CN108680672B - 一种用于气相色谱填充柱的硅藻土红色担体及其制备方法 - Google Patents
一种用于气相色谱填充柱的硅藻土红色担体及其制备方法 Download PDFInfo
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Abstract
一种用于气相色谱填充柱的硅藻土红色担体,最可几孔径为200nm~800nm、孔容0.89~1.13cm3/g、比表面积为8~12m3/g;担体中SiO2含量≥85%,Al2O3含量≤10%,Fe2O3含量≤5%,CaO、K2O和Na2O总含量≤0.2%。制备方法包括如下步骤:(1)预处理;(2)硅藻土、水、聚乙二醇和黏土按照一定比例混合;(3)在0.15~0.40MPa下压缩成型;(4)真空条件下冷冻干燥;(5)按照一定升温程序焙烧,最高温度800℃;(6)粉碎与筛分;(7)清洗与干燥。依照上述方法制备的硅藻土红色担体,具有特定多孔结构和孔径分布窄等特点。利用该担体制备的天然气、二甲醚专用分析柱,不仅柱效高、特异吸附性小,而且分离度好,性能优于国内同类担体。
Description
技术领域
本发明属于化工领域,具体涉及一种用于气相色谱填充柱的硅藻土红色担体及其制备方法。
背景技术
气相色谱技术是一种成熟且广泛应用的复杂混合物的分离分析方法。气相色谱分析样品组分的分离是在色谱柱内完成的。在一定色谱条件下,由于被分析组分物质与固定相之间相互作用,使其在固定相中保留时间不同而得到分离。气相色谱分析中,待测组分的分离效果与固定相密切相关。在填充柱气‐液色谱中的固定液需先涂渍到担体表面,担体一般为化学惰性的多孔性固体颗粒。
硅藻土是以硅藻遗骸沉积为主生成的一种生物沉积岩,由于其具有独特的多孔结构,被广泛用于制备气相色谱填充柱的担体。硅藻土担体分为红色担体和白色担体。红色担体具有孔径较小、表面孔道密集,比表面积较大、机械强度好等特点,适用于非极性或弱极性组分的分离。根据相关书籍所述(达世禄,色谱学导论,武汉大学出版社,1999;刘国诠,余兆楼,色谱柱技术,化学工业出版社,2005),硅藻土和粘结剂混合后经900℃煅烧后制得用于气相色谱的硅藻土红色载体。
1970年,Ottenstein等申请了美国发明专利(3542584),首次提出利用硅藻土为原料制备气相色谱担体。高秀香等(发明专利申请号03102268.5)公开了一种气相色谱填充柱硅藻土担体及其制备方法:该担体是将硅藻土在800~1150℃下煅烧至少5小时后,经冷却、粉碎、筛分、干燥而成,可用于高碳数烷烃的分析。目前,市场上销售的红色担体有上海试剂厂的201,大连丰盈分子筛制造有限公司的6201和国外的Chromosorb P等。国外生产红色载体的性能明显优于国内产品,但是其制备方法属于商业秘密,尚未见公开报道。
因此,发展一种以中国产硅藻土为原料制备气相色谱填充柱用硅藻土红色担体的方法,对于色谱分析材料国产化,提高色谱分析效率,降低企业运行成本具有重要现实意义。
发明内容
本发明所提供的硅藻土红色担体,具有特定多孔结构和孔径分布窄等特点。对于天然气中烷烃、烯烃组成、液化气中二甲醚等分析,填充柱的柱效高,且分离度好,性能优于国内同类担体。
本发明的技术方案为:一种硅藻土担体,所述硅藻土担体中孔径10~105nm的孔容为0.89~1.13cm3/g,孔径102~103nm的孔容比为66.1~80.4%,最可几孔径为200nm~800nm、BET比表面积为8~12m3/g。
优选地,所述担体中SiO2含量≥85%,Al2O3含量≤10%,Fe2O3含量≤5%,CaO、K2O和Na2O总含量≤0.2%。
本发明还提供上述硅藻土担体的制备方法,包括如下步骤:
(1)预处理:将硅藻土浸泡在碱液中0.5~1小时;
(2)混合:将硅藻土、水、聚乙二醇-4000和黏土混合,得混合物;
(3)成型:将所述混合物压缩得成型物;
(4)冻结、干燥:将成型物冻结后,经真空冷冻干燥得干燥物;
(5)焙烧:将干燥物焙烧,得到焙烧物;
(6)依次经粉碎、筛分、清洗、干燥,得所述硅藻土担体。
优选地,所述步骤(1)中,在80℃~100℃下将硅藻土浸泡在0.1M氢氧化钠或氢氧化钾溶液中,预处理0.5~1小时,硅藻土的粒度<600目。
优选地,所述步骤(2)中,以质量比计,硅藻土为20份、水为15~25份、聚乙二醇-4000为0.5~5份,黏土为0.5~1份,黏土粒度<1000目,黏土中的CaO、K2O、Na2O总含量≤5%。
优选地,所述步骤(3)中,所述混合物在0.15~0.4MPa条件下挤条成型。
优选地,所述步骤(4)中,冷冻的条件:从室温25℃降温至0℃~-2℃,降温速度<-2℃/min;在0℃~-2℃下冷冻48小时,再于-15℃下冷冻12小时。真空冷冻干燥的条件为-0.097MPa、-54℃和8小时。
优选地,所述步骤(5)中,所述焙烧过程的升温程序为25~100℃,升温速率为5℃/min;100~300℃,升温速率为2℃/min;350~600℃,升温速率为5℃/min;600~800℃(优选850℃),升温速率为2℃/min;800℃或850℃,恒温1~2小时。
本发明还提供上述制备方法得到的硅藻土担体在气相色谱填充柱中的应用。
优选地,用于天然气、二甲醚专用分析柱的理论塔板数>3000。
本发明所提供的硅藻土红色担体,具有特定孔径分布窄、特异性吸附小等特点,可用于制备气相色谱填充柱。特别是,制备的天然气、二甲醚专用分析柱性能明显优于其它国内色谱填充柱。
附图说明
图1-1、图1-2为本发明实施例3制备的硅藻土红色担体的电子扫描电镜照片;
图2-1、图2-2为本发明实施例3中冷冻干燥后聚乙二醇颗粒的电子扫描电镜照片。
具体实施例
聚乙二醇-4000购自辽阳奥克股份有限公司,黏土购自河北绿宸矿产品加工厂(粒度<1000目),去离子水自制。硅藻土分别由吉林长白硅藻土有限责任公司(简称吉林长白)和嵊州市华力硅藻土制品有限公司(简称浙江嵊州)提供,粒度<600目。
压汞法,又称汞孔隙率法,是测定中孔和大孔孔径分布的重要方法。采用Poremaster33孔径测定仪(美国Quantachrome)检测硅藻土担体样品孔径分布。BET比表面积检测法被广泛应用于研究颗粒表面吸附性能,采用NOVA2200e比表面及孔隙度测定仪(美国Quantachrome)检测硅藻土担体样品比表面积。
按照文献报道方法(郑水林,李杨.非金属矿,1997,118(4):49-50.),将天然硅藻土粗土进行擦洗提纯后作为担体制备的原料(以下简称硅藻土)。
(1)预处理:将硅藻土浸泡在碱液中0.5~1小时;以除去小部分粉尘并扩大硅藻土结构中孔道,然后过滤、清洗并干燥。
(2)混合:将硅藻土、水、聚乙二醇-4000和黏土混合,得混合物;
聚乙二醇的作用:1)造孔剂;2)润滑剂,便于压缩成型。
黏土的作用是粘结剂,提高焙烧后颗粒机械强度。
(3)成型:将所述混合物压缩得成型物;优选在一定压力作用下,利用挤条机压缩成型。
(4)冻结、干燥:将成型物冻结后,经真空冷冻干燥得干燥物;优选置于真空冷冻干燥机中干燥;
利用冷冻干燥工艺,制备担体的孔径分布窄。慢速(≤-2℃/min)冷冻条件下,水—聚乙二醇混合物冻结为亚微米级尺寸冰晶。当真空冷冻干燥时,冰升华被除去,形成相互贯通且均匀分布的聚乙二醇颗粒(下述实施例3中冷冻干燥后聚乙二醇颗粒的电子扫描电镜照片见图2-1、图2-2),而且有助于保持硅藻土颗粒间堆积的多孔结构,避免堆积孔坍塌。
(5)焙烧:将干燥物焙烧,得到焙烧物;优选置于马弗炉中焙烧,得到红色硅藻土焙烧物;
(6)粉碎、筛分:优选利用粉碎机粉碎焙烧物,用振动筛筛分,得到60~80目,80~100目,100~120目的红色硅藻土担体。
(7)清洗、干燥:优先利用去离子水清洗筛分后的硅藻土担体,去除粉尘,然后在105℃干燥24小时,最终得到可以用于制备色谱填充柱的红色硅藻土担体。
实施例1
以吉林长白硅藻土(<600目)为原料,在80℃下将硅藻土浸泡在0.1M氢氧化钠溶液中,预处理1小时;按质量比,将硅藻土(20份)、水(25份)、聚乙二醇-4000(5份)和黏土(1份)混合。在0.15MPa压力下压缩成型;将压缩成型的混合物从室温25℃降温至0℃~-2℃,降温速度<-2℃/min;并在0℃~-2℃下冷冻48小时,再于-15℃下冷冻12小时,然后将冻结物真空冷冻干燥,条件为-0.097MPa、-54℃和8小时。
将干燥后的硅藻土混合物置于马弗炉中焙烧,得到红色硅藻土焙烧物;焙烧过程的升温程序为25~100℃,升温速率为5℃/min;100~300℃,升温速率为2℃/min;350~600℃,升温速率为5℃/min;600~800℃,升温速率为2℃/min;800℃,恒温1小时。利用粉碎机粉碎焙烧物用振动筛筛分,得到60~80目,80~100目,100~120目的红色硅藻土担体;利用去离子水清洗筛分后的硅藻土担体,去除粉尘,然后在105℃干燥24小时,最终得到可以用于制备色谱填充柱的红色硅藻土担体。。
利用压汞法测定硅藻土担体(80~100目)的孔隙结构:孔径10~105nm的孔容1.13cm3/g;孔径102~103nm的孔容比为80.4%;最可几孔径为575nm。N2吸附法测定BET比表面积为8.1m3/g。担体中SiO2含量≥90%,Al2O3含量≤7%,Fe2O3含量≤3.5%,CaO、K2O和Na2O总含量≤0.14%。
实施例2
以浙江嵊州硅藻土为原料,在100℃下将硅藻土浸泡在0.1M氢氧化钾溶液中,预处理0.5小时;按照质量比,将硅藻土(20份)、水(15份)、聚乙二醇-4000(0.5份)和黏土(1份)混合。在0.30MPa压力下压缩成型;将压缩成型的混合物从室温25℃降温至0℃~-2℃,降温速度<-2℃/min;并在0℃~-2℃下冷冻48小时,再于-15℃下冷冻12小时,然后将冻结物真空冷冻干燥,条件为-0.097MPa、-54℃和8小时。
将干燥后的硅藻土混合物置于马弗炉中焙烧,得到红色硅藻土焙烧物;焙烧过程的升温程序为25~100℃,升温速率为5℃/min;100~300℃,升温速率为2℃/min;350~600℃,升温速率为5℃/min;600~850℃,升温速率为2℃/min;850℃,恒温2小时。利用粉碎机粉碎焙烧物用振动筛筛分,得到60~80目,80~100目,100~120目的红色硅藻土担体;利用去离子水清洗筛分后的硅藻土担体,去除粉尘,然后在105℃干燥24小时,最终得到可以用于制备色谱填充柱的红色硅藻土担体。
利用压汞法测定硅藻土担体(80~100目)的孔隙结构:孔径10~105nm的孔容0.95cm3/g;孔径102~103nm的孔容比为66.1%;最可几孔径为375nm。N2吸附法测定BET比表面积为10.4m3/g。担体中SiO2含量≥85%,Al2O3含量≤10%,Fe2O3含量≤5%,CaO、K2O和Na2O总含量≤0.23%。
实施例3.
以吉林长白硅藻土(<600目)为原料,在80℃下将硅藻土浸泡在0.1M氢氧化钠溶液中,预处理1小时;按照质量比,将硅藻土(20份)、水(20份)、聚乙二醇-4000(1份)和黏土(1份)混合。在0.40MPa压力下压缩成型;将压缩成型的混合物从室温25℃降温至0℃~-2℃,降温速度<-2℃/min;并在0℃~-2℃下冷冻48小时,再于-15℃下冷冻12小时,然后将冻结物真空冷冻干燥,条件为-0.097MPa、-54℃和8小时。
将干燥后的硅藻土混合物置于马弗炉中焙烧,得到红色硅藻土焙烧物,焙烧过程的升温程序为25~100℃,升温速率为5℃/min;100~300℃,升温速率为2℃/min;350~600℃,升温速率为5℃/min;600~800℃,升温速率为2℃/min;800℃,恒温1小时。经过利用粉碎机粉碎焙烧物用振动筛筛分,得到60~80目,80~100目,100~120目的红色硅藻土担体;利用去离子水清洗筛分后的硅藻土担体,去除粉尘,然后在105℃干燥24小时,最终得到可以用于制备色谱填充柱的红色硅藻土担体。制备的担体(80~100目)表观型貌见图1-1、图1-2。可以看出,制备的硅藻土担体是由粒度较均一的颗粒堆砌而成,表面多孔,具有微米和纳米孔道。
利用压汞法测定硅藻土担体(80~100目)的孔隙结构:孔径10~105nm的孔容0.83cm3/g;孔径102~103nm的孔容比76.4%;最可几孔径为487nm。N2吸附法测定BET比表面积为11.0m3/g。担体中SiO2含量≥90%,Al2O3含量≤7%,Fe2O3含量≤3.5%,CaO、K2O和Na2O总含量≤0.14%。
实施例4
本实施例说明不加聚乙二醇对担体的孔结构影响。
以吉林长白硅藻土(<600目)为原料,在80℃下将硅藻土浸泡在0.1M氢氧化钠溶液中,预处理1小时;按照质量比,将硅藻土(20份)、水(20份)和黏土(1份)混合。在0.40MPa压力下压缩成型;将压缩成型的混合物从室温25℃降温至0℃~-2℃,降温速度<-2℃/min;并在0℃~-2℃下冷冻48小时,再于-15℃下冷冻12小时,然后将冻结物真空冷冻干燥,条件为-0.097MPa、-54℃和8小时。
将干燥后的硅藻土混合物置于马弗炉中焙烧,得到红色硅藻土焙烧物,焙烧过程的升温程序为25~100℃,升温速率为5℃/min;100~300℃,升温速率为2℃/min;350~600℃,升温速率为5℃/min;600~800℃,升温速率为2℃/min;800℃,恒温1小时。经过利用粉碎机粉碎焙烧物用振动筛筛分,得到60~80目,80~100目,100~120目的红色硅藻土担体;利用去离子水清洗筛分后的硅藻土担体,去除粉尘,然后在105℃干燥24小时,最终得到红色硅藻土担体。
利用压汞法测定硅藻土担体的孔隙结构:孔径10~105nm的孔容0.47cm3/g;孔径102~103nm和103~105nm的孔容比分别为45.1%和35.9%;最可几孔径为226nm。N2吸附法测定BET比表面积为7.4m3/g。担体中SiO2含量≥90%,Al2O3含量≤6.5%,Fe2O3含量≤2.5%,CaO、K2O和Na2O总含量≤0.17%。
与实施例3所制备担体相比,不添加聚乙二醇制备担体的孔容小,且孔径102~103nm的孔容比小,孔径分布分散。
实施例5
本实施例说明按照本发明所述方法制备硅藻土担体的应用效果。
色谱担体:按照实施例(3)所述方法制备;
色谱柱:不锈钢填充柱,4mm×9m;
检测目标:天然气;
条件:TCD检测器;柱温:40℃;进样器和检测器温度:80℃;载气:H2,30ml/min。
以天然气为检测目标,对按照实施例(3)所述方法制备的硅藻土担体进行系统分析,结果如表1所示。可以看出,正戊烷保留时间为28min,说明制备的硅藻土担体惰性好,没有明显特异性吸附;色谱柱理论塔板数>3000,柱效高,分离度较好,色谱峰型基本对称。
表1本发明提供硅藻土担体的系统分析结果(天然气)
峰号 | 峰名 | 保留时间 | 半峰宽 | 理论塔板数 | 分离度 | 拖尾因子 | 不对称度 |
1 | 甲烷 | 3.020 | 0.113 | 3942.4 | 0.687 | 0.986 | 1.098 |
2 | 乙烷 | 3.188 | 0.113 | 4389.1 | 0.735 | 1.647 | 1.941 |
3 | 乙烯 | 4.197 | 0.113 | 5492.7 | 4.088 | 0.717 | 0.486 |
4 | 丙烷 | 5.148 | 0.170 | 5080.9 | 2.833 | 1.138 | 1.157 |
5 | 丙烯 | 6.327 | 0.237 | 3965.3 | 2.910 | 1.344 | 1.646 |
6 | 异丁烷 | 7.787 | 0.317 | 3359.7 | 2.651 | 1.782 | 2.520 |
7 | 正丁烷 | 9.408 | 0.388 | 3256.4 | 2.293 | 1.235 | 1.404 |
8 | 正/异丁烯 | 12.647 | 0.467 | 4080.4 | 0.726 | 1.075 | 1.181 |
9 | 反丁烯 | 16.417 | 0.887 | 1902.6 | 2.783 | 1.064 | 1.102 |
10 | 顺丁烯+丁二烯 | 19.597 | 0.668 | 4763.8 | 2.036 | 1.381 | 2.037 |
11 | 异戊烷 | 22.998 | 0.920 | 3462.0 | 2.141 | 0.922 | 0.789 |
12 | 正戊烷 | 28.380 | 0.902 | 5521.2 | 3.001 | 1.229 | 1.332 |
对比例1(对应实施例5)
色谱担体:大连丰盈分子筛制造有限公司生产的硅藻土红色担体(6201);
色谱柱:不锈钢填充柱,4mm×9m;
检测目标:天然气;
条件:TCD检测器;柱温:40℃;进样器和检测器温度:80℃;载气:H2,30ml/min。
以天然气为检测目标,对国产硅藻土担体6201进行系统分析,结果如表2所示。可以看出,异戊烷保留时间为34min,正戊烷未出峰,说明该担体惰性不佳,存在特异性吸附;分离度较好,色谱峰型基本对称,但是色谱柱理论塔板数<3000,柱效不高。
表2 6201担体的系统评价结果(天然气)
峰号 | 峰名 | 保留时间 | 半峰宽 | 理论塔板数 | 分离度 | 拖尾因子 | 不对称度 |
1 | 甲烷 | 2.690 | 0.120 | 2783.9 | 0.000 | 1.224 | 1.090 |
2 | 乙烷 | 4.007 | 0.323 | 850.7 | 2.970 | 1.173 | 1.240 |
3 | 乙烯 | 5.082 | 0.287 | 1740.9 | 1.762 | 1.245 | 1.375 |
4 | 丙烷 | 6.398 | 0.458 | 1079.6 | 1.767 | 1.361 | 1.594 |
5 | 丙烯 | 8.182 | 0.568 | 1148.1 | 1.737 | 1.411 | 1.740 |
6 | 异丁烷 | 10.032 | 0.800 | 871.1 | 1.362 | 1.182 | 1.416 |
7 | 正丁烷 | 13.965 | 0.977 | 1132.6 | 2.214 | 1.217 | 1.372 |
8 | 正/异丁烯 | 18.665 | 1.397 | 989.4 | 1.980 | 1.146 | 1.261 |
9 | 反丁烯 | 22.732 | 1.292 | 1715.8 | 1.513 | 1.086 | 1.139 |
10 | 顺丁烯+丁二烯 | 26.665 | 1.525 | 1693.7 | 1.386 | 1.094 | 1.156 |
11 | 异戊烷 | 34.065 | 1.990 | 1623.3 | 2.105 | 1.005 | 1.026 |
实施例6
本实施例说明按照本发明所述方法制备硅藻土担体的应用效果。
色谱担体:按照实施例(3)所述方法制备;
色谱柱:不锈钢填充柱,4mm×9m;
检测样品:含二甲醚的液化气;
条件:TCD检测器;柱温:40℃;进样器和检测器温度:80℃;载气:H2,30ml/min。
以含二甲醚的液化气为检测目标,对制备的硅藻土担体进行系统分析,结果如表3所示。可以看出,二甲醚、正戊烷的停留时间分别为11min、17min,说明担体惰性较好,未存在明显吸附,色谱柱理论塔板数>3000,柱效较高,分离度较好,峰型基本对称。
表3本发明提供硅藻土担体的系统分析结果(含二甲醚的液化气)
峰号 | 峰名 | 保留时间 | 半峰宽 | 理论塔板数 | 分离度 | 拖尾因子 | 不对称度 |
1 | 空气 | 2.240 | 0.105 | 2521.3 | 0.000 | 1.438 | 1.807 |
2 | 丙烷 | 3.123 | 0.137 | 2893.5 | 3.655 | 1.145 | 1.239 |
3 | 丙烯 | 4.823 | 0.215 | 2788.2 | 4.834 | 1.220 | 1.427 |
4 | 异丁烷 | 5.482 | 0.262 | 2431.3 | 1.381 | 1.549 | 2.088 |
5 | 正丁烷 | 7.340 | 0.357 | 2346.3 | 3.005 | 1.153 | 1.288 |
6 | 正/异丁烯 | 9.807 | 0.522 | 2670.5 | 3.071 | 1.130 | 1.230 |
7 | 二甲醚 | 11.423 | 0.533 | 2656.5 | 1.670 | 1.084 | 1.176 |
8 | 反丁烯 | 12.523 | 0.633 | 3054.6 | 1.043 | 1.241 | 1.535 |
9 | 顺丁烯 | 13.723 | 0.680 | 2601.1 | 1.029 | 1.378 | 1.424 |
10 | 异戊烷 | 15.423 | 0.852 | 2850.0 | 1.294 | 1.104 | 1.050 |
11 | 正戊烷 | 17.923 | 0.972 | 2453.6 | 1.632 | 0.829 | 0.565 |
对比例2(对应于实施例6)
色谱担体:大连丰盈分子筛制造有限公司生产的硅藻土红色担体(6201);
色谱柱:不锈钢填充柱,4mm×9m;
检测样品:含二甲醚的液化气;
条件:TCD检测器;柱温:40℃;进样器和检测器温度:80℃;载气:H2,30ml/min。
以含二甲醚的液化气为检测目标,对国产硅藻土担体6201进行系统分析,结果如表4所示。可以看出,色谱柱理论塔板数>3000,柱效高,分离度较好,峰型基本对称;但是二甲醚、正戊烷的停留时间分别为17min、28min,说明担体惰性不好,存在明显特异性吸附。
表4 6201硅藻土担体的系统分析结果(含二甲醚的液化气)
峰号 | 峰名 | 保留时间 | 半峰宽 | 理论塔板数 | 分离度 | 拖尾因子 | 不对称度 |
1 | 空气 | 2.855 | 0.122 | 3054.1 | 0.000 | 1.081 | 1.231 |
2 | 丙烷 | 3.065 | 0.128 | 3160.0 | 0.833 | 1.638 | 1.875 |
3 | 丙烯 | 4.325 | 0.217 | 2214.3 | 3.671 | 1.227 | 1.378 |
4 | 异丁烷 | 7.450 | 0.343 | 2613.2 | 5.580 | 1.385 | 1.707 |
5 | 正丁烷 | 8.528 | 0.443 | 2051.7 | 1.367 | 1.871 | 2.667 |
6 | 正/异丁烯 | 12.342 | 0.612 | 2263.9 | 3.633 | 1.237 | 1.421 |
7 | 二甲醚 | 17.248 | 0.770 | 2785.2 | 3.546 | 1.146 | 1.258 |
8 | 反丁烯 | 20.168 | 0.963 | 2435.5 | 1.692 | 0.875 | 0.847 |
9 | 顺丁烯 | 21.332 | 1.030 | 2376.2 | 0.569 | 1.765 | 2.100 |
10 | 异戊烷 | 24.827 | 1.018 | 3303.0 | 1.725 | 0.966 | 1.035 |
11 | 正戊烷 | 28.147 | 1.130 | 3349.9 | 1.552 | 1.064 | 1.108 |
通过天然气和液化气组成系统分析结果(表1-表4),可以看出本发明提供硅藻土担体惰性好,对烷烃和烯烃等组分没有特异性吸附。采用该担体制备的天然气、二甲醚专用柱,柱效高,具有分离度好、色谱峰型对称、不拖尾等特点,是一种性能优良的硅藻土红色担体。与市售的国产担体相比,本发明提供硅藻土担体性能优良,这与制备硅藻土担体具有较均一的孔道结构有关。
Claims (7)
1.一种硅藻土担体,其特征在于,所述硅藻土担体中孔径10~105nm的孔容为0.89~1.13cm3/g,孔径102~103nm的孔容比为66.1~80.4%,最可几孔径为200nm~800nm,BET比表面积为8~12m2/g;
所述硅藻土担体的制备方法,包括以下步骤:
(1)预处理:将硅藻土浸泡在碱液中0.5~1小时;
(2)混合:将硅藻土、水、聚乙二醇-4000和黏土混合,得混合物;
(3)成型:将所述混合物压缩得成型物;
(4)冻结、干燥:将成型物冻结后,经真空冷冻干燥得干燥物;
(5)焙烧:将干燥物焙烧,得到焙烧物;
(6)依次经粉碎、筛分、清洗、干燥,得所述硅藻土担体;
所述步骤(1)中,在80℃~100℃下将硅藻土浸泡在0.1M氢氧化钠或氢氧化钾溶液中;
所述步骤(2)中,以质量比计,硅藻土为20份、水为15~25份、聚乙二醇-4000为0.5~5份;
所述步骤(4)中,冷冻的条件:从室温25℃降温至0℃~-2℃,降温速度<-2℃/min;在0℃~-2℃下冷冻48小时,再于-15℃下冷冻12小时;真空冷冻干燥的条件为-0.097MPa、-54℃和8小时;
所述步骤(5)中,焙烧过程的升温程序为25~100℃,升温速率为5℃/min;100~300℃,升温速率为2℃/min;350~600℃,升温速率为5℃/min;600~800℃,升温速率为2℃/min;800℃,恒温1~2小时。
2.根据权利要求1所述的硅藻土担体,其特征在于,所述担体中SiO2含量≥85%,Al2O3含量≤10%,Fe2O3含量≤5%,CaO、K2O和Na2O总含量≤0.2%。
3.根据权利要求1所述的硅藻土担体,其特征在于,所述步骤(1)中,硅藻土的粒度<600目。
4.根据权利要求1所述的硅藻土担体,其特征在于,所述步骤(2)中,黏土粒度<1000目,黏土中的CaO、K2O、Na2O总含量≤5%。
5.根据权利要求1所述的硅藻土担体,其特征在于,所述步骤(3)中,所述混合物在0.15~0.4MPa条件下挤条成型。
6.权利要求1-5任意一项所述的硅藻土担体在气相色谱填充柱中的应用。
7.根据权利要求6所述的应用,其特征在于,用于天然气、二甲醚专用分析柱的理论塔板数>3000。
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