第32卷第4期燃料化學(xué)學(xué)報(bào)204年8月JOURNAL OF FUEL CHEMISTRY AND TECHNOLOGY文章編號:0253-240X2004)40510-03生物質(zhì)熱解油氣化試驗(yàn)研究朱錫鋒, Venderboschrh1.中國科技大學(xué)生物質(zhì)潔凈能源實(shí)驗(yàn)室,安徽合肥230026;2,. BIG Biomass Technology Group, enschede,7500AE, The netherlands)關(guān)鍵詞:生物質(zhì);生物油;熱解氣化中圖分類號:TQ517.2文獻(xiàn)標(biāo)識碼:B生物質(zhì)是一種環(huán)境友好可再生資源可以通過直徑0.3mm這樣既能滿足生物油的霧化效果又多種途徑轉(zhuǎn)化為液體燃料。生物質(zhì)熱解液化即是在不致孔口被生物油中的固體顆粒堵塞:解部分由缺氧狀態(tài)下對生物質(zhì)進(jìn)行快速加熱然后再對熱解長200mm、直徑18mm的無縫耐熱不銹鋼管組成產(chǎn)物進(jìn)行快速冷凝最后獲得一種稱為生物油旳液外繞加熱電阻絲加熱溫度通過可控硅溫控器進(jìn)行體燃料的技術(shù)。該技術(shù)以及生物油的特點(diǎn)主要有:調(diào)節(jié)泠卻部分由一強(qiáng)制空氣冷卻換熱器組成熱解熱解液化溫度為500℃遠(yuǎn)低于生物質(zhì)熱解氣化所高溫氣體流經(jīng)此換熱器后溫度能夠降低到50℃泠需800℃~1000℃因而工藝難度較小泩生物油體凝部分由兩個洗瓶組成第一個是水洗瓶第二個是積能量密度約為20×10JJ/m3為生物質(zhì)的10倍適酒精洗瓶用于過濾和吸收氣體中的固體殘余物計(jì)宜于遠(yuǎn)距離運(yùn)輸和大規(guī)模儲存泩物油成分雖然復(fù)量部分由高精度容積式氣體流量計(jì)組成氣體計(jì)量雜但不同生物質(zhì)所產(chǎn)的生物油具有良好的相互混合后送至室外。的特性便于大規(guī)模收集和轉(zhuǎn)化應(yīng)用泩物油屬于牛頓液體常溫下粘度系數(shù)為40cP~60cP與60號機(jī)械油相當(dāng)流動和霧化特性較好泩生物油含水為20%氧質(zhì)量分?jǐn)?shù)為50%熱值為16MJ/kg~18MJ/kg熱值偏低熱穩(wěn)定性較差圖1生物油無氧熱解試驗(yàn)裝置流程圖由上可見生物油只是一種初級液體燃料雖然Figure 1 Flow chart of bio-oil gasification without oxygen可以直接用于鍋爐等燃燒熱力設(shè)備但用于內(nèi)燃機(jī)I--piston pump :2--cracking tube :2'-temperature controller還需要經(jīng)過精制加工如先對生物油進(jìn)行熱解氣化ottle: 4 -ethanol制備合成氣然后再合成為高品位的液體燃料如甲washing bottle , 5--flowmeter醇和二甲醚等。1.2實(shí)驗(yàn)方法由于生物油在高溫作用下容易發(fā)考慮到生物油氧質(zhì)量分?jǐn)?shù)較高氣化時不需要生聚合反應(yīng)而結(jié)焦因此為避免針形霧化器孔口堵外部供氧或只需要提供少量的氧。本文在無外部供塞本實(shí)驗(yàn)采用的方法為氧情況下對生物油進(jìn)行了熱解氣化試驗(yàn)生物油中(1)試驗(yàn)開始時首先接通電源對熱解管進(jìn)行氫氧元素的質(zhì)量轉(zhuǎn)化率為85%而碳元素的轉(zhuǎn)化率空載加熱使其溫度較快上升到預(yù)定值只有55%由此說明生物油熱解氣化仍需外部提供(2)當(dāng)溫度達(dá)到預(yù)定值后開啟柱塞泵先將酒少量氧氣作為氣化劑。精按實(shí)驗(yàn)要求旳流量泵入熱解管,以清洗系統(tǒng)內(nèi)部實(shí)驗(yàn)部分管路和縮小正式實(shí)驗(yàn)時的溫度波動1.1實(shí)驗(yàn)裝置圖1所示是生物油熱解氣化試驗(yàn)3)當(dāng)溫度再次上升到預(yù)定值后將酒精切換裝置流程圖它主要包括進(jìn)料熱解冷卻凈化和計(jì)為生物講行正式試驗(yàn)并開始計(jì)時量五個部分。其中進(jìn)料部分由一臺柱塞泵組成泵中國煤化工先將生物油切換為酒的流量在2gmm-100gmn無級可調(diào)泵的出囗是精并CNMHG關(guān)閉加熱電源和柱塞針形霧化器孔口直徑可以變換試驗(yàn)采用的孔口泵電源收稿日期:2003-12-04;修回日期:20040610作者簡介燚962-),男,安徽南陵人,副教授,從事生物質(zhì)轉(zhuǎn)換技術(shù)研究,Eπilx加@usce,su,cn朱錫鋒等:生物質(zhì)熱解油氣化試驗(yàn)研究511〔5)試驗(yàn)前后對洗瓶進(jìn)行稱重并記錄氣體流1.3實(shí)驗(yàn)原料實(shí)驗(yàn)原料是一種木屑熱解液化得量計(jì)的讀數(shù)。為保證計(jì)量精度在前后時間段由酒到的生物油其主要特性和元素組成分別列于表1精熱解產(chǎn)生的氣體經(jīng)換熱器冷卻后由旁路引向室和表2。外而不經(jīng)過洗瓶和流量計(jì)表1生物油的主要特性Table 1 main characteristics of bio-oilDensityCaloric valueViscosityo(kg m ')QAMJ kg) n( mms)0.07表2生物油的元素分析Table 2 Ultimate analysis of bio-oilUltimate analysis wd/%Element analysis 10 /10-K41.57.650.70.20.0091.4實(shí)驗(yàn)參數(shù)為穩(wěn)定獲取生物油熱解氣化的實(shí)表3為生物油熱解氣經(jīng)過氣相色譜分析得到的驗(yàn)數(shù)據(jù)每次試驗(yàn)所采用實(shí)驗(yàn)參數(shù)均相同即熱解反氣體組分以及由這些組分計(jì)算獲得的熱解氣的質(zhì)應(yīng)溫度控制在(1000±10)℃;熱解管內(nèi)的壓力為量、密度和熱值。由表可見3000Pa,等于熱解系統(tǒng)的流動阻力損失泩生物油泵(1)生物油熱解氣氧氣組分為零氮?dú)饨M分很入質(zhì)量流量為3.5g/min正式試驗(yàn)10min。低組分最高的四種氣體依次分別是一氧化碳、氫2結(jié)果與分析氣、甲烷和二氧化碳。2.1熱解氣組分與特性按照上述實(shí)驗(yàn)方案本研2)生物油熱解氣的熱值為21.09MJ/kg乘以究對生物油熱解氣化進(jìn)行了若干次重復(fù)試驗(yàn)每次氣體密度則為16.45MJ/m3屬于品質(zhì)較好的中熱值試驗(yàn)均用去35g生物油并產(chǎn)生0.024m3熱解氣,燃?xì)饧瓤捎米鳛榫用裆钊細(xì)庖部勺鳛楣I(yè)原料數(shù)據(jù)重復(fù)性較好。用于生產(chǎn)合成氣表3生物油熱解氣的組分與特性Table 3 Concentration and properties of cracked gas from bio-oiVolume o/%031.510.000.2016.9237.739.384.000.120.090.05100.00ity p( kg m 3)Caloric valllue Q(MJ kg1)141.650.000.00554510090050.2551.8348.8749.9421.092.2熱解氣化質(zhì)量衡算試驗(yàn)使用35g生物油熱個重要評價指標(biāo)是其質(zhì)量轉(zhuǎn)化率表5所列是根據(jù)解產(chǎn)生了187g氣體,試驗(yàn)前后兩只洗瓶的質(zhì)量增上述實(shí)驗(yàn)結(jié)果計(jì)算獲得的碳、氬、氧以及這三種元素量為15.3g。據(jù)此可對生物油熱解氣化進(jìn)行質(zhì)量平總的質(zhì)量轉(zhuǎn)化率。由于生物油中的水分和灰分不能衡計(jì)算結(jié)果列于表4。由表可見,尚有少量殘余物熱解氣化故此處采用的計(jì)算基準(zhǔn)是干燥無灰基。質(zhì)如焦炭等粘附在管道內(nèi)壁上。物油拉氣化質(zhì)量轉(zhuǎn)化率表4生物油熱解氣化質(zhì)量衡算中國煤化-ncy of bio-oil gasificationTable 4 Mass balance of bio-oil gasificationCNMHGH 0 C+H+0)Input mass ma /gOutput mass mad /gMass balanceBio-oil m,/g15.381.6710.3927.44crackedCracked gas m dar /g2.3熱解氣賚量轉(zhuǎn)化率生物油熱解氣化的-Mass conversion efficiency n/% 55. 14 86.23 84.50 68.15512化致謝:本項(xiàng)研究是筆者在荷蘭BTG生物質(zhì)技術(shù)研究所從事訪問學(xué)者期間完成的在此謹(jǐn)向BTG表示衷心感謝參考文獻(xiàn)[Ⅰ]蘇學(xué)泳汪智微程從眀等.生物質(zhì)在流化床中旳熱解和氣化硏究J燃料化學(xué)學(xué)報(bào),2000,2×4)298305( SU Xue-yong, WANG Zhi-wei, CHENG Cong-ming et al. 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Renewable Energy, 2003(1): 11-14.)[10]朱錫鋒, VENDERBOSCHR H王俊三.燃料理論空燃比與其高位熱值之間的關(guān)系J]中國科技大學(xué)學(xué)報(bào),204,31)11-(ZHU Xi-feng, VENDERBOSCH R H, WANG Jun-san. Correlation between stoichiometrical ratio of air to fuel and its higherheating valud J]. Joumal of University of Science and Technology of China 2004, 3(1): 111-115.)Experimental research on gasification of bio-oilderived from biomass pyrolysisZHU Xi-feng Venderbosch R H(I. Laboratory of Biomass Clean Energy University of Science and Technology of China, Hefei 230026,Chin2. BTG Biomass Technology Group, Enschede, 7500AE, the NetherlandsAbstract Biomass can be converted into bio-oil by pyrolysis with high heating and cooling rates. Bio-oil is a crudeoil which can be upgraded into high quality liquid fuels for instance, it can be first gasified into syngas and then synthesized into methanol, dimethyl ether and so on. Considering bio-oil has high oxygen content bio-oil gasificationwithout any external supply of oxygen has been performed. Thexygen and hydrogen elements could reach as high as 85%, but thgen supply should be needed to improve the mass conversion effiH中國煤化 Conversion efficiencies olCNMHGKey words: biomass bio-oil i gasificationAuthor introduction: ZHU Xi-feng(1962), male, Associate Professor engaged in the research of biomass conversionE-mailxfzhu@@ustc.edu.cn