本文主要研究内容
作者王广辉（2019）在《莰烯酯化反应的热力学与动力学研究》一文中研究指出：酯类是羧酸的一类衍生物,广泛存在于自然界,一般它们是由酸(羧酸或无机含氧酸)与醇脱去一分子的水而形成,也可以由烯烃和羧酸直接加成获得,该过程没有水产生,原子利用率很高,同时简化了流程,降低了后续分离难度。例如乙酸环戊酯,乙酸环己酯,低级脂肪酸异龙脑酯等的合成。以酸性催化剂催化莰烯与低级脂肪酸生成的异龙脑酯具有清香的气味,可以用作香精香料、室内空气清新剂、爽身粉等日化用品的原料。另外异龙脑酯也是良好的润滑剂和溶剂,还可以作为反应的中间体以及合成药物的中间体。虽然对异龙脑酯的合成有一些文献报道,但是对合成异龙脑酯的热力学和动力学却鲜有研究。本文主要研究了三种异龙脑酯的合成,考察了不同的实验条件对莰烯与低级脂肪酸酯化结果的影响,并进行了条件优化。将实验数据进行拟合处理和计算,从而得出相应的热力学及动力学的相关参数。对工业化生产具有一定的指导意义。本文研究的主要内容如下:(1)乙酸异龙脑酯的合成研究以NKC-9树脂为催化剂,在搅拌釜反应器中对乙酸异龙脑酯的合成进行了系统的研究。优化之后的反应条件为:无水NKC-9树脂的用量为总液体物料质量的15%,搅拌的速率为400r·min-1,莰烯与乙酸的初始摩尔比为1:1.5,反应温度为308K。在优化的反应条件下,50min时莰烯的转化率达到92.68%,乙酸异龙脑酯的收率可以达到88.05%。因为溶液是非理想体系,用UNIFAC基团贡献法来进行校正,热力学计算得到反应的焓变△rH0为-29.54KJ·mol-1,熵变△rS0为-54.35J·(mol-K)-1,吉布斯自由能变△rG0为-13.35 kJ·mol-1,平衡常数表达式为:(?)采用拟均相(PH)模型对该反应进行了动力学研究,动力学方程表达式为:r=dacam/dt=Mcat(kfacamaAA-kraIA)其中：(?)(2)丙酸异龙脑酸的合成研究通过筛选发现以阳离子交换树脂NKC-9为催化剂对该反应具有较好的效果,在搅拌釜反应器中考察了莰烯和丙酸酯化反应的影响因素。优化工艺参数为:无水NKC-9树脂的用量为总液体物料质量的15%,搅拌的速率为400 r·min-1,莰烯与丙酸的初始摩尔比为1:1.5,反应温度为313K,反应时间为60min,此时莰烯的转化率93.88%,丙酸异龙脑酯收率可以达到89.21%。采用UNIFAC基团贡献法来对热力学参数进行校正,计算得到反应的焓变△rH0为-22.03kJ mol-1,熵变△rS0为-27.68J·(mol K)-1,吉布斯自由能变△rG0为-13.78 kJ·mol-1,平衡常数表达式为:(?)采用PH模型对该反应进行了动力学研究,动力学方程表达式为:r=dacam/dt=Mcat(kfacamaPA-kraIP)其中:(?)(3)丁酸异龙脑酯的合成研究在搅拌釜反应器中对丁酸异龙脑酯的合成进行了系统的研究。优化工艺参数为:无水NKC-9树脂用量为总液体物料质量的15%,搅拌速率为400r·min-1,莰烯与丁酸的初始摩尔比为1:1.2,反应温度为313K,反应时间为60min,此时莰烯的转化率93.14%,丁酸异龙脑酯收率可以达到88.07%。同样采用UNIFAC基团贡献法对热力学参数进行校正,计算得到反应的焓变△rH0为-17.93kJ.mol-1,熵变△rS0为-9.66J.(mol K).1,吉布斯自由能变△rG0为-1 5.06 kJ·mol-1,平衡常数表达式为:(?)采用PH模型对该反应进行了动力学研究,动力学方程表达式为:r=dacam/dt=Mcat(kfacamaBA-kraIB)其中(?)
Abstract
zhi lei shi suo suan de yi lei yan sheng wu ,an fan cun zai yu zi ran jie ,yi ban ta men shi you suan (suo suan huo mo ji han yang suan )yu chun tuo qu yi fen zi de shui er xing cheng ,ye ke yi you xi ting he suo suan zhi jie jia cheng huo de ,gai guo cheng mei you shui chan sheng ,yuan zi li yong lv hen gao ,tong shi jian hua le liu cheng ,jiang di le hou xu fen li nan du 。li ru yi suan huan wu zhi ,yi suan huan ji zhi ,di ji zhi fang suan yi long nao zhi deng de ge cheng 。yi suan xing cui hua ji cui hua kan xi yu di ji zhi fang suan sheng cheng de yi long nao zhi ju you qing xiang de qi wei ,ke yi yong zuo xiang jing xiang liao 、shi nei kong qi qing xin ji 、shuang shen fen deng ri hua yong pin de yuan liao 。ling wai yi long nao zhi ye shi liang hao de run hua ji he rong ji ,hai ke yi zuo wei fan ying de zhong jian ti yi ji ge cheng yao wu de zhong jian ti 。sui ran dui yi long nao zhi de ge cheng you yi xie wen suo bao dao ,dan shi dui ge cheng yi long nao zhi de re li xue he dong li xue que xian you yan jiu 。ben wen zhu yao yan jiu le san chong yi long nao zhi de ge cheng ,kao cha le bu tong de shi yan tiao jian dui kan xi yu di ji zhi fang suan zhi hua jie guo de ying xiang ,bing jin hang le tiao jian you hua 。jiang shi yan shu ju jin hang ni ge chu li he ji suan ,cong er de chu xiang ying de re li xue ji dong li xue de xiang guan can shu 。dui gong ye hua sheng chan ju you yi ding de zhi dao yi yi 。ben wen yan jiu de zhu yao nei rong ru xia :(1)yi suan yi long nao zhi de ge cheng yan jiu yi NKC-9shu zhi wei cui hua ji ,zai jiao ban fu fan ying qi zhong dui yi suan yi long nao zhi de ge cheng jin hang le ji tong de yan jiu 。you hua zhi hou de fan ying tiao jian wei :mo shui NKC-9shu zhi de yong liang wei zong ye ti wu liao zhi liang de 15%,jiao ban de su lv wei 400r·min-1,kan xi yu yi suan de chu shi ma er bi wei 1:1.5,fan ying wen du wei 308K。zai you hua de fan ying tiao jian xia ,50minshi kan xi de zhuai hua lv da dao 92.68%,yi suan yi long nao zhi de shou lv ke yi da dao 88.05%。yin wei rong ye shi fei li xiang ti ji ,yong UNIFACji tuan gong suo fa lai jin hang jiao zheng ,re li xue ji suan de dao fan ying de han bian △rH0wei -29.54KJ·mol-1,shang bian △rS0wei -54.35J·(mol-K)-1,ji bu si zi you neng bian △rG0wei -13.35 kJ·mol-1,ping heng chang shu biao da shi wei :(?)cai yong ni jun xiang (PH)mo xing dui gai fan ying jin hang le dong li xue yan jiu ,dong li xue fang cheng biao da shi wei :r=dacam/dt=Mcat(kfacamaAA-kraIA)ji zhong ：(?)(2)bing suan yi long nao suan de ge cheng yan jiu tong guo shai shua fa xian yi yang li zi jiao huan shu zhi NKC-9wei cui hua ji dui gai fan ying ju you jiao hao de xiao guo ,zai jiao ban fu fan ying qi zhong kao cha le kan xi he bing suan zhi hua fan ying de ying xiang yin su 。you hua gong yi can shu wei :mo shui NKC-9shu zhi de yong liang wei zong ye ti wu liao zhi liang de 15%,jiao ban de su lv wei 400 r·min-1,kan xi yu bing suan de chu shi ma er bi wei 1:1.5,fan ying wen du wei 313K,fan ying shi jian wei 60min,ci shi kan xi de zhuai hua lv 93.88%,bing suan yi long nao zhi shou lv ke yi da dao 89.21%。cai yong UNIFACji tuan gong suo fa lai dui re li xue can shu jin hang jiao zheng ,ji suan de dao fan ying de han bian △rH0wei -22.03kJ mol-1,shang bian △rS0wei -27.68J·(mol K)-1,ji bu si zi you neng bian △rG0wei -13.78 kJ·mol-1,ping heng chang shu biao da shi wei :(?)cai yong PHmo xing dui gai fan ying jin hang le dong li xue yan jiu ,dong li xue fang cheng biao da shi wei :r=dacam/dt=Mcat(kfacamaPA-kraIP)ji zhong :(?)(3)ding suan yi long nao zhi de ge cheng yan jiu zai jiao ban fu fan ying qi zhong dui ding suan yi long nao zhi de ge cheng jin hang le ji tong de yan jiu 。you hua gong yi can shu wei :mo shui NKC-9shu zhi yong liang wei zong ye ti wu liao zhi liang de 15%,jiao ban su lv wei 400r·min-1,kan xi yu ding suan de chu shi ma er bi wei 1:1.2,fan ying wen du wei 313K,fan ying shi jian wei 60min,ci shi kan xi de zhuai hua lv 93.14%,ding suan yi long nao zhi shou lv ke yi da dao 88.07%。tong yang cai yong UNIFACji tuan gong suo fa dui re li xue can shu jin hang jiao zheng ,ji suan de dao fan ying de han bian △rH0wei -17.93kJ.mol-1,shang bian △rS0wei -9.66J.(mol K).1,ji bu si zi you neng bian △rG0wei -1 5.06 kJ·mol-1,ping heng chang shu biao da shi wei :(?)cai yong PHmo xing dui gai fan ying jin hang le dong li xue yan jiu ,dong li xue fang cheng biao da shi wei :r=dacam/dt=Mcat(kfacamaBA-kraIB)ji zhong (?)
论文参考文献
论文详细介绍
论文作者分别是来自南京大学的王广辉，发表于刊物南京大学2019-07-02论文，是一篇关于莰烯论文,酯化论文,阳离子交换树脂论文,热力学论文,动力学论文,南京大学2019-07-02论文的文章。本文可供学术参考使用，各位学者可以免费参考阅读下载，文章观点不代表本站观点，资料来自南京大学2019-07-02论文网站，若本站收录的文献无意侵犯了您的著作版权，请联系我们删除。