CN105967240A - Method for preparing ammonium jarosite and trimanganese tetroxide by using potassium permanganate waste residues - Google Patents
Method for preparing ammonium jarosite and trimanganese tetroxide by using potassium permanganate waste residues Download PDFInfo
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- CN105967240A CN105967240A CN201610243636.8A CN201610243636A CN105967240A CN 105967240 A CN105967240 A CN 105967240A CN 201610243636 A CN201610243636 A CN 201610243636A CN 105967240 A CN105967240 A CN 105967240A
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- filtrate
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- potassium permanganate
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 49
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 title claims abstract description 44
- 229910052935 jarosite Inorganic materials 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000012286 potassium permanganate Substances 0.000 title claims abstract description 38
- 239000002699 waste material Substances 0.000 title claims abstract description 36
- 239000000706 filtrate Substances 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000002386 leaching Methods 0.000 claims abstract description 33
- 238000001914 filtration Methods 0.000 claims abstract description 31
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 22
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims abstract description 22
- 239000000047 product Substances 0.000 claims abstract description 21
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002244 precipitate Substances 0.000 claims abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 33
- 238000001556 precipitation Methods 0.000 claims description 30
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 229910021529 ammonia Inorganic materials 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000010941 cobalt Substances 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 239000010813 municipal solid waste Substances 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 235000011149 sulphuric acid Nutrition 0.000 claims description 8
- 239000001117 sulphuric acid Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- 239000011572 manganese Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 claims 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 229910001882 dioxygen Inorganic materials 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 10
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 abstract 2
- 229910052683 pyrite Inorganic materials 0.000 abstract 2
- 239000011028 pyrite Substances 0.000 abstract 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 229910052700 potassium Inorganic materials 0.000 abstract 1
- 239000011591 potassium Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 9
- 230000003749 cleanliness Effects 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 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 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010563 solid-state fermentation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/14—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides a method for preparing ammonium jarosite and trimanganese tetroxide by using potassium permanganate waste residues. The method comprises the following steps: carrying out reduction leaching of the potassium permangnate waste residues with pyrite, and filtering to obtain a leached filtrate; adding hydrogen peroxide to the obtained leached filtrate, under conditions of the temperature of 90-100 DEG C and the pH of 1.5-2.5, carrying out a reaction until a precipitate is no longer generated in the reaction process, and filtering, wherein the obtained filter residue is ammonium jarosite, and the filtrate is an iron-removed filtrate; adjusting the pH value of the iron-removed filtrate to 9-10.5, at the same time, heating to 60-90 DEG C, carrying out a reaction, after the reaction, filtering the product, to obtain a filter residue, namely a manganese hydroxide precipitate, and preparing trimanganese tetroxide with the obtained manganese hydroxide precipitate. The potassium permanganate waste residues are subjected to reduction leaching with the pyrite, and then an iron element and a manganese element are separated out of the leached filtrate, the technological process is simple, the preparation process has certain selectivity, and high-purity battery-grade products can be directly obtained.
Description
Technical field
The invention belongs to the process of industrial residue and utilize field, relating to a kind of method utilizing potassium permanganate waste residue to prepare ammonium jarosite and mangano-manganic oxide.
Background technology
Potassium permanganate is the chemicals that a class is important, is widely used to the field such as medical science, industry.The total output of world's potassium permanganate is 7～80,000 t/a in recent years, and wherein China's yield reaches about 3.6 ten thousand t/a, and through development for many years, China has become as the manufacturing country that potassium permanganate is maximum.At present, produce 1t potassium permanganate and about produce 0.75t (butt) manganese slag, special here claim potassium permanganate waste residue, wherein contain 4～the Mn oxide of 8% and manganese salt.The bulk deposition of potassium permanganate waste residue, not only causes the waste of promoter manganese, and environmentally safe constitutes a serious threat.
At present, the handling problems of potassium permanganate waste residue has been obtained for the concern of people.
CN 1715254A discloses a kind of integrated treatment and the method utilizing the waste residue producing potassium permanganate；CN 1127726A discloses a kind of method that waste residue producing potassium permanganate produces manganese sulfate, and it describes with ferrous ion as reducing agent, and leaching of manganese element and the method for ferrum element, the method is easily implemented, but product purity is relatively low, and added value is the highest.CN 1657423A discloses a kind of method reclaiming manganese sulfate from low-grade manganese carbonate and manganese oxide ore, described method is using troilite as reducing agent, leach the manganese element in low-grade manganese slag, but its follow-up purifying step is loaded down with trivial details, be difficult to equally obtain high value-added product.
Summary of the invention
Low for product purity present in existing potassium permanganate Solid state fermentation process, added value is low, and the problem such as purification process complex steps, the invention provides a kind of method utilizing potassium permanganate waste residue to prepare ammonium jarosite and mangano-manganic oxide.The present invention passes through troilite reducing leaching potassium permanganate waste residue, again ferrum element and manganese element are separated from leachate with the form of ammonium jarosite and mangano-manganic oxide respectively, technical process is simple, materials low cost, preparation process has certain selectivity, can directly obtain the LITHIUM BATTERY product of high cleanliness.
For reaching this purpose, the present invention by the following technical solutions:
The invention provides a kind of method utilizing potassium permanganate waste residue to prepare ammonium jarosite and mangano-manganic oxide, it is characterised in that said method comprising the steps of:
(1) with troilite, potassium permanganate waste residue carried out reducing leaching, and be filtrated to get leaching filtrate；
(2) in the leaching filtrate that step (1) obtains, hydrogen peroxide is added, at 90～100 DEG C, pH is to react under conditions of 1.5～2.5, filters when no longer producing precipitation to course of reaction, and gained filtering residue is ammonium jarosite ((NH4)Fe3(SO4)2(OH)6), filtrate is except ferrum filtrate；
(3) regulating step (2) gained is except the pH to 9～10.5 of ferrum filtrate, is simultaneously heated to 60～90 DEG C and reacts, and is filtered by product after reaction, and gained filtering residue is manganous hydroxide precipitation, prepares mangano-manganic oxide with gained manganous hydroxide precipitation.
Wherein, step (2) described reaction temperature can be 90 DEG C, 91 DEG C, 92 DEG C, 93 DEG C, 94 DEG C, 95 DEG C, 96 DEG C, 97 DEG C, 98 DEG C, 99 DEG C or 100 DEG C etc., it is not limited to cited numerical value, listed in the range of other numerical value the most feasible；The pH of step (2) described reaction can be 1.5,1.6,1.7,1.8,1.9,2.0,2.1,2.2,2.3,2.4 or 2.5 etc., it is not limited to cited numerical value, listed in the range of other numerical value the most feasible；Described in step (3), the pH of reaction can be 9,9.3,9.5,9.7,10.0,10.3 or 10.5 etc., it is not limited to cited numerical value, listed in the range of other numerical value the most feasible；Step (3) described reaction temperature can be 60 DEG C, 63 DEG C, 65 DEG C, 67 DEG C, 70 DEG C, 73 DEG C, 75 DEG C, 77 DEG C, 80 DEG C, 83 DEG C, 85 DEG C, 87 DEG C or 90 DEG C etc., it is not limited to cited numerical value, listed in the range of other numerical value the most feasible.
Above-mentioned steps (2) is to be separated from leachate with the form of ammonium jarosite by ferrum element；Step (2) gained is except ferrum richness manganese filtrate except ferrum filtrate；Step (3) be by manganese element with the form of mangano-manganic oxide from except ferrum richness manganese filtrate is separated.
Following as currently preferred technical scheme, but the restriction of the technical scheme provided not as the present invention, by the following technical programs, can preferably reach and realize technical purpose and the beneficial effect of the present invention.
As currently preferred technical scheme, step (1) carries out reducing leaching with troilite to potassium permanganate waste residue and comprises the following steps:
It is 10:(1～3 in mass ratio by potassium permanganate waste residue and the troilite through pretreatment) add to the sulphuric acid that concentration is 0.5～1.5mol/L, at ambient pressure in 80～100 DEG C of acidleach 1～3h.
Wherein, potassium permanganate waste residue and troilite can be 10:1,10:1.5,10:2,10:2.5 or 10:3 etc. in mass ratio, it is not limited to cited numerical value, listed in the range of other numerical value the most feasible；The concentration of described sulphuric acid can be 0.5mol/L, 0.7mol/L, 1.0mol/L, 1.3mol/L or 1.5mol/L etc., it is not limited to cited numerical value, listed in the range of other numerical value the most feasible；Described extraction temperature can be 80 DEG C, 83 DEG C, 85 DEG C, 87 DEG C, 90 DEG C, 93 DEG C, 95 DEG C, 97 DEG C or 100 DEG C etc., it is not limited to cited numerical value, listed in the range of other numerical value the most feasible；Described extraction time can be 1h, 1.5h, 2h, 2.5h or 3h etc., it is not limited to cited numerical value, listed in the range of other numerical value the most feasible.
In the present invention, described " normal pressure " refers to a normal atmosphere, for 101325Pa.
As currently preferred technical scheme, described pretreatment is for grinding and process of sieving.
Preferably, the mass ratio of described potassium permanganate waste residue and troilite is 5:1.
Preferably, described sulfuric acid concentration is 1.25mol/L.
Preferably, described acidleach temperature is 95 DEG C.
Preferably, described leaching time is 2h.
In the present invention, with the mass ratio of potassium permanganate waste residue and troilite as 5:1, sulfuric acid concentration is 1.25mol/L, under conditions of acidleach temperature is 95 DEG C and leaching time 2h, best to the leaching effect of potassium permanganate waste residue.
As currently preferred technical scheme, step is filtered into sucking filtration and/or filter pressing described in (1).
As currently preferred technical scheme, in step (2), the addition of hydrogen peroxide is to make the Fe in leaching filtrate2+All it is oxidized to Fe3+。
In the present invention, the hydrogen peroxide added must be excessive, to ensure to leach the Fe in filtrate2+All it is oxidized to Fe3+。
Preferably, step (2) described reaction temperature is 95 DEG C.
Preferably, the pH of step (2) described reaction is 2.5.
As currently preferred technical scheme, step (2) described course of reaction drips ammonia regulation pH.
Wherein, the dropping of ammonia must slowly be carried out, it is provided that a stable pH environment；In the present invention, the pH of course of reaction needs strict control, so that ferrum precipitation is completely, and other elements and impurity do not precipitate, thus prepare the ammonium jarosite of LITHIUM BATTERY product purity.In the present invention, ammonia can only be used to regulate pH, the ammonium jarosite of LITHIUM BATTERY product purity cannot be prepared according to other materials.
It is 10 as the pH of regulation reaction in currently preferred technical scheme, step (3).
Preferably, step (3) regulates pH to except ferrum filtrate added drop-wise ammonia.The pH of described course of reaction needs strict control, so that manganese precipitation is completely, and other elements and impurity do not precipitate, thus prepare high-purity manganous hydroxide precipitation, in order to prepare the mangano-manganic oxide of LITHIUM BATTERY product purity further.
Preferably, described in step (3), reaction temperature is 70 DEG C.
Preferably, described in step (3), the response time of reaction is 0.5～2h, such as 0.5h, 0.7h, 1h, 1.3h, 1.5h, 1.7h or 2h etc., it is not limited to cited numerical value, in the range of Suo Lie, other numerical value are the most feasible, and more preferably 0.5～1h.
As currently preferred technical scheme, step (3) with the method for the prepared mangano-manganic oxide of gained manganous hydroxide precipitation is:
Gained manganous hydroxide precipitation being added water and make slip, be passed through air stirring reaction 0.5～2h at 50～90 DEG C, then filtration drying obtains mangano-manganic oxide.
Wherein, the response time can be 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C or 90 DEG C etc., it is not limited to cited numerical value, listed in the range of other numerical value the most feasible；The described response time can be 0.5h, 0.7h, 1h, 1.3h, 1.5h, 1.7h or 2h etc., it is not limited to cited numerical value, listed in the range of other numerical value the most feasible.
As currently preferred technical scheme, purity >=99% of the ammonium jarosite that step (2) prepares.
Preferably, purity >=98% of mangano-manganic oxide that step (3) prepares, and its field trash mostly is the useful doping such as nickel, cobalt.
As currently preferred technical scheme, said method comprising the steps of:
(1) the potassium permanganate waste residue through grinding and sieve and troilite are added to the sulphuric acid that concentration is 1.25mol/L for 5:1 in mass ratio, at ambient pressure in 95 DEG C of acidleach 2h, and be filtrated to get leaching filtrate；
(2) adding hydrogen peroxide in the leaching filtrate that step (1) obtains, at 95 DEG C, pH is to react under conditions of 2.5, course of reaction drips ammonia regulation pH, filtering when no longer producing precipitation to course of reaction, gained filtering residue is ammonium jarosite, and filtrate is except ferrum filtrate；
(3) pH to 10 is regulated to step (2) gained except ferrum filtrate added drop-wise ammonia, it is simultaneously heated to 70 DEG C carry out reacting 0.5～1h, after reaction, product is filtered, gained filtering residue is manganous hydroxide precipitation, gained manganous hydroxide precipitation is added water and makes slip, being passed through air stirring reaction 0.5～2h at 50～90 DEG C, then filtration drying obtains mangano-manganic oxide.
Compared with prior art, the method have the advantages that
The present invention passes through troilite reducing leaching potassium permanganate waste residue, again ferrum element and manganese element are separated from leachate with the form of ammonium jarosite and mangano-manganic oxide respectively, technical process is simple, materials low cost, preparation process has certain selectivity, the LITHIUM BATTERY product of high cleanliness can be directly obtained by simple step, the purity of gained ammonium jarosite can reach 99%, the purity of mangano-manganic oxide can reach 98%, and its field trash mostly is the useful doping such as nickel, cobalt, can be used for producing lithium iron phosphate positive material and manganate cathode material for lithium.
Accompanying drawing explanation
Fig. 1 is the XRD diffraction pattern of the ammonium jarosite that the embodiment of the present invention 1 prepares；
Fig. 2 is the XRD diffraction pattern of the mangano-manganic oxide that the embodiment of the present invention 1 prepares；
Fig. 3 is the XRD diffraction pattern of the ammonium jarosite that the embodiment of the present invention 2 prepares；
Fig. 4 is the XRD diffraction pattern of the mangano-manganic oxide that the embodiment of the present invention 2 prepares；
Fig. 5 is the XRD diffraction pattern of the ammonium jarosite that the embodiment of the present invention 3 prepares；
Fig. 6 is the XRD diffraction pattern of the mangano-manganic oxide that the embodiment of the present invention 3 prepares；
Fig. 7 is the SEM scanning electron microscope (SEM) photograph of the ammonium jarosite that the embodiment of the present invention 3 prepares；
Fig. 8 is the XRD diffraction pattern of the ammonium jarosite that the embodiment of the present invention 4 prepares；
Fig. 9 is the XRD diffraction pattern of the mangano-manganic oxide that the embodiment of the present invention 4 prepares；
Figure 10 is the XRD diffraction pattern of the ammonium jarosite that the embodiment of the present invention 5 prepares；
Figure 11 is the XRD diffraction pattern of the mangano-manganic oxide that the embodiment of the present invention 5 prepares.
Detailed description of the invention
For the present invention is better described, it is simple to understand technical scheme, below the present invention is described in more detail.But following embodiment is only the simple example of the present invention, does not represent or limit the scope of the present invention, and scope is as the criterion with claims.
Specific embodiment of the invention part provides the method utilizing potassium permanganate waste residue to prepare ammonium jarosite and mangano-manganic oxide, said method comprising the steps of:
(1) with troilite, potassium permanganate waste residue carried out reducing leaching, and be filtrated to get leaching filtrate；
(2) in the leaching filtrate that step (1) obtains, hydrogen peroxide is added, at 90～100 DEG C, pH is to react under conditions of 1.5～2.5, filters when no longer producing precipitation to course of reaction, gained filtering residue is ammonium jarosite, and filtrate is except ferrum filtrate；
(3) regulating step (2) gained is except the pH to 9～10.5 of ferrum filtrate, is simultaneously heated to 60～90 DEG C and reacts, and is filtered by product after reaction, and gained filtering residue is manganous hydroxide precipitation, prepares mangano-manganic oxide with gained manganous hydroxide precipitation.
Described typical case but non-limiting example is as follows:
Embodiment 1:
(1) the potassium permanganate waste residue through grinding and sieve and troilite being added to the sulphuric acid that concentration is 0.5mol/L for 10:1 in mass ratio, at ambient pressure in 80 DEG C of acidleach 1h, the question response time terminates, and product carries out sucking filtration and obtains leaching filtrate；
(2) in the leaching filtrate that step (1) obtains, enough hydrogen peroxide are added to ensure to leach the Fe in filtrate2+All it is oxidized to Fe3+, at 95 DEG C, pH is to react under conditions of 1.5, is slowly added dropwise ammonia regulation pH, filters when no longer producing precipitation to course of reaction in course of reaction, and gained filtering residue is ammonium jarosite, and filtrate is except ferrum filtrate；
(3) continue to be slowly added dropwise ammonia regulation pH to 9 except ferrum filtrate to step (2) gained, it is simultaneously heated to 60 DEG C carry out reacting 0.5h, after reaction, product is filtered, gained filtering residue is manganous hydroxide precipitation, gained manganous hydroxide precipitation is added water and makes slip, being passed through air stirring reaction 0.5h at 50 DEG C, then filtration drying obtains mangano-manganic oxide.
The purity of the ammonium jarosite that the present embodiment prepares can reach 99%, and the purity of mangano-manganic oxide is more than 98%, and its field trash mostly is the useful doping such as nickel, cobalt.The most all can reach LITHIUM BATTERY product purity, its XRD diffraction pattern is as depicted in figs. 1 and 2.
Embodiment 2:
(1) the potassium permanganate waste residue through grinding and sieve and troilite being added to the sulphuric acid that concentration is 1mol/L for 10:2 in mass ratio, at ambient pressure in 90 DEG C of acidleach 2h, the question response time terminates, and product carries out sucking filtration and obtains leaching filtrate；
(2) in the leaching filtrate that step (1) obtains, enough hydrogen peroxide are added to ensure to leach the Fe in filtrate2+All it is oxidized to Fe3+, at 95 DEG C, pH is to react under conditions of 2, is slowly added dropwise ammonia regulation pH, filters when no longer producing precipitation to course of reaction in course of reaction, and gained filtering residue is ammonium jarosite, and filtrate is except ferrum filtrate；
(3) continue to be slowly added dropwise ammonia regulation pH to 10 except ferrum filtrate to step (2) gained, it is simultaneously heated to 75 DEG C carry out reacting 0.75h, after reaction, product is filtered, gained filtering residue is manganous hydroxide precipitation, gained manganous hydroxide precipitation is added water and makes slip, being passed through air stirring reaction 1h at 70 DEG C, then filtration drying obtains mangano-manganic oxide.
The purity of the ammonium jarosite that the present embodiment prepares can reach 99%, and the purity of mangano-manganic oxide can reach 98%, and its field trash mostly is the useful doping such as nickel, cobalt.All may be used to produce cell positive material, its XRD diffraction pattern is as shown in Figure 3 and Figure 4.
Embodiment 3:
(1) the potassium permanganate waste residue through grinding and sieve and troilite being added to the sulphuric acid that concentration is 1.5mol/L for 10:3 in mass ratio, at ambient pressure in 100 DEG C of acidleach 3h, the question response time terminates, and product carries out sucking filtration and obtains leaching filtrate；
(2) in the leaching filtrate that step (1) obtains, enough hydrogen peroxide are added to ensure to leach the Fe in filtrate2+All it is oxidized to Fe3+, at 95 DEG C, pH is to react under conditions of 2.5, is slowly added dropwise ammonia regulation pH, filters when no longer producing precipitation to course of reaction in course of reaction, and gained filtering residue is ammonium jarosite, and filtrate is except ferrum filtrate；
(3) continue to be slowly added dropwise ammonia regulation pH to 10.5 except ferrum filtrate to step (2) gained, it is simultaneously heated to 90 DEG C carry out reacting 1h, after reaction, product is filtered, gained filtering residue is manganous hydroxide precipitation, gained manganous hydroxide precipitation is added water and makes slip, being passed through air stirring reaction 2h at 90 DEG C, then filtration drying obtains mangano-manganic oxide.
The purity of the ammonium jarosite that the present embodiment prepares can reach 99%, the purity of mangano-manganic oxide can reach 98%, and its field trash mostly is the useful doping such as nickel, cobalt, all may be used to produce cell positive material, as shown in Figure 5 and Figure 6, the SEM scanning electron microscope (SEM) photograph of ammonium jarosite is as shown in Figure 7 for its XRD diffraction pattern.
Embodiment 4:
In step (2), reaction temperature is in addition to 90 DEG C, unclassified stores consumption is the most in the same manner as in Example 1 with preparation method, the purity of the ammonium jarosite that the present embodiment prepares can reach 99%, the purity of mangano-manganic oxide can reach 98%, and its field trash mostly is the useful doping such as nickel, cobalt, all may be used to produce cell positive material, its XRD diffraction pattern is as shown in Figure 8 and Figure 9.
Embodiment 5:
In step (2), reaction temperature is in addition to 100 DEG C, unclassified stores consumption is the most in the same manner as in Example 1 with preparation method, the purity of the ammonium jarosite that the present embodiment prepares can reach 99%, the purity of mangano-manganic oxide can reach 98%, and its field trash mostly is the useful doping such as nickel, cobalt, all may be used to produce cell positive material, its XRD diffraction pattern is as shown in Figure 10 and Figure 11.
Comparative example 1:
In addition to regulation pH to 3～4 (i.e. ＞ 1.5～2.5) in step (2), unclassified stores consumption is the most in the same manner as in Example 1 with preparation method, the purity of the ammonium jarosite that this comparative example prepares is 90%, and the purity of mangano-manganic oxide is 93%.
Comparative example 2:
In addition to regulation pH to 0.5 (i.e. ＜ 1.5～2.5) in step (2), unclassified stores consumption is the most in the same manner as in Example 1 with preparation method, the amount of the ammonium jarosite that this comparative example prepares is few, even cannot obtain ammonium jarosite, the purity of mangano-manganic oxide is less than 50%.
Comparative example 3:
In addition to regulation pH to 8 (i.e. ＜ 9～10.5) in step (2), unclassified stores consumption is the most in the same manner as in Example 1 with preparation method, the purity of the ammonium jarosite that this comparative example prepares is 99%, and the purity of mangano-manganic oxide is less than 10%.
Comparative example 4:
In addition to regulation pH to 11 (i.e. ＞ 9～10.5) in step (2), unclassified stores consumption is the most in the same manner as in Example 1 with preparation method, the purity of the ammonium jarosite that this comparative example prepares is 99%, and the purity of mangano-manganic oxide is 95%.
The result of integrated embodiment 1-5 and comparative example 1-4 can be seen that, the present invention passes through troilite reducing leaching potassium permanganate waste residue, again ferrum element and manganese element are separated from leachate with the form of ammonium jarosite and mangano-manganic oxide respectively, technical process is simple, materials low cost, preparation process has certain selectivity, the LITHIUM BATTERY product of high cleanliness can be directly obtained by simple step, the purity of gained ammonium jarosite can reach 99%, the purity of mangano-manganic oxide can reach 98%, and its field trash mostly is nickel, the useful doping such as cobalt, can be used for producing lithium iron phosphate positive material and manganate cathode material for lithium.
Applicant states, the present invention illustrates the method detailed of the present invention by above-described embodiment, but the invention is not limited in above-mentioned method detailed, does not i.e. mean that the present invention has to rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field is it will be clearly understood that any improvement in the present invention, and the equivalence of raw material each to product of the present invention is replaced and the interpolation of auxiliary element, concrete way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (10)
1. utilizing the method that potassium permanganate waste residue prepares ammonium jarosite and mangano-manganic oxide, its feature exists
In, said method comprising the steps of:
(1) with troilite, potassium permanganate waste residue carried out reducing leaching, and be filtrated to get leaching filtrate；
(2) adding hydrogen peroxide in the leaching filtrate that step (1) obtains, at 90～100 DEG C, pH is 1.5～2.5
Under conditions of react, filter when no longer producing precipitation to course of reaction, gained filtering residue is yellow ammonium ferrum
Vitriol, filtrate is except ferrum filtrate；
(3) regulating step (2) gained is except the pH to 9～10.5 of ferrum filtrate, is simultaneously heated to 60～90 DEG C and enters
Row reaction, filters product after reaction, and gained filtering residue is manganous hydroxide precipitation, precipitates with gained manganous hydroxide
Prepare mangano-manganic oxide.
Method the most according to claim 1, it is characterised in that with troilite to height in step (1)
Potassium manganate waste residue carries out reducing leaching and comprises the following steps:
By through the potassium permanganate waste residue of pretreatment and troilite in mass ratio for 10:(1～3) add to concentration and be
In the sulphuric acid of 0.5～1.5mol/L, at ambient pressure in 80～100 DEG C of acidleach 1～3h.
Method the most according to claim 2, it is characterised in that described pretreatment is for grinding and sieving
Process；
Preferably, the mass ratio of described potassium permanganate waste residue and troilite is 5:1；
Preferably, described sulfuric acid concentration is 1.25mol/L；
Preferably, described acidleach temperature is 95 DEG C；
Preferably, described leaching time is 2h.
4. according to the method described in any one of claim 1-3, it is characterised in that step (1) described mistake
Filter is sucking filtration and/or filter pressing.
5. according to the method described in any one of claim 1-4, it is characterised in that dioxygen in step (2)
The addition of water is to make the Fe in leaching filtrate2+All it is oxidized to Fe3+；
Preferably, step (2) described reaction temperature is 95 DEG C；
Preferably, the pH of step (2) described reaction is 2.5.
6. according to the method described in any one of claim 1-5, it is characterised in that step (2) is described instead
Ammonia regulation pH is dripped during Ying.
7. according to the method described in any one of claim 1-6, it is characterised in that regulation in step (3)
The pH of reaction is 10；
Preferably, step (3) regulates pH to except ferrum filtrate added drop-wise ammonia；
Preferably, described in step (3), reaction temperature is 70 DEG C；
Preferably, described in step (3), the response time of reaction is 0.5～2h, more preferably
0.5～1h.
8. according to the method described in any one of claim 1-7, it is characterised in that with institute in step (3)
The method obtaining the prepared mangano-manganic oxide of manganous hydroxide precipitation is:
Gained manganous hydroxide precipitation is added water and makes slip, at 50～90 DEG C, be passed through air stirring reaction
0.5～2h, then filtration drying obtains mangano-manganic oxide.
9. according to the method described in any one of claim 1-8, it is characterised in that step (2) prepares
Purity >=99% of ammonium jarosite；
Preferably, purity >=98% of mangano-manganic oxide that step (3) prepares, and its field trash mostly be nickel,
The useful doping such as cobalt.
10. according to the method described in any one of claim 1-9, it is characterised in that described method include with
Lower step:
(1) the potassium permanganate waste residue through grinding and sieve and troilite are added to dense for 5:1 in mass ratio
In the degree sulphuric acid for 1.25mol/L, at ambient pressure in 95 DEG C of acidleach 2h, and it is filtrated to get leaching filtrate；
(2) adding hydrogen peroxide in the leaching filtrate that step (1) obtains, at 95 DEG C, pH is the bar of 2.5
React under part, course of reaction drips ammonia regulation pH, enters when no longer producing precipitation to course of reaction
Row filters, and gained filtering residue is ammonium jarosite, and filtrate is except ferrum filtrate；
(3) regulate pH to 10 to step (2) gained except ferrum filtrate added drop-wise ammonia, be simultaneously heated to 70 DEG C
Carrying out reacting 0.5～1h, filtered by product after reaction, gained filtering residue is manganous hydroxide precipitation, by gained hydrogen-oxygen
Change manganese precipitation adds water and makes slip, is passed through air stirring reaction 0.5～2h, then crosses and be filtered dry at 50～90 DEG C
Dry obtain mangano-manganic oxide.
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