CN112432429B - 一种低温精馏提取液氧中氪氙的装置及方法 - Google Patents

一种低温精馏提取液氧中氪氙的装置及方法 Download PDF

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CN112432429B
CN112432429B CN202011199933.XA CN202011199933A CN112432429B CN 112432429 B CN112432429 B CN 112432429B CN 202011199933 A CN202011199933 A CN 202011199933A CN 112432429 B CN112432429 B CN 112432429B
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包汉波
何晖
李相承
康玉茹
朱程浩
李冬锋
李剑锋
吴秀杰
袁士豪
孙潇
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Hang Yang Group Co ltd
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Abstract

一种低温精馏提取液氧中氪氙的装置，该装置包括一级浓缩塔、二级浓缩塔、三级浓缩塔、高压氧泵、水浴式汽化器、高压节流阀、回热器、除杂除甲烷模块和换热器，一级浓缩塔下部一侧设有通过原料液氧管道，一级浓缩塔底部通过管道依次与高压氧泵、水浴式汽化器液氧通道、高压节流阀、回热器、除杂除甲烷模块、水浴式汽化器氧气通道、换热器氧气通道相连接，换热器氧气通道通过第六管道与三级浓缩塔上部相连接，二级浓缩塔安装在三级浓缩塔上方，二级浓缩塔顶部通过管道与一级浓缩塔中部相连接，二级浓缩塔与三级浓缩塔之间设有一个第二再沸器。该发明应用范围广，可独立运行，同时可处理大量液氧而不受空分装置规模限制，可大规模生产氪氙。

Description

一种低温精馏提取液氧中氪氙的装置及方法
技术领域
本发明涉及深冷低温精馏提取液氧中氪、氙气体的方法，涉及一种可以安全、经济地从普通液氧中提取氪、氙的装置和方法。
背景技术
氪、氙在大气中的含量极为微少，分别为1.14ppm（百万分之一）和0.08ppm，被称为“黄金气体”，因此直接从空气中提取非常困难。空分装置获得氧、氮是本领域已知的方法，由于氪、氙和碳氢化合物的沸点与液氧的沸点比较接近，浓缩在液氧中从空分装置排放到液氧贮槽，其中碳氢化合物、氪、氙的含量均低于100ppm，因此以液氧为原料，从中提取氪、氙气体蕴藏着较大的经济前景。
已知的获得氪氙的方法，从下塔塔釜引出一部分含氪氙的液氧送入贫氪塔进行精馏，贫氪塔底部得到含0.5%碳氢化合物、1%氪、0.1%氙的贫氪氙液氧，将此贫氪氙液氧从空分装置引出，用高压液氧泵加压到5.5MPa临界压力下汽化，再减压到0.5MPa后加入催化剂，加热至450℃，使得碳氢化合物与氧反应，反应生成的二氧化碳和水蒸汽通过分子筛除去，除去二氧化碳和水蒸汽的氧气经冷氮气冷却后再被送到安装在空分装置中的粗氪塔继续浓缩精馏获得氪氙混合物。
已知方法中，贫氪塔设置在空分装置内部，因此氪氙的生产受空分装置规模的限制，受到原料空气量的制约；此外，贫氪塔贫氪氙液氧中碳氢化合物的含量过高对空分装置的危险性极大。
发明内容
本发明的目的在于克服上述存在的不足，提供一种无须在空分装置中设置贫氪塔和粗氪塔，就可安全、经济地从液氧中提取氪氙的方法和装置。
本发明的目的是通过如下技术方案来完成：一种低温精馏提取液氧中氪氙的装置，该装置包括一级浓缩塔、二级浓缩塔、三级浓缩塔、高压氧泵、水浴式汽化器、高压节流阀、回热器、除杂除甲烷模块和换热器，所述一级浓缩塔的下部一侧设有通过原料液氧的第一管道，其一级浓缩塔的底部通过第四管道依次与高压氧泵、水浴式汽化器的液氧通道、高压节流阀、回热器、除杂除甲烷模块、水浴式汽化器的氧气通道、换热器的氧气通道相连接，所述换热器的氧气通道再再通过第六管道与三级浓缩塔的上部相连接，该二级浓缩塔安装在该三级浓缩塔的上方，所述二级浓缩塔顶部通过第九管道与一级浓缩塔中部相连接，该二级浓缩塔与三级浓缩塔之间还设有一个第二再沸器。
作为优选：所述一级浓缩塔的底部设置有第一再沸器，所述第一再沸器设有氮气管道，其第一再沸器通过液氮管道与一级浓缩塔在其顶部相连接，该液氮管道上设有一节流阀，所述一级浓缩塔顶部还设置有一冷凝器，所述冷凝器通过管道与一级浓缩塔顶部的气体相连接，该冷凝器侧面的下方通过第一液氧管道与二级浓缩塔顶部相连接做液氧喷淋，并通过所述第二液氧管道在一级浓缩塔顶部做液氧喷淋。
作为优选：所述二级浓缩塔的塔釜经过第二管道与所述一级浓缩塔相连接。
作为优选：所述三级浓缩塔顶部气体通过第五管道与第二再沸器相连接，所述第二再沸器再通过第三管道与所述三级浓缩塔顶部相连接做液氧喷淋。
作为优选：所述除杂除甲烷模块由催化反应炉和分子筛吸附器组成。
作为优选：所述一级浓缩塔、二级浓缩塔和三级浓缩塔集成在一个绝热箱内，所述绝热箱可固定安装也可灵活移动，以便处理不同地点的液氧或将分散的液氧集中处理生产。
一种低温精馏提取液氧中氪氙的装置提取液氧中氪氙的方法，包含以下步骤：
a) 将液氧送入一级浓缩塔精馏，精馏后得到的氧气分成两股，一股作为高纯氧产品采出，一股冷凝后一部分送入二级浓缩塔进行二次精馏，一部分作为一级浓缩塔塔顶喷淋液，将二级浓缩塔塔釜液氧送入一级浓缩塔作为一级浓缩塔喷淋液，从一级浓缩塔的塔釜引出一股液氧经过高压泵加压后汽化，经过除杂除甲烷模块除去碳氢化合物后经过换热器冷却并送入三级浓缩塔蒸馏，从三级浓缩塔的塔釜引出产品氪氙浓缩液；
b）一级浓缩塔中的再沸器通入中压氮气，氮气在塔釜的液氧中冷却到露点温度，液氧的冷量交换给氮气，氮气经过节流后作为一级浓缩塔的冷源；
c) 除杂除甲烷模块包括催化反应炉和分子筛吸附器,其中催化反应炉内部催化剂为含钯0.1%~0.8%触媒，优选0.5%，催化反应炉内部自带电加热，反应温度400~500℃，优选450℃，其中氧气与碳氢化合物反应生产水蒸汽和二氧化碳，随后经过分子筛吸附器，水蒸汽和二氧化碳被除去，分子筛吸附器内部填充4A或5A型号分子筛;
d) 换热器（31）的冷流股（33）来自一级浓缩塔冷凝器汽化后的冷氮气（35）；
e）一股流量5210Nm3/h，温度-160℃的冷氮气，压力为1.0~2.0MPa，优选1.5MPa，进入一级浓缩塔的再沸器与塔釜内的液氧进行换热，氮气被冷却到-170℃，经过节流阀到0.3MPa，形成液氮进入一级浓缩塔顶部作为冷源，与一级浓缩塔顶部的氧气进行换热，氧气被液化后分成两股，一股作为所述一级浓缩塔的喷淋液，一股作为二级浓缩塔的喷淋液。所述二级浓缩塔塔釜液氧从一级浓缩塔底部上方理论级板的位置导入塔内，所述二级浓缩塔的第二再沸器以三级浓缩塔顶部氧气为热源，与二级浓缩塔塔釜的液氧进行换热，冷却后液氧作为三级浓缩塔的喷淋液。
与已知方法相比，本发明的方法具有以下优点：
1.应用范围广，可脱离空分装置独立运行，同时可处理大量的液氧而不受空分装置规模的限制，可大规模生产氪氙；
2.设置三级浓缩，可同时生产氪氙浓缩物和高纯氧产品，通过逐级精馏，最终可获得纯度高于99.999%的高纯氧产品；
3.可实现氪氙混合物和高纯氧的同时回收，而且高纯氧的回收率高，可达到95%以上，提高了该装置附加值。
附图说明
图1为本发明的工艺流程图。
具体实施方式
下面将结合附图对本发明作详细的介绍：如附图1所示，一种低温精馏提取液氧中氪氙的装置，该装置包括一级浓缩塔1、二级浓缩塔2、三级浓缩塔3、高压氧泵15、水浴式汽化器17、高压节流阀19、回热器30、除杂除甲烷模块26和换热器31，所述一级浓缩塔1的下部一侧设有通入原料液氧的第一管道6，该一级浓缩塔1的底部通过第四管道14依次与高压氧泵15、水浴式汽化器17的液氧通道、高压节流阀19、回热器30、除杂除甲烷模块26、水浴式汽化器17的氧气通道、换热器31的氧气通道相连接，所述换热器31的氧气通道再通过第六管道29与三级浓缩塔3的上部相连接，所述二级浓缩塔2安装在该三级浓缩塔3的上方，该二级浓缩塔2顶部通过第九管道8与一级浓缩塔1中部相连接，所述二级浓缩塔2与三级浓缩塔3之间还设有一个第二再沸器25。
所述一级浓缩塔的底部设置有第一再沸器23，所述第一再沸器23设有氮气管道4，其第一再沸器23通过液氮管道5与一级浓缩塔1在其顶部相连接，该液氮管道5上设有一节流阀27，所述一级浓缩塔顶部还设置有一冷凝器24，所述冷凝器24通过管道12与一级浓缩塔1顶部的气体相连接，该冷凝器24通过第一液氧管道10与二级浓缩塔2顶部相连接做液氧喷淋，并通过所述第二液氧管道9在一级浓缩塔1顶部做液氧喷淋。
所述二级浓缩塔2的塔釜经过第二管道7与所述一级浓缩塔1相连接。所述三级浓缩塔3顶部气体通过第五管道21与第二再沸器25相连接，所述第二再沸器25再通过第三管道13与所述三级浓缩塔3顶部相连接做液氧喷淋。所述除杂除甲烷模块26由催化反应炉16和分子筛吸附器18组成。所述一级浓缩塔1、二级浓缩塔2和三级浓缩塔3集成在一个绝热箱内，所述绝热箱可固定安装也可灵活移动，以便处理不同地点的液氧或将分散的液氧集中处理生产。
本发明所述的低温精馏提取液氧中氪氙的方法，它是将液氧送入一级浓缩塔精馏，精馏后得到的氧气分成两股，一股作为高纯氧产品采出，一股冷凝后一部分送入二级浓缩塔进行二次精馏，一部分作为一级浓缩塔1塔顶喷淋液，将二级浓缩塔2塔釜液氧送入一级浓缩塔作为一级浓缩塔喷淋液，从一级浓缩塔的塔釜引出一股液氧经过高压泵加压后汽化，经过除杂除甲烷模块除去碳氢化合物后经过换热器冷却并送入三级浓缩塔精馏，从三级浓缩塔的塔釜引出产品氪氙浓缩液。
所述的一级浓缩塔1中的第一再沸器23通入中压氮气，氮气在塔釜的液氧中冷却到露点温度，这样液氧的冷量交换给氮气，氮气经过节流后作为一级浓缩塔1的冷源。
所述的除杂除甲烷模块26由催化反应炉16和分子筛吸附器18组成。其中催化反应炉16内部催化剂为含钯0.1%~0.8%触媒，优选0.5%，催化反应炉内部自带电加热，反应温度400~500℃，优选450℃，其中氧气与碳氢化合物反应生产水蒸汽和二氧化碳，随后经过分子筛吸附器，水蒸汽和二氧化碳被除去，分子筛吸附器内部填充4A或5A型号分子筛。
一股流量5210Nm3/h，温度-160℃的冷氮气，压力为1.0~2.0MPa，优选1.5MPa，进入一级浓缩塔1的第一再沸器23与塔釜内的液氧进行换热，氮气被冷却到-170℃，经过节流阀27到0.3MPa，形成液氮进入一级浓缩塔1顶部作为冷源，与一级浓缩塔1顶部经过管道12的氧气进行换热，氧气被液化后分成两股，一股作为所述一级浓缩塔1的喷淋液，一股作为二级浓缩塔2的喷淋液。所述二级浓缩塔2塔釜液氧7从一级浓缩塔1底部上方5块理论级板的位置导入塔内，所述二级浓缩塔2的第二再沸器25以三级浓缩塔3顶部氧气21为热源，与二级浓缩塔2塔釜的液氧进行换热，冷却后液氧13作为三级浓缩塔3的喷淋液。
具体实施例
以3000 Nm3/h液氧的生产为例。3000 Nm3/h原料液氧含100ppm氪，30ppm氙，100ppmCnHm（碳氢化合物），在一级浓缩塔1底部上方5块理论级的位置导入塔内，进行精馏，一级浓缩塔1的理论级为12。绝大部分高沸点的氪、氙和碳氢化合物冷凝下流到一级浓缩塔1的底部，低沸点的氧、氩和少量的氪、氙从下流液体中挥发出来到达塔顶，被液氮冷凝后一部分作为一级浓缩塔1的喷淋液，一部分送入二级浓缩塔2，低沸点的氧和氩从下流液体中挥发出来，高沸点的氪、氙冷凝下流到二级浓缩塔2的底部，将二级浓缩塔2底部的液氧送入一级浓缩塔底部上方5块理论板的位置进行精馏，原料液氧中的氪、氙和大部分烃类最终浓集在一级浓缩塔1的塔釜。
从一级浓缩塔1的底部引出700Nm3/h液氧，含447ppm氪，150ppm氙，432ppmCnHm，温度为-165℃，经过高压液氧泵加压到5.5MPa临界压力下汽化后复热至25℃，再减压到0.5MPa经过回热器30后进入除杂除甲烷模块26，除杂除甲烷模块26包括催化反应炉和分子筛吸附器。其中催化反应炉内部催化剂为含钯0.1%~0.8%触媒，优选0.5%，催化反应炉内部自带电加热，反应温度400~500℃，优选450℃，其中氧气与碳氢化合物反应生产水蒸汽和二氧化碳，随后经过分子筛吸附器，水蒸汽和二氧化碳被除去，分子筛吸附器内部填充4A或5A型号分子筛。
700Nm3/h氧气从除杂除甲烷模块26引出，经过水浴式汽化器17及换热器31冷却到-160℃，通过管道29进入三级浓缩塔的顶部进行精馏，三级浓缩塔3的理论板为12。
在三级浓缩塔3中，低沸点的氧、氩从下流液体中挥发出来到达塔顶，高沸点的氪、氙则冷凝下流到三级浓缩塔3底部，99.9%氪氙混合物浓缩富集在三级浓缩塔3塔釜。
一股流量5210Nm3/h，温度-160℃的冷氮气，压力为1.0~2.0MPa，优选1.5MPa，进入一级浓缩塔1的第一再沸器23与塔釜内的液氧进行换热，氮气被冷却到-170℃，经过节流阀27到0.3MPa，形成液氮进入一级浓缩塔1顶部作为冷源，与一级浓缩塔1顶部的氧气12进行换热，氧气被液化后分成两股，一股作为所述一级浓缩塔1的喷淋液，一股作为二级浓缩塔2的喷淋液。所述二级浓缩塔2塔釜液氧7从一级浓缩塔1底部上方5块理论级板的位置导入塔内，所述二级浓缩塔2的第二再沸器25以三级浓缩塔3顶部氧气21为热源，与二级浓缩塔2塔釜的液氧进行换热，冷却后液氧13作为三级浓缩塔3的喷淋液。
所述一级浓缩塔1塔顶从第七管道36带走的氧气中氪氙含量低于10ppm，所述二级浓缩塔2塔顶从第八管道8带走的氧气中氪氙含量低于50ppm。
所述的氮气可以是就近氮气管网提供或是就近的氮气压缩机提供。
本发明所述的低温精馏提取液氧中氪氙的装置可集成在一个可移动的绝热箱内，该绝热冷箱可固定安装也可灵活移动，以便处理不同地点的液氧或将分散的液氧集中处理生产，从而节省了大量原料液氧集中运输的费用和冷量损失。

Claims (4)

1.一种低温精馏提取液氧中氪氙的装置，该装置包括一级浓缩塔（1）、二级浓缩塔(2)、三级浓缩塔（3）、高压氧泵（15）、水浴式汽化器（17）、高压节流阀（19）、回热器（30）、除杂除甲烷模块（26）和换热器（31），其特征在于所述一级浓缩塔（1）的下部一侧设有通入原料液氧的第一管道(6)，该一级浓缩塔（1）的底部通过第四管道（14）依次与高压氧泵(15)、水浴式汽化器（17）的液氧通道、高压节流阀（19）、回热器（30）、除杂除甲烷模块（26）、水浴式汽化器（17）的氧气通道、换热器（31）的氧气通道相连接，所述换热器（31）的氧气通道再通过第六管道（29）与三级浓缩塔(3)的上部相连接，所述二级浓缩塔(2)安装在该三级浓缩塔（3）的上方，该二级浓缩塔（2）顶部通过第九管道（8）与一级浓缩塔(1)中部相连接，所述二级浓缩塔（2）与三级浓缩塔（3）之间还设有一个第二再沸器(25)；所述一级浓缩塔（1）的底部设置有第一再沸器（23），所述第一再沸器（23）设有氮气管道（4），该第一再沸器（23）通过液氮管道（5）与一级浓缩塔(1)在其顶部相连接，该液氮管道（5）上设有一节流阀(27)，所述一级浓缩塔（1）顶部还设置有一冷凝器（24），所述冷凝器（24）通过管道（12）与一级浓缩塔（1）顶部的气体相连接，该冷凝器（24）通过第一液氧管道（10）与二级浓缩塔（2）顶部相连接做液氧喷淋，并通过第二液氧管道（9）在一级浓缩塔(1)顶部做液氧喷淋；所述二级浓缩塔(2)的塔釜经过第二管道(7)与所述一级浓缩塔(1)相连接；所述三级浓缩塔(3)顶部气体通过第五管道(21)与第二再沸器(25)相连接，所述第二再沸器(25)再通过第三管道(13)与所述三级浓缩塔(3)顶部相连接做液氧喷淋。
2.根据权利要求1所述的低温精馏提取液氧中氪氙的装置，其特征在于所述除杂除甲烷模块(26)由催化反应炉（16）和分子筛吸附器（18）组成。
3.根据权利要求1所述的低温精馏提取液氧中氪氙的装置，其特征在于所述一级浓缩塔（1）、二级浓缩塔(2)和三级浓缩塔（3）集成在一个绝热箱内，所述绝热箱可固定安装也可灵活移动，以便处理不同地点的液氧或将分散的液氧集中处理生产。
4.一种利用权利要求1-3任意一项所述装置提取液氧中氪氙的方法，其特征在于包含以下步骤：
a) 将液氧送入一级浓缩塔精馏，精馏后得到的氧气分成两股，一股作为高纯氧产品采出，一股冷凝后一部分送入二级浓缩塔进行二次精馏，一部分作为一级浓缩塔（1）塔顶喷淋液，将二级浓缩塔塔釜液氧送入一级浓缩塔作为一级浓缩塔喷淋液，从一级浓缩塔的塔釜引出一股液氧经过高压泵加压后汽化，经过除杂除甲烷模块除去碳氢化合物后经过换热器冷却并送入三级浓缩塔精馏，从三级浓缩塔的塔釜引出产品氪氙浓缩液；
b）一级浓缩塔中的再沸器通入中压氮气，氮气在塔釜的液氧中冷却到露点温度，液氧的冷量交换给氮气，氮气经过节流后作为一级浓缩塔的冷源；
c) 除杂除甲烷模块（26）包括催化反应炉（16）和分子筛吸附器（18）,其中催化反应炉内部催化剂为含钯0.1%~0.8%触媒，催化反应炉内部自带电加热，反应温度400~500℃，其中氧气与碳氢化合物反应生产水蒸汽和二氧化碳，随后经过分子筛吸附器，水蒸汽和二氧化碳被除去，分子筛吸附器内部填充4A或5A型号分子筛；
d) 换热器（31）的冷流股（33）来自一级浓缩塔冷凝器汽化后的冷氮气（35）；
e）一股流量5210Nm3/h，温度-160℃的冷氮气，压力为1.0~2.0MPa，进入一级浓缩塔（1）的第一再沸器（23）与塔釜内的液氧进行换热，氮气被冷却到-170℃，经过节流阀(27)到0.3MPa，形成液氮进入一级浓缩塔（1）顶部作为冷源，与一级浓缩塔（1）顶部的氧气进行换热，氧气被液化后分成两股，一股作为所述一级浓缩塔(1)的喷淋液，一股作为二级浓缩塔(2)的喷淋液，所述二级浓缩塔(2)塔釜液氧（7）从一级浓缩塔（1）底部上方5块理论级板的位置导入塔内，所述二级浓缩塔(2)的第二再沸器（25）以三级浓缩塔（3）顶部氧气(21)为热源，与二级浓缩塔(2)塔釜的液氧进行换热，冷却后液氧(13)作为三级浓缩塔(3)的喷淋液。
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