Study of the Metal Phosphate Gatalysts for Selective Oxidation of Lower Alkanes

低级烷烃选择性氧化金属磷酸盐催化剂的研究

• 批准号: 07650935
• 负责人: MATSUURA Ikuya
• 金额: $ 1.6万
• 依托单位: Toyama University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07650935/
• 关键词: Metal phospate; Vanadyl pyrophosphate; Propane; Butane; Acrylonitrilr; Maleic anhydride; オルトリン酸塩; ピロリン酸塩; リン酸ジルコニウム; ピロリン酸ジバナジウム; イソブタン; イソブテン; メタクリルニトリル; アンモ酸化反応

1. The synthesis of acrolein through propylene oxidation and acrylonitrile through ammoxidation are important from an industrial viewpoint. In resent years, efforts have been made to synthesize acrylonitrile using propane insted of propylene. We studied oxidation and ammoxidation of rich propane over orthophosphates of the tetragonal type M^<5+>OPO_4 catalysts. The selectivity of catalyst for oxivativedehydrogenation of propane to propylene decreases in the order of V > Mo > Nb > Ta. The catalytic activities of M^<5+>OPO_4 depends on the M^<5+>=0 strength in the crystal. From these results a surface reaction model is suggested which refers to the clevage (001) surface plane of N^<5+>OPO_4.2. (VO)_2P_2O_7 is a unique catalyst possessing a surprisingly high selectivity for the oxidation of n-butane to maleic anhydride. We reports that (VO)_2P_2O_7 mixed with a divalent metal orthophosphate can be used to synthesize maleic anhydride from n-butane oxidation with high selectivity and activity. The catalyst of (VO)_2P_2O_7 mixed with M^<2+>_3 (PO_4)_2 (M^<2+>=Fe, Ni, Co, Zn) has extremly high activity for n-butane oxidation to maleic anhydride. The M^<2+>_3 (PO_4) _2 grains are easly covered by the (VO)_2P_2O_7. The (100) plane of (VO)_2P_2O_7 in mixed catalysts has a more regular configuration compared to the simple (VO)_2P_2O_7. This regularity of the (100) plane causes the high activity and selectivity for n-butane oxidation. The promotion effect of the metal phosphate for (VO)_2P_2O_7 is in the order of M^<2+>_3 (PO_4)_2 > M^<2+>_2P_2O_7 > M^<3+>PO_4. The different promotion effects come from the degree of surface regularity by intercaleted metal phosphates with different structure.

1.从工业观点来看，通过丙烯氧化合成丙烯醛和通过氨氧化合成丙烯腈是重要的。近年来，人们一直在努力用丙烷代替丙烯合成丙烯腈。研究了正磷酸盐四元系M^<5+>OPO_4催化剂上富丙烷的氧化和氨氧化反应。丙烷氧化脱氢制丙烯的选择性由高到低的顺序为V > Mo > Nb > Ta。M^<5+>OPO_4的催化活性取决于晶体中M^<5+>=0的强度。根据这些结果提出了一个表面反应模型，该模型是指N^<5+>OPO_4.2的clevage（001）表面。(VO)2P_2O_7是一种独特的催化剂，对正丁烷氧化制顺酐具有高的选择性。本文报道了（VO）_2P_2O_7与二价金属磷酸盐混合催化剂用于正丁烷氧化合成顺酐的高选择性和高活性。（VO）_2P_2O_7与M^<2+>_3（PO_4）_2（M^<2+>=Fe、Ni、Co、Zn）混合的催化剂对正丁烷氧化制顺酐具有很高的活性。（VO）_2P_2O_7容易包覆M^<2+>_3（PO_4）_2颗粒。混合催化剂中（VO）_2P_2O_7的（100）面构型比单纯的（VO）_2P_2O_7更规则。（100）面的这种规则性导致正丁烷氧化的高活性和选择性。金属磷酸盐对（VO）_2P_2O_7的促进作用大小顺序为M^<2+>_3（PO_4）_2 > M^<2+>_2P_2O_7 > M^<3+>PO_4。不同结构的金属磷酸盐插层后，其表面规整程度不同，促进效果也不同。

项目成果

I.Kanesaka et al.: "Polarizing Raman Spectra and Intentity Analysis of Na_4P_2O_7・10H_2O and P-O Stretches in (VO)_2P_2O_7" J.Raman Spectroscopy. 26. 997-1002 (1995)

I.Kanesaka 等人：“(VO)_2P_2O_7 中 Na_4P_2O_7·10H_2O 和 P-O 拉伸的偏振拉曼光谱和强度分析”J.Raman Spectroscopy 26. 997-1002 (1995)。

I.Matsuura: "Oxidation and ammoxidation of propane over tetragonal type M^<5+> OPO_4" Studies in Surface Science and Catatysis 82. 82. 271-279 (1994)

I.Matsuura：“四方型 M^<5 > OPO_4 上丙烷的氧化和氨氧化”表面科学和催化研究 82. 82. 271-279 (1994)

T. Ishimura: "Preparation of Maleic Anhyderide Synthesis Catalyst (VO)_2P_2O_7 and their catalytic properties" Shokubai. 38. 506-509 (1996)

T. Ishimura：“马来酸酐合成催化剂(VO)_2P_2O_7的制备及其催化性能”Shokubai。

I.Matsuura et al.: "Oxidation and Ammoxidation of Propane over Tetragonal Type M^<5+>OPO_4" Studies in Surface Science and Catalysis. 82. 271-279 (1994)

I.Matsuura 等人：“四方型 M^<5 >OPO_4 上丙烷的氧化和氨氧化”表面科学和催化研究。

I.Matsuura et al.: "Promotion Effect of Metal Phosphates on the Selective Oxifdation of Butane to Maleic Anhydride ; Using Vanadyl Pyrophosphate Catalyst" Science and Technology in Catalysis 1994. 185-190 (1995)

I.Matsuura等人：“金属磷酸盐对丁烷选择性氧化成马来酸酐的促进作用；使用焦磷酸氧钒催化剂”催化科学与技术1994.185-190(1995)