多原料高濃度混合共發(fā)酵制氣與純化提質(zhì)研究最終報(bào)告

周紅軍 江皓 聶紅

摘 要：該研究針對目前我國規(guī)?；锶?xì)夤こ淘蠁我弧a(chǎn)氣率低、裝備落后等技術(shù)瓶頸，旨在開發(fā)多種原料混合共發(fā)酵制氣關(guān)鍵技術(shù)，優(yōu)化高效率、低能耗厭氧發(fā)酵工藝與裝置，并對生物燃?xì)膺M(jìn)行純化提質(zhì)和高值利用研究，使生物燃?xì)夥謩e達(dá)到民用或燃?xì)獾囊蟆ａ槍π笄菁S便、作物秸稈、有機(jī)垃圾和農(nóng)產(chǎn)品廢棄物等四大類20多種不同原料成分分析及產(chǎn)氣潛力和特性研究，進(jìn)行了單一物料和不同物料混合的厭氧消化實(shí)驗(yàn)，以此建立了沼氣發(fā)酵原料特性及產(chǎn)氣性能數(shù)據(jù)庫，并研究多種原料的C/N比及營養(yǎng)物質(zhì)的合理調(diào)配技術(shù)，提高了單一原料的產(chǎn)氣效率。研究了畜禽糞便、有機(jī)垃圾等原料中的去除泥砂和有害雜質(zhì)工藝。針對秸稈發(fā)酵，著重研發(fā)原料切碎、貯存和預(yù)接種混合技術(shù)及裝置，提高秸稈產(chǎn)氣效率。研究了高濃度發(fā)酵（TS≥10%）和干發(fā)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(fā)酵工藝的影響，優(yōu)化了不同混合原料的發(fā)酵工藝參數(shù)，提高原料產(chǎn)氣率。開展了多原料高濃度混合共發(fā)酵制氣基礎(chǔ)研究。包括混合原料配比技術(shù)的研究；不同類型模型底物的厭氧水解動力學(xué)研究；不同單一原料的厭氧水解動力學(xué)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(shù)基礎(chǔ)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(jù)沼氣中硫化物的形態(tài)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(fā)展開了研究。該研究最終建立了不同發(fā)酵原料成分及其產(chǎn)氣特性的數(shù)據(jù)庫，兩種以上混合原料厭氧共發(fā)酵，進(jìn)料固形物含量大于10%，中溫沼氣產(chǎn)率大于1.2 Nm3/m3罐容天。建設(shè)了多原料共發(fā)酵的中試裝置一套。完成示范工程建設(shè)，形成產(chǎn)業(yè)化核心技術(shù)，達(dá)到如下指標(biāo)：產(chǎn)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(dá)到歐洲標(biāo)準(zhǔn)；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(guān)鍵詞：多原料發(fā)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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