Patent DE-102010048614-A1 (DE)
Title: Extracting cellulose, hemicellulose and lignin, or lignin and tannin, comprises extracting cellulose and hemicellulose using (zwitterionic)iminium salts, precipitating the extracted cellulose or hemicelluloses, and separating
Inventor: KANTLEHNER WILLI PROF DR
IPC: D21C3/20
Filed: 2010-10-15
Abstract: Extracting cellulose, hemicellulose and lignin, or lignin and tannin, comprises extracting cellulose and hemicellulose using an iminium salts (guanidinium salts) and/or zwitterionic iminium salts (A); precipitating the extracted cellulose or hemicelluloses from the iminium salt solution; and separating, where the cellulose and hemicellulose are from recycled biogenic material (biomass comprising hardwood, softwood, bamboo and crop wastes comprising corn stalks, wheat straw, rice straw, sugar cane or hay) in the form of flour, chips or snip. Extracting cellulose, hemicellulose and lignin, or lignin and tannin, comprises extracting cellulose and hemicellulose using an iminium salts (guanidinium salts) and/or zwitterionic iminium salts (A) of formula (C +>(NR 1>R 2>)(NR 3>R 4>)(NR 5>R 6>)) (Ia), (C +>(NR 1>R 2>)(NR 3>R 4>)-N(R 5>)(Q-Z ->)) (Ib), R-C +>H-N(R 1>)(R 2>)(X ->) (II), (III)-(VI); precipitating the extracted cellulose or hemicelluloses from the iminium salt solution; and separating, where the cellulose and hemicellulose are from recycled biogenic material (biomass comprising hardwood, softwood, bamboo and crop wastes comprising corn stalks, wheat straw, rice straw, sugar cane or hay) in the form of flour, chips or snip. In formula (Ia) and (Ib): Either R 1>-R 6> : alicyclyl, aryl, aralkyl, alkylaryl or heteroaryl (all optionally substituted further by OH, CN, nitro, halo, alkoxycarbonyl or aminocarbonyl) or aliphatic alkyl; or R 1>R 2>, R 3>R 4>, R 5>R 6> : cyclic structures; or R 1>R 5>, R 4>R 6> : a chain form, provided that (Ia) or (Ib) further comprises a bi- or tricyclic heterocyclic cation of type 1, when R 1>and R 3>and simultaneously R 4>and R 5>and/or R 1>with R 3>and simultaneously R 4>and R 5>and R 2>and R 6>are connected; X -> : OH ->, RO ->, R-COO ->, R-SO 3 ->, SO 4 2> ->, HSO 4 ->, RO-SO 3 ->, PO 4 3> ->, HPO 4 2> ->, H 2PO 4 ->, P(=O)(OR)(O ->) 2, P(=O)(OR1a)(OR1b)(O ->), P(=O)(OR1a)(R)(O ->) or P(R)(O ->) 2; R, R1a, R2a : 1-12C-alkyl, 5-8C-cycloalkyl, aryl, aralkyl, alkylaryl or heteroaryl (all optionally substituted by OH, halo, CN, NO 2, COOH or SO 3H); and Q-Z -> : R 1>, SO 3 ->, OSO 3 ->, PO 3 ->, P(O)(OR)O ->, COO ->or CSS ->. In formula (II)-(VI): Either R : H, dialkylamino, alkoxy, aryloxy and/or organic group; and R 1>-R 4> : alicyclyl, aryl, aralkyl, alkylaryl or heteroaryl (all optionally substituted further by OH, CN, nitro, halo, alkoxycarbonyl or aminocarbonyl) or aliphatic alkyl; or R 1>R 2>, R 3>R 4>, RR 1>, R 1>R 3>, RR 2> : rings e.g. lactam iminium structures; Y 1> : R 1>, R-OSO 2-, R 2N-SO 2-, -SO 2-R, Hal 2P(O)-, (RO) 2P(O)-, HalP(O)(OR)- , sulfur analogue of phosphrous derivatives, R-P(O)(OR), R-P(O)Hal, Hal 2P, R 3P(Cl)- or acyl R-CO; Hal : F, Cl or Br; and X : F, Cl, Br, I, BF 4, Al(OR) 4, FeBr 4, ZnCl 4, SbCl 6, TiCl 6, sulfate, hydrogen sulfate, ROSO 3 ->, sulfite, bisulfite, ROSOO ->, R-SO 3 ->, phosphate, oligomeric phosphates, hydrogen phosphate, dihydrogen phosphate, RO-P(O)(OH)O ->, (RO) 2P(O)O ->, Hal 2P(O)O ->, R-P(OR) 2O ->, R-P(O)(OR)O ->, carbonate, hydrogen carbonate, bicarbonate, RO-CO 2 ->, RO-CS 2-, R-COO ->, phenolates, corresponding sulfur analogues, R-C(=O)-N ->-C(=O)-R 1>, R-C(=O)-N ->-SO 2-R 1>, R-SO 2-N ->-SO 2-R 1>, P(=O)(OR 1>)(R)-N ->SO 2-R 1>, R-C(=O)(OR 1>)-N ->-C(=O)-R 2>, RO-C(=O)-N ->-C(=O)-R 1>, (R 2>) 2N-C(=O)-N ->-C(=O)-R 1>, RO-C(=O)-N ->-C(=O)-OR, or R 2N-C(=O)-N ->-C(=O)-N(R 1>) 2. Provided that: In formula (III)-(VI), when X is absent, R, R 1>-R 4>or Y 1>are substituted by a negatively charged group comprising SO 3 ->, OSO 3 ->, -O-P(OR) 2 ->, -PO(OR)O ->, -COO ->or -CSS ->; (III) and (IV) forms zwitterionic adducts from amides, ureas or their thio analogs, and Lewis acids such as BF 3, BCl 3, SbCl 5, AlCl 3, TiCl 4, FeCl 3, SnCl 2, SnCl 4or ZnCl 2; and (III) and (IV) are unsteady or unknown iminium salt obtained from an acid amide and electrophilic reagent comprising PCl 3, PBr 3or cyanuric chloride. [Image].