Pt-Ir/C/PTFE疏水催化剂及交换效率研究
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摘要
本论文用湿浸法和分步湿浸法研制了8种Pt(Ir)／C／PTFE疏水催化剂。用TEM、SEM、XRD分析技术对疏水催化剂的表面形貌、活性组分分布及物相进行分析，结果表明：活性组分较均匀地以颗粒状负载在载体上，平均粒径为0.03μm。
用AUTOSORB-1-C吸附仪对疏水催化剂的比表面积、孔体积及孔径分布进行分析，结果表明：疏水催化剂中Pt：Ir=3：1时，其比表面积最大，活性组分仅为Ir的催化剂比表面积最小；疏水催化剂的脱附、吸附平均孔径均在18.0±0.21(?)范围之内。
研究了8种疏水催化剂在323K温度下气-液对流、气汽并流、气汽-液对流的氢-氘同位素交换实验。结果表明：(1)在同位素催化交换过程中若将液体雾化则催化剂的催化活性比纯的气液对流方式高近10倍；(2)在Pt／C／PTFE疏水催化剂中加入Ir，当Pt：Ir=3：1时，疏水催化剂的催化活性在所研制的催化剂中催化活性最高；(3)比表面积大的疏水催化剂其催化活性也高，即疏水催化剂的催化活性随其比表面积的增大而增加。
研究了温度、压力对疏水催化剂氢同位素交换时交换柱上部排出的HDO摩尔量的影响。结果表明：在选择催化交换温度时须考虑压力条件。用疏水催化剂分别在五种不同温度下进行氢同位素交换实验，结果表明催化活性在313～333K之间变化不大，但当温度降低到305K或增加到343K时活性明显降低。
研究了不同氢气流速对疏水催化剂氢同位素交换实验结果的影响。结果表明：随氢气流速从2.381·min~(-1)增加到6.381·min~(-1)，催化剂的催化活性增加较快，从6.381·min~(-1)增加至9.381·min~(-1)，催化活性的增加就逐渐缓慢下来。
The preparation of eight hydrophobic catalysts of Pt(Ir)/C/PTFE by dipping method in single and multiple steps respectively has been described in this thesis. The species with their distribution of the active elements (Pt or Ir), and the topography on the surface have been investigated by transmission electron microscope(TEM), scanning electron microscope(SEM) and X-ray diffraction(XRD). Results indicate that the active elements were deposited on the carrier homogenously, and that the average diameter of the particles is 0.03μm.
The specific surface area, total pore volume and average pore radius have been determined using an adsorption meter. A maximum specific area for the catalyst was obtained when the ratio of Pt/Ir is 3:1, but it becomes the smallest when the active ingredient is Ir without Pt. The average aperture on the adsorption or desorption is 18.0±0.2lA.
The hydrogen isotope exchange reaction kinetics between deuterium-enriched water and hydrogen gas have been tested for the eight hydrophobic catalysts beds with the gas-liquid countercurrent gas-vapor co-current gas/vapor-liquid countercurrent modes, respectively. Results indicate that the mass transfer coefficient K_(ya) in the co-current mode is approximately one order of magnitude greater than that in the gas-liquid (without vapor) countercurrent mode, and that Pt-Ir/C/PTFE hydrophobic catalyst with the ratio of Pt /Ir as 3:1 can increase the catalytic activity obviously, and that the catalytic activity increases with the increasing of the specific surface area.
The effects of the temperature and pressure on the mole fraction of HDO in the top segement of the column have been examined for the hydrophobic catalyst. Results indicate that the selection of the optimum temperature for the exchange effect depends on the column pressure. The exchange efficiency on the hydrogen isotopes exchange has been examined for the hydrophobic catalysts at different temperature. The result indicates that the catalytic activities keep steady between 313K and 333K, and decrease obviously when the temperature is below 305K or above 343K.
The effect of the flow rate of hydrogen gas within the column on the efficient of the hydrogen isotope exchange has been studied for the hydrophobic catalyst. Results indicate that the catalytic activity increases rapidly with the increasing of hydrogen flow rate from 2.38 to 6.38 1 min~(-1), but the increase becomes very slowly as the flow rate increases from 6.38 to 9.38 1 min~(-1)
用AUTOSORB-1-C吸附仪对疏水催化剂的比表面积、孔体积及孔径分布进行分析，结果表明：疏水催化剂中Pt：Ir=3：1时，其比表面积最大，活性组分仅为Ir的催化剂比表面积最小；疏水催化剂的脱附、吸附平均孔径均在18.0±0.21(?)范围之内。
研究了8种疏水催化剂在323K温度下气-液对流、气汽并流、气汽-液对流的氢-氘同位素交换实验。结果表明：(1)在同位素催化交换过程中若将液体雾化则催化剂的催化活性比纯的气液对流方式高近10倍；(2)在Pt／C／PTFE疏水催化剂中加入Ir，当Pt：Ir=3：1时，疏水催化剂的催化活性在所研制的催化剂中催化活性最高；(3)比表面积大的疏水催化剂其催化活性也高，即疏水催化剂的催化活性随其比表面积的增大而增加。
研究了温度、压力对疏水催化剂氢同位素交换时交换柱上部排出的HDO摩尔量的影响。结果表明：在选择催化交换温度时须考虑压力条件。用疏水催化剂分别在五种不同温度下进行氢同位素交换实验，结果表明催化活性在313～333K之间变化不大，但当温度降低到305K或增加到343K时活性明显降低。
研究了不同氢气流速对疏水催化剂氢同位素交换实验结果的影响。结果表明：随氢气流速从2.381·min~(-1)增加到6.381·min~(-1)，催化剂的催化活性增加较快，从6.381·min~(-1)增加至9.381·min~(-1)，催化活性的增加就逐渐缓慢下来。
The preparation of eight hydrophobic catalysts of Pt(Ir)/C/PTFE by dipping method in single and multiple steps respectively has been described in this thesis. The species with their distribution of the active elements (Pt or Ir), and the topography on the surface have been investigated by transmission electron microscope(TEM), scanning electron microscope(SEM) and X-ray diffraction(XRD). Results indicate that the active elements were deposited on the carrier homogenously, and that the average diameter of the particles is 0.03μm.
The specific surface area, total pore volume and average pore radius have been determined using an adsorption meter. A maximum specific area for the catalyst was obtained when the ratio of Pt/Ir is 3:1, but it becomes the smallest when the active ingredient is Ir without Pt. The average aperture on the adsorption or desorption is 18.0±0.2lA.
The hydrogen isotope exchange reaction kinetics between deuterium-enriched water and hydrogen gas have been tested for the eight hydrophobic catalysts beds with the gas-liquid countercurrent gas-vapor co-current gas/vapor-liquid countercurrent modes, respectively. Results indicate that the mass transfer coefficient K_(ya) in the co-current mode is approximately one order of magnitude greater than that in the gas-liquid (without vapor) countercurrent mode, and that Pt-Ir/C/PTFE hydrophobic catalyst with the ratio of Pt /Ir as 3:1 can increase the catalytic activity obviously, and that the catalytic activity increases with the increasing of the specific surface area.
The effects of the temperature and pressure on the mole fraction of HDO in the top segement of the column have been examined for the hydrophobic catalyst. Results indicate that the selection of the optimum temperature for the exchange effect depends on the column pressure. The exchange efficiency on the hydrogen isotopes exchange has been examined for the hydrophobic catalysts at different temperature. The result indicates that the catalytic activities keep steady between 313K and 333K, and decrease obviously when the temperature is below 305K or above 343K.
The effect of the flow rate of hydrogen gas within the column on the efficient of the hydrogen isotope exchange has been studied for the hydrophobic catalyst. Results indicate that the catalytic activity increases rapidly with the increasing of hydrogen flow rate from 2.38 to 6.38 1 min~(-1), but the increase becomes very slowly as the flow rate increases from 6.38 to 9.38 1 min~(-1)
引文
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2 Itsuo I,Junko K,Kenzi T.The exchange reaction between deuterium and water vapor on platinu m deposited over a hydrophobic support[J]. Zeitschrift für Physikalische Chemie Neu Folge,Bd, 1977; 107:219-230.
3 Stevens WH. Process and catalyst for enriching a fluid with hydrogen isotopes[P].Canadian Patent:907292,1972-08-15.
4 Stevens WH.Process for hydrogen isotope and concentration between liquid water and hydrogen gas and catalyst assembly thereafter[P]. U. S. Patent: 3888974,1975.
5 Butler JP.Hydrogen isotope separation by catalyzed exchange between hydrogen and liquid water[J].Sep. Sci. Tech, 1980; 15(3):371～396.
6 Izawa H,Isomura S,Nakane R.Gaseous Exchange reaction between deuterium and water on hydrophobic catalyst supporting.platinum[J]. Nucl. Sci. Tech, 1979;16:741～749.
7 Wei Y-Z, Shimizu M.Kinetics of iodine poisoning of hydrophobic Pt/SDBC catalyst for hydrogen isotopic exchange[J]. Can J Chen Een,1997;75(6):502～528.
8 Andreev BM, Sakharovsky YA,Rozenkevich MB,et al. Installation for separation of hydrogen isotopes by the method of chemical isotopic exchange in the "water-hydrogen" system[J]. Fusion Tech, 1995;28:515～518.
9 Ionit G, Stefnescu I.The separation of deuterium and tritium on Pt/SDBB/PS and Pt/C/PTFE hydrophobic catalyst[J]. Fusion Tech, 1995;28:641～646.
10 Ionit G, Pecular. Process for preparation hydrophobic platinum catalyst[P]. Romanian Patent: 147684,1990.
11 Ionit G.Hydrophobic catalyst for isotopic exchange hydrogen-water[J].Revue Romanian of Chemistry, 1994;45(10): 888.
12 Bruggeman A, Meynendonckx L.Method for preparing a catalyst for an isotope exchange column[P].Eur Patent:0045522,1998-10-10.
13 Bruggeman A,Meynendonckx L,Parmentie G, et al.Development of the ELEX process for tritium separation at reprocessing plants[J].Radioact Waste Manage and the Nuclear Fuel Cycle, 1985;6: 237～255
14 Belapurkar AD,Gupta NM,Iyer RM.PTEE dispersed hydrophobic catalysts for hydrogen-water isotope exchange [J] .App Catal, 1988 ;43:1～31
15 Lee HS,Chung HS,,Kang HS,et al.Preparation and characterization of polystyrene-bounded catalyst[J].
Kaeri/TR-324/93,1993 ;86.
16 祁世纶．在并流反应床中液相水同位素交换反应的研究[J]．高等化学学报，1994；15：77～82．
17 毛世奇，缪增星，李洪等．用于水／氢同位素交换的Pt／SDB疏水性催化剂的研究[J]．核化学与放射化学，1987；9：34～37．
18 毛世奇，郁婷婷，李洪等．Pt-C-PTFE疏水催化剂的H_2O-H_2同位素交换研究[J]．核化学与放射化学，1990；12：107～112．
19 但贵萍，曾俊辉．疏水催化剂用于水中氚回收的实验[J]．化学研究与应用，1999；11：366～370．
20 但贵萍，卢瑶章，邱咏梅等．大粒径疏水催化剂的制备及氧化氚氢的性能研究[J]．原子能科学技术，1999；33：12～17．
21 卢瑶章，但贵萍．催化氧化氚化氢的大粒径疏水催化剂研制及性能测试．2001 GF报告。
22 韩延德，孙兴旗，汤启明等．氢-水催化交换实验小回路的建造、实验和催化性能的研究．’98核材料会议文集，17～28．
23 罗阳明，翁承文．Pt／C／PTFE疏水催化剂制备．’98中国工程物理研究院科技年报，237～238．
24 A．B．司梯勒斯．顾其威等译．催化剂生产[M]．上海：华东化工学院出版社，1991．
25 A．M．鲁宾斯坦．多相催化剂的X射线分析[M]．北京：科学出版社，1963．
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