JPH0268378A - Bleaching of lignocellulose substance - Google Patents
Bleaching of lignocellulose substanceInfo
- Publication number
- JPH0268378A JPH0268378A JP21258388A JP21258388A JPH0268378A JP H0268378 A JPH0268378 A JP H0268378A JP 21258388 A JP21258388 A JP 21258388A JP 21258388 A JP21258388 A JP 21258388A JP H0268378 A JPH0268378 A JP H0268378A
- Authority
- JP
- Japan
- Prior art keywords
- bleaching
- pulp
- stage
- bleach
- chlorine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004061 bleaching Methods 0.000 title claims abstract description 96
- 239000000126 substance Substances 0.000 title abstract description 12
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims abstract description 24
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000460 chlorine Substances 0.000 claims abstract description 17
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 17
- 239000004155 Chlorine dioxide Substances 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 15
- 235000019398 chlorine dioxide Nutrition 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims description 25
- 238000006073 displacement reaction Methods 0.000 claims description 19
- 239000012978 lignocellulosic material Substances 0.000 claims description 10
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims 1
- 239000007844 bleaching agent Substances 0.000 abstract description 35
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 16
- 238000006467 substitution reaction Methods 0.000 abstract description 3
- 229920001131 Pulp (paper) Polymers 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000002655 kraft paper Substances 0.000 description 5
- 229920005610 lignin Polymers 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 241001580935 Aglossa pinguinalis Species 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 241000180579 Arca Species 0.000 description 1
- 235000018185 Betula X alpestris Nutrition 0.000 description 1
- 235000018212 Betula X uliginosa Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001720 carbohydrates Chemical group 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 238000009895 reductive bleaching Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Paper (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はりグノセ！レロース物質の漂白方法に関し、更
に詳しくは、セルロースパルプの新規な動的置換漂白の
シーケンスに関する。[Detailed Description of the Invention] [Industrial Field of Application] The present invention is unique! The present invention relates to a method for bleaching reulose materials, and more particularly to a novel dynamic displacement bleaching sequence for cellulose pulp.
リグノセルロース物質を多くの用途に使用するためには
、化学的あるいは機械的作用により得られたパルプを漂
白する必要がある。クラフトパルプを包装資材のような
白さを必要としない用途に使う場合を除いては、通常、
塩素、次亜塩素酸塩（ハイポ）、二酸化塩素、酸素、過
酸化水素、苛性ソーダ等の漂白剤及び漂白助剤により漂
白して、未晒パルプの着色原因物質である残留リグニン
等を除去する必要がある。In order to use lignocellulosic materials in many applications, it is necessary to bleach the resulting pulp by chemical or mechanical action. Unless kraft pulp is used for applications that do not require whiteness, such as packaging materials,
It is necessary to bleach with bleaching agents and bleaching aids such as chlorine, hypochlorite (hypo), chlorine dioxide, oxygen, hydrogen peroxide, and caustic soda to remove residual lignin, etc., which is the coloring agent of unbleached pulp. There is.
強度を要求される化学パルプの漂白においては、パルプ
繊維自体の強度を高く保つために、炭水化物（セルロー
ス等）の分解に及ぼす影響を最小にするよう、過激な一
段の静的な漂白をさけ、温和に漂白剤・漂白条件を変え
ていく多段漂白を採るのが一般的である。When bleaching chemical pulp that requires strength, in order to keep the strength of the pulp fiber itself high, one-step static bleaching is avoided to minimize the effect on the decomposition of carbohydrates (cellulose, etc.). Multi-stage bleaching, in which the bleaching agent and bleaching conditions are gently changed, is commonly used.
≠多段漂白工程（シーケンス）は通常、最初に塩素処理
で未晒パルプ中に残留しているリグニンを塩素化しＯＴ
溶性を付加した後火にアルカリでリグニンを溶解抽出す
る。その後更に、次亜塩素酸塩、二酸化塩素等を用いて
、残留する少欧のリグニン等を分解除去し、白色度の高
いパルプを得る。≠In the multi-stage bleaching process (sequence), the lignin remaining in the unbleached pulp is usually chlorinated first by chlorine treatment, and then OT
After adding solubility, lignin is dissolved and extracted with alkali over fire. Thereafter, residual lignin and the like are decomposed and removed using hypochlorite, chlorine dioxide, etc. to obtain pulp with high whiteness.
塩素処理をＣ、アルカリ処理をＥ、次亜塩素塩
酸処理をＨ１二酸化塩素処理をＤ１過酸化水素△
処理をＰ１水洗浄処理（ｉ−ｗとして表わすと、この漂
白工程は、使用する漂白剤及び／又は漂白助剤の順序に
したがい、Ｃ−Ｅ−Ｈ−Ｅ−Ｄ％Ｃ−Ｅ−Ｄ−Ｅ−Ｄ、
Ｃ−Ｅ−Ｉ（−Ｄ−Ｐ等の複数段の漂白段で行なわれ
、又漂白段の間に水洗浄処理の段階を設けることができ
る。なお、本明細曹では以下、前記した各種の漂白剤処
理、漂白助剤処理及び水洗浄処理をそれぞれ漂白工程に
おける一段の漂白段として記載する。Chlorine treatment is C, alkali treatment is E, hypochlorite treatment is H1 chlorine dioxide treatment is D1 hydrogen peroxide Δ treatment is P1 water washing treatment (expressed as i-w, this bleaching process is based on the bleaching agent used and / or according to the order of bleaching aids, C-E-H-ED-D%C-E-D-ED-D,
C-E-I (-D-P, etc.) is carried out in multiple bleaching stages, and a water washing step can be provided between the bleaching stages. Bleach treatment, bleach aid treatment and water washing treatment are each described as a bleaching step in the bleaching process.
漂白工程の操作としては、静的漂白においては、各段ご
とにパルプと漂白剤を混合し、残留リグニン等と漂白剤
の反応を完全に行わせるため、混合した後はパルプと漂
白液が静的状態で充分滞留時間を取るべく漂白タワー内
を移動させ、更に、漂白タワーからの排出、洗浄が繰返
される。更に詳細には、通常のタワー漂白では、パルプ
とそれを取巻く漂白液は静的状態でタワー内を移動する
。このような状態では、パルプの周辺の漂白液中の漂白
剤だけがパルプによシ消費され、そして、漂白剤の活性
力は急激に消失される。一方、反応生成物はパルプから
溶出し、パルプの周シの漂白液中にごく薄い反応生成物
層を形成する。ところで、漂白液中の漂白剤のパルプに
対する拡散速度が遅＜、シかもバルブ周辺に生じた反応
生成物層が、パルプに対する漂白剤の拡散を遅らせ、場
合によっては漂白剤も消費し活性力を消失させ、したが
って、パルプに対する漂白剤の拡散移動が大幅に遅くな
る。一般にパルプと漂白剤の反応は非常に短時間で終る
ことが知られているが、通常のタワー漂白では、前記の
ようにパルプに対する漂白剤の移動がないため、バルブ
表面への漂白剤の拡散に時間がかかり、各段の漂白に要
する時間は一般的に１〜４時間程度であり、全体で１０
時間以上を要した。In static bleaching, the pulp and bleach are mixed at each stage to allow the residual lignin to react completely with the bleach. The bleaching material is moved through the bleaching tower to ensure sufficient residence time under the desired conditions, and then discharged from the bleaching tower and washed are repeated. More specifically, in conventional tower bleaching, the pulp and surrounding bleaching solution move through the tower in a static state. Under such conditions, only the bleaching agent in the bleaching solution around the pulp is consumed by the pulp, and the active power of the bleaching agent is rapidly lost. On the other hand, the reaction products are eluted from the pulp and form a very thin layer of reaction products in the bleaching solution around the pulp. By the way, if the diffusion rate of the bleach in the bleaching solution into the pulp is slow, the reaction product layer formed around the valve may slow down the diffusion of the bleach into the pulp, and in some cases even consume the bleach and reduce its activity. dissipation, thus significantly slowing down the diffusive transfer of bleach to the pulp. It is generally known that the reaction between pulp and bleach is completed in a very short time, but in normal tower bleaching, there is no movement of bleach against the pulp as described above, so bleach diffuses onto the valve surface. The bleaching time for each stage is generally about 1 to 4 hours, and the total bleaching time is about 10 hours.
It took more than an hour.
この問題点を改善する方法として、パｌレブと漂白剤を
良く攪拌し、パルプと漂白剤との接触を良好にする方法
と、漂白剤の濃度を高くして時間を短縮する方法がある
が、いずれもパルプ品質を損うことと、コストが高くな
る等で実用的でなかった。There are two ways to improve this problem: one is to stir the pulp and bleach well to improve the contact between the pulp and bleach, and the other is to shorten the time by increasing the concentration of bleach. Both of these methods were impractical because they impaired the quality of the pulp and increased costs.
ヲプソン（Ｗ、 Ｈ，Ｒａｐｓｏｎ ） はダイナミ
ックブリーチングの名のもとに、パルプと漂白剤を動的
に接触させることにより、漂白時間を数分の程度に大幅
に短縮した方法を提案した（特公昭４８−３０９６３号
公報、英国特許第１．１００゜７２４号に対応）。この
方法は、一般に動的置換漂白と呼ばれ、漂白液をバルブ
マットに対し強制的に急速に通過させると、漂白液はパ
ルプに対し静的にとどまらず、高い相対速度でパルプの
周りを通過し、反応生成物をパルプの周りから連続的に
取り除くことができる。したがってパルプへの漂白剤の
拡散速度が大きくなり、パルプは実質的に大量の漂白剤
と動的に接触するため、漂白時間は大幅に短縮される。W.H. Rapson proposed a method called dynamic bleaching that dramatically shortened the bleaching time to a few minutes by dynamically bringing pulp and bleach into contact. Publication No. 48-30963, corresponding to British Patent No. 1.100°724). This method, commonly referred to as dynamic displacement bleaching, involves forcing the bleaching solution to rapidly pass through the valve mat, causing the bleaching solution to pass around the pulp at a high relative velocity rather than remaining static relative to the pulp. and the reaction products can be continuously removed from around the pulp. The rate of diffusion of the bleaching agent into the pulp is therefore increased and the pulp is in dynamic contact with a substantially larger amount of bleaching agent, so that the bleaching time is significantly reduced.
その際、加えられた漂白液はバルブマット中を移動し、
既にパルプマット中に存在する液を押し出しく置換し）
ながらパルプマットのすきまを流れてゆく。この時、置
換する液と置換される液との間にかなり明瞭な境界面が
生ずるため、両液間相互の漂白剤の混合が少なく、通常
のタワー漂白で必要とした漂白各段後の洗浄は必要とし
ない利点もある。この置換漂白の原理の実用化は、カミ
ャ社の開発したデイフユーザ−を応用することによって
成功している。そしてデイフユーザ−については、特公
昭４３−１９０８３号公報（米国特許第へ３４ａ３９０
号明細書に対応）、米国特許第３．５７４．５５１ ’
４明細書、特公昭４４−５３２２号公報（米国特許第へ
７０４．６０３号明細書に対応。）、特公昭４６−５７
００２号公報（米国特許第へ５９９．４４９号明細書に
対応。）、特開昭４７−１９１０７号公報（米国特許第
４８１５．３８６号、同第４９７へ５５８号明細書に対
応。）に記載されている。又更に、ザ拳ブリーチング・
オブ・パルプ（ＴｈｅＢｌｅａｃｈｉｎｇｏｆ Ｐｕ１
ｐ ）第５版、第２７５〜２９５頁、タビ−・プレス（
ＴＡＰＰＩ ＰＲＥＳＳ ）等に、その技術内容が発表
されている。At that time, the added bleach solution moves through the valve mat,
The liquid already present in the pulp mat is pushed out and replaced)
It flows through the gaps in the pulp mat. At this time, a fairly clear boundary surface is created between the displacing liquid and the displacing liquid, so there is less mixing of bleach between the two liquids, and the cleaning after each bleaching stage that is required in normal tower bleaching is reduced. There are also benefits that do not require it. The principle of displacement bleaching has been successfully put into practical use by applying a diffuser developed by Kamya. Regarding differential users, Japanese Patent Publication No. 43-19083 (U.S. Patent No. 34a390
No. 3,574,551'
4 specifications, Japanese Patent Publication No. 44-5322 (corresponding to U.S. Patent No. 704.603), Japanese Patent Publication No. 46-57
002 (corresponding to the specification of U.S. Patent No. 599.449), JP-A-47-19107 (corresponding to the specification of U.S. Patent No. 4815.386 and No. 497-558) has been done. Furthermore, the fist bleaching
The Bleaching of Pu1
p) 5th edition, pp. 275-295, Tabby Press (
The technical details have been published in publications such as TAPPI PRESS.
しかしながら、置換漂白ではパルプと漂白剤が動的に接
触し、短時間で漂白を終らせる特徴を有しているが、そ
の反面、漂白剤が短時間で消費されるため、漂白液中の
漂白剤は抽出側（スクリーン側）に達するまでに活性力
を失い、スクリーン側周辺のパルプは、常時漂白剤の濃
度が薄い状態で漂白されていることになり、静的漂白に
比し白色度の上がりが悪い。そしてスクリーン側のパル
プ白色度を高めるだめには漂白剤の添加を多くしなけれ
ばならないという欠点がある。動的置換漂白において所
望の白色度を維持して漂白薬品原単位を削減する方法（
特開昭５３−１４３７０５号公報、カナダ特許第１０９
５７６５号明細書に対応。）が提案されているが、この
方法は漂白温度を最適な白色度がなお達せられるレベル
まで低下させる方法であるため、定常操業時には適応０
Ｔ能であるが生産量が変化した場合、特に生産紙が上が
った場合には、各漂白段での滞留時間が短縮されるので
、この方法の適応は困難である。However, in displacement bleaching, the pulp and bleach come into contact dynamically, and bleaching can be completed in a short time, but on the other hand, because the bleach is consumed in a short time, The agent loses its activity by the time it reaches the extraction side (screen side), and the pulp around the screen side is always bleached with a low concentration of bleach, resulting in a lower whiteness than static bleaching. It doesn't rise well. Another disadvantage is that in order to increase the whiteness of the pulp on the screen side, a large amount of bleach must be added. A method for maintaining desired whiteness and reducing bleaching chemical consumption in dynamic displacement bleaching (
JP-A-53-143705, Canadian Patent No. 109
Corresponds to specification No. 5765. ) has been proposed, but since this method lowers the bleaching temperature to a level where the optimum brightness can still be achieved, it is not possible to adapt 0 during normal operation.
This method is difficult to adapt if the production capacity changes, especially if the production paper increases, since the residence time in each bleaching stage is shortened.
本出願人は前記した欠点を解決する方法として先に、リ
グノセルロース物質より得られたパルプを複数段の動的
ｉ置換漂白を含む漂白力７ｋによシ漂白するに当シ、少
なくとも１段の置換漂白を連続する複数段で行い、かつ
該複数段に分割して添加される漂白剤の使用量の合計を
１段置換漂白の漂白剤の使用所定量と同等以下とするり
グノセルローヌ物質の漂白方法を提案した（特開昭５９
−３０９８０号公報）。この方法により漂白剤の使用量
を低減することが可能となっだけれども、設備の増設、
大巾な改変をともなうという問題点を有していた。As a method for solving the above-mentioned drawbacks, the applicant first proposed that the pulp obtained from lignocellulosic material is bleached with a bleaching power of 7k including multiple stages of dynamic i-displacement bleaching. Bleaching of Gnocellulone substances by carrying out displacement bleaching in multiple successive stages, and by making the total amount of bleach added in the multiple stages equal to or less than the predetermined amount of bleach used in single-stage displacement bleaching. proposed a method (Japanese Unexamined Patent Publication No. 1983)
-30980 publication). Although this method makes it possible to reduce the amount of bleach used,
This had the problem of requiring extensive changes.
また既存の漂白シーケンス、例えば”／Ｃ−Ｅ−Ｈ−旬
渥り、Ｄ／石−Ｅ−Ｄ、 −（Ｅ）−Ｄ２の漂白シーケ
ンス（なお−（Ｅ）は所囁によりアルカリ処理Ｅを設け
ることを意味する。）においては、前者は所望の白色度
を維持して漂白薬品、アルカリ３１品の使用量を削減す
ることが困難であシ、高粘度漂白パルプ得ることができ
なかった。後者はＥ段とＤ１段での適性ｐＨがＥ段では
８〜１１．Ｄ１段では２〜５と大きな相違があり動的置
換漂白における漂白液、アルカリ液の混合は避けられず
各段における最適条件での安定操業が難かしいという問
題点を有していた。なお、動的置換漂白のシーケンスに
関しては、紙パルプ技術タイムス第２８巻第１２号（通
巻第３３３号）昭和６０年１１月１日発行第１〜６頁、
特に３頁表６゜紙バルブ技術タイムス第２９巻第２号（
通巻第３３６号）昭和６１年１月２０日発行第４〜５頁
、特に４頁表１．タビ−・ジャーナｙｖ （Ｔａｐｐｉ
Ｊｏｕｒｎａｌ ）第７０巻第１１号（１９８７年１１
月号）第５５〜６１頁、特に５６頁表、等に近年の実施
状況が示されている。In addition, existing bleaching sequences, such as "/C-E-H-Shun-Atsuri, D/Stone-E-D, -(E)-D2 bleaching sequence (-(E) is rumored to be alkali treatment E) In the former case, it was difficult to maintain the desired whiteness and reduce the amount of bleaching chemicals and alkalis used, and it was not possible to obtain high-viscosity bleached pulp. In the latter case, the optimum pH for stage E and stage D1 is 8 to 11 for stage E, and 2 to 5 for stage D1, which is a big difference, and mixing of the bleaching solution and alkaline solution in dynamic displacement bleaching is unavoidable, and the optimum pH for each stage is The problem was that stable operation under these conditions was difficult.For the sequence of dynamic displacement bleaching, please refer to Paper and Pulp Technology Times, Vol. 28, No. 12 (Continuous Volume No. 333), November 1, 1985. Japanese issue pages 1-6,
Especially on page 3, table 6゜Paper Valve Technology Times Vol. 29 No. 2 (
Volume 336) Published January 20, 1985, pages 4-5, especially page 4 Table 1. Tabby Jharnayv (Tappi
Journal ) Volume 70 No. 11 (November 1987
Recent implementation status is shown on pages 55 to 61 (monthly issue), especially the table on page 56.
本発明は前記した現状に鑑みてなされたもので、リグノ
セルロース材料の動的置換漂白において前記した欠点を
解決し、かつ通常の漂白シーケンスよシも漂白薬品、ア
ルカリ添加量を低減し、白色度、パルプ粘度の秀れたリ
グノセルロース物質の漂白方法を提供することにある。The present invention has been made in view of the above-mentioned current situation, and solves the above-mentioned drawbacks in dynamic displacement bleaching of lignocellulosic materials, reduces the amount of bleaching chemicals and alkali added, and improves the brightness of lignocellulosic materials. The object of the present invention is to provide a method for bleaching lignocellulosic material having excellent pulp viscosity.
本発明について概設すると、本発明はリグノセルロース
物質より得られたパルプを二酸化塩素／塩素段（Ｄ／Ｃ
）−アルカリ／次亜塩素酸塩段（Ｅ、、’Ｈ）−二酸化
塩素段（Ｄ）−二酸化塩素段（Ｄ）の漂白シーケンスで
動的置換漂白することを特徴とするリグノセルロース物
質の漂白方法に存する。To summarize the present invention, the present invention provides pulp obtained from lignocellulosic material at a chlorine dioxide/chlorine stage (D/C).
) - Alkali/hypochlorite stage (E,,'H) - Chlorine dioxide stage (D) - Chlorine dioxide stage (D) Bleaching of lignocellulosic materials characterized by dynamic displacement bleaching in the bleaching sequence It lies in the method.
本発明は一１１記のように動的置換漂白方法を行うこと
をＦ＋ｉｌ提としかつ前記特開昭５９−３０９８０号公
報に示す分割添加法を導入するに当り、従来の５段晒例
えば第１股Ｄ／Ｃ−第２段Ｅ−第３段Ｈ−第４段Ｅ−第
５段りにおいて、Ｄ段にＤ−Ｄとして分割添加法を採用
すると共に、分割添加法による漂白段の増加を避けるた
めに第３段ＨをＤに変更することを試み、多角的に検討
した結果、第２段をアルカリ／次亜塩素酸塩段とするこ
とにより所望の白色度を維持すると共に、漂白薬品、具
体的に塩水社及びアルカリ薬品の使用量の削減を達成し
たものである。The present invention is based on the dynamic substitution bleaching method as described in No. 111, and in introducing the divided addition method shown in JP-A-59-30980, the conventional five-stage bleaching method, for example, the first In the crotch D/C - 2nd stage E - 3rd stage H - 4th stage E - 5th stage, the divided addition method is adopted as D-D in the D stage, and the number of bleaching stages by the divided addition method is increased. In order to avoid this, we tried changing the third stage H to D, and after considering it from various angles, we decided to make the second stage an alkali/hypochlorite stage to maintain the desired degree of whiteness and to avoid bleaching chemicals. Specifically, we achieved a reduction in the amount of salt and alkali chemicals used.
本発明の構成を具体的に明らかにするために動的置換漂
白方法の実機におけるＤ／Ｃ−Ｅ Ｈ−Ｄのシーケンス
と対比して説明する。In order to specifically clarify the structure of the present invention, a comparison will be made with a D/C-E HD sequence in an actual machine of a dynamic displacement bleaching method.
”Ｃ−Ｅ−Ｈ−Ｄの実機における漂白条件は一般にＤ／
Ｃ段ではＤ／Ｃの比率は１ｏ〜３ｏ／９ｏ〜７゜（有効
塩素換算）、対パルプ添加量α１３〜０．４０％／１．
０〜２．０％（有効塩素換算）、漂白温度５０〜７０°
Ｃ１抽出液ｐＨ１，５〜五５である。"The bleaching conditions in the actual C-E-H-D machine are generally D/
In stage C, the D/C ratio is 1o~3o/9o~7o (available chlorine equivalent), and the amount α13~0.40%/1.
0-2.0% (effective chlorine equivalent), bleaching temperature 50-70°
The pH of the C1 extract is 1.5 to 55.
Ｅ段では対パルプアルカ！Ｊ （ＮａＯＨ） ｍ加ｉｔ
１．０〜２．５％、抽出液ｐＨ９，０〜１１．０程度
である。In the E stage, it's against Pulp Arca! J (NaOH) maddition
1.0 to 2.5%, and the pH of the extract is about 9.0 to 11.0.
Ｈ段では次亜塩素酸ソーダの対パルプ添加量０．５〜２
．０％（有効塩素換算）、漂白温度４５〜６５゛Ｃ１抽
出液ｐＨ９，０〜１１．８程度である。Ｄｔ役では二酸
化塩素の対パルプ添加ｉ［Ｌ２〜０．８％（有効塩素換
算）、漂白温度６０〜８０’Ｃ１抽出液ｐＨ３〜５程度
であり、動的置換漂白ンーケンス全体の全有効塩素消費
量は３８〜４８に９／ ＢＤＴ （ＢＤＴは乾燥パルプ
ｔｏｎをいう。）、全アルカリ消費量は３Ｏ−３６ｋｌ
？／ＢＤＴ程度であり、漂白後のパルプの白色度は８３
〜８６％、パルプ粘度１０〜１４ＣＴｌ程度である。In the H stage, the amount of sodium hypochlorite added to the pulp is 0.5 to 2.
．． 0% (in terms of available chlorine), bleaching temperature 45-65°C1 extract pH 9.0-11.8. In the Dt role, chlorine dioxide is added to the pulp i[L2~0.8% (in terms of available chlorine), bleaching temperature is 60~80'C1 extract pH is about 3~5, and the total available chlorine consumption of the entire dynamic displacement bleaching sequence is The amount is 38-48 9/BDT (BDT refers to dry pulp ton), the total alkali consumption is 3O-36kl
? /BDT, and the whiteness of the pulp after bleaching is 83.
~86%, and the pulp viscosity is approximately 10 to 14 CTl.
本発明は従来の”Ｃ−Ｅ−Ｈ−Ｄの動的置換漂白シーケ
ンスのＥ段に少量の次亜塩素酸塩を添加してＥ／’Ｈ段
とし、かつ従来法の第３段のＨ段をＤ段に変更したもの
である。In the present invention, a small amount of hypochlorite is added to the E stage of the conventional "C-E-H-D dynamic displacement bleaching sequence to create the E/'H stage, and the H The stage has been changed to D stage.
以下に本発明の漂白シーケンスＤ／Ｃ−Ｅ／Ｔ（−Ｄｔ
−Ｄ２について説明するっ
Ｄ／Ｃ段ではＤ／Ｃｔｖ比率は１０〜３ｏ／９ｏ〜７０
（有効塩素換算）、対パルプ添加量１１５〜０．４０％
／１．０〜２．０％（有効塩素換算）、漂白温度５ｏ〜
７ｏ″ｃ１抽出ｐＨ９，５〜五５であって、従来法と異
ならない。Ｅ／Ｈ段では対パルプアルカリ（ＮａＯＨ）
添加量１．０−２．５ ％、対パルプＨ（次亜塩素酸塩
）４加量Ｑ、１〜［１，５％（有効塩素換算）、抽出液
ｐＨ５〜９、好ましくはＴ）Ｈ６〜８であって、従来法
に比して次亜塩素酸塩の使用量が少ない。The bleaching sequence of the present invention D/C-E/T (-Dt
- Let me explain about D2. In the D/C stage, the D/Ctv ratio is 10~3o/9o~70
(effective chlorine equivalent), amount added to pulp 115-0.40%
/1.0~2.0% (effective chlorine equivalent), bleaching temperature 5o~
7o"c1 extraction pH 9.5 to 55, which is not different from the conventional method. In the E/H stage, pulp alkali (NaOH)
Addition amount 1.0-2.5%, addition to pulp H (hypochlorite) 4 addition Q, 1 to [1.5% (effective chlorine equivalent), extract pH 5 to 9, preferably T) H6 8, the amount of hypochlorite used is smaller than that of the conventional method.
Ｄｔ段では二酸化塩素の対パルプ添加量はα８Ｇ〜１．
４％（有効塩素換算）、漂白温度は６Ｇ〜８０℃、好ま
しくは６５〜７５°ｃ５抽出液ｐ）Ｔ２〜５、好ましく
は３〜４である。In the Dt stage, the amount of chlorine dioxide added to the pulp is α8G~1.
4% (in terms of available chlorine), the bleaching temperature is 6G to 80°C, preferably 65 to 75°C5 extract p) T2 to 5, preferably 3 to 4.
Ｄ２段では二酸化塩素の対パルプ添加量はｌ１１６゜〜
１．２％（有効塩素換Ｘ）、漂白温度は６０〜８０°Ｃ
５好ましくは６５〜７５°Ｃ１抽出液ｐＨ２〜５、好ま
しくは３〜４である。In the D2 stage, the amount of chlorine dioxide added to the pulp is 116° ~
1.2% (effective chlorine conversion X), bleaching temperature 60-80°C
5 Preferably 65-75°C1 Extract pH 2-5, preferably 3-4.
またＤｔ段とＤ２段の比率Ｉ）１／’Ｄｚは４０〜７０
／６０〜５０である。本発明の漂白シーケンスＤ／ｃ−
Ｅ、１−Ｄ、−Ｄ！全全体全有効塩素消費量（８４段、
Ｄｔ段、Ｄ２段に由来する）は３′５〜４３ゆ／ＢＤＴ
、全アルカリ消費量は１０〜２５ゆ／ ＢＤＴであシ
、漂白後のパルプ白色度は８５〜８６％、パルプ粘度は
１５〜１７ｃｐである。Also, the ratio I)1/'Dz of Dt stage and D2 stage is 40 to 70.
/60 to 50. Bleaching sequence of the present invention D/c-
E, 1-D, -D! Total total available chlorine consumption (84 stages,
(derived from Dt stage, D2 stage) is 3'5~43 Yu/BDT
The total alkali consumption is 10-25 Yu/BDT, the pulp whiteness after bleaching is 85-86%, and the pulp viscosity is 15-17 cp.
本発明のシーケンスのＤ！＋没とＤ２段の間にＷ段（洗
滌段）を加えてもよいし、場合によってはＤｔ段とＤ２
段の間にＥ段を設けてもよい。なお本発明の漂白シーケ
ンス全体の滞溜時間は６０〜９０分程度が好ましい。D! of the sequence of the present invention! A W stage (washing stage) may be added between the +Destination and D2 stages, or in some cases, a W stage (washing stage) may be added between the Dt stage and D2 stage.
An E stage may be provided between the stages. The residence time of the entire bleaching sequence of the present invention is preferably about 60 to 90 minutes.
本発明のリグノセルロース物質の漂白方法はクラフトバ
ルブ（ＫＰ）、アルカリパルプ（ＡＰ ）、サルファイ
ドパルプ（ｓｐ ）等の化学パルプはもちろん砕木バル
ブ（ＧＰ）、リファイナーメカニカルパルプ（ＲＭＰ）
、サーモメカニカルパルプ（ＴＭＰ）、ケミグラウン
ドウッドパルプ（ＣＧＰ） 、セミケミカルパルプ（ｓ
ｅｐ）等の製紙用機械パルプおよび古紙パルプ（脱墨さ
れた二次繊維）等に適用され、更には木材パルプ、非木
材パルプのいずれにも適用可能であることは言うまでも
ないが、好適なパルプとしてはクラフトパルプ、アルカ
リパルプであシ、これらのパルプはあらかじめ酸素漂白
されていてもよい。The method for bleaching lignocellulosic materials of the present invention can be applied to chemical pulps such as kraft pulp (KP), alkaline pulp (AP), sulfide pulp (SP), as well as ground wood pulp (GP) and refiner mechanical pulp (RMP).
, thermomechanical pulp (TMP), chemical ground wood pulp (CGP), semi-chemical pulp (s
It goes without saying that it can be applied to mechanical pulp for papermaking such as EP) and waste paper pulp (deinked secondary fiber), and can also be applied to both wood pulp and non-wood pulp, but it is a suitable pulp. Examples include kraft pulp and alkaline pulp, and these pulps may be oxygen bleached beforehand.
次に、本発明を実施例について説明するが、本発明はこ
れによりなんら限定されるものではない。Next, the present invention will be explained with reference to Examples, but the present invention is not limited thereto in any way.
カバ材の未晒クラフトパルプ（白色度２ＡＯ％、カッパ
ー１曲１９５）を１俊素漂白して得られた白色度４０．
０％カッパー価１Ｑ、５のクラフトバルブを漂白シーケ
ンスＤ／Ｃ−騎−Ｄｔ−Ｄ２で工場の実機によって下記
の第１表に示す条件により動的置換漂白した。この場合
のパルプ濃度は９８％、漂白シーケンス全体の滞溜時間
は７８分であった。なお比較例としてＤ／Ｃ−Ｅ−Ｈ−
Ｄの漂白シーケンスで工場の実機によって動的置換漂白
した結果を漂白条件とともに併せて第１表に示した。The whiteness obtained by bleaching unbleached birch wood kraft pulp (whiteness 2AO%, copper 195) with a whiteness of 40.
Kraft valves having a 0% kappa number of 1Q and 5 were subjected to dynamic displacement bleaching using the bleaching sequence D/C-Ki-Dt-D2 using an actual factory machine under the conditions shown in Table 1 below. The pulp density in this case was 98% and the residence time for the entire bleaching sequence was 78 minutes. As a comparative example, D/C-E-H-
Table 1 shows the results of dynamic displacement bleaching using the bleaching sequence D using an actual machine at the factory, along with the bleaching conditions.
なお表中の試験法は次の方法に従って行った白色度 Ｊ
ＩＳ Ｐ８１２３
前記表からみて、パルプ白色度８５．０を基準値とした
場合、本発明では薬品及びアルカリ消費量が低減され、
しかも高いパルプ粘度が達成されることは明らかである
。The test method in the table is the whiteness J
IS P8123 From the table above, when pulp whiteness of 85.0 is used as the reference value, the amount of chemicals and alkali consumed is reduced in the present invention,
Moreover, it is clear that high pulp viscosities are achieved.
以上の説明から明らかなように、本発明方法の新規な動
的置換漂白のシーケンスにより従来法に比較して漂白剤
の添加率を大巾に低下させ、アルカリ添加量を低下させ
、白色度およびパルプ粘度の秀れたパルプを提供するこ
とが可能となった。As is clear from the above description, the novel dynamic displacement bleaching sequence of the method of the present invention greatly reduces the addition rate of bleach and the amount of alkali addition compared to the conventional method, and reduces the whiteness and It has become possible to provide pulp with excellent pulp viscosity.
また本発明方法は大巾な設備の変更を必要としないとい
う点で設備上の利点が大でおる。Furthermore, the method of the present invention has a great advantage in terms of equipment in that it does not require extensive changes to the equipment.
Claims (1)
塩素／塩素段−アルカリ／次亜塩素酸塩段−二酸化塩素
段−二酸化塩素段の漂白シーケンスで動的置換漂白する
ことを特徴とするリグノセルロース物質の漂白方法。1. A lignocellulosic material characterized by subjecting the pulp obtained from the lignocellulosic material to dynamic displacement bleaching in a bleaching sequence of chlorine dioxide/chlorine stage - alkali/hypochlorite stage - chlorine dioxide stage - chlorine dioxide stage bleaching method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21258388A JPH0663189B2 (en) | 1988-08-29 | 1988-08-29 | Bleaching method for lignocellulosic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21258388A JPH0663189B2 (en) | 1988-08-29 | 1988-08-29 | Bleaching method for lignocellulosic material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0268378A true JPH0268378A (en) | 1990-03-07 |
| JPH0663189B2 JPH0663189B2 (en) | 1994-08-17 |
Family
ID=16625105
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21258388A Expired - Lifetime JPH0663189B2 (en) | 1988-08-29 | 1988-08-29 | Bleaching method for lignocellulosic material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0663189B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5001550A (en) * | 1988-11-11 | 1991-03-19 | General Electric Co. | Quadruplex encoder and decoder for EDTV system |
| JPH04222286A (en) * | 1990-11-30 | 1992-08-12 | Oji Paper Co Ltd | Method for bleaching lignocellulosic substance |
| CN102483279A (en) * | 2009-06-26 | 2012-05-30 | 鲜冻科技股份有限公司 | Continuous food freezing device and continuous food freezing method |
-
1988
- 1988-08-29 JP JP21258388A patent/JPH0663189B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5001550A (en) * | 1988-11-11 | 1991-03-19 | General Electric Co. | Quadruplex encoder and decoder for EDTV system |
| JPH04222286A (en) * | 1990-11-30 | 1992-08-12 | Oji Paper Co Ltd | Method for bleaching lignocellulosic substance |
| CN102483279A (en) * | 2009-06-26 | 2012-05-30 | 鲜冻科技股份有限公司 | Continuous food freezing device and continuous food freezing method |
| US9560858B2 (en) | 2009-06-26 | 2017-02-07 | Technican Co., Ltd. | Continuous food freezing device and continuous food freezing method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0663189B2 (en) | 1994-08-17 |
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