Preparation of Modified UiO-66 Catalyst and Its Catalytic Performance for NH_(3)-SCR Denitration

Zirconium-based metal-organic framework UiO-66 was successfully prepared by solvothermal method,and UiO-66 was modified by adding regulators such as formic acid,acetic acid,and hydrochloric acid.The NH_(3)-SCR reactivity of the samples was evaluated by the denitration activity evaluation system,and the UiO-66 and the regulator-modified UiO-66 were characterized by XRD,SEM,BET,FTIR,TG,NH_(3)-TPD,etc.,the effects of regulator types on the structure and properties of UiO-66 were investigated.The experimental results show that,after adding the modifier,the morphology of UiO-66 changes from irregular quadrilateral with serious agglomeration to particles with regular crystal shape and good dispersibility,and the crystal morphology of the catalyst is improved.In addition,after adding the modifier,UiO-66 has a larger specific surface area and stronger surface acidity,which optimizes the catalytic performance of UiO-66.The catalytic performance test results of NH_(3)-SCR show that the low-temperature activity of UiO-66 is poor,and it only shows a certain catalytic activity at higher temperatures.The catalytic activity of UiO-66 was significantly improved after adding the regulator.Among them,the UiO-66-HCl modified with hydrochloric acid had the best catalytic activity,and the denitration rate reached 70%when the denitration temperature was 380℃.

One-step green method to prepare progressive burning gun propellant through gradient denitration strategy

Gradiently denitrated gun propellant(GDGP)prepared by a“gradient denitration”strategy is obviously superior in progressive burning performance to the traditional deterred gun propellant.Currently,the preparation of GDGP employed a tedious two-step method involving organic solvents,which hinders the large-scale preparation of GDGP.In this paper,GDGP was successfully prepared via a novelty and environmentally friendly one-step method.The obtained samples were characterized by FT-IR,Raman,SEM and XPS.The results showed that the content of nitrate groups gradiently increased from the surface to the core in the surface layer of GDGP and the surface layer of GDGP exhibited a higher compaction than that of raw gun propellant,with a well-preserved nitrocellulose structure.The denitration process enabled the propellant surface with regressive energy density and good progressive burning performance,as confirmed by oxygen bomb and closed bomb test.At the same time,the effects of different solvents on the component loss of propellant were compared.The result showed that water caused the least component loss.Finally,the stability of GDGP was confirmed by methyl-violet test.This work not only provided environmentally friendly,simple and economic preparation of GDGP,but also confirmed the stability of GDGP prepared by this method.

Improvement of High-efficiency Green Catalysts for Flue Gas Denitrification

Based on the basic principle and mechanism of flue gas denitrification,the commonly used catalysts for flue gas denitrification were introduced firstly,and then the catalytic performance,stability and reaction mechanism of catalysts in the market were analyzed.Different types of catalysts were studied to look for green catalysts with high activity,sulfur resistance,water vapor resistance and other advantages.The mechanism of denitration reaction of green catalysts was discussed,and the laws of formation,propagation and consumption of active species in the reaction process were revealed to provide theoretical basis for optimizing catalyst design and improving reaction conditions.Then the research status and problems of new catalysts for flue gas denitrification were described.Finally,the future development direction of green catalysts for flue gas denitration was discussed to improve the performance and stability of catalysts and meet the performance requirements of denitration catalysts in different industries.

Feasibility Analysis of the Sintering Flue Gas Oxidation Method for Denitrification Technology Route

With the vigorous development of China’s iron and steel industry and the introduction of ultra-low emission policies, the emission of pollutants such as SO2 and NOx has received unprecedented attention. At present, the commonly used denitrification methods include selective catalytic reduction (SCR), active coke, etc. As a newly developed denitrification technology, oxidation denitrification is not widely used, and the technical level is mixed, and there might be problems such as yellow smoke, secondary pollution and ozone escape in the practical application. In this paper, problems existing in the denitrification process of sintering flue gas oxidation are analyzed, and a 320 m2 sintering machine is taken as an example. Comparing the denitrification technology of sintering industry, it could be seen that the denitrification technology route of oxidation method has low pollution, low cost and high comprehensive environmental benefits, and has greatly potential development.

Experimental studies on gas-phase mercury oxidation removal and denitration of coal combustion with NH_4 Br addition

In order to remove gas-phase mercury and NOx from flue gas, experimental studies on flue gas mercury oxidation removal and denitration of Guizhou anthracite combustion with NH4Br addition were carried out. The influence of NH4Br addition on the ignition temperature and combustion characteristics was studied using a thermogravimetric analyzer. The effects of the NHaBr addition amount on gas-phase mercury oxidation and removal were investigated in a bench scale of 6 kW fluidized bed combustor （FBC）. Mercury concentrations in flue gas were determined by the Ontario hydro method （OHM） and the mercury mass balance was obtained. Results show that the NH4Br addition has little influence on the ignition temperature of Guizhou anthracite. With the mercury mass balance of 95.47%, the proportion of particulate mercury Hg^p, gaseous mercury Hg^0 and Hg^2＋ are 75.28%, 11.60% and 13. 12%, respectively, as raw coal combustion. The high particulate mercury Hg^p in flue gas is caused by the high unburned carbon content in fly ash. When the NH4Br addition amount increases from 0 to 0. 3%, the concentration of gaseous Hg^0 and Hg^2＋ in flue gas decreases continuously, leading to the Hg^p increase accordingly. The oxidation rate of Hg^0 is positively correlated to the Br addition amount. It demonstrates that coal combustion with NH4Br addition can promote Hg^0 oxidation and removal. NOx concentration in flue gas exhibits a descending trend with the NHaBr addition and the removal rate reaches 17.31% with the addition amount of 0.3%. Adding NH4Br to coal also plays a synergistic role in denitration.

Sustainable recycling of titanium from TiO_(2) in spent SCR denitration catalyst via molten salt electrolysis

Spent catalyst used for denitration by selective catalytic reduction(spent SCR denitration catalysts) is one of the important urban mines due to the high content of TiO_(2)(~85 wt%) and the massive accumulation amount(over 100,000 tons),therefore,value-added reutilization of titanium in spent SCR catalysts is considerably meaningful.In this paper,a novel method is proposed for converting the titanium oxide in spent SCR denitration catalysts to metallic titanium.Specifically,titanium dioxide(TiO_(2)) was firstly obtained from spent SCR denitration catalysts after removing the impurities by hydrometallurgy process.Then,TiO_(2) is converted to Ti_(2)CO by carbothermic reduction method,and Ti_(2)CO was further purified by oleic acid capture.Finally,by utilizing the as-prepared Ti_(2)CO as the consumable anode in the NaCl-KCl molten salt,high-purity metallic titanium was deposited at cathode,all confirming the feasibility for the conversion of low-grade TiO_(2) in the spent catalysts,from 60 wt% to high-purity metallic Ti(99.5 wt%), furthermore,the energy consumption of this process is 3950 kWh tonne-1 Ti,which is lower than that of most traditional titanium metallurgy methods.The method herein can provide new insights for the value-added recycling of titanium resources in urban mines.

Comprehensive Solution to Flue Gas Desulfurization and Denitration of Circulating Fluidized Bed Boiler

With the advantages of high combustion efficiency, wide fuel flexibility and low concentrations of discharged pollutants, circulating fluid- ized bed （CFB） boiler has been widely used in recent years. However, in order to meet the requirement of new emission standard, it＇s necessary to add flue gas desulfurization and denitration devices. In this paper, the choice of flue gas purification processes for CFB boiler has been discussed firstly, and then the economy and rationality of the SNCR ＋ CFB-FGD ＋ COA comprehensive solution to flue gas desulfurization and denitration have been analyzed.

Relationship between the Standard Enthalpy of Formation and the Ratio of Standard Enthalpy of Formation and Exothermic Denitration Decomposition Peak Temperature of M(NTO)_n

A relationship is established, using the least squares method, between the standard enthalpy of formation and the standard enthalpy of formation divided by the exothermic denitration decomposition peak absolute temperature corresponding to β →0.

Denitration Performance of Modifi ed AC Loaded with Nano V_2O_5 with Different Morphologies

A series of V2O5 with various morphologies was prepared by the hydrothermal method and loaded on the modified active coke（AC） which was prepared by the impregnation methods. The prepared samples were characterized by BET, Boehm titration test, XRD, SEM and EDS. The SEM exhibited that the morphologies of the samples prepared were signifi cantly different from each other. Then the samples prepared were studied on the selective catalytic reduction（SCR） of NO with ammonia in the presence of oxygen. The SCR activity measurements were undertaken in a fixed-bed unit with a sieve plate in the middle. From the contrastive experiments, the results showed that linear V2O5/AC had the best denitration performance and the denitration rate was up to 57.41%. It was speculated that the linear V2O5 with the crystal faces（110） may show the best performance in SCR. And the durability results also showed that linear V2O5/AC produced a denitration rate of 47.7% after three regenerations.

某300 MW机组脱硝前紧凑空间粗颗粒飞灰预脱除关键技术研究及应用

燃煤机组由于煤质及燃烧等原因,锅炉尾部烟道烟气中的粗飞灰颗粒易造成烟道及脱硝催化剂不同程度的磨损。以某300 MW等级机组省煤器出口至脱硝入口烟道为研究对象,建立“A型折流富集+V型高效收灰+T型粗灰通道”的“A-V-T”型脱硝前粗颗粒飞灰预脱除结构,布置于省煤器出口的大截面低流速烟道内,通过数值模拟研究了布置粗颗粒飞灰预脱除装置前后不同粒径分布轨迹、脱除效果、阻力等条件的影响规律,并进行了工程应用。模拟结果表明:采用粗颗粒脱除技术后对原系统烟气侧流场状态影响小;随着飞灰粒径的增大,飞灰脱除率越高,其中50、200、500、1000μm粒径的飞灰脱除率分别为12.15%、59.40%、87.01%、93.62%,对粒径200μm及以上的粗颗粒脱除效率为85.15%,整体的收灰率为15.50%,新增阻力78 Pa。对某300 MW机组实施改造后,经试验,脱硝前对粒径200μm及以上粗颗粒灰脱除率为83.96%,整体灰的脱除率为14.91%,净增阻力73Pa,试验结果验证了数值模拟结果的合理性。

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。

W火焰锅炉SCR脱硝超低排放技术及应用

截至2021年底,全国已有超过95%的燃煤火电机组实现了氮氧化物超低排放,剩余均为燃用无烟煤的W火焰锅炉,其产生的氮氧化物质量浓度高达750~1200 mg/m^(3),实现超低排放难度大,是我国实现超低排放政策的“最后一公里”。目前,选择性催化还原(SCR)脱硝流场技术主要有“SCR分区混合动态调平技术”“全烟道断面混合流场技术”“常规精准喷氨技术”等。以某设计脱硝效率需高达95%的W火焰锅炉为例,通过计算流体力学(CFD)模拟的方式对比3种技术的性能指标,“SCR分区混合动态调平技术”的各项指标明显优于其他技术。工程改造后,在脱硝系统入口氮氧化物质量浓度为1000 mg/m^(3),出口低于50 mg/m^(3)时,可实时保持氨逃逸量小于3μL/L,远超常规SCR脱硝系统最高设计效率(93%),为W火焰锅炉氮氧化物超低排放提供了新的技术路线。

聚丙烯酰胺热分解与脱硝性能研究

选择三种不同类型聚丙烯酰胺作为高分子脱硝剂,通过热重分析、程序升温-质谱分析了三种不同类型的聚丙烯酰胺升温分解过程,同时考察其高温烟气脱硝性能。结果表明,三种不同的聚丙烯酰胺最终失重率大小为:阳离子型CPAM>非离子型NPAM>阴离子型APAM。通过程序升温-质谱检测显示,三种聚丙烯酰胺在升温分解过程中均首先发生端基酰胺基分解产生氨气,然后发生主链断裂。三种聚丙烯酰胺的热分解生成氨的表观活化能分别为CPAM 169.72 kJ/mol,APAM 246.58 kJ/mol和NPAM 210.18 kJ/mol。三种聚丙烯酰胺脱硝性能为NPAM>CPAM>APAM。脱硝活性与PAM分解产氨的速率和产氨量有关,产氨速率较慢、产氨量较高的NPAM脱硝活性较高,产氨量较低的APAM活性较差。优良的高分子脱硝剂需要较好的热稳定性以及更多分解氨的量。

氟碳铈矿除Ca、Si制备脱硝催化剂及其脱硝性能的研究

包头混合稀土精矿是氟碳铈矿(CeCO_(3)F)和独居石(CePO_(4))的共生矿物,结构复杂,难以分解,且Ca、Si杂质嵌布在矿物表面,影响了稀土矿物的脱硝活性,因此在使用天然矿物作为催化剂之前,有必要对其进行除杂预处理。采用酸浸固氟焙烧方案将氟碳铈矿制成脱硝催化剂,具体工艺为:第一步,HCl除Ca,HCl浓度为6mol/L,氟碳铈矿与NaCl(固氟剂)质量比为1∶5,混合并搅拌12h后于500℃下焙烧2h;第二步,HF除Si,HF浓度为13mol/L,除Ca后粉末与NaCl质量比为1∶5,混合并搅拌12h后于500°C下焙烧2h。氟碳铈矿除Ca、Si后制备的催化剂中Ca含量降至1.85%,Si含量降至0.17%,稀土元素含量相比原矿提高了约22%。氟碳铈矿除Ca、Si后,表面形成了发达的孔结构,比表面积增大,活性元素增多,且部分Ce的价态由+3价转变为+4价,还形成了晶格氧,这些组织结构的变化为催化剂脱硝过程提供了更多的氧化还原中心,使得催化剂脱硝性能显著提高。因此,用除杂后的氟碳铈矿作脱硝催化剂比直接用天然矿物具有更大的优势。

SCR脱硝系统的RBF条件积分滑模参数优化控制

针对选择性催化还原(SCR)脱硝系统在火电机组深度调峰下因系统特性随着机组负荷改变而难以控制的问题,提出基于径向基函数(RBF)的条件积分滑模优化控制方案,用条件积分滑模减少抖振与调节时间,用RBF实时逼近SCR脱硝系统特性改变下的未知扰动以提高系统鲁棒性。并提出一种纳什均衡量子粒子群寻优(NEQPSO)算法,以获得RBF条件积分滑模控制方案的最优参数,并在20%~100%的机组负荷下进行仿真实验。结果表明:优化后的RBF条件积分滑模控制与传统控制方案相比超调量降低50.26%、调节时间缩短13.55%,在干扰信号下超调量仅有1.50%,其响应速度更快、抗干扰能力更强、鲁棒性更好。

Ag_(2)O/TiO_(2)催化剂可见光催化脱硝性能

通过水热法制备锐钛矿TiO_(2)并与Ag_(2)O复合构建催化剂.利用BET,XRD,XPS等表征分析催化剂,并以NO为处理对象,探究反应条件对催化剂脱硝效率影响.结果表明,可见光下,当反应体系中NO浓度为23.6mg/m^(3)且氨气与氮气摩尔比为1:1时,Ag_(2)O/TiO_(2)(10%)的脱硝效率最佳达92.00%.进一步探究发现,改变反应体系中烟气湿度,脱硝效率基本不变.且同时存在CO_(2),SO_(2),NO等气体时,其脱硝效率可保持71.43%.表征结果显示与Ag_(2)O复合后比表面积增大,禁带宽度降低,PL谱峰强度降低,光电流密度提升.反应后的催化剂出现硝基非对称伸缩振动峰,因此推测,在反应进程中·O_(2)^(-),·OH,·O自由基作为氧化剂先将NO氧化为NO_(2),再进一步氧化为NO_(3)^(-),实现NO_(x)的脱除.当NH_(3)与NO_(2)的同时存在时,进一步将未完全反应的NO还原为N_(2),促进污染气体的转化,进一步提升脱硝效率.

微波加热技术在核工业中的应用研究进展

简述了微波加热的基本原理,综述了微波加热在辅助浸取铀矿物、二氧化铀陶瓷芯块烧结、硝酸盐热解脱硝、放射性废物处理、放射性元素分析前处理等核工业中的应用研究进展,指出了微波加热技术在核工业中应用所面临的主要问题和挑战,展望了未来的研究发展方向和应用前景。

SCR脱硝系统的串级自耦PID控制方法

针对选择性催化还原(SCR)脱硝系统具有多扰动、大惯性和模型不确定性等特性,提出了一种基于自耦比例积分微分(SCPID)控制理论的控制方法。该方法将SCR脱硝系统中的内部扰动、外界扰动与模型不确定性等一切复杂因素定义为总扰动,进而将该系统映射为线性扰动系统,据此构建了一个在总扰动反相激励下的受控误差系统,然后针对SCR脱硝系统的内环和外环系统分别设计了自耦PID控制器,使得控制力的量纲与被控系统相匹配,最后采用3个仿真试验验证所提方法的有效性。结果表明:所提出的SCPID控制方法响应速度快、无超调、抗干扰能力强,同时具有良好的鲁棒性。

氨再燃过程中NO还原及再生成机理

以氨再燃技术为应用背景,采用Chemkin软件选取Zhang机理在PFR反应器模型中进行NO/O_(2)/H_(2)O/N_(2)气氛下氨再燃的动力学模拟,考察了温度(1173~1573K)、氧浓度(0~4%)、再燃比(1%~30%)对再燃性能的影响.结果表明:在研究参数范围内,氨再燃脱硝效果显著,脱硝率可达97%以上,在1350~1469K温度窗口内能实现80%以上的脱硝率.并从反应路径角度对氨再燃过程中存在的NO还原区、平衡区、NO再生成区进行了分析.当氧浓度高于1.5%时,会出现NO再生成区,且氧浓度越高NO反弹越大最终NO浓度越高.而再燃比的影响需要综合考虑脱硝率和未反应氨,在(10%±3%)范围内为佳.

烧结烟气整体式低温脱硝催化剂的制备

针对钢铁行业烧结烟气脱硝治理,本文以堇青石为基材,通过真空涂敷催化剂浆液,制备了一种整体式低温SCR脱硝催化剂,研究了催化剂浆液配方、涂覆层厚度对催化剂性能的影响。结果表明,当催化剂浆液pH值=4.5、浆液粒度D50≤5μm、涂敷层厚度为83μm时,催化剂综合性能最优,催化剂抗磨损质量损失率≤1.2%,160℃烟气条件下脱硝率≥95%,SO_(2)/SO_(3)转化率≤0.19%。