CN113214872B - 一种蓄热式煤气化制氢透氢膜反应器 - Google Patents
一种蓄热式煤气化制氢透氢膜反应器 Download PDFInfo
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- CN113214872B CN113214872B CN202110299184.6A CN202110299184A CN113214872B CN 113214872 B CN113214872 B CN 113214872B CN 202110299184 A CN202110299184 A CN 202110299184A CN 113214872 B CN113214872 B CN 113214872B
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Abstract
本发明公开了一种蓄热式煤气化制氢透氢膜反应器，属于煤气化重整制氢技术领域。本发明的透氢膜反应器采用镍基尖晶石负载活性组分为催化剂，金属镍纤维膜为透氢膜，以煤气化本身所携带的水蒸汽和空气中的氧为氧化剂，在透氢膜反应器中进行煤气化制氢反应，并转化为氢气、一氧化碳和二氧化碳等混合气体，而后通过金属镍纤维膜，得到高纯度氢气。本发明装置使制氢和提纯过程耦合到一起进行，反应效率高，所用催化剂活性好，操作稳定，而且氢气产率高和纯度高，并将具有十分巨大的经济、社会和环境效益。
Description
技术领域
本发明涉属于新能源领域，特别是煤气化重整制氢的技术领域。
背景技术
近年来，随着可持续发展观念的深化和人类对于能源需求量的日益增加，不可再生的化石燃料的使用对环境的影响不容忽视，开发和利用清洁的新能源成为越来越迫切的需求。氢气作为一种可再生能源由于其资源丰富、清洁、能量高等特点已经吸引了人们越来越多的关注。目前液氢已广泛应用于航天、军事应用、化学电源等领域。近几年来中国在氢能关键技术上已取得突破，初步掌握氢能基础设施与燃料电池的开发应用技术，具有产业装备及燃料电池整车生产能力，实现了小规模示范运营，为氢能及燃料电池产业大规模商业化运营奠定良好的基础。未来氢能的接受性与市场规模主要取决于终端用氢的价格、绿色性与安全性。目前常见的制氢(不包括工业废气中回收氢气) 的主要方法有天然气(含石脑油、重油、炼厂气和焦炉气等)蒸汽转化制氢、煤(含焦炭和石油焦等)转化制氢、甲醇或氨裂解制氢和水电解制氢，这其中，煤(含焦炭和石油焦等)转化制氢技术应用最为广泛，但在煤气化制氢过程中总是有氧气、甲烷、二氧化碳等杂质气体产生。因此在实际应用中，通过高效的物理或化学手段等将氢气从众多混合物中分离。传统的气体分离主要采用精馏、结晶、吸收、干燥、溶液萃取等技术，这些方法操作繁琐，装置复杂并且消耗能量大。对比传统方法，膜分离方法可以在分子尺度对气体进行分离，且具有低能耗、装置简单等特点。
发明内容
本发明的目的在于克服已有煤气化制氢过程中产氢效率和纯度低的缺点，公开了一种蓄热式煤气化制氢透氢膜反应器以及反应器内的蓄热催化床中的催化剂和镍基多孔介质，以及金属镍膜透氢膜，能够获得高纯度氢气，将催化剂和储热材料耦合，大幅提高煤气化制氢的效率，并且节能环保，安全高效，方便维护。
一种蓄热式煤气化制氢透氢膜反应器，反应器内部设有蓄热催化床，蓄热催化床上部设有上套段，蓄热催化床下部设有下套段，蓄热催化床外周设有热源，蓄热催化床中的催化剂为镍基尖晶石负载活性组分，其组分为NiO-SBA-15/Al-MCM-41/MMT/Al2O3；热催化床中的蓄热材料为镍基多孔介质，其孔隙率为60％-98％和孔密度为5PPI–5000PPI；所述下段套形成预混段，预混段设有煤粉进口和水蒸气进口，上套段的腔体内设有提纯段，所述提纯段包括金属镍膜透氢膜，其组分为:40-70wt％的镍粉、4-7wt％聚砜和20-40 wt％N-甲基吡咯烷酮；废气出口与提纯段联通，上套段还设有氢气出口。
进一步地，所述提纯段为多个并间隔设置在上套段内。
进一步地，所述提纯段在上套段内形成水平阵列。
进一步地，所述蓄热催化床与上套段和下套段之间通过金属密封圈密封连接。
进一步地，所述煤粉进口设置在预混段的侧部，所述水蒸气进口设置在预混段底部，所述氢气出口设置在上套段的侧部，所述废气出口设置在上套段的顶部。
一种制备上述镍基尖晶石负载活性组分的方法，包括以下步骤：
将8.0g P123溶解于300mL浓度为2M的盐酸水溶液中，控温在35～40℃搅拌直至表面活性剂全部溶解后加入21.5mL正硅酸四乙酯，在相同温度下搅拌24h，然后将上述白色乳液转入至聚四氟乙烯内衬的水热反应釜中，在100 ℃水热处理24h；
釜内产物用去离子水充分洗涤后在100℃烘干12h，再于550℃焙烧6h 除去有机模板剂后得到载体SBA-15；
以柠檬酸镍为前驱体，称取一定量的六水合硝酸镍溶于去离子水中，然后加入与六水合硝酸镍摩尔比为1:1的柠檬酸，将上述混合物在100℃回流24h，得到1M柠檬酸镍水溶液，将一定量预先干燥的SBA-15载体浸渍于l M柠檬酸镍水溶液中，所得的混合物于80℃水浴上搅拌蒸干，然后置于120℃烘箱中干燥过夜；
干燥后的样品在流速为90mL/min的模拟空气流以1℃/min的速率升温至 550℃焙烧6h制得催化剂。
进一步地，所述的模拟空气由高纯O2和N2配制。
一种制备上述镍基多孔介质的方法，包括以下步骤
首先将镍粉或镍合金粉与少量的发泡剂混匀，发泡剂为金属氢化物，用量通常不超过1％，将混匀的混合物压制成无残余通孔的密实块体；
压实后进行轧制、模锻或挤压，以使其成为半成品；
然后，将可发泡的半成品加热到接近或高于混合物熔点的高温，在加热过程中，发泡剂分解，释放出大量的气体，迫使致密的压实材料膨胀，形成多孔隙的泡沫材料。
一种制备权利要求1所述透氢膜的方法，包括以下步骤：
将有机聚合物聚砜分解到N-甲基-2-吡咯烷酮中，搅拌24小时形成聚合物溶液；
平均粒径在1-1.5μm、纯度为99.9％的镍粉加入到聚合物溶液中，充分搅拌36小时以保证镍粉粒子均匀分散；
在室温下将纺丝溶液转移到不锈钢储料罐中进行脱气，铸膜液通过氮气加压通过喷丝板孔直径在1.5-3.0mm挤到自来水中，留有空气距0.5mm，以去离子水为芯液，芯液流速设定为0.14cm3/s，形成中金属镍膜前驱体；
金属镍膜前驱体在水中充分浸泡24h使相转化完全形成稳固的多孔结构；
然后，将金属镍膜前驱体放置在管式炉中，以3℃/min的升温速率升温到 600℃，然后在600℃下保温1h；
然后，50mol％H2-N2混合气体以30ml/min的流速通入炉中，然后以升温速率30℃/min升温到1200℃以上，保温3h以获得致密的金属镍膜；
烧结后，金属膜在氢气的气氛下以3℃/min的降温速率降到室温得到需要的透氢膜材料。
进一步地，所述纺丝溶液包括40-70wt％的镍粉、4-7wt％聚砜和20-40wt ％N-甲基吡咯烷酮。
将煤粉和水蒸气在预混段充分混合，并进入蓄热催化反应段，在催化剂作用下，利用煤粉和水蒸汽，从而发生重整反应，进而得到H2、CO和CO2等小分子气体。
本发明采用镍基尖晶石负载活性组分催化剂有效克服了烧结，辅助发达孔隙结构以提供通畅的扩散通道，以大比表面积、大中孔负载活性颗粒，不仅制氢选择性好，缩短了化学链重整制氢由于燃料氧化而引起的产氢延迟，也提高了氧传递性能，其通畅的吸附、扩散和反应通道，对吸热、放热的强化传递和交换具有益处。
本发明的蓄热材料为镍基多孔介质，其单位体积内具有较高的表面积，并且其多孔介质的无序性，使得其对通过介质内的空气具有极高的扰动性，促使流体在经过这种不规则的换热表面时会产生更多的扰动和漩涡，极大的削弱了换热边界层的厚度，从而大大提高了换热系数，实现了强化换热的目的。
本发明的透氢膜为金属镍透氢膜，具有良好的延展性和可塑性以及更高机械强度，相对于传统的分离膜具有较高的氢气透量。在温度升高至1000℃在含CO2、CO、H20的气氛下，表现出了较高的稳定性。通过顺流模式切换到逆流模式中金属镍透氢膜的透氢速率能提高4-8％。
附图说明
图1本发明的蓄热式煤气化制氢透氢膜反应器的结构示意图。
具体实施方式
下面结合附图，进一步阐述本发明。应理解，这些实施仅用于说明本发明而不用于限制本发明的发明范围。此外应理解，在阅读了本发明的讲授内容之后，本领域技术人员可以对本发明做各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
本实施例参见图1，透氧膜反应器装置的结构包括有煤粉进口1、水蒸气进口2、氢气出口3、废气出口4、预混段5、热源6、蓄热催化床7、金属密封圈8、提纯段9、不锈钢密封构件10、上套段11和下套段12；其特征在于：整个蓄热式煤气化制氢透氢膜反应器为纵向立式布置形式，装置内设置有蓄热催化床7 及与其通过金属密封圈8相连的下套段11上套段12；蓄热催化床7外侧周围设置热源6；在装置下套段12侧部和底部分别设置有煤粉进口1和水蒸气进口2；在装置上套段11侧部和顶部分别设置有氢气出口3和废气出口4；在上套段11中还设由金属镍纤维膜组成的透氢膜9；本装置的主体上、下部均设有防止漏气的不锈钢密封构件10；本装置中的蓄热催化剂床7和透氢膜9的化学物质的组成如下:
1.蓄热催化床中的催化剂为镍基尖晶石负载活性组分，其组分为 NiO-SBA-15/Al-MCM-41/MMT/Al2O3；
2.蓄热催化床中的蓄热材料为镍基多孔介质，其孔隙率为60％-98％和孔密度为5PPI–5000PPI；
3.透氢膜为金属镍膜透氢膜，其组分为:40-70wt％的镍粉、4-7wt％聚砜和20-40wt％N-甲基吡咯烷酮。
制备镍基尖晶石负载活性组分催化剂:以NiO/SBA-15为例，SBA-15介孔分子筛的制备方法如下，将8.0g P123溶解于300mL浓度为2M的盐酸水溶液中，控温在35～40℃搅拌直至表面活性剂全部溶解后加入21.5mL正硅酸四乙酯，在相同温度下搅拌24h，然后将上述白色乳液转入至聚四氟乙烯内衬的水热反应釜中，在100℃水热处理24h。斧内产物用去离子水充分洗涤后在100℃烘干12h，再于550℃焙烧6h除去有机模板剂后得到载体SBA-15。NiO/SBA-15 的制备。以柠檬酸镍为前驱体，称取一定量的六水合硝酸镍溶于去离子水中，然后加入与六水合硝酸镍摩尔比为1:1的柠檬酸，将上述混合物在100℃回流 24h，得到1M柠檬酸镍水溶液，将一定量预先干燥的SBA.15载体浸渍于l M 柠檬酸镍水溶液中，所得的混合物于80℃水浴上搅拌蒸干，然后置于120℃烘箱中干燥过夜。干燥后的样品在流速为90mL/min的模拟空气(由高纯O2和 N2配制)流以1℃/min的速率升温至550℃焙烧6h制得催化剂。
制备金属镍膜透氢膜:是结合相转化技术和烧结技术制备金属镍中空纤维膜，将有机聚合物聚砜分解到N-甲基-2-吡咯烷酮中，搅拌24小时形成聚合物溶液。平均粒径在1-1.5μm、纯度为99.9％的镍粉加入到聚合物溶液中，充分搅拌36小时以保证镍粉粒子均匀分散。在室温下将纺丝溶液(40-70wt ％的镍粉、4-7wt％聚砜和20-40wt％N-甲基吡咯烷酮)转移到不锈钢储料罐中进行脱气，铸膜液通过氮气加压通过喷丝板孔直径在1.5-3.0mm挤到自来水中，留有空气距0.5mm，以去离子水为芯液，芯液流速设定为0.14cm3/s，形成中金属镍膜前驱体。金属镍膜前驱体在水中充分浸泡24h使相转化完全形成稳固的多孔结构。然后，将金属镍膜前驱体放置在管式炉中，以3℃/min 的升温速率升温到600℃，然后在600℃下保温1h。然后，50mol％H2-N2 混合气体以30ml/min的流速通入炉中，然后以升温速率30℃/min升温到1200 ℃以上，保温3h以获得致密的金属镍膜。烧结后，金属膜在氢气的气氛下以 3℃/min的降温速率降到室温得到需要的透氢膜材料。
制备蓄热材料为镍基多孔介质，是采用粉末冶金法制造泡沫镍材料，首先将镍粉或镍合金粉与少量的发泡剂混匀，如发泡剂为金属氢化物，用量通常不超过1％。将混匀的混合物压制成无残余通(开)孔的密实块体。常用的压实方法有：单轴向压制、挤压、粉末轧制。压实后还要做进一步的加工，诸如轧制、模锻或挤压，以使其成为半成品。然后，将此种可发泡的半成品加热到接近或高于混合物熔点的高温。在加热过程中，发泡剂分解，释放出大量的气体(氢)，迫使致密的压实材料膨胀，形成多孔隙的泡沫材料。泡沫铝材的密度或其孔隙率可通过发泡剂添加量或其他工艺参数如加热温度、加热速度等调控。
本发明采用镍基尖晶石负载活性组分催化剂有效克服了烧结，辅助发达孔隙结构以提供通畅的扩散通道，以大比表面积、大中孔负载活性颗粒，不仅制氢选择性好，缩短了化学链重整制氢由于燃料氧化而引起的产氢延迟，也提高了氧传递性能，其通畅的吸附、扩散和反应通道，对吸热、放热的强化传递和交换具有益处。
本发明所述蓄热材料为镍基多孔介质，其单位体积内具有较高的表面积，并且其多孔介质的无序性，使得其对通过介质内的空气具有极高的扰动性，促使流体在经过这种不规则的换热表面时会产生更多的扰动和漩涡，极大的削弱了换热边界层的厚度，从而大大提高了换热系数，实现了强化换热的目的。
本发明所述透氢膜为金属镍透氢膜，具有良好的延展性和可塑性以及更高机械强度，金属镍透氢膜有较高的氢气透量。在温度升高至1000℃在含CO2、 CO、H20的气氛下，表现出了较高的稳定性。通过顺流模式切换到逆流模式中金属镍透氢膜的透氢速率能提高4-8％。
采用本实施例中的透氧膜反应器装置，将煤粉和水蒸气在预混段充分混合，并进入蓄热催化反应段，在催化剂作用下，利用煤粉和水蒸汽，从而发生重整反应，进而得到H2、CO和CO2等小分子气体。金属镍透氢膜相对于传统的氢透膜具有较高的氢气透量，经检测，现有技术中的制氢纯度为99％，本实施的制氢纯度为99.99％。
本发明的技术方案与现有技术的制氢成本如下，
通过上述表格可知，本发明的制氢成本远小于其他方案，因此提高了生产效率。
尽管已经示出和描述了本发明的实施例，对于本领域的普通技术人员而言，可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型，本发明的范围由所附权利要求及其等同物限定。
Claims (4)
1. 一种蓄热式煤气化制氢透氢膜反应器，其特征在于，反应器内部设有蓄热催化床，蓄热催化床上部设有上套段，蓄热催化床下部设有下套段，蓄热催化床外周设有热源，蓄热催化床中的催化剂为镍基尖晶石负载活性组分，其组分为NiO-SBA-15/Al-MCM-41/MMT/Al2O3；热催化床中的蓄热材料为镍基多孔介质，其孔隙率为60%- 98%和孔密度为5 PPI –5000 PPI；所述下套段形成预混段，预混段设有煤粉进口和水蒸气进口，上套段的腔体内设有提纯段，所述提纯段包括金属镍膜透氢膜，其组分为: 40-70 wt％的镍粉、4-7 wt％聚砜和20-40 wt％N-甲基吡咯烷酮；废气出口与提纯段联通，上套段还设有氢气出口，所述提纯段为多个并间隔设置在上套段内。
2.根据权利要求1所述的蓄热式煤气化制氢透氢膜反应器，其特征在于，所述提纯段在上套段内形成水平阵列。
3.根据权利要求1所述的蓄热式煤气化制氢透氢膜反应器，其特征在于，所述蓄热催化床与上套段和下套段之间通过金属密封圈密封连接。
4.根据权利要求1所述的蓄热式煤气化制氢透氢膜反应器，其特征在于， 所述煤粉进口设置在预混段的侧部，所述水蒸气进口设置在预混段底部，所述氢气出口设置在上套段的侧部，所述废气出口设置在上套段的顶部。
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