JP2007119955A - Method for producing high-whiteness deinked pulp - Google Patents
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本発明は印刷古紙の脱墨方法に関し、さらに詳しくは、印刷古紙からの脱墨パルプを製造する方法に係わり、特に脱墨効率を効率的に進める際に、インキ剥離工程の後工程に洗浄工程を有する脱墨パルプの製造方法に関する。 The present invention relates to a method for deinking used printing paper, and more particularly, to a method for producing deinked pulp from used printing paper, and in particular, when the deinking efficiency is advanced efficiently, a cleaning process is performed after the ink peeling process. It is related with the manufacturing method of the deinked pulp which has.
従来、印刷古紙を脱墨再生させるには、離解・除塵・漂白・分散・脱墨・洗浄の工程からなる方法で製造を行ってきた。また、特にインキ除去を進め白色度が６５％ＩＳＯ以上の高白色度古紙パルプを得るためには、前段及び後段の２段処理からなるフローテーター処理が必要であった。また、漂白の効率を上昇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のが主流であった。このように、最終工程に灰分除去工程を組み入れると、一般的には、そのろ液は前工程である脱墨工程の稀釈として使用することが多いので、灰分除去装置で除去した灰分が循環し、漂白工程での薬品原単位の悪化をもたらすという問題点があった。 In the past, in order to deink and recycle waste printed paper, it has been manufactured by a method comprising steps of disaggregation, dust removal, bleaching, dispersion, deinking and washing. Further, in particular, in order to proceed with ink removal and obtain a high whiteness waste paper pulp having a whiteness of 65% ISO or more, a floatator treatment consisting of a two-stage treatment of the former stage and the latter stage was necessary. In order to reduce the ash content of product pulp in order to increase the efficiency of bleaching, the mainstream is to incorporate an ash removal device into the final process as a cleaning facility. As described above, when the ash removal process is incorporated in the final process, the filtrate is generally used as a dilution of the deinking process, which is the previous process. Therefore, the ash removed by the ash removal device is circulated. However, there is a problem in that the chemical unit consumption in the bleaching process is deteriorated.
本発明者等は、先に、高灰分の印刷用紙からの脱墨パルプの製造方法（特許文献１）を提案し、更に、灰分除去装置の前後で役割の違う脱墨剤とし、漂白性を向上させる脱墨剤の有効な使用方法（特許文献２）を検討してきたが、フローテーター１段の処理で消費電力原単位の少ない高白色度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。 The present inventors have previously proposed a method for producing deinked pulp from high ash printing paper (Patent Document 1), and further used a deinking agent having different roles before and after the ash removing device to provide bleaching properties. We have studied the effective use of the deinking agent to improve (Patent Document 2), but the construction of a deinking system that can produce a high-whiteness pulp with low power consumption per unit of treatment by a single stage of the flotator has not been studied. Met.
印刷古紙から、インキを分離除去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いる。脱墨剤には、パルプ繊維からインキを剥離し、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 printed paper include alkali agents such as caustic soda, sodium silicate and sodium carbonate, bleaching agents such as hydrogen peroxide and hypochlorite, EDTA and DTPA. A deinking agent is used together with a metal chelating agent such as Deinking agents include those having a strong effect of peeling and 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.
離解工程で添加する脱墨剤は、剥離したインキを前段フローテーション工程で効率良く脱墨するため、パルプからのインキを剥離させて分散する能力と、フローテーターにおける泡への吸着性、インキ同士の凝集させる能力という、相反する効果のバランスをとったものを使用するため、離解工程で、パルプへの浸透力やインキ剥離性を著しく高めた脱墨剤は添加できず、印刷インキの剥離、分散が不充分となる問題点があった。 The deinking agent added in the disaggregation process is capable of deinking the separated ink efficiently in the previous flotation process, the ability to peel and disperse the ink from the pulp, the adsorptivity to the foam in the flowator, Because it uses a balance between the conflicting effects of the ability to agglomerate, deinking agents that have significantly improved pulp penetration and ink release properties cannot be added in the disaggregation process. There was a problem of insufficient dispersion.
ポリエチレングリコール型非イオン界面活性剤は、脱墨剤として古くから知られており、例えば、古紙をフローテーション方式によって脱インキする際の脱インキ剤として、ＲＯ−（ＸＯ）ｎ−Ｈ（式中Ｒは炭素数８〜２２のアルキル基など、ＸＯはオキシエチレンおよびオキシプロピレンのランダム付加重合物で、オキシエチレンを５０〜９５％含有、ｎは８〜１００の整数）（特許文献３）、ＲＯ−（Ｃ３Ｈ６Ｏ）ｍ（ＸＯ）ｎ−Ｈ（式中Ｒは炭素数８〜２２のアルキル基など、mは１〜５０の整数、ＸＯはオキシエチレンおよびオキシプロピレンのランダム付加重合物で、８〜１００の整数）（特許文献４）、天然油脂と多価アルコールの混合物にアルキレンオキシドを付加して得られる反応生成物および、ＲＯ−（ＡＯ）ｎ−Ｈ（式中Ｒは炭素数１２〜１８のアルキル基など、ＡＯは炭素数２〜４のオキシアルキレン基で、ｎは５以上の数）を一定の割合で含有（特許文献５）、ＲＯ−（ＰＯ）Ｘ（ＡＯ）Ｙ（ＰＯ）Ｚ−Ｈ（式中Ｒは炭素数８〜２２のアルキル基など、ＡＯはオキシアルキレン基で、ｘは１〜２０、ｙは１〜５０、zは１〜５０の数）（特許文献６）、Ｒ１Ｏ−（ＡＯ）ｎ−Ｈ（式中Ｒ１は炭素数１８を超え３６以下の炭化水素基、ＡＯはオキシエチレンおよびオキシプロピレンのランダム付加重合物で、ｎは１〜１０００の数）（特許文献７）、ＲＯ−（ＥＯ）（ＡＯ）×1（ＥＯ）−Ｈ、ＲＯ−（ＥＯ）（ＡＯ）×2（ＸＯ）−Ｈ、ＲＯ−（ＸＯ）（ＡＯ）×3（ＥＯ）−Ｈ、ＲＯ−（ＸＯ）（ＡＯ）×4（ＸＯ）−Ｈの混合物（式中Ｒは炭素数８〜３６のアルキル基など、ＡＯはオキシアルキレン基、ＸＯはオキシプロピレン基かオキシブチレン基で、×１〜×４オキシアルキレン基の付加モル数（特許文献８）、Ｒ１Ｏ−（ＡＯ）p−Ｈ（式中Ｒ１は炭素数１０〜１４のアルキル基、ＡＯはオキシアルキレン基で、pは１〜１００の整数）と、Ｒ２Ｏ−（ＰＯ）ｍ（ＥＯ）ｎ（ＸＯ）ｋ−Ｒ３（式中Ｒ２は炭素数１６〜２２のアルキル基など、Ｒ３は水素または炭素数２〜２４のアシル基、ＸＯはオキシアルキレン基で、ｍは１〜８、ｎは１０〜４０、ｋは重合ＸＯの炭素数の合計が３〜１２０の数）（特許文献９）などが開示されている。何れの場合も、フローテーションでインキを除去する際の脱墨剤として添加されているため、フローテーターで発泡しないものは、単独で使用できず、単独で発泡するもの、もしくは、起泡性の高い剤との混合物になっている。 Polyethylene glycol type nonionic surfactant has long been known as a deinking agent. For example, RO- (XO) n -H (in the formula, as a deinking agent when deinking used paper by a flotation method) R is an alkyl group having 8 to 22 carbon atoms, XO is a random addition polymer of oxyethylene and oxypropylene, containing 50 to 95% oxyethylene, and n is an integer of 8 to 100) (Patent Document 3), RO - (C 3 H 6 O) m (XO) n -H ( such as an alkyl group wherein R 8 to 22 carbon atoms, m is an integer of 1 to 50, XO is a random addition polymer of oxyethylene and oxypropylene And an integer of 8 to 100) (Patent Document 4), a reaction product obtained by adding an alkylene oxide to a mixture of natural oil and fat and a polyhydric alcohol, and RO- (AO) n- H (wherein R is an alkyl group having 12 to 18 carbon atoms, AO is an oxyalkylene group having 2 to 4 carbon atoms, and n is a number of 5 or more) in a certain ratio (Patent Document 5), RO— (PO) X (AO) Y (PO) Z- H (wherein R is an alkyl group having 8 to 22 carbon atoms, AO is an oxyalkylene group, x is 1 to 20, y is 1 to 50, z is 1 to 50) (Patent Document 6), R 1 O— (AO) n —H (wherein R 1 is a hydrocarbon group having 18 to 36 carbon atoms and AO is random addition of oxyethylene and oxypropylene) Polymer, where n is a number from 1 to 1000 (Patent Document 7), RO- (EO) (AO) × 1 (EO) -H, RO- (EO) (AO) × 2 (XO) -H, RO- (XO) (AO) × 3 (EO) -H, RO- (XO) (AO) × 4 (XO) a mixture of -H (wherein, R represents Such as an alkyl group of prime 8 to 36, AO is an oxyalkylene group, XO is an oxypropylene group or oxybutylene group, ×. 1 to × 4 molar number of addition of oxyalkylene group (Patent Document 8), R 1 O- (AO ) P- H (wherein R 1 is an alkyl group having 10 to 14 carbon atoms, AO is an oxyalkylene group, p is an integer of 1 to 100), and R 2 O— (PO) m (EO) n (XO K- R 3 (wherein R 2 is an alkyl group having 16 to 22 carbon atoms, R 3 is hydrogen or an acyl group having 2 to 24 carbon atoms, XO is an oxyalkylene group, m is 1 to 8, and n is 10 to 40, k is a number in which the total number of carbon atoms of polymerized XO is 3 to 120) (Patent Document 9) etc. In any case, as a deinking agent when removing ink by flotation Because it is added, it does not foam with a flotator It can not be used alone, which foaming by itself or has become a mixture of foaming highly agent.
また、フローテーション法、洗浄法、折衷法何れの脱インキ法においても使用できる脱インキ剤として、ＲＯ−（ＡＯ）ｎ−Ｈ（式中Ｒは炭素数８〜２４のアルキル基などの混合物、ＡＯは炭素数２〜４のオキシアルキレン基で、ｎは０または１以上の整数）（特許文献１０）が開示されているが、これも、フローテーション適性も持たせた汎用タイプにするために、1種類ではなく、起泡性の高い成分など、いくつかのものを混合させた脱インキ剤である。 In addition, as a deinking agent that can be used in any deinking method of the flotation method, the cleaning method, and the eclectic method, RO— (AO) n —H (wherein R is a mixture such as an alkyl group having 8 to 24 carbon atoms, AO is an oxyalkylene group having 2 to 4 carbon atoms, and n is an integer of 0 or 1) (Patent Document 10). This is also a general-purpose type having flotation suitability. This is a deinking agent that is not a single type, but a mixture of several components such as highly foaming ingredients.
一方、オフィス古紙処理剤として、ＲＯ−（ＡＯ）ｎ−Ｘ（式中Ｒは炭素数８〜２２の炭化水素基、ＡＯはオキシアルキレン基で、ｎは５〜５９の数、Ｘは水素原子、アルキル基またはアシル基）（特許文献１１）が開示されているが、対象古紙はオフィス古紙に限定されている上、フローテーション適性も持たせているため、比較例よりも発泡量は増加しており、操業上問題がある。 On the other hand, as an office waste paper treating agent, RO- (AO) n -X (wherein R is a hydrocarbon group having 8 to 22 carbon atoms, AO is an oxyalkylene group, n is a number of 5 to 59, and X is a hydrogen atom) , Alkyl group or acyl group) (Patent Document 11), but since the target waste paper is limited to office waste paper and has flotation suitability, the amount of foaming increases compared to the comparative example. And there are operational problems.
また、フローテーション処理により、印刷古紙を脱墨する方法において、フローテーション処理温度よりも曇点の高い脱墨剤と低い脱墨剤を併用する方法（特許文献１２）が開示されているが、これも、フローテーション適性を持たせるため、曇点が高く、起泡性の高い脱墨剤と併用することが必須であり、曇点が低く、発泡性の弱い脱墨剤単独では処理していない。 Moreover, in the method of deinking used printing paper by the flotation process, a method of using a deinking agent having a higher cloud point and a lower deinking agent than the flotation processing temperature is disclosed (Patent Document 12). In order to have flotation suitability, it is essential to use a deinking agent with a high cloud point and a high foaming property. Absent.
脱墨剤として、特定の疎水基の末端に、オキシエチレン、オキシプロピレンの順にブロック付加させた、Ｒ１Ｏ−（ＰＯ）ｍ（ＥＯ）ｎ（ＸＯ）ｋ−Ｒ２（式中Ｒ１は炭素数１２〜２２のアルキル基など、Ｒ２は水素または炭素数２〜２４のアシル基、ＸＯはオキシアルキレン基で、ｍは１〜８、ｎは１０〜４０、ｋは重合ＸＯの炭素数の合計が３〜１２０の数）（特許文献１３）を用い、フローテーションによって脱墨する方法が開示されているが、フローテーターで発泡することが必須であり、曇点が低く、処理温度では発泡しない脱墨剤を用いることは困難である。 As a deinking agent, R 1 O— (PO) m (EO) n (XO) k —R 2 (wherein R 1 is a block addition of oxyethylene and oxypropylene in this order at the end of a specific hydrophobic group) R 2 is hydrogen or an acyl group having 2 to 24 carbon atoms, XO is an oxyalkylene group, m is 1 to 8, n is 10 to 40, and k is the number of carbon atoms in the polymerized XO. (Patent Document 13), a method of deinking by flotation is disclosed, but it is essential to foam with a flotator, the cloud point is low, and the processing temperature is It is difficult to use a deinking agent that does not foam.
また、Ｒ１Ｏ−（ＡＯ）ｐ−Ｈ（式中Ｒ１は炭素数１４〜２４のアルキル基など、ＡＯはオキシエチレン基、オキシプロピレン基で、ＥＯの平均付加モル数が３０〜１６０、ＥＯ／ＰＯ付加モル比が１．５〜４．５）と、Ｒ２[−ＣＯＯ−（ＡＯ）ｍ−Ｒ３] ｎ（式中ｎは１以上の整数、Ｒ２はｎ個の−ＣＯＯＨを有する総炭素数１４〜２４のカルボン酸から全ての−ＣＯＯＨを除いた残基、Ｒ３は水素または炭素数１〜２０のアルキル基など、ＡＯはオキシエチレン基、オキシプロピレン基で、ＥＯの平均付加モル数が３０〜１６０、ＥＯ／ＰＯ付加モル比が１．５〜４．５）から選ばれる一種以上の脱墨剤でインキ剥離を行い、フローテーション後、４０〜８０℃の温水で洗浄する脱墨方法（特許文献１４）が開示されているが、この方法もフローテーションを前提としているため、曇点が低く、処理温度では発泡しない脱墨剤は用いておらず、フローテーション後の温水洗浄が必須となっている。
上記、何れの方法においても、フローテーションでの脱墨性を考慮しているため、疎水基を小さくして、曇点を上げている。従って、水に溶けすぎて界面活性は低下し、浸透力は小さくあるという欠点を有していた。
In any of the above methods, since the deinking property in the flotation is taken into consideration, the hydrophobic group is reduced to raise the cloud point. Accordingly, it has the disadvantages that it is too soluble in water and the surface activity is lowered and the penetrating power is small.
古紙からインキの分離効率を損なわずに、従来より電力原単位が低く、かつ、高白色度の脱墨古紙パルプを製造することができる脱墨法を提供するものである。 It is an object of the present invention to provide a deinking method that can produce deinked wastepaper pulp having a lower power intensity and a higher whiteness without impairing the separation efficiency of ink from wastepaper.
上記課題を解決するため、本発明者等は、前段および後段からなる２段フローテーションを用いずに、１段のフローテーション処理でも充分に脱墨を促進させ、漂白薬品の使用を極端に増加させずに消費電力原単位を大幅に低減させることができる方法について鋭意検討した。その結果、曇点が低い、特定の構造を持つ界面活性剤をパルパーに添加し、その後に洗浄処理を行うことで、効果的に目的を達成できることを見出した。 In order to solve the above-mentioned problems, the present inventors have promoted deinking sufficiently even in one-stage flotation treatment without using a two-stage flotation consisting of a front stage and a rear stage, and extremely increased the use of bleaching chemicals. We intensively studied a method that can greatly reduce the power consumption rate without doing so. As a result, it was found that the purpose can be effectively achieved by adding a surfactant having a low cloud point and having a specific structure to the pulper and then performing a cleaning treatment.
即ち。本発明は以下の発明を包含する。
（１）離解工程で下記一般式（I）で表され、曇点が０℃以上２５℃以下のポリエチレングリコール型非イオン性界面活性剤をパルパーに添加し、次いで ４０メッシュ以上１００メッシュ以下のワイヤー上でインキを洗浄するワイヤー洗浄工程を設け、その後の漂白工程あるいはニーディング工程で使用する脱墨剤としては、脂肪酸あるいは脂肪酸誘導体系の脱墨剤から選ばれる少なくとも１種類である印刷古紙から高白色度脱墨パルプを製造する方法。
That is. The present invention includes the following inventions.
(1) In the disaggregation step, a polyethylene glycol type nonionic surfactant having a cloud point of 0 ° C. or more and 25 ° C. or less is added to the pulper, and then a wire of 40 mesh or more and 100 mesh or less is represented by the following general formula (I). A deinking agent used in the subsequent bleaching or kneading step is provided with a wire washing step for washing the ink above, and is used as a deinking agent selected from fatty acid or fatty acid derivative-based deinking agents. A method for producing whiteness deinked pulp.
（２）前記界面活性剤の添加量が絶乾パルプに対して０．０１〜５質量％である（１）記載の印刷古紙から高白色度脱墨パルプを製造する方法。 (2) The method for producing high whiteness deinked pulp from the used printed paper according to (1), wherein the addition amount of the surfactant is 0.01 to 5% by mass with respect to the absolutely dry pulp.
（３）前記ワイヤー洗浄工程でのパルプ濃度が０．５〜２．０質量％である（１）又は（２）に記載の印刷古紙から高白色度脱墨パルプを製造する方法。 (3) A method for producing high-whiteness deinked pulp from used printed paper according to (1) or (2), wherein the pulp concentration in the wire washing step is 0.5 to 2.0% by mass.
上記本発明によれば、印刷古紙を離解する離解工程、除塵するスクリーニング工程、脱墨処理する前後段の２段からなるフローテーション工程、漂白及びソーキング処理をする漂白工程、分散処理する分散工程、洗浄処理する洗浄工程の組み合わせからなる高白色度脱墨パルプ製造設備から構成される古紙のパルプ化工程において、曇点が低く、特定の構造を持つ界面活性剤をパルパーに添加し、前段のフローテーション工程の代わりに、４０メッシュ以上１００メッシュ以下のワイヤー上でインキを洗浄するワイヤー洗浄工程を採用することにより、フローテーション工程を１段工程とし、且つ、漂白工程あるいはニーディング工程で使用する脱墨剤としては、インキ凝集性の強い脂肪酸あるいは、脂肪酸誘導体系の脱墨剤から選ばれる少なくとも１種類の脱墨剤を用いることによって、電力原単位が低く、かつ、高白色度の古紙パルプを製造することが可能となる。 According to the present invention, a disaggregation step for disaggregating used printing paper, a screening step for dust removal, a flotation step consisting of two stages before and after deinking, a bleaching step for bleaching and soaking, a dispersion step for dispersion treatment, In the pulping process of waste paper, which consists of a high whiteness deinked pulp manufacturing facility consisting of a combination of cleaning processes, a surfactant with a low cloud point and a specific structure is added to the pulper, By adopting a wire washing process for washing ink on a wire of 40 mesh or more and 100 mesh or less instead of the rotation process, the flotation process is made a one-stage process and the removal process used in the bleaching process or the kneading process. As the ink, a small amount selected from fatty acids with strong ink cohesion or fatty acid derivative-based deinking agents. By using Kutomo one cleaning solution, low electric power consumption rate, and it is possible to manufacture a high whiteness of waste paper pulp.
曇点が低く、特定の構造を持つ界面活性剤をパルパーに添加し、前段のフローテーション工程の代わりに、４０メッシュ以上１００メッシュ以下のワイヤー上でインキを洗浄するワイヤー洗浄工程を採用することにより、フローテーション工程を１段工程とできる理由について、発明者等は以下のように考えている。
即ち、印刷古紙からインキを除去し、１段フローテーションで高白色度のパルプを得ようとする場合、離解工程でパルプから充分にインキを剥離させ分散する必要があるが、フローテーション工程での脱インキ効率を向上させるため、パルプからインキを剥離させ分散する能力と、フローテーターにおけるインキの泡への吸着性、インキ同士の凝集性という、相反する効果のバランスを採った脱墨剤を添加しているため、パルプへの浸透性やインキ剥離性を著しく高めた界面活性剤は添加できず、インキの剥離が不充分になるという問題を有する。
By adding a surfactant with a low cloud point and a specific structure to the pulper and adopting a wire cleaning process that cleans the ink on a wire of 40 mesh or more and 100 mesh or less instead of the previous flotation process The inventors consider the reason why the flotation process can be a one-step process as follows.
That is, when removing the ink from the used printing paper and obtaining a high whiteness pulp by one-stage flotation, it is necessary to sufficiently peel and disperse the ink from the pulp in the disaggregation process. In order to improve the deinking efficiency, a deinking agent is added that balances the conflicting effects of the ability to peel and disperse the ink from the pulp, the ability of the ink to adsorb to the ink bubbles in the floatator, and the cohesiveness of the inks. For this reason, a surfactant having significantly improved permeability to the pulp and ink releasability cannot be added, and there is a problem that the ink is insufficiently peeled.
従って、パルパーでインキ剥離処理を行い、しかも、１段のフローテーターにおける脱インキ性のバランスを考慮した脱インキパルプを得るには、インキとパルプ、あるいはインキと塗工層との結合力を弱め、かつフローテーション適性に影響を与えない何らかの処理が必要であり、このような目的に適した薬剤、即ちパルプからのインキ剥離、洗浄を促進するための処理が不可欠である。本発明者等は、このような化合物として、曇点が低く、特定の構造を持つ界面活性剤が極めて好適であり、かつインキ剥離工程の後工程に、フローテーターの代わりに、洗浄工程を有する脱インキ処理を行う方法が、極めて好適であることを見出し、本発明を完成するに至った。上記一般式Ｉで表される界面活性剤が効果的であることの理由としては、曇点が０℃〜２５度と低い界面活性剤は、疎水性が強く、浸透性も高いため、インキの剥離力、洗浄性に優れるものと推測される。曇点が０℃より低くなると疎水性は強いものの、インキの剥離力、洗浄性が悪くなるため好ましくない。 Therefore, in order to obtain a deinked pulp that takes into consideration the balance of deinking in a single-stage floatator by performing an ink peeling treatment with a pulper, the bond strength between the ink and the pulp or the ink and the coating layer is weakened. In addition, some kind of treatment that does not affect the flotation suitability is necessary, and treatment suitable for such purpose, that is, treatment for accelerating the ink peeling from the pulp and washing is essential. The inventors of the present invention have a low cloud point and a surfactant having a specific structure as such a compound, and have a washing step instead of a floatator in the subsequent step of the ink peeling step. The inventors have found that a method for performing deinking treatment is extremely suitable, and have completed the present invention. The reason why the surfactant represented by the general formula I is effective is that the surfactant having a low cloud point of 0 ° C. to 25 ° C. is strong in hydrophobicity and high in permeability. It is presumed that the peel strength and cleaning properties are excellent. When the cloud point is lower than 0 ° C., the hydrophobicity is strong, but the ink peeling force and cleaning properties are deteriorated, which is not preferable.
さらに、一般式Ｉで表わされる界面活性剤が効果的である他の理由としては、インキ剥離工程の後工程で、強力な洗浄工程を有することにより、フローテーターにおける脱墨剤の影響を考慮する必要がなく、従来では使用できなかった、パルプへの浸透性、インキ剥離・分散性の高い界面活性剤を使用できることが挙げられる。 Furthermore, another reason why the surfactant represented by the general formula I is effective is to consider the influence of the deinking agent in the floatator by having a strong washing step after the ink peeling step. It is not necessary, and it is possible to use a surfactant having high permeability to pulp and high ink peeling / dispersibility, which could not be used conventionally.
一般に脱墨剤として知られる界面活性剤は、フローテーターにおける発泡性の観点から、処理温度と同等か、わずかに低い温度に曇点を持つものが有効であるとされており、本発明のような、曇点が０〜２５℃と低い界面活性剤を単独で用いている例はない。 A surfactant generally known as a deinking agent is considered to be effective if it has a cloud point at a temperature that is the same as or slightly lower than the processing temperature from the viewpoint of foamability in the floatator. There is no example in which a surfactant having a low cloud point of 0 to 25 ° C. is used alone.
本発明が対象としている古紙としては、新聞紙、チラシ、雑誌、書籍、事務用紙、その他複写機、ＯＡ機器から生じる印刷紙などを含む。印刷古紙としては、新聞紙、チラシ、雑誌、書籍、事務用紙、その他複写機、ＯＡ機器から生ずる印刷紙等、灰分が７％〜３５％含む古紙が挙げられ、中でも最も高白色度が得られにくいのは新聞紙であり、本発明の効果が顕著に現れるのは、印刷面が多く、印刷前の白紙白色度の低い新聞紙、印刷後時間の経過が３ヶ月以上の古紙等である。 The waste paper targeted by the present invention includes newspapers, flyers, magazines, books, office paper, other copiers, printing papers generated from OA equipment, and the like. Examples of the used printed paper include newspapers, flyers, magazines, books, office papers, printed papers produced from copiers and OA equipment, etc., and used papers containing 7% to 35% of ash content. Is newspaper, and the effects of the present invention are notable for newspapers with many printed surfaces and low whiteness before printing, and used paper whose time elapsed after printing is three months or more.
＜離解工程における離解条件＞
本発明の方法における離解工程では、パルパーに原料印刷古紙を固形分濃度１２〜１８％になるように希釈水を入れ、さらに薬品(水酸化ナトリウム)を、対パルプ０〜１．０質量％、好ましくは０〜０.５質量％添加する。本発明では、離解工程でさらに、界面活性剤を添加する。本発明で使用する界面活性剤はパルプからのインキ剥離、塗工層の分散を促進する界面活性剤であり、他の脱墨剤による発泡を著しく抑制することのない作用を有した界面活性剤が好ましく、離解時間としては１０〜３０分、好ましくは１０〜２５分、更に好ましくは１０〜１８分で、離解温度５〜５０℃、好ましくは２５〜５０℃で原料印刷古紙を離解する。
<Disaggregation conditions in disaggregation process>
In the disaggregation step in the method of the present invention, diluting water is added to the pulper so that the raw material printed waste paper has a solid content concentration of 12 to 18%, and a chemical (sodium hydroxide) is further added to pulp at 0 to 1.0 mass%, Preferably 0 to 0.5 mass% is added. In the present invention, a surfactant is further added in the disaggregation step. The surfactant used in the present invention is a surfactant that promotes ink peeling from the pulp and dispersion of the coating layer, and has a function that does not significantly suppress foaming by other deinking agents. The waste paper is disaggregated at a disaggregation temperature of 5 to 50 ° C., preferably 25 to 50 ° C. for a disaggregation time of 10 to 30 minutes, preferably 10 to 25 minutes, more preferably 10 to 18 minutes.
本発明で使用する界面活性剤は合成高分子系非イオン界面活性剤であり、親水基の種類によりポリエチレングリコール型とポリヒドロキシ型に分類される。ポリヒドロキシ型非イオン界面活性剤は、水に溶解しないものが多く、浸透性や剥離インキの洗浄性では劣るため、本発明では、ポリエチレングリコール型非イオン界面活性剤を使用する。本発明では、一般式（Ｉ）で表される曇点が０℃以上２５℃以下のポリエチレングリコール型非イオン性界面活性剤を対パルプ０.０１〜１.０質量％、好ましくは０.０３〜０.５質量％添加する。印刷古紙は印刷後三ヶ月以上経過するとインキの硬化が進み、インキが紙から剥離しづらくなるため浸透性に優れた本発明の界面活性剤を使用することで、インキを剥離しやすくしている。 The surfactant used in the present invention is a synthetic polymer-based nonionic surfactant, and is classified into a polyethylene glycol type and a polyhydroxy type depending on the type of hydrophilic group. Since many polyhydroxy type nonionic surfactants do not dissolve in water and are inferior in penetrability and detergency of release ink, a polyethylene glycol type nonionic surfactant is used in the present invention. In the present invention, a polyethylene glycol type nonionic surfactant having a cloud point of 0 ° C. or more and 25 ° C. or less represented by the general formula (I) is 0.01 to 1.0% by mass, preferably 0.03, based on pulp. Add ~ 0.5 wt%. Used paper is hardened after three months or more after printing, and it becomes difficult for the ink to be peeled off from the paper. .
一般式（Ｉ）で表されるポリエチレングリコール型非イオン界面活性剤を更に具体的に例示すれば、高級アルコールのオキシアルキレン基付加体である。これはインキの剥離力や浸透力が良好であるため、中性から弱アルカリ性でインキ剥離処理を行い、低発泡性で、かつ未剥離インキの少ない脱インキパルプを得るのに好適である。なお、アルキル基の炭素数が、１１以下のものは一般的に合成されておらず、利用する場合コスト的に非常に高いものとなってしまう。また、アルキル基の炭素数が１９以上、あるいはアルキル基の分子量に対するオキシアルキレン基の分子量が低くなってくると、水溶性に乏しくなり、反応系内での分散性が悪化して、浸透力が低下するばかりか、操作性にも問題が生じる。オキシアルキレン基としては、炭素数が２〜４が好ましく、オキシエチレン基、オキシプロピレン基が一般的であり、アルキル基の分子量に応じて、最適な曇点になるよう、付加モル数を変えることが望ましい。付加モル数は５以上が好ましく、３５以下が好ましい。 More specifically, the polyethylene glycol type nonionic surfactant represented by the general formula (I) is an oxyalkylene group adduct of a higher alcohol. This is suitable for obtaining a deinked pulp having a low foaming property and a small amount of unpeeled ink by performing an ink peeling treatment with neutral to weak alkalinity because of good ink peeling force and penetrating power. In addition, those having 11 or less carbon atoms in the alkyl group are generally not synthesized, and when used, the cost becomes very high. Further, when the carbon number of the alkyl group is 19 or more, or the molecular weight of the oxyalkylene group with respect to the molecular weight of the alkyl group becomes low, water solubility becomes poor, dispersibility in the reaction system deteriorates, and penetrating power is reduced. Not only does this decrease, but there will also be problems with operability. The oxyalkylene group preferably has 2 to 4 carbon atoms, and is generally an oxyethylene group or oxypropylene group, and the number of moles added is changed so as to obtain an optimal cloud point depending on the molecular weight of the alkyl group. Is desirable. The number of added moles is preferably 5 or more, and preferably 35 or less.
また、一般式（Ｉ）で表される界面活性剤の曇点は、低いほど疎水性が大きく、浸透性も高くなるが、反応系内で溶解せず、分散性が悪化するため、浸透性は低下し、剥離インキの洗浄性も悪化する。一方、曇点が高いものは、親水性が大きくなり、浸透性は低下することから、曇点が０〜２５℃と低い界面活性剤が望ましい。また処理温度は曇点より５℃〜２５℃高い処理温度で処理することが好ましい。インキ剥離工程や洗浄工程における処理温度が高い場合には、上記の理由から、界面活性剤の分散性を考慮して、曇点は高め、つまりやや親水性を強くする必要があり、逆に処理温度が低い場合には、疎水性を強めて曇点を下げ、浸透力を上げることが効果的である。処理温度としては、２０℃以下では、古紙の離解性やインキ剥離性が著しく低下するため、望ましくない。一方、８０℃以上では、蒸気などのコスト面、および界面活性剤の曇点を高くする必要があり、浸透性は著しく低下するため、望ましくない。 In addition, the lower the cloud point of the surfactant represented by the general formula (I), the higher the hydrophobicity and the higher the permeability, but it does not dissolve in the reaction system and the dispersibility deteriorates. Decreases and the washability of the release ink also deteriorates. On the other hand, those having a high cloud point have higher hydrophilicity and lower permeability, so a surfactant having a low cloud point of 0 to 25 ° C. is desirable. The treatment temperature is preferably 5 to 25 ° C. higher than the cloud point. When the processing temperature in the ink peeling process or washing process is high, for the reasons described above, it is necessary to increase the cloud point in consideration of the dispersibility of the surfactant. When the temperature is low, it is effective to increase the osmotic force by increasing the hydrophobicity to lower the cloud point. A treatment temperature of 20 ° C. or lower is not desirable because the disintegration property and ink releasability of waste paper are remarkably lowered. On the other hand, when the temperature is 80 ° C. or higher, it is necessary to increase the cost such as steam and the clouding point of the surfactant, and the penetrability is significantly lowered.
＜除塵工程＞
除塵工程は、クリーナー、スクリーンで原料中の異物を取り除く工程である。クリーナーで重量異物を取り除き、次にスクリーン、丸穴スクリーンやスリットスクリーンを用いて異物の除去を行う。本発明では高品質な脱墨古紙パルプを得るためにスリットスクリーン（１段目０．１５ｍｍスリット、２段目０．１５ｍｍスリット）を使用する。
<Dust removal process>
The dust removal step is a step of removing foreign substances in the raw material with a cleaner and a screen. Remove heavy foreign matter with a cleaner, and then remove foreign matter using a screen, round hole screen or slit screen. In the present invention, a slit screen (first stage 0.15 mm slit, second stage 0.15 mm slit) is used to obtain high-quality deinked waste paper pulp.
＜ワイヤー洗浄工程＞
ワイヤー洗浄工程では、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ワイヤー洗浄装置が用いられる。ワイヤー洗浄装置としては、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）等が挙げられる。一般的には、ワイヤー洗浄装置の目穴は、２０〜２００メッシュ程度までが考えられるが、灰分除去効率、洗浄効率の点から本発明では４０〜１００メッシュ、好ましく、更に好ましくは５０〜８０メッシュが適している。
<Wire cleaning process>
In the wire cleaning step, a wire cleaning device that preferentially removes ash in the raw material and minimizes fiber loss is used. Examples of the wire cleaning device include an extractor, a fall washer (manufactured by Eiko), and a double nip thickener (manufactured by Ishikawajima Industrial Machinery). In general, the eye hole of the wire cleaning device can be about 20 to 200 mesh, but 40 to 100 mesh is preferable in the present invention from the viewpoint of ash removal efficiency and cleaning efficiency, and more preferably 50 to 80 mesh. Is suitable.
本発明では、ワイヤー洗浄工程は前段フローテーション又は後段フローテーションのいずれかに代えて行う。前段フローテーション工程に代えて行う場合には、離解工程で剥離したインキや灰分が洗浄され除去されるため、漂白工程での漂白効率が上がることとなり、好ましい。 In the present invention, the wire cleaning step is performed in place of either the pre-stage flotation or the post-stage flotation. When it replaces with a former stage flotation process, since the ink and ash which peeled in the disaggregation process are wash | cleaned and removed, the bleaching efficiency in a bleaching process will rise and it is preferable.
前記ワイヤー洗浄装置の中では、紙料入口ゾーン、置換洗浄ゾーン、仕上がりゾーンの３ゾーンを有するドラムタイプの洗浄機であるフォールウォッシャー(栄工機製)が優れている。従来のドラムタイプの洗浄機は、紙料をマット状に形成させてしまい、ワイヤーとの接触回数が減少することにより洗浄効果が発揮されにくくなるデメリットがあったが、フォールウオッシャーの場合は、マットを形成させないために、強力な高速攪拌羽根を取りつけてある。紙料処理は入口濃度を４％以下の濃度で行うことができるが、好ましくは０．５〜２．０％、更に好ましくは、１．０〜１．５％である。０．５％より低い濃度の場合、ワイヤーの処理面積が多大なものとなるし、２％の濃度を越えるとインキ除去効率が極端に低下する。
（紙パ技協誌５３巻第９号第６４〜６７頁特に６５頁図１、特開平８−１７６９８５号、特開平９−１８８９８６号公報参照）
Among the wire cleaning devices, a fall washer (manufactured by Eiko), which is a drum type cleaning machine having three zones of a paper inlet zone, a replacement cleaning zone, and a finishing zone, is excellent. The conventional drum type washer has the disadvantage that the stock is formed in a mat shape and the number of contact with the wire is reduced, which makes it difficult to achieve the cleaning effect. In order to prevent formation of a high-speed stirring blade, a powerful high-speed stirring blade is attached. The paper material treatment can be performed at an inlet concentration of 4% or less, preferably 0.5 to 2.0%, and more preferably 1.0 to 1.5%. When the concentration is lower than 0.5%, the processing area of the wire becomes enormous, and when the concentration exceeds 2%, the ink removal efficiency is extremely lowered.
(See Paper-Pa-Technical Journal, Vol. 53, No. 9, pages 64 to 67, especially page 65, Fig. 1, JP-A-8-176985, JP-A-9-188986)
＜漂白工程＞
漂白工程は、薬品を使用してパルプを白くする工程であり、古紙再生には、一般的には、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。過酸化水素漂白は、過酸化水素対パルプ０．５〜４．０質量％、苛性ソーダ対パルプ１．５〜３．０質量％、珪酸ソーダ対パルプ０．５〜１．０質量％（ ＮａＯＨとして）で使用し、漂白時間は１〜４時間、漂白パルプ濃度は２０〜３５％、漂白温度は５０〜７５℃で行うことが好ましい。
<Bleaching process>
The bleaching step is a step of whitening the pulp using a chemical. Generally, hydrogen peroxide, hydrosulfide, thiourea dioxide, hypo, or the like is used for recycling used paper. Hydrogen peroxide bleaching is 0.5 to 4.0% by weight of hydrogen peroxide to pulp, 1.5 to 3.0% by weight of caustic soda to pulp, 0.5 to 1.0% by weight of sodium silicate to pulp (as NaOH) The bleaching time is preferably 1 to 4 hours, the bleached pulp concentration is 20 to 35%, and the bleaching temperature is preferably 50 to 75 ° C.
＜分散工程＞
分散工程は、ニーダーやディスパーザーで繊維からインキを剥離・分散させる工程である。ディスパーザー処理濃度は２０〜５０％、処理温度は４０〜９０℃で、微細インキを凝集させ、フローテーターでのインキ凝集性の強い脱墨剤をディスパーザー処理直前に対パルプ０〜０．５質量％添加することが好ましい。フローテーション前に脱墨剤がパルプに均一に混合できれば、漂白工程に脱墨剤を添加してもかまわない。
<Dispersing process>
The dispersion step is a step of peeling and dispersing the ink from the fiber with a kneader or a disperser. Disperser treatment concentration is 20 to 50%, treatment temperature is 40 to 90 ° C., fine ink is agglomerated, and deinking agent with strong ink agglomeration property in a floatator is applied to pulp 0 to 0.5 immediately before disperser treatment It is preferable to add mass%. If the deinking agent can be uniformly mixed with the pulp before the flotation, the deinking agent may be added to the bleaching step.
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が、例えば、脂肪酸の場合、花王（株）社製のＤＩ−２５４（オレイン酸）、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等が挙げられる。 Deinking agents with strong ink cohesion include fatty acid or fatty acid derivative-based deinking agents. For example, in the case of fatty acids, DI-254 (oleic acid) manufactured by Kao Corporation, Daiichi Kogyo Seiyaku Co., Ltd. K-4004-D manufactured by K.K. 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. are mentioned.
＜フローテーション脱墨工程＞
フローテーション工程は、フローテーターで空気にインキを吸着させインキを系外に除去する脱墨工程である。一般的にはフローテーターは２段~３段で処理され、１段ではフロスに含まれているパルプ分が多く歩留まりが低下するため、１次のフロスを２次に供給し、２次の精選原料を一次に戻す方式がとられている。本発明ではフローテーターは１段であり、処理濃度は０．７〜１．５％、フローテーター処理温度は１０〜５０℃、好ましくは３０〜４５℃で行う。
<Flotation deinking process>
The flotation process is a deinking process in which ink is adsorbed to the air by a flotator and the ink is removed from the system. Generally, the floatator is processed in two to three stages, and in the first stage, the pulp content in the floss is large and the yield is reduced. The method of returning the raw material to the primary is taken. In the present invention, the flotator is a single stage, the treatment concentration is 0.7 to 1.5%, and the flotation treatment temperature is 10 to 50 ° C, preferably 30 to 45 ° C.
＜洗浄工程＞
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、０．６〜１．５％のパルプスラリーを清水で希釈した後、１５〜３５％まで脱水洗浄することが好ましい。
<Washing process>
The washing step is a step of dewatering and washing fine ink that could not be removed by the flowator, and after diluting 0.6 to 1.5% of the pulp slurry with fresh water, it is preferable to dewater and wash to 15 to 35%.
＜白水循環＞
ワイヤー洗浄後のろ液（白水）は、固形分濃度が０．５〜１．５％あるため、一部を排水とした以外は、直接パルパーの希釈水として使用する。
<White water circulation>
Since the filtrate (white water) after wire washing has a solid content concentration of 0.5 to 1.5%, it is directly used as dilution water for the pulper except that a part thereof is drained.
以下、本発明を実施例により具体的に説明するが、実施例は本発明をなんら限定するものではない。本実施例中では、特に断らない限り、原料濃度は灰分込みの固形分濃度、薬品添加率は、対絶乾パルプあたりの質量％である。 EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, an Example does not limit this invention at all. In this example, unless otherwise specified, the raw material concentration is the solid content concentration including ash, and the chemical addition rate is mass% per dry pulp.
（白色度測定方法）
白色度シートは、漂白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)
For the whiteness sheet, after the bleached finished pulp is disaggregated, a sulfuric acid band is added to the pulp slurry in an amount of 20.0%, and a sheet having a basis weight of 60 g / m 2 is added according to Tappi test method T205os-71 (JIS P 8209). Produced. Thereafter, the whiteness of the fluorescence intensity cut was measured with a spectral whiteness colorimeter (manufactured by Suga Test Instruments).
＜実施例１＞
オフセット印刷新聞古紙６０％、チラシ古紙４０％からなる印刷古紙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０．３％、式（Ｉ）において、表１に示す曇点２０℃の界面活性剤を、絶乾パルプあたり純分換算で０．３％添加し、離解温度３５℃で１５分間離解した。離解後の原料を除塵工程にて処理し、１．０％に濃度調整後、ワイヤー洗浄機（フォールウオッシャー：栄工機製、５０メッシュワイヤー）にて処理した。
ワイヤー洗浄後のパルプスラリーは、約３％に希釈後、既存の脱墨パルプ製造設備にて、脱水処理、漂白処理、ディスパーザー処理、フローテーター処理、洗浄処理の順に従って処理して完成パルプを製造した。漂白条件は、過酸化水素添加率対パルプ３.０％、水酸化ナトリウム添加率対パルプ２．３％。珪酸ナトリウム添加率対パルプ水酸化ナトリウム換算０．７％、パルプ濃度約２８％、漂白時間２時間３０分、漂白温度６７℃で行った。フローテーター脱墨条件は、特殊脂肪酸誘導体（花王（株）社製、ＤＩ−１１２０）添加率０．１８％、脂肪酸（花王（株）社製、ＤＩ−２５４）添加率０．０３％、フローテーター処理濃度１．１％、フローテーター処理温度４２℃で行った。完成パルプの白色度、２段フローテーション法とのＤＩＰ工程歩留、製造電力原単位の差を表２に示す。
<Example 1>
The waste paper used for printing is composed of 60% waste paper for offset printing and 40% waste paper for flyers. The pulper is charged with 15% raw material concentration, 0.3% sodium hydroxide addition rate, and the cloud point of 20 ° C shown in Table 1 in the formula (I). The surfactant was added in an amount of 0.3% in terms of pure per absolute dry pulp, and disaggregated at a disaggregation temperature of 35 ° C. for 15 minutes. The raw material after disaggregation was processed in a dust removal process, and after adjusting the concentration to 1.0%, it was processed with a wire washer (Fall Washer: manufactured by Eiko Machine Co., Ltd., 50 mesh wire).
The pulp slurry after washing the wire is diluted to about 3%, and then processed in the order of dewatering, bleaching, disperser, floatator, and washing in the existing deinking pulp manufacturing equipment. Manufactured. The bleaching conditions were hydrogen peroxide addition rate to 3.0% pulp, sodium hydroxide addition rate to 2.3% pulp. Sodium silicate addition rate to pulp sodium hydroxide equivalent 0.7%, pulp concentration about 28%, bleaching time 2 hours 30 minutes, bleaching temperature 67 ° C. Flotator deinking conditions were as follows: Special fatty acid derivative (Kao Corporation, DI-1120) addition rate 0.18%, Fatty acid (Kao Corporation, DI-254) addition rate 0.03%, The rotator treatment concentration was 1.1%, and the flow rate was 42 ° C. Table 2 shows the whiteness of the finished pulp, the difference in the DIP process yield with the two-stage flotation method, and the production power intensity.
＜実施例２＞
ワイヤー洗浄機のワイヤーを８０メッシュとした以外は、実施例１と同様に処理し、完成パルプを製造した。完成パルプの白色度、従来の２段フローテーション法とのＤＩＰ工程歩留、製造電力原単位の差を表２に示す。
<Example 2>
A finished pulp was produced in the same manner as in Example 1 except that the wire of the wire washer was 80 mesh. Table 2 shows the differences in the whiteness of the finished pulp, the DIP process yield with respect to the conventional two-stage flotation method, and the production power intensity.
＜実施例３＞
ワイヤー洗浄機の処理濃度を０．３％とした以外は、実施例１と同様に処理し、完成パルプを製造した。完成パルプの白色度、従来の２段フローテーション法とのＤＩＰ工程歩留、製造電力原単位の差を表２に示す。
<Example 3>
A finished pulp was produced in the same manner as in Example 1 except that the treatment concentration of the wire washer was 0.3%. Table 2 shows the differences in the whiteness of the finished pulp, the DIP process yield with respect to the conventional two-stage flotation method, and the production power intensity.
＜実施例４＞
ワイヤー洗浄機の処理濃度を２．５％とした以外は、実施例１と同様に処理し、完成パルプを製造した。完成パルプの白色度、従来の２段フローテーション法とのＤＩＰ工程歩留、製造電力原単位の差を表２に示す。
<Example 4>
A finished pulp was produced in the same manner as in Example 1 except that the treatment concentration of the wire washer was 2.5%. Table 2 shows the differences in the whiteness of the finished pulp, the DIP process yield with respect to the conventional two-stage flotation method, and the production power intensity.
＜比較例１＞
実施例１において、離解工程で、式（Ｉ）で示す界面活性剤を添加しなかったこと以外は実施例１と同様に処理し、完成パルプを製造した。完成パルプの白色度、従来の２段フローテーション法とのＤＩＰ工程歩留、製造電力原単位の差を表２に示す。
<Comparative Example 1>
In Example 1, a finished pulp was produced in the same manner as in Example 1 except that the surfactant represented by the formula (I) was not added in the disaggregation step. Table 2 shows the differences in the whiteness of the finished pulp, the DIP process yield with respect to the conventional two-stage flotation method, and the production power intensity.
＜比較例２＞
表１に示す式（Ｉ）で表される構造で曇点＜０℃の界面活性剤とした他は、実施例１と同様に処理し、完成パルプを製造した。完成パルプの白色度、従来の２段フローテーション法とのＤＩＰ工程歩留、製造電力原単位の差を表２に示す。
<Comparative example 2>
A finished pulp was produced in the same manner as in Example 1 except that the surfactant represented by the formula (I) shown in Table 1 was used as a surfactant having a cloud point of <0 ° C. Table 2 shows the differences in the whiteness of the finished pulp, the DIP process yield with respect to the conventional two-stage flotation method, and the production power intensity.
＜比較例３＞
表１に示す式（Ｉ）で表される構造で曇点１０℃の界面活性剤とした他は、実施例１と同様に処理し、完成パルプを製造した。完成パルプの白色度、従来の２段フローテーション法とのＤＩＰ工程歩留、製造電力原単位の差を表２に示す。
<Comparative Example 3>
A finished pulp was produced in the same manner as in Example 1, except that the surfactant represented by the formula (I) shown in Table 1 was used as a surfactant having a cloud point of 10 ° C. Table 2 shows the differences in the whiteness of the finished pulp, the DIP process yield with respect to the conventional two-stage flotation method, and the production power intensity.
＜比較例４＞
表１に示す式（Ｉ）で表される構造で曇点３９℃の界面活性剤とした他は、実施例１と同様に処理し、完成パルプを製造した。完成パルプの白色度、従来の２段フローテーション法とのＤＩＰ工程歩留、製造電力原単位の差を表２に示す。
<Comparative example 4>
A finished pulp was produced in the same manner as in Example 1 except that the surfactant represented by the formula (I) shown in Table 1 was used as a surfactant having a cloud point of 39 ° C. Table 2 shows the differences in the whiteness of the finished pulp, the DIP process yield with respect to the conventional two-stage flotation method, and the production power intensity.
＜比較例５＞
表１に示す式（Ｉ）で表される構造で曇点４２℃の界面活性剤とした他は、実施例１と同様に処理し、完成パルプを製造した。完成パルプの白色度、従来の２段フローテーション法とのＤＩＰ工程歩留、製造電力原単位の差を表２に示す。
<Comparative Example 5>
A finished pulp was produced in the same manner as in Example 1 except that the surfactant represented by the formula (I) shown in Table 1 had a cloud point of 42 ° C. Table 2 shows the differences in the whiteness of the finished pulp, the DIP process yield with respect to the conventional two-stage flotation method, and the production power intensity.
＜比較例６＞
ワイヤー洗浄機のワイヤーを２４メッシュとした以外は、実施例１と同様に処理し、完成パルプを製造した。完成パルプの白色度、従来の２段フローテーション法とのＤＩＰ工程歩留、製造電力原単位の差を表２に示す。
<Comparative Example 6>
The finished pulp was manufactured in the same manner as in Example 1 except that the wire washer was 24 mesh. Table 2 shows the differences in the whiteness of the finished pulp, the DIP process yield with respect to the conventional two-stage flotation method, and the production power intensity.
＜比較例７＞
ワイヤー洗浄機のワイヤーを１５０メッシュとした以外は、実施例１と同様に処理し、完成パルプを製造した。完成パルプの白色度、従来の２段フローテーション法とのＤＩＰ工程歩留、製造電力原単位の差を表２に示す。
<Comparative Example 7>
The finished pulp was manufactured in the same manner as in Example 1 except that the wire of the wire washer was 150 mesh. Table 2 shows the differences in the whiteness of the finished pulp, the DIP process yield with respect to the conventional two-stage flotation method, and the production power intensity.
＜比較例８＞
脱墨工程に入れる脱墨剤を特殊脂肪酸誘導体（花王（株）社製、ＤＩ−１１２０）から、高級アルコール系脱墨剤（花王（株）社製、ＤＩ−７２８２）とし、添加率を対パルプ純分換算で０．１８％とした以外は、実施例１と同様に処理し、完成パルプを製造した。完成パルプの白色度、従来の２段フローテーション法とのＤＩＰ工程歩留、製造電力原単位の差を表２に示す。
<Comparative Example 8>
The deinking agent used in the deinking process is changed from a special fatty acid derivative (DI-1120, manufactured by Kao Corporation) to a higher alcohol deinking agent (DI-7282, manufactured by Kao Corporation). A finished pulp was produced in the same manner as in Example 1 except that the amount was 0.18% in terms of pure pulp. Table 2 shows the differences in the whiteness of the finished pulp, the DIP process yield with respect to the conventional two-stage flotation method, and the production power intensity.
＜比較例９＞
オフセット印刷新聞古紙６０％、チラシ古紙４０％からなる印刷古紙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０．３％、式（Ｉ）において、表１に示す曇点３９℃の界面活性剤を、絶乾パルプあたり純分換算で０．３％添加し、離解温度３５℃で１５分間離解した。離解後の原料を除塵工程にて処理し、１．１％に濃度調整後、一段目のフローテーターにて処理した。一段目のフローテーター処理後のパルプスラリーは、既存の脱墨パルプ製造設備にて脱水処理、漂白処理、ディスパーザー処理、フローテーター処理の順序で処理し製品パルプを製造した。漂白条件は過酸化水素添加率対パルプ３．０％、水酸化ナトリウム添加率対パルプ２．３％、珪酸ナトリウム添加率対パルプ水酸化ナトリウム換算０．７％、パルプ濃度を約２８％、漂白時間２時間３０分、漂白温度６７℃で行った。二段目のフローテーター脱墨条件は、特殊脂肪酸誘導体（花王社製、ＤＩ−１１２０）添加率０．０８％、脂肪酸（花王社製、ＤＩ−２５４）添加率０．０３％、二段目のフローテーター処理濃度１．１％、フローテーター処理温度４２℃で行った。完成パルプの白色度を表２に示す。
<Comparative Example 9>
Waste paper used for offset printing used paper 60%, used paper used for flyer 40% is fed into a pulper, the raw material concentration is 15%, the sodium hydroxide addition rate is 0.3%, and in Formula (I), the cloud point of 39 ° C. shown in Table 1 The surfactant was added in an amount of 0.3% in terms of pure per absolute dry pulp, and disaggregated at a disaggregation temperature of 35 ° C. for 15 minutes. The raw material after disaggregation was processed in a dust removal process, adjusted to a concentration of 1.1%, and then processed with a first-stage floatator. The pulp slurry after the first-stage floatator treatment was processed in the order of dehydration treatment, bleaching treatment, disperser treatment, and floatator treatment in the existing deinked pulp production equipment to produce product pulp. The bleaching conditions were hydrogen peroxide addition rate to pulp 3.0%, sodium hydroxide addition rate to pulp 2.3%, sodium silicate addition rate to pulp sodium hydroxide equivalent 0.7%, pulp concentration about 28%, bleaching The time was 2 hours 30 minutes at a bleaching temperature of 67 ° C. The second stage floatator deinking conditions were: 0.08% addition rate of special fatty acid derivative (Kao Corporation, DI-1120), 0.03% addition ratio of fatty acid (Kao Corporation, DI-254), 2nd stage This was carried out at a flow rate of 1.1% and a flow rate of 42 ° C. Table 2 shows the whiteness of the finished pulp.
実施例１〜４および比較例１〜９に示した通り、離解工程で一般式（Ｉ）で示される曇点が０℃以上２５℃以下のポリエチレングリコール型非イオン性界面活性剤をパルパーに添加し、次いで、４０メッシュ以上１００メッシュ以下のワイヤー洗浄工程を設け、その後の漂白工程あるいはニーディング工程で使用される脱墨剤として、脂肪酸あるいは脂肪酸誘導体系の脱墨剤の少なくとも一種類を使用することで、電力原単位が低く、かつ、高白色度の古紙パルプを製造することが可能となった。
As shown in Examples 1 to 4 and Comparative Examples 1 to 9, a polyethylene glycol type nonionic surfactant having a cloud point of 0 ° C. or higher and 25 ° C. or lower added to the pulper in the disaggregation step. Next, a wire washing step of 40 mesh or more and 100 mesh or less is provided, and at least one type of fatty acid or fatty acid derivative type deinking agent is used as a deinking agent used in the subsequent bleaching step or kneading step. As a result, it has become possible to produce waste paper pulp having a low power intensity and high whiteness.
Claims (3)
The method for producing high-whiteness deinked pulp from used printed paper according to claim 1 or 2, wherein the pulp concentration (mass%) in the wire washing step is 0.5% to 2.0%.
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| JP2009256808A (en) * | 2008-04-11 | 2009-11-05 | Toppan Printing Co Ltd | Method for recycling waste printed paper |
| JP2017179615A (en) * | 2016-03-28 | 2017-10-05 | 日本製紙株式会社 | Deinking method for uv printed matter |
| JP6713105B1 (en) * | 2019-05-15 | 2020-06-24 | 株式会社片山化学工業研究所 | Pulp cleaning |
| WO2020230351A1 (en) * | 2019-05-15 | 2020-11-19 | 株式会社片山化学工業研究所 | Pulp washing |
| US11560672B2 (en) | 2018-03-29 | 2023-01-24 | Nippon Paper Industries Co., Ltd. | Methods for deinking UV prints |
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| JP2004068175A (en) * | 2002-08-02 | 2004-03-04 | Oji Paper Co Ltd | Method for producing deinked pulp from printed waste paper |
| JP2004190176A (en) * | 2002-12-11 | 2004-07-08 | Oji Paper Co Ltd | Method for producing deinked pulp |
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| JP2009256808A (en) * | 2008-04-11 | 2009-11-05 | Toppan Printing Co Ltd | Method for recycling waste printed paper |
| JP2017179615A (en) * | 2016-03-28 | 2017-10-05 | 日本製紙株式会社 | Deinking method for uv printed matter |
| US11560672B2 (en) | 2018-03-29 | 2023-01-24 | Nippon Paper Industries Co., Ltd. | Methods for deinking UV prints |
| JP6713105B1 (en) * | 2019-05-15 | 2020-06-24 | 株式会社片山化学工業研究所 | Pulp cleaning |
| WO2020230351A1 (en) * | 2019-05-15 | 2020-11-19 | 株式会社片山化学工業研究所 | Pulp washing |
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