模拟轻质油品烷基化沉淀法脱硫

 以精制油品为溶剂,苯并噻吩(BT)、二苯并噻吩(DBT)、4,6—二甲基二苯并噻吩(4,6—DMDBT)作为模型含硫化合物组成模拟轻质油品,以卤代烃和四氟化硼钾为烷基化剂对模拟轻质油品烷基化沉淀脱硫进行了研究。考察了反应温度、反应时间、烷基化剂种类及其用量、溶剂等因素对总硫脱除的影响。实验结果表明：在反应温度30℃,CH3CH2Br：S=80：1(mol/mol),KBF4：S=30:1(mol/mol),反应时间在24h的条件下,总硫脱除率可以达到76.5%。     

电场作用下原油氧化脱硫研究

Oxidative desulfurization (ODS) of Azeri crude oil was studied under the electric field.By means of orthogonal experiments,the optimum conditions for desulfurization of crude oil were identified,while the effect of oxidative desulfurization under the electric field was compared with that of the single oxidative desulfurization method.The test results showed that the desulfurization reaction taking place under the electric field would be better than the traditional method.The desulfurization rate of crude oil could reach up to 77.06% at 115 ℃ at a distilled water amount of 10 m%,a desulfurizer dosage of 200 μg/g,and a demulsifier dosage of 50 μg/g.     

脱硫吸附剂中硅酸锌形成动力学及脱硫活性和稳定性研究

A new industrial S Zorb sorbent(Ni/Zn O-P) was prepared by using the spray drying technique. The other two traditional sorbents(Ni/Zn O-M and Ni/Zn O-H) were prepared in exactly the same way except the use of different silica-alumina binder matrices. The XRD, Rietveld quantitative phase analysis, BET, and laser particle size analysis were employed to characterize their physico-chemical properties. The deactivation mechanism and desulfurization kinetics of sorbent was investigated on a water vapor aging treatment device. It was shown that both the water vapor pressure and reaction temperature significantly could influence the formation rate of inactive Zn2 Si O4, which could decrease the sulfur storage capacity of sorbents. The Zn2 Si O4 content profiles could be fitted into the zero order equation, from which the apparent rate constant k and the activation energy E a were calculated. The matrix P greatly raised the E a of Zn2 Si O4 formation due to the less bridged hydroxyl silanol groups on its surface, which accounted for the high stability of Ni/Zn O-P. The desulfurization performance of the fresh and aged sorbents showed that the overall average sulfur conversion of Ni/Zn O-P(aged) was 92%, which was close to that of fresh sorbents(95%), and was higher than that of Ni/Zn O-M(aged)(86%) and Ni/Zn O-H(aged)(90%). Based on these findings, the application of Ni/Zn O-P can greatly improve the long-term running stability of the industrial unit.     

一种高效的油品深度氧化脱硫工艺开发成功

据悉，DS2Tech公司日前已成功开发一种用于原油及其衍生物如汽油、柴油、喷气燃料和燃料油深度脱硫的氧化脱硫工艺。该公司宣称这是迄今为止全球唯一有效的深度氧化脱硫工艺。     

负载银离子改性活性炭吸附二苯并噻吩研究

以活性炭为基体,通过硝酸盐溶液浸渍方法制备了负载银离子的改性活性炭,并将其作为脱硫吸附剂。通过静态吸附二苯并噻吩的实验,考察了吸附时问、银离子负载量等对改性活性炭吸附硫容量的影响,比较了负载前后活性炭的吸附等温线,研究了改性活性炭的再生性能。结果表明,银离子负载能显著提高活性炭对二苯并噻吩的吸附容量,但并不改变等温吸附线的类型。银离子负载活性炭经溶剂洗涤再生3次后,吸附容量有所下降。     

改性Y型分子筛吸附脱除模拟油品中氯辛烷

分别采用离子交换法和等体积浸渍法对Na-Y分子筛进行改性。利用低温氮气吸附 脱附、X射线衍射、X射线荧光光谱和氨气程序升温脱附等手段对改性分子筛进行表征。考察了改性方法、交换的离子类型、吸附时间、吸附温度和吸附剂与油品质量比等因素对改性分子筛吸附脱除模拟油品中氯辛烷性能的影响,并研究了其再生循环使用性能。结果表明：离子交换法制备的Cu-Y分子筛的吸附脱氯性能高于等体积浸渍法制备的CuO/Y分子筛。经Co²⁺、Cu²⁺、Ag⁺改性的Y型分子筛,其脱氯性能较Na-Y分子筛显著增加,其中Cu-Y分子筛的脱氯性能最好。当Cu-Y分子筛与油品质量比为1∶5、吸附温度为20 ℃、吸附时间为1 h时,脱氯率达到91.9%。NH₃-TPD表征显示,分子筛的表面酸性对其脱氯性能具有显著影响,分子筛表面总酸量越大,其脱氯性能越高。Cu-Y分子筛再生循环使用7次后,其比表面积及酸量有少量减小,导致其脱氯性能略微降低。     

溴化铜改性白土吸附脱除丙硫醇和二甲基硫醚的研究

室温下,考察了溴化铜改性白土对丙硫醇和二甲基硫醚的吸附脱除。每克吸附剂的饱和硫容达到196毫克硫。还考察了铜负载量及吸附剂焙烧温度对脱硫效果的影响。结果表明,吸附剂制备的最佳条件是铜负载量15%,150℃焙烧。从吡啶-红外光谱可以看出B酸有利于脱硫。在溴化铜和二甲基硫醚的反应产物的拉曼光谱上检测到了C-S及Cu-S的振动峰。根据杂化轨道理论和络合吸附反应,丙硫醇和二甲基硫醚在溴化铜改性白土上的吸附是基于S-M机理。     

改性Y型分子筛对石脑油脱硫效果的研究

NH4Y zeolite was prepared through ion-exchange of NaY zeolite with an ammonium salt. Then LaY zeolite was obtained through a secondary ion-exchange of NH4Y zeolite with a rare earth salt solution followed by calcination of the zeolite product. Dynamic adsorptive desulfurization of naphtha was conducted in the presence of the modified LaY zeolite, and the sulfur content of the treated naphtha samples was analyzed by microcoulometry. The test results showed that under dynamic conditions the LaY zeolite prepared through secondary ion-exchange of NH4Y zeolite, which was prepared using 1.0 mol/L ammonium salt, with the rare earth salt exhibited a better desulfurization efficiency. Furthermore, the LaY zeolite achieved a best desulfurization effect at an adsorption temperature of 45 ℃ and an adsorbent/oil ratio of 1:2.     

油品装车排气深度净化治理技术研究

通过对装车排气达标治理技术对比分析，确定了低温柴油吸收-总烃均化-催化氧化工艺治理山东某石化企业汽油、喷气燃料装车排气。在吸收油流量15~20 m3/h、吸收温度8~15 ℃、吸收压力0.2 MPa、催化氧化反应温度 250~350 ℃及反应空速5 000~20 000 h-1的操作条件下，研究了低温柴油吸收、总烃均化、催化氧化过程对汽油及喷气燃料装车排气治理的效果，净化气中非甲烷总烃排放质量浓度小于20 mg/m3，苯、甲苯、二甲苯排放浓度低于检出限值，满足国家及地方标准排放要求。该装置的投资回收期约为5年，具有一定的经济效益和明显的环保效益。     

改性分子筛的催化裂化脱硫活性研究

以催化裂化过程中含硫化合物的转化规律和转化机理为基础,通过分析不同元素改性对分子筛氢转移活性和裂化活性的影响规律,研究了改性分子筛在提高裂化催化剂脱硫活性方面的作用.     

Deep Desulfurization of Light Oil Using the Imitating Silver Salt ILs Method

Abstract

Sulfides in oils are harmful in many ways, in particular, deterioration of the environment resulting from sulfur dioxide. A novel desulfurization process for light oil has been investigated. A mixture consisting of benzothiophene (BT), dibenzothiophene (DBT), and oil fractions (235°C–270°C) refined by acid–alkali treatment was employed for alkylation desulfurization tests in a nitrogen atmosphere. The results showed that at a reaction temperature of 30°C, ratio of bromoethane (CH₃CH₂Br) to sulfur of 30:1 (mol/mol), ratio of silver tetrafluoroborate (AgBF₄) to sulfur of 6:1 (mol/mol), and reaction time of 16 hr, the desulfurization yield could reach 76.3%.     

柴油吸附脱硫技术研究进展

吸附脱硫是一项具有广阔发展空间及应用前景的脱硫技术,具有操作简单、投资少、无污染、适合于深度脱硫等优点。详细介绍了S-Zorb diesel、MeND、IRVAD、PSU-SARS、Exxon diesel及其他吸附脱硫技术的研究进展情况。     

吸附法车用燃料油脱硫技术进展

吸附法脱除汽油和柴油中含硫化合物,具有投资操作费用低等优点,因而具有较大的发展空间和潜力.综述了国内外汽油和柴油吸附脱硫技术在吸附工艺和吸附材料方面的研究进展,重点介绍了IRVAD工艺、S-Zorb工艺、PSU -SARS工艺、LADS工艺和Exxon工艺,以及活性炭、分子筛、金属氧化物等吸附材料的研究状况.     

Ni/ZnO吸附剂上溶剂油的超深度吸附脱硫

分别采用等体积浸渍法和共沉淀法制备了Ni质量分数为20%的Ni/ZnO吸附剂,采用N2吸附、X射线衍射和扫描电子显微镜研究了制备方法对Ni/ZnO吸附剂物化性质的影响,通过固定床吸附实验评价了Ni/ZnO吸附剂对溶剂油的吸附脱硫性能。实验结果表明,共沉淀法制备的Ni/ZnO吸附剂的比表面积和孔体积分别高达66.7m2/g和0.236cm3/g,吸附脱硫性能明显优于等体积浸渍法制备的Ni/ZnO吸附剂。在溶剂油中硫含量为145.0g/mL、吸附温度300℃、压力1.0MPa、进料液态空速6h-1、氢气与溶剂油体积比300(氢气体积为标准状况下的体积)的条件下,连续运转200h,共沉淀法制备的Ni/ZnO吸附剂对有机硫化物的脱除率始终大于90%,硫容量约为150mg/g。该吸附剂对原料有很好的适应性,可再生,多次循环使用后脱硫性能仅略有降低,具有潜在的工业应用价值。     

流化催化裂化汽油吸附法深度脱硫工艺的研究

以臭氧氧化活性炭为吸附剂,对流化催化裂化(FCC)汽油进行吸附脱硫研究,探索了最佳吸附条件和最佳再生条件。实验结果表明,在活性炭颗粒大小为80～100目、吸附温度为80℃、原料液态空速为1.70h-1的最佳吸附条件下,可使初始硫含量为796μg/g的FCC汽油的初始流出液的硫含量降到18μg/g,初始脱硫率达97.7%;在脱附剂为乙醇、再生温度为60℃、脱附剂液态空速为1.70h-1的最佳再生条件下再生活性炭,循环使用3次时仍可使初始流出液的硫含量降到45μg/g,初始脱硫率达94.3%。     

Deep Desulfurization of Model Gasoline by Adsorption on Mesoporous CeMCM-41

Abstract

Cerium atoms have been introduced into the framework of MCM-41 by a hydrothermal synthesis method with cetyltrimethylammonium bromide (CTMABr) as template, sodium silicate as silica source, and cerium chloride as cerium source. Desulfurization of various model fuels containing about 500 μg/g sulfur were studied over the synthesized CeMCM-41 with a liquid hourly space velocity of 7.5 hr^?1 at ambient conditions. The sulfur adsorption capacity was 10.0, 11.8, 14.0, and 15.4 mg(S)/g adsorbent for thiophene, dibenzothiophene (DBT), 4,6-dimethyldibenzothiophene (4,6-DMDBT), and tetrahydrothiophene (THT), respectively. The charges on S atom in thiophene, DBT, 4,6-DMDBT, and THT, calculated by using density functional theory (DFT), are ?0.159, ?0.211, ?0.214, and ?0.298, respectively, implying that the S-M bond between the adsorption sites and thiophene is much weaker than that between the adsorption sites and DBT, 4,6-DMDBT, or THT.     

液相吸附法燃油深度脱硫机理的研究进展

针对吸附脱硫的分子扩散和表面吸附两个过程。从分子尺寸选择、酸性位点吸附以及配位作用等方面综述了现有的吸附脱硫机理,介绍了各个机理指导下的液相吸附脱硫技术。指明了吸附脱硫机理的研究对开发高效燃油深度脱硫吸附剂和吸附脱硫新技术的指导意义。