JP6443291B2 - Method for producing deinked pulp - Google Patents
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- JP6443291B2 JP6443291B2 JP2015199464A JP2015199464A JP6443291B2 JP 6443291 B2 JP6443291 B2 JP 6443291B2 JP 2015199464 A JP2015199464 A JP 2015199464A JP 2015199464 A JP2015199464 A JP 2015199464A JP 6443291 B2 JP6443291 B2 JP 6443291B2
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- flotation
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- deinked pulp
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- 229920001131 Pulp (paper) Polymers 0.000 title claims description 45
- 238000004519 manufacturing process Methods 0.000 title claims description 28
- 238000000034 method Methods 0.000 claims description 152
- 230000008569 process Effects 0.000 claims description 132
- 238000005406 washing Methods 0.000 claims description 49
- 238000005188 flotation Methods 0.000 claims description 46
- 230000018044 dehydration Effects 0.000 claims description 41
- 238000006297 dehydration reaction Methods 0.000 claims description 41
- 238000004061 bleaching Methods 0.000 claims description 30
- 239000002761 deinking Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000006185 dispersion Substances 0.000 claims description 22
- 239000013055 pulp slurry Substances 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000010790 dilution Methods 0.000 claims description 8
- 239000012895 dilution Substances 0.000 claims description 8
- 238000007639 printing Methods 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 238000009897 hydrogen peroxide bleaching Methods 0.000 claims description 3
- 239000000123 paper Substances 0.000 description 25
- 239000003795 chemical substances by application Substances 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000010893 paper waste Substances 0.000 description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 14
- 239000000835 fiber Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 239000000428 dust Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 6
- 239000003814 drug Substances 0.000 description 6
- 229940079593 drug Drugs 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 238000012216 screening Methods 0.000 description 6
- 239000000470 constituent Substances 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000000701 coagulant Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
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- 230000007935 neutral effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000010802 sludge Substances 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000004931 aggregating effect Effects 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
- 230000007613 environmental effect Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000013054 paper strength agent Substances 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002351 wastewater 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
- 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 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
- 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
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000007796 conventional method 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
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 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
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 238000000691 measurement method 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
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000002245 particle Substances 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
- 238000004537 pulping Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 230000002463 transducing effect Effects 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、印刷古紙から再生パルプを得るための脱墨古紙パルプの製造方法に関し、特に、古紙由来の填料を含む灰分の歩留りを向上して、生産コストの低減と環境負荷の軽減を両立できる脱墨古紙パルプの製造方法に関する。 The present invention relates to a method for producing deinked waste paper pulp for obtaining recycled pulp from printed waste paper, and in particular, it is possible to improve the yield of ash containing fillers derived from waste paper and achieve both reduction of production cost and reduction of environmental burden. The present invention relates to a method for producing deinked waste paper pulp.
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・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ことを目的として、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ていて一定の歩留向上は可能となっている。しかし、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可能とす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, earnest research has been conducted on the recovery of ash in the floss and the recovery of fine fibers with the aim of improving the yield of fine fibers and fillers. Is possible. However, it has been difficult to further improve the yield while maintaining the ink removal property of the finished deinked pulp.
古紙再生処理工程において、フローテーション工程を経た後、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)が提案されている。他に、同様に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)も提案されている。しかし、これらを使用した場合、コストが非常に嵩むし、フローテーションでインキの除去が不完全な場合は、その後に脱墨パルプの歩留向上を目的として凝結剤、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大きな欠点があった。 In the used paper recycling process, a method of adding a coagulant to the pulp slurry after the flotation process and before the washing process and the dewatering process (for example, Patent Document 1) has been proposed. In addition, a method of adding a water-soluble amphoteric copolymer obtained by polymerizing (meth) acrylamide + cationic monomer + anionic monomer as a constituent component after flotation in the same manner (for example, Patent Document 2), ) Acrylamide and a cationic monomer as constituents, or (meth) acrylamide, a cationic monomer and (c) an anionic monomer as constituents, and (d) a crosslinkable monomer and / or (e) A method of adding a water-soluble ionic polyacrylamide copolymer polymerized using a chain transfer agent (Patent Document 3) has also been proposed. However, when these are used, the cost is very high, and if the ink is not completely removed by flotation, then a coagulant, a paper strength agent, a retention agent for the purpose of improving the yield of deinked pulp. , There was a major drawback that the ink removal property of the finished deinked pulp was significantly inferior.
従来の脱墨パルプの製造方法によれば、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、概ね白色度の高い脱墨パルプを製造することができる。確かに、刷古紙中のインキは完成の脱墨パルプの品質に悪影響を及ぼす。しかし、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有利である。さらに、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完成脱墨パルプ中に残留させることが有利である。 According to the conventional method of producing deinked pulp, the ink contained in the deinked pulp is removed together with the ash in the screening process, flotation process, washing process, dewatering process, etc. Pulp can be produced. Certainly, the ink in the used paper has an adverse effect on the quality of the finished deinked pulp. However, the ash content is relatively white, and it is advantageous in terms of cost and environment from the viewpoint of reducing wastes to remain in the pulp slurry as a constituent of the finished deinked pulp. Furthermore, the ash discharged in the filtrate without remaining in the deinked pulp accumulates as a scale in the piping of the inflow, so it is advantageous to leave it in the finished deinked pulp from the viewpoint of equipment maintenance. It is.
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を得ることができると同時に、スラッジ灰の低減と使用填料の低減を図ることができ、さらに排水のCOD量を抑制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 can obtain deinked pulp with high ash content and excellent residual ink removal properties from used printed paper, and at the same time, can reduce sludge ash and filler used. Another object of the present invention is to provide a method for producing deinked pulp that can further reduce the amount of COD in waste water.
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(除塵)工程、漂白工程、ニーディング(分散)工程、フローテーション(脱墨)工程、脱水・洗浄工程等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のみならず、その後のニーディング(分散)工程、フローテーション(脱墨)工程、脱水・洗浄工程もpH9.5を超えるアルカリ性領域で行われているのが一般的である。
本発明者らは検討を重ねた結果、脱水・洗浄工程で処理するパルプスラリーに酸を加えてpHを6.0〜9.5の中性のpH領域に維持して脱水・洗浄処理を行うことで、高歩留で、且つ、インキ除去性の優れた脱墨パルプを製造できることを見出し、以下の発明をなすに至った。
Conventionally, a method for producing deinked pulp from used printed paper consists of a combination of a disaggregation process, a screening (dust removal) process, a bleaching process, a kneading (dispersing) process, a flotation (deinking) process, and a dehydration / washing process. In the pulping process of waste paper, not only the bleaching process performed in an alkaline manner, but also the subsequent kneading (dispersing) process, flotation (deinking) process, and dehydration / washing process are performed in an alkaline region exceeding pH 9.5. It is common.
As a result of repeated investigations, the present inventors added acid to the pulp slurry to be treated in the dehydration / washing step to maintain the pH in a neutral pH range of 6.0 to 9.5 and perform the dehydration / washing treatment. As a result, it has been found that deinked pulp having high yield and excellent ink removability can be produced, and the following inventions have been made.
(1)印刷古紙の離解工程、脱墨処理するフローテーション工程、インキ分散処理する分散工程、漂白工程、脱水・洗浄工程を全工程中に少なくとも有している一連の工程に従った脱墨パルプの製造方法において、前記分散工程と漂白工程が連続する組み合わせ工程部分を中間工程として有し、前記離解工程から該中間工程に至る前段の工程と該中間工程とを含む一連の工程をpH7.0〜13.0の範囲から選択されるpH条件下で処理する工程とするとともに、該中間工程後の後段の工程中に、前記フローテーション工程と、pH6.0〜9.5の範囲に調整して処理する脱水・洗浄工程とを配置し、該後段の工程中の脱水・洗浄工程より発生するろ液を主として後段の工程における希釈水及び/又は洗浄水として使用することを特徴とする脱墨パルプの製造方法。
(2)前記後段の工程における脱水・洗浄工程をpH6.0〜9.5の範囲で処理する工程に調整する手段が、該脱水・洗浄工程に導入されるパルプスラリーに酸を添加することよりなる手段であることを特徴とする(1)項に記載の脱墨パルプの製造方法。
(3)前記酸が硫酸であることを特徴とする(2)項に記載の脱墨パルプの製造方法。
(4)前記後段の工程におけるフローテーション工程後の脱水・洗浄工程から排出されるろ液の主要部を該後段の工程におけるフローテーション工程の希釈水及び/又は該脱水・洗浄工程の洗浄水として使用することを特徴とすることを特徴とする(1)項〜(3)項のいずれか1項に記載の脱墨パルプの製造方法。
(5)前記後段の工程におけるフローテーション工程を、pH6.0〜9.5の範囲に調整して脱墨処理する工程とすることを特徴とする(1)項〜(4)項のいずれか1項に記載の脱墨パルプの製造方法。
(6)前記中間工程における漂白工程がアルカリ過酸化水素漂白工程であることを特徴とする(1)項〜(5)項のいずれか1項に記載の脱墨パルプの製造方法。
(7)前記前段の工程における離解工程後に、フローテーション工程と引き続く脱水・洗浄工程を配置し、該前段工程における脱水・洗浄工程より排出されるろ液を離解工程の希釈水として使用するとともに、前記後段の工程における脱水・洗浄工程より排出されるろ液の一部を該離解工程の希釈水として使用することを特徴とする(1)項〜(6)項のいずれか1項に記載の脱墨パルプの製造方法。
(8)前記前段の工程、前記中間工程及び前記後段の工程よりなる一連の工程が、離解工程、前段のフローテーション工程、前段の脱水・洗浄工程、中間工程、後段のフローテーション工程、後段の脱水洗浄工程を該順序となるように全工程中に配置した一連の工程であることを特徴とする(1)項〜(7)項のいずれか1項に記載の脱墨パルプの製造方法。
(1) Deinked pulp according to a series of steps including at least a disintegration process of used printing paper, a flotation process for deinking, a dispersion process for dispersing ink, a bleaching process, and a dehydration / washing process. In the production method, a combination process part in which the dispersion process and the bleaching process are continued is an intermediate process, and a series of processes including the preceding process from the disaggregation process to the intermediate process and the intermediate process is performed at pH 7.0. In addition to the step of treating under a pH condition selected from the range of ˜13.0, the flotation step and the pH of 6.0 to 9.5 are adjusted during the subsequent step after the intermediate step. And a dehydration / washing process to be processed in the process, and the filtrate generated from the dehydration / washing process in the latter process is mainly used as dilution water and / or washing water in the latter process. Manufacturing method of deinking pulp that.
(2) Means for adjusting the dehydration / washing process in the latter process to a process in the range of pH 6.0 to 9.5, by adding acid to the pulp slurry introduced into the dehydration / washing process The method for producing deinked pulp according to item (1), characterized in that:
(3) The method for producing deinked pulp according to (2), wherein the acid is sulfuric acid.
(4) The main part of the filtrate discharged from the dehydration / washing process after the flotation process in the latter process is used as dilution water in the flotation process and / or washing water in the dehydration / washing process in the latter process. The method for producing a deinked pulp according to any one of (1) to (3), wherein the deinked pulp is used.
(5) Any one of (1) to (4), wherein the flotation process in the subsequent process is a process of adjusting the pH to a range of 6.0 to 9.5 and performing a deinking process. 2. A method for producing deinked pulp according to item 1.
(6) The method for producing deinked pulp according to any one of (1) to (5), wherein the bleaching step in the intermediate step is an alkali hydrogen peroxide bleaching step.
(7) After the disaggregation step in the preceding step, a flotation step and a subsequent dehydration / washing step are arranged, and the filtrate discharged from the dehydration / washing step in the preceding step is used as dilution water in the disaggregation step, A part of the filtrate discharged from the dehydration / washing step in the subsequent step is used as the dilution water in the disaggregation step, according to any one of items (1) to (6) A method for producing deinked pulp.
(8) A series of processes including the preceding process, the intermediate process, and the subsequent process includes a disaggregation process, a pre-stage flotation process, a pre-stage dehydration / washing process, an intermediate process, a post-stage flotation process, and a post-stage flotation process. The method for producing a deinked pulp according to any one of items (1) to (7), wherein the dehydrating and washing steps are a series of steps arranged in all steps so as to be in this order.
本発明の方法によれば、インキ除去性を損なわずに印刷古紙由来の填料を含む灰分及び繊維成分の歩留を向上させた高白色の古紙脱墨パルプが提供されるので、紙製品へ、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こと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 method of the present invention, a high-white waste paper deinked pulp with improved yield of ash and fiber components containing fillers derived from used printed paper without impairing ink removability is provided. It is possible to blend high-priced deinked pulp that is cheaper than kraft pulp, mechanical pulp, and the like, and it is possible to reduce the environmental burden, thereby expanding the range of used paper.
以下、本発明の脱墨パルプの製造方法について詳細に説明する。
(原料印刷古紙)
本発明の方法において、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%含む古紙が挙げられる。本発明の方法は、多量の表面処理剤を含む脱墨性が悪い一部の中性新聞紙を含む印刷古紙、特に高灰分の塗工紙にも効果的である。
Hereinafter, the manufacturing method of the deinked pulp of this invention is demonstrated in detail.
(Recycled raw paper)
In the method of the present invention, examples of the used printing paper used 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 method of the present invention is also effective for used printing paper including some neutral newspapers having a large amount of surface treatment agent and having poor deinking property, particularly coated paper having a high ash content.
(離解工程)
本発明の方法を実施する一連の工程における離解工程について特に制限は無い。離解工程における好ましい処理においては、原料印刷古紙を固形分濃度12〜18質量%になるように稀釈水に入れ、更にアルカリ薬品(水酸化ナトリウム等)を対パルプ0〜3.0質量%、好ましくは0.1〜2.5質量%添加して行う処理が挙げられる。アルカリ薬品添加による離解処理時のpH値は、一般的にはpH10.0〜13.0とされる。
離解工程で脱墨剤を使用する場合には、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%添加する。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分であり、離解温度は10〜50℃、好ましくは30〜50℃である。
(Disaggregation process)
There is no restriction | limiting in particular about the disaggregation process in a series of processes which implement the method of this invention. In a preferable treatment in the disaggregation step, the raw printed paper is put in diluted water so as to have a solid content concentration of 12 to 18% by mass, and further an alkali chemical (such as sodium hydroxide) is added to 0 to 3.0% by mass of pulp, preferably Includes a treatment performed by adding 0.1 to 2.5% by mass. The pH value during the disaggregation treatment with the addition of an alkaline chemical is generally set to pH 10.0 to 13.0.
In the case of using a deinking agent in the disaggregation step, 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 with respect to pulp, preferably Add 0.03-0.3 mass%. 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、高級アルコールと脂肪酸のハイブリットタイプ等があるが、例えば、次のものを挙げることができるが、これらに限定されるものではない。
花王(株)社製のDI−7020、DI−7030、DI−767、DI−7282、DI−7300、DI−7250、日新化学研究所(株)社製のDIA−Z−100、DIA−Z−5000、東邦化学(株)社製のネオスコア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、FT−517、B−B剤、第一工業製薬(株)社製ダイホープ940、ダイホープ960、日華(株)社製リポブライトDP−810等。
Examples of deinking agents with strong ink peelability include higher alcohol-based deinking agents, amphoteric deinking agents, and hybrid types of higher alcohols and fatty acids. It is not limited.
DI-7020, DI-7030, DI-767, DI-7282, DI-7300, DI-7250, manufactured by Kao Corporation, DIA-Z-100, DIA- manufactured by Nissin Chemical Laboratory Co., Ltd. Z-5000, Neoscore FW-780, Neoscore FW-790, Neoscore FW-795, FT-467, FT-470, FT-487, FT-511, FT-513, FT-514, manufactured by Toho Chemical Co., Ltd. , FT-515, FT-517, BB agent, Daihope 940, Daihope 960, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Lipobright DP-810, manufactured by Nikka Corporation.
(除塵工程)
本発明の方法を実施する一連の工程には除塵のためのスクリーニング工程を配置することができる。除塵のためのスクリーニング工程としては特に制限はない。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く、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。
(Dust removal process)
A screening step for dust removal can be arranged in a series of steps for carrying out the method of the present invention. There is no particular limitation on the screening process for dust removal. It is sufficient that foreign substances in the raw material can be removed with a screen cleaner, and 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.
(中間工程)
本発明の方法を実施する一連の工程は、インキ分散処理する分散工程と漂白工程とを組み合わせた中間工程部分を有する。中間工程は分散工程−漂白工程の組み合わせと分散工程−漂白工程―分散工程の組み合わせのいずれかの組み合わせ工程とすることができる。
中間工程における分散工程は分散機によりインキ成分等を分散処理する工程である。分散機としては、低速・高濃度用軸タイプの分散機や、ディスクタイプの分散機の使用が適している。低速・高濃度用軸タイプの分散機としては、一軸型又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。このタイプのディスパーザーは、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ており、回転数50〜300rpmの低速で、処理濃度20質量%〜50質量%の高濃度、好ましくは、25質量%〜40質量%で、温度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質量%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質量%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。
(Intermediate process)
A series of steps for carrying out the method of the present invention has an intermediate step portion in which a dispersion step for carrying out ink dispersion treatment and a bleaching step are combined. The intermediate step can be any combination step of a combination of a dispersion step-bleaching step and a combination of a dispersion step-bleaching step-dispersion step.
The dispersion step in the intermediate step is a step of dispersing the ink components and the like with a disperser. As the disperser, a low speed / high concentration shaft type disperser or a disk type disperser is suitable. As the low-speed / high-concentration shaft type disperser, a uniaxial or biaxial kneader type disperser is preferable. This type of disperser has a rotary blade attached to a shaft-like rotor and a fixed blade attached to a casing, and a processing concentration of 20% by mass to 50% by mass at a low speed of 50 to 300 rpm. Is preferably processed 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% by mass, it is difficult to apply a mechanical load, ink dispersibility / dirt dispersibility is lowered, and energy required for temperature increase is enormous, which is not suitable. In addition, if the treatment concentration exceeds 50 mass% and the concentration is high, it is difficult to squeeze mechanically.
分散機としては、一般的には次のものが使用されるが、特定の機種に限定するものではない。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)等。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等。一方、ディスクタイプのディスパーザーとしては、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)、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。ただし、これらの機種に限定されるものではない。 As a disperser, the following are generally used, but are not limited to a specific model. As a single-axis kneader, kneading disperser KD (product name: manufactured by IH IFOIT Paper Technology), disperser (product name: manufactured by Aikawa Tekko), disperser (product name: manufactured by ASEC), Disperser (trade name: manufactured by Sanei Regulator Co., Ltd.), CCE type kneading machine (trade name: manufactured by Niihama Pump Manufacturing Co., Ltd.), kneader (trade name: manufactured by Hyakuma Yamamoto Manufacturing Co., Ltd.), etc. Two-shaft kneaders manufactured by Niihama Pump Mfg. Co., Ltd. and Yamamoto Hyakuma Mfg. On the other hand, as a disc type disperser, Disperser HTD (trade name: manufactured by IH IFOIT Paper Technology Co., Ltd.), KRIMA hot dispersion equipment (trade name: manufactured by Cellwood), Koni Disc (trade name: Aikawa) Iron Disperser, Conical Dispersion System / HI Preheater / OptiFinner Disperser (trade name: Metso SHI) and the like are used. However, it is not limited to these models.
(漂白工程)
本発明の方法を実施する一連の工程中の中間工程部分における漂白工程は漂白薬品を使用して漂白処理を行う工程である。漂白工程で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。本発明の方法では主として過酸化水素を使用してアルカリ過酸化水素漂白を行う。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1.0〜3.0質量%、珪酸ソーダは、対パルプ1.0〜3.5質量%添加する。
(Bleaching process)
The bleaching step in the intermediate step part of the series of steps for carrying out the method of the present invention is a step of performing a bleaching treatment using a bleaching chemical. Hydrogen peroxide, hydrosulfide, thiourea dioxide, hypo, etc. are used as bleaching chemicals in the bleaching process. In the method of the present invention, alkaline hydrogen peroxide bleaching is mainly performed using hydrogen peroxide. Hydrogen peroxide is added in an amount of 0.5 to 5.0 mass% with respect to the pulp. Even if the amount added is further increased, the increase in whiteness tends to saturate. Caustic soda is added to 1.0 to 3.0 mass% of pulp, and sodium silicate is added to 1.0 to 3.5 mass% of pulp.
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し、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。
漂白処理時のパルプ濃度は15〜35質量%、好ましくは25〜30質量%であり、濃度が15質量%より低くなると過酸化水素の反応性が悪くなる。また、35質量%より高い濃度にすると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。
The bleaching time is 10 minutes to 5 hours, preferably 1.5 to 3 hours. If the bleaching time is too short, it is not preferable because the hydrogen peroxide does not react sufficiently, and even if the bleaching time is longer than 5 hours, the consumption of hydrogen peroxide proceeds. Not suitable because yellowing occurs.
The pulp concentration at the time of bleaching is 15 to 35% by mass, preferably 25 to 30% by mass. When the concentration is lower than 15% by mass, the reactivity of hydrogen peroxide is deteriorated. On the other hand, if the concentration is higher than 35% by mass, it is not preferable because the mixture with chemicals 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.
(フローテーション工程)
本発明を実施する一連の工程において、前記中間工程より後段の工程における脱墨処理を行うフローテーション工程は、インキ凝集性の高い脱墨剤を用いて行われる。脱墨剤をパルプに均一に混合することができれば、フローテーション工程の直前の漂白工程に脱墨剤を添加してもよい。中間工程における分散工程でのディスパーザー処理により剥離したインキをその後のフローテーション工程で除去する、という順序で処理することが好ましい。分散工程で剥離したインキを直接脱水・洗浄工程で除去する方法を採用すると、インキ粒子が洗浄ろ液とともに白水に含まれて循環してパルプの完成白色度に悪影響を与える恐れがあるため好ましくない。
(Flotation process)
In a series of steps for carrying out the present invention, the flotation step of performing the deinking process in the step subsequent to the intermediate step is performed using a deinking agent having high ink aggregating properties. If the deinking agent can be uniformly mixed with the pulp, the deinking agent may be added to the bleaching step immediately before the flotation step. It is preferable to process in the order that the ink peeled by the disperser process in the dispersion process in the intermediate process is removed in the subsequent flotation process. Adopting a method that directly removes ink separated in the dispersion process in the dehydration / washing process is undesirable because the ink particles may be circulated in the white water together with the washing filtrate to adversely affect the finished whiteness of the pulp. .
インキ凝集性の強い脱墨剤としては、例えば、次に挙げる脂肪酸あるいは脂肪酸誘導体系の脱墨剤があるが、これらに限定されるものではない。
脂肪酸の場合、花王(株)社製のDI−254(オレイン酸)、DI−268、第一工業製薬(株)社製のK−4004−D等がある。また、脂肪酸誘導体系の場合、花王(株)社製のDI−1120、DI−1050、日新化学研究所(株)社製のDIY−23543、第一工業製薬(株)社製のペーパーエイドW等がある。
Examples of deinking agents having strong ink aggregating properties include, but are not limited to, the following fatty acid or fatty acid derivative-based deinking agents.
In the case of fatty acids, there are DI-254 (oleic acid) and DI-268 manufactured by Kao Corporation, and K-4004-D manufactured by Daiichi Kogyo Seiyaku Co., Ltd. In the case of a fatty acid derivative, DI-1120 and DI-1050 manufactured by Kao Corporation, DIY-23543 manufactured by Nisshin Chemical Laboratory Co., Ltd., and Paper Aid manufactured by Daiichi Kogyo Seiyaku Co., Ltd. W etc.
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0.7〜1.5質量%で、フローテーターにおける処理温度は10〜55℃、好ましくは30〜50℃である。
フローテーション工程の処理pHは6.0〜9.5が適しており、7〜8.5がより好ましい。pHが6.0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9.5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を低減させる薬剤として、硫酸、塩酸のような酸が適しているが、調整用に苛性ソーダ、ケイ酸ソーダ等を用いてもよい。
Although there is no restriction | limiting in the form of the flotator in a flotation process, The process temperature in a floatator is 10-55 degreeC by process density | concentration 0.7-1.5 mass%, Preferably it is 30-50 degreeC.
The treatment pH in the flotation process is suitably 6.0 to 9.5, more preferably 7 to 8.5. When the pH is lower than 6.0, the corrosion of piping and equipment becomes a problem, and the equipment cost becomes expensive. Moreover, when pH exceeds 9.5, the ink removability of a deinked pulp will deteriorate remarkably. Moreover, as a chemical | medical agent which reduces the processing pH of a flotation, acids, such as a sulfuric acid and hydrochloric acid, are suitable, However, You may use caustic soda, sodium silicate etc. for adjustment.
(脱水・洗浄工程)
フローテーション処理を行なった後、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及び洗浄して除去する脱水・洗浄工程がある。処理pH値を6.0〜9.5に調整して脱水・洗浄処理することができる限り、洗浄装置に特に制限は無い。0.6〜1.5質量%のパルプスラリーを清水又は抄紙機のクリア白水で希釈した後、pHが6.0〜9.5の範囲となるように硫酸等の酸を添加して調整し、15〜35質量%まで脱水・洗浄することが好ましい。
脱水・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。
(Dehydration and washing process)
After the flotation treatment, there is a dehydration / washing process in which fine ink that could not be removed by the flotator is dehydrated and washed. The cleaning apparatus is not particularly limited as long as the treatment pH value can be adjusted to 6.0 to 9.5 and dehydration and cleaning can be performed. After diluting 0.6-1.5 mass% pulp slurry with clear water or clear white water of paper machine, adjust the pH by adding acid such as sulfuric acid so that the pH is in the range of 6.0-9.5. It is preferable to dehydrate and wash to 15 to 35% by mass.
There are extractor, fall washer (Eiko), and double nip thickener (Ishikawajima Sangyo), etc. as cleaning devices used in the dehydration / cleaning process, but the cleaning device preferentially removes ink in the raw material. 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前後のいずれか、または両方のパルプスラリーに酸を添加し、脱水・洗浄工程の直前のpHを6.0〜9.5とする。酸は、主に硫酸が好ましいが、pHを調整できるのであれば、塩酸、有機酸等でも構わない。また、脱水・洗浄工程直前のパルプスラリーに紙力剤、歩留剤、凝結剤等の薬剤を添加しても構わない。添加薬剤としては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、例えば、次のような薬剤が挙げられる。 In the method of the present invention, acid is added to one or both of the pulp slurries before and after the flotation step, and the pH immediately before the dehydration / washing step is set to 6.0 to 9.5. The acid is mainly preferably sulfuric acid, but hydrochloric acid, organic acid, etc. may be used as long as the pH can be adjusted. Further, chemicals such as a paper strength agent, a retention agent, and a coagulant may be added to the pulp slurry immediately before the dehydration / washing step. As the additive agent, any agent that improves the yield of ash and fiber can be suitably used. Examples thereof include the following agents.
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。
(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。)。
その他の市販の薬剤(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)。
上記薬剤の中では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. .
A drug comprising (meth) acrylamide, a water-soluble cationic monomer, and a water-soluble anionic monomer as constituents (generally referred to as amphoteric acrylamide, for example, Hariup AC manufactured by Harima Kasei Co., Ltd.).
Other commercially available drugs (for example, Polystron 372, KW-387-20 manufactured by Arakawa Chemical Co., Ltd., Acracac 208E manufactured by MT Aquapolymer Co., Accurac 100E, Fixage 621 manufactured by Kurita Kogyo Co., Ltd., Hymolock NR-70 manufactured by Hymo Co., Ltd. Realizer R500, Realizer R600, Kyowa Sangyo Keith Lock RP-532, etc.).
Among the above drugs, 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1ppm〜3000ppmであり、より好適なのは1000ppm〜2000ppmである。過添加の場合、灰分、繊維分とともにインキもパルプスラリーに吸着し、白色度の低下を招くとともに不経済であるため、必要最小限の添加に留める必要がある。 The addition amount of the drug is preferably 1 ppm to 3000 ppm, and more preferably 1000 ppm to 2000 ppm. In the case of excessive addition, the ink is adsorbed to the pulp slurry together with the ash and fiber components, resulting in a decrease in whiteness and being uneconomical. Therefore, it is necessary to keep the addition to the minimum necessary amount.
本発明の方法によれば、新聞古紙を主体とした印刷古紙よりISO白色度50%〜85%という幅広い範囲の脱墨パルプを高歩留で製造することが可能である。また、スラッジ灰の発生量を低減することが可能であることにより、環境にやさしい脱墨パルプの製造方法であると同時に、抄紙工程の使用填料を低減できるため、薬品コストの低減が可能な脱墨パルプの製造方法が提供される。 According to the method of the present invention, it is possible to produce deinked pulp in a wide range of ISO whiteness of 50% to 85% with a high yield from printed waste paper mainly composed of newspaper waste paper. In addition, the ability to reduce the amount of sludge ash generated is an environmentally friendly method of producing deinked pulp, and at the same time, the amount of filler used in the papermaking process can be reduced, so that chemical costs can be reduced. A method for producing black pulp is provided.
本発明の脱墨古紙パルプの製造方法は、前記の印刷古紙の離解工程、脱墨処理するフローテーション工程、インキ分散処理する分散工程、漂白工程、脱水・洗浄工程を含む限り、通常の古紙パルプの製造方法で採用されるその他の処理工程を含む一連の工程に従って実施することができる。一般的には、古紙に混入して製造工程内に持ち込まれる異物の除去を目的とするスクリーンやクリーナーなどを使用した異物除去工程乃至除塵工程(スクリーニング工程)も採用することができる。
また、前記中間工程より前段の工程において、前記離解工程、スクリーニング工程等を経たパルプスラリーを希釈して脱墨処理するフローテーション工程、該フローテーション工程後のパルプスラリーの脱水・洗浄工程等を配置して中間工程に導入する前のパルプスラリーを調製する方法を採用することもできる。
The method of producing the deinked waste paper pulp of the present invention is a normal waste paper pulp as long as it includes the above-mentioned disintegration process of the used waste paper, the flotation process for the deinking process, the dispersion process for the ink dispersion process, the bleaching process, and the dehydration / washing process. It can implement according to a series of processes including the other process process employ | adopted by the manufacturing method of this. Generally, a foreign matter removing process or a dust removing process (screening process) using a screen, a cleaner, or the like for the purpose of removing foreign substances mixed in the waste paper and brought into the manufacturing process can be employed.
In addition, a flotation process in which the pulp slurry that has undergone the disaggregation process, the screening process, etc. is diluted and deinked in the process preceding the intermediate process, and a pulp slurry dewatering / washing process after the flotation process are arranged. And the method of preparing the pulp slurry before introduce | transducing into an intermediate | middle process is also employable.
以下、実施例により本発明の方法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。以下に示す実施例及び比較例中の「%」は、白色度を除き全て「質量%」を意味する。
実施例1〜3は参考例である。
Hereinafter, the method of the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. In the examples and comparative examples shown below, “%” means “% by mass” except whiteness.
Examples 1 to 3 are reference examples.
(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13.7%、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918gであった。
Example 1
<Recycled raw paper>
60% of printed newspapers with ash content of 13.7% in the 525 ° C combustion method specified by JIS P8251 and 9.8% of ash content in the 900 ° C combustion method specified by JIS P8252, 40% of leaflets The used printed paper consisting of The mass of absolutely dry pulp occupying 1 kg of the used waste paper was 918 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−517)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, 0.10% of deinking agent (manufactured by Toho Chemical Co., Ltd., FT-517) was added to the absolute dry pulp mass, and the disaggregation treatment was carried out 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、絶乾パルプ質量に対して0.20%の脱墨剤(花王製、DI−1120)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。フローテーション直前のpHは10.5であった。
<Flotation process>
The dispersion after the bleaching treatment is put in a standard pulp disintegrator manufactured by Kumagai Riki Kogyo Co., Ltd., and after adding warm water at 40 ° C., 0.20% deinking agent (Kao Product, DI-1120). 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. The pH immediately before flotation was 10.5.
〈脱水・洗浄工程〉
上記フローテーション後のパルプスラリーに硫酸を添加し、pHを9.0に調整し、よく撹拌後に、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(ろ液)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。
<Dehydration and washing process>
Sulfuric acid is added to the pulp slurry after the above flotation, the pH is adjusted to 9.0, and after stirring well, 1000 ml is taken with a graduated cylinder, poured onto a 40 mesh wire, and the amount of squeezed water (filtrate) is 850 ml. A deinked pulp was obtained on the wire by dehydrating with a special spatula until it became.
(実施例2〜6、比較例1)
前記実施例1の方法におけるフローテーション工程前、及び、脱水・洗浄工程前において、硫酸を添加、又は、無添加とし、それぞれ表1に記載の通りにpH値を設定した以外は、実施例1と同様にして完成脱墨パルプを得た。
(Examples 2-6, Comparative Example 1)
Example 1 except that sulfuric acid was added or not added before the flotation process and before the dehydration / washing process in the method of Example 1, and the pH value was set as shown in Table 1, respectively. In the same manner, a finished deinked pulp was obtained.
〈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、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 concentration were measured according to JIS P 8225, and the total yield was calculated from the quantity balance before and after the dehydration washing process. The results are shown in Table 1.
(COD測定方法)
前記脱水・洗浄工程の搾水(ろ液)中のCOD量を求めた。COD量はJIS K 0102規格17に準じて各COD濃度を測定したのち、絶乾パルプ量あたりのCOD量(CODkg/パルプT)に換算した結果で示した。
(COD measurement method)
The amount of COD in the squeezed water (filtrate) in the dehydration and washing step was determined. The COD amount is shown as a result of measuring each COD concentration according to JIS K 0102 standard 17 and then converting it to the COD amount per COD (COD kg / pulp T).
(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、その結果を表1に示した。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 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, and the results are shown in Table 1. 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.
表1に示す結果に基づいて実施例1〜6と比較例1を比較すると分かるように、中間工程(分散工程−漂白工程)後に、フローテーション工程を経て洗浄工程に導入するパルプスラリーに酸を添加して、pH6.0〜9.5の範囲に調整することで、歩留向上が認められ、ワイヤー洗浄後のろ液中に溶出してくるCOD濃度も低下する。また、実施例5,6の結果から、フローテーション工程に導入するパルプスラリーのpHを中性領域に調整とすることで、更に、歩留向上、ろ液へのCOD溶出低減が顕著となり、白色度向上も可能となった。 As can be seen by comparing Examples 1 to 6 and Comparative Example 1 based on the results shown in Table 1, after the intermediate step (dispersion step-bleaching step), an acid is added to the pulp slurry introduced into the washing step via the flotation step. By adding and adjusting to pH 6.0-9.5, the yield improvement is recognized and the COD density | concentration which elutes in the filtrate after a wire washing | cleaning also falls. In addition, from the results of Examples 5 and 6, by adjusting the pH of the pulp slurry introduced into the flotation step to a neutral region, the yield is further improved and the COD elution is reduced in the filtrate. The degree of improvement was also possible.
本発明によれば、新聞古紙を主体とした印刷古紙から、スラッジ灰の発生量が少なく、排水のCOD濃度も低い環境にやさしい方法でインキ除去性に優れる再生パルプを高歩留まりで製造することができる脱墨パルプの製造方法が提供される。 According to the present invention, it is possible to produce recycled pulp excellent in ink removability and high yield from waste paper used mainly for newspaper waste by an environmentally friendly method that generates less sludge ash and low COD concentration in waste water. A method for producing a deinked pulp is provided.
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