CN117701885A - Treatment method of iron-containing vanadium slag filter cake - Google Patents
Treatment method of iron-containing vanadium slag filter cake Download PDFInfo
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- CN117701885A CN117701885A CN202210548445.8A CN202210548445A CN117701885A CN 117701885 A CN117701885 A CN 117701885A CN 202210548445 A CN202210548445 A CN 202210548445A CN 117701885 A CN117701885 A CN 117701885A
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- Prior art keywords
- iron
- filter cake
- temperature
- containing vanadium
- slag filter
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 37
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 32
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 29
- 239000002893 slag Substances 0.000 title claims abstract description 29
- 239000012065 filter cake Substances 0.000 title claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 24
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 22
- 239000000047 product Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000002006 petroleum coke Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005469 granulation Methods 0.000 claims abstract description 5
- 230000003179 granulation Effects 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 4
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000007921 spray Substances 0.000 claims abstract description 3
- 238000004537 pulping Methods 0.000 claims abstract 3
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- ZHXZNKNQUHUIGN-UHFFFAOYSA-N chloro hypochlorite;vanadium Chemical compound [V].ClOCl ZHXZNKNQUHUIGN-UHFFFAOYSA-N 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 238000007670 refining Methods 0.000 claims description 6
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000011268 mixed slurry Substances 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 238000010009 beating Methods 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims 1
- 235000013980 iron oxide Nutrition 0.000 claims 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 229910001935 vanadium oxide Inorganic materials 0.000 claims 1
- 239000002351 wastewater Substances 0.000 abstract description 5
- 238000009833 condensation Methods 0.000 abstract description 4
- 230000005494 condensation Effects 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 description 11
- 238000009835 boiling Methods 0.000 description 8
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002505 iron Chemical class 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229910000628 Ferrovanadium Inorganic materials 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 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
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 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 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000006199 nebulizer Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- -1 vanadate ions Chemical class 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
Abstract
The invention relates to a treatment method of an iron-containing vanadium slag filter cake, which comprises the following steps: (1) Uniformly pulping and mixing the iron-containing vanadium slag filter cake, water and petroleum coke, and then carrying out spray granulation; (2) The granulated raw materials are dehydrogenated and reduced into low-valence metal oxide under the protection of inert gas at a certain temperature; (3) The reduced raw materials undergo chlorination reaction at a certain temperature to obtain chloridized products of vanadium and iron, and condensation separation is carried out at a certain temperature to obtain corresponding chloride products. The method is green and environment-friendly, no wastewater is generated, the reaction condition is relatively mild, and the vanadium product with high purity and high added value is easy to obtain.
Description
Technical Field
The application relates to the technical field of recycling, in particular to a treatment method of an iron-containing vanadium slag filter cake.
Background
The chemical precipitation method is widely applied to the treatment of vanadium-containing wastewater, and comprises common methods such as an iron salt precipitation method, an ammonium salt precipitation method, an iron filings precipitation method and the like, wherein the iron salt precipitation method mainly utilizes the reaction of iron salt and vanadium ions in solution to generate yellow ferric vanadate (xFe) 2 O 3 ·yV 2 O 5 ·zH 2 O) precipitation of Fe 2+ And Fe (Fe) 3+ Can be used as a precipitator to react with vanadate ions in the solution to generate ferric vanadate precipitate.
At present, the main treatment means of ferric vanadate precipitation is generally secondary leaching-precipitation, and patent CN110273072A is a process route of reducing agent reduction, acidic impurity removal, alkaline iron precipitation and alkaline vanadium precipitation, and has the advantages of high impurity content and low added value of the produced product due to an inaccurate pH control mode, higher requirements on raw material grade or further refining treatment are required for obtaining a refined product, and a large amount of salt-containing wastewater is produced by an acid-base treatment method.
In the patent CN10923451A, ferric vanadate is mixed into crude vanadium slag, leaching of vanadium is carried out after sodium roasting, ammonium salt precipitation and roasting are carried out to obtain vanadium pentoxide, and in the vanadium leaching process, a large amount of ammonia nitrogen wastewater is generated due to the introduction of ammonium salt, so that the vanadium pentoxide is difficult to treat. And the temperature required by roasting the ammonium polyvanadate is higher, and the energy consumption is high.
In the patent CN110835696A, ferric vanadate is directly formed into a dispersion liquid and then mixed with an ammonifying agent, the dispersion liquid is dissolved under the heating condition to obtain purified vanadium liquid, and the purified vanadium liquid is cooled, crystallized and calcined to obtain a vanadium pentoxide product. Similar to the method of the patent, the problems of ammonia nitrogen wastewater treatment and high energy consumption are also existed.
In summary, for ferric vanadate filter cakes recovered by ferric salt precipitation, a cleaner and green treatment method is still needed.
The chlorination conversion condition of each main element in the iron-containing vanadium slag at different temperatures is shown in figure 1.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a treatment method of an iron-containing vanadium slag filter cake, which comprises the following steps:
(1) The iron-containing vanadium slag filter cake, water and petroleum coke after ball milling are pulped and mixed uniformly;
(2) Drying and granulating the mixed slurry under certain conditions;
(3) The granulated raw materials are dehydrogenated and reduced into low-valence metal oxide under the protection of inert gas at a certain temperature;
(4) The reduced raw materials undergo chlorination reaction at a certain temperature to obtain chloridized products of vanadium and iron, and condensation separation is carried out at a certain temperature to obtain a crude vanadium oxychloride product;
(5) Refining the crude vanadium oxychloride product to obtain a refined chloride product.
The iron-containing vanadium slag filter cake obtained in the step (1) is ferric vanadate precipitate (xFe) prepared by recovering vanadium in acid solution by a ferrovanadium coprecipitation method 2 O 3 ·yV 2 O 5 ·zH 2 O) may contain a small amount of Fe (OH) 3 And other metal salt or hydroxide impurities, the average particle size is 10-20 μm. The mass ratio of the ferric vanadate raw material dry basis to the petroleum coke is 1:0.25-1:0.3, and the solid content of the prepared spraying raw material slurry is 15-20%.
And (2) spraying the drying and granulating mode, wherein the spraying condition is that the inlet temperature is 250-350 ℃, the outlet temperature is 120-160 ℃, the frequency of an atomizer is 25-35 Hz, and the average particle size of the sprayed raw materials is 80-200 mu m.
And (3) the dehydrogenation temperature is 500-600 ℃.
The chlorination reaction in the step (4) is carried out in a boiling bed chlorination reactor, and the reaction temperature is 300-350 ℃. The condensing temperature of the chlorides of vanadium and iron is 250-350 ℃ of ferric chloride, and the condensing recovery temperature of vanadium oxychloride is-20 ℃.
And (3) the distillation temperature of the crude vanadium oxychloride in the step (5) is 130-140 ℃.
The treatment method has the following advantages:
(1) The ferrovanadium filter cake slurry is directly adopted to be fully mixed with the petroleum coke, so that uniform mixing of small particles can be easily realized in the solution.
(2) Because the ferric vanadate filter cake has certain viscosity, the ferric vanadate filter cake can be directly sprayed and granulated without adding other binders, so that the particles suitable for the chlorination operation of a boiling bed are obtained, and the drying of the filter cake is realized. The raw materials obtained by spray granulation are spherical, and the particle size distribution is centralized and uniform, thereby being beneficial to the operation of the ebullated bed chlorination reactor.
（3）Al 2 O 3 Chloridizing to produce AlCl 3 The boiling point of the catalyst is 178 ℃, V 2 O 5 VOCl produced by chlorination 3 The boiling point is 127.2 ℃, the difference of the boiling points is small, and Fe 2 O 3 Chloridizing FeCl 3 Boiling at 316 ℃, with VOCl 3 The boiling point difference is large. The mixed raw material obtained by granulation is roasted and dehydrogenated in inert atmosphere, and partial metal oxide in the raw material can be further reduced in the dehydrogenation process due to the existence of reducing agent carbon, so that the chlorination temperature of the mixed raw material can be effectively reduced, the chlorination conversion efficiency of impurity element Al can be further controlled, and the low-temperature reaction can also effectively reduce the processing cost of the reactor. The obtained chlorinated product FeCl 3 And VOCl 3 Can directly separate by adopting a fractional condensation mode, and VOCl 3 The product with higher added value can be further obtained through distillation.
(4) Compared with the existing treatment method for ferric vanadate solid, the method is green and efficient, and no wastewater is discharged.
Detailed description of the preferred embodiments
Example 1: pretreatment of raw materials
The iron-containing vanadium slag filter cake is obtained by oxidizing an acid solution obtained by dissolving vanadium-containing solid waste acid, precipitating with ferric sulfate, filtering and washing, and has the dry-basis composition shown in table 1, wherein the water content is 70 percent according to the iron-containing vanadium slag filter cake: petroleum coke: water = 1:0.09:4.75, the slurry was sprayed at an inlet temperature of 280 ℃, an outlet temperature of 135 ℃ and a nebulizer frequency of 30Hz. The particle size distribution of the raw materials before and after spraying is shown in Table 2. And filling the prepared mixed raw materials into a fluidized reactor, introducing argon, heating to 550 ℃, and carrying out dehydrogenation treatment for 2 hours. Continuously introducing argon for protection, cooling, and removing pretreated materials to serve as raw materials for chlorination reaction.
TABLE 1 composition of iron-vanadium slag (carbon free dry basis)
TABLE 2 particle size distribution of raw materials before and after spraying
Example 2: influence of temperature on the Chlorination conversion Effect
And (3) loading the pretreated raw materials into a boiling bed chlorination reactor, introducing argon, heating to different reaction temperatures, and switching an air source into chlorine to react to obtain flue gas and chloridized slag. And (3) introducing the flue gas into a condensing system for condensation, and absorbing residual chlorine through alkali liquor. Washing the chloridized slag in water to remove the surface attached chloride, filtering, drying the filter residue, weighing the total mass of the filter residue, detecting the content of various substances, and calculating the conversion condition of each element.
TABLE 3 Chlorination conversion of Main elements in iron-vanadium slag at different temperatures
When the chlorination temperature is raised to 325 ℃ or higher, as compared with the conversion rate of each element at different temperatures, V 2 O 5 The chlorination conversion rate of (2) can reach more than 90%, but when the temperature is higher than 400 ℃, al 2 O 3 The conversion rate of (C) is obviously increased, so that the chlorination conversion temperature is controlled at350 ℃, can effectively control Al 2 O 3 Is transformed and ensured V 2 O 5 The conversion of (2) is higher than 90%.
Example 3: refining of vanadium oxychloride crude product
Collecting the liquid chloridized substances generated after the reaction, and respectively measuring VOCl in the crude liquid chloridized products 3 And distilling at 130deg.C for 60min to obtain refined VOCl 3 The mass fractions thereof were measured respectively.
TABLE 4 crude VOCl 3 Purity before and after refining
From the results, al is contained in the reaction mixture at a low reaction temperature 2 O 3 The conversion rate of (C) is relatively low, and a coarse VOCl with higher mass fraction can be obtained 3 The product can be distilled once to obtain a refined product with higher added value.
Claims (8)
1. A disposal method of iron-containing vanadium slag filter cake is characterized in that the iron-containing vanadium slag filter cake and petroleum coke are fully mixed on a small particle scale by pulping, then granulation is carried out in a spray mode, the raw materials are subjected to anaerobic dehydrogenation after granulation, hydrogen elements in raw material slag are removed, and meanwhile, partial vanadium and iron oxides in the raw materials can be reduced to low valence states, so that chlorination reaction can be carried out at low temperature, the subsequent chlorination reaction temperature is effectively reduced, and the chlorination conversion rate of impurity elements is further controlled. The method comprises the following steps:
firstly, pulping and uniformly mixing an iron-containing vanadium slag filter cake, water and ball-milled petroleum coke;
step two, drying and granulating the mixed slurry under certain conditions;
thirdly, the granulated raw material is dehydrogenated and reduced into low-valence metal oxide under the protection of inert gas at a certain temperature;
fourthly, chloridizing the reduced raw materials at a certain temperature to obtain chloridized products of vanadium and iron, and condensing and separating at a certain temperature to obtain a crude vanadium oxychloride product;
and fifthly, refining the crude vanadium oxychloride product to obtain a refined chloride product.
2. The method for disposing the iron-containing vanadium slag filter cake according to claim 1, wherein the iron-containing vanadium slag filter cake in the first step is an iron vanadate precipitate (xFe 2 O 3 ·yV 2 O 5 ·zH 2 O) may contain a small amount of Fe (OH) 3 And other metal salt or hydroxide impurities, the average particle size is 10-20 μm.
3. The method for treating iron-containing vanadium slag filter cake according to claim 1, wherein the beating solid content in the first step is 10-30%, preferably 15-20%, the petroleum coke addition is 10-50%, preferably 25-35% of the vanadium iron slag dry basis mass, and the average particle size is 10-30 μm.
4. The method for treating iron-containing vanadium slag filter cake according to claim 1, wherein the drying and granulating mode in the second step is spraying, wherein the spraying condition is that the inlet temperature is 200-400 ℃, preferably 250-350 ℃, the outlet temperature is 100-200 ℃, preferably 120-160 ℃, and the frequency of an atomizer is 20-40 Hz, preferably 25-35 Hz.
5. The method for disposing iron-containing vanadium slag filter cake according to claim 1, wherein the average particle size of the raw material in the third step is 80-200 μm, and the inert gas is selected from argon or nitrogen, and the temperature is 300-700 ℃, preferably 500-600 ℃.
6. A method of treating a cake of iron-containing vanadium slag according to claim 1, characterized in that the chlorination reaction in the fourth step is carried out in an ebullated bed chlorination reactor at a temperature of 200-600 ℃, preferably 300-350 ℃.
7. The method for disposing iron-containing vanadium slag filter cake according to claim 1, wherein the condensing and recovering temperature of ferric chloride in the fourth step is 200-500 ℃, preferably 250-350 ℃, and the condensing and recovering temperature of the vanadium oxychloride crude product is-20-100 ℃, preferably-20 ℃.
8. The method for disposing iron-containing vanadium slag filter cake according to claim 1, wherein the refining method of the coarse product of vanadium oxychloride in the fifth step is distillation, and the distillation temperature is 120-150 ℃, preferably 130-140 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210548445.8A CN117701885A (en) | 2022-09-07 | 2022-09-07 | Treatment method of iron-containing vanadium slag filter cake |
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| CN202210548445.8A CN117701885A (en) | 2022-09-07 | 2022-09-07 | Treatment method of iron-containing vanadium slag filter cake |
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