TW202003855A - Integrated method for improving production rate of biogas using lignocellulosic depolymerization with anaerobic digestion - Google Patents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
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Abstract
Description
本發明係有關於一種沼氣生產方法，尤指涉及一種提升沼氣生成效率之生產方法，該方法係利用程序整合之方式，特別係指整合解聚前處理程序與厭氧消化程序者。The invention relates to a biogas production method, in particular to a production method for improving biogas generation efficiency. The method is a method of using program integration, and particularly refers to a person integrating a pre-depolymerization treatment process and an anaerobic digestion process.
針對沼氣生產技術，目前主要原料皆以畜殖場廢水、廚餘或都市固體廢棄物等為主，鮮少以纖維原料作為厭氧消化生產沼氣之原料，主要原因為纖維原料其結構堅韌，雖內含豐富之碳源，包括纖維素、半纖維素與木質素，但由於其交錯結構與組成關係，使其無法直接應用於沼氣生產產業。為解決纖維原料結構問題，可採用物理法、化學法、生物法、物理化學法或微生物法等。該物理法主要以機械方式例如研磨法將纖維原料之尺度大小，縮小至一定程度，增加接觸比表面積，但此類方法相當耗能。該化學法包括鹼法、稀酸法或溶劑法等，其中稀酸法主要將纖維原料之半纖維素水解為單糖，使原料結構鬆散，但對木質素含量較高之纖維原料，其纖維素及木質素之結構分離效果有限；鹼法處理方式，主要以去除木質素為主，但通常伴隨大量之廢液產生，造成廢液回收與高耗水量問題與缺陷。微生物法係以微生物進行纖維原料分解，分解速度與物理法或化學法比較相對較慢。 現有相關專利中，中國大陸CN101899474專利揭示一種秸稈沼氣化利用的預處理方法，係採用密封式存放進行腐敗分解，預處理分解時間需要8～15天，顯見此專利預處理時間較長。中國大陸CN104826855專利揭示一種對厭氧發酵的秸稈進行預處理的方法，係採用廢水潤濕纖維料源，密封式存放，並用80°C保溫，預處理時間6～24小時；惟此專利預處理時間較長，且須同時以80°C保溫。中國大陸CN102154374專利揭示之酸預處理水稻秸稈制取沼氣的方法，係採用稀酸溶液與纖維原料混合，然後密封於室溫下，預處理時間為30日，可見其預處理時間相當長。 因此，一般以纖維原料生產沼氣習知方法為以研磨或粉碎物理法處理後再進行厭氧消化，皆存在產氣效率比較低、發酵週期比較長之問題。故，ㄧ般習用者係無法符合使用者於實際使用時有效解決纖維原料轉化沼氣之低沼氣生成效率問題之所需。For biogas production technology, the main raw materials are currently livestock farm wastewater, kitchen waste or urban solid waste, etc. Fiber raw materials are rarely used as raw materials for anaerobic digestion to produce biogas. The main reason is that the fiber raw materials have a tough structure, although It contains abundant carbon sources, including cellulose, hemicellulose and lignin, but due to its interlaced structure and composition, it cannot be directly applied to the biogas production industry. In order to solve the structural problem of fiber raw materials, physical method, chemical method, biological method, physical chemical method or microbiological method can be used. The physical method mainly uses mechanical methods such as grinding to reduce the size of the fiber material to a certain extent and increase the contact specific surface area, but such methods are quite energy-consuming. The chemical method includes alkali method, dilute acid method or solvent method, etc., wherein the dilute acid method mainly hydrolyzes the hemicellulose of the fiber raw material into monosaccharides, so that the raw material structure is loose, but for the fiber raw material with high lignin content, the fiber The structural separation effect of lignin and lignin is limited; the alkaline treatment method is mainly based on the removal of lignin, but it is usually accompanied by a large amount of waste liquid, which causes problems and defects in waste liquid recovery and high water consumption. The microbiological method uses microbes to decompose fiber raw materials, and the decomposition rate is relatively slow compared to physical or chemical methods. Among the existing related patents, the CN101899474 patent in mainland China discloses a pretreatment method for straw biogas utilization, which uses sealed storage for decomposition and decomposition. The pretreatment decomposition time requires 8 to 15 days, which obviously shows that this patent has a longer pretreatment time. The patent CN104826855 in Mainland China discloses a method for pretreatment of anaerobic fermented straws, which uses waste water to wet the fiber source, is stored in a sealed manner, and is kept at 80°C for heat preservation. The pretreatment time is 6-24 hours; however, this patent pretreatment It takes a long time and must be kept at 80°C at the same time. The method for preparing biogas by acid pretreatment of rice straws disclosed in the patent of CN102154374 in mainland China is to use a dilute acid solution to mix with fiber raw materials, and then seal it at room temperature. The pretreatment time is 30 days, which shows that the pretreatment time is quite long. Therefore, the conventional method for producing biogas from fiber raw materials is the physical method of grinding or pulverization followed by anaerobic digestion, which has the problems of lower gas production efficiency and longer fermentation cycle. Therefore, general users cannot meet the needs of users to effectively solve the problem of low biogas generation efficiency of fiber raw materials converted into biogas during actual use.
本發明之主要目的係在於，克服習知技藝所遭遇之纖維原料轉化沼氣之低生成效率問題，並提供一種透過結合纖維解聚前處理程序，提升厭氧消化沼氣生產效率，增加纖維原料沼氣生產產量之可提升纖維原料沼氣生成效率之解聚技術及其與厭氧消化之整合方法。 本發明之次要目的係在於，提供一種可有效提升纖維原料轉化沼氣之產量，透過解聚前處理程序、特定酸鹼值與操作條件下，將纖維原料（例如農林業剩餘資材或能源作物等）轉化為解聚物，再經過厭氧消化程序生產沼氣成為氣態燃料，可作為生質電力或運輸燃料之來源供給之可提升纖維原料沼氣生成效率之解聚技術及其與厭氧消化之整合方法。 為達以上之目的，本發明係一種可提升纖維原料沼氣生成效率之解聚技術及其與厭氧消化之整合方法，其係包含：解聚前處理程序：將纖維原料轉化為解聚物，該解聚前處理程序包含下列步驟：物理性粉碎破壞與溶劑混合步驟：將該纖維原料粗切至所需尺寸，接著混入一定比例酸液溶劑，均勻攪拌混合，其中該酸液溶劑濃度係介於0.0～5.0% ；以及加溫加壓反應與蒸汽爆裂步驟：將上述步驟依序加入蒸汽爆裂反應器中再次均勻混合後，進行加溫加壓反應，反應溫度介於160～200°C、反應時間介於0.5～10.0分鐘，待反應完成時將該蒸汽爆裂反應器壓力瞬間閃化降至常壓，使反應產物同時閃化出料至閃化集料槽得到解聚物；以及厭氧消化程序：將該解聚物進行厭氧消化處理產生沼氣，該厭氧消化程序包含下列步驟：調整酸鹼度步驟：以氫氧化鈉調整該解聚物酸鹼值至中性酸鹼值範圍；以及調控S/I ratio與厭氧消化反應步驟：將經過酸鹼值調整處理之解聚物加入厭氧反應器中，同時投入厭氧汙泥微生物，調控該解聚物與該厭氧汙泥微生物混合比率（Substrate/Inoculum ratio, S/I ratio），並調控厭氧消化反應條件，使反應溫度介於25～65°C，攪拌速度介於20～100 rpm，反應時間介於5～20日；其中，S/I ratio表示方式為CODsubstrate /VSinoculum ，將該解聚物之化學需氧量（Chemical oxygen demand, COD）取作分子，該厭氧汙泥微生物之揮發性固體含量（Volatile solid, VS）取作分母時之比率介於1～4。 於本發明上述實施例中，該纖維原料係包含纖維素（cellulose）與半纖維素（hemicellulose）之農業廢棄物、林業廢棄物及能源作物之料源。 於本發明上述實施例中，該物理性粉碎破壞與溶劑混合步驟係將該纖維原料打碎至1～5公分。 於本發明上述實施例中，該酸液溶劑係為無機酸液溶劑或有機酸液溶劑。 於本發明上述實施例中，該解聚物之酸鹼值係調整至介於5～7之中性酸鹼值範圍。 於本發明上述實施例中，該加溫加壓反應與蒸汽爆裂步驟係使用批次式蒸汽爆裂反應器進行加溫加壓反應。 於本發明上述實施例中，該厭氧汙泥微生物係取自畜殖場廢水處理廠 、造紙業廢水處理廠或一般廢水處理廠經厭氧廢水處理後之沉澱池底層汙泥。 於本發明上述實施例中，該調控S/I ratio與厭氧消化處理步驟係使用批次式厭氧反應器進行厭氧消化反應。 於本發明上述實施例中，該纖維原料藉由該解聚前處理程序與該厭氧消化程序處理後，其沼氣生成效率比傳統之纖維料源直接進行厭氧消化處理提升2倍以上。The main purpose of the present invention is to overcome the low generation efficiency of biogas conversion from fiber raw materials encountered in conventional techniques, and to provide a combination of fiber depolymerization pre-treatment process to improve the production efficiency of anaerobic digestion biogas and increase the production of fiber raw biogas Depolymerization technology that can increase the production efficiency of biogas from fiber raw materials and its integration with anaerobic digestion The secondary objective of the present invention is to provide a method that can effectively increase the yield of biogas converted from fiber raw materials. Through pre-depolymerization treatment procedures, specific pH values and operating conditions, the fiber raw materials (such as agricultural and forestry surplus materials or energy crops, etc.) ) It is converted into depolymerization, and then biogas is produced by anaerobic digestion process to become gaseous fuel. It can be used as a source of biomass power or transportation fuel to improve the efficiency of biogas generation of fiber raw materials and its integration with anaerobic digestion method. In order to achieve the above purpose, the present invention is a depolymerization technology that can improve the biogas generation efficiency of fiber raw materials and its integration method with anaerobic digestion. It includes: pre-depolymerization pretreatment process: converting fiber raw materials into depolymerization, The depolymerization pre-treatment procedure includes the following steps: physical crushing and destruction and solvent mixing step: roughly cutting the fiber raw material to a desired size, then mixing a certain proportion of acid liquid solvent, uniformly stirring and mixing, wherein the concentration of the acid liquid solvent is Within 0.0～5.0%; and the step of heating and pressurizing reaction and steam burst: add the above steps in sequence to the steam burst reactor and mix again uniformly, then perform heating and pressurizing reaction, the reaction temperature is between 160～200°C, The reaction time ranges from 0.5 to 10.0 minutes. When the reaction is completed, the pressure of the steam burst reactor is instantaneously flashed to atmospheric pressure, so that the reaction product is flashed out and discharged to the flash tank to obtain depolymerization; and anaerobic Digestion process: The anaerobic digestion process is carried out to produce biogas. The anaerobic digestion process includes the following steps: pH adjustment step: adjusting the pH value of the depolymerization to neutral pH range with sodium hydroxide; and Regulate the S/I ratio and anaerobic digestion reaction steps: add the depolymerized after pH adjustment to the anaerobic reactor, and put anaerobic sludge microorganisms at the same time to regulate the depolymerized and anaerobic sludge microorganisms Substrate/Inoculum ratio, S/I ratio, and adjust the anaerobic digestion reaction conditions, so that the reaction temperature is between 25 and 65°C, the stirring speed is between 20 and 100 rpm, and the reaction time is between 5 and 20 days ; Where S/I ratio is expressed as COD substrate /VS inoculum , the chemical oxygen demand (COD) of the depolymer is taken as the molecule, and the volatile solid content of the anaerobic sludge microorganism (Volatile solid, VS) The ratio when taken as the denominator is between 1 and 4. In the above embodiments of the present invention, the fiber raw material is a source of agricultural waste, forestry waste, and energy crops including cellulose and hemicellulose. In the above embodiments of the present invention, the physical crushing and solvent mixing step is to crush the fiber raw material to 1 to 5 cm. In the above embodiments of the present invention, the acid liquid solvent is an inorganic acid liquid solvent or an organic acid liquid solvent. In the above embodiments of the present invention, the pH value of the depolymer is adjusted to a neutral pH range of 5-7. In the above embodiments of the present invention, the heating and pressurizing reaction and the steam bursting step use a batch type steam bursting reactor to perform the heating and pressurizing reaction. In the above embodiment of the present invention, the anaerobic sludge microorganisms are taken from the sludge in the sedimentation tank bottom layer after the anaerobic wastewater treatment in the livestock farm wastewater treatment plant, papermaking wastewater treatment plant or general wastewater treatment plant. In the above embodiments of the present invention, the step of adjusting the S/I ratio and the anaerobic digestion treatment process uses a batch anaerobic reactor to perform the anaerobic digestion reaction. In the above embodiment of the present invention, after the fiber raw material is processed by the depolymerization pretreatment process and the anaerobic digestion process, the biogas generation efficiency is increased by more than 2 times compared with the traditional fiber source directly performing anaerobic digestion process.
請參閱『第１圖』所示，係本發明可提升纖維原料沼氣生成效率之解聚技術及其與厭氧消化之整合方法之流程示意圖。如圖所示：本發明係一種可提升纖維原料沼氣生成效率之解聚技術及其與厭氧消化之整合方法，係以解決纖維原料轉化沼氣之低沼氣生成效率問題，透過整合解聚前處理程序，將纖維原料其堅韌與緊密結構進行解聚與破壞，增加厭氧消化沼氣生產效率與提升反應速率，縮短沼氣生產時程。本發明中之解聚前處理程序係以酸催化蒸汽爆裂方式，進行纖維原料解聚，分離其纖維素（cellulose）、半纖維素（hemicellulose）與木質素（lignin），將部分纖維素與半纖維素溶於液相成為五碳糖與六碳糖之單糖或寡糖型態，而其固相為經解聚後之結構破壞之富含纖維素固渣。上述酸催化蒸汽爆裂之產物可直接進行厭氧消化程序，於特定操作條件下，得到高效率之沼氣生成效果。本方法係包含： 解聚前處理程序s1：將纖維原料轉化為解聚物，該解聚前處理程序s1包含下列步驟： 物理性粉碎破壞與溶劑混合步驟s11：將該纖維原料經過粉碎方式粗切至所需尺寸（例如打碎至1～5公分大小），接著混入一定比例無機酸液溶劑或有機酸液溶劑，酸液濃度介於0.0～5.0%，均勻攪拌混合，其中該纖維原料係包含纖維素（cellulose）與半纖維素（hemicellulose）之農業廢棄物、林業廢棄物及能源作物之料源；以及 加溫加壓反應與蒸汽爆裂步驟s12：將上述步驟s11依序加入批次式蒸汽爆裂反應器中再次均勻混合製備測試用試樣，而後進行加溫加壓反應，反應溫度介於160～200°C、反應時間介於0.5～10.0分鐘，待反應完成時將該蒸汽爆裂反應器壓力瞬間閃化降至常壓，使反應產物同時閃化出料至閃化集料槽，所得反應產物亦稱解聚物；以及 厭氧消化程序s2：將該解聚物進行厭氧消化處理產生沼氣，該厭氧消化程序s2包含下列步驟： 調整酸鹼度步驟s21：以氫氧化鈉調整該解聚物酸鹼值至中性酸鹼值範圍，該中性酸鹼值範圍介於5～7；以及 調控S/I ratio與厭氧消化處理步驟s22：將此經過酸鹼值調整處理之解聚物採用批次式厭氧反應器進行厭氧消化處理，同時投入厭氧汙泥微生物，調控該解聚物與該厭氧汙泥微生物混合比率（Substrate/Inoculum ratio, S/I ratio），該S/I ratio表示方式為CODsubstrate
/VSinoculum
，將該解聚物之化學需氧量（Chemical oxygen demand, COD）取作分子，該厭氧汙泥微生物之揮發性固體含量（Volatile solid, VS）取作分母時之比率介於1～4，並調控厭氧消化反應條件，使反應溫度介於25～65°C，攪拌速度介於20～100 rpm，反應時間介於5～20日；其中，該厭氧汙泥微生物係取自畜殖場廢水處理廠、造紙業廢水處理廠或一般廢水處理廠經厭氧廢水處理後之沉澱池底層汙泥。透過本發明，稻稈與蔗渣轉化沼氣之生成效率分別可達到每公克解聚物乾重300毫升沼氣與200 毫升沼氣以上，達到提升沼氣生成效率之結果。 如是，藉由上述揭露之流程構成一全新之可提升纖維原料沼氣生成效率之解聚技術及其與厭氧消化之整合方法。 如前所述，一般以纖維原料生產沼氣習知方法為以研磨或粉碎物理法處理後再進行厭氧消化。當運用時，本發明專利以粉碎處理後直接厭氧消化試驗作為對照組；將稻稈、蔗渣及木片等三種纖維原料粉碎至1.0公分大小，分析其總固體含量與化學需氧量性質，稻稈之總固體含量與化學需氧量分別為94.0%與1639 mg/g，蔗渣則為95.2%與1075 mg/g，及木片之總固體含量與化學需氧量分別為89.4%與1884 mg/g。厭氧汙泥微生物取自養豬場廢水經三段式廢水處理後之沉澱池底層汙泥，取固定厭氧汙泥微生物之總量10 g VS，厭氧消化S/I ratio等於1的稻稈、蔗渣及木片投入量分別為6.1 g、9.3 g及5.3 g，厭氧消化反應溫度為35°C，厭氧消化攪拌速度為40 rpm，厭氧消化時間為14日。 以下，基於實施例對本發明進一步具體地進行說明，但本發明未受以下實施例之任何限定。 [實施例一] 請參閱『第２圖及第３圖』所示，係分別為本發明實施例一纖維原料直接生產沼氣與經解聚技術處理後生產沼氣之結果比較圖、以及本發明實施例一稻稈、蔗渣及木片之沼氣產量比較圖。如圖所示：本試驗分別先將稻稈、蔗渣及木片等纖維原料粉碎至1.0公分大小、混合純水與硫酸至稀酸比例為1.5%，攪拌均勻，並加入於蒸汽爆裂反應器進行200°C、持壓1分鐘之批次式反應。然後取出解聚物，以12N氫氧化鈉調整其酸鹼值至7。然後進行厭氧消化處理，此部分操作條件與前述相同，厭氧消化之S/I ratio等於1，厭氧消化反應溫度為35°C，厭氧消化攪拌速度為40 rpm，厭氧消化時間為14日。其沼氣生成效率與以研磨或粉碎物理法處理後再進行厭氧消化之對照組進行比較，稻稈纖維原料，原料直接厭氧消化與原料先經解聚前處理，再經厭氧消化之沼氣生成效率分別為 84 mL/g-TS與250 mL/g-TS；蔗渣纖維原料，分別為67 mL/g-TS與213 mL/g-TS；及木片纖維原料，分別為123 mL/g-TS與271 mL/g-TS，顯示本發明之解聚技術及其與厭氧消化之沼氣生產整合方法，沼氣生成效率分別提升2.97、3.18及2.20倍。如第２、３圖所示，其中第２圖為纖維料源（RS：稻稈、SC：蔗渣、WD：木片）原料（raw）與解聚處理後（de-ag）在S/I = 1下，酸鹼度調整為7後經歷14天生產沼氣累積量之差異。及第３圖中灰階長條表示纖維原料直接生產沼氣，黑色長條表示纖維原料先經解聚技術後生產沼氣。由第２、３圖可證，本發明之整合解聚前處理程序與厭氧消化程序處理纖維原料生產沼氣，與直接厭氧消化處理生產沼氣比較，顯見本發明所提方法係可有效提升纖維原料沼氣生成效率。 [實施例二] 請參閱『第４圖』所示，係本發明實施例二稻稈纖維原料經解聚技術處理後生產沼氣之結果示意圖。如圖所示：本試驗以稻稈纖維原料，先將稻稈粉碎至1.0公分大小、混合純水與硫酸至稀酸比例為1.5%，攪拌均勻，並加入於蒸汽爆裂反應器進行200°C、持壓1分鐘之批次式反應。然後取出解聚物，以12N氫氧化鈉調整其酸鹼值至6，並分析其總固體含量（Total solid, TS）與化學需氧量性質，稻稈解聚物總固體含量為36.8%，化學需氧量為390 mg/g。厭氧汙泥微生物取自養豬場廢水經三段式廢水處理後之沉澱池底層汙泥，取固定厭氧汙泥微生物之總量 10 g VS，S/I ratio等於1或2時之稻稈解聚物投入量分別為25.6 g與51.2 g。投入厭氧汙泥微生物與稻稈解聚物於厭氧反應器內，厭氧消化反應溫度為35°C，厭氧消化攪拌速度為40 rpm，厭氧消化時間為7日。利用本發明提升稻稈纖維原料沼氣生成效率之厭氧消化結果如第４圖所示，顯示經由本發明之解聚前處理程序與厭氧消化程序整合，稻稈之沼氣生成量在S/I ratio = 1與S/I ratio = 2分別為318 mL/g-TS與338 mL/g-TS，甲烷佔沼氣之組成分別為65%與64%。 由上述實施例一、二可知，本發明於最適化之解聚前處理操作參數、解聚物酸鹼值與厭氧消化操作條件下，可得到高沼氣生成量，以稻稈與蔗渣為例，沼氣生成量分別為每公克乾重338毫升與213毫升。藉此生產沼氣成為氣態燃料，可作為生質電力或運輸燃料之來源供給。 綜上所述，本發明係一種可提升纖維原料沼氣生成效率之解聚技術及其與厭氧消化之整合方法，可有效改善習用之種種缺點，透過纖維解聚前處理，快速地將纖維原料轉化為解聚物，然後進行厭氧消化處理產生沼氣，此方法效果與傳統直接將纖維原料進行厭氧消化相比，可縮短纖維原料厭氧消化時間，快速完成厭氧消化程序，並提升纖維原料沼氣生成效率，有效解決纖維原料轉化沼氣之低沼氣生成效率問題 ，進而使本發明之産生能更進步、更實用、更符合使用者之所須，確已符合發明專利申請之要件，爰依法提出專利申請。 惟以上所述者，僅為本發明之較佳實施例而已，當不能以此限定本發明實施之範圍；故，凡依本發明申請專利範圍及發明說明書內容所作之簡單的等效變化與修飾，皆應仍屬本發明專利涵蓋之範圍內。Please refer to "Figure 1", which is a schematic flow chart of the depolymerization technology of the present invention that can improve the biogas generation efficiency of fiber raw materials and its integration method with anaerobic digestion. As shown in the figure: the present invention is a depolymerization technology that can improve the biogas generation efficiency of fiber raw materials and its integration method with anaerobic digestion, to solve the problem of low biogas generation efficiency of biogas conversion from fiber raw materials, through integrated depolymerization pretreatment The procedure is to disaggregate and destroy the tough and compact structure of the fiber raw material, increase the efficiency of anaerobic digestion biogas production and increase the reaction rate, and shorten the biogas production time. The depolymerization pre-treatment procedure in the present invention is to depolymerize the fiber raw materials by acid-catalyzed steam burst, separate the cellulose, hemicellulose and lignin, and part of the cellulose and hemicellulose Cellulose dissolves in the liquid phase and becomes a monosaccharide or oligosaccharide form of five-carbon sugar and six-carbon sugar, and its solid phase is a cellulose-rich solid slag whose structure is destroyed by depolymerization. The products of the above acid-catalyzed steam explosion can be directly subjected to an anaerobic digestion process, and under specific operating conditions, a high-efficiency biogas generation effect can be obtained. The method includes: pre-depolymerization treatment procedure s1: converting the fiber raw material into depolymerization, the pre-depolymerization treatment procedure s1 includes the following steps: physical crushing destruction and solvent mixing step s11: the fiber raw material is subjected to coarse grinding Cut to the required size (for example, crushed to a size of 1 to 5 cm), and then mix with a certain proportion of inorganic acid liquid solvent or organic acid liquid solvent, the concentration of acid liquid is between 0.0 and 5.0%, and stir and mix evenly. Sources of agricultural wastes, forestry wastes and energy crops containing cellulose and hemicellulose; and heating and pressure reaction and steam burst step s12: adding the above step s11 to the batch in sequence The test sample is prepared by uniformly mixing again in the steam burst reactor, and then heated and pressurized. The reaction temperature is between 160 to 200°C and the reaction time is between 0.5 to 10.0 minutes. When the reaction is completed, the steam burst reaction The pressure of the reactor flashes down to atmospheric pressure instantaneously, so that the reaction product flashes out to the flash tank at the same time, and the resulting reaction product is also called depolymerization; and the anaerobic digestion procedure s2: the depolymerization is subjected to anaerobic digestion The biogas is generated by the treatment. The anaerobic digestion process s2 includes the following steps: pH adjustment step s21: adjusting the pH value of the depolymerized polymer to a neutral pH value range with sodium hydroxide, the neutral pH value range is 5 to 7; and adjust the S/I ratio and anaerobic digestion treatment step s22: the depolymerized polymer with pH adjustment treatment is subjected to anaerobic digestion treatment using batch anaerobic reactor, and the anaerobic sludge microbe Adjust the microbial mixing ratio of the depolymer and the anaerobic sludge (Substrate/Inoculum ratio, S/I ratio), the S/I ratio is expressed as COD substrate /VS inoculum , and the chemical oxygen demand of the depolymer (Chemical oxygen demand, COD) is taken as the molecule, and the ratio of the volatile solid content (Volatile solid, VS) of the anaerobic sludge microorganism as the denominator is between 1 and 4, and the anaerobic digestion reaction conditions are adjusted to make the reaction The temperature is between 25 and 65°C, the stirring speed is between 20 and 100 rpm, and the reaction time is between 5 and 20 days. Among them, the anaerobic sludge microorganisms are taken from livestock farm wastewater treatment plant and paper industry wastewater treatment plant Or the bottom sludge of the sedimentation tank after the anaerobic wastewater treatment of the general wastewater treatment plant. Through the present invention, the generation efficiency of biogas converted from rice straw and bagasse can reach 300 ml biogas and 200 ml biogas per gram of depolymerized dry weight, respectively, to achieve the result of improving biogas generation efficiency. If so, the process disclosed above constitutes a new depolymerization technology that can increase the biogas generation efficiency of fiber raw materials and its integration with anaerobic digestion. As mentioned above, the conventional method for producing biogas from fiber raw materials is to grind or pulverize physically before anaerobic digestion. When used, the patent of the present invention uses the direct anaerobic digestion test after crushing as a control group; the three fiber materials such as rice straw, bagasse and wood chips are crushed to a size of 1.0 cm, and the total solid content and chemical oxygen demand properties are analyzed. The total solids content and chemical oxygen demand of stalks were 94.0% and 1639 mg/g, the bagasse was 95.2% and 1075 mg/g, and the total solids content and chemical oxygen demand of wood chips were 89.4% and 1884 mg/g, respectively. g. The anaerobic sludge microorganisms are taken from the bottom sludge of the sedimentation tank after the three-stage wastewater treatment of the pig farm wastewater. The total amount of fixed anaerobic sludge microorganisms is 10 g VS, and the anaerobic digestion S/I ratio is equal to 1. The input amounts of stalks, bagasse and wood chips were 6.1 g, 9.3 g and 5.3 g, respectively, the anaerobic digestion reaction temperature was 35°C, the anaerobic digestion stirring speed was 40 rpm, and the anaerobic digestion time was 14 days. Hereinafter, the present invention will be further specifically described based on examples, but the present invention is not limited by the following examples. [Embodiment 1] Please refer to "Figure 2 and Figure 3", which are the comparison diagrams of the results of biogas produced directly from fiber raw materials and biogas produced by depolymerization technology, and the implementation of the present invention. Example 1 Comparison graph of biogas production of rice straw, bagasse and wood chips. As shown in the figure: in this experiment, the fiber raw materials such as rice straw, bagasse and wood chips were crushed to a size of 1.0 cm, and the ratio of mixed pure water and sulfuric acid to dilute acid was 1.5%, stirred evenly, and added to the steam burst reactor for 200 Batch reaction at °C, holding pressure for 1 minute. Then remove the depolymer and adjust its pH to 7 with 12N sodium hydroxide. Then perform anaerobic digestion treatment. The operating conditions of this part are the same as the previous ones. The S/I ratio of anaerobic digestion is equal to 1, the reaction temperature of anaerobic digestion is 35°C, the stirring speed of anaerobic digestion is 40 rpm, and the anaerobic digestion time is 14th. The biogas generation efficiency is compared with the control group which is treated by grinding or crushing physical method and then subjected to anaerobic digestion. Rice straw fiber raw material, raw material direct anaerobic digestion and raw material first undergo pre-depolymerization pretreatment and then anaerobic digestion of biogas The production efficiency is 84 mL/g-TS and 250 mL/g-TS respectively; bagasse fiber raw materials are 67 mL/g-TS and 213 mL/g-TS respectively; and wood chip fiber raw materials are 123 mL/g- TS and 271 mL/g-TS show that the depolymerization technology of the present invention and its integration method with anaerobic digestion biogas production, the biogas generation efficiency is increased by 2.97, 3.18 and 2.20 times, respectively. As shown in Figures 2 and 3, Figure 2 is the fiber source (RS: rice straw, SC: bagasse, WD: wood chips) raw material (de) and after depolymerization (de-ag) at S/I = Under 1, the pH value is adjusted to the difference of the accumulated amount of biogas produced after 14 days after 7 adjustments. And the gray scale bar in Figure 3 indicates that the fiber raw material directly produces biogas, and the black bar indicates that the fiber raw material is first produced by depolymerization technology and then biogas is produced. As shown in Figures 2 and 3, the integrated depolymerization pretreatment process and anaerobic digestion process of the present invention process fiber raw materials to produce biogas. Compared with direct anaerobic digestion process to produce biogas, it is obvious that the method proposed by the present invention can effectively improve fiber Raw biogas generation efficiency. [Embodiment 2] Please refer to "Figure 4", which is a schematic diagram of the results of biogas production after the treatment of the rice straw fiber raw material by depolymerization technology. As shown in the figure: this experiment uses rice straw fiber raw materials, firstly crushing rice straw to 1.0 cm size, mixing pure water and sulfuric acid to dilute acid ratio of 1.5%, stirring evenly, and adding it to the steam burst reactor for 200°
s1‧‧‧解聚前處理程序 步驟s11‧‧‧物理性粉碎破壞與溶劑混合 步驟s12‧‧‧加溫加壓反應與蒸汽爆裂 s2‧‧‧厭氧消化程序 步驟s21‧‧‧調整酸鹼度步驟 步驟s22‧‧‧調控S/I ratio與厭氧消化反應 s1‧‧‧Process before disaggregation Step s11 ‧‧‧ Physical crushing and destruction and solvent mixing Step s12‧‧‧‧Heating pressure reaction and steam burst s2‧‧‧Anaerobic digestion procedure Step s21‧‧‧ Adjust pH Step s22‧‧‧Adjust S/I ratio and anaerobic digestion reaction
第１圖，係本發明可提升纖維原料沼氣生成效率之解聚技術及其與厭 厭氧消化之整合方法之流程示意圖。 第２圖，係本發明實施例一纖維原料直接生產沼氣與經解聚技術處理 理後生產沼氣之結果比較圖。 第３圖，係本發明實施例一稻稈、蔗渣及木片之沼氣產量比較圖。 第４圖，係本發明實施例二稻稈纖維原料經解聚技術處理後生產沼氣之結果示意圖。Figure 1 is a schematic flow chart of the depolymerization technology of the present invention that can improve the biogas generation efficiency of fiber raw materials and its integration method with anaerobic digestion. Figure 2 is a graph comparing the results of biogas produced directly from fiber raw materials and biogas produced after treatment by depolymerization technology in Example 1 of the present invention. Figure 3 is a comparison chart of biogas production of rice straw, bagasse and wood chips according to Example 1 of the present invention. Figure 4 is a schematic diagram of the results of biogas production after the treatment of depolymerization technology for the rice straw fiber material in Example 2 of the present invention.
s1‧‧‧解聚前處理程序 s1‧‧‧Process before disaggregation
s11‧‧‧物理性粉碎破壞與溶劑混合步驟 s11‧‧‧ Physical crushing and solvent mixing steps
s12‧‧‧加溫加壓反應與蒸汽爆裂步驟 s12‧‧‧Heating and pressure reaction and steam burst steps
s2‧‧‧厭氧消化程序 s2‧‧‧Anaerobic digestion procedure
s21‧‧‧調整酸鹼度步驟步驟 s21‧‧‧Adjust pH steps
s22‧‧‧調控S/I ratio與厭氧消化反應步驟 s22‧‧‧Regulation of S/I ratio and anaerobic digestion reaction steps
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| TWI773074B (en) * | 2021-01-05 | 2022-08-01 | 行政院原子能委員會核能研究所 | Method of producing biogas |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI773074B (en) * | 2021-01-05 | 2022-08-01 | 行政院原子能委員會核能研究所 | Method of producing biogas |
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