生物质与废轮胎共热解及催化对热解油的影响

生物质稻壳与废轮胎以不同比例组成的均匀混合物在管式固定床内共热解,MCM-41和SBA-15作为催化剂,对产生的热解油性质进行了研究。结果表明,随着废轮胎在混合物中比例增加,热解油产率和热值在增加,而黏度和密度在降低。当稻壳占到60%（质量）时,热解液体产率为44.5%（质量）,热解油热值为40 MJ·kg-1,热值与柴油接近;温度对热解油的产率和组分柠檬精油的生成影响较大。对组成一定的混合物,在热解温度500℃时二者均达到最大。通过对热解油主要组分柠檬精油和氧含量的分析说明,共热解过程中组分间可以产生一定的相互作用,并具有协同效果,体现在柠檬精油组分的含量低于加权后的浓度,氧含量大于加权后的数值;与没有催化剂存在情况相比,MCM-41和SBA-15的存在能显著降低热解液体的黏度和密度,其中,SBA-15的降低效果更为明显。     

The influence of non-carcinogenic petroleum-based process oils on tire compounds’ performance

High aromatic oils which have been widely used as process oils in tire the industry contain high concentrations of polycyclic aromatic hydrocarbons (PAHs). These aromatic compounds (PAHs) have proved to be carcinogenic as well as posing a threat to the environment. Since the beginning of 2010, the use of high aromatic process oils has been banned under the EU regulation 1907/2007 commonly called REACH (registration, evaluation, authorization and restriction of chemicals). The so-called regulation has given rise to challenges to the oil and tire industries in replacing high aromatic process oils with safer alternatives. In the present work, four types of low aromatic petroleum-based process oils, namely mild and high-viscosity naphthenic oils (LNAP and HNAP), treated distillate aromatic extract (TDAE) and mildly extracted solvate (MES), were investigated and their effect on plasticization and durability properties of two different low and high oil-extended tire formulations were evaluated. The compatibility of oils with rubber was investigated as well. The results showed that a number of properties such as abrasion resistance and tire rolling resistance were improved by using non-carcinogenic oils, while tire grip properties were declined. Considering oil–rubber compatibility, TDAE and MES were found to be more compatible with rubbers.     

环保型橡胶填充油的研究进展

环保橡胶油和常规橡胶油最大的区别就在于其多环芳烃(PAHs)含量的不同。详细介绍了PAHs的危害性以及欧盟REACH法规对化学品,尤其是轮胎用橡胶油中PAHs含量的限量要求。提出了探究发展环保橡胶填充油油的必要性;重点介绍了环保型橡胶填充油的研究现状和生产工艺,国内橡胶填充油的生产企业和生产情况。提出应尽快实现环保橡胶填充油的工业化生产以满足应用需求。     

Platinum catalysts supported on hydrothermally stable mesoporous aluminosilicate for the catalytic oxidation of polycyclic aromatic hydrocarbons (PAHs)

Catalytic oxidation of polycyclic aromatic hydrocarbons (PAHs) was studied over platinum catalysts supported on the hydrothermally stable mesoporous aluminosilicate (SM-41). Naphthalene was chosen as a model reactant of PAHs, due to the simplest and the least toxic PAHs. Zeolite seeds crystallization method was used for synthesis of SM-41. Pt/SM-41 catalyst showed higher activity than Pt/MCM-41 for catalytic oxidation of naphthalene in the presence of 10 vol.% water vapor. Hydrothermal stability and hydrophobicity of Pt/SM-41 must be beneficial for the catalytic oxidation of naphthalene in the presence of water vapor.     

Production of aromatic hydrocarbons by co-cracking of bio-oil and ethanol over Ga2O3/HZSM-5 catalysts

The catalytic cracking of bio-oil is important to produce aromatic hydrocarbons, which can partially replace gasoline or diesel to greatly reduce carbon emissions from transportation. To further promote the formation of aromatic hydrocarbons, this work studied the effects of the preparation method and the acid strength of Ga₂O₃/HZSM-5 on catalytic cracking of the bio-oil distilled fraction systematically. The preparation method of Ga₂O₃/HZSM-5 had an important effect on its catalytic activity: the Ga₂O₃/HZSM-5 prepared by physical mixing showed the low dispersion of active phases and poor pore structure, resulting in its insufficient activity and severe coke deposition; the Ga₂O₃/HZSM-5 prepared by precipitation exhibited the higher activity, while many polycyclic aromatic hydrocarbons unfavorable for the subsequent utilization were in the oil phase; the Ga₂O₃/HZSM-5 prepared by impregnation showed the highest activity and 35.5% (mass) selectivity of the oil phase, including 80.3% monocyclic aromatic hydrocarbons and 12.0% polycyclic aromatic hydrocarbons. The Brønsted acidity of Ga₂O₃/HZSM-5 decreased with Si/Al ratio, leading to the decline in reactant conversion, oil phase selectivity and quality. Meanwhile, the polymerization between monocyclic aromatic hydrocarbons and oxygenates was promoted to produce many polycyclic aromatic hydrocarbons and even coke, causing catalyst deactivation.     

热解条件对西湾煤与秸秆流化床加压共热解的影响

在流化床加压热解装置中考察温度、压力、气氛和生物质掺混比等条件对西湾煤与秸秆共热解特性的影响,结果表明:在600℃,0.3 MPa,100%N₂气氛条件下,随着生物质掺混比增加,共热解油产率先增加后降低,实验值均大于计算值;当生物质掺混比为30%(质量分数)时,共热解油的实验值达到最大(16.90%),高于计算值(13.05%);热解压力由常压升至1.0 MPa时,受高氢分压作用下较多的氢分子参与自由基的加氢饱和作用,共热解油产率先增加后降低,在0.3 MPa时共热解油产率达到最大(17.90%);100%(体积分数,下同)N₂,100%CO₂和50%CO₂+50%H₂气氛下的共热解油产率分别为16.73%,16.55%和16.07%;与焦油相比,共热解油的密度变化不大,在元素中碳的质量分数由79.32%降低至71.80%,硫的质量分数由0.60%降低至0.31%,n(H)/n(C)增加;共热解油中脂肪烃、芳香烃和含氧化合物的质量分数降低,酚类组分的质量分数增加,三环及以上的多环产物裂解为小分子化合物,油品质量得到改善。     

生物质与催化裂化油浆共热解协同作用研究

基于生物质焦油氧含量高、品质差的缺陷,本文提出将生物质与重油共转化利用的方法。以催化裂化油浆（FCC）、稻壳（RH）、木屑（PS）为原料,通过低温固定床热解实验对其共热解产物分布进行了研究。结果表明,在FCC的供氢作用下,共热解有利于焦油中含氧化合物的脱除,随着生物质比例增加,反应过程中脱羧基、脱羰基反应减弱,脱羟基反应增强,产物中CO、CO₂产率较计算值增加幅度减小,水的产率较计算值逐渐增大。焦油中烃类物质增加,其中芳香烃以二元环和四元环增加为主,脂肪烃中以C₁₃~C₂₀增加为主。整体上,共热解过程促进了半焦产率的增加,焦油产率虽无明显改变但品质得到了显著提升。     

生物质与催化裂化油浆共热解协同作用研究

基于生物质焦油氧含量高、品质差的缺陷,本文提出将生物质与重油共转化利用的方法。以催化裂化油浆（FCC）、稻壳（RH）、木屑（PS）为原料,通过低温固定床热解实验对其共热解产物分布进行了研究。结果表明,在FCC的供氢作用下,共热解有利于焦油中含氧化合物的脱除,随着生物质比例增加,反应过程中脱羧基、脱羰基反应减弱,脱羟基反应增强,产物中CO、CO₂产率较计算值增加幅度减小,水的产率较计算值逐渐增大。焦油中烃类物质增加,其中芳香烃以二元环和四元环增加为主,脂肪烃中以C₁₃~C₂₀增加为主。整体上,共热解过程促进了半焦产率的增加,焦油产率虽无明显改变但品质得到了显著提升。     

改性介孔分子筛对布洛芬的吸附与控制释放

采用合成后改性将氨基嫁接进介孔MCM41和SBA-15孔道内,对功能化的2种分子筛进行药物吸附与控制释放的研究。利用红外光谱仪(IR)、智能重量分析仪(IGA)等表征手段对吸附剂的物理结构和化学组成进行表征。对药物布洛芬(IBU)的吸附量进行比较,结果表明,氨基改性的MCM41(MCM41-NH2)对布洛芬的吸附性能大...     

锯末快速热解气的在线催化裂解

采用Py-GC/MS装置对锯末进行快速热解并对热解气进行在线检测,研究了HZSM-5分子筛和SBA-15介孔催化剂对热解气进行在线催化裂解的效果。结果表明,热解气经HZSM-5催化裂解后,乙酸、羟基乙醛、呋喃类以及酚类物质的产率都大幅降低,同时形成了大量的芳香烃产物,主要是甲苯和二甲苯;而热解气经SBA-15催化裂解后,乙酸产率降低、羟基乙醛产率稍有降低、呋喃类和酚类物质的产率增加,只检测到了极少的烃类产物。由此可知,这两种催化剂对热解气有着不同的催化裂解效果：HZSM-5具有较好的催化脱氧功效;而SBA-15则基本不具有催化脱氧形成烃类产物的能力,但其介孔结构能够允许生物质裂解过程中形成的分子较大的低聚物进入其中并发生二次裂解,从而形成小分子产物。     

GC/MS内标法测定全钢载重子午线轮胎中的多环芳短含量

介绍轮胎中多环芳烃的危害以及来源,采用气质联用结合内标法测定了不同品牌和规格的全钢载重子午线轮胎主要部位受限制的8种多环芳烃的含量。各部位样品的超声波萃取液经气质联用的选择离子监测模式采集数据后,根据内标法建立的标准曲线计算其中的多环芳烃含量。本方法灵敏、准确、可靠且适用于轮胎中各部位多环芳烃含量的测定。     

Development of micellar solid-phase microextraction fiber based on CTAB-templated mesoporous silica electrochemically assisted self-assembled on wire: Application to chromatographic determination of polycyclic aromatic hydrocarbons

This paper describes the development of a new micellar solid-phase microextraction fiber based on cetyltrimethylammonium bromide-templated mesoporous silica electrochemically assisted self-assembled on copper wire for sensitive determination of polycyclic aromatic hydrocarbons by HPLC. After optimization of experimental parameters, non-polar analytes of PAHs were successfully determined in water samples after microextraction by CTAB/MCM-41 copper fiber as micellar organic platform. The proposed method indicated good linearity in the range 0.01–82.5 µg L^?1 and limits of detection in the range 3–46 ng L^?1. Relative standard deviations of the method were obtained in the range 3.1–8.3%.     

神木原煤萃取产物中多环芳烃含量的研究

对神术原煤分别用苯及石油醚作萃取溶剂进行索式萃取,采用硅胶柱层析纯化,利用气相色谱/质谱联用仪（GC／MS）分别对上述萃取液的硅胶层析产物进行了解折,并对其中的9种多环芳烃（PAHs）进行了定量测定;研究了不同萃取剂所得萃取液中多环芳烃的分布。结果表明,神木原煤中的PAHs以两环、三环和四环PAHs为主,苯萃取液与石油醚苹取液中PAHs的分布大体相同,但在丰度上有很大差别。     

高效液相色谱法测定水源中苯并芘的方法研究

多环芳烃(PAHs)是煤,石油,木材,烟草,有机高分子化合物等有机物不完全燃烧时产生的挥发性碳氢化合物,是重要的环境和食品污染物。本方法是通过对高效液相色谱仪的开发应用,完成生活饮用水/水源水中苯并芘的方法研究,初步建立地下水污染地质调查评价阶段有机污染物测定方法的技术体系。     

生物油蒸馏残渣与废弃塑料催化共热解协同作用的研究

利用热重分析仪和两段式固定床研究了生物油蒸馏残渣(DR)与废弃塑料(MS)的共热解特性,探索了DR与MS混合比、无催化、原位催化及异位催化对产物分布及液相产物化学组分的影响,以及共热解产物的相对选择性与协同作用。结果表明：随着混合比的增加,液相产率呈现增长趋势;相比于无催化,原位催化、异位催化下液相产物中芳烃相对含量增高、含氧化合物相对含量降低。在原位催化下,DR与MS在脂肪族化合物与含氧化合物上表现出的协同作用与异位催化、无催化相反。对于单环芳烃,DR与MS的协同作用参数值大小关系为：无催化>异位催化>原位催化;对于脂肪烃,在DR∶MS=1∶1时,无催化、原位与异位催化下的协同作用参数最大,分别为-20.7%、25.2%、-41.2%;对于脂环烃,在DR∶MS=2∶1时,无催化、原位与异位催化下的协同作用参数最大,分别为184.2%、132.5%、50.0%;对于多环芳烃,DR与MS在不同催化方式下均表现为负协同作用。     

Room temperature blue-green photoluminescence of MCM-41, MCM-48 and SBA-15 mesoporous silicas in different conditions

The photoluminescence (PL) properties of siliceous MCM (MCM-41 and MCM-48) and SBA-15, no Na-containing MCM-41, and modified SBA-15 by silylation were comparatively investigated in dry and damp conditions, displaying the highest PL intensity of MCM-48. The PL intensity of MCM-41 is lower than that of SBA-15 in dry conditions, but reverse in damp conditions. In comparison with that of Na-containing MCM-41, the PL intensity of MCM-41 without Na⁺ is stronger. The PL intensity of modified SBA-15 by silylation is decreased in dry conditions, and however, against moisture and degradation in damp conditions. Twofold coordinated silicon centers in the tested samples are responsible for the blue-green bands at 440 nm. The shoulder peaks around 460–490 nm occurred in damp conditions are assigned to peroxy free radicals.     

YEAR TIME MODULATION OF n-ALKANES,PAH, NITRO-PAH AND ORGANIC ACIDS AT MONTELIBRETTI ROME,ITALY

The organic fraction of airborne particulates was investigated at Montelibretti RM, Italy, over 12 months and n-alkanes, polycyclic aromatic hydrocarbons, nitrated polycyclic aromatics and aliphatic acids were evaluated. The year time modulations were acquired from all groups of compounds, both in quantitative (cumulative concentrations) and qualitative (percent compositions) terms. Some distribution indexes and diagnostic ratio rates drawn from congener abundances provided information about the twin nature (anthropogenic and biogenic) of sources of organic particulate. Briefly, unlike past decades the appearance of the Montelibretti location was that of a site affected overall by local pollution, as a consequence of both direct anthropogenic emissions and secondary oxidized compounds. The occurrence of polycyclic aromatic hydrocarbons (PAHs) seemed to depend overall upon vehicle emission (diesel powered in particular), although a second, unknown source with year time modulation was present, apparently not associated with biomass/wood burning. By contrast, nitro-PAHs were mainly associated to oxidation of parent PAHs. In summer, PAHs were found at concentrations similar to those measured in 1993–1995, whilst in winter they were three times more abundant than previously reported.     

Mesoporous silicas containing carboxylic acid: Preparation,thermal degradation,and catalytic performance

The calcination and thermal degradation behaviors of surfactants in mesoporous silicas SBA-15 and MCM-41 were investigated by FT-IR, ¹³C CP/MAS NMR, TG/DTA, and GPC. It was found that carboxylic acid-containing products were generated as active components in the mesopores of SBA-15 and MCM-41 from the triblock copolymer (PEO)₂₀(PPO)₇₀(PEO)₂₀ and cetyltrimethylammonium bromide (CTAB), respectively; the latter materials were used as templates. The carboxylic acid-containing mesoporous silica obtained showed a catalytic activity for hydrolysis of sucrose. The acidity was evaluated by means of NaOH titration. The acidity sensitively depended on both the calcination temperature and the atmosphere; the maximum appeared at 150 °C in air for SBA-15 where the highest activity was observed. However, the product in MCM-41 showed a lower catalytic activity than that in SBA-15. The SBA-15 product was easily leached from the mesopores of SBA-15 into the solution, but the degree of leaching for MCM-41 was considerably smaller than that for SBA-15.     

Co-pyrolysis of soybean soapstock with iron slag/aluminum scrap,and characterization and analysis of their products

Soybean soapstock(SS) is one of the main solid wastes produced in the refinery of edible oil processing. In this study, the co-pyrolysis of SS with iron slag(IS) and aluminum scrap(AS) was carried out in a tubular furnace. The gas, liquid and solid products were characterized and the char yield decreased with increasing IS/AS ratio. IS and AS can improve the gas yield, and when the ratio of SS/IS was 1:0.25, the total pyrolysis gas and hydrogen contents were significantly increased. The content ...     

轮胎中多环芳烃的检测技术

概述欧盟2005／69／EC指令【多环芳烃（PAHs）指令】和欧盟REACH法规对轮胎中有PAHs含量的限制。介绍气相色谱、气相色谱一质谱、高效液相色谱、液相色谱一质谱和核磁共振等检测方法在PAHs检测中的应用。分析核磁共振检测PAHs的特点和ISO21464：2012与ISO21464：2009中核磁共振检测方法的差异,提出我国轮胎企业应采用与欧盟环保法规同步的核磁共振法检测PAHs。