JPS61155233A - Settable cement composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for producing a hardening cement composition suitable for filling cavities, for example, in underground mines, a dry mixture from which the cement composition can be produced, and The present invention relates to a novel mineral composition that can constitute the main component of the cement composition.

BACKGROUND OF THE INVENTION One known method for filling cavities in underground mines involves the use of a first aqueous slurry containing cement;
a second aqueous slurry containing an inorganic salt that promotes the curing and assimilation of - to the location of the cavity, where they can be mixed together and cured within the cavity to form a solidified body. Form a filling composition such as: This method is called "pressure filling".

Various materials have been developed for use in this field. The second aqueous slurry is typically calcium sulfate (
In particular, it contains natural or synthetic anhydrite) and lime (calcium oxide and/or calcium hydroxide), and it is also common to include clays such as bentonite.

In underground mines, high alumina cements are advantageous because they are less skin invasive and easier to handle than conventional Pol 1-Rand cements. 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 (B, S,) 915, Part 2 are required to exhibit an initial set time of 2 to 6 hours and a final set time of less than 2 hours after initial set. ing. This can create significant problems in underground mining operations, making it difficult to maintain strict control and monitoring of the mixing and pumping process. Relatively short curing times make the equipment for pumping and mixing cement slurries
To prevent the device from becoming clogged with hardened material, it requires thorough rinsing after the full cavity filling operation. 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.

There is a clear 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 which avoid or reduce the problems associated with short initial set times. .

[Summary of the Invention] The present invention provides a method in which a ground mineral composition is mixed with an alkali metal or alkaline earth metal source in the presence of water and an alkaline state, and wherein the mineral composition is
An object of the present invention is to provide a method for producing a curable cement composition containing an 12O3 phase.

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. It is in.

Furthermore, the present invention provides novel compositions containing at least 15% by weight of 4CaQ-38u,03.SO2, up to 1% by weight of free lime, and less than 25% by weight of (,aO.28Jll).
, +13 and less than 10% by weight of 12CaD -7
An object of the present invention is to provide a mineral composition containing AuEL03.

The mineral compositions described herein are capable of exhibiting long and controlled setting times when ground and mixed with water, and are therefore particularly useful as a base component for the above-described cement compositions.

The mineral composition of the present invention can be produced by first heating a mixture of a CaO source, a HeJ2,03 source, and a 3Al2O3 source in appropriate proportions to a temperature of initial melting without applying iron-oxidizing conditions. Can be produced as clinker.

The produced clinker may be cooled and ground, ie, granulated, by any suitable means.

[DESCRIPTION OF A MORE PREFERRED EMBODIMENT] The mineral composition to be used in the method of the present invention can be described as a ``sulfoaluminaus''. 4Ca
The mineral properties of O ・3Aβdan03 ・3Al2O3 are known as Klein compounds, and 3CaO
・38ρyu03 ・Can be represented by CaSO4 or C7^8g. Clinkers containing Klein compounds, their preparation and use as swelling agents in portland cement compositions are described in U.S. Pat. .419,136. However, in practicing the present invention, it is preferred to use the novel mineral compositions described above.

The mineral composition to be used in the present invention is at least 2
It usually contains 5% by weight, preferably at least 35% by weight, especially at least 45% by weight. In principle, the use of very pure raw materials in electric reverberatory furnaces makes it possible to obtain mineral clinkers with almost 100% C and A3s, although the production costs are relatively high.

Up to 55% by weight of CIA, s, typically about 50% by weight C,X3S of the mineral composition is suitable for many applications, or up to 65% or 68% by weight
In applications consisting of 300%, it is also applicable to have C, AJ≦min of up to 85%. The numerical value of weight % is determined from chemical analysis by calculation of the electrophase composition, and checked by X-ray diffraction.

It has been found that the presence of significant amounts of free lime (Cab) is undesirable as it leads to premature hardening of cement l-compositions containing mineral compositions. Therefore, it is preferred that the free lime content be less than 0.5% by weight of the mineral composition, especially less than 0.2% by weight, and ideally free lime should not be substantially removed from the mineral composition.

The presence of significant amounts of CaO 2AuHO3 (abbreviated as CA2) indicates mineral i1. It has been confirmed that the hardening time of cement compositions produced from fi-fi products can significantly impair the development of steel strength. In particular, CA2 min is 10% of the mineral composition.
The amount should be less than 5% by weight, preferably less than 5% by weight, especially less than 3% by weight. Ideally, CA2 is substantially absent.

However, relatively high levels, such as 20
Seal by inserting CA2 of weight % or more by number.

The mineral properties of +2caO・78J25LO3 (abbreviated as Cl2A'7) react slowly with water to form lime, so the content of C and YA in the mineral composition is low to avoid early hardening. , preferably less than 5% by weight. However, particularly with respect to the strength development of the cement composition, C1IA7 may be present in small amounts in mineral compositions, preferably at least 0.5% by weight, typically up to 4% by weight, especially about 3% by weight.
We have found that retaining % by weight is beneficial. Nevertheless, CnA.

It is also possible to use mineral compositions that are substantially free of minerals.

In order to obtain a high ClA35 content in a mineral composition, it is necessary to limit the amounts of various other phases therein. That is, calcium titanate (CaO・TlO
21) The content of CT (abbreviated as CT) is preferably less than 5% by weight, particularly less than 1% by weight, ideally substantially present. Iron oxide (Fex03, abbreviated as F) is present in the composition as 4CaO・8ρ,03・FeY03 (C9A
Since it forms a ferrite phase close to F (abbreviated as F),
Limiting the amount of Klein compound by removing lime and alumina from the composition. Considering the dilution effect that adversely affects the strength development of the curable cement composition, the content of the ferrite phase should be less than 10% by weight, preferably 5% by weight.
Ideally, it should be practically non-existent.

Since silica (Si02, abbreviated as S) tends to exist as a CαAs phase in mineral compositions, it has a tendency to combine with 8J2,03 which can contribute to the formation of Klein compounds. Therefore, the 5i02 content in the mineral composition is 10
Preferably it is less than 5% by weight, preferably less than 5% by weight, especially less than 3% by weight.

Surprisingly, insofar as the content of GzA3S is to be maximized, considerable amounts, even up to 20% by weight of CaO.Aj2.03(C
A), or allow the presence of up to 60% by weight, for example up to 45% by weight, of CA together with tartar without significantly modifying the low reactivity of the mineral composition with water. can.

The mineral composition is greater than the amount necessary to form Cz8,s.
It does not contain 503. That is, it is preferable that calcium sulfate (CaSO4 or Os) be substantially absent from the mineral composition. However, excess CaSO
4 may be desirable as it aids in 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 of 503 min of 85% by weight.

The mineral compositions according to the invention can be prepared by sintering or melting the raw materials in any suitable furnace, such as a Portland cement clinker rotary kiln or a reverberatory furnace, typically at a temperature of at least 1200°C.

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 Can source is limestone. A suitable SO3 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 fuel having a high sulfur content. It is also possible to use a suitable hel, 03: aluminum metal, such as bauxite or aluminum scrap, which has a combustion energy that contributes to the combustion of the clinker material.

It may be necessary to adjust the fineness of the raw materials 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, a fineness of 90% corresponding to passing through a British Standard 90 micron sieve is usually suitable, and coarser raw materials are acceptable when using the melt method. It is.

In order to obtain maximum benefits, careful control within the dual parameters of mineral composition is important. Such control as well as selection and coordination of raw materials is well within the capabilities of the cement manufacturer. The type of method used, for example the sintering method in a Portland cement clinker rotary kiln (not specially adapted or processed, generally the practical limits are set by the amount of liquid that can be present during combustion) or the CzA3 that can be produced.
When limiting the S plate, any excess calcium aluminate may be present in the clinker as monocalcium aluminate C rather than calcium dialuminate CA2. To avoid the formation of CA2 in the clinker, the composition should be balanced towards the lime enriched region of C+-F, preferably with up to 5% by weight of C1+87 present.

There is a need to ensure that the combustion environment remains oxidizing to the iron. The reason is that the reduction of Fe(I[) is Ca
While imparting Fe(II) which acts as O substitution,
C, AF no longer occurs and the C, AF content may become excessive and form undesirable dish free lime. The presence of FeO in the aluminate phase of the clinker can impair the strength development of the cement composition.

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 potentially producing high levels of Cl2A fumes. It is the main goal. However, regulating the rate of volatilization of SO3 from calcium sulfate (
Oxygen levels within the furnace or kiln can be adjusted (preferably minimized) and can be used as a fine control to prevent or limit the formation of CA2. 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 to produce 50% 4
CaO・38ρQ03・SO3 and 15% CaOH8ft! 203 and 20% 2CaO・An (103・5
i02 and a small amount of CaO・28l1Q03 or 12
CaO・7AuQO3 and CaO・TiO2 and 4C
A typical sulfoalumina composition can be produced by producing a clinker having a ferrite phase with a composition similar to aO.AρΩ03.Fe403. CaO・ At least some of the bow 03 phase is 4CaO
・3Au! :LO3.3Can be replaced with Al2O3, and vice versa. In particular, the composition contains at least 25% by weight, especially 45% by weight of 4CaO.
Contains 3AuQ03.3Al2O3.

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 combustion temperatures. Furthermore, by modifying the main clinker phase, fluorine reduces its reactivity and can thus contribute to the retardation of the reaction of the mineral composition with 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,
Where 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 less than 1% by weight.
It does not exclude levels of fluorine up to or higher than that.

This is accomplished by rapidly cooling the mineral clinker either 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 particularly hard (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 done by mixing crushed clinker with water, [1] a medium containing an alkali metal (such as Na or K) or an alkaline earth (such as Na or K).
For example, this can be achieved by mixing with a Ca source in an alkaline state. 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 a preferred embodiment, the ground mineral clinker uses the aqueous slurry as a source of calcium ions;
For example, it is hydrated by mixing with an aqueous slurry containing a mixture of calcium sulfate and lime (calcium oxide and/or hydroxide). Although lime can be supplied neat (i.e. in the form of slaked lime or hydrated lime), in environments where strength rather than long pumpability is required, conventional por-1-lan-1 cements may be used as a source of lime. It is possible to use it as Common Pol I, Lan I, and Cemen 1 usually contain calcium sulfate and can therefore be used as sources in suitable applications of the present invention.

That is, for example, the mineral composition can be mixed with the activating composition in any suitable ratio (199-99°1 in common type l ratio), in which case the activating composition is (a) 5-90°
%, preferably 40-85% calcium sulfate, (b)
5-60%, preferably 10-25% of lime source (Ca(
(expressed as 011)2), (c) up to 10%, preferably 1-10%, in particular 2-5% of one or more additional inorganic salts, (d) up to 25%, preferably 05-25%,
Especially 5-15% clay such as hentonite and (e)
2%, preferably up to 0.5% retarder, and these percentages represent components (a) to (e) on a dry weight basis.
It is for the sum of .

The sulfoaluminous compositions are particularly useful for filling underground mine cavities by pump filling. Compared to high alumina cement slurry, the sulfoalumina composition slurry (first slurry) can be left in the mixing pumping device for a long period of time due to its extremely low hydration reactivity in terms of wood quality (C, A 3≦-). I can do it. That is, B of high alumina cement
, the minimum 24-hour strength according to 5.915 or 4[]MNm~
2, whereas the 24-hour strength of a typical ground mineral clinker according to the present invention is about 0.5 MNm=. Generally, sulfoaluminous compositions of this type have not been permitted as cements per se for building or construction work. Thus, the present invention eliminates the need to remove the first slurry from the mixing pumping system after each implantation operation, allowing the slurry to normally remain in such a system during field transfer without fear of clogging due to hardening. I can do it. 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 CIIAZ+ and CA, which are known to be reactive 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. The tendency to set within periods of less than 20 hours can be easily overcome by incorporating relatively inexpensive retarders, especially citric acid, into the slurry. It is surprising that the lignically 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).

In order to fill cavities using the pressure-feed filling method, sulfoalumina clinker is ground into a fine powder that does not cause sedimentation of particles generated when the aqueous suspension is kept for a long period of time. Preferably at least 95% by weight of the material,
In particular, the particle size distribution is such that at least 98% by weight has a particle size of less than 45 microns. To achieve this, it may be necessary to use grinding aids such as propylene glycol or triethanolamine.

It is also possible to use a suspension agent such as cellulose ether, which is added to the clinker before, during or after grinding, or added to the drainage water. (The use of a suspending agent may prevent rapid settling of relatively coarse ground clinker particles, or the use of such coarse materials is undesirable because it tends to inhibit crystal growth during the hydration-sedimentation reaction.) 1 The pumpability of the 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) mixed with the first slurry by the pressure filling method to form the cement 1 to composition contains calcium sulfate,
Clay (e.g. bentonite) and hydrated lime with a small amount of alkali metal sulfate (e.g. K!1LsO4,)
It is preferable to contain it together with a curing and/or solidification accelerator.

The calcium sulfate may be supplied, for example, as gypsum hand hydrate, natural anhydrite, synthetic anhydrite or a mixture thereof; it is particularly preferred that the calcium sulfate is at least 50% by weight anhydrite. In particular, 250% of cardim sulfate
Grind to sub-micron particle size. The reason for this is that it has been confirmed that coarse particles can sometimes delay the development of strength of cement compositions. However, it has also been found that excess particles having a particle size of less than 2 microns can sometimes retard curing.

Hentonite was 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 is of primary interest that any CA phase in the mineral composition has a tendency to react with calcium sulfate and hydrated lime from the second slurry to form calcium ettringitolfoaluminate hydrate.

- By way of example, the method of the invention will be described with reference to the accompanying drawings, in which:

Mixer/pump means 1 for mixing sulfoalumina composition and water
It is mixed into a slurry therein and pumped along a first pipe 2 towards an outlet 3 adjacent to a cavity location 4 of the underground mine. This cavity location can be surrounded by a weir plate or by a large bag placed at an appropriate location. The slurry is mixed with the second slurry by the means 5 and pumped along the second pipe 6 connected to the first pipe 2 by the Y adapter 7 located near the cavity position.
When operating the mixer/pump means 1, 5 at the same time,
Two types of slurry are sprayed and mixed adjacent to the outlet 3 and enter the cavity. The resulting mixture is hydrated and hardened to a solidified product that completely or partially fills the cavity, and this solidified product is typically processed through steps 1 to 1.
Contains linkite or other calcium sulfoaluminate woodylate.

If strength is not of primary importance, the cavity can be filled with a 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 in many other applications, and for this reason, suitable fineness (fine or coarser than the levels specified above for filling cavities in underground mines) can be used.
It may be crushed. The mineral composition of the invention can be ground with auxiliary materials, such as Portland cement clinker, gypsum, anhydrite, high alumina cement clinker, granulated blast furnace slag (for example, with slag in amounts up to 60 heavy weight of total dry solids). Fuel ash (for example, with ash in an amount up to 50% by weight of total dry solids) or other! Inter-milling or otherwise mixing with all inert substances conventionally included in existing hydraulic or volcanic ash materials, pigments, hydrated lime, hentonite, mortar or concrete, or any mixture thereof. I also take this into account. If the auxiliary material contains available alumina, the alumina may also increase the amount of Ettringai or other calcium sulfoaluminate hydrates formed during hydration. Where the mineral clinker is
It is suitable to mix with one or more of the above-mentioned materials as a mixture of finely divided materials and finely divided materials.

The poor initial reactivity (imparting good flowability) and subsequent rapid strength development exhibited by mineral compositions makes them suitable for use in specialized groutes such as tile adhesives and self-leveling bed mortars. become suitable.

We also boast of the use of mineral compositions, especially in mixtures with hentonite, as a basis for casting plasters, in particular as a basis 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 has a relatively low density (
It also contributes to the production of molds (which are advantageous for the production of decorative molds for ceilings). The low density of the mineral composition/hennite mixture makes it suitable as a lightweight insulating plaster or bone grafting material.

Water may be present in the curable composition in an amount of 2 to 99 percent by weight and 15 to 90 percent by weight of the total composition, depending on the application. For pressure filling, the amount of water is preferably between 55 and 75% by weight, whereas for other purposes, such as building materials and mining grouts, the amount of water is between 25 and 40% by weight.
It is possible to do this.

Apart from pump filling and similar treatments, curable compositions can also be prepared by directly mixing the solid components with water. That is, in commercial practice, the ground mineral composition and other solid components can be supplied to the end user as a dry mixture, which the end user is required to mix with water. Of course, this does not preclude the end user 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 the 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 dry ingredients which, when mixed with or added to water, provide a slurry containing the alkali metal or alkaline earth metal source in an alkaline state. Typically, the second pack of the two-piece pack contains calcium sulfate, clay, alkali metal sulfate, and a curing and/or setting accelerator.

Next, the present invention will be explained with reference to examples.

Example 1 A raw material mixture consisting of 4348 parts by weight of hawkide, 31.96 parts by weight of limestone, 24.57 parts by weight of anhydrite, and 1.22 parts by weight of charcoal was produced. The analysis of the three main components is shown in Table 1 below (values are weight%, L
, 0, I is the ignition loss).

Turtle-”--l Bauxite Limestone Anhydrite 5IOp
5.8 0.7 0.3
A Sentence QOs 81. ?
0.2 0.1F+40. ,
1.7 0. l 0. lCaO
1,655,441,8 So, 0.5 -
58.47iOq 3.0
−” −F
---1,1L, 0.1. ,
0.18 43.4
0.7 This raw material mixture was heated in a heavy oil-fired reverberatory furnace at 145
It was fired at 0°C. 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 18 parts by weight of charcoal was produced. The analytical values for limestone and anhydrite were as shown in Table 1 above, and the chemical analysis values for bauxite were 41% as shown in Table 2 below.

ゝ＼、＼１、、、、、、Table 2 Bauxite 510, 6:58i, o3
a6. .

Fe! 103 0.9Mnc03
Less than 0.01P! 10 ta
0.15T+024.0 CaO 0J Mg0 0 , 3SO30.07 L+0 0.95Na! 20
'0.07L, 0.1.
0.3 This raw material mixture was slurried in water, fed to a coal fired rotary kiln, and sintered at 1450''c.

(The charcoal shown in the composition of the raw material mixture indicates the ash mixed into the material during sintering. This is the opposite of Example 1, where charcoal was added at the start to simulate coal firing.) The chemical analysis and calculated composition of the produced clinker are shown in Tables 3 and 4, respectively.

Chemical analysis of brittle barley mineral clinker (weight%)￥jui
i Exampleヱ5inQ4.3 4.8 A sentence, 0347.7 4B, 0Fe4)03
1.1 +, fi
Mn! 103
0.01p, o50.09 Tie, 12.3 2. l CaO38,0' 37.8 Mg0 1.5 0
．． fiSO3e, o e, e K! IOO,180,42 L,O,1,0,10,6 Free lime 0.08 0.1
2 Table 1 Example of calculated composition (weight %) of mineral clinker” Tsuse Yuzu C A3s 45.7
50.3C AS 19.8
21.0CA
lfl, 8 1? ,7C,AF
3.4 4.8CT
4.3
3.11CaSOa O,O
Q, 0CA2 2.8”
0.60 is A'1(1, G O,
The value of 0*2.8 was obtained by X-ray diffraction measurements.

Example 3 Four raw material mixture samples were produced. Each sample contains 4348% hawkide, 3196% 0 limestone and 24%
It contained 57% by weight of anhydrite, and the chemical analysis values of these components were as listed in Table 1 above. Charcoal was not present in these particular samples. The roughness of these il (materials) was changed. That is, +90 micron residual was sample No.
01% by weight for l, 14 NO for test, 4.0% by weight for 2 Teha,
Sample No. 3 Teha 9.3% by weight, try-on No. 4: 2
It was 0.05% by weight.

Each tryout was fired at 1450° C. in a furnace with pilot scale heavy oil. Determine the phase composition of each clinker produced and perform the following fifth step.
The results shown in the table were obtained.

Pigeon sac mineral clinker composition (weight %) sample” Sushi 111Y, Mico PkO, 00,040, OUo, 03
Each mineral clinker sample was crushed to 450 m2/g.

1 part by weight of ground clinker was mixed with 25 parts by weight of water for 30 seconds using a high shear stirrer to produce an aqueous slurry. The time during which the slurry can be pumped (s2t, ie, the time during which the slurry can be pumped) was determined by measuring the shear resistance of the slurry.

This measurement was also performed on a slurry to which 0.2% by weight of citric acid was added. The results obtained are shown in Table 6 below.

1st table Possible time for pumping (hours) Trial 2 course additives 1 2 3
4 None 15 12
15 1502% citric acid 24
20 >24 >24701 parts by weight of anhydrite, 18 parts by weight of hydrated lime, 5 parts by weight of hentoni 1-, 0.5 parts by weight of thorium carbonate, 0
4 parts by weight of lithium carbonate, and using a high shear stirrer, the mixture was reduced to 1 part by weight! 1 part was mixed with 2.5 parts water for 30 seconds. 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 7: 30 20
25 30 punch strength 2 hours 2.0
+, 7 2.3' 2.224
Time 3.8 3.5 4.1
3.97 days 4.7 4.8 5.0
4.828 days 5.0 4.8
5.3 4.8 Examples 4-I 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 the darning composition was cured under atmospheric conditions for a specified period of time, the compressive strength of the cured composition was determined.

Example 4 composition.

Sand 50 parts by weight Mineral clinker 25 Hydrated lime 15 Anhydrite 10 Citric acid 1 Water 225 Initial hardening Approximately 6 minutes Compressive strength (sealed bag) = 3 hours 7.7 N/mm26
Time 6.7 1 day 16.9 3 days 19.7 11 days 26.3 28 days 29.7 The above composition can be used as a grout that hardens quickly and quickly imparts strength, for example as a tile adhesive. It was useful for this purpose.

Example 5 Composition: Sand 50 parts by weight Mineral clinker 25 Hydrated lime 15 Anhydrite lO Citric acid 1 Melment ro+tl' Water 20 Initial hardening, about 10 minutes Compressive strength (sealed bag): 3 hours 14.4 N/mm2
6 hours 22.7 1 day 38.6 3 days 41.3 8 days 481 28 days 604 Melment FIO is a superplasticizer based on melamine-pormaldehyde polymers (manufactured by Deutsche Karlschistofwerke AG). ). The superplasticizer reduces water requirements and thereby provides high strength cement compositions.

This composition is useful as a filler material for shrinkage compensators in road and airport runway kettles.

Example 6 Composition - Sand 50 parts by weight Mineral clinker 15 Anhydrite 6 Citric acid 1 Water 225 Initial hardening - Approximately 30 minutes Compressive strength 6 hours 18.9 N/mm2
This composition is suitable as a good quality grout.

Example 7 Composition; Sand 50 parts by weight Mineral clinker 15 Anhydrite 6 Citric acid 0.25 Water 20 Initial hardening: Approximately 20 minutes Compressive strength (sealed bag), 3 hours 4.5 N/mm2 Example 8 This composition Example 7 except that the amount was reduced to 18 parts by weight.
It was the same as described in. Initial curing takes approximately 17 minutes, and compressive strength (sealed bag) after 1 day is 27.0 N/mm2
Met.

Example 9 This composition was the same as described in Example 7 except that the water was reduced to 16 parts by weight.

Initial hardening, approximately 12 minutes Compressive strength (sealed bag) 3 hours 7.7N/mm27
Day 328 Day 28 299 Example 10 This composition was the same as described in Example 7 except that the water was reduced to 14 parts by weight. Initial curing is about 5 minutes °C1
Compressive strength after 3 hours (Mizuma bag) is 7.4 N/mm2
There was.

Example 11 The composition was the same as described in Example 9 except that the amount of citric acid was 0.125 parts by weight. Initial curing takes approximately 5 minutes, and compressive strength (sealed bag) after 3 hours is 5.1 N/
It was mm2.

Example 12 Composition - Sand 50 parts Mineral clinker 25 Hydrated lime 15 Anhydrite 10 Crushed fuel ash 25 Citric acid 1 Water 35 Initial hardening Approximately 15 minutes Compressive strength (dense 1 bag), 3 hours 5. ON/mm2
6 hours 87 1 day 20.5 4 days 245 9 days 225 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, about 5 minutes compressive strength, 1 day 14.1 N/mm2
Example 14 Composition: Sand 50 parts by weight Mineral clinker 18 Anhydrite 35 Citric acid 0.5 Water 17.86 Initial hardening
Approximately 40 minutes compressive strength (sealed bag), 3 hours 3.4 N/mm2 I/V Composition: Sand 70 parts by weight Mineral clinker 25 Anhydrite 5 Citric acid 05 Water 30 Initial hardening: Approximately 20 minutes compressive strength (sealed bag) . 3 hours 3, 3N/mm2
Example 16 Composition: Sand 50 parts by weight Mineral clinker 25 Hydrated lime 15 Anhydrite lO Ground slag 35 Citric acid 1 Water 30 Initial hardening 3 minutes Hard hardening: 10 minutes Compressive strength 3 hours 3.3 N/mm2 Initially prepared aqueous The mixture had a putty-like consistency.

Example 17 Organic clinker having the chemical analysis and phase composition described in Example 1 was ground to a specific surface area of 445 m27 kHz. This grinding composition was mixed with 25 times its weight of water to form a first slurry, a portion of which was tested to determine pumping life.

From 2.5% by weight of potassium sulfate, 0.3% by weight of lithium carbonate, lO heavy state benite, 15% by weight of hydrated lime, and 722% by weight of finely ground anhydrite. A mixture was prepared. This mixture is then divided into 2 parts of its weight.
A second slurry was formed by mixing with 5 times as much water.

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 sulfoalumina mineral clinker was produced. This clinker is 502 heavy view type Oc, A3s, 18.3% by weight C
2AS, 4.1% by weight CaSO4, 4.1% by weight
CT of.

3.4 wt% C, AF and 17.6 wt% CA2
The phase composition was as follows. The balance relative to 100% consisted of insignificant amounts of unimportant components. CA or C,UA was not confirmed by X-ray diffraction.

This mineral clinker was ground to a specific surface area of 440 m2/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.

8th Table 17 30 2.44 4.00+8 18
0.32 2.501!3 22 0.11
8 3.34 Although the present invention has been described above merely by means of examples, it is of course obvious that the details thereof may be modified 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. 1- ・Mikizun 15th Rubke p negative, 2 ・f)
l n layout 3・ Oshi 0゜4・・゛2A゜bacterial 5, Mi piece “su′／・cho・°〉゛↑dan, 6−
Taku 2/l layout Y.

Claims (1)

[Claims] 1) At least 15% by weight of 4CaO.3Al_2O_
In mineral compositions containing 3.SO_3, 1.0
Less than 25% by weight of free lime and less than 25% by weight of CaO.2
Al_2O_3 and 10% by weight or less of 12CaO.7A
A mineral composition characterized by containing l_2O_3. 2) A composition according to claim 1 containing up to 60% by weight of CaO.Al_2O_3. 3) Less than 5% by weight of CaO・TiO_2 and 10% by weight
less than 20% by weight of ferrite phase and less than 20% by weight of CaO/Al
The composition according to claim 1, which contains _2O_3. 4) At least 25% by weight of 4CaO.3Al_2O_
The composition according to claim 1, 2 or 3, containing 3.SO_3. 5) A composition according to any one of claims 1 to 4 containing less than 0.5% by weight of free lime. 6) A composition according to claim 5 containing less than 0.2% by weight of free lime. 7) The composition according to any one of claims 1 to 6, containing less than 5% by weight of CaO.2Al_2O_3. 8) The composition according to any one of claims 1 to 7, containing less than 5% by weight of 12CaO.7Al_2O_3. 9) The composition according to any one of claims 1 to 8, wherein the CaSO_4 phase is substantially absent. 10) In preparing a curable cement composition by mixing a ground mineral composition with an alkali metal or alkaline earth metal source in an alkaline state in the presence of water, the mineral composition is 4CaO.3Al_2O_3.SO_3. A method for producing a curable cement composition comprising a phase. 11) The mineral composition contains at least 25% by weight of 4CaO
- The method according to claim 10, which contains 3Al_2O_3.SO_3. 12) The method according to claim 10 or 11, wherein the alkali metal or alkaline earth metal source is Portland cement. 13) A method according to claim 10 or 11, in which the mineral composition is mixed with calcium sulfate and lime in the presence of water. 14) The method of claim 13, wherein at least 50% by weight of the calcium sulfate is anhydrite. 15) Mixing the mineral composition in the presence of water with at least one additional component selected from bentonite and other clays, lithium carbonate, other hardening and/or setting promoters and alkali metal sulfates. Section 10~
The composition according to any of paragraph 14. 16) The method according to any one of claims 10 to 15, wherein the mineral composition is according to any one of claims 1 to 9. 17) The mineral composition is formed into a first aqueous slurry which is mixed in an alkaline state with a second aqueous slurry containing an alkali metal or alkaline earth metal source. Any method described. 18) The second slurry comprises calcium sulfate, lime, and optionally at least one additional component selected from bentonite and other clays, lithium carbonate, other curing and/or setting accelerators, and alkali metal sulfates. 18. The method according to claim 17, comprising: 19) A dry mixture in which the curable composition can be prepared according to the method according to any of claims 10 to 16 by mixing with water. 20) A two-piece pack in which the curable composition can be produced according to the method described in claim 17 or 18, the first pack consisting of components for forming a first slurry by mixing with water. , the second pack is a two-part pack consisting of ingredients to form a second slurry by mixing with water. 21) A solidified object formed by curing a cement composition produced according to the method according to any one of claims 10 to 18.