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Refining of hydrochars/ hydrothermally carbonized biomass into activated carbons and their applications
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK). (Niklas Hedin)ORCID iD: 0000-0002-4176-1899
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Hydrothermally treated biomass could not only be used as a fuel or a fertilizer but it can also be refined into high-value products. Activated carbons are one of those. In the studies of this thesis, four different hydrothermally carbonized (HTC) biomasses, including horse manure, grass cuttings, beer waste and biosludge, have been successfully made into activated carbons. The activated carbon materials were in the forms of powdered activated carbons, powdered composites of activated carbon and iron oxide nano-crystals, and activated carbon discs.

The HTC biomasses and the activated carbons were characterized and analyzed using several methods. The biomasses were carbonized to different extent during the hydrothermal treatment, which depended on the different natures of the biomasses. The HTC biomasses were activated into powdered activated carbons by both physical activation, using CO2, and by chemical activation, using H3PO4. Full factorial design matrices were applied to design experiments and study the influence of different parameters used during both physical and chemical activation. Activated carbons with embedded iron oxide nanoparticles were synthesized through hydrothermal carbonization followed by CO2 activation. These composites had high surface areas and showed a strong magnetism, and the powders could be separated from liquid phase by applying a magnetic field. Strong and dense activated carbon discs were also prepared from powdered HTC beer waste by pulsed current processing (PCP) and a subsequent CO2 activation procedure. The potential for carbon dioxide separation from nitrogen, and methylene blue adsorption in aqueous solution, were assessed for the powdered activated carbons produced from HTC biomasses. They showed good performance in both applications. 

Place, publisher, year, edition, pages
Stockholm: Department of Materials and Environmental Chemistry (MMK), Stockholm University , 2014. , 68 p.
Keyword [en]
Hydrothermally carbonized biomass, activated carbon, full factorial design, activated carbon disc, nanoparticles, iron oxide, CO2 separation, methylene blue, adsorption
National Category
Materials Chemistry
Research subject
Materials Chemistry
Identifiers
URN: urn:nbn:se:su:diva-107672ISBN: 978-91-7447-994-2 (print)OAI: oai:DiVA.org:su-107672DiVA: diva2:749329
Public defence
2014-11-18, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 13:00 (English)
Opponent
Supervisors
Funder
Berzelii Centre EXSELENT
Note

At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 1: In press.

Available from: 2014-10-27 Created: 2014-09-23 Last updated: 2015-05-07Bibliographically approved
List of papers
1. Iron Oxide Nanoparticles Embedded in Activated Carbons Prepared from Hydrothermally Treated Waste Biomass
Open this publication in new window or tab >>Iron Oxide Nanoparticles Embedded in Activated Carbons Prepared from Hydrothermally Treated Waste Biomass
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2014 (English)In: ChemSusChem, ISSN 1864-5631, E-ISSN 1864-564X, Vol. 7, no 3, 875-882 p.Article in journal (Refereed) Published
Abstract [en]

Particles of iron oxide (Fe3O4; 20-40nm) were embedded within activated carbons during the activation of hydrothermally carbonized (HTC) biomasses in a flow of CO2. Four different HTC biomass samples (horse manure, grass cuttings, beer production waste, and biosludge) were used as precursors for the activated carbons. Nanoparticles of iron oxide formed from iron catalyst included in the HTC biomasses. After systematic optimization, the activated carbons had specific surface areas of about 800m(2)g(-1). The pore size distributions of the activated carbons depended strongly on the degree of carbonization of the precursors. Activated carbons prepared from highly carbonized precursors had mainly micropores, whereas those prepared from less carbonized precursors contained mainly mesopores. Given the strong magnetism of the activated carbon-nano-Fe3O4 composites, they could be particularly useful for water purification.

Keyword
biomass, carbon, hydrothermal carbonization, iron, magnetic properties
National Category
Chemical Sciences
Identifiers
urn:nbn:se:su:diva-104574 (URN)10.1002/cssc.201300912 (DOI)000332070900024 ()
Note

AuthorCount:5;

Available from: 2014-06-12 Created: 2014-06-11 Last updated: 2017-12-05Bibliographically approved
2. Activated carbons for water treatment prepared by phosphoric acid activation of hydrothermally treated beer waste
Open this publication in new window or tab >>Activated carbons for water treatment prepared by phosphoric acid activation of hydrothermally treated beer waste
2014 (English)In: Industrial & Engineering Chemistry Research, ISSN 0888-5885, E-ISSN 1520-5045, Vol. 53, no 40, 15389-15397 p.Article in journal (Refereed) Published
Abstract [en]

Activated carbons were produced by chemical activation of hydrothermally carbonized (HTC) beer waste, withphosphoric acid as the activation agent. The activation was optimized within a full factorial design, using the outcome of 19different experiments. Four different parameters (concentration of the acid, activation time, activation temperature, flow rate)were analyzed with respect to their influence on the median pore size. The concentration of H3PO4 had a strong positive effecton the median pore size. The specific surface areas of these activated carbons were ∼1000 m2/g, which compared wellcommercially available activated carbons. The activated carbons had mostly large pores with a size of ∼4 nm, and a significantamount of acid surface groups. Scanning electron microscopy (SEM) revealed that the morphology of the HTC beer wastechanged significantly after the chemical activation. The capacity to adsorb methylene blue from aqueous solutions was 341 mg/g,for one of the activated carbons at pH 7. A Langmuir model described the uptake of the dye quite well, which suggested ahomogeneous adsorption of Methylene Blue (MB).

National Category
Materials Chemistry
Research subject
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-107670 (URN)10.1021/ie5004569 (DOI)000343016500010 ()
Funder
Berzelii Centre EXSELENT
Available from: 2014-09-23 Created: 2014-09-23 Last updated: 2017-12-05Bibliographically approved
3. Strong discs of activated carbons from hydrothermally carbonized beer waste
Open this publication in new window or tab >>Strong discs of activated carbons from hydrothermally carbonized beer waste
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2014 (English)In: Carbon, ISSN 0008-6223, E-ISSN 1873-3891, Vol. 78, 521-531 p.Article in journal (Refereed) Published
Abstract [en]

Strong and dense activated carbon discs (ACDs) were synthesized and studied. The discs were produced in a multistep manner from a precursor based on hydrothermally treated beer waste (HTC-BW). The precursor was processed by pulsed current processing (PCP) into ACDs. These discs were activated by physical activation in CO2 at an elevated temperature. The ACDs had surface areas of ∼500 m2/g and contained significant amounts of micro-, meso-, and macropores. The effect on the temperature during the PCP and the presence of tar in the precursor were studied with respect to the properties of the discs. The ACDs had strengths up to 7.2 MPa with densities up to 1.4 g/cm3. The density is the highest reported for discs of activated carbon.

National Category
Materials Chemistry
Research subject
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-107668 (URN)10.1016/j.carbon.2014.07.036 (DOI)000341463900055 ()
Funder
Berzelii Centre EXSELENT
Available from: 2014-09-23 Created: 2014-09-23 Last updated: 2017-12-05Bibliographically approved
4. Activated carbons prepared from hydrothermally carbonized waste biomass used as adsorbents for CO2
Open this publication in new window or tab >>Activated carbons prepared from hydrothermally carbonized waste biomass used as adsorbents for CO2
2013 (English)In: Applied Energy, ISSN 0306-2619, E-ISSN 1872-9118, Vol. 112, 526-532 p.Article in journal (Refereed) Published
Abstract [en]

Activated carbons prepared from hydrothermally carbonized (HTC) waste biomass were studied with respect to the adsorption of carbon dioxide. The physically activated carbons (PAC) exhibited a large adsorption of CO2 of 1.45 mmol/g at a small partial pressure of CO2 (10 kPa and a temperature of 0 degrees C). These PACs were prepared by activation in a stream of CO2 and had significant amounts of ultramicropores, which were established by analyzing the adsorption of CO2 with a density functional theory. The uptake at such low pressures of CO2 is of most importance for an adsorption-driven CO2 capture from flue gas at large power stations, as it is difficult to imagine a pressurization of the flue gas. The capacities to adsorb CO2 of the different activated carbons were compared with both the micropore volumes as established by N-2 adsorption, and the ultramicropore volumes as established by CO2 adsorption. The ultramicropore volume is of crucial importance for the capture of CO2 from flue gas. PAC from HTC grass cuttings and from horse manure had the largest ultramicropore volumes. In general, the PAC showed excellent cyclability of adsorption/desorption of CO2 and a minimal capacity loss after subsequent cycles. In addition, the PAC showed a rapid adsorption of CO2. Both characteristics are essential for the eventual use of such PACs in the adsorption driven separation of CO2 from flue gas. A chemically activated carbon (CAC) was prepared by treating hydrothermally carbonized beer waste with H3PO4 and a heat treatment in a flow of N-2. This CAC showed a significant amount of mesopores in the range of 5 nm, in addition to micropores. The apparent selectivity for the activated carbons for CO2-over-N-2 adsorption was determined at 0 degrees C and 10 kPa.

Keyword
Hydrothermally carbonized biomass, Activated carbon, Separation of CO2, Horse manure, Grass cuttings
National Category
Natural Sciences
Identifiers
urn:nbn:se:su:diva-100666 (URN)10.1016/j.apenergy.2013.02.028 (DOI)000329377800055 ()
Conference
4th International Conference on Applied Energy (ICAE), JUL 01-04, 2012, Suzhou, PEOPLES R CHINA
Note

AuthorCount:4;

Available from: 2014-02-12 Created: 2014-02-10 Last updated: 2017-12-06Bibliographically approved

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