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1.
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%。  相似文献   

2.
A new method for nitric oxide (NO) removal was developed by combining dielectric barrier discharge (DBD) and negative pulse corona (NPC). The effects of gas composition (O2, CO2, and H2O) on NO removal were investigated with this method, and the effect of alcohols (methanol and ethanol) addition on NO removal was also investigated as well as the reaction mechanisms to enhance the NO removal efficiency. The experimental results showed that O2, CO2, and H2O had obvious inhibition effects on NO removal, and the negative effects were in the following order:O2 > CO2 > H2O. The addition of methanol or ethanol in the reaction system could mitigate the negative effects of O2, CO2, and H2O on NO removal, and also eliminated the production of NO2. The positive effect of alcohols addition with DBD-NPC denitration method was also validated in the simulated flue gas, in which the NOx (NO, NO2) was mainly converted into N2.  相似文献   

3.
电镀废水中共存阳离子对Fe(Ⅱ)/O2去除无机磷的影响   总被引:1,自引:0,他引:1       下载免费PDF全文
李婷  董文艺  王宏杰  林进南  张岍  欧阳峰 《化工学报》2013,64(10):3782-3789
通过序批试验,考察了有氧条件下,共存阳离子对亚铁除磷效率的影响并以实际电子废水为考察对象,对比研究Fe(Ⅱ)/O2与传统石灰工艺的除磷效果及相关技术经济指标。结果表明:NH4+-N对同步氧化Fe(Ⅱ)除磷效率几乎没有影响;Zn(Ⅱ)可通过与磷酸根反应产生沉淀提高磷的去除率。Mn(Ⅱ)可与新生三价铁形成稳定络合物,促进亚铁氧化并改善铁磷沉淀物混凝沉淀性能,当Mn(Ⅱ)投加量为1.0 mg·L-1时,反应60 min后,磷的去除率提高11%。Cu(Ⅱ)能高效催化亚铁氧化,从而使亚铁除磷效率显著提高,在Cu(Ⅱ)浓度为0.05 mg·L-1时,除去45%水中磷所需时间由空白的60 min缩短为5 min,Cu(Ⅱ)是所选共存阳离子中最为高效的亚铁除磷催化剂。以实际电镀废水为研究对象,在共存离子的促进作用下,Fe(Ⅱ)/O2对废水中磷的去除效果优于传统石灰法,且药剂成本及产泥量均低于直接投加石灰的除磷工艺。  相似文献   

4.
燃煤锅炉污染物超低排放标准对电厂脱硫和脱硝系统提出了更高的要求。CaO作为脱硫剂可以实现循环流化床锅炉烟气中SO2的高效脱除,焦炭作为还原剂直接还原NO,同时CaO的存在对焦炭还原NO起催化作用,可以实现燃煤烟气中SO2/NO的联合脱除。为了探究连续温度变化对CaO/生物质焦联合脱硫脱硝性能的影响,在钙循环捕集CO2技术背景下,研究了等速升温流态化下CaO/生物质焦的SO2/NO联合脱除特性。探究了烟气中O2和CO2对CaO/椰壳焦脱除SO2/NO的影响。结果表明,O2通过对椰壳焦表面碳原子的活化作用降低了异相还原NO温度,在300~950℃等速升温过程中CaO/椰壳焦的NO脱除效率逐渐增加,780℃以上能实现100%脱硝。O2也提高了CaO/椰壳焦的脱硫效率。CO2与CaO的碳酸化反应以及与椰壳焦的气化反应对同时脱除SO2/NO有明显抑制作用。O2和CO2共同作用下,在500~800℃内CaO/椰壳焦的脱硝效率随温度升高而增加,脱硫效率先降低后升高。NO促进了CaO/椰壳焦脱除SO2,而SO2对脱硝有抑制作用。800℃时CaO/椰壳焦同时脱除SO2和NO的效率分别为97.7%和93.9%。  相似文献   

5.
SO2 and NO emitted from coal-fired power plants have caused serious air pollution in China. In this study, a test system for NO oxidation using O3 is established. The basic characteristics of NO oxidation and products forms are studied. A separate test system for the combined removal of SO2 and NOx is also established, and the absorption characteristics of NOx are studied. The characteristics of NO oxidation and NOx absorption were verified in a 35 t·h-1 industrial boiler wet combined desulfurization and denitrification project. The operating economy of ozone oxidation wet denitrification technology is analyzed. The results show that O3 has a high rate and strong selectivity for NO oxidation. When O3 is insufficient, the primary oxidation product is NO2. When O3 is present in excess, NO2 continues to get oxidized to N2O5 or NO3. The removal efficiency of NO2 in alkaline absorption system is low (only about 15%). NOx removal efficiency can be improved by oxidizing NOx to N2O5 or NO3 by increasing ozone ratio. When the molar ratio of O3/NO is 1.77, the NOx removal efficiency reaches 90.3%, while the operating cost of removing NOx per kilogram is 6.06 USD (NO2).  相似文献   

6.
碳质材料催化臭氧氧化(CMs/O3)体系具有除污性能强、臭氧利用率高和无金属溶出的特点, 但受制于CMs催化性能的易失性, 该方法目前仍处于实验室研发阶段。本文系统阐述了CMs/O3体系的反应原理, 并认为表面催化氧化与均相羟自由基(HO·)反应是去除水中溶解性有机物的主要途径;详细分析了影响非均相反应机理与体系处理效能的关键因素, 并指出在反应过程中, 碳表面碱性活性点位的消耗与酸性含氧基团的累积可导致其催化性能的降低, 而选择以中孔结构为主的碳质材料, 优化溶液pH值和臭氧相对投加量等操作参数, 将有利于降低CMs内部的传质阻力, 显著提高对目标污染物的去除率。基于新近发表的文献, 本文综述了CMs/O3对多种有机污染物和实际废水的处理效能, 并认为多壁碳纳米管(MWCNT)的引入与新型固着、负载技术的使用, 有望提升CMs/O3在微污染水体深度净化领域的实用化水平。同时, 努力将CMs/O3与现有技术相耦合, 建立经济、高效的组合工艺也是当前应用研究的重要方向。  相似文献   

7.
姚婷  段钰锋  朱纯  周强  佘敏  陈亚南 《化工学报》2016,67(4):1467-1474
采用10 g·L-1 NH4Br溶液对原始稻壳焦进行浸渍改性制备了脱汞吸附剂。利用比表面积及孔隙度分析仪、扫描电子显微镜/X射线能谱分析仪对改性前后稻壳焦吸附剂物理化学性质进行表征。在固定床汞吸附实验台上对吸附剂床层出口元素汞(Hg0)和二价汞(Hg2+)进行同步检测,研究了不同温度下N2气氛和N2+6.4 %(体积)O2气氛中改性稻壳焦的汞氧化吸附特性。50℃下N2气氛、N2+6.4%(体积)O2气氛以及150℃下N2气氛中固定床出口均未明显检测到Hg2+,50℃和150℃时脱汞率均可达90%。温度为150℃时,在N2+6.4%(体积)O2气氛中吸附剂的总汞(HgT)脱除效率为98.2%,其中82.2%的Hg0被吸附脱除,其余则被O2非均相氧化为Hg2+而氧化脱除。通过对程序升温管式炉出口HgT进行检测研究了吸附剂表面吸附态汞的脱附特性。汞脱附峰值温度300℃表明吸附态汞可能以Hg-Br化合物的形式赋存于改性稻壳焦表面,220~350℃的脱附温度说明吸附态汞有较高的热稳定性。100.14%~118.62%的汞平衡率验证了实验结果的准确性。  相似文献   

8.
曲践  李保卫  郑坤灿  武文斐 《化工学报》2016,67(10):4468-4476
传统随机孔模型基于简单一步反应建立,不适用于处理O2/CO2气氛下焦炭颗粒复杂气固反应。针对此问题,基于焦炭本身具有多种碳基的特点,以及焦炭颗粒在O2/CO2气氛下燃烧的特性,建立复杂气固反应下的多种碳基随机孔模型和孔隙结构模型。模拟直径为100 μm的焦炭颗粒在O2/CO2气氛下燃烧的过程,使用FORTRAN语言自主编程计算并分析结果。研究表明,燃烧初期颗粒呈现竞争效应,孔隙内部气体浓度产生剧烈波动。波动的生成原因是化学反应与物理扩散之间的竞争,可以通过增加环境氧浓度和减小焦炭颗粒粒径来改善。所提出的多种碳基随机孔模型对于表征O2/CO2气氛下焦炭颗粒的燃烧特性有着良好的适应性。  相似文献   

9.
刘逸锋  沈本贤  皮志鹏  陈华  赵基钢 《化工学报》2016,67(12):5015-5023
为提高Ce基脱硫助剂对石油加工过程中流化催化裂化(FCC)烟气深度脱硫效果,采用实验与密度泛函理论(DFT)探究了SO2、O2在CeO2表面的反应过程。通过60℃、200℃反应温度下SO2、O2与CeO2的反应,对反应前后CeO2样品的XRD、IR、XPS谱图比较分析,探索S、Ce的价态变化和相对含量转变规律,从而推测SO2可能的反应路径。基于密度泛函理论模拟构造了O2单分子和SO2、O2双分子在CeO2(111)和MgAl2O4(111)O空位表面可能产生的吸附构型;利用LST/QST方法搜索SO2氧化反应过程,计算各步反应能垒。结果表明CeO2(111)相比MgAl2O4(111)具有更好的SO2催化效果,其中CeO2在反应中起到了晶格O传递作用,并进一步推断SO3的脱附过程是整个反应的速率控制步骤。  相似文献   

10.
刘国华  刘芳  常新  杨飞 《化工进展》2011,30(2):432-437
将传统A/O工艺的好氧单元分为两段,在各反应器中设置填料,构建了A/O1/O2生物膜系统,对锦纶废水进行处理,研究了污染物在系统各段的降解情况,并借助红外光谱分析方法探讨了污染物中官能团的变化规律。结果表明,A/O1/O2生物膜系统处理锦纶废水的效果良好,COD、NH4+-N和TN的平均去除率分别为92.70%、85.35%和58.85%。当有机负荷从1.64~4.61 kg/(m3·d) 变化时,A段、O1段和O2段中COD、NH4+-N和TN的降解变化趋势均不相同。对于COD的去除,A段、O1段和O2段的平均贡献率分别为63.08%、29.72%和4.16%;对于NH4+-N的去除,O1段和O2段的平均贡献率分别为23.80%和75.99%;对于TN的去除,A段、O1段和O2段的平均贡献率分别为74.97%、19.77%和4.09%。经A段缺氧、O1段和O2段好氧处理后,废水中酰胺化合物、氨基酸和脂肪族化合物含量减少,出现了无机的NH4+、NO3、HCO3以及碳水化合物。  相似文献   

11.
高级氧化技术是一种新型、绿色的水处理工艺,通过各种强化技术更快、更多地产生具有强氧化性的羟基自由基,使其与废水中的有机物发生链式反应,从而将废水中的有机物快速高效降解为无害的无机盐。采用两种典型的高级氧化技术:电芬顿和臭氧,一体化处理船舶生活污水,研究结果表明:在电流密度20 mA/cm2,芬顿试剂n(H2O2):n(Fe2+)=3:1,C(Fe2+)为0.01 mol/L,氧气速率2 L/min,臭氧投加量6 g/L时,电芬顿-臭氧一体化装置能有效降解船舶生活污水中的污染物,当处理时间为120 min时,对COD去除率可达86.4%。  相似文献   

12.
流化床富氧燃烧湿烟气循环兼具经济与环保优势。湿烟气循环(O2/CO2/H2O)条件下煤焦与O2、CO2及H2O的反应同时发生。为探究O2/CO2/H2O气氛下煤焦-O2、煤焦-CO2、煤焦-H2O反应间的相互作用机制,在自制高精度热重实验装置上系统考察了O2、CO2、H2O及其混合气氛下,典型烟煤焦在900℃的反应特性。基于吸附和脱附原理的Langmuir-Hinshelwood(L-H)机理性模型分别计算了烟煤焦与O2、CO2和H2O反应的动力学参数。通过采用单独活性位点与竞争活性位点两种假设分析了O2/CO2、O2/H2O和CO2/H2O气氛下烟煤焦-O2、烟煤焦-CO2和烟煤焦-H2O两两反应间的作用机制,揭示了H2O分子优先吸附于烟煤焦表面活性位点,O2分子次之,而CO2分子相对滞后。O2/CO2/H2O气氛下烟煤焦-O2、烟煤焦-CO2、烟煤焦-H2O反应表现出部分竞争反应活性位点,传统的单独活性位点与竞争活性位点假设均无法准确描述其反应速率特性。基于H2O分子优先,O2分子次优先吸附的原理,建立了O2、CO2、H2O混合气氛下煤焦反应速率L-H动力学方程,方程计算结果与实验值良好吻合。研究结果为深入分析煤焦颗粒流化床富氧燃烧特性及构建可靠、准确的燃烧反应模型提供了理论支撑。  相似文献   

13.
刘露  骆嘉钦  阚青  马晓迅 《化工进展》2020,39(11):4685-4692
采用自行设计的介质阻挡耦合电晕放电等离子体反应装置进行了模拟烟气同时脱硫脱硝的研究,分别考察乙醇胺(HOCH2CH2NH2,MEA)在不同模拟烟气体系中对NO、SO2脱除的影响,深入探讨了MEA在放电过程中与NO的作用机理。结果表明:在N2/O2/SO2/NO体系中,0.56% MEA的加入可以显著消除O2对NO脱除的抑制作用;在N2/CO2/SO2/NO体系中,MEA会吸收进入体系中的部分CO2,以减弱CO2对NO脱除的抑制;在N2/O2/CO2/H2O/NO/SO2体系中,0.56% MEA的加入既可以有效减弱H2O的影响,也可以使NO的脱除率达到71.28%,继续将MEA的体积分数增大至1.20%时,可将该体系下NO脱除率提高到81.25%;同时,MEA可以在短时间内高效吸收体系内的SO2,且几乎不受其他气体成分的影响,SO2脱除率保持在95%左右。  相似文献   

14.
掌握Fe2+/H2O2体系O2的生成路径,可为避免H2O2无效分解,开发经济高效的Fe2+/H2O2体系利用技术指明方向。采用添加自由基捕获剂的方法,探究Fe2+/H2O2体系内各种自由基对O2生成速率的影响,进而确定O2的生成路径。结果表明:Fe2+/H2O2体系内不会产生大量O2-·,O2-·不是生成O2的主要反应物质;O2-·被全部捕获后,体系中仍产生大量O2-·,但此时无O2生成,证明生成O2的反应由·OH和HO2·两种自由基直接参与。分析认为反应·OH+HO2·-H2O+O2是体系内O2生成的主要路径。控制Fe2+/H2O2体系定向生成·OH,抑制HO2·的产生,是提高Fe2+/H2O2体系中H2O2利用率的有效手段。  相似文献   

15.
A transient kinetic model was developed for the CO oxidation by O2 over a Pt/Rh/CeO2/γ-Al2O3 three-way catalyst. The experiments which were modelled consisted of periodically switching between a feed stream containing 0.5 mol% CO in helium and a feed stream containing 0.5 mol% O2 in helium, with a frequency from 0.1 to 0.25 Hz, in the temperature range 393–433 K. These temperatures are representative for cold start conditions. The transient experiments yield information about the reaction mechanism. A transient kinetic model based on elementary reaction steps was developed which describes the experimental data in the above mentioned range of experimental conditions adequately. The kinetic model consists of two monofunctional and one bifunctional contribution. The first monofunctional reaction path comprises competitive adsorption of CO and O2 on the noble metal surface followed by a surface reaction. The second monofunctional reaction path consists of CO adsorption on an oxygen atom adsorbed on the noble metal surface, followed by a reaction to CO2. The bifunctional reaction path involves a reaction between CO adsorbed on the noble metal surface and oxygen from ceria at the noble metal/ceria interface. Also, reversible adsorption of carbon dioxide on the support is taken into account. The kinetic parameters, i.e. preexponential factors and activation energies for the different elementary reaction steps, and the oxygen storage capacity were estimated using multi-response non-linear regression analysis of the oxygen, carbon monoxide and carbon dioxide outlet concentrations.  相似文献   

16.
NO removal using CH4 as a reductant in a dual-bed system has been investigated with Co-NaX and Ag-NaX catalysts, which were prepared by Co2+-, Ag+-ion exchange into zeolite NaX, respectively, and activation for 5 h at 500 °C. The experimental result has been compared with that of a Co-NaX-CO catalyst, additionally pre-treated under CO flow for the Co-NaX catalyst. The cobalt crystal structure of a Co-NaX-CO catalyst is Co3O4, which promotes NO oxidation to NO2 by excess O2 at a low temperature (523 K). The mechanical mixture of Co-NaX-CO and Ag-NaX catalysts shows a synergy effect on NO reduction to N2 by CH4 in the presence of excess O2 and H2O, but the NO reduction decreases quickly as time passes. However, the NO reduction to N2 in a deNO bed at 523 K and a deNO2 bed at 423 K, which are relatively lower than the reaction temperatures for common SCR systems, still remained at 67% even in a H2O 10% gas mixture after 160 min.  相似文献   

17.
The mechanism of the NO/C3H6/O2 reaction has been studied on a Pt-beta catalyst using transient analysis techniques. This work has been designed to provide answers to the volcano-type activity behaviour of the catalytic system, for that reason, steady state transient switch (C3H6/NO/O2 → C3H6/Ar/O2, C3H6/Ar/O2 → C3H6/NO/O2, C3H6/NO/O2 → Ar/NO/O2, Ar/NO/O2 → C3H6/NO/O2, C3H6/NO/O2 → C3H6/NO/Ar and C3H6/NO/Ar → C3H6/NO/O2) and thermal programmed desorption (TPD) experiments were conducted below and above the temperature of the maximum activity (Tmax). Below Tmax, at 200 °C, a high proportion of adsorbed hydrocarbon exists on the catalyst surface. There exists a direct competition between NO and O2 for Pt free sites which is very much in favour of NO, and therefore, NO reduction selectively takes place over hydrocarbon combustion. NO and C3H6 are involved in the generation of partially oxidised hydrocarbon species. O2 is essential for the oxidation of these intermediates closing the catalytic cycle. NO2 is not observed in the gas phase. Above Tmax, at 230 °C, C3H6 ads coverage is negligible and the surface is mainly covered by Oads produced by the dissociative adsorption of O2. NO2 is observed in gas phase and carbon deposits are formed at the catalyst surface. From these results, the state of Pt-beta catalyst at Tmax is inferred. The reaction proceeds through the formation of partially oxidised active intermediates (CxHyOzNw) from C3H6 ads and NOads. The combustion of the intermediates with O2(g) frees the Pt active sites so the reaction can continue. Temperature has a positive effect on the surface reaction producing active intermediates. On the contrary, formation of NOads and C3H6 ads are not favoured by an increase in temperature. Temperature has also a positive effect on the dissociation of O2 to form Oads, consequently, the formation of NO2 is favoured by temperature through the oxygen dissociation. NO2 is very reactive and produces the propene combustion without NO reduction. These facts will determine the maximum concentration of active intermediates and consequently the maximum of activity.  相似文献   

18.
The thermodynamic redox properties for a series of ceria–zirconia solid solutions have been measured by determining their oxidation isotherms between 873 and 1073 K. Isotherms were obtained using Coulometric titration and using O2 titration of samples equilibrated in flowing mixtures of H2 and H2O. Samples having the following compositions were studied after calcinations at 973 and 1323 K: CeO2, Ce0.92Zr0.08O2, Ce0.81Zr0.19O2, Ce0.59Zr0.41O2, Ce0.50Zr0.50O2, Ce0.25Zr0.75O2, Ce0.14Zr0.86O2, and ZrO2. While the oxidation enthalpy for CeO2 was between −750 and −800 kJ/mol O2, the oxidation enthalpies for each of the solid solutions were between −500 and −550 kJ/mol O2 and essentially independent of the extent of reduction. The shapes of the isotherms for the solid solutions were affected by the oxidation entropies, which depended strongly on the sample composition and the extent of reduction. With CeO2, Ce0.92Zr0.08O2, and Ce0.14Zr0.86O2, the samples remained single-phase after calcination at 1323 K and the thermodynamic redox properties were unaffected. By contrast, Ce0.59Zr0.41O2 formed two phases following calcination at 1323 K, Ce0.78Zr0.22O2 (71 wt.%) and Ce0.13Zr0.87O2 (29 wt.%); the isotherm changed to that which would be expected for a physical mixture of the two phases. A model is presented which views reduction of the solid solutions in terms of the local atomic structure, with the formation of “pyrochlore-like” clusters causing the increased reducibility of the solid solutions. Some of the changes in reducibility are associated with the number of sites from which oxygen can be removed in order to form pyrochlore-like clusters.  相似文献   

19.
Both NO decomposition and NO reduction by CH4 over 4%Sr/La2O3 in the absence and presence of O2 were examined between 773 and 973 K, and N2O decomposition was also studied. The presence of CH4 greatly increased the conversion of NO to N2 and this activity was further enhanced by co-fed O2. For example, at 773 K and 15 Torr NO the specific activities of NO decomposition, reduction by CH4 in the absence of O2, and reduction with 1% O2 in the feed were 8.3·10−4, 4.6·10−3, and 1.3·10−2 μmol N2/s m2, respectively. This oxygen-enhanced activity for NO reduction is attributed to the formation of methyl (and/or methylene) species on the oxide surface. NO decomposition on this catalyst occurred with an activation energy of 28 kcal/mol and the reaction order at 923 K with respect to NO was 1.1. The rate of N2 formation by decomposition was inhibited by O2 in the feed even though the reaction order in NO remained the same. The rate of NO reduction by CH4 continuously increased with temperature to 973 K with no bend-over in either the absence or the presence of O2 with equal activation energies of 26 kcal/mol. The addition of O2 increased the reaction order in CH4 at 923 K from 0.19 to 0.87, while it decreased the reaction order in NO from 0.73 to 0.55. The reaction order in O2 was 0.26 up to 0.5% O2 during which time the CH4 concentration was not decreased significantly. N2O decomposition occurs rapidly on this catalyst with a specific activity of 1.6·10−4 μmol N2/s m2 at 623 K and 1220 ppm N2O and an activation energy of 24 kcal/mol. The addition of CH4 inhibits this decomposition reaction. Finally, the use of either CO or H2 as the reductant (no O2) produced specific activities at 773 K that were almost 5 times greater than that with CH4 and gave activation energies of 21–26 kcal/mol, thus demonstrating the potential of using CO/H2 to reduce NO to N2 over these REO catalysts.  相似文献   

20.
In this work, a new innovative absorption system containing both thiourea dioxide (TD) and FeEDTA was used to NO removal. The independently influences of O2 volume concentration, TD concentration, original pH value and absorbent temperature on NO removal in bubbling device were examined preliminarily. The results revealed that the NO removal efficiency firstly increased and then decreased with the increasing of the three independent variables (O2 volume concentration, TD concentration and temperature). However, the NO removal efficiency monotonously increased to some extent with pH value increasing from 6.5 to 10.5. In addition, the respective effects of the four variables and the interactive function of them on NO removal were checked with the response surface methodology (RSM) by central composite design (CCD). The calculative model showed that pH value possessed a main positive independent impact on NO removal. Furthermore, the interactive effects between any two factors were expounded by the 3D surface and counter plots. Finally, the optimum absorption conditions for the maximum NO removal at 94.3% experimentally and 95.8% statistically were obtained in O2 volume content of 6.0%, TD concentration of 0.02 mol·L-1, original pH value of 10.5 and absorption temperature of 42 ℃.  相似文献   

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