新型复合分子筛的制备及其吸附脱硫性能研究

用碱处理沸石ZSM-5的浆液作为硅铝源,合成了一系列新型微孔-介孔复合分子筛,采用X射线衍射（XRD）、比表面积分析法（BET）对其进行了表征,并模拟汽油吸附脱硫对制备的分子筛进行了性能评价。结果表明,产物为具有微孔、介孔双孔分布的复合分子筛,其中介孔孔径主要集中在2．6nm。复合分子筛的最佳合成条件如下：n（SiO2）：n（CTAB）：n（H2O）为1．00：0．15：60．00,在80℃水浴中用1．0mol／LNaOH溶液处理1h,控制体系pH值为10．50,晶化温度为100℃,晶化时间为24h,在550℃马弗炉中焙烧6h。负载过渡金属离子如Fe^3＋,Ag^＋,Co^2＋,Ni^2＋等可改善复合分子筛的吸附脱硫性能,经Fe^3＋改性后其饱和吸附量可高达37．74mg／g。     

Cu/Ce-MCM-41分子筛的制备及其在吸附脱硫中的应用

合成了不同Cu／Si比（Ce／Si比皆为0．01）的Cu／Ce—MCM-41分子筛，用于在常温常压下吸附汽油模拟溶液中的含硫化合物，结果显示吸附剂中脱硫能力最好的是Cu／Si比为0．02的吸附剂。XRD、FT-IR、比表面测定等表征结果表明，样品具有MCM-41典型的规整有序的孔道结构，并且合成的特定阶段加入超声作用，可以优化其结构从而提高脱硫率。适宜的吸附条件为常温常压吸附，剂油比为0．019，吸附时间为2h。另外，该吸附剂对分子尺寸较大的二苯并噻吩也有较好的脱硫效果，而且经过高温焙烧再生后，仍具有较高的脱硫容量。在芳香化合物竞争吸附的体系中，Cu／Ce-MCM-41仍然具有较好的选择吸附性能，说明所掺杂的金属离子之间可能形成了协同作用，从而使吸附剂同时拥有了较高的脱硫容量和选择性。     

分子筛吸附脱硫生产清洁燃料

分子筛吸附脱硫技术因具有投资成本低、操作条件温和、脱硫率高等优点而备受关注。本文综述了分子筛吸附脱硫领域的最新研究成果,着重介绍了改性分子筛的吸附性能与分子筛的再生性能,并对分子筛吸附脱硫的进一步研究进行了展望。     

选择性吸附脱硫分子筛催化剂的制备及性能

采用酸性法与液相离子交换相结合的方法制得Ni（Ⅱ）HY和Ce（Ⅳ）Y分子筛,利用静态吸附脱硫法考察了吸附温度和时间对Ni（Ⅱ）HY分子筛吸附催化裂化（FCC）汽油脱硫效果的影响。结果表明,在吸附温度为80℃、吸附时间为8h的最优条件下,Ni（Ⅱ）HY分子筛的脱硫率达到92．6％。在动态条件下,采用具有2个串联反应器,并分别装填Ni（Ⅱ）HY,Ce（IV）Y分子筛的固定床处理后FCC汽油的硫含量低于10ug／g。     

Cuo／13X分子筛的制备及其在汽油深度吸附脱硫中的应用

为有效达到汽油深度脱硫的目的,以13X分子筛为载体,采用浸渍法制备了用于催化裂化汽油深度脱硫的吸附剂CuO/13X,考察了CuO/13X的制备条件和吸附脱硫条件对其脱硫效果的影响。适宜的制备条件为CuSO_4溶液浓度0．2mol/L,浸渍时间6h,干燥温度100℃,焙烧温度350℃,焙烧时间2h;适宜的吸咐条件为常温、常压吸附,剂油比1:4,吸附时间0．5h。在最优条件下,CuO/13X对4种模拟汽油中硫的脱除率均在88%以上,CuO/13X的硫容可达4．0mg/g左右。     

磁性Cu(Ⅰ)-Y分子筛的制备及其在磁稳定床中吸附脱硫的研究

首先在磁性基质上合成Na-Y分子筛，再用Cu（NO3）2溶液在135℃进行水热离子交换，然后在氮气中500℃焙烧活化，制得磁性Cu（Ⅰ）-Y分子筛吸附剂，在磁稳定床（MSB）中考察了吸附温度、操作压力、空速和磁场强度等操作条件对其脱硫性能的影响，使用含多种噻吩的正辛烷为模型汽油。结果表明，磁性Cu（Ⅰ）-Y分子筛在MSB中适宜的脱硫操作条件是常温、常压、体积空速为10h、磁场强度为10kA／m，此时其对模型汽油的饱和硫容量为6．51％。     

分子筛脱硫剂的制备及其吸附脱硫性能研究

利用铵盐离子交换的方法对NaY分子筛进行改性制备了HY型分子筛,HY型分子筛分别采用与硝酸铜溶液进行二次离子交换和浸渍法制得两种CuY型分子筛脱硫剂A和脱硫剂B。利用改性的Y型分子筛脱硫剂进行直馏柴油静态吸附脱硫实验,结果表明,HY型分子筛经过浸渍法和离子交换法两种改性方法制备的脱硫剂其脱硫效果又进一步增强,其中以硝酸铜溶液离子交换法制备的脱硫剂A脱硫效果最好,其脱硫率接近70％。     

Co对Cu~+-13X分子筛选择吸附脱硫性能的影响

采用液相离子交换法制备了Cu+-13X和Co2+/Cu+-13X两种分子筛吸附剂,运用XRD,SEM,FTIR等手段对其进行表征。通过静态吸附实验与动力学吸附实验研究了两种吸附剂对模拟汽油的吸附性能,并采用Langmuir模型对静态吸附平衡数据进行拟合,同时采用Crank单孔扩散模型对动力学吸附数据进行拟合。实验结果表明,当Co2+/Cu+-13X吸附剂中Co含量为2.35%(w)时,Co2+/Cu+-13X吸附剂的吸附脱硫效果最佳;Co2+/Cu+-13X吸附剂对噻吩(TP)和苯并噻吩(BT)的最大吸附量相对于Cu+-13X吸附剂分别提高了42.1%和18.8%;Co与Cu之间可发生协同作用,Co2+抑制Cu+向Cu2+的转换,有助于提高吸附剂的脱硫性能;两种吸附剂与噻吩类硫化物之间主要是π配位作用,不存在S-M配位作用;采用Crank单孔扩散模型可很好地描述两种吸附剂的动力学吸附过程,且在TP和BT双组分动力学吸附过程中,Co2+可提高Cu+-13X吸附剂对BT的吸附选择性。     

Cu(Ⅱ)-Ce(Ⅳ)/13X分子筛的制备及其脱硫性能研究

采用离子交换法制备Cu2+和Ce4+同时改性的Cu(Ⅱ)-Ce(Ⅳ)/13X分子筛吸附剂,同时制备单一金属离子Cu2+改性的Cu(Ⅱ)/13X和Ce4+改性的Ce(Ⅳ)/13X。采用X射线粉末衍射（XRD）、氮气吸附-脱附等手段对吸附剂进行表征。将碳四烃中的典型硫化物二甲基二硫化物、甲硫醚、叔丁硫醇溶于正庚烷中进行吸附脱硫研究。结果表明：与未改性的13X分子筛相比,Cu2+和Ce4+改性的Cu(Ⅱ)-Ce(Ⅳ)/13X分子筛的比表面积和孔体积有所降低,平均孔径和介孔数量增加,由于两种金属的协同作用,使得Cu(Ⅱ)-Ce(Ⅳ)/13X表现出更好的脱硫性能;Cu(Ⅱ)-Ce(Ⅳ)/13X吸附剂对二甲基二硫化物、甲硫醚、叔丁硫醇的脱除效率均高于单一金属改性后的Ce(Ⅳ)/13X和Cu(Ⅱ)/13X吸附剂;Cu(Ⅱ)-Ce(Ⅳ)/13X吸附剂具有良好的再生性能,第1次再生后脱硫率为新鲜吸附剂的98%。     

HMS分子筛负载磷钨酸催化剂的制备及其脱硫性能

以HMS分子筛为载体、磷钨酸(H3PW12O40,简写为PW12)为活性组分,通过超声浸渍法和水热分散法制备了系列PW12/HMS催化剂,并采用FTIR,XRD,SEM,TEM,BET等手段对催化剂的结构和形貌进行表征。以模拟柴油中苯并噻吩的氧化脱除为探针反应对催化剂的脱硫性能进行了研究,考察了催化剂制备方式、PW12负载量、萃取剂类型、催化剂及氧化剂的用量、预氧化时间等因素对脱硫率的影响。表征结果显示,催化剂保持了HMS分子筛的介孔结构及PW12的Keggin结构。实验结果表明,在水热分散法制备的负载量30%(w)的PW12/HMS催化剂用量0.15 g、n(H2O2)∶n(S)=8、萃取剂为乙腈、预氧化时间6min、模拟柴油10 m L、V(模拟柴油)∶V(萃取剂)=1∶1、反应温度60℃、反应时间60 min的条件下,脱硫率达97.81%。     

Preparation of Cu-, Zn-, Co-Zeolites and Application for Adsorptive Desulfurization of Saudi Arabian Medium Crude

A series of Cu(II)-, Zn(II)-, Co(II)-loaded zeolites were successfully prepared by liquid phase ion-exchange method and characterized by X-ray diffraction(XRD), N2-adsorption specific surface area measurement(BET), X-ray fluorescence(XRF), and scanning electron microscopy(SEM) techniques. The adsorptive desulfurization performance of different adsorbents for treating Saudi Arabian medium crude oil was investigated, and the results showed that desulfurization efficiency declined in the following order: Zn(II)X Cu(II)Y Co(II)X Cu(II)X Co(II)Y Zn(II)Y. The best desulfurization efficiency of 41.01% was achieved by using Zn(II)X as the adsorbent under the optimized conditions.The desulfurization performance of Zn(II)X in different distillates showed that a better performance was obtained in heavy petroleum fractions. Furthermore, the distribution of sulfur compounds in distillates after desulfurization was analyzed and the results showed that the adsorbent Zn(II)X could preferably adsorb aromatic sulfides such as thiophenes,benzothiophenes, and dibenzothiophenes. These results suggested that the π-complexation between zinc ions and sulfides would be crucial to the excellent desulfurization efficiency of Zn(II)X. In addition, the used adsorbent could be regenerated by heating at 700 °C in air, and around 84% of desulfurization capacity was recovered after the first cycle of regeneration.     

塔中油田汽提法原油脱硫化氢工艺技术

为了减少塔中联合站处理装置中大量高含H2S原油对非抗硫工艺管线和设备造成的严重腐蚀,消除外输原油和天然气H2S浓度严重超标带来的安全隐患,中国石油塔里木油田公司借鉴国内首套重质原油干法汽提脱硫装置在塔河油田三号联合站试验成功并且安全平稳运行的经验,在塔中作业区水平一转油站建成了日处理能力1 000 t的汽提法原油脱硫装置,对塔中一号气田试采单井原油进行脱硫处理,通过对温度、进液量及汽提比等参数进行不断优化将装置调整到最佳运行状态,采用3018固体脱硫剂对汽提脱硫装置中产生的高含H2S尾气进行全部回收,有效地防止了大气污染。     

Simple Techniques for Evaluation of Crude Oil Compatibility

Abstract

Blending crude oils or crude oils and condensates of different origin may give rise to deposit related problems due to incompatibility. Although the problem has been recognized, there are as yet no standard methods for the determination and quantification of crude oil compatibility. This study focused on the compatibility of stock tank oils in storage depots and refineries. Using blends of Arabian Medium and Gippsland crude oils as a model system, various simple techniques were investigated and compared with the results of the in-house Shell stability test (the Po/FRmax test): microscopy, a modified Hot Filtration Test, a modified ASTM spot test and a modified Shell Spot test. All techniques (with the exception of the ASTM spot test) were capable of identifying an unstable regime, but the onset of asphaltenes flocculation varied with the experimental conditions. Sample pretreatment was found to be a necessary prerequisite for obtaining meaningful data. The Shell Spot Test appears to be a fast and simple method for monitoring crude oil compatibility in the downstream business.     

Desulfurization of FCC Gas Oil by Solvent Extraction, Photooxidation, and Oxidizing Agents

A deep desulfurization process for FCC gas oil by a combination of liquid-liquid extraction, photochemical reaction, and treating with oxidation agents has been investigated. The process often represented by the model heterocyclic compounds, benzothiophenes (BTs) and dibenzothiophenes (DBTs). The process is comprised of three stages. Extraction of the sulfur-containing compounds from a catalytic cracked gas oil by acetonitrile, photooxidation, and photodecomposition of the sulphur compounds in the acetonitrile phase by ultraviolet irradiation from a high pressure mercury lamp, and recovery of the sulphur from the irradiated oil and treatment with oxidizing agent. The process was carried under conditions of room temperature and atmospheric pressure. Acetonitrile/water azeotropic mixture has been recycled successfully through distillation column. The sulfur in this gas oil has been decreased from 1800 ppm to 550 ppm after photo-desulfurization, and 508 ppm after treatment with the oxidizing agents. The total yield of the oil was 90-95%.     

塔河油田重质原油脱硫工艺优化与应用

塔河油田属于奥陶系油气藏,所产原油物性主要表现为粘度高、密度大、富含硫化氢,进入油田生产系统后,对设备装置、原油储罐、管线等关键要害部位腐蚀较大,往往造成系统不稳定,同时在生产环节中,塔河原油容易逸散出高浓度的硫化氢,对环境和人造成极大的影响和危害。如何结合现有实际情况,降低原油硫化氢含量是需要解决的问题。针对问题,提出了在上游原油集输站库加装静态混合器进行脱硫工艺优化的解决措施,使原油硫化氢含量、脱硫剂单位成本费用两项关键控制指标大幅降低,取得了较好的经济效益和社会效益,具有较强的推广价值和应用前景。     

Progress in the Technology for Desulfurization of Crude Oil

The poor quality of crude oil obviously leads to high sulfur contents of oil products,and the technology for desulfurization of crude oil is urgently needed so that the sulfur contents in petroleum product could be reduced from the root.This paper describes the progress in technology for desulfurization of crude oil.The present technologies for desulfurization of crude oil include caustic washing,dry gas desulfurization,hydrodesulfurization(HDS),etc.The new combined technologies for desulfurization of cr...     

大型原油浮顶罐焊接材料国产化应用

目前我国在大量制造10×10^4m。双盘式浮顶原油罐,以保证国家原油储备达到90天原油进口量的目标。在四川石化工程10×10^4m。浮顶原油罐上,特别是罐体用高强钢12MnNiVR重要焊缝上首次采用了国产焊材（罐壁纵缝气电立焊除外）。通过在2台10×10^4m,双盘式浮顶原油罐上的施工实践和检测结果,表明我国大型原油储罐在焊材质量、生产供应和施工焊接工艺技术水平上已完全具备焊材国产化的能力。     

燃料油选择性吸附脱硫研究进展

依据燃料油中硫化物与吸附剂表面活性点相互作用的类型,综述了π络合吸附、S—M配位吸附、酸性位吸附和多活性位吸附等选择性吸附脱硫方式的研究进展。认为通过结合多种选择性吸附原理,制备具有多种活性位的吸附剂,达到深度脱硫过程中高选择性和高吸附容量的目的,是燃料油深度脱硫吸附剂研究和开发的主要方向。     

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.