CN114293035A - Method for preparing calcium carbonate by enriching vanadium from vanadium-containing steel slag - Google Patents
Method for preparing calcium carbonate by enriching vanadium from vanadium-containing steel slag Download PDFInfo
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- steel slag
- containing steel
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- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 184
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 183
- 239000002893 slag Substances 0.000 title claims abstract description 120
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 106
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 99
- 239000010959 steel Substances 0.000 title claims abstract description 99
- 238000000034 method Methods 0.000 title claims abstract description 89
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 51
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000011575 calcium Substances 0.000 claims abstract description 90
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 90
- 239000007788 liquid Substances 0.000 claims abstract description 74
- 238000002386 leaching Methods 0.000 claims abstract description 68
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000001556 precipitation Methods 0.000 claims abstract description 34
- 230000008569 process Effects 0.000 claims abstract description 26
- 238000000926 separation method Methods 0.000 claims abstract description 26
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 25
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 25
- 239000012535 impurity Substances 0.000 claims abstract description 24
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 22
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000012266 salt solution Substances 0.000 claims abstract description 19
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 24
- 238000009423 ventilation Methods 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 16
- 239000000292 calcium oxide Substances 0.000 description 15
- 235000019270 ammonium chloride Nutrition 0.000 description 14
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 14
- 238000005273 aeration Methods 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 9
- 238000000605 extraction Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000001099 ammonium carbonate Substances 0.000 description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 235000012501 ammonium carbonate Nutrition 0.000 description 3
- 239000000378 calcium silicate Substances 0.000 description 3
- 229910052918 calcium silicate Inorganic materials 0.000 description 3
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000009628 steelmaking Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910000628 Ferrovanadium Inorganic materials 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
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005276 aerator Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000002308 calcification Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000015598 salt intake Nutrition 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
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- 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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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for preparing calcium carbonate by combining vanadium-enriched steel slag containing vanadium, which comprises the following steps: (1) mixing vanadium-containing steel slag and an ammonium salt solution, performing selective leaching of calcium to obtain vanadium-rich slag and a calcium-rich liquid, vacuumizing in the selective leaching process, and absorbing the pumped ammonia gas to obtain ammonia water; (2) mixing the ammonia water obtained in the step (1) and the calcium-rich liquid obtained in the step (1), and carrying out impurity separation to obtain a purified liquid; (3) and (3) introducing micro-nano carbon dioxide bubbles into the purified liquid obtained in the step (2), carrying out precipitation reaction, and carrying out solid-liquid separation to obtain a calcium carbonate product. The method can realize the efficient selective leaching of calcium in the vanadium-containing steel slag, improve the vanadium grade and the subsequent leaching rate of vanadium, recycle ammonia gas and obtain good effect in the aspect of economy and environmental protection.
Description
Technical Field
The invention relates to the technical field of hydrometallurgy and comprehensive utilization of solid waste resources, in particular to a method for preparing calcium carbonate by combining vanadium-enriched steel slag containing vanadium.
Background
The steel slag containing vanadium is a byproduct for smelting vanadium-titanium magnetite and is V-containing formed by steelmaking of vanadium-containing molten iron2O51-10% steel slag (compared with vanadium slag, the calcium content of the steel slag is large), and the production process has two ways, one is that the residual vanadium in the semisteel is oxidized into the slag after steel making, and the other is that the molten iron without converting the vanadium slag is directly used for steel making to obtain the steel slag containing vanadium. The vanadium-containing steel slag has the following characteristics: (1) the CaO content is high, generally 30-60%, the crystallization is perfect, the texture is dense, and the dissociation degree is poor; (2) the components are complex and the fluctuation is large; (3) the vanadium content is low, the vanadium is dispersed and distributed in various mineral phases, and the occurrence state is complex. Because the content difference between vanadium and calcium oxide is very different, how to effectively extract vanadium from the vanadium-containing steel slag is still a difficult problem in the field of metallurgy.
At present, there are 2 approaches for extracting vanadium from steel slag containing vanadium, firstly, the steel slag containing vanadium returns to iron making and vanadium enrichment to refine slag containing high vanadium, then further vanadium extraction is carried out, namely, the steel slag containing vanadium is used as fusing agent to be added into sintering ore to enter into blast furnace smelting, vanadium is melted in molten iron, and vanadium blowing is carried out to obtain vanadiumThe high-grade vanadium slag is used as a raw material for extracting vanadium or smelting ferrovanadium. Although the process can recover valuable elements such as iron, manganese and the like and reduce the energy consumption of the iron-steel ratio, phosphorus is easily circularly enriched in molten iron, and the dephosphorization task of the steel slag is aggravated; and the steel slag has more impurities and relatively low effective CaO content, which can reduce the grade of sinter and increase the energy consumption in the iron-making process, so the method cannot be popularized. The other vanadium-containing steel slag treating process includes direct vanadium extracting process, sodium salt roasting, calcification roasting, calcium reducing roasting, direct acid leaching and other steps. Sodium salt or soda is used as an additive, low-valence vanadium is oxidized into soluble sodium salt of 5-valence vanadium by roasting, and water or carbonation leaching is adopted. The process has the advantages of low vanadium leaching rate, high sodium salt consumption, air pollution and difficult treatment in the roasting process, and the process is not suitable for V2O5The converter steel slag with low content and high content of CaO. The calcified roasting is to leach vanadium by using lime as roasting flux and by means of carbonating leaching. The method has certain selectivity to materials, has the problems of low conversion rate, high cost and the like for common steel slag, and is not suitable for large-scale production. The calcium-reducing roasting is proposed by Amiri, and aims to solve the problem that vanadium is difficult to leach due to the high CaO content in the vanadium-containing steel slag. The calcium-reducing roasting is to mix the steel slag and Na3PO4、Na2CO3Mixed roasting of Na3PO4Form Ca by combining with CaO3(PO4)2And the vanadium and sodium generate water-soluble sodium vanadate, and then the water is soaked to dissolve out the vanadium. However, the method only stays in the laboratory research stage, the proportion of phosphate is large, the cost is high, and the industrial popularization is not available at present. Direct acid leaching refers to complete wet vanadium extraction without a roasting process, but because the CaO content in the steel slag is high, the acid consumption is higher, and the cost is higher; the acid leaching process needs to be carried out in a strong acid solution, and the obtained leachate has more impurities and is difficult to carry out subsequent separation.
In conclusion, because the calcium oxide content of the vanadium-containing steel slag is high, no matter which vanadium extraction process is adopted, a series of technical problems exist, the vanadium extraction cost is increased, and the vanadium extraction index is reduced. Therefore, in order to solve the problem of extracting vanadium from the vanadium-containing steel slag, the pretreatment is carried out before extracting vanadium from the vanadium-containing steel slag, and the reduction of the content of calcium oxide is necessary. The decalcification process of the vanadium-containing steel slag mainly comprises two types of table reselection and wet leaching. Wherein, the decalcification rate of the table concentrator is low, the decalcification calcium can not be recycled, and a certain amount of vanadium can be lost in the process. Compared with a table concentrator gravity separation method, the wet leaching method has high decalcification rate and good selectivity and mainly comprises an acid leaching method and an ammonium chloride leaching method. CN106834749A and CN103131867A adopt hydrochloric acid and sulfuric acid respectively to purify calcium in the vanadium-containing steel slag, but the acid cannot be recycled, and the consumption is large. CN111560523A proposes that calcium in vanadium-containing steel slag is selectively purified by adopting non-additive ammonium chloride, so that the selective removal of calcium and the enrichment of vanadium are realized, but 30-60% of ammonium carbonate or ammonium bicarbonate of the vanadium-containing steel slag is required to be added in the process of preparing calcium carbonate so as to ensure the ammonium content in the calcium precipitation filtrate, the addition amount of the ammonium salt is large, and the loss of a large amount of ammonium in the whole process can be seen according to ammonium balance and the recycling of a large amount of ammonium is not realized.
Therefore, a new method for preparing calcium carbonate by combining vanadium-containing steel slag and enriched vanadium is needed to be developed.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a method for preparing calcium carbonate by combining vanadium enrichment of vanadium-containing steel slag, which realizes high-efficiency selective leaching of calcium and enrichment of vanadium, the leaching rate of calcium is more than or equal to 64%, the grade of vanadium is improved by more than 20%, leachate is recycled, and no waste water or waste gas is discharged in the process, so that the method is a high-efficiency and clean vanadium-rich method.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for preparing calcium carbonate by combining vanadium-enriched steel slag containing vanadium, which comprises the following steps:
(1) mixing vanadium-containing steel slag and an ammonium salt solution, performing selective leaching of calcium to obtain vanadium-rich slag and a calcium-rich liquid, vacuumizing in the selective leaching process, and absorbing the pumped ammonia gas to obtain ammonia water;
(2) mixing the ammonia water obtained in the step (1) and the calcium-rich liquid obtained in the step (1), and carrying out impurity separation to obtain a purified liquid;
(3) and (3) introducing micro-nano carbon dioxide bubbles into the purified liquid obtained in the step (2), carrying out precipitation reaction, and carrying out solid-liquid separation to obtain a calcium carbonate product.
The vanadium in the vanadium-containing steel slag is mainly wrapped in calcium silicate, so that vanadium is exposed after calcium is leached, the granularity of the residual vanadium-rich slag is obviously reduced compared with that of the original steel slag, and the subsequent vanadium extraction efficiency can be greatly improved. Ammonia water is prepared by cooling and absorbing ammonia gas volatilized in the calcium leaching process and is used for adjusting the pH value of the calcium-rich liquid, magnesium, aluminum, iron, silicon and the like leached in the reaction process are separated out in a precipitation mode, so that not only is the impurity in the calcium-rich liquid removed, but also NH in the process is realized4 +And (4) recycling. Calcium leached by reaction passes through micro-nano CO2Aerating to generate fine calcium carbonate, so that high-value utilization of calcium is realized. The whole process has no waste gas and waste water discharge, and is an economical, clean and environment-friendly high-efficiency calcium and vanadium leaching method.
Preferably, the ammonium salt solution is an ammonium chloride solution.
Preferably, V in the vanadium-containing steel slag in the step (1)2O5The content is 1 to 3.5%, and may be, for example, 1%, 1.3%, 1.6%, 1.9%, 2.2%, 2.4%, 2.7%, 3%, 3.3%, or 3.5%, but is not limited to the above-mentioned values, and other values not shown in the above range are also applicable.
Preferably, the content of CaO in the vanadium-containing steel slag is 30 to 50%, for example, 30%, 33%, 35%, 37%, 39%, 42%, 44%, 46%, 48%, or 50%, etc., but is not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, SiO in the vanadium-containing steel slag2The content is 20 to 30%, and may be, for example, 20%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, or 30%, but is not limited to the values listed, and other values not listed in the range are also applicable.
Preferably, the steel slag containing vanadium has a TFe content of 1 to 5%, for example, 1%, 1.5%, 1.9%, 2.4%, 2.8%, 3.3%, 3.7%, 4.2%, 4.6%, or 5%, etc., but not limited to the above-mentioned values, and other values not listed in this range are also applicable.
Preferably, the steel slag containing vanadiumAl2O3The content is 10 to 20%, and may be, for example, 10%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, or 20%, but is not limited to the values listed, and other values not listed in the range are also applicable.
Preferably, the vanadium-containing steel slag in step (1) has a particle size of-74 μm of 60-80%, for example, 60%, 64%, 68%, 72%, 76% or 80%, and the specific values therebetween are limited by space and for brevity, and the present invention is not exhaustive. In the invention, the particle size of the vanadium-containing steel slag is preferably controlled within the range, so that the leaching rate can be better improved.
Preferably, the mass ratio of the ammonium salt solution to the vanadium-containing steel slag in the step (1) is (20-40): 1, for example, 20:1, 24:1, 25:1, 28:1, 30:1, 32:1, 35:1, 36:1, 38:1 or 40:1, and the specific values therebetween are limited by space and for the sake of brevity, and the present invention is not exhaustive.
The invention further prefers the mass ratio to be in the range, and can realize better leaching of calcium in the vanadium-containing steel slag under the condition of adopting lower ammonium salt concentration.
Preferably, the molar concentration of the ammonium salt solution in the step (1) is 1-5M, for example, 1M, 1.5M, 2M, 2.5M, 3M, 3.5M, 4M, 4.5M or 5M, and the specific values therebetween are limited by space and for brevity, the present invention is not exhaustive.
M in the invention refers to mol/L.
Preferably, the pH of the ammonium salt solution in step (1) is 4.0-5.0, for example, 4.0, 4.1, 4.2, 4.3, 4.5, 4.6, 4.7, 4.8 or 5.0, and the specific values therebetween are not exhaustive for the sake of brevity and brevity.
Preferably, the degree of vacuum of the vacuum in step (1) is 0.05-0.1 MPa, such as 0.05MPa, 0.06MPa, 0.07MPa, 0.08MPa, 0.09MPa or 0.1MPa, and the specific values therebetween are limited by space and for brevity, the present invention is not exhaustive.
Preferably, the temperature of the selective leaching in the step (1) is 90-100 ℃, for example, 90 ℃, 92 ℃, 94 ℃, 96 ℃, 97 ℃, 98 ℃, 99 ℃, 100 ℃, and the specific values therebetween are limited by space and for brevity, and the present invention is not exhaustive.
In the present invention, it is further preferable that the temperature for the selective leaching is in the above range, and the leaching rate is more excellent.
Preferably, the selective leaching time is 1-3 h, for example, 1h, 1.5h, 2h, 2.5h or 3h, and the specific values therebetween are limited to the space and for brevity, and the present invention is not exhaustive.
Preferably, the stirring speed of the selective leaching is 300-350 rpm, for example, 300rpm, 310rpm, 320rpm, 330rpm, 340rpm or 350rpm, and specific values therebetween are limited to the space and for the sake of brevity, and the present invention is not exhaustive.
Preferably, the vanadium-rich slag of step (1) has a particle size of 80-95% of 23 μm, for example, 80%, 82%, 83%, 84%, 85%, 88%, 90%, 92% or 95%, and the specific values therebetween are not exhaustive for reasons of space and simplicity.
Preferably, the pH of the calcium-rich liquid is 5.5-6.3, for example, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2 or 6.3, and the specific values therebetween are not exhaustive for the sake of brevity and simplicity.
Preferably, the concentration of the ammonia water is 20-25 wt%, for example, 20%, 21%, 22%, 23%, 24% or 25%, and the specific values therebetween are limited to space and for brevity, the present invention is not exhaustive.
Preferably, the pH value of the impurity separation in the step (2) is 9-10, for example, 9, 9.2, 9.4, 9.6, 9.8 or 10, and the specific values therebetween are limited to space and for brevity, and the present invention is not exhaustive.
Preferably, the stirring rate for impurity separation is 100-200 rpm, such as 100rpm, 110rpm, 120rpm, 130rpm, 140rpm, 150rpm, 160rpm, 180rpm or 200rpm, and specific values therebetween, which are not exhaustive for reasons of space and simplicity.
Preferably, the temperature for separating the impurities is 20 to 30 ℃, for example, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃ or 30 ℃, and the specific values therebetween are limited by space and for brevity, and the present invention is not exhaustive.
The invention adopts the aeration mode to introduce the micro-nano carbon dioxide, the adopted device is not particularly limited, and any device which can be used for aeration and is well known to the technical personnel in the field can be adopted, for example, the micro-porous gas distribution device can be a micro-porous gas distribution device, and the material of the micro-porous gas distribution device is titanium, stainless steel, nickel or nickel alloy sintering filter element or a titanium powder metallurgy sintering aerator. The shape of the micropore gas distribution device is a rod shape, a semispherical shape, a flat plate shape or any other shape; the diameter of the micropores of the micropore gas distribution device is 0.1-1 μm, and may be, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1 μm, and the specific values therebetween are not limited to space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the size of the micro-nano carbon dioxide bubbles in the step (3) is 0.1-1 μm, for example, 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm or 1 μm, and the specific points between the above values are not exhaustive for the sake of space and simplicity.
Preferably, the aeration pressure of the micro-nano carbon dioxide bubbles is 0.1-0.5 MPa, for example, 0.10MPa, 0.15MPa, 0.17MPa, 0.2MPa, 0.25MPa, 0.28MPa, 0.3MPa, 0.32MPa, 0.35MPa, 0.4MPa, 0.45MPa or 0.5MPa, and the specific values therebetween are limited to space and simplicity, and the invention is not exhaustive.
Preferably, the aeration flow rate of the micro-nano carbon dioxide bubbles is 0.5-2L/(min · L purified liquid), and for example, may be 0.5L/(min · L purified liquid), 0.7L/(min · L purified liquid), 0.9L/(min · L purified liquid), 1.1L/(min · L purified liquid), 1.3L/(min · L purified liquid), 1.5L/(min · L purified liquid), 1.7L/(min · L purified liquid), 1.9L/(min · L purified liquid), or 2.0L/(min · L purified liquid), and specific point values between the above values are limited to space and are not exhaustive, for simplicity.
Preferably, the aeration time of the micro-nano carbon dioxide bubbles is 10-30 min, for example, 10min, 13min, 15min, 18min, 20min, 22min, 25min, 27min or 30min, and specific values therebetween are limited by space and for simplicity, and the present invention is not exhaustive.
Preferably, the temperature of the precipitation reaction is 40 to 60 ℃, for example, 40 ℃, 43 ℃, 45 ℃, 48 ℃, 50 ℃, 52 ℃, 55 ℃, 57 ℃ or 60 ℃, and the specific values therebetween are limited to the space and the brevity, and the present invention is not exhaustive.
Preferably, the calcium-precipitated liquid obtained by the solid-liquid separation in the step (3) is recycled to the step (1) to be used as the ammonium salt solution for selective leaching in a recycling way.
The calcium in the vanadium-containing steel slag mainly exists in the forms of active calcium oxide or calcium silicate and the like, and the steel slag is alkaline. The main component of the liquid after calcium precipitation is NH4 +And Cl-The solution is weakly acidic ammonium chloride solution, so the alkaline vanadium-containing steel slag can be directly leached by adopting the solution after calcium precipitation.
The solid-liquid separation in the above process is not particularly limited in the present invention, and any device and method for solid-liquid separation known to those skilled in the art can be used, and may be adjusted according to the actual process, such as filtration, centrifugation, or sedimentation, or may be a combination of different methods.
As a preferred technical scheme of the invention, the method comprises the following steps:
(1) mixing vanadium-containing steel slag (V)2O51-3.5% of CaO, 30-50% of SiO220-30% of TFe, 1-5% of TFe,Al2O310-20%) and 1-5M in molar concentration, and 4.0-5.0 in pH, wherein the mass ratio of the ammonium salt solution to the vanadium-containing steel slag is (20-40): 1, the calcium is selectively leached at 90-100 ℃ and 300-350 rpm, the vacuum degree is simultaneously vacuumized until the vacuum degree is kept at 0.05-0.1 MPa, the pumped ammonia gas is absorbed to obtain 20-25 wt% ammonia water, and the selective leaching time is 1-3 h, so that 80-95% of vanadium-rich slag with the granularity of-23 mu M and calcium-rich liquid with the pH of 5.5-6.3 are obtained;
(2) mixing the ammonia water obtained in the step (1) and the calcium-rich liquid obtained in the step (1), and carrying out impurity separation under the conditions of pH 9-10, 100-200 rpm and 20-30 ℃ to obtain a purified liquid;
(3) introducing micro-nano carbon dioxide bubbles with the size of 0.1-1 mu m into the purified liquid obtained in the step (2), wherein the ventilation pressure is 0.1-0.3 MPa, the ventilation flow is 0.5-2L/(min. L purified liquid), the ventilation time is 10-30 min, precipitation reaction is carried out at 40-60 ℃, and solid-liquid separation is carried out to obtain a calcium carbonate product and a liquid after calcium precipitation;
and (3) circulating the calcium-precipitated liquid to the step (1) to be used as an ammonium salt solution for circulating selective leaching.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the method for preparing calcium carbonate by combining vanadium-enriched steel slag containing vanadium and enriching the vanadium has the advantages of selective extraction and separation of calcium in the steel slag containing vanadium, no additional addition, low cost, high leaching rate of calcium of more than or equal to 60 percent, high leaching rate of more than or equal to 67 percent under the optimal condition, high vanadium grade of more than 16 percent, high vanadium grade of more than 20 percent under the optimal condition, good process selectivity and no loss of vanadium;
(2) the method for preparing calcium carbonate by combining vanadium enrichment of vanadium-containing steel slag adopts a vacuumizing mode, so that ammonia gas generated in the process can be recovered while the leaching rate is improved, and the recovered ammonia water is used for adjusting the pH value of the calcium-rich liquid, so that the impurity removal rate is more than or equal to 99%, ammonia loss in the reaction process is avoided, the leaching solution is purified, and the method is green and environment-friendly;
(3) according to the method for preparing calcium carbonate by combining vanadium enrichment with vanadium-containing steel slag, the grade of vanadium in the vanadium-rich slag is improved, the vanadium wrapped by calcium silicate is exposed, the granularity of the vanadium-rich slag is obviously reduced, and the subsequent vanadium extraction efficiency is increased by more than 20%;
(4) according to the method for preparing calcium carbonate by combining vanadium enrichment with vanadium-containing steel slag, calcium precipitation is carried out by selecting a micro-nano aeration method, the calcium precipitation rate is more than 99%, the obtained particle size is fine, and the average particle size of calcium carbonate is controlled to be less than or equal to 10 mu m under the optimal condition.
Drawings
FIG. 1 is a schematic flow chart of a method for jointly preparing calcium carbonate by enriching vanadium from vanadium-containing steel slag according to an embodiment of the present invention.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
As a specific embodiment of the present invention, there is provided a method for preparing calcium carbonate by combining steel slag containing vanadium and enriched with vanadium, as shown in fig. 1, the method comprises the following steps:
(1) mixing vanadium-containing steel slag and an ammonium salt solution, selectively leaching calcium, vacuumizing, and absorbing the pumped ammonia gas to obtain ammonia water to obtain vanadium-rich slag and a calcium-rich solution;
(2) mixing the ammonia water obtained in the step (1) and the calcium-rich liquid obtained in the step (1), and carrying out impurity separation to obtain a purified liquid and separated impurities;
(3) introducing micro-nano carbon dioxide bubbles into the purified liquid obtained in the step (2), carrying out precipitation reaction, and carrying out solid-liquid separation to obtain a fine calcium carbonate product and a liquid after calcium precipitation;
and (3) circulating the calcium-precipitated liquid to the step (1) to be used as an ammonium salt solution for circulating selective leaching.
Example 1
The embodiment provides a method for preparing calcium carbonate by combining vanadium-enriched steel slag containing vanadium, which comprises the following steps:
(1) vanadium-containing steel slag (V) with mixed-74 mu m accounting for 80 percent2O53.5% of CaO, 30% of SiO230% of TFe, 5% of Al2O3Content of 20%) and concentration of 5M, ammonium chloride solution with pH of 4.0, the mass ratio of ammonium chloride solution and steel slag containing vanadium is 40:1, put into vacuum reactor, 90 deg.C, 350rpm carry on the selective leaching of calcium, vacuumize at the same time to the vacuum degree keeps in 0.1MPa, ammonia gas that is taken out is absorbed and got the ammonia water with concentration of 25 wt%, the time for selective leaching is 2h, get the particle size-23 μ M and account for 90% vanadium-rich slag and calcium-rich liquid with pH of 5.5;
(2) mixing the ammonia water obtained in the step (1) and the calcium-rich liquid obtained in the step (1), carrying out impurity separation (magnesium, aluminum, silicon, iron and other impurities are separated out in a precipitation form) under the conditions of pH10, 200rpm and 20 ℃, and filtering to obtain a purified liquid;
(3) introducing micro-nano carbon dioxide bubbles with the size of 0.1 mu m into the purified liquid obtained in the step (2), wherein the ventilation pressure is 0.2MPa, the ventilation flow is 0.5L/(min. L purified liquid), the ventilation time is 30min, precipitation reaction is carried out at 60 ℃, and filtering is carried out to obtain a fine calcium carbonate product and a liquid after calcium precipitation;
and (3) circulating the calcium-precipitated liquid to the step (1) to be directly used as an ammonium chloride solution for circulating selective leaching.
Example 2
The embodiment provides a method for preparing calcium carbonate by combining vanadium-enriched steel slag containing vanadium, which comprises the following steps:
(1) vanadium-containing steel slag (V) with mixed-74 mu m accounting for more than 70 percent2O52.5% of CaO, 50% of SiO220% of TFe, 1% of Al2O310 percent of ammonium chloride solution and 3M of concentration and 4.6 of pH, the mass ratio of the ammonium chloride solution to the vanadium-containing steel slag is 30:1, the ammonium chloride solution and the vanadium-containing steel slag are placed in a vacuum reactor, calcium is selectively leached at 95 ℃ and 320rpm, the vacuum degree is simultaneously pumped till 0.05MPa, the pumped ammonia gas is absorbed to obtain 22 weight percent of ammonia water, the selective leaching time is 1h, and 80 percent of vanadium-rich slag with the granularity of-23 mu M and 6.3 of vanadium-rich slag with the pH value of 6.3 are obtainedCalcium liquid;
(2) mixing the ammonia water obtained in the step (1) and the calcium-rich liquid obtained in the step (1), carrying out impurity separation (magnesium, aluminum, silicon, iron and other impurities are separated out in a precipitation form) at the conditions of pH9.5, 150rpm and 25 ℃, and filtering to obtain a purified liquid;
(3) introducing micro-nano carbon dioxide bubbles with the size of 1 mu m into the purified liquid obtained in the step (2), wherein the ventilation pressure is 0.5MPa, the ventilation flow is 1L/(min. L purified liquid), the ventilation time is 20min, and precipitation reaction is carried out at 40 ℃ and filtration is carried out to obtain a fine calcium carbonate product and a liquid after calcium precipitation;
and (3) circulating the calcium-precipitated liquid to the step (1) to be directly used as an ammonium salt solution for circulating selective leaching.
Example 3
The embodiment provides a method for preparing calcium carbonate by combining vanadium-enriched steel slag containing vanadium, which comprises the following steps:
(1) vanadium-containing steel slag (V) with mixed-74 mu m accounting for more than 60 percent2O51% of CaO, 35% of SiO228% of TFe content, 4% of Al2O317 percent of ammonium chloride solution and 1M of concentration and 5.0 of pH, the mass ratio of the ammonium chloride solution to the vanadium-containing steel slag is 20:1, the ammonium chloride solution and the vanadium-containing steel slag are placed in a vacuum reactor, calcium is selectively leached at 100 ℃ and 300rpm, the vacuum degree is simultaneously pumped until the vacuum degree is kept at 0.01MPa, the pumped ammonia gas is absorbed to obtain 20 weight percent of ammonia water, the selective leaching time is 3 hours, and 95 percent of vanadium-rich slag with the particle size of-23 mu M and calcium-rich liquid with the pH of 6.0 are obtained;
(2) mixing the ammonia water obtained in the step (1) and the calcium-rich liquid obtained in the step (1), carrying out impurity separation (magnesium, aluminum, silicon, iron and other impurities are separated out in a precipitation form) under the conditions of pH9, 100rpm and 30 ℃, and carrying out centrifugal separation to obtain a purified liquid;
(3) introducing micro-nano carbon dioxide bubbles with the size of 0.5 mu m into the purified liquid obtained in the step (2), wherein the ventilation pressure is 0.1MPa, the ventilation flow is 2L/(min. L purified liquid), the ventilation time is 10min, carrying out precipitation reaction at 50 ℃, and carrying out centrifugal separation to obtain a fine calcium carbonate product and a liquid after calcium precipitation;
and (3) circulating the calcium-precipitated liquid to the step (1) to be directly used as an ammonium salt solution for circulating selective leaching.
Example 4
The embodiment provides a method for preparing calcium carbonate by combining vanadium-enriched steel slag containing vanadium, which is consistent with the embodiment 1 except that the particle size of the steel slag containing vanadium is reduced from-74 microns to 80 percent to 70 percent.
Example 5
The embodiment provides a method for preparing calcium carbonate by combining vanadium-enriched steel slag containing vanadium, which is consistent with the embodiment 1 except that the particle size of the steel slag containing vanadium is reduced from-74 microns to 80 percent to 60 percent.
Example 6
The embodiment provides a method for preparing calcium carbonate by combining vanadium-enriched steel slag containing vanadium, which is consistent with the embodiment 1 except that the mass ratio of an ammonium salt solution to the steel slag containing vanadium is reduced from 40:1 to 20: 1.
Example 7
This example provides a method for preparing calcium carbonate by combining vanadium-enriched steel slag containing vanadium, which is the same as that in example 1 except that the temperature of the calcium leaching reaction is increased from 90 ℃ to 95 ℃.
Example 8
The embodiment provides a method for preparing calcium carbonate by combining vanadium enrichment of vanadium-containing steel slag, which is characterized in that micro-nano CO is introduced into the calcium carbonate2The bubble size increased from 0.1 μm to 0.5. mu.m, and the remaining conditions were the same as in example 1.
Example 9
The embodiment provides a method for preparing calcium carbonate by combining vanadium enrichment of vanadium-containing steel slag, which is characterized in that micro-nano CO is introduced into the calcium carbonate2The bubble size increased from 0.1 μm to 1 μm, and the remaining conditions were identical to those of example 1.
Example 10
This example provides a method for preparing calcium carbonate by combining vanadium-enriched steel slag containing vanadium, which is the same as example 1 except that the reaction temperature of calcium leaching is reduced from 90 ℃ to 85 ℃.
Example 11
The embodiment provides a method for jointly preparing calcium carbonate by enriching vanadium from vanadium-containing steel slag, which is consistent with the embodiment 1 except that the pH value is 11 after the ammonia water in the step (1) and the calcium-enriched liquid in the step (1) are mixed.
Example 12
The embodiment provides a method for jointly preparing calcium carbonate by enriching vanadium from vanadium-containing steel slag, which is consistent with the embodiment 1 except that the pH value is 8 after the ammonia water in the step (1) and the calcium-enriched liquid in the step (1) are mixed.
Comparative example 1
The comparative example provides a method for preparing calcium carbonate by combining vanadium enrichment of vanadium-containing steel slag, which does not adopt a micro-nano aeration method to introduce CO2Otherwise, carbon dioxide was introduced directly in a conventional manner, and the remaining conditions were the same as in example 1.
Comparative example 2
The comparative example provides a method for preparing calcium carbonate by combining vanadium-enriched steel slag containing vanadium, and the method is consistent with the example 1 except that an atmospheric pressure reactor is adopted for the calcium leaching reaction and vacuum pumping is not carried out.
Comparative example 3
The comparative example provides a method for preparing calcium carbonate by combining vanadium-enriched steel slag containing vanadium, and the method is consistent with the example 1 except that the calcium leaching reaction is carried out by adopting a closed reactor.
Comparative example 4
The comparative example provides a process for purifying and recovering calcium components in vanadium-containing steel slag, which is specifically carried out by adopting example 1 in CN 111560523B.
In comparative example 4, the leaching rate of calcium is about 61%, although the leaching rate is basically free from decomposition and volatilization loss of ammonium salt, ammonium carbonate is added again in each circulation of the whole system, the ammonium is not recycled, in comparative example 4, the calcium precipitation solution is added with diluted hydrochloric acid dropwise to neutralize redundant carbonate and bicarbonate (the excessive ammonium carbonate is needed to be added in the early stage to ensure that the calcium can be fully precipitated), in order to avoid that the recycled calcium precipitation solution cannot reach the expected leaching rate of calcium, the excessive hydrochloric acid is needed to remove the carbonate and the bicarbonate, the excessive addition of the hydrochloric acid causes the pH value of the calcium precipitation solution to be not in accordance with the requirement, ammonia water is needed to be added to adjust the pH value, the whole operation is more complicated, and the ammonium is not recycled essentially. The test method comprises the following steps: testing the vanadium content in the vanadium-rich slag and the calcium content in the vanadium-containing steel slag and the vanadium-rich slag by adopting an ICP-OES method, and calculating the leaching rate of calcium according to the change of the calcium content in the slag before and after leaching; measuring the calcium concentration in the solution before and after calcium precipitation by adopting ICP-OES to calculate the calcium precipitation rate; and detecting the particle size of the calcium carbonate by adopting a particle size analyzer method.
The test results of the above examples and comparative examples are shown in table 1.
TABLE 1
From table 1, the following points can be seen:
(1) it can be seen from the comprehensive examples 1 to 3 that the method for preparing calcium carbonate by combining vanadium enrichment and steel slag containing vanadium provided by the invention realizes the recycling of ammonia and the high-efficiency leaching of calcium by selectively leaching with an ammonium salt solution under a negative pressure condition, and can effectively avoid the entrainment of impurities, wherein the leaching rate of calcium is more than or equal to 67%, the vanadium grade promotion rate is more than or equal to 25%, the calcium precipitation rate is more than or equal to 99%, and the average particle size of the obtained calcium carbonate is moderate and less than or equal to 10 μm;
(2) it can be seen from the combination of example 1 and example 10 that the reaction temperature of calcium leaching in example 10 is reduced from 90 ℃ to 85 ℃ in example 1, and the leaching rate of calcium is reduced from 69.72% to 60.2%, thereby showing that the invention further preferably controls the leaching temperature within a specific range, and the leaching rate of calcium is remarkably improved;
(3) it can be seen from the combination of the example 1 and the examples 11 to 12 that, although the pH of the calcium-rich solution mixed with the ammonia water does not affect the leaching rate and the precipitation rate of calcium, the purity of calcium carbonate in the example 11 is only 87%, while the purity of calcium carbonate in the example 1 is as high as 99.9%, and the purity of calcium carbonate in the example 12 is greater than 99.9%, but the pH is too high after mixing, so that part of calcium is precipitated in a precipitation form, and the final recovery amount of calcium carbonate is reduced, thereby indicating that the purity and the yield of calcium carbonate are better ensured by the step of removing impurities with ammonia water and preferably controlling the pH value;
(4) it can be seen from the combination of the example 1 and the comparative example 1 that the calcium deposition rate in the example 1 is as high as 99.42% compared with the calcium deposition rate in the comparative example 1 obtained by introducing carbon dioxide by the micro-nano aeration method, and the calcium deposition rate in the comparative example 1 is only 18.75%, compared with the conventional method in the comparative example 1, the micro-nano aeration method is adopted to prepare fine calcium carbonate, and the calcium deposition rate is remarkably improved;
(5) it can be seen from the comprehensive example 1 and comparative examples 2 to 3 that the calcium leaching rate is significantly improved by adopting a vacuumizing mode.
And (2) a cyclic test, taking example 1 as an example, directly recycling the calcium-precipitated liquid obtained in example 1 to be used as an ammonium chloride solution in the step (1) for cyclic use without any treatment, wherein the composition and other process parameters of the vanadium-containing steel slag are the same as those in example 1, and the cyclic test is continuously performed for 15 times. The results of the cycling tests are shown in table 2.
TABLE 2
As can be seen from Table 2, the calcium precipitation solution obtained by the method for jointly preparing calcium carbonate by enriching vanadium from vanadium-containing steel slag can be recycled without any treatment, and the leaching rate of calcium does not decrease after the recycling.
The present invention is described in detail with reference to the above embodiments, but the present invention is not limited to the above detailed structural features, that is, the present invention is not meant to be implemented only by relying on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The method for preparing calcium carbonate by combining vanadium-enriched steel slag containing vanadium with the calcium carbonate is characterized by comprising the following steps of:
(1) mixing vanadium-containing steel slag and an ammonium salt solution, performing selective leaching of calcium to obtain vanadium-rich slag and a calcium-rich liquid, vacuumizing in the selective leaching process, and absorbing the pumped ammonia gas to obtain ammonia water;
(2) mixing the ammonia water obtained in the step (1) and the calcium-rich liquid obtained in the step (1), and carrying out impurity separation to obtain a purified liquid;
(3) and (3) introducing micro-nano carbon dioxide bubbles into the purified liquid obtained in the step (2), carrying out precipitation reaction, and carrying out solid-liquid separation to obtain a calcium carbonate product.
2. The method according to claim 1, wherein V in the vanadium-containing steel slag of step (1)2O5The content is 1-3.5%;
preferably, the content of CaO in the vanadium-containing steel slag is 30-50%;
preferably, SiO in the vanadium-containing steel slag2The content is 20-30%;
preferably, the content of TFe in the vanadium-containing steel slag is 1-5%;
preferably, Al in the vanadium-containing steel slag2O3The content is 10-20%.
3. The method according to claim 1 or 2, wherein the vanadium-containing steel slag of step (1) has a particle size of-74 μm in the range of 60 to 80%.
4. The method according to any one of claims 1 to 3, wherein the mass ratio of the ammonium salt solution to the vanadium-containing steel slag in the step (1) is (20-40): 1;
preferably, the molar concentration of the ammonium salt solution is 1-5M, and the pH value is 4.0-5.0.
5. The method according to any one of claims 1 to 4, wherein the degree of vacuum of the evacuation in step (1) is 0.05 to 0.1 MPa.
6. The method according to any one of claims 1 to 5, wherein the temperature of the selective leaching in step (1) is 90 to 100 ℃;
preferably, the time for selective leaching is 1-3 h;
preferably, the stirring speed of the selective leaching is 300-350 rpm.
7. The method according to any one of claims 1 to 6, wherein the vanadium-rich slag in the step (1) has a particle size of 80 to 95% of 23 μm;
preferably, the concentration of the ammonia water is 20-25 wt%.
8. The method according to any one of claims 1 to 7, wherein the pH value of the impurity separation in the step (2) is 9 to 10;
preferably, the stirring speed of the impurity separation is 100-200 rpm;
preferably, the temperature for separating the impurities is 20-30 ℃.
9. The method according to any one of claims 1 to 8, wherein the micro-nano carbon dioxide bubbles in the step (3) have a size of 0.1 to 1 μm;
preferably, the ventilation pressure of the micro-nano carbon dioxide bubbles is 0.1-0.5 MPa;
preferably, the ventilation flow rate of the micro-nano carbon dioxide bubbles is 0.5-2L/(min & L of purified liquid);
preferably, the ventilation time of the micro-nano carbon dioxide bubbles is 10-30 min;
preferably, the temperature of the precipitation reaction is 40-60 ℃.
10. The method according to any one of claims 1 to 9, characterized in that the calcium-precipitation solution obtained by the solid-liquid separation in the step (3) is recycled to the step (1) for selective leaching as an ammonium salt solution.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115367780A (en) * | 2022-10-24 | 2022-11-22 | 生态环境部华南环境科学研究所(生态环境部生态环境应急研究所) | Method and device for efficiently leaching barium carbonate in barium slag through negative pressure boiling |
| CN115927881A (en) * | 2022-12-23 | 2023-04-07 | 中国科学院过程工程研究所 | Method for extracting vanadium from vanadium-containing steel slag and simultaneously preparing calcium sulfate |
| CN116173703A (en) * | 2022-12-07 | 2023-05-30 | 西南科技大学 | Mineralizing CO from electrolytic manganese slag 2 Method for synergistic solidification of metal ions and mineralized products |
| CN116462217A (en) * | 2023-01-18 | 2023-07-21 | 国家能源集团科学技术研究院有限公司 | Method for preparing calcium carbonate by utilizing steel slag |
| CN116812957A (en) * | 2023-04-25 | 2023-09-29 | 原初科技（北京）有限公司 | Fixing CO by solar heating 2 And integrated system and method for preparing calcium carbonate |
| CN117105253A (en) * | 2023-07-13 | 2023-11-24 | 郑州中科新兴产业技术研究院 | Method for preparing high added value calcium carbonate by wet carbonization of metallurgical slag rich in free CaO |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0308713D0 (en) * | 2002-04-18 | 2003-05-21 | Bayer Ag | Process for the utilization of vanadium in chromium ore as ammonium metavanadate |
| WO2015176429A1 (en) * | 2014-05-23 | 2015-11-26 | 中国科学院过程工程研究所 | Method for extracting vanadium by leaching vanadium-containing raw material fired clinkers with ammonium bicarbonate solution |
| CN107236870A (en) * | 2017-06-22 | 2017-10-10 | 中国科学院过程工程研究所 | A kind of method of v-bearing steel slag carbonization vanadium extraction |
| CN110408790A (en) * | 2018-04-27 | 2019-11-05 | 中国科学院过程工程研究所 | A kind of method that pressure leaching v-bearing steel slag produces vanadium product |
| US20200039838A1 (en) * | 2017-01-11 | 2020-02-06 | Institute Of Process Engineering, Chinese Academy Of Sciences | System for extracting vanadium from leaching solution containing vanadium chromium silicon and for preparing vanadium pentoxide and processing method therefor |
| CN111560523A (en) * | 2020-06-05 | 2020-08-21 | 昆明理工大学 | New process for purifying and recovering calcium components in vanadium-containing steel slag |
-
2021
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0308713D0 (en) * | 2002-04-18 | 2003-05-21 | Bayer Ag | Process for the utilization of vanadium in chromium ore as ammonium metavanadate |
| WO2015176429A1 (en) * | 2014-05-23 | 2015-11-26 | 中国科学院过程工程研究所 | Method for extracting vanadium by leaching vanadium-containing raw material fired clinkers with ammonium bicarbonate solution |
| US20200039838A1 (en) * | 2017-01-11 | 2020-02-06 | Institute Of Process Engineering, Chinese Academy Of Sciences | System for extracting vanadium from leaching solution containing vanadium chromium silicon and for preparing vanadium pentoxide and processing method therefor |
| CN107236870A (en) * | 2017-06-22 | 2017-10-10 | 中国科学院过程工程研究所 | A kind of method of v-bearing steel slag carbonization vanadium extraction |
| CN110408790A (en) * | 2018-04-27 | 2019-11-05 | 中国科学院过程工程研究所 | A kind of method that pressure leaching v-bearing steel slag produces vanadium product |
| CN111560523A (en) * | 2020-06-05 | 2020-08-21 | 昆明理工大学 | New process for purifying and recovering calcium components in vanadium-containing steel slag |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115367780A (en) * | 2022-10-24 | 2022-11-22 | 生态环境部华南环境科学研究所(生态环境部生态环境应急研究所) | Method and device for efficiently leaching barium carbonate in barium slag through negative pressure boiling |
| CN116173703A (en) * | 2022-12-07 | 2023-05-30 | 西南科技大学 | Mineralizing CO from electrolytic manganese slag 2 Method for synergistic solidification of metal ions and mineralized products |
| CN115927881A (en) * | 2022-12-23 | 2023-04-07 | 中国科学院过程工程研究所 | Method for extracting vanadium from vanadium-containing steel slag and simultaneously preparing calcium sulfate |
| CN116462217A (en) * | 2023-01-18 | 2023-07-21 | 国家能源集团科学技术研究院有限公司 | Method for preparing calcium carbonate by utilizing steel slag |
| CN116812957A (en) * | 2023-04-25 | 2023-09-29 | 原初科技（北京）有限公司 | Fixing CO by solar heating 2 And integrated system and method for preparing calcium carbonate |
| CN117105253A (en) * | 2023-07-13 | 2023-11-24 | 郑州中科新兴产业技术研究院 | Method for preparing high added value calcium carbonate by wet carbonization of metallurgical slag rich in free CaO |
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