574139 A7 B7 五、發明説明（1 ) 發明領域 本發明主要係關於一種含硫粉狀活性碳之製備方法，特 別地，係關於一種利用含碳原料直接製得含硫粉狀活性碳 之製備方法， 發明背景 隨著高度工業化的發展以及人口的急遽增加，垃圾、有 毒物質對空氣、及水的污染已成為現代都市中揮之不去的 夢魘。據統計，在台灣每天約產生超過20,000噸之都市垃 圾，而這些垃圾大部分經由垃圾焚化爐高溫燃燒處理。然 而，在燃燒過程中/各式各樣包含有機或無機的垃圾都可 能會產生許多廢氣，若未經妥善處理，即會形成二次污 染。 目前粉狀活性碳廣泛應用於工業上廢氣與毒性物質之處 理上，其中對於煙道廢氣中之重金屬與戴奥辛之吸附效果 更佳。一般都市垃圾焚化爐燃燒後之廢氣，大都需經過半 乾式噴霧塔與袋式集塵器予以處理再排放至大氣中，而粉 狀活性碳則可在上述之處理過程中噴入，藉以去除有害性 氣體。然而微量即會對人體造成極大威脅之元素汞（HgG)或 氧化後之汞金屬離子（Hg2 + )如氯化汞，卻無法由一般的粉 狀活性碳完全吸附，必須經由添加硫成為含硫粉狀活性碳 與汞形成硫化汞（HgS)而去除。 目前含硫粉狀活性碳之製備為首先生成粉狀活性碳，再 經由置於含硫離子如硫化鋼、硫化钟、二硫化碳等無機硫 化物之溶液中反應，使粉狀活性碳的表面吸附硫而製得。 -4- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐)574139 A7 B7 V. Description of the invention (1) Field of the invention The present invention relates mainly to a method for preparing sulfur-containing powdered activated carbon, and in particular, to a method for preparing sulfur-containing powdered activated carbon directly from carbon-containing raw materials. Background of the Invention With the development of a high degree of industrialization and the rapid increase in population, the pollution of air and water by garbage and toxic substances has become a lingering nightmare in modern cities. According to statistics, more than 20,000 tons of municipal waste is produced in Taiwan every day, and most of this waste is processed by high-temperature combustion of waste incinerators. However, during the combustion process / various types of waste containing organic or inorganic materials, many exhaust gases may be generated, and if not properly treated, secondary pollution may form. At present, powdered activated carbon is widely used in industrial waste gas and toxic substances. Among them, the adsorption effect of heavy metals and dioxin in flue gas is better. Most of the waste gas from the combustion of general municipal waste incinerators needs to be treated by semi-dry spray towers and bag dust collectors before being discharged to the atmosphere. Powdered activated carbon can be sprayed during the above-mentioned treatment process to remove harmful substances.性 气。 Sexual gas. However, trace amounts of elemental mercury (HgG) or oxidized mercury metal ions (Hg2 +) such as mercury chloride cannot be completely adsorbed by ordinary powdered activated carbon, and must be added to sulfur by adding sulfur. Powdered activated carbon forms mercury sulfide (HgS) with mercury and is removed. At present, sulfur-containing powdered activated carbon is prepared by first generating powdery activated carbon, and then reacting in a solution containing sulfur ions such as sulfurized steel, sulfurized bell, carbon disulfide and other inorganic sulfides to adsorb sulfur on the surface of the powdered activated carbon. And made. -4- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)
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574139 A7 B7 五、發明説明（2 ) 然而隨著含硫量之增加，粉狀活性碳的表面積卻相對減 少，造成所製得之含硫粉狀活性碳整體的吸附作用因而未 見顯著提升。 再者，目前製備粉狀活性碳的方法係採用含碳原料製 造，隨著環保意識的抬頭，目前已研究出許多利用廢輪胎 以製得碳黑再行製備粉狀活性碳的方法，如中華民國專利 公告第462984號。利用廢輪胎製備碳黑可一併解決大量廢輪 胎的處理問題，然而將廢輪胎製成碳黑，再製成粉狀活性 碳不但過程複雜，且消耗極大之能源。 基於此，本發明乃致力於開發一新穎且節約能源之利用 含碳原料如廢輪胎及碳黑直接製備含硫粉狀活性碳之方 法，以同時達到增加硫含量及不減少活性碳表面積，且可 再利用廢輪胎及碳黑之目的。 發明概述 本發明之目的在於提供一種含硫粉狀活性碳之製備方 法，其包含將含碳原料如廢輪胎及碳黑進行熱裂解反應， 並於熱裂解反應時導入含硫溶液，以製得該含硫粉狀活性 碳。本發明具有可直接將含碳原料製成含硫粉狀活性碳之 優點，可簡化製程、節約能源並降低成本，所製得之含硫 粉狀活性碳具有大表面積，而深具產業利用性。 圖式簡要說明 本發明將以下列圖示進一步說明，其中 圖1表示含硫粉狀活性碳製備示意圖； 圖2表示含硫溶液導入速率-產物比率關係圖； -5- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 574139 A7 B7 五、發明説明（3 ) 圖3表示含硫溶液導入速率-表面積關係圖； 圖4表示熱裂解反應時間-產物比率關係圖；及 圖5表示熱裂解反應時間-表面積關係圖。 元件符號說明 1表示氮氣源 2表示氮氣控制閥門 3表示氧氣驅趕裝置 4表示蠕動幫浦 5表示含硫溶液導入口 6表示導入孔 7表示加熱管 8表TF反應爐 9表示廢輪胎 10表示冷卻管 1 1表示產物收集袋 12表示產物控制閥門 13表示可燃氣排放孔. 14表示衝擊吸收瓶 15表示冰浴槽 發明詳細說明 本發明係關於一種含硫粉狀活性碳之製備方法，其係將 含碳原料，於導入含硫溶液之環境中進行熱裂解反應，以 製得該含硫粉狀活性碳。 根據本發明，可提供做為含碳原料包含碳黑及廢輪胎， -6 - 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 574139 A7 B7 五、發明説明（4 ) 其中廢輪胎包含但不限於卡車輪胎（truck tires)、汽車輪胎 (automobile tires)或一般交通工具輪胎（vehicles tires)。該等 廢輪胎先經去除金屬帶（metallic belt)，但仍保留輪胎中之合 成中心股（synthetic cords)。此預先處理過的廢輪胎於小規模 製造含硫粉狀活性碳時，視需要可先粉碎成小塊，然於大 量製造時，則可將整個預先處理過的廢輪胎進行反應。 裝574139 A7 B7 V. Description of the invention (2) However, as the sulfur content increases, the surface area of the powdered activated carbon is relatively reduced, resulting in the overall adsorption of the sulfur-containing powdered activated carbon that has not been significantly improved. In addition, the current method for preparing powdered activated carbon is to use carbon-containing raw materials. With the rising awareness of environmental protection, many methods have been developed by using waste tires to produce carbon black and then preparing powdered activated carbon, such as China. Republic of China Patent Bulletin No. 462984. The use of waste tires to prepare carbon black can also solve the problem of treating a large number of waste tires. However, making waste tires into carbon black and then making powdered activated carbon is not only a complicated process and consumes a lot of energy. Based on this, the present invention is dedicated to developing a novel and energy-saving method for directly preparing sulfur-containing powdered activated carbon using carbon-containing raw materials such as waste tires and carbon black, so as to simultaneously increase the sulfur content and not reduce the surface area of activated carbon, and The purpose of reusing waste tires and carbon black. SUMMARY OF THE INVENTION The object of the present invention is to provide a method for preparing sulfur-containing powdered activated carbon, which comprises subjecting carbon-containing raw materials such as waste tires and carbon black to a thermal cracking reaction, and introducing a sulfur-containing solution during the thermal cracking reaction to obtain The sulfur-containing powdered activated carbon. The invention has the advantages of directly making carbon-containing raw materials into sulfur-containing powdered activated carbon, which can simplify the process, save energy and reduce costs. The obtained sulfur-containing powdered activated carbon has a large surface area and has deep industrial applicability . Brief description of the drawings The present invention will be further explained with the following diagrams, in which FIG. 1 shows a schematic diagram of the preparation of sulfur-containing powdered activated carbon; FIG. 2 shows the relationship between the introduction rate of sulfur-containing solution and the product ratio; Standard (CNS) A4 specification (210 X 297 mm) 574139 A7 B7 V. Description of the invention (3) Figure 3 shows the sulfur-containing solution introduction rate-surface area relationship diagram; Figure 4 shows the thermal cracking reaction time-product ratio relationship diagram; and Fig. 5 is a graph showing the time-surface area relationship of the thermal cracking reaction. Description of component symbols 1 indicates a nitrogen source 2 indicates a nitrogen control valve 3 indicates an oxygen drive device 4 indicates a peristaltic pump 5 indicates a sulfur-containing solution inlet 6 indicates an introduction hole 7 indicates a heating tube 8 indicates a TF reaction furnace 9 indicates a waste tire 10 indicates a cooling tube 1 1 indicates a product collection bag 12 indicates a product control valve 13 indicates a flammable gas discharge hole. 14 indicates an impact absorption bottle 15 indicates an ice bath. Detailed description of the invention The present invention relates to a method for preparing sulfur-containing powdered activated carbon, which contains carbon The raw materials are subjected to a thermal cracking reaction in an environment where a sulfur-containing solution is introduced to obtain the sulfur-containing powdered activated carbon. According to the present invention, carbon black and waste tires can be provided as carbon-containing raw materials. -6-This paper size is applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) 574139 A7 B7 V. Description of the invention (4) The waste tires include but are not limited to truck tires, automobile tires, or general vehicle tires. These scrap tires were first removed from the metallic belt, but the synthetic cords in the tires remained. This pre-treated waste tire can be pulverized into small pieces as needed when manufacturing sulfur-containing powdered activated carbon on a small scale. However, during mass production, the entire pre-treated waste tire can be reacted. Hold
本發明所言之「熱裂解反應」係指在無氧或缺氧狀態 下，加熱含碳原料使其分解產生可燃氣、燃油及碳，然而 「熱裂解反應」產物成分及比例因熱裂解反應之起始物質 及操作條件而不同。此熱裂解反應為一吸熱反應，且可視 需要選定不同之反應溫度，根據本發明，所進行的熱裂解 溫度為約3 00 °C至約900°C，較佳係為約800°C至約900°C。熱 裂解反應中無氧或缺氧狀態維持方法為熟習該項技術者所 熟知，在一較佳實施例中，該熱裂解反應無氧或缺氧狀態 的維持係採一氧氣驅趕裝置處理。另一方面，熱裂解反應 的反應時間可視所需之含硫量及表面積大小而決定，較佳 係為小於200分鐘，更佳係為約50分鐘至約180分鐘。 本發明之特徵在於廢輪胎進行熱裂解反應時導入含硫溶 液。本發明所言之「含硫溶液」係指可提供硫離子之溶 液，其包含硫化钾或碳化鈉等無機硫化物溶液，較佳係為 硫化鈉溶液。該導入的含硫溶液可作為活化劑，在熱裂解 反應中，該含硫溶液被加熱成為蒸氣，該蒸氣可穿透入含 碳原料中，並製造出孔徑大小不同之孔隙，同時，硫離子 也立刻被吸附於活性碳表面而形成含硫粉狀活性碳；另一 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 574139 A7 B7 五、發明説明（5 )The "thermal cracking reaction" referred to in the present invention refers to heating carbon-containing raw materials to decompose to produce combustible gas, fuel oil, and carbon in an anaerobic or anoxic state. The starting materials and operating conditions vary. This thermal cracking reaction is an endothermic reaction, and different reaction temperatures can be selected according to the needs. According to the present invention, the thermal cracking temperature is about 300 ° C to about 900 ° C, preferably about 800 ° C to about 900 ° C. The method for maintaining the anaerobic or anoxic state in the thermal cracking reaction is well known to those skilled in the art. In a preferred embodiment, the maintenance of the anaerobic or anoxic state of the thermal cracking reaction is performed by an oxygen driving device. On the other hand, the reaction time of the thermal cracking reaction may be determined depending on the required sulfur content and surface area, and is preferably less than 200 minutes, and more preferably about 50 minutes to about 180 minutes. The present invention is characterized in that a sulfur-containing solution is introduced when a waste tire is subjected to a thermal cracking reaction. The "sulfur-containing solution" referred to in the present invention refers to a solution capable of providing sulfur ions, and includes an inorganic sulfide solution such as potassium sulfide or sodium carbide, and is preferably a sodium sulfide solution. The introduced sulfur-containing solution can be used as an activator. In the thermal cracking reaction, the sulfur-containing solution is heated into steam, and the steam can penetrate into the carbon-containing raw material, and produce pores with different pore sizes. At the same time, sulfur ions It is also immediately adsorbed on the surface of activated carbon to form sulfur-containing powdered activated carbon; another paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) 574139 A7 B7 V. Description of the invention (5)
裝 方面，因硫離子之粒子較大，在被吸附的同時也會撞擊活 性碳表面而增大表面積，此撞擊作用使得硫離子吸附於活 性碳之表面吸附作用中所減少的吸附表面積增加，這兩種 作用的競合，使含硫量與表面積於不同反應條件下會有所 不同。當吸附的作用大於撞擊作用時，該含硫粉狀活性碳 之表面積隨含硫量增加而減小，然而當撞擊作用大於吸附 作用時，則使得該含硫粉狀活性碳之表面積隨含硫量增加 而增加。此與習用含硫粉狀活性碳表面積因含硫量增加而 減少之機制大不相同。 於熱裂解反應中，反應越劇烈（如含硫溶液導入速率越大 和濃度越大）或反應時間越久，撞擊之效應亦增大，使得活 性碳的表面積亦增大，然而另一方面，因含碳原料的充分 反應，產生較多的副產物如燃油及可燃氣，含繞粉狀活性 碳的比例反而因反應機會增加而減少。根據本發明，該含 硫溶液係以約0.5 0至約2 . OOmg-溶液/ g C-sec之速度導入熱 裂解反應中。且該含硫溶液濃度可依所需之硫含量及表面 積調整所需之濃度，於.製造一般使用之含硫粉狀活性碳 時，該含硫離子之濃度為約0.001M至約0.15M，以使用硫化 鈉溶液為例，含硫溶液濃度約為0.0 1重量％至1.0重量％。 又，為使該含硫溶液之導入更順暢，可使用氮氣作為導入 氣體，以防止發生溶液倒流，較佳地，氮氣的導入速率為 約0.3公升/分鐘至約0.8公升/分鐘。 於該熱裂解反應完成後，此高溫之熱裂解反應產物可再 經一冷卻步驟予以冷卻，如經由一冷卻管冷卻，或經冰浴 -8- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 574139In terms of equipment, due to the larger particles of sulfur ions, the surface area of the activated carbon will also be increased while being adsorbed. This impact will increase the surface area of adsorption reduced by the adsorption of sulfur ions on the surface of activated carbon. The competition between the two effects makes the sulfur content and surface area different under different reaction conditions. When the adsorption effect is greater than the impact effect, the surface area of the sulfur-containing powdered activated carbon decreases as the sulfur content increases. However, when the impact effect is greater than the adsorption effect, the surface area of the sulfur-containing powdered activated carbon varies with the sulfur content. The amount increases. This is very different from the mechanism by which the surface area of conventional sulfur-containing powdered activated carbon decreases due to an increase in sulfur content. In the thermal cracking reaction, the more violent the reaction (such as the greater the introduction rate and concentration of the sulfur-containing solution) or the longer the reaction time, the greater the impact of the impact, which increases the surface area of the activated carbon. The full reaction of carbon raw materials produces more by-products such as fuel oil and combustible gas, and the proportion of powdered activated carbon is reduced due to increased reaction opportunities. According to the present invention, the sulfur-containing solution is introduced into the thermal cracking reaction at a rate of about 0.50 to about 2,000 mg-solution / g C-sec. And the concentration of the sulfur-containing solution can be adjusted according to the required sulfur content and surface area. When manufacturing sulfur-containing powdered activated carbon for general use, the concentration of the sulfur-containing ion is about 0.001M to about 0.15M, Taking the use of a sodium sulfide solution as an example, the concentration of the sulfur-containing solution is about 0.01 to 1.0% by weight. In order to make the introduction of the sulfur-containing solution smoother, nitrogen gas may be used as an introduction gas to prevent the backflow of the solution. Preferably, the introduction rate of the nitrogen gas is about 0.3 liters / minute to about 0.8 liters / minute. After the thermal cracking reaction is completed, the high-temperature thermal cracking reaction product can be cooled through a cooling step, such as cooling through a cooling pipe, or through an ice bath. 8- This paper is in accordance with China National Standard (CNS) A4 (210 X 297 mm) 574139
冷卻。此冷卻步驟除可降低熱裂解反應產物之溫度外，更 可將其他副產物如可燃氣等冷卻而導人溶於水中，經此處 理’万可產生最少之可燃氣’以免對環境造成二次污染， 此外’所產生的燃油亦可生產替代性柴油，而作為能源使 用。 本备月具有多項優點·（1)因硫離子的吸附作用與撞擊作 用可同時增加粉狀活性後之含硫量及表面積；（2 )因於單 一步騾中同時完成自含碳原料至含硫粉狀活性碳之製造， 可大幅減少能源的使用及縮短製造時間；（3)因本發明可直 接利用廢輪胎作為含碳原料，可回收廢輪胎再利用，而減 少環境負擔。 兹以下列實例予以詳細說明本發明，惟並不意味本發明 僅侷限於此等實例所揭示之内容。 ^11-L含硫粉狀活性碳之製備 參考圖1之含硫粉狀活性碳製備示意圖，其中含碳原料係 為預先除去金屬帶並粉碎為約1至2cm3小塊之廢輪胎9，將 廢輪胎9置入一包含加熱管7之反應爐8中，並利用一氧氣驅 趕裝置3去除該反應爐8之氧氣。利用加熱管7將該等廢輪胎 9加熱至800°C至90CTC，進行熱裂解反應。 在熱裂解反應的同時，利用一蠕動幫浦4將不同濃度之硫 化鈉溶液經一含硫溶液導入口 5導入該反應爐7之一導入孔6 中，並調整導入速率為0.50至2.OOmg-溶液/g-含碳原料-s e c。同時利用一氮氣源1及一氮氣控制閥門2以〇 5公升/分 鐘之速率導入氮氣。 -9 - 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐) 574139 A7 B7 五、發明説明（7 ) 此熱裂解反應進行後，將產物經一冷卻管1 0冷卻，並由 一產物控制閥門1 2將含硫粉狀活性碳收集於一產物收集袋 1 1中，並將可燃氣經一可燃氣排放孔1 3排放，而產生的燃 油則由複數個置於冰浴槽1 5中之衝擊吸收瓶1 4而吸收。 實例2 :含硫粉狀活性碳之性質 含硫溶液導入速率與產物比率:根據實例1之方法，於反 應溫度800 °C進行熱裂解反應6 0分鐘，並於不同含硫溶液 (硫化鈉）導入速率下製備含硫粉狀活性碳，以觀察產物比率 的變化，其結果顯示於圖2。依此結果.，導入速率越大，產 物比率越低，此係因導入速率增大使得較多原料被撞擊並 能充分反應而釋出燃油及可燃氣，而有較低之產物比率。 含硫溶液導入速率與表面積:根據實例1之方法，於反應 溫度800°C進行熱裂解反應6 0分鐘，並於不同含硫溶液（硫 化鈉）導入速率下製備含硫粉狀活性碳，以觀察含硫粉狀活 性碳表面積的變化，其結果顯示於圖3。依此結果，導入速 率越大，含硫粉狀活性碳的表面積越大，此係因導入速率 增大使得硫離子之撞擊力增大，而形成較多孔洞，故有較 大之表面積。 熱裂解反應時間與產物比率:根據實例1之方法，於反應 溫度900 °C及硫化鋼導入速率為1.0 m g -溶液/ g -含碳原料-s e c之條件下進行熱裂解反應，以製備含硫粉狀活性碳，以 觀察熱裂解反應時間對產物比率的影響，其結果顯示於圖 4。依此結果，反應時間越久，產物比率越低，此係因反應 時間增大使得較多原料被穿透並能充分反應而釋出燃油及 -10- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 574139 A7 B7 五、發明説明（8 ) 可燃氣，而有較低之產物比率。 裝 熱裂解反應時間與產物比率:根據實例1之方法，於反應 溫度900°C及硫化鈉導入速率1.0 mg-溶液/g-含碳原料-sec 之條件下進行熱裂解反應，以製備含硫粉狀活性碳，以觀 察熱裂解反應時間對含硫活性碳表面積的影響，其結果顯 示於圖5。依此結果，反應時間越久，含硫粉狀活性碳的表 面積越大，此係因反應時間增大使得較多原料被撞擊而形 成較多孔洞，故有較大之表面積。 含硫溶液濃度與表面積、孔徑及硫含量••根據實例1之方 法，於反應溫度900°C及硫化鈉導入速率為1.0 mg-溶液/g-含碳原料-sec之條件下進行熱裂解反應100分鐘，以製備含 硫粉狀活性碳，以觀察於不同含硫溶液濃度下，含硫活性 碳表面積、孔徑及硫含量的變化，其結果顯示於下表1 : 表1 硫化納溶液 (wt %) 表面積 (m2/g) 平均孔徑 (A) 硫含量 (wt %) 硫含量增加 (wt %) 0.01 461 22.78 0.94 0.28 0.10 563 20.72 1.09 0.43 0.20 578 20.61 1.11 0.45 0.50 588 21.06 1.59 0.93cool down. In addition to reducing the temperature of the thermal cracking reaction product, this cooling step can also cool other by-products such as flammable gas and dissolve it in water. After this treatment, 'the least amount of flammable gas can be produced' to avoid causing secondary damage to the environment. Pollution, in addition to the fuel produced, can also be used to produce alternative diesel for energy use. This month has many advantages: (1) The sulfur content and surface area after powdery activity can be increased at the same time due to the adsorption and impact of sulfur ions; (2) Because the carbon material to the The manufacture of sulfur powdered activated carbon can greatly reduce the use of energy and shorten the manufacturing time; (3) Because the present invention can directly use waste tires as carbon-containing raw materials, the waste tires can be recycled and reused, thereby reducing the environmental burden. The following examples are used to explain the present invention in detail, but it is not meant to limit the present invention to only those disclosed in these examples. ^ 11-L Preparation of sulfur-containing powdered activated carbon Refer to Figure 1 for the preparation of sulfur-containing powdered activated carbon. The carbon-containing raw materials are waste tires 9 that have metal strips removed in advance and crushed into small pieces of about 1 to 2 cm3. The waste tire 9 is placed in a reaction furnace 8 containing a heating tube 7 and the oxygen in the reaction furnace 8 is removed by an oxygen driving device 3. These waste tires 9 are heated to 800 ° C to 90CTC by a heating tube 7 to perform a thermal cracking reaction. During the thermal cracking reaction, a peristaltic pump 4 is used to introduce sodium sulfide solutions of different concentrations through a sulfur-containing solution introduction port 5 into one of the introduction holes 6 of the reaction furnace 7, and the introduction rate is adjusted to 0.50 to 2.OOmg -Solution / g-carbon-containing raw material-sec. At the same time, a nitrogen source 1 and a nitrogen control valve 2 were used to introduce nitrogen at a rate of 0.05 liters / minute. -9-This paper size is in accordance with Chinese National Standard (CNS) A4 (210X 297 mm) 574139 A7 B7 V. Description of the invention (7) After the thermal cracking reaction has proceeded, the product is cooled through a cooling pipe 10 and cooled by A product control valve 12 collects sulfur-containing powdered activated carbon in a product collection bag 11 and discharges combustible gas through a combustible gas discharge hole 13. The fuel oil produced is placed in an ice bath 1 The shock absorber 14 in 5 absorbs it. Example 2: Properties of sulfur-containing powdered activated carbon Sulfur-containing solution introduction rate and product ratio: According to the method of Example 1, thermal cracking reaction was performed at a reaction temperature of 800 ° C for 60 minutes, and in different sulfur-containing solutions (sodium sulfide) Sulfur-containing powdered activated carbon was prepared at the introduction rate to observe the change in product ratio. The results are shown in FIG. 2. According to this result, the larger the introduction rate, the lower the product ratio. This is because the increase in the introduction rate causes more raw materials to be impacted and can fully react to release fuel and flammable gas, and has a lower product ratio. Sulfur-containing solution introduction rate and surface area: According to the method of Example 1, a thermal cracking reaction was performed at a reaction temperature of 800 ° C for 60 minutes, and sulfur-containing powdered activated carbon was prepared at different introduction rates of sulfur-containing solution (sodium sulfide). The change in the surface area of the sulfur-containing powdered activated carbon was observed, and the results are shown in FIG. 3. According to this result, the larger the introduction rate, the larger the surface area of the sulfur-containing powdered activated carbon. This is because the impact rate of sulfur ions increases due to the increase in the introduction rate, which results in the formation of more porous holes, which results in a larger surface area. Thermal cracking reaction time to product ratio: According to the method of Example 1, the thermal cracking reaction was performed under the conditions of a reaction temperature of 900 ° C and a sulfide steel introduction rate of 1.0 mg-solution / g-carbon-containing raw material-sec to prepare sulfur-containing The powdered activated carbon was used to observe the effect of thermal cracking reaction time on the product ratio. The results are shown in FIG. 4. According to this result, the longer the reaction time, the lower the product ratio. This is because the increase in reaction time allows more raw materials to be penetrated and can fully react to release fuel. -10- This paper size applies Chinese National Standard (CNS) A4 Specifications (210 X 297 mm) 574139 A7 B7 V. Description of the invention (8) Combustible gas with low product ratio. Thermal cracking reaction time and product ratio: According to the method of Example 1, the thermal cracking reaction was performed under the conditions of a reaction temperature of 900 ° C and a sodium sulfide introduction rate of 1.0 mg-solution / g-carbon-containing raw material-sec to prepare sulfur-containing Powdered activated carbon was used to observe the effect of thermal cracking reaction time on the surface area of sulfur-containing activated carbon. The results are shown in FIG. 5. According to this result, the longer the reaction time, the larger the surface area of the sulfur-containing powdered activated carbon. This is because the larger the reaction time, the more raw materials are impacted to form more porous holes, so the surface area is larger. Sulfur solution concentration and surface area, pore size and sulfur content • According to the method of Example 1, the thermal cracking reaction was performed under the conditions of a reaction temperature of 900 ° C and a sodium sulfide introduction rate of 1.0 mg-solution / g-carbon-containing raw material-sec. 100 minutes to prepare sulfur-containing powdered activated carbon to observe the changes in the surface area, pore size, and sulfur content of sulfur-containing activated carbon at different sulfur-containing solution concentrations. The results are shown in Table 1 below: Table 1 Sodium sulfide solution (wt %) Surface area (m2 / g) Average pore size (A) Sulfur content (wt%) Sulfur content increase (wt%) 0.01 461 22.78 0.94 0.28 0.10 563 20.72 1.09 0.43 0.20 578 20.61 1.11 0.45 0.50 588 21.06 1.59 0.93
依此結果，隨著含硫溶液濃度增加，含硫量亦增加，在 0.5 0重量％之硫化鈉反應下，含硫粉狀活性碳的孔徑因硫 原子的撞擊效應大於吸附效應而相較於0.1 0或0.2 0重量％為 大，且其整體表面積與0.10或0.20重量％之硫化鈉相比亦較 -11 - 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) 574139 A7 B7 五 發明説明（9 大，故本發明可兼顧增大硫含量及不影響表面積之優點。 實例3 :含硫粉狀活性碳於吸附汞離子之應用 本實例係以依據實例1所製得之含硫粉狀活性碳於一吸收 反應器中進行汞離子之吸附。經加熱1 m g / L之氯化汞溶液 之蒸汽在作為攜帶氣體的氮氣帶領下，充填於該吸收反應 器中，使吸收反應器中氯化汞濃度達到24至26 pg/Nm3。 於此時將含硫粉狀活性碳加入該吸收反應器中進行汞離子 之吸附，並於不同時間取樣量測吸收反應器中汞離子之濃 度。經含硫粉狀活性碳的吸附，該吸收反應器中之汞離子 含量漸漸下降，並最後達到一常數值；而當停止加入該含 硫粉狀活性碳時，汞離子之濃度又回到起始濃度（24至26 pg/Nm3)。由此可知，汞離子確可由本發明製得之含硫粉 狀活性碳而吸附，且吸附效率超過8 6.5 %，故經由加入該 含硫粉狀活性碳，確可達到減少環境中，特別是垃圾焚化 爐中汞離子之功效。 上述實施例僅為說明本發明之原理及其功效，而非限制 本發明。因此，習於此技術之人士對上述實施例所做之修 改及變化仍不達背本發明之精神。本發明之權利範圍應如 後述之申請專利範圍所列。 -12- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐)According to this result, as the concentration of the sulfur-containing solution increases, the sulfur content also increases. Under the reaction of 0.5% by weight of sodium sulfide, the pore diameter of the sulfur-containing powdered activated carbon is larger than that of the sulfur atom due to the impact effect of the sulfur atom. 0.1 0 or 0.2 0% by weight is large, and its overall surface area is also -11 compared to 0.10 or 0.20% by weight of sodium sulfide-This paper size applies to China National Standard (CNS) A4 specifications (210X297 mm) 574139 A7 B7 5 Description of the invention (9 large, so the present invention can take into account the advantages of increasing the sulfur content and not affecting the surface area. Example 3: Application of sulfur-containing powdered activated carbon for adsorption of mercury ions. This example is based on the Sulfur powder activated carbon is adsorbed by mercury ion in an absorption reactor. The steam heated by 1 mg / L mercury chloride solution is filled in the absorption reactor under the guidance of nitrogen as a carrier gas to make the absorption reaction. The concentration of mercury chloride in the reactor reached 24 to 26 pg / Nm3. At this time, sulfur-containing powdered activated carbon was added to the absorption reactor to adsorb mercury ions, and the mercury ion in the absorption reactor was sampled and measured at different times. Concentration. For the adsorption of sulfur powdered activated carbon, the mercury ion content in the absorption reactor gradually decreases and finally reaches a constant value; when the addition of the sulfur-containing powdered activated carbon is stopped, the mercury ion concentration returns to the initial concentration (24 to 26 pg / Nm3). It can be seen that mercury ions can indeed be adsorbed by the sulfur-containing powdered activated carbon prepared by the present invention, and the adsorption efficiency exceeds 86.5%. Therefore, by adding the sulfur-containing powdered activated carbon, The effect of reducing mercury ions in the environment, especially in the waste incinerator, can be achieved. The above-mentioned embodiments are only for explaining the principle of the present invention and its effects, rather than limiting the present invention. Therefore, those skilled in the art will be more comfortable with the above-mentioned embodiments. The modifications and changes made still do not meet the spirit of the present invention. The scope of the rights of the present invention should be listed in the scope of the patent application to be described later. -12- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 public) (Centimeter)
裝 訂Binding