WO2001009055A1 - Elements constitutifs d'une composition a base de ciment: pre-traitement destine a en limiter le potentiel d'adsorption - Google Patents

Elements constitutifs d'une composition a base de ciment: pre-traitement destine a en limiter le potentiel d'adsorption Download PDF

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Publication number
WO2001009055A1
WO2001009055A1 PCT/US2000/021205 US0021205W WO0109055A1 WO 2001009055 A1 WO2001009055 A1 WO 2001009055A1 US 0021205 W US0021205 W US 0021205W WO 0109055 A1 WO0109055 A1 WO 0109055A1
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component
ash
adsoφtion
cementitious
fly ash
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PCT/US2000/021205
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English (en)
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WO2001009055A9 (fr
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Robert Douglas Young
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Robert Douglas Young
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Application filed by Robert Douglas Young filed Critical Robert Douglas Young
Priority to EP20000953819 priority Critical patent/EP1210301A1/fr
Priority to US09/830,238 priority patent/US6706111B1/en
Priority to AU66202/00A priority patent/AU776805B2/en
Priority to JP2001514261A priority patent/JP2003529514A/ja
Priority to NZ517540A priority patent/NZ517540A/en
Priority to CA 2380090 priority patent/CA2380090A1/fr
Publication of WO2001009055A1 publication Critical patent/WO2001009055A1/fr
Publication of WO2001009055A9 publication Critical patent/WO2001009055A9/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10—Coating or impregnating
    • C04B20/1018—Coating or impregnating with organic materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/06—Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
    • C04B18/08—Flue dust, i.e. fly ash
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/02—Treatment
    • C04B20/023—Chemical treatment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • Field of the Invention relates to a method of pretreating any component of a cementitious composition, particularly ash, that exhibits a high or highly varying adsorption characteristic, or both.
  • the treatment method transforms the chemical adso ⁇ tion characteristic of the component to a low constant value for use in processes that utilize the component.
  • An important aspect of the present invention is that the method shifts the process of controlling the adso ⁇ tion effects of the components from the end user to the component marketer.
  • the present invention relates to a method of treating a component or components of a cementitious composition that contains an appropriate surface mo ⁇ hology, such as that exhibited by unbumed carbon or zeolite materials in fly ash, or both, for which the component exhibits the ability to adsorb chemicals from an aqueous solution.
  • the approach of the method is to satiate the adso ⁇ tive potential associated with the surface mo ⁇ hology by adding effective, trace amounts of a treatment agent or agents to the component(s) prior to addition of the component to the composition slurry.
  • satiation of the adso ⁇ tion potential occurs only after the treated component is placed in an aqueous solution.
  • the addition to the aqueous solution (the composition slurry) enables mass transport of the intentionally added effective, trace amount of agent(s) to the adso ⁇ tion sites.
  • the air entrainment quality of a cementitious composition has been controlled by the end user of the composition. Because of high or high variable adso ⁇ tion characteristics, or both, the end user has the tedious task of adding the proper quantities of the various components of the cementitious composition. It is often by trial and error that a proper mix is achieved. There is a tremendous need for a way to control the consistency of the adso ⁇ tion characteristics of mix components at the component supplier. There are numerous components of cementitious compositions which have varying adso ⁇ tion potentials requiring control.
  • Ash is a byproduct of the combustion process.
  • the major producer of ash in the United States is coal fired power plants, which generate on the order of 1 x 10 8 tons of fly and bottom ash annually.
  • a significant portion of the ash is pozzolanic in nature, which means that in the presence of moisture the ash will react with calcium hydroxide at ordinary temperatures to form compounds possessing cementitious properties.
  • This pozzolanic nature of ash enables ash to be substituted for Portland cement in concrete in amounts up to 50%. While there are other uses for ash, the use of ash in concrete represents the single largest application that beneficially utilizes ash in a product. Unfortunately, however, the majority of ash that is generated at coal fired power plants is never utilized. Federal clean air standards imposed upon coal burning power plants caused the power plants to reduce the combustion temperature in the boilers in order to reduce NO x emissions. The reduced combustion temperature causes a substantial increase in the amount of unbumed carbon present in the ash.
  • the unbumed carbon in the ash exhibits some of the characteristics of a low-grade activated carbon, in particular, the ability to adsorb a wide range of chemicals.
  • ash with a high amount of unbumed carbon is referred to as an ash with a high loss on ignition (LOI) content.
  • LOI occurs when the ash is heated in the presence of air to temperatures that completely combust the unbumed carbon to gaseous CO 2 Ash with high LOI has traditionally been considered to be ash with high adso ⁇ tion potential.
  • the adso ⁇ tion potential of a high LOI ash is detrimental to the use of the ash as a Portland substitute in concrete due to the ash's tendency to adsorb important cementitious chemical admixtures from the concrete during the mixing process rendering the admixtures unavailable to effect their intended pu ⁇ ose.
  • Virtually all large scale commercial concrete applications require the use of cementitious admixtures for pu ⁇ oses such as entraining air for freeze-thaw protection, reducing water content for higher strength, and retarding or accelerating the initial set of the concrete.
  • LOI is not a good indicator of ash adso ⁇ tion potential.
  • the specific amount of unbumed carbon in the ash is a function of the specific combustion condition of the boiler when the coal is burned.
  • Changing demands for electrical power result in changing combustion conditions which in turn results in varying amounts of unbumed carbon in the ash.
  • the variability associated with the amount of unbumed carbon in the ash increases with increasing LOI.
  • different loads of ash that are delivered to the concrete manufacturer will differ in LOI content and the amount of difference increases as the average LOI content increases.
  • the changing combustion conditions influence the surface mo ⁇ hology of the unbumed carbon, which directly influences the specific adso ⁇ tion potential of the unbumed carbon. Therefore, two different ash samples with the same LOI can exhibit radically different adso ⁇ tion potentials.
  • some combustion conditions can produce a surface mo ⁇ hology on the mineral phase of the ash that is capable of adso ⁇ tion in a manner analogous to activated carbon.
  • This zeolitic type of adso ⁇ tion cannot be predicted based on the LOI of the ash.
  • the continuously varying adso ⁇ tion potential of the ash (and all of the components to the cementitious composition) means that the admixture dosage necessary to compensate for the adso ⁇ tion effect does not remain constant.
  • the concrete industry, as a whole, is a low technology industry with low profit margins, and as such employs a trial and error method of determining the necessary compensatory admixture dosage.
  • Their preferred embodiment includes placing the ash into an enclosed vessel followed by the introduction of the fluorine and/or chlorine gas for a time period from 10 to 60 minutes. After this time, the prepared ash is usable as a Portland substitute without appreciable admixture adso ⁇ tion by the unbumed carbon in the ash.
  • Fluorine and chlorine gas are highly corrosive and are potentially lethal in relatively small doses to living organisms.
  • the capital required to build a treatment facility from special corrosive resistant materials is high.
  • the cost of the gas is high relative to the selling price of the ash.
  • the approach of the present invention is to provide a treatment and method for treating the ash without the problems of the known art.
  • trace amounts of solid and/or liquid chemicals are added to the ash prior to the use of the ash in a subsequent process in order to mitigate the adso ⁇ tion potential of the ash.
  • Implementation of the approach of the present invention is well suited for either the ash generator or ash marketer because this approach results in greater product uniformity and eliminates the end user's concern over the adso ⁇ tion effect of the unbumed carbon in the ash.
  • the present invention does not satiate the unbumed carbon during the treatment process, but rather the process enables the correct amount of chemicals to be present in the ash so as to satiate the adso ⁇ tion effect when the ash is in an aqueous solution.
  • Chemicals found to be useful for this pu ⁇ ose are members of the family of chemicals that strongly adsorb onto carbon and/or zeolitic substrates.
  • highly effective chemicals have been identified that are not corrosive, not harmful to the environment, do not pose a health risk to personnel handling the ash, remain in the ash with changing environmental conditions, and are very inexpensive relative to the selling price of the ash.
  • An object of the present invention is to provide a novel treatment and method for treating any component or components of a cementitious composition that utilizes a treatment chemical or agent that is supplied to the component before the component is introduced into the utilizing process to control the apparent chemical adso ⁇ tion potential of the component. It is an object of the present invention to provide a novel treatment and method for treating any component(s) of a cementitious composition that lowers its adso ⁇ tion potential, particularly for chemicals added during the utilizing process.
  • Another object of the present invention is to provide a novel treatment and method for treating ash that introduces the treatment chemical or chemicals into commercially "bad” ash simply, easily, and of low capital cost such that the total treatment cost of the ash is a very small fraction of the commercial selling price of the treated ash.
  • Still another object of the present invention is to provide a novel treatment and method for treating ash that does not pose an increased threat to the environment, to the health or safety of workers, or to equipment exposed to the treated ash relative to the untreated ash.
  • Yet another object of the present invention is to provide a novel treatment and method for treating any component(s) of a cementitious composition that utilizes a treatment chemical or chemicals that remains in the component or final product with changing environmental conditions. It is another object of the present invention to provide a novel treatment and method for treating any component(s) of a cementitious composition that utilizes a treatment chemical or chemicals for the component that becomes effective when the component is placed in an aqueous solution. Still another object of the present invention is to provide a novel treatment and method for treating any component(s) of a cementitious composition that utilizes a treatment chemical or chemicals that is an anionic surfactant.
  • Another object of the present invention is to provide a novel treatment and method for treating ash that utilizes a treatment chemical or chemicals that is sodium lauryl sulfate.
  • applicant's present invention provides for a novel treatment and method for treating any component(s) of a cementitious composition that involves dispersing amounts (even trace amounts) of a treatment chemical or agents into the component before the component is used in a utilizing process.
  • the treatment chemical or chemicals work in combination with the utilizing process to produce the effect of controlling the apparent chemical adso ⁇ tion potential of the component in the utilizing process.
  • a treatment chemical or chemicals is selected.
  • a subfamily of chemicals that beneficially interact with both the intended component and the utilizing process are selected from a family of chemicals that strongly adsorb onto carbon and/or zeolitic substrates.
  • a subset of chemicals is next selected from the subfamily of chemicals which would not realistically increase the risk to the environment, workers' health or safety, or integrity of equipment that is exposed to the treated component relative to the risks imposed by untreated component.
  • a candidate set of chemicals is selected from the subset of chemicals for which the cost of treatment is significantly below the commercial selling price of the treated component.
  • the necessary or effective amount of the treatment chemical or chemicals is determined and the treatment chemical or chemicals is prepared for introduction into the component.
  • Fig. 1 is a chart of adso ⁇ tive indices for various ash types.
  • Fig. 2 is a chart of time resolved LOI for Carbo Power Plant ash.
  • Fig. 3 is a chart of LOI versus Adso ⁇ tive Index.
  • Fig. 4 is a flow chart of the analysis of components of the present invention.
  • Ash possessing a consistently low adso ⁇ tion potential is marketable as a pozzolan into products such as concrete.
  • highly adso ⁇ tive ash or ash with highly varying adso ⁇ tion potential, or both is usually not marketable because the use of the ash can cause problems with the control of process utilizing the ash.
  • ash with varying adso ⁇ tion potential is transformed into an ash with a low and consistent adso ⁇ tion potential relative to the utilizing process.
  • undesirable ash is transformed into a desirable and marketable product for both the ash generator and the ash disposal agent.
  • the present invention speaks preferably to a treatment and method of treating ash with high and/or highly varying adso ⁇ tion potential
  • the present invention is also applicable to other components of cementitious composition as was discussed above.
  • applicant has developed a treatment and method of treating a component that exhibits high and/or highly varying chemical adso ⁇ tion potential.
  • LOI is not used as a measure of adso ⁇ tive potential due to the low degree of correlation between LOI and the adso ⁇ tive potential.
  • the adso ⁇ tion potential of a sample component, for example, ash is however quantified by measuring the specific amount of Methylene Blue (C 16 H I8 C1N 3 S) that the ash adsorbs when placed in an aqueous solution.
  • the weight of Methylene Blue adsorbed by the ash divided by the weight of the ash is referred to as the material adso ⁇ tive index for the sample ash.
  • the material adso ⁇ tive index for the sample ash For example, one pound of Methylene Blue adsorbed by 1000 pounds of ash would equate to a material adso ⁇ tive index of 0.001.
  • a chart of adso ⁇ tive indices for various ash types is illustrated in Fig. 1.
  • a chart of LOI variations as a function of adso ⁇ tive index is shown in Fig. 2. It should be understood that similar charts may be prepared for other components of cementitious compositions including sand, cement, stone, crushed stone, gravel, mortar, cement aggregates, clay, lime, limestone, and various siliceous and aluminum materials.
  • the component should be treated in accordance with the present invention.
  • Selection of the treatment chemical or chemicals for functionality is based upon the mo ⁇ hological aspects of the component and the compatibility with the targeted application.
  • the adso ⁇ tion of chemicals onto the surface of component is a complicated subject, which is further exacerbated by continual changes in the surface mo ⁇ hology of the component or components, and in the case of ash, induced in part by changing operational conditions at the ash generating plant. It is difficult to predict initially which chemical or chemicals will adsorb best on any given component. However, the preferred chemical or chemicals will possess all or most of the following characteristics.
  • a subfamily of chemicals that beneficially interact with both the intended component, components, or ash and the process of interest are selected from a family of chemicals that adsorb, preferably strongly, onto carbon and/or zeolitic surfaces. Due to the myriad of possible detrimental interactions, candidate treatment chemicals must be identified using an experimental approach. Next, a subset of chemicals is selected from the subfamily of chemicals which would not realistically increase the risk to the environment, workers' health and safety, or integrity of the equipment that is exposed to the treated ash relative to the risks imposed by untreated ash. A candidate set of chemicals is then selected from the subset of chemicals for which the cost of treatment is significantly below the commercial selling price of the treated ash.
  • One subfamily of chemicals shown to be useful in the embodiments is detergents including surfactants and emulsifiers.
  • Initial tests utilized anionic surfactants, more particularly sodium lauryl sulfate (SLS), as the treatment chemical, and favorable results were obtained.
  • SLS sodium lauryl sulfate
  • another surfactant for use was nonionic; namely, an ethoxylate, and more particularly, a nonylphenol ethoxylate surfactant (NP-9).
  • NP-9 nonylphenol ethoxylate
  • the nonylphenol ethoxylate has been shown to be highly effective at controlling the apparent adso ⁇ tion potential of Carbo ash, an ash used as a Portland replacement in concrete in the amount of 20% in a certain area of the United States.
  • FIG. 3 A chart of time resolved LOI for the Carbo Power Plant ash is illustrated in Fig. 3.
  • the treated ash does not adversely affect the other chemical admixtures that are added to the concrete by the manufacturers.
  • this treated ash does not pose an environmental, safety, or health risk relative to the untreated ash, and the treatment cost is on the order of a few percent of the selling price of the ash to the concrete manufacturer.
  • the weight of this treatment chemical or chemicals to be added to the ash must be determined. To determine this weight a scale factor is experimentally determined for the treatment chemical or chemicals. This scale factor is then multiplied by the material adso ⁇ tive index to determine the appropriate weight of treatment chemical or chemicals.
  • the scale factor for nonylphenol ethoxylate has been found by experimentation to be 0.57. Overall it is preferred that only a trace amount of treatment chemical or chemicals be added to the ash. This trace amount will be in the range of about 0.001% to about 2.0% solid to solid, and yet may be as broad as about 0.001% to about 20% solid to solid in some unusual cases.
  • the treatment chemical or chemicals must be prepared for introduction into the ash. Solid chemicals are ground or milled into fine particulate powders. Liquids can be atomized or formed into aerosols, or can be adsorbed into fine particulate ash, clay or other suitable carrier substrate material.
  • All chemicals that exist unaltered from their intended structure when heated to a vapor state can be vapor deposited onto fine particulate ash, clay or other suitable carrier substrate material.
  • the treatment chemical or chemicals After the treatment chemical or chemicals is prepared, there are two fundamental methods that can be used to disperse the treatment chemical or chemicals into the component. These include mixing and combined flows. Mixing involves the use of either a batch or continuous mixer and usually requires the use of two or more containers to buffer the flow of ash for loading the untreated ash into the mixer and unloading the treated ash. Examples of such containers include silos and transportation containers.
  • the form of the treatment chemical or chemicals used for mixing can be solid in the form of a fine particulate, a liquid, a liquid adsorbed onto a substrate such as clay or ash, or a chemical that is vapor deposited onto a suitable substrate such as clay or ash.
  • the degree of dispersion of the treatment chemical or chemicals into the ash is dependent upon the mixing time and the design of the mixer. Introduction of the treatment chemical or chemicals into the ash by the mixing method is well suited for treatment at the facilities of the ash generator, ash marketer, and end user of the ash.
  • combined flows is a preferred method which can be implemented at low cost, can treat ash faster, and can effectively disperse the treatment chemical or chemicals into the ash.
  • the combined flows method combines one or more ash flows with one or more treatment chemical flows utilizing either naturally or artificially induced turbulence as the means of dispersing the treatment chemical or chemicals into the ash. This method has high utility because flows of ash already exist to move the ash around the ash generation facility, ash terminal facility and end user facility.
  • Examples where the combined flows method is useful include, but are not limited to, the flow of flue gas which transports the ash from the boiler to either a precipitator or a storage silo, between storage silos, or between a silo and some form of transportation container.
  • a precipitator or a storage silo between storage silos, or between a silo and some form of transportation container.
  • solids in the form of a fine particulate, liquids adsorbed onto a fine particulate, or chemicals vapor deposited onto a fine particulate can be used, the combined flows method is particularly useful when atomized liquids or aerosols are used.
  • the presumed mechanism of the present invention is competitive adso ⁇ tion. In other words the addition of a trace amount of chemical to the component does not inherently alter the characteristic mo ⁇ hological surface adso ⁇ tion at the particulate level.
  • the component acts as a carrier to deliver the correct dosage of treatment chemical to the utilizing process.
  • the utilizing process enables the conditions for the treatment chemical or chemicals to compete for the adso ⁇ tion sites in the component, thus leaving the chemicals that are intentionally added to the utilizing process for their intended pu ⁇ ose.
  • the adso ⁇ tion coefficient of a component is quantifiable by measuring the specific amount of Methylene Blue adsorbed by the component when placed in an aqueous solution. Any other known techniques, such as BET, may be utilized to obtain such a coefficient.
  • Example 1 The present disclosure contemplates an additive or agent which is mixed in the fly ash (having unbumed carbon or activated charcoal) in a relatively small portion.
  • the unbumed carbon is so evenly distributed and widely dispersed that it is a practical impossibility to extract it. While it can be exposed to subsequent heat and the temperature raised so high that the unbumed carbon is combusted, that is a counter productive process because the heat impacts other aspects of the mixture.
  • fly ash is indeed a mixture, the better process is to assay the fly ash and determine the presence or absence of activated charcoal or unbumed carbon. If present in any amount, and especially above about 1%, then the activated charcoal needs to be treated in accordance with the procedure suggested by this disclosure. The fly ash thereby obtains a controlled adso ⁇ tion potential.
  • the test is carried out to determine how many drops of the agent are required. If more than 10 drops are required, then the fly ash is not suitable. It is not suitable because it will degrade air entrainment. So long as the VR entrainment agent requires fewer than 10 drops, then the fly ash is assayed as a usable and useful additive.
  • This test protocol described below as the foam index test, is essentially a well known standard to determine the acceptance or rejection of fly ash for use in cement based products. Sometimes, the fly ash is so laden with the activated carbon that it takes upwards of several hundred drops, even as many as 600 drops of the VR agent added to observe the change indicative of air bubble entrainment.
  • the fly ash can be successfully added in the slurry and the finished and cured concrete will not be susceptible to damage during cold weather.
  • the present disclosure contemplates an additive to the fly ash which negates the previously discussed air entrainment problem.
  • problem traces from the presence of the chemically active charcoal, i.e., elemental carbon distributed randomly throughout the fly ash.
  • the detergent is an anionic surfactant which enhances the separation of selected materials.
  • the detergent is sodium lauryl sulfate, identified below as SLS.
  • SLS is given by the formula of N a CH 3 (CH 2 ) ⁇ SO 4 .
  • This sulfate uses the four oxygen atoms to provide a negative charge countered by the reactive sodium.
  • the lauryl is defined as an alkane chain.
  • SLS added typically are about 0.1% to about 0.5% by weight.
  • Example 2 It was discovered that an ash treated with a surfactant, an ethoxylate, and more specifically a nonylphenol ethoxylate, by atomizing the surfactant into a flow of ash will exhibit a reduction in the amount of Methylene Blue that is adsorbed by the ash.
  • the adso ⁇ tive sites on the surface of the ash are not satiated by the surfactant at the time of treatment but by the process of placing the ash in aqueous solution.
  • the solution enables mass transport for the surfactant to reach the adso ⁇ tion sites on the ash. It should be understood that there are numerous analytical techniques for evaluating or determining an adso ⁇ tion coefficient or factor which correlates to the adso ⁇ tion potential of the cementitious composition.
  • the present invention may utilize any of these known (or even yet to be discovered) techniques, but the amount of treatment agent to be added to the given component is proportional to the amount of the component. It is also possible that the treatment chemical or chemicals will be the same chemicals that are intentionally added by the utilizing process, such as cementitious admixtures that may be added during concrete manufacturing. However, since the utility of the present invention relies on the pretreatment of the ash before the utilizing process, in most cases the treatment chemical or chemicals will differ from chemicals intentionally added during the utilizing process. As previously stated, the present invention can also be used to process one or more individual components of the cementitious mix. An air entrainment agent (AEA) or treatment agent is added to compensate for adsorbtivity mandated by that component.
  • EAEA air entrainment agent
  • a procedure is set forth by which a cementitious component particulate is measured. This step 10 involves the segregation of a measured sample. Because it is a sample, it should be taken in a representative proportion. More will be noted concerning that proportion below.
  • the particulate sample is taken for measurement from a flowing stream of the component.
  • the different components can be sampled; all of these comprising important constituent parts in the manufacture of cementitious compositions as previously discussed.
  • the size of the particles should be noted.
  • the gravel is graded to any particular size controlled or defined by a screen system. It can be a single size of gravel, or it can be a mix of two or three different sizes, or a range of sizes.
  • the sand can be screened and measured, and can comprise a uniform size, or it can be any size grains in a specified range.
  • both the sand and gravel are commonly obtained by strip mining in river beds and the like.
  • the sand and the gravel are screened to a specified standard for each component.
  • the cement may be ground to a selected mesh appropriate for the particular concrete pour specifications.
  • the fly ash which is added to the composition may be ground to a selected mesh for that pour specification.
  • the process step 10 shown in Fig. 4 involves the obtaining of a measured portion of the particulate material, i.e., specified sample size of a few grams of sufficient particulate material to fill a 200 or 500 ml sample holder.
  • the next step 12 shown in Fig. 4 involves the addition of a reagent.
  • a reagent There are numerous acid base reagents available.
  • the preferred reagent is Methylene Blue which is 3, 7 - Bis(dimethylamino)phenothiazin-5-ium chloride; C.I. Basic Blue 9; it is sometimes known as methylthionine chloride or tetramethylthionine chloride.
  • the reagent is mixed in a ratio of one gram of reagent to 10,000 g of water. That water solution of the reagent is placed in a container and the particulate is added to it. This procedure can progress along either of two routes, i.e., the liquid reagent is added to the particulate or the particulate is added to the liquid. In either instance, the granulated or particulate material is tested by adding the reagent to it, commingling the liquid with the particulate material. Still referring to Fig. 4, the reagent is separated from the particulate material at step 14, thereby recovering the reagent.
  • Step 16 is executed, which is the assay of the reagent.
  • Step 16 commonly is done with a first measurement of the reagent in the liquid prior to exposure to the particulate material.
  • the change in color is noted and is an indicator of the amount of chemical reaction that is implicated in this process. It is readily accomplished to measure the change in color before and after readings are taken. This indicates, in some measure, the amount of the color agent which has been tied up in the particulate material.
  • 1 Og of a subject fly ash is placed into a beaker containing 50g of 100 PPM (parts per million) aqueous Methylene Blue solution, with a magnetic stirring bar rotating at approximately 100-200 RPM (revolutions per minute), for a period of five minutes. After five minutes the stirring is stopped and the slurry is allowed to settle for five minutes. An aliquot of the supernatant is drawn through a 13mm diameter micro-filter with a 0.75 ⁇ m pore size borosilicate glass filtering medium affixed onto a syringe. A total of 10ml of the subject solution is collected. The filtered solution is placed into a glass vial and capped to prevent contamination.
  • the color of the subject solution can be compared visually with reference standard vials containing different known dye concentrations, such that the dye concentration of the subject material can be determined via the comparison. Standardized color charts can also be used. Alternatively, the dye concentration in the subject sample can be quantified through the use of a photospectrometer.
  • the adso ⁇ tive coefficient or index is calculated by dividing the weight of dye adsorbed from the total aqueous dye solution by the weight of the fly ash used. A typical fly ash adso ⁇ tive index is 0.0002g/g.
  • the remediation chemical that must be added to the fly ash is directly related to the adso ⁇ tive index. For example, let be the proportionality constant.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Civil Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

Cette invention concerne un procédé de pré-traitement destiné à un élément support d'une composition à base de ciment, en particulier de la cendre légère. On analyse une certaine quantité d'un quelconque composant d'une composition à base de ciment afin de limiter le potentiel d'adsorption dudit composant dans la composition. On traite ensuite cette quantité au moyen d'une dose efficace d'agent de traitement pour en limiter le potentiel d'adsorption. Selon un mode de réalisation particulier, on traite la cendre légère avec un détergent afin d'en limiter le potentiel d'adsorption et ultérieurement d'empêcher la consommation d'air par ladite cendre une fois celle-ci intégrée dans un matériau à base de ciment.
PCT/US2000/021205 1999-08-03 2000-08-03 Elements constitutifs d'une composition a base de ciment: pre-traitement destine a en limiter le potentiel d'adsorption WO2001009055A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP20000953819 EP1210301A1 (fr) 1999-08-03 2000-08-03 Elements constitutifs d'une composition a base de ciment: pre-traitement destine a en limiter le potentiel d'adsorption
US09/830,238 US6706111B1 (en) 1999-08-03 2000-08-03 Method for pretreating components of a cementitious composition to control adsorption potential
AU66202/00A AU776805B2 (en) 1999-08-03 2000-08-03 Method for pretreating components of a cementitious composition to control adsorption potential
JP2001514261A JP2003529514A (ja) 1999-08-03 2000-08-03 セメント組成物の成分に前処理を受けさせて吸着ポテンシャルを制御する方法
NZ517540A NZ517540A (en) 1999-08-03 2000-08-03 Method for pretreating carrier components of a cementitious composition to control adsorption potential
CA 2380090 CA2380090A1 (fr) 1999-08-03 2000-08-03 Elements constitutifs d'une composition a base de ciment: pre-traitement destine a en limiter le potentiel d'adsorption

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US14685499P 1999-08-03 1999-08-03
US60/146,854 1999-08-03
US16965799P 1999-12-08 1999-12-08
US60/169,657 1999-12-08

Related Child Applications (2)

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US09/830,238 A-371-Of-International US6706111B1 (en) 1999-08-03 2000-08-03 Method for pretreating components of a cementitious composition to control adsorption potential
US10/800,980 Division US20040200389A1 (en) 2001-04-24 2004-03-15 Method for pretreating components of a cementitious composition to control adsorption potential

Publications (2)

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WO2001009055A1 true WO2001009055A1 (fr) 2001-02-08
WO2001009055A9 WO2001009055A9 (fr) 2002-09-12

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EP (1) EP1210301A1 (fr)
JP (1) JP2003529514A (fr)
AU (1) AU776805B2 (fr)
CA (1) CA2380090A1 (fr)
NZ (1) NZ517540A (fr)
PL (1) PL364518A1 (fr)
WO (1) WO2001009055A1 (fr)

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WO2004067198A1 (fr) * 2003-01-24 2004-08-12 Boral Material Technologies Inc. Systeme et procede pour traiter des cendres volantes
EP1973859A2 (fr) * 2006-01-20 2008-10-01 Cognis IP Management GmbH Composes et procedes de traitement des cendres volantes
US7892349B2 (en) 2003-01-24 2011-02-22 Boral Material Technologies Inc. Sacrificial agents for fly ash concrete
US8652249B2 (en) 2009-05-06 2014-02-18 Ruetgers Polymer Ltd. Amine sacrificial agents and methods and products using same

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Publication number Priority date Publication date Assignee Title
US8629079B2 (en) 2011-04-14 2014-01-14 Basf Se Process for producing a catalyst for the oxidation of ethylene to ethylene oxide

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JPH08337449A (ja) * 1995-06-09 1996-12-24 Chugoku Electric Power Co Inc:The 石炭灰の高品質化方法及び装置

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JPH08337449A (ja) * 1995-06-09 1996-12-24 Chugoku Electric Power Co Inc:The 石炭灰の高品質化方法及び装置

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004067198A1 (fr) * 2003-01-24 2004-08-12 Boral Material Technologies Inc. Systeme et procede pour traiter des cendres volantes
US7892349B2 (en) 2003-01-24 2011-02-22 Boral Material Technologies Inc. Sacrificial agents for fly ash concrete
US7892350B2 (en) 2003-01-24 2011-02-22 Boral Material Technologies Inc. Sacrificial agents for fly ash concrete
US7901505B2 (en) 2003-01-24 2011-03-08 Boral Material Technologies Inc. Sacrificial agents for fly ash concrete
EP1973859A2 (fr) * 2006-01-20 2008-10-01 Cognis IP Management GmbH Composes et procedes de traitement des cendres volantes
EP1973859A4 (fr) * 2006-01-20 2014-09-03 Cognis Ip Man Gmbh Composes et procedes de traitement des cendres volantes
US8652249B2 (en) 2009-05-06 2014-02-18 Ruetgers Polymer Ltd. Amine sacrificial agents and methods and products using same

Also Published As

Publication number Publication date
CA2380090A1 (fr) 2001-02-08
AU776805B2 (en) 2004-09-23
EP1210301A1 (fr) 2002-06-05
PL364518A1 (en) 2004-12-13
NZ517540A (en) 2004-03-26
JP2003529514A (ja) 2003-10-07
WO2001009055A9 (fr) 2002-09-12
AU6620200A (en) 2001-02-19

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