BrØnsted酸性离子液体在萃取氧化二苯并噻吩中的应用

 以具有BrØnsted酸性的吡咯烷酮离子液体N-甲基-2-吡咯烷酮氟硼酸盐([Hnmp]BF₄)为萃取剂和催化剂, 含30%质量分数H₂O₂的双氧水为氧化剂, 二苯并噻吩(DBT)的正辛烷溶液作为模型油, 同时进行萃取脱硫和氧化脱硫, 考察了n(H₂O₂)/n(S)、DBT初始浓度和反应温度对脱硫率的影响. 结果表明, [Hnmp]BF₄-H₂O₂体系产生的羟基自由基能将DBT氧化成相应的砜而进入离子液体相, 从而脱除了模型油中的S; 当n(H₂O₂)/n(S)=3、反应温度为60℃、模型油与离子液体等体积时, 在60min内可将油相中的S质量浓度为1550μg/ml 的DBT完全氧化脱除; DBT初始浓度越高, S的完全脱除就越困难. 离子液体重复再生使用7次后, 脱硫率明显降低.     

TiO_2基硫磺回收催化剂表面化学特性研究

随着炼油工业和天然气工业的快速发展,针对SO2排放的环保要求日益严格。对于炼油加工和天然气净化过程所产生的含硫酸性气体,硫磺回收加尾气处理工艺是主要的治理方式,其中TiO2基硫磺回收催化剂逐步得到广泛应用。通过一系列的XPS、XRD、TEM、FT-IR、CO2-TPD、NH3-TPD和吡啶红外分析表征手段,进一步认识到钛基催化剂的表面化学特性,其活性组分为锐钛矿相TiO2,晶粒为纳米级晶粒,具有弱碱性位和中强碱性位。     

Catalytic oxidative desulfurization of fuels in acidic deep eutectic solvents with [(C6H13)3P(C14H29)]3PMo12O40 as a catalyst

Deep eutectic solvents (DESs) are a new class of green solvents analogous to ionic liquids due to their biodegradable capacity and low cost. However, the direct extractive desulfurization of diesel oil by DESs cannot meet the government’s standard. In this work, amphiphilic polyoxometalates were synthesized and characterized by FT-IR and mass spectrometry. The oxidative desulfurization results showed that benzothiophene (BT) could be completely removed by employing a [(C₆H₁₃)₃P(C₁₄H₂₉)]₃PMo₁₂O₄₀, DES (ChCl/2Ac) and H₂O₂ system. It was also found that the organic cation of catalysts played a positive role in oxidative desulfurization. The reaction conditions, such as reaction temperature and time, the amount of catalyst and DES and H₂O₂/S (O/S) molar ratio, were optimized. Different sulfides were tested to determine the desulfurization selectivity of the optimal reaction system, and it was found that 97.2% of dibenzothiophene (DBT) could be removed followed by 80.7% of 4-MDBT and 76.0% of 4,6-DMDBT. After reaction, the IR spectra showed that the catalyst [(C₆H₁₃)₃P(C₁₄H₂₉)]₃PMo₁₂O₄₀ was stable during the reaction process and the oxidative product was dibenzothiophene sulfone (DBTO₂). Furthermore, the catalyst can be regenerated and recycled for four runs with little loss of activity.     

Synthesis of amphiphilic peroxophosphomolybdates for oxidative desulfurization of fuels in ionic liquids

Three amphiphilic peroxophosphomolybdates [C₄mim]₃PMo₄O₂₄, [C₈mim]₃PMo₄O₂₄ and [C₁₆mim]₃PMo₄O₂₄ were synthesized and characterized. These catalysts were used for extraction and catalytic oxidative desulfurization of fuel with H₂O₂ as an oxidant and ionic liquid [C₄mim]BF₄ as an extractant. It was found that [C₁₆mim]₃PMo₄O₂₄ showed the highest catalytic activity and the sulfur content could decrease to 7.5 ppm. In contrast, the desulfurization system shows very low performance without H₂O₂ or ionic liquid. The detailed reaction conditions were optimized including reaction time, temperature, the dosage of H₂O₂ and catalyst, and different sulfur compounds. After the reaction, the catalysts and the ionic liquid can be cycled 8 times with a little decrease in desulfurization efficiency.     

Influence of catalyst support structure on ethene/decene metathesis and coke formation over WO3/SiO2 catalyst

8wt%WO3/SiO2 metathesis (disproportionation) catalysts with different pore structures were prepared by the incipient-wetness-impregnation method. The as-synthesized catalysts were characterized by N2 adsorption-desorption, scanning electron microscopy (SEM), X-ray diffraction (XRD), UV-visible diffuse reflectance spectroscopy (DRS) and scanning transmission electron microscopy-high-angle annular dark field (STEM HAADF). The results of STEM HAADF showed that WO3 species were not uniformly distributed on the SiO2 support. The experimental results of 8wt%WO3/SiO2 performance in ethene/decene metathesis revealed that the catalytic effect of 8wt%WO3/SiO2 catalyst and coke formation over it were closely related to the support pore structure: The 8wt%WO3/SiO2 catalyst with a more complicated pore structure showed better catalytic performance but the coke deposition rate was also faster.     

Co掺杂对CuO/ CeO2-Co3O4优先氧化CO催化性能的影响

采用共沉淀-浸渍法制备了一系列不同Ce/Co物质的量比的CeO₂-Co₃O₄载体和CuO负载量(质量分数)为7% 的CuO/CeO₂-Co₃O₄催化剂,考察了它们在富氢气氛中对CO的优先氧化性能。采用BET、XRD、H₂-TPR等对催化剂进行了表征。测试结果表明:Ce/(Co+Ce)物质的量比为0.9时,CuO/ CeO₂-Co₃O₄催化剂活性最好。少量的Co掺杂有利于提高催化剂的比表面积和铜物种在载体上的分散,少量的Co进入了CeO₂的晶格,增强了钴铈相互作用,进而提高了载体的氧化还原性能。      

应用于脱硫体系的FeCl4离子液体腐蚀行为研究

目的解决1-丁基-3-甲基咪唑四氯化铁(FeCl₄)离子液体在天然气脱硫过程中存在的腐蚀问题。 方法基于失重法,在不同温度、水含量、再生温度下研究了FeCl₄对304不锈钢的腐蚀行为,并通过SEM、XRD、XPS等表征手段分析了其腐蚀机理。 结果FeCl₄对304不锈钢的腐蚀速率随着浸泡温度、水含量的升高而增大,随着再生温度的升高呈现先增大后减小的趋势,且在70 ℃时腐蚀速率最低(0.380 mm/a)。 结论FeCl₄电离出的Cl-通过穿透腐蚀产物膜对金属基体造成的腐蚀是FeCl₄水溶液中304不锈钢腐蚀的主要原因,提高再生温度可有效抑制Cl-的电离,进而减缓腐蚀的进行。      

Vanadium-catalyzed extractive oxidesulfurization of commercial diesel in ionic liquid with combined oxidizing agents

A series of vanadium catalysts were synthesized and employed in pyridinium phosphate [HPy][H₂PO₄] with various oxidants for extractive catalytic oxidesulfurization (ECODS) of diesel. The VO(acac)₂ showed high catalytic activity with HNO₃/H₂SO₄ and ionic liquid via microwave radiations in the MECODS of diesel. The sulfur removal could reach 98.9% in 210?s at 500?W, which was superior to that of the simple ECODS (89.3%) under optimal conditions (V_diesel?=?20?mL, VIL/Vdiesel volume ratio?=?0.075, m(VO(acaca)₂)/m_diesel?=?0.5?wt%, V(HNO₃)/V(H₂SO₄)?=?1 and T?=?80?°C). The catalytic system could be regenerated six times without significant loss of activity.     

Mathematical modeling of catalytic behavior of catalyst pellets in crude oils after blocking by liquid sulfur

The sulfur recovery unit converts H₂S to elemental sulfur by the Claus process. The process occurs during two combustion and catalytic reactions. Alumina (γ-Al₂O₃) and bauxite (Al₂O₃H₂O) are the main Claus catalysts in crude oils. The volume distribution of micro- and macropores and the parameter of Bethe lattice representing the complex structure of catalyst pellets pores are the most important parameters affecting catalyst performance. This research is aimed at evaluating these parameters impact on effective efficiency of catalyst bed after blocking by liquid sulfur for the second and third reactors. It can be done by considering micro- and macropores as a function of pellet diameter. The results show that pellets with a minimum coordination number or Bethe lattice parameter of 6 are more suitable to use in catalytic reactors. There is a great consistency between the modeling results and the industrial ones. In addition, a catalytic pellet with a diameter of 4.55 mm has the most optimal performance for sulfur recycling processes in industrial crude oil.     

Removal of basic nitrogen compounds from fuel oil with [C4mim]Br/ZnCl2 ionic liquid

Metal-based ionic liquid [C₄mim]Br/ZnCl₂ was synthesized, and its structure was characterized using FTIR spectroscopy and a mass spectrometer. The denitrogenation performance of the ionic liquid was investigated using coker diesel oil as feedstock. Experiment results showed that [C₄mim]Br/ZnCl₂ presented a good denitrogenation performance, obtaining about 94.95% basic N-removal efficiency under the condition with a temperature of 50°C, 1:1 (w/w) IL:oil, extraction time of 30 min. In addition, the basic N-removal efficiency can still reach above 50% at 1:7 IL/oil (w/w) during four recycles of the ionic liquid.     

溶胶-凝胶法固载化离子液体催化剂的表征及烷基苯合成工艺条件优化

采用溶胶-凝胶法制备出固载化离子液体催化剂,表征了催化剂的结构和性质,采用正交实验优选出了使用固载化催化剂合成烷基苯的最佳反应条件。结果表明,固载化离子液体催化剂的大部分孔径为19.5 nm;固载化离子液体催化剂的酸密度为2.145 mmol/g;在固定床反应器中,在n（苯）/n（长链烯烃）为8,温度为200℃,空速为1 h-1,压力为3.5 MPa的最佳反应条件下,烯烃转化率为94.35%。     

吗啡啉磷钨酸盐的合成及其催化氧化脱除汽油中噻吩

以N-甲基吗啡啉、溴代正丁烷和磷钨酸为原料,通过两步法合成了新型离子液体N-甲基-N-丁基吗啡啉磷钨酸盐([Nbmm]_3PW_(12)O_(40)),并对含噻吩的模拟油进行催化氧化脱硫反应。利用1H NMR,FTIR,XRD,TGA等方法对[Nbmm]_3PW_(12)O_(40)的结构进行了分析,考察了其热稳定性和溶解性,优化了模拟油脱硫的反应条件并研究了催化脱硫活性。表征结果显示,[Nbmm]_3PW_(12)O_(40)中存在磷钨酸盐结构,具有良好的热稳定性,仅能溶于强极性溶剂。实验结果表明,[Nbmm]_3PW_(12)O_(40)对含噻吩的模拟油进行脱硫反应时,适宜的反应条件为:脱硫时间3 h、脱硫温度5 0℃、m([Nbmm]_3PW_(12)O_(40))∶m(模拟油)=0.8、m(H2O2)∶m(模拟油)=0.06,在该条件下,模拟油中噻吩的脱硫率能够达到83.29%。[Nbmm]_3PW_(12)O_(40)在催化氧化脱硫反应中具有较好的重复使用性。     

水热合成Cu-Bi2WO6催化剂及用于光催化氧化脱硫的研究

采用水热法合成了可见光催化剂Cu-Bi2WO6,并对其进行X射线粉末衍射(XRD)、紫外-可见漫反射(UV-Vis DRS)表征。以噻吩的正辛烷溶液作为模型化合物,以催化剂的pH值、用量、光照时间、空气流率等工艺条件为考察对象,研究了Cu-Bi2WO6光催化氧化脱除模型化合物中含硫化合物的性能。结果表明,Cu的复合使Bi2WO6的可见光吸收带发生红移,吸收强度也有较大幅度的提高。在中性条件下制备的催化剂活性最高,在空气通入量为300mL/min,催化剂加入量为0.5mg/L时,400W金卤灯照射180min,Cu-Bi2WO6光催化氧化脱硫效果较好,脱硫率可达到97%以上。     

超声波辐照浸渍法制备MnO2/γ-A12O3催化剂及其柴油催化氧化脱硫性能

 分别采用超声波辐照浸渍法和普通浸渍法制备了MnO₂/γ-Al₂O₃催化剂,运用电感耦合等离子体原子发射光谱（ICP-AES）和X射线衍射（XRD）对催化剂进行表征,在空气-异丁醛-MnO₂/γ-Al₂O₃体系中评价其对加氢柴油的氧化脱硫催化性能,并考察了反应温度、异丁醛用量、空气流量、溶剂类型和剂/油体积比对柴油氧化脱硫反应的影响。结果表明,超声波辐照浸渍法制备的MnO₂/γ-Al₂O₃催化剂对柴油氧化脱硫的催化性能明显优于普通浸渍法制备的催化剂。最适宜的催化柴油氧化脱硫反应的条件为：乙腈为溶剂、加氢柴油30 mL、温度35℃、异丁醛20 mmol、空气流量0.06 L/min、超声波辐照浸渍法制备的MnO₂/γ-Al₂O₃催化剂0.08 g、剂/油体积比1/6和催化氧化时间10 min。在此条件下可将柴油硫质量分数从542μg/g 降至31μg/g,柴油脱硫率和回收率分别为94.3%和93.3%。     

Implementation of CPA EoS for simultaneous solubility modeling of CO2 and H2S in ionic liquid [OMIM][Tf2N]

In this study, solubility of pure CO₂ and H₂S and their mixture in [OMIM][Tf₂N] modeled applying CPA EoS. CPA combines the SRK equation with an advanced association term, which is similar to that of SAFT. From a practical point of view, the target in the CPA project was to develop a thermodynamic model capable of describing complex equilibria of mixtures containing polar/associating chemicals through a simple procedure with respect to the SAFT.

The AAD% for binary systems, including H₂S+ IL and CO₂+ IL are 6.81, 5.21 respectively. Moreover, AAD% equal to 13.89 was achieved for the ternary system.     

介孔CuO/SiO2用于汽油氧化-吸附脱硫

 利用[(C₁₆H₃₃) N(CH₃)₃]₃-[PW₁₂O₄₀]双亲催化剂与H₂O₂组成的催化氧化体系对汽油进行氧化后,以介孔SiO₂为载体等体积浸渍法制备的介孔CuO/SiO₂为吸附剂,采用固定床连续流动式吸附脱硫评价装置,考察了CuO/SiO₂的CuO负载量、焙烧温度、焙烧时间和吸附温度对汽油脱硫率的影响,并对介孔CuO/ SiO₂吸附剂性质进行了XRD表征。结果表明,采用在焙烧温度为400℃、焙烧时间为2.0 h、CuO负载量为2%制备的CuO/SiO₂, 在吸附温度为120℃时,汽油氧化-脱硫的脱硫效果较好,汽油脱硫率可达56.82%。     

Optimal activated carbon for separation of CO2 from (H2 + CO2) gas mixture

Seven types of activated carbon were used to investigate the effect of their structure on separation of CO₂ from (H₂ + CO₂) gas mixture by the adsorption method at ambient temperature and higher pressures. The results showed that the limiting factors for separation of CO₂ from 53.6 mol% H₂ + 46.4 mol% CO₂ mixture and from 85.1 mol% H₂ + 14.9 mol% CO₂ mixture were different at 20 C and about 2 MPa. The best separation result could be achieved when the pore diameter of the activated carbon ranged from 0.77 to 1.20 nm, and the median particle size was about 2.07 lm for 53.6 mol% H₂ ? 46.4 mol% CO₂ mixture and 1.41 lm for 85.1 mol% H₂ + 14.9 mol% CO₂ mixture. The effect of specific area and pore diameter of activated carbon on separation CO₂ from 53.6 mol% H₂ ? 46.4 mol% CO₂ mixture was more significant than that from 85.1 mol% H₂ ? 14.9 mol% CO₂ mixture. CO₂ in the gas phase can be decreased from 46.4 mol% to 2.3 mol%–4.3 mol% with a two-stage separation process.     

La-BiVO4催化剂的制备及其光催化还原CO2

为扩展广东惠州炼油厂和石油化工总厂二期工程,中国海洋石油总公司(中海油)选择了CB&I的4项技术。这是CB&I最近在中国的第一项关于电子油门气化技术的授权。电子油门气化技术可用来从煤和石油焦油中制备清洁的合成气体以供发电、制氢和炼油厂蒸汽使用,且可用于煤炭化工工业中制备从肥料到甲醇再到合成天然气的一系列产品。     

The CPA EoS application to model CO2 and H2S simultaneous solubility in ionic liquid [C2mim][PF6]

The CPA EoS was utilized for solubility modeling of pure CO₂ and H₂S and their mixture in [C₂MIM][PF₆]. The model is comprised of SRK EoS in addition to Wertheim's association term. Up to now, several associating models such as SAFT variants have been successfully applied to such systems. Considering the complexity and time consuming nature of SAFT EoSs, CPA can be a good alternative due to its accuracy and simplicity with respect to the SAFT.

The AAD % for binary systems including H₂S+ IL and CO₂+ IL are 11.78, 10.40 respectively. Moreover, the ternary system show AAD% equal to 16.51.     

复合SiO2-WO3催化剂的制备、表征及氧化脱除苯并噻吩性能

 采用溶胶-凝胶法制备了SiO₂-WO₃催化剂,并采用XRD、FT-IR、BET、TG-DTA等方法对催化剂进行表征。以苯并噻吩(BT)为模型化合物,H₂O₂为氧化剂,考察了催化剂的活性元素、制备方法、n(W)/n(Si)和焙烧温度对其催化氧化脱硫活性的影响。结果表明,W的引入降低了SiO₂的比表面积,SiO₂-WO₃催化剂中W的主物相为WO₃。在以W为活性组元,且n(W)/n(Si)为0.1时,500℃焙烧得到的SiO₂-0.1WO₃催化剂具有最好的催化脱硫活性。在模拟油20 mL、催化剂SiO₂-0.1WO₃用量0.04 g、n(H₂O₂)/n(S)为15.9、乙腈/模拟油体积比0.3、65℃反应60 min的条件下,苯并噻吩模拟油脱硫率可达99.3%。