汽油噻吩硫的烷基化脱除技术

介绍了英国BP公司利用烷基化技术脱除催化裂化汽油中噻吩硫的OATS技术 ,该技术将硫含量降低到10 μg/g以下 ,同时还可以降低烯烃含量 ,不损失汽油的辛烷值 ,提高柴油的产率。该技术目前正处于工业试验阶段     

硅胶负载杂多酸吸附脱除模拟油中的氮化物

以硅胶为载体,利用等体积浸渍法负载3种不同杂多酸制备一种吸附剂,以喹啉的十二烷溶液为模拟油,考察酸负载量、反应时间、反应温度、剂油质量比对油品脱氮率的影响。结果表明,在酸负载量为40%(w),反应温度为50℃,反应时间为45min,剂油质量比为1∶5的条件下,吸附剂可有效吸附脱除模拟油中的氮化物,脱氮率达到90%以上。采用傅里叶红外光谱(FT-IR)对吸附剂的物化性质进行了表征。     

减四线糠醛抽出油的萃取法脱硫和脱氮

以中国石油化工股份有限公司茂名分公司的减四线糠醛抽出油为原料,采用二甘醇、三甘醇、四甘醇、聚乙二醇200、聚乙二醇400、环丁砜6种萃取溶剂,进行了萃取脱硫、脱氮研究,筛选出适宜的萃取剂聚乙二醇200,并考察了聚乙二醇200萃取工艺条件对脱硫、脱氮效果的影响,及其二级和三级萃取的脱硫、脱氮效果。结果表明,聚乙二醇200对减四线糠醛抽出油中的硫醇、喹啉类化合物具有较好的脱除效果。适宜的萃取条件为萃取时间15min、超声波振荡时间10min、萃取温度60℃、剂/油体积比1。     

HPWA-SBA-15催化氧化吸附脱除汽油中的噻吩硫

以纯硅介孔分子筛SBA-15为载体,磷钨酸为活性组分,采用直接合成法制备HPWA(磷钨酸)-SBA-15催化剂,并用XRD,BET法对负载磷钨酸后的SBA-15的结构进行分析。以过氧化氢特丁基为氧化剂,二苯并噻吩(DBT)的异辛烷溶液为模拟油进行实验,对介孔分子筛催化剂HPWA-SBA-15的氧化吸附脱硫性能进行研究。结果表明,负载磷钨酸以后,催化剂Nb-SBA-15仍具有规则的二维六方介孔结构,仍属于介孔分子材料;磷钨酸负载量为30%时脱硫效果最佳;Nb-SBA-15催化剂具有较高的催化活性和稳定性。在反应温度为70℃,反应时间为60 min,催化剂用量占总质量的2.2%时,脱硫率达到了100%。     

萃取法脱除工业戊烷中硫化物的萃取剂研究

 以工业戊烷为原料,在萃取温度15 ℃、静置时间15 min、剂油比为1:1的条件下,考察了多种萃取剂的萃取脱硫性能。实验结果表明,糠醛和NaOH溶液作为单一萃取剂的效果较好,可将工业戊烷中的硫由原来的40.3 mg/L降低到1mg/L; 5%NaOH溶液与95%乙醇在较宽的体积比范围内进行复配可将戊烷中硫含量降低到1mg/L; 当N,N-二甲基甲酰胺与5%NaOH溶液按照体积比为1:1进行复配时,可将戊烷中的硫含量降低到1 mg/L,但N,N-二甲基甲酰胺含量过高则会抑制复合萃取剂的脱硫效果。     

环烷酸锰催化水热裂解脱除渣油中的噻吩硫

采用水热裂解脱硫技术脱除减压渣油中的噻吩硫,对比了分散型催化剂与油溶性催化剂的催化脱硫性能,考察了水热裂解脱硫的工艺条件,采用元素分析、飞行时间质谱和GC-MS等分析手段对水热裂解产物进行了分析,并初步探讨了噻吩类硫化物的脱硫机理。实验结果表明,水热裂解脱硫的最佳工艺条件为:环烷酸锰为催化剂、反应温度360℃、油水质量比为7∶3、反应时间48 h,在此条件下渣油脱硫率为54.04%。表征结果显示,水热裂解后渣油的平均相对分子质量降低约50%,水热裂解的油样在经焦化后硫含量低于3%(w)。     

利用离子液体萃取脱除并回收正辛烷中噻吩的研究

 用盐酸三乙胺(Et3NHCl)和无水AlCl3按不同的摩尔比合成了离子液体,并评价了其对模型汽油中噻吩硫的脱除与回收效果。实验结果表明,选用无水AlCl3与Et3NHCl的摩尔比为2.0的离子液体进行萃取脱硫实验,当萃取时间为40 min、温度为40 ℃、剂油体积比为0.02时,脱硫率可达到90%以上;离子液体不仅可以重复使用4次,而且还可以通过减压蒸馏的方法进行再生,在再生过程中可回收约52.34%的噻吩。     

Cu-BTC吸附剂对模拟油中有机氯化物的脱除性能

采用水热合成法制备了苯-1,3,5-三甲酸铜(Cu-BTC)吸附剂,利用X射线衍射、扫描电镜、N2吸附-脱附和热重分析等手段对其进行表征;通过静态吸附法用Cu-BTC吸附脱除模拟油中的3-氯-2-甲基-1-丙烯(A)、1,4-二氯丁烷(B)、3-氯-2-甲基苯胺(C)和5-氯-2-甲基苯胺(D),考察吸附时间、吸附温度...     

航空煤油中硫醇硫的脱除工艺研究

针对航空煤油中硫醇硫含量严重超标的情况,采用预载复合脱硫催化剂HPA-304、脱色脱氮催化剂HPT-108和白土精制剂对航空煤油进行精制处理,并优化了催化剂和稀释剂的填装方案。结果表明,在反应温度为50℃、反应压力为1.0 MPa、空速为1～2 h-1的工艺条件下,催化剂HPT-108及白土精制剂都能将航空煤油中的碱性氮化物完全脱除;催化剂HPA-304可将航空煤油中的硫醇硫由90μg/g脱除至小于20μg/g。     

高硫焦代油工程电气调试中的问题及措施

针对中国石化齐鲁分公司炼油厂高硫焦代油项目电气部分调试中遇到的问题.及时分析处理,为今后机组调试和机组运行中出现类似问题提供借鉴。     

Desulfurization of Simulated Oils by Microwave Chemical Methods

Abstract

Microwave technology was introduced for the desulfurization of sulfurous crude oil and the influence of microwave processes on removing benzothiophene sulfur and bi-benzothiophene sulfur in simulated oils was studied in this article. The results manifested that the desulfurization efficiencies of BBPV, formylhydroperoxide and peroxyacetic acid for an oil sample (simulated oil 2) containing bi-benzothiophene were better than for the oil sample (simulated oil 1) containing benzothiophene. When dosages of BBPV increased from 0.5% to 4%, the desulfurizing efficiencies of simulated oil 1 and 2 were raised from 19.8% to 53.7%, and 48.0% to 64.2%, respectively. With the increase of temperature, the reaction order desulfurization of the simulated oils by microwave increased, and the rate of the microwave reaction increased. The desulfurizing efficiency increases along with the temperature in the same time.     

甲基叔丁基醚萃取蒸馏脱硫的研究

采用萃取蒸馏法将甲基叔丁基醚(MTBE)萃取到萃取剂中,蒸馏得到低硫MTBE产品,并对萃取剂及萃取蒸馏的操作条件进行了优化。实验结果表明,在水中添加非质子极性助溶剂ZRD制得的TMS萃取剂的脱硫效果较好,MTBE在TMS萃取剂中的溶解度为10.5。采用TMS萃取剂的最佳实验条件为:MTBE 50 m L、萃取温度15℃、TMS与MTBE的体积比3.0、萃取时间15 s、相分离时间7 min、蒸馏温度75℃、蒸馏时间25 min。在最佳实验条件下,MTBE的硫含量可从98.1μg/g降至8.4μg/g、脱硫率为91.44%、MTBE的质量收率为99.69%;TMS循环使用5次均可保证MTBE的硫含量降至10μg/g以下。该方法避免了因萃取剂硫含量富集而无法获得低硫MTBE产品的弊端。     

金属络合类离子液体用于汽油萃取脱硫的研究

本文由原料[Et₃NH]Cl、无水FeCl₃和无水CuCl合成了离子液体[Et₃NH]Cl-FeCl₃/CuCl,考察了其萃取脱硫性能。结果表明：在对模拟汽油（噻吩溶于正辛烷）和FCC汽油脱硫时,离子液体[Et₃NH]Cl-FeCl₃/CuCl均表现出了较好的脱硫性能。当离子液体和模拟汽油的体积比V(IL):V(oil)=0.08,时间t=50min,温度T=50℃时,模拟汽油中噻吩的脱除率能够达到 93.9%。在相同的温度和时间条件下,当离子液体和FCC汽油的体积比V(IL):V(oil)=0.1时,经过三次萃取,能够获得低硫（硫含量小于10μg/g）FCC汽油,FCC汽油的收率为94.3%。离子液体具有较好的循环使用能力,循环使用5次后,汽油中噻吩的脱除率没有明显降低。     

离子液体萃取脱硫的研究

合成了一系列离子液体用于模拟油的萃取脱硫实验,考察了不同离子液体及其与模拟油的质量比、反应温度和反应时间等因素对模拟油萃取脱硫效果的影响。实验结果表明,离子液体1-丁基-3-乙基咪唑氯盐([BEIM]Cl)的萃取脱硫效果明显优于其他离子液体。当以[BEIM]Cl为萃取剂时,萃取脱硫的最优条件为:[BEIM]Cl与模拟油的质量比1.0,萃取温度30℃,萃取时间30min。在此条件下,单级脱硫率可达52.02%;经5级脱硫后,总脱硫率高达96.56%。采用溶剂反萃取法对[BEIM]Cl进行了再生,再生后[BEIM]Cl的脱硫率可达新鲜[BEIM]Cl的95%。     

乙苯萃取精馏分离甲醇与碳酸二甲酯二元共沸物

根据萃取精馏原理,采用正交试验设计,运用计算机对实验数据进行最优化处理,确定了萃取精馏分离甲醇与碳酸二甲酯二元共沸物的最佳工艺条件：以乙苯为萃取剂,单圈玻璃为填料,回流比控制在7：1,萃取剂滴加速率为6ml／min,萃取剂配比为5：1。以此工艺路线分离所得的碳酸二甲酯纯度为99．99％。     

甲苯萃取精馏分离甲醇与碳酸二甲酯共沸物

根据萃取精馏原理,采用正交试验设计,运用计算机对实验数据进行最优化处理,确定了萃取精馏分离甲醇与碳酸二甲酯二元共沸物的最佳工艺条件:以甲苯为萃取剂,单圈为填料,回流比为5:1,滴加速率为5:1,萃取剂配比为2:1,以上述工艺条件,进行DMC-甲醇分离,所得的碳酸二甲酯纯度为99.99%。     

The Extractive Desulfurization of Fuels Using Ionic Liquids Based on FeCl3

Abstract

Six Lewis acid ionic liquids were synthesized and employed as extractants for desulfurization of the model oil containing dibenzothiophene (DBT). Very promising ionic liquid was 1-butyl-3-methylimidazolium chloride-FeCl3 ([bmim]Cl/FeCl3), which performed best in the studied ionic liquids under the same operating conditions. It can remove DBT from model oil after continuous extraction for four steps, and the desulfurization efficiency can reach 97.9% under mild reaction conditions. Other sulfur-containing compounds were also investigated. The used ionic liquid could be regenerated six times without a significant decrease in activity.     

Deep Desulfurization of Model Oil by Extraction with a Low-viscosity Ionic Liquid [BMIM]SCN

In this work, a low-viscosity ionic liquid 1-buthyl-3-methylimidazole thiocyanate ([BMIM]SCN) was utilized as extractant for the extractive desulfurization of thiophene in model oil. Several conditions were investigated respectively, including extraction time, temperature, and volume ratio of ionic liquid to model oil. Also the kinetics of extraction of thiophene were proposed. Under the optimal extractive conditions, the removal of thiophene in model oil was 55.6%. Other sulfur compounds and real oil were also investigated. Furthermore, the total desulfurization efficiency could reach 98.3%. In addition, the ionic liquid could be recycled seven times with negligible decrease in activity.     

Preliminary Research on Desulfurization of Simulated Diesel Fuel with Peroxotungstate Biquaternary Ammonium Salt/H2O2 System

Abstract

A biquaternary ammonium salt catalyst, chloride-1,4-dibenzyl-diaza-bi-cyclo [2.2.2] octane peroxotungstate (peroxotungstate biquaternary ammonium salt), was prepared, the structure of which was determined through infrared spectrometry, and was applied in desulfurization of simulated diesel fuel. Under the circumstances in which the close ion-pair of biquaternary ammonium cation and peroxotungstate anion was formed, the mechanism of phase transfer catalysis was offered with analyzing experimental process and data. The desulfurization efficiency reached 99.35% when the reaction temperature was 60°C, the reaction time was 20 min, and the molar ratio of peroxotungstate biquaternary ammonium salt to H₂O₂ was 0.015.