煤系高岭土制备多品种氧化铝和硅质无机填料研究
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摘要
综合运用矿物学、材料学理论知识与地质背景资料,对平朔矿区煤系高岭土的矿物学特征及其成因模式进行了探讨。以煤系高岭土为原料,采用预脱硅碱石灰烧结法工艺成功制备出了多品种氧化铝和硅质无机填料如白炭黑、活性硅酸钙等。对煤系高岭土的热力学性质进行了探讨,考察了活化温度,碱浸反应的碱液浓度、液固比、脱硅温度、pH值等对预脱硅效果的影响。系统研究了熟料烧结、水淬、碳化、干燥、焙烧等工艺条件对脱硅煤系高岭土制备多品种氧化铝的影响,并获得了一套最佳工艺条件参数,在此工艺条件下制备的超细氢氧化铝和高比表面积γ-A103的理化性能均达到或超过了国家标准。详细研究了反应温度及时间、pH值、CO2通气速度、分散剂等对脱硅液制备白炭黑的影响,并对碱浸脱硅液制备的白炭黑和活性硅酸钙进行了表征。以白炭黑和活性硅酸钙为填料制备了橡胶/无机填料复合材料,并对复合材料的硫化性能、力学性能及气体阻隔性能进行表征。研究发现,硅质无机填料改善了复合材料阻隔性能,起到了很好的填充和补强效果。
The coal-bearing kaolin from Pingshuo Opencast Mine Area was analyzed by the theoretical knowledge of mineralogy, material sciences and geological background, and mineralogical characteristic and orgin of the kaolin were discussed. Multiform alumina and inorganic fillers such as silica and activity calcium silicate were successfully prepared by pre-desilication and soda lime sintering method from coal-bearing kaolin. The effect of the activation temperature of coal-bearing kaolin, alkali concentration、the ratio of liquid to solid、activity temperature、pH on the pre-desilication was discussed. The conditions including sintering of clinker、water quenching、 carbonation、drying、calcination affected on the preparation of Multiform alumina from coal-bearing kaolin was system studied, and the reasonable procession parameters was obtained. The physical and chemical properties of the untra-fine aluminum hydroxide and high surface area7-Al2O3prepared under this process conditions meet or exceed national standards. The impact of reaction temperature and time、pH、ventilation speed of CO2、dispersant on the preparation of silica was detailed studied, and the silica and activity calcium silicate prepared from the de-silication solution were characterized. Used silica and activity calcium silicate as the filler, rubber/inorganic filler composites were prepared. The curing properties, mechanical and gas barrier properties of composites materials were characterized, the results indicates that the inorganic fillers improved the gas barrier properties of the composites materials, and played very good filling and reinforcing effect.
The coal-bearing kaolin from Pingshuo Opencast Mine Area was analyzed by the theoretical knowledge of mineralogy, material sciences and geological background, and mineralogical characteristic and orgin of the kaolin were discussed. Multiform alumina and inorganic fillers such as silica and activity calcium silicate were successfully prepared by pre-desilication and soda lime sintering method from coal-bearing kaolin. The effect of the activation temperature of coal-bearing kaolin, alkali concentration、the ratio of liquid to solid、activity temperature、pH on the pre-desilication was discussed. The conditions including sintering of clinker、water quenching、 carbonation、drying、calcination affected on the preparation of Multiform alumina from coal-bearing kaolin was system studied, and the reasonable procession parameters was obtained. The physical and chemical properties of the untra-fine aluminum hydroxide and high surface area7-Al2O3prepared under this process conditions meet or exceed national standards. The impact of reaction temperature and time、pH、ventilation speed of CO2、dispersant on the preparation of silica was detailed studied, and the silica and activity calcium silicate prepared from the de-silication solution were characterized. Used silica and activity calcium silicate as the filler, rubber/inorganic filler composites were prepared. The curing properties, mechanical and gas barrier properties of composites materials were characterized, the results indicates that the inorganic fillers improved the gas barrier properties of the composites materials, and played very good filling and reinforcing effect.
引文
1.许红亮,刘钦甫.我国煤系高岭岩资源特征及加工利用现状[J].中国非金属工业导刊,2003,5：8-13.
2.晏达宇.我国煤系共伴生矿产资源及开发利用的意义[J].煤炭加工与综合利用,2004(6)：44-47.
3.陈福,赵恩录,张文玲等.纳米高岭土的制备方法及应用展望[J].陶瓷,2007,(5)：9.
4.韩炜,陈敬中,严春杰等.高岭土深加工研究方向及其纳米化探讨[J].矿产综合利用,2003,(4)：27-28.
5. Sibel Kahraman, Muserref Onal, Yuksel Sankaya, et al. Characterization of silica polymorphs in kaolins by X-ray diffraction before and after phosphoric acid digestion and thermal treatment[J]. Analytica Chemical Acta,2005,552(1-2):201-206.
6. San Cristobal, Castello R, Martin Luengo M A, et al. Zeolites prepared from calcined and mechanically modified kaolins:A comparative study [J]. Applied Clay Science,2010,49(3):239-246.
7. Franco, F. Ruiz Cruz, M. D. Factors influencing the intercalation degree ('reactivity') of kaolin minerals with potassium acetate, formamide, dimethylsulphoxide and hydrazine [J]. Clay Minerals,2004,39 (2): 193-205
8.袁树来.中国煤系高岭岩(土)及加工利用[M].北京：中国建材工业出版社,2001.
9.程宏飞,刘钦甫,王陆军等.我国高岭十的研究进展[J].化工矿产地质,2008,30(2)：125-128.
10.韩跃新,印万中.矿物材料[M].北京：科学出版社,2006：60-70.
11. Valaskova, M.; Rieder, M.; Matejka, V.; et al., Exfoliation/delamination of kaolinite by low-temperature washing of kaolinite-urea intercalates [J]. Applied Clay Science 2007,35 (1-2):108-118.
12. Pavlidou. S, Papaspyrides C. D, A review on polymer-layered silicate nano-composites [J]. Progress In Polymer Science 2008,33 (12):1119-1198.
13. Wang, Y. Q, Zhang H. F, Wu Y. P, et al. Preparation and properties of natural rubber/rectorite nano-composites [J]. European Polymer Journal 2005,41 (11):2776-2783.
14. Theng, B. K. G. Organo-clay complexes and interactions [J]. Geoderma,2002,109(1-2):161-162.
15. Fripiat J. J, Letellier M, Levitz. P.et al. Interaction of Water with Clay Surfaces [and Discussion]. Philosophical Transactions of the Royal Society of London [J]. Series A, Mathematical and Physical Sciences 1984,311 (1517):287-299.
16. Lagaly G, Barrer R. M, Goulding. K. Clay-Organic Interactions [and Discussion]. Philosophical Transactions of the Royal Society of London [J]. Series A, Mathematical and Physical Sciences 1984,311 (1517):315-332.
17. Jepson W. B. Kaolins:Their Properties and Uses. Philosophical Transactions of the Royal Society of London [J]. Series A, Mathematical and Physical Sciences 1984,311 (1517):411-432.
18. Zhangzhu Lu, Min Ren, Hengbo Yin, et al. Preparation of nanosized anatase TiO2-coated kaolin composites and their pigmentary properties [J]. Powder Technology,2009,196 (2):122-125.
19. Liew Y M, Kamarudin H, Mustafa A M. Processing and characterization of calcined kaolin cement powder [J]. Construction and building Materials,2012,30:794-802.
20. Lagaly G, Introduction:from clay mineral-polymer interactions to clay mineral-polymer nanocomposities [J]. Applied Clay Science 1999,15(1-2):1-9.
21.张先如,孙嘉,许政.PEG在微波诱导下对高岭石插层及剥片的研究[J].无机化学学报,2005,21(9)；]321-1326.
22.韩敏芳.非金属矿物材料制备与工艺[M].北京：化学工业出版社,2004：208-209.
23. Frost R. L. Effect of water on the formamide-intercalation of kaolinite [J]. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy,2000,56:1711-1729.
24.赵杏媛,张有瑜.粘土矿物与粘土矿物分析[M].北京：海洋出版社,1990,108.
25.夏华,李学强,孟祥庆.高岭土/吡啶插层复合物的制备与表征[J].矿物学报,2003,23(3)：216-218.
26.王万军.高岭石有机插层复合物的制备、表征及应用探讨[D].中南大学博士学位论文,2005,1：38.
27.郑直等.中国主要高岭土矿床[M].北京：科技出版社,1987.
28.沈永和.论高岭岩[M].北京：地质出版社,1959.
29.杨雅秀,张乃娴.中国粘土矿物[M].北京：地质出版社,1994,33-43.
30.刘钦甫,张鹏飞.华北晚古生代煤系高岭岩物质组成和成矿机理研究[M].北京：海洋出版社,1997.1-23.
31. Chen P. Y, Lin M. L, Zheng Z. On the origin of the name kaolin and the kaolin deposits of the Kauling and Dazhou areas, Kiangsi, China [J]. Applied Clay Science,1997,12(1-2):1-25.
32.刘钦甫,许红亮,张鹏飞.煤系不同类型高岭岩中高岭石结晶度的划分[J].煤炭学报2000,25(6)：576-580.
33.杨晓杰,刘冬明,楮立孔等.煤系高岭岩成矿机理[J].煤炭学报,2006,(01)85-89.
34.韩冲,李全海.安徽淮北朔里煤矿硬质高岭土矿石特征及自然类型划分[J].安徽地质,2008,18(01)：26-28.
35.郝临山,彭建喜,董秀桃.大同高岭岩煤矸石资源的矿物学研究[J].大同大学学报(自然科学版),2007,04.
36.黄岑丽,袁文峰.河曲—保德矿区煤系高岭岩矿床特征与利用方向[J].中国煤炭地质,2008,20(05)：20-23.
37.张宪良,宋宝祥,任大伟.煤系高岭岩中碳质特性研究[J].中国非金属工业导刊,2009,06：35-37.
38.许红亮,刘钦甫.我国煤系高岭土煅烧研究现状[J].煤炭加工与综合利用,1999,02：30-34.
39.李昌福,刘述宗,孙凤琴等.朔州煤系硬质高岭岩煅烧试验研究[J].矿冶,2002,11(04)：52-58.
40.杨晓昕,王春梅,杨克锐.不同煅烧制度对煅烧高岭土活性的影响[J].山东建材,2006,04：41-46.
41.郑水林,李杨,许霞.入烧原料细度对煅烧高岭土物化性能的影响研究[J].中国粉体技术,2002,8(03)：13-15.
42.胡浩然,谭伟.煅烧高岭土的成分、结构与火山灰活性的关系[J].土木建筑学术文库,2007,08：164-166.
43.赵鸣,李书同,何素芹等.改性煤系高岭土矿粉填充橡胶的结构与性能[J].矿物学报,2006,26(01)：113-117.
44.许红亮,王萌,刘钦甫.煤系高岭十/二甲基亚砜插层复合材料研究[J].功能材料,2010,41(4)620-622.
45.肖曲,管俊芳,高惠民等.宜昌煤系高岭土补强天然橡胶试验研究[J].矿产综合利用,2009,04：20-23.
46. G K Dhaliwal, G J Wilson. Measurement of the unsaturation of butyl rubbers by the iodine index method [J]. Rubber Chem. And Tech,1994,67(4):567-571.
47.程继刚.丁基胶塞的配方设计要点[J].橡胶工业,1995,42(11)：60-67.
48.程先忠,喻雨清,沈上越.煤系高岭土制备医用橡胶填料的技术研究[J].矿产综合利用,2007,4：24-29.
49.王旭,黄锐.中国塑料[M],2000,14(6)：34.
50.王文一,王国全.工程塑料应用[M].2003,3](8)： 15.
51.赫丽华,宁荣吕,孔杰.工程塑料应用[M],2002,30(4)：53.
52.顾圆春,邱桂学,包艳.聚丙烯/弹性体/纳米高岭土三元复合材料的研究[J].塑料工业,2004,32(10)：15-17
53.沈王庆,黄辉.活化煤系高岭土吸附城市生活污水中磷的研究[J].煤炭转化,2011,34(1)：78-82.
54.薛顺来.煤系高岭土脱除噻吩效果的研究[D].天津大学硕士论文,2007.8：11-35。
55.赵振民,杨报礼.用煤系高岭土生粉低压溶出法生产工业硫酸铝的工艺[P].专利号200510022751.4.
56.张诚.煤系高岭岩湿法制聚合氯化铝和高模数液体硅酸钠[P].专利中请号：200410058137.9
57.冯臻.以煤矸石为原料制备铝盐和白炭黑[J].煤炭加工与综合利用,2005,05：32-33.
58.宋恩玉.硬质高岭土生产聚合氯化铝和白炭黑[J].非金属矿,1999,22(03)：28-31.
59.黄小敏,李保民,刘光芬.利用高岭岩(或高岭土)生产聚合氯化铝和白炭黑的研究[J].非金属矿,1991,(1)：30-32
60. Howell PH, A carana, Towne M K. Production of molecular sieve adsorbents from kaolin minerals [P]. Brit. Patent, GB 980891 (A),1965-01-20.
61.蒋荣立,周怀兰,吕小丽等.煤系高岭土合成吸附干燥剂4A分子筛的试验研究[J].中国矿业大学学报,2005,34(6)：793-797.
62.孔德顺,艾德春,李志等.煤矸石合成P型沸石分子筛的研究[J].安徽农业科学,2011,39(11)6320-6321.
63.高俊,高智,简丽等.偏高岭土水热合成沸石晶化行为的研究[J].无机化学学报,2001,17(5)751-754.
64.高俊,简丽,乔淑萍等.煤系高岭土合成洗涤用沸石工艺研究[J].现代化工,1999,19(04)29-3.
65.江露英,吴丽芳,张巍等.煤系高岭土微波合成NaA分子筛干燥剂[J].硅酸盐通报,2010,29(06)：1263-1269.
66.黎水平,吴其胜.煤系高岭土制备碱性分子筛材料[J].材料科学与工程学报,2009,27(02)233-237.
67.吴杰,秦永宁,马智等.由煤系高岭土合成小晶粒NaY分子筛及其应用[J].化学工业与工程,2006,23(01)：18-20.
68.赫军凯,王陆军,刘饮甫等.淮北煤系高岭土作为FCC催化剂载体的矿物学研究[J].矿物学报,2011,31(02)：274-280.
69.任忠胜.单晶相莫来石生产应用试验与性能测试[J].矿石综合利用,2000,25(05)：19-21.
70.徐慧译.高岭土热分解期间莫来石形成的两个阶段[J].国外耐火材料,2004,29(04)：47-52.
71.杜晶,薛群虎,周永生等.高纯煤系高岭土合成莫来石研究[J].非金属矿,2006,29(01)：32-34.
72.倪文,刘凤梅.煤矸石合成莫来石熟料研究[J].矿物岩石,1998,18(04)：38-42
73.吴小贤,房明浩,孙古兴等.用煤系高岭土制备轻质隔热材料的研究[J].人工晶体学报,2009,38(S)：399-403
74.刘明,高立春,徐利华.碳热还原氮化法制备(3-Sialon粉体的研究[J].人工晶体学报.2008.37(5)：1260-1263.
75.符岩,张阳春等.氧化铝厂设计[M].北京：冶金工业出版社,2007：2-3.
76.毕诗文.氧化铝生产工艺[M].北京：化学工业出版社,2005：15-17.
77.张战军.从高铝粉煤灰提取氧化铝等有用资源的研究[D].西北大学博士论文,2007.
78.姚志通.固体废弃物粉煤灰的资源化利用[D].浙江大学博士学位论文,2010.
79.方荣利,陆胜等.利用粉煤灰制备高纯超细氧化铝粉体的研究[J].环境工程,2003,5(21)：40-42.
80. PARK H. C, PARKY J, STEVRENS R. Synthesis of alumina from high purity alum derive from coal fiy ash [J]. Materials science and Engineering,2004,367:166-170.
81.滕英跃,张永锋,白杰等.高铝煤矸石制备超细氧化铝和硅酸钠联产工艺[J].化工进展,2011,30(2)：455-462.
82.蔡晋强,张顶烈.以高铝矸石为原料制取多用途氢氧化铝[J].煤炭加工与综合利用,1997(3)27-311.
83.黄维刚.煤系高岭岩提取氢氧化铝的主要影响因素[J].煤炭加工与综合利用,1997(6)：20-23
84.赵玉福.煤系高岭岩的开发利用一浅谈特种氧化铝的生产及发展前景[J].有色冶炼,1999(2)：26-29
85.王文颖.油页岩灰渣提取铝与纳米氧化铝粉体的制备研究[D].吉林大学硕士学位论文,2008：1-63.
86. Mingzhu Liu, Huaming Yang. Large surface area mesoporous Al2O3 from kaolin:Methodology and characterization [J]. Applied Clay Science,2010(50):554-559.
87. Huaming Yang, Mingzhu Liu, Jing Ouyang. Novel synthesis and characterization of nanosized γ-Al2O3 from kaolin [J]. Applied Clay Science,2010 (47):438-443.
88.冯杰,李勇,刘松等.用高岭十中矿制备纳米氧化铝[J].非金属矿,2010,33(5)：55-57.
89.周竹发,吴铭敏等.利用高岭土制备纳米氧化铝[J].材料科学与工程学报,2008,26(3)：335-338.
90.吴铭敏.高岭十制备纳米氧化铝工艺研究[D].苏州大学硕士学位论文.2009：1-80.
91. Kureti S., Weisweiler W. A new route for the synthesis of high surface area y-aluminium oxide xerogel[J], Applied Catalysis A:General,2002 (225):251-259.
92. Maria Lucia Pereira Antunes, Helena de Souza Santos, Persio de Souza Santos.Characterization of the aluminum hydroxide microcrystals formed in some alcohol-water solutions [J]. Materials Chemistry and Physics,2002(76):243-249.
93. Vaidya S.D, Thakkar N.V. Effect of temperature, pH and ageing time on hydration of rho alumina by studying phase composition and surface properties of transition alumina obtained after thermal dehydration [J]. Materials Letters,2001(51):295-300.
94.薛茹君.煤系高岭岩预脱硅烧结法提取氧化铝[J].非金属矿,2003,26(5)：17-20.
95.薛茹君,朱克亮.煤系高岭岩脱硅技术[J].非金属矿,2000,23(6)：9-11.
96.罗劲松,胡大千,冯红艳等.通化地区煤系高岭岩制备纳米级a-Al2O3[J].非金属矿,2003,26(2)：20-21.
100.任根宽,张克俭.石灰烧结法从煤系高岭土提取氧化铝的研究[J].轻金属,2010,12：21-24.
101.任根宽,张克俭.煤矸石提取氧化铝工艺研究[J].无机盐工业,2010,42(8)：54-56.
102.高孟华,公明明,王吉晶等.煤矸石的活化及氧化铝提取[J].中国矿业,2007,16(6)：87-91.
103. Aidong Tang, Linna Su, Chuanchang Li. Effect of dry grinding on the physicochemical properties of silica materials prepared from kaolin residue[J]. Powder Technology,2012 (218):86-89.
104. Temuujin J, Burmaa G, Amgalan J.et. al. MacKenzie, Preparation of porous silica from mechanically activated kaolinite[J]. Journal of Porous Materials,2001,8 (3):233-238.
105. Wattanasiriwech S, Wattanasiriwech D, Svasti J. Production of amorphous silica nano-particles from rice straw with microbial hydrolysis pre-treatment [J]. Journal of Non-Crystalline Solids,2010(356): 1228-1232.
106.张庆军,莫文玲,王古乐.沉淀法制备纳米白炭黑的结构及性质的研究[J].硅酸盐通报,2005(4)：118-120.
107.刘欣梅,潘正鸿,李国等.用煤系高岭土制取白炭黑的研究[J].石油大学学报(自然科学版),2005,25(2)：121-125.
108.张其春,叶巧明.高岭土煅烧制白炭黑[J].应用化学,1999,16(5)：91-93.
109.冯杰,周竹发,吴铭敏,何琴等.高岭土制备超细白炭黑的研究[J].化工新型材料,2007,35(11)：73-75.
110.赵增立,高峰,张济宇等.煤系高岭岩酸法制取白炭黑[J].煤化工,1999,(1)：29-33.
111. J. TEMUUJIN, G. BURMAA, J. AMGALAN..Preparation of Porous Silica from Mechanically Activated Kaolinite[J]. Journal of Porous Materials,2001(8):233-238.
112.彭小芹,顾淑英,黄涛等.快速硫化硅橡胶的制备研究[J].功能材料,2010,41(10)：1820-1823.
113.彭小芹,顾淑英,黄涛等.水化硅酸钙粉体对硅橡胶的补强作用[J].土木建筑与环境工程,2010,5(10)：109-114.
114.彭小芹.合成水化硅酸盐纳米粉体胶凝材料研究[D].重庆大学博十论文,2004：1-90.
115.彭小芹,杨巧,黄滔等.水化硅酸钙超细粉体微观结构分析[J].沈阳建筑大学学报(自然科学版),2008,24(05)：823-828.
116.叶家元.水化硅酸钙的微观结构特征及其结构模拟[D].中国建筑科学研究总院硕士论文,2007：5.
117.伍泽广,石松林,刘饮甫.煤系高岭土制备微孔硅酸钙[J].金属矿山,2011,415(01)：162-164.
118.伍泽广,石松林,刘钦甫.微乳法制备纳米硅酸钙粉体[J].矿物学报,2010(S)：126-127.
119.张锐.现代材料分析方法[M].北京：化学工业出版社,2007.
120.张伦和.铝土矿资源合理开发与利用[J].轻金属,2012(2)：3-7.
121.王祝堂.近年米欧亚非大陆铝十矿与氧化铝工业发展概览[J].世界有色金属,2009(1)：76-79.
122.陈祺,关慧勤,熊慧.世界铝工业资源—铝土矿、氧化铝开发利用情况[J].矿业与投资,2007(1)：27-33.
123. Jin-Ha Lee,Sung-Churl Choi,Dong-Sik Bae,Kyong-Sop Han. Synthesis and microstructure of silica-doped alumina composite membrane by sol-gel process [J], Journal of Materials Science Letters,1999, 18(17):1367-1369.
124. Bukaemskii A. A, Avramenko. S. S, Tarasova L. S. Ultrafine α-Al2O3 Explosive Method of Synthesis and Properties [J]. Combustion, Explosion, and Shock Waves,2002,38(4)::478-483.
125.陈胜福,黄坚,李建文.多品种氧化铝开发进展、动向及市场现状[J].材料导报,2006,20(7)：22-26.
126.张文豪.我国多品种氧化铝生产的发展[J].有色金属工业,2004,9：54-55.
127.张秋,杨云峰,王海平等.白炭黑的制备研究进展[J].中国粉体工业,2007,6：12-14.
128.罗地亚扩大欧美白炭黑产能[J].中国粉体工业,2011,2：36.
129.扬子江.罗地亚高分散性白炭黑产能增长40%[J].世界橡胶工业,2011.3：41.
130. Strφm R. A, Masmoudi Y, Rigacci A. Strengthening and aging of wet silica gels for up-scaling of aerogel preparation [J]. Journal Sol-Gel Science and Technology, (2007) 41:291-298.
129. Wang Lijiu, Zhao Shanyu. Synthesis and Characteristics of Mesoporous Silica Aerogels with one step Solvent Exchange/Surface Modification [J]. Journal of Wuhan University of Technolotgy-Mater.2009, 8:613-618.
130.王志,毕诗文,杨毅宏等.溶液质量浓度对铝酸钠溶液碳酸化分解的影响[J].东北大学学报,2002,23(6)：560-563.
130. Li H, Addai M J, Thomas J C, et al. The influence of Al(III) super-saturation and NaOH concentration on the rate of crystallization of A1(OH)3 precursor particles from sodium aluminate solutions [J]. Colloid and Interface Science,2005,286:511-519.
131.陈智连.从CFB灰中提取超细氢氧化铝及氧化铝的工艺研究[D].吉林大学硕士学位论文,2009:32-34.
132. Audet D.R, Laroeque J.E. Development of model for Precipitation of productivity of alumina hydrate precipitation[A].Light Metals [C].Penisywania:Metal lurgical Soc of AIME,1989:21-31
133.程斌,于运花,黄玉强.填料手册[M].北京：中国石化出版社,2002.
134. Raos G, MorenoM, Elli S-Computational expermi ents on filled rubber viscoelasticity:What is the role of particle-particle interac-tions [J]·Macromolecules,2006,39(19):6744-6751.
135. WagnerH D, VaiaR A·Nanocomposites:Issues at the inter-face [J]. MaterialsToday,2004,7(11):38-42.
136.朱玉荪,孙志斌.沉淀法白炭黑的生产现状和市场发展趋势[J].橡胶科技市场,2009,11：5-7
137.徐世传.我国无机填料的生产和应用概况[J].橡胶科技市场,2009,23：5-11.
138. Qinfu Liu, Yude Zhang, Hongliang Xu. Properties of vulcanized rubber nanocomposites filled with nanokaolin and precipitated silica [J]. Applied Clay Science,2008,42 (1-2):232-237.
139.沈鑫远,李祖明,华建坤等.天然橡胶纳米复合材料的制备方法和技术研究进展[J].黑龙江科技信息,2011(08)：44.
140.王小萍,贾德民,陈玉坤.天然橡胶/蒙脱土纳米复合材料结构和性能的研究[M].北京：化学工业出版社,2005：24-26.
141. Suzuki N, Ito M, Yatsuyanagi F-Reinforcement effect of MAA on nano-CaCO3-filled EPDM vulcanizates and possible mechanism [J]. Polymer,2005,46:193-201.
142. Jeon H S, Rameshwaram J K, et al. Characterization of polyisoprene-clay nanocomposites prepared by solution blengding[J]. Polymer.2003,44(19):5749-5758.
143. Choi S S. Difference in bound rubber formation of silica and carbon black with styrene-butadiene rubber.Polym Adv Technol,2002,13(6):466-474.
145. Gert Heinrich, Manfred Kluppel, Thomes A Vilgis. Rein-forcement of elastomers [J].Current Opinionin Solid State and Materials Science,2002, (6):195-203.
146. Choi S S, Park B H,Song Hanjong. Influence of filler typeand content on properties of styrene-butadiene rubber (SBR) compound reinforced with carbon black or silica[J]. PolymAdv Technol,2004,15 (3): 122-127.
147.贾超,卢咏来,张立群.不同形态纳米填料增强硅橡胶复合材料的研究进展[J].合成橡胶工业,2011,34(2)：154-159.
148.赵国璋.橡胶基纳米复合材料制备及性能研究[D].上海大学博士学位论文,2011.
149.干文涛.天然橡胶/蒙脱土纳米复合材料的阻隔性及相关性能研究[D].华南理工大学博士学位论文,
2.晏达宇.我国煤系共伴生矿产资源及开发利用的意义[J].煤炭加工与综合利用,2004(6)：44-47.
3.陈福,赵恩录,张文玲等.纳米高岭土的制备方法及应用展望[J].陶瓷,2007,(5)：9.
4.韩炜,陈敬中,严春杰等.高岭土深加工研究方向及其纳米化探讨[J].矿产综合利用,2003,(4)：27-28.
5. Sibel Kahraman, Muserref Onal, Yuksel Sankaya, et al. Characterization of silica polymorphs in kaolins by X-ray diffraction before and after phosphoric acid digestion and thermal treatment[J]. Analytica Chemical Acta,2005,552(1-2):201-206.
6. San Cristobal, Castello R, Martin Luengo M A, et al. Zeolites prepared from calcined and mechanically modified kaolins:A comparative study [J]. Applied Clay Science,2010,49(3):239-246.
7. Franco, F. Ruiz Cruz, M. D. Factors influencing the intercalation degree ('reactivity') of kaolin minerals with potassium acetate, formamide, dimethylsulphoxide and hydrazine [J]. Clay Minerals,2004,39 (2): 193-205
8.袁树来.中国煤系高岭岩(土)及加工利用[M].北京：中国建材工业出版社,2001.
9.程宏飞,刘钦甫,王陆军等.我国高岭十的研究进展[J].化工矿产地质,2008,30(2)：125-128.
10.韩跃新,印万中.矿物材料[M].北京：科学出版社,2006：60-70.
11. Valaskova, M.; Rieder, M.; Matejka, V.; et al., Exfoliation/delamination of kaolinite by low-temperature washing of kaolinite-urea intercalates [J]. Applied Clay Science 2007,35 (1-2):108-118.
12. Pavlidou. S, Papaspyrides C. D, A review on polymer-layered silicate nano-composites [J]. Progress In Polymer Science 2008,33 (12):1119-1198.
13. Wang, Y. Q, Zhang H. F, Wu Y. P, et al. Preparation and properties of natural rubber/rectorite nano-composites [J]. European Polymer Journal 2005,41 (11):2776-2783.
14. Theng, B. K. G. Organo-clay complexes and interactions [J]. Geoderma,2002,109(1-2):161-162.
15. Fripiat J. J, Letellier M, Levitz. P.et al. Interaction of Water with Clay Surfaces [and Discussion]. Philosophical Transactions of the Royal Society of London [J]. Series A, Mathematical and Physical Sciences 1984,311 (1517):287-299.
16. Lagaly G, Barrer R. M, Goulding. K. Clay-Organic Interactions [and Discussion]. Philosophical Transactions of the Royal Society of London [J]. Series A, Mathematical and Physical Sciences 1984,311 (1517):315-332.
17. Jepson W. B. Kaolins:Their Properties and Uses. Philosophical Transactions of the Royal Society of London [J]. Series A, Mathematical and Physical Sciences 1984,311 (1517):411-432.
18. Zhangzhu Lu, Min Ren, Hengbo Yin, et al. Preparation of nanosized anatase TiO2-coated kaolin composites and their pigmentary properties [J]. Powder Technology,2009,196 (2):122-125.
19. Liew Y M, Kamarudin H, Mustafa A M. Processing and characterization of calcined kaolin cement powder [J]. Construction and building Materials,2012,30:794-802.
20. Lagaly G, Introduction:from clay mineral-polymer interactions to clay mineral-polymer nanocomposities [J]. Applied Clay Science 1999,15(1-2):1-9.
21.张先如,孙嘉,许政.PEG在微波诱导下对高岭石插层及剥片的研究[J].无机化学学报,2005,21(9)；]321-1326.
22.韩敏芳.非金属矿物材料制备与工艺[M].北京：化学工业出版社,2004：208-209.
23. Frost R. L. Effect of water on the formamide-intercalation of kaolinite [J]. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy,2000,56:1711-1729.
24.赵杏媛,张有瑜.粘土矿物与粘土矿物分析[M].北京：海洋出版社,1990,108.
25.夏华,李学强,孟祥庆.高岭土/吡啶插层复合物的制备与表征[J].矿物学报,2003,23(3)：216-218.
26.王万军.高岭石有机插层复合物的制备、表征及应用探讨[D].中南大学博士学位论文,2005,1：38.
27.郑直等.中国主要高岭土矿床[M].北京：科技出版社,1987.
28.沈永和.论高岭岩[M].北京：地质出版社,1959.
29.杨雅秀,张乃娴.中国粘土矿物[M].北京：地质出版社,1994,33-43.
30.刘钦甫,张鹏飞.华北晚古生代煤系高岭岩物质组成和成矿机理研究[M].北京：海洋出版社,1997.1-23.
31. Chen P. Y, Lin M. L, Zheng Z. On the origin of the name kaolin and the kaolin deposits of the Kauling and Dazhou areas, Kiangsi, China [J]. Applied Clay Science,1997,12(1-2):1-25.
32.刘钦甫,许红亮,张鹏飞.煤系不同类型高岭岩中高岭石结晶度的划分[J].煤炭学报2000,25(6)：576-580.
33.杨晓杰,刘冬明,楮立孔等.煤系高岭岩成矿机理[J].煤炭学报,2006,(01)85-89.
34.韩冲,李全海.安徽淮北朔里煤矿硬质高岭土矿石特征及自然类型划分[J].安徽地质,2008,18(01)：26-28.
35.郝临山,彭建喜,董秀桃.大同高岭岩煤矸石资源的矿物学研究[J].大同大学学报(自然科学版),2007,04.
36.黄岑丽,袁文峰.河曲—保德矿区煤系高岭岩矿床特征与利用方向[J].中国煤炭地质,2008,20(05)：20-23.
37.张宪良,宋宝祥,任大伟.煤系高岭岩中碳质特性研究[J].中国非金属工业导刊,2009,06：35-37.
38.许红亮,刘钦甫.我国煤系高岭土煅烧研究现状[J].煤炭加工与综合利用,1999,02：30-34.
39.李昌福,刘述宗,孙凤琴等.朔州煤系硬质高岭岩煅烧试验研究[J].矿冶,2002,11(04)：52-58.
40.杨晓昕,王春梅,杨克锐.不同煅烧制度对煅烧高岭土活性的影响[J].山东建材,2006,04：41-46.
41.郑水林,李杨,许霞.入烧原料细度对煅烧高岭土物化性能的影响研究[J].中国粉体技术,2002,8(03)：13-15.
42.胡浩然,谭伟.煅烧高岭土的成分、结构与火山灰活性的关系[J].土木建筑学术文库,2007,08：164-166.
43.赵鸣,李书同,何素芹等.改性煤系高岭土矿粉填充橡胶的结构与性能[J].矿物学报,2006,26(01)：113-117.
44.许红亮,王萌,刘钦甫.煤系高岭十/二甲基亚砜插层复合材料研究[J].功能材料,2010,41(4)620-622.
45.肖曲,管俊芳,高惠民等.宜昌煤系高岭土补强天然橡胶试验研究[J].矿产综合利用,2009,04：20-23.
46. G K Dhaliwal, G J Wilson. Measurement of the unsaturation of butyl rubbers by the iodine index method [J]. Rubber Chem. And Tech,1994,67(4):567-571.
47.程继刚.丁基胶塞的配方设计要点[J].橡胶工业,1995,42(11)：60-67.
48.程先忠,喻雨清,沈上越.煤系高岭土制备医用橡胶填料的技术研究[J].矿产综合利用,2007,4：24-29.
49.王旭,黄锐.中国塑料[M],2000,14(6)：34.
50.王文一,王国全.工程塑料应用[M].2003,3](8)： 15.
51.赫丽华,宁荣吕,孔杰.工程塑料应用[M],2002,30(4)：53.
52.顾圆春,邱桂学,包艳.聚丙烯/弹性体/纳米高岭土三元复合材料的研究[J].塑料工业,2004,32(10)：15-17
53.沈王庆,黄辉.活化煤系高岭土吸附城市生活污水中磷的研究[J].煤炭转化,2011,34(1)：78-82.
54.薛顺来.煤系高岭土脱除噻吩效果的研究[D].天津大学硕士论文,2007.8：11-35。
55.赵振民,杨报礼.用煤系高岭土生粉低压溶出法生产工业硫酸铝的工艺[P].专利号200510022751.4.
56.张诚.煤系高岭岩湿法制聚合氯化铝和高模数液体硅酸钠[P].专利中请号：200410058137.9
57.冯臻.以煤矸石为原料制备铝盐和白炭黑[J].煤炭加工与综合利用,2005,05：32-33.
58.宋恩玉.硬质高岭土生产聚合氯化铝和白炭黑[J].非金属矿,1999,22(03)：28-31.
59.黄小敏,李保民,刘光芬.利用高岭岩(或高岭土)生产聚合氯化铝和白炭黑的研究[J].非金属矿,1991,(1)：30-32
60. Howell PH, A carana, Towne M K. Production of molecular sieve adsorbents from kaolin minerals [P]. Brit. Patent, GB 980891 (A),1965-01-20.
61.蒋荣立,周怀兰,吕小丽等.煤系高岭土合成吸附干燥剂4A分子筛的试验研究[J].中国矿业大学学报,2005,34(6)：793-797.
62.孔德顺,艾德春,李志等.煤矸石合成P型沸石分子筛的研究[J].安徽农业科学,2011,39(11)6320-6321.
63.高俊,高智,简丽等.偏高岭土水热合成沸石晶化行为的研究[J].无机化学学报,2001,17(5)751-754.
64.高俊,简丽,乔淑萍等.煤系高岭土合成洗涤用沸石工艺研究[J].现代化工,1999,19(04)29-3.
65.江露英,吴丽芳,张巍等.煤系高岭土微波合成NaA分子筛干燥剂[J].硅酸盐通报,2010,29(06)：1263-1269.
66.黎水平,吴其胜.煤系高岭土制备碱性分子筛材料[J].材料科学与工程学报,2009,27(02)233-237.
67.吴杰,秦永宁,马智等.由煤系高岭土合成小晶粒NaY分子筛及其应用[J].化学工业与工程,2006,23(01)：18-20.
68.赫军凯,王陆军,刘饮甫等.淮北煤系高岭土作为FCC催化剂载体的矿物学研究[J].矿物学报,2011,31(02)：274-280.
69.任忠胜.单晶相莫来石生产应用试验与性能测试[J].矿石综合利用,2000,25(05)：19-21.
70.徐慧译.高岭土热分解期间莫来石形成的两个阶段[J].国外耐火材料,2004,29(04)：47-52.
71.杜晶,薛群虎,周永生等.高纯煤系高岭土合成莫来石研究[J].非金属矿,2006,29(01)：32-34.
72.倪文,刘凤梅.煤矸石合成莫来石熟料研究[J].矿物岩石,1998,18(04)：38-42
73.吴小贤,房明浩,孙古兴等.用煤系高岭土制备轻质隔热材料的研究[J].人工晶体学报,2009,38(S)：399-403
74.刘明,高立春,徐利华.碳热还原氮化法制备(3-Sialon粉体的研究[J].人工晶体学报.2008.37(5)：1260-1263.
75.符岩,张阳春等.氧化铝厂设计[M].北京：冶金工业出版社,2007：2-3.
76.毕诗文.氧化铝生产工艺[M].北京：化学工业出版社,2005：15-17.
77.张战军.从高铝粉煤灰提取氧化铝等有用资源的研究[D].西北大学博士论文,2007.
78.姚志通.固体废弃物粉煤灰的资源化利用[D].浙江大学博士学位论文,2010.
79.方荣利,陆胜等.利用粉煤灰制备高纯超细氧化铝粉体的研究[J].环境工程,2003,5(21)：40-42.
80. PARK H. C, PARKY J, STEVRENS R. Synthesis of alumina from high purity alum derive from coal fiy ash [J]. Materials science and Engineering,2004,367:166-170.
81.滕英跃,张永锋,白杰等.高铝煤矸石制备超细氧化铝和硅酸钠联产工艺[J].化工进展,2011,30(2)：455-462.
82.蔡晋强,张顶烈.以高铝矸石为原料制取多用途氢氧化铝[J].煤炭加工与综合利用,1997(3)27-311.
83.黄维刚.煤系高岭岩提取氢氧化铝的主要影响因素[J].煤炭加工与综合利用,1997(6)：20-23
84.赵玉福.煤系高岭岩的开发利用一浅谈特种氧化铝的生产及发展前景[J].有色冶炼,1999(2)：26-29
85.王文颖.油页岩灰渣提取铝与纳米氧化铝粉体的制备研究[D].吉林大学硕士学位论文,2008：1-63.
86. Mingzhu Liu, Huaming Yang. Large surface area mesoporous Al2O3 from kaolin:Methodology and characterization [J]. Applied Clay Science,2010(50):554-559.
87. Huaming Yang, Mingzhu Liu, Jing Ouyang. Novel synthesis and characterization of nanosized γ-Al2O3 from kaolin [J]. Applied Clay Science,2010 (47):438-443.
88.冯杰,李勇,刘松等.用高岭十中矿制备纳米氧化铝[J].非金属矿,2010,33(5)：55-57.
89.周竹发,吴铭敏等.利用高岭土制备纳米氧化铝[J].材料科学与工程学报,2008,26(3)：335-338.
90.吴铭敏.高岭十制备纳米氧化铝工艺研究[D].苏州大学硕士学位论文.2009：1-80.
91. Kureti S., Weisweiler W. A new route for the synthesis of high surface area y-aluminium oxide xerogel[J], Applied Catalysis A:General,2002 (225):251-259.
92. Maria Lucia Pereira Antunes, Helena de Souza Santos, Persio de Souza Santos.Characterization of the aluminum hydroxide microcrystals formed in some alcohol-water solutions [J]. Materials Chemistry and Physics,2002(76):243-249.
93. Vaidya S.D, Thakkar N.V. Effect of temperature, pH and ageing time on hydration of rho alumina by studying phase composition and surface properties of transition alumina obtained after thermal dehydration [J]. Materials Letters,2001(51):295-300.
94.薛茹君.煤系高岭岩预脱硅烧结法提取氧化铝[J].非金属矿,2003,26(5)：17-20.
95.薛茹君,朱克亮.煤系高岭岩脱硅技术[J].非金属矿,2000,23(6)：9-11.
96.罗劲松,胡大千,冯红艳等.通化地区煤系高岭岩制备纳米级a-Al2O3[J].非金属矿,2003,26(2)：20-21.
100.任根宽,张克俭.石灰烧结法从煤系高岭土提取氧化铝的研究[J].轻金属,2010,12：21-24.
101.任根宽,张克俭.煤矸石提取氧化铝工艺研究[J].无机盐工业,2010,42(8)：54-56.
102.高孟华,公明明,王吉晶等.煤矸石的活化及氧化铝提取[J].中国矿业,2007,16(6)：87-91.
103. Aidong Tang, Linna Su, Chuanchang Li. Effect of dry grinding on the physicochemical properties of silica materials prepared from kaolin residue[J]. Powder Technology,2012 (218):86-89.
104. Temuujin J, Burmaa G, Amgalan J.et. al. MacKenzie, Preparation of porous silica from mechanically activated kaolinite[J]. Journal of Porous Materials,2001,8 (3):233-238.
105. Wattanasiriwech S, Wattanasiriwech D, Svasti J. Production of amorphous silica nano-particles from rice straw with microbial hydrolysis pre-treatment [J]. Journal of Non-Crystalline Solids,2010(356): 1228-1232.
106.张庆军,莫文玲,王古乐.沉淀法制备纳米白炭黑的结构及性质的研究[J].硅酸盐通报,2005(4)：118-120.
107.刘欣梅,潘正鸿,李国等.用煤系高岭土制取白炭黑的研究[J].石油大学学报(自然科学版),2005,25(2)：121-125.
108.张其春,叶巧明.高岭土煅烧制白炭黑[J].应用化学,1999,16(5)：91-93.
109.冯杰,周竹发,吴铭敏,何琴等.高岭土制备超细白炭黑的研究[J].化工新型材料,2007,35(11)：73-75.
110.赵增立,高峰,张济宇等.煤系高岭岩酸法制取白炭黑[J].煤化工,1999,(1)：29-33.
111. J. TEMUUJIN, G. BURMAA, J. AMGALAN..Preparation of Porous Silica from Mechanically Activated Kaolinite[J]. Journal of Porous Materials,2001(8):233-238.
112.彭小芹,顾淑英,黄涛等.快速硫化硅橡胶的制备研究[J].功能材料,2010,41(10)：1820-1823.
113.彭小芹,顾淑英,黄涛等.水化硅酸钙粉体对硅橡胶的补强作用[J].土木建筑与环境工程,2010,5(10)：109-114.
114.彭小芹.合成水化硅酸盐纳米粉体胶凝材料研究[D].重庆大学博十论文,2004：1-90.
115.彭小芹,杨巧,黄滔等.水化硅酸钙超细粉体微观结构分析[J].沈阳建筑大学学报(自然科学版),2008,24(05)：823-828.
116.叶家元.水化硅酸钙的微观结构特征及其结构模拟[D].中国建筑科学研究总院硕士论文,2007：5.
117.伍泽广,石松林,刘饮甫.煤系高岭土制备微孔硅酸钙[J].金属矿山,2011,415(01)：162-164.
118.伍泽广,石松林,刘钦甫.微乳法制备纳米硅酸钙粉体[J].矿物学报,2010(S)：126-127.
119.张锐.现代材料分析方法[M].北京：化学工业出版社,2007.
120.张伦和.铝土矿资源合理开发与利用[J].轻金属,2012(2)：3-7.
121.王祝堂.近年米欧亚非大陆铝十矿与氧化铝工业发展概览[J].世界有色金属,2009(1)：76-79.
122.陈祺,关慧勤,熊慧.世界铝工业资源—铝土矿、氧化铝开发利用情况[J].矿业与投资,2007(1)：27-33.
123. Jin-Ha Lee,Sung-Churl Choi,Dong-Sik Bae,Kyong-Sop Han. Synthesis and microstructure of silica-doped alumina composite membrane by sol-gel process [J], Journal of Materials Science Letters,1999, 18(17):1367-1369.
124. Bukaemskii A. A, Avramenko. S. S, Tarasova L. S. Ultrafine α-Al2O3 Explosive Method of Synthesis and Properties [J]. Combustion, Explosion, and Shock Waves,2002,38(4)::478-483.
125.陈胜福,黄坚,李建文.多品种氧化铝开发进展、动向及市场现状[J].材料导报,2006,20(7)：22-26.
126.张文豪.我国多品种氧化铝生产的发展[J].有色金属工业,2004,9：54-55.
127.张秋,杨云峰,王海平等.白炭黑的制备研究进展[J].中国粉体工业,2007,6：12-14.
128.罗地亚扩大欧美白炭黑产能[J].中国粉体工业,2011,2：36.
129.扬子江.罗地亚高分散性白炭黑产能增长40%[J].世界橡胶工业,2011.3：41.
130. Strφm R. A, Masmoudi Y, Rigacci A. Strengthening and aging of wet silica gels for up-scaling of aerogel preparation [J]. Journal Sol-Gel Science and Technology, (2007) 41:291-298.
129. Wang Lijiu, Zhao Shanyu. Synthesis and Characteristics of Mesoporous Silica Aerogels with one step Solvent Exchange/Surface Modification [J]. Journal of Wuhan University of Technolotgy-Mater.2009, 8:613-618.
130.王志,毕诗文,杨毅宏等.溶液质量浓度对铝酸钠溶液碳酸化分解的影响[J].东北大学学报,2002,23(6)：560-563.
130. Li H, Addai M J, Thomas J C, et al. The influence of Al(III) super-saturation and NaOH concentration on the rate of crystallization of A1(OH)3 precursor particles from sodium aluminate solutions [J]. Colloid and Interface Science,2005,286:511-519.
131.陈智连.从CFB灰中提取超细氢氧化铝及氧化铝的工艺研究[D].吉林大学硕士学位论文,2009:32-34.
132. Audet D.R, Laroeque J.E. Development of model for Precipitation of productivity of alumina hydrate precipitation[A].Light Metals [C].Penisywania:Metal lurgical Soc of AIME,1989:21-31
133.程斌,于运花,黄玉强.填料手册[M].北京：中国石化出版社,2002.
134. Raos G, MorenoM, Elli S-Computational expermi ents on filled rubber viscoelasticity:What is the role of particle-particle interac-tions [J]·Macromolecules,2006,39(19):6744-6751.
135. WagnerH D, VaiaR A·Nanocomposites:Issues at the inter-face [J]. MaterialsToday,2004,7(11):38-42.
136.朱玉荪,孙志斌.沉淀法白炭黑的生产现状和市场发展趋势[J].橡胶科技市场,2009,11：5-7
137.徐世传.我国无机填料的生产和应用概况[J].橡胶科技市场,2009,23：5-11.
138. Qinfu Liu, Yude Zhang, Hongliang Xu. Properties of vulcanized rubber nanocomposites filled with nanokaolin and precipitated silica [J]. Applied Clay Science,2008,42 (1-2):232-237.
139.沈鑫远,李祖明,华建坤等.天然橡胶纳米复合材料的制备方法和技术研究进展[J].黑龙江科技信息,2011(08)：44.
140.王小萍,贾德民,陈玉坤.天然橡胶/蒙脱土纳米复合材料结构和性能的研究[M].北京：化学工业出版社,2005：24-26.
141. Suzuki N, Ito M, Yatsuyanagi F-Reinforcement effect of MAA on nano-CaCO3-filled EPDM vulcanizates and possible mechanism [J]. Polymer,2005,46:193-201.
142. Jeon H S, Rameshwaram J K, et al. Characterization of polyisoprene-clay nanocomposites prepared by solution blengding[J]. Polymer.2003,44(19):5749-5758.
143. Choi S S. Difference in bound rubber formation of silica and carbon black with styrene-butadiene rubber.Polym Adv Technol,2002,13(6):466-474.
145. Gert Heinrich, Manfred Kluppel, Thomes A Vilgis. Rein-forcement of elastomers [J].Current Opinionin Solid State and Materials Science,2002, (6):195-203.
146. Choi S S, Park B H,Song Hanjong. Influence of filler typeand content on properties of styrene-butadiene rubber (SBR) compound reinforced with carbon black or silica[J]. PolymAdv Technol,2004,15 (3): 122-127.
147.贾超,卢咏来,张立群.不同形态纳米填料增强硅橡胶复合材料的研究进展[J].合成橡胶工业,2011,34(2)：154-159.
148.赵国璋.橡胶基纳米复合材料制备及性能研究[D].上海大学博士学位论文,2011.
149.干文涛.天然橡胶/蒙脱土纳米复合材料的阻隔性及相关性能研究[D].华南理工大学博士学位论文,
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