皮胶原为模板制备纤维状钛锂离子筛前驱体

吴远彬; 杨茹; 邓胜连; 张理元

doi:10.7513/j.issn.1004-7638.2021.02.010

皮胶原为模板制备纤维状钛锂离子筛前驱体

doi: 10.7513/j.issn.1004-7638.2021.02.010

吴远彬^{1, 2, 3,},
杨茹¹,
邓胜连¹,
张理元^{1, 2, 3, ,}

1.
内江师范学院化学化工学院，四川内江 641112
2.
果蔬类废弃物资源化四川省高校重点实验室，四川内江 641112
3.
内江师范学院院士(专家)工作站，四川内江 641112

基金项目: 四川省科技计划项目(项目号2019YJ0383)

详细信息

作者简介:
吴远彬(1992—)，男，四川西昌人，硕士生，实习研究员，主要从事锂吸附材料研究，E-mail：654094849@qq.com

通讯作者:
张理元，博士，副教授，E-mail：zhangliyuansir@126.com

中图分类号: TF823，TQ424
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- 文章访问数: 239
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- 被引次数: 0
出版历程
- 收稿日期: 2021-02-24
- 刊出日期: 2021-04-10

Preparation of fibrous titanium-lithium ion sieve precursor with skin collagen as the template

Wu Yuanbin^{1, 2, 3
,},
Yang Ru¹,
Deng Shenglian¹,
Zhang Liyuan^{1, 2, 3
, ,}

1.
College of Chemistry and Chemical Engineering, Neijiang Normal University, Neijiang 641112, Sichuan, China
2.
Key Laboratory of Fruit Waste Treatment and Resource Recycling of the Sichuan Provincial College, Neijiang 641112, Sichuan, China
3.
Academician (Expert) Workstation of Neijiang Normal University, Neijiang 641112, Sichuan, China

摘要

摘要: 为解决传统的粉末状钛锂离子筛渗透性和流动性差的问题，以皮胶原作为模板剂，廉价易得的Ti(SO₄)₂为钛源，乙酸锂为锂源，经皮胶原负载钛、锂及固相反应制备具有纤维结构的钛锂离子筛前驱体(Li₂TiO₃)。探究加入不同试剂、不同处理方法、不同pH值等因素对合成钛锂离子筛前驱体(Li₂TiO₃)的影响。采用扫描电子显微镜和X射线衍射仪对试样进行了表征。结果表明：加入单宁，控制试验pH=4.0在750 ℃条件下保温8 h制备的钛锂离子筛前驱体纤维结构较好，晶相组成为单斜结构β-Li₂TiO₃。
- 钛锂离子筛 /
- 前驱体 /
- 皮胶原 /
- 纤维结构 /
- 单宁
Abstract: In order to solve the poor permeability and fluidity of traditional powder titanium-lithium ion sieve, fibrous precursor of titanium-lithium ion sieve (Li₂TiO₃) was prepared via the solid-state reaction with skin collagen as the template, Ti(SO₄)₂ and lithium acetate as the titanium and lithium source respectively. The effects of reagent, treatment method and pH value on the synthesis of titanium-lithium ion sieve precursor were investigated. The samples were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The results show that a good fibrous precursor of titanium-lithium ion sieve can be obtained by adding tannin, controlling pH=4.0 and holding at 750 ℃ for 8 h, with the obtained sample composed of monoclinic β-Li₂TiO₃.
- titanium-lithium ion sieve /
- precursor /
- collagen /
- fiber structure /
- tannin

HTML全文

图 1 皮胶原的SEM图片

Figure 1. SEM image of skin collagen

下载: 全尺寸图片幻灯片

图 2 不同处理方法得到的样品SEM图像

Figure 2. SEM images of the samples prepared with different approaches

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图 3 加入不同试剂后样品的SEM图像

Figure 3. SEM images of the samples after adding various reagents

下载: 全尺寸图片幻灯片

图 4 加入单宁后在750℃条件下煅烧8 h制备的Li₂TiO₃的XRD图谱

Figure 4. XRD patterns of Li₂TiO₃ prepared by calcining at 750 ^oC for 8 h after adding tannin

下载: 全尺寸图片幻灯片

图 5 不同pH处理的样品的SEM图像

Figure 5. SEM images of the samples with different pH values

下载: 全尺寸图片幻灯片

表 1 主要试验试剂

Table 1. The main reagents

化学试剂	规格	生产厂家规格
皮胶原	分析纯(AR)	中国林业科学研究院林产化学工业研究所科技开发总公司单宁化工实验室
柠檬酸三钠	分析纯(AR)	成都市科龙化工试剂厂
柠檬酸(一水)	分析纯(AR)	成都市科龙化工试剂厂
氯化钠	分析纯(AR)	成都金山化学试剂有限公司
甲酸	分析纯(AR)	成都金山化学试剂有限公司
无水乙醇	分析纯(AR)	成都金山化学试剂有限公司
硫酸钛	分析纯(AR)	国药集团化学试剂有限公司
碳酸氢钠	分析纯(AR)	成都市科龙化工试剂厂
乙酸锂	分析纯(AR)	山东西亚化学工业有限公司
硫酸	分析纯(AR)	成都金山化学试剂有限公司
三乙醇胺	分析纯(AR)	成都金山化学试剂有限公司
单宁	分析纯(AR)	成都市新都区木兰镇工业开发区
戊二醛25%	分析纯(AR)	成都市科隆花心品有限公司

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表 2 主要试验仪器

Table 2. The main experimental instrument

试验仪器	型号	生产厂家
扫描电子显微镜	VEGA3SBH	TESCAN
磁力搅拌器	HJ-4	常州未来仪器制造有限公司
pH计	pH-902	常州爱德克斯仪器仪表有限公司
ZNCL-GS智能磁力搅拌器	ZNCL-GS240*150	上海予申仪器有限公司
电热鼓风干燥箱	101-2BS	天津宏诺仪器有限公司
优普系列超纯水器	UPH-IV-10T	成都超纯科技有限公司
精密节能电炉	SX2-5-12TP	济南精密科学仪器仪表有限公司
低速大容量离心机	TDL-5-A	上海安亭科学仪器厂
超声波清洗机	QT系列	天津市瑞普电子仪器公司
电子天平	JA5003	上海舜宇恒平科学仪器有限公司
X射线衍射仪	DX-2700	丹东浩圆仪器有限公司

下载: 导出CSV

参考文献(31)

[1]	Xu X, Chen Y, Wan P, et al. Extraction of lithium with functionalized lithium ion-sieves[J]. Progress in Materials Science, 2016,(84):276−313.
[2]	Gruber P W, Medina P A, Keoleian G A, et al. Global lithium availability, a constraint for electric vehicles[J]. Journal of Industrial Ecology, 2011,15(5):760−775. doi: 10.1111/j.1530-9290.2011.00359.x
[3]	Grosjean C, MirandaI P H, Perrin M, et al. Assessment of world lithium resources and consequences of their geographic distribution on the expected development of the electric vehicle industry[J]. Renewable and Sustainable Energy Reviews, 2012,16(3):1735−1744. doi: 10.1016/j.rser.2011.11.023
[4]	Ogawa Y, Koibuchi H, Suto K, et al. Effects of the chemical compositions of salars de Uyuni and Atacama brines on lithium concentration during evaporation[J]. Resource Geology, 2014,4(2):91−101.
[5]	Meshram P, Pandey B D, Mankhand T R. Extraction of lithium from primary and secondary sources by pre-treatment, leaching and separation: a comprehensive review[J]. Hydrometallurgy, 2014,150:192−208. doi: 10.1016/j.hydromet.2014.10.012
[6]	Liu Yuanhui, Deng Tianlong. Progresses on the process and technique of lithium recovery from salt lake brines around the world[J]. World Sci-Tech R & D, 2006,28(5):69−75. (刘元会, 邓天龙. 国内外从盐湖卤水中提锂工艺技术研究进展[J]. 世界科技研究与发展, 2006,28(5):69−75. doi: 10.3969/j.issn.1006-6055.2006.05.010
[7]	Lemaire J, Svecova L, Lagallarde E, et al. Lithium recovery from aqueous solution by sorption/desorption[J]. Hydrometallurgy, 2014,143:1−11. doi: 10.1016/j.hydromet.2013.11.006
[8]	Wu X, Wen Z, Lin B, et al. Sol-gel synthesis and sintering of nano-size Li₂TiO₃ powder[J]. Materials Letters, 2008,62(6−7):837−839. doi: 10.1016/j.matlet.2007.06.073
[9]	Chitrakar R, Makita Y, Ooi K, et al. Synthesis of iron-doped manganese oxides with an ion-sieve property: lithium adsorption from bolivian brine[J]. Industrial & Engineering Chemistry Research, 2014,53(9):3682−3688.
[10]	Sun S Y, Cai L J, Nie X Y, et al. Separation of magnesium and lithium from brine using a desal nanofiltration membrane[J]. Journal of Water Process Engineering, 2015,7:210−217. doi: 10.1016/j.jwpe.2015.06.012
[11]	Song J, Li X M, Zhang Y, et al. Hydrophilic nanoporous ion-exchange membranes as a stabilizing barrier for liquid-liquid membrane extraction of lithium ions[J]. Journal of Membrane Science, 2014,471:372−380. doi: 10.1016/j.memsci.2014.08.010
[12]	Ji Z Y, Chen Q B, Yuan J S, et al. Preliminary study on recovering lithium from high Mg²⁺/Li⁺ ratio brines by electrodialysis[J]. Separation and Purification Technology, 2017,172:168−177. doi: 10.1016/j.seppur.2016.08.006
[13]	Wang L, Meng C G, Ma W. Study on Li⁺ uptake by lithium ion-sieve via the pH techniqu[J]. Colloids & Surfaces A-Physicochemical & Engineering Aspects, 2009,334(1−3):34−39.
[14]	Zhang Q H, Li S, Sun S Y, et al. Lithium selective adsorption on 1-D MnO nanostructure ion-sieve[J]. Advanced Powder Technology, 2009,20(5):432−437. doi: 10.1016/j.apt.2009.02.008
[15]	Bai C, Guo M, Zhang H F, et al. The research progress of extracting lithium from brine by lithium ion sieve[J]. Chemical Industry and Engineering Progress, 2017,36(3):802−809.
[16]	Shi Xichang, Yu Liangliang, Chen Baizhen, et al. Preparation and adsorption property of spinel-type lithium ion-sieve[J]. Journal of Central South University (Science and Technology), 2011,42(8):2198−2203. (石西昌, 余亮良, 陈白珍, 等. 尖晶石型锂离子筛的制备及其吸附性能[J]. 中南大学学报(自然科学版), 2011,42(8):2198−2203.
[17]	Chitrakar R, Kanoh H, Miyai Y, et al. Recovery of lithium from seawater using manganese oxide adsorbent (H_1.6Mn_1.6O₄) derived from Li_1.6Mn_1.6O₄[J]. Industrial & Engineering Chemistry Research, 2001,40(9):2054−2058.
[18]	Zhang L Y, Zhou D L, He G, et al. Synthesis of H₂TiO₃-lithium adsorbent loaded on ceramic foams[J]. Materials Letters, 2015,145:351−354. doi: 10.1016/j.matlet.2015.01.142
[19]	Park K, Benayad A, Kang D, et al. Nitridation-driven conductive Li₄Ti₅O₁₂ for lithium ion batteries[J]. Journal of the American Chemical Society, 2008,130(45):14930−14931. doi: 10.1021/ja806104n
[20]	Xu X, Zhou Y, Fan M, et al. Lithium adsorption performance of a three-dimensional porous H₂TiO₃-type lithium ion-sieve in strong alkaline Bayer liquor[J]. RSC Advances, 2017,7:18883−18891. doi: 10.1039/C7RA01056G
[21]	Nugroho A, Kim S J, Chung K Y, et al. Facile synthesis of nanosized Li₄Ti₅O₁₂ in supercritical water[J]. Electrochemistry Communications, 2011,13(6):650−653. doi: 10.1016/j.elecom.2011.03.037
[22]	Onodera Y, Iwasaki T, Hayashi H, et al. A new inorganic material with high selective adsorbability for Li⁺[J]. Journal of the Ceramic Society of Japan, 1989,97(1129):888−894. doi: 10.2109/jcersj.97.888
[23]	Zhang L F, Chen B Z, Shi X C, et al. Synthesis and adsorption property of H₂TiO₃ type adsorbent[J]. The Chinese Journal of Nonferrous Metals, 2010,20(9):1850−1854.
[24]	Chung W J, Torrejos R E C, Park M J, et al. Continuous lithium mining from aqueous resources by an adsorbent filter with a 3D polymeric nanofiber network infused with ion sieves[J]. Chemical Engineering Journal, 2017,309:49−62. doi: 10.1016/j.cej.2016.09.133
[25]	Deng D H, Wu H, Liao X P, et al. Synthesis of unique mesoporous ZrO₂-carbon fiber from collagen fiber[J]. Microporous and Mesoporous Materials, 2008,116(1−3):705−709. doi: 10.1016/j.micromeso.2008.05.018
[26]	Cai Li. Synthesis and photo-catalytic activity of mesoporous TiO₂fiber using collagen fiber as a template[J]. Journal of Functional Materials, 2013,44(23):3447−3451. (蔡莉. 胶原纤维为模板制备介孔TiO₂纤维及光催化活性研究[J]. 功能材料, 2013,44(23):3447−3451. doi: 10.3969/j.issn.1001-9731.2013.23.020
[27]	Zhang Liyuan, You Yaohui, You Jia, et al. Preparation and photocatalytic performance of fibrous Gd-doped TiO₂ using collagen fiber as template[J]. Journal of Synthetic Crystals, 2019,48(2):312−320. (张理元, 由耀辉, 尤佳, 等. 胶原纤维为模板制备Gd掺杂纤维状二氧化钛及光催化性能研究[J]. 人工晶体学报, 2019,48(2):312−320. doi: 10.3969/j.issn.1000-985X.2019.02.024
[28]	Zhang Bin, Chen Tijun, Wang Lingyun, et al. Study on ultrasonic dispersion of graphene nanoplatelets[J]. Journal of Functional Materials, 2019,50(8):8133−8139. (张斌, 陈体军, 王凌云, 等. 石墨烯纳米片超声分散的研究[J]. 功能材料, 2019,50(8):8133−8139. doi: 10.3969/j.issn.1001-9731.2019.08.019
[29]	Schofield P, Mbugua D M, Pell A N. Analysis of condensed tannins: a review[J]. Animal Feed Science and Technology, 2001,91(1−2):21−40. doi: 10.1016/S0377-8401(01)00228-0
[30]	Shi B, He X Q, Haslam E. Pofyphenol-Gelatin interaction[J]. Journal of American Leather Chemists Association, 1994,89(4):98−104.
[31]	Tao Yuhu. Preparation and properties of triethanolamine modified basalt fiber/natural rubber composites[J]. Science & Technology Vision, 2018,(10):256−258. (陶玉虎. 三乙醇胺改性玄武岩纤维/天然橡胶复合材料的制备及性能研究[J]. 科技视界, 2018,(10):256−258.