CN115007111B - 一种用于吸附硫代硫酸盐体系中的金的核壳材料的制备方法 - Google Patents
一种用于吸附硫代硫酸盐体系中的金的核壳材料的制备方法 Download PDFInfo
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- 239000010931 gold Substances 0.000 title claims abstract description 26
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 25
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000000696 magnetic material Substances 0.000 claims abstract description 4
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000000047 product Substances 0.000 claims description 24
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- 238000000034 method Methods 0.000 abstract description 18
- 239000003463 adsorbent Substances 0.000 abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 13
- 238000000926 separation method Methods 0.000 abstract description 8
- 238000011084 recovery Methods 0.000 abstract description 7
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- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract description 2
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- 238000001179 sorption measurement Methods 0.000 description 28
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- 230000005291 magnetic effect Effects 0.000 description 14
- 239000000377 silicon dioxide Substances 0.000 description 13
- 238000002386 leaching Methods 0.000 description 10
- 125000003396 thiol group Chemical group [H]S* 0.000 description 8
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
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Abstract
本发明公开一种用于吸附硫代硫酸盐体系中的金的核壳材料的制备方法,属于湿法冶金、贵金属回收领域。本发明所述方法采用在碱性条件下同时完成二价铁与三价铁的共沉淀、正硅酸乙酯的水解及硅烷化试剂的水解缩合三种反应,最终合成出一种核壳式Fe3O4@SiO2材料。该材料不仅能够有效回收硫代硫酸盐体系中的金(Ⅰ),且具有工艺流程简单,耗时短,能耗投入低等特点,体现出良好的应用前景;此外,制备的磁性材料在吸附硫代硫酸盐体系中的金(Ⅰ)后,能够通过磁铁的作用实现从矿浆中将载金吸附剂快速分离出来,无需进行固液分离操作,可大大降低回收成本。
Description
技术领域
本发明涉及一种用于吸附硫代硫酸盐体系中的金的核壳材料的制备方法,属于湿法冶金、贵金属回收领域。
背景技术
在黄金的湿法提取技术中,硫代硫酸盐法凭借其环保无毒、高效和不与多数贱金属反应的特点成为了一种极具应用潜力的提金技术。然而,缺乏合适有效的回收方法成了限制硫代硫酸盐法发展的一大难题。吸附是一种简单、高效、经济、安全且无二次污染的方法,被认为是最有前途的分离回收技术之一。活性炭、壳聚糖、硅胶等材料已被研究用于吸附回收硫代硫酸盐体系中的金,并且都取得了一定的成效,这些载金吸附剂可以通过过滤或离心分离等操作从溶液中分离出来。然而,在工业条件下回收硫代硫酸盐浸出液中的金时,这些分离操作会耗费大量人力物力,增加使用成本。因此,对材料进行改进,开发一种高效低成本的分离方法是必要的。近年来,磁性纳米材料(Fe3O4)凭借磁性强易分离的优异特性在吸附方面得到广泛关注;但裸露的Fe3O4纳米粒子极不稳定,容易受外界环境的影响。
发明内容
本发明的目的在于提供一种用于吸附硫代硫酸盐体系中的金的核壳材料的制备方法,即在碱性条件下同时完成二价铁与三价铁的共沉淀、正硅酸乙酯及硅烷化试剂的水解缩合三种反应,最终合成出一种经巯基修饰的核壳式磁性二氧化硅材料,将其应用于回收硫代硫酸盐体系中的金(Ⅰ) 时,对溶液中金(Ⅰ) 的富集效益明显,吸附后利用磁铁可快速实现固液分离,具体包括以下步骤:
(1)将FeCl3·6H2O和FeCl2·4H2O依次溶于蒸馏水中,并加入分散剂。其中FeCl3·6H2O和FeCl2·4H2O分别作为合成Fe3O4内核的原料,在碱性条件下发生的反应;其次,使用同源铁源可以减少杂质离子的引入,尽可能使反应体系中的成分简单化。
(2)将溶解有正硅酸乙酯(TEOS)和3-巯丙基三甲氧基硅烷(MPTMS)的乙醇溶液转移至(1)中,并使溶液混合均匀。
(3)向步骤(2)所得混液缓慢滴加氨水至溶液pH在8 ~ 12之间,边加边搅拌。
(4)室温反应15 min后,将反应装置转移至40 ~ 80 ℃下的水浴锅中恒温搅拌反应20 ~ 480 min,产物磁分离后置于盐酸溶液中搅拌12 h,之后以乙醇和蒸馏水依次洗涤,直至滤液呈中性,将磁性材料置于真空烘箱中烘干得到核壳式Fe3O4@SiO2材料,将所得材料直接用于吸附硫代硫酸盐体系中的金(Ⅰ)。
优选的,本发明步骤(1)中所用的分散剂为聚乙二醇PEG400,其它满足要求的分散剂也可以用于本发明。
优选的,本发明步骤(1)中的FeCl3·6H2O、FeCl2·4H2O、聚乙二醇及水的固液比为g:g:mL:mL。
优选的,本发明步骤(2)中使用的正硅酸乙酯、3-巯丙基三甲氧基硅烷、乙醇的体积比为为(0.085~0.1983):(0.0083~0.0833):1。
优选的,本发明步骤(3)中所述氨水需在15 min内滴完,氨水的作用分别是作为沉淀剂和调节反应体系的pH。
优选的,本发明步骤(4)中的盐酸浓度为0.05~3 mol/L,加入盐酸的目的为除去生成物中改性剂与铁盐直接反应生成的非核壳结构的杂质,避免对实验结果造成影响。
本发明的有益效果为:
(1)本发明制备的巯基修饰的核壳式Fe3O4@SiO2材料兼具四氧化三铁具有磁性易分离和二氧化硅性质稳定的特点,巯基在材料表面上的嫁接更是增强了其吸附Au (Ⅰ) 的性能;该吸附剂的pH适用范围广,对硫代硫酸盐体系中金(Ⅰ) 的吸附容量大。
(2)本发明所述方法改进了传统多步法合成核壳式磁性材料耗时费力的缺点,采用“一锅法”成功地制备出了目标物,极大地节省了材料制备过程所需的时间及降低了试剂消耗。
(3)本发明制备的吸附剂具有良好的磁效应,与其他常规吸附剂相比,吸附完成后无需过滤或离心操作,通过磁铁即可快速实现从矿浆中分离出载金吸附剂,这极大地降低了回收成本。
具体实施方式
下面结合具体实施例对本发明作进一步详细说明,但本发明的保护范围并不限于所述内容。
实施例1
一种用于硫代硫酸盐提金的核壳式Fe3O4@SiO2材料的制备方法,具体包括如下步骤:
(1)分别将2g FeCl3·6H2O和3g FeCl2·4H2O依次溶于装有30mL蒸馏水的圆底烧瓶中,并向其中加入10 mL PEG400作为分散剂。
(2)量取2.55 mL的TEOS和0.25 mL的MPTMS充分溶解于30 mL乙醇中(此时的体积比为0.085:0.0083:1),将其转移至(1)中,搅拌使溶液混合均匀。
(3)向混合溶液中缓慢滴加氨水调节溶液的pH为8,边加边搅拌,氨水在15 min内滴完。
(4)室温反应15 min后,将反应装置转移至40 ℃下的水浴锅中恒温搅拌反应20min,将产物磁分离后置于0.1 mol/L的盐酸溶液中搅拌12 h,以乙醇和蒸馏水依次洗涤,直至滤液呈中性,置于真空烘箱中烘干制得巯基修饰的核壳式磁性二氧化硅材料,保存备用。
吸附过程:向体积为100mL,Au(S2O3)2 3-浓度为10 mg/L的溶液中加入0.2 g步骤(4)中制得的吸附剂,吸附前将pH值调节至10,吸附12h后,测得吸附率为70.16%,负载量为3.51kg/t。
实施例2
一种用于硫代硫酸盐提金的核壳式Fe3O4@SiO2材料的制备方法,具体包括如下步骤:
(1)分别将2 g FeCl3·6H2O和3 g FeCl2·4H2O依次溶于装有30 mL蒸馏水的圆底烧瓶中,并向其中加入10 mL PEG400作为分散剂。
(2)量取3.4 mL的TEOS和0.5 mL的MPTMS充分溶解于30 mL乙醇中(此时的体积比为0.1133:0.0167:1),将其转移至(1)中,搅拌使溶液混合均匀。
(3)向混合溶液中缓慢滴加氨水调节溶液的pH为10,边加边搅拌,氨水在15 min内滴完。
(4)室温反应15 min后,将反应装置转移至50 ℃下的水浴锅中恒温搅拌反应40min,将产物磁分离后置于0.05 mol/L的盐酸溶液中搅拌12 h,以乙醇和蒸馏水依次洗涤,直至滤液呈中性,置于真空烘箱中烘干制得巯基修饰的核壳式磁性二氧化硅材料,保存备用。
吸附过程:向体积为100mL,Au(S2O3)2 3-浓度为10 mg/L的溶液中加入0.2 g步骤(4)中制得的吸附剂,吸附前将pH值调节至9,吸附12h后,测得吸附率为84.3%,负载量为4.2kg/t。
实施例3
一种用于硫代硫酸盐提金的核壳式Fe3O4@SiO2材料的制备方法,具体包括以下步骤:
(1)分别将2 g FeCl3·6H2O和3 g FeCl2·4H2O依次溶于装有30 mL蒸馏水的圆底烧瓶中,并向其中加入10 mL PEG400作为分散剂。
(2)量取5.1 mL的TEOS和1.5 mL的MPTMS充分溶解于30 mL乙醇中(此时的体积比为0.1700:0.050:1),将其转移至(1)中,搅拌使溶液混合均匀。
(3)向混合溶液中缓慢滴加氨水调节溶液的pH为12,边加边搅拌,氨水在15 min内滴完。
(4)室温反应15 min后,将反应装置转移至70 ℃下的水浴锅中恒温搅拌反应60min,将产物磁分离后置于3 mol/L的盐酸溶液中搅拌12 h,以乙醇和蒸馏水依次洗涤,直至滤液呈中性,置于真空烘箱中烘干制得巯基修饰的核壳式磁性二氧化硅材料,保存备用。
吸附过程:向体积为100mL,Au(S2O3)2 3-浓度为20 mg/L的溶液中加入0.2 g步骤(4)中制得的吸附剂,吸附前将pH值调节至8,吸附24 h后,测得吸附率为79.13%,负载量为7.91kg/t。
实施例4
一种用于硫代硫酸盐提金的核壳式Fe3O4@SiO2材料的制备方法,具体包括如下步骤:
(1)分别将2 g FeCl3·6H2O和3 g FeCl2·4H2O依次溶于装有30 mL蒸馏水的圆底烧瓶中,并向其中加入10 mL PEG400作为分散剂。
(2)量取5.95 mL的TEOS和2.5 mL的MPTMS充分溶解于30 mL乙醇中(此时的体积比为0.1983:0.0833:1),将其转移至(1)中,搅拌使溶液混合均匀。
(3)向混合溶液中缓慢滴加氨水调节溶液的pH为11,边加边搅拌,氨水在15 min内滴完。
(4)室温反应15 min后,将装置转移至80 ℃下的水浴锅中恒温搅拌反应120 min,将产物磁分离后置于1.5 mol/L的盐酸溶液中搅拌12 h,以乙醇和蒸馏水依次洗涤,直至滤液呈中性,置于真空烘箱中烘干制得巯基修饰的核壳式磁性二氧化硅材料,保存备用。
吸附过程:以某含金矿石的浸出液为例,浸液中金的浓度为12.86 mg/L,向体积为100mL的浸金液中加入0.2 g步骤(4)中制得的吸附剂,吸附前将pH值调节至10,吸附12 h后,测得吸附率为38.91%,负载量为2.5 kg/t。
实施例5
一种用于硫代硫酸盐提金的核壳式Fe3O4@SiO2材料的制备方法,具体包括以下步骤:
(1)分别将2 g FeCl3·6H2O和3 g FeCl2·4H2O依次溶于装有30 mL蒸馏水的圆底烧瓶中,并向其中加入10 mL PEG400作为分散剂。
(2)量取3.4 mL的TEOS和1 mL的MPTMS充分溶解于30 mL乙醇中(此时的体积比为0.1133:0.0333:1),将其转移至(1)中,搅拌使溶液混合均匀。
(3)向混合溶液中缓慢滴加氨水调节溶液的pH为12,边加边搅拌,氨水在15 min内滴完。
(4)室温反应15 min后,将反应装置转移至70 ℃下的水浴锅中恒温搅拌反应480min,将产物磁分离后置于1 mol/L的盐酸溶液中搅拌12 h,以乙醇和蒸馏水依次洗涤,直至滤液呈中性,置于真空烘箱中烘干制得巯基修饰的核壳式磁性二氧化硅材料,保存备用。
吸附过程:以某含金矿石的浸出液为例,浸液中金的浓度为12.86 mg/L,向体积为100mL的浸金液中加入0.2 g步骤(4)中制得的吸附剂,吸附前将pH值调节至9,吸附12 h后,测得吸附率为52.26%,负载量为3.36 kg/t。
对比实施例1
制备一种非核壳结构的无磁性吸附剂吸附硫代硫酸盐体系中的金,具体包括以下步骤:
(1)量取3.4 mL的TEOS和1 mL的MPTMS充分溶解于30 mL乙醇中(此时的体积比为0.1133:0.0333:1),搅拌使溶液混合均匀。
(2)向步骤(1)溶液中缓慢滴加氨水调节溶液的pH为12,边加边搅拌,氨水在15min内滴完。
(3)室温反应15 min后,将反应装置转移至70 ℃下的水浴锅中恒温搅拌反应480min后置于1 mol/L的盐酸溶液中搅拌12 h,以乙醇和蒸馏水依次洗涤,直至滤液呈中性,置于真空烘箱中烘干制得巯基修饰的二氧化硅材料,保存备用。
吸附过程:以某含金矿石的浸出液为例,浸液中金的浓度为12.86 mg/L,向体积为100mL的浸金液中加入0.2 g步骤(3)中制得的吸附剂,吸附前将pH值调节至9,吸附12 h后,测得吸附率为36.58%,负载量为2.35 kg/t。
以上结果证实在其他条件不变时制备得到的具有核壳结构的吸附剂对硫代硫酸盐溶液中金的吸附性能更好,且更易于分离。
以上对本发明的具体实施方式作了详细说明,但是本发明并不限于上述实施方式,在本领域普通技术人员所具备的知识范围内,还可以在不脱离本发明宗旨的前提下作出各种变化。
Claims (1)
1.核壳式Fe3O4@SiO2材料在吸附硫代硫酸盐体系中的金中的应用,所述核壳式Fe3O4@SiO2材料的具体制备过程如下:
(1)将FeCl3·6H2O和FeCl2·4H2O依次溶于蒸馏水中,并加入分散剂;
(2)将溶解有正硅酸乙酯和3-巯丙基三甲氧基硅烷的乙醇溶液添加至步骤(1)的混合溶液中,并使溶液混合均匀;
(3)向步骤(2)所得混液缓慢滴加氨水至溶液pH在8 ~ 12之间,边加边搅拌;
(4)室温反应15 min后,将反应装置转移至40 ~ 80 ℃下的水浴锅中恒温搅拌反应20~ 480 min,产物磁分离后置于盐酸溶液中搅拌12 h,之后以乙醇和蒸馏水依次洗涤,直至滤液呈中性,将磁性材料置于真空烘箱中烘干得到核壳式Fe3O4@SiO2材料;
步骤(1)中的FeCl3·6H2O、FeCl2·4H2O、聚乙二醇及水的固液比为2:3:10:30,g:g:mL:mL;
步骤(1)中所用的分散剂为聚乙二醇PEG400;
步骤(2)中使用的正硅酸乙酯、3-巯丙基三甲氧基硅烷、乙醇的体积比为(0.085~0.1983):(0.0083~0.0833):1;
步骤(3)中所述氨水需在15 min内滴完;
步骤(4)中的盐酸浓度为0.05~3 mol/L。
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