CN115557778A - 陶瓷组合物、微滤陶瓷膜及其制备方法与应用 - Google Patents

陶瓷组合物、微滤陶瓷膜及其制备方法与应用 Download PDF

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CN115557778A
CN115557778A CN202211303564.3A CN202211303564A CN115557778A CN 115557778 A CN115557778 A CN 115557778A CN 202211303564 A CN202211303564 A CN 202211303564A CN 115557778 A CN115557778 A CN 115557778A
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microfiltration
ceramic membrane
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membrane
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李丹
石勇
卞铁铮
祝菁泽
马金成
杨佳丽
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Jiangsu Tianhe Green Hydrogen Energy Technology Co ltd
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Abstract

本发明涉及陶瓷组合物、微滤陶瓷膜及其制备方法与应用。该陶瓷组合物，包含如下组分：陶瓷骨料，0.01～5wt％的造孔剂，增塑剂，和0.01～5wt％的颗粒粘结剂，基于所述陶瓷组合物的总重量，其中，所述陶瓷骨料为TiO2、ZrO2、Al2O3、SiO2中的一种或多种，粒径为1～500μm。利用本申请组合物制备得到的陶瓷微滤膜具有高孔隙率和大的孔径，将所制得的陶瓷膜用于过滤电解制氢工艺中循环的碱液，可以有效的去除碱液中的悬浮物，保证电解水制氢过程的运行稳定性。

Description

陶瓷组合物、微滤陶瓷膜及其制备方法与应用
技术领域
本发明涉及陶瓷组合物以及微滤陶瓷膜，特别是用于制氢技术领域的微滤陶瓷膜以及应用于电解槽碱液循环处理。
背景技术
氢能是高效清洁环保型能源，是实现碳中和的重要支撑。目前，商业化制氢技术中电解水制氢技术成熟，应用广泛。碱性水电解是实现大规模制氢的关键技术，也是目前最成熟的制氢技术之一。在大规模应用过程中，长期稳定循环运行是核心关键。但是，碱水电解制氢系统在运行过程中，容易存在催化剂脱落、极板电腐蚀等问题，导致碱液在循环过程中槽内容易积累大量悬浮物，增加体系内阻，导致系统单位电耗增加。目前碱水电解槽中碱液循环过程中常使用的是镍网过滤器，这种过滤器存在着孔径较大的问题，碱液中的悬浮物不易去除，从而依然存在运行时间延长，电解槽单位电耗增加的问题。
发明内容
本申请提供一种用于制备微滤陶瓷膜的陶瓷组合物，包含如下组分：
陶瓷骨料，0.01～5wt％的造孔剂，增塑剂，和0.01～5wt％的颗粒粘结剂，基于所述陶瓷组合物的总重量，
其中，所述陶瓷骨料为TiO2、ZrO2、Al2O3、SiO2中的一种或多种，粒径为1～500μm。
在一种实施方式中，所述造孔剂为无机碳粉颗粒、碳纤维或二维碳纳米片中的一种或多种；优选地，无机碳粉颗粒的粒径为100nm～5μm；碳纤维直径10nm～500nm；二维碳纳米片大小为10～100nm×10～100nm。
在一种实施方式中，所述粘结剂为TiO2、ZrO2、Al2O3、SiO2中的一种或多种，粒径为5～200nm。
在一种实施方式中，增塑剂为聚乙烯醇；优选地，聚乙烯醇为质量分数20％的聚乙烯醇水溶液，添加量为0.01～3％体积分数。
另一方面，本申请还提供一种微滤陶瓷膜的制备方法，包括：
S1提供上述陶瓷组合物；
S2将所述陶瓷组合物经球磨后，形成陶瓷膜坯体；
S3将所述陶瓷膜坯体煅烧，得到所述微滤陶瓷膜。
在一种实施方式中，煅烧温度为1000～2000℃，煅烧时间2～10h。
在一种实施方式中，所述微滤陶瓷膜的孔隙率为30-70％，平均孔径为15-100μm。
在一种实施方式中，所述微滤陶瓷膜的孔隙率为30-60％，平均孔径为15-100μm。
本申请还涉及本申请的微滤陶瓷膜在电解制氢中的应用。本申请还涉及一种电解液循环处理方法，包括：使经分离器分离的来自电解槽的电解液进入包含本申请微滤陶瓷膜的过滤器，得到过滤的电解液；
将过滤的电解液输送回所述电解槽。
本申请的陶瓷组合物包含了无机碳粉颗粒、碳纤维或二维碳纳米片等作为造孔剂，可以通过调控造孔剂的大小和用量，调节所制备的陶瓷膜的孔隙率，从而可以制备出高通量的陶瓷膜；该高高通量陶瓷膜用于处理电解制氢的循环电解液特别是循环碱液时，可以有效去除碱液中的悬浮物，进而保证电解槽的长期稳定性。
附图说明
图1为实施例1所得管式陶瓷膜的电镜照片。
具体实施方式
下面通过附图和实施例对本申请进一步详细说明。通过这些说明，本申请的特点和优点将变得更为清楚明确。
在这里专用的词“示例性”意为“用作例子、实施例或说明性”。这里作为“示例性”所说明的任何实施例不必解释为优于或好于其它实施例。尽管在附图中示出了实施例的各种方面，但是除非特别指出，不必按比例绘制附图。
此外，下面所描述的本申请不同实施方式中涉及的技术特征只要彼此之间未构成冲突就可以相互结合。
本申请涉及一种微滤陶瓷膜，其孔隙率为30-60％，平均孔径为15-100μm，具有高通量，并且机械强度大，抗磨污染能力强。该微滤陶瓷膜特别适合用作电解槽碱液循环处理用的过滤器。
一方面，本申请涉及一种用于制备微滤陶瓷膜的陶瓷组合物，包含如下组分：
陶瓷骨料，
0.01～5wt％的造孔剂，
增塑剂，和
0.01～5wt％的粘结剂，
基于所述陶瓷组合物的总重量。
在一种实施方式中，所述陶瓷骨料为TiO2、ZrO2、Al2O3、SiO2中的一种或多种，粒径为1～500μm。该陶瓷骨料的用量占陶瓷组合物的总重量的大多数，例如可以为80wt％以上，90wt％以上。
在一种实施方式中，所述造孔剂可以为无机碳粉颗粒、碳纤维或二维碳纳米片。本申请采用无机碳粉颗粒、碳纤维或二维碳纳米片等作为造孔剂，通过调控造孔剂的大小和用量，从而可以起到调节微滤陶瓷膜的孔隙率的作用，价格便宜且操作简单。在一种实施方式中，无机碳粉颗粒的粒径可以为100nm～5μm。碳纤维的直径可以为10nm～500nm；二维碳纳米片大小可以为10～100nm×10～100nm等。造孔剂的用量可以为0.01～5wt％，基于所述陶瓷组合物的总重量。本申请使用的造孔剂为纳米尺度的无机碳颗粒、碳纤维或者二维碳纳米片，且使用量低，因而得到具有适当孔径和孔隙率的微滤陶瓷膜。
在一种实施方式中，所述粘结剂为TiO2、ZrO2、Al2O3、SiO2中的一种或多种，粒径为5～200nm。使用这种粒度较小的材料，能够在烧结过程中起到粘结大的陶瓷骨料颗粒的作用，从而增加陶瓷颗粒间的结合力。粘结剂的用量可以为0.01～5wt％，基于所述陶瓷组合物的总重量。
在一种实施方式中，增塑剂可以为聚乙烯醇。所用的聚乙烯醇可以为聚乙烯醇水溶液，例如质量分数5-30％例如10-20％的聚乙烯醇水溶液。聚乙烯醇的添加量可以为0.01～3体积％，基于所述陶瓷组合物的总体积。
使用该组合物制备微滤陶瓷膜时，可以包括如下步骤：
S1提供上述陶瓷组合物；
S2将所述陶瓷组合物经球磨后，形成陶瓷膜坯体；
S3将所述陶瓷膜坯体煅烧，得到所述微滤陶瓷膜。
S2步骤中，将所述陶瓷组合物球磨到表陶瓷粉体表面光滑后用于形成陶瓷膜坯体。
可以将球磨后的混料采用干压成型法形成管式或者片式陶瓷膜坯体，之后放在通风处自然晾干。
S3步骤中，将晾干后的陶瓷膜坯体放入马弗炉在一定温度下煅烧。在一种实施方式中，煅烧温度可以为1000～2000℃。
所得到的微滤陶瓷膜孔隙率为30-60％，平均孔径为15-100μm，具有高通量，并且机械强度大，抗磨污染能力强。该微滤陶瓷膜特别适合用作电解槽碱液循环处理用的过滤器，用于碱性水电解制氢过程中过滤循环碱液。因而，可以用于电解制氢中的应用，作为电解槽电解液特别是碱液循环处理用的过滤器。具体为电解水制氢系统中，气液分离后的电解液(碱液)经过冷却，进入陶瓷膜过滤器，出来的滤液循环回电解槽。利用本申请组合物制备得到的陶瓷微滤膜具有高孔隙率和大的孔径，将所制得的陶瓷膜用于电解制氢工艺中过滤循环的碱液，可以有效的去除碱液中的悬浮物，保证电解水制氢过程的运行稳定性。
本申请还涉及一种电解液循环处理方法，包括：
使经分离器分离的来自电解槽的电解液进入包含本申请的微滤陶瓷膜的过滤器，得到过滤的电解液；
将过滤的电解液输送回所述电解槽。
在电解水制备氢气的工艺中，从阳极部分流出的电解液中含有氧气，从阴极部分流出的电解液中含有氢气，可以通过气液分离去除电解液中的氧气和氢气，经过冷却之后，使电解液进入包含有本申请微滤陶瓷膜的过滤器进行过滤，去除其中的悬浮物，之后将电解液返回电解槽循环使用。
通常电解水制备氢气的工艺中使用的电解液为碱液例如KOH溶液。使用本申请高通量的陶瓷膜处理循环的电解液(例如碱液)，比起常用的镍丝网过滤精度更高，能够有效的去除电解液(例如碱液)中的悬浮沉淀物，保证电解槽的长期稳定性。
实施例1
陶瓷膜制备:将100μm的Al2O3粉体作为陶瓷骨料，质量分数0.3％的1μm碳粉颗粒作为造孔剂，0.1％体积分数的聚乙烯醇作为增塑剂和质量分数0.5％的200nm TiO2粉体作为粘结剂一起放进球磨罐球磨到陶瓷粉体表面光滑后，并压成管式素坯，自然风干后，放入马弗炉中在1700℃下煅烧4h，得到管式陶瓷膜，膜平均孔径约为20μm，孔隙率48.5％。所制得的膜其表面电镜照片如图1所示(日立S-4800型冷场发射扫描电镜(FE-SEM)，所制备的膜敲碎后取小块样品烘干喷金后进行测试)。
将所制得的管式陶瓷膜放入电解水制氢系统过滤器中，用于处理碱液循环水，去除电解液中的悬浮物。在恒定电解电流(121A)下测定随时间的产氢量、电压V、小室电压V0、碱液温度等，结果如表1所示。可以稳定运行2000h，电解槽能耗几乎没有改变。
表1
时间 产氢量 电解电流A 电压V 小室电压V0 碱液温度
1h 1m<sup>3</sup>/h 121 34.4 1.72 75/80℃
5h 1m<sup>3</sup>/h 121 34.4 1.72 75/80℃
10h 1m<sup>3</sup>/h 121 34.2 1.71 75/80℃
15h 1m<sup>3</sup>/h 121 34.6 1.73 75/80℃
20h 1m<sup>3</sup>/h 121 34.2 1.72 75/80℃
25h 1m<sup>3</sup>/h 121 34.2 1.71 75/80℃
30h 1m<sup>3</sup>/h 121 34.6 1.73 75/80℃
40h 1m<sup>3</sup>/h 121 34.4 1.72 75/80℃
50h 1m<sup>3</sup>/h 121 34.4 1.72 75/80℃
70h 1m<sup>3</sup>/h 121 34.6 1.73 75/80℃
100h 1m<sup>3</sup>/h 121 34.4 1.72 75/80℃
150h 1m<sup>3</sup>/h 121 34.4 1.72 75/80℃
200h 1m<sup>3</sup>/h 121 34.2 1.71 75/80℃
250h 1m<sup>3</sup>/h 121 34.4 1.72 75/80℃
300h 1m<sup>3</sup>/h 121 34.2 1.71 75/80℃
作为对比，电解槽过滤器采用60目镍丝网过滤器时，电解槽稳定运行2000h，电解槽能耗增大约10％。
实施例2
陶瓷膜制备:将200μm的TiO2粉体作为陶瓷骨料，质量分数0.1％的2μm碳粉颗粒作为造孔剂，0.2％体积分数的聚乙烯醇作为增塑剂和质量分数0.5％的500nm TiO2粉体作为粘结剂一起放进球磨罐球磨到陶瓷粉体表面光滑后，并压成管式素坯，自然风干后，放入马弗炉中在1800℃下煅烧4h，得到管式陶瓷膜，膜平均孔径约为35μm，孔隙率41.3％。
将所制得的管式陶瓷膜放入电解水制氢系统过滤器中，用于处理碱液循环水，去除电解液中的悬浮物。在恒定电解电流(125A)下稳定运行4000h，电解槽能耗几乎没有改变。
实施例3
陶瓷膜制备:将200μm的TiO2粉体，质量分数0.2％的100nm碳纳米纤维，0.5％体积分数的聚乙烯醇和质量分数0.5％的500nm ZrO2粉体一起放进球磨罐球磨到陶瓷粉体表面光滑后，并压成管式素坯，自然风干后，放入马弗炉中在1800℃下煅烧4h，得到管式陶瓷膜，膜平均孔径约为38μm，孔隙率52.1％。
将所制得的管式陶瓷膜放入电解水制氢系统过滤器中，用于处理碱液循环水，去除电解液中的悬浮物。在恒定电解电流(130A)下稳定运行4000h，电解槽能耗几乎没有改变。
实施例4
陶瓷膜制备:300μm的Al2O3粉体，质量分数0.5％的10×20nm碳二维纳米片，0.8％体积分数的聚乙烯醇和质量分数0.5％的1μm ZrO2粉体一起放进球磨罐球磨到陶瓷粉体表面光滑后，并压成管式素坯，自然风干后，放入马弗炉中在1800℃下煅烧6h，得到管式陶瓷膜，膜平均孔径约为45μm，孔隙率55.8％。
将所制得的管式陶瓷膜放入电解水制氢系统过滤器中备用，用于处理碱液循环水，去除电解液中的悬浮物。在恒定电解电流(140A)稳定运行10000h，电解槽能耗几乎没有改变。
以上结合了优选的实施方式对本申请进行了说明，不过这些实施方式仅是范例性的，仅起到说明性的作用。在此基础上，可以对本申请进行多种替换和改进，这些均落入本申请的保护范围内。

Claims (10)

1.一种用于制备微滤陶瓷膜的陶瓷组合物，包含如下组分：
陶瓷骨料，
0.01～5wt％的造孔剂，基于所述陶瓷组合物的总重量；
增塑剂，和
0.01～5wt％的颗粒粘结剂，基于所述陶瓷组合物的总重量；
其中，所述陶瓷骨料为TiO2、ZrO2、Al2O3、SiO2中的一种或多种，粒径为1～500μm。
2.根据权利要求1的陶瓷组合物，其中，
所述造孔剂为无机碳粉颗粒、碳纤维或二维碳纳米片中的一种或多种。
3.根据权利要求2的陶瓷组合物，其中，无机碳粉颗粒的粒径为100nm～5μm；碳纤维直径为10nm～500nm；二维碳纳米片大小为10～100nm×10～100nm。
4.根据权利要求1的陶瓷组合物，其中，所述粘结剂为TiO2、ZrO2、Al2O3、SiO2中的一种或多种，粒径为5～200nm。
5.根据权利要求1的陶瓷组合物，其中，增塑剂为聚乙烯醇；优选地，聚乙烯醇为质量分数5～30％的聚乙烯醇水溶液，添加量为0.01～3％体积分数。
6.一种微滤陶瓷膜的制备方法，包括：
S1提供权利要求1-3中任一项的陶瓷组合物；
S2将所述陶瓷组合物经球磨后，将球磨后表面光滑的陶瓷粉体压制形成陶瓷膜坯体；
S3将所述陶瓷膜坯体煅烧，得到所述微滤陶瓷膜。
7.根据权利要求6所述的制备方法，其中，煅烧温度为1000～2000℃，煅烧时间2～10h。
8.根据权利要求6或7的制备方法得到的微滤陶瓷膜，其中，所述微滤陶瓷膜的孔隙率为30-60％，平均孔径为15-100μm。
9.权利要求8的微滤陶瓷膜在电解制氢中的应用。
10.一种电解液循环处理方法，包括：
使经分离器分离的来自电解槽的电解液进入包含权利要求8的微滤陶瓷膜的过滤器，得到过滤的电解液；
将过滤的电解液输送回所述电解槽。
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