WO2015055879A1

WO2015055879A1 - Refractory concrete composition

Info

Publication number: WO2015055879A1
Application number: PCT/ES2014/070776
Authority: WO
Inventors: Edouard GONZÁLEZ ROUBAUD; David PÉREZ OSORIO; Cristina PRIETO RÍOS; Isabel GIRBES CLARI; Luis Miguel ORDÓÑEZ BELLOC
Original assignee: Abengoa Solar New Technologies, S.A.
Priority date: 2013-10-14
Filing date: 2014-10-13
Publication date: 2015-04-23
Also published as: ES2535781A1; ES2535781B1

Abstract

The invention relates to a refractory concrete composition with low thermal conductivity and increased resistance, to the method for the production thereof, and to the use of same as a structural concrete coating for elements subjected to high temperatures which are simultaneously required to bear structural compression forces, such as nuclear reactors, storage facilities and tanks, foundations and furnaces.

Description

REFRACTORY CONCRETE COMPOSITION

DESCRIPTION The present invention relates to a refractory concrete composition of low thermal conductivity and high strength. Likewise, the present invention relates to the process for obtaining said composition and its use as a structural concrete cladding for elements subjected to high temperatures that at the same time need to withstand structural compression stresses, such as nuclear reactors, tanks and storage tanks, foundations and ovens. Therefore, the present invention could be framed in the field of construction, in architectural and engineering works. STATE OF THE TECHNIQUE

Currently there are refractory concretes used as insulators for use in high temperature applications (450-1700 ° C). These insulating refractory materials are mainly composed of aluminum and silica materials that allow to increase the thermal resistance of concrete at very high temperatures. In this sense, there is a composition comprising high and low density alumina and colloidal silica refractory material (ES2197180), but which is very expensive due to its content in aluminous materials.

On the other hand, there are currently compositions with excellent compression resistance such as a hydraulic cement composed of a portland cement, plaster, water and plasticizer, which allows reducing the demand for water (W01997038947), a concrete consisting mainly of portland cement, sand (silicon), and Glenium-106 that reaches a compressive strength of 100 MPa at 28 days (WO2006027645) or a projection concrete comprising Portland cement, aggregates with a size less than 2 mm, additives and water (W01999058465). However, none of these compositions is refractory.

Therefore, it would be desirable to have a concrete composition of low thermal conductivity and high compressive strength, the cost of which (lower than the concrete in the state of the art with alumina content) allows its use in commercial applications.

DESCRIPTION OF THE INVENTION

The present invention solves the problems mentioned in the state of the art by providing a refractory concrete composition with the following properties:

- thermal conductivity less than 0.45 W / mK;

- 90-day compressive strength greater than 20 MPa and tensile strength greater than 1 MPa; Y

- resistance without degradation at temperatures up to 450 ° C;

- minimum fluid consistency, cone greater than 10 cm, to be pumpable; Y

- be light.

The first aspect of the invention relates to a composition characterized in that it comprises:

• at least one conventional cement in a proportion of 400 to 700 kg / m ³ ;

• a light aggregate, consisting of sand and gravel, in a proportion of 500 to 850 kg / m ³ ;

• at least one active water reducing dispersing agent in a proportion of 2 to 10 kg / m ³ ;

• fly ash in a proportion of 50 to 200 kg / m ³ ; Y

• water in a proportion of 100 to 350 kg / m ³ , and where the a / c _e fect¡va ratio is 0.45 to 0.75.

In the present invention, the term "conventional or common cement" refers to that cement with a low alkali content that has a low chemical vulnerability and high compressive strength. As examples of this type of cement, mention, but not limited to, CEM I 42.5R / SR and CEM I 52.5R / SR cements, which refers to a Portland cement type I of high strength 42.5 MPa and 52.5 MPa respectively at 28 days with high initial resistance (R) and sulfate resistant (/ SR).

Throughout the present invention the term "light aggregates" refers to aggregates of a ceramic nature, preferably of the light expanded clay type, with a density of less than 2000 kg / m ³ Examples include, among others, expanded clay sand (EA) with a grain size of less than 4 mm (sand AE 0/4) and expanded clay gravel (AE) with a grain size of less than 10 mm (gravel AE 3/10). The densities indicated above for expanded clay give said clay the low weight characteristic, that is, the designation of light clay, characteristic that contributes to the final concrete conductivity being less than 0.45 W / mK as desired, thus obtaining a refractory concrete of low conductivity (insulator).

In the present invention, the term "water reducing active dispersing agent" refers to an additive capable of strongly reducing the water content of the composition without modifying the consistency. This additive makes the fresh concrete have better workability and pumpability properties.

The term "fly ash type F" refers, in the present invention, to that fly ash produced by calcining charcoal or Bituminous that contains less than 15% calcium carbonate (lime) and contains silica, aluminum and iron.

The term "effective water / cement ratio" or "a / c _e fect¡va" refers, in the present invention, to the ratio between the amount of water in the batch plus the amount of water contained in aggregates and additives, and the amount of cement of the kneaded. This relationship indicates the mechanical strength of concrete as it is related to its density. In a preferred embodiment, the invention relates to the composition defined above, where the ratio a / c _and date is from 0.49 to 0.71, more preferably from 0.65.

In another preferred embodiment, the invention relates to the composition defined above, which further comprises an aerator in a proportion less than 0.30% by mass with respect to the final composition, more preferably less than 0.10% by mass with respect to to the final composition.

In another preferred embodiment, the aerator is BASF Microair-100.

In another preferred embodiment, the invention relates to the composition defined above, wherein the cement is gray Portland cement of category CEM I 42.5 R or CEM I 52.5 R, preferably CEM I 52.5 R. In another preferred embodiment , the invention relates to the composition defined above, where the cement is in a proportion between 430 and 550 kg / m ³ , more preferably 445 kg / m ³

In another preferred embodiment, the invention relates to the composition defined above, where the light aggregate is selected from expanded clays with densities of less than 2000 kg / m ³ , and preferably with densities of less than 1600 kg / m ³ . In another preferred embodiment, the invention relates to the composition defined above, where the light aggregate is selected from expanded clay sand of grain size less than 4 mm and expanded clay gravel of grain size less than 10 mm.

In the present invention, "fine aggregate" means one with a grain size of less than 4 mm and "coarse aggregate" means one with a grain size of less than 1.2 mm. In the present invention, sand, in particular the expanded clay sand AE 0/4 can be defined as "fine aggregate", since this term refers to aggregates with small grain size, in particular less than 4 mm.

In the present invention, gravel, in particular expanded clay gravel AE 3/10 can be defined as "coarse aggregate", since this term refers to aggregates with grain size greater than fine aggregate, particularly with aggregate size grain less than 1, 2 mm.

In another preferred embodiment, the invention relates to the composition defined above, where the light aggregate is in a proportion between 650 and 850 kg / m ³ , more preferably 698 kg / m ³

In another preferred embodiment, the invention relates to the composition defined above, wherein the water reducing active dispersing agent is a concrete superplasticizer, more preferably of the type lignosulfonates, naphthalene sulfonates, melamine sulphonates or polycarboxylates.

Even more preferably the dispersing agent is in a proportion between 4.0 and 5.0 kg / m ³ , more preferably 4.5 kg / m ³ . In another preferred embodiment, the invention relates to the composition defined above, where the fly ash is of type F. In another preferred embodiment, the invention relates to the composition defined above, where the fly ash is in a proportion of between 80 and 120, more preferably in a proportion of 106 kg / m ³ In a second aspect, the present invention relates to the procedure for obtaining the composition defined above, which comprises the steps of: a) measuring the humidity of the light aggregate and adjusting the amount of water and aggregate with respect to the final composition;

b) adding, in the order described, water, the water-reducing active dispersing agent, conventional cement and fly ash to a kneading device;

c) add the fine aggregate or sand to the mixture obtained in b); Y

d) add the coarse aggregate or gravel on the mixture obtained in c);

Before proceeding with the preparation of the composition of the concrete of the invention, the humidity of the aggregates that form the light aggregate (sand and gravel) must be measured beforehand so that, if necessary, adjust or correct the dosage of the final composition by redosing aggregates and water in the mixture.

The humidity of the aggregates is determined by burning aggregates or hygrometric balances of a previous sample.

If any of the light aggregate fractions, that is, if the fine aggregate fraction or the coarse aggregate fraction had moisture, the excess thereof must be deducted from the total amount of water necessary to obtain the composition of the invention. . In case both fractions had moisture, the sum of both must be deducted from the amount of total water necessary to obtain the composition of the invention. This quantity of discounted water has to be replaced by more aggregate in the same amount, fine or coarse respectively, until obtaining the amount of water and aggregates mentioned to obtain the composition of the invention for use as concrete.

In a preferred embodiment, the process described above further comprises a step e) of adding an aerator, after step d) of adding the coarse aggregate. In another preferred embodiment, the invention relates to the method of obtaining the composition defined above, where the kneading device is selected from a planetary vertical mixer or a concrete mixer, a concrete mixer truck and a concrete plant. The third aspect of the present invention relates to the use of the composition described above as structural concrete cladding, preferably as cladding of structural concrete of containment structures, more preferably as structural concrete cladding of nuclear reactors, industrial facilities subjected to high temperatures , storage tanks and tanks, foundations or furnaces, even more preferably as a structural concrete coating of a thermal storage tank of a pressurized fluid.

The last aspect of the present invention relates to a thermal storage tank of a pressurized fluid, either liquid or gas, comprising an external layer of post-tensioned concrete with a characteristic resistance greater than 50 MPa and an internal layer of refractory concrete that It acts as a thermal barrier between the fluid and the post-tensioned concrete, characterized in that the inner layer is composed of the composition of the invention described above.

Throughout the description and the claims the word "comprises" and its variants are not intended to exclude other technical characteristics, additives, components or steps. For those skilled in the art, other objects, advantages and features of the invention will be derived partly from the description and partly from the practice of the invention. The following examples are provided by way of illustration, and are not intended to be limiting of the present invention.

BRIEF DESCRIPTION OF THE FIGURES

Fig. 1: Vertical section and side view of the accumulator tank of example 3.

Fig. 2: Cross section of 90 ° made to the accumulator tank of example 3.

EXAMPLES Example 1: Composition of concrete without venting

The following table 1 shows a composition of the concrete of the invention without aeration. Table 1: Example of the composition of the concrete of the invention.

%,

Components kg / m ³ Origin Type

mass

Cement CEM l-52,5-R 432 31, 3 La Unión Cemento

Andorra

Fly Ash 103 7.5 Addition

(Teruel)

Glenium Superplasticizer

4.37 0.3 BASF Additive C303 SCC

Expanded Clay

Arena AE 0/4 Arlita 474 34.3 Arciresa

Light

Gravel AE 3/10 Arlita 204 14.8 Arciresa Clay Expanded Light

Water 163 1 1, 8 - -

As for aggregates, an expanded clay with two different granulometries is used. The following table 2 shows the main parameters of these aggregates according to the granulometry. To achieve the required thermal conductivity, the density of the aggregates must be between 500 and 2000 kg / m ³ , and more preferably between 1000 and 1600 kg / m ³ .

Table 2: Requirements

Being p _SS d the density of the saturated dry surface dry or as apparent density and p _r the relative density of the aggregate. The difference between the two is expressed as the degree or percentage of water absorption that the aggregate admits.

As for additives, the BASF Glenium C303-SCC superplasticizer has been used.

As for fly ash, one of type F has been used.

The following table 3 shows some results of different tests performed. Table 3: Kneads tested

It is found that the use of additions such as fly ash improves the contact interface of the aggregate with the water-cement mixture, the workability of the concrete, and increases the compressive strength.

The values of compressive strength, tensile strength and thermal conductivity have been validated according to standardized tests.

As for the characterization in the fresh state of refractory concrete, the Abrams settlement or cone test has been carried out, according to the specifications of the UNE EN 12350-2: 2006 standard (AENOR 2006). This test is used to determine the consistency of the mixture at the time of concrete pouring. It also allows to check the homogeneity of the concrete through the segregation of the mixture.

Regarding the characterization in the hardened state of refractory concrete, tests of compressive strength of cylindrical specimens have been carried out, according to the UNE 12390-3: 2001 standard (AENOR 2001). The results are shown in the following table 4.

Table 4: Compressive strength (MPa)

Indirect tensile strength tests of cylindrical specimens UNE 12390-6: 2010 (AENOR 2010) as well as thermal conductivity have also been performed. The results of indirect tensile tests are shown in the following table 5.

Table 5: Indirect tensile strength (MPa)

Indirect tensile strength

(MPa)

Am.1 1, 58

Am.2 1, 57 For thermal conductivity tests, conductivity measurements have been made both at room temperature (method A) according to the application of the UNE EN 12667 standard, and at 150 ° C and 250 ° C (method B). The thermal conductivity results are shown in table 6.

Table 6: Thermal conductivity (W / mK)

Example 2: Composition of concrete with aerator

The following table 7 shows another concrete dosage of the invention together with the amounts of materials used.

Table 7: Example of composition of the concrete of the invention

Kneading 1 Kneading 2 Kneading 3

Components kg / m ^at % kg / m ^at % kg / m ^at % mass mass mass

CEM Cement I- 445 29.03% 445 29.03% 445 29.03% 52.5-R

Fly ash type 106 6.92% 106 6.92% 106 6.92% F

Superplasticizer 4.5 0.29% 4.5 0.29% 4.5 0.29% Glenium C303 SCC

Arena AE 0/4 Arlita 488 31, 84% 488 31, 84% 488 31, 84%

Gravel AE 3/10 210 13.7% 210 13.7% 210 13.7% Arlita

Water 279 18.2% 279 18.2% 279 18.2%

Ventilating Microair- 0.33 0.02% 0.67 0.04% 1, 34 0.09% 100

The following table 8 shows some results of different tests performed: Table 8: Properties of the composition of the invention

The values of compressive strength and thermal conductivity have been validated according to standardized tests. To achieve this refractory concrete with the desired properties, both of the compositions of Examples 1 and 2, the manufacturing method described below must be followed: A measurement of the moisture contained in the aggregates is first carried out in order to , if necessary, adjust or correct the dosage of refractory concrete by redosing the aggregates and water in the mixture.

Once the humidity of the aggregates is corrected, the mixture of the refractory concrete is manufactured in a kneading device.

First, the superplasticizer additive is added to the water. Cement, fly ash and fine aggregate are added in that order. Once the desired consistency is achieved, the coarse aggregate and the aerating additive are added.

Example 3: Use of the composition of the invention as a structural concrete coating of a thermal storage tank of a pressurized fluid.

The composition of the invention of examples 1 or 2, that is with or without aeration, can be used as a structural concrete siding for the manufacture of a thermal storage tank. As a preferred embodiment, we present a tank like the one described in the Spanish patent application with application number P201200796, with application date August 6, 2012. It is a cylindrical steam accumulator tank consisting of two layers, an outer layer of post-tensioned concrete and an inner layer of refractory concrete.

Figure 1 shows the vertical section of a steam accumulator comprising the concrete composition of the invention. In it you can see the double layer formed by the cylindrical concrete body post-tensioned (1) in its outer part and the cylindrical body of a refractory concrete composed of the composition of the invention, particularly that of examples 1 or 2, (2) in its inner face. This cylindrical shape has two semi-ellipsoids at its ends, the semi-ellipsoidal body of post-tensioned concrete (3) and the semi-ellipsoidal body of a refractory concrete composed of the composition of the invention, particularly that of examples 1 or 2, (4) , so that it allows a better distribution of the tensions generated by the pressure and the temperature inside the accumulator as well as minimizing the loss of useful volume with respect to the spherical cap.

Figure 2 shows the 90 ° cross section made to the concrete accumulator where the post-tensioned concrete base (5) can be seen.

Claims

1 . - Composition characterized because it includes:

• at least one conventional cement in a proportion of 400 to 700 kg/m ³ ;

• a light aggregate, consisting of sand and gravel, in a proportion of 500 to 850 kg/m ³ ;

• at least one active water-reducing dispersing agent in a proportion of 2 to 10 kg/m ³ ;

• fly ash in a proportion of 50 to 200 kg/m ³ ; and

• water in a proportion of 100 to 350 kg/m ³ ,

where the _effective w/c ratio is 0.45 to 0.75.

2. - The composition according to claim 1, where the effective w/ _c ratio is 0.49 to 0.71.

3. - The composition according to claim 2, where the effective _w /c ratio is 0.65.

4. - The composition according to any of claims 1 to 3, which also comprises an aerant in a proportion of less than 0.3% by mass with respect to the final composition.

5. - The composition according to claim 4, wherein the aerant is in a proportion of less than 0.1% by mass with respect to the final composition.

6. - The composition, according to any of claims 1 to 5, where the cement is selected from gray Portland cement of category CEM I 42.5 R or CEM I 52.5 R.

7. - The composition, according to any of claims 1 to 6, where the cement is in a proportion of between 430 and 550 kg/m ³ .

8. - The composition according to claim 7, where the cement is in a proportion of 445 kg/m ³

9. - The composition according to any of claims 1 to 8, wherein the light aggregate is selected from expanded clays with densities less than 2000 kg/m ³ ,

10. - The composition according to claim 9, wherein the light aggregate is selected from expanded clays with densities less than 1600 kg/m ³ .

eleven . - The composition according to any of claims 1 to 10, wherein the light aggregate is expanded clay sand with a grain size of less than 4 mm and expanded clay gravel with a grain size of less than 10 mm.

12. - The composition, according to any of claims 1 to 1 1, where the light aggregate is in a proportion of between 650 and 850 kg/m ³ .

13. - The composition according to claim 12, where the light aggregate is in a proportion of 698 kg/m ³ .

14. - The composition according to any of claims 1 to 13, wherein the active water-reducing dispersing agent is a concrete superplasticizer.

15. - The composition according to claim 14, where the superplasticizer is in a proportion of between 4.0 and 5.0 kg/m ³ .

16. - The composition according to claim 15, where the superplasticizer is in a proportion of 4.5 kg/m ³ .

17. - The composition, according to any of claims 1 to 16, where the fly ash is type F.

18.- The composition, according to any of claims 1 to 17, where the fly ash is in a proportion of between 80 and 120 kg/m ³

19.- The composition according to claim 18, where the fly ash is in a proportion of 106 kg/m ³ .

20. - Procedure for obtaining the composition, according to any of claims 1 to 19, which comprises the steps of: a) measuring the humidity of the light aggregate and adjusting the amount of water and aggregate with respect to the final composition;

b) adding, in the order described, the water, the active water-reducing dispersing agent, the conventional cement and the fly ash to a kneading device;

c) add the fine aggregate to the mixture obtained in b); and

d) add the coarse aggregate to the mixture obtained in c);

twenty-one . - The procedure according to claim 20, which also comprises a step e) of adding an aerant, after step d) of adding the coarse aggregate.

22. - The procedure, according to any of claims 20 or 21, wherein the mixing device is selected from a vertical axis planetary mixer, a concrete mixer truck or a concrete plant.

23. - Use of the composition, according to any of claims 1 to 19 as a structural concrete coating.

24. Use of the composition, according to claim 23, as a coating of the structural concrete of containment structures.

25. Use of the composition, according to claim 24, as a coating for the structural concrete of nuclear reactors, industrial facilities subjected to high temperatures, storage tanks and deposits, foundations and furnaces.

26. Use of the composition according to claim 25, as a structural concrete lining of a thermal storage tank for a pressurized fluid.

27. Thermal storage tank for a pressurized fluid, whether liquid or gas, comprising an external layer of post-tensioned concrete with a characteristic resistance greater than 50 MPa and an internal layer of refractory concrete that acts as a thermal barrier between the fluid and the post-tensioned concrete, characterized in that the internal layer is composed of the composition described according to any of claims 1 to 19.