CN100516257C - Method for recovering and reusing niobium and niobium alloy waste - Google Patents
Method for recovering and reusing niobium and niobium alloy waste Download PDFInfo
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- CN100516257C CN100516257C CNB2007100188542A CN200710018854A CN100516257C CN 100516257 C CN100516257 C CN 100516257C CN B2007100188542 A CNB2007100188542 A CN B2007100188542A CN 200710018854 A CN200710018854 A CN 200710018854A CN 100516257 C CN100516257 C CN 100516257C
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The present invention discloses process of recovering niobium and niobium alloy from niobium containing wastes including ingot head, turnings and leftover from extrusion, forging and machining. The process includes cleaning the wastes; and smelting in a vacuum annealing furnace and die pressing into electrode block; or pressing and welding to from electrode block. When the niobium alloy leftover has lower alloy element content, it is produced into sintered strip through hydrogenating reduction, dehydrogenating, pressing and sintering. The process can recover niobium and niobium alloy effectively in low cost and saving in niobium resource.
Description
Technical field
The present invention relates to a kind of recycling method of waste material, be specifically related to the recycling method of a kind of niobium and niobium alloy waste material.
Background technology
Niobium is the proportion minimum in refractory metal, its fusing point height (2468 ℃), thermal conductivity is better, neutron-capture cross section is little (1.1 * 10-28m2), low temperature (196 ℃) ductility is good, and good high-temperature intensity, temperature-room type plasticity, welding property and alkaline-resisting metallic corrosion performance are arranged.At room temperature, except that hydrofluoric acid, oleum and highly basic, nearly all salts solution and mineral acid do not work with niobium; Niobium is also good in anti-liquid uranium below 1200 ℃, magnesium corrosive ability; They are widely used in aspects such as electronics, superconduction chemical industry.At present, the niobium alloy of external use in a large number and large-scale production has the C-103 (Nb-10Hf-1Ti-0.5Zr) and the Muscovite 5BH Ц (Nb-5W-2Mo-1Zr) of the U.S.; The Nb-1Zr alloy has been widely used for building the piping system that 980～1200 ℃ of following liquid metal heat exchange mediums pass through.
Niobium is non-renewable resource, the application of niobium and niobium alloy material is increasingly extensive to have consumed a large amount of niobium resources, an important channel that solves following niobium shortage of resources is exactly the direct recycling that realizes material, and this is than much with low cost as the mineral recycling with waste material; Have information to show: Russia has realized the recycling of niobium alloy.
Summary of the invention
The objective of the invention is to overcome the deficiency of existing coating conductor barrier layer technology of preparing, provide a kind of workable, need not to adopt specific installation, can reduce the cost recovery of niobium alloy, and save the recycling method of the niobium and the niobium alloy waste material of niobium resource.
To achieve these goals, the technical solution used in the present invention is: the recycling method of a kind of niobium and niobium alloy waste material is characterized in that this method may further comprise the steps:
(1) processing of ingot casting rising head: the ingot casting rising head is sawn into the piece that width is 50mm, and because of the ingot casting rising head does not have oxide skin, only need adopt volume percent when reclaiming is HF: HNO
3: H
2O=1: 3: 4 concentrated acid liquid soaked 10～20 minutes, very fast again proposition, put into life water and washed down and dry;
(2) processing of ladle barrow bits: the ladle barrow bits are meant the scurf of taking off of melting ingot casting, at first the car bits being put into the metal cleaner aqueous solution boils, 20kg crumb 1kg detergent, the oil that will waft at water surface skims one by one, until there not being oil to waft till the surface, oil go clean after, again the car bits are poured into water washes down metal cleaner in the clean hopper; The long-pending per-cent of part is HF: HNO
3: H
2O=2: 3: 14 acid solution, car bits are put in batches with Louing basket pave, immerse soak 1～6 minute in the described acid solution after, from acid solution, propose rapidly to immerse in the off-the-shelf tank, with flowing water acid solution is thoroughly washed down, be flushed in the groove water become limpid till after pull out, control water, put into baking oven and dry; Car bits with oven dry adopt manual sorting's way, choose foreign peoples's car bits, wood chip, broom rod and the end of a thread of sneaking into; Less car bits will carefully sort the back and inhale the chip that removes lathe tool with magnet;
(3) the contract processing of tail of extruding: extruding is contracted tail along the section that circumferentially is sawn into 30～70mm, again these sections are sawn into semicircle; Be HCl: H with volume percent again
2O=1: 2 hydrochloric acid solution soaks, and iron is with after the niobium alloy major part is separated, and knocks out with flat chisel and the hammer iron with bulk, and the iron of material heart portion will go with the drilling machine brill; Going clean material piece to put into volume percent the iron major part is HF: HNO
3: H
2O=1: 3: 4 concentrated acid liquid soaks, and will expect to take out from described concentrated acid liquid every 3 hours, brushes away the pale precipitation thing on material surface with plastic bruss, will be behind the concentrated acid liquid precipitate than pouring out of cleaning, and pouring into and pouring out concentrated acid liquid is HF: HNO with the volume percent of volume
3: H
2O=1: 3: 4 newly join concentrated acid liquid, will expect that once more piece puts into concentrated acid liquid, so repeat repeatedly, dry till back depressed portions site surface do not have jaundice, turning black and changing color place up to material; After soaking with dilute hydrochloric acid liquid again, pull, put into mobile water very soon out and rinse well, pull back concave surface out and dry down;
(4) processing of forging caput and sheet material corner: caput and sheet material corner are put into the immersion of concentrated acid liquid, to expect from acid solution, to take out every 3 hours, with the pale precipitation thing that brushes away the material surface, the acid solution post precipitation will be poured out than muddy lower floor, and pouring into and pouring out concentrated acid liquid is HF: HNO with the volume percent of volume
3: H
2O=1: 3: 4 newly join concentrated acid liquid, will expect that once more piece puts into concentrated acid liquid, so repeat, dry till back depressed portions site surface do not have jaundice, turning black and changing color place up to material; Clean with clean material piece washing out method again;
(5) forge the processing of the finish turning bits of rod: at first the car bits are put into the metal cleaner aqueous solution and boil, the oil that will waft at water surface skims one by one, greasy dirt go clean after, again the car bits are poured into water washes down metal cleaner in the clean hopper; The long-pending per-cent of part is HF: HNO
3: H
2O=1: 3: 4 composite concentrated acid solution, the car bits are put into bottom sponge plastics container in batches to be paved, immerse soak 10～15 minutes in the described concentrated acid liquid after, from concentrated acid liquid, propose rapidly to immerse in the off-the-shelf tank, pull out after with flowing water acid solution thoroughly being washed down, clean with clean car bits washing out method again;
(6) the niobium alloy bits of cleaning are put in the vacuum annealing furnace, behind the lid lid, the heat-up rate that adopts 10 ℃/3 minutes was 950～1200 ℃ of insulations 1～2 hour, below stove internal cooling to 100 ℃, come out of the stove, for melting is convenient once more, need niobium alloy car bits are put into the punching block of 50 * 50 * 300mm, be pressed into electrode block with 200 tons of oil press gradation;
(7) contract tail and ingot casting rising head of electrode block, caput and the edges of boards angle that car bits are pressed into, extruding put into the argon arc welding case, and down, other material piece is welded into smelting electrode in last order according to electrode block; When electrode block is not enough, will with batch the niobium alloy lath as soldering pallet, the material piece of other kind is welded on the supporting plate.
The recycling method of a kind of niobium and niobium alloy waste material is characterized in that this method may further comprise the steps:
(1) processing of ingot casting rising head: the ingot casting rising head is sawn into the piece that width is 50mm, and because of the ingot casting rising head does not have oxide skin, only need adopt volume percent when reclaiming is HF: HNO
3: H
2O=1: 3: 4 concentrated acid liquid soaked 10～20 minutes, very fast again proposition, put into life water and washed down and dry;
(2) processing of ladle barrow bits: the ladle barrow bits are meant the scurf of taking off of melting ingot casting, at first the car bits being put into the metal cleaner aqueous solution boils, 20kg crumb 1kg detergent, the oil that will waft at water surface skims one by one, until there not being oil to waft till the surface, oil go clean after, again the car bits are poured into water washes down metal cleaner in the clean hopper; The long-pending per-cent of part is HF: HNO
3: H
2O=2: 3: 14 acid solution, car bits are put in batches with Louing basket pave, immerse soak 1～6 minute in the described acid solution after, from acid solution, propose rapidly to immerse in the off-the-shelf tank, with flowing water acid solution is thoroughly washed down, be flushed in the groove water become limpid till after pull out, control water, put into baking oven and dry; Car bits with oven dry adopt manual sorting's way, choose foreign peoples's car bits, wood chip, broom rod and the end of a thread of sneaking into; Less car bits will carefully sort the back and inhale the chip that removes lathe tool with magnet;
(3) the contract processing of tail of extruding: extruding is contracted tail along the section that circumferentially is sawn into 30～70mm, again these sections are sawn into semicircle; Be HCl: H with volume percent again
2O=1: 2 hydrochloric acid solution soaks, and iron is with after the niobium alloy major part is separated, and knocks out with flat chisel and the hammer iron with bulk, and the iron of material heart portion will go with the drilling machine brill; Going clean material piece to put into volume percent the iron major part is HF: HNO
3: H
2O=1: 3: 4 concentrated acid liquid soaks, and will expect to take out from described concentrated acid liquid every 3 hours, brushes away the pale precipitation thing on material surface with plastic bruss, will be behind the concentrated acid liquid precipitate than pouring out of cleaning, and pouring into and pouring out concentrated acid liquid is HF: HNO with the volume percent of volume
3: H
2O=1: 3: 4 newly join concentrated acid liquid, will expect that once more piece puts into concentrated acid liquid, so repeat repeatedly, dry till back depressed portions site surface do not have jaundice, turning black and changing color place up to material; After soaking with dilute hydrochloric acid liquid again, pull, put into mobile water very soon out and rinse well, pull back concave surface out and dry down;
(4) processing of forging caput and sheet material corner: caput and sheet material corner are put into the immersion of concentrated acid liquid, to expect from acid solution, to take out every 3 hours, with the pale precipitation thing that brushes away the material surface, the acid solution post precipitation will be poured out than muddy lower floor, and pouring into and pouring out concentrated acid liquid is HF: HNO with the volume percent of volume
3: H
2O=1: 3: 4 newly join concentrated acid liquid, will expect that once more piece puts into concentrated acid liquid, so repeat, dry till back depressed portions site surface do not have jaundice, turning black and changing color place up to material; Clean with clean material piece washing out method again;
(5) forge the processing of the finish turning bits of rod: at first the car bits are put into the metal cleaner aqueous solution and boil, the oil that will waft at water surface skims one by one, greasy dirt go clean after, again the car bits are poured into water washes down metal cleaner in the clean hopper; The long-pending per-cent of part is HF: HNO
3: H
2O=1: 3: 4 composite concentrated acid solution, the car bits are put into bottom sponge plastics container in batches to be paved, immerse soak 10～15 minutes in the described concentrated acid liquid after, from concentrated acid liquid, propose rapidly to immerse in the off-the-shelf tank, pull out after with flowing water acid solution thoroughly being washed down, clean with clean car bits washing out method again;
(6) niobium alloy material piece and the crumb after will cleaning made powder, adopt tubular type hydrogenation furnace hydrogenated niobium alloy material piece and car bits, other powder in the stove is cleaned, use burner hearth of wipes of alcohol again, the car of packing into after drying bits or material piece, opening mechanical pump vacuumizes, when being extracted into 1Pa, vacuum lights hydrogen, be warming up to 600 ℃ with 10 ℃/minute heat-up rates, be incubated 2 hours, material piece insulation 4～5 hours, the pressure substantially constant that keeps hydrogen in the hydrogenation process, when temperature drops to 400 ℃ in the stove, will expect to release the cooling of heating chamber trickle, come out of the stove; Car after hydrogenation bits and material piece are put into strong crusher pulverize, with the 250 purpose sieves sieve that shakes, screen overflow is put into ball mill more for a long time, charges into alcohol and argon gas, with ball mill ball milling 90 minutes, dries after sieving after the capping; Powder is put into tube furnace, when being evacuated down to 1.2Pa, the magazine of adorning powder is pushed burner hearth, begin to heat up, insulation was 1 hour when furnace temperature reached 116 ℃, continue to heat up, heat-up rate is 3.5 ℃/minute again, and insulation was 3 hours when furnace temperature reached 700 ℃, when vacuum tightness time outage cooling for 1Pa, when temperature is 600 ℃, magazine is released burner hearth trickle, blowing out, come out of the stove when furnace temperature is lower than 100 ℃; With all powdered alloys pack into mix the powder machine and mix fully after, the sampling analysis alloying element content replenishes an amount of alloying element according to analytical results, mixes with mixed powder machine once more, prepares sintered bar behind pressed compact, sintering.
The present invention compared with prior art has the following advantages: the present invention adopts methods such as cutting, pickling, letter sorting, hydrogenation, dehydrogenation, the waste material that has prepared the niobium alloy recovery of cleaning, make it become reusable raw material, of the present invention workable, do not need to adopt specific installation, solve nearly all pure niobium and niobium alloy salvage material problem, reduced the cost recovery of niobium alloy, saved the niobium resource.
Embodiment
The present invention will be further described below in conjunction with embodiment.
Embodiment 1
The recovery of pure niobium bits and edges of boards angle and caput, tube head: the niobium bits adopt finish turning bits washing out method to reclaim.The cleaning of tubing, at first tubing that will be thinner (internal diameter is below 20mm) is longitudinally cast aside, make its inwall expose out, again caput, tube head and edges of boards angle are put into concentrated acid liquid and soaked, will expect from acid solution, to pull out every 3 hours, the acid solution post precipitation will be poured out than muddy lower floor's acid solution, allocate a certain amount of eo-acid again into, once more they are put into acid solution, so repeat, till material depressed portions site surface does not have variable color place, handle with clean material piece washing out method again.Consider car to be worth doing put into 50 * 50 * 300mm punching block, be pressed into electrode block with 200 tons of oil presses.Contract tail, ingot casting rising head of electrode block, caput and edges of boards angle, the extruding that car bits are pressed into put into the argon arc welding case, and down, other material piece is welded into smelting electrode in last order according to electrode block; If electrode block is not enough, can with batch the niobium alloy lath as soldering pallet, onboard with other material piece weldering.The chemical ingredients (wt.%) of the niobium ingot of reclaimed materials melting sees the following form:
| Foreign matter content | Zr | C | N | O | H | Ta | Fe | Si | W | Ni | Mo | Hf | Ti |
| GB | 0.02 | 0.01 | 0.01 | 0.025 | 0.0015 | 0.3 | 0.01 | 0.005 | 0.05 | 0.005 | 0.020 | 0.02 | 0.03 |
| Analytical value | 0.01 | 0.01 | 0.01 | 0.023 | 0.0015 | 0.28 | 0.008 | 0.0028 | 0.04 | 0.0020 | 0.016 | 0.016 | 0.025 |
Embodiment 2
The recovery of Nb-1Zr alloy car bits and edges of boards angle and caput, tube head: the ladle barrow bits adopt clean car bits washing out method to handle.When tubing cleans, at first tubing that will be thinner (internal diameter is below 20mm) is longitudinally cast aside, its inwall is exposed, caput, tube head and edges of boards angle are put into concentrated acid liquid again and soaked, will expect to take out from acid solution every 3 hours, the acid solution post precipitation will be poured out than muddy lower floor's acid solution, allocate a certain amount of eo-acid again into, to expect that once more piece puts into acid solution, so repeat, and dry up to material and adopt clean material piece washing out method to clean till back depressed portions site surface has variable color place again.Consider car to be worth doing put into 50 * 50 * 300mm punching block, press with 200 tons of oil presses and repeatedly make electrode block.Contract tail, ingot casting rising head of electrode block, caput and edges of boards angle, the extruding that car bits are pressed into put into the argon arc welding case, and down, other material piece is welded into smelting electrode in last order according to electrode block; If electrode block is not enough, can with batch the niobium alloy lath as soldering pallet, onboard with other material piece weldering.The chemical ingredients (wt.%) of the niobium ingot of reclaimed materials melting sees the following form:
| Foreign matter content | Zr | C | N | O | H | Ta | Fe | Si | W | Ni | Mo | Hf | Ti |
| GB | 0.8-1.2 | 0.01 | 0.01 | 0.025 | 0.0015 | 0.3 | 0.01 | 0.005 | 0.05 | 0.005 | 0.020 | 0.02 | 0.03 |
| Analytical value | 1.0 | 0.01 | 0.01 | 0.023 | 0.0015 | 0.28 | 0.008 | 0.0028 | 0.04 | 0.0020 | 0.016 | 0.016 | 0.025 |
Embodiment 3
The recovery of C-103 (Nb-10Hf-1Ti-0.7Zr) alloy material: the ingot casting rising head is sawn into the piece that width is 50mm, adopts clean material piece washing out method to clean.The ladle barrow bits adopt clean car bits washing out method to clean.Forge the head and the sheet material corner of rod: caput is put into concentrated acid liquid soak, to expect from acid solution, to take out every 3 hours, with the pale precipitation thing that brushes away the material surface, the acid solution post precipitation will be poured out than the acid solution of cleaning, allocate a certain amount of eo-acid again into, to expect that once more piece puts into acid solution, so repeat, dry till back depressed portions site surface do not have jaundice, turning black and changing color place up to material; Clean with clean material piece washing out method again.Push the tail employing of contracting and push the tail processing washing out method that contracts.The finish turning bits that forge rod are put into buck boil, the oil that will waft at water surface skims one by one, greasy dirt go clean after, again the car bits are poured into water washes down buck in the clean hopper; Join concentrated acid solution, car bits put into basket in batches with Louing, immerse soak 10～15 minutes in the acid solution after, from acid solution, propose in the off-the-shelf tank of immersion rapidly; Adopt clean car bits washing out method to clean again.The car bits will be pressed into electrode just can carry out the melting purification, need the annealing of niobium alloy car bits is put into the niobium alloy bits of cleaning in the vacuum annealing furnace, behind the lid lid, the heat-up rate that adopts 10 ℃/3 minutes is come out of the stove below stove internal cooling to 100 ℃ 950～1200 ℃ of insulations 1～2 hour.For melting is convenient once more, need the niobium alloy bits are pressed into electrode, consider car to be worth doing put into 50 * 50 * 300mm punching block, be pressed into electrode block with 200 tons of oil presses.Contract tail, ingot casting rising head of electrode block, caput and edges of boards angle, the extruding that car bits are pressed into put into the argon arc welding case, and down, other material piece is welded into smelting electrode in last order according to electrode block; If electrode block is not enough, can with batch the niobium alloy lath as soldering pallet, onboard with other material piece weldering.The chemical ingredients of the niobium ingot of reclaimed materials melting (≤wt.%) see the following form:
| Foreign matter content | Hf | Ti | Zr | W | Ta | C | O | N | H |
| GB | 9.0-11.0 | 0.7-1.3 | 0.7 | 0.5 | 0.5 | 0.015 | 0.026 | 0.015 | 0.002 |
| Analytical value | 10.2 | 0.9 | 0.5 | 0.48 | 0.39 | 0.01 | 0.019 | 0.009 | 0.001 |
Embodiment 4
The recovery of 5BH Ц (Nb-5W-2Mo-1Zr) alloy material: the ingot casting rising head reclaims and adopts clean material piece washing out method to clean.The ladle barrow bits reclaim and adopt clean car bits washing out method.Push the tail recovery employing of contracting and push the tail processing washing out method that contracts.Forge the head and the sheet material corner of rod: caput is put into concentrated acid liquid soak, to expect from acid solution, to take out every 3 hours, brush away the pale precipitation thing on material surface, the acid solution post precipitation will be poured out than the upper strata acid solution of cleaning, allocate a certain amount of eo-acid again into, to expect that once more piece puts into acid solution, so repeat, dry till back depressed portions site surface do not have jaundice, turning black and changing color place up to material; Adopt clean material piece washing out method to clean again.The finish turning bits that forge rod are at first put into buck and are boiled, and the oil that will waft at water surface skims one by one, oil go clean after, again the car bits are poured into water washes down buck in the clean hopper.Join concentrated acid solution, car bits put in batches with Louing paved in the basket, immerse soak 10～15 minutes in the acid solution after, from acid solution, propose rapidly with flowing water acid solution to be washed down in the off-the-shelf tank of immersion; Adopt clean car bits washing out method to clean again.Convenient for melting, need the niobium alloy bits are pressed into electrode, the niobium alloy bits of cleaning are put in the vacuum annealing furnace, behind the lid lid, the heat-up rate that adopted 10 ℃/3 minutes is incubated 1～2 hour at 950～1200 ℃, comes out of the stove below stove internal cooling to 100 ℃; Consider car to be worth doing put into 50 * 50 * 300mm punching block, be pressed into electrode block with 200 tons of oil presses.Contract tail, ingot casting rising head of electrode block, caput and edges of boards angle, the extruding that car bits are pressed into put into the argon arc welding case, and down, other material piece is welded into smelting electrode in last order according to electrode block; If electrode block is not enough, can with batch the niobium alloy lath as soldering pallet, onboard with other material piece weldering.The chemical ingredients (wt.%) of the niobium ingot of reclaimed materials melting sees the following form
| Constituent content | W | Mo | Zr | C | N | O | H | Fe | Cu | Si | Ti | Ta |
| Standard | 4.5-5.5 | 1.5-2.5 | 0.8-1.5 | 0.03 | 0.003 | 0.03 | 0.002 | ＜0.002 | ＜0.002 | ＜0.003 | ＜0.002 | 0.3 |
| Analytical value | 4.8 | 1.74 | 1.1 | 0.01 | 0.0026 | 0.02 | 0.001 | ＜0.0014 | ＜0.0014 | ＜0.0028 | ＜0.0014 | 0.28 |
Embodiment 5
The recovery of 5BH Ц (Nb-5W-2Mo-1Zr) alloy material: the recovery of ingot casting rising head adopts clean material piece washing out method to clean.The ladle barrow bits reclaim and adopt clean material piece washing out method to clean.Push the recovery employing of the tail that contracts and push the tail processing washing out method that contracts.Forge the head and the sheet material corner of rod: caput is put into concentrated acid liquid soak, to expect from acid solution, to take out every 3 hours, brush away the pale precipitation thing on material surface, the acid solution post precipitation will be poured out than the upper strata acid solution of cleaning, allocate a certain amount of eo-acid again into, to expect that once more piece puts into acid solution, so repeat, dry till back depressed portions site surface do not have jaundice, turning black and changing color place up to material; Clean with clean material piece washing out method again.The car bits that at first will forge the finish turning of rod are put into buck and are boiled, and the oil that will waft at water surface skims one by one, oil go clean after, again the car bits are poured into water washes down buck in the clean hopper.Join concentrated acid solution, car bits put into basket in batches with Louing pave, immerse soak 10～15 minutes in the acid solution after, from acid solution, propose in the off-the-shelf tank of immersion rapidly; Adopt clean car bits washing out method to clean again.Convenient for melting, need the annealing of niobium alloy bits is put into the niobium alloy bits of cleaning in the vacuum annealing furnace, behind the lid lid, the heat-up rate that adopted 10 ℃/3 minutes is incubated 1～2 hour at 950～1200 ℃, comes out of the stove below stove internal cooling to 100 ℃.For melting is convenient once more, need the niobium alloy bits are pressed into electrode, consider car to be worth doing put into 50 * 50 * 300mm punching block, be pressed into electrode block with 200 tons of oil presses.Contract tail, ingot casting rising head of electrode block, caput and edges of boards angle, the extruding that car bits are pressed into put into the argon arc welding case, and down, other material piece is welded into smelting electrode in last order according to electrode block; If electrode block is not enough, can with batch the niobium alloy plate as soldering pallet, onboard with other material piece weldering.
Because the alloying element of niobium alloy waste material is at standard min, alloy is expected powder process only, joins powder, pressed compact, sintered bar legal system and is equipped with sintering.
The chemistry (wt.%) of the niobium ingot of reclaimed materials melting sees the following form
| Constituent content | W | Mo | Zr | C | N | O | H | Fe | Cu | Si | Ti | Ta |
| Standard | 4.5-5.5 | 1.5-2.5 | 0.8-1.5 | 0.03 | 0.003 | 0.03 | 0.002 | ＜0.002 | ＜0.002 | ＜0.003 | ＜0.002 | 0.3 |
| Analytical value | 5.3 | 1.91 | 1.2 | 0.01 | 0.0023 | 0.027 | 0.001 | ＜0.0014 | ＜0.0014 | ＜0.0028 | ＜0.0014 | 0.23 |
Claims (2)
1, the recycling method of a kind of niobium and niobium alloy waste material is characterized in that this method may further comprise the steps:
(1) processing of ingot casting rising head: the ingot casting rising head is sawn into the piece that width is 50mm, and because of the ingot casting rising head does not have oxide skin, only need adopt volume percent when reclaiming is HF: HNO
3: H
2O=1: 3: 4 concentrated acid liquid soaked 10～20 minutes, very fast again proposition, put into life water and washed down and dry;
(2) processing of ladle barrow bits: the ladle barrow bits are meant the scurf of taking off of melting ingot casting, at first the car bits being put into the metal cleaner aqueous solution boils, 20kg crumb 1kg detergent, the oil that will waft at water surface skims one by one, until there not being oil to waft till the surface, oil go clean after, again the car bits are poured into water washes down metal cleaner in the clean hopper; The long-pending per-cent of part is HF: HNO
3: H
2O=2: 3: 14 acid solution, car bits are put in batches with Louing basket pave, immerse soak 1～6 minute in the described acid solution after, from acid solution, propose rapidly to immerse in the off-the-shelf tank, with flowing water acid solution is thoroughly washed down, be flushed in the groove water become limpid till after pull out, control water, put into baking oven and dry; Car bits with oven dry adopt manual sorting's way, choose foreign peoples's car bits, wood chip, broom rod and the end of a thread of sneaking into; Less car bits will carefully sort the back and inhale the chip that removes lathe tool with magnet;
(3) the contract processing of tail of extruding: extruding is contracted tail along the section that circumferentially is sawn into 30～70mm, again these sections are sawn into semicircle; Be HCl: H with volume percent again
2O=1: 2 hydrochloric acid solution soaks, and iron is with after the niobium alloy major part is separated, and knocks out with flat chisel and the hammer iron with bulk, and the iron of material heart portion will go with the drilling machine brill; Going clean material piece to put into volume percent the iron major part is HF: HNO
3: H
2O=1: 3: 4 concentrated acid liquid soaks, and will expect to take out from described concentrated acid liquid every 3 hours, brushes away the pale precipitation thing on material surface with plastic bruss, will be behind the concentrated acid liquid precipitate than pouring out of cleaning, and pouring into and pouring out concentrated acid liquid is HF: HNO with the volume percent of volume
3: H
2O=1: 3: 4 newly join concentrated acid liquid, will expect that once more piece puts into concentrated acid liquid, so repeat repeatedly, dry till back depressed portions site surface do not have jaundice, turning black and changing color place up to material; After soaking with dilute hydrochloric acid liquid again, pull, put into mobile water very soon out and rinse well, pull back concave surface out and dry down;
(4) processing of forging caput and sheet material corner: caput and sheet material corner are put into the immersion of concentrated acid liquid, to expect from acid solution, to take out every 3 hours, with the pale precipitation thing that brushes away the material surface, the acid solution post precipitation will be poured out than muddy lower floor, and pouring into and pouring out concentrated acid liquid is HF: HNO with the volume percent of volume
3: H
2O=1: 3: 4 newly join concentrated acid liquid, will expect that once more piece puts into concentrated acid liquid, so repeat, dry till back depressed portions site surface do not have jaundice, turning black and changing color place up to material; Clean with clean material piece washing out method again;
(5) forge the processing of the finish turning bits of rod: at first the car bits are put into the metal cleaner aqueous solution and boil, the oil that will waft at water surface skims one by one, greasy dirt go clean after, again the car bits are poured into water washes down metal cleaner in the clean hopper; The long-pending per-cent of part is HF: HNO
3: H
2O=1: 3: 4 composite concentrated acid solution, the car bits are put into bottom sponge plastics container in batches to be paved, immerse soak 10～15 minutes in the described concentrated acid liquid after, from concentrated acid liquid, propose rapidly to immerse in the off-the-shelf tank, pull out after with flowing water acid solution thoroughly being washed down, clean with clean car bits washing out method again;
(6) the niobium alloy bits of cleaning are put in the vacuum annealing furnace, behind the lid lid, the heat-up rate that adopts 10 ℃/3 minutes was 950～1200 ℃ of insulations 1～2 hour, below stove internal cooling to 100 ℃, come out of the stove, for melting is convenient once more, need niobium alloy car bits are put into the punching block of 50 * 50 * 300mm, be pressed into electrode block with 200 tons of oil press gradation;
(7) contract tail and ingot casting rising head of electrode block, caput and the edges of boards angle that car bits are pressed into, extruding put into the argon arc welding case, and down, other material piece is welded into smelting electrode in last order according to electrode block; When electrode block is not enough, will with batch the niobium alloy lath as soldering pallet, the material piece of other kind is welded on the supporting plate.
2, the recycling method of a kind of niobium and niobium alloy waste material is characterized in that this method may further comprise the steps:
(1) processing of ingot casting rising head: the ingot casting rising head is sawn into the piece that width is 50mm, and because of the ingot casting rising head does not have oxide skin, only need adopt volume percent when reclaiming is HF: HNO
3: H
2O=1: 3: 4 concentrated acid liquid soaked 10～20 minutes, very fast again proposition, put into life water and washed down and dry;
(2) processing of ladle barrow bits: the ladle barrow bits are meant the scurf of taking off of melting ingot casting, at first the car bits being put into the metal cleaner aqueous solution boils, 20kg crumb 1kg detergent, the oil that will waft at water surface skims one by one, until there not being oil to waft till the surface, oil go clean after, again the car bits are poured into water washes down metal cleaner in the clean hopper; The long-pending per-cent of part is HF: HNO
3: H
2O=2: 3: 14 acid solution, car bits are put in batches with Louing basket pave, immerse soak 1～6 minute in the described acid solution after, from acid solution, propose rapidly to immerse in the off-the-shelf tank, with flowing water acid solution is thoroughly washed down, be flushed in the groove water become limpid till after pull out, control water, put into baking oven and dry; Car bits with oven dry adopt manual sorting's way, choose foreign peoples's car bits, wood chip, broom rod and the end of a thread of sneaking into; Less car bits will carefully sort the back and inhale the chip that removes lathe tool with magnet;
(3) the contract processing of tail of extruding: extruding is contracted tail along the section that circumferentially is sawn into 30～70mm, again these sections are sawn into semicircle; Be HCl: H with volume percent again
2O=1: 2 hydrochloric acid solution soaks, and iron is with after the niobium alloy major part is separated, and knocks out with flat chisel and the hammer iron with bulk, and the iron of material heart portion will go with the drilling machine brill; Going clean material piece to put into volume percent the iron major part is HF: HNO
3: H
2O=1: 3: 4 concentrated acid liquid soaks, and will expect to take out from described concentrated acid liquid every 3 hours, brushes away the pale precipitation thing on material surface with plastic bruss, will be behind the concentrated acid liquid precipitate than pouring out of cleaning, and pouring into and pouring out concentrated acid liquid is HF: HNO with the volume percent of volume
3: H
2O=1: 3: 4 newly join concentrated acid liquid, will expect that once more piece puts into concentrated acid liquid, so repeat repeatedly, dry till back depressed portions site surface do not have jaundice, turning black and changing color place up to material; After soaking with dilute hydrochloric acid liquid again, pull, put into mobile water very soon out and rinse well, pull back concave surface out and dry down;
(4) processing of forging caput and sheet material corner: caput and sheet material corner are put into the immersion of concentrated acid liquid, to expect from acid solution, to take out every 3 hours, with the pale precipitation thing that brushes away the material surface, the acid solution post precipitation will be poured out than muddy lower floor, and pouring into and pouring out concentrated acid liquid is HF: HNO with the volume percent of volume
3: H
2O=1: 3: 4 newly join concentrated acid liquid, will expect that once more piece puts into concentrated acid liquid, so repeat, dry till back depressed portions site surface do not have jaundice, turning black and changing color place up to material; Clean with clean material piece washing out method again;
(5) forge the processing of the finish turning bits of rod: at first the car bits are put into the metal cleaner aqueous solution and boil, the oil that will waft at water surface skims one by one, greasy dirt go clean after, again the car bits are poured into water washes down metal cleaner in the clean hopper; The long-pending per-cent of part is HF: HNO
3: H
2O=1: 3: 4 composite concentrated acid solution, the car bits are put into bottom sponge plastics container in batches to be paved, immerse soak 10～15 minutes in the described concentrated acid liquid after, from concentrated acid liquid, propose rapidly to immerse in the off-the-shelf tank, pull out after with flowing water acid solution thoroughly being washed down, clean with clean car bits washing out method again;
(6) niobium alloy material piece and the crumb after will cleaning made powder, adopt tubular type hydrogenation furnace hydrogenated niobium alloy material piece and car bits, other powder in the stove is cleaned, use burner hearth of wipes of alcohol again, the car of packing into after drying bits or material piece, opening mechanical pump vacuumizes, when being extracted into 1Pa, vacuum lights hydrogen, be warming up to 600 ℃ with 10 ℃/minute heat-up rates, be incubated 2 hours, material piece insulation 4～5 hours, the constant pressure that keeps hydrogen in the hydrogenation process, when temperature drops to 400 ℃ in the stove, will expect to release the cooling of heating chamber trickle, come out of the stove; Car after hydrogenation bits and material piece are put into strong crusher pulverize, with the 250 purpose sieves sieve that shakes, screen overflow is put into ball mill more for a long time, charges into alcohol and argon gas, with ball mill ball milling 90 minutes, dries after sieving after the capping; Powder is put into tube furnace, when being evacuated down to 1.2Pa, the magazine of adorning powder is pushed burner hearth, begin to heat up, insulation was 1 hour when furnace temperature reached 116 ℃, continue to heat up, heat-up rate is 3.5 ℃/minute again, and insulation was 3 hours when furnace temperature reached 700 ℃, when vacuum tightness time outage cooling for 1Pa, when temperature is 600 ℃, magazine is released burner hearth trickle, blowing out, come out of the stove when furnace temperature is lower than 100 ℃; With all powdered alloys pack into mix the powder machine and mix fully after, the sampling analysis alloying element content replenishes an amount of alloying element according to analytical results, mixes with mixed powder machine once more, prepares sintered bar behind pressed compact, sintering.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100188542A CN100516257C (en) | 2007-10-12 | 2007-10-12 | Method for recovering and reusing niobium and niobium alloy waste |
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| CNB2007100188542A CN100516257C (en) | 2007-10-12 | 2007-10-12 | Method for recovering and reusing niobium and niobium alloy waste |
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| CN100516257C true CN100516257C (en) | 2009-07-22 |
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| CN102399990A (en) * | 2011-11-28 | 2012-04-04 | 镇江中孚复合材料有限公司 | Method for extracting niobium oxide from waste and old niobium-containing high-temperature alloy |
| JP6412501B2 (en) * | 2013-10-08 | 2018-10-24 | 昭和電工株式会社 | Method for producing niobium granulated powder |
| CN107746970A (en) * | 2017-09-26 | 2018-03-02 | 国核宝钛锆业股份公司 | A kind of zirconium and zircaloy electrode preparation method |
| CN109616714A (en) * | 2018-11-26 | 2019-04-12 | 天津普兰能源科技有限公司 | The recovery method of niobium base electrode material in a kind of electrode slice |
| CN111168074A (en) * | 2020-01-15 | 2020-05-19 | 北京科技大学 | Preparation method of Nb521 alloy powder for low-cost 3D printing |
| CN111621642A (en) * | 2020-03-05 | 2020-09-04 | 国核宝钛锆业股份公司 | Method for recovering and purifying Nb sawdust residue |
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