硅钛比对TS-1分子筛催化甲醇羰基化反应性能的影响

程灵超; 郑博玄; 高希然; 迪丽努尔·艾力; 方亚平; 艾沙·努拉洪

doi:10.13568/j.cnki.651094.651316.2020.05.13.0003

您当前的位置：

首页 >

文章列表页 >

硅钛比对TS-1分子筛催化甲醇羰基化反应性能的影响

化学与化工 | 更新时间：2026-01-21

- 硅钛比对TS-1分子筛催化甲醇羰基化反应性能的影响
- 硅钛比对TS-1分子筛催化甲醇羰基化反应性能的影响
- 新疆大学学报（自然科学版中英文） 2021年38卷第1期页码：37-43
- 作者机构：
  
  1. 煤炭洁净转化与化工过程新疆维吾尔自治区重点实验室
  2. 新疆大学化学化工学院
- 作者简介：
- 基金信息：
  
  国家级大学生创新项目（201910755071）;新疆维吾尔自治区重点实验室开放课题（2017D04005）
- DOI：10.13568/j.cnki.651094.651316.2020.05.13.0003
  中图分类号： TQ225.24;TQ426
- 纸质出版：2021
- 稿件说明：
移动端阅览
[1]程灵超,郑博玄,高希然,等.硅钛比对TS-1分子筛催化甲醇羰基化反应性能的影响[J].新疆大学学报(自然科学版)(中英文),2021,38(01):37-43.
[1]程灵超,郑博玄,高希然,等.硅钛比对TS-1分子筛催化甲醇羰基化反应性能的影响[J].新疆大学学报(自然科学版)(中英文),2021,38(01):37-43. DOI： 10.13568/j.cnki.651094.651316.2020.05.13.0003.

DOI：10.13568/j.cnki.651094.651316.2020.05.13.0003.

摘要

对TS-1分子筛而言

它的各种物理性质影响其反应活性.通过调节和控制催化剂的物理性质能够提高产物选择性和收率

降低副产物

从而提高反应活性.本文考察了TS-1分子筛的硅钛比对甲醇羰基化反应性能的影响.在合成TS-1分子筛时

通过控制硅源和钛源的比值得到了不同硅钛比的TS-1分子筛.结果表明:硅钛比大时(例如:硅钛比为64)

TS-1沸石分子筛的非骨架钛含量和锐钛矿含量较少

甲醇羰基化反应效果较好;反应温度为300℃时

甲醇转化率为30%

乙酸甲酯和甲酸甲酯选择性之和为26%

反而硅钛比较小(例如:硅钛比为34和41)时

TS-1沸石分子筛的非骨架钛含量和锐钛矿含量较多

甲醇羰基化反应性能较差.甲醇转化率仅为5%

乙酸甲酯和甲酸甲酯选择性之和仅为4%.产生以上结果的原因之一是硅钛比大

TS-1沸石分子筛结晶完全、杂质少、孔道通畅;其二为钛分布合理

其三为所生成的中间产物可能继续进行反应生成二甲醚、乙醇及裂解生成CO2、CO、干气等副产物.

Abstract

For TS-1 molecular sieve

its various physical properties affect its reaction activity. By adjusting and controlling the physical properties of the catalyst

the selectivity and yield of the products can be improved

and the by-products can be reduced

so as to improve the reaction activity.The effect of Si/Ti ratio of TS-1 molecular sieve on methanol carbonylation was investigated in this paper. In the synthesis of TS-1 zeolites

TS-1 zeolites with different Si/Ti ratios were obtained by controlling the ratio of Si to Ti

the result shows that when the ratio of Si to Ti is high(e.g. the ratio of Si to Ti is 64)

the content of non framework titanium and anatase in TS-1 Zeolite is less

and the effect of methanol carbonylation is better

when the reaction temperature is 300 ℃

the conversion of methanol is 30%

and the total selectivity of methyl acetate and methyl formate is 26%

and when the ratio of Si to Ti is low(e.g. the ratio of Si to Ti is 34 or 41)

TS-1 zeolites have high content of non framework titanium and anatase

and poor performance of methanol carbonylation. The conversion of methanol is only 5%

and the selectivity of methyl acetate and methyl formate is only 4%. One of the reasons for the above results is the high ratio of Si to Ti

complete crystallization

less impurities and smooth pore channels of TS-1 Zeolite; the second is that the titanium distribution is reasonable; the third is that the intermediate products may continue to react to produce dimethyl ether

ethanol and pyrolysis to produce CO2

dry gas and other by-products.

关键词

Keywords

references

艾沙·努拉洪,莫文龙,马凤云.焙烧方法和焙烧条件对纳米Au/HZSM-5催化剂金粒径和催化性能的影响[J].燃料化学学报,2016,44(6):710-717.Aisha Nulahong,MO W L,MA F Y.Effects of calcination methods and calcination conditions on gold particle size and catalytic performance of nano Au/HZSM-5 Catalyst[J].J Fuel Chem Technol,2016,44(6):710-717.(in Chinese)

毛东森,夏建超.分子筛硅铝比及晶粒粒径对Cu-Zn O-Al2O3/HZSM-5催化剂直接合成二甲醚反应性能的影响[J].燃料化学学报,2012,40(2):235-240.MAO D S,XIA J C.Effects of Si/Al ratio and grain size of zeolite on direct synthesis of dimethyl ether over Cu O-Zn O-Al2O3/HZSM-5 Catalyst[J].J Fuel Chem Technol,2012,40(2):235-240.(in Chinese)

谢克昌,李忠.甲醇及其衍生物[M].北京：化学工业出版社,2002.XIE K C,LI Z.Methanol and its derivatives[M].Beijing:Chemical Industry Press,2002.(in Chinese)

应卫勇,曹发海,房鼎业.碳一化工主要产品生产技术[M].北京：化学工业出版社,2004.YING W Y,CAO F H,FANG D Y.Production technology of main products of carbon one chemical industry[M].Beijing:Chemical Industry Press,2004.(in Chinese)

张海涛,曹发海,刘殿华,等.合成气直接合成二甲醚与甲醇的热力学分析[J].华东理工大学学报(自然科学版),2001(2):198-201.ZHANG H T,CAO F H,LIU D H,et al.Thermodynamic analysis of direct synthesis of dimethyl ether and methanol from Syngas[J].Journal of East China University of Science and Technology (Natural Science Edition),2001(2):198-201.(in Chinese)

刘昌俊,许根慧.一碳化工产品及其发展方向[J].化工学报，2003,54:524-530.LIU C J,XU G H.C1 chemical products and trend of development[J].CIESC Journal,2003,54:524-530.(in Chinese)

周晓红.二甲醚的用途与发展前景分析[J].煤炭加工与综合利用,2002(4):33-35.ZHOU X H.Application and development prospect of dimethyl ether[J].Coal Processing and Comprehensive Utilization,2002(4):33-35.(in Chinese)

陆家亮,赵素平.中国能源消费结构调整与天然气产业发展前景[J].天然气工业,2013,33(11):9-15.LU J L,ZHAO S P.Adjustment of energy consumption structure and development prospect of natural gas industry in China[J].Natural Gas Industry,2013,33(11):9-15.(in Chinese)

艾沙·努拉洪,赵艳慧,毕坤豪,等.Au、Pt改性HZSM-5纳米沸石催化剂上的甲醇羰基化反应性能研究[J].新疆大学学报(自然科学版),2019,36(2):160-168+173.Aisha Nulahong,ZHAO Y H,BI K H,et al.Performance of Au and Pt modified HZSM-5 nano zeolite catalysts for methanol carbonylation[J].Journal of Xinjiang University (Natural Science Edition),2019,36(2):160-168+173.(in Chinese)

艾沙·努拉洪,莫文龙,马凤云.基于脉冲微反装置的Au/HZSM-5催化剂上正丁烷反应性能研究[J].分子催化,2014(6):544-552.Aisha Nulahong,MO W L,MA F Y.Study on the performance of Au/HZSM-5 Catalyst for n-butane reaction based on pulse microreactor[J].Journal of Molecular Catalysis,2014(6):544-552.(in Chinese)

艾沙·努拉洪.纳米Au/HZSM-5沸石催化剂的制备与正丁烷转化研究[D].大连:大连理工大学,2013.Aisha Nulahong.Preparation of nano Au/HZSM-5 zeolite catalyst and its application in n-butane conversion[D].Dalian:Dalian University of Technology,2013.(in Chinese)

丁孝涛,张培青,安立敦,等.载金微孔分子筛催化剂研究进展[J].分子催化,2010(1):93-98.DING X T,ZHANG P Q,AN L D,et al.Research progress of gold loaded microporous molecular sieve catalysts[J].Journal of Molecular Catalysis,2010(1):93-98.(in Chinese)

PESTRYAKOV A N,BOGDANCHIKOVA N,SIMAKOV A,et al.Catalytically active gold clusters and nanoparticles for COoxidation[J].Surface Science,2007,601(18):3792-3795.

LIU G L,NIU T,CAO A,et al.The deactivation of Cu-Co alloy nanoparticles supported on Zr O2for higher alcohols synthesis from syngas[J].Fuel,2016,176:1-10.

KANG N,YANG Q L,AN K,et al.Mixed oxides of La-Ga-O modified Co/Zr O2for higher alcohol synthesis from syngas[J].Catalysis Today,2018,Online.

CHENG K,ZHANG L,KANG J,et al.Selective transformation of syngas into gasoline range hydrocarbons over mesoporous H-ZSM-5-supported cobalt nanoparticles[J].Chemistry,2015,21(5):1928-1937.

CHOI S M,KANG Y J,KIM S W.Effect ofγ-alumina nanorods on CO hydrogenation to higher alcohols over lithium-promoted Cu Zn-based catalysts[J].Applied Catalysis A:General,2018,549:188-196.

DA W B,HAM H,CHO J M,et al.Effect of Mn promoter on Rh/tungsten carbide on product distributions of alcohols and hydrocarbons by CO hydrogenation[J].RSC Advances,2016,6(103):101535-101543.

GAO S,LI X,LI Y,et al.Effects of gallium as an additive on activated carbon-supported cobalt catalysts for the synthesis of higher alcohols from syngas[J].Fuel,2018,230:194-201.

HUAN G C,ZHANG M,ZHU C,et al.Fabrication of highly stable Si O2encapsulated multiple Cu Fe nanoparticles for higher alcohols synthesis via CO hydrogenation[J].Catalysis Letters,2018,148(4):1080-1092.

HUI D S,ZHEN Y S.A Miracle Metal@Zeolite for selective conversion of syngas to ethanol[J].Chem,2020,6:1-12.

WANG C,ZHANG J,QIN G,et al.Direct Conversion of Syngas to Ethanol within Zeolite Crystals[J].Chem,2020,6(3).

XU H S,CHEN Q L,JAWAID M,et al.Catalytic properties of ZSM-5 based Cu-Zn catalysts applies to ethanol synthesis from syngas[J].Matec Web of Conferences,2016,67:01012.

WANG D,BI Q,YIN G,et al.Photochemical preparation of anatase Titania supported Gold catalyst for ethanol synthesis from CO2hydrogenation[J].Catalysis Letters,2017,148(1):1-12.

LUK H T,MONDELLI C,FERRE D C,et al.Status and prospects in higher alcohols synthesis from syngas[J].Chemical Society Reviews,2017,46(5):1358-1426.

KANG X,ZHENG H B,XING Z Q,et al.Advances in bifunctional catalysis for higher alcohol synthesis from syngas[J].Chinese Jounal of Catalysis,2013,34(1):116-129.

周颖,张利雄.简单水热合成法制备介孔ZSM-5分子筛[J].南京工业大学学报(自然科学版),2016,38(1):19-26+32.ZHOU Y,ZHANG L X.Preparation of mesoporous ZSM-5 molecular sieves by simple hydrothermal synthesis[J].Journal of Nanjing University of Technology (Natural Science Edition),2016,38(1):19-26+32.(in Chinese)

孙爽,孙成元.浅谈水热合成法在晶体合成中的应用[J].内蒙古民族大学学报(自然科学版),2014,29(5):520-524.SUN S,SUN C Y.Application of hydrothermal synthesis in crystal synthesis[J].Journal of Inner Mongolia University for Nationalities(Natural Science Edition),2014,29(5):520-524.(in Chinese)

李钢,郭新闻,王祥生.水热法合成的钛硅分子筛催化性能研究[J].石油学报:石油加工,1999(5):75-78.LI G,GUO X W,WANG X S.Study on catalytic performance of titanium silicalite synthesized by hydrothermal method[J].Acta Petrologica Sinica:Petroleum Processing,1999(5):75-78.(in Chinese)

浏览量

320

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

Au、Pt改性HZSM-5纳米沸石催化剂上的甲醇羰基化反应性能研究