摘要
近几年随着洁净煤技术的蓬勃发展,选煤工业也得到了迅速的发展。选煤厂处理能力的迅速扩张,使得其主要的副产品-细粒煤泥增多,且采煤机械化程度的提高,原煤中煤泥含量显著增加,导致大量煤泥对选煤厂的闭路循环造成威胁。传统药剂浮选细粒难,选煤效果大多较差,出于对环境污染和石油短缺的忧虑,高效、廉价、环境友好的生物基起泡剂正受到广泛的重视,世界各国都在研制利用天然原料合成的浮选药剂代替石化产品生产的浮选药剂。表面活性剂-烷基糖苷的加入可以降低药耗量,提高精煤产率,改善精煤质量,且无毒无害,操作简便,符合当今研制浮选药剂的主要趋势。
本文以葡萄糖和天然高级脂肪醇为原料,采用两步法工艺合成烷基糖苷(Alkyl Polyglucoside简称APG)。通过单因素试验确定了最佳反应工艺条件为：采用复合催化剂其与葡萄糖的比0.015：1、醇糖比(5-6)：1、反应时间3.5h、反应温度(118℃),减小葡萄糖粒度且葡萄糖分批加料,二次醇交换后萃取再进行高温蒸馏。
对实验合成的APG红外图谱分析可见,1500cm-1—1650cm-1和1200cm-1—1000cm-1附近有C-O-C键的骨架振动峰、C-O键和C-O-C键的伸缩振动峰,其官能团基本符合商品APG。通过GC-MS也分析得出合成APG有十二烷基-α-D-吡喃葡萄糖苷和吡喃半乳糖苷。并检测APG的表面活性、临界胶束浓度、乳化性能、起泡和泡沫稳定性、浊点、硬水稳定性等性能,结果表明APG具有良好起泡剂的一般性质
对淮北五沟、海孜、百善、刘二和任楼矿五种不同煤种的原煤分别以杂醇、合成和商品APG类浮选剂为起泡剂进行可比性试验,说明合成的APG类浮选起泡剂的煤种适应性及精煤选择性好。考察了捕收剂和起泡剂作用于百善矿浮选时的最佳用量,以烷基糖苷为起泡剂和柴油为捕收剂采用正交实验通过评价精煤的可燃体回收率,得到最佳组合为矿浆浓度80g/L、起泡剂100g/t,捕收剂1200g/t。
图[10]表[36]参[72]
In recent years coal preparation industry has been made a big advance with the development of clean coal technology., It lead to making its main product-fine coal increase that the capacity of washery was expanded rapidly. Then it caused a threat on the closed circuit that coal slime significantly increased in slurry preparation plant. traditional flotation agent has difficult fine flotation, mostly poor flotation effect is bad. Considering the pollution and shortage of the oil, bio-based foaming agent is at a premium. nations of the world were researching the flotation medicament synthesized with natural raw material to replac the petrochemical. Alkyl polyglycoside can reduce drug consumption, improve the yield and quality of clean coal, non-toxic harmless and easy to operate. at the same time Alkyl polyglycoside is keeping with the current development of the flotation reagent.
In this thesis alkyl polyglucosides are prepared by the renewable resource glucose and the natural fatty alcohol with the indirect method. The optimized synthesis craft: the catalyst mixed with p-toluenesulfonic acid and sulfuric acid, the quality ratio of catalyst to glucose is 0.015:1, alcohol to glucose is (5～6):1, at 118℃and pH=3-6, the reaction time is 3.5h,during the reaction starch glucose addition in batchs.
The structure of APGs is analyzed by means of infrared absorption spectroscopy, recording the characteristic absorption skeleton vibration peaks C-O-C (1500cm-1-1650cm-1), and the stretching vibration peaks C-O and C-O-C (1100cm-1-1000cm-1).The spectrum proves the structure of APGs. It is also analysised by GC-MS that the alkyl polyglycosides is composed with dodecyl-a-D-glucopyranoside and glucopyranoside.At the time, the surface tension, CMC, emulsion properties, foaming and stability properties, cloud point and stability in hard water are determined. It is conformed that APGs have excellent surface active.
The compare test of foaming agent was taken with miscellaneous alcohol, synthetic and commodity APG to the coal sample got from the coal mine Wugou Huaibei, Haizi, Baishan,Liuer and Renlou, the result indicates that the selectivity of alkyl polyglycosides class synthetic foaming agents is better than others.In Order to improve the flotation technology of Baishan coal preparation plant. The orthogonal design is used to get the optimized floatation compositions for the slurry with APG as foaming agentand diesel as collector. Depend on the recovery of the burnable matter, the best combination ofthe optimized floatation compositions is Al* B3* C2:pulp density 80g/L, foaming agent 100g/t, collector agent 1200g/t.
Figure [10] table [36] reference [72]
引文
[1]吴式瑜.中国选煤迅速发展的25年[J].煤炭加工与综合利用.2007(5)：3-4.
[2]徐博等.煤泥浮选技术与实践[M].北京：化学工业出版社.2006.2-5
[3]简用康.煤泥的浮选[M].北京：煤炭工业出版社,1983.13-18
[4]Kim J Y, Song M G, Kim J D. Zeta potential of nanobubbles generated by ultrasonication in aqueous alkyl polyglucoside solutions[J]. Colloid Interface Sci,2000,223:285-291.
[5]吴建军,马喜平,邱海燕.烷基多苷的应用[J].日用化学工业,2004.34(3)：181-183.
[6]Wegener,M.Surfactants systems for microemulsin and their importance for application[J].Tenside Surfactants Detergents,2001,38(1):24-29.
[7]孙岩.新表面活性剂[M].北京：化学工业出版社,2003：276-285.
[8]刘少杰,孙立新等.添加剂对烷基糖苷微乳液相图的影响[J].精细化工,2005(4)256-260.
[9]李晓林,于永水,高立彬等.新一代绿色表面活性剂-烷基糖苷[J].2002,6(2)：87-91.
[10]于宁.烷基糖苷的合成及物化性能分析[D].大连：大连理工大学,2004.13-17.
[11]K.Fukuda,U.Olsson.Microemulsion formed by alkyl polyglucoside and an alkylglycerol ether with weakly charged films[J]. Colloids and Surfaces B: Biointerfaces 20 (2001) 129-135.
[12]紫金岭,李干佐,张高勇等.绿色表面活性剂-烷基(聚)葡糖苷结构体系[J].化学通报,2002(8)506-514.
[13]Vishal Y.Joshi,mahesh M.kadam. Comparison of QSAR and QSPR Based Aquatic Toxicity for Mixed Surfactants [J]. Journal of surfactants and detergents 2007 Vol.10 (no.1)
[14]秦勇,张高勇.蒽酮法烷基多苷(APG)初级生物降解性的研究[J].环境科学研究,2003,16(4)：28-31.
[15]张兴.十八烷基糖苷的降解性预测合成与性能分析[D].西安：西安交通大学,2003：3-7.
[16]H. Messinger, W. Aulmann, M. Kleber, W. Koehl Investigations on the effects of alkyl polyglucosides on development and fertility [J]. Food and Chemical Toxicology, 2007,8(45),1375-1382
[17]李晓林,于永水,高立彬等.新一代绿色表面活性剂-烷基糖苷[J].2002,6(72)：87-91.
[18]Gruetzke Juergen; Schmidt Stefan Dr Process for the preparation of alkyl polyglycosides EP 700925(1996).
[19]Giampiero Borsotti; Eniricerche S.p.a Process for preparing APG'sUS 5527892(1994).
[20]Patrick M.Mccurry Jr; Janet R. Varvil; Carl E. Pickens Process for making alkyl polyglycosides US 5512666(1996)
[21]Patrick M.Mccurry Jr; Eskuchen Rainer; Schulz Paul Procwss for producing light colored alkyl polyglucosides with partially sulfated fatty alcohol catalysts US 5478930(1995)
[22]Corma Camos Avelino; Iborra Chornet Sara; Primo Millo Jaime; Miquel Sophie Process and catalysts for the selective preparation of alkyl glycosides ES 2110367(1998)
[23]刘祥.固体超强酸催化常压合成烷基糖苷[J].上海化工,2004(4)27-29.
[24]朱文均,杨以安等.固载杂多酸PW12/SiO2催化合成烷基糖苷的研究[J].苏州大学学报,2000,16(1)94-97.
[25]马万勇,班青等.一种淀粉酶催化合成烷基糖苷的方法[P].CN 101168761A.
[26]吕树样,邓宇.合成十二烷基葡萄糖昔的工艺条件[J].精细石油化工,2003.(2)：4-7
[27]Stephen Bradford Kong, Sonia H. Burciaga. Low Residue Cleaning Solution for Disinfecting Wipes Comprising a C8-10 Alkyl Polyglycoside [P]. US 7,345,015 B1. 5-18-2008.
[28]Joshi David P, Masser Heidrun. Toilet soap bar composition with alkyl polyglucoside surfactant [P].EP:0463912,1992-01-12.
[29]李和平,朱克庆.淀粉基表面活性剂烷基糖苷及其应用[J].化工进展,1997(5)：31-33.
[30]Kiewert E, Jeschke P, Middelhavve B, Carrer G, Cleaning compositions for hard surfaces.DE4210365(1993)和 Mustafa G Body cleaning compositions, especiakky conditioning shampoo compositions. JP20000191471A2(2000).
[31]Hill K, Rybinski W von, toll G, Akyl Polyglucoside:Technology,Properties and Application.Wwinheim:VCH,1997:201-213.
[32]伍明华,陈焕钦.烷基多苷一种适用于化妆品的表面活性剂[J].香料香精化妆 品,1996(4)：18-20.
[33]窦红梅,许承阳.甲基葡萄糖苷-无渗透钻井液的研究和评价[J].青海石油,2006(12)：89-94.
[34]孙立明,陈仲祥,翟丽萍.新型钻井液甲基葡萄糖苷的合成研究[J].河北化工,2002(6)：25-26.
[35]井涛.正丁基葡萄糖苷的合成与表征[D].山东：山东大学,2007：15-19
[36]王杰.生物基表面活性剂的合成和应用性能研究[D].安徽：安徽理工大学,2007：3-15
[37]Marian Wlodzimierz Sulek, Tomasz Wasilewski. Tribological Properties of Aqueous Solutions of Alkyl Polyglucosides[J]. Wear(2006):193-204
[38]Virginia Lazarowitz.Use of carboxylate alkyl polyglycoside surfactant to increase the foam of other anionic surfactants[P].US 6248792 (2001).
[39]于珍祥,马菊瑛,曹玉英等.烷基糖苷表面活性剂的制备方法[P].CN92102625.04-12-1992
[40]杨秀全.一种浅色透明烷基糖苷的制备工艺[P].CN 1634949A 07-06-2005.
[41]金玉芹.用于制备烷基糖苷的催化剂[P].CN1315311A 10-03-2001.
[42]刘士荣.一种用固载杂多酸催化剂的烷基糖苷的制备方法[P].CN 101239999A08-13-2008.
[43]金玉芹,肖福奎,朴贞顺等.烷基糖苷的市场状况及合成工艺进展[J].精细化工1998,15(5)：5-7.
[44]劳国强,李颖.展示APG的美好前景[J].日用化学品科学,2001,24(2)：30-32.
[45]上海发凯有限公司5000t/a烷基糖苷(APG)生产装置试车成功[J].日用化学品科学,2007,14(5).
[46]Dengwei Jing, Jian Zhang,Gaoyong Zhang. Phase Behavior of DNA in the Presence of cetyltrimethylammonium Bromide/alkyl polyglucoside surfactant Mixture[J], Colloid & Polymer Science(2004)282:1089-1096.
[47]Olivier Gorius,Jean-Noel Bertho, Jean-Marc Nuzillard Determination and prediction of the average polymerization degree of alkyl polyglucosides analytica chimica acta 440(2001):231-237.
[48]周世军,苏琼.烷基糖苷合成工艺的发展[J].西北民族大学学报.2008(3)20-24.
[49]柴金岭,李干佐,张高勇等.绿色表面活性剂-烷基(聚)葡糖苷缔合结构体系[J].化学通报,2002(8)：506-515.
[50]中国煤炭教育协会职业教育教材编审委员会.选煤工艺：浮选[M].北京：煤炭工业出版社,2007：207-209
[51]丁立亲.浮选的理论和实践[M].北京：煤炭工业出版社,1987：40-60
[52]谢广元,张明旭,边炳鑫等.选矿学[M].江苏：中国矿业大学出版社,2001：430-455
[53]王淀佐.浮选剂作用原理[M].北京：冶金出版社,1982：3-6
[54]赵本军.浮选过程中捕收剂和起泡剂的综合作用[J]能源技术与管理,2004(2)：59-60
[55]陈红.非离子表面活性剂在煤浮选中的应用[J].煤炭技术.2000,(04)：58-59
[56]Moxon, N.T., Keast-Jones, R.,1986. The effect of collector emulsification using non-ionic surfactants on the flotation of coarse coal particles. Int. J. Miner. Process.18, 21-32.
[57]Ates_ok, G, C_elik, M.S.,2000. A new flotation scheme for a difficult-to-float coal using pitch additive in dry grinding. Fuel 79,1509-1513.
[58]Busmante, H., Warren, L.J.,1984. The joint effect of rank and grain size on the flotation of Australian bituminous coals. Int. J. Miner. Process.13,13-28.
[59]Asplin, R.A., Sadr-Kazemi, N., Cilliers, J.J.,1998. The effect of surfactant concentration on batch flotation mineral flux and froth structure. Miner. Eng.11, 257-269.
[60]Flynn, S.A., Woodburn, E.T. A froth ultra-fine model for the selective separation of coal from mineral in a dispersed air flotation cell. Powder Technol.1987 49,127-142.
[61]Jia, R., Harris, G.H., Fuerstenau, D.W.,2000. An improved class of universal collectors for the flotation of oxidized and/or low-rank coal. Int. J. Miner. Process.58, 99-118.
[62]Jameson, G.J., Nam, S., Young, M.M.,1977. Physical factors affecting recovery rates in flotation. Miner. Sci. Eng.9,103-118
[63]Lynch, A.J., Johnson, N.M., Manlapig, E.V., Thorne, C.G.,1974. The behaviour of minerals in sulphide flotation processes, with reference to simulation and control. J. S. Afr. Inst. Min. Metall.,349-361.
[64]郑伟.我国浮选起泡剂的研究进展[J].云南冶金,2003(10)：155-158
[65]徐初阳,聂容春,唐明康.高效复合选煤浮选药剂的研究[J]煤炭科学技术,2003(06)：11-13
[66]郭得等.脱泥浮选工艺的实践与认识[J].煤炭学报,2000,25(2)：208-211
[67]F·麦罗等.浮选起泡剂的基本性质及其对浮选的影响[J].国外金属矿选2007(4)：31-36
[68]《选煤标准使用手册》编委会,选煤标准使用手册[M].北京：中国标准出版社,1999.
[69]郑描.浮游选煤降灰工艺和作用机理的研究[D].安徽理工大学,2006：49-51
[70]蓝仁华,伍明华,杨卓如等.二步法合成十二烷基多苷机理及动力学探讨[J].高校化学工程学报2001,15(3)248-253.
[71]紫金岭,李干佐,张高勇等.绿色表面活性剂—烷基(聚)葡糖苷结构体系[J].化学通报,2002(8)506-514.
[72]胡飞,温其标.淀粉原料表面活性剂发展概况[J].广西化工1997,(1)28-31.
