FI108790B - Titanium-containing additive and its use to increase the durability of refractory masonry furnaces - Google Patents

Description

108790

The present invention relates to a titanium-containing additive consisting of residues from the preparation of TiO2 for use in the furnace in order to increase the resistance of the refractory masonry and to its use for increasing the durability of the furnace refractory masonry.

For furnaces, particularly blast furnaces, iron, steel and 10 are used as feed additives in higher quantities of natural ilmenite, which serves as a source of titanium. Usually, natural ilmenite is crushed into pieces about 50 mm in size and added directly to the furnace. The addition of ilmenite has the effect of binding the nitrogen contained in the crude iron to the form of titanium nitrides or titanium carbonitrides. It provides the removal of I nitrogen from metal smelters. The deposition of the titanium compounds thus formed into the interior walls of the refractory masonry furnaces, particularly the blast furnace iron. 20 dan congregation nest, increases the durability of masonry. However, natural ilmenite must be quarried at the highest cost, and the natural sources of high quality ilmenite will then diminish.

According to DE 4 018 568 C2 there is known a process for treating loaded residues from the production of titanium dioxide, which are subjected to an exothermic reaction in which the evaporation of water gives a dry product, where the process is ... (pulp from titanium dioxide * "30) and residues from the zinc production of the jarosite process are mixed for the exothermic reaction with electrostatic precipitates and the Ca2 that the 2 108790 mixture heats up between 120 ° C and 180 ° C due to the exothermic reaction.

DE 2 125 073 B2 discloses a refractory material suitable for lining heating units which is resistant to both high temperatures and molten acid slags and contains from 44 to 85% by weight of refractory additives such as silicon carbide, chromium ore or silicon nitride, at least one binder based on orthophosphoric acid.

From DE 3 937 312 A1, there is known a method of making a building material, preferably in the form of an adjoining building material, suitable for underground structures, fast-acting or fast or late-bearing, wherein the loaded residues from the titanium dioxide production and the zinc produced by the jarosite method are for an exothermic reaction with electrostatic precipitator ash and evaporation salts from waste incineration plants with CaCl2 · 2H2O / NaCl resulting in an exothermic reaction.

DE 3 008 251 B1 discloses a 'I' as a subfloor, a refractory material, especially for duct and funnel mouthpieces, for cast steel smelters having an Al203 content of 20-32% and a SiO2 content of 60%. - 70% and the content of side oxides such as TiO2, Fe2O3 and Na2O is less than 10% and containing Ca0 and MgO, whereby CaO and MgO '*. the content is 1.5 to 10%. In this case, it is intended to provide a casting product of higher purity.

It is an object of the present invention to provide a titanium-containing additive that replaces natural ilmenite as an additive in metallurgical processes, and enables its use in an economical and environmentally friendly manner to increase the durability of furnace refractory masonry.

Said object is achieved in accordance with the invention by means of a titanium-containing additive consisting of residues from the preparation of TiO 2 and one or more constituents of carbon, carbonaceous residues, iron, iron oxide and iron or iron oxide containing residues, in particular - 10 cents, in the preparation of titanium-containing raw materials such as ilmenite, and the slag or mixture of ilmenite and slag is extracted, for example, after a sulphate process with sulfuric acid, whereby titanium is extracted in the form of titanyl sulphate. The insoluble residue thus formed is separated by means of a thickener and a rotary filter and then recovered. This residue still contains about 20 to 65% by weight of TiO 2. Even with the new extraction, the residue is not completely capable of leaching TiO 2, which results in significant amounts of TiO 2 being deposited. Other titanium dioxide pigments may also be used in accordance with the invention. TiO2 residues from menthol manufacturing processes such as the chloride process.

. '!! A particular advantage of the titanium-containing additive according to the invention is that iron and / or iron oxide containing residues derived from the production of TiO2 can be used simultaneously. The residues containing iron oxide, .. · are mainly oxide-containing (FeO-,? Fe2O3). - or Fe304) in the form of dusts, filter liquids or filter cakes.

30 Iron and iron oxide residues are generated in various industries which, despite their high iron content, cannot be diverted for direct use due to their composition and consistency. One typical product is combustion waste. Combustion residues are produced as residue 35 in the manufacture of sulfuric acid by decomposition of sulfur chelate or iron 108790 4 phases. The iron content of combustion wastes can vary between 30% and 60%. Another iron and iron oxide-containing residue is a rolling mill. Rolling milling is about the oxidation layers that are formed during rolling and forging of steel and wire drawing. In the rolling mill, dandruff is removed from the metal surface to be rolled during rolling, for example by means of a water jet. In addition, iron and iron oxide-containing residues are generated in all areas of iron making and in the production of 10 iron oxides for the production of paint pigments.

One very particular advantage of the additive according to the invention is that carbon and carbonaceous residues can be used to make the titanium-containing additive. Coal and carbonaceous residues are preferred sources of energy.

i

One preferred embodiment of the invention is a titanium-containing additive containing 5 to 95% by weight of residues from the preparation of TiO 2 and 5 to 95% by weight of carbon. A particularly preferred embodiment of the invention is a titanium additive containing from 50 to 95% by weight of residues from the preparation of TiO 2 and from 50 to 95% by weight of carbon.

!!! One preferred embodiment of the invention is a titanium-containing additive containing 10 to 80% by weight of residues from the manufacture of TiO2, 5 to 70% by weight of carbon and 5 to 40% by weight of iron and / or iron oxide. · Diphenic residues.

·: ··: Titanium-containing additive is prepared by:. · *. the ingredients are mixed and homogenized in a manner known per se.

According to the invention, the titanium-containing additive mentioned above is a powder blend having a grain size of 50 to 5000 µm.

The compositions of the invention can be supplied to furnaces to repair thin refractory linings.

5, 108790

One preferred embodiment of the invention is a titanium-containing additive in the form of sintered bodies.

The sintered bodies are prepared by feeding a homogeneous mixture into a sintering mold and then sintering in a manner known per se. The sintered material can then be crushed to the desired size.

Another embodiment of the invention is a titanium-containing additive consisting of residues from the preparation of TiO 2, one or more binders and one or more constituents selected from carbon, carbonaceous residues, iron, iron oxide and iron or iron oxide, and in the form of briquettes, pellets or granules. Said moldings can then be treated at a temperature of 100-1000 ° C. Briquette moldings can be cylindrical, circular, oval, rectangular, or cubic; :: of. The binders according to the invention are all available hydraulic, ceramic and. chemical binders and swelling binders.

One preferred embodiment of the invention is *! ' such that the binders are Portland cement, blast furnace slag cement, aluminous cement and, preferably, coal filter power ash from coal power plants, - containing the following components:

Portlandsement- Blast furnace slag- Aluminate (wt%) ment (wt%) ment (wt-%) ··. CaO 62 - 65 50 - 55 38 - 42 30 Si02 1 6 - 2 1 25 - 30 4 -7 I A1203 2 - 6 8 - 10 48 - 52

Ti02 2-6 8-10 48-52

Fe 2 O 3 2 - 4 1-2 0, 5-1.5

Mn 2 O 3 0.05 - 0.2 0.3 - 0.6 0.05 - 0.15 35 MgO 1-2 3-4 0.5-1.5 6 108790 Electric filter ash (% by weight)

Si02 47 - 53 A1203 26 - 30 5 Fe203 6 -8

CaO 2.4-3.0

MgO 1.9 - 2.5 K20 3.0 - 4.6

Na 2 O 0.6 - 1.1 10

One preferred embodiment of the invention is a titanium additive in the form of briquettes, pellets, or granules containing 20 to 90% by weight of residues from the preparation of TiO2, 5 to 70% by weight of iron and / or iron oxide containing residues and 2 30% by weight of binders.

One preferred embodiment of the invention is a titanium additive in the form of *, '·· in the form of briquettes, pellets or granules containing 20 to 80% by weight of residues from the preparation of TiO2, 5 to 70% by weight of carbon and 2 30% by weight of binders.

One preferred embodiment of the invention is: • a titanium additive in the form of briquettes, pellets or granules containing 20 to 80% by weight of residues from the preparation of TiO 2, 5 to 50% by weight • of iron and / or iron oxide containing residues , 2-50% by weight of carbon and 2-30% by weight of binders.

: ·· When mixing into briquettes, as homogenous a mixture as possible can be achieved, which requires a minimum of 30 to 3-5 minutes mixing time. The water content is 2-30% by weight. The water content must be adjusted to allow physical treatment of the '' mixture.

The moldings require a cure time of up to 14 days. The cure time can be reduced by conventional heat treatment with ta-35.

7 108790

The pellets and granules can be prepared in a manner known per se from the homogeneous mixture described above under the conditions described above.

According to the invention, it is possible to use 5 titanium-containing additives in the form of a powder mixture and molds to be introduced into the furnace in order to increase the durability of its refractory masonry. The use of the invention in ovens takes place especially in the iron, steel and foundry industries.

1 illustrates the invention.

Figure 1 illustrates a titanium-containing additive consisting of residues from the preparation of TiO 2, one or more binders for blast furnace slag cement, aluminate-15 cement and electrofiltering ash, and one or more constituents for , iron, iron oxide and iron or. ·: Iron oxide-containing residues, flow-through of briquettes, pellets and granules, In step 20, the residues 2 from the preparation of TiO2, the residues containing iron and iron oxides 3, and the carbon ... and residues 4 containing carbon are fed to sieve 5. Seq. *. lot 13 is delivered via balance 6 to the belt conveyor. The material is fed to mixer 7. Mixer 7 is fed. Binders 8 and water 9 are also provided. The homogeneous mixture is fed in batches to a briquetting, pelletizing or granulating device 10, preferably mounted on a movable support 1. After the required bonding time, the molded articles are transported by belt conveyor 11 to the finished product warehouse 12.

The moving chassis 1 may be a truck or a trailer thereof. The apparatus according to the invention makes it possible to utilize the resulting carbonaceous residues and the resulting iron and iron oxide-containing residues which would otherwise have to be deposited on site. A particular advantage is that the shaped bodies according to the invention can be manufactured directly in the iron, steel and foundry industry and fed to furnaces.

The invention is illustrated by examples.

5 To determine the tensile strength (puncture strength), the molds were subjected to a continuously increasing force on the test press until they broke. The force applied to the briquettes as they break is a measure of their breaking strength.

Example 1

50% by weight of the leaching residue from the preparation of TiO2 by the sulfate process containing 51% by weight of TiO2, 23% by weight of SiO2, 2% by weight of Al2O3, 6% by weight of CaO were introduced into the mixer. and 5% by weight Fe 2 O 3, 15 and 30% by weight rolling mill containing 67% by weight Fe 2 O 3, 2% by weight SiO 2, 2% by weight CaO and 2% by weight carbon. Thereafter, 13 wt% · * ·· blast furnace slag Portland cement containing 51 wt% CaO, 27 wt% SiO 2, 4.5 wt% Al 2 O 3, 4.5 wt% was added thereto with stirring. % 20 TiO 2, 1.5 wt% Fe 2 O 3, 0.5 wt% Mn 2 O 3, and 3.5 wt% MgO, 1.5 wt% electrostatic precipitator ash containing 50 wt% -% SiO 2, 28% Al 2 O 3, 7% Fe 2 O 3, 3.2% CaO, 2.2% MgO, 3.8% K 2 O: and 0.9% by weight of Na 2 O and 5.5% by weight of aluminous cement,. . Containing 40% by weight of CaO, 6.5% by weight of SiO2, 25% by weight; 1% by weight Al 2 O 3, 25% by weight TiO 2, 1.0% by weight FE 2 O 3, 0.1% by weight Mn 2 O 3 and 1.0% by weight MgO, and the mixture is stirred -; ··· was thoroughly 5 minutes. Thereafter, 0.5 L of water was added to the mixture and the mixture was homogenized for 5 minutes. A homogeneous mixture was fed into a briquette press. A pressure of 120 bar was applied to the briquette press to obtain cylindrical moldings (briquettes) having an outside diameter of 80 mm and a length of 40 mm. The moldings obtained after 14 days of curing time had a breaking strength of 3500 N and a breaking strength of 1000 N at 3 000 N after heating for 1½ hours in a 100% CO atmosphere at 1000 ° C. contained 25.0 wt.% TiO 2, 23.0 wt.%

Fe 2 O 3, 16.6 wt% SiO 2, 6.5 wt% Al 2 O 3, 12.4 wt-5% CaO, 0.5 wt% C, 0.1 wt% Na and 0.07 wt% K.

Example 2

Cylindrical shaped bodies (briquettes) were prepared as described in Example 1, using 60% by weight of the leaching residue from the preparation of TiO 2 by the sulphate process (composition similar to Example 1), 30% by weight of rolling mill and wt.% blast furnace slag cement (composition similar to Example 1). The cylindrical shape-15 pieces had an outside diameter of 80 mm and a length of 40 mm. After 14 days of setting time, the cylindrical molds had a breaking strength of 3500 N and a tensile strength of 1 700 hours after heating in a 100% CO gas: 1000 atmosphere at 3700 N. The cylindrical molded pieces contained 29.5 wt.% TiO 2, 22.0 wt.% Fe 2 O 3, 15.0 wt.% SiO 2, 7.0 wt.% Al 2 O 3, 10.3 wt.% CaO, 2.8 wt% C, 0.1 wt% Na and 0.08 wt% K;

Example 3,. Cylindrical shaped bodies (briquettes) were prepared as described in Example 1, using 50% by weight of a leaching residue obtained from the preparation of TiO 2 by the sulfate process (composition similar to Example 1), 25% by weight. % rolling mill sediment (composition similar to Example 1), 10% by weight of digestion residues (containing 72% by weight Fe2O3, 6% by weight TiO2, 7% by weight SiO2, 3% by weight) % Al 2 O 3 and 2% by weight CaO), 10.5% by weight blast furnace slag cement (composition similar to pre-35 in Example 1), 3.5% by weight aluminum cement (composition 10108790 similar to Example 1), and 1% by weight of electrostatic precipitator ash (composition similar to Example 1). The cylindrical moldings had an outside diameter of 80 mm and a length of 40 mm. After 14 days of setting time, the cylindrical molds had a breaking strength of 3400 N and a breaking strength after 1½ hours of heating in 100% CO at 1000 ° C was 4050 N. The cylindrical molds contained 25.0 wt% TiO2, 27.0 wt% Fe2O3, 16.0 wt% SiO2, 6.0 wt% Al2O3, 10.0 wt% CaO, 3, 3 wt% C, 0.12 wt% Na and 0.1 wt% K.

Example 4 50% by weight of the solubilization residue from the preparation of TiO 2 by the sulfate process and 50% by weight of the carbon were thoroughly mixed. A powder product with an average grain size of less than 2 mm was formed. The mixture contained 23.0 wt% TiO 2, 2.5 wt%

Fe 2 O 3, 10.0 wt% SiO 2, 2.0 wt% Al 2 O 3, 3.3 wt% CaO, 49.0 wt% C, 0.12 by weight of Na and 0.1 to 20% by weight of K.

", Example 5 40% by weight of the leaching residue from the preparation of TiO 2 by the sulphate process (composition similar to Example 1) and 20% by weight of the combustion residues from the decomposition (composition similar to Example 3). ) was mixed with each other (5 min) The mixture was homogenized with 40% carbon by weight for 2 minutes The resulting powdery mixture had an average grain size of less than 2 mm and contained 19.0% TiO 2: a, 16.5 wt% Fe 2 O 3; 9.5 wt% SiO 2, 2.6 wt% Al 2 O 3, 3.2 wt% CaO, 43.0 wt% C, 0.1 wt.% Na and 0.08 wt.% K.

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Claims (10)

1. Titanium-containing additive intended to be fed into a furnace to increase the pourability of the refractory masonry thereof, characterized in that it consists of Tests derived from the TiO iron, iron oxide and iron or iron oxide-containing tests. Titanium-containing additive according to claim 1, characterized in that it contains 5-95% by weight of residues derived from the TiO 2 preparation and 5-95% by weight koi. Titanium-containing additive according to claim 1, 15 k characterized in that it contains 10 - 80% by weight of residues derived from TiO 2 production and 5 - 70% by weight koi and 5-40% by weight iron and / or iron -! .. *: oxide-containing residues. i i ; * ·· 4. Titanium-containing additive according to claims 20 to 1-3, characterized in that it exists in * ·· form of sintered pieces. 5. Titanium-containing additive intended to be fed into a furnace to increase the pourability of the refractory masonry (characterized in that it consists of residues originating from The TiO 2 -frame, one or more binder and one or more constituents, selected from koi, carbonaceous residues, iron, iron oxide and iron or iron oxide-containing residues in the form of briquettes, pellets or granules. 6. A titanium-containing additive according to claim 5, characterized in that the bonding agent is Portland cement, blast furnace slag Portland cement, aluminate cement or electro-filter ash. Titanium-containing additive according to claim 5, characterized in that it contains 20-90% by weight of residues derived from the TiO2 preparation, 14% and 70% by weight of iron and / or iron oxide-containing residues and 2-30% by weight. % binder. Titanium-containing additive according to claim 5, characterized in that it contains 20-80% by weight of residues derived from the TiO2 preparation, 5-70% by weight koi and 2-30% by weight binder. Titanium-containing additive according to claim 5, characterized in that it contains 20 - 80% by weight of residues derived from the TiO 2 preparation, 5 - 50% by weight iron and / or iron oxide-containing residues, 2-50% by weight carbon and 2-30% by weight binder. Use of a titanium-containing additive according to claims 1-9 to increase the pourability of the refractory brick in an oven. • · i · I · * · fill * ·; - »» »i