TWI400227B - 潛熱儲存材料及用於潛熱儲存材料之二烷醚的製法 - Google Patents
潛熱儲存材料及用於潛熱儲存材料之二烷醚的製法 Download PDFInfo
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- 238000006384 oligomerization reaction Methods 0.000 claims description 2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
-
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
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Description
本發明係關於一種從直鏈醇製備潛熱儲存材料之方法，及以二烷醚作為潛熱儲存材料。
相變材料(PCMs-Phase Change Materials)可以透過在一選定的溫度範圍使之融化或固化而釋放或吸收或儲存熱量，並因而產生如同潛熱儲存材料的作用。這個蓄熱原理可以應用在例如，建築物的牆體隔熱上。這樣的潛熱儲存材料是以例如，微膠囊的形態混入塗牆粉或石膏灰膠紙夾板中，並且在白天承受劇烈的熱影響期間液化掉。所吸收的熱被儲存在牆壁內而使室內保持涼爽。在黃昏時刻和夜間冷卻之後，液態的蓄熱材料固化並將結晶熱釋放到周圍環境。室內因而被暖化。
潛熱儲存材料主要是添加了石蠟烴和石蠟烴混合物。商業上所販售之供PCM-應用的石蠟烴混合物有例如，Rubitherm27和Rubitherm31。上述Rubitherm-混合物的主成分是一種C18
石蠟烴，其含量則僅59或39質量%。該等石蠟烴混合物由鏈長範圍在C17
至C21
，或者C17
至C30
的偶數一和非偶數直鏈石蠟烴組成，所具有之直鏈部分則達98.0或95.6質量%。
石蠟烴亦可從商業上所販售之α-烯烴經過氫化而製得。此等石蠟烴的範圍在C16
至C18
，但是線性度僅有大約90至小於95質量%，其缺點則是因為分枝狀的副產物以致於熔化焓(enthalpy of fusion)相對地明顯低於高線性度的石蠟烴。
已知由具有不同鏈長及/或高分枝部分的偶數和非偶數石蠟烴所組成的混合物，缺點在於，其具有寬幅或者多種不同的熔化峰，而有關溫度如果彼此相距太遠，則在一般的情況下，可能的熔化焓就僅有一部份是實質有用的。
因此，本發明之課題是要提供一種高線性度的化合物，像是石蠟烴之，具有確定鏈長的化合物，以供作為潛熱儲存材料來使用。藉此即可達成下列優點：其一是，超純的石蠟烴和石蠟烴混合物相較，其熔化範圍明顯較窄，因此，在微小的溫度差異下，儲存容量就已經可以完全地被利用。此外，純物質的熔化焓明顯高於混合物。
本發明是由各獨立請求項的標的來加以界定。較佳的實施態樣則是記載於依附項的標的或以下的說明中。
純物質，尤其是特定鏈長的直鏈石蠟烴，比分枝石蠟烴或石蠟烴混合物具有較高的熔化熱和較窄的熔化範圍。PCM的熔化溫度可以透過選擇石蠟烴的結構和鏈長而在一整個大溫度範圍上做調節。
這些石蠟烴主要滿足下列各自獨立的特點：
a)其等具有高達95質量%以上，特別是高達98質量%以上之偶數鏈長；
b)其等高達95質量%以上，特別是高達97質量%以上僅有一種特定C-數；以及
c)其等高達95質量%以上是直鏈狀的。
二烷醚分別具有兩個殘基R，以致於極限值相對應地比較低。二烷醚主要滿足下列各自獨立的特點：
a)其等具有高達91質量%以上，特別是高達95質量%以上之偶數鏈長；
b)其等高達91質量%以上，特別是高達94質量%以上僅有一種特定C-數；以及
c)其等高達91質量%以上，特別是高達95質量%以上是直鏈狀的。
特別是醇類，經淨化或者選擇，使其等業已滿足該等石蠟烴的上述極限值者，不僅可以用來製造二烷醚，也可以用來製造石蠟烴。
潛熱儲存材料係由直鏈脂族醇經由脫水反應而產生二烷醚或烯烴(olefin)，最後再接著被氫化成石蠟烴。本發明所稱脂族醇是指C-數大於等於6且較佳為具有終端羥基的醇類。特別合適的起始物質，如果是石蠟烴則為十六烷醇(cetylalcohol)或十八烷醇(stearyl alcohol)，而如果是二烷醚則是十二烷醇(lauryl alcohol)或十四烷醇(myristyl alcohol)。
發明人等意外地發現，供PCM-應用的直鏈石蠟烴尤其以直鏈醇經脫水反應而形成直鏈烯烴，並接著經過氫化而製成之石蠟烴特別合適。所添加的直鏈醇作為單區分是可以容易取得的，且以來自可以重新生長出來的植物性或動物性原料為佳，尤其是植物性的，像是棕櫚油、棕櫚仁油(Palmkernl)、椰子油、菜籽油或其他的植物油。
可以從天然原料取得的醇類具有出色的，例如，＞98質量%的高線性度。因此由其所獲得的石蠟烴出奇地合適於應用在PCMs上。除了天然來源以外，根據齊格勒合成法(Ziegler Synthese)的乙烯齊聚反應(Ethylen-Oligomerisa-tion)而得到的醇類也可以作為本發明所添加之醇類的另一個來源。
另外也可以使用從合成的醇類經過脫水反應而製成的石蠟烴。這些石蠟烴在一般的情況下鏈長範圍是從C16
到C18
，只是線性度常常只有93到99%。
應用直鏈石蠟烴作為PCMs已為人所熟知，從脂醇製僅石蠟烴也同樣是已知的。然而，截至目前為止有關從經過脫水反應的醇類，尤其是那些從可以重新生長出來的原料取得者，所製成的石蠟烴，尚未見被記載為供作為潛熱儲存材料用者。
以前，熟習此項技術者的出發點一直認為從石蠟烴製作醇類是一個比較高級的步驟，因為醇類比石蠟烴有更高的價值。既然如此也就不期待反過來的途徑，也就是從一種醇類來製造一種石蠟烴在經濟上有什麼意義。然而，情況顯示，從醇類脫水反應所得到的石蠟烴提供了特別純質的石蠟烴，而且這個純質的石蠟烴本身比起僅輕微受到污染的石蠟烴有明顯較佳的性質。
對於這個特殊用途而言，石蠟烴的價格在脂族醇的價格之上。在潛熱儲存器中的必要添加量直接和所利用的熔化熱，亦即，物質相關；其具有高了20%的熔化熱，相對應地，為達成相同效果所必需添加的量也較少。例如，相同儲存容量的織物可以用比較輕的重量來製造，因而可以明顯地提高穿著的舒適性。
直脂族醇的另一種脫水反應產物是二烷醚。二烷醚同樣是非極性的，且其特色是熔化峰尖銳及熔化熱高。尤其雙十二烷基醚(didodecylether)和雙十四烷基醚(ditetra-decyl ether)具有和例如，C18
或C22
石蠟烴相似的熔化溫度。適合用於脫水反應以形成二烷醚的催化劑為氧化鋁，包括波希米亞氧化鋁(boehmischer Tonerde)。
比較藉由脂族醇-脫水反應製成的產物，二烷醚及烯烴/石蠟烴，二烷醚的優點在於其等可以經濟地加以製造，因為每2莫耳的脂族醇只須排除1莫耳的水。只要有需求，醚類可藉抗氧化劑使其穩定以阻止過氧化物的形成，基於此，在PCMs經常使用於其中之微-或大膠囊(Micro-oder Macrokapseln)內，醚類的分解會因膠囊層(常見為一聚合物層)而充分地減到最低限度。
潛熱儲存材料主要是由一高分子材料作為膠囊壁，做成平均粒子尺寸在1到200μm範圍內之微膠囊，或者平均粒子尺寸從大於200μm到2cm的範圍之大膠囊。合適的高分子材料可以舉例如，苯乙烯-二乙烯苯-聚合物(Styrol-Divinylbenzol-polymere)，或不飽和聚酯。尤其是囊壁材料，因為需要良好的經時(老化)穩定性，而以硬質塑膠聚合物(duroplastische Polymere)特別合適。適用的硬質塑膠高分子材料可以舉例如，網絡聚合的甲醛樹脂、網絡聚合的聚脲和網絡聚合的聚氨酯，以及網絡聚合的甲基丙烯酸酯聚合物(Methacrylsureesterpolymere)。
熔化溫度和熔化熱是利用DSC-分析理論來測定。在一設定的加熱-和冷卻速率下，測定起始溫度(Onset-Temperature)(熔化溫度)和曲線下的面積(熔化熱)。利用DSC所取得之石蠟烴與石蠟烴混合物的熔化溫度和熔化熱分別記述在試驗部分。
第1圖石蠟烴Rubitherm27和Rubitherm31的C-鏈分佈；第2圖C16至C22石蠟烴(純的)的DSC-圖；第3圖Rubitherm31/Di-C12醚/C20-石蠟烴之DSC-圖比對；第4圖Rubitherm27/C18-石蠟烴/C16-石蠟烴之DSC-圖比對；第5圖Di-C12/C14/C16/C18-醚之DSC-圖；第6圖合成的/天然來源的十六烷之DSC-圖比對。
用以測定熔化焓[J/g]和起始溫度的DSC-分析評估是根據DIN 53765來實施。所有的DSC-曲線都是用Firma Netzsch的DSC 204 F1儀器，在10K/min的加熱-和冷速率下進行測定。
市售的PCMs是Rubitherm27、Rubitherm31。Rubitherm27和Rubitherm31具有如第1圖所示的組成(以GC測得)，此外，顯示出如以下所示之利用DSC所測出之特性：
直鏈脂族醇的脫水反應試驗係如下述，就十六烷醇經脫水反應而形成直鏈烯烴(試驗1)和十六碳烯(Hexadecen)的氫化來加以說明。
將2474g的NACOL16-99(純度99.5%，來自可重新長出的原料)和500g的Al2
O3
以及60mL的二甲苯加入一6-L燒瓶中，並且在水分離析器上加熱至195℃，保持4.5小時。在這個過程中產生180mL的水。所生成的十六碳烯在真空中餾出。獲得一由α-烯烴和內烯烴組成的混合物。
試驗1中所獲得之十六碳烯685g係依習知方法，透過一異相的含Ni催化劑，在20bar的H2
-壓力下，98℃，進行超過7小時的氫化，並且在冷卻後加以過濾。
具有C16
至C22
鏈長的脂族醇係依試驗1和2的記載添加，並獲得下列的石蠟烴：
重複試驗1和2，但是所添加的醇類是使用一得自齊格勒合成法的合成脂族醇(十六烷醇)，純度95.6%。
重複試驗2，但是所添加的烯烴是使用一合成的烯烴(十六碳烯，Chevron Phillips公司)，純度94.2%。
根據不同的製造方法所得到之純度不同的石蠟烴，其等之起始溫度和熔化熱的對照係以十六烷為例，示於下表。
將十八烷和二十二烷以重量比1：1、2：1和3：1的比例混合，並重新測定DSC-曲線。
直鏈脂族醇之部分脫水反應將例示如以下所載之，從十二烷醇經脫水反應形成直鏈二烷醚。
依據已知方法，以10kg/h的量將NACOL12-99(純度99.2%，來自可重新生長出來的原料)在260℃下通過Al2
O3
-球導入一填充床反應器(Φ=60mm，1=900nm)。接著在真空中餾出所產生之雙十二烷基醚(didodecylether)。
第1圖石蠟烴Rubitherm27和Rubitherm31的C-鏈分佈；
第2圖C16至C22石蠟烴(純的)的DSC-圖；
第3圖Rubitherm31/Di-C12醚/C20-石蠟烴之DSC-圖比對；
第4圖Rubitherm27/C18-石蠟烴/C16-石蠟烴之DSC-圖比對；
第5圖Di-C12/C14/C16/C18-醚之DSC-圖；
第6圖合成的/天然來源的十六烷之DSC-圖比對。
Claims (9)
- 一種用以從直鏈脂族醇製造一潛熱儲存材料的方法，其中，脂族醇係透過蒸餾而純化，以在醇類的階段獲得：˙大於95質量%的直鏈脂族醇，˙大於95質量%的具有偶數鏈長之脂族醇，及˙高達95質量%以上的僅具一特定C-數的脂族醇，接著，將上述直鏈脂族醇經脫水反應以形成烯烴並接著經氫化成石蠟烴，其中該石蠟烴係使用作為一相變材料，其係藉由液化而吸收熱量，並在冷卻後、固化時釋放蓄熱。
- 如申請專利範圍第1項之方法，其中該石蠟烴高達98質量%以上具有偶數鏈長。
- 如申請專利範圍第1項之方法，其中該石蠟烴高達97質量%以上僅有一種特定C-數。
- 如申請專利範圍第1項的方法，其中該脂族醇是十六烷醇或十八烷醇。
- 如申請專利範圍第1項的方法，其中該脂族醇係由天然的植物原料取得。
- 如申請專利範圍第1項的方法，其中該脂族醇係依據齊格勒合成法通過乙烯齊聚反應(oligomerization)而製成。
- 如申請專利範圍第1項的方法，其中該潛熱儲存材料被一作為膠囊壁之高分子材料密封在平均粒子尺寸為1至200μm的範圍之微膠囊，或平均粒子尺寸在大於200μm至2cm的範圍之大膠囊(macro-capsule)內。
- 如申請專利範圍第1項的方法，其中該石蠟烴係十六烷、十八烷、二十烷或二十二烷，且該脂肪醇係由天然的植物原料取得。
- 如申請專利範圍第1至8項任一項的方法，其中該脂肪醇係大於98質量%為直鏈的。
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| ES2685072T3 (es) * | 2009-10-30 | 2018-10-05 | Kao Corporation | Método para producir olefinas |
| DE102009054802B4 (de) * | 2009-12-16 | 2017-08-17 | Holmenkol Gmbh | Verwendung von Fettalkoholethern als Gleitmittel für Sportgeräte, Gleitmittelzusammensetzung und Verfahren zur Beschichtung eines Sportgeräts |
| CN103108899A (zh) | 2010-07-20 | 2013-05-15 | 巴斯夫欧洲公司 | 包含微胶囊化潜热蓄热器材料的聚酰胺模制品 |
| US8957133B2 (en) | 2010-07-20 | 2015-02-17 | Basf Se | Polyamide moldings comprising microencapsulated latent-heat-accumulator material |
| CN102417812A (zh) * | 2011-09-28 | 2012-04-18 | 兰州理工大学 | 正十四醇相变微胶囊及其制备方法 |
| JP6061106B2 (ja) * | 2012-08-10 | 2017-01-18 | Jsr株式会社 | 蓄熱材用組成物 |
| CN104884412A (zh) | 2012-12-26 | 2015-09-02 | 花王株式会社 | 烯烃的制造方法 |
| CN103468223A (zh) * | 2013-09-30 | 2013-12-25 | 天津工业大学 | 一种相变储能材料大胶囊及其制备方法 |
| EP3816260B1 (en) * | 2018-06-28 | 2023-03-08 | Kaneka Corporation | Heat storage material composition and use thereof |
| JP7674144B2 (ja) * | 2021-04-27 | 2025-05-09 | 協同油脂株式会社 | 蓄冷熱剤組成物 |
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| US5525251A (en) * | 1994-11-18 | 1996-06-11 | Store Heat And Produce Energy, Inc. | Thermal energy storage compositions to provide heating and cooling capabilities |
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| KR20160032256A (ko) | 2016-03-23 |
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| WO2009092349A3 (de) | 2009-12-23 |
| KR20100106593A (ko) | 2010-10-01 |
| US20160257628A1 (en) | 2016-09-08 |
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