PL228402B1 - Method for producing activated carbon from molasses - Google Patents

Description

(21) Filing Number: 404248 (®1) Int.CI.

C01B 32/318 (2017.01)

Patent Office of the Republic of Poland (22) Date of application: 07/06/2013 (54) Manufacturing method of activated carbon from molasses

(73) The right holder of the patent: (43) Application was announced: 08/12/2014 BUP 25/14 (45) The grant of the patent was announced: WEST POMERANIAN UNIVERSITY OF TECHNOLOGY IN SZCZECIN, Szczecin, PL (72) Inventor (s): BEATA MICHALKIEWICZ, Szczecin, PL KAROLINA MENCFELD, Chociwel, PL WERONIKA KAMIŃSKA, Gościm, PL 30/03/2018 WUP 03/18 (74) Representative: thing, pat. Renata Zawadzka

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PL 228 402 B1

Description of the invention

The subject of the invention is a method of producing activated carbon from molasses - a by-product of the production of sugar from sugar cane or sugar beet.

Industrial activated carbon is obtained in the process of carbonization and activation of materials containing elemental carbon. The carbonization stage consists in annealing at a temperature of 500-900 ° C without access to air of solid organic raw material. The resulting intermediate is then activated by chemical or physical factors. Chemical activation consists in treating the char with solutions of liquid inorganic compounds. The mixture is dried and subjected to heat treatment at a temperature of 400-900 ° C. The most popular activators are: KOH, NaOH, H3PO4, ZnCl2. The end product is active carbon with high porosity and a strongly developed specific surface.

The production of activated carbons is based on natural organic raw materials with a polymeric structure. Wood (35% share in the total consumption of raw materials), hard coal (28%), lignite (14%), peat (10%) are used on a large scale for this purpose, and locally such waste products, nut shells or fruit seeds (10% ). Currently, a lot of research is devoted to obtaining activated carbons from waste materials. Primarily suitable by-products from the food industry. They are known from the literature of M. Ahmedn, W.E. Marshall, R.M. Rao, Bioresource Technology 71 (2000) 113, and F. Rodriguez-Reinoso, Y. Nakagawa, J. Silvestre-Albero, J.M. Juarez-Galan, M. Molina-Sahio, Microporous and Mesoporous Materials 115 (2008) 603, N. Spahisa, A. Addounb, H. Mahmoudia, N. Ghaffourc, Desalination 222 (2008) 519 methods of making porous carbon materials using olive pits . In the literature, N. Bagheri, J, Abdei, Chem Eng Res Des. (2011), DOI: 10.1016 / j.cherd.2011.02.002, the use of corn on the cob for the production of carbon materials is described. The description of the Polish patent application P386878 describes a method of producing porous carbon material from appropriately prepared taqua nuts from the Phytelephas macrocarpa palm. In the publication of Y. Chen, Y. Zhu, Z. Wang, Y. Li, L. Wang, L. Ding, X. Gao, Y. Ma, Y. Guo, Advances in Colloid and Interface Science 163 (2011) 39 indicates the possibility of using rice husks as a substrate to obtain active carbons with a large specific surface. In addition, the apricot kernels described by C. Sentorun-Shalaby, M.G. Ucak-Astarlioglu, L. Artok, C. Sarici, Microporous and Mesoporous Materials 88 (2006), 126, peach pits described in the literature C. Gomez-de-Salazar, A. Sepulveda-Escribano, F. Rodriguez-Reinoso, Adsorption 11 , (2005), 663, fruit shells reported in literature D. Prahas, Y, Karlika, N. Indraswati, S. Ismadji, Chemical Engineering Journal 140 (2008), 32, or nut shells described by E. David, A. Talaie , V. Stanciu, A. Nicolae, Journal of Materials Processing Technology 157, (2004), 290. In addition, they are known from the literature of G. Bello, AR Garc, R. Arriagada, A. Sepulveda-Escribano, F. Rodr Guez-Reinoso, Microporous and Mesoporous Materials 56, (2002), 139 and G. Onyestyak, A. Bota, Microporous and Mesoporous Materials 120, (2009), 84 methods of obtaining active carbons from eucalyptus wood and spruce, oak and beech wood. There are also known methods of obtaining activated carbons from palm shells described by M. Ahmad, W. WanDaud, M. Aroua, Journal of Porous Materials 14, (2007), 393 and from coconut shells presented by D.C.S. Azevedo, J.C.S. Araujo, M. Bastos-Neto, A. Eurico, B. Torres, E.F. Jaguaribe, C.L. Cavalcante, Microporous and Mesoporous Materials 100, (2007), 361.

Obtaining activated carbon from molasses - a by-product of sugar production has been described in the publication by one group of researchers: K. Legrouri, E. Khouya, M. Ezzine, H. Hannache, R. Denoyel, R. Pallier, R. Naslain, Journal of Hazardous Materials B 118, (205), 259. Their method of preparation is that a 37 N solution of sulfuric acid as activator was added to molasses in the liquid state, and then the samples were carbonized under nitrogen and water vapor. Obtained by this method of active carbon having surface area 1214 m ² / g.

From the Polish patent application P. 397285 there is known a method of producing activated carbon from molasses, which consists in drying beet and / or sugar cane molasses at a temperature of 70 ° C to 200 ° C, then grinding and impregnating the obtained powder activator in a weight ratio of 1: 0.1-15. The mixture is dried at a temperature of from 80 ° C to 150 ° C, and the obtained product is ground and carbonized in an atmosphere of a chemically inert gas at a temperature of 400 ° C to 1000 ° C. The carbon material is then treated with HCl solution, then washed with distilled water and dried at 50 ° C to 250 ° C to obtain activated carbon. Preferably, KOH club NaOH and / or ZnCl ₂ and / or Na ₂ CO 3 and / or K ₂ CO 3 are used as activator. Preferably an inert gas

The chemical is administered at a rate of 100-700 ml / min. Preferably, nitrogen or argon is used as the chemically inert gas.

It has surprisingly turned out that it is possible to obtain activated carbon without having to dry the molasses and prepare an activator solution.

The method of producing activated carbon from molasses according to the invention, consisting in adding an activator to molasses, drying the mixture obtained, grinding it and carbonating it in a chemically inert gas at a temperature of 400 ° C to 1000 ° C, treating the carbon material with HCl solution, washing with distilled water and drying at a temperature of 50 ° C to 250 ° C, characterized in that the undried, liquid molasses is mixed with a solid activator in a weight ratio of 1: 0.1-20, then the mixture is dried at a temperature of 80 ° C up to 200 ° C. KOH and / or NaOH and / or ZnCl2 and / or Na2CO3 and / or K2CO3 are used as activators. Preference is given to using cane and / or beet molasses. Preferably, the chemically inert gas is fed at a rate of 100-700 ml / min. Preferably, nitrogen or any noble gas is used as the chemically inert gas.

The method according to the invention allows to obtain active carbon with a high specific surface area of 200-2500 m ² / g from a waste product from sugar production, which is molasses. The proposed method makes it possible to obtain activated carbon from liquid molasses, thus omitting the drying stage, using KOH, NaOH, ZnCl2, Na2CO3, K2CO3 as the activator. The advantage of the process is that generally accepted methods of producing activated carbons using the new raw material are applied. This means that it would be simple and cheap to adapt existing installations producing activated carbon from traditional raw materials to the proposed method. The omission of the molasses drying step and the use of activators in a solid form, rather than the usual solution, saves time and energy during the process.

The subject of the invention is illustrated in the following examples. The specific surface area of the obtained activated carbons was determined by liquid nitrogen adsorption using the BET method.

Example 1 g of liquid cane molasses was mixed with a NaOH activator in a weight ratio of 1: 0.7 and left for 3 hours. The mixture was then dried at 200 ° C. The powdered material was carbonized under an inert gas - nitrogen atmosphere (100 ml / min) at a temperature of 650 ° C. The carbon material was then treated with 5 N HCl, washed with distilled water and dried at 150 ° C. The specific surface area of the thus obtained activated carbon was 2470 m ² / g.

Example 2 g of liquid cane molasses are mixed with a 1:10 weight ratio KOH activator and left for 3 hours. The mixture was then dried at 100 ° C. The powdered material was carbonized under an inert atmosphere of argon (300 ml / min) at a temperature of 800 ° C. The carbon material was then treated with 5 N HCl, washed with distilled water and dried at 200 ° C. The specific surface area of the thus obtained activated carbon was 1070 m ² / g.

Example 3 g of liquid cane molasses was mixed with Na2CO3 activator in a weight ratio of 1:20 and left for 2 hours. The mixture was then dried at 100 ° C. The powdered material was carbonized under an inert atmosphere of argon (300 ml / min) at a temperature of 400 ° C. The carbon material was then treated with 5 N HCl, washed with distilled water and dried at 100 ° C. The specific surface area of the thus obtained activated carbon was 410 m ² / g.

Example 4 g of liquid cane molasses was mixed with activator K 2 CO 3 in a weight ratio of 1: 4 and left for 3 hours. The mixture was then dried at 80 ° C. The powdered material was carbonized under an inert atmosphere of helium (300 ml / min) at 800 ° C. The carbon material was then treated with 5 N HCl, washed with distilled water and dried at 180 ° C.

The specific surface area of the thus obtained activated carbon was 780 m ² / g.

Example 5 g of liquid cane molasses are mixed with a ZnCl2 activator in a weight ratio of 1:10 and left for 1 hour. The mixture was then dried at 110 ° C. The powdered material was carbonized under an inert gas - nitrogen atmosphere (550 ml / min) at 1000 ° C. The carbon material was then treated with 5 N HCl, washed with distilled water and dried at 160 ° C. The specific surface area of the thus obtained activated carbon was 980 m ² / g.

PL 228 402 B1

Example 6 g of liquid cane molasses were mixed with activator NaOH and KOH in a weight ratio of 1: 1: 1 and left for 4 hours. The mixture was then dried at 130 ° C. The powdered material was carbonized under an inert atmosphere of argon (150 ml / min) at 1000 ° C. The carbon material was then treated with 5 N HCl, washed with distilled water and dried at 200 ° C. The specific surface area of the thus obtained activated carbon was 1270 m ² / g.

Example 7 g of liquid cane molasses were mixed with activator KOH and Na2CO3 in a weight ratio of 1: 2: 1 and left for 3 hours. The mixture was then dried at 140 ° C. The powdered material was carbonized under an inert gas - nitrogen atmosphere (850 ml / min) at a temperature of 500 ° C. The carbon material was then treated with 5 N HCl, washed with distilled water and dried at 200 ° C. The specific surface area of the thus obtained activated carbon was 1030 m ² / g.

Example 8 g of liquid cane molasses was mixed with a ZnCl2 activator in a weight ratio of 1: 0.1 and left for 3 hours. The mixture was then dried at 120 ° C. The powdered material was carbonized under an inert gas - nitrogen atmosphere (900 ml / min) at a temperature of 900 ° C. The carbon material was then treated with 5 N HCl, washed with distilled water and dried at 50 ° C. The specific surface area of the thus obtained activated carbon was 500 m ² / g.

Example 9 g of liquid cane molasses were mixed with an activator of NaOH and ZnCl2 in a weight ratio of 1: 0.5: 1 and left for 4 hours. The mixture was then dried at 160 ° C. The powdered material was carbonized under an inert gas - nitrogen atmosphere (400 ml / min) at a temperature of 900 ° C. The carbon material was then treated with 5 N HCl, washed with distilled water and dried at 200 ° C. The specific surface area of the thus obtained activated carbon was 950 m ² / g.

Example 10 g of liquid cane molasses was mixed with the activator Na2CO2, K2CO3 in a weight ratio of 1: 5: 5 and left for 5 hours. The mixture was then dried at 140 ° C. The powdered material was carbonized under an inert gas - nitrogen atmosphere (600 ml / min) at a temperature of 750 ° C. The carbon material was then treated with 5 N HCl, washed with distilled water and dried at 250 ° C. The specific surface area of the thus obtained activated carbon was 1320 m ² / g.

Claims (4)

Patent claims 1. The method of producing activated carbon from molasses consisting in adding an activator to molasses, drying the obtained mixture, its grinding and carbonization in a chemically inert gas at a temperature of 400 ° C to 1000 m ² / g, treating the carbon material with HCl solution, washing with distilled water and drying at a temperature of 50 ° C to 250 ° C, characterized in that the undried liquid molasses is mixed with a solid activator in a weight ratio of 1: 0.1-20, and the mixture is dried at a temperature of 80 ° C to 200 ° C, using KOH and or NaOH and / or ZnCl2 and or Na2CO3 and or K2CO3 as activator. 2. The method according to p. The process of claim 1, characterized in that cane and / or beet molasses is used. 3. The method according to p. The process of claim 1, characterized in that the chemically inert gas is fed at a rate of 100-900 ml min. 4. The method according to p. The process of claim 1, wherein the chemically inert gas is nitrogen or any noble gas.