Source: https://patents.google.com/patent/US9353434B2/en
Timestamp: 2018-11-17 07:38:18
Document Index: 611843856

Matched Legal Cases: ['§119', 'Application No. 60', 'art=26188', 'Application No. 2', 'Application No. 2', 'Application No. 2']

US9353434B2 - Methods for providing prophylactic surface treatment for fluid processing systems and components thereof - Google Patents
Methods for providing prophylactic surface treatment for fluid processing systems and components thereof Download PDF
US9353434B2
US9353434B2 US12444519 US44451907A US9353434B2 US 9353434 B2 US9353434 B2 US 9353434B2 US 12444519 US12444519 US 12444519 US 44451907 A US44451907 A US 44451907A US 9353434 B2 US9353434 B2 US 9353434B2
US12444519
US20100112378A1 (en )
Mark A. Deininger
Mikhail Pozvonkov
D. Morgan Spears
Leonid V. Budaragin
C3 International LLC
In one embodiment, the invention relates to a method for creating a diffused thin film surface treatments on one or more interior surfaces of closed or partially closed fluid transport or processing systems providing improved surface prophylaxis against fouling. The method involves contacting the interior surfaces to be treated with a metal compound composition, and converting the metal compound composition to metal oxide for example by heating the surfaces to the desired temperature after all or a part of the system has been assembled. Embodiments of the present invention can be performed in situ on existing fluid processing or transport systems, which minimizes the disruption to the surface treatment created by welds, joints, flanges, and damage caused by or during the system assembly process.
This application claims benefit of priority under PCT Chapter 1, Article 8, and 35U.S.C. §119(e) of U.S. Provisional Application No. 60/851,354, entitled “METHOD FOR PROVIDING PROPHYLACTIC SURFACE TREATMENT FOR FLUID PROCESSING SYSTEMS AND COMPONENTS THEREOF,” filed on Oct. 12, 2006, which is incorporated herein by reference.
The invention relates to methods for creating a metal oxide surface treatment on one or more surfaces of fluid transport or processing systems providing improved surface prophylaxis against fouling. The methods can be performed in situ on existing fluid processing or transport systems, which minimizes the disruption to the surface treatment created by welds, joints, flanges, and damage caused by or during the system assembly process. The invention also relates to articles having one or more surfaces comprising at least one metal oxide.
During operation, various industrial process systems suffer degradation to the working sections of the system being attacked by various chemicals and conditions. This occurs in the oil industry, colorants industry, cosmetics industry, food industry, pharmaceutical industry, chemical industry, and within closed systems such as cooling systems, heating and air conditioning systems, and many others. Additional systems that are affected by surface degradation are furnaces, boilers, internal combustion engines, gas turbine engine systems, rockets, etc. In any continuous or intermittent process system there is the risk of surface degradation due to the exposure of materials to certain chemicals and conditions. The surfaces exposed to the process may degrade due to the material itself degrading, eroding, or corroding, or the degradation may be in the form of deposits that accumulate on the material, affecting performance of one sort of another, e.g. flow efficiency through a pipe. Any kind of degradation is generally referred to as “fouling.” The typical solution to these types of fouling is to upgrade the material used to construct the functional item, be it a pipe, a heat exchanger. etc. For example, a pipe may be constructed of a nickel alloy stainless steel, rather than of common carbon steel, in an attempt to improve its inner and outer surface longevity and/or functionality. As another example, tanks used to hold various chemical materials may experience material deposits or reactions on the inner surface of the tank, which can adversely affect the overall process efficiency. Coating or lining the interior of the tank with glass may help to reduce these reactions because of the comparatively unreactive nature of the glass. In another example, a heat exchanger may be made from a high nickel content alloy to allow it to withstand high temperature operation (as in the case of a hydrocarbon-fuel gas turbine system) while also reducing the amount of precipitates and deposits that might be occurring due to the caustic environment in which the heat exchanger is required to operate. In yet another example, an exhaust valve for use in an internal combustion engine may be made from a particular alloy in an effort to reduce the amount of carbon deposits forming on its surface; carbon deposits are a well known source of operational and emission problems for internal combustion engines.
Many industrial processes use materials to contain and transport various fluids, slurries, or vapors, and those materials can become degraded during use. These problems are known as “flow assurance” issues, which is the industry term for the growth of flow restrictions in various pipes, tubes, heat exchangers, and process containers, etc. For instance, the interior of a pipeline used in an industrial process may have its effective cross-sectional area reduced during operation by deposits from the chemicals carried within the pipe during various processes. In other cases, the vaporous or liquid elements carried within a heat exchanger may precipitate the growth of crystalline deposits if favorable conditions (temperature, pressure, presence of catalytic elements, etc.) exist within the system. In one example of this problem, crystals of various elements may grow during fluid processing operation because certain exposed molecules within the material surface of the interior of a conduit serve to catalyze the growth of some types of fibers on the interior wall of the conduit. For example, carbon fibers grow on the interior of metal pipes used for ethylene transport, petro-chemical cracking tubes, petroleum refinery heaters, natural gas turbine blades, propane and LPG transport tanks, etc. While the mechanism of carbon fiber formation is not entirely clear, it is believed that exposed iron or other atoms at the surface of a steel or iron pipe in, e.g., a petroleum processing facility, may play a role in decomposing hydrocarbons flowing in the pipe into carbon. Because carbon has some solubility in iron, a steel or iron pipe may absorb this carbon. When the pipe material becomes saturated with carbon, amorphous carbon fibers begin to grow rapidly at process temperatures in the range of about 400° C. to about 800° C. Such deposits and/or fibrous growths affect the boundary layer development of the fluids and/or vapors passing through the pipe's interior, and can cause a significant restriction in the pipe's ability to transfer fluids, vapors, or slurries. Furthermore, a corrosive environment, especially due to the presence of water and impurities or salts dissolved in it, cause corrosion of metal pipes leading to eventual failure. Also, it is known that petrochemical process fluids flowing through a metal tube at high temperature can cause metal wastage in what is known as metal dusting, wherein the tube's inner surface is eroded by various mechanisms. Accordingly, there is a need in the art for a way to prevent or significantly inhibit the growth of carbon fibers while at the same time inhibiting chemical attack of corrosive elements on the substrate, such as those that result in metal dusting of components within a system.
In another example, at high process pressures and at temperatures above 0° C., methane gas, present in the petrochemical stream may react with water to form ice-like structures called hydrates. Hydrate formation in production-stream flow lines in the petroleum industry is also of great concern. Production-stream flow lines carry the raw, produced fluids from the wellhead to a processing facility. If a flow line is operated in the “hydrate region” (i.e., under conditions at which hydrates can form in an oil or gas wellstream), hydrates can deposit on the pipe's inner wall and agglomerate until they completely block the flow line and stop the transport of hydrocarbons to the processing facility. Attempts to prevent hydrate formation typically involve injecting additives into the process fluid, but this can be a costly solution.
Furthermore, combustion buildup known as slag or scale often forms on the flame-heated surfaces of furnaces, boilers, heater tubes, preheaters, and reheaters. The degree of combustion buildup depends on the quality of the fuel being burned. Clean natural gas, for example, produces little or no combustion buildup, while coal, a “dirtier” fuel, produces significant combustion buildup. In particular, coal-fired power plants experience significant combustion buildup on boiler vessels in contact with the coal combustion products. That buildup decreases heat transfer through the surface to the substance being heated, and therefore wastes energy. Also, such combustion buildup increases the applied temperature necessary to cause the substance to achieve a desired temperature. That increased temperature stresses the boiler vessel, and may lead to material failure. Preventing combustion buildup on the flame-heated surfaces of a fluid transport or processing system would reduce energy consumption and extend equipment lifetime.
Chemical solvents such as kerosene or diesel fuel, or stronger aromatic solvents such as xylene or toluene.
Dispersants that act as surfactants
Mechanical cleaning methods such as pigging or jetting
Thermal cleaning methods that involve hot oil or diesel fuel, or the external application of high heat to break down surface deposits
These methods involve considerable time and effort on the part of process plant maintenance personnel, reducing output or throughput of a system and causing the associated loss of revenue to the plant.
Various embodiments of the present invention are described herein. These embodiments are merely illustrations of the present invention. Numerous modifications and adaptations thereof will be readily apparent to those skilled in the art without departing from the spirit and scope of the invention.
The invention described herein provides a method for protecting surfaces of fluid transport or process equipment. As used herein, the term “fluid processing or transport system, or a component thereof” means any equipment within which fluid (used herein to include any material that is wholly or partially in a gaseous or liquid state, and includes, without limitation, liquids, gases, two-phase systems, semi-solid system, slurries, etc.) flows or is stored, such as pipes, tubes, conduits, heat exchangers, beds, tanks, reactors, nozzles, cyclones, silencers, combustion chambers, intake manifolds, exhaust manifolds, ports, etc., as well as any equipment within which a chemical or physical change occurs, wherein at least one of the components participating in the chemical or physical change is a fluid. The method of the invention protects the surfaces of such equipment by decreasing or preventing degradation, whether through deposition of material on the surfaces, through infiltration of material into the surfaces, or through corrosive attack on the material surface. The method is adapted to be used, in some embodiments, on fluid process equipment, or portions thereof, after assembly, resulting in significantly decreased interruption or interference with the protective functions of the coating by welds, joints, or other structures within the equipment that are created when the equipment is built or assembled.
In further embodiments, the at least one metal oxide coating appears uniform and without cracks or holes from about 100× to about 1000× magnification.
FIG. 1 shows a photograph of a cross section of an untreated pipe revealing crystalline growth that restricts flow through the pipe.
FIG. 3 shows a photograph of a steel coupon coated with “Zircon” after one hour exposed to Aqua Regia.
FIG. 4 shows a photograph of a steel coupon coated with “Glass” after one hour exposed to Aqua Regia.
FIG. 5 shows a photograph of a steel coupon coated with “YSZ” after one hour exposed to Aqua Regia.
FIG. 6 shows a photograph of a steel coupon coated with “Clay” after one hour exposed to Aqua Regia.
FIG. 7 shows TEM micrograph at 10,000× magnification of a steel substrate having a Y/Zr oxide coating in cross-section.
As used herein, the term “rare earth metal” includes those metals in the lanthanide series of the Periodic Table, including lanthanum. The term “transition metal” includes metals in Groups 3-12 of the Periodic Table (but excludes rare earth metals). The term “metal oxide” particularly as used in conjunction with the above terms includes any oxide that can form or be prepared from the metal, irrespective of whether it is naturally occurring or not. The “metal” atoms of the metal oxides of the present invention are not necessarily limited to those elements that readily form metallic phases in the pure form. “Metal compounds” include substances such as molecules comprising at least one metal atom and at least one oxygen atom. Metal compounds can be converted into metal oxides by exposure to a suitable environment for a suitable amount of time.
As used herein, the term “phase deposition” includes any coating process onto a substrate that is subsequently followed by the exposure of the substrate and/or the coating material to an environment that causes a phase change in either the coating material, one or more components of the coating material, or of the substrate itself. A phase change may be a physical phase change, such as for example, a change from fluid to solid, or from one crystal phase to another, or from amorphous to crystalline or vice versa. “Adaptable to provide” indicates the ability to make available. For example, an “article adaptable to provide a surface in a fluid processing or transport system” is an article, such as a pipe, that has a surface that is or can be assembled into such a system by using manufacturing, construction, and/or assembly steps.
“Alike or different,” when describing three or more substituents for example, indicates combinations in which (a) all substituents are alike, (b) all substituents are different, and (c) some substituents are alike but different from other substituents.
The metal carboxylate composition, in some embodiments of the present invention, comprises one or more metal salts of one or more carboxylic acid (“metal carboxylate”). Metal carboxylates suitable for use in the present invention include at least one metal atom and at least one carboxylate radical —OC(O)R bonded to the at least one metal atom. As stated above, metal carboxylates can be produced by a variety of methods known to one skilled in the art. Non-limiting examples of methods for producing the metal carboxylate are shown in the following reaction schemes:
Monocarboxylic acids where R is hydrogen or unbranched hydrocarbon radical, such as, for example, HCOOH-formic, CH3COOH-acetic, CH3CH2COOH—propionic, CH3CH2CH2COOH(C4H8O2)-butyric, C5H10O2-valeric, C6H12O2-caproic, C7H14-enanthic; further: caprylic, pelargonic, undecanoic, dodecanoic, tridecylic, myristic, pentadecylic, palmitic, margaric, stearic, and nonadecylic acids:
Monocarboxylic acids where R is a branched hydrocarbon radical, such as, for example, (CH3)2CHCOOH-isobutyric, (CH3)2CHCH2COOH—3-methylbutanoic, (CH3)3CCOOH-trimethylacetic, including VERSATIC 10 (trade name) which is a mixture of synthetic, saturated carboxylic acid isomers, derived from a highly-branched C10 structure;
Monocarboxylic acids in which R is a branched or unbranched hydrocarbon radical containing one or more double bonds, such as, for example, CH2═CHCOOH-acrylic, CH3CH═CHCOOH-crotonic, CH3(CH2)7CH═CH(CH2)7COOH-oleic, CH3CH═CHCH═CHCOOH-hexa-2,4-dienoic, (CH3)2C═CHCH2CH2C(CH3)═CHCOOH—3,7-dimethylocta-2,6-dienoic, CH3(CH2)4CH═CHCH2CH═CH(CH2)7COOH-linoleic, further: angelic, tiglic, and elaidic acids;
Monoaromatic carboxylic acids, in which R is a branched or unbranched hydrocarbon radical that contains one aryl substituent, such as, for example, C6H5COOH—benzoic, C6H5CH2COOH-phenylacetic, C6H5CH(CH3)COOH—2-phenylpropanoic, C6H5CH═CHCOOH-3-phenylacrylic, and C6H5C≡CCOOH-3-phenyl-propiolic acids;
Saturated dicarboxylic acids, in which R is a branched or unbranched saturated hydrocarbon radical that contains one carboxylic acid group, such as, for example, HOOC—COOH-oxalic, HOOC—CH2—COOH-malonic, HOOC—(CH2)2—COOH-succinic, HOOC—(CH2)3—COOH-glutaric, HOOC—(CH2)4—COOH-adipic; further: pimelic, suberic, azelaic, and sebacic acids;
Unsaturated dicarboxylic acids, in which R is a branched or unbranched hydrocarbon radical that contains one carboxylic acid group and at least one carbon-carbon multiple bond, such as, for example, HOOC—CH═CH—COOH-fumaric; further: maleic, citraconic, mesaconic, and itaconic acids;
Polybasic oxyacids, in which R is a branched or unbranched hydrocarbon radical containing at least one hydroxyl substituent and at least one carboxylic acid group, such as, for example, HOOC—CHOH—COOH-tartronic, HOOC—CHOH—CH2—COOH-malic, HOOC—C(OH)═CH—COOH-oxaloacetic, HOOC—CHOH—CHOH—COOH-tartaric, and HOOC—CH2—C(OH)COOH—CH2COOH-citric acids.
R—C(R″)(R′)—COOH (I)
Metal alkoxides suitable for use in the present invention include at least one metal atom and at least one alkoxide radical —OR2 bonded to the at least one metal atom. Such metal alkoxides include those of formula II:
M(OR2)z (II)
in which M is a metal atom of valence z+:
z is a positive integer, such as, for example, 1, 2, 3, 4, 5, 6, 7, and 8;
R2 can be alike or different and are independently chosen from unsubstituted and substituted alkyl, unsubstituted and substituted alkenyl, unsubstituted and substituted alkynyl, unsubstituted and substituted heteroaryl, and unsubstituted and substituted aryl radicals,
wherein substituted alkyl, alkenyl, alkynyl, heteroaryl, and aryl radicals are substituted with one or more alike or different substituents independently chosen from halogen, hydroxy, alkoxy, amino, heteroaryl, and aryl radicals.
In some embodiments, z is chosen from 2, 3, and 4.
Metal alkoxides are available from Alfa-Aesar and Gelest, Inc., of Morrisville, Pa. Lanthanoid alkoxides such as those of Ce, Nd, Eu, Dy, and Er are sold by Kojundo Chemical Co., Saitama, Japan, as well as alkoxides of Al, Zr, and Hf, among others. See. e.g. http://www.kojundo.co.jp/English/Guide/material/lanthagen.html.
1. Aliphatic series alcohols from methyl to dodecyl including branched and isostructured.
2. Aromatic series alcohols: benzyl alcohol -C6H5CH2OH; phenyl-ethyl alcohol-C8H10O; phenyl-propyl alcohol -C9H12O, and so on.
Metal alkoxides useful in the present invention can be made according to many methods known in the art. One method includes converting the metal halide to the metal alkoxide in the presence of the alcohol and its corresponding base. For example:
Other ligands are possible on the metal β-diketonates useful in the present invention, such as, for example, alkoxides such as —OR2 as defined above, and dienyl radicals such as, for example, 1,5-cyclooctadiene and norbornadiene.
The applying of the metal compound composition may be accomplished by various processes, including dipping, spraying, flushing, vapor deposition, printing, lithography, rolling, spin coating, brushing, swabbing (e.g., with an absorbent “pig” of fabric or other material that contains the metal compound composition and is drawn through the apparatus), pig train (in which the metal compound composition, trapped between two or more pigs, is pushed through a system by compressed air, for example), or any other means that allows the metal compound composition to contact the desired portions of the surface to be treated. In this regard, the metal compound composition may be liquid, and may also comprise a solvent. The optional solvent may be any hydrocarbon and mixtures thereof. In some embodiments, the solvent can be chosen from carboxylic acids; toluene; benzene; alkanes, such as for example, propane, butane, isobutene, hexane, heptane, octane, and decane; alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and isobutanol; mineral spirits; β-diketones, such as acetylacetone; ketones such as acetone; high-paraffin, aromatic hydrocarbons; and combinations of two or more of the foregoing. Some embodiments employ solvents that contain no water or water in trace amounts or greater, while other embodiments employ water as the solvent. In some embodiments, the metal compound composition further comprises at least one carboxylic acid.
The metal compound composition can applied in some embodiments in which the composition has a temperature less than about 250° C. That composition also can be applied to the substrate in further embodiments at a temperature less than about 50° C. In other embodiments, the liquid metal compound composition is applied to the substrate at room temperature. In still other embodiments, that composition is applied at a temperature greater than about 250° C.
The conversion environment may be accomplished in a number of ways. For example, a conventional oven may be used to bring the coated substrate up to a temperature exceeding approximately 250° C. for a given period of time. In some embodiments, the environment of the coated substrate is heated to a temperature exceeding about 400° C. but less than about 500° C. for a chosen period of time. In other embodiments, the environment of the coated substrate is heated to a temperature ranging from about 400° C. to about 650° C. In further embodiments, the environment is heated to a temperature ranging from about 400° C. to about 550° C. In still further embodiments, the environment is heated to a temperature ranging from about 550° C. to about 650° C., from about 650° C. to about 800° C., or from about 800° C. to about 1000° C. Depending on the size of the components and/or process equipment, pipes, etc., the time period may be extended such that sufficient conversion of a desired amount of the metal compound to metal oxides has been accomplished.
CeO2—ZrO2 where CeO2 is about 10-90 wt %
Mixtures of these compositions are also suitable for use in the invention.
The invention relates, in some embodiments, to diffused coatings and thin films (and articles coated therewith) containing at least one rare earth metal oxide, and at least one transition metal oxide. As used herein, “diffused” means that metal oxide molecules, nanoparticles, nanocrystals, larger domains, or more than one of the foregoing, have penetrated the substrate. The diffusion of metal oxides can range in concentration from rare interstitial inclusions in the substrate, up to the formation of materials that contain significant amounts of metal oxide. A thin film is understood to indicate a layer, no matter how thin, composed substantially of metal oxide. In some embodiments, a thin film has very little or no substrate material present, while in other embodiments, a thin film comprises atoms, molecules, nanoparticles, or larger domains of substrate ingredients. In some embodiments, it may be possible to distinguish between diffused portions and thin films. In other embodiments, a gradient may exist in which it becomes difficult to observe a boundary between the diffused coating and the thin film. Furthermore, some embodiments may exhibit only one of a diffused coating and a thin film. Still other embodiments include thin films in which one or more species have migrated from the substrate into the thin film. The terms “metal oxide coating” and “surface comprises at least one metal oxide” include all of those possibilities, including diffused coatings, thin films, stacked thin films, and combinations thereof.
Additional embodiments employ various heating steps to reduce or eliminate the formation of other species. For example, carbide formation can be lessened during metal oxide formation in some embodiments by applying a metal compound precursor composition containing a metal carboxylate to a surface, subjecting the surface to a low-temperature bake at about 250° C. under a vacuum, introducing air and maintaining the temperature, and then increasing the temperature to about 420° C. under vacuum or inert atmosphere to convert the metal carboxylate into the metal oxide. Without wanting to be bound by theory, it is believed that the low-temperature bake drives off most or all of the carboxylate ligand, resulting in an oxide film substantially free of metal carbide.
The process of the invention may permit the use of coatings on a wide variety of materials, including application of CeO2 and ZrO2 coatings to ceramics and/or solid metals previously not thought possible of being coated with these materials. Some embodiments of the present invention provide a relatively low temperature process that does not damage or distort many substrates, does not produce toxic or corrosive water materials, and can be done on site, or “in the field” without the procurement of expensive capital equipment.
In some embodiments of the present invention, a substrate which comprises at least a portion of a component's structure is placed within a vacuum chamber, and the chamber is evacuated. Optionally, the substrate can be heated or cooled, for example, with gas introduced into the chamber or by heat transfer fluid flowing through the substrate mounting structure. If a gas is introduced, care should be taken that it will not alter the substrate in an unintended manner, such as by oxidation of a hot iron-containing surface by an oxygen-containing gas. Introduced gas optionally can be evacuated once the substrate achieves the desired temperature. Vapor of one or more metal compounds, such as cerium(IV) 2-hexanoate, enters the vacuum chamber and deposits on the substrate. A specific volume of a fluid composition containing the metal compound can provide a specific amount of compound to the surface of the substrate within the vacuum chamber, depending on the size of the chamber and other factors. Optionally, a chosen gas is vented into the chamber and fills the vacuum chamber to a chosen pressure, in one example, equal to one atmosphere. The chamber is heated to a temperature sufficient to convert at least some of the compounds into oxides, for example, 450° C., for a discrete amount of time sufficient for the conversion process, for example, thirty minutes. In this example, a ceria layer forms on the substrate. Optionally, the process can be repeated as many times as desired, forming a thicker coating of ceria on the substrate. In some embodiments, the component can be cooled relative to ambient temperature, such as, for example, to liquid nitrogen temperature, to aid the deposition process. In other embodiments, a reducing atmosphere may be used to convert at least a portion of the metal oxides to metal.
As used herein in reference to process gases used to carry out the process of the invention, the term “high temperature” means a temperature sufficiently high to convert the metal compound to metal oxide, generally in the range of about 200° C. to about 1000° C., such as, for example, about 200° C. to about 400° C., or about 400° C. to about 500° C., about 500° C. to about 650° C., about 650° C. to about 800° C., or about 800° C. to about 1000° C. Process gases at even higher temperatures can be used, so that, when the gas is passed through the fluid transport or processing system during the process of some embodiments of the invention, the temperature of the gas exiting the system is within the range given above.
In some applications, where it is desirable to reduce a metal oxide to a pure metal, the treated substrate may be exposed to a reducing agent, such as hydrogen or other known reducing agent using known means for oxide reduction. For example, 7% hydrogen in argon heated to 350° C. can be used to form platinum in certain embodiments. Other metals that may be desired, such as for catalytic purposes, for example, include but are not limited to platinum, palladium, rhodium, nickel, cerium, gold, silver, zinc, lead, rhenium, ruthenium, and combinations of two or more thereof.
As described above, the method of the invention may be used to provide prophylactic coatings to internal surfaces of fluid transport or processing systems, and has particular utility in the area of fluid transport or processing systems in the petroleum and natural gas industries, where carbon fouling, corrosion, and hydrogen embrittlement are particular problems in pipelines and processing equipment. For example, coating with the ceria, or yttria-stabilized zirconia, or a combination of ceria and zirconia will significantly reduce carbon fouling on steel surfaces exposed to petroleum or other hydrocarbons at temperatures of around 570° C., in effect providing protection against any effective or measurable carbon deposition. Uncoated steel surfaces exposed to similar conditions become sufficiently fouled with carbon as to require cleaning after about 18 months of service. Inhibition of carbon fouling occurs during exposure to petroleum or other hydrocarbons at temperatures as high as 900° C. Similar improvement in fouling will occur in fluid processing systems used to process natural gas.
Five 2″×2″ coupons of mirror-finish SS304 steel (McMaster-Carr) were individually designated “Uncoated,” “Zircon,” “Glass,” “YSZ,” and “Clay.” Those compositions mimic chemically and thermally inert materials by the same names known in nature and industry, in an inventive manner. A wide range of similar materials can suggest additional compositions to be used as embodiments of the present invention. The “Uncoated” coupon was given no coating, to function as the control. Each of the other coupons were coated on one side with the following compositions in accordance with embodiments of the present invention:
YSZ: Yttrium 2-ethylhexanoate powder (2.4% wt., Alfa-Aesar) was dissolved into 2-ethylhexanoic acid (60% wt., Alfa-Aesar) with stirring at 75-80° C. for one hour. Once the composition was cooled to room temperature, zirconium 2-ethylhexanoate (36.6% wt., Alfa-Aesar) and chromium 2-ethylhexanoate (1% wt., Alfa-Aesar) were mixed in. The composition was spin-coated onto the steel substrate.
The coated steel coupons were placed in a vacuum oven, and evacuated to about 20-60 millitorr. The coupons were heated to 450° C., and then allowed to cool to room temperature. The process of depositing and heating was repeated to apply eight coatings of the appropriate composition on each coupon.
Each coated coupon was assembled into a test cell having a glass cylinder (1″ inner diameter×1.125″ tall) clamped to the coated portion of the coupon. A rubber gasket formed a seal between the glass cylinder and the coupon. Aqua Regia was prepared from HNO3 (1 part, by vol., 70%, stock #33260, Alfa-Aesar) and HCl (3 parts, by vol., ˜37%, stock #33257, Alfa-Aesar), poured into the glass cylinder, and allowed to contact the coupon for one hour. Then, the coupon was removed, rinsed, and photographed. The photographs of the tested coupons appear in FIGS. 2-6.
Coupon Performance
Uncoated 0
Glass 7-8
YSZ 0-1
Observation of the Zircon and Glass coupons at magnifications of 100× to 1,000×before exposure to Aqua Regia revealed uniform, non-porous, mostly amorphous coatings. Observation of the YSZ coupon at those same magnifications revealed a surface coating having a crystalline structure. Observation of the Clay coupon revealed uneven coverage, likely due to the humidity-catalyzed reaction and premature solidification. Preparation and application of the Clay composition in a moisture and/or oxygen-free environment may improve the Clay coating's characteristics and performance.
FIG. 7 shows a TEM micrograph at 10,000× magnification of a stainless steel SS304 substrate (104) having eight coats of an yttria/zirconia composition (102). The figure illustrates a diffused coating, labeled Oxide-To-Substrate Interlayer (106). In this example, the diffused coating is about 10 nm thick. The TEM also shows crystal planes, indicating the nanocrystalline nature of the yttria/zirconia.
The interior oil-contacting surfaces of a boiler for a petroleum fractional distillation column are cleaned and then flushed with a well-stirred room temperature composition containing cerium(III) 2-ethylhexanoate (203 g; all weights are per kilogram of final composition), chromium(III) acetylacetonate (10.1 g), and cerium(IV) oxide nanoparticles (10.0 g, 10-20 nm, Aldrich) in 2-ethylhexanoic acid (777 g), and the composition is drained from the boiler. Steam at 500° C. heats the boiler in the usual manner for 30 minutes, and then the boiler is allowed to cool. A substantially non-porous cerium oxide coating stabilized by chromium oxide forms on the oil-contacting surfaces of the boiler.
Under an ethanol-saturated nitrogen atmosphere, the cleaned milk-contacting surfaces of a milk pasteurizer are flushed with a well-stirred composition containing titanium(IV) ethoxide in ethanol (500 g, 20% Ti, Aldrich) and dry ethanol (500 g), and the composition is drained. Dry nitrogen heated to 450° C. flushes through the pasteurizer for fifteen minutes, and the pasteurizer is allowed to cool under a flow of room-temperature nitrogen. Analysis will reveal a titanium dioxide coating on the milk-contacting surfaces of the pasteurizer.
A clean automobile exhaust manifold is dipped in a stirred bath containing a first composition that contains zirconium(IV) 2,2,6,6-tetramethyl-3,5-heptanedionate (459 g), yttrium(III) 2,2,6,6-tetramethyl-3,5-heptanedionate (72.9 g), and hexanes (to 1 kg) so the composition contacts interior and exterior surfaces. Optionally, openings can be plugged so the first composition does not contact the interior surfaces. The manifold is removed from the composition, suspended, and rotated to allow excess composition to drip into the bath. Microwave radiation irradiates exterior surfaces for ten minutes, and an yttria-stabilized zirconia coating forms on the exterior of the manifold. The exhaust-contacting surfaces of the manifold are flushed with a second composition containing zirconium(IV) 2,2,6,6-tetramethyl-3,5-heptanedionate (459 g), yttrium(III) 2,2,6,6-tetramethyl-3,5-heptanedionate (72.9 g), platinum(II) acetylacetonate (1.01 g), and hexanes (to 1 kg), and the composition is drained from the manifold. Argon gas heated to 450° C. is passed through the interior of the manifold for 30 minutes. Then, argon gas containing 7% hydrogen heated to 350° C. passes through the interior of the manifold for 30 minutes. An yttria-stabilized zirconia coating will form on the interior surface of the manifold. The interior surface also will contain platinum metal sites to catalyze the oxidation of partially-combusted hydrocarbon fuel. Moreover, an yttria-stabilized zirconia coating will form to protect the exterior of the manifold from corrosion. Optionally, the manifold can be cooled to room temperature and then slowly lowered into a liquid nitrogen bath for a time.
As previously stated, detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention that may be embodied in various forms. It will be appreciated that many modifications and other variations that will be appreciated by those skilled in the art are within the intended scope of this invention as claimed below without departing from the teachings, spirit, and intended scope of the invention. Furthermore, the foregoing description of various embodiments does not necessarily imply exclusion. For example, “some” embodiments may include all or part of “other” and “further” embodiments within the scope of this invention.
1. A method for decreasing or preventing fouling on an interior surface of a pipe or tube of a fluid processing or transport system, comprising:
applying at least one metal compound composition to the surface with a pig train, wherein the at least one metal compound composition consists of
zirconium 2-ethylhexanoate,
chromium 2-ethylhexanoate,
silicon 2-ethylhexanoate, and
2-ethylhexanoic acid; and
exposing the surface with the applied at least one metal compound composition to an environment that will convert at least some of the zirconium 2-ethylhexanoate, at least some of the chromium 2-ethylhexanoate, and at least some of the silicon 2-ethylhexanoate to at least one metal oxide;
wherein the at least one metal oxide is resistant to fouling.
2. The method of claim 1, wherein at least a portion of the at least one metal oxide is present in a diffused coating.
3. The method of claim 2, wherein the diffused coating penetrates the surface from ®Angstroms to 600 Angstroms.
4. The method of claim 1, wherein the interior surface of the pipe or tube of the fluid processing or transport system has a surface area greater than 100 square feet.
5. The method of claim 1, wherein the interior surface of the pipe or tube of the fluid processing or transport system has a surface area ranging from 100 square feet to 100,000 square feet.
6. The method of claim 1, wherein the interior surface of the pipe or tube of the fluid processing or transport system has a surface area ranging from 100,000 square feet to 1,000,000 square feet.
7. The method of claim 4, wherein the fluid processing or transport system is a pipeline.
8. The method of claim 4, wherein the fluid processing or transport system is an ethylene cracker.
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US15437036 Active US9879815B2 (en) 2006-10-12 2017-02-20 Methods for providing prophylactic surface treatment for fluid processing systems and components thereof
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