CN111455163A - Production process for extracting vanadium from stone coal - Google Patents
Production process for extracting vanadium from stone coal Download PDFInfo
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- CN111455163A CN111455163A CN201910045906.8A CN201910045906A CN111455163A CN 111455163 A CN111455163 A CN 111455163A CN 201910045906 A CN201910045906 A CN 201910045906A CN 111455163 A CN111455163 A CN 111455163A
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- Prior art keywords
- vanadium
- carbon
- leaching
- sulfuric acid
- stone coal
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- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 62
- 239000003245 coal Substances 0.000 title claims abstract description 43
- 239000004575 stone Substances 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 45
- 238000002386 leaching Methods 0.000 claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 230000003647 oxidation Effects 0.000 claims abstract description 28
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 28
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 23
- 229920005989 resin Polymers 0.000 claims abstract description 23
- 238000001179 sorption measurement Methods 0.000 claims abstract description 21
- 230000001580 bacterial effect Effects 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 239000012141 concentrate Substances 0.000 claims abstract description 10
- 239000002351 wastewater Substances 0.000 claims abstract description 10
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 7
- 238000000502 dialysis Methods 0.000 claims abstract description 7
- 238000009792 diffusion process Methods 0.000 claims abstract description 7
- 239000000428 dust Substances 0.000 claims abstract description 7
- 150000002500 ions Chemical class 0.000 claims abstract description 7
- 239000000779 smoke Substances 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 239000012528 membrane Substances 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 239000002699 waste material Substances 0.000 claims description 12
- 238000003795 desorption Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004088 foaming agent Substances 0.000 claims description 6
- 238000012856 packing Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 241000605222 Acidithiobacillus ferrooxidans Species 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- 239000004576 sand Substances 0.000 claims description 5
- 239000002893 slag Substances 0.000 claims description 5
- 238000005188 flotation Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 4
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 claims description 3
- 241000605272 Acidithiobacillus thiooxidans Species 0.000 claims description 3
- 241001655237 Thiococcus Species 0.000 claims description 3
- 238000005273 aeration Methods 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 239000003011 anion exchange membrane Substances 0.000 claims description 3
- 239000003957 anion exchange resin Substances 0.000 claims description 3
- 239000010692 aromatic oil Substances 0.000 claims description 3
- LUXKKWCMHGCOBJ-UHFFFAOYSA-N azanium vanadium chloride Chemical compound [V].[Cl-].[NH4+] LUXKKWCMHGCOBJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 3
- 239000002283 diesel fuel Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000011081 inoculation Methods 0.000 claims description 3
- 239000003350 kerosene Substances 0.000 claims description 3
- 239000010687 lubricating oil Substances 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 claims description 3
- 239000010665 pine oil Substances 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000012629 purifying agent Substances 0.000 claims description 3
- 230000002000 scavenging effect Effects 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 3
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- PHIQPXBZDGYJOG-UHFFFAOYSA-N sodium silicate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-][Si]([O-])=O PHIQPXBZDGYJOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000013589 supplement Substances 0.000 claims description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 241000589925 Leptospirillum Species 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 230000005855 radiation Effects 0.000 claims 1
- KJDNAUVRGACOHX-UHFFFAOYSA-N sulfuric acid;vanadium Chemical compound [V].OS(O)(=O)=O KJDNAUVRGACOHX-UHFFFAOYSA-N 0.000 claims 1
- 238000000605 extraction Methods 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000003723 Smelting Methods 0.000 abstract description 2
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 5
- 239000010445 mica Substances 0.000 description 4
- 229910052618 mica group Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000002918 waste heat Substances 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 210000003000 inclusion body Anatomy 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241000589921 Leptospirillum ferrooxidans Species 0.000 description 1
- 241000605118 Thiobacillus Species 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/10—Roasting processes in fluidised form
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/002—Inorganic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/008—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/302—Treatment of water, waste water, or sewage by irradiation with microwaves
-
- 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
- C22B3/18—Extraction of metal compounds from ores or concentrates by wet processes with the aid of microorganisms or enzymes, e.g. bacteria or algae
-
- 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
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/04—Frothers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/06—Depressants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; Specified applications
- B03D2203/02—Ores
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- 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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- Environmental & Geological Engineering (AREA)
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- Materials Engineering (AREA)
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- Hydrology & Water Resources (AREA)
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- Biotechnology (AREA)
- Biochemistry (AREA)
- Water Supply & Treatment (AREA)
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- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the technical field of vanadium extraction and smelting of stone coal vanadium ore. In particular to a production process for extracting vanadium from stone coal, which comprises the steps of 1, floating and carbon-selecting high-carbon stone coal; step 2, roasting the high-carbon concentrate by a fluidized bed; step 3, performing bacterial oxidation on the calcine, the smoke dust, the low-carbon stone coal and the carbon separation tailings of the fluidized bed; step 4, ion membrane diffusion dialysis; step 5, leaching vanadium by sulfuric acid; step 6, resin adsorption; step 7, desorbing the loaded vanadate radical resin; step 8, precipitating vanadium by ammonium chloride; step 9, removing ammonia nitrogen from the wastewater through microwave irradiation; step 10, calcining; the method has the advantages of simplified process, high automation degree, high productivity and vanadium leaching rate and little environmental pollution.
Description
Technical Field
The invention belongs to the technical field of vanadium extraction and smelting of stone coal vanadium ore. In particular to a production process for extracting vanadium from stone coal.
Background
Vanadium in stone coal is mainly V3+、V4+And V5+The valence being present, V3+Not only insoluble in water but also in acids or bases, V4+Insoluble in water but soluble in acid, V5+Both in water and in acid. Direct acid leaching can only leach V4+And V5+Vanadium in the valence state. In the prior art, the low-valence vanadium can be oxidized into V by methods of acid mixing curing, roasting and the like4+And V5+The oxidation degree of the vanadium is lower, and the ratio of low valence state to high valence state vanadium is less; the main reason is that the mineral composition of the stone coal is generally quartz and vanadium mica, the particles of useful minerals are fine, the embedding relationship is complex, most of the useful minerals are present in the vanadium mica, and the particle sizes of a lot of vanadium mica are micro-fine particles and ultra-micro particles, so that the monomers are difficult to dissociate and expose even in fine grinding in the ore grinding process, wherein a part of the vanadium mica exists in the quartz particles or aggregates in the form of inclusion bodies, the particles of the inclusion bodies are very fine and only have the size of several to dozens of micrometers, the monomer is difficult to dissociate or expose during roasting, and the leaching and extraction of the vanadium are greatly influenced.
Disclosure of Invention
Aiming at the problems, the invention aims to provide a stone coal vanadium extraction production process which is simplified in process, high in automation degree, high in capacity and vanadium leaching rate and small in environmental pollution.
The purpose of the invention is realized by the following technical scheme: a production process for extracting vanadium from stone coal comprises the following production steps:
step 1, floating and carbon selecting of high-carbon stone coal: the roughing parameters are that the granularity of stone coal is-0.074 mm and accounts for 80-90%, the inhibitor BKD-5/water glass/sodium hexametaphosphate is 600-minus 1000g/t, the collector kerosene/diesel oil/aromatic oil/lubricating oil is 100-minus 200g/t, the foaming agent pine oil/sec-octanol/methyl isobutyl carbinol is 80-120g/t, and the roughing time is 3-5 min; scavenging the foaming agent under the condition of 30-70g/t for 1-3 min; selecting the inhibitor for 1-3min under the condition of 150-;
step 2, roasting the high-carbon concentrate by a fluidized bed: feeding the high-carbon concentrate subjected to carbon flotation and separation by the high-carbon stone coal in the step 1 into a fluidized bed for roasting, wherein the roasting temperature is 800-880 ℃, the pressure at the bottom of the furnace is 9-14kPa, and the carbon content of both the roasted sand and the smoke dust is lower than 3%;
step 3, performing bacterial oxidation on the roasted sand and the smoke dust of the fluidized bed, the low-carbon stone coal and the carbon-selecting tailings together, wherein the carbon content is required to be less than 4.0 percent by weight, the granularity is 0.037mm, the coal pulp concentration is 10-15 percent, and thiobacillus ferrooxidans/thiobacillus thiooxidans/thiobacillus ferrooxidans/leptospirillum thiophyllus/thiococcus thermophilus 10-30 × 10 are adopted7The inoculation mode of cell/m L bacterial liquid has initial pH value of 1.8-2.0, initial potential of 650-700mV, oxidation temperature of 30-35 ℃, and aeration quantity of 0.8-1.0m3H, the oxidation time is 15-30 d;
step 4, ion membrane diffusion dialysis: testing the oxidized liquid generated by bacterial oxidation to detect vanadium, and if the oxidized liquid contains vanadium, entering the step 6 to perform resin adsorption; if no vanadium is contained, the diffusion dialysis treatment is carried out by adopting an anion exchange membrane, and the current density is 200-2The voltage is 3.0-4.0V, the liquid temperature is 40-60 ℃, the recovery rate of sulfuric acid is more than 85 percent, and the rejection rate of impurity ions is more than 90 percent;
step 5, leaching vanadium with sulfuric acid: carrying out sulfuric acid leaching on oxidation slag generated by bacterial oxidation to obtain vanadium;
step 6, resin adsorption: adsorbing the leachate leached by sulfuric acid by using transformed D301(Cl) anion exchange resin;
step 7, desorbing the loaded vanadate radical resin;
step 8, ammonium chloride vanadium precipitation: adjusting pH value of desorption solution to 8.0, adding purifying agent magnesium sulfate/ammonium sulfate, and purifying and stirring at room temperature for more than 1 hr to remove impurities such as phosphorus and silicon. Adding ammonium chloride at room temperature to precipitate vanadium, wherein the pH value is 7.0-8.5, and the addition amount of agricultural ammonium chloride is 60-90kg/m3Counting, stirring for 1-2h, and aging for 4-5 h; the obtained ammonium metavanadate enters a calcining procedure through washing, filtering and the like, and ammonia nitrogen is removed from waste liquid obtained by vanadium precipitation by adopting microwave;
and 9, removing ammonia nitrogen from the wastewater by microwave irradiation: before ammonia nitrogen removal treatment, the waste liquid obtained by vanadium precipitation is subjected to ammonia nitrogen concentration testing detection and modified activated carbon addition operation, the mass ratio of the modified activated carbon to ammonia nitrogen in the ammonia nitrogen waste water is 2-120: 1, and the ammonia nitrogen waste water added with the modified activated carbon is irradiated in a microwave field to remove ammonia nitrogen. The microwave power is 200-4 +The modified activated carbon is one or more of sodium hydroxide/potassium hydroxide/sodium chloride/potassium chloride/sodium silicate nonahydrate/hydrochloric acid/sulfuric acid, and the activated carbon is subjected to modification treatment;
step 10, calcining: calcining the wet ammonium metavanadate produced in the step 8 in a drying kiln in a heating mode of electric/coal heating for 2-3h at 600 ℃ to produce orange-red 98% powder vanadium, namely vanadium pentoxide;
further, in step 5, vanadium is leached by sulfuric acid in the oxidation slag generated by bacterial oxidation, the leaching temperature is normal temperature, the leaching agent is water and concentrated sulfuric acid, the pH value is 1.5-3.0, the liquid-solid ratio is 1.1-3.5: 1, and the leaching time is 1-3.5 h. Leaching products are leaching residues and leaching liquid, the leaching residues are washed, filter-pressed and stockpiled, and the leaching liquid is subjected to resin adsorption;
further, in step 6, the pH value is 1.5-2.5, the adsorption temperature is normal temperature, the resin packing density is 0.65-0.75g/m L, the packing porosity is 20-40%, the adsorption contact time is 10-15min, the adsorbed products are the solution after adsorption and the loaded vanadate resin, and the solution after adsorption returns to step 3;
further, for the step 7, 100-200 g/L sodium hydroxide/potassium hydroxide solution is adopted for cyclic desorption, the desorption temperature is normal temperature, the contact time is 6-8min, and the desorbed resin is regenerated by hydrochloric acid conversion and enters the next cycle period;
further, in the step 1, high-carbon concentrate and carbon separation tailings are produced by floating and carbon separation of the high-carbon stone coal;
further, the waste heat generated in the step 2 can be comprehensively utilized for production heating, living heating or power generation and the like;
further, step 4 produces sulfuric acid, which can be sold or returned to bacterial oxidation as a supplement to sulfuric acid or to sulfuric acid leaching of vanadium, and a waste stream, which is neutralized and discharged.
Has the advantages that:
1. high-carbon stone coal and low-carbon stone coal are separately treated, then the high-carbon stone coal is subjected to carbon flotation, and the high-carbon stone coal, the low-carbon stone coal and the carbon-selecting tailings are combined for bacterial oxidation after roasting, so that the influence of carbon in the stone coal in the bacterial oxidation process is eliminated, and the carbon and heat in the stone coal are efficiently utilized;
2. v in stone coal raw ore3+、V4+And V5+Regardless of the size of the components, the leaching rate of vanadium oxidized by bacteria can reach more than 90 percent, which is far higher than the leaching rate of normal stone coal conventional roasting by 50-75 percent, and the recovery rate of vanadium is high;
3. the whole production process has no open circuit, and vanadium is fully recovered;
4. no HCl and Cl2The pollution is reduced, the waste gas of the roasting additive is not discharged, the production is clean, and the environmental protection requirement is met;
5. the waste heat of the high-carbon concentrate fluidized bed roasting can be comprehensively utilized, the dilute sulfuric acid in the waste liquid can be comprehensively recovered, and the high-efficiency utilization of components can be realized in a production system;
6. the process has the advantages of less sulfuric acid consumption, renewable sulfuric acid, low production cost, reduced purchasing burden of sulfuric acid and reduced environmental pollution;
7. the process investment is low, the automatic control can be realized, the labor intensity of workers is low, and the method is suitable for large-scale industrialization;
8. the equipment is simple and easy to select, the complicated and difficult selection of equipment such as a flat kiln, a vertical kiln, a rotary kiln and the like for conventional roasting of the stone coal is not needed, and the bed energy rate of the roasting of the high-carbon concentrate fluidized bed is far higher than that of the flat kiln, the vertical kiln and the rotary kiln;
9. the process can be split into a plurality of individual small processes.
Drawings
Is free of
Detailed Description
The following is a detailed description of the present invention for further explanation. The invention is not limited to the claims, and all modifications, equivalents and flow variations that may be made by using the teachings of the invention, or directly or indirectly applied to other related arts, are intended to be covered by the scope of the invention.
Example 1: a production process for extracting vanadium from stone coal comprises the following production steps:
step 1, floating and carbon selecting of high-carbon stone coal: the roughing parameters are that the granularity of stone coal is-0.074 mm and accounts for 80-90%, the inhibitor BKD-5/water glass/sodium hexametaphosphate is 600-minus 1000g/t, the collector kerosene/diesel oil/aromatic oil/lubricating oil is 100-minus 200g/t, the foaming agent pine oil/sec-octanol/methyl isobutyl carbinol is 80-120g/t, and the roughing time is 3-5 min; scavenging the foaming agent under the condition of 30-70g/t for 1-3 min; selecting under the condition of 150-;
step 2, roasting the high-carbon concentrate by a fluidized bed: feeding the high-carbon concentrate subjected to carbon flotation and separation by the high-carbon stone coal in the step 1 into a fluidized bed for roasting, wherein the roasting temperature is 800-880 ℃, the pressure at the bottom of the furnace is 9-14kPa, the carbon content of the roasted sand and the smoke dust is lower than 3%, and the generated waste heat can be comprehensively utilized for production heating, life heating or power generation and the like;
step 3, performing bacterial oxidation on the roasted sand and the smoke dust of the fluidized bed, the low-carbon stone coal and the carbon-dressing tailings: claim containsThe weight percentage of carbon is less than 4.0 percent, the granularity of 0.037mm accounts for 70-90 percent, the concentration of ore pulp is 10-15 percent, thiobacillus ferrooxidans/thiobacillus thiooxidans/leptospirillum ferrooxidans/thiococcus phyllophilus/thiobacillus thermophilus 10-30 × 10 percent is adopted7The inoculation mode of cell/m L bacterial liquid has initial pH value of 1.8-2.0, initial potential of 650-700mV, oxidation temperature of 30-35 ℃, and aeration quantity of 0.8-1.0m3H, the oxidation time is 15-30 d;
step 4, ion membrane diffusion dialysis: testing the oxidized liquid generated by bacterial oxidation to detect vanadium, and if the oxidized liquid contains vanadium, entering the step 6 to perform resin adsorption; if no vanadium is contained, the diffusion dialysis treatment is carried out by adopting an anion exchange membrane, and the current density is 200-2The voltage is 3.0-4.0V, the liquid temperature is 40-60 ℃, the recovery rate of sulfuric acid is more than 85 percent, the rejection rate of impurity ions is more than 90 percent, sulfuric acid and waste liquid are generated, the sulfuric acid can be sold or returned to bacterial oxidation to be used as the supplement of the sulfuric acid or the sulfuric acid for vanadium leaching, and the waste liquid is discharged after neutralization treatment;
step 5, leaching vanadium with sulfuric acid: leaching vanadium from oxidation slag generated by bacterial oxidation by sulfuric acid at normal temperature, wherein the leaching agent is water and concentrated sulfuric acid, the pH value is 1.5-3.0, the liquid-solid ratio is 1.1-3.5: 1, and the leaching time is 1-3.5 h. Leaching products are leaching residues and leaching liquid, the leaching residues are washed, filter-pressed and stockpiled, and the leaching liquid is subjected to resin adsorption;
step 6, resin adsorption, namely adsorbing the leachate leached out by sulfuric acid by using transformed D301(Cl) anion exchange resin, wherein the pH value is 1.5-2.5, the adsorption temperature is normal temperature, the resin packing density is 0.65-0.75g/m L, the packing porosity is 20-40%, the adsorption contact time is 10-15min, the adsorbed products are adsorbed liquid and loaded vanadate resin, and the adsorbed liquid returns to the step 3;
step 7, desorption of the loaded vanadate resin, namely performing cyclic desorption by adopting a sodium hydroxide/potassium hydroxide solution of 100-200 g/L, wherein the desorption temperature is normal temperature, the contact time is 6-8min, and the desorbed resin is regenerated by hydrochloric acid transformation and enters the next cycle period;
step 8, ammonium chloride vanadium precipitation: adjusting pH of desorbed desorption solution to 8, adding purifying agent magnesium sulfate/ammonium sulfate, purifying at room temperature for more than 1 hr under stirring to remove phosphorusSilicon, and the like. Adding ammonium chloride at room temperature to precipitate vanadium, wherein the pH value is 7.0-8.5, and the addition amount of agricultural ammonium chloride is 60-90kg/m3Counting, stirring for 1-2h, and aging for 4-5 h; the obtained ammonium metavanadate enters a calcining procedure through washing, filtering and the like, and ammonia nitrogen is removed from waste liquid obtained by vanadium precipitation by adopting microwave;
and 9, removing ammonia nitrogen from the wastewater by microwave irradiation: before ammonia nitrogen removal treatment, the waste liquid obtained by vanadium precipitation is subjected to ammonia nitrogen concentration testing detection and modified activated carbon addition operation, the mass ratio of the modified activated carbon to ammonia nitrogen in the ammonia nitrogen waste water is 2-120: 1, and the ammonia nitrogen waste water added with the modified activated carbon is irradiated in a microwave field to remove ammonia nitrogen. The microwave power is 200-4 +The modified activated carbon is one or more of sodium hydroxide/potassium hydroxide/sodium chloride/potassium chloride/sodium silicate nonahydrate/hydrochloric acid/sulfuric acid, and the activated carbon is subjected to modification treatment;
step 10, calcining: and (3) calcining the wet ammonium metavanadate produced in the step (8) in a drying kiln in a heating mode of electric/coal heating for 2-3h at 600 ℃ to produce orange-red 98% powder vanadium, namely vanadium pentoxide.
Claims (5)
1. A production process for extracting vanadium from stone coal is characterized by comprising the following steps: comprises the following production steps:
step 1, floating and carbon selecting of high-carbon stone coal: the roughing parameters are that the granularity of stone coal is-0.074 mm and accounts for 80-90%, the inhibitor BKD-5/water glass/sodium hexametaphosphate is 600-minus 1000g/t, the collector kerosene/diesel oil/aromatic oil/lubricating oil is 100-minus 200g/t, the foaming agent pine oil/sec-octanol/methyl isobutyl carbinol is 80-120g/t, and the roughing time is 3-5 min; scavenging the foaming agent under the condition of 30-70g/t for 1-3 min; selecting the inhibitor for 1-3min under the condition of 150-;
step 2, roasting the high-carbon concentrate by a fluidized bed: feeding the high-carbon concentrate subjected to carbon flotation and separation by the high-carbon stone coal in the step 1 into a fluidized bed for roasting, wherein the roasting temperature is 800-880 ℃, the pressure at the bottom of the furnace is 9-14kPa, and the carbon content of both the roasted product and the smoke dust is lower than 3%;
step 3, performing bacterial oxidation on the roasted sand and the smoke dust of the fluidized bed, the low-carbon stone coal and the carbon-selecting tailings together, wherein the weight percentage of carbon is required to be less than 4.0 percent, the granularity of 0.037mm accounts for 70-90 percent, the concentration of ore pulp is 10-15 percent, and thiobacillus ferrooxidans/thiobacillus thiooxidans/thiobacillus ferrooxidans/leptospirillum/thiococcus phyllus/thiothermophilus thiooxidans 10-30 × 10 percent are adopted7The inoculation mode of cell/m L bacterial liquid has initial pH value of 1.8-2.0, initial potential of 650-700mV, oxidation temperature of 30-35 ℃, and aeration quantity of 0.8-1.0m3H, the oxidation time is 15-30 d;
step 4, ion membrane diffusion dialysis: testing the oxidized liquid generated by bacterial oxidation to detect vanadium, and if the oxidized liquid contains vanadium, entering the step 6 to perform resin adsorption; if no vanadium is contained, the diffusion dialysis treatment is carried out by adopting an anion exchange membrane, and the current density is 200-2The voltage is 3.0-4.0V, the liquid temperature is 40-60 ℃, the recovery rate of sulfuric acid is more than 85 percent, and the rejection rate of impurity ions is more than 90 percent;
step 5, leaching vanadium with sulfuric acid: carrying out sulfuric acid leaching on oxidation slag generated by bacterial oxidation to obtain vanadium;
step 6, resin adsorption: adsorbing the leachate leached by sulfuric acid by using transformed D301(Cl) anion exchange resin;
step 7, desorbing the loaded vanadate radical resin;
step 8, ammonium chloride vanadium precipitation: adjusting pH value of desorption solution to 8.0, adding purifying agent magnesium sulfate/ammonium sulfate, and purifying and stirring at room temperature for more than 1 hr to remove impurities such as phosphorus and silicon. Adding ammonium chloride at room temperature to precipitate vanadium, wherein the pH value is 7.0-8.5, and the addition amount of agricultural ammonium chloride is 60-90kg/m3Counting, stirring for 1-2h, and aging for 4-5 h; the obtained ammonium metavanadate enters a calcining procedure through washing, filtering and the like, and waste liquid obtained by vanadium precipitation is subjected to ammonia nitrogen removal by microwaves;
and 9, removing ammonia nitrogen from the wastewater by microwave irradiation: before ammonia nitrogen removal treatment, the waste liquid obtained by vanadium precipitation is subjected to ammonia nitrogen concentration testing detection and modified activated carbon addition operation, the mass ratio of the modified activated carbon to ammonia nitrogen in the ammonia nitrogen waste water is 2-120: 1, and the ammonia nitrogen waste water added with the modified activated carbon is irradiated in a microwave field to remove ammonia nitrogen. Microwave power 200-1500W, 70-95 ℃, microwave radiation for 6-12min, ammonia nitrogen removal rate more than 99 percent, and the waste liquid after ammonia nitrogen removal conforms to national NH4 +The modified activated carbon is one or more of sodium hydroxide/potassium hydroxide/sodium chloride/potassium chloride/sodium silicate nonahydrate/hydrochloric acid/sulfuric acid, and the activated carbon is subjected to modification treatment;
step 10, calcining: and (3) calcining the wet ammonium metavanadate produced in the step (8) in a drying kiln in a heating mode of electric/coal heating for 2-3h at 600 ℃ to produce orange-red 98% powder vanadium, namely vanadium pentoxide.
2. The process for producing vanadium from stone coal as claimed in claim 1, wherein in step 5, vanadium leaching is carried out by sulfuric acid of the oxidized slag generated by bacterial oxidation at normal temperature, the leaching agent is water and concentrated sulfuric acid, the pH value is 1.5-3.0, the liquid-solid ratio is 1.1-3.5: 1, and the leaching time is 1-3.5 h. The leaching products are leaching residues and leaching liquid, the leaching residues are washed, filter-pressed and stockpiled, and the leaching liquid is subjected to resin adsorption.
3. The process for producing vanadium from stone coal as claimed in claim 1 or 2, wherein in step 6, pH value is 1.5-2.5, adsorption temperature is normal temperature, resin packing density is 0.65-0.75g/m L, packing porosity is 20-40%, adsorption contact time is 10-15min, after adsorption, the product is solution after adsorption and vanadate-loaded resin, and solution after adsorption is returned to step 3.
4. The process as claimed in claim 3, wherein step 7, the process comprises using 100-200 g/L NaOH/KOH solution for cyclic desorption, the desorption temperature is normal temperature, the contact time is 6-8min, and the resin after desorption is regenerated by hydrochloric acid conversion and enters the next cycle.
5. The process of claim 1, wherein step 4 produces sulfuric acid for sale or return to bacterial oxidation as a supplement to sulfuric acid or sulfuric acid vanadium leaching, and a waste stream that is neutralized and discharged.
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