中國(guó)歡學(xué)逼擺2010,27(6):355361Chinese Agricultural Science Bulletin秸稈生物質(zhì)熱裂解技術(shù)的研究進(jìn)展王偉文,馮小芹,段繼海(青島科技大學(xué),山東青島266042)摘要:生物質(zhì)能源因其具有優(yōu)良的環(huán)境友好性和可再生性而備受關(guān)注。開發(fā)利用生物質(zhì)能源對(duì)廢棄資源回收、能源結(jié)構(gòu)轉(zhuǎn)換、環(huán)境改善和保護(hù)等方面具有重大意義。筆者綜述了目前生物質(zhì)能的主要利用和開發(fā)形式,分析了生物質(zhì)的熱裂解機(jī)理、生物質(zhì)熱裂解技術(shù)的幾種典型工藝和各種裂解裝置的特點(diǎn)。此外,開發(fā)出規(guī)?；a(chǎn)和成套設(shè)備的熱裂解工藝是目前亟待解決的重要課題,亦是生物質(zhì)熱解發(fā)展的一種趨勢(shì)。關(guān)鍵詞:生物質(zhì);熱裂解;熱裂解機(jī)理;裂解工藝;反應(yīng)器中圖分類號(hào):TQ91文獻(xiàn)標(biāo)志碼:A論文編號(hào):20102596Research Progress on Biomass Pyrolysis Techniques of StrawWang Weiwen, Feng Xiaoqin, Duan Jihai(Qingdao University of Science and Technology, Qingdao Shandong 266042)Abstract: Biomass energy has attracted consle attention owing to its excellent environmentalfriendliness and renewability. It is significant to explore and utilize the biomass energy in various aspects,including waste recycling, conversion of energy structure, environmental improvement and protection, and soforth. The author reviewed the application and development of biomass energy, and analyzed the mechanism ofpyrolysis and the typical technology of biomass pyrolysis process, as well as the characteristics of a variety ofcracker. In addition, developing a large-scale production and reactor was an important issue and also thetendency of biomass pyrolysis in the thermal cracking processKey words: biomass; thermal cracking: pyrolysis mechanism; cracking process; reactor0引言階段。面對(duì)能源危機(jī),生物質(zhì)作為可再生資源,是發(fā)展的生物質(zhì)快速熱裂解的研究始于20世紀(jì)70年代。一個(gè)走向,它的開發(fā)利用是當(dāng)前國(guó)內(nèi)外廣泛關(guān)注的重目前存在的主要問題是快速裂解的條件不易控制,熱犬課題。中國(guó)作為農(nóng)業(yè)大國(guó),生物質(zhì)資源十分豐富,能利用率不高,對(duì)產(chǎn)率影響較大。另外,生物燃料油的每年農(nóng)作物秸稈產(chǎn)量達(dá)7億t。秸稈作為潔凈能源具有精制也是亟待解決的難題之一。低污染性、資源分布廣、產(chǎn)量大、可再生性強(qiáng)等特點(diǎn),1生物質(zhì)能源利用技術(shù)—熱裂解故其能源利用既是中國(guó)開拓新的能源途徑、緩解能1.1生物質(zhì)能的主要利用和開發(fā)形式源供需矛盾的戰(zhàn)略措施,也是解決“三農(nóng)問題”、保證社生物質(zhì)能轉(zhuǎn)化技術(shù),即生物質(zhì)原料轉(zhuǎn)化為高品位會(huì)經(jīng)濟(jì)持續(xù)發(fā)展的重要任務(wù)。中國(guó)的相關(guān)研發(fā)機(jī)構(gòu)雖能源的技術(shù),可分為直接燃燒、生物化學(xué)轉(zhuǎn)化和熱化學(xué)然在木質(zhì)纖維素水解、可發(fā)酵糖生物利用以及代謝產(chǎn)轉(zhuǎn)化3大類。圖1形象地表述了生物質(zhì)的利用形式物分離與純化等方法和關(guān)鍵技術(shù)上取得了重大突破生物質(zhì)作為一種可再生能源,早在19世紀(jì)已經(jīng)出但在快速熱裂解技術(shù)開發(fā)中,尚未突破規(guī)模化生產(chǎn)和現(xiàn)很成熟的生物化學(xué)轉(zhuǎn)化制燃料乙醇、沼氣等技術(shù),但成套設(shè)備的難關(guān),大多停留在中試和中試之前的研發(fā)是生物質(zhì)快速熱裂解生產(chǎn)生物質(zhì)液體燃料的技術(shù)還不中國(guó)煤化工第一作者簡(jiǎn)介:王偉文,女,1968年出生,副教授,博士,研究方向:多相流體的流動(dòng)CNMH區(qū)鄭州略3號(hào)61信箱Tel: 0532-84022752, E-mail: wwwang@qust.edu.cn收稿日期:20100906,修回日期:20101011356中國(guó)農(nóng)學(xué)逼報(bào)htp:/www.casb.org.cn直接燃燒生物化學(xué)轉(zhuǎn)化厭氧發(fā)酵沼氣生物酶轉(zhuǎn)化高壓加氫乙醇、甲醇等汽油柴油生物質(zhì)成型/干餾催化精制固體(焦炭)汽油/柴油乳化乳化油高壓液化精制熱化學(xué)轉(zhuǎn)化」「快速熱解液體(生物油)蒸汽重整L分離提純化學(xué)品部分氧化氣體LF合成一液體燃料圖1生物質(zhì)能轉(zhuǎn)化技術(shù)成熟。目前對(duì)生物質(zhì)轉(zhuǎn)化利用方式的研究主要集中見途徑在熱化學(xué)轉(zhuǎn)化方面,其中熱化學(xué)轉(zhuǎn)化主要有熱解干生物質(zhì)熱解液化技術(shù)是其利用的主要形式之一,該餾、熱解氣化和熱解液化3種。熱解干餾技術(shù)可將木技術(shù)很大程度上能緩解當(dāng)今社會(huì)的能源危機(jī)以及環(huán)境質(zhì)生物質(zhì)轉(zhuǎn)為炭燃?xì)夂投喾N化學(xué)品;熱解氣化可將生污染,是人類開發(fā)可再生資源的一種非常有效的途徑物質(zhì)主要轉(zhuǎn)化為可燃?xì)怏w可用作生活燃?xì)庖部捎米?2秸稈生物質(zhì)熱裂解原理制氫或合成氣的原料還可通過鍋爐或內(nèi)燃機(jī)等轉(zhuǎn)化生物質(zhì)熱裂解是指生物質(zhì)在完全缺氧或有限氧供為熱能或電能;熱解液化是在中溫快速加熱條件下使應(yīng)條件下的熱降解,最終生成炭、可冷凝氣體(生物生物質(zhì)迅速熱解,并使熱解氣迅速冷凝獲得初級(jí)液體燃油)和可燃?xì)怏w(不可冷凝)的過程。生物質(zhì)熱裂解燃料(生物油)該燃料可以直接燃燒使用,提質(zhì)后可用是復(fù)雜的熱化學(xué)反應(yīng)過程包含分子鍵斷裂、異構(gòu)化和作為內(nèi)燃機(jī)燃料。小分子聚合等反應(yīng)。生物質(zhì)主要由纖維素半纖維素生物質(zhì)是唯一可轉(zhuǎn)化成可替代常規(guī)液態(tài)石油燃料和木質(zhì)素3種主要組成物四以及一些可溶于極性或和其他化學(xué)品的可再生碳資源而熱化學(xué)高效轉(zhuǎn)化利弱極性溶劑的提取物組成。半纖維素主要在225~用技術(shù)又是生物質(zhì)能源開發(fā)利用的最主要途徑因此350℃分解:纖維素主要在325-375℃分解:木質(zhì)素在生物質(zhì)熱解技術(shù)越來越受到研究者的關(guān)注。如圖250500℃分解。半纖維素和纖維素主要產(chǎn)生揮發(fā)性2顯示了生物質(zhì)通過熱解轉(zhuǎn)化為生物燃油的幾種常物質(zhì),而木質(zhì)素主要分解成炭。試驗(yàn)表明,纖維素在325℃時(shí)開始熱分解,隨著溫度升高降解逐步加劇,至固體生物質(zhì)623643℃時(shí)降解為低分子碎片,其降解過程為嗎直接液化「間接液化(C6HIoOShr n C6HgoOs高壓液化][常壓液化][高溫液化][熱解氣體]CHIdOH0+2 CH液化油氣體精制cH2C—CH+H2CHy-CHoH匚精制合成中國(guó)煤化工化學(xué)品燃料油CNMHG圖2生物質(zhì)熱化學(xué)轉(zhuǎn)化方法及產(chǎn)物王偉文等:秸稈生物質(zhì)熱裂解技術(shù)的研究進(jìn)展357·半纖維素結(jié)構(gòu)上帶有支鏈,比纖維素更容易分解,其熱解機(jī)理與纖維素相似。其反應(yīng)方程式可概括為:生物質(zhì)一快通→生物油+炭+氣CO2+CH4+CH,O按溫度、升溫速率、固體停留時(shí)間(反應(yīng)時(shí)間)和粒荷蘭 Twente(喬特)大學(xué) Elly Hoekstra等研發(fā)了徑等實(shí)驗(yàn)條件可將熱解分為:(1)炭化(慢熱解)溫¨一套及時(shí)去除裂解氣中焦和灰分的新型工藝。該系統(tǒng)度不超過500℃,產(chǎn)物以炭為主;(2)快速熱解溫度一主要由內(nèi)部裝的氣體過濾器的連續(xù)流化床反應(yīng)器組般控制在500600℃,產(chǎn)物以可冷凝氣為主,其被冷凝成,其過濾器是由金屬絲制成的,孔徑為0005mm后變成生物燃油;(3)氣化,溫度為700-800℃,產(chǎn)物以反應(yīng)器用電子烤箱加熱。物料采用螺紋進(jìn)料,顆粒受不易冷凝氣為主。熱發(fā)生裂解反應(yīng),部分裂解氣通過過濾器凈化進(jìn)入冷2生物質(zhì)熱裂解工藝凝系統(tǒng),也有部分裂解氣經(jīng)旋風(fēng)分離器進(jìn)入冷凝器,經(jīng)目前,世界各地的研究機(jī)構(gòu)相繼開發(fā)了各式各樣冷凝后得到生物油。與只有旋風(fēng)分離器而沒有過濾器的生物質(zhì)熱解工藝,依據(jù)生物質(zhì)熱裂解技術(shù)的基本的工藝相比,該系統(tǒng)具有良好的工藝穩(wěn)定性,反應(yīng)過程原理,大體可分為炭化、氣化和液化工藝中氣相停留時(shí)間短,可以防止熱解蒸氣的二次裂解21生物質(zhì)炭化產(chǎn)物油只含有微量的固體、堿金屬、灰分等雜質(zhì)穩(wěn)定性生物炭化工藝最早是先成型后炭化。隨著技術(shù)好、不宜老化等優(yōu)點(diǎn)。但是加工能力(07kgh)小。的不斷進(jìn)步,出現(xiàn)了先炭化后成型的生產(chǎn)工藝,較前William J. DeSisto等提出了鼓泡流化床反應(yīng)器者能充分利用余熱。中國(guó)科學(xué)院蘭州化學(xué)物理研究的工藝流程。流化床內(nèi)采用玻璃粉為換熱介質(zhì)。物料提出的生物質(zhì)連續(xù)炭化工藝省去了機(jī)械成型環(huán)節(jié),大進(jìn)入反應(yīng)器內(nèi)與加熱的玻璃粉接觸,在溫度為400大節(jié)省了能源。生物質(zhì)炭化壓縮成型等工藝在中國(guó)600℃范圍內(nèi)獲得熱量后發(fā)生裂解反應(yīng)產(chǎn)生的裂解氣發(fā)展比較成熟。先進(jìn)入凈化器,再冷凝,最后經(jīng)靜電沉淀器被收集。液22生物質(zhì)氣化相產(chǎn)率在反應(yīng)溫度500℃時(shí)達(dá)到最大,而氣相形成物生物質(zhì)氣化反應(yīng)過程主要取決于氣化劑的選擇、在600℃時(shí)才增強(qiáng)。反應(yīng)器的表觀速度為50-60cm/s,氣化爐中反應(yīng)溫度和壓力的控制物料的停留時(shí)間。裂解氣停留時(shí)間≌2.0s。生物質(zhì)進(jìn)料量為1g/minYu r Xie等考察了添加劑對(duì)于生物質(zhì)高溫蒸汽Roel J. M. Westerhof等研發(fā)了一套實(shí)驗(yàn)室規(guī)模氣化過程的影響。反應(yīng)溫度為800℃,鎳催化下H2產(chǎn)的連續(xù)化生產(chǎn)生物質(zhì)燃料油的流化床反應(yīng)器工藝流率最高達(dá)到359%(不添加任何催化劑時(shí),H產(chǎn)率為程。該工藝中流化床反應(yīng)器內(nèi)的換熱介質(zhì)為硅砂,其102%)。反應(yīng)溫度為900℃,FeO3催化下H2產(chǎn)率最高平均粒徑為025mm。物料的平均粒徑為1mm,最大達(dá)406%不添加任何催化劑時(shí)H2產(chǎn)率為238%)。相粒徑為2mm。物料處理能力為1kgh。反應(yīng)過程中同氣化溫度下,加入添加劑能有效地提高產(chǎn)氣率,并且允許物料的停留時(shí)間達(dá)25min。試驗(yàn)中采用實(shí)驗(yàn)室規(guī)能改善氣體產(chǎn)品的質(zhì)量。但是高溫氣化不僅要求設(shè)備模的噴霧器對(duì)裂解油進(jìn)行穩(wěn)定化處理。當(dāng)反應(yīng)溫度從具有良好的耐熱性,且消耗大量的熱能。 Weerawut330℃增加到450℃時(shí),裂解油的產(chǎn)量隨之增加。但當(dāng)Chaiwat研究了低溫下生物質(zhì)的氣化過程。低溫空反應(yīng)溫度從450℃增加到530℃時(shí),產(chǎn)油量基本保持不氣作氣化劑可使焦油產(chǎn)率50w%減少到20w%,而變溫度升至580℃時(shí),產(chǎn)油量反而減少。反應(yīng)溫度CO2的產(chǎn)率會(huì)增加且所得不凝氣的熱值較低。根據(jù)不360℃時(shí),產(chǎn)油量58w%,反應(yīng)溫度580℃時(shí),產(chǎn)油量同工藝條件,生物質(zhì)氣化產(chǎn)生的不凝氣可以是低熱值6w%。相比于530℃時(shí),產(chǎn)物油中含焦炭量5w%或中熱值氣,在氣體產(chǎn)物中或多或少都含有一定量的360℃含焦炭量較少(2w%)。因此,在此系統(tǒng)中反應(yīng)焦油和水分,而不凝氣中的焦油不易清除。另外,相對(duì)溫度為360℃時(shí)所得生物油的質(zhì)量較好于液體生物燃料而言氣體燃料運(yùn)輸時(shí)要求設(shè)備要具上述工藝在改善裂解產(chǎn)物質(zhì)量和產(chǎn)油率上都有所有一定的承壓能力且密封性良好。突破,但是均為實(shí)驗(yàn)室規(guī)模的研究,處理量低、生產(chǎn)能23生物質(zhì)快速熱解——液化力小。為此,青島科技大學(xué)刈研發(fā)了下吸式移動(dòng)床秸由于液體產(chǎn)物易于運(yùn)輸存儲(chǔ)等諸多優(yōu)點(diǎn)和隨之稈閃汽中國(guó)煤化工0g的工業(yè)化而來的人們對(duì)其研究興趣的日益高漲對(duì)液體產(chǎn)物產(chǎn)生產(chǎn)解產(chǎn)生的燃?xì)鉃榱崖氏鄬?duì)較高的快速熱解技術(shù)的研究和應(yīng)用越來越受到解爐CNMH步冷卻后送入空氣人們的重視脫除倉(cāng),以脫除物料空隙中的空氣,并對(duì)物料進(jìn)一步干358中田農(nóng)學(xué)逼報(bào)htp:/www.casb.org.cn導(dǎo)熱油去氣體冷凝器作冷卻器活性炭固體冷凝冷卻劑物料干燥氣脫出倉(cāng)熱裂解爐氣固分離器風(fēng)除塵氣體冷凝器氣體排空真空泵氣體冷凝器氣體洗滌塔低沸點(diǎn)生物質(zhì)油來導(dǎo)熱油生物質(zhì)炭混合研磨新型燃料圖3秸稈裂解工藝流程示意燥預(yù)熱然后排空。洗滌塔主要由冷凝器冷凝下來的熱方式在很大程度上決定了產(chǎn)物的最終分布和生物油生物質(zhì)油部分回流用液體對(duì)氣體進(jìn)一步洗滌凈化冷的質(zhì)量、產(chǎn)率等,并且對(duì)于生產(chǎn)過程中條件的控制和熱凝下來的部分生物質(zhì)油作為產(chǎn)品,所得產(chǎn)品不含固體能的利用有著重要影響。因此,反應(yīng)器類型和加熱方懸浮物透明度好質(zhì)量高。氣體洗滌塔頂?shù)睦淠鞑墒降倪x擇是各種快速裂解工藝的關(guān)鍵環(huán)節(jié)。用導(dǎo)熱油作冷凝劑,與裂解爐出氣冷卻器串接被加熱3生物質(zhì)熱裂解的核心裝置的導(dǎo)熱油用于物料干燥。該工藝比較顯著的特點(diǎn):熱反應(yīng)器是生物質(zhì)進(jìn)行熱解的重要裝置,是目前國(guó)裂解爐用自身產(chǎn)生的燃?xì)饧訜釤崃勘怀浞掷?不需內(nèi)外關(guān)注的焦點(diǎn)炯。美國(guó)加拿大和芬蘭等國(guó)對(duì)生物要任何化石燃料;整個(gè)裝置不排放任何污染物洗滌塔質(zhì)熱解裝置的研究已經(jīng)較為成熟,并研發(fā)了固定床、流底流出的含渣高,沸點(diǎn)物量少化床、真空移動(dòng)床、引流床、夾帶流、多爐裝置、旋轉(zhuǎn)爐、對(duì)比分析各種工藝方法,秸稈快速熱裂解具有類旋轉(zhuǎn)錐反應(yīng)器和輻射爐等反應(yīng)器。代表工藝有似的基本工藝流程即物料經(jīng)粉碎、干燥后,在反應(yīng)器 Tenet、GIT、 Ensyn、 GIEC. NREL和 Laval等。但是內(nèi)進(jìn)行反應(yīng),反應(yīng)所得產(chǎn)物一般都含有炭、焦油、裂解由于制造及工藝條件的限制,而用于工業(yè)化生產(chǎn)的只氣等成分。其中,可冷凝部分的裂解氣冷凝后即為目有輸送床和循環(huán)流化床反應(yīng)器的產(chǎn)物生物油,其他產(chǎn)物可通過相應(yīng)的凈化工藝或能荷蘭喬特( Twente)大學(xué)提出的旋轉(zhuǎn)錐式反應(yīng)器具量循環(huán)工藝進(jìn)行處理。目前,中國(guó)在快速熱裂解技術(shù)有產(chǎn)油率高、不用載氣等優(yōu)點(diǎn),但生產(chǎn)規(guī)模小,能耗較開發(fā)中,尚未突破規(guī)?；a(chǎn)和成套設(shè)備的大關(guān)生物高。美國(guó)喬治亞理工學(xué)院GT設(shè)計(jì)的攜帶床反應(yīng)器質(zhì)快速熱裂解產(chǎn)品(生物質(zhì)油和木炭)在中國(guó)國(guó)內(nèi)市場(chǎng)產(chǎn)油率也較高卻需要大量熱煙并產(chǎn)生大量低熱值的中尚屬空白。因此,想要生物質(zhì)熱解制生物油技術(shù)走不凝氣浪費(fèi)能源。加拿大森林工程師協(xié)會(huì)開發(fā)的循向較大規(guī)模的工業(yè)化生產(chǎn),必須研究開發(fā)出一套新工環(huán)流化床反應(yīng)器美國(guó)太陽能研究所(SER)開發(fā)的渦藝,而新工藝開發(fā)的關(guān)鍵技術(shù)就是生物質(zhì)裂解裝置的旋反應(yīng)器加拿大拉瓦爾(Lava)大學(xué)開發(fā)的多層真空設(shè)計(jì)。熱解磨反應(yīng)器都存有各自的不足之處,簡(jiǎn)述如表在生物質(zhì)快速熱裂解的各種工藝中,反應(yīng)器和加1。表15種常見閃速熱裂解反應(yīng)器的特性評(píng)價(jià)反應(yīng)器類型喂入顆粒尺寸設(shè)備復(fù)雜程度性氣體需要量設(shè)備尺寸擴(kuò)大規(guī)模中等燒蝕反應(yīng)器中國(guó)煤化工引流床復(fù)雜旋轉(zhuǎn)錐復(fù)雜CNMHG復(fù)雜王偉文等:秸稈生物質(zhì)熱裂解技術(shù)的研究進(jìn)展359·世界上生物質(zhì)熱裂解工藝還未實(shí)現(xiàn)規(guī)模化的工業(yè)0) Hertwich E G, Zhang x P. 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