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蒸发脱氨络合法制备的双氧水络合萃取分离钨钼前驱体料液(英文)

2022-04-04 来源:好走旅游网
Available online at www.sciencedirect.com : ScienceDirect ELSEⅥER Press Trans.Nonferrous Met.Soc.China 23(2013)1 139—1 146 Transactions of Noilferrous Metals Society of China www.tnmsc.cn Precursor solution prepared by evaporation deamination complex method for solvent separation of Mo and W by H202一complexation Wen-juan GUAN ,Gui.qing ZHANG ,Cong-jie GAO , 1.School of Metallurgical Science and Engineering,Central South University,Changsha 4 1 0083,China; 2.Key Laboratory of Hunan Province for Metallurgy and Material Processing of Rare Metals, Central South University,Changsha 4 1 0083,China Received 21 September 2012;accepted 22 November 2012 Abstract:An novel method on preparation of precursor solution for solvent separation of molybdenum fMo1 and tungsten f、v1 by hydrogen peroxide(H202)一complexation from the ammonium tungstate solution containing high Mo was sudited.The precursor solution was obtained via evaporation deamination and H,O2-complex transformation processes.Then it was extracted with a mixture extractant of tri—alkyI phosphine oxide(TRPO)and tributyI phosphate(TBP)to separate Mo and、 The results indicated that the evaporation deamination complex method reduced the acid consumption by more than 90%in comparison with the traditional directly acid regulation complex method.The transfclrmation rates of W and Mo were higher than 95%and the decomposition rate of H,O,was less than 1 5%at a 1.8—1.9 times H,O,dosage,45-50。C。initial pH of 1.80-1.90 and transformation volume ratio of 1 00%for 60 min in the H,O2-complexation transformation process.The minimum extraction rate of W was 2%。the maximum extraction rate of Mo was 82.6%and the highest separation coeficifent was 76.7 in a single—stage extraction. Key words:tungsten;molybdenum;solvent extraction separation;precursor solution;H,O, especially when the content of Mo js high.The precursor l IntrOductiOn In recent years,with the continuous and heavy solution of this method is H,O2-complex solution by adding H,O,into the mixed solution Of W and Mo. However,W and Mo lead to a violent heterogeneous consumption of high-class tungsten resources[1],the content of Mo in the available resources is higher and catalytic decomposition of H202 when pH>7[12].Thus, the alkaline tungstate solution containing Mo must be higher[2,3】.Presently,the methods which have been widely used in industry are based on the property adjusted to be acidic(pH=2—4)before adding H202. The sodium tungstate solution containing Mo can be diference between thiomolybdate and tungstate『4—61. These methods can meet the requirements for processing modified to be acidic by directly adding inorganic acid 『1 3-1 51,which is so—called“directly acid regulation complex mefhod”.However,it is confronted wim difhculties for the ammonium tungstate solution tungstate solution containing low Mo(m(Mo)/m(W03)< 2%1 but are not applicable to separate Mo from tungstate solution with high mass ratio of Mo to W because of too containing Mo by such a way.The first is the precipitation of a 1arge amount of crystal which is hardly soluble in H2O々solution at room temperature.The second is the high consumption of inorganic acid.For example,the ammonium tungstate solution containing high content of Mo was obtained from Luanchuan high cost[7].It is of great signiifcance to develop suitable process for the separation of Mo from tungstate solutions containing high content of Mo[8,9]. The method of solvent extraction separation of Mo and W by H202一complexation is based on the property difference between molybdenum peroxide and tungstate [16,17],in which the pH value is 9—10,the total NH4 concentration is about 4 mol/L and there is 2—2.5 mol/L peroxide[1 0,11].It provides obvious advantages including environmenta1 friendliness and low cost. NH+combined wjth HC0 or C0j一.Thus,the acid Foundation item:Project(2010ZX07212—008)suppoaed by the Major Science and Technology Program for Water Pollution Control and Treatment Corresponding author:Gui-qing ZHANG;Tel:+86・73 1-88830472;E-mail:gqzhang@163.corn DOI:10 1016/S1003—6326(13)62576-5 1140 Wen-juan GUAN,et al/Trans.Nonferrous Met.Soc.China 23(2013)1139—1146 consumption of ammonium solution is much higher than 豳af of sodium solution with a same pH regulation.刀】e high acid consumption increases the cost of Mo八v separation and the large amount of inorganic salt formed during acid.base neutralization causes the environmenta1 pollution. A novel method on preparation of the precursor solution from the ammonium tungstate solution was developed in this work.The precursor solution was obtained via processes of evaporation deamination and H2O2-complex transformation.In this method,the NH4HCO3 and(NH4)2CO3 in the ammonium solution were decomposed and removed in the form of NH and CO2 gases at high temperature,which lowered the pH of the solution and reduced the acid consumption.The removed NH3 and CO2 gases could be recovered by condensing.Thus。compared with the directly acid regulation complex method,the evaporation deamination complex method provides obvious advantages including low inorganic acid consumption,low cost and environmental friendliness.In this work.the behaviors of W,Mo and HEO,in the evaporation deamination and H2O2-complex transformation processes under different conditions were investigated to explore the most appropriate experimental conditions.And the precursor solution was ex仃acted with TRP0/TBP to determine whether it was qualified to separate Mo and W_ 2 Experimental 2.1 Experimental lfow Figure 1 shows the experimental flow of preparation Ammonium tungstate solution containing high Mo content 一一一一一l一一一一一一一一一一一 叵五五西 i. Evaporation deamination  iIl 一一一 一 Precursor solution for solvent separati ̄on of W and Mo by H2O2一complexation Fig.1 Flowchart of preparation of precursor solution by evaporation deamination complex method for solvent separation of Mo and W by H202一complexation of the precursor solution from ammonium tungstate solution containing high Mo content by the evaporation deamination complex method. 2.2 Reagents The ammonium tungstate solution contained 129 g/L WO3.16.6 g/L Mo and its pH was 9.22.It was obtained from the process of directly solvent extraction of tungsten from autoclave—soda leaching liquor of scheelite and provided by a plant of the China Molybdenum Co,,Ltd in Luanchuan,Henan Province, China.H202 was used as complex agent.Ammonium hydroxide(NH4OH)and the sulfuric acid(H2SO4)were used to adjust pH value of the solution.All reagents used were of analytical grade and the solutions were prepared in deionized water. The organic extractants,tri—alkyl phosphine oxide (TRPO,industrial grade,purity>93%)and tributyl phosphate(TBP,analytical grade,purity>98.5%),were employed for extraction without purification.The commercial sulfonated kerosene was employed as djluent. 2.3 Experimental methods The evaporation deamination tests were carried out by stiring and heating the ammonium tungstate solution samples of 500 mL in a beaker immersed in an electro thermostatic water bath for a specified time.The temperature was higher than 90。C.The pH value of the concentrated solution was adjusted to 3—4 bv adding 1:3 H7SO4 after evaporation concentration.Then a suitable amount of water was put into the beaker and the temperature continued to keep higher than 90。C for about 0.5 h.After that,the crystallization slurry was removed from the water bath for cooling without solid-liquid separation. The H,O2-complex transformation tests were carried out by mixing and heating a certain amount of H202 reagent and the crystallization slurry after cooling in a beaker immersed in an electro thermostatic water bath.The initial pH value was adjusted by adding 1:3 H2SO4 or l:1 NH40H and the transformation volume was adjusted by adding the pure water.The concentrations of WO3,Mo and H202 in the clarified complex solution were determined at regular intervals. The extraction tests were carried out by mixing a certain volume organic phase and aqueous solution in a 250 mL.conical flask immersed in a water bath and constant temperature oscillator for a specia1 time.After equilibration,the phases were allowed to separate in separating funnels and their volmues were measured.The concentrations of WO1 and Mo in aqueous were Wen-juan GUAN,et al/Trans.Nonferrous Met.Soc.China 23(2013)1 139—1 146 determined,and the extraction rates of W0 ,Mo and the 1 141 The pH value of the concentrated solution slowly decreased with the volatilization of ammonia.w0 — and Mo0 —continuously polymerized to APT and separation coeficifent 8 o were calculated. The concentration of H2O,was determined by potassium permanganate titration;the concentrations of WO and Mo in aqueous were determined by colorimetry using potassium thiocyanate and ammonium thiocyanate, respectively;the concentrations of W0 and Mo in secondary ammonium molybdenum(APM)at pH about 7.The reactions are as follows: 12(NH4)2WO4一 organic were calculated by subtraction method. The concentrated volume ratio .the transformation volume ratio and the H202 dosage Q were defined as : ×100% (1) a、v (3) where V is the volume; is the molar concentration;the subscripts“raw”.‘‘con”.“com’’and‘‘rea’’represent the ammonium tungstate solution,concentrated solution, H2O2一complex solution and H2O2 reagent,respectively. High concentration of H202 resulted in a long stable standing time[1 6].The stability of the H202一complex solution Q was defined as Q = F/H2O2,com× 0m n(w+M c。m x 。m (4) The transformation rates TM of M(WO3 or Mo)and the decomposition rate D of H2O2 were calculated as follows: PM∞m× d|0m = PM,raw×Vrw ×100% (5) DH202= oo% (6) PH o …rea× re where P is mass concentration. 2.4 Experimental principle The NH4HCO3 solution decomposed at temperature higher than 30。C and the(NH4)2CO3 solution decomposed at temperature higher than 70。C.Most of the NH4HCO3 and(NH4)2CO3 in the ammonium solution could be removed in the forms of NH3 and C02 gases in the evaporation deamination process at a temperature higher than 90。C,and the removed NH3 and CO2 could be recovered by condensing method.The reactions are as follows: 2NH4HCO3一(NH4)2CO3+H2O+CO2个 (7) (NH4)2CO3一H2O+2NH3个+CO2个 (8) (NH4)1o[H2 Wl2O42】・4H20+14NH3个+3H2O(9) 7(NH4)2MoO4一 (NH4)6[Mo7O24】・4H20+8NH3个 (10) H202 was added into the crystallization slurry and it reacted with W or Mo to form tungstate peroxide or molybdenum peroxide.The reactions are as follows: [H2 w12O42】 +24H2O2+2OH一= 6[W20l1(H20)2] +14H2O (11) 2Mo7o14+28H2O2+2OH一= 7[Mo2O11(H20)2] +15H2O The complex reaction of APT with H2O,progressed very slowly at room temperature.In order to increase the reaction rate,a certain temperature was kept during the H2O2-complex transformation process.The H202一complex solution after cooling was the precursor solution for solvent separation of Mo and W The qualified precursor solution was clear,transparent and stable.and by extracting with TRPO/TB a good separation effect of W and Mo could be obtained. 3 Results and discussion 3.1 Evaporation deamination Figure 2 shows the change law of the crystallization rates Of W and Mo and the pH value of the concentrated solution in the evaporation deamination process at 90。C. The results indicated that the pH value of the concentrated solution was decreased from 9.22 to 7.26 with the decrease of concentrated volume ratio from 1 00%to 1 7%.W began to crystallize when =80%. Although the solubility Of APM in water was much greater than that of AP a little Mo co—crystallized wi£b W in the form of isomorphism.phase『1 81.The crystallization rates of W increased from 5.50%to 84.4 1%with the decrease of concentrated volmue ratio rfom 80%to 17%.while the crystallization rates of Mo increased from 3.99%t0 32.01%. The relationship between the acid consumption and pH value was compared with that of the directly acid regulation complex method in Tf 1e 1.The results indicated that this method reduced acid consumption by more than 90%in comparison to the directly acid 1142 Wen-juan GUAN,et al/Trans.Nonferrous Met.Soc.China 23(2013)1 139—1 146 0 20 40 6O 8O 100 Transfotination time/rain Fig.2 Relationship between crystallization rates of W and Mo solution pH and concentrated volume ratio regulation complex method because the solution pH \≥Jo .I口0 ∞要oJ∞II卫 /0艺 0甚I10一 量 ∞昌JJL value had decreased from 9.22 to 7.26 in the evaporation concentration process and most of the NH4HCO3 and 0/0 0 z LIO。 窭 0暑∞0 II10u。Q (NH4)2CO3 had been removed. 3.2 H,O2-complex transformation 3.2.1 Efrects of H2O,dosage The effects of H2O2 dosage on the H2O2-complex transformation process was investigated in the range of Transformation time/ain r1.62-2.0 times『101.The result is shown in Fig.3. It can be seen rfom Figs.3(a)and(b)that the initial transforrnation rate of W was 14%一18%.but that of MO was 72%-82%.The reason was that the crystallization rate of W was much higher than that of MO in the evaporation deamination process.The transformation rates of W and Mo increased with the increase of transformation time at a constant H,O,dosage or increased with the increase of HEO,dosage at a constant transformation time.This result indicated that high dosage of H2O7 resulted in fast complex reaction of W and MO wih H2t02.Figure 3(c)shows that the decomposition rate of HEO,increased with the increase of transformation time or decreased with the increase of H202 dosage.Turbidity was seen in the H202一complex Transformation time/min Fig.3 Effects of H202 dosage on H202一complex transformation process at initial pH 1.80.temperature 50。C and solution at a H2O2 dosage of Q=I.6 times for 55 min, while the decomposition rate of H,O,was 24.86%and D in the H,O2-complex solution was 1.24.In order to transformation volume ratio 1 00%:(a)Transformation rate of w;(b)Transformation rate of Mo;(C)Decomposition rate of H202 and Q, Table 1 Relationships between acid consumption and pH value of evaporation deamination complex method(EDCM)and directly acid regulation complex method(DACM) Wen-juan GUAN,et al/Trans.Nonferrous Met.Soc.China 23(2013)1139—1146 l143 ensure the stability of the complex solution,the Q value should be higher than 1.4. A H202 dosage of Q=1.8—2.0 times was thought to be optimum.Under the experimental condition.the transformation rates of W and Mo were higher than 95% and the decomposition rate of H2O,was 1ower than 20% for a transformation time of 60 min.while the p values in the H202-complex solutions were higher than 1.5 and the solutions were clear and transparent during the experiment. 3.2.2 Ef_fects of transformation temperature and time Figure 4 shows the effects of transformation temperature and time on the H202-complex transformation process.It can be seen from Fig.4 that the transformation rates of W and Mo and the decomposition rate of H2O2 increased with the increase Of打ansformation time at a constant temperature or increased with the \≥l}0 0甚.increase I I10一 量盘∞磊J上 of transformation temperature at a constant time.The result indicated mat high temperature resulted in fast complex reaction of W and Mo with HE02 and fast decomposition of H2O2 or H2O2-complex. The transformation rates of W and Mo changed a little with the transformation time from 60 min to 1 20 arin at 40。C.40-90 min at 50。C and 35—55 min at 60 。C.TO ensure high仃ansformation rates of W and Mo. 1ow decomposition rate of H202 and good stability of the H202一complex solution.a temperature range of 45—50。C nad time of 60 min were selected. 3.2.3 Effects of initia1 pH value of H2O2-complex solution The initial pH value of the H202-complex solution before pH regulation was 1.6—2.1 at a H202 dosage of Q=1.8—2.0 times.It can be seen rfom Eqs.(11)and(12) mat 0H—was consumed during the complex reactions of W and Mo with H2O2.Thus,the PH value decreased in the process of H2O2-complex trans formation. Figure 5 shows the effects of initial PH value on the H202-complex transformation process.The result indicated that the initial pH value of H202-complex solution had a little influence on the transformation rates of W and Mo.The decomposition rate of HEO,decreased with the increase of initial PH value.An initial pH value of 1.8-1.9 was considered to be optimum. 3.2.4 Effects of transformation volume ratio le 2 shows the effects of the transformation volume ratio on the H202一complex transformation process.The result indicated that the transformation volume ratio of r/=77%一98%had little influence on the transformation rates of W and Mo.and the stabilities of all of the H2O2-complex solutions obtained at different transformation volume ratios were good.However.1ow Transformation time/min /o 0誊I10一苗量oJ∞磊 0 王{ BJ I10葛∞0qITransformation time/min Transformation time/min Fig.4 Effects of transformation temperature and time on H202-comple rtansformation process at H202 dosage of Q=1.8 times.initial pH 1.80 and trnasformation volume ratio r/=100%: (a)Transformation rate of w;(b)Transformation rate of Mo;(c) Decomposition rate of H202 and Q transformation volume ratio 卵 resulted in low decomposition rate of H2O,and high concentrations Of W and Mo in the HEO2-complex solution.Thus.the transformation volume ratio r/could be selected according to the practical needs of concentrations of W and Mo in the extraction process. Under the optimum conditions of H2O2 dosage Il08Q 1144 Wen-juan GUAN,etal/Trans.Nonferrous Met.Soc.China 23(2013)1139—1146 0/n/0荟 0焉基盘∞磊JjL  \ 0 }I 0 =|BJ I10暑∞0盆II10u Q in the ammonium tungstate solution at the beginning of the evaporation concentration.Thus the practical utilization ratios of W and Mo in the evaporation deamination complex method were close to 1 00%. 3.3 Extraction The precursor solution prepared by the evaporation deamination complex method contained 1 6 1.3 g/L WO3, 20.29 g/L Mo and pH was 1.75.The Q value in the precursor solution was 1.70.It was extracted wifh TRPO/TBP to separate W and Mo.The result is shown in Fig.6. Initial pH oftransformation 窘 暑 号 曼 【工] 6。 20 Initial pH of aqueous Initia1 pH oftransformation Fig.6 Result of solvent separation of W and Mo by H2O2一 Fig.5 Effects of initial pH value of H202一complex solution on complexation using aqueous solution containing 127——129 eYE WO3,15.9—16.1 g/L Mo with 2%(v/v)TRPO and 80%(v/v) TBP at oil to water(O/A)phase ratio of 2:1,temperature 20。C and contact time 5 min H202一complex transformation process at H202 dosage of Q=I.9, temperature 45。C and transformation volume ratio r/=100%for 60 min:(a)Transformation rates of W and Mo:fb) Decomposition rate of H2O2 and O It can be seen from Fig.6 that the extraction rates of Q=1.8-1.9 times,temperature of 45-50。C,time of 60 min.initial pH value of 1.80-1.90 and transformation volume ratio =100%,the transformation rates of W and W and Mo decreased with the increase of initial pH value of aqueous solution.The minimum extraction rate of W was 2%,the maximum extraction rate of Mo was 82.6% and the hi【ghest separation coefficient was 76.7 in a single-stage extraction.The phase separation property in extraction was good 砀e aqueous solution and rafinate fMo were hilgher than 95%.the decomposition rate of HEO2 was lower than 1 5%and the Q value in the H,02-complex solution was higher than 1.6. There was large crystals of W and Mo not dissolved in the H202一complex transformation process because large crystals resulted in slow dissolution.These crystals were clear,transparent and stable.The results demonstrated that the precursor solution prepared by the evaporation deamination complex method could meet the requirements for separation of W and Mo bv H,0,一 were retumed to the evaporation deamination process after solid-liquid separation.and they were re.dissolved complexation『10,111. Table 2 Effects of transformation volume ratio叩on HzOz—complex transformation process at initial pH of 1.90 and temperature of 45。Cfor 60min 98 l27 16.8 21,2 96.5 97.3 99.2 1.9 77 163 14.0 1O.7 1.68 1.74 98.3 Wen-juan GUAN,et al/Trans.Nonferrous Met.Soc.China 23(2013)1 139—1 146 1 145 4 Conclusions 1、The qualified precursor solution for solvent separation of Mo and W by H202一complexation was prepared by the evaporation deamination complex method.This method has reduced acid consumption by more than 90%in comparison with the traditional directly acid regulation complex method.The high transformation rates of W and Mo and low decomposition rate of H2O2 have been ensured.The precursor solution was clear,transparent and stable,and by extracting with TRPO/TBP,a good separation effect of W and Mo has been obtained. 2 Most of the NH4HCO3 and(NH4)2C03 in the ammonium tungstate solution containing high content of Mo have been removed in the forlylS of NH3 and CO2 gases in the evaporation deamination process.pH value of the solution decreased from 9.22 tO 7.26 with the decrease of concentrated volume ratio from 1 00%to 1 7%.and then the crystallization rates of W and Mo were 84.41%and 32.01%,respectively. 31 Under optimum conditions of H202 dosage of p=1.8-1.9 times,temperature of 45—50。C,time of 60 min.initia1 pH of 1.80-1.90 and transfc)rmation volume ratio of ̄/=100%.the transformation rates of W and Mo were higher than 95%,the decomposition rate of H2O2 was lower than 15%and the Q value in the H,O2-complex solution was higher than 1.6.The practica1 utilization ratios of W and Mo in this method were close to 100%. 4、Separation of W and Mo from the precursor solution prepared by the evaporation deamination complex method has been carried out by using a mixture extractant of 2%fv/v)TRPO and 80%(v/v)TBR The minimum extraction rate of W was 2%.the maximum extraction rate of Mo was 82.6%and the highest separation coefifcient 0/w was 76.7 in a single—stage extraction at an oi1 to water ratio Of 2:1.temperature of 20。C and contact time of 5 min. Acknowledgement The authors want to thank Professor Qi—xiu ZHANG(School of Metallurgical Science and Engineering.Centra1 South University)for valuable discussions concerning this work.The authors also express sincere thanks to the China Molybdenum Co., Ltd.f0r financial support. 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Changsha:Central South University Press,2010:236—237.(in Chinese) 1146 Wen-juan GUAN,et al/Trans.Nonferrous Met.Soc.China 23(2013)1139—1146 蒸发脱氨络合法制备的 双氧水络合萃取分离钨钼前驱体料液 关文娟1,2张责清1,2高从增 , 1.中南大学冶金科学与工程学院,长沙410083; 2.中南大学稀有金属冶金与材料制各湖南省重点试验室,长沙410083 摘要:采用一种新方法制备双氧水络合萃取分离钨钼的前驱体料液。高钼钨酸铵溶液经蒸发脱氨和络合转化步 骤得到前驱体料液,然后用三烷基氧膦(TRPO) ̄I磷酸三丁酯(TBP)的混合萃取剂萃取分离钨和钼。结果表明:与 传统的“直接调酸络合法”相比,“蒸发脱氨络合法”能减少90%以上的耗酸量;在络合转化过程中控制H2O2 用量1.8-1.9倍、温度45~50。C、初始pH值1.80~1.90、时间60 min和络合转化体积比100%,W、Mo的转化率 高于95%,H2O2的分解率低于15%;萃取过程中w的单级萃取率最低为2%,Mo的单级萃取率最高为82.6%, 分离系数最高为76.7。 关键词:钨;钼:萃取分离;前驱体料液;H2O2 (Edited by Hua YANG) 

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