CN106895256B - 色素水合物促进剂及其在制备高储气密度气体水合物中的应用 - Google Patents
色素水合物促进剂及其在制备高储气密度气体水合物中的应用 Download PDFInfo
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Abstract
本发明属于能源材料技术领域，公开了色素水合物促进剂及其在制备高储气密度气体水合物中的应用。所述色素水合物促进剂是由水和色素均匀混合而成。所述的应用为1)预处理阶段：将色素水合物促进剂加入高压反应釜内，采用待反应气体，排空；2)水合反应阶段：低温下，通入高压气体，反应一段时间，得到高储气密度的固态气体水合物。本发明的色素水合物促进剂，具有来源广泛，价格低廉，绿色环保，性能稳定，能够极大能缩短水合诱导时间，增大储气量，提高储气密度；同时对温度和压力条件没有特殊要求，制备方法快速简单，有望商业化。
Description
技术领域
本发明属于能源材料技术领域，具体涉及一种色素水合物促进剂及其在制备高储气密度气体水合物中的应用。
背景技术
气体水合物是水与甲烷、乙烷、CO2以及H2S等小分子气体形成的非化学计量性笼状晶体物质，又称为笼型水合物。形成水合物的水分子通过氢键相连形成一些多面体笼孔，尺寸合适的分子可以填充进这些笼孔中，使其具有热力学稳定性。在标准状态下，每立方米的水合物可以储存160～180立方米的气体。近年来，气体水合物技术涉及的领域越来越广，主要包括天然气储运、气体分离、海水淡化、污水处理、溶液浓缩、空调蓄冷等。然而，生成条件苛刻、诱导时间长、形成速率缓慢、储气量低等缺点极大地限制了该技术的推广，因此，寻找新型高效的促进剂是气体水合物技术得以在以上领域成功应用的关键。
促进气体水合物快速生成技术是水合物领域的热点问题，这是水合物应用技术的基础。科研工作者对此进行了大量研究，提出各种方法以促进水合物快速生成，例如合理的反应器形式(使用搅拌式反应器)、改变操作条件(在超声波、超重力、微波环境下进行水合物生成研究)、强化传质、传热条件(喷雾法、鼓泡法、管道螺旋流动法)、加入促进剂等。其中，使用促进剂可以避免设备的投资增长和流程复杂化，同时提高水合物生成速率。
表面活性剂是使用最多的促进剂，十二烷基硫酸钠(SDS)作为表面活性剂的代表，是目前使用最广泛的高效水合物促进剂。但是大多数表面活性剂来自不可再生的石油能源，价格高昂，不是一种环境友好型的促进剂。本发明采用色素作为水合物促进剂，价格低廉，环境友好，并且很多色素可以直接从植物的根、茎、叶中提取。
发明内容
为了克服当前技术的缺点与不足，本发明的目的在于提供一种色素水合物促进剂。
本发明的另一个目在于提供上述水合物促进剂在制备高储气密度气体水合物中的应用。本发明以色素作为水合物形成促进剂，制备高储气密度气体水合物，具有反应速度快，储气量高，原料来源广泛，无污染等优点。
本发明的目的通过以下技术方案实现：
一种色素水合物促进剂，是由水和色素均匀混合而成；具体由100质量份的水和0.01～10质量份的色素均匀混合而成。
所述的色素为叶绿素铜钠、苏木精、黑色素、茜素红、茜素黄R、靛蓝、藏花橙G、皂黄、叶绿素b、叶绿酸、花青素、芹菜素、木樨草素、桑色素、紫苏色素、紫玉米色素、葡萄皮色素、高粱红色素、菊花黄色素、红花素、血红素、胆红素、胭脂虫红、紫胶红、藻青素、藻蓝色素、苏木藻色素、虾壳色素、龙虾红色素、蟹壳色素、叶绿素铜、叶绿酸铁钠盐、叶绿素锌钠、茶绿素、菠菜色素、苜蓿色素、斑蝥黄、藏红花酸、虾青素、藏红花色素、红花红色素、红花黄A、红花黄色素、草莓色素、红球甘蓝、紫甘蓝色素、接骨木色素、萝卜红、越橘红、黑米色素、紫菜色素、红曲色素、黄红曲色素、红曲红色素、法夫酵母色素、可可色素、焦糖色素、乌贼色素、植物碳黑、甜菜红色素、栀子蓝色素、辣椒红、南瓜黄色素、沙棘黄、密蒙黄色素、柑橘皮黄色素、柑橘黄、枸杞色素、银杏黄色素、蒲公英色素、黑豆红、黑芝麻色素、玫瑰色素、苦水玫瑰色素、玫瑰茄红、杨梅色素、子壳棕、绒花红色素、黑加仑色素、紫菜苔色素、甜菜黄色素、胭脂红、诱惑红、日落黄、柠檬黄、亮蓝、喹啉黄、多穗柯棕、儿茶黑色素、金樱子棕、番茄红素、玉米黄素、原花青素、天竺葵色素、矢车菊色素、牵牛花色素、茶黄色素、决明子红色素、紫草色素、紫草红色素、桑椹红色素、槐豆胚芽色素、花生衣色素、紫青芋色素、苏木色素、紫蓝红色素、虎杖色素、凤仙花红色素、茜草色素、姜黄素、蓝锭果红、罗望子色素、薯蓣色素、板栗壳色素、火棘果色素、紫甘薯红色素、芸豆色素、柚皮苷、叶黄素、胡萝卜素中的一种以上；优选叶绿素铜钠、茜素黄R、苏木精、黑色素、茜素红、靛蓝、藏花橙G、皂黄的一种以上。
上述色素水合物促进剂在高储气密度气体水合物中的应用，具体包含以下步骤：
1)预处理阶段：将色素水合物促进剂加入高压反应釜内，采用待反应气体，排空(2～5min)，充分除去反应釜内空气，
2)水合反应阶段：低温下，通入高压气体，反应一段时间，得到高储气密度的固态气体水合物。
步骤(1)中所述的气体为甲烷、二氧化碳、氢气、氧气、氮气、硫化氢、氩气、氪气、氙气、乙烷、乙烯、丙烷中的一种或以上。
步骤(2)中所述低温为0～10℃；所述高压气体的压力为3～15兆帕；所述反应的时间为1～10h。
与现有技术相比，本发明具有如下优点及有益效果：
(1)本发明采用色素溶液作为快速制备高储气密度气体水合物促进剂，具有原料便宜易得、无毒害、无污染等优点，切合“绿色化学”的环保理念；
(2)本发明所采用的色素，重现性好，原料可直接使用；
(3)本发明所述的高储气密度气体水合物的制备方法简单，可极大提高水合物形成动力学和储气量，媲美当前广为采用的表面活性剂(尤其是SDS)，具有相当的实用价值。
具体实施方式
下面结合具体实施例对本发明作进一步地具体详细描述，但本发明的实施方式不限于此，对于未特别注明的工艺参数，可参照常规技术进行。
实施例1
一种色素水合物促进剂为质量分数为0.1％的色素溶液，由99.9克水和0.1克叶绿素铜钠配制而成；
所述色素水合物促进剂在制备高储气密度气体水合物中的应用即快速制备高储气密度气体水合物的方法：将80克色素水合物促进剂加入高压反应釜中(有效体积为500mL)，排空3min，在0℃下向高压反应釜中充入压力为9.5兆帕的甲烷气体，在色素水合物促进剂的作用下快速生长形成高储气密度的固体水合物，记录一定时间间隔的储气量，结果如表1所示。
实施例2
一种色素水合物促进剂为质量分数为0.05％的色素溶液，由99.95水和0.05克叶绿素铜钠配制而成；
所述色素水合物促进剂在制备高储气密度气体水合物中的应用即快速制备高储气密度气体水合物的方法：将80克色素水合物促进剂加入高压反应釜中(有效体积为500mL)，排空4min，在4℃下向高压反应釜中充入压力为8.5兆帕的甲烷气体，在色素促进剂的作用下快速生长形成高储气密度的固体水合物，记录一定时间间隔的储气量，结果如表1所示。
实施例3
一种色素水合物促进剂为质量分数为2％的色素溶液，由98克水和2克茜素黄R配制而成；
所述色素水合物促进剂在制备高储气密度气体水合物中的应用即快速制备高储气密度气体水合物的方法：将80克色素水合物促进剂加入高压反应釜中(有效体积为500mL)，排空3min，在1℃下向高压反应釜中充入压力为5.5帕的甲烷气体，在色素促进剂的作用下快速生长形成高储气密度的固体水合物，记录一定时间间隔的储气量，结果如表1所示。
实施例4
一种色素水合物促进剂为质量分数为5％的色素溶液，由95克水和5克苏木精配制而成；
所述色素水合物促进剂在制备高储气密度气体水合物中的应用即快速制备高储气密度气体水合物的方法：将80克色素水合物促进剂加入高压反应釜中(有效体积为500mL)，排空3min，在10℃下向高压反应釜中充入压力为10兆帕的甲烷气体，在色素促进剂的作用下快速生长形成高储气密度的固体水合物，记录一定时间间隔的储气量，结果如表1所示。
实施例5
一种色素水合物促进剂为质量分数为1％的色素溶液，由99克水和1克黑色素配制而成；
所述色素水合物促进剂在制备高储气密度气体水合物中的应用即快速制备高储气密度气体水合物的方法：将80克色素水合物促进剂加入高压反应釜中(有效体积为500mL)，排空4min，在3℃下向高压反应釜中充入压力为7兆帕的甲烷气体，在色素促进剂的作用下快速生长形成高储气密度的固体水合物，记录一定时间间隔的储气量，结果如表1所示。
实施例6
一种色素水合物促进剂为质量分数为2％的色素溶液，由98克水，1g茜素红和1克靛蓝配制而成；
所述色素水合物促进剂在制备高储气密度气体水合物中的应用即快速制备高储气密度气体水合物的方法：将80克色素水合物促进剂加入高压反应釜中(有效体积为500mL)，排空4min，在3℃下向高压反应釜中充入压力为12兆帕的氢气，在色素促进剂的作用下快速生长形成高储气密度的固体水合物，记录一定时间间隔的储气量，结果如表1所示。
实施例7
一种色素水合物促进剂为质量分数为3％的色素溶液，由97克水，1.5g茜素黄R、1.5g茜素红配制而成；
所述色素水合物促进剂在制备高储气密度气体水合物中的应用即快速制备高储气密度气体水合物的方法：将80克色素水合物促进剂加入高压反应釜中(有效体积为500mL)，排空5min，在0℃下向高压反应釜中充入压力为5兆帕的氩气，在色素促进剂的作用下快速生长形成高储气密度的固体水合物，记录一定时间间隔的储气量，结果如表1所示。
实施例8
一种色素水合物促进剂为质量分数为1％的色素溶液，由99克水，0.5克苏木精和0.5克茜素黄R配制而成；
所述色素水合物促进剂在制备高储气密度气体水合物中的应用即快速制备高储气密度气体水合物的方法：将80克色素水合物促进剂加入高压反应釜中(有效体积为500mL)，排空5min，在1℃下向高压反应釜中充入压力为8兆帕的混合气体(65％甲烷和35％氢气)，在色素促进剂的作用下快速生长形成高储气密度的固体水合物，记录一定时间间隔的储气量，结果如表1所示。
实施例9
一种色素水合物促进剂为质量分数为3％的色素溶液，由97克水，1克苏木精，1克茜素红和1克靛蓝配制而成；
所述色素水合物促进剂在制备高储气密度气体水合物中的应用即快速制备高储气密度气体水合物的方法：将80克色素水合物促进剂加入高压反应釜中(有效体积为500mL)，排空3min，在0℃下向高压反应釜中充入压力为5兆帕的甲烷，在色素促进剂的作用下快速生长形成高储气密度的固体水合物，记录一定时间间隔的储气量，结果如表1所示。
实施例10
一种色素水合物促进剂为质量分数为4％的色素溶液，由96克水，2克黑色素，1克藏花橙G和1克皂黄配制而成；
所述色素水合物促进剂在制备高储气密度气体水合物中的应用即快速制备高储气密度气体水合物的方法：将80克色素水合物促进剂加入高压反应釜中(有效体积为500mL)，排空4min，在0℃下向高压反应釜中充入压力为6.5兆帕的甲烷，在色素促进剂的作用下快速生长形成高储气密度的固体水合物，记录一定时间间隔的储气量，结果如表1所示。
对比例1
本对比例的一种快速制备高储气密度气体水合物的方法：在0℃下向高压反应釜(有效体积500mL)里80克水中充入压力为7.5兆帕的甲烷气体，记录一定时间间隔的储气量，结果如表1所示。
对比例2
本对比例一种水合物促进剂为质量分数为1％的促进剂水溶液，由99克水和1克十二烷基硫酸钠(SDS)均匀混合而成。
一种快速制备高储气密度气体水合物的方法：将80克水合物促进剂加入高压反应釜中(有效体积为500mL)，排空4min，在0℃下向高压反应釜中充入压力为9.5兆帕的甲烷气体，在十二烷基硫酸钠促进剂的作用下快速生长形成高储气密度的固体水合物，记录一定时间间隔的储气量，结果如表1所示。
表1水合物储气结果
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其它的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
Claims (6)
1.一种色素水合物促进剂，其特征在于：是由水和色素均匀混合而成；具体由100质量份的水和0.01～10质量份的色素均匀混合而成；所述色素为叶绿素铜钠、茜素黄R、苏木精、黑色素、茜素红、靛蓝、藏花橙G、皂黄的一种以上。
2.根据权利要求1所述色素水合物促进剂在高储气密度气体水合物中的应用。
3.根据权利要求2所述的应用，其特征在于：具体包含以下步骤：
1)预处理阶段：将色素水合物促进剂加入高压反应釜内，采用待反应气体，排空；
2)水合反应阶段：低温下，通入高压气体，反应一段时间，得到高储气密度的固态气体水合物。
4.根据权利要求3所述的应用，其特征在于：步骤(1)中所述的气体为甲烷、二氧化碳、氢气、氧气、氮气、硫化氢、氩气、氪气、氙气、乙烷、乙烯、丙烷中的一种以上。
5.根据权利要求3所述的应用，其特征在于：步骤(2)中所述低温为0～10℃；所述高压气体的压力为3～15兆帕。
6.根据权利要求3所述的应用，其特征在于：所述反应的时间为1～10h。
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