EP1144723A2 - Method for coating apparatuses and parts of apparatuses used in chemical manufacturing - Google Patents

Method for coating apparatuses and parts of apparatuses used in chemical manufacturing

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Publication number
EP1144723A2
EP1144723A2 EP19990967007 EP99967007A EP1144723A2 EP 1144723 A2 EP1144723 A2 EP 1144723A2 EP 19990967007 EP19990967007 EP 19990967007 EP 99967007 A EP99967007 A EP 99967007A EP 1144723 A2 EP1144723 A2 EP 1144723A2
Authority
EP
Grant status
Application
Patent type
Prior art keywords
polymer
metal
parts
layer
according
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
EP19990967007
Other languages
German (de)
French (fr)
Other versions
EP1144723A3 (en )
EP1144723B1 (en )
Inventor
Bernd Diebold
Axel Franke
Stephan Hüffer
Jürgen KORKHAUS
Thilo Krebs
Wolfgang Loth
Joachim Nilges
Bernd Rumpf
Jürgen STURM
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 surface coating of apparatuses or parts of apparatuses used in chemical manufacturing. Walls of apparatuses, walls of containers and walls of reactors, dischargers, fixtures, pumps, filters, compressors, centrifuges, columns, dryers, comminuting machines, internal fittings and combinations are examples for said apparatuses or parts of apparatuses. The inventive method is characterised in that a metal layer or a metal polymer dispersion layer is currentlessly deposited on the apparatus/es or parts of apparatuses to be coated by contacting the parts to a metal electrolytic solution which contains a reduction means and optionally the dispersed polymer or polymer mixture in addition to the metal electrolyte, whereby at least one polymer is halogenated.

Description

A process for coating apparatuses and apparatus parts for chemical plant

The invention relates to a process for Oberf lächenbeschichtung of apparatuses and apparatus parts for chemical plant - including for example, are apparatus, tank and reactor walls, discharge devices, valves, pumps, filters, compressors, centrifuges, columns, dryers, Zerkleinerungsmaschi - NEN, baffles, to understand filler and mixing elements - characterized in that a metal layer or a metal polymer dispersion layer on the or normally separates the apparatuses to be coated or apparatus parts, by contacting the parts with a metal electrolyte solution comprising an addition to the metal electrolyte, optionally containing reducing agent and the polymer or polymer mixture to be deposited in dispersed form, wherein at least one polymer is halogenated. Then annealed optional. Further objects of the invention are surfaces of apparatuses and apparatus parts for chemical - see plant, which have been coated by the inventive process, and the use of the coating containing a metal component, at least one halogenated polymer and optional other polymers, for reducing the tendency of the coated surfaces to accumulate solids from fluids, causing fouling. Finally, the invention relates to apparatuses and apparatus parts for chemical plant construction, which are coated by the novel process.

Deposits in apparatuses and apparatus parts for chemical plant construction represent a serious problem in the chemical industry. are particularly affected apparatus, container and reactor walls, discharge devices, valves, pumps, filters, compressors, centrifuges, columns, dryers, shredders, internals, packing elements and mixing elements. These deposits are referred to as fouling.

The coverings can act in a variety of damaging or hindering the process and lead to the need for appropriate reactors or processing machines turn ERS repeated and clean.

With pads encrusted measuring devices can be erroneous and cause misleading results may occur due to the incorrect operation. Another problem that arises from the formation of deposits is due to the fact that, especially in the Bel molecular parameters such as molecular weight or degree of crosslinking gen different from any product specifications in polymerization reactors. If deposits during the current

Release the service, they can contaminate the product (eg specks in paints, inclusions in suspension beads). Unwanted deposits can in the case of reactor, packing elements or mixing elements, continues to lead to an undesirable change in the residence of the apparatus or impair the effectiveness of the internals or mixing elements as such. Crashing coarse parts of deposits can lead to blockage of extractor and processing devices, while small parts can lead to impairment of the product produced.

The deposits whose formation is to be prevented, it is coverings, which may be caused for example by reactions with or on surfaces. Other reasons are adhesion to surfaces that may be caused by van der Waals forces, polarization effects or electrostatic double layers. Other important effects are stagnation of the motion at the surface and, optionally, reactions in said stagnating layers. Finally, include: precipitation from solutions, evaporation residues, Vercrak- effect of locally hot surfaces and microbiological activities.

The causes are dependent on the particular material combinations and can be effective alone or in combination. During the operations, for which the undesirable deposits are formed, rather well studied (eg AP Watkinson and DI Wilson, Experimental Thermal Fluid Sci. 1997, 14, 361 and references cited therein), there are few uniform concepts for preventing the above deposits. The previously known methods have disadvantages.

Mechanical solutions have the disadvantage that they can cause significant additional costs. Additional reactor internals may continue to significantly change the flow profile of fluids in the reactors and thus require an expensive redevelopment of the process. Chemical additives can lead to undesired contamination of the product and in some cases pollute the environment. For these reasons, it is increasingly looking for ways to reduce the fouling tendency by modifying the chemical reactors, reactor parts and processing machines for chemical products directly.

Object of the present invention is therefore to provide a method for surface modification of apparatuses and apparatus parts for chemical plant construction,

- which reduces on the one hand the inclination of the surfaces to accumulate solids to form deposits, the method according treated areas should have a good shelf life, and wherein the inventive method should be inexpensive applicable to difficult to access areas, and on the other hand ensures that the product or products are not contaminated by additives.

Furthermore, the object of the present invention is to provide protected surfaces of apparatuses and apparatus parts for chemical plant construction, and, finally, to use apparatuses and apparatus parts for chemical plant construction.

The inventive object is achieved by a method for coating the surfaces of apparatuses and apparatus parts for chemical plant construction, characterized in that a metal layer or a metal polymer -Dispersionsschicht on or separates the apparatus to be coated or apparatus parts energized by the parts contacted with a metal electrolyte solution which contains a reducing agent addition to the metal electrolyte, and optionally, the polymer or polymer mixture to be deposited in dispersed form, wherein at least one polymer is halogenated halo-.

This solution of the problem according to the invention is a process for the electroless deposition of metal layers based polymer dispersion, 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 used for coating of the known apparatuses and apparatus parts of the chemical plant. The metal layer of the invention includes fully an alloy or alloy-like mixed phase of a metal and at least one other element. The inventively preferred metal-polymer dispersion phases comprise a polymer within the scope 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 forthcoming Trains t phosphorus-containing nickel alloy containing 5 to 12 wt .-% are.

The inventively preferred metal-polymer dispersion layer, which is also referred to as a composite layer containing a metal component and at least one polymer as part of the inventions fertil at least one halogenated polymer and optionally further polymers which are dispersed in the metal component.

In contrast to the galvanic deposition, the required electron to be in a chemical or autocatalytic deposition neutrons 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 electrolyte solution which has optionally previously mixed with a stable ized polymer dispersion.

The metal electrolyte solutions usually commercially available or freshly prepared metal electrolyte solutions are used, which conces- addition to the electrolyte, the following components are prepared: phosphite, a reducing agent such as an alkali metal hypo- or borohydride (e.g., NaBH 4), a buffer mixture to adjust the pH; are optionally an activator such as an alkali metal fluoride, preferably NaF, KF or LiF; Carboxylic acids and optionally a deposition moderator, for example, 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.

The optional to use halogenated polymer of the method according invention is halogenated, preferably fluorinated. Examples of suitable fluorinated polymers are ethylene Polytetrafluorine-, perfluoroalkoxy polymers (PFA, for example with Ci-Ca -Alkoxyein- units), copolymers of tetrafluoroethylene and perfluoroalkyl vinyl ethers, for example perfluorovinyl propyl ether. Particularly preferred are polytetrafluoroethylene (PTFE) and perfluoroalkoxy polymers (PFA, according to DIN 7728, part 1, January 1988). When insert molding usefully commercially available polytetramethylene fluoroethylene dispersions (PTFE dispersions) are 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 particularly preferred because the use of spherical particles results in very homogeneous layers composite. Advantage of the use of spherical particles is faster layer growth and better, in particular longer thermal stability of the baths, which provides 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 liter), or an ionic detergent (for example, alkyl and haloalkylsulfonates, alkylbenzenesulfonates, alkylphenol ether sulfates, tetraalkylammonium salts or optionally contain mixtures of said substances, from 15 to 60 g per liter of ionic detergent) to stabilize the dispersion. It can be added in addition also fluorinated surfactants (neutral and ionic), typically 1-10 wt .-% are used, based on the total amount of surfactant.

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, the deposition rate can be increased. 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, for example NaF or KF, increases the deposition rate.

Commercial Nickelelektrolytlösun- are particularly preferred gen containing Ni 2+, Natriumhypophosph.it, 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 P0 2 -H 2 0 at a PTFE content of from 1 to 25 g / 1 included.

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

For contacting the parts to be coated are immersed in immersion baths which contain the metal electrolyte solution. Another embodiment of the method according to the invention is that the containers to be coated with metal electrolyte - are filled solution. Another suitable method is to pump the electrolyte solution through the part to be coated; This variant in particular when the diameter of the part to be coated is much smaller than the length recommended.

Preferably is annealed following the dipping operation, at temperatures of 200 to 400 ° C, especially at from 315 to 380 ° C. The tem- is perungsdauer minutes to 3 hours is generally from 5, preferably 35 to 60 minutes.

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 50 .mu.m, in particular from 5 to 25 microns. The polymer content of the dispersion coating is 5 to 30 vol .-%, preferably 15 to 25 vol .-%. The present invention further treated surfaces exhibit excellent durability.

In another embodiment, the metal-polymer dis- persionsschicht contains an additional polymer to enhance the properties of the coating antihaf Tenden on. This polymer can be halogenated or nichc-halogenated. Particularly preferred is the use of polytetrafluoroethylene or ethylene polymers and ethylene copolymers or polypropylene, said ultra high molecular weight polyethylene (UHM PE) is particularly preferred. Here, a polyethylene is under UHM PE understood that w is a molar mass of 10 6 g or more and an intrinsic viscosity of at least 15 dl / g, preferably at least 20 dl / g.

This polymer optionally used is also available as a dispersion or slurry to be in an aqueous surfactant solution, wherein the order of addition of the dispersions is not critical. however, preferable is the simultaneous metering of the two polymer dispersions. Aqueous dispersions of UHM PE are commercially available, for example from the company Clariant GmbH, or can be readily prepared by dispersing the UHM PE in a suitable aqueous surfactant solution itself be prepared. Suitable detergents are neutral (for example, polyglycols, alkyl phenol ethoxylate, or optionally mixtures thereof, 80 to 120 g of neutral detergent per liter), ionic detergents ether sulfates (for example, alkyl and haloalkylsulfonates, alkylbenzenesulfonates, alkylphenol, said tetraalkyl ammonium salts or optionally mixtures of materials, 15 to 60 g per liter of ionic detergent) containing. It can be added in addition also fluorinated surfactants (neutral or ionic), typically 1-10 wt .-%, based on the total amount of surfactant used.

It is important that the particles of the further, halogenated or non-halogenated polymer are coarser than that of the halogenated polymer. Thus, average particle diameter of 5 to 50 microns have been found to be advantageous. Particularly advantageous are 25-35 microns. It is possible, when using the additional coarser polymer spherical particles, but the particles of the additional polymer may also be shaped irregularly.

It is important that the particle diameter distribution of the various polymers is to be regarded overall as bimodal. be 1 to 20 g per liter of the immersion bath solution, preferably 5 to

10 g of coarse polymer added.

Another object of the present invention is a procedural for producing modified, ie coated surfaces of apparatuses and apparatus parts for chemical plant construction, particularly adhesive, are durable and heat resistant and therefore solve the problem of the invention in a special way.

This method is characterized in that applying microns thick metal-phosphorus layer by electroless chemical deposition before application of the metal-polymer dispersion layer additionally contains a 1 to 15 microns, preferably 1 to. 5

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 brought into a second immersion bath, which also includes a stabilized polymer dispersion, in addition to the metal electrolyte. Here, the metal-poly- mer dispersion layer forms.

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

The electroless chemical deposition of a 1 to 15 micron thick metal-phosphorus layer for improving adhesion is carried out by the already-described metal electrolyte baths, however, where no stabilized polymer dispersions are added into diesel sem 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 by bringing the workpiece in the above-described immersion bath which also contains a stabilized polymer dispersion, in addition to the metal electrolyte. Here, the metal-polymer dispersion layer forms.

If the one embodiment is chosen which provides for the additional use of a non-halogenated polymers, it is preferable to dispense with a heat treatment of the finished coating. In a preferred embodiment of the method according to the invention is in the additional metal-phosphorus layer is nickel-phosphorus or copper-phosphorus, nickel-phosphorus is particularly preferable.

The inventive method can, due to its ease of handling in all risk of deposits surfaces of apparatuses and apparatus parts for chemical plant use, the surfaces of metal surfaces preferably sawn Sonders preferably made of steel, are.

Container and apparatus walls may be present in different containers, apparatus or reactors used in chemical reactions.

For containers are, for example, quench or collecting such as wells, silos, tanks, barrels, drums or gas tank.

- In the apparatuses and reactors is liquid, gas / liquid, liquid / liquid, solid / liquid, gas / solid or gas reactors, which are realized, for example, in the following ways:

- a stirring, jet loop and jet reactors,

Jet pumps,

Residence-time, static mixers,

Stirred columns - tubular reactors,

Zylinderrührer,

Bubble columns,

Jet and Venturi scrubbers,

Fixed bed reactors, - reaction columns

evaporator

Hub reactors

Extraction columns,

Kneading and mixing reactors and extruders - mills,

Belt reactors,

Rotary kilns or circulating fluidized beds; At discharge devices are, for example, be dispensing nozzle, discharge hopper, discharge pipes, valves, Austragshähne or ejectors.

- For valves is, for example, taps and valves, rupture discs, check valves or disks.

When pumps are, for example, centrifugal, tooth wheel-, screw, progressing cavity, rotary piston, reciprocating, diaphragm, screw trough or jet liquid pumps act also to reciprocating, reciprocating diaphragm, rotary lobe, rotary vane, liquid ring, rolling on piston, liquid ring vacuum pumps or propellants.

Filter apparatuses is, for example, fluid filter, fixed-bed filters, gas filters, sieves or traps.

In compressors are, for example, reciprocating, reciprocating diaphragm, rotary piston, rotary vane, annular liquid, rotation, roots, screw, jet or turbo compressors.

For centrifuges are, for example, centrifuges or solid bowl screen jacket, said plate, solid bowl - worm (decanter), Siebschnecken- and pusher centrifuges are preferred.

In columns is container with trays, wherein bubble-cap, valve or sieve trays are preferred. In addition, the columns with different packings such as saddles, Raschig rings or balls can be filled.

- For shredding machines is, for example,

Breakers, wherein hammer, impact, roller or jaw crushers are preferred; or mills, said hammer, Schlagkorb-, pen, impact, pipe, drum, ball, vibratory, roll mills are preferred.

For installations in reactors, tanks and vessels, for example, to thermal sleeves, baffles, foam breakers, packing elements, spacers, centering, flange, static mixers, for analysis DIE designating instruments such as pH or IR probes, conductivity meters, level measurement devices or foam probes.

In extruder elements are, for example, worm shafts, -elements, extruder barrel, screw plasticizing or injection nozzles.

Another object of the invention are available rate by the appA Inventions proper method for surface modification and apparatus parts for chemical plant construction. Preferably, the preparation of the surfaces according to the invention is carried out by applying the method according to the invention.

Another object of the invention is to deposit to form deposits, the use of surface modification according to the invention for reducing the tendency of the coated surfaces, solids. The deposits whose formation is inventively prevented, have already been described.

Another object of the invention are coated apparatuses and apparatus parts for chemical plant construction. The reactors of invention proper, reactor parts and processing machines for chemical products are characterized by a longer tool life, reduced Abschaltquoten and reduced cleaning expense.

The reactors according to the invention can be used for many different types of reactions such as polymerizations, syntheses of bulk or fine chemicals or pharmaceu- tical products and their precursors, and cracking reactions. The methods are continuous, semi-continuously or batchwise, with the use of the apparatuses and apparatus parts for chemical plant construction according to the invention in continuously operated process especially offers.

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

Working Example:

In attempts to optimize the process Styropor ® -production (according to EP-A 0575872) on a laboratory scale (41-stirred tank) was parallel to the non-coated steels V2A steels used according to the invention with a modified surface. For the coating procedure was as follows:

1. A coating with nickel-PTFE

The coating was performed in two stages. First, several parts of the autoclave was expanded: stirrer, thermocouple sleeves, current disturber, cover and parts of the reactor inside. These parts were immersed at a temperature of 88 ° C in a pan containing 2 liters of an aqueous nickel salt solution, the solution having the following composition: 27 g / 1 NiS0-6 H 2 0, 21 g / 1 NaH 2 P0 2 .2H 2 0, 20 g / 1 of lactic acid CH 3 CHOHC0 2 H, 3 g / 1 propionic acid C 2 H 5 CO 2 H, 5 g / 1 Na-citrate, 1 g / 1 NaF. The pH was 4.8. The procedure was 45 minutes to obtain the desired layer thickness of 9 microns.

After this step has not been flushed.

Subsequently, the reactor parts were dipped in a second bath, which was next to 2 liters of an analogous nickel salt solution is added in addition to 20 ml, which is 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 10 microns / h the process was terminated in 90 minutes (coating thickness 15 microns). The coated reaction door sections were rinsed with water, dried and heated for one hour at 350 ° C.

2. Coating with nickel-PTFE / PE-UHM

The coating was performed in two stages. First, several parts of the autoclave was expanded: stirrer, thermocouple sleeves, current disturber, cover and parts of the reactor inside. These parts were immersed at a temperature of 88 ° C in a pan containing 2 liters of an aqueous nickel salt solution, the solution having the following composition: 27 g / 1 NiS0-6 H 2 0, 21 g / 1 NaH 2 P0 2 .2H 2 0, 20 g / 1 of lactic acid CH 3 CHOHC0 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. The procedure was 45 minutes to obtain the desired layer thickness of 9 microns.

After this step has not been flushed.

Subsequently, the reactor parts were dipped in a second bath, the addition of 20 ml, which is 1 volume had been added in addition to 2 liters of an analogous nickel salt solution .-% of a PTFE dispersion with a density of 1.5 g / ml; further 7 g / 1 UHM PE (Clariant AG) were added. This PTFE / UHM PE dispersion contained 50 wt .-% solids. At a deposition rate of 10 microns / h the process was terminated in 90 minutes (coating thickness 15 microns). The coated reactor parts were rinsed with water and dried at room temperature. In the heat treatment was dispensed with.

The reactor parts were installed in a test autoclave for Styrofoam production. In order for the stirred tank contained both coated and uncoated parts in Polymerization - try could be tested under identical conditions. The method described according to one method, at the in EP-B 0575872 (p. 5, line 8 et seq) leans, was polymerized as follows:

2.61 g of NaP 2 0 were dissolved at room temperature in 89.7 ml of water. While stirring, a solution of 4.89 g MgS0 4 -7 H 2 0 was added to 44.8 ml of water to this solution and stirred for an additional 5 minutes.

In the stirred tank, which contained the coated inserts described above, 1,4 1 of water were placed and a 4 P 4 solution with stirring for 2 θ 7 -MgSθ. Subsequently, 1523 ml of styrene (freshly distilled) together with 4.23 g of dicumyl peroxide and 2.26 g of dibenzoyl peroxide was added. In the organic phase, 0.55 g and 1.7 g methylstyrene Luwax® were further dissolved with stirring. It was saturated with nitrogen and heated in 2 hours to 90 ° C. 2 hours after exceeding the 80 ° C threshold was 0.23 g of a 40 wt. -% solution of Mersolat® K30 together with 0.18 g of a 20 wt. -% aqueous sodium hydroxide solution and 0.12 g of acrylic acid (100%) was added further 50 minutes later were 123.5 g of n-heptane was added. Meanwhile, the temperature was kept constant at 90 ° C and polymerization is completed the suspension.

After a total of 20 hours, the reaction was stopped and cooled within 1 hour at room temperature and stirred tank emptied.

The inspection of the stirred tank showed that at all coated with the inventive coating Make a significantly lower polymer coating was visible than at uncoated points. The polymer coatings on coated with a coating according to the invention points could be removed more easily than the deposits on the uncoated places. The analysis is presented in Table 1. Partial could be rubbed off manually with an inventive loading coating coated areas of the deposit on. If the coating on coated with a coating according to the invention bodies had to be removed by dissolution in toluene or other suitable solvent, the solution times were significantly shorter than in coverings of non-coated areas.

For evaluation, the deposits were weighed to baffles and agitators.

1 baffle was not coated,

Empty weight: 61.51 g uncoated baffles 1 was coated by the inventive process with Ni-PTFE

Empty weight: 60.78 g coated baffles 1 was coated by the inventive process with Ni-PTFE / PE-UHM

Empty weight: coated 62,04g The polymerization examples were repeated, uncoated in each case 1 experiment with a stirrer and a stirrer coated with 1 test with an inventive coating

Empty weight: 490,52g uncoated Empty weight: 493,28g coated

The stirrer speeds can be seen from Table 1 below.

Table 1

nd not determined

Also, the Terluran production were on a laboratory scale (41-autoclave) used in parallel with V2A-steel steels with a modified surface by an inventive coating at basic experiments for process optimization. The polymerization examples were carried out according to DE-A 197 28 629 and EP-A 0,062,901, each of Example 1, but the proportions have been adjusted to the 2-liter autoclave and the stirrer speed was varied according to Table 2 below.

Starting with a total of 661.61 g butadiene was added tert-dodecyl mercaptan ( "TDM") in the presence of 6.59 g, 4.6 g of potassium stearate, 1.23 g of potassium persulfate, 1.99 g sodium bicarbonate and 824 g of water at 67 ° C polymerized. The reactor was emptied and inspected.

the agitator was coated. Again, it was observed that deposits on occurred significantly reduced coated by the novel process sites and removed more easily than could at uncoated points.

were weighed deposits on the impellers.

3 experiments were reproduced, uncoated in each case 1 experiment with a stirrer and

1 experimental coated with a stirrer Ni-P-PTFE

Empty weight: 376,53g uncoated

Empty weight: coated 378,49g

with otherwise identical reaction and process conditions.

Table 2:

Claims

claims
1. A process for coating apparatuses and apparatus parts for chemical plant construction, characterized in that a metal layer or a metal polymer -Dispersions - layer on the electrolessly deposited or the apparatuses to be coated or apparatus parts, by treating the parts with a metal contacted electrolyte solution containing a reducing agent in addition to the metal electrolyte, and, optionally, the polymer or polymer mixture to be deposited in dispersed form, wherein at least one polymer is halogenated.
2. The method according to claim 1, characterized in that it is in the chemical apparatuses and apparatus parts for
Plant to apparatus, container and Reaktorinnenwandungen, discharge devices, valves, line systems, pumps, filters, compressors, centrifuges, columns, dryers, comminution machines, internals, packing elements and mixing elements Han delt, which consist of a metallic material.
3. The method according to claim 1 and 2, characterized in that there is used as metal-nickel or copper electrolyte, an electrolyte solution and the reducing agent is a hypophosphite or a borohydride.
4. The method according to claim 1 to 3, characterized in that is added to the metal electrolyte solution, a dispersion of a halogenated polymer.
5. The method according to claim 1 to 4, characterized in that is used as the metal electrolyte, a nickel salt solution, which is reduced in situ with an alkali metal hypophosphite and is added as halogenated polymer, a polytetramethylene fluoroethylene dispersion.
6. Process according to claims 1 to 5, characterized in that one uses a halogenated polymer of particles having an average diameter of 0.1 to 1.0 microns..
7. The method according to claims 1 to 6, characterized in that a halogenated polymer is used composed of spherical particles having an average diameter of 0.1 to 1.0 microns.
8. Process according to claims 1 to 7, characterized in that depositing a nickel-phosphorus polytetrafluoroethylene layer having a thickness of 1 to 100 microns.
5 9. Process according to claims 1 to 8, characterized in that one deposits a layer of nickel-phosphorus polytetrafluoroethylene having a thickness of 3 to 50 microns.
10. The method according to claims 1 to 9, characterized gekennzeich- net 10 in that a nickel-phosphorus polytetrafluoroethylene
deposited layer having a thickness of 5 to 25 microns.
11. The method according to claims 1 to 10, characterized in that the metal electrolyte solution, a further dis-
15 persion adding a halogenated or non-halogenated polymer.
12. The method according to claim 11, characterized in that as an additional polymer is a polytetrafluoroethylene
20 or polyethylene or polypropylene.
13. The method according to claims 11 to 12, characterized in that as an additional fluoroethylene polymer is a polyethylene or polypropylene or polytetramethylene of particles
25 is used with an average diameter of 5 to 50 microns.
14. The method according to claims 1 to 13, characterized in that before application of the metal-polymer dispersion layer initially an additional 1 to 15 microns thick
electroless chemically deposited 30 metal-phosphorus layer.
15. The method of claim 1 to 14, characterized in that as an additional layer is deposited, a nickel-phosphorus layer.
35
16, apparatuses and apparatus parts for chemical plant construction, obtainable by the process according to claims 1 to 15 °.
17 apparatus, tank and reactor walls, Austragsvorrich- 40 obligations, valves, line systems, pumps, filters, compressors, centrifuges, columns, dryers, comminution machines, internals, packing elements and mixing elements, obtainable by the process according to claims 1 to sixteenth
45 18. Use of apparatus, container and reactor walls,
Discharge devices, valves, line systems, pumps, filters, compressors, centrifuges, columns, dryers, size reduction machines, internals, packing elements and mixing elements according to claims 18 and 19 for preventing or reducing deposits from Fiuiden.
EP19990967007 1998-12-30 1999-12-24 Method for coating apparatuses and parts of apparatuses used in chemical manufacturing Not-in-force EP1144723B1 (en)

Priority Applications (3)

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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/EP1999/010371 WO2000040774A3 (en) 1998-12-30 1999-12-24 Method for coating apparatuses and parts of apparatuses used in chemical manufacturing

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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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CA (2) CA2358099A1 (en)
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EP1144724A2 (en) 2001-10-17 application
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