EP1144725A2 - Method for coating reactors for high pressure polymerisation of 1-olefins - Google Patents

Method for coating reactors for high pressure polymerisation of 1-olefins

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Publication number
EP1144725A2
EP1144725A2 EP19990965554 EP99965554A EP1144725A2 EP 1144725 A2 EP1144725 A2 EP 1144725A2 EP 19990965554 EP19990965554 EP 19990965554 EP 99965554 A EP99965554 A EP 99965554A EP 1144725 A2 EP1144725 A2 EP 1144725A2
Authority
EP
Grant status
Application
Patent type
Prior art keywords
layer
metal
characterized
phosphorus
microns
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.)
Granted
Application number
EP19990965554
Other languages
German (de)
French (fr)
Other versions
EP1144725B1 (en )
Inventor
Andreas Deckers
Stephan Hüffer
Roger Klimesch
Götz LERCH
Dieter Littmann
Jürgen STURM
Wilhelm Weber
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.)
BASF SE
Original Assignee
BASF SE
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

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Classifications

    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28HEAT EXCHANGE IN GENERAL
    • F28FDETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F19/00Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers
    • F28F19/02Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/16Chemical 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
    • C23C18/1601Process or apparatus
    • C23C18/1603Process or apparatus coating on selected surface areas
    • C23C18/1614Process or apparatus coating on selected surface areas plating on one side
    • C23C18/1616Process or apparatus coating on selected surface areas plating on one side interior or inner surface
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/16Chemical 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
    • C23C18/1601Process or apparatus
    • C23C18/1633Process of electroless plating
    • C23C18/1655Process features
    • C23C18/1662Use of incorporated material in the solution or dispersion, e.g. particles, whiskers, wires
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/16Chemical 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
    • C23C18/31Coating with metals
    • C23C18/32Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12556Organic component
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771Transition metal-base component
    • Y10T428/12861Group VIII or IB metal-base component
    • Y10T428/12944Ni-base component
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31678Of metal

Abstract

The invention relates to a method for coating a reactor. Said method is characterised in that a metal layer or a metal polymer dispersion layer is deposited on the inner surface of the reactor in a currentless manner by contacting the surfaces to a metal electrolytic solution which contains a reduction means and a halogenated polymer in dispersed form in addition to the metal electrolyte. Said halogenated polymer can optionally be deposited.

Description

A method for coating reactors for high pressure polymerization of l-01efinen

description

The invention relates to a method for coating reactors for high pressure polymerization of 1-olefins. Furthermore, this invention relates to reactors and high-pressure reactor equipment for the polymerization or copolymerization of 1-olefins especially ethylene, comprising the inventively coated reactors, and to a process for the preparation of ethylene homo- and copolymers in the present invention reactors.

The preparation of Homopolymerisäten and copolymers of

Ethylene in the high-pressure process is an industrially carried out on a large scale process. In these methods, pressures above 500 bar and temperatures of 150 ° C and above. The process is generally carried out in autoclaves or in tubular reactors. High-pressure autoclave are known in so-called squat or elongated embodiments. The known tubular reactors (Ullmanns Encyclopadie der technischen Chemie, Volume 19, pages 169 and S. 173 et seq (1980), Verlag Chemie Weinheim, Deerfield Beach, Basel) are characterized by simple handling and low maintenance, and are opposite stirred autoclave advantageous. The achievable in the above equipment sales are limited.

To increase the capacity of existing equipment, the aim is to achieve the highest possible sales. however, limiting polymerization temperature and polymerization, which have a specific upper limit depending on the product type. For low density LDPE LDPE waxes and polymers, this upper limit is about 330 ° C; above it may settlements spontaneous ethylene decomposition. Below a temperature of 150 ° C may cause heat dissipation problems. Furthermore, the resulting pressure loss is limiting; this pressure loss increases with decreasing temperature.

Decisive polymerization for the operation of a tubular reactor to Ethylenpoly- is a good heat dissipation. This heat removal is preferably accomplished by jacket cooling. Here, a cooling medium, generally performed by the so-called water cooling circuit. The temperature of the cooling medium is of great importance. In Kühlme- diumstemperaturen below 150 ° C may form a laminar layer of polyethylene, which act as an insulator and can reduce the heat dissipation drastically. If the temperature of the cooling medium is too high, so the temperature difference between the reaction medium and cooling medium is too low, which also results (see unsatisfactory heat transfer numbers. For example, E. Fitzer, W. Fritz, Chemical Reaction Engineering, 2nd Edition, page 152 ff., 5 Springer Verlag Heidelberg, 1982).

In practice, however, a slowly flowing layer of polyethylene observed even at temperatures above 150 ° C, which leads to a reduction in heat dissipation. One method that decision

10 are provided to impede this layer, is the so-called "stimuli". (EP-B 0567818, page 3, line 6 et seq.), The flow rate is drastically increased by periodic pressure reduction and briefly eliminates the laminar layers. By the periodic pressure reduction, however, is the average pressure during

15 of the operation decreased, which lowers the density of the ethylene and thus decreases conversion and molecular weight of the product. In addition, the periodic pressure reduction causes a considerable mechanical stress in the apparatus, which leads to increased repair costs and thus results in economic disadvantages.

20

The formation of laminar boundary layers in tubular reactors or stirred autoclave for ethylene also has negative consequences for the quality of the ethylene polymers. The one material with a much longer residence time in the

25 reactors is usually high molecular weight, which manifests itself macroscopically in the form of so-called specks noticeable. But Stipp-containing material has less good mechanical properties because it forms in the material crack-places where material failure takes place, and is also disadvantageous from the optical impression.

30

Try the tubes with PTFE (polytetrafluoroethylene) coating, were not successful. Although PTFE serves as a heat-resistant incompatible with polyethylene material, but it also acts as an insulator and in thin layers to deteriorate

35 heat transfer. Similar problems are also observed in processes involving the application of monolayer silane layers on the surface to be protected (Polymer Mater. Sci. And Engineering, Proceedings of the ACS Division of Polymeric Materials Science and Engineering (1990), Volume 62, pages 259 . to

40263).

45 It was therefore the task

provide a method by which the revenue could be improved in reactors particularly for high pressure polymerization of ethylene, which method should be based on the coating of the reactors;

provide correspondingly treated reactors,

to use these reactors for the construction of high-pressure reactors, and -

manufacture in the inventive reactors polymers of 1-olefins.

It has now a process for coating a reactor found, characterized in that a metal layer or a metal polymer -Dispersionsschicht on the reactor inner surface of a reactor for high pressure polymerization of ethylene is deposited without current by reacting the surfaces with a metal -Elektro- contacted lytlösung containing a reducing agent in addition to the metal electrolyte, and optionally a halogenated polymer to be deposited in dispersed form halo. Furthermore, according to the invention coated reactors for the polymerization Hochdruckpoly- found from ethylene. Finally, reactors according to the invention were used for the high pressure polymerization of ethylene and a process for the high pressure polymerization of ethylene found.

The coated with an antiadhesive metal coating or metal-polymer dispersion bed reactors allow a significantly improved conversion as compared to non-coated reactors.

This solution of the object of the invention is to provide a method for electroless deposition of metal layers or metal-polymer dispersion phases, which is known per se (W. Riedel: Functional nickel, Verlag Eugen Leize, Saulgau, 1989, pages 231-236, ISBN 3 -750480-044-x). The deposition of the metal layer or the metal-polymer dispersion phases is used to coat the inner walls of the known high-pressure reactor. The deposited by the inventive method metal layer comprises an alloy or alloy-like mixed phase of a metal and at least one other element. The metal-polymer dispersion phases invention additionally comprise a polymer, in the context of the invention, a halogenated polymer, which is dispersed in the metal layer. In the metal alloy is preferably a metal-boron alloy or a metal-phosphorus alloy with a boron or phosphorus content of 0.5 to 15 wt -.%.

In a particularly preferred embodiment of the Inventions according coatings is so-called "chemical nickel systems", which are phosphorus-containing nickel alloys with a phosphorus content of from 0.5 to 15 wt .-%; especially before - High phosphorus-containing nickel alloy containing 5 to 12 wt .-% are Trains t.

In contrast to the galvanic deposition The required electrons are in chemical or autocatalytic deposition of metal-phosphorus or metal-boron not provided by an external power source available, but by chemical reaction in the electrolyte itself (oxidation of a reducing agent). The coating is carried out, for example, by dipping the workpiece into a metal Ξlektrolytlösung, which was mixed with a stabilized polymer dispersion before.

The metal electrolyte solutions usually commercially available or freshly prepared metal electrolyte solutions are used, which conces- addition to the electrolyte, the following components shall be: a reducing agent such as a hypophosphite or soil Ranat (e.g. NaBH 4), a buffer mixture to adjust the pH value, an alkali metal fluoride such as NaF, KF or LiF, carboxylic acids as well as a deposition moderator such as Pb 2+. In this case, the reducing agent is selected so that the corresponding element to be incorporated in the reducing agent is already present.

Commercial Nickelelektrolytlösun- are particularly preferred gen containing Ni 2+, hypophosphite, carboxylic acids and fluoride and possibly deposition moderators, such as Pb 2+. Such solutions are sold, for example, by Riedel, electroplating and Filtertechnik GmbH, Halle, Westphalia, and Atotech Germany GmbH, Berlin. Especially preferred are solutions having a pH of about 5 and about 27 g / 1 NiS0-6 H 2 0 and about 21 g / 1 NaH 2 pO 2 -H 2 0 at a PTFE content of from 1 to 25 g / 1 included.

The optional to use halogenated polymer of the method according invention is preferably fluorinated. Examples of suitable fluorinated polymers include polytetrafluoroethylene, perfluoro alkoxy-polymers (PFA, for example with C - to C 8 -alkoxy units),

Copolymers of tetrafluoroethylene and perfluoroalkyl perfluorovinyl propyl ether, for example. Particularly preferred are poly tetrafluoroethylene (PTFE) and perfluoroalkoxy polymers (PFA, according to DIN 7728, part 1, January 1988).

When insert molding preferably commercial Polytetrafluorethane Thylen dispersions (PTFE dispersions) can be used. PTFE dispersions, preferably having a solids content of 35 to 60 wt .-% and an average particle diameter of 0.05 to 1.2 microns, preferably 0.1 to 0.3 microns used. spherical particles are preferably used because the use of spherically-driven particles leads to very homogeneous composite layers. Advantage of the use of spherical particles is faster layer growth and better, especially longer Thermo - stability of the baths, which offers both economic benefits. This is particularly evident in comparison to systems using irregular polymer particles which are obtained by grinding the corresponding polymer. In addition, the dispersions used may be a nonionic detergent (for example, polyglycols, alkyl phenol ethoxylate, or optionally mixtures of said substances, from 80 to 120 g of neutral detergent per lithium ter), or an ionic detergent (for example, alkyl and halo alkyl sulfonates, alkyl benzene sulfonates, alkylphenol ether sulfates, tetraalkylammonium salts, or optionally mixtures of said substances, from 15 to 60 g per liter of ionic detergent) to stabilize the dispersion contained.

For the coating is carried out at a slightly elevated temperature, but must not be so high that it comes to the destabilization of the dispersion. As for temperatures 40 to 95 ° C have been found suitable. Temperatures of 80 to 91 ° C are preferred and particularly preferred is 88 ° C.

Deposition rates of 1 to 15 microns / hour have proven to be useful. The deposition rate can be influenced by the composition of baths as follows:

the deposition rate is increased by higher temperatures, there being a maximum temperature is limited for example by the stability of the optionally added polymer dispersion. the deposition rate is decreased by lower temperatures.

the deposition rate is increased by higher concentrations of electrolyte, lowered by lower; with concentrations of 1 g / 1 to 20 g / 1 Ni 2+ are useful, preferred are concentrations of 4 g / 1 to 10 g / 1; for Cu 2+ 1 g / 1 to 50 g / 1 are useful. By higher concentrations of reducing agent, the deposition rate can also increase;

By increasing the pH of the deposition can be increased speed. It is preferable to provide a pH of between 3 and 6, particularly preferably 4 to 5.5 a.

Addition of activators such as alkali metal fluorides, such as NaF or KF, the Abscheidegeschwindig- increased ness.

The polymer content of the dispersion coating is mainly influenced by the amount of the added polymer dispersion and the choice of detergents. The concentration of the polymer plays a major role; high polymer concentrations of

Immersion baths lead to a disproportionately higher polymer content in the metal-phosphorus polymer dispersion layer or metal-boron polymer dispersion layer.

It has been found that the inventive treated surfaces provide good heat transfer, even though the coatings can have a not inconsiderable thickness of 1 to 100 microns. Preferred are 3 to 20 .mu.m, in particular from 5 to 16 microns. The polymer content of the dispersion coating is 5 to 30 vol .-%, preferably 15 to 25 vol .-%, particularly preferably 19 to 21 vol .-% are. The present invention further treated surfaces exhibit excellent durability.

Preferably, following the dipping operation, a heat treatment at 200 to 400 ° C, especially at from 315 to 380 ° C is carried out. The conditioning is generally from 5 minutes to 3 hours, preferably 35 to 60 minutes.

Another object of the present invention is a method for producing a coated reactor, the adhering a loading Sonders, having durable and heat-resistant coating and therefore achieves the object of the present invention in a particular manner.

This method is characterized in that prior to the on - bringing the metal-polymer dispersion layer in addition, a 1 to 15 microns, preferably 1 to 5 microns thick metal-phosphorus layer is applied by electroless chemical deposition.

The electroless chemical deposition of a 1 to 15 micron thick metal-phosphorus layer for improving adhesion is again carried out by metal-electrolyte baths, however, where no stabilized polymer dispersion is added in this case. Conditioning is preferably omitted at this time, since this adversely affects the adhesion of the subsequent metal-polymer dispersion layer in general. After deposition of the metal-phosphorus layer, the workpiece is introduced into a second dip Ge, which also includes a stabilized polymer dispersion, in addition to the metal electrolyte. Here, the metal-polymer dispersion layer forms.

Preferably, a heat treatment at 100 to 450 ° C, in particular at 315 to 400 ° C is carried out subsequently. The annealing time is generally 5 minutes to 3 hours, preferably 35 to 45 minutes.

Suitable reactors for the high pressure polymerization of ethylene are, as initially performed, high-pressure autoclave or tubular reactors used, said tubular reactors are preferred. Rohrför--shaped reactors can be particularly well by a preferred variant of the process according to the invention coated by dispersion mixture through the reactor to be coated pum t the metal electrolyte solution or the metal-electrolyte polymer.

In one embodiment, the use of tubular reactors, is coated pipes the invention can be easily fitted to the high-pressure, replacing uncoated tubes in polymerization plants.

The ethylene polymerization in the systems of the invention, which contain tubes according to the invention usually takes place at temperatures of 400 to 6000 bar, preferably from 500 to 5000 bar, and more preferably 1000 to 3500 bar.

The reaction temperature is 150 to 450 ° C, preferably 160 to 250 ° C are.

As a monomer in the ethylene polymerization process according to the invention is particularly suitable. It can also copolymerization sate produced with ethylene, in principle any radically copolymerizable with ethylene olefins suitable as comonomers. preference

1-olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-decene,

Acrylates such as acrylic acid, methyl acrylate, acrylic acid ethyl ester, acrylic acid-n-butyl acrylate or tert. -bu- tylester; Methacrylic acid, methyl methacrylate, Metnacryisaure- ethyl ester, methacrylic acid n-butyl ester or methacrylic acid ter. butyl;

- vinyl carboxylates, vinyl acetate being particularly preferred,

Unsaturated dicarboxylic acids, particularly preferably maleic acid,

- unsaturated dicarboxylic acid derivatives, particularly preferably maleic anhydride and alkylimides of maleic acid such as methylmaleimide.

Hydrogen as molecular weight, aliphatic aldehydes, ketones, CH-acidic compounds, such as mercaptans or alcohols, olefins and alkanes are suitable.

The polymerization can be started with oxygen-containing gases such as air, but also with organic peroxy compounds or organic azo compounds such as AIBN (azobisisobutyronitrile). organic peroxo compounds are preferred, with benzoyl peroxide and di-tert-butyl peroxide are particularly preferred.

The polymers of ethylene produced by the inventive process may have very different molecular weights depending on the reaction conditions. Preferred molecular weights M w are from 500 to 600,000 g.

A particular advantage of the present invention produced by the ethylene polymers is their low fisheye count, which is usually specified in the form of a fisheye score, wherein a low fisheye score usually corresponds to a low fisheye count. The polymethyl risate according to the invention are particularly suitable for producing moldings and sheetlike structures, such as films or bags.

The invention will be explained with reference to a working example.

Working Example:

1. Electroless nickel system

The removed reactor tube (length 150 m, diameter 15 mm) was contacted at a temperature of 88 ° C with an aqueous Nikkeisalzlösung, wherein the solution had the following composition: 27 g / 1 NiS0 4 -6 H 2 0, 21 g / 1 NaH 2 P0-2 H 2 0, lactic acid CH 3 2 H CHOHC0 20 g / 1, propionic acid C 2 H 5 C0 2 H 3 g / 1, sodium citrate 5 g / 1 NaF, 1 g / 1 (Note: Chemical electroless nickel electrolyte solutions of these and other con- centration are commercially available, for example from Riedel electroplating and Filtertechnik GmbH, Halle, Westphalia; or Atotech Germany GmbH, Berlin)). The pH was 4.8. In order to obtain uniform layer thicknesses, the solution was pumped at a flow rate of 0.1 m / s through the tube. At a deposition rate of 12 .mu.m / h, the process after 75 min is completed. The layer thickness obtained was 16 microns. Subsequently, the coated tube was rinsed with water, dried and heated for one hour at 400 ° C.

Nickel-PTFE system

The preparation was carried out in two stages. First, the expanded 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 / 1

NiS0 4 -6 H 2 0, 21 g / 1 NaH 2 P0 2 -2H 2 0, 20 g / 1 of lactic acid CH 3 CH0HC0 2 H, 3 g / 1 propionic acid C 2 H 5 C0 2 H, 5 g / 1 Na citrate, 1 g / 1 NaF. The pH was 4.8. In order to obtain uniform layer thicknesses, the solution was pumped at a flow rate of 0.1 m / s through the tube. At a deposition rate of 12 microns / h 25 min. worked to obtain the scored layer thickness of 5 microns.

After this step has not been rinsed,

Subsequently, the nickel salt solution was further mixed with 1 vol .-% of a PTFE dispersion with a density of 1.5 g / ml. This PTFE dispersion containing 50 wt .-% solids. At a deposition rate of 8 microns / h the process was completed in two hours (film thickness 16 microns). The coated tube was rinsed with water, dried and heated for one hour at 350 ° C.

Polymerization Examples 1 to 3

The polymerization was carried out in a reactor of 400 m. A detailed description of the reactor and the polymerization can be found in DE-A 40 10 271st 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 below.

Polymerization was carried out at a pressure of 3000 bar. The molecular weight regulator used was propionaldehyde. The temperature of the coolant water was 200 ° C. The maximum reaction temperature was - adjusted by dosing the appropriate amount of peroxide solution - as in high-pressure tube reactors usual.

The fisheye score was determined by means of an automatic in-line measurement device (Fa. Brabender, Duisburg, "the Autogra-"). For this purpose a small part of the polymer melt by means of a 10 cm wide slit die at 200 ° C was formed into a film whose thickness was approximately 0.5 mm. By means of a video camera and an automatic counting the number of fish-eyes was determined. then carried the classification in the fisheye score based on the number.

Table 1: Dimensions of the reaction zones of the test reactor

In each case, only coated zone number 1 according to the invention and taken the appropriate experiments. The results are shown in Table 2 below. It is expected that a coating of the remaining zone leads to a further increase in the conversion.

Table 2: Polymerizations in differently coated Reaktorer.

Claims

claims
1. A process for coating a reactor for the high pressure polymerization of l-01efinen, characterized in that depositing a metal layer or a metal polymer dispersion layer on the internal reactor surface normally by contacting the surfaces with a metal electrolyte solution which, in addition the metal electrolyte, comprises a reducing agent and optionally a halogenated polymer to be deposited in dispersed form halo.
2. The method according to claim 1, characterized in that as the metal-electrolyte a nickel or copper electrolyte - solvent and used as the reducing agent is a hypophosphite or a soil Ranat.
3. The method according to claim 1, characterized in that is added to the metal electrolyte solution, a dispersion of a halogenated polymer th.
4. The method according to claim 1, characterized in that is used as the metal electrolyte, a nickel salt solution, which is reduced in situ with a Alkalihypophosph.it, and the one persion added as halogenated polymer is a polytetrafluoroethylene dis-.
5. The method of claim 1 to 4, characterized in that one of spherical particles used a halogenated polymer with an average diameter of 0.1 to 1.0 microns.
6. The method of claim 1 to 5, characterized in that one of spherical particles used a halogenated polymer with an average diameter of 0.1 to 0.3 microns.
7. Process according to claims 1 to 6, characterized in that depositing a nickel-phosphorus polytetrafluoroethylene layer having a thickness of 1 to 100 microns.
8. Process according to claims 1 to 7, characterized in that depositing a nickel-phosphorus polytetrafluoroethylene layer having a thickness of 3 to 20 microns.
9. The method according to claims 1 to 8, characterized gekennzeich- net that a nickel-phosphorus polytetrafluoroethylene layer having a thickness of 5 to 16, it to separate out.
10. The method according to claims 1 to 9, characterized in that initially electrolessly on the inside of the reactor, an additional 1 to 15 microns thick metal-phosphorus layer and then a metal-phosphorus-polymer dispersion -
5 is deposited layer.
11. The method according to claim 1 to 9, characterized in that as an additional metal-phosphorus layer, a nickel-phosphorus layer, a copper-phosphorus layer, a nickel-boron
10 layer or a copper-boron layer with a thickness of 1 to 5 microns is deposited.
12. On the inside coated reactor, obtainable by a process of claims 1 to 11.
15
13. On the inside coated reactor according to claim 12, in particular a tubular reactor, coated with a metal-phosphorus polymer dispersion layer having a thickness of 3 to 20 microns.
20
14. A reactor according to claims 12 and 13, ranging from 3 to 20 microns carrying a nickel-phosphorus layer of thickness of 1 to 15 microns under the nickel-phosphorus polytetrafluoroethylene dispersion layer thickness.
25
15. Use of reactors, in particular tubular reactors, according to claims 12 to 14 in high-pressure process for the polymerization or copolymerization of ethylene.
30 16. A process for the continuous polymerization or copolymerization of ethylene at pressures from 500 to 6000 bar and temperatures of up to 150 to 450 ° C, characterized in that 12 to 15 by carrying out the polymerization in a high pressure reactor as claimed.
35
40
5
EP19990965554 1998-12-30 1999-12-24 Method for coating reactors for high pressure polymerisation of 1-olefins Not-in-force EP1144725B1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE1998160526 DE19860526A1 (en) 1998-12-30 1998-12-30 Heat exchanger having a reduced tendency to form deposits and processes for their preparation
DE19860526 1998-12-30
PCT/EP1999/010372 WO2000040775A3 (en) 1998-12-30 1999-12-24 Method for coating reactors for high pressure polymerisation of 1-olefins

Publications (2)

Publication Number Publication Date
EP1144725A2 true true EP1144725A2 (en) 2001-10-17
EP1144725B1 EP1144725B1 (en) 2003-07-16

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EP19990964672 Not-in-force EP1144724B1 (en) 1998-12-30 1999-12-24 Heat exchanger with a reduced tendency to produce deposits and method for producing same
EP19990967007 Not-in-force EP1144723B1 (en) 1998-12-30 1999-12-24 Method for coating apparatuses and parts of apparatuses used in chemical manufacturing
EP19990965554 Not-in-force EP1144725B1 (en) 1998-12-30 1999-12-24 Method for coating reactors for high pressure polymerisation of 1-olefins

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EP19990964672 Not-in-force EP1144724B1 (en) 1998-12-30 1999-12-24 Heat exchanger with a reduced tendency to produce deposits and method for producing same
EP19990967007 Not-in-force EP1144723B1 (en) 1998-12-30 1999-12-24 Method for coating apparatuses and parts of apparatuses used in chemical manufacturing

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EP (3) EP1144724B1 (en)
JP (3) JP2003511551A (en)
KR (1) KR20010103724A (en)
CN (3) CN1636305A (en)
CA (2) CA2358099A1 (en)
DE (2) DE19860526A1 (en)
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EP1144723A2 (en) 2001-10-17 application
EP1144723A3 (en) 2002-11-13 application
ES2197710T3 (en) 2004-01-01 grant
JP2002534606A (en) 2002-10-15 application
EP1144725B1 (en) 2003-07-16 grant
WO2000040775A3 (en) 2000-11-09 application
US6617047B1 (en) 2003-09-09 grant
CN1338008A (en) 2002-02-27 application
WO2000040774A2 (en) 2000-07-13 application
US6513581B1 (en) 2003-02-04 grant
JP2002534605A (en) 2002-10-15 application
CN1636305A (en) 2005-07-06 application
WO2000040775A2 (en) 2000-07-13 application
US6509103B1 (en) 2003-01-21 grant
CA2358099A1 (en) 2000-07-13 application
WO2000040773A3 (en) 2000-11-09 application
JP2003511551A (en) 2003-03-25 application
ES2204184T3 (en) 2004-04-16 grant
WO2000040774A3 (en) 2002-09-26 application
CN1332810A (en) 2002-01-23 application
DE19860526A1 (en) 2000-07-06 application
DE59903362D1 (en) 2002-12-12 grant
EP1144724A2 (en) 2001-10-17 application
CA2358097A1 (en) 2000-07-13 application
EP1144724B1 (en) 2002-11-06 grant
WO2000040773A2 (en) 2000-07-13 application
KR20010103724A (en) 2001-11-23 application
EP1144723B1 (en) 2003-04-09 grant

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