1279436 玖、發明說明: 【發明所屬之技術領域】 本創作係關於一種燃料氣化及焦炭反應過程的測量方法;尤指 一種採用特製的固定床式氣化爐、溫度監測技術、產氣處理程序 與特定的操作方法及儀器,而能降低反應測量干擾,並準確地測 出燃料氣化及焦炭反應過程與反應特性的測量方法。 【先前技術】 按,根據1998底年世界初級能源推估,全球石油蘊藏量約可 維持41年使用量、天然氣約6 3年、抽礦約7 7年、而煤則可維持 218年。隨著石油與天然氣的日漸稀少,加之鈾礦發電廣受環保人 士的批評。相較之下,由於煤炭較能提供長久而安定的能源來源, 因而煤炭在能源開發所扮演的角色將與日倶增。煤可說是地球上 現今蘊藏量最為豐富的化石燃料,據估計目前全球可資利用的煤 炭量約為7.6兆噸,由於其含量豐富,因而廣泛用於產生熱能及 電能。以台灣能源利用為例,2003年煤炭的供應比例即佔總能源 的 32·6% 。 過去以來,煤炭的消耗係以粉煤直接燃燒為主,例如發電業。 粉煤直接燃燒雖然直接而快速,但是,其卻伴隨著嚴重的環境污 染問題,如煤灰、硫氧化物及氮氧化物等物質的排放。除了上述 各類空氣污染物外,煤炭燃燒的另一重要產物即為二氧化碳,而 二氧化碳的排放問題已是溫室氣體減量中最重要對象。例如聯合 國1992年6月在巴西里約召開的地球高峰會議所簽署的「氣候變 化綱要公約」及1997年12月於日本京都召開的第三次締約國大 會所簽訂的「京都議定書」,目標皆在於抑制地球的增温現象及 溫室氣體的減量。此外,我國在1998年5月所召開的「全國能源 會議」中,亦建議以優先推動節約能源及提升能源效率為二氧化 碳減量之策略。 !279436 又 煤炭燃燒除是發雷紫搞Ii 金過程重要的原料。其方煤炭也是煉鋼或治 膝ϋ + π先將煤厌送入煉焦爐内,經乾餾後 使二氣’焦炭進一步被送至高爐内作為還原劑, =的氧化^原成金屬鐵,且供給熱能使還原的鐵熔化為液體 =與熔化的㈣分開。至於錄氣,輕_化學工場進行加工。 =之’若。將煤厌中的揮發份去除後,殘餘的固態物質,即焦炭, 將疋煉鋼程序中不可或缺的還原劑。 檢視上述的工業發電或煉鋼,煤炭皆是不可或缺的原料。若 和石油及天然氣等化石燃料比較,煤炭目前具有許多優點,諸如 價格便宜、開採容易、儲量豐富及相關開發技術成熟等。儘管如 此,由於煤炭為固態燃料,因此其燃燒效率較天然氣或石油為低。 為提高煤炭的發電效率並減少空氣污染物的排放,淨煤技術 (clean coal technology)的研究及發展已成為現今能源開發的重 要目標。 在新近發展的淨煤技術中,煤炭氣化(gas i f i cat i on)堪稱為 一重要的發展技術。所謂氣化是係利用缺氧燃燒的技巧,藉由控 制固定比例的燃料與氧化劑,經過不完全的燃燒後,即可得到潔 淨的燃氣如氫氣(H2)、一氧化碳(C0)與曱烷(CH4)。上述燃氣可供 燃燒以發電或作為化學工業的原料,使得煤炭氣化之燃氣燃燒效 能和天然氣近似。若將氣化所產生一氧化碳再與水蒸汽發生轉化 反應而產生氫氣,其可做為燃料電池(fuel cell)的原料。至於殘 餘的固態物主成份是焦炭及礦物態的雜質,其中焦炭即成為煉鋼 製程重要的原料。綜而言之,煤炭氣化的應用甚為多元。 氣化複循環系統(Integrated Gasification Combined Cycle,IGCC)的設立可說是煤炭氣化及淨煤技術重要的實際應 用,因而已成為眾所矚目焦點,此係因該系統具有高發電效率及 優異的環保效能之故。所謂氣化複循環系統係將煤炭置於氣化爐 中,於高溫及不足氧的操作環境下將固態燃料轉化為合成燃氣 1279436 CO、H2及CH4,經除塵、除硫和除氮後,再送至複循環機組作為燃 料發電。目前IGCC效率約達45%左右,較傳統燃煤發電的35%高 出甚多,此外,IGCC發電薇中C〇2排放量也較低。至於省水量, 因IGCC能有效將蒸汽回收再利用,因而可節約35%左右的用水。 由於IGCC於合成氣燃燒前已先將污染物去除,因而除硫率及除氮 率約達90%及99%。根據美國能源部的推估,至2008年及2015年 IGCC的綜合發電效率可達52%及60%左右,由此可看出煤炭在IGCC 能源化的潛力。 事實上,除了煤炭外,上述的氣化技術及IGCC系統也可以用 其他有機物質如都市廢棄物、農業生質物或污泥做為燃料。在整 個IGCC系統中,氣化爐的建構及氣化操作條件堪稱為關鍵技術。 惟,良好的氣化操作實仰賴於準確的測量方法,方能正確地反映 出即時的運轉狀況,得知燃料氣化及焦炭反應的特性,並做出最 適化的操作決策。由於燃料氣化過程將產生粒狀物質、焦油及其 他氣狀污染物,如硫化氫、氰氣、氨氣等,上述物質對於測量儀 器將造成干擾及損害,進而影響氣化測量數據的正確性。 【發明内容】 有鑑於上述問題,發明人乃研究出一種「燃料氣化及焦炭反應 過程的測量方法」,除可監測燃料的氣化反應過程、去除產氣中 的干擾物質或雜質,並準確地測出燃氣濃度外,藉由燃氣濃度的 分佈情形將可進一步推求焦炭的反應情形。 為達成上述目的之技術内容,係提供一種「燃料氣化及焦炭反 應過程的測量方法」,其前置處理先將煤炭置於烘箱乾燥後,將定 量的煤炭藉由進料裝置送入固定床式氣化爐中,並控制氧化劑流 量由爐體下方送入。煤炭於氣化爐内受熱氣化後,架設之熱感應 器可監測出燃料的吸熱及放熱情形。燃氣上昇且經由冷凝、水洗、 過濾及乾燥等處理程序後,即可產出潔淨且無干擾性物質的燃 氣,而後以氣相層析儀及氣體分析儀準確地測量燃氣中各類氣體 1279436 的濃度’進而由測量的結果評估燃料的反應性及實際應用之適用 性。 【實施方式】 本發明方法疋以如第一圖所示之測量系統作為優選的實施例 結構,其不但可產出潔淨的氣化燃氣以顯著降低測量干擾,而使 得測量結果極為準確,測量的結果更可做為燃料反應性及實際應 用性之評估依據,該測量系統包括: 一反應爐體(10),具有爐管(11)及爐床(12),爐管(11)外圍 繞設加熱器(13),並以氧化鋁(14)加以包覆,爐管(11)可為不繡 鋼管,爐床(12)可為不繡鋼網,加熱器(13)可為環繞的電熱棒, 藉由温度控制器(15)及功率控制器(16)的使用,而可對爐管(11) 進行昇溫加熱; 一上架設管(20)及下架設管(30),上架設管設置於爐管(11) 頂端形成相連通,上架設管(20)旁連接螺桿(21),由馬達(22)帶 動螺桿轉動,使煤炭燃料經由入料斗(23)進入爐管(Π)中而掉落 於爐床(12),又,下架設管(30)設置於爐管(11)底端’其底端封 閉,於周面上設置一進氣管(31),進氣管伸入下架設管(30)内部, 進氣管連接流量計(32)以控制氧化劑流量,進氣管末端可接至供 應氧化劑之鋼瓶(33),並使氧化劑可由進氣管(31)導入下架設管 (30)而由下往上進入爐管(11)中; 一反應監測裝置(40),具有數據擷取系統(41)及熱感應器 (42),上述數據擷取系統包含電腦、數據擷取卡及數據擷取軟體, 其連接熱感應器(42),熱感應器可為K型熱電偶,其直接穿入爐 管(11)内,並架設於爐床(12)中,而能監測爐管(11)内部燃料反 應之溫度,又熱感應器(42)所測得的溫度將送至温度控制器(15) 及功率控制器(16),以做為加熱器(13)運轉之依據; 一氣體處理系統(50) ’具有冷凝管(51)、水洗槽(52)、過濾 1279436 裔(53)及乾燥塔(54)四個處理單元。所述之冷凝管(51)可為不續 鋼管(511) ’外圍可環繞銅管(512) ’氣化後之高温燃氣(513)由不 繡鋼管内部流通,冰冷水(514)則流入鋼管(512),冷凝管(51)下 方連接一多通管(515),可收集凝結之焦油;水洗槽(52)可為錐形 瓶’其外接二條塑膠管,水洗槽内裝半滿之水,進氣端塑膠管(5 21) 沒入水中,排氣端塑膠管(522)則位於水上;過濾器(53)可為壓克 力材質製成之夾層,内具〇.45//m網目之濾紙(531);乾燥塔(54) 可為壓克力製成之流通槽,内具可吸水分之乾燥石夕膠(541); 一氣體'/辰度測ΐ裝置(6 0)’具有氣相層析儀(61)及氣體分析 儀(62),藉由氣針(63)定時定量抽取燃氣,並打入氣相層析儀(61) 中,將可得知燃氣内氫氣的濃度,而藉由抽氣泵的運轉,將燃氣 送入氣體分析儀(62)中,並配合數據擷取系統(41)的運作,則可 疋時測出燃乳内曱烧、一氧化碳及一氧化碳的濃度。由上述氫氣、 曱烷、一氧化碳及二氧化碳的濃度,可得知燃料在各種操作參數 的反應特性,而由一氧化碳及二氧化碳的濃度比值,進而可得知 焦炭的反應特性。 本發明方法的技術内容,請配合參看第二圖所示,其前置處 理之煤炭在烘箱乾燥後,將固定質量的煤炭燃料先倒進入料斗(23) 内,並啟動馬達(22)帶動螺桿(21),將煤炭燃料推入上架設管(2〇) 中,使其落入爐管(11)並堆集於爐床上(12),氧化劑則經由進氣 管(31)由下方進入爐管(11)。以加熱器(13)加熱爐管(11),使煤 炭受熱氣化。煤炭反應期間以數據擷取系統(41)及熱感應器(42) 監測並紀錄氣化反應溫度。氣化產生之氣體上昇且進入冷凝管 (51),藉由熱交換使燃氣中的焦油冷凝為液體,可由多通管(515) 流出並加以收集,而氣化生成的可燃氣則經過水洗槽(52),藉由 水浴燃氣方式可去除氣狀污染物及較粗粒徑之粒狀物質。而後燃 氣再流經過濾器(53),過濾器内之濾紙(531)可進一步濾除燃氣内 較細粒徑的粒狀物質。最後,燃氣流過乾燥塔(54),乾燥塔内之 矽膠(541)可除去燃氣中因水浴所含之水氣。燃氣經由上述之冷 1279436 凝、水洗、過濾、及乾燥等處理單元後,即可產出潔淨且無干擾性 物質的燃氣,以利後續的測量。而後將燃氣引至氣相層析儀 (GOW-MAC SERIES 400 GC) (61)及氣體分析儀(Fuji ZRJF5Y23_ae RYR-YKLYYCY-A)(62)以測量氫氣、甲燒、一氧化碳及二氧化碳的 濃度,由上述的氣體濃度可得知煤炭燃料的反應過程 ,並可由一 氧化碳及二氧化碳的濃度比值得知焦炭的反應情形。 為了先行瞭賴料在高温環境下與空氣反應的基本特性,第 三圖所示為煤炭置於空氣中的熱重分析(升温速率為2Q 口_, 進氣量為l〇〇ffll/rair〇結果,其中實線部份代表礙炭重量隨溫度增 加的變化量,而虛線則代表煤炭在單位溫度變化下之消耗量(即煤 分對Ϊ度f=)。整體而言,圖中可看出微分曲線有三 = 出現在Μ左右,應是煤炭之中固有水 個波峰出現約在516。°左右,此時煤炭重 里大里遞減’右依煤財似分析來 / 的固定碳燃燒所造成;而最德應疋禪㈣㈣及4刀1279436 玖, invention description: [Technical field of invention] This creation is about a method for measuring fuel gasification and coke reaction process; especially a special fixed bed gasifier, temperature monitoring technology, gas production process With specific operating methods and instruments, it can reduce the reaction measurement interference and accurately measure the fuel gasification and coke reaction process and reaction characteristics. [Prior Art] According to the world's primary energy estimation in the end of 1998, the global oil reserves can be maintained for about 41 years, natural gas for about 63 years, mining for about 7 years, and coal for 218 years. With the increasing scarcity of oil and natural gas, uranium mine power generation has been widely criticized by environmentalists. In contrast, coal is playing a more important role in energy development because coal is more capable of providing a long-lasting and stable source of energy. Coal is arguably the most abundant fossil fuel on the planet today. It is estimated that the globally available coal is about 7.6 megatons, which is widely used to generate heat and electricity because of its rich content. Take Taiwan's energy utilization as an example. In 2003, the proportion of coal supply accounted for 32.6% of total energy. In the past, coal consumption was dominated by direct combustion of pulverized coal, such as the power generation industry. Although direct combustion of pulverized coal is direct and rapid, it is accompanied by serious environmental pollution problems such as emissions of coal ash, sulfur oxides and nitrogen oxides. In addition to the above-mentioned various types of air pollutants, another important product of coal combustion is carbon dioxide, and carbon dioxide emissions have become the most important target for greenhouse gas reduction. For example, the "Kyoto Protocol" signed by the United Nations at the Earth Summit in Rio, Brazil, in June 1992, and the "Kyoto Protocol" signed at the Third Meeting of States Parties in Kyoto, Japan in December 1997, aim to Suppress the warming of the earth and the reduction of greenhouse gases. In addition, in the “National Energy Conference” held in May 1998, China also proposed to give priority to promoting energy conservation and energy efficiency as a strategy for carbon dioxide reduction. !279436 And coal burning is an important raw material for the process of making Ii gold. The coal is also steel or knee ϋ + π first put the coal into the coke oven, after the dry distillation, the second gas 'coke is further sent to the blast furnace as a reducing agent, = oxidation of the original metal iron, and The heat supplied can cause the reduced iron to melt into a liquid = separate from the molten (four). As for the recording of gas, light _ chemical workshop for processing. =之如如. After removing the volatiles from the coal, the residual solid matter, coke, will be an indispensable reducing agent in the steelmaking process. Examining the above-mentioned industrial power generation or steelmaking, coal is an indispensable raw material. Compared with fossil fuels such as oil and natural gas, coal currently has many advantages, such as low price, easy mining, abundant reserves and mature development technologies. Despite this, since coal is a solid fuel, its combustion efficiency is lower than that of natural gas or petroleum. In order to improve the power generation efficiency of coal and reduce the emission of air pollutants, the research and development of clean coal technology has become an important goal of energy development today. Among the newly developed clean coal technologies, coal gasification (gas i f i cat i on) is an important development technology. The so-called gasification is the use of anaerobic combustion techniques, by controlling a fixed proportion of fuel and oxidant, after incomplete combustion, you can get clean gas such as hydrogen (H2), carbon monoxide (C0) and decane ( CH4). The above gas can be burned to generate electricity or as a raw material for the chemical industry, so that the gas combustion effect of coal gasification is similar to that of natural gas. If carbon monoxide produced by gasification is converted into water and then reacted with water vapor to generate hydrogen, it can be used as a raw material for a fuel cell. As for the residual solids, the main components are coke and mineral impurities, and coke becomes an important raw material for the steelmaking process. In summary, the application of coal gasification is diversified. The establishment of the Integrated Gasification Combined Cycle (IGCC) can be said to be an important practical application of coal gasification and clean coal technology, and has thus become the focus of attention. This system has high power generation efficiency and excellent performance. The reason for environmental protection. The so-called gasification and recirculation system places coal in a gasifier, and converts the solid fuel into synthetic gas 1279436 CO, H2 and CH4 under high temperature and under-oxygen operating environment. After dust removal, sulfur removal and nitrogen removal, It is sent to the double cycle unit to generate electricity as fuel. At present, the efficiency of IGCC is about 45%, which is much higher than that of traditional coal-fired power generation of 35%. In addition, IGCC power generation has a lower C〇2 emission. As for water saving, IGCC can effectively recycle steam, which can save about 35% of water. Since IGCC has removed contaminants before syngas combustion, the sulfur removal rate and nitrogen removal rate are about 90% and 99%. According to the US Department of Energy's estimates, the combined power generation efficiency of IGCC in 2008 and 2015 can reach 52% and 60%, which shows the potential of coal in IGCC energy. In fact, in addition to coal, the above gasification technology and IGCC system can also be used as fuel for other organic materials such as municipal waste, agricultural biomass or sludge. In the entire IGCC system, the construction of the gasifier and the gasification operating conditions are called key technologies. However, good gasification operations rely on accurate measurement methods to accurately reflect the immediate operating conditions, to understand the characteristics of fuel gasification and coke reaction, and to make optimal operational decisions. As the fuel gasification process will produce particulate matter, tar and other gaseous pollutants, such as hydrogen sulfide, cyanide gas, ammonia gas, etc., the above substances will cause interference and damage to the measuring instrument, thereby affecting the correctness of the gasification measurement data. . SUMMARY OF THE INVENTION In view of the above problems, the inventors have developed a "measurement method for fuel gasification and coke reaction process", in addition to monitoring the gasification reaction process of the fuel, removing interfering substances or impurities in the gas production, and accurately In addition to measuring the gas concentration, the reaction of the coke can be further derived by the distribution of the gas concentration. In order to achieve the technical content of the above purpose, a "method for measuring fuel gasification and coke reaction process" is provided, which pre-processes the coal in an oven and then feeds the quantitative coal into the fixed bed through the feeding device. In the gasifier, the oxidant flow rate is controlled to be fed from below the furnace body. After the coal is heated and vaporized in the gasifier, the built-in thermal sensor can monitor the heat absorption and heat release of the fuel. After the gas rises and is processed through condensation, water washing, filtration and drying, it can produce clean and non-interfering substances, and then accurately measure various gases in the gas by gas chromatography and gas analyzer. The concentration of gas 1279436, in turn, evaluates the reactivity of the fuel and the suitability of the application from the results of the measurements. [Embodiment] The method of the present invention adopts a measurement system as shown in the first figure as a preferred embodiment structure, which not only can produce clean gasification gas to significantly reduce measurement interference, but also makes measurement results extremely accurate, and measurement The result can be used as a basis for evaluation of fuel reactivity and practical applicability. The measuring system comprises: a reaction furnace body (10) having a furnace tube (11) and a hearth (12), and the furnace tube (11) is surrounded by The heater (13) is provided and coated with alumina (14), the furnace tube (11) can be a non-embroidered steel tube, the hearth (12) can be a stainless steel mesh, and the heater (13) can be surrounded. The electric heating rod can heat up the furnace tube (11) by using the temperature controller (15) and the power controller (16); the upper erection tube (20) and the lower erection tube (30) are erected The tube is arranged at the top end of the furnace tube (11) to form a phase communication, and the upper erecting tube (20) is connected to the screw (21), and the motor (22) drives the screw to rotate, so that the coal fuel enters the furnace tube through the hopper (23). Dropped in the hearth (12), and the lower erection tube (30) is placed at the bottom end of the furnace tube (11) The end is closed, and an intake pipe (31) is disposed on the circumferential surface, the intake pipe extends into the lower erection pipe (30), and the intake pipe is connected to the flow meter (32) to control the flow of the oxidant, and the end of the intake pipe can be connected to An oxidant cylinder (33) is supplied, and the oxidant can be introduced into the lower erection tube (30) from the intake pipe (31) and into the furnace tube (11) from bottom to top; a reaction monitoring device (40) having data acquisition The system (41) and the thermal sensor (42), the data capture system comprises a computer, a data capture card and a data capture software, which is connected to the thermal sensor (42), and the thermal sensor can be a K-type thermocouple, Directly penetrates into the furnace tube (11) and is installed in the hearth (12), and can monitor the temperature of the fuel reaction inside the furnace tube (11), and the temperature measured by the heat sensor (42) will be sent to the temperature. The controller (15) and the power controller (16) serve as the basis for the operation of the heater (13); a gas treatment system (50) 'has a condenser tube (51), a water washing tank (52), and a filter of 1279436 ( 53) and drying tower (54) four processing units. The condensing pipe (51) may be a non-continuous steel pipe (511) 'peripherally surrounding the copper pipe (512) 'the gasified high-temperature gas (513) is circulated inside the non-embroidered steel pipe, and the ice-cold water (514) flows in. Steel pipe (512), a multi-pass pipe (515) is connected under the condensing pipe (51) to collect the condensed tar; the washing tank (52) can be a conical flask, which is connected with two plastic pipes, and the washing tank is half filled. Water, the plastic tube at the inlet end (5 21) is not in the water, the plastic tube (522) at the exhaust end is located on the water; the filter (53) can be a sandwich made of acrylic material with a 〇.45// m mesh filter paper (531); drying tower (54) can be a flow channel made of acrylic, with a dry water-absorbing gel (541); a gas '/ Chen degree measuring device (6 0 ) With a gas chromatograph (61) and a gas analyzer (62), the gas is periodically extracted by a gas needle (63) and pumped into a gas chromatograph (61) to learn The concentration of hydrogen in the gas, and by the operation of the pump, the gas is sent to the gas analyzer (62), and in conjunction with the operation of the data extraction system (41), the internal combustion of the fuel can be detected. Concentration of carbon monoxide and carbon monoxide. From the concentrations of the above-mentioned hydrogen, decane, carbon monoxide and carbon dioxide, the reaction characteristics of the fuel in various operating parameters can be known, and the reaction ratio of the coke can be known from the concentration ratio of carbon monoxide and carbon dioxide. For the technical content of the method of the present invention, please refer to the second figure. After the pre-treated coal is dried in the oven, the fixed-quality coal fuel is first poured into the hopper (23), and the motor (22) is driven to drive the screw. (21), push the coal fuel into the upper erection tube (2〇), drop it into the furnace tube (11) and accumulate it on the hearth (12), and the oxidant enters the furnace tube from below through the intake pipe (31). (11). The furnace tube (11) is heated by a heater (13) to heat and vaporize the coal. The gasification reaction temperature is monitored and recorded by the data acquisition system (41) and the thermal sensor (42) during the coal reaction. The gas generated by the gasification rises and enters the condensation pipe (51), and the tar in the gas is condensed into a liquid by heat exchange, which can be discharged from the multi-pass pipe (515) and collected, and the combustible gas generated by the gasification is washed with water. The trough (52) can remove gaseous contaminants and coarser granular material by means of water bath gas. The post-combustion gas then flows through the filter (53), and the filter paper (531) in the filter further filters out the finer-grained particulate matter in the gas. Finally, the gas flows through the drying tower (54), and the silicone (541) in the drying tower removes the moisture contained in the gas from the water bath. After the gas is treated by the above-mentioned cold 1279436 treatment, such as condensation, water washing, filtration, and drying, the clean and non-interfering gas can be produced to facilitate subsequent measurement. The gas is then directed to a gas chromatograph (GOW-MAC SERIES 400 GC) (61) and a gas analyzer (Fuji ZRJF5Y23_ae RYR-YKLYYCY-A) (62) to measure the concentration of hydrogen, methyl, carbon monoxide and carbon dioxide. The reaction process of the coal fuel can be known from the above gas concentration, and the reaction condition of the coke can be known from the concentration ratio of carbon monoxide and carbon dioxide. In order to firstly understand the basic characteristics of the reaction with air in a high temperature environment, the third figure shows the thermogravimetric analysis of the coal placed in the air (the heating rate is 2Q port _, the intake air amount is l〇〇ffll/rair〇 As a result, the solid line portion represents the amount of change in the weight of the carbon with the increase in temperature, and the broken line represents the consumption of the coal under the change of the unit temperature (ie, the coal point has a degree of twist f =). Overall, the figure can be seen There are three differential curves appearing around the Μ, which should be caused by the peak of the intrinsic water in the coal, which is about 516 ° °, when the coal is heavy and the mile is reduced by the fixed carbon burning of the coal-like analysis. The most German should be Zen (four) (four) and 4 knives
^ ^ 7〇〇〇c J 是煤炭樣品中,燃點較高的少,物^ 〃疋小巾s波動,㈣象應 線的變化不大,幾乎毫無:燃燒所形成。此後微分曲 分成份為灰份。 文動呈現水平狀態,剩下的物質大部 第四圖所不為煤厌在=猶冗因备 丁,饮μ、+、枷旦古、土糾種不门化溫度(800、900、1〇〇〇°C) :、y、1 ,反應器爐床内之反應溫度隨時間變化 :二t二H二f鐘2到15分鐘之間’無論在何種氣化溫度, 曲線變化分為兩階段。第一階段反應之溫产 於氣化温度,此階段主要原Λ ^ 、^的曰口小 Μ Γ 煤反強烈地吸熱所造成,所吸 tur 解。從第三圖的熱重分析可以得知,當煤 厌從η劇進人南溫中,其將促使反應劇烈 第二階段反應溫度隨著時間的增加而略高於氣化 1 要是因職反賴造成。當職錢之後 因先前熱解反應而氣化成氣體,此反應又稱為去揮== Γ279436 氣體燃點較低’使得揮發份燃燒而造成溫度上升。一旦反應溫度 逐漸趨於穩定後’去揮發反應的重要性將漸降低,轉由焦炭反應 變成較重要。綜言之,此處所發展之溫度監測技術可得知燃料的 氣化反應依序經歷了吸熱(乾燥、熱解及去揮發)、放熱(燃燒)及 焦炭反應。 接著’第五圖所示為在不同氣化溫度(8〇〇、9〇〇、1〇〇(rc)時, 依上述測量方法所測得之氫氣、甲烷、一氧化碳及二氧化碳的濃 度。在溫度800°C的實驗中,本測量方法可看出氫氣濃度從起初 31%隨時間迅速地下降,甲烷生成濃度也從最高15分鐘時將近8% 逐漸下降’到50分鐘時濃度趨近零。此外,初始C0濃度大於C〇2, 其原因在於去揮發跟裂解反應同時進行,但經過35分鐘後CO濃 度逐漸地小於C〇2,變成燃燒反應漸佔優勢。而在氣化溫度為9〇〇 °C實驗中’雖然氫氣生成濃度隨時間也是呈現大幅下降的趨勢, 但所測得的起始濃度大約47%,比8〇〇°C氫氣濃度31%相較之下高 出許多。至於甲烷,氣化初期其生成濃度也較800°C呈現倍數增 加’達17%左右,但濃度下降趨勢與氫氣相同,c〇與C〇2之生成濃 度’雖然初始C0濃度大幅領先c〇2,但隨時間C0的濃度呈現遞減, 相反地’ C〇2逐漸遞增,兩者之間彼此相互競爭,到實驗結束c〇 濃度還是微高於C〇2生成濃度。由於C0的生成可用以說明焦炭的 反應性,上述的結果顯示焦炭於900°C之反應較800°c為佳。至於 >里度10〇〇c之貫驗’可發現氮氣初始生成濃度更南達65%,而曱 烧初始生成濃度卻低於900°C時,此係因在此高温(1〇〇〇。(3 )環境下 甲烷裂解成氫氣之趨勢較明顯,故濃度反而降低。至於C0與C〇2 之生成濃度,由於焦炭的反應更為明顯,故CO濃度遠高於c〇2生 成濃度 配合參看第六圖所示,為依上述測量結果所得在三種不同氣 化温度下,C0與C〇2濃度比值分佈圖,二者的比值可做為煤炭氣 化反應及焦炭反應之重要指標。整體而言,隨氣化溫度的提高, 我們可看出二者的比值亦明顯上升,由此可知氣化溫度對焦炭反 11 1279436 ^具有重大影響’故第七圖所示為三種不同氣化温度之煤炭反應 =其說明當氣化溫度為_、_、⑽代時,煤炭 轉 =36.73%、37.97%及 54.55%。另一方面,__度比值隨 =的變化顯示’當反應時間達15 ^分鐘時,該分佈曲線出 银Ϊ大值現象由於⑺可視為氣化之重要產物,而⑶2則為燃燒 的重要結果,故上述的最大值分佈正可說明氣燃 過程的競爭態勢。 —4上所述本么明燃料氣化及焦炭反應過程的測量方法」, =由自行架設之1U定床式氣化爐,並配合溫度監測及氣體處理, 、,可產出潔淨且無干擾性物質的燃氣,而藉由濃度量測及數據 ,析’進而可提供燃料氣化及焦炭反應之完整且精確的反應資 :亦即’本發明方法係利用自然法則技術思想之高度創作,符 a發明專利要件,爰依法俱文提出申請。 【圖式簡單說明】 (一) 圖式簡單說明 第^圖:·實施本發明方法之測量系統示意圖。 ==圖:實施本發明方法之流程圖(代表圖)。 1.圖實轭本發明方法之煤炭置於空氣中的熱重分析圖 #四圖··實施本發明方法之煤炭反應溫度監測圖。 圖·.實施本發明方法之燃氣濃度分佈圖。 ··實施本發明方法之⑽™2比值分佈圖。 β •實施本發明方法之煤炭反應率。 (二) 主要部份代表符號說明 (1)測量系統 (10)反應爐體 (12)爐床 (14)氧化鋁 (16)功率控制器 (11)爐管 (13)加熱器 (15)温度控制器 (20)上架設管 12 1279436 (21)螺桿 (23)入料斗 (31)進氣管 (33)鋼瓶 (41)數據擷取系統 (50)氣體處理系統 (511)不繡鋼管 (513) 南温燃氣 (514) 冰冷水 (52) 水洗槽 (522)進氣端塑膠管 (53) 過濾器 (54) 乾燥塔 (60)氣體濃度測量裝置 (62)氣體分析儀 (22)馬達 (30)下架設管 (32)流量計 (40)反應監測裝置 (42)熱感應器 (51)冷凝管 (512)銅管 (514) 冰冷水 (515) 多通管 (521)錐形瓶 (523)排氣端塑膠管 (531)濾紙 (541)矽膠 (61)氣相層析儀 (63)氣針 13^ ^ 7〇〇〇c J is the coal sample, the ignition point is higher, the material 〃疋 〃疋 波动 fluctuation, (4) the change of the line is not big, almost nothing: the formation of combustion. Thereafter, the differential component is ash. The literary movements are in a horizontal state, and the remaining material is not in the fourth picture. The coal is tired of being ridiculously ridiculous, drinking μ, +, 枷旦古, soil rectification temperature (800, 900, 1 〇〇〇°C) :, y, 1, the reaction temperature in the reactor hearth changes with time: two t two H two f clocks between 2 and 15 minutes 'No matter what gasification temperature, the curve changes are divided into Two stages. The temperature of the first-stage reaction is produced at the gasification temperature. At this stage, the main Λ^, ^ 曰 小 小 Γ 煤 反 反 反 反 反 反 反 反 反 反 反 反 。 。 。 。 。 。 。 。 。 。 。 。 From the thermogravimetric analysis in the third figure, it can be known that when the coal nuisance enters the south temperature from the η drama, it will promote the reaction. The reaction temperature in the second stage is slightly higher than the gasification over time. Lai caused. After the job, it is vaporized into a gas due to the previous pyrolysis reaction. This reaction is also called de-swing == Γ 279436. The gas has a lower ignition point, causing the volatiles to burn and causing the temperature to rise. Once the reaction temperature gradually stabilizes, the importance of the de-volatile reaction will gradually decrease, and the conversion from coke becomes more important. In summary, the temperature monitoring technology developed here shows that the gasification reaction of the fuel undergoes endothermic (drying, pyrolysis and devolution), exothermic (combustion) and coke reaction. Then, the fifth figure shows the concentration of hydrogen, methane, carbon monoxide and carbon dioxide measured at the different gasification temperatures (8 〇〇, 9 〇〇, 1 〇〇 (rc) according to the above measurement method. In the 800 °C experiment, the measurement method shows that the hydrogen concentration decreases rapidly from the initial 31% with time, and the methane production concentration also decreases from nearly 8% at the highest 15 minutes' to a concentration of zero at 50 minutes. The initial C0 concentration is greater than C〇2, because the de-evaporation and the cleavage reaction proceed simultaneously, but after 35 minutes, the CO concentration is gradually less than C〇2, and the combustion reaction becomes dominant. At the gasification temperature of 9〇〇 In the °C experiment, although the hydrogen production concentration also showed a significant decrease with time, the measured initial concentration was about 47%, which was much higher than the 8〇〇°C hydrogen concentration of 31%. As for methane. At the initial stage of gasification, the concentration of formation is also increased by more than about 1% at 800 °C, but the concentration declines the same as that of hydrogen, and the concentration of c〇 and C〇2 is generated, although the initial C0 concentration is significantly ahead of c〇2, but Presented at a concentration of C0 over time Decrease, on the contrary, 'C〇2 gradually increases, and the two compete with each other. By the end of the experiment, the concentration of c〇 is still slightly higher than the concentration of C〇2. Since the formation of C0 can be used to explain the reactivity of coke, the above results It is shown that the reaction of coke at 900 ° C is better than 800 ° C. As for the "test of 10 〇〇 c", it can be found that the initial concentration of nitrogen is 65% more, and the initial concentration of smoldering is less than 900. At °C, this is due to the obvious tendency of methane to be cleaved into hydrogen at this high temperature (1〇〇〇.(3) environment, so the concentration is decreased. As for the formation concentration of C0 and C〇2, the reaction due to coke is more Obviously, the concentration of CO is much higher than that of c〇2. See the sixth figure. The ratio of the ratio of C0 to C〇2 concentration at three different gasification temperatures is obtained according to the above measurement results. It can be used as an important indicator of coal gasification reaction and coke reaction. Overall, as the gasification temperature increases, we can see that the ratio of the two also rises significantly. It can be seen that the gasification temperature coke inverse 11 1279436 ^ has Significant impact, so the seventh picture shows Coal reaction at three different gasification temperatures = which indicates that when the gasification temperature is _, _, and (10) generation, the coal turns = 36.73%, 37.97%, and 54.55%. On the other hand, the __ degree ratio changes with = When the reaction time reaches 15 ^ minutes, the distribution curve shows a large value of silver 由于 because (7) can be regarded as an important product of gasification, and (3) 2 is an important result of combustion, so the above maximum distribution can explain the gas combustion process. The competitive situation. The measurement method of the fuel gasification and coke reaction process described in the above-mentioned 4, = 1U fixed-bed gasification furnace set up by itself, combined with temperature monitoring and gas treatment, can produce cleanliness And the gas without interfering substances, and by concentration measurement and data, can provide a complete and accurate reaction of fuel gasification and coke reaction: that is, the method of the present invention utilizes the natural law technical idea Highly creative, the symbol a invention patent, and apply for it according to law. BRIEF DESCRIPTION OF THE DRAWINGS (I) Brief Description of Drawings Fig.: A schematic diagram of a measuring system for carrying out the method of the present invention. == Figure: Flowchart (representative figure) for carrying out the method of the invention. 1. Figure yoke Thermogravimetric analysis diagram of the coal of the method of the present invention placed in air #4图······················· Figure. Gas concentration profile for carrying out the method of the invention. • (10) TM2 ratio distribution map for carrying out the method of the invention. β • The coal reaction rate for carrying out the process of the invention. (2) Main part representative symbol description (1) Measurement system (10) Reaction furnace body (12) Hearth (14) Alumina (16) Power controller (11) Furnace tube (13) Heater (15) Temperature The controller (20) is provided with a pipe 12 1279436 (21) screw (23) into the hopper (31) intake pipe (33) cylinder (41) data extraction system (50) gas processing system (511) non-embroidered steel pipe (513 South Temperature Gas (514) Ice Cold Water (52) Washing Tank (522) Inlet End Plastic Tube (53) Filter (54) Drying Tower (60) Gas Concentration Measuring Device (62) Gas Analyzer (22) Motor (30) lower erection tube (32) flow meter (40) reaction monitoring device (42) heat sensor (51) condensing tube (512) copper tube (514) ice cold water (515) multi-pass tube (521) conical flask (523) Exhaust end plastic tube (531) filter paper (541) silicone (61) gas chromatograph (63) gas needle 13