EP0746595A1 - Method for partially building and/or repairing at high temperatures industrial facilities including a structure made of refractory materials, and prefabricated element therefor - Google Patents

Abstract

A method for repairing industrial facilities at high temperatures using at least one prefabricated element (1) made of mullite-crystallized refractory product with an alumina content of 30-80%, preferably 50-80%, made of refractory materials securely attached to the structure (11) of the facility by using an oxygen-containing carrier gas stream to spray a mixture of particles capable of exothermically reacting with the oxygen and particles of a refractory material, whereby a coherent refractory mass (14) is formed in situ for attaching said element to said structure.

Description

 "Method of repair and / or partial hot construction of industrial installations comprising a structure of refractory materials and prefabricated element used". The present invention relates to a method of repair and / or partial hot construction of industrial installations comprising a structure of refractory materials, in particular installations operating by indirect heating using flues, such as batteries of furnaces with coke, according to which use is made of at least one prefabricated element made of refractory materials which is secured to said structure by reactive spraying, by means of a current of carrier gas containing oxygen, of a mixture of particles capable of reacting exothermically with oxygen and particles of a refractory material, preferably inert.

As in industrial installations, as defined above, structures made of refractory materials, which are generally of siliceous and silica nature, must always be maintained at a temperature above 300 ° C to avoid their weakening by polymorphic transformation, hot repair methods have long been proposed for their repair. These methods can also be used for partial constructions of such installations, in particular for modifying an existing structure by adding a wall or a flue gas evacuation pipe for example. This is how glassy silica bricks, characterized by a very low coefficient of expansion, have been developed and implemented in a conventional manner to carry out such hot repairs. However, it was found that these repairs were not gas-tight, particularly in the case of coke oven batteries.

French patent FR 2541440-B1 (Glaverbel) describes a hot repair process using, on the one hand, such bricks of vitreous silica and, on the other hand, a ceramic welding process for making the joints of the new masonry as well as the complete reloading of the structure (GB 1.330.894 and GB 2.110.200 A from Glaverbel). In this process, the vitreous silica bricks preferably have a chamfer to facilitate the production of the joints. In another patent using the same ceramic welding process (DE 3643420 Al, Fosbel Europe), the full-thickness repair bricks are this time fitted and then brought to the operating temperature before filling the space between the old and the new masonry by ceramic welding without, however, completely recharging the repaired area by ceramic welding.

In general, although the bricks of vitreous silica, when brought to high temperature, start a slow process of crystallization (in cristobalite and tridymite), they nevertheless keep their sensitivity to creep when they are subjected to a load at high temperature.

This effect is observed in coke ovens where repairs of this type in the vicinity of the flues show noticeable subsidence after some time of commissioning.

One of the essential aims of the present invention is to propose a new method to remedy the aforementioned drawbacks calling into question the reliability of this type of repair or partial construction, and this in a relatively simple and economically justified manner.

For this purpose, according to the invention, one uses, on the one hand, a element prefabricated in a refractory product with mullitic crystallization having an alumina content of between 30 and 85% and preferably between 50 and 80% of alumina, and, on the other hand, a mixture of particles which can react exothermically with oxygen and particles of a refractory material, the composition of which is such as to form in situ a refractory mass which is compatible with the composition and the coefficient thermal expansion of the above-mentioned element and structure to which this mass must be fixed, and this taking into account the stresses to which the latter will be subjected under the working conditions.

Advantageously, according to the invention, for the above-mentioned projection, at least one of the products of the group formed, on the one hand, by the following metals: Al, Si, Mg, is used as particles which can react exothermically with oxygen. , Ca, Fe, Cr, Zr, Sr, Ba and Ti, and, on the other hand, by the compounds of these metals which can, by decomposition, form with oxides derived from these metals, mixed oxides, so as to constitute a binding phase for the aforementioned particles of refractory material. According to a particular embodiment of the invention, for installations comprising heat treatment chambers heated with the aid of flues, the above-mentioned prefabricated element is placed on the side of these and on the side of the heat treatment chamber will apply the aforementioned coherent refractory mass.

The invention also relates to a prefabricated element for the repair or partial hot construction of industrial installations comprising a structure made of refractory materials, in particular installations operating by indirect heating using flues, such as coke oven batteries. , may in particular be suitable for the implementation of the above method.

This prefabricated element is characterized in that it is based on a refractory product with mullitic crystallization having an alumina content of between 30 and 85% and preferably between 50 and 80% of alumina and which preferably has a rectangular prismatic shape, one of the faces of which is provided with means for making a mechanical coupling with a coherent refractory mass formed by reactive projection on this face.

Other details and particularities of the invention will emerge from the description given below, by way of nonlimiting example, with reference to the appended drawings, of some particular embodiments of the method according to the invention and of an element prefabricated for implementing this process.

Figure 1 is a sectional view along line I-I of Figure 2, of a prefabricated element according to a preferred embodiment of the invention. Figure 2 is a front view of the prefabricated element according to this preferred embodiment.

FIG. 3 represents a vertical section of a portion of the wall of a coke oven repaired by the implementation of the method according to the invention.

Figure 4 is a partial horizontal section of a reconstruction of a portion of flues according to the method of the invention.

FIG. 5 represents a graph showing the expansion curve in% as a function of the temperature of different refractory products.

In these figures, the same reference numbers refer to analogous or identical elements. The present invention therefore relates both to the hot repair of industrial installations comprising a structure of refractory materials and to the hot reconstruction of part of such industrial installations and hot modifications to them.

More concretely, the process according to the invention is based on the dissociation of the stresses encountered at the level of the heat exchange wall of a structure made of refractory materials from an industrial installation. Thus, according to the invention, the stresses exerted on this wall are considered, on the one hand, on the heating side where the flues are located, for example, and on the other hand, on the opposite side of this wall where the chamber is located heat treatment.

The invention is therefore applicable in all industrial installations where such a situation occurs. However, since coke ovens constitute industrial installations where repairs to the heat exchange walls must be carried out regularly, the description given below will be limited to this particular application. To physically carry out the above-mentioned dissociation, two separate materials are used at the place where the repair of the wall in question is to take place, which are joined so as to produce a "two-layer" panel at this location. Thus, on the flue side, a refractory product is used that is well suited to the stresses encountered at this location. On the other hand, on the side of the heat treatment chamber, a refractory coating will be formed which is well adapted to the stresses which are specific to it. According to the invention, elements prefabricated in a refractory product with mullitic crystallization having an alumina content of between 30 and 85% and preferably between 50 and 80% of alumina (the remainder being essentially formed of silica), which is secured to the wall to be repaired on the side of the heat treatment chamber by projection, by means of a gas stream carrier containing oxygen, of a mixture of particles of exothermically oxidizable material and particles of a refractory material. The composition of this mixture is chosen in such a way as to form in situ a refractory mass which is compatible with the composition and the coefficient of thermal expansion, on the one hand, of the element and, on the other hand, of the masonry of origin, and this taking into account the stresses to which this mass will be subjected in the working conditions. It has been found that this prefabricated element has the advantage of having good resistance to thermal shock, while guaranteeing high refractoriness, mechanical strength and creep resistance over a wide range of temperatures. Furthermore, unpredictably, it has been found that it is possible, simply by a judicious choice of the components of the mixture and their content in the latter, to form by reactive projection of this mixture a coherent refractory mass, which has excellent compatibility with the prefabricated elements used and the original masonry of the wall to be repaired, whether in terms of thermal expansion, refractoriness or from the point of view of chemical behavior.

In addition, according to the invention, although the refractory mass thus deposited by the reactive projection on the prefabricated elements may have a chemical nature different from that of these elements, this refractory mass constitutes with these elements a very good interface. Advantageously, the aforementioned refractory coating fixing the prefabricated elements in the wall to be repaired is obtained by the projection, by means of a carrier gas rich in oxygen, of a mixture comprising a granular fraction of inert refractory particles based on oxides such that: Si0 ₂ , Al ₂ 0 ₃ , Zr0 ₂ , MgO, Cr ₂ 0 ₃ , Ti0 ₂ , CaO, in different mineralogical varieties and / or associated forms, depending on technological interest, a fraction pulverulent composed of oxidizable particles of metallic nature such as: Al, Si, Mg, Fe, Cr, Zr, Ti and, in certain particular embodiments, such as those described in the international patent application PCT / BE92 / 00012 of the same holder, chemicals which, by decomposition, form, with the oxides from oxidizable particles, mixed oxides so as to constitute a binding phase for inert refractory particles. The term “chemical substance” should be understood to mean in particular metallic peroxides, such as Ca0 ₂ , Mg0 ₂ , Ba0 ₂ , Sr0 ₂ or metallic salts such as A1C1 ₃ , SiCl ₄ , MgCl ₂ .

By refractory particles based on the oxides mentioned, it is necessary to understand their different mineralogical varieties such as tridymite, cristobalite and silica glass for Si0 _{2 as} well as associated forms like zircon ZrSi0 ₄ , spinel MgAl ₂ 0 _A , zirconia stabilized with CaO or MgO, the solid solution Al ₂ 0 ₃ -Cr ₂ 0 ₃ in any proportion, etc ..., which each have a particular technological interest depending on the intended application.

When the aforementioned structure, that is to say the original masonry, is essentially made of siliceous refractory, as is generally the case with the walls of coke ovens, a mixture of oxidizable and refractory particles is used for the projection reactive materials which are chosen in such a way as to form a coherent refractory mass which is also essentially siliceous. According to the invention, it has also been found that by choosing the nature and the relative content of the various oxidizable and refractory components of the mixture to form a refractory mass by reactive spraying which, at working temperature, in particular at 1200 ° C., has an overall relative expansion difference compared to that of the prefabricated element of less than 0.5%, and in particular for repairs or reconstructions extending over at least 2 meters, less than 0.3%, good compatibility with the prefabricated elements defined above is obtained, which ensures perfect adhesion of this mass as well to the old masonry of the wall to be repaired only to the prefabricated elements on which it is applied on the side of the thermal chamber.

The attachment between the projected coherent refractory mass and the prefabricated elements is further favored by providing, on the latter, on the side of the heat treatment chamber, means for carrying out the mechanical attachment between the latter and the projected refractory mass.

The prefabricated element according to the invention, as shown in the figures, in particular in Figures 1 and 2, is formed by a block of rectangular prismatic shape 1, the face 2 of which intended to be directed towards the heat treatment chamber is provided means for carrying out, in addition to the ceramic connection obtained by reactive spraying, a mechanical coupling with the refractory mass applied to this face 2. In this particular embodiment these means are formed by a notch 3 in the form of a mortise extending parallel to the longitudinal edges of this block over the entire length of the latter and substantially in the middle of its face 2.

In addition, this block advantageously has, at its upper 4, lower 5 and lateral 6 and 7 sides, corresponding nesting means, so as to allow precise and stable dry stacking of several blocks 1 on each other. . As shown in FIGS. 1 to 3, these interlocking means are: at the lower 5 and lateral 7 faces, a groove 8 also extending over the entire length of these faces and, at the opposite upper 4 and lateral 6 faces, a rib corresponding 9 can engage in a groove 8 of a superimposed block. Below are given concrete examples of embodiment allowing the object of the invention to be illustrated further.

Example 1 This example concerns the repair of a partition wall between flues and a thermal chamber of coke ovens as shown diagrammatically in FIG. 4 appended.

The damaged area of the wall to be repaired was first cleaned so as to free the healthy parts of its structure.

The wall to be repaired had a total thickness of 11 cm, while the thickness of the blocks 1 was 5 cm. The repair or the actual reconstruction started with the face on the side of the flue 10. Prefabricated blocks 1, as shown in FIGS. 1 and 2, having an alumina content of the order of 50%, were laid dry. one on the other so that the rib of a given block engages in the groove of an adjacent superimposed block.

Once the building in mullitic blocks erected, the junction between the new masonry, formed by these blocks 1, and the old masonry 11 of the wall as well as the covering of the face 2 of the blocks directed towards the heat treatment chamber 12 were produced by reactive spraying in an oxygen stream containing 13% by weight of Si with an average diameter of 20 microns, 12% by weight of Ca0 ₂ with an average diameter of 10 microns and 75% of Si0 ₂ , in the form of tridymite and cristobalite with an average diameter of 300 microns.

This reactive projection was continued until the total thickness of the repaired area of the wall had the same thickness as the wall to be repaired. Thanks to the good resistance to thermal shocks of the mullitic blocks 1, according to the invention, these could have been brought directly from room temperature to the place of installation. The repaired area, which restored the profile and thickness of the old masonry 11, therefore consisted of masonry 13 of mullitic nature on the side of the flue 10 and of a siliceous refractory layer 14 formed by reactive projection, firmly linked to blocks 1 by ceramic connection and mechanical anchoring in the notches 3 on the side of the heat treatment chamber.

Figure 4, which is a partial horizontal section, shows a variant of this example 1 and relates to the partial reconstruction of a flue 10. This variant is somewhat different from the example shown in Figure 3 by the fact that 'A connection must be made between the repaired area and the transverse walls 15 of the flue 10.

To do this, the blocks 1 are cut to size and bevel so as to be able to form at the place where the transverse walls join the partition wall with the heat treatment chamber 12 a slot 16 with inclined edges in which the refractory mass 14 formed by reactive projection can easily be introduced to link the transverse walls to the above-mentioned partition wall, and in particular to the blocks 1 used for repairing the latter.

Example 2 This example mainly concerns the repair of large areas of a heat exchange wall between flues and a heat treatment chamber. It can therefore be as well the case illustrated by FIG. 3 as that illustrated by FIG. 4. Since the repair block 1, for example for a coke oven, must both resist thermal shocks during the pose and get closer on the plan of the expansion, of the behavior of the original masonry 11 in silica bricks and that of the refractory layer 14 formed by reactive projection, it was found, in a rather unforeseen manner, as already indicated above, that a block 1 of mullitic nature represents an interesting compromise to satisfy these two conflicting requirements.

However, when the length of the area to be repaired is large (several meters), a variant of the invention consists in using a mixture of repair to be sprayed, in which part of the refractory charge has been replaced. crystallized silica (cristobalite and tridymite) with a fraction of vitreous silica, the particle size of which is between 100 and 500 μm and preferably between 200 and 400 μm.

The graph shown in Figure 5 gives different expansion curves for the products involved in the repair and hot reconstruction of industrial installations. Thus, curve A relates to the expansion in% as a function of the temperature of a crystallized silica brick, curve B relates to the refractory mass 14 obtained by reactive spraying of a mixture corresponding to the formulation given in Example 1, curve C is that of the mullitic block 1, curve D is that of a glassy silica brick and, finally, curve B 'is that of a refractory mass obtained by reactive projection of a mixture corresponding to the following formulation : Components Weight (%) Average particle diameter (μm)

If 13 20

Ca0 ₂ 12 10

Si0 ₂ crystallized 50 300 (Tridymite + cristo¬ balite)

Si0 ₂ glassy 25 300 This set of expansion curves shows that curves A and B practically coincide so that hot repair of silica bricks can be expected, on which a refractory mass obtained from the above mixture is formed. free of vitreous silica, will not present any problem from the dilation point of view.

On the other hand, if we consider curves B and C we see that there is a relatively large difference between these two curves.

It has, however, been observed, according to the invention, and as it follows from Example 1, that despite this deviation, in an entirely unpredictable manner, practical tests have shown that there is perfect compatibility between the two products concerned for the envisaged conventional repairs and reconstructions.

If we consider, finally, the curve B ', we note that the addition of vitreous silica to the mixture to be sprayed makes it possible to considerably reduce the difference between curve C of the mullitic block and curve B' relating to the sprayed mixture.

Consequently, the benefit of this addition is to reduce the mechanical stresses, at the working temperature, which can result from a thermal detuning on a long interface, and this without this addition having a negative influence on the mechanical properties of the repaired area.

It is understood that the invention is not limited to the particular embodiments of the concrete examples but that other variants can be envisaged within the framework of the invention, as well as regards the shape and the dimensions of the Mullitic blocks and the means for carrying out the possible mechanical anchoring of the projected refractory mass 14 on the face 2 of these blocks. Thus, the mortise-shaped notch 3 does not, for example, necessarily have to extend to the longitudinal edges of the face 2, but could for example extend obliquely or perpendicularly to these edges. Thus, instead of forming continuous grooves across the entire length of the repaired surface, the notches 3 in the assembled blocks could form interrupted grooves.

It is the same for the mixture of particles intended to form, by reactive projection, the refractory mass 14 on the face 2 of the blocks 1, which could vary within wide limits. In fact, both the chemical and physical nature of the particles entering this mixture as well as the relative ratio of the quantities used for each of the components of this mixture can vary within relatively wide limits as long as care is taken to avoid this mass projected refractory may by chemical reaction degrade the blocks 1 and that the total expansion of this mass and of the blocks at working temperature cannot cause the refractory mass to fall off on the blocks 1. The permissible difference between these expansions largely depends part of the surface to be repaired. Thus, for relatively small areas, a larger deviation is allowed only when the area to be repaired is relatively large, where it is necessary to ensure that the expansions are as close as possible to each other. Finally, the prefabricated element 1 may have a hole, preferably of rectangular section, facilitating the manipulation of the element during its installation.

Claims

1. Method for repair and / or partial hot construction of industrial installations comprising a structure made of refractory materials (11), in particular installations operating by indirect heating using flues (10), such as oven batteries with coke, according to which use is made of at least one prefabricated element (1) made of refractory materials which is secured to said structure (11) by projection, by means of a current of carrier gas containing oxygen , of a mixture of particles which can react exothermically with oxygen and of particles of a refractory material, so as to form in situ a coherent refractory mass (14) allowing the above-mentioned element to be fixed to the structure of refractory materials, characterized in that, on the one hand, a prefabricated element (1) is used in a refractory product with mullitic crystallization having an alumina content of between 30 and 85% and of preferably between 50 and 80% of alumina, and, on the other hand, a mixture of particles which can react exothermically with oxygen and particles of a refractory material, the composition of which is such as to form a refractory mass in situ. (14) which is compatible with the composition and the coefficient of thermal expansion of the above-mentioned element (1) and of the structure (11) to which this mass (14) must be attached, and this taking account of the stresses to which the latter will be subject to the working conditions.

2. Method according to claim 1, characterized in that at least one of the products of the group formed, on the one hand, by the following metals, is used for the aforementioned spraying, as particles capable of reacting exothermically with oxygen: Al, Si, Mg, Ca, Fe, Cr, Zr, Sr, Ba and Ti, and, on the other hand, by the compounds of these metals which, by decomposition, can form with oxides derived from these metals, mixed oxides, so as to constitute a binding phase for the aforementioned particles of refractory material.

3. Method according to claim 2, characterized in that one uses as compounds of the aforementioned metals, at least one of the peroxides of the group formed by Ca0 ₂ , Mg0 ₂ , Ba0 ₂ , Sr0 ₂ and / or salts of these metals such as 1Α1C1 ₃ , SiCl, MgCl ₂ .

4. Method according to any one of claims 1 to 3, characterized in that one uses for the aforementioned projection as particles of refractory material, at least one of the oxides chosen from the group comprising Si0 ₂ , Al ₂ 0 ₃ , Zr0 ₂ , MgO, Cr ₂ 0 ₃ , Ti0 ₂ , CaO.

5. Method according to any one of claims 1 to 4, characterized in that, when the aforementioned structure is essentially in siliceous refractory, use is made of a mixture of oxidizable and refractory particles making it possible to form a coherent mass in refractory also essentially siliceous.

6. Method according to any one of claims 1 to 5, characterized in that use is made of a mixture of oxidizable and refractory particles which, by projection by means of a current of carrier gas, makes it possible to form a coherent refractory mass exhibiting an overall relative expansion difference at 1200 ° C. compared to that of the prefabricated element of less than 0.5% and, in particular for repairs or reconstructions extending over at least 2 meters, less than 0, 3%

7. Method according to any one of claims 1 to 6, characterized in that, for installations comprising heat treatment chambers (12) heated using flues (10) the side of the latter is placed. prefabricated element (1) above and on the side of the heat treatment chamber (12) is applied the coherent refractory mass (14) above.

8. Method according to claim 7, characterized in that the refractory mass (14) is applied in the form, on the one hand, of a seal and connection between the prefabricated element (1) and the aforementioned structure (11), and, on the other hand, a coating covering the aforementioned prefabricated element on the side of the heat treatment chamber (12).

9. Method according to claim 8, characterized in that use is made of a prefabricated element (1) having on the side of the heat treatment chamber (12) means (3) for achieving a mechanical coupling between this element (1) and the aforementioned refractory mass (14).

10. Method according to claim 9, characterized in that these means comprise at least one notch (3) substantially in the form of a mortise.

11. Method according to any one of claims 1 to 10, characterized in that, when use is made of several superimposed prefabricated elements (1), the latter have at their contact faces (4, 5) means d 'nesting (8, 9).

12. Method according to any one of claims 8 to 11, characterized in that one carries out by means of the aforementioned prefabricated element (1) and a coating formed of the aforesaid refractory mass (14) a wall or portion of wall of which at most half the thickness is formed by the prefabricated element (1) and the other part of this thickness is formed by the aforementioned coating (14) covering this element (1) on the side of the heat treatment chamber.

13. Prefabricated element for the repair or partial hot construction of industrial installations comprising a structure made of refractory materials, in particular installations operating by indirect heating using flues (10), such as coke oven batteries, in particular for the implementation of the method according to any one of the preceding claims, characterized in that it is based on a refractory product with mullitic crystallization having an alumina content of between 30 and 85% and preferably between 50 and 80% of alumina. .

14. Prefabricated element according to claim 13, characterized in that it has a rectangular prismatic shape, one of the faces (2) of which is provided with means (3) for achieving mechanical attachment with a coherent refractory mass (14) formed by projection. reactive on this face (2).

15. Prefabricated element according to claim 13 or 14, characterized in that it has, on at least two of its opposite faces (4, 5) corresponding fitting means (8, 9).