CN102557908B - 2-(环己-1'-烯基)环己酮的制备方法 - Google Patents
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- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
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Abstract
本发明披露一种2-(环己-1’-烯基)环己酮的制备方法，该方法使用特定的固体酸性催化剂，在特定温度条件下，由环己酮进行自缩合反应而制备2-(环己-1’-烯基)环己酮。该固体酸性催化剂具有化学式：AlxSyOz，其中x、y、z表示原子比，且x为1至4，y为1至3，z为可满足存在于该催化剂内呈氧化态的Al与S的价需求的数值。本发明的制备方法可在相对温和的反应条件下由环己酮自缩合制备2-(环己-1’-烯基)环己酮；可提高2-(环己-1’-烯基)环己酮的产率；并可减少对生产设备的腐蚀。
Description
技术领域
本发明涉及一种2-(环己-1’-烯基)环己酮的制备方法，其通过使用特定的催化剂，在特定温度条件下，由环己酮进行缩合反应而制备2-(环己-1’-烯基)环己酮。
背景技术
2-(环己-1’-烯基)环己酮是一种重要的化工产品，其用途广泛，除可作为环氧树酯的改性剂、塑料增塑剂、聚合物的交联剂外，还是合成重要精细有机化学品邻苯基苯酚的中间体。邻苯基苯酚的应用十分广泛，可用于合成染料、表面活性剂、阻燃剂、塑料稳定剂和医药产品等，并随着其用途的不断开发，其市场需求量也持续增长。
邻苯基苯酚的生产方式有六种：一、环己酮缩合脱氢法，二、联苯磺化或卤化水解法，三、氨基联苯重氮化水解法，四、氯苯高压水解法，五、二苯并呋喃(dibenzofuran)法，六、氯苯和苯酚偶合法。上述合成方法中，目前最广泛使用之制程为环己酮缩合脱氢法。环己酮缩合脱氢制程可分为两阶段反应，第一阶段是将环己酮置于酸或碱性催化剂下，进行缩合反应，得到二聚物2-(环己-1’-烯基)环己酮，第二阶段则以含有Pt等金属之催化剂，进行2-(环己-1’-烯基)环己酮的脱氢反应，制得邻苯基苯酚。
如上所述，2-(环己-1’-烯基)环己酮是由环己酮于酸或碱的催化下，在环己酮分子之间发生缩合反应而生成，其反应式如下：
环己酮自缩合反应通常会生成两种共振异构物(I)和(II)，但通常以2-(环己-1’-烯基)环己酮(II)为主，此两种化合物均能再进行后续的脱氢反应，以制备邻苯基苯酚。
目前已发表有关使用于环己酮自缩合以生产2-(环己-1’-烯基)环己酮的催化剂专利，大致可分为无机强酸强碱、有机酸、有机金属化合物和固体酸催化剂四大类。
美国第4,002,693号专利采用硫酸作为催化剂，2-(环己-1’-烯基)环己酮产率约为37％。然而，以硫酸作为催化剂存在着许多弊端。其一，硫酸的腐蚀性较大，对反应设备的投资较高；其二，若使用浓硫酸作为催化剂，其强氧化性及强脱水性会使反应的副产物增多，如使用较稀的硫酸虽可降低副反应的发生，但会导致反应体系中存在过多的水，进而降低反应的转化率；其三，催化剂硫酸无法重复使用，工艺成本耗费高，且反应废水易造成环保间题。
美国第3,980,716号专利披露可使用脂肪族羧酸、环烷酸、杂多酸、乙二胺四乙酸及乙酰丙酮与Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Zr、Mo、Cd、Sn、W等金属所形成的化合物，或以上金属的醇盐，作为环己酮自缩合产生二聚物反应的催化剂，其中以硬脂酸钒作为催化剂的效能较 佳，其环己酮转化率可达71％，二聚物选择性则为89％，但此反应须在无空气的状态下进行，且反应温度需高达190℃，才有较高的转化率。
美国第3,880,930号专利以磺酸型阳离子交换树酯、苯磺酸或对甲苯磺酸，催化环己酮自缩合生产二聚物，转化率最高可达59.9％，选择性90％，但酸性树酯的最大缺点是耐热性较差，须减压进行反应以降低反应温度，否则催化剂容易失活，设备投资成本与能源的损耗较高，而苯磺酸及对甲苯磺酸属于有机强酸，也存在着与硫酸相同的缺点，容易对设备造成腐蚀。
中国科学院山西煤化研究所的研究显示以5％NaNO2-稀土元素/γ-Al2O3作为环己酮双聚催化剂，使用固定床反应器在反应温度350℃下进行反应，环己酮转化率为52.4％，二聚物选择性为99.2％，然而其转化率较低，反应温度过高，能源耗用大，在工艺上不具优势[精细化工，1994，第11卷，第5期，第42-45页]。
中国第101205170号专利提出了改良后的催化剂，以假软水铝石(假勃姆石，pseudo-boehmite)前驱物锻烧后得到的Al2O3作为催化剂，于批式反应器中进行环己酮自缩合反应，其产率可达七成以上。
发明内容
有鉴于前述环己酮自缩合生产二聚物的工艺技术的缺点，本发明的目的在于提供一种2-(环己-1’-烯基)环己酮的制备方法，其可在相对温和的反应条件下，由环己酮自缩合制备2-(环己-1’-烯基)环己酮。
本发明的另一目的在于提供一种可以提高2-(环己-1’-烯基)环己酮产率的2-(环己-1’-烯基)环己酮的制备方法。
本发明的又一目的在于提供一种可减少生产设备腐蚀的2-(环己-1’-烯基)环己酮的制备方法。
根据本发明，使用一种新式固体酸性催化剂催化环己酮自缩合反应，以从环己酮制备得到2-(环己-1’-烯基)环己酮，其中该固体酸性催化剂的化学式为：
AlxSyOz
其中x、y、z表示原子比，且x为1至4，y为1至3，z为可满足存在于该催化剂内呈氧化态的Al与S的(化合)价需求的数值。根据本发明一个具体实施方式，其中，x为1至2，而y为1至2。
根据本发明一个优选的具体实施方式，该固体酸性催化剂可例如将Al(OH)3以浓度介于0.5至2.5M的硫酸溶液浸渍1小时，经干燥后以450℃以上温度煅烧而制得。此外，该固体酸性催化剂的添加量占反应液总重的2重量％以上；反应温度介于100至160℃之间，优选介于130至150℃之间。
本发明可应用于批次工艺及连续式工艺，包含连续搅拌反应器(Continuous Stirred Tank Reactor，CSTR)、固定床反应器(Packed Bed Reactor)、流化床反应器(Fluidized Bed Reactor)等。
以下通过具体实施例进一步说明本发明的特点与功效，但不以实施例说明限制本发明的范围。
具体实施方式
本说明书中所记载的转化率、选择率根据下列方程式计算：
转化率(％)＝{[环己酮添加浓度-环己酮剩余浓度](mol)/环己酮添加浓度(mol)}×100％
选择率(％)＝{2×产出的二聚物(mo1)/[环己酮添加浓度-环己酮剩余浓度](mol)}×100％
(实施例1-3)
(1)催化剂制备
将Al(OH)3以浓度0.6M的硫酸溶液浸渍，于室温下放置1小时后抽气过滤，干燥后经450℃以上温度煅烧，即得实验用催化剂。
(2)缩合反应测试
将568.2克环己酮和23.7克自制催化剂置于附有搅拌器的1L不锈钢制反应器中，控制反应温度分别为130℃、140℃、150℃，反应期间以反应物环己酮自身为带水剂，并另外通入氮气辅助移除反应所产生的水。于反应时间2小时、4小时及6小时取样，样品以气相层析仪及水分滴定仪分析，其结果列于表1中。
表1温度对2-(环己-1’-烯基)环己酮生成的影响
由表1实验结果可知，本发明生物催化剂可有效进行环己酮自缩合反应，并随着反应温度的升高，而提高反应速率与产率。
(实施例4-6)
(1)催化剂制备
以与实施例1-3相同的制备方法制备实验用催化剂。
(2)缩合反应测试
将568.2克环己酮及49.41克、77.48克、108.23克自制催化剂分别置于附有搅拌器的1L不锈钢制反应器中，控制反应温度为140℃，反应期间以反应物环己酮自身为带水剂，并另外通入氮气辅助移除反应所产生的水。于反应时间2小时、4小时及6小时取样，样品以气相层析仪及水分滴定仪分析，其实验结果列于表2中。
表2催化剂浓度对2-(环己-1’-烯基)环己酮生成的影响
由表2实验结果可知，增加催化剂添加量可有效提高反应速率，并在维持7成以上产率的前提下，可有效缩短反应时间。
Claims (1)
1.一种2-(环己-1’-烯基)环己酮的制备方法，所述方法使用固体酸性催化剂，在介于130至150℃的范围内的温度下，由环己酮进行自缩合反应而制备2-(环己-1’-烯基)环己酮，其中，所述固体酸性催化剂具有以下化学式：
AlxSyOz
其中，x、y、z表示原子比，且x为1至2，y为1至2，z为可满足存在于所述催化剂内呈氧化态的Al与S的价需求的数值，
其中，所述固体酸性催化剂占反应液总重的2重量％以上。
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| TWI549749B (zh) * | 2015-05-07 | 2016-09-21 | China Petrochemical Dev Corp Taipei Taiwan | A catalyst composition for preparing o-phenylphenol and a process for preparing o-phenylphenol using the catalyst composition |
| CN106632387B (zh) * | 2016-12-13 | 2018-08-10 | 浙江华贝药业有限责任公司 | 一种工业合成中间体季戊四醇双缩二苯酮的合成工艺 |
| TWI759615B (zh) * | 2019-07-22 | 2022-04-01 | 中國石油化學工業開發股份有限公司 | 2-環己烷基環己醇之製法 |
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| US20120059193A1 (en) | 2012-03-08 |
| US8519192B2 (en) | 2013-08-27 |
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