CN106890626A - 吸附材料与其形成方法与吸附式热泵 - Google Patents
吸附材料与其形成方法与吸附式热泵 Download PDFInfo
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Abstract
本发明涉及一种吸附材料,包括:石墨烯卷,是石墨烯片沿着轴心卷绕而成,且石墨烯卷垂直于轴心的剖面为螺旋状;以及改质剂,接枝至石墨烯卷的层间与外侧上,且改质剂具有亲水基。本发明还涉及上述吸附材料的形成方法,以及包括上述吸附材料的吸附式热泵。本发明的吸附材料可用于热泵中。
Description
技术领域
本发明关于吸附材料,更特别关于其形成方法与应用。
背景技术
相较于气体压缩机制冷技术,吸附式制冷技术具有稳定可靠、节能环保、无噪音等优点。吸附式热泵藉由材料吸收热能并释放水气,于冷端吸附凝结水气,周期性的冷却和加热吸附材料,使热能转换为冷能。理论上,吸附剂的制冷能力指标(Specific Cooling Power,SCP)与其吸附量、吸脱附的速度,以及热交换有关。一般多孔性材料能吸附的水量仅为其孔洞内的体积,因吸附性有限而使其难以在吸附热汞的空调应用上担当大任。现有材料存在吸附量不高及吸附速率过慢问题,常见改善手法为增加比表面积、加大孔洞尺寸、或增加高热导材料。然而上述方法存在许多问题,比如材料热传导特性下降、脱附速率降低、孔洞加大造成结构亦崩解,造成循环性降低。
综上所述,目前亟需新的吸附材料以进一步应用于热泵中。
发明内容
本发明的目的之一在于提供一种在吸附量、脱附量与脱附时间方面均优的吸附材料。
本发明的另一目的在于提供一种形成上述吸附材料的方法。
本发明的再一目的在于提供一种利用上述吸附材料的吸附式热泵。
本发明一实施例提供的吸附材料,包括:石墨烯卷,是石墨烯片沿着轴心卷绕而成,且石墨烯卷垂直于轴心的剖面为螺旋状;以及改质剂,接枝至石墨烯卷的层间与外侧上,且改质剂具有亲水基。
本发明一实施例提供的吸附材料的形成方法,包括:(a)混合石墨与插层剂,以形成第一插层石墨;(b)混合第一插层石墨与改质剂后,施加微波至混合物以形成第二插层石墨;(c)将第二插层石墨置于醇类中进行超音波震荡,以形成吸附材料,其中吸附材料包括:石墨烯卷,是石墨烯片沿着轴心卷绕而成,且石墨烯卷垂直于轴心的剖面为螺旋状;以及改质剂,接枝至石墨烯卷的层间与外侧上,且改质剂具有亲水基。
本发明一实施例提供的吸附式热泵,包括:吸附/脱附部份,具有吸附材料以吸附/脱附制冷剂;蒸发部份,用以蒸发制冷剂,且蒸发部份连接至吸附/脱附部份;以及冷凝部份,用以冷凝制冷剂,且冷凝部份连接至吸附/脱附部份,其中吸附材料包括:石墨烯卷,是石墨烯片沿着轴心卷绕而成,且石墨烯卷垂直于轴心的剖面为螺旋状;以及改质剂,接枝至石墨烯卷的层间与外侧上,且改质剂具有亲水基。
与现有技术相比,本发明的吸附材料在吸附量、脱附量与脱附时间方面均优于现有技术中的硅胶、分子筛4A、以及石墨烯卷与PMAA,可用于热泵中。
附图说明
图1是本发明一实施例中的吸附材料的剖面图;
图2是本发明一实施例中的吸附式热泵的示意图;
图3A、图3B、图4A与图4B是本发明一实施例中的产物的TEM图;
图5是本发明一实施例中的产物于干燥状态与吸水状态的XRD图谱;
图6是本发明实施例中,PMAA、石墨烯卷、与接枝PMAA的石墨烯卷的IR图谱;
图7是本发明一实施例中的不同吸附材料的吸附量对时间的曲线;
图8是本发明一实施例中的不同吸附材料的脱附量对时间的曲线;
其中,符号说明
10 吸附材料; 11 石墨烯卷;
13 轴心; 15 改质剂;
20 吸附式热泵; 21 吸附/脱附部份;
23 制冷剂; 25 蒸发部份;
27 冷凝部份。
具体实施方式
本发明一实施例提供吸附材料的形成方法。首先,(a)混合石墨与插层剂,以形成第一插层石墨。上述插层剂可为硫酸、过氯酸、硝酸、磷酸、硬脂酸、或上述的组合。举例来说,可将石墨置于插层剂如过氯酸与硝酸的溶液后,搅拌至石墨不再起泡,即得第一插层石墨。
接着(b)混合第一插层石墨与改质剂后施加微波至上述混合物,使改质剂进入第一插层的石墨中并接枝其上,以形成第二插层石墨。上述改质剂具有亲水基,比如界面活性剂、亲水性高分子、或上述的组合。举例来说,界面活性剂可为十二烷基苯磺酸钠(SDBS)、聚氧乙烯基醚硫酸盐(AES)、聚氧乙烯烷基醚(APEO)、或聚乙烯聚胺脂肪酸胺盐(AE)。上述亲水性高分子的重均分子量介于10000至500000之间。若亲水性高分子的重均分子量过高,则不易受热挠动亲水性高分子分子链,无法使水分子结晶能在低温下破坏而脱附,影响脱附性能。举例来说,亲水性高分子包括聚甲基丙烯酸(PMAA)、聚乙烯醇(PEG)、聚丙烯腈(PAN)、丙烯酸酯-丙烯酰胺共聚物、乙烯-马来酸酐共聚物、羧甲基纤维素、或淀粉接枝的聚丙烯腈。在另一实施例中,亲水性高分子的亲水基是磺酸钠,且亲水性高分子包括聚苯乙烯磺酸钠(PSS)或木质磺酸钠。在又一实施例中,亲水性高分子的亲水基是胺基,且亲水性高分子包括聚丙烯酰胺(PAM)、聚乙烯吡咯烷酮(PVP)、聚乙烯亚胺(PEI)、或聚二甲基二烯丙基氯化铵(PDDA)。另一方面,石墨与改质剂的重量比介于1:0.5至1:5之间。若改质剂的比例过低,则无法有效增加产物的吸水量。若改质剂的比例过高,则因亲水性高分子上过多的亲水基(如COO-)与水形成氢键结合,而不易脱附。
接着(c)将第二插层石墨置于醇类下并进行超音波震荡,使第二插层石墨分层成石墨烯片,且石墨烯片沿着轴心卷绕而成石墨烯卷。在一实施例中,醇类可为常见醇类如乙醇。如图1所示,吸附材料10中的石墨烯卷11垂直于轴心13的剖面为螺旋状,且改质剂15接枝至石墨烯卷11的层间与外侧上。可以理解的是,图1所示的剖面仅为示意,石墨烯卷11可具有更多或更少的卷绕层数,且层与层的间距也不一定一致。值得注意的是,上述步骤(a)、(b)、与(c)的顺序不可随意变换。举例来说,若是未进行步骤(a)即取改质剂直接与石墨混合并施加微波,改质剂将无法进入未经插层剂插层的石墨的层间(层距不足以***改质剂),则改质剂只会接枝于石墨的最外层,最后形成的石墨烯卷的层间将不具有接枝的改质剂。另一方面,若是在进行步骤(a)与(c)后才加入改质剂,则改质剂只会接枝于石墨烯卷的外侧而不会接枝于石墨烯卷的层间,此将大幅降低产物的吸水性质。
在本发明其他实施例中,可进一步以保水剂包覆上述石墨烯卷,可维持其于多次吸水/脱水循环后的吸水量。在本发明一实施例中,保水剂可为海藻酸钠、聚丙烯酸或其盐类、聚氧乙烯、或聚乙烯醇。
在一实施例中,上述吸附材料可应用于吸附式热泵中。如图2所示,吸附式热泵20可包含:吸附/脱附部份21,其具有上述吸附材料10以吸附/脱附制冷剂23。吸附式热泵20亦包含蒸发部份25连接至吸附/脱附部份21,用以蒸发该制冷剂23。吸附式热泵20亦包含冷凝部份27连接至吸附/脱附部份21,用以冷凝制冷剂23。在一实施例中,制冷剂可为水。关于吸附式热泵的原理与细节,可参考美国专利US7497089。
为了让本发明的上述和其他目的、特征、和优点能更明显易懂,下文特举数实施例配合所附附图,作详细说明如下:
实施例
在下述实施例中,亲水性高分子为聚甲基丙烯酸(Poly(Methacrylic Acid),PMAA,购自Scientific polymer products,INC.的CAT709,其重均分子量为130000)。界面活性剂为十二烷基苯磺酸钠(Sodium Dodecyl BenzeneSulphonate,SDBS)。石墨材料为粒径小于100mesh的石墨粉(购自中央碳素的EGS-743)。
比较例1(石墨烯卷)
将适量石墨粉加入200mL的过氯酸(70-72wt%)/硝酸(≥65wt%)(v/v=0.25至1)溶液中搅拌均匀,直到石墨不冒泡(约2小时),以形成过氯酸与硝酸插层的石墨(呈膨胀悬浮状)。接着将过氯酸与硝酸插层的石墨加入过量酒精,并以超音波震荡约1小时,直到不再冒气泡。离心清洗去除多余的插层剂与酒精,即得石墨烯卷。
实施例1(石墨烯卷接枝PMAA)
将适量石墨粉加入200mL的过氯酸(70-72%重量比)/硝酸(≥65%重量比)(v/v=0.25至1)溶液中搅拌均匀,直到石墨不冒泡(约2hr),以形成过氯酸与硝酸插层的石墨(呈膨胀悬浮状)。接着以吸管去除多余的插层剂后,加入10g PMAA并搅拌均匀。将上述混合物置入微波反应器后施加微波,进行热裂解加成反应1分钟。由于PMAA上有大量负电荷的COO-官能基,可藉电荷吸引扩散进入已插层的石墨层间,形成PMAA插层的石墨。此时样品颜色略呈棕黑色。将PMAA插层的石墨加入过量酒精,并以超音波震荡约1小时,直到不再冒气泡。离心清洗去除多余的插层剂、PMAA、与酒精,收集产物并进行物性与结构分析。产物的电子显微镜TEM照片如图3A、图3B、图4A与图4B。由图3A可知,有相当数量的石墨烯片卷曲呈纳米卷状,由图3B可知石墨层间距与纳米碳管相近。由图4A可知石墨烯卷的层间距为0.6nm至0.8nm之间。由图4B可知石墨烯卷内径为2nm。
取上述产物进行XRD分析,如图5所示。产物于(002)位置有峰值,当石墨烯卷由干燥状态开始吸水后,(002)位置峰值由上方往下方移动,显示PMAA高分子吸水过程,将使原本卷挠的结构松开,并扩大石墨层间距至约为0.34nm。如图5所示,吸水后的产物中,石墨烯层打开而使原(002)位置峰值变小许多这样的变化将有助于调控石墨烯卷中PMAA的吸水量。当温度升高,上述产物将释放结晶水。
为了确认定PMAA是否接枝于石墨烯卷材料上,利用红外线光谱仪(FT-IR)量测PMAA、比较例1的石墨烯卷、与实施例1的产物,如图6所示。PMAA的C=O特征峰为1718cm-1,而实施例1的产物中C=O特征峰偏移至1656cm-1,可证明实施例1的反应步骤确实可将PMAA反应接枝于石墨烯卷上。
接着将实施例1的产物、PMAA、硅胶(购自Aldrich,比表面积为300m2/g,孔洞约10nm)、分子筛4A(购自Alfa,孔洞尺寸为0.4nm)置入恒温恒湿箱,吸湿条件为RH=80%,25℃,测试结果如图7所示。分子筛4A的水气吸附速率较快,但饱和吸附量仅16%,而硅胶则达到30%以上。实施例1的产物的吸附量达58%以上(尚未饱和),显见石墨烯卷结构可让水气的吸附容量有较大的弹性空间。
接着将上述吸水后的材料置于80℃下的进行水气脱附率实验,测试结果如图8所示。实施例1的产物其水气脱附率最高(于14分钟可脱附70wt%),硅胶需30分钟以上水气脱附率才能达70%wt,而分子筛4A则无法脱附水气。
硅胶、分子筛4A、比较例1的石墨烯卷、PMAA、与实施例1的产物的吸附/脱附性质如第1表所示。
第1表
由第1表可知,实施例1的吸附量、脱附量与脱附时间均优于硅胶、分子筛4A、比较例1的石墨烯卷与PMAA。
接着以体积法量测吸附等温线并以克劳西斯-克拉柏龙方程式(Clausius-Clapeyron Equation)计算硅胶、分子筛4A、与实施例1的产物的吸附热,另在忽略显热变化下,以吸脱附循环的特性来计算材料理想性能系数(Coefficient of Performance,COP)、及单位制冷率(Specific Cooling Power,SCP),如第2表与第3表所示。实施例1的产物的COP为硅胶的COP的1.21倍,且实施例1的产物的SCP为硅胶的SCP的2.1倍。
第2表
吸附热(MJ/mole) | COP | |
硅胶 | 0.5043 | 0.809 |
分子筛4A | 0.7569 | 0.539 |
实施例1 | 0.4165 | 0.979 |
第3表
吸脱附循环量ΔX | 循环时间(min) | SCP(W/Kg) | |
硅胶 | 0.10 | 60 | 63 |
分子筛4A | 0.02 | 35 | 22 |
实施例1 | 0.16 | 45 | 133 |
实施例2(石墨烯卷接枝SDBS)
将适量石墨粉加入200mL的过氯酸(70-72%重量比)/硝酸(≥65%重量比)(v/v=0.25至1)溶液中搅拌均匀,直到石墨不冒泡(约2hr),以形成过氯酸与硝酸插层的石墨(呈膨胀悬浮状)。接着以吸管去除多余的插层剂后,加入5g SDBS并搅拌均匀。将上述混合物置入微波反应器后施加微波,进行热裂解加成反应1分钟。由于SDBS上有负电荷的SO3 -官能基,可藉电荷吸引扩散进入已插层的石墨层间,形成SDBS插层的石墨。此时样品颜色略呈棕黑色。将样品加入过量酒精,并以超音波震荡约1小时,直到不再冒气泡。离心清洗去除多余的插层剂、SDBS、与酒精,即得石墨烯卷接枝SDBS的产物。
实施例3(石墨烯卷接枝SDBS与PMAA)
将适量石墨粉加入200mL的过氯酸(70-72%重量比)/硝酸(≥65%重量比)(v/v=0.25至1)溶液中搅拌均匀,直到石墨不冒泡(约2hr),以形成过氯酸与硝酸插层的石墨(呈膨胀悬浮状)。接着以吸管去除多余的插层剂后,加入5g SDBS并搅拌均匀。将上述混合物置入微波反应器后施加微波,进行热裂解加成反应1分钟。由于SDBS上有负电荷的SO3 -官能基,可藉电荷吸引扩散进入已插层的石墨层间,形成SDBS插层的石墨。接着加入10g PMAA并搅拌均匀。将上述混合物置入微波反应器后施加微波,进行热裂解加成反应1分钟。由于PMAA上有大量负电荷的COO-官能基,可藉电荷吸引扩散进入已插层SDBS的石墨层间,形成PMAA与SDBS插层的石墨。此时样品颜色略呈棕黑色。将样品加入过量酒精,并以超音波震荡约1小时,直到不再冒气泡。离心清洗去除多余的插层剂、SDBS、PMAA与酒精,即得石墨烯卷接枝SDBS与PMAA的产物。
实施例4(保水剂包覆的具PMAA接枝石墨烯卷)
将实施例3的石墨烯卷产物,加入2g海藻酸钠(购自振芳公司,型号160-200QG)并搅拌均匀。由于本身具有带电荷的巨大分子,在水合后,可产生粘度,并可与多价金属离子作用产生凝胶反应,形成海藻酸钠包覆的石墨烯卷。接着以实施例1的水气吸附实验确认产物的吸水性。
实施例5(保水剂包覆的具PMAA接枝石墨烯卷)
将实施例3的石墨烯卷产物,加入4g聚丙烯酸铵(购自景明化工,型号03311)并搅拌均匀,形成聚丙烯酸铵包覆的石墨烯卷。接着以实施例1的水气吸附实验确认产物的吸水性。
实施例6(保水剂包覆的具PMAA接枝石墨烯卷)
将实施例3的石墨烯卷产物,加入1g聚乙烯醇(购自Aldrich,型号341584)并搅拌均匀,形成聚乙烯醇包覆的石墨烯卷。接着以实施例1的水气吸附实验确认产物的吸水性。
第4表
虽然本发明已以数个较佳实施例发明如上,然其并非用以限定本发明,任何熟习此技艺者,在不脱离本发明的精神和范围内,当可作任意的更动与润饰,因此本发明的保护范围当视后附的申请专利范围所界定者为准。
Claims (12)
1.一种吸附材料,包括:
石墨烯卷,是石墨烯片沿着轴心卷绕而成,且该石墨烯卷垂直于该轴心的剖面为螺旋状;以及
改质剂,接枝至该石墨烯卷的层间与外侧上,且该改质剂具有亲水基。
2.如权利要求1所述的吸附材料,其中该石墨烯卷与该改质剂的重量比介于1:0.5至1:5之间。
3.如权利要求1所述的吸附材料,其中该改质剂为界面活性剂、亲水性高分子或上述的组合。
4.如权利要求3所述的吸附材料,其中该界面活性剂为十二烷基苯磺酸钠、聚氧乙烯基醚硫酸盐、聚氧乙烯烷基醚或聚乙烯聚胺脂肪酸胺盐。
5.如权利要求3所述的吸附材料,其中该亲水性高分子的重均分子量介于10000至500000之间。
6.如权利要求3所述的吸附材料,其中该亲水性高分子为聚甲基丙烯酸、聚乙烯醇、聚丙烯腈、丙烯酸酯-丙烯酰胺共聚物、乙烯-马来酸酐共聚物、羧甲基纤维素或淀粉接枝的聚丙烯腈。
7.如权利要求3所述的吸附材料,其中该亲水性高分子的亲水基是磺酸钠,且该亲水性高分子为聚苯乙烯磺酸钠或木质磺酸钠。
8.如权利要求3所述的吸附材料,其中该亲水性高分子的亲水基是胺基,且该亲水性高分子为聚丙烯酰胺、聚乙烯吡咯烷酮、聚乙烯亚胺或聚二甲基二烯丙基氯化铵。
9.如权利要求1所述的吸附材料,更包括保水剂包覆该石墨烯卷,且该保水剂为海藻酸钠、聚丙烯酸或其盐类、聚氧乙烯或聚乙烯醇。
10.一种吸附材料的形成方法,包括:
(a)混合石墨与插层剂,以形成第一插层石墨;
(b)混合该第一插层石墨与改质剂后,施加微波至混合物以形成第二插层石墨;
(c)将该第二插层石墨置于醇类中进行超音波震荡,以形成吸附材料,其中该吸附材料包括:
石墨烯卷,是石墨烯片沿着轴心卷绕而成,且该石墨烯卷垂直于该轴心的剖面为螺旋状;以及
该改质剂,接枝至该石墨烯卷的层间与外侧上,且该改质剂具有亲水基。
11.如权利要求10所述的吸附材料的形成方法,其中该插层剂为硫酸、过氯酸、硝酸、磷酸、硬脂酸或上述的组合。
12.一种吸附式热泵,包括:
吸附/脱附部份,具有吸附材料以吸附/脱附制冷剂;
蒸发部份,用以蒸发该制冷剂,且该蒸发部份连接至该吸附/脱附部份;以及
冷凝部份,用以冷凝该制冷剂,且该冷凝部份连接至该吸附/脱附部份,
其中该吸附材料包括:
石墨烯卷,是石墨烯片沿着轴心卷绕而成,且该石墨烯卷垂直于该轴心的剖面为螺旋状;以及
改质剂,接枝至该石墨烯卷的层间与外侧上,且该改质剂具有亲水基。
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TW201723142A (zh) | 2017-07-01 |
TWI592475B (zh) | 2017-07-21 |
US20170173556A1 (en) | 2017-06-22 |
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