以甜菜和红糖为底物的EGSB生物制氢反应器的启动与运行
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摘要
氢气作为能源对于当今世界的资源短缺和环境恶化是一个理想的解决方案。目前的大规模氢气生产技术存在诸多弊端,且缺乏可持续性,导致氢能源的利用率还很低。发酵法生物制氢技术具有应用于大规模生产的潜力,但仍需在提高产氢效率和寻找廉价原料等重要问题上深入研究。甜菜作为一种含糖量很高的经济作物,价格低廉,种植广泛,理论上非常适合作为发酵产氢的底物。本研究根据已有的生物制氢理论,使用甜菜作为底物,通过与高效的膨胀颗粒污泥床反应器(EGSB)结合进行生物制氢实验。另外选择红糖为底物在同一反应器内进行了对比实验。
以红糖为底物的实验中,COD范围从2000-8000 mg/L,启动HRT为6h。COD提升到8000 mg/L水平后,HRT依次变为4h、3h、2h,并各持续7d。实验获得了最高为5.73 L/(L·d)的产氢速率,此时氢气含量为48.44%,系统HRT为2h,pH值为4.36,OLR为97.2 kg COD/(m3·d)。平均氢气含量为41.27%,pH范围是4.23-4.55。系统达到稳定后,发酵液中乙醇和乙酸为主要产物,形成了典型的乙醇型发酵。
使用甜菜为底物时由于条件的限制,甜菜采取提取液的利用形式。OLR控制策略与使用红糖为底物时相似,经过56天的运行,系统在成功实现了乙醇型发酵的情况下,状态稳定。在COD同为8000mg/L水平,HRT分别处于6h、4h、3h和2h情况下,获得的最大产氢速率分别达到3.80、4.63、4.92和5.54 L/(L·d),pH值范围是3.46-3.86。整个运行阶段产氢速率最高为5.54 L/(L·d),此时氢气含量为49.63%,系统HRT为2h,pH值为3.57,OLR为97.9 kg COD/(m3·d)。
通过与使用红糖为底物的实验进行对比,认为甜菜作为底物进行发酵法生物制氢是可行的,但在产氢效果和利用率上仍存在不足,底物的合理制备方式也需要继续深入研究。
Hydrogen energy is an ideal solution to the global energy crises and environmental degradation.The current industrial hydrogen production technology has many disadvantages and unsustainability, which cause the utilization rate of hydrogen energy still very low. Fermentative biohydrogen production has an enormous potential to the large scale industrial production, but still need us to pay great attention to raise the production rate and find cheap raw materials. Sugarbeet is a cash crop with high sucrose content which had low price and been grown widely. It is theoretically fit for being the substrate of fermentative hydrogen production. This study chose sugarbeet as substrate for biohydrogen production using an expanded granular sludge bed reactor (EGSB).Brown sugar was also selected as a comparing fermentative substrate.
In the experiment which substrate was brown sugar, COD was increased from 2000 to 8 000 mg/L gradually, the starting HRT was 6h.When the COD was increased at the level of 8 000 mg/L, the HRT began to shorten to 4h,3h and 2h,each kept for 7d.A maximum hydrogen production rate of 5.73 L/(L·d) was achieved, when hydrogen content was 48.44%, HRT was 2h, pH was 4.36 and OLR was 97.2 kg COD/(m3·d). The average hydrogen content of biogas during the experiment was 41.27%, and the pH range was 4.23～4.55.In the steady operation period, the dominant liquid end products were ethanol and acetic acid, which represented ethanol-type fermentation.
Because of the technical problem in the bench scale study, water extract of sugarbeet was used as substrate instead of sugarbeet pulp.The same OLR control strategy which has been used in former study was employed here. The system was stable within 56d operation and Ethanol-type fermentation was formed.When the COD was around 8000 mg/L,HRT was 6h, 4h,3h and 2h, the maximum hydrogen production rates were 3.80,4.63,4.92 and 5.54 L/(L-d), respectively. pH range was 3.46-3.86.The maximum hydrogen production rate during this experiment was 5.54 L/(L·d), when hydrogen content was 49.63%,HRT was 2h, pH was 3.57 and OLR was 97.9 kg COD/(m3·d).
The results of the two experiments verified the feasibility of fermentative hydrogen production from sugarbeet, but the hydrogen production rate and utilization rate of substrate were still improvable. It was also need to pay more attention to the feeding form of sugarbeet.
以红糖为底物的实验中,COD范围从2000-8000 mg/L,启动HRT为6h。COD提升到8000 mg/L水平后,HRT依次变为4h、3h、2h,并各持续7d。实验获得了最高为5.73 L/(L·d)的产氢速率,此时氢气含量为48.44%,系统HRT为2h,pH值为4.36,OLR为97.2 kg COD/(m3·d)。平均氢气含量为41.27%,pH范围是4.23-4.55。系统达到稳定后,发酵液中乙醇和乙酸为主要产物,形成了典型的乙醇型发酵。
使用甜菜为底物时由于条件的限制,甜菜采取提取液的利用形式。OLR控制策略与使用红糖为底物时相似,经过56天的运行,系统在成功实现了乙醇型发酵的情况下,状态稳定。在COD同为8000mg/L水平,HRT分别处于6h、4h、3h和2h情况下,获得的最大产氢速率分别达到3.80、4.63、4.92和5.54 L/(L·d),pH值范围是3.46-3.86。整个运行阶段产氢速率最高为5.54 L/(L·d),此时氢气含量为49.63%,系统HRT为2h,pH值为3.57,OLR为97.9 kg COD/(m3·d)。
通过与使用红糖为底物的实验进行对比,认为甜菜作为底物进行发酵法生物制氢是可行的,但在产氢效果和利用率上仍存在不足,底物的合理制备方式也需要继续深入研究。
Hydrogen energy is an ideal solution to the global energy crises and environmental degradation.The current industrial hydrogen production technology has many disadvantages and unsustainability, which cause the utilization rate of hydrogen energy still very low. Fermentative biohydrogen production has an enormous potential to the large scale industrial production, but still need us to pay great attention to raise the production rate and find cheap raw materials. Sugarbeet is a cash crop with high sucrose content which had low price and been grown widely. It is theoretically fit for being the substrate of fermentative hydrogen production. This study chose sugarbeet as substrate for biohydrogen production using an expanded granular sludge bed reactor (EGSB).Brown sugar was also selected as a comparing fermentative substrate.
In the experiment which substrate was brown sugar, COD was increased from 2000 to 8 000 mg/L gradually, the starting HRT was 6h.When the COD was increased at the level of 8 000 mg/L, the HRT began to shorten to 4h,3h and 2h,each kept for 7d.A maximum hydrogen production rate of 5.73 L/(L·d) was achieved, when hydrogen content was 48.44%, HRT was 2h, pH was 4.36 and OLR was 97.2 kg COD/(m3·d). The average hydrogen content of biogas during the experiment was 41.27%, and the pH range was 4.23～4.55.In the steady operation period, the dominant liquid end products were ethanol and acetic acid, which represented ethanol-type fermentation.
Because of the technical problem in the bench scale study, water extract of sugarbeet was used as substrate instead of sugarbeet pulp.The same OLR control strategy which has been used in former study was employed here. The system was stable within 56d operation and Ethanol-type fermentation was formed.When the COD was around 8000 mg/L,HRT was 6h, 4h,3h and 2h, the maximum hydrogen production rates were 3.80,4.63,4.92 and 5.54 L/(L-d), respectively. pH range was 3.46-3.86.The maximum hydrogen production rate during this experiment was 5.54 L/(L·d), when hydrogen content was 49.63%,HRT was 2h, pH was 3.57 and OLR was 97.9 kg COD/(m3·d).
The results of the two experiments verified the feasibility of fermentative hydrogen production from sugarbeet, but the hydrogen production rate and utilization rate of substrate were still improvable. It was also need to pay more attention to the feeding form of sugarbeet.
引文
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[3]Hawkes F. R.,Dinsdale R.,Hawkes D.L.,et al.Sustainable fermentative hydrogen production:challenges for process optimization. Int. J.Hydrogen Energy,2002, 27:1339-1347
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[5]Fernando A. Lopes Pinto,Olga Troshina, Peter Lindblad.A brief look at three decades of research on cyanobacterial hydrogen evolution. Int. J. Hydrogen Energy,2002, 27:1209-1215
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[8]S.Kumazawa, A.Mitsui.Characterization and optimization of hydrogen photoproduction by a saltwater blue-green alga, Oscillatoria sp. Miami BG7.Ⅰ.Enhancement through limiting the supply of nitrogen nutrients. Int. J.Hydrogen Energy,1981,6(4):339-348
[9]E.N. Kondratieva, I.N.Gogotov. Production of molecular hydrogen in microor-ganisms. Adv. Biochem.Eng. Biotechnol.,1983,28:139-191
[10]D.Das, T. N. Veziroglu.Hydrogen production by biological processes:a survey of literature. Int. J.Hydrogen Energy,2001,26:13-28
[11]G. Y.Jung, J.R.Kim, J. Y.Park, et al.Hydrogen production by a new chemoheterotrophic bacterium Citrobacter sp.Y19.Int. J.Hydrogen Energy,2002,27:601-610
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