JP5401852B2 - Ash processing method - Google Patents
Ash processing method Download PDFInfo
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- JP5401852B2 JP5401852B2 JP2008174348A JP2008174348A JP5401852B2 JP 5401852 B2 JP5401852 B2 JP 5401852B2 JP 2008174348 A JP2008174348 A JP 2008174348A JP 2008174348 A JP2008174348 A JP 2008174348A JP 5401852 B2 JP5401852 B2 JP 5401852B2
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- acid
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- ash
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- 238000003672 processing method Methods 0.000 title description 3
- 239000007788 liquid Substances 0.000 claims description 98
- 238000000034 method Methods 0.000 claims description 44
- 239000000123 paper Substances 0.000 claims description 32
- 238000000605 extraction Methods 0.000 claims description 31
- 239000002253 acid Substances 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 22
- 239000010881 fly ash Substances 0.000 claims description 17
- 150000007524 organic acids Chemical class 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 12
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- 150000002484 inorganic compounds Chemical class 0.000 claims 1
- 229910010272 inorganic material Inorganic materials 0.000 claims 1
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- 238000000926 separation method Methods 0.000 description 19
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 15
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- 238000012423 maintenance Methods 0.000 description 2
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
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- QGGOCWIJGWDKHC-FSIIMWSLSA-N (2s,3s,4r,5r)-2,4,5-trihydroxy-3-methoxy-6-oxohexanoic acid Chemical compound OC(=O)[C@@H](O)[C@@H](OC)[C@H](O)[C@@H](O)C=O QGGOCWIJGWDKHC-FSIIMWSLSA-N 0.000 description 1
- MIJYXULNPSFWEK-GTOFXWBISA-N 3beta-hydroxyolean-12-en-28-oic acid Chemical compound C1C[C@H](O)C(C)(C)[C@@H]2CC[C@@]3(C)[C@]4(C)CC[C@@]5(C(O)=O)CCC(C)(C)C[C@H]5C4=CC[C@@H]3[C@]21C MIJYXULNPSFWEK-GTOFXWBISA-N 0.000 description 1
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
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- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
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- AEMOLEFTQBMNLQ-YMDCURPLSA-N D-galactopyranuronic acid Chemical compound OC1O[C@H](C(O)=O)[C@H](O)[C@H](O)[C@H]1O AEMOLEFTQBMNLQ-YMDCURPLSA-N 0.000 description 1
- QUUCYKKMFLJLFS-UHFFFAOYSA-N Dehydroabietan Natural products CC1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 QUUCYKKMFLJLFS-UHFFFAOYSA-N 0.000 description 1
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- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- JKLISIRFYWXLQG-UHFFFAOYSA-N Epioleonolsaeure Natural products C1CC(O)C(C)(C)C2CCC3(C)C4(C)CCC5(C(O)=O)CCC(C)(C)CC5C4CCC3C21C JKLISIRFYWXLQG-UHFFFAOYSA-N 0.000 description 1
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- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
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Landscapes
- Processing Of Solid Wastes (AREA)
- Paper (AREA)
Description
本発明は、灰を湿式抽出処理する方法に関し、更に詳しくは、薬品添加量が少ないため環境に対する負荷の小さい灰の処理方法に関する。 The present invention relates to a method for subjecting ash to a wet extraction process, and more particularly to a method for treating ash that has a low environmental impact because the amount of chemical addition is small.
灰を湿式抽出処理する技術は、主にゴミ焼却施設から発生する灰や飛灰を有効利用する際に問題となる塩素や重金属を除去する目的で使用されている。また、カルシウムや亜鉛など、有用物を分離回収する手段や重金属を不溶化させる手段としても使用される。 The technology for wet extraction of ash is mainly used for the purpose of removing chlorine and heavy metals that are problematic when using ash and fly ash generated from garbage incineration facilities effectively. It is also used as a means for separating and recovering useful substances such as calcium and zinc and a means for insolubilizing heavy metals.
灰の成分を可溶化又は不溶化させるためには、湿式抽出処理のｐＨ調整が行われる。例えば、塩素を抽出するためにｐＨを７〜９とすること（特許文献１）、亜鉛を抽出するためにｐＨを７〜１１として洗浄した後、硫酸を加えてｐＨ４〜６とすること（特許文献２）、重金属を抽出するために処理液のアルカリ土類金属濃度を１．５％以上とすること（特許文献３）が開示されている。 In order to solubilize or insolubilize the ash component, the pH of the wet extraction process is adjusted. For example, the pH is adjusted to 7 to 9 for extracting chlorine (Patent Document 1), and the pH is set to 7 to 11 for extracting zinc, and then sulfuric acid is added to adjust the pH to 4 to 6 (patent) Document 2) discloses that the alkaline earth metal concentration of the treatment liquid is 1.5% or more in order to extract heavy metals (Patent Document 3).
次に、ｐＨ調整に使用する酸については、燐酸（特許文献４）、鉱酸（特許文献５）、塩酸と硝酸の使用（特許文献６）が開示されており、無機の酸を使用することが一般的である。 Next, as for the acid used for pH adjustment, phosphoric acid (Patent Document 4), mineral acid (Patent Document 5), use of hydrochloric acid and nitric acid (Patent Document 6) are disclosed, and an inorganic acid should be used. Is common.
また、ｐＨ調整に使用するアルカリについては、アルカリ土類金属（特許文献３）が開示されており、無機のアルカリを使用することが一般的である。
さらに、湿式抽出処理後の液には有害な重金属が含まれるため、キレート剤を添加して重金属を不溶化し、灰の中に固定化する方法が提案されている（特許文献７）。
Moreover, about the alkali used for pH adjustment, alkaline-earth metal (patent document 3) is disclosed and it is common to use an inorganic alkali.
Furthermore, since harmful heavy metals are contained in the liquid after the wet extraction treatment, a method has been proposed in which a chelating agent is added to insolubilize heavy metals and fix them in ash (Patent Document 7).
灰の湿式抽出処理には抽出後の固液分離処理が伴うが、灰は粒子が細かいために、マットを形成し、脱水性が悪くなる。これを解消するため、フィルタープレス機等が開発されているが、機器に灰が入り込み、メンテナンスに多大な手間がかかるというのが現状である。 The ash wet extraction process involves a solid-liquid separation process after extraction, but the ash forms fine mats and forms a mat, resulting in poor dehydration. In order to solve this problem, filter press machines and the like have been developed. However, the present situation is that ashes enter the equipment and much maintenance is required.
製紙工場内で発生した灰と液を接触させる方法については、バイオマスの酸加水分解処理で発生した強い酸性の液を製紙工程の廃棄物の焼却灰と接触させて中和処理する方法（特許文献８）が開示されているが、この液に木材由来の有機酸が含まれているかどうかは明確ではなく、該有機酸の作用・効果について開示も示唆もされていない。
従来技術による灰の湿式抽出処理では、ｐＨ調整のため処理液に無機の酸やアルカリを添加し、更に、処理液にキレート剤を添加するため、多量の薬品を必要とし、環境負荷が大きいという課題がある。また、灰を湿式抽出後に固液分離する工程では、灰の粒子がマットを形成してフィルターが目詰まりし、多量の水や薬品で洗浄しなければならないため、環境負荷が大きいという課題がある。本発明は、環境負荷を小さくすることができる灰の処理方法を提供することを目的とする。 In the conventional wet ash extraction process, an inorganic acid or alkali is added to the treatment liquid for pH adjustment, and a chelating agent is added to the treatment liquid. There are challenges. Also, in the process of solid-liquid separation after wet extraction of ash, the ash particles form a mat and the filter is clogged, and the filter must be washed with a large amount of water and chemicals, so there is a problem that the environmental burden is large. . An object of this invention is to provide the processing method of ash which can make environmental impact small.
本発明者らはかかる課題を解決するため鋭意検討した結果、製紙工場内で発生した液に無機の酸またはアルカリ及び木材由来の有機酸が含まれており、灰の抽出と有害金属の固定化を同時に行うことができるばかりでなく、該液は製紙工程で加温されている（３０〜６０℃程度）ので、灰の抽出性に優れることを見出した。 As a result of intensive studies to solve such problems, the present inventors have found that the liquid generated in the paper mill contains an inorganic acid or alkali and an organic acid derived from wood, and extracts ash and immobilizes harmful metals. It was found that the liquid was heated in the papermaking process (about 30 to 60 ° C.), so that the ash extractability was excellent.
また、製紙工場内で発生した液には繊維質が含まれており、この繊維質が灰の間に入ることで、湿式抽出後に灰を固液分離する際に、脱水性を改善でき、目詰まりも防げるため、機器のメンテナンスに伴う負荷を低減できることを見出した。 In addition, the liquid generated in the paper mill contains fibers, and when these fibers enter the ash, the dehydration can be improved when the ash is separated into solid and liquid after wet extraction. It was found that the load associated with equipment maintenance can be reduced to prevent clogging.
さらに良いことには、通常、排液を工場外に排出する際には、中和処理及び化学的酸素要求量（ＣＯＤ）低減処理を施す必要があるが、本発明において上記の液として排液を使用すると、排液が灰によって中和され、液中のＣＯＤ成分が灰に補足されるので、中和処理とＣＯＤ低減処理を同時に行うことができるため、薬品使用量を大幅に削減できることを見出し、本発明を完成させるに至った。 Even better, normally, when discharging the waste liquid outside the factory, it is necessary to carry out a neutralization process and a chemical oxygen demand (COD) reduction process. Since the effluent is neutralized by the ash and the COD component in the liquid is captured by the ash, the neutralization process and the COD reduction process can be performed at the same time. The headline and the present invention have been completed.
上記目的を達成することができる本発明は以下の各発明から選択された発明である。 The present invention capable of achieving the above object is an invention selected from the following inventions .
（２）前記液が、クラフトパルプ製造工程から発生する液である（１）に記載の灰の処理方法。 (2) The ash treatment method according to (1), wherein the liquid is a liquid generated from a kraft pulp manufacturing process.
（３）前記液が、クラフトパルプ製造工程の酸処理段、酸洗浄段、オゾン漂白段、過酸化水素漂白段、酸素脱リグニン段、アルカリ抽出段、各段付随のパルプ洗浄段の少なくとも一つから排出される液である（１）又は（２）に記載の灰の処理方法。 (3) The liquid is at least one of an acid treatment stage, an acid washing stage, an ozone bleaching stage, a hydrogen peroxide bleaching stage, an oxygen delignification stage, an alkali extraction stage, and an associated pulp washing stage in the kraft pulp manufacturing process. The ash treatment method according to (1) or (2), wherein the ash is discharged from the slag.
（４）前記液が、クラフトパルプ製造工程の蒸解工程から発生する液である（１）又は（２）に記載の灰の処理方法。 (4) The ash treatment method according to (1) or (2), wherein the liquid is a liquid generated from a cooking process of a kraft pulp manufacturing process.
（５）前記液が、製紙工場内の少なくとも二箇所から発生した液を混合して得られる液である（１）〜（４）のいずれか１項に記載の灰の処理方法。 (5) The ash treatment method according to any one of (1) to (4), wherein the liquid is a liquid obtained by mixing liquids generated from at least two places in a paper mill.
（６）前記液が、クラフトパルプ製造工程から発生する無機物を含む液と、その他製紙工場内で発生した有機酸と無機物を含む液を混合して得られる液である（１）〜（５）のいずれか１項に記載の灰の処理方法。 (6) The said liquid is a liquid obtained by mixing the liquid containing the inorganic substance which generate | occur | produces from a kraft pulp manufacturing process, and the liquid containing the organic acid and inorganic substance which generate | occur | produced in other paper manufacture factories (1)-(5). The processing method of the ash of any one of these.
（７）前記クラフトパルプ製造工程から発生する無機物を含む液が、苛性化工程から発生する液である（１）〜 (7) The liquid containing the inorganic substance generated from the kraft pulp manufacturing process is a liquid generated from the causticizing process (1) to
（６）のいずれか１項に記載の灰の処理方法。 The method for treating ash according to any one of (6).
（８）前記液を希釈または濃縮した液を使用する（１）〜（７）のいずれか１項に記載の灰の処理方法。 (8) The ash treatment method according to any one of (1) to (7), wherein a solution obtained by diluting or concentrating the solution is used.
（９）前記湿式抽出を多段で行う（１）〜（８）のいずれか１項に記載の灰の処理方法。 (9) The ash treatment method according to any one of (1) to (8), wherein the wet extraction is performed in multiple stages.
本発明は、灰の湿式抽出、固液分離に使用する薬品の量を大幅に削減し、更に製紙排水の処理に使用する薬品の量を大幅に削減し、環境負荷を小さくすることを可能とする。 The present invention greatly reduces the amount of chemicals used for wet extraction of ash and solid-liquid separation, and further reduces the amount of chemicals used for papermaking wastewater treatment, thereby reducing the environmental burden. To do.
本発明で用いられる灰は、特に限定するものではなく、焼却灰、燃焼灰、焼却飛灰、溶融飛灰、飛灰、灰塵、ゴミ処理溶融飛灰、石炭灰、ＲＰＦ灰、タイヤ灰、木屑灰、ペーパースラッジ灰、これらの混合物等如何なるものでも良いが、湿式抽出する目的物に合わせて選択されることが好ましい。例えば、塩素を抽出する場合には、ＲＰＦ灰を含む灰、亜鉛を抽出する場合はタイヤを含む灰が好ましい。 The ash used in the present invention is not particularly limited, and incineration ash, combustion ash, incineration fly ash, molten fly ash, fly ash, ash dust, garbage processing molten fly ash, coal ash, RPF ash, tire ash, wood waste Any one of ash, paper sludge ash, a mixture thereof, and the like may be used, but it is preferably selected in accordance with the object to be wet-extracted. For example, when extracting chlorine, ash containing RPF ash is preferable, and when extracting zinc, ash including tires is preferable.
本発明で用いられる製紙工場内で発生した有機酸と無機物を含む液は、特に限定するものではなく、例えばクラフトパルプ製造工程から得られる液、蒸解工程、酸素脱リグニン工程、漂白工程、抄紙工程、各工程に付随する洗浄工程等如何なる工程から得られるものでも良いが、設備の腐食を防ぐことを考慮すると、塩素を含まない、酸素脱リグニン工程、漂白工程の酸洗浄段や酸処理段、オゾン処理段等から得られる液が好適に用いられる。 The liquid containing an organic acid and an inorganic substance generated in the paper mill used in the present invention is not particularly limited. For example, a liquid obtained from a kraft pulp manufacturing process, a cooking process, an oxygen delignification process, a bleaching process, and a papermaking process. In addition, it may be obtained from any process such as a cleaning process accompanying each process, but considering the prevention of corrosion of equipment, it does not contain chlorine, oxygen delignification process, acid cleaning stage or acid treatment stage of bleaching process, A liquid obtained from an ozone treatment stage or the like is preferably used.
本発明で用いられる製紙工場内で発生した無機物を含む液は、特に限定されるものではなく、例えば塗工工程、苛性化工程、洗浄工程等如何なる工程から得られるものでも良いが、不純物が少ない苛性化工程から得られる緑液や白液が好適に用いられる。 The liquid containing an inorganic substance generated in the paper mill used in the present invention is not particularly limited, and may be obtained from any process such as a coating process, a causticizing process, and a cleaning process, but has few impurities. A green liquor or white liquor obtained from the causticizing step is preferably used.
本発明における製紙工場内で発生した液に含まれる有機酸とは、木材に含まれるリグニン由来のバニリン酸、シリンガ酸、フェノール酸、抽出成分由来の脂肪酸、プリカチン酸、アビエチン酸、ネオアビエチン酸、パルストリン酸、レボピマール酸、デヒドロアビエチン酸、ピマール酸、イソピマール酸、サンダラコピマール酸等の樹脂酸、オレアノール酸、バス酸、プロトバス酸、セルロース又はヘミセルロース由来の乳酸、グリコール酸、蓚酸、琥珀酸、マレイン酸、２−フランカルボン酸、５−ホルミル−２−フランカルボン酸、ギ酸、フマル酸、酒石酸、３−ヒドロキシプロパン酸、２−ヒドロキシプロパン二酸、２，３−ジヒドロキシプロパン酸、２−ヒドロキシペンタン二酸、２，３−ヒジドロキシペンタン二酸、４−Ｏ−メチル−Ｄ−グルクロン酸、アルドビオウロン酸、アルドトリオウロン酸、アルドテトラオウロン酸、アルドペンタオウロン酸、アルドヘキサオウロン酸、ガラクツロン酸、リグニン−ヘミセルロース複合体由来のアルドビオウロン酸等が挙げられる。また、木材由来の成分は、クラフトパルプ製造工程で複雑に反応するため、ここに列挙していない構造の有機酸も多数存在する。 The organic acid contained in the liquid generated in the paper mill in the present invention is lignin-derived vanillic acid, syringic acid, phenolic acid, fatty acids derived from extracted components, pricatic acid, abietic acid, neoabietic acid, Resin acid such as pulstronic acid, levopimaric acid, dehydroabietic acid, pimaric acid, isopimaric acid, sandaracopimaric acid, oleanolic acid, bath acid, protobasic acid, lactic acid, glycolic acid, oxalic acid, maleic acid, maleic derived from cellulose or hemicellulose Acid, 2-furancarboxylic acid, 5-formyl-2-furancarboxylic acid, formic acid, fumaric acid, tartaric acid, 3-hydroxypropanoic acid, 2-hydroxypropanedioic acid, 2,3-dihydroxypropanoic acid, 2-hydroxypentane Diacid, 2,3-hydridopentanedioic acid, 4-O-methyl -D- glucuronic acid, Arudobiouron acid, aldo trio uronic acid, aldo tetra Ou Ron acid, aldo penta Ou Ron acid, aldo hexa Ou Ron acid, galacturonic acid, lignin - such Arudobiouron acid derived from hemicellulose complex thereof. In addition, since wood-derived components react in a complicated manner in the kraft pulp manufacturing process, there are many organic acids having structures not listed here.
本発明における製紙工場内で発生した液に含まれる無機物とは、工程で使用された硫酸、二酸化塩素、過酸化水素、苛性ソーダ、水酸化マグネシウム、工程から回収された苛性ソーダ、硫化ソーダ等が挙げられる。 Examples of the inorganic substance contained in the liquid generated in the paper mill in the present invention include sulfuric acid, chlorine dioxide, hydrogen peroxide, caustic soda, magnesium hydroxide used in the process, caustic soda recovered from the process, sodium sulfide, and the like. .
本発明で用いられる製紙工場内で発生した有機酸と無機物を含む液は、希釈または濃縮することができる。また、少なくとも二種類の液を任意の割合で混合することもできる。混合液を更に希釈、または濃縮できることは言うまでもない。希釈、濃縮、混合の割合は、液のｐＨとＣＯＤ量、抽出する目的物によって適宜調整される。例えば酸処理濾液を水で希釈してｐＨ調整することや、ｐＨが３程度の酸洗浄濾液と、有機酸を多く含みｐＨが１０程度の酸素脱リグニン濾液を混合することができる。 The liquid containing an organic acid and an inorganic substance generated in the paper mill used in the present invention can be diluted or concentrated. Further, at least two kinds of liquids can be mixed at an arbitrary ratio. It goes without saying that the mixture can be further diluted or concentrated. The ratio of dilution, concentration, and mixing is appropriately adjusted depending on the pH and COD amount of the liquid and the target product to be extracted. For example, the acid-treated filtrate can be diluted with water to adjust the pH, or an acid-washed filtrate having a pH of about 3 and an oxygen delignin filtrate having a high organic acid and a pH of about 10 can be mixed.
本発明で用いられる湿式抽出機は、特に限定するものではなく、公知の機器、例えばスクリュープレス脱水機やベルト型濾過濃縮機、真空脱水とプレスを組み合わせた脱水機等を用いることができる。また、湿式抽出の条件は特に限定するものではなく、公知の条件を採用することができる。例えば、灰を固液質量比1：０．１〜1：１０００で抽出することができる。灰の洗浄を効果的に行いながら、洗浄液を最小とする点から、灰と液の質量比は１：０．１〜1：１００が好ましい。必要に応じてｐＨ調整剤や製紙工程外から調達した有機酸、重金属の不溶化剤等の薬品を添加することができる。灰の抽出時にスラリーを攪拌することができるし、二酸化炭素を含むガスを添加することができるし、脱水時にシャワー水をかけることもできる。 The wet extractor used in the present invention is not particularly limited, and a known device such as a screw press dehydrator, a belt type filter concentrator, a dehydrator that combines vacuum dehydration and press, or the like can be used. Moreover, the conditions of wet extraction are not specifically limited, A well-known condition is employable. For example, ash can be extracted at a solid-liquid mass ratio of 1: 0.1 to 1: 1000. The mass ratio of ash to liquid is preferably 1: 0.1 to 1: 100 from the viewpoint of minimizing the cleaning liquid while effectively cleaning the ash. If necessary, chemicals such as pH adjusters, organic acids procured from outside the papermaking process, and heavy metal insolubilizers can be added. The slurry can be stirred during ash extraction, a gas containing carbon dioxide can be added, and shower water can be poured during dehydration.
本発明における灰の湿式抽出に先立ち、公知の条件で湿式抽出したスラリーを原料として使用することができる。また、本発明における灰の湿式抽出は多段で行うことができる。排液の処理と灰の抽出処理を効率よく行うためには、酸性排液での湿式抽出とアルカリ性排液での湿式抽出を多段で行うことが好適である。 Prior to the wet extraction of ash in the present invention, a slurry wet-extracted under known conditions can be used as a raw material. Moreover, the wet extraction of ash in the present invention can be performed in multiple stages. In order to efficiently perform drainage treatment and ash extraction treatment, it is preferable to perform wet extraction with acidic drainage and wet extraction with alkaline drainage in multiple stages.
以下に実施例及び比較例を挙げて本発明を具体的に説明する。なお、実施例１〜３及び５〜７は参考実施例である。 The present invention will be specifically described below with reference to examples and comparative examples. In addition, Examples 1-3 and 5-7 are reference examples.
各種測定は下に示す規格に従った。これ以降の実施例及び比較例においても、各種測定は同様にして行った。
ｐＨの測定：ＪＩＳ Ｚ ８８０２−１９８４
ＣＯＤの測定：ＪＩＳ Ｋ ０８０６−１９９７
塩素の測定：ＪＩＳ Ａ １１５４−２００３、１２記載のイオンクロマトグラフ法
鉛の測定：ＪＩＳ Ｋ ０４００−５２−２０−１９９８
Various measurements followed the standards shown below. In the following examples and comparative examples, various measurements were performed in the same manner.
Measurement of pH: JIS Z 8802-1984
Measurement of COD: JIS K 0806-1997
Measurement of chlorine: ion chromatograph method described in JIS A 1154-2003, 12 Measurement of lead: JIS K 0400-52-20-1998
＜実施例１＞
製紙工場のボイラから発生したＲＰＦ、タイヤ、木屑由来の飛灰と前記製紙工場の総合排水（温度３０℃）を質量比１：１０で混合し、３０分攪拌して湿式抽出した。抽出後のスラリーをブフナー漏斗にて固液分離した。処理前後の液のｐＨとＣＯＤ、及び固液分離後の液中に溶出した塩素と鉛の量を測定した。使用した総合排水には、蓚酸と硫酸が含まれていた。
<Example 1>
RPF generated from the boiler of the paper mill, tires, wood ash-derived fly ash and the general waste water (temperature 30 ° C.) of the paper mill were mixed at a mass ratio of 1:10, stirred for 30 minutes, and wet-extracted. The slurry after extraction was subjected to solid-liquid separation using a Buchner funnel. The pH and COD of the liquid before and after the treatment, and the amounts of chlorine and lead eluted in the liquid after solid-liquid separation were measured. The total wastewater used contained oxalic acid and sulfuric acid.
＜実施例２＞
製紙工場のボイラから発生したＲＰＦ、タイヤ、木屑由来の飛灰と前記製紙工場から排出されたパルプの酸処理濾液（温度６０℃）を質量比１：１０で混合し、３０分攪拌して湿式抽出した。抽出後のスラリーをブフナー漏斗にて固液分離した。処理前後の液のｐＨとＣＯＤ、及び固液分離後の液中に溶出した塩素と鉛の量を測定した。使用したパルプの酸処理濾液には、硫酸、２−フランカルボン酸、５−ホルミル−２−フランカルボン酸が含まれていた。
<Example 2>
RPF generated from the boiler of a paper mill, tires, fly ash derived from wood chips, and acid-treated filtrate (temperature 60 ° C.) of pulp discharged from the paper mill are mixed at a mass ratio of 1:10, stirred for 30 minutes, and wet. Extracted. The slurry after extraction was subjected to solid-liquid separation using a Buchner funnel. The pH and COD of the liquid before and after the treatment, and the amounts of chlorine and lead eluted in the liquid after solid-liquid separation were measured. The acid treatment filtrate of the used pulp contained sulfuric acid, 2-furancarboxylic acid, and 5-formyl-2-furancarboxylic acid.
＜実施例３＞
製紙工場のボイラから発生したＲＰＦ、タイヤ、木屑由来の飛灰と前記製紙工場から排出された酸洗浄濾液とパルプの酸素脱リグニン濾液の混合液（温度５０℃）を質量比１：１０で混合し、湿式抽出した。抽出後のスラリーをブフナー漏斗にて固液分離した。処理前後の液のｐＨとＣＯＤ、及び固液分離後の液中に溶出した塩素と鉛の量を測定した。使用した酸洗浄濾液には硫酸と２−フランカルボン酸が、パルプの酸素脱リグニン濾液には、苛性ソーダが含まれていた。
<Example 3>
Mixing a mixture of RPF, tires, and wood fly fly ash generated from a paper mill boiler, acid wash filtrate discharged from the paper mill, and pulp oxygen delignification filtrate (temperature 50 ° C.) at a mass ratio of 1:10. And wet extracted. The slurry after extraction was subjected to solid-liquid separation using a Buchner funnel. The pH and COD of the liquid before and after the treatment, and the amounts of chlorine and lead eluted in the liquid after solid-liquid separation were measured. The acid wash filtrate used contained sulfuric acid and 2-furancarboxylic acid, and the pulp oxygen delignification filtrate contained caustic soda.
＜実施例４＞
製紙工場のボイラから発生したＲＰＦ、タイヤ、木屑由来の飛灰と前記製紙工場から排出された酸洗浄濾液と蒸解工程から発生した黒液の混合液（温度５０℃）を質量比１：１０で混合し、湿式抽出した。抽出後のスラリーをブフナー漏斗にて固液分離した。処理前後の液のｐＨとＣＯＤ、及び固液分離後の液中に溶出した塩素と鉛の量を測定した。使用した酸洗浄濾液には、硫酸と２−フランカルボン酸が、黒液には、苛性ソーダ、バニリン酸が含まれていた。
<Example 4>
A mixture of RPF, tires, wood chips fly ash generated from a paper mill boiler, acid wash filtrate discharged from the paper mill and black liquor generated from the cooking process (temperature 50 ° C.) at a mass ratio of 1:10. Mixed and wet extracted. The slurry after extraction was subjected to solid-liquid separation using a Buchner funnel. The pH and COD of the liquid before and after the treatment, and the amounts of chlorine and lead eluted in the liquid after solid-liquid separation were measured. The acid washing filtrate used contained sulfuric acid and 2-furancarboxylic acid, and the black liquor contained caustic soda and vanillic acid.
＜実施例５＞
製紙工場のボイラから発生したＲＰＦ、タイヤ、木屑由来の飛灰と前記製紙工場から排出されたパルプの過酸化水素処理濾液を２倍希釈した液（温度３０℃）を質量比１：１０で混合し、湿式抽出した。抽出後のスラリーをブフナー漏斗にて固液分離した。処理前後の液のｐＨとＣＯＤ、及び固液分離後の液中に溶出した塩素と鉛の量を測定した。使用したパルプの過酸化水素処理濾液には苛性ソーダ及び蓚酸が含まれていた。
<Example 5>
Mixing RPF, tires, wood ash fly ash generated from a paper mill boiler and a hydrogen peroxide-treated filtrate of pulp discharged from the paper mill (temperature 30 ° C) at a mass ratio of 1:10 And wet extracted. The slurry after extraction was subjected to solid-liquid separation using a Buchner funnel. The pH and COD of the liquid before and after the treatment, and the amounts of chlorine and lead eluted in the liquid after solid-liquid separation were measured. The hydrogen peroxide treated filtrate of the pulp used contained caustic soda and oxalic acid.
＜実施例６＞
製紙工場のボイラから発生したＲＰＦ、タイヤ、木屑由来の飛灰と前記製紙工場の苛性化工程から発生した弱液とパルプの酸処理工程から排出された濾液と希釈水を混合して得られた液（温度５０℃）を質量比１：１０で混合し、湿式抽出した。抽出後のスラリーをブフナー漏斗にて固液分離した。処理前後の液のｐＨとＣＯＤ、及び固液分離後の液中に溶出した塩素と鉛の量を測定した。使用した弱液には苛性ソーダが、パルプの酸処理濾液には、硫酸、２−フランカルボン酸、５−ホルミル−２−フランカルボン酸が含まれていた。
<Example 6>
It was obtained by mixing RPF, tires, wood ash derived fly ash generated from a paper mill boiler, weak liquid generated from the causticization process of the paper mill, filtrate discharged from the pulp acid treatment process, and dilution water. The liquid (temperature 50 ° C.) was mixed at a mass ratio of 1:10 and wet-extracted. The slurry after extraction was subjected to solid-liquid separation using a Buchner funnel. The pH and COD of the liquid before and after the treatment, and the amounts of chlorine and lead eluted in the liquid after solid-liquid separation were measured. The weak liquid used contained caustic soda, and the acid-treated filtrate of the pulp contained sulfuric acid, 2-furancarboxylic acid, and 5-formyl-2-furancarboxylic acid.
＜実施例７＞
製紙工場のボイラから発生したＲＰＦ、タイヤ、木屑由来の飛灰と前記製紙工場から排出されたパルプの酸洗浄処理濾液（温度５０℃）を質量比１：１０で混合し、湿式抽出した。抽出後のスラリーをブフナー漏斗にて固液分離後、再び酸洗浄処理濾液で湿式抽出、固液分離した。処理前後の液のｐＨとＣＯＤ、及び固液分離後の液中に溶出した塩素と鉛の量を測定した。使用したパルプの酸洗浄濾液には、硫酸、２−フランカルボン酸、５−ホルミル−２−フランカルボン酸が含まれていた。
<Example 7>
RPF generated from a boiler of a paper mill, tires, fly ash derived from wood chips and acid-washed filtrate (temperature of 50 ° C.) of pulp discharged from the paper mill were mixed at a mass ratio of 1:10 and wet-extracted. The slurry after extraction was subjected to solid-liquid separation with a Buchner funnel, and then again wet-extracted and solid-liquid separated with an acid washing treatment filtrate. The pH and COD of the liquid before and after the treatment, and the amounts of chlorine and lead eluted in the liquid after solid-liquid separation were measured. The acid washing filtrate of the used pulp contained sulfuric acid, 2-furancarboxylic acid and 5-formyl-2-furancarboxylic acid.
＜比較例１＞
液を水道水（２０℃）とした以外は実施例１と同様の操作を行った。処理前後の液のｐＨと固液分離後の液中に溶出した塩素と鉛の量を測定した。水道水から蓚酸、２−フランカルボン酸、５−ホルミル−２−フランカルボン酸、バニリン酸は検出されなかった。
<Comparative Example 1>
The same operation as in Example 1 was performed except that the liquid was tap water (20 ° C.). The pH of the liquid before and after the treatment and the amounts of chlorine and lead eluted in the liquid after solid-liquid separation were measured. Succinic acid, 2-furancarboxylic acid, 5-formyl-2-furancarboxylic acid, and vanillic acid were not detected from tap water.
＜比較例２＞
液を水道水（２０℃）とした以外は実施例５と同様の操作を行った。２回目に行った処理前後の液のｐＨと固液分離後の液中に溶出した塩素と鉛の量を測定した。
<Comparative example 2>
The same operation as in Example 5 was performed except that the liquid was tap water (20 ° C.). The pH of the liquid before and after the second treatment and the amounts of chlorine and lead eluted in the liquid after solid-liquid separation were measured.
＜比較例３＞
液を水道水（２０℃）に硫酸とクエン酸を添加した混合液とした以外は比較例１と同様の操作を行った。
<Comparative Example 3>
The same operation as in Comparative Example 1 was performed except that the liquid was a mixed liquid obtained by adding sulfuric acid and citric acid to tap water (20 ° C.).
実施例１〜７で得られた液の性質を表１に、比較例１〜３より得られた液の性質を表２に示す。 The properties of the liquids obtained in Examples 1 to 7 are shown in Table 1, and the properties of the liquids obtained from Comparative Examples 1 to 3 are shown in Table 2.
表１の実施例と表２の比較例との比較から明らかなように、灰の湿式抽出処理に製紙工場内から発生する有機酸と無機物を含む液を用いると塩素の溶出量が大幅に増加する。理由には無機物が含まれていることと、液温が高いことが考えられる。一方、有機酸のキレート効果によって溶出する鉛の量が低減する。そのため、重金属の不溶化処理に用いる薬品を大幅に削減することが可能であり、環境負荷を低減できる。製紙工場内から発生する液中の有機酸の中で、どのような成分が有効であるかについては今後の研究が必要であるが、パルプ由来の成分に鉛を補足する効果があると思量される。 As is clear from the comparison between the examples in Table 1 and the comparative examples in Table 2, the use of a liquid containing organic acids and inorganic substances generated from the paper mill in the ash wet extraction process greatly increases the amount of chlorine eluted. To do. It is conceivable that the reason is that an inorganic substance is contained and the liquid temperature is high. On the other hand, the amount of lead eluted due to the chelating effect of the organic acid is reduced. Therefore, it is possible to greatly reduce the chemicals used for the insolubilization treatment of heavy metals, and the environmental load can be reduced. Future research is necessary to determine what components are effective among the organic acids in the liquid generated from the paper mill, but it is thought that they have the effect of supplementing lead to pulp-derived components. The
また、製紙工場で発生する液は工場外へ排出する場合、中和処理とＣＯＤ低減処理を行う必要があるが、表１から明らかなように、灰の湿式抽出前後で液が中性化し、ＣＯＤも削減される。そのため、中和処理とＣＯＤ低減処理に用いる薬品も大幅に削減することが可能であり、環境負荷を低減できる。 In addition, when the liquid generated in the paper mill is discharged outside the factory, it is necessary to perform neutralization treatment and COD reduction treatment. As is clear from Table 1, the liquid is neutralized before and after wet extraction of ash, COD is also reduced. Therefore, the chemicals used for the neutralization process and the COD reduction process can be greatly reduced, and the environmental load can be reduced.
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