添加硫沥青球炭化机理的研究

通过元素分析、气相色谱（GC）及热重分析（TG－DTG）等方法,对不熔化添加硫沥青球的炭化过程进行了研究,并且对比了不添加硫沥青球的炭化情况。结果表明：在450～550℃范围内,添加硫沥青球中的硫主要以H2S的形式脱除,同时生成部分COS（400～550℃）及微量的CS2（400℃）。添加硫沥青球的炭化缩聚反应在400℃反应速率最大。     

添加硫促进沥青球的不熔化

制备了不同硫含量的各种粒级的添加硫沥青球,并且选择合适的工艺条件进行氧化稳定化处理,结果表明：硫的添加能有效地促进沥青球的不熔化,缩短不溶化时间,对于０．６～１．０ｍｍ的沥青球,添加硫后使其不熔化时间由原来的３０ｈ以上缩短到３．１ｈ。     

沥青球在流化床反应器中氧化不熔化及后续炭化行为的研究

用流化床反应器对沥青球进行了氧化不熔化处理,考察了不同温度下沥青球的氧化行为及其后续炭化行为。采用热重分析仪、傅里叶变换红外光谱仪、元素分析仪及扫描显微镜对氧化沥青球和炭化球进行了表征。结果表明:流化床反应器强化了沥青球氧化不熔化的传热和传质过程,在0.21 m/s的临界流态化气速下,以0.5℃/min快速升温至300℃进行沥青球的不熔化处理,得到具有良好表面形貌和球形度的氧化沥青球及其炭化球,极大改善了沥青球制备过程中氧化不熔化的耗时、耗能问题。     

煤沥青球的氧化不熔化过程特性

氧化不熔化过程是煤沥青基球状活性炭制备中的核心工艺,对其过程特性和动力学机理的认识是实现氧化过程工艺优化的关键。本文以煤沥青萃取球为原料,通过实验研究,重点探讨了粒径范围、升温速率和氧化温度对其氧化不熔化过程的影响,并确定氧化动力学参数及其反应机理函数。结果表明：氧化不熔化过程可分为轻组分热解、初步氧化、氧化增重和恒温氧化失重4个阶段。煤沥青球经过氧化不熔化后,C、H含量减少,O含量增加,表面光滑平整。减小粒径并选取合适的升温速率（0.25～0.5℃·min^-1）以及氧化温度（275～325℃）,更有利于氧化不熔化快速稳定地进行。粒径范围为0.3～0.6 mm的煤沥青球在升温速率为0.5℃·min^-1、氧化温度为300℃的条件下活化能最小,各个阶段的值分别为83.34、293.19、302.25和357.05 kJ·mol^-1。     

煤焦油沥青纤维的不熔化过程研究

以硫化法制得的高软化点（２５５ ℃） 煤焦油沥青为原料,通过熔融纺丝、氧化不熔化及炭化处理制备煤焦油基沥青纤维。探讨了不熔化终温对产品炭纤维抗拉强度的影响,借助于元素分析、气相色谱分析（ＧＡ）、ＤＴＡ、ＴＧ 和红外光谱分析等表征手段,对沥青纤维的不熔化过程进行了研究。结果表明：氧化终温强烈影响着炭纤维的抗拉强度;煤焦油沥青纤维在空气中的不熔化过程在低于３４０ ℃时表观上表现为恒重恒热,氧化反应主要发生于２００～３４０ ℃之间。     

沥青球的空气氧化稳定化反应特性研究

用 TGA、 DTG和 DTA法研究了石油沥青球和煤沥青球在空气中的热反应特性,研究了沥青球氧化稳定化的反应特点及其与沥青球组成与结构的关系。结果表明：石油沥青球由于与氧气的反应活性较强,更难于不熔化;增加萘含量和提高原沥青的软化点有利于沥青球的不熔化。     

含硫天然气集输过程颗粒沉积机理与控制

针对我国含硫天然气集输过程中出现的硫颗粒沉积问题,对硫沉积来源、沉积机理以及科学防控措施进行了相关调研,为含硫天然气集输过程中的硫颗粒沉积防治提供借鉴。酸性气田开发中的硫沉积带来了广泛的井筒及管道设备堵塞、减产以及腐蚀问题。井筒硫沉积来源主要为含硫物质如多硫化物发生化学反应生成硫单质,及酸性天然气中溶解的硫单质随着输送中压力下降过程析出。集输管道中的硫沉积机理更为复杂。通过采用合理配产和局部优化改造等措施可减缓井筒和地面设施的硫沉积现象。当严重硫堵时采用加注硫溶剂、局部加热等方式进行清堵作业。     

沥青球空气氧化不熔化的研究

采用空气氧化实现了０．１５４～１．００ｍｍ范围四种球径沥青球的不熔化。并应用差示扫描量热法ＤＳＣ谱图表征沥青球的不熔化程度。概述沥青球空气氧化增重和炭化收率间的关系，应用红外光谱初步探讨了沥青球空气氧化不熔化的机理。     

稀土配合物二硫代氨基甲酸盐类的合成及其性能研究

随着现代有机合成技术的提高，新的含硫有机配体不断涌现，化学家们合成了大量结构新颖的稀土含硫配合物。这类化合物往往具有良好的生物活性、橡胶硫化促进性能及摩擦学性能，在生物、材料及工业应用方面具有潜在的应用前景。对稀土配合物配体二苄基二硫代氨基甲酸钠（NaDBTC）及其（INd（DBTC）3（HMPA）2]）的合成进行了研究。     

沥青球在空气中的不熔化及炭化

以空气为氧化介质，以０．５℃／ｍｉｎ的升温速度，在不同氧化终温及氧化时间下，对沥青球进行不熔化处理。利用元素分析及红外光谱研究了不熔化过程及其对炭化性质的影响；并利用ＴＧ－ＤＴＧ分析了沥青球的炭化过程。     

Influence of organic sulfur compounds and metals on mesophase formation

The influence of organic sulfur compounds and metals on the texture of the mesophase formed in pitch during the carbonization process was investigated by the addition of organic sulfur compounds and organometallic compounds to the cracked oil obtained from Khafji asphalt and polyvinyl chloride (PVC) pitch. These pitches, containing sulfur and metals, have been examined by polarised light microscopy, and quinoline insolubles (QI), sulfur and metal contents were determined. The existence of either organic sulfur compounds or organometallic compounds in the pitch has no effect on mesophase texture. However, the coexistence of sulfur and metals (such as vanadium or nickel) has a great effect on mesophase texture. From these results, sulfur and metals coexisting in the pitch have a catalytic effect which activates the thermal decomposition and the thermal polymerization reactions of the pitch. Furthermore, the precursors of mesophase (β resin) are formed abundantly in the pitch by these reactions. These precursors promote the nucleation of mesophase spherules, and a large number of mesophase spherules are formed in the pitch at the same time. Therefore, these spherules coalesce with each other before growing to large spheres and lead to a fine mosaic texture.     

Shell-Paques生物脱硫技术及其应用

Shell-Paques技术是具有代表性的生物脱硫及硫回收工艺,其采用脱氮硫杆菌并使之在弱碱性溶液条件下吸收H2S,从含硫酸性气中脱除H2S,并在自然产生的微生物及空气的作用下,将所吸收的硫化物氧化成元素硫。该技术具有净化效率高、适应范围广、操作维护方便、环保效益好、副产生物硫磺等特点,可用于合成气、天然气、炼厂气等含有H2S的酸性气的净化过程。介绍了Shell-Paques生物脱硫技术的基本原理、工艺流程、技术特点及其在国内外的应用概况。     

Sulfur Nanoparticles Synthesis and Characterization from H2S Gas, Using Novel Biodegradable Iron Chelates in W/O Microemulsion

Sulfur nanoparticles were synthesized from hazardous H₂S gas using novel biodegradable iron chelates in w/o microemulsion system. Fe³⁺–malic acid chelate (0.05 M aqueous solution) was studied in w/o microemulsion containing cyclohexane, Triton X-100 and n-hexanol as oil phase, surfactant, co-surfactant, respectively, for catalytic oxidation of H₂S gas at ambient conditions of temperature, pressure, and neutral pH. The structural features of sulfur nanoparticles have been characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), energy dispersive spectroscopy (EDS), diffused reflectance infra-red Fourier transform technique, and BET surface area measurements. XRD analysis indicates the presence of α-sulfur. TEM analysis shows that the morphology of sulfur nanoparticles synthesized in w/o microemulsion system is nearly uniform in size (average particle size 10 nm) and narrow particle size distribution (in range of 5–15 nm) as compared to that in aqueous surfactant systems. The EDS analysis indicated high purity of sulfur (>99%). Moreover, sulfur nanoparticles synthesized in w/o microemulsion system exhibit higher antimicrobial activity (against bacteria, yeast, and fungi) than that of colloidal sulfur.     

In situ plasma diagnostics of the chemistry behind sulfur doping of CVD diamond films

Microwave plasma enhanced chemical vapour deposition (CVD) has been used to grow sulfur doped diamond films using a 1% CH₄/H₂ gas mixture with various levels of H₂S addition (100–5000 ppm), upon undoped Si substrates. X-Ray photoelectron spectroscopy has shown that S is incorporated into the diamond at number densities (≤0.2%) that are directly proportional to the H₂S concentration in the gas phase. Four-point probe measurements showed the resistivity of these S-doped films to be a factor of three lower than undoped diamond grown under similar conditions. Sulfur containing diamond film was also obtained using a 0.5% CS₂/H₂ gas mixture, although the high resistivity of the sample indicated that the sulfur had been incorporated into the diamond lattice in a different manner compared with the H₂S grown samples. Molecular beam mass spectrometry has been used to measure simultaneously the concentrations of the dominant gas phase species present during growth, for a wide range of H₂S doping levels (1000–10 000 ppm in the gas phase). CS and CS₂ have been detected in significant concentrations in the plasma region as a result of gas phase reactions. Additional measurements from a 1% CS₂/H₂ plasma gave similar species mole fractions except that no CS was detected. These results suggest that CS may be the first step toward CS bond formation in the film and thereby a pathway allowing S incorporation into diamond. Optical emission spectroscopy has shown the presence of S₂ in both gas mixtures, consistent with the observed deposition of sulfur on the cool chamber walls.     

锰系可再生高温脱硫剂的制备及其性能测试

煤气的高温脱硫净化是 IGCC 和 DRI 生产的瓶颈,直接影响整个过程的热效率。在50℃、pH值约为9的条件下采用硝酸锰、硝酸铝混合溶液与氨水进行共沉淀,制备了锰含量不同的脱硫剂,在固定床反应器中考察了脱硫剂的硫化及再生性能,并利用XRD、SEM、BET等手段表征了脱硫剂在硫化/再生过程中的物相和结构变化。共沉淀法制备的脱硫剂Mn/Al分散性好,在850℃高温下进行脱硫反应可以定量快速进行。脱硫硫容与脱硫剂锰含量呈正比,Mn-S/Mn-O交换原子比在0.90~0.95之间,改变空速和进口H₂S含量并不改变脱硫硫容。采用O₂浓度为3%的稀释空气在850℃下再生,再生后的硫容稳定,说明所制备的脱硫剂可用于高温可再生脱硫。     

催化裂化烟气硫转移剂的研究现状

催化裂化烟气硫转移剂的发展历史悠久,通过将烟气中的SOx转换成H2S,不仅能降低烟气中SOx的排放,还能将其进一步制成硫磺,变废为宝。综述了国内外催化裂化烟气硫转移剂的技术进展,重点介绍了镁铝尖晶石型硫转移剂发展以及应用情况,指出了其存在的问题及发展方向。     

Structure of K2Co3-loaded activated carbon fiber and its deodorization ability against H2S gas

Coal tar pitch containing finely dispersed KOH was spun centrifugally, followed by stabilization through heating to 330°C under a (1:1) mixture of air and CO₂ and carbonization/activation by heating to 850°C under CO₂. The activated carbon fiber obtained possessed of a specific surface area of 491 m²g⁻¹ and contained ca. 2% of K as K₂CO₃ over the peripheral region of fiber. The fiber showed high deodorization ability against 30 ppm of H₂S gas in air at ambient temperature. H₂S gas did not diffuse to the most interior parts of the fiber and was oxidized around outer regions of the fiber. Elemental sulphur was deposited in the fiber after H₂S absorption. The deodorization mechanism was discussed. The role and action of the K₂CO₃ supported was explained.     

Catalyst modification and process design considerations for the oxidation of low concentrations of hydrogen sulfide in natural gas

Low concentrations of hydrogen sulfide (H₂S) in natural gas can be selectively oxidized over an activated carbon catalyst to elemental sulfur, water and a small fraction of sulfur dioxide (SO₂). Efforts to improve catalyst performance and product sulfur quality have been made by a) modification of the catalyst composition b) removal of the heavy hydrocarbons from the feed and c) choice of reaction conditions. The use of a guard bed to absorb heavy hydrocarbons and operation at elevated pressures show positive results. A preliminary flow diagram incorporating these findings has been prepared for a small commercial unit capable of processing sour natural gas containing 1.0% H₂S.     

高含硫气藏地层物性对硫沉积影响机理模拟研究

高含硫气藏属于一类特殊气藏。开发过程中,常有硫沉积现象。硫沉积将降低地层孔隙度和渗透率,影响气井的产能,严重的硫沉积甚至会导致气井报废。引入空气动力学中描述气固流动的理论,建立了描述硫微粒运移的动力学模型和描述微粒沉降的携带微粒临界气流速度模型。以上述两模型为基础,并考虑沉积的硫微粒对地层孔隙度和渗透率的影响,建立了高含硫气藏硫微粒运移沉积数学模型。利用该模拟研究了地层物性对硫沉积的影响机理。在定产量生成的情况下,孔隙度越高,硫微粒的沉积速度越慢;渗透率越低,硫沉积速度越快。因此,致密的高含硫气藏中硫沉积是影响气藏开发的重要因素,合理制定气藏开采速度、防止硫沉积是低孔、低渗高含硫气藏高效开发的关键。