Article(id=1320098210610267099, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1320098188355285873, articleNumber=null, orderNo=null, doi=10.14062/j.issn.0454-5648.20230809, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1697731200000, receivedDateStr=2023-10-20, revisedDate=1699632000000, revisedDateStr=2023-11-11, acceptedDate=null, acceptedDateStr=null, onlineDate=1792665539648, onlineDateStr=2026-10-22, pubDate=1726761600000, pubDateStr=2024-09-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1792665539648, onlineIssueDateStr=2026-10-22, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1792665539647, creator=13701087609, updateTime=1792665539647, updator=13701087609, issue=Issue{id=1320098188355285873, tenantId=1146029695717560320, journalId=1263187385517883426, year='2024', volume='52', issue='9', pageStart='2755', pageEnd='3090', issueExtLink='null', onlineDate='null', pubDate='1726761600000', pubDateStr='2024-09-20', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1792665534341, creator='13701087609', updateTime=1792666312798, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1320101453507711442, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1320098188355285873, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1320101453507711443, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1320098188355285873, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=3047, endPage=3054, ext={EN=ArticleExt(id=1320098210840953820, articleId=1320098210610267099, tenantId=1146029695717560320, journalId=1263187385517883426, language=EN, title=Study on Synthesis and Properties of Iron-Containing Mordenite Molecular Sieves, columnId=1319726165087077079, journalTitle=Journal of the Chinese Ceramic Society, columnName=Research Article, runingTitle=null, highlight=null, articleAbstract=
Introduction

In recent years, mordenite molecular sieves with various properties have been successfully synthesized by template method. Although the template method has received a lot of attention, the addition of the templating agents especially organic templating agents, would increase the cost of raw materials, and could be harmful to environment. Therefore, the method without organic template is more economical and environmentally friendly. Recently, the synthesis and applications of mordenite modified by hetero-atom have getting more and more attentions, and the performance of modified mordenite molecular sieve shows better. The common methods for modifying mordenite molecular sieve include ion exchange method and impregnation method. Some researchers have synthesized monolithic iron-containing mordenite (Fe-MOR) by template-free method, which has excellent CO2/N2 separation performance and high carbon dioxide capture performance. In addition, Fe-MOR zeolite can catalytically decompose N2O into N2 and O2, which can effectively reduce the N2O content in the atmosphere. In this work, Fe-MOR zeolite was synthesized by hydrothermal method without organic template. A novel rod-cluster-shaped Fe-MOR zeolite was controllably synthesized by fine adjustment of pH and crystallization time, and its CO2 adsorption properties were investigated.

Methods

Deionized water, tetraethyl orthosilicate, concentrated hydrochloric acid, ferric nitrate, aluminum sulfate and sodium hydroxide were used. A mixture with n(Fe) : n(SiO2) : n(Na2O) : n(H2O) : n(Al2O3) : n(HCl)=0.002 5∶1.000 0∶x∶30.000 0∶0.066 5∶y (n is molar ratio, x=0.300 0~0.580 0, y=0.100 0~0.150 0) was obtained, then the mixture was transferred into a polytetrafluoroethylene lined stainless steel autoclave and crystallized at 180°C for 7 to 14 days. When the reaction finished, a white powder sample was obtained after post-treatment.

The crystalline phase and crystallinity of the samples were analyzed by PANalytical X'Pert Powder (XRD). S-3400N scanning electron microscope (SEM) was used to observe the morphology of the samples. The elemental composition of the samples was analyzed by S8-tiger X-ray fluorescence spectrometer (XRF). The static CO2 adsorption performance of the samples was measured by ASAP-2460 physical adsorption analyzer. A fixed-bed apparatus and a Hiden Analytical HPR-20 on-line mass spectrometer were used to determine the dynamic CO2 adsorption performance of the samples.

Results and discussion

The crystalline phase of the product is effected by the amount of sodium hydroxide or the concentration of hydrochloric acid used in the initial gel mixture. The pH value of the initial gel mixture is crucial for the synthesis of pure phase Fe-MOR. The XRD results show that the peak intensity of MOR decreases gradually with the decrease of Na2O molar ratio from 0.4 to 0.36, indicating the crystallinity of samples related tod the basicity in a certain range. When the molar ratio of Na2O/SiO2 is 0.4 or 0.375, the pure phase MOR with rod-shaped cluster was obtained, in which the single rod is approximately hexagonal and the morphology is uniform. When the molar ratio of Na2O/SiO2 is in the range of 0.3-0.58, the analcite will arise if the alkalinity of the system is too high, and the amorphous phase will appear if the alkalinity is too low. This means that moderate alkalinity is conducive to the interaction of silicon, aluminum and other components, promoting the nucleation and growth of the crystallization, contributing to the synthesis of pure mordenite. Moreover, when the molar ratio of Na2O/SiO2 is 0.4, the pure phase of Fe-MOR can be controllably synthesized by adjusting the molar ratio of concentrated hydrochloric acid.

The pure phase Fe-MOR molecular sieves can also be synthesized by shortening the crystallization time under the constant pH. The axial size of the synthesized samples also decreases with the decrease of the crystallization time. The results show that the longer the crystallization time is, the better the axial growth of the crystals, but when the crystallization time is less than 7 days, the hetero-crystalline phase of analcite appears.

The static adsorption capacity of CO2 on Fe-MOR samples was similar because the adsorption mainly depends on the atmosphere pressure. The capacity of dynamic adsorption of CO2 is due to the difference of the suitable site of electric field in the 8-membered ring channel of MOR, which determines the adsorption capacity in the dynamic CO2 penetration under low partial pressure of CO2. The microstructure of Fe-MOR molecular sieves synthesized under different conditions are different, which results in the difference of CO2 dynamic adsorption capacity of several samples.

Conclusions

The results show that the pH of the gel mixture and crystallization time affected the synthetic products. When the amount of hydrochloric acid is constant, the high alkalinity results in analcite crystals while the low alkalinity results in amorphous phase. When the amount of sodium hydroxide is high, increasing the amount of hydrochloric acid will result in the pure Fe-MOR molecular sieves. The axial size of the crystal will decrease with the shortening of the synthesis time under appropriate pH value. When the crystallization time was less than 7 days, the hetero-crystalline phase of analcite appeared, which was attributed to the short synthesis time leading to incomplete crystallization. Rod cluster Fe-MOR molecular sieves were synthesized by hydrothermal method without organic template and showed good static and dynamic adsorption capacity for CO2, and the static adsorption capacity was up to 3.57 mmol/g.

, authors=Ying CHENG, Shimin CHENG, Guangyu TAN, Shengpeng LI, Chuang WANG, Dongxue YIN, Qian WANG, Long YUAN, authorsList=Ying CHENG, Shimin CHENG, Guangyu TAN, Shengpeng LI, Chuang WANG, Dongxue YIN, Qian WANG, Long YUAN, authorCompany=null, correspAuthors=Shimin CHENG, authorNote=

CHENG Ying (1992-), female, Bachelor, Engineer. E-mail:

, correspAuthorsNote=
CHENG Shimin (1984-), male, Ph.D., Senior Engineer. E-mail:
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含铁丝光沸石(Fe-MOR)分子筛因其独特的结构特点和良好的应用潜力,近年开始引起较多的关注。采用无有机模板剂法水热合成含铁丝光沸石分子筛,通过精细调节合成过程的酸碱度及晶化时间可控的合成出棒簇状形貌的Fe-MOR分子筛。通过粉末X射线衍射仪,扫描电子显微镜,X射线荧光分析仪,CO2静态吸附,CO2吸附穿透试验分别对所得产物进行结构性质表征及CO2吸附性能测试。成功将Fe元素引入到丝光沸石分子筛的骨架结构中,所合成的形貌新颖的Fe-MOR分子筛样品CO2静态吸附量最高可以达到3.57 mmol/g。

, authors=程莹, 程士敏, 谭广宇, 李盛鹏, 王闯, 尹冬雪, 王倩, 袁龙, authorsList=程莹, 程士敏, 谭广宇, 李盛鹏, 王闯, 尹冬雪, 王倩, 袁龙, authorCompany=null, correspAuthors=程士敏, authorNote=

程莹(1992—),女,学士,工程师。

, correspAuthorsNote=
程士敏(1984—),男,博士,高级工程师。
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含铁丝光沸石分子筛的合成及性能
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程莹 , 程士敏 , 谭广宇 , 李盛鹏 , 王闯 , 尹冬雪 , 王倩 , 袁龙
硅酸盐学报 | 研究论文 2024,52(9): 3047-3054
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硅酸盐学报 |研究论文 2024 , 52 (9) : 3047 -3054
含铁丝光沸石分子筛的合成及性能
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程莹 , 程士敏 , 谭广宇, 李盛鹏, 王闯, 尹冬雪, 王倩, 袁龙
作者信息
  • 正大能源材料(大连)有限公司,辽宁 大连 116000
通讯作者:
程士敏(1984—),男,博士,高级工程师。
作者简介:

程莹(1992—),女,学士,工程师。

Study on Synthesis and Properties of Iron-Containing Mordenite Molecular Sieves
Ying CHENG , Shimin CHENG , Guangyu TAN, Shengpeng LI, Chuang WANG, Dongxue YIN, Qian WANG, Long YUAN
Affiliations
  • Chia Tai Energy Materials (Dalian) Co., Ltd., Dalian 116000, Liaoning, China
  • Corresponding Author:
    CHENG Shimin (1984-), male, Ph.D., Senior Engineer. E-mail:

    CHENG Ying (1992-), female, Bachelor, Engineer. E-mail:

出版时间: 2024-09-20 doi: 10.14062/j.issn.0454-5648.20230809
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含铁丝光沸石(Fe-MOR)分子筛因其独特的结构特点和良好的应用潜力,近年开始引起较多的关注。采用无有机模板剂法水热合成含铁丝光沸石分子筛,通过精细调节合成过程的酸碱度及晶化时间可控的合成出棒簇状形貌的Fe-MOR分子筛。通过粉末X射线衍射仪,扫描电子显微镜,X射线荧光分析仪,CO2静态吸附,CO2吸附穿透试验分别对所得产物进行结构性质表征及CO2吸附性能测试。成功将Fe元素引入到丝光沸石分子筛的骨架结构中,所合成的形貌新颖的Fe-MOR分子筛样品CO2静态吸附量最高可以达到3.57 mmol/g。

含铁丝光沸石  /  模板剂  /  二氧化碳吸附性能
Introduction

In recent years, mordenite molecular sieves with various properties have been successfully synthesized by template method. Although the template method has received a lot of attention, the addition of the templating agents especially organic templating agents, would increase the cost of raw materials, and could be harmful to environment. Therefore, the method without organic template is more economical and environmentally friendly. Recently, the synthesis and applications of mordenite modified by hetero-atom have getting more and more attentions, and the performance of modified mordenite molecular sieve shows better. The common methods for modifying mordenite molecular sieve include ion exchange method and impregnation method. Some researchers have synthesized monolithic iron-containing mordenite (Fe-MOR) by template-free method, which has excellent CO2/N2 separation performance and high carbon dioxide capture performance. In addition, Fe-MOR zeolite can catalytically decompose N2O into N2 and O2, which can effectively reduce the N2O content in the atmosphere. In this work, Fe-MOR zeolite was synthesized by hydrothermal method without organic template. A novel rod-cluster-shaped Fe-MOR zeolite was controllably synthesized by fine adjustment of pH and crystallization time, and its CO2 adsorption properties were investigated.

Methods

Deionized water, tetraethyl orthosilicate, concentrated hydrochloric acid, ferric nitrate, aluminum sulfate and sodium hydroxide were used. A mixture with n(Fe) : n(SiO2) : n(Na2O) : n(H2O) : n(Al2O3) : n(HCl)=0.002 5∶1.000 0∶x∶30.000 0∶0.066 5∶y (n is molar ratio, x=0.300 0~0.580 0, y=0.100 0~0.150 0) was obtained, then the mixture was transferred into a polytetrafluoroethylene lined stainless steel autoclave and crystallized at 180°C for 7 to 14 days. When the reaction finished, a white powder sample was obtained after post-treatment.

The crystalline phase and crystallinity of the samples were analyzed by PANalytical X'Pert Powder (XRD). S-3400N scanning electron microscope (SEM) was used to observe the morphology of the samples. The elemental composition of the samples was analyzed by S8-tiger X-ray fluorescence spectrometer (XRF). The static CO2 adsorption performance of the samples was measured by ASAP-2460 physical adsorption analyzer. A fixed-bed apparatus and a Hiden Analytical HPR-20 on-line mass spectrometer were used to determine the dynamic CO2 adsorption performance of the samples.

Results and discussion

The crystalline phase of the product is effected by the amount of sodium hydroxide or the concentration of hydrochloric acid used in the initial gel mixture. The pH value of the initial gel mixture is crucial for the synthesis of pure phase Fe-MOR. The XRD results show that the peak intensity of MOR decreases gradually with the decrease of Na2O molar ratio from 0.4 to 0.36, indicating the crystallinity of samples related tod the basicity in a certain range. When the molar ratio of Na2O/SiO2 is 0.4 or 0.375, the pure phase MOR with rod-shaped cluster was obtained, in which the single rod is approximately hexagonal and the morphology is uniform. When the molar ratio of Na2O/SiO2 is in the range of 0.3-0.58, the analcite will arise if the alkalinity of the system is too high, and the amorphous phase will appear if the alkalinity is too low. This means that moderate alkalinity is conducive to the interaction of silicon, aluminum and other components, promoting the nucleation and growth of the crystallization, contributing to the synthesis of pure mordenite. Moreover, when the molar ratio of Na2O/SiO2 is 0.4, the pure phase of Fe-MOR can be controllably synthesized by adjusting the molar ratio of concentrated hydrochloric acid.

The pure phase Fe-MOR molecular sieves can also be synthesized by shortening the crystallization time under the constant pH. The axial size of the synthesized samples also decreases with the decrease of the crystallization time. The results show that the longer the crystallization time is, the better the axial growth of the crystals, but when the crystallization time is less than 7 days, the hetero-crystalline phase of analcite appears.

The static adsorption capacity of CO2 on Fe-MOR samples was similar because the adsorption mainly depends on the atmosphere pressure. The capacity of dynamic adsorption of CO2 is due to the difference of the suitable site of electric field in the 8-membered ring channel of MOR, which determines the adsorption capacity in the dynamic CO2 penetration under low partial pressure of CO2. The microstructure of Fe-MOR molecular sieves synthesized under different conditions are different, which results in the difference of CO2 dynamic adsorption capacity of several samples.

Conclusions

The results show that the pH of the gel mixture and crystallization time affected the synthetic products. When the amount of hydrochloric acid is constant, the high alkalinity results in analcite crystals while the low alkalinity results in amorphous phase. When the amount of sodium hydroxide is high, increasing the amount of hydrochloric acid will result in the pure Fe-MOR molecular sieves. The axial size of the crystal will decrease with the shortening of the synthesis time under appropriate pH value. When the crystallization time was less than 7 days, the hetero-crystalline phase of analcite appeared, which was attributed to the short synthesis time leading to incomplete crystallization. Rod cluster Fe-MOR molecular sieves were synthesized by hydrothermal method without organic template and showed good static and dynamic adsorption capacity for CO2, and the static adsorption capacity was up to 3.57 mmol/g.

iron-containing mordenite  /  template  /  carbon dioxide adsorption
程莹, 程士敏, 谭广宇, 李盛鹏, 王闯, 尹冬雪, 王倩, 袁龙. 含铁丝光沸石分子筛的合成及性能. 硅酸盐学报, 2024 , 52 (9) : 3047 -3054 . DOI: 10.14062/j.issn.0454-5648.20230809
Ying CHENG, Shimin CHENG, Guangyu TAN, Shengpeng LI, Chuang WANG, Dongxue YIN, Qian WANG, Long YUAN. Study on Synthesis and Properties of Iron-Containing Mordenite Molecular Sieves[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (9) : 3047 -3054 . DOI: 10.14062/j.issn.0454-5648.20230809
  • 大连市重点科技研发计划项目(2023YF16GX024)
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2024年第52卷第9期
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doi: 10.14062/j.issn.0454-5648.20230809
  • 接收时间:2023-10-20
  • 首发时间:2026-10-22
  • 出版时间:2024-09-20
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  • 收稿日期:2023-10-20
  • 修回日期:2023-11-11
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大连市重点科技研发计划项目(2023YF16GX024)
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    正大能源材料(大连)有限公司,辽宁 大连 116000

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程士敏(1984—),男,博士,高级工程师。
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2种不同金属材料的力学参数
科
Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)
属
Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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