以锰结核氨浸渣为主要原料制备介孔玻璃工艺研究
|
摘要
氨浸渣是大洋锰结核经氨浸工艺提取Co、Ni、Cu等有价金属后的粉末状固体残渣,如果不能及时合理地被利用,长期堆放不仅需要大笔维护费用,而且占用大量土地,还会造成环境污染。如果能用氨浸渣为原料,生产介孔玻璃,就能够变废为宝,还可解决环境污染问题。因此,研究以氨浸渣为主要原料制备介孔玻璃的工艺具有潜在的社会与经济效益。
本文首次以大洋锰结核氨浸渣、石英砂、硼砂为原料,采用熔融-熔离-溶解法成功制备了介孔玻璃。玻璃组成位于Na_2O-B_2O_3-SiO_2三元系相图的分相区内,熔融实验温度控制在1250℃～1300℃,恒温时间60min～120min。熔离温度控制在450℃～600℃,恒温480min～1440min。溶解实验分别选择盐酸和硫酸为溶解介质,浓度为0.2mol/L、0.4mol/L和0.6mol/L,溶解温度为70℃和90℃。研究表明,当原料配比为氨浸渣60.0%,石英砂33.5%,硼砂6.5%;熔融温度1250℃;恒温时间120min可以制成不含结晶体颜色均匀的玻璃。研究对比了熔离温度和熔离时间对介孔玻璃性能的影响发现,熔离温度为500℃,熔离时间1440min,可制得孔径比较均匀的介孔玻璃。此外还研究了,溶解介质酸的种类、酸的浓度、溶解温度和溶解时间对样品酸溶率的影响发现,制备介孔玻璃的优化酸溶条件:盐酸的浓度为0.6 mol/L,溶解时间2h,溶解温度90℃。制得样品的孔性能参数为:比表面积18.65m~2/g,平均孔径5.643nm,孔容积0.024ml/g。初步进行了以大洋锰结核氨浸渣、石英砂、硼砂为原料,采用熔融-熔离-溶解法制备介孔玻璃的经济技术评价。本项研究为大洋锰结核氨浸渣的合理利用提供了新的途径和关键技术参数。
The ammonia leaching residue is the residues of manganese nodules after the extraction of Co, Ni, Cu by ammonia leaching process.If could not be reasonablely used in time,long time deposite will spend a lot in maintenance and take up much space,even environmental pollutions.Using ammonia leaching residue as raw materials for mesoporous glass production,will not only reuse the deposite,but can solve the environmental problems.So it is of great benefit to study the process of making mesoporous glass with ammonia leaching residue.
Melting, phase separation and dissolution is used for making mesoporous glass from ammonia leaching residue, SiO2 and borax.
The composition of the glass is in the three phases area of Na_2O- B_2O_3- SiO_2 system .The temperature of melting is controled between 1250 and 1300℃, the time of the same temperature is 60～120min.
Phase separation temperature is between 450 and 600℃,the time is from480min to 1440 min. HCl and H_2SO_4 was used as solvent in the experiment,concentration were 0.2mol/L、0.4mol/L and 0.6mol/L,dissovled tempearature were 70 and 90℃.
The research show that when 60.0% ammonia leaching residue, 33.5% SiO_2 and 6.5% borax are used as raw material, dissovled tempearature is 1250℃for 120min,different well-proportioned color glass without nodules could be made.
Comparations of the effect of melting temperature and time for mesoporous glass showed that when the temperature is 500℃and time is 1440min, well-proportioned mesoporous glass of the same aperture could be made.
Furthur more,the study proved that the kind and concentration of solvent acid,disolved temperature and time will effect the acid losing,and the optimization of making mesoporous glass:the concentration of HCl is 0.6 mol/L,disolved temperature is 90℃and time is 2h.
The structure parameters of the samples are that BET surface area is 18.65m~2/g,Average pore diameters is 5.643nm, and pore volume is0.024ml/g. Economic and technical estimation of the method,which melting, phaseseparation and dissolve is used in making mesoporous glass from ammonia leaching residue, SiO_2 and borax ,were also be introduced in the paper.
本文首次以大洋锰结核氨浸渣、石英砂、硼砂为原料,采用熔融-熔离-溶解法成功制备了介孔玻璃。玻璃组成位于Na_2O-B_2O_3-SiO_2三元系相图的分相区内,熔融实验温度控制在1250℃～1300℃,恒温时间60min～120min。熔离温度控制在450℃～600℃,恒温480min～1440min。溶解实验分别选择盐酸和硫酸为溶解介质,浓度为0.2mol/L、0.4mol/L和0.6mol/L,溶解温度为70℃和90℃。研究表明,当原料配比为氨浸渣60.0%,石英砂33.5%,硼砂6.5%;熔融温度1250℃;恒温时间120min可以制成不含结晶体颜色均匀的玻璃。研究对比了熔离温度和熔离时间对介孔玻璃性能的影响发现,熔离温度为500℃,熔离时间1440min,可制得孔径比较均匀的介孔玻璃。此外还研究了,溶解介质酸的种类、酸的浓度、溶解温度和溶解时间对样品酸溶率的影响发现,制备介孔玻璃的优化酸溶条件:盐酸的浓度为0.6 mol/L,溶解时间2h,溶解温度90℃。制得样品的孔性能参数为:比表面积18.65m~2/g,平均孔径5.643nm,孔容积0.024ml/g。初步进行了以大洋锰结核氨浸渣、石英砂、硼砂为原料,采用熔融-熔离-溶解法制备介孔玻璃的经济技术评价。本项研究为大洋锰结核氨浸渣的合理利用提供了新的途径和关键技术参数。
The ammonia leaching residue is the residues of manganese nodules after the extraction of Co, Ni, Cu by ammonia leaching process.If could not be reasonablely used in time,long time deposite will spend a lot in maintenance and take up much space,even environmental pollutions.Using ammonia leaching residue as raw materials for mesoporous glass production,will not only reuse the deposite,but can solve the environmental problems.So it is of great benefit to study the process of making mesoporous glass with ammonia leaching residue.
Melting, phase separation and dissolution is used for making mesoporous glass from ammonia leaching residue, SiO2 and borax.
The composition of the glass is in the three phases area of Na_2O- B_2O_3- SiO_2 system .The temperature of melting is controled between 1250 and 1300℃, the time of the same temperature is 60～120min.
Phase separation temperature is between 450 and 600℃,the time is from480min to 1440 min. HCl and H_2SO_4 was used as solvent in the experiment,concentration were 0.2mol/L、0.4mol/L and 0.6mol/L,dissovled tempearature were 70 and 90℃.
The research show that when 60.0% ammonia leaching residue, 33.5% SiO_2 and 6.5% borax are used as raw material, dissovled tempearature is 1250℃for 120min,different well-proportioned color glass without nodules could be made.
Comparations of the effect of melting temperature and time for mesoporous glass showed that when the temperature is 500℃and time is 1440min, well-proportioned mesoporous glass of the same aperture could be made.
Furthur more,the study proved that the kind and concentration of solvent acid,disolved temperature and time will effect the acid losing,and the optimization of making mesoporous glass:the concentration of HCl is 0.6 mol/L,disolved temperature is 90℃and time is 2h.
The structure parameters of the samples are that BET surface area is 18.65m~2/g,Average pore diameters is 5.643nm, and pore volume is0.024ml/g. Economic and technical estimation of the method,which melting, phaseseparation and dissolve is used in making mesoporous glass from ammonia leaching residue, SiO_2 and borax ,were also be introduced in the paper.
引文
[1] 黎青, 陈玲燕. 多孔材料的应用与发展[J]. 材料导报, 1995, 9(006): 10～13.
[2] Gibson L J. Cellular Solids[J]. MRS Bulletin(USA), 2003, 28(4): 270～271.
[3] 白青龙, 张春花, 王冀敏. 多孔材料的研究进展[J]. 内蒙古民族大学学报: 自然科学版, 2004, 19(005): 528～531.
[4] 段曦东. 多孔陶瓷的制备, 性能及应用[J]. 陶瓷研究, 1999, 14(003): 12～17.
[5] 张俊彦, 张平, 甘秋兰, et al. 多孔材料代表单元的性质[J]. 工程力学, 2004, 21(002): 124～128.
[6] Yuan H, Kurashina K, de B J, et al. A preliminary study on osteoinduction of two kinds of calcium phosphate ceramics[J]. Biomaterials, 1999, 20(19): 1799～1806.
[7] Li H, Eddaoudi M, O K M. Design and synthesis of an exceptionally stable and highly porous metal-organic framework[J]. Nature, 1999, 402: 276～279.
[8] 汤慧萍, 张正德. 金属多孔材料发展现状[J]. 稀有金属材料与工程, 1997, 26(001): 1～6.
[9] 刘培生, 李铁藩. 多孔金属材料的应用[J]. 功能材料, 2001, 32(001): 12～15.
[10] 王连星, 姚治才. 多孔陶瓷材料[J]. 硅酸盐通报, 1998, 17(001): 41～45.
[11] 刘富德, 陈森凤. 多孔陶瓷材料的发展状况[J]. 材料导报, 2000, 14(006): 33～34.
[12] 王慧, 陈永洁. 多孔陶瓷——绿色功能材料[J]. 中国陶瓷, 2002, 38(003): 6～8.
[13] 张宇民, 韩杰才. 多孔陶瓷材料制备工艺研究进展[J]. 兵器材料科学与工程, 2002, 25(002): 62～67.
[14] 段曦东. 多孔陶瓷的制备, 性能及应用[J]. 陶瓷研究, 1999, 14(003): 12～17.
[15] Saje M, Pan J, Needleman A. Void nucleation effects on shear localization in porous plastic solids[J]. International Journal of Fracture, 1982, 19(3): 163～182.
[16] Kresge C T, Leonowicz M E, Roth W J, et al. Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism[J]. Nature, 1992, 359(6397): 710～712.
[17] Works C G, TREATED BOROSILICATE GLASS. In ; Google Patents: 1938; .
[18] 胥焕岩, 王升高. 多孔玻璃的性质, 用途及制备[J]. 武汉化工学院学报, 2000, 22(001): 40～43.
[19] 王德宪. 多孔玻璃的性质及用途[J]. 玻璃, 1997, 24(006): 32～35.
[20] 黄光锋, 卢安贤. 多孔玻璃应用研究的新进展[J]. 玻璃与搪瓷, 2006, 34(004): 49～52.
[21] 杨南如, 余桂郁. 溶胶—凝胶法的基本原理与过程[J]. 硅酸盐通报, 1993, 12(002): 56～63.
[22] 杨南如, 余桂郁. 溶胶-凝胶法简介[J]. 硅酸盐通报, 1992, 2: 56～63.
[23] 刘世权, 许淑惠. 玻璃粉末的烧结[J]. 玻璃与搪瓷, 1995, 23(005): 34～38.
[24] 刘世权, 卢君强. 影响多孔玻璃孔结构的因素[J]. 硅酸盐通报, 2000, 19(002): 13～15.
[25] 朱新文, 江东亮. 有机泡沫浸渍工艺——一种经济实用的多孔陶瓷制备工艺[J]. 硅酸盐通报, 2000, 19(003): 45～51.
[26] 朱明珍, 刘庆国. 多孔陶瓷材料的制备技术[J]. 材料科学与工程, 1996, 14(003): 33～39.
[27] Zanotti J M, Bellissent-Funel M C, Chen S H. Relaxational dynamics of supercooled water in porous glass[J]. Physical Review E, 1999, 59(3): 3084～3093.
[28] H A, Neumann H B, Schmidt P W, et al. Fractal surface and cluster structure of controlled-pore glasses and Vycor porous glass as revealed by small-angle x-ray and neutron scattering[J]. Physical Review B, 1988, 38(2): 1462～1467.
[29] Holwech I, N B. Dielectric dispersion measurements of salt-water-saturated porous glass[J]. Physical Review B, 1989, 39(17): 12845～12852.
[30] 张云, 管永诗. 大洋锰结核资源的研究现状[J]. 矿产保护与利用, 2000, (006): 39～42.
[31] GLASBY G P. Deep Seabed Mining: Past Failures and Future Prospects[J]. Marine Georesources and Geotechnology, 2002, 20(2): 161～176.
[32] Sollas W J. Report on the Tetractinellida Collected by HMS Challenger During the Years 1873-1876[M]. Johnson Reprint Corp, 1965.
[33] Rosenshield G. Choosing the Right Card: Madness, Gambling, and the Imagination in Pushkin's" The Queen of Spades"[J]. PMLA, 1994, 109(5): 995～1008.
[34] 于留春. 开发利用海洋能源 实现社会持续发展[J]. 梅山科技, 2002, (002): 41～43.
[35] 牛京考. 大洋多金属结核开发研究述评[J]. 中国锰业, 2002, 20(002): 20～26.
[36] 盛桂浓. 大洋多金属结核资源的开发[J]. 中国锰业, 1992, 10(002): 54～56.
[37] 牛京考. 中国对大洋多金属结核研究与开发述评[J]. 中国矿业, 1996, 5(005): 5～6.
[38] 白志民, 蒋训雄. 大洋多金属结核与富钴结壳浸出渣的纳米属性[J]. 科学通报, 2002, 47(011): 869～872.
[39] 简曲. 开发利用大洋资源应作为国家的一项基本资源政策[J]. 中国矿业, 1999, 8(005): 44～46.
[40] 白志民, 文智慧, 常有军, et al. 大洋锰结核氨浸渣制备防锈涂料及其性质[J]. 硅酸盐学报, 2005, 33(5):
[41] 白志民, 常有军, 陈锦, et al. 大洋锰结核氨浸渣作为陶瓷原料的实验研究[J]. 矿物岩石, 2005, : 03.
[42] 刘平, 许淑惠. 玻璃的分相与析晶 (一)[J]. 玻璃与搪瓷, 1994, 22(001): 23～32.
[43] 刘平, 陈显求, 许淑惠. 玻璃的分相与析晶 (二)[J]. 玻璃与搪瓷, 1994, 22(2): 28～32.
[44] 刘平;陈显求;许淑惠. 玻璃的分相与结晶 (三)[J]. 玻璃与搪瓷, 1994, 22(003): 28～32.
[45] 刘平, 许淑惠. 玻璃的分相与结晶 (四)[J]. 玻璃与搪瓷, 1994, 22(004): 36～41.
[46] 刘平, 许淑惠. 玻璃的分相与结晶 (五)[J]. 玻璃与搪瓷, 1994, 22(005): 38～41.
[47] 刘平, 许淑惠. 玻璃的分相与结晶 (六)[J]. 玻璃与搪瓷, 1994, 22(006): 21～23.
[48] 刘平, 陈显求, 许淑惠. 玻璃的分相与析晶 (七)[J]. 玻璃与搪瓷, 1995, 23(1): 31～33.
[49] 刘平, 许淑惠. 玻璃的分相与结晶 (八)[J]. 玻璃与搪瓷, 1995, 23(002): 34～38.
[50] von M I. Struktur und Eigenschaften[J]. :
[51] Pego R L. Front Migration in the Nonlinear Cahn-Hilliard Equation[J]. Proceedings of the Royal Society of London. Series A, Mathematical and Physical Sciences, 1989, 422(1863): 261～278.
[52] AKIKAKOS N, BATES P W, FUSCO G. Slow motion for the Cahn-Hilliard equation in one space dimension[J]. Journal of differential equations, 1991, 90(1): 81～135.
[53] Finson M, Probstein R. A theory of dust comets. 1. Model and equations[J]. The Astrophysical Journal, 1968, 154: 327.
[54] Oxtoby D W, Kashchiev D. A general relation between the nucleation work and the size of the nucleus in multicomponent nucleation[J]. The Journal of Chemical Physics, 1994, 100: 7665.
[55] 陆佩文. 无机材料科学基础[J]. 武汉: 武汉工业大学出版社, 1996, 167: 188.
[56] 曹志峰, 张希艳. 多孔玻璃微珠的研制及其吸附性能研究[J]. 硅酸盐学报, 2002, 30(003): 402～406.
[2] Gibson L J. Cellular Solids[J]. MRS Bulletin(USA), 2003, 28(4): 270～271.
[3] 白青龙, 张春花, 王冀敏. 多孔材料的研究进展[J]. 内蒙古民族大学学报: 自然科学版, 2004, 19(005): 528～531.
[4] 段曦东. 多孔陶瓷的制备, 性能及应用[J]. 陶瓷研究, 1999, 14(003): 12～17.
[5] 张俊彦, 张平, 甘秋兰, et al. 多孔材料代表单元的性质[J]. 工程力学, 2004, 21(002): 124～128.
[6] Yuan H, Kurashina K, de B J, et al. A preliminary study on osteoinduction of two kinds of calcium phosphate ceramics[J]. Biomaterials, 1999, 20(19): 1799～1806.
[7] Li H, Eddaoudi M, O K M. Design and synthesis of an exceptionally stable and highly porous metal-organic framework[J]. Nature, 1999, 402: 276～279.
[8] 汤慧萍, 张正德. 金属多孔材料发展现状[J]. 稀有金属材料与工程, 1997, 26(001): 1～6.
[9] 刘培生, 李铁藩. 多孔金属材料的应用[J]. 功能材料, 2001, 32(001): 12～15.
[10] 王连星, 姚治才. 多孔陶瓷材料[J]. 硅酸盐通报, 1998, 17(001): 41～45.
[11] 刘富德, 陈森凤. 多孔陶瓷材料的发展状况[J]. 材料导报, 2000, 14(006): 33～34.
[12] 王慧, 陈永洁. 多孔陶瓷——绿色功能材料[J]. 中国陶瓷, 2002, 38(003): 6～8.
[13] 张宇民, 韩杰才. 多孔陶瓷材料制备工艺研究进展[J]. 兵器材料科学与工程, 2002, 25(002): 62～67.
[14] 段曦东. 多孔陶瓷的制备, 性能及应用[J]. 陶瓷研究, 1999, 14(003): 12～17.
[15] Saje M, Pan J, Needleman A. Void nucleation effects on shear localization in porous plastic solids[J]. International Journal of Fracture, 1982, 19(3): 163～182.
[16] Kresge C T, Leonowicz M E, Roth W J, et al. Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism[J]. Nature, 1992, 359(6397): 710～712.
[17] Works C G, TREATED BOROSILICATE GLASS. In ; Google Patents: 1938; .
[18] 胥焕岩, 王升高. 多孔玻璃的性质, 用途及制备[J]. 武汉化工学院学报, 2000, 22(001): 40～43.
[19] 王德宪. 多孔玻璃的性质及用途[J]. 玻璃, 1997, 24(006): 32～35.
[20] 黄光锋, 卢安贤. 多孔玻璃应用研究的新进展[J]. 玻璃与搪瓷, 2006, 34(004): 49～52.
[21] 杨南如, 余桂郁. 溶胶—凝胶法的基本原理与过程[J]. 硅酸盐通报, 1993, 12(002): 56～63.
[22] 杨南如, 余桂郁. 溶胶-凝胶法简介[J]. 硅酸盐通报, 1992, 2: 56～63.
[23] 刘世权, 许淑惠. 玻璃粉末的烧结[J]. 玻璃与搪瓷, 1995, 23(005): 34～38.
[24] 刘世权, 卢君强. 影响多孔玻璃孔结构的因素[J]. 硅酸盐通报, 2000, 19(002): 13～15.
[25] 朱新文, 江东亮. 有机泡沫浸渍工艺——一种经济实用的多孔陶瓷制备工艺[J]. 硅酸盐通报, 2000, 19(003): 45～51.
[26] 朱明珍, 刘庆国. 多孔陶瓷材料的制备技术[J]. 材料科学与工程, 1996, 14(003): 33～39.
[27] Zanotti J M, Bellissent-Funel M C, Chen S H. Relaxational dynamics of supercooled water in porous glass[J]. Physical Review E, 1999, 59(3): 3084～3093.
[28] H A, Neumann H B, Schmidt P W, et al. Fractal surface and cluster structure of controlled-pore glasses and Vycor porous glass as revealed by small-angle x-ray and neutron scattering[J]. Physical Review B, 1988, 38(2): 1462～1467.
[29] Holwech I, N B. Dielectric dispersion measurements of salt-water-saturated porous glass[J]. Physical Review B, 1989, 39(17): 12845～12852.
[30] 张云, 管永诗. 大洋锰结核资源的研究现状[J]. 矿产保护与利用, 2000, (006): 39～42.
[31] GLASBY G P. Deep Seabed Mining: Past Failures and Future Prospects[J]. Marine Georesources and Geotechnology, 2002, 20(2): 161～176.
[32] Sollas W J. Report on the Tetractinellida Collected by HMS Challenger During the Years 1873-1876[M]. Johnson Reprint Corp, 1965.
[33] Rosenshield G. Choosing the Right Card: Madness, Gambling, and the Imagination in Pushkin's" The Queen of Spades"[J]. PMLA, 1994, 109(5): 995～1008.
[34] 于留春. 开发利用海洋能源 实现社会持续发展[J]. 梅山科技, 2002, (002): 41～43.
[35] 牛京考. 大洋多金属结核开发研究述评[J]. 中国锰业, 2002, 20(002): 20～26.
[36] 盛桂浓. 大洋多金属结核资源的开发[J]. 中国锰业, 1992, 10(002): 54～56.
[37] 牛京考. 中国对大洋多金属结核研究与开发述评[J]. 中国矿业, 1996, 5(005): 5～6.
[38] 白志民, 蒋训雄. 大洋多金属结核与富钴结壳浸出渣的纳米属性[J]. 科学通报, 2002, 47(011): 869～872.
[39] 简曲. 开发利用大洋资源应作为国家的一项基本资源政策[J]. 中国矿业, 1999, 8(005): 44～46.
[40] 白志民, 文智慧, 常有军, et al. 大洋锰结核氨浸渣制备防锈涂料及其性质[J]. 硅酸盐学报, 2005, 33(5):
[41] 白志民, 常有军, 陈锦, et al. 大洋锰结核氨浸渣作为陶瓷原料的实验研究[J]. 矿物岩石, 2005, : 03.
[42] 刘平, 许淑惠. 玻璃的分相与析晶 (一)[J]. 玻璃与搪瓷, 1994, 22(001): 23～32.
[43] 刘平, 陈显求, 许淑惠. 玻璃的分相与析晶 (二)[J]. 玻璃与搪瓷, 1994, 22(2): 28～32.
[44] 刘平;陈显求;许淑惠. 玻璃的分相与结晶 (三)[J]. 玻璃与搪瓷, 1994, 22(003): 28～32.
[45] 刘平, 许淑惠. 玻璃的分相与结晶 (四)[J]. 玻璃与搪瓷, 1994, 22(004): 36～41.
[46] 刘平, 许淑惠. 玻璃的分相与结晶 (五)[J]. 玻璃与搪瓷, 1994, 22(005): 38～41.
[47] 刘平, 许淑惠. 玻璃的分相与结晶 (六)[J]. 玻璃与搪瓷, 1994, 22(006): 21～23.
[48] 刘平, 陈显求, 许淑惠. 玻璃的分相与析晶 (七)[J]. 玻璃与搪瓷, 1995, 23(1): 31～33.
[49] 刘平, 许淑惠. 玻璃的分相与结晶 (八)[J]. 玻璃与搪瓷, 1995, 23(002): 34～38.
[50] von M I. Struktur und Eigenschaften[J]. :
[51] Pego R L. Front Migration in the Nonlinear Cahn-Hilliard Equation[J]. Proceedings of the Royal Society of London. Series A, Mathematical and Physical Sciences, 1989, 422(1863): 261～278.
[52] AKIKAKOS N, BATES P W, FUSCO G. Slow motion for the Cahn-Hilliard equation in one space dimension[J]. Journal of differential equations, 1991, 90(1): 81～135.
[53] Finson M, Probstein R. A theory of dust comets. 1. Model and equations[J]. The Astrophysical Journal, 1968, 154: 327.
[54] Oxtoby D W, Kashchiev D. A general relation between the nucleation work and the size of the nucleus in multicomponent nucleation[J]. The Journal of Chemical Physics, 1994, 100: 7665.
[55] 陆佩文. 无机材料科学基础[J]. 武汉: 武汉工业大学出版社, 1996, 167: 188.
[56] 曹志峰, 张希艳. 多孔玻璃微珠的研制及其吸附性能研究[J]. 硅酸盐学报, 2002, 30(003): 402～406.