Cellulose Hydrolysis Using Hydrogen Chloride Gas-Air Mixtures

Authors

DOI:

https://doi.org/10.37482/0536-1036-2022-3-191-202

Keywords:

microcrystalline cellulose, microcrystalline cellulose hydrolysis, hydrogen chloride, degree of polymerization, hydrogen chloride adsorption by cellulose, gas-air mixtures

Abstract

Abstract. Microcrystalline cellulose (MCC) is a common product used in pharmaceutical, food and other industries. MCC is obtained by liquid-phase hydrolysis of cotton or wood bleached pulp with diluted 0.5–10.0 % mineral acids at a temperature of 100–140 °C. This process requires significant consumption of acid, water, and heat energy. Production of MCC in general is very expensive, which determines its high cost and the need to find alternative methods of cellulose hydrolysis. It is proposed to hydrolyze cellulose with concentrated hydrochloric acid produced by absorption of hydrogen chloride. We studied the processes of hydrogen chloride adsorption by bleached wood pulp with 8–18 % humidity. It is shown that adsorption of hydrogen chloride is determined by pulp humidity and is 3–5 % of the dry pulp mass. The sorption of hydrogen chloride leads to the formation of hydrochloric acid with a concentration of 25–40 % in the raw material moisture, significant heating of the mass and rapid hydrolysis of the amorphous cellulose fraction. It has been found that the use of pure hydrogen chloride for saturation causes strong darkening and humification of pulp. We recommend the use of hydrogen chloride gas-air mixtures to saturate the pulp, which will significantly reduce the sorption temperature and eliminate the strong darkening of the pulp during hydrolysis. The adsorption of hydrogen chloride by cellulose proceeds at an extremely high rate and is accompanied by the formation of a clearly visible sorption front at a temperature of 45–60 °C. Hydrolysis occurs for 15–30 min at 40–60 °C until the amorphous cellulose fraction is completely decomposed. A very small amount of monosaccharides is formed (4 % of dry pulp). The yield of MCC is high, more than 95 %. These circumstances are probably related to the recrystallization of a part of the amorphous fragments of cellulose macromolecules, which is a characteristic of hydrolysis with concentrated acids. The product obtained by cellulose hydrolysis is identical to MCC according to the data of IR spectroscopy, X-ray diffraction and viscometry. The article shows the high efficiency of cellulose hydrolysis with hydrogen chloride gas-air mixtures compared to traditional methods of MCC production.

Downloads

Download data is not yet available.

Author Biographies

Sergey D. Pimenov, Saint Petersburg State Forest Technical University

Postgraduate Student; ResearcherID: AAC-9435-2020

Georgy V. Mzokov, Saint Petersburg State Forest Technical University

Process Engineer; ResearcherID: AAD-5436-2020

Alexander I. Sizov, Saint Petersburg State Forest Technical University

Candidate of Engineering, Assoc. Prof.; ResearcherID: AAI-2030-2020

References

Болтовский В.С. Способы получения микрокристаллической целлюлозы // Тр. БГТУ . Сер. 2: Химические технологии, биотехнологии, геоэкология. 2021. № 1(241). С. 40–50. Boltovskiy V.S. Production Method Microcrystalline Cellulose (Review). Proceedings of BSTU, issue 2, Chemical Engineering, Biotechnologies, Geoecology, 2021, no. 1 (241), pp. 40–50. (In Russ.). https://doi.org/10.52065/2520-2669-2021-241-1-40-50

Емельянова И.З. Химико-технический контроль гидролизных производств. М.: Лесн. пром-сть, 1976. 328 с. Emel’yanova I.Z. Chemical and Engineering Control of Hydrolysis Production. Moscow, Lesnaya promyshlennost’ Publ., 1976. 328 p. (In Russ.).

Левинский М.И., Мазанко А.Ф., Новиков И.Н. Хлористый водород и соляная кислота. М.: Химия, 1985. 157 с. Levinskiy M.I., Mazanko A.F., Novikov I.N. Hydrogen Chloride and Hydrochloric Acid. Moscow, Khimiya Publ., 1985. 157 p. (In Russ.).

Носкова О.А., Зырянова О.А., Вельможин С.Д. Использование древесной целлюлозы для получения беленой порошковой целлюлозы // Вестн. ПНИПУ . Химическая технология и биотехнология. 2016. № 4. С. 57–69. Noskova O.A., Zyryanova O.A., Velmozhin S.D. Application of the Wood Pulp for Receiving Bleached Powder Cellulose. PNRPU Bulletin. Chemical Technology and Biotechnology, 2016, no. 4, pp. 57–69. (In Russ.). https://doi.org/10.15593/22249400/2016.4.04

Патент 2188208 С1 РФ. Способ получения микрокристаллической целлюлозы: № 2001110549/04: заявл. 17.04.2001: опубл. 27.08.2002 / Ф.Х. Хакимова, Т.Н. Ковтун, О.А. Носкова. Khakimova F.Kh., Kovtun T.N., Noskova O.A. Method for Production of Microcrystalline Cellulose. Patent RF no. RU 2 188 208 C1, 2002. (In Russ.).

Патент 2192432 С1 РФ. Способ получения порошковой целлюлозы: № 2001120616/04: заявл. 23.07.2001: опубл. 10.11.2002 / Ф.Х. Хакимова, Т.Н. Ковтун, О.А. Носкова, А.Я. Перевалов. Khakimova F.Kh., Kovtun T.N., Noskova O.A., Perevalov A.Ja. Method of Production of Powder Cellulose. Patent RF no. RU 2 192 432 C1, 2002. (In Russ.).

Пименов С.Д. Разработка способа получения гидролизат-массы из древесной целлюлозы для производства МКЦ : выпуск. квалификац. работа магистра. СП б.: СП б ГЛТУ , 2019. С. 71. Pimenov S.D. Development of a Method for Obtaining Hydrolyzate Mass from Wood Pulp for the Production of MCC: Master’s Thesis. Saint Petersburg, SPbFTU Publ., 2019, p. 71. (In Russ.).

Сарымсаков А.А., Балтаева М.М., Набиев Д.С., Рашидова С.Ш., Югай С.М. Диспергированная микрокристаллическая целлюлоза и гидрогели на ее основе // Химия растит. сырья. 2004. № 2. С. 11–16. Sarymsakov A.A., Baltayeva M.M., Nabiyev D.S., Rashidova S.Sh., Yugay S.M. Dispersed Microcrystalline Cellulose and Hydrogels Based on It. Khimija Rastitel’nogo Syr’ja = Chemistry of Plant Raw Materials, 2004, no. 2, pp. 11–16. (In Russ.).

Справочник химика / под ред. Б.П. Никольского. 2-е изд., перераб. и доп. Т. 3: Химическое равновесие и кинетика. Свойства растворов. Электродные процессы. М.; Л.: Химия, 1965. 1005 с. Handbook of a Chemist. Ed. by Nikol’skiy. Vol. 3: Chemical Equilibrium and Kinetics. The properties of solutions. Electrode processes. Moscow, Khimiya Publ., 1965. 1005 p. (In Russ.).

Сунайт В.Н. Получение порошковой целлюлозы из древесной массы: дис. … канд. техн. наук. СП б., 2019. 134 с. Sunayt V.N. Obtaining Powder Cellulose from Wood Pulp: Cand. Eng. Sci. Diss. Saint Petersburg, 2019. 134 p. (In Russ.).

Холькин Ю.И. Технология гидролизных производств М.: Лесн. пром-сть, 1989. 496 с. Khol’kin Yu.I. Hydrolysis Production Technology. Moscow, Lesnaya promyshlennost’ Publ., 1989. 496 p. (In Russ.).

Целлюлоза и ее производные / под ред. Н. Байклза и Л. Сегала; пер. с англ. под ред. З.А. Роговина. Т. 2. М.: Мир, 1974. 510 с. Cellulose and Cellulose Derivatives. Ed. by N.M. Bikles, L. Segal. Transl. from English. Ed. by Z.A. Rogovin. Moscow, Mir Publ., 1974, vol. 2. 510 p. (In Russ.).

Чалов Н.В., Лещук А.Е. Непрерывный гидролиз полисахаридов растительной ткани 46–48 %-ной соляной кислотой. Сообщение 3. Поглощение хлористого водорода влажной древесиной // Изв. вузов. Лесн. журн. 1966. № 6. С. 139–143. Chalov N.V., Leshchuk A.E. Continuous Hydrolysis of Plant Tissue Polysaccharides with 46–48 % Hydrochloric Acid. Report 3. Absorption of Hydrogen Chloride by Wet Wood. Lesnoy Zhurnal = Russian Forest Journal, 1966, no. 6, pp. 139–143. (In Russ.). http://lesnoizhurnal.ru/apxiv/1966/201966.pdf

Шейхет Ф.И. Материаловедение химикатов, красителей и моющих средств. М.: Легкая индустрия, 1969. 323 с. Sheykhet F.I. Materials Science of Chemicals, Dyes and Detergents. Moscow, Legkaya industriya Publ., 1969. 323 p. (In Russ.).

Щербакова Т.П., Котельникова Н.Е., Быховцева Ю.В. Сравнительное изучение образцов порошковой и микрокристаллической целлюлозы различного природного происхождения. Физико-химические характеристики // Химия растит. сырья. 2011. № 3. С. 33–42. Shcherbakova T.P., Kotel’nikova N.E., Bykhovtseva Yu.V. Comparative Study of Samples of Powder and Microcrystalline Cellulose of Various Origin. Physical and Chemical Characteristics. Khimija Rastitel’nogo Syr’ja = Chemistry of Plant Raw Materials, 2011, no. 3, pp. 33–42. (In Russ.).

Battista O.A. Hydrolysis and Crystallization of Cellulose. Industrial and Engineering Chemistry, 1950, vol. 42, no. 3, pp. 502–507. https://doi.org/10.1021/ie50483a029

Battista O.A., Hill D., Smith P.A. Level-Off D.P Cellulose Products. Patent US no. 2,978,446, 1961.

Battista O.A., Smith P.A. Microcrystalline Cellulose. Industrial and Engineering Chemistry, 1962, vol. 54, no. 9, pp. 20–29. https://doi.org/10.1021/ie50633a003

Chaerunisaa A.Y., Sriwidodo S., Abdassah M. Microcrystalline Cellulose as Pharmaceutical Excipient. Pharmaceutical Formulation Design – Recent Practices. Ed. by U. Ahmad, J. Akhtar. London, IntechOpen, 2019. https://doi.org/10.5772/intechopen.88092

El-Sakhawy M., Hassan M.L. Physical and Mechanical Properties of Microcrystalline Cellulose Prepared from Agricultural Residues. Carbohydrate Polymers, 2007, vol. 67, iss. 1, pp. 1–10. https://doi.org/10.1016/j.carbpol.2006.04.009

Higgins F.J., Ho G.E. Hydrolysis of Cellulose Using HCl: A Comparison between Liquid Phase and Gaseous Phase Processes. Agricultural Wastes, 1982, vol. 4, iss. 2, pp. 97–116. https://doi.org/10.1016/0141-4607(82)90019-1

Huntley C.J., Crews K.D., Abdalla M.A., Russell A.E., Curry M.L. Influence of Strong Acid Hydrolysis Processing on the Thermal Stability and Crystallinity of Cellulose Isolated from Wheat Straw. International Journal of Chemical Engineering, 2015, vol. 2015, art. 658163. https://doi.org/10.1155/2015/658163

Ibrahim M.M., El-Zawawy W.K., Jüttke Y., Koschella A., Heinze T. Cellulose and Microcrystalline Cellulose from Rice Straw and Banana Plant Waste: Preparation and Characterization. Cellulose, 2013, vol. 20, pp. 2403–2416. https://doi.org/10.1007/s10570-0139992-5

Ioelovich M. Green Technology of Microcrystalline Cellulose. SITA, 2018, vol. 20, iss. 2, pp. 3–7.

Karppi A., Vuorenpalo V.-M., Robertsen L., Parviainen K., Dahl O., Vanhatalo K. Process for Producing Microcellulose. Patent CA no. CA 2801987 A1, 2011.

Microcrystalline Cellulose (MCC) Market by Application (Food & Beverage, Pharmaceutical, Cosmetics & Personal Care), Raw Material Source (Wood-based, Nonwoodbased), and Region (North America, Europe, APAC, RoW) – Global Forecasts to 2024. Report. 2019. 109 p. Available at: https://www.marketsandmarkets.com/Market-Reports/microcrystallinecellulose-market-59144224.html (accessed 12.12.19).

Palme A., Theliander H., Brelid H. Acid Hydrolysis of Cellulosic Fibres: Comparison of Bleached Kraft Pulp, Dissolving Pulps and Cotton Textile Cellulose. Carbohydrate Polymers, 2016, vol. 136, pp. 1281–1287. https://doi.org/10.1016/j.carbpol.2015.10.015

Park S., Baker J.O., Himmel M.E., Parilla P.A., Johnson D.K. Cellulose Crystallinity Index: Measurement Techniques and Their Impact On Interpreting Cellulase Performance. Biotechnology for Biofuels, 2010, vol. 3, art. 10. https://doi.org/10.1186/1754-6834-3-10

Segal L., Creely J.J., Martin A.E., Jr., Conrad C.M. An Empirical Method for Estimating the Degree of Crystallinity of Native Cellulose Using the X-Ray Diffractometer. Textile Research Journal, 1959, vol. 29, iss. 10, pp. 786–794. https://doi.org/10.1177/004051755902901003

Tan Z., Eustace S., Sestrick M., Ondov J. Method of Making Bleached Microcrystalline Cellulose. Patent EU no. EP 3 294 951 B1, 2016.

Vanhatalo K.M., Dahl O.P. Effect Acid Hydrolysis Parameters on Properties of Microcrystalline Cellulose. BioResources, 2014, vol. 9, no. 3, pp. 4729–4740. https://doi.org/10.15376/biores.9.3.4729-4740

Yusrina RRAK, Sutriyo, Suryadi H. Preparation and Characterization of Microcrystalline Cellulose Produced from Betung Bamboo (Dendrocalamus asper) through Acid Hydrolysis. Journal of Young Pharmacists, 2018, vol. 10, iss. 2, pp. s79–s83. https://doi.org/10.5530/jyp.2018.2s.15

Published

2022-06-08

How to Cite

Pimenov С. ., Mzokov Г. ., and Sizov А. . “Cellulose Hydrolysis Using Hydrogen Chloride Gas-Air Mixtures”. Lesnoy Zhurnal (Forestry Journal), no. 3, June 2022, pp. 191-02, doi:10.37482/0536-1036-2022-3-191-202.

Issue

Section

TECHNOLOGY OF WOOD CHEMICAL PROCESSING AND PRODUCTION OF WOOD-POLYMER COMPOSITES