以木薯淀粉为原料,十二烷基苯磺酸钠为酯化剂,NaOH为催化剂,采用微波法制备十二烷基苯磺酸木薯淀粉酯,并考察其合成的工艺条件。探讨了十二烷基苯磺酸钠与木薯淀粉葡萄糖单元的摩尔比、反应时间、反应温度和pH值对产物取代度的影响,用正交实验分析对制备工艺进行优化,并通过红外、X射线和热重分析表征了酯化淀粉的结构及其热稳定性。结果表明,在十二烷基苯磺酸钠与木薯淀粉葡萄糖单元摩尔比为0.06、反应时间5 h、反应温度80℃和pH为10的条件下制备的十二烷基苯磺酸酯淀粉的取代度最佳,取代度为0.010 0。红外和X射线谱图证明了酯化淀粉结构的改变,热重分析表明酯化淀粉亲水性与热稳定性有所下降。

Dodecyl benzene sulfonic acid cassava starch ester was prepared by microwave method with cassava starch as the raw material , sodium dodecyl benzene sulfonate as the esterification agent and sodium hydroxide as the catalyst .The effects of synthetic condition , such as molar ratio ( sodi-um dodecyl benzene sulfonate to glucose unit of cassava starch ) , reaction time , incubated tempera-ture and pH value , on the substitution degree were investigated .The best conditions by orthogonal design were the molar ratio of sodium dodecyl benzene sulfonate to cassava at 0.06 , reaction time 5 h and the incubated temperature 80 ℃, at which the degree of substitution was 0.010 0 .FT-IR and XRD revealed the changes in the structure of the esterified starch , and TG analysis also dis-played the decline of the hydrophilic and thermal stability of the esterified starch .

以中国石油化工股份有限公司上海石油化工研究院开发的SEB-08稀乙烯法制乙苯烷基化催化剂为基础,研究生产过程中稀乙烯法制乙苯的原料可能携带的工艺杂质,如甲苯、非芳烃、硫化氢、水和碱性物质等对烷基化反应的影响。结果表明:(1)循环苯中甲苯的存在使烷基化反应产物中的二甲苯含量上升,影响乙苯产品质量;(2)丙烯对烷基化反应产物中的二甲苯含量影响不大,但丙苯含量大幅上升;(3)正己烷、环己烷、正戊烷和1-戊烯等重质非芳烃使烷基化反应产物中的二甲苯以及重质芳烃含量有不同程度上升;(4)催化干气携带水会对乙烯转化率有一定影响,水体积分数超过1 000×10-6时,乙烯转化率下降明显,催化剂失活速率加快;(5)以乙醇胺为代表的碱性物质对烷基化反应影响最明显,由于催化剂活性中心为酸性,碱性物质引起催化剂不可逆失活;(6)硫化氢含量增加,对催化剂性能以及产品质量影响较小,但对设备及管道的腐蚀程度增加。通过研究工艺杂质对烷基化反应的影响,可为正确判断现有干气制乙苯装置生产中烷基化反应产物组成变化提供依据,为确保装置长周期稳定运行提供参考。

Based on SEB-08 catalyst for alkylation of benzene with dilute ethylene to ethylbenzene,devel-oped by Shanghai Research Institute of Petrochemical of Sinopec,the influence of the impurities in the raw material,such as toluene,non-aromatics,hydrogen sulfide,water and alkaline substances,on the alkylation reaction of dilute ethylene with benzene was investigated. The experimental results showed that:(1)the toluene in the recycling benzene increased the content of xylene in the products,which affected the quality of ethylbenzene;(2)propylene in FCC off-gas had little influenc on the contents of xylene in the products,but the content of propylbenzene increased significantly;(3)the heavy non-aromatics such as n-hexane,cyclohexane,n-pentane and 1-pentene,increased the contents of xylene and heavy aromatics in the products;(4)water in FCC off-gas had certain influence on the activity of the catalyst. When the water content was over 1 000 × 10 - 6 ,ethylene conversion decreased sign

从分子水平研究了催化裂化轻循环油（LCO）经加氢处理后进行催化裂化生成苯、甲苯、二甲苯和乙苯等轻质芳烃（BTXE）的反应规律。认为加氢LCO中重质单环芳烃（包括烷基苯和环烃基苯）的含量及催化裂化反应条件是影响轻质芳烃产率的关键,适宜的加氢处理深度（加氢LCO氢质量分数为11.00%）、催化裂化较高的反应温度（大于550℃）和较大的剂油比（大于8）有利于生产轻质芳烃。在实验条件范围内,LCO中环烃基苯的表观裂化反应比例大于73.4%,表观缩合反应比例小于14.7%,且高温有利于LCO中环烃基苯的裂化反应。加氢LCO经催化裂化反应生成轻质芳烃的单程产率可达14.3%,约占催化裂化产物中单环芳烃总量的1/3。

The reaction rule on production of light aromatics (BTXE)of benzene,toluene,xylene and ethylbenzene from hydrotreated LCO by FCC process is studied on molecular level. The results show that the content of heavy monocyclic aromatics in hydrotreated LCO and FCC reaction conditions are the key factors which influence the yield of BTXE and that the optimal reaction conditions for con-verting LCO to light aromatics are:moderate hydrotreating severity (hydrogen content 11.00% in hy-drotreated LCO),high reaction temperature (over 550 ℃)and middle ratio of catalyst to oil (more than 8)of FCC process. In the range of experimental conditions,the proportion of the apparent cracking re-action of monocyclic aromatic hydrocarbons in hydrotreated LCO is above 73.4%,the condensation re-action is less than 14.7%,and the rest is unconverted monocyclic aromatics. Increasing FCC reaction temperature is favorable for monocyclic aromatics cracking. The once-through yield of light aromatics reache

以乙烯裂解焦油为原料、苯甲醛为交联剂,在对甲基苯磺酸的催化作用下合成了缩合多环多核芳香烃(COPNA)树脂。采用傅里叶变换红外光谱、核磁共振氢谱、热重分析、Brown-Ladner法对乙烯裂解焦油和COPNA树脂的组成、结构及耐热性进行了分析。研究表明:乙烯裂解焦油富含多环芳香烃,且不含长链烷基侧链,空间位阻小,适合作为COPNA树脂的原料。所制COPNA树脂的耐热性、残炭率和β树脂含量较乙烯裂解焦油明显提高,起始热分解温度超过200℃,500℃残炭率达到34.57%,β树脂质量分数为23.02%。

Condensed polynuclear aromatic (COPNA) resin was synthesized from ethylene pyrolysis oil with benzaldehyde as a cross-linking agent in the presence of p-toluene sulfonic acid. The composition, structure and heat resistance of ethylene pyrolysis oil and COPNA resin obtained were analyzed by Fourier transform infrared spectroscopy (FTIR), hydrogen nuclear magnetic resonance (1H-NMR), thermogravimetry and Brown-Ladner method. The results show that ethylene pyrolysis oil is a desirable raw material to prepare COPNA resin for its high content aromatics, small steric hindrance and containing no long alkyl side chains. The COPNA resin po-ssesses good thermal stability, high carbon yield and content of β resin compared with ethylene pyrolysis oil. The COPNA resin has onset decomposition temperature above 200 ℃, carbon yield up to 34.57% at 500 ℃ and mass percentage ofβresin of 23.02%.

针对重烷基苯磺酸盐(HABS)生产废水高pH、高COD、高亚硫酸盐的特点,应用催化氧化-芬顿联合处理工艺进行现场中试实验及参数确定.中试规模为5 t/d,通过优化参数得到催化氧化最优条件为pH=8,曝气量为50 m3·h-1,停留时间为90 min;芬顿氧化段最优条件为30%双氧水投加量1.00 mL/L.采用上述工艺运行方案处理HABS生产废水,出水水质满足GB8978—1996中的I级排放标准,是一种经济可行的工艺.

According to the characters of HABS industrial wastewater of high pH, high COD and high concentration of sulfite, a pilot reactor with catalytic oxidation-Fenton combined treatment process was built, and the pilot scale experiments were employed to discuss the optional parameters. A pilot scale is 5 t/d. After optimized, the optimal optional parameters in catalytic oxidation stage were pH 8, aeration rate 50 m3/h, HRT 90 min. The optimal optional parameters in Fenton stage were dosage of H2O2(30%) 1?00 mL/L. The effluent quality can meet the first class requirements of Sewage Discharge Standard in GB8978-1996, which suggests the process is economical and feasible.