NL8000744A - PROCESS FOR PROCESSING A PROCESS TO PROCESS, STORAGE REFRACTORY ALMOST ODOR-FREE MASS. - Google Patents

Description

Br / O / lh / 64

Method for the preparation of a directly processable, refractory, virtually odorless mass to be stored.

The invention relates to a process for the preparation of an immediately processable, refractory, virtually odorless mass, in which a formulation based on granular burned bauxite, corundum, chamotte and mixtures thereof is added as an additive, clay and an acid phosphate solution as binder. wherein the additive contains ground sulfur and / or phosphorus components and optionally metal grinding.

Refractory masses based on granular additives, such as chamotte, silimanite, bauxite and cow-beef, a fine pipe-earth-containing material, such as calcined or non-calcined clay and an acid phosphate binder, are known. Such masses are used in the form of directly processable, storable stamping masses and refractory sealants. They excel in use because of their great mechanical strength and especially very good slag resistance. There are also known casting compositions which, in addition to the granular aggregate stopper, fine clay-containing material and phosphate binder, also contain a curing agent, such as melting magnesia and calcium aluminate cement. The masses are distinguished by their fast curing and great strength.

Various measures have been proposed to prevent the ligation reaction of such masses with phosphate binders during storage and to allow the masses to be stored for more months to more than half a year. According to German patent specification 23 33 351, the addition of oxalic acid and / or glycerol is added in order to slow down the ligation reaction in the presence of monoaluminum phosphate. In addition to oxalic acid, other acids such as citric, tartaric, succinic and gluconic acids are used to slow down the reaction between the phosphoric acid and the refractory raw materials (Am. Ceram. Soc. Buil. 661-665 (1966)). . In addition, a reaction product of monoaluminum phosphate and ethanolamine must be added as binder to clay-containing refractory compositions according to German patent specification 26 38 592.

However, in the preparation of clay-containing masses with the phosphate agent monoaluminum phosphate in the form of 50% solution or technical phosphoric acid, it has been found that with certain granular additives the preparation, storage, processing and. hardening of the masses deteriorate.

During the mixing of the components and also during long storage times, a long-lasting excessive development of 10 harmful gases, such as H 2 S and PH 2, took place, the storage times became short and the processing, binding and strength does not. The aforementioned drawbacks often occurred with additives, such as chamotte, bauxite and corundum, which, due to their pre-treatment with heat, contain sulfur and / or phosphorus-reduced components in the form of a sintering. In addition, the aforementioned additives also contain fine metal grinding, which is produced by grinding in crushing and grinding devices lined with steel. In addition, the use of the aforementioned additives 20 in the presence of the acidic binder solution released H2S and residual gases, which can be determined qualitatively and quantitatively with a carrier tube.

The invention provides a process for the preparation of an immediately processable, refractory, substantially odorless mass, in which reduced components of sulfur and / or phosphorus and optionally a metal pulp containing additive of chamotte, bauxite and corundum are used.

According to the method of the invention, the formulation 0.3-3 wt% 30% hydrogen peroxide ((^ C ^) is added and the mixing is carried out at room temperature until the end of the oxidation reaction. In another embodiment of the process of the invention, after first mixing, 0.1-0.5 wt.% Potassium-35 permanganate (KMnO2) can be added, after which the whole is mixed until the oxidation reaction has expired. Also advantageous is the addition of 0.3-1 wt.% 30% hydrogen peroxide and 0.1-0.5 wt.% Potassium permanganate.

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When the method of the invention is used, there is no strong development of gases harmful to health which contain odor, H 2 S and PH 2, when the mass is mixed and stored, the storage time is increased or the processing property of the mass clearly improved and a refractory lining element of high strength is obtained in connection therewith at the place of processing.

The mass of the invention to be processed directly may be in the form of a stamping or casting mass or of a refractory sealant, the forms of which are known in a known manner, in particular distinguished by the granularity of the additive and the moisture content or the processing properties. In addition to the granular additive, refractory clay and, as a binder, technical phosphoric acid and / or monoaluminum phosphate must be added in the form of a 50% solution. The amounts of binder, hydrogen peroxide, potassium permanganate and the rest of the water are each based on the amount of the dry admixture-clay mixture.

In addition to or as a partial replacement for the refractory clay, it can be assumed known that fine calcined pipe clay can be used to increase the refractory properties of the mass.

The invention is elucidated on the basis of Examples 1-8 and 9-14, the data of which in the tables, respectively. A and B are included. Bauxite, roasted chamotte and corundum are used as additives, the quantity of H2S and PH2-containing gases being determined of the additives with reduced components of sulfur and / or phosphorus. This is done with a gas pump, in which the reagent in the tube for testing i ^ S contains a mercury complex and which for the testing of PH2 consists of a gold compound (carrier tube).

For the processing of mortar and sealant, the weft depth, as determined according to Schuier, is used as a measure immediately after preparation and after a longer storage time. For the determination, a cylinder with a diameter of 25 mm, provided with a guide rod, with a total weight of approximately 35 kg, is used, after the drop of which cylinder from a height of 100 mm has the impact depth in the sample. pole.

-4-

For the processability of the mashed potatoes 5 immediately after preparation and after long storage, the measure used is the compactibility with the Fischer ram. A cylinder with a diameter of 50 mm and a height of approximately 50 mm is punched from the mass with a punch of 6.5 kg from a height of 50 mm. The height of the cylinder is determined after 4 rams or strokes 10 (2 on each of the end faces of the cylinder) and then again after a total of 10 strokes (+ 3 on each of the end faces of the cylinder). The height after 10 strokes, based on that after 4 strokes, expressed in percent, is considered to be compressibility.

In the examples, each of the components of the mass is given in weight percent.

The refractory kit of Example I with corundum as an additive without reduced ingredients exhibited satisfactory storage and processing properties. However, no matter how little, a gas evolution had been observed in the preparation. In Examples 2.5 and 9, the mixtures showed a very strong development of harmful gases and an unsatisfactory shelf life. The other examples concern formulations of refractory sealants, stamping masses and a casting mass of the invention, which were practically free from harmful gas developments, which were easy to process and also had a sufficient shelf life. In. Example IV of the invention 2% 30% hydrogen peroxide was added, which amount was considered optimal in view of the properties of the mortar. Finally, examples 7, 10 and 11 show the advantage of using potassium permanganate. Different additives are used in Examples 8 and 13. Example XIV shows the formulation of a casting mass of the invention, wherein the part a with calcium aluminate cement as a hardener in dry form and the part b in liquid form are mixed together, immediately followed by molding and curing the mass.

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Claims (5)

1. A process for the preparation of an immediately processable, refractory, substantially odor-free mass, in which a formulation based on granulated bauxite, corundum, chamotte and the mixture thereof as an additive, clay and acid phosphate solution as binder is used. mixed, the addition containing reduced sulfur and / or phosphorus components and optionally metal grinding, characterized in that 0.3-3 wt.% of 30% hydrogen peroxide is added to the formulation, after which the whole is heated at room temperature , mixed until the oxidation reaction is finished. 2. Process according to claim 1, characterized in that after being first mixed, 0.5% by weight of potassium permanganate is added to the formulation and the mixing is carried out at room temperature until the oxidation reaction has ended. A method according to claim 1 or. 2, characterized in that 0.3-1 wt.% 30% hydrogen peroxide and 0.1-0.5 wt.% Potassium permanganate are added to the formulation. 4. Instantly processable, refractory, substantially odorless mass to be stored, obtained by the method of claims 1-3. 5. Articles and constructions, provided with elements of the mass of claim 4. 8000744