The adoption of pyrolysis oils as renewable alternatives to conventional fossil fuels is limited by their high acidity, elevated water content, and inherent instability. In this study, esterification was used to upgrade pyrolysis oils derived from two feedstocks: beech wood as a representative biomass source and refused-derived fuel (RDF) as a waste-based material. The esterification was conducted using 1-hexanol as the alcohol and Amberlyst36 as a heterogeneous sulfonic acid-based catalyst. Esterification was studied using oil to 1-hexanol volume ratios of 3:1 (E31) and 1:1 (E11). In both cases, esterification improved the quality of the pyrolysis oils by reducing the water content by 98% for beech wood-based oils and at least 66% for RDF waste-based oils, reducing the total acid number (TAN) by 71% for beech wood-based oils and 78% for RDF waste-based oils, while simultaneously increasing their higher heating values (HHVs) from 15 to 34 MJ/kg for beech wood oils and from 37 to 40 MJ/kg for RDF-waste oils. Using the E31 pyrolysis oil to 1-hexanol ratio thus led to much improved oil properties, while using the E11 mixing ratio further reduced the water content, increased the H/C ratio, lowered the acidity, and improved the heating value. However, its benefits were mainly associated with dilution by unreacted 1-hexanol. The findings underscore the potential of 1-hexanol esterification to enhance the properties of pyrolysis oils for both biomass- and waste-based feedstocks, thereby expanding the applicability of these upgraded oils as sustainable fuels. Furthermore, this work contributes to providing knowledge on the feasibility of upgrading waste-derived pyrolysis oils by esterification.

Methanol is a chemical raw material with high potential for facilitating the green transition in industrial processes. The synthesis of methanol from alternative carbon sources, especially the utilisation of steel mill off-gases, is explored. An experimental setup featuring a demonstration plant for methanol synthesis is described. The results focus on the measurement of the temperature profile along the reactor axis, which provides a novel way of an inside view into an industrial-sized reactor tube. The temperature measurements show the initial deactivation of a fresh batch of methanol catalyst, which is in accordance with literature. They also indicate a stable temperature profile in the reactor over time during the utilisation of blast furnace gas and demonstrate the feasibility of methanol production from this alternative carbon source. Disturbances in the feed gas could be handled reliably and did not influence methanol production.

The system integration of cross-industrial networks in the Carbon2Chem (R) project relies on numerical simulations. Hence, this study validates the methanol synthesis loop models vs. the measurements from a demonstration plant, focusing on the thermodynamic, kinetic, and dynamic aspects. The plant can produce up to 500 L per week of methanol from real blast furnace gases of the thyssenkrupp steel plant in Duisburg. Despite its small size, it comprises a recycle gas loop and an original reactor tube of 6 m in length. After validation, the simulation models are used to analyze the dynamic operation limits of the plant, and they are transferred to the model of an industrial size to analyze the operation of cross-industrial networks with volatile boundary conditions.

Carbohydrates are a group of compounds abundantly present in pyrolysis bio-oils. Their quantitative analysis however presents many challenges such as possible co-elution with other oxygenates when liquid chromatographic methods are used. For a cheaper and faster analysis, spectrophotometric methods are a convenient alternative. Most of the absorption spectrometry-based methods stem from the reaction scheme, where the carbohydrates are converted into furfural or 5-hydroxymethylfurfural (HMF) derivatives and simultaneously react with colorizing agents such as phenol or anthrone. Alternatively, the produced compounds can be determined in the UV region without the addition of colorizing agent. An obvious problem arises when these furanic compounds are already present in the mixture, which is the case with most biomass-based pyrolysis bio-oils. In this study, we quantified the responses of 26 potential interferents that are expected to be present in the water-soluble fraction of bio-oils as well as 13 different carbohydrates. To mitigate the interferences, we used styrene-divinylbenzene polymeric resin adsorbents to separate the less polar interferents from the aqueous bio-oil extract and naturally formed bio-oil aqueous phases. A derivatization-GC-MS method was used as a reference for comparison of the results. We found that the adsorption step is crucial for acquiring more precise and accurate results. The anthrone method was the least susceptible to interferences and simultaneously produced results that were the closest to the reference GC-MS method. Statistical analysis showed no significant differences between the optimized anthrone method and the reference GC-MS method.

Accurate and reliable determination of carbonyl content in bio-oils from pyrolysis and hydrothermal liquefaction (HTL) of biomass is crucial not only for estimating the storage stability of the sample but also for creating an adequate design of the hydrotreatment process allowing long-term operation. The composition of bio-oils from various feedstocks can, however, significantly differ from woody bio-oils, which were utilized to develop the Faix method, the most frequently used for carbonyl determination. In this study, we present a limitation of this method when used for the analysis of bio-oils prepared from protein-rich biomass. These bio-oils are known to have a high nitrogen content, which can be present in the form of possibly interfering compounds. In this study, nitrogen interferences were identified, and a correction step mitigating the underestimation of carbonyl content was introduced. This novel approach was tested for 13 crude bio-oils prepared by pyrolysis or HTL from 10 different feedstocks with a wide range of nitrogen content. Besides crude bio-oils, five hydrotreated HTL oils from sewage sludge were also analyzed. For bio-oils or hydrotreated products with increased nitrogen content but containing less than 0.5 mmol/g of carbonyls, without the correction step, the method can provide zero and in extreme cases even negative values. Statistical analysis of results showed that the introduction of the correction step can be crucial for bio-oils containing more than 2 wt% of nitrogen and especially hydrotreated bio-oils from protein-rich biomass.

A demonstration plant designed for methanol synthesis with steel mill gases was operated continuously for the first time over a period of 5 weeks. The reactor represents a single tube with typical dimensions of an industrial tube bundle reactor with a boiling water cooling jacket and is incorporated into a full loop of unreacted gases. Temperature profile along reactor axis and gas composition in gas recycle stream are measured online. In several experiments, the operating range of the plant was determined. Additionally, the reactor and the loop were simulated and the results agree well with experimental values.

Fast pyrolysis is one of the most promising conversion processes for producing advanced biofuels, which can be used as substitute for fuel oils or chemicals. Herbaceous biomass due to its comparatively high amount of cellulose and catalytically active inorganic content results in pyrolysis oil with high water content even if the original biomass was dry. Such bio‐oil separates into two phases: an upper aqueous phase and a bottom tarry phase. The phase separation by decantation is not an efficient method to reduce the water content and total acid number because a part of valuable components will be lost to the aqueous phase. To improve the quality of bio‐oils producing single‐phase liquids by staged condensation seems to be the better method. The minimum condensation temperature which leads to single‐phase liquid bio‐oils was determined to be around 66°C for wheat/barley straw and 62°C for miscanthus. A further increase in temperature will result in bio‐oils with lower water content and total acid number, but goes along with higher losses of organics to the second condensation stage.

Tar removal from gasification gases is a determinant step to guarantee the operational feasibility of gasification-to-chemicals/energy systems. However, this is a very complex process requiring catalytic materials to proceed under reasonably low temperatures and to convert the tars into fuel gases (i.e., CHx). The use of Fe-based catalysts for application has been reported before, however, there are still unsolved questions related to its stability and interaction with some species of gasification gases. Therefore, we evaluated carbon-supported Fe for the decomposition of tar using simulated gasification gases, and toluene, naphthalene, and benzene as models for tar. The effects of temperature (565 < T < 665 °C) and co-feeding CO on the catalytic activity and stability were inspected at laboratory and bench scales. The activity of catalysts for decomposing tars was in the following order: benzene > toluene e > naphthalene. Moreover, there was evidence validating a reversible elemental step toluene⇔benzene over the Fe surface. The characterization of the spent catalysts evidenced the oxidation of the active phase and the carbon deposition on the surface. The formation of FexOy caused a marked loss of activity. Conversely, the carbides were stable and still active for tar decomposition.

One of the easiest ways to minimize the overall costs of bio-oil production is to minimize biomass transportation and, thus, pyrolysis should be performed at or close to the biomass original location. Thus, we applied ablative fast pyrolysis (AFP), as the only potentially mobile pyrolysis unit, to convert residual lignocellulosic biomass into bio-oil. Four different biomass types were converted to bio-oils: beech and poplar wood, straw and miscanthus. To study reliably the influence of biomass type on bio-oil yields, physicochemical properties and composition, pyrolysis was carried out at a constant temperature of 550 degrees C. Titrations and spectroscopic methods were used for the characterization of the main oxygenate groups. GC-MS was used for the quantification of more than 120 volatile compounds. Such a thorough analytical study of AFP bio-oils, heretoforemissing in scientific literature, allowed us to reliably discuss the differences in bio-oils' relative to the knowledge of biomass composition. Significant differences between the bio-oils were observed, with the lowest content of carboxylic and carbonyl groups in the straw bio-oil. The amount of carboxylic and phenolic groups in all the bio-oils was in the typical range observed for bio-oils unlike the carbonyls and levoglucosan content, which was lower than typical for biooils from other pyrolysis units.

The overall aim of the project “BioMates” is to develop a conversion process for agricultural residues (cereal straw) or energy crops (miscanthus) into a liquid intermediate with reliable properties for the co-processing in existing petroleum refineries. The process is divisible into two individual steps—ablative fast pyrolysis and mild hydrotreatment. Both biomass feedstocks were pyrolysed in a laboratory plant and optimal parameters leading to highest organic liquid yield were determined to be 540 °C at the hot surface, 50 bar hydraulic pressure and 80 rpm of rotational speed of the ablation plate. Different setups for condensation and catalytic vapour upgrade were tested and best results regarding highest organic yield with lowest water content could be achieved with a two-stage condensation operating at about 68 °C condensation temperature in the first stage. Here, a total yield of 41 wt% in (oxygenated) organic compounds could be achieved in the first stage condensate compared to only 36 wt% in the tarry phase of single stage condensation. Catalysts for direct upgrading of vapours were tested but found to be inappropriate in the current setup. For mild hydrotreatment conventional sulphidized catalyst and newly developed non-sulphidized catalysts were tested. The new catalysts showed high initial reactivity but fast deactivation. Currently, the commercial catalyst with NiMo-system on Al 2 O 3 -support performed best, especially at 8 MPa hydrogen supply pressure and 360 °C operating temperature. Here, water content below 1 wt%, a density of organic product below 0.9 kg dm −3 and a lower heating value above 39 MJ kg −1 was achieved. Electrochemical compression and purification can supply hydrogen at necessary pressure and flow rate with acceptable energy demand and by that can replace mechanical compression on the supply side and pressure swing adsorption system in the recycle loop. The project aims were fully achieved in TRL3-4 and will be demonstrated in TRL5 until the end of the project.

ABSTRACT Fast pyrolysis is one of the most promising conversion processes for producing advanced biofuels, which can be used as substitute for fuel oils or chemicals. This article investigates the fast pyrolysis of two common types of biomass: a mixture of wheat/barley straw as typical agriculture residue and miscanthus as fast‐growing energy plant. All experiments were performed using an ablative hot surface reactor. It was observed that the product yields using wheat/barley straw and miscanthus are almost similar on mass basis. Noteworthy were the higher share on reaction water and a lower content of organics in the wheat/barley straw based pyrolysis bio‐oil. As a result of the high total water content (about 48 wt%), the bio‐oil separated into two phases: an upper aqueous phase and a bottom tarry phase. The amount of water‐soluble organic compounds contained in the aqueous phase of bio‐oil derived from miscanthus pyrolysis can be attributed to the higher amount of hemicellulose present in miscanthus compared to straw. The phase separation by decantation is not an efficient method to reduce the water content and total acid number because a part of valuable components will be lost to the aqueous phase. Significance The production of bio‐oils through fast pyrolysis technologies (mainly small scale and fluidized bed reactor systems) is widely described in literature. Therefore, the main objective of this work lies in the comparison of yield and quality of bio‐oils from different biomasses (straw as example for agricultural residues and miscanthus representing dedicated energy crops) in the same ablative hot surface reactor with a capacity of about 5 kg/hr.

Gasification of biomass can play a major role in the future’s energy system as a source of renewable electricity, process heat, fuels, and chemicals. The composition of wood poses some constraints for the operation: below a certain limit of gasification agent, parts of the carbon stay solid and must be considered as an efficiency loss. Thermodynamic calculations allow the determination of this solid carbon boundary and give hints for the process optimization. Several examples for gasifiers, gas cleaning approaches—primarily focusing on tar as the main operating difficulty and dust—and producer gas applications are given and evaluated, including some aspects of scale. Finally, the great potential for the production of transportation fuels and base chemicals from renewable resources is discussed. Possible products are methane, methanol, dimethyl ether, gasoline, Fischer–Tropsch liquids and mixed alcohols. If installations for the gasification of woody biomass with chemicals production are combined with water electrolysis from renewable electricity, the carbon conversion efficiency of the process will be raised to 100% or the combined PBtX-installation (Power and Biomass to X) will offer significant balancing power to the electricity transmission network.

Bio-oil properties and composition can be improved by the modification of the pyrolysis-vapours condensation-step just before the bio-oil is created. This improvement can lead to a decrease in water and acid content, and to an increase in the homogeneity of bio-oil. In this work, we studied the influence of the condensation temperature (5-100 degrees C) in the first condensation stage (cooler) of ablative fast pyrolysis on the composition of a miscanthus bio-oil. We carried out the analysis of physicochemical properties (density, viscosity, elemental composition, water content, micro Conradson carbonization residue and higher heating value) of seven bio-oils condensed at different temperatures. Volatile compounds were quantified by a GC-MS method; the sum of the main oxygenated groups (acids and carbonyls) in the whole sample was quantified by titration methods.

Chemie Ingenieur TechnikVolume 90, Issue 9 p. 1150-1150 VortragFree Access Verbesserte Pyrolyseöle durch katalytische Dampfbehandlung und gestufte Kondensation für die Nutzung in Raffinerien S. Conrad, Corresponding Author S. Conrad stefan.conrad@umsicht.fraunhofer.de Fraunhofer UMSICHT, Fraunhofer-Institut für Umwelt-, Sicherheits- und Energietechnik, Bioraffinerie und Biokraftstoffe, Osterfelder Straße 3, 46047 Oberhausen, DeutschlandCorrespondence: S. Conrad (stefan.conrad@umsicht.fraunhofer.de), Fraunhofer UMSICHT, Fraunhofer-Institut für Umwelt-, Sicherheits- und Energietechnik, Bioraffinerie und Biokraftstoffe, Osterfelder Straße 3, 46047 Oberhausen, DeutschlandSearch for more papers by this authorT. Schulzke, T. Schulzke Fraunhofer UMSICHT, Fraunhofer-Institut für Umwelt-, Sicherheits- und Energietechnik, Bioraffinerie und Biokraftstoffe, Osterfelder Straße 3, 46047 Oberhausen, DeutschlandSearch for more papers by this authorV. Heil, V. Heil Fraunhofer UMSICHT, Fraunhofer-Institut für Umwelt-, Sicherheits- und Energietechnik, Bioraffinerie und Biokraftstoffe, Osterfelder Straße 3, 46047 Oberhausen, DeutschlandSearch for more papers by this author S. Conrad, Corresponding Author S. Conrad stefan.conrad@umsicht.fraunhofer.de Fraunhofer UMSICHT, Fraunhofer-Institut für Umwelt-, Sicherheits- und Energietechnik, Bioraffinerie und Biokraftstoffe, Osterfelder Straße 3, 46047 Oberhausen, DeutschlandCorrespondence: S. Conrad (stefan.conrad@umsicht.fraunhofer.de), Fraunhofer UMSICHT, Fraunhofer-Institut für Umwelt-, Sicherheits- und Energietechnik, Bioraffinerie und Biokraftstoffe, Osterfelder Straße 3, 46047 Oberhausen, DeutschlandSearch for more papers by this authorT. Schulzke, T. Schulzke Fraunhofer UMSICHT, Fraunhofer-Institut für Umwelt-, Sicherheits- und Energietechnik, Bioraffinerie und Biokraftstoffe, Osterfelder Straße 3, 46047 Oberhausen, DeutschlandSearch for more papers by this authorV. Heil, V. Heil Fraunhofer UMSICHT, Fraunhofer-Institut für Umwelt-, Sicherheits- und Energietechnik, Bioraffinerie und Biokraftstoffe, Osterfelder Straße 3, 46047 Oberhausen, DeutschlandSearch for more papers by this author First published: 24 August 2018 https://doi.org/10.1002/cite.201855040AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume90, Issue9Special Issue: ProcessNet-Jahrestagung und 33. DECHEMA-Jahrestagung der Biotechnologen 2018September 2018Pages 1150-1150 RelatedInformation

Tar removal from gasification gases is a determinant step to guarantee the operational feasibility of gasification-to-chemicals/energy systems. This study aimed to develop novel carbon-supported catalysts for the elimination of tarry aromatics (toluene, naphthalene and benzene) from gasification gases. Effects of reaction temperature (700 < T < 900 °C) and catalyst nature (Fe0 and Ni0) on the activity were assessed by considering thermo-catalytic conversion and steam reforming, under a simulated gasification gas. The catalysts (Ni and Fe) and support (AC) were characterized by X-ray diffraction (XRD), N2 physisorption, thermogravimetric analysis (TGA), transmission electron microscopy (TEM) and compositional analyses. Both catalysts and support, presented a mesoporous-like texture with a considerable high surface area (690 < SBET < 743 m2/g). Furthermore, dispersion of the metal nanoparticles (active phase) was uniform as confirmed by TEM images. Results from activity tests suggest that Ni/AC has higher effectivity for converting tars than Fe/AC, as confirmed by the low apparent activation energies (34 < Eapp < 98 kJ/mol) for naphthalene and benzene conversion between 700 and 900 °C. The conversion was 100% above 850 °C; nevertheless; below 750 °C, a sharp reduction in benzene conversion was observed, which was attributed to reversible carbon deposition.

Rigid polyurethane (PU) foams are widely used for instance in building insulation. Two component systems comprising of a polyol as component A and a diisocyanate as component B are generally applied. Both components are produced from fossil oil resources. The liquid products from fast pyrolysis of biomass contain a large variety of organic compounds with -OH functional groups. This gives rise to the idea to substitute the polyol component in PU foams with such biomass based intermediates. Pyrolysis condensates derived from woody and herbaceous biomass were dried and samples of PU foams were produced with varying amounts of condensate substituting the polyol component. Especially the foams made from condensates produced from straw showed good insulation properties, which were expressed as low thermal conductivity. Here, with a substitution degree of 80% a thermal conductivity of 0.0283 Wm(-1)K(-1) was achieved, which was 8% lower than for the foams produced from commercial components (0.0308 Wm(-1)K(-1)). Preliminary results for the measurement of com-pressive strength indicated that the required value of 150 kPa can easily be achieved, especially with a high degree of substitution. These results show a high potential for the application of bio-based intermediates in the building sector. Further research on other properties is necessary, but the main requirements for thermal conductivity are already met without optimization of the catalyst/stabilizer system.

The outlet of a mechanical biological treatment plant for mixed municipal solid waste is further processed to produce RRBF (Refined Renewable Biomass Fuel) within the frame of the EU Life+ project MARSS (Material Advanced Recovery Sustainable Systems). The input for the MARSS processing is dry and has small particle sizes below 40 mm, which makes it impossible to be burnt in standard grate firing systems. The main purpose of this study was to examine whether RRBF is a suitable fuel for bubbling fluidized bed combustion for the decentralised production of combined heat and power. RRBF was fed into a bubbling fluidized bed combustion plant with a nominal fuel input of 100 kW in 3 combustion tests. Proximate and ultimate analyses were performed for original RRBF and fly ash. The fuel analyses showed high ash contents between 25 and 37 weight-%, while the lower heating value lay in the range of 10.5-12.9 MJ kg(-1). The ash softening temperature was above 1150 degrees C and therefore no bed agglomeration was observed. Combustion at around 900 degrees C could be maintained without preheating of the combustion air. The carbon content of the fly ash was about 1 %, which indicates complete combustion in the bubbling fluidized bed with sufficient residence time. The content of phosphorous in the fly ash was above 1 % and therefore this is an interesting material for prospective phosphorous recovery, potentially together with sewage sludge or ash from sewage sludge combustion. RRBF is a suitable solid fuel for fluidized bed combustion. (C) 2017 Elsevier Ltd. All rights reserved.

In fundamental heterogeneous catalyst development, testing is usually performed with rather small amounts of catalyst. Transferring the results in terms of performance and catalyst lifetime to industrial relevant pilot-scale is hardly feasible. Thus, a new modular test system has been developed which allows large-scale testing of heterogeneous catalysts in fixed-bed or slurry mode, enabling a wide range of test conditions with regard to particle size, gas composition, pressure, and reaction temperature. The test system has been used for higher alcohol synthesis and one-step dimethyl ether synthesis.

The BioMates technology aims to convert residues and 2nd generation biomass like straw and miscanthus into high-quality bio-based intermediates (the "BioMates"), of compatible properties with conventional refmery conversion units, allowing their direct and risk-free integration to any refinery towards the production of hybrid fuels. The quality of primary liquid product from ablative fast pyrolysis need further upgrading by mild hydrotreatment due to high oxygen content in organic compounds. To reduce the necessary hydrogen amount for this second step towards the production of BioMates the primary vapours coming from pyrolysis are directly contacted with a catalyst prior to condensation to remove some of the oxygen by decarboxylation and decarbonylation. 6 different catalysts are tried in a side stream experimental setup: 2 activated carbons, gamma-Al2O3 and 3 zeolites. 2 catalyst candidates - activated carbon SC40 and HZSM-5 loaded with 10 % Nickel - improved all relevant parameters of tarry phase product: increased organics, carbon and hydrogen content, reduced oxygen content and total acid number and increased higher heating value. Due to missing mass balance for the experiments, a comprehensive interpretation of the overall system performance is not possible.