CN108866342B - Device and method for treating waste catalyst containing noble metal - Google Patents
Device and method for treating waste catalyst containing noble metal Download PDFInfo
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- CN108866342B CN108866342B CN201810998585.9A CN201810998585A CN108866342B CN 108866342 B CN108866342 B CN 108866342B CN 201810998585 A CN201810998585 A CN 201810998585A CN 108866342 B CN108866342 B CN 108866342B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000002699 waste material Substances 0.000 title claims description 31
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 90
- 229910052802 copper Inorganic materials 0.000 claims abstract description 81
- 239000010949 copper Substances 0.000 claims abstract description 81
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003546 flue gas Substances 0.000 claims abstract description 15
- 239000000428 dust Substances 0.000 claims abstract description 14
- 239000000779 smoke Substances 0.000 claims abstract description 5
- 238000004062 sedimentation Methods 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 60
- 239000002893 slag Substances 0.000 claims description 54
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 238000007599 discharging Methods 0.000 claims description 14
- 239000000155 melt Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 10
- 239000011449 brick Substances 0.000 claims description 10
- 230000000630 rising effect Effects 0.000 claims description 10
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 9
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 9
- 239000004571 lime Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 238000007664 blowing Methods 0.000 claims description 7
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 7
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000000571 coke Substances 0.000 claims description 5
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 5
- 230000000171 quenching effect Effects 0.000 claims description 5
- 238000003723 Smelting Methods 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000003949 liquefied natural gas Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 5
- 230000008929 regeneration Effects 0.000 abstract description 3
- 238000011069 regeneration method Methods 0.000 abstract description 3
- 239000002920 hazardous waste Substances 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- -1 platinum group metals Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
Classifications
-
- 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
- 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
- C22B11/026—Recovery of noble metals from waste materials 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
- C22B4/00—Electrothermal treatment of ores or metallurgical products for obtaining metals or alloys
- C22B4/04—Heavy metals
-
- 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
- C22B7/009—General processes for recovering metals or metallic compounds from spent catalysts
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a device and a method for treating a noble metal-containing dead catalyst, belonging to the field of hazardous waste disposal and resource regeneration and solving the problem of easy secondary pollution existing in the prior device. The device for treating the noble metal-containing dead catalyst comprises an electric furnace, a settling chamber, a bag-type dust remover, a smoke exhaust fan and an exhaust barrel which are sequentially connected, wherein an electrode is arranged at the top of the electric furnace, an electrode lifting device is arranged on a furnace shell of the electric furnace, the lower end of the electrode is inserted into the electric furnace, and the top of the electrode is connected with the electrode lifting device; a furnace mouth is arranged on the side wall below the electric furnace, and a copper discharge mouth is arranged at the bottom of the electric furnace; and a flue gas outlet is arranged on the side wall above the electric furnace and is connected with the sedimentation chamber. The invention has the characteristics of adjustable furnace size, high noble metal recovery rate, easy furnace opening and arcing, low equipment investment and the like.
Description
Technical Field
The invention belongs to the field of hazardous waste disposal and resource regeneration, and particularly relates to a device and a method for treating a noble metal-containing dead catalyst.
Background
More than 90% of petrochemical reactions are carried out by catalysts, and the catalysts used are platinum-based catalysts comprising various platinum-group metals as catalytic components supported on a carrier such as alumina. The original activity of the regenerated catalyst is damaged, and the catalyst becomes a waste catalyst when the activity of the regenerated catalyst is lower than an acceptable level after multiple times of regeneration. With the rapid development of petrochemical industry, the increment of the waste petrochemical catalyst is also rapidly increased. The waste catalyst in petrochemical industry often contains some toxic components, mainly heavy metals and volatile organic compounds, has great environmental risk, and is particularly important to carry out innocent treatment. In addition, the petrochemical waste catalyst contains noble metals and other valuable metals in higher content, and some of the noble metals and other valuable metals are even far higher than the content of corresponding components in certain lean ores, so that the metal grade is high, and the noble metals and other valuable metals can be recycled as secondary resources. The comprehensive recycling of the petrochemical waste catalyst can improve the resource utilization rate, can avoid the environmental problems caused by the waste catalyst, and realizes sustainable development.
At present, the wet recovery of the waste catalyst is the most studied and widely used method at home and abroad. The method comprises the steps of dissolving the main components of the waste industrial catalyst by acid, alkali or other solvents, removing impurities from filtrate, purifying, separating to obtain sulfide or metal hydroxide which is difficult to dissolve in water, drying, and further processing into a final product according to the requirement. The waste catalyst is treated by a wet method, the carrier of the waste catalyst often exists in the form of insoluble residues, if no proper treatment method is adopted, a large amount of solid waste can cause secondary damage, and if the carrier is dissolved together with metal, the separation of the metal and the carrier can generate a large amount of waste liquid which is easy to cause secondary pollution. In addition, the residue after wet recovery of noble metals still contains a certain amount of platinum group metals (generally 30-50 g/t), and the method has the advantages of long process flow, complicated operation and high cost.
Disclosure of Invention
The invention aims to provide a device for treating a waste catalyst containing noble metal, which solves the problem that the existing device is easy to cause secondary pollution.
The invention also aims to provide a method for treating the waste catalyst containing noble metal, which aims to solve the problems of long process flow, complicated operation and high cost of the existing method.
The technical scheme of the invention is as follows: the device for treating the noble metal-containing dead catalyst comprises an electric furnace, a settling chamber, a bag-type dust remover, a smoke exhaust fan and an exhaust barrel which are sequentially connected, wherein an electrode is arranged at the top of the electric furnace, an electrode lifting device is arranged on a furnace shell of the electric furnace, the lower end of the electrode is inserted into the electric furnace, and the top of the electrode is connected with the electrode lifting device; a furnace mouth is arranged on the side wall below the electric furnace, and a copper discharge mouth is arranged at the bottom of the electric furnace; and a flue gas outlet is arranged on the side wall above the electric furnace and is connected with the sedimentation chamber.
As a further improvement of the invention, the electric furnace adopts graphite electrodes, the number of the electrodes is 1 or 3, and the electrode lifting device is fixed on the electric furnace shell.
As a further improvement of the invention, the width of the hearth of the electric furnace is 0.8-2m, and the total height of the hearth is 1-2.2m. The flue gas outlet is provided with a movable sealing ring which is connected with a subsequent flue to prevent smoke leakage.
The method for treating the waste catalyst containing noble metal by using the device comprises the following steps:
A. 200kg to 500kg of crushed copper is added into an electric furnace, the electrode is lowered to be contacted with the crushed copper, the metal copper is melted into copper liquid under the action of the electrode, the electrode is gradually lifted along with the rising of the copper liquid level,
B. feeding: mixing the waste catalyst and lime powder uniformly, adding the mixed material into an electric furnace from a furnace mouth, gradually lifting the electrode along with the rising of the liquid level of a molten pool, and ensuring that the electrode is inserted 100-200mm below the liquid level of the melt;
stopping feeding when the liquid level of the molten pool rises to 200mm from the furnace mouth, lifting the electrode, blowing gas into the electrode through the oxygen blowing pipe to stir the melt, stirring the melt for 15-20 minutes, and fully mixing the slag phase and the copper phase; after stirring, lowering the electrode, enabling the electrode to be inserted into the molten pool for 100-200mm below the liquid level, and preserving heat for 20-40 minutes;
C. discharging: tilting the furnace body after heat preservation is completed, discharging slag from a furnace mouth, and carrying out water quenching on the discharged slag; after the slag is placed, the furnace body is shaken up, copper liquid is kept at the bottom, then the furnace mouth is continuously fed, and the operation is repeated; and after the last slag discharge, the furnace body is shaken up, and a copper discharge port below the furnace body is boiled by oxygen, so that the copper liquid with the captured noble metal is placed into a die from the copper discharge port for casting, and a crude copper ingot rich in the noble metal is obtained. The pouring basket can be directly placed into a mould through a chute or placed into a tundish, and manually poured into the mould for casting.
D. The flue gas generated by smelting firstly removes large-particle dust through a settling chamber, then removes small-particle dust through a bag-type dust remover, and finally the flue gas reaches the standard and is discharged.
As a further improvement of the invention, the mass ratio of the waste catalyst to the lime powder is 1:1.0-1.5.
As a further improvement of the invention, the gas blown in from the furnace mouth through the oxygen blowing pipe is nitrogen or argon or liquefied natural gas to stir the melt, and the contact area of the copper phase and the slag phase is enlarged, so that the noble metal is better absorbed by copper; the lining of the electric furnace is made of one or two of carbon bricks and magnesia chrome bricks.
As a further improvement of the invention, after the electrode in the step B is positioned at the liquid level of the molten pool, calcium fluoride is added from a furnace mouth, and the adding proportion of the calcium fluoride is 1-3%.
As a further improvement of the invention, the feeding and the deslagging are carried out 10-12 times in total.
As a further improvement of the invention, the slag is discharged in the step C, and the electrode is connected with the electric furnace lining by coke for arc starting in the next furnace opening mode.
As a further improvement of the invention, slag is discharged in the step C, an arc striking mode adopts a pre-buried metal rod in the next furnace opening, and the electrode is connected with the metal rod for conducting electricity to strike an arc.
The principle of the device of the invention is as follows: firstly, melting broken copper, then adding the waste catalyst and lime powder into an electric furnace from a furnace mouth in a manual mode, melting the materials under the action of an electrode, and because the density of copper is greatly settled at the bottom, slagging is carried out on the rest part of the waste catalyst and auxiliary materials, slag floats above a molten liquid, noble metals in the waste catalyst are absorbed by the copper liquid through boiling and continuous stirring of the melt in the smelting process, and after repeated feeding, stirring, heat preservation and deslagging processes, the noble metals in the waste catalyst are continuously enriched in the blister copper, and the blister copper is discharged from a copper discharge port below the furnace body and is cast to obtain blister copper containing the noble metals.
The flue gas generated by smelting firstly removes large-particle dust through a settling chamber, then removes small-particle dust through a bag-type dust remover, and finally the flue gas reaches the standard and is discharged.
The method of the invention is that the waste catalyst containing noble metal and lime powder are melted under the action of the electrode, the metal copper is used as the trapping agent of noble metal, so that the noble metal is enriched in the metal copper, alumina, silicon dioxide and the like in the catalyst are produced in the form of slag, the environmental problem caused by piling up the waste catalyst is effectively solved, the noble metals platinum and palladium in the waste catalyst are efficiently recovered, and the method has good environmental benefit and economic benefit.
The invention has the characteristics of adjustable furnace size, high noble metal recovery rate, easy furnace opening and arcing, low equipment investment and the like.
The invention has the following advantages:
1. the method can be operated continuously or intermittently, coke can be used for communicating the electrode with the furnace wall to conduct electricity to start an arc when the furnace is stopped and then opened, or an iron rod or a copper rod can be inserted into a melt after the furnace is stopped in advance, and the electrode is lowered to be connected with the iron rod or the copper rod to start the arc.
2. The fire-resistant material of the electric furnace adopts one or two of conductive carbon bricks and magnesia chrome bricks to be mixed at intervals. The size of the hearth of the electric furnace can be adjusted according to the treatment capacity, and the electric furnace can be used for miniaturized treatment of the waste catalyst containing noble metal.
3. Copper is used as a collecting agent of noble metal, and the blister copper is discharged from a copper discharge port below the furnace body and is cast to obtain the blister copper containing noble metal. The situation that the furnace body tilts too much and the blister copper cannot be completely poured out when the slag and the blister copper are discharged from the upper furnace mouth is avoided.
4. The process flow is simple, and the labor personnel number is greatly reduced. The recovery rate of noble metal is high, the platinum content in slag is less than 5g/t, and the palladium content is less than 5 g/t.
Drawings
FIG. 1 is a schematic structural view of an apparatus for treating a spent catalyst containing noble metals;
FIG. 2 is a schematic view showing the structure of an electric furnace in an apparatus for treating a noble metal-containing spent catalyst;
FIG. 3 is a schematic diagram of an arcing scheme;
fig. 4 is a schematic diagram of another arcing scheme.
In the figure: 1-an electric furnace, 2-a settling chamber, 3-cloth bag dust removal, 4-a fan, 5-an exhaust drum, 11-an electrode lifting device, 12-a furnace shell, 13-an electrode, 14-a flue gas outlet, 15-a furnace mouth, 16-a copper placing mouth and 17-a metal rod; 18-lining the electric furnace; 19-coke; a 20-copper layer; 21-slag layer.
Detailed Description
The following examples are given to further illustrate the gist of the present invention, but the present invention is not limited thereto.
As shown in the figure, the device for treating the noble metal-containing dead catalyst comprises an electric furnace 1, a settling chamber 2, a bag-type dust collector 3, a smoke exhaust fan 4 and an exhaust funnel 5 which are sequentially connected, wherein an electrode 13 is arranged at the top of the electric furnace 1, an electrode lifting device 11 is arranged on a furnace shell 12 of the electric furnace 1, the lower end of the electrode 13 is inserted into the electric furnace 1, and the top of the electrode 13 is connected with the electrode lifting device 11; a furnace mouth 15 is arranged on the side wall below the electric furnace 1, and a copper discharge mouth 16 is arranged at the bottom of the electric furnace 1; a flue gas outlet 14 is arranged on the side wall above the electric furnace 1, and the flue gas outlet 14 is connected with the sedimentation chamber 2.
The electric furnace adopts graphite electrode to heat, and electrode 13 quantity is 1 or 3, and electrode elevating gear 11 is fixed on the electric furnace shell, and when the electric furnace rotated, the electrode rotated along with the furnace body. The flue gas outlet 14 is provided with a movable sealing ring. The inner lining of the electric furnace is built on the inner side of the furnace shell, and the outer layer of the furnace body is the furnace shell made of steel plates.
FIG. 3 is a schematic illustration of one manner of arcing in a process for treating a spent catalyst containing precious metals; fig. 4 is a schematic diagram of another arcing scheme. In the figure, the lower layer of the inner cavity of the electric furnace (1) is a copper layer 20, and the upper layer is a slag layer 21.
Example 1
200kg of broken copper is added into an electric furnace, the electrode is lowered to be contacted with the broken copper, metallic copper is melted into a copper liquid layer 20 under the action of the electrode, the electrode is gradually lifted along with the rising of the copper liquid level, a single electrode is adopted as the electrode in the heating process, the lining of the electric furnace is made of magnesia chrome bricks, the width of a furnace hearth of the electric furnace is 0.8m, and the total height of the furnace hearth is 1m.
The following waste catalyst: mixing the lime powder in the mass ratio of 1:1.0, and uniformly mixing the mixed materials. The mixed material is added into the electric furnace from the furnace mouth in a manual mode, and the electrode is gradually lifted along with the rising of the liquid level of the molten pool, so that the electrode is ensured to be inserted 100-200mm below the liquid level of the melt.
Stopping feeding when the liquid level of the molten pool rises to 200mm from the furnace mouth, lifting the electrode, leading the electrode to be out of the liquid level of the molten pool, and adding 1% calcium fluoride into the molten pool to reduce the melting point of slag. The melt was stirred with nitrogen or argon through an oxygen lance for 15 minutes to thoroughly mix the slag phase and copper phase and to enrich as much of the precious metal in the copper liquid as possible. After stirring, the electrode is lowered, the electrode is inserted into the molten pool for 100-200mm below the liquid level, and the temperature is kept for 20 minutes.
When in slag discharging, the electric furnace tilts under the action of the driving device, slag is poured out from a slag outlet (furnace mouth), the discharged slag is subjected to water quenching, and then the water quenched slag is piled up or sold.
And (3) shaking the furnace body after the slag is placed, keeping the copper liquid at the bottom, then continuously feeding the copper liquid from a furnace mouth, repeating the operations, feeding and discharging slag for ten times, discharging the slag when the furnace is required to be stopped, lifting the electrode to be above the residual liquid level, inserting a copper rod into the center of the residual melt, and connecting the electrode with the copper rod for conducting electricity when the furnace is opened next time to start an arc.
And after the last slag discharge, the furnace body is shaken up, and a copper discharge port below the furnace body is boiled by oxygen, so that the copper liquid with the captured noble metal is placed into a die from the copper discharge port for casting, and a crude copper ingot rich in the noble metal is obtained.
Example 2
400kg of broken copper is added into an electric furnace, the electrode is reduced to be contacted with the broken copper, metallic copper is melted into copper liquid under the action of the electrode, the electrode is gradually lifted along with the rising of the copper liquid level, a single electrode is adopted as the electrode in the heating process, the lining of the electric furnace is arranged at intervals of magnesia chrome bricks and carbon bricks, the width of a furnace chamber of the electric furnace is 1.8m, and the total height of the furnace chamber is 2m.
The following waste catalyst: mixing the lime powder in the mass ratio of 1:1.4, and uniformly mixing the mixed materials. The mixed material is added into the electric furnace from the furnace mouth in a manual mode, and the electrode is gradually lifted along with the rising of the liquid level of the molten pool, so that the electrode is ensured to be inserted 100-200mm below the liquid level of the melt.
Stopping feeding when the liquid level of the molten pool rises to 200mm from the furnace mouth, lifting the electrode, leading the electrode to be out of the liquid level of the molten pool, stirring the molten pool for 20 minutes by using nitrogen through an oxygen blowing pipe, fully mixing slag phase and copper phase, and enriching precious metals in the copper liquid as much as possible. After stirring, the electrode is lowered, the electrode is inserted into the molten pool for 100-200mm below the liquid level, and the temperature is kept for 30 minutes.
When in slag discharging, the electric furnace tilts under the action of the driving device, slag is poured out from a slag outlet (furnace mouth), the discharged slag is subjected to water quenching, and then the water quenched slag is piled up or sold.
And (3) shaking the furnace body after the slag is placed, keeping the copper liquid at the bottom, then continuously feeding the copper liquid from a furnace mouth, repeating the operations, feeding and discharging slag for 12 times, discharging the slag when the furnace is required to be stopped, lifting the electrode to be above the residual liquid level, inserting an iron rod into the center of the residual melt, and connecting the electrode with the iron rod for conducting electricity when the furnace is opened next time to start an arc.
After the last slag discharge, the furnace body is shaken up, a copper discharge port below the furnace body is boiled by oxygen, so that copper liquid with noble metals trapped is discharged from the copper discharge port to a tundish, and the copper liquid is poured into a die manually to be cast to obtain crude copper rich in noble metals.
Example 3
500kg of broken copper is added into an electric furnace, the electrode is lowered to be contacted with the broken copper, metal copper is melted into copper liquid under the action of the electrode, the electrode is gradually lifted along with the rising of the copper liquid level, a single electrode is adopted as the electrode in the heating process, the lining of the electric furnace is made of carbon bricks, the width of a furnace chamber of the electric furnace is 2m, and the total height of the furnace chamber is 2.2m.
The following waste catalyst: mixing the lime powder in the mass ratio of 1:1.5, and uniformly mixing the mixed materials. The mixed material is added into the electric furnace from the furnace mouth in a manual mode, and the electrode is gradually lifted along with the rising of the liquid level of the molten pool, so that the electrode is ensured to be inserted 100-200mm below the liquid level of the melt.
Stopping feeding when the liquid level of the molten pool rises to 200mm from the furnace mouth, lifting the electrode, leading the electrode to be out of the liquid level of the molten pool, and adding 1.5% calcium fluoride into the molten pool to reduce the melting point of slag. The liquefied natural gas is used to stir the melt for 20 minutes through an oxygen lance, so that the slag phase and the copper phase are fully mixed, and the noble metal is enriched in the copper liquid as much as possible. After stirring, the electrode is lowered, the electrode is inserted into the molten pool for 100-200mm below the liquid level, and the temperature is kept for 40 minutes.
When in slag discharging, the electric furnace tilts under the action of the driving device, slag is poured out from a slag outlet (furnace mouth), the discharged slag is subjected to water quenching, and then the water quenched slag is piled up or sold.
And (3) shaking the furnace body after the slag is placed, keeping the copper liquid at the bottom, then continuously feeding the copper liquid from the furnace mouth, repeating the operations, and discharging slag for 12 times, wherein the slag is discharged when the furnace is required to be stopped, the electrode is lifted to be above the residual liquid level, and the electrode and the furnace wall are connected by coke for conducting arc starting when the furnace is opened next time.
After the last slag discharge, the furnace body is shaken up, a copper discharge port below the furnace body is boiled by oxygen, so that copper liquid with noble metals trapped is discharged from the copper discharge port to a tundish, and the copper liquid is poured into a die manually to be cast to obtain crude copper rich in noble metals.
Example 4: the difference from example 2 is that the charging is stopped when the bath level rises to 200mm from the furnace mouth, the electrode is lifted up to bring the electrode out of the bath level, at which time 2% calcium fluoride is added to the bath to lower the melting point of the slag.
Claims (9)
1. The method for treating the noble metal-containing dead catalyst is characterized in that a treatment device comprises an electric furnace (1), a settling chamber (2), a bag-type dust collector (3), a smoke exhaust fan (4) and an exhaust barrel (5) which are sequentially connected, an electrode (13) is arranged at the top of the electric furnace (1), an electrode lifting device (11) is arranged on a furnace shell (12) of the electric furnace (1), the lower end of the electrode (13) is inserted into the electric furnace (1), and the top of the electrode (13) is connected with the electrode lifting device (11); a furnace mouth (15) is arranged on the side wall below the electric furnace (1), and a copper discharge mouth (16) is arranged at the bottom of the electric furnace (1); a flue gas outlet (14) is arranged on the side wall above the electric furnace (1), and the flue gas outlet (14) is connected with the sedimentation chamber (2);
the processing method comprises the following steps:
A. 200-500kg of crushed copper is added into an electric furnace (1), an electrode (13) is lowered to be in contact with the crushed copper, metallic copper is melted into copper liquid under the action of the electrode, and the electrode is gradually lifted along with the rising of the copper liquid level;
B. feeding: mixing the waste catalyst and lime powder uniformly, adding the mixed material into an electric furnace from a furnace mouth (15), gradually lifting the electrode along with the rising of the liquid level of a molten pool, and ensuring that the electrode is inserted 100-200mm below the liquid level of the melt;
stopping feeding when the liquid level of the molten pool rises to 200mm from a furnace mouth (15), lifting the electrode, blowing gas into the electrode out of the liquid level of the molten pool through an oxygen blowing pipe, stirring the melt for 15-20 minutes, and fully mixing the slag phase and the copper phase; after stirring, lowering the electrode, enabling the electrode to be inserted into the molten pool for 100-200mm below the liquid level, and preserving heat for 20-40 minutes;
C. discharging: tilting the furnace body after heat preservation is completed, discharging slag from a furnace mouth (15), and carrying out water quenching on the discharged slag; after the slag is placed, the furnace body is shaken up, copper liquid is kept at the bottom, then the furnace mouth (15) is used for continuously feeding, and the operation is repeated;
after the last slag discharge, the furnace body is shaken up, and a copper discharge port below the furnace body is boiled by oxygen, so that copper liquid with noble metals trapped is placed into a die from the copper discharge port for casting to obtain a crude copper ingot rich in noble metals;
D. the flue gas generated by smelting firstly removes large-particle dust through a settling chamber, then removes small-particle dust through a bag-type dust remover, and finally the flue gas reaches the standard and is discharged.
2. The method for treating a noble metal-containing spent catalyst according to claim 1, characterized in that: the mass ratio of the waste catalyst to the lime powder is 1:1.0-1.5.
3. The method for treating a noble metal-containing spent catalyst according to claim 2, characterized in that: the gas blown in from the furnace mouth (15) through the oxygen blowing pipe is nitrogen or argon or liquefied natural gas to stir the melt; the electric furnace lining (18) adopts one or two of carbon bricks and magnesia chrome bricks for mixed use.
4. A method for treating a spent catalyst containing noble metal according to claim 3, characterized in that: and (3) adding calcium fluoride from a furnace mouth (15) after the electrode in the step B is positioned at the liquid level of the molten pool, wherein the adding proportion of the calcium fluoride is 1-3%.
5. The method for treating a spent catalyst containing noble metal according to claim 4, wherein: the feeding and the deslagging are carried out for 10-12 times.
6. The method for treating a noble metal-containing spent catalyst according to claim 5, wherein: and C, discharging slag, and starting an arc by connecting the electrode (13) with the electric furnace lining (18) through coke (19) in the next furnace opening mode.
7. The method for treating a noble metal-containing spent catalyst according to claim 5, wherein: and C, discharging slag, adopting a pre-buried metal rod (17) in an arc starting mode when the furnace is opened next time, and connecting and conducting the electrode and the metal rod to start the arc.
8. The method for treating a noble metal-containing spent catalyst according to claim 1, characterized in that: the electric furnace adopts graphite electrodes, the number of the electrodes (13) is 1 or 3, and the electrode lifting device (11) is fixed on the electric furnace shell.
9. The method for treating a noble metal-containing spent catalyst according to claim 1 or 2, characterized in that: the width of the hearth of the electric furnace is 0.8-2m, and the total height of the hearth is 1-2.2m.
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