CN115141932A - Valuable metal recovery method and application thereof - Google Patents
Valuable metal recovery method and application thereof Download PDFInfo
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- CN115141932A CN115141932A CN202210736811.2A CN202210736811A CN115141932A CN 115141932 A CN115141932 A CN 115141932A CN 202210736811 A CN202210736811 A CN 202210736811A CN 115141932 A CN115141932 A CN 115141932A
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- valuable metals
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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
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B11/00—Making pig-iron other than in blast furnaces
- C21B11/10—Making pig-iron other than in blast furnaces in electric furnaces
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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
- C22B11/00—Obtaining noble metals
- C22B11/02—Obtaining noble metals by dry processes
- C22B11/021—Recovery of noble metals from waste materials
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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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/02—Obtaining nickel or cobalt 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
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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
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/34—Obtaining molybdenum
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D17/00—Arrangements for using waste heat; Arrangements for using, or disposing of, waste gases
- F27D17/004—Systems for reclaiming waste heat
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D17/00—Arrangements for using waste heat; Arrangements for using, or disposing of, waste gases
- F27D17/008—Arrangements for using waste heat; Arrangements for using, or disposing of, waste gases cleaning gases
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a valuable metal recovery method and application thereof, comprising the following steps: mixing the waste residue containing valuable metals and the ingredients, and then carrying out high-temperature reaction in a plasma melting furnace; the auxiliary materials comprise auxiliary materials, and the auxiliary materials comprise alkaline components and acidic components; the alkaline component comprises CaO and the acidic component comprises SiO 2 And Al 2 O 3 The molar ratio of the alkaline component to the acidic component after the reaction is 1.6-1.2, the method for recovering valuable metals opens up a new feasible path, reduces the risk of environmental pollution, performs resource utilization on byproducts formed by the system, solves the technical problem of waste residue treatment, and is suitable for industrialization.
Description
Technical Field
The invention belongs to the field of recycling of waste residues containing valuable metals, and particularly relates to a valuable metal recycling method and application thereof.
Background
A large amount of metals exist in waste residues generated in waste incineration and chemical industry, the metals contain a large amount of valuable metals, the conventional waste residues are treated by landfill and cement kiln in a coordinated mode, the waste residues occupy a large amount of land, and the risk of environmental pollution caused by improper landfill exists. The cement kiln co-treatment is to burn the garbage at 860-1000 ℃; mixing the burned residues into a cement kiln decomposing furnace according to a certain proportion, and calcining the residues together with cement raw materials to form cement clinker; and gas generated by incineration is burnt at high temperature, decomposed and discharged into the atmosphere through a kiln tail purification system. In the process, harmful substances are not subjected to targeted harmless treatment, so the risk of environmental pollution is not eliminated.
Therefore, it is urgent to develop a method for recovering valuable metals and the application thereof.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a valuable metal recovery method and application thereof, which can effectively improve the recovery rate of the waste residue containing valuable metals.
The invention also provides an application of the valuable metal recovery method in recovering the waste residue containing valuable metals.
According to an embodiment of the first aspect of the invention, a method for recovering valuable metals comprises the following steps: mixing the waste residue containing valuable metals and the ingredients, and then carrying out high-temperature reaction in a plasma melting furnace; the auxiliary materials comprise auxiliary materials, and the auxiliary materials comprise alkaline components and acidic components; the alkaline component comprises CaO and the acidic component comprises SiO 2 And Al 2 O 3 The molar ratio of the basic component to the acidic component after the reaction is 1.
The mechanism for recovering valuable metals provided by the invention is as follows:
the plasma is used as a heat source to form high temperature, and can promote the carbonization and the cracking of organic matters in the waste residue to generate CO and H 2 Reducing atmosphere such as small molecule gas, and reducing solid such as carbon;
under the action of a heat source, the auxiliary materials form glassy state melts to wrap heavy metal substances in a vitrified grid, so that a glassy state inorganic substance byproduct is formed, and the loss of the heavy metal substances is avoided;
the plasma can promote various reactions, for example, the products of the organic matters can perform oxidation-reduction reaction with heavy metal substances wrapped in the vitrified grid, so that valuable metals are reduced into simple metal substances;
under the action of gravity, the materials in the plasma melting furnace are layered and divided into an upper glass body layer and a lower metal layer, the upper layer is discharged from a glass body discharge port and then cooled to form a glass body byproduct, the lower layer is deposited at the bottom of the furnace, and is discharged out of the furnace from a metal discharge port intermittently or continuously to form a reducing metal byproduct (containing valuable metals) after being cooled, and then the reducing metal byproduct is recycled.
The synthesis gas generated by the system is purified by a tail gas treatment system and then directly subjected to waste heat utilization or used as combustible gas resource utilization.
In a plasma gasification melting furnace, providing high-temperature and high-activity reducing atmosphere by using plasma equipment, converting residual organic matters in waste residues containing valuable metals into organic matters, simultaneously melting inorganic matters in the waste residues and reacting auxiliary materials to obtain glassy state melts, wrapping heavy metal substances in a vitrification mesh, and forming a glassy state inorganic matter byproduct; an important feature of the plasma as a heat source is: heat supply and oxygen supply can be completely separated, so that the high temperature formed in the furnace can improve the reducing capability of carbon and keep the whole reducing atmosphere in the furnace; the valuable metals (such as Mo, co, ni, V, fe and the like) in the inorganic by-products forming the vitreous state can be reduced into the metallic state under the conditions of high temperature and reducing atmosphere in the furnace, the material layer is layered in the melting tank under the action of gravity and is divided into an upper vitreous body layer and a lower metal layer, the upper layer is cooled to form the vitreous by-products after being discharged from a vitreous body discharge port, the lower layer is deposited at the bottom of the furnace, and the reducing metal by-products (containing the valuable metals) are formed after being intermittently or continuously discharged from a metal discharge port outside the furnace and cooled to be recycled. The synthesis gas generated by the system is purified by a tail gas treatment system and then directly subjected to waste heat utilization or is used as combustible gas for resource utilization.
The valuable metal recovery method provided by the embodiment of the invention has at least the following beneficial effects:
1. the plasma is used as a heat source, heat supply and oxygen supply can be completely separated, the high temperature formed in the furnace can improve the reducing capability of carbon, and the whole reducing atmosphere in the furnace is kept; the high-energy plasma excited by the plasma can promote chemical reaction and improve the reduction rate of the metal.
According to some embodiments of the invention, the waste residue includes a component of organic matter.
According to some embodiments of the invention, the furnish comprises CaO, siO 2 And Al 2 O 3 A mixture of (a).
According to some embodiments of the invention, the ingredients comprise, in parts by weight, 9 to 43 parts of the CaO and the SiO 2 19 to 70 portions of Al 2 O 3 8 to 39 portions.
According to some embodiments of the invention, the added mass of the burden is no more than 20% of the mass of the slag.
According to some embodiments of the invention, the furnish further comprises coke.
The coke promotes the formation of a reducing atmosphere in the furnace, and if materials forming the reducing atmosphere in the furnace exist in the raw materials, the coke can not be added.
According to some embodiments of the invention, the recycling method further comprises performing an ingredient test after the mixing, and if not, performing a second blending.
According to some embodiments of the invention, the coke is 0 to 4 parts and the CaO is 9 to 43 parts by weight.
According to some embodiments of the invention, the temperature in the plasma melting furnace is 1450-1600 ℃.
The material mixture after batching can ensure good fluidity at the melting temperature, the viscosity of the mixture at the melting temperature in the material after batching is less than 25pas, the viscosity can ensure that the vitreous body has good fluidity in the melting state, the vitreous body can be smoothly discharged out of a melting furnace, the range of the molar ratio of the alkaline component to the acidic component is higher or lower than the range of the molar ratio of the alkaline component to the acidic component, and the fluidity of the mixture can not be ensured, thereby influencing the recovery of valuable metals.
According to some embodiments of the invention, the pressure in the plasma melting furnace is between-5 and-30 Pa.
Under the pressure, the temperature in the system can be ensured not to be lost, and the flue gas is taken away.
The flue gas is formed by heating a small amount of water or other volatile substances contained in the material, and a certain amount of water, CO and N contained in the flue gas can be produced in the plasma melting furnace 2 The flue gas of (1).
According to some embodiments of the invention, the recovery process further comprises water quenching the product obtained from the high temperature reaction.
According to some embodiments of the invention, the water quench cooling temperature is 25-55 ℃.
According to some embodiments of the invention, flue gas generated in the process of treating materials by the melting furnace is discharged out of the furnace through a smoke discharge pipeline at the top of the plasma melting furnace, and is directly subjected to waste heat utilization after passing through a tail gas purification treatment system or is purified to be used as combustible gas for resource utilization.
According to a second aspect of the embodiment of the invention, the application of the recovery method of the valuable metals in the recovery of the waste slag containing the valuable metals is provided.
The application of the valuable metal recovery method in recovering the waste slag containing valuable metals has at least the following beneficial effects:
the average recovery rate of the metal in the metal waste residue can reach more than 89%, a large amount of valuable metals are contained in the metal waste residue, and the metal waste residue can be purified by adopting a corresponding metallurgical process subsequently, so that higher metal utilization value is realized. The process for treating valuable metal incineration waste residues through plasma gasification and melting has 1-30t/d of industrial application cases, wherein the power consumption cost is about 1kw/kg of waste residues.
According to some embodiments of the invention, the metal value comprises a metal value comprising Mo, co, ni, V, fe.
According to some embodiments of the invention, the metal value comprises a pt-, rh-, pd-containing metal value.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a process flow diagram of a method for recovering valuable metals according to example 1 of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
Example 1
The embodiment discloses a method for recovering valuable metals, wherein the used waste slag contains Fe, and the method comprises the following specific steps:
s1: the method comprises the steps of carrying out component measurement on waste residues containing valuable metals, then batching, and measuring and batching results are shown in table 1, wherein a process flow chart of a valuable metal recovery process method is shown in figure 1, wherein after batching is finished, the molar ratio of alkaline components to acidic components is n (CaO)/n (SiO) 2 +Al 2 O 3 ) About 1;
TABLE 1 waste residue compounding of valuable metals
S2: under the action of 1600 ℃ of a plasma torch in a melting furnace, the glass state melt wraps heavy metal substances in a vitrification grid, wherein valuable metals can be reduced into a metal state under the conditions of high temperature and reducing atmosphere in the furnace, the metal state is deposited at the bottom of the furnace under the action of gravity, and is discharged out of the furnace from a metal outlet at the bottom in a clearance or continuously, and a vitreous by-product is discharged out of the furnace from a vitreous slag outlet at the upper layer.
By taking the middle 10h of continuous operation as the actual measurement time, the result is as follows: after being mixed and put into a furnace, fe 2 O 3 The percentage of (3) is 23.3 percent, the charging amount is 40kg/h, the continuous 10h charging amount is 400kg, and then the Fe charged into the furnace 2 O 3 The total amount of (1) was 93.2kg (23.3% = 400= 93.2), the Fe content was 65.2kg (93.2 × 56 × 2/160= 65.2%), the total iron content measured in the recovered metal from the melting furnace bottom over 10 hours was about 59kg, and the Fe recovery rate was 90.4% (59/65.2 = 90.4%).
Example 2
The embodiment discloses a method for recovering valuable metals containing Ni, which comprises the following steps:
s1: the slag containing valuable metals is subjected to component measurement and then is mixed, and the measurement and mixing results are shown in table 1, wherein the molar ratio of the alkaline component to the acidic component after the mixing is finished is n (CaO)/n (SiO) 2 +Al 2 O 3 ) About 1;
TABLE 2 waste residue compounding of valuable metals
S2: under the action of 1600 ℃ of a plasma torch in a melting furnace, the glass state melt wraps heavy metal substances in a vitrification grid, wherein valuable metals can be reduced into a metal state under the conditions of high temperature and reducing atmosphere in the furnace, the metal state is deposited at the bottom of the furnace under the action of gravity, and is discharged out of the furnace from a metal outlet at the bottom in a clearance or continuously, and a vitreous by-product is discharged out of the furnace from a vitreous slag outlet at the upper layer.
The measured time is 10h in the middle of continuous operation, and the result is as follows: the content of NiO after the combination of NiO and the melting furnace is 1.2 percent, the charging amount is 40kg/h, the charging amount of the NiO for 10 continuous hours is 400kg, the total amount of the NiO charged into the melting furnace is 3.8kg (1.1 percent by 400= 4.4), the Ni content is 3.6kg (4.4 percent by 75/(75 + 16) = 3.6), the total iron content measured in the metal recovery discharged from the melting furnace bottom within 10 hours is 3.2kg, and the recovery rate of Fe is 88.9 percent (3.2/3.6 =88.9 percent).
Comparative example 1
The present comparative example discloses a method for recovering valuable metals containing Fe, and differs from example 1 in that:
the molar ratio of the alkaline component to the acidic component after the batching is n (CaO)/n (SiO) 2 +Al 2 O 3 ) About 1.5; the rest conditions are the same.
The middle 10h of continuous operation is the actual measurement time, under the condition, the viscosity of the system is increased, and the normal flow of the mixed material cannot be ensured, so that the recovery rate of metal is influenced, and the recovery rate of Fe is 62.2%.
The embodiments of the present invention have been described in detail with reference to the drawings, but the present invention is not limited to the embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention.
Claims (10)
1. A method for recovering valuable metals, which is characterized by comprising the following steps: mixing the waste residue containing valuable metals and the ingredients, and then carrying out high-temperature reaction in a plasma melting furnace;
the auxiliary materials comprise auxiliary materials, and the auxiliary materials comprise alkaline components and acidic components;
the alkaline component includes CaO, and the alkaline component,
the acidic component comprises SiO 2 And Al 2 O 3 At least one of (a) and (b),
the molar ratio of the alkaline component to the acidic component after the reaction is 1.6-1.2.
2. The method for recycling valuable metals according to claim 1, wherein the burden includes 9 to 43 parts by weight of the CaO and the SiO 2 19 to 70 portions of Al 2 O 3 8 to 39 portions.
3. A method for recovering a valuable metal as claimed in claim 1, characterized in that said burden further includes coke.
4. The method according to claim 3, wherein the coke is 0 to 4 parts by weight, and the CaO is 9 to 43 parts by weight.
5. The method for recovering valuable metals according to claim 1, wherein the temperature in the plasma melting furnace is 1450 to 1600 ℃.
6. The method according to claim 1, wherein a pressure in the plasma melting furnace is in a range of-5 to-30 Pa.
7. The method for recovering valuable metals according to claim 1, further comprising water quenching the product obtained by the high-temperature reaction.
8. The method for recovering valuable metals according to claim 7, wherein the temperature of the water quenching cooling is 25 to 55 ℃.
9. Use of a method of recovering a valuable metal according to any one of claims 1 to 8 for recovering a slag containing valuable metals.
10. The use according to claim 9, wherein the metal comprises a valuable metal comprising any of Mo, co, ni, V and Fe.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210736811.2A CN115141932A (en) | 2022-06-27 | 2022-06-27 | Valuable metal recovery method and application thereof |
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| CN202210736811.2A CN115141932A (en) | 2022-06-27 | 2022-06-27 | Valuable metal recovery method and application thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4952237A (en) * | 1987-12-22 | 1990-08-28 | Alcan International Limited | Method and apparatus for recovery of non-ferrous metals from dross |
| CN108704926A (en) * | 2018-07-04 | 2018-10-26 | 加拿大艾浦莱斯有限公司 | A kind of processing of plasma fusing fly ash and metal recovery utilize system |
| CN111889487A (en) * | 2020-08-03 | 2020-11-06 | 天津大学 | Method for solidifying heavy metal by plasma fusion through multi-source solid waste synergistic treatment |
| CN113118181A (en) * | 2021-04-13 | 2021-07-16 | 光大环保技术研究院（深圳）有限公司 | Method for preparing vitreous body and decarbonizing by using hazardous waste incineration ash in synergy mode |
-
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- 2022-06-27 CN CN202210736811.2A patent/CN115141932A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4952237A (en) * | 1987-12-22 | 1990-08-28 | Alcan International Limited | Method and apparatus for recovery of non-ferrous metals from dross |
| CN108704926A (en) * | 2018-07-04 | 2018-10-26 | 加拿大艾浦莱斯有限公司 | A kind of processing of plasma fusing fly ash and metal recovery utilize system |
| CN111889487A (en) * | 2020-08-03 | 2020-11-06 | 天津大学 | Method for solidifying heavy metal by plasma fusion through multi-source solid waste synergistic treatment |
| CN113118181A (en) * | 2021-04-13 | 2021-07-16 | 光大环保技术研究院（深圳）有限公司 | Method for preparing vitreous body and decarbonizing by using hazardous waste incineration ash in synergy mode |
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