CN114318015B - Treatment and utilization method of waste vanadium catalyst - Google Patents
Treatment and utilization method of waste vanadium catalyst Download PDFInfo
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Abstract
The invention discloses a method for treating and utilizing a waste vanadium catalyst, and belongs to the field of metallurgical engineering. It comprises the following steps: 1. collecting a waste vanadium catalyst generated in the sulfuric acid industry, and drying, crushing and screening to obtain a vanadium-containing raw material; 2. adding vanadium-containing material onto molten aluminum liquid, and blowing CO and NH into the lower part of the container 3 Stirring, heating the aluminum liquid and the liquid level, and controlling the temperature of the aluminum liquid and the liquid level to react between 680 and 900 ℃; 3. standing the vanadium-containing raw material and aluminum liquid after the reaction in the second step, and then skimming slag to obtain a vanadium nitride-containing material and collecting the vanadium nitride-containing material; 4. and (3) adding the vanadium nitride material into the smelted molten steel, and carrying out vanadium nitride microalloy reaction. The invention can directly add the treated waste vanadium catalyst into molten steel smelting, has stable vanadium yield, has ideal vanadium increasing effect on molten steel, and improves the product performance obtained by final smelting.
Description
Technical Field
The invention belongs to the technical field of metallurgical engineering, and particularly relates to a method for treating and utilizing a waste vanadium catalyst.
Background
Vanadium is a very important, thin, dispersed metal source with very low surface content and is widely used in various fields of industry. Wherein V is 2 O 5 As a catalyst, it is used in the sulfuric acid industry, and therefore, a large amount of spent vanadium-containing catalyst is produced in the sulfuric acid industry every year. The scrapped vanadium-containing catalyst, namely the waste vanadium catalyst, contains 3 to 12 percent of V 2 O 5 1-3% Fe 2 O 3 1-5% of K 2 O，5-15％SO 2 (in sulfate radical SO) 4 2- In the form of (a) diatomaceous earth (in the form of SiO) 2 The form is mainly present), and the like, therefore, the method is not only a dangerous waste, but also a relatively important vanadium and potassium resource, and can not be discarded at will. However, the recycling of the spent vanadium catalyst as a resource often requires specialized equipment and a large amount of investment, and at the same time, secondary pollution is likely to occur, and the environment is polluted, so that a new process is needed to realize the direct utilization of the spent vanadium catalyst and solve the problems of high utilization cost and environmental pollution.
Since many grades of steel have greatly improved their mechanical properties after addition of vanadium, metallic vanadium is often used in the iron and steel industry as an important microalloying element, and vanadium is currently mainly added to iron and steel materials in the form of ferrovanadium. However, because the smelting cost and the environmental protection cost of the ferrovanadium alloy are high, the ferrovanadium alloy is high in price, the ferrovanadium alloy brings cost pressure to ferrous metallurgy, and more importantly, the ferrovanadium alloy smelting needs high-grade raw materials and is easy to produce environmental pollution. Accordingly, engineers have proposed using vanadium-containing raw materials, such as vanadium-containing minerals, vanadium-containing steel slag, and spent vanadium catalysts produced in the sulfuric acid industry, to directly effect alloying of vanadium in the iron and steel smelting process by a reduction method, a process called direct alloying of minerals.
Among them, many scholars have made systematic studies on the comprehensive recycling of the spent vanadium catalyst. For example, by hydrometallurgical extraction of vanadium pentoxide into solution, followed by precipitation by addition of ammonium salt, NH4VO is obtained 3 Finally roasting to obtain pure vanadium pentoxide, and extracting other components such as potassium sulfate independently to prepare the potassium sulfate fertilizer. In addition, the solution containing vanadate is obtained through leaching by using chlorogenic acid, and then extracting, separating and back-extracting. However, these processes are long, consume a large amount of acid and alkali in the comprehensive utilization process or the quality of the obtained product is not high.
As another example, will contain V 2 O 5 The waste vanadium catalyst is reduced and is added into molten steel instead of vanadium-containing alloy, so that the performance of the prepared product is improved. However, the technology has the problems of unstable vanadium yield and low utilization efficiency of the waste vanadium catalyst when being actually used at present, so that the industrial application is difficult to truly realize
The Chinese patent application number is: CN201810716719.3, publication date: patent literature of 11.30.2018 discloses a method for recycling waste vanadium catalyst, which comprises the following steps: step A: washing the waste vanadium catalyst by using a solution containing a diester-resistant precipitant and oxalic acid; and (B) step (B): drying the waste vanadium catalyst in a spin-drying way to obtain a dried waste vanadium catalyst; step C: soaking the dried waste vanadium catalyst in an oxalic acid solution containing 30-80% by mass, heating to 30-40 ℃, adding 2-8% by mass of vanadium pentoxide into the solution, heating to 80-102 ℃, and reacting for 2-5 hours to obtain an intermediate product containing the waste vanadium catalyst; step D: and roasting the intermediate product at 100-550 ℃ until no gas is discharged, and obtaining the waste vanadium catalyst containing vanadium pentoxide. Although the scheme can realize the treatment of toxic substances in the waste vanadium catalyst, the recovery treatment process is complex, the required process cost and labor cost are low, the finally obtained waste vanadium catalyst containing vanadium pentoxide still needs further treatment to be utilized, and the finally obtained waste vanadium catalyst cannot be directly added into molten steel to be smelted, so that the method is not ideal for practical use.
The Chinese patent application number is: CN201210304763.6, publication date: patent literature on 11/28/2012 discloses a method for increasing vanadium content in molten steel, which is characterized in that: during tapping, V is added into molten steel according to the addition amount of 2-3 kg/t steel in the molten steel alloying process 2 O 5 Vanadium slag with the content of 8-10wt%; after tapping, adding 1-2 kg of composite deoxidizer, 0.4-0.6 kg of slag modifier and 1.5-2.5 kg of slag former of lime and 1.2-1.0 kg of slag former of steel into molten steel, and then adding SiC or aluminum particles on the slag surface according to the adding amount of 0.2-1.0 kg of steel, and covering a ladle cover; argon or nitrogen with the pressure of 0.3-0.4 MPa and the flow rate of 140-160 m < 3 >/h is used for bottom blowing for 4-6 minutes from the bottom of the ladle, the alkalinity of refining slag is controlled to be 2.0-2.8, the oxygen content is controlled to be 5-20 ppm, and the vanadium content of molten steel is increased to 0.010-0.015 wt%. Although this scheme will V 2 O 5 Adding the alloy into molten steel to prepare steel, thereby realizing V 2 O 5 V in (C) but in actual use, it was found that V was directly used 2 O 5 Adding into molten steel for corresponding treatment and utilization, and finally obtaining products with properties which do not reach the ideal degree for V 2 O 5 The utilization rate of the vanadium slag and the yield of the V do not meet ideal requirements, and the scheme is to add the vanadium slag into molten steel for utilization, and is not necessarily applicable to waste vanadium catalysts.
Disclosure of Invention
1. Problems to be solved
Aiming at the problem that the actual effect of the treatment and utilization process of a large amount of waste vanadium catalysts generated in the sulfuric acid industry is not ideal in the prior art, the invention provides the treatment and utilization method of the waste vanadium catalysts, which can directly add the treated waste vanadium catalysts into molten steel smelting after treating the waste vanadium catalysts through a unique process, has stable vanadium yield, ideal vanadium increasing effect on the molten steel and improves the product performance obtained by final smelting.
2. Technical proposal
In order to solve the problems, the invention adopts the following technical scheme.
A method for the treatment and utilization of a spent vanadium catalyst, the method comprising the steps of:
1. pretreatment of
Collecting a waste vanadium catalyst generated in the sulfuric acid industry, and drying, crushing and screening to obtain a vanadium-containing raw material;
2. synthetic vanadium nitride
Preparing a container filled with molten aluminum, adding vanadium-containing material onto the molten aluminum, and blowing CO and NH into the lower part of the container 3 Stirring, heating the aluminum liquid and the liquid level, and controlling the temperature of the aluminum liquid and the liquid level to react between 680 and 900 ℃;
3. generating vanadium nitride material
Standing the vanadium-containing raw material and aluminum liquid after the reaction in the second step, and then skimming slag to obtain a vanadium nitride-containing material and collecting the vanadium nitride-containing material;
4. microalloying
And (3) adding the vanadium nitride material obtained in the step (III) into molten steel for smelting, and carrying out vanadium nitride microalloy reaction.
As a further improvement of the technical scheme, the reaction time of the second step is 2-4h.
As a further improvement of the technical scheme, in the second step, CO and NH are introduced in 0.5-1h from the beginning of the reaction 3 The volume ratio of (2-4) is 1; in the following 1-2h, CO and NH are introduced 3 Is 1:1 by volume; in the last 0.5-1h of the reaction, CO and NH are introduced 3 The volume ratio of (2) to (5) is 1.
As a further improvement of the technical scheme, in the second step, the mass ratio of the aluminum liquid to the vanadium-containing raw material is (10-50): 1.
As a further improvement of the technical scheme, in the second step, the aluminum liquid and the surface of the liquid are heated from the upper part of the container through industrial microwaves.
As a further improvement of the technical scheme, in the first step, the mass percentage of vanadium in the vanadium-containing raw material is not less than 5%.
As a further improvement of the technical scheme, the molten steel is deoxidized before the step four is started.
In the fourth step, after the vanadium nitride-containing material is added into the molten steel, argon is blown into the molten steel and stirred for 10-30min.
As a further improvement of the technical scheme, in the fourth step, the smelting temperature of molten steel is not more than 1600 ℃.
In the fourth step, lime is added into the molten steel for desulfurization treatment after the fourth step is completed.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention relates to a method for treating and utilizing a waste vanadium catalyst, which is implemented by bubbling CO and NH 3 The mixed gas of the aluminum solution and the vanadium-containing raw material, namely the waste vanadium catalyst, can carry out nitriding reaction while carrying out reduction reaction, so that V in the waste vanadium catalyst 2 O 5 The vanadium catalyst can be fully reduced into VN, so that the vanadium catalyst can be added into molten steel to realize nitrogen and vanadium increase of the molten steel, and the performance of the finally prepared steel is improved;
(2) The invention relates to a method for treating and utilizing a waste vanadium catalyst, which is characterized in that V is treated by 2 O 5 In the process of reducing VN, the reaction time is divided into three stages, and the three stages are controlled to be introducedCO and NH of (c) 3 The synthesis rate of VN is improved to the greatest extent, and the vanadium yield and the utilization rate of the waste vanadium catalyst of the method are improved;
(3) According to the method for treating and utilizing the waste vanadium catalyst, provided by the invention, the reduction reaction of the vanadium pentoxide is promoted due to the catalytic action of microwaves on the oxide in an industrial microwave heating mode, so that the reaction can be carried out at the low temperature of 680-900 ℃, and V at a high temperature is avoided 2 O 5 And K 2 O or SiO 2 Will first form composite oxide to inhibit V 2 O 5 Even if reduced to an elemental substance, the reduction is very easy to volatilize and secondarily oxidize, and there is a problem that more impurity oxides are reduced to an elemental substance;
(4) The invention relates to a method for treating and utilizing a waste vanadium catalyst, which is characterized in that V 2 O 5 In the reduction process of (2), partial nitrite contained in the waste vanadium catalyst is reduced or decomposed to generate SO 2 And discharged into the flue gas, thereby achieving the effect of reducing the sulfur content in the vanadium nitride-containing material finally added into the molten steel and meeting the requirements of subsequent molten steel refining.
Detailed Description
The inventor by aiming at the existing V 2 O 5 The reduction technique of the above-mentioned catalyst has been studied and found that the reduction technique of the conventional vanadium-containing catalyst has the following problems.
First, although it can be shown theoretically that V in vanadium-containing materials 2 O 5 Direct reduction in a steelmaking furnace or ladle is possible, but in the actual operation process, the smelting time is short, the contact of materials is difficult, and V is caused 2 O 5 The reduction rate of the vanadium is not high, and the final vanadium yield is also low.
Secondly, since vanadium is very active, even V in vanadium-containing materials 2 O 5 Is reduced and is easily oxidized secondarily, thereby reducing the yield, and a method for preventing the secondary oxidation is needed.
Third, because vanadium has strong volatility, V in vanadium-containing materials (such as vanadium slag, vanadium-containing catalysts, etc.) 2 O 5 Vanadium is easy to volatilize out and enter the flue gas in the reduction process, so that the yield is reduced, and a method for fixing vanadium is needed to inhibit volatilization.
Fourth, since some sulfur is contained in the sulfuric acid industry waste vanadium catalyst, the increase of sulfur in molten steel is easily caused in the process of utilization, so that a part of sulfur needs to be removed in advance in order to control the influence of sulfur.
Aiming at the problems, the invention designs a treatment and utilization method of a waste vanadium catalyst, which is mainly used for treating a large amount of waste vanadium catalyst generated in the sulfuric acid industry, and directly using the treated waste vanadium catalyst in molten steel smelting, so as to improve the vanadium content in the molten steel and the performance of the finally prepared steel, and the specific process, principle and effect of the method are described below.
1. Pretreatment of
And collecting a waste vanadium catalyst produced in the sulfuric acid industry, drying, removing a support body such as large-particle impurities (e.g. ceramic balls) by using a vibration screening method, crushing, screening and the like to obtain a vanadium-containing raw material with the particle diameter of 0.1-1.5mm, wherein the mass percent of vanadium in the vanadium-containing raw material is not less than 5%.
2. Synthetic vanadium nitride
Preparing a container filled with molten aluminum, adding pretreated vanadium-containing raw material onto the molten aluminum, and blowing CO and NH into the lower part of the container 3 The liquid level is stirred, so that the aluminum liquid and the waste vanadium catalyst are mixed and stirred more strongly, and meanwhile, industrial microwave heating is applied from the top, and the temperature of the aluminum liquid and the liquid level is controlled to be 680-900 ℃.
The reaction time is required to be according to V 2 O 5 And the residual amount of S is adjusted, generally 2 to 4 hours, and V after the reaction is required 2 O 5 The residual amount is controlled to be less than 0.2%, and the residual amount of S is controlled to be less than 1.5%. During the period of bubbling CO and NH 3 The ratio of the mixed gas in the reaction chamber is required to be adjusted in different reaction processes, so that the reaction effect is ensured. Specifically, CO and NH are introduced in 0.5-1h from the beginning of the reaction 3 The volume ratio of (2-4) is 1; in the following 1-2h, the flow-through is conductedCO and NH in 3 Is 1:1 by volume; in the last 0.5-1h of the reaction, CO and NH are introduced 3 The volume ratio of (2) to (5) is 1. In this process, V is realized 2 O 5 Is converted into VN. The mass ratio of the aluminum liquid to the vanadium-containing raw material is (10-50): 1, and the flow rates of carbon monoxide and ammonia gas are required to be determined according to the actual situation of the aluminum liquid, so that the aluminum liquid can be fully stirred, the aluminum liquid and the waste vanadium catalyst can be promoted to be stirred, and meanwhile, the nitriding effect of vanadium is ensured.
In this step, CO and NH are blown in 3 The mixed gas of the aluminum solution and the vanadium-containing raw material, namely the waste vanadium catalyst, can carry out nitriding reaction while carrying out reduction reaction, and the chemical reaction equation comprises the following four steps:
V 2 O 5 +5CO＝2V+5CO 2
3V 2 O 5 +10Al＝6V+5Al 2 O 3
2NH 3 +V＝2VN+3H 2
V 2 O 5 +5H 2 ＝2V+5H 2 O
the four above reactions together constitute the following reaction:
2V 2 O 5 +CO+2Al+4NH 3 ＝4VN+Al 2 O 3 +CO 2 +6H 2 O
CO produced by the reaction 2 And H 2 O, due to the presence of Al liquid, undergoes a reduction reaction and is largely converted into CO and H 2 The corresponding reaction equations are as follows:
2Al+3CO 2 ＝Al 2 O 3 +3CO
2Al+3H 2 O＝Al 2 O 3 +3H 2
due to the presence of aluminum, it is able to directly participate in the reduction of vanadium pentoxide on the one hand and to convert CO on the other hand 2 And H 2 O is reduced out, so that the reducing atmosphere is ensured; in addition, ammonia (NH) 3 ) The reduced vanadium is directly synthesized into vanadium nitride, thereby avoiding vanadiumVolatilizing and secondary oxidizing.
Meanwhile, in the reaction process, industrial microwaves are used as a heat source to heat the vanadium-containing raw material on the aluminum liquid, and the reduction reaction of vanadium pentoxide is promoted due to the catalytic action of the microwaves on oxides, so that the reaction can be carried out at the low temperature of 680-900 ℃.
If a technical route for synthesizing vanadium nitride by high-temperature reduction is adopted, V is at high temperature 2 O 5 And K 2 O or SiO 2 Will first form a complex oxide, thereby inhibiting V 2 O 5 Even if V is reduced 2 O 5 Reduced to elemental species, also very volatile and secondarily oxidized, and more impurity oxides are reduced to elemental species. For example, siO 2 Will be reduced to Si, thereby limiting the use of spent vanadium catalyst after treatment. If only low temperature reduction is used, then again due to V 2 O 5 Is difficult to restore and cannot go on.
Thus, two key technologies are creatively introduced here: firstly, pure aluminum solution is introduced as a reducing medium to reduce CO 2 At the same time absorb V 2 O 5 The generation of VN is promoted by the oxygen in the catalyst; and secondly, microwave heating is applied to the waste vanadium catalyst on the aluminum liquid to control the temperature. The combination of these two techniques results in V 2 O 5 The low-temperature reduction to form VN is realistic, and the prepared VN contains almost no carbon. In particular, on the basis, the invention also relates to V 2 O 5 In the process of reducing VN, the reaction time is divided into three stages, and CO and NH which are introduced into the reaction kettle by controlling three stages 3 The synthesis rate of VN is improved to the greatest extent, and the yield of vanadium and the utilization rate of the waste vanadium catalyst of the method are further improved, so that the overall effect of the method is improved obviously.
In addition, at V 2 O 5 In the reduction process of (2), partial nitrite contained in the waste vanadium catalyst is reduced or decomposed to generate SO 2 And discharged into the flue gas, thereby reducing the sulfur content in the vanadium nitride-containing material finally added into the molten steelThe effect of the amount meets the requirement of subsequent molten steel refining.
3. Generating vanadium nitride material
Standing the mixed liquid in the container after the reaction in the second step for 1-2h, then skimming slag, collecting the obtained vanadium nitride-containing material again, crushing and ball pressing again to prepare vanadium nitride-containing ball pressing particles (vanadium nitride ball materials for short), wherein the yield of vanadium nitride is generally above 80%.
4. Microalloying
And (3) putting the vanadium nitride ball material obtained in the step (III) on the surface of molten steel when the molten steel is refined in an LF furnace, performing a vanadium nitride microalloying reaction, and adjusting the proportion relation of the put materials according to actual needs. In the operation process, a plurality of places needing to be paid attention are firstly needed to be deoxidized when a ladle filled with molten steel enters an LF furnace station, so that oxidation loss of vanadium nitride during the microalloying reaction of the vanadium nitride is prevented, and Al, ferrosilicon, calcium silicate or the like can be used as deoxidizers according to different steel types; secondly, after the vanadium nitride ball material is put into the molten steel, argon is blown into the molten steel and is strongly stirred, the time is controlled between 10 minutes and 30 minutes, the specific time is required to be adjusted according to the proportion of the material input, and the purpose is to promote the ball material to fully contact with the molten steel, and the molten steel is utilized to absorb vanadium nitride in the ball material; thirdly, the temperature needs to be controlled in the process, the temperature cannot be rapidly increased, the temperature is controlled to be not more than 1600 ℃, otherwise, the loss of vanadium nitride is easy to cause; fourthly, after the above operation, about 0.003 to 0.008 percent of sulfur is increased in the molten steel, and lime is required to be properly added for desulfurization.
By the method, the waste vanadium catalyst can be directly put into molten steel for microalloying reaction after being treated, so that nitrogen and vanadium are increased while molten steel is realized, the performance of finally prepared steel is improved, the yield of vanadium is stable, the utilization rate of the waste vanadium catalyst is high, and the method has higher economic value. Meanwhile, the waste vanadium catalyst contains SO 2 And K 2 O can promote the dissolution of CaO when reacting with molten steel, thereby realizing rapid slagging.
The invention will be further described with reference to specific examples.
Example 1
An LF refining furnace in a steel mill is filled with 100 tons of molten steel, and needs to smelt steel with 0.02 percent of vanadium nitride.
The specific operation is as follows:
and selecting a waste vanadium catalyst of a certain sulfuric acid plant, removing large-particle impurities, drying, crushing, screening, and adjusting the vanadium content ratio to obtain a material with the vanadium content of 7% and the diameter of 0.5-1 mm.
In a closed smelting furnace, 1500kg of molten aluminum is melted by electric heating, 100kg of waste vanadium catalyst is added, and the top heating is performed by an industrial microwave oven, wherein the temperature of the whole melt is controlled at 760 ℃, and the reaction time is 2.5h. Wherein, CO: NH within the first 0.5h 3 =2:1, CO: NH in mid-1 h 3 =1:1, CO: NH in later 1h 3 =1:2, yielding a treated spent vanadium catalyst containing vanadium nitride.
After standing for 1h, slag is removed from the waste vanadium catalyst on the aluminum liquid, and the waste vanadium catalyst is crushed and pressed into balls after cooling, so that vanadium nitride ball materials are prepared.
After entering the LF furnace station, the ladle is deoxidized by utilizing ferrosilicon, the oxygen content is controlled below 200ppm, then the ladle is put into molten steel of the LF furnace according to the material ratio of 11kg/t molten steel, other smelting operations are normally carried out after argon blowing and stirring for 12min, after 40min, the ladle is taken out of the LF station, the vanadium content in the molten steel before and after alloying is detected to be 0.001% and 0.028%, and the comprehensive yield of the vanadium is 87.6%.
Example 2
An LF refining furnace in a certain steel plant is filled with 150 tons of molten steel, and needs to smelt the steel grade containing 0.03 percent of vanadium nitride.
The specific operation is as follows:
and selecting a waste vanadium catalyst of a certain sulfuric acid plant, removing large-particle impurities, drying, crushing, screening, and adjusting the vanadium content ratio to obtain a material with the vanadium content of 10% and the diameter of 0.5-1 mm.
In a closed smelting furnace, 1500kg of molten aluminum is melted by electric heating, 80kg of waste vanadium catalyst is added, and the top heating is performed by an industrial microwave oven, wherein the temperature of the whole melt is controlled at 900 ℃, and the reaction time is 3 hours. Wherein, front partCO: NH within 1h 3 =2.5:1, CO: NH in mid-1.5 h 3 =1:1, CO: NH in late 0.5h 3 =1:3, yielding a treated spent vanadium catalyst containing vanadium nitride.
After standing for 1.5 hours, the waste vanadium catalyst on the aluminum liquid is slagging-off, broken after cooling, pressed into balls, and the vanadium nitride ball material is prepared.
After entering the LF furnace station, the ladle is deoxidized by utilizing ferrosilicon, the oxygen content is controlled below 150ppm, then the ladle is put into molten steel of the LF furnace according to the material ratio of 10kg/t molten steel, other smelting operations are normally carried out after stirring for 15min by blowing argon, the ladle is taken out of the LF station after 42min, the vanadium content in the molten steel before and after alloying is detected to be 0.001% and 0.038%, and the comprehensive yield of the vanadium is 89.7%.
Example 3
An LF refining furnace in a steel mill is filled with 100 tons of molten steel, and needs to smelt steel with 0.02 percent of vanadium nitride.
The specific operation is as follows:
and selecting a waste vanadium catalyst of a certain sulfuric acid plant, removing large-particle impurities, drying, crushing, screening, and adjusting the vanadium content ratio to obtain a material with the vanadium content of 7% and the diameter of 0.5-1 mm.
In a closed smelting furnace, 1500kg of molten aluminum is melted by electric heating, 100kg of waste vanadium catalyst is added, and the top heating is performed by an industrial microwave oven, wherein the temperature of the whole melt is controlled at 680 ℃, and the reaction time is 4 hours. Wherein, CO: NH in the first 1h 3 =4:1, CO: NH in mid-2 h 3 =1:1, CO: NH in later 1h 3 =1:5, yielding a treated spent vanadium catalyst containing vanadium nitride.
After standing for 2 hours, slag is removed from the waste vanadium catalyst on the aluminum liquid, and the waste vanadium catalyst is crushed and pressed into balls after cooling, so that vanadium nitride ball materials are prepared.
After entering the LF furnace station, the ladle is deoxidized by utilizing ferrosilicon, the oxygen content is controlled below 200ppm, then the ladle is put into molten steel of the LF furnace according to the material ratio of 11kg/t molten steel, other smelting operations are normally carried out after argon blowing and stirring for 12min, after 40min, the ladle is taken out of the LF station, the vanadium content in the molten steel before and after alloying is detected to be 0.001% and 0.026%, and the comprehensive yield of the vanadium is 85.7%.
Example 4
An LF refining furnace in a certain steel plant is filled with 150 tons of molten steel, and needs to smelt the steel grade containing 0.03 percent of vanadium nitride.
The specific operation is as follows:
and selecting a waste vanadium catalyst of a certain sulfuric acid plant, removing large-particle impurities, drying, crushing, screening, and adjusting the vanadium content ratio to obtain a material with the vanadium content of 10% and the diameter of 0.5-1 mm.
In a closed smelting furnace, 1500kg of molten aluminum is melted by electric heating, 80kg of waste vanadium catalyst is added, and the top heating is performed by an industrial microwave oven, wherein the temperature of the whole melt is controlled at 800 ℃, and the reaction time is 3.5h. Wherein, CO: NH in the first 1h 3 =3:1, CO: NH in mid-1.5 h 3 =1:1, CO: NH in later 1h 3 =1:3.5, yielding a treated spent vanadium catalyst containing vanadium nitride.
After standing for 1.5 hours, the waste vanadium catalyst on the aluminum liquid is slagging-off, broken after cooling, pressed into balls, and the vanadium nitride ball material is prepared.
After entering the LF furnace station, the ladle is deoxidized by utilizing ferrosilicon, the oxygen content is controlled below 150ppm, then the ladle is put into molten steel of the LF furnace according to the material ratio of 10kg/t molten steel, other smelting operations are normally carried out after stirring for 15min by blowing argon, the ladle is taken out of the LF station after 42min, the vanadium content in the molten steel before and after alloying is detected to be 0.001% and 0.043%, and the comprehensive yield of the vanadium is 91.6%.
The examples of the present invention are merely for describing the preferred embodiments of the present invention, and are not intended to limit the spirit and scope of the present invention, and those skilled in the art should make various changes and modifications to the technical solution of the present invention without departing from the spirit of the present invention.
Claims (9)
1. A method for treating and utilizing a waste vanadium catalyst is characterized in that: the method comprises the following steps:
1. pretreatment of
Collecting a waste vanadium catalyst generated in the sulfuric acid industry, and drying, crushing and screening to obtain a vanadium-containing raw material;
2. synthetic vanadium nitride
Preparing a container filled with molten aluminum, adding vanadium-containing raw material onto the molten aluminum, and blowing CO and NH into the lower part of the container 3 Stirring, heating the aluminum liquid and the liquid level, and controlling the temperature of the aluminum liquid and the liquid level to react between 680 and 900 ℃;
in 0.5-1h of the beginning of the reaction, CO and NH are introduced 3 The volume ratio of (2-4) is 1; in the following 1-2h, CO and NH are introduced 3 Is 1:1 by volume; in the last 0.5-1h of the reaction, CO and NH are introduced 3 The volume ratio of (2) to (5) is 1;
3. to produce the material containing vanadium nitride
Standing the vanadium-containing raw material and aluminum liquid after the reaction in the second step, and then skimming slag to obtain a vanadium nitride-containing material and collecting the vanadium nitride-containing material;
4. microalloying
And (3) adding the vanadium nitride-containing material obtained in the step (III) into molten steel for smelting, and carrying out vanadium nitride microalloy reaction.
2. The method for treating and utilizing the waste vanadium catalyst according to claim 1, wherein the method comprises the following steps: the reaction time of the second step is 2-4h.
3. The method for treating and utilizing the waste vanadium catalyst according to claim 2, wherein the method comprises the following steps: in the second step, the mass ratio of the aluminum liquid to the vanadium-containing raw material is (10-50): 1.
4. A method for treating and utilizing a spent vanadium catalyst according to claim 3, wherein: in the second step, the aluminum liquid and the surface of the liquid are heated from the upper part of the container through industrial microwaves.
5. The method for treating and utilizing the waste vanadium catalyst according to claim 1, wherein the method comprises the following steps: in the first step, the mass percentage of vanadium in the vanadium-containing raw material is not less than 5%.
6. The method for treating and utilizing a spent vanadium catalyst according to any one of claims 1 to 5, wherein: and step four, before starting, deoxidizing the molten steel.
7. The method for treating and utilizing a spent vanadium catalyst according to any one of claims 1 to 5, wherein: in the fourth step, after the materials containing vanadium nitride are put into molten steel, argon is blown into the molten steel and stirred for 10-30min.
8. The method for treating and utilizing a spent vanadium catalyst according to any one of claims 1 to 5, wherein: in the fourth step, the smelting temperature of molten steel is not more than 1600 ℃.
9. The method for treating and utilizing a spent vanadium catalyst according to any one of claims 1 to 5, wherein: and in the fourth step, lime is added into the molten steel for desulfurization treatment after the fourth step is completed.
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| CN101172585A (en) * | 2007-09-30 | 2008-05-07 | 冯良荣 | Method for producing vanadium nitride |
| CN101713014A (en) * | 2009-11-03 | 2010-05-26 | 广东延能新材料科技有限公司 | Steel additive agent vanadium nitride alloy powder core-spun wire |
| CN108906030A (en) * | 2018-03-08 | 2018-11-30 | 湖南三丰钒业有限公司 | A kind of recovery and treatment method of spent vanadium catalyst |
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| FR2101139A1 (en) * | 1970-08-28 | 1972-03-31 | Hollandse Metallurg He | Vanadium carbonitride and/or nitride prepn |
| US3745209A (en) * | 1970-09-09 | 1973-07-10 | Hollandse Metall Ind Billiton | Process for the preparation of vanadium(carbo)nitride |
| US4562057A (en) * | 1984-03-29 | 1985-12-31 | Union Carbide Corporation | Preparation of low-carbon vanadium nitride |
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| CN101713014A (en) * | 2009-11-03 | 2010-05-26 | 广东延能新材料科技有限公司 | Steel additive agent vanadium nitride alloy powder core-spun wire |
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