CN115432724B - Recycling treatment method of magnesium ammonium waste salt - Google Patents
Recycling treatment method of magnesium ammonium waste salt Download PDFInfo
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- CN115432724B CN115432724B CN202211323501.4A CN202211323501A CN115432724B CN 115432724 B CN115432724 B CN 115432724B CN 202211323501 A CN202211323501 A CN 202211323501A CN 115432724 B CN115432724 B CN 115432724B
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- ammonium
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- carbonate
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- 239000002699 waste material Substances 0.000 title claims abstract description 48
- 150000003839 salts Chemical class 0.000 title claims abstract description 46
- JWSMTBMIGYJJJM-UHFFFAOYSA-N magnesium;azane Chemical compound N.[Mg+2] JWSMTBMIGYJJJM-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000004064 recycling Methods 0.000 title claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 37
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011777 magnesium Substances 0.000 claims abstract description 25
- 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 23
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 21
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 21
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 18
- 235000019341 magnesium sulphate Nutrition 0.000 claims abstract description 18
- 238000002386 leaching Methods 0.000 claims abstract description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 13
- 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
- 238000003763 carbonization 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 8
- 239000007789 gas Substances 0.000 claims description 22
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 19
- 239000001095 magnesium carbonate Substances 0.000 claims description 19
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 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 9
- 239000012452 mother liquor Substances 0.000 claims description 9
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002893 slag Substances 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 238000010000 carbonizing Methods 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000009423 ventilation 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
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000010413 mother solution Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 abstract description 24
- 239000011572 manganese Substances 0.000 abstract description 24
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 23
- 230000008901 benefit Effects 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- 238000001953 recrystallisation Methods 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
- 235000002639 sodium chloride Nutrition 0.000 description 33
- 235000014380 magnesium carbonate Nutrition 0.000 description 17
- 230000008569 process Effects 0.000 description 11
- 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
- 239000013078 crystal Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 5
- 239000003337 fertilizer Substances 0.000 description 5
- 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 5
- 239000000203 mixture Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 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
- 229910005965 SO 2 Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000006028 limestone Substances 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
- 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
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000009615 deamination Effects 0.000 description 2
- 238000006481 deamination reaction Methods 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
- 239000007788 liquid Substances 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
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011265 semifinished product Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000004480 active ingredient Substances 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
- 230000009286 beneficial effect 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
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 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
- 238000000746 purification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 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
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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 resource treatment method of magnesium ammonium waste salt, which comprises the following steps: (1) low temperature calcination; (2) carbonization; (3) leaching; (4) removing impurities; (5) cooling and crystallizing; (6) recrystallization. The invention takes magnesium ammonium sulfate waste salt generated by an electrolytic manganese factory as a raw material, and volatile substances generated by thermal reaction of carbonate minerals and magnesium ammonium salt are carbonized to prepare ammonium bicarbonate after being absorbed by water; the solid after thermal reaction is soaked in water, removed with impurities and separated, and the filtrate is used for producing magnesium sulfate. The invention can well separate magnesium and ammonium in the magnesium ammonium waste salt, can obtain two products of ammonium bicarbonate and magnesium sulfate heptahydrate, can utilize intermediate products generated during recycling, and has good economic benefit and environmental protection benefit.
Description
Technical Field
The invention belongs to the field of comprehensive utilization of industrial solid wastes, and particularly relates to a resource treatment method of magnesium ammonium waste salt in an electrolytic manganese production process.
Background
The production process mainly comprises the steps of preparing qualified electrolyte from manganese ore, then carrying out electrolysis to obtain electrolytic manganese, and recycling the electrolyzed anode liquid after acid addition, so that the soluble metal ions in the ore are accumulated in a circulating way, especially magnesium ions reach higher concentration quickly in the circulating process, and are separated out in the form of magnesium ammonium sulfate hexahydrate double salt in the impurity removal stage of the electrolyte to produce 1 ton of electrolytic manganese, and the generated magnesium ammonium waste salt reaches about 1 ton. The waste magnesium ammonium salt also contains about 1-5% of manganese sulfate, meanwhile, due to the property of co-crystallizing the ammonium sulfate and the magnesium sulfate to generate double salt, the double salt is difficult to separate effectively at low cost in a crystallization separation mode, the mixture lacks market demands, the waste salt is not utilized well, and an electrolytic manganese plant needs to spend money for disposal every year.
At present, the disposal and utilization of the magnesium ammonium waste salt mainly comprises the following three methods:
(1) And alkaline substances such as lime, magnesium oxide or sodium hydroxide are adopted to convert ammonium into ammonia gas for evaporation, and meanwhile, 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 method has poor economic benefit, 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 used as active ingredients of the fertilizer, and the proportion of the nitrogen, the phosphorus, the potassium and the magnesium is regulated by adding the potassium, the phosphorus and the nitrogen, so that the compound fertilizer is manufactured. The method has two problems, namely, the waste salt contains manganese, and although manganese is a trace element required by plant generation, not all soil needs manganese, and the application amount of the waste salt is strictly limited as a trace fertilizer; secondly, 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 fertilizer required to be added is large, so that a small electrolytic manganese plant taking manganese carbonate ore as a raw material produces 3 ten thousand tons of waste salt every year, at least 15 ten thousand tons of compound fertilizer can be produced, and development of application market is a great challenge.
(3) Mixing manganese carbonate ore and waste salt, calcining at 550 deg.C and high Wen Xiazuo to obtain semi-finished product mainly containing magnesium sulfate and manganese sulfate, generating mixed gas mainly containing ammonia and sulfur dioxide, two-stage absorbing the mixed gas to prepare ammonium sulfate, and second-stage absorbing to prepare ammonia water, calcining the semi-finished product solid at 1200 deg.C to obtain solid slag mainly containing magnesium oxide and manganese dioxide and SO 2 Gas, and 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 flow is longer, the investment is huge, the energy consumption is higher, the economic benefit is not obvious, and the method is not suitable for the application of a small electrolytic manganese plant.
In summary, for small electrolytic manganese plants, a method for economically and efficiently recycling magnesium ammonium waste salt with simple process is urgently needed, and the aim of clean production is urgently needed in the field of comprehensive utilization of industrial solid waste.
Disclosure of Invention
The invention aims at: the recycling treatment method of magnesium ammonium waste salt with simple process can well separate magnesium and ammonium in the magnesium ammonium waste salt 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 intermediate products generated during recycling can be utilized, so that the recycling treatment method has good economic benefit and environmental protection benefit.
The technical scheme of the invention is as follows:
a resource treatment method of magnesium ammonium waste salt comprises the following steps:
(1) Low temperature calcination: grinding and mixing magnesium ammonium waste salt and carbonate mineral uniformly, introducing gas and heating, and reacting to obtain solid and gas volatile CO 2 、NH 3 And H 2 O；
(2) Carbonizing: collecting the gas volatile matters obtained in the step (1) by using water, performing carbonization reaction on the obtained ammonium carbonate solution, and filtering the reaction product to obtain ammonium bicarbonate solid and ammonium bicarbonate mother liquor;
(3) Leaching: leaching the solid obtained after the reaction in the step (1) by using water, and separating the solid while the solid is hot to obtain calcium sulfate dihydrate slag and filtrate;
(4) Removing impurities: adding a impurity removing reagent into the filtrate obtained in the step (3), and heating to remove impurities and recycle manganese to obtain 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 (5) recrystallizing: recrystallizing the magnesium sulfate heptahydrate solid obtained in the step (5) to obtain an industrial grade magnesium sulfate heptahydrate product and a magnesium sulfate-containing mother solution.
Further, the carbonate mineral in step (1) is a calcium carbonate-or magnesium carbonate-containing ore, specifically magnesite, dolomite or limestone, and more preferably magnesite.
Further, in the step (1), the molar ratio of carbonate mineral carbonate to ammonium contained in magnesium ammonium waste salt 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 ventilation flow of each kilogram of solid is 1.5-50L/min.
Further, in the step (2), the carbonization reaction is carried out after the total ammonia nitrogen content in the ammonium carbonate solution reaches 22-70 g/L, and further, the carbonization reaction is carried out 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 atmospheres, preferably 3.0 to 6.0 atmospheres.
Further, the liquid-solid ratio of the hot leaching in the step (3) is 1-4: 1, more preferably the heat leaching is 2 to 3:1, the leaching temperature is 80-100 ℃, and the cooling crystallization temperature is 0-30 ℃.
Further, the impurity removing agent in the step (4) is magnesium carbonate and hydrogen peroxide.
The principle related to the technical scheme is as follows:
1. heating stage
(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. Gaseous volatile water absorption stage
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
By utilizing the characteristics that magnesium sulfate is easy to dissolve in water, the solubility is extremely obvious along with the temperature change, and calcium sulfate is slightly soluble in water, simultaneously, by utilizing the heat carried by the solid after deamination, magnesium sulfate is leached out by hot water with proper amount of water, and after impurity removal, magnesium sulfate heptahydrate is obtained by 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= Mn, ca, zn, pb and other metal ions)
Fe 3+ +3OH - →Fe(OH) 3 ↓
The invention provides a resource treatment method of magnesium ammonium waste salt, which realizes the resource utilization of the magnesium ammonium waste salt, and specifically comprises the following steps:
1. an inexpensive deamination agent containing magnesium carbonate or calcium carbonate is used,at a lower temperature (typically below 400 ℃), the ammonium in the magnesium ammonium waste salt is converted into an ammonium carbonate solution, and the CO of the electrolytic manganese plant is reused 2 And (3) carbonizing the waste gas to obtain an ammonium bicarbonate product, and simultaneously performing partial carbon emission reduction.
2. The magnesium in the waste salt is used as a magnesium source, the magnesium sulfate heptahydrate product is obtained with low preparation cost, the product quality reaches the industrial primary product, and the magnesium sulfate yield is further improved by adopting the ore containing magnesium carbonate.
3. The whole production process is conventional chemical equipment, relies on electrolytic manganese production, is compact, simple, energy-saving and environment-friendly, generates little waste gas, waste water and waste residue, and does not detect ammonia and SO in tail gas after three-stage water absorption at a set lower ventilation rate 2 Can be directly discharged.
4. Under the optimized reaction condition, can effectively inhibit the decomposition of ammonium sulfate into SO 2 The effective utilization rate of ammonium sulfate is improved, so that the main component of the escaped volatile gas is NH 3 、CO 2 And H 2 O is directly converted into ammonium carbonate by condensation absorption, so that the generation of ammonium carbamate can be avoided.
5. The ammonium bicarbonate mother liquor obtained in the step (2) can be used for manganese precipitation in an electrolytic manganese plant; the calcium sulfate dihydrate slag obtained in the step (3) can be sent to a cement plant to serve as a retarder; the manganese carbonate waste residue containing magnesium and iron obtained in the step (3) can be recycled for the acid leaching process 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, and can also react with the ammonium carbonate solution obtained in the step (2) to obtain magnesium carbonate, and the magnesium carbonate 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 recrystallization step after being purified, and the process can be used for recycling magnesium ammonium waste salt, and the produced intermediate product can be applied to the process and an electrolytic manganese plant, so that good environmental protection benefit is achieved.
In summary, by adopting the technical scheme, the invention has the beneficial effects that:
the invention can well separate magnesium and ammonium in the magnesium ammonium waste salt generated by the electrolytic manganese factory to obtain carbonic acidThe product of ammonium hydrogen and magnesium sulfate heptahydrate only needs to additionally use hydrogen peroxide and carbonate mineral substances in the implementation process, and utilizes CO of an electrolytic manganese plant 2 The waste gas is carbonized, part of carbon emission reduction is carried out, part of mother liquor containing magnesium sulfate generated in the process can be recycled, the other part of mother liquor containing magnesium sulfate and the generated ammonium carbonate solution generate magnesium carbonate to be used as a reagent for removing impurities, the raw materials adopted are low in price, the yield of magnesium sulfate can be further improved, intermediate products generated in the recycling treatment can be utilized, the final product calcium sulfate dihydrate slag can be used as a retarder to be sent to a cement plant, and the ammonium bicarbonate solid and the industrial magnesium sulfate heptahydrate have great market demands, so that the invention has good economic benefit and environmental protection benefit.
Drawings
FIG. 1 is a flow chart of the recycling treatment of magnesium ammonium waste salt.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the particular embodiments described herein are illustrative only and are not intended to limit the invention, i.e., the embodiments described are merely some, but not all, of the embodiments of the invention.
Example 1
1000g of magnesium ammonium waste salt is taken as a raw material, wherein the magnesium content is 6.8%, the ammonium ion content is 8.7%, the manganese content is 0.98%, the water content is 23%, 450g of dolomite powder is taken, the magnesium carbonate content is 27.3%, the calcium carbonate content is 58%, two solids are mixed, the two solids are ground and mixed by a grinder, the mixture is placed in a tube furnace, the reaction temperature is set to be 350 ℃ for calcination, air and water vapor are introduced, the total flow rate of each kilogram of gas is 10L/min, the water vapor content is 10%, the reaction is carried out for 1.5 hours, and the generated volatile gas is carbonized when the total ammonia nitrogen content in the solution is absorbed by water until the total ammonia nitrogen content reaches 30 g/L; the calcined solid is leached by 2L hot water at 90 ℃, 10mL of hydrogen peroxide aqueous solution with the mass fraction of 27.5% and 20g of magnesium carbonate are added into the filtrate to remove impurities, primary crystal prismatic magnesium sulfate heptahydrate is obtained by cooling and crystallization, and industrial grade magnesium sulfate heptahydrate is obtained by recrystallization.
Example 2
1000g of magnesium ammonium waste salt is taken as a raw material, wherein the magnesium content is 6.8%, the ammonium ion content is 8.7%, the manganese content is 0.98%, the water content is 23%, 500g of limestone is taken, the magnesium carbonate content is 2%, the calcium carbonate content is 79%, two solids are mixed, the two solids are ground and mixed by a grinder, the mixture is placed in a tubular furnace, the reaction temperature is set to 400 ℃, air and water vapor are introduced, the total flow rate of each kilogram of gas is 20L/min, the water vapor content is 7.5%, calcination is carried out for 1.5h, and the generated volatile gas is absorbed by water until the total ammonia nitrogen content in the solution reaches 40g/L, and carbonization is carried out; the calcined solid is leached by 2L hot water at 90 ℃, 10mL of hydrogen peroxide aqueous solution with the mass fraction of 27.5% and 20g of magnesium carbonate are added into the filtrate to remove impurities, primary crystal prismatic magnesium sulfate heptahydrate is obtained by cooling and crystallization, and industrial grade magnesium sulfate heptahydrate is obtained by recrystallization.
Example 3
1000g of magnesium ammonium waste salt is taken as a raw material, wherein the magnesium content is 6.8%, the ammonium ion content is 8.7%, the manganese content is 0.98%, the water content is 23%, 400g of magnesite is taken, the magnesium carbonate content is 78%, two solids are mixed and ground by a grinder, the mixture is placed in a tube furnace, the reaction temperature is set to be 450 ℃, air and water vapor are introduced, the total flow rate of each kilogram of gas is 50L/min, the water vapor content is 4%, the calcination is carried out for 1.5h, and the generated volatile gas is absorbed by water until the total ammonia nitrogen content in the solution reaches 50 g/L; the calcined solid is leached by 2L hot water at 90 ℃, 10mL of hydrogen peroxide aqueous solution with the mass fraction of 27.5% and 20g of magnesium carbonate are added into the filtrate to remove impurities, primary crystal prismatic magnesium sulfate heptahydrate is obtained by cooling and crystallization, and industrial grade magnesium sulfate heptahydrate is obtained by recrystallization.
Example 4
Taking 1000g of magnesium ammonium 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%, the water content is 23%, 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 a grinder, placing the mixture into a tube furnace, setting the reaction temperature to be 500 ℃, introducing air, calcining for 2 hours at a gas flow rate of 20L/min per kilogram, absorbing the generated volatile gas by water until the total ammonia nitrogen content in the solution reaches 40g/L, and carbonizing; the calcined solid is leached by 2L hot water at 90 ℃, 10mL of hydrogen peroxide water solution with the mass fraction of 27.5% and 20g of magnesium carbonate are added into the filtrate to remove impurities, primary crystal prismatic magnesium sulfate heptahydrate is obtained by cooling and crystallization, and industrial grade magnesium sulfate heptahydrate is obtained by recrystallization.
For the Mg leaching rate, the ammonium radical removal rate, the ammonium radical residual quantity in the solid and the SO in the absorption liquid in examples 1 to 4 3 2- The content was measured as shown in table 1.
Table 1 results of the tests of examples 1 to 4
* And (3) calculating the leaching rate of Mg: the total magnesium leached (containing crystallized and crystallized magnesium) divided by the total magnesium in the magnesium ammonium waste salt does not account for the magnesium contained in the carbonate ore.
As can be seen from Table 1, the low reaction temperature and the introduction of steam effectively suppressed the side reaction of the decomposition of ammonium sulfate to sulfur dioxide.
Test example 1
The ammonium bicarbonate solution obtained by absorbing water in example 3 was tested for an ammonium content of 61g/L, CO 3 2- (containing HCO) 3- ) Taking 500mL of solution with the content of 109g/L, placing the solution into a high-pressure reaction kettle, introducing CO under the pressure of 3.5 atmospheres 2 ，CO 2 The flow rate is 2.5L/min, and the reaction is carried out for 120min, so as to obtain 205g of acicular ammonium bicarbonate crystals.
Test example 2
500g of primary crystalline magnesium sulfate heptahydrate obtained in example 3 was taken, 100g of water was added, heated to 80 ℃, stirred and dissolved, cooled to 15 ℃, recrystallized to obtain 432g of secondary crystalline magnesium sulfate heptahydrate crystals, and the impurity content in the prepared magnesium sulfate heptahydrate was detected as shown in table 2.
TABLE 2 detection results 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 industrial grade or reagent grade (chemical purity).
In conclusion, the method for recycling the magnesium ammonium waste salt relies on electrolytic manganese production, is compact and simple, saves energy and protects environment, and has good economic benefit and environmental benefit.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (7)
1. The resource treatment method of the magnesium ammonium waste salt is characterized by comprising the following steps of:
(1) Low temperature calcination: grinding and mixing magnesium ammonium waste salt and carbonate mineral uniformly, introducing gas and heating, and reacting to obtain solid and gas volatile CO 2 、NH 3 And H 2 O; the carbonate mineral is an ore containing calcium carbonate or magnesium carbonate;
(2) Carbonizing: collecting the gas volatile matters obtained in the step (1) by using water, performing carbonization reaction on the obtained ammonium carbonate solution, and filtering the reaction product to obtain ammonium bicarbonate solid and ammonium bicarbonate mother liquor;
(3) Leaching: leaching the solid obtained after the reaction in the step (1) by using water, and separating the solid while the solid is hot to obtain calcium sulfate dihydrate slag and filtrate;
(4) Removing impurities: adding a impurity removing reagent into the filtrate obtained in the step (3), and heating to remove impurities to obtain manganese carbonate waste residue containing magnesium and iron and filtrate; the impurity removing reagent is magnesium carbonate and hydrogen peroxide;
(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 (5) recrystallizing: 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 solution.
2. The method for recycling magnesium ammonium waste salt according to claim 1, wherein the molar ratio of carbonate mineral carbonate to ammonium contained in the magnesium ammonium waste salt in the step (1) is 0.50 to 1: 1.
3. the method for recycling magnesium ammonium waste salt according to claim 1, wherein the reaction temperature in the step (1) is 260-500 ℃ and the reaction time is 0.5-3 hours.
4. The method for recycling magnesium ammonium waste salt according to claim 1, wherein 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 ventilation flow per kilogram of solid is 1.5-50L/min.
5. The method for recycling magnesium ammonium waste salt according to 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.
6. The method for recycling magnesium ammonium waste salt according to claim 1, wherein the temperature in the step (2) is 15-30 ℃, and the partial pressure of carbon dioxide is 1.0-10.0 atm.
7. The method for recycling magnesium ammonium waste salt according to claim 1, wherein in the step (3), the liquid-solid ratio is 1-4: 1, leaching temperature is 80-100 ℃, and cooling crystallization temperature is 0-30 ℃.
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