CN1060824C - 直接电化学气相合成碳酰氯的方法 - Google Patents
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Abstract
具有导质子膜4的电化学槽1用于直接电化学气相合成碳酰氯的工艺中。向电化学槽1的阳极2提供作为离析物的干HCl气和干CO气。阳极氧化HCl气所生成的氯自由基直接与CO气反应生成碳酰氯,而同时产生的质子通过隔膜4迁移至阴极3并在此还原为氢气,或当有氧存在时还原为水。
Description
本发明涉及一种将氯化氢电化学转化为碳酰氯的方法。根据迄今以来的常规方法,碳酰氯是由游离氯催化生成的。氯一般是由NaCl电解生产得到的,其中将例如由异氰酸盐的生产过程中产生的HCl气进一步处理为氢氯酸,或者氯是由电解氢氯酸水溶液回收得到的再循环氯。
US5411641中描述了一种生产氯的电化学方法,其中在电化学槽中用干法直接氧化HCl生成氯并且产生质子。甚至在伴随氢的制备中在阴极侧使用含水电解液时,该方法也可在与常规电解氢氯酸水溶液相比明显更为优越的操作电压下进行。
本发明的目的是以氯化氢气体为原料用电化学方法直接生产碳酰氯。
本发明为达到上述目的是将HCl气和干CO气作为离析物提供给装配有导质子膜的电化学槽的阳极,并且由阳极氧化HCl气所生成的氯自由基直接与CO气反应生成碳酰氯,而同时产生的质子通过该膜迁移至阴极并且在用含水HCl生产的情况时,质子被还原为氢,或当有氧存在时被还原为水。
在该工艺中,根据下列反应式,一般地氯自由基与CO气在阳极发生阳极氧化以生成碳酰氯
该反应优选以下述方式进行,即除了电化学阳极氧化外,在活性扩散型阳极含碳的载体材料中发生氯分子与CO气生成碳酰氯的放热催化反应,反应式如下
由于在该反应中生成碳酰氯自由基,从而可以使阳极过电位降低0.2-0.6V。
该方法可以便利地以如下方式进行,即为了减少电化学槽的操作电压,使氧气在阴极3还原并且与通过隔膜扩散过来的质子相互反应生成水而被消耗。
然而,另一方面该方法也可以用下述方法进行,即阴极3在氢氯酸水溶液中操作,其中生成作为第二产物的氢气。
为了调整其导电性,另外还需用湿氧气湿润该隔膜,湿氧气是与离析气一起提供给阴极的。
根据优选的实施方案,阴极和阳极的电化学反应在2巴-6巴的压力下进行。
本发明方法的进一步发展在于,在回收装置中冷却和液化在操作压力下由阳极侧抽出的碳酰氯气流并且在回收装置的第二面使该液化的碳酰氯减压和气化,其中产生液化所需的冷冻能力并且同时去除在第一面的液化碳酰氯中所存在的任何HCl和CO离析气。而后可将任何此种离析气返回到电化学槽中。
该电化学槽在一个封闭体系中进行操作是有利的,该体系还包括回收装置,操作压力为2巴-10巴,优选为在2巴-6巴的压力下进行,用此种方法可以使封闭体系和电化学槽之间的压差实质上为零,这样即使使用较高的压力,电化学槽也可在几乎没有压力的条件下操作。
与常规碳酰氯生产工艺相比,可以获得下述优点:
-加入适量的CO可以使干氯化氢以气相直接发生电化学反应生成碳酰氯。
-如果适当调节离析气混合物的组成,可以将产物气体中的游离氯的含量减少至可忽略的低量值。然而,即使仍然含有少量的HCl和CO,该产物气也可直接用于特定的化学过程中,例如异氰酸盐或聚碳酸酯的生产,在此种情况中这些余量的气体在通过该过程时呈惰性,而后与由异氰酸盐或聚碳酸酯形成过程中释放出来的HCl气流相结合,该HCl气流可以作为电化学碳酰氯生产中的离析气而重新输入。任何未反应的残余碳酰氯不破坏该电化学反应。如果浓度适当,它们至多起到气体扩散型阳极的扩散阻挡物的作用。
-由于与常规碳酰氯生产中所需的大量连续生产步骤相比,该电解设备的设计较为简单,从而使厂房和设备的成本显著减少(较低的投资成本)。
-在常规碳酰氯生产中,即使使用含水的氢氯酸进行电解,100kg的氯所需能量也为约180kWh/,由于需要大量的泵或压缩机并且由于需要冷冻剂(外来冷却)而使许多生产步骤能耗非常高。考虑到这些,根据本发明的方法具有相当合适的操作成本。
-从纯热力学观点看,HCl气与氧的电化学反应在低至约0.18V的电压下是放热反应。然而,实用时,300-400mV的氧过电位以及离子交换膜的电阻降低了能量平衡。
-由于其放热特性,在电化学过程中所直接含有的CO和COCl自由基对于电解电位具有积极影响。电位可以减少约200-600mV。
以下的附图和实施例用于进一步说明本发明。
图1为直接电化学生产碳酰氯的电解槽结构示意图。
图2为使用碳酰氯回收装置的耐压系统中的碳酰氯电解单元的基本结构。
将首先描述在阴极和阳极处发生的该电化学过程的一般反应机理。
1.阴极过程
在阴极,输入的氧气在设置于两个电极之间的导质子膜的界面处发生催化氧还原(催化剂为例如Pt、Ir或Pd)。用与PEM燃料电池相似的方法,将氧或输入的含有氧的气体混合物(原料气)用水湿润达到其饱和点。该反应根据下列反应式进行:
当考虑到反应式(1)中形成的水时,用预湿润原料气的方法调节导质子膜的水平衡。
2.电解质
用与PEM燃料电池相似的方法,将在离子迁移通道中具有质子化磺酸根的含氟聚合物制得的单层导质子膜用作阴极和阳极之间的固体电解质。如上所述,通过湿润该阴极侧可改善质子传导性。
3.阳极过程
基本过程包括直接氧化干HCl气以得到氯和质子,并将其输入作为电解质的隔膜中,根据下述反应在阳极和导质子膜之间的界面处发生催化氧化(催化剂为Pt、Ir、Rh或Pd)。在没有其它反应物存在时,直接氧化HCl产生干氯,干氯立即与同时供入的干CO气反应。可存在两个反应路径,且均为放热反应:
3.1对直接氧化HCl的直接影响
因此在反应的两个步骤中,氯化氢的氧化过程直接或间接地受到CO的影响。反应步骤中所释放的热至少部分地转化为直接电化氧化HCl的活化能的减少量,结果是降低了槽压。
3.2间接过程
任何没有与CO或COCl自由基反应的氯自由基重新结合得到Cl2。与电极结合使用的电化学活性催化剂的常规载体材料为乙炔黑形式的碳,其中电解释放的产物气Cl2和COCl2穿过该微孔载体层。此处的载体层被作为活性炭表面,在约80℃的常规槽温下,该层不能催化电化学反应,而是催化放热反应,
此后获得具有如下组成的干阳极产物气体:
COCl2+未反应的HCl气+未反应的CO+可能为痕量的Cl2。
进行上述反应所用的电化学槽的描述如下。
根据图1的电化学槽1基本上是由气体扩散型阳极2、气体扩散型阴极3和设置于电极之间并作为电解质的导质子膜4所组成的。此种膜电解质可作为电化学燃料电池的膜电解质商购到。阳极2由多孔、催化活性的活性炭基片5组成,该基片的内表面与隔膜3相连而其外表面与导电气体分流器6相连,并且该导电气体分流器6与阳极电流分配器7相连。阴极3与阳极的结构相似,它由催化活性炭基片8、导电气体分流器9和电流分配器10构成。铂、铱、铑和钯作为主要催化材料。此种气体扩散型阳极和阴极也可商购到(例如由GDE气体扩散型电极公司(Frankfurt am Main)出售的ELAT型电极)。
阳极2设置于阳极气室11中,而阴极3设置于阴极气室12中。除了进出口外,两个气室11和12是密封的。将HCl和CO的干离析气混合物通过进料口13输入阳极气室11中并且将氧和饱和水蒸气通过进料口14输入阴极气室12中。阴极还原反应中产生的水蒸气与离析气流一起确保隔膜4的充分湿润,从而使其不至于干燥。过量的水蒸气与未反应的氧一起通过出口16排出。
根据上述反应机理在气体扩散型阳极产生碳酰氯(COCl2),其中碳酰氯通过产物口15被排出。在阳极和阴极进行的电化学反应是在40-80℃温度下,槽压为0.8-1.2V并且电流密度约3kA/m2的条件下进行的。然而,该过程也可在更高电流密度下进行。该离析气是根据上述反应式以化学计量比加入的。然而,为了抑制游离氯的形成,提供给阳极的CO气也可以超化学计量的量加入。
在图2所示的进一步发展的电解槽中,许多具有与图1相似结构的电化学槽1被连接成串联或并联形式并安置在壳体18内作为双极电槽组17。
密闭的压力室19构成气密、耐压的封闭体系(设计最大压力为10巴),其中相对于实际操作压力的压差实际上为零。干离析气混合物HCl+CO通过离析气管线20和压缩机21提供给阳极。通过离析气管线22和压缩机23向阴极提供O2+H2O作为离析气。用压缩机21和23可以将离析气混合物压缩至具有高达约6巴的压力。
设置于电槽组17出口的产物管线24与碳酰氯回收装置25相连,在回收装置中,在电槽组17中所生成的碳酰氯通过热交换管组26的冷凝作用而发生液化。液态碳酰氯通过管线27流入储存容器28中。液化所需的冷冻能力是在回收装置25中将从储存容器28中输出来的液态碳酰氯减压而产生的。在末端,热交换管26通过上升管线29与储存容器28相连。恰好在回收装置25之前,液态碳酰氯流经上升管线29内的膨胀阀31。由于减压作用液态碳酰氯发生气化。在此情况下,碳酰氯作为冷冻剂以使基本上由碳酰氯组成的产物气体凝结。任何存在于产物气体中的未反应的HCl和CO离析气由冷凝作用和再气化所去除。得到的纯气态碳酰氯经由输出管线32被排出。减压作用将电槽组17中主要的超压离析气减至约为标准压力或后续反应所需的低初始压力,因此穿过电解槽的输出管线32上无需设置耐压设备。由HCl和CO组成并在回收装置25的顶部浓缩的残余气体通过返回管线33再循环至阳极入口。电槽组17阴极侧的出口与废气管线34相连以排出过量的氧和水蒸气。压力室19通过加压口35用惰气(例如氮气)加压,并且保持与压缩机21和23产生的初始离析气压力基本相同的压力。另外电化学槽必须具有耐压设计。该装置同时向反应设备提供了惰性气氛,该反应设备可以用简单的方法监控离析气或产物气的泄漏。
Claims (7)
1.一种将氯化氢电化学转化为碳酰氯的方法,包括下列步骤:
a)将作为离析物的干HCl气体和干CO气体提供给设置有质子传导膜(4)的电化学槽(1)的活性扩散阳极(2);
b)在阳极氧化所述HCl产生氯自由基和氢质子;
c)使步骤b)生成的氯自由基直接与CO气体反应生成碳酰氯;
d)使b)步骤产生的质子通过所述质子传导隔膜迁移至阴极(3);和
e)使在阴极存在的质子还原生成氢气,或当有氧存在时还原生成水。
2.根据权利要求1的方法,其特征在于,为了减少电化学槽的操作电压,使氧气在阴极(3)还原并且与通过所述膜扩散的质子反应生成水。
3.根据权利要求1的方法,其特征在于,阴极(3)在氢氯酸水溶液中操作并且生成作为第二产物的氢气。
4.根据权利要求2的方法,其特征在于,为了调整其导电性,通过向阴极(3)提供湿氧气使所述膜(4)发生附加湿润。
5.根据权利要求1的方法,其特征在于,在阴极(3)和阳极(2)的电化学反应在压力为2巴-10巴下进行。
6.根据权利要求5的方法,其特征在于,将由阳极侧排出的碳酰氯气流在回收装置(25)中在压力下冷却和液化,因此而除去任何存在于碳酰氯中的HCl和CO离析气体。
7.根据权利要求6的方法,其特征在于,所述电化学槽在还包括回收装置(25)的密闭体系(19)中在2巴-10巴的压力下进行操作,以致于与其中进行反应的部分相比仅有少量压差。
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DE19543678A DE19543678A1 (de) | 1995-11-23 | 1995-11-23 | Verfahren zur direkten elektrochemischen Gasphasen-Phosgensynthese |
DE19543678.4 | 1995-11-23 |
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EP (1) | EP0866890B1 (zh) |
JP (1) | JP2000501143A (zh) |
KR (1) | KR19990071564A (zh) |
CN (1) | CN1060824C (zh) |
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DE (2) | DE19543678A1 (zh) |
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HK (1) | HK1018081A1 (zh) |
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EP0866890B1 (de) | 2000-02-09 |
MX203057B (es) | 2001-07-13 |
DE19543678A1 (de) | 1997-05-28 |
TW420726B (en) | 2001-02-01 |
MX9803973A (es) | 1998-09-30 |
ES2144784T3 (es) | 2000-06-16 |
WO1997019205A1 (de) | 1997-05-29 |
DE59604440D1 (de) | 2000-03-16 |
EP0866890A1 (de) | 1998-09-30 |
HK1018081A1 (en) | 1999-12-10 |
JP2000501143A (ja) | 2000-02-02 |
KR19990071564A (ko) | 1999-09-27 |
US5961813A (en) | 1999-10-05 |
CA2237637A1 (en) | 1997-05-29 |
CN1202937A (zh) | 1998-12-23 |
BR9611499A (pt) | 1999-07-13 |
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