CN116854491A - Vanadium erosion resistant refractory material - Google Patents

Vanadium erosion resistant refractory material Download PDF

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Publication number
CN116854491A
CN116854491A CN202310883906.1A CN202310883906A CN116854491A CN 116854491 A CN116854491 A CN 116854491A CN 202310883906 A CN202310883906 A CN 202310883906A CN 116854491 A CN116854491 A CN 116854491A
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equal
vanadium
refractory material
less
erosion resistant
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宋振
霍勇成
刘泉林
周立伟
黄效礼
宋林良
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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    • C04B35/495Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
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Abstract

The invention relates to the field of refractory materials, in particular to a vanadium erosion resistant refractory material, which has a chemical formula as follows: (Mg) a Ca b Sr c Ba 1‑a‑b‑c ) x (V d Nb e Ta f Mn 1‑d‑e‑f ) 2 O x+5 The crystal structure of the crystal belongs to a trigonal system; has adjustable component proportion, wherein x is more than or equal to 2 and less than or equal to 3, a is more than or equal to 0 and less than or equal to 0.1,0.8 and less than or equal to b is more than or equal to 1, c is more than or equal to 0 and less than or equal to 0.1,0.9 and less than or equal to d is more than or equal to 1, e is more than or equal to 0 and less than or equal to 0.05, and f is more than or equal to 0 and less than or equal to 0.05. According to the invention, the vanadium-containing compound is introduced into the refractory material, so that the vanadium erosion resistance of the material can be effectively improved, and the refractory material has better adaptability and flexibility due to the component proportion and the replaceability of the precursor, so as to meet the requirements of different industrial equipment.

Description

Vanadium erosion resistant refractory material
Technical Field
The invention relates to the field of refractory materials, in particular to a vanadium erosion resistant refractory material.
Background
V 2 O 5 Is an important upstream product for vanadium-nitrogen alloy production, and is widely applied to the fields of chemical industry, aviation, aerospace and the like. However, at present V is industrially produced 2 O 5 Heating in a melting furnace is required, and V in a molten state 2 O 5 Corrosion of refractory materials is a serious problem. Conventional lining materials for melting furnaces such as clay bricks and chrome corundum bricks are at a high temperature in liquid state V 2 O 5 Under the action of the furnace lining, serious corrosion is easy to occur, the service life of the furnace lining is short, and the production cost is increased by frequently replacing the refractory material. In addition, spalling of the refractory material can also reduce the purity of the final product and affect yield. Studies have shown that chemical corrosion and physical scouring of the molten oxides are the main causes of severe lining corrosion.
The vanadium melting furnace can be made of various refractory materials, such as conventional silica bricks (SiO 2 ) Fused cast aluminum oxide product (Al 2 O 3 ) Chrome corundum brick (Cr) 2 O 3 -Al 2 O 3 ) Fused cast mullite (Al) 2 O 3 -SiO 2 ) Magnesia-chrome spinel (MgCr) 2 O 4 ) Magnesia-alumina spinel (MgAl) 2 O 4 ) And magnesia carbon bricks (MgO-C), etc. Currently used for preparing V 2 O 5 The lining material of the melting furnace is mainly high alumina refractory material, and the main phases of the lining material are corundum, mullite and glass phase. Due to the high alumina bricks and V 2 O 5 The reaction occurs at high temperature to form a low melting point substance, and thus has a problem in terms of service life.
Vanadium can form oxides in different valence states under different conditions of temperature and oxygen partial pressure. V (V) 2 O 3 About 2243K (1970 ℃ C.), V 2 O 4 Forms a refractory binary system with other oxides, and V 2 O 5 Then it is a stable phase with a melting point of about 953K (680 c). V (V) 2 O 5 With Al 2 O 3 The initial liquid phase formation temperature therebetween is about 913K (640 ℃) such that V 2 O 5 Rapidly reacts and erodes the refractory material at the operating temperature of the melting furnace.
The destruction of the alkaline refractory by vanadium is mainly developed by erosion of the bonding phase. V (V) 2 O 5 The high-alumina brick is deeply infiltrated and is deteriorated, and the high-alumina brick is mainly eroded by melting and infiltration modes. Magnesium chromium (MgAl) 2 O 4 ) Spinel refractory pair V 2 O 5 Erosion and penetration of the melt are strong, however MgO therein is resistant to V 2 O 5 React to form MgV 2 O 6 Reducing its corrosion resistance. The magnesium carbon (MgO-C) brick forms a decarburized layer under the vanadium leaching condition, and if the magnesium carbon (MgO-C) brick is not sintered effectively, the decarburized layer structure is loose and has poor bonding strength, so that the brick body is easy to be washed out by a molten pool and peeled off and damaged.
Therefore, there is a need for a new refractory material that is resistant to vanadium attack for the lining of a melting furnace to reduce the number of repairs, reduce the production cost, and improve the purity and yield of the final product.
Disclosure of Invention
In view of the above-mentioned problems in the background art, an object of the present invention is to provide a refractory material resistant to vanadium attack, which can effectively improve the resistance to vanadium attack of the material by containing a vanadium compound in the refractory material, and the composition ratio and the replaceability of the precursor of the refractory material make the refractory material have better adaptability and flexibility so as to meet the requirements of different industrial equipments.
The technical scheme provided by the invention is as follows: a refractory material resistant to vanadium attack, said refractory material having the chemical formula:
(Mg a Ca b Sr c Ba 1-a-b-c ) x (V d Nb e Ta f Mn 1-d-e-f ) 2 O x+5 the crystal structure of the crystal belongs to a trigonal system;
has adjustable component proportion, wherein x is more than or equal to 2 and less than or equal to 3, a is more than or equal to 0 and less than or equal to 0.1,0.8 and less than or equal to b is more than or equal to 1, c is more than or equal to 0 and less than or equal to 0.1,0.9 and less than or equal to d is more than or equal to 1, e is more than or equal to 0 and less than or equal to 0.05, and f is more than or equal to 0 and less than or equal to 0.05.
Further, the precursors include, but are not limited to, calcium compounds including calcium hydroxide, calcium carbonate, vanadium compounds including vanadate, ammonium vanadate, and oxides.
Further, the composition ratio of the divalent and pentavalent metal elements and O in the refractory material may be optimized according to the sintering temperature and the final application of the material.
Further, the composition ratio of the refractory material can be characterized and verified by means of X-ray diffraction, a scanning electron microscope and energy spectrum analysis.
Further, the refractory material may also include other suitable additives including ceramic fibers, reinforcing particles to further improve the physical and mechanical properties of the material.
Further, the refractory material exists in a block, a sheet, a granule, a coating or other forms so as to adapt to various application scenes.
Further, the refractory material is synthesized by a solid phase reaction method.
Further, the refractory material is subjected to sintering, hot pressing or other suitable process to enhance the compactness and mechanical strength of the material.
Further, the refractory material is used for resisting vanadium erosion, has excellent high temperature resistance, is stably used in a high temperature environment of 1000 ℃ to 1400 ℃, and is suitable for high temperature industrial equipment including but not limited to a steel furnace, an oil refining furnace and a chemical reactor.
The beneficial effects of the invention are as follows: the new idea of synthesizing refractory brick with vanadium corrosion resistance by introducing vanadium-containing compound is provided. V occupies lattice sites, and when liquid V2O5 contacts with the V, the V and the O only can generate dynamic balance V ion exchange, and a new phase is not generated through chemical reaction, so that the V-type V-ion alloy has very excellent vanadium corrosion resistance.
In practical application, the component proportion can be flexibly adjusted according to specific industrial equipment and process requirements so as to obtain the optimal material performance, the structure and interaction of the materials can be controlled by adjusting the proportion among different precursors, so that the optimal combination of the materials is achieved, and the flexibility enables the refractory material of the invention to have wide application potential in different industrial fields.
The disclosed vanadium erosion resistant refractory has a number of advantages including, but not limited to, high temperature stability, resistance to vanadium erosion, and flexible regulation, and can be used in a variety of high temperature industrial equipment such as steel furnaces, oil refiners, chemical reactors, etc., to protect the equipment from vanadium erosion.
Therefore, the vanadium erosion resistant refractory provided by the invention has the following advantages:
1. excellent vanadium corrosion resistance: through reasonable component design and regulation, the refractory material can effectively resist liquid V 2 O 5 And prolonging the service life of the vanadium melting furnace.
2. The production cost is reduced: the service life of the refractory material is prolonged, the frequency of replacing the refractory material is reduced, and the cost of maintaining and replacing the refractory material is reduced, thereby reducing the production cost.
3. The product quality is improved: the excellent performance of the refractory material can prevent the refractory material from peeling off and damaging the structure, reduce the impurity inclusion and pollution, and improve the purity and yield of the final product.
Drawings
Figure 1 is a schematic representation of XRD measurements of example 1 of the present invention.
Fig. 2 is a schematic diagram of the compact structure of the block structures of example 1 and example 2 of the present invention.
Figure 3 is a schematic representation of XRD measurements of example 2 of the present invention.
Detailed Description
The invention is illustrated below by means of specific examples, without limiting the invention.
Example 1:
the invention provides a preparation method of the material, which comprises the following steps:
1) Weighing materials: according to the general formula Mg 0.01 Ca 2.97 Sr 0.01 Ba 0.01 V 2 O 8 Is to weigh high purity MgCO in sequence 3 ,CaCO 3 ,SrCO 3 ,BaCO 3 ,V 2 O 5 Weighing a proper amount of fluxing agent;
2) Placing the powder obtained in the step 1) into an agate mortar, adding a proper amount of alcohol for grinding for 20-40 minutes, scraping the powder attached to the mortar wall after the powder is dried, dry-grinding for 10-30 minutes, and then placing the powder into a high-temperature alumina crucible;
3) Placing the high-temperature alumina crucible in a box furnace, setting a program for presintering, heating to 600 ℃ at a heating rate of 5-10 ℃/min for presintering, preserving heat for 2-6 hours, cooling to room temperature along with the furnace, taking out a sample, and placing the sample in a ball milling tank for ball milling for 4 hours;
4) XRD was measured and the results are shown in FIG. 1;
5) Filling the powder subjected to ball milling treatment in the step 3) into a custom-made die coated with a layer of lubricant, then placing the die into a tablet press, lifting the pressure to about 10Mpa, and maintaining the pressure for 1 minute in the state to realize high compaction of the powder and form a compact structure with a block-shaped structure, as shown in fig. 2;
6) Transferring the solid block in the step 5) into a high-temperature alumina crucible again, placing the crucible in a box furnace, heating to 1300 ℃, calcining for 3-10 hours under high temperature, cooling to 800 ℃ at a cooling speed of 5-10 ℃/min, and cooling to room temperature along with the furnace;
7) The block is tested for vanadium corrosion resistance at 1300 ℃, and the specific steps are as follows: will V 2 O 5 Filling powder into the central recess of the block obtained in the step 6), placing in a high-temperature furnace, heating to 1300 ℃, preserving heat for 4 hours, taking out the block after cooling along with the furnace, cutting vertically, and measuring V 2 O 5 Erosion depth;
in the step 1) of the preparation method of the vanadium erosion resistant material, the fluxing agent can be alkali metal chloride or B 2 O 3 、H 3 BO 3 At least one of them. The amount of fluxing agent was 1wt% relative to the total weight of the raw materials.
The preparation method of the vanadium erosion resistant material disclosed by the invention comprises the steps 2) and 6) of sufficiently improving the purity of the synthesized sample.
Example 2:
weighing materials: according to the general formula Ca 2 (V 0.95 Nb 0.02 Ta 0.02 Mn 0.01 ) 2 O 7 Is to weigh high purity CaCO in sequence 3 ,V 2 O 5 ,Nb 2 O 5 ,Ta 2 O 5 ,MnO 2 Weighing a proper amount of fluxing agent;
the XRD pattern is shown in FIG. 3, otherwise identical to that of example 1.
Comparative example 1
Machining commercial silica bricks into the shape of the block materials in the examples;
the block is tested for vanadium corrosion resistance at 1300 ℃, and the specific steps are as follows: will V 2 O 5 Filling powder into the central recess of the block, placing in a high-temperature furnace, heating to 1300 ℃, preserving heat for 4h, cooling with the furnace, taking out the block, vertically cutting and measuring V 2 O 5 Erosion depth;
comparative example 2
Processing commercial high-alumina bricks into the shape of block materials in the embodiment;
the block is tested for vanadium corrosion resistance at 1300 ℃, and the specific steps are as follows: will V 2 O 5 Filling powder into the central recess of the block, placing in a high-temperature furnace, heating to 1300 ℃, preserving heat for 4h, cooling with the furnace, taking out the block, vertically cutting and measuring V 2 O 5 Erosion depth.
Table 1: vanadium erosion test results
Depth of vanadium attack
Example 1 <1mm
Example 2 1mm
Comparative example 1 >5mm
Comparative example 2 >5mm
By measuring the results of the vanadium attack depths of comparative example 1, example 2, comparative example 1 and comparative example 2, it was found that: example 1 measured V 2 O 5 Depth of attack of<1mm, V measured in example 2 2 O 5 Erosion depth of 1mm, V measured in example 3 2 O 5 Depth of attack of>5mm, V measured in example 4 2 O 5 Depth of attack of>5mm, it is seen that the vanadium attack depths of examples 1 and 2 are much lower than those of comparative examples 1 and 2.
The vanadium erosion resistant refractory material provided by the invention has wide application prospect, and the technical effect and economic benefit of the invention are obvious. The preparation method of the refractory material is simple and feasible, has relatively low cost, and can be conveniently applied to the industrial fields of vanadium melting furnaces and the like, thereby promoting the development of related industries.
Meanwhile, the vanadium erosion resistant refractory material can be further optimized and improved according to specific requirements. By adjusting the proportion and the formula of the core protection component and the expansion component, more refractory material combinations can be explored while the vanadium resistance is ensured, so as to meet the requirements of different industrial fields on refractory materials.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.

Claims (9)

1. A refractory material resistant to vanadium attack, characterized in that the refractory material has the chemical formula:
(Mg a Ca b Sr c Ba 1-a-b-c ) x (V d Nb e Ta f Mn 1-d-e-f ) 2 O x+5 the crystal structure of the crystal belongs to a trigonal system;
has adjustable component proportion, wherein x is more than or equal to 2 and less than or equal to 3, a is more than or equal to 0 and less than or equal to 0.1,0.8 and less than or equal to b is more than or equal to 1, c is more than or equal to 0 and less than or equal to 0.1,0.9 and less than or equal to d is more than or equal to 1, e is more than or equal to 0 and less than or equal to 0.05, and f is more than or equal to 0 and less than or equal to 0.05.
2. A vanadium erosion resistant refractory according to claim 1 wherein: the precursors include, but are not limited to, calcium compounds including calcium hydroxide, calcium carbonate, vanadium compounds including vanadate, ammonium vanadate, and oxides.
3. A vanadium erosion resistant refractory according to claim 1 wherein: the composition ratio of divalent and pentavalent metallic elements and O in the refractory material may be optimized according to the sintering temperature and the final application of the material.
4. A vanadium erosion resistant refractory according to claim 1 wherein: the composition ratio of the refractory material can be characterized and verified by means of X-ray diffraction, a scanning electron microscope and energy spectrum analysis.
5. A vanadium erosion resistant refractory according to claim 1 wherein: the refractory material also includes other suitable additives including ceramic fibers, reinforcing particles to further improve the physical and mechanical properties of the material.
6. A vanadium erosion resistant refractory according to claim 1 wherein: the refractory material exists in a block, sheet, granular, coating or other forms to adapt to various application scenarios.
7. A vanadium erosion resistant refractory according to claim 1 wherein: the refractory material is synthesized by a solid phase reaction method.
8. A vanadium erosion resistant refractory according to claim 1 wherein: the refractory material is subjected to sintering, hot pressing or other suitable process treatments to enhance the compactness and mechanical strength of the material.
9. A vanadium erosion resistant refractory according to any one of claims 1 to 8 wherein: the refractory material is used for resisting vanadium erosion, has excellent high temperature resistance, is stably used in a high-temperature environment of 1000-1400 ℃, and is suitable for high-temperature industrial equipment including but not limited to a steel furnace, an oil refining furnace and a chemical reactor.
CN202310883906.1A 2023-07-19 2023-07-19 Vanadium erosion resistant refractory material Pending CN116854491A (en)

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