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1. Deactivating species in the transformation of crude bio-oil with methanol into hydrocarbons on a HZSM-5 catalyst

Author:
Bilbao, Javier,   et al.   ; Valle, Beatriz; Castaño, Pedro; Olazar, Martin; Gayubo, Ana G.;     Show all 5 Authors
Source:
Journal of catalysis 2012 v.285 no.1 pp. 304-314
ISSN:
0021-9517
Subject:
lignocellulose; sawdust; crystals; carbon; stable isotopes; fluidized beds; methylene chloride; Fourier transform infrared spectroscopy; oxidation; gas chromatography-mass spectrometry; polymerization; zeolites; temperature; biomass; lignin; nuclear magnetic resonance spectroscopy; aromatic compounds; methanol; catalysts; biofuels; nickel; pyrolysis
Abstract:
... A study has been carried out by using different techniques (TPO, FTIR, Raman, ¹³C NMR, GC/MS of the coke dissolved in CH₂Cl₂) on the nature of the coke deposited on a HZSM-5 catalyst modified with Ni in the transformation of the crude bio-oil obtained by flash pyrolysis of lignocellulosic biomass (pine sawdust) into hydrocarbons. The reaction system has two steps in-line. In the first one, the com ...
DOI:
10.1016/j.jcat.2011.10.004

2. Biomass Oxidative Flash Pyrolysis: Autothermal Operation, Yields and Product Properties

Author:
Bilbao, Javier,   et al.   ; Amutio, Maider; Lopez, Gartzen; Aguado, Roberto; Olazar, Martin;     Show all 5 Authors
Source:
Energy & Fuels 2012 v.26 no.2 pp. 1353-1362
ISSN:
1520-5029
Subject:
biofuels; biomass; energy requirements; organic compounds; oxygen; pyrolysis
Abstract:
... Biomass autothermal flash pyrolysis has been carried out by adding oxygen to the reaction environment in a bench-scale plant provided with a conical spouted bed reactor, at 500 °C and using two oxygen concentrations in the inlet gas stream (2.5 and 4.1 vol %, which correspond to equivalence ratios of 15 and 25, respectively). An increase in the oxygen concentration leads to an increase in gas and ...
DOI:
10.1021/ef201662x

3. Effect of space velocity on the hydrocracking of Light Cycle Oil over a Pt–Pd/HY zeolite catalyst

Author:
Bilbao, Javier,   et al.   ; Gutiérrez, Alazne; Arandes, José M.; Castaño, Pedro; Olazar, Martin; Barona, Astrid;     Show all 6 Authors
Source:
Fuel processing technology 2012 v.95 pp. 8-15
ISSN:
0378-3820
Subject:
acidity; catalysts; catalytic cracking; distillates; gasoline; liquid petroleum gas; oils; streams; yields; zeolites
Abstract:
... The effect of space velocity (WHSV) has been studied in the single-step hydrocracking of the LCO (Light Cycle Oil) obtained as byproduct in catalytic cracking (FCC) units, over a bifunctional catalyst of Pt–Pd supported on a high acidity HY zeolite. Accordingly, the hydrocracking and hydrodesulphurization conversions and yields of product fractions (medium distillates, naphtha, LPG and dry gas) ha ...
DOI:
10.1016/j.fuproc.2011.11.003

4. Deactivating Species Deposited on Pt–Pd Catalysts in the Hydrocracking of Light-Cycle Oil

Author:
Bilbao, Javier,   et al.   ; Castaño, Pedro; Gutiérrez, Alazne; Hita, Idoia; Arandes, José M.; Aguayo, Andrés T.;     Show all 6 Authors
Source:
Energy & Fuels 2012 v.26 no.3 pp. 1509-1519
ISSN:
1520-5029
Subject:
Fourier transform infrared spectroscopy; acidity; aluminum oxide; catalysts; comprehensive two-dimensional gas chromatography; cracking; gas chromatography-mass spectrometry; oxidation; palladium; platinum; topology; zeolites
Abstract:
... The nature and composition of the coke deposited on Pt–Pd catalysts supported on acid carriers during the hydroprocessing (hydrocracking and hydrotreating) of light-cycle oil (LCO) has been studied. Five types of supports have been used: a commercial cracking catalyst, alumina, Hβ zeolite, and two HY zeolites (with different acidities). The hydrocracking runs have been performed at 350 °C and 50 b ...
DOI:
10.1021/ef2019676

5. Enhancement of aromatic hydro-upgrading on a Pt catalyst by promotion with Pd and shape-selective supports

Author:
Bilbao, Javier,   et al.   ; Gutiérrez, Alazne; Arandes, José M.; Castaño, Pedro; Olazar, Martin;     Show all 5 Authors
Source:
Fuel processing technology 2012 v.101 pp. 64-72
ISSN:
0378-3820
Subject:
acidity; alkanes; aromatic compounds; catalysts; distillates; gases; liquid petroleum gas; streams; temperature; yields; zeolites
Abstract:
... The effect of the composition of the metallic function (Pt and Pt–Pd) and acid function (HUSY and Hβ zeolites) in the catalysts has been studied in the hydrocracking of LCO in the 350–400°C range. The remaining operating conditions are: 50bar; H₂/LCO molar ratio (nH₂), 8.90molH₂ (molLCO)⁻¹; space velocity (WHSV), 4h⁻¹; time on stream (TOS), 0–24h. The reaction indices studied are the conversions o ...
DOI:
10.1016/j.fuproc.2012.03.014

6. Effect of Pressure on the Hydrocracking of Light Cycle Oil with a Pt–Pd/HY Catalyst

Author:
Bilbao, Javier,   et al.   ; Gutiérrez, Alazne; Arandes, José M.; Castaño, Pedro; Olazar, Martin;     Show all 5 Authors
Source:
Energy & Fuels 2012 v.26 no.9 pp. 5897-5904
ISSN:
1520-5029
Subject:
air; aromatic compounds; catalysts; combustion; distillates; gasoline; oils; streams
Abstract:
... The effect of pressure (35–75 bar) has been studied on the hydrocracking of light cycle oil (LCO) on a Pt–Pd/HY catalyst. The remaining operating conditions are as follows: 400 °C; H₂/LCO molar ratio (nH₂), 10 molH₂ (molLCO)⁻¹; space velocity (WHSV), 2 h–¹; time on stream, 0–24 h. The reaction indices studied are the conversions of hydrocracking and hydrodesulphurisation, the selectivity of naphth ...
DOI:
10.1021/ef3009597

7. Joint Transformation of Methanol and n-Butane into Olefins on an HZSM-5 Zeolite Catalyst in Reaction–Regeneration Cycles

Author:
Bilbao, Javier,   et al.   ; Aguayo, Andrés T.; Gayubo, Ana G.; Ateka, Ainara; Gamero, Mónica; Olazar, Martin;     Show all 6 Authors
Source:
Industrial & Engineering Chemistry Research 2012 v.51 no.40 pp. 13073-13084
ISSN:
1520-5045
Subject:
air; alkenes; butanes; catalysts; combustion; engineering; kinetics; methanol; temperature; zeolites
Abstract:
... The joint transformation of methanol and n-butane has been studied under energy-neutral conditions (methanol/n-butane molar ratio of 3/1) on an HZSM-5 zeolite catalyst in order to determine the reactivation kinetics and optimize the process conditions for maximizing the light olefin production rate. The methodology for determining the reactivation kinetics combines the kinetic models for the main ...
DOI:
10.1021/ie301142k

8. Polyethylene Cracking on a Spent FCC Catalyst in a Conical Spouted Bed

Author:
Bilbao, Javier,   et al.   ; Elordi, Gorka; Olazar, Martin; Castaño, Pedro; Artetxe, Maite;     Show all 5 Authors
Source:
Industrial & Engineering Chemistry Research 2012 v.51 no.43 pp. 14008-14017
ISSN:
1520-5045
Subject:
acidity; air; alkanes; alkenes; aromatic compounds; bentonite; catalysts; catalytic cracking; coatings; combustion; cracking; crystals; engineering; gasoline; heat; hydrogen; mass transfer; melting; micropores; polyethylene; polyolefin; porous media; zeolites
Abstract:
... The catalytic cracking of HDPE (high density polyethylene) at 500 °C using a spent FCC catalyst agglomerated with bentonite (50 wt %) has been studied in a conical spouted bed reactor. The reaction is carried out in continuous regime (1 g min–¹ of HDPE is fed) with no bed defluidization problems. The results obtained, namely, total conversion, and high yields of gasoline (C₅–C₁₁ fraction) (50 wt % ...
DOI:
10.1021/ie3018274

9. Production of Light Olefins from Polyethylene in a Two-Step Process: Pyrolysis in a Conical Spouted Bed and Downstream High-Temperature Thermal Cracking

Author:
Bilbao, Javier,   et al.   ; Artetxe, Maite; Lopez, Gartzen; Elordi, Gorka; Amutio, Maider; Olazar, Martin;     Show all 6 Authors
Source:
Industrial & Engineering Chemistry Research 2012 v.51 no.43 pp. 13915-13923
ISSN:
1520-5045
Subject:
aromatic compounds; engineering; ethylene; polyethylene; propylene; pyrolysis; quartz; thermal cracking; waxes
Abstract:
... A two-step process has been used for the selective production of light olefins by the thermal cracking of high-density polyethylene. The plastic has been continuously fed into a conical spouted-bed reactor (CSBR) operating at 500 °C, which yields 93 wt % of waxes (C₂₁₊) and C₁₂–C₂₁ hydrocarbons. The volatile product stream has been cracked downstream in a multitubular (quartz tubes) reactor in the ...
DOI:
10.1021/ie300178e

10. Flash pyrolysis of forestry residues from the Portuguese Central Inland Region within the framework of the BioREFINA-Ter project

Author:
Bilbao, Javier,   et al.   ; Amutio, Maider; Lopez, Gartzen; Alvarez, Jon; Moreira, Rui; Duarte, Gustavo; Nunes, Joao; Olazar, Martin;     Show all 8 Authors
Source:
Bioresource technology 2013 v.129 pp. 512-518
ISSN:
0960-8524
Subject:
wastes; ketones; shrubs; phenols; carbohydrates; acids; feedstocks; forestry; Acacia dealbata; pyrolysis; Spartium junceum; aldehydes; Cytisus; forests
Abstract:
... The feasibility of the valorization by flash pyrolysis of forest shrub wastes, namely bushes (Cytisus multiflorus, Spartium junceum, Acacia dealbata and Pterospartum tridentatum) has been studied in a conical spouted bed reactor operating at 500°C, with a continuous biomass feed and char removal. High bio-oil yields in the 75–80wt.% range have been obtained for all of the materials, with char yiel ...
DOI:
10.1016/j.biortech.2012.11.114
PubMed:
23266853

11. Minimum Spouting Velocity of Conical Spouted Beds Equipped with Draft Tubes of Different Configuration

Author:
Bilbao, Javier,   et al.   ; Altzibar, Haritz; Lopez, Gartzen; Olazar, Martin;     Show all 4 Authors
Source:
Industrial & Engineering Chemistry Research 2013 v.52 no.8 pp. 2995-3006
ISSN:
1520-5045
Subject:
chemistry; engineering; experimental design; hydrodynamics; prediction
Abstract:
... The hydrodynamics and the influence of the geometric and operating factors on the minimum spouting velocity have been studied in draft tube conical spouted beds with materials of different size and density. Two draft tube configurations have been used: nonporous and open-sided tubes. Based on an experimental design, the factors of greater influence have been extracted and the general correlations ...
DOI:
10.1021/ie302407f

12. Cracking of High Density Polyethylene Pyrolysis Waxes on HZSM-5 Catalysts of Different Acidity

Author:
Bilbao, Javier,   et al.   ; Artetxe, Maite; Lopez, Gartzen; Amutio, Maider; Elordi, Gorka; Olazar, Martin;     Show all 6 Authors
Source:
Industrial & Engineering Chemistry Research 2013 v.52 no.31 pp. 10637-10645
ISSN:
1520-5045
Subject:
acidity; catalysts; engineering; ethylene; polyethylene; propylene; pyrolysis; waxes; zeolites
Abstract:
... High density polyethylene (HDPE) cracking has been carried out in a thermal-catalytic two-step unit for the selective production of light olefins. Continuous pyrolysis of HDPE has been conducted in a conical spouted bed reactor at 500 °C, and the volatiles formed (mainly waxes) have been transformed in a downstream fixed bed catalytic reactor at 500 °C. The effect of catalyst acidity on product yi ...
DOI:
10.1021/ie4014869

13. Membrane Reactors for in Situ Water Removal: A Review of Applications

Author:
Bilbao, Javier,   et al.   ; Diban, Nazely; Aguayo, Andres T.; Urtiaga, Ane; Ortiz, Inmaculada;     Show all 5 Authors
Source:
Industrial & Engineering Chemistry Research 2013 v.52 no.31 pp. 10342-10354
ISSN:
1520-5045
Subject:
catalysts; catalytic activity; cosmetics; engineering; industrial applications; pervaporation; poisoning; temperature; thermodynamics; vapors
Abstract:
... This paper reviews the investigated applications of membrane reactors for in situ water removal during catalytic reactions in the food, pharmaceutical, cosmetics, and petrochemical sectors. The global target in the works reported herein was the design of a compact and more efficient catalytic reactor (process intensification). By applying in situ water removal, two objectives have been pursued: i) ...
DOI:
10.1021/ie3029625

14. Operating conditions for attenuating Ni/La₂O₃–αAl₂O₃ catalyst deactivation in the steam reforming of bio-oil aqueous fraction

Author:
Bilbao, Javier,   et al.   ; Remiro, Aingeru; Valle, Beatriz; Aguayo, A.T.; Gayubo, Ana G.;     Show all 5 Authors
Source:
Fuel processing technology 2013 v.115 pp. 222-232
ISSN:
0378-3820
Subject:
biofuels; carbon; catalysts; combustion; fluidized beds; hydrogen; lignin; nickel; steam; temperature
Abstract:
... A study was carried out on the effect of temperature (in the 500–800°C range) and space–time (between 0.10 and 0.45gcₐₜₐₗyₛₜ h(gbᵢₒ₋ₒᵢₗ)⁻¹) on Ni/La₂O₃–αAl₂O₃ catalyst deactivation by coke deposition in the steam reforming of bio-oil aqueous fraction. The experiments were conducted in a two-step system, provided with a thermal step at 200°C for the pyrolytic lignin retention and an on-line step of ...
DOI:
10.1016/j.fuproc.2013.06.003

15. Steam gasification of biomass in a conical spouted bed reactor with olivine and γ-alumina as primary catalysts

Author:
Bilbao, Javier,   et al.   ; Erkiaga, Aitziber; Lopez, Gartzen; Amutio, Maider; Olazar, Martin;     Show all 5 Authors
Source:
Fuel processing technology 2013 v.116 pp. 292-299
ISSN:
0378-3820
Subject:
biomass; catalysts; cracking; gasification; polycyclic aromatic hydrocarbons; sand; sawdust; silica; steam; wood
Abstract:
... Olivine and γ-alumina have been used as primary catalysts for tar elimination in the continuous steam gasification of pine wood sawdust in a bench-scale plant provided with a conical spouted bed reactor. A comparison of the performance of each catalyst with that observed for a bed made up of inert silica sand shows that both catalysts have a significant activity for tar cracking/reforming, given t ...
DOI:
10.1016/j.fuproc.2013.07.008

16. Steam Reforming of the Bio-Oil Aqueous Fraction in a Fluidized Bed Reactor with in Situ CO2 Capture

Author:
Bilbao, Javier,   et al.   ; Remiro, Aingeru; Valle, Beatriz; Aramburu, Borja; Aguayo, Andrés T.; Gayubo, Ana G.;     Show all 6 Authors
Source:
Industrial & Engineering Chemistry Research 2013 v.52 no.48 pp. 17087-17098
ISSN:
1520-5045
Subject:
adsorbents; biofuels; carbon dioxide; catalysts; cracking; dolomite; engineering; fluidized beds; hydrogen; hydrogen production; lignin; steam; temperature
Abstract:
... The effect of CO₂ capture in hydrogen production by steam reforming of the bio-oil aqueous fraction was studied. The reforming and cracking activity of the adsorbent (dolomite) and the relationship between these reactions and those corresponding to the catalyst (reforming and water gas shift (WGS)) were considered. The experiments were conducted in a two-step system with the first step at 300 °C f ...
DOI:
10.1021/ie4021705

17. Steam Reforming of Raw Bio-oil in a Fluidized Bed Reactor with Prior Separation of Pyrolytic Lignin

Author:
Bilbao, Javier,   et al.   ; Remiro, Aingeru; Valle, Beatriz; Aguayo, A. T.; Gayubo, Ana G.;     Show all 5 Authors
Source:
Energy & Fuels 2013 v.27 no.12 pp. 7549-7559
ISSN:
1520-5029
Subject:
adsorbents; biofuels; carbon; carbon dioxide; carbon monoxide; catalysts; cracking; dolomite; fluidized beds; gasification; hydrogen; hydrogen production; lignin; methane; steam; temperature; volatilization
Abstract:
... The effect that operating conditions (temperature, steam/carbon molar ratio, and space-velocity) have on the steam reforming of raw bio-oil has been studied in a two-step reaction unit. In the first step (operated at 500 °C), a carbonaceous solid (pyrolytic lignin) deposits by repolymerization of certain bio-oil components, and the remaining volatiles are reformed in the second step (fluidized bed ...
DOI:
10.1021/ef401835s

18. Operating and Peak Pressure Drops in Conical Spouted Beds Equipped with Draft Tubes of Different Configuration

Author:
Bilbao, Javier,   et al.   ; Altzibar, Haritz; Lopez, Gartzen; Olazar, Martin;     Show all 4 Authors
Source:
Industrial & Engineering Chemistry Research 2014 v.53 no.1 pp. 415-427
ISSN:
1520-5045
Subject:
chemistry; engineering; experimental design; prediction
Abstract:
... Operating and peak pressure drops have been studied in conical spouted beds equipped with draft tubes of different configuration using materials of different size. The draft tubes used are nonporous and open-sided ones. Based on an experimental design, the factors of greater influence on both pressure drops have been determined and general correlations valid for fine and coarse materials have been ...
DOI:
10.1021/ie402031t

19. Effect of Operating Conditions on Dimethyl Ether Steam Reforming in a Fluidized Bed Reactor with a CuO–ZnO–Al2O3 and Desilicated ZSM-5 Zeolite Bifunctional Catalyst

Author:
Bilbao, Javier,   et al.   ; Vicente, Jorge; Ereña, Javier; Oar-Arteta, Lide; Olazar, Martin; Gayubo, Ana G.;     Show all 6 Authors
Source:
Industrial & Engineering Chemistry Research 2014 v.53 no.9 pp. 3462-3471
ISSN:
1520-5045
Subject:
acidity; catalysts; engineering; fluidized beds; hydrogen; hydrogen production; sodium hydroxide; steam; zeolites
Abstract:
... This paper studies the effect of operating conditions in dimethyl ether (DME) steam reforming on a bifunctional catalyst synthesized with CuO–ZnO–Al₂O₃ metallic function and a HZSM-5 zeolite treated with NaOH to moderate acidity. The experimentation has been carried out in a fluidized bed reactor in the 225–325 °C range, with space time between 0.1 and 2.2 gcₐₜₐₗyₛₜ h/gDME, steam/DME molar ratio b ...
DOI:
10.1021/ie402509c

20. Intensifying Propylene Production by 1-Butene Transformation on a K Modified HZSM-5 Zeolite-Catalyst

Author:
Bilbao, Javier,   et al.   ; Epelde, Eva; Gayubo, Ana G.; Olazar, Martin; Aguayo, Andrés T.;     Show all 5 Authors
Source:
Industrial & Engineering Chemistry Research 2014 v.53 no.12 pp. 4614-4622
ISSN:
1520-5045
Subject:
aluminum oxide; bentonite; catalysts; chemistry; engineering; propylene; streams; temperature; zeolites
Abstract:
... The effect operating conditions have in the selective transformation of 1-butene into propylene has been studied on a catalyst of HZSM-5 zeolite (SiO₂/Al₂O₃ = 280) modified with 1 wt % K (of moderate acid strength) and agglomerated with bentonite and alumina. The kinetic runs have been performed in a fixed bed reactor under the following operating conditions: 400–600 °C; space time, up to 1.6 (gcₐ ...
DOI:
10.1021/ie500082v