CN114438335B - Treatment method of titanium-containing blast furnace slag - Google Patents
Treatment method of titanium-containing blast furnace slag Download PDFInfo
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- CN114438335B CN114438335B CN202111634908.4A CN202111634908A CN114438335B CN 114438335 B CN114438335 B CN 114438335B CN 202111634908 A CN202111634908 A CN 202111634908A CN 114438335 B CN114438335 B CN 114438335B
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- furnace slag
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- containing blast
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- 239000002893 slag Substances 0.000 title claims abstract description 95
- 239000010936 titanium Substances 0.000 title claims abstract description 88
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 86
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 54
- 238000002386 leaching Methods 0.000 claims abstract description 81
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000001914 filtration Methods 0.000 claims abstract description 37
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- 239000007791 liquid phase Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- 229910019440 Mg(OH) Inorganic materials 0.000 claims 1
- 238000000227 grinding Methods 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 8
- 239000012066 reaction slurry Substances 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 239000002910 solid waste Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 34
- 150000001768 cations Chemical class 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000002002 slurry Substances 0.000 description 16
- 239000011777 magnesium Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000010440 gypsum Substances 0.000 description 8
- 229910052602 gypsum Inorganic materials 0.000 description 8
- 229910052925 anhydrite Inorganic materials 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000004913 activation Effects 0.000 description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 241000276425 Xiphophorus maculatus Species 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 229940095564 anhydrous calcium sulfate Drugs 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229940095672 calcium sulfate Drugs 0.000 description 1
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical group O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229940057307 dihydrate calcium sulfate Drugs 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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
- 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
- C22B7/04—Working-up slag
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/06—Sulfating roasting
-
- 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
- C22B21/00—Obtaining aluminium
- C22B21/0007—Preliminary treatment of ores or scrap or any other metal source
-
- 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
- C22B21/00—Obtaining aluminium
- C22B21/0015—Obtaining aluminium by wet processes
- C22B21/0023—Obtaining aluminium by wet processes from waste materials
-
- 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
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1204—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent
- C22B34/1209—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent by dry processes, e.g. with selective chlorination of iron or with formation of a titanium bearing slag
-
- 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
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by 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
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
- C22B34/124—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors
- C22B34/125—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors containing a sulfur ion as active agent
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to the field of industrial solid waste utilization, and particularly discloses a titanium-containing blast furnace slag treatment method, which comprises the following steps of: mixing titanium-containing blast furnace slag with concentrated sulfuric acid to obtain a material to be roasted; roasting the material to be roasted at the temperature of 80-380 ℃ to obtain roasting slag; mixing dilute acid and/or sulfate solution with roasting slag, leaching, and filtering to obtain mixed leaching solution containing Ti, al and Mg components. The invention has simple process and high efficiency, and can improve the filtering efficiency of the reaction slurry.
Description
Technical Field
The invention relates to the field of industrial solid waste utilization, in particular to a titanium-containing blast furnace slag treatment method.
Background
The titaniferous blast furnace slag is industrial solid waste generated after vanadium titanomagnetite is smelted by a blast furnace, and the titanium-containing blast furnace slag is treated by sulfuric acid leaching in the prior art, so that various valuable components such as Ti, al, mg and the like can be transferred into a liquid phase at the same time, and then extraction and separation of the valuable components are realized by a filtering mode. The method is simple to operate, the using amount of the auxiliary agent is small, and the method is one of the processes with good prospect in the recycling treatment of the titanium-containing blast furnace slag, but the leaching slurry can be in a viscous state after the process is reacted, so that the filtration and separation efficiency of liquid and solid phases is seriously influenced, and a suction filtration or press filtration mode is required to be adopted in the subsequent filtration, so that the industrial energy consumption is increased.
Therefore, in order to solve the defects existing in the prior art of treating the titanium-containing blast furnace slag by the sulfuric acid leaching method, the art needs to propose a titanium-containing blast furnace slag treatment method to solve the defects and limitations of the prior art.
Disclosure of Invention
The invention aims to provide a titanium-containing blast furnace slag treatment method which has simple process and high efficiency, can improve the filtration efficiency of reaction slurry and is beneficial to filtering out liquid phase.
The technical scheme for realizing the purpose of the invention is as follows:
the treatment method of the titanium-containing blast furnace slag specifically comprises the following steps:
mixing titanium-containing blast furnace slag with concentrated sulfuric acid to obtain a material to be roasted;
roasting the material to be roasted at the temperature of 80-380 ℃ to obtain roasting slag;
mixing the roasting slag with the non-lattice cation solution, leaching, and filtering to obtain a mixed leaching solution containing Ti, al and Mg components.
The extraction method is particularly suitable for the high-titanium blast furnace slag, wherein the high-titanium blast furnace slag is tailings generated after vanadium titanomagnetite is treated by a blast furnace smelting process. The method is not only suitable for high-titanium blast furnace slag, but also suitable for slag containing titanium, magnesium and aluminum components.
The principle adopted by the invention is as follows:
the main reason that the existing process for directly leaching titanium-containing blast furnace slag by sulfuric acid causes the leaching slurry to be in a viscous state is that calcium sulfate dihydrate is generated in the reaction process, and the calcium sulfate dihydrate has high bound water content, uneven grain size distribution and plate-shaped crystal forms, so that the calcium sulfate dihydrate is easy to stack together in the filtration process, is strictly seamless with each other, and is unfavorable for filtering out liquid phase.
The invention is an improvement to the traditional method of extracting valuable components by only leaching titanium-containing blast furnace slag with sulfuric acid solution, firstly, the method of roasting with concentrated sulfuric acid at low temperature is adopted to react with the valuable components Ti, al and Mg in the titanium-containing blast furnace slag, corresponding soluble salts are generated by activation, the generation of calcium sulfate dihydrate containing crystal water is avoided under the high temperature condition, and the calcium-containing product is mainly sheet anhydrousCalcium sulfate, i.e., ii-anhydrite; and extracting and separating valuable components from the roasting slag by leaching the roasting slag by using a non-lattice cation solution. The definition of non-lattice cations in the present invention is: except Ca in calcium sulfate crystal system 2+ All cations other than those are referred to as non-lattice cations. In the process of the invention, the non-lattice cation solution which is leached by mixing with the roasting slag is selected from dilute sulfuric acid or sulfate solution, wherein the selection range of the sulfate solution comprises Ca removal 2+ Soluble sulfate composed of all metal cations except for those of the metal cations, in consideration of the fact that it is preferable not to introduce other impurity ions into the reaction system, and because of Al 3+ And Mg (magnesium) 2+ The sulfate of the present invention is preferably magnesium sulfate or aluminum sulfate, since it is originally present in the titanium-containing blast furnace slag.
H in leaching process + 、Mg 2+ 、Al 3+ The controllable addition of the method can prevent the conversion of the II-anhydrite into the gypsum (the II-anhydrite is anhydrous calcium sulfate and the gypsum is dihydrate calcium sulfate), the gypsum can not be generated under the reaction condition, the leached slurry is not gelatinised after the reaction is finished, the liquid-solid separation can realize natural sedimentation, and the filtration efficiency of the titanium-containing blast furnace slag system treated by the sulfuric acid method is further improved.
Compared with the prior art, the invention has the beneficial effects that:
(1) The method adopts the mode of roasting the titanium-containing blast furnace slag at a low temperature with concentrated sulfuric acid to activate Ti, mg and Al components, adopts the mode of leaching with dilute sulfuric acid and/or sulfate solution to extract the Ti, mg and Al components, has simple process, short flow and high component extraction efficiency, and is beneficial to industrial popularization;
(2) The low-temperature roasting method adopted by the invention has lower energy consumption, the roasting temperature does not reach the decomposition temperature of the roasting auxiliary concentrated sulfuric acid, and SO is not generated in the reaction process 2 The gas has little influence on the environment;
(3) The method adopts a method of roasting and leaching after extracting Ti, mg and Al components, the amount of the auxiliary agent added in the roasting process and the leaching process is small, and compared with the traditional method of directly leaching the titanium-containing blast furnace slag by using sulfuric acid solution to extract valuable components, the method avoids the problems of resource waste and environmental pollution caused by residual acid liquor due to the use of excessive reaction auxiliary agent;
(4) The calcium component in the slag and the dilute sulfuric acid of the titanium-containing blast furnace slag after roasting treatment generate small-sized flaky anhydrous calcium sulfate, namely II-anhydrite, and then the structure of the II-anhydrite is not changed after leaching by non-lattice cation solution, and gypsum with large-sized and platy structures is not generated, so that the leaching slurry is not in a gelatinous form, can be settled and layered freely, greatly improves the filtering efficiency of the reaction slurry, and is beneficial to filtering out liquid phase.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the drawings that are needed in the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic flow chart of the method for treating titanium-containing blast furnace slag according to the present invention.
FIG. 2 is a graph showing the filtration performance of leached slurries obtained after leaching of roasting slag with deionized water and sulfuric acid of varying concentrations.
FIG. 3 is a schematic diagram of the microstructure of the leached product after deionized water leaching of the roasting slag.
FIG. 4 is a schematic diagram of the microstructure of the leached product after leaching the roasting slag with dilute sulfuric acid.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The present invention provides a method for treating titanium-containing blast furnace slag, which may include the steps of:
step S1, high-temperature acidolysis;
mixing titanium-containing blast furnace slag with concentrated sulfuric acid to obtain a material to be roasted, and roasting the material to be roasted at 80-380 ℃ to activate Ti, mg and Al components to obtain roasting slag, thereby completing the high-temperature acidolysis process.
The following effects can be achieved by roasting when the temperature is raised to 80-380 ℃:
(1) The maximum efficiency activation of Ti, mg and Al components can be ensured;
(2) For concentrated sulfuric acid, too high a temperature will cause its decomposition to produce SO 2 The decomposition rate of the gas increases with the temperature, which affects the sufficiency of the chemical reaction and causes pollution to the environment; the temperature is lower than 80 ℃, which results in low activation efficiency and insufficient activation.
(3) The reaction of sulfuric acid and titanium-containing blast furnace slag is promoted by adopting a roasting mode, so that H generated in the reaction process 2 O evaporates quickly, so gypsum is avoided. Preferably, in step S1, the temperature is raised to 100 to 150 ℃ to perform calcination, and at this temperature, activation efficiency can be ensured while ensuring more sufficient activation.
Further, the mass ratio of the titanium-containing blast furnace slag to the concentrated sulfuric acid can be 1 (0.1-10). The mass ratio of the titanium-containing blast furnace slag to the concentrated sulfuric acid is 1 (0.1-10), so that the elements in the titanium-containing blast furnace slag can be ensured to react with the concentrated sulfuric acid; preferably, the mass ratio of the titanium-containing blast furnace slag to the concentrated sulfuric acid is 1 (1-2); more preferably, the mass ratio of the titanium-containing blast furnace slag to the concentrated sulfuric acid is 1:1.5, and under the more preferred ratio, the complete reaction of elements in the titanium-containing blast furnace slag can be ensured, and the raw materials can be saved to the greatest extent.
Further, before high-temperature acidolysis, in order to make the titanium-containing blast furnace slag and concentrated sulfuric acid mixed more uniformly, the method further comprises a step of crushing the titanium-containing blast furnace slag so that particles with the particle size of more than 80% of the materials to be roasted meet 30-200 mu m; preferably, more than 80% of the particles meet 50-160 μm, and the particles with the size facilitate the uniform mixing of the raw materials and the concentrated sulfuric acid, thereby being beneficial to the full implementation of the roasting reaction. For example, the titanium-containing blast furnace slag may be pulverized, classified, and then mixed with concentrated sulfuric acid.
Further, the baking time after reaching the baking temperature may be 0.1 to 5 hours. The heating rate has less influence on the reaction, for example, the heating rate can be 1 ℃/min to 10 ℃/min, the furnace can be heated to the preset stability, then the sample is put into the furnace for roasting, and the obtained activating effect is the same as that of the sample which is put into the furnace at room temperature and then heated.
S2, leaching;
mixing the roasting slag with the non-lattice cation solution, leaching, and filtering to obtain a mixed leaching solution containing Ti, al and Mg.
Further, the leaching temperature can be 25-100 ℃; when the leaching temperature is lower than 25 ℃, the leaching rate is poor, and when the leaching temperature is higher than 100 ℃, the energy consumption is too high. For example, the leaching temperature is 50 to 80 ℃. The leaching time may be confirmed according to the amount or phenomenon of the actual roasting slag, and may be, for example, 0.2 to 1.5 hours.
Further, the heating rate of leaching can be 3-8 ℃/min, and the metal elements such as Ti, al, mg and the like in the roasting slag can be fully leached in a short time under the heating rate.
In this step, the non-lattice cation solution may be a dilute sulfuric acid and/or sulfate solution, and the sulfate solution may be selected from aluminum sulfate or magnesium sulfate solution. H in leaching process + 、Mg 2+ And/or Al 3+ The controllable addition of the catalyst can prevent the conversion of II-anhydrite to gypsum, gypsum can not be generated under the reaction condition, leaching slurry is not gelatinous after the reaction is finished, natural sedimentation separation of liquid and solid can be realized, and the filtration efficiency of a titanium-containing blast furnace slag system treated by a sulfuric acid method is further improved, so that the concentration of non-lattice cation solution can be 0.1-3 mol/L, and the mass ratio of roasting slag to non-lattice cation solution can be 1 (0.1-10). Preferably, the concentration of the non-lattice cation solution is 0.2-1 mol/L, and the mass ratio of the roasting slag to the non-lattice cation solution is 1 (4-8); more preferably, the non-lattice cation solution is concentratedThe degree is 0.6mol/L, and the mass ratio of the roasting slag to the non-lattice cation solution is 1:6; under the more preferable proportion, the leaching of Ti, mg and Al components in the roasting slag is ensured to be larger, the viscosity of the reaction slurry can be reduced to the greatest extent, and the filtering efficiency is increased.
S3, filtering;
filtering the mixture obtained after leaching to obtain leaching residues and leaching liquid. Wherein the leaching slag is mainly Ca-rich leaching slag; the leaching solution is mainly leaching solution rich in Ti, mg and Al.
Further, the titanium-containing blast furnace slag treatment method further comprises a step S4 of boiling hydrolysis:
extracting Ti component from the leaching solution by boiling hydrolysis to obtain titanium leaching solution; ti is mainly extracted in the form of meta-titanic acid, and Mg and Al components are enriched in a liquid phase.
Further, the titanium-containing blast furnace slag treatment method further comprises the step S5 of step-by-step precipitation:
and (3) carrying out fractional precipitation by adjusting the pH value of the titanium extraction leaching solution to obtain Al and Mg respectively. Adding alkaline solution into the titanium extraction leaching solution, and respectively extracting Al and Mg components in the liquid phase at different pH values. Since the solubility product constants of Al and Mg are different, the pH value can be adjusted to ensure that Mg and Al in the hydrolysate respectively generate Mg (OH) 2 And Al (OH) 3 。
In the above step, the alkaline solution is ammonia water or sodium hydroxide solution. In the step of fractional precipitation, alkaline solution such as ammonia water or sodium hydroxide is added, the pH value of the leaching solution can be changed, and Al and Mg in the titanium leaching solution can be sequentially separated and extracted under different pH values.
Further, the method also comprises a pretreatment drying step before the high-temperature acidolysis step, specifically: drying the titanium-containing slag at 60-120 ℃ for 6-12 h. In the actual process, part of the titanium-containing blast furnace slag may be accumulated in the tailing dam, and there may be a problem of rainwater infiltration, so the titanium-containing slag may be dried before the high-titanium blast furnace slag is mixed with the concentrated sulfuric acid. In one embodiment of the invention, the titanium-containing blast furnace slag is pretreated and dried before high-temperature acidolysis, wherein the drying temperature is 60-120 ℃ and the drying time is 6-12 h. In the case of the blast furnace slag immediately after tapping, since the blast furnace slag itself is high in temperature, it is not necessary to dry the blast furnace slag. If the high titanium blast furnace slag is placed in an open tailing pond for a period of time, the placed tailings are required to be dried, and the drying temperature is 60-120 ℃.
For a better understanding of the above-described exemplary embodiments of the present invention, they are further described below in conjunction with specific examples.
Example 1
Mixing titanium-containing blast furnace slag with the mass ratio of 1:1.4 with concentrated sulfuric acid, roasting at a high temperature of 130 ℃ for 40min, leaching roasting slag by adopting dilute sulfuric acid, wherein the leaching process comprises the following condition parameters: sulfuric acid concentration 0.2mol/L, liquid-solid ratio 6, leaching temperature 60 deg.C, leaching time 30min.
Example 2
The difference is that the sulfuric acid concentration is 0.5mol/L compared with example 1.
Example 3
The difference is that the sulfuric acid concentration is 0.6mol/L compared with example 1.
Example 4
The difference is that the sulfuric acid concentration is 0.7mol/L compared with example 1.
Example 5
The difference is that the sulfuric acid concentration is 0.8mol/L compared with example 1.
Comparative example
Mixing titanium-containing blast furnace slag with the mass ratio of 1:1.4 with concentrated sulfuric acid, roasting at a high temperature of 130 ℃ for 40min, leaching the roasting slag by deionized water, wherein the leaching process comprises the following condition parameters: the liquid-solid ratio is 6, the leaching temperature is 60 ℃, and the leaching time is 60min.
The leaching slurries obtained in examples 1 to 5 and comparative examples were subjected to liquid-solid separation, and the filtration performance of the obtained leaching slurries was shown in fig. 2.
In addition, the microstructure of the leached product after leaching the roasting slag of the deionized water experimental group and the dilute sulfuric acid experimental group after carrying out a plurality of groups of experiments by adopting deionized water and the dilute sulfuric acid with different concentrations is respectively obtained, wherein fig. 3 is a microstructure diagram of the leached product of the comparative example; FIG. 4 is a microstructure of the leach product of example 3.
As can be seen from fig. 2 (the column in fig. 2 shows the filtration time, the curve a shows the viscosity of the slurry, and the curve B shows the filtration efficiency), the slurry has poor filtration performance when the slurry obtained by leaching deionized water is subjected to liquid-solid separation by the same filtration method, and the leaching solution and the leaching residue cannot be completely separated when the filtration time reaches 30min, and the leaching solution is basically stopped from being filtered at this time, the filtration efficiency is about 50%, and the viscosity of the slurry is about 38mpa·s. The viscosity of the acid leaching slurry obtained after leaching by dilute sulfuric acid is 15-20 mPa.s, the filtering performance of the leaching slurry is very good, the complete filtration can be basically realized between 12 and 15s, and the filtration rate is as high as about 98%.
As can be seen from fig. 3, the micro morphology of the leached slag obtained by leaching with deionized water is a regular diamond-shaped platy structural particle with smooth surface, which is typical morphology of dihydrate gypsum, has good crystal integrity and no cross growth between the particles, and the platy structural particles are easily stacked horizontally together in the filtration process of the water-immersed slurry to form a compact stacking structure, which is not beneficial to filtering out liquid, thereby resulting in poor filtration performance of the water-immersed slurry.
As can be seen from FIG. 4, the microstructure of the leached slag obtained by leaching with dilute sulfuric acid is a space formed by a lamellar structure inside, but the overall appearance of the structure is similar to a prismatic body, the lamellar structure is the shape of II-anhydrite, and more gaps are formed between the sheets, thereby being beneficial to filtering out liquid phase.
While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (8)
1. A method for treating titanium-containing blast furnace slag is characterized by comprising the following steps:
step S1, high-temperature acidolysis: mixing titanium-containing blast furnace slag with concentrated sulfuric acid to obtain a material to be roasted, and roasting the material to be roasted at 100-150 ℃ to activate Ti, mg and Al components to obtain roasting slag, thereby completing the high-temperature acidolysis process;
s2, leaching; mixing roasting slag with a dilute sulfuric acid solution, leaching, and filtering to obtain a mixed leaching solution containing Ti, al and Mg;
s3, filtering; filtering the mixture obtained after leaching to obtain leaching residues and leaching liquid;
step S4, boiling hydrolysis: extracting Ti component from the leaching solution by boiling hydrolysis to obtain titanium leaching solution; ti is extracted in the form of meta-titanic acid, and Mg and Al components are enriched in a liquid phase;
step S5, step-by-step precipitation: and (3) carrying out fractional precipitation by adjusting the pH value of the titanium extraction leaching solution to obtain Al and Mg respectively.
2. The method for treating titanium-containing blast furnace slag according to claim 1, wherein the mass ratio of the titanium-containing blast furnace slag to the concentrated sulfuric acid is 1:1.5.
3. The method for treating a titanium-containing blast furnace slag according to claim 1 or 2, wherein the method further comprises grinding the titanium-containing blast furnace slag before mixing the titanium-containing blast furnace slag with concentrated sulfuric acid, and classifying the slag so that the grain size of 80% or more thereof satisfies 30 μm to 200 μm.
4. The method for treating titanium-containing blast furnace slag according to claim 1 or 2, wherein the roasting time is 0.1 to 5 hours.
5. The method for treating a titanium-containing blast furnace slag according to claim 1 or 2, wherein the leaching temperature is 25 ℃ to 100 ℃.
6. The method for treating titanium-containing blast furnace slag according to claim 1 or 2, further comprising extracting titanium in the mixed leaching solution by boiling hydrolysis after obtaining the mixed leaching solution containing Ti, al, mg.
7. The method for treating a titanium-containing blast furnace slag according to claim 6, wherein after extracting titanium from the mixed leaching solution, the mixed leaching solution is subjected to fractional precipitation by adjusting the pH to obtain Al (OH) respectively 3 、Mg(OH) 2 。
8. The method for treating a titanium-containing blast furnace slag according to claim 1, 2 or 7, further comprising drying the titanium-containing blast furnace slag at 60 ℃ to 120 ℃ for 6 hours to 12 hours before mixing the titanium-containing blast furnace slag with concentrated sulfuric acid.
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