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A method of selective adsorption and recovery of gold from waste thiourea liquid with biomass-based adsorbent prepared from phyllostachys pubescens was proposed. The charcoal, after being activated in H2O-CO2 atmosphere, has more nanopores with smaller size on its surface, compared to being activated by CO2 alone, which greatly increases the specific surface area of the adsorbent material. Based on exploration of the effects of factors, including type of adsorbent material, pH value, adsorbent dosage, adsorption temperature, and adsorption time, on the adsorption of gold in waste thiourea liquid, the appropriate adsorption conditions were obtained as follows: pH of 6, adsorbent dosage of 8 g/L, adsorption temperature of 25 ℃, and adsorption time of 3.5 h. It is found that activation in H2O-CO2 can bring the activated carbon with better adsorption effect, and the removal rate of gold from waste thiourea liquid by adsorption can exceed 96%. The adsorption isothermal model is used to fit the process of gold adsorption from waste thiourea liquid by the carbon activated in H2O-CO2 atmosphere, and the results show that such gold adsorption process follows Freundlich model and is a physical adsorption process.

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提出一种以毛竹为原料制备生物质吸附剂、选择性地从硫脲废液中吸附回收金的方法。竹炭在H2O-CO2气氛中活化后表面的纳米孔洞比单独使用CO2活化的活性炭孔洞数量更多且尺寸更小,大大增加了吸附材料的比表面积。探究了吸附材料种类、pH值、吸附剂用量、吸附温度、吸附时间对硫脲废液中金吸附脱除的影响,得到适宜的吸附条件为:pH=6、吸附剂用量8 g/L、吸附温度25 ℃、时间3.5 h,其中采用H2O-CO2协同活化的活性炭吸附效果较好,可吸附脱除硫脲废液中96%以上的金。采用吸附等温模型拟合了H2O-CO2协同活化的活性炭在硫脲废液中吸附金的过程,结果表明,协同活化的活性炭吸附硫脲废液中金的过程更符合Freundlich模型,为物理吸附过程。

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姚丽(1987—),女,江西新余人,工程师,主要从事锂矿物加工及锂离子电池及材料方面的研究。E-mail:

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姚丽(1987—),女,江西新余人,工程师,主要从事锂矿物加工及锂离子电池及材料方面的研究。E-mail:

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(a)BC;(b)AC-1;(c)AC-2

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(a)Langmuir模型;(b)Freundlich模型

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AuCuFeMgZnNi
0.837 50.030 01.335 04.870 00.430 00.025 0
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硫脲废液主要化学成分(质量浓度)

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AuCuFeMgZnNi
0.837 50.030 01.335 04.870 00.430 00.025 0
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样品名称BET比表面积/(m2·g-1孔隙体积/(cm3·g-1平均孔径/nm
BC613.1450.2330.614
AC-1862.7430.4050.666
AC-21 489.6400.7930.723
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吸附材料的BET比表面积测定仪结果

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样品名称BET比表面积/(m2·g-1孔隙体积/(cm3·g-1平均孔径/nm
BC613.1450.2330.614
AC-1862.7430.4050.666
AC-21 489.6400.7930.723
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实验编号金属质量浓度/(mg·L-1
AuCuFeMgZnNi
132.0820.81986.434 093.72318.7622.39
234.4221.681 064.134 145.34328.4322.81
333.2521.541 002.854 137.07326.8922.75
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AC-2在适宜条件下的吸附验证实验结果

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实验编号金属质量浓度/(mg·L-1
AuCuFeMgZnNi
132.0820.81986.434 093.72318.7622.39
234.4221.681 064.134 145.34328.4322.81
333.2521.541 002.854 137.07326.8922.75
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T/℃Langmuir模型Freundlich模型
qmaxbR2nKR2
1539.2300.058 50.997 21.348 32.471 00.997 1
2526.0400.124 70.969 71.414 52.884 70.995 9
3518.8750.308 60.927 51.623 23.814 90.991 0
4518.8390.407 50.939 61.712 74.537 80.995 1
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模型拟合参数

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T/℃Langmuir模型Freundlich模型
qmaxbR2nKR2
1539.2300.058 50.997 21.348 32.471 00.997 1
2526.0400.124 70.969 71.414 52.884 70.995 9
3518.8750.308 60.927 51.623 23.814 90.991 0
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生物质吸附剂吸附回收硫脲废液中金的研究
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姚丽 1, 2 , 钟盛文 1, 2
矿冶工程杂志 | 冶金 2024,44(4): 223-228
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矿冶工程杂志 | 冶金 2024, 44(4): 223-228
生物质吸附剂吸附回收硫脲废液中金的研究
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姚丽1, 2 , 钟盛文1, 2
作者信息
  • 1.江西理工大学 材料冶金化学学部,江西 赣州 341000
  • 2.江西理工大学 江西省动力电池及材料重点实验室,江西 赣州 341000
  • 姚丽(1987—),女,江西新余人,工程师,主要从事锂矿物加工及锂离子电池及材料方面的研究。E-mail:

Adsorption and Recovery of Gold from Waste Thiourea Liquid by Biomass-Based Adsorbent
Li YAO1, 2 , Shengwen ZHONG1, 2
Affiliations
  • 1.Faculty of Materials, Metallurgy and Chemistry, Jiangxi University of Science and Technology, Ganzhou 341000, Jiangxi, China
  • 2.Jiangxi Key Laboratory of Power Batteries and Materials, Jiangxi University of Science and Technology, Ganzhou 341000, Jiangxi, China
出版时间: 2024-08-01 doi: 10.3969/j.issn.0253-6099.2024.04.043
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提出一种以毛竹为原料制备生物质吸附剂、选择性地从硫脲废液中吸附回收金的方法。竹炭在H2O-CO2气氛中活化后表面的纳米孔洞比单独使用CO2活化的活性炭孔洞数量更多且尺寸更小,大大增加了吸附材料的比表面积。探究了吸附材料种类、pH值、吸附剂用量、吸附温度、吸附时间对硫脲废液中金吸附脱除的影响,得到适宜的吸附条件为:pH=6、吸附剂用量8 g/L、吸附温度25 ℃、时间3.5 h,其中采用H2O-CO2协同活化的活性炭吸附效果较好,可吸附脱除硫脲废液中96%以上的金。采用吸附等温模型拟合了H2O-CO2协同活化的活性炭在硫脲废液中吸附金的过程,结果表明,协同活化的活性炭吸附硫脲废液中金的过程更符合Freundlich模型,为物理吸附过程。

吸附剂  /  金  /  竹炭  /  改性  /  活化  /  活性炭  /  硫脲废液  /  吸附模型

A method of selective adsorption and recovery of gold from waste thiourea liquid with biomass-based adsorbent prepared from phyllostachys pubescens was proposed. The charcoal, after being activated in H2O-CO2 atmosphere, has more nanopores with smaller size on its surface, compared to being activated by CO2 alone, which greatly increases the specific surface area of the adsorbent material. Based on exploration of the effects of factors, including type of adsorbent material, pH value, adsorbent dosage, adsorption temperature, and adsorption time, on the adsorption of gold in waste thiourea liquid, the appropriate adsorption conditions were obtained as follows: pH of 6, adsorbent dosage of 8 g/L, adsorption temperature of 25 ℃, and adsorption time of 3.5 h. It is found that activation in H2O-CO2 can bring the activated carbon with better adsorption effect, and the removal rate of gold from waste thiourea liquid by adsorption can exceed 96%. The adsorption isothermal model is used to fit the process of gold adsorption from waste thiourea liquid by the carbon activated in H2O-CO2 atmosphere, and the results show that such gold adsorption process follows Freundlich model and is a physical adsorption process.

adsorbent  /  gold  /  charcoal  /  modification  /  activation  /  activated carbon  /  waste thiourea liquid  /  adsorption model
姚丽, 钟盛文. 生物质吸附剂吸附回收硫脲废液中金的研究. 矿冶工程杂志, 2024 , 44 (4) : 223 -228 . DOI: 10.3969/j.issn.0253-6099.2024.04.043
Li YAO, Shengwen ZHONG. Adsorption and Recovery of Gold from Waste Thiourea Liquid by Biomass-Based Adsorbent[J]. Mining and Metallurgical Engineering, 2024 , 44 (4) : 223 -228 . DOI: 10.3969/j.issn.0253-6099.2024.04.043
1941年首次发现金可以溶解于硫脲溶液中。硫脲对环境无害、对人体无毒,且金在硫脲溶液中的溶解速度比金在氰化物溶液中的溶解速度快,因此硫脲浸金工艺在世界范围内得到了广泛应用[1]。随之而来的是每年产生大量含金硫脲废液[2]。含金硫脲废液的积累不仅会造成重金属污染,还会造成贵金属浪费[3-4]。因此,从硫脲废液中回收金不仅具备重要的经济意义,还能对环境产生积极影响。
目前,从硫脲废液中回收金的主要方法是铝粉置换沉淀法和离子交换树脂法[5]。铝粉置换沉淀法从硫脲废液中回收金的回收率可达98%,但置换产物中的贵金属含量很低(金质量分数仅2%),后续的分离提纯十分困难[6]。离子交换树脂法可在含有砷、铜和锑的溶液中选择性吸附金硫脲络合物,但在吸附过程中也会吸附大量铁,且吸附完成后很难从离子交换树脂中洗脱分离金[7]。为了快速高效地从硫脲废液中提金,采用内部孔隙结构发达、比表面积大、吸附能力强的活性炭(AC)吸附废液中金已成为近几年的研究热点[8]。本文提出一种以毛竹为原料制备生物质吸附剂并选择性地从硫脲废液中提取金的方法。
实验所用毛竹来自湖南省沅陵县,硫脲废液由中南大学某课题组提供。采用电感耦合等离子体发射光谱仪(ICP-OES,ThermoFisher Scientific iCAP 7200)测定废液主要化学成分,结果见表1
毛竹经粉碎后使用10~20目(0.85~2.00 mm)筛子筛分。将筛分后的样品置于80 ℃去离子水中搅拌2 h,完成样品除尘。完成除尘后,将样品烘干,并在管式炉内700 ℃碳化处理8 h,制备得到竹炭(BC)。活性炭样品1(AC-1)由BC在CO2流量1 L/min条件下850 ℃活化1.5 h制成;活性炭样品2(AC-2)由BC在H2O-CO2流量1 L/min条件下850 ℃活化1.5 h制成。每组实验重复3次后,均匀采样检测。
在装有机械搅拌器的500 mL玻璃烧杯中,在恒温水浴锅下进行吸附试验。浸出前,为调节硫脲废液的pH值,制备了硅酸钠和氢氧化钠溶液。将约100 mL硫脲废液倒入烧杯中,搅拌速度300 r/min,加热到设定温度时,在烧杯中加入一定量吸附材料,吸附后的吸附材料经过滤从废液中离心分离出来。最后,对滤液称量并使用电感耦合等离子体光谱仪(ICP)检测滤液中金含量。吸附剂的吸金效果由去除率来衡量:
式中:ε为去除率,%;ρ吸附前ρ吸附后分别为吸附前和吸附后硫脲废液中金质量浓度,mg/L。
条件实验每组重复3次,以计算误差棒。考虑到溶液pH值对金属离子形态、吸附过程以及吸附剂表面活性基团的影响,首先研究了pH值对吸附过程的影响,通过NaOH和Na2SiO3溶液将硫脲废液pH值分别调整为2、3、4、5、6;吸附剂用量分别设定为2、4、6、8、10、12 g/L;采用恒温水浴对硫脲废液加热,温度分别设置为15、25、35、45、55 ℃;吸附时间分别设置为0.5、1.0、1.5、2.0、2.5、3.0、3.5、4.0 h。
采用ICP(IRIS Intrepid II XSP)分析实验样品化学成分,采用扫描电镜(JEOL,JSM-6490LV)表征吸附剂形貌;采用V-Sorb 2800TP比表面积分析仪测定BET比表面积和孔径分布;采用傅里叶变换红外光谱仪(FTIR-650)表征吸附剂表面官能团;采用Thermo Escalab 250Xi X射线光电子能谱仪分析表面结合和元素形态。
图1为3种吸附剂的SEM图。由图1可知,BC内部为蜂窝状细胞结构,沿细胞壁呈六边形分布,且这些蜂窝状孔洞的内部结构具有一定深度。活化修饰后细胞中六边形蜂窝状结构消失,AC-1比BC具有更大的比表面积和孔隙率,这是由于活化修饰后细胞壁除了微孔还出现了纳米孔;AC-2具有毛细管内结构,这是半纤维素和可溶性糖在BC中溶解所致。H2O-CO2活化改性可使BC内部结构疏松分散,进一步增大材料内部孔隙。H2O-CO2气氛活化的样品(AC-2)细胞壁表面粗糙度增加,出现了大量纳米孔。
测试了3种吸附剂的BET比表面积、孔隙体积及平均孔径,结果见表2。由表2可知,AC-2样品BET比表面积、孔隙体积和平均孔径均最大,BC样品BET比表面积、总孔容和平均孔径均最小。BET比表面积和总孔隙体积结果验证了SEM分析结果。
3种样品的孔径分布曲线如图2所示。由图2可见,AC-2孔径分布较集中,大部分为2 nm以下的微孔。这些微孔具有较强的吸附潜力,在较低的压力范围内,样品可迅速接近吸附饱和。AC-2具有较大的表面积和孔容积,并且具有大量的微孔,因此AC-2可以提供更多的吸附和反应位点来提高催化活性。
3种样品的氮气吸附等温线如图3所示。3种样品的氮气吸附-解吸等温线均为IV型分支,滞回线为H4,为典型的介孔结构特征[9-11]。由此可以看出,混合气体协同活化可以产生吸附能力增强的活性炭。
SEM和BET结果表明,BC可以被活化和改性,使得其比表面积增大,吸附性能也会增加。此外,在H2O-CO2气氛中协同活化制得的AC-2比在CO2气氛中活化制得的AC-1具有更发达的孔隙结构和更高的比表面积。因此,采用混合气体活化的活性炭拥有更大的比表面积和更多的孔容积,吸附能力更强[12]
3种样品的红外光谱见图4。从图4可以看出,3种样品各官能团的特征吸收峰位置均发生了明显变化,强度也有所不同。3种吸附剂均有吸附峰在1 000~1 300 cm-1范围内,属于C—O拉伸振动[13]。AC-1和AC-2有吸收峰在1 400~1 600 cm-1范围内,属于拉伸振动,在2 700~3 000 cm-1范围内的吸收峰则由碳氢化合物的拉伸振动引起[14]。AC-2在1 697.63 cm-1处的吸收峰属于典型的COOH不对称拉伸振动峰,表明部分碳原子被氧化成羧基[15]。BC和AC-2在3 200~3 650 cm-1范围内的吸收峰属于O—H基团伸缩振动。BC在H2O-CO2中活化后,部分碳原子被氧化成羧基,AC-2表面含氧官能团增多,活性炭吸附空间加大,使得AC-2吸附能力更强。
在硫脲浸出中,金与硫脲形成强阳离子络合物:
考虑到pH>7时金属水解对吸附结果影响较大,本文研究的pH值范围为2~6。吸附剂用量10 g/L、温度35 ℃、吸附时间4 h条件下,pH值对吸附过程的影响如图5所示。从图5可以看出,同样的pH值条件下,AC-2的金去除率最大,BC的金去除率最小。随着pH值从2增加到5,BC对溶液中金的吸附去除率由20.14%显著提高到78.92%,AC-1和AC-2的金吸附去除率则增长缓慢。此后随着pH值进一步升高,BC的金去除率没有明显变化,表明此时BC对硫脲废液中金的吸附达到饱和,而AC-1和AC-2的金去除率仍在增加。总的来说,3种样品对溶液中金去除率均随着pH值增加而增加。适宜的pH值为6。
pH=6,其他条件不变,吸附剂用量对溶液中金去除率的影响如图6所示。从图6可以看出,吸附剂用量对硫脲废液中金的提取有显著影响。随着吸附剂用量从2 g/L增加到8 g/L,3种样品的金去除率均增加;吸附剂用量超过8 g/L后,AC-2的金去除率几乎不再随着吸附剂用量增加而改变,但AC-1和BC的金去除率仍呈上升趋势。SEM和BET分析结果表明,AC-2表面有大量纳米孔,比AC-1和BC比表面积更大。因此,在相同用量条件下,AC-2的金去除率更高。适宜的吸附剂用量为8 g/L。
吸附剂用量8 g/L,其他条件不变,吸附温度对吸附过程的影响见图7。从图7可以看出,虽然3种吸附剂的金去除率均随着吸附温度升高略有提高,但增幅不明显,说明与其他因素相比,吸附温度对吸附效果的影响较小。生物炭对硫脲废液中金的吸附主要涉及物理吸附。考虑能量消耗,吸附温度选择25 ℃。
吸附温度25 ℃,其他条件不变,吸附时间对吸附过程的影响如图8所示。从图8可以看出,吸附时间0.5~1.0 h内,3种样品的金去除率均随着吸附时间增加而快速上升,吸附时间1.0 h时,AC-2、AC-1和BC的金去除率分别达到67.24%、46.85%和35.42%;之后再延长吸附时间,3种样品的金去除率均缓慢上升,吸附时间3.5 h时,AC-2和AC-1的金去除率达到最大值,分别为96.98%和90.87%。进一步延长时间,金去除率不再改变,表明硫脲废液中金的吸附达到饱和。适宜的吸附时间为3.5 h。
选择AC-2作为硫脲废液中金的吸附剂,适宜的硫脲废液中回收金的吸附条件为:pH=6、吸附剂用量8 g/L、吸附温度25 ℃、吸附时间3.5 h。在此条件下,硫脲废液经吸附后可脱除96%以上的金。在适宜条件下进行了3次验证实验,结果见表3。由表3可知,3次验证实验结果一致。Na2SiO3的加入可以在很大程度上提高金的溶解电流密度,使得硫脲溶液对金的溶解具有选择性,溶液中96%以上的金可被优先吸附。
图9为活性炭吸附示意图。活性炭表面有发达的孔隙结构,增加了其与气体或化学物质的接触。当化学物质或气体被吸收到活性炭内孔时,由于分子间的相互吸引,会不断吸引更多的分子,直到活性炭的孔被填满。微孔是活性炭大比表面积和高吸附能力的来源。活性炭上的微孔可以提供更多的吸附和反应位点,提高催化活性。
采用XPS研究了在适宜条件下硫脲废液中AC-2吸附金后表面化学物质的变化,结果如图10所示。可以看出,AC-2吸附硫脲废液中的金后,在85.97 eV处检测到一个明显的Au4f峰,其中AC-2在85.09 eV和88.89 eV处分别有Au4f5/2和Au4f7/2两个明显的峰。这一结果表明,硫脲废液中的金可以吸附在AC-2表面,Au在溶液中的价态为+1价。
吸附等温线一般用来描述在一定温度下平衡吸附量与平衡温度的关系,可用来判断吸附材料与被吸附物相互作用的机理。为了进一步研究吸附热力学,分别在不同温度和不同金质量浓度下进行了一系列吸附等温实验。重金属离子在吸附剂表面的吸附行为通常可以用Langmuir和Freundlich等温线[16]来描述:
Langmuir模型:
Freundlich模型:
式中:q为吸附容量,mg/g;c0c分别为吸附前和吸附后硫脲废液中金的质量浓度,mg/L;V为硫脲废液体积,L;qmax为饱和吸附容量,mg/g;bKn均为与吸附有关的常数和经验参数。
使用两种模型拟合吸附容量与溶液平衡浓度的关系,结果如图11所示,各模型拟合参数如表4所示。
图11表4可以看出,Freundlich模型在拟合AC-2吸附硫脲废液中金时优于Langmuir模型。不同温度下,Freundlich模型的lgq与lgc呈较好的线性关系,表明硫脲废液中金的吸附符合Freundlich模型,为物理吸附[17]
1)使用H2O-CO2和CO2分别对毛竹进行改性及活化,获得竹基活性炭,作为吸附硫脲废液中金的吸附材料。SEM、BET和FTIR检测结果表明,使用H2O-CO2协同活化的活性炭吸附材料有更多的纳米孔洞,比表面积比CO2单独活化的活性炭吸附材料比表面积大大增加。此外,在活化过程中,H2O-CO2协同活化的吸附材料中一部分碳原子被氧化成羧基,其表面的含氧基团大量增加,活性炭分子结构增大,吸附空间更大。这使得经H2O-CO2协同活化得到的吸附材料吸附能力强于单独在CO2气氛中活化得到的吸附材料。
2)采用生物炭从硫脲废液中吸附提金,适宜的吸附条件为:pH=6、吸附剂用量8 g/L、吸附温度25 ℃、吸附时间3.5 h。在相同条件下,AC-2吸附效果较好,可吸附脱除废液中96%以上的金。
3)采用Freundlich和Langmuir等温模型拟合了AC-2在硫脲废液中吸附金的过程,结果表明,AC-2吸附硫脲废液中的金更符合Freundlich模型,吸附过程为物理吸附。
  • 江西省重大科技研发专项“揭榜挂帅”项目(20213AAE02010)
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doi: 10.3969/j.issn.0253-6099.2024.04.043
  • 接收时间:2024-03-03
  • 首发时间:2026-03-18
  • 出版时间:2024-08-01
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  • 收稿日期:2024-03-03
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江西省重大科技研发专项“揭榜挂帅”项目(20213AAE02010)
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    1.江西理工大学 材料冶金化学学部,江西 赣州 341000
    2.江西理工大学 江西省动力电池及材料重点实验室,江西 赣州 341000
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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