JPH058133B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF THE INVENTION The present invention relates to a method for producing a curable cement composition suitable for filling cavities, for example, in underground mines, a dry mixture from which the cement composition can be produced, and a new method comprising a main component of the cement composition. The invention relates to mineral clinker compositions. BACKGROUND OF THE INVENTION One known method for filling cavities in underground mines involves the use of a first aqueous slurry containing cement and a second aqueous slurry containing an inorganic salt to promote hardening and solidification of the cement. The slurry is pumped to the location of the cavity where they are mixed together to form a filler composition that can cure within the cavity to form a solidified body. This method is called “pressure filling”.
Various materials have been developed for use in this field. The second aqueous slurry typically contains calcium sulfate (particularly natural or synthetic anhydrite) and lime (calcium oxide and/or hydroxide), and also commonly includes clays such as bentonite. In underground mines, high alumina cement is advantageous because it is less skin invasive and easier to handle than regular Portland cement. For this reason, high alumina cements are commonly used in pressure-filling methods. However, high alumina cement has the disadvantage of a very short curing time. That is, high alumina cements as defined in British Standard (BS) 915, Part 2 are required to exhibit an initial set time of 2 to 6 hours and a final set time of no more than 2 hours after initial set. This can create serious problems in underground mining operations where strict control and monitoring of the mixing and pumping process becomes difficult. The relatively short setting time requires that the equipment for pumping and mixing the cement slurry be flushed clean after the full cavity filling operation to prevent the equipment from becoming clogged with hardening material. This may require part or even the entire mixing and pumping system to be renewed or mechanically cleaned, a waste of time especially when production is interrupted at the mine. And it becomes an expensive job. It is clear that there is a need in the industry for a method of producing satisfactory cement compositions based on materials that have the advantages associated with high alumina cements, but that avoid or reduce the problems associated with short initial set times. . _The mineral _{phase 4CaO.3Al2O3.SO3} is known as Klein compound _{, 3CaO.3Al2O3.CaSO4 or}
Also expressed as C ₄ A _s-3 s. Certain clinkers containing Klein compounds, their manufacture and use also as swelling agents in portland cement compositions are known (U.S. Pat. Nos. 3,155,526 (Klein), 3,251,701 (Klein), No. 3857714 (Mehta) and No. 4419136 (Rice)). For example, US Pat. No. 4,419,136 discloses an expansive clinker containing Portland cement clinker, gypsum and C ₄ A ₃ . These clinkers are ground separately before being mixed with gypsum. Expansive clinker (it has a high content, i.e. 21~
When containing 40% free lime) U.S. Patent No.
No. 3155526 or (Portland Cement Phase,
(especially when containing 3CaO.SiO ₂ and/or 2CaO.SiO ₂ ) may be produced according to the disclosure of US Pat. No. 3,251,701. UK Patent No. 2040278 (LaFarge Foundu
International) discloses a high mechanical strength refractory cement, which contains 10-30 parts _C4A3 clinker and 70-90 parts _alumina clinker, the latter being
Contains 30-75% _{CaO.Al2O3 . C4A3} clinker has a chemical composition: 35-37% by weight CaO, 48-54% by _{weight Al2O3} , 9-14% by weight _{SO3 ,} 0-4% by weight
_Fe2O3 and _0-4 wt% _SiO2 . None of these prior art documents disclose the mineral clinker composition according to the present invention or mention the above-mentioned problems associated with conventional pump filling methods. [Summary of the Invention] The present invention provides novel compositions containing from 25 to 68% by weight of
4CaO・3Al ₂ O ₃・SO ₃ and substantially 2CaO・Al ₂ O ₃・
Contains SiO ₂ present as SiO ₂ phase, optionally
The remainder of the composition is less than 1.0% by weight of free lime, less than 25% by weight of CaO.2Al ₂ O ₃ , less than 10% by weight of
12CaO・7Al ₂ O ₃ , less than 5% by weight of CaO・TiO ₂ ,
Less than 10% by weight of ferrite phase, up to 60% by weight
A mineral clinker composition is provided which is characterized in that it essentially contains at least one component selected from the group consisting of CaO.Al ₂ O ₃ and up to 4.1% by weight of CaSO ₄ . The mineral clinker compositions of the present invention can exhibit long and controlled setting times when ground and mixed with water. The present invention also provides a method of mixing a ground mineral clinker composition in water with an alkali metal or alkaline earth metal source under alkaline conditions in producing an effect cement composition. The present invention also provides a curable cement composition produced by the method described above, a solidified product formed by curing the cement composition, and a dry mixture that can be produced by mixing the cement composition with water. The mineral clinker composition of the present invention comprises a CaO source;
First, a cranker can be produced by heating a mixture of an Al ₂ O ₃ source, an SO ₃ source, and a SiO ₂ source in appropriate proportions to at least an initial melting temperature under oxidizing conditions for iron. The produced clinker may be cooled and ground, ie, granulated, by any suitable means. DESCRIPTION OF A MORE PREFERRED EMBODIMENT The mineral clinker compositions to be used in the process of the invention can be described as "sulfoaluminous", they contain at least 25% by weight, preferably at least 35% by weight, especially It usually contains at least 45% by weight of C ₄ A ₃ . However, in principle, by using extremely pure raw materials in the electric reverberatory furnace, production costs are relatively high, but approximately 100%
It becomes possible to obtain mineral clinker with % C ₄ A ₃ . Up to 55% by weight of mineral composition
C ₄ A ₃ S content, typically about 50% by weight C ₄ A ₃ min is suitable for many applications, but up to 65 wt % or even 68 wt % C ₄ A ₃ min or In applications where _C4A3 content is up to ₈₅ % by weight, it is also applicable. The weight percent values are determined from chemical analysis by calculation of the electrophase composition and checked by X-ray diffraction. It has been determined that the presence of significant amounts of free lime (CaO) is undesirable as it leads to premature hardening of cement compositions containing mineral compositions. Therefore, the free lime content is less than 0.5% by weight of the mineral composition, in particular 0.2%.
Preferably less than % by weight, and ideally free lime should be substantially removed from the mineral composition. It has been found that the presence of significant amounts of CaO.2Al ₂ O ₃ (abbreviated as CA ₂ ) can significantly impair the setting time and strength development of cement compositions prepared from mineral compositions. In particular, the CA ₂ min should be less than 10%, preferably less than 5%, especially less than 3% by weight of the mineral composition. Ideally, CA ₂ is virtually absent. However, if a slower development of strength and longer curing times are acceptable or higher levels of mineral composition are used in the slurry, relatively high levels, such as 20 wt _. I can accept it. Since the mineral phase of 12CaO 7Al ₂ O ₃ (abbreviated as C ₁₂ A ₇ ) reacts slowly with water to form lime, C ₁₂ A ₇ min in the mineral composition is Low amounts, preferably less than 5% by weight, are suitable. However, particularly with respect to strength development of cementitious compositions, C ₁₂ A ₇ may be present in mineral compositions in small amounts, preferably at least 0.5% by weight, typically 4% by weight.
It has been found that it is beneficial to maintain up to 3% by weight in particular. Nevertheless, it is also possible to use mineral compositions substantially free of C ₁₂ A ₇ . In order to obtain a high C ₄ A ₃ content in a mineral composition, it is necessary to limit the amounts of various other phases therein. In other words, the content of calcium titanate (CaO・TiO ₂ , abbreviated as CT) is 5
Preferably it is present in less than % by weight, especially less than 1% by weight, ideally substantially absent. Iron oxide (Fe ₂ O ₃ , abbreviated as F) is present in the composition as 4CaO.
Removal of lime and alumina from the composition limits the amount of Klein compounds since they form a ferrite phase close to Al _{2 O} 3 .Fe ₂ O ₃ (abbreviated as C ₄ AF). Considering the dilution effect that adversely affects the strength development of the curable cement composition, the content of the ferrite phase is less than 10% by weight, preferably 5% by weight.
Ideally, it should be virtually non-existent. Since silica (SiO ₂ , abbreviated as S) is present as a C ₂ AS phase in mineral compositions, it combines with Al ₂ O ₃ which can contribute to the formation of Klein compounds.
It is therefore preferred that the SiO ₂ content in the mineral composition is less than 10% by weight, preferably less than 5% by weight and especially less than 3% by weight. Surprisingly, as far as maximizing _{the C4A3} content is concerned, considerable amounts, e.g. up to 20% by weight, of CaO.
Al ₂ O ₃ (abbreviated as CA), or the presence of up to 60% by weight, e.g. up to 45% by weight of CA together with the retarder is tolerated without significantly modifying the low reactivity of the mineral composition with water. can do. The mineral composition should not contain more SO ₃ than is necessary to form C ₄ A ₃ . That is, calcium sulfate (CaSO ₄ or C) is preferably substantially absent from the mineral composition. However, an excess of CaSO ₄ may be desirable as it aids melt formation in melt processes for the production of mineral clinker when a corresponding dilution of the physical properties of the product is acceptable. The preferred mineral composition according to the invention is characterized by a maximum SO ₃ min of 8.5% by weight. The mineral composition according to the invention can be prepared in any suitable furnace for the raw material, such as a Portland cement clinker rotary kiln or a reverberatory furnace, for at least 1200 min.
It can be produced by sintering or melting, usually at temperatures of .degree. In general, raw materials are selected and matched to produce the highest economic level of Klein compounds. This usually requires the use of raw materials with relatively high purity. A suitable CaO source is limestone. A suitable SO ₃ source is calcium sulfate, such as gypsum hemihydrate or anhydride. Moreover, it is also possible to introduce sulfur from other sources, for example by firing the furnace with a fuel having a high sulfur content. Appropriate
The Al ₂ O ₃ source is bauxite, but it is also possible to use aluminum metal, such as aluminum scrap, which has combustion energy that contributes to the combustion of the clinker material. It may be necessary to adjust the fineness of the raw material to ensure that the free lime content of the final clinker is as low as possible. For example, when using the rotary kiln sintering method, 90%
A fineness equivalent to passing through a 90 micron sieve is usually suitable, and coarser materials are acceptable when using the melt process. Careful control of the mineral composition within the above-mentioned parameters is important to obtain maximum benefits. Such control as well as selection and coordination of raw materials is well within the capabilities of the cement manufacturer. the amount of C ₄ A 3 that the type of process used, e.g. sintering in a Portland cement clinker rotary kiln (unless specially adapted, practical limits are generally set by the amount of liquid that may be present during _combustion ); If you want to limit any excess calcium aluminate in the clinker, add calcium dialuminate CA ₂
Rather, it should be present as monocalcium aluminate CA. To avoid the formation of CA ₂ in the clinker, the composition should be balanced towards the lime-rich region of C ₁₂ A ₇ , preferably 5
Up to % by weight of C ₁₂ A ₇ is present. It is necessary to ensure that the combustion environment remains oxidizing to the iron. The reason is that while the reduction of Fe() gives Fe() which acts as CaO replacement, _C4AF no longer occurs and _C12A7 becomes over-content, leaving _an undesirable amount of free lime. This is because they may form. The presence of FeO in the aluminate phase of clinker can impair the strength development of cement compositions. Under unfavorable conditions in the furnace, calcium sulfate decomposes into sulfur trioxide and calcium oxide, leaving undesirable free lime inclusions in the final clinker and possibly producing high levels of _{C12A7 .} It is noteworthy that this occurs. However, from calcium sulfate
Oxygen levels within the furnace or kiln can be adjusted to adjust (preferably minimize) the rate of volatilization of SO ₃ and thus utilize this as a fine control to prevent or limit the formation of CA ₂ I can do it. Also, the formation of free lime can be minimized by avoiding excess calcium sulfate in the raw mixture. When coal is used as a fuel, ash should be considered as one of the raw materials to ensure that the proper balance of components in the composition is maintained. Appropriate raw materials are sintered in a rotary kiln for 50
%4CaO・3Al ₂ O ₃・SO ₃ and 15% CaO・
Al ₂ O ₃ , 20% 2CaO・Al ₂ O ₃・SiO ₂ , and a small amount of
CaO・2Al ₂ O ₃ or 12CaO・7Al ₂ O ₃ and CaO・
Typical sulfoalumina compositions can be produced by producing clinker having a ferrite phase with a composition similar to TiO ₂ and 4CaO.Al ₂ O _{3.Fe 2} O ₃ . At least some of the CaO.Al ₂ O ₃ phase can be replaced by 4CaO.3Al ₂ O _{3.SO 3} and vice versa. In particular, the composition comprises at least 25% by weight, especially 45% by weight.
Contains 4CaO・3Al ₂ O ₃・SO ₃ . It may be advantageous to incorporate a fluorine source, such as calcium fluoride ( _CaF2 ), into the combination to allow combustion to proceed at relatively low temperatures. Furthermore, by modifying the main clinker phase, fluorine reduces its reactivity and can therefore contribute to the retardation of the reaction between the mineral composition and water. That is, increasing the level of fluorine in a mineral composition tends to increase the time that a slurry containing the composition is ready for pumping. For example, when a pumpable time of 1 to 4 days is desired, such as in coal mining applications, the fluorine level retained in the mineral clinker is typically 0.15 to 0.25% by weight, but up to 1% by weight or more. It does not exclude high levels of fluorine. Mineral clinker can be quickly cooled by water cooling or in a conventional Portland cement clinker cooler. However, it is also possible to slowly cool the clinker from the melt. The cooled clinker can then be ground to a level of fineness suitable for the intended application. The mineral compositions to be used in the present invention are not significantly hydraulic (ie harden very slowly on reaction with water). Therefore, in order to produce cement compositions from mineral compositions, the latter compositions require activation. This is the process by which crushed clinker is mixed with alkali metals (e.g. Li, Na, etc.) in an aqueous medium.
or K) or alkaline earth (e.g. Ca)
This can be achieved by mixing with the source in alkaline conditions. The alkali or alkaline earth metal (or rather its cation) can be supplied, for example, in the form of the corresponding hydroxide, sulphate, chloride, carbonate or aluminate. In certain preferred embodiments, the ground mineral clinker is hydrated by mixing the aqueous slurry with an aqueous slurry containing a source of calcium ions, such as a mixture of calcium sulfate and lime (calcium oxide and/or hydroxide). hardened. Although lime can be supplied neat (i.e. in the form of slaked lime or hydrated lime), it is possible to use ordinary Portland cement as a source of lime in environments where strength rather than long pumpability is desired. . Ordinary Portland cement usually contains calcium sulfate and can therefore be used as a source in suitable applications of the present invention. That is, for example, the mineral composition is mixed with the activating composition in any suitable ratio (usually 1:99 to 99:9 by weight).
1), in which the activation composition comprises (a) 5-90%, preferably 40-85% calcium sulfate, (b) 5-60%, preferably 10-25% lime. (c) _up to 10%, preferably from 1 to 10%, especially from 2 to 5%, of one or more additional inorganic salts; (d) up to 25%, preferably from 0.5 to 5%; (d) up to 25%, preferably from 0.5 to 5%; 25%, especially 5-15% clay such as bentonite and (e)2
%, preferably up to 0.5% of retardant, these amounts being % of components (a) to (e) on a dry weight basis.
It is for the sum of . Sulfoaluminous compositions are particularly useful for filling cavities in underground mines by pump filling. The inherently very low hydration reactivity of C ₄ A ₃ , in contrast to high alumina cement slurries, allows the slurry of sulfoaluminous compositions (first slurry) to remain in the mixing pumping equipment for extended periods of time. . i.e. Minimum 24 as per BS915 for high alumina cement
While the hourly strength is 40 MN m ^-2 , the 24-hour strength of the typical crushed mineral clinker according to the present invention is approximately
It is 0.5MNm ^-2 . Generally, sulfoaluminous compositions of this type have not been permitted per se for building or construction work as cements. Therefore,
The present invention makes it unnecessary to remove the first slurry from the mixing pumping system after each implantation operation, and the slurry can normally remain in such a system during field transfer without fear of clogging due to hardening. . This not only saves time and materials, but also improves site conditions due to less waste material and less washing water. As mentioned above, the mineral compositions of the present invention may contain various phases, such as C ₁₂ A ₇ and CA, which are known to react with water. Surprisingly, however, it appears that the presence of these phases in amounts not exceeding the above-mentioned upper limits does not adversely affect the hardening of the mineral composition in the aqueous slurry. 20
The tendency to set within a period of time can be easily overcome by incorporating relatively inexpensive retarders, especially citric acid, into the slurry. It is surprising that the inherently slow setting properties of mineral compositions are exhibited even in the substantial absence of a calcium sulfate phase (calcium sulfate is well known in cement technology as a set retarder). For filling cavities by pressure-filling, the sulfoalumina clinker should be ground to a fineness such that no sedimentation of the particles formed when the aqueous suspension is maintained for long periods of time occurs. Preferably the particle size distribution is such that at least 95% by weight of the material, especially at least 98% by weight, has a particle size of less than 45 microns. To achieve this, grinding aids,
For example, it may be necessary to use propylene glycol or triethanolamine. It is also possible to use suspending agents such as cellulose ethers, which can be added to the clinker before, during or after grinding, or added to the metering water. (Although the use of suspending agents can prevent rapid settling of relatively coarse ground clinker particles, the use of such coarse materials is undesirable because it tends to inhibit crystal growth during the hydration-sedimentation reaction.)
The pumpability of the first slurry can be improved by adding small amounts of citric acid, for example to the clinker or ground clinker entering the clinker grinding mill or to the metering water. The aqueous slurry (second slurry) that is mixed with the first slurry to form the cement composition in a pump-filling process is composed of calcium sulfate, clay (e.g. bentonite) and hydrated lime with a small amount of alkali metal sulfate (e.g. K ₂ SO ₄ ) and a curing and/or solidification accelerator. The calcium sulfate can be supplied, for example, as gypsum hemihydrate, natural anhydrite, synthetic anhydrite or mixtures thereof; it is particularly preferred that the calcium sulfate is at least 50% by weight anhydrite. In particular, the calcium sulfate is ground to a particle size of less than 250 microns. The reason for this is that it has been determined that coarse particles may delay the strength development of cement compositions. However, it has also been determined that excess particles having a particle size of less than 2 microns may retard curing. Bentonite has been found to be effective in helping to maintain solids in suspension in the second slurry and curable composition. Suitable promoters are salts of alkali metals, especially lithium, such as carbonates. It has been determined that the presence of an alkali metal sulfate promotes the formation of ettringite, which is desirable to be present in the curable composition. It can be noted that any CA phase in the mineral composition tends to react with calcium sulfate and hydrated lime from the second slurry to form ettringite or other calcium sulfoaluminate hydrates. By way of example, the method of the invention will be explained with reference to the accompanying drawings, in which: FIG. The sulfoaluminous composition and water are mixed into a slurry in mixer/pump means 1 and pumped along a first pipe 2 towards an outlet 3 adjacent a cavity location 4 of the underground mine. This cavity location may be surrounded by a dam or may be a large bag located at an appropriate location. Other materials including calcium sulfate, lime, bentonite and water are mixed into the second slurry by another mixer/pump means 5 and the first by a Y-adapter 7 located near the cavity location.
The liquid is fed under pressure along a second pipe 6 connected to the pipe 2. In use, when the two mixer/pump means 1, 5 are operated simultaneously, the two slurries enter the cavity adjacent to the outlet 3 in atomized mixing. The resulting mixture hydrates and hardens to a solid that completely or partially fills the cavity, and this solid usually contains ettrin guide or other calcium sulfoaluminate hydrate. If strength is not of primary importance, the cavity can be filled with the curable composition as a foam using conventional blowing agents to produce a reduced density, low cost filling composition. The mineral compositions of the present invention can be used for many other applications and may therefore be ground to a suitable fineness (fine or coarser than the levels specified above for filling cavities in underground mines). be. The mineral composition of the invention may be combined with auxiliary materials such as Portland cement clinker, gypsum, anhydrite, high alumina cement clinker, granulated blast furnace slag (e.g. with slag in an amount of up to 60% by weight of total dry solids), pulverized fuel ash (e.g. 50% by weight of total dry solids)
ash) or with other potentially hydraulic or volcanic ash substances, pigments, hydrated lime, bentonite, mortan or any inert substances conventionally included in concrete or any mixture thereof; Otherwise, they can also be mixed. If the auxiliary material contains available alumina, the alumina may also enrich the ettrin guide or other calcium sulfoaluminate hydrates formed during hydration. In some cases, it may be appropriate to combine the mineral clinker with one or more of the above materials, either as a coarse material, as a finely ground material, or as a mixture of coarse and fine materials, to match the desired physical properties. There is. The poor initial reactivity (imparting good flowability) and subsequent rapid strength development exhibited by the mineral composition makes it suitable for use in specialty grouts such as tile adhesives and self-leveling bed mortars. Become. The mineral compositions, especially in mixtures with bendonite, can also be used as a basis for casting plasters, in particular for the production of high-quality molds with fine details. In addition to its function as a suspending agent during the preparation of the initial slurry, bentonite also contributes to the production of plasters with a relatively low density, which is advantageous, for example, for the production of decorative molds for ceilings. The low density of the mineral composition/bentonite mixture makes it suitable as a lightweight insulating plaster or bone material. Water may be added to the total composition of the curable composition depending on the application.
It can be present in amounts of ~99% by weight, especially 15-90% by weight. For pressure filling, the amount of water is
55-75% by weight is preferred, whereas for other purposes such as building materials and mining grouts the amount of water can be 25-40% by weight. Apart from pump filling and similar treatments, curable compositions can be prepared by directly mixing the solid components with water. That is, in commercial practice, the ground mineral composition and other solid ingredients can be supplied to the end user as a dry mixture, so that the end user is only required to mix it with water. It is. Of course, the end user is not precluded from adding additional ingredients as appropriate for his or her particular application. For pump filling and similar operations, the solid components can be supplied, for example, in half packs. That is, one pack contains a dry ground mineral composition and optionally other ingredients such as suspending aids and set retarders for mixing with or addition to water to produce a first slurry. and the second pack contains a drying component which, when mixed with or added to water, provides a slurry containing the alkali metal or alkaline earth metal source in an alkaline state. Typically, the second pack of the two-part pack contains calcium sulfate, clay, alkali metal sulfate, and a curing and/or curing accelerator. Next, the invention will be explained with reference to examples. Example 1 A raw material mixture consisting of 43.48 parts by weight of bauxite, 31.96 parts by weight of limestone, 24.57 parts by weight of anhydrite, and 1.22 parts by weight of charcoal debris was produced. The analysis of the three main components is shown in Table 1 below (values are weight%).
and LOI is loss on ignition).

[Table] This raw material mixture was heated to 1450℃ in a heavy oil-fired reverberatory furnace.
It was fired in The chemical analysis and calculated composition of the produced clinker are shown in Tables 3 and 4 below, respectively. Example 2 A raw material mixture consisting of 57.7 parts by weight of bauxite, 55.1 parts by weight of limestone, 22.2 parts by weight of anhydrite, and 1.8 parts by weight of charcoal was produced. The analytical values for limestone and anhydrite are shown in Table 1 above, and the chemical analysis (% by weight) for bauxite is shown in Table 2 below. Table 2 Bauxite SiO ₂ 6.5 Al ₂ O ₃ 86.0 Fe ₂ O ₃ 0.9 Mn ₂ O ₃ Less than 0.01 P ₂ O ₅ 0.15 TiO ₂ 4.0 CaO 0.3 MgO 0.3 SO ₃ 0.07 K ₂ O 0.95 Na ₂ O 0.07 LOI 0.3 This raw material The mixture was slurried in water, fed to a coal-fired rotary kiln, and sintered at 1450°C.
(The charcoal debris shown in the composition of the raw material mixture indicates the ash content mixed into the material during sintering.
The opposite is true. ) The chemical analysis and calculated composition of the produced clinker are shown in Tables 3 and 4, respectively.

【table】

[Table] Example 3 Four types of raw material mixture samples were produced. Each sample is
It contained 43.48% by weight of bauxite, 31.96% by weight of limestone and 24.57% by weight of anhydrite, and the chemical analysis values of these components were as listed in Table 1 above. No charcoal was included in these particular samples. The roughness of these samples was varied. That is, +
90 micron residue is 0.1% by weight in sample No. 1;
The content was 4.0% by weight in No. 2, 9.3% by weight in Sample No. 3, and 20.5% by weight in Sample No. 4. Each sample was heated to 1450°C in a pilot-scale heavy oil oven.
It was fired in The phase composition of each produced clinker was determined and the results shown in Table 5 below were obtained.

[Table] Each mineral clinker sample was ground to 450 m ² /g.
One part by weight of ground clinker was mixed with 2.5 parts by weight of water for 30 seconds using a high shear stirrer to produce an aqueous slurry. The pumpable time (ie, the time during which the slurry was in a pumpable state) was determined by measuring the shear resistance of the slurry. This measurement was also carried out on a slurry to which 0.2% by weight of citric acid was added. The results obtained are shown in Table 6 below.

[Table] A mixture consisting of 70.1 parts by weight of anhydrite, 18 parts by weight of hydrated lime, 5 parts by weight of bentonite, 0.5 parts by weight of sodium carbonate, and 0.4 parts by weight of lithium carbonate was produced. One part by weight of the mixture was mixed with 2.5 parts by weight of water for 30 seconds using a shear stirrer. The resulting slurry was mixed with a slurry containing ground mineral clinker, and the setting time and strength development of the resulting cement composition was measured. The measurement results are shown in Table 7 below.

TABLE Examples 4-16 These examples describe cement compositions containing ground mineral clinker produced by the process described in Example 2. The solid components described below were mixed with water in the amounts (expressed in parts by weight) described below, and the curing time of the resulting composition was determined. After curing such compositions under atmospheric conditions for a specified period of time, the compressive strength of the cured compositions was determined. Example 4 Composition: Sand 50 parts by weight Mineral clinker 25 Hydrated lime 15 Anhydrite 10 Citric acid 1 Water 22.5 Initial hardening: Approximately 6 minutes Compressive strength (sealed bag): 3 hours 7.7N/mm ² 6 hours 6.7 1 day 16.9 3 days 19.7 11 days 26.3 28 days 29.7 The above compositions were useful as rapidly curing, early strength grouts, for example as tile adhesives. Example 5 Composition: Sand 50 parts by weight Mineral clinker 25 Hydrated lime 15 Anhydrite 10 Citric acid 1 Melment F10 1 Water 20 Initial hardening: Approximately 10 minutes Compressive strength (sealed bag): 3 hours 14.4N/mm ² 6 hours 22.7 1 day 38.6 3 days 41.3 8 days 48.1 28 days 60.4 Melment F10 is a superplasticizer based on melamine-formaldehyde polymers (manufactured by Süddeutsche Karlstikstwerke AG)
It is. This superplasticizer can reduce water requirements, thereby imparting high strength cement compositions. This composition is useful as a filling material for roads and airport runways and shrinkage compensators. Example 6 Composition: Sand 50 parts by weight Mineral clinker 15 Anhydrite 6 Ordinary Portland cement 29 Citric acid 1 Water 22.5 Initial setting: Approximately 30 minutes Compressive strength: 6 hours 16.9 N/mm ² This composition is a good quality grout. It is suitable as Example 7 Composition: Sand 50 parts by weight Mineral clinker 15 Anhydrite 6 Ordinary Portland cement 29 Citric acid 0.25 Water 20 Initial hardening: Approx. 20 minutes Compressive strength (sealed bag): 3 hours 4.5N/mm ^2Example 8 This composition The material was the same as described in Example 7 except that the water was reduced to 18 parts by weight. Initial curing takes approximately 17 minutes, and the compressive strength (sealed bag) after 1 day is
It was 27.0N/ ^mm2 . Example 9 This composition was the same as described in Example 7 except that the water was reduced to 16 parts by weight. Initial cure: approximately 12 minutes Compressive strength (sealed bag): 3 hours 7.7 N/mm ² 7 days 32.8 28 days 29.9 Example 10 This composition was as described in Example 7 except that the water was reduced to 14 parts by weight. It was the same. Initial curing takes about 5 minutes, and compressive strength (sealed bag) after 3 hours is
It was 7.4N/ ^mm2 . Example 11 This composition was the same as described in Example 9 except that the amount of citric acid was 0.125 parts by weight.
Initial curing took about 5 minutes, and the compressive strength (sealed bag) after 3 hours was 5.1 N/mm ² . Example 12 Composition: Sand 50 parts by weight Mineral clinker 25 Hydrated lime 15 Anhydrite 10 Crushed fuel ash 25 Citric acid 1 Water 35 Initial hardening: Approximately 15 minutes Compressive strength (sealed bag): 3 hours 5.0N/mm ² 6 hours 8.7 1 day 20.5 4 days 24.5 9 days 22.5 The physical properties of this composition are suitable for producing bed mortars. Example 13 Composition: Sand 50 parts by weight Mineral clinker 29 Hydrated lime 15 Anhydrite 6 Citric acid 1 Water 26 Initial hardening: Approximately 5 minutes Compressive strength: 1 day 14.1 N/mm ² Example 14 Composition: Sand 50 parts by weight Mineral Clinker 18 Ordinary Portland cement 28 Anhydrite 3.5 Citric acid 0.5 Water 17.86 Initial hardening: Approximately 40 minutes Compressive strength (sealed bag): 3 hours 3.4N/mm ² Examples 15 Composition: Sand 70 parts by weight Mineral clinker 25 Ordinary Portland cement 40 Anhydrite 5 Citric acid 0.5 Water 30 Initial hardening: Approximately 20 minutes Compressive strength (sealed bag): 3 hours 3.3N/mm ² Examples 16 Composition: Sand 50 parts by weight Mineral clinker 25 Hydrated lime 15 Anhydrite 10 Grinding Slag 35 Citric acid 1 Water 30 Initial cure: 3 minutes Hard cure: 10 minutes Compressive strength: 3 hours 3.3 N/mm ² The aqueous mixture initially prepared had a putty-like consistency. Example 17 A mineral clinker having the chemical analysis and phase composition described in Example 1 was ground to a specific surface area of 445 m ² /Kg. This grinding composition was mixed with 2.5 times its weight of water to form a first slurry, a portion of which was tested as a sample to determine pumping life. A mixture was prepared consisting of 2.5% by weight potassium sulfate, 0.3% by weight lithium carbonate, 10% by weight bentonite, 15% by weight hydrated lime and 72.2% by weight finely ground anhydrite. This mixture was then mixed with 2.5 times its weight of water to form a second slurry. The first and second slurries were spray mixed in equal amounts as in a pump-fill operation to form a hardenable cement composition, and the strength was determined again after 2 hours and 24 hours. The measurement results of pumping life and strength are shown in Table 8 below. Example 18 A sulfoaluminous mineral clinker was produced. This clinker contains 50.2% by weight C ₄ A ₃ and 18.3% by weight
_C2AS , 4.1 wt% _CaSO4 , 4.1 wt% CT, 3.4
It had a phase composition consisting of wt% _C4AF and 17.6wt% _CA2 . The balance relative to 100% consisted of insignificant amounts of non-weight components. CA
Or C ₁₂ A ₇ was not confirmed even by X-ray diffraction. This mineral clinker was ground to a specific surface area of 440 m ² /Kg and mixed with 2.5 times its weight of water to form a first slurry. This was mixed with the same second slurry as described in Example 17. Table 8 shows the measurement results of pumping life and strength. Example 19 A composition was formed by mixing equal parts by weight of the ground mineral clinker described in Examples 17 and 18. The resulting composition was slurried and mixed with a second slurry as described in Example 17. Table 8 shows the measurement results of pumping life and strength.

[Table] Although the present invention has been explained above merely by means of examples, it is of course obvious that the details can be changed within the scope of the present invention.

[Brief explanation of the drawing]

The accompanying drawing is a flow sheet diagram illustrating a typical pressure-feed filling method. DESCRIPTION OF SYMBOLS 1... Mixer/pump means, 2... First piping, 3... Outlet, 4... Cavity position, 5... Mixer/pump means, 6... Second piping.

Claims (1)

[Scope of Claims] 1 25 to 68% by weight of 4CaO.3Al ₂ O _{3.SO 3} and substantially 2CaO.Al _{2 O} 3.SiO existing as _two phases.
Contains _SiO2 , optionally with the remainder of the composition not more than 1.0% by weight of free lime, less than 25% by weight of CaO.
2Al ₂ O ₃ , up to 10% by weight of 12CaO.7Al ₂ O ₃ , less than 5% by weight of CaO.TiO ₂ , less than 10% by weight of ferrite phase, up to 60% by weight of CaO.Al ₂ O ₃ and 4.1% by weight A mineral clinker composition characterized in that it essentially contains at least one component selected from the group consisting of up to _CaSO4 . 2. Mineral clinker composition according to claim 1, characterized in that said composition contains less than 20% by weight of CaO.Al ₂ O ₃ . 3. The composition contains 35 to 65% by weight of 4CaO.
The mineral clinker composition according to claim 1 or 2, characterized in that it contains 3Al ₂ O ₃ .SO ₃ . 4. A mineral clinker composition according to any one of claims 1 to 3, characterized in that the composition contains less than 0.5% by weight of free lime. 5. The mineral clinker composition of claim 4, wherein the composition contains less than 0.2% free lime. 6 The composition contains less than 5% by weight of CaO.2Al ₂ O ₃
The mineral clinker composition according to any one of claims 1 to 5, characterized in that it comprises: 7 The composition contains less than 5% by weight of 12CaO.
The mineral clinker composition according to any one of claims 1 to 6, characterized in that it contains 7Al ₂ O ₃ . 8. Mineral clinker composition according to any one of claims 1 to 7, characterized in that the CaSO ₄ phase is substantially absent. 9. A mineral clinker composition according to any one of claims 1 to 8, characterized in that the composition contains less than 10% by weight of _SiO2 . 10. The mineral clinker composition according to any one of claims 1 to 9, wherein the composition is in a pulverized form. 11. A method for producing a curable cement composition by mixing a pulverized mineral clinker composition with an alkali metal or alkaline earth metal source in the presence of water under alkaline conditions, wherein said mineral clinker composition contains 25 to 68 wt. % _{of 4CaO.3Al2O3.SO3 and} substantially _{2CaO3.Al2O.SiO2} present as _{two phases .}
Optionally, the balance of the composition is 1.0% by weight.
Free lime, less than 25% by weight CaO.2Al ₂ O ₃ ,
12CaO・7Al ₂ O ₃ up to 10% by weight, less than 5% by weight CaO・TiO ₂ , less than 10% by weight ferrite phase,
A method for producing a curable cement composition, characterized in that it essentially contains at least one component selected from the group consisting of up to 60% by weight of CaO.Al ₂ O ₃ and up to 4.1% by weight of CaSO ₄ . 12. The method for producing a curable cement composition according to claim 11, wherein the alkali metal or alkaline earth metal source is Portland cement. 13. A method for producing a hardenable cement composition according to claim 11, characterized in that the mineral composition is mixed with calcium sulfate and lime in the presence of water. 14. At least 50% by weight of said calcium sulfate
14. The method for producing a curable cement composition according to claim 13, wherein said gypsum is anhydrite. 15. characterized in that said mineral composition is mixed in the presence of water with at least one further component selected from bentonite and other clays, lithium carbonate and other solidification and/or hardening accelerators and alkali metal sulfates. A method for producing a curable cement composition according to any one of claims 11 to 14. 16 The composition contains less than 20% by weight of CaO.Al ₂ O ₃
A method for producing a curable cement composition according to any one of claims 11 to 15, characterized by comprising: 17 The composition contains 35 to 65% by weight of 4CaO.
A method for producing a curable cement composition according to claims 11 to 15, characterized in that it contains 3Al ₂ O ₃ .SO ₃ . 18. A method for producing a curable cement composition according to claims 11 to 15, characterized in that the composition contains less than 0.5% by weight of free lime. 19. A method for producing a curable cement composition according to claims 11 to 15, characterized in that the composition contains less than 0.2% free lime. 20 The composition contains less than 5% by weight of CaO.
16. A method for producing a curable cement composition according to claims 11 to 15, characterized in that it contains 2Al ₂ O ₃ . 21 The composition contains less than 5% by weight of 12CaO.
16. A method for producing a curable cement composition according to claims 11 to 15, characterized in that it contains 7Al ₂ O ₃ . 22. A method for producing a curable cement composition according to claims 11 to 15, characterized in that the CaSO ₄ phase is substantially absent. 23. A method for producing a curable cement composition according to claims 11 to 15, characterized in that the composition contains less than 10% by weight of _SiO2 . 24. wherein said mineral composition is formed in the form of a first aqueous slurry, said first aqueous slurry being mixed under alkaline conditions with a second aqueous slurry comprising an alkali metal or alkaline earth metal source. A method for producing a curable cement composition according to any one of claims 11 to 23. 25. The second slurry further contains at least one component selected from calcium sulfate, lime, and optionally bentonite and other clays, lithium carbonate and other solidification and/or hardening accelerators, and alkali metal sulfates. 25. A method for producing a curable cement composition according to claim 24. 26 A dry mixture, the mixture comprising a ground mineral clinker composition, the mineral clinker composition comprising:
Contains 25 to 68% by weight _{of 4CaO.3Al2O3.SO3 and SiO2} substantially present as _two phases of _{2CaO.Al2O3.SiO} , optionally with the remainder of the composition not exceeding 1.0% by weight _. free lime, less than 25% by weight CaO.2Al ₂ O ₃ ,
12CaO・7Al ₂ O ₃ up to 10% by weight, less than 5% by weight CaO・TiO ₂ , less than 10% by weight ferrite phase,
an alkali metal or alkaline earth in the presence of water, essentially containing at least one component selected from the group consisting of up to 60% by weight of CaO.Al ₂ O ₃ and up to 4.1% by weight of CaSO ₄ A dry mixture that can be mixed with water to produce a hardenable cement composition according to a method of producing a hardenable cement composition by mixing with a metal source under alkaline conditions. 27. A ground mineral clinker composition, the mineral clinker composition containing from 25 to 68% by weight of 4CaO.
3Al ₂ O ₃ · SO ₃ and 2CaO · Al ₂ O ₃ · SiO _{2 containing SiO 2 present} as two phases, optionally free lime with the remainder of the composition not exceeding 1.0% by weight, 25% by weight
Less than CaO・2Al ₂ O ₃ , less than 10% by weight
12CaO・7Al ₂ O ₃ , less than 5% by weight of CaO・TiO ₂ ,
Less than 10% by weight of ferrite phase, up to 60% by weight
essentially containing at least one component selected from the group consisting of CaO.Al ₂ O ₃ and up to 4.1% by weight of CaSO ₄ in the presence of water with an alkali metal or alkaline earth metal source and alkaline conditions The mineral composition is formed in the form of a first aqueous slurry, and the first aqueous slurry is mixed under alkaline conditions with a second aqueous slurry comprising an alkali metal or alkaline earth metal source. a two-part pack from which a settable composition can be made according to a method for making a settable cement composition, wherein a first part has components for forming a first slurry upon mixing with water; A two-part pack characterized in that part 2 contains a component for forming a second slurry by mixing with water. 28 Milled mineral clinker composition, the mineral clinker composition containing from 25 to 68% by weight of 4CaO.
3Al ₂ O ₃ · SO ₃ and 2CaO · Al ₂ O ₃ · SiO _{2 containing SiO 2 present} as two phases, optionally free lime with the remainder of the composition not exceeding 1.0% by weight, 25% by weight
less than CaO・2Al ₂ O ₃ , less than 10% by weight 12CaO・
7Al ₂ O ₃ , <5% by weight CaO・TiO ₂ , 10% by weight
Less than ferrite phase, up to 60% by weight CaO
essentially comprising at least one component selected from the group consisting of Al ₂ O ₃ and up to 4.1% by weight of CaSO ₄ mixed with an alkali metal or alkaline earth metal source in alkaline conditions in the presence of water. A hardened object formed by solidifying a cement composition produced according to the method for producing a hardenable cement composition. 29 25 to 68% by weight of 4CaO・3Al ₂ O ₃・SO ₃ and substantially exists as 2CaO・Al ₂ O ₃・SiO ₂ phases
Contains _SiO2 , optionally with the remainder of the composition not more than 1.0% by weight of free lime, less than 25% by weight of CaO.
2Al ₂ O ₃ , up to 10% by weight of 12CaO.7Al ₂ O ₃ , less than 5% by weight of CaO.TiO ₂ , less than 10% by weight of ferrite phase, up to 60% by weight of CaO.Al ₂ O ₃ and 4.1% by weight A method for producing a mineral clinker composition basically comprising at least one component selected from the group consisting of CaO ₄ up to CaO source, Al ₂ O ₃
1. A method of production, characterized in that a mixture of a suitable proportion of a source, a source of SO ₃ and a source of SiO ₂ is heated under oxidizing conditions for iron to at least the temperature of initial melting.