Stabilization of gas hydrate by addition of anti-freeze protein like peptide-modified polymer particles

通过添加抗冻蛋白（如肽改性聚合物颗粒）稳定天然气水合物

• 批准号: 15360512
• 负责人: TSUTSUMI Hiromori
• 金额: $ 4.74万
• 依托单位: Yamaguchi University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15360512/
• 关键词: methane hydrate; polymer additive; stabilization; gas storage; carbon dioxide hydrate; anti-freeze protein; peptide; 安定化効果; 固相合成

Gas hydrate is one of the inclusion compounds, which consist of water and gas molecules. Usual procedure for preparation of gas hydrate is compressing and cooling of the system with gas and water. Stabilization and controlled formation of methane hydrate is a key technology for its utilization. However, growth inhibitor of methane hydrate has been investigated mainly. We proposed polymeric additives for stabilization of methane hydrate. Merits of polymeric additives are (1) low volatility, (2) recyclability, and (3) chemical stability of them. We proposed that the equilibrium temperature-equilibrium pressure curve (T-P curve) of gas hydrate formation will be shift to higher temperature and lower pressure side by addition of surface modified polymer particles into the gas-water system. This means that stabilization of gas hydrate by addition of the polymer particles.First, we added the poly(styrene-co-divinylbenzene), (PSt) particles to the system with methane and water. Addition of PSt … More particles shifted the T-P curve of methane hydrate to lower temperature and higher pressure. We also prepared surface-modified PSt particles. For example, p-alkoxybenzylalcohol-unit modified PSt particles (c-PSOH) were examined under similar condition. However, addition of c-PSOH particles did not shift the T-P curve of methane hydrate. It is known that anti-freeze protein(AFP) interacts with water molecules and inhibits the growth of ice.AFP has alanine (Ala)-rich peptide sequence. We modified c-PSOH particles with alanine-rich sequence, -(Ala)_<10>-, -(Ala)_5-, and -(Ala)-. The particles with Ala-rich sequence could not stabilize methane hydrate. However, storage ratio of methane in the formed hydrate was higher than that of the additive-free hydrate. This suggests that alanine-rich sequence modified PSt particles inhibit ice formation, i.e., methane-free solid.Similar experiments were performed in the system with water and carbon dioxide. Carbon dioxide hydrate is also stabilized by addition of PSt particles into the carbon dioxide and water system. Less

天然气水合物是一种由水分子和气体分子组成的包合物。天然气水合物制备的基本步骤是压缩和冷却气体和水的体系。甲烷水合物的稳定和可控生成是其利用的关键技术。而对甲烷水合物生长抑制剂的研究主要集中在甲烷水合物的生长抑制剂上。我们提出了用于稳定甲烷水合物的高分子添加剂。聚合物添加剂的优点是（1）低挥发性，（2）可再循环性，和（3）它们的化学稳定性。提出了在气水体系中加入表面改性的聚合物颗粒，可以使天然气水合物生成的平衡温度-平衡压力曲线（T-P曲线）向高温低压侧移动。首先，我们将苯乙烯-二乙烯基苯共聚物（PSt）颗粒加入到甲烷和水的体系中。添加PSt ...更多信息 颗粒使甲烷水合物的T-P曲线向低温高压方向移动。我们还制备了表面改性的PSt颗粒。例如，在类似条件下检查对烷氧基苄醇单元改性的PSt颗粒（c-PSOH）。然而，添加c-PSOH颗粒没有移动甲烷水合物的T-P曲线。抗冻蛋白（AFP）具有富含丙氨酸（Ala）的肽段序列，能与水分子相互作用，抑制冰的生长。我们用富含丙氨酸的序列-（Ala）_<10>-、-（Ala）_5-和-（Ala）-修饰了c-PSOH颗粒。富Ala序列的颗粒不能稳定甲烷水合物。但是，甲烷在所形成的水合物中的储存率高于不含添加剂的水合物。这表明富含丙氨酸的序列修饰的PSt颗粒抑制冰的形成，即，在具有水和二氧化碳的系统中进行类似的实验。二氧化碳水合物也通过将PSt颗粒添加到二氧化碳和水体系中来稳定。少

项目成果

堤 宏守, 山田真史, 鬼村健二郎, 大石 勉: "メタンハイドレートの生成・分解に及ぼす高分子添加剤の効果"第52回高分子討論会講演予稿集. 52巻. 4342-4343 (2003)

Hiromori Tsutsumi、Masashi Yamada、Kenjiro Onimura、Tsutomu Oishi：“聚合物添加剂对甲烷水合物的产生和分解的影响”第 52 届聚合物研讨会论文集。 4342-4343 (2003)。

Effects of Surface Modified Polymer Particles on Methane Hydrate Formation and Decomposition

表面改性聚合物颗粒对甲烷水合物形成和分解的影响

• 发表时间: 2004
• 期刊: Polymer Preprints, Japan 53(1)
• 作者: Hiromori Tsutsumi;Masashi Yamada;Kenjiro Onimura;Tsutomu Oishi
• 通讯作者: Tsutomu Oishi

メタンガスハイドレートの生成・分解に及ぼす高分子添加剤の効果

聚合物添加剂对甲烷水合物生成和分解的影响

• 发表时间: 2003
• 期刊: 第52回高分子討論会講演予稿集 52巻
• 作者: 堤 宏守;山田真史;鬼村謙二郎;大石 勉
• 通讯作者: 大石 勉

Control of methane hydrate generation with polymer additives

用聚合物添加剂控制甲烷水合物的生成

• 发表时间: 2003
• 期刊: Polymer Preprint, Japan 52(5)
• 作者: Hiromori Tsutsumi;Masashi Yamada;Tamie Suetugu;Kenjiro Onimura;Tsutomu Oishi
• 通讯作者: Tsutomu Oishi

堤 宏守, 山田真史, 末次民枝, 鬼村健二郎, 大石 勉: "メタンハイドレートの安定性に対する高分子添加剤の効果"資源・素材学会2003年秋季大会講演予稿集. (2003)

Hiromori Tsutsumi、Masashi Yamada、Tamie Suetsugu、Kenjiro Onimura、Tsutomu Oishi：“聚合物添加剂对甲烷水合物稳定性的影响”日本资源与材料学会 2003 年秋季会议论文集（2003 年）。