收稿日期:2004-09-20　修回日期:2004-11-12作者简介：张密林(1955-)，男，吉林人,1982年毕业于吉林
大学，博士，教授(博士生导师)，研究方向为无机纳米材料。
(锌、铜、锰)复合脱硫剂的制备及性能研究
张密林，张红霞，陈　野
(哈尔滨工程大学化工学院，黑龙江哈尔滨　150001)
  摘要：用共沉淀法制备纳米脱硫剂前躯物，以硅铝酸盐为载体造粒成型，经450℃煅烧6h 得到三元金属氧化物脱硫剂，此脱硫剂在240℃无氧条件下精脱H 2S ，且颗粒平均直径为1.0mm 时，其穿透硫容可达33.5%，是一种适合于中低温条件下脱硫的脱硫剂。
关键词：脱硫剂；氧化锌；氧化锰；氧化铜
中图分类号:TQ113126+　文献标识码:A  文章编号:1006-7906(2004)06-0029-03
reactor technology
  氧化锌脱硫剂广泛应用于合成氨、制氢、煤化
工、石油炼制等行业[1]，以其脱硫精度高，使用简便，性能稳定可靠，硫容高而占据着重要地位。但单一
氧化锌脱硫剂只有在400℃以上才有较高的脱硫能力，而目前许多行业和化工过程需要中温甚至低温精脱硫；同时，单一氧化锌脱硫剂用空气再生时，温度过高则热烧结严重，温度过低又易形成硫酸盐[2]。因此，脱硫剂的改性已成为克服其缺点的关键。而在氧化物脱硫剂中添加传递电子能力强的金属氧化物时，具有空轨道的H 2S 分子将易接受电子，从而降低反应的活化能，增加反应的活性中心，提高脱硫剂的低温活性[3]。本实验在ZnO 中添加MnO 2和CuO 碱性助剂，对其脱硫性能进行了研究。1　实验部分1.1　脱硫剂的制备
在反应器中加入分散剂水溶液，其用量是共沉淀反应所用溶液质量的1%;60℃条件下同时滴加Zn 2+、Cu 2+、Mn 2+的硝酸盐混合溶液和沉淀剂碳酸钠溶液；反应30min 后，过滤、洗涤、干燥24h 。将脱硫剂前驱物与硅铝酸盐(质量分数20%)混合成
型，经450℃煅烧6h 即为复合金属氧化物脱硫剂。
本实验通过正交法制备了不同配比的氧化物脱硫剂，进行脱硫性能测试，最终确定其最佳质量比为ZnO ∶CuO ∶MnO 2=76.2%∶7.8%∶16.0%。1.2　脱硫剂的结构表征
通过X 射线衍射(XRD )对脱硫剂的结构进行
表征。测试采用日本理学D/Max -A 型X 射线衍
射仪，铜靶k
α辐射，波长值1.54178nm ，管电压30kV ，管电流20mA ，扫描范围10°～70°，扫描速度为0.1°/s 。透射电镜(TEM )测试采用日本电子公司1200-EX 型透射电镜仪，工作电压80kV ，放大倍
数为1×105。1.3　脱硫反应过程
在直径7.0mm 的石英反应管内加入适量脱硫剂，石英反应管置于脱硫反应炉内，并通入载气N 2，使H 2S 气体与脱硫剂发生脱硫反应。尾气通入硝
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通报,1982,(4):34～40.
　第25卷第6期化学工业与工程技术
Vol 125No.6　2004年12月Journal of Chemical Indust ry &Engineering
Dec.,2004
酸银检测液，一旦硫化氢发生穿透，硝酸银溶液颜即明显变黑。立即停止硫化氢的通入，继续通氮气吹扫20min ，然后降温卸出脱硫剂。脱硫反应装置如图1所示。脱硫剂穿透硫容评价指标如下:
  硫容量=吸附的硫质量
脱硫剂的质量
×100
%
图1　脱硫反应装置
1-N 2钢瓶;2-N 2减压阀;3-气体调节阀;4-转子流量计;5-H 2S 生成器;6-酸式滴定管;7-脱硫反应炉;8-石英反应管;9-011mol/LAgNO 3溶液检测管;10-湿式气体流量计;11-皂膜流量计
2　实验结果与讨论
2.1　脱硫剂的TEM 和XRD 分析
图2为脱硫剂无担载的TEM 照片，从图中得知无担载的复合脱硫剂的平均粒径约为50nm 。氧化物微粒尺寸小，比表面积大，因此引起表面原子数增加，而这些大量的缺少邻近配位的表面原子极不稳定，易与其它原子结合，大大增加了纳米粒子的活性[4]。当纳米粒子暴露在反应气中就会吸附气体，并与气体进行反应
。
图2　无担载的脱硫剂粉末的TEM 照片
  图3为纳米氧化锌及纳米锌铜锰三元氧化物的
XRD 谱图,a 为氧化锌纳米粉体的XRD 衍射峰,b 为纳米锌铜锰三元氧化物的XRD 衍射峰。由图3可见,b 的峰强度明显变弱，且无明显的铜锰氧化物衍射峰，其原因可能有二:(1)铜锰含量较低;(2)三重金属氧化物组分间发生了某种作用，降低了其它氧化物的散能力，从而改变了其它组分的峰高[5]
。
图3　无载体脱硫剂的XRD 谱图
2.2　载体含量对硫容影响
硅铝酸盐热稳定性较好，在1000℃以下煅烧
无失重，且脱硫剂的煅烧温度及脱硫温度均远低于
硅铝酸盐载体的分解温度，因此本实验采用硅铝酸盐作载体。表1是脱硫剂载体质量分数与硫容的关系。从实验结果得知，载体质量分数在10%～30%之间变化，硫容值却较稳定。综合考虑脱硫剂的强度及单位质量脱硫剂的脱硫能力，本实验选择载体质量分数为20%。
表1　载体质量分数与硫容的关系
载体质量分数,%1015202530硫容,%
33.2
33.0
32.9
33.432.85
2.3　煅烧温度对硫容的影响
图4为煅烧温度与硫容的关系曲线。采用不同的煅烧温度制备脱硫剂，通过测试脱硫剂的硫容，分析煅烧温度对脱硫剂硫容的影响。煅烧温度在450℃时，脱硫剂的脱硫效果最佳，硫容为33.5%；煅烧温度在650℃时，硫容开始下降；当煅烧温度达到750℃时，脱硫剂的硫容已下降到19.7%。其原因
是600℃以上高温煅烧时，晶粒会逐渐长大，导致多孔性减小；低温分解小孔多，比表面积大[6]。但考虑到分解产率及分解速度，温度不宜过低，故煅烧温度应控制在450℃
。
图4　脱硫剂煅烧温度与硫容关系曲线
・
03・化学工业与工程技术2004年第25卷第6期　
2.4　煅烧时间的确定
在450℃进行煅烧时间与分解产率的研究，结果见图5。随着煅烧时间的延长，脱硫剂前驱物的分解产率不断增大，但自6h 以后分解产率趋于平稳，产率为82.1%。本实验采用煅烧时间6h
。
图5　煅烧时间与脱硫剂前驱物分解产率
2.5　脱硫温度的确定
在200～350℃的温度范围内进行脱硫能力测试，图6为脱硫温度与硫容的关系曲线。200～260
℃范围内，脱硫剂具有良好的脱硫能力，且脱硫温度为240℃时硫容最大，为3315%；温度超过280℃时，硫容开始大幅度下降，从280℃的3310%下降到350℃的2413%。这是由于在ZnO 脱硫剂中添加了碱性助剂MnO 2和CuO ，降低了反应的活化能，增加了反应的活性中心，使脱硫剂的低温活性提高
。
图6　脱硫温度与硫容关系曲线2.6　脱硫剂颗粒尺寸对硫容的影响
本实验对颗粒平均直径为0.28,0.34,1.0,2.0和5.0mm 的脱硫剂进行了脱硫评价。如图7所
示，随着粒径尺寸增大曲线呈下降趋势，其原因为脱硫剂颗粒尺寸的减小，增大了硫化氢与其发生接触反应的面积，从而提高了脱硫反应的硫容。考虑到
实验过程中脱硫剂装填的方便性，本实验采用颗粒平均直径为1.0mm 的脱硫剂进行脱硫能力测试
。
图7　平均粒径与硫容关系曲线
3　结　论
a )由正交实验研究得到(锌、铜、锰)三元金属氧
化物脱硫剂中，锌、铜、锰的最佳质量分数分别为76.2%,7.8%,16.0%。
b )煅烧温度为450℃、煅烧时间为6h 、脱硫温度为240℃时，脱硫剂的硫容最大为33.5%。
c )载体质量分数对脱硫剂的硫容影响不大。但为提高脱硫剂的强度及单位质量脱硫剂的脱硫能力，本实验选择载体质量分数为20%。
d )脱硫剂颗粒尺寸的减小，增大了脱硫剂的比表面积，提高了脱硫剂的硫容。为使脱硫剂装填性能良好，采用颗粒平均直径为1.0mm 最佳。
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・
13・　张密林等(锌、铜、锰)复合脱硫剂的制备及性能研究
T echnical progress for combined control of sulfur dioxide
and nitric oxides
QIU Hong2en,W U Dan,WA N G Rui
(Department of Chemical Engineering,Hainan University,
Haikou570228,China)
  Abstract:Sulfur dioxide and nitric oxides are mainly derived from flue gas,and the flue gas treatment is one of the im portant missions of environment protection.The advantages and disadvantages of the tradi2 tional methods which remove SO2and NO x from flue gas by wet desulfu2 rization and NH3sele
cted catalytic reduction are described.Some tech2 nologies for combined control of SO2and NO x are introduced concerning their current progress,basic principle,process characteristics and appli2 cations.
  K ey w ords:Flue gas;Desulfurization;Denitrification;Electron beam;Pulsed corona discharge;Adsorption
Characteristics and application of airlift loop reactors
N I E Da2shi,CUI Ying2ying,
ZHA N G Qiang,S UN Dang2ru
(School of Environmental and Chemical Engineering,Shanghai
University,Shanghai201800,China)
  Abstract:The characteristics and factors of influence on airlift loop reactors are discussed in detail and the a pplications of airlift loop reactors are mentioned.The development of future research is also presented.  K ey w ords:Airlift loop reactor;Characteristics;Application N ew progress on polymer m atrix nanometer inorganic composite
ZHA N G Yan2hui1,2,TIA N Yan2wen1,S HA O Zhong2cai3
(1.Chemical Engineering Department of North China Institute of
Technology,Taiyuan030051,China;2.School of Material
&Metallurgy,Northeastern University,Shenyang110004,China;
3.Institute of Chemical Engineering Branch,Shenyang Institute of
Technology,Shenyang110026,China)
  Abstract:Polymer matrix nanometer inorganic composite is a new type of composite material with excellent quality and it has become the focus of material science.The characteristics,preparation methods and applications of the polymer matrix nanometer inorganic composite are re2 viewed.The foreground and the problems should be regarded in the de2 veloping process are expounded.
  K ey w ords:Polymer;Nanometer;Inorganic material;C om posite
R eview of synthesis and separation processes of o2chlorotoluene
L U Jian2mei
(Jiangsu Chemical Industry Design Institute Co.,Ltd.,
Nanjing210024,China)
  Abstract:The synthesis and separation processes of o2chloro2 toluene are described.
  K ey w ords:o2Chlorotoluene;p2Chlorotoluene;Synthesis;Sepa2 ration
R esearch progresses of condensation process of diazinon
L IU Jin2hong1,2,TA O Xian2ping2,TA N G Chun2dong2
(1.College of Chemistry and Chemical Engineering,Nanjing University of Technology,Nanjing210009,China;2.Department of Chemical Engineering,Nantong Vocational College,
Nantong226007,China)
  Abstract:The research progresses of the condensation process of organophosphorus insecticide—diazinon,are reviewed.
  K ey w ords:Diazinon;Condensation
R esearch progress in preparation of liquid fluorescent
whitening agents
ZHU Kai,ZHU Xin2bao,MA O L ian2shan (College of Chemical Eegineering,Nanjing Forestry University,
Nanjing210037,China)
  Abstract:Research progress in the preparation of bis2triaziny2 lamin o2stilbene derivative liquid fluorescent whitening agents is re2 viewed.Preparing process and properties of the liquid fluorescent whitening agents disulfonate compound and the liquid fluorescent whitening agents containing tetra2sulfonate compound are introduced. The methods such as adding chemical auxiliary,removing salts and im2 purities with crystallizing,precipitating,washing and filtering to im2 prove the water2solubility and stability of the products are reviewed.The membrane technology applied in separation and purification of fluoresent whitening agent is described as well.
  K ey w ords:Liquid fluorescent whitening agent;Preparation;te2 tra2Sulfonate compound
Study on anti2aging perform ance of regenerated asphalt
ZHA O Xiao2z heng,GA O Ming,
L IA O Ke2jian,YA N Feng,W EI Yi
(Liaoning University of Petroleum and Chemical Technology,
Fushun113001,China)
  Abstract:Regenerated asphalt has special performance compared with the general asphalt,however,there is no unitary method to inves2 tigate the anti2aging performance of regenerated asphalt.The anti2aging performance of two regenerated asphalt,from Shentie and Shenben highways,as well as their original asphalt—Liaohe AH290,are investi2 gated by anti2aging index method and softening point rate elevated con2 stant method.The reliability of the two methods are certified by result of experiment.
  K ey w ords:Regenerated asphalt;Anti2aging performance;Aging index;Softening point
C atalytic synthesis of butanone1,2-propanediol ketal over
phosphotungstic acid catalyst supported on active carbon
YA N G S hui2jin,PA N S hi2tian
(Department of Chemistry and Environmental Engineering
of Hubei Normal University,Huangshi435002,China)
  Abstract:Butanone1,2-propanediol ketal is synthesized by bu2 tanone and1,2-propanediol with the presence of phosphotungstic acid catalyst supported on active carbon.The influences of the molar ratio of butanone to1,2-propanediol,the dosage of catalyst and the reaction time on the yield are studied.The results show,when the molar ratio of butanone to1,2-propanediol is1∶1.5,the mass ratio of catalyst to re2 actants is1.0%,and the reaction time is1h,then the yield of butanone 1,2-propanediol ketal is up to81.8%.
  K ey w ords:Butanone1,2-propanediol ketal;Phosphotungstic acid catalyst supported on active carbon;Catalytic synthesis
R esearch on zinc2copper2m anganese multi2oxides desulphurizer
ZHA N G Mi2lin,ZHA N G Hong2xia,CHEN Ye
(Department of Chemical Engineering,Harbin
Engineering University,Harbin150001,China)
  Abstract:The predecessor of nanometer desulphurizer is prepared by coprecipitation,and the silicoaluminate is used as su pport for mold2 ing.The ternary metal oxide desulphurizer is obtained by calcining under 450℃for6h,and is used to remove H2S under the condition of240℃and oxygen free.The penetrate sulfide capacity is up to33.5%when the average diameter of the granule is1.0mm.The desulphurizer is suitable to use under the condition of low or middle tem perature.
・
Ⅰ
・
　2004Vol125No.6Journal of Chemical Indust ry&Engineering
  K ey w ords:Desulphurizer;Zinc oxide;Manganese oxide;Copper oxide
Experimental study of batch extractive distillation process
ZHOU Yang,L I Wen2xiu
(Department of Chemical Engineering,Shenyang Institute of Chemical Technology,Shenyang110142,China)
  Abstract:Complex column is applied in batch extractive distilla2 tion,the purity of the top product is over95%.The ratio of yield to op2 erating time is defined as objective function,in order to provide experi2 mental data for simulation and industrialization.The main factors that influence the batch extractive distillation such as reflux ratio R,the middle reflux quantity V m(the reflux quantity from middle vessel to stripping section),and the solvent quantity S are studied.The experi2 mental results show that when R is5～10,V m is3.2～712mL/min, S is1.2～2.2mL/min,with the increase of the above factors,the ob2 jective function increases at first but decreases latter.
  K ey w ords:Batch distillation;Batch extractive distillation;Reflux ratio;Reflux quantity of middle;Solvent quantity
Study on disposing phenol2containing w astew ater
by trivalent chromium ion modified bentonite
WA N G Dai2z hi
(Department of Chemistry and Environmental Engineering of Hubei Normal University,Huangshi435002,China)
  Abstract:The optimal conditions of adsorbing phenol by trivalent chromium ion modified bentonite are studied.The results show that the adsorption efficiency is satisfactory,and the adsorption equilibrium can be reached quickly.The alkali conditions are helpful to adsorb.The best result of phenol removing rate is over83%,and the phenol content in treated water is less than the third discharging level in the national stan2 dard.
  K ey w ords:Trivalent chromium ion modified bentonite;Phenol; Adsorption;Removing rate
Evaluation of surface activity and electrochemistry
characteristics of metal anode
DIN G Ze2hua
(Nantong Jiangshan Pesticide Chemical Industrial
Co.,Ltd.,Nantong226006,China)
  Abstract:The surface activity and electrochemistry characteristics of metal anode are evaluated by determining the chlorine2liberating and oxygen2liberating electric potential of electrodes,and testing the polariz2 ing curve and life span of electrode.The result can be used to administer the metal anode electrolyzer.
  K ey w ords:Metal anode;Chlorine2liberating electric potential; Oxygen2liberating electric potential;Polarizing curve;Electrode life span test
Study on preparation of superfine calcium carbonate under different calcinations regulation and concentration
ZHA N G Fei2peng,L U Zhong2yuan,SON G Kai2ping (College of Material Science and Engineering of Southwestern University of Science and Technology,Mianyang621010,China)
  Abstract:The calcinations regulation of limestone and the concen2 tration of calcium hydroxide solution have effects on the granularity of the calcium carbonate crystal.The influences of different calcinations regulation and concentration of calcium hydroxide solution on the granu2 larity of superfine calcium carbonate in the solid2liquid2gas system(Ca (OH)2-H2O-CO2)are discussed.
  K ey w ords:Superfine calcium carbonate;Calcinations regulation;Concentration;Granularity
Study on production of building m aterials by
mixing concrete with alkali w aste
WA N G J un,KON G De2jing
(Scientific Research Center of Tianjing Alkali Plant,
Tianjing300450,China)
  Abstract:The test for producing building materials by mixing con2 crete with alkali waste is introduced.The influences of alkali waste on the performance of concrete are explored by producing test block of dif2 ferent material ratio by some certain processes.
  K ey w ords:Alkali waste;Concrete test block;Com pression strength;Water absorption rate
Mechanism discussion and treatment of nitric acid offgas
ZEN G Xiang2gen
(Nitrogenous Fertilizer Plant,Nanjing Chemical Industry
Corporation,Nanjing210035,China)
  Abstract:According to the mechanism of NO x absorption in nitric acid plant,the approaches and measures for reducing the content of ni2 tric oxides are discussed,and the clean production control is considered as the prime approach which can instead of the terminal control to dis2 pose the nitric acid offgas.The four methods for nitric acid offgas treat2 ment are evaluated.
  K ey w ords:Nitric acid;Nitric oxides;Offgas treatment;Absorp2 tion tower;Clean production
Application of vulcanized bond technology for conveyer belt
QIN Xiang2xia
(Nitrogenous Fertilizer Plant of Nanjing Chemical Industry
Corporation,Nanjing210048,China)
  Abstract:Bond is required in installation of belt conveyer;the quality of the bond has great effects on th
e safety performance and life span of the conveyer belt in operation.The vulcanized bond methods, steps,precautions and effects are introduced.
  K ey w ords:Conveyer belt;Bond;Core body;Vulcanization Applications of HPLC in the analysis of pesticides residue
ZHU Zheng2bin
(Educational College of Nanjing Chemical Industry Corporation,
Nanjing210048,China)
  Abstract:The applications of HPLC in the analysis of pesticides residue are introduced.Some methods for analysing of pesticides,herbi2 cides and bactericides are discussed,and the development of HPLC ap2 plying in the analysis of pesticides residue is put forward as well.
  K ey w ords:HPLC;Pesticide residue;Analysis;Application
Instrument selection and computer2controlling
scheme of terephthalic acid hydrogenation
experimental device
HUA Dun
(Research Institute of Nanjing Chemical Industrial Group,
Nanjing210048,China)
  Abstract:The instrument selection and com puter2controlling sys2 tem design of terephthalic acid hydrogenation pilot experimental device in Research Institute of Yangzi Petrochemical Industrial Corporation are made.The test and running indicate that the instrument selection and computer2controlling system design reach high level,the device is oper2 ated conveniently and run stably,and the precision of determination and controlling has reached or outreached the design specification.
  K ey w ords:Instrument selection;Com puter2controlling scheme; Pilot experimental device
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・Journal of Chemical Indust ry&Engineering2004Vol125No.6　

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