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Mikkola, Jyri-Pekka
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Publications (10 of 258) Show all publications
Saeid, S., Kråkström, M., Tolvanen, P., Kumar, N., Eränen, K., Mikkola, J.-P., . . . Salmi, T. (2020). Advanced Oxidation Process for Degradation of Carbamazepine from Aqueous Solution: Influence of Metal Modified Microporous, Mesoporous Catalysts on the Ozonation Process. , 10(1)
Open this publication in new window or tab >>Advanced Oxidation Process for Degradation of Carbamazepine from Aqueous Solution: Influence of Metal Modified Microporous, Mesoporous Catalysts on the Ozonation Process
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2020 (English)Other (Other academic)
Abstract [en]

Carbamazepine (CBZ), a widely used pharmaceutical compound, is one of the most detected drugs in surface waters. The purpose of this work was to identify an active and durable catalyst, which, in combination with an ozonation process, could be used to remove CBZ and its degradation products. It was found that the CBZ was completely transformed after ozonation within the first minutes of the treatment. However, the resulting degradation products, 1-(2-benzaldehyde)-4-hydro-(1H,3H)-quinazoline-2-one (BQM) and 1-(2-benzaldehyde)-(1H,3H)-quinazoline-2,4-dione (BQD), were more resistant during the ozonation process. The formation and degradation of these products were studied in more detail and a thorough catalytic screening was conducted to reveal the reaction kinetics of both the CBZ and its degradation products. The work was performed by non-catalytic ozonation and with six different heterogeneous catalysts (Pt-MCM-41-IS, Ru-MCM-41-IS, Pd-H-Y-12-EIM, Pt-H-Y-12-EIM, Pd-H-Beta-300-EIM and Cu-MCM-41-A-EIM) operating at two temperatures 20 °C and 50 °C. The influence of temperature on degradation kinetics of CBZ, BQM and BQD was studied. The results exhibited a notable difference in the catalytic behavior by varying temperature. The higher reactor temperature (50 °C) showed a higher activity of the catalysts but a lower concentration of dissolved ozone. Most of the catalysts exhibited higher removal rate for BQM and BQD compared to non-catalytic experiments in both temperatures. The Pd-H-Y-12-EIM catalyst illustrated a higher degradation rate of by-products at 50 °C compared to other catalysts.

Keywords
carbamazepine, ozone, zeolites, catalysts synthesis and characterization, catalytic ozonation
National Category
Chemical Process Engineering Other Chemical Engineering Organic Chemistry Other Chemistry Topics Bioenergy
Identifiers
urn:nbn:se:umu:diva-166888 (URN)10.3390/catal10010090 (DOI)
Projects
Bio4Energy
Available from: 2020-01-07 Created: 2020-01-07 Last updated: 2020-01-07
Ma, C., Shukla, S. K., Samikannu, R., Mikkola, J.-P. & Ji, X. (2020). CO2 Separation by a Series of Aqueous Morpholinium-Based Ionic Liquids with Acetate Anions. ACS Sustainable Chemistry & Engineering, 8(1), 415-426
Open this publication in new window or tab >>CO2 Separation by a Series of Aqueous Morpholinium-Based Ionic Liquids with Acetate Anions
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2020 (English)In: ACS Sustainable Chemistry & Engineering, E-ISSN 2168-0485, Vol. 8, no 1, p. 415-426Article in journal (Refereed) Published
Abstract [en]

In this work, CO2 absorption capacities in a series of aqueous N-alkyl-N-methylmorpholinium-based ILs with acetate as the counterpart anion were investigated. Among these ILs, N-butyl-N-methylmorpholinium acetate ([Bmmorp][OAc]) with the highest CO2 absorption capacity was screened for thermodynamic modeling. The non-random two-liquid model and the Redlich–Kwong equation of state (NRTL-RK model) were used to describe the phase equilibria. The CH4 absorption capacity in the aqueous [Bmmorp][OAc] was also measured in order to verify the results predicted from the thermodynamic modeling, and the comparison shows the reliability of the model prediction. The parameters were embedded into the commercial software Aspen Plus. After that, the aqueous [Bmmorp][OAc] solutions with 30–40 wt % of water were selected to carry out process simulation for CO2 separation from biogas, and it was found that using these aqueous [Bmmorp][OAc] gave rise to lower energy usage and smaller size of equipment than other physical solvents. The results suggest that aqueous [Bmmorp][OAc] solution can be used as an alternative to organic solvents and has the potential to decrease the cost of CO2 separation.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2020
Keywords
CO2 separation, ionic liquids, thermodynamic modeling, process simulation
National Category
Water Engineering Other Physics Topics Physical Chemistry Applied Mechanics Oceanography, Hydrology and Water Resources
Identifiers
urn:nbn:se:umu:diva-167245 (URN)10.1021/acssuschemeng.9b05686 (DOI)
Projects
Bio4Energy
Available from: 2020-01-14 Created: 2020-01-14 Last updated: 2020-01-14Bibliographically approved
Shukla, S. K., Nikjoo, D. & Mikkola, J.-P. (2020). Is basicity the sole criterion for attaining high carbon dioxide capture in deep-eutectic solvents?. Physical Chemistry, Chemical Physics - PCCP
Open this publication in new window or tab >>Is basicity the sole criterion for attaining high carbon dioxide capture in deep-eutectic solvents?
2020 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084Article in journal (Refereed) Epub ahead of print
Abstract [en]

A critical analysis of the role of Hammett basicity (H−) and aqueous basicity (pKa) in CO2 uptake in deep-eutectic solvents (DESs) suggests that neither H− nor pKa correlates with the CO2 w/w% capacity in the studied DESs. Instead, strong “synergistic interactions” between donor and acceptor moieties satisfactorily relate to the w/w% of CO2 in DESs.

Place, publisher, year, edition, pages
The Royal Society of Chemistry, 2020
National Category
Other Environmental Engineering Energy Systems
Identifiers
urn:nbn:se:umu:diva-166621 (URN)10.1039/C9CP06017K (DOI)
Projects
Bio4Energy
Available from: 2019-12-19 Created: 2019-12-19 Last updated: 2019-12-20
Mohammadi, M., Shafiei, M., Abdolmaleki, A., Karimi, K., Mikkola, J.-P. & Larsson, C. (2019). A morpholinium ionic liquid for rice straw pretreatment to enhance ethanol production. Industrial crops and products (Print), 139, Article ID 111494.
Open this publication in new window or tab >>A morpholinium ionic liquid for rice straw pretreatment to enhance ethanol production
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2019 (English)In: Industrial crops and products (Print), ISSN 0926-6690, E-ISSN 1872-633X, Vol. 139, article id 111494Article in journal (Refereed) Published
Abstract [en]

Rice straw was successfully pretreated with a novel and inexpensive morpholinium ionic liquid, 1-H-3-methylmorpholinium chloride ([HMMorph][Cl]). The influence of water (30, 40, 50% w/w) and dimethyl sulfoxide (DMSO) (10, 30% w/w), as co-solvents, pretreatment time (2, 3, 5 h), temperature (90, 105, 120 °C), solid loading (5, 6.7, 10% w/w), and straw particle size (<0.177, 0.177–0.841 mm, and 0.841–2 mm) were investigated for maximum ethanol production. The best results were obtained in 50% water, at 120 °C and 5% (w/w) solid loading for 5 h from 0.177 – 0.841 mm straw particles. The hydrolysis yield was increased from 33.2% to 70.1%, while ethanol production yield was improved from 21.9% to 64% of the theoretical maximum. The performance of the IL was comparable to 1-ethyl-3-methylimidazolium acetate. Simple synthesis process and dilute solution required for the pretreatment with [HMMorph][Cl] offers cost reductions in the use of ILs in biofuel production.

Place, publisher, year, edition, pages
Elsevier, 2019
Keywords
Ethanol, Hydrolysis, Morpholinium ionic liquid, Rice straw
National Category
Bioenergy
Identifiers
urn:nbn:se:umu:diva-161787 (URN)10.1016/j.indcrop.2019.111494 (DOI)000484646900063 ()2-s2.0-85067492224 (Scopus ID)
Projects
Bio4Energy
Available from: 2019-08-05 Created: 2019-08-05 Last updated: 2019-11-13Bibliographically approved
Jogi, R., Mäki-Arvela, P., Virtanen, P., Kumar, N., Hemming, J., Smeds, A., . . . Mikkola, J.-P. (2019). Biocrude production through hydro‐liquefaction of wood biomass in supercritical ethanol using iron silica and iron Beta zeolite catalysts. Journal of chemical technology and biotechnology (1986), 94(11), 3736-3744
Open this publication in new window or tab >>Biocrude production through hydro‐liquefaction of wood biomass in supercritical ethanol using iron silica and iron Beta zeolite catalysts
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2019 (English)In: Journal of chemical technology and biotechnology (1986), ISSN 0268-2575, E-ISSN 1097-4660, Vol. 94, no 11, p. 3736-3744Article in journal (Refereed) Published
Abstract [en]

BACKGROUND: In the production of biofuels from lignocellulosic material, biocrude plays a key role. The present work deals with the biocrude production through hydrothermal liquefaction (HTL) of birch wood in supercritical ethanol over 5 wt. % Fe‐H‐Beta‐150 (SiO2 to Al2O3 ratio of 150) or 5 wt. % Fe‐SiO2 catalyst.

RESULTS: The liquid and solid products were characterized with various analytical techniques such as GC‐MS, GC‐FID, SEC, ICP‐MS, p‐XRD, SEM, and solid‐state 13C MAS NMR respectively. The results revealed that 5 wt. % Fe‐H‐Beta‐150, a strongly Brønsted acidic catalyst, enhanced the biocrude formation when compared with a non‐acidic 5 wt. % Fe‐SiO2 catalyst. Hemicellulose and lignin degradation occurred resulting in formation of mainly sugars, acids‐esters and phenolic compounds in liquid phase. The gaseous atmosphere of hydrogen also enhanced the degradation of biomass. The biocrude yield from birch was 25 wt. % over 5 wt. % Fe‐H‐Beta‐150. The Brønsted acidic catalyst gave higher dissolution efficiency and its clear catalytic effect was observed in comparison to non‐acidic 5 wt. % Fe‐SiO2. The degradation level of lignin in presence of 5 wt. % Fe‐H‐Beta‐150 was high 68 wt. % aromatic products were formed, while only 38 wt. % was obtained with 5 wt. % Fe‐SiO2.

CONCLUSIONS: Hydrogen atmosphere enhances the fractionation of birch wood when compared to argon atmosphere. 5 wt. % Fe‐H‐Beta‐150 catalyst enhanced very strongly the degradation of hemicellulose and lignin in biomass to sugars and acid‐esters as well as phenolic compounds, respectively compared to the non‐acidic 5 wt. % Fe‐SiO2 catalyst.

Place, publisher, year, edition, pages
John Wiley & Sons, 2019
Keywords
hydrothermal liquefaction (HTL), birch, supercritical ethanol, hydrogen atmosphere, iron supported zeolite
National Category
Chemical Process Engineering Organic Chemistry Polymer Chemistry
Identifiers
urn:nbn:se:umu:diva-162429 (URN)10.1002/jctb.6181 (DOI)000485843100001 ()
Projects
Bio4Energy
Available from: 2019-08-20 Created: 2019-08-20 Last updated: 2019-11-05Bibliographically approved
Salmi, T., Eränen, K., Tolvanen, P., Mikkola, J.-P. & Russo, V. (2019). Determination of kinetics and equilibria of heterogeneously catalyzed gas-phase reactions in gradientless autoclave reactors by using the total pressure method: Methanol synthesis. Chemical Engineering Science
Open this publication in new window or tab >>Determination of kinetics and equilibria of heterogeneously catalyzed gas-phase reactions in gradientless autoclave reactors by using the total pressure method: Methanol synthesis
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2019 (English)In: Chemical Engineering Science, ISSN 0009-2509, E-ISSN 1873-4405Article in journal (Refereed) Epub ahead of print
Abstract [en]

Rapid methods are very valuable in the determination of the kinetic and mass transfer effects for heterogeneously catalyzed reactions. The total pressure method is a classical tool in the measurement of the kinetics of gas-phase reactions, but it can be successfully applied to the kinetic measurements of gas-phase processes enhanced by solid catalysts. A general theory for the analysis of heterogeneously catalyzed gas-phase kinetics in gradientless batch reactors was presented for the case of intrinsic kinetic control and combined kinetic-diffusion control in porous catalysts. The concept was applied to gas-phase synthesis of methanol from carbon monoxide and hydrogen on a commercial copper-based catalyst (CuO/ZnO/Al2O3 R3-12 BASF). The reaction temperature was 180–210 °C and the initial total pressure was varied between 11 and 21 bar in a laboratory-scale autoclave reactor equipped with a rotating basket for the catalyst particles. The initial molar ratios CO-to-H2 were approximately 1:2, 1:3 and 1:4. The experimental data from methanol synthesis were compared with numerical simulations and a good agreement between the experiments and model simulations was achieved. The predicted equilibrium agrees with previously reported values.

Place, publisher, year, edition, pages
Elsevier, 2019
Keywords
Kinetics, Total pressure method, Modelling, Methanol synthesis, Solid catalyst, Gradientless reactor
National Category
Other Chemistry Topics Metallurgy and Metallic Materials Chemical Process Engineering Energy Engineering Applied Mechanics
Identifiers
urn:nbn:se:umu:diva-166128 (URN)10.1016/j.ces.2019.115393 (DOI)
Projects
Bio4Energy
Available from: 2019-12-12 Created: 2019-12-12 Last updated: 2019-12-12
Khokarale, S. G. & Mikkola, J.-P. (2019). Efficient and catalyst free synthesis of acrylic plastic precursors: methyl propionate and methyl methacrylate synthesis through reversible CO2 capture. Green Chemistry, 21, 2138-2147
Open this publication in new window or tab >>Efficient and catalyst free synthesis of acrylic plastic precursors: methyl propionate and methyl methacrylate synthesis through reversible CO2 capture
2019 (English)In: Green Chemistry, ISSN 1463-9262, E-ISSN 1463-9270, Vol. 21, p. 2138-2147Article in journal (Refereed) Published
Abstract [en]

Methyl propionate (MP) and methyl methacrylate (MMA) are considered as industrially important precursors upon large-scale acrylic plastic production. The existing industrial synthetic protocols of these precursors utilize expensive catalysts accompanied with toxic and explosive gases such as carbon monoxide, ethylene and hydrogen. Herein, we for the first time report highly selective, catalyst-free and room temperature synthesis of MP and MMA precursors through organic superbase involved reversible CO2 capture approach. In short, initially equimolar mixture of organic superbase 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) and methanol were reversibly reacted with molecular CO2 and the obtained switchable ionic liquid, [DBUH][MeCO3] further reacted with an equivalent amount of propionic anhydride or methacrylic anhydride to form MP or MMA, respectively. These reactions were accomplished in different solvents such as DMSO and methanol whereupon, in case of methanol, separation of reaction products occurs from in-situ formed DBU derivatives such as [DBU][propionate] or [DBU][methacrylate]. In case of both MP and MMA synthesis, after use of methanol as a solvent, good recovery of alcoholic solution of esters were achieved where 85% and 92% yields of MP and MMA were obtained, respectively.The molecular DBU was recovered using NaCl saturated alkaline solution. Further, the recovered MMA with methanol was polymerised to poly-MMA using a benzoyl peroxide induced free radical polymerisation process. The synthesis and separation of MP or MMA as well as recovery of DBU was monitored by NMR analysis. Hence, unlike DMSO, methanol not only performed as a regent in CO2 capture and as a solvent media in MP, MMA and poly-MMA synthesis but also assisted in the recovery of DBU from the reaction mixture. Most importantly, here we represented a more efficient, safer and single solvent based alternative synthetic approach for the synthesis of acrylic plastic precursors MP or MMA compared to existing industrial methods. Also, no toxic or expensive catalysts were required.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2019
National Category
Organic Chemistry
Identifiers
urn:nbn:se:umu:diva-157484 (URN)10.1039/C9GC00413K (DOI)000465398000029 ()
Projects
Bio4Energy
Available from: 2019-03-22 Created: 2019-03-22 Last updated: 2019-08-29Bibliographically approved
Mohammadi, M., Shafiei, M., Karimi, K., Abdolmaleki, A., Mikkola, J.-P. & Larsson, C. (2019). Improvement of ethanol production from birch and spruce pretreated with 1-H-3-methylmorpholinium chloride. Electronic Journal of Biotechnology, 41, 95-99
Open this publication in new window or tab >>Improvement of ethanol production from birch and spruce pretreated with 1-H-3-methylmorpholinium chloride
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2019 (English)In: Electronic Journal of Biotechnology, ISSN 0717-3458, E-ISSN 0717-3458, Vol. 41, p. 95-99Article in journal (Refereed) Published
Abstract [en]

Background: Pretreatment is the critically important step for the production of ethanol from lignocelluloses. In this study, hardwood birch (Betula pendula) and softwood spruce (Norway spruce) woods were pretreated with a newly synthesized morpholinium ionic liquid, 1-H-3-methylmorpholinium chloride ([HMMorph][Cl]), followed by enzymatic hydrolysis and fermentation to ethanol.

Results: [HMMorph][Cl] was synthesized using inexpensive raw materials, i.e., hydrochloric acid and N-methyl morpholine, following a simple process. The influence of pretreatment time (2, 3, 5, and 8 h) and temperature (120 and 140°C) in terms of hydrolysis efficiency was investigated. Glucose yields from enzymatic hydrolysis were improved from 13.7% to 45.7% and 12.9% to 51.8% after pretreatment of birch and spruce woods, respectively, under optimum pretreatment conditions (i.e., at 140°C for 3 h) as compared to those from pristine woods. Moreover, the yields of ethanol production from birch and spruce were increased to 34.8% and 44.2%, respectively, while the yields were negligible for untreated woods.

Conclusions: This study demonstrated the ability of [HMMorph][Cl] as an inexpensive agent to pretreat both softwood and hardwood.

Place, publisher, year, edition, pages
Elsevier, 2019
Keywords
Betula, Biofuels, Cellulase, Cellulose, Ethanol, Hydrolysis, Ionic liquid, Lignin, Lignocellulose, Morpholinium ionic liquid, Pretreatment
National Category
Chemical Process Engineering
Identifiers
urn:nbn:se:umu:diva-162903 (URN)10.1016/j.ejbt.2019.07.004 (DOI)000484693400013 ()2-s2.0-85071470411 (Scopus ID)
Projects
Bio4Energy
Available from: 2019-08-30 Created: 2019-08-30 Last updated: 2019-11-14Bibliographically approved
Shukla, S. K., Khokarale, S. G., Bui, T. Q. & Mikkola, J.-P. (2019). Ionic Liquids: Potential Materials for Carbon Dioxide Capture and Utilization. Frontiers in Materials, 6, Article ID 42.
Open this publication in new window or tab >>Ionic Liquids: Potential Materials for Carbon Dioxide Capture and Utilization
2019 (English)In: Frontiers in Materials, ISSN 2296-8016, Vol. 6, article id 42Article, review/survey (Refereed) Published
Abstract [en]

The nonvolatility, structure-tunability and high CO2 uptake capacity render ionic liquids (ILs) the most exciting materials for the carbon dioxide (CO2) capture and fixation to value-added chemicals. The aim of this mini-review is to give a brief idea about the development of the potential ILs for CO2 capture, the mechanism involved in the CO2 binding and the application of ILs in the conversion of CO2 to useful chemicals. The mechanisms and nature of interactions in between IL-CO2 have been discussed in terms of the nature of cation, anion, presence of functional group and the extent of interaction between the components of ILs. The fixation of CO2 to linear and cyclic carbonates and electroreduction of CO2 to carbon-rich fuels in ILs has been accounted in detail. At the end, future challenges in terms of commercializing the ILs for CO2 capture and utilization technology are discussed.

Place, publisher, year, edition, pages
Frontiers Media S.A., 2019
National Category
Other Chemistry Topics
Identifiers
urn:nbn:se:umu:diva-157480 (URN)10.3389/fmats.2019.00042 (DOI)000462456000001 ()
Available from: 2019-03-22 Created: 2019-03-22 Last updated: 2019-04-12Bibliographically approved
Samikannu, R., Shukla, S. K., Samikannu, A. & Mikkola, J.-P. (2019). Lutidinium-Based Ionic Liquids for Efficient Dissolution of Cellulose. New Journal of Chemistry, 43(5), 2299-2306
Open this publication in new window or tab >>Lutidinium-Based Ionic Liquids for Efficient Dissolution of Cellulose
2019 (English)In: New Journal of Chemistry, ISSN 1144-0546, E-ISSN 1369-9261, Vol. 43, no 5, p. 2299-2306Article in journal (Refereed) Published
Abstract [en]

Herein, we have studied the potential of lutidinium-based ILs (1-allyl-3,5-dimethylpyridinium chloride [3,5-ADMPy]Cl and 1-allyl-3,4-dimethylpyridinium chloride [3,4-ADMPy]Cl) in the dissolution of cellulose, and their structures were confirmed by 1H and 13C NMR spectra, respectively. [3,5-ADMPy]Cl exhibited the highest capacity in cellulose dissolution. In fact, it dissolved 20 wt% of cellulose within 12 min and 26 wt% of cellulose in 35 min at 118 °C. The crystallinity and morphology of native and regenerated cellulose were characterised by X-ray diffraction (XRD), scanning electron microscopy (SEM) and CP/MAS 13C NMR spectroscopy. These techniques clearly suggest that the crystallinity of cellulose is reduced upon treatment in lutidinium-based ILs. The thermogravimetric analysis (TGA) showed that regenerated cellulose had thermal stability close to that of native cellulose.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2019
Keywords
Cellulose dissolution, Ionic Liquids, X-ray diffraction, Cross polymerization/magic angle spinning C NMR, Thermogravimetric analysis, viscosity, scanning electron microscopy
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:umu:diva-154779 (URN)10.1039/C8NJ04698K (DOI)000459581000027 ()
Projects
Bio4Energy
Available from: 2019-01-02 Created: 2019-01-02 Last updated: 2019-08-29Bibliographically approved
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