JP6304023B2 - Method for producing deinked pulp - Google Patents
Method for producing deinked pulp Download PDFInfo
- Publication number
- JP6304023B2 JP6304023B2 JP2014265135A JP2014265135A JP6304023B2 JP 6304023 B2 JP6304023 B2 JP 6304023B2 JP 2014265135 A JP2014265135 A JP 2014265135A JP 2014265135 A JP2014265135 A JP 2014265135A JP 6304023 B2 JP6304023 B2 JP 6304023B2
- Authority
- JP
- Japan
- Prior art keywords
- pulp
- treatment
- ink
- dispersion
- bleaching
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920001131 Pulp (paper) Polymers 0.000 title claims description 36
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000006185 dispersion Substances 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 42
- 239000002761 deinking Substances 0.000 claims description 31
- 238000004061 bleaching Methods 0.000 claims description 24
- 238000005188 flotation Methods 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
- 230000007935 neutral effect Effects 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 11
- 239000000428 dust Substances 0.000 claims description 6
- 238000007639 printing Methods 0.000 claims description 4
- 238000010979 pH adjustment Methods 0.000 claims description 2
- 238000004537 pulping Methods 0.000 claims description 2
- 239000000976 ink Substances 0.000 description 44
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000000123 paper Substances 0.000 description 24
- 239000000047 product Substances 0.000 description 21
- 239000003795 chemical substances by application Substances 0.000 description 17
- 230000008569 process Effects 0.000 description 15
- 239000000835 fiber Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 239000010893 paper waste Substances 0.000 description 11
- 238000005259 measurement Methods 0.000 description 9
- 235000011121 sodium hydroxide Nutrition 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 150000004665 fatty acids Chemical class 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 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 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000007844 bleaching agent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- -1 fatty acid salt Chemical class 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 238000009897 hydrogen peroxide bleaching Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000203 mixture 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
- 239000002562 thickening agent Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 239000002655 kraft paper Substances 0.000 description 2
- 238000010297 mechanical methods and process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000009896 oxidative bleaching Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 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
- 235000002568 Capsicum frutescens Nutrition 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-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
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229940053200 antiepileptics fatty acid derivative Drugs 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010130 dispersion processing Methods 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction 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
- 230000035699 permeability Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 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、印刷古紙から製造される古紙パルプのチリを低減させる方法に関し、さらに詳しくは新聞古紙を主体とする印刷古紙を脱墨再生する際にダートを効率よく低減させ、脱墨パルプの品質を向上させることを目的とする。 The present invention relates to a method for reducing dust in used paper pulp produced from printed used paper, and more specifically, reducing darts efficiently when deinking and regenerating printed used paper mainly made from newspaper used paper, and the quality of deinked pulp. It aims at improving.
従来、印刷古紙を脱墨し再生させるには、離解・除塵・漂白・分散・脱墨・洗浄の工程の組み合わせからなる方法で製造を行ってきた。また、特に脱墨パルプのダートを低減させるためには、スクリーン、クリーナー等の除塵機を高性能化するか、分散工程でニーディングを強化する事が必要であった。しかし、近年、印刷古紙の中に、灰分が多く、表面処理剤により極端に脱墨性の劣る中性新聞紙の混入割合が著しく増加しており、これまで一般的に行われていた脱墨パルプフローではインクを主体とするダートを十分に除去する事が困難となってきた。 Conventionally, in order to deink and recycle used printing paper, it has been manufactured by a method comprising a combination of the steps of disaggregation, dust removal, bleaching, dispersion, deinking, and washing. In order to reduce the dirt of deinked pulp, it was necessary to improve the performance of dust removers such as screens and cleaners, or to strengthen kneading in the dispersion process. However, in recent years, there has been a marked increase in the mixing ratio of neutral newsprint paper, which has a lot of ash and is extremely inferior in deinking properties, due to the surface treatment agent. In the flow, it has been difficult to sufficiently remove the dirt mainly composed of ink.
一方、ダートを極力低減させ、ＢＫＰと同等もしくはそれに準ずる品質を有するＤＩＰが望まれていたが、これまで、新聞古紙や雑誌古紙をはじめとする印刷古紙からこれに該当する品質の古紙パルプを製造することは極めて困難であった。 On the other hand, DIP has been desired to reduce the dirt as much as possible and to have a quality equivalent to or equivalent to BKP, but until now, it has been manufacturing waste paper pulp of the corresponding quality from waste paper used in newspapers and magazines. It was extremely difficult to do.
従来のダートを低減させる技術には、マイカープロセッサーをはじめとする、一軸のローター集面に送り刃と戻り刃が配置され、かつステーターの刃と各刃間に十分な間隙を有したミキサーを用いることを特徴とするもの（例えば、特許文献１）、パルプ濃度２０〜３５％にして酸化型漂白剤を添加した後、機械的に攪拌して酸化漂白するとともに、漂白した後の繊維懸濁液をパルプ濃度１０〜３０％にして、還元漂白剤を添加した後、機械的に攪拌して還元漂白しているもの（例えば、特許文献２参照）、三段以上のディスパーザーを使用し、同時に一段以上は高温のディスクタイプのディスパーザーで処理するもの（例えば、特許文献３）があるが、繊維からインキを強制的に剥離しても剥離したインキが微細化してしまい、その後のフローテーションを強化しなければ、十分なダートの減少効果は望めない。 Conventional techniques to reduce dirt use a mixer that has a feed blade and a return blade on the surface of a uniaxial rotor, such as a car car processor, and that has a sufficient gap between the stator blade and each blade. (For example, Patent Document 1), after adding an oxidizing bleaching agent with a pulp concentration of 20 to 35%, mechanically stirring and oxidative bleaching, and bleaching the fiber suspension The pulp concentration is 10 to 30%, the reducing bleach is added, and the mixture is mechanically stirred to reduce and bleach (for example, refer to Patent Document 2). One or more stages are processed with a high-temperature disk-type disperser (for example, Patent Document 3). However, even if the ink is forcibly separated from the fiber, the separated ink becomes finer, and the subsequent ink is removed. If you do not strengthen the over implementation, not be expected decrease a sufficient effect of dirt.
一方、白色度６５％ＩＳＯ以上の高白色度の脱墨パルプを得るための方法としては、漂白工程で過酸化水素を過剰に加えるか、過酸化水素漂白の前後の何れかに二酸化チオ尿素漂白工程を設ける方法、漂白の効率を向上させるために製品パルプの灰分を下げる対策として灰分除去装置を洗浄設備として最終工程に組み入れる方法（例えば、特許文献４）、灰分除去装置の前後で役割の違う脱墨剤を使用し、漂白性を向上させる方法（例えば、特許文献５）、温度の違う二段の漂白工程で漂白を行う方法（例えば、特許文献６）等があるが、いずれも中性領域でのフローテーション処理と組み合わせて、高白色度でかつダートの少ないパルプが得られる脱墨システムの構築については未検討であった。 On the other hand, as a method for obtaining high whiteness deinked pulp having a whiteness of 65% or more, hydrogen peroxide is excessively added in the bleaching step, or thiourea dioxide bleaching is performed either before or after the hydrogen peroxide bleaching. A method of providing a process, a method of incorporating an ash removal device into the final process as a cleaning facility as a measure to lower the ash content of product pulp in order to improve the efficiency of bleaching (for example, Patent Document 4), and a role different before and after the ash removal device There are a method for improving bleachability using a deinking agent (for example, Patent Document 5) and a method for performing bleaching in a two-stage bleaching process at different temperatures (for example, Patent Document 6). In combination with the flotation treatment in the area, the construction of a deinking system that can obtain pulp with high whiteness and low dirt has not been studied.
印刷古紙からインキを分離除去し、脱墨パルプを漂白するために従来から使用されてきた薬品としては、苛性ソーダ、珪酸ソーダ、炭酸ソーダ等のアルカリ剤、過酸化水素、次亜塩素酸塩、二酸化チオ尿素、ハイドロサルファイト等の漂白剤、ＥＤＴＡやＤＴＰＡ等の金属キレート剤と共に、脱墨剤が使用されてきた。脱墨剤には、パルプ繊維からインキを剥離し、微細分散させる効果の強いものやインキを凝集させフローテーション工程でのインキ捕集能を高める効果の強いもの等がある。 Conventional chemicals used to separate and remove ink from used printing paper and bleach deinked pulp include alkaline agents such as caustic soda, sodium silicate and sodium carbonate, hydrogen peroxide, hypochlorite, and dioxide. Deinking agents have been used with bleaching agents such as thiourea and hydrosulfite, and metal chelating agents such as EDTA and DTPA. Deinking agents include those having a strong effect of peeling and finely dispersing ink from pulp fibers, and those having a strong effect of aggregating ink and enhancing the ability of collecting ink in the flotation process.
例えば、従来から、脱墨剤として、高級アルコール硫酸塩、ポリオキシアルキレン高級アルコール硫酸塩、脂肪酸あるいは、脂肪酸塩、アルキルベンゼンスルホン酸塩、高級アルコール及びアルキルフェノールのアルキレンオキサイド付加物、多価アルコールエステルアルキレンオキサイド付加物等が使用されている。 For example, conventionally, as a deinking agent, higher alcohol sulfate, polyoxyalkylene higher alcohol sulfate, fatty acid or fatty acid salt, alkylbenzene sulfonate, alkylene oxide adduct of higher alcohol and alkylphenol, polyhydric alcohol ester alkylene oxide Additives are used.
一般的に、効果的な脱墨剤とされているのは、高級脂肪酸のアルキレンオキサイド付加物又はそのエーテル化合物又はエステル化合物等であり、特開昭５８−１０９６９６号公報、特開昭６２−２７６０９３号公報、特開平５−２５７９０号公報等（特許文献６，７，８）に記載されているが、これらの脱墨剤の捕集効果を最大限に発揮させ高白色度でかつダートの少ないパルプが得られるシステムの構築については未検討であった。 Generally, an effective deinking agent is an alkylene oxide adduct of a higher fatty acid or an ether compound or an ester compound thereof. JP-A-58-109696, JP-A-62-276093 No. 5, JP 25-25790 A, etc. (Patent Documents 6, 7, 8). However, the collection effect of these deinking agents is maximized, and the whiteness is high and the dirt is small. The construction of a system for obtaining pulp has not been studied.
本発明の目的は、上記のような問題を解消し、特に脱墨性の悪い一部の中性新聞を含む印刷古紙から製造される脱墨パルプのダートを大幅に低減させて、高白色度で高品質の脱墨古紙パルプを製造することができる方法を提供するものである。 The object of the present invention is to solve the above-mentioned problems, particularly by greatly reducing the deinking pulp dirt produced from printed old paper including some neutral newspapers with poor deinking properties. The present invention provides a method capable of producing high quality deinked waste paper pulp.
本発明者らは、機械的な手法で最も未剥離インキの低減が可能な高温のディスパーザー処理によりパルプから剥離された遊離インキは微細化しやすく、通常のアルカリ領域でのフローテーション工程で取り除くことが非常に困難であったものが、中性領域にｐＨが調整されているフローテーターによりフローテーションを行うことで効率よく除去ができることを見出し、以下の発明を成すに至った。 The inventors of the present invention are able to reduce the free ink peeled from the pulp by a high-temperature disperser treatment that can reduce the most unpeeled ink by a mechanical method, and remove it by a flotation process in a normal alkaline region. However, it has been found that it can be efficiently removed by flotation with a flotator whose pH is adjusted in the neutral region, and the following inventions have been made.
（１）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、
前記一連の工程中に９０〜１３０℃の高温分散処理を行う高温分散工程を配置し、該高温分散工程の後工程中にｐＨ６〜９の中性領域におけるフローテーションにより脱墨処理を行う中性フローテーション工程を配置することを特徴とする脱墨パルプの製造方法。
(1) In a method of pulping used printing paper through a series of steps having at least a disaggregation step, a dust removal step, a bleaching step, a dispersion step, a flotation step, and a washing step,
A high temperature dispersion step for performing a high temperature dispersion treatment at 90 to 130 ° C. is arranged in the series of steps, and the neutralization is performed by flotation in a neutral region of pH 6 to 9 during the subsequent step of the high temperature dispersion step. A method for producing deinked pulp, comprising a flotation step.
（２）前記高温分散工程が、該高温分散工程の前工程から送られてくるパルプスラリーをそのままの状態で分散処理し、連続して該分散処理したパルプスラリーの温度を９０〜１３０℃に昇温してさらに高温分散処理を行う工程である、上記の脱墨パルプの製造方法。 (2) The high-temperature dispersion step disperses the pulp slurry sent from the previous step of the high-temperature dispersion step as it is, and continuously raises the temperature of the dispersed pulp slurry to 90 to 130 ° C. The method for producing deinked pulp as described above, which is a step of performing a high-temperature dispersion treatment by heating.
（３）前記高温分散工程が、該高温分散工程の前工程から送られてくるパルプスラリーをそのままの状態で軸タイプの分散機により分散処理し、連続して該分散処理したパルプスラリーの温度を９０〜１３０℃に昇温してさらにディスクタイプの分散機により高温分散処理を行う工程である、上記いずれかの脱墨パルプの製造方法。 (3) In the high-temperature dispersion step, the pulp slurry sent from the previous step of the high-temperature dispersion step is dispersed as it is with a shaft-type disperser, and the temperature of the pulp slurry subjected to the dispersion treatment is continuously set. The method for producing any one of the above deinked pulps, which is a step of raising the temperature to 90 to 130 ° C. and further performing high-temperature dispersion treatment with a disk-type disperser.
（４）前記一連の工程が、分散工程として、軸タイプの分散機による分散工程とディスクタイプの分散機による分散工程からなる複数の分散工程を有する工程である、上記いずれかの脱墨パルプの製造方法。 (4) The deinked pulp according to any one of the above, wherein the series of steps is a step having a plurality of dispersion steps consisting of a dispersion step using a shaft-type disperser and a dispersion step using a disk-type disperser as the dispersion step. Production method.
（５）前記中性フローテーション工程におけるパルプスラリーのｐH６〜９への調整が、硫酸の添加によるｐH調整である、上記いずれかの脱墨パルプの製造方法。 (5) The method for producing deinked pulp according to any one of the above, wherein the adjustment of the pulp slurry to pH 6 to 9 in the neutral flotation step is pH adjustment by addition of sulfuric acid.
（６）前記離解工程が、水酸化ナトリウムを添加したアルカリ性条件下における処理工程である、上記いずれかの脱墨パルプの製造方法。 (6) The method for producing any one of the deinked pulps, wherein the disaggregation step is a treatment step under alkaline conditions to which sodium hydroxide is added.
（７）上記いずれかの脱墨パルプの製造方法に従って製造される、０．００４〜５．０ｍｍ２のダート個数が５０００〜５００００個／ｍ２以下で、ＩＳＯ白色度が５０％〜８５％の古紙パルプ。 (7) According to any one of the above deinked pulp manufacturing methods, 0.004 to 5.0 mm 2 of dart number is 5000 to 50000 pieces / m 2 or less, and ISO whiteness is 50% to 85%. Waste paper pulp.
本発明により、原料古紙の品質によらず、チリが低減し、品質が向上している脱墨パルプが得られるので、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紙製品に高配合する事が可能となり、古紙の利用範囲が広がる。 According to the present invention, a deinked pulp having reduced chili and improved quality can be obtained regardless of the quality of the raw waste paper. Therefore, deinked pulp cheaper than kraft pulp, mechanical pulp, etc. is highly blended in paper products. This makes it possible to expand the range of used paper.
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％〜３５％含む古紙等があげられる。本発明の方法は、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の処理に特に効果的である。 In the method of the present invention, examples of the used printed paper as a raw material include newspaper, fine coated paper, high ash coated paper, non-coated paper, and the like containing 7% to 35% ash. The method of the present invention is particularly effective for the treatment of printed waste paper including some neutral newspapers that have 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は特に制限は無いが、好ましい離解処理として、原料印刷古紙を固形分濃度１２〜１８％になるように稀釈水に入れ、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％添加して行う処理が挙げられる。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分であり、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。 The disaggregation step in the method of the present invention is not particularly limited, but as a preferable disaggregation treatment, the raw material printed waste paper is placed in diluted water so as to have a solid content concentration of 12 to 18%, and further a chemical (sodium hydroxide) is added to the pulp. The process performed by adding 0-3.0 mass%, preferably 0.1-2.5 mass% is mentioned. 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）製のダイホープ９４０、ダイホープ９６０、日華（株）製リポブライトＤＰ−８１０等があるが、これらに限定されるものではない。 Examples of deinking agents with strong ink releasability include higher alcohol deinking agents, such as DI-7020, DI-7030, DI-767, DI-7282 manufactured by Kao Corporation, and Nisshin Chemical Research. DIA-Z-100, DIA-Z-5000, Toyo Chemical Co., Ltd. Neoscore FW-780, Neoscore FW-790, Neoscore FW-795, FT-467, FT-470, FT- 487, FT-511, FT-513, FT-514, FT-515, BB agent, Daihope 940, Daihope 960 manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Lipobright DP-810 manufactured by Nikka Co., Ltd. However, it is not limited to these.
本発明の方法における除塵工程としては特に制限は無い。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 as a 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.
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、原料中の灰分を優先的に除去し、繊維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 cleaning equipment used in the cleaning process includes extractors, fall washers (Eiko), and double nip thickener (Ishikawajima Sangyo), but the cleaning equipment preferentially removes ash in the raw material. A washing machine that minimizes fiber loss is preferred. 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.
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。本発明の方法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％であり、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. Hydrogen peroxide is used in the method of the present invention. 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%. 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をパルプに均一に混合できれば、漂白工程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る。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。しかし、これらに限定されるものではない。 If the deinking agent can be uniformly mixed with the pulp before flotation, the deinking agent may be added to the bleaching step. As the deinking agent having strong ink cohesion, there are fatty acid or fatty acid derivative-based deinking agents. For example, 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 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. is there. However, it is not limited to these.
本発明の方法で行う分散処理には低速・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％で、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 dispersion processing performed by the method 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ものではない。しかし、１０〜２５％の処理濃度で、１２００〜１８００ｒｐの高速で、空転動力負荷を差し引いた実動力負荷が５〜３０ｋＷ／ｔ程度で、弱い機械力を与えながら撹拌処理を行う、いわゆるマイカプロセッサーのような高速撹拌装置では高いダート減少効果や高い剥離効果が得られないため本発明の方法には適さない。 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. Further, as the biaxial kneader, those manufactured by Niihama Pump Manufacturing Co., Ltd., Yamamoto Hyakuma Manufacturing Co., Ltd., etc. are used, but are not limited to specific models. However, a so-called mica processor that performs agitation while applying a weak mechanical force at a processing concentration of 10 to 25%, a high speed of 1200 to 1800 rp, an actual power load of about 5 to 30 kW / t after subtracting the idling power load. Such a high-speed stirring device is not suitable for the method of the present invention because a high dart reduction effect and a high peeling effect cannot be obtained.
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.
本発明の方法の高温分散工程における分散機による分散処理時の温度は、９０〜１３０℃である。９０℃未満の処理では、十分なダート減少効果と過酸化水素や二酸化チオ尿素等の漂白薬品による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。しかしながら、９０〜１３０℃の範囲でディスパーザー処理を行った場合、パルプ繊維からのインキ剥離が促進され、パルプ繊維そのものの未剥離インキは大幅に低減するものの、繊維より剥離させたインキが微細化し遊離インキが増加するため、パルプシートにしたときにシートの表面に遊離インキがダートとして残留する。そのため、高温のディスパーザー処理後、インキ除去効率が格段に向上する中性領域でのフローテーション処理が最も好ましいインキ除去方法である。 The temperature during the dispersion treatment by the disperser in the high-temperature dispersion step of the method of the present invention is 90 to 130 ° C. If the treatment is less than 90 ° C., a sufficient dart reduction effect and a bleaching effect by bleaching chemicals such as hydrogen peroxide and thiourea dioxide cannot be obtained. On the other hand, if it exceeds 130 ° C., yellowing of the pulp occurs. However, when the disperser treatment is performed in the range of 90 to 130 ° C., the ink peeling from the pulp fiber is promoted, and the unpeeled ink of the pulp fiber itself is greatly reduced, but the ink peeled from the fiber becomes finer. Since the free ink increases, the free ink remains as a dirt on the surface of the sheet when the pulp sheet is formed. Therefore, the most preferable ink removing method is a flotation treatment in a neutral region where the ink removing efficiency is remarkably improved after the high-temperature disperser treatment.
高温分散工程における分散機には、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。 In addition to hydrogen peroxide and thiourea dioxide, alkaline chemicals may be added to the disperser in the high temperature dispersion step. 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.
本発明の方法では、高温のディスパーザー処理後に、繊維より剥離された微細化した遊離インキを効率よく除去するため中性領域でのフローテーションを行う。洗浄工程で除去する方法の場合には、洗浄濾液とともに白水内を微細化した遊離インキが循環し、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。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を超えると遊離インキの除去効果が著しく悪化し、脱墨パルプのダート個数が上昇する。 In the method of the present invention, after the high-temperature disperser treatment, flotation is performed in a neutral region in order to efficiently remove the fine free ink peeled off from the fibers. In the case of the method of removing in the washing step, the free ink refined in the white water is circulated together with the washing filtrate, which is not preferable because it 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. The treatment pH in the flotation process 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, when the pH exceeds 9, the effect of removing free ink is remarkably deteriorated, and the number of darts in the deinked pulp is increased.
フローテーション工程の後の洗浄工程は、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工程であり、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。 The washing step after the flotation step is a step of dehydrating and washing fine ink that could not be removed by the flotator, and there is no particular limitation on the washing apparatus, but 0.6 to 1.5% pulp slurry is treated with fresh water or It is preferable to dehydrate and wash to 15 to 35% after dilution with clear white water of a paper machine.
本発明の方法により得られたパルプは、０．００４〜５．０ｍｍ２のダート個数が５０００〜５００００個／ｍ２以下であることが好ましい。ダート個数５００００個を超えるものは、ＢＫＰに比べて大きく見劣りする。また、ダート個数５０００個／ｍ２未満とするには、莫大な薬品、エネルギーが必要となるため好ましくない。また、本発明は上記脱墨パルプを１０質量％〜１００質量％配合した紙の発明を含む。１０％未満の配合率では抄紙時に上記効果が消失してしまうため、好ましくない。本発明の方法で得られた脱墨パルプは白色度さえ適度に合わせれば、ダートが少ないため紙に５０質量％以上配合することが可能である。 The pulp obtained by the method of the present invention preferably has a dart count of 0.004 to 5.0 mm 2 of 5000 to 50000 pieces / m 2 or less. Those with a dart count exceeding 50000 are significantly inferior to BKP. In addition, in order to make the number of dirt less than 5000 / m 2 , enormous chemicals and energy are required, which is not preferable. Moreover, this invention includes the invention of the paper which mix | blended 10 mass%-100 mass% of the said deinked pulps. A blending ratio of less than 10% is not preferable because the above effect disappears during papermaking. The deinked pulp obtained by the method of the present invention can be blended in paper at 50% by mass or more because there is little dirt if the whiteness is appropriately adjusted.
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製造される脱墨パルプのＩＳＯ白色度が５０％〜８５％のものまで幅広く製造できるが、いずれもダートの低減された品質を達成することが可能となる。 According to the method of the present invention, deinked pulp produced from waste paper used mainly for newspaper waste paper can be widely manufactured from ISO whiteness of 50% to 85%, all of which achieve reduced dart quality. It becomes possible.
本発明の脱墨パルプの製造方法によれば、高温分散工程で９０〜１３０℃の高温ディスパーザー処理を行い、その後のフローテーション工程をｐＨ６〜９の中性領域で行うことにより、印刷古紙からのインキ剥離効果に優れ、パルプ繊維に残留している未剥離インキの少ない脱墨パルプを製造できる。このように、残留している未剥離インキの少ない脱墨パルプを製造できる理由は定かではないが、以下のように推測される。印刷古紙上の未剥離インキは、現在、機械的な手法で最も未剥離インキの低減が可能とさせる高温のディスパーザー処理により、遊離インキとなるが、このパルプから剥離した遊離インキは微細化しやすく、遊離インキの持つ自らの電荷でインキ同士が反発し合っているため、通常のアルカリ領域でのフローテーション工程では微細化した遊離インキを取り除くことが非常に困難であった。しかし、中性領域でのフローテーションを行うことで遊離インキの持っている電荷による反発を低減させることができ、微細化した遊離インキでもフローテーションで除去することができる。これらの作用によって、脱墨パルプに残留する未剥離インキ、遊離インキの両方のインキが少なくなり、良質な脱墨パルプが得られる、と考えられる。 According to the method for producing deinked pulp of the present invention, a high temperature disperser treatment at 90 to 130 ° C. is performed in a high temperature dispersion step, and a subsequent flotation step is performed in a neutral region of pH 6 to 9, thereby It is possible to produce a deinked pulp having an excellent ink peeling effect with little unremoved ink remaining in the pulp fiber. Thus, although the reason which can manufacture the deinked pulp with few remaining unpeeled inks is not certain, it estimates as follows. Unreleased ink on used printed paper is now free ink by a high-temperature disperser treatment that enables the most reduction of unreleased ink by a mechanical method. Since the inks repel each other due to their own charge of the free ink, it has been very difficult to remove the fine free ink in the normal flotation process in the alkaline region. However, by performing flotation in the neutral region, repulsion due to the charge of free ink can be reduced, and even fine free ink can be removed by flotation. By these actions, it is considered that both unexfoliated ink and free ink remaining in the deinked pulp are reduced, and a high-quality deinked pulp can be obtained.
以下に、実施例に基づいて本発明を詳細に説明するが、各実施例は本発明の技術的範囲をなんら限定するものではない。各実施例及び比較例において、百分率（％）は白色度以外すべて質量％を意味し、また、薬品添加率は、対絶乾パルプ当たりの質量％で示した。古紙パルプの品質は、以下に示したダート評価方法によるダート個数で評価した。特にことわりが無い限り原料濃度は灰分込みの固形分濃度、薬品添加率は質量％である。各実施例では、完成パルプ６０ＡＤＴ／Ｄの脱墨パルプ製造設備を使用した。 Hereinafter, the present invention will be described in detail based on examples. However, the examples do not limit the technical scope of the present invention. In each of the examples and comparative examples, the percentage (%) means mass% except whiteness, and the chemical addition rate is expressed as mass% per dry pulp. The quality of the waste paper pulp was evaluated by the number of darts according to the dart evaluation method shown below. Unless otherwise specified, the raw material concentration is the solid content concentration including ash, and the chemical addition rate is mass%. In each example, a deinked pulp production facility for finished pulp 60ADT / D was used.
＜ダート評価方法＞
脱墨パルプを１５０メッシュワイヤー上に分取し、パルプ１ｇ当たり約２０リットルのフィルター通過清水を用いて、繊維から遊離しているインクを完全に洗浄後、坪量６０ｇ／ｍ２の手すき紙をＪＩＳ Ｐ ８２２２に示される試験用手すき紙の調製方法に準じて５枚作製した。手すき紙５枚中の中心１０ｃｍ×１０ｃｍ中に含まれる０．００４〜５．０ｍｍ２サイズのダート個数を王子計測機器社製ダートアナライザー（ＤＩＰ−２００）を用いて測定した。測定結果は、パルプ１ｍ２あたりの個数に換算し、ダート個数とした。
<Dirt evaluation method>
The deinked pulp is dispensed onto a 150 mesh wire, and the ink released from the fiber is thoroughly washed with about 20 liters of filtered fresh water per gram of pulp, and then a handsheet having a basis weight of 60 g / m 2 is removed. Five sheets were produced in accordance with the method for preparing a test handsheet shown in JIS P 8222. The number of darts of 0.004 to 5.0 mm 2 size contained in the center 10 cm × 10 cm in 5 handsheets was measured using a Dart Analyzer (DIP-200) manufactured by Oji Scientific Instruments. The measurement result was converted to the number per 1 m 2 of pulp and used as the number of dirt.
＜白色度測定方法＞
完成パルプを離解後、パルプスラリーに硫酸バンドを対絶乾パルプ２０．０％加え、Ｔａｐｐｉ試験法Ｔ２０５ｏｓ−７１（ＪＩＳ Ｐ ８２０９）に従って、坪量６０ｇ／ｍ２のシートを作製した。その後、パルプの白色度は分光白色度測色計（スガ試験機製）で蛍光強度カットの白色度を測定した。
<Whiteness measurement method>
After the finished pulp was disaggregated, 20.0% of the dried pulp was added to the pulp slurry, and a sheet having a basis weight of 60 g / m 2 was prepared according to Tappi test method T205os-71 (JIS P 8209). Thereafter, the whiteness of the fluorescence intensity cut was measured with a spectral whiteness colorimeter (manufactured by Suga Test Instruments).
実施例１
新聞紙及びチラシを主体とする古紙（灰分含有量１３．５％）の原料をパルパーに仕込み原料濃度１５％、水酸化ナトリウム添加率対パルプ０．４％、高級アルコール系脱墨剤（花王社製、ＤＩ−７０２０）添加率対パルプ０．１２％、離解時間１５分、離解温度３５℃で離解した、離解後のパルプスラリーを除塵処理し、１．０％に濃度調整後、前段フローテーター（王子エンジニアリング（株）製）にて処理した。前段フローテーターの脱墨条件は、フローテーター処理濃度１．１％、フローテーター処理温度３８℃で行った。
Example 1
Raw paper (mainly ash content: 13.5%) made up of newspapers and leaflets is charged into a pulper, the raw material concentration is 15%, the sodium hydroxide addition rate is 0.4% of pulp, and a higher alcohol deinking agent (manufactured by Kao) , DI-7020) Addition rate vs. pulp 0.12%, disaggregation time 15 minutes, disaggregation temperature of 35 ° C. The pulp slurry after disaggregation was dust-removed and the concentration was adjusted to 1.0%. Processed by Oji Engineering Co., Ltd. The deinking conditions for the first-stage flow-rater were as follows: the flow-rate treatment concentration was 1.1% and the flow-rate treatment temperature was 38 ° C.
前段フローテーターで脱墨処理した後のパルプスラリーは、エキストラクター、ディスクシックナーで洗浄後、スクリュープレスで脱水し、加温ミキサーで７５℃まで昇温後、軸タイプの分散機として相川鉄工社製ディスパーザーを用いて一段目の分散処理（パルプ濃度約２８％、電力原単位約４０ｋｗｈ／パルプＴ）をし、その後漂白を行なった。漂白条件は過酸化水素添加率対パルプ３．５％、水酸化ナトリウム添加率対パルプ２．０％、珪酸ナトリウム添加率対パルプ水酸化ナトリウム換算０．６％、パルプ濃度約２６．５％で、漂白時間１５０分で行った。次いで、温度、濃度を保持したまま、軸タイプの分散機として前記相川鉄工社製ディスパーザーを用いて二段目の分散処理（電力原単位約２０ｋｗｈ／パルプＴ）をし、連続して温度１１０℃まで昇温後、ディスクタイプの分散機としてＣｅｌｌｗｏｏｄ社製のＫＲＩＭＡホットディスパーザーを用いて三段目の分散処理を行なった。 The pulp slurry after deinking with the first stage floatator is washed with an extractor and disc thickener, dehydrated with a screw press, heated to 75 ° C with a heating mixer, and manufactured by Aikawa Tekko Co., Ltd. as a shaft type disperser. First-stage dispersion treatment (pulp concentration: about 28%, power intensity: about 40 kwh / pulp T) was performed using a disperser, and then bleaching was performed. The bleaching conditions were as follows: hydrogen peroxide addition rate to pulp 3.5%, sodium hydroxide addition rate to pulp 2.0%, sodium silicate addition rate to pulp sodium hydroxide equivalent 0.6%, pulp concentration about 26.5% The bleaching time was 150 minutes. Next, while maintaining the temperature and concentration, the second-stage dispersion treatment (power intensity of about 20 kwh / pulp T) was performed using the Aikawa Tekko Disperser as a shaft type disperser, and the temperature was continuously changed to 110. After raising the temperature to 0 ° C., the third stage dispersion treatment was performed using a KRIMA hot disperser manufactured by Cellwood as a disk-type disperser.
その後、フローテーターに送る上記三段目の分散処理パルプスラリーを硫酸でｐＨ７．５とし、王子エンジニアリング社製のフローテーターで脱墨処理を行なった。フローテーターの脱墨条件は、特殊脂肪酸誘導体（花王社製、ＤＩ−１１２０）添加率０．１１％、フローテーター処理濃度１．１％、フローテーター処理温度４０℃で行った。ディスクシックナーにて脱水洗浄後、製品パルプのダート数及び白色度を測定した。結果を表１に示す。 Thereafter, the third-stage dispersion treated pulp slurry to be sent to the flowator was adjusted to pH 7.5 with sulfuric acid, and deinking was performed with a flowator manufactured by Oji Engineering. The deinking conditions of the floatator were performed at a special fatty acid derivative (Kao Corporation, DI-1120) addition rate of 0.11%, a floatator treatment concentration of 1.1%, and a floatator treatment temperature of 40 ° C. After dehydration washing with a disc thickener, the number of darts and whiteness of the product pulp were measured. The results are shown in Table 1.
実施例２
フローテーターに送る前記三段目の分散処理パルプスラリーを硫酸でｐＨ６．５とし、フローテーターで脱墨処理を行なった以外は、実施例１と同様に処理し、製品パルプを製造した。製品パルプのダート数及び白色度の測定結果を表１に示す。
Example 2
A product pulp was produced in the same manner as in Example 1 except that the third-stage dispersion-treated pulp slurry to be sent to the floatator was adjusted to pH 6.5 with sulfuric acid and subjected to deinking with a floatator. Table 1 shows the measurement results of the dart number and whiteness of the product pulp.
実施例３
フローテーターに送る前記三段目の分散処理パルプスラリーを硫酸でｐＨ８．５とし、フローテーターで脱墨処理を行なった以外は、実施例１と同様に処理し、製品パルプを製造した。製品パルプのダート数及び白色度の測定結果を表１に示す。
Example 3
A product pulp was produced in the same manner as in Example 1 except that the third-stage dispersion-treated pulp slurry to be sent to the floatator was adjusted to pH 8.5 with sulfuric acid and subjected to deinking with a floatator. Table 1 shows the measurement results of the dart number and whiteness of the product pulp.
実施例４
ディスクタイプの分散機による前記三段目の分散処理を９５℃で行なった以外は、実施例１と同様に処理し、製品パルプを製造した。製品パルプのダート数及び白色度の測定結果を表１に示す。
Example 4
A product pulp was produced in the same manner as in Example 1 except that the third-stage dispersion treatment using a disk-type disperser was performed at 95 ° C. Table 1 shows the measurement results of the dart number and whiteness of the product pulp.
実施例５
ディスクタイプの分散機による前記三段目の分散処理を１２５℃で行なった以外は、実施例１と同様に処理し、製品パルプを製造した。製品パルプのダート数及び白色度の測定結果を表１に示す。
Example 5
A product pulp was produced in the same manner as in Example 1 except that the third-stage dispersion treatment using a disk-type disperser was performed at 125 ° C. Table 1 shows the measurement results of the dart number and whiteness of the product pulp.
比較例１
フローテーターに送る前記三段目の分散処理パルプスラリーを硫酸でｐＨ９．５とし、フローテーターで脱墨処理を行なった以外は、実施例１と同様に処理し、製品パルプを製造した。製品パルプのダート数及び白色度の測定結果を表１に示す。
Comparative Example 1
A product pulp was produced in the same manner as in Example 1 except that the third-stage dispersion-treated pulp slurry to be sent to the floatator was adjusted to pH 9.5 with sulfuric acid and deinked with a floatator. Table 1 shows the measurement results of the dart number and whiteness of the product pulp.
比較例２
フローテーターに送る前記三段目の分散処理パルプスラリー（ｐＨ１０．２）に硫酸を添加せずにフローテーターで脱墨処理を行なった以外は、実施例１と同様に処理し、製品パルプを製造した。製品パルプのダート数及び白色度の測定結果を表１に示す。
Comparative Example 2
A product pulp is produced in the same manner as in Example 1 except that the third-stage dispersion-treated pulp slurry (pH 10.2) to be sent to the floatator is deinked with a floatator without adding sulfuric acid. did. Table 1 shows the measurement results of the dart number and whiteness of the product pulp.
比較例３
ディスクタイプの分散機による前記三段目の分散処理を８０℃で行なった以外は、実施例１と同様に処理し、製品パルプを製造した。製品パルプのダート数及び白色度の測定結果を表１に示す。
Comparative Example 3
A product pulp was produced in the same manner as in Example 1 except that the third-stage dispersion treatment with a disk-type disperser was performed at 80 ° C. Table 1 shows the measurement results of the dart number and whiteness of the product pulp.
比較例４
ディスクタイプの分散機による前記三段目の分散処理を行わなかった以外は、実施例１と同様に処理し、製品パルプを製造した。製品パルプのダート数及び白色度の測定結果を表１に示す。
Comparative Example 4
A product pulp was produced in the same manner as in Example 1 except that the third-stage dispersion treatment with a disk-type disperser was not performed. Table 1 shows the measurement results of the dart number and whiteness of the product pulp.
実施例１〜５及び比較例１、２を比較すると明らかなように、分散機による漂白パルプスラリーの分散処理を９０〜１３０℃で行なう処理と、該分散処理パルプスラリーを中性ｐH領域に調整したフローテーターによる脱墨処理とを組み合わせることにより、ダート捕集除去が極めて高く白色度が優れている脱墨パルプを得ることができる。なお、比較例１，２で得られたものの場合もダート低減は認められるが、このダートの数値は１５０メッシュ洗浄後のパルプのシートであることにより低減しているものであり、アルカリ性領域でのフローテーターによる脱墨処理結果は、遊離インクが多く、白色度は上昇しないことを示している。
また、高温のディスクタイプディスパーザーによる処理を行わなかった場合や９０℃を超えない条件でディスパーザー処理を行った場合は、白色度を向上させることはできないし、ダートを低減させる効果も明らかに低い。
As is clear when Examples 1 to 5 and Comparative Examples 1 and 2 are compared, the dispersion treatment of bleached pulp slurry by a disperser is performed at 90 to 130 ° C., and the dispersion treated pulp slurry is adjusted to a neutral pH region. By combining with the deinking treatment by the floater, it is possible to obtain deinked pulp having extremely high dirt collection and removal and excellent whiteness. In addition, even in the case of those obtained in Comparative Examples 1 and 2, dart reduction is recognized, but the value of this dart is reduced by being a pulp sheet after 150 mesh washing, in the alkaline region The result of the deinking process by the flotator indicates that there is much free ink and the whiteness does not increase.
In addition, when the treatment with a high-temperature disc type disperser is not performed or when the disperser treatment is performed under a condition that does not exceed 90 ° C., the whiteness cannot be improved and the effect of reducing the dirt is also clearly shown. Low.
本発明の方法によれば、原料古紙の品質によらず、チリが低減し、品質が向上している脱墨パルプが得られるので、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紙製品に高配合する事が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 deinked pulp having reduced quality and improved quality can be obtained regardless of the quality of the raw paper, so that a cheaper deinked pulp than kraft pulp, mechanical pulp, etc. This makes it possible to add a high amount of waste paper to widen the range of used paper.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014265135A JP6304023B2 (en) | 2014-12-26 | 2014-12-26 | Method for producing deinked pulp |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014265135A JP6304023B2 (en) | 2014-12-26 | 2014-12-26 | Method for producing deinked pulp |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2016125153A JP2016125153A (en) | 2016-07-11 |
| JP6304023B2 true JP6304023B2 (en) | 2018-04-04 |
Family
ID=56356717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2014265135A Active JP6304023B2 (en) | 2014-12-26 | 2014-12-26 | Method for producing deinked pulp |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6304023B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110050099A (en) | 2016-09-30 | 2019-07-23 | 王子控股株式会社 | The manufacturing method of paper pulp, slurry, sheet material, laminate and paper pulp |
| CN108729279B (en) * | 2018-06-07 | 2020-12-01 | 南阳中昊科技有限公司 | New method for recycling waste paper |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11200269A (en) * | 1997-12-26 | 1999-07-27 | Nippon Paper Industries Co Ltd | Deinking method of printed waste paper |
| JP2003073987A (en) * | 2001-09-03 | 2003-03-12 | Oji Paper Co Ltd | Method for neutralization, deinking and pulping of printed waste paper |
| DE10254862A1 (en) * | 2002-11-25 | 2004-06-03 | Degussa Ag | Process for decolourization of printing ink from waste paper by flotation thinking |
| JP4952255B2 (en) * | 2007-01-11 | 2012-06-13 | 王子製紙株式会社 | Method for producing deinked pulp |
| JP5401935B2 (en) * | 2008-11-12 | 2014-01-29 | 王子ホールディングス株式会社 | Method for producing deinked pulp |
| JP5310370B2 (en) * | 2009-08-07 | 2013-10-09 | 王子ホールディングス株式会社 | Method for producing deinked pulp |
-
2014
- 2014-12-26 JP JP2014265135A patent/JP6304023B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2016125153A (en) | 2016-07-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4752543B2 (en) | Method for producing high whiteness deinked pulp | |
| US8657995B2 (en) | Method of producing recycled paper pulp from waste printed paper as raw material | |
| JP4952255B2 (en) | Method for producing deinked pulp | |
| JP5401935B2 (en) | Method for producing deinked pulp | |
| JP6304023B2 (en) | Method for producing deinked pulp | |
| JP5310370B2 (en) | Method for producing deinked pulp | |
| JP6492798B2 (en) | Method for producing deinked waste paper pulp | |
| JP4604962B2 (en) | Method for producing high whiteness deinked pulp | |
| JP3943913B2 (en) | Method for producing recycled pulp | |
| JP4760446B2 (en) | Method for producing waste paper pulp | |
| JP6004325B2 (en) | Method for producing waste paper deinked pulp | |
| JP6583005B2 (en) | Manufacturing method and manufacturing system of deinked waste paper pulp | |
| JP3191828B2 (en) | Deinking and bleaching of used printing paper | |
| JP6443290B2 (en) | Method for producing deinked waste paper pulp | |
| JP2007231429A5 (en) | ||
| JP6443291B2 (en) | Method for producing deinked pulp | |
| JP6304024B2 (en) | Method for producing deinked pulp | |
| JP5770619B2 (en) | Method for producing deinked pulp | |
| JP2004068175A (en) | Method for producing deinked pulp from printed waste paper | |
| JP5479968B2 (en) | Method for producing deinked pulp | |
| JP2002249993A (en) | Method for producing deinked pulp | |
| JPS6260515B2 (en) | ||
| JP3098021B2 (en) | How to make high brightness waste paper pulp | |
| JP2009035843A (en) | Method for producing deinked pulp | |
| CN117511288A (en) | Deinking agent and deinking process for thermal transfer waste paper |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20161130 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20171030 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20171122 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20180119 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20180206 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20180219 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6304023 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |