催化裂化烟气脱硫、脱氮吸附剂的初步研究

 在微型连续床式反应装置上,考察了催化裂化催化剂吸附烟气中 SO₂、NO_x的性能。当SO₂、NO_x的体积分数分别为1800和1900 μL/L、反应温度为220℃、微正压操作时,新鲜吸附剂90%的SO₂脱除率维持在140~200s,70%的NO_x脱除率维持在220~470s;吸附容量为11.4~16.2 mg/g。SO₂、NO_x与吸附剂以物理吸附和化学吸附方式相作用;吸附运转剂表面的S和N分别以SO^2-₄和 NO^-₃存在。     

硅酸锆负载壳聚糖吸附废水中铅离子的工艺研究

以颗粒状硅酸锆(ZrSiO4)作为载体,通过浸渍的方法将壳聚糖负载其上,制得壳聚糖-ZrSiO4吸附剂。用该吸附剂处理废水中的铅离子(Pb2+),考察了体系pH值、温度、时间等工艺条件对吸附和脱附效果的影响。结果表明,在Pb2+溶液初始质量浓度为5.0 mg/L,pH值为6.0,吸附剂用量为24.0 g/L,吸附温度为30℃,吸附时间为1 h的优化条件下,该吸附剂对溶液中Pb2+的最大吸附率为86.4%,相应其最大吸附容量为180.1μg/g;用去离子水洗涤壳聚糖-ZrSiO4饱和吸附剂,调节脱附体系pH值为2.0,在10℃震荡10 min,该吸附剂对Pb2+的脱附率可达93.5%。     

Fe 3+x-TiO2/Shell光催化剂的制备及其对石油的光催化降解

 以自制的贝壳基规整吸附体为载体,采用浸渍煅烧法制备了Fe ³⁺_x-TiO₂/Shell光催化剂。采用XRD、SEM-EDS和UV-Vis等技术对制备的Fe ³⁺_x-TiO₂/Shell光催化剂进行表征。以石油为降解对象,考察了Fe³⁺掺杂量、Fe ³⁺_x-TiO₂/Shell的负载次数及光照时间对Fe ³⁺_x-TiO₂/Shell光催化活性的影响。结果表明,Fe³⁺掺杂量为0.7%(m(Fe³⁺ )/m(TiO₂)×100%)、Fe ³⁺_0.7-TiO₂负载次数为4次时,制备的Fe ³⁺_0.7-TiO₂/Shell光催化剂的光催化活性最高,300 W碘钨灯照射16 h,石油的光催化降解率达76%。     

改性蒙脱土与壳聚糖复合吸附剂制备及对Cu2+吸附性能评价

以壳聚糖和改性蒙脱土为原料,制备了改性蒙脱土与壳聚糖复合吸附剂.考察了复合吸附剂用量、显色剂双硫腙用量、溶液pH、反应温度及反应时间对Cu2+吸附率的影响.结果表明,在复合吸附剂用量0.4 mL,吸附时间30 min,显色剂用量1.5 mL,溶液pH 5.5～6.5,cu2+浓度(o.1～0.5)×10-3mg·mL-1,反应温度60℃的条件下,复合吸附剂对Cu2+的吸附率可达90%以上.     

阳离子对 HPAM/Cr3+弱凝胶性能的影响

为揭示相同价态阳离子对弱凝胶成胶性能的影响规律, 研究了 Mg²⁺、 Ca²⁺、 Na⁺、 K⁺四种常见阳离子对部分水解聚丙烯酰胺（HPAM） /Cr³⁺弱凝胶成胶黏度和稳定性的影响。结果表明, 阳离子浓度过低或过高均会抑制HPAM/Cr⁺体系的成胶; HPAM质量浓度为3 g/L时, 利于HPAM成胶的单一阳离子浓度适宜范围分别为Mg²⁺ 0.4～9 g/L、 Ca²⁺ 1.2～18 g/L、 Na⁺ 9～30 g/L、 K⁺ 16～55 g/L; 阳离子半径越小、 对凝胶成胶黏度和稳定性的影响越大; 四种阳离子对弱凝胶成胶黏度的影响顺序为Mg²⁺>Ca²⁺>Na⁺>K⁺, 对弱凝胶稳定性的影响顺序为Mg²⁺>Ca²⁺、 Na⁺>K⁺。图3参12     

Na+质量浓度对三元复合体系的影响

 阳离子对三元复合体系(表面活性剂+聚合物+NaOH,alkaline/surfactant/polymer,简称ASP)的性能影响较大。在纯水配制的三元复合体系中,利用NaOH和NaCl的质量分数来调节其中Na⁺的质量浓度,考察三元复合体系中Na⁺质量浓度对体系黏度及其与原油之间油-水界面张力的影响。结果表明,三元复合体系中Na⁺质量浓度达到较高值时,三元复合体系黏度就不再变化。在三元复合体系中,无论是NaOH质量分数高而NaCl质量分数低,还是NaCl质量分数高而NaOH质量分数低,只要体系中Na⁺质量浓度在5200~7700 mg/L,就能与原油形成超低油 水界面张力,这是三元复合体系Na⁺质量浓度的变化导致表面活性剂分子在油-水界面上的吸附发生变化的结果。     

稀土元素对Cu~+-13X分子筛吸附2,5-二甲基噻吩和苯并噻吩的影响

采用离子交换法制备了Cu~+-13X及负载稀土元素Ce的Cu~+-13X分子筛(Ce/Cu~+-13X)吸附剂,分别从静态吸附平衡及动力学测试两方面考察了两种吸附剂对2,5-二甲基噻吩和苯并噻吩的吸附性能;分别采用Langmuir模型和修正的Langmuir模型对单、双组分静态吸附平衡数据进行拟合,采用Crank单孔扩散模型对动力学数据进行拟合。拟合结果表明,数据与模型吻合均很好。计算得到了Ce/Cu~+-13X吸附剂对2,5-二甲基噻吩和苯并噻吩单组分的最大吸附量分别为165.1,193.0 mg/g,分别大于Cu~+-13X吸附剂对2,5-二甲基噻吩和苯并噻吩的最大吸附量(153.6,180.2 mg/g)。负载稀土元素对Cu~+-13X吸附剂的吸附性能有一定的促进作用,能够减弱2,5-二甲基噻吩和苯并噻吩之间的竞争吸附。     

适用于酸性高密度压井液的缓蚀剂WX1A的制备与性能研究

为减小以提盐废卤为基液制备的酸性高密度无固相压井液的腐蚀性,以二乙醇胺、甲醛和苯乙酮为原料采用正交实验法制备了一种适用于该类压井液的醛酮胺类缓蚀剂WX1A,利用失重法、电化学分析和SEM扫描电镜研究了该缓蚀剂对N80、P110 钢片在压井液（以pH为3 的普钙老水制备的酸性高密度无固相压井液）中不同条 件下的缓蚀效果。结果表明：在二乙醇胺、甲醛、苯乙酮摩尔比1.2:2:1.2,反应温度110℃,反应时间10 h,反应pH1 条件下合成的缓蚀剂WX1A的缓蚀效果最佳;该缓蚀剂的最佳用量为80 mg/L,在此加量下,当温度从60℃升至80℃,缓蚀剂WX1A对N80 钢片和P110 钢片的缓蚀率从87.07%和88.09%分别增至93.12%和92.62%;在密度1.6、1.7、1.8 g/cm³ 的压井液中,缓蚀剂WX1A 对N80 钢和P110 钢片的缓蚀率均在90%上,在120℃、2 MPa 和150℃、4 MPa条件下缓蚀剂WX1A在密度1.6 g/cm³的压井液中对N80 和P110 钢片的缓蚀率均达到94％以上。压井液中添加该缓蚀剂后,缓蚀剂通过吸附在金属基体表面形成较为完整的保护膜,自腐蚀电流密度从10^-4 A/cm²降低到10^-5A/cm²,降低了压井液对普通碳钢的腐蚀性。图5 表7 参16     

负载型杂多酸的制备、表征及其对煤焦油的脱氮性能

采用等体积浸渍法制备了3种负载型杂多酸吸附剂,通过傅里叶红外光谱、N_2吸附-脱附(BET)对吸附剂进行了表征。以煤焦油为原料,硅胶负载杂多酸为吸附剂,考察了不同条件对煤焦油脱氮率的影响,分别应用拟一阶、拟二阶动力学模型、Freundlich吸附等温方程和Langmuir吸附等温方程对实验数据进行了拟合。结果表明,在磷钨酸负载质量分数为30%、吸附温度为60℃、吸附时间为50min、剂油质量比为1∶5的条件下煤焦油的脱氮率为85.7%。吸附过程符合准二级动力学模型,吸附剂对碱性氮化物的理论平衡吸附量为qe′=7.161mg/g,Langmuir吸附等温式的拟合度较好,吸附作用为单分子层吸附。     

超声法制备介孔TiO2及组合技术脱硫

 以钛酸丁酯为钛源、十六烷基三甲基溴化铵（CTAB）为模板剂,在超声波强化作用下制备介孔TiO₂,并采用XRD、FT-IR、TG-DTA、UV-Vis、TEM和EDX分析手段对所得样品进行表征,以苯并噻吩为模型化合物,考察其光催化氧化脱硫性能。结果表明,在450℃下焙烧2 h、n(TiO₂)/n(CTAB)=1/0.04的条件下,可得到球形粒子状、颗粒分布均匀、紫外光吸收边为387 nm、禁带宽度为3.32 eV、晶粒粒径6.93 nm、平均孔径3.21 nm、比表面积147.134 m²/g、孔容0.259 cm³/g的锐钛矿型介孔TiO₂。在催化剂用量15 mg、H₂O₂作为氧化剂、n_S/n_O=1/200、萃取剂甲醇5 mL、吸附时间40 min、20℃反应3 h的条件下,对5 mL苯并噻吩石油醚溶液的脱硫率为98.62%。     

A novel La3+–Zn2+–Al3+–MoO42− layered double hydroxides photocatalyst for the decomposition of dibenzothiophene in diesel oil

A new type of photocatalyst, La³⁺-Zn²⁺-Al³⁺-MoO₄^2? layered double hydroxide (LDH) (La:Zn:Al = 1:7:2), was prepared by a complexing agent-assisted homogeneous precipitation technique. The LDHs were used as catalysts for the desulfurization of diesel oil under UV irradiation. As revealed by the results, the catalyst showed superior desulfurization efficiency and recycling performance. Under UV irradiation, the desulfurization efficiency was 84% in 60 min. In La³⁺–Zn²⁺–Al³⁺–MoO₄^2? LDHs, the introduction of MoO₄^2? increased the interlayer space for promoting the adsorption of dibenzothiophene, and MoO₄^2? might act as the active sites for the oxidation of dibenzothiophene, resulting in the high desulfurization efficiency.     

硅-铝催化剂酸中心失活与再生的分析

含 Si、Al 元素的固体酸催化剂,其活性来源于其酸性,催化剂的失活与再生一定程度上是其酸性中心的失活与再生。L酸中心具有吸引孤对电子的空轨道,空轨道是L酸中心的活性中心;B酸中心能提供 H⁺,H⁺是B酸中心的活性中心。L酸中心的空轨道被孤对电子占据后,L酸中心失去活性,B酸中心给出 H⁺后也会失去活性。烯烃在L酸中心作用下生成了环正碳离子,环正碳离子从失活的L酸中心获取H^-生成了环烷烃,而失活的L酸中心在给出 H^-的同时,占据活性中心的1对电子被去掉,变成为空轨道,这样L酸中心又具有吸引孤对电子的能力,又恢复了活性。如果环正碳离子提供 H⁺给失活的B酸中心,C⁺与相邻的提供 H⁺的C原子各自的2个sp³轨道相互作用形成-C=C-双键,即生成了环烯烃,使失活的B酸中心再次获得 H⁺后其活性也得到了恢复。     

MANAGEMENT OF COAL MACERALS IN THE LIQUEFACTION OF LOW RANK COALS

ABSTRACT

Three Alberta subbituminous coals were selected to investigate the contribution of different macerals to liquefaction. These coals represent the full range of geographic, rank and geological variations present In the Alberta Plains Coal Region. In addition, for comparison, two U.S. lignites (Texas and North Dakota) were included in these investigations. To enhance maceral concentration, density fractionation was carried out on these samples. Though liquefaction yields appear to increase with increase in vitrinite (huminite) content, a clear-cut correlation between conversion and maceral content is not established because of (a) uncertain behaviour of semi-inert macerals and (b) differences in behaviour within the vitrinite (huminite) macera1 group.     

Prediction of Caged Polyaza Polynitroamine (Tetracyclo-HMX) as Energetic Compound

By fusing four HMX rings into a cage, a powerful nitroamine explosive was predicted. The heat of formation (HOF) of hetero pentacyclo-icosane nitro compound of dodecanitrododecaza-pentacyclo[9.5.1.1^3,9. 1^5,15. 1^7,13]icosane (DNDAPI or, alternatively, tetracyclo-HMX) was obtained by using density functional theory B3LYP method with 6-31G? basis set. The isodesmic reactions designed for the evaluation of HOF keep most of the basic ring structures of the title compounds and thus ensure the credibility of the result. The value of HOF is 1394.59 kJ/mol. The predicted detonation velocity of the title compound is 10.6 km/s and detonation pressure is 56.8 GPa, even at 90% of its theoretical density. These values are much larger than those of the widely used 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX), indicating that DNDAPI is a promising candidate of high energy material. The dissociation energy for the N-NO₂ bond in the cage skeleton of the title compound is 125.36 kJ/mol.     

Effect of Severity on Hydrotreating of Demetallized Oil Monitored by 1H-NMR Spectroscopy

Abstract

A study on aromatic hydrogenation of demetallized oil has been carried out using a commercial catalyst under pilot plant reaction conditions similar to those found in industrial processes. The feedstock was contacted with the catalysts in a trickled bed reactor unit at 330°C, 350°C, and 370°C. A combination of physicochemical characterization of feed and products and ¹H-NMR spectra was used to monitor changes in the aromatic fractions caused by variation in reaction temperature. Analysis of the ¹H-NMR spectra, along with the quantitative variation in the areas of the resonance lines, showed that the diaromatics with relatively long alkyl changes present in the lightest distillation cuts of the products were highly hydrogenated. In contrast, smaller changes in aromaticity in the heaviest fractions were observed under the same conditions. A limit of about 2 wt% of the integrals corresponding to the diaromatic+ species suggests a thermodynamical limitation of hydrogenation under the studied reaction conditions.     

4,10-Dinitro-2,6,8,12-tetraoxa-4,10-diazatetracyclo[5.5.0.05,903,11]dodecane Synthesis

4,10-Dinitro-2,6,8,12-tetraoxa-4,10-diazatetracyclo[5.5.0.0^5,90^3,11]dodecane (TEX) was obtained by nitrolysis of 1,4-diformyl-2,3,5,6-tetrahydroxypiperazine reaction using a mixture of fuming nitric acid and concentrated sulfuric acid. The optimal process temperature was 54–56°C. The yield of the synthesis depends inter alia on the rate the reactants are introduced into the reaction medium and on the time of conditioning of the reaction mixture. A maximal yield of ca. 40% was achieved at the reactant addition time of 2 h and conditioning time of 2 h. None of the other nitrating mixtures examined proved superior to the conventional nitrating mixture. The product was examined by high-performance liquid chromatography (HPLC), nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR), and differential scanning calorimetry (DSC) techniques and the results are reported.     

Effects of low-salinity water coupled with silica nanoparticles on wettability alteration of dolomite at reservoir temperature

Wettability alteration in porous media is one of the mechanisms for enhancing oil recovery through injecting low-salinity water into carbonate reservoirs, in which active ions can remove the carboxylic oil component from the rock surface, altering the rock's wettability toward a water-wet condition. This study investigated the concomitant effects of low-salinity water and hydrophilic SiO₂ nanoparticles on oil-wet dolomite rock. Results revealed that low-salinity water coupled with hydrophilic nano-SiO₂ in oil-wet dolomite rock remarkably affected the wettability alteration of the rock, showing that the simultaneous presence of ions in water and hydrophilic nano-SiO₂ led to considerable wettability alteration compared with using just low-salinity water.     

Research on paleo-fluid sources and hydrocarbon preservation conditions in marine carbonates in the central Yangtze, China

87Sr/86Sr,δ18O andδ13C ratios of calcite,dolomite,gypsum filling vugs and fissures in marine carbonates and their host rocks from the Sinian to the middle Triassic,are employed to trace the possible source and migration path of key fluids related to development of hydrocarbon,hydrocarbon preservation condition are then discussed further.Comprehensive research,based on the paleo-fluid,the property of formation water and the deformation intensity etc.,indicates that the preservation conditionsin the Shizhu synclinorium zone and Fangdoushan anticlinorium zone are the most predominant in the central Yangtze.Three sets of fluid systems in the Shizhu synclinorium zone are identified.Little fluid exchange occurs between the upper-middle fluid system and the lower fluid system,so two independent preservation units have developed.Both the Permian and the Triassic in the upper preservation unitsand the Dengying Formation of the Sinian and the lower Cambrian in the lower preservation units havegood preservation conditions.The preservation condition in the lower association(Z-S)located in the Huaguoping synclinorium zone in the western Hubei and Hunan is better than that in other tectonic units,where the fluids in the lower association migrated vertically across strata when the fluid isolating intervalswere destroyed,the regional seals are absent and the conditions for the preservation of hydrocarbon accumulations are totally destroyed.The preservation condition is increasingly more favorable from the western Jiangxi and Hunan to the western Hubei&eastern Chongqing on the whole.     

定量核磁共振氢谱法测定苄基喹啉季铵盐产品中二聚体的含量

目的 苄基喹啉季铵盐(BQC)是一种常用的酸化缓蚀剂，其合成中的副产物苄基喹啉季铵盐二聚体(BQD)被发现对金属腐蚀具有更高效的缓蚀作用。为了明确合成产物中BQD的有效含量，建立了测定BQD含量的定量核磁共振氢谱法。方法 通过合成并提纯得到了BQD,使用元素分析、质谱、核磁、红外等手段对其结构进行表征；以氘代氯仿作溶剂，选择化学位移在δ 12附近的BQD单峰和化学位移在δ 5附近的内标物二溴甲烷的单峰作为定量峰，根据两峰的面积之比，计算得到产物中BQD的有效含量。结果 合成产物中BQD质量分数为11.6%,与加入BQD纯品的比对实验结论基本一致。结论 建立的核磁共振氢谱内标法是一种简便、快捷、结果可靠的BQD含量检测方法。