laquelle on ajoute comme polymère halogéné une dispersion de polytétrafluoro-éthylène.
  5. Procédé selon la revendication 1 à 4, caractérisé par le fait qu'on utilise un polymère halogéné composé de particules sphériques ayant un diamètre moyen de 0,1 à 1,0 µm.
  6. Procédé selon la revendication 1 à 5, caractérisé par le fait qu'on utilise un polymère halogéné composé de particules sphériques ayant un diamètre moyen de 0,1 à 0,3 µm.
  7. Procédé selon la revendication 1 à 6, caractérisé par le fait qu'on dépose une couche de nickel-phosphore-polytétrafluoroéthylène ayant une épaisseur de 1 à 100 µm.
  8. Procédé selon la revendication 1 à 7, caractérisé par le fait qu'on dépose une couche de nickel-phosphore-polytétrafluoroéthylène ayant une épaisseur de 3 à 20 µm.
  9. Procédé selon la revendication 1 à 8, caractérisé par le fait qu'on dépose une couche de nickel-phosphore-polytétrafluoroéthylène ayant une épaisseur de 5 à 16 µm.
  10. Procédé selon les revendications 1 à 9, caractérisé par le fait qu'on dépose sur la face interne du réacteur d'abord sans courant une couche supplémentaire de métal-phosphore épaisse de 1 à 15 µm et ensuite une couche de dispersion de métal-phosphore-polymère.
  11. Procédé selon la revendication 1 à 9, caractérisé par le fait qu'on dépose comme couche de métal-phosphore supplémentaire une couche de nickel-phosphore, une couche de cuivre-phosphore, une couche de nickel-bore ou une couche de cuivre-bore ayant une épaisseur de 1 à 5 µm.
  12. Réacteur revêtu sur la face interne, pouvant être obtenu conformément au procédé selon les revendications 1 à 11.
  13. Réacteur revêtu sur la face interne selon la revendication 12, en particulier réacteur tubulaire, revêtu avec une couche de dispersion de métal-phosphore-polymère d'une épaisseur de 3 à 20 µm.
  14. Réacteur selon les revendications 12 et 13, qui porte sous la couche de dispersion de nickel-phosphore-polytétrafluoroéthylène d'une épaisseur de 3 à 20 µm une couche de nickel-phosphore d'une épaisseur de 1 à 15 µm.
  15. Utilisation de réacteurs, en particulier de réacteurs tubulaires, selon les revendications 12 à 14 dans des procédés à haute pression pour la polymérisation ou la copolymérisation d'éthylène.
  16. Procédé pour la polymérisation ou la copolymérisation en continu d'éthylène à des pressions de 500 à 6000 bar et des températures allant jusqu'à 150 à 450°C, caractérisé par le fait qu'on effectue la polymérisation dans un réacteur à haute pression selon les revendications 12 à 15.
EP99965554A 1998-12-30 1999-12-24 Procede pour appliquer un revetement sur des reacteurs destines a la polymerisation haute pression de 1-olefines Expired - Lifetime EP1144725B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19860526A DE19860526A1 (de) 1998-12-30 1998-12-30 Wärmeüberträger mit verringerter Neigung, Ablagerungen zu bilden und Verfahren zu deren Herstellung
DE19860526 1998-12-30
PCT/EP1999/010372 WO2000040775A2 (fr) 1998-12-30 1999-12-24 Procede pour appliquer un revetement sur des reacteurs destines a la polymerisation haute pression de 1-olefines

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EP1144725A2 EP1144725A2 (fr) 2001-10-17
EP1144725B1 true EP1144725B1 (fr) 2003-07-16

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EP99965554A Expired - Lifetime EP1144725B1 (fr) 1998-12-30 1999-12-24 Procede pour appliquer un revetement sur des reacteurs destines a la polymerisation haute pression de 1-olefines
EP99964672A Expired - Lifetime EP1144724B1 (fr) 1998-12-30 1999-12-24 Echangeur de chaleur presentant une tendance reduite a former des depots, et son procede de production
EP99967007A Expired - Lifetime EP1144723B1 (fr) 1998-12-30 1999-12-24 Procede pour appliquer un revetement sur des appareils ou des parties d'appareils utilises pour la construction d'installations chimiques

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EP99964672A Expired - Lifetime EP1144724B1 (fr) 1998-12-30 1999-12-24 Echangeur de chaleur presentant une tendance reduite a former des depots, et son procede de production
EP99967007A Expired - Lifetime EP1144723B1 (fr) 1998-12-30 1999-12-24 Procede pour appliquer un revetement sur des appareils ou des parties d'appareils utilises pour la construction d'installations chimiques

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EP (3) EP1144725B1 (fr)
JP (3) JP2003511551A (fr)
KR (3) KR20010100009A (fr)
CN (3) CN1636305A (fr)
AT (3) ATE237006T1 (fr)
CA (2) CA2358099A1 (fr)
DE (4) DE19860526A1 (fr)
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DE59903362D1 (de) 2002-12-12
KR20010100009A (ko) 2001-11-09
EP1144723B1 (fr) 2003-04-09
EP1144723A2 (fr) 2001-10-17
ATE237006T1 (de) 2003-04-15
KR20010103724A (ko) 2001-11-23
CN1338008A (zh) 2002-02-27
ATE245210T1 (de) 2003-08-15
DE59905005D1 (de) 2003-05-15
WO2000040774A2 (fr) 2000-07-13
WO2000040775A2 (fr) 2000-07-13
EP1144725A2 (fr) 2001-10-17
US6617047B1 (en) 2003-09-09
EP1144723A3 (fr) 2002-11-13
DE59906313D1 (de) 2003-08-21
EP1144724A2 (fr) 2001-10-17
WO2000040775A3 (fr) 2000-11-09
ES2197710T3 (es) 2004-01-01
CA2358099A1 (fr) 2000-07-13
EP1144724B1 (fr) 2002-11-06
US6509103B1 (en) 2003-01-21
DE19860526A1 (de) 2000-07-06
JP2003511551A (ja) 2003-03-25
ATE227360T1 (de) 2002-11-15
JP2002534605A (ja) 2002-10-15
WO2000040774A3 (fr) 2002-09-26
JP2002534606A (ja) 2002-10-15
KR20010100013A (ko) 2001-11-09
WO2000040773A2 (fr) 2000-07-13
CN1332810A (zh) 2002-01-23
ES2204184T3 (es) 2004-04-16
WO2000040773A3 (fr) 2000-11-09
US6513581B1 (en) 2003-02-04
CA2358097A1 (fr) 2000-07-13
CN1636305A (zh) 2005-07-06

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