CN109207724B - A kind of extraction solvent and extraction method for simultaneously extracting and separating vanadium and chromium from vanadium-chromium solution - Google Patents
A kind of extraction solvent and extraction method for simultaneously extracting and separating vanadium and chromium from vanadium-chromium solution Download PDFInfo
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- 238000000605 extraction Methods 0.000 title claims abstract description 188
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 86
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 86
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 64
- 239000011651 chromium Substances 0.000 title claims abstract description 64
- 239000002904 solvent Substances 0.000 title claims abstract description 54
- WFISYBKOIKMYLZ-UHFFFAOYSA-N [V].[Cr] Chemical compound [V].[Cr] WFISYBKOIKMYLZ-UHFFFAOYSA-N 0.000 title claims description 27
- 239000003085 diluting agent Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 22
- 150000001408 amides Chemical class 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000003350 kerosene Substances 0.000 claims abstract description 11
- 150000008282 halocarbons Chemical class 0.000 claims abstract description 7
- 125000003368 amide group Chemical group 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 239000012074 organic phase Substances 0.000 claims description 79
- 239000000243 solution Substances 0.000 claims description 70
- 125000000217 alkyl group Chemical group 0.000 claims description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 22
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 239000012670 alkaline solution Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000003929 acidic solution Substances 0.000 claims description 9
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000000284 extract Substances 0.000 claims description 6
- 238000002386 leaching Methods 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000003723 Smelting Methods 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000009854 hydrometallurgy Methods 0.000 abstract description 2
- RMXTYBQNQCQHEU-UHFFFAOYSA-N ac1lawpn Chemical compound [Cr]#[Cr] RMXTYBQNQCQHEU-UHFFFAOYSA-N 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 18
- 239000002893 slag Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 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 3
- 239000002253 acid Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- DZMDPHNGKBEVRE-UHFFFAOYSA-N 1-chloroheptane Chemical compound CCCCCCCCl DZMDPHNGKBEVRE-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical class [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002308 calcification Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052740 iodine Chemical class 0.000 description 1
- 239000011630 iodine Chemical class 0.000 description 1
- -1 iodo hydrocarbons Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/32—Carboxylic acids
-
- 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
- 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
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/32—Obtaining chromium
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
本发明涉及湿法冶金技术领域,具体地说是一种从含钒铬溶液中同时萃取分离钒铬的萃取溶剂及萃取方法,其特征在于该萃取溶剂由萃取剂和稀释剂混合组成,所述的萃取剂为溶解度低于0.5g/L水溶性酰胺,所述的稀释剂为惰性有机溶剂,所述的萃取剂为N‑烷基酰胺和N,N,N,N‑四烷基二酰胺或含有多个酰胺基团等低水溶性酰胺中的一种或多种,所述的稀释剂为磺化煤油、白油和常温下为液态的卤代烃类化合物等惰性有机溶剂中的一种或多种,通过配制萃取溶剂、萃取、洗涤、反萃铬、反萃钒的工艺步骤得到高纯度的钒溶液或含钒沉淀物和铬铬液,具有工艺简单、萃取能力强、平衡快、分离选择性好、易反萃且经济环保等优点。The invention relates to the technical field of hydrometallurgy, in particular to an extraction solvent and an extraction method for simultaneously extracting and separating vanadium and chromium from a solution containing vanadium and chromium. The extraction agent is that the solubility is lower than 0.5g/L water-soluble amide, the diluent is an inert organic solvent, and the extraction agent is N-alkylamide and N,N,N,N-tetraalkyldiamide Or contain one or more of low water-soluble amides such as multiple amide groups, and the diluent is one or more in inert organic solvents such as sulfonated kerosene, white oil and liquid halogenated hydrocarbon compounds at normal temperature. One or more, through the process steps of preparing extraction solvent, extraction, washing, stripping chromium, stripping vanadium to obtain high-purity vanadium solution or vanadium-containing precipitate and chromium-chromium solution, which has the advantages of simple process, strong extraction ability and fast balance. , good separation selectivity, easy stripping and economical and environmental protection.
Description
技术领域technical field
本发明涉及湿法冶金技术领域,具体地说是一种工艺简单、萃取能力强、平衡快、选择性好、易反萃分离且经济环保的从含钒铬溶液中同时萃取分离钒铬的萃取溶剂及萃取方法。The invention relates to the technical field of hydrometallurgy, in particular to an extraction method for simultaneously extracting and separating vanadium and chromium from a vanadium-chromium solution, which is simple in process, strong in extraction capacity, fast in balance, good in selectivity, easy in stripping and separation, and economical and environmentally friendly. Solvents and methods of extraction.
背景技术Background technique
众所周知,钒和铬都是重要的战略资源,它们广泛应用于各行各业。但是钒铬性质非常相似,一般都是共生于钒钛磁铁矿中,对于焙烧后的钒铬渣,其水浸液中钒铬的分离提纯是目前很难解决的问题。As we all know, both vanadium and chromium are important strategic resources, and they are widely used in various industries. However, the properties of vanadium and chromium are very similar, and they are generally symbiotic in vanadium-titanium magnetite. For the vanadium-chromium slag after roasting, the separation and purification of vanadium-chromium in the water immersion solution is a difficult problem to solve at present.
针对以上问题,公开号为CN1073414的专利公开一种化学法处理钒铬废液的方法,先以三氯化铁与五价钒再弱酸性溶液中形成沉淀,过滤后再以硫酸和硫酸铵提铬,但是该工艺避免钒铬同时沉淀,只能对低浓度的钒铬液有较好的效果。中国专利CN101121962A发明一种伯仲复合胺萃取分离钒铬的办法,该专利分离钒铬效果较好,但是工序复杂,且耗能较多。中国专利CN102127654采用亚熔盐法提取钒铬,以分步结晶得到钒酸钠和铬酸钠,该工艺所得产品价值较高,但是产品不纯,消耗较多试剂,且回收率并不高。In view of the above problems, the patent publication number CN1073414 discloses a method for chemically treating vanadium-chromium waste liquid. First, ferric chloride and pentavalent vanadium are used to form precipitation in a weakly acidic solution, and after filtration, they are extracted with sulfuric acid and ammonium sulfate. However, this process avoids the simultaneous precipitation of vanadium and chromium, and can only have a good effect on low-concentration vanadium-chromium solutions. Chinese patent CN101121962A invents a method for extracting and separating vanadium and chromium with primary and secondary complex amines. The patent has good effect of separating vanadium and chromium, but the process is complicated and energy consumption is high. Chinese patent CN102127654 adopts the sub-molten salt method to extract vanadium and chromium, and obtains sodium vanadate and sodium chromate by fractional crystallization. The value of the product obtained by this process is higher, but the product is impure, consumes a lot of reagents, and the recovery rate is not high.
发明内容SUMMARY OF THE INVENTION
本发明的目的是解决上述现有技术的不足,提供一种工艺简单、萃取能力强、平衡快、选择性好、易反萃分离且经济环保的从含钒铬溶液中同时萃取分离钒铬的方法。The object of the present invention is to solve the above-mentioned deficiencies of the prior art, and to provide a method for simultaneously extracting and separating vanadium and chromium from a vanadium-chromium solution, which is simple in process, strong in extraction ability, fast in balance, good in selectivity, easy to strip and separate, and economical and environmentally friendly. method.
本发明解决其技术问题所采用的技术方案是:The technical scheme adopted by the present invention to solve its technical problems is:
一种从含钒铬溶液中同时萃取分离钒铬的萃取溶剂,其特征在于该萃取溶剂由萃取剂和稀释剂混合组成,所述的萃取剂为溶解度低于0.5g/L的水溶性酰胺,所述的稀释剂为惰性有机溶剂。A kind of extraction solvent that simultaneously extracts and separates vanadium-chromium from vanadium-chromium solution, it is characterized in that this extraction solvent is made up of extraction agent and diluent mixing, and described extraction agent is the water-soluble amide whose solubility is lower than 0.5g/L, The diluent is an inert organic solvent.
本发明所述的萃取剂为N-烷基酰胺和N,N,N,N-四烷基二酰胺或含有多个酰胺基团的溶解度低于0.5g/L的水溶性酰胺中的一种或多种,所述的稀释剂为磺化煤油、白油和常温下为液态的卤代烃类化合物的惰性有机溶剂中的一种或多种。The extraction agent of the present invention is one of N-alkylamide and N,N,N,N-tetraalkyldiamide or water-soluble amide containing multiple amide groups and the solubility is lower than 0.5g/L Or more, the diluent is one or more of sulfonated kerosene, white oil and inert organic solvent of halogenated hydrocarbon compound which is liquid at normal temperature.
本发明所述的萃取剂和稀释剂二者中有一个在25℃是固体或两者在25℃都是固体时,萃取溶剂中萃取剂的质量占比为2%~100%,稀释剂的质量占比为0~98%,当萃取剂和稀释剂在25℃均为液体时;萃取溶剂中萃取剂的体积占比为5%—100%,稀释剂的体积占比为0~95%。When one of the extractant and the diluent described in the present invention is solid at 25°C or both are solid at 25°C, the mass ratio of the extractant in the extraction solvent is 2% to 100%, and the weight of the diluent is 2% to 100%. The mass ratio is 0~98%, when both the extractant and the diluent are liquid at 25°C; the volume ratio of the extractant in the extraction solvent is 5%-100%, and the volume ratio of the diluent is 0~95% .
本发明所述的N-烷基酰胺和N,N,N,N-四烷基二酰胺或含有多个酰胺基团的溶解度低于0.5g/L的水溶性酰胺中,酰基中烷基的碳原子数为 1~18,可以是直链烷基也可以是支链烷基。In the N-alkylamides and N,N,N,N-tetraalkyldiamides of the present invention or the water-soluble amides containing multiple amide groups and the solubility of which is lower than 0.5g/L, the alkyl group in the acyl group The number of carbon atoms is 1 to 18, and it may be a straight-chain alkyl group or a branched-chain alkyl group.
本发明所述的N-烷基酰胺中与氮原子直接相连的烷基中碳原子数为 1~18,所述的N,N,N,N-四烷基二酰胺中与氮原子直接相连的两个烷基为相同的烷基或不同的烷基,并且这两个与氮原子直接相连的两个烷基的碳原子数分别为 1~18,可以是直链烷基也可以是支链烷基。The number of carbon atoms in the alkyl group directly connected to the nitrogen atom in the N-alkylamide of the present invention is 1 to 18, and the N,N,N,N-tetraalkyldiamide is directly connected to the nitrogen atom. The two alkyl groups are the same alkyl group or different alkyl groups, and the carbon atoms of the two alkyl groups directly connected to the nitrogen atom are 1 to 18, which can be straight-chain or branched. Alkyl.
本发明所述的磺化煤油碳原子数为11~17,所述白油型号为1#~7#,所述常温下为液态的卤代烃类化合物为氯代烃、溴代烃或碘代烃的惰性有机溶剂中的一种或多种。The carbon number of the sulfonated kerosene of the present invention is 11-17, the type of the white oil is 1#-7#, and the halogenated hydrocarbon compound that is liquid at room temperature is chlorinated hydrocarbon, brominated hydrocarbon or iodine One or more of the inert organic solvents that replace hydrocarbons.
一种从含钒铬溶液中同时萃取分离钒铬的方法,其特征在于该萃取分离方法的工艺步骤如下:A method for simultaneously extracting and separating vanadium and chromium from a vanadium-containing chromium solution is characterized in that the processing steps of this extraction and separation method are as follows:
(1).配制萃取溶剂:萃取溶剂由萃取剂和稀释剂混合组成,所述的萃取剂为溶解度低于0.5g/L的水溶性酰胺,所述的稀释剂为惰性有机溶剂,两者混合配成萃取溶剂作为有机相;(1). Preparation of extraction solvent: the extraction solvent is composed of a mixture of an extractant and a diluent. The extractant is a water-soluble amide with a solubility of less than 0.5 g/L, and the diluent is an inert organic solvent. The two are mixed. Dubbed extraction solvent as organic phase;
(2).萃取:取步骤(1)中的萃取溶剂萃取含钒铬溶液,含钒铬溶液的PH为1.3~10,萃取温度为10~90℃,相比O/A=0.4~4.0,时间为 1~10 min,萃取方式为逆流萃取、分馏萃取或错流萃取,萃取级数为 1~35 级,得到负载有机相;(2) Extraction: take the extraction solvent in step (1) to extract the vanadium-containing chromium solution, the PH of the vanadium-chromium-containing solution is 1.3-10, the extraction temperature is 10-90 ℃, compared with O/A=0.4-4.0, The time is 1-10 min, the extraction method is counter-current extraction, fractional extraction or cross-current extraction, and the number of extraction stages is 1-35 to obtain the loaded organic phase;
(3).洗涤:用溶液洗涤步骤(2)中得到的负载有机相,溶液的pH为1.2~9.0,温度为10~90℃,相比O/A=0.4~40,时间为 1~10 min,得到洗涤后的有机相;(3). Washing: washing the loaded organic phase obtained in step (2) with a solution, the pH of the solution is 1.2~9.0, the temperature is 10~90℃, the ratio O/A=0.4~40, and the time is 1~10 min, to obtain the organic phase after washing;
(4).反萃铬:取碱性溶液反萃步骤(3)中得到的洗涤后的有机相,萃取温度为 10℃~60℃,相比O/A=1~20,时间为 1~8 min,所述的碱性溶液pH为7.2~10.0, 反萃取方式为逆流萃取或错流萃取,萃取级数为 1~10 级,得到高纯度铬液和负载钒的有机相;(4). Back-extraction of chromium: take the alkaline solution for back-extraction of the washed organic phase obtained in step (3), the extraction temperature is 10 ℃ ~ 60 ℃, compared with O/A = 1 ~ 20, and the time is 1 ~ 8 min, the pH of the alkaline solution is 7.2-10.0, the back-extraction method is counter-current extraction or cross-current extraction, and the number of extraction stages is 1-10, to obtain high-purity chromium solution and vanadium-loaded organic phase;
(5).反萃钒:取碱性溶液反萃步骤(4)中得到的负载钒的有机相,萃取温度为 10℃~60℃,相比 O/A=1~10,时间为 1~10 min,所述的碱性溶液pH为7.5~13.5,反萃取方式为逆流萃取或错流萃取,萃取级数为 1~10级,得到高纯度钒液。(5). Back-extraction of vanadium: take the alkaline solution for back-extraction of the vanadium-loaded organic phase obtained in step (4), the extraction temperature is 10 ℃ ~ 60 ℃, compared with O/A = 1 ~ 10, and the time is 1 ~ For 10 min, the pH of the alkaline solution is 7.5-13.5, the back-extraction method is counter-current extraction or cross-current extraction, and the extraction stages are 1-10 to obtain a high-purity vanadium solution.
本发明所述的含钒铬溶液包括钒钛磁铁矿冶炼废渣浸出液,两种及两种以上含钒或铬的多金属硫酸介质的混合溶液,其中,溶液中同时含有钒和铬,或只含有钒或铬;钒的价态是四价或五价,或是四价与五价钒的混合物;铬的价态是三价或六价,或是三价和六价的混合物。The vanadium-containing chromium solution of the present invention includes vanadium titanomagnetite smelting waste slag leaching solution and a mixed solution of two or more polymetallic sulfuric acid media containing vanadium or chromium, wherein the solution contains both vanadium and chromium, or only Contains vanadium or chromium; the valence state of vanadium is tetravalent or pentavalent, or a mixture of tetravalent and pentavalent vanadium; the valence state of chromium is trivalent or hexavalent, or a mixture of trivalent and hexavalent.
本发明所述的步骤(4)和步骤(5)中碱性物质为氨水、氢氧化钠、氢氧化钾、氢氧化钙、碳酸钠、碳酸铵、碳酸钾、氯化铵、硫酸铵的一种或几种混合物。In the step (4) and step (5) of the present invention, the alkaline substance is a mixture of ammonia water, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, ammonium carbonate, potassium carbonate, ammonium chloride, and ammonium sulfate. species or a mixture of several.
所述的步骤(3)中溶液为酸性溶液,该酸性溶液包括硫酸或硝酸等不易被氧化的无机酸,或含有这几种无机酸的一种或两种混合物。The solution in the step (3) is an acidic solution, and the acidic solution includes inorganic acids that are not easily oxidized such as sulfuric acid or nitric acid, or a mixture containing one or both of these inorganic acids.
本发明由于该萃取溶剂由萃取剂和稀释剂混合组成,所述的萃取剂为溶解度低于0.5g/L水溶性酰胺,所述的稀释剂为惰性有机溶剂,所述的萃取剂为N-烷基酰胺和N,N,N,N-四烷基二酰胺的溶解度低于0.5g/L水溶性酰胺中的一种或多种,所述的稀释剂为磺化煤油、白油和常温下为液态的卤代烃类化合物等惰性有机溶剂中的一种或多种,通过配制萃取溶剂、萃取、洗涤、反萃铬、反萃钒的工艺步骤得到高纯度的钒液和铬液,上述步骤中使用的萃取剂和稀释剂原料易得,对钒铬萃取能力强,选择性好,易反萃分离钒铬,得到高纯度的钒液和铬液;增加有机相洗涤工序,有效去除负载有机相可能含有的其他杂质;有机相可循环再生,多次进行萃取反应,有利于成本的降低,具有工艺简单、萃取能力强、平衡快、选择性好、易反萃分离且经济环保等优点。In the present invention, because the extraction solvent is composed of an extractant and a diluent, the extractant is a water-soluble amide with a solubility lower than 0.5 g/L, the diluent is an inert organic solvent, and the extractant is N- The solubility of alkylamide and N,N,N,N-tetraalkyldiamide is lower than one or more of 0.5g/L water-soluble amide, and the diluent is sulfonated kerosene, white oil and normal temperature One or more of inert organic solvents such as liquid halogenated hydrocarbon compounds, etc., obtain high-purity vanadium liquid and chromium liquid through the process steps of preparing extraction solvent, extraction, washing, back-extracting chromium, and back-extracting vanadium, The extractant and diluent used in the above steps are easy to obtain, have strong vanadium-chromium extraction ability and good selectivity, and are easy to strip and separate vanadium and chromium to obtain high-purity vanadium liquid and chromium liquid; an organic phase washing process is added to effectively remove the Other impurities that may be contained in the organic phase are loaded; the organic phase can be recycled and regenerated, and the extraction reaction can be carried out multiple times, which is beneficial to cost reduction. advantage.
具体实施方式Detailed ways
一种从含钒铬溶液中同时萃取分离钒铬的萃取溶剂,其特征在于该萃取溶剂由萃取剂和稀释剂混合组成,所述的萃取剂为溶解度低于0.5g/L的水溶性酰胺,所述的稀释剂为惰性有机溶剂,所述的萃取剂为N-烷基酰胺和N,N,N,N-四烷基二酰胺的溶解度低于0.5g/L的水溶性酰胺中的一种或多种,优选的,所述的单取代酰胺,其中烷基R中碳原子数为6~10,优选的,所述的双取代酰胺,其中两个烷基R可以相同,也可不同;烷基R中碳原子数为6~10,所述的稀释剂为磺化煤油、白油和常温下为液态的卤代烃类化合物等惰性有机溶剂中的一种或多种,所述的萃取剂和稀释剂二者中有一个在25℃是固体或两者在25℃都是固体时,萃取溶剂中萃取剂的质量占比为2%~100%,稀释剂的质量占比为0~98%,当萃取剂和稀释剂在25℃均为液体时;萃取溶剂中萃取剂的体积占比为5%—100%,稀释剂的体积占比为0~95%,所述的N-烷基酰胺和N,N,N,N-四烷基二酰胺的溶解度低于0.5g/L水溶性酰胺中,酰基中烷基的碳原子数为 1~18,可以是直链烷基也可以是支链烷基,所述的N-烷基酰胺中与氮原子直接相连的烷基中碳原子数为 1~18,可以是直链烷基也可以是支链烷基,所述的N,N,N,N-四烷基二酰胺中与氮原子直接相连的两个烷基为相同的烷基或不同的烷基,并且这两个与氮原子直接相连的两个烷基的碳原子数分别为 1~18,可以是直链烷基也可以是支链烷基,所述的磺化煤油碳原子数为11~17,所述白油型号为1#~7#,所述常温下为液态的卤代烃类化合物为氯代烃、溴代烃或碘代烃等惰性有机溶剂中的一种或多种,该萃取分离方法的工艺步骤如下:(1).配制萃取溶剂:萃取溶剂由萃取剂和稀释剂混合组成,所述的萃取剂为溶解度低于0.5g/L水溶性酰胺,所述的稀释剂为惰性有机溶剂,两者混合配成萃取溶剂作为有机相;(2).萃取:取步骤(1)中的萃取溶剂萃取含钒铬溶液,优选为酸性溶液,含钒铬溶液的PH为1.3~5,萃取温度为10℃~70℃,相比O/A=0.4~3,时间为 1~8min,得到负载有机相,萃取方式为逆流萃取、分馏萃取或错流萃取,萃取级数为 1~10 级,得到负载有机相;(3).洗涤:用酸性溶液洗涤步骤(2)中得到的负载有机相,酸性溶液的pH为1.2~5,温度为10℃~70℃,相比O/A=0.4~2,时间为 1~8 min,得到洗涤后的有机相;(4).反萃铬:取碱性溶液反萃步骤(3)中得到的洗涤后的有机相,萃取温度为 10℃~60℃,相比O/A=1~15,时间为 1~8 min,所述的碱性溶液pH为7.2~9.0, 反萃取方式为逆流萃取或错流萃取,萃取级数为 1~10 级,得到高纯度铬液和负载钒的有机相;(5).反萃钒:取碱性溶液反萃步骤(4)中得到的负载钒的有机相,萃取温度为 10℃~60℃,相比 O/A=1~8,时间为 1~10 min,所述的碱性溶液pH为7.5~13.5,反萃取方式为逆流萃取或错流萃取,萃取级数为 1~10级,得到高纯度钒液,所述的含钒铬溶液包括钒钛磁铁矿冶炼废渣浸出液,两种及两种以上含钒或铬的多金属硫酸介质的混合溶液,其中,溶液中同时含有钒和铬,或只含有钒或铬;钒的价态是四价或五价,或是四价与五价钒的混合物;铬的价态是三价或六价,或是三价和六价的混合物,所述的步骤(4)和步骤(5)中碱性物质为氨水、氢氧化钠、氢氧化钾、氢氧化钙、碳酸钠、碳酸铵、碳酸钾、氯化铵、硫酸铵的一种或几种混合物,所述的步骤(3)中酸性溶液包括硫酸或硝酸等不易被氧化的无机酸,或含有这几种无机酸的一种或两种混合物。A kind of extraction solvent that simultaneously extracts and separates vanadium-chromium from vanadium-chromium solution, it is characterized in that this extraction solvent is made up of extraction agent and diluent mixing, and described extraction agent is the water-soluble amide whose solubility is lower than 0.5g/L, The diluent is an inert organic solvent, and the extractant is one of the water-soluble amides of N-alkylamide and N,N,N,N-tetraalkyldiamide whose solubility is lower than 0.5g/L. One or more, preferably, the single-substituted amide, wherein the number of carbon atoms in the alkyl R is 6~10, preferably, the two-substituted amide, wherein the two alkyl R can be the same or different ; The number of carbon atoms in the alkyl R is 6~10, and the described diluent is one or more of inert organic solvents such as sulfonated kerosene, white oil and liquid halogenated hydrocarbon compounds at normal temperatures, and the described When one of the extractant and diluent is solid at 25°C or both are solid at 25°C, the mass ratio of the extractant in the extraction solvent is 2%~100%, and the mass ratio of the diluent is 0~98%, when both the extractant and the diluent are liquid at 25°C; the volume ratio of the extractant in the extraction solvent is 5%-100%, and the volume ratio of the diluent is 0~95%. The solubility of N-alkylamide and N,N,N,N-tetraalkyldiamide is lower than 0.5g/L water-soluble amide, the number of carbon atoms in the alkyl group in the acyl group is 1-18, which can be straight chain alkane The alkyl group can also be a branched chain alkyl group. The number of carbon atoms in the alkyl group directly connected to the nitrogen atom in the N-alkyl amide is 1 to 18, which can be a straight chain alkyl group or a branched chain alkyl group. The two alkyl groups directly connected to the nitrogen atom in the N,N,N,N-tetraalkyldiamide are the same alkyl group or different alkyl groups, and the two alkyl groups directly connected to the nitrogen atom are the same alkyl group or different alkyl groups. The number of carbon atoms of the base is 1-18 respectively, which can be a straight-chain alkyl group or a branched-chain alkyl group. The carbon number of the sulfonated kerosene is 11-17, and the type of the white oil is 1#-7# , the halogenated hydrocarbon compounds that are liquid at room temperature are one or more of inert organic solvents such as chlorinated hydrocarbons, brominated hydrocarbons or iodo hydrocarbons, and the process steps of the extraction and separation method are as follows: (1). Preparation of extraction solvent: the extraction solvent is composed of an extraction agent and a diluent. The extraction agent is a water-soluble amide with a solubility of less than 0.5 g/L, and the diluent is an inert organic solvent. The two are mixed to form an extraction solvent as Organic phase; (2). Extraction: take the extraction solvent in step (1) to extract the vanadium-containing chromium solution, preferably an acidic solution, the PH of the vanadium-chromium solution is 1.3~5, the extraction temperature is 10 ℃~70 ℃, phase The ratio O/A=0.4~3, the time is 1~8min, and the loaded organic phase is obtained. The extraction method is countercurrent extraction, fractional distillation extraction or cross-flow extraction, and the number of extraction stages is 1~10, and the loaded organic phase is obtained; (3) .washing: washing the loaded organic phase obtained in step (2) with an acidic solution, the pH of the acidic solution is 1.2~5, the temperature is 10℃~70℃, the ratio O/A=0.4~2, and the time is 1~8 min, to obtain the washed organic phase; (4). Reverse Chromium extraction: take the washed organic phase obtained in the alkaline solution back extraction step (3), the extraction temperature is 10 ℃ ~ 60 ℃, compared with O/A = 1 ~ 15, the time is 1 ~ 8 min, the said The pH of the alkaline solution is 7.2-9.0, the back-extraction method is counter-current extraction or cross-current extraction, and the number of extraction stages is 1-10 to obtain high-purity chromium solution and vanadium-loaded organic phase; (5). Back-extraction of vanadium: Take the vanadium-loaded organic phase obtained in the back-extraction step (4) with an alkaline solution. The pH of the solution is 7.5-13.5, the back-extraction method is counter-current extraction or cross-current extraction, and the number of extraction stages is 1-10 to obtain a high-purity vanadium solution. The vanadium-chromium solution includes vanadium-titanium magnetite smelting waste residue leachate, Mixed solution of two or more kinds of polymetallic sulfuric acid medium containing vanadium or chromium, wherein the solution contains both vanadium and chromium, or only contains vanadium or chromium; the valence state of vanadium is tetravalent or pentavalent, or tetravalent The mixture of valence and pentavalent vanadium; the valence of chromium is trivalent or hexavalent, or a mixture of trivalent and hexavalent, and the alkaline substances in the steps (4) and (5) are ammonia water, hydroxide One or more mixtures of sodium, potassium hydroxide, calcium hydroxide, sodium carbonate, ammonium carbonate, potassium carbonate, ammonium chloride, and ammonium sulfate, the acidic solution in the step (3), including sulfuric acid or nitric acid, is not easily absorbed. Oxidized inorganic acids, or a mixture containing one or both of these inorganic acids.
N-烷基酰胺(结构式)如下:N-alkylamides (structural formula) are as follows:
N,N,N,N-四烷基二酰胺(结构式)如下:N,N,N,N-Tetraalkyldiamides (structural formula) are as follows:
N,N,N,N-四烷基二酰胺含有如下形式结构式:N,N,N,N-tetraalkyldiamides have the following structural formula:
实施例1Example 1
(1). 配制萃取溶剂:用质量占比10% +90%磺化 煤油混合配成萃取溶剂作为有机相; (1). Preparation of extraction solvent: 10% by mass +90% sulfonated kerosene is mixed to prepare extraction solvent as organic phase;
(2). 萃取:取步骤(1)中的萃取溶剂,4级逆流萃取pH为1.9钠化焙烧钒铬渣浸出液,温度为60℃,相比O/A=0.4,时间为1 min,得到负载有机相;(2). Extraction: take the extraction solvent in step (1), 4-stage countercurrent extraction pH is 1.9 sodium roasting vanadium-chromium slag leaching solution, temperature is 60 ℃, compared to O/A=0.4, time is 1 min, get load organic phase;
(3). 洗涤:用硫酸溶液洗涤步骤(2)的负载有机相,pH为1.4,温度为60℃,相比O/A=3,时间为5 min,得到洗涤后的有机相;(3). Washing: wash the loaded organic phase of step (2) with sulfuric acid solution, pH is 1.4, temperature is 60°C, compared to O/A=3, time is 5 min, to obtain the washed organic phase;
(4). 反萃铬:用pH为7.5的氨水溶液8级错流反萃步骤(3)的有机相,温度为40℃,相比O/A=2,时间为6 min,得到纯度为99.25%铬液和负载钒的有机相;(4). Back-extraction of chromium: 8-stage cross-flow back-extraction of the organic phase of step (3) with an ammonia solution with a pH of 7.5 at a temperature of 40 °C, compared with O/A = 2, and a time of 6 min, the purity is 99.25% chromium solution and vanadium-loaded organic phase;
(5).反萃钒:用pH为12.5的氨水溶液9级逆流反萃步骤(4)的负载钒的有机相,温度为30℃,相比O/A=2,时间为8min,得到纯度为99.87%钒液。(5). Back-extraction of vanadium: 9-stage countercurrent back-extraction of the vanadium-loaded organic phase in step (4) with an aqueous ammonia solution with a pH of 12.5 at a temperature of 30°C, compared with O/A=2, and a time of 8 minutes to obtain the purity It is 99.87% vanadium solution.
实施例2Example 2
(1).配制萃取溶剂:用质量占比20% +80%磺化煤油 混合配成萃取溶剂作为有机相; (1). Preparation of extraction solvent: 20% by mass +80% sulfonated kerosene is mixed to prepare extraction solvent as organic phase;
(2).萃取:取步骤(1)中的萃取溶剂,3级逆流萃取pH为1.7钠化焙烧钒铬渣浸出液,温度为50℃,相比O/A=0.5,时间为3min,得到负载有机相;(2). Extraction: take the extraction solvent in step (1), 3-stage countercurrent extraction pH is 1.7 sodium roasting vanadium-chromium slag leaching solution, the temperature is 50 ℃, the ratio O/A=0.5, the time is 3min, and the load is obtained. The organic phase;
(3).洗涤:用硫酸溶液洗涤步骤(2)的有机相,pH为1.6,温度为40℃,相比O/A=2,时间为1 min,得到洗涤后的有机相;(3). Washing: washing the organic phase of step (2) with sulfuric acid solution, the pH is 1.6, the temperature is 40°C, compared with O/A=2, the time is 1 min, and the washed organic phase is obtained;
(4).反萃铬:用pH为7.7的氨水溶液7级错流反萃步骤(3)的有机相,温度为20℃,相比O/A=1,时间为4 min,得到纯度为99.37%铬液和负载钒的有机相;(4). Back-extraction of chromium: 7-stage cross-flow back-extraction of the organic phase of step (3) with an ammonia solution with a pH of 7.7 at a temperature of 20 °C, compared with O/A = 1, and a time of 4 min, the obtained purity is 99.37% chromium solution and vanadium-loaded organic phase;
(5).反萃钒:用pH为12.9的氨水溶液7级逆流反萃步骤(4)的有机相,温度为20℃,相比O/A=5,时间为9 min,得到纯度为99.82%钒液。(5). Back-extraction of vanadium: 7-stage countercurrent back-extraction of the organic phase of step (4) with an ammonia solution with a pH of 12.9, a temperature of 20 °C, a comparison of O/A=5, a time of 9 min, and a purity of 99.82 % vanadium solution.
实施例3Example 3
(1).配制萃取溶剂:用质量占比30% +70% 3#白油 混合配成萃取溶剂作为有机相; (1). Preparation of extraction solvent: 30% by mass +70% 3# white oil is mixed into extraction solvent as organic phase;
(2).萃取:取步骤(1)中的萃取溶剂,3级逆流萃取酸度为pH为1.6的钙化被烧钒铬渣,温度为40℃,相比O/A=0.7,时间为1 min,得到负载有机相;(2). Extraction: take the extraction solvent in step (1), and extract the calcified vanadium-chromium slag with an acidity of pH 1.6 in a three-stage countercurrent extraction at a temperature of 40 °C, a ratio of O/A = 0.7, and a time of 1 min. , to obtain a loaded organic phase;
(3).洗涤:用硫酸溶液洗涤步骤(2)的有机相,pH为1.5,温度为30℃,相比O/A=1,时间为4 min,得到洗涤后的有机相;(3). Washing: wash the organic phase of step (2) with sulfuric acid solution, pH is 1.5, temperature is 30°C, compared with O/A=1, time is 4 min, and the washed organic phase is obtained;
(4).反萃铬:用pH为7.9的氨水溶液7级逆流反萃步骤(3)的有机相,温度为30℃,相比O/A=4,时间为8 min,得到纯度为99.41%铬液和负载钒的有机相;(4). Back-extraction of chromium: 7-stage counter-current back-extraction of the organic phase of step (3) with an ammonia solution with pH 7.9, the temperature is 30 °C, compared to O/A=4, the time is 8 min, and the purity is 99.41 % chromium solution and vanadium-loaded organic phase;
(5).反萃钒:用pH为12.7的氨水溶液8级逆流反萃步骤(4)的有机相,温度为50℃,相比O/A=4,时间为5 min,得到纯度为99.79%钒液。(5). Back-extraction of vanadium: 8-stage countercurrent back-extraction of the organic phase of step (4) with an ammonia solution with a pH of 12.7, a temperature of 50 °C, a comparison of O/A=4, a time of 5 min, and a purity of 99.79 % vanadium solution.
实施例4Example 4
(1).配制萃取溶剂:用质量占比40% +60% 5#白油混合配成萃 取溶剂作为有机相; (1). Preparation of extraction solvent: 40% by mass +60% 5# white oil is mixed into extraction solvent as organic phase;
(2).萃取:取步骤(1)中的萃取溶剂,2级错流萃取pH为1.5的钙化被烧钒铬渣浸出液,温度为30℃,相比O/A=1,时间为3 min,得到负载有机相;(2). Extraction: take the extraction solvent in step (1), and extract the calcified vanadium-chromium slag leaching solution with a pH of 1.5 in a second-stage cross-flow extraction at a temperature of 30 °C, a ratio of O/A=1, and a time of 3 min , to obtain a loaded organic phase;
(3).洗涤:用硫酸溶液洗涤步骤(1)的有机相,pH为1.8,温度为50℃,相比O/A=4,时间为2 min,得到洗涤后的有机相;(3). Washing: wash the organic phase of step (1) with sulfuric acid solution, pH is 1.8, temperature is 50°C, compared with O/A=4, time is 2 min, and the washed organic phase is obtained;
(4).反萃铬:用pH为8.0的氨水溶液5级错流反萃步骤(2)的有机相,温度为10℃,相比O/A=5,时间为7 min,得到纯度为99.19%铬液和负载钒的有机相;(4). Back-extraction of chromium: 5-stage cross-flow back-extraction of the organic phase of step (2) with an ammonia solution with a pH of 8.0 at a temperature of 10 °C, compared with O/A = 5, and a time of 7 min, the obtained purity is 99.19% chromium solution and vanadium-loaded organic phase;
(5).反萃钒:用pH为13.0的氨水溶液5级逆流反萃步骤(3)的有机相,温度为10℃,相比O/A=6,时间为2 min,得到纯度为99.90%钒液。(5). Back-extraction of vanadium: 5-stage countercurrent back-extraction of the organic phase of step (3) with an ammonia solution with a pH of 13.0 at a temperature of 10 °C, compared with O/A=6, and a time of 2 min, the purity is 99.90 % vanadium solution.
实施例5Example 5
(1).配制萃取溶剂:用质量占比50% +50%氯庚烷混合配成萃取 溶剂作为有机相; (1). Preparation of extraction solvent: 50% by mass +50% chloroheptane is mixed to prepare extraction solvent as organic phase;
(2).萃取:取步骤(1)中的萃取溶剂,1级错流萃取pH为1.4 钙化焙烧钒铬渣浸出液,温度为20℃,相比O/A=1.1,时间为4 min,得到负载有机相;(2). Extraction: take the extraction solvent in step (1), first-stage cross-flow extraction pH 1.4 calcification roasting vanadium-chromium slag leaching solution, temperature is 20 ℃, compared to O/A=1.1, time is 4 min, get load organic phase;
(3).洗涤:用硫酸溶液洗涤步骤(2)的有机相,pH为1.7,温度为10℃,相比O/A=2.5,时间为4 min,得到洗涤后的有机相;(3). Washing: wash the organic phase of step (2) with sulfuric acid solution, pH is 1.7, temperature is 10°C, compared to O/A=2.5, time is 4 min, and the washed organic phase is obtained;
(4).反萃铬:用pH为8.3的氨水溶液4级逆流反萃步骤(3)的有机相,温度为60℃,相比O/A=3,时间为2min,得到纯度为99.35%铬液和负载钒的有机相;(4). Back-extraction of chromium: 4-stage countercurrent back-extraction of the organic phase of step (3) with an ammonia solution with a pH of 8.3 at a temperature of 60 °C, compared with O/A=3, and a time of 2 minutes, the purity is 99.35%. Chromium solution and vanadium-loaded organic phase;
(5).反萃钒:用pH为13.1的氨水溶液3级逆流反萃步骤(4)的有机相,温度为40℃,相比O/A=1,时间为7 min,得到纯度为99.83%钒液。(5). Back-extraction of vanadium: 3-stage countercurrent back-extraction of the organic phase of step (4) with an ammonia solution with a pH of 13.1, a temperature of 40 °C, a comparison of O/A=1, a time of 7 min, and a purity of 99.83 % vanadium solution.
实施例6Example 6
(1).配制萃取溶剂:用质量占比60% +40%溴己烷混合配成 萃取溶剂作为有机相; (1). Preparation of extraction solvent: 60% by mass +40% bromohexane is mixed to prepare extraction solvent as organic phase;
(2).萃取:取步骤(1)中的萃取溶剂,1级逆流萃取酸度为1.3钒铬混合酸性溶液,温度为10℃,相比O/A=1.2,时间为5 min,得到负载有机相;(2). Extraction: take the extraction solvent in step (1), the first-stage countercurrent extraction acidity is 1.3 vanadium-chromium mixed acid solution, the temperature is 10 ° C, the ratio O/A=1.2, the time is 5 min, and the loaded organic Mutually;
(3).洗涤:用硫酸溶液洗涤步骤(2)的有机相,pH为1.6,温度为35℃,相比O/A=3.5,时间为3 min,得到洗涤后的有机相;(3). Washing: wash the organic phase of step (2) with sulfuric acid solution, pH is 1.6, temperature is 35°C, compared with O/A=3.5, time is 3 min, and the washed organic phase is obtained;
(4).反萃铬:用pH为8.5的氨水溶液2级逆流反萃步骤(3)的有机相,温度为55℃,相比O/A=2.5,时间为5 min,得到纯度为99.36%铬液和负载钒的有机相;(4). Back-extraction of chromium: 2-stage countercurrent back-extraction of the organic phase of step (3) with an aqueous ammonia solution with a pH of 8.5, the temperature is 55 °C, the ratio of O/A=2.5, the time is 5 min, and the purity is 99.36 % chromium solution and vanadium-loaded organic phase;
(5).反萃钒:用pH为13.2的氨水溶液2级逆流反萃步骤(4)的有机相,温度为55℃,相比O/A=6,时间为3 min,得到纯度为99.91%钒液。(5). Back-extraction of vanadium: 2-stage countercurrent back-extraction of the organic phase of step (4) with an aqueous ammonia solution with a pH of 13.2 at a temperature of 55 °C, compared with O/A=6, and a time of 3 min, the purity is 99.91 % vanadium solution.
实施例7Example 7
(1).配制萃取溶剂:用质量占比20%+80%磺化煤油混合配成萃取溶剂作为有 机相; (1). Preparation of extraction solvent: 20% by mass +80% sulfonated kerosene is mixed to prepare extraction solvent as organic phase;
(2).萃取:取步骤(1)中的萃取溶剂,3级逆流萃取酸度为1.6钒铬混合酸性溶液,温度为30℃,相比O/A=1.8,时间为6 min,得到负载有机相;(2). Extraction: take the extraction solvent in step (1), 3-stage countercurrent extraction of a vanadium-chromium mixed acid solution with an acidity of 1.6, a temperature of 30 °C, a ratio of O/A = 1.8, and a time of 6 min, to obtain a loaded organic Mutually;
(3).洗涤:用硫酸溶液洗涤步骤(2)的有机相,pH为1.5,温度为55℃,相比O/A=3.0,时间为6 min,得到洗涤后的有机相;(3). Washing: washing the organic phase of step (2) with sulfuric acid solution, pH is 1.5, temperature is 55°C, compared to O/A=3.0, time is 6 min, and the washed organic phase is obtained;
(4).反萃铬:用pH为8.0的氨水溶液2级逆流反萃步骤(3)的有机相,温度为45℃,相比O/A=2.0,时间为6 min,得到纯度为99.46%铬液和负载钒的有机相;(4). Back-extraction of chromium: 2-stage countercurrent back-extraction of the organic phase of step (3) with an aqueous ammonia solution with a pH of 8.0, the temperature is 45 °C, the ratio of O/A=2.0, the time is 6 min, and the purity is 99.46 % chromium solution and vanadium-loaded organic phase;
(5).反萃钒:用pH为13.0的氨水溶液4级逆流反萃步骤(4)的有机相,温度为45℃,相比O/A=5,时间为4 min,得到纯度为99.93%钒液。(5). Back-extraction of vanadium: 4-stage countercurrent back-extraction of the organic phase of step (4) with an ammonia solution with a pH of 13.0 at a temperature of 45 °C, compared with O/A=5, and a time of 4 min, the purity is 99.93 % vanadium solution.
实施例8Example 8
(1).配制萃取溶剂:用质量占比30%+70%4#白油混合配成萃取溶剂作为有机 相; (1). Preparation of extraction solvent: 30% by mass +70% 4# white oil is mixed into extraction solvent as organic phase;
(2).萃取:取步骤(1)中的萃取溶剂,4级逆流萃取酸度PH为1.9钒铬混合酸性溶液,温度为40℃,相比O/A=1.8,时间为2 min,得到负载有机相;(2). Extraction: take the extraction solvent in step (1), 4-stage countercurrent extraction of a mixed acid solution of vanadium and chromium with an acidity of PH of 1.9, a temperature of 40°C, a ratio of O/A = 1.8, and a time of 2 minutes to obtain a load The organic phase;
(3).洗涤:用硫酸溶液洗涤步骤(2)的有机相,pH为1.5,温度为40℃,相比O/A=2.5,时间为3 min,得到洗涤后的有机相;(3). Washing: washing the organic phase of step (2) with sulfuric acid solution, the pH is 1.5, the temperature is 40°C, the comparison O/A=2.5, the time is 3 min, and the washed organic phase is obtained;
(4).反萃铬:用pH为8.0的氨水溶液2级逆流反萃步骤(3)的有机相,温度为35℃,相比O/A=3.0,时间为2 min,得到纯度为99.46%铬液和负载钒的有机相;(4). Back-extraction of chromium: 2-stage countercurrent back-extraction of the organic phase of step (3) with an aqueous ammonia solution with a pH of 8.0, the temperature is 35 °C, the ratio of O/A=3.0, the time is 2 min, and the purity is 99.46 % chromium solution and vanadium-loaded organic phase;
(5).反萃钒:用pH为12.8的氨水溶液6级逆流反萃步骤(4)的有机相,温度为25℃,相比O/A=4,时间为1 min,得到纯度为99.93%钒液。(5). Back-extraction of vanadium: 6-stage countercurrent back-extraction of the organic phase of step (4) with an ammonia solution with a pH of 12.8 at a temperature of 25 °C, compared with O/A=4, and a time of 1 min, the purity is 99.93 % vanadium solution.
综上所述,利用本发明的工艺方法,能得到高纯度的钒液和铬液。To sum up, using the process method of the present invention, high-purity vanadium liquid and chromium liquid can be obtained.
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