ES2525416B1 - RESIDUE OF SANITARIES FOR THE DEVELOPMENT OF CEMENTS, PROCEDURE OF OBTAINING AND CEMENTS THAT UNDERSTAND IT - Google Patents

Abstract

Residue of sanitary ware for the manufacture of cements, procedure for obtaining and cements that comprise it. # The present invention describes a waste obtained from the sanitary ware or landfill industry or from recycling plants as a pozzolanic component of cements. A method of obtaining these sanitary waste and another method of manufacturing cements (common cements and white cements) using this waste is also presented. This type of waste is collected directly in the industry that produces sanitary ware ceramics, in landfills or in recycling plants, where its management is carried out. With this invention a possible commercial outflow to this waste could be facilitated.

Description

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DESCRIPTION

Residue of sanitary ware for the elaboration of cements, procedure of obtaining and cements that comprise it.

SECTOR OF THE TECHNIQUE

The present invention is framed in the construction sector, and more specifically in the cement industry, which forced by a foreseeable decrease in the materials currently used and a hardening of national and international environmental policies will demand alternative products, which present technological advantages , environmental and economic viable for the sector.

STATE OF THE TECHNIQUE

Sanitary waste can have two origins: a) Of the ceramic sanitary ware industry that are constituted by those products rejected for sale that do not meet the requirements demanded by the manufacturer and; b) Landfills or recycling plants that are constituted by those products from the rehabilitation or renovation of homes, industries, etc.

In the manufacturing process of ceramic products, natural materials are used as raw material, which contain a high proportion of clay minerals, which by means of a dehydration process, followed by another controlled cooking at temperatures between 700 ° C and 1290 ° C acquire its characteristic properties of "cooked clay". Therefore, the manufacturing process of the ceramic materials itself entails high cooking temperatures, which can lead to the activation of clay minerals, providing pozzolanic activity to them.

The incorporation of these sanitary waste in the manufacture of cements would allow the concept of sustainability to be introduced in the construction sector, a sector that is traditionally considered as disrespectful of the environment, thus being in line with European and national policies sustainable development.

The present invention describes a new use of sanitary waste for the manufacture of common cements and white cements.

BRIEF DESCRIPTION OF THE INVENTION

An object of the invention is a waste based on sanitary ware products directly from the sanitary ware or landfill industry, which has a pozzolanic activity and a particle size of less than 63 pm. It has been observed that the fineness of the material is decisive in its pozzolanic activity.

Another object of the invention is the process for obtaining sanitary waste of the invention, which comprises the following steps:

a) collection of starting waste in the ceramic sanitary ware industry or from landfills or recycling plants,

b) drying the residue of a) in an oven at 105 ° C to constant weight, to facilitate the crushing and grinding process,

c) crushing or milling of the residue of b) the time necessary to obtain a size less than 63 pm, which is considered suitable for use as a pozzolanic material and

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d) sieving the residue of c) with a sieve of 63 | jm to obtain the homogeneous sanitary waste.

Another object of the invention is the common or white cement, hereinafter cement of the invention, which comprises the sanitary waste of the invention as a component in said cement in a percentage of between 0.1% and 55%.

In a preferred embodiment of the invention the common cement comprises the sanitary waste as the main component in said cement in a percentage of between 6% and 55%.

In another preferred embodiment of the invention the common cement comprises the sanitary waste as an additional minor component in said cement in a percentage of between 0.1% and 5%.

In another preferred embodiment the white cements manufactured comprise the sanitary waste as the main component in said cement in a percentage of between 6% and 55% or as an additional minor component in said cement in a percentage of between 0.1% and 5% and have a value of the parameter L * of the CIELAB coordinates greater than or equal to 85.

Another object of the invention is the process for obtaining the cement of the invention, hereinafter the method of the invention, which comprises the following steps:

a) mixing the sanitary waste of the invention with a cement in a proportion between 0.1% and 55% to ensure proper homogenization, and

b) storage of the mixture of a) in a sealed place to avoid carbonation and humidification thereof.

DETAILED DESCRIPTION

The present invention is based on the fact that it has been observed that from sanitary waste (Figure 1) it is possible to obtain a product that acts as a pozzolanic material useful as an additive for the manufacture of cements when prepared as a homogeneous product, with a fine grain size less than 63 pm (particle size similar to cement) (Figure 2). This waste can come from the ceramic sanitary ware industry, constituted by those products rejected for sale that do not meet the requirements demanded by the manufacturer, and from landfills or recycling plants, constituted by those products from the rehabilitation or housing, industry, etc. reforms and can thus offer a commercial outlet to this waste material.

This sanitary waste (Figure 2), is introduced into the cements as the main component (6-55% by mass) and is framed within natural calcined pozzolans (Q) and also as a minor component (percentages below 5% by mass) , provided that it is not already included as a majority component. With this product, different types of cements can be obtained, depending on the dosages made, being also possible for the use of white cements.

The sanitary waste described in the present invention can be considered as calcined natural pozzolans, where according to the UNE-EN 197-1: 2011 standard (Spanish Standard UNE-EN 197-1: 2011 "Cement. Part 1: Composition, specifications and conformity criteria of common cements ", December 2011), calcined natural pozzolans (Q) are defined as materials of volcanic origin, clays, slates or sedimentary rocks activated by heat treatments and in accordance with section 5.2.3.1. pozzolanic materials P, Q).

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These calcined natural pozzolans, as set out in section 5.2.3.1. of the UNE EN 197-1 standard, they are characterized by being essentially composed of silicon dioxide (> 65% by mass) and aluminum oxide (> 20%), as well as iron oxide and other minor oxides. In addition, they are characterized by having a reactive silicon dioxide content greater than 25% by mass (> 45% by mass). The chemical composition of these sanitary waste is in line with the above, as indicated in the values shown within the parentheses.

In this way and according to the UNE-EN 197-1: 2011 standard, they could be used as the main component (percentages up to 55% by mass) in the manufacture of cement CEM ll / AQ, CEM ll / BQ, CEM IV / A, CEM IV / B, CEM V / A and CEM V / B, and can also be used as a minor component (percentages below 5% by mass) giving rise to any of the main types of cement (CEM I, CEM II, CEM III, CEM IV and CEM V) provided that it is not already included as a majority component.

In addition, according to the UNE 80305: 2012 and UNE-EN 197-1: 2011 standard, with these sanitary wastes, homologous white cements type BL ll / AQ, BL ll / BQ, IV / can be obtained depending on the dosages A, BL IV / B and BL V or cements of any type (BL I, BL II, BL III, BL IV and BL V) if used as minor components.

Thus, an object of the invention is a sanitary waste useful for the manufacture of cements, hereinafter a sanitary waste of the invention, which possesses a pozzolanic activity and a particle size suitable for this purpose with a particle size of less than

63 pm

Another object of the invention is the procedure for obtaining the waste of toilets of the invention, hereinafter procedure for obtaining the waste of toilets of the invention, which comprises the following steps:

a) collection of starting waste in the ceramic sanitary ware industry or from landfills or recycling plants,

b) drying the residue of a) in an oven at 105 ° C to constant weight, to facilitate the crushing and grinding process,

c) crushing or grinding the residue of b) the time necessary to obtain a size less than 63 pm, which is considered suitable for use as a pozzolanic material, and

d) sieving the residue from c) with a 63 pm sieve to obtain the homogeneous sanitary waste.

The cements with which the invention was made are a gray Portland cement of resistant class 42.5 R and a white common cement of resistant class 52.5 R according to UNE-EN 197-1: 2011, although it is not limiting; The difference in the use of one cement or another will influence the final performance, and the final behavior of the invention can be adapted to the characteristics of the cement used.

Also, if the process of incorporation of sanitary waste was carried out directly in the cement factory, these could be added and ground together with the clinker, in the appropriate percentages for the manufacture of the different types of common cements of the UNE-EN 197-1: 2011 standard.

Another object of the invention is cement, hereinafter cement of the invention, which comprises the sanitary waste of the invention as a component in said cement in a percentage of between 0.1% and 55%.

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In a preferred embodiment of the invention the common cement comprises the sanitary waste as the main component in said cement in a percentage of between 6% and 55%.

In another preferred embodiment of the invention the common cement comprises the sanitary waste as an additional minor component in said cement in a percentage of between 0.1% and 5%.

In another preferred embodiment the white cements manufactured comprise the sanitary waste as the main component in said cement in a percentage of between 6% and 55% or as an additional minor component in said cement in a percentage of between 0.1% and 5% and have a value of the parameter L * of the CIELAB coordinates greater than or equal to 85.

Another object of the invention is the process for obtaining the cement of the invention, hereinafter procedure for obtaining the cement of the invention, which comprises the following steps:

a) mixing the sanitary waste of the invention with a cement in a proportion between 0.1% and 55% to ensure proper homogenization, and

b) storage of the mixture of a) in a sealed place to avoid carbonation and humidification thereof.

Another particular object of the invention is the process for obtaining cement where the proportion between sanitary waste and the cement of a) meets the following formula:

fTltotal - ^ cement ^ residue

mcement - rTlfotal (1 “X)

^ residue - X mj0ja |

being:

Rritotai '■ total mass of the mixture to be made mcement - mass of cement used, mass - mass of the toilet waste.

- X: percentage in terms of one toilet waste.

BRIEF DESCRIPTION OF THE FIGURES

Figure 1. Initial aspect of the sample of ceramic sanitary ware.

Figure 2. Appearance of the milled and screened sample below 63 pm.

Figure 3. Graph showing the compressive strengths obtained in mortars made with 20% and 30% dosing at the ages indicated.

Figure 4. Graph showing the flexural strengths obtained in mortars made with 20% and 30% dosing at the ages indicated.

Figure 5. Graph showing the solubility curve of calcium oxide at 40 ° C and the values corresponding to the gray cement cement pozzolanicity test at the ages of 8 and 15 days, carried out for the invention with a 20% and 30% dosage. Figure 6. Graph showing the solubility curve of calcium oxide at 40 ° C and the values corresponding to the pozzolanicity test of common white cements at the ages of 8 and 15 days, carried out for the invention with 20% and 30% dosage.

EXAMPLES OF EMBODIMENT OF THE INVENTION

In this example of the invention a mixture of cement with sanitary waste is carried out as a component. Sanitary waste (Figure 1), could act in the

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cements as the main component (6-55% by mass) and would be framed within calcined natural pozzolans (Q) and also as a minor component (percentages below 5% by mass), provided that it is not already included as a majority component, according to the UNE-EN 197-1: 2011. with this sanitary waste of the invention can be obtained, depending on the dosages made, cements of type CEM ll / AQ, CEM ll / BQ, CEM IV / A, CEM IV / B, CEM V / A and CEM V / B, or cements of any type (CEM I, CEM II, CEM III, CEM IV and CEM V) if used as minority components. Also, with these sanitary residues, depending on the dosages made, homologous white cements type BL ll / AQ, BL ll / BQ, IV / A, BL IV / B and BL V or cements of any type can be obtained (BL I , BL II, BL III, BL IV and BL V) if used as minor components, according to the UNE 80305: 2012 and UNE-EN 197-1: 2011 standards.

To study the conformity of this sanitary waste with the standard and its possibility of being used as a pozzolanic material, it was collected directly from the ceramic sanitary ware industry or from landfills or recycling plants. It was then conditioned, based primarily on drying the sample in an oven at 105 ° C. Subsequently, the material was crushed, reducing its size and facilitating subsequent grinding in a ring mill. Once this milling was achieved, the sample was sieved to obtain a homogeneous product, with a fineness lower than 63 pm, similar to that of cement, as can be seen in Figure 2.

The chemical composition of the sanitary waste thus obtained is characterized by being essentially composed of silicon dioxide (> 65% by mass) and aluminum oxide (> 20%), as well as iron oxide and other minor oxides. In addition, they are characterized by having a reactive silicon dioxide content greater than 25% by mass (> 45% by mass).

For use as an active addition to the cement, it is necessary to perform a grinding and sieving of the material, obtaining a homogeneous product, with a fineness of less than 63 pm, as can be seen in Figure 2.

Subsequently, the different cements are manufactured that must meet the mechanical, physical and chemical requirements required in points 7.1, 7.2 and 7.3 of the UNE EN 197-1: 2011 standard, respectively. Additionally, in the case of homologous white cements, they must comply with the additional physical requirement of whiteness required in 7.1.2. of the UNE 80305: 2012 standard.

Regarding the mechanical properties of gray portland cements type ll / AQ, type ll / B-Q and type IV / A that contain this sanitary material as a main component in a percentage between 6% - 20%, 21% - 30% and 11% - 30% by mass, respectively, could be used to manufacture Portland cements with a strength class 32.5 (N and R) and 42.5 (N and R), according to the mechanical requirements set out in Table 3 of the UNE standard EN 197-1: 2011. When its content is between 31% - 35% by mass, portland cements type ll / BQ and type IV / A could be used to manufacture cements of a strength class 32.5 (N and R), 42.5 N, complying with the requirements mechanics established in the table indicated above. When the content is between 36% -55% by mass, CEM IV / B and CEM V / B type cements, resistant classes of 32.5 N could be achieved.

As for homologous white cements type ll / AQ, type ll / BQ and type IV / A containing as main component this white sanitary ceramic material in a percentage between 6% - 20.21% - 35% and 11% - 35% by mass, respectively, could be used to manufacture white cements with a strength class 32.5 (N and R), 42.5 (N and R) and 52.5 (N and R), according to the mechanical requirements established in Table 3 of the UNE standard EN 197-1: 2011. When the content is between 36% - 55% by mass, the

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Cements BL IV / B and type BL V / B can be achieved resistant classes of 32.5 N. Figures 3 and 4 show the results obtained with different cements manufactured with the sanitary waste.

As for the physical requirements (setting time and volume stability), obtained according to UNE EN 196-3: 2005 + A1: 2009, it is obtained that gray and white portland cements type II (AQ and BQ) and type IV / A that contain this sanitary waste as the main component, comply with the specifications set out in table 3 of the standard indicated above, presenting set times greater than 60 minutes and an expansion of less than 10 mm.

Regarding the additional physical requirement of whiteness; required in point 1.1.2 of the UNE 80305: 2012 standard for white cements; It has been determined according to the UNE 80117: 2012 standard. All white common cements type ll / AQ (6% - 20% by mass), type ll / BQ (21% - 35% by mass) and type IV / A (11% - 35% by mass) which they incorporate as a component The main ceramic material has a value of the parameter L * of the CIELAB coordinates greater than or equal to 85, thus fulfilling the requirement established by the UNE 80305 standard of white cements (Table 1).

Table 1. Results of luminosity

 Cement type

 L *

 White Cement BL 52.5 R

 92.77

 White cement with 10% by mass of white sanitary waste

 91.70

 White cement with 20% by mass of white sanitary waste

 90.82

 White cement with 30% by mass of white sanitary waste

 88.88

In relation to the chemical requirements for the content of chlorides and sulfates determined according to the methodology described in the UNE EN 196-2: 2006 standard, it was obtained that the cements containing this sanitary waste as the main component comply with the requirements established in Table 4 of the UNE EN 197-1: 2011 standard, as shown in Table 2.

Table 2. Chloride and sulfate content of the cements containing as a component ______________________ main the waste of sanitary ware ______________________

 Cement type

 Main component (% toilet waste) Property (% by mass of final cement)

 Chloride content

 Sulfate content (S03)

 EMC ll / A-Q

 6-20 0.00- 0.001 3.48-2.97

 EMC ll / B-Q

 21 -35 0.001 - 0.001 3.48-2.94

 EMC IV / A

 11-35 0.001 - 0.001 3.30-2.43

 EMC IV / B

 36-55 0.001 -0.002 2.39-1.70

 EMC V / A

 18-30 0.001 -0.001 3.05-2.61

 EMC V / B

 31 -49 0.001 -0.002 2.57-1.92

 BL ll / A-Q

 6-20 0.014-0.013 2.73-2.33

 BL ll / B-Q

 21 -35 0.012-0.011 2.31 - 1.91

 BL IV / A

 11-35 0.014-0.011 2.59-1.91

 BL IV / B

 36-55 0.010-0.009 1.88-1.34

 BL V / A

 18-30 0.013-0.011 2.39-2.05

 BLV / B

 31 -49 0.011-0.009 2.02-1.51

 Maximum content according to UNE EN 197-1: 2011 standard

 <0.10 <3.5-4

In addition to these chemical requirements, the UNE EN 197-1: 2011 standard establishes that CEM IV type pozzolanic cements must comply with the property of pozzolanicity, according to the test described in UNE EN 196-5: 2011. Type IV cements containing 5 as a main component this sanitary ceramic residue between 18% - 35% by mass and 11% - 35% by mass meet this requirement at 8 and 15 days, respectively (Figure 5 and 6).

Claims (9)

5 10 fifteen twenty 25 30 35 40 Four. Five fifty ES 2 525 416 Al 1. Residual of sanitary ware from the ceramic industry of sanitary ware or of the dumps or recycling plants and useful for the elaboration of cements characterized because it has pozzolanic activity and a granulometry of less than 63 pm. 2. Procedure for obtaining the sanitary waste according to claim 1 characterized in that it comprises the following steps: a) collection of sanitary waste from the ceramic sanitary ware industry or from landfills or recycling plants, b) drying the residue of a) in an oven at 105 ° C to constant weight, c) crushing or grinding the residue of b) the time required to obtain a size less than 63 pm, and d) sieving the residue of c) with a 63 pm sieve to obtain the sanitary waste homogeneous. 3. Cement characterized in that it comprises the sanitary waste according to claim 1. 4. Cement according to claim 3 characterized in that the sanitary waste is comprised between 0.1% and 55% as a component in said cement. 5. Cement according to claim 4 characterized in that the sanitary waste is comprised between 0.1% and 5% as a component in said cement. 6. Cement according to claim 4 characterized in that the sanitary waste is comprised between 6% and 55% as a component in said cement. 7. Cement according to claim 4, characterized in that the sanitary waste has a value of the parameter L * of the CIELAB coordinates greater than or equal to 85. 8. - Procedure for obtaining the cement according to claims 3 to 7, characterized in that it comprises the following steps: a) mixing the sanitary waste according to claim 1 with a cement in a proportion between 0.1 and 55% to ensure proper homogenization, and b) storage of the mixture of a) in a sealed place to avoid carbonation and humidification thereof. 9. Method according to claim 8 characterized in that in the mixing stage the proportions between the sanitary waste and the cement meet the following formula: f ^ total - ^ cement ^ waste ^ cement - total (EX) ^ residue - X mtotal being: mtotai: total mass of the mixture to be made mcemento '■ mass of cement used mmSiduo- mass of the toilet waste. X \ percentage as much for one toilet waste.