ispltaИзвестия Санкт-Петербургской лесотехнической академииIzvestia Sankt-Peterburgskoj lesotehniceskoj akademii2079-43042658-5871СПбГЛТУ10.21266/2079-4304.2021.235.274-295isplta-230Research ArticleДРЕВЕСИНОВЕДЕНИЕ, ТЕХНОЛОГИЯ И ОБОРУДОВАНИЕ ДЕРЕВОПЕРЕРАБОТКИWOOD SCIENCE. MECHANICAL WOODWORKING INDUSTRYПолучение гидрогелей технических лигниновObtaining hydrogels of technical ligninsЕвстигнеевЭ. И.EvstigneyevE. I.

ЕВСТИГНЕЕВ Эдуард Иванович – профессор кафедры технологии лесохимических продуктов, химии древесины и биотехнологии, доктор химических наук

194021, Институтский пер., д. 5, Санкт-Петербург

EVSTIGNEYEV Edward I. – DSc (Chemistry), Professor, Department of technologies of timber-chemical products, chemistry of wood and biotechnology

194021. Institutsky per. 5. St. Petersburg

edward_evst@mail.ruГриненкоЕ. В.GrinenkoE. V.

ГРИНЕНКО Елена Владимировна – доцент кафедры химии, кандидат химических наук

194021, Институтский пер., д. 5. Санкт-Петербург

GRINENKO Elena V. – PhD (Chemistry), Assistant Professor of the Department of chemistry

194021. Institutsky per. 5. St. Petersburg

gip95@mail.ruВасильевА. В.VasilievA. V.

ВАСИЛЬЕВ Александр Викторович – заведующий кафедрой химии, доктор химических наук, профессор

194021, Институтский пер., д. 5, Санкт-Петербург

VASILYEV Aleksander V. – DSc (Chemistry), Head of the Department of chemistry

194021. Institutsky per. 5. St. Petersburg

aleksvasil@mail.ruСанкт-Петербургский государственный лесотехнический университет имени С.М. КироваРоссияSt. Petersburg State Technical UniversityRussian FederationСанкт-Петербургский государственный лесотехнический университет имени С.М. КироваРоссияSt.Petersburg State Forest Technical UniversityRussian Federation2021060320240235270291Copyright © Евстигнеев Э.И., Гриненко Е.В., Васильев А.В., 20242024Евстигнеев Э.И., Гриненко Е.В., Васильев А.В.Evstigneyev E.I., Grinenko E.V., Vasiliev A.V.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://izvestiya-lta.spbftu.ru/jour/article/view/230

Методами потенциометрического титрования, ИК-спектроскопии, твердофазной ЯМР-спектроскопии 13С и химического анализа исследовано гелеобразование технических лигнинов (окисленного гидролизного, сульфатного, натронного и лигносульфонатов) и лигнина Пеппера при взаимодействии с солями металлов: CaCl2, Mg(NO3)2,FeSO4, Co(NO3)2, Pb(NO3)2, Fe(NO3)3, CuSO4, AgNO3. Установлено, что способностью к гелеобразованию обладают соединения, представляющие собой соли слабого основания и сильной кислоты; катион металла имеет стандартный потенциал выше определенного значения, обладает умеренной способностью к гидролизу, а гидроксид катиона, образующийся в реакции гидролиза, имеет относительно низкую растворимость. При формировании геля образуется соединение состава R–COO–Mez+–OOC–R z = 2,3. Предложена схема межмолекулярных связей в точке образования гидрогеля лигнина, в соответствии с которой смежные молекулы лигнина связываются между собой тремя типами связей: ионной между карбоксильными группами лигнина и катионами металла, координационной между катионами металла и молекулами воды, входящими в координационную сферу; и водородными, связывающими все компоненты системы в единое целое. Гидрогели лигнина обладают высокой сорбционной способностью по отношению к тяжелым металлам, таким как свинец, железо и медь, составляющей в зависимости от содержания кислых групп в лигнине и молярной массы сорбата ~ 25–50% от массы лигнина. Это открывает возможность использовать новый вид гидрогелей лигнина для очистки сточных вод химических предприятий.

Potentiometric titration, IR-spectroscopy of 13C solid-state NMR spectroscopy, and chemical analysis were used to study the gelation of technical lignins (oxidized hydrolysis, Kraft, sodium, and lignosulfonates) and Pepper lignin in interaction with metal salts: CaCl2, Mg(NO3)2,FeSO4, Co(NO3)2, Pb(NO3)2, Fe(NO3)3, CuSO4, AgNO3. It has been established that compounds that are salts of a weak base and a strong acid have the ability to gelation; the metal cation has a standard potential above a certain value, has moderate hydrolysis ability, and the cation hydroxide formed in the hydrolysis reaction has a relatively low solubility. During gel formation, a compound of the composition R–COO–Mez+–OOC–R z = 2,3 is formed. A scheme of intermolecular bonds at the point of lignin hydrogel formation is proposed, according to which adjacent lignin molecules bind to each other by three types of bonds: ionic between carboxyl groups of lignin and metal cations, coordination between metal cations and water molecules included in the coordination sphere, and hydrogen connecting all the components of the system into a single whole. Lignin hydrogels have a high sorption ability with respect to heavy metals such as lead, iron and copper, which, depending on the content of acid groups in lignin and the molar mass of the sorbate, is ~ 25–50% by weight of lignin. This opens up the possibility of using a new type of lignin hydrogels for wastewater treatment of chemical plants.

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The authors declare that there are no conflicts of interest present.