(NH_4)_2SO_4改性Cr/V双金属催化剂的制备及乙烯聚合研究
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摘要
在Phillips催化剂基础上开发出CrOx-VOx/SiO_2双中心催化剂,并用(NH_4)_2SO_4对其进行改性,考察了(NH_4)_2SO_4的浸渍方式、浸渍量和催化剂焙烧温度对乙烯聚合行为和产物结构与性能的影响。结果表明,(NH_4)_2SO_4改性的铬钒双金属催化剂的乙烯聚合活性得到提高,且随(NH_4)_2SO_4负载量的增加,活性呈现先增加后降低的趋势。采用共浸渍制备的催化剂的乙烯聚合活性大于分布浸渍法。(NH_4)_2SO_4对V活性组分有促进作用,使改性催化剂的均聚产物分子质量增加,加入1-己烯共聚单体后,分子质量进一步增加。
A Cr Ox-VOx/Si O_2 bimetallic catalyst is developed on the basis of Phillips catalyst and modified with(NH_4)_2SO_4.The influences of calcination temperature for catalyst,and impregnation method and amount of(NH_4)_2SO_4 on polymerization behavior of ethylene and properties of product are investigated. The results show that the addition of(NH_4)_2SO_4 helps Cr Ox-VOx/Si O_2 bimetallic catalyst improve activity in ethylene polymerization. With the increase of(NH_4)_2SO_4 dosage,the activity of the catalyst increases first and decreases then.The activity of the catalyst prepared by co-impregnation method is greater than that made by distribution impregnation method.(NH_4)_2SO_4 can promote V active site and hence increases the molecular weight of homopolymer produced.The addition of 1-hexene can further increase the molecular weight of homopolymer.
A Cr Ox-VOx/Si O_2 bimetallic catalyst is developed on the basis of Phillips catalyst and modified with(NH_4)_2SO_4.The influences of calcination temperature for catalyst,and impregnation method and amount of(NH_4)_2SO_4 on polymerization behavior of ethylene and properties of product are investigated. The results show that the addition of(NH_4)_2SO_4 helps Cr Ox-VOx/Si O_2 bimetallic catalyst improve activity in ethylene polymerization. With the increase of(NH_4)_2SO_4 dosage,the activity of the catalyst increases first and decreases then.The activity of the catalyst prepared by co-impregnation method is greater than that made by distribution impregnation method.(NH_4)_2SO_4 can promote V active site and hence increases the molecular weight of homopolymer produced.The addition of 1-hexene can further increase the molecular weight of homopolymer.
引文
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[2]Heidemeyer P,Pfeiffer J. Special requirements on compounding technology for bimodal polyolefines and their industrial application[J].Macromolecular Symposia,2015,181(1):167-176.
[3]Cheng R,Liu B,Xue X,et al. a supproted metal-oxide-doubleactive-center catalyst for ethylene polymerization,preparation method and application thereof:WO,WO/2013/155982[P].2013.
[4]Cheng R,Xue X,Liu W,et al. Novel SiO2-supported chromium oxide(Cr)/vanadium oxide(V)bimetallic catalysts for production of bimodal polyethylene[J].Macromolecular Reaction Engineering,2015,9(5):462-472.
[5]Zhao N,Cheng R,He X,et al.A Novel SiO2-supported Cr-V bimetallic catalyst making polyethylene and ethylene/1-hexene copolymers with bimodal molecular weight distribution[J].Macromolecular Chemistry&Physics,2014,215(18):1753-1766.
[6]Zhao N,Cheng R,He X,et al.A Novel SiO2-supported Cr-V bimetallic catalyst making polyethylene and ethylene/1-hexene copolymers with bimodal molecular weight distribution[J].Macromolecular Chemistry&Physics,2014,215(18):1434-1445.
[7]蒋文伟.超强酸催化剂的研究进展[J].精细化工,1997,(1):46-49.
[8]Arata K. Solid superacids[J]. Advances in Catalysis,1990,37:165-211.
[9]毛东森,卢冠卢.负载型氧化物固体超强酸催化剂的制备及应用[J].化学通报,2001,64(5):000278-000284.
[10]唐新硕.超强酸催化剂[J].石油化工,1981,(12):4+47-58.
[11]Soled S,Dispenziere N,Saleh R.4.25 Butene dimerization over sulfate and tungstate modified solid acids[J]. Studies in Surface Science&Catalysis,1994,90:537-541.
[12]Soled S L,Dispenziere N C,Saleh R Y,et al.Dimerization catalyst and process therefor[J].1992.
[13]Mcdaniel M P.Chapter 3-A review of the phillips supported chromium catalyst and its commercial use for ethylene polymerization[J].Advances in Catalysis,2010,53:123-606.
[14]Mc Daniel,Deslauriers,Paul J,et al. Methods of preparing active chromium/alumina catalysts via treatment with sulfate and polymers produced using the chromium/alumina catalysts[J].2005.
[15]刘科伟,陈天朗.硫酸铵的热分解[J].化学研究与应用,2002,14(6):737-738.
[16]Chinone T,Okazaki S. Effect of sulfate ion on catalytic activity of molybdenum trioxide-titanium dioxide for reduction of NOx[J].1978.
[17]Okazaki S,Kumasaka M,Yoshida J,et al. Effect of sulfate ion on the catalytic activity of molybdenum oxide-titanium dioxide(Mo OxTi O2)for the reduction of nitric oxide with ammonia[J].Industrial&Engineering Chemistry Product Research&Development,1981;20(2):301-304.
[18]孙巧巧.新型氟改性、钛氟改性硅胶负载型铬钒双中心聚乙烯催化剂研究[D].上海:华东理工大学,2013.
[19]李文博.加压条件下无机铬钒双中心乙烯聚合催化剂及其烷基铝预还原研究[D].上海:华东理工大学,2017.
[20]薛新.新型高效复合型CrOx-VOx/SiO2聚乙烯催化剂的研究[D].上海:华东理工大学,2011.