TWI651266B - Spherical activated carbon and method of producing the same - Google Patents
Spherical activated carbon and method of producing the same Download PDFInfo
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Abstract
本發明之球狀活性炭係一體成型之球狀活性炭。該球狀活性炭之平均粒徑為1.5 mm以上、4.0 mm以下,該球狀活性炭之細孔徑為50 nm以上、10000 nm以下之範圍內細孔容積為0.01 ml/g以上、0.24 ml/g以下之範圍。The spherical activated carbon of the present invention is a spherical activated carbon integrally molded. The average particle diameter of the spherical activated carbon is 1.5 mm or more and 4.0 mm or less, and the pore volume of the spherical activated carbon is 50 nm or more and 10000 nm or less, and the pore volume is 0.01 ml/g or more and 0.24 ml/g or less. The scope.
Description
本發明係關於一種球狀活性炭及該球狀活性炭的製造方法。 The present invention relates to a spherical activated carbon and a method of producing the spherical activated carbon.
於化學工業中,活性炭被用於分離製程、精製、觸媒或溶劑回收,進而亦被用於與地球環境污染問題有關之排水處理、防公害對策或醫療用途等多種用途。 In the chemical industry, activated carbon is used in separation processes, refining, catalysts, or solvent recovery, and is also used in various applications such as drainage treatment, pollution prevention measures, or medical applications related to global environmental pollution problems.
例如,於專利文獻1中揭示有一種粉末狀活性炭及平均粒徑為數mm左右之粒狀活性炭。 For example, Patent Document 1 discloses a powdery activated carbon and a granular activated carbon having an average particle diameter of about several mm.
又,以石油溚或乙烯塔底油等重質烴油為原料的活性炭(專利文獻1)以及以樹脂為原料的活性炭(專利文獻2)為人們所熟知。 Further, activated carbon (Patent Document 1) using a heavy hydrocarbon oil such as petroleum crucible or ethylene bottom oil, and activated carbon using a resin as a raw material (Patent Document 2) are well known.
【專利文獻1】日本公開專利公報「日本專利特開2005-119947號公報」 [Patent Document 1] Japanese Laid-Open Patent Publication No. 2005-119947
【專利文獻2】日本公開專利公報「日本專利特開2000-233916號公報」 [Patent Document 2] Japanese Laid-Open Patent Publication No. 2000-233916
【非專利文獻1】真田雄三及其他2人「新版活性炭基礎與應用」,株式會社講談社,1992年3月1日 [Non-patent Document 1] Mr. Sanada and other two people "New Activated Carbon Foundation and Application", Kodansha, Inc., March 1, 1992
在使用活性炭時,要求降低壓力損失及抑制粉塵。 When using activated carbon, it is required to reduce pressure loss and suppress dust.
將活性炭填充到管柱等裝置中,使包含固定濃度目標物質之流體流通、使用時,為了使相對於目標物質的單位體積效果達到最大,需要緊密地填充活性炭粒子。 When the activated carbon is filled into a device such as a column and the fluid containing a fixed concentration target substance is used and used, in order to maximize the effect per unit volume with respect to the target substance, it is necessary to closely fill the activated carbon particles.
然而,活性炭粒徑較小時,或者活性炭產生粉塵量較大時,會導致活性炭粒子間空隙被堵塞。另外,該等情況下,由於裝置過濾器等堵塞,壓力損失變大,從而可能導致裝置的負載變大。又,使用活性炭處理大流量流體時,可能會出現小粒徑活性炭或所產生之粉塵飛散的現象。 However, when the activated carbon particle size is small, or when the amount of dust generated by the activated carbon is large, the voids between the activated carbon particles are blocked. Further, in such cases, the pressure loss becomes large due to clogging of the device filter or the like, which may cause the load of the device to become large. Moreover, when a large-flow fluid is treated with activated carbon, there may be a phenomenon in which small-sized activated carbon or generated dust scatters.
此外,使活性炭與包含目標物質之流體(氣體或液體)接觸後,要分別使活性炭及目標物質分離時,需要實施例如過濾等處理。但是,如果活性炭粒子較小,或者產生粉塵量較多,分離就需要花費大量時間及成本。 Further, when the activated carbon and the target substance are separated from each other by bringing the activated carbon into contact with a fluid (gas or liquid) containing the target substance, it is necessary to carry out a treatment such as filtration. However, if the activated carbon particles are small or the amount of dust generated is large, separation takes a lot of time and cost.
尤其是,上述粉末狀活性炭粒度基本都較小,填充到裝置中使用時壓力損失會變大,且流體處理量受到制約。 In particular, the above-mentioned powdered activated carbon has a substantially small particle size, and the pressure loss becomes large when it is used in a device, and the amount of fluid treatment is restricted.
又,如此使用粉末狀活性炭時,處理大流量流體時粉末可能會飛散。 Moreover, when powdered activated carbon is used as such, the powder may scatter when a large flow of fluid is treated.
與此相對,若為平均粒徑數mm左右之粒狀活性炭,可以降低填充時的壓力損失,實現大流量的流體處理。 On the other hand, in the case of granular activated carbon having an average particle diameter of about several mm, the pressure loss at the time of filling can be reduced, and fluid processing at a large flow rate can be realized.
然而,一直以來,於粒狀活性炭之製造方法中,一般採用對粉末炭與黏合劑混合,製造粒狀顆粒之方式。即,藉由以往的製造方法所獲得之粒狀活性炭並非一體成型而成。因此,以往的粒狀活性炭強度較弱,如果將該種粒狀活性炭填充到裝置中使用,會產生大量粉塵,且難以與流體分離。 However, conventionally, in the method for producing granular activated carbon, a method in which powdered carbon and a binder are mixed to produce granular particles is generally employed. That is, the granular activated carbon obtained by the conventional production method is not integrally molded. Therefore, the conventional granular activated carbon is weak in strength, and if the granular activated carbon is used in the apparatus, a large amount of dust is generated and it is difficult to separate from the fluid.
又,以往的粒狀活性炭一般使用椰殼活性炭等,故雜質較多,粉塵以外之雜質溶離等也存在問題。 Moreover, since the conventional granular activated carbon generally uses coconut shell activated carbon or the like, there are many impurities, and there are problems in that impurities other than dust are dissolved.
鑒於以上內容,要求開發出一種可以抑制壓力損失及粉塵的活性炭。 In view of the above, it is required to develop an activated carbon which can suppress pressure loss and dust.
為解決上述問題,本發明者等銳意研究後發現,若採用粒徑為數mm左右、一體成型之球狀活性炭,可以抑制壓力損失及粉塵,並完成本發明。 In order to solve the above problems, the inventors of the present invention have conducted intensive studies and found that the use of a spherical activated carbon having a particle diameter of about several mm can suppress pressure loss and dust, and the present invention has been completed.
即,本發明提供一種球狀活性炭,其係平均粒徑為1.5mm以上、4.0mm以下且一體成型之球狀活性炭,且係細孔徑為50nm以 上、10000nm以下之範圍內細孔容積為0.01ml/g以上、0.24ml/g以下之範圍的球狀活性炭。 That is, the present invention provides a spherical activated carbon which is an integrally formed spherical activated carbon having an average particle diameter of 1.5 mm or more and 4.0 mm or less, and has a pore diameter of 50 nm. A spherical activated carbon having a pore volume of 0.01 ml/g or more and 0.24 ml/g or less in the range of 10,000 nm or less.
進而,本發明提供一種具有上述特徵之球狀活性炭的製造方法。 Further, the present invention provides a method for producing a spherical activated carbon having the above characteristics.
根據本發明,可以提供一種可抑制壓力損失及粉塵之活性炭。 According to the present invention, it is possible to provide an activated carbon which can suppress pressure loss and dust.
以下,針對本發明所涉及之球狀活性炭之一實施方式進行具體說明。 Hereinafter, an embodiment of the spherical activated carbon according to the present invention will be specifically described.
本實施方式所涉及之球狀活性炭(以下亦簡稱為「球狀活性炭」)之平均粒徑為1.5mm以上、4.0mm以下,細孔徑為50nm以上、10000nm以下之範圍內細孔容積為0.01ml/g以上、0.24ml/g以下。另外,細孔徑及細孔容積之詳細說明如後所述。 The spherical activated carbon (hereinafter also referred to simply as "spherical activated carbon") according to the present embodiment has an average particle diameter of 1.5 mm or more and 4.0 mm or less, and a pore volume of 0.01 ml in a range of pore diameter of 50 nm or more and 10000 nm or less. /g or more, 0.24 ml/g or less. In addition, the detailed description of the pore diameter and the pore volume will be described later.
於本說明書中,球狀活性炭係指球形活性炭。球狀活性炭之球形度並無特別限定,優選短長徑比為0.7以上,更優選為0.8以上,尤其優選為0.9以上。短長徑比係短徑相對於長徑之比。可藉由周知之方法,例如球狀活性炭投影圖像中最大長度及最小長度之平均值,計算出長 徑及短徑。短長徑比越接近1,球狀活性炭越接近球形。另外,球狀活性炭之短長徑比若為0.7以上,使用球狀活性炭時,球狀活性炭粒子之間的碰撞所產生之磨損會進一步降低,從而可以充分抑制粉塵的產生。 In the present specification, spherical activated carbon means spherical activated carbon. The sphericity of the spherical activated carbon is not particularly limited, and the short aspect ratio is preferably 0.7 or more, more preferably 0.8 or more, and particularly preferably 0.9 or more. The short aspect ratio is the ratio of the short diameter to the long diameter. The length can be calculated by a well-known method, such as the average of the maximum length and the minimum length in the spherical activated carbon projection image. Trail and short diameter. The closer the short aspect ratio is to 1, the closer the spherical activated carbon is to the spherical shape. Further, when the short aspect ratio of the spherical activated carbon is 0.7 or more, when spherical activated carbon is used, the abrasion caused by the collision between the spherical activated carbon particles is further lowered, and the generation of dust can be sufficiently suppressed.
本實施方式所涉及之球狀活性炭係一體成型之球狀活性炭。「一體成型之球狀活性炭」係指成型為一次粒子且具有球狀之活性炭。本實施方式所涉及之球狀活性炭具有後述細孔徑及細孔容積,因此,亦稱為具有多孔性及球狀之一次粒子活性炭。相對於例如聚集顆粒燒結體等以往之球狀活性炭,本實施方式所涉及之球狀活性炭的機械強度優異。例如,與以往球狀活性炭相比,本實施方式所涉及之球狀活性炭具有更高之抗壓碎力,或者具有更低之水中振盪磨損率。 The spherical activated carbon according to the present embodiment is a spherical activated carbon integrally molded. "Integrally formed spherical activated carbon" means activated carbon which is formed into primary particles and has a spherical shape. Since the spherical activated carbon according to the present embodiment has a pore diameter and a pore volume to be described later, it is also referred to as a porous and spherical primary particle activated carbon. The spherical activated carbon according to the present embodiment is excellent in mechanical strength with respect to a conventional spherical activated carbon such as an aggregated particle sintered body. For example, the spherical activated carbon according to the present embodiment has a higher crush resistance than the conventional spherical activated carbon, or has a lower water oscillating wear rate.
自抑制球狀活性炭填充層壓力損失上升之觀點出發,本實施方式所涉及之球狀活性炭之平均粒徑下限值為1.5mm以上,優選為1.7mm以上,更優選為1.8mm,尤其優選為2.0mm以上。此外,自充分實現填充層中球狀活性炭與流體之上述接觸性的觀點出發,其上限值為4.0mm以下,優選為3.5mm以下,更優選為3.0mm以下。使平均粒徑位於該範圍內,即可充分增大球狀活性炭的粒子間空隙。因此,若採用此種球狀活性炭,將球狀活性炭填充到管柱或分離塔等裝置中,使包含目標物質之流體與之接觸時,可以充分減小壓力損失。 The lower limit of the average particle diameter of the spherical activated carbon according to the present embodiment is 1.5 mm or more, preferably 1.7 mm or more, and more preferably 1.8 mm, and particularly preferably, from the viewpoint of suppressing an increase in pressure loss of the spherical activated carbon packed bed. 2.0mm or more. Further, from the viewpoint of sufficiently achieving the above-described contact property between the spherical activated carbon and the fluid in the packed bed, the upper limit is 4.0 mm or less, preferably 3.5 mm or less, and more preferably 3.0 mm or less. When the average particle diameter is within this range, the interparticle voids of the spherical activated carbon can be sufficiently increased. Therefore, when such a spherical activated carbon is used, the spherical activated carbon is filled in a device such as a column or a separation tower, and when a fluid containing a target substance is brought into contact therewith, the pressure loss can be sufficiently reduced.
於本實施方式中,球狀活性炭之平均粒徑可以依據JIS K 1474進行評價。即,根據JIS K 1474操作所獲得之結果,製作球狀活性炭之累積粒度分佈曲線圖。由橫軸50%點之垂直線與累積粒度分佈曲線圖 的交點,沿縱軸畫水平線,計算交點所表示之篩孔(mm)。將該篩孔值設為球狀活性炭之平均粒徑。 In the present embodiment, the average particle diameter of the spherical activated carbon can be evaluated in accordance with JIS K 1474. Namely, a cumulative particle size distribution curve of spherical activated carbon was produced in accordance with the results obtained by the operation of JIS K 1474. Vertical line and cumulative particle size distribution curve from 50% of the horizontal axis The intersection point, draw a horizontal line along the vertical axis, and calculate the sieve hole (mm) indicated by the intersection point. The mesh value was defined as the average particle diameter of the spherical activated carbon.
於本說明書中,細孔徑係指球狀活性炭所具有之細孔的細孔直徑。於本實施方式中,細孔徑及細孔容積可藉由例如周知之水銀壓入法測定。此外,細孔徑及細孔容積可藉由例如後述交聯重質瀝青之性狀等進行調整。 In the present specification, the pore diameter refers to the pore diameter of the pores of the spherical activated carbon. In the present embodiment, the pore diameter and the pore volume can be measured by, for example, a known mercury intrusion method. Further, the pore diameter and the pore volume can be adjusted by, for example, the properties of the crosslinked heavy pitch described later.
於本說明書中,細孔容積係指活性炭特定細孔徑範圍內細孔之體積。 In the present specification, the pore volume refers to the volume of the pores in the specific pore size range of the activated carbon.
自抑制球狀活性炭於後述製造方法中生產率降低之觀點出發,本實施方式所涉及之球狀活性炭於細孔徑為50nm以上、10000nm以下之範圍內細孔容積下限值為0.01ml/g以上,優選為0.02ml/g以上,更優選為0.03ml/g以上,尤其優選為0.05ml/g以上。此外,自防止球狀活性炭之抗壓碎力降低的觀點出發,其上限值為0.24ml/g以下,優選為0.22ml/g以下,更優選為0.20ml/g以下,尤其優選為0.18ml/g以下。 The spherical activated carbon according to the present embodiment has a pore volume lower limit value of 0.01 ml/g or more in a range of pore diameters of 50 nm or more and 10000 nm or less, from the viewpoint of the production efficiency of the spherical activated carbon in the production method to be described later. It is preferably 0.02 ml/g or more, more preferably 0.03 ml/g or more, and particularly preferably 0.05 ml/g or more. Further, from the viewpoint of preventing the crushing resistance of the spherical activated carbon from decreasing, the upper limit is 0.24 ml/g or less, preferably 0.22 ml/g or less, more preferably 0.20 ml/g or less, and particularly preferably 0.18 ml. /g below.
此外,自抑制球狀活性炭生產率降低之觀點出發,本實施方式所涉及之球狀活性炭於細孔徑為10nm以上、10000nm以下之範圍內細孔容積下限值為0.01ml/g以上,優選為0.02ml/g以上,更優選為0.03ml/g以上,尤其優選為0.04ml/g以上。此外,自防止球狀活性炭之抗壓碎力降低的觀點出發,其上限值為0.28ml/g以下,優選為0.27ml/g以下,更優選為0.26ml/g以下,尤其優選為0.25ml/g,最優選為0.24ml/g以下。 In addition, the spherical activated carbon according to the present embodiment has a pore volume lower limit value of 0.01 ml/g or more, preferably 0.02, in a range of a pore diameter of 10 nm or more and 10000 nm or less from the viewpoint of suppressing a decrease in the productivity of the spherical activated carbon. Mol/g or more is more preferably 0.03 ml/g or more, and particularly preferably 0.04 ml/g or more. Further, from the viewpoint of preventing the crushing resistance of the spherical activated carbon from decreasing, the upper limit is 0.28 ml/g or less, preferably 0.27 ml/g or less, more preferably 0.26 ml/g or less, and particularly preferably 0.25 ml. /g is most preferably 0.24 ml/g or less.
根據本實施方式,藉由使球狀活性炭滿足上述範圍,可充分形成後述不熔化時所需要之孔,從而可以有效地進行不熔化,製造球狀活性炭。此外,可以對難以參與球狀活性炭吸附能力之細孔容積的增加進行抑制,因此,球狀活性炭之密度變高,球狀活性炭之單位體積性能提高。 According to the present embodiment, by making the spherical activated carbon satisfy the above range, the pores required for the infusibility described later can be sufficiently formed, and the insolubilization can be efficiently performed to produce the spherical activated carbon. Further, the increase in the pore volume which is difficult to participate in the adsorption ability of the spherical activated carbon can be suppressed, and therefore, the density of the spherical activated carbon becomes high, and the unit volume performance of the spherical activated carbon is improved.
於本實施方式中,細孔容積可藉由例如周知之水銀壓入法評價。 In the present embodiment, the pore volume can be evaluated by, for example, a well-known mercury intrusion method.
本實施方式所涉及之球狀活性炭為一次粒子,與聚集顆粒燒結而成之以往的球狀活性炭相比,具有較高的機械強度。本實施方式之球狀活性炭之抗壓碎力優選為1.20kg/個以上,更優選為1.25kg/個以上,尤其優選為1.30kg/個。抗壓碎力例如根據球狀活性炭之用途具有足夠大小即可,例如,可以為10.0kg/個以下。 The spherical activated carbon according to the present embodiment is a primary particle and has higher mechanical strength than a conventional spherical activated carbon obtained by sintering aggregated particles. The crushing resistance of the spherical activated carbon of the present embodiment is preferably 1.20 kg/piece or more, more preferably 1.25 kg/piece or more, and particularly preferably 1.30 kg/piece. The crushing resistance may be sufficient, for example, according to the use of the spherical activated carbon, and may be, for example, 10.0 kg/piece or less.
抗壓碎力可藉由以下方法進行測定。即,隨機抽取球狀活性炭之試樣粒子(例如30粒),使用簡易顆粒硬度計(筒井理化學器械株式會社製),測定試樣粒子被壓碎的瞬間的硬度。繼而,剔除硬度測定值中的最大值、最小值,計算剩餘測定值(例如28粒之測定值)之平均值,將其視為該球狀活性炭之抗壓碎力。 The crush resistance can be measured by the following method. In other words, the sample particles (for example, 30 particles) of the spherical activated carbon are randomly sampled, and the hardness at the moment when the sample particles are crushed is measured using a simple particle hardness meter (manufactured by Tsutsui Chemical Instruments Co., Ltd.). Then, the maximum value and the minimum value in the hardness measurement values are removed, and the average value of the remaining measurement values (for example, the measured value of 28 particles) is calculated and regarded as the crush resistance of the spherical activated carbon.
於本說明書中,粉塵係指球狀活性炭中所含之微粉。此外,粉塵量係指該粉塵的量,具體為藉由後述粉塵量之測定而計算出的量。 In the present specification, dust refers to the fine powder contained in the spherical activated carbon. Further, the amount of dust refers to the amount of the dust, and is specifically the amount calculated by measuring the amount of dust described later.
於本實施方式中,自抑制球狀活性炭填充層中壓力損失上升之觀點出發,以及充分顯現球狀活性炭之分離能力的觀點出發,球狀活 性炭每1g中所含粉塵量優選為2000μg以下,更優選為1500μg以下,尤其優選為1200μg以下,最優選為1000μg以下。粉塵量越少越好,其下限值可以為0μg以上。 In the present embodiment, from the viewpoint of suppressing an increase in pressure loss in the spherical activated carbon packed bed, and from the viewpoint of sufficiently exhibiting the separation ability of the spherical activated carbon, the spherical shape The amount of dust contained per 1 g of the charcoal is preferably 2000 μg or less, more preferably 1500 μg or less, particularly preferably 1200 μg or less, and most preferably 1000 μg or less. The smaller the amount of dust, the better, and the lower limit value may be 0 μg or more.
本實施方式所涉及之球狀活性炭之粉塵量可藉由後述特定方法進行測定。粉塵量可藉由例如一體成型之製造方法而降低。 The amount of dust of the spherical activated carbon according to the present embodiment can be measured by a specific method described later. The amount of dust can be reduced by, for example, a one-piece manufacturing method.
如果將球狀活性炭放入水中,於水中振盪,則球狀活性炭彼此之間發生碰撞,導致球狀活性炭被削除、剝落。於本實施方式中,根據此時剝落之球狀活性炭量,計算出水中振盪磨損率。具體為,水中振盪磨損率可根據以下公式計算得出。 If the spherical activated carbon is placed in water and oscillated in water, the spherical activated carbon collides with each other, and the spherical activated carbon is removed and peeled off. In the present embodiment, the oscillating wear rate in water is calculated based on the amount of spherical activated carbon peeled off at this time. Specifically, the water oscillating wear rate can be calculated according to the following formula.
水中振盪磨損率(%)=(A-B)/A×100(%)...(式1) Oscillation wear rate in water (%) = (A - B) / A × 100 (%) ... (Formula 1)
A:水中振盪前球狀活性炭之質量(g) A: mass of spherical activated carbon before shaking in water (g)
B:水中振盪後球狀活性炭之質量(g) B: mass of spherical activated carbon after shaking in water (g)
本實施方式所涉及之球狀活性炭之水中振盪磨損率優選為5%以下,更優選為4.5%以下。另外,水中振盪磨損率越低,球狀活性炭之強度越大,故球狀活性炭彼此之間碰撞而產生之粉塵量變少。 The spherical activated carbon of the spherical activated carbon according to the present embodiment preferably has an oscillating wear rate of 5% or less, and more preferably 4.5% or less. Further, the lower the oscillating wear rate in the water, the greater the strength of the spherical activated carbon, and the amount of dust generated by the collision of the spherical activated carbons with each other is reduced.
比表面積係使待評價物質吸附氣體分子,根據吸附之氣體分子量與氣體分子之吸附截面積之比計算得出。具體為,藉由BET法計算氮吸附量,將氮分子之吸附截面積設為0.162nm2,計算比表面積。另外,比表面積亦稱為specific surface area(SSA)。 The specific surface area is obtained by adsorbing gas molecules to the substance to be evaluated, and calculating the ratio of the molecular weight of the adsorbed gas to the adsorption cross-sectional area of the gas molecules. Specifically, the nitrogen adsorption amount was calculated by the BET method, and the adsorption cross-sectional area of the nitrogen molecule was set to 0.162 nm 2 to calculate the specific surface area. In addition, the specific surface area is also referred to as a specific surface area (SSA).
本實施方式所涉及之比表面積係氣體分子採用氮,於液氮溫度下使球狀活性炭吸附氮時的比表面積。比表面積可藉由例如後述活化程度進行調整。 The specific surface area of the gas molecules of the specific surface area according to the present embodiment is nitrogen, and the specific surface area when the spherical activated carbon adsorbs nitrogen at the liquid nitrogen temperature. The specific surface area can be adjusted by, for example, the degree of activation described later.
自發揮球狀活性炭吸附功能之觀點出發,本實施方式所涉及之球狀活性炭之比表面積優選為100m2/g以上,更優選為300m2/g以上,尤其優選為400m2/g以上。比表面積若為100m2/g以上,則可充分發揮球狀活性炭之吸附功能。自上述觀點出發,比表面積越大越好,但在可充分獲得球狀活性炭期待之吸附功能的範圍內即可,例如可以為4000m2/g以下。 From play of the spherical activated carbon adsorption function viewpoint, the present embodiment of the spherical activated carbon is preferably a specific surface area of 100m 2 / g or more, more preferably 300m 2 / g or more, particularly preferably 400m 2 / g or more. When the specific surface area is 100 m 2 /g or more, the adsorption function of the spherical activated carbon can be sufficiently exhibited. From the above viewpoints, the larger the specific surface area, the better, but it may be within a range in which the desired adsorption function of the spherical activated carbon can be sufficiently obtained, and may be, for example, 4,000 m 2 /g or less.
本實施方式所涉及之球狀活性炭可浸染其他物質。其他物質可列舉例如酸、鹼以及金屬等可以浸染到活性炭中之周知物質。酸具體可列舉例如磷酸、硫酸等非揮發性酸,檸檬酸、蘋果酸等有機酸等。此外,鹼具體可列舉例如碳酸鉀、碳酸鈉、氫氧化鉀、氫氧化鈉等。又,金屬具體可列舉例如鉑、銀、鐵、鈷等過渡元素及其化合物等。 The spherical activated carbon according to the present embodiment can be impregnated with other substances. Other examples include well-known substances which can be impregnated into activated carbon, such as an acid, a base, and a metal. Specific examples of the acid include nonvolatile acids such as phosphoric acid and sulfuric acid, and organic acids such as citric acid and malic acid. Further, specific examples of the base include potassium carbonate, sodium carbonate, potassium hydroxide, and sodium hydroxide. Further, specific examples of the metal include transition elements such as platinum, silver, iron, and cobalt, and compounds thereof.
如此,本實施方式所涉及之球狀活性炭優選該球狀活性炭每1g中所含粉塵量在2000μg以下。 As described above, in the spherical activated carbon according to the embodiment, the amount of dust contained per 1 g of the spherical activated carbon is preferably 2000 μg or less.
進而,本實施方式所涉及之球狀活性炭優選水中振盪磨損率為5%以下。 Further, the spherical activated carbon according to the present embodiment preferably has an underwater vibration wear ratio of 5% or less.
進而,本實施方式所涉及之球狀活性炭優選短長徑比為0.7以下。 Further, the spherical activated carbon according to the present embodiment preferably has a short aspect ratio of 0.7 or less.
進而,本實施方式所涉及之球狀活性炭優選浸染鹼或酸。 Further, the spherical activated carbon according to the present embodiment is preferably impregnated with a base or an acid.
根據本實施方式所涉及之球狀活性炭,可抑制壓力損失及粉塵量。因此,可以將此種球狀活性炭用於多種用途。此外,和以往之活性炭相比,本實施方式所涉及之球狀活性炭之抗裂性亦良好。 According to the spherical activated carbon according to the present embodiment, the pressure loss and the amount of dust can be suppressed. Therefore, such spherical activated carbon can be used for various purposes. Further, the spherical activated carbon according to the present embodiment is also excellent in crack resistance as compared with the conventional activated carbon.
本實施方式所涉及之球狀活性炭之製造方法若可獲得具有上述特徵之球狀活性炭,則並無特別限定。以下,針對本實施方式所涉及之球狀活性炭之製造方法(以下亦簡稱為「本製造方法」)的一實施方式進行說明。 The method for producing a spherical activated carbon according to the present embodiment is not particularly limited as long as spherical activated carbon having the above characteristics can be obtained. Hereinafter, an embodiment of a method for producing spherical activated carbon according to the present embodiment (hereinafter also simply referred to as "the present manufacturing method") will be described.
本製造方法使用重質烴油作為球狀活性炭之原料。關於重質烴油,可列舉例如選自由石油溚、煤焦油或乙烯塔底油等所組成之群組中的一種或兩種以上。 This manufacturing method uses heavy hydrocarbon oil as a raw material of spherical activated carbon. The heavy hydrocarbon oil may, for example, be one or more selected from the group consisting of petroleum hydrazine, coal tar, and ethylene bottom oil.
其中,若為乙烯塔底油,可對製造乙烯時所生成之塔底油輕質成分減壓蒸餾而獲得。 Among them, in the case of an ethylene bottom oil, it can be obtained by vacuum distillation of a light component of a bottom oil which is produced when ethylene is produced.
此外,亦可將包含呋喃樹脂或酚醛樹脂、源自化石燃料或源自植物的樹脂作為球狀活性炭之原料。 Further, a furan resin or a phenol resin, a fossil fuel-derived or plant-derived resin may be used as a raw material of the spherical activated carbon.
本製造方法詳細包括(1)交聯重質瀝青的製造、(2)對交聯重質瀝青添加添加劑、(3)交聯重質瀝青的成型、(4)添加劑的提取、(5)不熔化以及(6)煅燒.活化共計六個製程。以下,依次針對各製程進行說明。 The manufacturing method includes (1) manufacture of crosslinked heavy asphalt, (2) addition of additive to crosslinked heavy asphalt, (3) molding of crosslinked heavy asphalt, (4) extraction of additives, and (5) no Melting and (6) calcination. The activation has a total of six processes. Hereinafter, each process will be described in order.
(1)交聯重質瀝青的製造 (1) Manufacture of crosslinked heavy asphalt
本製造方法首先製造交聯重質瀝青。該交聯重質瀝青的製造製程如後所述,係確保與由芳香族化合物所組成之黏度調整用添加物具 有適當不互溶性,進而於添加劑提取製程中實現球狀瀝青多孔化所需要的製程。 This manufacturing method first produces crosslinked heavy asphalt. The manufacturing process of the crosslinked heavy asphalt is as described later, and it is ensured that the viscosity adjusting additive is composed of an aromatic compound. It is suitable for the immiscibility and further the process required to achieve the spheroidal asphalt porosity in the additive extraction process.
關於交聯重質瀝青,例如對常溫下為液狀之重質烴油進行交聯處理以及熱處理即可。藉此,可以獲得常溫下為固體之交聯重質瀝青。交聯重質瀝青之具體製造方法記載於例如日本專利第4349627號公報。 For the crosslinked heavy pitch, for example, a heavy hydrocarbon oil which is liquid at normal temperature may be subjected to a crosslinking treatment and a heat treatment. Thereby, a crosslinked heavy pitch which is solid at normal temperature can be obtained. A specific method for producing a crosslinked heavy pitch is described in, for example, Japanese Patent No. 4349627.
(2)對交聯重質瀝青添加添加劑 (2) Adding additives to crosslinked heavy asphalt
繼而,對所獲得之交聯重質瀝青添加添加劑,從而調整交聯重質瀝青之黏度,使交聯重質瀝青之黏度適合于球狀化。 Then, an additive is added to the obtained crosslinked heavy asphalt to adjust the viscosity of the crosslinked heavy asphalt, so that the viscosity of the crosslinked heavy asphalt is suitable for spheroidization.
關於添加劑,可列舉例如後述萘等黏度調整用添加劑等。 For the additive, for example, an additive for viscosity adjustment such as naphthalene to be described later may be mentioned.
對交聯重質瀝青添加添加劑並加熱混合後,成型交聯重質瀝青,從而獲得球狀瀝青。 After adding an additive to the crosslinked heavy asphalt and heating and mixing, the crosslinked heavy pitch is formed to obtain a spherical asphalt.
於本製造方法中,添加到源自重質烴油之交聯重質瀝青中之添加劑優選為沸點200℃以上、優選205℃以上、更優選210℃以上之2或3環芳香族化合物或其混合物。 In the present production method, the additive added to the crosslinked heavy pitch derived from the heavy hydrocarbon oil is preferably a 2- or 3-ring aromatic compound having a boiling point of 200 ° C or higher, preferably 205 ° C or higher, more preferably 210 ° C or higher or mixture.
作為此種優選添加劑之具體例,可列舉例如選自由萘、甲萘、苯萘、苄萘、甲蒽、菲、聯苯等所組成之群組中的一種或兩種以上。其中,添加劑優選為萘。 Specific examples of such a preferred additive include, for example, one or more selected from the group consisting of naphthalene, methylnaphthalene, phenylnaphthalene, benzylnaphthalene, formazan, phenanthrene, and biphenyl. Among them, the additive is preferably naphthalene.
關於交聯重質瀝青中添加劑之添加量,若將交聯重質瀝青與添加劑之混合物總量設為100質量百分比,則其下限值優選為26質量百分比以上,更優選為27質量百分比以上,尤其優選為28質量百分比以上。若添加劑之添加量在下限值以下,則有可能無法使所獲得之多孔性球狀瀝青形成足夠的孔。又,其上限值優選為50質量百分比以下,更優選為45 質量百分比以下,尤其優選為40質量百分比以下。若添加劑之添加量在上限值以上,則交聯重質瀝青與添加劑之混合物中交聯重質瀝青量相對地變少,造成製造效率降低。又,於後述製程中會形成必要以上之提取孔,因此,可能導致所獲得之球狀活性炭之強度不充分。藉由使添加劑量在該範圍內,於後述製程中可有效地自球狀瀝青中提取添加劑,使所獲得之多孔性球狀瀝青形成足夠的孔。另外,若多孔性瀝青之孔足夠,於後述不熔化製程中,可藉由氧化反應對多孔性球狀瀝青內部進行交聯反應,保證多孔性球狀瀝青之球形並實施碳化。另外,例如若將萘添加量設為25質量百分比,則多孔性瀝青之孔不充分,可能發生熔融。 When the total amount of the additive of the crosslinked heavy pitch and the additive is 100% by mass, the lower limit is preferably 26% by mass or more, and more preferably 27% by mass or more. It is especially preferably 28 mass% or more. When the amount of the additive added is at most the lower limit value, the obtained porous spherical pitch may not be formed into a sufficient pore. Further, the upper limit thereof is preferably 50% by mass or less, more preferably 45% by mass. It is below the mass percentage, and particularly preferably 40 mass% or less. When the amount of the additive added is at least the upper limit value, the amount of the crosslinked heavy pitch in the mixture of the crosslinked heavy pitch and the additive is relatively small, resulting in a decrease in manufacturing efficiency. Further, since the extraction holes of more than necessary are formed in the process described later, the strength of the obtained spherical activated carbon may be insufficient. By setting the amount of the additive in this range, the additive can be efficiently extracted from the spherical pitch in the later-described process, and the obtained porous spherical pitch can form a sufficient pore. In addition, when the pores of the porous pitch are sufficient, the inside of the porous spherical asphalt can be cross-linked by an oxidation reaction in the infusibilization process to be described later, and the spherical shape of the porous spherical pitch can be secured and carbonized. In addition, when the amount of naphthalene added is, for example, 25 mass%, the pores of the porous pitch are insufficient, and melting may occur.
另外,藉由上述添加劑而形成之孔包含在細孔徑為50nm以上、10000nm以下範圍內球狀活性炭細孔容積的一部分中。 Further, the pores formed by the above additives are contained in a part of the pore volume of the spherical activated carbon in the range of pore diameters of 50 nm or more and 10000 nm or less.
(3)交聯重質瀝青的成型 (3) Forming of crosslinked heavy asphalt
繼而,對添加有添加劑之交聯重質瀝青進行成型。此時,優選預先使交聯重質瀝青與添加劑之混合物混合均勻。交聯重質瀝青與添加劑之混合物優選藉由加熱而形成之熔融混合物。 Then, the crosslinked heavy pitch to which the additive is added is molded. At this time, it is preferred to uniformly mix the mixture of the crosslinked heavy pitch and the additive in advance. The mixture of crosslinked heavy asphalt and additives is preferably a molten mixture formed by heating.
交聯重質瀝青的成型可於熔融混合物狀態下進行,或者亦可先冷卻熔融混合物然後對其粉碎,於熱水中攪拌等,進行成型。另外,為使之後的添加劑提取製程容易,優選將交聯重質瀝青成型為粒徑6.0mm以下之球狀瀝青。 The molding of the crosslinked heavy pitch may be carried out in the state of a molten mixture, or the molten mixture may be cooled and then pulverized, stirred in hot water, or the like, and molded. Further, in order to facilitate the subsequent additive extraction process, it is preferred to form the crosslinked heavy pitch into a spherical pitch having a particle diameter of 6.0 mm or less.
例如以包含懸浮劑之水作為分散介質,於常壓或加壓條件下對交聯重質瀝青與添加劑之均勻混合物進行熔融、分散,從而可以獲得球狀瀝青。 For example, water containing a suspending agent is used as a dispersion medium, and a homogeneous mixture of the crosslinked heavy pitch and the additive is melted and dispersed under normal pressure or under pressure to obtain a spherical asphalt.
關於獲得球狀瀝青之其他方法,亦可參考例如日本專利特公昭59-10930號公報所揭示的方法。具體為,可將交聯重質瀝青與黏度調整用添加劑之混合物以熔融狀態押出成棒狀,或者對其拉伸,然後冷卻固化,對所獲得之棒狀瀝青進行粉碎,製成長度/直徑之比在5以下的棒狀瀝青,之後,以棒狀瀝青軟化點以上之溫度,於含有懸浮劑之熱水中攪拌混合,成型為球狀。 For other methods of obtaining the spheroidal pitch, for example, the method disclosed in Japanese Patent Publication No. Sho 59-10930 can also be referred to. Specifically, the mixture of the crosslinked heavy asphalt and the viscosity adjusting additive may be extruded into a rod shape in a molten state, or may be stretched, then cooled and solidified, and the obtained rod-shaped pitch is pulverized to prepare a length/diameter. The rod-shaped pitch having a ratio of 5 or less is then stirred and mixed in hot water containing a suspending agent at a temperature higher than the softening point of the rod-like pitch to form a spherical shape.
於本實施方式中,上述棒狀瀝青的尺寸決定了球狀活性炭之平均粒徑。因此,為使球狀活性炭之平均粒徑為1.5mm以上、4.0mm以下,優選使棒狀瀝青長度方向之尺寸為1.5~10mm左右。此外,押出棒狀瀝青時管口口徑優選為1.5mm~10mm左右。 In the present embodiment, the size of the rod-shaped pitch determines the average particle diameter of the spherical activated carbon. Therefore, in order to make the average particle diameter of the spherical activated carbon 1.5 mm or more and 4.0 mm or less, it is preferable that the dimension of the rod-shaped pitch in the longitudinal direction is about 1.5 to 10 mm. Further, when the rod-shaped pitch is extruded, the diameter of the nozzle is preferably about 1.5 mm to 10 mm.
將按照上述方式獲得之棒狀瀝青放入加熱至交聯重質瀝青與添加劑之混合物軟化點以上的熱水中,棒狀瀝青軟化變形,變成球狀瀝青。 The rod-shaped pitch obtained in the above manner is placed in hot water heated to a softening point or higher than the mixture of the crosslinked heavy pitch and the additive, and the rod-shaped pitch is softened and deformed to become a spherical pitch.
又,對交聯重質瀝青與添加劑之熔融混合物冷卻後粉碎,於熱水中攪拌時熱水的溫度(以下,將該溫度稱為「球狀化溫度」)可根據交聯重質瀝青與添加劑之熔融混合物黏度適當設定。 Further, the molten mixture of the crosslinked heavy pitch and the additive is cooled and pulverized, and the temperature of the hot water when the mixture is stirred in hot water (hereinafter, the temperature is referred to as "spheroidized temperature") can be based on crosslinking of heavy asphalt and The viscosity of the molten mixture of the additive is appropriately set.
於本實施方式中,球狀化溫度下限值優選為95℃以上,更優選為97℃以上,尤其優選為98℃以上。又,其上限值優選為120℃以下,更優選為115℃以下,尤其優選為110℃以下。將球狀化溫度設定為該範圍,從而可以有效地獲得球狀瀝青。另外,若球狀化溫度較低,交聯重質瀝青與添加劑之混合物不會變形,有可能無法有效地使棒狀瀝青實現球狀化。另一方面,若球狀化溫度過高,交聯重質瀝青與添加劑之混合物 會變為草袋狀,或者該熔融混合物碎裂,可能導致最終獲得的球狀活性炭粒徑變小。 In the present embodiment, the spheroidization temperature lower limit is preferably 95 ° C or higher, more preferably 97 ° C or higher, and particularly preferably 98 ° C or higher. Further, the upper limit thereof is preferably 120 ° C or lower, more preferably 115 ° C or lower, and particularly preferably 110 ° C or lower. The spheroidization temperature is set to this range, so that the spherical pitch can be efficiently obtained. Further, if the spheroidization temperature is low, the mixture of the crosslinked heavy pitch and the additive does not deform, and the rod-shaped pitch may not be effectively spheroidized. On the other hand, if the spheroidization temperature is too high, a mixture of crosslinked heavy asphalt and additives It may become a straw bag, or the molten mixture may be broken, which may result in a smaller particle size of the finally obtained spherical activated carbon.
另外,於熱水中使棒狀瀝青球狀化時,優選實施攪拌等操作。此時,若攪拌力較小,球狀瀝青會沉澱,且球狀瀝青彼此之間會發生熔合。另一方面,若攪拌力過高,則剪力可能會造成球狀瀝青被撕裂。因此,優選適當選擇於熱水中球狀瀝青會浮游.流動之最佳攪拌機構以及攪拌轉速。另外,使球狀瀝青流動的方法並不限定於攪拌,亦可採用其他適當的方法。 Further, when the rod-shaped pitch is spheroidized in hot water, it is preferred to carry out an operation such as stirring. At this time, if the stirring force is small, the spherical asphalt will precipitate, and the spherical asphalt will fuse with each other. On the other hand, if the stirring force is too high, the shearing force may cause the spherical asphalt to be torn. Therefore, it is preferred to properly choose the spherical asphalt to float in hot water. The best mixing mechanism for the flow and the stirring speed. Further, the method of flowing the spherical asphalt is not limited to stirring, and other appropriate methods may be employed.
進而,本實施方式更優選於存在懸浮劑之條件下將上述交聯重質瀝青與上述添加劑之混合物熔融、懸浮、分散於熱水中。即,使棒狀瀝青球狀化時,更優選於熱水中添加懸浮劑。含有懸浮劑之熱水具有提高球狀瀝青分散性,並防止球狀瀝青彼此之間互相熔合的作用。因此,本實施方式優選將交聯重質瀝青與添加劑之混合物熔融、懸浮、分散於熱水中,獲得球狀瀝青。 Further, in the present embodiment, it is more preferable that the mixture of the above-mentioned crosslinked heavy pitch and the above additive is melted, suspended, and dispersed in hot water in the presence of a suspending agent. That is, when the rod-shaped pitch is spheroidized, it is more preferable to add a suspending agent to hot water. The hot water containing the suspending agent has an effect of improving the dispersibility of the spherical asphalt and preventing the spherical asphalt from being fused to each other. Therefore, in the present embodiment, it is preferred that the mixture of the crosslinked heavy pitch and the additive is melted, suspended, and dispersed in hot water to obtain a spherical pitch.
於本實施方式中,懸浮劑可列舉例如聚乙烯醇(以下亦稱為「PVA」)、黃原膠、部分皂化聚醋酸乙烯酯、甲基纖維素、羧甲基纖維素、聚丙烯酸及其鹽類、聚乙二醇及其醚衍生物、酯衍生物澱粉、明膠等水溶性高分子化合物等。 In the present embodiment, the suspending agent may, for example, be polyvinyl alcohol (hereinafter also referred to as "PVA"), xanthan gum, partially saponified polyvinyl acetate, methyl cellulose, carboxymethyl cellulose, polyacrylic acid and the like. Salts, polyethylene glycols and ether derivatives thereof, ester derivative starches, water-soluble polymer compounds such as gelatin, and the like.
此時,懸浮劑之濃度可適當設定。另外,懸浮劑之濃度越高,球狀瀝青之沉降速度越低,因此,用更小之攪拌力即可分散球狀瀝青,且可抑制剪力造成球狀瀝青撕裂等。 At this time, the concentration of the suspending agent can be appropriately set. Further, the higher the concentration of the suspending agent, the lower the sedimentation speed of the spherical asphalt, so that the spherical asphalt can be dispersed with a smaller stirring force, and the shearing force of the spherical asphalt can be suppressed.
本實施方式使用PVA作為懸浮劑時,PVA相對於上述熱水之含量下限值為0.1質量百分比以上,優選為0.15質量百分比以上,更優選為0.23質量百分比以上,尤其優選為0.3質量百分比以上。又,其上限值優選為20質量百分比以下,更優選為15質量百分比以下,尤其優選為10質量百分比以下。 In the present embodiment, when PVA is used as the suspending agent, the lower limit of the content of PVA with respect to the above-mentioned hot water is 0.1 mass% or more, preferably 0.15 mass% or more, more preferably 0.23 mass% or more, and particularly preferably 0.3 mass% or more. Further, the upper limit thereof is preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 10% by mass or less.
熱水溫度下限值優選為95℃以上,更優選為97℃以上,尤其優選為98℃以上。又,其上限值優選為120℃以下,更優選為115℃以下,尤其優選為110℃以下。 Hot water lower limit temperature is preferably 95 ℃, more preferably 97 ℃, particularly preferably not less than 98 ℃. Further, the upper limit thereof is preferably 120 ° C or lower, more preferably 115 ° C or lower, and particularly preferably 110 ° C or lower.
進而,本實施方式亦可同時使用懸浮劑與增黏劑,或者僅單獨使用增黏劑。 Further, in the present embodiment, a suspending agent and a tackifier may be used at the same time, or only a tackifier may be used alone.
球狀化時,關於棒狀瀝青與含有懸浮劑之熱水的量比,優選液比較高。藉此,可以降低棒狀瀝青彼此之間碰撞等而產生的小粒徑化、變形的影響。 When spheroidizing, a rod on the amount of asphalt and water containing a suspending agent ratio, the liquid is preferably relatively high. Thereby, it is possible to reduce the influence of the small particle diameter and deformation caused by the collision of the bar-shaped pitches with each other.
(4)添加劑的提取 (4) Extraction of additives
繼而,去除所獲得之球狀瀝青中所包含之添加劑,於之後的不熔化製程中,形成用於使氧化性氣體擴散至球狀瀝青內部的孔。 Then, the additive contained in the obtained spherical asphalt is removed, and in the subsequent infusibilization process, pores for diffusing the oxidizing gas into the interior of the spherical asphalt are formed.
於本實施方式中,交聯重質瀝青與添加劑具有不互溶性,因此,推測球狀瀝青內部呈交聯重質瀝青與添加劑的海島結構。因此,本製造方法優選使用溶劑去除球狀瀝青中所包含之添加劑部分,從而於之後的不熔化製程中對球狀瀝青形成作為氧氣通道之孔。 In the present embodiment, the crosslinked heavy pitch and the additive have immiscibility, and therefore, it is presumed that the inside of the spherical asphalt is an island structure in which heavy asphalt and an additive are crosslinked. Therefore, the present production method preferably removes the additive portion contained in the spherical pitch using a solvent, thereby forming a pore as an oxygen passage for the spherical asphalt in the subsequent infusing process.
溶劑與球狀瀝青之漿料的質量比優選為7以上,更優選為9以上,尤其優選為13。若溶劑與球狀瀝青之漿料的質量比小於7,則無 法充分提取粒子內部之添加劑,於之後的不熔化製程中無法對球狀瀝青形成作為氧氣通道之孔。 The mass ratio of the solvent to the slurry of the spherical pitch is preferably 7 or more, more preferably 9 or more, and particularly preferably 13. If the mass ratio of the solvent to the slurry of the spherical asphalt is less than 7, then no The method sufficiently extracts the additive inside the particle, and in the subsequent infusibilization process, the pore of the spherical asphalt cannot be formed as an oxygen passage.
關於用於從球狀瀝青中提取、去除添加劑之溶劑,可列舉脂肪族化合物。該脂肪族化合物可列舉例如丁烷、戊烷、己烷、庚烷等脂族烴,石腦油、煤油等脂族烴主體之混合物,甲醇、乙醇、丙醇、丁醇等脂族醇類等,其中,優選使用正己烷。 As the solvent for extracting and removing the additive from the spherical pitch, an aliphatic compound can be cited. Examples of the aliphatic compound include aliphatic hydrocarbons such as butane, pentane, hexane, and heptane, mixtures of aliphatic hydrocarbons such as naphtha and kerosene, and aliphatic alcohols such as methanol, ethanol, propanol, and butanol. Etc., among them, n-hexane is preferably used.
此時,正己烷與球狀瀝青之漿料的質量比優選為7以上,更優選為9以上,尤其優選為13以上。若正己烷與球狀瀝青之漿料的質量比小於7,則無法充分提取粒子內部之添加劑,於之後的不熔化製程中無法對球狀瀝青形成作為氧氣通道之孔。 At this time, the mass ratio of the slurry of n-hexane and the spherical pitch is preferably 7 or more, more preferably 9 or more, and particularly preferably 13 or more. If the mass ratio of the slurry of n-hexane to the spherical pitch is less than 7, the additive inside the particles cannot be sufficiently extracted, and the pores which are the oxygen passages cannot be formed on the spherical pitch in the subsequent infusibilization process.
本實施方式優選充分形成用於使不熔化時的氧擴散至內部的孔。因此,優選充分地實施從球狀瀝青中提取添加劑之操作。 In the present embodiment, it is preferable to sufficiently form a hole for diffusing oxygen in the non-melting state to the inside. Therefore, it is preferred to sufficiently carry out the operation of extracting the additive from the spherical asphalt.
若如此使用溶劑,可以維持球狀瀝青之形狀,僅有效地去除添加劑。 If the solvent is used as such, the shape of the spherical asphalt can be maintained, and only the additive can be effectively removed.
於本製造方法中若從球狀瀝青中去除添加劑,則可於球狀瀝青中藉由提取添加劑而形成通孔,從而可以獲得具有均勻多孔性之多孔性球狀瀝青。 When the additive is removed from the spherical pitch in the present production method, the through hole can be formed by extracting the additive in the spherical pitch, whereby the porous spherical pitch having uniform porosity can be obtained.
於本實施方式中,多孔性球狀瀝青之軟化點受到交聯重質瀝青軟化點的極大影響。另外,若軟化點過低,則後述用於實現不熔化的熱處理時,多孔性球狀瀝青可能會軟化或熔融,並不優選。 In the present embodiment, the softening point of the porous spherical pitch is greatly affected by the softening point of the crosslinked heavy asphalt. Further, when the softening point is too low, the porous spherical pitch may be softened or melted during the heat treatment for achieving non-melting, which is not preferable.
於本實施方式中,多孔性球狀瀝青之軟化點越高越好。為提高多孔性球狀瀝青之軟化點,優選實施交聯瀝青之重質化。若該軟化點 過高,則交聯瀝青中會生成異向性成分,有可能難以實施交聯重質瀝青之球狀化、添加物的提取以及後述均勻之活化處理等。 In the present embodiment, the higher the softening point of the porous spherical pitch, the better. In order to increase the softening point of the porous spherical asphalt, it is preferred to carry out the weighting of the crosslinked asphalt. If the softening point If it is too high, an anisotropic component may be formed in the crosslinked asphalt, and it may be difficult to perform spheroidization of the crosslinked heavy pitch, extraction of the additive, and uniform activation treatment described later.
因此,於本實施方式中,多孔性球狀瀝青之軟化點優選為150℃以上、350℃以下,更優選為200℃以上、300℃,尤其優選為220℃以上、280℃以下。 Therefore, in the present embodiment, the softening point of the porous spherical pitch is preferably 150° C. or higher and 350° C. or lower, more preferably 200° C. or higher and 300° C., and particularly preferably 220° C. or higher and 280° C. or lower.
此外,多孔性球狀瀝青之甲苯不溶份與瀝青之碳化收率具有良好的相關關係,具有甲苯不溶份越高,碳化收率越高之趨勢。因此,甲苯不溶份優選為40%以上,更優選為50%以上。 In addition, the toluene insoluble fraction of the porous spherical asphalt has a good correlation with the carbonization yield of the asphalt, and the higher the toluene insoluble fraction, the higher the carbonization yield. Therefore, the toluene-insoluble matter is preferably 40% or more, and more preferably 50% or more.
(5)不熔化 (5) does not melt
接著,由多孔性球狀瀝青形成遇熱不熔之多孔性球狀不熔化瀝青。對此,本製造方法利用從球狀瀝青中提取添加劑而形成之孔,使氧化性氣體均勻地擴散至多孔性球狀瀝青內部,實施交聯處理。藉此,可以形成多孔性球狀不熔化瀝青。更具體為,例如於流動層中使氣體流過多孔性球狀瀝青,以100℃以上、350℃以下,優選為120℃以上、320℃以下,更優選為130℃以上、300℃以下之溫度進行加熱即可。 Next, a porous spherical infusible pitch which is infusible by heat is formed from the porous spherical pitch. On the other hand, in the production method, the pores formed by extracting the additive from the spherical asphalt are used to uniformly diffuse the oxidizing gas into the inside of the porous spherical asphalt, and the crosslinking treatment is carried out. Thereby, a porous spherical infusible pitch can be formed. More specifically, for example, the gas flows through the porous spherical pitch in the fluidized layer at a temperature of 100 ° C or more and 350 ° C or less, preferably 120 ° C or more and 320 ° C or less, more preferably 130 ° C or more and 300 ° C or less. It can be heated.
關於氧化性氣體,可以使用O2、O3、SO3、NO2、空氣等氧化性氣體,或者用氮氣、二氧化碳氣體、水蒸氣等惰性氣體稀釋該等氧化性氣體的混合氣體。 As the oxidizing gas, an oxidizing gas such as O 2 , O 3 , SO 3 , NO 2 or air may be used, or a mixed gas of these oxidizing gases may be diluted with an inert gas such as nitrogen gas, carbon dioxide gas or water vapor.
此外,關於交聯處理之程度,可藉由元素分析計算氧化處理,之後再根據多孔性瀝青元素分析的氧含量進行判斷。此時,氧含量為5質量百分比以上即可,優選實施氧化處理以確保氧含量優選為8質量百 分比以上、25質量百分比以下,更優選為10質量百分比以上、23質量百分比以下,尤其優選為11質量百分比以上、21質量百分比以下。 Further, regarding the degree of the crosslinking treatment, the oxidation treatment can be calculated by elemental analysis, and then the oxygen content of the porous asphalt element analysis can be judged. In this case, the oxygen content may be 5 mass% or more, and oxidation treatment is preferably performed to ensure that the oxygen content is preferably 8 mass%. The ratio is more than 25 parts by mass, more preferably 10% by mass or more and 23% by mass or less, and particularly preferably 11% by mass or more and 21% by mass or less.
(6)煅燒.活化 (6) Calcination. activation
最後,將多孔性球狀不熔化瀝青煅燒成碳,對該碳形成細孔。另外,不熔化製程中所形成之球狀活性炭的孔用於在不熔化時使氧擴散。經過該煅燒.活化製程後,掌管最終吸附能力的細孔形成為球狀活性炭。例如,於非氧化性環境氣體中,以600℃以上、優選為650℃以上、更優選為700℃以上之溫度對多孔性球狀不熔化瀝青進行熱處理,從而可獲得球狀碳成型體。 Finally, the porous spherical infusible pitch is calcined into carbon to form pores in the carbon. Further, the pores of the spherical activated carbon formed in the non-melting process are used to diffuse oxygen when not melted. After the calcination. After the activation process, the pores that govern the final adsorption capacity are formed into spherical activated carbon. For example, in the non-oxidizing atmosphere, the porous spherical infusible pitch is heat-treated at a temperature of 600 ° C or higher, preferably 650 ° C or higher, and more preferably 700 ° C or higher, whereby a spherical carbon molded body can be obtained.
繼而,利用常規方法,對球狀碳成型體進行煅燒、活化。此時,在以二氧化碳及水蒸氣等溫和之氧化性氣體為主要成分之活性氣體環境中,對球狀碳成型體實施活化處理。藉此,可以獲得本實施方式所涉及之球狀活性炭。 Then, the spherical carbon molded body is calcined and activated by a conventional method. At this time, the spherical carbon molded body is subjected to an activation treatment in an active gas atmosphere containing a mild oxidizing gas such as carbon dioxide or water vapor as a main component. Thereby, the spherical activated carbon concerning this embodiment can be obtained.
於本實施方式中,針對球狀碳成型體,優選以600℃以上、更優選以650℃以上、尤其優選以700℃以上之溫度使活性氣體發揮作用。藉此,亦可同時開展球狀碳成型體之碳化以及活化,故自製程經濟性的觀點出發,優選此操作。 In the present embodiment, the spherical carbon molded body preferably has an active gas at 600 ° C or higher, more preferably 650 ° C or higher, and particularly preferably 700 ° C or higher. Thereby, carbonization and activation of the spherical carbon molded body can be simultaneously performed, and this operation is preferable from the viewpoint of the economics of the self-made process.
於本實施方式中,對於按上述方式而獲得之球狀活性炭,進而亦可浸染酸、鹼或金屬等其他物質。對球狀活性炭浸染其他物質時可以使用周知之方法。例如,若使球狀活性炭浸染或承載金屬,則可以使用該球狀活性炭作為觸媒等。 In the present embodiment, the spherical activated carbon obtained as described above may be further impregnated with other substances such as an acid, an alkali or a metal. A well-known method can be used for infiltrating other substances into the spherical activated carbon. For example, if the spherical activated carbon is impregnated or supported with a metal, the spherical activated carbon can be used as a catalyst or the like.
接著,以實施例所示內容,針對本發明進行更詳細的說明,不過,本發明並不限定於該等實施例。 Next, the present invention will be described in more detail with reference to the examples, but the present invention is not limited to the examples.
活性炭之平均粒徑依據JIS K 1474進行評價。具體為,依據JIS K 1474製作累積粒度分佈曲線圖,由橫軸50%點之垂直線與累積粒度分佈曲線圖的交點,沿縱軸畫水平線,計算交點所表示之篩孔(mm),將該篩孔值設為平均粒徑。 The average particle diameter of the activated carbon was evaluated in accordance with JIS K 1474. Specifically, a cumulative particle size distribution curve is prepared according to JIS K 1474, and a horizontal line is drawn along the vertical axis from the intersection of the vertical line of the 50% point of the horizontal axis and the cumulative particle size distribution curve, and the sieve hole (mm) represented by the intersection point is calculated. The mesh value is set to an average particle diameter.
關於活性炭之細孔徑及細孔容積,採用水銀壓入法之細孔容積水銀測孔儀(MICROMERITICS公司製「AUTOPORE 9200」),測定活性炭之細孔徑及細孔容積。具體為,將活性碳放入試樣容器內,以2.67Pa以下的壓力進行30分鐘的脫氣。接著,將水銀導入至試樣容器內,慢慢加壓,將水銀朝活性碳的細孔壓入。繼而,根據此時壓力與水銀壓入量之間的關係,使用以下各計算公式,計算活性碳的細孔容積分佈。 The pore diameter and the pore volume of the activated carbon were measured by a pore volume mercury porosimeter ("AUTOPORE 9200" manufactured by MICROMERITICS Co., Ltd.) by a mercury intrusion method, and the pore diameter and pore volume of the activated carbon were measured. Specifically, activated carbon was placed in a sample container, and degassing was performed for 30 minutes at a pressure of 2.67 Pa or less. Next, mercury is introduced into the sample container, and the pressure is gradually applied to press the mercury into the pores of the activated carbon. Then, based on the relationship between the pressure at this time and the amount of mercury intrusion, the pore volume distribution of the activated carbon was calculated using the following calculation formulas.
關於細孔直徑的計算,當以壓力(P)將水銀壓入至直徑(D)之圓筒形細孔的情況下,將水銀表面張力設為「γ」,將水銀與細孔壁之間的接觸角設為「θ」,由於表面張力與作用於細孔截面上的壓力相互均衡,-πDγcosθ=π(D/2) 2 .P...(式2)關係式成立。因此,D=(-4γcosθ)/P...(式3) Regarding the calculation of the pore diameter, when mercury is pressed into the cylindrical pores of the diameter (D) by the pressure (P), the surface tension of the mercury is set to "γ", and between the mercury and the pore walls. The contact angle is set to "θ", and since the surface tension and the pressure acting on the cross section of the pore are balanced with each other, -πDγcos θ = π(D/2) 2 . The relationship of P...(Formula 2) is established. Therefore, D = (-4 γ cos θ) / P (Expression 3)
於本說明書中,將水銀表面張力設為484dyne/cm,將水銀與碳之間的接觸角設為130度,將壓力P設為MPa,並且以μm表示細 孔直徑D,藉由下式:D=1.24/P...(式4)計算壓力P與細孔直徑D的關係。 In the present specification, the surface tension of mercury is set to 484 dyne/cm, the contact angle between mercury and carbon is set to 130 degrees, the pressure P is set to MPa, and fine is expressed in μm. The pore diameter D is calculated by the following formula: D = 1.24 / P (Formula 4). The relationship between the pressure P and the pore diameter D is calculated.
另外,本實施例中細孔直徑為50~10000nm範圍內的細孔容積,相當於在對應之水銀壓入壓力範圍所壓入的水銀體積。 Further, in the present embodiment, the pore volume having a pore diameter in the range of 50 to 10,000 nm corresponds to the volume of mercury pressed in the corresponding mercury intrusion pressure range.
根據以下步驟,評價活性炭之粉塵量。 The amount of dust of the activated carbon was evaluated according to the following procedure.
1)預先以110℃對薄膜過濾器(ADVANTEC製直徑47mm、孔徑1μm)乾燥1小時後,於乾燥器中放置冷卻,之後,用精密天平稱量,精確到0.1mg。 1) The film filter (ADVANTEC diameter 47 mm, pore diameter 1 μm) was dried in advance at 110 ° C for 1 hour, and then placed in a desiccator to be cooled, and then weighed with a precision balance to the nearest 0.1 mg.
2)取乾燥試樣5g放入100ml錐形瓶中,用精密天平稱量,精確到0.1mg。 2) Take 5 g of the dried sample into a 100 ml Erlenmeyer flask and weigh it with a precision balance to the nearest 0.1 mg.
3)向錐形瓶中加入純水100ml,放入超音波清洗機(日本EMERSON製Bransonic台式超音波清洗器1510J-MT)中清洗3分鐘。 3) 100 ml of pure water was added to the Erlenmeyer flask, and the mixture was washed in an ultrasonic cleaning machine (Bransonic Desktop Ultrasonic Cleaner 1510J-MT, manufactured by EMERSON, Japan) for 3 minutes.
4)用孔徑為106μm之篩子對超音波清洗後之懸浮液進行過濾,並用安裝於微孔過濾器抽吸裝置上的薄膜過濾器對濾液進行過濾。用純水流過上述3)製程之錐形瓶壁面,並用薄膜過濾器對其亦進行過濾。 4) The ultrasonically cleaned suspension was filtered with a sieve having a pore size of 106 μm, and the filtrate was filtered with a membrane filter attached to a microfilter suction device. The wall of the conical flask of the above 3) process was flowed with pure water and filtered through a membrane filter.
5)將上述4)製程中殘留於篩上之試樣放回錐形瓶中,加入純水100ml後,重複上述3)與上述4)操作共計3次。 5) Put the sample remaining on the sieve in the above 4) process back into the Erlenmeyer flask, and after adding 100 ml of pure water, repeat the above 3) and the above 4) operation a total of 3 times.
6)以110℃對過濾後之薄膜過濾器乾燥1小時後,於乾燥器中放置冷卻30分鐘,之後,用精密天平稱量,精確到0.1mg。 6) After drying the filtered membrane filter at 110 ° C for 1 hour, it was left to cool in a desiccator for 30 minutes, and then weighed with a precision balance to the nearest 0.1 mg.
7)根據下式計算碳粉量。 7) Calculate the amount of toner according to the following formula.
碳粉量=(B-A)/S...(式5) Toner amount = (B-A) / S... (Formula 5)
A:過濾前薄膜過濾器之質量(g) A: Quality of the membrane filter before filtration (g)
B:過濾後薄膜過濾器之質量(g) B: mass of the membrane filter after filtration (g)
S:試樣質量(g) S: sample quality (g)
根據以下方法評價活性炭之水中振盪磨損率。 The oscillating wear rate in the water of activated carbon was evaluated according to the following method.
1)將預先以110℃乾燥1小時的薄膜過濾器(孔徑0.3μm)於乾燥器中放置冷卻,之後,用精密天平稱量,精確到0.1mg。 1) A membrane filter (pore size: 0.3 μm) which was previously dried at 110 ° C for 1 hour was placed in a desiccator and cooled, and then weighed with a precision balance to the nearest 0.1 mg.
2)稱取乾燥試樣約10g,精確到0.1mg,移入200ml分液漏斗中,加入純水50ml後,用振盪機(IWAKI產業製KM-SHAKER型號V-S振幅40mm、振盪頻率250次往復/分鐘)振盪120分鐘。 2) Weigh about 10g of dry sample, accurate to 0.1mg, transfer to a 200ml separatory funnel, add 50ml of pure water, and use a oscillating machine (IWKI industrial KM-SHAKER model VS amplitude 40mm, oscillation frequency 250 times reciprocating / minute ) Oscillation for 120 minutes.
3)用孔徑150μm之篩子過濾懸浮液,使用薄膜過濾器抽吸、過濾濾液。用純水流過上述2)製程之分液漏斗壁面,並用薄膜過濾器對其亦進行過濾。 3) The suspension was filtered through a sieve having a pore size of 150 μm, and the filtrate was suctioned and filtered using a membrane filter. Pure water was passed through the wall of the separatory funnel of the above 2) process, and it was also filtered with a membrane filter.
4)以110℃對薄膜過濾器乾燥30分鐘後,於乾燥器中放置冷卻30分鐘,準確稱取薄膜過濾器之重量,精確到0.1mg。 4) After drying the membrane filter at 110 ° C for 30 minutes, it was left to cool in a desiccator for 30 minutes, and the weight of the membrane filter was accurately weighed to the nearest 0.1 mg.
5)根據下式,計算水中振盪磨損率。 5) Calculate the oscillating wear rate in water according to the following formula.
水中振盪磨損率(%)=(b-a)/s×100...(式6) Oscillation wear rate in water (%) = (b-a) / s × 100 (Equation 6)
a:過濾前薄膜過濾器之質量(g) a: mass of membrane filter before filtration (g)
b:過濾後薄膜過濾器之質量(g) b: mass of the membrane filter after filtration (g)
s:試樣質量(g) s: sample quality (g)
使用比表面積連續流動式氣體吸附法的比表面積測定器(MICROMERITICS公司製「FLOWSORB」),測定試樣(碳質材料)之氣體吸附量,藉由BET公式計算比表面積。 The gas adsorption amount of the sample (carbonaceous material) was measured using a specific surface area measuring device ("FLOWSORB" manufactured by MICROMERITICS) using a specific surface area continuous flow gas adsorption method, and the specific surface area was calculated by the BET formula.
具體為,將試樣填充到試樣管中,使含有30vol%氮之氦氣流過該試樣管,同時進行以下操作,計算試樣對氮的吸附量。即,將試樣管冷卻至-196℃,使試樣吸附氮。接著,將試樣管恢復至室溫。此時,利用導熱率型檢測器測定從多孔性球狀碳質物質試樣上脫離之氮量,將其作為吸附氣體量(v)。繼而,使用由BET公式推導之近似公式:Vm=1/(v.(1-x))...(式7)計算於液態氮溫度下,利用氮吸附之一點測定法(相對壓力x=0.3),計算出Vm,並根據以下公式:比表面積=4.35×Vm(m2/g)...(式8)計算試樣之比表面積。另外,上述各計算公式中,v為實測之吸附量(cm3/g),x為相對壓力。 Specifically, the sample was filled in a sample tube, and a sample containing 30 vol% of nitrogen was passed through the sample tube, and the following operation was performed to calculate the amount of nitrogen adsorbed by the sample. That is, the sample tube was cooled to -196 ° C to adsorb nitrogen to the sample. Next, the sample tube was returned to room temperature. At this time, the amount of nitrogen desorbed from the porous spherical carbonaceous material sample was measured by a thermal conductivity type detector, and this was taken as the amount of adsorbed gas (v). Then, using the approximate formula derived from the BET formula: V m =1/(v.(1-x)) (Expression 7) is calculated at the liquid nitrogen temperature, using a point measurement method of nitrogen adsorption (relative pressure x) = 0.3), Vm was calculated, and the specific surface area of the sample was calculated according to the following formula: specific surface area = 4.35 × V m (m 2 /g) (Equation 8). Further, in each of the above calculation formulas, v is the actually measured adsorption amount (cm 3 /g), and x is the relative pressure.
依據JIS K1474-1991法測定填充密度。 The packing density was measured in accordance with JIS K1474-1991.
使用數位顯微鏡(KEYENCE公司製「VHX-700F」),計算試樣之短長徑比。 The short length to diameter ratio of the sample was calculated using a digital microscope ("VHX-700F" manufactured by KEYENCE Corporation).
具體為,以平均提取的方式將30粒試樣粒子分散於培養皿中,用數位顯微鏡測定每個粒子之長軸與短軸長度。繼而,根據長軸與短軸長度比,計算出短長徑比,最大為1。在以下實施例等中,將30個粒子之短長徑比的平均值設為短長徑比。 Specifically, 30 sample particles were dispersed in a petri dish by an average extraction method, and the major axis and minor axis length of each particle were measured by a digital microscope. Then, according to the ratio of the long axis to the short axis length, the short aspect ratio is calculated, and the maximum is 1. In the following examples and the like, the average value of the short aspect ratios of the 30 particles was set to the short aspect ratio.
抗壓碎力可藉由以下方法計算。即,隨機抽取球狀活性炭之試樣粒子30粒,使用簡易顆粒硬度計(筒井理化學器械株式會社製),測定試樣粒子被壓碎的瞬間的硬度。從硬度測定值中剔除最大值及最小值,計算出28粒試樣粒子硬度測定值的平均值,設為該試樣粒子之抗壓碎力。 The crush resistance can be calculated by the following method. In other words, 30 pieces of the sample particles of the spherical activated carbon were randomly sampled, and the hardness at the moment when the sample particles were crushed was measured using a simple particle hardness meter (manufactured by Tsutsui Chemical Instruments Co., Ltd.). The maximum value and the minimum value were excluded from the hardness measurement values, and the average value of the measured values of the particle hardness of 28 sample pieces was calculated, and the crush resistance of the sample particles was determined.
對內容積為25公升之不鏽鋼製耐壓容器中投入比重(15℃下試樣質量與4℃下等體積純水質量之比)為1.08、製造乙烯時所生成之塔底油(乙烯塔底油)10.0kg。自反應容器下方以3.7L/min速度吹入空氣,於0.4MPa之加壓條件下,自230℃升溫至250℃,進行吹氣反應4小時20分鐘。從而獲得9.5kg吹氣焦油。以385℃對所獲得之吹氣焦油3.0kg進行熱重質化處理,之後,進而減壓餾去輕質成分,從而獲得吹氣瀝青1.4kg。所獲得之瀝青軟化點為203℃,甲苯不溶份為58%。 The specific gravity (ratio of the mass of the sample at 15 ° C to the mass of the equal volume of pure water at 4 ° C) in a stainless steel pressure vessel having an internal volume of 25 liters is 1.08, and the bottom oil (ethylene bottom) generated when ethylene is produced. Oil) 10.0kg. Air was blown from the lower side of the reaction vessel at a rate of 3.7 L/min, and the temperature was raised from 230 ° C to 250 ° C under a pressurized condition of 0.4 MPa, and a blowing reaction was carried out for 4 hours and 20 minutes. Thereby 9.5 kg of blowing tar was obtained. The obtained crude tar of 3.0 kg of the obtained tar was subjected to thermal heavy treatment at 385 ° C, and then the light component was distilled off under reduced pressure to obtain 1.4 kg of a blown pitch. The obtained pitch had a softening point of 203 ° C and a toluene-insoluble fraction of 58%.
將上述吹氣瀝青0.72kg與萘0.28kg投入帶有攪拌葉片、內容積為1.5L之耐壓容器中,以200℃熔融混合,然後冷卻至140~160℃並押出,獲得直徑為2mm之棒狀成型體。接著,將該棒狀成型體粉碎成長度約2.0mm至2.8mm。在將作為懸浮劑之1.2重量百分比之聚乙烯醇(皂化率=88%)溶解並加熱至100℃之水溶液1L中,投入上述粉碎物約450ml。藉由攪拌、分散使粉碎物實現球狀化,之後冷卻,用水置換上述聚乙烯醇水溶液,從而獲得球狀瀝青成型體漿料。藉由過濾去除大部分水後,利用球狀瀝青漿料7倍重量之正己烷提取、去除球狀瀝青漿料中之萘,獲得多孔性球狀瀝青。使用流體化床,對上述方式獲得之多孔性球狀瀝青通入加熱空氣,同時用1小時從室溫升溫至150℃,然後以 20℃/h之升溫速度從150℃升溫至260℃,之後以260℃保持1小時進行氧化。藉此,獲得遇熱不熔之多孔性球狀不熔化瀝青。繼而,使用流體化床,於包含50vol%水蒸氣之氮氣環境中,以850℃對多孔性球狀不熔化瀝青進行活化處理至填充密度為0.79g/ml,獲得球狀活性炭。對所獲得之球狀活性炭之平均粒徑、細孔徑分佈、粉塵量、水中振蕩磨損率、比表面積、短長徑比進行評價。 0.72 kg of the above-mentioned air-blown pitch and 0.28 kg of naphthalene were put into a pressure-resistant container with a stirring blade and an internal volume of 1.5 L, melt-mixed at 200 ° C, and then cooled to 140 to 160 ° C and extruded to obtain a rod having a diameter of 2 mm. Shaped body. Next, the rod-shaped molded body was pulverized to a length of about 2.0 mm to 2.8 mm. Into 1 L of an aqueous solution in which 1.2% by weight of polyvinyl alcohol (saponification ratio = 88%) as a suspending agent was dissolved and heated to 100 ° C, about 450 ml of the above-mentioned pulverized product was charged. The pulverized material is spheroidized by stirring and dispersion, and then cooled, and the aqueous polyvinyl alcohol solution is replaced with water to obtain a spherical asphalt molded body slurry. After removing most of the water by filtration, the naphthalene in the spherical asphalt slurry was extracted and removed by using 7 times by weight of the spherical asphalt slurry in n-hexane to obtain a porous spherical pitch. Using a fluidized bed, the porous spherical asphalt obtained in the above manner was passed through heated air while being heated from room temperature to 150 ° C for 1 hour, and then The temperature increase rate of 20 ° C / h was raised from 150 ° C to 260 ° C, and then maintained at 260 ° C for 1 hour for oxidation. Thereby, a porous spherical infusible pitch which is infusible by heat is obtained. Then, using a fluidized bed, the porous spherical infusible pitch was activated at 850 ° C in a nitrogen atmosphere containing 50 vol% of water vapor to a packing density of 0.79 g/ml to obtain a spherical activated carbon. The average particle diameter, pore diameter distribution, dust amount, water oscillating wear rate, specific surface area, and short aspect ratio of the obtained spherical activated carbon were evaluated.
如表1及2所示,除了分別變更吹氣瀝青與萘熔融混合時之瀝青量、萘量、球狀化時棒狀成型體投入量、球狀化溫度、聚乙烯醇濃度、提取萘時之正己烷量以及活化後之填充密度以外,其他操作與實施例1相同,獲得實施例2~8之活性炭。 As shown in Tables 1 and 2, in addition to changing the amount of asphalt, the amount of naphthalene, the amount of rod-shaped molded body during spheroidization, the spheroidization temperature, the concentration of polyvinyl alcohol, and the extraction of naphthalene, respectively, when the blowing pitch and naphthalene are melt-mixed, respectively. Other operations were the same as in Example 1 except for the amount of n-hexane and the packing density after activation, and the activated carbons of Examples 2 to 8 were obtained.
如表1所示,除了調整吹氣瀝青與萘熔融混合時之瀝青量、萘量、棒狀成型體尺寸、球狀化時棒狀成型體投入量、球狀化溫度、聚乙烯醇濃度、提取萘時之正己烷量以外,其他操作與實施例1相同,獲得多孔性球狀瀝青。 As shown in Table 1, in addition to adjusting the amount of asphalt, the amount of naphthalene, the size of the rod-shaped molded body, the amount of the rod-shaped molded body when spheroidized, the spheroidizing temperature, the polyvinyl alcohol concentration, and the like, Other than the amount of n-hexane in the case of extracting naphthalene, other operations were carried out in the same manner as in Example 1 to obtain a porous spherical pitch.
利用靜置層對所獲得之多孔性球狀瀝青通入加熱空氣,同時用1小時從室溫升溫至150℃,然後以20℃/h之升溫速度從150℃升溫至260℃,之後以260℃保持1小時進行氧化。藉此,獲得遇熱不熔之多孔性球狀不熔化瀝青。繼而,利用靜置層,於包含50vol%水蒸氣之氮氣環境中,以850℃對多孔性球狀不熔化瀝青進行活化處理至填充密度為0.70g/ml,獲得活性炭。 The porous spherical pitch obtained by the standing layer was heated with air, and was heated from room temperature to 150 ° C for 1 hour, and then heated from 150 ° C to 260 ° C at a temperature increase rate of 20 ° C / h, and then 260 Oxidation was carried out for 1 hour at °C. Thereby, a porous spherical infusible pitch which is infusible by heat is obtained. Then, the porous spherical infusible pitch was activated at 850 ° C in a nitrogen atmosphere containing 50 vol% of water vapor using a standing layer to a packing density of 0.70 g/ml to obtain activated carbon.
如表1所示,除了調整吹氣瀝青與萘熔融混合時之瀝青量、萘量、棒狀成型體尺寸、球狀化時棒狀成型體投入量、球狀化溫度、聚乙烯醇濃度、提取萘時之正己烷量以外,其他操作與實施例1相同,獲得多孔性球狀瀝青。 As shown in Table 1, in addition to adjusting the amount of asphalt, the amount of naphthalene, the size of the rod-shaped molded body, the amount of the rod-shaped molded body when spheroidized, the spheroidizing temperature, the polyvinyl alcohol concentration, and the like, Other than the amount of n-hexane in the case of extracting naphthalene, other operations were carried out in the same manner as in Example 1 to obtain a porous spherical pitch.
利用靜置層對所獲得之多孔性球狀瀝青通入加熱空氣,同時用1小時從室溫升溫至150℃,然後以20℃/h之升溫速度從150℃升溫至300℃,之後以300℃保持1小時進行氧化。藉此,獲得遇熱不熔之多孔性球狀不熔化瀝青。繼而,利用靜置層,於包含50vol%水蒸氣之氮氣環境中,以850℃對多孔性球狀不熔化瀝青進行活化處理至填充密度為0.68g/ml,獲得活性炭。 The porous spherical pitch obtained by the standing layer is heated with air, and is heated from room temperature to 150 ° C for 1 hour, and then heated from 150 ° C to 300 ° C at a temperature increase rate of 20 ° C / h, and then 300 Oxidation was carried out for 1 hour at °C. Thereby, a porous spherical infusible pitch which is infusible by heat is obtained. Then, the porous spherical infusible pitch was activated at 850 ° C in a nitrogen atmosphere containing 50 vol% of water vapor using a standing layer to a packing density of 0.68 g/ml to obtain activated carbon.
除了將瀝青設為0.75kg、萘量設為0.25kg以外,其他操作與實施例1相同,製作活性炭,但於煅燒.活化製程中多孔性球狀不熔化瀝青成型體熔融,無法維持其形狀(球狀)。 The operation was the same as in Example 1 except that the pitch was 0.75 kg and the amount of naphthalene was 0.25 kg, but the activated carbon was produced, but calcined. In the activation process, the porous spherical infusible pitch molded body is melted, and the shape (spherical shape) cannot be maintained.
如表1所示,除了調整吹氣瀝青與萘量、球狀化溫度、聚乙烯醇濃度以及己烷量以外,其他操作與實施例1相同,製作活性炭,但於煅燒.活化製程中多孔性球狀不溶性瀝青成型體熔融,無法維持其形狀(球狀)。 As shown in Table 1, except that the amount of the blown asphalt and the amount of naphthalene, the spheroidization temperature, the polyvinyl alcohol concentration, and the amount of hexane were adjusted, the other operations were the same as in Example 1, and activated carbon was produced, but calcined. In the activation process, the porous spherical insoluble pitch molded body is melted, and the shape (spherical shape) cannot be maintained.
如表1所示,除了調整吹氣瀝青與萘量、球狀化溫度以及聚乙烯醇濃度以外,其他操作與實施例1相同,製作活性炭。其結果為,交聯重質瀝青之成型製程中所獲得之瀝青成型體的形狀全部為橢圓形。 As shown in Table 1, activated carbon was produced in the same manner as in Example 1 except that the amount of the blown asphalt and the amount of naphthalene, the spheroidization temperature, and the polyvinyl alcohol concentration were adjusted. As a result, the shape of the asphalt molded body obtained in the molding process of the crosslinked heavy asphalt is all elliptical.
將直徑為1.0mm之棒狀成型體粉碎為長度約1.0mm至1.5mm,並且如表1所示,除了調整吹氣瀝青與萘量、球狀化溫度、聚乙烯醇濃度以及己烷量以外,其他操作與實施例1相同,獲得活性炭。 The rod-shaped molded body having a diameter of 1.0 mm was pulverized to a length of about 1.0 mm to 1.5 mm, and as shown in Table 1, except for adjusting the amount of the blown asphalt and the amount of naphthalene, the spheroidization temperature, the polyvinyl alcohol concentration, and the amount of hexane. Other operations were the same as in Example 1, and activated carbon was obtained.
針對球狀白鷺X7000H(大阪GAS CHEMICALS株式會社),開展與實施例1相同之評價。 The same evaluation as in Example 1 was carried out for the spherical egret X7000H (Osaka GAS CHEMICALS Co., Ltd.).
針對KURARAY COAL SW(KURARAY CHEMICALS株式會社),開展與實施例1相同之評價。 The same evaluation as in Example 1 was carried out for KURARAY COAL SW (KURARAY CHEMICALS Co., Ltd.).
上述各實施例及比較例之結果匯總於表1及2中。 The results of the above respective examples and comparative examples are summarized in Tables 1 and 2.
表1中「尺寸」係指棒狀成型體之尺寸,「投入量」係指棒狀成型體之投入量。此外,「懸浮劑」例如為PVA。又,「Rhex」係指提取時之己烷質量比,更具體為,正己烷相對於球狀瀝青漿料之質量比(正己烷量/球狀瀝青漿料量)。 In Table 1, "size" means the size of the rod-shaped molded body, and "input amount" means the amount of input of the rod-shaped molded body. Further, the "suspending agent" is, for example, PVA. Further, "Rhex" means the mass ratio of hexane at the time of extraction, and more specifically, the mass ratio of n-hexane to the spherical pitch slurry (the amount of n-hexane / the amount of the spherical pitch slurry).
表2中「D1」係指熔融,「D2」係指全部為橢圓形。此外,「Vp1」係指10~10000nm範圍內之細孔容積,「Vp2」係指50~10000nm範圍內之細孔容積。又,「Asw」係指水中振盪磨損率,「Rasp」係指短長徑比,「Sp」係指抗壓碎力。 In Table 2, "D1" means melting, and "D2" means all of them are elliptical. Further, "Vp1" means a pore volume in the range of 10 to 10,000 nm, and "Vp2" means a pore volume in the range of 50 to 10,000 nm. Also, "Asw" refers to the oscillating wear rate in water, "Rasp" refers to the short aspect ratio, and "Sp" refers to the crush resistance.
本發明適宜用作例如分離製程、精製、觸媒或溶劑回收等的活性炭。 The present invention is suitably used as an activated carbon such as a separation process, purification, catalyst or solvent recovery.
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