JP6304024B2 - Method for producing deinked pulp - Google Patents
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- JP6304024B2 JP6304024B2 JP2014265162A JP2014265162A JP6304024B2 JP 6304024 B2 JP6304024 B2 JP 6304024B2 JP 2014265162 A JP2014265162 A JP 2014265162A JP 2014265162 A JP2014265162 A JP 2014265162A JP 6304024 B2 JP6304024 B2 JP 6304024B2
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- 229920001131 Pulp (paper) Polymers 0.000 title claims description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 238000000034 method Methods 0.000 claims description 57
- 239000003795 chemical substances by application Substances 0.000 claims description 40
- 238000005188 flotation Methods 0.000 claims description 29
- 238000005406 washing Methods 0.000 claims description 28
- 238000004061 bleaching Methods 0.000 claims description 23
- 239000002761 deinking Substances 0.000 claims description 23
- 239000006185 dispersion Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 16
- 239000000701 coagulant Substances 0.000 claims description 15
- 230000014759 maintenance of location Effects 0.000 claims description 15
- 239000013054 paper strength agent Substances 0.000 claims description 15
- 239000013055 pulp slurry Substances 0.000 claims description 14
- 230000007935 neutral effect Effects 0.000 claims description 11
- 239000000428 dust Substances 0.000 claims description 7
- 238000004537 pulping Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 description 40
- 239000000123 paper Substances 0.000 description 28
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 22
- 238000011156 evaluation Methods 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 229940079593 drug Drugs 0.000 description 13
- 239000003814 drug Substances 0.000 description 13
- 239000000835 fiber Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000006872 improvement Effects 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 239000010893 paper waste Substances 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920002401 polyacrylamide Polymers 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 238000009841 combustion method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009897 hydrogen peroxide bleaching Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000628997 Flos Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229940053200 antiepileptics fatty acid derivative Drugs 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010130 dispersion processing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011234 economic evaluation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- -1 polydadomac Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/64—Paper recycling
Landscapes
- Paper (AREA)
Description
本発明は、古紙パルプの製造方法に関し、特に印刷古紙から高い灰分含有量の維持とインキ除去性に優れている脱墨パルプの製造方法に関するものである。 The present invention relates to a method for producing waste paper pulp, and more particularly, to a method for producing deinked pulp excellent in maintaining high ash content and excellent ink removability from printed waste paper.
従来、抄紙段階における填料や微細繊維の歩留向上については、種々の歩留剤及び歩留りシステムが検討され、採用されている。最も多く採用されてきたシステムはカチオン性ポリマーを用いたポリマー単独処方である。古紙再生処理工程においても、微細繊維、填料等の歩留率の向上を図るために、フロス中の灰分の回収や、微細繊維の回収について鋭意研究が行われ、ある一定の歩留向上は可能であったものの、完成脱墨パルプのインキ除去性を維持したまま、もう一段の歩留向上をさせることは困難であった。 Conventionally, various yield agents and yield systems have been studied and adopted for improving the yield of fillers and fine fibers in the papermaking stage. The most widely adopted system is a single polymer formulation using a cationic polymer. Even in the used paper recycling process, in order to improve the yield rate of fine fibers and fillers, earnest research has been conducted on the collection of ash in the floss and the collection of fine fibers, and a certain yield improvement is possible. However, it was difficult to further improve the yield while maintaining the ink removal property of the finished deinked pulp.
例えば、古紙再生処理工程において、現状のアルカリ性領域のフローテーションを経た後、洗浄工程及び脱水工程の前のパルプスラリーに凝結剤を添加する方法(例えば、特許文献1)や、同様に現状のアルカリ性領域のフローテーションを経た後、(メタ)アクリルアミド+カチオン性モノマー+アニオン性モノマーを構成成分として重合した水溶性両性共重合体を添加する方法(例えば、特許文献2)、更に(メタ)アクリルアミドと、カチオン性モノマーとを構成成分とし、又は(メタ)アクリルアミドと、カチオン性モノマーと、(c)アニオン性モノマーとを構成成分とし、さらに(d)架橋性モノマー及び/又は(e)連鎖移動剤を使用して重合した水溶性イオン性ポリアクリルアミド系共重合体を添加する方法(特許文献3)などがある。しかし、現在の古紙脱墨工程で行われているアルカリ性領域でのフローテーションでは、古紙に由来する汚れや印刷インクが完全に除去されないため、その後に脱墨パルプの歩留向上を目的に凝結剤、紙力剤、歩留剤を用いると、完成の脱墨パルプのインキ除去性が著しく劣るという問題があった。 For example, in the used paper recycling treatment process, after passing through the current alkaline region flotation, a method of adding a coagulant to the pulp slurry before the washing step and the dewatering step (for example, Patent Document 1), as well as the current alkaline After passing through the flotation of the region, a method of adding a water-soluble amphoteric copolymer obtained by polymerizing (meth) acrylamide + cationic monomer + anionic monomer as a constituent component (for example, Patent Document 2), and (meth) acrylamide and A cationic monomer as a constituent component, or (meth) acrylamide, a cationic monomer, and (c) an anionic monomer as a constituent component, and (d) a crosslinkable monomer and / or (e) a chain transfer agent. There is a method of adding a water-soluble ionic polyacrylamide copolymer polymerized by using (Patent Document 3). However, the flotation in the alkaline area currently used in the used paper deinking process does not completely remove the dirt and printing ink derived from the used paper, so the coagulant is used to improve the yield of deinked pulp afterwards. When the paper strength agent and the retention agent are used, there is a problem that the ink removal property of the finished deinked pulp is remarkably inferior.
従来の脱墨パルプの製造方法は、脱墨パルプに含まれているインキを灰分とともにスクリーニング工程、フローテーション工程、洗浄工程、脱水工程等で除去することで、概ね白色度の白い脱墨パルプを製造している。しかし、インキは完成の脱墨パルプの品質に悪影響を及ぼすものの、灰分は比較的白く、完成の脱墨パルプの構成成分としてパルプスラリー中に残留させることがコスト的にも、また、廃棄物を低減させるという観点から環境的にも、さらには、脱墨パルプ中に残留せずにろ液中に排出された灰分は流送の配管中のスケールとして堆積したりするため設備メンテナンスの面からも有利な事である。 The conventional deinked pulp manufacturing method removes the ink contained in the deinked pulp together with ash in the screening process, flotation process, washing process, dehydrating process, etc. Manufacture. However, although the ink has an adverse effect on the quality of the finished deinked pulp, the ash is relatively white, and it can remain in the pulp slurry as a constituent of the finished deinked pulp in terms of cost and waste. From the viewpoint of reducing the environmental impact, and further, from the aspect of equipment maintenance, the ash discharged in the filtrate without remaining in the deinked pulp accumulates as a scale in the piping of the inflow. It is advantageous.
本発明は、上記従来の問題点に鑑み、印刷古紙から高灰分で残インキ除去性に優れた脱墨パルプが得られ、スラッジ灰の低減と使用填料の低減を図ることができる脱墨パルプの製造方法を提供することを課題とする。 In view of the above-mentioned conventional problems, the present invention provides a deinked pulp having high ash content and excellent residual ink removal properties from used printed paper, and is capable of reducing sludge ash and reducing the amount of filler used. It is an object to provide a manufacturing method.
従来、印刷古紙から脱墨パルプを製造する方法において、離解工程、スクリーニング工程、漂白工程、ニーディング工程、フローテーション工程、洗浄工程の組合せからなる古紙のパルプ化工程において、アルカリ性で行う漂白工程、ニーディング工程を経た後のフローテーション工程はpH9を超えてpH11程度までの範囲のアルカリ性領域で行われてきた。本発明者らは検討を重ねた結果、該フローテーション工程をH6〜9の中性領域で行うことでインキを十分に除去し、その後の洗浄工程に送るパルプスラリーに凝結剤、紙力剤、歩留剤の1以上の薬剤を添加することで、高歩留で、かつ、インキ除去性の優れた脱墨パルプを提供できることを見出し、下記の発明を完成するに至った。 Conventionally, in a method for producing deinked pulp from used printed paper, in a pulping process of used paper consisting of a combination of a disaggregation process, a screening process, a bleaching process, a kneading process, a flotation process, and a washing process, a bleaching process performed in an alkaline manner, The flotation process after the kneading process has been performed in an alkaline region in the range of more than pH 9 to about pH 11. As a result of repeated investigations, the inventors have sufficiently removed the ink by performing the flotation process in the neutral region of H6 to 9, and the coagulant, the paper strength agent, It has been found that adding one or more chemicals as a retention agent can provide a deinked pulp with high yield and excellent ink removability, and the following invention has been completed.
印刷古紙を、離解工程、除塵工程、漂白工程、分散工程、フローテーション工程、洗浄工程を少なくとも有する一連の工程によってパルプ化する方法において、漂白工程及び分散工程を経たパルプスラリーをフローテーション工程においてpH6〜9の中性領域で脱墨処理し、その後の洗浄工程の直前のパルプスラリーに対して凝結剤、紙力剤及び歩留剤から選ばれる1種以上を添加して洗浄処理することを特徴とする脱墨パルプの製造方法。 In a method of pulping used printed paper through a series of steps including at least a disaggregation step, a dust removal step, a bleaching step, a dispersion step, a flotation step, and a washing step, the pulp slurry that has undergone the bleaching step and the dispersion step has a pH of 6 in the flotation step. It is characterized by performing deinking treatment in a neutral region of ˜9, and adding one or more selected from a coagulant, a paper strength agent and a retention agent to the pulp slurry immediately before the subsequent washing step. A method for producing deinked pulp.
前記洗浄工程における凝結剤、紙力剤及び歩留剤から選ばれる1種以上の薬剤の添加量が100ppm〜3000ppmである上記脱墨パルプの製造方法。 The said deinking pulp manufacturing method whose addition amount of 1 or more types of chemical | medical agents chosen from the coagulant | flocculant, a paper strength agent, and a retention agent in the said washing | cleaning process is 100 ppm-3000 ppm.
前記一連の工程が、離解工程、除塵工程、分散工程、漂白工程、フローテーション工程、洗浄工程を順次実施して印刷古紙から脱墨パルプを製造する工程である上記いずれかの脱墨パルプの製造方法。 Manufacture of one of the above deinked pulps, wherein the series of steps is a step of manufacturing deinked pulp from waste printed paper by sequentially performing a disaggregation process, a dust removal process, a dispersion process, a bleaching process, a flotation process, and a washing process. Method.
本発明によれば、印刷古紙から脱墨パルプを製造する方法において、離解工程、スクリーニング工程、漂白工程、ニーディング工程、フローテーション工程、洗浄工程を少なくとも有する組合せ工程による古紙のパルプ化方法において、フローテーション工程をH6〜9の中性領域で行うことでインキを十分に除去し、その後のパルプスラリーに凝結剤、紙力剤、歩留剤の1以上の薬剤を添加することで、優れたインキ除去性を維持したまま、歩留を大幅に向上させることができる。そのため、古紙由来の填料を含む灰分の歩留を向上させて、紙製品にクラフトパルプ、メカニカルパルプ等より安価な脱墨パルプを高配合する事が可能となるとともに環境負荷の軽減も可能となり、古紙の利用範囲が広がる。 According to the present invention, in a method for producing deinked pulp from used printed paper, in a pulping method of used paper by a combination step having at least a disaggregation step, a screening step, a bleaching step, a kneading step, a flotation step, and a washing step, By removing the ink sufficiently by carrying out the flotation process in the neutral region of H6-9, adding one or more agents of a coagulant, a paper strength agent, and a retention agent to the subsequent pulp slurry is excellent. The yield can be greatly improved while maintaining the ink removability. Therefore, it is possible to improve the yield of ash containing fillers derived from waste paper, to highly blend deinked pulp cheaper than kraft pulp, mechanical pulp, etc. into paper products, and to reduce the environmental burden, The range of used paper is expanded.
以下、本発明の脱墨パルプの製造方法の実施形態について、詳細に説明する。
原料となる印刷古紙の例としては、新聞紙、微塗工紙、高灰分の塗工紙、非塗工紙等、灰分を7%〜40%含む古紙があげられる。本発明は、多量の表面処理剤により脱墨性が悪い一部の中性新聞紙を含む印刷古紙にも効果的である。
Hereinafter, embodiments of the method for producing deinked pulp of the present invention will be described in detail.
Examples of the used printing paper as a raw material include used paper containing 7% to 40% ash, such as newspaper, fine coated paper, high ash coated paper, and non-coated paper. The present invention is also effective for used printed paper including some neutral newspapers having poor deinking properties due to a large amount of surface treatment agent.
本発明の方法における離解工程について特に制限は無いが、好ましい処理として、まず、原料印刷古紙を離解機に入れ、固形分濃度12〜18%になるように稀釈水を入れ、更に薬品(水酸化ナトリウム)を対パルプ0〜3.0質量%、好ましくは0.1〜2.5質量%添加する。脱墨剤を添加する場合には、パルプ繊維への浸透性が強く、インキの剥離性の強いものが好ましく、脱墨剤を対パルプ0.01〜0.5質量%、好ましくは0.03〜0.3質量%加える。離解時間は、10〜30分、好ましくは10〜25分、更に好ましくは10〜18分、離解温度は10〜50℃、好ましくは30〜50℃で離解することが好ましい。 There is no particular limitation on the disaggregation step in the method of the present invention, but as a preferable treatment, first, the raw printed paper is put into a disaggregator, diluted water is added so that the solid content concentration becomes 12 to 18%, and further chemicals (hydroxylation) Sodium) is added to the pulp in an amount of 0 to 3.0% by mass, preferably 0.1 to 2.5% by mass. In the case of adding a deinking agent, those having strong permeability to pulp fibers and strong ink peelability are preferable, and the deinking agent is 0.01 to 0.5% by mass, preferably 0.03% by weight of the pulp. Add ~ 0.3 wt%. The disaggregation time is 10 to 30 minutes, preferably 10 to 25 minutes, more preferably 10 to 18 minutes, and the disaggregation temperature is 10 to 50 ° C., preferably 30 to 50 ° C.
インキの剥離性の強い脱墨剤としては、高級アルコール系脱墨剤、両性脱墨剤等があり、例えば、花王(株)製のDI−7020、DI−7030、DI−767、DI−7282、日新化学研究所(株)製のDIA−Z−100、DIA−Z−5000、東邦化学(株)製のネオスコアFW−780、ネオスコアFW−790、ネオスコアFW−795、FT−467、FT−470、FT−487、FT−511、FT−513、FT−514、FT−515、B−B剤、第一工業製薬(株)製ダイホープ940、ダイホープ960、日華(株)製リポブライトDP−810等があるがこれらに限られるものではない。 Examples of deinking agents with strong ink peelability include higher alcohol deinking agents and amphoteric deinking agents, such as DI-7020, DI-7030, DI-767, and DI-7282 manufactured by Kao Corporation. DIA-Z-100, DIA-Z-5000 manufactured by Nissin Chemical Laboratory, Neoscore FW-780, Neoscore FW-790, Neoscore FW-795, FT-467, FT manufactured by Toho Chemical Co., Ltd. -470, FT-487, FT-511, FT-513, FT-514, FT-515, BB agent, Daiho Kogyo Co., Ltd., Daihope 940, Daihope 960, Nikka Corporation Lipobright There is DP-810 etc., but it is not limited to these.
本発明の方法における除塵工程で用いる装置には特に制限は無い。スクリーン・クリーナーで原料中の異物を取り除くことが可能であればよいが、スリットスクリーン(1段目0.15mmスリット以下、2段目0.15mmスリット以下)を使用することが好ましい。クリーナーは重量異物を効率良く取り除くことが可能であればいずれでもよい。 There is no restriction | limiting in particular in the apparatus used at the dust removal process in the method of this invention. Although it is sufficient that foreign substances in the raw material can be removed with a screen cleaner, it is preferable to use a slit screen (first stage 0.15 mm slit or less, second stage 0.15 mm slit or less). Any cleaner may be used as long as it can efficiently remove heavy foreign matter.
古紙再生の漂白薬品としては過酸化水素、ハイドロサルファイド、二酸化チオ尿素、ハイポ等が使用される。本発明では過酸化水素を使用する。また、本発明の方法ではアルカリ過酸化水素漂白を行うが、過酸化水素は対パルプ0.5〜5.0質量%添加する。これ以上添加量を増やしても白色度上昇はサチュレーションする傾向にある。苛性ソーダは、対パルプ1.5〜3.0質量%、珪酸ソーダは、対パルプ1.5〜3.5質量%添加し、漂白時間は10分間〜5時間、好ましくは1.5〜3時間で行う。漂白時間が短すぎると過酸化水素が十分に反応しきらないため好ましくない、また5時間より長くしても逆に過酸化水素の消費が進み、残過酸化水素がなくなった時点からパルプの黄色化が起きるため、適切ではない。漂白パルプ濃度は15〜35%、好ましくは25〜30%、濃度が15%より低くなると過酸化水素の反応性が悪くなる。また、35%より高い濃度にするとディスパーザーでの薬品との混合に斑ができるため、好ましくない。また、漂白時のpHは、10.5〜12.0が好ましく、この範囲を外れると過酸化水素の漂白性が劣る。漂白温度は50〜120℃で行うことが効果的である。 Hydrogen peroxide, hydrosulfide, thiourea dioxide, hypo, etc. are used as bleaching chemicals for recycled used paper. In the present invention, hydrogen peroxide is used. Further, in the method of the present invention, alkaline hydrogen peroxide bleaching is performed, and hydrogen peroxide is added in an amount of 0.5 to 5.0% by mass with respect to pulp. Even if the amount added is further increased, the increase in whiteness tends to saturate. Caustic soda is added to 1.5 to 3.0% by mass of pulp, and sodium silicate is added to 1.5 to 3.5% by mass of pulp. Bleaching time is 10 minutes to 5 hours, preferably 1.5 to 3 hours. To do. If the bleaching time is too short, hydrogen peroxide will not react sufficiently, which is not preferable. Also, if the bleaching time is longer than 5 hours, the consumption of hydrogen peroxide will increase, and the yellow color of the pulp will start from the point when there is no remaining hydrogen peroxide. It is not appropriate because it will occur. The bleaching pulp concentration is 15 to 35%, preferably 25 to 30%, and when the concentration is lower than 15%, the reactivity of hydrogen peroxide is deteriorated. On the other hand, if the concentration is higher than 35%, it is not preferable because the mixture with the chemical in the disperser is uneven. Further, the pH during bleaching is preferably 10.5 to 12.0. If the pH is outside this range, the bleaching property of hydrogen peroxide is inferior. It is effective to carry out the bleaching temperature at 50 to 120 ° C.
また、フローテーション前に脱墨剤がパルプに均一に混合できれば、漂白工程前後に係わらず、いずれに脱墨剤を添加してもよい。インキ凝集性の強い脱墨剤としては、脂肪酸あるいは、脂肪酸誘導体系の脱墨剤があり、例えば、脂肪酸の場合、花王(株)製のDI−254(オレイン酸)、DI−268、第一工業製薬(株)製のK−4004−D等がある。また、脂肪酸誘導体系の場合、花王(株)製のDI−1120、DI−1050、日新化学研究所(株)製のDIY−23543、第一工業製薬(株)製のペーパーエイドW等があるがこれらに限られるものではない。 Further, as long as the deinking agent can be uniformly mixed with the pulp before flotation, the deinking agent may be added to any of them before and after the bleaching step. Deinking agents having strong ink cohesion include fatty acid or fatty acid derivative-based deinking agents. For example, in the case of fatty acids, DI-254 (oleic acid), DI-268, Daiichi manufactured by Kao Corporation. K-4004-D manufactured by Kogyo Seiyaku Co., Ltd. is available. In the case of fatty acid derivatives, DI-1120 and DI-1050 manufactured by Kao Corporation, DIY-23543 manufactured by Nissin Chemical Laboratory Co., Ltd., Paper Aid W manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Yes, but not limited to these.
本発明の分散工程(ニーディング工程)で行う分散機による処理には低速・高濃度用軸タイプの分散機または、ディスクタイプの分散機が適している。低速・高濃度用軸タイプの分散機としては、一軸型または二軸型のニーダータイプのディスパーザーが好ましい。軸状のローターに取り付けられた回転刃と、ケーシングに取り付けられた固定刃を有し、回転数50〜300rpmの低速で、処理濃度20%〜50%(以下パルプ濃度%は質量%を意味する)の高濃度、好ましくは、25%〜40%、温度は25℃〜100℃、好ましくは40〜90℃で処理する。軸タイプの分散機では、繊維間の摩擦作用が主体となって、インキ剥離・ダートの分散が起こる。処理濃度が20%未満では、機械的負荷がかかりにくく、インキ剥離・ダートの分散性が低下する上、温度上昇に必要なエネルギーが莫大となるため、適さない。また、処理濃度50%を越えて高濃度にすると機械的に搾水するのは困難である。 A low-speed, high-concentration shaft type disperser or a disk-type disperser is suitable for the processing by the disperser performed in the dispersion step (kneading step) of the present invention. As the low-speed and high-concentration shaft type disperser, a uniaxial or biaxial kneader type disperser is preferable. It has a rotary blade attached to a shaft-shaped rotor and a fixed blade attached to a casing, and has a processing concentration of 20% to 50% (hereinafter, pulp concentration% means mass%) at a low speed of 50 to 300 rpm. ), Preferably at 25% to 40%, and at a temperature of 25 ° C to 100 ° C, preferably 40 to 90 ° C. In the shaft type disperser, the frictional action between the fibers is the main, and the ink peeling and dirt dispersion occur. If the treatment concentration is less than 20%, it is difficult to apply a mechanical load, and ink dispersibility / dirt dispersibility is lowered, and energy required for temperature increase is enormous, which is not suitable. Further, if the treatment concentration exceeds 50% and the concentration is high, it is difficult to squeeze water mechanically.
一般的には、一軸型ニーダーとして、ニーディング・ディスパージャーKD(商品名:アイ・エイチ・アイ フォイト ペーパーテクノロジー社製)、ディスパーザー(商品名:相川鉄工社製)、ディスパーザー(商品名:アセック社製)、ディスパーザー(商品名:三栄レギュレーター社製)、CCE型ニーディングマシン(商品名:新浜ポンプ製作所社製)、ニーダー(商品名:山本百馬製作所社製)などが使用され、また、二軸型ニーダーとして、新浜ポンプ製作所社製、山本百馬製作所製のものなどが使用されるが、特定の機種に限定されるものではない。 In general, as a single-shaft kneader, kneading disperser KD (trade name: manufactured by IH IFOIT Paper Technology), disperser (trade name: manufactured by Aikawa Tekko), disperser (trade name: ASEC), disperser (trade name: manufactured by Sanei Regulator Co., Ltd.), CCE type kneading machine (trade name: manufactured by Niihama Pump Manufacturing Co., Ltd.), kneader (product name: manufactured by Hyakuma Yamamoto Manufacturing Co., Ltd.), etc. In addition, as the biaxial kneader, those manufactured by Niihama Pump Manufacturing Co., Ltd., Yamamoto Hyakuma Manufacturing Co., Ltd., and the like are used, but are not limited to specific models.
また、ディスクタイプの分散機としては、ディスク型ディスパーザーまたはコニカル型ディスパーザーであれば特に制限はない。構造的にはディスクリファイナーと似ているが、ディスクプレートの構造が異なっている。また、コニカル型ディスパーザーは回転刃がコニカル状になっている。回転数300rpm〜2500rpm、処理濃度20%以上で処理する。軸タイプの分散機と異なる点は、繊維と刃の衝突作用が主体となってインキ剥離・ダートの分散が起こる点である。一般的には、ディスク型ディスパーザーとして、ディスパージャーHTD(商品名:アイ・エイチ・アイ フォイトペーパーテクノロジー社製)、KRIMAホットディスパージョン設備(商品名:Cellwood社製)などが使用され、また、コニカル型ディスパーザーとして、コニディスク(商品名:相川鉄工社製)、コニカルディスパージョンシステム/HIプリヒーター/OptiFinerディスパーザー(商品名:メッツォ SHI社製)などが使用されるが、特定の機種に限定されるものではない。 Further, the disk type disperser is not particularly limited as long as it is a disk type disperser or a conical type disperser. Structurally similar to a disc refiner, but the disc plate has a different structure. Further, the conical type disperser has a rotating blade in a conical shape. Processing is performed at a rotational speed of 300 rpm to 2500 rpm and a processing concentration of 20% or more. The difference from the shaft type disperser is that the ink and the dirt are dispersed mainly by the collision action of the fiber and the blade. Generally, as a disk-type disperser, a disperser HTD (trade name: manufactured by IH / IFOIT PAPER TECHNOLOGY), a KRIMA hot dispersion facility (trade name: manufactured by Cellwood), etc. are used. As conical type dispersers, conical discs (trade name: manufactured by Aikawa Tekko Co., Ltd.), conical dispersion systems / HI pre-heaters / Optifiner dispersers (product name: manufactured by Metso SHI), etc. are used. It is not limited.
分散機の組み合わせとして特に好ましいものは、低速・高濃度用軸タイプの分散機で2回、ディスクタイプの分散機で1回、この順に処理を行うことが効率的且つ効果的である。1回目若しくは2回目の分散処理である低速・高濃度用軸タイプの分散機による分散処理は、処理濃度20%〜50%の高濃度、好ましくは、25%〜40%、温度は25℃〜100℃、好ましくは40〜90℃で処理する。軸タイプの分散機では、繊維間の摩擦作用が主体となって、インキ剥離・ダートの分散が起こる。処理濃度が20%未満では、機械的負荷がかかりにくく、インキ剥離・ダートの分散性が低下する上、温度上昇に必要なエネルギーが莫大となるため、適さない。また、処理濃度50%を越えて高濃度にすると機械的に搾水するのは困難である。また、次の過酸化水素漂白工程での漂白効果を高めるため、温度は25℃以上に高める必要があるが、100℃を超えると過酸化水素の分解が生じるため、好ましくない。 A particularly preferable combination of the dispersing machines is efficient and effective to perform processing in this order twice with a low-speed / high-concentration shaft type dispersing machine and once with a disk-type dispersing machine. The dispersion process by the low-speed / high-concentration shaft type disperser which is the first or second dispersion process is a high concentration of treatment concentration 20% to 50%, preferably 25% to 40%, and the temperature is 25 ° C. The treatment is performed at 100 ° C, preferably 40 to 90 ° C. In the shaft type disperser, the frictional action between the fibers is the main, and the ink peeling and dirt dispersion occur. If the treatment concentration is less than 20%, it is difficult to apply a mechanical load, and ink dispersibility / dirt dispersibility is lowered, and energy required for temperature increase is enormous, which is not suitable. Further, if the treatment concentration exceeds 50% and the concentration is high, it is difficult to squeeze water mechanically. In order to enhance the bleaching effect in the subsequent hydrogen peroxide bleaching step, the temperature needs to be raised to 25 ° C. or higher. However, if it exceeds 100 ° C., hydrogen peroxide is decomposed, which is not preferable.
本発明の方法でディスク型の分散機による分散処理を行う場合の温度は90〜130℃である。90℃未満の処理では、十分なダート減少効果と二酸化チオ尿素の漂白効果が得られず、一方、130℃を超えるとパルプの黄変が生じるため適さない。ディスク型分散機には、過酸化水素、二酸化チオ尿素のほかにアルカリ薬品を添加してもよい。アルカリ薬品としては、水酸化ナトリウムが好ましい。過酸化水素添加量は、絶乾パルプ質量に対して0.05〜3質量%、二酸化チオ尿素の添加量は、絶乾パルプ質量に対して0.1〜2質量%で、特に好ましくは0.2〜1.0質量%である。 The temperature in the case of performing the dispersion process by the disk type disperser in the method of the present invention is 90 to 130 ° C. If the treatment is less than 90 ° C., sufficient dart reduction effect and bleaching effect of thiourea dioxide cannot be obtained, while if it exceeds 130 ° C., yellowing of the pulp occurs, which is not suitable. In addition to hydrogen peroxide and thiourea dioxide, alkaline chemicals may be added to the disk type disperser. As the alkaline chemical, sodium hydroxide is preferable. The amount of hydrogen peroxide added is 0.05 to 3% by mass with respect to the mass of the absolutely dry pulp, and the amount of thiourea dioxide added is 0.1 to 2% by mass with respect to the mass of the absolutely dry pulp, particularly preferably 0. .2 to 1.0% by mass.
高温のディスパーザー処理後に続きフローテーション工程を行う。ディスパーザー処理により剥離したインクを特に中性領域のフローテーター工程で除去することが効率的である。洗浄工程で除去する方法の場合には、洗浄慮液とともに白水内を循環し、パルプの完成白色度に影響を与える恐れがあるので好ましくない。フローテーション工程でのフローテーターの形式に制限はないが、処理濃度は0.7〜1.5%、フローテーター処理温度は10〜55℃、好ましくは30〜50℃で行うことが好ましい。 A flotation process is performed after the high-temperature disperser treatment. It is efficient to remove the ink that has been peeled off by the disperser treatment, particularly in the neutral zone flowator process. In the case of the method of removing in the washing step, it is not preferable because it circulates in the white water together with the washing solution and may affect the finished whiteness of the pulp. Although there is no restriction | limiting in the form of the flotator in a flotation process, it is preferable to carry out at a processing concentration of 0.7 to 1.5% and a flotator processing temperature of 10 to 55 ° C, preferably 30 to 50 ° C.
本発明の方法におけるフローテーション工程の処理pHは6〜9が適しており、7〜8.5がより好ましい。pHが6より低いと配管、設備の腐食が問題となり、設備費が高価になる。また、pHが9を超えると脱墨パルプのインキ除去性が著しく悪化する。また、フローテーションの処理pHを調整する薬剤として、硫酸、塩酸、苛性ソーダ、ケイ酸ソーダ等が用いられるが、これらに限られるものではない。 The treatment pH in the flotation step in the method of the present invention is suitably 6-9, more preferably 7-8.5. When the pH is lower than 6, corrosion of piping and equipment becomes a problem, and equipment costs are expensive. On the other hand, if the pH exceeds 9, the ink removal property of the deinked pulp is significantly deteriorated. Further, sulfuric acid, hydrochloric acid, caustic soda, sodium silicate, or the like is used as an agent for adjusting the flotation treatment pH, but is not limited thereto.
本発明の方法には、pH6〜9の中性領域でフローテーションを行なった後、フローテーターで取り除けなかった微細なインキを脱水洗浄する洗浄工程がある。洗浄装置に特に制限は無いが、0.6〜1.5%のパルプスラリーを清水または抄紙機のクリア白水で希釈した後、15〜35%まで脱水洗浄することが好ましい。また、洗浄工程で使用する洗浄装置としてはエキストラクター、フォールウオッシャー(栄工機製)、ダブルニップシックナー(石川島産業機械製)等があるが、洗浄装置は、原料中のインキ分を優先的に除去し、繊維分、灰分のロスを最小限に止める洗浄機であることが好ましい。中でもワイヤー洗浄機が好ましく、目穴は、20〜200メッシュ程度までが考えられるが、好ましくは40〜100メッシュが良く、更に好ましくは、50〜80メッシュが適している。 The method of the present invention includes a washing step of dehydrating and washing fine ink that has not been removed by a flotator after flotation in a neutral region of pH 6-9. Although there is no restriction | limiting in particular in a washing | cleaning apparatus, After diluting 0.6-1.5% pulp slurry with fresh water or the clear white water of a paper machine, it is preferable to carry out dehydration washing to 15-35%. The cleaning equipment used in the cleaning process includes extractors, fall washers (Eiko), and double nip thickeners (Ishikawajima Sangyo), but the cleaning equipment preferentially removes ink in the raw materials. However, it is preferable that the washing machine can minimize loss of fiber and ash. Among them, a wire washer is preferable, and the eye hole can be about 20 to 200 mesh, preferably 40 to 100 mesh, and more preferably 50 to 80 mesh.
本発明の方法では、フローテーション工程の後の洗浄工程の直前の脱墨パルプスラリーに凝結剤、紙力剤、歩留剤の1つ以上を添加する。凝結剤、紙力剤、歩留剤の具体例については、例えばポリアクリルアミドのように紙力剤として、または歩留剤として市販されているものもあるので、個々の薬剤を凝結剤、紙力剤、歩留剤の何れかに明確に区別して分類することは必ずしも正確ではないが、使用できる具体的な薬剤としては、通常、凝結剤、紙力剤、歩留剤の何れかの添加薬剤として使用される以下のものが挙げられる。 In the method of the present invention, one or more of a coagulant, a paper strength agent, and a retention agent are added to the deinked pulp slurry immediately after the washing step after the flotation step. Specific examples of the coagulant, paper strength agent, and retention agent are commercially available as a paper strength agent, such as polyacrylamide, or as a retention agent. Although it is not always accurate to classify it clearly as either an agent or a retention agent, as a specific agent that can be used, it is usually a coagulant, a paper strength agent, or a retention agent. The following are used as:
ポリアクリルアミド、硫酸アルミニウム、ポリダドマック、ポリアミン、ポリエチレンイミン、2−(メタクリロイルオキシ)エチルトリメチルアンモニウムクロリド重合物、変性ポリエチレンイミン等が主材となっている薬剤から選択された何れか1つ若しくは複数の混合物から成るもの、あるいは、 (メタ)アクリルアミドと水溶性カチオン性モノマーと水溶性アニオン性モノマーを構成成分とした薬剤(総称して両性アクリルアミドであり、例えば、ハリマ化成社製「ハリアップAC」が挙げられる。)。その他市販の薬剤、例えば、荒川化学社製ポリストロン372、KW−387−20、MTアクアポリマー社製アキュラック208E、アキュラック100E、栗田工業社製フィクサージュ621、ハイモ社製ハイモロックNR−70、ソマール社製リアライザーR500、リアライザーR600、協和産業社製キースロックRP−532 等。これらの薬剤のうち、灰分及び繊維分の歩留を向上させる薬剤であれば好適に使用できる。中でも両性アクリルアミドを成分とする薬剤が歩留向上に特に有効である。 One or more mixtures selected from drugs mainly composed of polyacrylamide, aluminum sulfate, polydadomac, polyamine, polyethyleneimine, 2- (methacryloyloxy) ethyltrimethylammonium chloride polymer, modified polyethyleneimine, etc. Or a drug composed of (meth) acrylamide, a water-soluble cationic monomer, and a water-soluble anionic monomer (generally referred to as amphoteric acrylamide, for example, “Hariup AC” manufactured by Harima Chemical Co., Ltd.) .) Other commercially available drugs such as Polystron 372, KW-387-20 manufactured by Arakawa Chemical Co., Inc. Acracac 208E manufactured by MT Aquapolymer Co., Accurac 100E, Fixage 621 manufactured by Kurita Kogyo Co., Hymolock NR-70 manufactured by Hymo Co., Ltd. Realizer R500, Realizer R600 manufactured by Somaar, Keith Lock RP-532 manufactured by Kyowa Sangyo Co., Ltd. Of these agents, any agent that improves the yield of ash and fibers can be preferably used. Among them, a drug containing amphoteric acrylamide as a component is particularly effective for improving the yield.
上記薬剤の添加量は、好ましくは100ppm〜3000ppmであり、より好ましくは1000ppm〜2000ppmである。100ppm未満では効果が低くなる恐れがあり、一方3000ppmを超えて添加してもさらなる効果の改善は少なく、不経済でかつ系内に汚れが出る恐れがある。 The amount of the drug added is preferably 100 ppm to 3000 ppm, more preferably 1000 ppm to 2000 ppm. If it is less than 100 ppm, the effect may be low. On the other hand, even if it is added in excess of 3000 ppm, there is little improvement in the effect, which is uneconomical and may cause contamination in the system.
本発明の方法により、新聞古紙を主体とした印刷古紙より脱墨パルプとしてISO白色度が50%〜85%のものまで幅広く製造できるが、いずれの場合もインキ除去性に優れる高歩留の脱墨パルプを提供することが可能となる。一方、スラッジ灰の発生量を低減して環境にやさしい脱墨パルプの製造方法を提供できるとともに、抄紙工程の使用填料を低減できるため、薬品コストの低減も可能となる。 According to the method of the present invention, it is possible to produce a wide range of deinked pulps having an ISO whiteness of 50% to 85% from printed newspapers mainly composed of used newspapers. In any case, high yield removal with excellent ink removability is possible. It becomes possible to provide black pulp. On the other hand, it is possible to provide an environmentally friendly deinked pulp production method by reducing the amount of sludge ash generated, and also reduce the cost of chemicals because the filler used in the papermaking process can be reduced.
以下に実施例を用いて本発明をさらに詳しく説明するが、本発明はこれらの実施例に限定されるものではない。以下に示す実施例、比較例、参考例中の「%」は、白色度を除き、全て「質量%」を意味する。
また、市販薬剤を含む凝結剤、紙力剤、歩留剤の使用量は、「絶乾パルプ質量に対する割合(質量%)」で示した。なお、「絶乾パルプ質量」は、各工程においてその都度、一定量の試料を採取し、濾紙を用いた濾過により固形分と水分とを分離し、当該固形分を、その質量が一定になるまで105℃の乾燥機中で乾燥することによって求めた。
実施例8及び10は参考例である。
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples, comparative examples, and reference examples shown below, “%” means “% by mass” except for the whiteness.
Moreover, the usage-amount of the coagulant | flocculant containing a commercially available chemical | medical agent, a paper strength agent, and a retention agent was shown by the "ratio (mass%) with respect to the absolute dry pulp mass." In addition, “absolutely dry pulp mass” means that a certain amount of sample is taken each time in each step, solid content and moisture are separated by filtration using filter paper, and the mass of the solid content becomes constant. Until drying in a dryer at 105 ° C.
Examples 8 and 10 are reference examples.
添加薬剤としては以下の3種類を用いた。
市販薬剤I:ハリマ化成株式会社製、商品名ハリアップAC(歩留剤として。)
市販薬剤 II:荒川化学株式会社製、商品名KW−387−20(紙力剤として。)
市販薬剤 III:栗田工業株式会社製、商品名フィクサージュ621(凝結剤として。)
The following three types were used as additive drugs.
Commercial drug I: Harima Kasei Co., Ltd., trade name Hariup AC (as a retention agent)
Commercially available drug II: manufactured by Arakawa Chemical Co., Ltd., trade name KW-387-20 (as a paper strength agent)
Commercially available drug III: manufactured by Kurita Kogyo Co., Ltd., trade name Fixage 621 (as a coagulant)
(実施例1)
〈原料印刷古紙〉
JIS P8251で規定される525℃燃焼法での灰分が13.1%、かつ、JIS P8252で規定される900℃燃焼法での灰分が9.8%である印刷新聞60%と、チラシ40%とからなる印刷古紙を原料古紙として用いた。当該原料古紙1kgに占める絶乾パルプ質量は928gであった。
Example 1
<Recycled raw paper>
60% of printed newspapers with ash content of 13.1% in the 525 ° C combustion method specified in JIS P8251 and 9.8% in the 900 ° C combustion method specified in JIS P8252, 40% of leaflets The used printed paper consisting of The mass of the absolutely dry pulp occupying 1 kg of the used waste paper was 928 g.
〈離解工程〉
前記原料古紙を熊谷理機工業(株)製の標準パルプ離解機に入れ、30℃の水を加えて固形分濃度を3%とし、絶乾パルプ質量に対して0.4%の苛性ソーダと、絶乾パルプ質量に対して0.10%の脱墨剤(東邦化学製、FT−515)とを加え、JIS P8220に準じて、離解処理を20分間実施した。
<Disaggregation process>
Put the raw waste paper into a standard pulp disintegrator manufactured by Kumagaya Riki Kogyo Co., Ltd., add water at 30 ° C. to a solid content concentration of 3%, 0.4% caustic soda with respect to the absolute dry pulp mass A deinking agent (FT-515, manufactured by Toho Chemical Co., Ltd.) of 0.10% with respect to the mass of the absolutely dry pulp was added, and the disaggregation treatment was performed for 20 minutes according to JIS P8220.
〈除塵工程〉
離解処理後の離解液に対し、0.15mmのスリット幅を持つ6カットスクリーンプレートを備えたフラットスクリーン(熊谷理機工業製)を用いて除塵処理を行った。
<Dust removal process>
The disaggregation solution after the disaggregation treatment was subjected to a dust removal treatment using a flat screen (manufactured by Kumagai Riki Kogyo Co., Ltd.) equipped with a 6-cut screen plate having a slit width of 0.15 mm.
〈分散工程〉
除塵処理後の離解液を、150メッシュワイヤーにて固形分濃度が30%になるまで濃縮脱水した。脱水の後、絶乾パルプ質量に対して1.5%の苛性ソーダと、絶乾パルプ質量に対して1.5%のケイ酸ソーダと、絶乾パルプ質量に対して1.5%の過酸化水素と、30℃の水とを加え、固形分濃度を25%に調製した。その後、熊谷理機工業(株)製のPFIミルを用いて、1000回転の分散処理をJIS P8221−2に準じて実施した。
<Dispersing process>
The decontaminated solution after the dust removal treatment was concentrated and dehydrated with a 150 mesh wire until the solid content concentration became 30%. After dehydration, 1.5% caustic soda with respect to the absolute dry pulp mass, 1.5% sodium silicate with respect to the absolute dry pulp mass, and 1.5% peroxidation with respect to the absolute dry pulp mass Hydrogen and water at 30 ° C. were added to adjust the solid concentration to 25%. Thereafter, using a PFI mill manufactured by Kumagai Riki Kogyo Co., Ltd., 1000 rotation dispersion processing was performed according to JIS P8221-2.
〈漂白工程〉
上記分散処理後の分散液をビニール袋に入れ、これを70℃の恒温水槽に入れて120分間保持することにより漂白処理を行った。
<Bleaching process>
The dispersion after the dispersion treatment was placed in a plastic bag, and this was placed in a constant temperature water bath at 70 ° C. and held for 120 minutes for bleaching treatment.
〈フローテーション工程〉
上記漂白処理後の分散液を熊谷理機工業(株)製の標準パルプ離解機に入れ、40℃の温水を加えた後、硫酸でパルプスラリーのpHを7.5に調整し、さらに、絶乾パルプ質量に対して0.20%の脱墨剤(花王製、DI−3000)を加えた。そして、1分間の解繊処理を行ってパルプを水中によく分散させると共に、脱墨剤とパルプとをよく混合し、固形分濃度1%、40℃のパルプスラリーを調製した。その後、このパルプスラリーを、(株)IHIフォイトペーパーテクノロジー製のMTフローテーターに入れ、5分間のフローテーションによる脱墨処理を行った。
<Flotation process>
The dispersion after the bleaching treatment is placed in a standard pulp disintegrator manufactured by Kumagai Riki Kogyo Co., Ltd., 40 ° C. warm water is added, and the pH of the pulp slurry is adjusted to 7.5 with sulfuric acid. 0.20% of a deinking agent (Kao, DI-3000) was added to the dry pulp mass. Then, the fiber was defibrated for 1 minute to thoroughly disperse the pulp in water, and the deinking agent and the pulp were mixed well to prepare a pulp slurry having a solid content of 1% and 40 ° C. Then, this pulp slurry was put into MT flowtater made by IHI Voith Paper Technology Co., Ltd. and subjected to deinking treatment by flotation for 5 minutes.
〈洗浄工程〉
上記フローテーション後のパルプを攪拌下で対パルプ0.05%の割合でポリアクリルアミドを添加し、メスシリンダーで1000ml分取し、40meshワイヤー上に流し入れて、搾水量が850mlになるまで専用のヘラを用いて脱水させ、ワイヤー上に完成脱墨パルプを得た。
<Washing process>
Polyacrylamide is added to the pulp after the above flotation at a ratio of 0.05% with respect to the pulp, and 1000 ml is taken with a graduated cylinder, poured onto a 40 mesh wire, and a dedicated spatula until the squeezed amount reaches 850 ml. Was used to obtain a finished deinked pulp on the wire.
(実施例2〜10、比較例1〜3、参考例)
前記実施例1の方法におけるフローテーション工程において、それぞれ表1に記載のとおりのpH調整を行い、前記洗浄工程前の脱墨パルプスラリーにそれぞれ表1に記載のとおりの薬剤の種類、添加量を変えて添加した以外は、実施例1と同様にして完成脱墨パルプを得た。
(Examples 2 to 10, Comparative Examples 1 to 3, Reference Example)
In the flotation step in the method of Example 1, the pH adjustment as shown in Table 1 was performed, respectively, and the type and addition amount of the drug as shown in Table 1 were added to the deinked pulp slurry before the washing step, respectively. A finished deinked pulp was obtained in the same manner as in Example 1 except that the addition was changed.
〈評価〉
(歩留向上の評価/全歩留の測定)
フローテーション工程を経たパルプ1000gを40meshワイヤーで搾水質量が850gになるまでワイヤー上でパルプを転がすように脱水洗浄処理し、脱水洗浄前パルプ、脱水洗浄後パルプ、搾水の3か所のパルプ質量、および、濃度をJIS P 8225に準じて測定し、脱水洗浄工程前後の物量バランスから全歩留を算出し、下記の評価基準により、歩留向上の評価を行った。その結果を表1に示した。
<Evaluation>
(Evaluation of yield improvement / Measurement of total yield)
1000g of pulp after the flotation process is dehydrated and washed so that the pulp is rolled on the wire until the squeezed mass reaches 850g with a 40 mesh wire, pulp before dehydration washing, pulp after dehydration washing, and pulp from 3 parts of squeezed water The mass and the concentration were measured according to JIS P 8225, the total yield was calculated from the quantity balance before and after the dehydration washing process, and the yield improvement was evaluated according to the following evaluation criteria. The results are shown in Table 1.
(評価基準)
◎:全歩留が87.0%以上であった。
○:全歩留が85.0%以上87.0%未満であった。
△:全歩留が83.0%以上85.0%未満であった。
×:全歩留が83.0%未満であった。
(Evaluation criteria)
A: The overall yield was 87.0% or more.
○: The total yield was 85.0% or more and less than 87.0%.
Δ: Total yield was 83.0% or more and less than 85.0%.
X: The total yield was less than 83.0%.
(遊離インキ除去性の評価/白色度の測定)
フローテーション工程を経て、洗浄工程後に得られた完成脱墨パルプに、絶乾パルプ質量に対して15%の硫酸アルミニウムを加えてよく攪拌し、繊維から剥離している遊離インキを繊維に定着させた。その後、JIS P 8222に準じて、熊谷理機工業(株)の手抄き機を用いて手抄き紙を作製した。手抄き紙の作製後、JIS P8148に準じて白色度を測定した。そして、下記の評価基準により、遊離しているインキ除去性の評価を行った。その結果を表1に示した。
(Evaluation of free ink removability / Measurement of whiteness)
After completion of the flotation process, 15% aluminum sulfate is added to the finished deinked pulp obtained after the washing process and stirred well to fix the free ink peeled from the fiber to the fiber. It was. Thereafter, according to JIS P 8222, hand-made paper was prepared using a hand-making machine manufactured by Kumagai Riki Kogyo Co., Ltd. After producing the handmade paper, the whiteness was measured according to JIS P8148. Then, according to the following evaluation criteria, the free ink removal property was evaluated. The results are shown in Table 1.
(評価基準)
◎:白色度が68%以上であった。
○:白色度が67%以上68%未満であった。
△:白色度が66%以上67%未満であった。
×:白色度が66%未満であった。
ここでいう「白色度」は、主にフローテーションによる脱墨処理で除去できなかった遊離インキがどの程度残留しているかを示す指標となり、白色度が高いほど、残留している遊離インキが少ないことを意味する。
(Evaluation criteria)
A: Whiteness was 68% or more.
○: Whiteness was 67% or more and less than 68%.
Δ: Whiteness was 66% or more and less than 67%.
X: The whiteness was less than 66%.
The “whiteness” here is an index indicating how much free ink that could not be removed mainly by the deinking process by flotation remains. The higher the whiteness, the less free ink remains. Means that.
(経済性の評価)
凝結剤、紙力剤、歩留剤の薬剤を添加するとコストが嵩むため、添加量に対して経済性の評価を行った。その結果を表1に示した。
(Evaluation of economic efficiency)
When adding a coagulant, a paper strength agent, or a retention agent, the cost increases. Therefore, economic evaluation was performed on the amount added. The results are shown in Table 1.
(評価基準)
◎:薬剤添加量が0〜1000ppm以下
○:薬剤添加量が1000ppmを超え2000ppm以下であった。
△:薬剤添加量が2000ppmを超え3000ppm以下であった。
×:薬剤添加量が3000ppm超であった。
(Evaluation criteria)
A: The amount of drug added was 0 to 1000 ppm or less. O: The amount of drug added exceeded 1000 ppm and was 2000 ppm or less.
(Triangle | delta): The chemical | medical agent addition amount exceeded 2000 ppm and was 3000 ppm or less.
X: The amount of drug added was more than 3000 ppm.
(総合評価)
上記の歩留向上、及びインキ除去性についての評価結果を基にして、下記の評価基準により総合評価を行った。
(評価基準)
◎:上記の3つの評価のうち、ひとつ以上が◎で、かつ、残りが○であった。
○:上記の3つの評価の全てが○であった。
△:上記の3つの評価のうち、ひとつ以上が△で、かつ、残りが○又は◎であった。
×:上記の3つの評価のうち、ひとつ以上が×であった。
(Comprehensive evaluation)
Based on the above evaluation results for yield improvement and ink removability, comprehensive evaluation was performed according to the following evaluation criteria.
(Evaluation criteria)
A: Among the above three evaluations, one or more were A, and the rest were B.
○: All of the above three evaluations were ○.
Δ: Among the above three evaluations, one or more were Δ, and the remaining were ○ or ◎.
X: One or more of the above three evaluations was x.
表1に示す結果から、いずれの薬剤も洗浄工程前に添加することで歩留向上が認められ、中性領域での脱墨後の歩留向上が顕著である。また、中性領域で脱墨を行うことで、インキ除去性が著しく良好になることが分かる。 From the results shown in Table 1, the yield improvement is recognized by adding any chemical before the washing step, and the yield improvement after deinking in the neutral region is remarkable. In addition, it can be seen that deinking is performed in a neutral region, so that ink removability is remarkably improved.
実施例2、3、6、7と比較例1、2を比較すると分かるように、中性領域で脱墨を行っていない場合はインキ除去性が著しく劣ることが分かる。また、比較例3および参考例の結果が示すように、洗浄工程前に添加する薬剤の添加量が低すぎると歩留向上は望めず、添加率が高すぎても歩留向上のコスト対価が著しく劣り、経済性が大きく悪化する。 As can be seen from a comparison between Examples 2, 3, 6, and 7 and Comparative Examples 1 and 2, it can be seen that the ink removability is remarkably inferior when deinking is not performed in the neutral region. In addition, as the results of Comparative Example 3 and Reference Example show, the yield improvement cannot be expected if the amount of the chemical added before the washing process is too low, and the cost price for improving the yield is too high even if the addition rate is too high. It is extremely inferior and the economy is greatly deteriorated.
以上の結果から、フローテーション工程をpH6〜9の中性領域で行い、その後の洗浄工程の直前のパルプスラリーに対し、凝結剤、紙力剤、歩留剤の1つ以上を添加することで、脱墨効果、漂白効果を向上させ、かつ、インキ除去性の優れた脱墨パルプを製造することができる。 From the above results, the flotation step is performed in a neutral region of pH 6-9, and one or more of a coagulant, a paper strength agent, and a retention agent is added to the pulp slurry immediately before the subsequent washing step. In addition, it is possible to produce a deinked pulp having improved deinking and bleaching effects and excellent ink removability.
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