CN116173703A - Mineralizing CO from electrolytic manganese slag 2 Method for synergistic solidification of metal ions and mineralized products - Google Patents
Mineralizing CO from electrolytic manganese slag 2 Method for synergistic solidification of metal ions and mineralized products Download PDFInfo
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- CN116173703A CN116173703A CN202211564989.XA CN202211564989A CN116173703A CN 116173703 A CN116173703 A CN 116173703A CN 202211564989 A CN202211564989 A CN 202211564989A CN 116173703 A CN116173703 A CN 116173703A
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- electrolytic manganese
- manganese slag
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- 239000011572 manganese Substances 0.000 title claims abstract description 116
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 90
- 239000002893 slag Substances 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 47
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 19
- 230000001089 mineralizing effect Effects 0.000 title description 6
- 238000007711 solidification Methods 0.000 title description 2
- 230000008023 solidification Effects 0.000 title description 2
- 230000002195 synergetic effect Effects 0.000 title description 2
- 239000000047 product Substances 0.000 claims abstract description 81
- 238000002386 leaching Methods 0.000 claims abstract description 57
- 239000000243 solution Substances 0.000 claims abstract description 46
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 230000007935 neutral effect Effects 0.000 claims abstract description 25
- 239000000706 filtrate Substances 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 239000012065 filter cake Substances 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 17
- 239000012266 salt solution Substances 0.000 claims abstract description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 36
- 229910021532 Calcite Inorganic materials 0.000 claims description 23
- 230000033558 biomineral tissue development Effects 0.000 claims description 23
- 239000002994 raw material Substances 0.000 claims description 21
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 18
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 12
- 229910001424 calcium ion Inorganic materials 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 235000019270 ammonium chloride Nutrition 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 9
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 8
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 4
- 239000005695 Ammonium acetate Substances 0.000 claims description 4
- 229940043376 ammonium acetate Drugs 0.000 claims description 4
- 235000019257 ammonium acetate Nutrition 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 239000002910 solid waste Substances 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 239000003546 flue gas Substances 0.000 claims description 3
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 9
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000004134 energy conservation Methods 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 239000011777 magnesium Substances 0.000 description 18
- 239000012071 phase Substances 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 description 8
- 230000018109 developmental process Effects 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 4
- 238000000643 oven drying Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000010183 spectrum analysis Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000010363 phase shift Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/80—Destroying solid waste or transforming solid waste into something useful or harmless involving an extraction step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
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- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides an electrolytic manganese slag mineralized CO 2 A method of co-curing metal ions and mineralized products, the method comprising the steps of: mixing electrolytic manganese slag powder and neutral salt solution according to a preset liquid-solid ratio, and leaching at a first temperature and a first stirring rotation speed for a first period of time to obtain a first solid-liquid mixture; filtering the first solid-liquid mixture to obtain leaching liquid and leaching slag; mixing the leaching solution with concentrated ammonia water at a predetermined ratio, and introducing CO at a first rate 2 Stirring the gas at a second temperature for reacting for a second period of time to obtain a second solid-liquid mixture; suction filtering the second solid-liquid mixture to obtain a filter cake and a filtrate; washing and drying filter cakeObtaining mineralized products. The mineralized product is obtained by the method. The invention can utilize electrolytic manganese slag to treat CO 2 In-situ curing and CO curing 2 Simultaneously and cooperatively solidifying heavy metal Mn in electrolytic manganese slag 2+ /Mg 2+ High-value utilization of electrolytic manganese slag, energy conservation, environmental protection and the like.
Description
Technical Field
The invention belongs to the technical field of environmental engineering, in particular to an electrolytic manganese slag mineralized CO 2 A method for co-curing metal ions and mineralized products.
Background
The electrolytic manganese slag is an industrial solid waste which is produced after leaching of manganese ore in the production process of electrolytic manganese metal and takes gypsum as a main phase, and the production process is accompanied by a large amount of CO due to the higher content of calcium ions 2 Is discharged from the reactor; thus the electrolytic manganese slag is suitable for mineralizing CO 2 Is a raw material of (a) a powder.
At present, scholars at home and abroad mineralize CO from electrolytic manganese slag 2 The prior art adopts a direct method to add ammonium carbonate, ammonium bicarbonate or add CO 2 Ammonia water is added simultaneously to convert calcium sulfate dihydrate in electrolytic manganese into calcium carbonate, thereby realizing CO 2 Is a mineralization of (a). Because the electrolytic manganese slag has complex chemical composition, raw materials directly participate in chemical reaction after being not purified, and SiO contained in the raw materials 2 、Al 2 O 3 、Fe 2 O 3 The impurities are transferred into the mineralized product, so that the purity of the mineralized product is affected, and the mineralized product is limited in application; on the other hand, heavy metal Mn which affects the recycling utilization of electrolytic manganese slag is not recycled in the whole mineralization process 2+ The treatment is carried out, so that the water is transferred into mineralized filtrate or mineralized solid products, thereby not only limiting the application of the solid products, but also improving the treatment cost of the filtrate; the whole mineralization process has higher economic and environmental cost.
Up to now, no neutral salt is used as an auxiliary agent, and electrolytic manganese slag is used as a raw material for mineralizing CO 2 Relevant reports of a technology for cooperatively solidifying heavy metal ions.
Disclosure of Invention
The invention aims to solve the defects existing in the prior artAt least one of (a) and (b). For example, one of the purposes of the invention is to provide a method for recycling CO from electrolytic manganese slag while realizing low-carbon production in electrolytic manganese industry by using neutral salt as an auxiliary agent 2 Mineralizing and high-value utilizing electrolytic manganese slag to mineralize CO 2 A method for co-curing metal ions and mineralized products.
To achieve the above object, an aspect of the present invention provides an electrolytic manganese slag mineralizing CO 2 Co-curing metal ions Mn 2+ /Mg 2+ The method comprising the steps of:
mixing electrolytic manganese slag powder and neutral salt solution according to a preset liquid-solid ratio, and leaching at a first temperature and a first stirring rotation speed for a first period of time to obtain a first solid-liquid mixture;
filtering the first solid-liquid mixture to obtain leaching liquid and leaching slag of electrolytic manganese slag;
mixing the leaching solution with concentrated ammonia water according to a predetermined ratio, and introducing CO at a first rate 2 Stirring the gas at a second temperature for reacting for a second period of time to obtain a second solid-liquid mixture;
filtering the second solid-liquid mixture to obtain a filter cake and filtrate; and (5) washing and drying the filter cake to obtain a mineralized product.
In an exemplary embodiment of an aspect of the present invention, the method may further include the steps of:
the filtrate obtained by suction filtration of the second solid-liquid mixture is used for leaching electrolytic manganese slag powder instead of the neutral salt solution circularly until the concentration of calcium ions in the leaching solution is lower than 0.03g/100mL;
and recovering ammonium sulfate and neutral salt auxiliary agent from the filtrate after the circulation is completed by evaporation and crystallization.
In an exemplary embodiment of an aspect of the present invention, the concentration of the neutral salt solution may be 1 to 6mol/L, and the liquid-solid ratio of the neutral salt solution to the electrolytic manganese slag powder may be 3 to 20:1mL/g, the first temperature may be room temperature to 100 ℃, and the first period of time may be 30 to 180 minutes.
One exemplary aspect of the inventionIn the embodiment, the volume ratio of the leaching solution to the concentrated ammonia water is 12-60: 1mL/mL mixing, introducing CO 2 The first rate of gas may be 50-200 mL/min, the second temperature may be 20-100deg.C, and the second time period may be 30-180 min;
the concentration of the ammonia water may be 25 to 28%.
In an exemplary embodiment of an aspect of the present invention, the electrolytic manganese slag powder may be obtained by drying, crushing and ball milling the electrolytic manganese slag raw material.
In an exemplary embodiment of an aspect of the present invention, the electrolytic manganese slag raw material may include industrial solid waste generated after acid leaching of rhodochrosite in the electrolytic manganese metal production process or CaSO-containing raw material generated when acid leaching-electrolysis process is used for producing electrolytic manganese using pyrolusite or the like as raw material 4 ·2H 2 Acid leaching slag of O.
In an exemplary embodiment of an aspect of the invention, the imported CO 2 The gas may include CO released during the acid leaching of rhodochrosite 2 CO-containing gases, or emissions from coal-fired flue gases 2 Or CO of technical grade purity 2 And (3) gas.
In an exemplary embodiment of an aspect of the present invention, the electrolytic manganese slag powder may have a particle size of 80 to 200 mesh;
the neutral salt solution may include one or more of an ammonium acetate solution, an ammonium chloride solution, a sodium acetate solution, and a sodium chloride solution.
In a further aspect the invention provides a mineralized product which can mineralize CO by electrolytic manganese slag as described in any one of the preceding 2 Co-curing metal ions Mn 2+ /Mg 2+ Obtained by the method of (2).
In an exemplary embodiment of another aspect of the invention, the mineralized product may be in the form of a mixture of one or more of vaterite, calcite, aragonite, and of the formula (Ca, mn) CO 3 、(Ca，Mg)CO 3 The whiteness of the mineralized product can be 97-99.6.
Compared with the prior art, the beneficial effects of the invention can comprise at least one of the following:
(1) The invention uses electrolytic manganese slag and CO released in the electrolytic manganese slag forming process 2 As raw materials, neutral salt is used as an auxiliary agent to realize CO of electrolytic manganese slag 2 And obtaining light calcium carbonate; realizes low-carbon production in electrolytic manganese industry, simultaneously utilizes electrolytic manganese slag as a resource, and aims at CO 2 Emission reduction, resource protection, conservation and high-value utilization, and has important ecological and sustainable development significance;
(2) The invention realizes the mineralization of CO by the electrolytic manganese slag 2 Simultaneously and cooperatively solidifying heavy metal ion Mn which seriously affects the recycling utilization of electrolytic manganese slag 2+ The method comprises the steps of carrying out a first treatment on the surface of the Has important environmental significance for the green development of mineralization process;
(3) The mineralization process provided by the invention uses neutral salt as an auxiliary agent, so that the economic cost is low, and the equipment corrosion is low; the whole process realizes the recycling and recovery of the auxiliary agent; for CO 2 The low cost development of mineral carbonation fixing techniques is of great importance.
Drawings
The foregoing and other objects and/or features of the invention will become more apparent from the following description taken in conjunction with the accompanying drawings in which:
FIG. 1 shows the XRD patterns of mineralized products prepared according to example 1 of the present invention;
FIG. 2 shows an SEM image of a mineralized product prepared according to example 1 of the invention;
FIG. 3 shows an EDS spectrum of the mineralized product prepared according to example 1 of the present invention;
FIG. 4 shows the XRD patterns of mineralized products prepared according to example 2 of the present invention;
FIG. 5 shows an SEM image of a mineralized product prepared according to example 2 of the present invention;
FIG. 6 shows an EDS spectrum of the mineralized product prepared according to example 2 of the present invention;
FIG. 7 shows the XRD patterns of mineralized products prepared according to example 3 of the present invention;
FIG. 8 shows an SEM image of a mineralized product prepared according to example 3 of the invention;
FIG. 9 shows an EDS spectrum of the mineralized product prepared according to example 3 of the present invention;
FIG. 10 shows the XRD patterns of mineralized products prepared according to example 4 of the present invention;
FIG. 11 shows the XRD patterns of the evaporated crystalline product of the circulating filtrate obtained in example 4 of the present invention;
FIG. 12 shows an SEM image of a mineralized product prepared according to example 4 of the invention;
fig. 13 shows EDS patterns of mineralized products prepared according to example 4 of the present invention.
Detailed Description
Hereinafter, the electrolytic manganese slag mineralization CO of the present invention will be described in detail with reference to exemplary embodiments 2 A method for co-curing metal ions and mineralized products.
In a first exemplary embodiment of the present invention, an electrolytic manganese slag mineralized CO is provided 2 Co-curing metal ions Mn 2+ /Mg 2+ The method comprising the steps of:
the neutral salt solution and the electrolytic manganese slag powder are mixed according to a preset liquid-solid ratio, and then leached for a first period of time at a first temperature and a first stirring rotation speed, so as to obtain a first solid-liquid mixture. Here, the particle size of the electrolytic manganese slag powder may be 80 to 200 mesh, for example, 100 mesh, 150 mesh, 190 mesh, etc. The neutral salt solution may include one or more of an ammonium acetate solution, an ammonium chloride solution, a sodium acetate solution, and a sodium chloride solution.
And carrying out suction filtration on the first solid-liquid mixture to obtain leaching liquid and leaching slag of the electrolytic manganese slag. The leached slag can be used for producing building material products such as cement, building blocks and the like after being washed.
Mixing the leaching solution with concentrated ammonia water according to a predetermined ratio, and introducing CO at a first rate 2 The gas is stirred at a second temperature for a second period of time to obtain a second solid-liquid mixture.
Filtering the second solid-liquid mixture to obtain a filter cake and filtrate; and (5) washing and drying the filter cake to obtain a mineralized product.
In this exemplary embodiment, the method may further include the steps of:
the filtrate obtained by suction filtration of the second solid-liquid mixture is used for leaching electrolytic manganese slag powder instead of the neutral salt solution circularly until the concentration of calcium ions in the leaching solution is lower than 0.03g/100mL; and (3) recovering ammonium sulfate and neutral salt auxiliary agent from the filtrate after the circulation is completed by evaporation and crystallization.
In the present exemplary embodiment, the concentration of the neutral salt solution may be 1 to 6mol/L, for example, 2mol/L, 3mol/L, 5mol/L, etc. The neutral salt solution and the electrolytic manganese slag powder can be mixed according to a liquid-solid ratio of 3-20: 1mL/g, e.g., 5:1mL/g, 10:1mL/g, 15:1mL/g, etc. The first temperature may be room temperature to 100 ℃, for example, 30 ℃,50 ℃, 70 ℃, 90 ℃, etc. The first period of time may be 30 to 180 minutes, for example, 50 minutes, 80 minutes, 150 minutes, etc. The first stirring rotation speed can be 120-240 r/min, for example, 150r/min, 200r/min, 220r/min, etc.
In the present exemplary embodiment, the volume ratio of the leachate to the concentrated ammonia water may be 12 to 60:1mL/mL mix, e.g., 15:1mL/mL, 20:1mL/mL, 30:1mL/mL, 40:1mL/mL, 50:1mL/mL, etc. The CO is introduced into 2 The first rate of gas may be 50 to 200mL/min, e.g., 80mL/min, 120mL/min, 180mL/min, etc. The second temperature may be 20 to 100 ℃, for example, 30 ℃,50 ℃, 70 ℃, 90 ℃, etc. The second time period may be 30 to 180 minutes, for example, 50 minutes, 80 minutes, 150 minutes, etc. The concentration of the aqueous ammonia may be 25 to 28%, for example, 26%, 27%, or the like.
In this exemplary embodiment, the electrolytic manganese slag powder may be obtained by drying, crushing and ball milling the electrolytic manganese slag raw material. Further, the electrolytic manganese slag raw material can comprise industrial solid waste generated after the acid leaching of rhodochrosite in the production process of electrolytic manganese metal or CaSO (soluble organic phase shift keying) generated when pyrolusite and the like are used as raw materials to produce electrolytic manganese by adopting an acid leaching-electrolysis process 4 ·2H 2 Acid leaching slag of O.
In the present exemplary embodiment, the imported CO 2 The gas may include CO released during the acid leaching of rhodochrosite 2 CO-containing gases, or emissions from coal-fired flue gases 2 Is used for the gas mixture of the (a),or CO of technical grade purity 2 And (3) gas.
In a second exemplary embodiment of the present invention, a mineralized product is provided that can mineralize CO by electrolytic manganese slag as described in the first exemplary embodiment above 2 Co-curing metal ions Mn 2+ /Mg 2+ Obtained by the method of (2).
In the present exemplary embodiment, the mineralized product may be in the form of a mixture of one or more of vaterite, calcite, aragonite. The mineralized product may have the chemical formula (Ca, mn) CO 3 、(Ca，Mg)CO 3 The whiteness of the mineralized product can be 97 to 99.6, e.g., 98, 99, etc.
For a better understanding of the above-described exemplary embodiments of the present invention, they are further described below in conjunction with specific examples.
Example 1
Placing 20g of electrolytic manganese slag sample into a 250mL conical flask, adding 200mL of 5mol/L ammonium acetate solution into the conical flask, placing the conical flask into a shaking table, reacting at a rotation speed of 180r/min for 70min, and performing suction filtration to obtain filtrate for later CO 2 After the filter cake is cleaned, the filter cake is continuously used as a raw material for CaSO 4 ·2H 2 Leaching of O to CaSO 4 ·2H 2 O is completely leached and then will not contain CaSO 4 ·2H 2 And (3) cleaning filter residues of O, and drying at 40 ℃ for later use.
400mL of the Ca was taken 2+ Pouring the leaching solution into a 500mL beaker, adding 15mL of concentrated ammonia water into the beaker, placing the beaker into a water bath kettle with stirring, and introducing industrial-grade CO into the solution at a rate of 120mL/min 2 Stirring and reacting for 60min at room temperature, filtering, stirring at 120r/min, washing filter cake, and oven drying at 105deg.C to obtain mineralized product calcium carbonate, mn in the product 2+ Content of 3.62%, mg 2+ 0.53% of the total content of the product, and 98.3% of whiteness; the carbonatation filtrate is circularly used for electrolytic manganese slag or CaSO in electrolytic manganese slag leaching slag 4 ·2H 2 O is leached, after 6 times of cyclic utilization, the concentration of calcium ions in the leaching solution is 0.013g/100mL, and the leaching solution is evaporated and crystallized for 72 hours at 60 ℃ and returnedAmmonium acetate and a small amount of ammonium sulfate are recovered.
FIG. 1 shows the XRD patterns of mineralized products prepared according to example 1 of the present invention; FIG. 2 shows an SEM image of a mineralized product prepared according to example 1 of the invention; FIG. 3 shows an EDS spectrum of the mineralized product prepared according to example 1 of the present invention.
As can be seen from fig. 1, the mineralized product obtained in example 1 has calcite as a phase, and diffraction peaks of calcite are relatively sharp, which indicates that the crystallization degree of calcite crystals is relatively good; no diffraction peaks of other crystals were found except calcite, indicating a higher purity of the mineral product, whose phase was the only calcite.
As can be seen from fig. 2 and 3, calcite, a mineralized product obtained in example 1, was in the form of granules, and the fine granules were combined into irregularly large granules; the mineralized product is found to contain a certain amount of magnesium and manganese in addition to calcium carbonate through energy spectrum analysis; wherein Mn is 2+ Content of 3.62%, mg 2+ Is 0.53%; the analysis shows that the calcium ion leaching solution successfully realizes the Mn heavy metal in the mineralization process 2+ 、Mg 2+ Is cured.
Example 2
Placing 20g of electrolytic manganese slag sample into a 250mL conical flask, adding 300mL of 4mol/L ammonium chloride solution into the conical flask, placing the conical flask into a shaking table, reacting at a rotation speed of 240r/min for 160min, and performing suction filtration to obtain filtrate for later CO 2 After the filter cake is cleaned, the filter cake is continuously used as a raw material for CaSO 4 ·2H 2 Leaching of O to CaSO 4 ·2H 2 O is completely leached and then will not contain CaSO 4 ·2H 2 And (3) cleaning filter residues of O, and drying at 40 ℃ for later use.
500mL of the Ca was taken 2+ Pouring the leaching solution into a 600mL beaker, adding 25mL of concentrated ammonia water into the beaker, placing the beaker into a water bath kettle with stirring, and introducing industrial-grade CO into the solution at a rate of 180mL/min 2 Stirring gas at 100deg.C for 90min, vacuum filtering, stirring at 150r/min, washing filter cake, oven drying at 105deg.C to obtain mineralized product mixture of aragonite and calcite, mn in the product 2+ 25.86% of the content of Mg 2+ The content of (2) is 1.53 percent, and the whiteness is 98.7 percent; mineralized filtrate is recycled to be used for electrolytic manganese slag or CaSO in electrolytic manganese slag leaching slag 4 ·2H 2 O is leached, after 4 times of cyclic utilization, the concentration of calcium ions in the leaching solution is 0.008g/100mL, and the leaching solution is evaporated and crystallized at 60 ℃ for 96 hours to recover ammonium chloride and ammonium sulfate.
FIG. 4 shows the XRD patterns of mineralized products prepared according to example 2 of the present invention; FIG. 5 shows an SEM image of a mineralized product prepared according to example 2 of the present invention; fig. 6 shows EDS patterns of mineralized products prepared according to example 2 of the present invention.
As can be seen from fig. 5 and 6, the main phase of the mineralized product obtained in example 2 was calcite, and a large number of diffraction peaks of aragonite were present in the product in addition to calcite, indicating that the crystalline phase of the mineralized product was a mixture of calcite and aragonite. The phase of the mineralized product was changed compared to example 1, indicating that the crystalline form of the mineralized product could be regulated by the adjustment of the process conditions.
As can be seen from fig. 4, calcite, a mineralized product obtained in example 2, was in a regular rhombohedral shape with relatively complete crystal development; the aragonite is fibrous, has a microscopic diameter of 200-500nm and an aspect ratio of 10-100; the fibrous aragonite and rhombohedral calcite are interwoven. The mineralized product is found to contain a certain amount of magnesium and manganese in addition to calcium carbonate through energy spectrum analysis; wherein Mn is 2+ 25.86% of the content of Mg 2+ 1.53% of (C); the analysis shows that the calcium ion leaching solution successfully realizes the Mn heavy metal in the mineralization process 2+ 、Mg 2+ Is cured.
Example 3
Placing 20g of electrolytic manganese slag sample into a 250mL conical flask, adding 200mL of 2mol/L ammonium chloride solution and 200mL of 2mol/L sodium chloride solution into the conical flask, placing the conical flask into a shaking table, reacting at room temperature for 90min at a shaking table rotating speed of 240r/min, and performing suction filtration to obtain filtrate which is used for later CO 2 After the filter cake is cleaned, the filter cake is continuously used as a raw material for CaSO 4 ·2H 2 Leaching of O to CaSO 4 ·2H 2 O is completely leached and then will not contain CaSO 4 ·2H 2 Washing the residue of O, oven drying at 40deg.C, and preparingIs used.
400mL of the Ca was taken 2+ Pouring the leaching solution into a 500mL beaker, adding 20mL of concentrated ammonia water into the beaker, placing the beaker into a water bath kettle with stirring, and introducing industrial-grade CO into the solution at a rate of 200mL/min 2 Stirring gas at 60deg.C for 60min, vacuum filtering at stirring speed of 150r/min, cleaning filter cake, and oven drying at 105deg.C to obtain mineralized vaterite product, mn in the product 2+ Content of 8.58%, mg 2+ 1.18% of (C) and 97.5% of whiteness; the carbonatation filtrate is circularly used for electrolytic manganese slag or CaSO in electrolytic manganese slag leaching slag 4 ·2H 2 O is leached, after 3 times of cyclic utilization, the concentration of calcium ions in the leaching solution is 0.004g/100mL, and the leaching solution is evaporated and crystallized for 144 hours at 50 ℃ to recover ammonium chloride, sodium chloride and ammonium sulfate.
FIG. 7 shows the XRD patterns of mineralized products prepared according to example 3 of the present invention; FIG. 8 shows an SEM image of a mineralized product prepared according to example 3 of the invention; fig. 9 shows EDS patterns of mineralized products prepared according to example 3 of the present invention.
As can be seen from fig. 7, the mineralized product obtained in example 3 was vaterite, and the diffraction peak of vaterite was sharp, indicating that the degree of crystallization of vaterite crystals was good; no diffraction peaks were found for crystals other than vaterite, indicating a higher purity of mineralized product, whose phase was the only vaterite.
As can be seen from fig. 8 and 9, the mineralized product vaterite obtained in example 3 was in a regular spherical shape and the crystal development was more complete; spherical vaterite of different diameters interweave with each other; it can be seen from the figure that there is a small amount of rhombohedral particles in addition to vaterite. The mineralized product is found to contain a certain amount of magnesium and manganese in addition to calcium carbonate through energy spectrum analysis; wherein Mn is 2+ Content of 8.58%, mg 2+ 1.18% of (C); the analysis shows that the calcium ion leaching solution successfully realizes the Mn heavy metal in the mineralization process 2+ 、Mg 2+ Is cured.
Example 4
50kg of electrolytic manganese slag sample is taken and placed in a 500L stainless steel reaction kettle, 400L of 4mol/L ammonium chloride solution is added into the reaction kettle,placing a stirring rod into a stainless steel reaction kettle, enabling the rotation speed of the stirring rod to be 240r/min, reacting for 4 hours at 60 ℃, then performing filter pressing by using a plate filter press, and using filtrate for later CO 2 After the filter cake is cleaned, the filter cake is continuously used as a raw material for CaSO 4 ·2H 2 Leaching of O to CaSO 4 ·2H 2 O is completely leached and then will not contain CaSO 4 ·2H 2 And (3) cleaning filter residues of O, and naturally drying in the shade for later use.
400L of the Ca is taken 2+ Pouring the leaching solution into a 500L stainless steel reaction kettle, adding 25L of concentrated ammonia water into the stainless steel reaction kettle, and introducing industrial-grade CO into the solution at a rate of 20L/h 2 Stirring and reacting 4L of filter pressing at room temperature, stirring at 150r/min, washing filter cake, and drying at 105 ℃ to obtain mineralized product aragonite-calcite mixture, wherein Mn is contained in the product 2+ 11.52% of Mg 2+ 2.44% of the total content of the product, 97.3% of whiteness; the carbonatation filtrate is circularly used for electrolytic manganese slag or CaSO in electrolytic manganese slag leaching slag 4 ·2H 2 O is leached, after 5 times of cyclic utilization, the concentration of calcium ions in the leaching solution is 0.024g/100mL, 1000mL of the leaching solution is taken and evaporated and crystallized at 50 ℃ for 96 hours to recover ammonium chloride and ammonium sulfate.
FIG. 10 shows the XRD patterns of mineralized products prepared according to example 4 of the present invention; FIG. 11 shows the XRD patterns of the evaporated crystalline product of the circulating filtrate obtained in example 4 of the present invention; FIG. 12 shows an SEM image of a mineralized product prepared according to example 4 of the invention; fig. 13 shows EDS patterns of mineralized products prepared according to example 4 of the present invention.
As can be seen from fig. 10, the mineralized product obtained in example 4 had calcite as a phase, and diffraction peaks of calcite were sharp, indicating that the crystallinity of calcite crystals was good; no diffraction peaks of other crystals are found except calcite, which indicates that the mineralized product has higher purity and the phase is the only calcite phase. As can be seen from fig. 11, the main phase of the product obtained by evaporating and crystallizing the circulating filtrate is ammonium chloride, and a small amount of ammonium sulfate is also contained, so that the recovery of the auxiliary agent is successfully realized.
As can be seen from FIGS. 12 and 13, calcite, a mineralized product obtained in example 4, was irregularly granular but crystallineThe breeding is complete; the calcite crystals of the different particles are interwoven together. The mineralized product is found to contain a certain amount of magnesium and manganese in addition to calcium carbonate through energy spectrum analysis; wherein Mn is 2+ 11.52% of Mg 2+ 2.44%; the analysis shows that the calcium ion leaching solution successfully realizes the Mn heavy metal in the mineralization process 2+ 、Mg 2+ Is cured.
In summary, the beneficial effects of the present invention may include at least one of the following:
(1) The invention uses electrolytic manganese slag and CO released in the electrolytic manganese slag forming process 2 As raw materials, neutral salt is used as an auxiliary agent to realize CO of electrolytic manganese slag 2 And obtaining light calcium carbonate; realizes low-carbon production in electrolytic manganese industry, simultaneously utilizes electrolytic manganese slag as a resource, and aims at CO 2 Emission reduction, resource protection, conservation and high-value utilization, and has important ecological and sustainable development significance;
(2) The invention realizes the mineralization of CO by the electrolytic manganese slag 2 Simultaneously and cooperatively solidifying heavy metal ion Mn which seriously affects the recycling utilization of electrolytic manganese slag 2+ The method comprises the steps of carrying out a first treatment on the surface of the Has important environmental significance for the green development of mineralization process;
(3) The mineralization process provided by the invention uses neutral salt as an auxiliary agent, so that the economic cost is low, and the equipment corrosion is low; the whole process realizes the recycling and recovery of the auxiliary agent; for CO 2 The low cost development of mineral carbonation fixing techniques is of great importance.
Although the invention has been described above in connection with exemplary embodiments, it will be apparent to those of ordinary skill in the art that various modifications can be made to the above-described embodiments without departing from the spirit and scope of the claims.
Claims (10)
1. Mineralized CO of electrolytic manganese slag 2 Co-curing metal ions Mn 2+ /Mg 2+ Is characterized in that it comprises the steps of:
mixing electrolytic manganese slag powder and neutral salt solution according to a preset liquid-solid ratio, and leaching at a first temperature and a first stirring rotation speed for a first period of time to obtain a first solid-liquid mixture;
filtering the first solid-liquid mixture to obtain leaching liquid and leaching slag of electrolytic manganese slag;
mixing the leaching solution with concentrated ammonia water according to a predetermined ratio, and introducing CO at a first rate 2 Stirring the gas at a second temperature for reacting for a second period of time to obtain a second solid-liquid mixture;
filtering the second solid-liquid mixture to obtain a filter cake and filtrate; and (5) washing and drying the filter cake to obtain a mineralized product.
2. Electrolytic manganese slag mineralization of CO according to claim 1 2 Co-curing metal ions Mn 2+ /Mg 2+ Wherein said method further comprises the steps of:
the filtrate obtained by suction filtration of the second solid-liquid mixture is used for leaching electrolytic manganese slag powder instead of the neutral salt solution circularly until the concentration of calcium ions in the leaching solution is lower than 0.03g/100mL;
and recovering ammonium sulfate and neutral salt auxiliary agent from the filtrate after the circulation is completed by evaporation and crystallization.
3. Electrolytic manganese slag mineralization of CO according to claim 1 2 Co-curing metal ions Mn 2+ /Mg 2+ The method is characterized in that the concentration of the neutral salt solution is 1-6 mol/L, and the liquid-solid ratio of the neutral salt solution to the electrolytic manganese slag powder is 3-20: 1mL/g, wherein the first temperature is between room temperature and 100 ℃, and the first time period is between 30 and 180 minutes.
4. Electrolytic manganese slag mineralization of CO according to claim 1 2 Co-curing metal ions Mn 2+ /Mg 2+ The method is characterized in that the volume ratio of the leaching solution to the concentrated ammonia water is 12-60: 1mL/mL mixing, introducing CO 2 The first rate of the gas is 50-200 mL/min, the second temperature is 20-100 ℃, and the second time period is 30-180 min;
the concentration of the strong ammonia water is 25-28%.
5. Electrolytic manganese slag mineralization of CO according to claim 1 2 Co-curing metal ions Mn 2+ /Mg 2+ The method is characterized in that the electrolytic manganese slag powder is obtained by drying, crushing and ball milling pretreatment of electrolytic manganese slag raw materials.
6. Electrolytic manganese slag mineralization of CO according to claim 5 2 Co-curing metal ions Mn 2+ /Mg 2+ The method is characterized in that the electrolytic manganese slag raw material comprises industrial solid waste generated after the acid leaching of rhodochrosite in the production process of electrolytic manganese metal or CaSO-containing raw material generated when pyrolusite and the like are used as raw materials to produce electrolytic manganese by adopting acid leaching-electrolysis process 4 ·2H 2 Acid leaching slag of O.
7. Electrolytic manganese slag mineralization of CO according to claim 1 2 Co-curing metal ions Mn 2+ /Mg 2+ The method is characterized in that the introduced CO 2 The gas comprises CO released in the acid leaching process of rhodochrosite 2 CO-containing gases, or emissions from coal-fired flue gases 2 Or CO of technical grade purity 2 And (3) gas.
8. Electrolytic manganese slag mineralization of CO according to claim 1 2 Co-curing metal ions Mn 2+ /Mg 2+ The method is characterized in that the granularity of the electrolytic manganese slag powder is 80-200 meshes;
the neutral salt solution comprises one or more of ammonium acetate solution, ammonium chloride solution, sodium acetate solution and sodium chloride solution.
9. Mineralized product, characterized in that it is mineralized CO by means of an electrolytic manganese slag according to any one of claims 1-8 2 Co-curing metal ions Mn 2+ /Mg 2+ Is a square of (2)Obtained by the method.
10. The mineralization product according to claim 9, wherein the mineralization product is in the form of a mixture of one or more of vaterite, calcite, aragonite, and having the chemical formula (Ca, mn) CO 3 、(Ca，Mg)CO 3 The whiteness of mineralized products is 97-99.6.
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Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB387439A (en) * | 1930-11-12 | 1933-02-09 | Hoesch Koelnneuessen Ag Fuer B | Improvements in and relating to the treatment of basic phosphate slags |
| WO1998036102A1 (en) * | 1997-02-17 | 1998-08-20 | Buka Technologies Pty. Ltd. | Refining zinc sulphide ores |
| US20110139628A1 (en) * | 2008-05-30 | 2011-06-16 | Aalto University Foundation | Method of producing calcium carbonate from waste and byproducts |
| CN102260797A (en) * | 2011-07-22 | 2011-11-30 | 湘潭电化集团有限公司 | Production process for reclaiming manganese from manganese-containing waste water and waste slag by using waste gas |
| US20130336859A1 (en) * | 2010-10-26 | 2013-12-19 | Bahman Tavakkoli | Production of high purity precipitated calcium carbonate |
| CN105417584A (en) * | 2015-12-09 | 2016-03-23 | 西南科技大学 | Method for recycling manganese from electrolyzed manganese ore residues |
| CN106119556A (en) * | 2016-06-27 | 2016-11-16 | 李果 | A kind of Application way of steel plant zinc smoke ash |
| CN106636667A (en) * | 2016-12-23 | 2017-05-10 | 中南大学 | Method for recycling manganese and silver from manganese-silver ores |
| CN107128963A (en) * | 2017-07-10 | 2017-09-05 | 长江师范学院 | A kind of method for the spherical ball aragonite calcium carbonate that utilization electroslag prepared sizes distribution is concentrated |
| CN109004307A (en) * | 2018-08-14 | 2018-12-14 | 深圳市华慧品牌管理有限公司 | The recyclable device of valuable metal in waste and old nickel cobalt manganese lithium ion battery |
| CN113046558A (en) * | 2021-02-09 | 2021-06-29 | 广东省科学院稀有金属研究所 | Method for recovering lead and calcium in electrolytic manganese slag |
| CN113321224A (en) * | 2021-06-30 | 2021-08-31 | 北京科技大学 | Resource utilization electrolytic manganese slag and solidified CO2Method (2) |
| CN113800546A (en) * | 2021-09-28 | 2021-12-17 | 中国科学院山西煤炭化学研究所 | CO (carbon monoxide)2Method for preparing micro-nano calcium carbonate by mineralizing calcium-containing solid waste residues |
| US20220024778A1 (en) * | 2018-12-04 | 2022-01-27 | Aalto University Foundation Sr | Method of extracting and carbonating calcium from alkaline industrial waste or by-product materials |
| CN114293035A (en) * | 2021-12-28 | 2022-04-08 | 中国科学院过程工程研究所 | Method for preparing calcium carbonate by enriching vanadium from vanadium-containing steel slag |
-
2022
- 2022-12-07 CN CN202211564989.XA patent/CN116173703A/en active Pending
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB387439A (en) * | 1930-11-12 | 1933-02-09 | Hoesch Koelnneuessen Ag Fuer B | Improvements in and relating to the treatment of basic phosphate slags |
| WO1998036102A1 (en) * | 1997-02-17 | 1998-08-20 | Buka Technologies Pty. Ltd. | Refining zinc sulphide ores |
| US20110139628A1 (en) * | 2008-05-30 | 2011-06-16 | Aalto University Foundation | Method of producing calcium carbonate from waste and byproducts |
| US20130336859A1 (en) * | 2010-10-26 | 2013-12-19 | Bahman Tavakkoli | Production of high purity precipitated calcium carbonate |
| CN102260797A (en) * | 2011-07-22 | 2011-11-30 | 湘潭电化集团有限公司 | Production process for reclaiming manganese from manganese-containing waste water and waste slag by using waste gas |
| CN105417584A (en) * | 2015-12-09 | 2016-03-23 | 西南科技大学 | Method for recycling manganese from electrolyzed manganese ore residues |
| CN106119556A (en) * | 2016-06-27 | 2016-11-16 | 李果 | A kind of Application way of steel plant zinc smoke ash |
| CN106636667A (en) * | 2016-12-23 | 2017-05-10 | 中南大学 | Method for recycling manganese and silver from manganese-silver ores |
| CN107128963A (en) * | 2017-07-10 | 2017-09-05 | 长江师范学院 | A kind of method for the spherical ball aragonite calcium carbonate that utilization electroslag prepared sizes distribution is concentrated |
| CN109004307A (en) * | 2018-08-14 | 2018-12-14 | 深圳市华慧品牌管理有限公司 | The recyclable device of valuable metal in waste and old nickel cobalt manganese lithium ion battery |
| US20220024778A1 (en) * | 2018-12-04 | 2022-01-27 | Aalto University Foundation Sr | Method of extracting and carbonating calcium from alkaline industrial waste or by-product materials |
| CN113046558A (en) * | 2021-02-09 | 2021-06-29 | 广东省科学院稀有金属研究所 | Method for recovering lead and calcium in electrolytic manganese slag |
| CN113321224A (en) * | 2021-06-30 | 2021-08-31 | 北京科技大学 | Resource utilization electrolytic manganese slag and solidified CO2Method (2) |
| CN113800546A (en) * | 2021-09-28 | 2021-12-17 | 中国科学院山西煤炭化学研究所 | CO (carbon monoxide)2Method for preparing micro-nano calcium carbonate by mineralizing calcium-containing solid waste residues |
| CN114293035A (en) * | 2021-12-28 | 2022-04-08 | 中国科学院过程工程研究所 | Method for preparing calcium carbonate by enriching vanadium from vanadium-containing steel slag |
Non-Patent Citations (6)
| Title |
|---|
| NANFANGWANG等: "Recovery of soluble manganese from electrolyte manganese residue using a combination of ammonia and CO2", HYDROMETALLURGY, vol. 164, 24 June 2016 (2016-06-24), pages 288 - 294, XP029667846, DOI: 10.1016/j.hydromet.2016.06.019 * |
| 卢忠远, 康明, 姜彩荣, 涂铭旌: "利用电石渣制备针叶形碳酸钙的研究", 功能材料, no. 08, 25 April 2006 (2006-04-25), pages 1238 - 1241 * |
| 戴顺喜: "化学", vol. 1, 31 May 1991, 高等教育出版社, pages: 67 - 68 * |
| 杜兵;汝振广;但智钢;王军;: "电解锰渣处理处置技术及资源化研究进展与展望", 桂林理工大学学报, no. 01, 15 February 2015 (2015-02-15), pages 152 - 159 * |
| 杜冬云等: "CO2 回收电解锰渣中可溶性锰的结晶动力学", 中南民族大学学报( 自然科学版), vol. 36, no. 3, 30 September 2017 (2017-09-30), pages 1 - 5 * |
| 杨葵华;黎国兰;罗玲;: "从废旧锌锰电池中制取碳酸锰的工艺研究", 绵阳师范学院学报, no. 02, 15 February 2010 (2010-02-15), pages 57 - 59 * |
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