200934924 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種將木質纖維素漿脫木素及漂白及改良 選擇率之方法，藉由該方法以可見光及化學試剤處理分子 氧流以產生單重態氧’且接著在製漿程序過程+將單重態 氧流應用於紙漿。 〜 【先前技術】 Ο 氧脫木素作用為在習知漂白之前使用分子氧(亦即普通 氧）及驗來移除未漂白之化學漿t很大一部分木質^將 氧漂白視為與氧脫木素作用同義。該方法通常以分子氧在 高廢及高溫下進行。通常將分子氧應用於未漂白之牛皮紙 :，但亦可應用於其他化學衆。目前氧脫木素作用為商業 製私’且已有許多專利公開。此等專利描述分子氧之 用、布置、階段數、製程條件·亦即時間與溫度 進料之添加。 久驗/氧 通常不將氧漂白應用於機械漿 〇 (諸如低亞硫酸納(二硫亞磺酸納))或氧化劑(諸如：::劑 或其組合漂白機械漿。 氧化氫） 氧脫木素作用涉及相當複雜之化學。在高堡 下，氧反應形成自由基及陰離子，包括可物牛 由基、過氧化物陰離子及經基自由基氧化物自 式與木質素相互作用；然而其亦可使纖維素：：雜方 量損失及紙漿強度降低。 k成產 可將導致產量損失之纖維素降解分成兩類：隨機鏈裂解 135183.doc 200934924 (random chain cleavage)及"剝落"反應（"peeIing" reacti〇n)。歸因 於所存在之自由基之量，在氧脫木素作用中可能在沿聚合 鏈之任一點發生之隨機鏈裂解更為顯著❶"剝落"造成鏈末 端之單塘單元受攻擊並相繼移除。通常在牛皮紙衆中剝落 並不成為問題，因駿性鏈末#已被轉化成更穩定之氧化 . 形式。然而，當隨機鏈裂解過多時，剝落會成為問題，因 •為形成了具有還原性端基之兩個新鏈末端。 氧化學係獨特的。分子氧具有正常（最低能量）組態，其 0 為含有兩個未成對電子（亦即自由基）之三重態。然而，氧 分子之第一激發態為單重態。溶液中之單重態氧壽命在微 秒範圍内（在水中為3微秒），但在氣態下壽命很長（72分 鐘）。單重態氧可藉由迪爾·阿德反應（DielsAlder reacti〇n) 或烯反應選擇性地與碳碳雙鍵反應。在各種製漿製程後天 然木質素或經改質之木質素含有諸如烯基、酚基及非酚基 之官能基，其可能與單重態氧反應（Frimer，义叹，桌 /F卷/抝，第2124 頁，CRC press， ® 1985)。 關於紙漿及造紙工業中之單重態氧化學之先前技術通常 屬於以下類別之一： 1.藉由使用含氣化合物與含氧化合物組合原位產生單重 態氧之方法（美國專利第4〇〇812〇號；Szab〇等人、， C/zew. 7^如0/.，28, 183,1994)。在此等方法中， 可由含氣化合物（例如次氣酸鹽）及由單重態氧進行漂 白。 135183.doc 200934924 2. 以紫外光在氧存在下直接照射pH值在8與13之間的木 質纖維素漿混合物之方法（Turner，美國專利第 4,294,654號）。Turner之實例1提出其方法中不需光敏 劑，且事實上在其方法中在有或沒有光敏劑下所報導 之結果相同。先前已在美國專利第2，161，045號中報導 -使用300-420 nm之特定紫外光直接照射紙漿來促進漂 白。 3. 使用電暈（或其他）放電法產生"活性"氣體之方法， Ο 該"活性"氣體用於稠度為15-95°/。之化學及機械漿脫木 素及漂白（美國專利第3,806,404號’ Liebergott等人）。 Liebergott在實例1中揭示對軟木材使用活性氧’但κ 值之減少適中。如由Turner(美國專利第4,294,654號） 所指出，如由Liebergott所發現’活性氮極其有效’ 而在相同反應條件下活性氧之有效性卻低得多。 4. 利用經由光氧化產生之單重態氧、使用純木質素模型 化合物之方法，主要與纖維素之回色現象（color reversion)有關（G. Gellerstedt，K. Krinstad及E· L. Lindfors， "Singlet Oxygen Oxidation of Lignin Structures"於 Oxygen reaction with organic compounds and polymers ^， 編輯 B. Rlnby 及 J. F. Rabek，第 302-310 頁，John Wiley & Sons, 1978) °200934924 IX. Description of the Invention: [Technical Field] The present invention relates to a method for delignifying and bleaching and improving the selectivity of lignocellulosic pulp, by which a molecular oxygen stream is treated by visible light and chemical test to produce Singlet oxygen' and then the singlet oxygen stream is applied to the pulp during the pulping process. ~ [Prior Art] 氧 Oxygen delignification works by using molecular oxygen (also known as ordinary oxygen) and testing to remove unbleached chemical pulp before conventional bleaching. A large part of wood is treated as oxygen bleaching. The role of lignin is synonymous. This method is usually carried out with molecular oxygen at high waste and high temperatures. Molecular oxygen is often applied to unbleached kraft paper: but it can also be applied to other chemical groups. At present, oxygen delignification is commercially available and many patents have been published. These patents describe the use of molecular oxygen, the arrangement, the number of stages, the process conditions, i.e., the addition of time and temperature feeds. Long-term oxygen/oxygen is generally not applied to mechanical pulp (such as sodium sulfite (sodium disulfite) or oxidants (such as::: or a combination of bleaching mechanical pulp. Hydrogen peroxide) The role of priming involves quite complex chemistry. Under the high castle, oxygen reacts to form free radicals and anions, including the ketone-based, peroxide anion and trans-radical oxides, which interact with lignin; however, it can also make cellulose::hetero Loss of volume and reduction in pulp strength. K-production can divide cellulose degradation that leads to yield loss into two categories: random chain cleavage 135183.doc 200934924 (random chain cleavage) and "peeling" reaction ("peeIing" reacti〇n). Due to the amount of free radicals present, the random chain cleavage that may occur at any point along the polymer chain in oxygen delignification is more pronounced "exfoliation" causing the single-cell unit at the end of the chain to be attacked and successively Remove. It is usually not a problem to peel off in kraft paper, because the end of chain # has been converted into a more stable oxidation. However, when the random chain is cleaved too much, spalling can be a problem because the formation of two new chain ends with reducing end groups. The Department of Oxidation is unique. Molecular oxygen has a normal (lowest energy) configuration, where 0 is the triplet state of two unpaired electrons (ie, free radicals). However, the first excited state of the oxygen molecule is a singlet state. The singlet oxygen lifetime in the solution is in the microsecond range (3 microseconds in water), but it is very long in the gaseous state (72 minutes). Singlet oxygen can be selectively reacted with a carbon-carbon double bond by a Diels Alder reacti or aene reaction. Natural lignin or modified lignin contains functional groups such as alkenyl, phenolic and non-phenolic groups after various pulping processes, which may react with singlet oxygen (Frimer, sigh, table/F roll/拗, p. 2124, CRC press, ® 1985). Prior art relating to singlet oxidation in the pulp and paper industry generally falls within one of the following categories: 1. A method for generating singlet oxygen in situ by combining a gas-containing compound with an oxygenate (U.S. Patent No. 4,812) Nickname; Szab〇 et al., C/zew. 7^, eg 0/., 28, 183, 1994). In such methods, bleaching can be carried out by a gas-containing compound (e.g., a hypoxanthate) and from a singlet oxygen. 135183.doc 200934924 2. A method of directly irradiating a mixture of woody cellulose having a pH between 8 and 13 in the presence of oxygen in the presence of oxygen (Turner, U.S. Patent No. 4,294,654). Example 1 of Turner teaches that no photosensitizer is required in the process, and in fact the results reported in the process with or without photosensitizer are the same. It has been previously reported in U.S. Patent No. 2,161,045 that the use of specific ultraviolet light of 300-420 nm directly illuminates the pulp to promote bleaching. 3. Use the corona (or other) discharge method to generate the "active" gas method, Ο the "activity" gas for a consistency of 15-95°/. Chemical and mechanical pulp delignification and bleaching (US Patent No. 3,806,404 'Liebergott et al.). Liebergott reveals in Example 1 that the use of reactive oxygen species for softwoods is reduced, but the reduction in kappa values is moderate. As indicated by Turner (U.S. Patent No. 4,294,654), the active nitrogen is found to be extremely effective as discovered by Liebergott, and the effectiveness of active oxygen is much lower under the same reaction conditions. 4. The use of pure lignin model compounds by means of photooxidation of singlet oxygen, mainly related to the color reversion of cellulose (G. Gellerstedt, K. Krinstad and E. L. Lindfors, " Singlet Oxygen Oxidation of Lignin Structures" in Oxygen reaction with organic compounds and polymers ^, edited by B. Rlnby and JF Rabek, pp. 302-310, John Wiley & Sons, 1978)
Liebergott藉由使用高稠度氣相漂白方法研究化學漿之 漂白。將高稠度定義為15-95%(亦即5-85%之水）。在其原 話中，"'活性’或|電子激發'單重態氧或高能氧三重態係...... 135183.doc 200934924 藉由使相應氣體......通過無電極放電或通過微波放電或通 過電容脈衝放電或藉由’電漿喷射'而產生"("'active' or 'electronically excited' singlet oxygen or high energy oxygen triplet is ... produced by passing the respective gas...through an electrodeless discharge, or through a microwave discharge, or through a condensed pulsed discharge or by a 'plasma jet.··’）。Liebergott 在實 例1-(1)中揭示對軟木材使用氧之電子激發態，其中'於55 kPa下使氧以速率0.009公升/分鐘通過電暈放電，於其中其 〇 被作用以 120伏特之初級電位（primary potential)'('oxygen，at a rate of 0.009 liter/min, at 55 kPa, was passed through a corona discharge, where it was acted upon by a primary potential of 120 volts.’）。然而，他們表明在其方法中形成之氣體混合物並 非單重態氧，而是身我。此外，如Turner所指出，在 Liebergott之表I中之資料表明[按照Liebergott之方法所產 生之]活性氧在木質纖維素漿脫木素及漂白中僅些微有 效。參考Liebergott專利之表I表明在漂白之後，紙漿之κ值 〇 w 為22.6，其表示僅減少1.4個單位，將其轉化為減少百分數 為僅僅5.8%。 最後，Szabo將紙漿懸浮於H202之水溶液中且接著將 NaCIO添加至該溶液中。H2〇2與NaCIO進行化學反應從而 產生約10%之單重態氧。此為單一步驟方法。此外，無法 確保殘餘H202或NaCIO不會進行一些漂白。因此，所見漂 白結果可能未必歸因於單重態氧。另外，他們的資料（表2) 並未顯示與單獨之NaCIO相比，H202/NaC10之活性顯著增 135183.doc 200934924 加。事實上’單獨之NaCIO顯示高於HzOs/NaCIO之脫木素 作用及選擇率。 【發明内容】 本文揭示一種在化學或機械漿中增強脫木素作用或漂白 之新穎方法，其包含以單獨步驟光化學產生單重態氧及隨 後將單重態氧輸送至紙漿以達成漂白或增白。較佳地，吾 人藉由以可見光及至少一種化學試劑處理分子氧流從而將 分子氧轉化成單重態氧且在製漿過程中將所得單重態氧流 應用於紙漿來增強氧脫木素製程中木質纖維素漿之漂白。 【實施方式】 本發明提供一種將木質纖維素漿脫木素或漂白之方法， 其包含以下步驟：a)提供紙漿之水性或非水性混合物；b) 提供分子氧流，在可見光及至少一種化學試劑存在下使分 子氧反應從而使一部分分子氧光化學轉化成單重態氧丨及 c)隨後使紙漿或紙漿混合物與單重態氧流接觸。 本發明亦提供使用單重態氧製造之紙漿或紙製品。 將木質纖維素原材料轉化成未漂白及隨後漂白之紙漿需 要極其錯綜複雜之一系列化學反應及物理加工，通常需要 兩個或兩個以上包括不同反應之階段。第一階段稱作製 漿且第一階段稱作漂白》然而兩者均包括脫木素作用。 使用木材或其他植物材料之化學或機械處理來產生紙 漿，接著將其製成紙製品。在化學製漿中，"蒸煮 (digestion)製程（例如牛皮紙或亞硫酸鹽）其令各種化學品 之/合液使木質素、非纖維材料及其他雜質溶解或改質以釋 135183.doc 200934924 出紙衆。在機械製漿中，機械研磨運動將含纖維素之纖維 自木材基質中分離。機械製漿之一種方法使 製 機：其通常具有兩個金屬板，其中至少一個板以高速旋 轉’將木屑饋入精製區且在精製機中心(眼孔)與其他精製 機區域之間於高廢及高溫下碎裂。另一方法(稱為"磨木漿 (groundwood))為將木材壓在快速旋轉之磨石面上，其中 磨钱作用將纖維自木材基質撕裂。此等方法之許多變型為 ❹Liebergott studied chemical pulp bleaching by using a high consistency gas phase bleaching process. The high consistency is defined as 15-95% (ie 5-85% water). In its original words, "activity" or |electron excitation's singlet oxygen or high energy oxygen triplet system... 135183.doc 200934924 by passing the corresponding gas... through an electrodeless discharge Produced by microwave discharge or by pulse discharge of a capacitor or by 'plasma injection' ("'active' or 'electronically excited' singlet oxygen or high energy oxygen triplet is ... produced by passing the respective gas. ..through an electrodeless discharge, or through a microwave discharge, or through a condensed pulsed discharge or by a 'plasma jet.··'). Liebergott discloses in Example 1-(1) the use of oxygen in the excited state of softwood, where 'at 55 kPa, oxygen is passed through a corona discharge at a rate of 0.009 liters per minute, in which the enthalpy is applied to a primary of 120 volts. 'primary potential' ('oxygen, at a rate of 0.009 liter/min, at 55 kPa, was passed through a corona discharge, where it was acted upon by a primary potential of 120 volts.'). However, they show that the gas mixture formed in its method is not singlet oxygen, but is me. Furthermore, as pointed out by Turner, the data in Table I of Liebergott indicates that [as produced by the method of Liebergott] the active oxygen is only slightly effective in the delignification and bleaching of lignocellulosic pulp. Table I of the Liebergott patent indicates that after bleaching, the kappa κ value of the pulp is 22.6, which means that only 1.4 units are reduced, which is converted to a reduction percentage of only 5.8%. Finally, Szabo suspends the pulp in an aqueous solution of H202 and then adds NaCIO to the solution. H2〇2 chemically reacts with NaCIO to produce about 10% of singlet oxygen. This is a single step method. In addition, there is no guarantee that some H202 or NaCIO will not undergo some bleaching. Therefore, the results of the bleaching may not be attributed to singlet oxygen. In addition, their data (Table 2) did not show a significant increase in the activity of H202/NaC10 compared to NaCIO alone 135183.doc 200934924 plus. In fact, 'NaCIO alone shows a delignification effect and selectivity higher than HzOs/NaCIO. SUMMARY OF THE INVENTION Disclosed herein is a novel method of enhancing delignification or bleaching in a chemical or mechanical slurry comprising photochemically producing singlet oxygen in a separate step and subsequently delivering singlet oxygen to the pulp for bleaching or whitening . Preferably, the invention enhances the oxygen delignification process by treating the molecular oxygen stream with visible light and at least one chemical agent to convert the molecular oxygen to singlet oxygen and applying the resulting singlet oxygen stream to the pulp during the pulping process. Bleaching of lignocellulosic pulp. [Embodiment] The present invention provides a method for delignifying or bleaching a lignocellulosic pulp comprising the steps of: a) providing an aqueous or non-aqueous mixture of pulp; b) providing a molecular oxygen stream, in visible light and at least one chemical The molecular oxygen is reacted in the presence of a reagent to photochemically convert a portion of the molecular oxygen to singlet oxygen and c) the pulp or pulp mixture is then contacted with a singlet oxygen stream. The invention also provides pulp or paper products made using singlet oxygen. The conversion of lignocellulosic raw materials into unbleached and subsequently bleached pulp requires an extremely intricate series of chemical reactions and physical processes, usually requiring two or more stages including different reactions. The first stage is called pulping and the first stage is called bleaching. However both contain delignification. Chemical or mechanical treatment of wood or other plant material is used to produce the pulp which is then made into a paper product. In chemical pulping, "digestion processes (such as kraft paper or sulfite) which cause various chemicals/liquids to dissolve or modify lignin, non-fibrous materials and other impurities to release 135183.doc 200934924 Out of the paper. In mechanical pulping, mechanical grinding motion separates cellulose-containing fibers from the wood matrix. One method of mechanical pulping makes the machine: it usually has two metal plates, at least one of which rotates at a high speed 'feeds wood chips into the refining zone and is high between the center of the refiner (eye hole) and other refining machine areas Disintegration and fragmentation at high temperatures. Another method (referred to as "groundwood) is to press the wood against a rapidly rotating grindstone surface where the grinding action tears the fibers from the wood matrix. Many variations of these methods are
已头例如，半化學、熱-機械及化學-熱-機械製漿。 氧脫木素作用"為在習知漂白之前使用分 除未漂白之化學聚中很大一部分木質素。氧漂白視= 脫木素作用同義。該方法通常以分子氧在高壓及高溫下進 行。通常將分子氧應用於未漂白之牛皮紙聚，但亦可應用 於其他化學漿。 作為單階段或多㈣製程之氧脫木素作用前技術中 已為人所熟知。通常不將氧漂白應用於機械漿。可在氧脫 木素製程中之多個階段之一使用本發明。 般而s ’以還原劑（低亞硫酸鈉（二硫亞磺酸鈉））或氧 化劑（諸如過氧化氫）或低亞硫酸鈉與過氧化氫之組合使機 械漿漂白或增白。 本發明方法中所使用之木質纖維素漿可由來自於天然來 源（諸如（但不限於）硬木材、軟木材、樹膠、稻草、蔗渣及/ 或竹材）之任何含木質纖維素材料、藉由各種化學半化 學、機械或組合製漿製程製備。化學及半化學製漿製程包 括（但不限於）牛皮紙、經改質牛皮紙、牛皮紙且添加硫磺 135183.doc 200934924 及/或蒽醌，及亞硫酸鹽。機械製漿製程包括（但不限於）磨 石磨木漿、加壓磨木衆、精製機機械聚、熱_精製機機械 漿、壓力精製之機械漿、熱·機械漿、壓力/壓力熱-機械 漿、化學-精製機·機械漿、化學_熱_機械漿、熱_化學·機械 漿、熱·機械-化學漿及長纖維化學_機械漿^ h/p W 編輯G A Sm〇〇k(Atianta, G A, TAPPI Press, 1989)描述化學及機械製讓。 將術語"氧"或"雙原子氧"視為與分子氧（亦即普通氧）同 β 義。氧具有開殼層三重基態（3〇2)之電子組態（該三重基態 具有佔據兩個簡併分子軌道之兩個未成對電子）且為空氣 中兩種主要組份之一。 術語"單重態氧"係指氧之第一電子激發態（1〇2)(亦稱作 單重態A-alg)，其中所有電子自旋均成對。單重態氧具有 比三重基態氧高之能量。單重態氧在溶液（微秒範圍）及氣 相（小於2小時）中具有有限壽命。 ◎本發明提供一種產生單重態氧之方法，其係由以下步驟 組成··提供分子氧源、可見光源、化學試劑，其中分子氧 源將分子氧流提供於含有該化學試劑之一個腔室或一系列 腔室中；使分子氧與化學試劑在來自於光源之可見光存在 下接觸。 在本發明之方法中使用之單重態氧係利用可見光及化學 試劑所產生。在腔室中在光敏性化學試劑存在下將分子氧 曝露於可見光導致產生單重態氧。接著使單重態氧流與紙 漿混合物接觸。單重態氧與紙漿反應引起脫木素作用。 135183.doc •12- 200934924 在本發明之方法中使用之可見光具有400 nm至700⑽之 間的波長。可見光源係選自(但不限於)由以下光源組成之 群：幽素燈、鶴或榮光燈、發光二極體（LED)、雷射器或 其組合。可使用具有滤光器以限制波長為可見光之任何光 源》 本發明之方法藉由將一部分分子氧轉化成單重態氧而提 絲脫木素製程增加之選擇率。將選擇枝義為紙聚之固 有黏度與紙漿之κ值之比率。固有黏度為纖維素分子量及 〇.纖維素降解之量度。κ值為紙衆之木質素含量或可漂白性 (bleachability)之為人熟知之指示值。其指示在木漿蒸煮過 程中為獲得具有指定白度所需漂白劑之量。選擇率愈高表 明製程愈佳，且漿產品愈理想。本發明提供基於分子量資 料之選擇率改良為至少約9%。 適用於本發明之化學試劑包括（但不限於）光敏劑染料、 顏料、芳族烴、輔酶或生物化學試劑、金屬鹽及過渡金屬 , 錯合物。光敏劑染料包括（但不限於）亞甲基藍（methyiene blue)、孟加拉玫瑰紅（r〇se bengai)、曙紅、結晶紫 (crystal violet)及吖啶橙（acridine 〇range)。適用於本發明 之顏料包括（但不限於）葉綠素（cWoropb】】）、血紫質 (hemat〇P〇rphyrines)及黃素（fIavin)。適用於本發明之芳族 烴包括（但不限於）紅螢烯（rubrene)及蒽（anthracene)。適用 於本發明之辅酶或生物化學試劑包括（但不限於）吡哆醛 (pyridoxal)類及補骨脂素（？5〇1>3|61^)類。適用於本發明之 金屬鹽包括（但不限於）硫化鎘及硫化辞。適用於本發明之 135183.doc -13- 200934924 過渡金屬錯合物包括（但不限於）釕及聯吡啶。適用於本發 明之化學試劑可吸收380-900 nm;較佳400-700 nm範圍内 之光（可見光）。可將化學試劑附著至氣體過濾器、玻璃 珠、金屬絲網或催化床。 光敏劑染料顯示螢光及磷光，反映兩種單獨之電子激發 -態，亦即單重態及三重態。首先藉由光之吸收產生單重 態，但其具有短壽命，藉由螢光衰變至基態及藉由電子系 統間穿越至三重態。此等光敏劑之三重態以較慢之速率衰 ❹ 冑至基態。最有效之光敏劑具有高量子產率之長壽命三重 態。 为子氧至單重態氧之轉化率視所使用之溶劑及化學試劑 而定且作為量子產率量測。例如，對於甲醇中之孟加拉玫 瑰紅而s H態氧形成之量子產率0(^02)=0.76。孟加拉 玫瑰紅之激發三重態形成之量子產率為〇76。因此，所有 三重態氧（分子氧）均轉化成單重態氧。較佳將至少ι〇%之 >子氧轉化成單重態氧。分子氧至單重態氧之轉化率可為 5/。至100/〇刀子氧至單重態氧之轉化率較佳為1〇%至 100/〇 ’且最佳為20%至刚。/。。供應至含有化學試劑及可 見光之腔至中之》子氧及/或空氣較佳含有小於6莫耳 之水（H2〇)，較佳小於3 5 ppm。 在牛皮紙氧脫木素作用系統中，單重態氧可產生且在添 加至第氧反應器之别添加至,,混合器"及/或添加於反應器 系統中之第-氧反應器之前的主要裝料位置，且與蒸汽管 線分離。 135183.doc -14- 200934924 在機械聚之情況下’可將單重態氧在製漿製程過程中於 機械漿精製機之眼孔處或經由用於磨石磨木漿之稀釋水應 用於機械漿°亦可在製漿製程中之其他點處（諸如在儲 槽、洗滌步驟、漂白步驟處）應用。典型機械製漿條件在 該項技術中為人所熟知。 以經烘箱乾燥之紙漿之重量計，紙漿混合物之固體之稠 度可為0.5%至28%。稠度可高達28%或高達2〇%或較佳高 達14°/❶。稠度為至少〇.5%，或至少3%或至少5%，或至少 8°/〇。較佳地，紙漿混合物之稠度為5%至28%，且最佳， 紙漿之稠度為9%至14%。適用於本發明之紙漿混合物包含 該紙漿、水及/或有機溶劑。該有機溶劑係選自由丙酮、 乙腈、乙醇、甲醇、異丙醇、乙酸或其組合所組成之群。 水與有機溶劑之比率為約1〇〇:0至約1:99，較佳1〇〇:〇至 80:20，且更佳 1〇〇:〇 至 9〇:1〇。 化學製漿由若干單元操作組成，其中之一為氧脫木素作 用。在化學漿之氧脫木素製程中，苛性鹼消耗範圍為〇至 24公斤/噸’相當於pH範圍為7至12，較佳至少85 ;反應 器溫度範圍為2(TC至160°C或25t：至160°C，較佳80°C至 150七，且更佳85。〇至125乞；且壓力範圍為大氣壓至1 MPa，較佳mo MPa，且更佳〇 5-〇 8 Mpa。較佳地壓 力為至少0.1 MPa。正是在化學漿之氧脫木素製程中之此 等條件下使單重態氧與紙漿接觸。通常在氧脫木素製程 中’分子氧之消耗量可為1至1〇〇公斤/嘲紙疲，較佳為5至 50公斤/嘴紙漿，且最佳介於5至25公斤/噸紙漿之間。 135183.doc 15 200934924 在本發明中，在一腔室中經由可見（非紫外（uv))光與化 學試劑之組合處理呈單㈣之氧，隨後將其制於紙浆。 此與TUrner之先前專利形成對比，在Turner之專利中使用 uv或電暈放電。與可見光相比，uv光產生反應性更大而 選擇性更小之物質，諸如可導致紙漿降解之自由基；產生 UV光比產生可見光花費更大；且與可見光相比，—光對 皮膚及人類眼睛之危害更大且更難以安置於紙漿廠或造紙 廠中。因此使用可見光之本發明比美國專利第4,294,654號 之方法有利。Turner提出在其方法中不需要光敏劑；參見 Turner之實例i，其中在其方法中使用或不使用光敏劑所報 導之結果相同。在本發明中，化學試劑/光敏劑為該方法 之必需要素。與Turner之方法相比，本發明從未將光能直 接應用於紙漿，從而消除如美國專利第2，161，〇45號中所述 之纖維素對光之吸收。 與Liebergott使用藉由放電方法產生之具有15_95%稠度 之活性氧所獲得之結果相比，現已令人驚奇地發現（如本 發明中所示）藉由使用可見光及化學試劑在溫和反應中特 異性地產生單重態氧，且將所得單重態氧曝露於紙漿從而達 成用於低稠度紙漿之脫木素作用及漂白之高效方法。本發 明中對於未漂白之牛皮紙軟木漿所述之資料（在表1中針對 亞甲基藍及表3中針對孟加拉玫塊紅）說明與以分子氧進行 之氧脫木素作用相比，在本發明之單重態氧存在下氧脫木 素作用之選擇率改良。對於亞甲基藍，κ值自使用分子氧 之22.7降低至使用單重態氧之2〇2，顯示使用單重態氧具 135183.doc -16- 200934924 Ο ❹ 有較大漂白度及可漂白性。κ值之降低為理想的。如表4 針對亞甲基藍所示，在以分子氧進行之氧脫木素過程中， 固有黏度自起始紙衆之778 g/mL急劇降低至…#，而 在以單重態氧進行之氧脫木素過程中，固有黏度降低少得 多至773 g/mL。分子氧比單重態氧導致更多纖維素降 解。以亞甲基藍作為化學試劑時（如實m中所示）本發明中 之方法產生23.5%之顯著選擇率改良，且以孟加拉玫瑰红 作為化學試劑時（如實例3中所示）本發明中之方法產生 W之顯著選擇率改良。本發明所獲得之選擇率改良對 於紙聚及/或由該紙漿製備之紙提供較高之聚合度，宜藉 由相同κ值下纖維素之較高黏度來證實。 '、 如本發明之實例U及表U所示之未漂白之機械漿，發現 與分子氧相比’使用單重態氧令人驚奇地顯示選擇率改良 為9.49%。以分子氧進行之氧脫木素作用顯示κ值自57 9辦 加至67.6’而以單重態氧進行之氧脫木素作用顯示κ㈣ 5:9 =至52.0。而如由尺寸排除層析法所量測的起始紙 裝之重量平均分子量為_，_道爾頓（她。η)，以分子氧 ::: =作用之重量平均分子量_，_道_頓 且以單重態氧進行之氧脫木素作用之重量 523,000道爾頓。 刀卞重旖 本發明υ使用可見光及化學試劑（光化學反應）來產生單 重態氧^及2)以兩個步驟進行該方法，即單獨產生單重態 氧及接著將該單重態氧輸送至紙漿。 “ 以下所示之實例係用於說明而非加以限制。 135183.doc -17· 200934924 實例 實例1-12及相應之表1·12顯示單重態氧之以下應用： 壓力之影響··周圍壓力（實例1)及40 psig(實例2-12)。 化學试劑之影響·亞甲基藍（實例1及2)、孟加拉玫塊紅 (實例3、0-12)、曙紅Y(實例4)及化學試劑之混合物（實例5) 歧管長度之影響-6.25 cm(實例6)及12.5 cm(實例2-5 'Τη) 氣體之影響-氧（實例1-12)及壓縮空氣（實例3) © 與單重態氧組合之添加劑之影響·瓜爾膠（實例7)、過氧 化物（實例8) 光源之影響-鹵素500W(實例1-8、10· 12)及螢光燈（實例9) 供給之影響-軟木材（實例1_9、12)、硬木材（實例1〇)及機 械漿（實例11)。 紙漿稠度之影響-低、中及高（實例12)。 在實例中使用之一般程序 在DMSO中之尺寸排除層析法（SEC): ❹ 於二甲亞硬中（DMSO)製備用於SEC之纖維素樣品的程 序。藉由將纖維素轉化成經甲基纖維素衍生物而使其可 - 溶。將約75 mg之樣品及1.6 g之聚甲醛添加至含有丨.0%For example, semi-chemical, thermo-mechanical and chemical-thermo-mechanical pulping. Oxygen delignification " is used to separate a large portion of lignin from unbleached chemical poly prior to conventional bleaching. Oxygen bleaching = the effect of delignification is synonymous. This method is usually carried out under high pressure and high temperature with molecular oxygen. Molecular oxygen is usually applied to unbleached kraft paper, but it can also be applied to other chemical pulps. It is well known in the art of oxygen delignification prior to single or multiple (four) processes. Oxygen bleaching is generally not applied to mechanical pulp. The invention can be used in one of several stages in the oxygen delignification process. The mechanical pulp is bleached or whitened by a reducing agent (low sodium sulfite (sodium disulfoxide)) or an oxidizing agent (such as hydrogen peroxide) or a combination of sodium hyposulfite and hydrogen peroxide. The lignocellulosic pulp used in the process of the invention may be derived from any lignocellulose-containing material from natural sources such as, but not limited to, hardwood, softwood, gum, straw, bagasse and/or bamboo, by various Chemical semi-chemical, mechanical or combined pulping process preparation. Chemical and semi-chemical pulping processes include, but are not limited to, kraft paper, modified kraft paper, kraft paper, and the addition of sulfur 135183.doc 200934924 and/or hydrazine, and sulfite. Mechanical pulping processes include (but are not limited to) grindstone wood pulp, pressurized milled wood, refiner mechanical poly, hot refiner mechanical pulp, pressure refined mechanical pulp, thermal and mechanical pulp, pressure / pressure heat - Mechanical pulp, chemical-refining machine, mechanical pulp, chemical_heat_mechanical pulp, heat_chemical·mechanical pulp, heat·mechanical-chemical pulp and long-fiber chemistry_mechanical pulp^h/p W Edit GA Sm〇〇k( Atianta, GA, TAPPI Press, 1989) describes chemical and mechanical manufacturing. The term "oxygen" or "diatomic oxygen" is considered to be synonymous with molecular oxygen (i.e., ordinary oxygen). Oxygen has an electronic configuration of the triplet ground state (3〇2) of the open shell (the triple ground state has two unpaired electrons occupying two degenerate molecular orbitals) and is one of the two major components in the air. The term "single-state oxygen" refers to the first electronically excited state of oxygen (1〇2) (also known as singlet A-alg), in which all electron spins are paired. Singlet oxygen has a higher energy than triple ground state oxygen. Singlet oxygen has a finite lifetime in solution (microsecond range) and gas phase (less than 2 hours). The present invention provides a method for producing singlet oxygen, which is composed of the following steps: providing a molecular oxygen source, a visible light source, and a chemical reagent, wherein the molecular oxygen source supplies a molecular oxygen stream to a chamber containing the chemical reagent or In a series of chambers; contacting molecular oxygen with a chemical agent in the presence of visible light from a source. The singlet oxygen used in the process of the present invention is produced using visible light and a chemical reagent. Exposure of molecular oxygen to visible light in the presence of a photosensitive chemical in the chamber results in the production of singlet oxygen. The singlet oxygen stream is then contacted with the pulp mixture. Singlet oxygen reacts with the pulp to cause delignification. 135183.doc • 12- 200934924 The visible light used in the method of the present invention has a wavelength between 400 nm and 700 (10). The source of visible light is selected from, but not limited to, a group consisting of a light source, a crane or glory lamp, a light emitting diode (LED), a laser, or a combination thereof. Any light source having a filter to limit the wavelength to visible light can be used. The method of the present invention increases the selectivity of the delignification process by converting a portion of the molecular oxygen to singlet oxygen. The ratio of the viscosity of the paper to the κ value of the pulp is selected. The intrinsic viscosity is a measure of the molecular weight of the cellulose and the degradation of cellulose. The κ value is a well-known indicator of the lignin content or bleachability of the paper. It indicates the amount of bleach required to achieve a specified whiteness during wood pulp cooking. The higher the selectivity, the better the process and the better the pulp product. The present invention provides improved selectivity based on molecular weight data to at least about 9%. Chemical agents suitable for use in the present invention include, but are not limited to, photosensitizer dyes, pigments, aromatic hydrocarbons, coenzymes or biochemical agents, metal salts and transition metals, complexes. Photosensitizer dyes include, but are not limited to, methyiene blue, rhododendron, magenta, crystal violet, and acridine 〇range. Pigments suitable for use in the present invention include, but are not limited to, chlorophyll (cWoropb), hematium P〇rphyrines, and flavin (fIavin). Aromatic hydrocarbons suitable for use in the present invention include, but are not limited to, rubrene and anthracene. Coenzymes or biochemical agents suitable for use in the present invention include, but are not limited to, pyridoxal and psoralen (?5〇1>3|61^). Metal salts suitable for use in the present invention include, but are not limited to, cadmium sulfide and sulfuric acid. Suitable for use in the present invention 135183.doc -13- 200934924 Transition metal complexes include, but are not limited to, hydrazine and bipyridine. The chemical reagents suitable for use in the present invention absorb light (visible light) in the range of 380-900 nm; preferably in the range of 400-700 nm. Chemical reagents can be attached to gas filters, glass beads, wire mesh or catalytic beds. The photosensitizer dye exhibits fluorescence and phosphorescence, reflecting two separate electronic excitation states, namely singlet and triplet states. First, a singlet state is produced by absorption of light, but it has a short lifetime, decaying to the ground state by fluorescence, and crossing to the triplet state by the electron system. The triplet of these photosensitizers decays to a ground state at a slower rate. The most effective photosensitizers have a long-life triplet with high quantum yield. The conversion rate for the oxygen to singlet oxygen depends on the solvent and chemical reagent used and is measured as a quantum yield. For example, for the Bengal rose in methanol and the s H oxygen formation, the quantum yield is 0 (^02) = 0.76. The quantum yield of the triplet formation of Bengal rose red is 〇76. Therefore, all triplet oxygen (molecular oxygen) is converted to singlet oxygen. Preferably, at least ι% of the > suboxygen is converted to singlet oxygen. The conversion of molecular oxygen to singlet oxygen can be 5/. The conversion to 100/〇 knife oxygen to singlet oxygen is preferably from 1% to 100/〇' and most preferably from 20% to just. /. . The oxygen and/or air supplied to the chamber containing the chemical reagent and the visible light preferably contains less than 6 moles of water (H2?), preferably less than 35 ppm. In the kraft oxygen delignification system, singlet oxygen can be produced and added to the oxygen reactor before, to the mixer &/or to the first oxygen reactor in the reactor system. The main loading location is separated from the steam line. 135183.doc -14- 200934924 In the case of mechanical polymerization, singlet oxygen can be applied to the mechanical pulp at the eye hole of the mechanical pulp refiner during the pulping process or via the dilution water for grinding the wood pulp. ° can also be applied at other points in the pulping process, such as at the storage tank, washing step, bleaching step. Typical mechanical pulping conditions are well known in the art. The solids of the pulp mixture may have a consistency of from 0.5% to 28% by weight of the oven dried pulp. The consistency can be as high as 28% or as high as 2% or preferably as high as 14°/❶. The consistency is at least 〇.5%, or at least 3% or at least 5%, or at least 8°/〇. Preferably, the consistency of the pulp mixture is from 5% to 28%, and most preferably, the consistency of the pulp is from 9% to 14%. A pulp mixture suitable for use in the present invention comprises the pulp, water and/or organic solvent. The organic solvent is selected from the group consisting of acetone, acetonitrile, ethanol, methanol, isopropanol, acetic acid or a combination thereof. The ratio of water to organic solvent is from about 1 〇〇:0 to about 1:99, preferably 1 〇〇: 〇 to 80:20, and more preferably 1 〇〇: 〇 to 9 〇: 1 〇. Chemical pulping consists of several unit operations, one of which is oxygen delignification. In the oxygen delignification process of chemical pulp, the caustic consumption range is from 〇 to 24 kg / ton' equivalent to a pH range of 7 to 12, preferably at least 85; the reactor temperature range is 2 (TC to 160 ° C or 25t: to 160 ° C, preferably 80 ° C to 150 7 , and more preferably 85 ° 〇 to 125 乞; and the pressure range is from atmospheric pressure to 1 MPa, preferably mo MPa, and more preferably 〇 5 - 〇 8 Mpa. Preferably, the pressure is at least 0.1 MPa. It is in the process of the oxygen delignification process of the chemical pulp that the singlet oxygen is contacted with the pulp. Usually, the molecular oxygen consumption in the oxygen delignification process can be 1 to 1 kg / ridiculous paper fatigue, preferably 5 to 50 kg / mouth pulp, and preferably between 5 and 25 kg / ton of pulp. 135183.doc 15 200934924 In the present invention, in a cavity The chamber is treated with a single (four) oxygen via a combination of visible (non-ultraviolet (uv)) light and chemical reagents, which are then made into pulp. This is in contrast to the previous patent of Türner, which uses uv or electricity in the Turner patent. Halo discharge. Compared to visible light, uv light produces more reactive and less selective substances, such as free radicals that can cause pulp degradation. Producing UV light is more expensive than producing visible light; and compared to visible light, light is more harmful to the skin and human eyes and more difficult to place in a pulp mill or paper mill. Thus the invention using visible light is comparable to U.S. Patent No. 4,294,654. The method is advantageous. Turner proposes that no photosensitizer is required in its method; see Turner's example i, in which the results reported in the method are the same with or without the use of a photosensitizer. In the present invention, the chemical/photosensitizer is An essential element of the method. The present invention has never applied light energy directly to the pulp as compared to the method of Turner, thereby eliminating the absorption of light by cellulose as described in U.S. Patent No. 2,161, the disclosure of which is incorporated herein. Compared to the results obtained by Liebergott using active oxygen produced by a discharge method with a consistency of 15_95%, it has now surprisingly been found (as shown in the present invention) to be specific in mild reactions by using visible light and chemical reagents. Singlet oxygen is produced and the resulting singlet oxygen is exposed to the pulp to achieve an efficient process for delignification and bleaching of low consistency pulp. The information described in the invention for unbleached kraft softwood pulp (in Table 1 for methylene blue and Table 3 for Bengal rose) is illustrated in the present invention as compared to the oxygen delignification with molecular oxygen. The selectivity of oxygen delignification was improved in the presence of heavy oxygen. For methylene blue, the K value was reduced from 22.7 using molecular oxygen to 2〇2 using singlet oxygen, indicating the use of singlet oxygen 135183.doc -16- 200934924 Ο ❹ Larger bleaching and bleachability. The reduction in κ is ideal. As shown in Table 4 for methylene blue, in the oxygen delignification process with molecular oxygen, the intrinsic viscosity is 778 g from the starting paper. /mL sharply decreased to...#, while in the oxygen delignification process with singlet oxygen, the intrinsic viscosity decreased much to 773 g/mL. Molecular oxygen causes more cellulose degradation than singlet oxygen. When methylene blue is used as a chemical reagent (as shown in the real m), the method of the present invention produces a significant selectivity improvement of 23.5%, and when the rose bengal red is used as a chemical reagent (as shown in Example 3), the method of the present invention is produced. The significant selection rate of W is improved. The improved selectivity obtained by the present invention provides a higher degree of polymerization for paper polymerization and/or paper prepared from the pulp, and is preferably confirmed by the higher viscosity of cellulose at the same k value. 'Unbleached mechanical pulp as shown in Example U and Table U of the present invention, it was found that the use of singlet oxygen surprisingly showed a selectivity improvement of 9.49% compared to molecular oxygen. The oxygen delignification by molecular oxygen showed that the kappa value was increased from 57 9 to 67.6' and the oxygen delignification by singlet oxygen showed κ (4) 5:9 = to 52.0. And the weight average molecular weight of the starting paper as measured by size exclusion chromatography is _, _ Dalton (her. η), the weight average molecular weight of molecular oxygen::: = _, _ _ The weight of the oxygen delignification by singlet oxygen is 523,000 Daltons. The present invention uses visible light and chemical reagents (photochemical reactions) to generate singlet oxygen and 2) to carry out the process in two steps, i.e., to generate singlet oxygen separately and then to transport the singlet oxygen to the pulp. “The examples shown below are for illustration and not limitation. 135183.doc -17· 200934924 Example Examples 1-12 and Tables 1·12 show the following applications for singlet oxygen: Pressure effects · Ambient pressure ( Examples 1) and 40 psig (Examples 2-12). Effects of Chemical Reagents · Methylene Blue (Examples 1 and 2), Bengal Rose (Examples 3, 0-12), Eosin Y (Example 4), and Chemical Reagents Mixture (Example 5) Effect of Manifold Length - 6.25 cm (Example 6) and 12.5 cm (Example 2-5 'Τη) Effect of Gas - Oxygen (Example 1-12) and Compressed Air (Example 3) © and Single Effect of additive for heavy oxygen combination · Guar (Example 7), peroxide (Example 8) Effect of light source - Halogen 500W (Examples 1-8, 10·12) and Fluorescent lamps (Example 9) Effect of supply - softwood (Examples 1-9, 12), hardwood (Example 1) and mechanical pulp (Example 11). Effect of pulp consistency - low, medium and high (Example 12). General procedure used in the examples in DMSO Size Exclusion Chromatography (SEC): Procedure for preparing cellulose samples for SEC in dimethyl hard (DMSO) by converting cellulose into It is soluble by methylcellulose derivative. About 75 mg of sample and 1.6 g of polyoxymethylene are added to contain 丨.0%.
LiCl及500 ppm BHT之56 g DMSOt。將此混合物在攪拌 下於110°C加熱40分鐘。將此溶液稱作蒸煮溶液（c〇〇k solution)。在樣品製備步驟中，聚甲醛分解成甲醛，其隨 後與纖維素反應形成可溶於DMSO中之衍生物。 所使用之層析條件為： 135183.doc -18 - 200934924 ❹ 層析儀： Waters Alliance 2000 GPCV 第一偵測器： Waters Differential Refractometer > 45 °C 第二偵測器： Waters Single Capillary Viscometer » 45 °C 管柱： 1 PL-Gel Mixed A 管柱溫度： 45〇C ' 移動相： 含0.5% LiCl及3.0 %福馬林之DMSO 流動速率： 0.2 ml/min 運行時間： 100 min 樣品濃度： 0.06重量％ 注射體積： 325 μΐ 内標： THF 214校正標準 : 普魯蘭(Pulullan) 藉由將9.6 g移動相添加至0.4 g蒸煮溶液中來製備分析物 溶液。將分析物溶液經0.45 μιη耐綸過濾器過濾❶使用普 魯蘭校正及Waters Empower軟體處理折射率層析圖。在選 擇率之計算中提出重量平均分子量（Mw)。 藉由標準方法測定壓縮纖維素片樣品之TAPPI亮度指數 及 CIE L*a*b *色彩空間值。（美國製漿造紙工業技術協會 (ΤΑΡΡΙ)試驗方法Τ452-"紙漿、紙及紙板之亮度（在457 nm 之定向反射率（（Brightness of pulp，paper & paperboard (directional reflectance at 457 nm))")。對於各樣品，使用 X-Rite 532光譜密度計在樣品片表面獲取5個讀數。L*a*b* 量測之觀測角度為2。。 κ值：根據TAPPI標準方法T236 cm_85測定紙漿之κ值。 135183.doc 19 200934924 固有黏度.根據ISO 5351·"紙漿-銅乙二胺（CED)溶液中 極限黏度值之測定（Pulps-Determining of limiting viscosity mimber in cupriethylenediamine (CED) s〇luti〇n)”來測定紙 漿之固有黏度。 選擇率.將選擇率定義為固有黏度與1<;值之比率。使用 選擇率來評估紙漿漂白或脫木素作用之效益，因為黏度與 . 纖維素分子量相關且κ值提供漂白度及可漂白性之量度。 在表2-12中，所列之選擇率係由固有黏度與κ值之比率計 〇 算且亦由SEC重量平均分子量與κ值之比率計算。 選擇率=固有黏度/κ值 或=重量平均分子量/1€值 選擇率改良=(單重態氧選擇率資料_對照分子氧選擇率 資料）/對照分子氧選擇率資料*1 〇〇% 可根據來自固有黏度之資料或來自分子量之資料計算選 擇率改良。 實例1 执備包括二頸圓底燒瓶，其裝備有機械攪拌器帶有氣 體起泡器之冷凝器、帶有在進入圓底燒瓶前填充有亞甲基 藍之U型管（或縮端管）的氣體入口，·及5〇〇 w攜帶型鹵素工 作光源（Stanley Tools, Manufacturer No. XG_1〇〇9)，如圖！ 中所示。向燒瓶中裝入110.82 g去離子水、3 〇 g氳氧化鈉 (NaOH)、0.18 g硫酸鎂（MgS〇4)及6 〇 g起始κ值為54 4之軟 木漿。在氫氧化鈉及硫酸鎂完全溶解後添加軟木漿。將反 應燒瓶加熱至回流（100。〇歷時4小時。分子氧自氧儲槽流 135183.doc -20- 200934924 出且以單獨流在一腔室中經由可見光與化學試劑之組合處 理，接著將處理後之氧流應用於紙漿混合物。分子氧之流 速介於110至140 mL/min之間且更通常為125 mL/min，如 由 Agilent 流量計 ADM 2000(Agilent Technologies, Inc., Wilmington，DE)所量測。對於分子氧實驗’以銘箔覆蓋亞 甲基藍。在單重態氧實驗過程中應用來自鹵素燈（500 W) 之光。初始實驗係在大氣壓下進行。 乾燥後以原樣使用未漂白、預水解之牛皮紙軟木材（來 〇 自 J. D. Irving, St· John, NB，Canada 之加拿大雲杉 (Canadian spruce))衆。其起始κ值為54.4，其起始固有黏度 為778 mL/g且其重量平均分子量為984,000道爾頓。使用亞 曱基藍作為光敏劑獲得樣品編號# 1A及IB。 表1 使用亞甲基藍或孟加拉玫瑰紅作為光敏劑，周圍壓力之分子氧與單重態氧相 比，對軟木材之效應。 樣品 編號 描述 固有黏度 h].mL/g K值 Mw (g/mol) SEC 根據[η] 之選擇率 根據Mw 之選擇率 根據[η] 之選择率改良 根據Mw之 1A 分子氧 668 22.7 978,000 29.4 43,100 ----------- 1B 單重 態氧 733 20.2 896,000 36.3 44,300 23.5% 2.78% 由本發明之實例1-表1顯而易見，在藉由使分子氧通過 具有化學試劑及可見光之腔室以產生單重態氧（隨後將其 應用於紙漿）而產生之單重態氧存在下，未最佳化之周圍 壓力系統可達成顯著的選擇率改良。K值自使用分子氧之 22.7降低至使用單重態氧之2〇·2，顯示使用單重態氧具有 較大漂白度及可漂白性。κ值之降低為理想的。表1證明使 135183.doc •21· 200934924 用分子氧時，固有黏度自778 g/mL急劇下降至668 g/mL， 而使用單重態氧時，固有黏度僅輕微下降至773 g/mL。分 子氧比單重態氧導致更多纖維素降解。該方法產生23.5% 之顯著選擇率改良（如由固有黏度與κ值之比率所量測）。 在實例2-12中，以下高壓實驗裝置包含壓縮氧儲槽，其 將加壓氧饋入填充有玻璃絨、Drierite®無水硫酸鈣（W. A. Hammond Drierite Company LYD, Xenia, OH)及蝴梦酸玻 璃珠（尺寸3 mm)(長達12.5 cm長度塗覆有光敏劑染料）之整 〇 體壓力歧管（Ace Glass, Vineland, NJ，目錄號64 48)。該歧 管將加壓單重態氧饋入具有通至背壓調節器（Swagelok， Huntingdon Valley, PA)之可程式化控制器（Parr Instrument Co.，Moline, IL，型號4561 及4843)之3 00-mL反應器。將安 全遮罩（RAD-GARD®，Instruments For Research and Industry, Inc.，Cheltenham, PA)置於 500 W Stanley® 攜帶型 鹵素工作光源與壓力歧管之間，如圖2中所示。分子氧自 氧儲槽流經化學試劑腔室且接著流入紙漿混合物。分子氧 〇 w 之流速介於110至140 mL/min之間且更通常為125 mL/min， 如由 Agilent 流量計 ADM 2000 (Agilent Technologies，Inc.，LiCl and 56 g DMSOt of 500 ppm BHT. This mixture was heated at 110 ° C for 40 minutes with stirring. This solution is referred to as a cooking solution (c〇〇k solution). In the sample preparation step, polyoxymethylene is decomposed into formaldehyde, which then reacts with the cellulose to form a derivative soluble in DMSO. The chromatographic conditions used are: 135183.doc -18 - 200934924 层析 Chromatograph: Waters Alliance 2000 GPCV First Detector: Waters Differential Refractometer > 45 °C Second Detector: Waters Single Capillary Viscometer » 45 °C Column: 1 PL-Gel Mixed A Column temperature: 45〇C 'Moving phase: DMSO with 0.5% LiCl and 3.0% Formalin Flow rate: 0.2 ml/min Operating time: 100 min Sample concentration: 0.06 weight % Injection volume: 325 μΐ Internal standard: THF 214 Calibration standard: Pullullan The analyte solution was prepared by adding 9.6 g of mobile phase to 0.4 g of cooking solution. The analyte solution was filtered through a 0.45 μηη nylon filter and the refractive index chromatogram was processed using a Pullan calibration and Waters Empower software. The weight average molecular weight (Mw) is proposed in the calculation of the selectivity. The TAPPI brightness index and CIE L*a*b* color space values of the compressed cellulose sheet samples were determined by standard methods. (American Pulp and Paper Industry Technical Association (ΤΑΡΡΙ) Test Method Τ 452-" Brightness of pulp, paper and paperboard (Brightness of pulp, paper & paperboard (directional reflectance at 457 nm)) ") For each sample, 5 readings were taken on the surface of the sample using an X-Rite 532 spectral densitometer. The observation angle of the L*a*b* measurement was 2. κ value: determined according to the TAPPI standard method T236 cm_85 κ value of pulp. 135183.doc 19 200934924 Intrinsic viscosity. According to ISO 5351·"Pulps-Determining of limiting viscosity mimber in cupriethylenediamine (CED) s〇 Luti〇n)” to determine the inherent viscosity of pulp. Selectivity. Define selectivity as the ratio of intrinsic viscosity to 1<; value. Use selectivity to evaluate the benefits of pulp bleaching or delignification because of viscosity and fiber. The molecular weight is related and the kappa value provides a measure of bleaching and bleachability. In Table 2-12, the listed selectivity is calculated from the ratio of intrinsic viscosity to kappa and also by SEC weight. The ratio of the average molecular weight to the κ value is calculated. Selectivity = intrinsic viscosity / κ value or = weight average molecular weight / 1 value selection improvement = (single-state oxygen selectivity data - control molecular oxygen selectivity data) / control molecular oxygen selection Rate data*1 〇〇% The selectivity can be improved based on data from intrinsic viscosity or from molecular weight. Example 1 A two-necked round bottom flask equipped with a mechanical stirrer with a gas bubbler With a gas inlet filled with a methylene blue U-shaped tube (or a narrowed tube) before entering the round bottom flask, and a 5 〇〇w portable halogen working light source (Stanley Tools, Manufacturer No. XG_1〇〇9), As shown in Figure !, the flask was charged with 110.82 g of deionized water, 3 〇g of sodium cerium oxide (NaOH), 0.18 g of magnesium sulfate (MgS〇4), and 6 〇g of softwood with a κ value of 54 4 . Pulp. Add softwood pulp after completely dissolving sodium hydroxide and magnesium sulfate. Heat the reaction flask to reflux (100 〇 for 4 hours. Molecular oxygen from oxygen storage tank 135183.doc -20- 200934924 and flow separately Visible light and chemistry in a chamber The combined treatment of the agent is followed by application of the treated oxygen stream to the pulp mixture. The molecular oxygen flow rate is between 110 and 140 mL/min and more typically 125 mL/min, as described by Agilent Flowmeter ADM 2000 (Agilent Technologies). , Inc., Wilmington, DE). For the molecular oxygen experiment, the methylene blue was covered with a foil. Light from a halogen lamp (500 W) was applied during the singlet oxygen experiment. The initial experiment was carried out under atmospheric pressure. After drying, unbleached, prehydrolyzed kraft softwood (from Canadian spruce of J. D. Irving, St. John, NB, Canada) was used as it was. It has an initial K value of 54.4, an initial intrinsic viscosity of 778 mL/g and a weight average molecular weight of 984,000 Daltons. Sample No. #1A and IB were obtained using fluorenyl blue as a photosensitizer. Table 1 uses methylene blue or bengal red as a photosensitizer, the effect of molecular oxygen at ambient pressure on soft wood compared to singlet oxygen. The sample number describes the intrinsic viscosity h].mL/g K value Mw (g/mol) SEC According to the selectivity of [η] according to the selectivity of Mw according to the selectivity of [η], according to Mw 1A molecular oxygen 668 22.7 978,000 29.4 43,100 ----------- 1B singlet oxygen 733 20.2 896,000 36.3 44,300 23.5% 2.78% It is apparent from the examples 1 to 1 of the present invention that the molecular oxygen is passed through a chamber having chemical reagents and visible light. The unoptimized ambient pressure system achieves significant selectivity improvements in the presence of singlet oxygen produced by the chamber to produce singlet oxygen, which is then applied to the pulp. The K value was reduced from 22.7 using molecular oxygen to 2 〇·2 using singlet oxygen, indicating greater bleaching and bleachability using singlet oxygen. The decrease in the κ value is ideal. Table 1 demonstrates that when molecular oxygen was used for 135183.doc •21· 200934924, the intrinsic viscosity dropped sharply from 778 g/mL to 668 g/mL, while in singlet oxygen, the intrinsic viscosity decreased only slightly to 773 g/mL. Molecular oxygen causes more cellulose degradation than singlet oxygen. This method yielded a significant selectivity improvement of 23.5% (as measured by the ratio of intrinsic viscosity to kappa value). In Examples 2-12, the following high pressure experimental apparatus included a compressed oxygen storage tank that fed pressurized oxygen into a glass wool filled with Drierite® anhydrous calcium sulfate (WA Hammond Drierite Company LYD, Xenia, OH) and a dream glass A whole body pressure manifold (Ace Glass, Vineland, NJ, Cat. No. 64 48) with beads (size 3 mm) (up to 12.5 cm length coated with photosensitizer dye). The manifold feeds pressurized singlet oxygen into a 3,000 controller with a programmable controller (Parr Instrument Co., Moline, IL, Models 4561 and 4843) that leads to a back pressure regulator (Swagelok, Huntingdon Valley, PA). -mL reactor. A safety mask (RAD-GARD®, Instruments For Research and Industry, Inc., Cheltenham, PA) was placed between the 500 W Stanley® portable halogen working light source and the pressure manifold as shown in Figure 2. Molecular oxygen flows from the oxygen storage tank through the chemical reagent chamber and then into the pulp mixture. The molecular oxygen 〇 w flow rate is between 110 and 140 mL/min and more typically 125 mL/min, as described by Agilent Flowmeter ADM 2000 (Agilent Technologies, Inc.,
Wilmington，DE)所量測。對於分子氧實驗，以鋁箔覆蓋化學 試劑。在單重態氧實驗過程中應用來自鹵素燈（500 W)之 光。 在實例9(單重態氧實驗之一）中，使用兩個Craftsman® 23 W螢光工作光源。 實例2 135183.doc -22- 200934924 在Parr反應器中裝入180 g去離子水、19.31 g軟木漿 (18.0 g烘箱乾燥之紙漿）及0.0072 g NaOH。在氫氧化鈉及 硫酸鎂完全溶解之後添加軟木漿。將反應燒瓶在275 kPa 下加熱至l〇〇°C歷時90分鐘。整體壓力反應器歧管（Ace Glass，Vineland，NJ)係以玻璃絨、Drierite®無水硫酸鈣及 塗覆有亞曱基藍光敏劑之玻璃珠填充。對於對照分子氧實_ 驗’以鋁箔覆蓋亞甲基藍光敏劑。在單重態氧實驗過程中 應用來自鹵素燈（500 W)之光。紙漿稠度為10〇/〇。 〇 在規定時間之後’在抽氣真空下以Whatman #41濾紙在 布氏漏斗（Buchner funnel)上分離經反應之紙漿。量測濾液 之pH值介於7.9與9.4之間。藉由添加約5〇〇 mL去離子水至 抽氣真空下之漏斗來沖洗紙漿。再次藉由添加約500 mL去 離子水至抽氣真空下之漏斗沖洗紙漿。接著將紙漿空氣乾 燥隔夜，隨後在40°C下真空烘箱中乾燥2小時。對於樣品 編號#2A及2B所添加之MgS〇4之量為〇.〇 g。對於樣品編號 #2C及2D所添加之MgS04之量為0.009 g。 表2 使用亞甲基藍作為光敏劑’面壓之分子氡與單重態氧相比，對軟木材之 效應。 樣品 編號 描述 固有黏度 [η] · mL/g κ值 Mw (g/mol) SEC 根據[η] 之選擇率 根據Mw 之選擇率 根據[η] 之選擇率 改良，％ 根據Mw 之選擇率 改良，％ TAPPI 亮度 2A 分子氧 24.0 905,000 24.3 37,700 - - 26.8 2B 單重 態氧 04/ 24.1 1,060,000 26.8 44,000 10.3 25.8 2C 分子氧 607 24.9 842,000 24.4 33,800 - • 26 8 2D 單重 態氧 646 23.3 952,000 27.7 40,800 13.5 20.6 26.9 表2證明藉由使用高壓實驗裝置，使用亞甲基藍作為化學 135183.doc -23- 200934924 試劑時無MgS〇4之選擇率改良為10.3%而有MgS〇4時為 13.5%。在其餘各表中’將MgS〇4添加於分子氧及單重態氧實 例中。如實例7中所述’ MgS〇4為選擇性試劑（selectivityagent)。 實例3 在本實例中，如實例2中所述裝填Parr反應器。如實例2 中所述製備壓力歧管’其例外為’光敏劑為孟加拉玫塊紅 且使用壓縮氧氣（或壓縮空氣）作為氣體。對於樣品編號# 3A、3B、3C及3D所添加之MgS〇4之量為0.009 g。 ❹ 表3 使用孟加拉玫魂紅作為光敏劑，高歷之分子氧與單重態氧相比，對軟木 材之效應。 樣品 編號 描述 固有黏度 [η] > mL/g 1C值 Mw (g/mol) SEC 根據[η]之 選擇率 根據Mw 之選擇率 根據[η] 之選擇率 改良，％ 根據Mw 之選擇率 改良，％ TAPPI 亮度 3A 分子氧 607 24.9 842,000 24.4 33,800 - - 26.8 3B 單重 態氧 711 21.3 930,000 33.4 43,700 36.9 29.4 26.9 3C 空氣- M.O. 646 27.8 943,000 23.2 33,900 * 24.6 3D 空氣- S.O. 665 26.3 892,000 25.3 33,900 8.8 6.0 24.1 M.O.=分子氧且S.O.=單重態氧 對於未漂白之牛皮紙軟木漿所述之資料（在表3中針對孟 加拉玫瑰紅）說明與以分子氧進行之氧脫木素作用相比， 在本發明之單重態氧存在下氧脫木素作用之選擇率改良為 3 6.9%(樣品編號38)»藉由尺值自使用分子氧之24.9(樣品編 號3 A)降低至使用單重態氧之21.3(樣品編號3B)獲得39.9% 之高選擇率改良（基於固有黏度與κ值之比率）’顯示使用單 重態氧具有較大漂白度及可潆白性。κ值之降低為理想 的。表3亦顯示在以分子氧進行之氧脫木素作用過程中， 135183.doc -24- 200934924 固有黏度自起始紙漿之778 g/mL急劇降低至607 g/mL(樣品 編號3 A) ’而在使用單重態氧時’固有黏度降低少得多， 至711 g/mL (樣品編號3Β)β分子氧比單重態氧導致更多纖 維素降解。 實例4 在本實例中’如實例2中所述裝填parr反應器。如實例2 中所述製備壓力歧管，其例外為，光敏劑為曙紅γ。對於 樣品編號# 4A及4B所添加之MgS〇4之量為0.009 g。 表4 使用曙紅Y作為光敏劑’高壓之分子氧與單重態氡相比，對軟木材之效應。 樣品 編號 描述 固有黏度 [η] > mL/g K值 Mw (g/mol) SEC 根據[η] 之選擇率 根據Mw 之選擇率 根據[η] 之選擇率 改良，％ 根據Mw 之選擇率 改良，％ TAPPI 亮度 4A 分子氧 607 24.9 842,000 24.2 33,800 - 26-8 4B 單重 態氧 548 22.3 883,000 24.6 39,600 0.82 17.1 27.6 實例5 在本實例中，如實例2中所述裝填parr反應器。如實例2 中所述製備壓力歧管，其例外為，光敏劑為等量亞甲基藍 ❹ 與孟加拉玫瑰紅之混合物。對於樣品編號# 5A及5B所添加 之MgS〇4之量為0.009 g。 表5 使用亞曱基藍與孟加拉玫瑰紅之混合物作為光敏劑，高壓之分子氣與單重態 氧相比，對軟木材之效應。 ’ 樣品 編號 描述 固有黏度 [η] - mL/g κ值 Mw (g/mol) SEC 根據[η] 之選擇率 根據Mw 之選擇率 根據[η] 之選擇率 改良，％ 根據Mw 之遘擇率 改良，％ TAPPI 亮度 5A 分子氧 607 24.9 842,000 244~ 33,800 - 26.8 5B 單重 態氧 647 23.2 873,000 27.9 37,600 14.3 11.8 25.1 表5顯示當使用亞甲基藍與孟加拉玫瑰紅之混合物作為化 135183.doc •25· 200934924 學S式劑時’選擇率改良更接近匹配使用亞曱基藍時之結果。 實例6 在本實例中’如實例2中所述裝填Parr反應器。如實例2 中所述製備壓力歧管’其例外為，光敏劑為長度6.25 cm 之孟加拉玫瑰紅。對於樣品編號# 6A及6B所添加之MgS〇4 之量為0.009 g。 表6 使用孟加拉玫塊紅(長度=6.25 cm)作為光敏劑，高壓之分子氧與單重皞負. 比，對軟木材之效應。 、〜乳子 樣品 編號 描述 固有黏度 [η]， mL/g κ值 Mw (g/mol) SEC 根據[η] 之選擇率 根據Mw 之選擇率 根據[η] 之選擇率 改良，％ 根據Mw 之選擇率 改良，％ TAPPI 亮度 6A 分+氧 607 24.9 842,000 24.4 33,800 26.8 6B 單重 態氧 645 22.8 873,000 28.3 38,300 16.0 11.8 28.7 表ό證明減少孟加拉玫瑰紅（化學試劑）之表面積相應地 改變選擇率改良。 實例7 在本實例中’如實例2中所述裝填Pair反應器。如實例2 中所述製備壓力歧管，其例外為，光敏劑為孟加拉玫瑰 紅。亦添加瓜爾膠》對於樣品編號# 7 A及7B所添加之 MgSCU之量為〇.009 g且所添加之瓜爾膠之量為〇 19呂。 使用孟加拉玫瑰紅作為光敏劑_添加瓜爾膠，高壓之分子氧與單重態 ， 對軟木材之效應。 樣品 編號 7A 描述 石子氧 固有黏度 [η] 1 mL/g 639 K值 24.0 Mw (g/mol) SEC rx4； nnn 根據[η] 之選擇率 OC C. 根據Mw 之選擇率 ΊΑ ΟΑΛ 根據[η] 之選擇率 改良，％ 根據Mw 之選擇率 改良，％ TAPPI 亮度 7B 單重 態氡 670 ^ 20.4 860,000 Ζ0.0 32.8 1 J〇,7UU 42,200 23,3 25.1 28.0 135183.doc -26- 200934924 實例7及8顯示在兩種不同選擇性試劑-瓜爾膠及過氧化 氫存在下單重態氧之效應。選擇性試劑為通常在氧脫木素 作用過程t添加之化學品。在先前技術中所報導之選擇性 試劑分為五類：（1)氧化劑，諸如（但不限於）過氧化氫、 氣、二氧化氣；（2)移除或鈍化過渡金屬離子之錯合劑，諸 如（但不限於）硫酸鎂（MgS〇4)、葡糖酸鈉或葡糖酸鎂、黏 康酸（muconic acid)、乙二胺四乙酸（EDTA)及其鹽、二伸 乙三胺五乙酸（DTPA)及其鹽；（3)減少所存在之自由基之 量的自由基清除劑，諸如（但不限於）黏康酸 '葡糖酸鈉或 葡糖酸鎂、1·羥基亞乙基_丨，2_二膦酸鈉（HEDp) ; 吸附在 纖維素纖維上之纖維素保護材料，諸如（但不限於）硫酸鎂 (MgSOd、酚、酚及硫酸鎂、瓜爾膠及半纖維素；及（5)其 他，包括（但不限於）酶、界面活性劑、有機溶劑（有機溶劑 法）’及廢液。 如表7中所示，在瓜爾膠存在下，選擇率改良為 23.3%(樣品編號7B)，而過氧化氫產生對選擇率改良有害 之羥基自由基（hydroxide radical)(樣品編號8B)。 實例8 在本實例中，如實例2中所述裝填Parr反應器。如實例2 中所述製備壓力歧管，其例外為，光敏劑為孟加拉玫瑰紅 與過氧化氫組合。對於樣品編號# 8A及8B所添加之MgS04 之量為0.009 g。對於樣品編號# 8a及8B所添加之H2〇2之 量為 0.6437 g。 135183.doc •27- 200934924 表8 使用孟加拉玫瑰紅作為光敏劑-添加H2〇2，高壓之分子氧與單重態氧相比，對 軟木材之效應。 樣品 編號 描述 因有黏度 [η] > mL/g κ值 Mw (g/mol) SEC (10s) a 據[η] 之選擇率 根據Mw 之選擇率 根據[η] 之選擇率改 良，％ 根據Mw 之選擇率 改良，％ TAPPI 亮度 8A 分子氡 603 22.4 928,000 26.9 41,400 - 27.7 8B 單重 態氧 602 22.3 856,000 27.0 38,400 0.37 -7.25 28.6 實例9 在本實例中，如實例2中所述裝填parr反應器。如實例2 中所述製備壓力歧管’其例外為，光敏劑為孟加拉玫瑰 紅。使用兩個Craftsman® 23 W螢光工作燈作為光源。對於 樣品編號# 9A及9B所添加之MgS04之量為0.009 g。 表9 使用孟加拉玫瑰紅作為光敏劑-螢光，高壓之分子氧與單重態氧相比，對軟木 材之效應。 樣品 編號 描迷 固有黏度 [η] · mL/g K值 Mw (g/mol) SEC 根據[η] 之選擇率 根據Mw 之選擇率 根據[η] 之選擇率 改良，％ 根據Mw 之選擇率 改良，％ TAPPI 亮度 9A 分子氧 607 24.9 842,000 24.4 33,800 - - 26.8 9B 單重 態氧 579 23.2 883,000 24.9 38,100 2.05 15.1 27.2 表9中之資料說明螢光燈亦可用作產生單重態氧之光 源。 實例10 在本實例中’如實例2中所述裝填parr反應器。如實例2 中所述製備壓力歧管’其例外為，光敏劑為孟加拉玫瑰 紅。乾燥後以原樣使用未漂白、預水解之牛皮紙硬木材 (購自 Appleton Paper Inc·，Roaring Springs, PA-40-45%紅橡 木（RED OAK)，10-15% 白橡木（WHITE OAK)，連同白楊 135183.doc -28- 200934924 (poplar)及白蠟樹（ash))漿。其起始<值為15 2，其起始固有 黏度為668 mL/g，且其重量平均分子量為1〇8〇〇〇〇道爾 頓。對於樣品編號# 1〇A及1〇B所添加之河㈡…之量為 0.009 g 〇 表10 使用孟加拉魏紅作為光鋪，高壓之分子氧與單重錄她，對硬木材之 效應》 〇 樣品 編號 1 Α Λ 描述 固有黏度 [η] · mL/g <1式 _ 一 -κ值 Mw (g/mol) SEC 根據[η] 之選擇率 根據Mw 之選擇率 根據[η] 之選擇率 改良，％ _根據Mw 之選擇率 TAPPI 亮度 1UA 1 no 分子乳 ea壬 010 anQ " 10.8 1,000,000 57.0 92.600 35 6 lUc 早重 態氧 OZo 10.5 1,060,000 59.8 101,000 4.91 9.03 36.6 表10中之資料證明在硬木材之氧脫木素作用及漂白中增 加之選擇率改良。選擇率改良不如軟木材一樣大因為硬 木材含有比軟木材少之木質素。基於sec 1^以與<值之比 率’獲得9.03%之選擇率改良（樣品編號i〇b)。 實例11 ❹ 在本實例中，如實例2中所述裝填Parr反應器。如實例2 中所述製備壓力歧管，其例外為，光敏劑為孟加拉玫瑰 紅乾燥後以原樣使用未漂白、預水解之機械衆。其起始 κ值為57.9’其重量平的合尽 篁十巧刀子量為089,000道爾頓，且 T·亮度為47.6。對於樣品編_ "A及ιιβ所添加之 MgS04之量為 〇.〇〇9 g。 表11 使用孟加拉恤輪，峨獅比，對機械浆之 樣品 編號 描述 _ K值 Mw (g/mol) SEC --------------- <選1率 根據Mw 之選擇率改良，％ 亮度 11A 分子氧 6ΤΓ~~~ 621,000 11B 單重態氧 52Λ 523,000 -------------- - 58.6 ------- 9.49 56.1 135183.doc -29, 200934924 與實例1-10及實例12中使用之化學漿不同，表11中所述 之資料使用機械漿。表11說明與使用分子氧所獲得之結果 相比，使用單重態氧對機械漿之氧脫木素作用的選擇率改 良。樣品編號# 11B顯示使用單重態氧獲得9.49%之選擇率 改良（基於SEC Mw與κ值之比率）。由於樣品編號# 11A及 11B在溶液中不完全溶解，因此並未獲得該等樣品之固有 黏度。 實例12 〇 在本實例中，如實例2中所述裝填Parr反應器。如實例2 中所述製備壓力歧管，其例外為，光敏劑為孟加拉玫瑰紅 且使稠度變化-25%之高稠度，樣品編號#12A及12B ; 10% 之中等稠度，樣品編號#12C及12D ;及5%之低稠度，樣品 編號#12E及12F。對於樣品編號# 12A-12F所添加之MgS04 之量為0,009 g。 表12 在不同稠度下，使用孟加拉玫瑰紅作為光敏劑，高壓之分子氧與單重態氧相 比，對軟木材之效應。 樣品 編號 描述 固有黏度 [η] , mL/g κ值 Mw (g/mol) SEC 根據[η] 之選擇率 根據Mw 之選擇率 根據[η] 之選擇率 改良，％ 根據Mw 之選擇率 改良，％ TAPPI 亮度 12A 分子氧 572 23.2 853,000 24.7 36,800 - - 26,3 12B 單重 態氧 536 22.7 821,000 23.6 36,200 4.2 •1.63 26.2 12C 分子氧 607 24.9 884,000 24.4 35,500 - - 26.8 12D 單重 態氧 711 21.3 930,000 33.4 43,700 36.9 23.0 26.9 12E 分子氧 586 22.1 950,000 26.5 435000 27.9 12F 單重 態氧 592 22.2 874,000 26.7 39,400 0.75 -7.0 29.6 表12中之資料證明在不同稠度下使用單重態氧增加之選 擇率改良。在10%之中等稠度時獲得使用單重態氧之最佳 135183.doc -30- 200934924 選擇率改良。 【圖式簡單說明】 圖1為根據本發明之一實施例使用周圍壓力之實驗室系 統的方塊圖，該系統係用於產生可用於增強脫木素作用或 漂白之單重態氧。 囷2為根據本發明之一實施例使用高壓之實驗室系統的 方塊圖，該系統係用於產生可用於增強脫木素作用或漂白 之單重態氧。 © 圖3為根據本發明之一實施例具有五腔寘裝置、使用高 壓之可能工業規模系統的方塊圖，該系統係用於產生可用 於增強脫木素作用或漂白之單重態氧。更多或更少之腔室 亦可實現。 圖4為根據本發明之一實施例使用高壓之可能兩階段工 業系統之一部分的方塊圖，該系統係用於產生可用於增強 脫木素作用或漂白之單重態氧。具有一或多個階段之相同 配置亦可實現。 ❹ 13S183.docMeasured by Wilmington, DE). For the molecular oxygen experiment, the chemical reagent was covered with aluminum foil. Light from a halogen lamp (500 W) was applied during the singlet oxygen experiment. In Example 9 (one of the singlet oxygen experiments), two Craftsman® 23 W fluorescent working light sources were used. Example 2 135183.doc -22- 200934924 The Parr reactor was charged with 180 g of deionized water, 19.31 g of softwood pulp (18.0 g oven dried pulp) and 0.0072 g of NaOH. Softwood pulp was added after the sodium hydroxide and magnesium sulfate were completely dissolved. The reaction flask was heated to 1 ° C for 90 minutes at 275 kPa. The bulk pressure reactor manifold (Ace Glass, Vineland, NJ) was filled with glass wool, Drierite® anhydrous calcium sulfate, and glass beads coated with a fluorene-based blue photosensitizer. The methylene blue photosensitizer was covered with aluminum foil for the control molecular oxygen. Light from a halogen lamp (500 W) was applied during the singlet oxygen experiment. The consistency of the pulp is 10 〇 / 〇. 〇 After the specified time, the reacted pulp was separated on a Buchner funnel with a Whatman #41 filter paper under suction vacuum. The pH of the filtrate was measured between 7.9 and 9.4. The pulp was rinsed by adding about 5 〇〇 mL of deionized water to the funnel under suction vacuum. The pulp was again rinsed by adding about 500 mL of deionized water to the funnel under suction vacuum. The pulp air was then dried overnight and then dried in a vacuum oven at 40 ° C for 2 hours. The amount of MgS〇4 added for sample numbers #2A and 2B is 〇.〇 g. The amount of MgS04 added for sample numbers #2C and 2D was 0.009 g. Table 2 uses methylene blue as a photosensitizer. The effect of molecular pressure on the soft wood compared to singlet oxygen. Sample No. Description Intrinsic viscosity [η] · mL/g κ value Mw (g/mol) SEC According to the selectivity of [η], the selectivity of Mw is improved according to the selectivity of [η], and % is improved according to the selectivity of Mw. % TAPPI brightness 2A Molecular oxygen 24.0 905,000 24.3 37,700 - - 26.8 2B singlet oxygen 04/ 24.1 1,060,000 26.8 44,000 10.3 25.8 2C Molecular oxygen 607 24.9 842,000 24.4 33,800 - • 26 8 2D singlet oxygen 646 23.3 952,000 27.7 40,800 13.5 20.6 26.9 2 Prove that the selectivity of MgS〇4 was improved to 10.3% when using methylene blue as the chemical 135183.doc -23- 200934924 reagent by using a high-pressure experimental apparatus, and 13.5% when there was MgS〇4. In the remaining tables, MgS〇4 was added to the molecular oxygen and singlet oxygen examples. As described in Example 7, 'MgS〇4 is a selectivity agent. Example 3 In this example, a Parr reactor was charged as described in Example 2. The pressure manifold was prepared as described in Example 2 with the exception that the photosensitizer was Bengal Rose Red and compressed oxygen (or compressed air) was used as the gas. The amount of MgS〇4 added to sample numbers #3A, 3B, 3C, and 3D was 0.009 g. ❹ Table 3 uses the beauty of Bengal red as a photosensitizer, and the effect of molecular oxygen in the high calendar on softwood compared to singlet oxygen. Sample No. Description Intrinsic viscosity [η] > mL/g 1C value Mw (g/mol) SEC According to the selectivity of [η], the selectivity of Mw is improved according to the selectivity of [η], and % is improved according to the selectivity of Mw. , % TAPPI Brightness 3A Molecular Oxygen 607 24.9 842,000 24.4 33,800 - - 26.8 3B Singlet Oxygen 711 21.3 930,000 33.4 43,700 36.9 29.4 26.9 3C Air - MO 646 27.8 943,000 23.2 33,900 * 24.6 3D Air - SO 665 26.3 892,000 25.3 33,900 8.8 6.0 24.1 MO = molecular oxygen and SO = singlet oxygen. The information described for unbleached kraft pulp (in Table 3 for Bengal Rose Bengal) is compared to the oxygen delignification by molecular oxygen, in the present invention. The selectivity of oxygen delignification in the presence of singlet oxygen was improved to 3 6.9% (Sample No. 38) » by the ruler from 24.9 (sample number 3 A) using molecular oxygen to 21.3 using singlet oxygen (sample No. 3B) A high selectivity improvement of 39.9% (based on the ratio of intrinsic viscosity to kappa value) 'shows greater bleaching and chalkiness with singlet oxygen. A decrease in the κ value is desirable. Table 3 also shows that in the process of oxygen delignification by molecular oxygen, the intrinsic viscosity of 135183.doc -24- 200934924 sharply decreased from 778 g/mL of the starting pulp to 607 g/mL (sample No. 3 A). Intrinsic viscosity decreases much less when using singlet oxygen, up to 711 g/mL (sample number 3Β). Beta molecular oxygen causes more cellulose degradation than singlet oxygen. Example 4 In this example, a parr reactor was charged as described in Example 2. A pressure manifold was prepared as described in Example 2 with the exception that the photosensitizer was eosin gamma. The amount of MgS〇4 added to sample Nos. #4A and 4B was 0.009 g. Table 4 uses Eosin Y as a photosensitizer. The effect of high pressure molecular oxygen on softwood compared to singlet ruthenium. Sample No. Description Intrinsic viscosity [η] > mL/g K value Mw (g/mol) SEC According to the selectivity of [η], the selectivity of Mw is improved according to the selectivity of [η], and % is improved according to the selectivity of Mw. % TAPPI Brightness 4A Molecular Oxygen 607 24.9 842,000 24.2 33,800 - 26-8 4B Singlet Oxygen 548 22.3 883,000 24.6 39,600 0.82 17.1 27.6 Example 5 In this example, a parr reactor was charged as described in Example 2. A pressure manifold was prepared as described in Example 2 with the exception that the photosensitizer was a mixture of equal amounts of methylene blue quinone and bengal rose red. The amount of MgS〇4 added to sample numbers #5A and 5B was 0.009 g. Table 5 uses a mixture of amidoxime blue and rose bengal as a photosensitizer, the effect of high pressure molecular gas on softwood compared to singlet oxygen. 'Sample number description intrinsic viscosity [η] - mL/g κ value Mw (g/mol) SEC According to the selection rate of [η] according to the selectivity of Mw according to the selection rate of [η], % according to the selection rate of Mw Modified, % TAPPI Brightness 5A Molecular Oxygen 607 24.9 842,000 244~ 33,800 - 26.8 5B Singlet Oxygen 647 23.2 873,000 27.9 37,600 14.3 11.8 25.1 Table 5 shows when a mixture of methylene blue and bengal red is used as 135183.doc •25· 200934924 In the case of the S-type agent, the selectivity improvement is closer to the result of matching the use of the fluorene blue. Example 6 In this example, a Parr reactor was loaded as described in Example 2. The pressure manifold was prepared as described in Example 2 with the exception that the photosensitizer was Bengal Rose Red, 6.25 cm in length. The amount of MgS〇4 added to sample numbers #6A and 6B was 0.009 g. Table 6 uses Bengal red (length = 6.25 cm) as a photosensitizer, the effect of high molecular oxygen and single weight, compared to softwood. , ~ milk sample number description intrinsic viscosity [η], mL / g κ value Mw (g / mol) SEC according to the selection rate of [η] according to the selection rate of Mw according to the selection rate of [η], % according to Mw Selectivity improvement, % TAPPI brightness 6A min + oxygen 607 24.9 842,000 24.4 33,800 26.8 6B singlet oxygen 645 22.8 873,000 28.3 38,300 16.0 11.8 28.7 The evidence demonstrates that reducing the surface area of Bengal Rose Red (chemical reagent) correspondingly changes the selectivity. Example 7 In this example, a Pair reactor was loaded as described in Example 2. A pressure manifold was prepared as described in Example 2 with the exception that the photosensitizer was Bengal Rose Bengal. Also added is guar gum. The amount of MgSCU added for sample numbers #7 A and 7B is 009.009 g and the amount of guar gum added is 〇 19 碌. Use Bengal Rose Red as a photosensitizer _ add guar gum, high molecular oxygen and singlet, the effect on soft wood. Sample No. 7A Describes the inherent viscosity of stone oxygen [η] 1 mL/g 639 K value 24.0 Mw (g/mol) SEC rx4; nnn Selectivity θ C according to [η]. According to Mw selectivity ΊΑ ΟΑΛ according to [η] The selectivity is improved, % is improved according to the selection rate of Mw, % TAPPI brightness 7B singlet state 氡 670 ^ 20.4 860,000 Ζ 0.0 32.8 1 J〇, 7UU 42,200 23, 3 25.1 28.0 135183.doc -26- 200934924 Examples 7 and 8 The effect of singlet oxygen in the presence of two different selective reagents, guar and hydrogen peroxide, is shown. The selective agent is a chemical that is usually added during the oxygen delignification process. The selective agents reported in the prior art are classified into five categories: (1) oxidizing agents such as, but not limited to, hydrogen peroxide, gas, and dioxins; (2) removing or inactivating transition metal ion complexing agents, Such as, but not limited to, magnesium sulfate (MgS〇4), sodium gluconate or magnesium gluconate, muconic acid, ethylenediaminetetraacetic acid (EDTA) and its salts, diethylenetriamine Acetic acid (DTPA) and its salts; (3) free radical scavengers that reduce the amount of free radicals present, such as, but not limited to, muconic acid 'sodium gluconate or magnesium gluconate, 1 · hydroxy-ethylene Base_丨, 2_bisphosphonate (HEDp); Cellulosic protective material adsorbed on cellulose fibers such as, but not limited to, magnesium sulfate (MgSOd, phenol, phenol and magnesium sulfate, guar and semi-fiber) And (5) other, including (but not limited to) enzymes, surfactants, organic solvents (organic solvent method)' and waste liquid. As shown in Table 7, in the presence of guar gum, the selectivity is improved to 23.3% (sample No. 7B), while hydrogen peroxide produces a hydroxide radical that is detrimental to the selectivity improvement ( Item No. 8B). Example 8 In this example, a Parr reactor was charged as described in Example 2. A pressure manifold was prepared as described in Example 2 with the exception that the photosensitizer was a combination of Bengal Rose Bengal and hydrogen peroxide. The amount of MgS04 added for sample numbers #8A and 8B was 0.009 g. The amount of H2〇2 added for sample numbers #8a and 8B was 0.6437 g. 135183.doc •27- 200934924 Table 8 Using Bengal Rose Red Photosensitizer - Addition of H2〇2, high pressure molecular oxygen compared to singlet oxygen, effect on soft wood. Sample number description due to viscosity [η] > mL/g κ value Mw (g/mol) SEC (10s a) The selectivity of [η] is improved according to the selectivity of [η] according to the selectivity of [w], % is improved according to the selectivity of Mw, % TAPPI brightness is 8A molecule 氡 603 22.4 928,000 26.9 41,400 - 27.7 8B singlet oxygen 602 22.3 856,000 27.0 38,400 0.37 -7.25 28.6 Example 9 In this example, a parr reactor was charged as described in Example 2. A pressure manifold was prepared as described in Example 2 with the exception that the photosensitizer was Bengal Rose Bengal. Craftsman® 23 W Fluorescent Work The lamp was used as the light source. The amount of MgS04 added for sample numbers #9A and 9B was 0.009 g. Table 9 Using Bengal Rose Bengal as a photosensitizer-fluorescent, high pressure molecular oxygen compared to singlet oxygen, effect on soft wood The sample number describes the intrinsic viscosity [η] · mL/g K value Mw (g/mol) SEC According to the selection rate of [η] according to the selectivity of Mw according to the selection rate of [η], % according to the selection rate of Mw Improved, % TAPPI Brightness 9A Molecular Oxygen 607 24.9 842,000 24.4 33,800 - - 26.8 9B Singlet Oxygen 579 23.2 883,000 24.9 38,100 2.05 15.1 27.2 The information in Table 9 shows that fluorescent lamps can also be used as a source of singlet oxygen. Example 10 In this example, a parr reactor was loaded as described in Example 2. The pressure manifold was prepared as described in Example 2 with the exception that the photosensitizer was Bengal Rose Bengal. After drying, use unbleached, prehydrolyzed kraft hardwood (purchased from Appleton Paper Inc., Roaring Springs, PA-40-45% Red Oak (RED OAK), 10-15% White Oak (WHITE OAK), together with Poplar 135183.doc -28- 200934924 (poplar) and ash (ash) pulp. Its initial < value is 15 2, its initial intrinsic viscosity is 668 mL/g, and its weight average molecular weight is 1〇8〇〇〇〇Dalton. For the sample number #1〇A and 1〇B, the amount of river (2) added is 0.009 g. 〇 Table 10 Using Bengal Weihong as a light shop, high molecular oxygen and single recording her, the effect on hard wood 〇 Sample No. 1 Α Λ Describe intrinsic viscosity [η] · mL/g <1 _ _ κ value Mw (g/mol) SEC Selectivity according to [η] according to the selectivity of Mw according to the selectivity of [η] Improvement, % _ according to Mw selectivity TAPPI brightness 1UA 1 no molecular emulsion ea壬010 anQ " 10.8 1,000,000 57.0 92.600 35 6 lUc early heavy oxygen OZo 10.5 1,060,000 59.8 101,000 4.91 9.03 36.6 The information in Table 10 proves in hard wood The oxygen delignification effect and the increased selectivity in bleaching are improved. The improvement in selectivity is not as great as that of soft wood because hardwood contains less lignin than softwood. A selectivity improvement of 9.03% was obtained based on sec 1^ at a ratio of < value (sample number i〇b). Example 11 ❹ In this example, a Parr reactor was charged as described in Example 2. A pressure manifold was prepared as described in Example 2 with the exception that the photosensitizer was Bengal Rose Red and the unbleached, prehydrolyzed machine was used as it was. Its initial κ value is 57.9', its weight is equal to 089,000 Daltons, and T·luminance is 47.6. The amount of MgS04 added to the sample _ "A and ιιβ is 〇.〇〇9 g. Table 11 Using the Bengali-style wheel, the lion-to-lion ratio, the sample number of the mechanical pulp is described _ K value Mw (g/mol) SEC --------------- <Selection rate according to Mw The selectivity is improved, % brightness 11A molecular oxygen 6ΤΓ~~~ 621,000 11B singlet oxygen 52Λ 523,000 -------------- - 58.6 ------- 9.49 56.1 135183.doc - 29, 200934924 Unlike the chemical pulps used in Examples 1-10 and Example 12, the materials described in Table 11 used mechanical pulp. Table 11 shows that the selectivity of the oxygen delignification of mechanical pulp is improved using singlet oxygen as compared to the results obtained using molecular oxygen. Sample No. #11B shows a 9.49% selectivity improvement using singlet oxygen (based on the ratio of SEC Mw to κ values). Since sample numbers #11A and 11B were not completely dissolved in the solution, the intrinsic viscosity of the samples was not obtained. Example 12 〇 In this example, a Parr reactor was charged as described in Example 2. A pressure manifold was prepared as described in Example 2 with the exception that the photosensitizer was Bengal Rose Bengal and the consistency was changed to a consistency of -25%, sample numbers #12A and 12B; 10% medium consistency, sample number #12C and 12D; and 5% low consistency, sample numbers #12E and 12F. The amount of MgS04 added for sample number #12A-12F was 0,009 g. Table 12 Effect of high pressure molecular oxygen on softwood compared to singlet oxygen at different consistency using bengal red as a photosensitizer. The sample number describes the intrinsic viscosity [η], mL/g κ value Mw (g/mol). The selectivity of SEC according to [η] is improved according to the selectivity of [η] according to the selectivity of Mw, and % is improved according to the selectivity of Mw. % TAPPI brightness 12A molecular oxygen 572 23.2 853,000 24.7 36,800 - - 26,3 12B singlet oxygen 536 22.7 821,000 23.6 36,200 4.2 •1.63 26.2 12C molecular oxygen 607 24.9 884,000 24.4 35,500 - - 26.8 12D singlet oxygen 711 21.3 930,000 33.4 43,700 36.9 23.0 26.9 12E Molecular Oxygen 586 22.1 950,000 26.5 435000 27.9 12F Singlet Oxygen 592 22.2 874,000 26.7 39,400 0.75 -7.0 29.6 The data in Table 12 demonstrates the improved selectivity of singlet oxygen at different consistency. The best use of singlet oxygen is obtained at an equal consistency of 10%. 135183.doc -30- 200934924 Selectivity improvement. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a block diagram of a laboratory system using ambient pressure for producing singlet oxygen that can be used to enhance delignification or bleaching, in accordance with one embodiment of the present invention.囷 2 is a block diagram of a laboratory system using high pressure in accordance with an embodiment of the present invention for producing singlet oxygen that can be used to enhance delignification or bleaching. Figure 3 is a block diagram of a possible industrial scale system using a five-chamber device with high pressure, which is used to generate singlet oxygen that can be used to enhance delignification or bleaching, in accordance with one embodiment of the present invention. More or fewer chambers can also be implemented. 4 is a block diagram of a portion of a possible two-stage industrial system using high pressure for producing singlet oxygen that can be used to enhance delignification or bleaching, in accordance with an embodiment of the present invention. The same configuration with one or more stages can also be implemented. ❹ 13S183.doc