Article(id=1172619711125795443, tenantId=1146029695717560320, journalId=1146120122248306696, issueId=1172619710446321994, articleNumber=1009-2617(2024)03-0250-08, orderNo=null, doi=10.13355/j.cnki.sfyj.2024.03.006, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1703952000000, receivedDateStr=2023-12-31, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1757503925353, onlineDateStr=2025-09-10, pubDate=1718812800000, pubDateStr=2024-06-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1757503925353, onlineIssueDateStr=2025-09-10, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1757503925353, creator=13701087609, updateTime=1757503925353, updator=13701087609, issue=Issue{id=1172619710446321994, tenantId=1146029695717560320, journalId=1146120122248306696, year='2024', volume='43', issue='3', pageStart='215', pageEnd='340', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=0, createTime=1757503925191, creator=13701087609, updateTime=1758768108393, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1177922079165923462, tenantId=1146029695717560320, journalId=1146120122248306696, issueId=1172619710446321994, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1177922079165923463, tenantId=1146029695717560320, journalId=1146120122248306696, issueId=1172619710446321994, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=250, endPage=257, ext={EN=ArticleExt(id=1172619711411008117, articleId=1172619711125795443, tenantId=1146029695717560320, journalId=1146120122248306696, language=EN, title=Mechanism of the Effect of Hard Agglomeration on the Efficiency of Magnesium Oxide Acidizing Leaching Rate in Lightly Fired Powders, columnId=1152626641181700664, journalTitle=Hydrometallurgy of China, columnName=Experiment Research, runingTitle=null, highlight=null, articleAbstract=

The leaching of magnesium from lightly fired powders obtained from low temperature calcination of magnesite by hydrochloric acid acidification was studied. The effects of addition method of hydrochloric acid, concentration of hydrochloric acid, liquid volume/solid mass ratio, external force way and reaction time on magnesium leaching rate were investigated. The leaching kinetics of lightly fired powders under ultrasonic condition was analyzed by using shrinkage core model. And the particle size distribution, mineral composition and mineral distribution characteristics of leaching residue were further analyzed. The results show that under the conditions of slowly adding hydrochloric acid, hydrochloric acid concentration of 14.8%, liquid volume/solid mass ratio of 9.8/1, stirring speed of 400 r/min and leaching time of 12.5 min, the leaching rate of magnesium can reach 70.48%. Using ultrasound can cause hard agglomeration to produce cracks or disintegration, which is beneficial to solid-liquid mass transfer, and the magnesium leaching rate is increased to 90.56%. The leaching process of lightly fired powders conforms to the mixed control model of surface chemical reaction and product layer diffusion. The ratio of magnesium to oxygen in the hard agglomeration is 1.33, the edge is 1.65, and there is a large amount of unreacted magnesium in the hard agglomeration. The particle size of the leaching slag is reduced from 42.61 μm to 24.39 μm by ultrasonic action. The ultrasonic bubble vibration force and the shock wave formed by the cavitation collapse can effectively prevent the formation of hard agglomeration or make the hard agglomeration re-disaggregate.

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白丽梅(1979—),女,博士,教授,博士生导师,主要研究方向为非金属矿深加工和难选矿产资源高值利用。E-mail:
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刘宇(1999—),女,硕士研究生,主要研究方向为矿物新材料。

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刘宇(1999—),女,硕士研究生,主要研究方向为矿物新材料。

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刘宇(1999—),女,硕士研究生,主要研究方向为矿物新材料。

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AIChE Journal, 2006, 52(4):1318-1325., articleTitle=Design of high-temperature,gas-phase synthesis of hard or soft TiO2 agglomerates, refAbstract=null), Reference(id=1177245354362815434, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172619711125795443, doi=null, pmid=null, pmcid=null, year=2018, volume=null, issue=null, pageStart=null, pageEnd=null, url=null, language=null, rfNumber=[18], rfOrder=17, authorNames=祖坎, journalName=声场作用下可吸入颗粒物团聚动力学特性及对过滤器工作效率的影响研究, refType=null, unstructuredReference=祖坎. 声场作用下可吸入颗粒物团聚动力学特性及对过滤器工作效率的影响研究[D]. 上海: 上海交通大学, 2018., articleTitle=null, refAbstract=null), Reference(id=1177245354434118603, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1172619711125795443, doi=null, pmid=null, pmcid=null, year=2017, volume=36, issue=13, pageStart=157, pageEnd=158, url=null, language=null, rfNumber=[19], rfOrder=18, authorNames=刘中常, journalName=价值工程, refType=null, unstructuredReference=刘中常. 纳米材料中纳米粒子团聚的原因及解决方法[J]. 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1—盐酸;2—恒流蠕动泵;3—搅拌器;4—反应容器;5—水槽。

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a—化学反应控制;b—产物层扩散控制;c—混合控制。

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a—轻烧粉原料;b—酸浸渣(无超声);c—酸浸渣(有超声)。

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MgO CaO Fe2O3 Al2O3 SiO2
92.49 1.13 0.61 0.77 5.00
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轻烧粉的主要化学组成 %

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MgO CaO Fe2O3 Al2O3 SiO2
92.49 1.13 0.61 0.77 5.00
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盐酸添加方式 镁浸出率/%
正向 缓慢添加 68.83
快速添加 65.92
反向 缓慢添加 70.48
快速添加 68.26
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盐酸添加方式对镁浸出率的影响

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盐酸添加方式 镁浸出率/%
正向 缓慢添加 68.83
快速添加 65.92
反向 缓慢添加 70.48
快速添加 68.26
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液固体积质量比 终点pH 镁浸出率/%
7.6/1 8.40 65.10
9.8/1 7.85 70.48
10.8/1 6.13 66.73
12.0/1 3.06 63.23
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液固体积质量比对终点pH、镁浸出率的影响

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液固体积质量比 终点pH 镁浸出率/%
7.6/1 8.40 65.10
9.8/1 7.85 70.48
10.8/1 6.13 66.73
12.0/1 3.06 63.23
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外力作用方式 镁浸出率/%
超声 35.26
搅拌 70.48
超声+搅拌 83.02
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不同外力作用方式下的镁浸出率

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外力作用方式 镁浸出率/%
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表面化学反应控制 产物层扩散控制 混合控制
kr/min-1 R2 kd/min-1 R2 km/min-1 R2
0.000 56 0.974 0.000 28 0.975 0.000 99 0.994
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超声下收缩核模型的化学反应速率常数和线性拟合相关系数

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表面化学反应控制 产物层扩散控制 混合控制
kr/min-1 R2 kd/min-1 R2 km/min-1 R2
0.000 56 0.974 0.000 28 0.975 0.000 99 0.994
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硬团聚对轻烧粉氧化镁酸化浸出率的影响机制研究
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刘宇 1, 2, 3 , 白丽梅 1, 2, 3 , 马玉新 1, 2, 3 , 李绍英 1, 2, 3 , 赵留成 1, 2, 3
湿法冶金 | 试验研究 2024,43(3): 250-257
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湿法冶金 | 试验研究 2024, 43(3): 250-257
硬团聚对轻烧粉氧化镁酸化浸出率的影响机制研究
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刘宇1, 2, 3, 白丽梅1, 2, 3 , 马玉新1, 2, 3, 李绍英1, 2, 3, 赵留成1, 2, 3
作者信息
  • 1 华北理工大学 矿业工程学院, 河北 唐山 063210
  • 2 矿产资源绿色开发与生态修复协同创新中心, 河北 唐山 063210
  • 3 河北省矿业开发与安全技术实验室, 河北 唐山 063210
  • 刘宇(1999—),女,硕士研究生,主要研究方向为矿物新材料。

通讯作者:

白丽梅(1979—),女,博士,教授,博士生导师,主要研究方向为非金属矿深加工和难选矿产资源高值利用。E-mail:
Mechanism of the Effect of Hard Agglomeration on the Efficiency of Magnesium Oxide Acidizing Leaching Rate in Lightly Fired Powders
Yu LIU1, 2, 3, Limei BAI1, 2, 3 , Yuxin MA1, 2, 3, Shaoying LI1, 2, 3, Liucheng ZHAO1, 2, 3
Affiliations
  • 1 College of Mining Engineering, North China University of Science and Technology, Tangshan 063210, China
  • 2 Collaborative Innovation Center for Green Development and Ecological Restoration of Mineral Resources, Tangshan 063210, China
  • 3 Hebei Mining Development and Safety Technology Laboratory, Tangshan 063210, China
出版时间: 2024-06-20 doi: 10.13355/j.cnki.sfyj.2024.03.006
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研究了采用盐酸酸化法从菱镁矿低温煅烧所得轻烧粉中浸出镁,考察了盐酸添加方式、盐酸浓度、液固体积质量比、外力作用方式和反应时间对镁浸出率的影响,采用收缩核模型分析了超声条件下轻烧粉的浸出动力学,并进一步分析浸渣的粒度分布、矿物成分及矿物嵌布特征。结果表明:在反向缓慢添加盐酸、盐酸浓度14.8%、液固体积质量比9.8/1、搅拌速度400 r/min、浸出时间12.5 min条件下,镁浸出率达70.48%;引入超声可使硬团聚产生裂纹或碎解,有利于固液传质,将镁浸出率提高至90.56%;轻烧粉的浸出过程符合表面化学反应及产物层扩散的混合控制模型;硬团聚内部镁氧比为1.33,边缘为1.65,内部有大量未反应的镁,超声作用使浸渣粒度由42.61 μm减小至24.39 μm,超声的气泡振动力和空泡破灭形成的冲击波可有效防止硬团聚的形成或使硬团聚重新碎解分散。
轻烧粉  /  镁  /  浸出  /  盐酸  /  硬团聚  /  机制  /  动力学

The leaching of magnesium from lightly fired powders obtained from low temperature calcination of magnesite by hydrochloric acid acidification was studied. The effects of addition method of hydrochloric acid, concentration of hydrochloric acid, liquid volume/solid mass ratio, external force way and reaction time on magnesium leaching rate were investigated. The leaching kinetics of lightly fired powders under ultrasonic condition was analyzed by using shrinkage core model. And the particle size distribution, mineral composition and mineral distribution characteristics of leaching residue were further analyzed. The results show that under the conditions of slowly adding hydrochloric acid, hydrochloric acid concentration of 14.8%, liquid volume/solid mass ratio of 9.8/1, stirring speed of 400 r/min and leaching time of 12.5 min, the leaching rate of magnesium can reach 70.48%. Using ultrasound can cause hard agglomeration to produce cracks or disintegration, which is beneficial to solid-liquid mass transfer, and the magnesium leaching rate is increased to 90.56%. The leaching process of lightly fired powders conforms to the mixed control model of surface chemical reaction and product layer diffusion. The ratio of magnesium to oxygen in the hard agglomeration is 1.33, the edge is 1.65, and there is a large amount of unreacted magnesium in the hard agglomeration. The particle size of the leaching slag is reduced from 42.61 μm to 24.39 μm by ultrasonic action. The ultrasonic bubble vibration force and the shock wave formed by the cavitation collapse can effectively prevent the formation of hard agglomeration or make the hard agglomeration re-disaggregate.

magnesite  /  magnesium  /  leaching  /  hydrochloric acid  /  hard agglomeration  /  mechanism  /  kinetics
刘宇, 白丽梅, 马玉新, 李绍英, 赵留成. 硬团聚对轻烧粉氧化镁酸化浸出率的影响机制研究. 湿法冶金, 2024 , 43 (3) : 250 -257 . DOI: 10.13355/j.cnki.sfyj.2024.03.006
Yu LIU, Limei BAI, Yuxin MA, Shaoying LI, Liucheng ZHAO. Mechanism of the Effect of Hard Agglomeration on the Efficiency of Magnesium Oxide Acidizing Leaching Rate in Lightly Fired Powders[J]. Hydrometallurgy of China, 2024 , 43 (3) : 250 -257 . DOI: 10.13355/j.cnki.sfyj.2024.03.006
世界已探明菱镁矿储量约为130亿t,我国菱镁矿储量居世界第一,占世界总储量的22.5%[1]。轻烧粉是菱镁矿经750~1 100 ℃煅烧获得的粗加工镁制品,分解后烧失率在50%左右,MgO含量可提高近1倍,初步实现富集[2]。轻烧粉因具有高热稳定性和电绝缘性,适用于耐火材料的制备[3],也广泛应用于化工、农业、轻工、环境保护、钢铁冶金等行业[4];但轻烧粉中含有的SiO2、CaO、Fe2O3、Al2O3等杂质,限制了其高附加值利用,因此,镁的深度提取是制备高值利用轻烧粉的关键。
采用化学选矿法可进一步去除杂质,实现深度除杂,大大提高镁利用率。目前轻烧粉的化学选矿法主要有氨浸法[5-6]、碳化法[7-8]和酸浸法[9-13]。其中,氨浸法是将轻烧粉与铵盐溶液反应,之后加入沉淀剂沉淀分离镁,该法浸出率低,能耗较大,成本较高;碳化法是将轻烧粉消化碳化后制成碱式碳酸镁中间产物,再煅烧生成氧化镁的提镁工艺,该法所用CO2气体绿色无污染,但工艺流程较长,相关研究较少;酸浸法是将轻烧粉与酸反应生成镁盐溶液,后续再经煅烧得到氧化镁,该法因流程较短,操作简便得到广泛应用,但酸用量、浓度及反应时间均须严格控制,才能避免产生反应放热造成的硬团聚问题。
试验采用盐酸为浸出剂浸出轻烧粉中的镁,研究了不同盐酸添加方式、盐酸浓度、液固体积质量比、反应时间和外力作用方式对轻烧粉镁浸出率的影响规律,探讨了硬团聚对镁浸出影响的相关机制,以期为酸浸法提镁工艺提供技术参考。
试验原料:某低品位菱镁矿矿石经颚式破碎、对辊筛分至粒径<2 mm,混匀后缩分取样并置于马弗炉中于650 ℃下煅烧4 h所得轻烧粉,烧失率达49%以上,其X射线衍射图谱如图1所示,主要化学组成见表1
图1看出:轻烧粉的主要衍射峰为MgO,同时含有少量SiO2。由表1看出:轻烧粉MgO质量分数为92.49%,SiO2质量分数为5.00%,还含有微量铁、钙、铝等杂质元素。
试验试剂:浓盐酸(37%)、氨水、氯化铵、三乙醇胺、铬黑-T、EDTA标准溶液,均为分析纯;自制蒸馏水。
试验设备:Micro-x型马弗炉、H2025G型电动搅拌器、DHC-9070A型电热鼓风干燥箱、D/MAX2500PC X型射线衍射仪、Scios型聚焦离子束发射扫描电子显微镜、CP214型精密电子天平、烧杯、量筒、恒流蠕动泵、滴定管等。
轻烧粉中各氧化物与盐酸的浸出反应见式(1),M代表Mg、Ca、Fe、Al;SiO2不与盐酸反应。
MxOy+HCl→MCl+H2O。
用盐酸浸出轻烧粉后所得浸出液中含Mg2+、Ca2+、Fe3+、Al3+,利用各离子的氢氧化物溶度积差异,通过控制溶液体系pH即可实现Fe3+、Al3+和Mg2+的有效分离。
酸浸试验装置如图2所示。取一定量轻烧粉、一定体积37%盐酸及对应体积蒸馏水,将三者以不同的添加方式倒入500 mL烧杯中。在常压室温下施加搅拌或在超声条件下反应一定时间。反应结束后,真空抽滤,分离浆液,测定并记录滤液体积,采用EDTA络合滴定法对滤液中的Mg2+进行定量分析,计算Mg2+浸出率。计算公式为
x=$\frac{cV{M}_{r}}{mw}$×100%。
式中:x—Mg2+浸出率,%;c—滤液中Mg2+浓度,mol/L;V—滤液体积,L;Mr—氧化镁相对分子质量;m—轻烧粉质量,g;w—轻烧粉中氧化镁质量分数,%。
在盐酸浓度14.8%、搅拌速度400 r/min、液固体积质量比9.8/1、浸出时间12.5 min条件下,考察4种盐酸添加方式对镁浸出率的影响,试验结果见表2。正向添加是将轻烧粉直接加入浓度14.8%盐酸中;反向添加是以水作轻烧粉的预分散剂,加入未稀释的盐酸到预先分散了轻烧粉的水中,使最终盐酸浓度为14.8%。正向和反向均采用缓慢添加和快速添加方式分别进行,缓慢添加的盐酸流量为0.7 L/h,快速添加的盐酸流量为4 L/h。由表2看出:镁浸出率在反向添加盐酸方式下优于正向添加,且缓慢添加优于快速添加,镁浸出率从68.26%提高到70.48%。这是因为反向添加是将轻烧粉预先分散在水中,在轻烧粉表面、各颗粒之间形成一层液膜,阻止颗粒相互靠近,再加入盐酸,可有效抑制硬团聚的形成[14]。分散的轻烧粉和盐酸充分接触有利于提高镁离子浸出率;同时缓慢添加盐酸能控制轻烧粉与盐酸的接触速度,使溶液过饱和度一直维持在较低状态,也大大降低放热的剧烈程度,有效避免硬团聚现象出现。因此,确定以反向缓慢添加盐酸方式为宜。
采用反向缓慢添加盐酸方式,在搅拌速度400 r/min、浸出时间12.5 min条件下,考察盐酸浓度对轻烧粉中镁浸出率的影响,试验结果如图3所示。
图3看出,随盐酸浓度增大,镁浸出率呈先升高后降低趋势:盐酸浓度为14.8%时,镁浸出率达最高,为70.48%;盐酸浓度继续增大,镁浸出率快速降低。盐酸浓度较低时,溶液黏度较低,利于传质扩散,促进浸出反应进行,而且可适当缓冲轻烧粉和盐酸反应的放热现象,减少因局部放热产生的团聚现象;但此时溶液中离子浓度较低,浸出反应较为缓慢;因此适当增大盐酸浓度可加速镁离子的浸出;盐酸浓度进一步增大,镁浸出率显著下降,主要是因为盐酸浓度过大,反应过程剧烈放热,造成盐酸挥发,导致与轻烧粉反应的盐酸量减少,同时盐酸浓度高,颗粒间距离小,轻烧粉遇酸反应剧烈,迅速形成硬团聚阻止了内部轻烧粉与盐酸的反应。因此,确定反应的最佳盐酸浓度为14.8%。
采用反向缓慢添加盐酸方式,在盐酸浓度14.8%、搅拌速度400 r/min、浸出时间12.5 min条件下,通过改变轻烧粉添加量的方式改变液固体积质量比,考察液固体积质量比对镁浸出率的影响,试验结果见表3
表3看出:随液固体积质量比增大,镁浸出率呈先升高后降低趋势,在液固体积质量比增至9.8/1时,镁浸出率达最大,为70.48%。液固体积质量比较小时,反应终点溶液呈碱性,部分Mg2+以氢氧化镁形式存在,镁浸出率降低;随液固体积质量比增大,溶液体量增多,可减缓反应放热现象出现硬团聚,但氧化镁添加量减少,使镁浸出率降低,且反应后溶液呈酸性,无法将杂质离子与镁离子分离。因此,确定反应的最佳液固体积质量比为9.8/1。
采用反向缓慢添加盐酸方式,在盐酸浓度14.8%、液固体积质量比9.8/1、浸出时间12.5 min条件下,考察搅拌速度对镁浸出率的影响,试验结果如图4所示。
图4看出,随搅拌速度增大,镁浸出率先逐渐升高后趋于稳定:搅拌速度增至400 r/min后,镁浸出率达最大,为70.48%;之后继续增大搅拌速度,镁浸出率无明显变化。无搅拌条件下,轻烧粉因重力作用沉降于容器底部,与浸出液接触不充分,镁浸出率较低;随搅拌速度增大,搅拌力引起液流强湍流运动对矿物产生机械力,使浸出液与轻烧粉颗粒的流动性增大,浸出液与矿物颗粒之间接触更充分,有利于镁的浸出。但搅拌力仅能使矿物在液体环境中充分分散,无法重新分散反应过程中产生的硬团聚;且搅拌速度增大至一定程度后,固液体系的传热传质状况已达平衡状态,继续增大搅拌速度对镁浸出反应影响不大。因此,确定反应的最佳搅拌速度为400 r/min。
采用反向缓慢添加盐酸方式,在盐酸浓度14.8%、液固体积质量比9.8/1、搅拌速度400 r/min、浸出时间12.5 min条件下,分别采用搅拌、超声(300 W)、超声+搅拌3种外力作用方式进行浸出试验,不同外力作用方式下的镁浸出率见表4
表4看出:单一超声作用下,镁浸出率较低;外加搅拌作用,镁浸出率得到明显提高;超声+搅拌作用方式下的镁浸出率相对较大,为83.02%。这是因为单一超声作用对矿粉的作用力弱,矿粉仍粘附于容器底部,无法与盐酸充分接触,导致浸出率较低。搅拌作用力可增大浸出液与矿粉接触概率,同时加入超声,可使反应体系形成大量的空泡,气泡振动力和空泡破灭形成的冲击波使矿粉在反应液中分散效果更好,能有效避免硬团聚的形成或对已形成的硬团聚进行重新碎解,更有利于浸出反应的进行。
采用反向缓慢添加盐酸方式,在盐酸浓度14.8%、液固体积质量比9.8/1、搅拌速度400 r/min条件下,分别在无超声和有超声条件下考察浸出时间对镁浸出率的影响,试验结果如图5所示。
图5看出:在无超声条件下,浸出时间从5 min延长至300 min,镁浸出率从68.7%升至71.11%左右,镁浸出率仅提高了约3%;但引入超声后,在考察时间范围内,镁浸出率提高9%左右,相较无超声条件升高幅度较大,进一步说明引入超声可提高镁浸出率。
试验通过分析浸出动力学,确定浸出反应的控制步骤,进一步判断超声作用对轻烧粉的镁浸出作用。轻烧粉与盐酸的整个化学反应过程为液-固反应,液-固反应一般可用收缩核模型来解释,通常可分为表面化学反应控制、产物层扩散控制或混合模型控制[15],模型方程见式(3)~(5)。
$1-(1-x)^{\frac{1}{3}}=k_{\mathrm{r}} t$
$1-\frac{2}{3} x-(1-x)^{\frac{2}{3}}=k_{\mathrm{d}} t$
$\frac{1}{3} \ln (1-x)+(1-x)^{-\frac{1}{3}}-1=k_{\mathrm{m}} t_{\circ}$
式中:x—浸出率,%;krkdkm—表面化学反应控制、产物层扩散控制、混合控制化学反应速率常数,min-1;t—反应时间,min。
采用不同模型对轻烧粉浸出反应过程进行对比分析,分别计算表观速率常数和拟合相关系数,利用浸出动力学模型进行回归分析,结果见表5
表5图6看出:超声作用下的浸出数据与混合控制模型拟合相关系数均优于其他模型,说明浸出过程符合表面化学反应及产物层扩散的混合控制模型。外加超声作用能使矿物颗粒或产生的硬团聚产生裂纹,加速矿粒表面生成物的剥离,促进颗粒与溶液间的传质,大大加快浸出速度。
基于上述浸出试验研究结果,分别对有超声和无超声作用下所得酸浸渣进行磨片,分析浸渣形态,探究超声作用对镁浸出的影响机制。
图7为轻烧粉原料及无超声和有超声作用下所得酸浸渣的SEM分析结果。可以看出:轻烧粉多为单独分散的小颗粒物,仅有较少的大颗粒;而酸浸渣中出现带有裂隙的较大颗粒,这是反应过程中小颗粒反应物团聚在一起形成的硬团聚,粉体颗粒之间结合紧密甚至出现类似穿插生长的状态。硬团聚[16]主要是由于颗粒间的范德华力、库仑力和化学键作用所致,通过增大搅拌速度和延长反应时间,仍无法轻易破坏其结构,而超声的引入会使大块硬团聚表面出现裂隙,或直接碎解成小颗粒。
图8为无超声和有超声作用下所得酸浸渣的粒度分布。可以看出:无超声作用下所得酸浸渣颗粒平均粒径为42.61 μm,存在较多大颗粒,细小颗粒较少,硬团聚现象较为严重;超声作用下酸浸渣分散性好,硬团聚明显减少,颗粒粒度分布更集中,小颗粒占比提高,平均粒径减小至24.39 μm。超声作用可将硬团聚碎解为较小颗粒,使轻烧粉和盐酸的接触面积增大,从而提高镁浸出率。
图9为无超声作用下酸浸渣硬团聚的EDS图谱。硬团聚内部(图9(a))镁氧比为1.65(镁62.20%,氧37.80%),边缘(图9(b))镁氧比为1.33(镁57.19%,氧42.81%),内部镁氧比与氧化镁理论值更接近,说明硬团聚的内部有大量未反应氧化镁包覆在其中,无法与盐酸充分接触并反应。反应生成的硬团聚越多,硬团聚粒径越大,被包覆的镁越多,镁浸出率越低。
氧化镁活性与镁的酸浸速度呈正相关性,氧化镁活性越高,镁浸出速度越快,浸出达到平衡所需时间越短。采用枸橼酸显色时间对轻烧粉氧化镁进行表征,其显色时间为76 s,化学活性高;但化学活性过高会造成浸出过程中轻烧粉氧化镁与浸出液反应迅速并剧烈放热[17],为达到稳定状态会降低自身的表面自由能,从而产生矿物颗粒相互聚集靠拢硬化的现象生成硬团聚[18],造成硬团聚内部矿物与浸出液无法充分接触,大大降低镁浸出率。在超声作用下反应体系形成大量气泡,气泡振动力和空泡破灭形成的冲击波不仅可作用于硬团聚表面的开口缝隙,还可作用于颗粒间和颗粒内的闭口缝隙(如图10所示),使颗粒间的颈部缝合发生断裂,在一定程度上引起氢键等化学键的断裂[19],使顽固的硬团聚发生碎解,分散成小颗粒。
采用盐酸酸化法从菱镁矿低温煅烧所得轻烧粉中浸出镁,在以缓慢添加方式加入14.8%盐酸、液固体积质量比9.8/1、搅拌速度400 r/min、反应时间12.5 min条件下,轻烧粉中的镁浸出率为70.48%;相同条件下引入超声(300 W)后,镁浸出率可提升至83.02%;继续延长浸出时间至300 min,镁浸出率可达90.56%。超声作用产生的气泡振动力和空泡破灭形成的冲击波可在硬团聚孔隙发生作用,使硬团聚表面产生裂隙或碎解成小颗粒,有利于固液传质,显著提高镁浸出率。在后续试验中,可采用在液相反应中添加表面活性剂等方法来消除硬团聚,提高镁浸出率,该法对镁的综合利用具有一定参考价值。
  • 河北省自然科学基金(钢铁联合)资助项目(E2022209127)
  • 河北省高等学校科学技术研究项目(CXY2023008)
  • 河北省教育厅自然科学研究项目(QN2024215)
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2024年第43卷第3期
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doi: 10.13355/j.cnki.sfyj.2024.03.006
  • 接收时间:2023-12-31
  • 首发时间:2025-09-10
  • 出版时间:2024-06-20
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  • 收稿日期:2023-12-31
基金
河北省自然科学基金(钢铁联合)资助项目(E2022209127)
河北省高等学校科学技术研究项目(CXY2023008)
河北省教育厅自然科学研究项目(QN2024215)
作者信息
    1 华北理工大学 矿业工程学院, 河北 唐山 063210
    2 矿产资源绿色开发与生态修复协同创新中心, 河北 唐山 063210
    3 河北省矿业开发与安全技术实验室, 河北 唐山 063210

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白丽梅(1979—),女,博士,教授,博士生导师,主要研究方向为非金属矿深加工和难选矿产资源高值利用。E-mail:
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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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