JP2015229157A - Processing method of oil-containing sludge - Google Patents
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F11/00—Treatment of sludge; Devices therefor
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Abstract
Description
本発明は、鋼材の圧延工程などで発生する含油スラッジの処理方法に関する。より詳しくは、含油スラッジから油分を分離する技術に関する。 The present invention relates to a method for treating oil-containing sludge generated in a steel material rolling process or the like. More specifically, the present invention relates to a technique for separating oil from oil-containing sludge.
鋼材及び鋼板の熱間圧延工程において発生するミルスラッジには、１〜１０質量％程度の油分が含まれる。この含油スラッジは鉄源となるため、製鉄工程において再利用することが望ましいが、油を含んだまま製鉄工程へ戻すと、例えば焼結工程などで排ガスに黒煙が発生するなどの問題が生じる。このため、含油スラッジを鉄原料として回収再利用するためには、油分を除去する必要がある。 Mill sludge generated in the hot rolling process of steel and steel contains about 1 to 10% by mass of oil. Since this oil-impregnated sludge is an iron source, it is desirable to reuse it in the iron making process. However, if the oil-containing sludge is returned to the iron making process while containing oil, problems such as black smoke being generated in the exhaust gas during the sintering process occur. . For this reason, in order to collect and reuse oil-containing sludge as an iron raw material, it is necessary to remove oil.
従来、含油スラッジ中の油分を除去する方法としては、例えば、アルカリ塩の混合物とノニルフェノール系非イオン界面活性剤と水からなる洗浄剤で、含油スラッジを洗浄する方法がある（特許文献１，２参照）。また、洗浄剤として珪酸ナトリウムなどのアルカリ金属水酸化物を用いる方法もある（特許文献３参照）。 Conventionally, as a method for removing oil from oil-containing sludge, for example, there is a method of cleaning oil-containing sludge with a cleaning agent comprising a mixture of an alkali salt, a nonylphenol nonionic surfactant and water (Patent Documents 1 and 2). reference). There is also a method using an alkali metal hydroxide such as sodium silicate as a cleaning agent (see Patent Document 3).
更に、洗浄剤として、ノニオン系やアニオン系の界面活性剤と水酸化ナトリウムとを含む水溶液を用いる方法も提案されている（特許文献４参照）。一方、回転キルン型燃焼炉を使用して、含油スラッジに含まれる油分を燃焼除去する方法も知られている（例えば、特許文献５参照）。 Furthermore, a method using an aqueous solution containing a nonionic or anionic surfactant and sodium hydroxide as a cleaning agent has been proposed (see Patent Document 4). On the other hand, a method of burning and removing oil contained in oil-containing sludge using a rotary kiln-type combustion furnace is also known (see, for example, Patent Document 5).
しかしながら、特許文献１，２に記載の方法で用いられているノニルフェノール系非イオン界面活性剤は、内分泌かく乱作用がある所謂環境ホルモンの疑いがあり、使用を控える動きがある。一方、特許文献３に記載の処理方法で使用している洗浄剤はそのような心配はないが、効果が十分に得られない場合がある。 However, the nonylphenol nonionic surfactants used in the methods described in Patent Documents 1 and 2 are suspected of so-called environmental hormones having endocrine disrupting action, and there is a movement to refrain from using them. On the other hand, the cleaning agent used in the treatment method described in Patent Document 3 does not have such a concern, but the effect may not be sufficiently obtained.
また、特許文献４に記載の処理方法では、十分に鹸化することが難しいため、脱油効果が低いという問題点がある。更に、特許文献５に記載の処理方法、燃焼排ガスの処理に多大の経費を必要とするなどの問題がある。 Further, the treatment method described in Patent Document 4 has a problem that the effect of deoiling is low because it is difficult to sufficiently saponify. Furthermore, there is a problem that a large amount of expense is required for the treatment method described in Patent Document 5 and the treatment of combustion exhaust gas.
そこで、本発明は、簡便な処理で、効率よく油分を分離することが可能な含油スラッジの処理方法を提供することを主目的とする。 Therefore, the main object of the present invention is to provide a method for treating oil-containing sludge capable of separating oil efficiently by simple treatment.
本発明に係る含油スラッジの処理方法は、含油スラッジを含むスラリーに、珪酸ナトリウムとポリオキシエチレンアルキルエーテル系界面活性剤とを添加し、撹拌する工程を有する。
本発明の含油スラッジの処理方法では、前記含油スラッジ１００質量部に対して、前記珪酸ナトリウムを、ＳｉＯ２換算で１〜２．５質量部添加してもよい。
また、前記含油スラッジ１００質量部に対して、前記ポリオキシエチレンアルキルエーテル系界面活性剤を、０．０５〜１質量部添加することもできる。
一方、前記ポリオキシエチレンアルキルエーテル系界面活性剤としては、例えばＨＬＢが８以上のものを使用することができる。
また、前記含油スラッジは、例えば製鉄工程で発生したミルスラッジである。
The method for treating oil-containing sludge according to the present invention includes a step of adding sodium silicate and a polyoxyethylene alkyl ether surfactant to a slurry containing oil-containing sludge and stirring.
In the method for treating oil-containing sludge of the present invention, 1 to 2.5 parts by mass of the sodium silicate may be added in terms of SiO 2 with respect to 100 parts by mass of the oil-containing sludge.
Moreover, 0.05-1 mass part of said polyoxyethylene alkyl ether type-surfactants can also be added with respect to 100 mass parts of said oil-containing sludge.
On the other hand, as the polyoxyethylene alkyl ether surfactant, for example, one having an HLB of 8 or more can be used.
Further, the oil-containing sludge is, for example, mill sludge generated in the iron making process.
本発明によれば、従来よりも簡便な処理で、効率よく含油スラッジから油分を除去することができる。 According to the present invention, oil can be efficiently removed from oil-containing sludge by a simpler process than before.
以下、本発明を実施するための形態について、詳細に説明する。なお、本発明は、以下に説明する実施形態に限定されるものではない。 Hereinafter, embodiments for carrying out the present invention will be described in detail. Note that the present invention is not limited to the embodiments described below.
本実施形態の含油スラッジの処理方法は、製鉄工程で発生したミルスラッジなどの含油スラッジから油分を分離する方法であり、含油スラッジを含むスラリーに珪酸ナトリウム（珪酸ソーダ）及びポリオキシエチレンアルキルエーテル系界面活性剤を添加して撹拌する工程を行う。本実施形態の含油スラッジの処理方法により処理を行うスラリーは、例えば、含油スラッジに水を添加してスラリー化することにより得られる。なお、含油スラッジを採取する際に十分な水分を一緒に採取できる場合には、さらに水を加える必要はない。 The treatment method of the oil-containing sludge of this embodiment is a method of separating oil from oil-containing sludge such as mill sludge generated in the iron making process, and sodium silicate (sodium silicate) and polyoxyethylene alkyl ether-based interface in the slurry containing oil-containing sludge An activator is added and stirred. The slurry to be treated by the method for treating oil-containing sludge of the present embodiment is obtained, for example, by adding water to the oil-containing sludge to form a slurry. In addition, when sufficient water | moisture content can be extract | collected together when extract | collecting oil-containing sludge, it is not necessary to add water further.
（スラリー化工程）
スラリー化工程では、撹拌槽に含油スラッジと水を入れスラリーとする。その際、水の添加比率は、処理対象の含油スラッジの種類や状態に応じて適宜選択することができるが、例えば製鉄工程で発生したミルスラッジの場合、含油スラッジ１質量部に対して、水を１〜３質量部とすることができる。これにより、スラッジと薬剤とが混合しやすくなり、これらを十分に接触させることが可能となる。なお、含油スラッジの添加する水は、工業用水や上水などを使用することができる。
(Slurry process)
In the slurrying step, oil-containing sludge and water are placed in a stirring tank to form a slurry. At that time, the addition ratio of water can be appropriately selected according to the type and state of the oil-containing sludge to be treated. For example, in the case of mill sludge generated in the iron making process, water is added to 1 part by mass of the oil-containing sludge. It can be 1 to 3 parts by mass. Thereby, it becomes easy to mix a sludge and a chemical | medical agent and it becomes possible to make these contact sufficiently. The water added to the oil-containing sludge can be industrial water or clean water.
また、スラリー化工程では、蒸気などの加熱手段を用いて、含油スラッジの温度を４０℃以上とすることが好ましく、５０℃以上にすることがより好ましく、６０℃以上にすることが更に好ましい。このように、含油スラッジの温度を上げることにより、スラッジに付着している油分を軟質化して、分離・除去しやすくすることができる。 In the slurrying step, the temperature of the oil-containing sludge is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, and still more preferably 60 ° C. or higher by using a heating means such as steam. Thus, by raising the temperature of the oil-containing sludge, the oil component adhering to the sludge can be softened and easily separated and removed.
（撹拌工程）
撹拌工程では、前述したスラリー化工程により得たスラリーに、珪酸ナトリウムとポリオキシエチレンアルキルエーテル系界面活性剤とを添加して撹拌する。ここで、珪酸ナトリウム（珪酸ソーダ）は、「水ガラス」とも言われており、一般にＮａ２Ｏ・ｎＳｉＯ２・ｍＨ２Ｏの分子式で表される。また、珪酸ナトリウムには、含油スラッジを分散させる効果及びアルカリによる脱脂する効果がある。
(Stirring process)
In the stirring step, sodium silicate and a polyoxyethylene alkyl ether surfactant are added to the slurry obtained by the slurrying step described above and stirred. Here, sodium silicate (sodium silicate) is also referred to as “water glass” and is generally represented by a molecular formula of Na 2 O.nSiO 2 .mH 2 O. Further, sodium silicate has an effect of dispersing oil-containing sludge and an effect of degreasing with alkali.
本実施形態の含油スラッジの処理方法で用いる珪酸ナトリウムは、特に限定されるものではないが、ＪＩＳ Ｋ１４０８に規定される珪酸３号が好適である。含油スラッジに対する珪酸ナトリウムの添加量は、少ないと効果が弱く、多いと不経済である。具体的には、珪酸３号を用いる場合は、含油スラッジ１００質量部に対して、珪酸３号を３〜８質量部添加することが好ましく、４〜６質量部添加することがより好ましい。 The sodium silicate used in the method for treating oil-containing sludge of the present embodiment is not particularly limited, but silicic acid No. 3 defined in JIS K1408 is preferable. If the amount of sodium silicate added to the oil-containing sludge is small, the effect is weak, and if it is large, it is uneconomical. Specifically, when using silicic acid No. 3, it is preferable to add 3-8 mass parts of silicic acid No. 3 with respect to 100 mass parts of oil-containing sludge, and it is more preferable to add 4-6 mass parts.
また、その他の珪酸ナトリウムを用いる場合は、含油スラッジ１００質量部に対して、ＳｉＯ２換算で１〜２．５質量部添加することが好ましく、１．２〜１．８質量部添加することがより好ましい。なお、珪酸３号とその他の珪酸ナトリウムで、好適な添加量が異なるのは、成分組成（Ｎａ２ＯとＳｉＯ２との比率）が異なるためである。 In the case of using other sodium silicate per 100 parts by weight of oil-containing sludge, it is preferable to add 1 to 2.5 parts by weight in terms of SiO 2, it is added 1.2-1.8 parts by weight More preferred. In silicate No. 3 and other sodium silicate, the preferred amount is different, (ratio between Na 2 O and SiO 2) component composition are different.
本実施形態の含油スラッジの処理方法では、界面活性剤として、ポリオキシアルキレンアルキルエーテル系ノニオン界面活性剤を用いる。ポリオキシアルキレンアルキルエーテル系ノニオン界面活性剤は、浸透力及び洗浄力を有し、珪酸ナトリウムと併用することで、相乗効果を発揮する。 In the oil-containing sludge treatment method of this embodiment, a polyoxyalkylene alkyl ether nonionic surfactant is used as the surfactant. The polyoxyalkylene alkyl ether nonionic surfactant has penetrating power and detergency, and exhibits a synergistic effect when used in combination with sodium silicate.
ポリオキシアルキレンアルキルエーテル系ノニオン界面活性剤の構造及び物性は、特に限定されるものではないが、スラリーに添加するため、水に分散してスラッジと接触する必要がある。そこで、本実施形態の含油スラッジ処理方法には、ＨＬＢが８以上のポリオキシアルキレンアルキルエーテル系ノニオン界面活性剤を用いることが好ましい。また、ポリオキシアルキレンアルキルエーテル系ノニオン界面活性剤の添加量は、費用対効果の観点から、含油スラッジ１００質量部に対して、０．０５〜１質量部とすることが好ましく、より好ましくは０．１〜０．５質量部である。 The structure and physical properties of the polyoxyalkylene alkyl ether-based nonionic surfactant are not particularly limited, but in order to be added to the slurry, it is necessary to disperse in water and contact with the sludge. Therefore, it is preferable to use a polyoxyalkylene alkyl ether nonionic surfactant having an HLB of 8 or more in the oil-containing sludge treatment method of the present embodiment. The addition amount of the polyoxyalkylene alkyl ether-based nonionic surfactant is preferably 0.05 to 1 part by mass, more preferably 0 with respect to 100 parts by mass of the oil-containing sludge, from the viewpoint of cost effectiveness. .1 to 0.5 parts by mass.
撹拌時のスラリーの温度は、特に限定されるものではないが、脱油効果向上の観点から、６０〜９０℃とすることが好ましい。また、撹拌時間も、特に限定されるものではないが、スラリーが所要温度（例えば、撹拌温度が８５℃の場合は８３〜８８℃程度）になってから１０〜６０分間が好ましく、より好ましくは２０〜３０分間程度である。 Although the temperature of the slurry at the time of stirring is not specifically limited, It is preferable to set it as 60-90 degreeC from a viewpoint of the deoiling effect improvement. Further, the stirring time is not particularly limited, but is preferably 10 to 60 minutes, more preferably after the slurry has reached the required temperature (for example, about 83 to 88 ° C when the stirring temperature is 85 ° C). About 20-30 minutes.
所要時間スラリーを撹拌した後、撹拌を停止すると、１０〜３０分間程度で、油分がスラリー上面に分離する。そこで、油分のみを別の槽に移すことにより、油分が除去されたミルスケールを含むスラリーが得られる。なお、水とミルスケールを分離するためには、脱水機にかけてもよいし、ヤードなどで天日干しにしてもよい。そして、前述した処理により得られるミルスケールは、鉄源として再利用が可能である。 When the stirring is stopped after stirring the slurry for the required time, the oil component is separated on the upper surface of the slurry in about 10 to 30 minutes. Then, the slurry containing the mill scale from which the oil component was removed is obtained by transferring only the oil component to another tank. In order to separate the water and the mill scale, they may be put on a dehydrator or sun-dried in a yard or the like. And the mill scale obtained by the process mentioned above can be reused as an iron source.
本実施形態の含油スラッジの処理方法は、珪酸ナトリウムとポリオキシアルキレンアルキルエーテル系ノニオン界面活性剤とを併用しているため、従来よりも簡便な方法で、効率よく含油スラッジから油分を分離することができる。珪酸ナトリウムやポリオキシアルキレンアルキルエーテル系ノニオン界面活性剤をそれぞれ単独で使用した場合、十分に油分を除去することができないが、これらを併用することにより、高い除去効果を得ることができる。 The method for treating oil-containing sludge of the present embodiment uses sodium silicate and a polyoxyalkylene alkyl ether nonionic surfactant in combination, so that oil can be efficiently separated from oil-containing sludge by a simpler method than before. Can do. When sodium silicate or polyoxyalkylene alkyl ether nonionic surfactant is used alone, the oil cannot be sufficiently removed, but by using these together, a high removal effect can be obtained.
以下、本発明の実施例及び比較例を挙げて、本発明の効果について具体的に説明する。本実施例においては、本発明の範囲内及び範囲外の薬剤を使用して含油スラッジを処理し、油分の分離性能を評価した。 Hereinafter, the effects of the present invention will be specifically described with reference to Examples and Comparative Examples of the present invention. In this example, oil-containing sludge was treated using chemicals within and outside the scope of the present invention, and the oil separation performance was evaluated.
具体的には、１Ｌビーカーに油分５．２質量％を含む含油スラッジ２００ｇ及び水（水道水）を３００ｇ入れて、スラリーを作製した。次に、スラリーが入ったビーカーをヒーターに載置し、卓上用の撹拌機で撹拌しながら８５℃になるまで撹拌した。そして、スラリーの温度を８５℃で一定とし、下記表１に示す実施例及び比較例の薬剤を添加して、３０分間撹拌を継続した。なお、試験中に蒸発などにより水位が低下する場合は、純水を添加して調整した。また、下記表１に示す各薬剤の添加量は、含油スラッジ１００質量あたりの量（質量部）である。 Specifically, 200 g of oil-containing sludge containing 5.2% by mass of oil and 300 g of water (tap water) were put into a 1 L beaker to prepare a slurry. Next, the beaker containing the slurry was placed on a heater and stirred until it reached 85 ° C. while stirring with a desktop stirrer. And the temperature of slurry was made constant at 85 degreeC, the chemical | medical agent of the Example and comparative example which are shown in following Table 1 was added, and stirring was continued for 30 minutes. When the water level decreased due to evaporation during the test, pure water was added for adjustment. Moreover, the addition amount of each chemical | medical agent shown in following Table 1 is the quantity (mass part) per 100 mass of oil-containing sludge.
３０分経過後、ヒーターによる加熱及び撹拌を止め、スラリーを静置した。そして、３０分間静置した後、デカンテーションにより浮上した油を別の容器に移し、ビーカーにスラッジを１００ｇ程度スパーテルで取出し、使い捨て紙の上に広げて、１昼夜室内で乾燥させた。乾燥後のスラッジを約２５ｇ採取し、正確な質量を測定した後、ソックスレー抽出方式でｎ−Ｈｅｘを溶媒として油分を抽出し、その質量を測定することにより、処理後の油分含有量を求めた。以上の結果を下記表１に示す。 After 30 minutes, heating with the heater and stirring were stopped and the slurry was allowed to stand. And after leaving still for 30 minutes, the oil which floated by decantation was moved to another container, about 100g of sludge was taken out with the spatula in the beaker, and it spread on the disposable paper, and was dried indoors day and night. About 25 g of dried sludge was sampled and the exact mass was measured. Then, the oil content was extracted using n-Hex as a solvent by Soxhlet extraction method, and the mass content was measured to determine the oil content after the treatment. . The above results are shown in Table 1 below.
上記表１に示すように、珪酸ナトリウムと、ポリオキシエチレンアルキルエーテル系界面活性剤を併用した実施例１〜４は、薬剤を添加しなかった比較例１、珪酸ナトリウムのみを添加した比較例２、水酸化ナトリウムや炭酸ナトリウムを単独で使用した比較例３，４、ポリオキシエチレンアルキルエーテル系界面活性剤のみを添加した比較例５，６、珪酸ナトリウムとポリオキシエチレンアルキルエーテル系界面活性剤以外の界面活性剤を併用した比較例７〜１１に比べて、油分含有量を大幅に低減することができた。 As shown in Table 1 above, Examples 1 to 4 in which sodium silicate and a polyoxyethylene alkyl ether surfactant were used in combination were Comparative Example 1 in which no chemical was added, and Comparative Example 2 in which only sodium silicate was added. Comparative Examples 3 and 4 using sodium hydroxide and sodium carbonate alone, Comparative Examples 5 and 6 adding only polyoxyethylene alkyl ether surfactants, other than sodium silicate and polyoxyethylene alkyl ether surfactants Compared with Comparative Examples 7 to 11 in which these surfactants were used in combination, the oil content could be greatly reduced.
以上結果から、本発明の含油スラッジ処理方法は、簡単な処理で効率よく含油スラッジから油分を除去できることが確認された。 From the above results, it was confirmed that the oil-containing sludge treatment method of the present invention can efficiently remove oil from the oil-containing sludge by simple treatment.
Claims (5)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014117713A JP2015229157A (en) | 2014-06-06 | 2014-06-06 | Processing method of oil-containing sludge |
| PCT/JP2015/062971 WO2015186456A1 (en) | 2014-06-06 | 2015-04-30 | Method for treating oil sludge |
| TW104117084A TW201545994A (en) | 2014-06-06 | 2015-05-28 | Method for treating oil sludge |
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| JP2014117713A JP2015229157A (en) | 2014-06-06 | 2014-06-06 | Processing method of oil-containing sludge |
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| CN108950572A (en) * | 2018-07-16 | 2018-12-07 | 苏州帝瀚环保科技股份有限公司 | It is ground the processing method of greasy filth |
| CN110606633A (en) * | 2019-09-12 | 2019-12-24 | 广西博世科环保科技股份有限公司 | Oily sludge recycling and reducing treatment method and treatment system |
| CN111718105B (en) * | 2020-07-16 | 2023-12-12 | 兰州理工大学 | Treatment device and method for degrading oily sludge based on ozone oxidation and hydrogen peroxide |
| CN112479518B (en) * | 2020-11-30 | 2023-03-17 | 华东理工大学 | Comprehensive treatment process of cold-rolled aged oil sludge |
| WO2024047742A1 (en) * | 2022-08-30 | 2024-03-07 | 清水建設株式会社 | Method for treating oil-containing sludge, method for recovering oil from oil-containing sludge, apparatus for treating oil-containing sludge, apparatus for recovering oil from oil- containing sludge, system for treating oil-containing sludge, and system for recovering oil from oil-containing sludge |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2001162107A (en) * | 1999-12-10 | 2001-06-19 | Lion Corp | Oil separating agent |
| JP2003027147A (en) * | 2001-07-19 | 2003-01-29 | Nippon Steel Corp | Degreasing method for scale |
| JP2007260484A (en) * | 2006-03-27 | 2007-10-11 | Nippon Steel Corp | Treatment method of oil-containing sludge |
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| JPS53100969A (en) * | 1977-02-17 | 1978-09-02 | Nippon Steel Corp | Oil removing wet treating method of oil containing hot rolling sludge |
| JP3141501B2 (en) * | 1992-03-24 | 2001-03-05 | 栗田工業株式会社 | Mill sludge deoiling method and deoiling agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001162107A (en) * | 1999-12-10 | 2001-06-19 | Lion Corp | Oil separating agent |
| JP2003027147A (en) * | 2001-07-19 | 2003-01-29 | Nippon Steel Corp | Degreasing method for scale |
| JP2007260484A (en) * | 2006-03-27 | 2007-10-11 | Nippon Steel Corp | Treatment method of oil-containing sludge |
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| WO2015186456A1 (en) | 2015-12-10 |
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