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1.
李静  张启俭  齐平  韩丽  邵超 《工业催化》2017,25(6):19-23
二甲醚是一种理想的氢载体,可用于解决氢的储存和运输。以Pt/TiO_2为部分氧化催化剂,结合Ni/Al_2O_3重整催化剂,考察钛前驱体和焙烧温度对二甲醚部分氧化重整制氢反应的影响。结果表明,以Ti(C4H9O)4为原料制备的TiO_2为金红石相,Ti(SO4)2或Ti O(OH)2为原料制备的TiO_2为锐钛矿相;以Ti(C4H9O)4为原料制备的Pt/TiO_2-E催化剂催化性能略好,转化率接近100%,H2收率约90%,表明金红石相TiO_2负载的Pt催化剂略佳;以Ti(SO4)2为原料制备的Pt/TiO_2-S催化剂500℃焙烧可获得金红石相TiO_2。与Pt/Al_2O_3催化剂相比,Pt/TiO_2催化剂具有更好的催化性能,H2收率超过90%,而Pt/Al_2O_3催化剂H2收率约80%。  相似文献   

2.
蛋白土具有良好的应用前景,但是其自然白度较低制约了其开发应用。蛋白土硫酸铵煅烧法可去除其中的显色金属氧化物,提高蛋白土的白度,同时提取其中Al2O3。本文采用热重-差示扫描量热(TG-DSC)、同步热分析与红外质谱(TG-FTIR-MS)联用系统,结合X射线衍射对煅烧过程的固相及气相产物进行了表征分析,明析了其化学过程。结果表明,蛋白土中的Al2O3和Fe2O3在200~350℃时反应生成(NH43(Al,Fe)(SO43,同时逸出NH3和H2O;350~450℃时,进一步反应转化为NH4(Al,Fe)(SO42,同时逸出NH3、H2O、SO2和O2;450~550℃时,NH4(Al,Fe)(SO42分解生成(Al,Fe)2(SO43,同时逸出NH3、H2O、SO2和O2;550~750℃时(Al,Fe)2(SO43分解生成Al2O3和Fe2O3,同时逸出SO2和O2。采用Kissinger微分法与Ozawa积分法分别计算出4个阶段表观活化能后取二者平均值,分别为101.74kJ/mol、104.52kJ/mol、201.40kJ/mol、232.51kJ/mol,并获得对应4个热化学反应阶段的频率因子、反应级数和动力学方程。  相似文献   

3.
周鑫晨  章学来  华维三  郑钦月 《化工进展》2019,38(10):4520-4533
利用电热恒温水槽、高低温交变试验箱搭建蓄放热实验平台,研究了9种增稠剂对NH4Al(SO4)2·12H2O蓄放热性能的影响,测试分析了NH4Al(SO4)2·12H2O改性后的循环稳定性能。结果表明,质量分数为2%的黄原胶、1%的瓜尔豆胶或1%的羟乙基纤维素均能较好改善NH4Al(SO4)2·12H2O的放热性能且对相变潜热的削弱程度不大,对应改性NH4Al(SO4)2·12H2O的主要参数变化为:熔点分别降低1.0℃、1.3℃、1.3℃,蓄热时长分别增加94%、35%、9%,蓄热相变平台分别增加125%、63%、5%,过冷度分别减小43%、45%、34%,结晶过程温度变化分别减小84%、87%、73%,放热时长分别增加27%、11%、50%,相变潜热分别减小5.8%、8.3%、4.1%。增稠剂对NH4Al(SO4)2·12H2O放热性能的改性效果会受到降解反应影响,而2%黄原胶的改性效果相对其他两种增稠剂较好,循环过程中改性材料的结晶过程温度始终保持在60℃以上。60次循环后,改性材料主要参数相比纯材料的变化为:熔点下降0.2℃,蓄热相变平台减小15%,蓄热时长增加13%,结晶过程温度变化减小87%,过冷度减小42%,放热时长增加36%,相变潜热减小1.6%。  相似文献   

4.
A series of SiO2-supported MoO3, V2O5, and Pt catalysts were prepared for the study of model soot oxidation with simulated diesel exhaust gas. Composite samples of Pt with the metal oxides demonstrated higher oxidation activities than the single-component SiO2-supported MoO3, V2O5 or Pt catalysts in the absence of SO2 in the reactant gas. Based on the effects of NO2 on carbon oxidation, a synergistic reaction mechanism was suggested to explain the effects of combining Pt with the oxides: Pt catalyzes the oxidation of NO with gas phase O2 to NO2, while MoO3 and V2O5 catalyze the oxidation of carbon with NO2. Finally, the effects of SO2 on the carbon oxidation reaction were examined and discussed.  相似文献   

5.
简述了NH3和NO在催化剂表面吸附、转化活化和反应历程及H2O和SO2对以上反应行为的影响。分析表明,NH3氧化脱氢进而与NO反应是决定NH3反应性和最终产物的关键。NO以气态(Eley-Rideal机理)或硝基类物质等吸附态(Langmuir-Hinshelwood机理)形式参与选择催化还原(SCR)反应。提高催化剂酸性和氧化还原循环性能,利于NH3和NO吸附和转化及相互间反应。高温时,H2O影响轻微,而SO2增强催化剂酸性,提高脱硝活性。低温时,H2O和SO2抑制NO吸附和转化活化,导致硫铵盐累积和活性位转变为硫酸盐使催化剂失活。因此,提高抗H2O、抗SO2性能是低温脱硝催化剂研发的重要方向。而发展在线升温等再生工艺以解决硝酸盐或含硫化合物导致的失活问题,对保障低温脱硝系统长期稳定运行具有重要意义。  相似文献   

6.
The delaminated Fe203-pillared clay shows high activities for selective catalytic reduction (SCR) of NO by NH2. Temperature program desorption (TPD) studies show that large amounts of NO., are adsorbed on the pillared clay catalyst at the SCR reaction temperatures (i.e. near 400°C). This result indicates that a Langmuir-Hinshelwood type mechanism (for reaction between chemisorbed NO, and NH, on the surface to form N2) is operative for the pillared clay catalyst, which is in contrast to the SCR reaction on the commercial vanadia-based catalysts. The SCR activities for the delaminated Fe203-pillared clay catalyst are higher than that of a commercial-type V2O5 + WO3/TiO2 catalyst under SO2 + H20 free conditions, but became lower in the presence of SO2 +l H20. However, when promoted by doping 1-3% Cr203, the pillared clay catalyst exhibits higher SCR activities than the commercial-type catalyst in the presence of S02 + H2O at all practical SCR reaction temperatures  相似文献   

7.
Combined effect of H2O and SO2 on V2O5/AC the activity of catalyst for selective catalytic reduction (SCR) of NO with NH3 at lower temperatures was studied. In the absence of SO2, H2O inhibits the catalytic activity, which may be attributed to competitive adsorption of H2O and reactants (NO and/or NH3). Although SO2 promotes the SCR activity of the V2O5/AC catalyst in the absence of H2O, it speeds the deactivation of the catalyst in the presence of H2O. The dual effect of SO2 is attributed to the SO42− formed on the catalyst surface, which stays as ammonium-sulfate salts on the catalyst surface. In the absence of H2O, a small amount of ammonium-sulfate salts deposits on the surface of the catalyst, which promote the SCR activity; in the presence of H2O, however, the deposition rate of ammonium-sulfate salts is much greater, which results in blocking of the catalyst pores and deactivates the catalyst. Decreasing V2O5 loading decreases the deactivation rate of the catalyst. The catalyst can be used stably at a space velocity of 9000 h−1 and temperature of 250 °C.  相似文献   

8.
任永胜  何婷婷  谢娟  蔡超 《化工学报》2018,69(7):2838-2850
采用等温溶解法研究333.15 K体系(K+,NH4+//Cl-,SO42--H2O)和(K+,NH4+//Cl-,SO42--(CH2OH)2-H2O)[w((CH2OH)2)=30%]的固液相平衡关系。测定了平衡溶液的溶解度数据及物化性质,包括密度、黏度、折射率、pH。根据实验数据,绘制了相应的干盐相图、水图及物化性质-组成图。实验中的物化性质(黏度、密度、折射率、pH)随J(2NH4+)的变化呈现相似性规律。实验结果表明:在333.15 K下,体系(K+,NH4+//Cl-,SO42--H2O)和(K+,NH4+//Cl-,SO42--(CH2OH)2-H2O)[w((CH2OH)2)=30%]的相图相似,均含有一个四元共饱和点,四条单变曲线及四个固相结晶区域。这两个体系均为复杂体系,存在(K,NH4)Cl、(NH4,K)Cl、(K,NH42SO4、(NH4,K)2SO4四种固溶体。实验所获数据和结论,可优化以硫酸盐型固体废弃物为硫酸根来源,转化法生产硫酸钾工艺。  相似文献   

9.
对国内某1000MW燃煤发电机组失活选择性催化还原(SCR)催化剂进行CeO2改性再生。对再生前后样品进行N2吸附-脱附、扫描电子显微镜(SEM)、X射线荧光光谱(XRF)、傅里叶变换红外光谱(FTIR)对比表征分析。在自制固定床反应系统上对CeO2改性再生催化剂(CeReCat)进行Hg0氧化性能测试,同时研究了SO2、H2O、NO和NH3对Hg0氧化性能的影响。结果表明,CeO2改性再生方法可有效清洗失活SCR催化剂表面杂质,恢复催化剂表面活性位点和孔隙结构,可使Ce、V两种活性元素得到有效负载。CeO2改性后的样品Hg0氧化性能显著提升,3.0 CeReCat具有最佳Hg0的氧化效率。此外,烟气中加入600μL/L SO2后,3.0 CeReCat仍具有高达74.4%的Hg0氧化效率,抗SO2性能较好。烟气中的NO可轻微促进Hg0的氧化。由于竞争吸附作用,烟气中的H2O和NH3会抑制Hg0的氧化。CeO2改性再生催化剂置于SCR系统下层时,由于烟气NH3浓度较低而具有较高Hg0氧化效率,具有良好的应用前景。  相似文献   

10.
电解锰渣已成为阻碍电解锰行业发展的瓶颈,其中锰渣含有的大量石膏是限制其资源化利用的关键。针对锰渣中石膏浸出问题,本文研究了NH4HCO3和NH4Cl用量、浸出初始pH、浸出时间、浸出温度对锰渣中石膏转变规律的影响。研究结果表明,当锰渣与NH4HCO3和NH4Cl之间的质量比为20∶8∶1.5、固液比为1∶5、浸出初始pH为7.5、浸出温度为70℃、浸出时间为120min时,石膏的浸出率达到90.0%;浸出锰渣主要物相含有CaCO3、SiO2、Ca2Mn2(OH)4Si4O11·2H2O、Mg5.0Al6Fe4Si2.5Al1.5O10(OH)8以及KAl3Si3O10(OH)2等,其中浸出锰渣中MnO含量由未浸出前的7.45%提高到14.71%。转变规律表明,NH4HCO3与锰渣中的石膏反应转变成(NH4)2SO4和CaCO3,而NH4Cl作为盐试剂可进一步促进石膏的溶解,从而提高石膏的浸出率。  相似文献   

11.
The inhibition effect of H2O on V2O5/AC catalyst for NO reduction with NH3 is studied at temperatures up to 250 °C through TPD, elemental analyses, temperature-programmed surface reaction (TPSR) and FT-IR analyses. The results show that H2O does not reduce NO and NH3 adsorption on V2O5/AC catalyst surface, but promotes NH3 adsorption due to increases in Brønsted acid sites. Many kinds of NH3 forms present on the catalyst surface, but only NH4+ on Brønsted acid sites and a small portion of NH3 on Lewis acid sites are reactive with NO at 250 °C or below, and most of the NH3 on Lewis acid sites does not react with NO, regardless the presence of H2O in the feed gas. H2O inhibits the SCR reaction between the NH3 on the Lewis acid sites and NO, and the inhibition effect increases with increasing H2O content. The inhibition effect is reversible and H2O does not poison the V2O5/AC catalyst.  相似文献   

12.
Synthetic conditions that produce long zeolite-L crystals in hexagonal columnar structures with flat basal and side planes were investigated. The gels with the molar compositions of Al2O3:SiO2:K2O:H2O = a:b:c:d, where a = 1.3–2.0, b = 20–24, c = 10.2–10.5, and d = 1000–1400 and with Al2(SO4)3 as the Al source produced zeolite-L with sharp edged hexagonal columnar structures and flat basal and side planes upon heating at 180 °C for 3 d. The crystal size, in particular the length, increased with increasing the SiO2, H2O, or Al2O3 content, but with decreasing the K2O content. While the length increased, the width decreased upon increasing both Al2(SO4)3 and H2O contents, leading to the production of sharp-edged hexagonal columnar crystals. In the case where a = 1.7, b = 20, c = 10.9, and d = 1030, sharp edged hexagonal columnar crystals with the length up to 20 μm and the width of 2.3 μm were produced. When Al(OH)3, a more commonly used Al source, was used instead of Al2(SO4)3, crystals with blunt edges and round planes were produced. Furthermore, the size decreased with increasing the Al(OH)3 content. While KCl and NaCl had a negligible effect on the morphology change, LiCl and MgCl2 led to a dramatic decrease in size by 96% and 91%, respectively, even with in the presence of 0.2 and 0.001 equivalents, respectively, with respect to the amount of Al2O3 content. The addition of CaCl2 led to the production of an unknown phase. The use of mixed base, i.e., the KOH and NaOH mixture in the mole ratio of 6:4.9, led to the formation of crystals whose one end was connected to a bundle of narrow and long crystals.  相似文献   

13.
The influence of the thermal treatments of Pt/SO42−-Zr(OH)4 catalysts on the activity for the metal-catalyzed reaction of cyclohexane dehydrogenation and the acid-catalyzed reaction of n-butane isomerization, were studied in this work. A mutual antagonism between the conditions for optimal activity of the acid and metal functions was found and was seemingly related to the crystallization of the support. In order to be able to isomerize n-butane, SO42−-Zr(OH)4 had first to be calcined in air at Tcalc>400 °C. The onset of activity and strong acid properties coincided with the appearance of the tetragonal crystal phase. SO42−-Zr(OH)4 supported Pt, prepared from chloroplatinic acid, was tried to be converted to the metal state (Pt0) in order to have full catalytic capacity. When Pt/SO42−-Zr(OH)4 was first calcined in air at Tcalc>400 °C, Pt remained in a seemingly oxidized state, with no de/hydrogenation properties even after reduction in H2 at 300 °C. Under certain conditions, Pt metal properties were improved: (i) calcining Pt/SO42−-Zr(OH)4 in air at Tcalc<400 °C; (ii) calcining Zr(OH)4 at Tcalc>400 °C before sulfating the support; and (iii) calcining Pt/SO42−-Zr(OH)4 in N2 instead of air. In these cases, though Pt dehydrogenation activity increased, the activity of the acid function decreased (iii) or was practically null ((i) and (ii)). The support was amorphous in case (i) and mainly monoclinic in case (ii). Sulfate loss and conversion into the monoclinic phase occurred in case (iii). As compared to sulfate-free Pt/ZrO2, sulfur poisoning always decreased the metal activity of sulfated catalysts but the decrease was higher for mainly tetragonal sulfate-doped catalysts. The final conclusion is that the optimum activation conditions for the metal and acid functions in Pt/SO42−-Zr(OH)4 are mutually excluding. The deleterious effect of SO42−-ZrO2 (SZ) on Pt metal activity is closely related to the growth and/or the presence of the tetragonal phase and cannot be prevented if a high activity of the acid function is demanded by the reacting system.  相似文献   

14.
The release and reduction of NOx in a NOx storage-reduction (NSR) catalyst were studied with a transient reaction analysis in the millisecond range, which was made possible by the combination of pulsed injection of gases and time resolved time-of-flight mass spectrometry. After an O2 pulse and a subsequent NO pulse were injected into a pellet of the Pt/Ba/Al2O3 catalyst, the time profiles of several gas products, NO, N2, NH3 and H2O, were obtained as a result of the release and reduction of NOx caused by H2 injection. Comparing the time profiles in another analysis, which were obtained using a model catalyst consisting of a flat 5 nmPt/Ba(NO3)2/cordierite plate, the release and reduction of NOx on Pt/Ba/Al2O3 catalyst that stored NOx took the following two steps; in the first step NO molecules were released from Ba and in the second step the released NO was reduced into N2 by H2 pulse injection. When this H2 pulse was injected in a large amount, NO was reduced to NH3 instead of N2.

A only small amount of H2O was detected because of the strong affinity for alumina support. We can analyze the NOx regeneration process to separate two steps of the NOx release and reduction by a detailed analysis of the time profiles using a two-step reaction model. From the result of the analysis, it is found that the rate constant for NOx release increased as temperature increase.  相似文献   


15.
We have investigated the catalytic behavior of Pt encapsulated TiO2 nanotubes for the water gas shift reaction as well as the hydrogenation of CO. Pt–TiO2 nanotube catalysts were prepared by employing fine fiber shaped crystals of [Pt(NH3)4](HCO3)2 complex as a structure determining template material. The turnover frequencies (TOF) of these nanotube catalysts were more than one order of magnitude larger than conventional impregnation Pt/TiO2 catalysts, and the selectivity for methanol in CO–H2 reaction was extraordinary high compared to the impregnation catalysts. The XPS and XRD analyses of the nanotubes revealed characteristic electronic state of reduced TiO2 (Ti3+ in rutile structure) with zerovalent Pt even after the calcination at 773 K. In WGS reaction, electron rich Ti3+ on the nanotube wall may play an important role to activate water molecules for the oxidation of CO. In CO–H2 reaction, similar promotion effect of Ti3+ species may be operating for selective methanol formation by supplying active OH(a).  相似文献   

16.
A reliable method to continuously monitor NH3 in a gas stream containing CO—NO—O2 and H2O has been developed. The method is based on a quantitative oxidation of NH3 to NO on a Pt catalyst. The extent of this reaction is affected by temperature, excess oxygen present, and space-velocity. There is a significant effect of inlet O2 concentration on extent of various reactions in the CO—NO—O2—H2O system on a Pt/γAl2O3 catalyst. At fixed space-velocity and catalyst temperature, and for fixed reactor inlet concentrations of CO and NO. there is negligible CO—NO reaction either in the absence of oxygen or in the presence of excess oxygen. However, short of the stoichiometric amount of O2 required for CO oxidation, there is appreciable CO—NO (and possibly also CO—NO—H2O) reaction whose extent increases with increasing oxygen concentration. This increase is especially dramatic in a narrow window of O2: concentrations near the stoichiometric point. Interestingly enough, near the stoichiometric point, self-sustained isothermal oscillations in the outlet CO and NO concentrations are also observed (Subramaniam and Varma. submitted for publication)  相似文献   

17.
The activity of several catalysts are studied in the soot combustion reaction using air and NO/air as oxidising agents. Over Al2O3-supported catalysts NO(g) is a promoter for the combustion reaction with the extent of promotion depending on the Na loading. Over these catalysts SO42− poisons this promotion by preventing NO oxidation through a site blocking mechanism. SiO2 is unable to adsorb NO or catalyse its oxidation and over SiO2-supported Na catalysts NO(g) inhibits the combustion reaction. This is ascribed to a competition between NO and O2. Over Fe-ZSM-5 catalysts the presence of a NOx trapping component does not increase the combustion of soot in the presence of NO(g) and it is proposed that this previously reported effect is only seen under continuous NOx trap operation as NO2 is periodically released during regeneration and thus available for soot combustion. Experiments during which the [NO](g) is varied show that CO, rather than an adsorbed carbonyl-like intermediate, is formed upon reaction between NO2 (the proposed oxygen carrier) and soot.  相似文献   

18.
王雪莹  黄雪莉  黄河  罗清龙  邹雪净 《化工学报》2020,71(11):5059-5066
新疆卤水硝酸盐矿主要含有Na+、K+、Mg2+、Cl-、NO3-、SO42-六种离子,属于高元复杂体系,其合理利用和开发需要不同温度下的相平衡研究作为理论支撑。采用等温溶解平衡法,对Na+, K+, Mg2+//Cl-, NO3-, SO42--H2O体系在-15℃、NaCl·2H2O饱和条件下的相平衡进行了研究,并构建了相图。相图中有六个零变量点和八个两盐结晶区,只存在一种复盐KCl·MgCl2·6H2O。八个两盐结晶区,分别对应于NaCl·2H2O+Na2SO4·10H2O、NaCl·2H2O+NaNO3、NaCl·2H2O+KCl、NaCl·2H2O+KNO3、NaCl·2H2O+MgSO4·7H2O、NaCl·2H2O+MgCl2·8H2O、NaCl·2H2O+Mg(NO3)2·6H2O和NaCl·2H2O+KCl·MgCl2·6H2O,其中NaCl·2H2O+Na2SO4·10H2O共晶区最大,在低温时,硫酸钠的溶解度最小,降温过程中较易结晶析出。与该体系在25℃下的相图相比,复盐种类减少5种,零变量点减少19个,相关系得以极大简化。  相似文献   

19.
Xinjiang brine nitrate mine mainly contains six kinds of ions: Na+, K+, Mg2+, Cl-, NO3-, and SO42-, belonging to a high-element complex system, and its rational utilization and development require phase equilibrium studies at different temperatures as theoretical support. The phase equilibrium of the system Na+, K+, Mg2+//Cl-, NO3-, SO42--H2O saturated with NaCl·2H2O at -15℃ was investigated using the isothermal solution equilibrium method. According to the measured data, the phase diagrams were constructed. Only one double salt KCl·MgCl2·6H2O was found in the system. There are six invariant points and eight two-salt crystallization fields corresponding to NaCl·2H2O+Na2SO4·10H2O, NaCl·2H2O+NaNO3, NaCl·2H2O+KCl, NaCl·2H2O+KNO3, NaCl·2H2O+MgSO4·7H2O, NaCl·2H2O+MgCl2·8H2O, NaCl·2H2O + Mg(NO3)2·6H2O and NaCl·2H2O+KCl·MgCl2·6H2O. The crystallization area of NaCl·2H2O+Na2SO4·10H2O occupies the largest part because of its low solubility, and they will crystallize out easily from the mixed solution in the cooling process. Compared with the phase diagram of the system at 25℃, there are 5 types of double salts reduced, 19 zero variable points reduced, and the phase relationship is greatly simplified.  相似文献   

20.
W. Zou  R.D. Gonzalez   《Catalysis Today》1992,15(3-4):443-453
The effect of pretreatment on the dispersion of supported noble metal Catalyst prepared from amine precursors in basic solution have been studied. The following metal precursors were used: Pt(NH3)4(NO3)2, Pd(NH3)4(NO3)2, Ru(NH3)6Cl3 and [Rh(NH3)5Cl]Cl2 Pretreatment in oxygen, prior to reduction in H2 at 400C, resulted in poor dispersions for Ru and Rh, moderate dispersions for Pd and high dispersions for Pt. Pretreatment in H2 resulted in poor dispersions for Pd and Pt and high dispersions for Ru and Rh. Decomposition of the adsorbed Pt and Pd precursors in argon resulted in very high dispersions.  相似文献   

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