WO2006076160A1 - Surfaces a faible energie pour reduction de la corrosion et de l'encrassement - Google Patents

Surfaces a faible energie pour reduction de la corrosion et de l'encrassement Download PDF

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Publication number
WO2006076160A1
WO2006076160A1 PCT/US2005/047101 US2005047101W WO2006076160A1 WO 2006076160 A1 WO2006076160 A1 WO 2006076160A1 US 2005047101 W US2005047101 W US 2005047101W WO 2006076160 A1 WO2006076160 A1 WO 2006076160A1
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WIPO (PCT)
Prior art keywords
layer
metal surface
organometallic
metal
organometallic compound
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PCT/US2005/047101
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English (en)
Inventor
Ian A. Cody
Hyung S. Woo
Mark A. Greaney
George Stephens
Mohsen Yeganeh
Shawn M. Dougal
Ashley E. Cooper
Hugh L. Huffman
Thomas Bruno
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Exxonmobil Research And Engineering Company
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Priority to JP2007550401A priority Critical patent/JP2008527172A/ja
Priority to EP05855625A priority patent/EP1838461A1/fr
Priority to CA002594305A priority patent/CA2594305A1/fr
Publication of WO2006076160A1 publication Critical patent/WO2006076160A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B05D7/16—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies using synthetic lacquers or varnishes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
    • C10G75/04—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of antifouling agents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
    • C10G9/16—Preventing or removing incrustation
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
    • B05D1/185—Processes for applying liquids or other fluent materials performed by dipping applying monomolecular layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/60—Deposition of organic layers from vapour phase

Definitions

  • This invention relates to a method for reducing fouling and corrosion of metal surfaces. More particularly, metal surfaces such as piping and heat exchangers that transport or contain corrosive and contaminated materials can be protected by formation of organometallic coatings that are in the range of monolayers in thickness.
  • Fouling of metal surfaces such as the piping, heat exchangers and reactors used in refineries and chemical plants result in significant costs including cleaning and equipment down times.
  • Such fouling can occur from a number of sources such as crudes, distillates, process feedstocks and the like.
  • costs may also include energy costs associated with more extreme operating conditions necessitated by the presence of foulants such as coke and attendant safety issues.
  • the costs associated with cleaning and equipment down times can run into annual costs in the hundreds of millions of dollar range.
  • the typical coatings for industrial conduits are generally in the micron to millimeter range in thickness. This is usually to ensure good surface coverage as well as provide a protective layer of sufficient thickness to be robust during operating conditions. However, such thick coatings may limit heat exchange,
  • This invention relates to a process for mitigating both corrosion and fouling of metal surfaces which comprises: contacting the metal surface with an organometallic compound capable of bonding to the metallic surface and forming a layer of organometallic molecules which is 1 to 10 molecular layers thick, which layer will not undergo substantial decomposition at temperatures up to 450 0 C and which layer has a surface energy lower than 50 millijoule/m 2 .
  • Another embodiment relates to a process for mitigating fouling and corrosion in refinery and chemical plant equipment having metal surfaces which comprises: contacting the metal surface with an organometallic compound capable of bonding to the metallic surface and forming a layer of organometallic molecules which is 1 to 10 molecular layers thick, which layer will not undergo substantial decomposition at temperatures up to 450 0 C 5 which layer has a surface energy lower than 50 millijoule/m 2 , and which layer is deposited on greater than 25% up to 100% of the metal surface.
  • Yet another embodiment relates to a process for mitigating fouling in refinery and chemical plant equipment having metal surfaces which comprises: heating the metal surface in an oxygen-containing atmosphere at temperatures of from 100 0 C to 500 0 C for a time sufficient to clean said metal surface of carbonaceous residues, contacting the metal surface with an organometallic compound capable of bonding to the metallic surface and forming a layer of organometallic molecules which is 1 to 10 molecular layers thick, which layer will not undergo substantial decomposition at temperatures up to 45O 0 C, which layer has a surface energy lower than 50 millijoule/m 2 , and which layer is deposited on greater than 25% up to 100% of the metal surface.
  • a still further embodiment relates to a process for mitigating fouling in refinery and chemical plant equipment having metal surfaces containing corrosion layers which comprises: contacting a metal surface containing a corrosion layer with at least one of high pressure water or steam to produce a water or steam cleaned metal surface; heating the water or steam cleaned metal surface in an oxygen-containing atmosphere at temperatures of from 100 0 C to 500 0 C for a time sufficient to further.clean said metal surface of carbonaceous residues, contacting the further cleaned metal surface with an organometallic compound capable of bonding to the metallic surface and forming a layer of organometallic molecules which is 1 to 10 molecular layers thick, which layer will not undergo substantial decomposition at temperatures up to 450 0 C, which layer forms a surface having a water contact angle between 95 to 160 degrees, and which layer is deposited on greater than 25% up to 100% of the metal surface.
  • a metal surface capable of resisting fouling when exposed to corrosive or coke forming at atmospheric or greater pressures which comprises a metal surface and a layer of organometallic molecules deposited on said metal surface, said layer of organometallic molecules being 1 to 10 molecular layers thick, which layer will not undergo substantial decomposition at temperatures up to 45O 0 C, which layer has a surface energy lower than 50 millijoule/m 2 , and which layer is deposited on greater than 25% up to 100% of the metal surface.
  • Treatments with silicate sols, or paints rich in silicon or aluminum typically produce relatively thick surfaces (micron to millimeter) that can provide a physical boundary that protects the underlying metal from corrosion.
  • the surface is created by reaction of an organometallic such that the organic moiety is retained (chemisorbed), yielding a stable, thin near monolayer surface that is more resistant to spalling and cracking than thicker coatings and has a low surface energy needed to discourage and reject potential deposits.
  • an organometallic such that the organic moiety is retained (chemisorbed), yielding a stable, thin near monolayer surface that is more resistant to spalling and cracking than thicker coatings and has a low surface energy needed to discourage and reject potential deposits.
  • Figure 1 is a photograph showing the scanning electron microscopy micrographs of steel coupons exposed to hot crude together with corresponding graphs showing the sulfur content using energy dispersive spectroscopy.
  • Figure 2 is a photograph showing a cross section of the scanning electron microscopy micrographs of steel coupons exposed to hot crude.
  • Figure 3 is a graph showing wt.% silicon as a function of wt.% carbon on various steel samples.
  • Figures 4A and 4B are plots of Gibbs Free Energy vs. surface energy (4A) and the corresponding plot of surface energy vs. water contact angle (4B).
  • Figure 5 is a graph showing surface energy as a function of water contact angle.
  • Figure 6 is a photograph showing the fouling of carbon steel coupons as a function of water contact angle.
  • feedstocks are prone to produce fouling of process equipment.
  • feeds include crude which can contain contaminants that foul equipment by depositing residue and/or corrosive components.
  • contaminants include salts, metals, sulfur- and nitrogen-containing species, distillation bottoms and the like.
  • Corrosive components include acidic compounds such as sulfur-containing acidic species and naphthenic acids.
  • Such contaminated feeds produce coke and other undesirable deposits that limit flow and heat exchange.
  • This invention relates to a metal surface and a process using said metal surfaces wherein an organometallic coating is used to protect metal surfaces, especially those present in refinery and chemical plants.
  • Most refinery and chemical plant process equipment is made from carbon steel and alloys thereof.
  • Stainless steel is more resistant to corrosion but is less frequently employed as a metal of fabrication because of the increased cost.
  • the organometallics used in the present process are those which are capable of bonding to a metal surface and which will not decompose at the temperature to which the metallic surface is exposed.
  • Most organometallics used in the prior art to protect metallic surfaces are employed as precursors and are converted to oxides which function as the protective coating.
  • the organometallic compound, not its oxide functions as the protective coating.
  • the present organometallic coating functions as a chemical protective layer in the monolayer range as compared to a physical barrier provided by the much thicker prior art coatings.
  • the metallo components of the organometallic compounds are from Groups 4 to 15 based on the IUPAC format for the Periodic Table having Groups 1 to 18, preferably Group 14, more preferably silicon and tin, especially silicon.
  • the organo components of the organometallic compounds are hydrocarbyl groups having from 1 to 30 carbon atoms, preferably from 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms.
  • the hydrocarbyl groups may be aliphatic or aromatic groups which aliphatic or aromatic groups may be substituted with functional groups such as oxygen, halogen, hydroxy and the like.
  • Preferred hydrocarbyl groups include methyl, ethyl, methoxy, ethoxy and phenyl.
  • Preferred organometallic compounds include alkysilanes, alkoxysilanes, silanes, silazanes and alkyl and phenyl siloxanes.
  • Especially preferred compounds include alkyl- or alkoxysilanes having from 1 to 20 alkyl or alkoxy groups, especially tetraalkoxy compounds such as tetraethoxy-silane, alkylsilanes having from 1 to 6 alkyl groups, especially hexamethyl-disiloxane.
  • the organometallic coating on the metallic surface should have a low energy surface.
  • low energy surface is meant a coating having a surface free energy lower than 50 milli Joules/square meter (mJ/m 2 ), preferably between 21 to 45 mJ/m 2 .
  • the surface free energy is determined by measuring the water contact angle.
  • the low surface energy of the layer ensures a low interfacial energy at, for example, the interface between crude oil and the coated layers, even at the higher temperature conditions found in typical heat exchangers, e.g., 200 0 C to 400 0 C for a crude pre-heat exchanger train. This in turn provides for a weak interaction of foulants and corrosive species with the surface resulting in a reduction in fouling and corrosion rate.
  • the amount of covering of the organometallic coating layer ranges from greater than 25% of the metal surface to 100% of the metal surface, preferably from 50 to 100%, more preferably from 80 to 100%.
  • the amount of metal surface covered is most preferably 100% or as close to 100% as possible.
  • the metal surface to be protected is preferably clean of carbonaceous deposits such as coke. This is important in continuous processes in which a feed is heated while in contact with a metal surface such as pipes used in refinery and chemical plant service, heat exchangers and furnace tubes.
  • a metal surface such as pipes used in refinery and chemical plant service, heat exchangers and furnace tubes.
  • the metal surface is preferably cleaned by heating in the presence of an oxygen-containing gas, preferably air, at temperatures of from 200 0 C to 500 0 C, preferably 300 0 C to 400 0 C for a time suff ⁇ cient to remove the desired deposits, particularly carbonaceous deposits.
  • the heating typically occurs at atmospheric pressure although higher pressures are acceptable.
  • a water wash may be used to remove salts.
  • the cleaned metal surface may also be treated with a solution of metal salt to enhance the effectiveness of the organometallic coating process.
  • a carbon steel surface may be first treated with a Cr salt solution.
  • the cleaned and heated metal surface is then subjected to organometallic coating by exposing the heated metal to organometallic compound in the gaseous phase, liquid phase or mixed liquid-vapor phase.
  • the organometallic compound may be sparged into the vapor state using a carrier gas such as nitrogen or the organometallic may be mixed with a carrier liquid such as cyclohexane, xylene, water carbon tetrachloride, chloroform, fuel oil, lube boiling range hydrocarbon, crude oil and the like as a dilute solution, e.g., up to 5 vol.%.
  • the organometallic coating process should preferably take place in the absence of an oxygen- containing gas.
  • the temperature of the coating process may range from ambient to 500 0 C.
  • the upper temperature range for coating is a function of the stability of the particular organometallic used for coating.
  • the extent of the surface modification by organometallic coating can be measured using water contact angles. This test measures the contact angle of water in contact with the modified metal surface. An example of a test procedure for measuring water contact angles is ASTM D-5725. High water contact angles imply high hydrophobicity and good coverage of the underlying metal (or metal oxide/sulfide) surface by the organometallic coating. For the metal surfaces modified according to the invention, measured water contact angles are between 95 to 160 degrees, preferably 110 to 150 degrees.
  • the thickness of the organometallic coating ranges from 1 to 10 molecular layers thick, preferably 1 to 3 molecular layers thick, more preferably a monolayer thick. The thickness of the molecular layer may be controlled by the deposition process, e.g., by controlling the time of exposure of the metal surface to the organometallic compound and controlling the pressure under which the coating is applied.
  • Organometallic molecules according to the invention should be maintained below 450 0 C, preferably below 400 0 C, more preferably below 35O 0 C.
  • Some decomposition of organometallic coating may occur depending on the nature of the organometallic employed as coating and the operating temperature employed.
  • phenyl silanes as coating agent can be stable at higher temperatures and may be used in more severe service than alkyl silanes.
  • substantially decomposition of the layer of organometallic molecules is meant that the organometallic molecules in the coating (covering) layer are reduced to less than 25% coverage of the metal surface.
  • the behavior of the present organometallic coatings is believed to be at least in part a function of the organo moiety. While not wishing to be bound to any particular theory, it appears that the organo moiety minimizes the interaction energy with both polar and non-polar hydrocarbons and mitigates fouling and corrosion in this manner. Minimizing corrosion can be linked with minimizing fouling. For example, corrosion tends to increase the metal surface area creating a trap for foulants. Ordinary ceramic coatings of metals surfaces rely on a physical barrier to mitigate corrosion. However, ceramic coatings will not be as effective as organometallics because surface energies may still be high, i.e., greater than 100 mJ/m 2 . The same reasoning applies to oxide coatings used to provide a physical barrier.
  • metals particularly steels and alloys thereof, can be provided with a low surface energy monolayer or near monolayer of organometallic coating that resists both corrosion and fouling deposits in refineries and chemical plants.
  • organometallic coating examples include crude preheat trains, steam cracker transfer lines, and transfer lines used in polymer manufacture.
  • the material to be protected by organometallic coating may also be other metals as well as non-metal materials such as ceramics.
  • An example of a refinery process which illustrates the invention are heat exchangers common to many refinery units such as boilers. These exchangers are periodically taken out of service for cleaning resulting in unit down time as well as cleaning costs.
  • the heat exchangers after traditional cleaning would be heated in air to remove carbonaceous deposits and then coated with an organometallic such as hexamethyl disiloxane (HMDSO) by exposing the heated (300 0 C to 400 0 C) clean metal surface to HMDSO at low pressure in an oxygen-free environment until a coating is achieved, typically in less than 1 hour. The unit is then ready to be returned to service.
  • HMDSO hexamethyl disiloxane
  • SEM micrographs shown in Figure 2 were also obtained from cross sections of the same coupons.
  • the images from HMDSO treated coupon shows very little variation along the edge of the coupon/epoxy interface while thermally treated coupon shows very rough texture along the edge of the coupon/epoxy interface.
  • the coupon/epoxy interface shows the roughness of the exterior surface of the coupons.
  • This example is directed to a procedure to provide coverage of a steel surface and illustrates the importance of providing a surface from which most of the carbonaceous deposits have been removed.
  • Carbon steels tend to retain more carbonaceous contaminants than stainless steels and for best effect should be pretreated.
  • a preheat in air or O 2 at about 350 0 C may be adequate to eliminate any carbonaceous residue in many cases.
  • This methodology can also apply to treatment of exchangers previously in service.
  • Various samples of steel bearing different amounts of carbon deposits were treated with HMDSO at 20 torr pressure and 300 0 C for varying time periods to remove different amounts of carbon deposits from the steel samples. The results are shown in Figure 3 which is a graph showing wt.% silicon versus wt.% carbon based on the weight of the coupon.
  • TlA is a carbon - 1/2 % molybdenum steel
  • 1018 is a carbon steel
  • 310 and 304 are stainless steels.
  • Run 5 is also a stainless steel.
  • the wt.% Si on the steel samples is dependent on the amount of carbonaceous deposit remaining. At about 30 wt.% carbon, the amount of Si starts to increase and continues to increase as the amount of carbon remaining decreases.
  • Modification can be affected over a range of conditions and from different media. Vacuum deposition of HMDSO is effective in providing surfaces that resist corrosion and fouling as illustrated by experiments in Example 1 above.
  • Surfaces can be modified from a mixed liquid- vapor phase using, e.g., high boiling lube hydrocarbons to solubilize the organosilane. Treatments can also be performed by sparging an inert gas (e.g. N 2 or Ar) into liquid modifier to transport vapor to the reaction site. In this mode treatment times may need to be several hours to ensure a near monolayer is formed. Treatment temperatures may range from 200 0 C to 500 0 C for stainless steel, and are preferably 300 0 C to 400 0 C for carbon steel.
  • Reagent choice may vary depending on the intended service and/or limits of conditions for treatment.
  • Various alkoxysilanes and alkyl and aryl substituted siloxanes and silazanes are examples of organometallics.
  • Figures 4A and 4B are plots of Gibbs Free Energy versus surface energy (4A) and the corresponding plot of surface energy versus water contact angle (4B).
  • the strength of adsorption of the foulant materials from a liquid onto the surface can be determined using the Gibbs and adsorption isotherm equations.
  • the Gibbs equation relates the interfacial coverage to the interfacial energy and the adsorption isotherm equation, such as the Langmuir adsorption isotherm equation relates the interfacial coverage to the Gibbs free energy of adsorption.
  • the interfacial energy is a function of the surface energy of the liquid and the surface energy of the solid. Since the surface energy of the solid is low, the interaction between the solid and the oil is a weak dispersion.
  • the interfacial energy, y ⁇ s can be written as a function of the surface energy of the solid, ⁇ s , and the surface energy of the liquid, % as:
  • Curve B of Figure 4A shows the variation of minimum Gibbs free energy of adsorption with the solid surface energy. It shows that the adsorption is weak if the interfacial energy is low and the surface energy of the solid is close to the surface energy of the liquid.
  • FIG. 4B shows the relationship between the surface energy of the solid and the water contact angle, ⁇ , for low surface energy solids using:
  • a water contact angle should be larger than 98 degrees.
  • a measure of the extent of surface modification by the surface modification step can be made using a device to calculate the extent to which water beads up on the treated surface (the water contact angle). High angles imply high hydrophobicity and good coverage of the underlying substrate by the modifier. There is a correlation between reduced fouling propensity and higher water contact angle, as can be seen from Figure 5 which is a graph showing surface energy as a function of water contact angle.
  • the water contact angles were measured using a Kruss Automated Angle tester with a DSA 100 Device Control Panel. The instrument was calibrated using high purity water. The calculations of water contact angles were made using images captured on video camera. The contour of the drop is traced and the curve tracing used to calculate the average contact angle. When the surface is uneven, the drop contour cannot be seen all the way down to the surface and a certain distance is excluded from the water contact angle analysis. The corresponding contour is compiled from the drop contour that can be measured. Data from captured images are averaged in the water contact angle calculations. The left and right contact angles from several measurements are averaged to give an overall contact angle in degrees.
  • Carbon steel coupons were exposed to Maya whole crude at 35O 0 C for 3 hours to simulate conditions that might exist in a crude pre-heat exchanger.
  • the coupons were variously modified with octatridecyl trichloro silane to affect different levels of coverage.
  • Multiple treatments with an intervening air calcination step generated coupons with the highest contract angles (above 130 degrees). These coupons formed very little measurable deposit whereas the coupons with lower contact angles and particularly the untreated carbon steel coupon showed significant deposits, measurable by both a weight gain and by a decline in electrical resistivity.
  • Figure 6 shows the fouling of the coupons as a function of water contact angle. The high water contact angles are achievable on steel surfaces that are fresh or have previously been in surface and subsequently cleaned.
  • Heat exchanger tubes from prior service are usually found to have a combination of iron sulfides mixed with carbonaceous deposits.
  • Refiners clean such tube bundles with high pressure water ("hydroblasting") to scour loosely held residues from the tube surface, both inside and out, then return them to service.
  • Tubes undergoing this treatment usually retain a sulfide/oxide layer that is different from the original fresh metal surface that typically comprises iron and iron oxides (if carbon steel) or perhaps spinel type oxides of Fe and Cr if higher alloy steels are used.
  • Carbon steel and 5-Cr steel tubes that have been in service for months or years in crude preheat service typically show low to moderate water contact angles (80 degrees or less) following hydroblasting and drying. This is correlated with a high surface energy, associated with mixed metal oxides and or sulfide eg FeS. For example, SEM shows that the carbon steel tubes retained a 20 micron thick iron sulfide layer after hydroblasting and drying.
  • Subsequent air heating at 35O 0 C for 1 hr. further lowers the water contact angle (i.e. raises the surface energy) indicating that a very hydrophilic (presumably hydroxylated) surface is generated. This can be a good substrate for subsequent reaction with the right surface modifier.
  • Table 2 below indicates that effective surfaces to resist fouling (and corrosion) can be generated whether the surface is fresh or has been in service.
  • Range of values indicates typical surface in homogeneities from sample to sample and across the surface of a given sample

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Abstract

L'invention concerne des surfaces métalliques et un procédé de réduction de l'encrassement de surfaces métalliques, plus particulièrement de surfaces métalliques telles que des tuyauteries et des échangeurs thermiques transportant ou contenant des matières corrosives et polluées susceptibles d'être protégées par la formation de revêtements organométalliques compris dans une fourchette de monocouches en termes d'épaisseur.
PCT/US2005/047101 2005-01-10 2005-12-28 Surfaces a faible energie pour reduction de la corrosion et de l'encrassement WO2006076160A1 (fr)

Priority Applications (3)

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JP2007550401A JP2008527172A (ja) 2005-01-10 2005-12-28 腐食および汚れを低減する低エネルギー表面
EP05855625A EP1838461A1 (fr) 2005-01-10 2005-12-28 Surfaces a faible energie pour reduction de la corrosion et de l'encrassement
CA002594305A CA2594305A1 (fr) 2005-01-10 2005-12-28 Surfaces a faible energie pour reduction de la corrosion et de l'encrassement

Applications Claiming Priority (4)

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US64267505P 2005-01-10 2005-01-10
US60/642,675 2005-01-10
US68741105P 2005-06-03 2005-06-03
US60/687,411 2005-06-03

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