CN113562770B - Method for recycling iron and sodium resources in red mud in gradient manner and fully utilizing tailings - Google Patents
Method for recycling iron and sodium resources in red mud in gradient manner and fully utilizing tailings Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 57
- 239000011734 sodium Substances 0.000 title claims abstract description 55
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 35
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 34
- 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 title claims abstract description 22
- 238000004064 recycling Methods 0.000 title claims abstract description 16
- 238000002386 leaching Methods 0.000 claims abstract description 46
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000007787 solid Substances 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 23
- 238000011084 recovery Methods 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 10
- 239000000919 ceramic Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000000047 product Substances 0.000 claims abstract description 9
- 239000012065 filter cake Substances 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000005245 sintering Methods 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims abstract description 3
- 238000003825 pressing Methods 0.000 claims abstract description 3
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 3
- 239000006104 solid solution Substances 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000001276 controlling effect Effects 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 3
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000012360 testing method Methods 0.000 claims description 3
- OOIOHEBTXPTBBE-UHFFFAOYSA-N [Na].[Fe] Chemical compound [Na].[Fe] OOIOHEBTXPTBBE-UHFFFAOYSA-N 0.000 claims description 2
- NJFMNPFATSYWHB-UHFFFAOYSA-N ac1l9hgr Chemical compound [Fe].[Fe] NJFMNPFATSYWHB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052595 hematite Inorganic materials 0.000 claims description 2
- 239000011019 hematite Substances 0.000 claims description 2
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims 1
- 238000001238 wet grinding Methods 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 238000000748 compression moulding Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 229910001570 bauxite Inorganic materials 0.000 description 5
- 238000004131 Bayer process Methods 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000011449 brick Substances 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 238000011074 autoclave method Methods 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/132—Waste materials; Refuse; Residues
- C04B33/1321—Waste slurries, e.g. harbour sludge, industrial muds
- C04B33/1322—Red mud
-
- 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
- C22B26/10—Obtaining alkali metals
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Metallurgy (AREA)
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- Inorganic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Dispersion Chemistry (AREA)
- Structural Engineering (AREA)
- Treatment Of Sludge (AREA)
Abstract
The invention discloses a method for recycling iron and sodium resources in red mud in a gradient manner and fully utilizing tailings, which comprises the steps of grinding a red mud raw material, adding sulfuric acid, and carrying out acid leaching to dissolve Fe and Na; adding excessive ammonia water into the leachate to obtain Fe (OH) 3 Solid, p-Fe (OH) 3 Calcining the solid to obtain Fe 2 O 3 Producing a product; separating Fe (OH) from the solid and liquid 3 NaOH is added into the solid solution for chemical reaction, and the residual solution after the chemical reaction is subjected to evaporative crystallization to obtain sodium salt Na 2 SO 4 (ii) a And carrying out filter pressing on the leaching tailings, adding auxiliary materials into a filter cake, and carrying out wet grinding, uniform mixing, compression molding and sintering to obtain the building ceramic products with different purposes. The method has the advantages of simple treatment process, low cost, no introduction of other secondary pollution, avoidance of the atmosphere control process and the generation of a large amount of polluting gases in the conventional iron recovery process, better application prospect in the field of comprehensive utilization of red mud, and suitability for industrial popularization.
Description
Technical Field
The invention belongs to the technical field of industrial solid waste recycling, and particularly relates to a method for recycling iron and sodium resources in red mud and integrally recycling tailings, which is particularly suitable for fully recycling red mud rich in iron, aluminum, sodium and other metal elements.
Background
The red mud is a large amount of industrial waste residue generated after bauxite is leached out of Al in the bauxite by a high-concentration NaOH solution. The specific process comprises the following steps:al in bauxite under the experimental conditions of high temperature and high pressure 2 O 3 Will react with NaOH solution to generate sodium aluminate. With formation of sodium aluminate, other constituents of bauxite, e.g. SiO 2 、Fe 2 O 3 、TiO 2 Oxides and the like do not react with bases. Separating the solid which is insoluble in NaOH solution and still exists in solid form to obtain the red mud. In the process of solid-liquid separation, a part of NaOH solution is still separated with the solid matter, therefore, the finally obtained waste is usually a slurry-like fluid, and because the Fe content is slightly excessive 2 O 3 These wastes usually appear dark red or brick red, so they are called red mud.
The recycling of red mud is always a difficult problem and technical difficulty in the alumina industry. Reported in the literature, 1 ton of Al per produced 2 O 3 In this case, about 1.5 to 2.0 tons of red mud must be produced. China, as the first major alumina producing country in the world, discharges nearly one hundred million tons of red mud every year, and accumulates more than 13 hundred million tons of red mud. Fe in red mud 2 O 3 The content of the sodium-containing compound is generally high, and further, the sodium-containing compound contains 4 to 10 percent of Na 2 And O. The large amount of stockpiling of the red mud not only occupies a large amount of land and causes serious pollution to the environment, but also causes serious waste of bauxite resources with larger gaps in the market; in addition, most of the existing aluminum factories at home and abroad adopt conveying yards, damming wet-process stockpiling or dry-process stockpiling for the treatment of the red mud, and alkali-containing waste liquid in the red mud can pollute the ground surface and underground water sources, thereby seriously damaging the ecological natural environment. In conclusion, fe in red mud is fully and reasonably recovered 2 O 3 And Na 2 And the tailings are utilized to prepare the building material, so that the graded full-scale utilization of the red mud is effectively realized, the reduction, harmless and resource utilization of the red mud are realized, and the method has remarkable and profound environmental, social and economic significance.
In order to solve the problems, a great deal of research and exploration is carried out on the treatment and application of the red mud for a long time at home and abroad. The sodium removal of the red mud is easy to realize, but Fe in the red mud 2 O 3 There is currently no suitable method for recovery. The main methods at the present stage include an acid method and an alkali method: the acid-soluble method has high yield of alumina and low energy consumption, but has no proper idea for the treatment of ions in subsequent solution and the treatment of tailings, which also results in that the method is not applied to mature industrialization; the alkali method mainly comprises a sodium carbonate decomposition method, a hydrothermal reaction method, an autoclave reaction method and the like, the recovery rate of alumina in the sodium carbonate decomposition method is low, the concentration of alumina in a solution obtained by the hydrothermal method is low, and the hydrothermal method is difficult to match with a Bayer process main body dissolution process, and the autoclave method can recover a part of sodium in the alumina, but the temperature of the autoclave method generally reaches above 260-280 ℃, and the high-temperature and high-pressure operation often causes high production energy consumption and has high equipment requirement, so that the application of the method is limited to a certain extent.
Therefore, in view of the above-mentioned current situation, it is necessary to further search for research and treatment of red mud, and a new method capable of treating and utilizing red mud on a large scale is proposed.
Disclosure of Invention
The invention aims to solve the problems of low comprehensive utilization rate, high cost, easy secondary pollution to the environment and the like of the existing red mud utilization technology, and provides a method for recycling iron and sodium resources comprehensively, simple in treatment process, low in cost and environment-friendly in a gradient manner, and recycling iron and sodium resources and tailings in the red mud in a full-scale manner.
In order to realize the purpose, the method for recycling iron and sodium resources in red mud and completely utilizing tailings in a gradient manner adopts the following processes and steps:
1) Raw material treatment
The red mud raw material is crushed or ball-milled into fine red mud material with the granularity of-0.074 mu m and the mass percentage content of 60-95%. Generally, the mass percentage content of the fine red mud material with the granularity controlled at the grain size of-0.074 mu m accounts for 75-90 percent, thereby not only meeting the requirements of the red mud treatment process, but also saving the energy consumption of ore grinding. .
2) Acid leaching
Dissolving the fine red mud with Fe and Na under the conditions of liquid-solid ratio of 20-60mL/g and sulfuric acid mass concentration of 10-40%, controlling leaching time at 30-120min and leaching temperature at 25-90 ℃, and performing solid-liquid separation to obtain leachate and leaching tailings. The principle of the optimized selection of the process parameters of the step, namely the liquid-solid ratio, the sulfuric acid mass concentration, the leaching time and the leaching temperature, is to comprehensively consider the leaching rate of Fe, the leaching rate of Na, the system processing capacity and the production cost, generally, the liquid-solid ratio is 40-60mL/g, the sulfuric acid mass concentration is 25-40%, and the leaching rate of Fe is more than or equal to 85.0% and the leaching rate of Na is more than or equal to 80.0% by comprehensively regulating and controlling the liquid-solid ratio, the sulfuric acid mass concentration, the leaching time and the leaching temperature.
3) Recovery of iron-iron resource from ammonia water
In the solution after the steps, fe is Fe 3+ Exist in the form of (1). At this time, an excessive amount of ammonia water is added to the leachate obtained in step 2) to react, and a flocculent precipitate Fe (OH) is generated in the solution 3 (ii) a For the Fe (OH) containing flocculent precipitate 3 Subjecting the solution to solid-liquid separation to obtain Fe (OH) 3 Solid, p-Fe (OH) 3 Calcining the solid to obtain Fe 2 O 3 And (5) producing the product.
4) Sodium resource recovery
The ammonia water is adopted as the precipitator, and Fe (OH) is separated out by solid-liquid separation in step 3) 3 The solid solution contains more NH 4 + 、Na + And SO 4 2- Adding NaOH to carry out chemical reaction, and returning ammonia gas generated by the chemical reaction to the step 3) to carry out ammonia water iron precipitation; evaporating and crystallizing the residual solution after the chemical reaction to obtain the sodium salt Na 2 SO 4 。
5) Full-scale utilization of leaching tailings
Carrying out filter pressing on the leaching tailings obtained in the step 2), adding auxiliary materials, namely a silicon-aluminum raw material and a calcium-magnesium raw material into a filter cake, testing the water content and designing the adding proportion of different auxiliary materials, controlling the phase composition and components according to the requirements of the ceramic raw material components, and carrying out wet grinding, uniform mixing, press forming and sintering to obtain building ceramic products with different purposes, thereby realizing the step full-scale utilization of iron-sodium resources in the red mud and the leaching tailings.
Of course, according to market demands, the building material product can also be prepared by wet grinding, uniformly mixing, press forming and maintaining.
Compared with the prior art, the method for recycling iron and sodium resources and tailings in red mud in a gradient manner in a full-quantitative manner has the following beneficial effects:
(1) The method utilizes CaO and SiO in dilute acid solution 2 And Al 2 O 3 Is low, mainly because the several components are mostly present as mineral phases. And Fe 2 O 3 And Na 2 The O can be well dissolved in the acid liquor because the iron component mainly exists as hematite which is easy to dissolve in the acid liquor and the sodium component is derived from the added salt, so the method can realize the separation of Fe and Na resources from other oxides and has higher separation efficiency.
(2) Compared with the reported large-scale application methods at home and abroad, such as calcium oxide sintering method, hydrothermal method and high-temperature high-pressure water chemical method, the scheme provided by the method is carried out under mild conditions of low temperature and low pressure, and Fe is realized 2 O 3 With Na 2 High recovery rate of O, and Fe in red mud 2 O 3 With Na 2 The final recovery rates of O reach more than 85.0 percent and 80.0 percent respectively.
(3) The method provided by the invention realizes energy conservation and consumption reduction in the red mud recycling process, realizes the step recycling of various resources in the red mud, and improves the resource utilization rate. In addition, the method also eliminates the pollution of alkali carried by the red mud to the environment, and is a red mud treatment process with large-scale application prospect.
(4) In addition, the liquid used in the method is basically in closed-loop circulation, and has low pollution and no tail gas.
Drawings
Fig. 1 is a technical route chart of the method for the step recovery of iron and sodium resources in red mud and the full-scale utilization of tailings.
Detailed Description
The method is characterized in that Bayer process red mud is used as a raw material, and a low-temperature low-pressure water chemical method is adopted to recover Fe in the red mud 2 O 3 With Na 2 And O, realizing the step recycling of different resources in the red mud component. In order to describe the present invention, the method for the step recovery of iron and sodium resources in red mud and the full-scale utilization of tailings of the present invention will be further described in detail with reference to the following examples. The present invention is not limited to the embodiments, and simple modifications made according to the essence of the present invention should be covered within the scope of the present invention.
The bayer process red mud used in the examples of the present invention had the following composition (wt.%) in table 1:
TABLE 1 Bayer Process Red mud Main chemical composition (wt.%)
| Composition (I) | Al 2 O 3 | SiO 2 | Fe 2 O 3 | CaO | TiO 2 | Na 2 O | MgO |
| Content (%) | 23.38 | 17.55 | 27.72 | 16.65 | 4.21 | 4.69 | 2.62 |
As can be seen from the technical route chart of the method for the step recovery of iron and sodium resources in red mud and the full-scale utilization of tailings, which is shown in FIG. 1, the technical route of the method is as follows: raw material treatment (fine grinding), acid leaching, iron precipitation by ammonia water, iron resource recovery, sodium resource recovery (evaporative crystallization), and full-scale utilization of leaching tailings (ceramsite, sintered brick and ceramic tile). The specific treatment process comprises the following steps:
1) Adding a certain amount of red mud into 30-40 wt% sulfuric acid solution, and adding H 2 SO 4 The liquid-solid ratio of the red mud and the red mud is respectively 50mL/g and 60mL/g, the mixture is transferred to a three-neck flask after being uniformly mixed, the stirring speed is regulated, the temperature control program is set, the temperature of a water bath kettle is raised to 90 ℃, the reaction lasts for 120min, and then circulating water in a condensation pipe is opened. In addition, in order to verify the influence of the leaching temperature on the leaching behavior of Fe and Na, the leaching behavior of Fe and Na in red mud was studied under experimental conditions of room temperature (25 ℃), a sulfuric acid concentration of 25%, a liquid-solid ratio of 50mL/g, and a leaching time of 1 hour. After the reaction is finished, the slurry is filtered while hot, liquid and solid are separated, and the red mud filter cake is reserved. Then, a proper amount of red mud filter cake is weighed for standby.
2) In the reaction step 1), the leachate obtained under different leaching conditions is subjected to ICP-MS analysis, so that the method can be known as follows: when the concentration of sulfuric acid is 30 percent, H 2 SO 4 The liquid-solid ratio of the Fe-Na mixed solution to the red mud is 50mL/g, the leaching time is 0.5min, and the leaching temperature is 25 ℃, the concentration of the Fe and the Na can reach 72.5mg/L and 45.7mg/L; when the concentration of sulfuric acid is 30 percent, H 2 SO 4 When the liquid-solid ratio of the Fe-Na mixed solution to the red mud is 50mL/g, the leaching time is 120min and the leaching temperature is 90 ℃, the volume is determined to be 250mL of solution, and the concentrations of Fe and Na can reach 341mg/L and 54.2mg/L; when the concentration of sulfuric acid is 30 percent, H 2 SO 4 The liquid-solid ratio of the Fe to the red mud is 60mL/g, the leaching time is 120min, and the leaching temperature is 90 ℃, the volume is determined to be 250mL of solution, and the concentration of Fe and Na can reach 567mg/L and 83.4mg/L; when the concentration of sulfuric acid is 40 percent, H 2 SO 4 The liquid-solid ratio of the Fe-Na mixed solution to the red mud is 60mL/g, the leaching time is 120min, and the leaching temperature is 90 ℃, the volume is determined to be 250mL of solution, and the concentrations of Fe and Na can reach 641mg/L and 104mg/L. The experimental data show that the leaching rate of Fe and Na in the raw ore can be increased by increasing the liquid-solid ratio in the system and obviously increasing the solubility of Fe and Na in the leaching liquid. At the moment, the leaching rate of Fe and Na can reach 85.47 percent and 80.14 percent;
3) Transferring the filtrate obtained in step 2) to an erlenmeyer flask, wherein the solution contains a large amount of Fe 3+ . To be able to remove Fe in solution 3+ Converting into precipitate and recovering, wherein OH in the solution is adjusted - The solubility of the ions. The probe of the pH meter was added to the solution and the aqueous ammonia solution was added continuously to the flask. Filtering the solution until the content of floccule in the conical flask is not changed any more to obtain Fe (OH) 3 Thereby further realizing the recovery of Fe in the red mud.
4) Adding NaOH into the filtrate obtained by separating the slurry obtained in the step 3), recovering ammonia gas, and heating, evaporating and crystallizing on an electric heating plate after no gas overflows, so as to obtain Na salt, thereby realizing the recovery of Na resources in the red mud.
5) Testing the water content of the red mud filter cake obtained in the step 1), designing the adding proportion of different auxiliary materials, namely a silicon-aluminum raw material and a calcium-magnesium raw material, and grinding, uniformly mixing, preparing and sintering by a wet method to obtain different types of ceramic products, such as building ceramic products and the like of ceramic granules, ceramic tiles, sintered bricks and the like, so that the graded full-scale utilization of the red mud resource is realized.
Claims (2)
1. A method for recycling iron and sodium resources and tailings in a full-scale manner from red mud in a gradient manner, wherein iron components mainly exist in hematite which is easily dissolved in acid liquor, and the method is characterized by comprising the following steps:
1) Raw material treatment
Crushing or ball-milling the red mud raw material into a fine red mud material with the granularity of-0.074 mu m and the mass percentage content of 60-95%; the chemical component of the red mud is mainly Al 2 O 3、 SiO 2、 Fe 2 O 3、 CaO、TiO 2、 Na 2 O and MgO;
2) Acid leaching
Dissolving the fine red mud material with Fe and Na under the conditions of liquid-solid ratio of 40-60mL/g and sulfuric acid mass concentration of 25-40%, controlling leaching time at 30-120min and leaching temperature at 25-90 ℃, and performing solid-liquid separation to obtain leachate and leaching tailings; comprehensively regulating and controlling the liquid-solid ratio, the mass concentration of sulfuric acid, the leaching time and the leaching temperature to ensure that the leaching rate of Fe is more than or equal to 85.0 percent and the leaching rate of Na is more than or equal to 80.0 percent;
3) Recovery of iron-iron resource from ammonia water
Adding excessive ammonia water into the leachate obtained in the step 2) for reaction to generate flocculent precipitate Fe (OH) 3 (ii) a For the Fe (OH) containing flocculent precipitate 3 Subjecting the solution to solid-liquid separation to obtain Fe (OH) 3 Solid, p-Fe (OH) 3 Calcining the solid to obtain Fe 2 O 3 A product;
4) Sodium resource recovery
Step 3) solid-liquid separation of Fe (OH) 3 The solid solution contains more NH 4 + 、Na + And SO 4 2- Adding NaOH to carry out chemical reaction, and returning ammonia gas generated by the chemical reaction to the step 3) to carry out ammonia water iron precipitation; evaporating and crystallizing the residual solution after the chemical reaction to obtain the sodium salt Na 2 SO 4 ；
5) Full-scale utilization of leaching tailings
Carrying out filter pressing on the leaching tailings obtained in the step 2), adding auxiliary materials, namely a silicon-aluminum raw material and a calcium-magnesium raw material into a filter cake, testing the water content and designing the adding proportion of different auxiliary materials, controlling the phase composition and components according to the requirements of the components of the ceramic raw materials, grinding and uniformly mixing by a wet method, and carrying out press forming and sintering to obtain building ceramic products with different purposes, thereby realizing the step full-quantitative utilization of iron-sodium resources in the red mud and the leaching tailings.
2. The method for the full-scale utilization of iron and sodium resources and tailings in the gradient recovery of red mud of claim 1, wherein the method comprises the following steps: the mass percentage of the granularity of the fine red mud material in the step 1) is controlled to be-0.074 mu m, and the content is 75-90%.
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