Kinetics of nitrogen-, oxygen- and sulfur-containing compounds hydrotreating during co-processing of bio-crude with petroleum stream

Zhu, Cheng; Gutiérrez, Oliver Y.; Santosa, Daniel M.; Flake, Matthew; Weindl, Roland; Kutnyakov, Igor V.; Shi, Hui; Wang, Huamin

doi:10.1016/j.apcatb.2022.121197

Cited by 22 publications

(21 citation statements)

References 65 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The catalysts from these tests were rinsed with acetone at room temperature in the reactor after the tests, and the spent catalysts at the top, middle, and bottom positions in the reactor were collected for analysis. To evaluate the catalytic activity, the spent catalysts have been resulfided and tested using HDS of DBT, a well-established model reaction to measure the HDS activity of catalysts. The HDS of DBT can undergo two reaction pathways: direct desulfurization (DDS pathway) to produce biphenyl and hydrogenation (HYD pathway), which yields sulfur-containing and partially hydrogenated intermediates that are further desulfurized .…”

Section: Resultsmentioning

confidence: 99%

“…The HDS of DBT can undergo two reaction pathways: direct desulfurization (DDS pathway) to produce biphenyl and hydrogenation (HYD pathway), which yields sulfur-containing and partially hydrogenated intermediates that are further desulfurized. 26 The details of the DBT HDS reaction network are reported in our previous publication, 25 and the rate constant measurement results are summarized in the Supporting Information (Table S1).…”

Section: Catalytic Activities Of Fresh and Spent Catalysts In Probementioning

confidence: 99%

See 1 more Smart Citation

Impact of Coprocessing Biocrude with Petroleum Stream on Hydrotreating Catalyst Stability

et al. 2022

Self Cite

View full text Add to dashboard Cite

Coprocessing of biocrudes from hydrothermal liquefaction (HTL) of biomass and wastes with petroleum streams in refinery hydroprocessing has significant potential to accelerate the production of renewable transportation fuels in the near term. However, HTL biocrudes with some problematic characteristics can potentially cause faster deactivation of the catalysts, which is one of the biggest barriers to the adoption of biocrude in the current refinery process. In this work, we investigated the deactivation modes of a sulfide NiMo/Al2O3 hydrotreating catalyst used for coprocessing HTL biocrude (from wastewater sludge) with straight-run diesel. Spent catalysts were collected after coprocessing diesel with different biocrudes after >300 h time on stream and characterized by various techniques. Their catalytic activities were evaluated by model compound testing. Loss of catalyst activity was observed after coprocessing biocrudes. No structural change of the catalyst after coprocessing biocrudes was observed, and catalyst deactivation was largely due to catalyst fouling by carbonaceous species and metal contaminants (such as Fe and K) from biocrudes. Inorganic contaminant deposition leads to the external coating of the catalyst pellets on the top of the reactor, whereas the carbonaceous species potentially bind near the sulfide active phase, thereby blocking access to the active edge sites. Pretreatment of the HTL biocrude can reduce problematic species and alleviate catalyst deactivation during coprocessing.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Catalytic Activities Of Fresh and Spent Catalysts In Probementioning

confidence: 99%

Impact of Coprocessing Biocrude with Petroleum Stream on Hydrotreating Catalyst Stability

et al. 2022

Self Cite

View full text Add to dashboard Cite

show abstract

“…[46,47] The 2D and 3D GC × GC chromatograms of the algal HTL oil (Figure S2) showed the presence of fatty amides, mainly composed of C16 and C18 chains. Zhu et al [50] recently reported that the hydroconversion of tertiary and secondary amides over NiMo/Al 2 O 3 sulfide catalyst occurs via two pathways: deoxygenation followed by denitrogenation of the intermediate amine (main route) and denitrogenation followed by deoxygenation of the alkanol intermediate. Primary fatty amides should react similarly.…”

Section: Resultsmentioning

confidence: 99%

Catalytic Hydrotreatment of Algal HTL Bio‐Oil over Phosphide, Nitride, and Sulfide Catalysts

et al. 2023

View full text Add to dashboard Cite

Global energy demand and environmental concerns about limiting CO 2 emissions have been growing recently. This is why fuel production from renewable resources has become a priority. In this context, microalgae represent an attractive alternative carbon source. In this work, different supported catalysts, including metal phosphide, nitride, and sulfide, were tested for the hydroconversion of bio-oil issued from the hydrothermal liquefaction of microalgae. Supported Ni phosphide catalysts promoted the decarboxylation and decar-bonylation route, while NiMo nitride promoted the hydrodeoxygenation pathway. NiW sulfide catalysts were the most performant, producing a hydrotreated oil with the best higher heating value (HHV), lower aromaticity degree, and lower average molar mass. Among sulfide catalysts, NiWS/SiO 2 À Al 2 O 3 was the least active, probably due to the inhibition of acid sites by the nitrogen compounds. However, NiWS/Al 2 O 3 performed better, showing high hydrogenation performances, which contributed to the conversion of refractory compounds.

show abstract

“…Properties of the bio-oils and VGO will be provided in the Results and Discussion section. A commercial sulfided NiMo/γ-Al 2 O 3 catalyst was used for this study, and its properties have been reported in detail in our previous publication …”

Section: Experimental Methodsmentioning

confidence: 99%

“…A commercial sulfided NiMo/γ-Al 2 O 3 catalyst was used for this study, and its properties have been reported in detail in our previous publication. 26 Coprocessing Tests. A bench-scale hydrotreater was used for the coprocessing tests.…”

Section: ■ Experimental Methodsmentioning

confidence: 99%

Coprocessing Biomass Fast Pyrolysis and Catalytic Fast Pyrolysis Oils with Vacuum Gas Oil in Refinery Hydroprocessing

et al. 2022

View full text Add to dashboard Cite

Fast pyrolysis and catalytic fast pyrolysis (CFP) have been considered to be promising approaches for converting lignocellulosic biomass into liquid bio-oils followed by upgrading to produce fuel-range hydrocarbon products. Coprocessing fast pyrolysis and CFP bio-oils with petroleum feedstocks leverages the existing petroleum refining infrastructure, which reduces capital expenditure for the overall conversion technologies for biomass to fuel and enables fast adoption of the technologies and biofuels. Here, we reported the coprocessing of different woody fast pyrolysis and CFP bio-oils with petroleum vacuum gas oil (VGO) at 5−25% bio-oil blending levels over a NiMo sulfide catalyst for hydrotreating/mild hydrocracking. The catalyst activities over ∼300 h time on stream, the product yield and properties, and the biogenic carbon content in products are provided. Coprocessing of the raw fast pyrolysis bio-oil in our configuration was not successful because the instability of the bio-oil resulted in reactor plugging, and bio-oil stabilization by hydrogenation enabled their stable coprocessing with VGO, whereas the CFP bio-oil can be coprocessed without pretreatment. Simultaneous hydrodesulfurization, hydrodeoxygenation, and hydrocracking reactions occurred during coprocessing, and no obvious decrease in hydrodesulfurization and hydrocracking conversion of VGO was observed, suggesting the minimal impact of coprocessed bio-oils on the reaction of VGO and also the simultaneous conversion of bio-oil and VGO to produce fuel products with muchreduced S and O content. Biogenic carbon content in coprocessed products calculated by yield mass balance, together with results from isotopic measurements, indicates biogenic carbon incorporation into liquid hydrocarbon products. Higher biogenic carbon incorporation into fuel products was observed when coprocessing CFP bio-oils as compared to the fast pyrolysis bio-oils, and over 90% of carbon in CFP bio-oil was incorporated into liquid hydrocarbon products.

show abstract

Kinetics of nitrogen-, oxygen- and sulfur-containing compounds hydrotreating during co-processing of bio-crude with petroleum stream

Cited by 22 publications

References 65 publications

Impact of Coprocessing Biocrude with Petroleum Stream on Hydrotreating Catalyst Stability

Impact of Coprocessing Biocrude with Petroleum Stream on Hydrotreating Catalyst Stability

Catalytic Hydrotreatment of Algal HTL Bio‐Oil over Phosphide, Nitride, and Sulfide Catalysts

Coprocessing Biomass Fast Pyrolysis and Catalytic Fast Pyrolysis Oils with Vacuum Gas Oil in Refinery Hydroprocessing

Contact Info

Product

Resources

About