{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,9]],"date-time":"2026-09-09T16:26:22Z","timestamp":1788971182852,"version":"build-2803163510"},"reference-count":52,"publisher":"MDPI AG","issue":"23","license":[{"start":{"date-parts":[[2025,11,22]],"date-time":"2025-11-22T00:00:00Z","timestamp":1763769600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100005802","name":"Ministry of Research, Innovation, and Digitization","doi-asserted-by":"publisher","award":["PN 23.06.02.01 (InteGral)"],"award-info":[{"award-number":["PN 23.06.02.01 (InteGral)"]}],"id":[{"id":"10.13039\/501100005802","id-type":"DOI","asserted-by":"publisher"}]},{"name":"Petroleum\u2013Gas University of Ploie\u0219ti, Romania","award":["30833\/2024 (BIOMAT)"],"award-info":[{"award-number":["30833\/2024 (BIOMAT)"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>Biochar activation is achieved by removing tar formed in the pores during the thermal treatment of biomass, thereby increasing pore volume. This process typically involves entraining tar with steam at elevated temperatures for extended durations. In this study, a reduction in lignin content in grape seeds through partial solubilization, prior to thermal treatment, is proposed. Initially, grape seeds were treated with a basic sodium sulfide solution, followed by conditioning with either phosphoric acid or zinc chloride and then drying and calcination. The synthesized adsorbents were characterized using scanning electron microscopy (SEM), textural analysis, Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and evaluation of toluene adsorption capacity. Textural analysis indicated that conditioning with phosphoric acid or zinc chloride increased the specific surface area of biochar by over 20%, with a higher increase observed for phosphoric acid treatment. The toluene adsorption capacity of the adsorbents was assessed in a continuous fixed-bed system. Biochar pretreated with ZnCl2 exhibited an adsorption capacity of 0.11 cm3 of toluene per gram, while biochar pretreated with phosphoric acid demonstrated a capacity of 0.14 cm3 per gram. These results indicate that preliminary delignification of grape seed biomass maintains its adsorption capacity of toluene at levels comparable to other adsorbents, despite a lower activation temperature.<\/jats:p>","DOI":"10.3390\/molecules30234505","type":"journal-article","created":{"date-parts":[[2025,11,24]],"date-time":"2025-11-24T13:09:25Z","timestamp":1763989765000},"page":"4505","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["Synthesis and Characterization of Biochar Obtained by Partial Delignification of Waste Biomass"],"prefix":"10.3390","volume":"30","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-0217-929X","authenticated-orcid":false,"given":"Gabriel","family":"Vasilievici","sequence":"first","affiliation":[{"name":"National Institute for Research Development for Chemistry and Petrochemistry-ICECHIM-Bucure\u0219ti, 202 Spl. Independen\u021bei, 060021 Bucharest, Romania"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mia","family":"Sanda","sequence":"additional","affiliation":[{"name":"Department of Petroleum Refining Engineering and Environmental Protection, Petroleum-Gas University of Ploiesti, 39 Bucharest Blvd., 100680 Ploiesti, Romania"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Marian","family":"B\u0103jan","sequence":"additional","affiliation":[{"name":"Department of Petroleum Refining Engineering and Environmental Protection, Petroleum-Gas University of Ploiesti, 39 Bucharest Blvd., 100680 Ploiesti, Romania"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2267-9531","authenticated-orcid":false,"given":"Cristina","family":"Du\u0219escu-Vasile","sequence":"additional","affiliation":[{"name":"Department of Petroleum Refining Engineering and Environmental Protection, Petroleum-Gas University of Ploiesti, 39 Bucharest Blvd., 100680 Ploiesti, Romania"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1196-402X","authenticated-orcid":false,"given":"Ion","family":"Onu\u021bu","sequence":"additional","affiliation":[{"name":"Department of Petroleum Refining Engineering and Environmental Protection, Petroleum-Gas University of Ploiesti, 39 Bucharest Blvd., 100680 Ploiesti, Romania"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9562-7564","authenticated-orcid":false,"given":"Gheorghe","family":"Br\u0103noiu","sequence":"additional","affiliation":[{"name":"Department of Petroleum Geology and Reservoir Engineering, Petroleum-Gas University of Ploiesti, 39 Bucharest Blvd., 100680 Ploiesti, Romania"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Dorin","family":"Bombo\u0219","sequence":"additional","affiliation":[{"name":"Chemistry Department, Petroleum-Gas University of Ploiesti, 39 Bucharest Blvd., 100680 Ploiesti, Romania"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Abeer","family":"Baioun","sequence":"additional","affiliation":[{"name":"Chemistry Department, Faculty of Science, University of Damascus, Damascus P.O. Box 30621, Syria"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Anca Florentina","family":"Borcea","sequence":"additional","affiliation":[{"name":"Department of Petroleum Refining Engineering and Environmental Protection, Petroleum-Gas University of Ploiesti, 39 Bucharest Blvd., 100680 Ploiesti, Romania"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Andra-Ioana","family":"St\u0103nic\u0103","sequence":"additional","affiliation":[{"name":"Technological Highschool \u201cToma Socolescu\u201d, Gheorghe Grigore Cantacuzino St., 328, 100466, Ploie\u0219ti, Romania"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2025,11,22]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","unstructured":"Petrovi\u0107, J., Koprivica, M., Ercegovi\u0107, M., Simi\u0107, M., Dimitrijevi\u0107, J., Bugar\u010di\u0107, M., and Trifunovi\u0107, S. (2025). Synthesis and Application of FeMg-Modified Hydrochar for Efficient Removal of Lead Ions from Aqueous Solution. Processes, 13.","DOI":"10.3390\/pr13072060"},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"106704","DOI":"10.1016\/j.jaap.2024.106704","article-title":"Rapid pyrolysis of cellulose: Revealing the role of volatile matter and char structure evolution","volume":"182","author":"Sun","year":"2024","journal-title":"J. Anal. Appl. Pyrolysis"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"58","DOI":"10.1016\/j.micromeso.2018.04.013","article-title":"Adsorptive removal of toluene and carbon tetrachloride from gas phase using Zeolitic Imidazolate Framework-8: Effects of synthesis method, particle size, and pretreatment of the adsorbent","volume":"268","author":"Jafari","year":"2018","journal-title":"Microporous Mesoporous Mater."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"32752","DOI":"10.1021\/acsomega.3c03563","article-title":"Spontaneous Combustion Characteristics of Activated Carbon Modified via Liquid Phase Impregnation during Drying","volume":"8","author":"Li","year":"2023","journal-title":"ACS Omega"},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"97048","DOI":"10.1039\/C6RA18687D","article-title":"A superhydrophobic hyper-cross-linked polymer synthesized at room temperature used as an efficient adsorbent for volatile organic compounds","volume":"6","author":"Wang","year":"2016","journal-title":"RSC Adv."},{"key":"ref_6","unstructured":"Lancia, A., Musmarra, D., and Prisciandaro, D. (1992). Kirk-Othmer Encyclopedia of Chemical Technology, John Wiley & Sons. [4th ed.]."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"107342","DOI":"10.1016\/j.jaap.2025.107342","article-title":"Controlled hydrothermal carbonization of wood-derived lignin-rich lignocellulose: Redefining pyrolytic pathways to tailored biochar and hydrogen-enriched syngas","volume":"192","author":"Rizwan","year":"2025","journal-title":"J. Anal. Appl. Pyrolysis"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"5068","DOI":"10.1051\/e3sconf\/202235605068","article-title":"Measurement and prediction of breakthrough curve of low-concentration toluene adsorbed by activated carbon","volume":"356","author":"Sheng","year":"2022","journal-title":"E3S Web Conf."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"127968","DOI":"10.1016\/j.fuel.2023.127968","article-title":"Production and beneficial impact of biochar for environmental application: A review on types of feedstocks, chemical compositions, operating parameters, techno-economic study, and life cycle assessment","volume":"343","author":"Mishra","year":"2023","journal-title":"Fuel"},{"key":"ref_10","first-page":"111","article-title":"Activated carbon adsorption behaviour of toluene at various temperatures and relative humidity","volume":"45","year":"2019","journal-title":"Environ. Prot. Eng."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"240","DOI":"10.1016\/j.carbon.2014.10.092","article-title":"Factors governing the adsorption of ethanol on spherical activated carbons","volume":"83","year":"2015","journal-title":"Carbon"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"118798","DOI":"10.1016\/j.indcrop.2024.118798","article-title":"Enhancing the quality of products from slow pyrolysis of an agro-industrial biomass waste with natural mineral additives","volume":"216","author":"Ahmad","year":"2024","journal-title":"Ind. Crops Prod."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"120710","DOI":"10.1016\/j.indcrop.2025.120710","article-title":"Synergistic catalysis strategy of Lewis and Br\u00f8nsted acids for superior aromatic production in biomass pyrolysis","volume":"226","author":"Xia","year":"2025","journal-title":"Ind. Crops Prod."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"2922","DOI":"10.1039\/C7RA11740J","article-title":"Activated carbons modified by magnesium oxide as highly efficient sorbents for acetone","volume":"8","author":"Zhou","year":"2018","journal-title":"RSC Adv."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"226","DOI":"10.1007\/s13201-023-02034-w","article-title":"Zinc chloride activated carbon derived from date pits for efficient biosorption of brilliant green: Adsorption characteristics and mechanism study","volume":"13","author":"Akl","year":"2023","journal-title":"Appl. Water Sci."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"125325","DOI":"10.1016\/j.molliq.2024.125325","article-title":"Grape seeds waste activated carbon as an adsorber of paracetamol drug residue: Experimental and theoretical approaches","volume":"408","author":"Mabrouk","year":"2024","journal-title":"J. Mol. Liq."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"143319","DOI":"10.1016\/j.jclepro.2024.143319","article-title":"The joint production of green diesel and activated carbon from spent coconut shells (SCS): An energy techno-economic and Life Cycle Assessment case for China","volume":"472","author":"Ran","year":"2024","journal-title":"J. Clean. Prod."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"104","DOI":"10.1016\/j.jes.2017.06.032","article-title":"Behaviors and kinetics of toluene adsorption-desorption on activated carbons with varying pore structure","volume":"67","author":"Yang","year":"2018","journal-title":"J. Environ. Sci."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"100882","DOI":"10.1016\/j.cogsc.2024.100882","article-title":"Life cycle assessment of biochar as a green sorbent for soil remediation","volume":"46","author":"Osman","year":"2024","journal-title":"Curr. Opin. Green Sustain. Chem."},{"key":"ref_20","unstructured":"Howe-Grant, M., and Kroschwitz, J. (1996). Kirk-Othmer Encyclopedia of Chemical Technology, Wiley."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"221","DOI":"10.1016\/j.biortech.2015.02.035","article-title":"Development and characterization of activated hydrochars from orange peels as potential adsorbents for emerging organic contaminants","volume":"183","author":"Fernandez","year":"2015","journal-title":"Bioresour. Technol."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"19","DOI":"10.1016\/j.enceco.2024.10.002","article-title":"Assessment of the ecotoxicity of extracts from sugarcane bagasse biochars activated with zinc chloride","volume":"7","author":"Carolino","year":"2025","journal-title":"Environ. Chem. Ecotoxicol."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"116147","DOI":"10.1016\/j.jece.2025.116147","article-title":"One- and two-step H2O activation of fungus bran for calcium-rich biochar in tar steam reforming","volume":"13","author":"Guo","year":"2025","journal-title":"J. Environ. Chem. Eng."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"298","DOI":"10.1016\/j.biombioe.2010.08.067","article-title":"Thermogravimetric analysis as a new method to determine the lignocellulosic composition of biomass","volume":"35","author":"Carrier","year":"2011","journal-title":"Biomass Bioenergy"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"123","DOI":"10.1016\/j.biombioe.2013.03.020","article-title":"Porous structure and morphology of granular chars from flash and conventional pyrolysis of grape seeds","volume":"54","author":"Heras","year":"2013","journal-title":"Biomass Bioenergy"},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"365","DOI":"10.1016\/j.proeng.2013.12.193","article-title":"Characterization of biochar derived from rubber wood sawdust through slow pyrolysis on surface porosities and functional groups","volume":"68","author":"Shaabana","year":"2013","journal-title":"Procedia Eng."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"211","DOI":"10.1016\/S0360-0564(08)60615-X","article-title":"Theory of Physical Adsorption","volume":"4","author":"Terrell","year":"1952","journal-title":"Adv. Catal."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"2201502","DOI":"10.1002\/adma.202201502","article-title":"How Reproducible are Surface Areas Calculated from the BET Equation?","volume":"34","author":"Osterrieth","year":"2022","journal-title":"Adv. Mater."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"49","DOI":"10.1016\/S0167-2991(07)80008-5","article-title":"Is the BET equation applicable to microporous adsorbents?","volume":"160","author":"Rouquerol","year":"2007","journal-title":"Stud. Surf. Sci. Catal."},{"key":"ref_30","doi-asserted-by":"crossref","unstructured":"Ahmed, A., Bakar, M.S.A., Razzaq, A., Hidayat, S., Jamil, F., Amin, M.N., Sukri, R.S., Shah, N.S., and Park, Y.-K. (2021). Characterization and Thermal Behavior Study of Biomass from Invasive Acacia mangium Species in Brunei Preceding Thermochemical Conversion. Sustainability, 13.","DOI":"10.3390\/su13095249"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"600","DOI":"10.1016\/j.biombioe.2013.05.035","article-title":"Study of bio-oil and bio-char production from algae by slow pyrolysis","volume":"56","author":"Chaiwong","year":"2013","journal-title":"Biomass Bioenergy"},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"e11940","DOI":"10.1016\/j.heliyon.2022.e11940","article-title":"Activated carbon from biomass precursors using phosphoric acid: A review","volume":"8","author":"Neme","year":"2022","journal-title":"Heliyon"},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"102799","DOI":"10.1016\/j.jcou.2024.102799","article-title":"Cashew nut shell biomass: A source for high-performance CO2\/CH4 adsorption in activated carbon","volume":"83","author":"Giraldo","year":"2024","journal-title":"J. CO2 Util."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"S1155","DOI":"10.1016\/j.arabjc.2011.12.002","article-title":"Characterization of activated carbon prepared by phosphoric acid activation of olive stones","volume":"9","author":"Yakout","year":"2011","journal-title":"Arab. J. Chem."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"32","DOI":"10.1016\/j.cej.2007.08.032","article-title":"Activated carbon from jackfruit peel waste by H3PO4 chemical activation: Pore structure and surface chemistry characterization","volume":"140","author":"Prahas","year":"2008","journal-title":"Chem. Eng. J."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"603","DOI":"10.1351\/pac198557040603","article-title":"Reporting Physisorption Data for Gas\/Solid Systems with Special Reference to the Determination of Surface Area and Porosity","volume":"57","author":"Sing","year":"1985","journal-title":"Pure Appl. Chem."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"8214","DOI":"10.1021\/la050068y","article-title":"Hysteresis and Scanning Behavior of Mesoporous Molecular Sieves","volume":"21","author":"Tompsett","year":"2005","journal-title":"Langmuir"},{"key":"ref_38","unstructured":"Gregg, S.J., and Sing, K.S.W. (1982). Adsorption, Surface Area, and Porosity, Academic Press. [2nd ed.]."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"206","DOI":"10.1016\/j.cherd.2010.05.005","article-title":"Production of activated carbon from olive bagasse by physical activation","volume":"89","author":"Demiral","year":"2011","journal-title":"Chem. Eng. Res. Des."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"269","DOI":"10.1016\/j.ibiod.2017.07.011","article-title":"Microwave assisted synthesis and characterization of a ternary flocculant from chitosan, acrylamide and lignin","volume":"123","author":"Cui","year":"2017","journal-title":"Int. Biodeterior. Biodegrad."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"6105","DOI":"10.3390\/ma7096105","article-title":"Native Cellulose: Structure, Characterization and Thermal Properties","volume":"7","author":"Poletto","year":"2014","journal-title":"Materials"},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"1326","DOI":"10.1007\/s10924-020-01685-z","article-title":"Development and Characterization of Lignin Microparticles for Physical and Antioxidant Enhancement of Biodegradable Polymers","volume":"28","author":"Gomide","year":"2020","journal-title":"J. Polym. Environ."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"587","DOI":"10.1007\/s00226-021-01286-6","article-title":"Understanding the local structure of disordered carbons from cellulose and lignin","volume":"55","author":"Meng","year":"2021","journal-title":"Wood Sci. Technol."},{"key":"ref_44","doi-asserted-by":"crossref","unstructured":"Gea, S., Siregar, A.H., Zaidar, E., Harahap, M., Indrawan, D.P., and Perangin-Angin, Y.A. (2020). Isolation and Characterisation of Cellulose Nanofibre and Lignin from Oil Palm Empty Fruit Bunches. Materials, 13.","DOI":"10.3390\/ma13102290"},{"key":"ref_45","doi-asserted-by":"crossref","unstructured":"Frikha, K., Limousy, L., Arif, M.B., Thevenin, N., Ruidavets, L., Zbair, M., and Bennici, S. (2021). Exhausted Grape Marc Derived Biochars: Effect of Pyrolysis Temperature on the Yield and Quality of Biochar for Soil Amendment. Sustainability, 13.","DOI":"10.3390\/su132011187"},{"key":"ref_46","doi-asserted-by":"crossref","unstructured":"Mourgkogiannis, N., Nikolopoulos, I., Kordouli, E., Lycourghiotis, A., Kordulis, C., and Karapanagioti, H.K. (2024). The Influence of Biowaste Type on the Physicochemical and Sorptive Characteristics of Corresponding Biochar Used as Sustainable Sorbent. Sustainability, 16.","DOI":"10.3390\/su16072889"},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"161010","DOI":"10.1016\/j.scitotenv.2022.161010","article-title":"Transformation of phosphorus species during phosphoric acid-assisted pyrolysis of lignocellulose","volume":"866","author":"Chu","year":"2023","journal-title":"Sci. Total Environ."},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"80","DOI":"10.1016\/j.wsee.2022.12.001","article-title":"Synthesis, characterization, and photocatalytic degradation of anionic dyes using a novel ZnO\/activated carbon composite","volume":"5","author":"Machrouhi","year":"2023","journal-title":"Watershed Ecol. Environ."},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"155","DOI":"10.1016\/j.clay.2018.11.007","article-title":"Novel hierarchically porous allophane\/diatomite nanocomposite for benzene adsorption","volume":"168","author":"Deng","year":"2019","journal-title":"Appl. Clay Sci."},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/S0167-2991(08)61303-8","article-title":"Characterization of porous solids: An introductory survey","volume":"Volume 62","author":"Sing","year":"1991","journal-title":"Studies in Surface Science and Catalysis"},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"312","DOI":"10.1007\/s12209-019-00186-y","article-title":"Removal of Toluene by Adsorption\/Desorption Using Ultra-stable Y Zeolite","volume":"25","author":"Xu","year":"2019","journal-title":"Trans. Tianjin Univ."},{"key":"ref_52","doi-asserted-by":"crossref","first-page":"139821","DOI":"10.1016\/j.molstruc.2024.139821","article-title":"ZnO NPs-modified biochar derived from banana peels for adsorptive removal of methylene blue from water","volume":"1321","author":"Essa","year":"2025","journal-title":"J. Mol. Struct."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/30\/23\/4505\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,11,24]],"date-time":"2025-11-24T13:09:48Z","timestamp":1763989788000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/30\/23\/4505"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2025,11,22]]},"references-count":52,"journal-issue":{"issue":"23","published-online":{"date-parts":[[2025,12]]}},"alternative-id":["molecules30234505"],"URL":"https:\/\/doi.org\/10.3390\/molecules30234505","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2025,11,22]]}}}