多原料高濃度混合共發酵制氣與純化提質研究最終報告

周紅軍 江皓 聶紅

摘 要：該研究針對目前我國規模化生物燃氣工程原料單一、產氣率低、裝備落后等技術瓶頸，旨在開發多種原料混合共發酵制氣關鍵技術，優化高效率、低能耗厭氧發酵工藝與裝置，并對生物燃氣進行純化提質和高值利用研究，使生物燃氣分別達到民用或燃氣的要求。針對畜禽糞便、作物秸稈、有機垃圾和農產品廢棄物等四大類20多種不同原料成分分析及產氣潛力和特性研究，進行了單一物料和不同物料混合的厭氧消化實驗，以此建立了沼氣發酵原料特性及產氣性能數據庫，并研究多種原料的C/N比及營養物質的合理調配技術，提高了單一原料的產氣效率。研究了畜禽糞便、有機垃圾等原料中的去除泥砂和有害雜質工藝。針對秸稈發酵，著重研發原料切碎、貯存和預接種混合技術及裝置，提高秸稈產氣效率。研究了高濃度發酵（TS≥10%）和干發酵（TS≥20%）過程中混合原料的攪拌方式及混合程度對厭氧共發酵工藝的影響，優化了不同混合原料的發酵工藝參數，提高原料產氣率。開展了多原料高濃度混合共發酵制氣基礎研究。包括混合原料配比技術的研究；不同類型模型底物的厭氧水解動力學研究；不同單一原料的厭氧水解動力學研究；高濃度單相厭氧消化模型；固體床兩相厭氧消化模型；沼氣的生物脫硫技術基礎研究。采用甲烷氧化脫氧工藝去除沼氣中的氧，針對沼氣脫氧劑和沼氣脫氧工藝展開了研究。根據沼氣中硫化物的形態分布，采用多種吸附劑有針對性地吸附不同的硫化物，主要研究了精脫硫劑及脫硫工藝。采用碳酸丙烯酯法和加壓水洗法脫除沼氣中的CO2，針對吸收溶劑地研制及脫除CO2工藝的開發展開了研究。該研究最終建立了不同發酵原料成分及其產氣特性的數據庫，兩種以上混合原料厭氧共發酵，進料固形物含量大于10%，中溫沼氣產率大于1.2 Nm3/m3罐容天。建設了多原料共發酵的中試裝置一套。完成示范工程建設，形成產業化核心技術，達到如下指標：產品CH4 97%，CO 23%，H2S 10 ppm，甲烷回收率≥99%，壓力≤1.0 Mpa；純化能耗≤0.80 kwh/m3生物天然氣；精脫硫劑硫容≥10%，碚硫溫度為常溫；在貴金屬催化劑作用下，使垃圾場沼氣中的O2<0.60%達到歐洲標準；沼氣中硫化氫、羰基硫、二硫化碳、硫醇、硫醚和噻吩等硫化物脫至1 ppm以下。

關鍵詞：多原料發酵 甲烷 二氧化碳 硫化物 氧氣

Abstract：In order to solve some problems of the current large-scale biogas projects in China， such as a single raw material， low rate of gas production and backward equipment， this study aims to develop some key technologies of multi-materials co-fermentation， optimize fermentation process and apparatus for high efficiency and low energy consumption， develop biogas upgrading techniques， and make the production gas meet the requirements of civil gas or vehicle gas. For manure， crop residues， organic waste and agricultural waste， 20 different raw materials were analyzed. Anaerobic digestion experiments were carried out using single and mixed materials， in order to establish biogas fermentation feedstock characteristics and gas production performance database， and to study the allocation of C/N ratio and nutrients from different feedstock. The technologies of removing sediment and harmful impurities from manure， organic waste and other raw materials were studies. For straw， the technologies and devices of chopping raw material， storage， pre-inoculation and mixing were developed to improve the efficiency of gas production. In the fermentation of a high concentration （TS≥10%） and dry fermentation （TS≥20%），the effects of mixing method and degree were figured out. The fermentation parameters were optimized to improve the gas production rate.A series basic research of multi-material fermentation was studied， including the mixing technology of raw materials，anaerobic hydrolysis kinetics of different model substrate and single feedstock， high concentration of single-phase anaerobic digestion model， solid bed two-phase anaerobic digestion model， biogas biological desulfurization. Using methane oxidation process to remove oxygen in the biogas， the desoxidant and deoxidation process were studied. For different types of sulfide in biogas， the fine desulfurization process and agent were tested. Propylene carbonate absorbing and water scrubbing were applied for CO2 removal. This study eventually established database of various materials for fermentation. Using two or more materials for mixed anaerobic fermentation， the feed solid content was greater than 10%， and the yield of biogas was over 1.2 Nm3/（m3·day）.The demonstration projects were built up. The following indicators were achieved：CH4≥97%， CO2≤3%，H2S≤10 ppm，methane recovery≥99%， pressure≤1.0 MPa； energy consumption≤0.80 kwh/m3 biogas； fine desulfurizer sulfur capacity≥10%，O2<0.60%， sulfide<1ppm.

Key Words：Multi-material fermentation；Methane；Carbon dioxide；Sulfide；Oxygen

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