CN113817953A - Method for producing nitrogen-containing alloy additive by using vanadium-containing waste - Google Patents
Method for producing nitrogen-containing alloy additive by using vanadium-containing waste Download PDFInfo
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- CN113817953A CN113817953A CN202111153798.XA CN202111153798A CN113817953A CN 113817953 A CN113817953 A CN 113817953A CN 202111153798 A CN202111153798 A CN 202111153798A CN 113817953 A CN113817953 A CN 113817953A
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 111
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 80
- 239000000956 alloy Substances 0.000 title claims abstract description 80
- 239000002699 waste material Substances 0.000 title claims abstract description 57
- 239000000654 additive Substances 0.000 title claims abstract description 43
- 230000000996 additive effect Effects 0.000 title claims abstract description 41
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000002245 particle Substances 0.000 claims abstract description 39
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052742 iron Inorganic materials 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 24
- 238000003723 Smelting Methods 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000002485 combustion reaction Methods 0.000 claims abstract description 14
- 238000005121 nitriding Methods 0.000 claims abstract description 14
- 238000006722 reduction reaction Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 239000002893 slag Substances 0.000 claims description 23
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 19
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000007480 spreading Effects 0.000 claims description 4
- 238000003892 spreading Methods 0.000 claims description 4
- 230000000977 initiatory effect Effects 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 239000010431 corundum Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000003832 thermite Substances 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 20
- 230000008569 process Effects 0.000 abstract description 12
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001935 vanadium oxide Inorganic materials 0.000 abstract description 6
- 229910000831 Steel Inorganic materials 0.000 abstract description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
- 239000010959 steel Substances 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 238000005275 alloying Methods 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- -1 ammonium ions Chemical class 0.000 description 2
- 239000012611 container material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010891 electric arc Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 229910000756 V alloy Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/006—Making ferrous alloys compositions used for making ferrous alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/02—Alloys based on vanadium, niobium, or tantalum
- C22C27/025—Alloys based on vanadium, niobium, or tantalum alloys based on vanadium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
- C22C33/06—Making ferrous alloys by melting using master alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C35/00—Master alloys for iron or steel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention relates to the technical field of alloy additive production, in particular to a method for producing a nitrogenous alloy additive by using vanadium-containing waste, which comprises the steps of firstly drying and removing water and volatile impurities in the vanadium-containing waste, then separating vanadium element in the waste product through aluminothermic reduction reaction of the aluminum particles and complex vanadium oxide in the waste product containing vanadium, enriching the vanadium element in the vanadium-based alloy by utilizing the slagging action of a slagging agent, the vanadium pentoxide raw material and the iron particles improve the content of vanadium and iron in the vanadium-based alloy, so that the content of sulfur which is difficult to remove in the vanadium-containing waste product meets the requirement of the nitrogen-containing alloy additive on the content of impurities, the control of the content of elements in the nitrogen-containing alloy additive is realized, thereby ensuring the smooth proceeding of the nitriding combustion reaction, and the finally prepared nitrogenous alloy additive can be directly used in the alloying process of steel smelting, and is beneficial to reducing the whole smelting cost of steel.
Description
Technical Field
The invention relates to the technical field of alloy additive production, in particular to a method for producing a nitrogenous alloy additive by using vanadium-containing waste.
Background
The vanadium-containing waste is waste generated in a vanadium extraction process and a vanadium product processing process of a steel-making enterprise, mainly comprises ferric vanadate mud, ammonium vanadate and vanadium oxide, and the like, wherein the waste is not recycled, so that the loss of vanadium elements can be caused, the long-term accumulation can pollute the field environment, but the vanadium-containing waste is complex in composition, contains complex vanadium oxides, a large amount of ammonium ions, sulfides and other impurities, seriously hinders the research progress of recycling the vanadium-containing waste, and how to realize effective recycling of the vanadium elements in the vanadium-containing waste is always the key research direction of technical personnel in the field.
Disclosure of Invention
The invention provides a method for producing a nitrogenous alloy additive by using vanadium-containing waste, aiming at solving the technical problems that in the prior art, the vanadium-containing waste is complex in composition, impurities are difficult to remove completely, so that effective recycling is difficult to obtain, vanadium element loss is caused, and long-term accumulation causes environmental pollution.
In order to achieve the purpose of the invention, the embodiment of the invention adopts the following technical scheme:
the embodiment of the invention provides a method for producing a nitrogenous alloy additive by using vanadium-containing waste, which specifically comprises the following steps:
s1: drying and crushing the vanadium-containing waste, uniformly mixing the crushed vanadium-containing waste with vanadium pentoxide, aluminum particles, iron particles and a slag former, and using the mixture as a smelting raw material for later use, wherein the content of vanadium in the dried vanadium-containing waste is more than or equal to 30 wt%, and the mass ratio of the dry weight of the vanadium-containing waste to the vanadium pentoxide is less than or equal to 3: 7;
s2: heating the smelting raw materials to 1800-2000 ℃, and initiating an aluminothermic reduction reaction to obtain a vanadium-based alloy;
s3: and crushing the obtained vanadium-based alloy, spreading the crushed vanadium-based alloy in a container, and igniting the crushed vanadium-based alloy in a nitrogen environment to perform nitriding combustion to obtain the nitrogen-containing alloy additive.
Compared with the prior art, the method for producing the nitrogenous alloy additive by using the vanadium-containing waste provided by the invention has the advantages that firstly, water and ammonium ions in the waste are removed by drying, so that the safety of the subsequent thermite reduction reaction and nitriding combustion reaction is ensured; then carrying out aluminothermic reduction reaction on the aluminum particles and complex vanadium oxide in the vanadium-containing waste to obtain a vanadium simple substance, impurities in the vanadium-containing waste are enriched and the alumina and other substances generated by aluminothermic reduction reaction are separated from the vanadium-based alloy by utilizing the slagging action of the slagging medium, the vanadium pentoxide raw material and the iron particles can improve the content of vanadium element and iron element in the vanadium-based alloy, thereby reducing the content of vanadium-containing waste in the vanadium-based alloy, the content of sulfide impurities which are difficult to remove in the drying and smelting processes realizes the control of the content of elements in the nitrogenous alloy additive, ensures the smooth proceeding of the nitriding combustion reaction, finally prepares the nitrogenous alloy additive, realizes the effective recycling of vanadium-containing waste, and simultaneously prepares the nitrogenous alloy additive which can be directly used in the alloying process of steel smelting, thereby reducing the cost of the steel smelting.
Preferably, the vanadium-containing waste product used in the invention is a mixture of ammonium vanadate and ferric vanadate mud, wherein the water content of the ammonium vanadate is less than or equal to 35%, and the content of vanadium element in dry basis is V2O560.00-70.00 wt% of the total weight; the water content of the iron vanadate mud is less than or equal to 65.00 percent, the content of TV in dry basis is 15.00 to 35.00 percent, the content of TFe in dry basis is 20.00 to 35.00 percent, the mass ratio of the medium external ammonium vanadate in the vanadium-containing waste is 1: 0.1-0.5.
When the external ammonium vanadate and the iron vanadate mud contain a large amount of water, and the iron vanadate mud contains sulfides which are difficult to remove, the preferable components and mass ratio of the vanadium-containing waste are favorable for effectively controlling the contents of vanadium elements and other impurity elements in the vanadium-containing waste, the safety of subsequent reaction is ensured, and the content of sulfur elements in the vanadium alloy is controlled to be below 0.06 wt%.
Preferably, the effective components of the slag former used in the invention are MgO and CaO, wherein the content of the effective components is more than or equal to 90 wt%.
The preferable components and compositions of the slag former can control the melting point of the slag at 1800-1900 ℃, can prevent the slag formed in the smelting process from being solidified too early to influence the sedimentation process of the alloy, and avoids the phenomenon that the vanadium-based alloy is difficult to separate from the slag.
Preferably, the mass ratio of the vanadium pentoxide to the vanadium-containing waste, aluminum particles, iron particles and slag former used in the invention is 1: 0.5-1: 0.85-1.7: 0.7-1.3: 0.17-1.6.
The aluminum particles are important reactants of the aluminothermic reduction reaction in S2, and the optimal aluminum particle dosage can ensure that the complex vanadium oxide in vanadium pentoxide and vanadium-containing waste gas completely reacts, and simultaneously avoid excessive aluminum impurities from being doped into vanadium base and gold bell to influence the alloy quality; the optimized amount of the slag former can ensure the smooth operation of the aluminothermic reduction reaction, and can also ensure that the generated vanadium-based alloy can be smoothly settled and separated from molten slag, and the optimized amount of the vanadium pentoxide and the iron particles can adjust the element content in the vanadium-based alloy, so that the impurity content of sulfide which is difficult to remove in the drying and smelting process meets the requirement of the nitrogen-containing alloy additive on the impurity content, and the control of the element content in the nitrogen-containing alloy additive is realized, thereby ensuring the smooth operation of the nitriding combustion reaction, and preparing the nitrogen-containing alloy additive with the vanadium content of more than or equal to 45 wt% and the nitrogen content of more than or equal to 10 wt%.
Preferably, S1 the waste product containing vanadium is dried to water content less than 0.5 wt%, and crushed to particle size less than 60 mesh, the particle size of the used aluminum particles is 1.0mm-25.00mm, and the particle size of the used iron particles is 1.0mm-10.0 mm.
The optimized granularity of the raw materials can ensure that the smelting raw materials are mixed more uniformly, thereby accelerating the speed of the aluminothermic reduction reaction and saving the reaction time.
Preferably, the electrode ignition current of the smelted raw material in S2 is 7000A-10000A.
The ignition current is a key factor for enabling complex vanadium oxide in the vanadium-containing waste to start to react with aluminum particles, and the inventor finds that the initial temperature of the initiation reaction is 1800-2000 ℃, so the current is set to 7000A-10000A.
Preferably, in S3, the vanadium-based alloy is crushed to a particle size of less than or equal to 60 meshes, the container material in the nitriding combustion process is graphite or corundum, and the thickness of the vanadium-based alloy spread in the container is 100mm-500 mm.
The optimized container material can reduce the loss caused by nitridation in the vanadium-based alloy nitriding combustion process, combines the vanadium-based alloy granularity and the flat paving thickness, can ensure that the vanadium-based alloy is heated more uniformly in the smelting process, is also beneficial to the implementation of nitriding combustion reaction, ensures that the vanadium-based alloy raw material is nitrided more completely, and improves the reaction rate.
Preferably, nitrogen with the purity of more than or equal to 99 percent is continuously introduced in the nitridation combustion process of vanadium base, and the nitrogen pressure is controlled to be 6-15 MPa.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention is further illustrated below in the following examples.
Example 1
The embodiment provides a method for producing a nitrogen-containing alloy additive by using vanadium-containing waste, which is used for producing the nitrogen-containing alloy additive by using the vanadium-containing waste, wherein the used raw materials are as follows:
53.98kg of off-grade ammonium vanadate, wherein the water content is 32.5 percent, and the content of vanadium element in dry basis is V2O5Calculated as 67 wt%, the balance being impurities;
15kg of iron vanadate mud, wherein the moisture content is 58.26%, and the dry basis of the iron vanadate mud comprises 22.39 wt% of TV, 23.18 wt% of TFe and the balance of impurities;
110kg of vanadium pentoxide of which the active ingredient V is2O5The content of (D) is 95.6 wt%, and the balance is impurities;
80kg of aluminum particles with the granularity of 1.0-25.0mm, 96.41kg of iron particles with the granularity of 1.0-10.0mm and 60kg of slag former, wherein the effective components of the slag former are MgO and CaO, and the content is 92.1 wt%;
the method for preparing the nitrogenous alloy additive by adopting the raw materials comprises the following specific steps:
s1: drying the ammonium vanadate and the ferric vanadate mud to the water content of 0.3%, crushing the ammonium vanadate and the ferric vanadate mud to 50 meshes, and uniformly mixing the ammonium vanadate and the ferric vanadate mud with vanadium pentoxide, aluminum particles, iron particles and a slag former to obtain a smelting raw material;
s2: transferring the obtained smelting raw material to an electric arc furnace, controlling electrode current 8000A to enable the material to generate aluminothermic reduction reaction, separating and removing generated slag to obtain vanadium-based alloy, and testing to obtain vanadium-based alloy with TV (total weight) of 48.75%, Al (total weight) of 2.50%, and the balance of iron and a small amount of impurities;
s3: crushing the obtained vanadium-based alloy until the granularity is less than or equal to 60 meshes, spreading the vanadium-based alloy in a graphite furnace body in a nitriding synthetic furnace to form a raw material layer with the thickness of 300mm, filling nitrogen with the purity of more than or equal to 99.00 percent, igniting under the condition of nitrogen pressure of 12MPa to perform nitriding combustion reaction, cooling after the reaction is finished to obtain the nitrogen-containing alloy additive, and crushing and screening the obtained nitrogen-containing alloy additive to the particle size of 10mm-80mm for later use.
Example 2
The embodiment provides a method for producing a nitrogen-containing alloy additive by using vanadium-containing waste, which is used for producing the nitrogen-containing alloy additive by using the vanadium-containing waste, wherein the used raw materials are as follows:
65kg of other external ammonium vanadate, wherein the water content is 31.84 wt%, and the vanadium element in the dry basis is V2O5Calculated as 68.25 wt%, and the balance impurities;
25kg of iron vanadate mud, wherein the moisture content is 56.72%, and the dry basis thereof contains 26.19 wt% of TV, 25.41 wt% of TFe, and the balance of impurities;
120kg of vanadium pentoxide of which the active ingredient V is2O5The content of (D) is 96.52 wt%, and the balance is impurities;
95kg of aluminum particles with the granularity of 1.0-25.0mm, 99kg of iron particles with the granularity of 1.0-10.0mm and 50kg of slag former, wherein the effective components of the slag former are MgO and CaO, and the content of the slag former is 91.5 wt%;
the method for preparing the nitrogenous alloy additive by adopting the raw materials comprises the following specific steps:
s1: drying the ammonium vanadate and the ferric vanadate mud to the water content of 0.5%, crushing the ammonium vanadate and the ferric vanadate mud to 60 meshes, and uniformly mixing the ammonium vanadate and the ferric vanadate mud with vanadium pentoxide, aluminum particles, iron particles and a slag former to obtain a smelting raw material;
s2: transferring the obtained smelting raw material to an electric arc furnace, controlling electrode current 9000A to enable the material to generate aluminothermic reduction reaction, separating and removing generated slag to obtain vanadium-based alloy, and testing to obtain vanadium-based alloy containing 50.76 wt% of TV, 2.80 wt% of Al and the balance of iron and a small amount of impurities;
s3: crushing the obtained vanadium-based alloy until the granularity is less than or equal to 60 meshes, spreading the vanadium-based alloy in a graphite furnace body in a nitriding synthetic furnace to form a raw material layer with the thickness of 450mm, introducing nitrogen with the purity of more than or equal to 99.00 percent, igniting under the condition of 10MPa of nitrogen pressure to perform nitriding combustion reaction, cooling after the reaction is finished to obtain the nitrogen-containing alloy additive, and crushing and screening the obtained nitrogen-containing alloy additive to the particle size of 10mm-80mm for later use.
Comparative example 1
Compared with the method in the embodiment 2, the method for producing the nitrogen-containing alloy additive by utilizing the vanadium-containing waste has the advantages that the consumption of the slag former is 15kg, other raw materials and process parameters are consistent with those in the embodiment 1, and in the S2 aluminothermic reduction process, the generated slag and the vanadium-based alloy are difficult to separate and remove, so that the vanadium-based alloy is not obtained.
Comparative example 2
Compared with the method in the embodiment 2, except that the used other products of ammonium vanadate are 50kg in mass and the used ferric vanadate mud is 40kg in mass, the other raw materials and the technological parameters are consistent with those in the embodiment 1.
Comparative example 3:
compared with the method in the embodiment 2, except that the used other products of ammonium vanadate are 90kg in mass, the used ferric vanadate mud is 40kg in mass, the used aluminum particles are 100kg in mass, and the rest raw materials and process parameters are consistent with those in the embodiment 1.
Detection example: the contents of vanadium, nitrogen and sulfur, which are important impurities, in the nitrogenous alloy additives prepared in examples 1 and 2 and comparative examples 2 and 3 were examined, and the results are shown in table 1:
TABLE 1
As can be seen from the data in Table 1, the alloy additive produced by adopting the vanadium-containing waste is controlled by the amount of the raw materials and the process, the vanadium content is more than or equal to 45.00 wt%, the nitrogen content is more than or equal to 10.00 wt%, and the content of the key impurity sulfur is less than or equal to 0.06 wt%, so that the alloy additive can be directly used in the alloying process of steelmaking.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A method for producing a nitrogenous alloy additive from vanadium-containing waste comprises the following steps:
s1: drying and crushing the vanadium-containing waste, uniformly mixing the crushed vanadium-containing waste with vanadium pentoxide, aluminum particles, iron particles and a slag former, and using the mixture as a smelting raw material for later use, wherein the content of vanadium in the dried vanadium-containing waste is more than or equal to 30 wt%, and the mass ratio of the dry weight of the vanadium-containing waste to the vanadium pentoxide is less than or equal to 3: 7;
s2: heating the smelting raw materials to 1800-2000 ℃, and initiating an aluminothermic reduction reaction to obtain a vanadium-based alloy;
s3: and crushing the vanadium-based alloy, spreading the crushed vanadium-based alloy in a container, and igniting the crushed vanadium-based alloy in a nitrogen environment to perform nitriding combustion to obtain the nitrogen-containing alloy additive.
2. The method of claim 1, wherein the vanadium-containing waste is a mixture of ammonium vanadate and ferric vanadate paste, wherein the ammonium vanadate has a water content of 35% or less, and the content of vanadium in the dry basis is V2O560.00-70.00 wt% of the total weight; the water content of the iron vanadate mud is less than or equal to 65.00 percent, TV in dry basis is 15.00-35.00 percent, TFe in dry basis is 20.00-35.00 percent, the mass ratio of the medium external ammonium vanadate to the iron vanadate mud in the vanadium-containing waste is 1: 0.1-0.5.
3. The method for producing the nitrogen-containing alloy additive by using the vanadium-containing waste as claimed in claim 2, wherein the slag former comprises MgO and CaO as active ingredients, and the content of the active ingredients is not less than 90 wt%.
4. The method for producing the nitrogen-containing alloy additive by using the vanadium-containing waste as claimed in claim 2, wherein the mass ratio of the vanadium pentoxide to the vanadium-containing waste, the iron particles, the aluminum particles and the slag former is 1: 0.5-1: 0.85-1.7: 0.7-1.3: 0.17-1.6.
5. The method for producing the nitrogenous alloy additive from the vanadium-containing waste as set forth in claim 1, wherein the vanadium-containing waste is dried to a moisture content of 0.5 wt% or less in S1 and then crushed to a particle size of 60 mesh or less.
6. The method for producing nitrogenous alloy additives from vanadium-containing waste as set forth in claim 5, wherein the aluminum particles in S1 have a particle size of 1.0mm to 25.0mm, and the iron particles have a particle size of 1.0mm to 10.0 mm.
7. The method for producing the nitrogen-containing alloy additive from the vanadium-containing waste as set forth in claim 1, wherein the vanadium-based alloy is crushed to a particle size of 60 mesh or less in S3.
8. The method for producing the nitrogenous alloy additive from the vanadium-containing waste as set forth in claim 7, wherein the vessel used in the nitriding combustion process in S3 is made of graphite or corundum; the thickness of the vanadium-based alloy laid in the smelting container is 100mm-500 mm.
9. The method for producing the nitrogenous alloy additive from the vanadium-containing waste as set forth in claim 1, wherein the thermite reduction reaction in S2 is initiated by an electrode, and the electrode-initiated current is 7000A to 10000A.
10. The method for producing the nitrogen-containing alloy additive by using the vanadium-containing waste as claimed in claim 1, wherein nitrogen with purity of not less than 99% is continuously introduced during the nitridation combustion process of the vanadium-based alloy in S3, and the nitrogen pressure is controlled to be 6-15 MPa.
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| CN114921642A (en) * | 2022-03-14 | 2022-08-19 | 河钢承德钒钛新材料有限公司 | Preparation method of vanadium-containing alloy additive |
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