TWI419975B - Method of manufacturing protein filling agent by using animal hair - Google Patents
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本發明係關於一種以動物毛為原料製備製革用蛋白填料的方法,屬於製革中的廢渣資源的利用領域。The invention relates to a method for preparing a protein filler for leather making by using animal hair as a raw material, and belongs to the field of utilization of waste residue resources in leather making.
製革廢水的有毒有害物質主要來自脫毛程序所產生的含硫廢水,其中的COD達10000 mg/L以上,占製革廢水總負荷的40%左右,硫含量高達5500 mg/L以上,占製革廢水總硫含量的90%左右。因此用保毛脫毛法代替毀毛脫毛法,實現脫毛程序的清潔化是降低製革工業污染的根本所在。然而現在的製革企業卻冒天下之大不諱,寧願堅持毀毛法脫毛也不採用保毛脫毛法,究其原因並不是唯恐毛脫不乾淨,而是擔心毛一旦回收就會堆積如山,毛的資源化利用是保毛脫毛法得以推廣應用的瓶頸。The toxic and harmful substances in tannery wastewater mainly come from the sulfur-containing wastewater generated by the hair removal process. The COD of the tannery wastewater is above 10000 mg/L, accounting for about 40% of the total load of the tannery wastewater, and the sulfur content is above 5500 mg/L, accounting for the total amount of tannery wastewater. About 90% of the sulfur content. Therefore, using the hair removal hair removal method instead of the hair removal hair removal method, the cleaning of the hair removal process is the fundamental reason for reducing the pollution of the tanning industry. However, the current tannery companies are taking great risks in the world. They prefer to insist on ruining the hair and not using the hair removal method. The reason is not that the hair is not clean, but that the hair will be piled up like a mountain. Resource utilization is the bottleneck for the promotion and application of hair removal hair removal.
儘管目前保毛脫毛法在製革生產中所占比例很小,但其最終將成為脫毛工序的主導脫毛方法。原因有兩點:第一,現在普遍使用的毀毛脫毛法能導致嚴重的環境污染,而人類的環保意識正在增強,世界各國的環保法規也更加嚴格,保毛法取代毀毛法已是大勢所趨;第二,用保毛脫毛法代替毀毛脫毛法,能夠減少廢水處理成本,假如再解決毛的資源化利用問題,毛即將轉化為新的經濟增長點,如此以來,變廢為寶,一舉兩得,企業會熱衷於對現有生產製程進行投資改造。Although the current hair removal method accounts for a small proportion of leather production, it will eventually become the dominant hair removal method for the hair removal process. There are two reasons for this: First, the widespread use of hair removal and hair removal methods can lead to serious environmental pollution, and human environmental awareness is increasing. The environmental laws and regulations of countries around the world are also more stringent. Secondly, replacing the hair removal and hair removal method with hair removal hair removal method can reduce the cost of wastewater treatment. If the problem of resource utilization of hair is solved, Mao will soon be transformed into a new economic growth point. Thus, turning waste into treasure, killing two birds with one stone Enterprises will be keen to invest in the transformation of existing production processes.
目前,動物毛的回收利用研究大多集中在羊毛和豬毛。羊毛具有特殊的氈化性能和優良的可紡性,一般用於 生產毛氈和毛紡織品,而製革脫毛產生的廢羊毛沒有紡織價值,只能用於制氈或者直接丟棄;豬毛粗壯、硬度和斷裂強度大,一般用於製作毛刷等;牛毛既沒有良好的可紡性,又沒有足夠的強度,故有關牛毛利用的報導寥寥無幾,大都處於探索階段,離工業化的要求還相差甚遠。可見,現有的動物毛利用技術產品附加值很低,或者不回收而丟棄,嚴重污染環境。因此尋找動物毛的有效利用途徑,研發高附加值產品,已成為製革廢渣利用中的重要課題,同時也是保毛脫毛法能夠為製革企業所採用的技術前提。At present, most of the research on the recycling of animal hair is concentrated on wool and pig hair. Wool has special felting properties and excellent spinnability, generally used in Production of felt and wool textiles, and the waste wool produced by leather hair removal has no textile value, can only be used for felting or directly discarded; pig hair is thick and strong, hardness and breaking strength are large, generally used for making brushes, etc.; cattle hair is neither good The spinnability, but not enough strength, so there are very few reports on the use of cattle hair, mostly in the exploration stage, far from the requirements of industrialization. It can be seen that the existing animal hair utilization technology products have low added value, or are discarded without recycling, and seriously pollute the environment. Therefore, finding effective ways to use animal hair and developing high value-added products has become an important issue in the utilization of tannery waste, and it is also a technical premise that can be used by tanners.
本發明係提供一種以動物毛為原料製備製革用蛋白填料的方法,其特徵在於該方法包括以下步驟:(1)將動物毛用自來水洗淨,用至少能將毛淹沒的體積的0.01-0.5 M無機酸溶液浸泡10-48小時,再用自來水將毛洗至中性,瀝去水,自然晾乾;取上述毛600重量份,用至少能將毛淹沒的體積的2-30 wt%還原劑溶液浸泡10-48小時,瀝去水,晾乾,備用;(2)將上述預處理後的毛放入帶有攪拌器、溫度計和回流冷凝器的反應釜中,加入至少能將毛淹沒的體積的0.5-20 wt%的鹼性化合物溶液,升溫50-95℃,保溫2-20小時,得到黏稠狀液體;(3)將上述液體冷卻後,用無機酸溶液調整pH至5-8,得到固含量為10-20%富含角蛋白多肽的濾液,經濃縮乾燥即得製革用蛋白填料。The invention provides a method for preparing a protein filler for tanning by using animal hair as a raw material, characterized in that the method comprises the following steps: (1) washing the animal hair with tap water, using a volume of at least 0.01-0.5 which can submerge the hair. M-inorganic acid solution soak for 10-48 hours, then wash the hair to neutral with tap water, drain water, and dry naturally; take 600 parts by weight of the above hair, and reduce it with 2-30 wt% of the volume that can at least drown the hair. Soak the solution for 10-48 hours, drain the water, dry it, and set aside; (2) Put the pre-treated hair into a reaction kettle with a stirrer, thermometer and reflux condenser, and add at least the hair. a volume of 0.5-20 wt% of the alkaline compound solution, heating 50-95 ° C, 2-20 hours of incubation, to obtain a viscous liquid; (3) after cooling the above liquid, adjust the pH to 5-8 with a mineral acid solution A filtrate rich in keratin polypeptide having a solid content of 10-20% is obtained, and concentrated and dried to obtain a protein filler for leather making.
為了讓本發明之上述和其他目的、特徵、和優點能更明顯易懂,下文特舉較佳實施例,並配合所附圖示,作詳細說明如下:The above and other objects, features and advantages of the present invention will become more apparent from
本發明的目的是針對現有技術的不足而提供一種建立在保毛脫毛法基礎上的動物毛的利用技術,將動物毛水解製成蛋白填料,回用於製革生產的複鞣、填充工序,以消除用保毛脫毛法代替毀毛脫毛法的後顧之憂,同時也能降低製革廢水的處理難度。The object of the present invention is to provide a utilization technology of animal hair based on the hair removal hair removal method according to the deficiencies of the prior art, and hydrolyze the animal hair into a protein filler, and reuse the retanning and filling process for the leather production. Eliminate the worries of using the hair removal and hair removal method instead of the hair removal and hair removal method, and also reduce the difficulty of processing the tannery wastewater.
本發明的目的由以下技術措施實現,其中所述原料份數除特殊說明外,均為重量份數。The object of the present invention is achieved by the following technical measures, wherein the parts of the raw materials are all parts by weight unless otherwise specified.
以動物毛為原料製備製革用蛋白填料的方法包括以下步驟:1.將動物毛用自來水洗淨,用至少能將毛淹沒的體積的0.01-0.5 M無機酸溶液浸泡10-48小時,再用自來水將毛洗至中性,瀝去水,自然晾乾;取上述毛600份,用至少能將毛淹沒的體積的2-30 wt%還原劑溶液浸泡10-48小時,瀝去水,晾乾,備用;2.將上述預處理後的毛放入帶有攪拌器、溫度計和回流冷凝器的反應釜中,加入至少能將毛淹沒的體積的0.5-20 wt%的鹼性化合物溶液,升溫50-95℃,保溫2-20小時,得到黏稠狀液體;3.將上述液體冷卻後,用無機酸溶液調整pH至5-8,得到固含量為10-20%富含角蛋白多肽的濾液,經濃縮乾燥即得製革用蛋白填料。The method for preparing the protein filler for tanning by using animal hair comprises the following steps: 1. Washing the animal hair with tap water, soaking for 10 to 48 hours with a volume of 0.01-0.5 M inorganic acid solution capable of submerging the hair, and then using Tap water to wash the hair to neutral, drain the water, and dry naturally; take 600 parts of the above hair, soak for 2 to 48 hours with a 2-30 wt% reducing agent solution that can at least submerge the hair, drain the water, and dry Dry, standby; 2. The above pretreated hair is placed in a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, and a basic compound solution of at least 0.5-20 wt% capable of submerging the hair is added. Heating at 50-95 ° C, holding for 2-20 hours, to obtain a viscous liquid; 3. After cooling the above liquid, adjust the pH to 5-8 with a mineral acid solution to obtain a keratin-rich polypeptide having a solid content of 10-20%. The filtrate is concentrated and dried to obtain a protein filler for leather making.
其中動物毛為製革中保毛脫毛法得到的廢牛毛、廢羊毛或廢豬毛中的任一種。The animal hair is any one of waste cow hair, waste wool or waste pig hair obtained by the hair removal hair removal method in the leather making process.
無機酸為鹽酸或硫酸。The inorganic acid is hydrochloric acid or sulfuric acid.
還原劑為硫氫基乙醇、硫氫基乙酸鈉、Na2 S2 O3 、NaHSO3 、Na2 SO3 中的至少一種。The reducing agent is at least one of sulfhydrylethanol, sodium thioacetate, Na 2 S 2 O 3 , NaHSO 3 , and Na 2 SO 3 .
鹼性化合物為MgO、CaO、NaOH、KOH、Na2 CO3 、NaHCO3 中的至少一種。The basic compound is at least one of MgO, CaO, NaOH, KOH, Na 2 CO 3 , and NaHCO 3 .
本發明具有如下優點:1.本發明為製革生產中用保毛脫毛法取代毀毛脫毛法創造了條件,從根本上降低了製革廢水的污染物含量,有利於綜合廢水的處理及達標排放。The invention has the following advantages: 1. The invention creates conditions for replacing the hair removal and hair removal method by the hair removal and hair removal method in the leather production, and fundamentally reduces the pollutant content of the tannery wastewater, which is beneficial to the treatment of the integrated wastewater and the discharge of the standard.
2.本發明為動物毛提供了簡便易行的利用途徑,將毛製成蛋白填料回用於製革中的複鞣、填充程序,不僅解決了廢棄物的污染問題,而且提高了產品的附加值,具有顯著的環境和經濟效益。2. The invention provides a simple and easy way of utilizing animal hair, and the method of recycling the hair into protein for recycling and filling in the tanning not only solves the problem of waste pollution, but also increases the added value of the product. With significant environmental and economic benefits.
3.本發明製備的蛋白填料不僅具有良好的複鞣填充功能,還有一定的助染性能,產品性能達到國外同等蛋白填料的標準。3. The protein filler prepared by the invention not only has good retanning filling function, but also has certain dyeing performance, and the product performance reaches the standard of foreign equivalent protein filler.
下面通過實施例對本發明進行具體描述,有必要在此指出的是本實施例只用於對本發明進行進一步說明,不能理解為對本發明保護範圍的限制,該領域的技術熟練人員可以根據上述本發明的內容作出一些非本質的改進和調整。The present invention will be described in detail below with reference to the accompanying drawings. The content makes some non-essential improvements and adjustments.
將保毛脫毛法得到的廢牛毛600 g用自來水洗淨,用 0.01 M的鹽酸溶液1200 g浸泡48小時,再用自來水將牛毛洗至中性,瀝去水,用30 wt%的Na2 S2 O3 溶液3000 ml浸泡48小時,瀝去水,晾乾;將上述預處理後的牛毛放入帶有攪拌器、溫度計和回流冷凝器的反應釜中,加入0.5 wt%的NaOH溶液3000 ml,在溫度95℃水解20小時,得到粘稠狀液體;將水解液冷卻後,用硫酸溶液調整pH至5,得到固含量為10%的水解液3200 ml,經濃縮乾燥即得製革用蛋白填料。600 g of waste cow hair obtained by hair removal hair removal method was washed with tap water, soaked in 1200 g of 0.01 M hydrochloric acid solution for 48 hours, then washed with boiled water to neutrality, drained with water, and 30 wt% Na 2 S Soak the 2 O 3 solution in 3000 ml for 48 hours, drain the water, and dry it. Place the pre-treated bovine hair into the reaction vessel with a stirrer, thermometer and reflux condenser, and add 0.5 wt% NaOH solution to 3000 ml. Hydrolyzed at a temperature of 95 ° C for 20 hours to obtain a viscous liquid; after cooling the hydrolyzate, the pH was adjusted to 5 with a sulfuric acid solution to obtain 3200 ml of a hydrolyzate having a solid content of 10%, and the protein filler for tanning was obtained by concentration and drying. .
將保毛脫毛法得到的廢羊毛600 g用自來水洗淨,用0.5 M的硫酸溶液1000 g浸泡10小時,再用自來水將羊毛洗至中性,瀝去水,用15%的硫氫基乙醇和12%的硫氫基乙酸鈉溶液2000 ml浸泡10小時,瀝去水,晾乾;將上述預處理後的羊毛放入帶有攪拌器、溫度計和回流冷凝器的反應釜中,加入12 wt%的Na2 CO3 和7 wt%的NaHCO3 溶液2000 ml,在溫度70℃水解2小時,得到黏稠狀液體;將水解液冷卻後,用鹽酸溶液調整pH至7,得到固含量為20%的水解液1800 ml,經濃縮乾燥即得製革用蛋白填料。Wash 600 g of waste wool obtained by hair removal method with tap water, soak it in 1000 g of 0.5 M sulfuric acid solution for 10 hours, then wash the wool to neutral with tap water, drain water, and use 15% sulfhydryl ethanol. Soaked in 12 ml of 12% sodium thioacetate solution for 10 hours, drained water, and air-dried; put the above pretreated wool into a reaction kettle with a stirrer, thermometer and reflux condenser, add 12 wt % Na 2 CO 3 and 7 wt% NaHCO 3 solution 2000 ml, hydrolyzed at 70 ° C for 2 hours to obtain a viscous liquid; after cooling the hydrolyzate, adjust the pH to 7 with hydrochloric acid solution to obtain a solid content of 20% The 1800 ml of the hydrolyzate was concentrated and dried to obtain a protein filler for tanning.
將保毛脫毛法得到的廢豬毛600 g用自來水洗淨,用0.3 M的鹽酸溶液1500 g浸泡24小時,再用自來水將豬毛洗至中性,瀝去水,用2%的Na2 SO3 溶液2500 ml浸泡30小時,瀝去水,晾乾;將上述預處理後的豬毛放入帶有攪拌器、溫度計和回流冷凝器的反應釜中,加入20 wt%的KOH溶液2500 ml,在溫度50℃水解6小時,得到黏稠狀液體;將水解液冷卻後,用鹽酸溶液調整pH至8, 得到固含量為15%的水解液2600 ml,經濃縮乾燥即得製革用蛋白填料。Wash 600 g of waste pig hair obtained by hair removal method with tap water, soak it in 1500 g of 0.3 M hydrochloric acid solution for 24 hours, then wash the pig hair to neutral with tap water, drain water, use 2% Na 2 Soak the SO 3 solution in 2500 ml for 30 hours, drain off the water, and dry it. Place the pre-treated pig hair into a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, and add 2500 ml of 20 wt% KOH solution. The mixture was hydrolyzed at a temperature of 50 ° C for 6 hours to obtain a viscous liquid; after the hydrolyzate was cooled, the pH was adjusted to 8 with a hydrochloric acid solution to obtain 2,600 ml of a hydrolyzate having a solid content of 15%, and the protein filler for tanning was obtained by concentration and drying.
雖然本發明已以較佳實施例揭露如上,然其並非用以限定本發明,任何熟習此技藝者,在不脫離本發明之精神和範圍內,當可作些許之更動與潤飾,因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application.
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