TW201311558A - Method of preparing enhanced porous carbon - Google Patents

Method of preparing enhanced porous carbon Download PDF

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TW201311558A
TW201311558A TW101117694A TW101117694A TW201311558A TW 201311558 A TW201311558 A TW 201311558A TW 101117694 A TW101117694 A TW 101117694A TW 101117694 A TW101117694 A TW 101117694A TW 201311558 A TW201311558 A TW 201311558A
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carbon
porous carbon
magnesium carbonate
surface area
porous
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TW101117694A
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彼特 布蘭頓
陸安慧
李文翠
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英美煙草（投資）有限公司
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    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/16—Use of materials for tobacco smoke filters of inorganic materials
    • A24D3/163—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/318—Preparation characterised by the starting materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/485—Plants or land vegetals, e.g. cereals, wheat, corn, rice, sphagnum, peat moss

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The present invention relates to a method of preparing porous carbon. In particular, the carbon exhibits enhanced adsorption selectivity for low molecular weight aldehydes, such a formaldehyde, and for hydrogen cyanide. The method comprises applying magnesium carbonate to carbon prior to polycondensation and/or carbonisation, so that the porous carbon becomes impregnated with magnesium carbonate. The carbon is suitable for use in smoke filtration.

Description

製備增強的多孔性碳之方法 Method for preparing reinforced porous carbon

本發明係關於一種製備多孔性碳之方法。特別地，該碳展現對於低分子量醛、如甲醛，以及對於氫化氰(HCN)之增強吸附選擇性。該方法包含在聚縮合及/或碳化前施加碳酸鎂至碳，使得該多孔性碳成為經碳酸鎂浸漬。本發明之多孔性碳係特別有用於吸煙物件中之煙過濾，因為當相較於傳統活性碳時，其可提供改良之上述煙汽相組份的吸附。 This invention relates to a process for preparing porous carbon. In particular, the carbon exhibits enhanced adsorption selectivity for low molecular weight aldehydes such as formaldehyde, and for hydrogen cyanide (HCN). The method comprises applying magnesium carbonate to carbon prior to polycondensation and/or carbonization such that the porous carbon is impregnated with magnesium carbonate. The porous carbon system of the present invention is particularly useful for smoke filtration in smoking articles because it provides improved adsorption of the above described vapor phase components when compared to conventional activated carbon.

過濾係用於降低吸煙過程中吸入之菸草煙(tobacco smoke)的某些顆粒及/或汽相組份。重要的是這無須進而降低產品品質或風味之移除顯著程度的其他成分(如感官(organoleptic)成分)而達到。 Filtration is used to reduce certain particulate and/or vapor phase components of tobacco smoke inhaled during smoking. It is important that this is achieved without further reducing the quality of the product or the removal of a significant degree of flavoring of other ingredients, such as organoleptic ingredients.

吸煙物件過濾器可包含吸附某些煙組份之多孔性碳材料，其典型地係藉由物理吸附。此些多孔性碳材料可製自碳化形式之許多不同有機材料。二擇一地，使用合成碳，如藉由聚縮合反應製備之樹脂。 The smoking article filter may comprise a porous carbon material that adsorbs certain smoke components, typically by physical adsorption. Such porous carbon materials can be made from many different organic materials in a carbonized form. Alternatively, synthetic carbon, such as a resin prepared by a polycondensation reaction, is used.

由於多孔性碳材料之大表面積、微孔結構及高度表面反應性，其已變成廣泛用作為多功能吸附劑。 Due to the large surface area, microporous structure and high surface reactivity of the porous carbon material, it has become widely used as a multifunctional adsorbent.

多孔性碳通常製自包含椰殼、以植物為基質之材料、木粉、泥炭、骨(bone)、煤溚、樹脂及相關聚合物之材料。椰殼作為製造活性碳之原料係特別具吸引力 的，因為其便宜且容易取得，和亦為環境上能承受的。此外，自非常純且具有高表面積之椰殼活性碳材料製得係可能的。 Porous carbon is typically made from materials comprising coconut shells, plant-based materials, wood flour, peat, bone, coal gangue, resins, and related polymers. Coconut shell is particularly attractive as a raw material for the production of activated carbon. Because it is cheap and easy to obtain, and is also environmentally sustainable. Furthermore, it is possible to make a coconut shell activated carbon material which is very pure and has a high surface area.

如上所述，微孔性碳的替代來源係合成碳，如藉由聚合反應形成者，像是以樹脂為基質之合成碳。此些碳可(例如)藉由醛與酚之聚合而製備。 As noted above, an alternative source of microporous carbon is synthetic carbon, such as by polymerization, such as resin-based synthetic carbon. Such carbons can be prepared, for example, by polymerization of an aldehyde with a phenol.

此些合成碳係引人注目的，因為在製造過程中可控制某些其物理特性，允許其適合提供所欲過濾特徵。然而，此些材料相較於活性化椰碳及其類似物顯著地非常昂貴。 Such synthetic carbons are compelling because some of their physical properties can be controlled during the manufacturing process, allowing them to be adapted to provide the desired filtering characteristics. However, such materials are significantly more expensive than activated coconut carbon and its analogs.

多孔性碳材料在不同環境下作為吸附劑之性能與合適性係藉由材料的不同物理性質，包含粒子形狀與尺寸、孔徑、材料表面積等而測定。此些不同參數可藉由操縱製造多孔性碳之方法及條件來控制。 The properties and suitability of porous carbon materials as adsorbents in different environments are determined by the different physical properties of the materials, including particle shape and size, pore size, material surface area, and the like. These different parameters can be controlled by manipulating the methods and conditions for making porous carbon.

一般而言，多孔性材料之表面積越大則材料吸附量越大。然而，由於材料表面積增加，密度及結構完整性被降低。此外，材料表面積可能藉由增加孔隙數以及使孔隙更小而增加，由於孔隙尺寸接近目標分子之尺寸，不太可能目標分子將進入孔隙以及吸附至材料。若過濾材料具有相較於活性碳材料高的流率，這是特別為真的，如在吸煙物件的情況下。 In general, the larger the surface area of the porous material, the greater the amount of material adsorbed. However, density and structural integrity are reduced due to increased surface area of the material. In addition, the surface area of the material may increase by increasing the number of pores and making the pores smaller. Since the pore size is close to the size of the target molecule, it is unlikely that the target molecules will enter the pores and adsorb to the material. This is especially true if the filter material has a higher flow rate than the activated carbon material, as in the case of smoking articles.

用於製造多孔性碳之精確方法對其性質有很強的影響。因此，製造具有廣範圍的形狀、尺寸、尺寸分布、孔徑、孔隙體積、孔徑分布及表面積之碳粒子係可能 的，其各影響該等碳粒子作為吸附劑之有效性。磨損率(attrition rate)亦為一重要變數，低磨損率可期望避免在高速過濾器製造過程中產生粉塵(dust)。 The precise method used to make porous carbon has a strong influence on its properties. Therefore, it is possible to produce carbon particle systems with a wide range of shapes, sizes, size distributions, pore sizes, pore volumes, pore size distributions, and surface areas. Each affects the effectiveness of the carbon particles as an adsorbent. The attrition rate is also an important variable, and low wear rates can be expected to avoid the generation of dust during high speed filter manufacturing.

如Adsorption(2008)14：335-341中所解釋，常見椰碳實質上為微孔性，並且增加碳活化時間，導致微孔數及表面積增加但造成孔徑或孔隙分布無真實改變。 As explained in Adsorption (2008) 14:335-341, common coconut carbon is substantially microporous and increases the carbon activation time, resulting in an increase in the number of micropores and surface area but resulting in no real change in pore size or pore distribution.

根據本發明所屬技術領域中具有通常知識者所使用之命名法，吸附材料中直徑低於2nm之孔隙稱為「微孔」，以及具有介於2nm及50nm之間之直徑之孔隙稱為「中孔」。若孔隙直徑超過50nm，則其稱為「巨孔(macropores)」。具有大於500nm之直徑之孔隙通常不會顯著提供多孔性材料之吸附性。 According to the nomenclature used by those of ordinary skill in the art to which the present invention is used, pores having a diameter of less than 2 nm in the adsorbent material are referred to as "micropores", and pores having a diameter between 2 nm and 50 nm are referred to as "middles". hole". If the pore diameter exceeds 50 nm, it is called "macropores". Pores having a diameter greater than 500 nm generally do not significantly provide the adsorptivity of the porous material.

在成功地建立多孔性碳材料展現自菸草煙的汽相優異的非所欲物質一般過濾(general filtration)的同時，有某些煙汽組份展現相當低程度的吸附，且此些組份包括低分子量醛(如甲醛)及氫化氰(HCN)。 While successfully establishing a porous carbon material that exhibits an excellent undesired general filtration of the vapor phase of tobacco smoke, certain smoke components exhibit a relatively low degree of adsorption, and such components include Low molecular weight aldehydes (such as formaldehyde) and hydrogen cyanide (HCN).

在多孔性碳表面上存在的不同化合物已發現亦影響碳吸附性質。 Different compounds present on the surface of porous carbon have been found to also affect carbon adsorption properties.

本發明追求提供一種用於製備多孔性碳之方法，該多孔性碳具有增強的低分子量醛與HCN之選擇性吸附。 The present invention seeks to provide a process for the preparation of porous carbon having enhanced selective adsorption of low molecular weight aldehydes with HCN.

發明摘述Summary of the invention

因此，在根據本發明第一觀點中，提供一種製備用於煙過濾之多孔性碳之方法，該方法包含在聚縮合及/或碳化前施加碳酸鎂至碳，使得該碳成為經碳酸鎂浸漬。 Accordingly, in accordance with a first aspect of the present invention, there is provided a method of preparing porous carbon for smoke filtration, the method comprising applying magnesium carbonate to carbon prior to polycondensation and/or carbonization such that the carbon is impregnated with magnesium carbonate .

根據本發明第二個觀點，提供一種多孔性碳，其藉由或可藉由根據第一觀點之方法獲得。 According to a second aspect of the invention, there is provided a porous carbon obtainable by or by a method according to the first aspect.

根據本發明第三個觀點，提供一種用於吸煙物件之過濾元件，其包含根據本發明第二觀點之多孔性碳。 According to a third aspect of the present invention, there is provided a filter element for a smoking article comprising porous carbon according to the second aspect of the present invention.

根據本發明第四個觀點，提供一種吸煙物件，其包含根據本發明第二觀點之多孔性碳。 According to a fourth aspect of the present invention, there is provided a smoking article comprising the porous carbon according to the second aspect of the present invention.

發明詳述Detailed description of the invention

本發明係關於一種方法，其包含施加碳酸鎂至多孔性碳，使得該多孔性碳成為經碳酸鎂浸漬，且因此具有增加的吸附劑性質。 The present invention is directed to a method comprising applying magnesium carbonate to a porous carbon such that the porous carbon is impregnated with magnesium carbonate and thus has increased adsorbent properties.

在本發明之一個具體實例中，多孔性碳係碳酸化形式(carbonated form)之有機材料，如椰殼。 In one embodiment of the invention, the porous carbon is an organic material in a carbonated form, such as a coconut shell.

在本發明之另一具體實例中，多孔性碳係以樹脂為基質之合成碳，如藉由醛與苯酚之聚縮合而製備之碳。若有的話，可使用可商購之聚縮物。 In another embodiment of the present invention, the porous carbon is a synthetic carbon based on a resin, such as carbon prepared by polycondensation of an aldehyde with phenol. If available, commercially available polycondensates can be used.

為了製造聚縮物，起始材料可為酚系化合物，如苯酚、間苯二酚、兒茶素、對苯二酚及間苯三酚，以及醛，如甲醛、乙二醛、戊二醛或糠醛。通常使用且較佳之反 應混合物包含間苯二酚(1,3-二羥苯)及甲醛，其在鹼性條件下彼此反應以形成膠狀聚縮物。聚縮合法通常在水性條件下進行。 In order to produce a polycondensate, the starting material may be a phenolic compound such as phenol, resorcinol, catechin, hydroquinone and phloroglucinol, and an aldehyde such as formaldehyde, glyoxal, glutaraldehyde. Or furfural. Usually used and better The mixture should contain resorcinol (1,3-dihydroxybenzene) and formaldehyde which react with each other under basic conditions to form a colloidal polycondensate. The polycondensation process is usually carried out under aqueous conditions.

聚縮合反應之速率與所得凝膠之交聯度可(例如)受到醇及催化劑之相對量影響。本發明所屬技術領域中具有通常知識者能夠知道如何調整用於達到所欲結果之此些成分的量。 The rate of crosslinking of the polycondensation reaction with the resulting gel can be affected, for example, by the relative amounts of alcohol and catalyst. Those of ordinary skill in the art to which the present invention pertains can know how to adjust the amount of such ingredients used to achieve the desired result.

為了製造所欲尺寸之粒子，已顯示在另外加工前降低聚縮物之尺寸係有利的。聚縮物的尺寸降低可使用常見機械尺寸降低技術或研磨進行。較佳地，尺寸降低步驟導致具有所欲尺寸分布之顆粒形成，藉此實質上避免粉末部分的形成。 In order to produce particles of the desired size, it has been shown to be advantageous to reduce the size of the polycondensate prior to additional processing. The reduction in size of the polycondensate can be done using common mechanical size reduction techniques or grinding. Preferably, the size reduction step results in the formation of particles having a desired size distribution whereby the formation of the powder portion is substantially avoided.

有機材料或聚縮物(其視情況地已降低粒徑)隨後接受熱裂解。熱裂解亦可描述為碳化。 The organic material or polycondensate, which optionally has a reduced particle size, is then subjected to thermal cracking. Thermal cracking can also be described as carbonization.

碳化描述在缺少空氣下熱裂解材料以移除作為揮發性化合物之大部分除碳以外的元素之程序。 Carbonization describes a procedure for thermally cracking a material in the absence of air to remove elements other than carbon that are volatile compounds.

碳化可使用任何合適方法達到，且這樣的方法對於本發明所屬技術領域中具有通常知識者是熟悉的。合適的方法包括粉末套管法(pit method)、滾筒法(drum method)及分解蒸餾。利用H3PO4或ZnCl2之碳化法增加材料中微孔的比例，且亦增加材料中碳的比例。然而，此方法亦可能增加碳材料中非所欲無機化合物的比例。這樣的無機化合物可藉由密集的(intensive)清洗程序移除。 Carbonization can be achieved using any suitable method, and such methods are familiar to those of ordinary skill in the art to which the invention pertains. Suitable methods include a powder pit method, a drum method, and decomposition distillation. The carbonization of H 3 PO 4 or ZnCl 2 increases the proportion of micropores in the material and also increases the proportion of carbon in the material. However, this method may also increase the proportion of undesired inorganic compounds in the carbon material. Such inorganic compounds can be removed by an intensive cleaning procedure.

條件可取決於規模而有所不同。然而，保溫(incubation)溫度及時間可分別介於300℃及1000℃之間，以及30分鐘及4小時之間。例如，熱裂解步驟可包括加熱經預處理碳至至少500℃的溫度及維持碳在該溫度下數小時。在一個具體實例中，熱裂解步驟包含在以10-200cm3/min的速率流動之N2下，以5-10℃/分鐘的速率加熱經預處理之碳至600℃。 Conditions can vary depending on size. However, the incubation temperature and time can be between 300 ° C and 1000 ° C, respectively, and between 30 minutes and 4 hours. For example, the thermal cracking step can include heating the pretreated carbon to a temperature of at least 500 ° C and maintaining carbon at the temperature for several hours. In one embodiment, the thermal cracking step comprises heating the pretreated carbon to 600 ° C at a rate of 5-10 ° C/min under N 2 flowing at a rate of 10-200 cm 3 /min.

在熱裂解後，冷卻碳，並且較佳例如藉由暴露於潮濕的N2流使碳表面去活化。此去活化係較佳的，因為高風險的導致赤熱之放熱O2吸附。 After pyrolysis, the carbon was cooled, and preferably, for example, by exposure to moist N 2 stream to the activated carbon surface. This deactivation system is preferred because of the high risk of exothermic O 2 adsorption of red heat.

接者，活化經熱裂解之碳，以增加表面積。在此方法中，材料中現存孔隙及坑(pits)被打開及擴大，以產生具有大表面積之材料，其富含微孔及中孔。 In addition, the thermally cracked carbon is activated to increase the surface area. In this method, existing pores and pits in the material are opened and expanded to produce a material having a large surface area rich in micropores and mesopores.

材料可藉由任何方法活化，且本發明所屬技術領域中具有通常知識者可知物理或化學方法可能是合適的。較佳地，材料係藉由物理方法活化，且最佳地，材料係使用氮和蒸氣，或者CO2而活化。 The materials may be activated by any method, and those of ordinary skill in the art to which the invention pertains may be aware that physical or chemical methods may be suitable. Preferably, the material system activated by physical methods, and, most preferably, the material-based vapor and nitrogen, or CO 2 activation.

在一個本發明之具體實例中，材料係藉由在窯(如旋轉窯)中經控制之氮氛圍下與蒸氣之反應而活化。 In one embodiment of the invention, the material is activated by reaction with a vapor under a controlled nitrogen atmosphere in a kiln (e.g., a rotary kiln).

在活化方法中，溫度係重要的。若溫度太低，則反應變慢且不經濟。換言之，若溫度太高，則反應變成擴散控制且導致材料損失。 In the activation process, the temperature is important. If the temperature is too low, the reaction becomes slow and uneconomical. In other words, if the temperature is too high, the reaction becomes diffusion controlled and results in material loss.

活化方法較佳進行30分鐘與4小時之間。最佳地，活化材料1小時。 The activation method is preferably carried out between 30 minutes and 4 hours. Optimally, the material was activated for 1 hour.

在一替代的具體實例中，材料係藉由與二氧化碳之反應而活化。在此情況中，材料之活化可在700℃與1100℃之間的溫度下進行，且較佳地活化係在800℃與1000℃之間的溫度下進行。最佳地，材料係在約900℃下活化。 In an alternate embodiment, the material is activated by reaction with carbon dioxide. In this case, the activation of the material can be carried out at a temperature between 700 ° C and 1100 ° C, and preferably the activation system is carried out at a temperature between 800 ° C and 1000 ° C. Most preferably, the material is activated at about 900 °C.

可使用化學活化方法。例如：KOH或ZnCl2可用於活化材料。然而，化學活化方法可能導致化學物質沉積於碳材料中，其可能是非所欲的。這樣的化學物質可能使用密集的清洗程序而移除。 A chemical activation method can be used. For example: KOH or ZnCl 2 can be used to activate the material. However, chemical activation methods may result in the deposition of chemicals in the carbon material, which may be undesirable. Such chemicals may be removed using intensive cleaning procedures.

活化後，材料粒徑降低10%至40%之間，且較佳材料粒徑降低20%至30%之間。 After activation, the particle size of the material is reduced by between 10% and 40%, and the preferred material size is reduced by between 20% and 30%.

根據本發明方法製得之材料將具有足夠小以提供對於煙過濾之大表面積的粒子。然而，活性碳材料的粒子應足夠大使通過過濾器之煙不受限制。亦重要的是，粒子係足夠大到，使他們不能成為夾帶於煙中且通過過濾器而被吸煙者吸入。碳係非有害的，但吸入碎片仍然對於使用者會是不愉快的。 The material produced in accordance with the method of the present invention will have particles small enough to provide a large surface area for smoke filtration. However, the particles of the activated carbon material should be sufficiently large that the smoke passing through the filter is not limited. It is also important that the particle systems are large enough that they cannot be entrained in the smoke and inhaled by the smoker through the filter. Carbon is not harmful, but inhaling debris is still unpleasant for the user.

另一方面，若碎片太大，則碎片的表面積對體積比率會是使得過濾效率降低。 On the other hand, if the fragments are too large, the surface area to volume ratio of the fragments may be such that the filtration efficiency is lowered.

考量此些因素，藉由所請方法製得之活性碳較佳應具有在10μm及1500μm之間範圍中之粒徑。較佳地，平均粒徑係介於100μm及1000μm之間，及更佳介於150μm及800μm之間。最佳地，活性碳材料之粒子具有250μm及750μm之間的平均尺寸。 In view of such factors, the activated carbon produced by the claimed method should preferably have a particle size in the range between 10 μm and 1500 μm. Preferably, the average particle size is between 100 μm and 1000 μm, and more preferably between 150 μm and 800 μm. Most preferably, the particles of the activated carbon material have an average size of between 250 μm and 750 μm.

活性碳表面積係藉由測量被材料吸附之氮體積的變化，其關於常溫下氮分壓。藉由源自於Brunauer’、Emmett及Teller之數學模式的結果分析導致一已知為BET表面積之數值。 The activated carbon surface area is measured by the change in the volume of nitrogen adsorbed by the material, which is related to the partial pressure of nitrogen at normal temperature. Analysis of the results by mathematical models derived from Brunauer', Emmett, and Teller resulted in a value known as the BET surface area.

本發明中所使用之活性碳材料的BET表面積理想地係為至少800m2/g，較佳至少900m2/g，且期望地至少1000、1100、1150、1200、1250、1300或1350m2/g。對於藉由本發明方法製得之碳材料的BET表面積之典型數值係高至約1000、1050、1100、1150、1200、1250、1300、1400、1500、1600、1700、1800或1900m2/g。具有介於1000m2/g及1500m2/g之間之BET表面積的多孔性碳材料係較佳的，且具有介於1200m2/g及1400m2/g之間之表面積的材料係最佳的。然而，MgCO3浸漬甚至對於具有低至450m2/g的低表面積之活性碳作用，如以下實例中所示。 In the present invention, the BET surface area of the activated carbon material is desirably used based at least 800m 2 / g, preferably at least 900m 2 / g, and desirably at least 1000,1100,1150,1200,1250,1300 or 1350m 2 / g . Typical values for the BET surface area of the carbon material produced by the process of the present invention are as high as about 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1400, 1500, 1600, 1700, 1800 or 1900 m 2 /g. 1000m between having a porous carbon material-based BET of between 2 / g and 1500m 2 / g surface area preferred, and has between 2 / surface area of between 2 / g 1200m g and materials based optimal 1400m . However, MgCO 3 impregnation even acts on activated carbon having a low surface area as low as 450 m 2 /g, as shown in the examples below.

活性碳材料中，微孔、中孔及巨孔之相對體積可使用熟知氮吸附及水銀孔隙度儀(mercury porosimetry)技術來估計。水銀孔隙度儀可用於估計中孔及巨孔之體積。氮吸附可用於估計微孔及中孔之體積，其使用所謂的BJH數學模式。然而，由於對於估計之理論基礎係不同的，藉由該等兩種方法獲得之數值無法直接彼此比較。 In activated carbon materials, the relative volumes of micropores, mesopores, and macropores can be estimated using well-known nitrogen adsorption and mercury porosimetry techniques. Mercury porosimeter can be used to estimate the volume of mesopores and macropores. Nitrogen adsorption can be used to estimate the volume of micropores and mesopores, using the so-called BJH mathematical model. However, since the theoretical basis for the estimation is different, the values obtained by the two methods cannot be directly compared with each other.

本發明之方法可使用具有通常適用於煙過濾的任何孔隙結構之活性碳材料，亦即其可包括微孔、中孔及 可能的巨孔。在本發明某些合適的碳材料中，至少20%但期望地不高於65%的孔隙體積(如藉由氮吸附之估計)係中孔。如本發明碳材料之經組合的微孔及中孔體積白分比，對於中孔體積之典型最小值係25%、35%或45%。對於這樣的體積之典型最大值係55%、60%或65%。較佳地，本發明碳材料之中孔係在25% and 55%之間之經組合的中孔及微孔體積範圍中。 The method of the present invention may use an activated carbon material having any pore structure generally suitable for smoke filtration, that is, it may include micropores, mesopores, and Possible giant holes. In some suitable carbon materials of the invention, at least 20% but desirably no more than 65% of the pore volume (as estimated by nitrogen adsorption) is mesopores. The combined micropore and mesopore volume white fraction of the carbon material of the present invention is typically 25%, 35% or 45% for the mesopore volume. A typical maximum for such a volume is 55%, 60% or 65%. Preferably, the pore structure of the carbon material of the present invention is in the range of combined mesoporosity and micropore volume between 25% and 55%.

本發明中所使用之多孔性碳材料較佳具有至少0.4cm3/g，且期望地至少0.5、0.6、0.7、0.8或0.9cm3/g之孔隙體積(如藉由氮吸附而估計)。具有至少0.5cm3/g的孔隙體積之碳材料係特別有用於作為用於菸草煙之吸附劑。具有顯著更高於較佳數值的孔隙體積之碳材料，可能密度低，且因此在香菸製造設備中不容易處理。這樣的碳材料對於為了該原因用於香菸或煙過濾器之用途係較不受歡迎的。 As used in the present invention, the porous carbon material preferably has at least 0.4cm 3 / g, and desirably at least 0.5,0.6,0.7,0.8 or 0.9cm 3 / g of pore volume (as estimated by nitrogen adsorption). A carbon material having a pore volume of at least 0.5 cm 3 /g is particularly useful as an adsorbent for tobacco smoke. Carbon materials having a pore volume that is significantly higher than the preferred values may be low in density and therefore not easily handled in cigarette manufacturing equipment. Such carbon materials are less desirable for use in cigarettes or smoke filters for this reason.

活性碳材料之孔隙結構及密度係緊密有關的。一般而言，材料孔隙體積越大，則密度越低。 The pore structure and density of activated carbon materials are closely related. In general, the larger the pore volume of the material, the lower the density.

本發明中所使用之活性碳材料較佳地具有大於0.25g/cm3，且較佳大於0.3g/cm3之總體密度(bulk densities)。活性碳材料可具有高至0.7g/cm3、0.6g/cm3或0.5g/cm3之總體密度。 The activated carbon material used in the present invention preferably has a bulk densities of more than 0.25 g/cm 3 and preferably more than 0.3 g/cm 3 . The activated carbon material may have an overall density of up to 0.7 g/cm 3 , 0.6 g/cm 3 or 0.5 g/cm 3 .

飽和碳酸鎂鹼性溶液可用於本發明。使用過量飽和溶液，且加入1%碳重量之飽和溶液。然而，亦可使用其他溶劑結合鎂鹽。此溶液可隨後藉由浸泡或噴塗而施加至碳，其中其用作為催化劑。 A saturated magnesium carbonate alkaline solution can be used in the present invention. An excess of saturated solution was used and a 1% carbon by weight saturated solution was added. However, other solvents may also be used in combination with the magnesium salt. This solution can then be applied to the carbon by soaking or spraying, where it is used as a catalyst.

在施加碳酸鎂後，不洗滌多孔性碳，以移除過量之碳酸鹽。 After the application of magnesium carbonate, the porous carbon is not washed to remove excess carbonate.

以上所述被認為是本發明較佳具體實例。然而，本發明所屬技術領域中具有通常知識者將認知到可進行變換及修改而不偏離本發明之範圍。 The above description is considered to be a preferred embodiment of the present invention. However, it will be appreciated by those of ordinary skill in the art that the invention can be modified and modified without departing from the scope of the invention.

實例 Instance

製作一樣本，稱為「+ MgO3」。此係使用間苯二酚及甲醛(40：60比率)而合成。使用作為催化劑之碳酸鎂、使用飽和碳酸鎂鹼性溶液、以熱固化(在40℃三天或在90℃六小時)誘發聚縮合。凝膠形成，其係經乾燥(在室溫2天或在90℃過夜)。經乾燥之凝膠係在600-900℃、較佳800℃下2-8小時、較佳3至4小時於氮中熱裂解。在此特別實例中，不使用活化但活化可用於達到更高表面積及孔隙度。 Make the same book, called "+ MgO 3 ". This was synthesized using resorcinol and formaldehyde (40:60 ratio). The polycondensation was induced using magnesium carbonate as a catalyst, using a saturated magnesium carbonate alkaline solution, and thermally curing (three hours at 40 ° C or six hours at 90 ° C). Gel formation, which was dried (over 2 days at room temperature or overnight at 90 ° C). The dried gel is thermally cracked in nitrogen at 600-900 ° C, preferably 800 ° C for 2-8 hours, preferably 3 to 4 hours. In this particular example, no activation is used but activation can be used to achieve higher surface area and porosity.

使用索氏體(其為無機碳)作為控制組。此材料具有相似於上述段落所提及之樣本之表面積與孔隙度。兩種碳主要為具有450m2/g表面積及0.24 cm3/g孔隙體積之微孔。 Sorbite, which is inorganic carbon, was used as the control group. This material has surface area and porosity similar to those of the samples mentioned in the above paragraphs. The two carbons are mainly micropores having a surface area of 450 m 2 /g and a pore volume of 0.24 cm 3 /g.

如圖1中可見，具有經碳酸鎂浸漬之碳，有顯著降低丙烯醛、甲醛及HCN之程度以及降低其他組份。 As can be seen in Figure 1, having carbon impregnated with magnesium carbonate significantly reduces the extent of acrolein, formaldehyde and HCN and reduces other components.

總而言之，實例指出根據本發明之方法，施加碳酸鎂至多孔性碳提供具有增強煙汽相組份吸附之多孔性碳。 In summary, the examples indicate that the application of magnesium carbonate to porous carbon in accordance with the method of the present invention provides porous carbon with enhanced adsorption of the vapor phase component.

為了更充分瞭解本發明，參照圖1，其說明對於具有施加碳酸鎂之活性碳(+ MgCO3)與無施加碳酸鎂之活性碳(索氏體(sorbite))的比較，煙的某些成分百分比降低。 In order to more fully understand the present invention, reference is made to Figure 1, which illustrates certain components of smoke for comparison with activated carbon (+ MgCO 3 ) with applied magnesium carbonate and activated carbon (sorbite) without applied magnesium carbonate. The percentage is reduced.

Claims (12)

一種製備用於煙過濾之多孔性碳之方法，該方法包含在聚縮合及/或碳化前施加碳酸鎂至碳，使得該多孔性碳成為經碳酸鎂浸漬。 A method of preparing porous carbon for smoke filtration, the method comprising applying magnesium carbonate to carbon prior to polycondensation and/or carbonization such that the porous carbon is impregnated with magnesium carbonate. 如申請專利範圍第1項之方法，其中該碳係有機材料形式。 The method of claim 1, wherein the carbon is in the form of an organic material. 如申請專利範圍第2項之方法，其中該有機材料係以植物為基質之材料。 The method of claim 2, wherein the organic material is a plant-based material. 如申請專利範圍第3項之方法，其中該有機材料係椰殼。 The method of claim 3, wherein the organic material is a coconut shell. 如申請專利範圍第1項之方法，其中該碳係以樹脂為基質之合成碳。 The method of claim 1, wherein the carbon is a synthetic carbon based on a resin. 如申請專利範圍第5項之方法，其中該以樹脂為基質之合成碳係藉由醛與酚系化合物之聚縮合而製備。 The method of claim 5, wherein the resin-based synthetic carbon is prepared by polycondensation of an aldehyde with a phenolic compound. 如申請專利範圍第6項之方法，其中該酚系化合物係間苯二酚。 The method of claim 6, wherein the phenolic compound is resorcinol. 如申請專利範圍第6或7項之方法，其中該醛係甲醛。 The method of claim 6 or 7, wherein the aldehyde is formaldehyde. 如上述申請專利範圍中任一項之方法，其中該碳酸鎂係藉由浸泡或噴塗而施加至該多孔性碳。 A method according to any one of the preceding claims, wherein the magnesium carbonate is applied to the porous carbon by dipping or spraying. 一種多孔性碳，其係藉由或可藉由如上述申請專利範圍中任一項之方法獲得。 A porous carbon obtained by or by a method as claimed in any one of the above claims. 一種用於吸煙物件之過濾元件，其包含如申請專利範圍第10項之多孔性碳。 A filter element for smoking articles comprising porous carbon as in claim 10 of the patent application. 一種吸煙物件，其包含如申請專利範圍第10項之多孔性碳。 A smoking article comprising porous carbon as in claim 10 of the patent application.
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