CN114686702A - Method for purifying magnesium from serpentine normal-pressure sulfuric acid leaching solution in one pot - Google Patents
Method for purifying magnesium from serpentine normal-pressure sulfuric acid leaching solution in one pot Download PDFInfo
- Publication number
- CN114686702A CN114686702A CN202210356080.9A CN202210356080A CN114686702A CN 114686702 A CN114686702 A CN 114686702A CN 202210356080 A CN202210356080 A CN 202210356080A CN 114686702 A CN114686702 A CN 114686702A
- Authority
- CN
- China
- Prior art keywords
- magnesium
- pot
- reaction
- serpentine
- sulfuric acid
- 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
- 239000011777 magnesium Substances 0.000 title claims abstract description 102
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 85
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 70
- 238000005580 one pot reaction Methods 0.000 title claims abstract description 66
- 238000002386 leaching Methods 0.000 title claims abstract description 49
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 title claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 45
- 230000003647 oxidation Effects 0.000 claims abstract description 29
- 238000000926 separation method Methods 0.000 claims abstract description 20
- 230000001590 oxidative effect Effects 0.000 claims abstract description 19
- 239000007800 oxidant agent Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 230000001105 regulatory effect Effects 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 54
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 52
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 31
- 239000000347 magnesium hydroxide Substances 0.000 claims description 31
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 31
- 229910052759 nickel Inorganic materials 0.000 claims description 24
- 229910052804 chromium Inorganic materials 0.000 claims description 17
- 229910052748 manganese Inorganic materials 0.000 claims description 17
- 239000000395 magnesium oxide Substances 0.000 claims description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 12
- 238000000746 purification Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 230000002431 foraging effect Effects 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000003518 caustics Substances 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 238000006757 chemical reactions by type Methods 0.000 abstract description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 3
- 239000011707 mineral Substances 0.000 abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 58
- 238000011084 recovery Methods 0.000 description 55
- 238000001914 filtration Methods 0.000 description 30
- 229910052742 iron Inorganic materials 0.000 description 27
- 239000011651 chromium Substances 0.000 description 25
- 239000011572 manganese Substances 0.000 description 23
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 15
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 235000021110 pickles Nutrition 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000003723 Smelting Methods 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000002893 slag Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 2
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 description 2
- 229910052898 antigorite Inorganic materials 0.000 description 2
- 229910052620 chrysotile Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000011112 process operation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- CWBIFDGMOSWLRQ-UHFFFAOYSA-N trimagnesium;hydroxy(trioxido)silane;hydrate Chemical compound O.[Mg+2].[Mg+2].[Mg+2].O[Si]([O-])([O-])[O-].O[Si]([O-])([O-])[O-] CWBIFDGMOSWLRQ-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- -1 Cr and the like Chemical compound 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 229910052599 brucite Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 229910052899 lizardite Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- IBPRKWGSNXMCOI-UHFFFAOYSA-N trimagnesium;disilicate;hydrate Chemical compound O.[Mg+2].[Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IBPRKWGSNXMCOI-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
- C22B26/22—Obtaining magnesium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/32—Obtaining chromium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Metallurgy (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to the field of mineral resource utilization, and particularly discloses a method for purifying magnesium from a serpentine normal-pressure sulfuric acid leaching solution in one pot, which comprises the steps of carrying out one-pot three-section reaction treatment on the leaching solution obtained by the serpentine normal-pressure sulfuric acid leaching, and then carrying out solid-liquid separation to obtain a purified magnesium solution; the one-pot three-section reaction process comprises the following steps: regulating pH of the leachateA2.0-3.0, adding an oxidant to carry out first-stage oxidation treatment; subsequent control of the pH of the SystemBAdding an oxidant to 4.5-6, and performing second-stage oxidation treatment; readjusting the pH of the SystemCCarrying out a third stage of reaction after the reaction reaches 7-8 ℃; one-pot three-sectionIn the reaction process, the temperature of the first stage oxidation reaction and the second stage oxidation reaction is 60-80 ℃, and the temperature of the third stage oxidation reaction is 80-90 ℃. Under the one-pot three-section treatment process, the invention is matched with the joint control of the reaction type, the pH value and the temperature of each section, can realize the cooperation, can effectively separate magnesium and each ion with high selectivity in one pot, and is beneficial to obtaining high-purity magnesium solution.
Description
Technical Field
The invention relates to the field of comprehensive utilization of resources, in particular to a serpentine wet-process pure magnesium method.
Background
Serpentine is a generic name of water-containing magnesium-rich silicate minerals, and its chemical composition is 3 mgo.2sio2·2H2O, dark greenish, brown or yellow, mostly speckled, named after the polished surface like a serpentine, has a hardness of 2 to 3.5 and a density of 2.2 to 3.69/cm3. The crystal structure is a double-layer structure formed by combining a layer of silicon-oxygen tetrahedron and a layer of brucite octahedron in a ratio of 1: 1. Serpentine can be generally classified into three groups according to mineral structure: (1) chrysotile (Chrysotile) having a cylindrical structure; (2) lizardlite (Lizardite) with a smooth structure; (3) antigorite (Antigorite) having an alternating wavelike structure. All serpentine minerals, whether fibrous or not, are layered structures, similar to kaolinite. Six-fold coordinated Mg in ore2+Can be A13+、Ni2+、Fe2+、Fe3+、Mn2+And the like, particularly in the case of aluminum serpentine (zoblitzite), nickel serpentine (gamierite), and iron serpentine (greenallte). General snakeThe veined stones contain a small amount of metals such as iron, aluminum, chromium, nickel, cobalt, manganese, and the like. Therefore, serpentine is an important potential resource of nickel and cobalt.
Hydrometallurgy of serpentine is a main means of resource utilization, and hydrometallurgy processes related in the industry at present mainly include hydrochloric acid leaching process, high-pressure sulfuric acid leaching process and normal-pressure sulfuric acid leaching process. The hydrochloric acid leaching process has mild leaching condition, small equipment investment and the Cl-The method can effectively destroy the colloid stability, reduce the solution viscosity and is beneficial to operation and separation, but because the hydrochloric acid is volatile and has high cost, the method has higher requirement on the recovery of the hydrochloric acid and is not beneficial to industrial large-scale application. The high-pressure sulfuric acid leaching process is usually applied to smelting treatment of serpentine ore with high nickel grade, can effectively control leaching of iron and is usually used for extracting nickel in serpentine; however, the high-temperature leaching process has high energy consumption, high cost and high requirement on ore grade. Compared with the high-pressure sulfuric acid leaching process, the normal-pressure sulfuric acid leaching process is commonly used for smelting low-grade serpentine, the leaching selectivity is not ideal, the leaching solution has multiple metal ions and has the characteristics of high iron, high magnesium, low nickel and the like, the element separation difficulty of the leaching solution obtained by the process is high, and SO is added4 2-The colloid structure is difficult to damage, the colloid is easy to form in the leaching and purifying impurity removing stages, the operation is difficult, the slag amount generated in the impurity removing process is large, and the leaching solution contains SO4 2-And the purification difficulty of valuable elements such as nickel, magnesium and the like is high.
Aiming at the element recovery of the low-grade sulfuric acid normal-pressure leachate, the main means in the industry is classified recovery step by step, for example, the publication number is CN103395796A, a comprehensive utilization method of serpentine is disclosed, and the steps are as follows: leaching serpentine with sulfuric acid, and filtering to obtain a first filtrate; adding an oxidant to the first filtrate; adding a pH value regulator to perform precipitation reaction, and filtering to obtain an iron-aluminum mixture and a second filtrate; adding water and sodium hydroxide into the iron-aluminum mixture, and filtering to obtain an iron precipitate and a sodium metaaluminate solution; adding sulfide into the second filtrate for reaction, and filtering to obtain a nickel-cobalt mixture and a third filtrate; adding an oxidant into the third filtrate for reaction; then adding an alkaline adsorbent, filtering to obtain a magnesium sulfate solution, and adding ammonia water to prepare the magnesium hydroxide.
For smelting of low-grade serpentine sulfuric acid normal-pressure leachate, the industry mostly carries out multi-step separation process classification smelting, the process is low in treatment efficiency and low in process operability, and the recovery rate of target elements and the product purity need to be improved.
Disclosure of Invention
The invention aims to provide a method for purifying magnesium from a serpentine normal-pressure sulfuric acid leaching solution (also referred to as leaching solution for short) by one pot, and aims to provide a method for selectively separating magnesium ions and other ions in the leaching solution and improving the recovery rate and purity of magnesium.
In consideration of treatment value, the low-grade serpentine is recovered by a sulfuric acid normal-pressure acid leaching process, the leachate obtained by the process is a sulfuric acid system with high iron, high magnesium, low nickel and rich trace impurity elements, and the leachate of the type is difficult to realize one-pot separation and recovery of magnesium, and mainly comprises the following steps: (1) the system is a high-iron sulfuric acid system, the solution is easy to form colloid, the sulfate ions are difficult to damage the colloid structure, the separation and recovery of magnesium and other components are influenced, and the process operation difficulty is large, for example, the filtration is difficult; (2) in the system, abundant metal impurity components exist, and the components are difficult to realize one-pot high-selectivity separation with magnesium; (3) the recovery rate, purity and whiteness of magnesium are not ideal. Aiming at the problem that the one-pot high-selectivity separation of the serpentine sulfuric acid normal-pressure acid leaching solution is difficult to realize, the invention provides the following improved process:
a method for purifying magnesium from a serpentine normal-pressure sulfuric acid leaching solution (also referred to as acid leaching solution for short) in one pot comprises the steps of carrying out one-pot three-section reaction treatment on the leaching solution subjected to the serpentine normal-pressure sulfuric acid leaching, and then carrying out solid-liquid separation to obtain a purified magnesium solution;
fe, Cr, Mn and Mg are dissolved in the leachate;
the one-pot three-section reaction process comprises the following steps: regulating and controlling the pH of the leachateA2.0 to 3.0, adding oxidationCarrying out first-stage oxidation treatment on the agent; subsequent control of the pH of the SystemBAdding an oxidant to 4.5-6, and performing second-stage oxidation treatment; readjusting the pH of the SystemCCarrying out a third stage of reaction after the reaction reaches 7-8 ℃;
in the process of one-pot three-section reaction, the temperature of the first-section oxidation reaction and the second-section oxidation reaction is 60-80 ℃, and the temperature of the third-section reaction is 80-90 ℃.
Aiming at the problems that the magnesium is difficult to purify in one pot and the technical operation difficulty is high due to the component characteristics of the normal-pressure sulfuric acid leaching solution, the invention innovatively provides a method for realizing the synergy by matching the combined control of the reaction type, the pH value and the temperature of each section under the one-pot and three-section treatment process, can solve the problem that the impurity elements and the magnesium are difficult to separate in one pot at high selectivity due to a normal-pressure acid leaching system, high iron, high impurity elements and a sulfuric acid system, can effectively separate the magnesium and each ion at high selectivity in one pot, is beneficial to obtaining a high-purity magnesium solution, and can also effectively improve the problem of poor manufacturability (such as poor filtering property) in the leaching solution treatment process in one pot, and is actually amplified by the industry.
The research of the invention finds that the three-stage reaction process of the first-stage oxidation, the second-stage oxidation and the third-stage reaction under the one-pot system and the combined control of the pH and the temperature of each stage reaction are the key points for synergistically solving the problem that the normal-pressure leachate is difficult to treat in one pot and improving the magnesium extraction and purification effects.
In the invention, the pickle liquor is obtained by pickling low-grade serpentine with sulfuric acid at normal pressure.
In the invention, the leachate is sulfuric acid pickle liquor of serpentine under normal pressure. The concentration of the sulfuric acid is, for example, 2 to 5 mol.L-1. The temperature of the normal pressure acid leaching is, for example, 80 to 100 ℃, and preferably 80 to 95 ℃.
In the invention, the leaching solution is a sulfuric acid system with high iron, low nickel and high magnesium. The concentrations are, for example: the concentration of Fe is 5-18 g/L; the concentration of Mn (II) is 0.2-0.5 g/L, Cr (III), the concentration is 0.10-0.40 g/L, Mg, and the concentration is 50-65 g/L. Further preferably, the concentration of Fe is 6-12 g/L; the concentration of Mn (II) is 0.12-0.4 g/L, Cr (III), the concentration of Mn (II) is 0.20-0.4 g/L, Mg, and the concentration of Mn (II) is 50-65 g/L. The technical scheme of the invention can show better industrial application value for one-pot treatment of the leachate, but does not exclude the application of the method of the invention to other leachate.
In the invention, the pickle liquor also contains at least one of nickel, cobalt and aluminum; wherein, in the leaching solution, the concentration of Ni is 0.20-0.6 g/L; the concentration of Co is 0.01-0.04 g/L; the concentration of Al is 0.2-2 g/L; further preferably, the concentration of Ni is, for example, 0.30 to 0.6 g/L; the concentration of Co is, for example, 0.02-0.03 g/L; the concentration of Al is 0.3-1.8 g/L. The technical scheme of the invention can realize one-pot high-selectivity separation of magnesium, iron, manganese, chromium, nickel, aluminum and cobalt in a sulfuric acid system, and has excellent magnesium smelting effect and efficiency.
In the invention, in the one-pot three-section treatment process, the pH value of the system is regulated and controlled by adopting an alkaline substance, such as at least one of magnesium oxide, alkali metal hydroxide, calcium oxide and ammonia water. The alkaline substance may be added in the form of solid or solution.
In the invention, in the one-pot three-stage treatment process, the oxidant is at least one of chlorate, oxygen or hydrogen peroxide.
In the invention, alkaline substances are added into the normal-pressure leaching solution in advance, and the pH of the system is regulated to the required pHAAnd introducing an oxidant at the required temperature of 60-80 ℃ to perform first-stage oxidation treatment in a one-pot reaction. The research of the invention finds that at the temperature and the pH value, the nucleation behavior and the morphology of the iron can be regulated and controlled unexpectedly, so that the separation selectivity of magnesium, iron and other elements in a one-pot system can be further improved unexpectedly, and the processing performance of one-pot treatment can be improved.
In the first stage of oxidation reaction, the dosage of the oxidant is 1.2-1.5 times of the theoretical molar weight for oxidizing Fe in the system. Preferably, the pH isAIs 2.0 to 3.0. The temperature of the first stage oxidation treatment is preferably 60 to 70 ℃, and more preferably 60 to 65 ℃.
In the invention, the time of the first stage oxidation treatment is preferably 0.5-1.0 h.
In the invention, after the first-stage oxidation treatment, the pH of the system is directly regulated and controlled to be pH without carrying out solid-liquid separationBAnd introducing an oxidant at the required temperature of 60-80 ℃ to perform second-stage oxidation treatment in the one-pot reaction. The research of the invention finds that under the synergistic premise of the first stage oxidation treatment, the selective oxidation of Mn in the system can be realized by further matching with the combined control of the process and the temperature of the second stage oxidation treatment, the concomitant oxidation of Cr in the system is avoided, and thus the invention can be combined with the first oxidation reaction to synergistically improve the one-pot separation selectivity of magnesium and other components and improve the one-pot separation recovery rate and purity of magnesium.
Preferably, in the second oxidation reaction stage, the amount of the oxidant is 1.2-1.5 times of the theoretical molar amount for oxidizing Mn in the system into Mn (IV).
In the invention, the temperature in the second-stage oxidation reaction process is preferably 60-70 ℃.
Preferably, the pH isB5.0 to 6.0.
Preferably, the time of the second stage oxidation reaction is 0.5-1.0 h.
In the invention, after the second stage of oxidation treatment, solid-liquid separation is not carried out, and the pH of the system is directly regulated and controlled to be pHCAnd carrying out the third stage reaction at the required temperature of 80-90 ℃, realizing the selective precipitation of other ions except magnesium, such as Cr and the like, and improving the nucleation behavior, thus being capable of unexpectedly and synergistically improving the separation effect of magnesium and other ions, improving the recovery rate and purity of magnesium and improving the enrichment effect of other elements in slag.
Preferably, the pH isCIs 7.0 to 8.0.
Preferably, the time of the third stage reaction is 2.0-3.0 h.
According to the invention, cooperation can be realized by matching with the combined control of the pH and the temperature of each section under the one-pot three-section reaction, so that the control of the nucleation behavior and the morphology of elements under the one-pot system is facilitated, and the morphology of the slag constructed under the condition can cooperate with the subsequent conditions to induce the nucleation selectivity of other elements, so that the control of the separation selectivity of Mg and other components is facilitated, the improvement of the recovery rate and the purity of magnesium is facilitated, and not only is the filtration difficulty reduced, and the process operability improved.
In the present invention, the magnesium solution may be treated by a known means. For example, a precipitant is added to a magnesium solution to carry out a magnesium precipitation reaction, thereby obtaining magnesium hydroxide.
The precipitant is at least one of ammonia water and alkali metal hydroxide, for example. The precipitant is in the form of a solution having a concentration of, for example, 1 mol. L-1～13mol·L-1。
Preferably, the pH value of the magnesium precipitation reaction process and the reaction end point is 8.8-9.5;
preferably, the temperature of the magnesium precipitation reaction process is 70-80 ℃;
preferably, the magnesium precipitation reaction time is 1-2 h.
In the invention, magnesium hydroxide is placed in alkali liquor for aging treatment, and then the magnesium hydroxide is subjected to solid-liquid separation and washing to prepare purified magnesium hydroxide;
preferably, the alkali liquor is an aqueous solution of alkali metal hydroxide, and the preferable concentration of the solute is 0.2 mol.L-1～0.5mol·L-1；
Preferably, the temperature for aging is 70 ℃ to 80 ℃;
preferably, the aging time is 60-120 min.
The invention discloses a preferable method for preparing high-purity magnesium hydroxide by using leachate, which comprises the following steps:
(1) adding alkaline substances into the serpentine sulfuric acid leaching solution, and regulating and controlling the pH of the system to be 2.0-3.0; then adding an oxidant, and carrying out a first-stage reaction at the temperature of 60-70 ℃; then, continuously adding alkaline substances without filtering until the pH value of the system is 4.5-6.0, adding an oxidant, and carrying out second-stage oxidation treatment at the temperature of 50-60 ℃; after treatment, filtering is not needed, alkaline substances are supplemented until the pH value of the system is 7.0-8.0, and heat preservation is carried out at 80-90 ℃ for third-stage reaction; after a subsequent filtration, a pure magnesium sulfate solution was obtained.
(2) Adding a certain amount of precipitator into the magnesium sulfate solution obtained after filtration at a certain temperature, and carrying out magnesium precipitation reaction. Controlling the pH value of the reaction process to be 8.8-9.5 and the temperature to be 70-80 ℃; the time is 1-2 h, and then the filtration is carried out to obtain Mg (OH)2. The magnesium sulfate solution and the precipitator in the step (2) are added in a bidirectional dropping mode.
(3) Washing the magnesium hydroxide with hot water for 3-5 times.
(4) Adding a sodium hydroxide solution with a certain concentration into magnesium hydroxide for reaction, filtering and washing, controlling the reaction temperature to be 70-80 ℃, and the reaction time to be 60-120 min, so as to obtain a high-purity magnesium hydroxide product meeting the quality standard.
Compared with the prior art, the invention has the following advantages and beneficial effects:
aiming at the problems that the extraction liquid component characteristics of the serpentine normal-pressure sulfuric acid leaching are difficult to realize magnesium purification in one pot and the process operation difficulty is large, the invention innovatively provides that under the one-pot three-section treatment process, the cooperation of the reaction type, the pH and the temperature of each section is realized, the cooperation can be realized, the problem that the magnesium is difficult to separate from the magnesium in one pot at high selectivity caused by high iron and rich impurity elements of a normal-pressure acid leaching system can be solved, the magnesium and each ion can be effectively separated at high selectivity in one pot, the high-purity magnesium solution is obtained, the recovery rate of the magnesium and the enrichment recovery rate of other components in slag are improved, and the method can also effectively improve the problem of poor manufacturability (such as poor filterability) in the extraction liquid one-pot treatment process and is actually amplified by industry.
Drawings
FIG. 1 is an XRD pattern of the product of example 1;
FIG. 2 is an SEM image of the product of example 1;
the specific implementation mode is as follows:
the technical scheme of the application is explained in detail by combining the following embodiments:
according to the chemical industry standard HG/T3607-2007 of industrial magnesium hydroxide, the industrial magnesium hydroxide can be divided into three types:
class I: used mainly as raw material of flame retardant, [ Mg (OH) ]2]Mass fraction/% > is more than or equal to 97.5;
and II: mainly used as raw materials for producing magnesium oxide and magnesium salt; [ Mg (OH)2]Mass fraction/% > or more than 93
Class III: the method is mainly used for flue desulfurization, wastewater treatment, agricultural fertilizers, soil conditioners and the like; [ Mg (OH)2]The mass fraction/% > or more than 92.
Therefore, the Mg (OH) produced by the process of the invention2The purity requirement of the product meets the I-type standard of the industry.
The acid leaching solution is obtained by leaching low-grade serpentine with sulfuric acid under normal pressure, and the concentration (g.L) of main elements in the serpentine normal-pressure sulfuric acid leaching solution-1)：Mg 60，Fe 12.89，Al 1.54，Cr(III)0.33，Co(II)0.025，Mn(II)0.40，Ni(II)0.55。
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not used as limitations of the present invention.
Example 1:
step (1): one-pot treatment:
the pH of the serpentine leachate (pickle liquor) was adjusted to 300mL using a 10% MgO slurryAWhen the temperature is adjusted to 2.0, sodium chlorate with 1.3 times of the iron content is added, and the temperature is kept at 60 ℃ for the first-stage oxidation treatment for 30 minutes; without filtration, the pH of the leachate is continuously adjusted by using 10% MgO slurryBWhen the temperature is adjusted to 5.5 ℃, introducing oxygen (1.3 times of the molar weight of manganese), and carrying out second-stage oxidation treatment for 30 minutes at the temperature of 70 ℃; without filtration, the pH was adjusted by continued use of a 10% MgO slurryCKeeping the temperature to 7.0 ℃, and carrying out a third-stage reaction for 2 hours at 80 ℃;
after the treatment of one pot and three sections is finished, filtering is carried out, and the filtering speed is 12mg/min cm2The content of nickel in the filtrate after filtration is 0.13 mg.L-1The content of cobalt is 0.07 mg.L-1The content of manganese is 0.43 mg.L-1ICP was not measured due to the very low levels of chromium and iron; in the slag of the methodThe recovery rate of iron is more than 99.99 percent, the recovery rate of nickel is 99.97 percent, the recovery rate of manganese is 99.87 percent, the recovery rate of chromium is more than 99.99 percent, and the loss rate of magnesium is less than 0.7 percent.
Step (2): magnesium deposition and aging:
dropwise adding ammonia water into the purified solution to perform precipitation reaction, wherein the reaction temperature is 70 ℃, and the pH values of the reaction process and the reaction end point are 8.9; the reaction time is 1.0h, and Mg (OH) is obtained by filtering and washing2Washing the resulting Mg (OH)2Using 0.10 mol.L-1NaOH was aged (temperature 70 ℃ C.) for 1.0 h. The sulfur content of the magnesium hydroxide was 0.17%, the total recovery rate of magnesium was 80%, no Cr element was detected in the magnesium hydroxide, the purity of the magnesium hydroxide was 98.63%, and the whiteness was 98.6%. The XRD and SEM images of magnesium hydroxide are shown in fig. 1 and 2.
Example 2:
step (1): one-pot treatment:
300mL of serpentine leachate (pickle liquor, same as in example 1), adding sodium chlorate with 1.4 times of iron content when the pH of the leachate is adjusted to 3 by 10% MgO slurry, and carrying out first-stage oxidation treatment at 60 ℃ for 40 minutes; adjusting the pH value of the leaching solution to 6 by 10 percent MgO slurry, then introducing hydrogen peroxide with the manganese content being 1.4 times, and carrying out second-stage oxidation treatment for 40min at the temperature of 60 ℃; continuously adjusting the pH value by using 10 percent MgO slurry until the pH value is adjusted to 8, and carrying out a third-stage reaction 2H at the temperature of 90 ℃;
after the treatment of one pot and three sections is finished, filtering is carried out, and the filtering speed is 15mg/min cm2The content of nickel in the filtrate after filtration is 0.074 mg.L-1The content of cobalt is 0.019 mg.L-1The content of manganese is 1.48 mg.L-1The content of chromium is 0.041 mg.L-1The content of iron is 0.014 mg.L-1(ii) a In the method, the recovery rate of iron is more than 99.9 percent, the recovery rate of nickel is 99.92 percent, the recovery rate of manganese is 99.57 percent, the recovery rate of chromium is more than 99.99 percent, and the loss rate of magnesium is less than 0.8 percent
Step (2): magnesium deposition and aging:
adding ammonia water into the purified solution, controlling the charging temperature at 30 deg.C, heating to 80 deg.C when the pH of the system reaches 9, and controllingThe pH during and at the end of the reaction was 9.2; the reaction is kept for 1.5h, and then Mg (OH) is obtained after filtration and washing2Washing the resulting Mg (OH)2Using 0.15 mol.L-1Aging NaOH (at 80 ℃) for 1.5h, wherein the total recovery rate of magnesium is 82%, the sulfur content of magnesium hydroxide is 0.18%, Cr element is not detected in the magnesium hydroxide, the purity of the magnesium hydroxide is 98.71%, and the whiteness is 99.6%.
Example 3:
step (1): one-pot treatment (pilot treatment):
the serpentine leachate (pickle liquor, same as in example 1) was 300L, and when the pH of the leachate was adjusted to 2.5 with 10% MgO slurry, sodium chlorate having an iron content of 1.5 times was added, and the solution was subjected to a first oxidation treatment at 65 ℃ for 50 minutes; adjusting the pH value of the leachate to 5 by 10 percent MgO slurry, introducing oxygen with the manganese content being 1.5 times, and carrying out second-stage oxidation treatment for 50 minutes at the temperature of 65 ℃; continuously adjusting the pH value by using 10 percent MgO slurry until the pH value is adjusted to 7.5, and carrying out a third-stage reaction for 2 hours at the temperature of 85 ℃;
after the treatment of one pot and three sections is finished, filtering is carried out, and the filtering speed is 73 g/h.dm2The content of nickel in the filtrate after filtration is 0.11 mg.L-1The content of cobalt is 0.09 mg.L-1The content of manganese is 0.41 mg.L-1The content of chromium is 0.85 mg.L-1Because the iron content is extremely low, ICP is not measured; in the method, the recovery rate of iron is more than 99.9 percent, the recovery rate of nickel is 99.98 percent, the recovery rate of manganese is 99.89 percent, the recovery rate of chromium is 99.7 percent, and the loss rate of magnesium is 1.2 percent.
Step (2): magnesium deposition and aging:
adding ammonia water into the solution purified and purified in the step (1), controlling the feeding temperature to be 40 ℃, heating to 75 ℃ when the pH of the system reaches 8.8, carrying out heat preservation reaction, controlling the pH of the reaction process and the reaction end point to be 9.1, and carrying out reaction for 2.0h, and then filtering and washing to obtain Mg (OH)2Washing the resulting Mg (OH)2Using 0.20 mol.L-1Aging NaOH (at 75 deg.C) for 2.0h, the total recovery of magnesium is 75%, the sulfur content of magnesium hydroxide is 0.16%, no Cr element is detected in magnesium hydroxide, the purity of magnesium hydroxide is 98.5%, and the whiteness is 99.3%.
Comparative example 1:
compared with the example 1, the difference is only that the temperature of the first stage oxidation process in the one-pot treatment process is 50 ℃; the other operations and parameters were the same as in example 1.
The results were: in the step (1), the filtration efficiency is 6mg/min cm2(ii) a The recovery rate of iron is 80%, the recovery rate of nickel is 95%, and the recovery rate of manganese is 96%; the recovery rate of chromium is 94 percent; the loss rate of magnesium is 10%; in the step (2), the total recovery yield of the magnesium hydroxide is 70%, the purity is 98.5%, and the whiteness is 98.6%; the magnesium hydroxide contains 0.0334% of Cr element and 0.2% of sulfur. The filtration performance and product quality such as purity and whiteness of the process are not as good as those of the process in example 1.
Comparative example 2:
compared with the example 1, the difference is only that the temperature of the second stage oxidation treatment process in the one-pot treatment process is 50 ℃; the other operations and parameters were the same as in example 1.
The results were: in the step (1), the recovery rate of iron is 98.8%, the recovery rate of nickel is 97.5%, the recovery rate of manganese is 70% and the recovery rate of chromium is 94%; the loss rate of magnesium is lower than 0.8%; in the step (2), the total yield of magnesium is 79%, the purity is 96.8%, and the whiteness is 89%; the sulfur content is 0.18 percent, and the Cr element is 0.0771 percent.
Comparative example 3:
compared with the example 1, the difference is only that the second stage oxidation treatment in the one-pot treatment process is 90 ℃; the other operations and parameters were the same as in example 1.
The results were: in the step (1), the recovery rate of iron is 97.7%, the recovery rate of nickel is 98%, and the recovery rate of manganese is 96%; the recovery rate of chromium is 80 percent, and the loss rate of magnesium is lower than 0.8 percent; in the step (2), the total yield of magnesium is 76%, the purity is 95.4%, and the whiteness is 87%; the sulfur content of the magnesium hydroxide is 0.21 percent, and the Cr element is 0.0419 percent.
Comparative example 4:
compared with the example 1, the difference is only that the third stage treatment in the one-pot treatment process is 60 ℃; the other operations and parameters were the same as in example 1.
The results were: in the step (1), the recovery rate of iron is 97%, the recovery rate of nickel is 96.4% and the recovery rate of manganese is 94%; the recovery rate of chromium is 95 percent; the loss rate of magnesium is 3%; in the step (2), the total yield of magnesium is 77%, the purity is 97.5%, and the whiteness is 98%; the sulfur content in the magnesium hydroxide was 0.18%.
Comparative example 5:
the only difference compared to example 1 is the pH during the second stage of the one-pot of step (1)BIt was 4.0. The other parameters were the same as in example 1.
The results were: in the step (1), the recovery rate of iron is 98%, the recovery rate of nickel is 97%, the recovery rate of manganese is 73%, and the recovery rate of chromium is 94%; the loss of magnesium was 1%.
In the step (2), the total recovery rate of magnesium is 80%, the sulfur content of magnesium hydroxide is 0.2%, the purity of magnesium hydroxide is 96.4%, and the whiteness is 87%.
Comparative example 6:
the only difference compared to example 1 is the pH during the second stage of the one-pot of step (1)BWas 6.5.
The results were: in the step (1), the recovery rate of iron is 96%, the recovery rate of nickel is 97%, the recovery rate of chromium is 82% and the recovery rate of manganese is 96%; the loss rate of magnesium was 0.9%.
In the step (2), the total recovery rate of magnesium is 78%; the purity of the magnesium hydroxide is 95.1%, the sulfur content is 0.23%, and the whiteness is 88%.
Claims (10)
1. The method for purifying magnesium in one pot from the serpentine normal-pressure sulfuric acid leaching solution is characterized in that the leaching solution subjected to the serpentine normal-pressure sulfuric acid leaching is subjected to one-pot three-section reaction treatment, and then solid-liquid separation is carried out to obtain a purified magnesium solution;
fe, Mn, Cr and Mg are dissolved in the leachate;
the one-pot three-section reaction process comprises the following steps: regulating pH of the leachateA2.0-3.0, adding an oxidant to carry out first-stage oxidation treatment; subsequent control of the pH of the SystemBAdding an oxidant to 4.5-6, and performing second-stage oxidation treatment; readjusting the pH of the SystemCCarrying out a third stage of reaction after the reaction reaches 7-8 ℃;
in the process of one-pot three-section reaction, the temperature of the first-section oxidation reaction and the second-section oxidation reaction is 60-80 ℃, and the temperature of the third-section reaction is 80-90 ℃.
2. The method for one-pot magnesium purification from an atmospheric sulfuric acid leach solution of serpentine according to claim 1, wherein the concentration of sulfuric acid in the atmospheric sulfuric acid leach process is 2-5 mol-L-1(ii) a The temperature of the acid leaching process is 80-100 ℃.
3. The method for one-pot magnesium purification from a serpentine atmospheric sulfuric acid leach solution according to claim 1, wherein the concentration of Fe in the leach solution is 5-18 g/L; the concentration of Mn is 0.2-0.5 g/L, Cr, the concentration of Mn is 0.10-0.40 g/L, Mg, and the concentration of Mn is 50-65 g/L.
4. The method for one-pot magnesium purification from an atmospheric sulfuric acid leach solution of serpentine of claim 1, wherein the leach solution further comprises at least one of nickel, cobalt, and aluminum;
preferably, the concentration of Ni in the leaching solution is 0.20-0.6 g/L; the concentration of Co is 0.01-0.04 g/L; the concentration of Al is 0.2-2 g/L.
5. The method for one-pot magnesium purification from an atmospheric pressure leachate of serpentine as recited in claim 1, wherein the pH of the system is controlled by using an alkaline substance in the one-pot three-stage treatment process, wherein the alkaline substance is at least one of magnesium oxide, calcium oxide, alkali metal hydroxide and ammonia water.
6. The method of one-pot magnesium purification from an atmospheric sulfuric acid leach solution of serpentine of claim 1, wherein the oxidizing agent is at least one of chlorate, oxygen, hydrogen peroxide in a one-pot three-stage process.
7. The method of claim 1, wherein magnesium is purified from the atmospheric pressure sulfuric acid leachate of serpentine in one potThe method is characterized in that in the first stage of oxidation reaction, the dosage of the oxidant is Fe in the system2+1.2 to 1.5 times the theoretical molar weight of oxidation;
preferably, in the second oxidation reaction stage, the amount of the oxidant is 1.2-1.5 times of the theoretical molar amount for oxidizing Mn (II) in the system into Mn (IV).
8. The method for one-pot magnesium purification from a serpentine atmospheric sulfuric acid leach solution according to claim 1, wherein the time of the first stage oxidation reaction is 0.5-1 h;
preferably, the time of the second-stage oxidation reaction is 0.5-1 h;
preferably, the time of the third stage reaction is 2.0-3.0 h.
9. The method for one-pot purification of magnesium from an atmospheric sulfuric acid leach solution of serpentine as claimed in claim 1, wherein a precipitant is added to the magnesium solution to perform a magnesium precipitation reaction to produce magnesium hydroxide;
preferably, the pH value of the magnesium precipitation reaction process and the terminal point is 8.8-9.5;
preferably, the temperature of the magnesium precipitation reaction process is 70-80 ℃;
preferably, the magnesium precipitation reaction time is 1-2 h.
10. The method for one-pot purification of magnesium from an atmospheric sulfuric acid leach solution of serpentine according to claim 9, wherein the magnesium hydroxide is aged in a caustic solution, followed by solid-liquid separation and washing to obtain purified magnesium hydroxide;
preferably, the alkali liquor is an aqueous solution of alkali metal hydroxide, and the preferable concentration of the solute is 0.2 mol.L-1～0.5mol·L-1；
Preferably, the temperature for aging is 70 ℃ to 80 ℃;
preferably, the aging time is 60-120 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210356080.9A CN114686702B (en) | 2022-04-06 | 2022-04-06 | Method for purifying magnesium by serpentine normal pressure sulfuric acid leaching solution in one pot |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210356080.9A CN114686702B (en) | 2022-04-06 | 2022-04-06 | Method for purifying magnesium by serpentine normal pressure sulfuric acid leaching solution in one pot |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114686702A true CN114686702A (en) | 2022-07-01 |
| CN114686702B CN114686702B (en) | 2024-05-07 |
Family
ID=82143380
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210356080.9A Active CN114686702B (en) | 2022-04-06 | 2022-04-06 | Method for purifying magnesium by serpentine normal pressure sulfuric acid leaching solution in one pot |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114686702B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115821063A (en) * | 2022-12-09 | 2023-03-21 | 中国恩菲工程技术有限公司 | Method for purifying magnesium from serpentine |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456565A (en) * | 2009-01-09 | 2009-06-17 | 昆明理工大学 | Method for preparing magnesium hydrate nano powder by active acid leaching nickel-containing serpentine |
| CN101831542A (en) * | 2010-04-23 | 2010-09-15 | 北京科技大学 | Method for extracting metallic elements of ferrum, magnesium and calcium from molybdenum milltailings |
| CN102276099A (en) * | 2011-07-29 | 2011-12-14 | 广西银亿科技矿冶有限公司 | Comprehensive treatment method of waste water from laterite-nickel ore wet smelting |
| CN102781848A (en) * | 2010-03-10 | 2012-11-14 | 住友金属矿山株式会社 | Method for wastewater treatment for wastewater containing aluminum, magnesium and manganese |
| CN106661664A (en) * | 2014-07-18 | 2017-05-10 | 联盟镁公司 | Hydrometallurgical process to produce pure magnesium metal and various by-products |
| CN107164637A (en) * | 2017-06-30 | 2017-09-15 | 江苏省冶金设计院有限公司 | The system and method for handling titanium dioxide fused salt chlorimation abraum salt |
| CN107406906A (en) * | 2014-11-18 | 2017-11-28 | 联盟镁公司 | The method of gas washing in SA production magnesium compound and various accessory substances is used in HCl reclaims loop |
-
2022
- 2022-04-06 CN CN202210356080.9A patent/CN114686702B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456565A (en) * | 2009-01-09 | 2009-06-17 | 昆明理工大学 | Method for preparing magnesium hydrate nano powder by active acid leaching nickel-containing serpentine |
| CN102781848A (en) * | 2010-03-10 | 2012-11-14 | 住友金属矿山株式会社 | Method for wastewater treatment for wastewater containing aluminum, magnesium and manganese |
| CN101831542A (en) * | 2010-04-23 | 2010-09-15 | 北京科技大学 | Method for extracting metallic elements of ferrum, magnesium and calcium from molybdenum milltailings |
| CN102276099A (en) * | 2011-07-29 | 2011-12-14 | 广西银亿科技矿冶有限公司 | Comprehensive treatment method of waste water from laterite-nickel ore wet smelting |
| CN106661664A (en) * | 2014-07-18 | 2017-05-10 | 联盟镁公司 | Hydrometallurgical process to produce pure magnesium metal and various by-products |
| CN107406906A (en) * | 2014-11-18 | 2017-11-28 | 联盟镁公司 | The method of gas washing in SA production magnesium compound and various accessory substances is used in HCl reclaims loop |
| CN107164637A (en) * | 2017-06-30 | 2017-09-15 | 江苏省冶金设计院有限公司 | The system and method for handling titanium dioxide fused salt chlorimation abraum salt |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115821063A (en) * | 2022-12-09 | 2023-03-21 | 中国恩菲工程技术有限公司 | Method for purifying magnesium from serpentine |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114686702B (en) | 2024-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109234526B (en) | Treatment method of laterite-nickel ore | |
| CN102070198B (en) | Method for preparing high-purity manganese sulfate and high-purity manganese carbonate by reduction leaching of pyrolusite through scrap iron | |
| CN102329964B (en) | Method for separating and recovering vanadium and chromium from vanadium-chromium reduced waste residue | |
| CN102121068B (en) | Method for preparing vanadium pentoxide | |
| CN112939090B (en) | Manganese sulfate purification and crystallization method | |
| CN107954474B (en) | Method for producing vanadium product and basic chromium sulfate by using vanadium-chromium solution | |
| CN110629047B (en) | Method for separating and extracting vanadium and chromium from vanadium and chromium-containing solution | |
| CN102146513A (en) | Method for extracting vanadium from vanadium-containing ore by oxidation acid-leaching wet method | |
| CN113045060B (en) | Comprehensive utilization method of seawater resources | |
| AU2011341872A1 (en) | Method for enrichment-recovering ferronickel from raw material containing nickel, method for recovering nickel from enriched ferronickel, and method for recycling solution containing iron produced from same | |
| CN113929150A (en) | Production process for preparing iron oxide red serving as precursor of lithium iron phosphate by hydrothermal method of ferrous sulfate serving as titanium dioxide byproduct | |
| CN111172390B (en) | Method for treating valuable metal sulfide concentrate by using oxygen pressure | |
| CN114686702B (en) | Method for purifying magnesium by serpentine normal pressure sulfuric acid leaching solution in one pot | |
| CN103833156B (en) | A kind for the treatment of process of cold rolling chlorohydric acid pickling spent acid | |
| CN112410555A (en) | Comprehensive recovery method for flotation silver concentrate from zinc hydrometallurgy acidic leaching residue | |
| CN103757260A (en) | Treatment method of nickel-containing eluvial ores | |
| CN111560518B (en) | Treatment method of copper-containing molybdenum concentrate | |
| CN109182868B (en) | Low-impurity vanadium-aluminum alloy and preparation method thereof | |
| CN108977672B (en) | Method for preparing iron molybdate by taking molybdenum-removing slag as raw material | |
| CN116375084A (en) | Preparation method of vanadium pentoxide | |
| CN108441649B (en) | Method for extracting nickel from chemical precipitation nickel sulfide material | |
| CN113088693B (en) | Method for recovering vanadium, nickel and aluminum from sulfuric acid slaking leachate | |
| CN115286038A (en) | Method for producing ammonium metavanadate by taking phosphorus removal slag as raw material | |
| CN108342591A (en) | A kind of molybdenum copper novel method for separating | |
| CN109207742B (en) | Method for efficiently leaching cobalt and nickel from cobalt and nickel sulfide waste |
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 |