JP2018184615A - High-emissivity coating composition and production process thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat-radiation coating composition showing desirable mechanical strength characteristics and emissivity in a wide temperature range (for example, approximately 400°C to approximately 1,300°C).SOLUTION: A heat-radiation coating composition contains: an aggregate of an emission agent containing titanium dioxide of which a weight percentage is less than approximately 28 wt.% of the coating composition and at least approximately 10 wt.% of the coating composition; and a dry mixture of an aggregate of a matrix strength improver selected from at least one of ceramic boride, ceramic carbide and ceramic nitride.SELECTED DRAWING: None

Description

The present disclosure relates generally to compositions for high emissivity coatings that can be applied to various types of substrates and processes for making high emissivity coating compositions. More specifically, the present disclosure includes (1) a high emissivity coating composition with improved strength properties and (2) a high emissivity in which titanium dioxide (TiO ₂ ) is used as an emissivity improver. And (3) a manufacturing process for cost-effectively producing high emissivity coating compositions using industrial waste sources or industrial waste streams.

As energy demand increases and energy costs increase around the world, the need for energy users to save or save energy is inevitably increasing, especially in industrial associations. In many cases, industries using combustion heaters or furnaces, such as refineries and petrochemical complexes, have attempted to reduce fuel consumption by maximizing combustion heater efficiency. High emissivity coating technology effectively increases radiant heat transfer without compromising process reliability and safe operation for various high temperature applications,
It has become a proven tool to save energy.

Emissivity (represented by the symbol ε or e) can be broadly defined as the relative ability of a surface to emit energy by radiation. More specifically, emissivity can be defined as the ratio of the energy emitted by a particular material to the energy emitted by a black body at the same temperature. An increase in emissivity corresponds to an increase in thermal efficiency. The increase in thermal efficiency that is attributed to high emissivity coatings in high temperature combustion heater or furnace applications results in increased combustion heater or furnace performance or power and / or reduced fuel consumption and total energy demand.

The benefits and advantages of high emissivity coatings have led to various research and development efforts over the years to improve the performance of high emissivity coatings. In particular, a) increasing emissivity values to increase radiant heat transfer, b) improving coating adhesion to the substrate, c) extending coating life under multiple high temperature cycles, d) In order to reduce degradation, research has been conducted to develop radioactive coating compositions containing emissivity enhancers (“emissivity agents”).

Currently, several high emissivity coating compositions are commercially available. Radioactive agents in these compositions can come from a variety of sources. One commonly used emissive agent is silicon carbide (SiC), which can exhibit good emissivity enhancement performance up to moderate temperatures. However, the use of SiC as a radiation agent in applications with high operating temperatures (eg, combustion heaters, furnaces, preheaters, reformers, other refractory applications, or aerospace applications) And the substantial decrease in mechanical strength over time, and hence
This can lead to an overall reduction or degradation in the performance or function of coating compositions that rely on SiC as a radioactive agent.

"Thermal Degradation Study of Silicon Carbide Threa" published in August 1992
NASA Tech entitled "ds Developed for Advanced Flexible Thermal Protection Systems"
nical Memorandum 130952, K. Tran and P.M. M.M. Sawko is 400
It was found that a surface transition from SiC to SiO ₂ was observed at a temperature higher than 0 ° C. S
The surface transition from iC to SiO _{2 is due} to temperature-induced decomposition of SiC bonds followed by SiO _2.
Was due to the formation of The decomposition reaction of SiC at high temperature can be illustrated as follows: SiC + O ₂ → SiO ₂ + CO ₂

Such SiC degradation can have undesirable consequences of significant material shrinkage, unintended SiO ₂ passivation, and reduced coating composition life. Therefore, there is a need for improved emissive agents for high emissivity coating compositions, particularly with respect to improving emissive performance of radioactive coatings at high temperatures. Unfortunately, previous work on high emissivity coating compositions has not been able to fully consider or recognize that certain materials can potentially have significant impact on increasing emissivity values.

In addition to the above, while aspects of high emissivity coating performance are being studied and improved,
Existing processes for producing high emissivity coating compositions have not been able to properly consider or address certain economic aspects of the production of such compositions. In particular, various efforts have been made to develop high emissivity coatings with better performance, but such efforts have been linked to the production costs of such coating compositions and the end of high emissivity coating products. Prices are almost ignored or inevitably increased. Accordingly, there is a need to prepare, manufacture, or formulate high emissivity coating compositions in a more cost effective manner.

NASA Technical Memorandum 130952, `` Thermal Degradation Study of Silicon Carbide Threads Developed for Advanced Flexible Thermal Protection Systems ''

Embodiments of the subject matter described in this application can be used over a wide temperature range (eg, from about 400 ° C. to about 1300
Directed to a thermally emissive coating that exhibits desirable mechanical strength properties and emissivity over a range of ° C. Unlike other radioactive coatings that exhibit cracks and delamination from the substrate to which the coating is applied, embodiments of the subject matter described herein can be used at room temperature to temperatures typically used in decoking cycles, such as about Withstand repeated temperature cycles from 1000 ° C. up to about 1600 ° C. or higher without cracking or peeling from the underlying substrate. At the same time, the coating compositions according to the embodiments described herein exhibit a desired emissivity, for example as high as 0.99.

In one aspect, embodiments described herein include a collection of radioactive agents comprising titanium dioxide, wherein the weight percentage of titanium dioxide is less than about 28% by weight of the coating composition and at least about 10% by weight of the coating composition. (set), ceramic borides,
It is directed to a thermal radiation coating comprising a dry blend with a set of matrix strength improvers selected from ceramic carbide and at least one of ceramic nitride. In some embodiments of this aspect of the described subject matter, the coating is 30 on a dry basis.
Contains less than wt% SiC.

In another aspect, an embodiment described herein is a method of preparing a thermal radiation coating composition for a substrate, the method comprising obtaining titanium dioxide; providing a collection of radiation agents comprising titanium dioxide Providing a set of matrix strength improvers comprising at least one matrix strength improver selected from the group consisting of ceramic boride, ceramic carbide, and ceramic nitride; at least one filler is oxidized Providing a set of fillers selected from the group consisting of aluminum, silicon dioxide, magnesium oxide, calcium oxide, and boron oxide; and the set of radioactive agents;
Admixing the set of matrix strength improvers and the set of fillers to a method wherein the filler constitutes from about 2 wt% to about 60 wt% of the coating composition on a wet basis. . In some embodiments of this aspect of the described subject matter, the SiC is provided such that the coating composition comprises less than 30 wt% SiC on a dry basis.

In yet another aspect, the disclosed embodiment is a method for adjusting a thermal emissivity of a substrate using a thermal emissive coating composition, the method comprising identifying a target emissivity level or target emissivity adjustment Determining the titanium dioxide concentration of the coating composition expected to provide a target emissivity level or target emissivity adjustment; determining a set of substrate adhesion characteristics for the coating composition; And a step of determining a SiC concentration of the coating composition expected to provide a set of; and providing a thermal radiation coating composition comprising the determined titanium dioxide concentration and the determined SiC concentration. In some embodiments of this aspect of the described subject matter, the determined SiC concentration is less than 30 wt% SiC on a dry basis.

In another embodiment, the titanium dioxide used as a radiation agent or emissivity enhancer is obtained from a titanium dioxide containing waste stream from a polyolefin polymerization process.

In the drawings, identical reference numbers identify similar elements. The sizes and relative positions of elements in the drawings are not necessarily drawn to scale. For example, the shapes and angles of the various elements are not drawn to scale, and some of these elements are arbitrarily enlarged and arranged to improve the readability of the drawings. Further, the particular shapes of the illustrated elements are not intended to convey any information regarding the actual shape of the particular elements, they are simply selected so that they can be easily recognized in the drawings. .
Embodiments of the present disclosure will be described below with reference to the drawings.

1 is a flowchart of a process for extracting or obtaining TiO ₂ from a polyolefin catalyst waste for use in preparing a high emissivity coating composition in accordance with an embodiment of the present disclosure. 2 is a flowchart of a process for preparing or producing a high emissivity coating composition in accordance with an embodiment of the present disclosure. 2 is a flowchart of a process for applying a high emissivity coating composition to a substrate in accordance with an embodiment of the present disclosure. 2 is a cross-sectional photograph of a coating composition applied to a substrate after being subjected to pseudo-decoking conditions. 2 is a cross-sectional photograph of a coating composition applied to a substrate after being subjected to pseudo-decoking conditions. 2 is a cross-sectional photograph of a coating composition applied to a substrate after being subjected to pseudo-decoking conditions. It is a photograph of the inner wall surface of a high-temperature furnace coated with a commercially available SiC-containing coating composition after operating at a temperature range of 1000 ° C. It is a photograph of the inner wall surface of a high-temperature furnace coated with a commercially available SiC-containing coating composition after operating at a temperature range of 1000 ° C. It is a photograph of the inner wall surface of a high-temperature furnace coated with a commercially available SiC-containing coating composition after operating at a temperature range of 1000 ° C.

While specific embodiments of the present disclosure have been described herein for purposes of illustration, it will be understood that various modifications may be made without departing from the spirit and scope of the disclosure. Accordingly, the disclosure is not limited except as by the appended claims.

In the following description, certain specific details are set forth in order to provide a thorough understanding of various aspects of the disclosed subject matter. However, the disclosed subject matter may be practiced without these specific details. In some examples, known structures, including embodiments of the presently disclosed subject matter, and methods of mixing ceramic precursors, recovering titanium dioxide, and applying a high emissivity coating to a substrate. It has not been described in detail to avoid obscuring the description of other aspects of the disclosure.

Unless otherwise required by context, the term “comprise” and variations thereof (eg, “comprises” and “compr”) are used throughout this specification and the claims that follow.
ising ”) shall be construed non-exclusively (ie, including but not limited to)“ inclusive ”.

Throughout this specification, references to “one embodiment” or “an embodiment” include in the at least one embodiment the particular feature, structure, or characteristic described in connection with that embodiment. Means that. Therefore, throughout this specification, various places
The use of the phrases “in one embodiment” or “in an embodiment” does not necessarily all refer to the same aspects. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more aspects of the disclosure.

Embodiments of the present disclosure provide high emissivity where titanium dioxide (TiO ₂ ) is used as an emissivity enhancer, as opposed to prior high emissivity coating compositions where TiO ₂ was only used as a filler. Directed to the coating composition. However, in high temperature conditions, the present inventors have observed that exhibits an emissivity enhancing properties because of TiO ₂ is the temperature-induced TiO ₂ conversion microstructure. TiO ₂ has three natural forms, anatase, rutile, and brookite. Anatase is mainly used for photocatalytic applications because of its UV absorption properties. Anatase undergoes conversion at temperatures above 700 ° C. to produce rutile, which is commonly used in the pigment, cosmetic and ceramic industries. It has been observed by the inventors that rutile is stable at high temperatures and is a good energy emitting agent. Brookite is rarely used because of its limited availability.

The use of TiO ₂ as a filler in prior coating compositions typically has had a negative impact on the cost of the coating composition due to the high TiO ₂ cost. Embodiments of the present disclosure are coating compositions comprising TiO ₂ as a radioactive agent or emissivity enhancer, wherein the TiO ₂ is cost effective without including the overall function or characteristics of TiO ₂ in the coating composition. Provide what you get. Certain embodiments of the present disclosure is a coating composition containing TiO _2, TiO ₂ is industrial waste source, for example to provide those obtained from waste streams associated with production of polyolefin catalyst. Obtaining TiO ₂ from such types of waste sources results in a reduction in the cost of TiO ₂ , which is such TiO _2.
To improve the economic aspects of production of high emissivity coating compositions comprising: T from industrial waste sources
Processes, methods, or techniques for obtaining iO ₂ are detailed below in connection with aspects of the high emissivity coating composition manufacturing process.

As described in more detail below, the high emissivity coatings, coating systems, or coating compositions of the present disclosure are referred to herein as “coating compositions”. In addition, all percentages (%) are weight to weight percent and weight percent unless otherwise stated.
,% (W / w), wt% or simply%. The term `` wet admixture ''
Is a constituent of the coating composition in solution or with respect to the solution.
s) or relative weight percentage of components, the term `` dry admixtu
re) '' is a component or component of the dry coating composition that has been separated from water and any liquid reagent or prior to the addition of water and any liquid reagent.
ponents) relative percentage. One skilled in the art will understand how wet blend weight percentages and dry blend weight percentages are related or how they can be converted.

For the purposes of this disclosure, the term “set” is in accordance with known mathematical definitions (eg, An Introd
uction to Mathematical Reasoning: Numbers, Sets, and Functions, 「Chapter 11: P
roperties of Finite Sets '' by Peter J. Eccles, Cambridge University Press (1998)
) (In a manner corresponding to that described on page 140 for example)
, Defined as a non-empty original finite composition that mathematically exhibits at least one cardinality (the original number of sets) (ie, a set as defined herein is a unary or union, or Can be a multi-way set).

The coating composition of the present disclosure (in a wet blend) is (1) a collection or group of about 2 wt% to 60 wt% filler that is free of TiO ₂ ; (2) TiO ₂ and further includes silicon carbide A collection or group of about 5% to 70% by weight of radiation agent or emissivity improver, which can include (SiC) and / or chromium oxide (Cr ₂ O ₃ ), (3) about 5% to 20% A collection or group of weight percent matrix strength improvers, and (4) about 2% to 30% by weight
Contains a collection or group of binders by weight percent.

Fillers referred to in this disclosure are materials that are added to other materials in order to reduce consumption in high emissivity coating compositions of components that are more expensive than fillers. Without limitation, fillers useful in the present disclosure include aluminum oxide (Al ₂ O ₃ ), silicon dioxide (SiO ₂ ), magnesium oxide (MgO), calcium oxide (CaO), and boron oxide (B ₂ O ₃ ).

The emissive agent or emissivity enhancer referred to in this disclosure is a material that increases the emissivity of the high emissivity coating composition to which the emissive agent or emissivity enhancer is added. Without limitation, suitable radioactive agents or emissivity enhancers include titanium dioxide (TiO ₂ ), silicon carbide (SiC), chromium oxide (Cr ₂ O ₃ ), silicon dioxide (SiO ₂ ), iron oxide. (Fe
₂ O ₃ ), boron silicide (B ₄ Si), boron carbide (B ₄ C), silicon tetraboride (SiB ₄ ), molybdenum disilicide (MoSi ₂ ), tungsten disilicide (
WSi ₂ ), and zirconium diboride (ZrB ₂ ).

As used herein, a matrix strength enhancer or thermal strength enhancer is a material that increases the resistance to stress and thermal stress of a high emissivity coating composition comprising such matrix strength or thermal strength enhancer. Without limitation, in various embodiments, useful matrix or thermal strength enhancers include ceramic boride, ceramic carbide, and / or ceramic nitride (eg, ultra high temperature ceramics (
UHTC), etc., which exhibit high melting points, substantial chemical inertness, and relatively good oxidation resistance in extreme thermal environments. In certain embodiments, the matrix strength improver includes, but is not limited to, silicon carbide (SiC), hafnium diboride (HfB ₂ ), hafnium carbide (HfC), hafnium nitride (HfN),
Tantalum diboride (TaB ₂ ), Tantalum carbide (TaC), Tantalum nitride (TaN), Titanium diboride (TiB ₂ ), Titanium carbide (TiC), Titanium nitride (TiN), Zirconium diboride (ZrB) ₂ ), zirconium carbide (Zr
C), and zirconium nitride (ZrN). In addition, in certain embodiments, binders such as, but not limited to, phosphoric acid (H ₃ PO ₄ ), sodium aluminosilicate and / or potassium aluminosilicate, for example Al ₂ (H
_By forming ₂ P2O ₇ ), Al (PO ₃ ) ₃ , AlPO ₄ , and / or KAlSi ₃ O ₈ , the thermal strength can also be improved. A specific example of the binder is an aqueous solution containing phosphoric acid (H ₃ PO ₄ ) and sodium silicate.

The inventors have realized that there can be a component-dependent trade-off between the emissivity of the coating composition, adhesion to the substrate, and temperature stability. In other words, adjusting the weight percentage of a particular component in the coating composition can cause changes in the emissivity, temperature stability, and adhesion of the coating composition. In order to simultaneously improve emissivity, coating adhesion or adhesion, and high temperature thermal stability and chemical stability, some coating composition embodiments according to the present disclosure may comprise one or more other coating composition configurations. Contain or establish a specific weight percentage of TiO ₂ relative to the weight percentage of the element, eg, Al ₂ O ₃ . For example, certain coating composition embodiments comprise at least about 8% to 10% TiO ₂ by weight relative to the wet blend. In addition to or in lieu of the above, coating composition embodiments according to the present disclosure may be less than about 20% to 22% by weight relative to the wet blend.
Less than TiO ₂ and the weight percentage of Al ₂ O ₃ can be established or adjusted based on the choice of a given TiO ₂ weight percentage. In certain embodiments, the weight percentages of Al ₂ O ₃ and TiO ₂ can be varied or adjusted to obtain various emissivities and matrix attachment capabilities. In some embodiments, among others, T
If iO ₂ is recovered from a TiO ₂ waste source, the wet blend weight percentage of TiO ₂ and Al ₂ O ₃ can be selected to be about 20% and 22%, respectively. In embodiments where TiO ₂ is obtained from commercial sources, the wet blend percentage by weight of TiO ₂ and _Al 2 _{O 3,} it can be selected to be about 18% and 16%, respectively. In certain embodiments, TiO ₂
And the wet blend weight percentage of Al ₂ O ₃ can be selected to be about 10% and 32%, respectively. In the three embodiments, on a dry basis, SiC is less than 30 wt%, about 20
It is present in an amount less than wt%, between about 8 wt% and less than 30 wt%, and between about 8 wt% and about 20 wt%. In one specific embodiment, the SiC content is about 14 wt% on a dry basis.

In some embodiments, the use of a set or group of matrix strength improvers improves the strength as well as adhesion of the coating composition within the matrix. More specifically, the matrix strength improver decomposes at working or operating temperatures to form a new, modified or re-formulated matrix with other coating composition components, such as fillers. Or have the ability to create. Such matrix strength improvers can include one or more ceramic boride, ceramic carbide, or ceramic nitride. In many embodiments, SiC decomposes into SiO ₂ and CO ₂ at temperatures above about 400 ° C. to form a new matrix (Al ₂ O ₃ —SiO ₂ —SiC) with aluminum oxide and silicon dioxide. Acts as a matrix strength improver. The Al ₂ O ₃ —SiO ₂ —SiC ceramic matrix serves to improve the mechanical strength, ie the bond strength between the particles in the coating. The more SiC present in the coating, the greater the amount of Al ₂ O ₃ —SiO ₂ —SiC matrix produced. The inventors have observed that the resulting Al ₂ O ₃ —SiO ₂ —SiC matrix can increase the strength of the original matrix, but Al ₂ O ₃ —SiO ₂ —SiC.
It was also observed that too much matrix could cause defects in the matrix. As the SiC content in the coating composition reaches a certain level, these matrix defects become dominant and will cause a reduction in mechanical strength as evidenced by shrinkage of the coating composition. Such shrinkage can cause the coating composition to crack and peel when the coating is applied to the substrate to which the coating is applied. Furthermore, it was observed that the more SiC decomposes into SiO ₂ and the more CO ₂ is produced from the decomposition reaction, the more CO ₂ tends to diffuse throughout the coating composition. This CO ₂
Diffusion is evidenced by small bubbles or voids below the coating composition surface. These small bubbles or voids can also reduce the mechanical strength of the coating composition, which can shorten the useful life of the coating composition.

4A and 4B, after being subjected to conditions applied to the substrate and simulating multiple decoking cycles in a naphtha cracking furnace (ie, 22 cycles between room temperature and 1 hour hold at 1600 ° C.) 2 shows a photograph of a cross section of a coating composition according to embodiments described herein. In FIGS. 4A and 4B, there is no separation between the coating composition and the underlying substrate. FIG. 4C shows a cross-sectional photograph of a commercially available high emissivity coating composition applied to a substrate and subjected to the same quasi-decoking cycle as the samples of FIGS. 4A and 4B. The sample in FIG. 4C shows a visible crack between the coating and the substrate, demonstrating delamination between the coating and the substrate.

In addition to or in lieu of the above, in certain embodiments, the matrix strength improver comprises hafnium diboride (HfB ₂ ), hafnium carbide (HfC), hafnium nitride (HfN), tantalum diboride ( TaB ₂ ), tantalum carbide (TaC)
), Tantalum nitride (TaN), titanium diboride (TiB ₂ ), titanium carbide (TiC), titanium nitride (TiN), zirconium diboride (ZrB ₂ ), zirconium carbide (ZrC), and zirconium nitride One or more of (ZrN) can be included.

As stated above, the coating compositions of the present disclosure can include one or more chemicals or substances that serve as binders or binders. Such a binder facilitates the bond between the coating composition and the substrate to which the coating composition is applied. Furthermore, the binder facilitates or achieves support of the coating composition by promoting bonding between coating molecules (eg, between Al ₂ O ₃ and Al ₂ O ₃ molecules), which , Facilitating creation of the matrix structure of the coating composition matrix itself. In many embodiments, the binder is or includes an aqueous solution containing H ₃ PO ₄ . In various embodiments depending on the type of substrate,
The binder is or includes sodium silicate (Na ₂ SiO ₃ ). In certain embodiments, the binder facilitates or achieves support of an Al ₂ O ₃ —SiO ₂ —SiC matrix.

One embodiment of a high emissivity coating composition according to the present disclosure is about 2.8% to 75% A
l ₂ O ₃ , about 13.9% to 27.8% TiO ₂ , about 8.3% to 25.0% SiC
, About 4.2% to 11.1% chromium oxide Cr ₂ O ₃ , and about 5.6% SiO ₂ dry blend, wherein each of the percentages is a weight percentage. Corresponding coating compositions that are solution-type or slurry-type (wet admixtures) are from about 2% to 54% Al ₂ O ₃ , from about 10% to 40% TiO ₂ , from about 6% on a weight percentage basis. 18% SiC, about 3
% To 8% Cr ₂ O ₃ , about 4% SiO ₂ , and water containing about 2% to 28% H ₃ PO ₄ .

In addition to the above, a colorant can be included in the coating composition to form a colored coating composition. Non-limiting examples of colorants include cadmium yellow, cadmium orange, cadmium red, cadmium orange deep, cadmium lithopone orange, and cadmium lithopone red. The colorant range or dilution ratio can be obtained from the colorant manufacturer's specifications. Stabilizers known to improve high temperature strength in refractory applications can also be incorporated into the coating composition if desired. Non-limiting examples of stabilizers include bentonite, kaolin, magnesium alumina silica clay, stabilized zirconium oxide, plate-like alumina, and other ball clay stabilizers.

Aspects of high emissivity coating composition manufacturing process
Process Embodiment for Extracting or Obtaining TiO ₂ from Polyolefin Catalyst Waste FIG. 1 shows from a waste source, waste stream, or waste solution containing a polyolefin catalyst,
TiO ₂ for use in preparing a high emissivity coating, coating system or coating composition (hereinafter collectively referred to as coating composition) in accordance with embodiments of the present disclosure.
FIG. 2 shows a flowchart of a process 100 for extracting or obtaining The waste sources, waste streams, and waste solutions referred to herein are used interchangeably and include, but are not limited to, polymerization processes such as the production of polyolefins by polymerization of olefins. A process stream or process batch containing the catalyst is included. Waste sources, waste streams and waste solutions are not necessarily disposable, but include streams, solutions, and sources that contain spent catalyst and can be reactivated for reuse.

In the first process portion 110, at least one source comprising TiO ₂ and / or one or more forms of one or more Ti compounds or compositions from which TiO ₂ can be obtained or extracted. One, one or more forms from which TiO ₂ can be obtained or extracted, eg, TiO ₂ and / or TiO ₂
A waste source, waste stream, or waste solution comprising one or more Ti compounds or compositions is provided or obtained.

In embodiments of the present disclosure, a waste source, waste stream, or waste solution containing a catalyst associated with a polyethylene polymerization process is provided. Such a catalyst-containing waste source, waste stream, or waste solution can contain or hold TiO ₂ . In various embodiments, a catalyst-containing waste source, waste stream, or waste solution comprising TiO ₂ is a Ziegler
It can be derived from processes involving Natta catalysts, for example processes associated with the preparation and use of Ziegler-Natta catalysts.

In certain embodiments, the catalyst-containing waste source can be homopolymerized or copolymerized with other olefins, such as polypropylene, polybutene, polymethylpentene, polycycloolefin, polycritadiene, polyisopropene, amorphous It can be obtained from processes involving poly-α-olefins and polyacetylenes. In various embodiments, a suitable catalyst-containing waste source, waste stream, or waste solution obtains a sufficient or substantial amount of TiO ₂ therefrom in addition to or instead of the above, or TiO that can be extracted and generally requires a simple and / or economical extraction process
_It can be obtained from other processes that utilize catalyst systems that include a rich source and / or a Ti-containing source.

In certain embodiments, the source containing TiO _2, stream or solution, can be obtained from the ilmenite ore (i.e. ore based TiO ₂ source). For example, a source, stream, or solution containing TiO ₂ may be a membrane-based electrodialysis process (eg, a membrane-based electrodialysis process described in US Pat. No. 4,107,264).
Alternatively, it can be obtained from an ilmenite type ore using an organophosphate extraction process (such as the organophosphate extraction process for impurity removal described in US Pat. No. 4,168,297). In addition, or alternatively, in a specific embodiment, a source, stream, or solution comprising TiO ₂ provided in the first process portion 110 is a TiO ₂ pigment production process, such as US Pat. It can also be obtained from the TiO ₂ pigment production process described in US Pat. No. 094,834.

In the second process portion 120, a known amount and concentration of basic solution or basic material is added.
By introducing or added to TiO ₂ source under consideration (e.g., catalyst-containing waste and / or ore-based TiO ₂ source), for adjusting the pH value of the catalyst-containing waste source. In an exemplary embodiment, the basic solution is, but is not limited to, sodium hydroxide (NaOH)
And ammonium hydroxide (NH ₄ OH). For example, NaOH
The pH of the catalyst-containing waste source, waste stream, or waste solution is about 1.0 to 9
. It can be adjusted to 0 or about 2.0 to 8.0, or about 2.0 to 7.0. The catalyst-containing waste source, the waste stream or one or more other basic solution is used to adjust the pH of the waste solution, preferably, does not react with TiO _2.

In the third process portion 130, TiO ₂ is precipitated or separated from the considered (pH adjusted) TiO ₂ source, eg, catalyst-containing waste and / or ore-based TiO ₂ source. In many embodiments, the treated TiO ₂ source is allowed to settle, facilitating or achieving TiO ₂ precipitation. The duration allowed for settling or precipitation, and thus complete separation, can be adjusted or selected as required to achieve the desired separation.
For example, the TiO ₂ source can be allowed to settle for about 10 hours, 12 hours, 15 hours, or more.

In the fourth process portion 140, the precipitated TiO ₂ is recovered and washed thoroughly for removing impurities, eg, salts such as sodium chloride (NaCl). In some embodiments, the collected precipitated TiO ₂ is washed with deionized water, eg, about 3 to 6 times or more. Following washing, the precipitated TiO ₂ is heat treated in the presence of oxygen to thermally decompose TiO ₂ to rutile and / or remove volatile fractions. This heat treatment process may be performed at a temperature of about 900 ° C. to about 1100 ° C. The temperature of the heat treatment can be adjusted and is typically below the melting point of TiO ₂ which is about 1660 ± 10 ° C. The duration of the calcination or heat treatment process can be about 4 hours, 5 hours, or longer (eg, about 7 hours or longer).

In the fifth process portion 150, the resulting TiO ₂ is collected after completion of the calcination reaction or heat treatment process. The collected TiO ₂ may be cooled and then ground to an average particle size of less than about 65 mesh. One skilled in the art will appreciate that TiO ₂ can be readily ground to other average particle sizes or equivalent US sieve series or Tyler mesh sizes larger or smaller than 65 mesh.

Process Aspects for Preparing or Producing High Emissivity Coating Composition FIG. 2 illustrates a flowchart of a process 200 for preparing or producing a coating composition according to an embodiment of the present disclosure.

In the embodiment described with reference to FIG. 2, a process 200 for preparing or producing a coating composition is performed in a batch mode. It should be understood that the embodiments for preparing the coating compositions described herein are not limited to batch processes and that continuous processes can also be used. In the first process part 210, a mixing vessel or mixing tank is prepared. The mixing vessel is configured to facilitate mixing and dispensing of the particles or contents therein. A wide variety of mixing containers are known in the art. Generally such mixing vessels are equipped with at least some form of impeller, stirrer, and / or baffle,
In some cases, a rotating blade is also provided.

In the second process portion 220, a predetermined amount of ceramic precursor, emissive agent or emissivity enhancer, and matrix strength enhancer used to prepare the coating composition is introduced into the mixing vessel. Such ceramic precursors include aluminum oxide (Al
₂ O ₃ ), silicon dioxide (SiO ₂ ), magnesium oxide (MgO), calcium oxide (
A filler selected from CaO) and boron oxide (B ₂ O ₃ ) is included. Exemplary emissive agents or emissivity enhancers include titanium dioxide (TiO ₂ ), and in some embodiments, additional emissivity enhancers are silicon carbide (SiC), chromium oxide (Cr ₂ O ₃ ).
, Silicon dioxide (SiO ₂ ), iron oxide (Fe ₂ O ₃ ), boron silicide (B ₄ Si),
Boron carbide (B ₄ C), silicon tetraboride (SiB ₄ ), molybdenum disilicide (
MoSi ₂ ), tungsten disilicide (WSi ₂ ), and zirconium diboride (
ZrB ₂ ). Examples of matrix strength improvers include silicon carbide (S
iC), hafnium diboride (HfB ₂ ), hafnium carbide (HfC), hafnium nitride (HfN), tantalum diboride (TaB ₂ ), tantalum carbide (Ta
C), tantalum nitride (TaN), titanium diboride (TiB ₂ ), titanium carbide (TiC), titanium nitride (TiN), zirconium diboride (ZrB ₂ ), zirconium carbide (ZrC), and zirconium knight. Ride (ZrN) is included. In many embodiments, the ceramic precursor, emissive agent or emissivity enhancer, and matrix strength enhancer have a special or predetermined average particle size selected to ensure uniform mixing. For example, the ceramic precursor, emissive agent or emissivity enhancer, and matrix strength enhancer can have a particle size of about 65 mesh, about 200 mesh, or about 325 mesh.

In a third process portion 230, the components of the coating composition are mixed in a mixing vessel according to a set of mixing parameters intended to produce a well-mixed mixture that is substantially free of residues greater than about 250 microns. Stir or blend in.

In the fourth process portion 240, at least one binder is added to the mixing vessel. As mentioned above, the binder supports the coating composition matrix and helps promote the bond between the coating composition and the substrate or surface to which the coating composition is applied. Accordingly, the binder is selected based on the type of substrate to which the coating composition is applied. In some embodiments, the substrate is at least of a silica insulated brick, ceramic fiber, ceramic module, refractory brick, plastic refractory, castable refractory, fiberlite, ceramic tile, an array of fiber boards, and refractory mortar When selected from one, an aqueous solution containing phosphoric acid (H ₃ PO ₄ ) can be used as a binder. The concentration of phosphoric acid can be selected to be in the range of, for example, about 10%, 15%, or 20% volume / volume. In some embodiments, sodium silicate (Na ₂ SiO ₃ ) is a suitable binder when the substrate is a metal.

In the fifth process portion 250, following the addition of the binder to the mixing vessel, a uniform binder dispersion is obtained in which the mixture content comprising the ceramic precursor and the binder is evidenced by a residue not greater than about 250 microns. To stir or stir.

In the sixth process portion 260, the resulting coating composition is collected from the mixing vessel. The coating composition can be transferred to a bucket or individual container having a predetermined volume for storing, containing, receiving, or holding the coating composition.

Process Aspects for Applying Coating Composition to Substrate FIG. 3 is a flowchart of a process for applying a coating composition to a substrate according to an embodiment of the present disclosure.

In the first process portion 310, a substrate is prepared. Base material is silica insulated brick, ceramic fiber, ceramic module, refractory brick, plastic refractory, castable refractory, refractory mortar, fiber light, ceramic tile, fiberboard array,
And at least one of metals. The substrate can be an inner lining, structure and / or parts of a furnace (eg cracking furnace), combustion heaters, preheaters, reformers, other fireproof devices in the field, ceramic automotive parts, fireproof aerospace parts Or can be marine parts that are exposed to high temperatures during use.

In the second process portion 320, the substrate is prepared for coating. In certain embodiments,
Prior to coating, the substrate is cured, baked or cleaned. For example, the substrate can be cured by heating to a desired temperature for some specific duration to remove moisture and chemicals. In some embodiments, a dust collector is used to clean the substrate to remove dust or particles that can adversely affect or interfere with the bond between the substrate and the coating composition.

In a third process portion 330, a coating composition according to an embodiment of the present disclosure is provided. The coating composition can be prepared in the same or similar manner as described herein and can take the form of a slurry. Since particles or sediment in the coating composition may settle during storage, the coating composition is agitated, if necessary, to ensure complete particle dispersion prior to use. A portable electric mixer can be used to agitate the coating composition prior to applying it to the substrate in the field. It is understood that other types of mixers or agitators or stirrers can also be used.

In the fourth process portion 340, the coating composition is applied to the surface of the substrate in a controlled manner. The coating composition can be applied to the surface of the substrate using methods known to those skilled in the relevant art (ie, surface coating methods). Exemplary methods include application by brush, blade, or sprayer.

In a fifth process portion 350, the coated substrate is subjected to a drying process. For example, the coating on the substrate is dried for about 1 to 3 days or more.

The following representative examples 1-3 illustrate the effects, functions, and / or properties of coating compositions of the type described in this disclosure. Those skilled in the art will appreciate that the scope of the present disclosure is not limited to the following representative examples.

Example 1
Effect of Variation of TiO ₂ Content on Emissivity of Coating Composition This example illustrates the effect of TiO ₂ content on emissivity of the coating composition. In general terms, the emissivity increasing the amount of TiO ₂ is increased, this increase in emissivity as a result of increasing the TiO ₂ content is marked at 1000 ° C. from 400 ° C., 1100
Less obvious at 1300 ° C. and less obvious at 1300 ° C. this is,
The effect of increasing the TiO ₂ content on the emissivity value suggests that it decreases as the temperature that determines the emissivity value increases.

Experiments to investigate the effect of TiO ₂ content on the emissivity of the coating composition when TiO ₂ is used as the emissive agent or emissivity enhancer in preparing the coating composition according to the second process portion of FIG. Went.

Five radioactive coating compositions (A), (B), (C), (D), and (E) were prepared. After each of the coating compositions was prepared, they were applied by spraying them onto a test piece of insulated brick having a predetermined dimension. Spray coating of the high emissivity coating composition was performed using a commercially available sprayer. In order to achieve a smooth and good basis weight, the bulk density of the coating composition was controlled at about 1.50-1.70 kg / L. A nozzle diameter of about 1-2 mm and a pressure of about 4-5 bar were used. The distance between the nozzle and the coating surface was maintained at about 50 cm. The insulating brick was 20 × 20 × 2.5 cm and a coating rate of about 1.8 kg / m 2 was used. To cure the coating, the coated substrate was heated in a high temperature furnace at 800 ° C. for 5 hours, and then the coating was cooled to ambient temperature. The coated and cooled substrates were tested to determine their emissivity.

The emissivity was measured using a standard pyrometer. Each substrate sample was heated to the indicated temperature, the substrate temperature was measured, and the emissivity value was adjusted so that the pyrometer displayed the correct temperature. 400
The respective emissivity values of the coating compositions (A) to (E) at temperatures ranging from 0 C to 1300 C were measured. It will also be appreciated by those skilled in the art that as long as the same technique is used for each specimen, emissivity values can be measured by using other methods or techniques alternatively.

Preparation of Coating Compositions (A) to (E) Each coating composition (A) to (E) was prepared using a predetermined amount of ceramic precursor and emissivity improver. The ceramic precursor used was aluminum oxide (Al
₂ O ₃ ), silicon carbide (SiC), chromium oxide (Cr ₂ O ₃ ), silicon dioxide (
SiO ₂ ). Titanium dioxide (TiO ₂ ) was used as an emissivity improver. Except where otherwise stated, ceramic precursors and titanium dioxide were obtained from commercial sources. The ceramic precursor used to prepare each of the coating compositions (A) to (E) had an average particle size of less than about 325 mesh.

TiO in each of the final coating compositions (A) to (E) on a wet blend basis
The weight percentage of ₂ varied between about 10% and 40%, but SiC, Cr ₂ O ₃ ,
And the weight percentage of SiO ₂ was kept constant. In addition, the amount of filler can be reduced to reduce TiO
_In order to evaluate the hardening of the TiO ₂ content against the emissivity when the amount of ₂ is increased, Al ₂ O
The weight percentage of ₃ was varied to decrease between about 42% and 2% with respect to the increasing weight percentage of TiO ₂ .

The content of ceramic precursor in each of the coating compositions (A) to (E) was as follows:
Coating composition (A)
The coating composition (A) is about 42% Al ₂ O ₃ , 0% TiO ₂ , 18 by weight.
% SiC, 8% Cr ₂ O ₃ , and 4% SiO ₂ .
Coating composition (B)
The coating composition (B) is about 32% Al ₂ O ₃ , 10% TiO ₂ by weight, 1
It contained 8% SiC, 8% Cr ₂ O ₃ , and 4% SiO ₂ .
Coating composition (C)
The coating composition (C) is about 22% Al ₂ O ₃ , 20% TiO ₂ by weight, 1
It contained 8% SiC, 8% Cr ₂ O ₃ , and 4% SiO ₂ .
Coating composition (D)
The coating composition (D) is about 12% Al ₂ O ₃ , 30% TiO ₂ by weight, 1
It contained 8% SiC, 8% Cr ₂ O ₃ , and 4% SiO ₂ .
Coating composition (E)
The coating composition (E) is about 2% Al ₂ O ₃ , 40% TiO ₂ by weight, 18
% SiC, 8% Cr ₂ O ₃ , and 4% SiO ₂ .

Uniform mixing as evidenced by the introduction of the predetermined amount of ceramic precursor and emissivity improver described above into the mixing tank, followed by agitation, with no residue greater than about 250 microns present Achieved. Following stirring, about 17% volume / volume phosphoric acid (H ₃ P
An aqueous solution containing O ₄ ) was introduced into the mixing tank as a binder. More specifically, about 28% by weight of an aqueous solution containing 17% volume / volume H ₃ PO ₄ was added to the stirred mixture to a total of 100% by weight. The resulting mixture was stirred for several minutes from which a coating composition was obtained.

  The coating composition was applied to the substrate using the techniques described above.

Results As shown in Table 1, in coating compositions (A) to (E), increasing the TiO ₂ content results in an increase in emissivity, particularly at temperatures from about 400 ° C. to 1000 ° C. It was remarkable. More specifically, a weight percentage of TiO ₂ of about 20% or more is about 1000 ° C. compared to an emissivity value of about 0.93 to 0.96 in the absence of TiO _2. It resulted in an emissivity value of 0.98-0.99. In general, the inclusion of TiO _{2 in} a weight percentage of about 20% or more increases the emissivity value by about 1% to 6% depending on the temperature compared to the coating composition (A) excluding TiO _2. did. It was observed that at any temperature, the addition of TiO ₂ resulted in an increase in emissivity or at least no decrease.

Coating compositions (C), (D), and (E) were found to produce the highest emissivity values at different temperatures. These coating compositions have a T of about 20% or more.
contained iO ₂ and less than about 22% Al ₂ O ₃ . Furthermore, from about 400 ° C. to 1100
At a temperature of 0 ° C., it was found that a TiO ₂ weight percentage of at least about 10% caused the desired emissivity increase, ie 0.03 and 0.01 emissivity units, respectively.

The dry blend weight percentage of the components of the composition listed above is, for example, 28% by weight of H ₃ PO
_One skilled in the art understands that, for example, the specified wet weight percentage can be calculated for a total 72% percent dry weight, taking into account that the aqueous solution containing ₄ has been added to the mixing tank or vessel. Will be done.

Example 2
Effect of source of TiO _{2 on} emissivity of coating composition In this example, TiO ₂ obtained from a catalyst-containing waste stream is the same as a coating composition containing TiO ₂ from a non-waste commercial source Indicates to give an emissivity value.

Experiments were conducted to compare the effect of the source of TiO ₂ used as the emissive agent or emissivity enhancer on the emissivity of the coating composition prepared according to the second process portion 220 of FIG.

Four radioactive coating compositions (A), (B), (C), and (D) were prepared.
After each preparation of the coating composition, the coating composition was applied using the same substrates and techniques as described in Example 1 above. Next, the emissivity values of the coating compositions (A) to (D) at temperatures ranging from about 400 ° C. to 1300 ° C. were measured by the same method as described in Example 1 above.

Preparation of coating compositions (A) to (D) Each coating composition (A) to (D) was prepared using a predetermined amount of ceramic precursor and emissivity improver. The ceramic precursor is aluminum oxide (Al ₂ O ₃ )
, Silicon carbide (SiC), chromium oxide (Cr ₂ O ₃ ), and silicon dioxide (S
iO ₂ ). Titanium dioxide (TiO ₂ ) was used as an emissivity improver. Al
₂ O ₃ , SiC, Cr ₂ O ₃ , and SiO ₂ were obtained from the same commercial source that provided the same material in Example 1. TiO ₂ can be obtained from the same commercial source that provides the TiO ₂ used in Example 1, or a polyolefin catalyst-containing waste source, waste stream,
Or obtained from a waste solution, such as the sources described above with respect to process 100 of FIG.
Details of the process used to obtain TiO ₂ from the polyolefin catalyst-containing waste stream used in this example are described below. The ceramic precursor and emissivity enhancer used to prepare each of the coating compositions (A) to (D) had an average particle size of less than about 325 mesh.

Ti in each of the final coating compositions (A) and (B) on a wet blend basis
The O ₂ weight percentage was maintained at about 10%, and the respective TiO ₂ weight percentage of the final coating compositions (C) and (D) was maintained at about 20%. Coating compositions (A) and (
In B), the weight percentage of Al ₂ O ₃ was maintained at about 32 wt%. Coating composition (C
) And (D), the Al ₂ O ₃ weight percentage was maintained at about 22 wt%. SiC, C
The weight percentages of r ₂ O ₃ and SiO ₂ were kept constant for coating compositions (A) to (D). The content or amount of ceramic precursor and the source of TiO ₂ in each of the coating compositions (A) to (D) were as follows:
Coating composition (A)
The coating composition (A) is about 10% TiO ₂ by weight, 32% Al ₂ O ₃ , 1%
It contained 8% SiC, 8% Cr ₂ O ₃ , and 4% SiO ₂ . TiO ₂ was obtained from a commercial source.
Coating composition (B)
The coating composition (B) is about 10% TiO ₂ by weight, 32% Al ₂ O ₃ , 1%
It contained 8% SiC, 8% Cr ₂ O ₃ , and 4% SiO ₂ . TiO ₂ was obtained from a polyolefin catalyst-containing waste stream extraction process.
Coating composition (C)
The coating composition (C) is about 20% TiO ₂ , 22% Al ₂ O ₃ , 1% by weight.
It contained 8% SiC, 8% Cr ₂ O ₃ , and 4% SiO ₂ . TiO ₂ was obtained from a commercial source.
Coating composition (D)
Coating composition (D), by weight, about 20% of _TiO 2, 22% of the _Al 2 _O 3, 1
It contained 8% SiC, 8% Cr ₂ O ₃ , and 4% SiO ₂ . TiO ₂ was obtained from a polyolefin catalyst-containing waste stream extraction process.

Extraction of TiO ₂ from a polyolefin catalyst-containing waste stream The polyolefin catalyst-containing waste stream used as the source of TiO ₂ in Example 2 was obtained from a polyethylene manufacturing process.

A polyethylene catalyst-containing waste stream or effluent (hereinafter “PE catalyst waste”) was collected from the polyethylene manufacturing process. The pH of the PE catalyst waste was adjusted from about 2.0 to 7.0 by introducing a solution containing sodium hydroxide (NaOH). Upon pH adjustment, TiO ₂ and Al (OH) ₂ precipitated and the mixture was allowed to settle overnight. In order to remove salts such as sodium chloride (NaCl), the precipitate portion containing TiO ₂ was thoroughly washed with demineralized water about 4-5 times. The washed TiO ₂ is then dried overnight at about 500 ° C. to remove volatile fractions and to ensure that TiO ₂ is in its rutile form.
Calcinated at 00 ° C for about 5 hours. The resulting TiO ₂ was ground to an average particle size of less than about 65 mesh.

The ceramic precursor and TiO ₂ were introduced into the mixing tank and stirred therein. Following stirring, an aqueous solution containing about 17% volume / volume phosphoric acid (H ₃ PO ₄ ) was introduced into the mixing tank to form a binder. More specifically, about 28% by weight of 17% volume / volume H ₃ P
By adding an aqueous solution containing O ₄ to the stirred ceramic precursor and TiO ₂ ,
The total amount was 100% by weight. The resulting mixture was stirred for several minutes from which a coating composition was obtained.

The mixture was applied to the same type of substrate using the same technique as described in Example 1 above.

Results In the same manner as described in Example 1, emissivity values were determined for the test specimens holding coating compositions (A) to (D). The results showing the respective emissivity values of the coating compositions (A) to (D) are listed in Table 2 below. The result is that when 10% TiO ₂ and the ceramic precursor used are of equal weight fraction, the coating composition (B) is the same as the coating composition (A) at temperatures of about 1000 ° C. and 1300 ° C. It has essentially the same emissivity value, indicating that at temperatures of about 1100 ° C. and 1200 ° C., it has almost or almost the same emissivity value. In addition, the results show that when the weight fraction of 20% TiO ₂ is equal and the weight fraction of the ceramic precursor is the same, the coating composition (D) is approximately equal to the coating composition (C). Have the same emissivity value at a temperature of 1100 ° C.,
It has also been demonstrated to have almost or nearly identical emissivity values at temperatures of about 1000 ° C, 1200 ° C and 1300 ° C. These results indicate that the coating composition prepared using TiO ₂ from a polyolefin catalyst-containing waste source (which functions as a radioactive agent or emissivity enhancer) as described in this disclosure is not waste. TiO from commercial sources
₂ has the same, essentially the same, nearly the same or comparable emissivity values, depending on the temperature at which the emissivity is measured, as compared to the coating composition prepared using ₂ .

The dry blend weight percentage of the components of the composition listed above is, for example, 28% by weight of H ₃ PO
_One skilled in the art will appreciate that, for example, the specified wet weight percentage can be calculated for a total 72% percent dry weight, taking into account that the aqueous solution containing ₄ has been added to the mixing vessel. Will.

Example 3
High Emissivity Coating Composition Surface Adhesion Test An experiment was conducted to evaluate the bond between the high emissivity coating composition of the present disclosure and the substrate to which the coating composition was applied.

In this example, two coating compositions were prepared as described in the following paragraphs.

Preparation of coating compositions (A) and (B) Coating compositions (A) and (B) using a predetermined amount of ceramic precursor
Was prepared. The ceramic precursor contained aluminum oxide (Al ₂ O ₃ ), silicon carbide (SiC), chromium oxide (Cr ₂ O ₃ ), silicon dioxide (SiO ₂ ). Titanium dioxide (TiO ₂ ) was used as an emissivity improver. Al ₂ O ₃ , SiC, Cr ₂ O ₃
, And SiO ₂ were derived from commercial sources and exhibited an average particle size of less than about 425 mesh.
TiO ₂ was obtained from recovered polyethylene catalyst as described in Example 2 and had an average particle size of less than about 65 mesh. The ceramic precursor content in the coating compositions (A) to (B) was as follows:
Coating composition (A)
The coating composition (A) is about 32% Al ₂ O ₃ , 10% TiO ₂ by weight, 1
It contained 8% SiC, 8% Cr ₂ O ₃ , and 4% SiO ₂ .
Coating composition (B)
The coating composition (B) is about 22% Al ₂ O ₃ , 20% TiO ₂ by weight, 1
It contained 8% SiC, 8% Cr ₂ O ₃ , and 4% SiO ₂ .

The ceramic precursor and TiO ₂ were introduced into the mixing tank and stirred therein. Following stirring, an aqueous solution containing about 17% volume / volume phosphoric acid (H ₃ PO ₄ ) was introduced into the mixing tank to form a binder. More specifically, about 28% by weight of 17% volume / volume H ₃ P
An aqueous solution containing O ₄ was added to the stirred ceramic precursor to a total of 100% by weight. The resulting mixture was stirred at 25 rpm for several minutes before collecting the coating composition.

In this example, silica heat insulating brick was used as a base material. Prior to application of the coating composition, the substrate was cleaned using a dust collector. The coating composition was sprayed onto the substrate in a controlled manner using a 2.5 millimeter spray gun. More specifically, the sprayer pressure is about 5 to 6 bar and the amount of coating applied is about 1 to 1.6 kg.
/ M ² .

Prior to the adhesion test, the coated substrate was heated at about 800 ° C. for about 5 hours. The heated substrate was then cooled to ambient temperature.

The adhesion test was designed to simulate a decoking cycle performed in a naphtha cracking furnace. In operation of a naphtha cracking furnace, the furnace is heated to an operating temperature of about 1100 ° C., and typically there are 8 decoking cycles per year of operation. During the decoking cycle, the furnace heated to an operating temperature of about 1100 ° C. is cooled to ambient temperature. After cooling to ambient temperature, the furnace is again heated to the operating temperature and the second cycle begins. Hence,
To demonstrate that the radioactive coating composition has a service life of at least one year under typical annual decoking conditions, the coated substrate is about 16 hours over about 5 hours.
Adhesion tests are performed by heating to 00 ° C. (which is about 45% higher than the actual operating temperature of the naphtha cracking furnace), and then the heated substrate is cooled to ambient temperature for one decoking cycle. Was simulated. This pseudo decoking cycle was repeated 8 times. Following completion of one decoking cycle, the coating on the substrate was observed for shrinkage and cracking. Optical microscopy, scanning electron microscopy, and / or other observation techniques can be used to assess surface features and interfacial adhesion of the coating composition to the substrate. In this example, the heating and cooling process, followed by optical observation of the coating and substrate, evaluation of the coating composition surface condition and interfacial adhesion by inspection and measurement was repeated eight times. A cross-sectional photograph of a heat-resistant brick to which the coating compositions (A) and (B) are applied is presented in FIGS. 4A and 4B.

In order to evaluate the quality of the adhesion between the coating and the substrate, the coating composition (A)
And (B) were subjected to two types of adhesion tests according to ASTM number C1624-05. The first test was a pull-off test utilizing a dolly attached to the coating.
In the pull-off test, a force in a direction away from the surface on which the dolly was attached was applied to the dolly. An example of a device that is useful for performing adhesion tests is DeFe, Ogdensburg, NY.
PosiTest® pull-off adhesion tester available from lsko Corporation. The second test was a scratch test to evaluate the mechanical failure mode according to ASTM C1624-05.

Results As can be seen from optical observations, inspections and measurements of the coating and substrate, both coating compositions (A) and (B) exhibited good adhesion to the silica insulated brick substrate. At a coating thickness of 200 microns, the coating did not peel from the substrate even at a maximum load of 3000 psi. When tested in the scratch test, a coating thickness of 200 microns exhibited an adhesion strength of 38N. In addition, coating compositions (A) and (B)
Both withstood heat shock from 8 cycles of heating and cooling.

FIG. 4C is an optical image of a commercially available high emissivity coating composition sold by SZET under the trade name QZ, having a SiC content of about 23 wt% on a wet basis. The commercial coating peeled from the substrate as evidenced by cracks between the substrate and the coating.
Such delamination is evident on surfaces coated with a high emissivity coating that does not exhibit the same level of substrate adhesion, heat resistance, and mechanical properties as the coating compositions of the disclosed embodiments. 5A-5C are photographs of the inner wall surface of a naphtha cracking furnace coated with a commercially available high emissivity coating composition after 3 years of operation at 1200 ° C. FIG.
The coating compositions shown in FIGS. 5A-5C performed satisfactorily during the first three months of operation, during which time 3% to 4% energy savings were observed, but after the first three months had passed. Was dramatically reduced in performance, as evidenced by a reduction in energy savings of about 0.5%. In addition, after 3 months of operation, some peeling of the coating surface from the underlying substrate was also observed. After three years of such operation, the coating shown in FIGS. 5A-5C had a SiC content of about 22% on a dry basis. Based on this amount, it is estimated that the coating composition first applied to the furnace wall contained about 30% to 40% SiC on a dry basis. In FIGS. 5A-5C, the coating has begun to peel from the underlying substrate or has peeled due to insufficient adhesion and thermal properties of commercially available coatings. While not wishing to be bound by theory, the performance degradation demonstrated by coating delamination in FIGS. 5A-5C is a result of the SiC content of the original coating being 30% or more on a dry basis. It is thought that.

These results show that the coating composition (A) contains less than 30% SiC on a dry basis.
And (B) promote and maintain good adhesion to the silica insulated brick substrate and have and maintain good heat resistance under conditions simulating at least one year of operation of the naphtha cracking furnace. Show. Unlike the commercial coating composition illustrated in FIG. 4C, the coating compositions (A) and (B) did not delaminate from their respective substrates after 8 pseudo-decoking cycles. In addition, these results indicate that the coating compositions (A) and (B
TiO ₂ weight percentage range spanning ±) TiO ₂ weight percentage included in a weight percentage variation of about 5% to 20% (eg, about 10% to 15%) for the extremes in this range, and on a dry basis It has been shown that a coating composition of the present disclosure comprising less than 30% SiC can provide both improved emissivity and desirable substrate adhesion properties. For example, a wet blend weight percentage of at least about 8% to 10% TiO ₂ , or less than about 22% to less than 23% TiO ₂
A wet blend weight percentage, or a wet blend weight percentage of between about 10% and 20% TiO ₂ and a SiC content of less than 30% on a dry basis, or even less than about 20% on a dry basis. The disclosed coating composition provides improved emissivity and desirable substrate adhesion properties. In an exemplary coating composition embodiment of the present disclosure, the weight percentage of a particular set of components of the composition (eg, Al) when changing the TiO ₂ weight percentage from one particular coating composition to another particular coating composition. ₂ O ₃ weight percentage) can be adjusted accordingly, so that the weight percentages of the other composition components can remain constant.

The dry blend weight percentage of the components of the composition listed above is, for example, 28% by weight of H ₃ PO
_One skilled in the art will appreciate that, for example, the specified wet weight percentage can be calculated for a total 72% percent dry weight, taking into account that the aqueous solution containing ₄ has been added to the mixing vessel. Will.

The results reported in Examples 1-3 were surprising and / or unexpected. The results show that TiO ₂ can act as an emissivity improver in thermal radiation coating compositions and that TiO ₂ obtained from industrial waste sources or industrial waste streams such as those associated with polyolefin polymerization processes has improved. Produce coating compositions with emissivity (for example, an increase of 0.01 to 0.06 emissivity units or more) and a significant number of thermal cycles and / or adhesion properties to substrates that do not exhibit delamination over extended periods of time Shows that can be used to. Furthermore, in certain embodiments, a coating composition that provides both improved emissivity and substrate adhesion properties in accordance with embodiments described herein includes greater than about 30% SiC on a dry basis, and a suitable It is not necessary to include 20% to 22% TiO ₂ (eg, less than about 20% TiO ₂ ) and at least about 8% to 10% TiO ₂ on a wet blend basis to provide emissivity enhancement. Similarly, coating compositions according to certain embodiments of the present disclosure have greater than about 30% SiC on a dry basis, and 27% to 30% TiO2 (on a dry blend to provide adequate emissivity improvement). For example, less than about 27% to less than 29% (eg, less than about 28% TiO ₂ ) and at least about 11% TiO ₂ need not be included. In certain embodiments, a coating composition according to embodiments of the present disclosure comprises less than 30% SiC on a dry basis and between about 8% and 16% TiO on a wet blend.
₂ or between about 11% and 22% TiO ₂ on a dry blend basis.

Representative examples of coating compositions provided by the present disclosure are described in Examples 4-6 below. Those skilled in the art will appreciate that the scope of the present disclosure is not limited to the following compositions.

Example 4
A coating composition in the form of a slurry blend was prepared according to the present disclosure. The composition comprises
About 22 wt% aluminum oxide (Al ₂ O ₃ ), about 18 wt% silicon carbide (
SiC), about 8 wt% chromium oxide (Cr ₂ O ₃ ), about 4 wt% silicon dioxide (SiO ₂ )
₂ ), about 20 wt% titanium dioxide (TiO ₂ ), and about 17% volume / volume H ₃ PO
About 28% water containing ₄ was included. TiO ₂ was selected from a commercial source, or the treated polyolefin catalyst waste stream described in Example 2 above, or a combination of these two sources. TiO ₂ from commercial sources has a higher purity than TiO ₂ recovered from waste streams. For example, TiO ₂ from a commercial source exhibits a purity greater than 99%, while
TiO ₂ from the waste source has a purity of 80% to 90% due to the presence of Al (OH) ₃ that can be converted to Al ₂ O ₃ according to the embodiments described above.

  The coating composition was formulated using the process 200 of FIG.

The coating composition has a density of about 1.5-1.6 kg / liter, an emissivity greater than about 0.97 at about 1000 ° C., an emissivity greater than about 0.85 at about 1200 ° C. (Description of Example 1) And showed good surface adhesion to the coated substrate according to optical observations. The coating composition was applied directly to the substrate using a sprayer. Due to its improved emissivity and deposition capability, in a furnace including a surface coated with the coating composition described in this example, the reduction in fuel gas consumption is desirably about 4
%, Or a furnace throughput of about 30-32 tons / hour would result in about 100-200 kilograms of fuel gas / hour. The calculated reduction in fuel consumption is about 30 naphtha feedstock throughput.
Based on a cracking furnace with a fuel gas of ~ 32 tons / hour and a normal fuel consumption of about 5 tons / hour. After applying this example coating, the furnace fuel gas consumption was reduced by about 100-200 kilograms / hour or about 2% to 4%. This fuel gas savings remained constant after 10 decoking cycles.

Example 5
A coating composition in the form of a dry blend was prepared according to the present disclosure. The composition is about 3
0.5 wt% aluminum oxide (A1 ₂ O ₃ ), about 25.0 wt% silicon carbide (SiC), about 11.1 wt% chromium oxide (Cr ₂ O ₃ ), about 5.6 wt% Silicon dioxide (SiO ₂ ), and about 27.8 wt% titanium dioxide (TiO ₂ ). T
iO ₂ was selected from a commercial source, or the treated polyolefin catalyst waste stream described in Example 2, or a combination of commercial and waste sources. TiO ₂ from commercial sources has a higher purity than TiO ₂ recovered from waste streams. For example, the TiO ₂ from commercial sources exhibit a purity of greater than 99%, whereas, TiO ₂ from waste sources can be converted into _Al 2 _{O 3} in accordance with the embodiments described above Al _{(OH) 3} 80% because there is
To 90% purity.

The coating composition was formulated using the process 200 of FIG. However, the process part 240 is omitted. Ceramic precursors, ie Al ₂ O ₃ , SiC, Cr ₂ O ₃ , SiO
₂ and emissivity-enhancing TiO ₂ from commercial sources have an average particle size of less than about 325 mesh, while T from a polyolefin catalyst-containing waste stream treated according to Example 2
iO ₂ had an average particle size of less than about 65 mesh.

A coating composition in the form of a dry blend was prepared for easy transportation and storage.
Prior to coating the substrate, the dry coating blend is well mixed in a controlled manner (eg, depending on the mixer configuration) with a 17% strength by volume aqueous phosphoric acid solution. Alternatively, the particles were prevented from aggregating and sticking to the side of the mixing container.

The prepared coating was applied to the insulating brick that forms the inner wall of the furnace. This furnace is about 4
When operated at 50 ° C., the fuel gas was originally consumed at about 1.25 tons / hour. This coating has an emissivity of 0.98 when the coated furnace is operated at about 450 ° C .;
That led to fuel gas consumption of about 4% or 50 kg / hour.

Example 6
A coating composition in the form of a slurry blend was prepared according to the present disclosure. The composition comprises
About 2% by weight aluminum oxide (Al ₂ O ₃ ), about 18% by weight silicon carbide (S
iC), about 8 wt% chromium oxide (Cr ₂ O ₃ ), about 4 wt% silicon dioxide (SiO ₂₎
), About 40 wt% titanium dioxide (TiO ₂ ), and about 17% volume / volume H ₃ PO _4.
About 28% water by weight. TiO ₂ was selected from a commercial source, or the treated polyolefin catalyst waste stream described above, or a combination of these two sources.
TiO ₂ from commercial sources has a higher purity than TiO ₂ recovered from waste streams. For example, the TiO2 from commercial sources exhibit a purity of greater than 99%, whereas, TiO ₂ from waste sources can be converted into _Al 2 _{O 3} in accordance with the embodiments described above Al (OH
) Because of the presence of _{3, it} has a purity of 80% to 90%.

  The coating composition was formulated using the process 200 of FIG.

The coating composition has a density of about 1.5-1.6 kg / liter, an emissivity above about 0.98 at about 1000 ° C., an emissivity above about 0.86 at about 1200 ° C. (measured according to Example 1). And had very good surface adhesion to the coated substrate. The coating composition was applied directly to the insulating brick substrate using a sprayer as described in Example 1 above. The coating composition contributed to a reduction in heat loss of at least about 20% in the furnace when applied to exposed surfaces. This reduction in heat loss of 20% determines the temperature of the outer surface of the furnace before and after application of the coating composition and applies conventional heat transfer laws to conduct and ambient conditions through the furnace wall (e.g. Based on calculating the difference in heat loss due to convection on the furnace wall surface at room temperature and wind speed

Example 7
In order to evaluate the adhesion properties and adhesion properties of the high emissivity coating having the composition shown in Table 3 to the insulating brick base material, the scratch test method (ASTM C1624-05 (10
)) Was carried out with compositions 1, 2 and 3. In general, the scratch test method is a spherical conical needle containing a Rockwell C diamond tip or cemented carbide tip with a 120 ° cone angle and a 200 μm tip radius, with a constant needle speed across the test coating-substrate system. Creating scratches by pulling on. As the needle is pulled across the coated substrate system, a constant or incremental load is applied to the substrate by the needle at a fixed rate. If the load increases gradually, the critical load (Lc) is defined as the minimum load at which discernible failure occurs.

The driving force for coating damage in the scratch test is a combination of elasto-plastic indentation stress, friction stress and residual internal stress. In low load regimes, these stresses result in conformal or tensile cracking of the coating that still remains fully attached to the substrate. The occurrence of these stresses defines the first critical load. In the high load regime, another critical load is defined, which corresponds to the occurrence of coating detachment from the substrate by spalling, buckling or chipping.

In this example, each sample was scratched 3 times using a CSM Instruments SA Revest Scratch Tester (RST). RST is suitable for testing adhesion / tack strength of hard coatings on soft substrates as well as soft coatings on hard substrates. Measurements were made using a hard metal tip having a cone angle of 120 °. Test conditions and parameters are listed in Table 3. After the measurement, each sample was cleaned with duster spray, and the distance between the initial contact point with the needle and the place where the coating peeled off from the substrate was measured. The applied force / distance curve was used to determine the load corresponding to the location where delamination occurred. The load at which peeling occurred for each sample is reported in Table 4 below.

Each coating composition was prepared using the technique described in Example 1 above. Each sample was prepared by applying the wet coating composition to the insulating brick substrate as described in Example 3. Prior to the scratch test, the coating was baked at 1200 ° C. for 5 hours. The baked coating was 200 micrometers thick.

The results reported in Table 4 indicate that the sample composition peeled from the substrate with loads ranging from 21.4N to 38.8N. These results are representative of sample composition adherence to a thermally insulating brick substrate.

Additional Aspects of Formulation, Preparation, or Selection of Coating Composition According to some embodiments of the present disclosure, one or more other coating composition components (eg, fillers such as Al ₂ O ₃ ) How the emissivity is affected or can be expected to be affected when the TiO ₂ concentration is changed relative to the concentration of (for example, on a wet or dry blend weight percentage basis) By referring to or utilizing the explicit data, a target emissivity level for the coating composition under consideration, or a measure of emissivity enhancement for a set or group of coating compositions can be determined or estimated. Such data can be stored in electronic format (eg, a table or database) or non-electronic format. In addition, such data is T
When the iO ₂ concentration is varied (eg, relative to the filler), over a predetermined period, a significant period or a long period of time, eg, at least 6 months, about 1 year, or over a period of 1 year It can also include or specify how the coating composition attachment to one or more types of substrates is expected to be affected. Based on such data, a coating composition that provides the resulting improved emissivity and the desired substrate adhesion properties over a suitable period of time including the appropriate amount of TiO ₂ is identified, selected and easily prepared. be able to.

In order to address at least one of the foregoing problems, specific embodiments of the present disclosure have been described above. Although features, functions, processes, process parts, advantages, and alternative options associated with certain embodiments have been described in the context of these embodiments, other embodiments may exhibit such advantages and may be Not all embodiments necessarily have such advantages in order to fall within the scope of the disclosure. It will be appreciated that the features, functions, processes, process parts, advantages, and alternative options disclosed above may be desirably combined in different ways, processes, systems, or applications. The features, functions, processes, process parts or alternative options disclosed above, as well as various alternative options not currently foreseen or anticipated, changes, modifications or improvements that may be made by those skilled in the art are encompassed by the following claims .

The various embodiments described above can be combined to provide further embodiments.
All U.S. patents, U.S. patent application publications, U.S. patent applications, foreign patents, foreign patent applications and non-patent publications mentioned herein and / or listed in the application data sheet are hereby incorporated by reference in their entirety. Incorporated into. Aspects of the embodiments can be modified, if necessary, to provide further embodiments using various patent, application and publication concepts.

These and other modifications can be made to the embodiments in light of the above detailed description. In general, in the following claims, the terms used will not be construed as limiting the claims to the specific embodiments disclosed herein, but rather may be considered in accordance with the full equivalent scope given to the claims. It should be construed as including embodiments. Accordingly, the claims are not limited by the present disclosure.

These and other modifications can be made to the embodiments in light of the above detailed description. In general, in the following claims, the terms used will not be construed as limiting the claims to the specific embodiments disclosed herein, but rather may be considered in accordance with the full equivalent scope given to the claims. It should be construed as including embodiments. Accordingly, the claims are not limited by the present disclosure.
The following is an embodiment of the present disclosure.
[1]
A collection of radioactive agents comprising titanium dioxide, wherein the weight percentage of titanium dioxide is less than about 28% by weight of the coating composition and at least about 10% by weight of the coating composition; and
A set of matrix strength improvers selected from at least one of ceramic boride, ceramic carbide, and ceramic nitride;
A thermal radiation coating composition comprising a dry blend.
[2]
The heat-radiating coating composition of [1] above, wherein the coating composition comprises about 11 to 22% by weight of titanium dioxide.
[3]
The thermally emissive coating composition of [1] above, wherein the coating composition comprises at least about 10 wt% titanium dioxide and an emissivity value increased in a temperature range between about 400 ° C and 1300 ° C.
[4]
The thermal emissive coating composition of [1] above, wherein the coating composition comprises at least about 20 wt% titanium dioxide and an emissivity value of at least about 0.95 at a temperature of about 1000 ° C.
[5]
The thermal radiant coating composition of [1] above, wherein the emissivity value of the coating composition at a temperature of about 1000 ° C. increases as the weight percentage of titanium dioxide in the coating composition increases.
[6]
In addition to titanium dioxide, the set of radioactive agents consists of silicon carbide, chromium oxide, silicon dioxide, iron oxide, boron silicide, boron carbide, silicon tetraboride, molybdenum disilicide, tungsten disilicide, and zirconium diboride. The thermal radiation coating composition according to the above [1], comprising at least one radiation agent selected from the group.
[7]
The set of matrix strength improvers is silicon carbide, hafnium diboride, hafnium carbide, hafnium nitride, tantalum diboride, tantalum carbide, tantalum nitride, titanium diboride, titanium carbide, titanium nitride, diboron. The thermal radiation coating composition according to the above [1], comprising at least one matrix strength improver selected from the group consisting of zirconium fluoride, zirconium carbide, and zirconium nitride.
[8]
The thermal radiation coating composition according to the above [7], further comprising at least one filler selected from the group consisting of aluminum oxide, silicon dioxide, magnesium oxide, calcium oxide, and boron oxide.
[9]
Thermal radiation according to [1] above, wherein the coating composition further comprises a solution component, wherein the weight percentage of titanium dioxide in the wet blend of the coating composition is less than about 20% and at least about 10% by weight. Coating composition.
[10]
The thermal radiant coating composition of [1] above, wherein the weight percentage of titanium dioxide in the wet blend of the coating composition is between about 8 wt% and 16 wt%.
[11]
The thermal radiation coating composition according to [9] above, wherein the solution component contains a binder.
[12]
The thermal radiation coating composition according to [11] above, wherein the binder comprises phosphoric acid and / or sodium silicate.
[13]
The thermal radiation coating composition according to the above [1], further comprising about 2 wt% to about 60 wt% filler selected from aluminum oxide, silicon dioxide, magnesium oxide, calcium oxide and boron oxide.
[14]
The thermal radiation coating composition of [1] above, further comprising about 8% to less than 30% SiC on a weight basis on a dry basis.
[15]
The thermal radiant coating composition of [14] above, further comprising about 8% to about 20% SiC by weight on a dry basis.
[16]
A method of preparing a thermal radiation coating composition for a substrate, comprising:
Obtaining titanium dioxide;
Providing a set of radioactive agents comprising titanium dioxide;
Providing a set of matrix strength improvers comprising at least one matrix strength improver selected from the group consisting of ceramic boride, ceramic carbide, and ceramic nitride;
Providing a set of fillers, wherein the at least one filler is selected from the group consisting of aluminum oxide, silicon dioxide, magnesium oxide, calcium oxide, and boron oxide; and
Mixing the set of radioactive agents, the set of matrix strength improvers, and the set of fillers
Wherein the at least one filler comprises from about 2 wt% to about 60 wt% of the coating composition on a moisture basis.
[17]
The method of [16] above, wherein the titanium dioxide is obtained from at least one of an industrial waste source and an ore-based source.
[18]
The method of [17] above, wherein the industrial waste source comprises a polyolefin polymerization process waste source.
[19]
The method according to [18] above, wherein the industrial waste source comprises a Ziegler-Natta catalyst-containing waste source.
[20]
Obtaining titanium dioxide from the industrial waste source,
Adjusting the pH of the industrial waste source to between about 7.0 and about 9.0; and
Precipitating titanium dioxide from pH-adjusted industrial waste sources
The method according to [17] above, comprising:
[21]
The method of [20] above, wherein obtaining carbon dioxide from the industrial waste source further comprises subjecting the precipitated titanium dioxide to a pyrolysis process.
[22]
In addition to titanium dioxide, the set of radioactive agents consists of silicon carbide, chromium oxide, silicon dioxide, iron oxide, boron silicide, boron carbide, silicon tetraboride, molybdenum disilicide, tungsten disilicide, and zirconium diboride. The method according to [16] above, comprising at least one radioactive agent selected from the group.
[23]
The set of matrix strength improvers comprises silicon carbide, hafnium diboride, hafnium carbide, hafnium nitride, tantalum diboride, tantalum carbide, tantalum nitride, zirconium diboride, zirconium carbide, and zirconium nitride. The method according to [16] above, comprising at least one matrix strength improver selected from the group.
[24]
The method of [16] above, wherein the dry blend of the coating composition comprises less than about 28 wt% titanium dioxide and at least about 10 wt% titanium dioxide.
[25]
The method of [24] above, wherein the dry blend of the coating composition comprises less than about 22% by weight titanium dioxide and at least about 10% by weight titanium dioxide.
[26]
The method of [16] above, wherein the wet blend of the coating composition comprises less than about 20 wt% titanium dioxide and at least about 10 wt% titanium dioxide.
[27]
The method of [26] above, wherein the wet blend of the coating composition comprises less than about 16% by weight titanium dioxide and at least about 8% by weight titanium dioxide.
[28]
Increasing the emissivity value of the coating composition by adjusting the weight percentage of titanium dioxide present in the coating composition
The method according to [16], further comprising:
[29]
[28] The weight percentage of titanium dioxide in the coating composition is at least 20% on a wet basis, and the coating composition has an emissivity value of at least about 0.95 at a temperature of about 1000 ° C. ] Method.
[30]
Providing at least one binder selected from the group consisting of phosphoric acid and sodium silicate; and
Admixing the at least one binder with the set of radiation agents, the set of matrix strength improvers, and the set of fillers to form a coating composition.
The method according to [16], further comprising:
[31]
Providing a substrate having a plurality of surfaces; and
Applying the coating composition to at least one surface of the substrate;
The method according to [16], further comprising:
[32]
The substrate is selected from the group consisting of silica insulated bricks, ceramic fibers, ceramic modules, refractory bricks, plastic refractories, castable refractories, refractory mortar, fiber lights, ceramic tiles, arrays of fiber boards, and metals; The method according to [31] above.
[33]
The method of [32] above, wherein the substrate comprises a portion of a furnace, combustion heater, ceramic automotive part, refractory aerospace part, or marine part.
[34]
The method of [33] above, wherein the furnace comprises a cracking furnace.
[35]
The method of [16] above, wherein the wet blend of the coating composition contains from about 2% to about 60% by weight filler.
[36]
The method of [16] above, further comprising providing about 8% to less than 30% SiC on a dry basis on a weight basis.
[37]
The method of [36] above, comprising providing about 8% to about 20% SiC on a dry basis on a dry basis.
[38]
A method for adjusting the thermal emissivity of a substrate using a thermal radiation coating composition comprising:
Identifying a target emissivity level or target emissivity adjustment;
Determining the titanium dioxide concentration of the coating composition expected to provide the target emissivity level or the target emissivity adjustment;
Determining a set of substrate adhesion characteristics for the coating composition;
Determining the SiC concentration of the coating composition expected to provide the determined substrate adhesion characteristics; and
Providing a thermal radiation coating composition comprising a determined titanium dioxide concentration and a determined SiC concentration
Including a method.
[39]
The method of [38] above, wherein providing the thermal radiation coating composition comprising the determined titanium dioxide concentration comprises extracting titanium dioxide from an industrial waste stream or an ore-based titanium dioxide source.
[40]
The method of [39] above, wherein the industrial waste stream comprises a polyolefin polymerization process waste source.
[41]
The method of [40] above, wherein the polyolefin polymerization process waste source comprises a Ziegler-Natta catalyst containing waste source.
[42]
Extracting titanium dioxide from the industrial waste stream,
Adjusting the pH of the industrial waste stream to between about 7.0 and about 9.0; and
Precipitating titanium dioxide from a pH adjusted industrial waste stream
The method according to [41] above, comprising:
[43]
The method of [38] above, wherein determining the SiC concentration of the coating composition further comprises selecting a SiC concentration on a dry basis, such as from about 8% to less than 30% by weight.
[44]
The method of [43] above, wherein the SiC concentration on a dry basis is about 8% to about 20% on a weight basis.

Claims (44)

A collection of radiation agents comprising titanium dioxide, wherein the weight percentage of titanium dioxide is less than about 28% by weight of the coating composition and at least about 10% by weight of the coating composition; and of ceramic boride, ceramic carbide, and ceramic nitride A thermal radiation coating composition comprising a dry blend of a collection of matrix strength improvers selected from at least one. The thermally radiative coating composition of claim 1, wherein the coating composition comprises about 11-22 wt% titanium dioxide. The thermal radiant coating composition of claim 1, wherein the coating composition comprises at least about 10 wt% titanium dioxide and an increased emissivity value in a temperature range between about 400 ° C and 1300 ° C. The coating composition is at least about 20% by weight titanium dioxide and about 1000 ° C.
The thermally emissive coating composition of claim 1 comprising an emissivity value of at least about 0.95 at a temperature of. As the weight percentage of titanium dioxide in the coating composition increases, about 100
The thermally emissive coating composition of claim 1, wherein the emissivity value of the coating composition at a temperature of 0 ° C. increases. In addition to titanium dioxide, the set of radioactive agents consists of silicon carbide, chromium oxide, silicon dioxide, iron oxide, boron silicide, boron carbide, silicon tetraboride, molybdenum disilicide, tungsten disilicide, and zirconium diboride. The thermal radiation coating composition of claim 1 comprising at least one radiation agent selected from the group. The set of matrix strength improvers is silicon carbide, hafnium diboride, hafnium carbide, hafnium nitride, tantalum diboride, tantalum carbide, tantalum nitride, titanium diboride, titanium carbide, titanium nitride, diboron. The thermal radiation coating composition according to claim 1, comprising at least one matrix strength improver selected from the group consisting of zirconium fluoride, zirconium carbide, and zirconium nitride. The thermal radiation coating composition of claim 7, further comprising at least one filler selected from the group consisting of aluminum oxide, silicon dioxide, magnesium oxide, calcium oxide, and boron oxide. The coating composition further comprises a solution component, wherein the weight percentage of titanium dioxide in the wet blend of the coating composition is less than about 20 wt% and at least about 10 wt%;
The thermal radiation coating composition according to claim 1. The thermal radiant coating composition of claim 1, wherein the weight percentage of titanium dioxide in the wet blend of the coating composition is between about 8 wt% and 16 wt%.   The thermal radiation coating composition of claim 9, wherein the solution component comprises a binder. The thermal radiation coating composition of claim 11, wherein the binder comprises phosphoric acid and / or sodium silicate. The thermal radiation coating composition of claim 1, further comprising about 2 wt% to about 60 wt% filler selected from aluminum oxide, silicon dioxide, magnesium oxide, calcium oxide and boron oxide. The thermal radiation coating composition of claim 1, further comprising about 8% to less than 30% SiC on a dry basis on a dry basis. 15. The thermal radiation coating composition of claim 14, comprising about 8% to about 20% SiC on a dry basis on a dry basis. A method of preparing a thermal radiation coating composition for a substrate, comprising:
Obtaining titanium dioxide;
Providing a set of radioactive agents comprising titanium dioxide;
Providing a set of matrix strength improvers comprising at least one matrix strength improver selected from the group consisting of ceramic boride, ceramic carbide, and ceramic nitride;
Providing a set of fillers, wherein at least one filler is selected from the group consisting of aluminum oxide, silicon dioxide, magnesium oxide, calcium oxide, and boron oxide; and the set of radiation agents, the matrix strength improver And at least one filler is about 2 wt% to about 6 wt% of the coating composition on a moisture basis.
A method comprising 0 wt%. The method of claim 16, wherein the titanium dioxide is obtained from at least one of an industrial waste source and an ore-based source. The method of claim 17, wherein the industrial waste source comprises a polyolefin polymerization process waste source. The method of claim 18, wherein the industrial waste source comprises a Ziegler-Natta catalyst containing waste source. Obtaining titanium dioxide from the industrial waste source,
18. The method of claim 17, comprising adjusting the pH of the industrial waste source to between about 7.0 and about 9.0; and precipitating titanium dioxide from the pH adjusted industrial waste source. 21. The method of claim 20, wherein obtaining titanium dioxide from the industrial waste source further comprises subjecting precipitated titanium dioxide to a pyrolysis process. In addition to titanium dioxide, the set of radioactive agents consists of silicon carbide, chromium oxide, silicon dioxide, iron oxide, boron silicide, boron carbide, silicon tetraboride, molybdenum disilicide, tungsten disilicide, and zirconium diboride. 17. A method according to claim 16, comprising at least one radioactive agent selected from the group. The set of matrix strength improvers comprises silicon carbide, hafnium diboride, hafnium carbide, hafnium nitride, tantalum diboride, tantalum carbide, tantalum nitride, zirconium diboride, zirconium carbide, and zirconium nitride. 17. The method of claim 16, comprising at least one matrix strength enhancer selected from the group. The method of claim 16, wherein the dry blend of the coating composition comprises less than about 28 wt% titanium dioxide and at least about 10 wt% titanium dioxide. 25. The method of claim 24, wherein the dry blend of the coating composition comprises less than about 22% by weight titanium dioxide and at least about 10% by weight titanium dioxide. The method of claim 16, wherein the wet blend of the coating composition comprises less than about 20 wt% titanium dioxide and at least about 10 wt% titanium dioxide. 27. The method of claim 26, wherein the wet blend of the coating composition comprises less than about 16 wt% titanium dioxide and at least about 8 wt% titanium dioxide. The method of claim 16, further comprising increasing an emissivity value of the coating composition by adjusting a weight percentage of titanium dioxide present in the coating composition. The weight percentage of titanium dioxide in the coating composition is at least 20 on a moisture basis.
30. The method of claim 28, wherein the coating composition has an emissivity value of at least about 0.95 at a temperature of about 1000 <0> C. Providing at least one binder selected from the group consisting of phosphoric acid and sodium silicate; and admixing the at least one binder with the set of radiation agents, the set of matrix strength improvers, and the set of fillers The method of claim 16, further comprising forming a coating composition. 17. The method of claim 16, further comprising providing a substrate having a plurality of surfaces; and applying the coating composition to at least one surface of the substrate. The substrate is selected from the group consisting of silica insulated bricks, ceramic fibers, ceramic modules, refractory bricks, plastic refractories, castable refractories, refractory mortar, fiber lights, ceramic tiles, arrays of fiber boards, and metals; 32. The method of claim 31. 35. The method of claim 32, wherein the substrate comprises a portion of a furnace, combustion heater, ceramic auto part, refractory aerospace part, or marine part.   34. The method of claim 33, wherein the furnace comprises a cracking furnace. The method of claim 16, wherein the wet blend of the coating composition contains from about 2 wt% to about 60 wt% filler. The method of claim 16, further comprising providing from about 8% to less than 30% SiC on a dry basis on a weight basis. 37. providing about 8% to about 20% SiC on a dry basis on a dry basis;
The method described in 1. A method for adjusting the thermal emissivity of a substrate using a thermal radiation coating composition comprising:
Identifying a target emissivity level or target emissivity adjustment;
Determining the titanium dioxide concentration of the coating composition expected to provide the target emissivity level or the target emissivity adjustment;
Determining a set of substrate adhesion characteristics for the coating composition;
Determining a SiC concentration of the coating composition expected to provide the determined substrate adhesion characteristics; and providing a thermally radiative coating composition comprising the determined titanium dioxide concentration and the determined SiC concentration. Including. 40. The method of claim 38, wherein providing a thermal radiation coating composition comprising the determined titanium dioxide concentration comprises extracting titanium dioxide from an industrial waste stream or an ore-based titanium dioxide source. 40. The method of claim 39, wherein the industrial waste stream comprises a polyolefin polymerization process waste source. 41. The method of claim 40, wherein the polyolefin polymerization process waste source comprises a Ziegler-Natta catalyst containing waste source. Extracting titanium dioxide from the industrial waste stream,
42. The method of claim 41, comprising adjusting the pH of the industrial waste stream to between about 7.0 and about 9.0; and precipitating titanium dioxide from the pH adjusted industrial waste stream. 40. The method of claim 38, wherein determining the SiC concentration of the coating composition further comprises selecting a SiC concentration on a dry basis, such as from about 8% to less than 30% by weight. 44. The method of claim 43, wherein the SiC concentration on a dry basis is from about 8% to about 20% on a weight basis.