201211263 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種製造非木材纖維漿料之方法；特定言之，本 發明係關於一種以木聚醣酶對非木木材纖維材料進行一酵素處 理’以製造非木材纖維漿料之方法。 【先前技術】 於造紙工業中，主要係使用木質纖維材料來提供紙張漿料，而 木質纖維材料依其植物特性一般概分為木材類及非木材類二種， 木材纖維材料如松樹、揚木、尤加利樹等多年生植物，非木材纖 維材料則如稻桿、麥桿'蔗渣、棉桿、亞麻等一年生的常見農作 物。其中，非木材纖維材料由於其纖維長度普遍較短且雜質含量 多’因此於造紙工業中’通常係使用木材纖維材料作為製漿原料。 然而’木材纖維材料通常取自有價且生長緩慢之多年生植物，成 本較高且栽植不易；相較之下，非木材纖維材料則多屬農耕植物 中不具經濟價值之部分（如稻桿、麥桿、Μ、棉桿^，不僅取 得容易、生長時躲造紙之目㈣料栽植亦 破壞自然生態。 此外，造紙程序主要包含將木質纖維材料製成紙張聚料與藉由 紙張抄造再將紙張浆料製成紙張之二步驟。目前，紙張聚料之製 備方法主要包含化學製綠、半化學«法及機械製漿法等。其 中，與化學或半化學製漿法相比，機械製漿法由於具有建設費用 低、成漿得率高、對環境污染少等優點，因此逐漸受到重視… 另一方面，機械製漿法主要係利用機械作用力撕裂纖維素纖維並 進一步«，故於磨漿階段的能量消耗較高是其主要缺點。 201211263 目前已有結合較溫和的化學處理或結合酵素處理的 改良式機械製 浆法提出I例5之’美國專利中請案公開第2G050241785號中， 揭露_針葉木之機械製装方法，其教示於磨敷之前添加果膠分 解酵素先預處理原枓，以可降低隸動力損耗；中 國專利申請案 101130936號中’揭露—種降低機械梨精磨段之能量消耗 的方去其係於精磨段之磨毁程序之前，以水解酶對經粗磨後之 =素處理，以降低精磨段磨紧動力。 ° °目則造紙卫業主要皆著重於透過機械製t法並使用 木_維材料作為製t原料，以提供紙張漿料。本發明則提供一 種知用非木材纖維㈣之機械製聚方法除能避免使用大量化學 '劑而污染生態外’更將原本不具經濟價值之非木材纖維 材料轉為有價之再生資源，以減少天然資源之消耗並降低造紙成 太。 【發明内容】 本發明之—目的在於提供一種製造非木材纖維⑽之方法，包 含： 提供一非木材纖維材料； 對該非木材纖維材料進行一水解處理； ㈣水解處理之前或之後，以一木㈣酶_非木材纖維材 料進行一酵素處理；以及 一於該水解處理與該酵素處理之後，對該非木材纖維材料進行 一精製處理，以製得該非木材纖維漿料。 為讓本發明之上述目的、技術特徵及優點能更明顯易懂，下文 201211263 係以部分具體實施態樣進行詳細說明。 【實施方式】 以下將具體地描述根據本發明之部分具體實施態樣 ;惟，在不 背離本發明之精神下，本發明尚可以多種不同形式之態樣來實 踐’不應將本發明保護範圍解釋為限於說明書所陳述者。 本發明提供一種非木材纖維漿料之製造方法’其係使用不具經 濟價值之非木材纖維材料（如稻桿、麥桿等）取代木材纖維材料 • 作為造紙材料，且透過在磨漿處理之前進行一水解處理，並在水 解步驟之前或之後進一步利用木聚醣酶破壞非木材纖維材料中之 木聚醣構（蓋纖維材料中之纖維通常經木聚糖所包覆或與之交 錯存在）’以提高纖維離解效能，進而降低後續磨漿動力的消耗並 提高纖維得率與紙張物性。 具體言之，本發明之製造非木材纖維漿料之方法包含：提供一 非木材纖維材料；對該非木材纖維材料進行__水解處理；於該水 解處理之前或之後，以—木聚料對該非木材纖維材料進行二酵 =理；以及於該水解處理與該酵素處理之後，對該非木材纖維 材料進仃—精製處理，以製得該非木材纖維襞料。 … 可用於本發明方法令之非木材纖維材料 不具經濟價值之部分，可選自訂群組：箱桿二=物中 亞麻、及其組合，本發明之方法中，非木材纖維材料棉 :處:處理或酵素處理之前，較佳先進行如散漿及平篩 ，以初步去除雜質並保留所需之袓纖維材料。前 作為非木材纖維材料為例，可先將稻桿裁切成約2公分相桿 201211263 刀之大小，較佳約3公分至約6公分之大小後，放入一散聚機中， 隨後加人Ή ’進行散锻處理歷時約10分鐘至約2G分鐘；隨後， 將所得之展料進行—平篩處理，—般而言，平筛處理可透過一包 3又層篩具之平篩機來進行’其中上層篩具通常具有較大筛孔 (如可知用孔/同大小約〇 4毫米至約〇 6毫米之筛板)，下層篩具 則具有較小篩孔（如可採用約25G目至約35〇目之筛網）。將所得 之混料通過該雙㈣具，即可於上層篩板與下層筛_獲得所欲 之稻桿粗纖維材料，至此完成非木材纖維材料之前置處理。當然， 本發明之方法亦可採用任何f知方法，並視所取用之非木材纖維 材料的種類，進行初步錯雜質之前置處理，並不限於上述方式。 經初步去除雜質後之非木材纖維材料隨後進行水解處理及酵 素處理。經發現，不論於水解處理之前或之後進行酵素處理，均 能提供所欲之水解及酵素作用，此可由後附實施例窺知。因此， 根據本發明之方法，水解處理及酵素處理之先後順序並無特殊限 制’可視實際製程需要作調整。 於不受理論限制下，咸信水解處理可降低非木材纖維材料中雜 質（如半纖維）的含量，從而提高纖維離解程度。常用的水解處 理方法包含例如酸水解法、水水解法、蒸氣水解法等。酸水解法 係以無機酸或有機酸作為水解媒介來處理材料，以採用硫酸作為 水解劑為例，一般係將纖維材料置於濃度為約0.3重量％至約〇.5 重量％、溫度約100°C至約125°C之硫酸水溶液中來進行水解。水 水解法及蒸氣水解法則係單以水對纖維材料進行預水解的方法， 通常係將纖維材料置於溫度為約14〇。〇：至約18〇。(：之蒸氣環境 201211263 令，歷時約】〇分鐘劲⑽ 施態射，係、於1氣處理❹來知水解。於本發明之部分實 溫餘和蒸氣以進行水解處理 導入約！65〇C至约！m：之高 除上述水解法以外，本々員域中 間為约55分鐘至約65分鐘》 教導，亦可視需要採用其他有通*知識者，基於本說明書之 α水解法來進行水解處理。 於本發明之方法中，酵素處理 適作用溫度而定，且酵素添力 溫度端視所用之酵素本身的最 嫩，不應限定於_特=及處理時間係根據實際製程條件 適作用溫度，酵素處理步驟係 又而吕’考量木聚糖酶之最 處理時間約5分鐘5C至約95 C之溫度下進行， 勺.12〇 分綠，故 * α 至約<500活性單位/克 酵素濃度係約Ο·1活性單位/克 說明）。於本發明之部分酶之活性單位量測方法將於下文中 度下，以濃度分別約為2G、樣中’係於約45°c至約55°C之溫 之木聚醣酶水溶液酵 〇、8〇、1〇〇及200活性單位/克 分鐘。另外，在使用★理非木材纖維’歷時約55分鐘至約65 視需要以—其他酶，/糖酶之酵素處理之前 '期間或之後，可 酶等，進行額外之酵^ =維素酶、半纖維素酶、細胞壁酶、醋 木聚膽酶（Xyla 素，其應用範圍非係醋水解酵素中分解半纖維素的主要酵 ^ ；"廣泛，例如食品、動物飼料、紡織或造紙等。 於本發明之方法φ Β , ’即使用木聚糖酶破壞非木材纖維材料φ 聚糖結構’以提高纖維離解效能。可用於本發明方法之木聚糖酿 種類並無特殊限<木聚糖轉 菌屬、曲下群組：木霉屬'馬杜拉放線 屬、短柄霉、芽孢桿菌屬、纖維單孢菌屬、毛殼菌屬、 201211263 饮氏菌Μ、後狀芽抱得菌屬、絲、狀桿菌屬、腐質菌魇、Neocallimastix 屬、諾卡氏菌屬、瘤胃球菌屬、裂褶菌屬、鏈霉菌屬、熱單孢屬、 嗜熱真菌屬、及其組合。其中，相較於一般木聚醣酶，厭氣性真 菌由於通常生長於生存競爭壓力高之瘤胃（如反芻動物與單胃草 食性動物的消化道）中，故演化成可產生具高活性者（可參見 Anthony et al. 1994. Anaerobic fungi in herbivorous animals. Mycol. Λα. 98: 129-152，該文獻内容倂於此處以供參考），其同時具有高 活性、高專一性及耐熱性等優點。因此，本發明之方法中，較佳 係使用來自厭氣性真菌（anaerobic fungi，又稱為瘤胃真菌（rumen fungi))之木聚醣酶來進行酵素處理，如屬之木聚 St Ιφ ’且於本發明之部分實施態樣中係使用；^ 之木聚醣酶。此外，根據本發明之方法，木聚醣酶之來源 亦無特殊限制，可自天然木聚醣酶單離取得，或經由人工合成方 法（例如基因工程或胜肽合成儀）獲得，或可為進一步經修飾（相 關内容可參見台灣專利申請案公開第200720435號，該文獻内容 倂於此處以供參考）而提升活性、專一性及/或穩定性者。 根據本發明之方法，係於水解處理及酵素處理之後，對非木材 纖維材料進行一精製處理，以完成非木材纖維漿料之製備。所述 精製處理實質上係將經去除雜質且木聚糖結構經木聚糖酶破壞之 非木材纖維材料進行一機械磨漿處理，以將非木材纖維材料解纖 並轉化成粗紙漿。除下文實施例所揭示之方式之外，該機械磨漿 處理亦可透過任何習知之機械磨漿裝置或方法來達成，如木片盤 磨機械製漿（RMP)、熱機械製漿（TMP)等（此可參考//⑽办⑽灸 /or Pw/p ά 巧以如/叹如，Smook，（1992) ’該文獻内容倂於此 201211263 處以供參考）； 虑拽〜A 視所需之漿料條件（如游離度大小），該精製 = = :序，且每:一間較佳先- 實施態樣中，係進行二$—次絲㈣，於本發明之部分 序且每次磨浆程库办―，㈤次磨衆程序’較佳係進行三次磨聚程 八德 $ 成後，縣以—約325目之篩網慮除漿料水 刀後，始進行下一次磨毁程序。 保，所^之非木材纖料料可視需要脫除水分以便於 • 、&運送至下㈣'紙錢行紙張抄造。 纖=二!:::製，之安排，能將原本不具經濟價值之非木 作為機械製难f n査、棉桿等’轉為有價之再生資源， 二 ’之原料’能減少天然資源之消耗並降低造紙成本， 械製梁之方式亦能避免使用大量化學_而污染生態環境。 '下列/、體貫施態樣以進一步例示說明本發明 ，其中，所採 用之量測裝置及方法分別如下： 籲⑷加拿大標準游離度（CSF)之量測方法： 測量方式：使用IS0 5267_2標準測試方法測量，其中係秤取3 A克重（絕對乾重）之待測樣品，加水配製至1 〇〇〇毫升後， 以加拿大標準游離度測量器量測漿料之CSF值。 (B)酵素活性之量測方法： 測量方式：取90微升之3重量％的木聚醣（斯卑爾脫小麥木 聚聽，溶解於pH值為8.0之25毫莫耳濃度三經曱基胺基甲炫 (tris(hydroxymethyl)aminomethane )溶液）作為酵素反應基 201211263 質’將該酵素反應基質與ι〇微升特定濃度之木聚醣酶配方均 勻混合’並於60°C下，使混合物反應5分鐘。隨後，加入125 微升之二硝基水楊酸試劑終止反應，並升溫至98。(：且維持5 分鐘’進行呈色反應。最後，以540奈米之波長測定吸光值並 計算還原糖之量，即測得配方中之木聚醣酶的活性。其中，1 活性單位（U)係定義為該酵素量每分鐘每毫升可水解出1微 莫耳之還原糖（詳細方法可參見Georis等人之Sequence， overproduction and purification of the family 11 endo-p-l,4-xylanase encoded by the xyll gene of Streptomyces sp. S38, Gene Vol. 237, pages 123-133 )。 (C) 細漿得率之量測方法： 測量方式：秤取100公克磨漿完成後所得之漿料，以一平篩機 篩分該漿料以獲得細漿。其中，平篩機係包含一上層篩板（篩 孔約0.1毫米）及一下層篩網（筛孔為約3 2 5目），能通過上 層篩板且未通過下層篩網之漿料即稱為「細漿」。細漿得率即 代表通過上層篩板且未通過下層篩網之漿料的重量〇/0。 (D) 紙張物性之量測方法： 測量方式：本發明說明書中所提及之紙張相關物性係透過以下 標準量測方法所量測： 基重： ISO 536:1995 ( Paper and board-Determination of grammage ) ° 斷裂長: ISO 1924-2:1994 (Paper and board-Determination of tensile properties-Part 2:Constant rate of 201211263 elongation method) ° 撕裂指數：（km) Tappi T414 om-98( Internal tearing resistance of paper (Elmendorf-type method)) ° 破裂指數：ISO 2758:2001 (Paper-Determination of bursting strength ) 實施例1:衆料製備方法 (a) 取適量稻桿’並裁切成平均約3公分至約5公分之長 度，放入散漿機後加入常溫清水，進行散漿處理約15分鐘後， 以一具有〆雙層篩具（上層為孔洞0.5毫米之篩板，下層為325 目之篩網）之平篩機過篩處理，以取得上層（即通過上層篩板但 未通過下層篩網）稻桿粗纖維材料； (b) 將所得之稻桿粗纖維材料置於一蒸氣處理槽中進行蒸氣 水解處理，其中飽和蒸氣溫度約170°C，處理時間約60分鐘。 將經蒸氟水解處理後之稻桿粗纖維材料於約l〇5DC之溫度下烘 乾2小時以去除水分， (c) 秤取1000公克之經蒸氣水解處理的稻桿粗纖維材料並配 置成8重之稻桿粗纖維漿料’隨後添加一選定量之木聚糖酶 酵素則扣·Χ加心/以之XynUB，），並於約5〇〇c之溫 度下反應約1小時後脫水備用；以及 ⑷將經酵素處理後之稻桿粗纖維材料以日本krk公司之磨 漿機進行三次機械磨_理’其中每次機械磨衆處理完成後，先 以- 325目之筛網瀝除裂料水分後，始進行下一次的磨漿程序， 最後將磨漿完成之漿料脫水備用。 201211263 實施例2:酵讀量之影響 依實施例備料 中所添加之料4輕彳料_ 们，其中步驟⑷ 80及〇活性單位謝繼分縣10、20、40、 以 第1圖所示抑）里㈣料1至4及比較紫料5之游離度並紀錄如 田第201211263 VI. Description of the Invention: [Technical Field] The present invention relates to a method for producing a non-wood fiber slurry; in particular, the present invention relates to a xylanase for a non-wood wood fiber material. Process 'to make a non-wood fiber slurry. [Prior Art] In the paper industry, wood fiber materials are mainly used to provide paper pulp, and lignocellulosic materials are generally classified into wood and non-wood according to their plant characteristics. Wood fiber materials such as pine and rosewood Perennial plants such as eucalyptus and non-wood fiber materials are common annual crops such as rice straw, straw rod, bagasse, cotton stalk, and flax. Among them, non-wood fiber materials generally use wood fiber materials as pulping materials because of their generally short fiber length and high impurity content. However, 'wood fiber materials are usually taken from valuable and slow-growing perennial plants, which are costly and difficult to plant; in contrast, non-wood fiber materials are mostly non-economical parts of agricultural plants (such as rice straw and wheat straw). Μ, 棉, cotton rod ^, not only easy to get, the purpose of hiding paper when growing (four) planting also destroys the natural ecology. In addition, the papermaking process mainly consists of making the wood fiber material into paper material and papermaking by paper The second step of making paper. At present, the preparation method of paper aggregate mainly includes chemical green, semi-chemical and mechanical pulping methods, among which, compared with chemical or semi-chemical pulping, mechanical pulping has The construction cost is low, the rate of slurry formation is high, and the pollution to the environment is low. Therefore, the mechanical pulping method mainly uses mechanical force to tear the cellulose fiber and further «, so in the refining stage The high energy consumption is the main disadvantage. 201211263 There is an improved mechanical pulping method combined with mild chemical treatment or enzyme treatment. In the 'U.S. Patent No. 2G050241785, the disclosure of the Japanese Patent Application No. 2G050241785, discloses a mechanical manufacturing method for a softwood, which teaches the addition of pectin decomposing enzyme to pre-treatment of the original crucible before grinding to reduce the loss of power. In Chinese Patent Application No. 101130936, the invention discloses that the energy consumption of the mechanical pear refining section is reduced until it is subjected to the grinding process of the fine grinding section, and the hydrolyzed enzyme is used to treat the coarsely ground Reduce the grinding force of the fine grinding section. ° ° The paper is mainly focused on the mechanical t-making method and the use of wood-dimensional materials as a t-material to provide paper pulp. The present invention provides a non-wood In addition to avoiding the use of a large number of chemical agents, the mechanical polymerization method of fiber (4) converts non-wood fiber materials that are not economically valuable into valuable renewable resources to reduce the consumption of natural resources and reduce papermaking. SUMMARY OF THE INVENTION The present invention is directed to a method of making a non-wood fiber (10) comprising: providing a non-wood fiber material; and performing a water on the non-wood fiber material (4) before or after the hydrolysis treatment, performing an enzyme treatment with a wood (4) enzyme_non-wood fiber material; and after the hydrolysis treatment and the enzyme treatment, the non-wood fiber material is subjected to a refining treatment to obtain the non- Wood fiber slurry. In order to make the above objects, technical features and advantages of the present invention more comprehensible, the following 201211263 is described in detail in some specific embodiments. [Embodiment] Hereinafter, a part according to the present invention will be specifically described. The present invention may be embodied in a variety of different forms without departing from the spirit and scope of the invention. The scope of the invention should not be construed as limited to the description. A method for producing a fiber slurry, which uses a non-wood fiber material (such as rice straw, straw, etc.) that is not economically valuable to replace the wood fiber material as a papermaking material, and is subjected to a hydrolysis treatment before the refining treatment, and Further utilizing xylanase to destroy wood aggregates in non-wood fiber materials before or after the hydrolysis step Structure (fibrous material of the cover fiber is typically coated with xylan wrong or the presence of the turn ') to increase the fiber dissociation efficiency, thereby reducing power consumption and the subsequent refining fibers to improve the yield and the physical properties of the paper. Specifically, the method for producing a non-wood fiber slurry of the present invention comprises: providing a non-wood fiber material; subjecting the non-wood fiber material to a hydrolysis treatment; before or after the hydrolysis treatment, using the wood material to the non-wood material The wood fiber material is subjected to a second fermentation process; and after the hydrolysis treatment and the enzyme treatment, the non-wood fiber material is subjected to a refining treatment to obtain the non-wood fiber material. The portion of the non-wood fiber material that can be used in the method of the present invention is not economically valuable, and can be selected from the group consisting of: box rod two = linen, and combinations thereof, in the method of the present invention, non-wood fiber material cotton: Prior to treatment or enzymatic treatment, it is preferred to perform, for example, slurry and flat sieving to initially remove impurities and retain the desired enamel fiber material. For example, as a non-wood fiber material, the rice straw can be first cut into a size of about 2 cm phase rod 201211263 knife, preferably about 3 cm to about 6 cm, and then placed in a scattering machine, followed by adding Ή 'The bulk forging process lasts from about 10 minutes to about 2G minutes; then, the resulting exhibit is subjected to a flat screen treatment. In general, the flat screen can be passed through a flat screen machine with a 3-layer sieve. To carry out 'the upper sieve usually has a large sieve hole (for example, a sieve with a hole size/same size of about 4 mm to about 6 mm), and the lower sieve has a smaller sieve hole (for example, about 25G can be used) The screen is about 35 mesh.) The resulting mixture is passed through the bis (four) tool to obtain the desired straw fiber material in the upper sieve and the lower sieve, and the non-wood fiber material is pretreated. Of course, the method of the present invention can also be carried out by any method known in the art, and the preliminary impurity pre-treatment is carried out depending on the type of the non-wood fiber material to be taken, and is not limited to the above. The non-wood fiber material after preliminary removal of impurities is subsequently subjected to hydrolysis treatment and enzyme treatment. It has been found that the desired hydrolysis and enzymatic action can be provided regardless of whether the enzyme treatment is carried out before or after the hydrolysis treatment, which can be seen from the following examples. Therefore, according to the method of the present invention, the order of hydrolysis treatment and enzyme treatment is not particularly limited to the actual process requirements. Without being bound by theory, the salt hydrolysis treatment can reduce the content of impurities (such as semi-fibers) in non-wood fiber materials, thereby increasing the degree of fiber dissociation. Commonly used hydrolysis treatment methods include, for example, an acid hydrolysis method, a water hydrolysis method, a vapor hydrolysis method, and the like. The acid hydrolysis method uses a mineral acid or an organic acid as a hydrolysis medium to treat the material, and sulfuric acid is used as a hydrolyzing agent. Generally, the fiber material is placed at a concentration of about 0.3% by weight to about 5% by weight, and the temperature is about 100. Hydrolysis is carried out in an aqueous solution of sulfuric acid from ° C to about 125 ° C. The water hydrolysis process and the steam hydrolysis process are methods of prehydrolyzing a fiber material by water alone, usually by placing the fiber material at a temperature of about 14 Torr. 〇: To about 18 baht. (: The steam environment 201211263 order, the duration is about 〇 劲 劲 (10) Shi 射 ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Up to about! m: the height is about 55 minutes to about 65 minutes in addition to the above hydrolysis method. The teaching may also be carried out by other skilled persons, and the hydrolysis may be carried out based on the α hydrolysis method of the present specification. In the method of the present invention, the enzyme treatment depends on the temperature of the application, and the enzyme addition temperature depends on the most tender enzyme itself, and should not be limited to the specific temperature and the treatment time according to the actual process conditions. The enzyme treatment step is carried out in the same way as Lu's xylanase treatment time of about 5 minutes 5C to about 95 C, spoon. 12 〇 green, so * α to about < 500 activity units / gram The enzyme concentration is about Ο·1 active unit/gram. The method for measuring the activity unit of some enzymes of the present invention will be carried out in the following moderately, at a concentration of about 2 G, respectively, in a sample of xylanase aqueous solution at a temperature of about 45 ° C to about 55 ° C. , 8 〇, 1 〇〇 and 200 active units / gram min. In addition, in the use of ★ non-wood fiber' for about 55 minutes to about 65 as needed - before or after the other enzymes, / carbohydrase enzyme treatment, enzymes, etc., for additional fermentation ^ = vitamins, Hemicellulase, cell wall enzyme, vinegar polychase (Xyla, its application range is not the main fermentation of hemicellulose in vinegar hydrolase; " extensive, such as food, animal feed, textile or paper. In the method of the present invention φ Β , 'that is, the xylanase is used to destroy the non-wood fiber material φ glycan structure' to improve the fiber dissociation efficiency. The xylan brewing type which can be used in the method of the invention has no special limitation < Glycogen, genus group: Trichoderma 'Medula genus, Brachypodium, Bacillus, Fibrospora, Chaetomium, 201211263 饮, 后 抱Genus, genus, genus, humic bacterium, Neocallimastix genus, Nocardia, rumen genus, genus Schizophyllum, Streptomyces, Thermomonospora, Thermophilic genus, and combinations thereof. Among them, anaerobic fungi compared to general xylanase It is usually grown in the rumen (such as the gastrointestinal tract of ruminants and monogastric herbivores), and it has evolved to produce highly active ones (see Anthony et al. 1994. Anaerobic fungi in herbivorous animals. </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> <RTIgt; A xylanase of anaerobic fungi (also known as rumen fungi) for enzymatic treatment, such as wood poly St Ι φ ' and used in some embodiments of the invention; Xylanase. Further, according to the method of the present invention, the source of the xylanase is not particularly limited, and may be obtained by natural xylanase isolation or by artificial synthesis methods (for example, genetic engineering or peptide synthesizer). Obtained, or may be further modified (for related content, see Taiwan Patent Application Publication No. 200720435, the disclosure of which is incorporated herein by reference) for According to the method of the present invention, after the hydrolysis treatment and the enzyme treatment, the non-wood fiber material is subjected to a refining treatment to complete the preparation of the non-wood fiber slurry. The refining treatment is substantially to remove impurities and The xylan structure is subjected to a mechanical refining treatment with a xylanase-destroyed non-wood fiber material to defibrate and convert the non-wood fiber material into a coarse pulp. In addition to the manner disclosed in the examples below, the mechanical mill Slurry treatment can also be achieved by any conventional mechanical refining device or method, such as wood chip grinding mechanical pulping (RMP), thermomechanical pulping (TMP), etc. (This can be referred to / (10) (10) moxibustion / or Pw / p ά 巧如如/叹如, Smook, (1992) 'The content of this document is for reference here at 201211263); Consider ~A depending on the desired slurry conditions (such as freeness), the refinement == : Preface, and each: a preferred first-implementation aspect, the system is carried out two $-secondary silk (four), in the partial sequence of the present invention and each refining process library -, (five) times grinding program 'better After three times of grinding, the eight-year-old, the county is - about 325 After addition of the slurry into consideration screen waterjet, the procedure starts once destroyed mill. The non-wood fiber material can be removed from the water as needed to facilitate the transportation of the paper to the next (four) paper money. Fibre = two!::: system, the arrangement, can be used as a mechanically difficult non-wood, as a mechanical rectification, cotton poles, etc. 'turned into valuable renewable resources, two 'materials' can reduce the consumption of natural resources And to reduce the cost of papermaking, the way of making beams can also avoid the use of a large number of chemicals - and pollute the ecological environment. The following is a further illustration of the invention to further illustrate the invention, wherein the measuring apparatus and method are as follows: (4) Canadian Standard Freeness (CSF) measurement method: Measurement method: using IS0 5267_2 standard The test method measures, wherein the sample to be tested is taken up to 3 A gram weight (absolute dry weight), and after adding water to 1 〇〇〇 ml, the CSF value of the slurry is measured by a Canadian standard freeness measuring device. (B) Measurement method of enzyme activity: Measurement method: Take 90 μl of 3% by weight of xylan (Spelt wheat wood polyphonic, dissolved in a pH of 8.0 at 25 mM concentration of three warts Tris (hydroxymethyl) aminomethane solution) as an enzyme reaction group 201211263 Qualitatively mixes the enzyme reaction substrate with ι 〇 microliters of a specific concentration of xylanase formula and at 60 ° C The mixture was reacted for 5 minutes. Subsequently, the reaction was terminated by the addition of 125 μl of dinitrosalicylic acid reagent and the temperature was raised to 98. (: and maintain for 5 minutes' color reaction. Finally, the absorbance is measured at a wavelength of 540 nm and the amount of reducing sugar is calculated, that is, the activity of the xylanase in the formulation is measured. Among them, 1 active unit (U) Is defined as the amount of the enzyme that can hydrolyze 1 micromolar of reducing sugar per minute per minute (for details, see Georis et al. Sequence, overproduction and purification of the family 11 endo-pl, 4-xylanase encoded by the xyll Gene of Streptomyces sp. S38, Gene Vol. 237, pages 123-133 ). (C) Method for measuring the yield of fine pulp: Measuring method: weighing 100 grams of slurry obtained after refining, using a flat sieve machine The slurry is sieved to obtain a fine slurry, wherein the flat sieve machine comprises an upper sieve plate (mesh opening of about 0.1 mm) and a lower sieve mesh (mesh opening of about 325 mesh), which can pass through the upper sieve plate and The slurry that does not pass through the lower screen is called “fine slurry.” The fine pulp yield represents the weight 浆料/0 of the slurry passing through the upper sieve plate and not passing through the lower sieve. (D) Measurement method of paper physical properties : Measurement method: paper related in the description of the present invention The sex system is measured by the following standard measurement methods: Basis Weight: ISO 536:1995 ( Paper and board-Determination of grammage ) ° Break Length: ISO 1924-2:1994 (Paper and board-Determination of tensile properties-Part 2 :Constant rate of 201211263 elongation method) ° Tear index: (km) Tappi T414 om-98(Interface tearing resistance of paper (Elmendorf-type method)) ° Fracture index: ISO 2758:2001 (Paper-Determination of bursting strength ) Example 1: Preparation method of the bulk material (a) Take an appropriate amount of rice straw 'and cut into an average length of about 3 cm to about 5 cm, put it into a pulper, add normal temperature water, and carry out the slurry treatment for about 15 minutes. Screening with a flat screen machine with a double-layer sieve (the upper layer is a 0.5 mm sieve and the lower layer is a 325 mesh sieve) to obtain the upper layer (ie through the upper sieve but not through the lower sieve) The rice straw crude fiber material; (b) The obtained rice straw crude fiber material is placed in a steam treatment tank for steam hydrolysis treatment, wherein the saturated vapor temperature is about 170 ° C, and the treatment time is about 60 minutes. The crude straw fiber material after the hydrofluorination treatment is dried at a temperature of about 10 DC 5 DC for 2 hours to remove moisture, and (c) 1000 g of the steam hydrolyzed straw fiber material is weighed and configured 8 heavy rice straw crude fiber slurry 'subsequent addition of a selected amount of xylanase enzyme is deducted from the heart / XynUB,), and reacted at about 5 ° C for about 1 hour after dehydration And (4) the enzyme-treated rice straw crude fiber material was mechanically ground three times with a refiner from Krk Corporation of Japan. After each mechanical abrasion treatment, the sieve was drained with a -325 mesh screen. After the water is cracked, the next refining process is started, and finally the slurry obtained by refining is dehydrated for use. 201211263 Example 2: Effect of leaven amount According to the material added in the preparation of the example 4 light feed _, wherein step (4) 80 and 〇 active unit Xie Ji county 10, 20, 40, as shown in Fig. 1 ()) in the (four) material 1 to 4 and compare the freeness of the purple material 5 and record as Tiandi
理之襞料（Hi轉明之方㈣時使时解處理及酵t (比較聚料5)，其4)、之游離度’係明顯低於未使用酵素處理: 果越好；且’游離度越低代表所得射4中纖維的解纖$ 後，則無㈣’自酵素濃度增加至-定程@ 、此對應_’顯見酵素濃度應視製程條件作合宜之搭配 實施例3:酵素處理對漿料得率之影響性 以量測方法(〇及⑼分別 漿得率’結果係記錄於表！ 量測前述漿料1至 中。 3及比較漿料5之細 表1According to the rationale (Hi turns to the side of the square (4) when the solution and the fermentation t (comparative aggregate 5), 4), the freeness ' is significantly lower than the unused enzyme treatment: the better the fruit; and 'freeness The lower the value represents the defibration of the fiber in the 4 shots, then there is no (four) 'from the enzyme concentration increased to - set @, this corresponds to _' obvious enzyme concentration should be appropriate according to the process conditions. Example 3: enzyme treatment The influence of the slurry yield is measured by the measurement method (〇 and (9) the respective pulp yields are recorded in the table! The above slurry 1 is measured. 3 and the comparison of the slurry 5 is shown in Table 1.
12 201211263 實施例4 :水解處理與酵素處理順序之影響 [紙張A2至A4及比較紙張A5之製備] 秤取100公克之前述漿料2，並以一平篩機篩分，其中，平篩機 係包含一上層篩板（篩孔約0· 1毫米）及一下層篩網（篩孔為約 325目）。取得能通過上層篩板且未通過下層篩網之細漿部分並脫 水備用。 將所得之漿料倒入約9公升之水中散漿十分鐘，隨後進行紙張 抄造，即，將適量漿料倒入漿料槽並打開漿料槽之出水控制閥， 透過150目之篩網使得漿料自然交織成紙後，壓榨並烘乾以製得 紙張A2。其中，所抄造之紙張的基重係預設為約60公克/平方公 尺0 以相同方式，分別使用前述漿料3、漿料4及比較漿料5進行紙 張抄造，以分別製得紙張A3、紙張A4及比較紙張A5。12 201211263 Example 4: Effect of hydrolysis treatment and enzyme treatment sequence [Preparation of paper A2 to A4 and comparative paper A5] 100 grams of the aforementioned slurry 2 was weighed and sieved by a flat sieve machine, wherein the flat sieve system was It comprises an upper sieve plate (mesh opening of about 0.1 mm) and a lower sieve (mesh opening of about 325 mesh). A portion of the fine slurry that can pass through the upper sieve plate and not through the lower sieve is taken and dehydrated for use. The obtained slurry was poured into about 9 liters of water and dispersed for ten minutes, and then paper was taken, that is, an appropriate amount of the slurry was poured into the slurry tank and the outlet water control valve of the slurry tank was opened, and the sieve was passed through a 150 mesh screen. After the slurry is naturally interwoven into paper, it is pressed and dried to obtain paper A2. Wherein, the basis weight of the paper to be copied is preset to be about 60 g/m 2 . In the same manner, the paper 3 is prepared by using the slurry 3, the slurry 4 and the comparative slurry 5, respectively, to obtain paper A3, respectively. , paper A4 and comparison paper A5.
以量測方法（E)分別量測紙張A2至A4及比較紙張A5之物性， 結果係記錄於表2中。 表2 紙張 A2 紙張 A3 紙張 A4 比較紙張 A5 斷裂長 (千公尺） 1.91 2.1 2.33 1.89 撕裂指數 (毫牛頓•平方公尺/公克） 4.42 4.49 4.49 4.43 13 201211263 破裂指數 0.91 1.03 1.11 0.83 (千帕•平方公尺/公克） [紙張B2至B4及比較紙張B5之製備] 以與實施例1相同之方式製備漿料2’、漿料3'、漿料4’及比較 漿料5’，惟，係先進行步驟(c)之酵素處理後，始進行步驟(b)之蒸 氣水解處理，並於蒸氣水解處理完成後進行步驟（d)之磨漿處理。 其中，步驟(c)中所添加之酵素量係使得酵素濃度分別為20 (漿料 2·)、40 (漿料31)、80 (漿料4')及0 (比較漿料5’，即不添加酵 素）活性單位/公克，且步驟(d)中所用之磨漿次數均為三次。 以與[紙張A2至A4及比較紙張A5之製備]相同之方式，使用漿 料2'、漿料3’、漿料4'及比較漿料5'進行紙張抄造，以分別製得 紙張B2、紙張B3、紙張B4及比較紙張B5，並以量測方法（E)分 別量測其物性，結果係記錄於表3中。 表3 紙張 B2 紙張 B3 紙張 B4 比較紙張 B5 斷裂長 (千公尺） 2.22 2.92 3.17 2.34 撕裂指數 (毫牛頓•平方公尺/公克） 3.74 4.50 5.22 3.28 破裂指數 (千帕•平方公尺/公克） 0.76 0.91 0.87 0.81 201211263 由表2及表3之結果可知，不論於水解處理之前或之後，於磨 漿處理前對非木材纖維進行一酵素處理均能提高以此漿料所製得 之紙張的物理性質，且酵素處理所用之酵素濃度越高，影響亦越 明顯。 實施例5 :非木材纖維材料種類之影響 [紙張C5至C7之製備] 以與[紙張B2至B4及比較紙張B4之製備]中相同之方式及參數 φ 條件，製備漿料5”、漿料6”及漿料7"，惟，係使用麥桿作為非木 材纖維材料。其中步驟(c)中所添加之酵素量係使得酵素濃度分別 為0 (漿料5")、100 (漿料6")及200 (漿料7")活性單位/公克。 隨後以與[紙張A2至A4及比較紙張A5之製備]中相同之方式， 使用漿料5"、漿料6”及漿料7"進行紙張抄造，以分別製得紙張 C5、紙張C6及紙張C7，並以量測方法(E)分別量測其物性，結果 係記錄於表4中。 表4 比較紙張C5 紙張 C6 紙張 C7 斷裂長（千公尺） 2.64 2.96 3.33 撕裂指數 (毫牛頓•平方公尺/公克） 4.25 4.33 4.29 破裂指數 (千帕•平方公尺/公克） 1.14 1.36 1.52 15 201211263 [紙張D2至D4之製備] 以與實施例1相同之方式製備漿料2"、製備漿料3”及漿料4"， 惟，係使用麥桿作為非木材纖維材料。其中步驟(c)中所添加之酵 素量係使得酵素濃度分別為20 (漿料2")、40 (漿料3")及80 (漿 料4")活性單位/公克。 以與[紙張A2至A4及比較紙張A5之製備]中相同之方式，使用 漿料2"、漿料3"及漿料4”進行紙張抄造，以分別製得紙張D2、 D3及紙張D4，並以量測方法(E)分別量測其物性，結果係記錄於 表5中。 表5 紙張D2 紙張D3 紙張D4 斷裂長 (千公尺） 3.50 3.83 4.22 撕裂指數 (毫牛頓•平方公尺/公克） 3.51 3.6 3.86 破裂指數 (千帕•平方公尺/公克） 1.36 1.44 1.70 由表4及表5之結果可知，透過水解處理及酵素處理之搭配， 本發明之方法可採用其他非木材纖維材料（如麥桿）作為紙漿原 料，提供具良好物性的紙張，且以相同製程安排來說，酵素處理 所用之酵素濃度越高，影響越明顯。 201211263 综上所述，本發明之方法使用非木材纖維材料取代習知方法所 使用之木材纖維材料製備紙張漿料，不僅能減少木材纖維材料的 消耗量，更能將原本不具經濟價值之非木材纖維材料（如稻桿、 麥桿等）回收利用成為再生資源；以及對非木材纖維材料進行一 水解處理及一酵素處理，可提高纖維離解效能，進而降低後續磨 漿動力的消耗，提高纖維得率與紙張物性。 上述實施例僅為例示性說明本發明之原理及其功效，並闡述本 發明之技術特徵，而非用於限制本發明之保護範疇。任何熟悉本 • 技術者在不違背本發明之技術原理及精神下，可輕易完成之改變 或安排，均屬本發明所主張之範圍。因此，本發明之權利保護範 圍係如後附申請專利範圍所列。 【圖式簡單說明】 第1圖係顯示根據本發明之方法所製得之漿料之游離度與酵素 劑量的關係圖。 【主要元件符號說明】 • (無） 17The physical properties of the papers A2 to A4 and the comparative paper A5 were measured by the measurement method (E), and the results are shown in Table 2. Table 2 Paper A2 Paper A3 Paper A4 Comparison Paper A5 Breaking Length (thousand meters) 1.91 2.1 2.33 1.89 Tearing Index (millitons/m2/g) 4.42 4.49 4.49 4.43 13 201211263 Bursting Index 0.91 1.03 1.11 0.83 (kPa • square meters/gram) [Preparation of Papers B2 to B4 and Comparative Paper B5] A slurry 2', a slurry 3', a slurry 4', and a comparative slurry 5' were prepared in the same manner as in Example 1. After the enzyme treatment of the step (c) is performed, the steam hydrolysis treatment of the step (b) is performed, and after the steam hydrolysis treatment is completed, the refining treatment of the step (d) is performed. Wherein, the amount of the enzyme added in the step (c) is such that the enzyme concentrations are 20 (slurry 2·), 40 (slurry 31), 80 (slurry 4'), and 0 (comparative slurry 5', ie The enzyme unit/g is not added, and the number of refining used in the step (d) is three times. In the same manner as [Paper A2 to A4 and preparation of Comparative Paper A5], papermaking was carried out using the slurry 2', the slurry 3', the slurry 4', and the comparative slurry 5' to prepare the paper B2, respectively. Paper B3, paper B4, and comparison paper B5 were measured for physical properties by measurement method (E), and the results are shown in Table 3. Table 3 Paper B2 Paper B3 Paper B4 Comparison Paper B5 Breaking Length (thousand meters) 2.22 2.92 3.17 2.34 Tearing Index (millitons • square meters / gram) 3.74 4.50 5.22 3.28 Bursting Index (kPa = 200 square meters / gram 0.76 0.91 0.87 0.81 201211263 It can be seen from the results of Table 2 and Table 3 that whether the non-wood fiber is treated with an enzyme before the refining treatment can improve the paper prepared by the slurry before or after the hydrolysis treatment. The physical properties, and the higher the concentration of the enzyme used in the enzyme treatment, the more obvious the effect. Example 5: Effect of non-wood fiber material type [Preparation of papers C5 to C7] A slurry 5", a slurry was prepared in the same manner as in [Paper B2 to B4 and Comparative Paper B4 Preparation] and the parameter φ. 6" and slurry 7", however, the use of straw as a non-wood fiber material. The amount of enzyme added in step (c) is such that the enzyme concentrations are 0 (slurry 5"), 100 (slurry 6"), and 200 (slurry 7") activity units/gram. Then, in the same manner as in [Paper A2 to A4 and Preparation of Comparative Paper A5], paper 5', slurry 6", and slurry 7" were used for paper making to separately produce paper C5, paper C6, and paper. C7, and measured by the measurement method (E), the results are recorded in Table 4. Table 4 Comparison paper C5 paper C6 paper C7 break length (thousand meters) 2.64 2.96 3.33 tear index (male Newton • Square meter/g) 4.25 4.33 4.29 Burst index (kPa = square meters / gram) 1.14 1.36 1.52 15 201211263 [Preparation of paper D2 to D4] Preparation of slurry 2", preparation of pulp in the same manner as in Example 1. Material 3" and slurry 4", except that straw was used as the non-wood fiber material. The amount of enzyme added in step (c) is such that the enzyme concentrations are 20 (slurry 2"), 40 (slurry 3"), and 80 (slurry 4") activity units/gram. In the same manner as in [Paper A2 to A4 and Preparation of Comparative Paper A5], papermaking is performed using the slurry 2", the slurry 3" and the slurry 4" to prepare the papers D2, D3 and the paper D4, respectively. The physical properties were measured by the measurement method (E), and the results were recorded in Table 5. Table 5 Paper D2 Paper D3 Paper D4 Breaking length (thousand meters) 3.50 3.83 4.22 Tearing index (millitons • square meters) / gram) 3.51 3.6 3.86 rupture index (kPa / square meter / gram) 1.36 1.44 1.70 From the results of Table 4 and Table 5, through the combination of hydrolysis treatment and enzyme treatment, the method of the present invention can use other non-wood fiber Materials (such as straw) are used as raw materials for pulp to provide paper with good physical properties, and the higher the concentration of the enzyme used for enzyme treatment, the more obvious the effect is in the same process arrangement. 201211263 In summary, the method of the present invention uses non- The wood fiber material replaces the wood fiber material used in the conventional method to prepare the paper pulp, which not only reduces the consumption of the wood fiber material, but also the non-wood fiber material which is not economical ( For example, rice straw, wheat straw, etc. are recycled as renewable resources; and a hydrolysis treatment and an enzyme treatment of non-wood fiber materials can improve fiber dissociation efficiency, thereby reducing the consumption of subsequent refining power, and increasing fiber yield and paper. The above embodiments are merely illustrative of the principles and effects of the present invention, and are illustrative of the technical features of the present invention, and are not intended to limit the scope of the present invention. Anyone skilled in the art will not depart from the technology of the present invention. The changes and arrangements that can be easily accomplished by the principles and spirits are within the scope of the invention. Therefore, the scope of protection of the present invention is as set forth in the appended claims. [Fig. 1] A graph showing the relationship between the freeness of the slurry prepared according to the method of the present invention and the dose of the enzyme. [Explanation of main component symbols] • (None) 17