CN117467858A - 一种含钒钨酸盐溶液净化分离回收钒和钨的方法 - Google Patents
一种含钒钨酸盐溶液净化分离回收钒和钨的方法 Download PDFInfo
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 66
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 54
- 239000010937 tungsten Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 42
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims abstract description 33
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 238000004064 recycling Methods 0.000 title abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 27
- 230000002308 calcification Effects 0.000 claims abstract description 20
- 238000002425 crystallisation Methods 0.000 claims abstract description 19
- 230000008025 crystallization Effects 0.000 claims abstract description 19
- 238000001816 cooling Methods 0.000 claims abstract description 17
- 238000001704 evaporation Methods 0.000 claims abstract description 16
- 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 claims abstract description 6
- 239000011734 sodium Substances 0.000 claims abstract description 6
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 6
- 239000000706 filtrate Substances 0.000 claims description 57
- 238000002386 leaching Methods 0.000 claims description 37
- 239000007790 solid phase Substances 0.000 claims description 37
- 239000007787 solid Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 239000011575 calcium Substances 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 11
- 229910052791 calcium Inorganic materials 0.000 claims description 11
- 238000011084 recovery Methods 0.000 claims description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000292 calcium oxide Substances 0.000 claims description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 7
- DNWNZRZGKVWORZ-UHFFFAOYSA-N calcium oxido(dioxo)vanadium Chemical compound [Ca+2].[O-][V](=O)=O.[O-][V](=O)=O DNWNZRZGKVWORZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- NWJUARNXABNMDW-UHFFFAOYSA-N tungsten vanadium Chemical compound [W]=[V] NWJUARNXABNMDW-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 5
- 239000001099 ammonium carbonate Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical compound [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 40
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004176 ammonification Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052804 chromium Inorganic materials 0.000 abstract description 3
- 239000011651 chromium Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 abstract description 3
- 239000011777 magnesium Substances 0.000 abstract description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 3
- 239000011259 mixed solution Substances 0.000 abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- 239000011574 phosphorus Substances 0.000 abstract description 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000010703 silicon Substances 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 description 5
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 4
- 238000009388 chemical precipitation Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
- C22B3/14—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions containing ammonia or ammonium salts
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Abstract
本发明涉及一种含钒钨酸盐溶液净化分离回收钒和钨的方法,所述方法为:将含钒钨酸盐溶液进行钙化反应、铵化反应得到偏钒酸铵和钨酸铵为主的溶液,溶液经冷却结晶析出偏钒酸铵晶体,结晶后液再经过蒸发结晶得到钨酸铵晶体。本发明先通过钙化反应、铵化反应将含钒钨酸盐溶液中的铁、铬、钠、镁、锰、磷、硅等大部分杂质去除,得到较为纯净的偏钒酸铵和钨酸铵混合溶液,然后通过冷却结晶和蒸发结晶实现偏钒酸铵和钨酸铵的分离。本发明工艺流程短简单,分离效果好,适用于工业化生产,具有良好的经济效益和应用前景。
Description
技术领域
本发明属于环保技术领域,具体涉及一种含钒钨酸盐溶液净化分离回收钒和钨的方法。
背景技术
废钒钛系SCR脱硝催化剂或含钒钨矿经过碱性溶液浸出或钠化焙烧-水浸工艺后,钒和钨主要进入浸出液中,需要对浸出液中的钒、钨进行分离。目前常用的净化分离方法主要包括化学沉淀法、离子交换法以及溶剂萃取法等。
化学沉淀法通过铵盐沉淀回收钒、钙盐沉淀回收钨,即向浸出液中加入铵盐,得到偏钒酸铵晶体和滤液;向滤液再加入钙盐得到钨酸铵沉淀,再经酸洗、煅烧得到三氧化钨,该方法工艺简单、回收成本低、处理量大,但产品杂质含量较高。离子交换法主要是利用离子交换树脂通过吸附和解吸浸出液中的钒和钨,实现钒和钨的分离提纯,该方法处理量小、使用成本高,不适合大规模工业应用。溶剂萃取法使用萃取剂对钒和钨进行分离,产品纯度高、处理量大、回收率高,但需要与化学沉淀法联合使用,导致工艺流程较长、生产成本偏高,且萃取剂存在污染问题。
CN106884090A公开了一种废弃脱硝催化剂中钒钨钛全回收的亚熔盐方法,包括预处理、亚熔盐浸出、二氧化钛回收、浸出液循环利用、钙化沉淀、钒钨分离、除钙、除钒等工艺,向钙化沉淀所得的钨钒酸钙中加入甲酸溶液选择性浸出钒,进行过滤除钨,得钨酸钙沉淀与含钒溶液,含钒溶液在经过硫酸沉淀除钙、氨水调PH得到偏钒酸铵溶液,该方法虽然实现了钒钨分离,但过程较为复杂。
CN113430384A公开一种碱性浸出液蒸发冷冻分离钨钒循环回用碱液的方法,首先将含钨钒矿置于反应釜内进行碱性溶液浸出得到废渣和含有钨钒的碱性浸出液,将碱性浸出液蒸发浓缩、冷却结晶首先分离出含杂质的钒酸钠复合晶体与碱性钨酸钠溶液;然后再将碱性钨酸钠溶液蒸发浓度得到钨酸钠晶体。该方案实现了钒和钨的结晶分离,但钒酸钠和钨酸钠两种产品均为中间产品,均含有大量的杂质,此外两次蒸发浓缩过程能耗较大。
发明内容
本发明的目的在于提供一种含钒钨酸盐溶液净化分离回收钒和钨的方法,首先通过钙化反应、铵化反应将含钒钨酸盐溶液中的铁、铬、钠、镁、锰、磷、硅等大部分杂质去除,得到较为纯净的偏钒酸铵和钨酸铵混合溶液,然后通过冷却结晶和蒸发结晶实现偏钒酸铵和钨酸铵的分离。本发明工艺流程短简单,分离效果好,适用于工业化生产,具有良好的经济效益和应用前景。
为解决上述技术问题,本发明所采取的技术方案是:一种含钒钨酸盐溶液净化分离回收钒和钨的方法,所述方法包括以下步骤:
(1)向含钒钨酸盐溶液中加入钙化剂进行钙化反应,然后液固分离,得到以钒酸钙和钨酸钙为主的固相1和滤液1;
(2)将固相1加入到水中制备成浆料,向浆料中加入铵化剂进行浸出反应,然后进行液固分离得到以偏钒酸铵和钨酸铵为主的滤液2和以碳酸钙为主的固相2;
(3)将滤液2进行冷却结晶,然后液固分离得到偏钒酸铵固相3和钨酸铵滤液3。
(4)当滤液3中钨浓度≥M时,滤液3进行蒸发结晶,然后液固分离得到钨酸铵固相4和滤液4;当滤液3中钨浓度≤M时,滤液3返回步骤2进行铵浸出反应。
本发明所述步骤(1)中,含钒钨酸盐溶液是指含钒钛钨系脱硝催化剂或钒钨矿经过NaOH溶液浸出或钠化焙烧-水浸得到的溶液。
本发明所述步骤(1)中,钙化剂为氧化钙、氢氧化钙、氯化钙的任意一种或几种,优选为氧化钙。
本发明所述步骤(1)中,钙化反应温度30-95℃,钙化剂中钙的摩尔量与溶液中钒和钨的摩尔量之比Ca/(V+W)为0.8-1.8,钙化时间20-120min,搅拌速度为200-500r/min。
本发明所述步骤(1)中,铵化剂为碳酸铵、碳酸氢铵、磷酸铵、磷酸氢铵中的任意一种或几种,优选为碳酸氢铵。
本发明所述步骤(2)中,浸出反应温度40-95℃,铵化剂中铵的摩尔量与固相1中钒和钨的摩尔量之比NH4 +/(V+W)为0.9-1.7,浸出时间30-150min,搅拌速度为200-500 r/min。
本发明所述步骤(3)中所述冷却结晶温度为0-30℃,结晶时间30-300min,搅拌速度为150-300r/min。
本发明所述步骤(4)中,蒸发结晶温度90-100℃,搅拌速度为150-300r/min,当滤液3密度达到2.8-4kg/L时停止加热;所述M为80-120g/L。
本发明所述步骤(1)中,滤液1可经蒸发浓缩后用于钒钛钨系脱硝催化剂或钒钨矿NaOH溶液浸出工艺。
本发明所述方法钒回收率≥90%,钨回收率≥64%;固相3纯度>99%,固相4纯度>98%。
采用上述技术方案所产生的有益效果在于:1、本发明首先通过钙化反应、铵化反应将含钒钨酸盐溶液中的铁、铬、钠、镁、锰、磷、硅等大部分杂质去除,得到较为纯净的偏钒酸铵和钨酸铵混合溶液,偏钒酸铵固相3纯度>99%,钨酸铵固相4纯度>98%。2、本发明通过冷却结晶和蒸发结晶实现偏钒酸铵和钨酸铵的分离,工艺流程短简单,分离效果好,钒回收率≥90%,钨回收率≥64%,适用于工业化生产。
附图说明
图1为本发明的工艺流程图。
具体实施方式
下面结合附图和实施例对本发明做进一步详细的说明。
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
实施例1
(1)取含钒钨酸盐溶液500mL,溶液中钒浓度为20.32g/L,钨浓度为18.32g/L,加入氧化钙进行钙化反应,温度为95℃,Ca/(V+W)为1.8,时间120min,搅拌速度为400/min,然后液固分离,得到以钒酸钙和钨酸钙为主的固相1和滤液1;
(2)将固相1加入到水中制备成浆料,向浆料中加入铵化剂进行浸出反应,浸出温度为90℃,NH4 +/(V+W)为1.7,浸出时间150min,搅拌速度为450r/min,然后进行液固分离得到以偏钒酸铵和钨酸铵为主的滤液2和以碳酸钙为主的固相2;
(3)将滤液2进行冷却结晶,冷却结晶温度为20℃,结晶时间300min,搅拌速度为200r/min,然后液固分离得到偏钒酸铵固相3和钨酸铵滤液3。
(4)经检测滤液3中钨浓度为17.95g/L,滤液3返回步骤2进行铵浸出反应。
经检测:偏钒酸铵纯度99.05%,钒收率95.23%,钨收率为0。
实施例2
(1)取含钒钨酸盐溶液500mL,溶液中钒浓度为20.32g/L,钨浓度为18.32g/L,加入氧化钙进行钙化反应,温度为90℃,Ca/(V+W)为1.5,时间90min,搅拌速度为300/min,然后液固分离,得到以钒酸钙和钨酸钙为主的固相1和滤液1;
(2)将固相1加入到五次循环滤液3中制备成浆料,其中五次循环滤液3中的钨浓度为83.59g/L,向浆料中加入铵化剂进行浸出反应,浸出温度为95℃,NH4 +/(V+W)为1.6,浸出时间120min,搅拌速度为300r/min,然后进行液固分离得到以偏钒酸铵和钨酸铵为主的滤液2和以碳酸钙为主的固相2;
(3)将滤液2进行冷却结晶,冷却结晶温度为0℃,结晶时间180min,搅拌速度为250r/min,然后液固分离得到偏钒酸铵固相3和钨酸铵滤液3。
(4)经检测滤液3中钨浓度为82.89g/L,将滤液3进行蒸发结晶,蒸发结晶温度95℃,搅拌速度为150r/min,当溶液密度达到2.8kg/L时停止加热,结晶完成后进行液固分离得到钨酸铵固相4和滤液4。
经检测:偏钒酸铵纯度99.32%,钒收率96.37%,钨酸铵纯度为98.73%,钨收率为65.23%。
实施例3
(1)取含钒钨酸盐溶液500mL,溶液中钒浓度为20.32g/L,钨浓度为18.32g/L,加入氧化钙进行钙化反应,温度为80℃,Ca/(V+W)为1.2,时间60min,搅拌速度为350/min,然后液固分离,得到以钒酸钙和钨酸钙为主的固相1和滤液1;
(2)将固相1加入到十次循环滤液3中制备成浆料,其中十次循环滤液3中的钨浓度为95.32g/L,向浆料中加入铵化剂进行浸出反应,浸出温度为85℃,NH4 +/(V+W)为1.4,浸出时间90min,搅拌速度为400r/min,然后进行液固分离得到以偏钒酸铵和钨酸铵为主的滤液2和以碳酸钙为主的固相2;
(3)将滤液2进行冷却结晶,冷却结晶温度为30℃,结晶时间300min,搅拌速度为200r/min,然后液固分离得到偏钒酸铵固相3和钨酸铵滤液3。
(4)经检测滤液3中钨浓度为95.6g/L,将滤液3进行蒸发结晶,蒸发结晶温度100℃,搅拌速度为200r/min,当溶液密度达到3kg/L时停止加热,结晶完成后进行液固分离得到钨酸铵固相4和滤液4。
经检测:偏钒酸铵纯度99.08%,钒收率93.69%,钨酸铵纯度为98.86%,钨收率为64.45%。
实施例4
(1)取含钒钨酸盐溶液500mL,溶液中钒浓度为20.32g/L,钨浓度为18.32g/L,加入氧化钙进行钙化反应,温度为80℃,Ca/(V+W)为1.2,时间60min,搅拌速度为350/min,然后液固分离,得到以钒酸钙和钨酸钙为主的固相1和滤液1;
(2)将固相1加入到十六次循环滤液3中制备成浆料,其中十六次循环滤液3中的钨浓度为105.54g/L,向浆料中加入铵化剂进行浸出反应,浸出温度为85℃,NH4 +/(V+W)为0.9,浸出时间30min,搅拌速度为200r/min,然后进行液固分离得到以偏钒酸铵和钨酸铵为主的滤液2和以碳酸钙为主的固相2;
(3)将滤液2进行冷却结晶,冷却结晶温度为0℃,结晶时间30min,搅拌速度为150r/min,然后液固分离得到偏钒酸铵固相3和钨酸铵滤液3。
(4)经检测滤液3中钨浓度为118.6g/L,将滤液3进行蒸发结晶,蒸发结晶温度100℃,搅拌速度为300r/min,当溶液密度达到4kg/L时停止加热,结晶完成后进行液固分离得到钨酸铵固相4和滤液4。
经检测:偏钒酸铵纯度99.15%,钒收率90.43%,钨酸铵纯度为98.62%,钨收率为66.97%。
以上实施例仅用以说明而非限制本发明的技术方案,尽管参照上述实施例对本发明进行了详细说明,本领域的普通技术人员应当理解:依然可以对本发明进行修改或者等同替换,而不脱离本发明的精神和范围的任何修改或局部替换,其均应涵盖在本发明的权利要求范围当中。
Claims (10)
1.一种含钒钨酸盐溶液净化分离回收钒和钨的方法,其特征在于,所述方法包括以下步骤:
(1)向含钒钨酸盐溶液中加入钙化剂进行钙化反应,然后液固分离,得到以钒酸钙和钨酸钙为主的固相1和滤液1;
(2)将固相1加入到水中制备成浆料,向浆料中加入铵化剂进行浸出反应,然后进行液固分离得到以偏钒酸铵和钨酸铵为主的滤液2和以碳酸钙为主的固相2;
(3)将滤液2进行冷却结晶,然后液固分离得到偏钒酸铵固相3和钨酸铵滤液3;
(4)当滤液3中钨浓度≥M时,滤液3进行蒸发结晶,然后液固分离得到钨酸铵固相4和滤液4;当滤液3中钨浓度≤M时,滤液3返回步骤2进行铵浸出反应。
2.根据权利要求1所述的一种含钒钨酸盐溶液净化分离回收钒和钨的方法,其特征在于,所述步骤(1)中,含钒钨酸盐溶液是指含钒钛钨系脱硝催化剂或钒钨矿经过NaOH溶液浸出或钠化焙烧-水浸得到的溶液。
3.根据权利要求1所述的一种含钒钨酸盐溶液净化分离回收钒和钨的方法,其特征在于,所述步骤(1)中,钙化剂为氧化钙、氢氧化钙、氯化钙的任意一种或几种。
4.根据权利要求1所述的一种含钒钨酸盐溶液净化分离回收钒和钨的方法,其特征在于,所述步骤(1)中,钙化反应温度30-95℃,钙化剂中钙的摩尔量与溶液中钒和钨的摩尔量之比Ca/(V+W)为0.8-1.8,钙化时间20-120min,搅拌速度为200-500r/min。
5.根据权利要求1所述的一种含钒钨酸盐溶液净化分离回收钒和钨的方法,其特征在于,所述步骤(1)中,铵化剂为碳酸铵、碳酸氢铵、磷酸铵、磷酸氢铵中的任意一种或几种。
6. 根据权利要求1所述的一种含钒钨酸盐溶液净化分离回收钒和钨的方法,其特征在于,所述步骤(2)中,浸出反应温度40-95℃,铵化剂中铵的摩尔量与固相1中钒和钨的摩尔量之比NH4 +/(V+W)为0.9-1.7,浸出时间30-150min,搅拌速度为200-500 r/min。
7.根据权利要求1-6任意一项所述的一种含钒钨酸盐溶液净化分离回收钒和钨的方法,其特征在于,所述步骤(3)中所述冷却结晶温度为0-30℃,结晶时间30-300min,搅拌速度为150-300r/min。
8.根据权利要求1-6任意一项所述的一种含钒钨酸盐溶液净化分离回收钒和钨的方法,其特征在于,所述步骤(4)中,蒸发结晶温度90-100℃,搅拌速度为150-300r/min,当滤液3密度达到2.8-4kg/L时停止加热;所述M为80-120g/L。
9.根据权利要求1-6任意一项所述的一种含钒钨酸盐溶液净化分离回收钒和钨的方法,其特征在于,所述步骤(1)中,滤液1可经蒸发浓缩后用于钒钛钨系脱硝催化剂或钒钨矿NaOH溶液浸出工艺。
10.根据权利要求1-6任意一项所述的一种含钒钨酸盐溶液净化分离回收钒和钨的方法,其特征在于,所述方法钒回收率≥90%,钨回收率≥64%;固相3纯度>99%,固相4纯度>98%。
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