CN1821427A - Hydrothermal method for recovering metal from waste hard alloy - Google Patents

Hydrothermal method for recovering metal from waste hard alloy Download PDF

Info

Publication number
CN1821427A
CN1821427A CNA2006100205399A CN200610020539A CN1821427A CN 1821427 A CN1821427 A CN 1821427A CN A2006100205399 A CNA2006100205399 A CN A2006100205399A CN 200610020539 A CN200610020539 A CN 200610020539A CN 1821427 A CN1821427 A CN 1821427A
Authority
CN
China
Prior art keywords
cobalt
alloy
tungsten
temperature
metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CNA2006100205399A
Other languages
Chinese (zh)
Other versions
CN1332045C (en
Inventor
戴受惠
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
HANJI INVESTMENT CO Ltd CHENGDU
Original Assignee
HANJI INVESTMENT CO Ltd CHENGDU
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by HANJI INVESTMENT CO Ltd CHENGDU filed Critical HANJI INVESTMENT CO Ltd CHENGDU
Priority to CNB2006100205399A priority Critical patent/CN1332045C/en
Publication of CN1821427A publication Critical patent/CN1821427A/en
Application granted granted Critical
Publication of CN1332045C publication Critical patent/CN1332045C/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

  • Manufacture And Refinement Of Metals (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

The present invention provides hydrothermal process for recovering Co and other metals from waste hard alloy. The process includes crushing waste hard alloy, soaking with HNO3, treating in high pressure caldron to separate out nitrate solution of Co and other metal elements, oxidize WC into WO3 powder, and reaction in fluidized bed to obtain WC-Co, etc. The present invention has short process, simple apparatus, low power consumption, high efficiency, no pollution and easy use in industrial production, and is suitable for recovering WC-Ni, WC-NiFe, WC-TiC-Co, WC-Mo<2C-Co, WC-(Nb.Ta)C-Co, WC-VC-Co, WC-Cr3C2-Co, WC-TiC-CoNi, etc.

Description

A kind of hydrothermal method reclaims the method for metal from scrap hard alloy
Technical field
The present invention relates to reclaim in a kind of WC-Co alloy the method for Co, W, belong to field of inorganic chemical engineering.
Background technology
The WC-Co alloy is the material of WC by the Co connection, is widely used as cutting tool, mould etc. in industrial circles such as space flight, automobile, electronics.China's annual output reaches 1.5 ten thousand tons, and wherein cobalt is the 900-3750 ton, but its waste and old product recovery utilization rate is extremely low, and the U.S. is more than 60%, and Japan is 20%.Co is strategic materials, is poor source in China, so its recycling is very important.Traditional recovery method has three kinds, i.e. high temperature expansion crush method, zinc alloy method and HCI or FeCO 3The leaching method.The former at first is heated to 1800-2300 ℃ of high temperature with the WC-Co fragment in indifferent gas gas, quenches then to make alloy pulverization because of Co expands, and further behind the ball milling and reclaim and obtain WC-Co.But this method energy consumption is big, cost is high, and form in removal process not only that some do not wish to occur as W 2C, free C and η be (W mutually 3nCo 3nC nOr W 6nCo 6nC n).The zinc alloy method is that the WC-Co fragment at first is immersed in 950 ℃ the fusing zinc water, zinc and cobalt generation eutectic reaction form low melting point Zn-Zo alloy and make the efflorescence of WC-Co fragment, make the zinc evaporation 1000-1050 ℃ of vacuum distilling then, and reclaim the spongy WC-Co that easily pulverizes.This method energy consumption is still very high, and reclaims impure inevitably Zn in the product.The third recovery method is with HCl, FeCO 3, HCl+FeCO 3For leaching broken the following the example of of hydro-thermal of solvent, though this method energy consumption is low, this method is difficult to recycle the WC-Co content of fine particle WC and low Co content.Cl -Ion tool severe corrosive, and bring impurities such as Fe impurity.
Summary of the invention
The objective of the invention is to overcome above Technology shortcoming, the flow process to simplify under the less energy-consumption condition makes various trade mark WC-Co alloys all can be recovered as powder such as high-purity Nano-class WC-Co or WC, W, Co.
The method that reclaims Co, W in the WC-Co alloy provided by the invention ties up in the autoclave, and waste and old WC-Co alloy forms Co salt and WO through the hydrothermal oxidization reaction 30.33H 2O and being recovered also can further be converted to WC-Co or Co, W, WC.
Wherein said hydrothermal oxidization method is with HNO 3Get and oxidation solvent for quenching.Owing to react under High Temperature High Pressure, speed of reaction is fast, and is easy to make the alloy reaction process to tend to be balanced, and through at a certain temperature, behind the reaction certain hour, Co forms Co salt Co (NO among the WC-Co 3) 2, WC is converted into WO 30.33H 2O.
Co salt and WO 30.33H 2O can make it directly to be recovered as WC-Co or WC, W, Co through " closed loop level Four fluidization process ", " closed loop level Four rotary fluid method " or " closed loop level Four displacement fluidization process ".Reclaim after product tool nano-scale particle size powder, be not with any metallic impurity, chlorion, with the goods that make of weight sintering, keep even surpassed the mechanics and the physicals level of former powder-product.
Specifically, the method that reclaims Co, W in the WC-Co alloy provided by the invention may further comprise the steps:
A, waste and old cobalt, tungstenalloy are particle diameter 1-3mm through mechanical fragmentation, with concentration 2-11M HNO 3Be solvent soaking; Wherein the grain fineness number of WC is approximately 0.5-5 μ m, and Co content is 6-25 Wt%;
B, in the autoclave of band magnetic stirring apparatus, titanium alloy lining 100-200 ℃ of constant temperature, handled 10-48 hour under the rotating speed 100-200rpm condition, W is converted into WO among the WC-Co 30.33H 2O, Co is converted into Xiao Suangu;
C, separation solid, liquid phase; Liquid phase is a cobalt salt solution, and solid phase is WO 30.33H 2O.
With WO 30.33H 2The O solid phase is diluted to the 20-30% solids solution with deionized water, and 8000-30000rpm high speed shear emulsification instrument was sheared 30 minutes, and with inlet temperature 230-250 ℃, temperature out 110-120 ℃ condition, supersonic spraying drying, decomposition and inversion are WO 3Carry out thermal chemical reaction through fluidized-bed and obtain nanometer W or WC;
With inlet temperature 230-250 ℃, temperature out 110-120 ℃ condition, it is CoO that supersonic spraying makes solution drying, decomposition and inversion with cobalt nitrate solution; Carry out thermal chemical reaction through fluidized-bed and obtain nano Co.
Also not separated solid, liquid mixture can be sheared 30 minutes with 8000-30000rpm high speed shear emulsification instrument, make the further dispersing and disintegrating of solid phase in the solution, with inlet temperature 230-250 ℃, temperature out 110-120 ℃ condition, it is WO that supersonic spraying makes the dry decomposition and inversion of mixed solution 3-CoO; Obtain the nano WC-Co powder through the fluid bed heat chemical reaction.
Described fluid bed heat chemical reaction is a kind of in " closed loop level Four fluidization process ", " the closed loop level Four rotary fluid method " or " closed loop level Four displacement fluidization process ".
In the aforesaid method, as the described waste and old cobalt of a step, tungstenalloy WC grain degree 1-5 μ m, Co content 10-23 Wt%, then HNO 3Concentration 2-3M; 130-150 ℃ of b step process temperature, time 4-24 hour.
As the described waste and old cobalt of a step, tungstenalloy WC grain degree 0.5-1 μ m, Co content 10-13 WtBelow the %, HNO then 3Concentration 3-11M; 150-200 ℃ of b step process temperature, time 24-40 hour.
The c step is separated employing membrane separation process, membrane pore size 0.08-0.6 μ m.
Above-mentioned recovery technology in like manner is applicable to the recycling of alloys such as WC-CoNi, WC-CoNiFe, WC-TiC-CoNi.Only different is that liquid phase is the nitrate solution of cobalt, nickel or cobalt, nickel, iron or cobalt, nickel, and solid phase is WO 30.33H 2O or WO 3-TiO 2Deng.Recovery method may further comprise the steps:
The alloy of the carbide of a, waste and old cobalt and/or nickel and/or iron and IVB, VB or group vib element is particle diameter 1-3mm through mechanical fragmentation, with concentration 2-11M HNO 3Be solvent soaking;
B, handled 10-48 hour under 100-200 ℃ of constant temperature in the autoclave of band magnetic stirring apparatus, titanium alloy lining, the carbide of IVB, VB or group vib element is converted into oxide compound in the alloy, and cobalt, nickel or iron are converted into nitrate; Such as, WC is converted into WO in the alloy 30.33H 2O, or WC-TiC is converted into WO 3-TiO 2Cobalt, nickel or iron are converted into nitrate;
C, separation solid, liquid phase; Liquid phase is cobalt, nickel or iron nitrate solution, and solid phase is the oxide compound of IVB, VB or group vib element, as WO 30.33H 2O or WO 3-TiO 2
Advantage of the present invention:
1, temperature of reaction is low, energy consumption is low.
2, flow process is brief, the rate of recovery is high, product purity is high.
3, equipment is simple, cost is low, be easy to enlarge batch process.
Below by embodiment, the present invention being further described, is limitation of the present invention but should not be construed as.Below be specific embodiment, those of ordinary skills can also make modification, replacement, the change of various ways according to technique scheme.All modification, replacement, changes of doing based on above-mentioned technological thought all belong to scope of the present invention.
Embodiment 1:
Getting wc grain size is 1-5 μ m, and Co content is the WC-Co fragment 0.23-0.24Mol of 20% massfraction, adds 3Mol HNO 330ml moves in the autoclave of titanium alloy lining, handles to make in 24 hours reacting completely 150 ℃ of rotating speed 120rpm magnetic agitation.The WO30.33H2O that obtains after the membrane sepn washing wherein contains the W75.2% massfraction with the EDS analysis, contain oxygen 24.5% massfraction, and Co is a trace, only less than 0.3% massfraction.The filtrate that obtains is analyzed with ICP-AES, and Co content is 98.5% massfraction of Co content in the former state (WC-Co fragment), and only several ppm of W content.
Embodiment 2:
Getting wc grain size is 0.5-1 μ m, and Co content is the WC-Co alloy fragment 0.23-0.24Mol of 13% massfraction, adds 30ml 7Mol HNO 3Move into autoclave and handled 24 hours at 160 ℃, the solid WO30.33H2O that obtains confirms that with XRD analysis solids is entirely WO 3Spectral line, when when 200 ℃ are handled, CoWO is arranged in the solid 4Phase.Analyzing Co with EDS, ICP-AES is trace.W is a trace in the analysis gained solution, and the Co rate of recovery is 98.5%.
Embodiment 3:
Getting wc grain size is 0.5 μ m, and Co content is the WC-Co fragment 0.23-0.24Mol of 6% massfraction, adds 30ml 9M HNO 3After, move into autoclave and handled 28 hours at 170 ℃.Through XRD, ICP-AES instrumental analysis, prove that respectively the WC complete oxidation is WO 3, wherein only have trace Co; And only containing several ppmW in the Co salts solution that obtains, 96.5% above Co has been quenched and has been got in the raw material.
Embodiment 4:
Getting wc grain size is 0.5-1 μ m, and Co content is the WC-Co alloy fragment 30Mol of 13% massfraction, adds liter 7Mol HNO 3, moving into titanium lined alloy volume is the autoclave of 5 liters, and 150 ℃ through temperature reaction 24 hours, and the gained reaction product is through sampling analysis, WO 3Middle Co is a trace, and W is a trace in the cobalt nitrate solution.Confirmatory reaction fully after, in mixture solution, add 1: 1 ethanolic soln, be diluted to that solid content is 40 in the solution Wt% sheared 30 minutes with 8000-3000rpm high speed shear emulsification instrument, and ullrasonic spraying drying then is at last by carrying out thermal chemical reaction one of in patent " closed loop level Four rotary fluid method ", " the closed loop level Four fluidized bed process " or " closed loop level Four displacement fluidization process ".Promptly in first reactor 350-450 ℃, N 2/ 10%H 2In carried out the first step low-temperature reduction one hour, generate WO 2.9-CoO; In the reactor of the second stage 500-600 ℃, N 2/ 10%H 2In carry out the second step reduction reaction 1.5 hours, generate W-Co; The CO/CO of carbon activity in third stage reactor＞1 2In the atmosphere, 800-850 ℃ was carried out carburizing reagent 2 hours; Activity is 0.4 CO in fourth stage reactor 2In/CO the atmosphere, 700-750 ℃ is gone uncombined carbon reaction 1 hour.Product WC-Co powder granularity＜0.2 μ m, no η phase, nothing trip carbon.
Embodiment 5
Get the WC-6%Co-20%Ni that the WC grain degree is 1-5 μ m (Wt%) alloy particle (ф 1-3mm) 0.23-0.24Mol and be dissolved in 3MolHNO 3Behind the 30ml, move in the autoclave of band magnetic agitation, titanium alloy lining 150 ℃ of reactions 24 hours, WO 30.33H 2O analyzes tungstenic 73.2% massfraction through EDS, and Co is a trace, and Ni content is less than 0.15%; Cobalt, nickel total amount are 97.8% of former content in the nitrate solution, and tungsten is trace.
Embodiment 6
Get the WC-6%Co-16%Ni-4%Fe that the WC grain degree is 1-5 μ m (Wt%) alloy particle (ф 1-3mm) 0.23-0.24Mol and be dissolved in 3MolHNO 3Among the 30ml, move in the titanium lining autoclave of band magnetic stirring apparatus, 150 ℃ were reacted 26 hours, got WO 30.33H 2O, analyzing tungsten recovery rate through EDS is 97.8%, cobalt, nickel, iron total content＜0.3% massfraction; Cobalt, nickel, iron total amount are 96.7% of former content in the nitrate solution, and tungsten is trace.
Embodiment 7
Get the WC-15%TiC-6%Co-20% that the WC grain degree is 1-5 μ m (Wt%) Ni alloy particle (ф 1-3mm) 0.23-0.24Mol and be dissolved in 3MolHNO 3Among the 30ml, move in the titanium lining autoclave of band magnetic stirring apparatus,, get WO 150 ℃ of magnetic agitation reactions 24 hours 3-TiO 2, analyze WO through X ray fluorescent spectrometer 379.6% massfraction, TiO 220.20% massfraction, cobalt, nickel trace; Cobalt, nickel total content are 98% massfraction of its former total content in the nitrate solution, and tungsten is trace.
In a word, the novel method flow process that reclaims metallic elements such as cobalt from hard alloy scraps provided by the invention is short, processing unit is simple, energy consumption is low, efficient is high, pollution-free, easy expansion is produced in batches, and is suitable for WC-Ni, WC-NiFe, WC-TiC-Co, WC-Mo 2C-Co, WC-(Nb.Ta) C-Co, WC-VC-Co, WC-Cr 3C 2Wimet such as-Co, WC-TiC-CoNi reclaims, and the alloy purity height of recovery is not with any metallic impurity, chlorion etc.

Claims (9)

1, a kind of method that reclaims metal from scrap hard alloy may further comprise the steps:
The surplus or excess alloy of the carbide of a, IVB, VB or group vib element and cobalt and/or nickel and/or ferrous metal is particle diameter 1-3mm through mechanical fragmentation, with concentration 2-11M HNO 3Be solvent soaking;
B, handled 10-48 hour under 100-200 ℃ of constant temperature in the autoclave of band magnetic stirring apparatus, titanium alloy lining, the carbide of IVB, VB or group vib element is converted into oxide compound in the alloy, and cobalt, nickel or iron are converted into nitrate;
C, separation solid, liquid phase; Liquid phase is cobalt, nickel or iron nitrate solution, and solid phase is the oxide compound of IVB, VB or group vib element.
2, the method that reclaims metal from scrap hard alloy according to claim 1, it is characterized in that: described IVB, VB or group vib element are tungsten, molybdenum, chromium, vanadium, niobium, tantalum, titanium, zirconium or hafnium.
3, the method that from scrap hard alloy, reclaims metal according to claim 2, it is characterized in that: described surplus or excess alloy is that waste and old cobalt, tungstenalloy may further comprise the steps:
A, waste and old cobalt, tungstenalloy are particle diameter 1-3mm through mechanical fragmentation, with concentration 2-11M HNO 3Be solvent soaking;
B, handled 10-48 hour under 100-200 ℃ of constant temperature in the autoclave of band magnetic stirring apparatus, titanium alloy lining, W is converted into WO among the WC-Co 30.33H 2O, Co is converted into Xiao Suangu;
C, separation solid, liquid phase; Liquid phase is a cobalt salt solution, and solid phase is WO 30.33H 2O.
4, the method for recovery cobalt metal according to claim 3, tungsten is characterized in that:
With WO 30.33H 2The O solid phase is diluted to the 20-30% solids solution with deionized water, and 8000-30000rpm high speed shear emulsification instrument was sheared 30 minutes, and with inlet temperature 230-250 ℃, temperature out 110-120 ℃ condition, supersonic spraying drying, decomposition and inversion are WO 3Carry out thermal chemical reaction through fluidized-bed and obtain nanometer W or WC;
With inlet temperature 230-250 ℃, temperature out 110-120 ℃ condition, it is CoO that supersonic spraying makes solution drying, decomposition and inversion with cobalt nitrate solution; Carry out thermal chemical reaction through fluidized-bed and obtain nano Co.
5, the method for recovery cobalt metal according to claim 3, tungsten is characterized in that:
Not separated solid, liquid mixture was sheared 30 minutes with 8000-30000rpm high speed shear emulsification instrument, make the further dispersing and disintegrating of solid phase in the solution, with inlet temperature 230-250 ℃, temperature out 110-120 ℃ condition, it is WO that supersonic spraying makes the dry decomposition and inversion of mixed solution 3-CoO; Obtain the nano WC-Co powder through the fluid bed heat chemical reaction.
6, according to the method for claim 4 or 5 described recovery cobalt metals, tungsten, it is characterized in that: a kind of in " closed loop level Four fluidization process ", " the closed loop level Four rotary fluid method " or " closed loop level Four displacement fluidization process " of described fluid bed heat chemical reaction.
7, according to the method for each described recovery cobalt metal of claim 3-6, tungsten, it is characterized in that: the described waste and old cobalt of a step, tungstenalloy WC grain degree 1-5 μ m, Co content 10-23wt%, then HNO 3Concentration 2-3M; 130-150 ℃ of b step process temperature, time 4-24 hour.
8, according to the method for each described recovery cobalt metal of claim 3-5, tungsten, it is characterized in that: the described waste and old cobalt of a step, tungstenalloy WC grain degree 0.5-1 μ m, below the Co content 10-13wt%, HNO then 3Concentration 3-11M; 150-200 ℃ of b step process temperature, time 24-40 hour.
9, according to the method for each described recovery cobalt metal of claim 3-8, tungsten, it is characterized in that: the c step is separated employing membrane separation process, membrane pore size 0.08-0.6 μ m.
CNB2006100205399A 2006-03-22 2006-03-22 Hydrothermal method for recovering metal from waste hard alloy Expired - Fee Related CN1332045C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB2006100205399A CN1332045C (en) 2006-03-22 2006-03-22 Hydrothermal method for recovering metal from waste hard alloy

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2006100205399A CN1332045C (en) 2006-03-22 2006-03-22 Hydrothermal method for recovering metal from waste hard alloy

Publications (2)

Publication Number Publication Date
CN1821427A true CN1821427A (en) 2006-08-23
CN1332045C CN1332045C (en) 2007-08-15

Family

ID=36923000

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2006100205399A Expired - Fee Related CN1332045C (en) 2006-03-22 2006-03-22 Hydrothermal method for recovering metal from waste hard alloy

Country Status (1)

Country Link
CN (1) CN1332045C (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101824543A (en) * 2010-05-27 2010-09-08 中南大学 Method for sulfidizing heavy metal waste and recovering valuable metals in heavy metal waste
CN102808086A (en) * 2012-08-31 2012-12-05 北京工业大学 Method for preparing ultrafine tungsten oxide nanopowder by recovering waste hard alloy with hydrothermal method
CN104313330A (en) * 2014-07-31 2015-01-28 惠州市斯瑞尔环境化工有限公司 A method of recovering heavy metals in waste hard alloys by adopting ferric sulfate as a solvent

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2110590C1 (en) * 1996-07-11 1998-05-10 Институт металлургии им.А.А.Байкова РАН Method of processing carbide waste originated from solid alloys

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101824543A (en) * 2010-05-27 2010-09-08 中南大学 Method for sulfidizing heavy metal waste and recovering valuable metals in heavy metal waste
CN101824543B (en) * 2010-05-27 2011-07-06 中南大学 Method for sulfidizing heavy metal waste and recovering valuable metals in heavy metal waste
CN102808086A (en) * 2012-08-31 2012-12-05 北京工业大学 Method for preparing ultrafine tungsten oxide nanopowder by recovering waste hard alloy with hydrothermal method
CN102808086B (en) * 2012-08-31 2014-07-16 北京工业大学 Method for preparing ultrafine tungsten oxide nanopowder by recovering waste hard alloy with hydrothermal method
CN104313330A (en) * 2014-07-31 2015-01-28 惠州市斯瑞尔环境化工有限公司 A method of recovering heavy metals in waste hard alloys by adopting ferric sulfate as a solvent

Also Published As

Publication number Publication date
CN1332045C (en) 2007-08-15

Similar Documents

Publication Publication Date Title
Li et al. Preparation of synthetic rutile by hydrochloric acid leaching of mechanically activated Panzhihua ilmenite
Lee et al. Recycling of WC–Co hardmetal sludge by a new hydrometallurgical route
Kordzadeh-Kermani et al. A modified process for leaching of ilmenite and production of TiO2 nanoparticles
US10369631B2 (en) Method for recycling waste cemented carbide by molten salt chemistry
US11247270B2 (en) Method for preparing vanadium and vanadium alloy powder from vanadium-containing materials through shortened process
KR101800784B1 (en) Recovery method of tungsten compound from waste hard metal
CN101041466A (en) Method for producing dichromium trioxide and ferrous oxalate by carbon ferro-chrome
KR101581860B1 (en) Method for preparing high-purity ammonium paratungstate using waste super hard metal scrap
Li et al. Combined milling–dissolution of Panzhihua ilmenite in sulfuric acid
Bian et al. Extraction of valuable metals from Ti-bearing blast furnace slag using ammonium sulfate pressurized pyrolysis–acid leaching processes
Wu et al. Synthesis of tungsten carbide nanopowders by direct carbonization of tungsten oxide and carbon: Effects of tungsten oxide source on phase structure and morphology evolution
WO2016024689A1 (en) Method for producing titanium carbonitride powder
Wang et al. Evaluation of a green-sustainable industrialized cleaner production for FeV50 and FeV80 alloys from vanadium slag by calcification roasting–ammonia on-line cycle
Simsek et al. Mechanochemical processing and microstructural characterization of pure Fe2B nanocrystals
CN1332045C (en) Hydrothermal method for recovering metal from waste hard alloy
Liu et al. Mechanochemical decomposition on (rare earth) bastnaesite concentrate in NaOH solution
EP3098199B1 (en) Process for the direct production of tungsten carbide powders of various grain sizes starting from scheelite
Sadeghi et al. Development of a safe and environmentally friendly sulfate process for the production of titanium oxide
Aboody et al. Production of high purity magnetic nickel powder from spent DRI catalyst via cementation method
Zhang et al. Enhancing the leaching performance of molybdenite and Co-white alloy simultaneously: A structure conversion process
CN114057195B (en) Preparation method of superfine tungsten carbide
Ahmadisoltansaraei et al. Preparation of NiO nanoparticles from Ni (OH) 2· NiCO 3· 4H 2 O precursor by mechanical activation
Li et al. Preparation ultrafine WC based on the new tungsten metallurgy system of “no ammonia transformation-no hydrogen reduction”
Wang et al. Decomposition kinetics of titania slag in eutectic naoh-nano 3 system
Yaraghi et al. Microstructural study of leached nitrided Malaysian ilmenite with coal-polystyrene reductant

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20070815

Termination date: 20130322