CN102154553B - Method for removing iron and aluminum from iron-based waste containing high-value elements through natural oxidation - Google Patents
Method for removing iron and aluminum from iron-based waste containing high-value elements through natural oxidation Download PDFInfo
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- CN102154553B CN102154553B CN201110046685XA CN201110046685A CN102154553B CN 102154553 B CN102154553 B CN 102154553B CN 201110046685X A CN201110046685X A CN 201110046685XA CN 201110046685 A CN201110046685 A CN 201110046685A CN 102154553 B CN102154553 B CN 102154553B
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- based waste
- acid
- natural oxidation
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 64
- 239000002699 waste material Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 42
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 27
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 230000003647 oxidation Effects 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 40
- 239000002253 acid Substances 0.000 claims abstract description 32
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims description 25
- 229910017052 cobalt Inorganic materials 0.000 claims description 21
- 239000010941 cobalt Substances 0.000 claims description 21
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 239000004411 aluminium Substances 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 17
- 150000002910 rare earth metals Chemical class 0.000 claims description 17
- 229910045601 alloy Inorganic materials 0.000 claims description 16
- 239000000956 alloy Substances 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 230000003020 moisturizing effect Effects 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 4
- 150000002978 peroxides Chemical class 0.000 claims description 4
- 241000408747 Lepomis gibbosus Species 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000002893 slag Substances 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052728 basic metal Inorganic materials 0.000 claims description 2
- 150000003818 basic metals Chemical class 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 239000011133 lead Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000003487 electrochemical reaction Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 abstract 2
- 239000003792 electrolyte Substances 0.000 abstract 1
- 238000004134 energy conservation Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 235000013495 cobalt Nutrition 0.000 description 21
- 239000000047 product Substances 0.000 description 14
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000000605 extraction Methods 0.000 description 5
- 229910001172 neodymium magnet Inorganic materials 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- YZHUMGUJCQRKBT-UHFFFAOYSA-M sodium chlorate Chemical compound [Na+].[O-]Cl(=O)=O YZHUMGUJCQRKBT-UHFFFAOYSA-M 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 229910016287 MxOy Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- -1 iron ion Chemical class 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- IWPMRMIANLLTTJ-UHFFFAOYSA-N cobalt(2+);sulfane Chemical compound S.[Co+2] IWPMRMIANLLTTJ-UHFFFAOYSA-N 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 201000004792 malaria Diseases 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000009868 nickel metallurgy Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet 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
- C22B59/00—Obtaining rare earth metals
-
- 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
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to a method for removing iron and aluminum from iron-based waste containing high-value elements through natural oxidation. The method is characterized in that iron-based waste is crushed and then mixed with water and a small amount of acid, so that the iron-based waste is in a humid electrolyte atmosphere in the air, and a series of complex oxidation reactions and electrochemical reactions occur, and elemental iron or ferrous iron and elemental aluminum are converted into + 3-valent oxide or hydroxide; and then the material oxidized by the air is subjected to the working procedures of acid dissolution, impurity removal, filtration and the like to obtain a solution which is removed with iron and aluminum and contains high-value elements, and the solution is further purified and separated to obtain a corresponding product of the high-value elements. The method has the advantages of short flow, simple equipment, energy conservation, small using amount of chemical raw materials, high dissolution rate of high-value elements, mild reaction conditions, environmental friendliness and the like.
Description
Technical field
The present invention relates to a kind of method that contains high value element iron-based waste material natural oxidation deironing aluminium, specifically belong to resource circulation utilization and technical field of wet metallurgy.
Background technology
In order to make more excellent more unique iron-based construction material and functional materials, general method is in iron, to add alloy element or alloying alloy.Along with the mass production of iron be widely used, caused the iron-based amount of waste material to grow with each passing day inevitably.And in these iron-based waste materials, contain high value scarce resources such as a considerable amount of rare earths, cobalt, nickel, copper.So, from contain high value element iron-based waste material (hereinafter to be referred as waste material or iron-based waste material), reclaim and extract the high value element, realize resource circulation utilization, be the problem that the insider tries to explore to study always, and disclose or delivered many methods.These methods can roughly reduce two big types: direct smelting process and hydrometallurgical extraction method.
The hydrometallurgical extraction method utilizes chemical means to destroy the ferrous alloy state exactly, removes low value element (like iron, aluminium etc.), and the high value element is separated the process that purification obtains corresponding product.The most key step is exactly how to realize the low value element in these class methods, and especially main body low value elemental iron and high value element separates.Because this step is related to the good and bad, high and low of many aspects such as yield, quality product, production cost and efficient, the environmental pollution of high value element.The existing method that just contains high value element iron-based waste material deironing extraction is below summarized as follows:
The one, dissolve method entirely: all dissolve the iron-based waste material with acid and oxygenant; Adopt separating of the realization of one of following method and ferro element then: 1. directly add and have optionally that precipitation agent makes the high value element form throw out, thereby realize itself and the separating of a large amount of ferro elements; 2. make ferro element form throw out, realize and the separating of high value element, as ferro element all being oxidized to+3 valency ions and add alkaline matter and form ferric hydroxide precipitate, or add alkaline metal salt make+3 valency iron produce siderotil salt deposition etc.; 3. make ferro element maintenance+divalent attitude, adopt extraction agent the high value elements by extraction in organic phase.These methods exist following one or more defectives: A, acid consumption big at least, and cost is high; The waste water that contains iron ion and spent acid that B, a large amount of needs of formation are handled; C, environmental pollution are serious; D, can not realize separating of high value element and ferro element fully, promptly high value element yield is low; E, ferrous ion be prone to oxidation by air and be extracted continue mixed mutually or the like with the high value element.
The 2nd, high-temperature oxidation: this is the method that generally adopts in the present industry, and this method makes ferrous alloy fully oxidation at high temperature alloy change into oxide compound, these materials is carried out operations such as acid is dissolved, removal of impurities, purification again and obtains high value element product.These class methods can be dissolved condition with the preferential stripping of high value element through control acid, and red stone lacks stripping as much as possible, thereby have practiced thrift sour consumption, have reduced some costs, and a large amount of ferro elements becomes sub product with the form of scum and sells.This has obviously had significant improvement than the full method of dissolving.But because after the iron-based waste material process high-temperature heating treatment, it is more difficult that the stripping of high value element also becomes, and reach the ideal yield, the high a lot of acid of necessary its theoretical amount of consumption rate; And some high value element such as cobalt, nickel etc. are stripping simultaneously almost, need at high temperature add again reductive agent it is changed into behind cobalt, the nickel matte could stripping; The abundant iron oxide based waste material complex equipments of high temperature needs to consume significant amount of energy and power in addition, causes production cost to increase.
The 3rd, bubbling air oxidation style: ZL97109971.5 " reclaims the method for useful element from the alloy that contains rare-earth-iron " and discloses a kind of method that from the alloy that contains rare-earth-iron, reclaims useful element: levigate to median size 5-50 μ m (providing maximum median size among the embodiment is 20 μ m) the rare-earth-iron alloy that contains cobalt; The furnishing slip; The limit adds rare nitric acid; The limit bubbling air, keeping pH is more than 5, controlled temperature is below 50 ℃; Need not consume too many nitric acid and just can make the dissolving of rare earth and cobalt become nitrate soln, ferro element then is filtered with the form of ironic hydroxide and removes.The defective of this method is: the one, and reaction needed is used nitric acid, and not only cost is higher, and has generation toxic gas NO and NO
2Danger; The 2nd, the reaction times is very long, stirs, ventilates, drips nitric acid, control pH and temperature, and not only power and manpower consumption are big, and the control difficulty is also not little, is unfavorable for large-scale production.
ZL03811515.8 " from the method for rare earth class transition metal alloy waste recovery useful element " discloses a kind of method from rare earth class-transition metal alloy waste recovery useful element: rare earth class-transition metal alloy waste material is immersed in the ammonium salt aqueous solution of mineral acid; Keep 40 ℃ to 90 ℃; Feeding contains the gas of aerobic; Need not consume too many mineral acid just can make waste material change into oxide compound or oxyhydroxide; Control certain condition again,, filter the solution of the rare earth, cobalt etc. of the ferro element that just can be removed with high value elements such as the preferential stripping rare earth of acid, cobalts.There is long reaction time equally in this method, and stirring, ventilation, temperature keep, and consume a large amount of power, manpower and energy, and production cost is higher; Also need consume the ammonium salt of mineral acid in addition.
Summary of the invention
The objective of the invention is to overcome the defective of above-mentioned existing method, adopt the method for air natural oxidation to change into oxide compound or oxyhydroxide to the iron-based waste material, simple to realize, efficient, reduce cost, purpose such as environmental friendliness.
Main technical schemes of the present invention may further comprise the steps:
(1) powder process:, make the iron-based waste material become granularity and be-40 purpose powders through milling methods such as machinery or air-flow or suction hydrogen.Reach-40 orders like the waste material granularity, then directly carry out step (2) without step (1).
(2) start reaction: levigated powder and water according to the weight ratio water: waste material=0.5～1.5: 1 ratio mixes in reactor, adds sour by waste material weight with 0.4～1molH+/Kg again and stirs.
(3) air natural oxidation: the material stand that step (2) is made is placed in the acidproof kiver or on the clean non-leakage acid-resistant floor;, material stirs when being leather hard for several times; And the sprinkling moisturizing makes material remain humidity; Make iron, ferrous and high value element changed into corresponding salt and/or oxyhydroxide and/or oxide compound under field conditions (factors), account for below total iron 20wt% until ferrous by the air natural oxidation.
(4) sour dissolved oxygen hydrolysis: stir the material that washings that a following water and/or step (7) obtain and step (3) obtain and drop in the reactor; And be warming up to 70～90 ℃; Gradation adds acid and oxygenant, no longer rises to more than 3 to pH, adjusts reaction end pH≤2 then; Continued insulated and stirred 0.5 to 1 hour, and the no ferrous ion of check.
(5) deironing aluminium: the material insulated and stirred step (4), slowly add alkaline matter, make pH=3.5～4.0, and continue to stir 20 to 40 minutes.
(6) filter: the material filtering of step (5) filtrating of containing the high value element of iron aluminium element that promptly has been removed, this filtrating is further separated purification can obtain corresponding high value element product.
(7) washing: filter residue and water that step (6) is obtained are warming up to 70～90 ℃ of agitator treatings and filtration, and filtrating is returned step (4) and used, and filter residue is a sub product.
The above " iron-based waste material " is to be main element with iron, adds one or more high value elements at least, like elements such as rare earth, cobalt, nickel, titanium, chromium, lead, bismuth, copper, manganese, zinc, the material of formed alloy state or ferrous state.
Preferred 40～100 orders of the above iron-based waste material granularity.
The above " acid " is hydrochloric acid or sulfuric acid.
The above " alkali " is the oxyhydroxide or the oxide compound of ammoniacal liquor and/or basic metal and/or earth alkali metal.
The above " oxygenant " is: oxymuriate or hypochlorite or ydrogen peroxide 50, and it can become the reaction of+3 valency iron to calculate according to remaining ferrous oxidation in the resulting material of step (3) with reference to consumption, but final consumption must guarantee that remnants are ferrous oxidized fully.
Following chemical reaction and electrochemical reaction take place in starting reaction and air natural oxidation step:
Following chemical reaction directly takes place with acid in the iron-based waste material that at first is metallic state or iron protoxide state:
2M+2nH
+=2M
N++ nH
2↑ (M is iron aluminium and high value element etc., and n is a natural number, down together) (a)
MxOy+H
+→ Mn
++ H
2O (x, y are natural number, down together) (b)
Secondly, because the subacidity that adds, the pH value rises to more than 3 very soon, and in malaria, following chemical reaction takes place ferrous ion etc. easily:
4Fe
2++O
2+10H
2O＝4Fe(OH)
3+8H
+?(c)
M
n++n?H
2O＝M(OH)n+2n?H
+ (d)
M(OH)n→MxOy·mH
2O (e)
And (c) hydrogen ion that produces of formula and (d) formula react immediately (a) with (b), the visible supplemental acid that midway need not, reaction (a) and (b) and (c) He (d) just carrying out naturally circularly, and part oxyhydroxide (e) formula will take place will react.
In addition, also be accompanied by the generation of following electrochemical reaction at least:
Negative pole M-ne=M
N+(f)
Fe
2+-e＝Fe
3+ (g)
Anodal 2H
++ 2e=H
2↑ (h)
O
2+2H
2O+4e＝4OH?(i)
Step (4) can need consume sour composition according to high value element in the resulting material of step (3) with sour reference consumption and calculate; High value element soluble salt and a large amount of ferro element be consumption acids no longer.Unoxidized ferrous iron material such as iron protoxide or ferrous hydroxide dissolve and the acid meeting that consumes during with oxidant reaction such as obtains at stoichiometric replenishing in the hydrolysis reaction that+3 valency iron ions are followed in acid, and available reaction formula is represented as follows (oxygenant is example with VAL-DROP):
FeO+2H
+＝Fe
2++H
2O (j)
6Fe
2++6H
++ClO
3 -＝6Fe
3++Cl
-+3H
2O (k)
Fe
3++3H
2O＝Fe(OH)
3↓+3H
+ (l)
Arrangement merges (j), (k), (l) formula, can be able to following formula (m)
6FeO+9H
2O+ClO
3 -＝6Fe(OH)
3↓+Cl
- (m)
In sum, the present invention has following significant advantage: 1. flow process and equipment are extremely simple, are fit to suitability for industrialized production; 2. practice thrift the consumption of power, manpower, energy and chemical feedstocks in a large number, reduce production costs; 3. the high value element leaching rate is apparently higher than high-temperature oxidation; 4. reaction conditions is gentle, and a large amount of ferro elements changes into red stone or ironic hydroxide sub product, and is very friendly to environment.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Embodiment
What below introduce is the practical implementation example as foregoing of the present invention; What need special instruction is that following examples are only unrestricted in order to technical scheme of the present invention to be described, although with reference to preferred embodiment the present invention is specified; Those of ordinary skill in the art is to be understood that; Can make amendment or be equal to replacement technical scheme of the present invention, and not break away from the aim and the scope of technical scheme of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Embodiment one
Referring to Fig. 1.
The Nd-Fe-B alloys waste material body refuse of getting 2000Kg process wet ball-milling to-40 orders (0.425mm) is (through detecting wherein REO 19.84wt%, Co 0.60wt%, Fe 56.5wt%, Al
2O
3L.46wt%, moisture content 22.1%, surplus are other material); Drop in the reactor with 1900L water and 10N hydrochloric acid 60L and to mix reaction, afterwards material in the pot is paved in clean non-leakage acidproof shallow hole, stir for several times; And sprinkling moisturizing; Make material keep half-dried dampness, be reduced to 5.3wt%, and recording solubility REO, to account for total REO percentage ratio be 8.2wt% until the ferrous percentage ratio that accounts for total iron.
Acid dissolved oxygen hydrolysis: the material input reactor that obtains 3000L water and above-mentioned steps; And the maintenance temperature is 70～90 ℃; Keep to stir, gradation adds hydrochloric acid and 27.5% industrial ydrogen peroxide 50, no longer rises to pH=3 to solution acidity and continues to add small amount of hydrochloric acid when above and transfer to terminal point pH=1～2; Add 5N hydrochloric acid 1380L and 100Kg27.5% industry ydrogen peroxide 50 altogether, continue insulated and stirred 0.5 hour after the no ferrous ion of check.
Deironing aluminium: slowly add the about 130L of 3N ammoniacal liquor under the insulated and stirred, regulate acidity, and continue to stir 20 minutes to pH=3.5～4.
Filter:, this filtrating is further separated the product that purification can obtain corresponding rare earth, cobalt element promptly the be removed first-time filtrate that contains rare earth, cobalt element of iron aluminium element of the material filtering that mixes up the pH value.
Washing: will go up the filter residue that step obtains and mix, and remain on 70～90 ℃ after the intensification and stir and washed and filtration in 0.5 hour, and obtain wash filtrate and sub product filter residue with water.
First-time filtrate and wash filtrate merging obtain 5760 liters of solution that contain rare earth and cobalt, and detected result sees " embodiment one " in the table one for details.
Embodiment two
Referring to Fig. 1.
With the spontaneous combustion in air of the Nd-Fe-B alloys waste material of a collection of greasy filth state just burn iron is transformed into ferrous state after, become-60 order materials through wet ball-milling again.Get this iron-based waste material 2000Kg, through detecting wherein REO23.5wt%, Co 0.65wt%, FeO 63.3wt%, Fe
2O
31.47wt%, Al
2O
31.32wt%, water 8.4wt%, surplus is other material, after mixing reaction in 750L water and the 5N hydrochloric acid 360L input reactor; Material in the pot is paved on clean non-leakage acid-resistant floor; Stir for several times, and spray moisturizing, make material keep half-dried dampness; Be reduced to 17.6% until the ferrous percentage ratio that accounts for total iron, and record this moment solubility REO to account for total REO percentage ratio be 12.6%.
The hydrolysis of acid dissolved oxygen: the material and the 3000L water that obtain above-mentioned steps drop into reactor; Temperature is risen to 70～90 ℃, keep stirring, gradation adds 5N hydrochloric acid 1480L and 65Kg VAL-DROP; Insulated and stirred 1 hour is continued after the no ferrous ion of check in pH=1～2 to terminal.
Deironing aluminium: last step material insulated and stirred, slowly add about 20 liters of 3N sodium hydroxide, adjustment acidity is to pH3.5～4.0, and continuation was stirred 40 minutes.
Filter:, this aqueous solution is further separated the product that purification promptly obtains elements such as corresponding rare earth, cobalt promptly the be removed aqueous solution that contains rare earth, cobalt element of iron aluminium element of the material filtering that mixes up the pH value.
Washing: stir and to go up the filter residue that step obtains down and mix, keep temperature to be 70～90 ℃ and stir also filtrations of washed twice in 0.5 hour with water.Obtain wash filtrate and sub product filter residue.
All filtrating merging are obtained 6160 liters of solution that contain rare earth and cobalt, and detected result sees " embodiment two " in the table one for details.
Comparative Examples: the high-temperature oxidation that generally adopts in the industry
The Nd-Fe-B alloys waste material is pressed high-temperature oxidation with steps of processing:
1, high-temperature oxidation process: the Nd-Fe-B alloys waste material of getting a collection of greasy filth state is through steps of processing: in the air spontaneous combustion just burn, pulverize and cross 100 mesh sieves, in air with 800～850 ℃ of calcinations and cross 100 mesh sieves once more; Do Comparative Examples with this iron-based waste material, contain REO 26%, Co 0.81%, FeO 2.16%, Al through detecting
2O
31.26%, surplus is Fe
2O
3Deng.
2, acid is dissolved and deironing aluminium process:
A, acid are dissolved: stir following above-mentioned material 2000Kg and 3000L water and drop into reactor; Keeping temperature is 80 ℃ to 90 ℃; Gradation adds 10N hydrochloric acid and the 29Kg VAL-DROP of 1350L, adds hydrochloric acid and VAL-DROP continued insulated and stirred 1.5 hours, and the no ferrous ion of check.
B, deironing aluminium: the material insulated and stirred of steps A, slowly add 1400 liters in 3N sodium hydroxide, make pH rise to 3.5～4.0, continue to stir 40 minutes.
C, filtration:, this aqueous solution is further separated the product that purification can obtain elements such as corresponding rare earth, cobalt promptly the be removed aqueous solution that contains rare earth, cobalt element of iron aluminium element of the material filtering of step B.
D, washery slag: the filter residue that step C is obtained mixes with water, is warming up to 80 ℃ and stirs also filtration of washed twice in 1 hour.Filtrating is retained, and filter residue is as by-product sale.
All filtrating merging are obtained 7900 liters of solution that contain rare earth and cobalt, and detected result sees " Comparative Examples " in the table one for details.
Embodiment three
Referring to Fig. 1.
The cobalt Rhometal that the nickel metallurgy converter slag obtains through operations such as " electric dilution ", " magnetic separation of cobalt sulfonium "; Through jaw crusher, dry type is levigate reaches-100 orders, contain Co 4.8wt%, Ni 16.2wt%, Cu1.12wt%, Fe 73.3wt%, surplus and be other material through detecting.
Get above-mentioned material 1500Kg; Drop in the reactor with 1200L water and 75Kg98% sulfuric acid and after the hybrid reaction material to be paved in clean non-leakage kiver, stir for several times, and spray moisturizing; Make material keep half-dried dampness, account for total iron 7.2wt% until ferrous.
Acid dissolved oxygen hydrolysis: stir the material and the 3000L water that obtain above-mentioned steps down and drop into reactor; Slowly the 5N sulfuric acid of adding 2460L and 180Kg available chlorine are 60% Losantin; Keeping temperature is 70～90 ℃; Added sulfuric acid and Losantin continued insulated and stirred 40 minutes, through the no ferrous ion of check.
Deironing: in the material of last step, slowly add about 38Kg oxygen lime powder, be adjusted to pH3.5～4.0, and continue to stir 40 minutes.
Filter:, this aqueous solution is further separated purification can obtain corresponding cobalt, nickel, copper products can the be removed aqueous solution that contains cobalt, nickel, copper of ferro element of last step material filtering.
Washing: will go up the filter residue that step obtains and mix, and be warming up to 70～90 ℃ and stir also filtration of washed twice in 0.5 hour, and obtain wash filtrate filter residue sub product with water.
All filtrating merging are obtained 6720 liters of solution that contain cobalt, nickel, copper, and detected result sees " embodiment three " in the table one for details.
Table one: embodiment and Comparative Examples contrast table
Explain:
1. embodiment one adopts similar neodymium iron boron waste material with embodiment two with Comparative Examples.Can reach a conclusion from comparing result: employing the inventive method has advantages such as the valuable element yield is high, and the soda acid unit consumption is low.
2. embodiment three adopts and embodiment one, two and the different waste material of Comparative Examples, thereby its soda acid unit consumption does not have comparability.
Claims (5)
1. method that contains high value element iron-based waste material natural oxidation deironing aluminium is characterized in that may further comprise the steps:
(1) powder process: the iron-based waste material is processed granularity be-40 purpose powders;
(2) start reaction: levigated powder and water by weight water: waste material=0.5～1.5: 1 mixed is even, presses waste material weight again with 0.4～1molH
+/ Kg adds acid and stirs;
(3) air natural oxidation: the material stand that step (2) is produced is placed in the acidproof kiver or on the clean non-leakage acid-resistant floor; Stir several times; And the sprinkling moisturizing makes material remain humidity; Make iron, ferrous and high value element changed into corresponding salt or oxyhydroxide or oxide compound under field conditions (factors), account for below total iron 20wt% until ferrous by the air natural oxidation;
(4) sour dissolved oxygen hydrolysis: stir the material that slag washing water that a following water and/or step (7) obtain and step (3) obtain and drop in the reactor; And being warming up to 70～90 ℃, gradation adds acid and oxygenant, keeps reaction end pH≤2; Continued insulated and stirred 0.5 to 1 hour, and the no ferrous ion of check;
(5) deironing aluminium: the material insulated and stirred step (4), slowly add alkaline matter, make pH=3.5～4.0, and continue to stir 20 to 40 minutes;
(6) filter: the material filtering of step (5) filtrating of containing the high value element of iron aluminium element that promptly has been removed, this filtrating is further separated purification can obtain corresponding high value element product;
(7) washing: filter residue and water that step (6) is obtained are warming up to 70～90 ℃ of agitator treatings and filtration, and filtrating is returned step (4) and used, and filter residue is a sub product;
Said iron-based waste material is to be main element with iron, the material of at least a formed alloy state or ferrous state in interpolation high value element rare earth, cobalt, nickel, titanium, chromium, lead, bismuth, copper, manganese, the zinc.
2. the method for iron-based waste material natural oxidation deironing aluminium according to claim 1 is characterized in that said iron-based waste material granularity 40～100 orders.
3. the method for iron-based waste material natural oxidation deironing aluminium according to claim 1 is characterized in that said acid is hydrochloric acid or sulfuric acid.
4. the method for iron-based waste material natural oxidation deironing aluminium according to claim 1 is characterized in that said alkaline matter is the oxyhydroxide or the oxide compound of ammoniacal liquor and/or basic metal and/or earth alkali metal.
5. the method for iron-based waste material natural oxidation deironing aluminium according to claim 1 is characterized in that said oxygenant is oxymuriate or hypochlorite and/or ydrogen peroxide 50.
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| PCT/CN2012/000090 WO2012113263A1 (en) | 2011-02-26 | 2012-01-18 | Method for removing iron and aluminum from iron-based waste material containing high-value elements through natural oxidation |
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| CN102154553B (en) * | 2011-02-26 | 2012-05-30 | 赣州力赛科新技术有限公司 | Method for removing iron and aluminum from iron-based waste containing high-value elements through natural oxidation |
| CN104232905B (en) * | 2014-06-16 | 2015-08-12 | 赣州力赛科新技术有限公司 | A kind of containing iron oxide based raw material of high value element hydrogen and uses thereof |
| CN105087967A (en) * | 2015-08-30 | 2015-11-25 | 常州市鼎日环保科技有限公司 | Device for recycling rare earth elements in neodymium iron boron waste materials |
| CN105132698A (en) * | 2015-09-27 | 2015-12-09 | 常州市奥普泰科光电有限公司 | Technology for extracting aluminum and zinc from high-aluminum zinciferous aluminum-zinc residues |
| CN106244802A (en) * | 2016-08-31 | 2016-12-21 | 中信大锰矿业有限责任公司 | A kind of method that manganese in electrolytic manganese residues reclaims |
| CN112843582B (en) * | 2021-01-21 | 2022-06-17 | 元素贵稀吉林省环境科技有限公司 | Method for recycling iron-containing and aluminum-containing hazardous waste with energy conservation |
| CN113444874B (en) * | 2021-05-18 | 2023-01-13 | 广东邦普循环科技有限公司 | Method for safely oxidizing and roasting neodymium iron boron powder and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1605638A (en) * | 2004-06-28 | 2005-04-13 | 辽宁美宝稀土材料有限公司 | Process for recovering rare earth from neodymium-ion-boron waste materials |
| CN1693493A (en) * | 2005-05-08 | 2005-11-09 | 西安西骏新材料有限公司 | Recovery method of valuable element in neodymium iron boron waste material |
| JP2006063370A (en) * | 2004-08-25 | 2006-03-09 | Nippon Magnetic Dressing Co Ltd | Method for recovering rare earth |
| CN101717859A (en) * | 2009-12-22 | 2010-06-02 | 赣州步莱铽新资源有限公司 | Method for recovering rare earth from wastes of neodymium iron boron |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3868439A (en) * | 1973-02-09 | 1975-02-25 | Univ Utah | Method of increasing copper production |
| JPS634028A (en) * | 1986-06-23 | 1988-01-09 | Sumitomo Metal Mining Co Ltd | Treatment for scrap containing rare earth element and iron |
| JP2982829B2 (en) * | 1991-02-05 | 1999-11-29 | 住友金属鉱山株式会社 | Recovery method for rare earth elements |
| CN1119216A (en) * | 1994-09-22 | 1996-03-27 | 泰兴市君泰稀土实业有限公司 | Process for preparing neodymium and neodymium-dysprosium compounds by recovering waste neodymium-iron-boron |
| JPH09217132A (en) * | 1996-02-13 | 1997-08-19 | Santoku Kinzoku Kogyo Kk | Method for recovering useful element from rare earth-iron alloy |
| CN102154553B (en) * | 2011-02-26 | 2012-05-30 | 赣州力赛科新技术有限公司 | Method for removing iron and aluminum from iron-based waste containing high-value elements through natural oxidation |
-
2011
- 2011-02-26 CN CN201110046685XA patent/CN102154553B/en active Active
-
2012
- 2012-01-18 WO PCT/CN2012/000090 patent/WO2012113263A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1605638A (en) * | 2004-06-28 | 2005-04-13 | 辽宁美宝稀土材料有限公司 | Process for recovering rare earth from neodymium-ion-boron waste materials |
| JP2006063370A (en) * | 2004-08-25 | 2006-03-09 | Nippon Magnetic Dressing Co Ltd | Method for recovering rare earth |
| CN1693493A (en) * | 2005-05-08 | 2005-11-09 | 西安西骏新材料有限公司 | Recovery method of valuable element in neodymium iron boron waste material |
| CN101717859A (en) * | 2009-12-22 | 2010-06-02 | 赣州步莱铽新资源有限公司 | Method for recovering rare earth from wastes of neodymium iron boron |
Non-Patent Citations (2)
| Title |
|---|
| 张万琰等.从钕铁硼废料中回收稀土及氧化钴的条件试验.《江西有色金属》.2001,第15卷(第4期),23-26. * |
| 许涛等.钕铁硼废料中钕、镝及钴的回收.《稀土》.2004,第25卷(第2期),31-34. * |
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