Is nitrification inhibition the bottleneck of integrating hydrothermal liquefaction in wastewater treatment plants?

Sewage sludge management poses challenges due to its environmental impact, varying composition, and stringent regulatory requirements. In this scenario, hydrothermal liquefaction (HTL) is a promising technology for producing biofuel and extracting phosphorus from sewage sludge. However, the toxic nature of the resulting process water (HTL-PW) raises concerns about integrating HTL into conventional wastewater treatment processes. This study investigated the inhibitory effects of HTL-PW on the activity of the main microbial functions in conventional activated sludge. Upon recirculation of the HTL-PW from the excess sludge into the wastewater treatment plant, the level of COD in the influent is expected to increase by 157 mgO2⋅L-1, resulting in 44% nitrification inhibition (IC50 of 197 mg⋅L-1). However, sorption of inhibitory compounds on particles can reduce nitrification inhibition to 27% (IC50 of 253 mg⋅L-1). HTL-PW is a viable carbon source for denitrification, showing nearly as high denitrification rates as acetate and only 17% inhibition at 157 mgO2⋅L-1 COD. Under aerobic conditions, heterotrophic organic nitrogen and organic matter conversion remains unaffected up to 223 mgO2⋅L-1 COD, with COD removal higher than 94%. This study is the first to explore the full integration of HTL in wastewater treatment plants for biofuel production from the excess activated sludge. Potential nitrification inhibition is concerning, and further long-term studies are needed to fully investigate the impacts.

Detection of volatile hydroperfluoroalkanes during hydrothermal liquefaction of perfluoroalkyl carboxylic acids at circumneutral pH.

Hydrothermal liquefaction (HTL) is a promising technology for converting wet organic waste such as sewage sludge into biocrude oil while simultaneously destroying per- and polyfluoroalkyl substances (PFAS). This study tracked the fate and degradation of six representative PFAS in water to address the effect of perfluoroalkyl chain length on degradation rates and the formation of volatile transformation products at 300-350 °C. While perfluorosulfonic acids were recalcitrant, perfluoroalkyl carboxylic acids (PFCAs) were rapidly and completely decarboxylated to hydroperfluoroalkanes (1 H-perfluoroheptane in the case of perfluorooctanoic acid). The volatile hydroperfluoroalkane was subsequently defluorinated without detectable fluorocarbon intermediates yielding 30-60 % defluorination for ammonium perfluoro(2-methyl-3-oxahexanoate), perfluorobutanoic acid and perfluorooctanoic acid after 2 h at 350 °C. Increasing temperature (especially at 350 °C) and longer perfluoroalkyl chains substantially enhanced the defluorination. This is the first study to report volatile hydroperfluoroalkanes from PFCAs in HTL, raising concern about the potential emission of long-lived greenhouse gasses into the atmosphere, but also opening new avenues for PFAS destruction through HTL.

Anaerobic digestion of wastewater from hydrothermal liquefaction of sewage sludge and combined wheat straw-manure.

Hydrothermal liquefaction (HTL) shows promise for converting wet biomass waste into biofuel, but the resulting high-strength process water (PW) requires treatment. This study explored enhancing energy recovery by anaerobic digestion using semi-batch reactors. Co-digesting manure with HTL-PW from wheat straw-manure co-HTL yielded methane (43-49% of the chemical oxygen demand, COD) at concentrations up to 17.8 gCOD·L-1, whereas HTL-PW from sewage sludge yielded methane (43% of the COD) up to only 12.8 gCOD·L-1 and complete inhibition occurred at 17 gCOD·L-1. Microbial community shifts confirmed inhibition of methanogenic archaea, while hydrolytic-fermentative bacteria were resilient. Differences in chemical composition, particularly higher levels of N-containing heterocyclic compounds in PW of sewage sludge, likely caused the microbial inhibition. The considerable potential of combining HTL with anaerobic digestion for enhanced energy recovery from straw-manure in an agricultural context is demonstrated, yet sewage sludge HTL-PW requires more advanced approaches to deal with methanogenesis inhibitors.

Wet oxidation of aqueous phase from hydrothermal liquefaction of sewage sludge.

Hydrothermal liquefaction (HTL) is a thermochemical process for the conversion of biomass into bio-crude oil. However, treatment of post-HTL aqueous by-products is an emerging issue towards the commercialisation of HTL technology. This study investigates the use of non-catalytic wet oxidation (WO) for the reduction of organic compounds and heat production at different temperatures (200-350 °C), residence times (RT) (2-180 min) and excess oxygen. The aqueous phase from HTL of sewage sludge is investigated, and 97.6% of the chemical oxygen demand (COD) and 96.1% of the total organic carbon (TOC) were removed at the highest temperature and retention time. The minimum energy requirement achieved was 9.6 kWh/kg COD removed at 200 °C for 180 min, and the exothermic reactions of the process can generate 28.3% of the required heat. GC-FID and -MS analysis revealed that the degradation of different groups of organic compounds generates acetic acid as an intermediate by-product of WO, being further oxidised at temperatures higher than 300 °C. NH4+and NH3 are generated from the decomposition of nitrogenated organic compounds showing the highest concentration of 704.5 mg NH4+ /L at 350 °C after 180 min.

Hydrothermal liquefaction of sewage sludge; energy considerations and fate of micropollutants during pilot scale processing.

The beneficial use of sewage sludge for valorization of carbon and nutrients is of increasing interest while micropollutants in sludge are of concern to the environment and human health. This study investigates the hydrothermal liquefaction (HTL) of sewage sludge in a continuous flow pilot scale reactor at conditions expected to reflect future industrial installations. The processing is evaluated in terms of energy efficiency, bio-crude yields and quality. The raw sludge and post-HTL process water and solid residues were analyzed extensively for micropollutants via HPLC-MS/MS for target pharmaceuticals including antibiotics, blood pressure medicine, antidepressants, analgesics, x-ray contrast media, angiotensin II receptor blockers, immunosuppressant drugs and biocides including triazines, triazoles, carbamates, a carboxamide, an organophosphate and a cationic surfactant. The results show that a positive energy return on investment was achieved for all three HTL processing temperatures of 300, 325 and 350 °C with the most beneficial temperature identified as 325 °C. The analysis of the HTL by-products, process water and solids, indicates that HTL is indeed a suitable technology for the destruction of micropollutants. However, due to the large matrix effect of the HTL process water it can only be stated with certainty that 9 out of 30 pharmaceuticals and 5 out of 7 biocides products were destroyed successfully (over 98% removal). One compound, the antidepressant citalopram, was shown to be moderately recalcitrant at 300 °C with 87% removal and was only destroyed at temperatures ≥325 °C (>99% removal). Overall, the results suggest that HTL is a suitable technology for energy efficient and value added sewage sludge treatment enabling destruction of micropollutants.

Primary sewage sludge filtration using biomass filter aids and subsequent hydrothermal co-liquefaction.

Hydrothermal liquefaction (HTL) is a promising technology for biofuel production and treatment of wastewater sludge. The current study investigates a novel utilization of biomass-assisted filtration of primary sludge to obtain high dry matter (DM) content sludge. Drastic improvements in filtration speed are achieved using different types of lignocellulosic biomass filter aids prepared via mechanical pre-treatment. The combined sludge-biomass filter cake is subsequently used as a feedstock for HTL and shows superior bio-crude yields and properties compared to their individual counterparts. The chemical energy recovery to bio-crude is increased to 75% compared to 46% for biomass and 67% for sludge on its own. The increased DM content of filter cakes (∼25%) compared to primary sludge (5%) increases the energy efficiency of HTL of primary sludge by a factor of 4.5. Introducing a biomass filteraid-HTL combination to a wastewater treatment plant would reduce the organic carbon load to treat by 62%. By combining sludge with lignocellulosic biomass the use of alkali catalyst can be avoided entirely which represents a major cost factor in HTL of lignocellulosics.

Effect of hydrothermal liquefaction aqueous phase recycling on bio-crude yields and composition.

Hydrothermal liquefaction (HTL) is a promising thermo-chemical processing technology for the production of biofuels but produces large amounts of process water. Therefore recirculation of process water from HTL of dried distillers grains with solubles (DDGS) is investigated. Two sets of recirculation on a continuous reactor system using K2CO3 as catalyst were carried out. Following this, the process water was recirculated in batch experiments for a total of 10 rounds. To assess the effect of alkali catalyst, non-catalytic HTL process water recycling was performed with 9 recycle rounds. Both sets of experiments showed a large increase in bio-crude yields from approximately 35 to 55wt%. The water phase and bio-crude samples from all experiments were analysed via quantitative gas chromatography-mass spectrometry (GC-MS) to investigate their composition and build-up of organic compounds. Overall the results show an increase in HTL conversion efficiency and a lower volume, more concentrated aqueous by-product following recycling.

Hydrothermal liquefaction of biomass: developments from batch to continuous process.

This review describes the recent results in hydrothermal liquefaction (HTL) of biomass in continuous-flow processing systems. Although much has been published about batch reactor tests of biomass HTL, there is only limited information yet available on continuous-flow tests, which can provide a more reasonable basis for process design and scale-up for commercialization. High-moisture biomass feedstocks are the most likely to be used in HTL. These materials are described and results of their processing are discussed. Engineered systems for HTL are described; however, they are of limited size and do not yet approach a demonstration scale of operation. With the results available, process models have been developed, and mass and energy balances determined. From these models, process costs have been calculated and provide some optimism as to the commercial likelihood of the technology.

Hydrothermal microwave processing of microalgae as a pre-treatment and extraction technique for bio-fuels and bio-products.

Microalgae are regarded as a promising source of lipids for bio-diesel production and bio-products. The current paper investigates the processing of microalgal slurries under controlled microwave irradiation. Microwave power was applied to reach temperatures of 80, 100, 120 and 140 °C at a constant residence time of 12 min. Microwave irradiation led to disruption of the algal cell walls which facilitated lipid extraction. The influence of inorganic material on microwave heating was assessed for three strains including, Nannochloropsis occulata, Chlorogloeopsis fritschii and Pseudochoricystis ellipsoidea. Mass balances were calculated and showed that the amount of carbon, nitrogen and total mass recovered in the residue was highly dependent on process conditions and algae strain. Hydrothermal microwave processing (HMP) was found to be an effective pre-treatment for hydrothermal liquefaction and extraction of lipids and phytochemicals.