Dielectric barrier discharge plasma synthesis of Ag/γ-Al_(2)O_(3) catalysts for catalytic oxidation of CO

In this study,Ag/γ-Al_(2)O_(3)catalysts were synthesized by an Ar dielectric barrier discharge plasma using silver nitrate as the Ag source andγ-alumina(γ-Al_(2)O_(3))as the support.It is revealed that plasma can reduce silver ions to generate crystalline silver nanoparticles(Ag NPs)of good dispersion and uniformity on the alumina surface,leading to the formation of Ag/γ-Al_(2)O_(3)catalysts in a green manner without traditional chemical reductants.Ag/γ-Al_(2)O_(3)exhibited good catalytic activity and stability in CO oxidation reactions,and the activity increased with increase in the Ag content.For catalysts with more than 2 wt%Ag,100%CO conversion can be achieved at 300°C.The catalytic activity of the Ag/γ-Al_(2)O_(3)catalysts is also closely related to the size of theγ-alumina,where Ag/nano-γ-Al_(2)O_(3)catalysts demonstrate better performance than Ag/micro-γ-Al_(2)O_(3)catalysts with the same Ag content.In addition,the catalytic properties of plasma-generated Ag/nano-γ-Al_(2)O_(3)(Ag/γ-Al_(2)O_(3)-P)catalysts were compared with those of Ag/nano-γ-Al_(2)O_(3)catalysts prepared by the traditional calcination approach(Ag/γ-Al_(2)O_(3)-C),with the plasma-generated samples demonstrating better overall performance.This simple,rapid and green plasma process is considered to be applicable for the synthesis of diverse noble metal-based catalysts.

g-C_(3)N_(4)/Ag/Ag_(2)O复合材料低功率紫外照射下降解罗丹明B

光催化降解技术高效、环保、节能的优点使其在环保领域具有广泛应用前景,为解决环境污染问题提供了新的思路。其中高效催化剂是实现污染物高效光催化降解的关键。g-C_(3)N_(4)半导体材料因优良的热稳定性和化学稳定性、易于合成以及能带结构易调控等优点在催化领域具有广阔的应用前景,但由于纯g-C_(3)N_(4)可见光利用率低、表面积小、导带位置较低,限制了其实际应用中的催化活性。本文通过光诱导还原方法实现了g-C_(3)N_(4)材料表面Ag/Ag_(2)O的原位负载,系统研究了Ag/Ag_(2)O负载量对材料催化性能的影响,实现低功率紫外光催化下水中罗丹明B的快速高效去除,研究发现50 mg的g-C_(3)N_(4)中在0.24 g/L的AgNO3溶液还原得到的g-C_(3)N_(4)/Ag/Ag_(2)O复合材料具有最佳的催化性能。同时将复合材料应用于实际水体中罗丹明B染料的催化降解,取得了良好催化效果。本研究为去除水环境有机物污染提供了一种高效、绿色的解决方法。

NH_(3)SO_(3)改性稀土尾矿催化剂NH_(3)-SCR脱硝活性及SO_(2)/H_(2)O耐受性能研究

采用球磨、微波焙烧方法制备了不同质量分数NH_(3)SO_(3)改性稀土尾矿NH_(3)-SCR脱硝催化剂。通过BET、SEM-EDS、XRD、NH_(3)-TPD、H_(2)-TPR分析了催化剂脱硝活性及SO_(2)/H_(2)O耐受性能。结果表明:NH_(3)SO_(3)改性使催化剂脱硝活性得到了显著提高,10%NH_(3)SO_(3)改性催化剂在300~350℃脱硝活性可达90%左右。SO_(2)/H_(2)O共同作用可将10%NH_(3)SO_(3)改性催化剂脱硝活性提高至97%,其促进作用保持了良好的稳定性,且具有可逆性。NH_(3)SO_(3)改性稀土尾矿后,催化剂比表面积、酸性位点及强度增加,表面活性物质分散度更高,弱化了尾矿矿物晶型,提高了催化剂吸附能力和氧化还原能力,从而提高催化脱硝活性,同时具备优良的SO_(2)/H_(2)O耐受性。

B_2O_3-CuO-Li_2CO_3对CSLST陶瓷微波介电性能影响的研究

研究了添加5%B2O3-CuO基础上再添加不同含量的Li2CO3复合烧结助剂对(Ca0.9375Sr0.0625)0.3(Li0.5Sm0.5)0.7TiO3(CSLST)陶瓷的烧结行为及微波介电性能的影响。研究结果表明:添加复合烧结助剂的陶瓷烧结后其晶相仍呈斜方钙钛矿结构。在不劣化微波介电性能的条件下,陶瓷的烧结温度可降至950℃,随Li2CO3含量的增加,添加复合烧结助剂的CSLST陶瓷的体积密度和介电常数εr逐渐降低。当Li2CO3添加量为0.5%时,在950℃保温5 h,所制得的陶瓷具有优良的微波介电性能:εr=84.7,Qf=1929 GHz,τf=28.76×10-6/℃。

288K下Li^+,K^+//CO_3^(2-),B_4O_7^(2-)-H_2O四元体系的相平衡

Solubilities and properties (density, conductivity and pH value) of solutions in the quaternary system Li +,K +//CO 2- 3,B 4O 2- 7-H 2O at 288 K were experimentally studied with the isothermal equilibrium method. The phase diagram of the system consisted of two invariant points E and F, five univariant curves, and four crystallization fields that belonged to K 2CO 3·3/2H 2O,Li 2 B 4O 7·3H 2O, K 2 B 4O 7 ·4H 2O and Li 2CO 3. The composition of the solution corresponding to E was w(CO 2- 3)=2.27 %, w(B 4O 2- 7) =6.05 %, w(K + ) =4.30%,w(Li + )=0.30 % and the equilibrium solids were Li 2 B 4O 7· 3H 2O+K 2 B 4O 7·4H 2O+Li 2CO 3;The composition of the solution for F was w(CO 2- 3) =22.45%,w(B 4O 2- 7)=1.88%,w(K + )=29.96%,w(Li + )=0.03% and the equilibrium solids were K 2CO 3·3/2H 2O+ K 2 B 4O 7·4H 2O+Li 2CO 3. K 2CO 3 possesses strong salting-out effect on K 2 B 4O 7,Li 2CO 3 and Li 2 B 4O 7.

BaCO_3/La_2O_3催化剂低温甲烷氧化偶联及床层热点效应

以BaCO3和不同的镧化合物作为催化剂组分,分别采用干混法和湿混法制备了BaCO3质量含量为2.5%～15%的BaCO3/La2O3催化剂,在微型固定床反应器上评价了催化剂的甲烷氧化偶联反应性能,考察了反应条件对催化剂性能的影响,以及催化剂床层中的热点效应,采用XRD和TPR对催化剂的结构和性能进行了表征。结果表明,不同方法制备的BaCO3/La2O3催化剂在较低炉温的条件下都具有好的甲烷氧化偶联反应性能,其中湿混法制备的10%BaCO3/La2O3催化剂性能最好,在烷氧比为2,反应气体空速为36000 mL.g-1.h-1的条件下,反应炉温在125℃时甲烷氧化偶联反应仍能平稳进行。存在于催化剂床层的热点是维持甲烷氧化偶联反应的关键。不同方法制备的BaCO3/La2O3催化剂其物相和氧化还原性能也有一定的差别。

Investigation of the characteristics and deactivation of catalytic active center of Cr-Al_2O_3 catalysts for isobutane dehydrogenation

Deactivation mechanism of Cr-Al2O3catalyst and the interaction of Cr-A1 in the dehydrogenation of isobutane, as well as the nature of the catalytic active center, were studied using XRD, SEM, XPS, H2-TPR, isobutane-TPR and TPO techniques. The results revealed that the deactivation of Cr-Al2O3 catalyst was mainly caused by carbon deposition on its surface. The Cr3＋ ion could not be reduced by hydrogen but could be reduced to Cr2＋ by hydrocarbons and monoxide carbon. The active center for isobutane dehydrogenation could be Cr2＋/Cr3＋ produced from Cr6＋ by the on line reduction of hydrocarbon and carbon monoxide. The binding energy of Al3＋ was strongly affected by the state of chromium cations in the catalysts.

Effect of Al_2O_3 Binder on the Precipitated Iron-Based Catalysts for Fischer-Tropsch Synthesis

A series of iron-based Fischer-Tropsch synthesis （FTS） catalysts incorporated with Al2O3 binder were prepared by the combination of co-precipitation and spray drying technology. The catalyst samples were characterized by using N2 physical adsorption, temperature-programmed reduction/desorption （TPR/TPD） and MSssbauer effect spectroscopy （MES） methods. The characterization results indicated that the BET surface area increases with increasing Al2O3 content and passes through a maximum at the Al2O3/Fe ratio of 10/100 （weight basis）. After the point, it decreases with further increase in Al2O3 content. The incorporation of Al2O3 binder was found to weaken the surface basicity and suppress the reduction and carburization of iron-based catalysts probably due to the strong K-Al2O3 and Fe-Al2O3 interactions. Furthermore, the H2 adsorption ability of the catalysts is enhanced with increasing Al2O3 content. The FTS performances of the catalysts were tested in a slurry-phase continuously stirred tank reactor （CSTR） under the reaction conditions of 260 ℃, 1.5 MPa, 1000 h^-1 and molar ratio of H2/CO 0.67 for 200 h. The results showed that the addition of small amounts of Al2O3 affects the activity of iron-based catalysts to a little extent. However, with further increase of Al2O3 content, the FTS activity and water gas shift reaction （WGS） activity are decreased severely. The addition of appropriate Al2O3 do not affect the product selectivity, but the catalysts incorporated with large amounts of Al2O3 have higher selectivity for light hydrocarbons and lower selectivity for heavy hydrocarbons.

Research on KOH/La-Ba-Al_2O_3 catalysts for biodiesel production via transesterification from microalgae oil

Alumina supports modified by lanthanum （La） and barium （Ba） were prepared by peptization. Catalysts with different KOH contents supported on modified alumina were prepared by impregnation method. Various techniques, including N2 adsorption-desorption （Brunauer-Emmet-Teller method, BET）, X-ray diffraction （XRD）, scanning electron microscopy （SEM）, and fourier transform infrared absorption spectroscopy （FT-IR）. Catalytic activity for microalgae oil conversion to methyl ester via transesterification was evaluated and analyzed by GC-MS and GC. BET results showed that the support possessed high specific surface area, suitable pore volume and pore size distribution. Activity results indicated that the catalyst with 25 wt% KOH showed the best activity for microalgae oil conversion. XRD and SEM results revealed that Al-O-K compound was the active phase for microalgae oil conversion. The agglomeration and changing of pore structure should be the main reasons for the catalyst deactivation when KOH content was higher than 30 wt%.

Li^+(K^+)/CO_3^(2-),B_4O_7^(2-)-H_2O三元体系288K相平衡研究

采用等温溶解平衡法研究了二个三元体系Li+ (K+ ) /CO32 - ,B4 O72 - -H2 O 2 88K时的相平衡及平衡液相的主要物化性质 (密度、电导率、pH)。研究发现 :这二个三元体系均为简单共饱和型 ,无复盐及固溶体形成 ;根据溶解度数据绘制了相图 ,相图中单变量曲线所对应的平衡固相分别为 :Li2 CO3,Li2 B4 O7·3H2 O ;K2 CO3·3 /2H2 O ,K2 B4 O7·4H2 O ;K2 CO3对K2 B4 O7有强烈的盐析作用 。

DBD coupled with MnOx/γ-Al2O3 catalysts for the degradation of chlorobenzene

This paper investigates the degradation of chlorobenzene by dielectric barrier discharge(DBD)coupled with MnOx/γ-Al2O3 catalysts.MnOx/γ-Al2O3 catalysts were prepared using the impregnation method and were characterized in detail by N2 adsorption/desorption,x-ray diffraction and x-ray photoelectron spectroscopy.Compared with the single DBD reactor,the coupled reactor has a better performance on the removal rate of chlorobenzene,the selectivity of COx,and the inhibition of ozone production,especially at low discharge voltages.The degradation rate of chlorobenzene and selectivity of COx can reach 96.3%and 53.0%,respectively,at the specific energy density of 1350 J l-1.Moreover,the ozone concentration produced by the discharge is significantly reduced because the MnOx/Al2O3 catalysts contribute to the decomposition of ozone to form oxygen atoms for the oxidation of chlorobenzene.In addition,based on analysis of the byproducts,the decomposition mechanism of chlorobenzene in the coupled reactor is also discussed.

K_2CO_3-KCl-K_2B_4O_7-H_2O四元体系298K介稳相平衡的实验研究

采用等温蒸发法研究了K2CO3-KCl-K2B4O7-H2O四元体系298 K介稳平衡相关系,并测定了该体系达介稳平衡时液相的密度、折光率和pH值等物化性质。根据实验数据,绘制了该体系298 K的介稳相图及物化性质-组成图。结果表明:该四元体系属简单共饱型,无复盐或固溶体形成;其溶解度等温图含有一个共饱点、三条单变量曲线和3个结晶相区。3个结晶相区分别对应于K2B4O7.4H2O,K2CO3.32 H2O和KCl。共饱点的平衡液相组成为w(K2CO3)=51.57%,w(KCl)=1.09%,w(K2B4O7)=1.29%,所对应的平衡固相为K2CO3.32 H2O+KCl+K2B4O7.4H2O。

CeO_2-Co_3O_4 Catalysts for CO Oxidation

CeO2-Co3O4 catalysts for low-temperature CO oxidation were prepared by a co-precipitation method. In combination with the characterization methods of N2 adsorption/desorption, XRD, temperature-programmed reduction （TPR）, and FT-IR, the influence of the cerium content on the catalytic performance of CeO2-Co3O4 was investigated. The results indicate that the prepared CeO2-Co3O4 catalysts exhibit a better activity than that of pure CeO2 or pure Co3O4. The catalyst with the Ce/Co atomic ratio 1 ： 16 exhibits the best activity, which converts 77% of CO at room temperature and completely oxidizes CO at 45 ℃.

Characterization and performance of Cu/ZnO/Al_2O_3 catalysts prepared via decomposition of M(Cu,Zn)-ammonia complexes under sub-atmospheric pressure for methanol synthesis from H_2 and CO_2

Methanol synthesis from hydrogenation of CO2 is investigated over Cu/ZnO/Al2O3 catalysts prepared by decomposition of M（Cu,Zn）-ammonia complexes （DMAC） at various temperatures.The catalysts were characterized in detail,including X-ray diffraction,N2 adsorption-desorption,N2O chemisorption,temperature-programmed reduction and evolved gas analyses.The influences of DMAC temperature,reaction temperature and specific Cu surface area on catalytic performance are investigated.It is considered that the aurichalcite phase in the precursor plays a key role in improving the physiochemical properties and activities of the final catalysts.The catalyst from rich-aurichalcite precursor exhibits large specific Cu surface area and high space time yield of methanol （212 g/（Lcat·h）;T=513 K,p=3MPa,SV=12000 h-1）.

Evaluation of H2 Influence on the Evolution Mechanism of NOx Storage and Reduction over Pt–Ba–Ce/c-Al2O3 Catalysts

In this investigation, Pt–Ba–Ce/c-Al2O3 catalysts were prepared by incipient wetness impregnation and experiments were performed to evaluate the influence of H2 on the evolution mechanism of nitrogen oxides (NOx) storage and reduction (NSR). The physical and chemical properties of the Pt–Ba–Ce/c- Al2O3 catalysts were studied using a combination of characterization techniques, which showed that PtOx, CeO2, and BaCO3, whose peaks were observed in X-ray diffraction (XRD) spectra, dispersed well on the c-Al2O3, as shown by transmission electron microscope (TEM), and that the difference between Ce3+ and Ce4+, as detected by X-ray photoelectron spectroscopy (XPS), facilitated the migration of active oxygen over the catalyst. In the process of a complete NSR experiment, the NOx storage capability was greatly enhanced in the temperature range of 250–350℃, and reached a maximum value of 315.3μmol·gcat^-1 at 350℃, which was ascribed to the increase in NO2 yield. In a lean and rich cycling experiment, the results showed that NOx storage efficiency and conversion were increased when the time of H2 exposure (i.e., 30, 45, and 60 s) was extended. The maximum NOx conversion of the catalyst reached 83.5% when the duration of the lean and rich phases was 240 and 60 s, respectively. The results revealed that increasing the content of H2 by an appropriate amount was favorable to the NSR mechanism due to increased decomposition of nitrate or nitrite, and the refreshing of trapping sites for the next cycle of NSR.

Li_2B_4O_7-Li_2CO_3—H_2O三元体系298K介稳相平衡研究

文章报道西藏扎布耶盐湖卤水三元子体系Li2B4O7—Li2CO3—H2O 298 K介稳平衡实验数据,并绘制出介稳平衡相图。结果表明:该三元体系属简单共饱型,无复盐或固溶体形成;介稳平衡相图中单变度曲线(AE和BE)对应的介稳平衡固相分别为:Li2B4O7.5H2O和Li2CO3。与该体系对应的稳定相图比较:碳酸锂与平衡相图中结晶形式一致;硼酸锂在介稳相图中的结晶形式为Li2B4O7.5H2O,而平衡相图中的结晶形式则为Li2B4O7.3H2O。

Carbon dioxide reforming of methane on monolithic Ni/Al_2O_3-based catalysts

Nickel-alumina catalysts supported on cordierite monoliths of honeycomb structure surpass essentially the conventional granulated ones with respect to the output in carbon dioxide reforming of methane. Adjusting the surface acid-base properties of catalysts by introduction of alkali metal （Na, K） oxides inhibits the carbonization and as a result, improves the operational stability of these catalysts. An effect of promotion of nickel-alumina based composite doped by lanthanum oxide is found. This effect, caused by an additional route for the CO2 activation on Ni-La2O3/Al2O3/cordierite catalyst, is displayed in increase of methane conversion under conditions of an oxidant excess.

Syngas production by combined carbon dioxide reforming and partial oxidation of methane over Ni/α-Al_2O_3 catalysts

Ni/α-Al2O3 catalysts were found to be active in the temperature range 600 ～ 900℃ for both CO2 reforming and partial oxidation of methane.The effects of Ni loading,reaction temperature and feed gas ratio for the combination of CO2 reforming and partial oxidation of CH4 over Ni/α-Al2O3 were investigated.Catalysts of xwt%Ni/α-Al2O3（x=2.5,5,8 and 12） were prepared by wet impregnating the calcined support with a solution of nickel nitrate.XRD patterns and activity tests have verified that the 5wt%Ni/α-Al2O3 was the most active catalyst,as compared with the other prepared catalyst samples.An increase of the Ni loading to more than 5wt% led to a reduction in the Ni dispersion.In addition,by combining the endothermic carbon dioxide reforming reaction with the exothermic partial oxidation reaction,the loss of catalyst activity with time on stream was reduced with the amount of oxygen added to the feed.

Selective Hydrogenation of Butyne-1,4-diol to Butane-1,4-diol over Ni/Al_2O_3-SiO_2 Catalysts

Ni/Al_2O_3-SiO_2 catalysts were synthesized via one-step method employing SiO_2 as an additive for the selective hydrogenation of butyne-1,4-diol(B_3D) to butane-1,4-diol(B1D). The prepared catalysts were evaluated by a series of characterization techniques including BET, XRD, SEM, EDX-mapping, TEM, H_2-TPR, XPS, NH_3-TPD and Py-FTIR. Compared to Ni/Al_2O_3 catalyst, the SiO_2-doped samples exhibited better B_3D conversion. SiO_2 could help to form a strong interaction between NiO with the support, which inhibited Ni agglomeration at high temperature, improved the Ni dispersion, and enhanced the hydrogenation activity. B_1D selectivity was mainly influenced by the quantity of Lewis acid sites in addition to the Ni dispersion. The catalyst with a silica loading of 6.4% demonstrated an excellent selectivity of 75.18%(by 13% higher than the contrastive Ni/Al_2O_3 catalyst), which was attributed to the larger amount of Lewis acid sites and the moderate interaction between NiO with the support, which could facilitate the nickel dispersion on a preferable surface area of 176.3 m^2/g of support.

Weakening internal diffusion effect in selective hydrodesulfurization of FCC gasoline by novel designed eggshell CoMoS/Al_2O_3 catalysts

A simple method for preparation of presulfided eggshell CoMoS/γ-Al2O3 catalysts with sharp boundary is developed, through which the eggshell thicknesses of Co and Mo could be easily regulated by controlling the impregnation time. According to the results characterized by EDS, XRD, HRTEM and FT-IR of adsorbed CO, the active component structures, the nature and/or the amount of active sites on the eggshell catalyst are similar to these on the uniform catalyst. The evaluation results of the catalytic performance in selective hydrodesulfurization （HDS） of FCC gasoline show the presence of significant internal diffusion inhibition effect on HDS of S-compounds especially in the uniform catalyst. Compared with uniform catalyst, the eggshell catalyst could remarkably reduce such an internal diffusion inhibition effect due to a shortened diffusion path of the reactants, thus showing higher HDS activity and selectivity.