Article(id=1171165155967680587, tenantId=1146029695717560320, journalId=1146123346816638986, issueId=1171165154017321083, articleNumber=1000-8063(2025)03-0068-08, orderNo=null, doi=10.13426/j.cnki.yky.2025.02.04, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1740067200000, receivedDateStr=2025-02-21, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1757157132379, onlineDateStr=2025-09-06, pubDate=1757433600000, pubDateStr=2025-09-10, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1757157132379, onlineIssueDateStr=2025-09-06, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1757157132379, creator=13701087609, updateTime=1757157132379, updator=13701087609, issue=Issue{id=1171165154017321083, tenantId=1146029695717560320, journalId=1146123346816638986, year='2025', volume='44', issue='3', pageStart='1', pageEnd='154', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=1, specialIssue=null, createTime=1757157131914, creator=13701087609, updateTime=1757582122913, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1172947695539994987, tenantId=1146029695717560320, journalId=1146123346816638986, issueId=1171165154017321083, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1172947695539994988, tenantId=1146029695717560320, journalId=1146123346816638986, issueId=1171165154017321083, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=68, endPage=75, ext={EN=ArticleExt(id=1171165156156424269, articleId=1171165155967680587, tenantId=1146029695717560320, journalId=1146123346816638986, language=EN, title=Effect of CO2 in Air on U Stability during the Neutralization Process of Acidic Waste Residue, columnId=null, journalTitle=Uranium Mining and Metallurgy, columnName=null, runingTitle=null, highlight=null, articleAbstract=

Alkaline materials were used to neutralize acidic waste residue. Open and closed experimental environments were set up with different dosing ratios and pH conditions.By monitoring the changes in pH, U, and $\mathrm{HCO}_{3}^{-}$ in the supernatant of the neutralization residue, and analyzing the mineral composition of the neutralization residue using XRD, the effect of CO2 on U stability during the neutralization process of acidic waste residue was studied. The results show that CO2 in the surrounding air during neutralization treatment affects the stability of pH and U in the neutralization residue. The fixation of CO2 by the neutralization residue under alkaline conditions is an acidification process. As the pH of the neutralization residue decreases, the CO2 fixed in the air transforms into $\mathrm{HCO}_{3}^{-}$, which gradually accumulates and causes the already stabilized U in the neutralization residue is leached out again. The pH adjustment experiment shows that there is no significant correlation between U and pH. The pH range for U leaching is 7.68~8.41, and $\mathrm{HCO}_{3}^{-}$ accumulates significantly in this range. There is a positive correlation between U and $\mathrm{HCO}_{3}^{-}$, with a correlation coefficient of 0.95. The production of $\mathrm{HCO}_{3}^{-}$ is a key factor affecting the stability of U in neutralization residue. When Ca(OH)2 is added excessively, secondary mineral CaCO3 will be generated in the neutralization residue. As CO2 is fixed, the pH of the neutralization residue decreases, and CaCO3 will partially dissolve and transform into $\mathrm{HCO}_{3}^{-}$. In the open experimental environment, only the 2.5% Ca(OH)2 experimental group and the 2.5% Mg(OH)2 experimental group maintain extremely low U leaching levels. After neutralization treatment, the pH of the neutralization residue is low, and very little CO2 is fixed in the air. $\mathrm{HCO}_{3}^{-}$ which affects U stabilityis hardly produced.

, correspAuthors=null, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, authorCompany=null, fund=null, authors=null, authorsList=Yang GAO, Juan SUN, Xiaochao LIU, Yifu AN, Xuyang WU, Lijiang REN), CN=ArticleExt(id=1171165343805391353, articleId=1171165155967680587, tenantId=1146029695717560320, journalId=1146123346816638986, language=CN, title=空气中CO2对酸性废渣中和过程中U稳定性的影响, columnId=1171165154847793280, journalTitle=铀矿冶, columnName=开采·选治, runingTitle=null, highlight=null, articleAbstract=采用碱性材料对酸性废渣进行中和处理,设置敞开、封闭试验环境,以及不同投加比和pH等条件,通过监测中和渣上清液中pH、U、$\mathrm{HCO}_{3}^{-}$变化,并借助XRD分析中和渣的矿物组成,研究CO2对酸性废渣中和过程中U稳定性的影响。结果表明,中和处理时周围空气中的CO2会影响中和渣pH与U的稳定性,中和渣在碱性条件下对CO2的固定是个酸化过程,随着中和渣pH下降,在空气中固定的CO2$\mathrm{HCO}_{3}^{-}$转变,$\mathrm{HCO}_{3}^{-}$逐渐累积,使中和渣中已稳定的U重新浸出。U与pH无明显相关性,U大量浸出的pH区间为7.68~8.41,此区间$\mathrm{HCO}_{3}^{-}$大量积累;U与$\mathrm{HCO}_{3}^{-}$成正相关关系,相关系数(R2)为0.95,$\mathrm{HCO}_{3}^{-}$的产生是影响中和渣中U稳定性的关键因素。Ca(OH)2投加过量时,中和渣中会有次生矿物CaCO3生成;随着CO2固定,中和渣pH下降,CaCO3会部分溶解转变为$\mathrm{HCO}_{3}^{-}$。敞开试验环境中,仅有2.5%Ca(OH)2试验组和2.5%Mg(OH)2试验组维持极低的U浸出水平,中和处理后中和渣pH较低,在空气中固定的CO2极少,影响U稳定的$\mathrm{HCO}_{3}^{-}$基本不产生。, correspAuthors=null, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=n+jBpSuiKWBvNpy4YXORHQ==, magXml=CeRz1raYDoaARHSWw/sgHw==, pdfUrl=null, pdf=pLerA04Q8JFfeFvlhJvyVA==, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=IlywMWN98BVxEguNwdynLQ==, mapNumber=null, authorCompany=null, fund=null, authors=

高扬(1991—),男,河北保定人,硕士,工程师,主要从事辐射防护与环境保护相关研究。

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高扬(1991—),男,河北保定人,硕士,工程师,主要从事辐射防护与环境保护相关研究。

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高扬(1991—),男,河北保定人,硕士,工程师,主要从事辐射防护与环境保护相关研究。

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Summary of experimental condition

, figureFileSmall=null, figureFileBig=null, tableContent=
组别 废渣属性 废渣量/g 试验环境 材料 投加比
1# 原废渣 50.0 敞开 Ca(OH)2 2.5%、5.0%、7.5%、10.0%
原废渣 50.0 封闭 Ca(OH)2 2.5%、5.0%、7.5%、10.0%
2# 2.5% Ca(OH)2中和后的废渣 50.0 敞开 Ca(OH)2 1.5%、3.0%、4.5%、6.0%、7.5%
10.0% Ca(OH)2中和后的废渣 50.0 敞开 CaCl2 1.5%、3.0%、4.5%、6.0%、7.5%
3# 原废渣 50.0 敞开 Mg(OH)2 2.5%、5.0%、7.5%、10.0%
), ArticleFig(id=1171209168686989802, tenantId=1146029695717560320, journalId=1146123346816638986, articleId=1171165155967680587, language=CN, label=表1, caption=

试验条件汇总

, figureFileSmall=null, figureFileBig=null, tableContent=
组别 废渣属性 废渣量/g 试验环境 材料 投加比
1# 原废渣 50.0 敞开 Ca(OH)2 2.5%、5.0%、7.5%、10.0%
原废渣 50.0 封闭 Ca(OH)2 2.5%、5.0%、7.5%、10.0%
2# 2.5% Ca(OH)2中和后的废渣 50.0 敞开 Ca(OH)2 1.5%、3.0%、4.5%、6.0%、7.5%
10.0% Ca(OH)2中和后的废渣 50.0 敞开 CaCl2 1.5%、3.0%、4.5%、6.0%、7.5%
3# 原废渣 50.0 敞开 Mg(OH)2 2.5%、5.0%、7.5%、10.0%
), ArticleFig(id=1171209168754098667, tenantId=1146029695717560320, journalId=1146123346816638986, articleId=1171165155967680587, language=EN, label=Table 2, caption=

ρ(U), ρ($\mathrm{HCO}_{3}^{-}$), and pH in the supernatant

, figureFileSmall=null, figureFileBig=null, tableContent=
2.5%Ca(OH)2试验组中和渣 10.0%Ca(OH)2试验组中和渣
Ca(OH)2投加比/% pH ρ(U)/(mg/L) ρ($\mathrm{HCO}_{3}^{-}$)/(g/L) CaCl2投加比/% pH ρ(U)/(mg/L) ρ($\mathrm{HCO}_{3}^{-}$)/(g/L)
0 6.34 0.06 0.12 0 8.62 0.04 0.21
1.5 7.63 0.02 0.11 1.5 8.13 1.26 2.14
3.0 8.02 1.89 2.38 3.0 7.68 0.98 1.78
4.5 8.18 0.54 0.67 4.5 7.14 0.23 0.45
6.0 8.41 0.30 0.33 6.0 6.94 0.03 0.03
7.5 9.15 0.21 0.20 7.5 6.53 0.07 0.03
), ArticleFig(id=1171209168821207532, tenantId=1146029695717560320, journalId=1146123346816638986, articleId=1171165155967680587, language=CN, label=表2, caption=

上清液中ρ(U)、ρ($\mathrm{HCO}_{3}^{-}$)及Ph

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2.5%Ca(OH)2试验组中和渣 10.0%Ca(OH)2试验组中和渣
Ca(OH)2投加比/% pH ρ(U)/(mg/L) ρ($\mathrm{HCO}_{3}^{-}$)/(g/L) CaCl2投加比/% pH ρ(U)/(mg/L) ρ($\mathrm{HCO}_{3}^{-}$)/(g/L)
0 6.34 0.06 0.12 0 8.62 0.04 0.21
1.5 7.63 0.02 0.11 1.5 8.13 1.26 2.14
3.0 8.02 1.89 2.38 3.0 7.68 0.98 1.78
4.5 8.18 0.54 0.67 4.5 7.14 0.23 0.45
6.0 8.41 0.30 0.33 6.0 6.94 0.03 0.03
7.5 9.15 0.21 0.20 7.5 6.53 0.07 0.03
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空气中CO2对酸性废渣中和过程中U稳定性的影响
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高扬 , 孙娟 , 刘晓超 , 安毅夫 , 武旭阳 , 任丽江
铀矿冶 | 开采·选治 2025,44(3): 68-75
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铀矿冶 | 开采·选治 2025, 44(3): 68-75
空气中CO2对酸性废渣中和过程中U稳定性的影响
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高扬, 孙娟, 刘晓超, 安毅夫, 武旭阳, 任丽江
作者信息
  • 中核第四研究设计工程有限公司,河北 石家庄 050021
  • 高扬(1991—),男,河北保定人,硕士,工程师,主要从事辐射防护与环境保护相关研究。

Effect of CO2 in Air on U Stability during the Neutralization Process of Acidic Waste Residue
Yang GAO, Juan SUN, Xiaochao LIU, Yifu AN, Xuyang WU, Lijiang REN
Affiliations
  • The Fourth Research and Design Engineering Corporation, CNNC, Shijiazhuang 050021, China
出版时间: 2025-09-10 doi: 10.13426/j.cnki.yky.2025.02.04
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采用碱性材料对酸性废渣进行中和处理,设置敞开、封闭试验环境,以及不同投加比和pH等条件,通过监测中和渣上清液中pH、U、$\mathrm{HCO}_{3}^{-}$变化,并借助XRD分析中和渣的矿物组成,研究CO2对酸性废渣中和过程中U稳定性的影响。结果表明,中和处理时周围空气中的CO2会影响中和渣pH与U的稳定性,中和渣在碱性条件下对CO2的固定是个酸化过程,随着中和渣pH下降,在空气中固定的CO2$\mathrm{HCO}_{3}^{-}$转变,$\mathrm{HCO}_{3}^{-}$逐渐累积,使中和渣中已稳定的U重新浸出。U与pH无明显相关性,U大量浸出的pH区间为7.68~8.41,此区间$\mathrm{HCO}_{3}^{-}$大量积累;U与$\mathrm{HCO}_{3}^{-}$成正相关关系,相关系数(R2)为0.95,$\mathrm{HCO}_{3}^{-}$的产生是影响中和渣中U稳定性的关键因素。Ca(OH)2投加过量时,中和渣中会有次生矿物CaCO3生成;随着CO2固定,中和渣pH下降,CaCO3会部分溶解转变为$\mathrm{HCO}_{3}^{-}$。敞开试验环境中,仅有2.5%Ca(OH)2试验组和2.5%Mg(OH)2试验组维持极低的U浸出水平,中和处理后中和渣pH较低,在空气中固定的CO2极少,影响U稳定的$\mathrm{HCO}_{3}^{-}$基本不产生。
CO2  /  $\mathrm{HCO}_{3}^{-}$  /  酸性废渣  /  中和  /  U稳定性

Alkaline materials were used to neutralize acidic waste residue. Open and closed experimental environments were set up with different dosing ratios and pH conditions.By monitoring the changes in pH, U, and $\mathrm{HCO}_{3}^{-}$ in the supernatant of the neutralization residue, and analyzing the mineral composition of the neutralization residue using XRD, the effect of CO2 on U stability during the neutralization process of acidic waste residue was studied. The results show that CO2 in the surrounding air during neutralization treatment affects the stability of pH and U in the neutralization residue. The fixation of CO2 by the neutralization residue under alkaline conditions is an acidification process. As the pH of the neutralization residue decreases, the CO2 fixed in the air transforms into $\mathrm{HCO}_{3}^{-}$, which gradually accumulates and causes the already stabilized U in the neutralization residue is leached out again. The pH adjustment experiment shows that there is no significant correlation between U and pH. The pH range for U leaching is 7.68~8.41, and $\mathrm{HCO}_{3}^{-}$ accumulates significantly in this range. There is a positive correlation between U and $\mathrm{HCO}_{3}^{-}$, with a correlation coefficient of 0.95. The production of $\mathrm{HCO}_{3}^{-}$ is a key factor affecting the stability of U in neutralization residue. When Ca(OH)2 is added excessively, secondary mineral CaCO3 will be generated in the neutralization residue. As CO2 is fixed, the pH of the neutralization residue decreases, and CaCO3 will partially dissolve and transform into $\mathrm{HCO}_{3}^{-}$. In the open experimental environment, only the 2.5% Ca(OH)2 experimental group and the 2.5% Mg(OH)2 experimental group maintain extremely low U leaching levels. After neutralization treatment, the pH of the neutralization residue is low, and very little CO2 is fixed in the air. $\mathrm{HCO}_{3}^{-}$ which affects U stabilityis hardly produced.

CO2  /  $\mathrm{HCO}_{3}^{-}$  /  acidic waste residue  /  neutralization  /  U stability
高扬, 孙娟, 刘晓超, 安毅夫, 武旭阳, 任丽江. 空气中CO2对酸性废渣中和过程中U稳定性的影响. 铀矿冶, 2025 , 44 (3) : 68 -75 . DOI: 10.13426/j.cnki.yky.2025.02.04
Yang GAO, Juan SUN, Xiaochao LIU, Yifu AN, Xuyang WU, Lijiang REN. Effect of CO2 in Air on U Stability during the Neutralization Process of Acidic Waste Residue[J]. Uranium Mining and Metallurgy, 2025 , 44 (3) : 68 -75 . DOI: 10.13426/j.cnki.yky.2025.02.04
铀矿及伴生放射性矿经过酸法采冶后,会产生大量含铀酸性废渣(pH=1.5~3.0)[1-2],对其安全处置前须先进行中和处理[3-4]。中和过程不仅能调节废渣酸度,还可促进铀的稳定化。
石灰是酸性废渣常用的碱性中和材料,但经石灰处理的铀矿冶废渣堆存几十年后,陆续出现U反溶问题[5]。U反溶过程受多种因素共同影响:1)化学因素。主要包括废渣中和不完全导致的残余酸释放[6]以及黄铁矿氧化等产酸矿物的氧化产酸作用[7]。2)环境因素。在中碱性条件下废渣中U仍存在一定的浸出风险[8],表明pH不是控制U稳定性的唯一因素。3)微生物因素。好氧型微生物氧化可促进U反溶[9-10],还原性微生物可对U进行原位固定[11-13]
目前,针对U稳定性的研究多集中在酸性废渣中和后铀的形态以及铀的价态等方面[14-16],没有考虑中和处理过程中空气中CO2对U稳定性的影响。笔者通过选择不同投加比的碱性材料对酸性废渣进行中和处理,研究在不同pH条件下,空气中CO2对中和渣中U稳定性的影响,以期为含U酸性废渣的安全处置提供技术支持。
试验用酸性废渣为伴生U的独居石酸溶渣,将酸溶渣自然风干、除杂、混匀、磨碎后过10目(2 mm)尼龙筛备用。酸溶渣pH为1.9,U质量分数为0.10%。碱性材料Ca(OH)2和Mg(OH)2,辅助材料CaCl2,均为分析纯;试验用水为去离子水,电导率≤10-6 S/cm。
酸性废渣的中和处理采用静态试验方式进行,将酸性废渣与碱性材料在搅拌器(300 r/min)中固固混匀10 min后,添加去离子水在搅拌器(100 r/min)中继续混匀5 min,最终控制液固体积质量比(简称液固比)为1∶1(mL/g),得到中和渣混合溶液。
设置敞开、封闭2种试验环境。封闭环境采用橡胶塞和铝塑盖隔绝空气,Ca(OH)2投加比分别为2.5%、5.0%、7.5%、10.0%,在整个试验周期内定期监测中和渣上清液中的pH与ρ(U)、ρ($\mathrm{HCO}_{3}^{-}$)变化;试验结束后进行固液分离将固体样品进行干燥处理,测试矿物组成。选择敞开环境中Ca(OH)2投加比为2.5%和10.0%的中和处理后的中和渣固体样品进行pH调节,pH调节材料为Ca(OH)2和CaCl2,材料投加比分别为1.5%、3.0%、4.5%、6.0%、7.5%,液固比为1∶1(mL/g),120 d后测试上清液中pH、ρ(U)、ρ($\mathrm{HCO}_{3}^{-}$)。此外,在敞开环境下进行酸性废渣与Mg(OH)2的中和试验,Mg(OH)2投加比同样设置为2.5%、5.0%、7.5%、10.0%,定期监测上清液中的pH与ρ(U)、ρ($\mathrm{HCO}_{3}^{-}$)变化。为减少长期试验水分流失,试验置于恒温恒湿箱(温度25 ℃,相对湿度96%)中进行。试验设计见表1
中和渣上清液pH采用酸度计(ST3100/F,OHAUS,USA)测定;ρ(U)采用电感耦合等离子体发射光谱仪(iCAP 7200,Thermo Fisher Scientific,USA)测定;ρ($\mathrm{HCO}_{3}^{-}$)采用酸碱滴定法测定;中和渣矿物组成采用XRD(Smartlab3,Rigaku,Japan)测试分析。
采用Microsoft Excel 2016进行数据统计分析,采用Jade 6.5进行XRD图谱解析,采用Origin Pro 9.0进行绘图。
在敞开与封闭试验环境条件下,Ca(OH)2投加量对中和渣上清液pH与ρ(U)影响见图1。可以看出,在敞开体系中,投加Ca(OH)2后,中和渣上清液的pH随着时间推移存在明显下降趋势,其中2.5%试验组在40 d内先下降后升高,40 d后又缓慢下降至6.0左右;ρ(U)在整个试验周期内一直维持在较低水平。5.0%试验组的pH在40 d内下降趋势最为明显,从11.17快速下降至8.91,40 d后又缓慢下降至8.0左右;而且U在40 d后快速浸出,试验结束时上清液中ρ(U)为1.18 mg/L,仍未达到平衡状态。7.5%试验组的pH在20 d内下降较快,20 d后缓慢下降至9.43;ρ(U)在120 d内一直维持在较低水平,120 d后U开始浸出,试验结束时ρ(U)从0.08 mg/L升至0.31 mg/L。10.0%试验组的pH在整个试验周期内缓慢下降至10.32,ρ(U)始终维持在极低水平。与敞开体系相比,封闭体系的中和渣上清液pH随时间推移下降趋势更为平缓,最终pH更高,各试验组ρ(U)始终处于极低水平。因此认为,在中和处理时周围空气会影响中和渣上清液的pH与ρ(U)变化。
从中和处理后中和渣的XRD谱图(图2)可以看出,除2.5%试验组外,敞开体系中和渣的矿物组成包括ZrSiO4、SiO2、Al2Ca3(SiO4)3、CaCO3、Mg3Al2(SiO4)3等,未有U矿物相衍射峰出露,其中硅酸盐矿物均为酸性废渣的原生矿物;敞开体系2.5%试验组和封闭体系所有试验组中和渣的XRD谱图未见CaCO3衍射峰,这与文献[17-18]的结果一致。CaCO3为次生矿物,来源于中和渣中多余的碱对空气中CO2的固定,其过程见反应式(1)~式(2),中和渣中多余的碱消耗H+会促进反应(1)和(2)的发生。图2(a)显示,Ca(OH)2投加比越大,CaCO3衍射峰的峰强越强;这是由于材料碱性越强消耗H+能力越强,通过溶解CO2生成的$\mathrm{CO}_{3}^{2-}$越多,生成的次生矿物CaCO3也越多。
$\mathrm{CO}_{2}+\mathrm{H}_{2} \mathrm{O} \longrightarrow \mathrm{H}_{2} \mathrm{CO}_{3}=2 \mathrm{H}^{+}+\mathrm{CO}_{3}^{2-},$
$\mathrm{Ca}^{2+}+\mathrm{CO}_{3}^{2-} \longrightarrow \mathrm{CaCO}_{3} \text { 。 }$
封闭体系上清液中未检测到$\mathrm{HCO}_{3}^{-}$,敞开体系中ρ($\mathrm{HCO}_{3}^{-}$)变化见图3。可以看出,2.5%Ca(OH)2和10.0%Ca(OH)2试验组在整个试验周期内ρ($\mathrm{HCO}_{3}^{-}$)均处于极低水平;5.0%Ca(OH)2试验组在20 d后$\mathrm{HCO}_{3}^{-}$快速浸出,至120 d时浸出速率变慢,逐渐达到平衡状态,试验结束时上清液中ρ($\mathrm{HCO}_{3}^{-}$)为2.66 g/L;7.5%Ca(OH)2试验组在150 d后才开始浸出,试验结束时仍维持上升趋势,ρ($\mathrm{HCO}_{3}^{-}$)为0.72 g/L。5.0%Ca(OH)2和7.5%Ca(OH)2试验组中$\mathrm{HCO}_{3}^{-}$浸出主要与中和渣pH下降相关,pH下降时中和渣对空气中CO2的固定过程见反应式(3),中和渣pH下降导致消耗H+能力降低,CO2$\mathrm{HCO}_{3}^{-}$转变,而且已经生成的次生矿物CaCO3也会随着pH下降而部分溶解,见反应式(4)。在5.0%Ca(OH)2和7.5%Ca(OH)2试验组中,ρ($\mathrm{HCO}_{3}^{-}$)变化趋势与图1(b)ρ(U)变化接近。因此得出,$\mathrm{HCO}_{3}^{-}$是控制中和渣中U浸出的关键因素,这与文献[19-20]结果一致。
$\mathrm{CO}_{2}+\mathrm{H}_{2} \mathrm{O} \rightleftharpoons \mathrm{H}_{2} \mathrm{CO}_{3} \rightleftharpoons \mathrm{H}^{+}+\mathrm{HCO}_{3}^{-},$
$\mathrm{CaCO}_{3}+\mathrm{CO}_{2}+\mathrm{H}_{2} \mathrm{O} \rightleftharpoons \mathrm{Ca}^{2+}+2 \mathrm{HCO}_{3}^{-} \text {。 }$
图1~图3可知,在对酸性废渣进行中和处理时,空气中CO2是影响U稳定性的主要因素。相较于封闭体系,敞开体系中和渣上清液pH下降幅度较大,主要因为其不仅受到酸性废渣中残余酸释放的影响,还受到空气中CO2的影响,中和渣在碱性条件下对CO2的固定是个酸化过程。当中和渣处于强碱性条件时,生成次生矿物CaCO3,无$\mathrm{HCO}_{3}^{-}$;随着CO2固定,中和渣pH下降,当pH下降至弱碱性条件时,固定的CO2主要以$\mathrm{HCO}_{3}^{-}$形式存在,同时,次生矿物CaCO3也会发生部分溶解,增加上清液中ρ($\mathrm{HCO}_{3}^{-}$),进而促进U浸出。因此,空气中CO2对中和处理的酸性废渣的影响主要有2个阶段:一是在碱性条件下固定生成CaCO3;二是弱碱性至中性条件(pH 7~9)下生成$\mathrm{HCO}_{3}^{-}$,$\mathrm{HCO}_{3}^{-}$与U化学配合生成游离的碳酸铀酰(如:$\mathrm{UO}_{2}\left(\mathrm{HCO}_{3}\right)_{3}^{-}$),促进U浸出。
对敞开体系中反应300 d的Ca(OH)2投加比分别为2.5%和10.0%的中和渣固相进行pH调节,120 d后上清液中ρ(U)、ρ($\mathrm{HCO}_{3}^{-}$)及pH见表2。随着pH调节,中和处理时已稳定的2.5%Ca(OH)2和10.0%Ca(OH)2试验组中和渣出现U重新浸出现象。2.5%试验组中和渣再次投加Ca(OH)2后,各试验组pH升高,3.0% Ca(OH)2试验组ρ(U)、ρ($\mathrm{HCO}_{3}^{-}$)最高,ρ(U)为1.89 mg/L,ρ($\mathrm{HCO}_{3}^{-}$)为2.38 g/L,$\mathrm{HCO}_{3}^{-}$来源于pH升高时中和渣对空气中CO2的固定。10.0%Ca(OH)2试验组中和渣投加CaCl2后,各试验组pH降低,1.5% CaCl2试验组ρ(U)、ρ($\mathrm{HCO}_{3}^{-}$)最高,ρ(U)为1.26 mg/L,ρ($\mathrm{HCO}_{3}^{-}$)为2.14 g/L,$\mathrm{HCO}_{3}^{-}$来源于pH下降时CaCO3的部分溶解。
上清液中ρ(U)与pH、ρ($\mathrm{HCO}_{3}^{-}$)的相关性见图4ρ(U)与pH无明显相关性,U大量浸出的pH区间为7.68~8.41,此区间$\mathrm{HCO}_{3}^{-}$大量积累;ρ(U)与ρ($\mathrm{HCO}_{3}^{-}$)成正相关,相关系数(R2)为0.95。因此,在pH调节过程中$\mathrm{HCO}_{3}^{-}$的产生是U浸出的主要因素。
Mg(OH)2投加比对中和渣上清液pH、ρ(U)、ρ($\mathrm{HCO}_{3}^{-}$)影响见图5~图6。与Ca(OH)2不同,Mg(OH)2具有缓释特性,各试验组pH呈现先上升后下降的变化趋势,至50 d时pH最高,各试验组最高pH分别为8.58、9.04、9.25、9.53;50 d后pH逐渐下降,试验结束时pH分别为7.15、8.08、8.47、8.54,且仍存在一定下降趋势。Mg(OH)2投加量越多,U浸出越快,ρ(U)也越高,2.5%Mg(OH)2试验组在整个试验周期内浸出ρ(U)极低;5.0%Mg(OH)2试验组在240 d内无明显U浸出现象,240 d后开始浸出,至试验结束ρ(U)为0.36 mg/L;7.5%Mg(OH)2试验组在50 d后U开始浸出,试验结束ρ(U)为7.81 mg/L;10.0%试验组在40 d后开始浸出,试验结束时ρ(U)为8.58 mg/L。ρ($\mathrm{HCO}_{3}^{-}$)变化趋势与ρ(U)类似,试验结束时各试验组均保持着较快的上升趋势。7.5%Mg(OH)2和10.0%Mg(OH)2试验组在pH上升时,中和渣对空气中CO2的固定过程见反应式(3)。Mg(OH)2为弱碱且具有缓释特征,消耗H+能力低于Ca(OH)2,其对CO2的固定受反应式(1)影响较小;5.0%Mg(OH)2试验组由于pH相对较低,对CO2的固定量较少,上清液中ρ($\mathrm{HCO}_{3}^{-}$)累积速率低于7.5%Mg(OH)2和10.0%Mg(OH)2试验组,因此U重新浸出具有较强的滞后性。
Ca(OH)2和Mg(OH)2对酸性废渣中和处理时,2.5%试验组在整个试验周期内都维持极低的ρ(U),U稳定性显著高于其他试验组。2.5%试验组中和处理后中和渣pH较低,在空气中固定的CO2极少,基本不产生影响U稳定的$\mathrm{HCO}_{3}^{-}$;其他试验组由于碱过量,在空气中固定的CO2较多,随着中和渣pH变化,$\mathrm{HCO}_{3}^{-}$大量累积,U稳定性遭到破坏而逐渐被浸出。10.0% Ca(OH)2试验组在整个试验周期内维持着较高pH,CaCO3$\mathrm{HCO}_{3}^{-}$转化较少,中和渣中U维持着较强的稳定性,试验结束时其pH仍呈下降趋势;随着CO2固定增多,$\mathrm{HCO}_{3}^{-}$逐渐生成,U存在较强的浸出风险。
1)在对酸性废渣进行中和处理时,周围空气中的CO2会影响中和渣pH与U的稳定性。中和渣在碱性条件下对CO2的固定是个酸化过程,中和渣pH下降,空气中固定的CO2转变为$\mathrm{HCO}_{3}^{-}$,$\mathrm{HCO}_{3}^{-}$逐渐累积会促进U浸出。U与$\mathrm{HCO}_{3}^{-}$浸出成正相关关系,$\mathrm{HCO}_{3}^{-}$是影响中和渣中U稳定性的关键因素。
2)Ca(OH)2投加过量时,中和渣中会有次生矿物CaCO3生成;随着CO2固定,中和渣pH下降,CaCO3会部分溶解转变为$\mathrm{HCO}_{3}^{-}$
3)敞开试验环境中,仅有2.5%Ca(OH)2试验组和2.5%Mg(OH)2试验组可以维持极低的U浸出水平,中和处理后中和渣pH较低,在空气中固定的CO2极少,影响U稳定的$\mathrm{HCO}_{3}^{-}$基本不产生。
  • 中国铀业有限公司-东华理工大学核资源与环境国家重点实验室联合创新基金(2023NRE-LH-02)
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2025年第44卷第3期
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doi: 10.13426/j.cnki.yky.2025.02.04
  • 接收时间:2025-02-21
  • 首发时间:2025-09-06
  • 出版时间:2025-09-10
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  • 收稿日期:2025-02-21
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中国铀业有限公司-东华理工大学核资源与环境国家重点实验室联合创新基金(2023NRE-LH-02)
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    中核第四研究设计工程有限公司,河北 石家庄 050021
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2种不同金属材料的力学参数

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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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