浸漬法制備高選擇性1-丁烯齊聚催化劑

肖林久， 陳家歡， 盛永剛， 李文澤， 王金豹

(沈陽化工大學 應用化學學院 遼寧省稀土化學及重點應用實驗室， 遼寧 沈陽 110142)

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肖林久， 陳家歡， 盛永剛， 李文澤， 王金豹

(沈陽化工大學 應用化學學院 遼寧省稀土化學及重點應用實驗室， 遼寧 沈陽 110142)

摘要：通過分步浸漬法制備/γ-Al2O3催化劑，并用于催化1-丁烯齊聚反應，考察了催化劑制備條件和反應條件對催化性能的影響，并與Fe2(SO4)3/γ-Al2O3催化劑進行性能比較。結果表明，在0.96 MPa、60℃、液時空速為5 h-1的反應條件下，采用Fe負載量為負載量為1.2 mmol/g(γ-Al2O3)的/γ-Al2O3 催化劑，1-丁烯齊聚反應的轉(zhuǎn)化率達到68.0%，二聚物選擇性為95.0%。α-Fe2O3是催化1-丁烯齊聚反應的活性組分，并能提高二聚體選擇性；此外，α-Fe2O3晶相與的相互作用對其催化1-丁烯齊聚反應的活性有重要影響，γ-Al2O3與的相互作用也對催化活性有一定的影響。Fe負載量為6%的/γ-Al2O3催化活性最高，此時NH3-TPD結果顯示，催化劑只存在較弱的酸中心和適中的酸量。

關鍵詞：1-丁烯齊聚； 催化劑；； 硫酸鐵

1　實驗部分

1.1原料和試劑

γ-Al2O3(Al2O3質(zhì)量分數(shù)98%，比表面積227.41 m2/g，平均孔徑5.08 nm)，濟南魯淮商貿(mào)有限公司產(chǎn)品；Fe(NO3)3·9H2O、(NH4)2SO4，分析純，天津市大茂化工試劑廠產(chǎn)品；Fe2(SO4)3，分析純，天津市耀華化工廠產(chǎn)品。

1.2催化劑的制備

將載體γ-Al2O3研磨、篩分，選用粒徑20～40目部分。將稱量的Fe(NO3)3溶于一定量的去離子水中，待溶解后快速加入定量的γ-Al2O3，使其浸漬均勻，超聲波下充分震蕩1 h，放置120℃下烘干，然后移至馬福爐中500℃焙燒1 h，取出冷卻至室溫，制得Fe負載量(質(zhì)量分數(shù)，以下同)分別為2%、4%、6%、8%、10%的Fe2O3/γ-Al2O3催化劑。

1.2.2Fe2(SO4)3/γ-Al2O3的制備

將載體γ-Al2O3研磨、篩分，選用粒徑20～40目部分。將稱量的Fe2(SO4)3溶于一定量的去離子水中，待溶解后快速加入定量的γ-Al2O3，使其浸漬均勻，超聲波下充分震蕩1 h，放置120℃下烘干，然后移至馬福爐中500℃焙燒3 h，取出冷卻至室溫，制得Fe擔載量為6%的Fe2(SO4)3/γ-Al2O3催化劑。

1.3反應裝置和流程

采用高壓微型固定床連續(xù)流動的不銹鋼反應器(內(nèi)徑8 mm，長70 mm)進行1-丁烯齊聚反應。采用北京東方儀器廠產(chǎn)SB-2型雙柱塞微量泵將反應原料從反應器底部送入反應床層。反應溫度控制在40～200℃范圍，由背壓調(diào)壓器控制反應壓力在0.8～1.8 MPa范圍。反應產(chǎn)物從背壓閥流出后，經(jīng)六通閥進入氣相色譜完成在線分析，隨時監(jiān)測反應狀況。

1.4聚合產(chǎn)物分析

采用北京北分瑞利分析儀器公司3420A型氣相色譜儀和面積歸一化法分析液體產(chǎn)物和尾氣組成。色譜儀配有30 m HJ.624毛細管柱和FID檢測器；氣化溫度240℃，柱溫220℃，檢測器溫度250℃；由色譜分析工作站處理數(shù)據(jù)。根據(jù)分析結果計算1-丁烯轉(zhuǎn)化率和液體產(chǎn)物各組分的選擇性。

1.5負載量計算方法

(1)

(2)

2　結果與討論

2.1.1表面分散狀態(tài)

圖1　不同焙燒溫度下負載Fe2O3得到的的XRD譜Fig.1　XRD patterns of Fe2O3·different calcination temperatures ●Fe2(SO4)3；■α-Fe2O3；▲γ-Al2O3；★Fe2O3

2.1.2催化劑的酸性

圖2　不同F(xiàn)e負載量的的 NH3-TPD曲線Fig.with different Fe loadings

w(Fe)/%: (1) 2; (2) 4; (3) 6; (4) 10; (4) 12

2.2.1負載Fe2O3焙燒溫度的影響

圖3　負載Fe2O3的焙燒溫度對所得催化劑催化1-丁烯齊聚反應轉(zhuǎn)化率的影響Fig.3　Effect of calcination temperature for loading Fe2O3 of/γ-Al2O3 catalyst on oligomerization conversion of 1-butene over the catalyst

2.2.2Fe負載量的影響

圖4　Fe負載量對催化劑催化 1-丁烯齊聚反應的影響Fig.catalyst on oligomerization of 1-butene at different temperatures

(a)x; (b)s(Dimers); (c)s(Trimers)

圖負載量對催化劑催化1-丁烯齊聚反應的影響Fig.catalyst on oligomerization of 1-buteneT=60℃; p=0.96 MPa; LHSV=5 h-1; w(Fe)=6% (1) x; (2) s(Dimers); (3) s(Trimers)

圖6　不同反應溫度下Fe負載量為6%的Fe2(SO4)3/γ-Al2O3催化劑催化1-丁烯齊聚反應的轉(zhuǎn)化率Fig.6　Conversion of 1-butene oligomerization vs reaction temperatures over Fe2(SO4)3/γ-Al2O3catalyst with 6% Fe loadingp=1.2 MPa; LHSV=1 h-1

2.4.1反應溫度的影響

圖7　反應溫度對催化劑催化 1-丁烯齊聚反應的影響Fig.7　Effects of reaction temperature on oligomerization of

(1)x; (2)s(Dimers); (3)s(Trimers)

2.4.2反應壓力的影響

圖8　反應壓力對催化劑催化 1-丁烯齊聚反應的影響Fig.8　Effects of reaction pressure on oligomerization of

(1)x; (2)s(Dimers); (3)s(Trimers)

2.4.3液時空速的影響

圖9　反應液時空速對催化劑催化 1-丁烯齊聚反應的影響Fig.9　Effects of liquid hourly space velocity on oligomerization of 1-butene over

(1)x; (2)s(Dimers); (3)s(Trimers)

3　結　論

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收稿日期：2015-05-18

基金項目：遼寧省科技技術攻關項目(2011223006)資助

文章編號：1001-8719(2016)04-0695-08

中圖分類號：O643.32

文獻標識碼：A

doi:10.3969/j.issn.1001-8719.2016.04.006

XIAO Linjiu, CHEN Jiahuan, SHENG Yonggang, LI Wenze, WANG Jinbao

(LiaoningProvince,KeyLaboratoryforRare-EarthChemistryandApplication,CollegeofAppliedChemistry,ShenyangUniversityofChemicalTechnology,Shenyang110142,China)

Abstract：/γ-Al2O3 catalyst was prepared by step-impregnation method, and its catalytic performance for 1-butene oligomerization was studied and compared with Fe2(SO4)3/γ-Al2O3 catalyst. The influences of the preparation and reaction conditions on the catalytic activity of /γ-Al2O3 for 1-butene oligomerization were investigated. The results showed that, on the reaction condition of pressure of 0.96 MPa, reaction temperature of 60℃ and liquid hourly space velocity of 5 h-1, with the /γ-Al2O3 of 6% Fe loading and 1.2 mmol/g(γ-Al2O3) loading as catalyst, the conversion rate of 1-butene oligomerization reached 68.0% and the dimerization selectivity was 95.0%. α-Fe2O3 is an active component in catalytic 1-butene oligomerization and high dimerization selectivity can be obtained. In addition, the interaction between α-Fe2O3 crystal phase and had an important influence on the catalytic activity of /γ-Al2O3 in 1-butene oligomerization and the interaction between γ-Al2O3and also had some influence. Catalyst activity of /γ-Al2O3 was maximum with 6% Fe loading, and its NH3-TPD results showed there existed weak acid sites and only a moderate amount of acid.

Key words：1-butene oligomerization； catalyst； /γ-Al2O3； ferric sulfate

通訊聯(lián)系人： 肖林久，男，教授，博士，從事精細化工、稀土材料、催化等方面的研究；Tel：024-89381616；E-mail：x109@163.com