CN115927881B - A method for extracting vanadium from vanadium-containing steel slag and simultaneously preparing calcium sulfate - Google Patents
A method for extracting vanadium from vanadium-containing steel slag and simultaneously preparing calcium sulfate Download PDFInfo
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 324
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 319
- 239000002893 slag Substances 0.000 title claims abstract description 126
- 238000000034 method Methods 0.000 title claims abstract description 106
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 95
- 239000010959 steel Substances 0.000 title claims abstract description 95
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 title claims abstract description 88
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 108
- 238000002386 leaching Methods 0.000 claims abstract description 103
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 88
- 239000007788 liquid Substances 0.000 claims abstract description 78
- 239000011575 calcium Substances 0.000 claims abstract description 62
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 59
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 44
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 36
- 239000007791 liquid phase Substances 0.000 claims abstract description 32
- 239000007790 solid phase Substances 0.000 claims abstract description 30
- 238000000926 separation method Methods 0.000 claims abstract description 28
- 238000001556 precipitation Methods 0.000 claims abstract description 22
- 230000001590 oxidative effect Effects 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims description 20
- 239000000292 calcium oxide Substances 0.000 claims description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 10
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 10
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000002351 wastewater Substances 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 5
- 239000002912 waste gas Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 62
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 27
- 230000008569 process Effects 0.000 description 27
- 239000000203 mixture Substances 0.000 description 20
- 238000000605 extraction Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 17
- 239000011734 sodium Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- 229910052742 iron Inorganic materials 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 239000002253 acid Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 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 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 9
- 229910001424 calcium ion Inorganic materials 0.000 description 9
- DNWNZRZGKVWORZ-UHFFFAOYSA-N calcium oxido(dioxo)vanadium Chemical compound [Ca+2].[O-][V](=O)=O.[O-][V](=O)=O DNWNZRZGKVWORZ-UHFFFAOYSA-N 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 239000012535 impurity Substances 0.000 description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 8
- 239000000378 calcium silicate Substances 0.000 description 6
- 229910052918 calcium silicate Inorganic materials 0.000 description 6
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 5
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000002308 calcification Effects 0.000 description 4
- WETINTNJFLGREW-UHFFFAOYSA-N calcium;iron;tetrahydrate Chemical compound O.O.O.O.[Ca].[Fe].[Fe] WETINTNJFLGREW-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 235000019253 formic acid Nutrition 0.000 description 4
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 101001121408 Homo sapiens L-amino-acid oxidase Proteins 0.000 description 2
- 102100026388 L-amino-acid oxidase Human genes 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229910000805 Pig iron Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- WEUCVIBPSSMHJG-UHFFFAOYSA-N calcium titanate Chemical class [O-2].[O-2].[O-2].[Ca+2].[Ti+4] WEUCVIBPSSMHJG-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-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
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
技术领域Technical Field
本发明涉及钒化工冶金技术领域，尤其涉及一种从含钒钢渣提钒同时制备硫酸钙的方法。The invention relates to the technical field of vanadium chemical metallurgy, and in particular to a method for extracting vanadium from vanadium-containing steel slag and simultaneously preparing calcium sulfate.
背景技术Background Art
含钒钢渣是冶炼钒钛磁铁矿的副产品，属于工业废渣，其生成途径主要有两种，一是半钢中残存的钒经炼钢后氧化进入渣中，生成V2O5＜1.5％的含钒钢渣；二是未经吹炼钒渣的铁水直接炼钢得到生成含有2％～5％V2O5的含钒钢渣，其中第二种途径是我国含钒钢渣的主要来源之一。含钒钢渣具有如下特点：(1)钒品位低，铁和氧化钙含量高，结晶完善，质地密实，解离度差；(2)成分复杂且波动，主要由硅酸钙、尖晶石、钙钛氧化物、镁-方铁石、金属铁、自由氧化物等组成；(3)钒含量较低，弥散分布于多种矿相中，赋存状态复杂，提钒难度较大。基于以上特点，利用含钒钢渣进行提钒已成为目前研究的热点及难点之一，迄今未见工业化报道。Vanadium-containing steel slag is a byproduct of smelting vanadium-titanium magnetite and belongs to industrial waste slag. There are two main ways to generate it. One is that the residual vanadium in the semi-steel is oxidized into the slag after steelmaking to generate vanadium -containing steel slag with V2O5 <1.5%; the other is that the molten iron without blowing the vanadium slag is directly used for steelmaking to generate vanadium-containing steel slag containing 2% to 5% V2O5 . The second way is one of the main sources of vanadium - containing steel slag in China. Vanadium-containing steel slag has the following characteristics: (1) low vanadium grade, high iron and calcium oxide content, perfect crystallization, dense texture, and poor dissociation degree; (2) complex and fluctuating composition, mainly composed of calcium silicate, spinel, calcium titanium oxide, magnesium-ferrite, metallic iron, free oxide, etc.; (3) low vanadium content, dispersed in a variety of mineral phases, complex occurrence state, and great difficulty in vanadium extraction. Based on the above characteristics, the use of vanadium-containing steel slag for vanadium extraction has become one of the hot spots and difficulties in current research, and no industrial reports have been seen so far.
目前，含钒钢渣主流的提钒方式有两种，一是对含钒钢渣进行火法冶炼，生成高品位钒渣，再进一步提取钒；二是含钒钢渣被用作直接提钒的原料，这通常需要经历湿法冶金工艺。At present, there are two mainstream ways to extract vanadium from vanadium-containing steel slag. One is to smelt the vanadium-containing steel slag by pyrometallurgy to generate high-grade vanadium slag, and then further extract vanadium; the other is to use the vanadium-containing steel slag as a raw material for direct vanadium extraction, which usually requires a hydrometallurgical process.
火法冶炼主要包括钢渣返回法和矿热炉还原冶炼法，前者是在烧结矿中添加含钒钢渣作为熔剂一同进入高炉进行冶炼，钒在铁水中得到富集后再经锤炼得到含钒量为30％～40％的高品位钒渣，该方法虽然可以有效回收含钒钢渣中钙、钒、铁等有价元素，降低烧结与炼铁成本，但当返回次数过多时，会使磷在铁水中富集从而增加转炉脱磷造渣的成本；后者是将含钒钢渣置于矿热炉内进行煅烧，通过控制炉内的还原性气氛，使钒还原富集于铁水内形成高钒生铁。随后通过控制感应炉内的氧化气氛，将高钒生铁中的钒氧化入渣，由此得到高品位钒渣，该方法存在钒、铁回收率不稳定、波动较大等问题。Fire smelting mainly includes slag return method and ore-reducing smelting method. The former is to add vanadium-containing slag as flux to the sintered ore and put it into the blast furnace for smelting. After the vanadium is enriched in the molten iron, it is hammered to obtain high-grade vanadium slag with a vanadium content of 30% to 40%. Although this method can effectively recover valuable elements such as calcium, vanadium, and iron in the vanadium-containing slag, and reduce the cost of sintering and ironmaking, when the number of returns is too many, phosphorus will be enriched in the molten iron, thereby increasing the cost of converter dephosphorization and slag making; the latter is to place the vanadium-containing slag in an ore-reducing furnace for calcination, and by controlling the reducing atmosphere in the furnace, the vanadium is reduced and enriched in the molten iron to form high-vanadium pig iron. Subsequently, by controlling the oxidizing atmosphere in the induction furnace, the vanadium in the high-vanadium pig iron is oxidized into slag, thereby obtaining high-grade vanadium slag. This method has problems such as unstable and large fluctuations in the recovery rate of vanadium and iron.
传统的湿法提钒多为焙烧(钠化焙烧、钙化焙烧、降钙焙烧、无盐焙烧)-水浸/酸浸/碳酸化浸出-沉钒，以及直接酸浸或碱浸的工艺流程。钠化焙烧是通过加入碳酸钠或氯化钠为添加剂，在高温条件下焙烧，将低价钒转化为五价钒酸盐，通过水或碳酸化浸出将可溶性钒酸盐转移至浸出液中。该工艺钒的污染严重，钒转浸率低，不适用于高钙含钒钢渣提钒。钙化焙烧是通过添加石灰等钙化合物做添加剂进行焙烧，生成难溶于水的钒酸钙，焙烧后的熟料用酸浸出。此法对物料有选择性，针对一般原料存在转化率偏低、成本偏高等问题，不适合大量生产。Amiri提出了添加磷酸盐降钙钠化焙烧法。以Na3PO4和Na2CO3为含钒钢渣钠化焙烧的添加剂，在焙烧过程中，CaO与Na3PO4反应生成Ca3(PO4)2，而钒与Na2CO3结合形成水溶性Na3VO4，后续可直接水浸提钒，减少酸耗。但此工艺磷酸盐配比大，成本高，目前只停留于实验室研究阶段，未进行工业化的推广。空白焙烧法在焙烧时不添加任何添加剂，仅在高温下依靠氧气将低价钒直接氧化为V2O5。后续利用硫酸浸出焙砂中的钒。该方法的优点为无添加剂加入，环境污染小，成本可控。但其存在钒浸出率和热利用效率低等问题，同时，钒与钢渣中的CaO结合生成难溶于水的钒酸钙会增加浸出过程的酸耗，增加生产成本。直接酸浸是指未经焙烧工序，完全湿法提钒，由于含钒钢渣钙、铁含量高，会增加酸耗，同时，此过程需要在强酸条件下进行，导致含钒溶液中杂质较多，给后续处理带来困难。亚熔盐湿法提钒法是利用亚熔盐有效分解固溶钒的物质，将钒以可溶性钒酸盐形式溶出并生成Ca(OH)2沉淀。但该方法存在高碱度条件下低钒浸取液难以分离，处理后残渣中Ca(OH)2、钾/钠盐含量较高，处理困难，成本增加等问题。此外，新兴的绿色分离和资源有效利用新技术，如选择性析出技术、微生物浸出技术、矿浆电解技术应用于含钒固废提钒效果较好，但工艺尚不成熟。Traditional wet vanadium extraction is mostly roasting (sodium roasting, calcium roasting, calcium reduction roasting, salt-free roasting) - water leaching/acid leaching/carbonation leaching - vanadium precipitation, as well as direct acid leaching or alkali leaching. Sodium roasting is to add sodium carbonate or sodium chloride as an additive, roasting under high temperature conditions to convert low-valent vanadium into pentavalent vanadate, and transfer soluble vanadate to the leachate through water or carbonation leaching. This process has serious vanadium pollution and low vanadium conversion rate, and is not suitable for vanadium extraction from high-calcium vanadium-containing steel slag. Calcification roasting is to add lime and other calcium compounds as additives for roasting to produce calcium vanadate that is insoluble in water, and the roasted clinker is leached with acid. This method is selective for materials, and is not suitable for mass production for general raw materials with problems such as low conversion rate and high cost. Amiri proposed a sodium roasting method of adding phosphate to reduce calcium. Na 3 PO 4 and Na 2 CO 3 are used as additives for sodium roasting of vanadium-containing steel slag. During the roasting process, CaO reacts with Na 3 PO 4 to generate Ca 3 (PO 4 ) 2 , while vanadium combines with Na 2 CO 3 to form water-soluble Na 3 VO 4 , which can be directly leached in water to reduce acid consumption. However, this process has a large phosphate ratio and high cost. It is currently only in the laboratory research stage and has not been promoted industrially. The blank roasting method does not add any additives during roasting, and only relies on oxygen to directly oxidize low-valent vanadium to V 2 O 5 at high temperature. Sulfuric acid is then used to leach the vanadium in the roasted sand. The advantages of this method are that no additives are added, environmental pollution is small, and cost is controllable. However, it has problems such as low vanadium leaching rate and heat utilization efficiency. At the same time, vanadium combines with CaO in the steel slag to generate calcium vanadate that is insoluble in water, which increases the acid consumption in the leaching process and increases production costs. Direct acid leaching refers to completely wet vanadium extraction without the roasting process. Due to the high calcium and iron content of vanadium-containing steel slag, acid consumption will increase. At the same time, this process needs to be carried out under strong acid conditions, resulting in more impurities in the vanadium-containing solution, which brings difficulties to subsequent treatment. The sub-molten salt wet vanadium extraction method uses sub-molten salt to effectively decompose the substance that dissolves vanadium, dissolves vanadium in the form of soluble vanadates and generates Ca(OH) 2 precipitates. However, this method has problems such as difficulty in separating low-vanadium leaching solution under high alkalinity conditions, high content of Ca(OH) 2 and potassium/sodium salts in the residue after treatment, difficulty in processing, and increased costs. In addition, emerging new technologies for green separation and effective utilization of resources, such as selective precipitation technology, microbial leaching technology, and slurry electrolysis technology, are applied to vanadium-containing solid waste for vanadium extraction, but the process is not yet mature.
CN102094123A提出了一种用高浓度的氢氧化钠介质从含钒钢渣中提取钒的方法，该方法反应温度为180～240℃，湿法提钒，过程中无废气、粉尘污染；缺点是碱浓度偏高，碱度为65％～90％，则导致介质循环利用时的蒸发浓缩需要的热量较高，则生产成本较高，且终渣中残余的钒量较高，浸出率不高，终渣中钒含量为0.3％～0.5％。CN102094123A proposes a method for extracting vanadium from vanadium-containing steel slag using a high-concentration sodium hydroxide medium. The method has a reaction temperature of 180-240°C and is a wet method for extracting vanadium. There is no waste gas or dust pollution during the process. The disadvantage is that the alkali concentration is relatively high, with the alkalinity being 65%-90%, which results in a high heat requirement for evaporation and concentration during the recycling of the medium, resulting in a high production cost. In addition, the amount of residual vanadium in the final slag is high, and the leaching rate is not high. The vanadium content in the final slag is 0.3%-0.5%.
CN102071321A中提出了用高碱度的氢氧化钾介质从含钒钢渣中提取钒、铬的方法，此方法不需要高温焙烧，反应温度为到160～240℃，湿法提钒铬，过程中有效杜绝了C12、HCl、SO2、粉尘等大气污染物，并降低了废水产生量和排放量；缺点是KOH介质价格昂贵，而KOH与钢渣的质量比为3:1到5:1、反应碱浓度为60％～90％，则损耗的KOH介质较多，导致生产成本偏高，产品效益降低。CN102071321A proposes a method for extracting vanadium and chromium from vanadium-containing steel slag using a high-alkalinity potassium hydroxide medium. This method does not require high-temperature roasting, and the reaction temperature is 160-240°C. It is a wet method for extracting vanadium and chromium. During the process, atmospheric pollutants such as C12 , HCl, SO2 , and dust are effectively eliminated, and the amount of wastewater generated and discharged is reduced. The disadvantage is that the KOH medium is expensive, and the mass ratio of KOH to steel slag is 3:1 to 5:1, and the reaction alkali concentration is 60%-90%, so a large amount of KOH medium is lost, resulting in high production costs and reduced product benefits.
因此，亟需开发更高效更清洁的提钒工艺。Therefore, there is an urgent need to develop more efficient and cleaner vanadium extraction processes.
发明内容Summary of the invention
鉴于现有技术中存在的问题，本发明提供一种从含钒钢渣提钒同时制备硫酸钙的方法，即为一种预脱钙后含钒钢渣钠化焙烧-钠盐浸出提钒的方法，实现了从含钒钢渣中高效的提钒，钒的浸出率≥80％，且提钒过程中无废水废气排出，是一种高效、清洁的提钒方法。In view of the problems existing in the prior art, the present invention provides a method for extracting vanadium from vanadium-containing steel slag and preparing calcium sulfate at the same time, that is, a method for extracting vanadium from vanadium-containing steel slag by sodium roasting after pre-decalcification-sodium salt leaching, which realizes efficient vanadium extraction from vanadium-containing steel slag, with a vanadium leaching rate of ≥80%, and no wastewater or waste gas is discharged during the vanadium extraction process, which is an efficient and clean vanadium extraction method.
为达此目的，本发明采用以下技术方案：To achieve this object, the present invention adopts the following technical solutions:
本发明提供一种从含钒钢渣提钒同时制备硫酸钙的方法，所述方法包括如下步骤：The present invention provides a method for extracting vanadium from vanadium-containing steel slag and simultaneously preparing calcium sulfate, the method comprising the following steps:
(1)混合醋酸溶液和含钒钢渣，经浸出反应和第一固液分离，得到含钒固相和含钙液相；(1) mixing an acetic acid solution and a vanadium-containing steel slag, and subjecting the mixture to a leaching reaction and a first solid-liquid separation to obtain a vanadium-containing solid phase and a calcium-containing liquid phase;
(2)混合硫酸溶液和步骤(1)所述含钙液相，经沉淀反应和第二固液分离，得到硫酸钙产品和沉钙后液，所述沉钙后液循环至步骤(1)中进行浸出反应；(2) mixing the sulfuric acid solution and the calcium-containing liquid phase of step (1), subjecting the mixture to a precipitation reaction and a second solid-liquid separation, to obtain a calcium sulfate product and a post-calcification liquid, wherein the post-calcification liquid is circulated to step (1) for a leaching reaction;
(3)混合碳酸钠和步骤(1)所述含钒固相并经氧化焙烧，得到含钒焙烧熟料；(3) mixing sodium carbonate and the vanadium-containing solid phase of step (1) and subjecting the mixture to oxidative roasting to obtain vanadium-containing roasted clinker;
混合所述含钒焙烧熟料和碳酸钠溶液，并经搅拌浸出和第三固液分离，得到含钒液；The vanadium-containing roasted clinker and the sodium carbonate solution are mixed, and subjected to stirring leaching and a third solid-liquid separation to obtain a vanadium-containing liquid;
步骤(2)和步骤(3)不分先后顺序。Step (2) and step (3) are performed in no particular order.
含钒钢渣提钒难的原因主要体现在两方面：一是含钒钢渣中高CaO不仅会在焙烧过程中生成难溶于水的钒酸钙，大幅降低钒浸出率，还会造成后续浸出过程及直接酸浸工艺的酸耗问题。因此提钒前的预除钙过程十分重要，可有效提高钒提取率的同时降低生产成本。二是含钒钢渣主要成分为硅酸钙、铁酸钙、钙钛氧化物、金属铁及自由氧化物等，其中钒主要以固溶体形式与以硅酸钙为主的复杂矿物及钙钛氧化物共存，所以实现钒提取的关键是强化分解固溶相。而钠化焙烧可以很好地破坏硅酸钙和铁酸钙等物相，实现钒的高效氧化，并形成可溶于水的钒酸钠，有利于后续浸出。此外，后续浸出过程采用碳酸钠为浸出剂，可以有效将钠化焙烧过程中高价钒和CaO结合生成的难溶于水的钒酸钙转化为更难溶的碳酸钙沉出，而钒与Na+结合生成可溶性钒酸钠进入浸出液，进一步提高钒的浸出率。该方法与传统含钒钢渣提钒工艺相比，可以充分提高钢渣钒转化率、杂质元素浸出较少、有效规避有害气体及废水排放、实现废液循环利用，降低生产成本，形成一条绿色清洁生产链。The reasons why it is difficult to extract vanadium from vanadium-containing steel slag are mainly reflected in two aspects: First, the high CaO in vanadium-containing steel slag will not only generate calcium vanadate that is insoluble in water during the roasting process, greatly reducing the vanadium leaching rate, but also cause acid consumption problems in the subsequent leaching process and direct acid leaching process. Therefore, the pre-calcification process before vanadium extraction is very important, which can effectively improve the vanadium extraction rate while reducing production costs. Second, the main components of vanadium-containing steel slag are calcium silicate, calcium ferrite, calcium titanium oxide, metallic iron and free oxides, among which vanadium mainly coexists in the form of solid solution with complex minerals and calcium titanium oxides mainly composed of calcium silicate, so the key to realizing vanadium extraction is to strengthen the decomposition of the solid solution phase. Sodium roasting can well destroy phases such as calcium silicate and calcium ferrite, realize efficient oxidation of vanadium, and form water-soluble sodium vanadate, which is conducive to subsequent leaching. In addition, the subsequent leaching process uses sodium carbonate as a leaching agent, which can effectively convert the insoluble calcium vanadate generated by the combination of high-valent vanadium and CaO during the sodium roasting process into more insoluble calcium carbonate precipitation, while vanadium combines with Na + to form soluble sodium vanadate that enters the leachate, further improving the leaching rate of vanadium. Compared with the traditional vanadium-containing steel slag vanadium extraction process, this method can fully improve the vanadium conversion rate of steel slag, reduce the leaching of impurity elements, effectively avoid harmful gases and wastewater emissions, realize the recycling of waste liquid, reduce production costs, and form a green and clean production chain.
优选地，步骤(1)中所述醋酸溶液的浓度为5～30％，例如可以是5％、8％、10％、12％、15％、18％、20％、22％、25％、28％或30％，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举。Preferably, the concentration of the acetic acid solution in step (1) is 5-30%, for example, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28% or 30%, as well as specific points between the above values. Due to space limitations and for the sake of simplicity, the present invention will no longer list them exhaustively.
本发明进一步优选醋酸溶液的浓度控制在上述范围内，针对复杂的含钒钢渣组分能够实现钙的选择性浸出，提高后续提钒率的同时避免钒在浸出反应过程中的损失。The present invention further preferably controls the concentration of the acetic acid solution within the above range, so as to achieve selective leaching of calcium for the complex vanadium-containing steel slag components, thereby improving the subsequent vanadium extraction rate and avoiding the loss of vanadium during the leaching reaction.
优选地，所述醋酸溶液与含钒钢渣的液固比为(4～10):1，例如可以是4:1、4.5:1、5:1、5.5:1、6:1、6.5:1、7:1、7.5:1、8:1、8.5:1、9:1、9.5:1或10:1，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举。本发明所述液固比的单位为mL/g。Preferably, the liquid-to-solid ratio of the acetic acid solution to the vanadium-containing steel slag is (4-10):1, for example, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1 or 10:1, as well as specific point values between the above values, which are not exhaustively listed in the present invention due to space limitations and for the sake of simplicity. The unit of the liquid-to-solid ratio in the present invention is mL/g.
优选地，步骤(1)中所述浸出反应的温度为25～40℃，例如可以是25℃、28℃、30℃、32℃、35℃、38℃或40℃，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举。本发明所述液固比的单位为ml/g。Preferably, the temperature of the leaching reaction in step (1) is 25-40°C, for example, 25°C, 28°C, 30°C, 32°C, 35°C, 38°C or 40°C, and specific point values between the above values are not exhaustively listed in the present invention due to space limitations and for the sake of simplicity. The unit of the liquid-to-solid ratio in the present invention is ml/g.
优选地，所述浸出反应的时间为0.5～2h，例如可以是0.5h、0.6h、0.7h、0.8h、0.9h、1h、1.1h、1.2h、1.3h、1.4h、1.5h、1.6h、1.7h、1.8h、1.9h或2h，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举。Preferably, the leaching reaction time is 0.5 to 2 h, for example, it can be 0.5 h, 0.6 h, 0.7 h, 0.8 h, 0.9 h, 1 h, 1.1 h, 1.2 h, 1.3 h, 1.4 h, 1.5 h, 1.6 h, 1.7 h, 1.8 h, 1.9 h or 2 h, as well as specific point values between the above values. Due to space limitations and for the sake of simplicity, the present invention will no longer list them exhaustively.
优选地，所述浸出反应在常压下进行。Preferably, the leaching reaction is carried out under normal pressure.
优选地，步骤(1)中所述含钒钢渣中钙以氧化钙计的质量分数为30～50％，例如可以是30％、32％、35％、38％、40％、42％、45％、48％或50％等，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举。Preferably, the mass fraction of calcium in the vanadium-containing steel slag in step (1) calculated as calcium oxide is 30-50%, for example, it can be 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48% or 50%, etc., as well as specific point values between the above values. Due to space limitations and for the sake of simplicity, the present invention will no longer list them exhaustively.
优选地，所述含钒钢渣中钒以五氧化二钒计的质量分数为1～5wt％，例如可以是1wt％、1.2wt％、1.4wt％、1.5wt％、1.8wt％、2.0wt％、2.2wt％、2.5wt％、2.8wt％、3.0wt％、3.5wt％、3.8wt％、4.0wt％、4.2wt％或5.0wt％等，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举。Preferably, the mass fraction of vanadium in the vanadium-containing steel slag calculated as vanadium pentoxide is 1 to 5wt%, for example, it can be 1wt%, 1.2wt%, 1.4wt%, 1.5wt%, 1.8wt%, 2.0wt%, 2.2wt%, 2.5wt%, 2.8wt%, 3.0wt%, 3.5wt%, 3.8wt%, 4.0wt%, 4.2wt% or 5.0wt%, etc., as well as specific point values between the above values. Due to space limitations and for the sake of simplicity, the present invention will no longer list them exhaustively.
优选地，所述含钒钢渣中总铁含量为11～23wt％，例如可以是11wt％、13wt％、15wt％、18wt％、20wt％、21wt％或23wt％等，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举。Preferably, the total iron content in the vanadium-containing steel slag is 11 to 23wt%, for example, it can be 11wt%, 13wt%, 15wt%, 18wt%, 20wt%, 21wt% or 23wt%, etc., as well as specific point values between the above values. Due to space limitations and for the sake of simplicity, the present invention will no longer list them exhaustively.
优选地，所述含钒钢渣中镁以氧化镁计的质量分数为5～12wt％，例如可以是5wt％、6wt％、7wt％、8wt％、9wt％、10wt％、11wt％或12wt％等，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举。Preferably, the mass fraction of magnesium in the vanadium-containing steel slag calculated as magnesium oxide is 5 to 12 wt%, for example, it can be 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt% or 12wt%, etc., as well as specific point values between the above values. Due to space limitations and for the sake of simplicity, the present invention will no longer list them exhaustively.
优选地，所述含钒钢渣中硅以二氧化硅计的质量分数为7～10wt％，例如可以是7wt％、7.2wt％、7.5wt％、7.8wt％、8wt％、8.2wt％、8.5wt％、8.8wt％、9wt％、9.2wt％、9.5wt％、9.8wt％或10wt％等，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举。Preferably, the mass fraction of silicon in the vanadium-containing steel slag as silicon dioxide is 7 to 10wt%, for example, it can be 7wt%, 7.2wt%, 7.5wt%, 7.8wt%, 8wt%, 8.2wt%, 8.5wt%, 8.8wt%, 9wt%, 9.2wt%, 9.5wt%, 9.8wt% or 10wt%, etc., as well as specific point values between the above values. Due to space limitations and for the sake of simplicity, the present invention will no longer list them exhaustively.
本发明选用醋酸溶液不仅能够将氧化钙等游离的钙溶出而且不与钒反应，不影响钒的收率，同时与还会与镁、铁等元素反应实现杂质的预脱除，简化后续除杂工序。The acetic acid solution selected in the present invention can not only dissolve free calcium such as calcium oxide but also does not react with vanadium, does not affect the yield of vanadium, and can also react with elements such as magnesium and iron to achieve pre-removal of impurities, thereby simplifying the subsequent impurity removal process.
优选地，步骤(2)中所述硫酸溶液的浓度为5～40wt％，例如可以是5wt％、10wt％、12wt％、15wt％、18wt％、20wt％、22wt％、25wt％、28wt％、30wt％、32wt％、35wt％、38wt％或40wt％等，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举。Preferably, the concentration of the sulfuric acid solution in step (2) is 5 to 40 wt%, for example, 5 wt%, 10 wt%, 12 wt%, 15 wt%, 18 wt%, 20 wt%, 22 wt%, 25 wt%, 28 wt%, 30 wt%, 32 wt%, 35 wt%, 38 wt% or 40 wt%, etc., as well as specific point values between the above values, are not exhaustively listed in the present invention due to space limitations and for the sake of simplicity.
优选地，所述硫酸溶液中硫酸根与含钙液相中钙离子的摩尔比为0.9～1.1:1，例如可以是0.9:1、0.92:1、0.95:1、0.98:1、1.0:1、1.02:1、1.05:1、1.08:1或1.1:1等，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举。Preferably, the molar ratio of sulfate in the sulfuric acid solution to calcium ions in the calcium-containing liquid phase is 0.9 to 1.1:1, for example, it can be 0.9:1, 0.92:1, 0.95:1, 0.98:1, 1.0:1, 1.02:1, 1.05:1, 1.08:1 or 1.1:1, etc., as well as specific point values between the above values. Due to space limitations and for the sake of simplicity, the present invention will no longer list them exhaustively.
优选地，步骤(3)中所述氧化焙烧中碳酸钠的含量为5～20wt％，例如可以是5％、8％、10％、11％、12％、13％、14％、15％、16％、17％、18％、19％或20％，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举。Preferably, the content of sodium carbonate in the oxidative roasting in step (3) is 5 to 20 wt%, for example, it can be 5%, 8%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20%, as well as specific points between the above values. Due to space limitations and for the sake of simplicity, the present invention will no longer list them exhaustively.
优选地，步骤(3)中所述氧化焙烧的温度为700～800℃，例如可以是700℃、710℃、720℃、730℃、740℃、750℃、760℃、770℃、780℃、790℃或800℃，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举。Preferably, the temperature of the oxidative roasting in step (3) is 700-800°C, for example, it can be 700°C, 710°C, 720°C, 730°C, 740°C, 750°C, 760°C, 770°C, 780°C, 790°C or 800°C, as well as specific point values between the above values. Due to space limitations and for the sake of simplicity, the present invention will no longer list them exhaustively.
优选地，所述氧化焙烧的时间为1～3h，例如可以是1h、1.2h、1.5h、1.8h、2h、2.2h、2.5h、2.8h或3h，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举。Preferably, the oxidative roasting time is 1 to 3 h, for example, 1 h, 1.2 h, 1.5 h, 1.8 h, 2 h, 2.2 h, 2.5 h, 2.8 h or 3 h, as well as specific point values between the above values, are no longer exhaustively listed in the present invention due to space limitations and for the sake of simplicity.
优选地，所述碳酸钠溶液由碳酸钠固体直接溶于水中得到。Preferably, the sodium carbonate solution is obtained by directly dissolving sodium carbonate solid in water.
优选地，所述碳酸钠溶液的浓度为10～40％，例如可以是10％、12％、15％、18％、20％、22％、25％、28％、30％、32％、35％、38％或40％，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举。Preferably, the concentration of the sodium carbonate solution is 10-40%, for example, it can be 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38% or 40%, as well as specific point values between the above values. Due to space limitations and for the sake of simplicity, the present invention will no longer list them exhaustively.
优选地，步骤(3)中所述碳酸钠溶液和含钒焙烧熟料的液固比为(1～10):1，例如可以是1:1、2:1、3:1、4:1、5:1、6:1、7:1、8:1、9:1或10:1，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举。本发明所述液固比的单位为mL/g。Preferably, the liquid-to-solid ratio of the sodium carbonate solution and the vanadium-containing roasted clinker in step (3) is (1-10):1, for example, it can be 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, as well as specific point values between the above values, which are not exhaustively listed in the present invention due to space limitations and for the sake of simplicity. The unit of the liquid-to-solid ratio in the present invention is mL/g.
优选地，步骤(3)中所述搅拌浸出的温度为60～95℃，例如可以是60℃、62℃、65℃、68℃、70℃、72℃、75℃、78℃、80℃、82℃、85℃、88℃、90℃、92℃或95℃，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举。Preferably, the temperature of the stirring leaching in step (3) is 60-95°C, for example, it can be 60°C, 62°C, 65°C, 68°C, 70°C, 72°C, 75°C, 78°C, 80°C, 82°C, 85°C, 88°C, 90°C, 92°C or 95°C, as well as specific point values between the above values. Due to space limitations and for the sake of simplicity, the present invention will no longer list them all.
优选地，所述搅拌浸出的时间为1～3h，例如可以是1h、1.2h、1.5h、1.8h、2h、2.2h、2.5h、2.8h或3h，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举。Preferably, the stirring leaching time is 1 to 3 hours, for example, it can be 1 hour, 1.2 hours, 1.5 hours, 1.8 hours, 2 hours, 2.2 hours, 2.5 hours, 2.8 hours or 3 hours, as well as specific point values between the above values. Due to space limitations and for the sake of simplicity, the present invention will no longer list them exhaustively.
优选地，所述搅拌浸出在常压下进行。Preferably, the agitated leaching is carried out under normal pressure.
优选地，所述含钒液中钒含量为0.5～1.5wt％，例如可以是0.5wt％、0.6wt％、0.7wt％、0.8wt％、0.9wt％、1.0wt％、1.1wt％、1.2wt％、1.3wt％、1.4wt％或1.5wt％等。Preferably, the vanadium content in the vanadium-containing liquid is 0.5-1.5wt%, for example, it can be 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt% or 1.5wt%.
优选地，所述含钒液中其他杂质含量为0.05～0.1wt％，例如可以是0.05wt％、0.06wt％、0.07wt％、0.08wt％、0.09wt％或0.1wt％等。Preferably, the content of other impurities in the vanadium-containing liquid is 0.05-0.1wt%, for example, it can be 0.05wt%, 0.06wt%, 0.07wt%, 0.08wt%, 0.09wt% or 0.1wt%.
本发明所述固液分离选用本领域公知的手段进行，例如可以是过滤、抽滤以及离心等手段，但非仅限于此。The solid-liquid separation of the present invention is carried out by means known in the art, such as filtration, suction filtration and centrifugation, but not limited thereto.
作为本发明优选地技术方案，所述方法包括如下步骤：As a preferred technical solution of the present invention, the method comprises the following steps:
(1)按(4～10):1的液固比混合浓度为5～30％的醋酸溶液和含钒钢渣，经浸出反应0.5～2h和第一固液分离，得到含钒固相和含钙液相；(1) mixing an acetic acid solution with a concentration of 5 to 30% and a vanadium-containing steel slag at a liquid-to-solid ratio of (4 to 10):1, subjecting the mixture to a leaching reaction for 0.5 to 2 hours and a first solid-liquid separation to obtain a vanadium-containing solid phase and a calcium-containing liquid phase;
(2)混合硫酸溶液和步骤(1)所述含钙液相，经沉淀反应和第二固液分离，得到硫酸钙产品和沉钙后液，所述沉钙后液循环至步骤(1)中进行浸出反应；(2) mixing the sulfuric acid solution and the calcium-containing liquid phase of step (1), subjecting the mixture to a precipitation reaction and a second solid-liquid separation, to obtain a calcium sulfate product and a post-calcification liquid, wherein the post-calcification liquid is circulated to step (1) for a leaching reaction;
(3)混合碳酸钠和步骤(1)所述含钒固相，碳酸钠占比5～20％，并经700～800℃氧化焙烧1～3h，得到含钒焙烧熟料；(3) mixing sodium carbonate and the vanadium-containing solid phase of step (1), wherein the sodium carbonate accounts for 5 to 20%, and oxidizing and roasting at 700 to 800° C. for 1 to 3 hours to obtain vanadium-containing roasted clinker;
按液固比(1～10):1混合所述含钒焙烧熟料和浓度为10～40％的碳酸钠溶液，并经60～95℃搅拌浸出1～3h和第三固液分离，得到含钒液；The vanadium-containing roasted clinker and a sodium carbonate solution with a concentration of 10-40% are mixed at a liquid-solid ratio of (1-10):1, and stirred and leached at 60-95°C for 1-3h and subjected to a third solid-liquid separation to obtain a vanadium-containing liquid;
步骤(2)和步骤(3)不分先后顺序。Step (2) and step (3) are performed in no particular order.
本发明中含钒钢渣的组成优选为1～5wt％V2O5、30～50wt％CaO、11～23wt％TFe、5～12wt％MgO、7～10wt％SiO2、1～3wt％Al2O3和1～4wt％TiO2。The composition of the vanadium -containing steel slag in the present invention is preferably 1-5wt% V2O5 , 30-50wt% CaO, 11-23wt% TFe, 5-12wt% MgO, 7-10wt% SiO2 , 1-3wt % Al2O3 and 1-4wt% TiO2 .
与现有技术相比，本发明至少具有以下有益效果：Compared with the prior art, the present invention has at least the following beneficial effects:
(1)本发明提供的从含钒钢渣提钒同时制备硫酸钙的方法能够实现从含钒钢渣中高效提钒，钒的浸出率≥80％，含钒液中钒含量高达0.9wt％以上且杂质含量低至0.08wt％以下。(1) The method for extracting vanadium from vanadium-containing steel slag and preparing calcium sulfate at the same time provided by the present invention can realize efficient extraction of vanadium from vanadium-containing steel slag, with a vanadium leaching rate of ≥80%, a vanadium content in the vanadium-containing liquid of up to 0.9wt% and an impurity content of less than 0.08wt%.
(2)本发明提供的从含钒钢渣提钒同时制备硫酸钙的方法中醋酸溶液钙选择性浸出阶段得到的含钙液相可通过酸化得到硫酸钙沉淀用于钙相关产品制备，副产制得的硫酸钙的纯度高达99.2wt％以上，得到的沉钙后液可返回钙浸出过程，实现循环利用，节约浸出成本、创造经济效益的同时，有效规避了废水排放的问题。(2) In the method for extracting vanadium from vanadium-containing steel slag and preparing calcium sulfate at the same time, the calcium-containing liquid phase obtained in the calcium selective leaching stage of the acetic acid solution provided by the present invention can be acidified to obtain calcium sulfate precipitation for the preparation of calcium-related products. The purity of the calcium sulfate obtained as a by-product is as high as 99.2wt%. The obtained calcium precipitation liquid can be returned to the calcium leaching process to achieve recycling, saving leaching costs, creating economic benefits, and effectively avoiding the problem of wastewater discharge.
(3)本发明提供的从含钒钢渣提钒同时制备硫酸钙的方法通过设置钙选择性浸出步骤可以有效脱除含钒钢渣中69％以上的钙，有效避免了焙烧过程中钙与氧化后得到的高价钒结合生成难溶于水的钒酸钙，提升钒后续浸出效果。(3) The method for extracting vanadium from vanadium-containing steel slag and preparing calcium sulfate at the same time provided by the present invention can effectively remove more than 69% of the calcium in the vanadium-containing steel slag by setting up a calcium selective leaching step, effectively avoiding the formation of calcium vanadate that is insoluble in water by combining calcium with the high-valent vanadium obtained after oxidation during the roasting process, thereby improving the subsequent leaching effect of vanadium.
(4)本发明提供的从含钒钢渣提钒同时制备硫酸钙的方法采用钠化焙烧，因碳酸钠具有碱性，可以更好地破坏硅酸钙和铁酸钙等物相，将钒暴露出来，高效地将低价钒转化为可溶性五价钒酸盐，有益于后续钒浸出。(4) The method for extracting vanadium from vanadium-containing steel slag and preparing calcium sulfate at the same time provided by the present invention adopts sodium roasting. Since sodium carbonate has alkalinity, it can better destroy physical phases such as calcium silicate and calcium ferrite, expose vanadium, and efficiently convert low-valent vanadium into soluble pentavalent vanadate, which is beneficial to subsequent vanadium leaching.
(5)本发明提供的从含钒钢渣提钒同时制备硫酸钙的方法浸出过程中采用碳酸钠为浸出剂，可以有效地将焙烧过程中钙与钒结合生成的难溶于水的钒酸钙转化为溶度积更低的碳酸钙沉出，而高价钒与钠离子结合生成溶于水的钒酸钠进入溶液，有效提高钒的浸出率。(5) The method for extracting vanadium from vanadium-containing steel slag and preparing calcium sulfate at the same time provided by the present invention uses sodium carbonate as a leaching agent during the leaching process, which can effectively convert the water-insoluble calcium vanadate generated by the combination of calcium and vanadium during the roasting process into calcium carbonate with a lower solubility product for precipitation, while the high-valent vanadium combines with sodium ions to generate water-soluble sodium vanadate that enters the solution, effectively improving the leaching rate of vanadium.
(6)本发明提供的从含钒钢渣提钒同时制备硫酸钙的方法得到的含钒液沉钒后经过处理可循环用于含钒焙烧熟料的浸出，整个过程无废水废气排放，是一种清洁的提钒方法。(6) The method for extracting vanadium from vanadium-containing steel slag and preparing calcium sulfate provided by the present invention can obtain a vanadium-containing liquid, which can be recycled for leaching vanadium-containing roasted clinker after vanadium precipitation. The whole process does not emit wastewater or waste gas, and is a clean vanadium extraction method.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1是本发明具体实施方式提供的从含钒钢渣提钒同时制备硫酸钙的方法流程示意图。FIG1 is a schematic flow diagram of a method for extracting vanadium from vanadium-containing steel slag and simultaneously preparing calcium sulfate provided by a specific embodiment of the present invention.
具体实施方式DETAILED DESCRIPTION
下面结合附图并通过具体实施方式来进一步说明本发明的技术方案。The technical solution of the present invention is further described below with reference to the accompanying drawings and through specific implementation methods.
下面对本发明进一步详细说明。但下述的实例仅仅是本发明的简易例子，并不代表或限制本发明的权利保护范围，本发明的保护范围以权利要求书为准。The present invention is further described in detail below. However, the following examples are only simplified examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention shall be subject to the claims.
需要理解的是，在本发明的描述中，术语“第一”、“第二”等仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”等的特征可以明示或者隐含地包括一个或者更多个该特征。在本发明的描述中，除非另有说明，“多个”的含义是两个或两个以上。It should be understood that, in the description of the present invention, the terms "first", "second", etc. are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Thus, a feature defined as "first", "second", etc. may explicitly or implicitly include one or more of the features. In the description of the present invention, unless otherwise specified, "plurality" means two or more.
作为本发明的一个具体实施方式，提供一种从含钒钢渣提钒同时制备硫酸钙的方法，如图1所示，所述方法包括如下步骤：As a specific embodiment of the present invention, a method for extracting vanadium from vanadium-containing steel slag and preparing calcium sulfate at the same time is provided, as shown in FIG1 , the method comprising the following steps:
(1)混合醋酸溶液和含钒钢渣，经浸出反应和第一固液分离，得到含钒固相和含钙液相；(1) mixing an acetic acid solution and a vanadium-containing steel slag, and subjecting the mixture to a leaching reaction and a first solid-liquid separation to obtain a vanadium-containing solid phase and a calcium-containing liquid phase;
(2)混合硫酸溶液和步骤(1)所述含钙液相，经沉淀反应和第二固液分离，得到硫酸钙产品和沉钙后液，所述沉钙后液循环至步骤(1)中进行浸出反应；(2) mixing the sulfuric acid solution and the calcium-containing liquid phase of step (1), subjecting the mixture to a precipitation reaction and a second solid-liquid separation, to obtain a calcium sulfate product and a post-calcification liquid, wherein the post-calcification liquid is circulated to step (1) for a leaching reaction;
(3)混合碳酸钠和步骤(1)所述含钒固相并经氧化焙烧，得到含钒焙烧熟料；(3) mixing sodium carbonate and the vanadium-containing solid phase of step (1) and subjecting the mixture to oxidative roasting to obtain vanadium-containing roasted clinker;
混合所述含钒焙烧熟料和碳酸钠溶液，并经搅拌浸出(钠盐浸钒)和第三固液分离，得到含钒液和浸出渣；The vanadium-containing roasted clinker and the sodium carbonate solution are mixed, and subjected to stirring leaching (leaching vanadium with sodium salt) and a third solid-liquid separation to obtain a vanadium-containing liquid and leached slag;
步骤(2)和步骤(3)不分先后顺序。Step (2) and step (3) are performed in no particular order.
为更好地说明本发明，便于理解本发明的技术方案，本发明的典型但非限制性的实施例如下：To better illustrate the present invention and facilitate understanding of the technical solution of the present invention, typical but non-limiting embodiments of the present invention are as follows:
示例性地本发明实施例和对比例所采用的含钒钢渣的组成为3.4wt％V2O5、35wt％CaO、21.5wt％TFe、10wt％MgO、8.5wt％SiO2、2.5wt％Al2O3和2.6wt％TiO2。Exemplarily, the compositions of the vanadium-containing steel slag used in the examples of the present invention and the comparative examples are 3.4 wt% V 2 O 5 , 35 wt% CaO, 21.5 wt% TFe, 10 wt% MgO, 8.5 wt% SiO 2 , 2.5 wt% Al 2 O 3 and 2.6 wt% TiO 2 .
实施例1Example 1
本实施例提供一种从含钒钢渣提钒同时制备硫酸钙的方法，所述方法包括如下步骤：This embodiment provides a method for extracting vanadium from vanadium-containing steel slag and preparing calcium sulfate at the same time, the method comprising the following steps:
(1)将5％的醋酸溶液与含钒钢渣按4:1的比例混合，25℃条件下200r/min搅拌浸出0.5h，过滤后得到含钒固相和含钙液相；(1) 5% acetic acid solution and vanadium-containing steel slag are mixed in a ratio of 4:1, stirred and leached at 200 r/min at 25° C. for 0.5 h, and filtered to obtain a vanadium-containing solid phase and a calcium-containing liquid phase;
(2)按硫酸根与钙离子的摩尔比为1:1混合硫酸溶液和步骤(1)所述含钙液相，经沉淀反应和第二固液分离，得到硫酸钙产品和沉钙后液，所述沉钙后液循环至步骤(1)中进行浸出反应；(2) mixing a sulfuric acid solution and the calcium-containing liquid phase of step (1) in a molar ratio of sulfate to calcium ion of 1:1, subjecting the mixture to a precipitation reaction and a second solid-liquid separation to obtain a calcium sulfate product and a post-calcification liquid, wherein the post-calcification liquid is circulated to step (1) for a leaching reaction;
(3)步骤(1)所述含钒固相与20％的碳酸钠混合后，于750℃氧化焙烧3h，得到含钒焙烧熟料。将含钒焙烧熟料与40％的碳酸钠溶液按液固比6:1进行混合，在95℃条件下浸出1.5h，过滤后得到浸出渣和含钒液。(3) The vanadium-containing solid phase in step (1) is mixed with 20% sodium carbonate, and then oxidatively roasted at 750° C. for 3 hours to obtain vanadium-containing roasted clinker. The vanadium-containing roasted clinker is mixed with 40% sodium carbonate solution at a liquid-solid ratio of 6:1, and leached at 95° C. for 1.5 hours, and filtered to obtain leached slag and vanadium-containing liquid.
浸出渣经洗涤，烘干，称重并分析残渣的钒含量，经检测含钒钢渣中钒的浸出率为87％。The leached slag was washed, dried, weighed and the vanadium content of the residue was analyzed. The vanadium leaching rate in the vanadium-containing steel slag was found to be 87%.
实施例2Example 2
本实施例提供一种从含钒钢渣提钒同时制备硫酸钙的方法，所述方法包括如下步骤：This embodiment provides a method for extracting vanadium from vanadium-containing steel slag and preparing calcium sulfate at the same time, the method comprising the following steps:
(1)将10％的醋酸溶液与含钒钢渣按6:1的比例混合，30℃条件下250r/min搅拌浸出1h，过滤后得到含钒固相和含钙液相；(1) mixing 10% acetic acid solution and vanadium-containing steel slag in a ratio of 6:1, stirring and leaching at 250 r/min at 30° C. for 1 h, and filtering to obtain a vanadium-containing solid phase and a calcium-containing liquid phase;
(2)按硫酸根与钙离子的摩尔比为1:1混合硫酸溶液和步骤(1)所述含钙液相，经沉淀反应和第二固液分离，得到硫酸钙产品和沉钙后液，所述沉钙后液循环至步骤(1)中进行浸出反应；(2) mixing a sulfuric acid solution and the calcium-containing liquid phase of step (1) in a molar ratio of sulfate to calcium ion of 1:1, subjecting the mixture to a precipitation reaction and a second solid-liquid separation to obtain a calcium sulfate product and a post-calcification liquid, wherein the post-calcification liquid is circulated to step (1) for a leaching reaction;
(3)步骤(1)所述含钒固相与10％的碳酸钠混合后，于800℃氧化焙烧2h，得到含钒焙烧熟料。将含钒焙烧熟料与25％的碳酸钠溶液按液固比5:1进行混合，在90℃条件下浸出2h，过滤后得到浸出渣和含钒液。(3) The vanadium-containing solid phase in step (1) is mixed with 10% sodium carbonate, and then oxidatively roasted at 800° C. for 2 hours to obtain vanadium-containing roasted clinker. The vanadium-containing roasted clinker is mixed with 25% sodium carbonate solution at a liquid-solid ratio of 5:1, and leached at 90° C. for 2 hours, and filtered to obtain leached slag and vanadium-containing liquid.
浸出渣经洗涤，烘干，称重并分析残渣的钒含量，经检测含钒钢渣中钒的浸出率为90.7％。The leached slag was washed, dried, weighed and the vanadium content of the residue was analyzed. The vanadium leaching rate in the vanadium-containing steel slag was found to be 90.7%.
实施例3Example 3
本实施例提供一种从含钒钢渣提钒同时制备硫酸钙的方法，所述方法包括如下步骤：This embodiment provides a method for extracting vanadium from vanadium-containing steel slag and preparing calcium sulfate at the same time, the method comprising the following steps:
(1)将15％的醋酸溶液与含钒钢渣按5:1的比例混合，35℃条件下270r/min搅拌浸出1.5h，过滤后得到含钒固相和含钙液相；(1) mixing 15% acetic acid solution and vanadium-containing steel slag in a ratio of 5:1, stirring and leaching at 270 r/min at 35° C. for 1.5 h, and filtering to obtain a vanadium-containing solid phase and a calcium-containing liquid phase;
(2)按硫酸根与钙离子的摩尔比为1:1混合硫酸溶液和步骤(1)所述含钙液相，经沉淀反应和第二固液分离，得到硫酸钙产品和沉钙后液，所述沉钙后液循环至步骤(1)中进行浸出反应；(2) mixing a sulfuric acid solution and the calcium-containing liquid phase of step (1) in a molar ratio of sulfate to calcium ion of 1:1, subjecting the mixture to a precipitation reaction and a second solid-liquid separation to obtain a calcium sulfate product and a post-calcification liquid, wherein the post-calcification liquid is circulated to step (1) for a leaching reaction;
(3)步骤(1)所述含钒固相与11％的碳酸钠混合后，于760℃氧化焙烧1.5h，得到含钒焙烧熟料。将含钒焙烧熟料与30％的碳酸钠溶液按液固比8:1进行混合，在85℃条件下浸出2.5h，过滤后得到浸出渣和含钒液。(3) The vanadium-containing solid phase in step (1) is mixed with 11% sodium carbonate, and then oxidatively roasted at 760° C. for 1.5 h to obtain vanadium-containing roasted clinker. The vanadium-containing roasted clinker is mixed with 30% sodium carbonate solution at a liquid-to-solid ratio of 8:1, and leached at 85° C. for 2.5 h, and filtered to obtain leached slag and vanadium-containing liquid.
浸出渣经洗涤，烘干，称重并分析残渣的钒含量，经检测含钒钢渣中钒的浸出率为85.2％。The leached slag was washed, dried, weighed and the vanadium content of the residue was analyzed. The vanadium leaching rate in the vanadium-containing steel slag was found to be 85.2%.
实施例4Example 4
本实施例提供一种从含钒钢渣提钒同时制备硫酸钙的方法，所述方法包括如下步骤：This embodiment provides a method for extracting vanadium from vanadium-containing steel slag and preparing calcium sulfate at the same time, the method comprising the following steps:
(1)将20％的醋酸溶液与含钒钢渣按7:1的比例混合，40℃条件下300r/min搅拌浸出2h，过滤后得到含钒固相和含钙液相；(1) mixing 20% acetic acid solution and vanadium-containing steel slag in a ratio of 7:1, stirring and leaching at 300 r/min at 40° C. for 2 h, and filtering to obtain a vanadium-containing solid phase and a calcium-containing liquid phase;
(2)按硫酸根与钙离子的摩尔比为1:1混合硫酸溶液和步骤(1)所述含钙液相，经沉淀反应和第二固液分离，得到硫酸钙产品和沉钙后液，所述沉钙后液循环至步骤(1)中进行浸出反应；(2) mixing a sulfuric acid solution and the calcium-containing liquid phase of step (1) in a molar ratio of sulfate to calcium ion of 1:1, subjecting the mixture to a precipitation reaction and a second solid-liquid separation to obtain a calcium sulfate product and a post-calcification liquid, wherein the post-calcification liquid is circulated to step (1) for a leaching reaction;
(3)步骤(1)所述含钒固相与15％的碳酸钠混合后，于740℃氧化焙烧3h，得到含钒焙烧熟料。将含钒焙烧熟料与35％的碳酸钠溶液按液固比9:1进行混合，在80℃条件下浸出1.5h，过滤后得到浸出渣和含钒液。(3) The vanadium-containing solid phase in step (1) is mixed with 15% sodium carbonate, and then oxidatively roasted at 740° C. for 3 hours to obtain vanadium-containing roasted clinker. The vanadium-containing roasted clinker is mixed with 35% sodium carbonate solution at a liquid-to-solid ratio of 9:1, and leached at 80° C. for 1.5 hours, and filtered to obtain leached slag and vanadium-containing liquid.
浸出渣经洗涤，烘干，称重并分析残渣的钒含量，经检测含钒钢渣中钒的浸出率为86％。The leached slag was washed, dried, weighed and the vanadium content of the residue was analyzed. The vanadium leaching rate in the vanadium-containing steel slag was found to be 86%.
实施例5Example 5
本实施例提供一种从含钒钢渣提钒同时制备硫酸钙的方法，所述方法包括如下步骤：This embodiment provides a method for extracting vanadium from vanadium-containing steel slag and preparing calcium sulfate at the same time, the method comprising the following steps:
(1)将25％的醋酸溶液与含钒钢渣按8:1的比例混合，33℃条件下350r/min搅拌浸出1h，过滤后得到含钒固相和含钙液相；(1) mixing 25% acetic acid solution and vanadium-containing steel slag in a ratio of 8:1, stirring and leaching at 350 r/min at 33° C. for 1 h, and filtering to obtain a vanadium-containing solid phase and a calcium-containing liquid phase;
(2)按硫酸根与钙离子的摩尔比为1:1混合硫酸溶液和步骤(1)所述含钙液相，经沉淀反应和第二固液分离，得到硫酸钙产品和沉钙后液，所述沉钙后液循环至步骤(1)中进行浸出反应；(2) mixing a sulfuric acid solution and the calcium-containing liquid phase of step (1) in a molar ratio of sulfate to calcium ion of 1:1, subjecting the mixture to a precipitation reaction and a second solid-liquid separation to obtain a calcium sulfate product and a post-calcification liquid, wherein the post-calcification liquid is circulated to step (1) for a leaching reaction;
(3)步骤(1)所述含钒固相与8％的碳酸钠混合后，于700℃氧化焙烧2h，得到含钒焙烧熟料。将含钒焙烧熟料与40％的碳酸钠溶液按液固比10:1进行混合，在70℃条件下浸出3h，过滤后得到浸出渣和含钒液。(3) After the vanadium-containing solid phase in step (1) is mixed with 8% sodium carbonate, the mixture is oxidatively roasted at 700° C. for 2 hours to obtain vanadium-containing roasted clinker. The vanadium-containing roasted clinker is mixed with 40% sodium carbonate solution at a liquid-solid ratio of 10:1, leached at 70° C. for 3 hours, and filtered to obtain leached slag and vanadium-containing liquid.
浸出渣经洗涤，烘干，称重并分析残渣的钒含量，经检测含钒钢渣中钒的浸出率为82％。The leached slag was washed, dried, weighed and the vanadium content of the residue was analyzed. The vanadium leaching rate in the vanadium-containing steel slag was found to be 82%.
实施例6Example 6
本实施例提供一种从含钒钢渣提钒同时制备硫酸钙的方法，所述方法包括如下步骤：This embodiment provides a method for extracting vanadium from vanadium-containing steel slag and preparing calcium sulfate at the same time, the method comprising the following steps:
(1)将30％的醋酸溶液与含钒钢渣按9:1的比例混合，28℃条件下310r/min搅拌浸出1.5h，过滤后得到含钒固相和含钙液相；(1) mixing 30% acetic acid solution and vanadium-containing steel slag in a ratio of 9:1, stirring and leaching at 310 r/min at 28° C. for 1.5 h, and filtering to obtain a vanadium-containing solid phase and a calcium-containing liquid phase;
(2)按硫酸根与钙离子的摩尔比为1:1混合硫酸溶液和步骤(1)所述含钙液相，经沉淀反应和第二固液分离，得到硫酸钙产品和沉钙后液，所述沉钙后液循环至步骤(1)中进行浸出反应；(2) mixing a sulfuric acid solution and the calcium-containing liquid phase of step (1) in a molar ratio of sulfate to calcium ion of 1:1, subjecting the mixture to a precipitation reaction and a second solid-liquid separation to obtain a calcium sulfate product and a post-calcification liquid, wherein the post-calcification liquid is circulated to step (1) for a leaching reaction;
(3)步骤(1)所述含钒固相与5％的碳酸钠混合后，于720℃氧化焙烧3h，得到含钒焙烧熟料。将含钒焙烧熟料与38％的碳酸钠溶液按液固比5:1进行混合，在95℃条件下浸出2.5h，过滤后得到浸出渣和含钒液。(3) The vanadium-containing solid phase in step (1) is mixed with 5% sodium carbonate, and then oxidatively roasted at 720° C. for 3 h to obtain vanadium-containing roasted clinker. The vanadium-containing roasted clinker is mixed with 38% sodium carbonate solution at a liquid-solid ratio of 5:1, and leached at 95° C. for 2.5 h, and filtered to obtain leached slag and vanadium-containing liquid.
浸出渣经洗涤，烘干，称重并分析残渣的钒含量，经检测含钒钢渣中钒的浸出率为80.4％。The leached slag was washed, dried, weighed and the vanadium content of the residue was analyzed. The vanadium leaching rate in the vanadium-containing steel slag was found to be 80.4%.
实施例7Example 7
本实施例提供一种从含钒钢渣提钒同时制备硫酸钙的方法，所述方法包括如下步骤：This embodiment provides a method for extracting vanadium from vanadium-containing steel slag and preparing calcium sulfate at the same time, the method comprising the following steps:
(1)将25％的醋酸溶液与含钒钢渣按6:1的比例混合，30℃条件下230r/min搅拌浸出1h，过滤后得到含钒固相和含钙液相；(1) mixing 25% acetic acid solution and vanadium-containing steel slag in a ratio of 6:1, stirring and leaching at 230 r/min at 30° C. for 1 h, and filtering to obtain a vanadium-containing solid phase and a calcium-containing liquid phase;
(2)按硫酸根与钙离子的摩尔比为1:1混合硫酸溶液和步骤(1)所述含钙液相，经沉淀反应和第二固液分离，得到硫酸钙产品和沉钙后液，所述沉钙后液循环至步骤(1)中进行浸出反应；(2) mixing a sulfuric acid solution and the calcium-containing liquid phase of step (1) in a molar ratio of sulfate to calcium ion of 1:1, subjecting the mixture to a precipitation reaction and a second solid-liquid separation to obtain a calcium sulfate product and a post-calcification liquid, wherein the post-calcification liquid is circulated to step (1) for a leaching reaction;
(3)步骤(1)所述含钒固相与12％的碳酸钠混合后，于790℃氧化焙烧2.5h，得到含钒焙烧熟料。将含钒焙烧熟料与30％的碳酸钠溶液按液固比10:1进行混合，在90℃条件下浸出2h，过滤后得到浸出渣和含钒液。(3) The vanadium-containing solid phase in step (1) is mixed with 12% sodium carbonate, and then oxidatively roasted at 790° C. for 2.5 hours to obtain vanadium-containing roasted clinker. The vanadium-containing roasted clinker is mixed with 30% sodium carbonate solution at a liquid-to-solid ratio of 10:1, and leached at 90° C. for 2 hours, and filtered to obtain leached slag and vanadium-containing liquid.
浸出渣经洗涤，烘干，称重并分析残渣的钒含量，经检测含钒钢渣中钒的浸出率为88.6％。The leached slag was washed, dried, weighed and the vanadium content of the residue was analyzed. The vanadium leaching rate in the vanadium-containing steel slag was found to be 88.6%.
实施例8Example 8
本实施例提供一种从含钒钢渣提钒同时制备硫酸钙的方法，所述方法包括如下步骤：This embodiment provides a method for extracting vanadium from vanadium-containing steel slag and preparing calcium sulfate at the same time, the method comprising the following steps:
(1)将10％的醋酸溶液与含钒钢渣按4:1的比例混合，25℃条件下290r/min搅拌浸出1.5h，过滤后得到含钒固相和含钙液相；(1) mixing 10% acetic acid solution and vanadium-containing steel slag in a ratio of 4:1, stirring and leaching at 290 r/min at 25° C. for 1.5 h, and filtering to obtain a vanadium-containing solid phase and a calcium-containing liquid phase;
(2)按硫酸根与钙离子的摩尔比为1:1混合硫酸溶液和步骤(1)所述含钙液相，经沉淀反应和第二固液分离，得到硫酸钙产品和沉钙后液，所述沉钙后液循环至步骤(1)中进行浸出反应；(2) mixing a sulfuric acid solution and the calcium-containing liquid phase of step (1) in a molar ratio of sulfate to calcium ion of 1:1, subjecting the mixture to a precipitation reaction and a second solid-liquid separation to obtain a calcium sulfate product and a post-calcification liquid, wherein the post-calcification liquid is circulated to step (1) for a leaching reaction;
(3)步骤(1)所述含钒固相与10％的碳酸钠混合后，于800℃氧化焙烧2.5h，得到含钒焙烧熟料。将含钒焙烧熟料与25％的碳酸钠溶液按液固比6:1进行混合，在95℃条件下浸出2.5h，过滤后得到浸出渣和含钒液。(3) The vanadium-containing solid phase in step (1) is mixed with 10% sodium carbonate, and then oxidatively roasted at 800° C. for 2.5 hours to obtain vanadium-containing roasted clinker. The vanadium-containing roasted clinker is mixed with 25% sodium carbonate solution at a liquid-solid ratio of 6:1, and leached at 95° C. for 2.5 hours, and filtered to obtain leached slag and vanadium-containing liquid.
浸出渣经洗涤，烘干，称重并分析残渣的钒含量，经检测含钒钢渣中钒的浸出率为89％。The leached slag was washed, dried, weighed and the vanadium content of the residue was analyzed. The vanadium leaching rate in the vanadium-containing steel slag was found to be 89%.
实施例9Example 9
本实施例提供一种从含钒钢渣提钒同时制备硫酸钙的方法，所述方法除醋酸溶液的浓度为1wt％外，其他条件与实施例2完全相同。This embodiment provides a method for extracting vanadium from vanadium-containing steel slag and preparing calcium sulfate at the same time. Except that the concentration of the acetic acid solution is 1wt%, other conditions of the method are exactly the same as those of Example 2.
实施例10Example 10
本实施例提供一种从含钒钢渣提钒同时制备硫酸钙的方法，所述方法除醋酸溶液的浓度为40wt％外，其他条件与实施例2完全相同。This embodiment provides a method for extracting vanadium from vanadium-containing steel slag and preparing calcium sulfate at the same time. Except that the concentration of the acetic acid solution is 40wt%, other conditions of the method are exactly the same as those of Example 2.
对比例1Comparative Example 1
本对比例提供一种从含钒钢渣提钒的方法，所述方法除不进行步骤(1)中的醋酸溶液对钙的选择性浸出以外，其他条件与实施例7完全相同。This comparative example provides a method for extracting vanadium from vanadium-containing steel slag. Except that the selective leaching of calcium by the acetic acid solution in step (1) is not performed, other conditions are exactly the same as those of Example 7.
对比例2Comparative Example 2
本对比例提供一种从含钒钢渣提钒的方法，所述方法除不进行步骤(3)中的氧化焙烧以外，其他条件与实施例2完全相同。This comparative example provides a method for extracting vanadium from vanadium-containing steel slag. Except that the oxidative roasting in step (3) is not performed, the other conditions of the method are exactly the same as those of Example 2.
对比例3Comparative Example 3
本对比例提供一种从含钒钢渣提钒的方法，所述方法除不进行步骤(3)中碳酸钠溶液替换为水以外，其他条件与实施例8完全相同。This comparative example provides a method for extracting vanadium from vanadium-containing steel slag. The method is completely the same as Example 8 except that the sodium carbonate solution is not replaced by water in step (3).
对比例4Comparative Example 4
本对比例提供一种从含钒钢渣提钒的方法，所述方法除步骤(1)中醋酸溶液替换为盐酸溶液以外，其他条件与实施例8完全相同。This comparative example provides a method for extracting vanadium from vanadium-containing steel slag. Except that the acetic acid solution in step (1) is replaced by a hydrochloric acid solution, the other conditions are exactly the same as those in Example 8.
对比例5Comparative Example 5
本对比例提供一种从含钒钢渣提钒的方法，所述方法除步骤(1)中醋酸溶液替换为甲酸溶液以外，其他条件与实施例8完全相同。This comparative example provides a method for extracting vanadium from vanadium-containing steel slag. Except that the acetic acid solution in step (1) is replaced by formic acid solution, other conditions are exactly the same as those in Example 8.
测试方法：对浸出渣进行洗涤，烘干，称重并分析残渣的钒含量，计算检测含钒钢渣中钒的浸出率；采用电感耦合等离子体发射光谱仪检测步骤(1)中得到的含钒固相中的钙含量并计算钙在预除钙中的去除率，同时利用该方法检测含钒液中杂质含量和钒含量；采用化学滴定法方法检测硫酸钙的纯度。Test method: washing and drying the leached slag, weighing and analyzing the vanadium content of the residue, calculating and detecting the leaching rate of vanadium in the vanadium-containing steel slag; using an inductively coupled plasma emission spectrometer to detect the calcium content in the vanadium-containing solid phase obtained in step (1) and calculate the removal rate of calcium in the pre-calcification, and at the same time using this method to detect the impurity content and vanadium content in the vanadium-containing liquid; using a chemical titration method to detect the purity of calcium sulfate.
以上实施例和对比例的测试结果如表1所示。The test results of the above embodiments and comparative examples are shown in Table 1.
表1Table 1
从表1可以看出如下几点：From Table 1, we can see the following points:
(1)综合实施例1～8可以看出，本发明提供的一种从含钒钢渣提钒同时制备硫酸钙的方法浸出率达80％以上，预除钙的钙去除率在69％以上，含钒液中钒含量高达0.9wt％以上且杂质含量低至0.08wt％以下，副产制得的硫酸钙的纯度高达99.2wt％以上；(1) It can be seen from Examples 1 to 8 that the method for extracting vanadium from vanadium-containing steel slag and preparing calcium sulfate at the same time provided by the present invention has a leaching rate of more than 80%, a calcium removal rate of pre-calcification of more than 69%, a vanadium content of more than 0.9wt% in the vanadium-containing liquid and a low impurity content of less than 0.08wt%, and a purity of the calcium sulfate obtained as a by-product of more than 99.2wt%;
(2)实施例9中除醋酸溶液的浓度较低外，其他条件与实施例2完全相同，但转化率明显低于实施例1～8，可见，醋酸浓度过低，无法有效去除含钒钢渣中的钙，大量钙残留于含钒固相中经高温氧化焙烧生成难溶的钒酸钙而降低钒浸出率；实施例10中除醋酸溶液的浓度较高外，其他条件与实施例2完全相同，但转化率明显低于实施例1～8，可见，醋酸浓度过高时，醋酸会与钢渣中的铁发生反应，铁离子与醋酸根会发生双水解，生成氢氧化铁胶体，影响水浸液的过滤性能及钙的浸出，大大降低工艺效率。此外，过高的酸浓度会将部分钒浸出，造成钒损失；(2) In Example 9, except for the lower concentration of the acetic acid solution, the other conditions are exactly the same as those in Example 2, but the conversion rate is significantly lower than that in Examples 1 to 8. It can be seen that the acetic acid concentration is too low to effectively remove the calcium in the vanadium-containing steel slag, and a large amount of calcium remains in the vanadium-containing solid phase, which is oxidized and roasted at high temperature to generate insoluble calcium vanadate, thereby reducing the vanadium leaching rate; In Example 10, except for the higher concentration of the acetic acid solution, the other conditions are exactly the same as those in Example 2, but the conversion rate is significantly lower than that in Examples 1 to 8. It can be seen that when the acetic acid concentration is too high, the acetic acid will react with the iron in the steel slag, and the iron ions and acetate will undergo double hydrolysis to generate iron hydroxide colloid, which will affect the filtration performance of the water extract and the leaching of calcium, greatly reducing the process efficiency. In addition, too high an acid concentration will leach out part of the vanadium, resulting in vanadium loss;
(3)对比例1中除钙选择性浸出以外，其他条件与实施例7完全相同，但转化率明显低于实施例7，表明本发明利用醋酸进行钙选择性浸出后，不仅可以提高钒的品位，还可以有效避免焙烧过程中生成难溶与水的钒酸钙，有利于钒的浸出；(3) In Comparative Example 1, except for the selective leaching of calcium, the other conditions are exactly the same as those in Example 7, but the conversion rate is significantly lower than that in Example 7, indicating that the selective leaching of calcium with acetic acid in the present invention can not only improve the grade of vanadium, but also effectively avoid the formation of calcium vanadate that is insoluble in water during the roasting process, which is beneficial to the leaching of vanadium;
(4)对比例2除没有钠化焙烧以外，其他条件与实施例2完全相同，但转化率明显低于实施例2，可见，钠化焙烧可以更好地破坏硅酸钙和铁酸钙等物相，将钒暴露出来，有效提高钒的氧化率并形成可溶于水的钒酸钠，有利于后续钒浸出；(4) In Comparative Example 2, except for the absence of sodium roasting, the other conditions are exactly the same as those of Example 2, but the conversion rate is significantly lower than that of Example 2. It can be seen that sodium roasting can better destroy phases such as calcium silicate and calcium ferrite, expose vanadium, effectively improve the oxidation rate of vanadium and form water-soluble sodium vanadate, which is beneficial to the subsequent vanadium leaching;
(5)对比例3除焙烧熟料浸出剂不一样以外，其他条件与实施例8完全相同，但转化率明显低于实施例8，可见，采用碳酸钠溶液为浸出剂，可以有效地将焙烧过程中生成的难溶于水的钒酸钙转化为溶于水的钒酸钠进入溶液，有效提高钒的浸出率；(5) In Comparative Example 3, except for the different leaching agent for the roasted clinker, the other conditions are exactly the same as those of Example 8, but the conversion rate is significantly lower than that of Example 8. It can be seen that the use of sodium carbonate solution as the leaching agent can effectively convert the water-insoluble calcium vanadate generated during the roasting process into water-soluble sodium vanadate and enter the solution, thereby effectively improving the leaching rate of vanadium;
(6)对比例4用盐酸代替醋酸进行含钒钢渣预除钙，一方面盐酸为强酸，会将部分钒溶出至液相中，无法实现钙的选择性浸出，导致钒损失，降低钒收率；另一方面盐酸浸钙后得到的含钒液相主要为氯化钙，相较于醋酸钙，其较难与硫酸反应生成硫酸钙沉淀，同时，也无法实现废液的循环利用；对比例5用甲酸代替醋酸进行含钒钢渣预除钙，虽然甲酸能够达到跟乙酸相同的效果，但由于甲酸价格偏高，会增加成本，因此选择更加经济性的乙酸作为钙浸出剂。(6) In Comparative Example 4, hydrochloric acid was used instead of acetic acid to pre-decalcify the vanadium-containing steel slag. On the one hand, hydrochloric acid is a strong acid, which will dissolve part of the vanadium into the liquid phase, and the selective leaching of calcium cannot be achieved, resulting in vanadium loss and reduced vanadium yield. On the other hand, the vanadium-containing liquid phase obtained after hydrochloric acid leaching is mainly calcium chloride, which is more difficult to react with sulfuric acid to form calcium sulfate precipitation compared with calcium acetate. At the same time, the recycling of waste liquid cannot be achieved. In Comparative Example 5, formic acid was used instead of acetic acid to pre-decalcify the vanadium-containing steel slag. Although formic acid can achieve the same effect as acetic acid, the price of formic acid is relatively high, which will increase the cost. Therefore, more economical acetic acid was selected as the calcium leaching agent.
本发明通过上述实施例来说明本发明的详细工艺流程，但本发明并不局限于上述详细工艺流程，即不意味着本发明必须依赖上述详细工艺流程才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。The present invention illustrates the detailed process flow of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed process flow, that is, it does not mean that the present invention must rely on the above-mentioned detailed process flow to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.
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