溶剂效应对脱除煤沥青中3,4-苯并芘的影响

研究了单种溶剂、混合溶剂对3,4-苯并芘的溶解选择性及煤沥青溶解量。并以顺丁烯二酸酐为改性剂、硫酸为催化剂,考察了溶剂效应对降低煤沥青中3,4-苯并芘的影响。研究表明,环己烷、甲苯,环己烷、乙酸丁酯组成的混合溶剂具有较好的3,4-苯并芘溶解选择性和合适的煤沥青溶解量。当环己烷∶甲苯=2∶1（体积比）和环己烷∶乙酸丁酯=2∶1（体积比）为反应溶剂时,能够高效地脱除煤沥青中3,4-苯并芘,煤沥青中3,4-苯并芘降低率分别达到88.26%和90.83%。其原因认为是此类溶剂能使包裹在沥青颗粒内部的3,4-苯并芘释放出来,且3,4-苯并芘与改性剂能够形成均相反应体系,大部分不具有致癌性的高相对分子质量环芳烃与改性剂之间形成两相体系,从而提高了改性剂与3,4-苯并芘的有效反应。     

用聚合物试剂减少煤沥青中3,4-苯并芘的研究

研究了用聚合物同煤沥青反应降低其中3,4-苯并芘的方法。实验采用3种聚合物同煤沥青反应,得出不同的聚合物对减少3,4-苯并芘的作用效果,通过对聚苯乙烯-丁二烯-苯乙烯、古马隆-茚树脂和聚乙二醇的研究发现:添加4%的古马隆-茚树脂对煤沥青中3,4-苯并芘的脱除效果较好,脱除率达到46.78%,最佳反应温度为270℃,煤沥青中的3,4-苯并芘的质量分数由1.43%降低到0.76%。     

脱除煤沥青中3,4-苯并芘及其机理研究

以聚乙二醇和三聚甲醛为复合改性剂,采用聚合物改性法脱除煤沥青中致癌多环芳烃3,4-苯并芘,在复合改性剂比例(聚乙二醇与三聚甲醛的比)为4∶6时脱除率可达76.0%。元素分析结果表明,改性煤沥青的C、S元素含量降低,H元素含量升高,C/H值和芳香度(fa)降低,说明改性煤沥青的软化点降低、体系的稳定性下降。红外光谱分析结果表明,聚乙二醇与3,4-苯并芘的反应属于O-烷基化反应,三聚甲醛与3,4-苯并芘的反应属于C-烷基化反应。     

煤沥青中致癌多环芳烃3,4-苯并芘检测方法的研究

3,4-苯并芘作为多环芳烃的典型代表,广泛存在于煤沥青中,是环境污染中的重要污染物,对其进行检测及防治,对人类环境及生态安全具有重要意义。本文简要论述了煤沥青中致癌多环芳烃3,4-苯并芘的危害及检测方法的研究进展,并提出了我国煤沥青中3,4-苯并芘的检测技术今后的研究重点及方向。     

新型柴油低温流动改进剂的制备与性能研究

以对甲苯磺酸为催化剂,二甲苯为溶剂,柠檬酸与聚乙二醇400反应生成CPC(柠檬酸-聚乙二醇400-柠檬酸),加入油酸,与CPC继续进行酯化反应得到CPC-S;CPC-S进一步用混合醇(十六醇和十八醇的摩尔比8∶2)接枝,得到新型爪形大分子柴油低温流动改进剂CPC-SHO。考察酸醇比、油酸比、混合醇比、溶剂用量、三步反应中每步反应的催化剂用量和反应时间对柴油冷滤点的影响。结果表明,酯化反应的最优条件为:第一步反应,酸醇摩尔比2.2∶1,催化剂用量0.5%,反应时间1.1 h,溶剂用量70%;第二步反应,n(CPC)∶n(油酸)为1∶1.1,催化剂用量0.7%,反应时间1 h,溶剂用量70%;第三步反应,n(CPC-S)∶n(混合醇)为1∶4,催化剂用量0.7%,溶剂用量80%,反应时间1.0 h。CPC-SHO对沈阳蜡化厂0^#柴油感受性最好,用量1 g/L时,冷滤点可降低12.5℃。     

新型柴油低温流动改进剂的制备与性能研究

以对甲苯磺酸为催化剂,二甲苯为溶剂,柠檬酸与聚乙二醇400反应生成CPC(柠檬酸-聚乙二醇400-柠檬酸),加入油酸,与CPC继续进行酯化反应得到CPC-S;CPC-S进一步用混合醇(十六醇和十八醇的摩尔比8∶2)接枝,得到新型爪形大分子柴油低温流动改进剂CPC-SHO。考察酸醇比、油酸比、混合醇比、溶剂用量、三步反应中每步反应的催化剂用量和反应时间对柴油冷滤点的影响。结果表明,酯化反应的最优条件为:第一步反应,酸醇摩尔比2.2∶1,催化剂用量0.5%,反应时间1.1 h,溶剂用量70%;第二步反应,n(CPC)∶n(油酸)为1∶1.1,催化剂用量0.7%,反应时间1 h,溶剂用量70%;第三步反应,n(CPC-S)∶n(混合醇)为1∶4,催化剂用量0.7%,溶剂用量80%,反应时间1.0 h。CPC-SHO对沈阳蜡化厂0~#柴油感受性最好,用量1 g/L时,冷滤点可降低12.5℃。     

催化加氢制备3,4-亚甲二氧基苯胺

3,4 亚甲二氧基硝基苯在95%乙醇溶剂中用雷尼镍催化加氢制备了3,4 亚甲二氧基苯胺。对催化剂用量和活性稳定性进行了研究,讨论了溶剂用量、温度、压力等因素对加氢反应的影响。结果表明最佳工艺参数为:雷尼镍∶乙醇∶3,4 亚甲二氧基硝基苯=0.15∶6∶1(质量比),反应温度40℃,氢压0.45～0.50MPa,搅拌速度450r/min,反应至不再吸氢为止,产品收率在97%以上,纯度为98%。     

4,5-二甲基-1,2-二苯胺的合成工艺改进

以3,4-二甲基苯胺为原料,合成了4,5-二甲基-1,2-二苯胺,产品收率达69%以上。在乙酰化、硝化反应中引入了1,2-二氯乙烷溶剂。用正交实验确定了最佳原料配比:n(3,4-二甲基苯胺)∶n(醋酸酐)∶n(硫酸)=1.00∶1.15∶1.10,硝化反应温度为13°C,反应时间为3.5h,硝化产物收率为90.56%,溶剂回收率95%以上。改进后,每摩尔母体的醋酸酐用量由303g减少至118g,浓硫酸用量由304g减少至108g。     

聚羧酸系混凝土减水剂的研究——大分子单体的制备与表征

通过衣康酸与聚乙二醇的酯化反应,制备出了一种可用于合成聚羧酸系减水剂的大分子单体。用正交实验研究了反应条件对酯化反应的影响,确定了最佳的酯化反应条件为:n(衣康酸)∶n(聚乙二醇-1000)=1∶1.1,催化剂用量为聚乙二醇-1000质量的4%,反应温度100℃,反应时间6 h,带水剂用量为聚乙二醇-1000质量的30%,阻聚剂用量为衣康酸质量的2%,在该条件下单酯化率可达到98.3%。通过红外光谱、核磁共振氢谱对大分子单体的结构进行了表征。     

2,2'-双氧代-4,4'-二苯基-5,5'-三亚甲基-6,6'-螺-双六氢嘧啶的绿色合成

以聚乙二醇-400为溶剂,以环己酮、苯甲醛、尿素为原料一锅煮合成2,2'-双氧代-4,4'-二苯基-5,5'-三亚甲基-6,6'-螺-双六氢嘧啶,探索催化剂及溶剂的用量、反应物配比、反应时间、反应温度对反应的影响,得到最佳反应条件为:n(环己酮)∶n(苯甲醛)∶n(尿素)=1.0∶2.5∶3.0、10 mL聚乙二醇-400、0.54 g对甲苯磺酸,反应温度100℃,反应时间5.0 h,产品收率为82.1%。     

Production of coal tar/petroleum pitch by the combined distillation of coal tar and heavy cycle oil at JSC Gubakhinskii Koks

Coal tar/petroleum pitch has been produced by the combined distillation of coal tar and heavy cycle oil from catalytic cracking, in industrial trials. In processing a 60: 40 mixture of those components, 306 t of pitch that meets the requirements for anode binder is produced. The benzo[a]pyrene content is lower in the petroleum–coal pitch than in regular coal pitch used in electrode production.     

Influence of tall oil and ultrasound treatment on pitch production from semicoking tar or the anthracene fraction

The properties of coal pitch obtained from blends of tall oil and semicoking tar or the anthracene fraction are investigated. Small additions of tall oil to semicoking tar (in the ratio 1: 6) increase the yield of pitch on thermal oxidation and its softening temperature but decrease the coke residue. On ultrasound treatment, chemical transformations of the molecules under the action of cavitation change the characteristics of the pitch produced on thermal oxidation. Primarily, however, the ultrasound permits reduction in the benzo[a]pyrene concentration in the mixture by almost half. On thermal oxidation, the benzo[a]pyrene concentration is further reduced, but most of its mass is concentrated in the pitch.     

Analysis by GC-MS of Polycyclic Aromatic Hydrocarbons in a Cream Containing Coal Tar

Qualitative and quantitative PAHs composition of a cream containing coal tar (5%), used in cutaneous diseases treatment, was studied. Eleven PAHs were analysed in pure coal tar and in the cream by GC-MS, after ultrasonic extraction by pyridine. Ten PAHs were found in pure coal tar: naphthalene, biphenyl, acenaphthylene, fluorene, phenanthrene, anthracene, carbazole, fluoranthene, pyrene and benzo[a]pyrene. No traces of 2,3-benzofluorene were detected. Seven PAHs were identified in the cream: naphthalene, biphenyl, acenaphthylene, fluorene, phenanthrene, fluoranthene and pyrene. 2,3-benzofluorene was also absent in the cream. Anthracene, carbazole and benzo[a]pyrene (one of the most toxic) were present in coal tar and not detected in the cream.

The seven PAHs found in the cream and in coal tar were quantified. Hydrocarbons concentrations were between 0.107 ± 0.0038 mg.g^?1 (for biphenyl) and 0.734 ± 0.0438 mg.g^?1 (for phenanthrene) in the cream and between 4.31 ± 0.23 mg.g^?1 (for biphenyl) and 21.9 ± 0.57 mg.g^?1 (for fluorene) in coal tar.     

Benefits of ultrasound in pitch production from coal tar and its mixtures with styrene distillation residue

Ultrasound treatment of coal tar increases the yield of pitch by a factor of 1.5 in subsequent oxidation by atmospheric oxygen. The yield of pitch may be regulated in terms of its softening temperature by changing the oxidation time. To obtain standard pitch, the following conditions are employed: ultrasound treatment for 3 h; initial oxidation temperature 260–270°C; final oxidation temperature 360–370°C; rate of air supply 63 L/h; oxidation time ~30–70 min, depending on the requirements on the final product. The concentration of aromatic derivatives of benzo[a]pyrene type in the pitch produced and in the liquid fraction (which may be used as a fuel) is considerably less than in the current industrial method. After ultrasound treatment, a 1: 1 mixture of coal tar and rectification residues from styrene yields pitch with satisfactory characteristics on oxidation by atmospheric air. That expands the range of raw materials for pitch production.     

Influence of the coke filler on the carcinogenicity of pitch–coke mixtures on carbonization

The emissions of benzo[a]pyrene at different temperatures and its concentration in the exhaust gases are measured in laboratory experiments on the carbonization (at temperatures up to 850°C) of coalpitch and petroleum-pitch binders and their mixtures with roasted petroleum and pitch coke. These pitch–coke mixtures are similar in composition to the anode mass used in aluminum production. The experiments confirm that the total benzo[a]pyrene emissions are much greater in the carbonization of petroleum pitch produced by cracking (T _so = 100°C) than for electrode pitch (T _so = 89°C) and other coal pitch. In most experiments, the benzo[a]pyrene emissions in the carbonization of pitch–coke mixtures is markedly less than for individual binder pitches. It is found that the benzo[a]pyrene emissions in the carbonization of a mixture based on pitch coke are much less than for a mixture based on petroleum coke in the high-temperature region that presents the greatest environmental hazard.     

Evaluation of Coal Tar Tumorigenic Potential in p53 +/− Mice

The potential of transgenic p53 +/ m mice for use as a short-term assay for identifying chemical carcinogens has been primarily evaluated using single chemicals. There have been no reports on the use of this model for assessing the carcinogenic potential of complex organic mixtures containing polycyclic aromatic hydrocarbons (PAHs). In this study, the ability of coal tar to induce a tumorigenic response in transgenic p53 +/ m mice was investigated. Transgenic p53 +/ m mice were fed diets containing 0.3% manufactured gas plant coal tar (MGP coal tar), 0.3% pharmaceutical grade coal tar (PG coal tar), or 100 ppm benzo[ a ]pyrene (B[ a ]P) for a total of 26 weeks. A group of mice were also treated ip with B[ a ]P (100 mg/kg body weight). Forestomach tumors were observed in 8% of the mice fed PG coal tar. Mice fed 100 ppm B[ a ]P had a 10% incidence of forestomach tumors. Bronchioalveolar adenomas were observed in 23% (3/13) of the mice fed PG coal tar. No lung tumors were observed in any of the mice given a single intraperitoneal injection of B[ a ]P or fed MGP coal tar or B[ a ]P for 260 days. These results are in contrast to results of previous studies performed with A/J and B6C3F1 mice that demonstrated MGP coal tar to be highly tumorigenic in mouse lung.     

Evaluation of PAH: DNA Adduct Formation in Rats Fed Coal Tar-Contaminated Diets

Previous studies have demonstrated that mouse lung is a target organ for the tumorigenic and genotoxic effects of coal tar. The present study evaluated PAH:DNA adduct formation in lung, liver, forestomach, and mammary gland of female CD rats fed various types of coal tar-contaminated diets. Coal tar-contaminated soil, an organic extract of contaminated soil, neat coal tar, and diets containing only B[ a ]P were evaluated. Ingestion of coal tar diets resulted in detectable levels of DNA adducts in lung and forestomach tissue. These adducts were primarily derived from benzo[ c ]fluorene and B[ a ]P. The adduct derived from benzo[ c ]fluorene was the most predominant. No adducts were detected in liver and mammary gland under the conditions employed in this study. The formation of a benzo[ c ]fluorene-derived DNA adduct in rat lung following coal tar exposure is consistent with previous studies performed with mice.     

Assessing the carcinogenicity of carbon-bearing binders

Methods of determining the carcinogenicity of carbon-bearing binders in terms of their benzo[a]pyrene content and the benzo[a]pyrene emissions in binder carbonization at temperatures up to 850°C are considered. In the laboratory, CARBORES-T and CARBORES-P binders with reduced benzo[a]pyrene content are studied, as well as the industrial carbon pitch from which they are derived. It is found that predicting the carcinogenicity of carbon-bearing binders in terms of their benzo[a]pyrene content is unsatisfactory, largely because the formation and emission of benzo[a]pyrene on binder heating is ignored. Quantitative determination of the benzo[a]pyrene emission in the carbonization of the binders may be regarded as a more reliable and more universal method. It may be used to compare the carcinogenicity of products derived from coal and petroleum, as well as binders that do not contain benzo[a]pyrene.