Hollow-fiber Membrane Biofilm Reactor Research Articles

Isobutyric and n-butyric acid production from H2 and CO2 by Clostridium luticellarii in a hollow fiber membrane biofilm reactor: Reactor operation and process modelling

Isobutyric and n-butyric acid production from H2 and CO2 by Clostridium luticellarii in a hollow fiber membrane biofilm reactor: Reactor operation and process modelling

Characteristics of denitrification and microbial community in respect to various H2 pressures and distances to the gas supply end in H2-based MBfR.

The hydrogen-based hollow fiber membrane biofilm reactor (H2-based MBfR) has shown to be a promising technology for nitrate (NO3––N) reduction. Hollow fiber membranes (HFM) operating in a closed mode in an H2-based MBfR often suffer from reverse gas diffusion, taking up space for the effective gas substrate and resulting in a reduction in the HFM diffusion efficiency, which in turn affects denitrification performance. In this work, we developed a laboratory-scale H2-based MBfR, which operated in a closed mode to investigate the dynamics of denitrification performance and biofilm microbial community analysis at different H2 supply pressures. A faster formation of biofilm on the HFM and a shorter start-up period were found for a higher H2 supply pressure. An increase in the H2 pressure under 0.08 MPa could significantly promote denitrification, while a minor increase in denitrification was observed once the H2 pressure was over 0.08 MPa. Sequencing analysis of the biofilm concluded that (i) the dominant phylum-level bacteria in the reactor during the regulated hydrogen pressure phase were Gammaproteobacteria and Alphaproteobacteria; (ii) when the hydrogen pressure was 0.04–0.06 MPa, the dominant bacteria in the MBfR were mainly enriched on the hollow fiber membrane near the upper location (Gas inlet). With a gradual increase in the hydrogen pressure, the enrichment area of the dominant bacteria in MBfR gradually changed from the upper location to the distal end of the inlet. When the hydrogen pressure was 0.10 MPa, the dominant bacteria were mainly enriched on the hollow fiber membrane in the down location of the MBfR.

Rapid enrichment of denitrifying methanotrophs in a series hollow-fiber membrane biofilm reactor

Denitrifying anaerobic methane oxidation (DAMO) process uses methane as electron donor to reduce nitrate/nitrite to dinitrogen, which is a potentially efficient, low-cost and clean biological nitrogen removal technology. However, slow microbial growth rate severely limits the application of this promising process. In this study, a series hollow-fiber membrane biofilm reactor (HfMBR) was operated for 90 days to achieve rapid enrichment of these denitrifying methanotrophs. Finally, the highest relative abundance of denitrifying methanotrophic archaea and bacteria (DAMO archaea and bacteria) reached 47.5% and 11.3%, respectively. And the average abundance of DAMO archaea and bacteria increased 92.9 and 136.6 times respectively during the 90-day enrichment. High growth rate of DAMO archaea with a doubling time of 11.6 days was achieved in the second HfMBR according to quantitative PCR results. The results implied that dissolved oxygen would inhibit the growth of DAMO archaea, but the series HfMBR could effectively counteract this unfavorable factor. This work provided theoretical guidance for the rapid enrichment of denitrifying methanotrophs and contributed to the application of methane-dependent denitrification process.

Compartmentation of microbial communities in structure and function for methane oxidation coupled to nitrification–denitrification

A hollow-fiber membrane biofilm reactor was designed and constructed to achieve simultaneous nitrification–denitrification coupled to methane oxidation in low O2/CH4 ratio and high nitrogen removal rate. Three O2/CH4 ratio stages were operated. Ammonia removal rates reached 77.5 and 95 mg/(L·d) at the O2/CH4 ratio of 1.47 and 2.1, respectively. Microbial community analysis revealed that aeration through physical partition and O2/CH4 ratio stages achieved compartmentation of microbial community in structure and function. Combined functional genes analysis using qPCR, the aeration through gas distributer was proved to promote the enrichment of autotrophic ammonia oxidizers in the suspended liquid/mixed filler samples, and the aeration through hollow-fiber membrane favored the growth of methanotrophs and heterotrophic nitrification-aerobic denitrification bacteria. This study helps to develop effective regulatory strategies for high nitrogen removal based on the understanding of the community assembly process and the key driving factors.

Nitric oxide and nitrite removal by partial denitrifying hollow-fiber membrane biofilm reactor coupled with nitrous oxide generation as energy recovery

ABSTRACT Nitrogen oxide (NOx) emissions cause significant impacts on the environment and must therefore be controlled even more stringently. This requires the development of cost-effective removal strategies which simultaneously create value-added by-products or energy from the waste. This study aims to treat gaseous nitric oxide (NO) by hollow-fibre membrane biofilm reactor (HFMBfR) in the presence of nitrite () and evaluate nitrous oxide (N2O) emissions formed as an intermediate product during the denitrification process. Accumulated N2O can be utilised in methane oxidation as an oxidant to produce energy. In the first stage of the study, the HFMBfR was operated by feeding only gaseous NO as the nitrogen source. During this period, the best performance was achieved with 92% NO removal efficiency (RE). In the second stage, both NO gas and were supplied to the system, and 91% NO and 99% reduction were achieved simultaneously with the maximum N2O generation of 386 ± 31 ppm. Lower influent carbon to nitrogen (C/N) ratios, such as 4.5 and 2.0, and higher −N loading rate of 158 mg N day−1 favoured N2O generation. An improved NO removal rate and N2O accumulation were seen with the increasing amount of in the medium. The 16S rDNA sequencing analysis revealed that Alicycliphilus denitrificans and Pseudomonas putida were the dominant species. The study shows that an HFMBfR can be successfully used to eliminate both and gaseous NO and simultaneously generate N2O by adjusting the system parameters such as C/N ratio, and loading.

Ammonia removal through combined methane oxidation and nitrification-denitrification and the interactions among functional microorganisms

It would be highly beneficial to use the methane produced by anaerobic digestion, which is low cost and accessible, as the carbon source in the removal of nitrogenous contaminants in wastewater. However, there is a knowledge gap regarding coupling systems that entail methane oxidation, nitrification, and denitrification, which restricts their industrial application. In this study, we acclimated a mixed culture to deal with simultaneous nitrification-denitrification coupled to methane oxidation in a laboratory-scale hollow-fiber membrane biofilm reactor, which achieved a steady ammonia removal rate of 38.09 mg N/(L•d). Furthermore, a series of batch experiments were conducted to test methane oxidation coupled to nitrate denitrification (AME-D3), nitrite denitrification (AME-D2), and simultaneous nitrification and denitrification (ME-SND). The molar ratio between methane consumed and nitrate reduced (C/N) equals 10 and 5 mol CH4C mol−1 NO3N in AME-D3 and AME-D2, averagely and respectively. Without methane injection, the removal of nitrates and nitrites was very low, indicating that the coupling of nitrate/nitrite denitrification and methane oxidation was beneficial. The average ammonia removal rates in the 20% O2 and 25% O2 groups were 20.06 and 22.03 mg N/(L•d) in the ME-SND system, respectively. Without methane, the ammonia oxidation rate declined, and large amounts of nitrite accumulated. As traditional ammonia and nitrite oxidation approaches are autotrophic, we proposed the possibility of heterotrophic nitrification-aerobic denitrification (HN-AD). To study the coupling systems, the microbial communities and functional bacteria were analyzed. The results indicated that the system contained a guild of methanotrophs (mainly Methylobacter) and HN-AD bacteria (mainly Chrysobacterium and Comamonas).

Effect of gas flow conditions for the treatment of nitric oxide pollutant gas in a hollow fiber membrane biofilm reactor

Nitrogen oxides (NOx) are one of the most important air pollutants, mainly caused by the combustion of fossil fuels and nitric acid production processes. The hollow fiber membrane biofilm reactor (HFMBR) is a suitable candidate for treatment of biodegradable gases such as NO which has a very low water solubility. In this study, NOx removal performance by denitrification process in an HFMBR using a non-porous polydimethylsiloxane (PDMS) based hollow fiber membrane (HFM) under various conditions was evaluated. A bioreactor was operated for 171 days under varying values of NO inlet load (44.6–89.2 mg m−2day-1), nitrate concentration (0−40 mg NO3−-N L-1), membrane inner pressure (0−400 mbarg), and different gas supplying modes as flow-through (open-end) or dead-end (closed-end). During this mode NO could be transferred completely from the gas phase to the biofilm, resulting in an increase in the removal efficiency. Over 4 weeks, the effect of gas supplying mode with a periodical switch of open-end/closed-end was evaluated for different on/off durations. 500 ppm NO/N2 gas was fed through the lumen of the membranes with a flow rate of 10 mL min-1 for 60, 30, and 15 s and gas outlet port was closed by the solenoid valve for an another 60, 30, and 15 s, respectively. The highest removal efficiency was obtained as 91 % when on/off time was 30/30 s. Results showed that overall performance of the reactor can be increased by modifying inner membrane pressure and gas supplying strategy.

Conversion of syngas (CO and H2) to biochemicals by mixed culture fermentation in mesophilic and thermophilic hollow-fiber membrane biofilm reactors

Syngas (CO/H2) fermentation provides an alternative method for organics utilization. The hollow-fiber membrane biofilm reactor (HfMBR) offers a potential way to use CO and H2 effectively. However, studies on syngas utilization by mixed culture fermentation (MCF) in HfMBR were seldom reported. This study is the first to demonstrate and compare the in-situ production of volatile fatty acids via syngas by mesophilic and thermophilic MCF, in which CO and H2 utilization exceeded 95% and even reached 100%. Acetate (4.22 g/L), butyrate (1.35 g/L), caproate (0.88 g/L), and caprylate (0.52 g/L) were detected at 35 °C, whereas acetate was the main metabolite at 55 °C. The proportion of acetate ranged from 47.5% to 62.7% at 35 °C and exceeded 90% at 55 °C in the batch mode. Notably, the acetate concentration and the production rate could reach 24.6 g/L and 16.4 g/(L.d), respectively, at pH 6.5 in the continuous mode at 55 °C. Thus, thermophilic conditions are preferable for high-purity and high-concentration acetate production from syngas. As revealed by Illumina high-throughput sequencing, Clostridium (41.6%) and Thermoanaerobacterium (92.8%) were the dominant bacteria under mesophilic and thermophilic conditions, respectively. This study demonstrates a potential technique for syngas (CO/H2) utilization and biochemicals production by MCF in HfMBR.

Mixed culture fermentation of synthesis gas in the microfiltration and ultrafiltration hollow-fiber membrane biofilm reactors

The effects of pore sizes on the in-situ utilization of synthesis gas (syngas, H2 and CO) mixed culture fermentation (MCF) in the hollow-fiber membrane biofilm reactor (HfMBR) are not clear. Thus, the ultrafiltration (R1) and microfiltration (R2) HfMBRs were constructed. Syngas was totally consumed within the formed biofilm in R1; contrarily, it accumulated notably in R2. In the batch mode of R1 and R2, volatile fatty acids (VFAs) of acetate, butyrate and caproate were the main metabolites, but the production rate of total VFA in R1 (61.9 mmol-C/(L·d)) was higher than that of R2 (27.6 mmol-C/(L·d)). In the continuous mode, the R1 performance was much better than that of R2, and the biofilm in R2 was even washed out. Furthermore, Clostridium (30.0%) was the main genus in the enriched biofilm of R1, which converted syngas to VFAs. Thus, the ultrafiltration membrane shall be the suitable candidate for syngas MCF.

Tunable production of ethanol and acetate from synthesis gas by mesophilic mixed culture fermentation in a hollow fiber membrane biofilm reactor

Abstract Researches on environmentally friendly pathways in mixed culture fermentation (MCF) to convert synthesis gas (syngas), including carbon monoxide (CO) and hydrogen (H2), to biofuels and chemicals are attracting worldwide attention. The hollow-fiber membrane biofilm reactor (HFMBR) offers a potential technology for in-situ utilization of syngas. In this work, the performance of syngas MCF in the HFMBR at acidic pH 4.5 was studied for the first time. Sole ethanol was produced using an HFMBR in batch mode and the maximum concentration reached 16.9 g/L. The results also showed that the partial pressure of H2 (PH2) and CO (PCO) could tune the acetate and ethanol production in HFMBR, in a manner whereby high PH2 and PCO favored ethanol production, while low PH2 and PCO benefited acetate production. Microbial analysis revealed that the dominant genus in the HFMBR biofilm was Clostridium (86.3%), which is consistent with the experimental results. Overall, the adjustable production of acetate and ethanol from syngas in an HFMBR would be useful for the utilization of syngas MCF in the future.

Chromium isotope fractionation during Cr(VI) reduction in a methane-based hollow-fiber membrane biofilm reactor

Chromium (Cr) isotope fractionation analysis is a promising tool for monitoring Cr(VI) reduction in natural aqueous systems. In addition, large amounts of CH4 in natural aqueous sediments are oxidized to CO2 through methanotrophs, thereby mitigating emissions to the atmosphere. However, the investigations on the Cr(VI) reduction process with methanotrophs, and the associated Cr isotope fractionation patterns are scarce. In this study, we have shown that Cr(VI) reduction can occur in the presence of CH4 as the sole electron donor in a hollow-fiber membrane reactor (HfMBR) after direct bacteria enrichment from sediment samples. Products of the methane oxidation by the methanotrophs are used by microbes to reduce Cr(VI) as shown by the progressive increase in δ53Cr with time in the CH4 feed reactor. The isotope fractionation factor (ε) of −2.62 ± 0.20‰ was obtained from the application of the Rayleigh distillation model. The results of Cr isotope fractionation analysis also explained the decrease of Cr(VI) concentration in the N2 feed reactor, where the δ53Cr values remained steady in the first two weeks but significantly increased in the last two weeks, indicating that physical adsorption and subsequent Cr(VI) reduction occurred. This study extended the application of Cr isotope fractionation, showing the suitability of this method for clarifying different Cr(VI) removal processes.

Hydrogen and carbon dioxide mixed culture fermentation in a hollow-fiber membrane biofilm reactor at 25 °C

There have been no reports of H2 and CO2 mixed-culture fermentation (MCF) at 25 °C in a hollow-fiber membrane biofilm reactor (HfMBR). In this study, H2 and CO2 MCF were conducted in an HfMBR at 25 °C producing metabolites including acetate, ethanol, butyrate, and caproate. Compared to pure culture fermentation (i.e., Clostridium carboxidivorans P7), the MCF in HfMBR at 25 °C produced a higher concentration of caproate in this study (3.4 g/L in batch 1 and 5.7 g/L in batch 2). The dominant genera were Clostridium_sensu_stricto_12 and Prevotella_7. The caproate was more likely formed from the pathway of acetate and ethanol rather than via butyrate and ethanol. Since caproate is more valuable than acetate and low temperature fermentation consumes less energy, this process of H2 and CO2 MCF at 25 °C is appropriate for industrial application.

Tracking the activity of the Anammox-DAMO process using excitation–emission matrix (EEM) fluorescence spectroscopy

Coupling of anaerobic ammonium oxidation (anammox) and denitrifying anaerobic methane oxidation (DAMO) microorganisms in a hollow-fiber membrane biofilm reactor (HfMBR) is a potential strategy for simultaneous anaerobic removal of nitrogen and methane in wastewater streams. In these systems, effluents contain dissolved organic substances from anammox and DAMO microorganisms, but their characteristics and relationships have not been investigated. In the present study, excitation-emission matrix (EEM) fluorescence spectroscopy was used to characterize effluent dissolved organic matter (EfDOM) from an Anammox-DAMO HfMBR. Four component types (Component 1–4) were identified by parallel factor analysis (PARAFAC) of EEM data. Component 1 was produced when anammox and DAMO microorganisms simultaneously starved, whereas Component 4 was only generated through the starving period of DAMO microorganisms, and the longer the starving period, the higher the fluorescence intensity of the components. Components 2 and 3 were generated via active and starving periods of co-cultures. More efficient nitrogen removal was accompanied by a higher fluorescence intensity and microbial activity. Compared to measuring both influent and effluent nitrogen concentrations, monitoring EfDOM can obtain other information about the reactor, such as nitrogen removal activity of the reactor, status of the microbes and the duration of starving period the reactor suffered, which therefore offers a complementary but direct tool for assessing reactor performance in complex co-culture systems.

Enhancement of acetate productivity in a thermophilic (55 °C) hollow-fiber membrane biofilm reactor with mixed culture syngas (H2/CO2) fermentation

Conversion of organic wastes to syngas is an attractive way to utilize wastes. The produced syngas can be further used to produce a variety of chemicals. In this study, a hollow-fiber membrane biofilm reactor with mix cultures was operated at 55°C to convert syngas (H2/CO2) into acetate. A high concentration of acetate (42.4g/L) was reached in batch experiment while a maximum acetate production rate of 10.5g/L/day was achieved in the continuous-flow mode at hydraulic retention time (HRT) of 1day. Acetate was the main product in both batch and continuous-flow experiments. n-Butyrate was the other byproduct in the reactor. Acetate accounted for more than 98.5 and 99.1% of total volatile fatty acids in batch and continuous modes, respectively. Illumina Miseq high-throughput sequencing results showed that microorganisms were highly purified and enriched in the reactor. The main genus was Thermoanaerobacterium (66% of relative abundance), which was usually considered as H2 producer in the literature, however, likely played a role as a H2 consumer in this study. This study provides a new method to generate the high producing rate and purity of acetate from syngas.

Simultaneous enrichment of denitrifying anaerobic methane-oxidizing microorganisms and anammox bacteria in a hollow-fiber membrane biofilm reactor.

In this study, the coculture system of denitrifying anaerobic methane oxidation (DAMO) microbes and anaerobic ammonium oxidation (anammox) bacteria was successfully enriched in a hollow-fiber membrane biofilm reactor (HfMBR) using freshwater sediment as the inoculum. The maximal removal rates of nitrate and ammonium were 78mgN/L/day (131mgN/m2/day) and 26mgN/L/day (43mgN/m2/day), respectively. Due to the high rate of methane mass transfer in HfMBR, the activity of DAMO archaea continued to increase during the enrichment period, indicating that HfMBR could be a powerful tool to enrich DAMO microorganisms. Effects of partial methane pressure, temperature, and pH on the cocultures were obvious. However, the microbial activity in HfMBR could be recovered quickly after the shock change of environmental factors. Furthermore, the result also found that DAMO bacteria likely had a stronger competitive advantage than anammox bacteria under the operating conditions in this study. High-throughput sequencing 16S rRNA genes illustrated that the dominant microbes were NC10, Euryarchaeota, Proteobacteria, Planctomycetes, and Chlorobi with relative abundance of 38.8, 26.2, 13.78, 6.2, and 3.6%, respectively.

Direct delivery of CO2 into a hydrogen-based membrane biofilm reactor and model development

A new hydrogen-based hollow fiber membrane biofilm reactor (MBfR) with double membrane technique was developed in this work and systematic research was conducted. A mathematical model was built up to predict pH and Langelier Saturation Index (LSI) in the hydrogen-based autotrophic denitrification system with minimal error. The model tested with varied CO2 pressures identified that increasing CO2 pressure resulted in pH decrease and prevention from precipitation. Long-term performance of the new MBfR was also evaluated. When CO2 was delivered at 0.05MPa, 99% nitrate was removed with a constant neutral pH in the reactor. In the long-term experiment, misdistributions of H2 and CO2 caused disparity of biomass communities on the H2 and CO2 modules, but functional bacteria existed on both modules; this suggested that despite of misdistribution, bubbleless H2 was still able to be transported by recirculation to the CO2 module and became available for the bacteria on the module.

Analysis of the Microbial Community in an Acidic Hollow-Fiber Membrane Biofilm Reactor (Hf-MBfR) Used for the Biological Conversion of Carbon Dioxide to Methane.

Hydrogenotrophic methanogens can use gaseous substrates, such as H2 and CO2, in CH4 production. H2 gas is used to reduce CO2. We have successfully operated a hollow-fiber membrane biofilm reactor (Hf-MBfR) for stable and continuous CH4 production from CO2 and H2. CO2 and H2 were diffused into the culture medium through the membrane without bubble formation in the Hf-MBfR, which was operated at pH 4.5–5.5 over 70 days. Focusing on the presence of hydrogenotrophic methanogens, we analyzed the structure of the microbial community in the reactor. Denaturing gradient gel electrophoresis (DGGE) was conducted with bacterial and archaeal 16S rDNA primers. Real-time qPCR was used to track changes in the community composition of methanogens over the course of operation. Finally, the microbial community and its diversity at the time of maximum CH4 production were analyzed by pyrosequencing methods. Genus Methanobacterium, related to hydrogenotrophic methanogens, dominated the microbial community, but acetate consumption by bacteria, such as unclassified Clostridium sp., restricted the development of acetoclastic methanogens in the acidic CH4 production process. The results show that acidic operation of a CH4 production reactor without any pH adjustment inhibited acetogenic growth and enriched the hydrogenotrophic methanogens, decreasing the growth of acetoclastic methanogens.

Actual Application of a H2-Based Polyvinyl Chloride Hollow Fiber Membrane Biofilm Reactor to Remove Nitrate from Groundwater

To evaluate the actual performance of the H2-based polyvinyl chloride hollow fiber membrane biofilm reactor (HF-MBfR), we used HF-MBfR to remove nitrate from the nitrate contaminated groundwater with the dissolved oxygen (~6.2 mg/L) in Zhangqiu city (Jinan, China). The reactor was operated over 135 days with the actual nitrate contaminated groundwater. The result showed that maximum of nitrate denitrification rate achieved was over 133.8 gNO3--N/m3d (1.18 gNO3--N/m2d) and the total nitrogen removal was more than 95.0% at the conditions of influent nitrate 50 mg/L, hydrogen pressure 0.05 MPa, and dissolved oxygen (DO) 6.2 mg/L, with the nitrate in effluent under the value limits of drinking water. The fluxes analysis showed that the electron-equivalent fluxes of nitrate, sulfate, and oxygen account for about 81.2%, 15.2%, and 3.6%, respectively, which indicated that nitrate reduction could consume more electrons than that of sulfate reduction and dissolved oxygen reduction. The nitrate reduction was not significantly influenced by sulfate reduction and the dissolved oxygen reduction. Based on the actual groundwater quality on site, the Langelier Saturation Index (LSI) was 0.4, and the membrane could be at the risk of surface scaling.

Review of syngas fermentation processes for bioethanol

Bioethanol is recognized as an important renewable and sustainable transportation fuel. Although synthesis gas (syngas: CO, H2, CO2) produced from lignocellulosic biomass (forest or agricultural biomass) is being used in the production of bioethanol by both chemical catalytic and biosynthetic processes, the latter are noted to have more advantages. In the biosynthesis process, such as the fermentation of syngas, bioethanol is produced along with acetate, butanol, butyrate, methane, peptone, and formaldehyde. Although progress has been made on research and development for the utilization of syngas on fermentation technology, the major barriers for the commercialization still include low yield, expensive biological catalyst, slow kinetics, low gas–liquid mass transfer, and challenges with catalytic separation and recycling. This paper presents a review on fermentation product impurities, microorganisms, chemical reactions, separation techniques, bioreactor types, fermentation conditions, gas–liquid mass transfer, current status of the technology and economics. It seems selection of the appropriate microorganism, nutrient medium, and appropriate hollow fiber membrane biofilm reactor might lead toward achieving an increased mass transfer efficiency for commercialization of the bioethanol.

Syngas fermentation of Clostridium carboxidivoran P7 in a hollow fiber membrane biofilm reactor: Evaluating the mass transfer coefficient and ethanol production performance

Gasification followed by syngas fermentation is a unique hybrid process for converting lignocellulosic biomass into fuels and chemicals. Current syngas fermentation faces several challenges with low gas–liquid mass transfer being one of the major bottlenecks. The aim of this work is to evaluate the performance of hollow fiber membrane biofilm reactor (HFM-BR) as a reactor configuration for syngas fermentation. The volumetric mass transfer coefficient (KLa) of the HFM-BR was determined at abiotic conditions within a wide range of gas velocity/flowrate passing through the hollow fiber lumen and liquid velocity/flowrate passing through the membrane module shell. The KLa values of the HFM-BR were higher than most reactor configurations such as stir tank reactors and bubble columns. A continuous syngas fermentation of Clostridium carboxidivorans P7 was implemented in the HFM-BR system at different operational conditions, including the syngas flow rate, liquid recirculation between the module and reservoir, and the dilution rate. It was found that the syngas fermentation performance such as syngas utilization efficiency, ethanol concentration and productivity, and ratio of ethanol to acetic acid depended not only on the mass transfer efficiency but also the characteristics of biofilm attached on the membrane module (biofouling or abrading of the biofilm). The HFM-BR results in a highest ethanol concentration of 23.93g/L with an ethanol to acetic acid ratio of 4.79. Collectively, the research shows the HFM-BR is an efficient reactor system for syngas fermentation with high mass transfer.