γ-Fe_2O_3/AC脱硫剂的制备及低温脱除CS_2性能
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摘要
以活性炭(AC)为载体,用FeSO_4·7H_2O为原料,采用沉淀法制备Fe负载脱硫剂,通过XRD、FTIR、FE-SEM、ICP、H_2-TPR等方法对脱硫剂进行表征。从制备方法和焙烧温度的角度,研究脱硫剂低温脱除CS_2的性能以及造成其差异的原因。结果表明:采用FeSO_4先沉淀后焙烧,焙烧气氛是氮气的γ-Fe_2O_3/AC-N_2法生成的γ-Fe_2O_3结晶度最高,并且有效地增加了活性炭表面碱性基团数量,提高了负载量和分散性,使脱硫效果大大提升,当焙烧时有O_2存在会生成α-Fe_2O_3降低脱硫剂脱除CS_2的活性;使用γ-Fe_2O_3/AC-N_2法焙烧温度在500℃时,结晶度最高,脱硫剂的脱硫效果最好,吸附量达到40.41mg/g,当温度超过500℃时生成了Fe_3O_4,降低了脱硫效果,用4种动力学模型对γ-Fe_2O_3/AC在活性炭载体上的脱硫过程进行动力学描述,发现Elovich模型可以更好地描述CS_2在脱硫剂上的脱硫过程,其化学控制是主要因素。
The iron loaded desulfurizers were prepared by precipitation method with AC as carrier and FeSO_4·7H_2O as raw material. The desulfurizers were characterized by XRD, FTIR, FE-SEM, ICP and H_2-TPR. The performance of the desulfurizers in the CS_2 low-temperature desorption was explored and the performance differences were analyzed from the aspects of preparation methods and calcination temperatures. The results showed that the crystallinity of generated γ-Fe_2O_3 was the highest when the precursors were calcined in N_2 after precipitation. The method increased the amount of basic groups on the surface of activated carbon, so that the capacity and dispersivity was increased. α-Fe_2O_3 wasgenerated when the calcination gas contained oxygen, thus reduced the activation of CS_2 desorption on the desulfurizer. The adsorption capacity reached 40.41 mg/g when the calcination temperature of γ-Fe_2O_3/AC-N_2 method was 500℃.Fe_3O_4 was generated when the temperature was over 500℃, which would reduce the desulfurization effect. The desulfurization process on γ-Fe_2O_3/AC was fitted by four kinetics models. It was shown that the Elovich model could best describe the desulfurization process of CS_2, and the main reaction control step was the chemical control.
The iron loaded desulfurizers were prepared by precipitation method with AC as carrier and FeSO_4·7H_2O as raw material. The desulfurizers were characterized by XRD, FTIR, FE-SEM, ICP and H_2-TPR. The performance of the desulfurizers in the CS_2 low-temperature desorption was explored and the performance differences were analyzed from the aspects of preparation methods and calcination temperatures. The results showed that the crystallinity of generated γ-Fe_2O_3 was the highest when the precursors were calcined in N_2 after precipitation. The method increased the amount of basic groups on the surface of activated carbon, so that the capacity and dispersivity was increased. α-Fe_2O_3 wasgenerated when the calcination gas contained oxygen, thus reduced the activation of CS_2 desorption on the desulfurizer. The adsorption capacity reached 40.41 mg/g when the calcination temperature of γ-Fe_2O_3/AC-N_2 method was 500℃.Fe_3O_4 was generated when the temperature was over 500℃, which would reduce the desulfurization effect. The desulfurization process on γ-Fe_2O_3/AC was fitted by four kinetics models. It was shown that the Elovich model could best describe the desulfurization process of CS_2, and the main reaction control step was the chemical control.
引文
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[2]RHODES C,RIDDELB S A,WESTA J,et al.Low-temperature hydrolysis of carbonyl sulfide and carbon disulfide:a review[J].Catalysis Today,2000,59(3):443-464.
[3]TONG S,LANA I G D,CHUANG K T.Appraisal of catalysts for the hydrolysis of carbon disulfide[J].Canadian Journal of Chemical Engineering,1992,70(3):516-522.
[4]胡典明,孔渝华,王先厚,等.MZX高温转化吸收型精脱硫剂的开发及工业应用[J].化学与生物工程,2005,22(9):40-42.HU D M,KONG Y H,WANG X H,et al.Development and industrial application of MZX high temperature conversion absorbent fine desulfurizer[J].Chemistry&Bioengineering,2005,22(9):40-42.
[5]张清建,孔渝华,王先厚,等.EZ-2宽温氧化锌精脱硫剂的工业应用[J].天然气化工(C1化学与化工),2006,31(5):41-43.ZHANG Q J,KONG Y H,WANG X H,et al.Industrial application of EZ-2 wide temperature zinc oxide fine desulfurizer[J].Natural Gas Chemical Industry,2006,31(5):41-43.
[6]赵传军,户春,李小燕.水煤气、半水煤气系统脱硫综合分析[J].化肥设计,2007,45(5):26-29.ZHAO C J,HU C,LI X Y.Comprehensive analysis of desulfurization in water gas and semi-water gas system[J].Fertilizer Design,2007,45(5):26-29.
[7]CLARK P D,DOWLING N I,HUANG M.Conversion of CS2 and COS over alumina and titania under Claus process conditions:reaction with H2O and SO2[J].Applied Catalysis B:Environmental,2001,31(2):107-112.
[8]黄镕.LYT-511氧化钛基中温有机硫水解剂的开发与应用[J].中氮肥,2006(6):63-66.HUANG R.Development and application of LYT-511 titanium dioxide based medium temperature organic sulfur hydrolyzate[J].M-Sized Nitrogenous Fertilizer Progress,2006(6):63-66.
[9]李凯.COS、CS2水解脱硫剂的开发及机理研究[D].昆明:昆明理工大学,2013.LI K.Study on the development and mechanism of COS and CS2hydrolytic desulfurizer[D].Kunming:Kunming University of Science and Technology,2013.
[10]LAI J,SHAFI K V P M,LOOS K,et al.Dopingγ-Fe2O3nanoparticles with Mn(III)suppresses the transition to theγ-Fe2O3structure[J].Journal of the American Chemical Society,2003,125(38):11470-11471.
[11]LIU C,YANG S,MA L,et al.Comparison on the performance ofα-Fe2O3,andγ-Fe2O3 for selective catalytic reduction of nitrogen oxides with ammonia[J].Catalysis Letters,2013,143(7):697-704.
[12]王燕,张战营,曹建亮,等.化学沉淀法制备纳米α-Fe2O3及其气敏性能研究[J].河南理工大学学报(自然科学版),2011,30(2):239-243.WANG Y,ZHANG Z Y,CAO J L,et al.Preparation of nanometerα-Fe2O3 by chemical precipitation method and its gas sensitivity[J].Journal of Henan Polytechnic University,2011,30(2):239-243.
[13]王栋,路春美,张信莉.沉淀过程对γ-Fe2O3催化剂物性及SCR脱硝性能的影响[C]//动力工程及工程热物理全国博士生学术论坛,2013.WANG D,LU C M,ZHANG X L.Effect of precipitation process on physical properties ofγ-Fe2O3 catalyst and SCR denitration performance[C]//Power Engineering and Engineering Thermophysics National Doctoral Academic Forum,2013.
[14]谭琦.碳镁储氢材料控制性制备及放氢动力学的研究[D].青岛:山东科技大学,2009.TAN Q.Controlled preparation of carbon-magnesium hydrogen storage material and kinetics of hydrogen desorption[D].Qingdao:Shandong University of Science and Technology,2009.
[15]JIA Z,PENG K,LI Y,et al.Preparation and application of novel magnetically separableγ-Fe2O3/activated carbon sphere adsorbent[J].Materials Science&Engineering B,2011,176(11):861-865.
[16]MACHALA L,TU?EK J,ZBO?IL R.Polymorphous transformations of nanometric iron(Ⅲ)oxide:a review[J].Chem.Mater,2011,23(14):3255-3272.
[17]李文娟.不同晶相金属氧化物微/纳结构材料的制备及其对重金属离子电化学检测的对比研究[D].合肥:中国科学技术大学,2015.LI W J.Preparation of micro/nano-structured materials with different crystalline phase oxides and their comparative studies on electrochemical detection of heavy metal ions[D].Hefei:University of Science and Technology of China,2015.
[18]KREHULA S,MUSI?S,?ELJKO S,et al.The influence of Zn-dopant on the precipitation ofα-FeOOH in highly alkaline media[J].Journal of Alloys&Compounds,2006,420(1/2):260-268.
[19]DELIYANNI E A,BAKOYANNAKIS D N,ZOUBOULIS A I,et al.Akaganeite-type beta-FeO(OH)nanocrystals:preparation and characterization[J].Microporous&Mesoporous Materials,2001,42(1):49-57.
[20]MOU X,LI Y,ZHANG B,et al.Crystal-phase-and morphology-controlled synthesis of Fe2O3,nanomaterials[J].European Journal of Inorganic Chemistry,2012(16):2684-2690.
[21]YI H,HE D,TANG X,et al.Effects of preparation conditions for active carbon-based catalyst on catalytic hydrolysis of carbon disulfide[J].Fuel,2012,97:337-343.
[22]GIULIANA Magnacca,GIUSEPPINA Cerrato,CLAUDIO Morterra,et al.Structural and surface characterization of pure and sulfated iron oxides[J].Chemistry of Materials,2003,15(3):675-687.
[23]LI K Z,HANEDA M,OZAWA M.The synthesis of iron oxides with different phases or exposure crystal planes and their catalytic property for propene oxidation[J].Advanced Materials Research,2012,463-464:189-193.
[24]刘秀丽.磁性铁基脱汞剂对燃煤烟气中气态HgO的吸附特性研究[D].青岛:山东科技大学,2015.LI X L.Study on the adsorption characteristics of magnetic ironbased amalgam on gaseous HgO in coal-fired flue gas[D].Qingdao:Shandong University of Science and Technology,2015.
[25]HUANG G,HE E,WANG Z,et al.Synthesis and characterization ofγ-Fe2O3 for H2S removal at low temperature[J].Industrial&Engineering Chemistry Research,2015,54(34):150-180.
[26]áLVAREZ-GUTIéRREZ N,GIL M V,RUBIERA F,et al.Kinetics of CO2 adsorption on cherry stone-based carbons in CO2/CH4separations[J].Chemical Engineering Journal,2017,307:249-257.
[27]HOY S,MCKAY G.Pseudo-second order model for sorption processes[J].Process Biochemistry,1999,34(5):451-465.
[28]黄铭珠.矿化垃圾粒径分布与其重金属(Cu2+)环境化学行为的相关性研究[D].太原:山西大学,2011.HUANG M Z.Study on the correlation between the size distribution of mineralized rubbish and the environmental chemical behavior of heavy metal(Cu2+)[D].Taiyuan:Shanxi University,2011.