31 5 pp x 0 40 mol% Ohe and Yokoyama, wt% 50 wt% 5 mol/dm 3 14 mol/dm % % 69% 6% Pauling Ni

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硝酸 - 水系の低濃度域における気液平衡に及ぼす塩効 Title 果を利用した硝酸の濃縮山本, 秀樹, 前田, 領平, 山口, 修平, 北口, 剛司, Author(s) 芝田, 隼次 Citation 化学工学論文集, 31(5): 331-337 Issue Date 2005

1 硝酸 - 水系の低濃度域における気液平衡に及ぼす塩効 Title 果を利用した硝酸の濃縮山本, 秀樹, 前田, 領平, 山口, 修平, 北口, 剛司, Author(s) 芝田, 隼次 Citation 化学工学論文集, 31(5): Issue Date 2005 URL Rights Type Journal Article Textversion publisher Kansai University

2 31 5 pp x 0 40 mol% Ohe and Yokoyama, wt% 50 wt% 5 mol/dm 3 14 mol/dm % % 69% 6% Pauling Nissan Engineering, wt% yhideki@kansai-u.ac.jp 3 Sloan, 1976; Vaillancourt, Copyright 2005 The Society of Chemical Engineers, Japan 331

3 Fig. 2 Vapor liquid equilibrium of methanol water system at kpa Fig. 1 Othmer-type equilibrium distillation apparatus Figure cm 3 13 cm 3 NF30-FA 0.1 K kpa Maripuri and Ratcliff, 1972 Figure % 0.36 K Herington 0.69% 0.20 K % 98.0% MOV-212F U 473 K wt% 50 wt% 200 g 5K 1 10 cm 3 BA kpa AT mol/dm 3 NaOH AA-6800 ICPs DA K 332

4 Table 1 Vapor liquid equilibrium data of nitric acid (1) water (2) salt (3) systems at kpa Mole fraction Liquid phase Vapor phase x 1 [ ] y 1 [ ] Boiling point t [ C] No salt Mg (NO 3 ) 2 : 30 wt% Mg (NO 3 ) 2 : 40 wt% Fig. 3 Vapor liquid equilibrium of nitric acid water system at kpa wt% 5 mol/dm g N K 1.0 kpa 320 K 1.0 kpa AT mol/dm 3 NaOH kpa Ellis and Thwaites, 1957 Figure kpa Table 1 Figure K 40 wt% Ca (NO 3 ) 2 : 40 wt% Ca (NO 3 ) 2 : 50 wt% LiNO 3 : 30 wt% LiNO 3 : 40 wt% LiNO 3 : 50 wt% NaNO 3 : 10 wt% NaNO 3 : 20 wt% Condition Experimental apparatus : Othmer-type 40 wt% 50 wt% 1 mol/kg Figure 5 1kg

5 Fig. 4 Vapor liquid equilibrium of nitric acid water lithium nitrate system at kpa Fig. 6 Relationship between crystallization ion radius and enthalpy of solution Fig. 7 Relationship between ionic radius and relative volatility ratio for nitric acid water salt systems Fig. 5 Vapor liquid equilibrium of nitric acid water salt systems at kpa Ohtaki, 1990 Figure 6 Figure 7 a a s a s/a Figure

6 Table 2 Results of simple distillation for nitric acid water lithium nitrate system at reduced pressure Table 3 Result of simple distillation for nitric acid water system at reduced pressure Feed Distillate Salt concentration [wt%] Concentration Concentration Yield [mol/dm 3 ] [mol/dm 3 ] [%] Conditions Amount of feed (salt free): 150 g, Temperature: 340 K, Pressure: about 0.8 kpa Feed Waste Distillate Concentration Concentration Yield Concentration Yield [mol/dm 3 ] [mol/dm 3 ] [%] [mol/dm 3 ] [%] Conditions Amount of feed (salt free): 150 g, Temperature: 320 K, Pressure: about 0.8 kpa Table 4 Component Mass balance of refining process I (simple distillation) for nitric acid (1) water (2) litium nitrate (3) system shown in Fig. 9 Distillate [wt%] Feed [wt%] Waste [wt%] ➀ ➁ ➂ ➃ HNO H 2 O LiNO Table 5 Component Mass balance of concentration process II (simple distillation) for nitric acid (1) water (2) system shown in Fig. 9 Feed [wt%] Waste [wt%] Distillate [wt%] ➄ ➅ ➆ HNO H 2 O Fig. 8 Relationship between relative volatility ratio and enthalpy of solution for nitric acid water salt system at kpa 5.0 mol/dm 3 Table 2 Nissan Engineering, wt% 8.2 mol/dm % 5.0 mol/dm 3 50 wt% Table K mol/dm % 4.2 mol/dm 3 Figure 9 2 I II 5.0 mol/dm mol/dm 3 Tables 4 5 Figure 9 I II 1 mol/kg

7 Fig. 9 Refining and concentration process of nitric acid 5.0 mol/dm 3 50 wt% 8.2 mol/dm % 14.0 mol/dm % 5.0 mol/dm mol/dm x 1 x 0 1 Nomenclature mole fraction of low-boiling component in liquid at existing salt [ ] mole fraction of low-boiling component in liquid at salt free basis [ ] y 1 mole fraction of low-boiling component in vapor [ ] a relative volatility at salt free [ ] a s relative volatility at salt addition [ ] Literature Cited Ellis, S. R. M. and J. M. Thwaites; Measurement of Vapor Liquid Equilibrium for Nitric Acid Water System, J. Appl. Chem., 7, 152 (1957) Ohe, S. and K. Yokoyama; Distillation with Use of Salt Effect, Isikawajimaharimagihou, 9, (1969) Maripuri, V. O. and G. A. Ratcriff; Measurement of Isothermal Vapor Liquid Equilibriums for Acetone n-heptane Mixtures using Modified Gillespie Still, J. Chem. Eng. Data, 17, (1972) Nissan Engineering, ed.; Unit Operation Series. Revision and Supplement. Distllation. 8. The Practice of Distillation, 820, Concentration of Dilute Nitric Acid, Bessatsu Kagakukougyou, 35, (1992) Ohtaki, H.; Hydration of Ion, Kyoritsusyuppan, Tokyo, Japan (1990) Sloan, J. G.; The Extractive Distillation Process for Nitric Acid Concentration Using Magnesium Nitrate, Adv. Chem. Ser., 155, (1976) Vaillancourt, J. A.; Use of Magnesium Nitrate in the Eextractive Distillation of Nitric Acid, Adv. Chem. Ser., 155, (1976) 336

8 Concentration of Nitric Acid Using the Salt Effect on Vapor Liquid Equilibrium of Nitric Acid Water Systems with Low Concentrations of Nitric Acid Hideki YAMAMOTO, Ryouhei MAEDA, Shuhei YAMAGUTI, Takeshi KITAGUTI and Junji SHIBATA Department of Chemical Engineering, Faculty of Engineering, Kansai University, , Yamate-cho, Suitashi, Osaka , Japan Keywords: Salt Effect, Nitric Acid, Nitrate Salt, Vapor Liquid Equilibrium, Concentration When involatile salts are added to an azeotropic mixture, the so-called salt effect changes the vapor liquid equilibrium, and has a big influence on relative volatility. Aqueous nitric acid is an azeotropic mixture, and cannot be concentrated by ordinary distillation. In this study, we measured the vapor liquid equilibrium of nitric acid water nitrate salt systems with azeotropic composition (x 0 40 mol%) for recycling of nitric acid in solutions from semiconductor manufacturing and metal-surface treatment processes. Aluminum nitrate, magnesium nitrate, calcium nitrate, lithium nitrate and sodium nitrate were used as nitrate salts. For each salt tested the salting-out effect was confirmed and the azeotropic point was eliminated completely by adding salts at concentration of wt%. Consequently, nitric acid could be separated by distillation from waste solution with a low concentration (under azeotropic composition) of nitric acid. Separation and concentration of nitric acid from dilute aqueous nitric acid was tested by simple distillation using 50 wt% lithium nitrate. As a result, nitric acid aqueous solution was concentrated from 5.0 to more than 14.0 mol/dm 3 (yield, 72.2%)

(Shigen to Sozai) Vol.116 p (2000) 石炭灰フライアッシュからのゼオライトのアルカリ水熱合成と生成物の陽イオン交換特性 * 1 1 村山憲弘山川洋亮 2 3 小川和男芝田隼次 Alkali Hydrothermal Synthesis of Zeol

(Shigen to Sozai) Vol.116 p (2000) 石炭灰フライアッシュからのゼオライトのアルカリ水熱合成と生成物の陽イオン交換特性 * 1 1 村山憲弘山川洋亮 2 3 小川和男芝田隼次 Alkali Hydrothermal Synthesis of Zeol 石炭灰フライアッシュからのゼオライトのアルカリ水 Title 熱合成と生成物の陽イオン交換特性 Author(s) 村山, 憲弘, 山川, 洋亮, 小川, 和男, 芝田, 隼次 Citation 資源と素材 : 資源素材学会誌, 116(4): 279-284 Issue Date 2000 URL http://hdl.handle.net/10112/5454 資源素材学会 (http://www.jstage.jst.go.