CN114214514B - Method for leaching and removing phosphorus in high-phosphorus calcified roasting vanadium-containing clinker and recycling leaching liquid - Google Patents
Method for leaching and removing phosphorus in high-phosphorus calcified roasting vanadium-containing clinker and recycling leaching liquid Download PDFInfo
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- CN114214514B CN114214514B CN202111339639.9A CN202111339639A CN114214514B CN 114214514 B CN114214514 B CN 114214514B CN 202111339639 A CN202111339639 A CN 202111339639A CN 114214514 B CN114214514 B CN 114214514B
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- 238000002386 leaching Methods 0.000 title claims abstract description 161
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 126
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 83
- 239000011574 phosphorus Substances 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 49
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000004064 recycling Methods 0.000 title claims abstract description 30
- 239000007788 liquid Substances 0.000 title claims abstract description 25
- 239000000243 solution Substances 0.000 claims abstract description 64
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 60
- 230000002308 calcification Effects 0.000 claims abstract description 19
- 239000003929 acidic solution Substances 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000002893 slag Substances 0.000 claims description 14
- 239000000292 calcium oxide Substances 0.000 claims description 12
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 12
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 6
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 6
- 229910001415 sodium ion Inorganic materials 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 14
- 239000002253 acid Substances 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 10
- 230000002378 acidificating effect Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical class [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- JKJKPRIBNYTIFH-UHFFFAOYSA-N phosphanylidynevanadium Chemical compound [V]#P JKJKPRIBNYTIFH-UHFFFAOYSA-N 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- DNWNZRZGKVWORZ-UHFFFAOYSA-N calcium oxido(dioxo)vanadium Chemical compound [Ca+2].[O-][V](=O)=O.[O-][V](=O)=O DNWNZRZGKVWORZ-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- -1 especially Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
-
- 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
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to the field of chemical industry, and discloses a method for leaching and removing phosphorus in high-phosphorus calcification roasting vanadium-containing clinker and recycling leaching liquid. The method comprises the following steps: (1) Mixing the vanadium-containing acidic solution as a leaching agent with the high-phosphorus calcified roasting vanadium-containing clinker for leaching, and keeping the pH value at 1.2-1.8 in the leaching process; filtering to obtain filter residue and leaching solution; (2) And (3) directly returning the leaching solution serving as a leaching agent to the step (1) for recycling. According to the method, the vanadium-containing acidic solution is used as a leaching agent to leach the high-phosphorus calcified vanadium-containing clinker, so that vanadium is not lost while phosphorus is effectively removed, the leaching solution can be used as the leaching agent for recycling, and the leaching agent can be continuously used after being recycled for a plurality of times only by a small amount of dephosphorizing agents for simple dephosphorization. The method has the characteristics of small vanadium loss, simple treatment, easy operation and low cost.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a method for leaching and removing phosphorus in high-phosphorus calcification roasting vanadium-containing clinker and recycling leaching liquid.
Background
At present, the common vanadium slag calcification roasting-acid leaching vanadium process adopts calcium salt as a roasting additive, roasting is carried out under the condition of high temperature and oxygen to obtain calcification roasting vanadium-containing clinker, the calcification roasting vanadium-containing clinker contains calcium vanadate which is insoluble in water but soluble in acid, the acid vanadium liquid can be obtained by adopting dilute sulfuric acid leaching, and qualified vanadium pentoxide products can be prepared by removing impurities, precipitating vanadium and roasting, and the wastewater treatment is simple and the cost is low. Although the calcification process flow is simple and the cost is low, the vanadium-containing solution obtained by leaching under the acidic condition has more impurities, especially, phosphorus and vanadium in the acidic vanadium solution easily form vanadium-phosphorus complex (heteropolyacid), and the vanadium precipitation rate and the product quality are seriously influenced, so that the vanadium pentoxide prepared by the vanadium solution has strict requirements on the phosphorus content, and the subsequent vanadium precipitation process can be smoothly carried out. The acid leaching solution vanadium precipitation test research of the acid leaching solution mentions that the V concentration of the acid leaching solution of the low-calcium vanadium slag reaches about 35g/L, and the phosphorus content is less than or equal to 0.042g/L to precipitate vanadium. The vanadium solution containing 35g/L of vanadium is limited, and the requirement that the phosphorus is less than 0.042g/L is met, so that the requirement that the vanadium is precipitated in the later stage to obtain satisfactory vanadium precipitation rate and the qualified vanadium pentoxide is prepared. Most of the vanadium precipitation in the calcification technology still needs to control the phosphorus content of the leaching solution below 0.02 g/L.
There are also many studies on the dephosphorization of acidic high-phosphorus vanadium liquid and the subsequent extraction of vanadium. For example, patent CN 104894374B discloses a method for dephosphorizing an acidic vanadium-containing solution, mainly comprising the steps of contacting the acidic vanadium-containing solution with hydrogen peroxide and zirconium sulfate under the condition of a pH value of 2.5-3.5 to achieve the purpose of deep dephosphorization, wherein the method allows the acidic vanadium-containing solution to have a large phosphorus concentration range, has less vanadium loss while dephosphorizing, and has higher zirconium sulfate cost; the patent application CN 108359797A discloses a method for selectively removing phosphorus in acidic vanadium liquid by adopting activated calcium silicate, wherein the calcined and activated powdery calcium silicate is added into vanadium solution obtained by calcified acid leaching of vanadium slag, the pH value of a solution system is regulated to 2.5-5.0, and the low-phosphorus vanadium liquid is obtained by filtering after stirring reaction.
Patent CN107164643B discloses a method for preparing vanadium slag powder by crushing and grinding high-calcium high-phosphorus vanadium slag, wherein the granularity of the vanadium slag powder is 120-320 meshes, a buffer solution with the pH value of 1.7-2.0 is prepared or weak acid with the pH value of 1.7-2.0 is used as a leaching agent, leaching dephosphorization treatment is carried out on the obtained vanadium slag powder in a leaching solution under the normal temperature condition, mechanical stirring is carried out in the leaching dephosphorization treatment process, the leaching time is 60min, and the liquid-solid ratio of the leaching agent to the vanadium slag powder is 100:1 (mL/g); carrying out solid-liquid separation on the mixed solution after leaching treatment to obtain phosphorus-containing filtrate and low-phosphorus vanadium slag; drying the obtained low-phosphorus vanadium slag, adding sodium salt, and roasting at a high temperature of 700-900 ℃ for 2 hours; the molar ratio of the sodium salt addition amount to the vanadium element is 0.1-0.3; extracting vanadium through a water leaching process; obtaining the low-phosphorus vanadium-containing solution. The operation procedure is complex, the volume of the phosphorus-containing filtrate is large, and the subsequent treatment cost is high.
Disclosure of Invention
The invention aims to solve the problems of complex dephosphorization process, high cost, large dephosphorization agent consumption, easy wastewater generation and the like in the prior art, and provides a method for leaching and removing phosphorus in high-phosphorus calcified roasting vanadium-containing clinker and recycling leaching liquid.
In order to achieve the above purpose, the invention provides a method for leaching and removing phosphorus in high phosphorus calcification roasting vanadium-containing clinker and recycling leaching liquid, which comprises the following steps:
(1) Mixing the vanadium-containing acidic solution as a leaching agent with the high-phosphorus calcified roasting vanadium-containing clinker for leaching, and keeping the pH value at 1.2-1.8 in the leaching process; filtering to obtain filter residue and leaching solution;
(2) And (3) directly returning the leaching solution serving as a leaching agent to the step (1) for recycling.
Preferably, the high-phosphorus calcified roasting vanadium-containing clinker is obtained by calcified roasting high-phosphorus vanadium slag;
Preferably, the weight ratio of CaO to V 2O5 in the high phosphorus calcification roasting vanadium-containing clinker is 0.3-0.6:1, a step of;
Preferably, the high phosphorus calcification roasting vanadium-containing clinker contains 9-10 wt% of V, 0.1-0.2 wt% of P, 4-5 wt% of Cr and 5-7 wt% of Mn.
Preferably, the pH of the vanadium-containing acidic solution is from 1 to 6.
Preferably, in the vanadium-containing acidic solution, the concentration of vanadium is 20-35g/L, the concentration of phosphorus is less than or equal to 0.3g/L, and the concentration of sodium ions is less than or equal to 0.5g/L.
Preferably, in step (1), the liquid-solid ratio of leaching agent to high phosphorus calcification calcined vanadium-containing clinker is 1-1.8 (mL/g).
Preferably, in step (1), the leaching is agitation leaching.
Preferably, in step (1), the temperature of the leaching is 20-45 ℃; the leaching time is 10-20min.
Preferably, the method further comprises: after the leaching solution is recycled for a certain number of times, when the phosphorus content in the leaching solution is more than or equal to 0.3g/L, a dephosphorizing agent is added for treatment, the pH value is regulated to 2.4-3.5, and then the leaching solution is continuously used as the leaching agent to be returned to the step (1) for recycling;
Preferably, the cycle is used a number of times ranging from 2 to 4.
Preferably, the dephosphorizing agent is selected from at least one of calcium oxide, calcium carbonate, calcium sulfate and ferric sulfate.
Preferably, when the dephosphorizing agent is added, the solid-to-liquid ratio of the dephosphorizing agent to the leaching solution is 0.3-1 (g/L).
According to the method disclosed by the invention, the vanadium-containing acidic solution is used as the leaching agent to leach the high-phosphorus calcified vanadium-containing clinker, so that vanadium is not lost while phosphorus is effectively removed, the leaching agent can be used as the leaching agent for recycling, and the leaching agent can be continuously used after being recycled for many times only by a small amount of dephosphorizing agents for simple dephosphorization. The method has the characteristics of small vanadium loss, simple treatment, easy operation and low cost, and the vanadium pentoxide meeting the quality requirement can be obtained by leaching the obtained filter residues through conventional acid leaching, directly precipitating vanadium and calcining.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides a method for leaching and removing phosphorus in high phosphorus calcification roasting vanadium-containing clinker and recycling leaching liquid, which comprises the following steps:
(1) Mixing the vanadium-containing acidic solution as a leaching agent with the high-phosphorus calcified roasting vanadium-containing clinker for leaching, and keeping the pH value at 1.2-1.8 in the leaching process; filtering to obtain filter residue and leaching solution;
(2) And (3) directly returning the leaching solution serving as a leaching agent to the step (1) for recycling.
In the invention, the high-phosphorus calcified roasting vanadium-containing clinker can be obtained by calcified roasting high-phosphorus vanadium slag.
In a preferred embodiment, the weight ratio of CaO to V 2O5 in the high phosphorus calcification baked vanadium-containing clinker is 0.3-0.6:1. specifically, the weight ratio of CaO to V 2O5 in the high-phosphorus calcification baked vanadium-containing clinker can be 0.3:1, 0.4:1, 0.5:1 or 0.6:1.
In a preferred embodiment, the high phosphorus calcification calcined vanadium-containing clinker contains 9 to 10 wt% of V, 0.1 to 0.2 wt% of P, 4 to 5 wt% of Cr and 5 to 7 wt% of Mn.
In a preferred embodiment, the pH of the vanadium-containing acidic solution is from 1 to 6;
Further preferably, in the vanadium-containing acidic solution, the concentration of vanadium is 20-35g/L, the concentration of phosphorus is less than or equal to 0.3g/L, and the concentration of sodium ions is less than or equal to 0.5g/L.
In a preferred embodiment, the vanadium-containing acidic solution may be obtained by adding vanadium pentoxide and phosphoric acid to a sulfuric acid solution, or is selected from the leaching solution obtained by leaching high-phosphorus vanadium-containing clinker with sulfuric acid
In a preferred embodiment, in step (1), the liquid-to-solid ratio of leaching agent to high phosphorus calcification calcined vanadium-containing clinker is in the range of 1 to 1.8 (mL/g). Specifically, the liquid-to-solid ratio may be 1mL/g, 1.1mL/g, 1.2mL/g, 1.3mL/g, 1.4mL/g, 1.5mL/g, 1.6mL/g, 1.7mL/g, or 1.8mL/g.
In a preferred embodiment, in step (1), the leaching is agitation leaching.
In a preferred embodiment, in step (1), the temperature of the leaching is from 20 to 45 ℃; the leaching time is 10-20min. Specifically, the temperature at the same point may be 20 ℃,25 ℃, 30 ℃, 35 ℃,40 ℃ or 45 ℃; the leaching time can be 10min, 11min, 12min, 13min, 14min, 15min, 16min, 17min, 18min, 19min or 20min.
In the invention, more phosphorus is accumulated in the leaching solution along with the increase of the recycling times, and at the moment, the leaching solution can be treated by using a small amount of phosphorus removing agent, and then the pH value is regulated, so that the leaching agent can be regenerated and continuously put into use. Compared with the traditional dephosphorization method using dephosphorization agent, the whole process greatly reduces the use of the dephosphorization agent, simplifies the steps and reduces the generation of wastewater. Thus, in a preferred embodiment, the method further comprises: after recycling for a certain number of times, when the phosphorus content in the leaching solution is more than or equal to 0.3g/L, a dephosphorizing agent is added for treatment, the pH value is regulated to 2.4-3.5, and then the leaching agent is continuously used as the leaching agent to be returned to the step (1) for recycling.
In a preferred embodiment, the cycle is used a number of times ranging from 2 to 4.
In a preferred embodiment, the dephosphorizing agent is selected from at least one of calcium oxide, calcium carbonate, calcium sulfate, and ferric sulfate.
Further preferably, when the dephosphorizing agent is added, the solid-to-liquid ratio of the dephosphorizing agent to the leachate is 0.3 to 1 (g/L).
In a preferred embodiment, caO and/or ammonia water may be used as a regulator to adjust the pH.
According to the invention, phosphorus can be preferentially removed from the vanadium-containing clinker, compared with a conventional method of acid leaching before phosphorus removal, the method avoids the formation of a vanadium and phosphorus coexisting solution in the acid leaching vanadium leaching process, and serious vanadium loss can be caused by phosphorus removal, and the vanadium precipitation rate and the vanadium product quality are affected.
The present invention will be described in detail by way of examples, but the scope of the present invention is not limited thereto.
The high phosphorus calcified roasting clinker used in the following examples and comparative examples was obtained by calcified roasting of high phosphorus vanadium slag, and the main components contained are shown in Table 1. The vanadium-containing acidic solution used in examples 1 and 3 was a leaching solution obtained by leaching a high-phosphorus vanadium-containing clinker with sulfuric acid, and the vanadium-containing acidic solution used in example 2 was prepared by adding vanadium pentoxide and phosphoric acid to a sulfuric acid solution, and the main components are shown in table 2.
TABLE 1
| Numbering device | V/％ | P/％ | Cr/％ | Mn/％ | CaO/V2O5 |
| Example 1 | 9.52 | 0.144 | 4.52 | 5.40 | 0.30 |
| Example 2 | 9.21 | 0.139 | 4.37 | 5.22 | 0.50 |
| Example 3 | 9.06 | 0.137 | 4.30 | 5.14 | 0.60 |
TABLE 2
Example 1
(1) 1000ML of vanadium-containing acidic solution is used as a leaching agent and 667g of calcified high-phosphorus vanadium-containing clinker is mixed and stirred for leaching, the pH value is kept at 1.5 in the leaching process, the leaching time is 15min, and the leaching temperature is 35 ℃; filtering to obtain filter residue and leaching solution;
(2) The leaching solution is directly returned to the step (1) for recycling for 3 times as a leaching agent, wherein the concentration of V in the leaching solution is 20.87g/L and the concentration of P is 2.3g/L, so 0.2g of CaO and 0.3g of calcium carbonate are added into the leaching solution (980 mL), then ammonia water is used for regulating the pH value to 2.8, filtering is carried out, the concentration of V in the detected solution is 20.25g/L, P and the concentration of sodium ions is 0.296g/L, and the leaching solution is continuously returned to the step (1) for recycling as the leaching agent.
Example 2
(1) Mixing 1000mL of vanadium-containing acidic solution as a leaching agent and 1000g of calcified high-phosphorus vanadium-containing clinker, stirring and leaching, wherein the pH value is kept at 1.2 in the leaching process, the leaching time is 10min, and the leaching temperature is 20 ℃; filtering to obtain filter residue and leaching solution;
(2) The leaching solution is directly returned to the step (1) for recycling for 2 times as a leaching agent, wherein the concentration of V in the leaching solution is 29.48g/L and the concentration of P is 3.89g/L, so that 0.5g of calcium sulfate and 0.2g of ferric sulfate are added into the leaching solution (1010 mL), the pH value is regulated to 2.4 by CaO, the leaching solution is filtered, the concentration of V in the detected solution is 28.01g/L, P g/L and the concentration of sodium ions is 0.31g/L, and the leaching solution is continuously returned to the step (1) for recycling as the leaching agent.
Example 3
(1) 1000ML of vanadium-containing acidic solution is used as a leaching agent and 556g of calcified high-phosphorus vanadium-containing clinker is mixed for leaching, the pH value is kept at 1.8 in the leaching process, the leaching time is 20min, and the leaching temperature is 45 ℃; filtering to obtain filter residue and leaching solution;
(2) The leaching solution is directly returned to the step (1) for recycling for 4 times as a leaching agent, wherein the concentration of V in the leaching solution is 36.20g/L and the concentration of P is 2.67g/L, so 0.1g of CaO, 0.3g of calcium sulfate and 0.5g of ferric sulfate are added into the leaching solution (1045 mL), then CaO and ammonia water are used for adjusting the pH value to 3.5, filtering is carried out, the concentration of V in the detected solution is 34.75g/L, P and the concentration of sodium ions is 0.10g/L, and the leaching solution is continuously returned to the step (1) for recycling as the leaching agent.
Comparative example 1
The calcified high-phosphorus vanadium-containing clinker with the same components and the same weight used in the example 1 is extracted with vanadium by adopting a traditional method, and the concrete process is as follows:
Clinker is mixed according to a liquid-solid ratio of 2.5:1 and a leaching agent (tap water) are mixed, reacted for 60 minutes at the pH value of 2.8 and the temperature of 50 ℃, solid-liquid separation is carried out to obtain residues and leaching liquid, a dephosphorizing agent (18.48 g of ferric sulfate) is added into the leaching liquid for dephosphorizing, and then a vanadium precipitating agent is added for precipitating vanadium.
Test example 1
Detecting the P content in the filter residue obtained in the step (1) in the embodiment 1-3, and calculating the dephosphorization rate; the P content in the leachate and the dephosphorized solution in comparative example 1 was measured, and the dephosphorization rate was calculated.
The results are shown in Table 3.
| Numbering device | Dephosphorization rate% |
| Example 1 | 87.13 |
| Example 2 | 93.32 |
| Example 3 | 96.12 |
| Comparative example 1 | 50.63 |
As is clear from the results in Table 3, the dephosphorization by the method of the present invention has excellent dephosphorization efficiency.
Test example 2
The filter residue obtained in the step (1) in the examples 1 to 3 is subjected to vanadium extraction by adopting the same leaching agent and vanadium precipitation agent as in the comparative example 1 under the same conditions, and the specific process is as follows: filtering the residue according to a liquid-solid ratio of 2.5:1 and a leaching agent (tap water) are mixed and react for 60 minutes under the conditions of pH value of 2.8 and temperature of 50 ℃, residues and leaching liquid are obtained through solid-liquid separation, and a vanadium precipitating agent is added into the leaching liquid for precipitating vanadium. And the vanadium yield from the maturation to the vanadium precipitation product was calculated and compared with that of comparative example 1, and the results are shown in table 4.
TABLE 4 Table 4
As can be seen from the data in Table 4, the method of the invention is adopted to carry out dephosphorization treatment on the vanadium-containing clinker, and then conventional leaching and vanadium precipitation are carried out, thereby reducing the influence of phosphorus in the vanadium precipitation process, improving the vanadium yield and reducing the vanadium loss.
Test example 3
The dephosphorization rate of each of the leaching solutions in example 2 was measured during the 2-cycle use, and the results are shown in Table 5.
TABLE 5
| Dephosphorization rate% | |
| First cycle | 94.13 |
| Second cycle | 93.26 |
As is clear from table 5, in the method of the present invention, the leaching solution obtained in step (1) was continuously recycled and used as a leaching agent, and still had excellent dephosphorization efficiency. The recycling reduces the generation of waste water and saves the cost.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (5)
1. The method for leaching and removing phosphorus in the high-phosphorus calcified roasting vanadium-containing clinker and recycling leaching liquid is characterized by comprising the following steps of:
(1) Mixing the vanadium-containing acidic solution as a leaching agent with the high-phosphorus calcified roasting vanadium-containing clinker for leaching, and keeping the pH value at 1.2-1.8 in the leaching process; filtering to obtain filter residue and leaching solution;
(2) Directly returning the leaching solution as a leaching agent to the step (1) for recycling;
in the vanadium-containing acidic solution, the concentration of vanadium is 20-35g/L, the concentration of phosphorus is less than or equal to 0.3g/L, and the concentration of sodium ions is less than or equal to 0.5g/L;
In the step (1), the liquid-solid ratio of the leaching agent to the high-phosphorus calcified roasting vanadium-containing clinker is 1-1.8mL/g;
The high phosphorus calcification roasting vanadium-containing clinker contains 9-10 wt% of V, 0.1-0.2 wt% of P, 4-5 wt% of Cr and 5-7 wt% of Mn;
The pH value of the vanadium-containing acidic solution is 1-6;
The method further comprises the steps of: after the leaching solution is recycled for 2-4 times, when the phosphorus content in the leaching solution is more than or equal to 0.3g/L, a dephosphorizing agent is added for treatment, the pH value is regulated to 2.4-3.5, and then the leaching solution is continuously used as the leaching agent to be returned to the step (1) for recycling;
the dephosphorizing agent is at least one of calcium oxide, calcium carbonate, calcium sulfate and ferric sulfate;
when the dephosphorizing agent is added, the solid-liquid ratio of the dephosphorizing agent to the leaching solution is 0.3-1g/L.
2. The method for leaching and removing phosphorus from high-phosphorus calcified roasting vanadium-containing clinker and recycling leaching liquid according to claim 1, wherein the high-phosphorus calcified roasting vanadium-containing clinker is obtained by calcification roasting high-phosphorus vanadium slag.
3. The method for leaching and removing phosphorus and recycling leaching liquid in the high-phosphorus calcified roasting vanadium-containing clinker according to claim 2, wherein the weight ratio of CaO to V 2O5 in the high-phosphorus calcified roasting vanadium-containing clinker is 0.3-0.6:1.
4. The method for leaching to remove phosphorus from high phosphorus calcified calcined vanadium-containing clinker and recycling the leaching solution according to claim 1, wherein in step (1), the leaching is agitation leaching.
5. The method for leaching and removing phosphorus from high phosphorus calcification roasting vanadium-containing clinker and recycling leaching liquid according to claim 1, wherein in the step (1), the leaching temperature is 20-45 ℃; the leaching time is 10-20min.
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