1.Introduction

Fossil fuels are contributing more than 82%of energy all over the globe,of which,50%comes from fuel oils and hence petroleum is still the primary source to ful fill these needs[1].Fuel oils are generally contaminated with organosulfur compounds comprising of thiols,aromatic sulfides,mercaptanes and benzothiophenes(BTs),where BTs contribute about 85%[2,3].These organosulfur ring compounds exist in non-substituted i.e.BT,dibenzothiophenes(DBT),as well as alkyl derivatives i.e.4-methyldibenzothiophene(4-MDBT)and 4,6-dimethyldibenzothiophene(4,6-DMDBT)[4].These sulfur(S)compounds adversely affect the quality of petroleum products by decreasing the API gravity and calorific value as well as contribute to environmental pollution by getting converted into SO x during combustion.Moreover,S species also lead to particulates production resulting in black exhaust fumes[5],causing impairment of pipelines,acid rain and poisoning of catalysts in oil re fineries[6].

Worldwide oil re fineries are now producing low S fuel oils(less than 50 ppm)to meet new regulation mandate[7]which is a challenging job.Several reports following different approaches are available in literature to cope with these challenges including hydrodesulfurization(HDS)[8,9],biodesulfurization(BDS)[10],adsorptive desulfurization[11],oxidative desulfurization(ODS)[12,13],and extraction through ionic liquids(ILs)etc.[14,15].HDS,operated at high temperature and pressure in the presence of excess hydrogen over a suitable catalyst,is quite effective for cyclic and aliphatic S containing hydrocarbons but less attractive towards BT and DBT[16].Also harsh operating conditions in HDS cause higher consumption of hydrogen and decrease of catalyst life resulting in highercosts[17].Similarly,the use of otherapproaches like BDS is hindered by low versatility of types of enzymes,slow reaction rates and low miscibility ofthe reactants[18].On the contrary,ODSis an interesting and conventionalprocess characterized by mild temperature and pressure operation in the presence of a suitable catalyst and oxidant i.e.ozone,perchlorate,potassium permanganate,nitric acid,nitrogen oxides,ter-butyl hydroperoxide and hydrogen peroxide where H2O2 has been reported with good activity[19].In addition to oxidant selection,various catalytic systems such as polyoxometalates,molybdates supported on alumina,tungsten,vanadium and titanium supported catalysts have been reported elsewhere[20].Apositive pointofthis approach isthatthe mostrefractory S containing compounds i.e.DBT and its derivatives show high reactivity[21]and are easily oxidized to highly polarized sulfones,which can be subsequently removed by distillation and solvent extraction[22].

Mo supported overalumina has been the choice ofresearcher for the ODS of DBT over the years with high activity.For example,Cedeno-Caero,et al.reported enhanced desulfurization activity using Al2O3 supported catalysts in the presence of H2O2 as oxidant[23].Similarly,Jia,et al.investigated ODS of DBT into sulfones in the presence of H2O2 and 14 wt%MoO3/Al2O3 catalyst[16].Apart from this,Fe supported over activated carbon using oxygen as the oxidant has been reported with good ODS activity[24].Similarly,good ODS activity has been reported on Fe based ILs for different S compounds earlier[25–27].These reports show that Fe can act as a good promoter to classical desulfurization catalysts.Thus,it can be assumed to test the ODS of DBT in the presence of Fe based catalyst avoiding the use of expensive ILs which can considerably limit process cost.To achieve this task,this study was aimed to develop an efficient and cost effective catalyst for the ODS of DBT under mild operating conditions with special emphasis on the use of extremely low Fe loading(2 wt%)as the promoter to classical Co–Mo/Al2O3 and Ni–Mo/Al2O3 catalysts in the presence of H2O2 and formic acid as oxidant systems.

2.Experimental

2.1.Chemical reagents

Chemical reagents in this study were of analytical grade and used without further purification.DBT was purchased from Acros Organics,New Jersey,USA.n-heptane,acetic acid,HCl and NaOH were purchased from RdH Laborchemikalien,GmbH and Co.Seelze.Alumina support(Al2O3),Cobalt II nitrate hexahydrate Co(NO3)2·6H2O,Nickel II nitrate hexahydrate Ni(NO3)2·6H2O,ammonium heptamolybdate tetrahydrate[(NH4)6Mo7O24·4H2O]and 30 wt%H2O2 were purchased from BDHLaboratory Supplies,Poole,England.Iron II sulfate heptahydrate(FeSO4·7H2O)waspurchased from Merck and Co.,Darmstadt,Germany.

2.2.Model fuel oil

The model oil comprised of 1000 ppm DBT(by dissolving 1 g of DBT in 1000 ml of n-heptane)from which working solutions of 200–1000 ppm were prepared to draw calibration curve for DBT.

2.3.Catalyst preparation

In order to confirm the presence and incorporation of metallic species onto Al2O3 support in the prepared catalysts,EDX spectra were recorded for Fe–Ni–Mo/Al2O3 using SEM[Model No:Nova NanoSEM-450].The data are shown in Table 1 and Fig.3,which shows corresponding peaks for Al,Ni,Mo and Fe,confirming results of XRD analysis.

当时因时间关系，霍元甲也不可能返回天津，李瑞东晚上设宴款待了霍元甲，并留他住在李宅的西跨院客房内，和李瑞东先生的弟子李进修住在一个房间内，次日晨，李瑞东让徒弟招呼客人用早餐，却不见了霍元甲，原来霍元甲天一亮就起来走了，为此李瑞东先生感到客人没用早餐就走了，很是过意不去，就叫弟子李进修追回来用早餐，李进修是个实在人，竟然追出去十几里也未能追上。

2.4.Support and catalyst characterization

Textural properties,elemental composition,and surface morphology of the prepared catalyst were characterized by X-ray diffraction(XRD),Atomic Absorption Spectroscopy(AAS),Energy Dispersive X-ray Analysis(EDX)and Scanning electron microscopy(SEM).

1.把好语音关。学生听不懂，很大一部分归结于读不准，没有正确的输入，自然没有有效输出。高一开学伊始，我就让学生重学48个音标，并强化自然拼读的学习，系统地学习语音变化的一些现象，如：连读、弱读、失去爆破、同化等。我将这些语音现象拆分成一个个小的知识点，每节课上课之前学一个知识点，这样既不耽误课程，也不会使学生一下子接受太多产生排斥心理。强化音标学习的同时让学生自己拼读每单元的新单词并在全班带读，这样学生会自己加强语音方面的学习，为后面的听力练习做好准备。

2.5.Catalytic activity test

ODS activity of the catalysts was tested using 800 ppm DBT solution(as model oil)in n-heptane in the presence of H2O2 and formic acid as oxidants.Effect of experimental parameters was tested including oxidant type,amount of oxidant,catalyst dose,reaction time and pH one by one while keeping others constant.In a classical experiment,10 ml of 800 ppm solution,0.4 g catalyst and 30 wt%oxidant were taken in a flask.The flask was sealed and shaken at fixed temperature for certain reaction time in water-bath shaker.After shaking,the solution was filtered and analyzed using double beam UV–vis spectrophotometer.Catalytic desulfurization activity was recorded in terms of DBT conversion using Eq.(1).

计算机编程语言不仅是计算机运行的指令，更是计算机编程人员和计算机之间的交流工具。经过近一百年的发展，计算机编程语言已经获得了巨大的发展，其语言丰富性和流畅性均达到了一定水准，计算机语言也发展出多种形式，这些语言各有优势，使用者可以根据具体的网络环境和实际需求进行选择，以使计算机编程语言呈现出最优异的性能。

where:

2.6.Analysis of reaction products

ODS reaction products were analyzed using UV–visible spectrophotometer model 160 A,Shimadzu,Japan.The wavelength was swept from 200 to 800 nm where DBT showed a strong peak at wavelength of maximum absorption(λmax)at 320 nm[30].

3.Results and Discussion

3.1.Textural properties and characterization of catalysts

3.1.1.XRD study

3.2.4.Influence of catalyst dose on ODS process

Fig.1.XRD pattern of fresh catalysts.

3.1.2.SEM and surface area analyses

Attributed to the fact that surface morphology,and distribution of active species play a key role in determining catalytic activity[39],textural characterizations of catalysts were performed using SEM[Model No:Nova NanoSEM-450]and the scans are depicted in Fig.2(a–c).SEM studies showed that there are irregular distributions ofsupportparticles with average particle size less than 10 μm indicating a closely packed particle structure.SEM scans further showed that particles of Co,Mo,Ni and Fe impregnated catalysts were more tightly packed than nascent support.These results were further supported by low surface area of the impregnated catalysts than mere support.

Fig.2.(a)SEM image of Nascent Al2O3.(b)SEM image of fresh Ni–Co–Mo/Al2O3.(c)SEM image of fresh Fe–Ni–Mo/Al2O3.

In order to get further insight of the particles distribution and porosity of the catalysts,surface area of fresh and spent catalysts was determined via N2-adsorption approach using BET surface area and porosity analyzer(Micromeritics TriStar II 3020).The data are shown in Table 1,which indicate that Al2O3 support was of low surface area having a structure close to impervious and packed nature.These data are consistent with SEM results showing irregular distribution with less porous nature of the catalyst.It can be seen that surface area of support considerably decreased with the impregnation of metals,which was more dominant in case of tri-metallic catalysts i.e.Fe–Ni–Mo/Al2O3 compared to bi-metallic i.e.Co–Mo/Al2O3 or Ni–Mo/Al2O3 attributed to the presence of extra metal in the earlier one[8].Asupport with low surface area can decrease catalyst cost many times compared to those with high surface area and hence Al2O3 with low surface area was chosen in this study without compromising on the over activity of the process.

Table 1 BET surface area and metal loadings of different catalysts

Catalyst Metal loading/wt% Surface area/m2·g−1 Co Ni Mo Fe Fresh Spent Alumina(Al2O3)– – – –21.84 –Co–Mo/Al2O3 2 – 5 – 2.08 0.78 Ni–Mo/Al2O3 – 2 5 – 2.05 0.77 Fe–Ni–Mo/Al2O3 – 2 5 2 1.71 0.54

Experiments were performed over a catalyst dose ranging from 0.2–1.4 g per 10 ml of 800 ppm DBT to check its effect on ODS activity.Higher catalytic dose provides more interactions between catalytic intermediates and DBT molecules and hence leads to greaterconversion[50,51].It is clear from Fig.7 that%DBT conversion over all catalysts increases with increase in catalyst dosage and stays above 95%at 0.4 g dose.Conversion above 98%means that extra catalyst dose would remain un-interacted with DBT molecules and hence no further change in the trend can be seen in Fig.7 at a catalyst dose of 0.4 g onward.

Interval-Number Evaluation for Sustainable Level of Small and Medium-Sized Shipping Companies

Catalysts were prepared by incipient wet impregnation method reported elsewhere[28,29]using powdered alumina as catalytic support.Stoichiometric amount of alumina was successively impregnated with aqueous solution of(NH4)6Mo7O24·4H2O,corresponding to 5 wt%of Mo followed by Co(NO3)2·6H2O or Ni(NO3)2·6H2O impregnation corresponding to 2 wt%of Co or Ni respectively.After each impregnation,the support with metal salt solution was stirred for 2 h in electric shaker.After shaking,solution was filtered and dried in oven at 120°C for 1 h,followed by calcination in muffle furnace at 500°C for 3 h converting each of the metallic species into oxide state.Similar protocol was followed for Fe promoted Co–Mo/Al2O3 and Ni–Mo/Al2O3 catalysts having 2 wt%Fe(using FeSO4.7H2O as Fe precursor)loadingsin allsamples.Atthe end of calcination,catalysts were stored in inert N2 environment.

对比观察实施sbar交班模式前后,护理人员在晨交班中的交班缺陷情况,同时了解晨交班所需时间,对医护人员开展满意度调查,满分为25分,分为非常满意、满意、一般、不满意、非常不满意五个层级,评分分别为1~5分,调查内容分别为信息明确简洁、重点突出、条理清晰、患者病情掌握情况、节省晨交班时间[4]。

3.2.5.Effect of amount of oxidant on ODS process

《刑法修正案八》将醉酒驾驶纳入到刑法处罚的范围是必然的，而且必须实现对该行为的全面监督，不能仅仅是以危险结果的发生为依据。我国目前已经在刑法中加入了危险驾驶罪，其中包括醉酒型危险驾驶罪，在具体的规定中，不需要考虑醉酒驾驶所造成的具体后果和情节，只要行为人存在醉酒驾驶的客观事实就构成该类犯罪，需要处以拘役以及罚金，因此需要对该罪名的犯罪构成要件进行研究，明确在何种情况下才能构成该类犯罪，这样才能更好地了解和研究醉酒型危险驾驶罪，并在实践中实现对社会安全的保护。

3.2.Catalytic activity tests

3.2.1.Effect of initial DBT concentration

The effect of initial DBT concentration over Ni–Co–Mo/Al2O3 and Fe–Ni–Mo/Al2O3 was investigated in a range of 200–1000 ppm as shown in Fig.4.A direct relation between conversion and initial DBT concentration exists which reaches to maximum at 800 ppm and becomes constant onward.As catalysis being strongly affected by surface interaction,thus higher concentration of DBT provides more chances of interaction between DBT molecules and catalytic active sites leading to higher conversion[40,41].It is believed that at lower concentration,there are phase transfer limitations among molecules of S and polar H2O2 resulting in lower DBT conversion,while higher DBT concentration allows greater such interactions leading to higher DBT conversion as visible from Fig.4.Based on these results,800 ppm is selected as optimum concentration for onward activity tests.

Fig.3.EDX spectrum of Fe–Ni–Mo/Al2O3.

Fig.4.Conversion of DBT as a function of initial concentration over Ni–Co–Mo/Al2O3 and Fe–Ni–Mo/Al2O3 catalyst.

3.2.2.Effect of contact time

以各因子的方差贡献率作为权重，计算12个海岛县经济发展水平的主成分得分。由旋转后累计方差贡献率可知，前3个主成分累计贡献率达到了96.403%，所以选取3个主成分。第一主成分得分计算公式为：

有淋巴转移的宫颈鳞癌中PTTG、VEGF-C、VEGFR-3表达阳性率及LMVD高于无淋巴转移的宫颈鳞癌(P<0.05)。见表2。

PTA（Primary Trait Analysis，简写PTA）即基本要素分析，是一种用于学生作业，尤其是开放性作业的评分工具。PTA量表的理论假设是：任何一种行为表现，包括行为的和认知的，都会有一系列基本要素，这些要素构成学生学习某些知识、技能或行为表现的基本单元。教师只要将学生在这些基本单元的行为表现进行评定，则学生在完成这些具体任务时的总体特征就可以得到适当的评定。

3.2.3.Effect of reaction temperature

Catalytic activity is strongly affected by the time given to the interaction of solute molecules and catalyst active sites.Thus,effect of contact time ODS of DBT at different intervals was tested and results are summarized in Fig.5,which shows that maximum DBT conversion was achieved at 90 min.These and other similar reports are supported by the fact that longer exposure facilitates better DBT–catalyst interaction leading to higher S removal[42,43].Comparatively longer reaction time in this study to previous reports can be attributed to low Fe loading keeping economic aspects in mind.120 min with 99%DBT conversion on Fe loaded catalysts is quite comparable with earlier reports[44]and Fenton's like reagent for the ODS of DBT[27].From Fig.5,it can be seen that Fe–Ni–Mo/Al2O3 exhibited maximum activity i.e.99%DBT conversion with overall ODS activity order as:Fe–Ni–Mo/Al2O3 ＞ Fe–Co–Mo/Al2O3＞ Ni–Co–Mo/Al2O3＞ Ni–Mo/Al2O3＞ Co–Mo/Al2O3＞ Mo/Al2O3.Furthermore,this work can be considered superior as higher DBT conversion(90%)with Mo loading much lower(5 wt%)was reported compared to previous reports(16 wt%Mo loading)with only 83%DBT conversion[45].From the comparison of reported literature shown in Table 2 for ODS of DBT as model oil,it can be concluded that low operating temperature and cost effective Fe based catalysts with 99%conversion in the current work can be considered as a promising forward step in the field of fuel oil desulfurization.

It is believed that both DBT oxidation and H2O2 decomposition are favored athig her temperature[50–52].Catalytic activity of the catalysts as a function of reaction temperature was tested in a range of 20–60 °C at 150 min reaction time and 0.4 g of catalyst dose.Results compiled in Fig.6 show a direct relation of DBT conversion with temperature reaching to maximum i.e.97%at60°C over Fe–Ni–Mo/Al2O3.An optimal temperature is required in ODS system ashighertemperature can cause side reaction leading to thermal decomposition of H2O2 which can adversely affect quality of the fuel[53].Furthermore,5 wt%Mo loading achieving a DBT conversion of 90%at 50°C demonstrates superior efficiency of the current catalyst–oxidant system to previous reports having 16 wt%Mo loading and 100°C reaction temperature[54].At any temperature,Fe–Ni–Mo/Al2O3 exhibited maximum activity among different catalysts tested supporting the data mentioned in Section 3.2.2 above,indicating the consistency and accurateness of the current experimental set-up.

XRD technique was used to get insight about the chemical composition,crystallinity and the presence ofCo,Mo,Niand Fe in Al2O3 supported catalysts.XRD runs were recorded at 2θ angular range between 10°and 80°and the scans are depicted in Fig.1 which show peaks for Al2O3 support,Mo[31,32]and Co attheirrespective positions[33].Furthermore,Fe(having a relatively weaker peak)was confirmed in XRD scan of Fe–Co–Mo–Al2O3 indicating the presence of crystalline iron oxide,though in small amount[34].It is further believed that the species in a material present at concentration lower than 5 wt%,cannot be properly detected by XRD technique[35]and hence very weak peaks for Co,Ni,Fe(2 wt%)and Mo 5 wt%were observed for all the oxide phases.The consistency of XRD analysis can be confirmed from the fact that almost all metals appeared at their previously reported peaks position i.e.cobalt oxide(Co3O4),at 2θ =32°,37°,45°,58°and 66°[36],Fe2O3 at 2θ:24°,33°,35°,40°,49°,54°and 57°[37]and NiO shows the characteristic peaks at 2θ =37°,43°and 63°[38].The appearance of weak peaks in XRD analysis for metallic species,specially Fe,required further unequivocal characterization tools i.e.EDX and Atomic Absorption Spectroscopy for catalyst characterization which are provided in the proceeding sections.

3.1.3.EDX and AAS analyses

Similarly,success fulincorp oration ofFe in catalytic samples was also tested via quantitative analyses for Fe impregnated catalysts(Fe–Ni–Mo/Al2O3)using AAS technique.In a classical AAS analysis,the catalyst sample(0.125 g)was digested in 10 ml mixture comprised of HNO3,H2SO4,HCl and HF in a ratio of 3:3:2.5:1.5 ml respectively.2.5 ml portion of the solution was then diluted to about 1.2 L and analyzed by AAS(GBC Avanta Ver.1.32 Atomic Absorption Spectrophotometer)at a wavelength of 248.3 nm operated in flame mode using air–acetylene mixture as fuel gas.The amount of Fe contents in the catalyst sample as calculated from AAS analysis,was 1.8 wt%,which is close to the theoretical value of 2 wt%.The minor loss in Fe contents could be attributed to experimental handling errors or leaching during the impregnation process.AAS results are in good agreement with EDX and XRD results,suggesting the presence of Fe as the promoter in catalysts under study.

在对照组治疗方案的基础上，再予杞竹地黄丸治疗，药物组成：枸杞子15 g，淡竹叶9 g，生地黄12 g，山茱萸20 g，牡丹皮10 g，山药15 g，泽泻9 g，茯苓15 g，女贞子12 g，旱莲草12 g，知母6 g，麦门冬15 g，甘草梢6 g，1剂/d，水煎200 mL，分早晚2次口服。治疗1个月为1个疗程，共1个疗程。

Fig.5.Catalytic conversion of DBT as a function of reaction time.

Table 2 Comparative analysis of DBT conversion via ODS from reported literature and current study

S.no Type of catalyst Type of oxidant/medium Reaction time/min Operating temperature/°C Max.DBT conversion/% Reference number 1 Polyoxometalates H2O2/CH3COOH 180 70 95 [46]2 Fe–Pc(NO2)4 O2 and air 120 100 98.7 [44]3 Co–Mo/Al2O3 Ni–Mo/Al2O3 Co–Ni–Mo/Al2O3 t-BuOOH 180 100 86 [45]4 Polyoxometalate anion[C18H37N(CH3)3]5[PV2Mo10O40]O2 240 70 98 [47]5 Ag–HPW/SiO2 H2O2 200 70 95 [48]6 Organometallic Ni Organometallic Pt Grignard reagent Not mentioned 93 [49]7 Fe–Ni–Mo/Al2O3 Fe–Co–Mo/Al2O3 H2O2/HCOOH 120 60 99 Current work

In ODS,H2O2 and formic acid have been tested in the presence of various Mo/Al2O3 supported catalysts[55]using Liquid–Liquid extraction approach.Amount of oxidant consumed in oxidation process can directly affect the efficiency as well as cost of the process.Unlike previous reports which did notfocus on the amount of oxidant in ODS of DBT[56],effect of the amount of H2O2 and formic acid were tested in the presence of Fe promoted Mo–Al2O3 catalysts and data are shown in Figs.8 and 9 respectively.It can be seen that ODS activity in case of H2O2 is higher compared to formic acid while 0.5 ml was the optimum amount of each oxidant for maximum DBT conversion(86%in case of H2O2 and 83%for formic acid).Moreover,Ni based catalysts ranked higher in activity than Co based ones which can be attributed to the fact that Ni2+with a 3d84S0 external orbital possesses higher reduction potential(E o)(−25 V)than Co(3d74S0)(−28 V),hence readily oxidizing the electron rich S center of DBT,exposing it for oxidation by H2O2 or formic acid leading to sulfoxide and finally sulfones formation[57].Apart from reduction potential,S of the DBT acts as a soft acid on Pearson theory,which would prefer to interact with a soft base.The crystal field splitting of“d”orbitals of Co2+and Ni2+result in low spin species with ionic radii of 79 and 83 picometer(pm)respectively.Ni2+with larger ionic radii acts as a softer base compared to Co2+and thus preferentially interacts with S of DBT(a soft acidic center)in the reaction mixture,leading to higher DBT conversion by Ni based catalysts.Figs.8 and 9 further show that Fe,in the presence of both,H2O2 and formic acid,enhances the catalytic activity of Co or Ni based catalysts based on Fenton's reaction.

3.3.Proposed mechanism of ODS

Fig.6.Catalytic conversion of DBT as a function of temperature.

ODS process usually leads to the formation of sulfones in the presence of H2O2 and/or formic acid[50,58]through a two-step mechanism with each step involving attack of oxygen atom on the S atom of DBT leading to final DBTO2 molecule over Mo/Al2O3 type catalysts[59].Higher oxidation ability by Fe promoted catalysts in the present study can be explained on the facts that Fe3+promotes the formation of performic acid.Performic acid with higher oxidizing power than formic acid converts MO2(M=Co,Mo,Ni or Fe)into MO3 type species,which readily react with DBT,gradually oxidizing it into sulfones[60].It is also assumed that enhanced activity of Fe based catalysts can be attributed to the fact that in the presence of H2O2,Fe2+readily oxidizes into Fe3+,dissociating H2O2 into OH− and OH•species,resulting in superoxide formation i.e.•OOH.This superoxide readily reacts with DBT molecule converting it into sulfoxide and ultimately into sulfone.These factors are summarized in a proposed mechanism depicted in Fig.10.

Fig.7.Conversion of DBT as a function of catalysts dose.

Fig.8.Conversion of DBT as a function of amount of H2O2.

4.Conclusions

Fig.10.Proposed mechanism for the catalytic ODS of DBT using H2O2 as oxidant.

The main focus of this study revolves around the promotion effect of cost effective Fe to classical Co or Ni based Mo/Al2O3 catalysts for the ODS of DBT in the presence of H2O2 and formic acid as oxidants at mild operating conditions.Experimental data showed that Fe greatly enhanced the oxidative desulfurization process following catalytic activity order as:Fe–Ni–Mo/Al2O3 ＞ Fe–Co–Mo/Al2O3 ＞ Ni–Co–Mo/Al2O3＞Ni–Mo/Al2O3＞Co–Mo/Al2O3＞Mo/Al2O3.H2O2 exhibited higher efficiency towards the oxidation process compared to formic acid.BET surface area,EDX,XRD,AAS and SEM characterization techniques were used to get insight about the textural structure and morphology of the catalysts.Current approach based on the application of mild operating conditions,low catalyst cost,high DBT conversion(99%)and simple mechanization can be considered as forward steps in the industrial desulfurization processing for fuel oil.

Fig.9.Conversion of DBT as a function of amount of formic acid.

Acknowledgments

The authors highly acknowledge Centralized Resource Laboratory(CRL),University of Peshawar for their technical and instrumental facilities.

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