催化裂化装置生产异戊烯的模拟计算研究

应用HYSIM模拟软件,对催化裂化(FCC)装置获取碳五馏分的各种方案进行了研究,并对各方案的优缺点进行了评述。仅有一套FCC装置的炼油厂或者同时拥有几套FCC装置但各装置稳定汽油辛烷值接近的炼油厂,推荐采用塔底方案。炼油化工型企业可考虑塔顶方案或侧线方案。     

助剂对Pd/树脂醚化催化剂催化性能的影响 Ⅰ.铝助剂的影响

研究了不同助剂对Ｐｄ／树脂醚化催化剂在临氢条件下对催化裂化汽油Ｃ５馏份与甲醇和Ｈ２反应的催化性能的影响。结果表明，在Ｐｄ／树脂醚化催化剂中引入Ｚｒ、Ｔｉ、Ｂ、Ｓｎ和Ａｌ等助剂后，都能改善催化剂的醚化、双键异构和二烯烃选择性加氢活性，其中以Ａｌ、Ｓｎ为最好。Ａｌ助剂的体积质量和负载方式对Ｐｄ－Ａｌ／树脂醚化催化剂的活性有影响。ＢＥＴ方法和Ｘ－射线荧光光谱分析（ＸＦＳＡ）表明，Ａｌ助剂对Ｐｄ－Ａｌ／树脂醚化催化剂的表面积、孔结构和Ｐｄ离子交换量影响较小。     

哈尔滨炼油厂MTBE装置试生产

介绍了哈尔滨炼油厂ＭＴＢＥ装置的工艺路线、新技术的应用及特点；催化剂的装填及应用情况；总结了生产过程中遇到的一系列问题及解决办法；探索了平稳生产的新徐径，以保证装置安全、平稳、长周期运行；同时对反应器操作温度、催化蒸馏塔操作压力、原料中醇烯比等因素对异丁烯转化率及ＭＴＢＥ产品的影响做了简单的总结。     

由碳五馏分合成甲基叔戊基醚工艺的研究

以催化裂化C_5馏分与工业甲醇为原料,D005型大孔强酸型阳离子交换树脂为催化剂,采用筒式膨胀床双反应器,考察了甲基叔戊基醚的合成工艺条件。一阶反应器的操作条件为：循环比为2：1,醇烯比为1.2：1,入口温度为70℃,空速为6 h~(-1),平均转化率为53.63%；二阶反应器的操作条件为：入口温度为50℃,空速为1.2h~(-1),平均转化率为71.32%,全调合方案可以使催化裂化汽油的辛烷值平均提高0.55个单位。     

TiSiW12O40/TiO2催化合成丙酸正丙酯

研究了固载杂多酸盐TiSiW12O40/TiO2催化丙酸与正丙醇的酯化反应，探讨了催化剂用量，反应时间及醇酸摩尔比对酯收率的影响。当醇酸摩尔比为1.3:1，催化剂的量为醇酸总质量的1.5%。反应时间为1.0h，酯产率可达71.4%以上，采用该催化剂合成丙酸正丙酯不仅酯化反应温度低，反应时间较短，催化剂用量少，而且可较好地回收利用，可降低成本；因此，TiSiW12O40/TiO2是合成丙酸正丙酯的优良催化剂，具有良好的应用前景。     

以杂多酸为催化剂合成乙二醇-乙醚的研究

研究了杂多酸催化无水乙醇和环氧乙烷(EO)制备乙醇乙醚的醚化反应,考察了不同种类的杂多酸以及醚化反应工艺条件对反应活性和选择性的影响.结果表明,PW_(12)催化剂的反应活性高、反应温度低、选择性好,当用PW_(12)作催化剂,乙醇与环氧化乙烷之比为3.0(mol),反应温度45℃,反应时间1h时,转化率和选择性均超过97%.     

Influence of Shaping Condition on Etherification Performance of Hβ Zeolite

Etherification reaction of FCC light gasoline over Hβ zeolite was investigated to decrease the light olefins in motor gasoline while enhancing octane. Etherification activity of several molecular sieve catalysts for FCC light gasoline was studied in a fixed-bed reactor. The influence of pore-enlarging agent (PEG) with different molecular weight, binder (γ-Al₂O₃), and peptizing agent (HNO₃) in the shaping process on etherification activity of Hβ zeolite was studied. The impregnating ways of precursor of oxides and the order of extruding and impregnating were also investigated. The results show that the activity of extruded Hβ zeolite before impregnating precursor of oxides is higher than the reverse order. The best shaping condition obtained was PEG-4000 10%, γ-Al₂O₃ 20%, and HNO₃ 10%. At the optimal reaction condition, the conversion of tert-olefins reached the peak. 62.93%, the yield of TAME, is also high and the technology can be applied to industry as well.     

利用抽余碳五馏份制备TAME

探索了以抽余Ｃ５为原料经与甲醇醚化制ＴＡＭＥ的过程。试验表明，在国产催化剂Ｄ５４型大孔阳离子交换树脂存在下，在反应温度６０℃、ＬＨＳＶ２．４ｈ－１、甲醇／异戊烯物质的量比１．００、反应压力０．２ＭＰａ的条件下，抽余Ｃ５中的异戊烯可与甲醇反应生成醚，异戊烯的转化率达６３．２６％，ＴＡＭＥ的选择性可达９９．６１％。     

Gas phase synthesis of MTBE on fluoride-modified zeolites

The gas phase synthesis of MTBE was studied using three series of zeolites modified by ion-exchange with ammonium fluoride, the parent materials being HY, H-mordenite, and HZSM-5. Modification of zeolites by fluoride-exchange was found to enhance the MTBE synthesis activity for all three types of zeolites without impairing their excellent selectivity to MTBE. The mechanism of activity enhancement by fluoride-modification appears to be related to the formation of extra-lattice Al rather than the presence of fluoride-ions.     

粗异戊烯的醚化

研究了苯磺酸型树脂催化的异戊烯和甲醇的醚化,考查了温度、醇烯比和空速对反应的影响。结果表明在反应温度为59～67℃、甲醇与异戊烯的摩尔比值为1 4～1 6、液时空速为1 1～1 5h-1时反应的转化率大于70%。