Assessing the feasibility of chemical recycling via steam cracking of untreated plastic waste pyrolysis oils: Feedstock impurities, product yields and coke formation.

Chemical recycling of plastic waste to base chemicals via pyrolysis and subsequent steam cracking of pyrolysis oils shows great potential to overcome the limitations in present means of plastic waste recycling. In this scenario, the largest concern is the feasibility. Are plastic waste pyrolysis products acceptable steam cracking feedstocks in terms of composition, product yields and coke formation? In this work, steam cracking of two post-consumer plastic waste pyrolysis oils blended with fossil naphtha was performed in a continuous bench-scale unit without prior treatment. Product yields and radiant coil coke formation were benchmarked to fossil naphtha as an industrial feedstock. Additionally, the plastic waste pyrolysis oils were thoroughly characterized. Analyses included two dimensional gas chromatography coupled to a flame ionization detector for the detailed hydrocarbon composition as well as specific analyses for heteroatoms, halogens and metals. It was found that both pyrolysis oils are rich in olefins (∼48 wt%) and that the main impurities are nitrogen, oxygen, chlorine, bromine, aluminum, calcium and sodium. Steam cracking of the plastic waste derived feedstocks led to ethylene yields of ∼23 wt% at a coil outlet temperature of 820 °C and ∼28 wt% at 850 °C, exceeding the ethylene yield of pure naphtha at both conditions (∼22 wt% and ∼27 wt%, respectively). High amounts of heavy products were formed when steam cracking both pyrolysis oils, respectively. Furthermore, a substantial coking tendency was observed for the more contaminated pyrolysis oil, indicating that next to unsaturated hydrocarbons, contaminants are a strong driver for coke formation.

Opportunities and challenges for the application of post-consumer plastic waste pyrolysis oils as steam cracker feedstocks: To decontaminate or not to decontaminate?

Thermochemical recycling of plastic waste to base chemicals via pyrolysis followed by a minimal amount of upgrading and steam cracking is expected to be the dominant chemical recycling technology in the coming decade. However, there are substantial safety and operational risks when using plastic waste pyrolysis oils instead of conventional fossil-based feedstocks. This is due to the fact that plastic waste pyrolysis oils contain a vast amount of contaminants which are the main drivers for corrosion, fouling and downstream catalyst poisoning in industrial steam cracking plants. Contaminants are therefore crucial to evaluate the steam cracking feasibility of these alternative feedstocks. Indeed, current plastic waste pyrolysis oils exceed typical feedstock specifications for numerous known contaminants, e.g. nitrogen (∼1650 vs. 100 ppm max.), oxygen (∼1250 vs. 100 ppm max.), chlorine (∼1460vs. 3 ppm max.), iron (∼33 vs. 0.001 ppm max.), sodium (∼0.8 vs. 0.125 ppm max.)and calcium (∼17vs. 0.5 ppm max.). Pyrolysis oils produced from post-consumer plastic waste can only meet the current specifications set for industrial steam cracker feedstocks if they are upgraded, with hydrogen based technologies being the most effective, in combination with an effective pre-treatment of the plastic waste such as dehalogenation. Moreover, steam crackers are reliant on a stable and predictable feedstock quality and quantity representing a challenge with plastic waste being largely influenced by consumer behavior, seasonal changes and local sorting efficiencies. Nevertheless, with standardization of sorting plants this is expected to become less problematic in the coming decade.

Development of Lignin-Based Mesoporous Carbons for the Adsorption of Humic Acid.

There is an increasing urge to make the transition toward biobased materials. Lignin, originating from lignocellulosic biomass, can be potentially valorized as humic acid (HA) adsorbents via lignin-based mesoporous carbon (MC). In this work, these materials were synthesized for the first time starting from modified lignin as the carbon precursor, using the soft-template methodology. The use of a novel synthetic approach, Claisen rearrangement of propargylated lignin, and a variety of surfactant templates (Pluronic, Kraton, and Solsperse) have been demonstrated to tune the properties of the resulting MCs. The obtained materials showed tunable properties (BET surface area: 95-367 m2/g, pore size: 3.3-36.6 nm, V BJH pore volume: 0.05-0.33 m3/g, and carbon and oxygen content: 55.5-91.1 and 3.0-12.2%, respectively) and good performance in terms of one of the highest HA adsorption capacities reported for carbon adsorbents (up to 175 mg/g).

Quantitative on-line analysis of sulfur compounds in complex hydrocarbon matrices.

An improved method for on-line measurement of sulfur containing compounds in complex matrices is presented. The on-line system consists of a specifically designed sampling system connected to a comprehensive two-dimensional gas chromatograph (GC×GC) equipped with two capillary columns (Rtx®-1 PONA×SGE BPX50), a flame ionization detector (FID) and a sulfur chemiluminescence detector (SCD). The result is an unprecedented sensitivity down to ppm level (1 ppm-w) for various sulfur containing compounds in very complex hydrocarbon matrices. In addition to the GC×GC-SCD, the low molecular weight sulfur containing compounds such as hydrogen sulfide (H2S) and carbonyl sulfide (COS) can be analyzed using a thermal conductivity detector of a so-called refinery gas analyzer (RGA). The methodology was extensively tested on a continuous flow pilot plant for steam cracking, in which quantification of sulfur containing compounds in the reactor effluent was carried out using 3-chlorothiophene as internal standard. The GC×GC-FID/-SCD settings were optimized for ppm analysis of sulfur compounds in olefin-rich (ethylene- and propylene-rich) hydrocarbon matrices produced by steam cracking of petroleum feedstocks. Besides that is primarily used for analysis of the hydrocarbon matrix, FID of the GC×GC-FID/-SCD set-up serves to double check the amount of added sulfur internal standard which is crucial for a proper quantification of sulfur compounds. When vacuum gas oil containing 780 ppm-w of elemental sulfur in the form of benzothiophenes and dibenzothiophenes is subjected to steam cracking, the sulfur balance was closed, with 75% of the sulfur contained in the feed is converted to hydrogen sulfide, 13% to alkyl homologues of thiophene while the remaining 12% is present in the form of alkyl homologues of benzothiophenes. The methodology can be applied for many other conversion processes which use sulfur containing feeds such as hydrocracking, catalytic cracking, kerogen evolution, bio-waste pyrolysis, supercritical water treatment, etc.

On-line Analysis of Nitrogen Containing Compounds in Complex Hydrocarbon Matrixes.

The shift to heavy crude oils and the use of alternative fossil resources such as shale oil are a challenge for the petrochemical industry. The composition of heavy crude oils and shale oils varies substantially depending on the origin of the mixture. In particular they contain an increased amount of nitrogen containing compounds compared to the conventionally used sweet crude oils. As nitrogen compounds have an influence on the operation of thermal processes occurring in coker units and steam crackers, and as some species are considered as environmentally hazardous, a detailed analysis of the reactions involving nitrogen containing compounds under pyrolysis conditions provides valuable information. Therefore a novel method has been developed and validated with a feedstock containing a high nitrogen content, i.e., a shale oil. First, the feed was characterized offline by comprehensive two-dimensional gas chromatography (GC × GC) coupled with a nitrogen chemiluminescence detector (NCD). In a second step the on-line analysis method was developed and tested on a steam cracking pilot plant by feeding pyridine dissolved in heptane. The former being a representative compound for one of the most abundant classes of compounds present in shale oil. The composition of the reactor effluent was determined via an in-house developed automated sampling system followed by immediate injection of the sample on a GC × GC coupled with a time-of-flight mass spectrometer (TOF-MS), flame ionization detector (FID) and NCD. A novel method for quantitative analysis of nitrogen containing compounds using NCD and 2-chloropyridine as an internal standard has been developed and demonstrated.

Potential of genetically engineered hybrid poplar for pyrolytic production of bio-based phenolic compounds.

Wild-type and two genetically engineered hybrid poplar lines were pyrolyzed in a micro-pyrolysis (Py-GC/MS) and a bench scale setup for fast and intermediate pyrolysis studies. Principal component analysis showed that the pyrolysis vapors obtained by micro-pyrolysis from wood of caffeic acid O-methyltransferase (COMT) and caffeoyl-CoA O-methyltransferase (CCoAOMT) down-regulated poplar trees differed significantly from the pyrolysis vapors obtained from non-transgenic control trees. Both fast micro-pyrolysis and intermediate pyrolysis of transgenic hybrid poplars showed that down-regulation of COMT can enhance the relative yield of guaiacyl lignin-derived products, while the relative yield of syringyl lignin-derived products was up to a factor 3 lower. This study indicates that lignin engineering via genetic modifications of genes involved in the phenylpropanoid and monolignol biosynthetic pathways can help to steer the pyrolytic production of guaiacyl and syringyl lignin-derived phenolic compounds such as guaiacol, 4-methylguaiacol, 4-ethylguaiacol, 4-vinylguaiacol, syringol, 4-vinylsyringol, and syringaldehyde present in the bio-oil.

Detailed compositional characterization of plastic waste pyrolysis oil by comprehensive two-dimensional gas-chromatography coupled to multiple detectors.

The detailed compositional characterization of plastic waste pyrolysis oil was performed with comprehensive two-dimensional GC (GC×GC) coupled to four different detectors: a flame ionization detector (FID), a sulfur chemiluminescence detector (SCD), a nitrogen chemiluminescence detector (NCD) and a time of flight mass spectrometer (TOF-MS). The performances of different column combinations were assessed in normal i.e. apolar/mid-polar and reversed configurations for the GC×GC-NCD and GC×GC-SCD analyses. The information obtained from the four detectors and the use of internal standards, i.e. 3-chlorothiophene for the FID and the SCD and 2-chloropyridine for the NCD analysis, enabled the identification and quantification of the pyrolysis oil in terms of both group type and carbon number: hydrocarbon groups (n-paraffins, iso-paraffins, olefins and naphthenes, monoaromatics, naphthenoaromatics, diaromatics, naphthenodiaromatics, triaromatics, naphthenotriaromatics and tetra-aromatics), nitrogen (nitriles, pyridines, quinolines, indole, caprolactam, etc.), sulfur (thiols/sulfides, thiophenes/disulfides, benzothiophenes, dibenzothiophenes, etc.) and oxygen containing compounds (ketones, phenols, aldehydes, ethers, etc.). Quantification of trace impurities is illustrated for indole and caprolactam. The analyzed pyrolysis oil included a significant amount of nitrogen containing compounds (6.4wt%) and to a lesser extent sulfur containing compounds (0.6wt%). These nitrogen and sulfur containing compounds described approximately 80% of the total peak volume for respectively the NCD and SCD analysis. TOF-MS indicated the presence of the oxygen containing compounds. However only a part of the oxygen containing compounds (2.5wt%) was identified because of their low concentrations and possible overlap with the complex hydrocarbon matrix as no selective detector or preparative separation for oxygen compounds was used.

Quantitative analysis of crude and stabilized bio-oils by comprehensive two-dimensional gas-chromatography.

Bio-oils produced by fast pyrolysis of lignocellulosic biomass have proven to be a promising, clean, and renewable energy source. To better assess the potential of using bio-oils for the production of chemicals and fuels a new comprehensive characterization method is developed. The combination of the analyical power of GC×GC-FID and GC×GC-TOF-MS allows to obtain an unseen level of detail for both crude and hydrotreated bio-oils originated from pine wood biomass. The use of GC×GC proves to be essential to capture the compositional differences between crude and stabilized bio-oils. Our method uses a flame ionization detector to quantify the composition, while GC×GC-TOF-MS is used for the qualitative analysis. This method allows quantification of around 150 tentatively identified compounds, describing approximately 80% of total peak volume. The number of quantified compounds in bio-oils is increased with a factor five compared to the present state-of-the-arte. The necessity of using multiple internal standards (dibutyl ether and fluoranthene) and a cold-on column injector is also verified.