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1.
采用热重-质谱-红外联用技术(TG-MS-FTIR),Ar气氛下对煤进行化学链气化实验,实时分析还原过程热解阶段和水蒸气气化反应阶段的过程中固体质量变化和生成气体成分。使用X射线光电子能谱对固相产物进行表面元素分析,探究化学链气化还原过程不同阶段固相产物中氮赋存形态的变化。研究结果表明:载氧体对化学链气化还原过程不同阶段含氮气体释放均有影响。热解阶段载氧体促进自由基的生成,加速了一次热解阶段含氮气体的释放,高温下,载氧体促使NH3转化为HCN;气化阶段载氧体的加入使半焦的石墨化程度降低,含氮气体释放速率增加。对固相产物中氮的赋存形态而言,载氧体会抑制热解阶段吡咯型氮的分解与转化,高温下,半焦的石墨化和有序化程度降低的同时,镶嵌在煤大分子里面的质子化吡啶裸露出来,质子化吡啶含量降低,吡啶型氮和吡咯型氮的含量大大提升。 相似文献
2.
生物质化学链气化(chemical looping gasification, CLG)为生物质能源的利用开辟了新途径,氧载体在CLG过程中具有重要作用,其性能是影响CLG反应过程的关键因素。本文重点阐述了CLG技术中氧载体的性能评价指标、类型、制备方法及其对CLG过程中产生焦油的影响。通过对比分析目前研究成果,指出Fe基氧载体在生物质CLG过程中应用最广泛,而Ni基氧载体具有较高的活性和较大的载氧能力,且对于CLG副产物焦油具有较高的催化转化效率。未来该领域研究的重点方向是开发高活性且环境友好的氧载体,推进CLG工艺的工业应用。本文为今后生物质CLG氧载体的开发与优化提供了借鉴。 相似文献
3.
基于NiO载氧体的煤化学链燃烧实验 总被引:2,自引:2,他引:2
采用流化床反应器并以水蒸气作为气化-流化介质,研究了以NiO为载氧体在800~960℃内的煤化学链燃烧反应特性。实验结果表明,载氧体与煤气化产物在反应器温度高于900℃体现了高的反应活性。随着流化床反应器温度的提高,气体产物中CO2的体积浓度(干基)呈单调递增;CO、H2、CH4的体积浓度(干基)呈单调递减;煤中碳转化为CO2的比率逐渐递增,碳的残余率逐渐递减。反应器出口气体CO2、CO、H2、CH4的生成率随反应时间呈单峰特性,H2生成率的峰值远小于CO的峰值;且随反应器温度升高,CO2生成率升高,CO、H2、CH4的生成率降低。反应温度高于900℃时,流化床反应器NiO载氧体煤化学链燃烧在9 min之内就基本完成,CO2含量高于92%。 相似文献
4.
目前化学链过程常用的Fe2O3/Al2O3载氧体会形成FeAl2O4,因热力学限制很难与水反应制氢。为了抑制FeAl2O4的形成,本文向Fe/Al载氧体中添加Mg,在固定床上进行煤化学链制氢(CLHG),深入分析Mg的作用机理并探究其对实验结果的影响。XRD结果表明,Mg质量分数从1%增加到26.5%时,MgAl2O4特征峰增强,FeAl2O4特征峰逐渐消失,说明Mg减弱了Fe和Al之间的相互作用。SEM显示Mg添加后载氧体颗粒减小,耐烧结性能优异。对比不同煤/载氧体质量比的实验,质量比为0.5/15时碳转化率和产氢量最高。在不同Mg含量的载氧体中,Fe40Mg20Al40具备最好的反应性能,碳转化率和产氢量为81.75%和1.7182L/g,比Fe40Al60分别增加10.2%和58.5%。Fe40Mg20Al40经10次循环,表面仅有轻微烧结,碳转化率和产氢量均在78%和1.52L/g以上,循环性能良好。添加Mg可以有效抑制FeAl2O4的生成,显著增强蒸汽氧化过程的反应活性,大幅提高氢气产量,十分适用于煤化学链制氢。 相似文献
5.
前期研究发现高弥勒指数晶面载氧体Fe2O3[104]具有高的化学链燃烧反应特性,且Co对煤及其热解中间产物具有催化气化和催化转化作用。通过正交实验优化制备Co-Fe2O3[104]/Al2O3载氧体体系结构,开展Co-Fe2O3[104]/Al2O3与褐煤的化学链燃烧,揭示载氧体与褐煤发生化学链燃烧的特性。结果表明:形貌控制制备的高弥勒指数晶面铁基载氧体Co-Fe2O3[104]/Al2O3(质量分数10%)促进了褐煤化学链燃烧过程中氧的迁移速率以及载氧体的还原程度,进而显著提高了载氧体与褐煤化学链燃烧的反应速率及反应效率。进一步通过CO多循环化学链燃烧反应、XRD和TEM表征了Co-Fe2O3[104]/Al2O3(10%)的可再生性及反应稳定性。 相似文献
6.
在热重分析仪和固定床反应器上对基于CoFe2O4载氧体的生物质化学链气化反应特性进行了研究,考察了载氧体与生物质质量比、水蒸气、反应温度对生物质化学链气化反应特性的影响,同时也对载氧体的循环反应性能进行了研究。通过XRD及SEM对新制备的和反应后的载氧体进行了表征。热重结果表明:CoFe2O4能够提供晶格氧,有效促进生物质气化。当CoFe2O4与生物质质量比为0.8,水蒸气体积分数为50%,温度为900 ℃时,气化反应效果最好。5次循环反应后,仍能获得较高品质的合成气,载氧体能够循环再生且未出现明显烧结团聚。 相似文献
7.
Nanhang Dong Ruiqiang Huo Ming Liu Lisheng Deng Zhengbing Deng Guozhang Chang Zhen Huang Hongyu Huang 《中国化学工程学报》2021,29(1):335-343
Chemical looping gasification (CLG) provides a novel approach to dispose the sewage sludge. In order to improve the reactivity of the calcined copper slag, NiO modification is considered as one of the good solutions. The copper slag calcined at 1100 ℃ doped with 20 wt% NiO (Ni20-CS) was used as an oxygen carrier (OC) in sludge CLG in the work. The modification of NiO can evidently enhance the reactivity of copper slag to promote the sludge conversion, especially for sludge char conversion. The carbon conversion and valid gas yield (Vg) increase from 67.02% and 0.23 m3·kg-1 using the original OC to 78.34% and 0.29 m3·kg-1 using the Ni20-CS OC, respectively. The increase of equivalent coefficient (Ω) facilitates the sludge conversion and a suitable Ω value is determined at 0.47 to obtain the highest valid gas yield (0.29 m3·kg-1). A suitable steam content is assigned at 27.22% to obtain the maximum carbon conversion of 87.09%, where an acceptable LHV of 12.63 MJ·m-3 and Vg of 0.39 m3·kg-1 are obtained. Although the reactivity of Ni20-CS OC gradually decreases with the increase in cycle numbers because of the generation of NiFe2O4-δ species, the deposition of sludge ash containing many metallic elements is beneficial to the sludge conversion. As a result, the carbon conversion shows a slight uptrend with the increase of cycle numbers in sludge CLG. It indicates that the Ni20-CS sample is a good OC for sludge CLG. 相似文献
8.
Peng Gao Yue Shen Min Zheng Guirong Bao Hua Wang Haitao Xie Lulu Wang 《加拿大化工杂志》2023,101(5):2444-2456
Chemical looping is a novel fuel conversion and material separation technology. It can be applied to obtain sulphur through selective oxidation of H2S. Further, chemical looping combustion (CLC) of sulphur can generate SO2 with a high concentration without NOx formation. The high SO2 concentration is adjustable and facilitates large-scale H2SO4 production. In this study, we examined the thermodynamics of the CLC of sulphur for H2SO4 production, which has not been reported previously. We analyzed the effects of reactor temperature and sulphur to Fe2O3 oxygen carrier (OC) ratios on sulphur allotrope transformations and on the distributions of reaction products. Moreover, the reactors were operated auto-thermally. Based on this design, we examined the effects of fuel reactor (FR) and air reactor temperatures on the minimum recirculation of the OC, as well as the gas and solid products and heat released from the air reactor. Our results showed that the CLC of sulphur with Fe2O3 OC could occur through an auto-thermal process. The FR in a sulphur CLC system should be operated over a temperature range of 800–950°C, with an Fe2O3 OC recirculation between 45 and 143 kg/kgS(s). Furthermore, when the FR was operated in the auto-thermal mode, we achieved 100% SO2 conversion. The findings of this study may be applied to reactor design for large-scale H2SO4 production through CLC of sulphur. 相似文献
9.
Chemical looping combustion (CLC) has the inherent property of separating CO2 from flue gases. This paper is concerned with the application of chemical looping to the combustion of a solid fossil fuel (a lignite and its char) in a technique whereby the fuel is gasified in situ using CO2 in the presence of a batch of supported copper oxide (the “oxygen carrier”) in a single reactor. As the metal oxide becomes depleted, the feed of fuel is discontinued, the inventory of fuel is reduced by further gasification and then the contents are re-oxidised by the admission of air to the reactor, to begin the cycle again. The choice of oxides is restricted because it requires an oxide which is exothermic during reduction to balance the endothermic gasification reactions. Copper has such oxides, but a key question is whether or not it can withstand temperatures at which gasification rates are significant (∼1173 K), particularly from the point of view of avoiding sintering and deactivation of the carrier in its reduced form. It was found that an impregnated carrier, made by impregnating a θ-alumina catalyst support (BET area 157 m2/g) with a saturated solution of copper and aluminium nitrates, acted as a durable carrier over 20 cycles of reduction and oxidation, using both Hambach lignite coal, and its char, and with air as the oxidising agent. During the course of the experiments, the BET surface area of the support fell from ∼60 m2/g, just after preparation, to around 6 m2/g after 20 cycles. However, this fall did not appear to affect the overall capacity of the oxygen carrier to react with fuels and its effect on the kinetics of the reaction with CO did not influence the outcome of the experiments, since the overall performance of the looping scheme is dominated by the much slower kinetics of the gasification reaction. The apparent kinetics of the gasification are faster in the presence of the looping agent: this is because the bulk concentration of CO in the presence of the looping agent is lower, and partly because the destruction of CO in the vicinity of a gasifying particle enhances the rate of removal of CO by mass transfer (and increases the local concentration of CO2). There was little evidence to suggest a direct reaction between carbonaceous and carrier solids, other than via a gaseous intermediate. However, the observation of finite rates of conversion in a bed of active carrier, fluidised by nitrogen, is a scientific curiosity, which we have not been able to explain satisfactorily. At 1173 K, as used here, rates of gasification of Hambach lignite, and its char, are significant. The CuO in the carrier decomposes at 1173 K to produce gas-phase O2 and Cu2O: both can react with CO produced by gasification, whilst the O2 can react directly with the char. 相似文献
10.
The performance of the Fe2O3/Al2O3 oxygen carrier modified by the alkali metals, Na and K, was studied by thermogravimetric analysis and in a laboratory-scale fluidized-bed reactor. Different factors, such as the alkali metal content, the alkali metal type, and the interaction between Na and K, were taken into account. Both Na and K had strong catalytic effects on the conversion of Fe2O3. A high K content caused serious agglomeration. Increasing the Na content led to slagging because of the low-melting point solid solution. The possibility of agglomeration and slagging was reduced when Na and K were added together. The oxygen carrier with 1.5 wt % Na and 1.5 wt % K had better combustion efficiency and optimal thermal stability. Na and K could enhance the attrition resistance and prolong the lifetime of the oxygen carriers. 相似文献
11.
化学链燃烧是近年来提出的一种具有高效、内分离CO2特点的新型燃烧方式。本文在立式管式炉实验装置上研究了温度对基于Fe2O3载氧体的煤化学链燃烧载氧体还原过程中汞析出特性的影响,探讨了不同燃烧温度下燃料反应器(FR)出口烟气组分的变化及其对汞迁移变化的影响。结果表明:在高温条件下(≥ 800℃),煤中的汞在载氧体还原过程中基本全部析出,180s时基本达到90%,并且随着温度升高而增加;FR出口烟气中的汞主要以单质态(Hg0)形式存在,各工况下的单质态汞占烟气中气态总汞比例都在88%以上,随着温度的升高,烟气中Hg0/HgT略有降低;温度对烟气组分具有影响,随着温度的升高,CO、NO和SO2浓度上升;对于汞而言,SO2会抑制Cl及Cl2的形成从而抑制Hg0向Hg2+转化,NO会直接或间接促进汞的氧化过程,FR烟气中以CO为主的还原性气氛不利于汞的氧化。 相似文献
12.
在日益增长的能源需求与日益严峻的全球气候变化带来的双重压力下,清洁、高效且经济的能源利用方法显得尤为重要。将化学链概念用于传统化石能源的转化是一种前景广阔的新技术。化学链燃烧利用载氧体间接转化含碳燃料,同时实现二氧化碳的捕集。俄亥俄州立大学研发了采用铁基载氧体和移动床反应器的化学链技术,可实现天然气、煤、生物质等多种燃料向电力、氢、液体燃料等产品的零排放转化。目前,合成气化学链(syngas chemical looping,SCL)和煤直接化学链(coal direct chemical looping,CDCL)技术两套25 kWth级小试装置已成功运行总计超过850 h,一套250 kWth级的高压SCL装置即将投入示范运行。 相似文献
13.
Oxygen carriers(OCs) with perovskite structure are attracting increasing interests due to their redox tunability by introducing various dopants in the structure. In this study, LaNi_xFe_(1-x)O_3(x = 0, 0.1, 0.3, 0.5, 0.7,1.0) perovskite OCs have been prepared by a citric acid–nitrate sol–gel method, characterized by means of X-ray diffraction(XRD) analysis and tested for algae chemical looping gasification in a fixed bed reactor. The effects of perovskite types, OC/biomass mass ratio(O/B), gasification temperature and water injection rate on the gasification performance were investigated. Lower Ni-doped(0≤x≤0.5) perovskites crystalized in the rhombohedra system which was isostructural with LaNiO_3, while those with composition 0.5≤x≤1 crystalized in the orthorhombic system. Despite the high reactivity for LaNiO_3, LaNi_(0.5) Fe_(0.5) O_3(LN5 F5) was found to be more stable at a high temperature and give almost as good results as LaNiO_3 in the formation of syngas. The relatively higher syngas yield of 0.833 m~3·kg~(-1) biomass was obtained under the O/B of 0.4, water injection rate of 0.3 ml·min~(-1) and gasification temperature at 850 °C. Continuous high yield of syngas was achieved during the first 5 redox cycles, while a slight decrease in the reactivity for LN5 F5 after 5 cycles was observed due to the adhesion of small grains occurring on the surface of OCs. However, an obvious improvement in the gasification performance was attained for LN5 F5 compared to raw biomass direct gasification, indicating that LN5 F5 is a promising functional OC for chemical looping catalytic gasification of biomass. 相似文献
14.
Phosphogypsum (PG) is a solid waste produced in the wet process of producing phosphoric acid.Lignite is a kind of promising chemical raw material.However,the high sulfur of lignite limits the utilization of lig-nite as a resource.Based on fluidized bed experiments,the optimal reaction conditions for the production syngas by lignite chemical looping gasification (CLG) with PG as oxygen carrier were studied.The study found that the optimal reaction temperature should not exceed 1123 K;the mole ratio of water vapor to lignite should be about 0.2;the mole ratio of PG oxygen carrier to lignite should be about 0.6.Meanwhile,commercial software Comsol was used to establish a fuel reaction kinetics model.Through computational fluid dynamics (CFD) numerical simulation,the process of reaction in fluidized bed were well captured.The model was based on a two-fluid model and coupled mass transfer,heat transfer and chemical reac-tions.This study showed that the fluidized bed presents a flow structure in which gas and solid coexist.There was a high temperature zone in the middle and lower parts of the fluidized bed.It could be seen from the results of the flow field simulated that the fluidized bed was beneficial to the progress of the gasification reaction. 相似文献
15.
This paper is concerned with the chemical looping combustion of coal in a technique whereby the fuel is gasified in situ using CO2 in the presence of a batch of supported copper oxide (the “oxygen carrier”) in a single reactor. As the metal oxide becomes depleted, the feed of fuel is discontinued, the inventory of fuel is reduced by further gasification and then the contents are re-oxidised by the admission of air to the reactor, to begin the cycle again. A catalyst support, impregnated with a saturated solution of copper and aluminium nitrates, acted as a durable oxygen carrier over numerous cycles of reduction and oxidation, using air as the oxidant. Two bituminous coals (Taldinskaya, Russia, and Illinois No. 5, USA) were investigated and compared with a lignite (Hambach, Germany). The lignite was highly reactive and was gasified completely by 15 mol% CO2 in N2 at 1203 K and 1 bar, so that there was no build up of char in the bed. The bituminous coals produced chars much less reactive than the lignite char, so that there was a steady accumulation of char in the bed with number of cycles, with the degree of accumulation being dependent on the reactivity of the char. Since the kinetics of gasification by CO2 of the chars from either bituminous coal were slow, their rates were controlled by intrinsic chemical kinetics and were not affected by the ability of the oxygen carrier to alter the rates of external mass transfer when gasification is rapid. However, it is likely that rates of gasification in the presence of the carrier are still larger than in its absence, owing to the overall lower [CO] present in the bulk of the fluidised bed during chemical looping. At the temperature used, the carrier was cycling between Cu and Cu2O, since CuO is only stable if the partial pressure of O2 exceeds 0.03 bar at 1203 K. The CuO decomposes to Cu2O and O2 relatively rapidly at these temperatures, once the oxygen concentration is effectively zero. It was impossible to ascertain in our experiments whether the oxygen so generated, after the switching of the air for nitrogen before the start of the succeeding cycle of gasification, made any substantial difference to the reactivity of the char present in the bed. The rate of oxidation of the carrier was found to be much more rapid than the rate of oxidation of the inventory of char. This allows a preferential oxidation of the carrier and most likely accounts for why progressively less CO and CO2 is produced during successive cycles with short periods of oxidation: the increasingly reduced carrier reacts more rapidly than the char. There was no obvious impact from the sulphur contained in the fuels, but longer-term testing is needed. No agglomeration between the carrier particles and the ash was observed, despite the high temperatures during oxidation. 相似文献
16.
17.
10MWth高硫石油焦化学链气化制合成气耦合硫磺回收新系统模拟研究 总被引:1,自引:0,他引:1
基于化学链气化技术依靠气固反应定向调控气化产物中H2S和SO2摩尔比为2的优势,将化学链气化与Claus工艺中的催化转化单元相结合,提出了高硫石油焦化学链气化制合成气和回收硫磺的新系统。针对系统核心单元,即化学链气化过程,基于Aspen Plus,开展热输入10 MWth的高硫石油焦化学链气化过程模拟,以赤铁矿石为载氧体,水蒸气为气化介质,重点考察了氧碳比、气化温度对化学链气化过程及硫转化过程的影响。结果发现,氧碳比的增大导致合成气产率显著降低,但系统从需要外部提供能量逐渐转变为对外部放热,在氧碳比0.8669~0.9535区间内,系统可以达到热量自平衡。同时,气化温度的提高对合成气产率是有利的,在975℃时达到2.15 m3/kg,主要是由于CO体积分数随气化温度增加而增加。氧碳比和气化温度的提高都会导致H2S浓度的降低和SO2浓度的提高。并且研究了当H2S和SO2摩尔比为2的最佳工况时,氧碳比和气化温度为反相关,其中氧碳比为0.8669,气化温度为900℃时,冷煤气效率为64.09%。 相似文献
18.
The reaction of three Chinese coals with Fe2O3 oxygen carrier (OC) was performed in a thermogravimetric analyzer (TGA), with special focuses on the effects of varying heating rate and coal rank on reactivity. Fourier transform infrared spectroscopy (FTIR) was used to in situ detect the emitted gases from TGA. Field scanning electron microscopy/energy-dispersive X-ray spectrometry (FSEM-EDX) was used to study the morphology and elemental compositions of the reaction residues collected from TGA and the related phase evaluation was further identified by X-ray diffraction (XRD). Through all these experiments, it was found that the pyrolysis of coal samples without Fe2O3 OC under N2 atmosphere underwent the dehydration and the ensuing primary and secondary pyrolysis stages. The increasing heating rate shifted the characteristic temperature (Tm) of the primary pyrolysis to a higher temperature and favored a more rapid generation of volatile matters. When the three coals reacting with Fe2O3 OC, TGA results demonstrated even over 200 °C, the reaction still experienced the partial pyrolysis at the relatively low temperature and the ensuing two reactions of Fe2O3 with the pyrolysis products at the primary and secondary stages. The coal of low rank with high volatile content should be preferred for the full conversion of coal into CO2. Furthermore, the activation energy of Fe2O3 OC reacting with PDS at its primary pyrolysis stage was the largest, more than 70 kJ/mol. Finally, SEM-EDX and further XRD analysis of the residues from the reaction of PDS with Fe2O3 OC indicated the reduced counterpart of Fe2O3 was Fe3O4, and some inert iron compounds such as Fe2SiO4 and FeAl2O4 were also generated, which might deteriorate the reactivity of Fe2O3 OC. 相似文献
19.
铁基载氧体是一种具有工业应用前景的载氧体,但存在氧利用率低、在高温下易烧结等问题。虽可通过制备双金属复合载氧体或添加惰性组分改进其性能,但均存在一定缺陷。若将活性组分和惰性材料融入到一个晶体结构制备尖晶石结构载氧体,则可实现利用双金属协同作用提高载氧体活性的同时,利用Al3+提高载氧体的稳定性。采用共沉淀法和溶胶凝胶法制备了具有尖晶石结构的NiFeAlO4载氧体,考察了制备方法、载氧体与煤质量比对NiFeAlO4载氧体化学链燃烧特性和循环稳定性的影响,并分析了载氧体对煤转化过程的作用。结果表明,溶胶凝胶法制备的NiFeAlO4载氧体具有更好的反应性,载氧体与煤质量比为20∶1时,碳转化率为86.7%,远高于煤单独热解时的碳转化率(34%),此时CO2体积分数为93.6%。对反应前后NiFeAlO4载氧体晶相结构和形貌进行分析,表明循环过程中经“还原-氧化”后生成的NiO和载氧体颗粒团聚是导致载氧体活性下降的主要原因。相较于载热作用,NiFeAlO4载氧体在煤化学链燃烧中主要起供氧作用,其不仅会促进挥发分向煤气的转化,且NiFeAlO4载氧体与焦炭之间也存在固-固反应,利于更多CO2的生成。 相似文献
20.
以水蒸气作为气化/流化介质,在流化床中研究了两种铁基复合载氧体的化学链气化反应特性及循环特性,并对气化过程中的反应机理、动力学方程进行了推断。结果表明:温度为920℃时,添加不同修饰物的铁基复合载氧体与煤焦气化的反应活性依次为Fe4Al6K1>Fe4Al6>Fe4Al6Ni1。在多次循环实验过程中,合成气成分保持稳定,表明Fe4Al6K1复合载氧体循环特性良好。XRD谱图分析表明,六次氧化还原实验后的铁基载氧体氧化态仍为Fe2O3。K+主要以铁酸钾形态存在,该结构有利于促进化学链气化反应。利用高斯函数对气化反应速率进行了峰拟合,拟合结果表明化学链气化主要分为3个阶段:化学链作用阶段、煤气化阶段以及Fe3O4向FeO转变的气化阶段。 相似文献