JP5285896B2 - Process for producing bleached alkaline chemical pulp - Google Patents
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- JP5285896B2 JP5285896B2 JP2007314917A JP2007314917A JP5285896B2 JP 5285896 B2 JP5285896 B2 JP 5285896B2 JP 2007314917 A JP2007314917 A JP 2007314917A JP 2007314917 A JP2007314917 A JP 2007314917A JP 5285896 B2 JP5285896 B2 JP 5285896B2
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- 229920001131 Pulp (paper) Polymers 0.000 title claims description 25
- 238000000034 method Methods 0.000 title description 57
- 238000010306 acid treatment Methods 0.000 claims description 52
- 238000004061 bleaching Methods 0.000 claims description 49
- 239000002253 acid Substances 0.000 claims description 36
- 238000010411 cooking Methods 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 23
- 239000003513 alkali Substances 0.000 claims description 19
- 239000012978 lignocellulosic material Substances 0.000 claims description 19
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 13
- 239000000460 chlorine Substances 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- 239000002023 wood Substances 0.000 claims description 6
- 239000011121 hardwood Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000011122 softwood Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 18
- 239000000126 substance Substances 0.000 description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 239000000123 paper Substances 0.000 description 11
- 239000004155 Chlorine dioxide Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 235000019398 chlorine dioxide Nutrition 0.000 description 9
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 6
- 150000004965 peroxy acids Chemical class 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- 239000002655 kraft paper Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- -1 hydride hydride Chemical compound 0.000 description 4
- 239000013055 pulp slurry Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MHSVJXJTONHWLL-VEDIPHOLSA-N (3e,5r)-5-methyl-3-(oxolan-2-ylidene)oxolane-2,4-dione Chemical compound O=C1[C@@H](C)OC(=O)\C1=C/1OCCC\1 MHSVJXJTONHWLL-VEDIPHOLSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- JFBJUMZWZDHTIF-UHFFFAOYSA-N chlorine chlorite Inorganic materials ClOCl=O JFBJUMZWZDHTIF-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000010446 mirabilite Substances 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QGGOCWIJGWDKHC-FSIIMWSLSA-N (2s,3s,4r,5r)-2,4,5-trihydroxy-3-methoxy-6-oxohexanoic acid Chemical group OC(=O)[C@@H](O)[C@@H](OC)[C@H](O)[C@@H](O)C=O QGGOCWIJGWDKHC-FSIIMWSLSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- TUAHMGHBHVFVON-UHFFFAOYSA-N CCCC(C(=O)C(=O)O)(Cl)Cl Chemical compound CCCC(C(=O)C(=O)O)(Cl)Cl TUAHMGHBHVFVON-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000218631 Coniferophyta Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 244000166124 Eucalyptus globulus Species 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 240000000797 Hibiscus cannabinus Species 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003500 enol ether group Chemical group 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- OLAPPGSPBNVTRF-UHFFFAOYSA-N naphthalene-1,4,5,8-tetracarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1C(O)=O OLAPPGSPBNVTRF-UHFFFAOYSA-N 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- NIFHFRBCEUSGEE-UHFFFAOYSA-N oxalic acid Chemical compound OC(=O)C(O)=O.OC(=O)C(O)=O NIFHFRBCEUSGEE-UHFFFAOYSA-N 0.000 description 1
- 230000000361 pesticidal effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229920001221 xylan Polymers 0.000 description 1
- 150000004823 xylans Chemical class 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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Description
本発明は、リグノセルロース物質を原料とし、アルカリ蒸解工程後に、元素状塩素及び次亜塩素酸共に用いない漂白工程を有する漂白アルカリ化学パルプの製造方法であって、アルカリ蒸解工程後に、酸処理工程、漂白工程、をこの順に有する漂白アルカリ化学パルプの製造方法に関するものである。 The present invention is a method for producing bleached alkaline chemical pulp using a lignocellulosic material as a raw material and having a bleaching step in which neither elemental chlorine nor hypochlorous acid is used after the alkali cooking step, and the acid treatment step after the alkali cooking step The present invention relates to a method for producing bleached alkaline chemical pulp having bleaching steps in this order.
漂白アルカリ化学パルプの製造方法には、ソーダパルプ法やクラフトパルプ法にて、木材チップ等のリグノセルロース物質を苛性ソーダのみ又は苛性ソーダと硫化ソーダの混合の蒸解液で蒸解し、得られたアルカリ化学パルプを、更にアルカリ酸素脱リグニンを行い又は行わず、洗浄精選を行った後、漂白工程を経るのが一般的である。また、ソーダパルプ法はクラフトパルプ法に比べ歩留が低く、パルプの強度が劣り、且つ、蒸解薬品の苛性ソーダの回収率が低い問題を有するため、クラフトパルプ法が現在主流の蒸解法となっている。 The method for producing bleached alkaline chemical pulp is a soda pulp method or a kraft pulp method, in which lignocellulosic materials such as wood chips are digested with only caustic soda or a mixture of caustic soda and sodium sulfide, and the resulting alkaline chemical pulp In general, a bleaching step is carried out after further washing and selection with or without alkaline oxygen delignification. The soda pulp method has a lower yield than the kraft pulp method, the strength of the pulp is inferior, and the recovery rate of caustic soda as a cooking chemical is low, so the kraft pulp method has become the mainstream cooking method. Yes.
アルカリ化学パルプの漂白方法には、主に下記の３方法がある。即ち、従来の塩素漂白方法、近年の無塩素漂白方法（Ｅｌｅｍｅｎｔａｌ Ｃｈｌｏｒｉｎｅ−Ｆｒｅｅ：ＥＣＦ）及び完全無塩素漂白方法（Ｔｏｔａｌｌｙ Ｃｈｌｏｒｉｎｅ−Ｆｒｅｅ：ＴＣＦ）である。 There are mainly the following three methods for bleaching alkaline chemical pulp. That is, they are a conventional chlorine bleaching method, a recent chlorine-free bleaching method (Elemental Chlorine-Free: ECF), and a complete chlorine-free bleaching method (Totally Chlorine-Free: TCF).
塩素漂白では、元素状塩素や次亜塩素酸塩と、二酸化塩素、酸素、過酸化水素、苛性ソーダ等の薬品との組合せによりアルカリ化学パルプを漂白処理するが、塩素漂白法において生成する有機塩素化合物が、環境に悪影響を及ぼす恐れがあり、近年の環境保護の高まりも受け、元素状塩素の使用が避けられている。更に、次亜塩素酸塩を使用する漂白方法においては、次亜塩素酸の使用により発生するクロロホルムが、人体に悪影響を及ぼす懸念もあるため、現在では、塩素と次亜塩素酸塩を含まないＥＣＦ及びＴＣＦによる漂白方法が主流になっている。 In chlorine bleaching, alkaline chemical pulp is bleached with a combination of elemental chlorine and hypochlorite and chemicals such as chlorine dioxide, oxygen, hydrogen peroxide, and caustic soda. However, there is a risk of adverse effects on the environment, and due to the recent increase in environmental protection, the use of elemental chlorine is avoided. Furthermore, in the bleaching method using hypochlorite, there is a concern that chloroform generated by the use of hypochlorous acid may adversely affect the human body, so it currently does not contain chlorine and hypochlorite. The bleaching method using ECF and TCF has become mainstream.
これらＥＣＦ及びＴＣＦによる漂白方法において使用する薬品は、ＥＣＦ漂白方法では、二酸化塩素、過酸化水素、オゾン、酸素、苛性ソーダ等が用いられ、ＴＣＦ漂白方法では、キレート剤、過酸化水素、オゾン、酸素、苛性ソーダ及び過酢酸等が用いられるが、ＥＣＦ漂白方法による漂白パルプはＴＣＦ漂白方法による漂白パルプより白色度が高く、コストも安価であるため、ＥＣＦ漂白方法の採用が国内では増加している。 The chemicals used in these ECF and TCF bleaching methods are chlorine dioxide, hydrogen peroxide, ozone, oxygen, caustic soda, etc. in the ECF bleaching method, and chelating agents, hydrogen peroxide, ozone, oxygen in the TCF bleaching method. Caustic soda, peracetic acid, and the like are used, but bleached pulp produced by the ECF bleaching method has higher whiteness and lower cost than bleached pulp produced by the TCF bleaching method. Therefore, the use of the ECF bleaching method is increasing in Japan.
アルカリ蒸解過程では、リグノセルロース物質のヘミセルロースであるキシランの側鎖を有する、４−Ｏ−メチルグルクロン酸残基が、アルカリ加水分解により脱メトキシールされ、ヘキセンウロン酸（ＨｅｘＡ）を生成する（例えば、Ｊｉａｎｇ，Ｚ−ｈ．，Ｌｉｅｒｏｐ，Ｂ．Ｖ．，Ｂｅｒｒｙ，Ｒ．Ｈｅｘｅｎｕｒｏｎｉｃ ａｃｉｄ ｇｒｏｕｐｓ ｉｎ ｐｕｌｐｉｎｇ ａｎｄ ｂｌｅａｃｈｉｎｇ ｃｈｅｍｉｓｔｒｙ．Ｔａｐｐｉ Ｊｏｕｒｎａｌ ８３（１）：１６７−１７５（２０００）参照。）。ＨｅｘＡの化学構造にはエノールエテール基を有し、特徴として、求電子および求核の攻撃を受けやすいため、ＥＣＦ漂白方法、ＴＣＦ漂白方法で使用される二酸化塩素、オゾン等を消費してしまうため、漂白薬品のコストアップの原因になる。また、ＨｅｘＡは二酸化塩素、オゾンとの反応により蓚酸（シュウ酸）を生成し、精選設備においてカルシウムと結合することで蓚酸カルシウムとなり、スケールの問題を発現する。 In the alkali cooking process, 4-O-methylglucuronic acid residues having a side chain of xylan, which is a lignocellulosic material hemicellulose, are demethoxylated by alkaline hydrolysis to produce hexeneuronic acid (HexA) (for example, Jiang). Zh., Lierop, BV, Berry, R. Hexenuronic acid groups in pulling and bleaching chemistry. Tapi Journal 83 (1): 167-175 (2000)). The chemical structure of HexA has an enol-ether group, and is characterized by being susceptible to electrophilic and nucleophilic attacks, thus consuming chlorine dioxide, ozone, etc. used in ECF bleaching and TCF bleaching methods. As a result, the cost of bleaching chemicals increases. HexA produces oxalic acid (oxalic acid) by reaction with chlorine dioxide and ozone, and becomes calcium oxalate when combined with calcium in a selective facility, which causes scale problems.
さらに、特許文献１には、ＥＣＦ漂白方法において、特に二酸化塩素を用いる漂白方法においては、漂白後のパルプが黄変化する問題を有し、この問題に対して、ＥＣＦ漂白工程の前工程で、硫酸などによりアルカリ化学パルプの酸処理を行い、黄変化の原因物質と考えられているＨｅｘＡを分解、除去する方法が開示されている。 Further, Patent Document 1 has a problem that the bleached pulp is yellowed in the ECF bleaching method, particularly in the bleaching method using chlorine dioxide, and for this problem, in the previous step of the ECF bleaching step, A method for decomposing and removing HexA, which is considered to be a causative substance for yellowing, by acid treatment of alkaline chemical pulp with sulfuric acid or the like is disclosed.
一方、アルカリ蒸解過程においては、過蒸解と未蒸解を避けるため、蒸解度合の指標として、カッパー価が広く使用されている。カッパー価とは、２５℃の温度と１０分間の反応時間の一定条件下で、０．１Ｎ過マンガン酸カリウムの１００ｍｌ添加量の半分が消費されるように、測定パルプのサンプル量を調整する測定方法である。 On the other hand, in the alkali cooking process, the kappa number is widely used as an index of the degree of cooking in order to avoid overcooking and uncooking. The kappa number is a measurement that adjusts the sample amount of the measuring pulp so that half of the added amount of 100 ml of 0.1 N potassium permanganate is consumed under a constant condition of a temperature of 25 ° C. and a reaction time of 10 minutes. Is the method.
一般的に、カッパー価は、パルプに含まれるリグニン含有量と相当すると考えられるが、最近では、ＨｅｘＡも過マンガン酸カリウムを消費する事が見出されているため、カッパー価は、リグニンおよびＨｅｘＡを含めた含有量を示しているといえる。因みに、１０μｍｏｌのＨｅｘＡは０．８４のカッパー価に相当する（例えば、Ｌｉ，Ｊ．，Ｇｅｌｌｅｒｓｔｅｄｔ，Ｇ．Ｔｈｅ ｃｏｎｔｒｉｂｕｔｉｏｎ ｔｏ ｋａｐｐａ ｎｕｍｂｅｒ ｆｒｏｍ ｈｅｘｅｎｅｕｒｏｎｉｃ ａｃｉｄ ｇｒｏｕｐｓ ｉｎ ｐｕｌｐ ｘｙｌａｎ．Ｃａｒｂｏｈｙｄｒａｔｅ Ｒｅｓｅａｒｃｈ ３０２：２１３−２１８（１９９７）参照。）。 In general, the kappa number is considered to correspond to the lignin content contained in the pulp, but recently, HexA has also been found to consume potassium permanganate, so the kappa number is determined to be lignin and HexA. It can be said that the content including is shown. By the way, 10 μmol of HexA corresponds to a kappa number of 0.84 (for example, Li, J., Gellerstedt, G. The contribution to kappa number from hexeneuronic acid groups in Rex. reference.).
カッパー価に関して、例えば、特許文献２には、次の酸処理の条件と効果を記載している。
（１）酸処理の条件は、温度：８５〜１５０℃、ｐＨ：２〜５、反応時間：５分〜１０時間。
（２）酸処理によりパルプのカッパー価が３〜６単位減少し、ＨｅｘＡ基が少なくとも５０％除去される。
Regarding the kappa number, for example, Patent Literature 2 describes the conditions and effects of the following acid treatment.
(1) Conditions for acid treatment are: temperature: 85 to 150 ° C., pH: 2 to 5, reaction time: 5 minutes to 10 hours.
(2) Acid treatment reduces the pulp kappa number by 3-6 units and removes at least 50% HexA groups.
前記特許文献２に記載の条件とその効果については、下記業界誌にも記載されている。例として、フィンランドのＵＰＭ−キミネ社ヴィサフォレスト工場では、酸処理の温度８６℃、ｐＨ３．５、滞留時間７時間の条件を使用した場合、カッパー価が３．５ポイント低下し、パルプ紙力が１５％減少した（例えば、Ｓｉｌｔａｌａ，Ｍ．，Ｗｉｎｂｅｒｇ，Ｋ．，Ａｌｅｎｉｕｓ，Ｍ．，Ｈｅｎｒｉｃｓｏｎ，Ｋ．，Ｌｏｎｎｂｅｒｇ，Ｂ．，Ｋｅｓｋｉｎｅｎ，Ｎ．Ｍｉｌｌ ｓｃａｌｅ ａｐｐｌｉｃａｔｉｏｎ ｆｏｒ ｓｅｌｅｃｔｉｖｅ ｈｙｄｒｏｌｙｓｉｓ ｏｆ ｈｅｘｅｎｕｒｏｎｉｃ ａｃｉｄ ｇｒｏｕｐｓ ｉｎ ＴＣＦｚ ｂｌｅａｃｈｉｎｇ ｏｆ ｋｒａｆｔ ｐｕｌｐ．Ｉｎ Ｐｒｏｃｅｅｄｉｎｇｓ ｏｆ １９９８ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｐｕｌｐ Ｂｌｅａｃｈｉｎｇ Ｃｏｎｆｅｒｅｎｃｅ，Ｂｏｏｋ １，ｐｐ．２７９−２８７参照。）。また、ブラジルのリオクラビン工場では、温度９０℃、ｐＨ３．５、滞留時間１４０分の酸処理条件下では、パルプのカッパー価が３．５ポイント減少し、同時にパルプの紙力が１０ポイント／１ポイントカッパー価下がった（例えば、Ｒａｔｎｉｅｋｓ，Ｅ．，Ｖｅｎｔｕｒａ，Ｊ．Ｗ．，Ｍｅｎｓｃｈ，Ｍ．Ｒ．，Ｚａｎｃｈｉｎ，Ｒ．Ａ．Ａｃｉｄ ｓｔａｇｅ ｉｍｐｒｏｖｅｓ ｐｒｏｄｕｃｔｉｏｎ ｉｎ ｅｕｃａｌｙｐｔｕｓ ｆｉｂｅｒ ｌｉｎｅ．Ｃａｎａｄａ Ｐｕｌｐ ＆ Ｐａｐｅｒ １０２（１２）：Ｔ３４５−Ｔ３４８（２００１）参照。）。 The conditions described in Patent Document 2 and the effects thereof are also described in the following industry magazines. For example, in the Finnish UPM-Kimine Visa Forest factory, when the acid treatment temperature of 86 ° C., pH 3.5, and residence time of 7 hours were used, the kappa number dropped by 3.5 points, and the pulp paper strength decreased. Reduced by 15% (e.g., Siltala, M., Winberg, K., Alenius, M., Henricson, K., Lonberg, B., Keskinen, N. Mill scale application for selective hydride hydride zigro hydride hydride sigmo fre hydride sigmo fro hydride hydride s? craft pull.In Proceedings of 1998 International Pulping Bleaching Conference Book 1, pp.279-287 reference.). In addition, at the Rio Clavin plant in Brazil, the pulp kappa number decreased by 3.5 points and the paper strength of the pulp increased by 10 points / 1 point at 90 ° C, pH 3.5, and residence time of 140 minutes. Copper value decreased (e.g., Ratnieks, E., Ventura, JW, Mensch, MR, Zanchin, RA Acid stage implant production in eucalyptus fiber line. Canada & Palp. 102). (See T345-T348 (2001).)
これら、紙・パルプ製造工場の実績から、酸処理を行ったパルプは、パルプ紙力が低下することが認められている。 From the results of these paper / pulp manufacturing factories, it is recognized that pulp subjected to acid treatment has reduced pulp paper strength.
このパルプ紙力低下の課題を改善する方策として、例えば、特許文献３には、酸処理工程において、硫酸の添加の他に、亜硫酸塩を添加することによりパルプの紙力が維持し、且つ、カッパー価を減少させる技術が開示されている。また、例えば、特許文献１は、酸処理工程での硫酸の添加の他に二酸化塩素発生システムからなる副産物質であるセスキ芒硝を添加する技術が開示されている。 As a measure for improving the problem of lowering pulp paper strength, for example, in Patent Document 3, in addition to the addition of sulfuric acid in the acid treatment step, the paper strength of pulp is maintained by adding sulfite, and A technique for reducing the kappa number is disclosed. Further, for example, Patent Document 1 discloses a technique of adding sesqui mirabilite, which is a by-product substance composed of a chlorine dioxide generation system, in addition to the addition of sulfuric acid in the acid treatment process.
然しながら、上記の特許文献に記載されている添加剤である、亜硫酸塩及びセスキ芒硝は、共に還元剤であり、弱酸でも薬品が以下の反応１にて分解する問題を有する。
（化１）
Ｎａ2ＳＯ3＋２Ｈ+→２Ｎａ+＋Ｈ2Ｏ＋ＳＯ2（反応１）
However, the additives described in the above-mentioned patent documents, both sulfite and sesqui mirabilite, are both reducing agents, and have a problem that the chemical decomposes in the following reaction 1 even with a weak acid.
(Chemical formula 1)
Na 2 SO 3 + 2H + → 2Na + + H 2 O + SO 2 (Reaction 1)
さらに、これらの還元剤の飽和溶液のｐＨは弱アルカリ性であるため酸処理工程で使用すると、酸処理の酸性溶液のｐＨが上がり、また、反応１により、酸の濃度が下がるため、特許文献１又は特許文献３に開示された技術により、酸処理を行ったパルプのカッパー価の減少、パルプ紙力の維持、ＨｅｘＡ基の除去等という向上効果が得られるかどうかは疑問に思われる。即ち、酸処理を行ったパルプのカッパー価の減少、パルプ紙力の維持、ＨｅｘＡ基の除去率向上等の課題がまだ残っている。
本発明が解決しようとする主たる課題は、リグノセルロース物質を原料とし、アルカリ蒸解工程後に、元素状塩素及び次亜塩素酸共に用いない漂白工程を有する漂白アルカリ化学パルプの製造方法であって、アルカリ蒸解工程後に、酸処理工程、漂白工程、をこの順に有する漂白アルカリ化学パルプの製造方法に関し、前記酸処理工程におけるパルプ紙力の維持、ＨｅｘＡ基の除去率向上、カッパー価の低減を図ることができる、漂白アルカリ化学パルプの製造方法を提供することにある。 The main problem to be solved by the present invention is a method for producing bleached alkaline chemical pulp using a lignocellulosic material as a raw material and having a bleaching step in which neither elemental chlorine nor hypochlorous acid is used after the alkali cooking step, Regarding a method for producing a bleached alkaline chemical pulp having an acid treatment step and a bleaching step in this order after the cooking step, the pulp paper strength in the acid treatment step can be maintained, the HexA group removal rate can be improved, and the kappa number can be reduced. An object of the present invention is to provide a method for producing bleached alkaline chemical pulp.
この課題を解決した本発明は、次のとおりである。
〔請求項１記載の発明〕
リグノセルロース物質を原料とし、アルカリ蒸解工程後に、元素状塩素及び次亜塩素酸共に用いない漂白工程を有する漂白アルカリ化学パルプの製造方法であって、
前記アルカリ蒸解工程後に、酸処理工程、前記漂白工程、をこの順に有し、
前記漂白工程前段の酸処理工程において、酸の添加と併せて、２ＫＨＳＯ 5 ・ＫＨＳＯ 4 ・Ｋ 2 ＳＯ 4 である一過硫酸塩化合物をカロ酸に換算した添加量が前記リグノセルロース物質の絶乾量（質量基準）に対して０．０５〜１．０％となるように添加し、
前記酸処理工程を、ｐＨ３．２〜４．０、温度９０〜１００℃、処理時間１〜５時間の処理条件で行う、
ことを特徴とする漂白アルカリ化学パルプの製造方法。
The present invention that has solved this problem is as follows.
[Invention of Claim 1]
Using a lignocellulosic material as a raw material, after the alkali cooking step, a method for producing bleached alkaline chemical pulp having a bleaching step in which neither elemental chlorine nor hypochlorous acid is used,
After the alkali cooking step, the acid treatment step, the bleaching step, in this order,
In the acid treatment step preceding the bleaching step, in addition to the addition of acid, the addition amount of the monopersulfate compound, which is 2KHSO 5 · KHSO 4 · K 2 SO 4 , converted to caloic acid is the absolute dryness of the lignocellulosic material. Add to 0.05 to 1.0% with respect to the amount (mass basis) ,
The acid treatment step is performed under treatment conditions of pH 3.2 to 4.0, temperature 90 to 100 ° C., treatment time 1 to 5 hours,
A method for producing bleached alkaline chemical pulp, characterized in that
〔請求項２記載の発明〕
前記リグノセルロース物質が、広葉樹チップ、針葉樹チップ及び非木材物質のいずれか一種以上からなる、請求項１記載の漂白アルカリ化学パルプの製造方法。
[Invention of Claim 2 ]
The lignocellulosic material is hardwood chips, consisting of any one or more softwood chips and non-wood materials, method for producing bleached alkaline chemical pulp according to claim 1 Symbol placement.
本発明によると、リグノセルロース物質を原料とし、アルカリ蒸解工程後に、元素状塩素及び次亜塩素酸共に用いない漂白工程を有する漂白アルカリ化学パルプの製造方法であって、アルカリ蒸解工程後に、酸処理工程、漂白工程、をこの順に有する漂白アルカリ化学パルプの製造方法に関し、前記酸処理工程におけるパルプ紙力の維持、ＨｅｘＡ基の除去率アップ、カッパー価低減の改善が図られる漂白アルカリ化学パルプの製造方法となる。 According to the present invention, a method for producing bleached alkaline chemical pulp using a lignocellulosic material as a raw material and having a bleaching step in which neither elemental chlorine nor hypochlorous acid is used after the alkali cooking step, wherein the acid treatment is performed after the alkali cooking step. The present invention relates to a method for producing bleached alkaline chemical pulp having a bleaching step and a bleaching step in this order. Become a method.
本発明は、リグノセルロース物質を原料とし、アルカリ蒸解工程後に、元素状塩素及び次亜塩素酸共に用いない漂白工程を有する漂白アルカリ化学パルプの製造方法であって、アルカリ蒸解工程後に、酸処理工程、漂白工程、をこの順に有する漂白アルカリ化学パルプの製造方法に関し、前記酸処理工程において、好ましくはｐＨ１．０〜５．０、より好ましくはｐＨ２．０〜４．０、好ましくは温度６０〜１００℃、より好ましくは温度７０〜９５℃、好ましくは反応時間１〜５時間、より好ましくは１．５〜３．５時間、大気圧の酸性水溶液にリグノセルロース物質の絶乾量に対する０．０５〜１．０％の過酸、好ましくは一過硫酸塩化合物のカロ酸、より好ましくは０．１〜０．５％の一過硫酸塩化合物のカロ酸を添加すると、カロ酸等を添加しない酸処理よりカッパー価が０〜２３．１％、ＨｅｘＡ基が１８．５〜３７．７％更に低下し、且つ、パルプの強度品質が同等で酸処理が改良された漂白アルカリ化学パルプが得られる。一過硫酸塩化合物のカロ酸の他の過酸としては、過蟻酸、過酢酸等を例示することができ、これらの過酸でも同様な効果が得られる。 The present invention is a method for producing bleached alkaline chemical pulp using a lignocellulosic material as a raw material and having a bleaching step in which neither elemental chlorine nor hypochlorous acid is used after the alkali cooking step, and the acid treatment step after the alkali cooking step In the acid treatment step, the pH is preferably from 1.0 to 5.0, more preferably from pH 2.0 to 4.0, and preferably from 60 to 100. ° C, more preferably a temperature of 70 to 95 ° C, preferably a reaction time of 1 to 5 hours, more preferably 1.5 to 3.5 hours, 0.05 to 3.5% of the dry amount of lignocellulosic material in an acidic aqueous solution at atmospheric pressure. When 1.0% peracid, preferably monopersulfate compound caloic acid, more preferably 0.1-0.5% monopersulfate compound caloic acid is added, Bleached alkaline chemical pulp with a kappa number of 0 to 23.1%, HexA group of 18.5 to 37.7%, and a pulp strength quality equivalent and improved acid treatment. Is obtained. Examples of other peracids of the monopersulfate compound caloic acid include formic acid, peracetic acid, and the like, and similar effects can be obtained with these peracids.
本発明において、酸処理工程のｐＨが１．０未満では、設備上困難であり、ｐＨが５．０を超えるとＨｅｘＡ基の除去率アップ、カッパー価低減の効果が見られない。 In the present invention, when the pH of the acid treatment step is less than 1.0, it is difficult on the equipment, and when the pH exceeds 5.0, the effect of increasing the HexA group removal rate and reducing the kappa number is not seen.
また、酸処理工程の温度が６０℃未満では、ＨｅｘＡ基の除去率アップ、カッパー価低減の効果が見られない。温度が１００℃を超えると圧力容器の設備が必要になり、設備の保全と操業の安全性の問題が生じる。 Moreover, if the temperature of an acid treatment process is less than 60 degreeC, the effect of the removal rate improvement of a HexA group and a kappa number reduction will not be seen. When the temperature exceeds 100 ° C., equipment for pressure vessels is required, which causes problems of equipment maintenance and operational safety.
更に、酸処理工程の反応時間が１時間未満では、ＨｅｘＡ基の除去率アップ、カッパー価低減の効果が見られない、反応時間が５時間を越えてもＨｅｘＡ基の除去率、カッパー価低減は頭打ちになり、費用対効果が見られない。 Furthermore, if the reaction time of the acid treatment step is less than 1 hour, the effect of increasing the HexA group removal rate and reducing the kappa number is not seen. Even if the reaction time exceeds 5 hours, the removal rate of HexA group and reducing the kappa number are not It has reached its peak and is not cost-effective.
さらには、過酸のリグノセルロース物質の絶乾量に対する添加量が、０．０５％未満では、ＨｅｘＡ基の除去率アップ、カッパー価低減の効果が見られない。添加量が１．０％を超えるとＨｅｘＡ基の除去率、カッパー価低減は頭打ちになり、費用対効果が見られない。 Furthermore, when the amount of peracid added relative to the absolute dry amount of the lignocellulosic material is less than 0.05%, the effects of increasing the HexA group removal rate and reducing the kappa number are not observed. When the addition amount exceeds 1.0%, the HexA group removal rate and the kappa number reduction reach a peak, and no cost-effectiveness is observed.
以下、本願発明をさらに詳しく説明する。
ＨｅｘＡ基は酸性環境において非常に不安定である。ＨｅｘＡ基を分解するには、酸処理が一般的な公知手段であり、分解物質は、主に２−フロン酸（約９０％）、５−フォルミル−２−フロン酸（約１０％）及び微量の蟻酸である（例えば、Ｊｉａｎｇ，Ｚ−ｈ．，Ｌｉｅｒｏｐ，Ｂ．Ｖ．，Ｂｅｒｒｙ，Ｒ．Ｈｅｘｅｎｕｒｏｎｉｃ ａｃｉｄ ｇｒｏｕｐｓ ｉｎ ｐｕｌｐｉｎｇ ａｎｄ ｂｌｅａｃｈｉｎｇ ｃｈｅｍｉｓｔｒｙ．Ｔａｐｐｉ Ｊｏｕｒｎａｌ ８３（１）：１６７−１７５（２０００）参照。）。しかし、酸処理工程はＨｅｘＡ基を完全に分解できないため、よりＨｅｘＡ基の高除去率の改良された酸処理工程が必要となっている。
Hereinafter, the present invention will be described in more detail.
HexA groups are very unstable in acidic environments. In order to decompose the HexA group, acid treatment is a generally known means, and decomposition substances mainly include 2-furonic acid (about 90%), 5-formyl-2-furonic acid (about 10%) and a trace amount. (See, for example, Jiang, Zh., Lierop, BV, Berry, R. Hexenuronic acid groups in pulling and bleaching chemistry. Tapi Journal 83 (1): 167-175 (2000)). . However, since the acid treatment step cannot completely decompose the HexA group, an acid treatment step with an improved removal rate of the HexA group is required.
例えば、オゾンによる漂白工程を初段に有するＥＣＦ漂白シーケンスにおいて、ＨｅｘＡ基はオゾンと反応し、テトラジアルドーズ、テトラウロン酸及び蓚酸の反応物質が生成される。一方、二酸化塩素による漂白工程を初段に有するＥＣＦ漂白シーケンスの場合では、ＨｅｘＡ基が二酸化塩素と反応し、テトラ酸、ペンタ酸、２−クロロ−２−デオキシペンタ酸、３−デオキシ−３，３−ジクロロ−２−オキソヘキサ酸等を生成する（例えば、Ｖｕｏｒｉｎｅｎ，Ｔ．，Ｆａｇｅｒｓｔｒｏｍ，Ｐ．，Ｒａｓａｎｅｎ，Ｅ．，Ｖｉｋｋｕｌａ，Ａ．Ｓｅｌｅｃｔｉｖｅ ｈｙｄｒｏｌｙｓｉｓ ｏｆ ｈｅｘｅｎｕｒｏｎｉｃ ａｃｉｄ ｇｒｏｕｐｓ ｏｐｅｎｓ ｎｅｗ ｐｏｓｓｉｂｉｌｉｔｉｅｓ ｆｏｒ ｄｅｖｅｌｏｐｍｅｎｔ ｏｆ ｂｌｅａｃｈｉｎｇ ｐｒｏｃｅｓｓｅｓ．Ｉｎ Ｐｒｏｃｅｅｄｉｎｇｓ ｏｆ １９９７ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｓｏｃｉｅｔｙ ｏｆ Ｗｏｏｄ ａｎｄ Ｐｕｌｐｉｎｇ Ｃｈｅｍｉｓｔｒｙ Ｃｏｎｆｅｒｅｎｃｅ，ｐｐ．Ｍ４−１〜Ｍ４−４参照。）。即ち、酸処理工程後のＨｅｘＡ基が残存すると、ＥＣＦ漂白工程で用いられる高価なオゾン、二酸化塩素を消費し、漂白薬品費の上昇を招くため、更なるＨｅｘＡ基の除去率を向上させる酸処理工程が必要である。 For example, in an ECF bleaching sequence having a bleaching step with ozone in the first stage, the HexA group reacts with ozone to produce reactants of tetradialdose, tetrauronic acid and succinic acid. On the other hand, in the case of an ECF bleaching sequence having a bleaching step with chlorine dioxide in the first stage, the HexA group reacts with chlorine dioxide, resulting in tetraacid, pentanoic acid, 2-chloro-2-deoxypentanoic acid, 3-deoxy-3,3. Producing dichloro-2-oxohexanoic acid and the like (eg, Vuorenen, T., Fagerstrom, P., Rasanen, E., Vikkula, A. Selective hydrology of hexenosociative groups of pesticidal groups. of 1997 International Society of Wood and Pulling C hemistry Conference, pp. M4-1 to M4-4). That is, if the HexA group remains after the acid treatment step, expensive ozone and chlorine dioxide used in the ECF bleaching step are consumed, leading to an increase in the bleaching chemical cost. Therefore, the acid treatment further improves the removal rate of the HexA group. A process is required.
本形態においては、リグノセルロース物質の種類、アルカリ蒸解の方法と条件、ＥＣＦ・ＴＣＦ漂白シーケンスの組合せ、アルカリ酸素脱リグニン有無等いずれにもかかわらず、ＥＣＦ・ＴＣＦ漂白工程に移行する前の酸処理工程で、過酸、特には一過硫酸塩化合物のカロ酸をリグノセルロース物質の絶乾量に対し０．０５〜１．０％、より好ましくは０．１〜０．５％添加することにより、更には、酸処理工程の処理条件として、好ましくはｐＨ１．０〜５．０、より好ましくはｐＨ２．０〜４．０、好ましくは温度６０〜１００℃、より好ましくは温度７０〜９５℃、好ましくは反応時間１〜５時間、より好ましくは１．５〜３．５時間で酸処理を行うことで、酸処理後のパルプのカッパー価を０〜２３．１％、ＨｅｘＡ基を１８．５〜３７．７％更に向上させることができることを見出したものである。 本発明者等の知見では、ＨｅｘＡ基と一過硫酸塩化合物のカロ酸との反応は、反応２にて行われると思われる。
本形態で使用するリグノセルロース物質としては、木材物質（広葉樹、針葉樹）のほか、非木材物質（ケナフト、わら、バガス、竹等）も使用することができる。そして、アルカリ蒸解法は、例えば、従来のキンベンショナル、改良されたソーダパルプ法、クラフトパルプ法等の蒸解法を例示することができる。 As the lignocellulosic material used in this embodiment, non-wood materials (such as kenaf, straw, bagasse, bamboo, etc.) can be used in addition to wood materials (hardwood, conifer). And the alkali cooking method can illustrate cooking methods, such as the conventional kimbennial, the improved soda pulp method, a kraft pulp method, for example.
また、本形態で採用することができる未晒パルプの製造工程の中のアルカリ酸素脱リグニン工程と洗浄・精選の工程における設備及び操業方法は、従来公知のものを好適に用いることができる。 Moreover, the conventionally well-known thing can be used suitably for the installation in the alkali oxygen delignification process in the manufacturing process of the unbleached pulp which can be employ | adopted by this form, and the process in the process of washing | cleaning / selection.
本形態では、カロ酸としてＥ．Ｉ．ｄｕ Ｐｏｎｔ ｄｅ Ｍｅｍｏｕｒｓ ＆ Ｃｏ．の商品であるオキソンを使用しているが、カロ酸は硫酸と過酸化水素の反応からなる生成物質であり、酸処理工程で硫酸が使用された場合、過酸化水素を添加することによりカロ酸が生成され（反応３）、オキソンを使用しなくともカロ酸の添加と同等の効果を得ることができる。なお、本発明者等の知見では、カロ酸を生成するためには、硫酸と過酸化水素のモル比の１：１から１：１／１６までが適正な範囲と思われる。
（化３）
Ｈ2ＳＯ4 ＋ Ｈ2Ｏ2→Ｈ2ＳＯ5＋Ｈ2Ｏ（反応３）
In this embodiment, E. coli as caroic acid. I. du Pont de Meurs & Co. Oxone, which is a product of the product, is produced by the reaction of sulfuric acid and hydrogen peroxide. When sulfuric acid is used in the acid treatment process, caloic acid is added by adding hydrogen peroxide. (Reaction 3), and the same effect as the addition of caroic acid can be obtained without using oxone. According to the knowledge of the present inventors, it is considered that an appropriate range is 1: 1 to 1: 1/16 of the molar ratio of sulfuric acid to hydrogen peroxide for producing caroic acid.
(Chemical formula 3)
H 2 SO 4 + H 2 O 2 → H 2 SO 5 + H 2 O (reaction 3)
〔その他〕
上記記載の本形態の酸処理工程が改良された漂白アルカリ化学パルプの製造方法においては、次のような効果がある。
[Others]
In the manufacturing method of the bleaching alkali chemical pulp by which the acid treatment process of this form of the said description was improved, there exist the following effects.
（１）本発明の酸処理工程が改良された漂白アルカリ化学パルプの製造方法において、例えば、酸処理のｐＨを１．０〜５．０、温度６０℃〜１００℃、反応時間を１〜５時間の条件下で酸の添加の他に、リグノセルロース物質の絶乾量に対し０．０５〜１．０％の過酸、特には一過硫酸塩化合物のカロ酸を添加することにより、酸処理後のパルプのカッパー価を０〜２３．１％、ＨｅｘＡ基を１８．５〜３７．７％更に向上させることができる。 (1) In the method for producing bleached alkaline chemical pulp improved in the acid treatment step of the present invention, for example, the pH of acid treatment is 1.0 to 5.0, the temperature is 60 ° C to 100 ° C, and the reaction time is 1 to 5 In addition to the addition of acid under time conditions, the addition of 0.05-1.0% peracid, in particular the monopersulfate compound caloic acid, relative to the absolute dryness of the lignocellulosic material, The kappa number of the treated pulp can be further improved by 0 to 23.1%, and the HexA group can be further improved by 18.5 to 37.7%.
（２）更に、漂白排水のＣＯＤ負荷が減少することにより地球環境を保護でき、排水処理薬品の費用も低減可能な効果がある。 (2) Further, since the COD load of bleaching wastewater is reduced, the global environment can be protected, and the cost of wastewater treatment chemicals can be reduced.
（３）酸処理工程の酸排水は塩素根がなく、且つ、リグニン、ＨｅｘＡ基の分解物質の有機物質が含まれるため、蒸解工程において生じる黒液に混合して、アルカリ蒸解法の薬品回収工程へ移行することにより、エネルギー源として利用可能であり、環境にも優しい技術となる。 (3) Acid drainage in the acid treatment process has no chlorine roots and contains organic substances such as lignin and HexA-based decomposition substances, so it is mixed with the black liquor produced in the cooking process, and the chemical recovery process for alkali cooking Can be used as an energy source and environmentally friendly technology.
以下に本発明の実施例を説明するが、本発明はこれらの実施例に何ら限定されるのではない。なお、実施例における酸処理は、ポリエチレン袋を用いて行った。 Examples of the present invention will be described below, but the present invention is not limited to these examples. In addition, the acid treatment in an Example was performed using the polyethylene bag.
（パルプのサンプル）
アルカリ酸素脱リグニン後の未晒広葉樹クラフトパルプ（ＬＵＫＰと略）は、実生産現場でＬＵＫＰサンプルを採取し、洗浄を行わず、試験を実施するまで５℃の冷蔵庫で保管して実施例に供した（パルプ濃度３２％；カッパー価１０．３；ＨｅｘＡ基５０．６ｍｍｏｌ／ｋｇ）。
(Pulp sample)
Unbleached hardwood kraft pulp after alkaline oxygen delignification (abbreviated as LUKP) is collected at the actual production site without taking a LUKP sample, washed, and stored in a refrigerator at 5 ° C. until the test is conducted. (Pulp concentration 32%; kappa number 10.3; HexA group 50.6 mmol / kg).
（比較例６）
本試験例では、カロ酸としてＥ．Ｉ．ｄｕ Ｐｏｎｔ ｄｅ Ｍｅｍｏｕｒｓ ＆ Ｃｏ．のオキソン（一過硫酸塩化合物 ＝ ２ ＫＨＳＯ5・ＫＨＳＯ4・Ｋ2ＳＯ4）（Ｓｉｇｍａ ＆ Ａｌｄｒｉｃｈ 商品番号 ２２８０３−６）を使用した。
( Comparative Example 6 )
In this test example, E. as caroic acid was used. I. du Pont de Meurs & Co. Of oxone (monopersulfate compound = 2 KHSO 5 · KHSO 4 · K 2 SO 4 ) (Sigma & Aldrich product number 22803-6) was used.
２５０ｇ（絶乾量）のＬＵＫＰを用意し、イオン交換水で１１％濃度スラリ−にパルプを稀釈し、次いで４Ｎ硫酸でｐＨを約２．１になるまでｐＨ調製を行い、１０％オキソン溶液を用いてＬＵＫＰ絶乾量に対するカロ酸に換算した添加量が０．０５％になるように添加した後、再度、イオン交換水でパルプ濃度１０％のパルプスラリーを調製した（硫酸添加率：２．１１％、ｐＨ：２．１）。このパルプスラリーを、８３℃の恒温槽にて１３５分間保持し、酸処理した。酸処理後のＬＵＫＰをろ過し、イオン交換水（２．５Ｌ）で洗浄した。得られたパルプについて、白色度、カッパー価、ＨｅｘＡ基の含有量を分析した。 Prepare 250 g (absolutely dry amount) of LUKP, dilute the pulp to 11% strength slurry with ion-exchanged water, then adjust the pH with 4N sulfuric acid until the pH is about 2.1, and add 10% oxone solution. And added so that the addition amount in terms of caloic acid relative to the LUKP absolute dry amount is 0.05%, and again a pulp slurry having a pulp concentration of 10% was prepared with ion-exchanged water (sulfuric acid addition rate: 2. 11%, pH: 2.1). This pulp slurry was held in a thermostatic bath at 83 ° C. for 135 minutes and acid-treated. LUKP after acid treatment was filtered and washed with ion-exchanged water (2.5 L). The obtained pulp was analyzed for whiteness, kappa number, and HexA group content.
（実施例及び比較例７〜１８）
カロ酸に換算した添加率が０．１％（実施例１〜３、比較例７〜９、比較例１１、比較例１６〜１８）、０．２％（比較例１２）、０．０３％（比較例１０）、０．３％（比較例１３）となるように、１０％オキソン溶液を添加し、表１に記載の条件以外は比較例６と同様な作業を行った。
( Examples and Comparative Examples 7 to 18 )
The addition rate converted to caroic acid is 0.1% ( Examples 1 to 3, Comparative Examples 7 to 9, Comparative Example 11, Comparative Examples 16 to 18 ), 0.2% ( Comparative Example 12 ), 0.03% ( Comparative Example 10 ) 10% oxone solution was added so that it might be 0.3% ( Comparative Example 13 ), and the same operation as Comparative Example 6 was performed except for the conditions described in Table 1.
カロ酸に換算した１０％オキソン溶液の添加率は０．１％であるが、パルプスラリーのｐＨを１．２（比較例９）（硫酸添加率：２．９４％、ｐＨ：１．２）、ｐＨを３．２（実施例１，２、比較例１６）（硫酸添加率：１．２４％、ｐＨ：３．２）、ｐＨを４．０（実施例３）（硫酸添加率：１．０８％、ｐＨ：４．０）、ｐＨを４．８（比較例１７）（硫酸添加率：０．３４％、ｐＨ：４．８）とした。 Although the addition rate of the 10% oxone solution converted to caroic acid is 0.1%, the pH of the pulp slurry is 1.2 ( Comparative Example 9 ) (sulfuric acid addition rate: 2.94%, pH: 1.2). The pH is 3.2 ( Examples 1 and 2, Comparative Example 16 ) (sulfuric acid addition rate: 1.24%, pH: 3.2), and the pH is 4.0 ( Example 3 ) (sulfuric acid addition rate: 1). 0.08%, pH: 4.0) and pH 4.8 ( Comparative Example 17 ) (sulfuric acid addition rate: 0.34%, pH: 4.8).
（比較例１〜５）
カロ酸を添加せずにパルプスラリーのｐＨを２．１（比較例１、比較例４、比較例５）（硫酸添加率：２．１１％、ｐＨ：２．１）、ｐＨを３．２（比較例２）（硫酸添加率：１．２４％、ｐＨ：３．２）、あるいはｐＨを４．０（比較例３）（硫酸添加率：１．０８％、ｐＨ：４．０）とした。
( Comparative Examples 1-5 )
The pH of the pulp slurry was 2.1 (Comparative Example 1, Comparative Example 4, Comparative Example 5) without adding caroic acid (sulfuric acid addition rate: 2.11%, pH: 2.1), and the pH was 3.2. (Comparative Example 2) (sulfuric acid addition rate: 1.24%, pH: 3.2), or pH 4.0 (Comparative Example 3) (sulfuric acid addition rate: 1.08%, pH: 4.0) did.
表１に記載の条件以外は、比較例６と同様な作業を行った。
（パルプ品質の測定方法）
酸処理後ＬＵＫＰは、「ＪＩＳ Ｐ ８１２１」記載のカナダ標準濾水度（フリーネス）で未叩解フリーネスを測定し、更に「ＪＩＳ Ｐ ８２２１−２」記載のＰＦＩミルにより５００ｍｌ ＣＳＦのフリーネスになるまで 叩解を行い、「ＪＩＳ Ｐ ８２２２」及び「ＪＩＳ Ｐ ８２２３」記載の方法にて手抄シートを作成し、紙質試験に供した。測定品質項目は、白色度、カッパー価、ＨｅｘＡ基、裂断長、伸び、比破裂度、比引裂度とした。
カッパー価：「ＪＩＳ Ｐ ８２１１」記載の方法にてカッパー価を測定した。
白色度 ：「ＪＩＳ Ｐ ８２１２」記載の方法を基にＩＳＯ白色度を求めた。
裂断長 ：「ＪＩＳ Ｐ ８１１３」記載の方法にて裂断長を測定した。
比破裂度 ：「ＪＩＳ Ｐ ８１１２」記載の方法を用いて比破裂度として示した。
比引裂度 ：「ＪＩＳ Ｐ ８１１６」記載の方法で比引裂度を測定した。
伸び ：「ＪＩＳ Ｐ ８１１３」記載の方法にて伸びを算出した。
ＨｅｘＡ基：次の文献に詳細に記載した方法にてＨｅｘＡ基の測定を行った。
＜文献＞
Ｄｙｅｒ，Ｔ．Ｊ．，Ｒａｇａｕｓｋａｓ，Ａ．Ｊ．，“Ｅｘａｍｉｎｉｎｇ ｔｈｅ ｉｍｐａｃｔ ｏｆ ｐｒｏｃｅｓｓ ｖａｒｉａｂｌｅｓ ｏｎ ｂｒｏｗｎ−ｓｔｏｃｋ ｋｒａｆｔ ｐｕｌｐ”．Ｉｎ：ＣＤ−ＲＯＭ Ｐｒｏｃｅｅｄｉｎｇｓ ｏｆ ２００３ Ｔａｐｐｉ Ｆａｌｌ Ｔｅｃｈｎｉｃａｌ Ｃｏｎｆｅｒｅｎｃｅ．Ｔａｐｐｉ Ｐｒｅｓｓ，Ａｔｌａｎｔａ，ＧＡ．論文の番号７−１。
結果を表１に示す。
The same operations as in Comparative Example 6 were performed except for the conditions described in Table 1.
(Method for measuring pulp quality)
After acid treatment, LUKP was measured for unbeaten freeness with Canadian standard freeness (freeness) described in “JIS P 8121”, and further beaten until it became 500 ml CSF freeness with PFI mill described in “JIS P 8221-2”. Then, a handsheet was prepared by the method described in “JIS P 8222” and “JIS P 8223” and used for a paper quality test. The measurement quality items were whiteness, kappa number, HexA group, break length, elongation, specific burst, and specific tear.
Copper number: The copper number was measured by the method described in “JIS P 8211”.
Whiteness: ISO whiteness was determined based on the method described in “JIS P 8212”.
Breaking length: The breaking length was measured by the method described in “JIS P 8113”.
Specific rupture degree: It was shown as a specific rupture degree using the method described in “JIS P 8112”.
Specific tear degree: The specific tear degree was measured by the method described in “JIS P 8116”.
Elongation: Elongation was calculated by the method described in “JIS P 8113”.
HexA group: The HexA group was measured by the method described in detail in the following document.
<Reference>
Dyer, T .; J. et al. Ragauskas, A .; J. et al. “Examining the impact of process variables on brown-stock craft pull”. In: CD-ROM Proceedings of 2003 Tapi Fall Technical Conference. Tappi Press, Atlanta, GA. Article number 7-1.
The results are shown in Table 1.
表１に示すように、一定の酸処理温度８３℃とｐＨ２．１では、実施例は比較例１よりパルプの白色度が０〜１ポイント高く、カッパー価が１６．５〜２３．１％低く、ＨｅｘＡ基が１８．５〜３７．７％低減した。同一の酸処理の温度９０℃とｐＨ３．２の条件下では、カロ酸の添加率０．１％（実施例１）が無添加（比較例２）に比べ白色度が０．３ポイント高く、カッパー価がほぼ同等であるが、ＨｅｘＡ基が２０．７％減少した。酸処理の温度９７℃とｐＨ４．０の条件下でも同様な結果が得られた。即ち、カロ酸の添加により、酸処理工程におけるパルプ紙力の維持、ＨｅｘＡ基の除去率向上、カッパー価の低減を図ることができることが知見される。 As shown in Table 1, at a constant acid treatment temperature of 83 ° C. and pH 2.1, the examples had 0 to 1 point higher whiteness of pulp and 16.5 to 23.1% lower kappa number than Comparative Example 1. , HexA group was reduced by 18.5-37.7%. Under the same acid treatment temperature of 90 ° C. and pH of 3.2, the addition rate of 0.1% of caloic acid ( Example 1 ) is 0.3 points higher than that of no addition (Comparative Example 2), Although the kappa number was almost the same, the HexA group decreased by 20.7%. Similar results were obtained even under conditions of acid treatment temperature of 97 ° C. and pH 4.0. That is, it is found that the addition of caroic acid can maintain the pulp paper strength in the acid treatment step, improve the removal rate of HexA groups, and reduce the kappa number.
温度及びｐＨが異なる酸処理を行ったパルプをフリーネス５００ｍｌＣＳＦになるまで叩解し、裂断長、伸び、比破裂度と比引裂度を測定した。結果を表２に示す。 The pulp treated with acid at different temperatures and pHs was beaten until the freeness reached 500 ml CSF, and the breaking length, elongation, specific rupture degree, and specific tear degree were measured. The results are shown in Table 2.
同一の酸処理の温度とｐＨの条件下では、実施例１，３、比較例１１は、各々の相当の比較例１、２、３に比べ裂断長、伸び、比破裂度、比引裂度全てほぼ同等の結果であり、カロ酸の添加により酸処理工程が改善されることが知見される。 Under the same conditions of acid treatment temperature and pH, Examples 1, 3 and Comparative Example 11 were compared with the corresponding Comparative Examples 1, 2 and 3, respectively, in terms of breaking length, elongation, specific burst degree and specific tear degree. All the results are almost the same, and it is found that the acid treatment process is improved by the addition of caroic acid.
本発明は、リグノセルロース物質を原料とし、アルカリ蒸解工程後に、元素状塩素及び次亜塩素酸共に用いない漂白工程を有する漂白アルカリ化学パルプの製造方法であって、アルカリ蒸解工程後に、酸処理工程、漂白工程、をこの順に有する漂白アルカリ化学パルプの製造方法として、適用可能である。 The present invention is a method for producing bleached alkaline chemical pulp using a lignocellulosic material as a raw material and having a bleaching step in which neither elemental chlorine nor hypochlorous acid is used after the alkali cooking step, and the acid treatment step after the alkali cooking step It is applicable as a method for producing bleached alkaline chemical pulp having bleaching steps in this order.
Claims (2)
前記アルカリ蒸解工程後に、酸処理工程、前記漂白工程、をこの順に有し、
前記漂白工程前段の酸処理工程において、酸の添加と併せて、２ＫＨＳＯ 5 ・ＫＨＳＯ 4 ・Ｋ 2 ＳＯ 4 である一過硫酸塩化合物をカロ酸に換算した添加量が前記リグノセルロース物質の絶乾量（質量基準）に対して０．０５〜１．０％となるように添加し、
前記酸処理工程を、ｐＨ３．２〜４．０、温度９０〜１００℃、処理時間１〜５時間の処理条件で行う、
ことを特徴とする漂白アルカリ化学パルプの製造方法。 Using a lignocellulosic material as a raw material, after the alkali cooking step, a method for producing bleached alkaline chemical pulp having a bleaching step in which neither elemental chlorine nor hypochlorous acid is used,
After the alkali cooking step, the acid treatment step, the bleaching step, in this order,
In the acid treatment step preceding the bleaching step, in addition to the addition of acid, the addition amount of the monopersulfate compound, which is 2KHSO 5 · KHSO 4 · K 2 SO 4 , converted to caloic acid is the absolute dryness of the lignocellulosic material. Add to 0.05 to 1.0% with respect to the amount (mass basis) ,
The acid treatment step is performed under treatment conditions of pH 3.2 to 4.0, temperature 90 to 100 ° C., treatment time 1 to 5 hours,
A method for producing bleached alkaline chemical pulp, characterized in that
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