工艺条件对煤液化油中酚类化合物的影响研究

煤炭直接液化油中含有种类丰富且数量可观的酚类化合物,研究影响酚类含量和组成的因素,对于深入研究煤液化产物中酚类化合物的生成机理具有重要的理论意义和实践意义.考察了煤液化过程中反应温度、催化剂及添加高分油三种工艺条件对煤液化油(41℃~220℃)中酚类含量分布的影响.结果表明:随着反应温度升高和催化剂加入都能增加煤液化油中总粗酚产率,而添加高分油方式则不太明显;另外,升高反应温度和添加高分油两种方式可以促进高级酚类中间体发生裂解、脱烷基及脱羟基等二次反应向生成分子量更小、结构更简单的低级酚类进行转化,而通过催化剂的加入可以抑制部分高级酚类向低级酚类的转化.     

艾丁褐煤直接液化产物中酚类形成影响因素研究

针对艾丁褐煤高氧含量的特征,通过高压釜对艾丁褐煤直接加氢液化进行试验研究,考察了反应温度、催化剂添加量、氢气初压和溶剂含量对艾丁褐煤液化产物酚类物质生成的影响。结果表明,艾丁褐煤直接液化生成酚类物质的最适宜条件为:反应温度430℃,催化剂添加量1%,氢气初压5.0 MPa,溶剂含量50%。各低级酚在总酚中的占比分别为:苯酚0. 39%,邻甲酚0. 51%,间甲酚1.08%,对甲酚0. 97%,二甲酚5. 07%。通过碱抽提煤液化油得到的酚类物质中的低级酚(苯酚+C1phenol+C2 phenol)在总酚中占比10.7%,低级酚主要集中在保留时间为24～33 min,高级酚占比较大,且随保留时间的延长既多又杂;提高反应温度、溶剂含量和催化剂添加量有利于提升总酚产率,促进煤反应生成酚类物质,氢气初压对总酚产率影响不大;提高反应温度和催化剂添加量能提升低级酚在总酚中的占比,使高级酚趋向于反应生成低级酚,提高溶剂含量和氢气初压抑制低级酚在总酚中的占比。煤直接液化工艺流程中,通过加氢反应,在低温分离过程中尽可能达到较高的酚产率,同时通过将高分进行循环,以延长高分的反应时间,提高油产率,即实行分级加氢液化将有利于控制和提高油和酚产率。     

煤液化油中低级酚生成的影响因素研究

为了探究反应温度、反应压力、催化剂添加量以及供氢溶剂对褐煤直接液化油中低级酚生成的影响以及低级酚生成的机理,利用模型化合物邻苄基苯酚在煤直接液化条件下进行加氢反应。实验结果表明:邻苄基苯酚在液化条件下主要发生桥键断裂反应生成低级酚,苯环不易被加氢饱和。温度升高对促进邻苄基苯酚桥键断裂有利;压力升高则不利于其桥键断裂;铁系催化剂添加量的增加会促进桥键断裂;供氢溶剂四氢萘相比十氢萘会抑制低级酚的生成。邻苄基苯酚加氢液化的产物以苯酚与甲苯为主,邻甲酚与苯相对较少。     

中/低温煤焦油酚类化合物的组成研究

借助GC-MS手段分析陕北中/低温煤焦油酚类化合物组成和分布情况.通过常减压蒸馏,将陕北中低温煤焦油切割成170℃～230℃,230℃～270℃,270℃～300℃,300℃～340℃和340℃～360℃五个窄馏分并计算收率,并用酸碱抽提法提取各窄馏分中的酚油;通过GC-MS分析了酚油中酚类化合物的组成及分布情况.结果表明,五个窄馏分分别检测出23,23,15,18和10种酚类化合物,酚类化合物占其所在馏分酚油的比率分别为96.89%,60.01%,50.90%,36.51%和36.37%.焦油中所含的酚类化合物占焦油总量的12.91%,酚类化合物主要为低级酚、C3～C4烷基苯酚和萘酚.     

Ni-Mo/Al_2O_3催化剂对废轮胎液化油催化加氢特性研究

以Ni-Mo/Al_2O_3为催化剂,利用1.8 L高压反应釜考察反应温度和氢压对废轮胎液化油加氢转化及脱硫、脱氮效果的影响。结果表明,通过提高反应温度和氢压,可以促进液化油中重组分的转化和硫氮元素的脱除,反应温度和氢压对于脱硫效果影响较明显,而对脱氮效果影响较小。在反应温度410℃、氢压8 MPa和停留时间2 h条件下,重组分全部转化,轻质油收率78%,脱硫率和脱氮率分别达到93.60%和35.63%,其中,汽油馏分中硫、氮含量较低,分别为10.72 mg·L~(-1)和12.04 mg·L~(-1)。     

ZnCl_2催化木质素加氢液化工艺研究

在高压反应釜中,以ZnC l2为催化剂,研究工艺条件对木质素加氢液化影响,并采用GC-MS技术对产物进行检测。结果表明,最佳工艺条件为：以甲醇为溶剂,催化剂添加量7%,反应温度310℃,固液比1∶5,加氢时间1 h。轻馏分产物GC-MS检测表明,主要有甲苯、苯酚、愈创木酚、苯甲醚,大部分产物为苯酚及其烷基取代物。     

国内文献摘要

<正>一种混有高温煤焦油的煤直接液化工艺本发明公开了一种混有高温煤焦油的煤直接液化工艺,包括对高温煤焦油进行净化处理,将净化处理后的高温煤焦油进行减压或常压蒸馏,切割成350℃的轻油馏分和350℃的重油馏分;煤粉与350℃的重油馏分混合成的油煤浆、氢气和催化剂在一级反应器内反应,反应温度为420-460℃,将一级     

ZnCl2催化木质素加氢液化工艺研究

在高压反应釜中,以ZnC l2为催化剂,研究工艺条件对木质素加氢液化影响,并采用GC-MS技术对产物进行检测。结果表明,最佳工艺条件为:以甲醇为溶剂,催化剂添加量7%,反应温度310℃,固液比1∶5,加氢时间1 h。轻馏分产物GC-MS检测表明,主要有甲苯、苯酚、愈创木酚、苯甲醚,大部分产物为苯酚及其烷基取代物。     

陕北中低温煤焦油减压馏分的GC-MS分析

以陕北中低温煤焦油轻油为原料,在减压(1 kPa)蒸馏装置中切取＜100℃,100℃～170℃,170℃～200℃,200℃～240℃,240℃～270℃,270℃～300℃和300℃～340℃7段馏分.利用气相色谱-质谱联用技术(GC-MS)鉴定了馏分中化合物的组成和结构.结果表明,蒸馏终温为340℃可得到煤焦油约95％(质量分数);在各个馏分中都分布有脂肪烃类化合物;蒽菲类化合物主要分布在170℃～240℃馏分中;低级酚主要分布在＜100℃馏分中,酚类含量约占45％,其中苯酚含量为7.46％,甲酚含量为13％;高级酚分布于100℃～170℃和170℃～200℃馏分中;270℃～300℃和300℃～340℃馏分中也有少量低级酚和烯烃被发现,可能是高温下长链脂肪烃和高级酚类化合物发生热裂解所致.     

煤液化中油馏分加氢精制和加氢裂解的研究

本文采用两段加氢精制工艺,对煤液化中油馏分的精制进行了系统的研究。研究发现,使用3665、3822两种催化剂,能一次获得符合加氢裂解要求的产品,脱氮率达99.9％。研究证明,两段精制工艺适合煤液化中油的加氢脱杂原子,第一段主要作用是进行加氢饱和,可采用活性较低的催化剂或在缓和的条件下进行,第二段作用是开环加氢脱氮。本文还研究了反应条件对脱氮率、H/C原子比、产品族组成、芳香度等的影响。     

酚醛树脂用生物油反应活性的测试与分析

生物油的反应活性是制备生物油-PF(酚醛树脂)的关键因素。首先利用酚单体取代基共轭效益参数(Rc)评价了生物油中主要酚类物质的理论反应活性,然后测定了生物油/甲醛的实际反应能力,并与苯酚/甲醛的反应能力进行了对比,以此来评价生物油的整体反应活性。结果表明:生物油中酚类物质的理论反应活性为苯酚的29%;在10 g生物油中加入2.0 g NaOH,并且当反应温度为80℃和反应时间为90 min时,生物油的实际反应能力是苯酚的31%左右。     

Stability of a phenol‐enriched olive oil during storage

The use of an emulsifier to stabilize the phenolic compounds added in the preparation of an enriched olive oil was evaluated. Two emulsifiers, lecithin and monoglyceride, were studied. The results showed lecithin to be the most convenient, due to the increase in the value of the oxidative stability of the phenol‐enriched oils in relation to the enrichments prepared with monoglycerides. After that, the shelf life of the prepared oils was evaluated during a period of 256 days of storage at 25°C in the dark. Oil quality parameters, total phenolic content, bitterness index and oxidative stability were studied during the storage period. Additionally, the phenolic composition and antioxidant capacity (by using the ORAC assay) were evaluated at the end of the storage. The phenolic enrichment of the oils allowed the shelf life of the oils to be extended compared with the control (virgin olive oil without phenol addition), delaying the appearance of peroxides and improving their oxidative stability. In addition, the higher content of phenolic compounds in the oils at all stages of storage is desirable in order to increase the intake of these beneficial compounds. Practical applications : The preparation of phenol‐enriched olive oils with a higher phenolic content than the commercial virgin olive oils is of special interest to increase the ingestion of these healthy compounds the daily intake of which is limited due to the high caloric value of olive oil. There are two key points in the development of this product: (i) the dispersion and stabilization of the phenol extract in the oil matrix and (ii) the stability of the phenols in the prepared oils to guarantee the phenol concentration during their shelf life. It is important to study the use of emulsifiers to determine if they allow an improvement in the dispersion of the phenolic extract, and their stabilization in the final product. In addition, the emulsifiers could mask the bitter taste of the enriched oils, which is desirable to increase consumer acceptance of the enriched oil.     

含有醌与偶氮双官能团的LB膜材料的合成及结构表征

2 氨基蒽醌在强酸性介质中与亚硝酸反应生成重氮盐 ,然后在弱碱性条件下与苯酚偶联制得 2 (4 羟基苯偶氮基 )蒽醌 ,产率为 82 %。以此为中间体 ,在四氢呋喃溶液中分别与 1 溴十二烷和 1 溴十六烷发生醚化反应生成LB膜材料 2 (4 十二烷氧苯偶氮基 )蒽醌 (DOPAzoAQ)和 2 (4 十六烷氧苯偶氮基 )蒽醌 (HOPAzoAQ) ,并运用元素分析、核磁共振、红外光谱、质谱等手段对产物结构进行确认。     

油墨用酚醛树脂的化学改性研究

对油墨用(烷基)酚醛树脂的化学改性研究进行了综述。分别讨论了(烷基)酚醛树脂的环氧化改性、松香改性、石油树脂改性及其他含不饱和键的化合物或聚合物改性,主要包括改性原理、改性方法及其应用情况。     

Isolation of a yeast,Trichosporon cutaneum,able to use low molecular weight phenolic compounds: application to olive mill waste water treatment

This study deals with the degradation of phenolic compounds in olive oil mill waste; a highly polluting material in olive oil‐producing countries because of its abundance and the toxicity of its phenolic compound content. This investigation confirms the ability of an isolated yeast, identified as Trichosporon cutaneum, to degrade phenolic compounds extracted from olive mill waste water (OMW). The yeast was adapted to the OMW by an enrichment culture. The results of this biotransformation were a decrease in the phenolic content and hence a reduction in the phytotoxic effects of the effluent after the yeast treatment. The kinetic growth of the isolated yeast on phenol over a range of concentrations (0.3–3.0 g dm^?3) was studied. The ability of the strain to assimilate simple monomeric phenols and alkyl phenols, at a concentration of 1 g dm^?3, in a synthetic liquid medium used as the sole carbon source was investigated in a batch culture. The aromatic ring cleavage pathway occurred in the yeast through catechol oxidation. Using various concentrations of ethyl acetate extract from OMW as the sole carbon source, the yeast exhibited growth on the substrate up to 7 g dm^?3 equivalent of phenols. A significant reduction of COD after the treatment of the OMW extract by the yeast isolate was noticed. The removal of phenol and COD exceeded 80% of the original loading after 8 days of treatment, for extracts containing initial COD in the range 19 to 72 g dm^?3. Copyright © 2004 Society of Chemical Industry     

[omim]BF4离子液体萃取酚类化合物的研究

采用水浴微波法合成离子液体萃取剂[omim]BF4.研究[omim]BF4对苯酚、邻甲酚等7种酚类化合物的萃取,考察了萃取时间、温度、相比及pH值对萃取效果的影响.实验结果表明:萃取10 min就可以达到平衡;随着温度升高或[omim]BF4与含酚水溶液相比的降低,分配系数降低;酚溶液在pH< pKa时,即酚类化合物主要以分子状态存在时,萃取效率较高.与萃取剂[bmim]PF6及传统有机溶剂相比,[omim]BF4萃取酚类化合物的分配系数处在同一数量级.同时对[omim]BF4萃取酚类化合物的机理进行了探讨,离子液体中的氟与酚类化合物的羟基形成了氢键.     

Phenolic compounds of sphagnum peat

The results of studies of various phenolic compounds, which are the constituents of Sphagnum magellanicum peat of different degrees of decomposition, showed that it is characterized by high concentrations of free phenol compounds, which include phenolcarboxylic acids, catechols, and flavonols. It was found that an increase in the degree of decomposition leads to a decrease in phenolcarboxylic acids in the composition of peat with a simultaneous considerable increase in the concentration of flavonols—an important group of biologically active phenol compounds.     

煤焦油馏分微波萃取神府煤热解液体产物的研究

为提高煤在萃取过程中的转化率,考察微波辅助萃取煤的工业化可行性。在微波辅助下,以神府低温煤焦油馏分为溶剂,在最优操作条件下萃取神府煤,将萃取混合液在510℃条件下热解,分析了热解液体产物的性质及组成,得到了加工方案。结果表明:液体产物主要由酚类化合物、芳烃化合物及烷烃组成,酚类含量较高,其在萃取热解液体产物中的比例均达到50%以上,主要由苯酚、C1～C4苯酚组成,大于C4苯酚的含量很小,其中由苯酚、C1-苯酚、C2-苯酚组成的低级酚含量占总酚含量的70%以上,因此对液体产物进行加工时,需要将低级酚类化合物从液体产物中先分离出来。     

Degradation of Aqueous Phenol and Chlorinated Phenols by Ozone

The degradation of phenol and its chlorinated derivatives with ozone is studied. The studied compounds are phenol (Ph), 4-chlorophenol (4-CPh) and 2,4-dichlorophenol (2,4-DCPh). The kinetic performances of each phenolic compound and their model mixture are examined. The pH influence on the decomposition dynamics for different phenolic compounds in the range 2–12 is investigated. The increase of the decomposition rate under increasing pH was observed. In the pH range studied, phenol and chlorophenols ozonation proceeds rapidly. The UV absorbency is used for the preliminary control of the degree of decomposition. The HPLC analysis is used to identify intermediates and final products formed during ozonation. It is shown that the basic intermediates are muconic and fumaric acids, malonic and maleic acids, catechol and hydroquinone. The final products are oxalic acid and formic acid. In the case of alkaline media, the principal final product is oxalic acid. Furthermore, intermediates and final decomposition products obtained at different pH are compared. According to the results obtained, the possible mechanism of ozonation by the reaction of hydroxylation and dechloration in the early stage is proposed. The BOD₅/COD ratio is used as a biodegradability measure for the comparison of biodegradability of initial compounds and final products composition.