研究與開發(fā)合成纖維工業(yè),2012,35(4):42CHINA SYNTHETIC FIBER INDUSTRY助劑對苯加氫Ru系催化劑催化性能的影響李建修,吳濟(jì)民’,常守欣2(1.平頂山工業(yè)職業(yè)技術(shù)學(xué)院化工系,河南平頂山467001;2.中國平煤神馬建工集團(tuán)土建處,河南平頂山467001)摘要:以三氯化釕(RuC3)、硫酸鋅(ZnSO4)和硫酸亞鐵(FeSO4)為原料,采用共沉淀法制備 Ru-Zn及Ru-FeZa催化劑研究了苯選擇加氫制環(huán)己烯過程中助劑Zn和Zm/Fe對Ru系催化劑催化加氫性能的影響,并利用透射電鏡等對催化劑進(jìn)行表征。結(jié)果表明RuZn催化劑粒子清晰較為分散,Rn-FeZn催化劑粒徑變大,比表面積變小;Ru系催化劑中加入助劑Zn,Ru/Zmn摩爾比為7時(shí)環(huán)己烯選擇性較高加入第三組分Fe,Zm/Fe摩爾比為10,環(huán)己烯選擇性進(jìn)一步提高; Ru-Fe-Zn催化劑具有很好的催化活性和穩(wěn)定性,苯轉(zhuǎn)化率達(dá)54.9%,環(huán)己烯選擇性達(dá)81.8%。關(guān)鍵詞:苯環(huán)己烯催化劑三氯化釘助劑加氫選擇性中圖分類號;TQ314.242文獻(xiàn)標(biāo)識(shí)碼:A文章編號:1001-0041(202)04-042-04苯加氫制環(huán)已烯,再由環(huán)己烯水合得到環(huán)己Ru/Zn摩爾比為7配置一定濃度的RuCl3及Zn醇生產(chǎn)己二酸的工藝是日本旭化成株式會(huì)社開發(fā)SO4·7H2O水溶液,攪拌30min;然后逐滴加人的,與傳統(tǒng)醇酮路線相比,安全節(jié)能,碳原子利用過量的沉淀劑NaOH溶液,加完后,繼續(xù)攪拌60率100%,無廢棄物和環(huán)境污染,具有經(jīng)濟(jì)性和環(huán)min,抽濾,得到黑色膠狀沉淀,經(jīng)過還原后備用。境友好等特點(diǎn)-3。同時(shí),作為中間產(chǎn)物的環(huán)己Ru-Fezn催化劑的制備:根據(jù)催化劑的組烯又是重要的有機(jī)合成體。因此,環(huán)已烯及其下成,按Zn/Fe摩爾比為10配置一定濃度的FeSO游產(chǎn)品有廣闊的市場前景46。和ZnSO4·7H2O水溶液攪拌30min;然后與自從河南神馬集團(tuán)引進(jìn)了該工藝,國內(nèi)很多定濃度的RuCl3溶液混合攪拌10min以上,再逐高等院校及科研單位開始跟蹤和研究該項(xiàng)技術(shù),滴加人過量的沉淀劑NaOH溶液,持續(xù)攪拌60并取得了一定進(jìn)展,但大多數(shù)只是停留在實(shí)驗(yàn)室min,抽濾,得到黑色膠狀沉淀,經(jīng)過還原后備用。階段,缺乏對長期生產(chǎn)中催化劑的穩(wěn)定性和工業(yè)1.3催化劑活性評價(jià)適用性的考察1)。作者針對傳統(tǒng)的Ru系催化采用WDF-0.25型高壓釜進(jìn)行催化劑活性劑,加入Zm或一定比例的Zn/Fe,以探求在加入評價(jià)。在250mL高壓釜進(jìn)行反應(yīng),反應(yīng)溫度廉價(jià)的助劑后,使得苯加氫Ru系催化劑的穩(wěn)定140-150℃,壓力SMPa,催化劑加入量0.5g,苯性和工業(yè)適用性有所提高。加入量70mL,另外加入70mL水,ZrO22.5gFeSO4·7H2O12.5g做溶劑,反應(yīng)時(shí)間30min1實(shí)驗(yàn)開始計(jì)時(shí),5,10,15min等每隔5min取樣1次,11原料及試劑通過氣相色譜分析,評價(jià)催化劑活性。以此方法三氯化釕(RuCl3nH2O):(Ru)為37%,分別對 Ru-Fe-Z和陽uZn催化劑進(jìn)行考察。昆明貴金屬研究所產(chǎn);硫酸亞鐵(FeSO4·7H2O)、4分析測試氫氧化鈉(NaOH):分析純,北京化工廠產(chǎn);硫酸氣相色譜分析:采用FID檢測,面積校正歸鋅(ZnsO4·7H20):天津市北方天醫(yī)化學(xué)試劑廠法定量計(jì)算苯加氫反應(yīng)的苯轉(zhuǎn)化率、環(huán)已烯收率產(chǎn);二氧化鋯(Z0O2):天津市贏達(dá)稀貴化學(xué)試劑和環(huán)己烯選擇性廠產(chǎn)。透射電鏡(TEM)觀察:使用日本JEM20112催化劑制備型高分辨電子透射電鏡觀察催化劑的形貌,加速采用共沉淀法分別制備Ru-Fe-Zn及Ru-Z收稿日期中國煤化工2120524催化劑。作者簡CNMHG主要從事工業(yè)催RuZn催化劑的制備:根據(jù)催化劑的組成,按化劑的應(yīng)用開發(fā)研究。E-mal:jix000@126.c0m。第4期李建修等助劑對苯加氫Ru系催化劑催化性能的影響電壓100kV。的選擇性影響較大,當(dāng)Zn/Fe摩爾比為10時(shí),出BET比表面積(S)及孔徑測定:采用美國現(xiàn)了一個(gè)極值點(diǎn)。因此,選擇Zn/Fe摩爾比為10US Nova version2.0物理吸附儀,氮?dú)庾魑劫|(zhì),較理想。液氮溫度(77K)下進(jìn)行吸附,測定吸附脫附等溫線。試樣量0.15~0.50g,150℃下脫氣1.5h粒徑分布分析:采用北京中美儀器科技有限公司Rse2006激光粒度分析儀測試。2結(jié)果與討論2.1催化劑表征由圖1可看出,Ru-Zn催化劑粒子清晰,相對較為分散,Ru- Fe-Zn許多粒子堆積在一起形成了粒子簇。采用分析軟件得到的平均粒子大小如Ru/Zn摩爾比8. Ru-Zn下:Ru-Zn平均粒徑約為5mm,Ru-FeZn的平均粒徑較大,以8-10mm的據(jù)多。70冊10圖1催化劑的TEM照片Zn/Fe摩爾比Fig. 1 TEM images of catalyst由表1可以看出,Ru-FeZn催化劑的Sr為圖2助劑添加量對Ru系催化劑性能的影響27m2/g,平均孔徑為159nm;RuZn催化劑的Fig 2 Effect of additive addition on properties of Ru catalystSBr為42m2/g,平均孔徑為112m。較大的孔徑2.3催化劑活性評價(jià)有利于中間產(chǎn)物環(huán)己烯的脫附和擴(kuò)散,減少了進(jìn)由表2可以看出,相同時(shí)間內(nèi),苯加氫制備環(huán)步加氫生成環(huán)己烷的機(jī)會(huì),因而有利于提高環(huán)已烯,RuFe-Zn催化劑活性明顯高于 Ru-Zn催化已烯的選擇性(2)。劑,其苯轉(zhuǎn)化率和環(huán)己烯收率均相應(yīng)較高,環(huán)己烯表1催化劑的比表面積及平均孔徑與粒徑選擇性相當(dāng)。這是因?yàn)榧尤肆说谌N金屬Fe,催Tab 1 Specific surface area, average pore化劑表面活性組分活化時(shí)間縮短的緣故。diameter and particle size of catalysts表2Ru-FeZn與RuZn催化劑的催化性能比較催化劑平均平均Tab 2 Catalytic activity comparison(m2·g)孔徑/m粒徑/mbetween Ru-Fe-Zn and Ru-Zn catalystsRu -Zn112Ru-Fe -Zn反應(yīng)時(shí)間/轉(zhuǎn)化率%選擇性,%收率,%nin Ru-Fe-Zn Ru-Zn Ru-Fe-Zn Ru-Zn Ru-Fe-Zn Ru-Zn2.2助劑添加量的影響1529415.990.36由圖2a可以看出,隨著Ru系催化劑中Zn2041.928.186.286.936.124.42556.0084.384.847.233.0含量的減少,苯加氫反應(yīng)轉(zhuǎn)化率增加,但目標(biāo)產(chǎn)物306.147.781.582453.139.3環(huán)己烯的選擇性降低。綜合比較,Ru/Zn摩爾比3575.354.877.480.058.343.9為7時(shí)較佳。由圖2b可以看出,在催化劑中助劑458326610.714.858.849.9zFe摩爾比對反應(yīng)影響較為復(fù)雜,當(dāng)其摩爾比2.4催化劑中國煤化工較小時(shí),即催化劑中Fe含量較大時(shí),反應(yīng)的轉(zhuǎn)化由表3CNMHGFe-Zn催化率較低。隨著Fe含量的降低,對目標(biāo)產(chǎn)物環(huán)已烯劑和Ruzn催化劑的苯轉(zhuǎn)化率和環(huán)己烯選擇性都合成纖維工業(yè)2012年第35卷較高,其特點(diǎn)是轉(zhuǎn)化率隨選擇性增加而減小。在Appl Catal A,2003,252(1):9相同反應(yīng)時(shí)間內(nèi), Ru-Fe-Zn催化劑的苯轉(zhuǎn)化率比2葉代停龐先朵,黃仲濤聚酰胺生產(chǎn)新技術(shù)苯不完全加氫Ru-Zn催化劑的要高,選擇性的降低量也相對較制環(huán)已烯的開發(fā)研究[J]高分子通報(bào)1993(3)[3]王東升,苯部分加氫制環(huán)己烯[J].石油化工,1991,20小。Ru-Fe-Zm催化劑的苯平均轉(zhuǎn)化率為54.9%,選擇性為81.8%。Fe離子的引入,對RuZn催化[4]王爭,趙淑惠劉壽長環(huán)已烯下游產(chǎn)品的開發(fā)研究[門]精劑的反應(yīng)轉(zhuǎn)化率、選擇性都有適當(dāng)提高。細(xì)化工中間體,2006,36(4):12-15表3Ru-FeZn與RuZn催化劑的穩(wěn)定性評價(jià)[5程永建,袁鵬,劉壽長環(huán)已烯下游產(chǎn)品的研究進(jìn)展[J].河Tab 3 Stability evaluation of Ru-Fe-Zn and Ru-Zn catalysts南化工,2006,23(8):1-4.轉(zhuǎn)化率,%選擇性,%[6]朱微娜,袁鵬,劉壽長,苯選擇加氫制環(huán)己烯下游產(chǎn)品的開批次Ru-ZnRu-Fe-ZnRu-Zn發(fā)研究[化工中間體,2006(4):9-13.54.882.0[7]劉壽長,李利民,王向宇苯選擇加氫制環(huán)已烯催化劑及其8l.9制造方法:中國,01122208[P].2004-11-2453.040.0[8]劉壽長,李利民,王向字.苯選擇加氫制環(huán)已烯催化劑,其57.779479.4制備方法及調(diào)變方法和再生方法:中國,200110060451.057.039.080.1[P],2007-3-158.638.679.885.8[9] Liu Shouchang, Wu Yongmei, Wang Zheng, et al. Study on42.783.3Ru-La/zrO2, catalyst prepared by precipitation method for se-lective hydrogenation of benzene to cyclohexene[J]. J Nature結(jié)論a.Ru系催化劑中加入助劑zn能明顯提高101 Liu Shouchang, du Zhong, Liu yanli,ta. Effect of Lanth苯加氫目標(biāo)產(chǎn)物環(huán)己烯的選擇性,其中Ru/zn摩num on performance of RuB amorphous alloy catalyst for benzene selective hydrogenation[ J].J Rare Earth, 2006, 24(4)爾比為7時(shí)較佳。456-460b.在助劑加入中,引入第三種組分Fe,可進(jìn) Liu Shouchang, Liu Zhongyi, Wang Zheng, et al. A novel amor-步提高苯加氫目標(biāo)產(chǎn)物環(huán)己烯的選擇性,加入phous alloy Ru- La-B/ZrO2 catalyst with activity and selectivity量按Zn/Fe摩爾比為10較理想。Ru-FeZn催化for benzene selective hydrogenation[J ]. Appl Catal A: Gen劑具有很好的催化活性和穩(wěn)定性,與傳統(tǒng)RuZ2006,31(1):49-5[12]Struijk J, D'Angremond M, Lacas-de Regt WJM, et al.Par催化劑相比更具工業(yè)應(yīng)用前景。tial liquid phase hydrogenation of benzene to cyclohexene owerruthenium catalysts in the presence of aqueous salt solution:參考文獻(xiàn)I. Preparation, characterizationcatalyst and study of a[1] DaSilva J W, Cobo A J G. The role of the titania and silica sup-mumber of process variables[ J]Catal A,1992,83(2)ports in Ru- Fe catalysts to partial hydrogenation of benzene[J]Effect of additive on catalytic performanceof Ru catalyst for benzene hydrogenationLi Jianxiu, Wu Jimin, Chang Shouxin(1. Department of Chemical Engineering, Pingdingshan Industrial College of Technology, Pingdingshan467001; 2. Construction Department, China Pingmei Shenma Jiangong Group, Pingdingshan 467001)Abstract: Ru-Zn and Ru-Fe-Zn catalysts were prepared using ruthenium trichloride(RuCl, ) zinc sulfate(ZnSO, )and ferrous sulfate( FeSO4)as raw material by coprecipitation process. The effect of the additives Zn and Zn/Fe on the catalytic per-formance of Ru catalysts for benzene hydrogenation to cyclohexene was studied. The catalysts were characterized by transmissionelectron microscopy. The results showed that Ru-Zn catalyst had a fairly good dispersion and clear particle size when Ru-Fe-Zncatalyst had greater particle size and lower specific surface area; the selectivity of cyclohexene was relatively high as Ru catalystwas incorporated with the additive Zn at Ru/ Zn mole ratio of 7 and was further improved as the third component Fe was added intthe catalyst and the Zn/Fe mole ratio was 10; Ru- Fe- n catalyst exhibited excell中國煤化工y, and the conversion rate of benzene reached 54. 9% and the selectivity of cylohexene was upCNMHGKey words: benzene; cyclohexene; catalyst; ruthenium trichloride; additive; hydrogenation; selectivity