CN115161479A - Method for preparing Ti-Al-Si alloy by using waste denitration catalyst - Google Patents
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- 239000002699 waste material Substances 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 40
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- 239000002893 slag Substances 0.000 claims abstract description 22
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- 238000004140 cleaning Methods 0.000 claims description 6
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- 229910001385 heavy metal Inorganic materials 0.000 description 3
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- 241000282414 Homo sapiens Species 0.000 description 2
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- 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
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- 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
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1218—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by dry processes
-
- 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
- C22B34/225—Obtaining vanadium from spent catalysts
-
- 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
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
- C22B34/365—Obtaining tungsten from spent catalysts
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
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- 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
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- Y02P10/20—Recycling
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Abstract
The invention discloses a method for preparing Ti-Al-Si alloy by using waste denitration catalyst, which comprises the following steps: the waste denitration catalyst is deashed, cleaned and ball-milled, a slag former is mixed with a reducing agent, and high-temperature thermal reduction is carried out in an argon atmosphere. The invention uses the slag former with lower viscosity, improves the recovery rate of valuable metals in the waste denitration catalyst, and simultaneously adopts a high-temperature thermal reduction process, thereby being beneficial to removing impurities and improving economic and environmental benefits.
Description
Technical Field
The invention relates to the technical field of solid waste recycling, in particular to a method for directly preparing Ti-Al-Si alloy by recycling waste denitration catalyst.
Background
In the modern times of taking coal resources as main energy sources, flue gas discharged from thermal power plants is one of pollution sources. Wherein NO x Can cause serious natural disasters such as acid rain and photochemical smog, so that NO is generated x Becomes an important environmental problem to be solved. In policy of nitrogen oxide control technology in thermal power plants (new edition 2021), provision is made: when the emission content can not meet the requirement of nitrogen oxide emission, a flue gas denitration facility is additionally arranged.
In a wide variety of NO remediation x Among the technologies, selective catalytic reduction (Selective catalytic reduction) is the most mature and widely used denitration technology. The method is that under the action of certain temperature and catalyst, ammonia or hydrocarbon is used as reductant to selectively react NO x A process for reduction to nitrogen and water. The method has little influence on the quality of the atmospheric environment, and is the most mature denitration technology with the highest denitration efficiency and the most extensive application at present. SCR technology is a reducing agent (NH) 3 ) Under the action of catalyst, NO in the flue gas is removed x Reducing to nitrogen and water. "Selective" means that ammonia selectively converts NO x The reaction of reduction is carried out. The catalytic reaction temperature is 320-400 ℃. The technology has no by-product, and the denitration efficiency can reach more than 80-90%. Generally, the life of a denitration catalyst is about 25000 hours, the denitration catalyst is deactivated after long-term use, a part of deactivated catalyst can be reactivated for use by cleaning and supplementing catalyst elements, but many irreparable denitration catalysts can only be buried. The landfill treatment not only occupies land resources but also causes irreversible pollution to the environment, and heavy metals in the landfill are accompanied byAlong with the circulation of the ecosphere, the ecological sphere enters the human body, and the health of human beings is influenced.
The waste denitration catalyst which can not be repaired by damage contains a large amount of heavy metal substances, wherein TiO 2 80-90 percent of SiO 2 The content is 6 to 10 percent, WO 3 Content of 4% -6%, V 2 O 5 The content is 0.4-1%. The metals have higher recovery value, the effective recovery of the metals can realize the resource recycling, reduce the environmental pollution and improve the use benefit. At present, the waste denitration catalyst is mainly divided into a pyrogenic method and a wet method, a great deal of research is centered on extracting metals such as V, W and the like in the waste denitration catalyst, and Ti with the largest content is ignored and only a small amount of reports are provided. And heavy metals in the waste denitration catalyst are recovered by a wet method, so that the process is too complex and is not beneficial to recycling of the metals.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for directly preparing a Ti-Al-Si alloy by using a waste denitration catalyst, and solves the problems that the recovery of metal titanium is lacked and the recovery process is complex in the recovery process of the waste denitration catalyst.
In order to solve the technical problem, the technical scheme adopted by the invention is as follows:
a method for preparing Ti-Al-Si alloy by using waste denitration catalyst comprises the following specific steps:
1) Pretreating the waste denitration catalyst: sequentially deashing, cleaning and ball-milling the waste denitration catalyst, and sieving the waste denitration catalyst by a sieve of 100-200 meshes;
2) Mixing raw materials: mixing the following raw materials by mass, 10-30 parts of pretreated waste denitration catalyst, 10-30 parts of reducing agent and 30-50 parts of slagging agent;
3) Pressing raw materials: pressing the mixed raw materials obtained in the step 2), wherein the pressure of a sample pressing machine is 200-400 Mpa, and then putting the sample pressing machine into a crucible;
4) Smelting: putting the crucible filled with the mixed raw materials in the step 3) into an induction furnace, introducing argon, smelting at 1400-1700 ℃, and preserving heat for 20-30 min to obtain a melt with the surface covered with slag;
5) Cooling and ingot lifting: cooling the melt obtained in the step 3), and removing slag covered on the surface through ingot lifting to obtain the Ti-Al-Si alloy.
Further, the mixed raw materials in the step 2) comprise the following components in parts by mass: 20-30 parts of pretreated waste denitration catalyst, 20-30 parts of reducing agent and 40-50 parts of slagging agent.
Further, the reducing agent is aluminum and calcium powder or an aluminum-calcium alloy.
Further, the mass components of the aluminum-calcium alloy are not less than 10 parts.
Further, the slagging agent is CaCO 3 、NaCO 3 、Na 3 AlF 6 And MgF 2 A mixture of (a); wherein the mass percentage of each component is CaCO 3 20～30％、NaCO 3 20～30％、Na 3 AlF 6 15 to 25 percent and MgF 2 15～25％。
Further, the mass ratio of the slagging agent is CaCO 3 ：NaCO 3 ：Na 3 AlF 6 ：MgF 2 ＝28：28：22：22。
Further, the smelting temperature in the step 4) is 1550-1700 ℃, and the heat preservation time is 30min.
Further, the waste denitration catalyst is a catalyst which is damaged and cannot be activated again.
Further, the purity of the argon in the step 4) is more than or equal to 99.999 percent.
Furthermore, before smelting, the waste denitration catalyst and the slagging agent are roasted at high temperature for 5 hours to remove water.
Compared with the prior art, the invention has the following beneficial effects:
1. the direct recovery method of the waste denitration catalyst provided by the invention has no wet treatment process, realizes resource recovery and utilization of the waste denitration catalyst by a one-step method, and has the advantages of simple preparation process and convenient control.
2. The invention provides a method for directly preparing Ti-Al-Si alloy by effectively recycling waste denitration catalyst, which takes aluminum-calcium alloy as reductionAgent, caCO 3 、NaCO 3 、Na 3 AlF 6 And MgF 2 As a slag former, na 3 AlF 6 And MgF 2 The melting point of the slag can be reduced, the furnace lining is protected, and the precious metal of the waste denitration catalyst is recycled in the process of no wet method after the high-temperature smelting in the induction furnace. And the density and viscosity of the slag former are low, so that the slag-metal separation can be better realized, and the recovery rate of valuable metals in the waste denitration catalyst is improved.
3. The method of the invention has the advantages that the recovery rate of titanium can reach 98 percent, the yield of silicon can reach 98 percent, the yield of W can reach 98 percent, and the yield of V can reach 97 percent.
Drawings
FIG. 1 is a flow chart of the process for preparing a Ti-Al-Si alloy according to the present invention;
FIG. 2 is an X-ray diffraction (XRD) analysis pattern of example 1;
FIG. 3 is a Scanning Electron Microscope (SEM) and X-ray energy spectral analysis (EDS) profile of example 1.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the present invention will be further described with reference to the following specific examples, but the embodiments of the present invention are not limited thereto.
Referring to fig. 1, the invention provides a method for directly preparing a Ti-Al-Si alloy from a waste denitration catalyst, which comprises the following specific steps:
1) Pretreating the waste denitration catalyst: sequentially performing deashing, cleaning and ball milling treatment on the waste denitration catalyst, and sieving the waste denitration catalyst by using a 100-mesh sieve; so that a relatively pure Ti-Al-Si alloy can be obtained afterwards.
2) Mixing raw materials: mixing raw materials according to the following mass components, 10-30 parts of pretreated waste denitration catalyst, 10-30 parts of reducing agent and 30-50 parts of slagging agent;
3) Pressing raw materials: pressing the mixed raw materials obtained in the step 2), and then putting the raw materials into a crucible;
4) Smelting: and (3) putting the crucible filled with the mixed raw materials in the step 3) into an induction furnace, introducing argon, smelting at 1400-1700 ℃, and preserving heat for 20-30 min to obtain a melt with the surface covered with slag. The reduction reaction is carried out in an argon atmosphere, so that the reduction product can be prevented from being oxidized;
5) Cooling and ingot lifting: cooling the melt obtained in the step 3), and removing slag covered on the surface through ingot forming to obtain the Ti-Al-Si alloy.
Preferably, the waste denitration catalyst and the slag former are roasted at high temperature before smelting; so as to remove the moisture and organic impurities in the furnace charge and improve the unit heat effect of the furnace charge. The calcination time is preferably 5 hours in order to achieve better crystal water extraction efficiency.
The preferable mixed raw materials comprise the following components in percentage by mass: 20-30 parts of waste denitration catalyst, 10-30 parts of reducing agent and 40-50 parts of slagging agent, so that the recovery efficiency of valuable metals in the waste denitration catalyst is improved.
The particle size of the reducing agent is preferably less than or equal to 100 meshes, so that the reaction speed and the yield can be improved; the purity of the reducing agent is preferably more than or equal to 99 percent, so that the reaction rate can be improved and the impurity content can be reduced.
The method selected by the invention is an aluminothermic reduction method, al is used as a main reducing agent, and Ca is used as a deoxidizing agent to be added, so that the purity of the alloy is improved, and the oxygen content is reduced.
The invention provides metallurgical titanium slag for recycling waste denitration catalysts, which comprises the following components in percentage by mass as shown in table 1.
TABLE 1 Components of waste denitration catalyst
The five-element slag system is selected, so that the fluidity of slag in the smelting process can be increased, the mass transfer efficiency is increased, harmful elements in the waste denitration catalyst are separated, the harmful elements in the alloy are reduced, and the purity of the alloy is improved.
In the invention, the technical problem to be solved is to provide a low-melting-point low-density slag phase for efficiently recovering valuable metals in the waste denitration catalyst, and the Ti-Al-Si alloy is directly prepared in one step.
Example 1
A method for directly preparing Ti-Al-Si alloy by using waste denitration catalyst is disclosed, wherein the composition of the waste denitration catalyst is shown in Table 2.
TABLE 2
The method comprises the following specific steps:
1) Removing ash from the waste denitration catalyst, cleaning, ball-milling and sieving to obtain a raw material with a particle size of less than 100 meshes;
2) 50g of waste denitration catalyst and CaCO 3 20g、NaCO 3 20g、Na 3 AlF 6 14g、MgF 2 Mixing 14g and 33g of reducer aluminum-calcium alloy uniformly;
3) Mixing the raw materials in the step 2), pressing, wherein the pressure of a sample pressing machine is 200Mpa, and then putting into a crucible;
4) Putting the crucible filled with the raw materials into a silicon-molybdenum furnace, heating to 1550 ℃, and preserving heat for 30min;
5) After smelting is finished, the sample is cooled along with the furnace, and ingot removal and slag removal are carried out to obtain the Ti-Al-Si alloy.
As shown in FIG. 2, the X-ray diffraction (XRD) analysis pattern of the alloy obtained in this example was determined. As shown in FIG. 2, among them, tiAl and Al 5 Ti 2 、Al 3 V 0.3 T 0.6 And Ti 5 Si 3 The detection of the alloy phase indicates that valuable elements in the waste denitration catalyst are effectively recovered. Among them, the element W is not easily detected by XRD because of its small content.
Referring to FIG. 3, a Scanning Electron Microscope (SEM) and X-ray energy spectrum analysis (EDS) profile of the alloy obtained in this example is shown. As can be seen from FIG. 3, the main phases of the alloy are TiAl alloy and TiSi alloy, and as can be seen from the EDS (scanning electron Spectroscopy), the bright part in the SEM spectrum is mainly TiSi alloy, the rest part is mainly TiAl alloy, and the oxygen content of the alloy is low, which is consistent with the XRD detection result.
The Inductively Coupled Plasma (ICP) detection shows that the yield of titanium is about 98%, the yield of silicon is about 98%, the recovery rate of W is about 97%, and the recovery rate of V is about 97%.
Example 2
A method for directly preparing Ti-Al-Si alloy by using waste denitration catalyst, the composition of the waste denitration catalyst is shown in Table 3,
TABLE 3
The method comprises the following specific steps:
1) Removing ash from the waste denitration catalyst, cleaning, ball-milling and sieving to obtain a raw material with a particle size of less than 100 meshes;
2) 100g of waste denitration catalyst, caCO 3 40g、NaCO 3 40g、Na 3 AlF 6 30g、MgF 2 Mixing 30g of aluminum-calcium alloy and 70g of reducing agent uniformly;
3) Mixing the raw materials in the step 2), pressing, wherein the pressure of a sample pressing machine is 400Mpa, and then putting into a crucible;
4) Putting the crucible filled with the raw materials into a silicon-molybdenum furnace, heating to 1700 ℃, and preserving heat for 30min;
5) After smelting is finished, the sample is cooled along with the furnace, and ingot taking and slag removal are carried out to obtain the Ti-Al-Si alloy.
The Inductively Coupled Plasma (ICP) detection shows that the yield of titanium is about 97%, the yield of silicon is about 95%, the recovery rate of W is about 98%, and the recovery rate of V is about 97%.
In conclusion, the direct recovery method of the waste denitration catalyst provided by the invention realizes resource recycling of the waste denitration catalyst through a one-step method, and has the advantages of simple preparation process and convenience in control. In addition, the recovery rate of titanium after smelting can reach 98%, the yield of silicon can reach 98%, the yield of W can reach 98%, and the yield of V can reach 97%, so that unexpected effects are achieved.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the technical solutions, and those skilled in the art should understand that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all that should be covered by the claims of the present invention.
Claims (10)
1. A method for preparing Ti-Al-Si alloy by using waste denitration catalyst is characterized by comprising the following specific steps:
1) Pretreating the waste denitration catalyst: sequentially deashing, cleaning and ball-milling the waste denitration catalyst, and sieving the waste denitration catalyst by a sieve of 100 to 200 meshes;
2) Mixing raw materials: mixing raw materials according to the following mass components, and then carrying out pretreatment on 10-30 parts of waste denitration catalyst, 10-30 parts of reducing agent and 30-50 parts of slag former;
3) Pressing raw materials: pressing the mixed raw materials in the step 2), wherein the pressure of a sample pressing machine is 200 to 400Mpa, and then putting the sample pressing machine into a crucible;
4) Smelting: putting the crucible filled with the mixed raw materials in the step 3) into an induction furnace, introducing argon, smelting at 1400-1700 ℃, and preserving heat for 20-30min to obtain a melt with the surface covered with slag;
5) Cooling and ingot lifting: cooling the melt obtained in the step 3), and removing slag covered on the surface through ingot lifting to obtain the Ti-Al-Si alloy.
2. The method for preparing the Ti-Al-Si alloy by using the waste denitration catalyst according to claim 1, wherein the mixed raw material in the step 2) comprises the following components in parts by mass: 20-30 parts of pretreated waste denitration catalyst, 20-30 parts of reducing agent and 40-50 parts of slag former.
3. The method of preparing a Ti-Al-Si alloy using the spent denitration catalyst according to claim 1, wherein the reducing agent is powder of aluminum and calcium, or an aluminum-calcium alloy.
4. The method for preparing the Ti-Al-Si alloy by using the waste denitration catalyst according to claim 3, wherein the mass component of the aluminum-calcium alloy is not less than 10 parts.
5. The device of claim 1The method for preparing the Ti-Al-Si alloy by using the waste denitration catalyst is characterized in that the slagging agent is CaCO 3 、NaCO 3 、Na 3 AlF 6 And MgF 2 A mixture of (a); wherein the mass percentage of each component is CaCO 3 20~30%、NaCO 3 20~30%、Na 3 AlF 6 15 to 25% and MgF 2 15~25%。
6. The method for preparing Ti-Al-Si alloy by using the waste denitration catalyst as claimed in claim 5, wherein the mass ratio of the slag former is CaCO 3 ：NaCO 3 ：Na 3 AlF 6 ：MgF 2 =28：28：22：22。
7. The method for preparing the Ti-Al-Si alloy by using the waste denitration catalyst as recited in claim 1, wherein the melting temperature in the step 4) is 1550 to 1700 ℃, and the holding time is 30min.
8. The method of preparing a Ti-Al-Si alloy using the spent denitration catalyst according to claim 1, wherein the spent denitration catalyst is a damaged catalyst that cannot be reactivated.
9. The method for preparing the Ti-Al-Si alloy by using the waste denitration catalyst according to claim 1, wherein the purity of the argon gas in the step 4) is not less than 99.999%.
10. The method for preparing the Ti-Al-Si alloy by using the waste denitration catalyst according to claim 1, wherein the waste denitration catalyst and the slag former are roasted at a high temperature for 5 hours to remove water before smelting.
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