CN115432724A - Resourceful treatment method of waste ammonium magnesium salt - Google Patents
Resourceful treatment method of waste ammonium magnesium salt Download PDFInfo
- Publication number
- CN115432724A CN115432724A CN202211323501.4A CN202211323501A CN115432724A CN 115432724 A CN115432724 A CN 115432724A CN 202211323501 A CN202211323501 A CN 202211323501A CN 115432724 A CN115432724 A CN 115432724A
- Authority
- CN
- China
- Prior art keywords
- ammonium
- magnesium
- carbonate
- waste
- magnesium sulfate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002699 waste material Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 41
- JWSMTBMIGYJJJM-UHFFFAOYSA-N magnesium;azane Chemical compound N.[Mg+2] JWSMTBMIGYJJJM-UHFFFAOYSA-N 0.000 title claims abstract description 39
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000007787 solid Substances 0.000 claims abstract description 33
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 claims abstract description 25
- 229940061634 magnesium sulfate heptahydrate Drugs 0.000 claims abstract description 25
- 239000012535 impurity Substances 0.000 claims abstract description 24
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 19
- 235000019341 magnesium sulphate Nutrition 0.000 claims abstract description 19
- 238000002386 leaching Methods 0.000 claims abstract description 16
- 238000004064 recycling Methods 0.000 claims abstract description 14
- 239000000706 filtrate Substances 0.000 claims abstract description 13
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 12
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 239000000047 product Substances 0.000 claims abstract description 9
- 229910001748 carbonate mineral Inorganic materials 0.000 claims abstract description 7
- 238000010000 carbonizing Methods 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 24
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 17
- 239000001095 magnesium carbonate Substances 0.000 claims description 17
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 239000012452 mother liquor Substances 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 238000003763 carbonization Methods 0.000 claims description 8
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000011656 manganese carbonate Substances 0.000 claims description 4
- 235000006748 manganese carbonate Nutrition 0.000 claims description 4
- 229940093474 manganese carbonate Drugs 0.000 claims description 4
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 4
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- MHKWSJBPFXBFMX-UHFFFAOYSA-N iron magnesium Chemical compound [Mg].[Fe] MHKWSJBPFXBFMX-UHFFFAOYSA-N 0.000 claims description 2
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical group O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims 1
- 125000005587 carbonate group Chemical group 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 abstract description 25
- 239000011572 manganese Substances 0.000 abstract description 25
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 24
- 239000011777 magnesium Substances 0.000 abstract description 24
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052749 magnesium Inorganic materials 0.000 abstract description 20
- 230000008901 benefit Effects 0.000 abstract description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000013067 intermediate product Substances 0.000 abstract description 4
- UGLUPDDGTQHFKU-UHFFFAOYSA-M [NH4+].S(=O)(=O)([O-])[O-].[Mg+] Chemical compound [NH4+].S(=O)(=O)([O-])[O-].[Mg+] UGLUPDDGTQHFKU-UHFFFAOYSA-M 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 15
- 230000008569 process Effects 0.000 description 14
- 150000003839 salts Chemical class 0.000 description 14
- 235000002639 sodium chloride Nutrition 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 6
- 235000011130 ammonium sulphate Nutrition 0.000 description 6
- 239000003337 fertilizer Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical group [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 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 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 235000019738 Limestone Nutrition 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000006028 limestone Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910005965 SO 2 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000010459 dolomite Substances 0.000 description 2
- 229910000514 dolomite Inorganic materials 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 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
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011265 semifinished product Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- YDFGNYADMVZAPO-UHFFFAOYSA-M O.O.O.O.O.O.S(=O)(=O)([O-])[O-].[NH4+].[Mg+] Chemical compound O.O.O.O.O.O.S(=O)(=O)([O-])[O-].[NH4+].[Mg+] YDFGNYADMVZAPO-UHFFFAOYSA-M 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- -1 ammonium ions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- PYLLWONICXJARP-UHFFFAOYSA-N manganese silicon Chemical compound [Si].[Mn] PYLLWONICXJARP-UHFFFAOYSA-N 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- 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
- C01F5/00—Compounds of magnesium
- C01F5/40—Magnesium sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/26—Carbonates or bicarbonates of ammonium
-
- 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
Abstract
The invention discloses a resourceful treatment method of waste ammonium magnesium salt, which comprises the following steps: (1) low-temperature calcination; (2) carbonizing; (3) leaching; (4) removing impurities; (5) cooling and crystallizing; and (6) recrystallizing. The method takes waste ammonium magnesium sulfate salt generated in an electrolytic manganese factory as a raw material, and volatile substances generated by the thermal reaction of carbonate minerals and the ammonium magnesium salt are absorbed by water and carbonized to prepare the ammonium bicarbonate; and (3) soaking the solid after the thermal reaction in water, removing impurities and separating, and using the filtrate for producing magnesium sulfate. The method can well separate magnesium and ammonium in the waste ammonium magnesium salt, can obtain two products of ammonium bicarbonate and magnesium sulfate heptahydrate, can utilize intermediate products generated during resource recycling, and has good economic benefit and environmental protection benefit.
Description
Technical Field
The invention belongs to the field of industrial solid waste comprehensive utilization, and particularly relates to a resourceful treatment method of waste ammonium magnesium salt in an electrolytic manganese production process.
Background
The production process mainly comprises the steps of preparing qualified electrolyte by using manganese ore, then electrolyzing to obtain electrolytic manganese, and recycling the electrolyzed anolyte after acid addition, so that easily soluble metal ions in ores are circularly accumulated, particularly magnesium ions, quickly reach higher concentration in the circulating process, and are separated out in the form of ammonium magnesium sulfate hexahydrate double salt at the impurity removal stage of the electrolyte to produce 1 ton of electrolytic manganese, and the generated ammonium magnesium waste salt reaches about 1 ton. The waste ammonium-magnesium salt also contains about 1-5% of manganese sulfate, and meanwhile, due to the property that ammonium sulfate and magnesium sulfate are co-crystallized to generate double salt, the waste ammonium-magnesium salt is difficult to be effectively separated in a crystallization separation mode at low cost, and the mixture lacks of market demands, so that the waste ammonium-magnesium salt is not well utilized, and an electrolytic manganese factory needs to spend funds to dispose every year.
At present, for the disposal and utilization of the ammonium magnesium waste salt, the following three methods are mainly used:
(1) The ammonium is converted into ammonia gas by using alkaline substances such as lime, magnesium oxide or sodium hydroxide and the like, and the ammonia gas is evaporated, and simultaneously, the magnesium is converted into magnesium sulfate or magnesium hydroxide. The method has the problems that a large amount of alkaline substances are needed, the price of the alkaline substances is high, the economic benefit of the method is poor, the obtained solid contains manganese, and the secondary treatment of the manganese-containing waste residue is difficult;
(2) Ammonium and magnesium in the waste salt are effective components of the fertilizer, and the compound fertilizer is prepared by adding potassium, phosphorus and nitrogen and adjusting the proportion of the nitrogen, the phosphorus, the potassium and the magnesium. The method has two problems, namely, the waste salt contains manganese which is a trace element required by plant growth, but not all soils need manganese, and the application amount of the manganese as a trace element is strictly limited; in the waste salt, magnesium sulfate and ammonium sulfate are main components, magnesium is a medium-amount fertilizer, and the amount of potassium, phosphorus and nitrogen fertilizers required to be added is large, so that 3 ten thousand tons of waste salt is produced in a small electrolytic manganese factory which takes manganese carbonate ore as a raw material, at least more than 15 ten thousand tons of compound fertilizer is produced, and the development of the application market of the compound fertilizer is a great challenge.
(3) Mixing manganese carbonate ore and waste salt, performing primary calcination treatment at 550 ℃ to generate a semi-finished product mainly containing magnesium sulfate and manganese sulfate, simultaneously generating mixed gas mainly containing ammonia and sulfur dioxide, performing two-stage absorption on the mixed gas, preparing ammonium sulfate by the primary absorption, preparing ammonia water by the secondary absorption, and then performing calcination treatment on the semi-finished product solid at the temperature of over 1200 ℃ to generate solid slag mainly containing magnesium oxide and manganese dioxide and SO 2 Gas, then SO 2 The gas is prepared into sulfuric acid, and the obtained solid slag is used for producing the silicon-manganese alloy. The treatment process has the advantages of long process flow, large investment, high energy consumption and unobvious economic benefit, and is not suitable for application in small electrolytic manganese plants.
In summary, for small electrolytic manganese plants, a method for recycling waste ammonium magnesium salt with simple process, economy and high efficiency is urgently needed, and the aim of achieving clean production is urgently needed in the field of comprehensive utilization of industrial solid waste.
Disclosure of Invention
The invention aims to: the recycling method of the waste ammonium-magnesium salt with simple process is provided, magnesium and ammonium in the waste ammonium-magnesium salt can be well separated to obtain two products of ammonium bicarbonate and magnesium sulfate heptahydrate, only hydrogen peroxide is needed to be additionally used for removing impurities in the implementation process, and the intermediate product generated in recycling can be utilized, so that the recycling method has good economic benefit and environmental protection benefit.
The technical scheme of the invention is as follows:
a resource treatment method of waste ammonium magnesium salt comprises the following steps:
(1) And (3) low-temperature calcination: grinding and mixing the waste ammonium magnesium salt and carbonate minerals uniformly, introducing gas for heating, and reacting to obtain solid and gas volatile matter CO 2 、NH 3 And H 2 O；
(2) Carbonizing: collecting the gas volatile matter obtained in the step (1) by using water, carrying out carbonization reaction on the obtained ammonium carbonate solution, and filtering a reaction product to obtain ammonium bicarbonate solid and ammonium bicarbonate mother liquor;
(3) Leaching: hot-dipping the solid obtained after the reaction in the step (1) with water, and separating while hot to obtain calcium sulfate dihydrate residue and filtrate;
(4) Removing impurities: adding an impurity removal reagent into the filtrate obtained in the step (3), and heating to remove impurities and recover manganese to obtain a filtrate;
(5) Cooling and crystallizing: cooling and crystallizing the filtrate obtained in the step (4), and filtering to obtain primary crystallized magnesium sulfate heptahydrate solid and magnesium sulfate-containing mother liquor;
(6) And (3) recrystallization: and (4) recrystallizing the primary crystallized magnesium sulfate heptahydrate solid obtained in the step (5) to obtain an industrial grade magnesium sulfate heptahydrate product and a mother liquor containing magnesium sulfate.
Further, the carbonate mineral in step (1) is an ore containing calcium carbonate or magnesium carbonate, specifically magnesite, dolomite or limestone, and more preferably magnesite.
Further, the molar ratio of the carbonate-containing mineral carbonate to the ammonium contained in the waste ammonium magnesium salt in the step (1) is 0.50-1: 1, more preferably 0.55 to 0.70:1.
further, the reaction temperature in the step (1) is 260 to 500 ℃, more preferably 320 to 450 ℃, and the reaction time is 0.5 to 3 hours.
Further, the gas introduced in the step (1) is air and water vapor, wherein the content of the water vapor is 0-10%, and the total flow of the gas introduced per kilogram of solid is 1.5-50L/min.
Further, carrying out a carbonization reaction after the total ammonia nitrogen content in the ammonium carbonate solution in the step (2) reaches 22-70 g/L, and preferably further carrying out the carbonization reaction after the total ammonia nitrogen content in the ammonium carbonate solution reaches 30-50 g/L.
Further, the temperature in the carbonization in the step (2) is 15 to 30 ℃, and the partial pressure of carbon dioxide is 1.0 to 10.0 atm, preferably 3.0 to 6.0 atm.
Further, the liquid-solid ratio of the hot leaching in the step (3) is 1-4: 1, and further preferably 2 to 3:1, the leaching temperature is 80-100 ℃, and the cooling crystallization temperature is 0-30 ℃.
Further, in the step (4), the impurity removal reagent is magnesium carbonate and hydrogen peroxide.
The principle involved in the above technical scheme is as follows:
1. heating phase
(NH 4 ) 2 SO 4 +MgCO 3 →2NH 3 ↑+CO 2 ↑+MgSO 4 +H 2 O↑
(NH 4 ) 2 SO 4 +CaCO 3 →2NH 3 ↑+CO 2 ↑+CaSO 4 +H 2 O↑
2. Water absorption stage of gaseous volatile
2NH 3 (g)+CO 2 (g)+H 2 O→(NH 4 ) 2 CO 3 (aq)
3. Carbonization stage
(NH 4 ) 2 CO 3 (aq)+CO 2 (g)→2NH 4 HCO 3 ↓
4. Magnesium leaching stage
The magnesium sulfate heptahydrate is obtained by utilizing the characteristics that the magnesium sulfate is easily dissolved in water, the solubility of the magnesium sulfate is very obvious along with the change of temperature, and the calcium sulfate is slightly dissolved in water, simultaneously, utilizing the heat carried by the solid after the ammonium removal, leaching the magnesium sulfate with proper amount of water in hot water, removing impurities, cooling and crystallizing.
5. Impurity removal reaction in magnesium sulfate solution
2Fe 2+ +H 2 O 2 →2Fe 3+ +H 2 O+H +
2H + +MgCO 3 →CO 2 +H 2 O+Mg 2+
M 2+ +MgCO 3 →MCO 3 ↓+Mg 2+ (M = metal ion such as Mn, ca, zn, pb, etc.)
Fe 3+ +3OH - →Fe(OH) 3 ↓
The invention provides a resource treatment method of waste ammonium magnesium salt, which realizes resource utilization of the waste ammonium magnesium salt and specifically comprises the following steps:
1. cheap magnesium or calcium carbonateDeaminating agent, converting ammonium in waste ammonium magnesium salt into ammonium carbonate solution at lower temperature (usually lower than 400 ℃), and reusing CO from electrolytic manganese factory 2 And carbonizing the waste gas to obtain an ammonium bicarbonate product, and simultaneously performing partial carbon emission reduction.
2. Magnesium in the waste salt is used as a magnesium source, a magnesium sulfate heptahydrate product is obtained at low preparation cost, the product quality reaches an industrial first-grade product, and the magnesium sulfate yield is further improved by adopting magnesium carbonate-containing ores.
3. The whole production process is conventional chemical equipment, depends on electrolytic manganese production, is compact and simple, saves energy, protects environment, generates little waste gas, waste water and waste residue, and does not detect ammonia and SO in tail gas after adopting three-level water absorption at a set lower ventilation rate 2 And can be directly discharged.
4. Under the optimized reaction condition, the decomposition of ammonium sulfate into SO can be effectively inhibited 2 The effective utilization rate of the ammonium sulfate is improved, and the main component of the escaped volatile gas is NH 3 、CO 2 And H 2 And O, condensing and absorbing and directly converting into ammonium carbonate, so that the formation of ammonium carbamate can be avoided.
5. The ammonium bicarbonate mother liquor obtained in the step (2) can be used for manganese precipitation in electrolytic manganese plants; the calcium sulfate dihydrate residue obtained in the step (3) can be sent to a cement plant as a retarder; the magnesium-iron-containing manganese carbonate waste residue obtained in the step (3) can be recycled for acid leaching in the electrolytic manganese process; the magnesium sulfate-containing mother liquor obtained in the step (5) can be reused for hot leaching in the step (3) after impurity removal and purification, can also react with the ammonium carbonate solution obtained in the step (2) to obtain magnesium carbonate, and can be used as an impurity removal reagent in the step (3) after heating and washing; the magnesium sulfate-containing mother liquor obtained in the step (6) can be reused in the step of recrystallization after impurity removal and purification, and therefore, the process can be used for resource utilization of waste ammonium magnesium salt, and the generated intermediate product can be applied to the process and an electrolytic manganese plant, so that the process has good environmental protection benefits.
In summary, by adopting the above technical scheme, the beneficial effects of the invention are as follows:
the method can well separate magnesium and ammonium in the waste ammonium magnesium salt generated by the electrolytic manganese plant,obtaining two products of ammonium bicarbonate and magnesium sulfate heptahydrate, only needing to additionally use hydrogen peroxide and carbonate minerals in the implementation process, and utilizing CO of electrolytic manganese plants 2 The waste gas is carbonized, partial carbon emission reduction is carried out, one part of the magnesium sulfate-containing mother liquor generated in the process can be recycled, the other part of the magnesium sulfate-containing mother liquor and the generated ammonium carbonate solution generate magnesium carbonate as an impurity removal reagent, the adopted raw materials are low in price, the yield of magnesium sulfate can be further improved, the generated intermediate products can be utilized during resource treatment, the final product, namely the calcium sulfate dihydrate residue can be used as a retarder and sent to a cement plant, and the ammonium bicarbonate solid and the industrial grade magnesium sulfate heptahydrate have great market demands, so that the method has good economic benefits and environmental protection benefits.
Drawings
FIG. 1 is a process diagram of the process for recycling waste ammonium magnesium salts.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
Taking 1000g of ammonium-magnesium waste salt as a raw material, wherein the magnesium content is 6.8%, the ammonium ion content is 8.7%, the manganese content is 0.98%, and the water content is 23%, taking 450g of dolomite powder, wherein the magnesium carbonate content is 27.3%, and the calcium carbonate content is 58%, mixing the two solids, grinding and mixing the two solids by using a grinder, placing the mixture in a tubular furnace, setting the reaction temperature to 350 ℃ for calcination, introducing air and water vapor, wherein the total flow of each kilogram of gas is 10L/min, the water vapor content is 10%, reacting for 1.5h, and absorbing the generated volatile gas by using water until the total ammonia nitrogen content in the solution reaches 30g/L for carbonization; leaching the calcined solid with 2L hot water at 90 ℃, adding 10mL of 27.5% aqueous hydrogen peroxide and 20g of magnesium carbonate into the filtrate to remove impurities, cooling and crystallizing to obtain primary crystalline prismatic magnesium sulfate heptahydrate, and recrystallizing to obtain industrial magnesium sulfate heptahydrate.
Example 2
Taking 1000g of ammonium-magnesium waste salt as a raw material, wherein the magnesium content is 6.8 percent, the ammonium ion content is 8.7 percent, the manganese content is 0.98 percent, and the water content is 23 percent, taking 500g of limestone, wherein the magnesium carbonate content is 2 percent, and the calcium carbonate content is 79 percent, mixing the two solids by grinding and grinding by a grinder, placing the mixture in a tubular furnace, setting the reaction temperature to be 400 ℃, introducing air and water vapor, wherein the total flow of each kilogram of gas is 20L/min, the water vapor content is 7.5 percent, calcining for 1.5h, absorbing the generated volatile gas by water, and carbonizing when the total ammonia nitrogen content in the solution reaches 40 g/L; leaching the calcined solid with 2L hot water at 90 ℃, adding 10mL of 27.5% aqueous hydrogen peroxide and 20g of magnesium carbonate into the filtrate to remove impurities, cooling and crystallizing to obtain primary crystalline prismatic magnesium sulfate heptahydrate, and recrystallizing to obtain industrial magnesium sulfate heptahydrate.
Example 3
Taking 1000g of waste ammonium-magnesium salt as a raw material, wherein the magnesium content is 6.8%, the ammonium ion content is 8.7%, the manganese content is 0.98%, and the water content is 23%, taking 400g of magnesite, wherein the magnesium carbonate content is 78%, mixing two solids, grinding the two solids by using a grinder, placing the mixture in a tubular furnace, setting the reaction temperature to be 450 ℃, introducing air and water vapor, wherein the total flow rate of each kilogram of gas is 50L/min, the water vapor content is 4%, calcining for 1.5h, absorbing the generated volatile gas by using water, and carbonizing when the total ammonia nitrogen content in the solution reaches 50 g/L; leaching the calcined solid with 2L hot water at 90 ℃, adding 10mL of 27.5 mass percent aqueous hydrogen peroxide and 20g of magnesium carbonate into the filtrate to remove impurities, cooling and crystallizing to obtain primary crystalline prismatic magnesium sulfate heptahydrate, and recrystallizing to obtain industrial magnesium sulfate heptahydrate.
Example 4
Taking 1000g of waste ammonium-magnesium salt as a raw material, wherein the waste ammonium-magnesium salt contains 6.8% of magnesium, 8.7% of ammonium ions, 0.98% of manganese and 23% of water, taking 600g of limestone, wherein the magnesium content is 1.2% and the calcium carbonate content is 79%, mixing the two solids, grinding and mixing the two solids by using a grinder, placing the mixture in a tubular furnace, setting the reaction temperature to be 500 ℃, introducing air, wherein the gas flow per kg is 20L/min, calcining for 2h, absorbing the generated volatile gas by using water, and carbonizing when the total ammonia nitrogen content in the solution reaches 40 g/L; leaching the calcined solid with 2L hot water at 90 ℃, adding 10mL of 27.5% aqueous hydrogen peroxide and 20g of magnesium carbonate into the filtrate to remove impurities, cooling and crystallizing to obtain primary crystalline prismatic magnesium sulfate heptahydrate, and recrystallizing to obtain industrial magnesium sulfate heptahydrate.
The Mg leaching rate, the ammonium radical removal rate, the residual ammonium radical in the solid and the SO in the absorption liquid in examples 1 to 4 were measured 3 2- The content was measured as shown in table 1.
Table 1 test results of examples 1 to 4
* Calculating the Mg leaching rate: the total amount of magnesium leached (including both crystallized and crystallized magnesium) was divided by the total amount of magnesium in the ammonium magnesium waste salt, not counting the magnesium contained in the carbonate ore.
As can be seen from Table 1, the low reaction temperature and the introduction of steam effectively inhibit the side reaction of decomposition of ammonium sulfate to sulfur dioxide.
Test example 1
The ammonium carbonate solution obtained by water absorption in example 3 was tested to have an ammonium content of 61g/L and CO 3 2- (containing HCO) 3- ) The content is 109g/L, 500mL of the solution is put into a high-pressure reaction kettle, and CO is introduced under 3.5 atmospheric pressures 2 ，CO 2 The flow rate is 2.5L/min, the reaction time is 120min, and needle-shaped ammonium bicarbonate crystals 205g are obtained.
Test example 2
500g of the primary crystalline magnesium sulfate heptahydrate obtained in example 3 was taken, 100g of water was added, the mixture was heated to 80 ℃, dissolved by stirring, cooled to 15 ℃, and recrystallized to obtain 432g of secondary crystalline magnesium sulfate heptahydrate crystals, and the impurity content in the prepared magnesium sulfate heptahydrate was measured as shown in Table 2.
TABLE 2 determination of impurity content in magnesium sulfate heptahydrate (%)
As can be seen from Table 2, the magnesium sulfate heptahydrate obtained in example 3 meets the standards of technical grade or reagent grade (chemical purity).
In conclusion, the method for recycling the ammonium magnesium waste salt relies on electrolytic manganese production, is compact and simple, saves energy, protects environment, and has good economic benefit and environmental benefit.
The above description is intended to be illustrative of the preferred embodiment of the present invention and should not be taken as limiting the invention, but rather, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (9)
1. A resource treatment method of waste ammonium magnesium salt is characterized by comprising the following steps:
(1) Low-temperature calcination: grinding and mixing the waste ammonium magnesium salt and carbonate minerals uniformly, introducing gas for heating, and reacting to obtain solid and gas volatile matter CO 2 、NH 3 And H 2 O；
(2) Carbonizing: collecting the gas volatile matter obtained in the step (1) by using water, carrying out carbonization reaction on the obtained ammonium carbonate solution, and filtering a reaction product to obtain ammonium bicarbonate solid and ammonium bicarbonate mother liquor;
(3) Leaching: hot-dipping the solid obtained after the reaction in the step (1) with water, and separating while hot to obtain calcium sulfate dihydrate residue and filtrate;
(4) Removing impurities: adding an impurity removal reagent into the filtrate obtained in the step (3), and heating to remove impurities to obtain magnesium-iron-containing manganese carbonate waste residues and filtrate;
(5) Cooling and crystallizing: cooling and crystallizing the filtrate obtained in the step (4), and filtering to obtain primary crystallized magnesium sulfate heptahydrate solid and magnesium sulfate-containing mother liquor;
(6) And (3) recrystallization: and (4) recrystallizing the primary crystallized magnesium sulfate heptahydrate solid obtained in the step (5) to obtain an industrial grade magnesium sulfate heptahydrate product and a magnesium sulfate-containing mother liquor.
2. The method for recycling waste ammonium magnesium salts according to claim 1, wherein the carbonate mineral in step (1) is an ore containing calcium carbonate or magnesium carbonate.
3. The method for recycling waste ammonium magnesium salts according to claim 1, wherein the carbonate mineral in step (1) contains carbonate groups in a molar ratio of 0.50 to 1:1.
4. the method for recycling waste ammonium magnesium salts according to claim 1, wherein the reaction temperature in step (1) is 260-500 ℃ and the reaction time is 0.5-3 h.
5. A method as claimed in claim 1, wherein the gas introduced in step (1) is air and water vapor, wherein the water vapor content is 0-10%, and the total flow rate of gas introduced per kg solid is 1.5-50L/min.
6. The method for recycling waste ammonium magnesium salts as claimed in claim 1, wherein the carbonization reaction is performed after the total ammonia nitrogen content in the ammonium carbonate solution in the step (2) reaches 22-70 g/L.
7. The method for recycling waste ammonium magnesium salts according to claim 1, wherein the temperature in step (2) is 15 to 30 ℃ and the partial pressure of carbon dioxide is 1.0 to 10.0 atm.
8. The method for recycling waste ammonium magnesium salts according to claim 1, wherein the liquid-solid ratio in step (3) is 1-4: 1, the leaching temperature is 80-100 ℃, and the cooling crystallization temperature is 0-30 ℃.
9. A resource utilization method of waste ammonium magnesium salt according to claim 1, characterized in that in the step (4), the impurity removal reagent is magnesium carbonate and hydrogen peroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211323501.4A CN115432724B (en) | 2022-10-27 | 2022-10-27 | Recycling treatment method of magnesium ammonium waste salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211323501.4A CN115432724B (en) | 2022-10-27 | 2022-10-27 | Recycling treatment method of magnesium ammonium waste salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115432724A true CN115432724A (en) | 2022-12-06 |
| CN115432724B CN115432724B (en) | 2023-11-21 |
Family
ID=84252356
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211323501.4A Active CN115432724B (en) | 2022-10-27 | 2022-10-27 | Recycling treatment method of magnesium ammonium waste salt |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115432724B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115872452A (en) * | 2022-12-27 | 2023-03-31 | 江西赣锋锂业集团股份有限公司 | Method for recovering magnesium and manganese from impurity-removing slag of spodumene leaching solution |
| CN115991496A (en) * | 2023-02-22 | 2023-04-21 | 西南科技大学 | Preparation method of hydrated magnesium ammonium sulfate |
Citations (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB581370A (en) * | 1942-08-19 | 1946-10-10 | Electro Manganese Corp | Improvements in or relating to the electrowinning of manganese |
| GB763451A (en) * | 1952-10-06 | 1956-12-12 | Wintershall Ag | Process for the preparation of easily-filtrable magnesia and ammonium sulphate |
| CN1401573A (en) * | 2002-09-13 | 2003-03-12 | 清华大学 | Method for integrated production of magnesium sulfate, magnesium carbonate and magnesium hydroxide from magnesite |
| CN101215108A (en) * | 2008-01-18 | 2008-07-09 | 沈阳化工学院 | Method for producing series function magnesium chemical products by using magnesite |
| CN101683988A (en) * | 2008-09-23 | 2010-03-31 | 东北大学 | Method for producing series magnesia chemical products by using material containing magnesium |
| CN101760646A (en) * | 2008-12-24 | 2010-06-30 | 中国恩菲工程技术有限公司 | Leaching method of magnesium-containing ore |
| CN102139905A (en) * | 2010-12-30 | 2011-08-03 | 何云 | Method for preparing mixed product of carbonate and magnesium sulfate from manganese-containing waste solution |
| CN103265083A (en) * | 2013-05-27 | 2013-08-28 | 青川县青云上锰业有限公司 | Method for producing feed-grade manganese sulfate monohydrate |
| US20170369329A1 (en) * | 2015-01-14 | 2017-12-28 | Imerys Usa, Inc. | A process for converting natural calcium carbonate into precipitated calcium carbonate |
| CN108396158A (en) * | 2018-02-24 | 2018-08-14 | 宁夏天元锰业有限公司 | A kind of processing method of the complex salt crystal object of electrolytic manganese process |
| CN108483501A (en) * | 2018-07-04 | 2018-09-04 | 绵阳师范学院 | A kind of method of comprehensive utilization of electrolytic manganese residues water lotion |
| CN108842053A (en) * | 2018-07-06 | 2018-11-20 | 中南大学 | The method of comprehensive utilization of Low grade manganese ore and electrolytic manganese crystallization double salt |
| CN108842052A (en) * | 2018-07-06 | 2018-11-20 | 中南大学 | The method of comprehensive utilization of electrolytic manganese anode slag and electrolytic manganese crystallization double salt |
| CN109422284A (en) * | 2017-08-24 | 2019-03-05 | 程相魁 | The integrated processes of flue gas desulfurization and the pollutant resources treatment of wastes with processes of wastes against one another of combustion gas deamination |
| CN109735709A (en) * | 2018-12-13 | 2019-05-10 | 江西赣锋循环科技有限公司 | A kind of method removing calcium and magnesium slag recycling lithium and prepare ternary precursor material |
| CN110655116A (en) * | 2019-10-31 | 2020-01-07 | 青川县青云上锰业有限公司 | Preparation method of agricultural manganese sulfate solution |
| CN111172561A (en) * | 2018-11-13 | 2020-05-19 | 云南创一磷业技术有限公司 | Method for separating magnesium in electrolytic manganese production process |
| CN111394598A (en) * | 2020-03-30 | 2020-07-10 | 龙岩紫云化学科技有限公司 | Method for extracting magnesium and co-producing calcium sulfate from magnesium-containing carbonate ore |
| WO2020181745A1 (en) * | 2019-03-12 | 2020-09-17 | 衢州华友钴新材料有限公司 | Method for efficiently separating cobalt/nickel magnesium manganese from crude cobalt/nickel salt raw material |
| CN111825106A (en) * | 2020-03-16 | 2020-10-27 | 宁夏天元锰业集团有限公司 | Two-stage calcination treatment method for electrolytic manganese metal ammonium sulfate slag |
| CN114804177A (en) * | 2022-04-08 | 2022-07-29 | 中冶南方都市环保工程技术股份有限公司 | Industrial solid waste electrolytic manganese slag mineralized CO 2 Resource utilization method |
-
2022
- 2022-10-27 CN CN202211323501.4A patent/CN115432724B/en active Active
Patent Citations (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB581370A (en) * | 1942-08-19 | 1946-10-10 | Electro Manganese Corp | Improvements in or relating to the electrowinning of manganese |
| GB763451A (en) * | 1952-10-06 | 1956-12-12 | Wintershall Ag | Process for the preparation of easily-filtrable magnesia and ammonium sulphate |
| CN1401573A (en) * | 2002-09-13 | 2003-03-12 | 清华大学 | Method for integrated production of magnesium sulfate, magnesium carbonate and magnesium hydroxide from magnesite |
| CN101215108A (en) * | 2008-01-18 | 2008-07-09 | 沈阳化工学院 | Method for producing series function magnesium chemical products by using magnesite |
| CN101683988A (en) * | 2008-09-23 | 2010-03-31 | 东北大学 | Method for producing series magnesia chemical products by using material containing magnesium |
| CN101760646A (en) * | 2008-12-24 | 2010-06-30 | 中国恩菲工程技术有限公司 | Leaching method of magnesium-containing ore |
| CN102139905A (en) * | 2010-12-30 | 2011-08-03 | 何云 | Method for preparing mixed product of carbonate and magnesium sulfate from manganese-containing waste solution |
| CN103265083A (en) * | 2013-05-27 | 2013-08-28 | 青川县青云上锰业有限公司 | Method for producing feed-grade manganese sulfate monohydrate |
| US20170369329A1 (en) * | 2015-01-14 | 2017-12-28 | Imerys Usa, Inc. | A process for converting natural calcium carbonate into precipitated calcium carbonate |
| CN109422284A (en) * | 2017-08-24 | 2019-03-05 | 程相魁 | The integrated processes of flue gas desulfurization and the pollutant resources treatment of wastes with processes of wastes against one another of combustion gas deamination |
| CN108396158A (en) * | 2018-02-24 | 2018-08-14 | 宁夏天元锰业有限公司 | A kind of processing method of the complex salt crystal object of electrolytic manganese process |
| CN108483501A (en) * | 2018-07-04 | 2018-09-04 | 绵阳师范学院 | A kind of method of comprehensive utilization of electrolytic manganese residues water lotion |
| CN108842052A (en) * | 2018-07-06 | 2018-11-20 | 中南大学 | The method of comprehensive utilization of electrolytic manganese anode slag and electrolytic manganese crystallization double salt |
| CN108842053A (en) * | 2018-07-06 | 2018-11-20 | 中南大学 | The method of comprehensive utilization of Low grade manganese ore and electrolytic manganese crystallization double salt |
| CN111172561A (en) * | 2018-11-13 | 2020-05-19 | 云南创一磷业技术有限公司 | Method for separating magnesium in electrolytic manganese production process |
| CN109735709A (en) * | 2018-12-13 | 2019-05-10 | 江西赣锋循环科技有限公司 | A kind of method removing calcium and magnesium slag recycling lithium and prepare ternary precursor material |
| WO2020181745A1 (en) * | 2019-03-12 | 2020-09-17 | 衢州华友钴新材料有限公司 | Method for efficiently separating cobalt/nickel magnesium manganese from crude cobalt/nickel salt raw material |
| CN110655116A (en) * | 2019-10-31 | 2020-01-07 | 青川县青云上锰业有限公司 | Preparation method of agricultural manganese sulfate solution |
| CN111825106A (en) * | 2020-03-16 | 2020-10-27 | 宁夏天元锰业集团有限公司 | Two-stage calcination treatment method for electrolytic manganese metal ammonium sulfate slag |
| CN111394598A (en) * | 2020-03-30 | 2020-07-10 | 龙岩紫云化学科技有限公司 | Method for extracting magnesium and co-producing calcium sulfate from magnesium-containing carbonate ore |
| CN114804177A (en) * | 2022-04-08 | 2022-07-29 | 中冶南方都市环保工程技术股份有限公司 | Industrial solid waste electrolytic manganese slag mineralized CO 2 Resource utilization method |
Non-Patent Citations (3)
| Title |
|---|
| HONGLIANG CHEN ET AL.: "Simultaneous immobilization of NH4 + and Mn2+ from electrolytic manganese residue using phosphate and magnesium sources", 《RSC ADVANCES》, no. 8, pages 4583 * |
| 杨葵华等: "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》, vol. 29, no. 2, pages 57 - 59 * |
| 熊雪良: "电解金属锰硫酸盐体系除镁技术研究进展", 《中国锰业》, vol. 34, no. 1, pages 5 - 8 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115872452A (en) * | 2022-12-27 | 2023-03-31 | 江西赣锋锂业集团股份有限公司 | Method for recovering magnesium and manganese from impurity-removing slag of spodumene leaching solution |
| CN115991496A (en) * | 2023-02-22 | 2023-04-21 | 西南科技大学 | Preparation method of hydrated magnesium ammonium sulfate |
| CN115991496B (en) * | 2023-02-22 | 2024-04-30 | 西南科技大学 | Preparation method of hydrated magnesium ammonium sulfate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115432724B (en) | 2023-11-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115432724B (en) | Recycling treatment method of magnesium ammonium waste salt | |
| CN102421707B (en) | Process for simultaneous production of potassium sulphate, ammonium sulfate, magnesium hydroxide and/or magnesium oxide from kainite mixed salt and ammonia | |
| US9169125B2 (en) | Method for producing high-purity lithium carbonate | |
| CN103395796B (en) | Comprehensive utilization method of serpentine and device used by method | |
| CN106517621B (en) | Recycling process of ammonium chloride-containing wastewater | |
| CN110304646B (en) | Method for efficiently separating fluorine, chlorine and nitrogen components from aluminum ash and co-producing aluminum oxide concentrate | |
| CN101760641B (en) | Technology for recovering magnesium from magnesium sulfate solution | |
| CN113025832B (en) | Nickel extraction and CO mineralization from laterite-nickel ore2Method (2) | |
| CN108330298B (en) | Method for extracting rubidium, cesium, lithium and potassium from polymetallic mica ore | |
| CN107814370B (en) | Circulating environment-friendly process method for preparing phosphate concentrate, product and application thereof | |
| CN113651342A (en) | Method for producing lithium product by processing lepidolite through nitric acid atmospheric pressure method | |
| JP5086021B2 (en) | Recovery method of rare earth elements | |
| KR101944518B1 (en) | Manufacturing method of high-concentration lithium solution from lithium carbonate | |
| CN101760646A (en) | Leaching method of magnesium-containing ore | |
| CN110217769B (en) | Method for producing calcium ammonium nitrate byproduct feed-grade DCP | |
| CN101760638B (en) | Method for recovering magnesium from magnesium sulfate solution | |
| CN101760637A (en) | Leaching technology of magnesium-containing ore | |
| CN102328947A (en) | Method for recovering strontium slag | |
| WO2001028925A1 (en) | Formulation of potassium sulfate, sodium carbonate and sodium bicarbonate from potash brine | |
| WO2023173776A1 (en) | Recovery method and recovery system for ternary precursor mother liquor | |
| CN101760643B (en) | Improved method for recovering magnesium from magnesium sulfate solution | |
| CN111533099B (en) | Production method of water-soluble monoammonium phosphate | |
| CN101760644B (en) | Leaching technique for magnesium-containing ore | |
| CN101760642B (en) | Process for recovering magnesium from magnesium sulfate solution | |
| RU2560359C2 (en) | Calcification method of producing lithium carbonate from lithium-bearing material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |