CN102076886A - 电化学直接胺化烃类的方法 - Google Patents
电化学直接胺化烃类的方法 Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
本发明涉及一种借助金刚石电极电化学直接胺化烃类的方法以及一种制备苯胺的方法。
Description
本发明涉及一种借助金刚石电极电化学直接胺化烃类的方法以及一种制备苯胺的方法。
胺类为许多化合物和工业部门的原料。例如用于制备聚氨酯的异氰酸酯的制备需要芳族有机化合物作为原料。然而,还将胺类用于制备染料。另外,胺类作为反应物在形成亚胺、羧酰胺/羧酰亚胺的亲核取代中具有众多用途。此外,胺类为农用化学品和药物以及表面活性剂、涂料和润滑剂的结构单元。
芳族胺,尤其是苯胺的工业制备目前在工业上借助两步法进行。这里,将芳族化合物借助硝化酸,即H2SO4和HNO3的混合物转化相应的硝基化合物。随后将芳族硝基化合物根据下列方案借助3当量氢气催化氢化。
该方法的缺点为必须适当处理的大量废料流的处理。该废料流包含各种芳族硝基化合物如硝基苯酚或硝基甲酚。该料流的直接焚烧是不可能的,因为它主要是含水排放物。因此在残渣可“热处理”之前必须蒸发水。这是非常耗能的方法。在US 6245242中描述了替换方法,其中将臭氧分解用于来自硝基苯工厂废水中有机成分的氧化降解。
在DE-A 10 2004 062 253中描述了催化直接胺化。然而,此时将芳族烃借助催化剂体系在氨中氧化胺化。
该方法的缺点为对工业方法来说转化率太低并且氧化剂如大气氧的化学计量使用以除去氢。另一个缺点是该方法不能用苯和氨作为唯一的试剂进行而额外需要氧化剂。苯胺收率太低使得该方法的经济性成为问题。
因此强烈需要不使用导致昂贵废料流的硝化酸,转化率超过5%且不使用其他氧化剂而制备胺类化合物的一步法。
该目的通过一种制备胺类的方法实现,其中在一个步骤中对有机化合物进行电化学胺化。
当将掺杂金刚石电极用作电极时,本发明方法是有利的。
当将硼掺杂金刚石电极用作阴极和阳极时,本发明方法是有利的。
当在1-20A/dm2的电流密度下进行本发明方法时,本发明方法是有利的。
当在电荷量为2-8F/mol基底之后停止电解时,本发明方法是有利的。
当电解连续进行时,本发明方法是有利的。
当电解期间温度为-50℃到50℃时,本发明方法是有利的。
当电解期间压力为1-30巴时,本发明方法是有利的。
当电解在无隔膜电解池中发生时,本发明方法是有利的。
当将浓度为1-99%的氨用作电解液时,本发明方法是有利的。
当在-50℃到-33℃的温度和大气压力下进行时,本发明方法是有利的。
当在室温和1-30巴的压力下进行时,本发明方法是有利的。
当将芳族化合物用作有机化合物时,本发明方法是有利的。
当将苯用作有机化合物时,本发明方法是有利的。
本领域技术人员已知的任何有机化合物可通过本发明方法胺化。这些有机化合物为选自取代和/或未取代的环状和/或无环的脂族和/或芳族化合物的烃类。这些取代和/或未取代的环状和/或无环的脂族和/或芳族化合物可具有选自氧、氮、磷和硫的杂原子和/或官能团如醇、羧酸、酯、胺、酰胺、硫醇、硫酮基团。优选有机化合物为甲烷、乙烷、正丙烷、异丙烷、正丁烷、异丁烷、叔丁烷、正戊烷、异戊烷、正己烷、苯、甲苯、邻二甲苯、间二甲苯、对二甲苯、二苯基甲烷、苯胺和吡啶、咪唑、苯乙烯、乙基苯、甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、乙二醇、丙二醇、丁二醇、乙烯、丙烯、丁烯、丁二烯、丙烯醛、丙烯酸、丙烯腈、己二酸。特别优选芳族化合物。非常特别优选苯。
电解所用电极选自铂、石墨、玻璃碳、钢和掺杂金刚石电极。优选阳极材料为石墨、玻璃碳、铂和掺杂金刚石电极。优选阴极材料为石墨、玻璃碳、铂、钢和掺杂金刚石电极。非常特别优选掺杂金刚石电极用于阴极和阳极。这里可使用氮掺杂或硼掺杂的金刚石电极。尤其优选硼掺杂金刚石电极用于阴极和阳极。
阳极和阴极的电极材料可以但不必相同。然而,优选阴极和阳极均包含硼掺杂金刚石电极。
这些硼掺杂金刚石电极在含水电解液中显示高氧过电压,从而可特别产生羟基。在NH3电解液的硼掺杂金刚石电极中所用的本发明电解通过相似的机理获得自由基NH2。
自由基NH2具有高反应性并导致在有机化合物上夺取H,随后通过自由基重组胺化。
可使用由CVD(化学气相沉积)法制备的掺杂金刚石电极。该电极例如由制造商Condias、Itzehoe,Diaccon、Fürth(德国)或Adamant Technologies、La-Chaux-de-Fonds(瑞士)市售。
同样可使用由HTHP法(高温高压:将工业金刚石粉末机械引入作为载体的金属板表面)制备的更便宜的掺杂金刚石电极。
HTHP-BDD电极由pro aqua、Niklasdorf(奥地利)市售,并且A.Cieciwa、R.Wüthrich和Ch.Comninellis在Electrochem.Commun.8(2006)375-382中描述了它们的性能。
可使用本领域技术人员已知的任何电解池如隔膜或无隔膜电解池、毛细狭缝电解池(capillary gap cell)或叠板电解池(stacked plate cell)进行电解。特别优选无隔膜电解池。多个电极的双极设置有利于实现最佳时空产率。
本发明电化学直接胺化在作为电解液的液态氨溶液中进行。优选浓度为1-99%的氨溶液。
在液态氨中电解在-50℃到50℃,特别优选-40℃到30℃的温度下进行。取决于所用电解液温度,反应期间压力为1-30巴,优选1-20巴。
电解期间支持电解质优选额外存在于电解液中。可将本领域技术人员已知的任何支持电解质用于电解。优选用于本发明方法的支持电解质选自铵盐、季铵盐和金属盐。铵盐选自乙酸铵、碳酸氢铵和硫酸铵。季铵盐选自甲基硫酸甲基三丁基铵、甲基硫酸甲基三乙基铵、四氟硼酸四丁基铵和四氟硼酸四乙基铵。特别优选甲基硫酸甲基三丁基铵。金属盐优选选自碱金属和碱土金属盐,特别优选选自氨基钠、乙酸钠、烷基磺酸钠、芳基磺酸钠、烷基硫酸钠、芳基硫酸钠、碳酸氢钠、氨基钾、乙酸钾、烷基磺酸钾、烷基硫酸钾和碳酸氢钾。
在本发明方法中电流密度优选为1-20A/dm2,特别优选2-10A/dm2。当使用金刚石电极作为阳极和阴极材料时,为避免在电极上沉积,可以短间隔改变极性。极性反转可间隔30秒-60分钟,优选间隔60秒-30分钟发生。
电解池内容物的混合可使用本领域技术人员已知的任何机械搅拌器和其他混合方法如使用Ultra turrax或超声波进行。
在引入2-8F/mol基底,特别优选2-4F/mol基底的电荷量之后停止反应。在以间歇法大气压力电解的情况下,通过关闭电源停止反应并将反应混合物温热至RT,然后从反应混合物中蒸除过量NH3。在以间歇法低压(低压指0-40巴)电解的情况下,为停止反应,关闭电源,然后使压力容器达到大气压力并从反应容器中蒸除过量NH3。在连续操作方法的情况下,排出部分电解液,然后温热至RT和/或达到大气压力。反应期间释放的氨气适当地用吸除。剩余的残渣通过本领域技术人员已知的方法如溶解、结晶、蒸馏和/或过滤后处理。
有机化合物也可通过本发明方法多胺化。为了从单胺化产物中分离多胺化产物,可使用本领域技术人员已知的所有分离方法。它例如可通过借助蒸馏和/或结晶从反应混合物中分离出单或多胺化产物进行。
本发明实施例
实施例1:在-40℃下在液态氨中茴香醚的胺化
在-40℃下将4.7g茴香醚和1.2g甲基硫酸甲基三丁基铵放入具有BDD阳极和BDD阴极(在每种情况下电极尺寸:70×20×5mm,浸渍面积:45×20mm,间隔:9mm)的玻璃烧杯电解池中。加入70.0g氨(液态)之后,在2A/dm2的电流密度下开始电解。电解期间将电压从9.7V增加到10.6V。引入2F/mol茴香醚的电荷量之后,停止电解并且使电解液达到室温。通过气相色谱分析蒸发NH3后剩余的残渣。
在反应混合物中二氨基苯作为胺化产物以18GC-面积%的量检测出。实施例2:在室温下在液态氨中苯的胺化
在室温下将4.0g苯和2.0g甲基硫酸甲基三丁基铵放入具有BDD阳极和BDD阴极(在每种情况下电极尺寸:70×20×5mm,浸渍面积:45×20mm,间隔:9mm)的高压釜中。用113.8g氨加压反应釜并且在2A/dm2的电流密度下开始电解。在电解过程中将电压从5.2V降到4.7V,而设备压力从12.1巴升到17.9巴。引入2F/mol苯的电荷量之后,停止电解并且使高压釜排气。通过气相色谱分析蒸发NH3后剩余的残渣。
在反应混合物中苯肼作为胺化产物以0.6GC面积%的量检测出。
Claims (14)
1.一种制备胺类的方法,其中在一个步骤中对有机化合物进行电化学胺化。
2.根据权利要求1的方法,其中将掺杂金刚石电极用作电极。
3.根据权利要求1或2的方法,其中将硼掺杂金刚石电极用作阴极和阳极。
4.根据上述权利要求1-3中任一项的方法,在1-20A/dm2的电流密度下进行。
5.根据权利要求1-4中任一项的方法,其中在2-8F/mol的电荷量后停止电解。
6.根据权利要求1-5中任一项的方法,其中电解连续进行。
7.根据权利要求1-6中任一项的方法,其中电解期间温度为-50℃到50℃。
8.根据权利要求1-7中任一项的方法,其中电解期间压力为1-30巴。
9.根据权利要求1-8中任一项的方法,其中电解在无隔膜电解池中进行。
10.根据权利要求1-9中任一项的方法,其中将浓度为1-99%的氨用作电解液。
11.根据权利要求1-10中任一项的方法,在-55℃到-33℃的温度和大气压力下进行。
12.根据权利要求1-10中任一项的方法,在室温和1-30巴的压力下进行。
13.根据权利要求1-12中任一项的方法,其中将芳族化合物用作有机化合物。
14.根据权利要求1-13中任一项的方法,其中将苯用作有机化合物。
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CN106414391A (zh) * | 2014-05-15 | 2017-02-15 | 科思创德国股份有限公司 | 通过在掺硼金刚石阳极上使未活化或去活化的芳族体系直接电化学胺化以制备1,5‑二氨基萘和1‑氨基‑5‑硝基萘的方法 |
CN108138340A (zh) * | 2015-10-15 | 2018-06-08 | 科思创德国股份有限公司 | 用于制备氨基官能的芳族化合物的方法 |
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KR20120006499A (ko) | 2009-04-06 | 2012-01-18 | 바스프 에스이 | 반응 혼합물로부터의 수소의 전기화학적 제거 방법 |
JP5415610B2 (ja) | 2009-04-06 | 2014-02-12 | ビーエーエスエフ ソシエタス・ヨーロピア | 水素を電気化学的に除去することによって、電流及び水素を発生させながら天然ガスを芳香族化合物に変換する方法 |
CN102548953B (zh) | 2009-07-10 | 2014-10-08 | 巴斯夫欧洲公司 | 将烃直接胺化成氨基烃并且包括氢气的电化学分离和氢气形成水的电化学反应的方法 |
PT2451769E (pt) | 2009-07-10 | 2015-02-10 | Basf Se | Método para aminação direta de hidrocarbonetos para formar amino-hidrocarbonetos com separação eletroquímica de hidrogénio |
US8739743B2 (en) * | 2012-03-27 | 2014-06-03 | Go Green Hybrid Fuel Systems | Hydrogen feed method and systems for engines |
US10392715B2 (en) | 2016-08-29 | 2019-08-27 | Wisconsin Alumni Research Foundation | Electrochemical reductive amination of furfural-based molecules |
JP6879549B2 (ja) * | 2017-04-27 | 2021-06-02 | 学校法人慶應義塾 | 排ガスを電解還元して有価物を回収する装置及び方法 |
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DE2154348A1 (de) * | 1971-11-02 | 1973-05-10 | Battelle Institut E V | Elektrochemisches verfahren zur herstellung aromatischer amine |
DE2429442C3 (de) * | 1974-06-19 | 1978-05-18 | Fritz, Heinz P., Prof. Dipl.-Chem. Dr., 8046 Garching | Verfahren zur Einführung von Nucleophilen in den gegebenenfalls alkylsubstituierten Kern des Benzols |
US6245242B1 (en) * | 1989-01-14 | 2001-06-12 | Basf Aktiengesellschaft | Cleanup of nitroaromatics-containing wastewaters |
DE19620861A1 (de) * | 1996-05-23 | 1997-11-27 | Basf Ag | Verfahren zur elektrochemischen Reduktion organischer Verbindungen |
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CN106414391B (zh) * | 2014-05-15 | 2019-08-30 | 科思创德国股份有限公司 | 通过在掺硼金刚石阳极上使未活化或去活化的芳族体系直接电化学胺化以制备1,5-二氨基萘和1-氨基-5-硝基萘的方法 |
CN108138340A (zh) * | 2015-10-15 | 2018-06-08 | 科思创德国股份有限公司 | 用于制备氨基官能的芳族化合物的方法 |
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