TWI531697B - Method and use of making adsorbent material from poultry feathers - Google Patents
Method and use of making adsorbent material from poultry feathers Download PDFInfo
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Description
本發明係有關於羽絨廢料之處理與應用,特別是指由禽類羽毛製成吸附材料之方法及用途。
習見羽絨製品中所使用之羽絨,大多係由絨(Down)及羽(Feather)所組成;絨(Down)是為不含毛桿的羽毛纖維,係用以作為保暖的主要材料,而羽(Feather)是為帶有羽桿的小羽毛,是用來提高羽絨呈現蓬鬆的功效;綜合絨及羽特色之羽絨製品,可具有輕便、柔軟、保暖的特點。
又,羽絨所使用之小羽毛,主要係採用6cm以下的水鳥羽毛(鴨毛和鵝毛),然而,鴨鵝羽毛的長短不一,長度從1cm~15cm以上都有,因此一般羽絨業者將羽毛群篩選後,6cm以上的鴨鵝羽毛廢料已沒有經濟利用價值,且數量龐大,業者可將其透過水解成生羽毛粉,再利用於飼料或肥料方面之用途,但鑒於鴨鵝之羽毛飽含角質及雙硫鍵,若不經高度水解,動物的消化系統將無法消化其應用之飼料產物;因此,羽絨業者往往在鴨鵝羽毛廢料的處理上,無論是廢棄處理或是再利用,均會造成不斐的負擔。
鑒於上述問題,並基於近一世紀以來,已有多種關於利用毛髮材料分解重組後應用於基礎生物材料之研究,是以,研究出適用於鴨鵝羽毛廢料再利用之方式,製成副產品來提升經濟效益,係羽絨業者在廢料處理上長久以來的問題。
本發明主要是關於禽類羽毛製成吸附材料之方法與應用,利
用篩選後之羽毛廢料,作成副產品提高其經濟價值,降低材料上的浪費並減低生產羽絨製品所耗費的成本。
本發明提供之由禽類羽毛製成吸附材料之方法,係先選取出羽毛材料,將該羽毛材料經過有洗滌去脂、乾燥滅菌等程序之前置處理,再將其粉碎成大小介於0.1μm~1cm的粉碎物,最後進行表面活化的改質處理,製作成可吸收預定物質之吸附材料。
禽類羽毛呈葉狀纖維體,且羽梗(10)上密佈有數以萬計的細小氣孔(20)(如圖一至圖三所示),具有吸收物質的特性,經粉碎處理後製成眾多細小的碎物或顆粒,其比表面積增加,可提升分子的活性,強化吸收之效能,可作為吸附材料,用以製造消臭用或過濾用之濾材,吸附或過濾氣態、液態或固態中預定的分子,諸如用以過濾水中較大(約大於0.4μm)之懸浮顆粒、雜質,或者是過濾水中的色素;而羽毛材料之粉碎物可根據欲吸收之物質極性的強弱,經過適當的表面改質處理,達到作為吸收如銅、鉛、鋅、鉻、鎂、鈣、砷等種類的金屬離子,如苯酚、染料等的有機溶劑,如甲醛、氨、苯、醋酸、硫化氫等的揮發性氣體或油汙的用途。
較佳者,羽毛材料係使用具有羽梗之禽類羽毛,且可選自於長度大於1cm之水鳥類羽毛(鴨毛或鵝毛),當然,亦可採用長度6cm~15cm以上無法用做羽絨填充材料之鴨鵝羽毛廢料。
較佳者,前置處理至少包含有一洗滌去脂程序及一乾燥滅菌程序,用以去除動物羽毛原有的氣味、表面所附的油脂、細菌。其中,洗滌去脂程序係以相對羽毛重量4~10%的介面活性劑製成水溶液,或是以pH7~10的鹼性水溶液,在25℃~90℃環境條件下,水洗0.5~2小時,水洗後,脫水;乾燥滅菌程序則是以110℃~140℃的高溫進行乾燥及滅菌。
較佳者,粉碎處理採行的方式可分為低階粉碎、中階粉碎和高階粉碎三種,可依需求選用其一方式或其組合。因羽毛具有一定程度的韌性,低階粉碎係以直接剪切粉碎的方式,將羽毛材料粉碎成平均粒徑1cm以下之粉碎物(粉碎絨);而中階粉碎則係一種低溫超微粉碎的方式,利用在-30至-120℃之低溫環境下,藉以使羽毛之韌性降低、脆性增加,讓加工之斷裂面平整,使羽梗之氣孔得以露出,其係可利用球磨式、氣流式或剪
切式的工法將羽毛材料進行粉碎,再經過篩節使平均粒徑為介於0.1μm~400μm之粉碎物;高階粉碎則係以溶解造粒提取角蛋白的方式,形成平均粒徑介於0.1μm~10μm之粉碎物。
較佳者,粉碎物的改質處理可經由活化助劑進行表面活化,或者可與輔材經熱塑或結合形成複合材料;其中,可採用之活化助劑可以是帶氧系之氧化劑、帶硫系之還原劑、酸處理之酸性助劑、鹼處理之鹼性助劑、尿素、環氧化物或乙二胺,而可採用之輔材可為熱融纖維、聚氨酯、聚乙烯醇、聚氯乙烯、聚乙烯、聚丙烯、甘油或二甘醇。
以下係藉由本發明較佳之實施例做進一步的說明,熟習此技藝之人士可由本說明書所揭示之內容輕易地瞭解本發明之優點與功效。本發明亦可藉由其他不同之實施方式加以施行或應用,說明書中所揭示之各細節亦可基於不同觀點與應用,在不悖離本發明所揭示之精神下賦予不同之修飾與變更。
10‧‧‧羽梗
20‧‧‧氣孔
圖一為顯微鏡中觀察之羽梗剖面圖。
圖二為顯微鏡中觀察之羽梗中具有不規則氣孔之結構圖。
圖三為顯微鏡中觀察之氣孔中孔壁為網狀細孔組織。
禽類動物之羽毛,諸如水鳥羽毛,又或是作為羽絨主要材料之鵝毛或鴨毛,其羽毛長短不一,長度從1cm~15cm以上都有,可配合參閱圖一至圖三,分別係透過x110、x950、x10000三種倍率觀察羽梗10切面之組織結構圖,可見羽梗10中密布有數以萬計的細小氣孔20,而根據不同的應用領域,經表面改質活化後,可用於吸附不同物質的分子。
羽梗10可透用物理機械法粉碎成介於0.1μm~1cm間多種不同等級的大小,不同等級的大小具有不同的比表面積,當比表面積越大,分子的活性越大,可吸附的物質越多。於粉碎後再根據所吸附物的極性強
弱,進行表面改質活化,可用於吸附或過濾氣態、液態或固態之分子。
本發明實施例所採用之羽毛材料,係為具有羽梗10之鴨毛或鵝毛,其長度多介於1~15cm之間,而基於廢物利用的目的,羽毛材料可選自經篩選羽絨材料後剩餘之羽毛廢料,其長度約介於6~15cm以上。首先,須將羽毛經過一前置處理的加工過程,其主要是用來去除動物羽毛本身所附之氣味、油脂、細菌等雜質,主要包括有一洗滌去脂程序或及一乾燥滅菌程序。於羽毛材料選取完成後,先經過洗滌去脂程序,其係利用約為羽毛材料重量4~10%的介面活性劑所製成水溶液,或是利用pH7~10的鹼性水溶液,在25℃~90℃環境條件下,將選取的羽毛材料水洗0.5~2小時,於水洗完成後進行脫水處理,而後進入乾燥滅菌程序,其係以高溫滅菌的方式,將脫水後的羽毛材料置於110℃~140℃的高溫環境下同時進行乾操及滅菌處理,至少持續20~40分鐘,待羽絨材料完全烘乾後,即完成前置處理的加工過程。
當前置處理完成後,則進入粉碎處理的流程,粉碎處理係將羽毛材料粉碎成0.1μm~1cm的粉碎物,藉以增加羽毛材料之比表面積,提高其表面氣孔吸附之能力。本發明之實施例,對於羽毛材料的粉碎處理,主要採行的方式有三,分別為直接剪切加工的低階粉碎、利用低溫環境超微粉碎加工的中階粉碎、以及溶解造粒加工的高階粉碎。
因羽毛具有一定的韌性,透過低階粉碎,可使羽毛材料以剪切力加工為1cm以下的粉碎物(粉碎絨),依後續處理上的需求,可進一步併用中階粉碎及高階粉碎之處理方式,取得更細微顆粒的粉碎物。
中階粉碎,係利用低溫環境降低羽毛之韌性,使其脆性增加,讓加工之斷裂面平整,羽梗之氣孔得以露出於表面,提高其吸收的性能;本實施例採行的中階粉碎,係將羽毛材料或經低階粉碎處理過之粉碎物置於-30至-120℃之環境中,再以球磨式、氣流式或剪切式的工法進行粉碎,使其形成粒徑約於0.1μm~400μm之粉碎物。
高階粉碎,則係以溶解造粒的方式,萃取出角蛋白顆粒,形成平均粒徑介於0.1μm~10μm之粉碎物;對於萃取角蛋白顆粒之方式,依其提取之角蛋白純度,可有多種萃取方式,本實施例採行之方法有二,一
為:將羽毛材料或經低階粉碎處理過之粉碎物以0.5M的硫化鈉(無機鹽類)溶液,加熱至30℃,在強鹼(pH10~13)的環境下,將羽毛材料(粉碎物)與溶液攪拌使其溶解,用濾紙收集上清液。在上清液緩倒入硫酸銨溶液(體積比1:1),收集沉澱下來的產物,沉澱物清水沖洗數次後可回溶至氫氧化鈉液,此為純化後的蛋白質顆粒:另一為:使用5%的2-羥基乙硫醇(為還原劑)為溶劑加入2.6M硫脲,5M的尿素製成溶液,再將羽毛材料或經低階粉碎處理過之粉碎物與此溶液攪拌,在鹼性(pH8.5)的環境下加入Tris-HCl使角蛋白沉澱,離心過濾後可得角蛋白顆粒。
粉碎處理完成後,即可進入後續之表面改質處理,作為製造各式濾材的吸附材料;本發明實施例之改質處理,主要採行的方式有兩種,一係利用活化助劑來對粉碎物進行表面的活化,另一則是利用輔材與粉碎物結合形成複合材料;經改質處理活化表面後,依其處理之方式,可應用於吸附金屬離子、有機溶劑、油汙或揮發性氣體等之濾材中。以下,茲依本發明各可行實施例之改質處理過程,配合其應用面說明如下:
(1)將0.1μm~400μm之粉碎物與輔材熱融纖維以重量1:1之比例混合,形成非織造布,可作為濾材,用以於常溫20~60℃下吸收廢水或汙水中的重金屬有害離子(銅離子)。
(2)利用活化助劑Na2S2O5對0.1μm~400μm的粉碎物進行表面活化,來提高對Pb2+的吸附能力,且可與聚丙烯(PP)融熔成濾心,用以吸收水中之金屬離子。
(3)藉由角蛋白顆粒具有與金屬離子相互作用的特性,將0.1μm~10μm之粉碎物(角蛋白顆粒)與輔材聚氨酯混合後製成多孔性的薄膜,可對金屬離子具有良好的吸收特性,使用於pH1.5~pH2.5之水中時,其吸附的效率最顯著。
(4)利用約1cm大小的粉碎物為主要材料加入適當輔材製作之濾材,可用於吸附非水溶性的有機溶劑,其與粉碎物可快速形成凝膠;再者,透過離心處理或藉由壓擠,可將溶劑與粉碎物分離,使濾材可重複使用。
(5)利用約400μm~1cm大小的粉碎物為主要材料加入適當
輔材製作之濾材,可用於過濾水中的大於0.4μm之顆粒懸浮雜質、及水中的色素。
(6)利用約1cm大小的粉碎物,以雙氧水作為活化助劑處理後,可用於吸收水溶液中的苯酚;於常溫約30℃、pH值介於2~3的水中,經過1天的時間可吸收其中至少70%的苯酚。
(7)採用約1cm大小的粉碎物,藉由羽毛梗中有親水基及親油基,以及羽梗的中空多孔結構,在與輔材聚丙烯、聚氯乙烯混合後,可製成布料形式,用於吸附水面上的各式油汙。
(8)利用粒徑介於0.1μm~1cm間的粉碎物,其比表面積較大且有強的疏水性和親有機物性,有利於揮發性有機化合物(VOC)之吸附。其透過利用活化助劑如檸檬酸、硫酸亞鐵、硫酸銅或磺化酞菁鈷表面活化後,可分別作為製備功能性甲醛之吸附材料、功能性氨之吸附材料或功能性苯之吸附材料。
(9)利用約400μm~1cm大小的粉碎物,加入0.1mol/L之NaOH溶液中,並添加活化助劑乙二胺或環氧氯丙烷,反應2小時,再用酸中和,可吸附鉻離子。
(10)利用約400μm~1cm大小的粉碎物,加入活化助劑硝酸或醋酸處理後,其角蛋白的部分胺基發生陽離子化,可吸附陰離子,如鉻離子。或與陽離子之間的靜電相互作用,形成化學吸附。
綜合上述,可知本發明具有極佳之進步及實用性,對於習知羽絨產業在羽毛廢料之處理上,均未見有相同或近似之手法存在於先,應符合申請專利之專利要件,爰依法之提出申請。唯以上所述者僅係本發明之較佳實方式及其合理之用途而已,故舉凡應用本發明說明書及申請專利範圍所為之其他等效方法結構變化者均屬可行,理應包含在本發明申請專利範圍內。
10‧‧‧羽梗
20‧‧‧氣孔
Claims (4)
- 一種由禽類羽毛製成吸附材料之方法,係包含:選取一羽毛材料,且該羽毛材料係為具有羽梗之禽類羽毛;將該羽毛材料進行清潔滅菌之前置處理;將前置處理後之羽毛材料進行粉碎處理,形成大小約介於0.1μm~1cm的粉碎物;及將形成的粉碎物進行改質處理,製成可吸收預定物質之吸附材料;其中,該粉碎物之改質處理係經由活化助劑進行表面活化,且該活化助劑可為帶氧系之氧化劑、帶硫系之還原劑、酸處理之酸性助劑、鹼處理之鹼性助劑、尿素、環氧化物或乙二胺。
- 如請求項1所述由禽類羽毛製成吸附材料之方法,其中該羽毛材料係可選自長度1cm以上之鴨毛或鵝毛。
- 如請求項1所述由禽類羽毛製成吸附材料之方法,其中羽毛材料之該粉碎處理可採用低階粉碎、中階粉碎或高階粉碎三種其一或任意組合;其中,該低階粉碎係直接剪切粉碎成平均粒徑1cm以下之粉碎物,該中階粉碎係於-30至-120℃之低溫環境下,以球磨、氣流或剪切的方式超微粉碎成平均粒徑介於0.1μm~400μm之粉碎物,該高階粉碎係以溶解造粒的方式,形成平均粒徑介於0.1μm~10μm之粉碎物。
- 如請求項1所述由禽類羽毛製成吸附材料之方法,其所製成之吸附材料可用於消臭或過濾,其可吸收之預定物質可為金屬離子、有機溶劑、油汙或揮發性氣體。
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