配NO2调节NOx氧化度双循环一塔硫硝同脱研究

以石灰浆液作吸收液,在筛板塔双循环模式下开展了模拟烟气同时脱硫脱硝实验,并通过配加NO2调节NOx氧化度来提高脱硝率.主要研究了液气比、吸收液温度、NO2/NOx (体积比)、SO2浓度等因素对脱硝率的影响.实验结果表明:当烟气量20 m3/h,SO2和NO进气体积分数分别为5.5×10-4和3×10-4,NO2/NOx为0.5,液气比4 L/m3,温度298 K的石灰浆液吸收烟气时,SO2和NOx的吸收率分别可达到96.63％和88.36％,实现了脱硫脱硝同塔完成.     

新型吸附-催化剂La-Cu-Na-γ-Al2O3同时脱除SO2和NO的实验研究

利用固定床连续流动反应器研究了新型吸附-催化剂La-Cu-Na-γ-Al2O3同时吸附脱除模拟烟气中SO2和NO的工艺条件、循环使用性能,模拟烟气组成是0.5%SO2、0.15%～0.057% NO、0%～8% O2,Ar平衡.通过对不同温度下比表面分析研究了La-Cu-Na-γ-Al2O3的热稳定性,利用程序升温表面反应(TPSR)研究了La-Cu-Na-γ-Al2O3的再生性能.结果表明,La-Cu-Na-γ-Al2O3的适宜工艺条件是SO2/NO为5.1～3.5、原料气含氧量大于4.5%、吸附温度448 K.La-Cu-Na-γ-Al2O3在循环使用过程中吸附能力下降.与NOXSO工艺的吸附-催化剂Na-γ-～2O3相比,La-Cu-Na-γ-Al2O3同时吸附SO2和NO的能力大(SO2/NO为5.1～3.5时,La-Cu-Na-γ-Al2O3同时吸附SO2和NO的吸附量分别是Na-γ-Al2O3的1.25和4.7倍.)、再生循环使用性能好、热稳定性好,将La-Cu-Na-γ-Al2O3应用于NOXSO工艺可望提高该工艺的脱硫脱氮效率.     

臭氧氧化结合氨法同时脱硫脱硝的实验研究

采用臭氧氧化结合氨水溶液的方法,在填料塔内开展了同时脱硫脱硝的实验研究。通过考察O_3与NO摩尔比[n(O_3)/n(NO)]、吸收液氨水质量分数、液气比、SO_2进口质量浓度以及NO进口质量浓度等因素对脱硫脱硝效率的影响,确定其最佳工艺操作条件,并在此条件下进行稳定性实验。结果表明:臭氧的加入显著地提高了脱硝效率,当n(O_3)/n(NO)=1.0时,脱硝效率可以达到85.7%;氨水质量分数的增加也在一定程度上提高了脱硝效率;最佳工艺操作条件为O_3与NO摩尔比为1.0、吸收液氨水质量分数为0.15%和液气比为40 L/m~3。在最佳工艺条件下,对SO_2和NO进口质量浓度分别为5 120 mg/m~3和600 mg/m~3的烟气进行脱除实验,其平均脱硫效率和脱硝效率可以达到100%和88.1%。该方法具有较高的脱除效率和广泛的应用前景。     

活性炭混合钢渣烧结烟气脱硫脱硝实验研究

采用混合法用钢渣与活性炭制备混合钢渣活性炭吸附剂，对其进行XRF, BET, SEM和FT-IR等表征，于可编程电加热固定床反应器中进行模拟烧结烟气脱硫脱硝实验，考察反应温度、SO2浓度及[NH3]/[NO]浓度比、O2含量等因素对混合钢渣活性炭的吸附及催化性能的影响。结果表明，模拟烧结烟气中SO2初始浓度0.06vol%, NO初始浓度0.04vol%, O2含量15vol%及反应温度120℃条件下，最高脱硫脱硝率分别为79%和34%。按浓度比[NH3]/[NO]=1通入还原剂NH3时，脱硫脱硝率均升高，表明钢渣具有一定催化还原作用。脱硝率随反应温度升高而下降，O2含量提高有利于混合钢渣活性炭对SO2和NO的吸附。掺混钢渣降低了吸附剂的比表面积，但钢渣中含一定量Fe2O3，具有一定催化还原作用，有利于NO吸附。同时，加入钢渣也是对固废资源的合理利用，达到“以废制污”的目的。     

活性焦联合脱硫脱硝工艺试验研究

为了开发活性焦联合脱硫脱硝工艺,选取一种商用活性焦在微型反应器上进行NH3对NO、SO2脱除影响及NO和SO2脱除交互影响试验,提出了活性焦联合脱硫脱硝工艺路线,并在实验室搭建的模拟装置上进行了工艺路线的模拟试验验证。结果表明,活性焦脱硝是低温SCR反应,NH3的存在使SO2吸附量提高约18%,说明NH3与SO2发生化学反应,有利于SO2脱除,但生成的硫铵会降低工业装置的稳定性;当活性焦无吸附NH3时,NO对SO2脱除无影响,当活性焦吸附NH3时,通入NO前后,SO2出口体积分数由0.15%降至0.13%左右,说明NO对SO2脱除有促进作用;通入SO2气体后,NO出口体积分数由0.045%迅速增至0.065%,说明SO2与NO争抢NH3,不利于脱硝。通过工艺路线模拟试验发现,当联合脱硫脱硝空速为400 h-1时,脱硫效率≥95%,脱硝效率≥70%,验证了活性焦联合脱硫脱硝工艺的可行性。     

废酸再生装置烟气脱硫脱硝运行实践

介绍了惠州炼化10 kt/a废酸再生装置进行废酸尾气H2O2-DNSTM工艺脱硫脱硝中试研究.以H2O2作为氧化剂,以钠碱作为吸收剂,脱硝技术路线采用部分烟气加温激活H2O2工艺.中试结果表明：NO转化率较高,达到68.6％;采用鼓泡吸收时,NOx吸收率在70％左右,效果较好;SO2转化率达97.4％;尾气出口NOx和SO2质量浓度分别为32 mg/m^3和14 mg/m^3,满足该地区排放要求.H2O2-DNSTM工艺具有脱硫脱硝效率较高、运行可靠稳定、维护保养简单、占地较小的优点,适用于现有废酸再生装置尾气处理系统的改造升级.     

低温等离子体用于柴油机尾气脱硝的实验

柴油机作为卡车、重型机械以及船舶的主动力装置仍被广泛采用,其尾气中氮氧化物的脱除技术也是目前的研究热点。本文搭建了模拟柴油机尾气的配气系统,采用介质阻挡放电产生低温等离子体（non-thermal plasma,NTP）的方法对模拟柴油机尾气进行了脱硝的实验研究。实验结果表明：针对本系统,电源效率和能量密度随着输入电压的增大而升高,当输入电压高于60V时,电源效率在90%以上;在O₂/N₂条件下,随着O₂浓度以及能量密度的增加,NO生成量逐渐增加,NO₂生成量先增加后降低最终趋于稳定;在NO/N₂条件下,低温等离子体对NO的脱除率接近100%;在NO/O₂/N₂条件下,随着NO浓度的增加,临界O₂浓度升高,O₂体积分数为1%时脱硝效率在90%以上,O₂体积分数高于14%时低温等离子体的脱硝率为负值,且随着能量密度的增加,生成的NO _x 浓度也更高,O₂浓度对低温等离子体的脱硝性能起决定性作用;在低能量密度时,加入NH₃会提高脱硝性能,高能量密度时NH₃会略微降低NTP的脱硝性能,当加入H₂O模拟真实柴油机尾气成分且喷氨时,获得的脱硝率最高为40.6%。     

烧结烟气联合脱硫脱硝试验研究

设计了一套500 m3/h烟气联合脱硫脱硝小试装置,将选择性催化还原(SCR)脱硝装置布置在脱硫工艺后,通过试验对循环流化床半干法脱硫与SCR脱硝工艺进行了研究。研究表明,脱硫效率随着喷水量、床内物料量的增大而增大,脱硝效率随着氨氮比的增大而增大;脱硫装置烟气出口温度控制在79℃时,循环流化床半干法脱硫效率在90%左右,可满足烧结烟气SO2最新排放标准的要求;在此条件下,将烧结烟气再热到300℃脱硝,脱硝效率可达50%,可满足烧结烟气NOx最新排放标准的要求。     

臭氧氧化结合硫代硫酸钠溶液喷淋同时脱硫脱硝

采用臭氧氧化结合湿法喷淋硫代硫酸钠溶液的方法开展模拟烟气同时脱硫脱硝实验研究。结果表明,采用臭氧氧化结合Na2S2O3-Na OH溶液湿法喷淋可以实现NOx和SO_2协同脱除:在O_3/NO摩尔比为1.1~1.2时,溶液中Na2S2O3浓度的增加会提高系统的NO_x脱除效率,烟气中SO2的存在会促进NOx的脱除,当SO2浓度为1030mg·m~(-3)、2.0%Na_2S_2O_3溶液作为喷淋液时可实现较高的SO_2脱除效率,同时NO_x脱除效率可达70%以上;喷淋液p H在2.5~9范围内变化时提高浆液p H有利于NOx的脱除,当p H=9时脱硝效率可达75%。180 min连续同时脱硫脱硝实验结果表明,硫代硫酸钠可有效促进NOx的脱除,并实现SO2较高的脱除效率,同时可实现系统同时脱硫脱硝连续稳定运行,喷淋吸收后烟气中NO_x的主要转化产物为NO~-_2,该方法作为一种有效的同时脱硫脱硝技术,具有一定的工业应用推广前景。     

以偏钛酸为原料的催化剂的脱硝性能研究

以偏钛酸为原料通过浸渍法和固相物质的热分解法来制备以NH3为还原剂选择性催化还原NOx的催化剂V2O5-WO3/TiO2。着重考察催化剂组成、NH3/NO摩尔比和模拟烟气中O2浓度对催化剂脱硝性能的影响。催化剂的脱硝性能测试结果表明催化剂V2O5(1.2%)-WO3(8.8%)/TiO2具有较高的催化活性和较宽的活性温度窗口,NO的转化率最高可达98.77%。综合考虑NH3逃逸、设备腐蚀和环境问题,NH3/NO摩尔比控制在1.2以内比较合适;富氧条件对脱硝催化反应的进行更有利。     

A Novel Dry Process for Simultaneous Removal of SO2 and NO from Flue Gas in a Powder‐Particle Fluidized Bed

A novel sorbent, potassium carbonate impregnated on porous fine alumina, was produced, and its reactive and regenerative properties were evaluated for dry‐type simultaneous removal of SO₂ and NO from flue gas under stack temperatures, by using a powder‐particle fluidized bed (PPFB) with I.D. of 53 mm as the reactor. High removal efficiencies for SO₂ and NO were achieved simultaneously. An apparent beneficial effect of SO₂ on the enhancement of NO removal was found based on a large amount of data. The alumina carrier was successfully regenerated and used repeatedly for the production of fresh sorbent particles. With no ammonia, low temperature, high removal efficiency, and no second waste emission as main characteristics, this dry process can be a competitive technology for pollution control of flue gas from power plants in the future.     

Performance with Respect to Flue Gas Composition of a Combined Desulfurization／Denitration Process Using Powder-Particle Fluidized Bed

A new combined desulfarizatinn/denitraticon (DeSOx/DeNOx) procees was teeted in this study. The procees uses the so-called powder-partlcle fluidized bed (PPFB) as the major reactor in which a coarse DeNOx catalyst, several hundrsd micrometers in size, is fluidized by flue gas as the fluidization medium particles while a contlnuogsly supplied fine DeSOx sorbent, several to tens of micrometers in dianteter, is entrained with the flue gas. Ammonin for NOx reduction is fed to the bottom of the bed, thus, SOx and NOx are simultaneously removed in the single reactor.By adopting a model gas, SO2-NO-HaO-N2-air, to simulate actual flue gas in a laboratory-scale PPFB, simultaneous SO2 and NO removals were explored with respect to various gas components of flue gas. It was found that the vaxlations of SO2 removal with concentrations (fractions) of oxygen, water vapor, SO2 and NO in flue gas are little affected by the simultaneous NOx reduction. However,the dependencles of NO removal upon such gas components are clveely related to the inter-actions between DeSOx sorbent and DeNOx catalyst.     

Simultaneous SO2/NOx removal by a powder-particle fluidized bed

Simultaneous dry removal of SO₂ and NO_x from flue gas has been investigated using a powder-particle fluidized bed. In a process of flue gas desulfurization by use of solid sorbents such as FeO (dust from a steel plant) and CuO, the smaller the particle size of sorbents, the higher the expected SO₂ conversion. In a powder-particle fluidized bed (PPFB), fine particles less than 40 μm in diameter fed into the bed are fluidized with coarse particles. But only the fine particles are entrained from the bed, and their residence time in the bed is remarkably long.

The reduction of NO_x with NH₃ in the fluidized bed is catalyzed by coarse particles or both coarse and fine particles. In this study, PPFB was applied to simultaneous dry SO₂/NO_x removal process, and several kinds of sorbents or catalysts were evaluated in a PPFB. Using the selected sorbents and catalysts, kinetic measurements were made in the temperature range of 300 to 600°C. SO₂ removal efficiencies were affected by reaction temperature, sorbent/S ratio, and static bed height. NO_x removal efficiencies in excess of 95% were achieved at NH₃/NO_x mole ratio of 1.0. When FeO was used as sorbent, SO₂ conversion increased with increasing temperature and reached 80% at 600°C.     

CO2对石灰石脱硫剂的活化作用

在间歇式鼓泡反应器的烟气脱硫实验装置中,研究了CO2气体活化处理对石灰石脱硫剂浆液烟气脱硫效率的影响. 依据脱硫过程中石灰石脱硫剂浆液pH值随脱硫反应时间的变化规律,初步分析了CO2对石灰石脱硫剂的活化作用及活化后石灰石脱硫剂的烟气脱硫过程机理. 结果表明,CO2气体的活化处理促进了石灰石在水溶液中的溶解,进而改善了石灰石脱硫剂浆液的烟气脱硫反应活性,使处理后的石灰石脱硫剂浆液的烟气脱硫效率和脱硫剂的利用率提高. 基于流化床反应器连续过程的实验结果,证实了CO2对石灰石脱硫剂的活化作用. 为提高石灰石在烟气脱硫中的反应活性提供了一种新的工艺,可用于烟气脱硫中对石灰石脱硫剂浆液的活化.     

Modelling of a fluidized bed carbonator reactor to capture CO2 from a combustion flue gas

In recent years several processes incorporating a carbonation-calcination loop in an interconnected fluidized bed reactor have been proposed as a way to capture CO₂ from flue gases. This paper is a first approximation to the modelling of a fluidized bed carbonator reactor. In this reactor the flue gas comes into contact with an active bed composed of particles with very different activities, depending on their residence time in the bed and in the carbonation-calcination loop. The model combines the residence time distribution functions with existing knowledge about sorbent deactivation rates and sorbent reactivity. The fluid dynamics of the solids (CSTR) and gases (PF) in the carbonator are based on simple assumptions. The carbonation rates are modelled defining a characteristic time for the transition between a fast reaction regime to a regime with a zero reaction rate. On the basis of these assumptions the model is able to predict the CO₂ capture efficiency for the flue gas depending on the operating and design conditions. Operating windows with high capture efficiencies are discussed, as well as those conditions where only modest capture efficiencies are possible.     

Removal of SO2 in Semi‐Dry Flue Gas Desulfurization Process with a Powder‐Particle Spouted Bed

Semi‐dry flue gas desulfurization was investigated with several kinds of SO₂ sorbents, such as slaked lime, limestone, Mg(OH)₂ and concrete pile sludge, in a powder‐particle spouted bed. Slurry droplets including sorbent fine particles were fed to a spouted bed of coarse inert particles spouted with hot gas containing SO₂. SO₂ removal efficiency was strongly affected by the approach to saturation temperature, Ca/S molar ratio and particle size of sorbent. Slaked lime showed the highest desulfurization efficiency. In this process, despite very short gas residence time, more than 90% SO₂ removal was easily achieved by choosing appropriate conditions.     

Removal of SO2 from flue gas using a new semidry flue gas desulfurization process with a powder-particle spouted bed

A spouted bed of binary particle mixture was applied to a low temperature desulfurization process in order to develop a new type of semidry flue gas desulfurization (FGD) technology. We investigated the effects of operating parameters, such as type of SO₂ sorbent, diameter of SO₂ sorbent particles, apparent residence time of gas in the bed, approach to saturation temperature and Ca/S molar ratio, on SO₂ removal in a bench-scale powder-particle spouted bed. We also investigated the utilization rate of SO₂ sorbent and ways to enhance the efficiency of SO₂ removal and SO₂ sorbent utilization. The experimental results showed that SO₂ removal is significantly affected by the approach to saturation temperature and Ca/S molar ratio, and that a high SO₂ removal efficiency and effective sorbent utilization can be obtained under appropriate operating conditions. Thus, this new simple process of flue gas desulfurization is highly efficient and has little impact on the environment.     

烟气气相组分及Ca(OH)_2对KMnO_4氧化NO的影响机理

在固定床反应器中考察了KMnO₄氧化烟气中NO的过程,分析了烟气组分H₂O、O₂及SO₂对NO氧化过程的影响规律,得到了Ca（OH）₂对KMnO₄氧化NO的影响机理。实验结果表明,H₂O是KMnO₄氧化NO的必要条件;在含H₂O条件下,O₂可以提高NO氧化率。SO₂与氧化剂反应生成无水钾镁钒类复盐K₂Mn₂（SO₄）₃对NO氧化具有负面作用;Ca（OH）₂的加入提高了氧化剂表面的固体碱度从而促进氧化过程进行;通过添加Ca（OH）₂可以降低SO₂对NO氧化过程的负面影响。根据气体成分和产物分析可知,KMnO₄在钙基吸收剂表面氧化烟气中NO的机理可能是KMnO₄以离子态将吸附在氧化剂表面的NO和SO₂氧化为NO₂和SO₃,生成的NO₂、SO₃再传递到氧化位临近的碱性位被吸收。     

Development of sorbent manufacturing technology by Agitation Fluidized Bed Granulator (AFBG)

Thousands of ppmv of hydrogen sulfide included in coal gas should be reduced to less than a hundred ppmv in the case of IGCC to prevent a gas turbine from being corroded, and few ppmv to prevent the performance of electrodes from declining in the case of MCFC. In the present paper a laboratory scale AEBG (Agitation Fluidized Bed Granulator) is made and improved. The sorbent for the removal of hydrogen sulfide is produced using an agitation fluidized bed granulator (ZnO 1.5 mole+TiO₂ l.0mole+bentonite 5.0 wt%). The techniques for fluidizing fine particles, classified in Geldart C group, in a fluidized bed are developed by installing an agitator blade in a fluidized bed granulator. The fine particles are fluidized and granulated successfully by using the techniques. Statistical, spectral and chaos analyses with granulated sorbent (100-300 Μm) are performed to investigate the hydrodynamics of granulates in a fluidized bed. The average absolute deviation, power spectral density functions, phase space trajectories, and Kolmogorov entropy obtained from pressure fluctuation are plotted as a function of fluidizing velocity. It is shown that the Kolmogorov entropy implying the rate of generation of information can be applied to the control of fluidization regimes.     

生物质—煤混合燃烧SO2排放特性研究

在自行研制的小型循环流化床试验台上,对生物质与褐煤混合燃烧烟气中SO2排放状况进行了研究。试验选取四种不同生物质(葵花秸秆、玉米秸秆、沙柳枝条、柳树枝条)与褐煤混合,在不同生物质种类、掺混比例和床温试验条件下测定了燃烧烟气中SO2析出状况;结果表明:掺混不同生物质,SO2析出程度存在明显差异;生物质掺混比例越高,SO2排放量越小;本文所选床温范围内,随着温度的升高,SO2排放量逐渐增大。