WO2016119718A1 - 一种提纯五氧化二钒的***及方法 - Google Patents
一种提纯五氧化二钒的***及方法 Download PDFInfo
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- WO2016119718A1 WO2016119718A1 PCT/CN2016/072520 CN2016072520W WO2016119718A1 WO 2016119718 A1 WO2016119718 A1 WO 2016119718A1 CN 2016072520 W CN2016072520 W CN 2016072520W WO 2016119718 A1 WO2016119718 A1 WO 2016119718A1
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- gas
- vanadium
- chlorination
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- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 title claims abstract description 196
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000007789 gas Substances 0.000 claims abstract description 151
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 115
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000003546 flue gas Substances 0.000 claims abstract description 54
- ZHXZNKNQUHUIGN-UHFFFAOYSA-N chloro hypochlorite;vanadium Chemical compound [V].ClOCl ZHXZNKNQUHUIGN-UHFFFAOYSA-N 0.000 claims abstract description 50
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 41
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims abstract description 22
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000460 chlorine Substances 0.000 claims abstract description 13
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 13
- 230000001590 oxidative effect Effects 0.000 claims abstract 2
- 239000007788 liquid Substances 0.000 claims description 46
- 229910052720 vanadium Inorganic materials 0.000 claims description 40
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 40
- CGFLRDJQEKNAGT-UHFFFAOYSA-N [V].O(Cl)Cl.[V] Chemical compound [V].O(Cl)Cl.[V] CGFLRDJQEKNAGT-UHFFFAOYSA-N 0.000 claims description 35
- 238000010992 reflux Methods 0.000 claims description 31
- 239000000843 powder Substances 0.000 claims description 28
- 238000003860 storage Methods 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 27
- 239000006096 absorbing agent Substances 0.000 claims description 26
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 25
- 229910052710 silicon Inorganic materials 0.000 claims description 25
- 239000010703 silicon Substances 0.000 claims description 25
- 238000007789 sealing Methods 0.000 claims description 22
- 238000004821 distillation Methods 0.000 claims description 20
- 239000002893 slag Substances 0.000 claims description 18
- 239000012535 impurity Substances 0.000 claims description 17
- 230000003647 oxidation Effects 0.000 claims description 17
- 238000007254 oxidation reaction Methods 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 17
- 239000000376 reactant Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000009835 boiling Methods 0.000 claims description 14
- 238000000746 purification Methods 0.000 claims description 11
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- 238000005243 fluidization Methods 0.000 claims description 3
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 claims description 2
- BVGNRFAXUJSLRW-UHFFFAOYSA-M [O-2].[O-2].[OH-].O.O.Cl.[V+5] Chemical compound [O-2].[O-2].[OH-].O.O.Cl.[V+5] BVGNRFAXUJSLRW-UHFFFAOYSA-M 0.000 claims 1
- 239000012530 fluid Substances 0.000 claims 1
- MXXWOMGUGJBKIW-YPCIICBESA-N piperine Chemical compound C=1C=C2OCOC2=CC=1/C=C/C=C/C(=O)N1CCCCC1 MXXWOMGUGJBKIW-YPCIICBESA-N 0.000 claims 1
- 229940075559 piperine Drugs 0.000 claims 1
- 235000019100 piperine Nutrition 0.000 claims 1
- IBYSTTGVDIFUAY-UHFFFAOYSA-N vanadium monoxide Chemical compound [V]=O IBYSTTGVDIFUAY-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000002351 wastewater Substances 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 15
- 238000001556 precipitation Methods 0.000 description 14
- 239000002994 raw material Substances 0.000 description 13
- 238000002386 leaching Methods 0.000 description 12
- 150000003863 ammonium salts Chemical class 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 2
- 239000012629 purifying agent Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 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
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 206010024769 Local reaction Diseases 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910021552 Vanadium(IV) chloride Inorganic materials 0.000 description 1
- WGKMWBIFNQLOKM-UHFFFAOYSA-N [O].[Cl] Chemical compound [O].[Cl] WGKMWBIFNQLOKM-UHFFFAOYSA-N 0.000 description 1
- GDQJRIJQPNLZBK-UHFFFAOYSA-A [V+5].O(Cl)Cl.[V+5].[Cl-].[V+5].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-] Chemical compound [V+5].O(Cl)Cl.[V+5].[Cl-].[V+5].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-] GDQJRIJQPNLZBK-UHFFFAOYSA-A 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- -1 ammonium ions Chemical class 0.000 description 1
- SKKMWRVAJNPLFY-UHFFFAOYSA-N azanylidynevanadium Chemical compound [V]#N SKKMWRVAJNPLFY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/0042—Degasification of liquids modifying the liquid flow
- B01D19/0052—Degasification of liquids modifying the liquid flow in rotating vessels, vessels containing movable parts or in which centrifugal movement is caused
- B01D19/0057—Degasification of liquids modifying the liquid flow in rotating vessels, vessels containing movable parts or in which centrifugal movement is caused the centrifugal movement being caused by a vortex, e.g. using a cyclone, or by a tangential inlet
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/04—Halides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Definitions
- the invention belongs to the field of chemical industry and material, and particularly relates to a system and a method for purifying vanadium pentoxide.
- Vanadium pentoxide is one of the important industrial vanadium products, widely used in the production of alloy additives such as vanadium iron and vanadium nitride, as well as catalysts, colorants, and hard alloy additives. With the continuous development of new energy technologies, the battery industry is increasingly demanding high-purity vanadium pentoxide (purity of more than 3N5), including all-vanadium flow batteries (VRB) with good large-scale energy storage performance and vanadium for electric vehicles.
- the acid salt is a lithium ion battery or the like.
- the vanadium solution is usually obtained by leaching a vanadium solution or a vanadium-rich material (such as ammonium polyvanadate, ammonium metavanadate, industrial grade vanadium pentoxide, etc.), and is purified by chemical precipitation or (and) solvent extraction/ion.
- a vanadium-rich material such as ammonium polyvanadate, ammonium metavanadate, industrial grade vanadium pentoxide, etc.
- the impurity removal process parameters are closely related to the impurity content of the raw materials, so the adaptability to the raw materials is poor; the calcium salt, magnesium salt purifying agent or extractant used in the purification process, the acid-base reagent, and the ammonium salt for vanadium precipitation are also It is easy to introduce impurities.
- it is generally required to use an expensive reagent with a high purity, so that the cost is too high, the scale cannot be produced, and the purity of the product is difficult to be stabilized at 3N5 or more.
- the related institution also proposes to adopt the repeated precipitation method to purify and remove the vanadium solution, that is, to utilize the ammonium salt precipitation property of the vanadium-containing solution to selectively select vanadium.
- the raw material chlorination-rectification purification-subsequent treatment is a common preparation process for high-purity materials, such as high purity. Silicon (polysilicon), high purity silica, and the like.
- vanadium chloride vanadium oxychloride vanadium has a large difference from the boiling points of common impurities such as iron, calcium, magnesium, aluminum, sodium, potassium, etc., it is easy to obtain high purity vanadium oxychloride by rectification, and from high purity three High-purity vanadium pentoxide can be prepared by hydrolysis of vanadium oxychloride by hydrolysis and precipitation of ammonium salts, followed by calcination. Therefore, the preparation of high-purity vanadium pentoxide by the chlorination method has a great advantage in principle.
- the patent has the following deficiencies: (1) Similar to the aforementioned Iowa State University study, the patent actually only gives the principle of chlorination, lacking specific operational solutions, such as chlorination including both boiling chlorine And include molten salt chlorination, and molten salt chlorination and boiling chlorination are completely different chlorination methods; for example, for chlorination reactors, "rotary kiln, fluidized furnace, boiling furnace, shaft furnace, Reactors such as multi-hearth furnaces actually cover almost all common mainstream reactors in the metallurgical industry, but different reactors have very different requirements for raw materials. Shaft furnaces can only handle "coarse" particles larger than 8 mm.
- fine particles need to be treated with pellets and pre-sintering, while boiling chlorination is generally suitable for processing fine particles, so for a specific vanadium raw material, it cannot be directly applied to rotary kiln, fluidized furnace, boiling furnace, shaft furnace, and more.
- the reactor such as a crucible furnace; and the "fluidizer” and the “boiling furnace” are essentially the same, but the name is different; thus, it can be seen that the operation modes and conditions of these reactors are very different.
- vanadium raw material chlorination technology still has the following two problems: (1) vanadium raw material chlorination roasting is a strong exothermic process, and the heat generated by the chlorination reaction can satisfy the solid and gas. In addition to the preheating of the reaction material, it is still necessary to remove the heat through the furnace wall to stabilize the chlorination temperature. Therefore, the solid and the gas usually enter the reactor at a near room temperature, and the chlorination reaction generates heat to preheat before participating in the reaction.
- the local reaction efficiency of the chlorination reactor is too low; (2) due to the need to remove the heat generated by the chlorination reaction by a large amount of heat dissipation to maintain the operating temperature, the operating conditions and environmental climate changes are liable to cause chlorination temperature fluctuations, resulting in chlorination selection. Reduced sex and efficiency require a reasonable heat balance supply and temperature regulation. Therefore, it is necessary to provide a reasonable heat supply and temperature control to effectively increase the chlorination efficiency and obtain a stable chlorination temperature to ensure the selectivity of chlorination to effectively suppress the chlorination of impurities.
- the temperature regulation of the chlorination process the improvement of the direct yield of vanadium, the reduction of waste discharge, the reduction of production energy consumption and the consumption of chlorine gas are the techniques for improving the preparation of high-purity vanadium pentoxide by chlorination. The key to economics.
- the present invention provides a system and method for purifying vanadium pentoxide to ensure good selectivity of low temperature chlorination, avoiding generation of a large amount of polluted wastewater, reducing production energy consumption of high purity vanadium pentoxide, and chlorine consumption. And operating costs.
- the present invention adopts the following technical solutions:
- the system for purifying vanadium pentoxide of the present invention comprising a feeding device 1, a low temperature chlorination fluidized bed 2, a rectification and purification device 3, a plasma oxidation device 4, an exhaust gas leaching absorber 5, an induced draft fan 6 and Chimney 7;
- the feeding device 1 comprises an industrial grade vanadium pentoxide silo 1-1, an industrial grade vanadium pentoxide screw feeder 1-2, a carbon powder silo 1-3 and a carbon powder screw feeder 1-4;
- the low temperature chlorination fluidized bed 2 comprises a chlorination bed feeder 2-1, a chlorinated fluidized bed main body 2-2, a chlorinated bed cyclone 2-3, a flue gas heat exchanger 2-4, a smoke Gas condenser 2-5, chlorinated bed acid sealed tank 2-6 and chlorination Bed spiral slag remover 2-7;
- the rectification and purification device 3 includes a distillation still 3-1, a rectification column 3-2, a distillate condenser 3-3, a reflux liquid collection tank 3-4, a silicon-containing vanadium oxychloride vanadium storage tank 3-5, Distillation section acid sealing tank 3-6, high purity vanadium oxychloride vanadium condenser 3-7 and high purity vanadium oxychloride vanadium storage tank 3-8;
- the plasma oxidation apparatus 4 includes an air filter purifier 4-1, a reactant nozzle 4-2, a plasma reactor 4-3, a primary cyclone 4-4, a secondary cyclone 4-5, and a spin Leaf pump 4-6 and gas compressor 4-7;
- the outlet of the bottom of the industrial grade vanadium pentoxide silo 1-1 is connected to the inlet of the industrial grade vanadium pentoxide screw feeder 1-2; the bottom of the carbon powder silo 1-3
- the discharge port is connected to the feed port of the carbon powder screw feeder 1-4; the discharge port of the industrial grade vanadium pentoxide screw feeder 1-2, the carbon powder screw feeder 1-
- the discharge ports of 4 are connected to the feed port of the chlorination bed feeder 2-1 through a pipe;
- the discharge port of the chlorination bed feeder 2-1 is connected to the inlet of the upper portion of the chlorinated fluidized bed main body 2-2 through a pipe; the bottom of the chlorination bed feeder 2-1
- the inlet port is connected to the nitrogen gas source manifold through a pipe;
- the chlorination bed cyclone separator 2-3 is disposed at the top center of the enlarged section of the chlorination fluidized bed main body 2-2;
- the chlorination bed cyclone separation The gas outlet at the top of the 2-3 is connected to the hot flue gas inlet of the flue gas heat exchanger 2-4 through a pipe; the cold flue gas outlet of the flue gas heat exchanger 2-4 passes through the pipe and the smoke a gas inlet of the gas condenser 2-5 is connected;
- a gas outlet of the flue gas condenser 2-5 is connected to a gas inlet of the chlorinated bed acid sealing tank 2-6 through a pipe;
- the chlorinated bed acid The gas outlet of the sealing tank 2-6 is connected
- the liquid outlet at the bottom of the flue gas condenser 2-5 is connected to the feed port of the rectification column 3-2 through a pipe; the vapor outlet of the distillation still 3-1 passes through the pipe and the rectification column 3 a vapor inlet of -2 is connected; a reflux port of the distillation pot 3-1 is connected to a liquid reflux outlet at the bottom of the rectification column 3-2 through a pipe; a gas outlet at the top of the rectification column 3-2 is passed a conduit is connected to the gas inlet of the distillate condenser 3-3; the liquid outlet of the distillate condenser 3-3 is connected to the liquid inlet of the reflux collection tank 3-4 via a conduit; The reflux liquid outlet of the reflux liquid collection tank 3-4 is connected to the reflux liquid inlet at the top of the rectification column 3-2 through a pipe; the discharge port of the reflux liquid collection tank 3-4 and the silicon-containing three Chlorine oxygen
- the inlets of the vanadium storage tanks 3-5 are connected by pipes; the spent gas
- the air inlet of the air filter purifier 4-1 is connected to the compressed air manifold through a pipeline; the air outlet of the air filter purifier 4-1 is respectively connected to the air inlet and the secondary of the reactant nozzle 4-2 through the pipeline
- the gas inlets of the cyclone separator 4-5 are connected; the liquid outlet of the high purity vanadium oxychloride vanadium storage tank 3-8 is connected to the chloride inlet of the reactant nozzle 4-2 through a conduit; the reactant a nozzle 4-2 is disposed at an upper center of the plasma reactor 4-3; a material outlet at the bottom of the plasma reactor 4-3 is connected to a gas inlet of the primary cyclone 4-4 through a conduit a gas outlet of the primary cyclone 4-4 is connected to a gas inlet of the rotary vane pump 4-6 through a pipe; a gas outlet of the rotary vane pump 4-6 passes through a pipe and the gas compressor
- the gas inlets of 4-7 are connected; the gas outlets of the gas compressors 4-7
- the gas outlet of the exhaust gas rinsing absorber 5 is connected to the gas inlet of the draft fan 6 through a pipe; the gas outlet of the draft fan 6 is connected to the gas inlet at the bottom of the chimney 7 through a pipe.
- the method for purifying vanadium pentoxide based on the above system of the present invention comprises the following steps:
- the industrial grade vanadium pentoxide powder in the industrial grade vanadium pentoxide silo 1-1 and the carbon powder of the carbon powder silo 1-3 are respectively passed through the industrial grade vanadium pentoxide spiral feeder 1 -2 and the carbon powder screw feeder 1-4 simultaneously enter the chlorination bed feeder 2-1 and then enter the chlorination fluidized bed main body 2-2; chlorine gas and nitrogen gas from the chlorine gas source main pipe
- the nitrogen of the gas source main pipe and the air of the compressed air main pipe are preheated by heat exchange between the flue gas heat exchanger 2-4 and the chlorinated flue gas, and then enter the chlorinated fluidized bed main body 2-2 to make vanadium pentoxide.
- the powder material such as carbon powder maintains fluidization and chemical reaction with it.
- the air causes some of the carbon powder to burn to provide heat to maintain the fluidized bed temperature.
- the chlorine gas and the carbon powder work together to chlorinate vanadium pentoxide and a small amount of impurities.
- the separator 2-3 removes the dust and falls back to the chlorination fluidized bed main body 2-2, and then pre-cools through the flue gas heat exchanger 2-4 and enters the flue gas condenser 2-5 to make the dust therein.
- the vanadium oxychloride is condensed to form a crude vanadium oxychloride vanadium, and the remaining tail gas is sealed into the exhaust gas leaching
- the crude vanadium oxychloride vapor formed by the flue gas condenser 2-5 enters the rectification column 3-2 and the distillation still 3-1, and is subjected to a rectification operation to obtain a vanadium-rich scrap rich in high-boiling impurities.
- the high purity vanadium oxychloride in the high purity vanadium oxychloride vanadium storage tank 3-8 enters the plasma reactor 4-3 through the reactant nozzle 4-2; the compressed air passes through the air filter purifier 4-1 After purging, the reactant reactor 4-2 enters the plasma reactor 4-3 to oxidize vanadium oxychloride to form vanadium pentoxide powder and chlorine-rich oxidized flue gas; The discharge port at the bottom of the plasma reactor 4-3 is discharged into the primary cyclone 4-4 to perform gas-solid separation, and the separated oxidized flue gas is separated by the rotary vane pump 4-6 and the gas.
- the machine 4-7 After being pressurized, the machine 4-7 is returned for industrial grade vanadium pentoxide chlorination; the vanadium pentoxide powder discharged from the bottom of the first stage cyclone 4-4 and the air filter purifier 4-1 Purifying air enters the secondary cyclone 4-5 together, and removes a small amount of chlorine gas entrained in the powder by thorough mixing and gas-solid separation, thereby obtaining a high-purity vanadium pentoxide product and sending it to a high-purity product silo; The chlorine-containing tail gas discharged from the secondary cyclone 4-5 enters the exhaust gas leaching absorber 5 for treatment; the tail gas is rinsed The gas discharged from the absorber 5 after being absorbed by the alkali solution is sent to the chimney 7 through the induced draft fan 6 and then emptied.
- One of the features of the present invention is that in the method for producing high-purity vanadium pentoxide powder, in the chlorinated fluidized bed main body 2-2, the amount of carbon powder added in the low-temperature chlorination process is industrial grade.
- the pentoxide vanadium powder has a mass of 10% to 20%, the chlorination operation temperature is 300 to 500 ° C, and the average residence time of the powder is 30 to 80 minutes.
- the second feature of the present invention is that, in the rectification column 3-2, the number of trays in the rectification operation rectification section is 5 to 10, and the number of trays in the stripping section is 10 to 20; During the rectification operation, the reflux ratio (ie, the ratio of the top flow to the discharge amount) is 15 to 40.
- the third feature of the present invention is that, in the plasma reactor 4-3, high-purity vanadium pentoxide is directly prepared by plasma oxidation of high-purity vanadium oxychloride, and the air is purified during the plasma oxidation process.
- the input amount is 2 to 50 times the theoretical amount.
- the purity of the high-purity vanadium pentoxide powder obtained by the invention is above 4N.
- the present invention has the following outstanding advantages:
- the chlorination gas is preheated while cooling the flue gas, so that the temperature distribution of the chlorination reactor is more uniform, and the low-temperature chlorination efficiency of the vanadium raw material is effectively improved;
- a part of the carbon powder is burned by appropriate amount of air to achieve heat balance supply and temperature regulation of the chlorination process, stabilize the chlorination operation temperature, improve the chlorination reaction efficiency and ensure good selectivity of chlorination, and avoid the formation of tetrachlorination.
- side reactions such as vanadium;
- the clean air is used to further remove a small amount of chlorine gas entrained in the vanadium pentoxide product through the cyclone separator, thereby effectively improving the product quality.
- the invention has the advantages of strong raw material adaptability, good selectivity of low temperature chlorination, non-polluting wastewater discharge, low chlorine gas consumption, low production energy consumption and low operation cost, stable product quality, and the like, and is suitable for high purity vanadium pentoxide of 4N or more.
- the large-scale industrial production of powder has good economic and social benefits.
- Figure 1 is a schematic view showing the configuration of a purified vanadium pentoxide system of the present invention.
- FIG. 1 is a schematic view of a system for purifying vanadium pentoxide according to the present invention.
- the system for purifying vanadium pentoxide used in this embodiment includes a feeding device 1, a low temperature chlorination fluidized bed 2, a rectification purification device 3, a plasma oxidation device 4, and an exhaust gas leaching absorber 5, Induced draft fan 6 and chimney 7;
- the feeding device 1 comprises an industrial grade vanadium pentoxide silo 1-1, an industrial grade vanadium pentoxide spiral feeder 1-2, a carbon powder silo 1-3 and a carbon powder screw feeder 1-4;
- the low temperature chlorination fluidized bed 2 comprises a chlorination bed feeder 2-1, a chlorinated fluidized bed main body 2-2, a chlorinated bed cyclone 2-3, a flue gas heat exchanger 2-4, a flue gas condensation 2-5, chlorinated bed acid sealed tank 2-6 and chlorinated bed spiral slag remover 2-7;
- the rectification and purification device 3 includes a distillation still 3-1, a rectification column 3-2, a distillate condenser 3-3, a reflux liquid collection tank 3-4, a silicon-containing vanadium oxychloride vanadium storage tank 3-5, and a rectification Segment acid sealing tank 3-6, high purity vanadium oxychloride vanadium condenser 3-7 and high purity vanadium oxychloride vanadium storage tank 3-8;
- the plasma oxidation apparatus 4 includes an air filter purifier 4-1, a reactant nozzle 4-2, a plasma reactor 4-3, a primary cyclone separator 4-4, a secondary cyclone separator 4-5, and a rotary vane pump. 4-6 and gas compressor 4-7;
- the outlet of the bottom of the industrial grade vanadium pentoxide silo 1-1 is connected with the inlet of the industrial grade vanadium pentoxide screw feeder 1-2; the outlet of the carbon powder silo 1-3 and the charcoal
- the feed ports of the powder auger feeders 1-4 are connected; the discharge ports of the industrial grade vanadium pentoxide screw feeder 1-2, the discharge ports of the carbon powder screw feeders 1-4 are all fed with the chlorination bed
- the feed ports of the 2-1 are connected by pipes;
- the discharge port of the chlorination bed feeder 2-1 is connected to the inlet of the upper part of the chlorination fluidized bed main body 2-2 through a pipe; the inlet of the bottom of the chlorination bed feeder 2-1 is piped and The nitrogen gas source manifold is connected; the chlorination bed cyclone separator 2-3 is disposed at the top center of the enlarged section of the chlorination fluidized bed main body 2-2; the gas outlet of the chlorinated bed cyclone separator 2-3 passes through the pipeline and the smoke
- the hot flue gas inlets of the gas heat exchangers 2-4 are connected; the cold flue gas outlets of the flue gas heat exchangers 2-4 are connected to the gas inlets of the flue gas condensers 2-5 through pipes; the flue gas condensers 2 -
- the gas outlet of 5 is connected to the gas inlet of the chlorinated bed acid sealing tank 2-6 through a pipe; the gas outlet of the chlorinated bed acid sealing tank 2-6 is connected to the gas inlet of the exhaust gas leaching absorb
- the liquid outlet at the bottom of the flue gas condenser 2-5 is connected to the feed port of the rectification column 3-2 through a pipe; the vapor outlet of the distillation still 3-1 is connected to the vapor inlet of the rectification column 3-2 through a pipe; The reflux port of the still 3-1 is connected to the liquid reflux outlet at the bottom of the rectification column 3-2 through a pipe; the gas outlet at the top of the rectification column 3-2 is passed through the gas inlet of the distillate condenser 3-3 through the pipe.
- the liquid outlet of the distillate condenser 3-3 is connected to the liquid inlet of the reflux liquid collection tank 3-4 through a pipe; the reflux liquid outlet of the reflux liquid collection tank 3-4 is passed through the pipe and the top of the rectification column 3-2
- the reflux liquid inlet is connected;
- the discharge port of the reflux liquid collection tank 3-4 is connected to the inlet of the silicon-containing vanadium oxychloride vanadium storage tank 3-5 through the pipeline;
- the silicon-containing vanadium oxychloride vanadium storage tank 3-5 is lacking
- the gas outlet is connected to the gas inlet of the acid sealing tank 3-6 of the rectifying section through a pipeline;
- the gas outlet of the rectifying acid sealing tank 3-6 is connected to the gas inlet of the exhaust gas eluting absorber 7 through a pipeline;
- the rectification tower 3 -2 of the distillate outlet is connected to the gas inlet of the high purity vanadium oxychloride condenser 3-7 through a pipe;
- the air inlet of the air filter purifier 4-1 is connected to the compressed air main pipe through a pipeline; the air outlet of the air filter purifier 4-1 is respectively connected to the air inlet of the reactant nozzle 4-2 and the secondary cyclone separator 4 through the pipeline
- the gas inlets of -5 are connected; the liquid outlet of the high purity vanadium oxychloride vanadium 3-8 is connected to the chloride inlet of the reactant nozzle 4-2 through a conduit; the reactant nozzle 4-2 is disposed in the plasma reactor The upper center of 4-3; the material outlet at the bottom of the plasma reactor 4-3 is connected to the gas inlet of the primary cyclone 4-4 through a pipe; the gas outlet of the primary cyclone 4-4 is piped and swirled.
- the gas inlets of the leaf pumps 4-6 are connected; the gas outlets of the rotary vane pumps 4-6 are connected to the gas inlets of the gas compressors 4-7 through pipes; the gas outlets of the gas compressors 4-7 are exchanged with the flue gas through the pipes
- the cold gas inlets of the heaters 2-4 are connected;
- the discharge port at the lower part of the cyclone separator 4-4 is connected to the gas inlet of the secondary cyclone 4-5 through a pipe; the gas outlet at the top of the secondary cyclone 4-5 is passed through the pipe and the exhaust gas leaching absorber 5
- the gas inlets are connected; the outlet of the bottom of the secondary cyclone 4-5 is connected to the high purity vanadium pentoxide product silo through a pipeline;
- the gas outlet of the exhaust gas leaching absorber 5 is connected to the gas inlet of the draft fan 6 through a pipe; the gas outlet of the draft fan 6 is connected to the gas inlet at the bottom of the chimney 7 through a pipe.
- the vanadium pentoxide powder is purified by the above system, and the specific method comprises: the industrial grade vanadium pentoxide powder in the industrial grade vanadium pentoxide silo 1-1 and the carbon powder in the carbon powder silo 1-3 respectively
- the industrial grade vanadium pentoxide screw feeder 1-2 and the carbon powder screw feeder 1-4 are simultaneously mixed into the chlorination bed feeder 2-1 and then enter the chlorination fluidized bed main body 2-2; from the chlorine gas source
- the chlorine of the main pipe, the nitrogen of the nitrogen gas source pipe and the air of the compressed air main pipe are preheated by the flue gas heat exchanger 2-4 and the chlorinated flue gas, and then enter the chlorinated fluidized bed main body 2-2 to make the pentoxide
- the powder material such as vanadium and carbon powder maintains fluidization and chemical reaction with it.
- the air causes some of the carbon powder to burn to provide heat to maintain the fluidized bed temperature.
- the chlorine gas and the carbon powder work together to cause vanadium pentoxide and a small amount of impurities to form chlorine.
- the chlorination residue and the chlorinated flue gas rich in vanadium oxychloride are formed; the chlorinated residue is sequentially discharged through the slag discharge port of the lower part of the chlorination fluidized bed main body 2-2 and the chlorination bed spiral slag discharge device 2-7.
- the chlorinated flue gas is removed by the chlorination bed cyclone 2-3 and returned to the chlorinated fluidized bed, and then exchanged by the flue gas
- the 2-4 pre-cooled and enters the flue gas condenser 2-5 to condense the vanadium oxychloride therein to form a crude vanadium oxychloride vanadium liquid, and the remaining tail gas is sealed by the chlorinated bed acid to seal the tank 2-6 and then enters the exhaust gas leaching absorption.
- the device 5 In the device 5;
- the crude vanadium oxychloride vapor formed by the flue gas condenser 2-5 enters the rectification column 3-2 and the distillation still 3-1, and is subjected to a rectification operation to obtain a vanadium-rich scrap rich in high-boiling impurities and rich in low-boiling impurities.
- the liquid collection tank 3-4 is refluxed to the rectification column 3-2, and the remaining portion is introduced into the silicon-containing vanadium oxychloride vanadium storage tank 3-5; the spent gas generated in the silicon-containing vanadium oxychloride vanadium storage tank 3-5 is rectified
- the segment acid is sealed 3-6 and sent to the exhaust gas leaching absorber 5.
- the silicon-containing vanadium oxychloride can be used in the chemical field; the high-purity vanadium oxychloride vapor is passed through the high-purity vanadium oxychloride condenser 3-7 After condensing to liquid, enter the high purity vanadium oxychloride vanadium storage tank 3-8;
- the high-purity vanadium oxychloride in the high-purity vanadium oxychloride vanadium storage tank 3-8 enters the plasma reactor 4-3 through the reactant nozzle 4-2; the compressed air is purified by the air filter purifier 4-1
- the nozzle 4-2 enters the plasma reactor 4-3 to oxidize vanadium oxychloride to form vanadium pentoxide powder and chlorine-rich oxidized flue gas; the oxidation product is emitted from the bottom of the plasma reactor 4-3.
- the discharge port is discharged into the first-stage cyclone 4-4, the gas-solid separation is performed, and the separated oxidized flue gas is pressurized by the rotary vane pump 4-6 and the gas compressor 4-7.
- vanadium pentoxide chlorination it is used for industrial grade vanadium pentoxide chlorination; the vanadium pentoxide powder discharged from the bottom of the first stage cyclone 4-4 enters the secondary cyclone separator together with the purified air from the air filter purifier 4-1. 5.
- the small amount of chlorine gas entrained in the powder is removed by thorough mixing and gas-solid separation, so that the high-purity vanadium pentoxide product is sent to the high-purity product silo; the chlorine-containing tail gas discharged from the secondary cyclone 4-5 enters the exhaust gas.
- the rinsing absorber 5 is treated; the gas discharged from the exhaust gas absorbing absorber 5 after being absorbed by the alkali solution is sent to the chimney 7 through the draft fan 6 and then emptied.
- the industrial grade vanadium pentoxide is used as the raw material, and the chemical composition thereof is shown in Table 1.
- the treatment amount is 70kg/h, and the preparation is high by low temperature chlorination, vanadium oxychloride rectification and plasma oxidation purification. Pure vanadium pentoxide product.
- the amount of carbon powder added in the low-temperature chlorination process is 20% of the quality of the industrial grade vanadium pentoxide powder, the chlorination operation temperature is 300 ° C, and the average residence time of the powder is 80 min;
- the rectification column 3-2 the number of trays in the rectification section is 5, the number of trays in the stripping section is 10, and the reflux ratio of the rectification operation is 40;
- the plasma reactor 4-3 the plasma Under the operating conditions that the amount of air introduced into the body oxidation process is twice the theoretical amount, the direct yield of vanadium is 82%, and the purity of the high-purity vanadium pentoxide product is 99.998 wt% (4N8).
- the amount of carbon powder added in the low-temperature chlorination process is 10% of the quality of the industrial grade vanadium pentoxide powder, the chlorination operation temperature is 500 ° C, and the average residence time of the powder is 30 min;
- the rectification column 3-2 the number of trays in the rectification section of the rectification section is 10, the number of trays in the stripping section is 20, and the reflux ratio of the rectification operation is 15;
- the plasma reactor 4-3 the plasma Under the operating conditions of 50 times the theoretical amount of air in the body oxidation process, the direct yield of vanadium is 85%, and the purity of the high-purity vanadium pentoxide product is 99.9995 wt% (5N5).
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Abstract
Description
V2O5 | Si | Ca | Al | Ti | Fe | Mn | Na | K | S |
98.8 | 0.0150 | 0.0275 | 0.0099 | 0.0260 | 0.0971 | 0.0293 | 0.1385 | 0.0714 | 0.1274 |
Claims (7)
- 一种提纯五氧化二钒的***,其特征在于,所述***包括加料装置(1)、低温氯化流化床(2)、精馏提纯装置(3)、等离子体氧化装置(4)、尾气淋洗吸收器(5)、引风机(6)和烟囱(7);所述加料装置(1)包括工业级五氧化二钒料仓(1-1)、工业级五氧化二钒螺旋加料器(1-2)、炭粉料仓(1-3)和炭粉螺旋加料器(1-4);所述低温氯化流化床(2)包括氯化床进料器(2-1)、氯化流化床主体(2-2)、氯化床旋风分离器(2-3)、烟气换热器(2-4)、烟气冷凝器(2-5)、氯化床酸封罐(2-6)和氯化床螺旋排渣器(2-7);所述精馏提纯装置(3)包括蒸馏釜(3-1)、精馏塔(3-2)、馏出物冷凝器(3-3)、回流液收集罐(3-4)、含硅三氯氧钒储罐(3-5)、精馏段酸封罐(3-6)、高纯三氯氧钒冷凝器(3-7)和高纯三氯氧钒储罐(3-8);所述等离子体氧化装置(4)包括空气过滤净化器(4-1)、反应物喷嘴(4-2)、等离子体反应器(4-3)、一级旋风分离器(4-4)、二级旋风分离器(4-5)、旋叶泵(4-6)和气体压缩机(4-7);所述工业级五氧化二钒料仓(1-1)底部的出料口与所述工业级五氧化二钒螺旋加料器(1-2)的进料口相连接;所述炭粉料仓(1-3)底部的出料口与所述炭粉螺旋加料器(1-4)的进料口相连接;所述工业级五氧化二钒螺旋加料器(1-2)的出料口、所述炭粉螺旋加料器(1-4)的出料口均与所述氯化床进料器(2-1)的进料口通过管道相连接;所述氯化床进料器(2-1)的排料口与所述氯化流化床主体(2-2)上部的进料口通过管道相连接;所述氯化床进料器(2-1)底部的进气口通过管道与氮气气源总管相连接;所述氯化床旋风分离器(2-3)设置于所述氯化流化床主体(2-2)的扩大段顶部中心;所述氯化床旋风分离器(2-3)顶部的出气口通过管道与所述烟气换热器(2-4)的热烟气入口相连接;所述烟气换热器(2-4)的冷烟气出口通过管道与所述烟气冷凝器(2-5)的气体入口相连接;所述烟气冷凝器(2-5)的气体出口通过管道与所述氯化床酸封罐(2-6)的气体入口相连接;所述氯化床酸封罐(2-6)的气体出口通过管道与所述尾气淋洗吸收器(5)的气体入口相连接;所述氯化流化床主体(2-2)下部的排渣口与所述氯化床螺旋排渣器(2-7)的进料口通过管道相连接;所述氯化流化床主体(2-2)底部的进气口通过管道与所述烟气换热器(2-4)的热气体出口相连接;所述烟气换热器(2-4)的冷气 体入口通过管道分别与氯气气源总管、氮气气源总管及压缩空气总管相连接;所述烟气冷凝器(2-5)底部的液体出口通过管道与所述精馏塔(3-2)的进料口相连接;所述蒸馏釜(3-1)的蒸气出口通过管道与所述精馏塔(3-2)的蒸气入口相连接;所述蒸馏釜(3-1)的回流口通过管道与所述精馏塔(3-2)底部的液体回流出口相连接;所述精馏塔(3-2)顶部的气体出口通过管道与所述馏出物冷凝器(3-3)的气体入口相连接;所述馏出物冷凝器(3-3)的液体出口通过管道与所述回流液收集罐(3-4)的液体入口相连接;所述回流液收集罐(3-4)的回流液体出口通过管道与所述精馏塔(3-2)顶部的回流液体入口相连接;所述回流液收集罐(3-4)的排料口与所述含硅三氯氧钒储罐(3-5)的入口通过管道相连接;所述含硅三氯氧钒储罐(3-5)的乏气出口通过管道与所述精馏段酸封罐(3-6)的气体入口相连接;所述精馏酸封罐(3-6)的气体出口通过管道与所述尾气淋洗吸收器(5)的气体入口相连接;所述精馏塔(3-2)的精馏物出口通过管道与所述高纯三氯氧钒冷凝器(3-7)的气体入口相连接;所述高纯三氯氧钒冷凝器(3-7)的液体出口与所述高纯三氯氧钒储罐(3-8)的液体入口通过管道相连接;所述蒸馏釜(3-1)底部设置了底流出口;所述空气过滤净化器(4-1)的进气口与压缩空气总管通过管道相连接;所述空气过滤净化器(4-1)的出气口通过管道分别与反应物喷嘴(4-2)的空气入口和二级旋风分离器(4-5)的气体入口相连接;所述高纯三氯氧钒储罐(3-8)的液体出口通过管道与所述反应物喷嘴(4-2)的氯化物入口相连接;所述反应物喷嘴(4-2)设置于所述等离子体反应器(4-3)的上部中心;所述等离子体反应器(4-3)底部的物料出口通过管道与所述一级旋风分离器(4-4)的气体入口相连接;所述一级旋风分离器(4-4)的气体出口通过管道与所述旋叶泵(4-6)的气体入口相连接;所述旋叶泵(4-6)的气体出口通过管道与所述气体压缩机(4-7)的气体入口相连接;所述气体压缩机(4-7)的气体出口通过管道与所述烟气换热器(2-4)的冷气体入口相连接;所述一级旋风分离器(4-4)下部的排料口通过管道与所述二级旋风分离器(4-5)的气体入口相连接;所述二级旋风分离器(4-5)顶部的气体出口通过管道与所述尾气淋洗吸收器(5)的气体入口相连接;所述二级旋风分离器(4-5)底部的出料口通过管道与高纯五氧化二钒产品料仓相连接;所述尾气淋洗吸收器(5)的气体出口通过管道与所述引风机(6)的气体入口相连接;所述引风机(6)的气体出口通过管道与所述烟囱(7)底部的气体入 口相连接。
- 一种基于权利要求1所述***的提纯五氧化二钒的方法,包括以下步骤:所述工业级五氧化二钒料仓(1-1)中的工业级五氧化二钒粉料和所述炭粉料仓(1-3)的炭粉分别经所述工业级五氧化二钒螺旋加料器(1-2)和所述炭粉螺旋加料器(1-4)同时进入所述氯化床进料器(2-1)混合后进入所述氯化流化床主体(2-2);来自氯气气源总管的氯气、氮气气源总管的氮气、压缩空气总管的空气以及来自所述气体压缩机(4-7)循环返回的含氯气体经所述烟气换热器(2-4)与氯化烟气换热预热后进入所述氯化流化床主体(2-2)中使五氧化二钒和炭粉维持流态化并与之发生化学反应,空气使部分炭粉发生燃烧提供热量维持流化床温度,氯气与炭粉共同作用使五氧化二钒和少量杂质发生氯化,形成氯化残渣和富含三氯氧钒的氯化烟气;氯化残渣依次经所述氯化流化床主体(2-2)下部的排渣口和氯化床螺旋排渣器(2-7)排出;氯化烟气经所述氯化床旋风分离器(2-3)将粉尘脱除并落回氯化流化床主体(2-2)后,再经所述烟气换热器(2-4)预冷却并进入烟气冷凝器(2-5)中使其中的三氯氧钒冷凝形成粗三氯氧钒液体,剩余尾气经所述氯化床酸封罐(2-6)后进入所述尾气淋洗吸收器(5)中;所述烟气冷凝器(2-5)形成的粗三氯氧钒液体依次进入所述精馏塔(3-2)和所述蒸馏釜(3-1)后进行精馏操作,得到富含高沸点杂质的富钒废料、富含低沸点杂质的含硅三氯氧钒蒸气和高纯三氯氧钒蒸气;含硅三氯氧钒蒸气经所述馏出物冷凝器(3-3)冷凝至液体后,部分经所述回流液收集罐(3-4)回流至所述精馏塔(3-2),其余部分进入所述含硅三氯氧钒储罐(3-5)中;含硅三氯氧钒储罐(3-5)中产生的乏气经所述精馏段酸封罐(3-6)后送往所述尾气淋洗吸收器(5)中;高纯三氯氧钒蒸气经所述高纯三氯氧钒冷凝器(3-7)冷凝至液体后进入所述高纯三氯氧钒储罐(3-8)中;所述高纯三氯氧钒储罐(3-8)中的高纯三氯氧钒经反应物喷嘴(4-2)进入等离子体反应器(4-3)中;压缩空气经所述空气过滤净化器(4-1)净化后经所述反应物喷嘴(4-2)进入所述等离子体反应器(4-3),使三氯氧钒发生氧化生成五氧化二钒粉体和富含氯气的氧化烟气;氧化产物由所述等离子体反应器(4-3)底部的出料口排出进入所述一级旋风分离器(4-4)后进行气固分离,分离产生的氧化烟气经所述旋叶泵(4-6)和所述气体压缩机(4-7)加压后返回用于工业级五氧化二钒氯化;所述一级旋风分离器(4-4)底部排出的五氧化二钒粉体与 来自所述空气过滤净化器(4-1)的净化空气一同进入所述二级旋风分离器(4-5),通过充分混合和气固分离脱除粉体中夹带的少量氯气,从而得到高纯五氧化二钒产品送往高纯产品料仓;所述二级旋风分离器(4-5)排出的含氯尾气进入所述尾气淋洗吸收器(5)进行处理;所述尾气淋洗吸收器(5)经碱溶液吸收处理后排出的气体经所述引风机(6)送入所述烟囱(7)后排空。
- 根据权利要求2所述的提纯五氧化二钒的方法,其特征在于,在所述氯化流化床主体(2-2)内,所述氯化过程炭粉添加量为工业级五氧化二钒粉料质量的10%~20%。
- 根据权利要求2所述的提纯五氧化二钒的方法,其特征在于,在所述氯化流化床主体(2-2)内,所述氯化操作温度为300~500℃,粉料的平均停留时间为30~80min。
- 根据权利要求2所述的提纯五氧化二钒的方法,其特征在于,在所述精馏塔(3-2)内,所述精馏操作精馏段的塔板数为5~10块,提馏段的塔板数为10~20块。
- 根据权利要求2所述的提纯五氧化二钒的方法,其特征在于,所述精馏操作的回流比为15~40。
- 根据权利要求2所述的提纯五氧化二钒的方法,其特征在于,在等离子体反应器(4-3)内,通过高纯三氯氧钒等离子体氧化直接制备高纯五氧化二钒,所述等离子体氧化过程中净化空气的通入量为理论用量的2~50倍。
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CA2973511C (en) | 2019-11-26 |
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JP2018506502A (ja) | 2018-03-08 |
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AU2016212452A1 (en) | 2017-08-31 |
EP3243799B1 (en) | 2018-09-12 |
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CA2973511A1 (en) | 2016-08-04 |
CN105984899B (zh) | 2017-05-17 |
US10294118B2 (en) | 2019-05-21 |
EP3243799A1 (en) | 2017-11-15 |
CN105984899A (zh) | 2016-10-05 |
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JP6371015B2 (ja) | 2018-08-08 |
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