{"created":"2023-06-19T10:29:12.701662+00:00","id":8946,"links":{},"metadata":{"_buckets":{"deposit":"e6b7fcd7-c854-412c-8801-c52f4ede95e6"},"_deposit":{"created_by":18,"id":"8946","owners":[18],"pid":{"revision_id":0,"type":"depid","value":"8946"},"status":"published"},"_oai":{"id":"oai:muroran-it.repo.nii.ac.jp:00008946","sets":["216:378","41:227"]},"author_link":["42156"],"item_81_date_granted_17":{"attribute_name":"学位授与年月日","attribute_value_mlt":[{"subitem_dategranted":"2016-03-23"}]},"item_81_degree_grantor_10":{"attribute_name":"学位授与機関","attribute_value_mlt":[{"subitem_degreegrantor":[{"subitem_degreegrantor_language":"ja","subitem_degreegrantor_name":"室蘭工業大学"},{"subitem_degreegrantor_language":"en","subitem_degreegrantor_name":"Muroran Institute of Technology"}],"subitem_degreegrantor_identifier":[{"subitem_degreegrantor_identifier_name":"10103","subitem_degreegrantor_identifier_scheme":"kakenhi"}]}]},"item_81_degree_name_11":{"attribute_name":"学位名","attribute_value_mlt":[{"subitem_degreename":"博士（工学）","subitem_degreename_language":"ja"}]},"item_81_description_25":{"attribute_name":"フォーマット","attribute_value_mlt":[{"subitem_description":"application/pdf","subitem_description_type":"Other"}]},"item_81_description_7":{"attribute_name":"抄録","attribute_value_mlt":[{"subitem_description":"石油系燃料はCoMo/Al2O3触媒を用いた水素化脱硫（Hydrodesulfurization: HDS）により有害な硫黄分が除去されている。環境規制の強化に伴ってHDS触媒の高性能化が求められているが，既存触媒の大幅な性能向上は難しく，新規の高活性HDS触媒としてリン化ロジウム（Rh2P）が注目されている。しかし一般に，貴金属リン化物触媒の調製に使用されるリン酸塩は還元に高温を要する。それにより活性金属種は凝集し，触媒性能が低下することから，貴金属リン化物を低温で合成する新しい触媒調製法の開発が不可欠である。本論文は，ナトリウム（Na）の添加とNaを固定化制御できるゼオライトを用いた高性能Rh2P系HDS触媒の新規調製法について検討した結果をまとめたものである。ゼオライト構成成分であるSiO2およびAl2O3担体のいずれでも，Na添加により触媒活性種であるRh2Pが生成する還元温度が低下することを確認した。これを基に，MFI担持Rh2P触媒の調製に対するNaの添加効果を詳細に検討した。HMFIはRhの高分散担持に有利な担体であったが，高温還元によっても触媒活性種のRh2Pが生成し難いため，この触媒は低活性であった。一方，容易にRh2Pが生成するNaMFIを担体に用いると高いHDS活性を示した。これはNaの添加によりAlとリン酸種との相互作用が弱められたためと考えられた。構造が異なるNa型ゼオライト（NaMOR，NaMFI，NaBEA）を使用し，Rh2P触媒の調製におけるNa添加効果の担体依存性を検討した。三次元細孔構造を有するNaMFIでは同じく三次元構造のNaBEAよりも熱安定性が高く，さらに一次元細孔構造のNaMORよりも分散性の良いRh2Pが生成するため，高いHDS活性を示すことを明らかにした。さらに，NaMFI担体のSi/Alを高くするとRh2Pの低温生成には有利であるが，その粒子径は低Si/Alほど小さいことを見出した。Si/Al比24のときに高いHDS活性が発現し，これは分散性の良いRh2Pが比較的低温で生成したためと推定した。これまでの結果から，高活性HDS触媒の調製にはRh2Pの低温合成だけでは不十分であり，担体により分散性を制御する必要性も示唆された。Rh2P/NaHMFI触媒はCoMo系触媒よりも高いHDS活性を示し，これはNa型の還元性向上効果とH型の分散性向上効果が同時に発現したためと結論付けられた。以上，Naとそれを固定化できるゼオライトを用いることで，高活性Rh2P系HDS触媒が調製可能であることを明らかにした。","subitem_description_language":"ja","subitem_description_type":"Abstract"},{"subitem_description":"Hydrodesulfurization (HDS) of petroleum fractions is one of the most important processes to produce low sulfur fuels. While CoMo catalyst has been widely used in the petroleum industry, fast-growing environmental pollution problems claim the development of a new HDS catalyst which is more active than the conventional one. Rhodium phosphide (Rh2P) has been recently received much attention as a new catalyst. However, its preparation procedure involves the reduction of phosphate species at higher temperatures, resulting in an aggregation of Rh species and thereby a lowering of catalytic activity. It is thus needed to establish a new method for preparing dispersed Rh2P catalysts at lower temperatures. In this study, catalyst preparation using sodium (Na) and zeolites was investigated to develop highly active HDS catalysts.Firstly, SiO2 and Al2O3, which are constitutive materials of zeolites, were used as supports. Na addition facilitated reduction of phosphates, resulting that Rh2P were easily formed on these supports at lower temperature. On Na-free HMFI, Rh species more strongly interacted with ion exchange site than that of NaMFI, but formation of Rh2P was difficult. Since Na addition weaken interaction between Al atoms in the zeolite and phosphate, Rh2P were also easily formed on NaMFI at lower temperatures. Furthermore, this catalyst showed an excellent performance in the HDS of thiophene.The influence of Na added was further investigated using three zeolites with different pore structures, MFI, BEA and MOR. Among them, NaMFI was the most effective support, on which well-dispersed active Rh2P was formed. The other zeolite supports were not enough because of insufficient thermal stability and diffusivity.Fine tuning of NaMFI characteristics was also carried out by changing Si/Al ratio. As the ratio increased in the range of 17-492, the reduction of the catalyst precursor occurred at lower temperatures to form Rh2P, while its particle size increased. Hence, NaMFI with a Si/Al ratio of 24 was found to be a favorable support for the preparing active catalysts.A partial exchange of Na+ in NaMFI framework with protons (H+) improved dispersion of Rh species and the resulting NaHMFI-supported Rh2P catalyst showed the highest HDS activity among the catalysts prepared in this study.In conclusion, the new method using Na and MFI zeolite has been successfully developed to prepare highly active Rh2P-based HDS catalyst, which is superior to the conventional CoMo catalyst.","subitem_description_language":"en","subitem_description_type":"Abstract"}]},"item_81_dissertation_number_13":{"attribute_name":"学位授与番号","attribute_value_mlt":[{"subitem_dissertationnumber":"甲第384号"}]},"item_81_identifier_registration":{"attribute_name":"ID登録","attribute_value_mlt":[{"subitem_identifier_reg_text":"10.15118/00008929","subitem_identifier_reg_type":"JaLC"}]},"item_81_link_5":{"attribute_name":"室蘭工業大学研究者データベースへのリンク","attribute_value_mlt":[{"subitem_link_text":"澤田 紋佳（SAWADA Ayaka）","subitem_link_url":"http://rdsoran.muroran-it.ac.jp/html/100000166_ja.html"}]},"item_81_subject_9":{"attribute_name":"日本十進分類法","attribute_value_mlt":[{"subitem_subject":"575","subitem_subject_scheme":"NDC"}]},"item_81_text_12":{"attribute_name":"学位の種別","attribute_value_mlt":[{"subitem_text_language":"ja","subitem_text_value":"課程博士"}]},"item_81_text_14":{"attribute_name":"報告番号","attribute_value_mlt":[{"subitem_text_language":"ja","subitem_text_value":"甲第384号"}]},"item_81_text_15":{"attribute_name":"学位記番号","attribute_value_mlt":[{"subitem_text_language":"ja","subitem_text_value":"博甲第384号"}]},"item_81_text_16":{"attribute_name":"研究科・専攻","attribute_value_mlt":[{"subitem_text_language":"ja","subitem_text_value":"物質工学専攻"}]},"item_81_version_type_24":{"attribute_name":"著者版フラグ","attribute_value_mlt":[{"subitem_version_resource":"http://purl.org/coar/version/c_970fb48d4fbd8a85","subitem_version_type":"VoR"}]},"item_access_right":{"attribute_name":"アクセス権","attribute_value_mlt":[{"subitem_access_right":"open access","subitem_access_right_uri":"http://purl.org/coar/access_right/c_abf2"}]},"item_creator":{"attribute_name":"著者","attribute_type":"creator","attribute_value_mlt":[{"creatorAffiliations":[{"affiliationNameIdentifiers":[{}],"affiliationNames":[{},{}]}],"creatorNames":[{"creatorName":"澤田, 紋佳","creatorNameLang":"ja"},{"creatorName":"SAWADA, Ayaka","creatorNameLang":"en"},{"creatorName":"サワダ, アヤカ","creatorNameLang":"ja-Kana"}],"familyNames":[{},{},{}],"givenNames":[{},{},{}],"nameIdentifiers":[{}]}]},"item_files":{"attribute_name":"ファイル情報","attribute_type":"file","attribute_value_mlt":[{"accessrole":"open_date","date":[{"dateType":"Available","dateValue":"2016-06-08"}],"displaytype":"detail","filename":"A384_summary.pdf","filesize":[{"value":"438.4 kB"}],"format":"application/pdf","licensetype":"license_note","mimetype":"application/pdf","url":{"label":"A384_summary","objectType":"abstract","url":"https://muroran-it.repo.nii.ac.jp/record/8946/files/A384_summary.pdf"},"version_id":"2df3c93f-029d-4e55-ae0f-4b55465e3b53"},{"accessrole":"open_date","date":[{"dateType":"Available","dateValue":"2019-03-26"}],"displaytype":"detail","filename":"A384.pdf","filesize":[{"value":"5.2 MB"}],"format":"application/pdf","licensetype":"license_note","mimetype":"application/pdf","url":{"label":"A384","objectType":"fulltext","url":"https://muroran-it.repo.nii.ac.jp/record/8946/files/A384.pdf"},"version_id":"f745208e-2dc9-4bd2-8aa1-d0566c44c1d4"}]},"item_language":{"attribute_name":"言語","attribute_value_mlt":[{"subitem_language":"jpn"}]},"item_resource_type":{"attribute_name":"資源タイプ","attribute_value_mlt":[{"resourcetype":"doctoral thesis","resourceuri":"http://purl.org/coar/resource_type/c_db06"}]},"item_title":"高性能リン化ロジウム系水素化脱硫触媒の新規調製法に関する研究","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"高性能リン化ロジウム系水素化脱硫触媒の新規調製法に関する研究","subitem_title_language":"ja"}]},"item_type_id":"81","owner":"18","path":["227","378"],"pubdate":{"attribute_name":"PubDate","attribute_value":"2016-06-08"},"publish_date":"2016-06-08","publish_status":"0","recid":"8946","relation_version_is_last":true,"title":["高性能リン化ロジウム系水素化脱硫触媒の新規調製法に関する研究"],"weko_creator_id":"18","weko_shared_id":-1},"updated":"2023-10-24T00:57:25.968738+00:00"}