CN1599808A - 电解碱金属氯化物水溶液的方法 - Google Patents

电解碱金属氯化物水溶液的方法 Download PDF

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CN1599808A
CN1599808A CNA028240464A CN02824046A CN1599808A CN 1599808 A CN1599808 A CN 1599808A CN A028240464 A CNA028240464 A CN A028240464A CN 02824046 A CN02824046 A CN 02824046A CN 1599808 A CN1599808 A CN 1599808A
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CN1327033C (zh
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A·布兰
F·格斯特曼恩
H·-D·平特
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Bayer Intellectual Property GmbH
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
    • C25B1/46—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells
    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • C25B15/021—Process control or regulation of heating or cooling
    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms

Abstract

一种按照以碱金属氢氧化物，特别是氢氧化钠水溶液作为阴极电解液的隔膜方法而电解碱金属氯化物特别是氯化钠水溶液的方法，其特征在于，调节阳极半电池中的碱金属氯化物溶液的温度和/或阳极半电池中的碱金属氯化物溶液的体积流量，以使流入阴极半电池的碱金属氢氧化物溶液的温度和由阴极半电池流出的碱金属氢氧化物溶液的温度之间的差不超过15℃。

Description

电解碱金属氯化物水溶液的方法
本发明涉及一种电解碱金属水溶液的方法。
采用气体扩散电极作为耗氧阴极以通过电解碱金属氯化物溶液如氯化钠溶液来制备氯和碱金属氢氧化物水溶液如氢氧化钠溶液(下面也称为苛性钠)是已知的。这里电解槽由阳极半电池和阴极半电池组成，并且该两半电池是由阳离子交换膜分隔开。阴极半电池由电解质室构成，该室通过气体扩散电极与气室分隔开。电解质室装满碱金属氢氧化物溶液。向气室供入氧、空气或富氧空气。含碱金属氯化物的溶液存在于阳极半电池中。
从EP-A 1067215中已知一种在应用气体扩散电极作为耗氧阴极情况下电解碱金属氯化物水溶液的方法，在该方法中，在阴极半电池的电解质室中的碱金属氢氧化物溶液的流速至少为1cm/s。按照EP-A1067215，该碱金属氢氧化物溶液的高流速起到了良好的混合作用，以达到电解质室中的碱金属氢氧化物的浓度的均匀性。与此相反，在不用气体扩散电极作为耗氧阴极的碱金属氯化物电解中，不需采用高的流速，因为电解运行过程中在阴极形成的氢对碱金属氢氧化物溶液有足够的混合作用。
EP-A 1067215中已知的方法的缺点在于，电流产率随碱金属氢氧化物溶液的流速增加而下降。另外，在阴极半电池中碱金属氢氧化物溶液的温度随流速的下降而剧烈上升。
本发明的目的在于提供一种电解碱金属氯化物水溶液的可简单操作的方法，该方法可在尽可能低的流速下运行，同时不会使电解槽或电解装置的性能，特别是由于阴极半电池中的碱金属氢氧化物溶液的过高温度而恶化。
本发明的目的通过权利要求1的特征部分达到。
由此，本发明的目的是提供一种按照以碱金属氢氧化物，特别是氢氧化钠水溶液作为阴极电解液的隔膜方法而电解碱金属氯化物特别是氯化钠水溶液的方法，在该方法中，调节阳极半电池中的碱金属氯化物溶液的温度和/或阳极半电池中的碱金属氯化物溶液的体积流量，以使流入阴极半电池的碱金属氢氧化物溶液的温度和由阴极半电池流出的碱金属氢氧化物溶液的温度之间的差不超过15℃。
惊人地发现，按照本发明方法，借助于阳极半电池中的碱金属氯化物溶液的温度，以及只要存在阳极电解液循环，即碱金属氯化物溶液的循环，还借助于该碱金属氯化物溶液的体积流量，就可成功地调节阴极半电池中碱金属氢氧化物溶液的温度。该两措施之一或两措施的组合，就可克服碱金属氢氧化物溶液的变热，特别是在碱金属氢氧化物溶液的流速小于1cm/s情况下也可实现。此外，碱金属氢氧化物溶液的进出之间的温差大于15℃，优选大于10℃是不希望的，因为在进出之间的大的温度梯度会伴随产生碱金属氢氧化物溶液的大的电导率梯度。
在阳极半电池中碱金属氯化物溶液的给定体积流量和给定流出温度下借助于碱金属氯化物溶液的较低流入温度或在碱金属氯化物溶液的给定的流入温度和给定的流出温度下借助于碱金属氯化物溶液的较高体积流量即可在电解过程中实现阴极半电池中的碱金属氢氧化物溶液的冷却，以使阴极半电池中的碱金属氢氧化物溶液不超过所需的温度。两种手段可彼此组合。碱金属氯化物溶液的体积流量可借助碱金属氯化物溶液的循环泵送量来调节。
本发明方法的优点在于，碱金属氢氧化物溶液的温度不必通过阴极半电池中至少是1cm/s的高流速来调节。因为随较高流速会使电流产率下降，所以在小于1cm/s的低流速下运行是特别有利的。
或者，碱金属氢氧化物溶液的温度调节也可借助于阴极半电池前设置的热交换器来实现。但是，这在本发明方法中是不需要的，因此节省了附加的设备投资，这种投资是由安置热交换器产生的。
在本发明的一个优选实施方案中，碱金属氯化物溶液从阳极半电池流出时的温度和碱金属氢氧化物溶液从阴极半电池流出时的温度为80-100℃，优选85-95℃。
另一实施方案是优选的，该方案中阴极半电池中的碱金属氢氧化物溶液的流速小于1cm/s。
本发明方法优选在采用气体扩散电极作为阴极的条件下运行。作为阳极电解液的碱金属氯化物溶液和作为阴极电解液的碱金属氢氧化物溶液由碱金属如钠或钾本身得到。优选是该碱金属氯化物溶液是氯化钠溶液，碱金属氢氧化物溶液是氢氧化钠溶液。
在阳极半电池中的碱金属氯化物溶液的体积流量与电解装置运行中的电流密度有关。在电流密度为2.5kA/m2时，每个半电池的体积流量为0.02-0.1m3/h。在电流密度为4kA/cm2时，其体积流量为0.11-0.25m3/h。
本发明方法可以以2-8kA/m2的电流密度运行。
实施例：
相应于下述实施例的碱金属氯化物水溶液的电解用由15个电解槽组成的电解装置进行。在各电解槽中应用气体扩散电极作为阴极，其中该气体扩散电极与离子交换膜之间的距离为3mm，离子交换膜和气体扩散电极之间的间隙长度为206cm。采用钛阳极作为阳极，钛阳极上涂有钌-铱-氧化物。阳极面积为2.5m2。采用Dupont公司的NafionNX 981作为离子交换膜。由阳极半电池流出的氯化钠溶液(NaCl)的浓度为210g/l。在阴极半电池中的苛性钠(NaOH)的浓度为30-33重量％。如在下述实施例中不明确给出，则其电流密度为2.45kA/m2，苛性钠的体积流量为3m3/h。该流量相应于离子交换膜和气体扩散电极之间间隙中的苛性钠的流速为0.85cm/s。
实施例的结果综述于表1、2和3。
实施例1
在上述条件下，阳极半电池中的氯化钠溶液的体积流量选为1.0m3/h。氯化钠溶液的温度在流入时为50℃，流出时为85℃。由此，阳极半电池的流入和流出之间的温差为35℃。苛性钠以80℃流入阴极半电极，以85℃流出。电流产率为96.20％。
实施例2
在上述条件下，阳极半电池中的氯化钠溶液的体积流量选为1.1m3/h。氯化钠溶液的温度在流入时为50℃，流出时为86℃。由此，阳极半电池的流入和流出之间的温差为36℃。苛性钠以79℃流入阴极半电池，以85℃流出。电流产率为96.09％。
实施例3
在上述条件下，阳极半电池中的氯化钠溶液的体积流量选为1.2m3/h。氯化钠溶液的温度在流入时为51℃，流出时为85℃。由此，阳极半电池的流入和流出之间的温差为34℃。苛性钠以76℃流入阴极半电池，以83℃流出。电流产率为96.11％。
实施例4
在上述条件下，阳极半电池中的氯化钠溶液的体积流量选为1.3m3/h。氯化钠溶液的温度在流入时为55℃，流出时为86℃。由此，阳极半电池的流入和流出之间的温差为31℃。苛性钠以77℃流入阴极半电池，以83℃流出。电流产率为95.63％。
实施例5(对比例)
在上述条件下，阳极半电池中的氯化钠溶液的体积流量选为1.3m3/h。电流密度为2.5kA/m2。氯化钠溶液的温度在流入时为85℃，流出时为86℃。由此阳极半电池的流入和流出之间的温差为1℃。在阴极半电池中的苛性钠的体积流量为10.5m3/h，相应于苛性钠在离子交换膜和气体扩散电极之间的间隙中的流速为2.95cm/s。苛性钠以80℃流入阴极半电池，以86℃流出。电流产率为95.4％。
实施例6
电流密度为4kA/m2。阳极半电池的氯化钠的体积流量选为2.08m3/h。氯化钠溶液的温度在流入时为77℃，流出时为86℃。由此，阳极半电池的流入和流出之间的温差为9℃。阴极半电池中的苛性钠的体积流量为3m3/h，相应于苛性钠在离子交换膜和气体扩散电极之间的间隙中的流速为0.85m/s。苛性钠以82℃流入阴极半电池，以87℃流出。电流产率为96.1％。这表明，本发明方法也可在较高电流密度下运行并具有良好的电流产率。
表1：阳极半电池中的测量值
实施例     NaCl流入温度[℃]     NaCl流出温度[℃]   NaCl温差[℃]     NaCl体积流量[m3/h]
    1     50     85     35     1
    2     50     86     36     1.1
    3     51     85     34     1.2
    4     55     86     31     1.3
    5     85     86     1     1.3
    6     77     86     9     2.08
表2：阴极半电池中的测量值
实施例     Na0H流入温度[℃]     NaOH流出温度[℃]   NaOH温差[℃]     NaOH体积流量[m3/h]
    1     80     85     5     3
    2     79     85     6     3
    3     76     83     7     3
    4     77     83     6     3
    5     80     86     6     10.5
    6     82     87     5     3
表3：电流密度和电流产率
  实施例     电流密度[kA/m2]     电流产率[％]
    1     2.45     96.20
    2     2.45     96.09
    3     2.45     96.11
    4     2.45     95.63
    5     2.5     95.40
    6     4.0     96.10

Claims (4)

1.一种按照以碱金属氢氧化物、特别是氢氧化钠水溶液作为阴极电解液的隔膜方法而电解碱金属氯化物、特别是氯化钠水溶液的方法，其特征在于，调节阳极半电池中的碱金属氯化物溶液的温度和/或阳极半电池中的碱金属氯化物溶液的体积流量，以使流入阴极半电池的碱金属氢氧化物溶液的温度和由阴极半电池流出的碱金属氢氧化物溶液的温度之间的差不超过15℃。
2.权利要求1的方法，其特征在于，碱金属氯化物溶液从阳极半电池流出时的温度和碱金属氢氧化物溶液从阴极半电池流出时的温度为80-100℃，优选85-95℃。
3.权利要求1或2之一的方法，其特征在于，阴极半电池中碱金属氢氧化物的流速小于1cm/s。
4.权利要求1-3之一的方法，其特征在于，应用气体扩散电极作为阴极。
CNB028240464A 2001-12-05 2002-11-22 电解碱金属氯化物水溶液的方法 Expired - Lifetime CN1327033C (zh)

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EP1453990A2 (de) 2004-09-08
AU2002363856A1 (en) 2003-06-17
AR037637A1 (es) 2004-11-17
HUP0600453A2 (en) 2007-05-02
AU2002363856A8 (en) 2003-06-17
KR20050044700A (ko) 2005-05-12
JP2005511897A (ja) 2005-04-28
ES2448399T3 (es) 2014-03-13
JP4498740B2 (ja) 2010-07-07
TW200304502A (en) 2003-10-01
US6890418B2 (en) 2005-05-10
US20030121795A1 (en) 2003-07-03
WO2003048419A3 (de) 2003-10-02
CN1327033C (zh) 2007-07-18
DE10159708A1 (de) 2003-06-18
WO2003048419A2 (de) 2003-06-12

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