CN108504863A - A kind of method that the useless hydrogenation catalyst of microwave treatment extracts nickel, aluminium, molybdenum - Google Patents
A kind of method that the useless hydrogenation catalyst of microwave treatment extracts nickel, aluminium, molybdenum Download PDFInfo
- Publication number
- CN108504863A CN108504863A CN201810202762.8A CN201810202762A CN108504863A CN 108504863 A CN108504863 A CN 108504863A CN 201810202762 A CN201810202762 A CN 201810202762A CN 108504863 A CN108504863 A CN 108504863A
- Authority
- CN
- China
- Prior art keywords
- hydrogenation catalyst
- molybdenum
- aluminium
- added
- nickel
- 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.)
- Pending
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 49
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 49
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 44
- 239000011733 molybdenum Substances 0.000 title claims abstract description 44
- 239000004411 aluminium Substances 0.000 title claims abstract description 35
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 35
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000000284 extract Substances 0.000 title description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 67
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 28
- 239000000706 filtrate Substances 0.000 claims abstract description 27
- 238000005516 engineering process Methods 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 18
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 239000000428 dust Substances 0.000 claims abstract description 16
- 239000000047 product Substances 0.000 claims abstract description 16
- 238000000605 extraction Methods 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 239000012047 saturated solution Substances 0.000 claims abstract description 14
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000012670 alkaline solution Substances 0.000 claims abstract description 11
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001556 precipitation Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000002244 precipitate Substances 0.000 claims abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 49
- 239000007787 solid Substances 0.000 claims description 18
- 239000003610 charcoal Substances 0.000 claims description 12
- 238000002386 leaching Methods 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 15
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 238000009825 accumulation Methods 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 229910052594 sapphire Inorganic materials 0.000 description 6
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- -1 hydroxides Sodium hydroxide Chemical class 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 235000013495 cobalt Nutrition 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- XGZRAKBCYZIBKP-UHFFFAOYSA-L disodium;dihydroxide Chemical compound [OH-].[OH-].[Na+].[Na+] XGZRAKBCYZIBKP-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 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
- C22B7/009—General processes for recovering metals or metallic compounds 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting 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
- C22B21/00—Obtaining aluminium
- C22B21/0015—Obtaining aluminium by wet processes
- C22B21/0023—Obtaining aluminium by wet processes from waste materials
- C22B21/003—Obtaining aluminium by wet processes 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0446—Leaching processes with an ammoniacal liquor or with a hydroxide of an alkali or alkaline-earth metal
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/34—Obtaining molybdenum
- C22B34/345—Obtaining molybdenum 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
- 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
- C22B7/006—Wet processes
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
-
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to the methods of a kind of useless hydrogenation catalyst extraction nickel of microwave treatment, aluminium, molybdenum, belong to secondary resource Comprehensive Recovery Technology field.A concentration of 15mol/L sodium hydroxides saturated solution will be added in useless hydrogenation catalyst first and be uniformly mixing to obtain pureed state material；Obtained pureed state material is obtained into clinker in microwave calcining, will be crushed after clinker natural cooling；Clinker after natural cooling is crushed is added in dilute alkaline solution, and 10 ~ 30min is leached under the conditions of temperature is 50 ~ 90 DEG C and obtains leachate and nickeliferous leached mud；Dust technology is added in obtained leachate and adjusts pH value 6.0~7.5, is then separated by filtration to obtain filtrate I and aluminum hydroxide precipitation product；Nitre acid for adjusting pH value 0.9~1.5 is added in obtained filtrate, is then separated by filtration to obtain filtrate II and precipitate molybdic acid product.The advantages that microwave calcining technology is introduced into dead catalyst comprehensive reutilization field by the present invention, has treatment process simple, easy to operate, and the time is short.
Description
Technical field
The present invention relates to the methods of a kind of useless hydrogenation catalyst extraction nickel of microwave treatment, aluminium, molybdenum, belong to secondary resource synthesis
Recovery technology field.
Background technology
For hydrogenation catalyst generally using metals such as molybdenum, nickel, cobalts as active component, these metals are usually with the shape of its oxide
Formula is dispersed on the carriers such as aluminium oxide or the aluminium oxide containing a small amount of auxiliary agent, is widely used in petroleum refining and chemical industry.
During use, activity is gradually lost due to the deposition of the impurity elements such as metal molybdenum and nickel in catalyst, is formd big
The solid refuse of amount.Because having adsorbed poisonous and harmful substance in dead catalyst and having contained a large amount of useful metals, if do not handled back
It receives, then causes environmental pollution and the wasting of resources.From the aspect of comprehensive utilization of resources and environmental protection, it is highly desirable pair plus hydrogen
Dead catalyst is recycled, and not only secondary resource is made to make full use of, and reduces environmental pollution.
The current research for having had some to recycling connection metal in dead catalyst, wherein Chinese patent
CN201410723849.1 discloses a kind of method recycling the hydrogenation catalyst that gives up.Specifically after oil removing, washed through persalt,
It after being passed through chlorine and air reaction under the action of ultrasonic wave, moves into full of heating in nitrogen, makes metal molybdenum, nickel or cobalt, vanadium
Chloride or oxychloride volatilization, separation gas-solid are mutually reprocessed.But this method technique is more complex.Patent
CN200710010894.2 discloses a kind of method from recovering high-purity molybdenum from molybdenum-containing dead catalyst.Specifically by dead catalyst powder
End be added prepare containing ammonium hydroxide, ammonium hydrogen carbonate, hydrogen peroxide alkaline solution in leach, filtered solid powder carries out oxidizing roasting
It is leached in alkaline solution again, nitre acid for adjusting pH value 0.8~1.2 is added in obtained filtrate, molybdic acid is settled out, is separated by filtration
Go out molybdic acid, obtained molybdic acid is dissolved in ammonium hydroxide, is then 2.0~3.0 with nitric acid adjustment pH value, is settled out ammonium molybdate, filtering point
From.But this method technique is not easy to operate, and technique is more complex.Patent CN200310105096.X discloses a kind of from aluminium scrap base
The method that nickel-containing catalyst recycles nickel and aluminium.Specifically dead catalyst powder is mixed with sodium carbonate, dosage is dead catalyst：
Sodium hydroxide（Weight ratio）=1:0.7 ~ 1.3, transition reaction, constant temperature time 1 are carried out in the sintering furnace that temperature is 700 ~ 1250 DEG C
After ~ 6h, aluminium, nickel slag then reducing-matting smelting are detached with boiling water dissolving sodium aluminate.The process economics are of high cost.
Invention content
The problem of existing for the above-mentioned prior art and deficiency, a kind of useless hydrogenation catalyst of microwave treatment of present invention offer carry
The method for taking nickel, aluminium, molybdenum.After useless hydrogenation catalyst sodium hydroxide supersaturated solution is mixed into pureed state by the present invention,
It is put into micro-wave oven and is roasted.Obtained clinker is leached to obtain nickel enrichment slag and leaching in normal pressure, dilute alkaline solution
Liquid.A small amount of dust technology is added in obtained leachate again and obtains aluminum hydroxide solid and rich in the filtrate of molybdenum element.By what is obtained
Filtrate is added appropriate nitric acid and is settled out molybdic acid.This method can strengthen pyroreaction using sodium hydroxide and moisture in microwave field
Characteristic and microwave by the dielectric loss inside dead catalyst directly will chemical reaction needed for energy transmission to reaction point
Son or atom characteristic, using microwave heating technique quickly heat, be evenly heated the advantages that, realize in relatively low microwave calcining temperature
Under degree, the α-Al of the metals such as molybdenum, nickel, cobalt will be wrapped up2O3With γ-Al2O3The alumina support of crystal form reacts generation with sodium hydroxide
Sodium aluminate soluble easily in water, by entering in leachate after leaching, molybdenum and nickel metallic element are also melted in leachate, and nickel is golden
Category state is constant, by entering in leached mud after leaching, realizes the separation of nickel and other metals first；It is added in leachate suitable
The dilute sulfuric acid of amount generates aluminum hydroxide precipitation, is then separated by solid-liquid separation, then realize the separation of aluminium and molybdenum element；The filter that will be obtained again
Suitable nitric acid is added in liquid, is settled out molybdic acid.This method is simple for process needed for extraction nickel, aluminium, molybdenum element；Time is short；
NaOH、HNO3Equal consumption is few；Indissoluble α-Al can be handled2O3Carrier；Nickel, aluminium, molybdenum leaching rate it is high the advantages that.The present invention passes through
Following technical scheme is realized.
A kind of method that the useless hydrogenation catalyst of microwave treatment extracts nickel, aluminium, molybdenum, is as follows：
Step 1, first by useless hydrogenation catalyst according to liquid-solid ratio be 0.29 ~ 0.39：A concentration of 15mol/L hydrogen is added in 1mL/g
Sodium oxide molybdena saturated solution is uniformly mixing to obtain pureed state material；
Step 2, the pureed state material for obtaining step 1 microwave power be 1.5 ~ 3.5kW, microwave calcining temperature be 300 ~
20 ~ 70min of microwave calcining obtains clinker under conditions of 800 DEG C, will be crushed after clinker natural cooling；
Step 3, by step 2 natural cooling crush after clinker according to liquid-solid ratio be 3 ~ 6：1mL/g is added to a concentration of 18 ~ 24g/
In LNaOH dilute alkaline solutions, 10 ~ 30min of leaching obtains leachate and nickeliferous leached mud under the conditions of temperature is 50 ~ 90 DEG C；
Step 4, the leachate for obtaining step 3 are added dust technology and adjust pH value 6.0~7.5, are then separated by filtration to obtain filtrate I
With aluminum hydroxide precipitation product；
Nitre acid for adjusting pH value 0.9~1.5 is added in step 5, the filtrate for obtaining step 4, is then separated by filtration to obtain II He of filtrate
Precipitate molybdic acid product.
The carrier of useless hydrogenation catalyst is aluminium oxide in the step 1, also contains molybdenum and nickel.
It is 0.8 ~ 1.2mm that the hydrogenation catalyst that gives up in the step 1, which prepares the length of side, and length is the square of 4 ~ 7mm.
The hydrogenation catalyst that gives up in the step 1 is taking off charcoal using Muffle furnace first, keeps leading under oxygen condition, is in temperature
1 ~ 3h of charcoal is taken off under the conditions of 600 ~ 700 DEG C.
The step 1, which gives up graininess sodium hydroxide is added in hydrogenation catalyst to be uniformly mixed, obtains mixed material, mixture
Material adds a concentration of 15mol/L sodium hydroxides saturated solution, wherein graininess sodium hydroxide and a concentration of 15mol/L hydroxides
Sodium hydroxide gross mass and useless hydrogenation catalyst quality are 1 in sodium saturated solution：1.1~3.
A concentration of 5 ~ 7.7mol/L of dust technology in the step 4.
Nitric acid is to analyze pure nitric acid in above-mentioned steps 5.
The beneficial effects of the invention are as follows：
（1）Microwave calcining technology is introduced into dead catalyst comprehensive reutilization field by the present invention, has treatment process simple, behaviour
Facilitate, the advantages that time is short.
（2）The present invention makes full use of secondary resource from useless hydrogenation catalyst comprehensive recovery nickel, aluminium, molybdenum.
（3）The present invention can handle indissoluble α-Al2O3The alumina support of crystal form.
（4）The NaOH consumptions of the present invention are few, and give up hydrogenation catalyst：Sodium hydroxide（Weight ratio）It is 1.1 ~ 3：1.
（5）The accumulation rate of nickel is high in slag of the present invention>97%.
（6）The rate of recovery of aluminium of the present invention>95%.
（7）The rate of recovery of molybdenum of the present invention>96%.
Description of the drawings
Fig. 1 is present invention process flow chart；
Fig. 2 is the clinker XRD diagram that the embodiment of the present invention 1 is prepared.
Specific implementation mode
With reference to the accompanying drawings and detailed description, the invention will be further described.
Embodiment 1
As shown in Figure 1, the microwave treatment is given up, the method for hydrogenation catalyst extraction nickel, aluminium, molybdenum, is as follows：
Step 1 first gives up 50g hydrogenation catalysts（The carrier of useless hydrogenation catalyst is aluminium oxide, also contains molybdenum and nickel, oxidation
Alumina supporter includes α-Al2O3With γ-Al2O3The aluminium oxide of crystal form, nickel content 1.72wt%, molybdenum content 5.96wt%, aluminium content
For 74.35wt%, C content is higher；The preparation length of side is 0.8mm, and length is the square of 4mm, does not take off charcoal）According to liquid-solid ratio be
0.29：1mL/g is added a concentration of 15mol/L sodium hydroxides saturated solution and is uniformly mixing to obtain pureed state material；
Step 2, by pureed state material that step 1 obtains in the item that microwave power is 1.5kW, microwave calcining temperature is 800 DEG C
Microwave calcining 50min obtains clinker under part, and it is 100 mesh that granularity will be crushed to after clinker natural cooling；Clinker XRD diagram such as Fig. 2 institutes
Show, as can be seen from Figure 2 Al exists by sodium aluminate, Mo by sodium molybdate, Ni in the form of NiO in clinker；
Step 3, by step 2 natural cooling crush after 20g clinkers according to liquid-solid ratio be 6：1mL/g is added to a concentration of 18g/
In LNaOH dilute alkaline solutions, leaching 10min obtains leachate and nickeliferous leached mud under the conditions of temperature is 85 DEG C；
Dust technology is added in step 4, the leachate for obtaining step 3（A concentration of 7mol/L of dust technology）PH value 7.0 is adjusted, then mistake
Filter isolated filtrate I and aluminum hydroxide precipitation product；
Nitre acid for adjusting pH value 1.0 is added in step 5, the filtrate for obtaining step 4, is then separated by filtration to obtain filtrate II and molybdic acid is heavy
Shallow lake product.
The accumulation rate of nickel is 98.2% in leached mud in the present embodiment, and the rate of recovery of aluminium is 96.2%, and the rate of recovery of molybdenum is
97.7%。
Embodiment 2
As shown in Figure 1, the microwave treatment is given up, the method for hydrogenation catalyst extraction nickel, aluminium, molybdenum, is as follows：
Step 1 first gives up 50g hydrogenation catalysts（The carrier of useless hydrogenation catalyst is aluminium oxide, also contains molybdenum and nickel, oxidation
Alumina supporter includes α-Al2O3With γ-Al2O3The aluminium oxide of crystal form, nickel content 1.72wt%, molybdenum content 5.96wt%, aluminium content
For 74.35wt%, C content is higher；The preparation length of side is 1.2mm, and length is the square of 7mm, does not take off charcoal）With graininess hydroxide
Sodium, which is uniformly mixed, obtains mixed material, and mixed material is 0.39 according to liquid-solid ratio：A concentration of 15mol/L hydroxides are added in 1mL/g
Sodium saturated solution is uniformly mixing to obtain pureed state material, wherein graininess sodium hydroxide and a concentration of 15mol/L sodium hydroxides
Sodium hydroxide gross mass and useless hydrogenation catalyst quality are 1 in saturated solution：1.19；
Step 2, by pureed state material that step 1 obtains in the item that microwave power is 3.5kW, microwave calcining temperature is 300 DEG C
Microwave calcining 70min obtains clinker under part, and it is 100 mesh that granularity will be crushed to after clinker natural cooling；
Step 3, by step 2 natural cooling crush after 20g clinkers according to liquid-solid ratio be 6：1mL/g is added to a concentration of 18g/
In LNaOH dilute alkaline solutions, leaching 10min obtains leachate and nickeliferous leached mud under the conditions of temperature is 85 DEG C；
Dust technology is added in step 4, the leachate for obtaining step 3（A concentration of 5mol/L of dust technology）PH value 7.5 is adjusted, then mistake
Filter isolated filtrate I and aluminum hydroxide precipitation product；
Nitre acid for adjusting pH value 1.5 is added in step 5, the filtrate for obtaining step 4, is then separated by filtration to obtain filtrate II and molybdic acid is heavy
Shallow lake product.
The accumulation rate of nickel is 97.4% in leached mud in the present embodiment, and the rate of recovery of aluminium is 95.2%, and the rate of recovery of molybdenum is
96.4%。
Embodiment 3
As shown in Figure 1, the microwave treatment is given up, the method for hydrogenation catalyst extraction nickel, aluminium, molybdenum, is as follows：
Step 1 first gives up 50g hydrogenation catalysts（The carrier of useless hydrogenation catalyst is aluminium oxide, also contains molybdenum and nickel, oxidation
Alumina supporter includes α-Al2O3With γ-Al2O3The aluminium oxide of crystal form, nickel content 1.72wt%, molybdenum content 5.96wt%, aluminium content
For 74.35wt%, C content is higher；The preparation length of side is 1.0mm, and length is the square of 6mm, is taking off charcoal using Muffle furnace first,
It keeps under the logical oxygen condition that oxygen flow is 800ml/min, de- charcoal 1h under the conditions of temperature is 600 DEG C）With graininess hydroxide
Sodium, which is uniformly mixed, obtains mixed material, and mixed material is 0.3 according to liquid-solid ratio：A concentration of 15mol/L sodium hydroxides are added in 1mL/g
Saturated solution is uniformly mixing to obtain pureed state material, and wherein graininess sodium hydroxide and a concentration of 15mol/L sodium hydroxides is full
It is 1 with sodium hydroxide gross mass in solution and useless hydrogenation catalyst quality：2；
Step 2, by pureed state material that step 1 obtains in the item that microwave power is 2.5kW, microwave calcining temperature is 600 DEG C
Microwave calcining 20min obtains clinker under part, and it is 100 mesh that granularity will be crushed to after clinker natural cooling；
Step 3, by step 2 natural cooling crush after 20g clinkers according to liquid-solid ratio be 3：1mL/g is added to a concentration of 20g/
In LNaOH dilute alkaline solutions, leaching 30min obtains leachate and nickeliferous leached mud under the conditions of temperature is 50 DEG C；
Dust technology is added in step 4, the leachate for obtaining step 3（A concentration of 6mol/L of dust technology）PH value 6.0 is adjusted, then mistake
Filter isolated filtrate I and aluminum hydroxide precipitation product；
Nitre acid for adjusting pH value 0.9 is added in step 5, the filtrate for obtaining step 4, is then separated by filtration to obtain filtrate II and molybdic acid is heavy
Shallow lake product.
The accumulation rate of nickel is 97.6% in leached mud in the present embodiment, and the rate of recovery of aluminium is 95.6%, and the rate of recovery of molybdenum is
96.7%。
Embodiment 4
As shown in Figure 1, the microwave treatment is given up, the method for hydrogenation catalyst extraction nickel, aluminium, molybdenum, is as follows：
Step 1 first gives up 50g hydrogenation catalysts（The carrier of useless hydrogenation catalyst is aluminium oxide, also contains molybdenum and nickel, oxidation
Alumina supporter includes α-Al2O3With γ-Al2O3The aluminium oxide of crystal form, nickel content 1.72wt%, molybdenum content 5.96wt%, aluminium content
For 74.35wt%, C content is higher；The preparation length of side is 1.0mm, and length is the square of 6mm, is taking off charcoal using Muffle furnace first,
It keeps under the logical oxygen condition that oxygen flow is 1000ml/min, de- charcoal 3h under the conditions of temperature is 700 DEG C）With graininess hydroxide
Sodium, which is uniformly mixed, obtains mixed material, and mixed material is 0.33 according to liquid-solid ratio：A concentration of 15mol/L hydroxides are added in 1mL/g
Sodium saturated solution is uniformly mixing to obtain pureed state material, wherein graininess sodium hydroxide and a concentration of 15mol/L sodium hydroxides
Sodium hydroxide gross mass and useless hydrogenation catalyst quality are 1 in saturated solution：3；
Step 2, by pureed state material that step 1 obtains in the condition that microwave power is 3kW, microwave calcining temperature is 500 DEG C
Lower microwave calcining 40min obtains clinker, and it is 100 mesh that granularity will be crushed to after clinker natural cooling；
Step 3, by step 2 natural cooling crush after 20g clinkers according to liquid-solid ratio be 4：1mL/g is added to a concentration of 22g/
In LNaOH dilute alkaline solutions, leaching 20min obtains leachate and nickeliferous leached mud under the conditions of temperature is 90 DEG C；
Dust technology is added in step 4, the leachate for obtaining step 3（A concentration of 5mol/L of dust technology）PH value 7.5 is adjusted, then mistake
Filter isolated filtrate I and aluminum hydroxide precipitation product；
Nitre acid for adjusting pH value 1.2 is added in step 5, the filtrate for obtaining step 4, is then separated by filtration to obtain filtrate II and molybdic acid is heavy
Shallow lake product.
The accumulation rate of nickel is 97.7% in leached mud in the present embodiment, and the rate of recovery of aluminium is 96.0%, and the rate of recovery of molybdenum is
96.8%。
Embodiment 5
As shown in Figure 1, the microwave treatment is given up, the method for hydrogenation catalyst extraction nickel, aluminium, molybdenum, is as follows：
Step 1 first gives up 50g hydrogenation catalysts（The carrier of useless hydrogenation catalyst is aluminium oxide, also contains molybdenum and nickel, oxidation
Alumina supporter includes α-Al2O3With γ-Al2O3The aluminium oxide of crystal form, nickel content 1.72wt%, molybdenum content 5.96wt%, aluminium content
For 74.35wt%, C content is higher；The preparation length of side is 0.9mm, and length is the square of 5mm, is taking off charcoal using Muffle furnace first,
It keeps under the logical oxygen condition that oxygen flow is 1200ml/min, de- charcoal 2h under the conditions of temperature is 650 DEG C）With graininess hydroxide
Sodium, which is uniformly mixed, obtains mixed material, and mixed material is 0.35 according to liquid-solid ratio：A concentration of 15mol/L hydroxides are added in 1mL/g
Sodium saturated solution is uniformly mixing to obtain pureed state material, wherein graininess sodium hydroxide and a concentration of 15mol/L sodium hydroxides
Sodium hydroxide gross mass and useless hydrogenation catalyst quality are 1 in saturated solution：2；
Step 2, by pureed state material that step 1 obtains in the item that microwave power is 2.0kW, microwave calcining temperature is 600 DEG C
Microwave calcining 50min obtains clinker under part, and it is 100 mesh that granularity will be crushed to after clinker natural cooling；
Step 3, by step 2 natural cooling crush after 20g clinkers according to liquid-solid ratio be 5：1mL/g is added to a concentration of 24g/
In LNaOH dilute alkaline solutions, leaching 30min obtains leachate and nickeliferous leached mud under the conditions of temperature is 70 DEG C；
Dust technology is added in step 4, the leachate for obtaining step 3（A concentration of 7.7mol/L of dust technology）PH value 6.8 is adjusted, then
It is separated by filtration to obtain filtrate I and aluminum hydroxide precipitation product；
Nitre acid for adjusting pH value 1.4 is added in step 5, the filtrate for obtaining step 4, is then separated by filtration to obtain filtrate II and molybdic acid is heavy
Shallow lake product.
The accumulation rate of nickel is 98.5% in leached mud in the present embodiment, and the rate of recovery of aluminium is 97.3%, and the rate of recovery of molybdenum is
97.6%。
The specific implementation mode of the present invention is explained in detail above in association with attached drawing, but the present invention is not limited to above-mentioned
Embodiment within the knowledge of a person skilled in the art can also be before not departing from present inventive concept
Put that various changes can be made.
Claims (6)
- A kind of method of hydrogenation catalyst extraction nickel, aluminium, molybdenum 1. microwave treatment is given up, it is characterised in that be as follows：Step 1, first by useless hydrogenation catalyst according to liquid-solid ratio be 0.29 ~ 0.39：A concentration of 15mol/L hydrogen is added in 1mL/g Sodium oxide molybdena saturated solution is uniformly mixing to obtain pureed state material；Step 2, the pureed state material for obtaining step 1 microwave power be 1.5 ~ 3.5kW, microwave calcining temperature be 300 ~ 20 ~ 70min of microwave calcining obtains clinker under conditions of 800 DEG C, will be crushed after clinker natural cooling；Step 3, by step 2 natural cooling crush after clinker according to liquid-solid ratio be 3 ~ 6：1mL/g is added to a concentration of 18 ~ 24g/ In LNaOH dilute alkaline solutions, 10 ~ 30min of leaching obtains leachate and nickeliferous leached mud under the conditions of temperature is 50 ~ 90 DEG C；Step 4, the leachate for obtaining step 3 are added dust technology and adjust pH value 6.0~7.5, are then separated by filtration to obtain filtrate I With aluminum hydroxide precipitation product；Nitre acid for adjusting pH value 0.9~1.5 is added in step 5, the filtrate for obtaining step 4, is then separated by filtration to obtain II He of filtrate Precipitate molybdic acid product.
- The method of hydrogenation catalyst extraction nickel, aluminium, molybdenum 2. microwave treatment according to claim 1 is given up, it is characterised in that：Institute The carrier for stating the hydrogenation catalyst that gives up in step 1 is aluminium oxide, also contains molybdenum and nickel.
- The method of hydrogenation catalyst extraction nickel, aluminium, molybdenum 3. microwave treatment according to claim 1 is given up, it is characterised in that：Institute It is 0.8 ~ 1.2mm to state the hydrogenation catalyst that gives up in step 1 and prepare the length of side, and length is the square of 4 ~ 7mm.
- The method of hydrogenation catalyst extraction nickel, aluminium, molybdenum 4. microwave treatment according to claim 1 is given up, it is characterised in that：Institute It states the hydrogenation catalyst that gives up in step 1 and is taking off charcoal using Muffle furnace first, keep leading under oxygen condition, be 600 ~ 700 DEG C of items in temperature 1 ~ 3h of charcoal is taken off under part.
- 5. microwave treatment according to claim 1 or 4 is given up, the method for hydrogenation catalyst extraction nickel, aluminium, molybdenum, feature exist In：The step 1, which gives up graininess sodium hydroxide is added in hydrogenation catalyst to be uniformly mixed, obtains mixed material, and mixed material adds again Enter a concentration of 15mol/L sodium hydroxides saturated solution, wherein graininess sodium hydroxide and a concentration of 15mol/L sodium hydroxides saturation Sodium hydroxide gross mass and useless hydrogenation catalyst quality are 1 in solution：1.1~3.
- The method of hydrogenation catalyst extraction nickel, aluminium, molybdenum 6. microwave treatment according to claim 1 is given up, it is characterised in that：Institute State a concentration of 5 ~ 7.7mol/L of dust technology in step 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810202762.8A CN108504863A (en) | 2018-03-13 | 2018-03-13 | A kind of method that the useless hydrogenation catalyst of microwave treatment extracts nickel, aluminium, molybdenum |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810202762.8A CN108504863A (en) | 2018-03-13 | 2018-03-13 | A kind of method that the useless hydrogenation catalyst of microwave treatment extracts nickel, aluminium, molybdenum |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108504863A true CN108504863A (en) | 2018-09-07 |
Family
ID=63377370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810202762.8A Pending CN108504863A (en) | 2018-03-13 | 2018-03-13 | A kind of method that the useless hydrogenation catalyst of microwave treatment extracts nickel, aluminium, molybdenum |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108504863A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111821995A (en) * | 2019-04-19 | 2020-10-27 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| CN113789446A (en) * | 2021-08-23 | 2021-12-14 | 常州大学 | Method for recovering molybdenum, vanadium and nickel metals from waste catalyst |
| CN113976136A (en) * | 2020-07-27 | 2022-01-28 | 中国石油化工股份有限公司 | Preparation method of hydrodemetallization catalyst |
| CN118086679A (en) * | 2024-03-29 | 2024-05-28 | 广东省科学院资源利用与稀土开发研究所 | Method for recovering vanadium from waste nickel aluminum powder for catalyst |
| CN118207420A (en) * | 2024-03-29 | 2024-06-18 | 广东省科学院资源利用与稀土开发研究所 | Method for separating nickel and aluminum by treating nickel and aluminum waste |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50102595A (en) * | 1974-01-16 | 1975-08-13 | ||
| CN102212694A (en) * | 2011-04-21 | 2011-10-12 | 江苏科创石化有限公司 | Method for extracting valuable metal from waste hydrogenation catalyst |
| CN102925690A (en) * | 2011-08-11 | 2013-02-13 | 荆门市格林美新材料有限公司 | Method for recovering valuable metals from waste and old Raney nickel catalyst |
| CN103074494A (en) * | 2011-10-25 | 2013-05-01 | 荆门市格林美新材料有限公司 | Method of recovering molybdenum and cobalt from waste cobalt-molybdenum catalyst |
| CN105253906A (en) * | 2015-10-27 | 2016-01-20 | 昆明理工大学 | Method for performing microwave treatment on middle-low-grade diaspore |
-
2018
- 2018-03-13 CN CN201810202762.8A patent/CN108504863A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50102595A (en) * | 1974-01-16 | 1975-08-13 | ||
| CN102212694A (en) * | 2011-04-21 | 2011-10-12 | 江苏科创石化有限公司 | Method for extracting valuable metal from waste hydrogenation catalyst |
| CN102925690A (en) * | 2011-08-11 | 2013-02-13 | 荆门市格林美新材料有限公司 | Method for recovering valuable metals from waste and old Raney nickel catalyst |
| CN103074494A (en) * | 2011-10-25 | 2013-05-01 | 荆门市格林美新材料有限公司 | Method of recovering molybdenum and cobalt from waste cobalt-molybdenum catalyst |
| CN105253906A (en) * | 2015-10-27 | 2016-01-20 | 昆明理工大学 | Method for performing microwave treatment on middle-low-grade diaspore |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111821995A (en) * | 2019-04-19 | 2020-10-27 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| CN113976136A (en) * | 2020-07-27 | 2022-01-28 | 中国石油化工股份有限公司 | Preparation method of hydrodemetallization catalyst |
| CN113976136B (en) * | 2020-07-27 | 2023-10-10 | 中国石油化工股份有限公司 | Preparation method of hydrodemetallization catalyst |
| CN113789446A (en) * | 2021-08-23 | 2021-12-14 | 常州大学 | Method for recovering molybdenum, vanadium and nickel metals from waste catalyst |
| CN118086679A (en) * | 2024-03-29 | 2024-05-28 | 广东省科学院资源利用与稀土开发研究所 | Method for recovering vanadium from waste nickel aluminum powder for catalyst |
| CN118207420A (en) * | 2024-03-29 | 2024-06-18 | 广东省科学院资源利用与稀土开发研究所 | Method for separating nickel and aluminum by treating nickel and aluminum waste |
| CN118207420B (en) * | 2024-03-29 | 2024-11-08 | 广东省科学院资源利用与稀土开发研究所 | Method for separating nickel and aluminum by treating nickel and aluminum waste |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108504863A (en) | A kind of method that the useless hydrogenation catalyst of microwave treatment extracts nickel, aluminium, molybdenum | |
| CN108486376A (en) | A method of leaching metal in waste lithium ion cell anode material | |
| CN104498718A (en) | Method for treating hard alloy grinding material | |
| CN104118911B (en) | A kind of method reclaiming tungstic oxide in discarded SCR catalyst completely | |
| CN109837393A (en) | A kind of selective recovery is given up the method for valuable metal in hydrogenation catalyst | |
| CN109148995A (en) | A kind of high manganese waste material of low cobalt and waste lithium cell positive electrode are jointly processed by method | |
| CN108439473A (en) | A kind of method that tungstenic scrap hard alloy prepares nanometer tungsten oxide | |
| CN112646977A (en) | Method for recovering vanadium, molybdenum, nickel and aluminum from petroleum refining waste catalyst | |
| CN113832349B (en) | Method for recycling lithium, nickel, cobalt and manganese from battery waste | |
| CN104946903A (en) | Method for recovering metal resource from zinc calcine through reduction roasting-leaching-zinc sinking | |
| CN106480320A (en) | A kind of method for reclaiming valuable metal from discarded SCR denitration | |
| CN108588403A (en) | One kind is from indissoluble α-Al2O3The method that platinum is recycled in base platinum-containing waste catalyst | |
| CN102011008A (en) | Method for preparing high-purity copper oxide superfine powder from waste printed circuit boards | |
| CN109706312A (en) | A method of vanadic anhydride and chemical electrode manganese dioxide are prepared simultaneously using vanadium chromium slag and low-grade pyrolusite | |
| CN106745134B (en) | A kind of method of sapphire diamond wire cutting waste material recycling | |
| CN106086417A (en) | A kind of method extracting copper and gold from waste mobile phone circuit board | |
| CN106673064A (en) | Method for producing ammonium paratungstate | |
| CN109593965A (en) | A method of recycling valuable element from aluminium base petroleum refining dead catalyst | |
| CN111534699A (en) | Method for recovering valuable substances from cemented carbide scrap | |
| CN115744991B (en) | Method for preparing tungsten oxide from tungsten-containing waste | |
| CN111392756A (en) | Process for extracting high-purity rare earth oxide from fluorescent powder waste | |
| WO2023029572A1 (en) | Preparation method for aluminum nitride | |
| CN111485122B (en) | Method for recycling niobium from waste NbTaZr alloy | |
| CN113215404B (en) | Method for preparing spherical cobaltosic oxide from cobalt-ammonia complex solution | |
| CN105755288B (en) | A kind of method that zinc in discarded cathodic ray-tube fluorescent powder is reclaimed based on self-propagating reaction and rare earth is enriched with |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180907 |