CN116178211A - 一种全氟异丁腈粗气中高含量酸性杂质的去除方法 - Google Patents

一种全氟异丁腈粗气中高含量酸性杂质的去除方法 Download PDF

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CN116178211A
CN116178211A CN202211704501.9A CN202211704501A CN116178211A CN 116178211 A CN116178211 A CN 116178211A CN 202211704501 A CN202211704501 A CN 202211704501A CN 116178211 A CN116178211 A CN 116178211A
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perfluoroisobutyronitrile
fiber
functional fiber
crude gas
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鲍金强
王泉高
张金彪
任章顺
于潇然
李前进
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Haohua Gas Co Ltd
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Abstract

本发明公开了一种全氟异丁腈粗气中高含量酸性杂质的去除方法，包括以下步骤：(1)将全氟异丁腈粗气通入一级吸附塔进行吸附，一级吸附塔中装填胺基改性的吸附功能纤维，吸附温度为0～50℃；吸附压力为0.01～0.3MPa；全氟异丁腈粗气流量为0.01～10L/min；(2)经过一级吸附塔后的全氟异丁腈进入二级吸附塔进行吸附，二级吸附塔中装填经预处理的多孔炭基吸附剂；吸附温度为0～50℃；吸附压力为0.01～0.3MPa；全氟异丁腈流量为0.01～5L/min。该方法可将全氟异丁腈粗气中高含量酸性杂质(含量大于100ppmw)去除至痕量水平，吸附剂无须频繁更换和再生，全氟异丁腈的损失少，方法简单高效。

Description

一种全氟异丁腈粗气中高含量酸性杂质的去除方法
技术领域
本发明涉及全氟异丁腈粗气中酸性杂质的去除方法。
背景技术
全氟异丁腈具有优良的电绝缘性能，可作为绝缘介质用于气体绝缘金属封闭开关设备(GIS)、气体绝缘输电线路(GIL)和气体绝缘开关柜中。其全球变暖潜能值(GWP)仅为SF6的1/10，臭氧破坏潜能为零，是一种绿色环保绝缘气体。
全氟异丁腈是采用脱水剂对七氟异丁酰胺进行脱水制备而得。所得粗气中由于存在酸性脱水剂及脱水后的酸性产物，导致粗气酸度偏高。酸性杂质会对电气设备的金属部件和绝缘材料造成腐蚀，直接影响电力开关设备的机械、导电以及绝缘性能。因此全氟异丁腈气体酸度是必须控制的指标。
全氟异丁腈气体中去除酸性杂质的常规方法一般有以下几种：(1)水洗法，该方法通过将全氟异丁腈粗气引入水洗塔，利用全氟异丁腈不溶于水、酸性杂质大量溶于水中的特性将酸去除。但该方法会引入大量的水分，增加后续去除水分的工艺难度。(2)碱洗法，该方法通过将全氟异丁腈粗气引入碱洗塔，利用碱液去除酸性杂质，但全氟异丁腈与碱也会发生反应。
专利文献CN110526834A公开了一种制备高纯全氟异丁腈方法。该专利以分子筛作为吸附剂，主要用以吸附全氟异丁腈原料气中的水分、不凝气体以及大部分未反应的含氟烯烃，同时也吸附微量酸性杂质。从该专利的实施例中，可以看出全氟异丁腈原料气经过单级分子筛吸附塔后，酸度由0.8～3.2ppmw降至0.1ppmw以下。但分子筛对酸性杂质吸附量低，根据实施例1-4原料中酸性杂质含量、经过分子筛吸附后酸性杂质含量、以及吸附所用分子筛的质量，计算得酸的吸附量仅为0.1～1mg/kg吸附剂。同时也会吸附一部分全氟异丁腈(吸附量为6～36g/kg吸附剂)，而且原料气中全氟异丁腈纯度越高，分子筛对全氟异丁腈的吸附量越大。
分子筛在全氟异丁腈中酸性杂质含量较低时有一定的除酸效果，但当全氟异丁腈中酸性杂质含量较高时，比如含量大于100ppmw，分子筛由于自身孔容小，会很快达到吸附饱和，需要频繁更换、再生吸附剂。同时造成产品全氟异丁腈的损失并且效率低下。因此，对于酸性杂质含量高的全氟异丁腈粗气，如何简单高效地将酸度降至痕量水平，是全氟异丁腈产业化过程中亟需解决的问题。
发明内容
本发明的目的在于提供一种全氟异丁腈粗气中高含量酸性杂质的去除方法，将全氟异丁腈粗气中高含量酸性杂质(含量大于100ppmw)去除至痕量水平，该方法吸附剂无须频繁更换和再生，全氟异丁腈的损失少，方法简单高效。
所述全氟异丁腈粗气是指由七氟异丁酰胺制备而得未经纯化的全氟异丁腈气体，其酸度以HF计，高于100ppmw。酸性杂质为由七氟异丁酰胺制备全氟异丁腈过程中所引入的酸性脱水剂及酸性产物。酸性脱水剂包括三氟乙酸酐、三氟甲磺酸酐、五氧化二磷、三氯氧膦或多聚磷酸等；酸性产物包括三氟乙酸、三氟甲磺酸、氯化氢或磷酸等。
为实现上述目的，本发明的技术方案是：一种全氟异丁腈粗气中高含量酸性杂质的去除方法，采用两级吸附的方式，包括以下步骤：
(1)将全氟异丁腈粗气通入一级吸附塔进行吸附，一级吸附塔中装填胺基改性的吸附功能纤维，吸附温度为0～50℃，优选15～30℃；吸附压力为0.01～0.3MPa，优选0.02～0.1MPa；全氟异丁腈粗气流量为0.01～10L/min，优选0.05～5L/min。经一级吸附塔吸附后，全氟异丁腈粗气的酸度，可由100ppmw以上降低至10ppmw以下。
所述胺基改性的吸附功能纤维，是将吸附功能纤维通过以下方法进行胺基改性所得：将多胺与去离子水以体积比1∶1～1∶5配成混合液，加热至90～150℃回流，将吸附功能纤维加入混合液中，吸附功能纤维与混合液质量比控制在1∶20～1∶100，回流反应2～15h，将吸附功能纤维从体系中取出，用甲醇或无水乙醇洗涤3～10次，再用去离子水洗涤直至水溶液为中性，洗涤后将纤维放入60～100℃烘箱中在抽真空状态下干燥至恒重，得到胺基改性的吸附功能纤维。
本发明所述的多胺是指乙二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺或多乙烯多胺等。
吸附功能纤维包括：天然纤维、聚烯烃纤维、聚氯乙烯纤维、聚乙烯醇纤维或聚丙烯腈纤维等。吸附功能纤维经过胺基改性得到相应胺基改性纤维，优选胺基改性的聚丙烯腈纤维。
胺基改性的吸附功能纤维技术指标可以用纤维的增重率来评定，增重率越高，则纤维的功能基含量越大，对酸性物质的吸附效果越好。本发明所采用的改性方法工艺简单，制得改性纤维的增重率可达20％～40％，改性纤维的柔韧性良好，综合力学性能满足使用要求，对酸性物质吸附效果优异。增重率按以下公式计算：
Figure BSA0000292603690000031
(2)经过一级吸附塔后的全氟异丁腈进入二级吸附塔进行吸附，二级吸附塔中装填经预处理的多孔炭基吸附剂；吸附温度为0～50℃，优选15～30℃；吸附压力为0.01～0.3MPa，优选0.02～0.1MPa；全氟异丁腈流量为0.01～5L/min，优选0.05～3L/min。经二级吸附塔后，全氟异丁腈的酸度可降至0.1ppmw以下。
步骤(2)中所述的多孔炭基吸附剂包括生物质基活性炭(例如木质活性炭、椰壳活性炭、煤质活性炭)和聚合物基多孔炭等；优选圆柱状煤质活性炭。
步骤(2)中多孔炭基吸附剂的预处理方法为：在惰性氛围下将多孔炭基吸附剂置于炭化炉中，以1～20℃/min速率升温至200～450℃，恒温1～6h；再以1～20℃/min速率升温至500～1200℃，恒温1～6h，然后降温至室温。惰性氛围优选氮气或氩气。
多孔炭基吸附剂经预处理后，比表面积为400～1300m2/g，优选900～950m2/g；孔容为0.4～0.8cm3/g，优选0.6～0.7cm3/g；颗粒直径为0.5～2mm，优选1.3～1.5mm；碘值700～1000mg/g，优选900～1000mg/g。
胺基改性的吸附功能纤维与多孔炭基吸附剂的使用质量比一般为1∶1～5∶1，优选质量比2∶1。
本发明方法相对于现有技术，具有以下有益效果：
1.本发明方法通过对吸附功能纤维进行胺基改性，改性纤维的增重率可达20％～40％，将该改性纤维联合预处理的炭基吸附剂用于全氟异丁腈粗气中高含量酸性杂质吸附，可将全氟异丁腈粗气的酸度由100ppmw以上降至0.1ppmw以下，方法简单高效。
2.本发明方法使用的吸附剂对酸性杂质吸附量高，且对全氟异丁腈吸附量小，对全氟异丁腈吸附量小于10g/kg吸附剂。对高含量酸性气体的吸附效果优于分子筛。
3.避免全氟异丁腈除酸过程中引入水分，降低去除水分的难度，节约生产成本。
具体实施方式
下面结合实施例对本发明技术方案做进一步说明，但并不将本发明局限于这些具体实施方式。
多孔炭基吸附剂预处理过程为：将多孔炭基吸附剂置于炭化炉中，以8℃/min速率升温至400℃，恒温4h；再以15℃/min速率升温至900℃，恒温5h，然后降温至室温。惰性氛围为氮气。
实施例1
胺基改性的吸附功能纤维制备：
将乙二胺与去离子水以体积比1∶1配成混合液，加热至113℃回流，将聚丙烯腈纤维加入混合液中，聚丙烯腈纤维与混合液质量比控制在1∶20，回流反应2h，将吸附功能纤维从体系中取出，用无水乙醇洗涤3次，再用去离子水洗涤直至水溶液为中性，洗涤后将纤维放入70℃烘箱中在抽真空状态下干燥直至恒重，得到乙二胺改性的聚丙烯腈纤维。改性纤维增重率为30％。
其中聚丙烯腈纤维(PANF)规格为2.5D/2.6dtex，纤维直径为9×10-3mm。
乙二胺改性的聚丙烯腈纤维结构式为：
Figure BSA0000292603690000051
n＝1500～3000。
将酸度(以HF计)为354ppmw的5.358kg全氟异丁腈粗气以3L/min的速度通入一级吸附塔中，吸附温度20℃，吸附压力0.1MPa。一级吸附剂为乙二胺改性的聚丙烯腈纤维。一级吸附剂填量为1.5kg。再以2L/min的速度通入二级吸附塔中，吸附温度25℃，吸附压力0.05MPa，二级吸附剂为预处理后的圆柱形煤质活性炭，比表面积为910m2/g；孔容为0.6cm3/g；颗粒直径为1.3mm；碘值930mg/g。二级吸附剂填量为0.5kg，共收集到5.301kg全氟异丁腈产品。
实施例2
胺基改性的吸附功能纤维制备：
将二乙烯三胺与去离子水以体积比1∶5配成混合液，加热至105℃回流，将聚丙烯腈纤维加入混合液中，聚丙烯腈纤维与混合液质量比控制在1∶100，回流反应15h，将吸附功能纤维从体系中取出，用无水乙醇洗涤10次，再用去离子水洗涤直至水溶液为中性，洗涤后将纤维放入70℃烘箱中在抽真空状态下干燥直至恒重，得到二乙烯三胺改性的聚丙烯腈纤维。改性纤维增重率为32％。
二乙烯三胺改性的聚丙烯腈纤维结构式为：
Figure BSA0000292603690000052
n＝1500～3000。
将酸度(以HF计)为231ppmw的5.522kg全氟异丁腈粗气以1L/min的速度通入一级吸附塔中，吸附温度15℃，吸附压力0.05MPa。一级吸附剂为二乙烯三胺改性的聚丙烯腈纤维。一级吸附剂填量为1kg。再以1.5L/min的速度通入二级吸附塔中，吸附温度20℃，吸附压力0.08MPa，二级吸附剂为预处理后的颗粒状木质活性炭。二级吸附剂填量为0.5kg，共收集到5.48kg全氟异丁腈产品。
实施例3
胺基改性的吸附功能纤维制备：
将三乙烯四胺与去离子水以体积比1∶2配成混合液，加热至102℃回流，将吸附功能纤维加入混合液中，吸附功能纤维与混合液质量比控制在1∶25，回流反应7h，将吸附功能纤维从体系中取出，用无水乙醇洗涤10次，再用去离子水洗涤直至水溶液为中性，洗涤后将纤维放入70℃烘箱中在抽真空状态下干燥直至恒重，得到三乙烯四胺基改性的吸附功能纤维。改性纤维增重率为35％。
将酸度(以HF计)为231ppmw的5.522kg全氟异丁腈粗气以1L/min的速度通入一级吸附塔中，吸附温度15℃，吸附压力0.05MPa。一级吸附剂为三乙烯四胺改性的聚丙烯腈纤维。一级吸附剂填量为1kg。再以1.5L/min的速度通入二级吸附塔中，吸附温度20℃，吸附压力0.08MPa，二级吸附剂为未经过预处理的颗粒状木质活性炭。二级吸附剂填量为0.5kg，共收集到5.492kg全氟异丁腈产品。
对实施例1～3中全氟异丁腈粗气、吸附后的产品进行分析检测，结果如表1、表2所示。
表1 全氟异丁腈粗气组分分析
检测项目 实施例1 实施例2 实施例3
酸度(以HF计)，ppmw 354 231 231
全氟异丁腈纯度，％ 86.5 95.3 95.3
表2 吸附后产物分析结果比较
检测项目 实施例1 实施例2 实施例3
酸度(以HF计)，ppmw 0.07 0.08 2.4
全氟异丁腈纯度，％ 87.3 95.9 95.8
由表1和表2分析数据可以看出，在实施例1和实施例2中，经过两级吸附后的全氟异丁腈粗气，其酸度均降至0.1ppmw以下。实施例3因活性炭未经过预处理，粗气酸度只能降到2.4ppmw，不能达到工艺指标要求。
对实施例1～2中吸附剂对全氟异丁腈中酸性杂质的吸附量进行计算，结果如表3所示。
表3 实施例1～2中吸附剂对全氟异丁腈中酸性杂质的吸附量
实施例1 实施例2
全氟异丁腈粗气质量/kg 5.358 5.522
全氟异丁腈粗气酸度/ppmw 354 231
吸附后产品质量/kg 5.301 5.48
吸附后产品酸度/ppmw 0.07 0.08
吸附剂质量(两级吸附剂质量之和)/kg 2.0 1.5
吸附剂对酸性杂质吸附量/mg/kg 948 850
由表3看出：本发明所选用的吸附剂，对全氟异丁腈中的酸性杂质吸附量高达850mg/kg以上，是分子筛对酸性杂质吸附量800倍以上，对酸性物质去除效果优异。吸附后产品的酸度值达到0.1ppmw以下。
对实施例1～2中吸附剂对全氟异丁腈的吸附量进行计算，结果见表4。
表4 实施例1～2中吸附剂对全氟异丁腈的吸附量
实施例1 实施例2
全氟异丁腈粗气质量/kg 5.358 5.522
全氟异丁腈粗气纯度/％ 86.5 95.3
吸附后的产品质量/kg 5.301 5.48
吸附后的产品纯度/％ 87.3 95.9
吸附剂质量(两级吸附剂质量之和)/kg 2.0 1.5
吸附剂对全氟异丁腈吸附量/g/kg 3.4 4.8
由表4看出：本发明制备的吸附剂，对全氟异丁腈的吸附量低，每千克吸附剂仅吸附3～5克全氟异丁腈，降低了全氟异丁腈在吸附过程中的损失，节约生产成本。

Claims (10)

1.一种全氟异丁腈粗气中高含量酸性杂质的去除方法，其特征在于采用两级吸附的方式，包括以下步骤：
(1)将全氟异丁腈粗气通入一级吸附塔进行吸附，一级吸附塔中装填胺基改性的吸附功能纤维，吸附温度为0～50℃；吸附压力为0.01～0.3MPa；全氟异丁腈粗气流量为0.01～10L/min；
所述胺基改性的吸附功能纤维，是将吸附功能纤维通过以下方法进行胺基改性所得：将多胺与去离子水以体积比1∶1～1∶5配成混合液，加热至90～150℃回流，将吸附功能纤维加入混合液中，吸附功能纤维与混合液质量比控制在1∶20～1∶100，回流反应2～15h，将吸附功能纤维从体系中取出，用甲醇或无水乙醇洗涤3～10次，再用去离子水洗涤直至水溶液为中性，洗涤后将纤维放入60～100℃烘箱中在抽真空状态下干燥直至恒重，得到胺基改性的吸附功能纤维；
(2)经过一级吸附塔后的全氟异丁腈进入二级吸附塔进行吸附，二级吸附塔中装填经预处理的多孔炭基吸附剂；吸附温度为0～50℃；吸附压力为0.01～0.3MPa；全氟异丁腈流量为0.01～5L/min。
2.根据权利要求1所述的去除方法，其特征在于步骤(2)中所述的多孔炭基吸附剂的预处理方法为：在惰性氛围下将多孔炭基吸附剂置于炭化炉中，以1～20℃/min速率升温至200～450℃，恒温1～6h；再以1～20℃/min速率升温至500～1200℃，恒温1～6h，然后降温至室温。
3.根据权利要求1所述的去除方法，其特征在于所述的多孔炭基吸附剂是指生物质基活性炭或聚合物基多孔炭。
4.根据权利要求3所述的去除方法，其特征在于所述的生物质基活性炭是指木质活性炭、椰壳活性炭或煤质活性炭。
5.根据权利要求1所述的去除方法，其特征在于所述的多孔炭基吸附剂是指圆柱状煤质活性炭。
6.根据权利要求1所述的去除方法，其特征在于胺基改性的吸附功能纤维与多孔炭基吸附剂的使用质量比为：1∶1～5∶1。
7.根据权利要求1所述的去除方法，其特征在于步骤(1)吸附温度为15～30℃；吸附压力为0.02～0.1MPa；全氟异丁腈粗气流量为0.05～5L/min；步骤(2)吸附温度为15～30℃；吸附压力为0.02～0.1MPa；全氟异丁腈流量为0.05～3L/min。
8.根据权利要求1所述的去除方法，其特征在于所述的多胺是指乙二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺或多乙烯多胺。
9.根据权利要求1所述的去除方法，其特征在于所述的吸附功能纤维是指天然纤维、聚烯烃纤维、聚氯乙烯纤维、聚乙烯醇纤维或聚丙烯腈纤维。
10.根据权利要求1所述的去除方法，其特征在于所述的胺基改性的吸附功能纤维是指胺基改性的聚丙烯腈纤维。
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GB1554052A (en) * 1977-08-05 1979-10-17 Vulikh A Purification of gases
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